Coating substrate

Abstract

The present invention provides a coated substrate comprising a transparent substrate having two major, opposed first and second surfaces, at least one surface of which is provided with a functional coating, the transparent substrate having at least SiO 2 deposited on and in contact with the functional coating. x , TiO y , and ZrO z (where x, y, and z are in the range of 1.8 to 2.2), the topcoat comprising 10 to 65 atomic % silicon, 8 to 38 atomic % titanium, and 25 to 80 atomic % zirconium, based on a total of 100 atomic % metals, and the topcoat has a thickness of 0.1 to 10 nm; a method for providing this coated substrate; and uses thereof.

Description

[Technical Field]

[0001] This invention relates to a functional coating and at least SiO x , TiO y , and ZrO z The present invention relates to a coated substrate provided with a magnetron-sputtered topcoat of a mixed metal oxide containing a mixed metal oxide, a method for providing the coated substrate, and the use of the topcoat. [Background technology]

[0002] Functional coatings, such as those containing magnetron-sputtered dielectric layers, are typically known to be susceptible to chemical and mechanical damage during their manufacture, transport, processing, storage, and / or handling. This limited mechanical resistance, chemical resistance, and corrosion resistance usually restricts their feasible use in contact with the external environment.

[0003] Various attempts are being made to provide glazing with coatings that have high chemical durability, mechanical durability, or both chemical and mechanical durability.

[0004] International Publication No. 2009115596A1 relates to a glazing comprising a thin-layer assembly deposited in a vacuum using a magnetron, which is essentially transparent and has lightfast and / or low emission properties, wherein the surface protective layer comprises a layer comprising titanium oxide and at least one other high-hardness metal oxide selected from the group including ZrO2, SiO2, and Cr2O3. The glazing of the above disclosure can withstand heat treatment at 550°C for 5 minutes without causing optical defects such as discoloration or pearlescent luster. In the mixed oxide, titanium oxide is present in a ratio of at least 40% by weight. The surface layer contains zirconium oxide in a ratio of 15-50% by weight.

[0005] International Publication No. 2010031808A1 relates to a glazing comprising at least one layer deposited by cathode spraying under vacuum, wherein the layer comprises one or more oxides, and the weight ratio of titanium oxide is at least 40% and 95% or less. The thickness of the layer in question, and optionally the thickness of another layer containing a metal oxide, is selected such that the layer provides at least 15% reflectance and at least 60% light transmittance on a 4 mm thick transparent "float" glass sheet. The layer or layer system in question further has mechanical resistance and / or chemical resistance equivalent to that of a layer produced by thermal decomposition to obtain a product having the same kind of optical properties.

[0006] However, the above solutions do not provide sufficient mechanical durability against the wear encountered during transport and storage conditions in typical dry brush tests and / or Automatic Wet Rub Tests (AWRTs).

[0007] International Publication No. 2018202595A1 relates to a coated substrate comprising a substrate, a soft coating provided on at least a portion of at least one surface of the substrate, a protective sol-gel coating provided on at least a portion of the aforementioned surface on the soft coating, a method for manufacturing such a coated substrate, and a glazing unit comprising such a coated substrate. The sol-gel coating comprises a mixture of titanium dioxide, silicon dioxide, and optionally bismuth oxide and / or cerium oxide in a theoretical weight ratio of titanium dioxide (TiO2) to silicon dioxide (SiO2) in the range of 0.10 to 3. If zirconium oxide is present, the zirconium oxide / silicon oxide ratio is in the range of 0.10 to 3. The titanium dioxide / zirconium oxide ratio is in the range of 0.10 to 10. The thickness of the sol-gel coating is typically in the range of 50 to 500 nm. The main drawback of this solution is the formation of a very thick protective layer, the need for an additional essential heating step to cure the sol-gel coating, and the resulting need for modifications to the production line, thus imposing further manufacturing constraints. In other words, an intermediate step is required where damage may occur before the coated substrate is protected by the sol-gel coating.

Summary of the Invention

Problems to be Solved by the Invention

[0008] There is still a need to develop a coated substrate, particularly a glass substrate, which is provided with a functional coating having improved mechanical resistance, chemical resistance, and corrosion resistance, but which has little impact on the emissivity and / or aesthetics of the coating.

[0009] There is still a need to develop a coated substrate, particularly a glass substrate, which is provided with a functional coating having improved mechanical resistance, chemical resistance, and corrosion resistance, but which has little impact on the emissivity and aesthetics of the coating, i.e., the optical properties of the functional coating are maintained.

Means for Solving the Problems

[0010] The object of the present invention is a coated substrate comprising a transparent substrate having two main opposite first and second surfaces, with a functional coating provided on at least one surface, wherein the transparent substrate has, on and in contact with the functional coating, at least SiO x , TiO y , and ZrO z (where x, y, z are in the range of 1.8 to 2.2) and a magnetron sputtered top coat of a mixed metal oxide is provided, the top coat contains, in total, for 100 atomic% of the metal, -10 to 65 atomic% of silicon, -8 to 38 atomic% of titanium, -25 to 80 atomic% of zirconium, and it is to provide a coated substrate characterized in that the top coat has a thickness of 0.1 to 10 nm.

[0011] A method for manufacturing the above coated substrate is also provided.

[0012] A heat-treated coated substrate and a plurality of glazing units are provided.

BRIEF DESCRIPTION OF THE DRAWINGS

[0013] This top coat is a magnetron sputtered mixed metal oxide containing at least SiO x , TiO y , and ZrO z (where x, y, z are in the range of 1.8 to 2.2), The top coat contains, in total for 100 atomic% of the metals including impurities, -10 to 65 atomic% silicon (Si), -8 to 38 atomic% titanium (Ti), -25 to 80 atomic% zirconium (Zr), and has a thickness of 0.1 to 10 nm. <00001​​​​​​​​​​​​The amount of each metal can be determined by methods available to those skilled in the art, such as X-ray photoelectron spectroscopy (XPS) and X-ray fluorescence (XRF). These analyses can be performed on a sputtered topcoat using common procedures well known in the art.

[0017] These amounts provide an optimal topcoat and, surprisingly, excellent mechanical durability against wear of functional coatings requiring transport or storage. Unexpectedly, contrary to the teachings in International Publication No. 2009115596A1, it was found that when titanium is used simultaneously with both silicon and zirconium to the extent requested, the required durability is not achieved with an amount of titanium oxide >40%.

[0018] This topcoat can have a thickness in the range of 0.1 to 10.0 nm, 0.5 to 5.0 nm, or 2.0 to 5.0 nm.

[0019] This thickness provides improved mechanical durability while simultaneously minimizing the optical contribution to the underlying functional coating. The topcoat is permanent in that it is not removed or altered by optional heat treatment of the transparent substrate. There is also no adverse effect on the optical properties of the underlying functional coating.

[0020] The refractive index n of this topcoat material within the claimed range depends on its final composition, but can be in the range of 1.90 to 2.25 at a wavelength of 550 nm.

[0021] The transparent substrate may be a glass substrate or a plastic substrate, such as poly(methyl meth)acrylate (PMMA), polycarbonate, polyethylene terephthalate (PET), polyolefin, polyvinyl chloride (PVC), or a mixture thereof. Transparency of the substrate is considered when T exceeds 10%, 20%, or 30%.

[0022] In most cases, transparent substrates are glass substrates.

[0023] The glass may be any type of glass, such as conventional float glass or plate glass, and may be any composition having any optical properties, for example, any value of visible light transmittance, ultraviolet light transmittance, infrared light transmittance, and / or total solar energy transmittance greater than 10%.

[0024] The glass substrate may be soda-lime glass, borosilicate glass, lead glass, or aluminosilicate glass. The substrate may be a regular transparent, colored, or ultra-transparent (i.e., lower Fe content and higher transmittance) glass substrate. Further examples of glass substrates include transparent, green, bronze, or blue-green glass substrates.

[0025] The glass may be annealed glass, tempered glass, or heat-strengthened glass.

[0026] The transparent glass substrate can have a thickness ranging from 0.5 mm to approximately 15 mm, or from 1 mm to approximately 10 mm, or from 1 mm to approximately 8 mm.

[0027] A transparent glass substrate can also be considered suitable for the present invention if it has a thickness in the range of 0.5 to 2 mm.

[0028] The transparent substrate typically has two main, opposite surfaces, a first and a second surface, with a functional coating provided on at least a portion of the first surface.

[0029] To protect the functional coating from mechanical and / or chemical damage during transport, storage, handling, processing, and / or final use, the topcoat is deposited on and in contact with at least a portion of the functional coating provided on at least one surface of a transparent substrate.

[0030] The same or different functional coatings can be applied to the second surface of the transparent substrate. In such cases, the topcoat can be applied on the functional coatings provided on one or both of the two coated surfaces, i.e., on one of the coatings on the first surface or the second surface, or on the coatings on both the first and second surfaces.

[0031] Within the scope of this invention, the term “functional coating” means a coating that alters one or more physical properties of a substrate, such as optical, thermal, chemical, or mechanical properties. Such functional coatings are not intended to be removed from the substrate during subsequent processing. Functional coatings are typically permanent or “non-removable” coatings.

[0032] Functional coatings may include solar control coatings, conductive coatings, anti-reflective coatings, decorative coatings, and / or low-emissivity coatings.

[0033] Functional coatings may be single-layer or thin-layer stacks, i.e., multilayer coatings, and may contain one or more metals, nonmetals, metalloids, semiconductors, or alloys, compounds, composite materials, combinations thereof, or blends thereof.

[0034] When discussing thin-layer stacks in this invention, it is typically understood that a first layer is first attached to the substrate, and then a second layer is attached on top of the first layer on the substrate. The sequential order of positions is considered starting from the substrate and progressing to the top layer.

[0035] Within the scope of this invention, the terms "down," "below," and "lower part" indicate the relative position of a layer facing the next layer within the layer order starting from the substrate. Within the scope of this invention, the terms "up" and "upper part" indicate the relative position of a layer facing the next layer within the layer order starting from the substrate.

[0036] Within the scope of the present invention, the relative positions of the layers in a stack do not necessarily indicate direct contact between the layers. That is, an intermediate layer may be provided between the first and second layers. For example, unless the object of the present invention is threatened, the first layer "deposited on top of" the substrate does not preclude the presence of one or more other coating layers of the same or different composition located between the film of the first layer and the substrate.

[0037] In some cases, a single layer may actually consist of several separate layers.

[0038] This topcoat is understood to be positioned above the functional coating applied to the first surface of the transparent substrate. That is, this topcoat is located furthest from the transparent substrate relative to the first deposited surface of the substrate and is typically in contact with air.

[0039] This topcoat is the outermost layer on top of the functional coating and is in direct contact with the final layer of the functional coating. In most cases, the final layer of the functional coating does not impart mechanical and / or chemical durability. In such cases, this topcoat imparts the mechanical and chemical durability of the functional coating.

[0040] In some cases, a functional coating may initially include a top coat that provides a certain degree of mechanical and / or chemical durability. In such cases, this top coat provides even greater mechanical and chemical durability to the functional coating, particularly considering abrasion.

[0041] Functional coatings can have a thickness in the range of 10 to 1000 nm.

[0042] Unless otherwise specified, all layer thicknesses here are geometric layer thicknesses.

[0043] In one embodiment of the present invention, the functional coating may be a solar control coating, wherein the solar control coating includes a coating that reflects or absorbs visible, infrared, or ultraviolet energy.

[0044] In one embodiment of the present invention, the functional coating may be a conductive coating, such as a coating for a conductive heating window, or a coating for a single or multilayer film that can function as an antenna.

[0045] Functional coatings may be low-emissivity coatings that typically allow visible wavelength energy, e.g., about 400 nm to about 780 nm, to pass through the coating, but can reflect shorter wavelength solar infrared energy and / or thermal infrared energy, and are typically intended to improve the thermal insulation properties of building glazing. "Low emissivity" means emissivity of less than about 0.3 or less than about 0.2.

[0046] The functional coating may be a single-layer metal oxide coating, a multi-layer metal oxide coating, a non-metal oxide coating, or a multi-layer coating.

[0047] In one embodiment of the present invention, the single-layer metal oxide coatings include zinc oxide doped with aluminum, gallium, or hafnium; mixed oxides of zinc and tin; tin oxide optionally doped with fluorine or antimony; and indium oxide optionally doped with tin.

[0048] In one embodiment of the present invention, the multilayer metal oxide coating includes a coating comprising at least one layer of a high refractive index material and at least one layer of a low refractive index material, i.e., a coating having layers of materials having alternating refractive indices. Such a coating is typically represented by a coating comprising a first layer of a material having a low or high refractive index, a second layer of a material having a high or low refractive index, a third layer of a material having a low or high refractive index, a fourth layer of a material having a high or low refractive index, and an optional protective layer. The low refractive index is typically a refractive index <1.8 or typically <1.7, while the high refractive index is typically a refractive index >1.8 or typically ≥1.9 or ≥2.0. Some layers may have intermediate refractive indices ranging from 1.7 to <1.9. The refractive index is typically considered at a wavelength of 550 nm.

[0049] In one embodiment of the present invention, the functional coating may be a multilayer coating comprising an alternating arrangement of n infrared reflective (IR) layers and n+1 dielectric layers, such that each IR layer is surrounded by two dielectric layers, where n≧1.

[0050] The IR layer may be made of silver, gold, palladium, platinum, or an alloy thereof. The functional layer may have a thickness of 2-30 nm, 5-20 nm, or 7-18 nm. These thickness ranges allow for good light transmittance while achieving the desired low emissivity and / or solar control function and / or conductivity.

[0051] The dielectric layer typically includes oxides, nitrides, oxynitrides, or oxycarbides of Zn, Sn, Ti, Zr, Si, In, Al, Bi, Ta, Hf, Mg, Nb, Y, Ga, Sb, Mg, Cu, Ni, Cr, Fe, B, or mixtures thereof.

[0052] In one embodiment of the present invention, the dielectric layer may include oxides, nitrides, oxynitrides, or oxycarbides of Zn, Sn, Ti, Zr, Si, In, Al, Nb, Sb, Ni, Cr, or mixtures thereof. Alternatively, the dielectric layer may include oxides, nitrides, or oxynitrides of Zn, Sn, Ti, Zr, Si, In, Al, Nb, Sb, Ni, Cr, or mixtures thereof.

[0053] These materials can ultimately be doped, and examples of dopants include aluminum, zirconium, or mixtures thereof. The dopant or dopant mixture can be present in amounts up to 15% by weight.

[0054] Typical examples of dielectric materials include, but are not limited to, silicon-based oxides, silicon-based nitrides, zinc oxide, tin oxide, mixed zinc-tin oxide, silicon nitride, silicon oxynitride, titanium oxide, aluminum oxide, zirconium oxide, niobium oxide, aluminum nitride, bismuth oxide, mixed zirconium silicon nitride, and mixtures of at least two of these, such as titanium zirconium oxide.

[0055] The dielectric layer may consist of a plurality of separate layers essentially comprising the above-mentioned material.

[0056] Each dielectric layer can have a thickness in the range of 0.1 to 200 nm, 0.1 to 150 nm, 1 to 120 nm, or 1 to 80 nm. Different dielectric layers can have different thicknesses. That is, the first dielectric layer can have a thickness that is the same as or different from the thickness of the second or third or any other dielectric layer, greater or less than that of the second or third or any other dielectric layer.

[0057] When there are two IR functional layers (n=2, the second dielectric layer is sandwiched between the two IR functional layers and can therefore be called the "internal dielectric layer").

[0058] When there are three IR functional layers (n=3), the second and third dielectric layers are sandwiched between the two IR functional layers, and can therefore be called "internal dielectric layers."

[0059] A multilayer coating may include a seed layer beneath at least one IR layer, and / or the coating may include a barrier layer above at least one IR layer. The seed layer is typically provided to facilitate the formation of a good quality film of the IR material, i.e., to obtain a uniform and stable layer of the IR material. The barrier layer is typically provided to facilitate the protection of the IR material from degradation induced by the formation of any layer above it, for example, to protect from oxygen or oxygen-containing species that may degrade the quality of the IR layer, and also to protect from degradation due to heat treatment.

[0060] A given IR layer may have either a seed layer or a barrier layer, or both. The first IR layer may have either a seed layer or a barrier layer, and the second IR layer may have either a seed layer or a barrier layer, and so on. Such configurations are not mutually exclusive. The seed layer and / or barrier layer may have a thickness of 0.1 to 35 nm, or 0.5 to 25 nm, or 0.5 to 15 nm, or 0.5 to 10 nm.

[0061] The multilayer coating may also include a thin layer of sacrificial material having a thickness of <15 nm or <9 nm, provided on and in contact with at least one functional layer. Examples of sacrificial materials include titanium, zinc, nickel, chromium, Ni oxides, Ni alloy oxides, Cr oxides, Cr alloy oxides, and NiCrO x NiCrO x N y Examples include zinc oxide, tin oxide, or other suitable materials, or mixtures thereof.

[0062] An absorbent layer can be provided in the dielectric layer to selectively change the transmittance of the coated article. In one example, the thickness of the absorbent layer can be adjusted so that the transmittance of the coated article is significantly adjusted without adversely affecting the color. Examples of absorbent layers include Ni, Cr, NiCr, and NiCrN. x , NiCrW, CrN, ZrN, TiN, Ti, Zr, NiO x These are some examples. Such an absorption layer can be arranged such that at least one IR layer is located above the absorption layer, and optionally such an absorption layer can be sandwiched between and in contact with first and second layers containing silicon nitride. The absorption layer can have a thickness in the range of 0.5 to 10 nm.

[0063] The multilayer coating may already include, in some cases, a top layer containing an oxide of Ti, Zr, or a mixed oxide of Ti and Zr having 45-65 wt% Ti; or an oxide of Si, Al; or an oxide of Zr and Al; or a nitride of Si, Al. Such a top layer can be replaced with this topcoat, or this topcoat can be applied on top of such a top layer.

[0064] A first example of a multilayer coating that functions as a low emissivity coating is a layer comprising at least one silver layer, but in the order of substrate / MeO / ZnO:AlSi / Ag / AlSi-MeO, where MeO is a metal oxide such as SnO2, TiO2, In2O3, Bi2O3, ZrO2, Ta2O5, SiO2, or Al2O3, or a mixture thereof.

[0065] A second example of a multilayer coating that functions as a low-emissivity coating includes: a first dielectric layer containing silicon nitride; a first layer containing Ni or NiCr; an infrared (IR) reflective layer containing silver; a second layer containing Ni or NiCr; and a second dielectric layer containing silicon nitride. Such a multilayer coating may optionally include a topcoat of mixed (oxy)nitrides of SiZr or mixed oxides of TiZr.

[0066] A third example of multilayer coating is, It includes an infrared (IR) reflective layer in contact with and sandwiched between the first and second layers, the second layer comprising NiCrOx; At a minimum, the second layer containing NiCrOx is oxidized in steps such that the first portion of the second layer closer to the infrared (IR) reflective layer is oxidized less than the second portion of the second layer further away from the infrared (IR) reflective layer.

[0067] A fourth example of a multilayer coating includes: a dielectric layer; a first layer containing zinc oxide located on the dielectric layer; an infrared (IR) reflective layer containing silver located on and in contact with the first layer containing zinc oxide; a layer containing NiCr oxide located on and in contact with the IR reflective layer; a second layer containing zinc oxide located on and in contact with the layer containing NiCr oxide; and another dielectric layer located on the second layer containing zinc oxide.

[0068] A fifth example of a multilayer coating includes: a first dielectric layer; a first infrared (IR) reflective layer containing silver located at least on the first dielectric layer; a first layer containing zinc oxide located at least on the first IR reflective layer and the first dielectric layer; a second IR reflective layer containing silver located on and in contact with the first layer containing zinc oxide; a layer containing NiCr oxide located on and in contact with the second IR reflective layer; a second layer containing zinc oxide located on and in contact with the layer containing NiCr oxide; and at least another dielectric layer located on the second layer containing zinc oxide.

[0069] A sixth example of a multilayer coating includes: a first dielectric layer; a first layer containing zinc oxide located on the dielectric layer; an infrared (IR) reflective layer containing silver located on and in contact with the first layer containing zinc oxide; a second layer containing zinc oxide located on the IR layer; and a second dielectric layer located on the second layer containing zinc oxide. The first and second dielectric layers may include multiple layers, in particular layers of various compositions in zinc oxide, i.e., layers of zinc oxide, layers of aluminum-doped zinc oxide, or layers of mixed zinc and tin oxides having a ratio of Sn / Zn in the range of 0.5 to 2 by weight, or a ratio of Sn / Zn in the range of 0.02 to 0.5 by weight; layers of silicon nitride; and layers of titanium oxide. The first and second layers containing zinc oxide may also have various compositions in zinc oxide, i.e., in particular layers of zinc oxide; aluminum-doped zinc oxide; mixed zinc and tin oxides; and mixed zinc, titanium, and aluminum oxides.

[0070] A seventh example of a multilayer coating includes, in order: a first dielectric layer; a first IR layer containing silver; a second dielectric layer; a second IR layer; and a third dielectric layer. The first, second, and third dielectric layers may include multiple layers, in particular layers of various compositions in zinc oxide, i.e., layers of zinc oxide, layers of aluminum-doped zinc oxide, or layers of mixed zinc and tin oxides having a ratio of Sn / Zn in the range of 0.5 to 2 by weight, or a ratio of Sn / Zn in the range of 0.02 to 0.5 by weight; layers of mixed zinc, titanium, and aluminum oxides; layers of silicon nitride; and layers of titanium oxide. In some cases, the IR layers may independently include metal barrier layers such as Ti, Ni, and NiCr.

[0071] An eighth example of a multilayer coating includes, in order: a first dielectric layer; a first IR layer containing silver; a second dielectric layer; a second IR layer; a third dielectric layer; a third IR layer; and a fourth dielectric layer. The first, second, third, and fourth dielectric layers may include multiple layers, in particular layers of various compositions in zinc oxide, i.e., layers of zinc oxide, layers of aluminum-doped zinc oxide, or layers of mixed zinc and tin oxides having a ratio of Sn / Zn in the range of 0.5 to 2 by weight, or a ratio of Sn / Zn in the range of 0.02 to 0.5 by weight; layers of mixed zinc, titanium, and aluminum oxides; layers of silicon nitride; and layers of titanium oxide. In some cases, the IR layers may independently include metal barrier layers such as Ti, Ni, and NiCr.

[0072] This coating substrate provides the advantage of a topcoat that protects against mechanical damage to a wide variety of multilayer coatings. At the same time, the optical properties remain within an acceptable range of variation compared to coatings without the topcoat, with Delta T < 2%, Delta R < 2%, and Delta E < 5.

[0073] The method for manufacturing the coated substrate is as follows: 1. A step of providing a transparent substrate having two main, first and second surfaces that are opposite to each other, 2. A step of depositing a functional coating on at least a portion of the first surface of a transparent substrate. 3. On and in contact with the functional coating, at least SiO x , TiO y , and ZrO z A step of depositing a topcoat containing a mixed metal oxide (where x, y, and z are in the range of 1.8 to 2.2) by magnetron sputtering technique, The top coat, with a total of 100 atomic percent of metal, -10 to 65 atomic percent silicon, -8 to 38 atomic percent titanium, -25 to 80 atomic percent zirconium, Includes, The top coat has a thickness of 0.1 to 10 nm. It includes at least [this].

[0074] The topcoat deposition step using magnetron sputtering allows for easy integration of the process into existing manufacturing lines where a functional coating is first applied to a transparent substrate. Magnetron deposition can also deposit topcoat layers with thicknesses of 0.1–10 nm. Such thin layers have been shown to be effective in providing the necessary mechanical durability without adversely affecting the chemical durability and optical properties of the functional coating.

[0075] Functional coatings can typically be deposited on substrates by chemical vapor deposition (CVD), atmospheric pressure CVD (APCVD), low-pressure CVD (LPCVD), plasma-enhanced chemical vapor deposition (PECVD), LPCVD (low-pressure chemical vapor deposition), physical vapor deposition, magnetron sputtering, and ion-assisted vapor deposition.

[0076] Individual layers of the same functional coating can be formed by different deposition methods. However, typically, they can be deposited using the same technique.

[0077] In some cases, at least one layer of the functional coating can be deposited by magnetron sputtering. In some cases, all layers of the functional coating are deposited by magnetron sputtering.

[0078] The topcoat is deposited using magnetron sputtering. Compared to CVD or sol-gel methods, magnetron sputtering provides optimal efficiency for topcoat deposition in terms of imparting mechanical and chemical durability. Layers deposited by magnetron sputtering are effective in thicknesses ranging from 0.1 to 10 nm, 0.5 to 5.0 nm, or 2.0 to 5.0 nm without any prior heating or additional process steps. The deposited layer does not adversely affect the optical properties of the functional coating, resulting in delta T < 2%, delta R < 2%, and delta E < 5.

[0079] The deposition of the topcoat using magnetron sputtering can be carried out using either a metal or ceramic target to obtain at least three elements of titanium, zirconium, or silicon.

[0080] At least three elements can be supplied independently from one or more ceramic or metal targets. The topcoat deposited on the functional coating by magnetron sputtering contains at least SiO x , TiO y , and ZrO z It contains a mixed metal oxide including (where x, y, and z are in the range of 1.8 to 2.2), The top coat, with a total of 100 atomic percent of metal, -10 to 65 atomic percent silicon, -8 to 38 atomic percent titanium, -25 to 80 atomic percent zirconium, If the top coat has a thickness of 0.1 to 10 nm, various combinations and alternatives for simultaneous sputtering can exist.

[0081] The metal target may include at least one of titanium, zirconium, or silicon. The metal target may include two or more of titanium, zirconium, or silicon.

[0082] The ceramic target may contain at least one oxide of titanium, zirconium, or silicon. The ceramic target may contain two or more oxides of titanium, zirconium, or silicon.

[0083] Ceramic targets may contain two elements selected from titanium, zirconium, or silicon, while metal targets may contain a third element.

[0084] In some cases, one element of the topcoat to be sputtered can be obtained simultaneously from both the ceramic target and the metal target.

[0085] The ceramic target may include at least one oxide of a metal and at least one metallic form of another metal.

[0086] The ceramic target may contain at least one oxide of titanium or zirconium, and silicon in metallic form.

[0087] In such cases, the three elements mentioned above can be obtained from multiple independent targets used in combination, a process also known as simultaneous sputtering, where each target is either ceramic or metallic.

[0088] Sputtering or deposition from two or more targets has the advantage of yielding a variety of topcoats containing at least silicon, titanium, and zirconium, which can be adjusted for desired mechanical durability. It also has the advantage of allowing adjustment of the deposition rate and / or easy replacement from one target to another depending on the material consumed during the process. Furthermore, it has the advantage of allowing adjustment of the topcoat's stoichiometry through the action of the gases used during sputtering.

[0089] In another case, the three elements mentioned above can be obtained from a single target.

[0090] A ceramic target may contain oxides of at least the three elements mentioned above, or a metal target may contain at least the three elements in metallic form.

[0091] The ceramic target may contain titanium and zirconium oxides, as well as silicon in metallic form.

[0092] Sputtering or deposition from a single target containing at least silicon, titanium, and zirconium has the advantage of yielding a reproducible and uniform topcoat.

[0093] The topcoat is typically sputtered in a gas stream containing argon, oxygen, or both. Various mixtures of each gas can be obtained to obtain the required stoichiometry of the topcoat.

[0094] One of the further advantages of this topcoat is that it is heat-treated, and such heat treatment protects the functional coating.

[0095] Even without heat treatment, the topcoat itself provides protection, so the heat treatment step is simply optional and should only be considered when necessary for the final application of the coated substrate.

[0096] The method for manufacturing the heat-treated coated substrate is as follows: 1. A step of providing a transparent substrate having two main, first and second surfaces that are opposite to each other, 2. A step of depositing a functional coating on at least a portion of the first surface of a transparent substrate. 3. On and in contact with the functional coating, at least SiO x , TiO y , and ZrO z A step of depositing a topcoat containing a mixed metal oxide (where x, y, and z are in the range of 1.8 to 2.2) by magnetron sputtering technique, The top coat, with a total of 100 atomic percent of metal, -10 to 65 atomic percent silicon, -8 to 38 atomic percent titanium, -25 to 80 atomic percent zirconium, Includes, The top coat has a thickness of 0.1 to 10 nm. 4. A step of heat treatment of the coated substrate, It includes at least [this].

[0097] In some embodiments of this method compatible with other embodiments of the present invention, the above ranges of Si, Ti, and Zr in the topcoat can vary independently of each other. For example, the amount of Si may be in the range of 15 to 60 atomic percent; the amount of Ti may be in the range of 10 to 35 atomic percent; or the amount of Zr may be in the range of 30 to 70 atomic percent. Thus, these amounts can vary independently for each metal, provided that the total is 100 atomic percent of the metal, including impurities.

[0098] Within the scope of the present invention, if steps exist in sequence, it is intended to mean that they are performed in the order described. However, additional intermediate steps can be added within that sequence. Such additional intermediate steps may be washing, transporting, moving, measuring, cutting, and the like.

[0099] The heat treatment may be bending (also known as curvature), annealing (also known as strengthening), or one of those that occur during a strengthening process.

[0100] One appropriate heat treatment involves heating the coated glass sheet in air to a temperature of at least 560°C, for example between 560°C and 700°C, particularly between approximately 640°C and 670°C, for approximately 3, 4, 6, 8, 10, 12, or even 15 minutes, depending on the type of heat treatment and the thickness of the glass sheet. This treatment may include a rapid cooling step after the heating step to create a stress difference between the surface and the center of the glass, so that when impact is applied, this so-called tempered glass sheet will safely break into small fragments. If the cooling step is not very strong, the glass is simply heat-strengthened, and in either case, better mechanical resistance is obtained.

[0101] Further heat treatment may be indicated in process steps such as 1) bending, 2) strengthening, 3) sintering of colored ceramic printing or silver busbar printing, 4) vacuum sealing of vacuum double glazing, and 5) firing of wet-coated low-reflection or anti-glare coatings.

[0102] The first method for manufacturing a double-sided coated substrate is, in order: 1. A step of providing a transparent substrate having two main, first and second surfaces opposite to each other, wherein the first surface is exposed. 2. A step of depositing a first functional coating on at least a portion of the first surface of a transparent substrate. 3. On and in contact with the first functional coating, at least SiO x , TiO y , and ZrO z A step of depositing a topcoat containing a mixed metal oxide (where x, y, and z are in the range of 1.8 to 2.2) by magnetron sputtering technique, The top coat, with a total of 100 atomic percent of metal, -10 to 65 atomic percent silicon, -8 to 38 atomic percent titanium, -25 to 80 atomic percent zirconium, Includes, The top coat has a thickness of 0.1 to 10 nm. 4. The step of turning the substrate over so that the second surface is exposed. 5. A step of depositing a second functional coating on at least a portion of the second surface of a transparent substrate to form a double-sided coated transparent substrate. 6. Depending on the case, a step of applying a second top coat, 7. Depending on the case, a step of heat treatment of the double-sided coated transparent substrate, It includes at least [this].

[0103] A second method for manufacturing a double-sided coated substrate is, in order: 1. A step of providing a transparent substrate having two main, first and second surfaces opposite to each other, wherein the first surface is exposed. 2. A step of depositing a first functional coating on at least a portion of the first surface of a transparent substrate. 3. On and in contact with the first functional coating, at least SiO x , TiO y , and ZrO z A step of depositing a topcoat containing a mixed metal oxide (where x, y, and z are in the range of 1.8 to 2.2) by magnetron sputtering technique, The top coat, with a total of 100 atomic percent of metal, -10 to 65 atomic percent silicon, -8 to 38 atomic percent titanium, -25 to 80 atomic percent zirconium, Includes, The top coat has a thickness of 0.1 to 10 nm. 4. The step of turning the substrate over so that the second surface is exposed. 5. A step of depositing a second functional coating on at least a portion of the second surface of a transparent substrate to form a double-sided coated transparent substrate. 6. Depending on the case, at least SiO2 on and in contact with the second functional coating. x , TiO y , and ZrO zA step of depositing a topcoat containing a mixed metal oxide (where x, y, and z are in the range of 1.8 to 2.2) by magnetron sputtering technique, The top coat, with a total of 100 atomic percent of metal, -10 to 65 atomic percent silicon, -8 to 38 atomic percent titanium, -25 to 80 atomic percent zirconium, Includes, The top coat has a thickness of 0.1 to 10 nm. 7. Depending on the case, a step of heat treatment of the double-sided coated transparent substrate, It includes at least [this].

[0104] Therefore, by such first and second methods, a transparent substrate can be provided having a first functional coating on at least a portion of the first surface and a second functional coating on at least a portion of the second surface, wherein at least one of the first or second functional coatings is provided with the topcoat described herein.

[0105] In this situation, the first and second functional coatings may be the same or different, and are selected from the aforementioned functional coatings in particular.

[0106] This topcoat proves even more useful in that it provides a functional coating with sufficient mechanical durability to allow coating onto a second surface on the opposite side of the transparent substrate.

[0107] In some cases compatible with the aforementioned alternative methods, the heat treatment step can be performed before or after the inversion step, i.e., the coated transparent substrate can be heat-treated before the second functional coating is applied.

[0108] Accordingly, the present invention also provides a heat-treated coating glazing comprising a functional coating and a topcoat of magnetron-sputtered mixed metal oxides comprising at least titanium, zirconium, and silicon, wherein the topcoat comprises at least SiO x , TiO y , and ZrO z (where x, y, and z are in the range of 1.8 to 2.2) The top coat is made up of 100 atomic percent of metal, including impurities. -10 to 65 atomic percent silicon, -8 to 38 atomic percent titanium, -25 to 80 atomic percent zirconium, Includes, The top coat has a thickness of 0.1 to 10 nm.

[0109] If the coated substrate can withstand heat treatments of the type of strengthening or bending without impairing its optical and / or energetic properties as manufactured, then the functional coating and / or coated substrate may be called "heat-treatable" or "strengthenable".

[0110] In some cases, functional coatings may be "self-matchable." This means that when the coated substrate is subjected to heat treatments of the type of strengthening or bending, there is little to no change in its optical and / or energetic properties.

[0111] Typically, the CIELAB 1976 value (L) is used to define the color of the coating substrate. * a * b * These are measured using a light source D65 / 10°.

[0112] TIFF0007857227000001.tif15170 represents the color change during heat treatment, i.e., the difference in color between before and after heat treatment.

[0113] ΔE in transmission and reflection *Self-matchability can be considered if the value is ≤5 or ≤2, and / or if there is no or slight change in the light transmission and reflection and energy values, i.e., the difference in values ​​before and after heat treatment in one glazing remains ≤5 or ≤2.

[0114] If the functional coating is self-adhering, this topcoat will not alter the self-adherence of such functional coating placed beneath it.

[0115] This has the advantage that, for the same application, for example, in the exterior of a building, non-heat-treated and heat-treated products can be placed next to each other. This also has the advantage that, while self-conformity as defined is guaranteed between the non-heat-treated and heat-treated products, a topcoat can be applied only to the heat-treated product or only to the non-heat-treated product.

[0116] The topcoat is designed to be in contact with the surrounding environment as far away from the substrate as possible. In specific cases compatible with another aspect of the present invention, the coated substrate may have at least one additional temporary protective layer on top of and in contact with the topcoat. As described below, such a “temporary” protective layer is typically removed by washing or heat treatment of the substrate.

[0117] In one embodiment of the present invention, the temporary protective layer may be a carbon temporary protective layer, a polymer temporary protective layer, or a peelable protective layer.

[0118] Examples of temporary carbon protective layers include layers typically formed by magnetron sputtering, having thicknesses of 0.5–15 nm, 1–10 nm, 1–7 nm, or any value in between. Such carbon protective coatings are typically removed by heat treatment of the transparent substrate and, as measured by colorimetric methods, are removed at a rate of, for example, 99–100%.

[0119] Examples of a temporary polymer protective layer include a layer formed by the evaporation or reaction products of a polymer coating composition containing polyvinyl alcohol, polyethylene, acrylic, etc., which can be subsequently removed by aqueous cleaning, solvent cleaning, vapor removal, thermal decomposition, or combustion. Such a polymer coating composition may be a liquid solution, emulsion, suspension, slurry, or dispersion.

[0120] Examples of peelable protective layers include coatings formed from polyamide liquid compositions.

[0121] The temporary protective coating can be removed, for example, by washing, burning, thermal decomposition, or peeling. Before or after the removal of the temporary protective coating, the substrate can be processed, for example, by cutting, trimming, bending, molding, and / or incorporating it into a manufactured article.

[0122] Therefore, all of the above methods may further include the step of depositing a carbon layer on a coated substrate.

[0123] The carbon protective topcoat has the advantage of also being able to be deposited by sputtering, and therefore can be included in the same process without major technical constraints.

[0124] The present invention provides a multilayer glazing unit comprising at least one coating substrate as described in the various embodiments described above.

[0125] Examples of multilayer glazing units include double or triple glazing or laminated glazing, where the coating substrate is associated with one or more other glass sheets, which may or may not be coated. In the case of multilayer glazing, the coating surface of the glazing can be positioned in contact with the space between the two glass sheets, and in the case of laminated glazing, it can be positioned in contact with the contact layer (P2 or P3).

[0126] Due to its mechanical resistance and chemical resistance, the coating surface of the coating substrate does not necessarily need to undergo edge removal before being incorporated into a multi-layer glazing unit. It can be placed on the outer surface of the multi-layer glazing unit, i.e., in contact with the external or internal environment of the building or vehicle (P1 or P4), and still achieve sufficient mechanical resistance and even chemical resistance. Therefore, a thin layer stack can be provided on the surface of a glass substrate facing the interior of the building or vehicle (P2 of a single non-laminated glass sheet, or P4 of laminated glass or a double glazing unit). In some cases, the coating stack can be placed in contact with the outside (P1).

[0127] The coating substrate of the present invention may be useful in architectural glazing (doors, windows, display shelves, insulated glass (IG) window units, etc.), electrical appliance applications (refrigerator doors, oven doors, etc.), and transportation applications (vehicle windows, skylights, windshields, side windows), where there is an increasing need for glass with very pronounced curvature and / or complex shapes (double curvature, S-shaped curvature, etc.).

[0128] In some cases, the coating material can be reinforced. As a result of its safety and strength, tempered glass is used in a variety of demanding applications, including windows, shower doors, architectural glass doors and tables, refrigerator trays, components of bulletproof glass, and various types of dishes and cooking utensils.

[0129] Therefore, the coated substrate is highly durable, in some cases both before and after optional heat treatment, i.e., it can withstand certain chemical and / or mechanical tests described below. Optical parameters can be optimized without losing the durability achieved by the functional coating applied to the coated substrate claimed herein.

[0130] In this specification, "chemical durability" or "chemically durable" is used synonymously with the technical terms "chemical stability" or "chemical resistance."

[0131] In this specification, "mechanical durability" or "of mechanical durability" is used synonymously with the technical terms "mechanical stability" or "mechanical resistance."

[0132] The present invention provides the use of a topcoat on a transparent substrate provided with a functional coating to increase durability by increasing abrasion resistance by at least 10%, at least 20%, or at least 40%, wherein the topcoat is at least SiO x , TiO y , and ZrO z A magnetron-sputtered mixed metal oxide containing (where x, y, and z are in the range of 1.8 to 2.2), The top coat is made up of 100 atomic percent of metal, including impurities. -10 to 65 atomic percent silicon, -8 to 38 atomic percent titanium, -25 to 80 atomic percent zirconium, It includes [material name], and the top coat has a thickness of 0.1 to 10 nm.

[0133] In some embodiments of this use compatible with other embodiments of the present invention, the above ranges of Si, Ti, and Zr in the topcoat can vary independently of each other. For example, the amount of Si may be in the range of 15 to 60 atomic percent; the amount of Ti may be in the range of 10 to 35 atomic percent; or the amount of Zr may be in the range of 30 to 70 atomic percent. Thus, these amounts can vary independently for each metal, however the total is 100 atomic percent of metal, including impurities. [Examples]

[0134] Mechanical stability was evaluated by the following wear test method, which is well known to those skilled in the art.

[0135] Other chemical durability tests were conducted, including the Cleveland test (3, 7, and 10 days), climate chamber test (3, 7, and 10 days), and salt spray test (2, 5, and 10 days). Since these results were comparable to the standard results obtained using the top layers, such as those in Comparative Examples 1 and 2 below, a detailed summary of these results will not be provided.

[0136] Typical mechanical durability tests were performed, such as the Automatic Wet Rub Test (AWRT-10, 50, 100, 250, 500, and 1000 cycles) or the Dry Brush Test (250 and 500 cycles). All tests passed successfully, so the summary of the results will not be described in detail, and the abrasion tests described herein, which expose the equipment to more severe abrasion conditions, will be performed.

[0137] The emissivity and aesthetics of the functional coating were measured, but there was no effect from this topcoat, so these will not be discussed. The optical properties remain within acceptable limits, and compared to the functional coating without the topcoat, using a D65 / 10° or D65 / 2° light source, Delta T < 2%, Delta R < 2%, and Delta E < 5.

[0138] Abrasion test The abrasion test is a dry abrasion test performed as described in the standard ISO 11998:1998, consisting of at least 1000 cycles using a 900g abrasive pad. In the present invention, these cycles are performed on a dry sample without any liquid being added.

[0139] This test was also performed on samples after heat treatment (referred to herein as "baking"). A typical test conducted involved at least 250 cycles.

[0140] The test results are obtained by visually evaluating the sample in comparison to a defined grade of a reference sample. For abrasion tests, the internal grade is set in the range of 0 to 10, with an acceptable value of 7 to 10. A single value is typically the average of at least three samples from a single experiment. The comparative examples in the table below were prepared in accordance with the embodiments of the present invention as internal verification of the procedure for each "run" of experiment (as set in the table below).

[0141] This abrasion test provides more severe and abrasive conditions than typical AWRT or dry brush tests known in the art.

[0142] The transparent substrate used in this embodiment of glazing, in which one stack of thin-layer stacks is provided, is standard float soda lime, which is transparent, 4 mm thick, and thoroughly cleaned before coating deposition.

[0143] The heat treatment conditions (or baking conditions) include placing the sample inside a convection furnace at a temperature of 670°C for 4 to 5 minutes.

[0144] In the following table: Ag represents silver. AZO2% represents a layer of aluminum-doped zinc oxide obtained from a ceramic target containing zinc oxide doped with 2 wt% aluminum oxide. SiN represents a layer of silicon nitride (Si3N4). TiO is TiO n This is a quasi-stoichiometric layer of titanium oxide obtained from a ceramic target (where n is 1.65 to 1.85). TZO has a ratio of 65 wt% TiO2 and 35 wt% ZrO2 (resulting in 74 atomic% Ti and 26 atomic% Zr) TiO x TiZrO2 is composed of / ZrO2. x This is a layer of titanium-zirconium mixed oxide obtained from a ceramic target. ZnO represents a layer of zinc oxide without dopants obtained from a zinc metal target. ZSO5 represents a mixed zinc-tin layer obtained from a metal target containing 52 wt% Zn and 48 wt% Sn. The ZTAO barrier layer (located on top of and in contact with the silver layer) consists of 85-95% by weight of ZnO and TiO x ZnO:TiO x This is a zinc-titanium-aluminum oxide layer obtained from a ceramic target composed of Al2O3, with a contact layer having a composition of Zn:Ti:Al of 86.3:10.4:3.3 atomic percent. As a seed layer (in contact with the silver layer), ZTAO is a layer of zinc-titanium-aluminum oxide obtained from a metal target with a ratio of 88.8 wt% Zn, 9.5 wt% Ti, and 1.7 wt% Al.

[0145] Unless otherwise specified, the standard deposition method for the seed layer is based on a gas flow of an 80 / 20 mixture of oxygen and argon. Silicon nitride was sputtered in a gas flow of argon and N2 having sufficient N2 to obtain a sufficiently stoichiometric Si3N4.

[0146] Unless otherwise specified, the thickness variation can be <5% for all thicknesses.

[0147] Examples 1 to 8 correspond to the sixth example of a multilayer coating including the aforementioned IR layer. Example 9 corresponds to the seventh example of a multilayer coating including the aforementioned IR layer.

[0148] Examples 1-4 - Comparative Examples C1-C4 The following stack was obtained: Glass / ZSO5 (25.4nm) / ZTAO (9.0nm) / Ag (18.0nm) / ZTAO (5.0nm) / ZSO5 (16.5nm) / SiN (20.0nm) / Top coat (5.0nm).

[0149] In Examples 1 to 4, topcoats according to one embodiment of the present invention were fabricated by simultaneously sputtering a 65 wt% TiOy and 35 wt% ZrOz ceramic target with a Si-ZrO2 ceramic target in a ratio of 65 to 35 wt% (where x, y, and z are in the range of 1.8 to 2.2) to obtain topcoats containing Si, Ti, and Zr in various atomic percent amounts shown in Table 1 within the claimed range.

[0150] In Comparative Examples 1-4, topcoats were prepared such that the topcoat contained Si, Ti, and Zr in various atomic percent amounts, as shown in Table 1, outside the claimed range.

[0151] Table 1 shows the results of various tests (average values ​​of tests repeated multiple times for each example and comparative example). The results clearly show that Examples 1-4 have better mechanical resistance than Comparative Examples C1-C4, and that they have a value of ≥7 in the wear test both before and after seizing.

[0152] Comparative Example 1 is a typical TiZrO topcoat obtained in the art by sputtering using a ceramic target of 65 wt% TiOy and 35 wt% ZrOz, and has (0 atomic% Si) and a value of <6.

[0153] Comparative Example 2 was a SiZrO topcoat (0 atomic% Ti) using a Si-ZrO2 ceramic target in a ratio of 65-35 wt%, and had a value of <6.

[0154] In Comparative Examples 3 and 4, topcoats containing less than 25 atomic% Zr (and more than 65 atomic% Si in the case of Comparative Example 3) were obtained, with a value of <8 without baking and a value of ≤6 after baking.

[0155] Depending on the amounts of Si, Ti, and Zr in the mixed metal oxide topcoat according to the present invention, the wear resistance performance of the topcoat can be greatly improved to a level that was previously unattainable, both before and after curing.

[0156] The abrasion resistance is combined with equivalent performance in all chemical durability tests and does not adversely affect the optical performance of the coating. As shown in Table 1 (Abrasion Resistance Without Baking), the increased abrasion resistance of Examples 1-4 compared to Comparative Example 1 indicates that the topcoat improves durability. TIFF0007857227000002.tif88170

[0157] Example 5 - Comparative Example C5 The following stack was obtained: Glass / ZSO5 (24.5nm) / ZnO (5.0nm) / Ag (17.0nm) / AZO (7.0nm) / ZSO5 (21.0nm) / SiN (22.0nm) / Top coat (4.0nm).

[0158] In Example 5, a topcoat according to one embodiment of the present invention was fabricated by sputtering a ceramic target of 18.5 wt% TiOy, 70.4 wt% ZrOz, and 11 wt% metallic Si (and (Y2O3) impurities present in the target) to obtain a topcoat containing 33.0 atomic% Si, 19.3 atomic% Ti, and 47.7 atomic% Zr within the claimed range (where x, y, and z are in the range of 1.8 to 2.2).

[0159] In Comparative Example 5, the topcoat was a typical TiZrO topcoat (0 atomic% Si) obtained in the art by sputtering using a ceramic target of 65 wt% TiOy and 35 wt% ZrOz.

[0160] The results of various tests are shown in Table 2 (average values ​​of tests repeated multiple times for each example and comparative example). The results clearly show that the glazing of Example 5 has the best mechanical resistance. This topcoat improves durability by increasing abrasion resistance by 41.7% (8.5 vs. 6.0) without adversely affecting the optical performance of the coating. TIFF0007857227000003.tif33170

[0161] Example 6 - Comparative Example C6 The following stack was obtained: Glass / TiO (19.0nm) / ZTAO (9.0nm) / Ag (12.0nm) / ZTAO (5.0nm) / ZSO5 (18.0nm) / SiN (18.0nm) / Top coat (5.0nm)

[0162] In Example 6, a topcoat according to one embodiment of the present invention was fabricated by simultaneous sputtering of a ceramic target of 65 wt% TiOy and 35 wt% ZrOz, and a ceramic target of Si-ZrO2 in a ratio of 65 to 35 wt% (where x, y, and z are in the range of 1.8 to 2.2), in order to obtain a topcoat containing the atomic percent amounts of Si, Ti, and Zr shown in Table 3 within the claimed range.

[0163] In Comparative Example 6, the topcoat was a typical TiZrO topcoat (0 atomic% Si) obtained in the art by sputtering using a ceramic target of 65 wt% TiOy and 35 wt% ZrOz.

[0164] The results of various tests are shown in Table 3 (average values ​​of tests repeated multiple times for each example and comparative example). The results clearly show that the glazing of Example 6 has the best mechanical resistance. This topcoat improves durability by increasing abrasion resistance by 87.5% (9.0 vs. 4.8) without adversely affecting the optical performance of the coating. TIFF0007857227000004.tif29170

[0165] Example 7 - Comparative Example C7 The following stack was obtained: Glass / TiO (23.0nm) / ZnO (5.0nm) / Ag (12.0nm) / AZO (5.0nm) / ZSO5 (16.0nm) / SiN (18.0nm) / Top coat (4.0nm)

[0166] In Example 7, a topcoat according to one embodiment of the present invention was fabricated by sputtering a ceramic target of 18.5 wt% TiOx, 70.4 wt% ZrOx, and 11 wt% metallic Si (and (Y2O3) impurities present in the target) to obtain a topcoat containing 33.0 atomic% Si, 19.3 atomic% Ti, and 47.7 atomic% Zr within the claimed range (where x, y, and z are in the range of 1.8 to 2.2).

[0167] In Comparative Example 7, the topcoat was a typical TiZrO topcoat (0 atomic% Si) obtained in the art by sputtering using a ceramic target of 65 wt% TiOy and 35 wt% ZrOz.

[0168] The results of various tests are shown in Table 4 (average values ​​of tests repeated multiple times for each example and comparative example). The results clearly show that the glazing of Example 7 has the best mechanical resistance. This topcoat improves durability by increasing abrasion resistance by 73.6% (9.2 vs 5.3) without adversely affecting the optical performance of the coating. TIFF0007857227000005.tif27170

[0169] Example 8 - Comparative Example C8 The following stack was obtained: Glass / ZSO5 (17.0nm) / TZO (16.6nm) / ZnO (5.0nm) / Ag (10.0nm) / AZO (7.0nm) / ZSO5 (16.0nm) / SiN (17.0nm) / Top coat (4.0nm)

[0170] In Example 8, a topcoat according to one embodiment of the present invention was fabricated by sputtering a ceramic target of 18.5 wt% TiOy, 70.4 wt% ZrOz, and 11 wt% metallic Si (and (Y2O3) impurities in the target) to obtain a topcoat containing 33.0 atomic% Si, 19.3 atomic% Ti, and 47.7 atomic% Zr within the claimed range (where x, y, and z are in the range of 1.8 to 2.2).

[0171] In Comparative Example 8, the topcoat was a typical TiZrO topcoat (0 atomic% Si) obtained in the art by sputtering using a ceramic target of 65 wt% TiOy and 35 wt% ZrOz.

[0172] The results of various tests are shown in Table 5 (average values ​​of tests repeated multiple times for each example and comparative example). The results clearly show that the glazing of Example 8 has the best mechanical resistance. This topcoat improves durability by increasing abrasion resistance by only 24.3% (9.2 vs. 7.4) without adversely affecting the optical performance of the coating. TIFF0007857227000006.tif36170

[0173] Example 9 - Comparative Example C9 The following stack was obtained: Glass / ZSO5 (36.9nm) / ZnO (5.0nm) / Ag (12.9nm) / AZO (7.0nm) / ZSO5 (21.0nm) / SiN (36.7nm) / ZSO5 (21.0nm) / ZnO (5.0nm) / Ag (13.8nm) / AZO (7.0nm) / ZSO5 (7.7nm) / SiN (20.0nm) / Top coat (4nm)

[0174] In Example 9, a topcoat according to one embodiment of the present invention was fabricated by sputtering a ceramic target of 18.5 wt% TiOy, 70.4 wt% ZrOz, and 11 wt% metallic Si (and (Y2O3) impurities in the target) to obtain a topcoat containing 33.0 atomic% Si, 19.3 atomic% Ti, and 47.7 atomic% Zr within the claimed range (where x, y, and z are in the range of 1.8 to 2.2).

[0175] In Comparative Example 9, the topcoat was a typical TiZrO topcoat (0 atomic% Si) obtained in the art by sputtering using a ceramic target of 65 wt% TiOy and 35 wt% ZrOz.

[0176] The results of various tests are shown in Table 6 (average values ​​of tests repeated multiple times for each example and comparative example). The results clearly show that the glazing of Example 8 has the best mechanical resistance. This topcoat improves durability by increasing abrasion resistance by 55.9% (9.2 vs 5.9) without adversely affecting the optical performance of the coating. TIFF0007857227000007.tif36170

[0177] Examples 10 and 11 - Comparative Example C10 In the case of comparative example C10, the following stack was obtained: Glass / ZSO5 (38.5 nm) / ZnO:Al (3.0 nm) / Ag (9.5 nm) / AZO (5.0 nm) / ZSO5 (16.0 nm) / SiN (22.0 nm) / TZO (3.0 nm). TZO is obtained in this art by sputtering using a ceramic target of 65 wt% TiOy and 35 wt% ZrOz (0 atomic% Si).

[0178] In Example 10, the following stack was obtained: Glass / ZSO5 (38.5 nm) / ZnO:Al (3.0 nm) / Ag (9.5 nm) / AZO (5.0 nm) / ZSO5 (16.0 nm) / SiN (22.0 nm) / Top coat (3 nm). The top coat was fabricated according to one embodiment of the present invention by sputtering a ceramic target of 18.5 wt% TiOy, 70.4 wt% ZrOz, and 11 wt% metallic Si (and (Y2O3) impurities in the target) to obtain a top coat containing 33.0 atomic% Si, 19.3 atomic% Ti, and 47.7 atomic% Zr within the claimed range (where x, y, and z are in the range of 1.8 to 2.2).

[0179] In Example 11, the following stack was obtained: Glass / ZSO5 (38.5nm) / ZnO:Al (3.0nm) / Ag (9.5nm) / AZO (5.0nm) / ZSO5 (16.0nm) / SiN (22.0nm) / TZO (3.0nm) / Top coat (3nm)

[0180] In Example 11, the TZO was obtained in the art by sputtering using a ceramic target of 65 wt% TiOy and 35 wt% ZrOz (0 atomic% Si), and the topcoat was prepared according to one embodiment of the present invention by sputtering a ceramic target of 18.5 wt% TiOy, 70.4 wt% ZrOz, and 11 wt% metallic Si (and (Y2O3) impurities in the target) to obtain a topcoat containing, to the claimed extent, 33.0 atomic% Si, 19.3 atomic% Ti, and 47.7 atomic% Zr (where x, y, and z are in the range of 1.8 to 2.2).

[0181] Therefore, Example 10 is another variation of Comparative Example C10 in which the initial TZO topcoat of Comparative Example C10 is replaced with a main topcoat of a mixed oxide of Si, Ti, and Zr, and Example 11 is a variation of Comparative Example C10 in which a main topcoat of a mixed oxide of Si, Ti, and Zr is applied on the upper surface of the initial TZO topcoat.

[0182] The colorimetric results in Table 7 show that the light transmittance values ​​and color differences are still within acceptable limits, with Delta T < 2%, Delta R < 2%, and Delta E < 5.

[0183] The results also show that the mechanical resistance of the mixed oxide topcoat of Si, Ti, and Zr is superior to that of the typical TZO topcoat of Comparative Example C10. TIFF0007857227000008.tif159170

Claims

1. A coated substrate comprising a transparent substrate having two main, opposite first and second surfaces, wherein a functional coating is provided on at least one surface, the transparent substrate having at least SiO on and in contact with the functional coating. ｘ , TiO ｙ , and ZrO ｚ A top coat is provided which is magnetron sputtered with a mixed metal oxide containing (where x, y, and z are in the range of 1.8 to 2.2), The top coat contains only silicon, titanium, zirconium, and optionally impurities as metal atoms. The impurities are yttrium, hafnium, and / or aluminum. The top coat, excluding impurities, is 100 atomic percent of metal in total. -15 to 60 atomic percent silicon, -8 to 35 atomic percent titanium, -30 to 70 atomic percent zirconium, Includes, A coated substrate characterized by having a top coat thickness of 0.1 to 10 nm.

2. The coated substrate according to claim 1, wherein the functional coating is a solar control coating, a conductive coating, an anti-reflective coating, a decorative coating, and / or a low-emissivity coating.

3. The coated substrate according to claim 1 or 2, wherein the functional coating is a single-layer metal oxide coating, a multi-layer metal oxide coating, a non-metal oxide coating, or a multi-layer coating.

4. The coated substrate according to claim 3, wherein the single-layer metal oxide coating comprises zinc oxide doped with aluminum, gallium, or hafnium; a mixed metal oxide of zinc and tin; tin oxide; tin oxide doped with fluorine or antimony; indium oxide; or indium oxide doped with tin.

5. The coated substrate according to claim 3, wherein the multilayer metal oxide coating comprises at least one layer of a high refractive index material and at least one layer of a low refractive index material.

6. The coated substrate according to claim 3, wherein the multilayer coating includes an alternating arrangement of n infrared reflective (IR) layers and n+1 dielectric layers, such that each IR layer is surrounded by two dielectric layers, and n ≥ 1.

7. Multilayer coating, a. At least one silver layer, in the order of substrate / MeO / ZnO:AlSi / Ag / AlSi-MeO, where MeO is a metal oxide; or b. A first dielectric layer containing silicon nitride; a first layer containing Ni or NiCr; an infrared (IR) reflective layer containing silver; a second layer containing Ni or NiCr; a second dielectric layer containing silicon nitride; or c. An infrared (IR) reflective layer in contact with and sandwiched between the first and second layers, wherein the second layer comprises NiCrOx; at least the NiCrOx-containing second layer is oxidized in steps such that the first portion of the second layer closer to the infrared (IR) reflective layer is oxidized less than the second portion of the second layer further away from the infrared (IR) reflective layer; or d. Dielectric layer; a first layer containing zinc oxide located on the dielectric layer; an infrared (IR) reflective layer containing silver located on and in contact with the first layer containing zinc oxide; a layer containing NiCr oxide located on and in contact with the IR reflective layer; a second layer containing zinc oxide located on and in contact with the layer containing NiCr oxide; another dielectric layer located on the second layer containing zinc oxide; or e. A first dielectric layer; a first infrared (IR) reflective layer containing silver located at least on the first dielectric layer; a first layer containing zinc oxide located at least on the first IR reflective layer and the first dielectric layer; a second IR reflective layer containing silver located on and in contact with the first layer containing zinc oxide; a layer containing NiCr oxide located on and in contact with the second IR reflective layer; a second layer containing zinc oxide located on and in contact with the layer containing NiCr oxide; at least another dielectric layer located on the second layer containing zinc oxide; or f. A first dielectric layer; a first layer containing zinc oxide located on the dielectric layer; an infrared (IR) reflective layer containing silver located on and in contact with the first layer containing zinc oxide; a second layer containing zinc oxide located on the IR layer; a second dielectric layer located on the second layer containing zinc oxide; or g. A first dielectric layer; a first IR layer containing silver; a second dielectric layer; a second IR layer; a third dielectric layer, where the first, second, and third dielectric layers may include multiple layers; or h. A first dielectric layer; a first IR layer containing silver; a second dielectric layer; a second IR layer; a third dielectric layer; a third IR layer; a fourth dielectric layer, where the first, second, third, and fourth dielectric layers may include multiple layers. A coating substrate according to claim 6, including the following:

8. The metal oxide MeO in at least one silver layer of the multilayer coating is SnO ２ , TiO ２ , In ２ O ３ , Bi ２ O ３ , ZrO ２ , Ta ２ O ５ , SiO ２ , or Al ２ O ３ , or a mixture thereof, the coated substrate according to claim 7.

9. A coated substrate according to any one of claims 1 to 8, having a first functional coating on at least a portion of a first surface and a second functional coating on at least a portion of a second surface, wherein at least one of the first or second functional coatings is provided with the top coat according to any one of claims 1 to 8.

10. The coating substrate according to any one of claims 1 to 8, wherein at least one temporary protective layer is further provided on and in contact with the topcoat, which is a mixed metal oxide magnetron sputtered thereon.

11. The coated substrate according to claim 10, wherein the temporary protective layer is a carbon temporary protective layer, a polymer temporary protective layer, or a peelable protective layer.

12. A heat-treated coated substrate comprising a transparent substrate having two opposite surfaces, wherein a functional coating is provided on at least one of the surfaces, the transparent substrate having at least SiO2 on and in contact with the functional coating. ｘ , TiO ｙ , and ZrO ｚ A top coat is provided which is magnetron sputtered with a mixed metal oxide containing (where x, y, and z are in the range of 1.8 to 2.2), The top coat contains only silicon, titanium, zirconium, and optionally impurities as metal atoms. The impurities are yttrium, hafnium, and / or aluminum. The top coat, excluding impurities, is 100 atomic percent of metal in total. -15 to 60 atomic percent silicon, -8 to 35 atomic percent titanium, -30 to 70 atomic percent zirconium, Includes, A coated substrate characterized by having a top coat thickness of 0.1 to 10 nm.

13. A multilayer glazing unit comprising at least one coating substrate according to any one of claims 1 to 11.

14. A method for manufacturing a coated substrate, in order: (1) A step of providing a transparent substrate having two main, opposite first and second surfaces, (2) A step of depositing a functional coating on at least a portion of the first surface of a transparent substrate, (3) On the functional coating and in contact therewith, at least SiO ｘ , TiO ｙ , and ZrO ｚ A step of depositing a topcoat containing a mixed metal oxide (where x, y, and z are in the range of 1.8 to 2.2) by magnetron sputtering technology, The top coat contains only silicon, titanium, zirconium, and optionally impurities as metal atoms. The impurities are yttrium, hafnium, and / or aluminum. The top coat, excluding impurities, is 100 atomic percent of metal in total. -15 to 60 atomic percent silicon, -8 to 35 atomic percent titanium, -30 to 70 atomic percent zirconium, Includes, A step in which the top coat has a thickness of 0.1 to 10 nm, A manufacturing method comprising at least the following.

15. A method for manufacturing a heat-treated coated substrate, in order: (1) A step of providing a transparent substrate having two main, opposite first and second surfaces, (2) A step of depositing a functional coating on at least a portion of the first surface of a transparent substrate, (3) On the functional coating and in contact therewith, at least SiO ｘ , TiO ｙ , and ZrO ｚ A step of depositing a topcoat containing a mixed metal oxide (where x, y, and z are in the range of 1.8 to 2.2) by magnetron sputtering technology, The top coat contains only silicon, titanium, zirconium, and optionally impurities as metal atoms. The impurities are yttrium, hafnium, and / or aluminum. The top coat, excluding impurities, is 100 atomic percent of metal in total. -15 to 60 atomic percent silicon, -8 to 35 atomic percent titanium, -30 to 70 atomic percent zirconium, Includes, A step in which the top coat has a thickness of 0.1 to 10 nm, (4) A step of heat treatment of the coating substrate, A manufacturing method comprising at least the following.

16. A method for manufacturing a double-sided coated substrate, in order: (1) A step of providing a transparent substrate having two main, opposite surfaces, a first and a second surface, wherein the first surface is exposed. (2) A step of depositing a first functional coating on at least a portion of the first surface of a transparent substrate, (3) On the first functional coating and in contact therewith, at least SiO ｘ , TiO ｙ , and ZrO ｚ A step of depositing a topcoat containing a mixed metal oxide (where x, y, and z are in the range of 1.8 to 2.2) by magnetron sputtering technology, The top coat contains only silicon, titanium, zirconium, and optionally impurities as metal atoms. The impurities are yttrium, hafnium, and / or aluminum. The top coat, excluding impurities, is 100 atomic percent of metal in total. -15 to 60 atomic percent silicon, -8 to 35 atomic percent titanium, -30 to 70 atomic percent zirconium, Includes, A step in which the top coat has a thickness of 0.1 to 10 nm, (4) The step of turning the substrate over so that the second surface is exposed, (5) A step of depositing a second functional coating on at least a portion of the second surface of a transparent substrate to form a double-sided coated transparent substrate. A manufacturing method comprising at least the following.

17. A method for producing a double-sided coated substrate according to claim 16, wherein after step (5) (6) On and in contact with the second functional coating, at least SiO ｘ , TiO ｙ , and ZrO ｚ A step of depositing a topcoat containing a mixed metal oxide (where x, y, and z are in the range of 1.8 to 2.2) by magnetron sputtering technology, The top coat contains only silicon, titanium, zirconium, and optionally impurities as metal atoms. The impurities are yttrium, hafnium, and / or aluminum. The top coat, excluding impurities, is 100 atomic percent of metal in total. -15 to 60 atomic percent silicon, -8 to 35 atomic percent titanium, -30 to 70 atomic percent zirconium, Includes, A step in which the top coat has a thickness of 0.1 to 10 nm, A manufacturing method that includes this.

18. A method for producing a double-sided coated substrate according to claim 17, wherein after step (6) (7) A step of heat treatment of the double-sided coated transparent substrate, A manufacturing method that includes this.

19. The method according to any one of claims 14 to 18, wherein the deposition of a topcoat containing at least silicon, titanium, and zirconium by magnetron sputtering is carried out using a target that is either metal or ceramic in order to obtain at least three elements of titanium, zirconium, or silicon.

20. The method according to any one of claims 14 to 18, wherein the deposition of a topcoat containing at least silicon, titanium, and zirconium by magnetron sputtering is carried out using a ceramic target containing titanium and zirconium oxides and metallic silicon.

21. Use of a topcoat for a transparent substrate provided with a functional coating to improve durability by increasing abrasion resistance by at least 10%, wherein the topcoat comprises at least SiO ｘ , TiO ｙ , and ZrO ｚ A mixed metal oxide that has been magnetron sputtered, containing (where x, y, and z are in the range of 1.8 to 2.2), The top coat contains only silicon, titanium, zirconium, and optionally impurities as metal atoms. The impurities are yttrium, hafnium, and / or aluminum. The top coat, excluding impurities, is 100 atomic percent of metal in total. -15 to 60 atomic percent silicon, -8 to 35 atomic percent titanium, -30 to 70 atomic percent zirconium, Includes, Use a top coat with a thickness of 0.1 to 10 nm.

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