Coated glass plate

Abstract

The present invention relates to a coated glass sheet, a method for producing the coated glass sheet, a double-insulating glazing comprising the coated glass sheet, and the use of the coated glass sheet and / or the double-insulating glazing in a building or vehicle, the coated glass sheet comprising a glass substrate and a coating suitable for reflecting infrared radiation, the coating being selected from the group consisting of oxides of zirconium and titanium Zr x Ti y O z and an atomic ratio of Zr based on Zr and Ti in the base layer is calculated as x / (x+y) and is 0.40 to 0.95.

Description

[Background technology]

[0001] The present invention relates to a coated glass sheet, in particular a coated glass sheet comprising a glass substrate and a coating. The present invention also relates to a method for producing said coated glass sheet.

[0002] There is a continuing demand from the glass manufacturing industry for coated glass substrates that are capable of meeting the stringent performance requirements of automotive and architectural glazing. Such glazing must meet the necessary standards of safety and energy efficiency, be shaped to fit the physical and aesthetic requirements of the structure in which it is installed, and perform its primary function of light transmission. It is also desirable for such glazing to be of a preferred color from a transmission and / or reflection standpoint.

[0003] The requirement to improve the energy efficiency of the structure in which glazing is installed is often met through the use of coatings. Glass coatings that provide low-emissivity (low-e) and / or solar control may be used to selectively absorb or reject light. Low-e and solar control coating stacks are typically composed of the following repeating sequence: '"Order of substrate / dielectric layer / [order of silver (Ag) layer / dielectric layer] n ', each layer does not necessarily have to have the same thickness or composition as the other layers.

[0004] It is becoming increasingly common in the glass manufacturing industry for "n" in the above sequence to be 2, 3, 4, or even 5 or more, allowing the production of coatings consisting of 2, 3, 4, or even 5 or more silver layers. Such coatings may be deposited by a physical vapor deposition process, for example sputtering.

[0005] To provide glazing that meets the required safety standards, glass sheets are often subjected to thermal strengthening, in which the glass sheets are heated to a temperature near or above the softening point of the glass and then rapidly cooled to stress the glass. Glass sheets can be strengthened to various degrees of stress and therefore to higher or lower strength as required.

[0006] Similarly, to provide glazing that conforms to a required shape, glass sheets are often subjected to hot bending, in which the glass sheets are heated to a temperature near or above the softening point of the glass and then bent using a suitable bending means.

[0007] In some cases, bending and tempering may occur simultaneously. Such processes, which use heat to change the shape and / or properties of the glass sheets, are known as "heat treating."

[0008] Much glazing comprises soda-lime-silica glass, often produced using the float process. Tempering or bending of standard float glass of the soda-lime-silica type is usually achieved by heating the glass to a temperature in the range of 580-690 °C, while the glass sheet is held in this temperature range for several minutes before the start of the actual tempering and / or bending process.

[0009] Thus, the term "heat treated" in the following description and claims refers to a thermal process such as bending and / or heat strengthening in which the coated glass sheet reaches a temperature in the range of 580-690°C for at least 5 minutes. Glass that has been subjected to such a treatment is said to be "heat treated".

[0010] Coated glass sheets may also be subjected to tempering and bending processes. However, coated glass sheets are often not suitable for heat treatment and may be damaged by heat treatment. Typical damage to coated glass sheets caused by heat treatment may be indicated by increased haze (often recognized as cloudiness), pinholes, and spots. The functionality of the glazing may be impaired, resulting in reduced light transmission and / or reduced effectiveness of the low-emissivity coating, exemplified by increased sheet resistance values. Thus, coated glass sheets damaged by heat treatment may be unacceptable due to reduced appearance and / or functional capabilities. Coated glass sheets that exhibit such damage upon heat treatment are known as "non-heat treatable". Conversely, a coated glass sheet is considered to be "heat treatable" if it can withstand heat treatment without significant damage.

[0011] It is therefore desirable to produce coated glass sheets that are "heat treatable."

[0012] Furthermore, it is common for glazing installations, such as facades, vehicles or windows, to incorporate glazing sheets that are not heat treated or are not coextensively heat treated. In particular, some glazing sheets that are tempered and / or bent may be placed side by side with glazing sheets that are not tempered and / or bent or are not coextensively tempered and / or bent. For example, a glazing installation may require the lower glass, which occupants may come into contact with, to be tempered by heat treatment, while the upper glass may be required to be cheaper as it only requires annealing. Furthermore, regulations may require glazing in high-rise buildings to be tempered by heat treatment to reduce the risk of glass breakage and falling. In this case, it is important that the color and transparency of the tempered sheets are not significantly different from the annealed sheets to prevent the installation from creating an aesthetically undesirable "checkerboard" effect. This may be achieved using products supplied as annealed and heat treated pairs, with the heat treated product being optically similar to the annealed product. It is therefore important to be able to carefully control the optical properties of the coated glazing when it is subjected to a heat treatment.

[0013] In some cases, it is also advantageous for the coated glazing material to be not only heat treatable, but also to show only negligible changes in its color and transparency after being subjected to a heat treatment process when the values ​​are compared before and after the heat treatment process. A coating that shows negligible changes in color and transparency after being subjected to a heat treatment process when the values ​​are compared before and after the heat treatment process can be supplied in place of the annealed and heat treated paired product and is therefore called a "single stock" coating. In particular, a coating with a ΔE* value of less than 3 is considered suitable for single stock applications. Instead of measuring values ​​before and after the heat treatment process, comparable coated glass sheet values ​​can be compared between an annealed first coated glass sheet and a heat treated second coated glass sheet having the same composition and coating composition.

[0014] The coating layer adjacent to the glass substrate (often referred to as the "base layer") is known to play a critical role in determining product performance. This is believed to be because the coating layer adjacent to the glass substrate is the critical interface between the surface of the substrate and the coating, and must adhere to the substrate. The coating layer adjacent to the glass surface also prevents the diffusion of sodium from the bulk glass into the coating, and such sodium is believed to degrade the performance of the precious metal infrared reflective layer. Sodium diffusion is believed to be exacerbated by heat treatment processes.

[0015] Previous functional coatings included TiO as a base layer. x The TiO x Using TiO as a base layer can produce attractive blue / green reflected colors without compromising IR reflectance. x It was found that coated glazing with a base layer showed unacceptable damage after heat treatment. x It is believed that the TiO layer does not provide a sufficient barrier to the movement of sodium ions.x Coatings containing the inclusion layer were considered to be "non-heat treatable."

[0016] Previous attempts at heat-treatable coatings have focused on SiN adjacent to the glass surface. x However, the SiN x is TiO x As a result, SiN does not offer such beneficial aesthetic properties when compared to x is used as the base layer for the toughenable coating, and TiO x is used in non-strengthenable coatings, complicating the manufacturing process and increasing the use of TiO x and SiN x This requires modification of the manufacturing facility to switch the equipment required for deposition of ZnO. Such modifications can require 2-3 days of downtime, which is costly.

[0017] Alternative compositions of the base layer have been investigated. For example, US Patent Publication No. 20190203529 discloses a functional building material for windows that includes a transparent glass substrate and a low-emissivity coating formed on the transparent glass substrate. The low-emissivity coating includes a vertical sequential stack on the transparent glass substrate that includes a lower barrier layer, and the lower barrier layer can include a first metal, a first composite metal, a first metal oxide, a first composite metal oxide, a first metal oxynitride, a first composite metal oxynitride, and combinations thereof.

[0018] Similarly, WO2008113786 discloses a glazing coated with a set of thin vacuum deposited layers. The glazing comprises one or more silver-based layers and a dielectric layer, at least one of the dielectric layers underneath at least one of the silver-based layers being made of TiMO x or TiMO x N y The layer contains a type of titanium oxide or oxynitride.

[0019] However, a need remains for heat-treatable coated glass sheets that have improved color performance, transparency, and low-emissivity performance. Summary of the Invention

[0020] It is therefore an object of the present invention to provide an improved heat treatable substantially transparent low emissivity coated glass sheet.

[0021] It is a further object of the present invention to provide heat-treatable coated glass sheets which have high light transmittance and low emissivity (corresponding to low sheet resistance) and / or exhibit good solar control properties, i.e. the glass sheets have a low solar energy transmittance combined with a sufficiently high light transmittance.

[0022] Further, in some cases, the present invention aims to provide a single stock coating such that the color change in the coated glass sheet caused by heat treatment, if desired, heat treated and non-heat treated coated glass sheets may be glazed next to each other in use without noticeable color difference.

[0023] According to a first aspect of the present invention, there is provided a coated glass sheet comprising a glass substrate and a coating, the coating comprising, in order from the glass substrate, a base layer adjacent and in contact with the glass substrate, a silver-based functional layer, and an upper dielectric layer, the base layer being made of an oxide of zirconium and titanium, Zr x Ti y O zand the atomic ratio of Zr based on Zr and Ti in the base layer, calculated as x / (x+y), is between 0.40 and 0.95. The inventors have surprisingly found that a coated glass sheet comprising such a base layer provides an improved heat-treatable coated glass sheet providing excellent infrared reflection properties. Thus, the coating is suitable for reflecting infrared radiation. Furthermore, such a base layer provides a heat-treatable coated glass sheet having high light transmittance and low emissivity (corresponding to low sheet resistance) and / or exhibiting good solar control properties, i.e., the glass sheet has a combination of low solar energy transmittance and sufficiently high light transmittance. Moreover, such coated glass sheets can be produced in an economically efficient and commercially desirable manner, meeting the optical properties required for the glass industry, e.g. in terms of haze, light transmittance and color, and also being robust enough to withstand thermal strengthening.

[0024] Without wishing to be bound by any particular theory, the inventors believe that the surprisingly good performance of the coated glass sheets of the present invention may be related to the high sodium blocking ability of the base layer, which prevents sodium migration from the glass substrate to the coating, which can degrade the performance of the coating.

[0025] Additionally, in some embodiments, the present invention provides coated glass sheets suitable for single stock applications. Additionally, some embodiments according to the present invention exhibit an attractive blue-green color in the glass side reflection.

[0026] Additionally, the base layer according to the present invention may be used to replace one or more layers in the lower dielectric layer in an existing coating stack design. In particular, TiO x Base layer and / or SiN x (Zn)SnO in the base layer and / or lower dielectric layer xOther layers, such as layers, can be replaced with a base layer according to the present invention. Advantageously, the base layer according to the present invention can be reduced in thickness compared to the original layer and can provide beneficial properties such as reduced haze and improved sheet resistance. Fewer and / or thinner layers in the stack design can lead to reduced material costs and can also reduce the number of coating processes required, leading to reduced capital expenditures and increased throughput.

[0027] (Base layer) As used herein, the atomic ratio of zirconium (Zr) based on zirconium and titanium (Ti) in the base layer is calculated as x / (x+y) and is calculated by dividing the atomic % of zirconium in the total composition by the sum of the atomic percentages of zirconium and titanium in the total composition. For example, a layer with atomic percent Zr(20), Ti(20), O(60) has an atomic ratio of metallic Zr of 0.5.

[0028] In some embodiments, the base layer consists essentially of titanium, oxygen, and zirconium with only trace amounts of other elements, which according to the present invention refers to impurities that together make up less than 5% by weight of the base layer, preferably less than 1% by weight of the base layer.

[0029] Alternatively, the base layer includes an additional element, such as yttrium, which helps to stabilise the layer. Preferably, the additional element is not present in more than 10% by weight of the base layer.

[0030] The atomic ratio of Zr based on Zr and Ti in the base layer (calculated as x / (x+y)) is preferably 0.50 to 0.90. The atomic ratio of Zr based on Zr and Ti in the base layer (calculated as x / (x+y)) is preferably 0.55 to 0.85. More preferably, the atomic ratio of Zr based on Zr and Ti in the base layer (calculated as x / (x+y)) is 0.60 to 0.80. Even more preferably, the atomic ratio of Zr based on Zr and Ti in the base layer, calculated as x / (x+y), is 0.62 to 0.67. A coated glass sheet including a base layer having such an atomic ratio of Zr has particularly good heat treatment performance, as discussed herein.

[0031] Preferably, the atomic % of titanium in the base layer, calculated as Ti in the total composition, is 1-25, preferably 5-20, more preferably 8-15.

[0032] Preferably, the atomic % of oxygen in the base layer, calculated as O in the total composition, is 60-70, preferably 62-66, more preferably 63-65.

[0033] Preferably, the atomic % of zirconium in the base layer, calculated as Zr in the total composition, is 12-35, preferably 15-25.

[0034] Preferably, the thickness of the base layer is 6 to 60, preferably 8 to 45, more preferably 10 to 30 nm.

[0035] Preferably, the Zr coefficient of the base layer, calculated by multiplying the thickness of the base layer in nm by the atomic ratio of Zr based on Zr and Ti in the base layer, is 1 to 35. More preferably, the Zr coefficient of the base layer, calculated by multiplying the thickness of the base layer in nm by the atomic ratio of Zr based on Zr and Ti in the base layer, is 5 to 20. Even more preferably, the Zr coefficient of the base layer, calculated by multiplying the thickness of the base layer in nm by the atomic ratio of Zr based on Zr and Ti in the base layer, is 7 to 15. The Zr coefficient of the base layer, calculated by multiplying the thickness of the base layer in nm by the atomic ratio of Zr based on Zr and Ti in the base layer, is 8 to 12.

[0036] The inventors have discovered that modifying the thickness and / or composition of the base layer such that the Zr factor remains within the preferred ranges above improves the response of the coated glass sheet to heat treatment. A lower Zr factor is associated with increased haze, while a higher Zr factor is associated with decreased conductivity and / or increased haze.

[0037] (Silver functional layer) The silver-based functional layer preferably consists essentially of silver without any additives, as is common in the field of low-emissivity and / or solar control coatings. However, modifying the properties of the silver-based functional layer by adding dopants, alloy additives, etc., or even by adding very thin metal or metal compound layers is not substantially impaired thereby and is within the scope of the present invention, as long as the silver-based functional layer has the necessary properties to function as a highly light-transmitting, low light-absorbing IR-reflective layer.

[0038] The thickness of each silver-based functional layer depends on its technical purpose. For typical low emissivity and / or solar control purposes, the preferred layer thickness of a single silver-based layer may be preferably 5-20 nm, more preferably 5-15 nm, even more preferably 5-13 nm, even more preferably 8-12 nm, most preferably 9-12 nm. With such layer thickness, light transmittance values ​​of more than 86% and normal emissivity of less than 0.05 after heat treatment can be easily achieved for a single silver coating according to the present invention. If better solar control properties are required, the thickness of the silver-based functional layer may be appropriately increased or several spaced apart functional layers may be provided, as further described below.

[0039] In some embodiments, the silver-based functional layer is in direct contact with the base layer. When the silver-based functional layer is in direct contact with the base layer, the thickness of the base layer is preferably between 20 nm and 60 nm.

[0040] In an alternative embodiment of the invention, the coated glass sheet preferably further comprises a lower dielectric layer between the base layer and the silver layer. Preferably, when the coated glass sheet comprises a lower dielectric layer between the base layer and the silver layer, the base layer has a thickness of 6 nm to 25 nm. Preferably, the lower dielectric layer has a thickness of 20 nm to 70 nm. The lower dielectric layer may comprise one or more of a growth promotion layer, a stabilization layer, a separation layer and / or a barrier layer necessary for the proper functioning of the coating.

[0041] It is within the scope of the present invention to apply the concept of the present invention to prepare low-emissivity and / or solar control coatings that include two or more silver-based functional layers. When more than one silver-based functional layer is provided, all silver-based functional layers are preferably separated by an intervening dielectric layer, collectively referred to herein as a "central anti-reflection layer", to form a Fabry-Perot interference filter. This allows the optical properties of the low-emissivity and / or solar control coating to be further optimized for each application.

[0042] Preferably, each silver-based functional layer is separated from an adjacent silver-based functional layer by an intervening central dielectric layer, which may comprise a combination of one or more of layers based on silicon (oxy)nitrides and / or aluminium (oxy)nitrides, layers based on zinc and tin oxides or tin oxides, and layers based on metal oxides such as zinc oxide.

[0043] In some embodiments, the coating further comprises a second silver-based functional layer between the silver-based functional layer and the top dielectric layer. Preferably, the coating further comprises a central dielectric layer between the silver-based functional layer and the second silver-based functional layer, and / or a second barrier layer between the second silver-based functional layer and the top dielectric layer.

[0044] In some embodiments, the coating further comprises a third silver-based functional layer between the second silver-based functional layer and the top dielectric layer. Preferably, the coating further comprises a second central dielectric layer between the second silver-based functional layer and the third silver-based functional layer, and / or a third barrier layer between the third silver-based functional layer and the top dielectric layer.

[0045] In some embodiments, the coating further comprises a fourth silver-based functional layer between the third silver-based functional layer and the top dielectric layer. Preferably, the coating further comprises a third central dielectric layer between the third silver-based functional layer and the fourth silver-based functional layer, and / or a fourth barrier layer between the fourth silver-based functional layer and the top dielectric layer.

[0046] In some cases, the central dielectric layer is made of zirconium and titanium oxide, Zr x Ti y O z In some embodiments, the central dielectric layer may comprise a layer comprising zirconium and titanium oxide, Zr x Ti y O zmay have an atomic ratio of Zr based on Zr and Ti, calculated as x / (x+y), of 0.40 to 0.95.

[0047] In some preferred embodiments, each silver-based functional layer is separated from another silver-based functional layer by an intervening central dielectric layer, which comprises at least, from the silver-based functional layer located closest to the glass substrate, a layer based on silicon (oxy)nitride and / or aluminum (oxy)nitride, a layer based on zinc and tin oxide or tin oxide, and a layer based on a metal oxide, such as zinc oxide.

[0048] Thus, for coated glass sheets comprising two or more silver-based functional layers, it is preferred that each silver-based functional layer is separated from an adjacent silver-based functional layer by an intervening central dielectric layer; Each central dielectric layer comprises at least, starting with the silver-based functional layer located closest to the glass substrate: a layer based on a mixed metal oxide comprising nickel and chromium; a layer mainly composed of a mixed metal oxide mainly composed of zinc and aluminum; - a layer based on silicon (oxy)nitride and / or aluminium (oxy)nitride, a layer based on tin oxide, preferably comprising zinc; a layer based on a metal oxide, such as zinc oxide; Equipped with.

[0049] (Top dielectric layer) Also in accordance with the first aspect of the invention, the coated glass comprises an upper dielectric layer. The top dielectric layer is made up of a top silver-based functional layer, (i) a layer based on tin oxide, preferably comprising zinc, or a layer based on zinc, preferably containing aluminium, or a layer based on tungsten nitride, and / or (ii) It may comprise a layer based on a silicon (oxy)nitride and / or an aluminium (oxy)nitride, or preferably a zinc-based layer with aluminium.

[0050] The layer based on tin oxide, preferably with zinc, in the upper dielectric layer may preferably have a thickness of 0.5 to 5 nm, more preferably 1 to 4 nm, even more preferably 1.5 to 3 nm. These preferred thicknesses allow easier deposition and improved optical properties such as haze, while maintaining mechanical durability.

[0051] The zinc-based layer, preferably containing aluminum in the upper dielectric layer, may preferably have a thickness of 0.5 to 5 nm, more preferably 1 to 4 nm, even more preferably 1.5 to 3 nm. These preferred thicknesses allow for easier deposition and improved optical properties such as haze, while maintaining mechanical durability.

[0052] The tungsten nitride based layer of the upper dielectric layer may increase absorption while minimizing the effect of the tungsten nitride based layer on the glass side reflected color perceived by the observer, so that the glass sheet may exhibit approximately the same appearance even if the light and / or energy transmission characteristics of a given coating stack are changed by modifying the thickness of the absorbing layer. The tungsten nitride based layer preferably has a thickness of 0.5-25 nm, more preferably 1-15 nm, even more preferably 2-8 nm, and even more preferably 3-5 nm.

[0053] The layers in the upper antireflection layer based on aluminum (oxy)nitride or silicon (oxy)nitride preferably have a thickness of at least 5 nm, preferably between 5 and 50 nm, more preferably between 10 and 40 nm, even more preferably between 10 and 30 nm, most preferably between 15 and 30 nm. Such thicknesses provide a further improvement in terms of the mechanical robustness of the coated glass pane. The layers based on aluminum (oxy)nitride or silicon (oxy)nitride may preferably be in direct contact with a layer comprising an oxide of zinc (Zn) in the upper dielectric layer.

[0054] A layer based on aluminum (oxy)nitride and / or silicon (oxy)nitride may constitute the majority of the top anti-reflective layer and provide stability (better protection during thermal treatment) and diffusion barrier properties. The layer is preferably deposited on a Si, Al or mixed SiAl target, e.g. Si, in a N2-containing atmosphere. 90 Al 10 The layers are deposited as Al-nitride and / or Si-nitride layers by reactive sputtering of the target. The composition of the layers based on aluminum (oxy)nitride and / or silicon (oxy)nitride is substantially stoichiometric Si 90 Al 10 N x Preferably, the layer of the upper dielectric layer is based on a substantially stoichiometric metal oxide. The use of a layer based on a substantially stoichiometric metal oxide, rather than a metal or less than 95% stoichiometric barrier layer, results in a very high optical stability of the coating during heat treatment, effectively helping to keep the optical changes during heat treatment small. Furthermore, the use of a layer based on a substantially stoichiometric metal oxide provides advantages in terms of mechanical robustness.

[0055] In order to further optimize the optical properties of the coated glass pane, the top and / or central dielectric layer may comprise further partial layers of suitable materials generally known as dielectric layers, in particular for low-emissivity and / or solar control coatings, in particular selected from one or more of the oxides of Sn, Ti, Zn, Nb, Ce, Hf, Ta, Zr, Al and / or Si, and / or (oxy)nitrides of Si and / or Al, or combinations thereof. However, when adding such further partial layers, it must be ensured that the heat-processability aimed at in the present invention is not thereby impaired.

[0056] In some cases, the upper dielectric layer is an oxide of zirconium and titanium, Zr x Ti y O z In some embodiments, the upper dielectric layer may comprise a layer comprising zirconium and titanium oxide, Zr x Ti y O z may have an atomic ratio of Zr based on Zr and Ti, calculated as x / (x+y), of 0.40 to 0.95.

[0057] (Growth promotion layer) Preferably, the coating further comprises a growth-promoting layer between the base layer and the silver-based functional layer, the growth-promoting layer serving as a growth-promoting layer for the subsequently deposited silver-based functional layer, the silver-based functional layer being preferably in direct contact with the growth-promoting layer.

[0058] In some embodiments, the growth-promoting layer may be in direct contact with the base layer and the silver layer such that there is no stabilization layer between the base layer and the silver layer. Preferably, when the growth-promoting layer is in direct contact with the base layer, the base layer has a thickness of 10 to 60 nm.

[0059] Preferably, the growth-promoting layer is based on zinc oxide. Zinc oxide and mixed zinc oxide are effective growth-promoting layers, which help to achieve low sheet resistance at a given thickness of the subsequently deposited silver-based functional layer. The growth-promoting layer based on zinc oxide is optionally mixed with a metal such as aluminum or tin in an amount of up to about 10% by weight (weight % refers to the target metal content). The usual content of said metal such as aluminum or tin is about 2% by weight, with aluminum being preferred in practice.

[0060] The zinc oxide-based growth promotion layer of the lower dielectric layer is preferably deposited by reactive sputtering from a zinc target in an atmosphere containing oxygen (O2) or by sputtering from an optionally aluminum-doped ceramic target based on zinc oxide, for example, in an atmosphere generally containing zero or only a small amount of oxygen, i.e. generally less than about 5% by volume of oxygen.

[0061] The growth promotion layer may preferably have a thickness of at least 2 nm. More preferably, the growth promotion layer may preferably have a thickness of 2 to 15 nm, or 3 to 12 nm. Even more preferably, the growth promotion layer may preferably have a thickness of 4 to 10 nm. Most preferably, the growth layer has a thickness of 5 to 8 nm.

[0062] (Stabilizing layer) Preferably, the coating further comprises a stabilizing layer between the base layer and the growth promoting layer. Preferably, the stabilizing layer is in direct contact with the base layer and / or is (Zn)SnO x Equipped with.

[0063] It is believed that the stabilization layer improves stability during heat treatment by providing a dense, thermally stable layer, and contributes to reducing haze after heat treatment.

[0064] Preferably, the stabilization layer comprises tin oxide, preferably zinc, (Zn)SnO x As used herein, (Zn)SnO xThe layer containing tin oxide, SnO x , or zinc tin oxide, ZnSnO x It may include any of the following.

[0065] When the stabilization layer comprises zinc tin oxide, the stabilization layer preferably comprises, in weight percent of the total metal content of the layer, 10-90 wt.% zinc and 90-10 wt.% tin, more preferably 40-60 wt.% zinc and 40-60 wt.% tin, even more preferably about 50 wt.% each of zinc and tin. In some preferred embodiments, the stabilization layer comprising zinc tin oxide comprises up to 18 wt.% tin, more preferably up to 15 wt.% tin, even more preferably up to 10 wt.% tin. The stabilization layer comprising zinc tin oxide is preferably deposited by reactive sputtering of a mixed ZnSn target in the presence of O2.

[0066] The thickness of the stabilization layer is preferably at least 0.5 nm. Preferably, the stabilization layer has a thickness of 0.5 to 15 nm, or 0.5 to 13 nm, or 1 to 12 nm. Furthermore, the stabilization layer may have a thickness of 1 to 7 nm, or 2 to 6 nm, or 3 to 6 nm. Most preferably, the stabilization layer has a thickness of 3 to 5 nm for coated glass sheets with a layer sequence comprising zinc tin oxide and a single silver-based functional layer. An upper thickness limit in the range of 8 nm is preferred due to the optical interference conditions required to maintain the optical interference boundary conditions for the antireflection of the functional layer, and also due to the resulting reduced heat treatability due to the reduced thickness of the base layer.

[0067] In another embodiment of the first aspect of the invention, when the coated glass sheet comprises two or more silver-based functional layers, it is preferred that the stabilization layer has a thickness of at least 10 nm. More preferably, the stabilization layer has a thickness of 10 nm to 20 nm. Even more preferably, the stabilization layer has a thickness of 12 nm to 16 nm. Most preferably, the stabilization layer comprises zinc tin oxide and has a thickness of 12 nm to 14 nm.

[0068] (separation layer) In some embodiments, the coating further comprises a separation layer between the stabilization layer and the growth-promoting layer, preferably in direct contact with the stabilization layer and / or comprising a metal oxide and / or an (oxy)nitride of silicon and / or an (oxy)nitride of aluminum and / or an alloy thereof.

[0069] When the coating sequence comprises two or more silver-based coating layers, the lower dielectric layer preferably consists of, in order from the glass substrate, a stabilizing layer and a growth-promoting layer. However, when the coating sequence comprises only a single silver-based coating layer, the lower dielectric layer may additionally comprise a separation layer between the stabilizing layer and the growth-promoting layer.

[0070] The separating layer may preferably be based on a metal oxide and / or an (oxy)nitride of silicon and / or an (oxy)nitride of aluminium and / or an alloy thereof.

[0071] The term "silicon (oxy)nitride" refers to silicon nitride (SiN x ) and silicon oxynitride (SiO x N y ), whereas the term "aluminum (oxy)nitride" includes aluminum nitride (Al) (AlN x ) and aluminum oxynitride (Al) (AlOxN y The layers of silicon nitride (Si), silicon oxynitride (Si), aluminum nitride (Al), and aluminum oxynitride (Al) are preferably substantially stoichiometric (e.g., in silicon nitride = Si3N4, SiN x The value of x in (x=1.33) may be substoichiometric or superstoichiometric, as long as it does not adversely affect the heat processability of the coating. One preferred composition of the base layer based on silicon (oxy)nitride and / or aluminum (oxy)nitride of the lower dielectric layer is the substantially stoichiometric mixed nitride Si 90 Al 10 N x It is.

[0072] Silicon (oxy)nitride and / or aluminum (oxy)nitride layers can be reactively sputtered from silicon (Si) and / or aluminum (Al) based targets in a sputtering atmosphere containing nitrogen and argon, respectively. The oxygen content of the silicon (oxy)nitride and / or aluminum (oxy)nitride based layers can result from residual oxygen in the sputtering atmosphere or from a controlled content of added oxygen in said atmosphere. Generally, it is preferred if the oxygen content of the silicon (oxy)nitride and / or aluminum (oxy)nitride is significantly lower than its nitrogen content, i.e. the atomic ratio O / N in the layer is kept significantly lower than 1. It is most preferred to use silicon nitride and / or aluminum nitride with a negligible oxygen content. This feature can be controlled by ensuring that the refractive index of the layer is not significantly different from that of an oxygen-free silicon nitride and / or aluminum nitride layer.

[0073] It is within the scope of the present invention to use mixed silicon (Si) and / or aluminum (Al) targets or to otherwise add metals or semiconductors to the silicon (Si) and / or aluminum (Al) components of the layer, so long as the essential barrier and protective properties of the layer are not lost, so long as the following conditions are met: For example, aluminum (Al) and silicon (Si) targets may be mixed, although other mixed targets are not excluded. Additional components may be present in amounts typically between 10 and 15% by weight. Aluminum is typically present in mixed silicon targets in amounts of 10% by weight.

[0074] In addition, the separation layer may preferably have a thickness of at least 0.5 nm, or may preferably have a thickness of 0.5-6 nm, more preferably 0.5-5 nm, even more preferably 0.5-4 nm, and most preferably 0.5-3 nm. These preferred thicknesses allow for further improvement of haze during heat treatment. The separation layer preferably provides protection during the deposition process and during subsequent heat treatment. The separation layer is preferably either substantially fully oxidized immediately after deposition or oxidized to a substantially fully oxidized layer during the deposition of a subsequent oxide layer.

[0075] When the separating layer is based on a metal oxide, it may preferably comprise a layer based on an oxide of Ti, Zn, NiCr, InSn, Zr, Al and / or Si.

[0076] When the separating layer is preferably based on a metal oxide, it is, for example, a slightly substoichiometric titanium oxide, e.g. TiO 1.98 They can be deposited as substantially stoichiometric or slightly substoichiometric oxides using non-reactive sputtering from a Ti-based ceramic target, by reactive sputtering of a Ti-based target in the presence of O2, or by depositing a thin Ti-based layer which is then oxidized. In the context of the present invention, "substantially stoichiometric oxide" means an oxide that is at least 95% but up to 100% stoichiometric, while "slightly substoichiometric oxide" means an oxide that is at least 95% but less than 100% stoichiometric.

[0077] In addition to the metal oxide and / or (oxy)nitride of silicon and / or (oxy)nitride of aluminum and / or alloys thereof on which it is based, the separation layer may further comprise one or more other chemical elements selected from at least one of the elements Ti, V, Mn, Co, Cu, Zn, Zr, Hf, Al, Nb, Ni, Cr, Mo, Ta, Si or alloys based on at least one of these materials used, for example, as dopants or alloying agents.

[0078] Preferably, however, a separation layer based on a metal oxide and / or (oxy)nitride of silicon and / or an (oxy)nitride of aluminium does not contain one or more other chemical elements.

[0079] In one preferred embodiment of the invention, the separating layer is based on a metal oxide, including oxide of zinc (Zn) and / or oxide of titanium (Ti).

[0080] In another preferred embodiment of the invention, the separation layer is based on a metal oxide, including an oxide of titanium.

[0081] When the layer sequence of the coated glass comprises one silver-based functional layer, it is particularly preferred that the separating layer is based on an oxide of titanium.

[0082] When the layer sequence comprises two or more silver-based functional layers, the separation layer may be based on an oxide of titanium, but it may also be preferred that when the layer sequence or stack comprises two or more silver-based functional layers, the layer sequence does not comprise a separation layer in the lower dielectric layer.

[0083] When the separating layer is mainly composed of a metal oxide, and the metal oxide is mainly composed of titanium oxide, the preferred thickness of the titanium oxide is 0.5 to 3 nm.

[0084] Thus, when the coating sequence comprises only a single silver-based coating layer, the lower dielectric layer may consist, in order from the glass substrate, of a zinc tin oxide layer in direct contact with the base layer, a separation layer in direct contact with the zinc tin oxide layer, and a zinc oxide layer in direct contact with the separation layer.

[0085] Alternatively, when the coating sequence comprises two or more silver-based layers, the lower dielectric layer may be composed of, in order from the glass substrate, a zinc tin oxide layer in direct contact with the base layer, and a zinc tin oxide layer in direct contact with the zinc oxide layer.

[0086] In a further embodiment, when the coating sequence includes two or more silver-based layers, preferably a zinc oxide growth-promoting layer can be in contact with the base layer and the silver-based layer. In this case, the thickness of the zirconium titanium oxide base layer can be increased. Alternatively, when the coating sequence includes two or more silver-based layer coatings, the coating sequence can include a zirconium titanium oxide base layer, a further zirconium titanium oxide stabilizing layer in contact with the base layer, and a zinc oxide layer in contact with the stabilizing layer. In this embodiment, the lower dielectric layer does not need a zinc tin oxide layer, making the coating structure simpler.

[0087] (Barrier layer) Preferably, the coating further comprises a barrier layer between the silver-based functional layer and the upper dielectric layer. Preferably, the barrier layer is in direct contact with the silver-based functional layer.

[0088] Preferably, when the coating comprises a plurality of silver-based functional layers, each silver-based functional layer is in direct contact with the barrier layer above. At least a portion of the barrier layer in direct contact with the silver-based functional layer is preferably deposited using non-reactive sputtering to avoid damaging the silver. It has been found that when the barrier layer comprises a layer of mixed metal oxide sputtered from a mixed metal oxide target, excellent protection of the silver-based functional layer during the deposition process and high optical stability during heat treatment can be achieved.

[0089] In some embodiments, the barrier layer comprises a layer based on zinc oxide. When the barrier layer comprises a layer based on zinc oxide, the oxide may be a mixed metal oxide such as ZnO:Al. In particular, good results are obtained when the ZnO:Al-based layer is sputtered from a conductive ZnO:Al target. The ZnO:Al may be deposited fully oxidized or slightly suboxidized.

[0090] The barrier layer may preferably comprise a layer based on zinc oxide having a thickness of at least 0.5 nm, more preferably the barrier layer comprises a layer based on zinc oxide having a thickness of 0.5-10 nm. Most preferably the barrier layer comprises a layer based on zinc oxide having a thickness of 1-10 nm. Furthermore, when the barrier layer comprises a layer based on zinc oxide, the barrier can in fact comprise multiple zinc oxide layers, such as layers based on mixed metal oxides, such as ZnO:Al, but also layers based on oxides of zinc and tin. Thus, suitable barrier layers are, in order from the glass substrate, ZnO:Al, ZnSnO x , ZnO:Al triple-layer. Such a triple barrier configuration may have a total thickness of 3-12 nm.

[0091] Furthermore, the triple barrier structure preferably has a silver-based functional layer followed by ZnO:Al / TiO x / ZnO:Al, ZnO:Al / ZnSnO x / ZnO:Al, TiO x / ZnSnO x / ZnO:Al, TiO x / ZnO:Al / TiO x , TiO x / ZnSnO x / TiO x , and ZnO:Al / ZnSnO x / TiO x The layer combination may be selected from the group consisting of:

[0092] Alternatively, the barrier layer may be NiCrO x Further, the barrier layer may comprise a layer based on a mixed metal oxide based on nickel and chromium, such as a layer of NiCrO x It has been found that a suitable protection of the silver-based functional layer during the deposition process and a high optical stability during heat treatment can be achieved when the coated glass pane comprises a mixed metal oxide based on nickel and chromium, such as a layer of NiCrO. This is especially true when the coated glass pane comprises two or more silver-based functional layers. However, xThe layer of NiCrO can also be used when the coated glass sheet comprises a single silver-based functional layer. x The layer is substoichiometric NiCrO x It is deposited as

[0093] Thus, in some embodiments, the barrier layer may preferably comprise a layer based on a mixed metal oxide based on nickel and chromium having a thickness of at least 0.5 nm, more preferably the barrier layer comprises a layer based on a mixed metal oxide based on nickel and chromium having a thickness of 0.5-10 nm, and most preferably the barrier layer comprises a layer based on a mixed metal oxide based on nickel and chromium having a thickness of 1-10 nm.

[0094] (protective layer) Preferably, the coated glass pane further comprises a protective layer, which is the outermost layer of the coating, in order to increase the mechanical and / or chemical robustness, e.g. scratch resistance. Preferably, the protective layer comprises a layer based on an oxide of zinc and tin. In addition to zinc and tin, the protective layer may comprise zirconium. Preferably, the layer based on an oxide of zinc, tin and zirconium comprises 12 to 35 atomic % zirconium. More preferably, the layer based on an oxide of zinc, tin and zirconium comprises 15 to 33 atomic % zirconium. Most preferably, the layer based on an oxide of zinc, tin and zirconium comprises 18 to 33 atomic % zirconium.

[0095] The inventors have discovered that coated glass sheets according to the invention can have excellent and controllable color properties. It is therefore possible to provide coated glass sheets with attractive colors.

[0096] In particular, glass panes with highly achromatic coatings are feasible, or, if desired, slightly or even strongly colored glass panes can be provided.

[0097] In certain embodiments, it is desirable to provide a coated glass sheet having an Rg a* of -6 to +6.5 and an Rg b* of -14 to -2.5.

[0098] Preferably, when the coated glass sheet comprises a coating that includes only one silver-based functional layer, the coated glass sheet has an Rg a* of -3 to +6.5 and an Rg b* of -14 to -4.

[0099] When the coated glass sheet includes a coating that includes two or more silver-based functional layers, it is preferred that the coated glass sheet has an Rg a* of -6 to +4.8 and an Rg b* of -18.5 to -2.3.

[0100] Such coated glazing is particularly suitable for architectural glazing.

[0101] The sheet resistance (Rs) depends on the number and thickness of the silver layers in the coating; the more silver layers or the thicker they are, the lower the measured sheet resistance. Preferably, the sheet resistance Rs is less than 8 Ω / □.

[0102] If the coated glass sheet comprises only one silver layer, the sheet resistance after deposition may be less than 8 Ω / □, preferably less than 7 Ω / □, and even more preferably less than 6 Ω / □.If the coated glass sheet comprises only one silver layer, preferably the sheet resistance after heat treatment is less than 7 Ω / □, preferably less than 6 Ω / □, and even more preferably less than 5 Ω / □.

[0103] When the coated glass sheet comprises two or more silver layers, the sheet resistance after deposition may be less than 5 Ω / □, preferably less than 4 Ω / □, and even more preferably less than 3 Ω / □.When the coated glass sheet comprises only two silver layers, the sheet resistance after heat treatment may be less than 4 Ω / □, preferably less than 3 Ω / □, and even more preferably less than 2 Ω / □.

[0104] It is desirable for the change in sheet resistance induced by the heat treatment to be negative, indicating that the silver functional layer is not damaged by the heat treatment, and therefore ΔRs is preferably negative.

[0105] The inventors have discovered that coated glass sheets according to the present invention can have excellent properties suitable for being subjected to a heat treatment process.

[0106] In some embodiments, the coated glass sheet is a heat treatable coated glass sheet. As defined herein, a coated glass sheet is considered to be "heat treatable" if it can withstand heat treatment without significant damage.

[0107] Preferably, the heat-treatable coated glass sheet undergoes a negative sheet resistance change ΔRs upon heat treatment.

[0108] Preferably, the heat-treatable coated glass sheet undergoes a positive change in light transmittance TL upon heat treatment. However, a large increase in light transmittance may be undesirable, as it may increase glare. Therefore, it is preferred that the increase in %TL is 10% or less, more preferably 5% or less.

[0109] Preferably, the heat treatable coated glass sheet, upon heat treatment, provides a heat treated coated glass sheet having a haze scan value of less than 90, more preferably less than 60, and even more preferably less than 50.

[0110] In some embodiments, the coated glass sheet is a heat-treated coated glass sheet. Preferably, the heat-treated coated glass sheet is a heat-bent coated glass sheet or a heat-strengthened coated glass sheet.

[0111] The coated glass sheet subjected to hot bending preferably has a radius of curvature of at least 2°.

[0112] A coated glass sheet that has been thermally strengthened is preferably at least twice as strong as annealed glass of similar thickness.A coated glass sheet that has been thermally strengthened is preferably at least four times as strong as annealed glass of similar thickness.

[0113] Preferably, the heat-strengthened heat-treated coated glass sheet has a surface strength of 400 to 1500 kg / m 2 When the heat-strengthened heat-treated coated glass sheet comprises a tempered glass sheet, the coated glass sheet preferably has a compressive stress of 750 to 1500 kg / m on the surface. 2 Alternatively, the heat-strengthened, heat-treated, coated glass sheet has a compressive stress of 400 to 700 kg / m2 on the surface. 2 Such glass sheets are known in the art as "thermally strengthened" rather than "strengthened" glass.

[0114] Thermally strengthened glass sheets are regulated by standards such as EN12600 and BS 6206:1981.

[0115] The thermally strengthened coated glass panes preferably achieve Class 1 of EN 12600.

[0116] Preferably, the thermally strengthened coated glass sheet achieves Class 1 of EN 12600 with failure mode type C. More preferably, the thermally strengthened coated glass sheet achieves Class 1(C)1 of EN 12600. Preferably, the thermally strengthened coated glass sheet meets Class C, more preferably Class B, even more preferably Class A of BS 6206:1981.

[0117] Glazing may be classified according to its resistance to manual attack according to EN 356. Preferably, the thermally strengthened coated glass panes comply with at least P1A and / or P6B according to EN 356.

[0118] Preferably, the glass sheet that has undergone thermal strengthening has been subjected to a heat soak process.

[0119] In some embodiments, the heat treated coated glass sheet has a ΔE* of 3 or less compared to a comparable annealed coated glass sheet. Preferably, the heat treated coated glass sheet has a ΔE* of 2 or less compared to a comparable annealed coated glass sheet. More preferably, the heat treated coated glass sheet has a ΔE* of 1 or less compared to a comparable annealed coated glass sheet.

[0120] In some embodiments, the heat treated coated glass sheets exhibit a haze scan value of less than 90. Preferably, the haze scan value is less than 80, and even more preferably less than 70. In some specialty applications where transparency is a priority, a haze scan value of less than 60, and preferably less than 50, is desired.

[0121] It will be understood that a coating according to the invention may include further coating layers, any further layers may contain additives, such as dopants, or reaction products of reactive sputtering gases, that modify their properties and / or facilitate their manufacture. In the case of oxide-based layers, nitrogen may be added to the sputtering atmosphere, leading to the formation of oxynitrides rather than oxides, and in the case of nitride-based layers, oxygen may be added to the sputtering atmosphere, leading to the formation of oxynitrides rather than nitrides.

[0122] When adding such further partial layers to the basic layer sequence of the glass pane of the invention, care must be taken by appropriate material, structure and thickness selection so that the primarily aimed properties, e.g. high thermal stability, are not thereby significantly impaired.

[0123] Also, in the context of the present invention, when a layer is said to be "based on" a particular material or materials, this means that the layer primarily comprises the material in at least 50 atomic percent by weight, unless otherwise specified.

[0124] The layer is ZnSnO x Based on the above, "ZnSnO x " means mixed oxides of Zn and Sn, as explained and defined elsewhere herein.

[0125] Disclosed herein are embodiments according to the invention that may provide particularly beneficial properties. The following layer sequence is provided starting from the glass substrate, but is not limited thereto. In the layer sequences below, " / " indicates the boundary of adjacent layers that abut each other at the boundary. For example, embodiments of the invention include a coating comprising: (i) Zr x Ti y O z / ZnSnO x / TiO x / AlZnO x / Ag / NiCrO x / AlZnO x / AlN x / ZnSnO x or (ii) Zr x Ti y O z / AlZnO x / Ag / AlZnO x / ZnSnO x / ZrO x or (iii) Zr x Ti y O z / AlZnO x / Ag / NiCr / AlZnO x / ZnSnOx / ZrO x or (iv) Zr x Ti y O z / AlZnO x / Ag / AlZnO x / ZnSnO x / Ag / AlZnO x / ZnSnO x / ZrO x The coated glass sheet may comprise, or preferably consist of,

[0126] According to a second aspect of the present invention there is provided a method for producing a coated glass sheet according to the first aspect of the present invention, the method comprising the steps of: (i) providing a glass substrate; (ii) providing a base layer; (iii) providing a silver-based functional layer; (iv) providing a top dielectric layer; Includes.

[0127] With respect to the second aspect of the invention, it should be understood that all features of the first aspect of the invention, such as the glass substrate, the base layer, the top dielectric layer and the silver-based functional layer, may be applied to the second aspect of the invention in any combination.

[0128] The invention is not limited to a specific manufacturing process of the coating. However, it is particularly preferred that at least one of the layers, and most preferably all layers, are applied by magnetron cathode sputtering, in which a metallic or semiconducting target is sputtered reactively or non-reactively in a suitable sputtering atmosphere, either in DC mode, pulse mode, medium wave mode or any other suitable mode. Depending on the material to be sputtered, planar or rotating tubular targets may be used.

[0129] Preferably, the base layer, and / or the silver-based functional layer, and / or the top dielectric layer are applied by physical vapour deposition.

[0130] Preferably, the base layer is applied by physical vapour deposition from a ceramic target in a substantially inert atmosphere or from one or more metallic targets in a substantially oxidising atmosphere.

[0131] A substantially inert atmosphere is defined herein as an atmosphere having 10% oxygen or less. A substantially oxidizing atmosphere is defined herein as an atmosphere having more than 10% oxygen.

[0132] In the context of the present invention, the term "non-reactive sputtering" includes sputtering an oxide target in a low oxygen atmosphere (i.e., zero or up to 10% volumetric oxygen) to provide a substantially stoichiometric oxide.

[0133] In some embodiments, the base layer is produced using reactive sputtering from a TiZr metal target in an Ar / O2 atmosphere. Alternatively, the base layer is produced by co-sputtering titanium and zirconium metal targets in an Ar / O2 atmosphere. Alternatively, the base layer is produced by co-sputtering TiZr metal targets in an atmosphere with less than 10% oxygen. x Zr y O x It is produced by sputtering from a ceramic target.

[0134] Layers based on oxides of Zn, Ti, ZnSn, InSn, Zr, Al, Sn and / or Si and / or (oxy)nitrides of Si and / or Al can be deposited from non-reactive sputtering. The layers can be sputtered from ceramic targets.

[0135] Layers based on oxides of Zn, Ti, ZnSn, InSn, Zr, Al, Sn and / or Si and / or (oxy)nitrides of Si and / or Al can also be deposited by reactive sputtering: the layers can be sputtered from one or more metal targets.

[0136] A layer may be applied to its final total thickness in a single coating pass. Alternatively, a single layer of final thickness may also be applied using multiple coating passes using the same coating chemistry. As used herein, sublayers of substantially the same composition provided by multiple passes are considered to be a single layer having a thickness equal to the sum of the thicknesses of the sublayers together.

[0137] In order to minimize light absorption in the coating and to suppress undesirable increases in light transmission during heat treatment, it is preferable to deposit all individual layers of the upper and lower dielectric layers with substantially stoichiometric compositions. The coating process is carried out by setting appropriate coating conditions such that any oxygen (or nitrogen) deficiency in any oxide (or nitride) layer of the anti-reflective layer of the coating is kept low, achieving high stability of light transmission and color of the coated glass sheet during heat treatment.

[0138] The light transmission values ​​referred to herein generally refer to the light transmission T of 90% of the area without any coating. L It is specified with reference to a coated glass sheet comprising a standard float glass sheet having a thickness of 4 mm.

[0139] The color of the coated glass sheets according to the invention, although achromatic reflection and transmission color of the coated glass sheets is usually targeted, can be greatly modified by suitable adaptation of the thicknesses of the individual layers according to the intended visual appearance of the product.

[0140] The thermal stability of the coated glass sheets according to the invention is reflected by the fact that the heat-treated coated glass sheets do not exhibit unacceptable levels of haze. If a significant increase in haze value (haze scan) is detected during heat treatment, this indicates that the coating is starting to become damaged.

[0141] According to a third aspect of the invention there is provided a multiple insulation glazing unit incorporating a coated glass pane according to the first and / or second aspect of the invention. Furthermore, the multiple insulation glazing unit according to the third aspect of the invention may be a laminated glazing unit and / or an insulating glazing unit.

[0142] According to a fourth aspect of the invention there is provided the use of a coated glass sheet according to or produced according to the preceding embodiments in a building or vehicle.

[0143] Features of the first and / or second aspects of the invention may be applied to the third and fourth aspects in any combination.

[0144] Embodiments of the present invention will now be described, by way of non-limiting example, with reference to Figures 1 to 7. [Brief description of the drawings]

[0145] [Figure 1] FIG. 1 is a schematic cross-sectional view of a coated glass sheet according to a first embodiment of the invention. [Diagram 2] FIG. 2 is a schematic cross-sectional view of a coated glass sheet according to a second embodiment of the invention. [Diagram 3] FIG. 4 is a schematic cross-sectional view of a coated glass sheet according to a third embodiment of the present invention. [Figure 4] FIG. 13 shows a chart of haze scan and sheet resistance Rs T after heat treatment versus atomic ratio of Zr based on Zr and Ti for a coated glass sheet with a coating comprising only one silver layer. [Diagram 5]FIG. 13 shows a chart of haze scan and post-heat treatment sheet resistance Rs T versus Zr coefficient for a coated glass plate with a coating comprising only one silver layer. [Figure 6] FIG. 13 shows a chart of haze scan and sheet resistance Rs T after heat treatment versus atomic ratio of Zr based on Zr and Ti for a coated glass sheet comprising a coating comprising two or more silver layers. [Figure 7] FIG. 1 shows a chart of haze scan and sheet resistance Rs T after heat treatment versus Zr coefficient for a coated glass plate with a coating comprising two or more silver layers. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0146] In the figures, like features are represented with like numbers.

[0147] FIG. 1 shows a coated glass sheet 100 according to a first embodiment of the invention comprising a glass substrate 1 and a coating 2, the coating 2 comprising, in order from the glass substrate 1, a base layer 3 adjacent and in contact with the glass substrate 1, a silver-based functional layer 5 and an upper dielectric phase 7, the base layer 3 comprising oxides of zirconium and titanium, the atomic ratio of Zr based on Zr and Ti in the base layer being between 0.40 and 0.95.

[0148] FIG. 2 shows a coated glass sheet 200 according to a second embodiment of the present invention, comprising a glass substrate 1 and a coating 2, the coating 2 comprising, in order from the glass substrate 1, a base layer 3 adjacent to and in contact with the glass substrate 1, a lower dielectric layer 4 comprising a stabilization layer 41, an isolation layer 42 and a growth layer 43, a silver-based functional layer 5, a barrier layer 6, an upper dielectric layer 7 and a protective layer 8, the base layer 3 comprising oxides of zirconium and titanium, the atomic ratio of Zr based on Zr and Ti in the base layer being 0.40-0.95.

[0149] FIG. 3 shows a coated glass sheet 300 according to a third embodiment of the present invention, comprising a glass substrate 1 and a coating 2, the coating 2 comprising, in order from the glass substrate 1, a base layer 3 adjacent and in contact with the glass substrate 1, a lower dielectric layer 4 comprising a stabilization layer 41, an isolation layer 42 and a growth layer 43, a first silver-based functional layer 51, a first barrier layer 61, a central dielectric layer 9, a second silver-based functional layer 52, a second barrier layer 62, an upper dielectric layer 7 and a protective layer 8, the base layer 3 comprising oxides of zirconium and titanium, the atomic ratio of Zr based on Zr and Ti in the base layer being 0.40-0.95.

[0150] Exemplary embodiments of the present invention will now be described, by way of example only.

[0151] In all examples, the coatings were deposited on standard float glass sheets of 4 mm thickness using AC and / or DC magnetron (or pulsed DC) sputtering devices with an area light transmission of 90% and applying medium frequency sputtering as required.

[0152] A base layer containing zirconium and titanium oxides was reactively co-sputtered from a first target of titanium metal and a second target of zirconium metal in an argon / oxygen (Ar / O2) sputtering atmosphere containing approximately 12% oxygen. The ratio of Zr to Ti was varied by changing the sputtering power on the targets. The power of the Ti target was varied between 0.4 and 1.5 kW, and the power of the Zr target was varied between 0.15 and 1.5 kW.

[0153] Dielectric layers of zinc and tin oxides were reactively sputtered from a zinc-tin target (weight ratio Zn:Sn approx. 50:50) in an argon / oxygen (Ar / O2) sputtering atmosphere.

[0154] Dielectric layers of zinc (Zn), tin (Sn), and zirconium (Zr) oxides were co-sputtered using metallic ZnSn (Zn:Sn weight ratio ≈50:50) and Zr targets in Ar / O2 or pure argon (Ar) atmosphere.

[0155] Titanium dioxide (TiO x ) layers were deposited from a metallic titanium (Ti) target in an argon / oxygen (Ar / O2) sputtering atmosphere.

[0156] A ZnO:Al growth-promoting top layer of the lower dielectric layer was sputtered from an Al-doped Zn target (aluminum (Al) content about 2 wt %) in an Ar / O 2 sputtering atmosphere.

[0157] In all experimental examples, the functional layer was made of substantially pure silver (Ag) without any added oxygen and with a residual oxygen partial pressure of 10 -5 It was sputtered from a silver target in an Ar sputtering atmosphere of less than mbar.

[0158] The barrier layer, located above the silver-based functional layer of zinc aluminum oxide (also called ZAO), was deposited by sputtering 2 wt. % AlO in a pure argon (Ar) sputtering atmosphere with less than 5 wt. % oxygen. x Conductive ZnO x : Sputtered from an Al target.

[0159] Table 1 provides details of a number of comparative coated glass sheets and coated glass sheets according to the invention. Comparative Example CE1 was prepared by sputtering a soda-lime-silica glass sheet, with the glass surface being coated with SiN x (20 nm), ZnSnO x (4nm), ZAO (8nm), Ag (10nm), NiCrO x (1nm), ZAO(6nm), SiN x (24 nm), ZnSnO x(9 nm) on a glass plate. CE1 is a "baseline" coating with acceptable properties in many situations. However, as noted above, it is desirable to provide alternative coatings that are more suitable for architectural and automotive applications.

[0160] Furthermore, Comparative Examples CE2 and CE3 and Examples 1 to 20 were produced in the same manner, but the SiN x The base layer is Zr x Ti y O z The layers are replaced with Zr x Ti y O z , ZnSnO x (4nm), ZAO (8nm), Ag (10nm), NiCrO x (1nm), ZAO(6nm), SiN x (24 nm), ZnSnO x (9 nm). As shown in Table 1, x Ti y O z The layer compositions and thicknesses varied.

[0161] [Table 1]

[0162] Immediately after depositing all coatings, the coated glass sheet parameters (sheet resistance (Rs), UV-Vis optical performance, etc.) of the coated glass plate were measured. The samples were then heat treated at around 650°C for 5 minutes. Afterwards, the haze scan, sheet resistance (Rs), UV-Vis optical performance were measured, and the change in light transmission (ΔTL) after heat treatment (ΔE*), and the change in color properties (represented by the change in a*, b*, and Y) were measured and calculated therefrom as follows: The measured and calculated results are shown in Table 1, such as haze, TL%AD - i.e. the percentage (%) value of the light transmittance of the glass substrate before heat treatment, ΔTL - i.e. the change in the percentage (%) of the light transmittance after heat treatment, Rs AD Ω / □ - i.e. the sheet resistance before heat treatment, ΔRS - i.e. the change in the sheet resistance during heat treatment, Rs T - i.e. the sheet resistance after heat treatment, Rf a* AD - i.e. the reflective a* color component of the film after deposition and before heat treatment, Rf b* AD - i.e. the reflective b* color component of the film after deposition and before heat treatment, and Rf ΔE* - i.e. a measure of the change in the film side reflectance during heat treatment.

[0163] The methods used to collect the data in Table 1 are described below.

[0164] CE2 and CE3 have unacceptably high haze scan values, which are apparently caused by the low Zr atomic fraction of 0.6 and / or the low Zr coefficient of 0.93.

[0165] Example 1 has improved haze scan values ​​compared to CE2 and CE3, which may be acceptable in some circumstances but is not better than the baseline coating. However, the improvement in sheet resistance with heat treatment is better for Example 1 when compared to CE1. Thus, the increase in the atomic percentage of Zr and / or Zr coefficient improved the properties of the coating.

[0166] Example 2 showed a good haze scan value of 70, lower than Comparative Examples CE1 and CE2. However, the color coordinates of the coating side reflection were within the desired range, with Example 1 showing a lower Rf ΔE* value than the other examples, indicating excellent color consistency after heat treatment.

[0167] Example 12 shows a good haze scan value of 63, excellent transmission before and after heat treatment, and an Rs T of less than 4. Rf a* and b* are slightly positive, which may be desirable in some circumstances, and do not change significantly with heat treatment as shown by the low Rf ΔE* value.

[0168] Example 15 exhibits an exceptional haze scan value of 45 and a good Rs AD of 6, which is significantly improved by heat treatment to provide an Rs T of less than 4.

[0169] 4 shows the haze scans of Comparative Examples CE2 and CE3 and Examples 1-20 versus the atomic ratio of Zr. It can be seen that the haze scan improves with increasing Zr atomic ratio, reaching a minimum value of 45 at a Zr ratio of 0.65, but increases above this. Good haze scan values ​​of less than 70 are achievable with a Zr atomic ratio of 0.55-0.85, and excellent haze scan values ​​of less than 60 are achievable with a Zr atomic ratio of 0.6-0.8.

[0170] Figure 4 also shows the Rs T of Comparative Examples CE2 and CE3, and Examples 1-20, versus the atomic fraction of Zr. As with the Haze scan, it can be seen that Rs T decreases as the atomic fraction of Zr increases, with a minimum Rs T of 3.6 at a Zr fraction of 0.58, and then increases for Zr atomic fractions above this. Good Rs T values ​​of less than 4 are achievable for Zr atomic fractions between 0.55 and 0.85.

[0171] Figure 5 shows the haze scans of Comparative Examples CE2 and CE3 and Examples 1-20 versus Zr factor. It can be seen that the haze scan improves as the Zr factor increases, reaching a minimum of 45 at a Zr factor of 10.53, but increases as the Zr factor increases beyond this. Good haze scan values ​​of less than 70 are achievable with Zr factors of 7-15, and excellent haze scan values ​​of less than 60 are achievable with Zr factors of 9-12.

[0172] FIG. 5 also shows the Rs T of Comparative Examples CE2 and CE3, and Examples 1-20, versus Zr factor. As with the Haze scan, it can be seen that Rs T decreases with increasing Zr factor to a minimum Rs T of 3.6 at a Zr factor of 11.69, and then increases for Zr factors above this. Good Rs T values ​​of less than 4 are achievable for Zr factors between 7 and 15.

[0173] Glass plates coated with two or more silver layers were investigated. The comparative CED was a ZnSnO x (13nm);ZAO(3nm);Ag(9.5nm);NiCrO x (1nm);ZAO(7nm);SiN x (40 nm); ZnSnO x (11nm);ZAO(14nm);Ag(12.8nm);NiCrO x (1nm);ZAO(5nm);SiN x (21 nm); ZnSnO x The silicon-based SiO2 nanotubes were prepared by sputtering a layer of (8 nm) of SiO2.

[0174] Examples D1 to D6 were prepared by sputtering using the same method.

[0175] In D1 and D3 to D6, the SiN x The base layer is Zr x Ti y O z Replace the layer with ZnSnO x (13nm);ZAO(3nm);Ag(9.5nm);NiCrO x(1nm);ZAO(7nm);SiN x (40 nm); ZnSnO x (11nm);ZAO(14nm);Ag(12.8nm);NiCrO x (1nm);ZAO(5nm);SiN x (21 nm); ZnSnO x (8 nm).

[0176] D2 is SiN x The base layer and the ZnSnO directly adjacent to the base layer of the CED x Both layers are 17.5 nm thick Zr x Ti y O z replaced by a single layer of ZAO(3nm); Ag(9.5nm); NiCrO x (1nm);ZAO(7nm);SiN x (40 nm); ZnSnO x (11nm);ZAO(14nm);Ag(12.8nm);NiCrO x (1nm);ZAO(5nm);SiN x (21 nm); ZnSnO x A coating according to the present invention was provided having a thickness of (8 nm).

[0177] [Table 2]

[0178] Examples D1-D6 exhibited superior sheet resistance compared to CED both before and after heat treatment. Additionally, Examples D1-D6 provide good, and in some cases excellent, haze scan results. As shown in FIG. 6, for coatings including two or more silver layers, increasing the atomic ratio of Zr to Zr and Ti in the base layer is associated with decreasing haze scan values, with atomic ratios of Zr to Zr and Ti between 0.6 and 0.8 being particularly beneficial.

[0179] The haze scan reaches a minimum at a Zr factor of 9.15, as shown in Figure 7. For coatings containing two or more silver layers, a Zr factor of 8-10 for the base layer is particularly beneficial.

[0180] The methods used to collect the data disclosed above include:

[0181] Light Transmittance - The values ​​stated for the percentage (%) change in light transmittance (ΔTL) upon heat treatment of coated glass sheets were derived from measurements using illuminant D65 over wavelengths from 350 to 1050 nm with a 10 degree observer field of view.

[0182] Sheet Resistance / Change in Sheet Resistance - Sheet resistance measurements were made using a NAGYSRM-12. This device utilizes an inductor to generate eddy currents in a 100mm x 100mm coated sample. This generates a measurable magnetic field whose magnitude is related to the resistivity of the sample. Using this method, the sheet resistance can be calculated. This equipment was used to measure the sheet resistance of samples before and after heat treatment at 650°C for 5 minutes.

[0183] Color Characteristics - The color characteristics of each experimental example are based on established CIE LAB L * ,a * ,b * The values ​​are measured and reported using coordinates (e.g., as described in paragraphs

[0030] and

[0031] of WO 2004 / 063111, incorporated herein by reference). In some circumstances, it is desirable for the coated glass sheet to exhibit achromaticity in transmission (T), glass side reflection (Rg), and coating, i.e., film, side reflection (Rf), i.e., a* and b* values ​​between -5 and +5, preferably between -2 and +2. However, in some applications and markets, a more blue color may be desirable, with a* and b* both less than 0, and even less than -5 for a strong blue color. Alternatively, in some cases, a bronze color may be desirable, with a* and b* both greater than 0, and even greater than 5.

[0184] Change in transmitted color during heat treatment, ΔE * =((Δa * ) 2 +(Δb * ) 2 +(ΔL * ) 2 ) 1 / 2 , where ΔL * , Δa * , and Δb * is the color value L of each coated glass sheet before and after heat treatment * , a * , b * A ΔE of less than 3 (e.g., 2 or 2.5) * The values ​​are favorable for layer sequences with one silver-based functional layer, which exhibit low and almost no noticeable color changes caused by the heat treatment. For layer sequences with two or more silver-based functional layers, the lower TΔE * The T value provides an indication of the stability of the sequence and * The lower the value, the better the result and appearance of the coated glass pane.

[0185] Haze Scan - A haze scoring system was applied to each of the experimental and comparative examples listed in Tables 1, 2 and 3, and the haze was measured after heat treatment. The quality assessment system described below was also used to more clearly distinguish the visual quality of the coatings under bright light conditions, a property that is not fully reflected in the standard haze value measured according to ASTM D1003.

[0186] The evaluation system considers the more macroscopic effects of visible defects in the coating, which cause local color changes if the coating is damaged or incomplete (haze scan in Table 1). The evaluation analyzes the light levels of images of the heat-treated samples taken using fixed lighting conditions and geometry.

[0187] To generate the image used to calculate the Haze Scan value, the sample is placed inside a black box 30 cm away from the camera lens. The sample is illuminated using a standard 1200 lumen light with a brightness of 2400-2800 lux when measured at the sample position. The sample is then photographed in 1 second with a standard aperture size and exposure length of f5.6, focal length of 105 mm, ISO 400. The grey scale of each pixel in the resulting image is then recorded. A value of 0 represents black and 255 represents white. A statistical analysis of these values ​​is performed to make an overall assessment of the haze of the sample, referred to here as the Haze Scan value. The lower the recorded Haze Scan value, the better the results. Generally, a Haze Scan value below 90, preferably below 80, and even more preferably below 70 is desirable. In some specialist applications where transparency is a priority, a Haze Scan value below 60 is desirable.

[0188] XPS Analysis - X-ray photoelectron spectroscopy (XPS) depth profiling was performed on a Thermo K-Alpha XPS using an argon ion etching beam operating at 1 keV (M), producing a beam current of 1.71 μA, rastered over a 2.0x4.0 mm area. An etching time of 15 seconds was used per level, resulting in a total of 100 levels of etching. The X-ray spot size used was 400 μm. The binding energy windows used to acquire the profiles were O1s, C1s, Zn2p, Sn3d, Zr3d, Si2p, Ca2p, Na1s, and Mg1s. Survey spectra (collecting the entire binding energy range from 0 to 1350 eV) were also collected to allow for detection of additional elements present within the coatings. As XPS is a quantitative technique, it can be used to determine the concentration of each element within the coating layer and to calculate the stoichiometry. For each coating, the average stoichiometry was calculated based on the average concentration of each element within the layer. To reduce the effects of surface contamination, the first few etch levels were removed.

[0189] Examples according to the invention incorporating only a single silver layer provided excellent color properties, in particular the coatings including only a single silver layer were within the color boxes a*-3 to +6.5 and b*-14 to -4 for Rg, and the coatings including two or more silver layers were within the color boxes a*-6 to 4.8, b*-18.5 to -2.3 for Rg.

[0190] As demonstrated by the examples, all coated glass sheets according to the invention exhibit good sheet resistance values ​​after deposition and a negative change in sheet resistance upon heat treatment, indicating that the silver functional layer is adequately protected from damage.

[0191] The examples according to the invention show good haze scan values ​​before and after heat treatment, indicating that the stack combination is not damaged by the heat treatment. The glass sheets of the invention also show low levels of visible damage according to tests simulating the use, processing and handling conditions of the coated glass sheets. Furthermore, the glass sheets show high light transmission and low emissivity and / or good solar control properties, and the optical properties remain stable even after heat treatment.

[0192] Surprisingly, the coatings according to the invention show parameters that indicate that the tempered glass sheets are suitable for the applications in which they are required. In particular, the haze scans of the examples according to the invention measured after heat treatment are significantly lower, in some cases even below 50.

Claims

1. A coated glass sheet comprising a glass substrate and a coating, the coating comprising, in order from the glass substrate: a base layer adjacent to and in contact with the glass substrate; A silver-based functional layer; an upper dielectric layer; Equipped with The base layer comprises an oxide of zirconium and titanium, ZrxTiyOz; the atomic ratio of Zr based on Zr and Ti in the base layer, calculated as x / (x+y), is 0.40 to 0.95; Coated glass plate.

2. 2. The coated glass sheet according to claim 1, wherein the atomic ratio of Zr based on Zr and Ti in the base layer, calculated as x / (x+y), is between 0.50 and 0.90, preferably between 0.55 and 0.85, more preferably between 0.60 and 0.80, even more preferably between 0.62 and 0.

67.

3. 3. Coated glass sheet according to claim 1 or 2, wherein the atomic % of titanium in the base layer, calculated as Ti in the total composition, is 1-25, preferably 5-20, more preferably 8-15.

4. 3. Coated glass sheet according to claim 1 or 2, wherein the atomic % of oxygen in the base layer, calculated as O in the total composition, is 60-70, preferably 62-66, more preferably 63-65.

5. 3. Coated glass sheet according to claim 1 or 2, wherein the atomic % of zirconium in the base layer, calculated as Zr in the total composition, is between 12 and 35, preferably between 15 and 25.

6. 3. Coated glass pane according to claim 1 or 2, wherein the base layer has a thickness of 6 to 60, preferably 8 to 45, more preferably 10 to 30 nm.

7. 3. The coated glass sheet according to claim 1 or 2, wherein the Zr coefficient of the base layer, calculated by multiplying the thickness in nm of the base layer by the atomic ratio of Zr based on Zr and Ti in the base layer, is between 1 and 35, preferably between 5 and 20, more preferably between 7 and 15, even more preferably between 8 and 12.

8. 3. The coated glass pane according to claim 1 or 2, wherein the coating further comprises a growth-promoting layer between the base layer and the silver-based functional layer, preferably the silver-based functional layer being in direct contact with the growth-promoting layer and / or the growth-promoting layer being based on zinc oxide.

9. 9. The coated glass sheet of claim 8, wherein the growth-promoting layer is in direct contact with the base layer.

10. 3. The coated glass sheet according to claim 1 or 2, wherein the coating further comprises a stabilization layer between the base layer and the growth-promoting layer, preferably the stabilization layer being in direct contact with the base layer.

11. 11. The coated glass sheet according to claim 10, wherein the coating further comprises a separation layer between the stabilization layer and the growth promotion layer, preferably the separation layer being in direct contact with the stabilization layer.

12. 3. The coated glass sheet according to claim 1 or 2, wherein the coating further comprises a barrier layer between the silver-based functional layer and the upper dielectric layer, preferably the barrier layer being in direct contact with the silver-based functional layer.

13. 3. The coated glass sheet according to claim 1 or 2, wherein the coating further comprises a second silver-based functional layer between the silver-based functional layer and the upper dielectric layer, preferably the coating further comprises a central dielectric layer between the silver-based functional layer and the second silver-based functional layer and / or a second barrier layer between the second silver-based functional layer and the upper dielectric layer.

14. 14. The coated glass sheet of claim 13, wherein the coating further comprises a third silver-based functional layer between the second silver-based functional layer and the top dielectric layer, preferably the coating further comprises a second central dielectric layer between the second silver-based functional layer and the third silver-based functional layer and / or a third barrier layer between the third silver-based functional layer and the top dielectric layer.

15. 3. The coated glass sheet of claim 1 or 2, wherein the coated glass sheet has an Rg a* of -6 to +6.5 and an Rg b* of -14 to -2.

5.

16. 3. The coated glass sheet according to claim 1, wherein the sheet resistance Rs is less than 8 Ω / □.

17. 3. The coated glass sheet according to claim 1 or 2, wherein the coated glass sheet is a heat-treatable coated glass sheet.

18. 3. The coated glass sheet according to claim 1 or 2, wherein the coated glass sheet is a heat-treated coated glass sheet, preferably the heat-treated coated glass sheet is a heat-bent coated glass sheet and / or a heat-strengthened coated glass sheet.

19. 20. The coated glass sheet of claim 18, wherein the thermally strengthened coated glass sheet achieves Class 1 of EN 12600.

20. 20. The coated glass sheet of claim 18, wherein the heat treated coated glass sheet has a change in color property ΔE* of 3 or less compared to a comparable annealed coated glass sheet.

21. 20. The coated glass sheet of claim 18, wherein the haze scan value is less than 90.

22. (i) providing a glass substrate; (ii) providing a base layer; (iii) providing a silver-based functional layer; (iv) providing a top dielectric layer; 3. A method for producing the coated glass pane of claim 1 or 2, comprising:

23. 23. Method for producing a coated glass sheet according to claim 22, wherein the base layer, and / or the silver-based functional layer, and / or the top dielectric layer are applied by physical vapour deposition.

24. A multi-layer glazing unit, preferably a laminated glazing unit and / or an insulating glazing unit, comprising a coated glass pane as defined in claim 1 or 2 or manufactured according to claim 22.

25. 25. Use of a coated glass pane according to claim 1 or 2, or produced according to claim 22, or use of a multiple insulation glazing unit according to claim 24, in a building or vehicle.

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