Toughenable coated substrate

Abstract

To provide a toughenable coated float glass substrate and a method of preparing the coated float glass, which address damage to the surface of the glass substrate and thereby not only meet a required aesthetic appearance of the glass but also achieve properties of glass required in both the architectural and automotive industries.SOLUTION: A float glass substrate comprises a first surface and a second surface. The first surface comprises one or more layers applied by chemical vapor deposition (CVD), and the second surface comprises one or more layers applied by physical vapor deposition (PVD). The one or more layers applied by physical vapor deposition (PVD) include at least one functional metal layer. The second surface further comprises a protective layer applied in direct contact with the second surface. The coated float glass substrate exhibits a transmission b* color value according to the CIE color space of 3 or less, and an external reflection b* of -5 or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a reinforceable coated substrate and a method for making the same. The present invention relates to a temperable coated glass substrate and a coated substrate having one or more layers deposited on each side of the substrate. After forming the coating layer on each side of the substrate, the coating layer can be thermally treated without significant damage. and a method for preparing a temperable coated glass substrate, which tempers the coated substrate. [Background technology]

[0002] It is known to deposit layers or coatings on substrates such as glass for a variety of purposes. For example, sol-gel type deposition methods are described in US Pat. Nos. 5,629,299, ... and 5,629,299. 4, each of which discloses a method of applying a silica sol to the surface of a substrate, followed by heating the substrate at a high temperature. Heating "stripping" the organic material creates a silica coating.

[0003] Other types of deposition methods include, for example, vaporizing a precursor onto the surface of a substrate, often at elevated temperatures. Examples include chemical vapor deposition (CVD) directed at the surface.

[0004] Indium tin oxide, doped tin oxide, doped zinc oxide, and doped cadmium oxide, etc. Methods for depositing conductive oxides such as silicon dioxide and silicon dioxide are also known. These methods include, but are not limited to: For example, chemical vapor deposition (CVD), flame pyrolysis, sputtering, or other types of physical vapor deposition. may be mentioned.

[0005] Glass coatings that provide low emissivity and / or solar control are applied using a physical vapor deposition process. , can be deposited by, for example, sputtering.

[0006] Sputtered low-emissivity (low-e) and solar control coatings on glass substrates The coating stack is Dielectric layer arrangement / (Ag / dielectric layer arrangement) n The thickness and / or composition of each of the n dielectric layers is The value of n can be 1 or 2, or even 3 or 4.

[0007] Coating glass substrates on both sides to create flat glass units for the architectural flat glass market In practice, the above technique is used to first coat one side of a glass substrate, for example. Products are available that are inverted and then coated on the other side. For example, NSG is a glass substrate that is with a self-cleaning or anti-reflective coating deposited by chemical vapor deposition (CVD) The other side of the glass substrate is coated with a physical vapor deposition (PVD) (sputter) low-emissivity coating. The coated glass products are manufactured by coating with

[0008] There are alternative products that have low-emissivity coatings applied to each side of the glass substrate, but One of the high-emissivity coatings is deposited by chemical vapor deposition, while the other low-emissivity coating is deposited by spat. The film was formed by tartering.

[0009] However, many coated glass articles prepared using the techniques described above have been heat-strengthened or Strengthening is difficult to achieve without damaging the coating layer, resulting in color uniformity. This leads to defective products in terms of lack of clarity or visual clarity.

[0010] In toughened or tempered glass, the glass substrate is processed by controlled thermal or chemical treatment to Its strength is increased compared to ordinary glass. By tempering or strengthening, the outside of the glass substrate When tempered or tempered glass breaks, the inner surface of the glass substrate is in tension and the outer surface is in compression. Unlike flat glass (also known as annealed glass), the induced stresses make tempered glass It breaks into small granular chunks rather than breaking into jagged pieces.

[0011] Coated glass sheets that are toughened and / or bent to provide safety are used in architectural and automotive applications. Desirable for many applications, both for automotive glazing and for thermal strengthening and / or bending of glass sheets. The glass plate is heated by heat treatment at a temperature near or higher than the softening point of the glass used. It is known that after processing, it is necessary to strengthen it by quenching or bend it using a bending means. The temperature range suitable for standard soda-lime-silica float glass is typically about 5 The glass sheet is heated to a temperature between 80°C and 690°C before the actual tempering and / or bending process begins. The temperature is maintained within this range for several minutes.

[0012] In the following description and claims, the terms "heat treated," "heat treated," and "heat treated" are used interchangeably. "Possible" refers to the process of hot bending and / or tempering as described above, and the process of applying heat to the coated glass sheet for a few minutes, e.g. For example, other thermal processes that reach temperatures in the range of approximately 580°C to 690°C for up to approximately 10 minutes. A coated glass sheet is considered heat treatable if it can withstand the heat treatment without significant damage. Typical damage caused by processing is high haze, pinholes, or spots.

[0013] When characterizing the thermal processability of low-emissivity (low-e) and / or solar control coatings The term or parameter "haze" often mentioned in the glass industry is the degree to which the haze of a coated glass sheet Complete removal of all types of defects that may occur during coating, heat treatment, processing, and / or handling For example, the known heat treatable Depending on the coated glass sheets, their optical properties and in particular the appearance of the reflected colour during and after heat treatment may be affected. Shows significant and noticeable changes.

[0014] Therefore, it is possible to maintain the thermal and optical properties of the coated glass sheet both before and after the heat treatment. This is desirable to maintain similar sheet resistance values ​​both before and after heat treatment, or in some cases In practice, the coated glass sheet is characterized by a low level of sheet resistance after heat treatment. obtain.

[0015] One side of the glass substrate (which can be tempered or simply annealed) is coated with a thin film of glass by chemical vapor deposition (CVD). one side is coated with a thin film coating and the other side is coated with a sputtered solar control coating. Although there are products that have been developed, these products often have limited applicability and are not suitable for PVD applications. The performance is comparable to that provided by coated glass substrates containing silver anti-reflective layers deposited by Not possible.

[0016] In the float glass process, a continuous strip of molten glass is pumped from a furnace into a large, shallow molten metal The glass is then poured into a metal bath to form a float ribbon. Tin is usually used as the molten metal. The glass floats on the tin and spreads out as it cools to form a flat surface. Rollers are used to pull or draw the glass into a glass sheet of the required thickness. The surface of the glass sheet that comes into contact with tin during manufacturing is the "tin" side of the glass sheet or substrate. It is known that the glass sheet comes into contact with the hydrogen or nitrogen atmosphere generated in the bath. The opposite side is conventionally known as the "air" side.

[0017] During the float process, steel lift-out rollers are typically used to remove the glass from the bath and into the annealing furnace. However, the glass is still soft during the movement of the glass by the steel rollers. Such damage appears as visible spots, streaks, and Damage typically appears as a streak. Damage clearly impairs the aesthetic appearance of the final glass product. In addition, these products must be sold at low prices or, in the worst case scenario, discarded entirely. and must be recycled.

[0018] Furthermore, the defects on the surface of the glass substrate that appear during fabrication are likely to be due to one or more coatings. This is often exacerbated when the coating layer is deposited on the tin side of the glass substrate. This is the case when the glass is subsequently heat treated (or tempered). [Prior art documents] [Patent documents]

[0019] [Patent Document 1] European Patent No. 1429997 [Patent Document 2] German Patent No. 10146687 [Patent Document 3] European Patent No. 1328483 [Patent Document 4] U.S. Patent No. 6,918,957 Summary of the Invention [Problem to be solved by the invention]

[0020] Therefore, the present invention addresses the appearance of such damage on the surface of a glass substrate and thereby Not only does it meet the required aesthetic appearance of glass, but it also meets the glass requirements of both the architectural and automotive industries. The objective is to achieve the characteristics of

[0021] Furthermore, the present invention provides a coated foil with acceptable parameters and appearance from both sides. The present invention is directed to a method for making tempered glass, Glanova (registered trademark). Chemically strengthened glass, available from NSG under the trade name (registered trademark), and borosilicate glass, etc. It can also be applied to the protection of other glass substrates. [Means for solving the problem]

[0022] Thus, according to a first aspect of the present invention, there is provided a temperable coated float glass substrate. hand, i) a first surface; ii) a second surface; and the first surface includes one or more layers deposited by chemical vapor deposition (CVD); the surface of the second substrate comprises one or more layers deposited by physical vapor deposition (PVD); The layer or layers deposited by physical vapor deposition (PVD) have at least one function. a conductive metal layer; the second surface further comprises a protective layer deposited in direct contact with the second surface; and The coated float glass substrate has a transmission b in the CIE color space of 3 or less. * Color values ​​below -5 external reflection b * A temperable coated float glass substrate is provided, which exhibits:

[0023] Preferably, in the reinforceable coated substrate according to the first aspect of the invention, the protective layer is silicon oxide. It contains a (SiOx) layer, where x is in the range of 1.5 to 2.0.

[0024] According to the CIE color space, the temperable coated substrate according to the invention has either b is also negative * and a * It is preferable to include a value, i.e., b *The value is blue in the CIE color space. In the color region, a * The value is in the green region of the CIE color space.

[0025] Also, with respect to the first aspect of the present invention, the protective layer may be deposited by physical vapor deposition (PVD). It is preferable that:

[0026] Preferably, the thickness of the protective layer is in the range of 10 nm to 100 nm. The thickness of the protective layer is in the range of 15 nm to 80 nm. Even more preferably, the thickness of the protective layer is However, most preferably, the thickness of the protective layer is in the range of 30 nm to 70 nm. Alternatively, the thickness of the protective layer is in the range of 30 nm to 60 nm, or can be in the range of 50 nm to 60 nm.

[0027] Regarding the first aspect of the present invention, in the temperable coated substrate, the second surface of the float glass The first surface of the float glass is exposed to nitrogen and hydrogen vapor during manufacture. It is preferable that the material is in contact with a gas atmosphere.

[0028] Also, with respect to the temperable coated substrate according to the first aspect of the present invention, the first surface of the glass substrate One or more layers deposited by chemical vapor deposition (CVD) on the surface, Silicon oxide (SiO2), tin oxide (SnO2), fluorine-doped tin oxide (SnO2: F), titanium oxide (TiO2), and antimony-doped tin oxide (SnO2:Sb) Preferably, the insulating layer comprises one or more doped or undoped oxide layers selected from:

[0029] Preferably, a coating is applied to the second surface of the temperable coating substrate by physical vapor deposition (PVD). One or more layers include a functional metal layer, which is preferably silver.

[0030] Furthermore, with regard to the temperable coated substrate according to the present invention, the coating is deposited by physical vapor deposition (PVD). The layer or layers may be Ti, V, Cr, Fe, or W, Ni, Nb, and combinations thereof. It is preferred to have at least one absorbing layer of gold and nitride type. At least one absorbing layer comprises tungsten (W), preferably tungsten nitride.

[0031] Furthermore, with respect to the temperable coated substrate according to the first aspect of the present invention, after heat treatment of the coated substrate The color change in transmission (ΔE * ) is preferably 10 or less. More preferably, the coated substrate The color change of the transmission after heat treatment (ΔE * ) is preferably 8 or 7 or less. or the color change in transmission (ΔE * ) is preferably 5 or less.

[0032] Furthermore, with respect to the temperable coated substrate according to the first aspect of the present invention, the thermal Reflectance color change after treatment (ΔE * ) is preferably 10 or less. The change in the color of reflection after heat treatment on each surface of the substrate (ΔE * ) is preferably 8 or 7 or less Most preferably, the color change in reflection (ΔE * ) is 5 or less It is preferable.

[0033] According to a second aspect of the present invention, a dual coated reinforced plastic according to the first aspect of the present invention is provided. 1. A method for preparing a float glass substrate that can be molded, comprising: i) providing a float glass substrate having a first surface and a second surface; The second surface of the glass substrate is in contact with molten tin during fabrication, and the first surface is in contact with nitrogen and contacting a bath atmosphere of hydrogen; ii) depositing one or more layers onto a first surface of a substrate by chemical vapor deposition (CVD); Top and iii) depositing one or more layers on the second surface of the substrate by physical vapor deposition (PVD); Tep and iv) Protecting by physical vapor deposition (PVD) before depositing one or more layers on the second surface This is a step in which a protective layer is deposited directly on the glass substrate, with a thickness of 10 nm to 100 nm. and v) The layer or layers deposited on each side of the coated glass substrate can be removed without degrading the substrate. heat treating the sheet to strengthen the glass; A method is provided that includes:

[0034] Regarding the second aspect of the present invention, the protective layer comprises a silicon oxide (SiOx) layer, where x is 1.5 It is preferable that the value is in the range of 1.0 to 2.0.

[0035] Additionally, one or more layers are deposited on the second surface of the substrate by physical vapor deposition (PVD). It is preferred that the functional metal layer comprises a functional metal layer, most preferably silver.

[0036] Furthermore, with respect to the second aspect of the present invention, the protective layer is deposited to a thickness of 30 nm to 70 nm. Preferably, the protective layer is deposited to a thickness in the range of 10 nm to 100 nm. More preferably, the protective layer is deposited to a thickness in the range of 15 nm to 80 nm. Preferably, the protective layer is deposited to a thickness in the range of 30 nm to 70 nm. Most preferably, the protective layer is deposited to a thickness in the range of 40 nm to 70 nm. The thickness of the protective layer can be deposited in the range of 30 nm to 60 nm, or even 50 nm to 60 nm.

[0037] Preferably, one or more films are deposited by chemical vapor deposition (CVD) on the first surface of the substrate. The layer is Silicon oxide (SiO2), tin oxide (SnO2), fluorine-doped tin oxide (SnO2: F), titanium oxide (TiO2), and antimony-doped tin oxide (SnO2:Sb) The laminated film includes one or more layers selected from the following:

[0038] In a method according to a second aspect of the invention, the second surface of the substrate is coated with a physical vapor deposition (PVD) layer. The layer deposited on the surface may be deposited after deposition of one or more layers on the first surface of the substrate.

[0039] According to a third aspect of the invention, there is provided a glass article comprising a temperable coating according to the first aspect of the invention. The use of a non-float glass substrate is provided.

[0040] According to a fourth aspect of the invention, there is provided a method for producing a temperable glazing according to the first aspect of the invention in an insulating glazing article. The use of a coated float glass substrate is provided.

[0041] According to a fifth aspect of the present invention, a windscreen, a sidelight, a skylight or a backlight may be provided. Temperable coated float glass according to the first aspect of the present invention for automotive glazing such as Kryte The use of a glass substrate is provided.

[0042] All features relating to the first aspect of the invention are also applicable to the second, third and fourth aspects of the invention. It will be understood that this also applies.

[0043] In the coated glass substrate according to the present invention, a protective layer of SiOx is formed on the "tin" side. The coating stack, when including a single silver-based functional layer, has the following arrangement, starting from the SiOx layer: : lower antireflection layer, silver-based functional layer, a barrier layer, and Top anti-reflection layer It is preferred that the compound contains:

[0044] Alternatively, a coated glass substrate according to the invention with a protective layer of SiOx deposited on the "tin" side. If the coating has two silver layers, the coating stack consists of the following layers, starting from the SiOx layer: array: lower antireflection layer, First silver-based functional layer, a barrier layer, central anti-reflection layer, a second silver-based functional layer, and Top anti-reflection layer It is preferred that the compound contains:

[0045] Regarding the coating arrangement used in the coated glass substrate according to the present invention, the lower anti-reflection layer The first is a protective silicon oxide (SiOx) layer, followed by oxides of zinc (Zn) and tin (Sn) and / or Preferably, it may include a tin (Sn) oxide-based layer and a Zn oxide-based top layer. .

[0046] The lower anti-reflection layer may be made of silicon (oxy)nitride, aluminum (oxy)nitride, and / or It may also preferably comprise one or more base layers of these alloy systems. and / or one or more bases of the alloy system thereof. The layers are a protective silicon oxide (SiOx) layer and an oxide of zinc (Zn) and tin (Sn) as the bottom anti-reflection layer. Preferably, the layer is positioned between the oxide-based layer and / or the tin (Sn) oxide-based layer.

[0047] Therefore, in one embodiment of the present invention, the coated glass sheet is coated with a protective silicon oxide SiOx Between the layer and the zinc (Zn) and tin (Sn) oxide and / or tin (Sn) oxide-based layer Silicon (oxy)nitrides and / or aluminum (oxy)nitrides and / or It is preferable that the lower anti-reflection layer has a base layer of the alloy system. The layer may include:

[0048] In coated glass substrates with silver-based functional layers, the lower anti-reflection layer may further comprise a separation layer. The separation is carried out by the formation of metal oxides and / or silicon (oxy)nitrides and / or aluminum (oxy)nitrides. Preferably, the metal oxides may be oxides and / or alloys thereof.

[0049] Furthermore, the separation layer has a thickness of 0.5 nm or more, preferably 0.5 nm to 6 nm, more preferably Preferably, the thickness is 0.5 nm to 5 nm, more preferably 0.5 nm to 4 nm, and most preferably 0.5 nm to 5 nm. It is preferable that the thickness of the film is 0.5 to 3 nm. These preferable thicknesses are obtained by the heat treatment. This allows for further improvement of haze. The separation layer is formed during the deposition process and subsequent heat treatment. It is preferred that the separation layer be essentially fully oxidized immediately after deposition. Preferably, the oxide layer is oxidized to a substantially fully oxidized layer during subsequent deposition of the oxide layer.

[0050] When the separation layer is a metal oxide-based layer, the separation layer may be formed of Ti, Zn, NiCr, InSn, Preferably, it may include a layer based on oxides of Zr, Al, and / or Si.

[0051] When the separating layer is preferably metal oxide based, the separating layer may be essentially stoichiometric or is a slightly substoichiometric oxide, e.g., a slightly substoichiometric titanium oxide-based crystalline targets, e.g., TiO 1.98 Non-reactive sputtering from the target by reactive sputtering of Ti-based targets in the presence of O2 using Ti It can be deposited by depositing a thin layer of the system and then oxidizing it. An "essentially stoichiometric oxide" is an oxide that is 95% or more but not more than 100% stoichiometric. "Slightly substoichiometric oxide" means an oxide with more than 95% of the stoichiometric amount. The use of TiOx as a separation layer means that the coating It is particularly preferred if the coating arrangement comprises a single silver-based functional layer.

[0052] The separation layer is a metal oxide and / or silicon (oxy)nitride and / or aluminum (oxy)nitride. (Oxy)nitrides and / or their alloys, plus the following elements: Ti, V, Mn, Co, C At least one of u, Zn, Zr, Hf, Al, Nb, Ni, Cr, Mo, Ta, and Si or an alloy based on at least one of these substances, for example dopa The composition may further include one or more chemical elements used as additives or alloys.

[0053] However, preferably, metal oxides and / or silicon (oxy)nitrides and / or arsenides are used. A separation layer based on an aluminum (oxy)nitride is free of one or more other chemical elements.

[0054] In a preferred embodiment of the present invention, the separating layer is made of an oxide of zinc (Zn) and / or titanium. It is a metal oxide system including oxide of titanium.

[0055] In another preferred embodiment of the present invention, the separation layer is a metal oxide comprising an oxide of titanium. It is a system.

[0056] The separating layer may be based on titanium oxide if the layer sequence includes one silver-based functional layer. is preferred, but if the layer system or stack contains more than one silver-based functional layer, the layer arrangement It may also be preferred that the lower antireflective layer does not include a separate layer.

[0057] Furthermore, when the separation layer is a metal oxide-based metal oxide, the titanium oxide The thickness of the film is preferably 0.5 nm to 3 nm.

[0058] The lower antireflective layer preferably contains three, four or more of the above-mentioned layers. This number will vary depending on the number of silver-based functional layers present in the array.

[0059] Silicon (oxy)nitride and / or aluminum (oxy)nitride and / or Alternatively, the base layer of these alloys may preferably have a thickness of 5 nm or more. Preferably, the lower antireflection layer is made of silicon (oxy)nitride and / or aluminum (oxy)nitride. The base layer of the material and / or alloy thereof has a thickness of 5 nm to 60 nm. More preferably, the lower anti-reflection layer is made of silicon (oxy)nitride and / or aluminum (oxy)nitride. The base layer of nitrides and / or their alloys is 10 nm to 50 nm, 15 nm to 45 nm The thickness of the lower anti-reflective layer is preferably 20 nm to 40 nm. (Oxy)nitrides of aluminum and / or (Oxy)nitrides of aluminum and / or their alloy bases The base layer has a thickness of 25 nm to 35 nm. This base layer is used for, among other purposes: It acts as a diffusion barrier especially on the glass side.

[0060] The term "(oxy)nitride of silicon" refers to silicon nitride (Si) (SiN x) and silicon oxynitride (Si)(SiOxN y ), whereas the term "aluminum (oxy)nitride" The "substance" is aluminum nitride (Al) (AlN x ) and aluminum oxynitride (Al) (Al O x N y ) includes both silicon nitride (Si), silicon oxynitride (Si), and aluminum nitride. The aluminum (Al) and aluminum oxynitride (Al) layers are essentially stoichiometric (e.g., Silicon nitride = Si3N4, SiN x The value of x is preferably 1.33, Sub-stoichiometric or even superstoichiometric coatings are acceptable as long as they do not adversely affect the heat treatability of the coating. The lower anti-reflection layer may be made of silicon (oxy)nitride and / or aluminum (oxy)nitride. ) One preferred composition of the nitride-based base layer is essentially stoichiometric mixed nitride Si 90 A l 10 N x is.

[0061] The silicon (oxy)nitride and / or aluminum (oxy)nitride layers are formed by the addition of nitrogen and argon. Silicon (Si) and / or aluminum (Al) are sputtered in a sputtering atmosphere containing silicon. It can be reactively sputtered from targets based on silicon (oxy)nitride and / or aluminum. The oxygen content of the base layer of a silicon (oxy)nitride system depends on the residual oxygen in the sputtering atmosphere and This can be attributed to the control of the added oxygen content in the atmosphere. ) If the oxygen content of the aluminum nitride is significantly less than its nitrogen content, i.e., It is generally preferable if the atomic ratio O / N in the lower anti-reflection layer is significantly less than 1. The base layer can be made of silicon nitride and / or aluminum nitride, which have a very low oxygen content. This feature is most preferred because the refractive index of the layer is oxygen-free silicon nitride and / or aluminum nitride. This can be controlled by ensuring that the refractive index of the layer is not too different.

[0062] Using mixed silicon (Si) and / or aluminum (Al) targets, or Silicon in the base layer of the lower anti-reflective layer is not lost as long as the essential barrier and protective properties of this layer are not lost. (Si) and / or aluminum (Al) components with metals or semiconductors added by other means is within the scope of the present invention. For example, an aluminum (Al) target and a silicon (Si) The target can be mixed with other mixed targets, and other mixed targets are not excluded. However, aluminum is typically present in an amount of 10% to 15% by weight. % of the mixed silicon target.

[0063] Zinc (Zn) and tin (Sn) oxide and / or tin (Sn) oxide in the bottom anti-reflection layer The material layer provides a dense and thermally stable layer and contributes to reducing haze after heat treatment. It is preferable that the lower anti-reflection layer has a function of increasing stability during heat treatment. The zinc (Zn) and tin (Sn) oxide and / or tin (Sn) oxide-based layer is 0.5 Preferably, the lower anti-reflection layer has a thickness of 100 nm or more. The tin (Sn) oxide and / or tin (Sn) oxide-based layer has a thickness of 0.5 nm to 15 nm. The thickness of the lower portion may be 0.5 nm to 13 nm, or 1 nm to 12 nm. Anti-reflection layer zinc (Zn) and tin (Sn) oxide and / or tin (Sn) oxide system The layer may have a thickness of 1 nm to 7 nm, or 2 nm to 6 nm, or 3 nm to 6 nm. More preferably, the lower anti-reflection layer is made of zinc (Zn) and tin (Sn) oxide and / or tin ( The oxide-based layer of Sn) is 3n in the coated glass sheet with a layer sequence including a single silver-based functional layer. The thickness of the film may be in the range of 1000 to 5000 nm. The upper limit of the thickness of about 8 nm is preferred due to the optical interference conditions. , and the thickness of the base layer required to maintain the optical interference boundary condition for the antireflection of the functional layer. This is because the heat treatability is reduced due to the reduction in thickness.

[0064] In an alternative embodiment of the first aspect of the present invention, the silver-based coated glass sheet If there is more than one functional layer, the bottom anti-reflection layer is zinc (Zn) and tin (Sn) oxide. and / or the tin (Sn) oxide-based layer preferably has a thickness of 12 nm or more. More preferably, the lower anti-reflection layer is made of zinc (Zn) and tin (Sn) oxide and / or tin. The Sn oxide layer preferably has a thickness of 12 nm to 20 nm. More preferably, the lower anti-reflection layer is made of oxides of zinc (Zn) and tin (Sn) and / or tin. The Sn oxide layer preferably has a thickness of 12 nm to 16 nm. However, most preferably, the lower anti-reflection layer is made of zinc (Zn) and tin (Sn) oxide. and / or the tin (Sn) oxide-based layer preferably has a thickness of 12 nm to 14 nm. stomach.

[0065] Zinc (Zn) and tin (Sn) oxide and / or tin (Sn) oxide in the bottom anti-reflection layer The material-based layer is silicon (oxy)nitride and / or aluminum (oxy)nitride and / or It is preferably positioned directly on top of these alloy-based layers.

[0066] The lower anti-reflection layer is made of zinc (Zn) and tin (Sn) oxide (abbreviated as ZnSnOx ) system layer is preferably 10% by weight to 90% by weight of zinc (Zn) in the weight percent of the total metal content of the layer, and Tin (Sn) 90% to 10% by weight, more preferably zinc (Zn) about 40% to 60% by weight % by weight and tin (Sn) about 40% to 60% by weight, and even more preferably zinc (Zn) and tin (Sn) at about 50% by weight each. The zinc (Zn) and tin (Sn) oxide layer of the lower anti-reflection layer is made of tin (Sn) 18 % by weight or less, more preferably tin (Sn) 15% by weight or less, even more preferably tin ( The oxide layer of Zn and Sn may contain up to 10% by weight of Zn and Sn. It may also preferably be deposited by reactive sputtering of a ZnSn target.

[0067] The separation layer is a metal oxide and / or silicon (oxy)nitride and / or aluminum (oxy)nitride. (Oxy)nitrides and / or their alloys, plus the following elements: Ti, V, Mn, Co, C At least one of u, Zn, Zr, Hf, Al, Nb, Ni, Cr, Mo, Ta, and Si or an alloy based on at least one of these substances, for example dopa The composition may further include one or more chemical elements used as additives or alloys.

[0068] However, preferably, metal oxides and / or silicon (oxy)nitrides and / or arsenides are used. A separation layer based on an aluminum (oxy)nitride is free of one or more other chemical elements.

[0069] In a preferred embodiment of the present invention, the separating layer is made of an oxide of zinc (Zn) and / or titanium. It is a metal oxide system including oxide of titanium.

[0070] In another preferred embodiment of the present invention, the separation layer is a metal oxide comprising an oxide of titanium. It is a system.

[0071] Furthermore, when the separation layer is a metal oxide-based metal oxide, the titanium oxide The thickness of the film is preferably 0.5 nm to 3 nm.

[0072] However, the layer sequence may have two or more silver-based functional layers and the separating layer may be a silicon (oxy)nitride. and / or aluminum (oxy)nitrides and / or alloys thereof. In this case, the lower anti-reflection layer is preferably a titanium oxide-based layer when the layer sequence includes one silver-based functional layer. Preferably, the layer arrangement or stack may comprise two or more layers. If there is more than one silver-based functional layer included, the separating layer of the lower anti-reflection layer is silicon (oxy)nitride. containing two or more layers of aluminium nitride and / or aluminium (oxy)nitride and / or their alloys. It may also be preferable to

[0073] A zinc (Zn) oxide-based top layer promotes growth for the subsequently deposited silver-based functional layer. The zinc (Zn) oxide-based top layer is approximately 10 wt. % (target % by weight of the total metal content, Optionally mixed with metals. The usual contents of the above metals, such as aluminum (Al) or tin (Sn), The content is about 2% by weight, and aluminum (Al) is actually preferred. ) or mixed zinc (Zn) oxides are very effective as growth promoting layers, It has been found that this helps achieve low sheet resistance for a given thickness of the subsequently deposited silver-based functional layer. The zinc (Zn) oxide-based top layer of the lower anti-reflection layer was found to be oxidized in the presence of oxygen (O2). It is reactively sputtered from a zinc (Zn) target at 1000 K or contains no oxygen or In an atmosphere containing only a small amount, typically less than about 5% by volume, e.g., ZnO:Al Preferably, the zinc (Zn) is deposited by sputtering from a ceramic target. The top layer of the oxide-based lower anti-reflection layer may preferably have a thickness of 2 nm or more. More preferably, the top layer of the zinc (Zn) oxide-based lower anti-reflection layer has a thickness of 2 nm to It is preferable that the thickness is 15 nm or 3 nm to 12 nm. The top layer of the zinc (Zn) oxide based lower anti-reflection layer has a thickness of 3 nm to 10 nm. It is most preferable to use a zinc (Zn) oxide based lower anti-reflection layer. The top layer may preferably have a thickness of 3 nm to 8 nm.

[0074] As is often the case in the field of low emissivity and / or solar control coatings, The silver-based functional layer(s) preferably consist essentially of silver without any additives. However, it functions as an IR reflective layer(s) with high light transmission and low light absorption. Doping agents are not particularly limited as long as they do not substantially impair the properties of the silver-based functional layer(s) required for achieving the desired results. By adding alloy additives, or even a very thin metal or metal compound layer, silver-based It is within the scope of the present invention to vary the properties of the functional layer(s).

[0075] The thickness of each silver-based functional layer depends on its technical purpose. For solar control purposes, the preferred layer thickness for a single silver-based layer is preferably 5 nm to 20 nm. , more preferably 5 nm to 15 nm, even more preferably 6 nm to 15 nm, and even more preferably More preferably, it may be 8 nm to 15 nm, and most preferably, it may be 8 nm to 14 nm. For a single silver coating, light transmission values ​​of over 86% and above are obtained after heat treatment for a given layer thickness. A normal emissivity of less than 0.05 can be easily achieved with the present invention. If control properties are required, the thickness of the silver-based functional layer can be increased sufficiently, or even less. As will be explained further, several spaced apart functional layers may be provided.

[0076] Preferably, the zinc (Zn) oxide-based top layer of the lower anti-reflection layer is directly adjacent to the silver-based functional layer. Preferably, the layer between the glass substrate and the silver-based functional layer is the lower anti-reflection layer described above. The laminate may consist of three, four or more layers.

[0077] The present invention relates to a coated glass sheet with only one silver-based functional layer, but the concept of the present invention can be divided into two parts. Suitable for the preparation of low-emissivity and / or solar control coatings with silver-based functional layers It is preferable within the scope of the present invention that more than one silver-based functional layer is provided. In this case, all of the silver-based functional layers are not covered by an intervening dielectric layer, collectively referred to herein as the "central antireflective layer." and spaced by layers of glass to form a Fabry-Perot interference filter, and The optical properties of the light control coating can be further optimized for each application.

[0078] Preferably, each silver-based functional layer is separated from the adjacent silver-based functional layer by an intervening central anti-reflective layer. The intervening central anti-reflective layer(s) are the following layers: Silicon (oxy)nitride and / or aluminum (oxy)nitride based layers, Zn and Sn oxynitrides Sn oxide and / or Sn oxide layers, and metal oxide layers such as Zn oxide may include one or more combinations of:

[0079] In some preferred embodiments, each silver-based functional layer is separated by an intervening central anti-reflective layer. Each central anti-reflective layer is spaced from the adjacent silver-based functional layer by a distance of 100 nm, and each central anti-reflective layer is located closest to the glass substrate. The silver-based functional layer is then coated with silicon (oxy)nitride and / or aluminum (oxy)nitride. Nitride-based layers, Zn and Sn oxide and / or Sn oxide-based layers, and Zn oxide, etc. The metal oxide layer comprises at least one of the above metal oxide layers.

[0080] The coated glass sheet according to the invention preferably also comprises a barrier layer. The barrier layer is a silver-based functional layer. Preferably, it is positioned in direct contact with the

[0081] The barrier layer may preferably be an oxide of Zn having a thickness of 0.5 nm or more, and more preferably Preferably, the barrier layer is a Zn oxide-based layer having a thickness of 0.5 nm to 10 nm. The barrier layer is a Zn oxide-based layer with a thickness of 1 nm to 10 nm.

[0082] When the barrier layer comprises a layer of mixed metal oxide sputtered from a mixed metal oxide target In addition, excellent protection of the silver-based functional layer during the deposition process and high optical stability during thermal treatment are achieved. When the barrier layer is made of zinc (Zn) oxide, the oxide is Zn The ZnO:Al based layer can be a mixed metal oxide such as ZnO:Al. Good results are achieved especially when the ZnO:Al is sputtered from a ZnO:Al target. It can be deposited so that it is fully oxidized or slightly suboxidized.

[0083] Furthermore, when the barrier layer includes a zinc (Zn) oxide-based layer, the barrier may be formed of a material such as ZnO:Al. Multiple layers, including mixed metal oxides as well as zinc (Zn) and tin (Sn) oxides. Thus, a suitable barrier layer may comprise a zinc oxide layer of ZnO:A. The total thickness of such a triple barrier configuration can be can be between 3 nm and 12 nm.

[0084] A further triple barrier configuration is the following combination of layers, starting from the silver-based functional layer: ZnO:Al / TiO x / ZnO:Al, ZnO:Al / ZnSnO x / ZnO:Al, TiO x / Zn SnO x / ZnO:Al, TiO x / ZnO:Al / TiO x , TiO x / ZnSnO x / TiO x , and ZnO:Al / ZnSnO x / TiO x may be selected from the group consisting of It is preferable that:

[0085] At least a portion of the barrier layer that is in direct contact with the silver-based functional layer is formed by the non-reactive oxide-based target. It is preferable to deposit it using sputtering to avoid damaging the silver.

[0086] Furthermore, instead of the barrier layer being a zinc (Zn) oxide-based material, the barrier layer may be a substoichiometric Theoretical NiCrO x When the layer contains nickel (Ni) and chromium-based mixed metal oxides, such as However, adequate protection of the silver-based functional layer during the deposition process and high optical stability during thermal treatment are achieved. It has further been found that it is possible to achieve this, in particular when the coated glass sheet comprises two or more silver-based functional layers. This is true when the coated glass sheet has a single silver-based functional layer, but also when the coated glass sheet has a substoichiometric Typical NiCrO x A layer of the above can be used.

[0087] Therefore, coated glass with two or more silver-based functional layers (and even three or four silver layers) In the glass plate, each silver-based functional layer is separated from the adjacent silver-based functional layer by an intervening central anti-reflection layer. Each central anti-reflection layer is formed in order from the silver-based functional layer positioned closest to the glass substrate. , i) Nickel (Ni) and chromium oxide or aluminum (Al) doped zinc an oxide-based top barrier layer, and / or ii) Zinc (Zn) and tin (Sn) oxide-based layer, or zinc and aluminum oxide a tungsten nitride-based layer, or a tungsten nitride-based layer, and / or iii) layers based on silicon (oxy)nitride and / or aluminum (oxy)nitride, and / or or iv) Zinc (Zn) and tin (Sn) oxide layer It is preferable that the composition contains at least

[0088] Also, with respect to the first aspect of the present invention, the coated glass preferably comprises a top anti-reflection layer. The upper anti-reflection layer is preferably i) Nickel (Ni) and chromium oxide or aluminum (Al) doped zinc an oxide-based top barrier layer, and / or ii) Zinc (Zn) and tin (Sn) oxide layer or zinc and aluminum or tin a layer based on nitride of tin, and / or iii) layers based on silicon (oxy)nitride and / or aluminum (oxy)nitride, or Lead and aluminum based layers It is preferred that the compound contains:

[0089] The Zn and Sn oxide and / or Sn oxide based layer of the upper antireflection layer is preferably 0.0 nm or more, more preferably 3 nm or 4 nm or more, and even 5 nm or more, but preferably The upper anti-reflection layer may have a thickness of at least 6 nm, more preferably at least 7 nm. The Zn and Sn oxide and / or Sn oxide-based layer is preferably 12 nm or less, more preferably 12 nm or less. The thickness is preferably 10 nm or less, particularly 7 nm to 9 nm. This makes deposition easier while maintaining mechanical durability and also improves optical properties such as haze. It can be improved.

[0090] The Zn oxide layer of the upper antireflection layer is preferably 0.5 nm or more, more preferably 0.5 nm or 1 nm or more, even 1.5 nm or more, but preferably less than 5 nm, more preferably Preferably, the thickness is 4 nm. These preferred thicknesses also improve mechanical durability. While maintaining the properties, deposition can be made easier and optical properties such as haze can be improved. .

[0091] Preferably, the layers of the top antireflective layer are essentially stoichiometric metal oxide based. The barrier layer is essentially a stoichiometric metal oxide barrier layer, not a barrier layer of 95% or less than stoichiometric. The use of a wall layer leads to extremely high optical stability of the coating during heat treatment. Furthermore, the photo-modification of the essentially stoichiometric metal oxide The use of layers of the system is beneficial in terms of mechanical robustness.

[0092] In the context of the present invention, the term "non-reactive sputtering" refers to essentially stoichiometric oxides. Oxide systems in a low-oxygen atmosphere (i.e., oxygen-free or less than 5% by volume of oxygen) to provide This includes sputtering the target.

[0093] Also, in the context of the present invention, when we say that a layer is a particular "system" of one or more materials, this Unless otherwise specified, the layer primarily contains one or more of the above substances in an amount of 50 atomic % or more. It means to

[0094] The layer is ZnSnO x In the case of the ZnSnO x " refers to the same as described elsewhere in this specification and It means the defined mixed oxide of Zn and Sn.

[0095] A layer of the upper antireflection layer based on aluminum (oxy)nitride or silicon (oxy)nitride is preferred. Preferably 5 nm or more, more preferably 5 nm to 50 nm, and even more preferably 10 nm to 45 nm , even more preferably 10 nm to 40 nm, most preferably 25 nm to 40 nm Such thicknesses may also result in further improvements in the mechanical robustness of the coated glass pane. The above-mentioned layers based on aluminum (oxy)nitride and silicon (oxy)nitride are used as the upper anti-reflection layer. It is preferable that the metal layer be in direct contact with the zinc (Zn) oxide-based layer of the stop layer.

[0096] Aluminum (oxy)nitride and silicon (oxy)nitride based layers are the majority of the top anti-reflection layer. The layer may be made up of a polymer to provide stability (improved protection during heat treatment) and diffusion barrier properties. , Si, Al, or mixed SiAl targets in a N2-containing atmosphere, e.g., Si 90 A l 10 By reactive sputtering of the target, Al nitride and / or Si nitride layers are formed. It is preferable that aluminum (oxy)nitride and / or silicon (oxy)nitride are deposited. The composition of the material layer is essentially stoichiometric Si 90 Al 10 N x It could be.

[0097] To minimize light absorption in the coating and reduce the increase in light transmittance during heat treatment, All of the individual layers of the top and bottom antireflective layers are deposited with essentially stoichiometric compositions. It is preferable that:

[0098] To further optimize the optical properties of the coated glass pane, a top anti-reflection layer is applied to the low-e and and / or solar control coatings, the dielectric layer of which is generally known, in particular Sn, Ti, Z oxides of Nb, Ce, Hf, Ta, Zr, Al and / or Si, and / or In particular, one or more of the (oxy)nitrides of Si and / or Al, or combinations thereof. The present invention may include further sub-layers of suitable materials selected for the purpose. When such other partial layers are added, it is necessary to ensure that the heat treatment property targeted in this specification is not impaired. should be confirmed.

[0099] Any further layers may contain additives that modify their properties and / or facilitate their manufacture, e.g. It will be understood that the dopant may contain other reactants such as dopants or reactive sputtering gases. In the case of oxide-based layers, adding nitrogen to the sputtering atmosphere produces oxynitrides instead of oxides. In the case of nitride-based layers, oxygen is added to the sputtering atmosphere. Adding a Cr-based SiO 2 solution can also result in the formation of an oxynitride rather than a nitride.

[0100] When any such further partial layers are added to the basic layer sequence of the glass pane of the present invention By selecting the appropriate material, structure and thickness, the main objective is to achieve, for example, high thermal stability. Care must be taken not to significantly impair the targeted properties.

[0101] Furthermore, the coated glass panes according to the invention preferably comprise one or more absorbent layers. The one or more absorber layers may be used as a lower anti-reflection layer and / or an upper anti-reflection layer depending on the number of silver-based functional layers. Preferably, it can be positioned on the antireflection layer.

[0102] At least one absorber layer is made of Ti, V, Cr, Fe, or W, Ni, Nb, and the like. More preferably, at least one absorber layer is made of a tantalum or titanium alloy. Tungsten (W), preferably tungsten nitride.

[0103] Furthermore, at least one absorbing layer based on tungsten is provided between the lower anti-reflection layer and / or the upper It is preferably located in the anti-reflection layer.

[0104] In the context of the present invention, at least one absorber layer is made of an (oxy)nitride of Si and / or an (oxy)nitride of Al. Preferably, the layer is in contact with at least one layer of an oxynitride and / or alloy thereof. More preferably, at least one absorber layer is made of an (oxy)nitride of Si and / or embedded between two layers of Al (oxy)nitrides and / or their alloys and in contact with them This configuration exhibits the lowest haze and the most neutral transmission or reflection before and after heat treatment. It is beneficial in that it has the potential to achieve brilliant colors.

[0105] Preferably, at least one absorber layer is in contact with at least one layer of an Al nitride system. More preferably, at least one absorbing layer is embedded between two layers of Al nitride type. be drawn into and come into contact with them.

[0106] Tungsten, preferably in the form of tungsten nitride, WNx, in the lower and / or upper anti-reflective layer. The tungsten-based absorbing layer is preferably 0.5 nm or more, more preferably 0.5 nm or 1 nm or more, even 1.5 nm or more, but preferably less than 10 nm, more preferably 8 nm These preferred thicknesses can also be used to maintain mechanical durability. This makes deposition easier and improves optical properties such as haze.

[0107] Embodiments of the present invention will now be described, by way of example only, with reference to the following examples. DETAILED DESCRIPTION OF THE INVENTION

[0108] experiment Silicon oxide (SiO ) was applied to the uncoated tin side of the float glass sheet. x ) Set up the base layer A series of experiments were carried out to evaluate the effect of a silicon oxide layer on the surface of a float glass substrate. After deposition on the "tin" side, an additional coating layer is deposited on top of the silicon oxide layer, resulting in an additional The coating layer includes at least one silver-based layer. The "air" side of the port was also coated with a series of coating layers.

[0109] Experiment 1 - Oxide deposited on the tin side of a glass substrate coated with a silver-based low-emissivity coating Comparison of results with and without a silicon (SiO2) underlayer Before the deposition of a series of coating layers (called a stack), a silicon oxide (SiOx) substrate is applied. The coating layer was deposited on the tin side of a float glass substrate. The emissivity coating is included. The sequence of layers is shown in Table 1.

[0110] MF - Single or dual magnet with AC and / or DC (or pulsed DC) power supply Using Netron, a 6mm thick standard float glass plate with a light transmittance of approximately 88% was coated with acid. A silicon dioxide (SiOx) layer and an additional coating layer were deposited.

[0111] The materials are listed in Table 1, with the geometric thickness of each layer given in nanometers in parentheses. The coating layer is obtained as follows. Zinc (Zn) and tin (Sn) oxide layers were deposited by argon / oxygen (Ar / O2) sputtering. Reactive sputtering from a zinc-tin target (weight ratio Zn:Sn approximately 50:50) in an atmosphere did. Titanium oxide (TiO x ) layer in an argon / oxygen (Ar / O2) sputtering atmosphere. It was deposited from a metallic titanium (Ti) target. The ZnOx layer was formed by sputtering with an Al-doped Zn target (aluminum The aluminum (Al) content was approximately 2% by weight. Functional layers of essentially pure silver (Ag) were deposited in an Ar sputtering atmosphere without the addition of oxygen. Oxygen partial pressure 10 -5 It was sputtered from a silver target at less than 1000 mbar. Silicon nitride (SiN x ) layer containing only residual oxygen was ) Mixed Si in the sputtering atmosphere 90 Al 10 It was reactively sputtered from a target. A layer of silicon oxide (SiOx) is deposited on a Si substrate in argon / oxygen (Ar / O2) 90 Al 10 It sputtered from. The AlN layer was sputtered in an argon / nitrogen (Ar / N2) atmosphere containing only residual oxygen. The material was reactively sputtered from an Al target in a vacuum chamber. A layer of ZnO was deposited on a ceramic ZnO:Al target (Al) in an Ar / O2 sputtering atmosphere. The aluminum (Al) content was approximately 10% by weight. A layer of NiCrOx was deposited on a nickel-chromium alloy target in an Ar / O2 sputtering atmosphere. (Nickel (Ni) about 80 wt% and chromium (Cr) about 20 wt%) reactively sputtered did. A layer of WNx was reactively sputtered from a metallic W target in an Ar / N2 sputtering atmosphere. Ta. The coating stack was deposited using standard process conditions.

[0112] [Table 1] Silicon oxide in a silver-based low-emissivity coating stack deposited on a float glass sheet Results with and without SiO2 underlayer

[0113] Tables 1, 2a, 2b and 3 show comparative coated glass sheets and coated glass sheets according to the invention. Details of the layer arrangement of the glass sheets are provided below along with the test results for each stack. Haze scan, oil rub test value, T L %-Percentage of light transmittance of glass substrate before heat treatment ( %) value, ΔT L - Change in light transmittance percentage (%) upon heat treatment, Rs AD - Sheet before heat treatment resistance, Rs HT - sheet resistance after heat treatment, ΔRs (ohm / sq) - change in thermal resistance, and T ΔE * -Measure of the change in transmission color during heat treatment.

[0114] The methods used to collect the data in Tables 1, 2a, 2b, and 3 are described below. The layers were deposited onto a glass plate in the order shown, starting with the top layer of each row.

[0115] Oil rub test - The oil rub test is carried out to check whether the cutting oil used to cut the glass plate is Serves to simulate the effect on mechanical robustness. Does not withstand oil rub test. Coated glass plates are difficult to process and are not suitable for most practical applications. The coated samples shown in Table 1 (and Table 2) , immersed in microscope oil with a refractive index of 1.52 (1.515-1.517) with an area of ​​1.2c The sample was rubbed with a 1.2 cm x 1.2 cm felt pad at a rate of 37 cycles per minute. It is subjected to 500 cycles with a load of 1,000g. Then, it is graded from 0 (perfect, undamaged) to 9 ( An internal evaluation system based on a completeness scale (complete removal of part of the coating stack) The oil-rubbed samples were evaluated using a swatch test. A score of 6 or less is preferred.

[0116] Heat treatment test - Coatings on glass substrates of the examples in Tables 1, 2a, 2b, and 3 Immediately after deposition, the coating stack parameters (sheet resistance (Rs), optical transmittance (T L ), haze scan, and color coordinates were measured for each coated glass substrate. The substrate was heat-treated at approximately 650°C for 5 minutes and 30 seconds. After that, the haze scan value, sheet resistance (Rs), the light transmittance percentage and the light reflectance percentage of both surfaces (T L , R Film , R Glass ) The light transmittance and light reflectance from both surfaces (T L , R Film , R Glass ) and color change during heat treatment (ΔE * ) was calculated from it.

[0117] The light transmittance and reflectance (%) of the coated glass plate examples in Tables 1 and 3 upon heat treatment are The stated values ​​for the changes are obtained from measurements according to EN410, see details there. and is incorporated herein by reference.

[0118] Sheet resistance / change in sheet resistance for example - NAGY SRM-12 This device measures the resistance of a 100mm x 100mm coated test piece using an inductor. This generates eddy currents in the material, which produce measurable currents whose magnitude is related to the resistivity of the sample. An electric field is generated. By this method, the sheet resistance can be calculated. The sheet resistance of the sample was measured before and after heat treatment at 650°C for 5 minutes and 30 seconds.

[0119] Color characteristics - well-established CIE LAB L * , a * , b * Coordinates (as referenced herein) For example, see paragraphs 0030 and 0031 of WO 2004 / 063111, which is incorporated herein by reference. The color properties of each of Samples 1 to 14 were measured and reported using a chromaticity tester (described in the literature). Transmitted color change T ΔE * =((Δa * ) 2 +(Δb * ) 2 +(ΔL * ) 2 ) 1 / 2 and , ΔL * , Δa * , and Δb * is the color value L of the coated glass sheet before and after heat treatment * , a * , b * The layer arrangement having one silver-based functional layer has a difference of less than 3 (e.g., 2 or 2.5). ) ΔE * This value indicates that the discoloration caused by the heat treatment is small and virtually unnoticeable. In layer arrangements containing two or more silver-based functional layers, a small T ΔE * The value is the stability of the sequence. and T ΔE * The lower the value, the better the result and appearance of the coated glass sheet.

[0120] The HazeScan-Haze scoring system was applied to each example. An assessment rating system is also used to more clearly differentiate the visual quality of coatings under bright light conditions. This is well within the standard haze values ​​measured according to ASTM D1003-61. It is a characteristic that is not reflected.

[0121] The rating system recognizes local color variations caused by damage or imperfections in the coating. This takes into account the more macroscopic effects of visible defects in the coating (haze scan in Table 1). In this assessment, images of heat-treated samples taken using fixed lighting conditions and geometry were Analyze the light levels.

[0122] To generate the image used to calculate the haze scan, the sample was held 30° from the camera lens. The sample is placed in a dark box at a distance of 2400 lux to 2800 lux. A standard 1200 lumen light is used to illuminate the sample. The sample is photographed using the same exposure length. The grayscale of each pixel in the resulting image is then calculated. The values ​​are recorded, where a value of 0 represents black and 255 represents white. A statistical analysis of these values ​​is performed to determine It gives a comprehensive assessment of the haze of the sample, referred to herein as the haze scan value. The smaller the noise scan value, the better the result.

[0123] Experiments 2a and 2b - Silver-based low-emission films in the presence of silicon oxide (SiO2) underlayers of various thicknesses Comparison of Glass Substrates Coated with Reflectance Coatings In Experiments 2a and 2b, the silver-based low-emissivity coatings listed in Table 1 for Examples 1 and 2 were used. Before each deposition of the coating stack, various thicknesses of silicon oxide (SiO2) underlayers were applied. The layer was deposited on a float glass substrate. After the tin side of the glass was coated, the silver-based low-emissivity coating stack of Example 1 shown in Table 1 was deposited. It piled up.

[0124] The silicon oxide (SiOx) layer was formed to a thickness of 7.5 mm (Example 1 only), 15 nm, 30 nm , and 60 nm were deposited on the tin side of a series of 6 mm float glass substrates.

[0125] Tables 2a and 2b show the results of the experiments on float glass sheets in the presence of SiO2 underlayers of various thicknesses. The deposited silver-based low-emissivity coatings listed in Examples 1 and 2 of Table 1 were Includes details of the scan results and average distribution values.

[0126] [Table 2a]

[0127] In each of Examples 4-8, the pyrogenic silica / titania based coating was applied to the air side of the glass. A film was formed on the substrate.

[0128] [Table 2b]

[0129] In each of Examples 9-12, the pyrogenic silica / titania based coating was applied to the air of the glass. A film was formed on the side.

[0130] As can be seen from Table 2a and Table 2b, the silicon oxide (SiO2) layer is formed to a thickness of 30 nm to 60 nm. When the film was deposited on a float glass substrate in the thickness range of A photographic method was used to analyze the images taken of each sample and then express the observed data as an "average haze" value. The Hayes scoring system is applied to each of the examples in Tables 2a and 2b using Haze scan measurements were recorded as described above. Photographs demonstrating the advantage of including a silicon oxide (SiOx) underlayer are shown in Figures 1 and 2. Shown in Figure 2.

[0131] Experiment 3 - Float glass coated with a silicon oxide (SiO2) underlayer and a silicon nitride-based layer Comparison of the substrate with a float glass substrate coated with only a silicon nitride based layer The tin film is deposited on the tin side of the float glass substrate and is then bonded to the glass substrate via at least one sputter deposition. A protective coating layer of oxide film positioned between further layers, including a metal layer. An additional benefit of using a silicon oxide (SiOx) underlayer is that the The refractive index of the glass substrate (1.51) is very close to that of the glass substrate (1.54). Therefore, the required optical properties can be achieved by, for example, a subsequent low-emissivity solar control coating. The properties are largely maintained and only a slight change is observed in the appearance of the coated glass sheet. The coating (Example 14) contained 50 nm of SiOx as the base SiNx layer. The ratio of the coating to the coating (Example 15) was increased by 50 nm. The details of the layer arrangement are shown in Table 3.

[0132] [Table 3]

[0133] Pyrolytic (CVD) coating on the "air" side of the float glass substrate and deposited on the tin side For Examples 13, 14, and 15 in Table 3, which have low-emissivity coatings, CIE L measured both before and after heat treatment at 50°C for 5 minutes *, a * , and b * Comparing the values ​​of are shown in Tables 4 and 5.

[0134] That is, the change in transmitted color during heat treatment, T ΔE * =((Δa * ) 2 +(Δb * ) 2 +( ΔL * ) 2 ) 1 / 2 Measure ΔL * , Δa * , and Δb * are the specimens before and after heat treatment. Covering glass color value L * , a * , b * The layer arrangement with one silver-based functional layer has the following: ΔE less than 3 (e.g., 2 or 2.5) * values ​​are preferred, and this value is the discoloration caused by heat treatment. In layer arrangements containing two or more silver-based functional layers, T ΔE * The value indicates the stability of the sequence, T ΔE * The smaller the value, the better the results for the coated glass plate. The appearance is excellent.

[0135] From Tables 4 and 5, it can be seen that, for Example 14, this product achieved acceptable color change after heat treatment. It can be seen that it is possible to obtain a strengthening of the coated substrate according to the invention. 15 does not withstand tempering, and increasing the thickness of the SiNx layer affects the color of the coated glass substrate when viewed in transmission. This leads to unacceptable yellowing of the coating.

[0136] Tables 6 and 7 show the results for Comparative Example 13, which does not have a change in layer thickness and does not have an SiOx protective layer. CIE measured on each side of the float glass Examples 14 and 15 described above compared to the recorded values. L* , a * , and b * Indicates the difference in values.

[0137] Furthermore, as can be seen from Tables 6 and 7, the presence of the SiN3 layer significantly improved the stack of Example 15. Deposited on the tin side of a float glass substrate and heat treated to some extent to improve defects However, the use of such coating layers can be difficult to achieve with heat treatment, especially when the deposited layers are thick. Glass substrates coated with such layers result in observed color changes on both the front and back of the float glass. This makes the product undesirable in terms of color and aesthetic appearance.

[0138] [Table 4] Color measurements recorded for the coatings of Examples 13, 14, and 15 before heat treatment were: show.

[0139] [Table 5] Color measurements recorded for the coatings of Examples 13, 14, and 15 after heat treatment were: show.

[0140] [Table 6]

[0141] [Table 7]

[0142] [Table 8] Changes in CIE lab measurements recorded for Examples 15, 16, and 17 after heat treatment Summary of the transformation.

[0143] From the results in Tables 6 and 7, compared with Example 14 having an additional layer of SiOx as a protective layer, , L of Comparative Example 13 * , a * , or b * Only small differences of less than 5 units were observed in the values ​​of It is clear that

[0144] In contrast, L in Example 14 * , a * , or b * The value of and the thickness of the base SiNx layer were increased. When compared with Comparative Example 15, it was found that there was a maximum difference of 29.89 units.

[0145] Another benefit highlighted by the results in Table 8 is that the comparative example 1 after heat treatment at 650°C for 5 minutes 3, 15 and L of Example 14 * , a * , b * The change in the value of ΔE indicates that the SiOx protective layer is effective. In Example 14, the measured value is very small. Unlike the values ​​obtained in Example 5 (stack with thickened SiNx layer), It was similar to the one in the original.

[0146] The results shown in Table 8, which summarizes the changes in values ​​observed for coated glass substrates after heat treatment, show that the coated ΔE of transmission and reflection of glass * It is preferred that the change in the values ​​recorded for each be less than 10. The values ​​observed for the coated glass substrate after heat treatment, ΔE of the transmission and reflection of the coated glass * to It is highly preferred that the change in the values ​​recorded for be less than 5.

[0147] Experiment 4 - Adding a visible light absorbing layer In another embodiment of the present invention, the visible light absorption to the bottom anti-reflective layer of the coating stack is The addition of a sintering layer (e.g., tungsten nitride, WNx) has been investigated. For example, further enhancement can be achieved by including a visible light absorbing layer in the lower anti-reflective layer of the coating stack. The benefit, i.e., the negative b of the reflection on both sides of the coated glass sheet * Effectively preserves the transparency value while preserving the original value. negative b * The benefit of this is a shift towards blue values ​​(i.e., blue values ​​due to transmission). It is possible.

[0148] This is particularly desirable if the first coating, deposited by, for example, CVD, is a visible stain. When making a double-sided coating containing a material that reflects in the blue region of the spectrum, The reason is that CVD coating has a high transmittance. * The effect of increasing the value, This is because it has the effect of giving the coated glass plate a yellowish tint in transmission. According to our findings, the lower anti-reflection layer of the coating sequence is made of tungsten nitride, WNx, etc. By adding a visible light absorbing layer, it is possible to avoid the yellow tint of the coating.

[0149] Another benefit of the additional visible light absorbing layer is that the reflected color on both sides of the coated glass pane is in any case extremely Very blue, i.e. b * The value is -15 or less. The specular color is all negative a * Show the value It is even more beneficial to do so.

[0150] A series of coatings were deposited on a float glass sheet as described in Table 9. The air side of the plate is coated with a thermal decomposition (CVD) coating. , silicon commercially available under the trade name Pilkington Activ® and titanium-based coatings. (Examples 1 and 2 are included for comparison.) The beneficial effects of this are shown in Table 10 for as-deposited values ​​and in Table 11 for heat-treated values. vinegar.

[0151] [Table 9]

[0152] [Table 10]

[0153] [Table 11]

[0154] As can be seen from the above discussion and results, the main advantage of the present invention is that it Chemical vapor deposition (CVD) and physical vapor deposition (PVD) or sputter coatings deposited on opposite surfaces It allows for the production of glass sheets that can be heat treated or tempered after the layer combination is applied. And so.

[0155] Yet another benefit provided by the present invention is that both types of deposition applied to glass substrates The goal is to maximize the benefits obtained from the process. For example, Self-cleaning coatings have much higher levels of light resistance than purely sputtered coatings. It has been shown to be active and can be deposited on one side of a glass sheet. In contrast, low haze, sheet resistance, and high selectivity for low-e / solar control purposes A silver-based low-emissivity (low-e) coating known to be The low-e coatings can be deposited by CVD and therefore have better performance than low-e coatings deposited by CVD.

[0156] Although there are coated glass products that utilize multiple technologies, unlike the present invention, no such Products cannot be heat strengthened.

[0157] Additionally, products can be toughened or annealed using multiple techniques to create coatings. Although there are products available, the selection of such products is limited and the coating does not contain a silver layer. The performance of the product is poor.

[0158] The sputter coating is applied to the tin side of the float glass substrate (i.e., the float glass ribbon). The CVD coating layer is deposited on the float glass (underside during the formation of the glass and the annealing process). (or air / gas) side (top surface during formation and annealing of the float glass ribbon in the float bath) ) by combining the techniques in a single dual-coated glass sheet according to the present invention. Therefore, the present invention provides a method for forming a high quality sputter coating on the atmosphere side of a glass substrate while maintaining the high quality of the sputter coating. The conventional limitation of sputter deposition is that this side is in contact with the roller during the manufacturing of the glass substrate. (This may result in marks or imperfections in the sputter coating.)

[0159] Thus, the present invention addresses the problems previously manifested in connection with the creation of such products. Various types of glass are used in the tempering or float glass manufacturing process, especially in annealing furnaces. Contact with the rollers of this type can lead to damage to the sputter coating, and in many cases Improvements in haze scan values ​​of over 25% have been made to address issues that would otherwise only become apparent upon strengthening. Overcome.

[0160] For example, a substrate may have a CVD coating on one side and sputtered silver on the second side. There are alternative methods by which heat-strengthened glass sheets with inclusion coatings can be produced. One example of this is CV D coated glass cut to size sheets are heat strengthened and then cut to size and tempered glass is The other option is to deposit a silver-based PVD coating on the opposite side, but there are many drawbacks to this approach. Inefficient use of PVD coating equipment, additional labor costs associated with manually feeding cut-to-size sheets into the equipment CVD coating on one side and silver-based PVD coating on the other side. Further disruption to the supply chain increases both the cost and time required to produce reinforced panels. The resulting complexity is as follows:

[0161] A second alternative method for producing such a final product is to provide a CVD coating on one side. Two tempered coated glass sheets are laminated together, one of which has a silver-based PVD coating on the other side. Such laminated glass sheets allow fabricators to temper the tin side of the glass substrate. However, this approach avoids the deposition of a functional coating on the final glass. The cost of manufacturing a sheet metal increases dramatically, resulting in two separate products that must be machined and then laminated together. Inventory must be maintained by the producer.

[0162] The present invention avoids both of the above-mentioned difficult situations and also provides a method for forming a CVD film on one side of a glass substrate. Heat-strengthened glass with a silver-based PVD coating on the second side of the glass substrate. This allows for the most efficient and cost-effective production of glass plates.

[0163] The refractive index of the SiOx protective layer described by this invention is close to that of the glass substrate, As a result, even if the protective layer is included, the film is not visible, particularly when viewed through the transmission. b *A further advantage of the present invention is that the appearance of the coated glass sheet is not significantly altered with respect to The refractive index of SiNx and the like (which is higher than the refractive index of the SiOx protective layer described by the present invention) is When alternative materials (with a high thermal conductivity) are used, the appearance of the coated glass panes changes significantly and in many cases In this case, this is a very high transmission of over 10 units. * This is the form of the value when viewed transparently. In this case, the protective layer according to the present invention gives the coated glass sheet an unattractive yellowish tint. Similar products made with SiOx of equivalent thickness used as a reinforcement material have superior reinforcement performance. (i.e., low haze), but also less than 10 units, more preferably less than 8 units; Even more preferably, substantially low permeation b of less than 6 units * It also has a value, which is given to the observer. It looks more beautiful.

[0164] A further benefit of the present invention is that, in addition to providing the benefits described above, the present invention, when viewed in reflection, especially the air-side reflection (i.e. the outermost when incorporated into an insulating glazing unit) The CVD coating on the surface also maintains a good appearance when viewed through a reflective surface. The monolithic glass sheets produced according to the present invention have a tensile strength in the range of 10 units to -10 units, more preferably More preferably, the air side deflection is between 7 units and -10 units, and even more preferably between 5 units and -10 units. shooting a * At the same time, the air-side reflection b * The recorded values ​​for are usually negative ( i.e., blue appearance), preferably in the range of 0 units to -30 units, more preferably -2 units to -27 units, and even more preferably in the range of -4 units to -25 units.

Claims

1. 1. A temperable coated float glass substrate, comprising: i) a first surface; ii) a second surface; and wherein the first surface includes one or more layers deposited by chemical vapor deposition (CVD). the second surface comprises one or more layers deposited by physical vapor deposition (PVD); The one or more layers deposited by physical vapor deposition (PVD) have at least one function. a conductive metal layer; the second surface further comprises a protective layer deposited in direct contact with the second surface; and The coated float glass substrate has a transmission b according to the CIE color space of 3 or less. ＊ Color value and -5 or less Lower external reflection b ＊ 1 shows a temperable coated float glass substrate.

2. 2. The reinforceable coated substrate of claim 1, wherein the protective layer is silicon oxide (SiOx). layer, and x is in the range of 1.5 to 20.

3. 2. The temperable coated substrate according to claim 1, wherein, according to the CIE color space, b ＊ and a ＊ The value is negative for external reflection of the temperable coated substrate.

4. 4. The temperable coated substrate according to claim 1, 2 or 3, wherein the protective layer is formed by physical vapor deposition ( Temperable coated substrates deposited by PVD.

5. The temperable coated substrate according to any one of claims 1 to 4, wherein the thickness of the protective layer is is a toughenable coated substrate in the range of 10 nm to 100 nm.

6. The temperable coated substrate according to any one of claims 1 to 5, wherein the thickness of the protective layer is is a toughenable coated substrate in the range of 30 nm to 70 nm.

7. The temperable coated substrate according to any one of claims 1 to 6, wherein the float glass The second surface of the glass contacts molten tin during manufacture, and the first surface of the float glass A temperable coated substrate whose surface is in contact with a bath atmosphere containing nitrogen and hydrogen during manufacture.

8. 8. The temperable coated substrate according to claim 1, wherein the glass substrate The one or more layers deposited by chemical vapor deposition (CVD) on the first surface include: Silicon oxide (SiO ２ ), tin oxide (SnO ２ ), fluorine-doped tin oxide (SnO ２ : F), titanium oxide (TiO ２ ), and antimony-doped tin oxide (SnO ２ : Sb) a reinforceable coated substrate comprising one or more doped or undoped oxide layers selected from 。

9. The reinforceable coated substrate according to any one of claims 1 to 8, wherein the functional metal layer is a temperable coated substrate comprising silver.

10. A reinforceable coated substrate according to any one of claims 1 to 9, wherein each surface of the coated substrate The color change in transmission after heat treatment (ΔE ＊ ) is 10 or less.

11. 11. The reinforceable coated substrate according to claim 1, wherein each of the coated substrates The change in color of the reflection after heat treatment of the surface (ΔE ＊ ) is 10 or less.

12. The temperable coated substrate according to any one of claims 1 to 11, wherein the coating is a physical vapor deposition (PV) D) the one or more layers deposited by Ti, V, Cr, Fe, or W, Ni, Reinforceable coatings comprising at least one absorbing layer based on Nb, its alloys and nitrides - Patent Application 20070122997 substrate.

13. 13. The reinforceable coated substrate of claim 12, wherein the at least one absorber layer is A temperable coated substrate comprising tungsten (W), preferably tungsten nitride.

14. The dual-coated temperable float glass according to any one of claims 1 to 13.

1. A method of preparing a substrate, comprising: i) providing a float glass substrate having a first surface and a second surface; The second surface of the glass substrate contacts molten tin during manufacturing, and the first surface contacts molten tin during manufacturing. contacting the catalyst with a bath atmosphere comprising nitrogen and hydrogen; ii) depositing one or more layers onto the first surface of the substrate by chemical vapor deposition (CVD); and iii) depositing one or more layers on the second surface of the substrate by physical vapor deposition (PVD); an accumulation step; iv) prior to depositing said one or more layers on said second surface, physical vapor deposition (PVD) depositing a protective layer directly on the glass substrate, the protective layer having a thickness of 10 nm to 1 a step having a thickness of 100 nm; v) degrading the one or more layers deposited on each side of the coated glass substrate; and heat treating the substrate to strengthen the glass without A method comprising:

15. 15. The method of claim 14, wherein the protective layer comprises a silicon oxide (SiOx) layer, x is in the range of 1.5 to 2.

0.

16. 16. The method of claim 14 or 15, wherein the deposition of the substrate is performed by physical vapor deposition (PVD). The method wherein the one or more layers deposited on the second surface include a functional metal layer.

17. 17. The method of claim 16, wherein the functional metal layer comprises silver.

18. The method according to any one of claims 14 to 17, wherein the protective layer has a thickness of 30 nm to 70 nm. Methods deposited to thicknesses in the nm range.

19. The method according to any one of claims 14 to 18, wherein the first surface of the substrate is The one or more layers deposited by chemical vapor deposition (CVD) include: Silicon oxide (SiO ２ ), tin oxide (SnO ２ ), fluorine-doped tin oxide (SnO ２ : F), titanium oxide (TiO ２ ), and antimony-doped tin oxide (SnO ２ : Sb) The method includes one or more layers selected from:

20. The method according to any one of claims 14 to 19, wherein the second surface of the substrate is The deposited physical vapor deposition (PVD) layer is formed on the first surface of the substrate. Or, the method is such that the layer is deposited after the deposition of multiple layers.

21. Temperable coated float according to any one of claims 1 to 13 in architectural flat glass articles. Use of glass substrate.

22. A temperable coating according to any one of claims 1 to 13 in an insulating glazing unit. Use of float glass substrate.

23. In automotive glass such as windshields, skylights, sidelights, or backlights Use of the temperable coated float glass substrate according to any one of claims 1 to 13.

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