Coated glass, method for manufacturing coated glass, and laminated glass

Abstract

This application provides a coated glass and its preparation method, as well as a laminated glass. The coated glass includes a first substrate and a coating structure. The coating structure is disposed on the surface of the first substrate. The coating structure includes at least two functional layers and an outermost protective layer. Each functional layer includes a metal layer. At least two functional layers are stacked on the surface of the first substrate. The outermost protective layer is connected to the side of the functional layers facing away from the first substrate. The material of the outermost protective layer includes an AlOxNy layer. The refractive index n of the AlOxNy layer satisfies the range of 1.67 ≤ n ≤ 1.77, and the extinction coefficient k of the AlOxNy layer satisfies the range of k ≤ 3.0E-3. The pencil hardness of the coating structure is ≥ 9H. The technical solution of this application enables the coating structure to have better heat treatment stability and overall mechanical stability.

Description

Technical Field

[0001] This application relates to the field of glass technology, and in particular to a coated glass and its preparation method, and laminated glass. Background Technology

[0002] Coated glass refers to glass coated with a special coating or film layer formed on the surface of a glass substrate using vapor deposition technology. Vapor deposition technology is further divided into chemical vapor deposition (CVD) and physical vapor deposition (PVD). In actual products, physical vapor deposition technology can be used to manufacture coated glass containing 1-4 silver layers. Due to the characteristics of silver layers, such as infrared reflection and good conductivity, coated glass containing silver layers can be used as heat-insulating glass or electrically heated glass. When heat-insulating glass is installed in vehicles, it can prevent light other than visible light from sunlight, especially infrared light, from entering the interior space, thereby significantly reducing air conditioning energy consumption and improving the thermal comfort of drivers and passengers. The temperature of electrically heated glass can rise with the passage of current, thereby achieving functions such as preventing fogging or defrosting, and de-icing, improving driving safety.

[0003] When coated glass is manufactured for use as heat-insulating or electrically heated glass in motor vehicles, it requires high-temperature heat treatment at at least 500°C and bending shaping, such as the baking and pressing bending processes for automotive glass. This necessitates that the coating or film on the coated glass not only meet the requirements for optical performance and appearance quality but also possess high mechanical properties, thermal stability, and chemical stability. Traditional coated glass containing a silver layer has poor mechanical properties and low hardness, making it easily scratched by hard objects during subsequent transportation, storage, handling, and processing, resulting in poor processing resistance. Summary of the Invention

[0004] The embodiments of this application provide a coated glass and its preparation method, as well as a laminated glass, which enables the coated structure to have better heat treatment stability and overall mechanical stability.

[0005] In a first aspect, this application provides a coated glass, comprising:

[0006] First substrate; and

[0007] A coating structure is disposed on the surface of a first substrate. The coating structure includes at least two functional layers and an outermost protective layer. Each functional layer includes a metal layer. At least two functional layers are stacked on the surface of the first substrate. The outermost protective layer is connected to the side of the functional layers facing away from the first substrate. The material of the outermost protective layer includes an AlOxNy layer. The refractive index n of the AlOxNy layer satisfies the range of 1.67 ≤ n ≤ 1.77. The extinction coefficient k of the AlOxNy layer satisfies the range of k ≤ 3.0E-3. The pencil hardness of the coating structure is ≥ 9H.

[0008] In this embodiment, the AlOxNy layer not only possesses high hardness, excellent dielectric properties, chemical stability, and high temperature resistance, but also exhibits excellent light transmittance in the visible light band. Therefore, the AlOxNy layer can protect the functional stack through its high hardness. Furthermore, the excellent dielectric properties, chemical stability, and high temperature resistance of the AlOxNy layer facilitate the formation of the coating structure during processing and prevent it from easily deteriorating due to temperature or the processing environment.

[0009] Furthermore, the optical thickness of the outermost protective layer needs to be maintained within a certain range to avoid the structure of the outermost protective layer having an excessive impact on the overall optical performance of the coated glass. Optical thickness refers to the total attenuation caused by absorbing and scattering matter per unit cross-sectional area when calculating radiative transmission. It reflects the material's ability to absorb and scatter light.

[0010] The refractive index (n) of the AlOxNy layer meets the range of 1.67 ≤ n ≤ 1.77, and the extinction coefficient (k) meets the range of k ≤ 3.0E-3. Compared to conventional silver-based protective layer SiNx materials, the AlOxNy layer has a lower refractive index. Given the same optical thickness of the outermost protective layer, the physical thickness of AlOxNy will be greater (optical thickness = physical thickness * refractive index (n)). A thicker outermost protective layer results in higher hardness and better protection for the functional layers.

[0011] The extinction coefficient k of the AlOxNy layer must be within the range of k≤3.0E-3 to avoid excessively large extinction coefficient k, which would lead to excessive light absorption by the film and affect the optical performance of the coated glass.

[0012] When the pencil hardness of the outermost protective layer is ≥9H, which is sufficient to protect the functional layers, the coated glass is less likely to be scratched by hard objects during transportation, storage, handling, and processing, thus improving its processing resistance and increasing the yield of coated glass.

[0013] In one possible implementation, in the AlOxNy layer, X satisfies 0≤x≤2, and Y satisfies 0≤y≤2.

[0014] In one possible implementation, the X to Y ratio in the AlOxNy layer is in the range of 0.8-1.2.

[0015] In one possible implementation, each of the functional stacks includes a lower dielectric layer, the metal layer, and an upper dielectric layer stacked sequentially.

[0016] In one possible implementation, the metal layer comprises at least one of Ag, Au, Cu, Al, and their alloys.

[0017] In one possible implementation, the lower dielectric layer comprises at least one of AZO, Ti alloy, NbOx, TiOx, NiCr, NiCrOx, ZnAlOx, ZnOx, and SnOx.

[0018] In one possible implementation, the coating structure further includes an intermediate layer located between two adjacent functional layers, the intermediate layer being made of at least one of ZnSnOx, SiAlZrNx, SiAlNx, SiNx, SiZrNx, ZnOx, AZO, ZnAlOx, ITO, and ZrOx.

[0019] In one possible implementation, the coating structure further includes an adhesion layer connected between the first substrate and one of the functional stacks, wherein the material of the adhesion layer includes at least one of SiAlZrNx, ZrOx, NbOx, SiNx, ZnSnOx, and SiZrNx.

[0020] In one possible implementation, the coating structure further includes a first protective layer located between the functional stack and the outermost protective layer, wherein the material of the first protective layer includes ZnSnOx.

[0021] In one possible implementation, the coating structure further includes a second protective layer located between the first protective layer and the outermost protective layer, the material of the second protective layer including TiOx.

[0022] Secondly, this application provides a laminated glass comprising a second substrate, an adhesive layer, and a coated glass as described above, wherein the adhesive layer is connected between the second substrate and the coated glass, and the coated structure is located between the first substrate and the second substrate.

[0023] Thirdly, this application provides a method for preparing coated glass, comprising:

[0024] Provide the first substrate:

[0025] A coating structure is formed on the surface of the first substrate by magnetron sputtering.

[0026] The coating structure includes at least two functional layers and an outermost protective layer. Each functional layer includes a metal layer. At least two functional layers are stacked on the surface of the first substrate. The outermost protective layer is connected to the side of the functional layers facing away from the first substrate. The material of the outermost protective layer includes an AlOxNy layer. The refractive index n of the AlOxNy layer satisfies the range: 1.67≤n≤1.77. The extinction coefficient k of the AlOxNy layer satisfies the range: k≤3.0E-3. The pencil hardness of the coating structure is ≥9H.

[0027] In one possible implementation, the target power source for magnetron sputtering the AlOxNy layer is a high-power pulsed magnetron sputtering power source, and the AlOxNy layer is deposited by sputtering Al target material in an Ar, O2, N2 atmosphere.

[0028] In one possible implementation, the high-power pulsed magnetron sputtering power supply operates at a voltage range of 550V-1000V, operates at a current range of 200A-525A, has a peak power range of 110kW-525kW, and has a duty cycle range of 3%-20%. Attached Figure Description

[0029] To more clearly illustrate the technical solution of this application, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0030] Figure 1 This is a cross-sectional schematic diagram of the laminated glass provided in the embodiments of this application;

[0031] Figure 2 yes Figure 1 A cross-sectional schematic diagram of the first embodiment of the coated glass shown;

[0032] Figure 3 yes Figure 1 A cross-sectional schematic diagram of the second embodiment of the coated glass shown;

[0033] Figure 4 yes Figure 1 A cross-sectional schematic diagram of the third embodiment of the coated glass shown;

[0034] Figure 5This is a schematic flowchart of a method for preparing coated glass provided in an embodiment of this application.

[0035] Figure label:

[0036] Laminated glass 1000, coated glass 1001, adhesive layer 1002, second substrate 1003, first substrate 100, coated structure 200, outermost protective layer 280, first stack 220, second stack 230, intermediate layer 250, adhesion layer 210, first protective layer 260, second protective layer 270, first lower dielectric layer 221, first metal layer 222, first upper dielectric layer 223, second lower dielectric layer 231, second metal layer 232, second upper dielectric layer 233, third stack 240, third lower dielectric layer 241, third metal layer 242, third upper dielectric layer 243, first intermediate layer 251, second intermediate layer 252, fourth stack 290, fourth lower dielectric layer 291, fourth metal layer 292, fourth upper dielectric layer 293, third intermediate layer 253. Detailed Implementation

[0037] For ease of understanding, the terminology used in the embodiments of this application will be explained first.

[0038] And / or: This is simply a way of describing the relationship between related objects. It indicates that there can be three kinds of relationships. For example, A and / or B can represent three situations: A exists alone, A and B exist simultaneously, and B exists alone.

[0039] Multiple: refers to two or more.

[0040] Connection: should be interpreted broadly. For example, the connection between A and B can be a direct connection between A and B, or an indirect connection between A and B through an intermediary.

[0041] The specific embodiments of this application will now be clearly described in conjunction with the accompanying drawings.

[0042] Please see Figure 1 , Figure 1 This is a cross-sectional schematic diagram of the laminated glass 1000 provided in an embodiment of this application. The laminated glass 1000 includes a coated glass 1001, an adhesive layer 1002, and a second substrate 1003. The adhesive layer 1002 connects the second substrate 1003 and the coated glass 1001. The coated glass 1001 includes a first substrate 100 and a coating structure 200. The coating structure 200 is disposed on at least one surface of the first substrate 100. Exemplarily, the coating structure 200 is located between the first substrate 100 and the second substrate 1003, that is, the side of the first substrate 100 where the coating structure 200 is disposed is connected to the adhesive layer 1002.

[0043] It should be noted that, Figure 1The purpose is merely to illustratively describe the connection relationship between the coated glass 1001, the adhesive layer 1002, and the second substrate 1003, and is not to specifically limit the connection positions, specific structures, or quantities of each device. Furthermore, the structures illustrated in the embodiments of this application do not constitute a specific limitation on the laminated glass 1000. In other embodiments of this application, the laminated glass 1000 may include components that are more... Figure 1 This may involve more or fewer components, or combining certain components, or splitting certain components, or different component arrangements. Figure 1 The components shown can be implemented in hardware, software, or a combination of both.

[0044] In this application, the laminated glass 1000 can be installed on a vehicle as a windshield, side window, rear window, or sunroof, etc.

[0045] Both the first substrate 100 and the second substrate 1003 can be transparent glass or ultra-transparent glass (ultra-white glass). Ultra-transparent glass has a low iron oxide (Fe2O3) content and a visible light transmittance greater than or equal to 90%. Transparent glass has a total iron content less than or equal to 0.1% and a visible light transmittance greater than or equal to 80%. By weight percentage, the first substrate 100 and the second substrate 1003 may include 0 to 0.1% iron oxide (Fe2O3), for example, the iron oxide (Fe2O3) content in the first substrate 100 and the second substrate 1003 may be less than or equal to 0.09%, less than or equal to 0.08%, less than or equal to 0.07%, less than or equal to 0.05%, less than or equal to 0.04%, less than or equal to 0.03%, less than or equal to 0.02%, less than or equal to 0.015%, or less than or equal to 0.01%, or even substantially no iron oxide (Fe2O3). For example, the first substrate 100 and the second substrate 1003 can be sodium-calcium-silicon ultra-transparent glass, borosilicate glass, or high-alumina glass, etc.

[0046] The adhesive layer 1002 is used to connect the first substrate 100 and the second substrate 1003 to improve the structural strength of the laminated glass 1000, enabling it to meet safety standards and regulatory requirements in more scenarios. The adhesive layer 1002 can be made of polyvinyl butyral (PVB), ethylene vinyl acetate (EVA), thermoplastic polyurethane elastomer (TPU), or ionomer polymer film (SGP), etc. For example, the adhesive layer 1002 can be a single-layer or multi-layer structure; multi-layer structures can include double-layer, triple-layer, quadruple-layer, and five-layer structures, etc. The adhesive layer 1002 can also have other functions, such as providing at least one colored area as a shaded zone to reduce sunlight interference with the human eye, adding infrared absorbers to provide sun protection or heat insulation, adding ultraviolet absorbers to provide ultraviolet protection, or having at least one layer of the multi-layer structure with a higher plasticizer content to provide sound insulation.

[0047] Please see Figure 2 , Figure 2 yes Figure 1 The diagram shows a cross-sectional view of a first embodiment of the coated glass 1001. The coated structure 200 includes at least two functional layers (not shown) and an outermost protective layer 280. The outermost protective layer 280 is connected to the side of the functional layers facing away from the first substrate 100. Each functional layer includes a lower dielectric layer (not shown), a metal layer (not shown), and an upper dielectric layer (not shown) stacked sequentially. A functional layer is either a first layer 220 or a second layer 230 as described below.

[0048] The lower dielectric layer, metal layer, and upper dielectric layer in each functional stack can be formed by magnetron sputtering. Specifically, in the direction away from the first substrate 100, the lower dielectric layer is located below the metal layer, meaning it is closer to the first substrate 100 than the metal layer. The upper dielectric layer is located above the metal layer, meaning it is further away from the first substrate 100 than the metal layer.

[0049] The metal layer has characteristics such as reflecting infrared rays and good conductivity. The coating structure 200 containing the metal layer enables the coated glass 1001 and the laminated glass 1000 to have heat insulation function, thereby significantly reducing air conditioning energy consumption and improving the thermal comfort of the driver and passengers. Depending on the needs of the actual application, the number of metal layers in the coating structure 200 can be, for example, two, three, four, five, or even more. In one possible implementation, the coating structure 200 can also be used as a transparent conductive film. In this case, the laminated glass 1000 has an electric heating function when energized, thus raising the temperature of the laminated glass 1000 and achieving functions such as preventing fogging or defrosting, improving driving safety. For example, the voltage applied to the laminated glass 1000 can be from 12V to 380V. The metal layer is made of any metal or metal alloy selected from silver, gold, copper, aluminum, and platinum. For example, Ag, AgCu alloy, and AgPt alloy are used. The physical thickness of the metal layer is 5nm-20nm (including the endpoint values ​​of 5nm and 20nm).

[0050] The lower dielectric layer and / or upper dielectric layer include at least one of AZO, Ti alloy, NbOx, TiOx, NiCr, NiCrOx, ZnAlOx, ZnOx, and SnOx. The thickness of the lower dielectric layer and / or upper dielectric layer ranges from 5 nm to 30 nm (inclusive of the endpoints 5 nm and 30 nm).

[0051] In each functional stack, the upper dielectric layer primarily protects the metal layer from damage by oxygen ions. The physical thickness of the upper dielectric layer is 5nm-30nm. The upper dielectric layer can be a single film or composed of multiple sub-films. The lower dielectric layer primarily protects the metal layer from damage by alkali metal ions and serves as a seed layer for the crystallization of the metal layer to improve its deposition density.

[0052] The outermost protective layer 280 is made of an AlOxNy layer. The refractive index n of the AlOxNy layer is in the range of 1.67 ≤ n ≤ 1.77, the extinction coefficient k of the AlOxNy layer is in the range of k ≤ 3.0E-3, and the pencil hardness of the coated structure is ≥ 9H. For example, the thickness of the outermost protective layer 280 can be in the range of 5 nm to 80 nm (inclusive).

[0053] The outermost protective layer 280 is primarily used to protect the metal layers in the functional stack from corrosion and mechanical damage, and to facilitate the adjustment of the mechanical, optical, and high-temperature heat treatment properties of the coating structure 200. The outermost protective layer 280 comprises all film layers in the coating structure 200 that are furthest from the first substrate 100 from the outermost edge of the functional stack.

[0054] In this embodiment, the AlOxNy layer not only possesses high hardness, excellent dielectric properties, chemical stability, and high temperature resistance, but also exhibits excellent light transmittance in the visible light band. Therefore, the AlOxNy layer can protect the functional stack through its high hardness. Furthermore, the excellent dielectric properties, chemical stability, and high temperature resistance of the AlOxNy layer facilitate the formation of the coating structure 200 during processing, and it is not easily deformed by temperature or the processing environment.

[0055] Furthermore, the optical thickness of the outermost protective layer 280 needs to be maintained within a certain range to avoid the structure of the outermost protective layer 280 having an excessive impact on the overall optical performance of the coated glass 1001. Optical thickness refers to the total attenuation caused by absorbing and scattering matter per unit cross-sectional area when calculating radiative transmission. It reflects the material's ability to absorb and scatter light.

[0056] The refractive index (n) of the AlOxNy layer meets the range of 1.67 ≤ n ≤ 1.77, and the extinction coefficient (k) meets the range of k ≤ 3.0E-3. Compared to conventional silver-based protective layer SiNx materials, the AlOxNy layer has a lower refractive index. Given the same optical thickness of the outermost protective layer 280, the physical thickness of AlOxNy will be greater (optical thickness = physical thickness * refractive index (n)). A thicker outermost protective layer 280 results in higher hardness and better protection for the functional layers.

[0057] The extinction coefficient k of the AlOxNy layer must be within the range of k≤3.0E-3 to avoid excessively large extinction coefficient k, which would lead to excessive light absorption by the film and affect the optical performance of the coated glass 1001.

[0058] When the outermost protective layer 280 has a pencil hardness ≥9H, which is sufficient to protect the functional layers, the coated glass 1001 is not easily scratched by hard objects during transportation, storage, handling and processing, which improves its processing resistance and increases the processing yield of the coated glass 1001.

[0059] In some possible implementations, in the AlOxNy layer, X satisfies 0 ≤ x ≤ 2, and Y satisfies 0 ≤ y ≤ 2. The ratio of X to Y in the AlOxNy layer can be in the range of 0.8-1.2.

[0060] In some possible embodiments, the coating structure 200 further includes an intermediate layer 250 located between two adjacent functional layers. The intermediate layer 250 is made of at least one of ZnSnOx, SiAlZrNx, SiAlNx, SiNx, SiZrNx, ZnOx, AZO, ZnAlOx, ITO, and ZrOx. The thickness of the intermediate layer 250 ranges from 30 nm to 75 nm (inclusive).

[0061] In this embodiment, the intermediate layer 250 can improve the flatness of the coating structure 200 and improve the reflective color. These intermediate layers 250 can be a single film layer or composed of multiple sub-film layers.

[0062] In some possible embodiments, the coating structure 200 further includes an adhesion layer 210, which is connected between the first substrate 100 and a functional stack. The material of the adhesion layer 210 includes at least one selected from SiAlZrNx, ZrOx, NbOx, SiNx, ZnSnOx, and SiZrNx. The thickness of the adhesion layer 210 ranges from 10 nm to 40 nm (inclusive of the endpoints 10 nm and 40 nm).

[0063] In this embodiment, the adhesion layer 210 is directly deposited on the surface of the first substrate 100 to reduce or prevent alkali metal ions from diffusing from the glass into the coating structure 200. It can also increase the adhesion between the coating structure 200 and the surface of the first substrate 100, and help to adjust the mechanical properties, optical properties and high-temperature heat treatment properties of the coating structure 200.

[0064] Please refer to the following for some possible implementations. Figure 2 The coating structure 200 also includes a first protective layer 260, which is located between the functional stack and the outermost protective layer 280. The material of the first protective layer 260 includes ZnSnOx. The thickness of the first protective layer 260 ranges from 0 nm to 25 nm (inclusive of the endpoint values ​​of 0 nm and 25 nm).

[0065] In some possible embodiments, the coating structure 200 further includes a second protective layer 270, which is located between the first protective layer 260 and the outermost protective layer 280. The material of the second protective layer 270 includes TiOx. The thickness of the second protective layer 270 ranges from 0 nm to 25 nm (inclusive of the endpoints 0 nm and 25 nm). Along the thickness direction of the coating structure 200, the adhesion layer 210, a functional stack (first stack 220), an intermediate layer 250, another functional stack (second stack 230), the first protective layer 260, the second protective layer 270, and the outermost protective layer 280 are sequentially stacked.

[0066] In the first possible implementation, please continue reading Figure 2 The coating structure 200 has two functional layers: a first layer 220 and a second layer 230. The first layer 220 includes a first lower dielectric layer 221, a first metal layer 222, and a first upper dielectric layer 223. The second layer 230 includes a second lower dielectric layer 231, a second metal layer 232, and a second upper dielectric layer 233. Specifically, the coating structure 200 includes, in sequence, an adhesion layer 210, a first lower dielectric layer 221, a first metal layer 222, a first upper dielectric layer 223, an intermediate layer 250, a second lower dielectric layer 231, a second metal layer 232, a second upper dielectric layer 233, a first protective layer 260, a second protective layer 270, and an outermost protective layer 280.

[0067] In the second possible implementation, please refer to Figure 3 , Figure 3 yes Figure 1 The diagram shows a cross-sectional view of a second embodiment of the coated glass 1001. The coated structure 200 has three functional layers: a first layer 220, a second layer 230, and a third layer 240. The first layer 220 includes a first lower dielectric layer 221, a first metal layer 222, and a first upper dielectric layer 223. The second layer 230 includes a second lower dielectric layer 231, a second metal layer 232, and a second upper dielectric layer 233. The third layer 240 includes a third lower dielectric layer 241, a third metal layer 242, and a third upper dielectric layer 243. The coated structure 200 also includes two intermediate layers 250: a first intermediate layer 251 and a second intermediate layer 252. The coating structure 200 specifically includes an adhesion layer 210, a first lower dielectric layer 221, a first metal layer 222, a first upper dielectric layer 223, a first intermediate layer 251, a second lower dielectric layer 231, a second metal layer 232, a second upper dielectric layer 233, a second intermediate layer 252, a third lower dielectric layer 241, a third metal layer 242, a third upper dielectric layer 243, a first protective layer 260, a second protective layer 270, and an outermost protective layer 280, which are stacked sequentially.

[0068] The thicknesses of the first metal layer 222, the second metal layer 232, and the third metal layer 242 are between 5 nm and 20 nm (inclusive). The thicknesses of the first lower dielectric layer 221, the first upper dielectric layer 223, the second lower dielectric layer 231, the second upper dielectric layer 233, the third lower dielectric layer 241, and the third upper dielectric layer 243 are between 5 nm and 20 nm (inclusive). The thicknesses of the first intermediate layer 251 and the second intermediate layer 252 are between 30 nm and 70 nm (inclusive). The thickness of the adhesion layer 210 is between 10 nm and 50 nm (inclusive). The thickness of the first protective layer 260 is between 0 nm and 20 nm (inclusive). The thickness of the second protective layer 270 is between 0 nm and 20 nm (inclusive).

[0069] In the third possible implementation, please refer to Figure 4 , Figure 4 yes Figure 1 The diagram shows a cross-sectional view of a third embodiment of the coated glass 1001. The coated structure 200 has four functional layers: a first layer 220, a second layer 230, a third layer 240, and a fourth layer 290. The first layer 220 includes a first lower dielectric layer 221, a first metal layer 222, and a first upper dielectric layer 223. The second layer 230 includes a second lower dielectric layer 231, a second metal layer 232, and a second upper dielectric layer 233. The third layer 240 includes a third lower dielectric layer 241, a third metal layer 242, and a third upper dielectric layer 243. The fourth layer 290 includes a fourth lower dielectric layer 291, a fourth metal layer 292, and a fourth upper dielectric layer 293. The coated structure 200 also includes three intermediate layers 250: a first intermediate layer 251, a second intermediate layer 252, and a third intermediate layer 253. The coating structure 200 specifically includes an adhesion layer 210, a first lower dielectric layer 221, a first metal layer 222, a first upper dielectric layer 223, a first intermediate layer 251, a second lower dielectric layer 231, a second metal layer 232, a second upper dielectric layer 233, a second intermediate layer 252, a third lower dielectric layer 241, a third metal layer 242, a third upper dielectric layer 243, a third intermediate layer 253, a fourth lower dielectric layer 291, a fourth metal layer 292, a fourth upper dielectric layer 293, a first protective layer 260, a second protective layer 270, and an outermost protective layer 280, which are stacked sequentially.

[0070] In addition to the structure described above, the laminated glass 1000 may also include two coated glass panes 1001 and an adhesive layer 1002 as described above. The two coated glass panes 1001 are arranged opposite each other on the side where the coating structure 200 is located, and the adhesive layer 1002 connects the two coating structures 200. The structure of any of the coated glass panes 1001 can be referred to the description above, and will not be repeated here.

[0071] This application also provides a method for preparing coated glass 1001, wherein the specific structure of coated glass 1001 can be referred to Figures 1-4 The improvements to coated glass 1001 described above, where there is no conflict, can all be applied to the description of coated glass 1001 above. Please refer to [link / reference]. Figure 5 , Figure 5 This is a schematic flowchart illustrating a method for preparing coated glass 1001 according to an embodiment of this application. The preparation method includes:

[0072] S100: Provides a first substrate 100.

[0073] S200: A coating structure 200 is formed on the surface of the first substrate 100 by a magnetron sputtering process;

[0074] The coating structure 200 includes at least two functional stacks and an outermost protective layer. Each functional stack includes a metal layer. The at least two functional stacks are stacked on the surface of the first substrate. The outermost protective layer is connected to the side of the functional stacks away from the first substrate. The material of the outermost protective layer includes an AlOxNy layer. The refractive index n of the AlOxNy layer satisfies the range: 1.67≤n≤1.77. The extinction coefficient k of the AlOxNy layer satisfies the range: k≤3.0E-3. The pencil hardness of the coating structure 200 is ≥9H.

[0075] In this application, the target power supply for magnetron sputtering the AlOxNy layer is a high-power pulsed magnetron sputtering power supply. The AlOxNy layer is deposited by sputtering Al target material in an Ar, O2, or N2 atmosphere. The operating voltage range of the high-power pulsed magnetron sputtering power supply is 550V-1000V, the operating current ranges from 200A to 525A, the peak power ranges from 110kW to 525kW, and the duty cycle ranges from 3% to 20%.

[0076] The use of HiPIMS power source deposition of AlOxNy layers (HiPIMS) alters the compactness of the AlOxNy layers (HiPIMS), thereby changing the refractive index n and extinction coefficient k of the AlOxNy layers (HiPIMS).

[0077] Comparative Examples 1-7 and Examples 1-5

[0078] This application prepares a 2.1 mm thick transparent glass substrate. Film structures of Comparative Examples 1-7 and Examples 1-5 are deposited on the surface of the transparent glass substrate using a magnetron sputtering process. The optical and mechanical properties of the coated glass 1001 test samples of Comparative Examples 1-7 and Examples 1-5 before high-temperature heat treatment, after high-temperature heat treatment, and after glass interlayer treatment are measured. The measurement results are recorded in Tables 1, 2, and 3. Each of the coated glass 1001 test samples of Comparative Examples 1-7 and Examples 1-5 includes three functional layers.

[0079] Table 1: Measurement results of the coated glass 1001 test samples from Comparative Examples 1-4

[0080]

[0081] It should be noted that in the table above, a passing haze test indicates that, after the test samples are assembled, the testing standard is ASTM D1003, and the haze value is ≤5%. The haze test measures whether the film layers and PVB film on the glass fog up, affecting the glass's light transmittance.

[0082] In the table above, a passing grade in the tapping test indicates:

[0083] The first step is to place the sample of the laminated coated glass 1001 at -18℃±2℃ for at least 2 hours.

[0084] The second step is to remove the sample from the aforementioned low temperature and place it at room temperature for 1-2 minutes, then place it on the sample box and tap it with a hammer.

[0085] The third step is to allow the sample to return to room temperature after being tapped, and wait for the condensate to evaporate.

[0086] The fourth step is to compare the sample with the standard sample and find the pattern that is closest to the standard sample. At this time, the value of the standard sample is the PUMMEL value.

[0087] Fifth, a PUMMEL value in the range of 3-7 indicates that the tapping test is qualified (including endpoint values ​​of 3 and 7).

[0088] One test involved tapping the glass to test the adhesion between the coating layer and the PVB film.

[0089] Comparative Example 1 shows the structure of a conventional triple silver film layer (three functional layers). As can be seen from the table, the outermost protective layer is SiNx(MF). The surface hardness of the coated glass was tested before and after heat treatment, and the results were 3H / 4H, respectively. The surface hardness is low and insufficient to resist various scratches during deep processing.

[0090] Comparative Example 2 uses SiZr target material to deposit SiZrO2 (MF) in Ar and O2 atmosphere to replace SiNx (MF) as the outermost protective layer of the triple silver film system. The surface hardness of the coated glass was tested before and after heat treatment, and the results were 7H / 6H, respectively. The surface hardness was enhanced, but it was still insufficient to resist various scratches during deep processing.

[0091] Comparative Example 3 uses Al target material to deposit AlON (MF) in Ar, N2, and O2 atmospheres to replace SiNx (MF) as the outermost protective layer of the triple silver film system. By controlling the amount of N2 and O2 introduced, x:y=1 in AlOxNy is made. The surface hardness of the coated glass is tested before and after heat treatment, and the results are 5H / 5H, respectively. The surface hardness is enhanced, but it is still insufficient to resist various scratches during deep processing.

[0092] Comparative Example 4 uses a HiPIMS power supply to sputter an Al target to deposit an AlOxNy film in an Ar, N2, and O2 atmosphere. By controlling the amount of N2 and O2 introduced, the x:y ratio in AlOxNy is made to be 5:1. The AlOxNy (HiPIMS) film replaces SiNx (MF) as the outermost protective layer of the triple silver film system. The surface hardness of the coated glass was tested before and after heat treatment, and the results were 6H / 6H, respectively. The surface hardness was enhanced, but it was still insufficient to resist various scratches during deep processing.

[0093] Table 2: Measurement results of the coated glass 1001 test samples of Comparative Examples 5-7 and Example 1

[0094]

[0095] Comparative Example 5 uses a HiPIMS power supply to sputter an Al target to deposit an AlOxNy film in an Ar, N2, and O2 atmosphere. By controlling the amount of N2 and O2 introduced, the x:y ratio in AlOxNy is made 2:1. The AlOxNy (HiPIMS) film replaces SiNx (MF) as the outermost protective layer of the triple silver film system. The surface hardness of the coated glass was tested before and after heat treatment, and the results were 8H and 7H, respectively. The surface hardness was enhanced, but it was still insufficient to resist various scratches during deep processing.

[0096] Comparative Example 6 uses a HiPIMS power supply to sputter an Al target to deposit an AlOxNy film in an Ar, N2, and O2 atmosphere. By controlling the amount of N2 and O2 introduced, the x:y ratio in AlOxNy is made 1:2. The AlOxNy (HiPIMS) film replaces SiNx (MF) as the outermost protective layer of the triple silver film system. The surface hardness of the coated glass was tested before and after heat treatment, and the results were 8H and 7H, respectively. The surface hardness was enhanced, but it was still insufficient to resist various scratches during deep processing.

[0097] Comparative Example 7 uses a HiPIMS power supply to sputter an Al target to deposit an AlOxNy film in an Ar, N2, and O2 atmosphere. By controlling the amount of N2 and O2 introduced, the x:y ratio in AlOxNy is made 1:5. The AlOxNy (HiPIMS) film replaces SiNx (MF) as the outermost protective layer of the triple silver film system. The surface hardness of the coated glass was tested before and after heat treatment, and the results were 6H / 6H, respectively. The surface hardness was enhanced, but it was still insufficient to resist various scratches during deep processing.

[0098] In Example 1, an AlOxNy film was deposited by sputtering an Al target using a HiPIMS power supply in an Ar, N2, and O2 atmosphere. By controlling the amount of N2 and O2 introduced, the x:y ratio in AlOxNy was made 1:1. The AlON (HiPIMS) film replaced the SiNx (MF) film as the outermost protective layer 280 of the triple silver film system. The surface hardness of the coated glass 1001 was tested before and after heat treatment, and the results were >9H / >9H, respectively. The surface hardness was greatly improved, which is sufficient to resist various scratches during deep processing.

[0099] Compared with Comparative Example 3, Example 1 used a HiPIMS power supply to provide instantaneous high power to the Al target, which greatly improved the ionization rate of the Al target, greatly enhanced the compactness of the prepared AlON film, and thus improved the surface hardness of the AlON film.

[0100] Table 3: Measurement results of the coated glass 1001 test samples in Examples 2-5

[0101]

[0102] In Example 2, an AlOxNy film was deposited by sputtering an Al target using a HiPIMS power supply in an Ar, N2, and O2 atmosphere. By controlling the amount of N2 and O2 introduced, the x:y ratio in AlOxNy was made 0.8:1. The AlOxNy (HiPIMS) film replaced SiNx (MF) as the outermost protective layer 280 of the triple silver film system. The surface hardness of the coated glass 1001 was tested before and after heat treatment, and the results were >9H / >9H, respectively. The surface hardness was greatly improved, which is sufficient to resist various scratches during deep processing.

[0103] In Example 3, an AlOxNy film was deposited by sputtering an Al target using a HiPIMS power supply in an Ar, N2, and O2 atmosphere. By controlling the amount of N2 and O2 introduced, the x:y ratio in AlOxNy was made 0.9:1. The AlOxNy (HiPIMS) film replaced SiNx (MF) as the outermost protective layer 280 of the triple silver film system. The surface hardness of the coated glass 1001 was tested before and after heat treatment, and the results were >9H / >9H, respectively. The surface hardness was greatly improved, which is sufficient to resist various scratches during deep processing.

[0104] In Example 4, an AlOxNy film was deposited by sputtering an Al target using a HiPIMS power supply in an Ar, N2, and O2 atmosphere. By controlling the amount of N2 and O2 introduced, the x:y ratio in AlOxNy was made 0.9:1. The AlOxNy (HiPIMS) film replaced SiNx (MF) as the outermost protective layer 280 of the triple silver film system. The surface hardness of the coated glass 1001 was tested before and after heat treatment, and the results were >9H / >9H, respectively. The surface hardness was greatly improved, which is sufficient to resist various scratches during deep processing.

[0105] In Example 5, an AlOxNy film was deposited by sputtering an Al target using a HiPIMS power supply in an Ar, N2, and O2 atmosphere. By controlling the amount of N2 and O2 introduced, the x:y ratio in AlOxNy was made 0.9:1. The AlOxNy (HiPIMS) film replaced SiNx (MF) as the outermost protective layer 280 of the triple silver film system. The surface hardness of the coated glass 1001 was tested before and after heat treatment, and the results were >9H / >9H, respectively. The surface hardness was greatly improved, which is sufficient to resist various scratches during deep processing.

[0106] By comparing Examples 1-5 and Comparative Examples 4-7, it can be seen that when using a HiPIMS power supply to sputter an Al target to deposit an AlOxNy film in an Ar, N2, and O2 atmosphere, and by controlling the amount of N2 and O2 introduced, the x:y ratio in AlOxNy is optimally between 0.8 and 1.2. At this point, the density and various properties of the AlOxNy (HiPIMS) film are closer to those of transparent ceramic AlON. Replacing SiNx (MF) with the AlOxNy (HiPIMS) film as the outermost protective layer 280 of the triple silver film system makes the triple silver film system sufficient to resist various scratches during deep processing.

[0107] Comparative Example 8 and Examples 6-8

[0108] This application prepares a 2.1 mm thick transparent glass substrate. The film structures of Comparative Example 8 and Examples 6-8 are deposited on the surface of the transparent glass substrate using a magnetron sputtering process. The optical and mechanical properties of the coated glass 1001 test samples of Comparative Example 8 and Examples 6-8 before high-temperature heat treatment, after high-temperature heat treatment, and after glass interlayer treatment are measured. The measurement results are recorded in Table 4. The coated glass 1001 test samples of Comparative Example 8 and Examples 6-8 each include two functional layers.

[0109] Table 4: Measurement results of the coated glass 1001 test samples of Comparative Example 8 and Examples 6-8

[0110]

[0111] Comparative Example 9, Example 9 and Example 10

[0112] This application prepares a 2.1 mm thick transparent glass substrate. The film structures of Comparative Examples 9, 9th Example, and 10 are deposited on the surface of the transparent glass substrate using a magnetron sputtering process. The optical and mechanical properties of the coated glass 1001 test samples of Comparative Examples 9, 9th Example, and 10 before high-temperature heat treatment, after high-temperature heat treatment, and after glass interlayer treatment are measured. The measurement results are recorded in Table 5. The coated glass 1001 test samples of Comparative Examples 9, 9th Example, and 10 all include four functional layers.

[0113] Table 5: Measurement results of the coated glass 1001 test samples of Comparative Example 9, Example 9 and Example 10

[0114]

[0115] It can be seen that the outermost protective layer provided in the embodiments of this application can still ensure that the pencil hardness of the coating structure is ≥9H in the four silver film system (four functional stacks).

[0116] The magnetron sputtering process parameters and measurement results of the outermost protective layer 280 in the coating structure 200 of Comparative Examples 1-7 and Examples 1-10 described above are shown in Table 6 below.

[0117] Table 6: Magnetron sputtering process parameters and measurement structures for the outermost protective layer 280 of Comparative Examples 1-7 and Examples 1-10

[0118]

[0119] The production speed of magnetron sputtering is 2 m / min. This application improves the density and surface hardness of the AlOxNy film by using a HiPIMS power supply to deposit AlOxNy film in Ar, O2, and N2 atmospheres, thereby improving the overall hardness of the low-emissivity film and giving the low-emissivity coated glass 1001 high mechanical properties and sufficient hardness to resist various scratches during deep processing.

[0120] The embodiments of this application have been described in detail above. Specific examples have been used to illustrate the principles and implementation methods of this application. The description of the above embodiments is only for the purpose of helping to understand the method and core ideas of this application. At the same time, for those skilled in the art, there will be changes in the specific implementation methods and application scope based on the ideas of this application. Therefore, the content of this specification should not be construed as a limitation of this application.

Claims

1. A coated glass, characterized in that, The application relates to a coated glass structure, comprising: a first substrate; and a coated structure arranged on the surface of the first substrate, the coated structure comprising at least two functional layers and an outermost protective layer, each of the functional layers comprising a metal layer, the at least two functional layers being arranged in a stack on the surface of the first substrate, the outermost protective layer being connected to the side of the functional layers away from the first substrate, the material of the outermost protective layer comprising an AlOxNy layer, the refractive index n of the AlOxNy layer satisfying the range: 1.67<=n<=1.77, the extinction coefficient k of the AlOxNy layer satisfying the range: k<=3.0E-3, the pencil hardness of the coated structure being >=9H, in the AlOxNy layer, x satisfies 0<=x<=2, and y satisfies 0<=y<=2, the ratio of x to y in the AlOxNy layer being in the range of 0.8-1.

2.

2. The coated glass according to claim 1, wherein, Each of the functional layers comprises a lower medium layer, the metal layer and an upper medium layer arranged in a stack.

3. The coated glass according to claim 2, wherein, The metal layer comprises any one of Ag, Au, Cu, Al or a metal alloy.

4. The coated glass according to claim 2 or 3, characterized in that, The lower medium layer comprises at least one of AZO, Ti alloy, NbOx, TiOx, NiCr, NiCrOx, ZnAlOx, ZnOx and SnOx.

5. The coated glass according to claim 1, wherein, The coated structure further comprises an intermediate layer arranged between two adjacent functional layers, the material of the intermediate layer comprising at least one of ZnSnOx, SiAlZrNx, SiAlNx, SiNx, SiZrNx, ZnOx, AZO, ZnAlOx, ITO and ZrOx.

6. The coated glass according to claim 1, wherein, The coated structure further comprises an adhesion layer arranged between the first substrate and one of the functional layers, the material of the adhesion layer comprising at least one of SiAlZrNx, ZrOx, NbOx, SiNx, ZnSnOx and SiZrNx.

7. The coated glass according to claim 1, wherein, The coated structure further comprises a first protective layer arranged between the functional layer and the outermost protective layer, the material of the first protective layer comprising ZnSnOx.

8. The coated glass according to claim 7, wherein, The coated structure further comprises a second protective layer arranged between the first protective layer and the outermost protective layer, the material of the second protective layer comprising TiOx.

9. A laminated glass characterized by The application further relates to a coated glass structure, comprising a second substrate, a bonding layer arranged between the second substrate and the coated glass structure, and the coated structure according to any one of claims 1-8, the coated structure being arranged between the first substrate and the second substrate.

10. A method of producing a coated glass, characterized by, The application further relates to a method for manufacturing a coated glass structure, comprising: providing a first substrate; forming a coated structure on the surface of the first substrate by a magnetron sputtering process; The coating structure comprises at least two functional layers and an outermost protective layer, each of the functional layers comprises a metal layer, the at least two functional layers are stacked on the surface of the first substrate, the outermost protective layer is connected to the side of the functional layers away from the first substrate, the material of the outermost protective layer comprises an AlOxNy layer, the refractive index n of the AlOxNy layer satisfies the range of 1.67≤n≤1.77, the extinction coefficient k of the AlOxNy layer satisfies the range of k≤3.0E-3, the pencil hardness of the coating structure is ≥9H, in the AlOxNy layer, x satisfies 0≤x≤2, and y satisfies 0≤y≤2, the ratio of x to y in the AlOxNy layer is in the range of 0.8-1.

2.

11. The method of claim 10, wherein the coating is applied to the glass sheet by a process selected from the group consisting of sputtering, chemical vapor deposition, and physical vapor deposition. The target power source for magnetron sputtering the AlOxNy layer is a high-power pulsed magnetron sputtering power source, and the AlOxNy layer is deposited by sputtering an Al target in an Ar, O2 and N2 atmosphere.

12. The method of claim 11, wherein the coating is applied to the glass sheet by a process selected from the group consisting of sputtering, chemical vapor deposition, and physical vapor deposition. The working voltage of the high-power pulsed magnetron sputtering power source is in the range of 550V-1000V, the working current of the high-power pulsed magnetron sputtering power source is in the range of 200A-525A, the peak power of the high-power pulsed magnetron sputtering power source is in the range of 110KW-525kW, and the duty cycle of the high-power pulsed magnetron sputtering power source is in the range of 3%-20%.

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