Coated glass, laminated glass and methods of making the same

Abstract

The application provides a coated glass, a laminated glass and a preparation method thereof. The coated glass comprises a first substrate and a coating structure. The coating structure is arranged on the surface of the first substrate. The coating structure comprises at least one functional stack. Each functional stack comprises a lower dielectric layer, a metal layer and an upper dielectric layer which are sequentially stacked. The lower dielectric layer is located on the side of the metal layer facing the first substrate. The metal layer is connected to the surface of the lower dielectric layer away from the first substrate. The upper dielectric layer comprises a CuxNiy layer. The CuxNiy layer is connected to the surface of the metal layer away from the lower dielectric layer. The technical scheme of the application can make the coating structure have better oxidation resistance, and make the perspective color of the coated glass be a neutral color.

Description

Technical Field

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

[0002] Infrared reflective glass generally possesses energy-saving, heat-insulating, and sun-shading thermal properties, making it popular with customers. Its main applications include energy-saving glass for glass curtain walls and automotive windshields. There are two main technologies for infrared reflective glass: one uses silver as the metal layer for the low-emissivity film, but its disadvantage is poor oxidation resistance. The other uses a silver alloy as the low-emissivity metal layer. For example, CN110642529A proposes using a silver-copper / silver-platinum alloy as the metal layer to improve the oxidation resistance of the infrared reflective film system. However, the copper / platinum doping amount is generally low, which cannot improve the product's color transmission. Summary of the Invention

[0003] The embodiments of this application provide a coated glass, a laminated glass, and a method for preparing the same, which enables the coated structure to have better anti-oxidation properties and makes the transparent color of the coated glass neutral.

[0004] In a first aspect, this application provides a coated glass, comprising:

[0005] First substrate; and

[0006] A coating structure includes at least one functional stack, each of the functional stacks including a lower dielectric layer, a metal layer and an upper dielectric layer stacked sequentially, the lower dielectric layer being located on the side of the metal layer facing the first substrate, the metal layer being connected to the surface of the lower dielectric layer facing away from the first substrate, and the upper dielectric layer including a CuxNiy layer being connected to the surface of the metal layer facing away from the lower dielectric layer.

[0007] In this embodiment, using the CuxNiy layer as the upper dielectric layer of the metal layer can solve the problem that the metal layer is easily oxidized and corroded in the atmospheric environment, and prevent the metal layer from losing its function of reflecting energy.

[0008] Furthermore, the CuxNiy layer has a strong bond with the metal layer, so the upper dielectric layer and the metal layer are not easy to fall off, thus avoiding the instability of the coating structure and affecting the optical performance of the laminated glass.

[0009] Furthermore, in coated glass where the top dielectric layer is NiCr, a reddish tinge often appears at the edges. Replacing the NiCr layer with a CuxNiy layer can improve the transparency of the coated glass, allowing it to maintain a neutral hue and thus enhancing its appearance, ultimately providing a better user experience.

[0010] In one possible implementation, during the alcohol wiping performance test, the coated structure is wiped with alcohol multiple times. When the coated structure shows signs of peeling, the number of alcohol wipings is greater than or equal to 50.

[0011] In one possible implementation, the ratio of X to Y in the CuxNiy layer is between 11 / 9 and 17 / 3.

[0012] In one possible implementation, the extinction coefficient K of the CuxNiy layer is between 2.70 and 3.10.

[0013] In one possible implementation, the metal layer is a silver layer.

[0014] In one possible implementation, the upper dielectric layer includes a first dielectric sublayer and a second dielectric sublayer. The first dielectric sublayer is connected to the metal layer, and the second dielectric sublayer is connected to the side of the first dielectric sublayer opposite to the metal layer. The material of the first dielectric sublayer includes the CuxNiy layer, and the material of the second dielectric sublayer includes at least one of AZO, Ti alloy, NbOx, TiOx, NiCr, NiCrOx, ZnAlOx, ZnOx, and SnOx.

[0015] In one possible implementation, the lower dielectric layer comprises at least one of AZO, Ti alloy, NbOx, TiOx, NiCr, NiCrOx, ZnAlOx, ZnOx, and SnOx.

[0016] In one possible implementation, the number of functional layers is at least two, and at least two functional layers are stacked together.

[0017] The coating structure further includes an intermediate layer located between two adjacent functional layers. The material of the intermediate layer includes at least one of ZnSnOx, SiAlZrNx, SiAlNx, SiNx, SiZrNx, ZnOx, AZO, ZnAlOx, ITO, and ZrOx.

[0018] 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.

[0019] 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.

[0020] 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.

[0021] Secondly, this application also provides a laminated glass, including 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.

[0022] In one possible implementation, the laminated glass has a reflective color Lab value for light incident at an 8° incident angle, where the value a satisfies: a≥-3; and the laminated glass has a reflective color Lab value for light incident at a 60° incident angle, where the value a satisfies: a≥-3.

[0023] In one possible implementation, the haze value of the laminated glass is ≤5%.

[0024] Thirdly, this application also provides a method for preparing laminated glass, comprising:

[0025] Provide the first substrate:

[0026] A coating structure is formed on the surface of the first substrate by magnetron sputtering to form coated glass;

[0027] The coating structure includes at least one functional stack, each of the functional stacks including a lower dielectric layer, a metal layer and an upper dielectric layer stacked sequentially, the lower dielectric layer covering the surface of the first substrate, the metal layer being connected to the surface of the lower dielectric layer opposite to the first substrate, and the upper dielectric layer including a CuxNiy layer being connected to the surface of the metal layer opposite to the lower dielectric layer.

[0028] In one possible implementation, after forming a coating structure on the surface of the first substrate using a magnetron sputtering process, the fabrication method further includes:

[0029] Provide a second substrate;

[0030] The second substrate and the coated glass are connected by an adhesive layer to form a laminated structure, wherein the laminated structure has a reflective color Lab value for light incident at an 8° incident angle, with the value a satisfying: a≥-2, and the laminated structure has a reflective color Lab value for light incident at a 60° incident angle, with the value a satisfying: a≥-3.

[0031] The laminated structure is heat-treated and then laminated to form laminated glass. Attached Figure Description

[0032] 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.

[0033] Figure 1 This is a cross-sectional schematic diagram of the laminated glass provided in the embodiments of this application;

[0034] Figure 2 yes Figure 1 A cross-sectional schematic diagram of the first embodiment of the coated glass shown;

[0035] Figure 3 yes Figure 1 A cross-sectional schematic diagram of the second embodiment of the coated glass shown;

[0036] Figure 4 yes Figure 1 A cross-sectional schematic diagram of the third embodiment of the coated glass shown;

[0037] Figure 5 This is a schematic flowchart of a method for preparing coated glass provided in an embodiment of this application.

[0038] Figure label:

[0039] 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

[0040] For ease of understanding, the terminology used in the embodiments of this application will be explained first.

[0041] 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.

[0042] Multiple: refers to two or more.

[0043] 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.

[0044] The specific embodiments of this application will now be clearly described in conjunction with the accompanying drawings.

[0045] 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.

[0046] It should be noted that, Figure 1 The 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.

[0047] In this application, the laminated glass 1000 can be installed on a vehicle as a windshield, side window, rear window, or sunroof, etc.

[0048] 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.

[0049] 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 a higher plasticizer content in at least one layer of the multi-layer structure to provide sound insulation.

[0050] 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 one functional stack (not shown). Each functional stack includes a lower dielectric layer (not shown), a metal layer (not shown), and an upper dielectric layer (not shown) stacked sequentially.

[0051] 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.

[0052] 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, de-icing, etc., improving driving safety. For example, the voltage of the laminated glass 1000 can be 12V to 380V. The metal layer can be a silver layer, and the physical thickness of the metal layer is 5nm-20nm (inclusive of the endpoint values ​​of 5nm and 20nm).

[0053] Infrared reflective glass generally possesses energy-saving, heat-insulating, and sun-shading thermal properties, making it popular with customers. Its main applications include energy-saving glass for glass curtain walls and automotive windshields. There are two main technologies for infrared reflective glass: one uses silver as the metal layer for the low-emissivity film, but its disadvantage is poor oxidation resistance. The other uses a silver alloy as the low-emissivity metal layer. For example, CN110642529A proposes using a silver-copper / silver-platinum alloy as the metal layer to improve the oxidation resistance of the infrared reflective film system. However, the copper / platinum doping amount is generally low, which cannot improve the product's color transmission.

[0054] Currently, the metal layer in general infrared reflective glass has poor oxidation resistance and corrosion resistance, making it prone to deformation and failure during processing. Furthermore, the metal layer can cause a greenish tint to the glass's transparency, which is detrimental to both aesthetics and safe driving.

[0055] Based on this, this application improves the oxidation and corrosion resistance of the coating structure by adjusting the structure of the upper dielectric layer of the coating structure, and makes the transparent color of the laminated glass neutral, so that the scenery seen through the laminated glass is more natural and beautiful, which is conducive to safe driving.

[0056] The lower dielectric layer covers the surface of the first substrate 100, and the metal layer is connected to the lower dielectric layer on the surface away from the first substrate 100. The upper dielectric layer includes a CuxNiy layer, which is connected to the metal layer on the surface away from the lower dielectric layer.

[0057] In this embodiment, using the CuxNiy layer as the upper dielectric layer of the metal layer can solve the problem that the metal layer is easily oxidized and corroded in the atmospheric environment, and prevent the metal layer from losing its function of reflecting energy.

[0058] Furthermore, the CuxNiy layer has a strong bond with the metal layer, so the upper dielectric layer and the metal layer are not easy to fall off, thus avoiding the instability of the coating structure and affecting the optical performance of the laminated glass.

[0059] Furthermore, in coated glass where the top dielectric layer is NiCr, a reddish tinge often appears at the edges. Replacing the NiCr layer with a CuxNiy layer can improve the transparency of the coated glass, allowing it to maintain a neutral hue and thus enhancing its appearance, ultimately providing a better user experience.

[0060] In some possible implementations, the ratio of X to Y in the CuxNiy layer is between 11 / 9 and 17 / 3. Specifically, the ratio of Cu to Ni in the CuxNiy layer can be 60:40, 70:30, or 80:20.

[0061] The extinction coefficient K of the CuxNiy layer is between 2.70 and 3.10.

[0062] In one possible implementation, the upper dielectric layer includes a first dielectric sublayer and a second dielectric sublayer. The first dielectric sublayer is connected to the metal layer, and the second dielectric sublayer is connected to the side of the first dielectric sublayer opposite to the metal layer. The material of the first dielectric sublayer includes a CuxNiy layer, and the material of the second dielectric sublayer includes at least one of AZO, Ti alloy, NbOx, TiOx, NiCr, NiCrOx, ZnAlOx, ZnOx, and SnOx.

[0063] The upper dielectric layer includes at least one of AZO, Ti alloy, NbOx, TiOx, NiCr, NiCrOx, ZnAlOx, ZnOx, and SnOx. The thickness of the lower dielectric layer and / or the upper dielectric layer ranges from 5 nm to 30 nm (inclusive).

[0064] 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.

[0065] 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).

[0066] 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.

[0067] 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).

[0068] 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.

[0069] In some possible implementations, please refer to [the relevant documentation]. 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 endpoints 0 nm and 25 nm).

[0070] In some possible embodiments, the coating structure 200 further includes a second protective layer 270 and an outermost protective layer 280. The second protective layer 270 is located between the first protective layer 260 and the outermost protective layer 280, and 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.

[0071] The outermost protective layer 280 is mainly 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 the outermost film layers of the functional stack furthest from the first substrate 100 in the coating structure 200. The outermost protective layer 280 can be a single film layer or composed of multiple sub-film layers. The physical thickness of the outermost protective layer 280 can be between 5 nm and 70 nm (inclusive).

[0072] In some embodiments, the material of the outermost protective layer 280 may also be selected from oxides, nitrides or oxynitrides of at least one element selected from Si, Zn, Mg, Sn, Ti, Nb, Zr, Ni, In, Al, Ce, W, Mo, Sb, Bi, and may specifically include ZrNx, SiOx, SiOxNy, SiAlZrNx, SiZrNx, SiNx, SiZrOx, SiAlZrOx, etc.

[0073] 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.

[0074] In the second possible implementation, please refer to Figure 3 , Figure 3 yes Figure 1The diagram shows a cross-sectional view of the 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.

[0075] 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 upper dielectric layer 223, the first lower dielectric layer 221, the second upper dielectric layer 233, the second lower dielectric layer 231, the third upper dielectric layer 243, and the third lower dielectric layer 241 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 214 is between 0 nm and 20 nm (inclusive).

[0076] In the third possible implementation, please refer to Figure 4 , Figure 4 yes Figure 1The diagram shows a cross-sectional view of the 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.

[0077] 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.

[0078] 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, as well as those mentioned in the previous question, can be applied to the description of coated glass 1001 above, unless there is any conflict. Please refer to [link / reference]. Figure 5 , Figure 5 This is a schematic flowchart illustrating a method for preparing laminated glass 1000 according to an embodiment of this application. The preparation method includes:

[0079] S100: Provides a first substrate 100.

[0080] S200: A coating structure 200 is formed on the surface of the first substrate 100 by a magnetron sputtering process to form a coated glass 1001.

[0081] The coating structure 200 includes at least one functional stack, each functional stack including a lower dielectric layer, a metal layer and an upper dielectric layer stacked sequentially. The lower dielectric layer covers the surface of the first substrate 100, the metal layer is connected to the surface of the lower dielectric layer opposite to the surface of the first substrate 100, and the upper dielectric layer includes a CuxNiy layer, which is connected to the surface of the metal layer opposite to the surface of the lower dielectric layer.

[0082] In addition to the steps described above, the preparation method may also include:

[0083] S300: Provides a second substrate 1003;

[0084] S400: The second substrate 1003 and the coated glass 1001 are connected by an adhesive layer 1002 to form a laminated structure, wherein the laminated structure has a reflective color Lab value for light incident at an 8° incident angle, and the a value satisfies: a≥-2; the laminated structure has a reflective color Lab value for light incident at a 60° incident angle, and the a value satisfies: a≥-3.

[0085] S500: The laminated structure is heat-treated and then laminated to form laminated glass 1000.

[0086] This application also provides upper dielectric layers made of various materials to investigate the extinction coefficient K values ​​of various film layers. Specific test results are shown in Table 1.

[0087] Table 1. Test structures for extinction coefficients of various material films.

[0088]

[0089] As can be seen from the six types of films in Table 1, the extinction coefficient of the Cu film is relatively smaller compared to that of the Ni and Cr films. During heating, the Cu layer absorbs less heat. When the aforementioned dielectric layer is connected to the metal layer (silver layer), the actual heating temperature of the metal layer is lower. This is because the dielectric layer is in close contact with the metal layer, and the heat absorption of the dielectric layer increases the heating temperature of the metal layer. This reduces the occurrence of reddening at the edges of the coated glass after heating.

[0090] Ni acts as an "adhesive" between metals, between metals and non-metals, and between metals and metal oxides. The presence of Ni can significantly improve the adhesion between the metal layer and other film layers, as demonstrated in the subsequent examples and comparative examples.

[0091] Comparative Examples 1-4 and Examples 1-4

[0092] This application prepares a 2.1 mm thick transparent glass substrate. The film structures of Comparative Examples 1-4 and Examples 1-4 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 1-4 and Examples 1-4 before high-temperature heat treatment, after high-temperature heat treatment, and after glass interlayer treatment are measured. The measurement results are recorded in Tables 2 and 3. Each of the coated glass 1001 test samples of Comparative Examples 1-4 and Examples 1-4 includes two functional layers.

[0093] Table 2: Measurement results of the coated glass 1001 test samples from Comparative Examples 1-4

[0094]

[0095] As shown in Table 2, Comparative Example 1, using AgCu as the first metal layer and NiCr as the first and second upper dielectric layers, exhibits satisfactory overall processing performance of the double-silver film system. However, in optical testing, the laminated glass displays reflective color Lab values ​​for light incident at an 8° angle and for light incident at a 60° angle. Before heat treatment and after lamination, the a values ​​in the 8° and 60° transmission Lab values ​​are -2.5 and -3.8, and -1.9 and -3.7, respectively, indicating an overall greenish tint in the field of vision. Views of the outside world through the windshield appear as if filtered through a green "filter," compromising both aesthetics and driving safety. Furthermore, the Cu doping in the AgCu alloy necessitates the separation of Ag and Cu during recycling, significantly increasing the cost of the target material.

[0096] To address the issues of a greenish tint in the transmission field of the laminated glass and the high cost of the AgCu alloy target in Comparative Example 1, Ag was used as the first metal layer, and Cu and NiCr as the first upper dielectric layers. The thickness of the Cu layer was increased to improve the transmission field color of the double-silver film system. In optical testing, the a values ​​of the transmission Lab values ​​at 8° and 60° before and after heat treatment were -0.9 and -2.3, and -0.4 and -2.1, respectively, indicating an overall neutral color in the transmission field. However, due to the poor adhesion between the Ag and Cu layers, the double-silver film system experienced delamination after five alcohol wipings both before and after heat treatment, indicating poor resistance to mechanical processing.

[0097] To address the poor film adhesion issue in Comparative Example 2, the NiCr in the first upper dielectric layer was increased from 0.5 nm to 1 nm in Comparative Example 3. The double silver film system experienced film detachment after 30 alcohol wipes both before and after heat treatment, which alleviated the film's resistance to mechanical processing. However, due to the increased NiCr layer thickness, the dielectric layer absorbed more heat, and the actual temperature of the Ag layer during the heating process was increased, resulting in reddening of the windshield edges.

[0098] Comparative Example 4 used Ag as the first metal layer and CuNi (Cu:Ni = 70:30wt%) as the first and second upper dielectric layers. In optical testing, the α values ​​in the 8° and 60° transmittance Lab values ​​before heat treatment and after lamination were -0.6 and -2.0, and 0 and -1.7, respectively. The overall field of view was neutral, and the view of the outside scenery through the windshield was natural, improving both aesthetics and driving safety. However, the haze test was unsatisfactory before, after, and after lamination, indicating that the view through the glass was not clear enough.

[0099] Table 3: Measurement results of the coated glass 1001 test samples in Examples 1-4

[0100]

[0101] From the data in Table 3, we can see that:

[0102] Example 1 uses Ag as the first metal layer and CuNi (Cu:Ni = 70:30wt%) as the first upper dielectric layer 223 and the second upper dielectric layer 233. The overall processing performance of the double silver film system is qualified. In optical testing, the α values ​​in the Lab values ​​of transmission at 8° and 60° before heat treatment and after lamination are -0.8 and -2.2, and -0.3 and -2.0, respectively. The overall field of view is neutral, and the view of the outside scenery through the laminated glass 1000 is very natural, improving both aesthetics and driving safety. At the same time, the cost of CuNi alloy is lower than that of AgCu alloy, reducing the cost of target material recycling. Currently, Ag in AgCu alloy is relatively expensive, requiring Ag to be separated and then replenished with AgCu to process into new targets, incurring separation and processing fees, as well as the cost of replenishing Ag and Cu at market prices.

[0103] Example 2 uses Ag as the first metal layer and CuNi (Cu:Ni = 80:20wt%) as the first upper dielectric layer 223 and the second upper dielectric layer 233. The overall processing performance of the double silver film system is qualified. In optical testing, the α values ​​in the Lab values ​​of transmission at 8° and 60° before heat treatment and after lamination are -0.6 and -2.0, and -0.1 and -1.8, respectively. The overall field of view is neutral, and the view of the outside scenery through the laminated glass 1000 is very natural, improving both aesthetics and driving safety. At the same time, the cost of CuNi alloy is lower than that of AgCu alloy, reducing the cost of the target material.

[0104] Example 3 uses Ag as the first metal layer and CuNi (Cu:Ni = 60:40wt%) as the first upper dielectric layer 223 and the second upper dielectric layer 233. The overall processing performance of the double silver film system is qualified. In optical testing, the α values ​​in the Lab values ​​of transmission at 8° and 60° before heat treatment and after lamination are -1.0 and -2.4, and -0.5 and -2.2, respectively. The overall field of view is neutral, and the view of the outside scenery through the laminated glass 1000 is very natural, improving both aesthetics and driving safety. At the same time, the cost of CuNi alloy is lower than that of AgCu alloy, reducing the cost of the target material.

[0105] Example 4 uses Ag as the first metal layer and CuNi (Cu:Ni = 65:25wt%) as the first upper dielectric layer 223 and the second upper dielectric layer 233. The overall processing performance of the double silver film system is qualified. In optical testing, the α values ​​in the Lab values ​​of transmission at 8° and 60° before heat treatment and after lamination are -0.7 and -2.1, and -0.2 and -1.9, respectively. The overall field of view is neutral, and the view of the outside scenery through the laminated glass 1000 is very natural, improving both aesthetics and driving safety. At the same time, the cost of CuNi alloy is lower than that of AgCu alloy, reducing the cost of the target material.

[0106] Comparative Example 5 and Examples 5-7

[0107] This application prepares a 2.1 mm thick transparent glass substrate. The film structures of Comparative Example 5 and Examples 5-7 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 5 and Examples 5-7 before high-temperature heat treatment, after high-temperature heat treatment, and after glass interlayer treatment are measured. The measurement results are recorded in Tables 2 and 3. The coated glass 1001 test samples of Comparative Example 5 and Examples 5-7 each include two functional layers.

[0108] Table 4: Measurement results of the coated glass 1001 test samples of Comparative Example 5 and Examples 5-7

[0109]

[0110] As can be seen from Table 4:

[0111] Comparative Example 5 used AgCu as the first metal layer and NiCr as the first, second, and third upper dielectric layers. The overall processing performance of the three-silver film system was satisfactory. However, in optical testing, the a values ​​of the 8° and 60° transmission Lab values ​​of the three-silver film system before heat treatment and after intercalation were -3.0 and -4.5, and -3.7 and -3.8, respectively. The overall field of view was greenish, and the sky seen through the skylight had a green "filter," which was not aesthetically pleasing. The oxidation resistance time of the three-silver film system before heat treatment was only 252 hours, making it easily oxidized and corroded. At the same time, the doping of Cu in the AgCu alloy required the separation of Ag and Cu during recycling, which greatly increased the cost of the target material.

[0112] Example 5 uses Ag as the first metal layer and CuNi (Cu:Ni = 70:30wt%) to replace NiCr (Ni:Cr = 80:20wt%) as the first upper dielectric layer 223. The overall processing performance of the three-silver film system is qualified, and the oxidation resistance time is increased from 252h to 306h, improving the oxidation resistance and corrosion resistance of the film. In optical testing, the a values ​​in the Lab values ​​of 8° and 60° transmission before heat treatment and after interlayering are 0.4 and -0.2, and -2.2 and -2.6, respectively. The overall field of view is neutral, and the sky is seen naturally through the interlayered glass 1000, improving aesthetics. At the same time, the cost of CuNi alloy is lower than that of the currently used AgCu alloy, reducing the cost of target material recycling.

[0113] Example 6 uses Ag as the metal layer, and CuNi (Cu:Ni = 70:30wt%) replaces NiCr (Ni:Cr = 80:20wt%) as the first upper dielectric layer 223 and the second upper dielectric layer 233. The overall processing performance of the three-silver film system is qualified, and the oxidation resistance time is increased from 252h to 450h, improving the oxidation resistance and corrosion resistance of the film. In optical testing, the a values ​​in the Lab values ​​of 8° and 60° transmission before heat treatment and after interlayering are 0.4 and -0.4, and -2.2 and -2.6, respectively. The overall field of view is neutral, and the sky is seen naturally through the interlayered glass 1000, improving aesthetics. At the same time, the cost of CuNi alloy is lower than that of AgCu alloy, reducing the cost of target material recycling.

[0114] Example 7 uses Ag as the metal layer, and CuNi (Cu:Ni = 70:30wt%) replaces NiCr (Ni:Cr = 80:20wt%) as the first upper dielectric layer 223, the second upper dielectric layer 233, and the third upper dielectric layer 243. The overall processing performance of the three-silver film system is qualified, and the oxidation resistance time is increased from 252h to 521h, improving the oxidation resistance and corrosion resistance of the film. In optical testing, the a values ​​in the Lab values ​​of 8° and 60° transmission before heat treatment and after interlayering are 0.5 and -0.4, and -2.3 and -2.7, respectively. The overall field of view is neutral, and the sky is seen naturally through the interlayered glass 1000, improving aesthetics. At the same time, the cost of CuNi alloy is lower than that of AgCu alloy, reducing the cost of target material recycling.

[0115] Table 5: Measurement results of the coated glass 1001 test samples from Examples 8-10

[0116]

[0117] As can be seen from Table 5:

[0118] Example 8 uses Ag as the metal layer, and CuNi (Cu:Ni = 60:40wt%) replaces NiCr (Ni:Cr = 80:20wt%) as the first upper dielectric layer 223, the second upper dielectric layer 233, and the third upper dielectric layer 243. The overall processing performance of the three-silver film system is qualified, and the oxidation resistance time is increased from 252h to 543h, improving the oxidation resistance and corrosion resistance of the film. In optical testing, the a values ​​in the Lab values ​​of 8° and 60° transmission before heat treatment and after interlayering are 0.7 and -0.2, and -2.1 and -2.5, respectively. The overall field of view is neutral, and the sky is seen naturally through the interlayered glass 1000, improving aesthetics. At the same time, the cost of CuNi alloy is lower than that of AgCu alloy, reducing the cost of target material recycling.

[0119] Example 9 uses Ag as the metal layer, and CuNi (Cu:Ni = 75:15wt%) replaces NiCr (Ni:Cr = 80:20wt%) as the first upper dielectric layer 223, the second upper dielectric layer 233, and the third upper dielectric layer 243. The overall processing performance of the three-silver film system is qualified, and the oxidation resistance time is increased from 252h to 507h, improving the oxidation resistance and corrosion resistance of the film. In optical testing, the a values ​​in the Lab values ​​of 8° and 60° transmission before heat treatment and after interlayering are 0.4 and -0.5, and -2.3 and -2.7, respectively. The overall field of view is neutral, and the sky is seen naturally through the interlayered glass 1000, improving aesthetics. At the same time, the cost of CuNi alloy is lower than that of AgCu alloy, reducing the cost of target material recycling.

[0120] In Example 10, Ag was used as the metal layer, and CuNi (Cu:Ni = 80:20wt%) replaced NiCr (Ni:Cr = 80:20wt%) as the first upper dielectric layer 223, the second upper dielectric layer 233, and the third upper dielectric layer 243. The overall processing performance of the three-silver film system was satisfactory, and the oxidation resistance time was increased from 252h to 485h, improving the oxidation resistance and corrosion resistance of the film. In optical testing, the a values ​​in the Lab values ​​of the 8° and 60° transmission tests before heat treatment and after lamination were 0.3 and -0.6, and -2.4 and -2.8, respectively. The overall field of view was neutral, and the sky was seen naturally through the laminated glass 1000, improving aesthetics. At the same time, the cost of CuNi alloy is lower than that of AgCu alloy, reducing the cost of target material recycling.

[0121] In summary, the above embodiments show that before the laminated glass undergoes heat treatment, the laminated structure has a reflective color Lab value for light incident at an 8° incident angle, with the value a satisfying a≥-2, and the laminated structure has a reflective color Lab value for light incident at a 60° incident angle, with the value a satisfying a≥-3.

[0122] After heat treatment, the laminated glass has a Lab value for reflected color transmission of light incident at an 8° incident angle, where the a value satisfies: a value ≥ -3. The laminated glass also has a Lab value for reflected color transmission of light incident at a 60° incident angle, where the a value satisfies: a value ≥ -3.

[0123] Furthermore, the haze tests of the embodiments provided in this application all passed. This indicates that the haze value of the coated glass is ≤5%.

[0124] In this embodiment, when the coated glass is applied to a vehicle, low haze means higher transparency and improved image quality. This enhances the clarity of the coated glass, providing a clearer view for the driver or passengers.

[0125] 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 laminated glass, characterized in that, Includes a second substrate, an adhesive layer, and coated glass: The coated glass includes: First substrate; A coating structure is disposed on the surface of a first substrate. The coating structure includes at least two functional stacks, which are stacked one on top of the other. Each functional stack includes a lower dielectric layer, a metal layer, and an upper dielectric layer stacked sequentially. The lower dielectric layer is located on the side of the metal layer facing the first substrate, and the metal layer is connected to the surface of the lower dielectric layer facing away from the first substrate. The upper dielectric layer includes a CuxNiy layer, which is connected to the surface of the metal layer facing away from the lower dielectric layer. The adhesive layer connects the second substrate and the coated glass, and the coating structure is located between the first substrate and the second substrate; The coating structure further includes an intermediate layer located between two adjacent functional layers. The material of the intermediate layer includes at least one of ZnSnOx, SiAlZrNx, SiAlNx, SiNx, SiZrNx, ZnOx, AZO, ZnAlOx, ITO, and ZrOx. The laminated glass has a reflective color Lab value for light incident at an 8° incident angle, with the value a satisfying: a≥-3; the laminated glass also has a reflective color Lab value for light incident at a 60° incident angle, with the value a satisfying: a≥-3.

2. The laminated glass according to claim 1, characterized in that, In the alcohol wiping performance test, the coated structure was wiped with alcohol multiple times. When the coated structure showed signs of peeling, the number of alcohol wipings was greater than or equal to 50.

3. The laminated glass according to claim 1, characterized in that, In the CuxNiy layer, the ratio of x to y is between 11 / 9 and 17 / 3.

4. The laminated glass according to claim 2, characterized in that, The extinction coefficient K of the CuxNiy layer is between 2.70 and 3.

10.

5. The laminated glass according to any one of claims 1-4, characterized in that, The metal layer is a silver layer.

6. The laminated glass according to claim 5, characterized in that, The upper dielectric layer includes a first dielectric sublayer and a second dielectric sublayer. The first dielectric sublayer is connected to the metal layer, and the second dielectric sublayer is connected to the side of the first dielectric sublayer opposite to the metal layer. The material of the first dielectric sublayer includes the CuxNiy layer, and the material of the second dielectric sublayer includes at least one of AZO, Ti alloy, NbOx, TiOx, NiCr, NiCrOx, ZnAlOx, ZnOx, and SnOx.

7. The laminated glass according to claim 5, characterized in that, The lower dielectric layer includes at least one of AZO, Ti alloy, NbOx, TiOx, NiCr, NiCrOx, ZnAlOx, ZnOx, and SnOx.

8. The laminated glass according to any one of claims 1-4, characterized in that, The coating structure further includes an adhesion layer, which is connected between the first substrate and one of the functional stacks. The material of the adhesion layer includes at least one of SiAlZrNx, ZrOx, NbOx, SiNx, ZnSnOx, and SiZrNx.

9. The laminated glass according to any one of claims 1-4, characterized in that, The coating structure further includes a first protective layer and an outermost protective layer. The first protective layer is located between the functional stack and the outermost protective layer. The material of the first protective layer includes ZnSnOx.

10. The laminated glass according to claim 9, characterized in that, The coating structure further includes a second protective layer, which is located between the first protective layer and the outermost protective layer, and the material of the second protective layer includes TiOx.

11. The laminated glass according to claim 1, characterized in that, The haze value of the laminated glass is ≤5%.

12. A method for preparing laminated glass, characterized in that, include: Provide the first substrate: A coating structure is formed on the surface of the first substrate by magnetron sputtering to form coated glass; The coating structure includes at least two functional stacks, which are stacked in layers. Each functional stack includes a lower dielectric layer, a metal layer, and an upper dielectric layer stacked sequentially. The lower dielectric layer covers the surface of the first substrate, and the metal layer is connected to the surface of the lower dielectric layer opposite to the first substrate. The upper dielectric layer includes a CuxNiy layer, which is connected to the surface of the metal layer opposite to the lower dielectric layer. Provide a second substrate; The second substrate and the coated glass are connected by an adhesive layer to form a laminated structure. The laminated structure has a reflective color Lab value for light incident at an 8° incident angle, with the value a ≥ -2. The laminated structure has a reflective color Lab value for light incident at a 60° incident angle, with the value a ≥ -3. The coated structure further includes an intermediate layer located between two adjacent functional laminates. The material of the intermediate layer includes at least one of ZnSnOx, SiAlZrNx, SiAlNx, SiNx, SiZrNx, ZnOx, AZO, ZnAlOx, ITO, and ZrOx. The laminated structure is heat-treated and then laminated to form laminated glass.

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