Three-silver Low-E coated glass for automobile, preparation method of three-silver Low-E coated glass and laminated glass

Abstract

The invention provides three-silver Low-E coated glass for an automobile, a preparation method of the three-silver Low-E coated glass and laminated glass, and relates to the technical field of glass, and the three-silver Low-E coated glass comprises a specific functional layer, a barrier layer, a dielectric layer and a protective layer which are matched in specific thickness. The coated glass can still maintain high visible light permeability and low radiation under the thickness of the three functional silver layers, has good heat insulation and light transmission effects, and is wide in color selectable range. The invention further provides a preparation method of the three-silver Low-E coated glass for the automobile.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of glass materials, and particularly relates to a three-silver Low-E coated glass for automobiles, a preparation method thereof and a laminated glass. BACKGROUND

[0002] Low-E glass is a coated glass product with a film system composed of multiple layers of metal or other compounds on the surface of the glass, which can not only allow solar energy and visible light to pass through, but also reflect infrared light, especially medium and far infrared light, back to the outside, so as to achieve the effects of controlling sunlight, saving energy and heat, and improving the environment.

[0003] The functional layer (usually a silver layer) in the low-E coated glass is the main layer structure for reducing radiation, so increasing the thickness and number of functional layers is the main means to achieve better heat insulation and heat preservation effects. Therefore, based on the higher requirements of consumers for heat insulation and heat preservation and the changing environment, the current high-performance coated glass gradually develops from single-silver and double-silver coated glass to three-silver and four-silver coated glass. However, the increase in the thickness of the functional layer is not conducive to the reduction of the light transmittance of the glass, and it also easily leads to a decrease in color selectivity. The existing three-silver Low-E coated glass is difficult to achieve a light transmittance of more than 70%, and the visible light transmittance color is difficult to be controlled at about 0. SUMMARY

[0004] The purpose of the present application is to provide a three-silver Low-E coated glass for automobiles, which improves the problems of low visible light transmittance, high visible light transmittance loss and poor color selectivity of the three-silver Low-E coated glass in the prior art.

[0005] Another purpose of the present application is to provide a preparation method of a three-silver Low-E coated glass for automobiles.

[0006] Still another purpose of the present application is to provide a laminated coated glass for automobiles.

[0007] In a first aspect, the present application provides a three-silver Low-E coated glass for automobiles, comprising a glass substrate and a composite coating structure arranged on the glass substrate. The composite coating structure comprises a first silver layer, a second silver layer and a third silver layer arranged in sequence from bottom to top, and a first dielectric combination layer arranged between the first silver layer and the second silver layer and a second dielectric combination layer arranged between the second silver layer and the third silver layer. The thickness of the second silver layer is higher than that of the third silver layer, and the thickness of the third silver layer is higher than that of the first silver layer; and the thickness of the second silver layer is not higher than 20 nm, and the thickness of the first silver layer is not higher than 12 nm; and the thickness of the composite coating structure is not higher than 320 nm.

[0008] Furthermore, in some embodiments of this application, the thickness of the second silver layer is 1.6 to 2 times the thickness of the first silver layer, and the thickness of the first silver layer is not less than 7 nm; The thickness of the second silver layer is 1.05 to 1.4 times the thickness of the third silver layer, and the thickness of the third silver layer is not less than 10 nm.

[0009] Furthermore, in some embodiments of this application, a first barrier layer and a second barrier layer are provided on the upper and lower sides of the third silver layer; the sum of the thicknesses of the first barrier layer, the third silver layer, and the second barrier layer is not higher than the thickness of the second silver layer.

[0010] Furthermore, in some embodiments of this application, the first barrier layer and the second barrier layer are continuous NiCr layers, and the thicknesses of the first barrier layer and the second barrier layer are respectively no higher than 0.8 nm.

[0011] Furthermore, in some embodiments of this application, both the first dielectric composite layer and the second dielectric composite layer include ZnAlO4 sequentially stacked. x Layer, ZnSnO x Layer, ZnAlO x layer.

[0012] Furthermore, in some embodiments of this application, the ZnSnO in the first dielectric composite layer x The thickness of the layer is lower than that of ZnSnO in the second dielectric composite layer. x layer.

[0013] Furthermore, in some embodiments of this application, the thickness of the first dielectric composite layer is 60-90 nm, and the thickness of the second dielectric composite layer is 70-100 nm.

[0014] Furthermore, in some embodiments of this application, the composite coating structure further includes a bottom protective layer and a top protective layer; The bottom protective layer is selected from SiAlZrN x ZrO x NbO x SiN x SiAlN x ZnSnO x SiZrN x At least one of the following; The top protective layer includes a sacrificial layer and a protective layer; the sacrificial layer is selected from ZrO. x NbO x At least one of the following; the protective layer is selected from SiAlZrN x SiZrNx SiN x At least one of them.

[0015] Furthermore, in some embodiments of this application, the thickness of the top protective layer is not higher than 30 nm and not lower than 20 nm.

[0016] Furthermore, in some embodiments of this application, a seed layer is further provided between the bottom protective layer and the first silver layer.

[0017] Secondly, this application also provides a method for preparing automotive triple-silver Low-E coated glass. The method involves sequentially forming a bottom protective layer, a seed layer, a first silver layer, a first dielectric composite layer, a second silver layer, a second dielectric composite layer, a first barrier layer, a third silver layer, a second barrier layer, a smoothing layer, a protective layer, and a sacrificial layer on a glass substrate using vacuum magnetron sputtering. The thickness of the second silver layer is greater than the thickness of the third silver layer, and the thickness of the third silver layer is greater than the thickness of the first silver layer. Furthermore, the thickness of the second silver layer is no greater than 20 nm, and the thickness of the first silver layer is no greater than 12 nm. The thickness of the composite coating structure is no greater than 320 nm.

[0018] Furthermore, in some embodiments of this application, during the vacuum magnetron sputtering coating process, the residual oxygen partial pressure in the vacuum magnetron sputtering equipment is not higher than 10. -8 Pa; the temperature of the glass substrate is controlled below 150°C.

[0019] Thirdly, this application also provides a laminated coated glass for automobiles, comprising clear glass, an adhesive layer, and a triple silver Low-E coated glass for automobiles prepared by the preparation method of the first aspect or the second aspect.

[0020] This application provides a triple-silver Low-E coated glass for automobiles. The coated glass comprises three silver functional layers with a dielectric composite layer interposed between them. The thickness of the silver layers is set and the thickness relationship between the silver layers is controlled to improve spectral selectivity and conductivity. This achieves high far-infrared, mid-infrared, and near-infrared reflectivity while maintaining high visible light transmittance. Simultaneously, it suppresses red, green, and blue bias in reflected visible light, making the glass closer to neutral colors. This improves upon the low light transmittance and color bias issues of existing triple-silver Low-E coated glass caused by the increased number of silver layers and dielectric composite layers. The triple-silver Low-E coated glass provided in this application also exhibits lower surface resistivity and good adhesion to the substrate, making it less prone to cracking during subsequent tempering.

[0021] This application also relates to laminated glass based on the aforementioned triple-silver Low-E coated glass. When the laminated glass uses 1.2-2.1mm coated glass + 0.76mm PVB + 1.2-2.1mm ordinary tempered glass, its visible light transmittance can reach over 70%, with the following visible light transmission colors: at*: -2±4; bt*: 4±4; visible light glass surface reflectance Rout: 16%±4; visible light glass surface color: aout*: -5±4; bout*: -9±4; visible light film surface reflection Rin: ≤17%; total solar transmittance TTS: <40%; solar transmittance TE: <38%; solar reflectance RE: >43%. Attached Figure Description

[0022] Figure 1 This is a schematic diagram of the structure of the triple silver Low-E coated glass provided in this application. Detailed Implementation

[0023] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0024] Triple-silver Low-E coated glass offers lower emissivity and higher thermal insulation efficiency compared to single-silver and double-silver Low-E coated glass, making it a preferred choice for automotive applications, especially automotive glass. However, due to the presence of three silver functional layers and a dielectric layer between them, triple-silver Low-E coated glass has a high layer thickness and complex structure, resulting in a significant decrease in visible light transmittance, making it difficult to achieve a visible light transmittance of over 70%. Current technologies often omit certain layers in the coating structure, such as protective layers, to achieve higher visible light transmittance, which negatively impacts the tempering stability and impact resistance of Low-E coated glass. Furthermore, laminated glass based on Low-E coated glass has even lower visible light transmittance than insulated glass due to the coating and lamination layers, making it even more difficult to achieve a visible light transmittance of over 70%. To address this technical problem, this application provides a triple-silver Low-E coated glass for automobiles. This coated glass employs a specific layer structure and a specific silver layer thickness to form a coating layer with a thickness not exceeding 320 nm. The number of coating layers does not exceed 16, resulting in a coated glass with visible light transmittance exceeding 70% and good tempering stability. Furthermore, when applied in laminated glass, it can achieve a visible light transmittance of over 70%. The specific technical solution is as follows: A triple-silver Low-E coated glass for automobiles includes a glass substrate and a composite coating structure disposed on the glass substrate. The composite coating structure includes a first silver layer, a second silver layer, and a third silver layer arranged sequentially from bottom to top, as well as a first dielectric composite layer disposed between the first silver layer and the second silver layer and a second dielectric composite layer disposed between the second silver layer and the third silver layer. The thickness of the second silver layer is greater than the thickness of the third silver layer, and the thickness of the third silver layer is greater than the thickness of the first silver layer; the thickness of the second silver layer is not greater than 20 nm, and the thickness of the first silver layer is not greater than 12 nm; the thickness of the composite coating structure is not greater than 320 nm.

[0025] It should be noted that the first dielectric composite layer and the second dielectric composite layer in this application are respectively disposed between two adjacent silver layers to form a Fabry-Perot interference cavity to improve optical performance; at the same time, they provide protection for the silver layers during the tempering process.

[0026] In this application, the thickness of the three silver layers in the triple-silver coated glass exhibits a thin-thick-thinning trend from the glass substrate to the top layer. The silver layer closest to the glass substrate is the thinnest to provide higher infrared reflectivity; the second silver layer is the thickest to provide improved near-infrared reflectivity and maintain a high visible light transmittance; and the thickness of the third silver layer is between that of the first and second silver layers and close to that of the second silver layer, thus improving infrared radiation while maintaining surface stability and providing a foundation for the stability of subsequent glass tempering. Furthermore, in this application, in addition to satisfying the above thickness relationships, it is necessary to further control the thickness range of the first, second, and third silver layers. This is because the applicant found that while an excessively thick first silver layer can improve infrared reflectivity to some extent, it leads to a more significant decrease in the visible light transmittance of the coated glass. Preferably, the thickness of the first silver layer is 7nm~12nm; a lower first silver layer thickness, while increasing the visible light transmittance of the coated glass, causes a sharp increase in the surface resistance of the coating, resulting in an increase in emissivity. The applicant also discovered that while an excessively thick second silver layer can improve the reflectivity of near-infrared light, it is difficult to maintain the transmittance of visible light, and it can lead to color shift, making it difficult to maintain the neutral color of the coated glass and hindering the color selectivity of the coated glass. Preferably, the thickness of the second silver layer is not less than 12 nm. The applicant unexpectedly discovered that although a higher second silver layer thickness is detrimental to visible light transmittance, a lower second silver layer thickness is also detrimental to visible light transmittance. The possible reason is that with a lower second silver layer thickness, the light interference in the Fabry-Perot interferometer cavity formed by the second silver layer, the first silver layer, and the third silver layer through the dielectric composite layer is prone to shift, resulting in a more obvious color shift and a decrease in visible light transmittance. The thickness of the third silver layer is between that of the first and second silver layers, preferably 8-15 nm.

[0027] For example, the thickness of the first silver layer can be 7nm, 7.5nm, 8nm, 8.5nm, 9nm, 9.5nm, 10nm, 10.5nm, 11nm, 11.5nm, or 12nm, as well as all ranges and sub-ranges between these values. It should be understood that, in embodiments, any of the above ranges can be combined with any other range. The thickness of the second silver layer can be 12nm, 12.5nm, 13nm, 13.5nm, 14nm, 14.5nm, 15nm, 15.5nm, 16nm, 16.5nm, 17nm, 17.5nm, 18nm, 18.5nm, 19nm, 19.5nm, or 20nm, as well as all ranges and sub-ranges between these values. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0028] The applicant also found that the sum of the thicknesses of the first, second, and third silver layers should not exceed 40 nm to achieve better optical performance. Within this range, the visible light transmittance of the laminated glass (1.2-2.1 mm coated glass + 0.76 mm PVB + 1.2-2.1 mm) based on the triple silver Low-E coated glass of this application can reach more than 70%.

[0029] In some preferred embodiments, the thickness of the second silver layer is 1.6 to 2 times the thickness of the first silver layer, and the thickness of the first silver layer is not less than 7 nm; The thickness of the second silver layer is 1.05 to 1.4 times the thickness of the third silver layer, and the thickness of the third silver layer is not less than 10 nm.

[0030] As mentioned above, the thickness of the third silver layer is between the thickness of the first silver layer and the thickness of the second silver layer, and is preferably close to the thickness of the second silver layer. This is because the applicant found that when the thickness of the third silver layer is too low, its infrared reflectivity will decrease significantly and it will not be conducive to bonding with the top protective layer, affecting the stability of the coating structure; while an excessively thick third silver layer will affect the visible light transmittance of the coated glass.

[0031] In some embodiments, a first barrier layer and a second barrier layer are provided on the upper and lower sides of the third silver layer; these are used to provide an anti-oxidation protection layer for the silver layer, preventing the silver layer from being oxidized during the tempering process of the coated glass; at the same time, the first barrier layer and the second barrier layer can also be oxidized to form an oxide layer during the process of providing anti-oxidation protection for the silver layer, thereby providing higher visible light transmittance for the coated glass.

[0032] Preferably, the thickness of the first and second barrier layers should not be too high. Since the first and second barrier layers protect the silver layer from oxidation and are more reactive than silver, they tend to diffuse into the silver layer. However, excessively thick first and second barrier layers have a relatively long formation process, leading to excessive diffusion of these materials into the silver layer, affecting the conductivity and infrared reflectivity of the silver layer. For example, the first and second barrier layers are continuous NiCr layers. Furthermore, the applicant also discovered that when the thicknesses of the first and second barrier layers satisfy the condition that the sum of the thicknesses of the first barrier layer, the third silver layer, and the second barrier layer is not greater than the thickness of the second silver layer, the resulting coated glass exhibits superior optical performance and tempered strength while ensuring its anti-oxidation properties. The reason for this may be that the relatively thicker second silver layer located inside the coating can provide the coated glass with higher compressive stress resistance. Appropriately thinning the third silver layer within a certain range, combined with the double barrier layers on both the inner and outer sides, can not only avoid Mie scattering caused by grain coarsening that may exist in the thicker third silver layer, thus affecting the decrease in infrared reflectivity and the increase in haze, but also easily lead to the peeling of the third silver layer. The double barrier layer can not only provide isolation from the external environmental influences of the silver layer, but also prevent the migration of lower ions to the silver layer. However, an excessively thick barrier layer, especially when the barrier layer is a NiCr layer, has a significant impact on visible light transmittance, and its color may limit the color neutrality of the coated glass. Therefore, by controlling the thickness of the third silver layer within the range of 8~15nm, and simultaneously limiting its sum with the thickness of the barrier layer and its relationship with the thickness of the second silver layer, the coated glass can possess properties such as visible light transmittance, infrared reflectivity, strength, oxidation resistance, and tempering crack resistance.

[0033] Preferably, the thickness of the first barrier layer and the second barrier layer is no higher than 0.8 nm; for example, the thickness of the first barrier layer can be 0.3 nm, 0.4 nm, 0.5 nm, 0.6 nm, 0.7 nm, or 0.8 nm; and the thickness of the second barrier layer can be 0.3 nm, 0.4 nm, 0.5 nm, 0.6 nm, 0.7 nm, or 0.8 nm.

[0034] In this application, the dielectric composite layer includes ZnAlO, which is beneficial for silver layer growth. x Layers and located in ZnAlO x Dielectric layer between layers: ZnSnO x Layer. That is, both the first dielectric composite layer and the second dielectric composite layer include ZnAlO4 sequentially stacked. x Layer, ZnSnO x Layer, ZnAlO x Layer. ZnSnO xAs a dielectric layer, the ZnAlO layer exhibits good chemical stability, high visible light transmittance, and a refractive index between 2 and 2.2, allowing for better adjustment of the refractive index while maintaining high visible light transmittance. x and ZnSnO x x is independently selected from any number in the range of 1 to 3.

[0035] Furthermore, it should be noted that in the ZnAlOx and ZnSnOx of this application, Zn and Al, and Zn and Sn are not present in a 1:1 atomic molar ratio. Instead, a certain amount of Al2O3 and a certain amount of SnO2 are doped into ZnO. The amount of Al2O3 and SnO2 added can be adjusted as needed. Preferably, the doping amount of Al2O3 and SnO2 in ZnO is 2-5% and 45-55%, respectively. The doping amount should not be too high. If the doping amount of Al2O3 is too high, it will easily lead to Al2O3 enrichment and form local insulation, which will lead to an increase in sheet resistance. In some preferred embodiments, the thickness of the ZnSnOx layer in the first dielectric composite layer is lower than that of the ZnSnOx layer in the second dielectric composite layer. For example, the thickness of the first dielectric composite layer is 60-90 nm, and the thickness of the second dielectric composite layer is 70-100 nm.

[0036] The composite coating structure of the coated glass provided in this application further includes a bottom protective layer and a top protective layer; the bottom protective layer is selected from SiAlZrN x ZrO x NbO x SiN x SiAlN x ZnSnO x SiZrN x At least one of the following; preferably: SiAlZrN x SiN x SiZrN x Any one of them.

[0037] The top protective layer includes a sacrificial layer and a protective layer; the sacrificial layer is selected from ZrO. x NbO x At least one of the following: the protective layer is selected from at least one of SiAlZrNx, SiZrNx, and SiNx; preferably, the sacrificial layer is ZrO. x It possesses high hardness, excellent acid and alkali resistance, weather resistance, and excellent scratch resistance, which are beneficial for optimizing the processing performance of coated glass. Among them, SiAlZrN... x ZrO x NbO xSiN x ZnSnO x SiZrN x x is independently selected from any number from 1 to 5. The thickness of the top protective layer is not higher than 30 nm and not lower than 20 nm, and while maintaining its protective function and strength, it does not have a significant adverse effect on the optical performance of the coated glass.

[0038] A seed layer is further provided between the bottom protective layer and the first silver layer to facilitate better growth of the silver layer; the seed layer is preferably ZnAlO. x More preferably, the ZnAlO coated glass type provided in this application... x The thicknesses of the silver layers are all equal, similar, or infinitely close to equal to ensure the growth state of each silver grain.

[0039] Secondly, this application also provides a method for preparing automotive triple-silver Low-E coated glass. The method involves sequentially forming a bottom protective layer, a seed layer, a first silver layer, a first dielectric composite layer, a second silver layer, a second dielectric composite layer, a first barrier layer, a third silver layer, a second barrier layer, a smoothing layer, a protective layer, and a sacrificial layer on a glass substrate using vacuum magnetron sputtering. The thickness of the second silver layer is greater than the thickness of the third silver layer, and the thickness of the third silver layer is greater than the thickness of the first silver layer. Furthermore, the thickness of the second silver layer is no greater than 20 nm, and the thickness of the first silver layer is no greater than 12 nm. The thickness of the composite coating structure is no greater than 320 nm.

[0040] The smoothing layer refers to the layer structure placed between the first barrier layer and the top protective layer. Its material can be any existing smoothing layer material, such as ZnAlO. x .

[0041] It should be noted that the glass substrate requires a rigorous cleaning process before magnetron sputtering coating to ensure a clean surface and prevent the introduction of impurities that could affect the film's performance and adhesion to the glass substrate. The specific steps are all existing technologies, such as conventional dust removal and degreasing processes, and therefore will not be detailed in this application, as this will not hinder those skilled in the art from understanding and implementing this solution.

[0042] Furthermore, in the preparation method provided in this application, depending on the material and thickness of each coating layer, the selected raw materials, atmosphere, and coating time are adjusted during the formation of the corresponding film layer by vacuum magnetron sputtering. However, the magnetron sputtering chamber needs to be evacuated before coating, and the temperature of the glass substrate is controlled by cooling during the magnetron sputtering process. Specifically, during the vacuum magnetron sputtering process, the residual oxygen partial pressure in the vacuum magnetron sputtering equipment is not higher than 10. -8Pa; the temperature of the glass substrate is controlled below 150°C.

[0043] For example, the preparation method of the automotive triple-silver Low-E coated glass includes the following steps: S1: Glass pretreatment: The original glass sheet is thoroughly cleaned to remove dust, oil and other impurities.

[0044] S2: Loading Glass: Transfer the cleaned glass into the vacuum chamber of the coating equipment.

[0045] S3: Vacuuming: Start the vacuum system to evacuate the chamber to the required high vacuum level.

[0046] S4: Target Preparation: Install and prepare the SiAlN target for high-performance coated glass used in new energy vehicles. x ZnSnO x Ag, NiCr, ZrO x ZnAlO x SiZrN x Target materials, etc.

[0047] S5: Pre-sputtering: The target material is briefly pre-sputtered to remove oxides, impurities, etc. on the target surface to ensure the coating quality.

[0048] S6: Coating Process: The magnetron sputtering power supply is turned on, causing target atoms or ions to be sputtered and deposited on the glass surface to form a coating layer. During the coating process, parameters such as sputtering power and gas flow rate are precisely controlled to obtain the desired coating thickness and performance. According to design requirements, SiAlZrN is formed by sequential sputtering. x ZnAlO x Ag, ZnAlO x ZnSnOx, ZnAlO x Ag, ZnAlO x ZnSnO x ZnAlO x NiCr, Ag, NiCr, ZnAlO x SiZrN x ZrO x Different target materials are used to form multilayer thin films, such as Figure 1 As shown.

[0049] For example, the ZnSnO x The layer can be formed by magnetron sputtering of a zinc tin oxide with 52% ZnO and 48% SnO2 as the target material and a 15:1 mixture of argon and oxygen as the process gas. For example, the ZnAlOx The layer can be formed by magnetron sputtering of a 20:1 mixture of argon and oxygen as a process gas using aluminum-doped zinc oxide as a target material. For example, the SiN x The layer can be formed by magnetron sputtering of a 1:1.5 mixture of argon and nitrogen as a process gas using a rotating silicon-aluminum target. For example, the NiCr layer can be formed by magnetron sputtering of a nickel-chromium target with 20% Ni and 80% Cr through Ar2 at 600 sccm. For example, the ZrO2 film can be formed by magnetron sputtering of a mixture of argon and oxygen in a process gas ratio of 40:1, with zirconium oxide as the target material. For example, the Ag layer can be formed by using silver as the target material and passing argon gas at 600 sccm through a magnetron sputtering method; For example, the SiAlZrN x The layer can be formed by magnetron sputtering using a rotating silicon-aluminum-zirconium target and a process gas mixture of argon and nitrogen in a 1:1.5 ratio.

[0050] S7: Venting: After the coating is completed, slowly vent the gas to atmospheric pressure.

[0051] S8: Unloading Glass: The coated glass is transferred out of the coating chamber.

[0052] Thirdly, this application also provides a laminated coated glass for automobiles, comprising, sequentially arranged, clear glass, an adhesive layer, and a triple-silver Low-E coated glass for automobiles prepared by the preparation method described in the first aspect or the method described in the second aspect. The adhesive layer can be a film made of transparent resin material, such as PVB film, SGP film, EVA film, TPU film, etc., which can be applied to laminated glass.

[0053] To facilitate understanding of the innovative aspects of this application by those skilled in the art, some preferred embodiments are provided below in conjunction with the accompanying drawings to illustrate the above technical solutions.

[0054] Example 1 This embodiment provides a triple-silver Low-E coated glass for automobiles, such as... Figure 1As shown, from bottom to top, the layers include a glass substrate, a silicon nitride layer (40 nm), a zinc-aluminum oxide layer (13 nm), a first silver layer (7.5 nm), a zinc-aluminum oxide layer (13 nm), a zinc-tin oxide layer (52 nm), a zinc-aluminum oxide layer (13 nm), a second silver layer (14 nm), a zinc-aluminum oxide layer (13 nm), a zinc-tin oxide layer (62 nm), a zinc-aluminum oxide layer (13 nm), a nickel-chromium alloy layer (0.5 nm), a third silver layer (12 nm), a nickel-chromium alloy layer (0.5 nm), a zinc-aluminum oxide layer (13 nm), a silicon-zirconium nitride layer (20 nm), and a zirconium oxide layer (5 nm). The fabrication process is achieved using vacuum magnetron sputtering deposition technology, and the specific steps are as follows: S1: Glass pretreatment: The original glass sheet is thoroughly cleaned to remove dust, oil and other impurities.

[0055] S2: Loading Glass: Transfer the cleaned glass into the vacuum chamber of the coating equipment.

[0056] S3: Vacuuming: Start the vacuum system to evacuate the chamber to the required high vacuum level.

[0057] S4: Target preparation: Install and prepare the target materials required for the silicon nitride layer, zinc aluminum oxide layer, silver layer, zinc tin oxide layer, nickel chromium alloy layer, silicon nitride zirconium layer, and zirconium oxide layer of high-performance coated glass for new energy vehicles.

[0058] S5: Pre-sputtering: The target material is briefly pre-sputtered to remove oxides, impurities, etc. on the target surface to ensure the coating quality.

[0059] S6: Coating Process: The magnetron sputtering power supply is turned on, causing target atoms or ions to be sputtered and deposited on the glass surface to form a coating layer. During the coating process, parameters such as sputtering power and gas flow rate are precisely controlled to obtain the desired coating thickness and performance. S61: A silicon nitride layer is formed by sputtering a rotating silicon aluminum as a target on the surface of a glass substrate. The sputtering atmosphere of the silicon nitride layer is argon:nitrogen = 500:750 sccm. S62: Aluminum-doped zinc oxide is used as the target material and sputtered on the surface of silicon nitride layer to form a zinc-aluminum oxide layer. The sputtering atmosphere of the zinc-aluminum oxide layer is argon:oxygen = 800:40 sccm. S63: Silver is used as the target material to sputter on the surface of the zinc oxide aluminum layer to form the first silver layer. The sputtering atmosphere of the first silver layer is argon 600 sccm. S64: Aluminum-doped zinc oxide is used as the target material and sputtered on the surface of the first silver layer to form a zinc-aluminum oxide layer. The sputtering atmosphere of the zinc-aluminum oxide layer is argon:oxygen = 800:40 sccm. S65: Zinc tin oxide with 52% ZnO and 48% SnO2 is used as the target material and sputtered on the surface of zinc aluminum oxide layer to form zinc tin oxide layer. The sputtering atmosphere of zinc tin oxide layer is argon:oxygen = 600:40 sccm; and the zinc tin oxide layer is formed. S66: Aluminum-doped zinc oxide is used as the target material, and zinc oxide aluminum layer is formed by sputtering on the surface of zinc oxide tin layer. The sputtering atmosphere of zinc oxide aluminum layer is argon:oxygen = 800:40 sccm. S67: Silver is used as the target material to sputter on the surface of the zinc oxide aluminum layer to form a second silver layer. The sputtering atmosphere of the second silver layer is argon 600 sccm. S68: Aluminum-doped zinc oxide is used as the target material and sputtered on the surface of the second silver layer to form a zinc-aluminum oxide layer. The sputtering atmosphere of the zinc-aluminum oxide layer is argon:oxygen = 800:40 sccm. S69: Zinc tin oxide with 52% ZnO and 48% SnO2 is used as the target material and sputtered on the surface of zinc aluminum oxide layer to form zinc tin oxide layer. The sputtering atmosphere of zinc tin oxide layer is argon:oxygen = 600:40 sccm. S610: Aluminum-doped zinc oxide is used as the target material, and zinc oxide aluminum layer is formed by sputtering on the surface of zinc oxide tin layer. The sputtering atmosphere of zinc oxide aluminum layer is argon:oxygen = 800:40 sccm. S611: Using 20%Ni and 80%Cr nickel-chromium as the target material, sputtering is performed on the surface of zinc oxide aluminum layer to form a nickel-chromium alloy layer. The sputtering atmosphere of the nickel-chromium alloy layer is argon 600 sccm. S612: Silver is used as the target material to sputter on the surface of the nickel-chromium alloy layer to form a third silver layer. The sputtering atmosphere of the third silver layer is argon 600 sccm. S613: Using 20%Ni and 80%Cr nickel-chromium as the target material, sputtering is performed on the surface of the third silver layer to form a nickel-chromium alloy layer. The sputtering atmosphere of the nickel-chromium alloy layer is argon 600 sccm. S614: Aluminum-doped zinc oxide is used as the target material and sputtered on the surface of the nickel-chromium alloy layer to form a zinc-aluminum oxide layer. The sputtering atmosphere of the zinc-aluminum oxide layer is argon:oxygen = 800:40 sccm. S615: Using silicon aluminum zirconium as the target material, a silicon zirconium nitride layer is formed by sputtering on the surface of zinc aluminum oxide layer. The sputtering atmosphere of the silicon zirconium nitride layer is argon:nitrogen 500:750 sccm. S616: Zirconia is used as the target material and sputtered on the surface of the silicon nitride zirconium layer to form a zirconium oxide layer. The sputtering atmosphere of the zirconium oxide layer is argon:oxygen = 800:20 sccm.

[0060] Examples 2 to 5 Examples 2 to 5 also provide a triple silver Low-E coated glass for automobiles. The preparation method differs from that of the examples in that when the thickness of the sputtered layer is different, the magnetron sputtering time is adjusted according to the thickness of the layer to obtain corresponding film layers of different thicknesses. The rest of the preparation method is the same as that of Example 1, and the corresponding triple silver Low-E coated glass for automobiles is obtained. The thickness of each layer of the obtained coated glass is shown in Table 1.

[0061] Comparative Examples 1 to 7 Comparative Examples 1 to 7 also provide a triple silver Low-E coated glass for automobiles. The preparation method of the glass differs from that of the examples in that when the thickness of the sputtered layer is different, the magnetron sputtering time is adjusted according to the thickness of the layer to obtain corresponding film layers of different thicknesses. The rest of the preparation method is the same as that of Example 1, and the corresponding triple silver Low-E coated glass for automobiles is obtained. The thickness of each layer of the coated glass is shown in Table 2.

[0062] Table 1

[0063] Table 2

[0064] The coated glasses obtained in Examples 1-5 and Comparative Examples 1-7 were respectively used to prepare laminated glass with a 0.76 mm thick PVB film (98% visible light transmittance) and a 2.1 mm thick ordinary tempered glass (90% visible light transmittance). Color experiments, optical performance tests, surface resistivity tests, and tempering stability tests were conducted on the products. The test results are shown in Tables 3 and 4. The tempering stability test of the coated glass involved tempering the coated glass and observing whether cracks appeared in the film layer.

[0065] Table 3

[0066] Table 4

[0067] As can be seen from Tables 3 and 4, even with three silver layers and a PVB interlayer, the laminated glass formed by the triple-silver coated glass provided in this application still achieves a visible light transmittance of over 70%, and even over 72%. Furthermore, its emissivity is reduced to below 0.020%, the film color is neutral with minimal color deviation, and its solar reflectivity meets the standard of over 43%, solar transmittance below 38%, and visible light reflectivity below 18%. Moreover, its surface resistance is controlled within 1.25 Ω / □. It is also less prone to cracking after tempering. Therefore, the laminated glass formed by the triple-silver coated glass provided in this application not only has high visible light transmittance and low emissivity, and its total solar transmittance meets the standard of below 40%, but also possesses low surface resistance and is less prone to cracking after tempering, making it particularly suitable for automotive windshields and sunroofs.

[0068] The above are merely specific embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A triple-silver Low-E coated glass for automobiles, characterized in that, It includes a glass substrate and a composite coating structure disposed on the glass substrate; The composite coating structure includes a first silver layer, a second silver layer, and a third silver layer arranged sequentially from bottom to top, as well as a first dielectric composite layer disposed between the first silver layer and the second silver layer and a second dielectric composite layer disposed between the second silver layer and the third silver layer. The thickness of the second silver layer is greater than the thickness of the third silver layer, and the thickness of the third silver layer is greater than the thickness of the first silver layer; and the thickness of the second silver layer is not greater than 20 nm, and the thickness of the first silver layer is not greater than 12 nm.

2. The automotive triple-silver Low-E coated glass according to claim 1, characterized in that, The thickness of the second silver layer is 1.6 to 2 times the thickness of the first silver layer, and the thickness of the first silver layer is not less than 7 nm; The thickness of the second silver layer is 1.05 to 1.4 times the thickness of the third silver layer, and the thickness of the third silver layer is not less than 10 nm.

3. The automotive triple-silver Low-E coated glass according to claim 1, characterized in that, The third silver layer has a first barrier layer and a second barrier layer on its upper and lower sides; the sum of the thicknesses of the first barrier layer, the third silver layer, and the second barrier layer is not greater than the thickness of the second silver layer.

4. The automotive triple-silver Low-E coated glass according to claim 3, characterized in that, The first barrier layer and the second barrier layer are continuous NiCr layers, and the thickness of the first barrier layer and the second barrier layer is no more than 0.8 nm.

5. The automotive triple-silver Low-E coated glass according to any one of claims 1 to 4, characterized in that, Both the first dielectric composite layer and the second dielectric composite layer comprise ZnAlO4 sequentially stacked. x Layer, ZnSnO x Layer, ZnAlO x layer.

6. The automotive triple-silver Low-E coated glass according to claim 5, characterized in that, ZnSnO in the first dielectric composite layer x The thickness of the layer is lower than that of ZnSnO in the second dielectric composite layer. x layer.

7. The automotive triple-silver Low-E coated glass according to claim 6, characterized in that, The thickness of the first dielectric composite layer is 60~90nm, and the thickness of the second dielectric composite layer is 70~100nm.

8. The automotive triple-silver Low-E coated glass according to claim 1, characterized in that, The composite coating structure also includes a bottom protective layer and a top protective layer; The bottom protective layer is selected from SiAlZrN x ZrO x NbO x SiN x SiAlN x ZnSnO x SiZrN x At least one of the following; The top protective layer includes a sacrificial layer and a protective layer; the sacrificial layer is selected from ZrO. x NbO x At least one of the following; the protective layer is selected from SiAlZrN x SiZrN x SiN x At least one of them.

9. The automotive triple-silver Low-E coated glass according to claim 8, characterized in that, The thickness of the top protective layer is no higher than 30nm and no lower than 20nm.

10. The automotive triple-silver Low-E coated glass according to claim 8, characterized in that, A seed layer is also provided between the bottom protective layer and the first silver layer.

11. A method for preparing triple-silver Low-E coated glass for automobiles, characterized in that, A bottom protective layer, a seed layer, a first silver layer, a first dielectric composite layer, a second silver layer, a second dielectric composite layer, a first barrier layer, a third silver layer, a second barrier layer, a smoothing layer, a protective layer, and a sacrificial layer are sequentially formed on a glass substrate using vacuum magnetron sputtering. The thickness of the second silver layer is greater than that of the third silver layer, and the thickness of the third silver layer is greater than that of the first silver layer. The thickness of the second silver layer is no greater than 20 nm, and the thickness of the first silver layer is no greater than 12 nm. The thickness of the composite coating structure is no greater than 320 nm.

12. The automotive triple-silver Low-E coated glass according to claim 11, characterized in that, During the vacuum magnetron sputtering coating process, the residual oxygen partial pressure in the vacuum magnetron sputtering equipment is no higher than 10. -8 Pa; the temperature of the glass substrate is controlled below 150°C.

13. A type of laminated coated glass for automobiles, characterized in that, The automotive triple silver Low-E coated glass comprises, in sequence, clear glass, an adhesive layer, and the automotive triple silver Low-E coated glass as described in any one of claims 1 to 10, or the automotive triple silver Low-E coated glass prepared by the preparation method described in any one of claims 11 to 12.

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