Double-silver coated glass capable of being tempered in different places and preparation method of double-silver coated glass

Abstract

The invention provides double-silver coated glass capable of being tempered in different places and a preparation method of the double-silver coated glass, and relates to the technical field of coated glass. The invention provides double-silver coated glass capable of being tempered in different places, which comprises a glass substrate, the bottom dielectric combination layer, the first Ag functional layer, the first metal sacrificial layer, the middle dielectric combination layer, the second metal sacrificial layer, the second Ag functional layer, the third metal sacrificial layer and the top dielectric protection combination layer are sequentially deposited on the surface of one side of the glass substrate from inside to outside. Each of the bottom dielectric combination layer and the middle dielectric combination layer is formed by laminating more than two dielectric layers; the top layer dielectric protection combination layer is formed by laminating more than two dielectric layers and a top layer protection layer, and the top layer protection layer is located at the outermost layer. The double-silver coated glass provided by the invention has excellent high-temperature resistance and supports remote tempering and laminated processing treatment, and the tempered product has excellent performance; and an excellent heat insulation effect is achieved.

Description

Technical Field

[0001] This invention relates to the field of coated glass technology, and in particular to a double-silver coated glass that supports tempering in different locations and its preparation method. Background Technology

[0002] Automotive coated glass is produced by depositing one or more thin films of metal, alloy, or metal compound on the glass surface using magnetron sputtering vacuum deposition technology. This process modifies the glass's optical properties to meet the specific needs of automotive applications. Currently, Low-E glass, widely used in the construction industry, is typically designed based on a planar tempering process. It involves uniformly heating to approximately 650°C (for 200-250 seconds) followed by air cooling, resulting in good stability of the film structure under these conditions. However, automotive glass tempering generally requires hot bending to achieve the desired curved shape. Automotive glass tempering involves heating the glass to its softening point (600-700°C) and applying external pressure to bend and shape it. This process requires a longer heat treatment time than Low-E glass (typically 400 seconds), which can easily lead to problems such as film cracking, desorption from the substrate, or decreased optical performance. Furthermore, silver-based functional films are commonly used in automotive coated glass to achieve high reflectivity of infrared radiation. However, silver is easily oxidized under high-temperature tempering conditions, and Ag particles tend to migrate and diffuse into adjacent films during heat treatment, thereby damaging the original film structure and causing quality defects such as reduced infrared reflectivity and localized film burning. In addition, existing automotive coated glass still has certain limitations in terms of overall heat insulation performance. Therefore, there is an urgent need to develop automotive coated glass that combines high-temperature temperability with excellent optical performance. Summary of the Invention

[0003] In view of this, the purpose of this invention is to provide a double-silver coated glass that can be tempered in different locations and a method for preparing the same. The double-silver coated glass provided by this invention has excellent high-temperature resistance, can be tempered in different locations, and has excellent thermal insulation performance.

[0004] To achieve the above-mentioned objectives, the present invention provides the following technical solution: The present invention provides a double silver-coated glass that supports tempering in different locations, comprising a glass substrate, and a bottom dielectric composite layer, a first Ag functional layer, a first metal sacrificial layer, an intermediate dielectric composite layer, a second metal sacrificial layer, a second Ag functional layer, a third metal sacrificial layer, and a top dielectric protection composite layer deposited sequentially from the inside out on one side surface of the glass substrate. Both the bottom dielectric composite layer and the intermediate dielectric composite layer are composed of two or more dielectric layers stacked together. The top dielectric protection layer is composed of two or more dielectric layers and a top protection layer, with the top protection layer located on the outermost layer. The dielectric material of each dielectric layer in the bottom dielectric composite layer, the intermediate dielectric composite layer, and the top dielectric protection composite layer is independently one or more of silicon nitride, silicon aluminum zirconium nitride, silicon aluminum zirconium oxide, titanium nitride, titanium oxide, zinc oxide, zinc oxide-doped aluminum, zinc tin oxide, niobium nitride, niobium oxide, silicon oxide, aluminum nitride, and aluminum oxide; the material of the top protective layer is one or more of silicon nitride, silicon oxide, silicon aluminum zirconium nitride, silicon aluminum zirconium oxide, titanium oxide, and zirconium oxide. The materials of any adjacent layers in the double-silver coated glass that supports off-site tempering are different.

[0005] Preferably, the thickness of the glass substrate is 1.8~12mm.

[0006] Preferably, the total thickness of the bottom dielectric composite layer is 20~55nm, and the total thickness of the intermediate dielectric composite layer is 70~130nm.

[0007] Preferably, the total thickness of the top dielectric protection composite layer is 20~55nm, and the thickness of the top protective layer is 2~15nm.

[0008] Preferably, the dielectric layer in the bottom dielectric composite layer is made of one or more of silicon aluminum zirconium nitride, silicon nitride, titanium oxide, zinc oxide, niobium oxide, zinc oxide doped with aluminum, and silicon oxide; the dielectric layer in the intermediate dielectric composite layer is made of one or more of zinc oxide doped with aluminum, silicon nitride, titanium oxide, zinc oxide, zinc tin oxide, and silicon oxide; and the dielectric layer in the top dielectric protection composite layer is made of one or more of zinc oxide doped with aluminum, silicon nitride, and zinc tin oxide.

[0009] Preferably, the thickness of the first Ag functional layer is 5~20nm, and the thickness of the second Ag functional layer is 3~20nm.

[0010] Preferably, the materials of the first metal sacrificial layer, the second metal sacrificial layer, and the third metal sacrificial layer are independently one or more of nickel-chromium alloy, nickel-chromium oxide, nickel-chromium nitride, titanium, titanium nitride, zinc-aluminum alloy, and zinc-aluminum oxide.

[0011] Preferably, the thicknesses of the first metal sacrificial layer, the second metal sacrificial layer, and the third metal sacrificial layer are independently 0.1~2nm.

[0012] This invention provides a method for preparing double-silver coated glass that supports tempering in different locations, as described in the above technical solution, comprising the following steps: The bottom dielectric composite layer, the first Ag functional layer, the first metal sacrificial layer, the intermediate dielectric composite layer, the second metal sacrificial layer, the second Ag functional layer, the third metal sacrificial layer, and the top dielectric protective composite layer are sequentially sputtered from the inside to the outside on one side surface of the glass substrate to obtain the double silver-coated glass that supports tempering in different locations.

[0013] This invention provides a double-silver coated laminated glass for automobiles, comprising a PVB film, a glass substrate laminated to one surface of the PVB film, and a tempered double-silver coated glass laminated to the other surface of the PVB film. The tempered double-silver coated glass is formed by tempering the double-silver coated glass that supports tempering in different locations as described in the above technical solution.

[0014] This invention provides a double-silver coated glass that supports tempering at different locations, comprising a glass substrate and, from the inside out, a bottom dielectric composite layer, a first Ag functional layer, a first metal sacrificial layer, an intermediate dielectric composite layer, a second metal sacrificial layer, a second Ag functional layer, a third metal sacrificial layer, and a top dielectric protection composite layer deposited on one side surface of the glass substrate; the bottom dielectric composite layer and the intermediate dielectric composite layer are each composed of two or more dielectric layers stacked together; the top dielectric protection composite layer is composed of two or more dielectric layers and a top protective layer stacked together, with the top protective layer located as the outermost layer. Compared with the prior art, this invention has the following beneficial effects: (1) The double-silver coated glass that can be tempered at different locations provided by this invention has excellent high-temperature resistance. The product supports hot bending and lamination processing at different locations. The appearance of the tempered product meets the appearance quality requirements in the national standard GB-T18915.2-2013 Coated Glass Part 2: Low Emissivity Coated Glass. The tempered product has a higher aesthetic value in terms of glass surface reflection color, and the glass surface reflection color after tempering tends to be stable and has higher heat reflection performance. The reason is: The double-silver coated glass provided by this invention is composed of more than 10 layers of thin films, including a double Ag functional layer, three metal sacrificial layers, and three dielectric composite layers (bottom dielectric composite layer, middle dielectric composite layer, and top dielectric protective composite layer). The double Ag functional layer provides excellent infrared heat insulation and a wide range of color adjustment capabilities. The metal sacrificial layers, distributed on both sides of the Ag functional layer, not only protect the Ag functional layer from high-temperature oxidation but also further enhance the photoelectric performance of the tempered Ag functional layer and its higher reflectivity in the infrared thermal band. Addressing the issue of stress concentration leading to film cracking in the metal functional layer during hot bending, the dielectric composite layers, through a careful combination of stress-inducing oxides and nitrides, create a self-balancing stress system within the multilayer film, significantly improving the overall adhesion and mechanical durability of the film, strengthening the protection of the Ag functional layer, promoting denser Ag functional layer deposition, and precisely controlling glass color parameters. The top dielectric protective composite layer is made of a high-hardness, chemically stable, and weather-resistant material, ensuring excellent protection for the underlying film system.

[0015] (2) The double silver-coated glass provided by the present invention has excellent heat insulation effect because: the double silver-coated glass in the present invention has more than 10 thin films, including two Ag functional layers, through reasonable combination of film materials, providing the product with excellent infrared heat insulation capability, significantly improving the reflectivity of the near-infrared band (780nm~2500nm), and the average near-infrared reflectivity of the provided double silver-coated glass can reach 69.8%, which makes it more effective in reflecting infrared heat. When applied to automotive glass, it can significantly block heat radiation from entering the car, reduce air conditioning energy consumption, and improve range.

[0016] This invention combines a robust film structure design with a high-quality functional layer to create a high-end coated glass product that supports tempering in different locations and has excellent optical performance, superior durability, and reliability. Attached Figure Description

[0017] Figure 1 This is a schematic diagram of the structure of the double-silver-coated glass that supports tempering in different locations, provided by the present invention. Figure 1In the middle, 001-glass substrate, 100-bottom dielectric composite layer, 200-first Ag functional layer, 300-first metal sacrificial layer, 400-intermediate dielectric composite layer, 500-second metal sacrificial layer, 600-second Ag functional layer, 700-third metal sacrificial layer, 800-top dielectric protection composite layer, 101-first dielectric layer, 102-second dielectric layer, 103-third dielectric layer, 401-fourth dielectric layer, 402-fifth dielectric layer, 403-sixth dielectric layer, 404-seventh dielectric layer, 801-eighth dielectric protection layer, 802-ninth dielectric protection layer, 803-top protection layer; Figure 2 This is a schematic diagram of the structure of the double-silver automotive coated laminated glass in the embodiment. Figure 2 In the middle, #1 is the outer surface of the double silver laminated coated glass car exterior, #2 is the coated surface of the double silver laminated coated glass car exterior, #3 is the PVB-connected surface of the ordinary float glass car interior, and #4 is the inner surface of the ordinary float glass car interior. Figure 3 This is a comparison of the infrared reflectance spectra of the double-silver automotive coated glass and 2.1mm clear glass in Example 1. Detailed Implementation

[0018] The present invention provides a double silver-coated glass that supports tempering in different locations, comprising a glass substrate, and a bottom dielectric composite layer, a first Ag functional layer, a first metal sacrificial layer, an intermediate dielectric composite layer, a second metal sacrificial layer, a second Ag functional layer, a third metal sacrificial layer, and a top dielectric protection composite layer deposited sequentially from the inside out on one side surface of the glass substrate. Both the bottom dielectric composite layer and the intermediate dielectric composite layer are composed of two or more dielectric layers stacked together. The top dielectric protection layer is composed of two or more dielectric layers and a top protection layer, with the top protection layer located on the outermost layer. The dielectric material of each dielectric layer in the bottom dielectric composite layer, the intermediate dielectric composite layer, and the top dielectric protection composite layer is independently one or more of silicon nitride, silicon aluminum zirconium nitride, silicon aluminum zirconium oxide, titanium nitride, titanium oxide, zinc oxide, zinc oxide-doped aluminum, zinc tin oxide, niobium nitride, niobium oxide, silicon oxide, aluminum nitride, and aluminum oxide; the material of the top protective layer is one or more of silicon nitride, silicon oxide, silicon aluminum zirconium nitride, silicon aluminum zirconium oxide, titanium oxide, and zirconium oxide. The materials of any adjacent layers in the double-silver coated glass that supports off-site tempering are different.

[0019] The present invention provides a double-silver coated glass that supports tempering at different locations, comprising a glass substrate. In this invention, the glass substrate is preferably ordinary float glass, such as clear glass or ultra-clear glass. In this invention, the thickness of the glass substrate is preferably 1.8~12mm; in this embodiment, ordinary float glass with a thickness of 2.1mm is used.

[0020] The present invention provides a double-silver coated glass supporting off-site tempering, comprising a bottom dielectric composite layer deposited on one side surface of the glass substrate. In the present invention, the bottom dielectric composite layer is composed of two or more dielectric layers stacked together. Each dielectric layer is independently made of one or more of the following: silicon nitride, silicon aluminum zirconium nitride, silicon aluminum zirconium oxide, titanium nitride, titanium oxide, zinc oxide, zinc oxide-doped aluminum, zinc tin oxide, niobium nitride, niobium oxide, silicon oxide, aluminum nitride, and aluminum oxide. Preferably, it is composed of one or more of the following: silicon aluminum zirconium nitride, silicon nitride, titanium oxide, zinc oxide, niobium oxide, zinc oxide-doped aluminum, and silicon oxide. In an embodiment of the present invention, the bottom dielectric composite layer is composed of three dielectric layers stacked together, arranged sequentially from the inside to the outside of the glass substrate surface: a first dielectric layer, a second dielectric layer, and a third dielectric layer. The materials of the first, second, and third dielectric layers are silicon nitride, titanium oxide, and zinc oxide, respectively; or silicon aluminum zirconium nitride, niobium oxide, and zinc oxide-doped aluminum, respectively; or silicon nitride, silicon oxide, and zinc oxide, respectively. In this invention, the total thickness of the bottom dielectric composite layer is preferably 20~55nm, and can be 30, 40, 50 or 53nm; this invention does not have any special requirements on the thickness of each dielectric layer in the bottom dielectric composite layer, as long as the total thickness of the bottom dielectric composite layer is met.

[0021] In this invention, the dielectric layer in the bottom dielectric composite layer is in contact with the glass substrate and has strong adhesion to the glass substrate. This adhesion smooths out microscopic defects on the glass surface, reduces the migration and aggregation of silver atoms on the glass surface, and thus helps form a continuous, uniform, dense, and low-resistance silver film. This ensures the entire film system is firmly "grown" on the glass and prevents sodium ions (Na+) in the glass from... + In subsequent high-temperature processes, substances such as α, β, and γ diffuse into the functional layer, contaminating the Ag layer and causing performance degradation.

[0022] The double-silver coated glass supporting off-site tempering provided by the present invention includes a first Ag functional layer deposited on the surface of the underlying dielectric composite layer, wherein the first Ag functional layer is a metallic Ag layer. In the present invention, the thickness of the first Ag functional layer is preferably 5~20nm, and can be 7, 7.5, 8, 8.5 or 10nm.

[0023] The double-silver coated glass supporting off-site tempering provided by the present invention includes a first metal sacrificial layer deposited on the surface of the first Ag functional layer. In the present invention, the material of the first metal sacrificial layer is preferably one or more of nickel-chromium alloy, nickel-chromium oxide, nickel-chromium nitride, titanium, titanium nitride, zinc-aluminum alloy, and zinc-aluminum oxide, preferably titanium, nickel-chromium nitride, or titanium nitride; the thickness of the first metal sacrificial layer is preferably 0.1~2 nm, and can be 0.4, 0.5, 0.55, 0.6, or 0.7 nm.

[0024] The present invention provides a double-silver coated glass supporting off-site tempering, comprising an intermediate dielectric composite layer deposited on the surface of a first metal sacrificial layer. In the present invention, each intermediate dielectric composite layer is composed of two or more dielectric layers stacked together. The material of each dielectric layer in the intermediate dielectric composite layer is independently one or more of silicon nitride, aluminum zirconium silicon nitride, aluminum zirconium silicon oxide, titanium nitride, titanium oxide, zinc oxide, zinc oxide-doped aluminum, zinc tin oxide, niobium nitride, niobium oxide, silicon oxide, aluminum nitride, and aluminum oxide, preferably one or more of zinc oxide-doped aluminum, silicon nitride, titanium oxide, zinc oxide, zinc tin oxide, and silicon oxide. In this embodiment of the invention, the intermediate dielectric composite layer is composed of four dielectric layers stacked together. Starting from the surface of the first metal sacrificial layer, the layers are sequentially a fourth dielectric layer, a fifth dielectric layer, a sixth dielectric layer, and a seventh dielectric layer. The materials of the fourth, fifth, sixth, and seventh dielectric layers are, in sequence, zinc oxide-doped aluminum, silicon nitride, titanium oxide, and zinc oxide; or, zinc oxide-doped aluminum, silicon nitride, zinc tin oxide, and zinc oxide; or, zinc oxide-doped aluminum, silicon nitride, silicon oxide, and zinc oxide. In this invention, the total thickness of the intermediate dielectric composite layer is preferably 70~130 nm, and can be 80, 90, 100, 110, 120, or 123 nm. This invention does not have special requirements for the thickness of each dielectric layer in the intermediate dielectric composite layer, as long as the total thickness of the intermediate dielectric composite layer is met.

[0025] In this invention, the intermediate dielectric composite layer serves as the "hub" connecting the two core functional units (Ag layers) in the "double silver" structure, requiring the highest level of technical expertise. It separates the two silver layers and their adjacent dielectric layers, forming a complex "Fabry-Perot" type interference filter structure. During the deposition of the upper dielectric layer and subsequent Ag layers, the plasma environment may cause slight damage or oxidation to the lower Ag layer. This dense intermediate dielectric composite layer further protects the underlying Ag layer from damage. Furthermore, the intermediate dielectric composite layer is the "soul" of the entire film system design; its thickness is precisely designed to enhance or weaken the optical interference effects generated by the upper and lower Ag films, flexibly adjusting the product's transmittance and color, resulting in a higher reflective aesthetic.

[0026] The double-silver coated glass supporting off-site tempering provided by the present invention includes a second metal sacrificial layer deposited on the surface of an intermediate dielectric composite layer. In the present invention, the material of the second metal sacrificial layer is preferably one or more of nickel-chromium alloy, nickel-chromium oxide, nickel-chromium nitride, titanium, titanium nitride, zinc-aluminum alloy, and zinc-aluminum oxide, more preferably titanium, nickel-chromium nitride, or titanium nitride; the thickness of the second metal sacrificial layer is preferably 0.1~2 nm, and can be 0.5, 0.55, 0.6, 0.65, or 0.7 nm.

[0027] The double-silver coated glass supporting off-site tempering provided by the present invention includes a second Ag functional layer deposited on the surface of the second metal sacrificial layer, wherein the second Ag functional layer is a metallic Ag layer. In the present invention, the thickness of the second Ag functional layer is preferably 3~20nm, and can be 5, 8, 8.5 or 15nm.

[0028] The double-silver coated glass supporting off-site tempering provided by the present invention includes a third metal sacrificial layer deposited on the surface of the second Ag functional layer. In the present invention, the material of the third metal sacrificial layer is preferably one or more of nickel-chromium alloy, nickel-chromium oxide, nickel-chromium nitride, titanium, titanium nitride, zinc-aluminum alloy, and zinc-aluminum oxide, more preferably titanium, nickel-chromium nitride, or titanium nitride; the thickness of the third metal sacrificial layer is preferably 0.1~2 nm, and can be 0.4, 0.5, 0.55, or 0.75 nm.

[0029] The present invention provides a double-silver coated glass supporting off-site tempering, comprising a top dielectric protection composite layer deposited on the surface of the third metal sacrificial layer. In the present invention, the top dielectric protection composite layer is composed of two or more dielectric layers and a top protective layer, with the top protective layer located as the outermost layer. In the present invention, the material of each dielectric layer in the top dielectric protection composite layer is independently one or more of silicon nitride, aluminum zirconium silicon nitride, aluminum zirconium silicon oxide, titanium nitride, titanium oxide, zinc oxide, zinc oxide-doped aluminum, zinc tin oxide, niobium nitride, niobium oxide, silicon oxide, aluminum nitride, and aluminum oxide, more preferably one or more of zinc oxide-doped aluminum, silicon nitride, and zinc tin oxide; the material of the top protective layer is one or more of silicon nitride, silicon oxide, aluminum zirconium silicon nitride, aluminum zirconium silicon oxide, titanium oxide, and zirconium oxide. In this embodiment of the invention, the top dielectric protection composite layer is composed of two dielectric layers and a top protective layer stacked together. Starting from the surface of the third metal sacrificial layer, the dielectric layers in the top dielectric protection composite layer are sequentially an eighth dielectric layer and a ninth dielectric layer. The materials of the eighth dielectric layer, the ninth dielectric layer, and the top protective layer are, in sequence, zinc oxide-doped aluminum, silicon nitride, and titanium oxide, or zinc oxide-doped aluminum, zinc tin, and silicon aluminum zirconium nitride, or zinc oxide-doped aluminum, silicon nitride, and zirconium oxide. In this invention, the total thickness of the top dielectric protection composite layer is preferably 20-55 nm, and can be 30, 40, 42, 45, 47, or 48 nm; the thickness of the top protective layer is preferably 2-15 nm, and can be 3, 5, 6, or 10 nm. This invention does not have special requirements for the thickness of each dielectric layer in the top dielectric protection composite layer, as long as they together with the top protective layer meet the total thickness of the top dielectric protection composite layer. In this invention, the thickness of each layer in the double-silver coated glass also affects the color, thermal properties, and weather resistance of the coated glass.

[0030] In this invention, the functions of the top-layer dielectric protection composite layer include: ① Improving adhesion: ensuring a firm bond between the top-layer protective layer and the Ag layer, preventing peeling; ② Stress buffering: the extremely hard outermost protective layer material (such as Si3N4) may have stress mismatch issues when directly bonded to the relatively soft Ag layer; the layer transition can act as a buffer; ③ Mechanical protection: the extremely high hardness gives the film excellent scratch and wear resistance, enabling it to withstand normal friction during production and transportation; ④ Chemical protection / weather resistance: the film structure design of the top-layer protective material can effectively block the penetration of water vapor, oxygen, and acid / alkali ions, preventing the internal Ag layer from being corroded and oxidized, and ensuring the long-term stability of the product in harsh environments; ⑤ Final optical fine-tuning: the thickness of this composite layer also affects the final color and transmittance of the product.

[0031] Figure 1This is a schematic diagram of the structure of a double-silver coated glass supporting off-site tempering provided in an embodiment of the present invention. The double-silver coated glass supporting off-site tempering provided in this embodiment of the present invention is used in automotive glass (referred to as double-silver automotive coated glass), comprising a glass substrate 001, and, sequentially deposited from the inside out on one side surface of the glass substrate 001, a bottom dielectric composite layer 100, a first Ag functional layer 200, a first metal sacrificial layer 300, an intermediate dielectric composite layer 400, a second metal sacrificial layer 500, a second Ag functional layer 600, a third metal sacrificial layer 700, and a top dielectric protective composite layer 800; wherein, the bottom dielectric composite layer 100... The 0 layer is composed of three dielectric layers stacked together, namely the first dielectric layer 101, the second dielectric layer 102, and the third dielectric layer 103; the intermediate dielectric combination layer 400 is composed of four dielectric layers stacked together, namely the fourth dielectric layer 401, the fifth dielectric layer 402, the sixth dielectric layer 403, and the seventh dielectric layer 404; the top dielectric protection combination layer 800 is composed of two dielectric layers (the eighth dielectric protection layer 801 and the ninth dielectric protection layer 802) and a top protection layer 803, wherein the top protection layer is located on the outermost layer. The double-silver coated glass supporting off-site tempering provided in this embodiment of the invention has the following material composition from the inside out (i.e. from 101 to 803) on the surface of the glass substrate 001: silicon nitride / titanium oxide / zinc oxide / metallic Ag layer / metallic titanium / zinc oxide-doped aluminum / silicon nitride / titanium oxide / zinc oxide / metallic titanium / metallic Ag layer / metallic titanium / zinc oxide-doped aluminum / silicon nitride / titanium oxide, or silicon aluminum zirconium nitride / niobium oxide / zinc oxide-doped aluminum / metallic Ag layer / nickel chromium nitride / zinc oxide-doped aluminum / silicon nitride / zinc tin oxide / zinc oxide-doped aluminum / nickel chromium nitride / metallic Ag layer / nickel chromium nitride / zinc oxide-doped aluminum / zinc tin oxide / silicon aluminum zirconium nitride, or silicon nitride / silicon oxide / zinc oxide / metallic Ag layer / titanium nitride / zinc oxide-doped aluminum / silicon nitride / zinc oxide / zinc oxide / metallic Ag layer / titanium nitride / zinc oxide-doped aluminum / silicon nitride / zinc oxide.

[0032] The double-silver coated glass supporting tempering in different locations provided by this invention has the following advantages: (1) Excellent thermal insulation: The rational design of the double-layer Ag functional layer structure and its dielectric / metal sacrificial layer improves the quality and photoelectric performance of the silver layer, significantly reduces the emissivity and surface resistance, effectively isolates thermal radiation (suitable for car windshields / sunroofs), and improves driving comfort; (2) Excellent tempering resistance: The bottom dielectric and metal sacrificial layer effectively block the diffusion of sodium ions and the thermal diffusion of silver particles in the glass, enhancing the tempering resistance and oxidation resistance. The performance is stable after being placed in air for 40 days, which is beneficial for subsequent tempering processing; it supports off-site hot bending and lamination processing, and the high temperature resistance (600~700℃) of the film structure is excellent. (3) Adjustable performance and high cost performance: The visible light transmittance, reflectance and surface resistivity of double silver coated glass can be flexibly adjusted through the thin film interference principle. Compared with ordinary glass, the color is adjustable and the thermal performance is better; compared with triple silver glass, although the total solar transmittance (tts) and solar reflectance (RE) values ​​are slightly inferior, the cost is significantly lower (due to production line / target material limitations).

[0033] This invention provides a method for preparing double-silver coated glass that supports tempering in different locations, as described in the above technical solution, comprising the following steps: Using magnetron sputtering, a bottom dielectric composite layer, a first Ag functional layer, a first metal sacrificial layer, an intermediate dielectric composite layer, a second metal sacrificial layer, a second Ag functional layer, a third metal sacrificial layer, and a top dielectric protective composite layer are sequentially sputtered from the inside out on one side surface of the glass substrate.

[0034] The present invention does not have special requirements for the conditions of magnetron sputtering, as long as the constituent layers of the corresponding materials and thicknesses can be obtained. The difference in the number of layers and materials is achieved by the target configuration and reaction gas control in the magnetron sputtering coating chamber, and the difference in film thickness is achieved by adjusting the sputtering power of the target.

[0035] In this embodiment of the invention, the specific steps for preparing the double-silver coated glass that supports tempering in different locations are as follows: Loading and cleaning: Uncoated glass substrates are placed into the conveying system by the film picker and sent to the cleaning machine for cleaning and drying via a bidirectional table and roller conveyor; Purification and Transmission: After being cleaned and dried, the glass substrates are sequentially transported via roller conveyors into the cleanroom, coating lock room, and buffer room. Coating: A clean, stain-free glass substrate enters the magnetron sputtering coating chamber. By precisely controlling the sputtering power of the target material at different positions, the sputtering deposition of each layer in the double silver coated glass is completed. Online testing: After coating, the glass is tested online using a photometer to measure parameters such as transmittance, reflectance, and color value; Unloading and stacking: Qualified glass is conveyed to the stacker machine via roller conveyor and bidirectional table to complete automatic stacking.

[0036] This invention provides a double-silver coated laminated glass for automobiles, comprising a PVB (polyvinyl butyral) film, a glass substrate laminated to one side of the PVB film, and a tempered double-silver coated glass laminated to the other side of the PVB film. The tempered double-silver coated glass is formed by tempering the double-silver coated glass that supports tempering in different locations as described in the above technical solution, and the coated side of the tempered double-silver coated glass is in contact with the PVB film.

[0037] In this invention, the tempering temperature is preferably 600~700℃, which can be 600, 650 or 700℃, and the time is preferably 350~450, which can be 380, 400, 420 or 450s.

[0038] The double-silver coated glass described in this invention, which supports tempering in different locations, conforms to the national standard requirements of "GB-T18915.2-2013 Coated Glass Part 2: Low Emissivity Coated Glass" after tempering, and exhibits a high-quality, high-stability glass surface reflective color. It significantly improves heat insulation (near-infrared high reflectivity >80%) compared to ordinary 2.1mm glass. When used in automotive glass, it can block a large amount of heat radiation from entering the vehicle, maintain a stable interior temperature, reduce the energy consumption of automotive air conditioning, and achieve a good range extension effect.

[0039] Figure 2 This is a schematic diagram of the structure of double-silver automotive coated laminated glass in an embodiment of the present invention.

[0040] In this invention, the glass substrate is preferably ordinary float glass, such as plain white glass or ultra-clear glass, and the thickness can be 2.1 mm.

[0041] This invention does not impose any special requirements on the PVB film; any PVB film well-known in the art can be selected according to the needs. For example, selecting a white PVB film, combined with the tempered double-silver coated glass, enables the double-silver coated laminated glass to have excellent heat insulation performance while maintaining high light transmittance, making it suitable for automotive windshields. Selecting a black PVB film, combined with the tempered double-silver coated glass, enables the double-silver coated laminated glass to not only have excellent ultraviolet and infrared blocking capabilities, but also improves the privacy of the vehicle interior due to its extremely low light transmittance, and provides significant sound insulation, making it suitable for automotive sunroofs.

[0042] To further illustrate the present invention, the following detailed description, in conjunction with examples, of the double-silver coated glass supporting off-site tempering and its preparation method provided by the present invention, should not be construed as limiting the scope of protection of the present invention.

[0043] In this embodiment, the double-silver automotive coated glass that supports off-site tempering is composed of ordinary float glass and 15 thin films, with the structure as follows: Figure 1 As shown, in this embodiment, starting from one side surface of the glass substrate, the... Figure 1 The film layers 101 to 803 are referred to as layers 1 to 15, respectively.

[0044] Example 1: A double-silver low-emissivity coated glass that supports tempering in different locations A type of double-silver coated automotive glass that supports off-site tempering is composed of ordinary float glass and 15 thin films. The ordinary float glass is 2.1mm thick plain glass. The thicknesses of the 15 thin films deposited by magnetron sputtering, from the inside to the outside of the ordinary float glass, are as follows: layer 1 is 15nm thick, layer 2 is 15nm thick, layer 3 is 20nm thick, layer 4 is 7.5nm thick, layer 5 is 0.7nm thick, layer 6 is 20nm thick, layer 7 is 25nm thick, layer 8 is 20nm thick, layer 9 is 35nm thick, layer 10 is 0.6nm thick, layer 11 is 8.5nm thick, layer 12 is 0.55nm thick, layer 13 is 15nm thick, layer 14 is 26nm thick, and layer 15 is 6nm thick.

[0045] The materials used in layers 1, 7, and 14 are silicon nitride; the materials used in layers 2, 8, and 15 are titanium oxide; the materials used in layers 3 and 9 are zinc oxide; the materials used in layers 4 and 11 are metallic Ag layers; the materials used in layers 5, 10, and 12 are metallic titanium; and the materials used in layers 6 and 13 are zinc oxide doped with aluminum.

[0046] Silicon nitride (SiN) x This thin film is a chemically stable material with excellent scratch resistance and high-temperature oxidation resistance. It bonds well with glass, and as a bottom dielectric material, it significantly enhances the adhesion of the silver layer, prevents sodium ions from diffusing into the film system, and protects the film structure. As an intermediate dielectric material, it protects the functional silver layer and adjusts its color. As a top dielectric protective layer material, it also enhances the overall hardness of the film system and improves its heat resistance and machinability.

[0047] Titanium oxide (TiO) x The thin film, acting as a dielectric layer, modulates the optical parameters of the film system structure. When located on either side of the silver layer, it effectively reduces visible light reflection and increases visible light transmittance by utilizing the principle of light interference. This means the coated glass appears more transparent, has a more neutral color, and provides better light transmission. As a protective layer, it significantly improves the mechanical strength (scratch resistance) and chemical stability (acid and alkali resistance) of the entire film system. Zinc oxide (ZnO) films have a hexagonal wurtzite crystal structure, and their surface energy can guide the deposited silver atoms to grow in a more uniform, dense and continuous manner, forming a smooth and flat ultrathin silver layer. A more continuous silver layer means lower resistance, which directly translates into higher infrared reflectivity, i.e., better Low-E (low-emissivity) performance.

[0048] Zinc oxide-doped aluminum (AZO) exhibits excellent thermal stability, low absorption of infrared radiation, and effective blocking of outdoor radiant heat. In the bottom and intermediate dielectric layers, AZO serves as a seed layer to aid in the deposition of high-quality Ag functional layers and blocks the diffusion of sodium ions into the glass. In the intermediate and top protective layers, AZO protects the Ag layer from high-temperature damage and enhances the tempering resistance of the film system.

[0049] Titanium (Ti) thin film serves as a sacrificial metal layer, forming a functional oxide layer that prevents the silver layer from oxidizing and diffusing. This dense Ti film effectively blocks impurities (such as water vapor and sodium ions) from the inside of the glass substrate from diffusing into the silver layer, protecting it from oxidation and ensuring that the silver layer has excellent low-emissivity (high infrared reflectivity) and conductivity.

[0050] The double silver-coated glass supporting off-site tempering was obtained by depositing various film layers on the surface of ordinary float glass using magnetron sputtering. The process parameters of each film layer during magnetron sputtering are shown in Table 1. In Table 1, 1#~15# correspond to the 1st to the 15th layers respectively.

[0051] Table 1. Process parameters for each film layer when using magnetron sputtering coating.

[0052] The tempering resistance of the double-silver coated automotive glass from Example 1 was tested to examine the degree of change in the coating layer with tempering time and to evaluate the stability of transmittance and color value after tempering. The heating conditions were as follows: tempering was carried out in a tempering furnace for 380s, 400s, and 420s (referred to as Example 1, Example 2, and Example 3, respectively), at a temperature of 650℃. The dimensions of the double-silver coated automotive glass were 2.1mm thick and 600×400mm. The test results are shown in Table 2.

[0053] Table 2 shows the effects of different heating times on the transmittance and color of double-silver coated glass at 650℃.

[0054] In Table 2, T represents the transmittance value, RgL represents the reflected brightness value, and Rga... and RGB The color reflected from the exterior of the car is defined as follows: a > 0 = red, a < 0 = green; b > 0 = yellow, a < 0 = blue. The exterior reflective color of a single tempered glass piece is light blue.

[0055] Table 2 shows that the color difference of the steel-backed glass surfaces in Experiment 1 and Experiment 2 is 0.75, the color difference between Experiment 1 and Experiment 3 is 0.37, and the color difference between Experiment 2 and Experiment 3 is 1.04. This indicates that different heating times at 650℃ have a negligible effect on color. The double-silver automotive coated glass exhibits excellent heat resistance and processing performance, good surface quality, and no quality problems such as poor haze or film burning. It also demonstrates good processing resistance and meets the requirements for off-site hot bending.

[0056] Using a Lambda 950 UV-Vis-NIR spectrophotometer, spectral analysis was performed on the double-silver coated automotive glass sample from Example 1 and a 2.1mm uncoated ordinary glass sample. The results are as follows: Figure 3 As shown. Figure 3 This image shows a comparison of the infrared reflectance spectra of double-silver automotive coated glass (tempered at 650℃ for 400s) and 2.1mm clear glass in Example 1. The average near-infrared (780nm~2500nm) reflectance of the double-silver automotive coated glass reaches 69.8%, far exceeding the 8.6% of ordinary uncoated glass. This allows it to more effectively reflect infrared heat, and its application in automotive glass can significantly block heat radiation from entering the vehicle, reducing air conditioning energy consumption and improving driving range.

[0057] In addition, the double silver coated glass of Example 1 was heated at 700°C for different times, and its transmittance and color changes were tested to evaluate its tempering performance at 700°C. The results are shown in Table 3.

[0058] Table 3. Changes in transmittance and color of the double-silver coated glass in Example 1 under different heating times at 700℃.

[0059] Table 3 shows that, under a tempering temperature of 700℃, the color difference between the tempered glass surfaces of Examples 4 and 5 is 0.42, the color difference between Examples 4 and 6 is 0.73, and the color difference between Examples 5 and 6 is 0.96. These results indicate that, based on the design of this film system structure, the effect of different heating times on the glass surface color is relatively small at this tempering temperature. This demonstrates that the double-silver automotive coated glass possesses excellent high-temperature processing performance, stable surface quality, and no defects such as haze or film burning. It exhibits good processing adaptability and thermal stability, meeting the technical requirements for off-site hot bending processing. Whether the heating temperature is 650℃ or 700℃, the double-silver automotive coated glass exhibits excellent high-temperature processing performance.

[0060] The low-emissivity double-silver coated glass provided in Example 1, which supports tempering in different locations, has significantly improved performance after tempering.

[0061] Optical performance optimization: Transmittance increased from 66.8% before tempering to 75% after tempering (tempering temperature 650℃, heating time 400s). Reflectance (Rga) =-2, Rgb =-5.5) exhibits a light blue tint, enhancing the product's aesthetics. After tempering, the haze is as low as 0.1. Under strong flashlight, the surface quality is visually exceptionally clear, avoiding common surface quality issues found in some double-silver automotive coated glass currently on the market. The resistivity after tempering is as low as 2.1Ω / sq, indicating that the optimized film structure design further enhances the photoelectric performance of the Ag functional layer after tempering, achieving excellent performance among double-silver coated glass products.

[0062] Examples 2 and 3 both involve the application of double-silver coated glass in automotive laminated glass: the structure of the double-silver coated laminated glass is as follows... Figure 2 As shown, the vehicle consists of 2.1mm double-silver coated automotive glass (outer side, outer surface is side 1, coated surface is side 2) + 0.76mm PVB film + ordinary float glass (inner side, PVB side is side 3, inner surface is side 4). The PVB film bonds side 2 of the double-silver coated glass to side 3 of the ordinary float glass through hot pressing. The uncoated ordinary float glass can be 1.8~2.1mm thick or used in conjunction with online silver-free coated glass. Different PVB films are used depending on the application scenario.

[0063] Example 2: A high-transparency blue double-silver coated laminated glass for automotive windshields It is composed of 2.1mm double-silver coated glass, 0.76mm white PVB film, and 2.1mm ordinary float glass. It possesses excellent UV / IR blocking capabilities, maintaining high light transmittance while exhibiting a blue reflective color, enhancing the overall aesthetics of the vehicle. The 0.76mm white PVB film used is based on polyvinyl butyral (PVB) resin and plasticized with plasticizers, combining high transmittance with safety, ensuring that the glass remains intact even if it breaks, protecting the safety of occupants.

[0064] The film thickness of the coated glass in this embodiment is as follows: the first layer is 10nm thick, the second layer is 15nm thick, the third layer is 25nm thick, the fourth layer is 8.5nm thick, the fifth layer is 0.5nm thick, the sixth layer is 30nm thick, the seventh layer is 30nm thick, the eighth layer is 35nm thick, the ninth layer is 25nm thick, the tenth layer is 0.55nm thick, the eleventh layer is 5nm thick, the twelfth layer is 0.75nm thick, the thirteenth layer is 35nm thick, the fourteenth layer is 10nm thick, and the fifteenth layer is 3nm thick.

[0065] The materials used in layers 1 and 15 are silicon aluminum zirconium nitride; the material used in layer 2 is niobium oxide; the materials used in layers 8 and 14 are zinc tin oxide; the materials used in layers 3, 6, 9, and 13 are zinc oxide-doped aluminum; the materials used in layers 4 and 11 are metallic Ag layers; the materials used in layers 5, 10, and 12 are nickel chromium nitride; and the material used in layer 7 is silicon nitride.

[0066] Various film layers were deposited on the surface of ordinary float glass using magnetron sputtering. The process parameters for each film layer during magnetron sputtering are shown in Table 4.

[0067] Table 4 Process parameters for each film layer during magnetron sputtering coating

[0068] Tempering conditions: The coated double-silver automotive glass substrate was placed in a tempering furnace for tempering at 650℃ for 450 seconds. The resulting surface quality was good, and the color was uniform.

[0069] Performance parameters of this embodiment: Visible light transmittance of the coated laminated glass is 72.9% (meets the national standard requirement of >70%), Ta (Transparent color a value) = -1.1, Tb (b-value of transmitted color) = -1.5, neutral transmitted color, Rga =-2.1、Rgb =-5.6, with a blue reflection outside the vehicle. Total solar transmittance (TTS) is 45%, and solar reflectance (RE) is 39.5%. Compared to ordinary float glass (TTS 89%, RE 9%), TTS is reduced by 47%, and RE is increased by 27%. The TTS and RE values ​​are also further optimized compared to mainstream double-silver coated laminated glass, indicating that it has better heat insulation performance while ensuring high light transmittance.

[0070] The prepared laminated glass is made into 100 A 100mm sample was subjected to a low-temperature freezing and knocking test in a -40℃ freezer to examine the adhesion of the coating layer on the coated glass under extremely cold conditions after heat treatment. The results after 10 minutes of testing in the freezer showed minimal film peeling, indicating good adhesion and excellent weather resistance.

[0071] Example 3: A low-transparency black double-silver coated laminated glass for automotive sunroofs This laminated glass is composed of a 2.1mm (glass substrate) double-silver automotive-grade coated glass, a 0.76mm PVB black film, and a 1.8mm uncoated ordinary float glass. The double-silver coated laminated glass, combined with the black film and green glass, provides excellent UV and infrared protection, while its extremely low transmittance of less than 3% enhances privacy within the vehicle. The PVB film ensures the integrity of the glass in the event of breakage, protecting occupants. The black film provides significant sound insulation, improving the quietness of the cabin.

[0072] The film thickness of the coated glass in this embodiment is as follows: the first layer is 8nm thick, the second layer is 25nm thick, the third layer is 20nm thick, the fourth layer is 10nm thick, the fifth layer is 0.6nm thick, the sixth layer is 30nm thick, the seventh layer is 48nm thick, the eighth layer is 35nm thick, the ninth layer is 10nm thick, the tenth layer is 0.65nm thick, the eleventh layer is 8nm thick, the twelfth layer is 0.5nm thick, the thirteenth layer is 22nm thick, the fourteenth layer is 15nm thick, and the fifteenth layer is 5nm thick.

[0073] The materials used in layers 1, 7, and 14 are silicon nitride; the materials used in layers 2 and 8 are silicon oxide; the materials used in layers 3 and 9 are zinc oxide; the materials used in layers 4 and 11 are metallic Ag layers; the materials used in layers 5, 10, and 12 are titanium nitride; the materials used in layers 6 and 13 are zinc oxide-doped aluminum; and the material used in layer 15 is zirconium oxide.

[0074] Various film layers were deposited on the surface of ordinary float glass using magnetron sputtering. The process parameters for each film layer during magnetron sputtering are shown in Table 5.

[0075] Table 5 Process parameters for each film layer during magnetron sputtering coating.

[0076] Tempering conditions: The coated double-silver automotive glass substrate was placed in a tempering furnace for tempering at 650℃ for 450 seconds. The resulting surface quality was good, and the color was uniform.

[0077] Performance parameters of this embodiment: Visible light transmittance of the coated laminated glass is 2.5%, Rga =-0.4, RGB =-1, the reflected color seen from outside the vehicle is black. The coated laminated glass was placed in a freezer at -40℃ for 10 minutes for a freeze-resistance test; the film adhesion was excellent, with no large-area peeling. The total solar transmittance (TTS) of this coated laminated glass is 15%, and the solar reflectance (RE) is 41%. Normal uncoated ordinary float glass has a total solar transmittance (TTS) of 89% and a solar reflectance (RE) of 9%. Compared to ordinary clear glass, the total solar transmittance is reduced by 74%, heat transmission is significantly suppressed, and heat reflection is increased by approximately 27%, resulting in significantly enhanced heat reflection. This fully demonstrates that the double-silver coated laminated glass of Example 3 has better heat insulation performance while maintaining extremely low transmittance.

[0078] The prepared laminated glass is made into 100 A 100mm sample was subjected to a low-temperature freeze-impact test in a -40℃ freezer to examine the adhesion of the coating layer on the coated glass under extremely cold conditions after heat treatment. The results after 10 minutes of testing in the freezer showed minimal coating peeling, indicating good adhesion and excellent weather resistance.

[0079] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A double-silver coated glass that supports tempering in different locations, characterized in that, It includes a glass substrate, and a bottom dielectric composite layer, a first Ag functional layer, a first metal sacrificial layer, an intermediate dielectric composite layer, a second metal sacrificial layer, a second Ag functional layer, a third metal sacrificial layer, and a top dielectric protective composite layer, which are deposited sequentially from the inside out on one side surface of the glass substrate. Both the bottom dielectric composite layer and the intermediate dielectric composite layer are composed of two or more dielectric layers stacked together. The top dielectric protection layer is composed of two or more dielectric layers and a top protection layer, with the top protection layer located on the outermost layer. The dielectric material of each dielectric layer in the bottom dielectric composite layer, the intermediate dielectric composite layer, and the top dielectric protection composite layer is independently one or more of silicon nitride, silicon aluminum zirconium nitride, silicon aluminum zirconium oxide, titanium nitride, titanium oxide, zinc oxide, zinc oxide-doped aluminum, zinc tin oxide, niobium nitride, niobium oxide, silicon oxide, aluminum nitride, and aluminum oxide; the material of the top protective layer is one or more of silicon nitride, silicon oxide, silicon aluminum zirconium nitride, silicon aluminum zirconium oxide, titanium oxide, and zirconium oxide. The materials of any adjacent layers in the double-silver coated glass that supports off-site tempering are different.

2. The double-silver coated glass supporting tempering in different locations according to claim 1, characterized in that, The thickness of the glass substrate is 1.8~12mm.

3. The double-silver coated glass supporting tempering in different locations according to claim 1, characterized in that, The total thickness of the bottom dielectric composite layer is 20~55nm, and the total thickness of the intermediate dielectric composite layer is 70~130nm.

4. The double-silver coated glass supporting tempering in different locations according to claim 1, characterized in that, The total thickness of the top dielectric protection composite layer is 20~55nm, and the thickness of the top protective layer is 2~15nm.

5. The double-silver coated glass supporting off-site tempering according to claim 1, 3, or 4, characterized in that, The dielectric layer in the bottom dielectric composite layer is made of one or more of the following: silicon aluminum zirconium nitride, silicon nitride, titanium oxide, zinc oxide, niobium oxide, zinc oxide doped with aluminum, and silicon oxide. The dielectric layer in the intermediate dielectric composite layer is made of one or more of the following: zinc oxide doped with aluminum, silicon nitride, titanium oxide, zinc oxide, zinc tin oxide, and silicon oxide. The dielectric layer in the top dielectric protection composite layer is made of one or more of the following: zinc oxide doped with aluminum, silicon nitride, and zinc tin oxide.

6. The double-silver coated glass supporting tempering in different locations according to claim 1, characterized in that, The thickness of the first Ag functional layer is 5~20nm, and the thickness of the second Ag functional layer is 3~20nm.

7. The double-silver coated glass supporting tempering in different locations according to claim 1, characterized in that, The materials of the first metal sacrificial layer, the second metal sacrificial layer, and the third metal sacrificial layer are independently one or more of the following: nickel-chromium alloy, nickel-chromium oxide, nickel-chromium nitride, titanium, titanium nitride, zinc-aluminum alloy, and zinc-aluminum oxide.

8. The double-silver coated glass supporting off-site tempering according to claim 1 or 7, characterized in that, The thicknesses of the first metal sacrificial layer, the second metal sacrificial layer, and the third metal sacrificial layer are independently 0.1~2nm.

9. The method for preparing double-silver coated glass supporting off-site tempering as described in any one of claims 1 to 8, characterized in that, Includes the following steps: The bottom dielectric composite layer, the first Ag functional layer, the first metal sacrificial layer, the intermediate dielectric composite layer, the second metal sacrificial layer, the second Ag functional layer, the third metal sacrificial layer, and the top dielectric protective composite layer are sequentially sputtered from the inside to the outside on one side surface of the glass substrate to obtain the double silver-coated glass that supports tempering in different locations.

10. A double-silver coated laminated glass for automobiles, characterized in that, The invention includes a PVB film, a glass substrate laminated to one surface of the PVB film, and a tempered double-silver coated glass laminated to the other surface of the PVB film, wherein the tempered double-silver coated glass is tempered from any one of claims 1 to 8.

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