Low-e glass and method for making the same

Abstract

The application discloses LOW-E glass and a preparation method thereof, and relates to the technical field of energy-saving glass, wherein the LOW-E glass comprises substrate glass, a first low-radiation layer and a copper alloy color adjusting layer which are sequentially arranged, the first low-radiation layer comprises a first silver layer; the copper alloy color adjusting layer comprises Cu x A 1‑x ; and the A comprises at least one of Zn, Ta and Nb. The LOW-E glass and the preparation method thereof are provided to solve the technical problem of greenish silver-based low-radiation LOW-E glass in the prior art.

Description

Technical Field

[0001] This invention relates to the field of energy-saving glass technology, and in particular to a LOW-E glass and its preparation method. Background Technology

[0002] Low-E glass is a key material in the field of building energy conservation. It achieves effective reflection of infrared radiation by depositing dielectric and functional layers on the glass surface. Traditional temperable low-E glass generally uses silver as the infrared reflective functional layer, combined with a silicon nitride (Si3N4) dielectric layer and a nickel-chromium (NiCr) protective layer, so as to maintain stable performance during the high-temperature tempering process of 650-700℃.

[0003] However, silver-based low-emissivity (LOW-E) glass suffers from a significant disadvantage in light transmission. Silver absorbs blue-violet light (wavelength <500 nm) more strongly in the visible light band, while its absorption of green light (wavelength 500-560 nm) and red light (>600 nm) is relatively weak. Furthermore, the interference and reflection of blue light by the dielectric layer (such as Si3N4) further weakens the transmission of blue light. As a result, the green light component dominates in the transmission spectrum, giving the building a greenish hue and affecting its aesthetic appeal. Summary of the Invention The main objective of this invention is to propose a LOW-E glass and its preparation method, aiming to solve the technical problem of greenish tint in existing silver-based low-emissivity LOW-E glass.

[0004] To achieve the above objectives, the present invention proposes a LOW-E glass, characterized in that the LOW-E glass comprises a substrate glass, a first low-emissivity layer and a copper alloy tinting layer disposed sequentially, wherein the first low-emissivity layer comprises a first silver layer; The copper alloy tinting layer includes: Cu x A 1-x The A includes at least one of Zn, Ta, and Nb.

[0005] In one implementation, 0.7 ≤ x ≤ 0.99.

[0006] In one embodiment, A comprises Zn, where 0.7 ≤ x ≤ 0.85.

[0007] In one embodiment, the first low-emissivity layer further includes a first dielectric layer and a first protective layer. The first dielectric layer is disposed between the substrate glass and the first silver layer, and the first protective layer is connected to the first silver layer and disposed on the side away from the substrate glass. And / or, the thickness of the copper alloy tinting layer is 1-15 nm.

[0008] In one embodiment, the Low-E glass further includes a top dielectric layer disposed on the side of the copper alloy tinting layer opposite to the first protective layer, and the top dielectric layer is the outermost layer of the Low-E glass.

[0009] In one embodiment, the LOW-E glass further includes a second lower sub-dielectric layer and a second upper sub-dielectric layer, with the second lower sub-dielectric layer and the second upper sub-dielectric layer respectively disposed on both sides of the copper alloy tinting layer. The second lower sub-dielectric layer is located between the copper alloy tinting layer and the first protective layer, and the second upper sub-dielectric layer is disposed close to the top dielectric layer.

[0010] In one embodiment, the LOW-E glass further includes a second low-emissivity layer, which includes a second silver layer and a second protective layer. The second silver layer and the second protective layer are sequentially disposed between the second upper sub-dielectric layer and the top dielectric layer. The second silver layer is located on the side of the second upper sub-dielectric layer closer to the top dielectric layer, and the second protective layer is located between the second silver layer and the top dielectric layer.

[0011] In one embodiment, the first low-emissivity layer further includes a first transition layer located between the first dielectric layer and the first silver layer; The second low-emissivity layer also includes a second transition layer, which is located between the second protective layer and the top dielectric layer.

[0012] This invention also proposes a method for preparing LOW-E glass, characterized by comprising the following steps: A first low-emissivity layer and a copper alloy color layer are sequentially deposited on the surface of the cleaned substrate glass. The first silver layer is deposited during the deposition of the first low-emissivity layer to obtain an intermediate product. The intermediate product is tempered at 650-700℃ for 3-5 minutes, and then cooled to obtain LOW-E glass.

[0013] In one embodiment, the copper alloy tinting layer is deposited using at least one of the following methods: (1) Under working gas, a copper alloy color layer is obtained by magnetron sputtering using a Cu-A alloy target; wherein, A includes at least one of Zn, Ta and Nb; (2) Under working gas, magnetron sputtering is performed simultaneously using a pure Cu target and an A-containing target to obtain a copper alloy color layer; wherein, the A-containing target is a single metal target or a multi-element alloy target: the single metal target is any one of a pure Zn target, a pure Ta target, and a pure Nb target; the multi-element alloy target is an alloy target composed of any two or three elements of Zn, Ta, and Nb.

[0014] The technical solution of this invention involves the preferential reaction of zinc, tantalum, or niobium in the copper alloy tinting layer with oxygen before copper under high-temperature tempering conditions (650-700℃), forming a dense oxide layer of zinc oxide, tantalum oxide, or niobium oxide thin film on the surface of the copper alloy tinting layer 4. The presence of these oxides modulates the interference conditions, causing the transmitted color to shift from red to a neutral color. This reduces the color coordinate a* value (red-green axis) from +10 to +15 for pure copper to -2 to +3.5, which is beneficial for adjusting the transmitted color of LOW-E glass closer to a neutral color, eliminating the green tint of traditional silver-based low-emissivity LOW-E glass, and meeting architectural aesthetic requirements. Attached Figure Description

[0015] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the structures shown in these drawings without creative effort.

[0016] Figure 1 This is a schematic diagram of the structure of the LOW-E glass of the present invention.

[0017] The substrate glass consists of: a first low-emissivity layer 2, a first dielectric layer 21, a first silver layer 22, a first protective layer 23, a first transition layer 24, a second lower dielectric layer 3, a copper alloy color-matching layer 4, a second upper dielectric layer 5, a second low-emissivity layer 6, a second silver layer 61, a second protective layer 62, a second transition layer 63, and a top dielectric layer 7.

[0018] The realization of the objective, functional features and advantages of the present invention will be further explained in conjunction with the embodiments and with reference to the accompanying drawings. Detailed Implementation

[0019] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0020] It should be noted that if the embodiments of the present invention involve directional indicators (such as up, down, left, right, front, back, etc.), the directional indicators are only used to explain the relative positional relationship and movement of the components in a specific posture. If the specific posture changes, the directional indicators will also change accordingly.

[0021] Furthermore, if the embodiments of this invention involve descriptions such as "first" or "second," these descriptions are for descriptive purposes only and should not be construed as indicating or implying their relative importance or implicitly specifying the number of technical features indicated. Thus, a feature defined with "first" or "second" may explicitly or implicitly include at least one of those features. Additionally, the use of "and / or" or "and / or" throughout the text includes three parallel solutions. For example, "A and / or B" includes solution A, solution B, or a solution where both A and B are satisfied simultaneously. Furthermore, the technical solutions of the various embodiments can be combined with each other, but this must be based on the ability of those skilled in the art to implement them. When the combination of technical solutions is contradictory or impossible to implement, it should be considered that such a combination of technical solutions does not exist and is not within the scope of protection claimed by this invention.

[0022] Low-E glass is a key material in the field of building energy conservation. It achieves effective reflection of infrared radiation by depositing dielectric and functional layers on the glass surface. Traditional temperable low-E glass generally uses silver as the infrared reflective functional layer, combined with a silicon nitride (Si3N4) dielectric layer and a nickel-chromium (NiCr) protective layer, so as to maintain stable performance during the high-temperature tempering process of 650-700℃.

[0023] However, silver-based low-emissivity (LOW-E) glass suffers from a significant disadvantage in light transmission. Silver absorbs blue-violet light (wavelength <500 nm) more strongly in the visible light band, while its absorption of green light (wavelength 500-560 nm) and red light (>600 nm) is relatively weak. Furthermore, the interference and reflection of blue light by the dielectric layer (such as Si3N4) further weakens the transmission of blue light. As a result, the green light component dominates in the transmission spectrum, giving the building a greenish hue and affecting its aesthetic appeal. To overcome the above-mentioned defects, the present invention proposes a LOW-E glass, wherein the LOW-E glass comprises a substrate glass 1, a first low-emissivity layer 2 and a copper alloy color-matching layer 4 arranged sequentially, and the first low-emissivity layer 2 comprises a first silver layer 22. The copper alloy tinting layer 4 includes: Cu x A 1-x The A includes at least one of Zn, Ta, and Nb.

[0024] Copper, due to its unique metallic luster and optical properties, can effectively control the reflected and transmitted colors of glass. However, pure copper film introduces a strong reddish tint. Under tempering high-temperature conditions (650-700℃), zinc, tantalum, or niobium in the copper alloy color-tuning layer 4 react preferentially with oxygen, forming a dense oxide layer of zinc oxide, tantalum oxide, or niobium oxide on the surface of the copper alloy color-tuning layer 4. The presence of these oxides modulates the interference conditions, causing the transmitted color to shift from red to a neutral color. This reduces the color coordinate a* value (red-green axis) from +10 to +15 for pure copper to -2 to +3.5, which helps to adjust the transmitted color closer to a neutral color, eliminating the greenish tint of traditional silver-based low-emissivity (LOW-E) glass and meeting architectural aesthetic requirements.

[0025] Under high-temperature tempering conditions (650-700℃), the oxide film layer formed by the reaction of zinc, tantalum, or niobium with oxygen prevents oxygen from diffusing inward, protecting the internal copper from oxidation. Simultaneously, the addition of zinc, tantalum, or niobium atoms reduces the size of the copper grains and increases the grain boundary density, making the copper alloy tinting layer 4 more compact and effectively blocking the channels for oxygen diffusion along the grain boundaries. The combined effect of these factors allows zinc, tantalum, or niobium to protect the copper, effectively avoiding the technical problem of copper easily oxidizing and failing as a tinting layer, thus ensuring its tinting performance.

[0026] Furthermore, the chemical composition of this technical solution is Cu. x A 1-x The copper alloy coloring layer 4 remains stable in air at 650-700℃, eliminating the need for nitrogen protection modifications to the tempering furnace, significantly lowering the equipment threshold and enabling high industrialization.

[0027] It should be noted that the first silver layer 22, as the core infrared reflective layer, is responsible for reflecting infrared thermal radiation in different wavelengths to reduce emissivity, which is beneficial for achieving low radiation. It should also be noted that the thickness of the first silver layer 22 is preferably 5-20 nm, which helps to balance cost and low radiation performance.

[0028] In an embodiment of the present invention, 0.7 ≤ x ≤ 0.99.

[0029] Limiting the range of x helps to reduce the amount of precious metals tantalum and niobium used while ensuring the color-tuning effect of the copper alloy color-tuning layer 4, thereby reducing the cost of the copper alloy color-tuning layer 4 and thus reducing production costs. The value of x includes, but is not limited to, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 0.99, or any interval formed by any two of the above values.

[0030] In an embodiment of the present invention, A includes Zn, where 0.7 ≤ x ≤ 0.85.

[0031] x is defined as the atomic percentage of Cu in the copper alloy tinting layer 4. Zinc has a high vapor pressure and is easily oxidized. If x > 0.85 (i.e., Cu content is too high and Zn content is too low), the protective effect of zinc on copper is insufficient, and the copper alloy tinting layer 4 is easily oxidized in high-temperature or oxidizing environments, resulting in a weakened tinting effect. If x < 0.7 (i.e., Cu content is too low and Zn content is too high), too much zinc oxide (ZnO) will be generated. Zinc oxide is white or grayish-white, which will weaken the metallic luster of the copper alloy and change the transmission / reflection spectrum, thus affecting the hue of the copper alloy tinting layer 4. Therefore, x needs to be limited to the range of 0.7 ≤ x ≤ 0.85 (i.e., Cu atomic ratio 70-85%, Zn atomic ratio 15-30%) to further ensure a balance between tinting effect and high-temperature resistance.

[0032] In an embodiment of the present invention, the first low-emissivity layer 2 further includes a first dielectric layer 21 and a first protective layer 23. The first dielectric layer 21 is disposed between the substrate glass 1 and the first silver layer 22, and the first protective layer 23 is connected to the first silver layer 22 and disposed on the side away from the substrate glass 1. And / or, the thickness of the copper alloy tinting layer 4 is 1-15 nm.

[0033] This technical solution employs a first dielectric layer 21 and a first protective layer 23. The first dielectric layer 21 functions to control the transmitted / reflected colors through optical interference, block sodium ion diffusion, and protect the first silver layer 22. The first protective layer 23 prevents the first silver layer 22 from being oxidized or agglomerated during high-temperature tempering. It should be noted that the chemical composition of the first protective layer 23 can be any one of NiCr and Ti, and its thickness can be 1-5 nm. The chemical composition of the first dielectric layer 21 can be any one of Si3N4 and SiAlNz, where 1 ≤ z ≤ 4 / 3, and its thickness can be 20-80 nm.

[0034] Furthermore, its chemical composition is Cu. x A 1-x Although the resistivity of the copper alloy toning layer 4 is slightly higher than that of the copper alloy toning layer 4 formed from pure copper, the 1-15 nm thickness of the copper alloy toning layer 4 has minimal impact on the overall emissivity, and the U value can be maintained at 1.2-1.4 W / (m²). 2 Within the range of K), this helps to ensure that the LOW-E glass with the copper alloy toning layer 4 still maintains low radiation performance. The thickness of the copper alloy toning layer 4 includes, but is not limited to, 1 nm, 2 nm, 3 nm, 4 nm, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, 10 nm, 11 nm, 12 nm, 13 nm, 14 nm, 15 nm, or any two of the above values ​​as endpoints.

[0035] Preferably, the thickness of the copper alloy color-tuning layer 4 is 2 nm-8 nm, and more preferably, the thickness of the copper alloy color-tuning layer 4 is 3 nm-5 nm. This technical solution further optimizes the thickness of the copper alloy color-tuning layer 4, which is more conducive to balancing cost, low radiation performance, and color-tuning performance.

[0036] In an embodiment of the present invention, the Low-E glass further includes a top dielectric layer 7, which is disposed on the side of the copper alloy tinting layer 4 away from the first protective layer 23, and the top dielectric layer 7 is the outermost layer of the Low-E glass.

[0037] This technical solution, by setting a top dielectric layer 7, can effectively isolate external oxygen and moisture, inhibit the oxidation and discoloration of the copper alloy layer, and ensure the long-lasting stability of the color tuning effect. At the same time, the top dielectric layer 7 can act as an optical matching layer to interfere and control the reflected light generated by the copper alloy layer, eliminate unwanted metallic luster or color deviation, and further control the hue of the LOW-E glass.

[0038] It should be noted that the chemical composition of the top dielectric layer 7 can be either Si3N4 or SiAlNz, and 1≤z≤4 / 3; the thickness of the top dielectric layer can be 20-80 nm.

[0039] In an embodiment of the present invention, the LOW-E glass further includes a second lower sub-dielectric layer 3 and a second upper sub-dielectric layer 5, and the second lower sub-dielectric layer 3 and the second upper sub-dielectric layer 5 are respectively disposed on both sides of the copper alloy tinting layer 4. The second lower sub-dielectric layer 3 is located between the copper alloy tinting layer 4 and the first protective layer 23, and the second upper sub-dielectric layer 5 is disposed close to the top dielectric layer 7.

[0040] A second upper sub-dielectric layer 5 and a second lower sub-dielectric layer 3 are disposed inside the second dielectric layer. The second upper sub-dielectric layer 5 and the second lower sub-dielectric layer 3 can prevent the copper alloy coloring layer 4 from directly contacting other film layers, avoid interlayer diffusion or electrochemical corrosion, and play a role in dielectric coverage and isolation.

[0041] It should be noted that the chemical composition of the second upper dielectric layer 5 and the second upper dielectric layer 5 can be either Si3N4 or SiAlNz, and 1≤z≤4 / 3, and the thickness of both can be 20-80 nm.

[0042] In an embodiment of the present invention, the LOW-E glass further includes a second low-emissivity layer 6, which includes a second silver layer 61 and a second protective layer 62. The second silver layer 61 and the second protective layer 62 are sequentially disposed between the second upper sub-dielectric layer 5 and the top dielectric layer 7. The second silver layer 61 is located on the side of the second upper sub-dielectric layer 5 closer to the top dielectric layer 7, and the second protective layer 62 is located between the second silver layer 61 and the top dielectric layer 7.

[0043] This technical solution utilizes a second silver layer 61 to further reduce the heat radiation of the LOW-E glass. A second protective layer 62 is used to prevent the second silver layer 61 from oxidizing or agglomerating during the high-temperature tempering process.

[0044] It should be noted that the chemical composition of the second protective layer 62 can be either NiCr or Ti; the thickness of the second protective layer 62 can be 1-5 nm. The thickness of the second silver layer 61 can be 5-20 nm.

[0045] In an embodiment of the present invention, the first low-emissivity layer 2 further includes a first transition layer 24, the first transition layer 24 being located between the first dielectric layer 21 and the first silver layer 22; The second low-emissivity layer 6 further includes a second transition layer 63, which is located between the second protective layer 62 and the top dielectric layer 7.

[0046] The first transition layer 24 is provided between the first dielectric layer 21 and the first silver layer 22, which can significantly improve the lattice matching degree and interfacial bonding force between the first dielectric layer 21 and the first silver layer 22, improve the adhesion between the first dielectric layer 21 and the first silver layer 22, prevent the first silver layer 22 from agglomerating or falling off during the high-temperature tempering process, and at the same time block high-energy particles from damaging the first silver layer 22 during the deposition of the first dielectric layer 21.

[0047] A second transition layer 63 is provided between the second protective layer 62 and the top dielectric layer 7, so that a buffer interface is formed between the second protective layer 62 and the top dielectric layer 7, which can effectively release the internal stress between the layers, avoid cracking of the multilayer film due to the difference in thermal expansion coefficient, and enhance the adhesion of the top dielectric layer 7 to the second protective layer 62.

[0048] In a preferred embodiment, the chemical composition of both the first transition layer 24 and the second transition layer 63 is TiOy, and 1≤y≤2; And / or, the thickness of the first transition layer 24 and the second transition layer 63 is 1-5 nm.

[0049] Non-stoichiometric TiOy (i.e., titanium oxide) combines high refractive index with optical control capabilities and certain chemical activity. Its incomplete oxidation state can absorb or block residual oxygen diffused to the interface, thereby protecting the first silver layer 22 from oxidation at high temperatures.

[0050] The thickness of both the first transition layer 24 and the second transition layer 63 is 1-5 nm. This ultra-thin thickness is sufficient to form a continuous and dense transition buffer layer, improving adhesion, without significantly increasing visible light absorption or altering the optical interference effect of the original film system due to excessive film thickness, thus ensuring that the transmittance of the glass is not negatively affected. The thickness of the first transition layer 24 and the second transition layer 63 includes, but is not limited to, 1 nm, 2 nm, 3 nm, 4 nm, 5 nm, or any two of the above values ​​as endpoints.

[0051] This invention also proposes a method for preparing LOW-E glass, characterized by comprising the following steps: A first low-emissivity layer 2 and a copper alloy color-coating layer 4 are sequentially deposited on the surface of the cleaned substrate glass 1. During the deposition of the first low-emissivity layer 2, the deposition of the first silver layer 22 is completed, and an intermediate product is obtained. The intermediate product is tempered at 650-700℃ for 3-5 minutes, and then cooled to obtain LOW-E glass.

[0052] This technical solution incorporates a copper alloy color-tuning layer 4 within the LOW-E glass. This copper alloy color-tuning layer 4 is not easily oxidized or degraded during tempering at 650-700℃ for 3-5 minutes. Furthermore, the copper alloy color-tuning layer 4 can shift the transmitted color from red to a neutral color, thereby adjusting the transmitted color of the LOW-E glass closer to a neutral color and eliminating the green tint of traditional LOW-E glass.

[0053] Meanwhile, the proposed method for preparing LOW-E glass involves first completing the entire coating process, followed by high-temperature tempering. This approach avoids damage to the film layers during deposition. Furthermore, the high temperature (650-700℃) of the tempering process promotes beneficial diffusion and structural densification of the copper alloy tinting layer 4. This not only improves the adhesion and oxidation resistance between film layers but also enables a one-step process for glass strengthening and optical performance optimization, simplifying the process and reducing costs.

[0054] Preferably, the step of obtaining the intermediate product includes the following steps: An intermediate product is obtained by sequentially depositing a first low-emissivity layer 2, a second lower dielectric layer 3, a copper alloy color layer 4, a second upper dielectric layer 5, a second low-emissivity layer 6, and a top dielectric layer 7 on the surface of the cleaned substrate glass 1.

[0055] Preferably, the first low-emissivity layer 2 is prepared by depositing a first dielectric layer 21, a first transition layer 24, a first silver layer 22 and a first protective layer 23 sequentially on the surface of the cleaned substrate glass 1. The second low-emissivity layer 6 is prepared by sequentially depositing a second silver layer 61, a second protective layer 62, and a second transition layer 63 on the surface of the second upper dielectric layer 5.

[0056] In embodiments of the present invention, the copper alloy color layer 4 is deposited using at least one of the following methods: (1) Under working gas, a Cu-A alloy target is used for magnetron sputtering to obtain a copper alloy color layer 4; wherein, A includes at least one of Zn, Ta and Nb; (2) Under working gas, magnetron sputtering is performed simultaneously using a pure Cu target and an A-containing target to obtain a copper alloy color layer 4; wherein the A-containing target is a single metal target or a multi-element alloy target: the single metal target is any one of a pure Zn target, a pure Ta target, and a pure Nb target; the multi-element alloy target is an alloy target composed of any two or three elements of Zn, Ta, and Nb.

[0057] In method (1), the high uniformity and batch stability of the film composition can be guaranteed in large-scale production. In method (2), there is no need to customize complex alloy targets. The ratio of Cu to A in the copper alloy color layer 4 can be quickly switched by simply adjusting the power ratio of the pure copper target and the A-containing target, which is highly flexible. At the same time, both of the above methods can deposit copper alloy color layer 4 with good optical color adjustment function, providing a technical path with both stability and flexibility for different mass production scales and performance requirements. In addition, the magnetron sputtering method for preparing copper alloy color layer 4 in this technical solution is highly compatible with existing coating production lines and is suitable for large-scale production of LOW-E glass.

[0058] Preferably, in both methods (1) and (2), the working gas is pure argon, and the flow rate of the working gas is 500-1200 cm⁻¹. 3 / min, air pressure is 0.3-0.5 Pa.

[0059] The type of working gas determines the ionization efficiency and bombardment quality; the flow rate of the working gas affects the gas renewal rate and impurity removal; if the working gas pressure is too low, the discharge is unstable, and if the working gas pressure is too high, the film layer is loose and the rate decreases. Therefore, this technical solution, by limiting the type, flow rate, and pressure of the working gas, is beneficial to stabilizing plasma discharge, controlling the energy of sputtered atoms and the deposition process, thereby regulating the density, uniformity, deposition rate, and compositional accuracy of the copper alloy toning layer 4, and obtaining a dense, well-bonded, and consistent copper alloy toning layer 4.

[0060] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following specific embodiments are only used to explain the present invention and are not intended to limit the present invention.

[0061] Example 1 S1. Clean and dry the substrate glass (sodium-calcium silicate glass), and place it under a vacuum of ≤5×10⁻⁶. -4 Pa's vacuum sputtering region; At a flow rate of 600 cm 3 In a mixed atmosphere of argon and nitrogen at a pressure of 0.4 Pa and a pressure of 0.4 Pa, magnetron sputtering was performed on the cleaned substrate glass surface using a Si target at a power of 20 kW to obtain a first dielectric layer with a thickness of 40 nm. At a flow rate of 500 cm 3 Under a pure argon atmosphere with a pressure of 0.3 Pa and an Ag target, magnetron sputtering was performed on the surface of the first dielectric layer at a power of 5 kW to obtain a first silver layer with a thickness of 10 nm. At a flow rate of 800 cm 3 Under a pure argon atmosphere with a gas pressure of 0.5 Pa and a NiCr target, magnetron sputtering was performed on the surface of the first silver layer at a power of 10 kW to obtain a first protective layer with a thickness of 3 nm. S2, at a flow rate of 600 cm³ 3 Under a mixed atmosphere of argon and nitrogen at a pressure of 0.3 Pa and a pressure of 0.3 Pa, magnetron sputtering was performed on the surface of the first protective layer using a Si target at a power of 30 kW to obtain a second sub-dielectric layer with a thickness of 50 nm. At a flow rate of 1200 cm 3 Under a pure argon atmosphere with a gas pressure of 0.4 Pa and a Cu-Zn alloy target, magnetron sputtering was performed on the surface of the second dielectric layer at a power of 6 kW to obtain a copper alloy coloring layer with a thickness of 5 nm. The Cu-Zn alloy target contains 80% Cu atoms by mass and 20% Zn atoms by mass. At a flow rate of 500 cm 3 In a mixed atmosphere of argon and nitrogen at a pressure of 0.3 Pa and a pressure of 0.3 Pa, magnetron sputtering was performed on the surface of a copper alloy color layer using a Si target at a power of 10 kW to obtain a second upper dielectric layer with a thickness of 20 nm. S3, at a flow rate of 600 cm³ 3 Under a pure argon atmosphere with a pressure of 0.4 Pa and an Ag target, magnetron sputtering was performed on the surface of the second upper dielectric layer at a power of 3 kW to obtain a second silver layer with a thickness of 15 nm. At a flow rate of 700 cm3 Under a pure argon atmosphere with a gas pressure of 0.4 Pa and a NiCr target, magnetron sputtering was performed on the surface of the second silver layer at a power of 20 kW to obtain a second protective layer with a thickness of 3 nm. At a flow rate of 800cm 3 Under a mixed atmosphere of argon and nitrogen at a pressure of 0.4 Pa and a pressure of 0.4 Pa, magnetron sputtering was performed on the surface of the second protective layer using a Si target at a power of 80 kW to obtain a top dielectric layer with a thickness of 50 nm, thus obtaining an intermediate product. S4. Temper the intermediate product at 680℃ for 4 minutes, and then cool it to obtain LOW-E glass.

[0062] The structure of the LOW-E glass in Example 1 is shown in the table below:

[0063] Example 2 Example 2 is basically the same as Example 1. The difference between Example 2 and Example 1 is that the preparation method of the color layer in Example 2 is different from that in Example 1.

[0064] The specific preparation method of the copper alloy color-correcting layer in Example 2 is as follows: at a flow rate of 800 cm⁻¹ 3 Under a pure argon atmosphere with a pressure of 0.4 Pa and a Cu-Zn alloy target, magnetron sputtering was performed on the surface of the second sub-dielectric layer at a power of 6 kW to obtain a copper alloy coloring layer with a thickness of 4 nm. The Cu-Zn alloy target has a Cu atom mass percentage of 85% and a Zn atom mass percentage of 15%.

[0065] The structure of the LOW-E glass in Example 2 is shown in the table below:

[0066] Example 3 Example 3 is basically the same as Example 1. The difference between Example 3 and Example 1 is that the preparation method of the color layer in Example 3 is different from that in Example 1.

[0067] The specific preparation method of the copper alloy color-correcting layer in Example 3 is as follows: at a flow rate of 600 cm⁻¹ 3 Under a pure argon atmosphere with a speed of 0.4 Pa and a pressure of 0.4 Pa, magnetron sputtering was performed simultaneously on the surface of the second sub-dielectric layer using pure Cu and pure Zn targets to obtain a copper alloy coloring layer with a thickness of 2 nm; wherein the sputtering power of the pure Cu target was 5 kW and the sputtering power of the pure Zn target was 2 kW.

[0068] The structure of the LOW-E glass in Example 3 is shown in the table below:

[0069] Example 4 Example 4 is basically the same as Example 1. The difference between Example 4 and Example 1 is that the preparation method of the color layer in Example 4 is different from that in Example 1.

[0070] The specific preparation method of the copper alloy color-matching layer in Example 4 is as follows: at a flow rate of 1200 cm⁻¹ 3 Under a pure argon atmosphere with a pressure of 0.4 Pa and a Cu-Ta alloy target, magnetron sputtering was performed on the surface of the second sub-dielectric layer at a power of 6 kW to obtain a copper alloy coloring layer with a thickness of 5 nm. The Cu-Ta alloy target has a Cu atom mass percentage of 95% and a Ta atom mass percentage of 5%.

[0071] The structure of the LOW-E glass in Example 4 is shown in the table below:

[0072] Example 5 Example 5 is basically the same as Example 1. The difference between Example 5 and Example 1 is that the preparation method of the color layer in Example 5 is different from that in Example 1.

[0073] The specific preparation method of the copper alloy color-matching layer in Example 5 is as follows: at a flow rate of 1200 cm⁻¹ 3 Under a pure argon atmosphere with a pressure of 0.4 Pa and a Cu-Nb alloy target, magnetron sputtering was performed on the surface of the second sub-dielectric layer at a power of 6 kW to obtain a copper alloy coloring layer with a thickness of 5 nm. The Cu-Nb alloy target has a Cu atom mass percentage of 90% and a Nb atom mass percentage of 10%.

[0074] The structure of the LOW-E glass in Example 5 is shown in the table below:

[0075] Example 6 Example 6 is basically the same as Example 1. The difference between Example 6 and Example 1 is that: in Example 6, a first transition layer is provided between the first dielectric layer and the first silver layer; and a second transition layer is provided between the second protective layer and the top dielectric layer.

[0076] In Example 6, step S1 specifically involves: Clean and dry the substrate glass (sodium-calcium silicate glass), and place it under a vacuum of ≤5×10⁻⁶. -4 Pa's vacuum sputtering region; At a flow rate of 600 cm 3In a mixed atmosphere of argon and nitrogen at a pressure of 0.4 Pa and a pressure of 0.4 Pa, magnetron sputtering was performed on the cleaned substrate glass surface using a Si target at a power of 20 kW to obtain a first dielectric layer with a thickness of 40 nm. At a flow rate of 500 cm 3 Under a mixed atmosphere of argon and oxygen at a pressure of 0.4 Pa and a Ti target, magnetron sputtering was performed on the surface of the first dielectric layer at a power of 5 kW; wherein the flow rate ratio of oxygen to argon was 1:2, resulting in a first transition layer with a thickness of 2 nm. At a flow rate of 500 cm 3 Under a pure argon atmosphere with a gas pressure of 0.3 Pa and an Ag target, magnetron sputtering was performed on the surface of the first transition layer at a power of 5 kW to obtain a first silver layer with a thickness of 10 nm. At a flow rate of 800 cm 3 Under a pure argon atmosphere with a gas pressure of 0.5 Pa and a NiCr target, magnetron sputtering was performed on the surface of the first silver layer at a power of 10 kW to obtain a first protective layer with a thickness of 3 nm.

[0077] Step S3 in Example 6 specifically includes: At a flow rate of 600 cm 3 Under a pure argon atmosphere with a pressure of 0.4 Pa and an Ag target, magnetron sputtering was performed on the surface of the second upper dielectric layer at a power of 3 kW to obtain a second silver layer with a thickness of 15 nm. At a flow rate of 700 cm 3 Under a pure argon atmosphere with a gas pressure of 0.4 Pa and a NiCr target, magnetron sputtering was performed on the surface of the second silver layer at a power of 20 kW to obtain a second protective layer with a thickness of 1-5 nm. At a flow rate of 500 cm 3 Under a mixed atmosphere of argon and oxygen at a pressure of 0.4 Pa and a Ti target, magnetron sputtering was performed on the surface of the first dielectric layer at a power of 5 kW; wherein the flow rate ratio of oxygen to argon was 1:5, resulting in a second transition layer with a thickness of 2 nm. At a flow rate of 800cm 3 Under a mixed atmosphere of argon and nitrogen at a pressure of 0.4 Pa and a pressure of 0.4 Pa, magnetron sputtering was performed on the surface of the second transition layer using a Si target at a power of 80 kW to obtain a top dielectric layer with a thickness of 20-80 nm, thus obtaining an intermediate product.

[0078] The structure of the LOW-E glass in Example 6 is shown in the table below:

[0079] Example 7 Example 7 is basically the same as Example 1. The difference between Example 7 and Example 1 is that no second low-emissivity layer is set in Example 7.

[0080] The structure of the LOW-E glass in Example 7 is shown in the table below:

[0081] Comparative Example 1 Comparative Example 1 is basically the same as Example 1, except that: in Comparative Example 1... Replace the Cu-Zn alloy target with a pure copper target.

[0082] Comparative Example 2 Comparative Example 2 is basically the same as Example 1, except that: Comparative Example 2 The mass percentage of Cu atoms in the Cu-Zn alloy target is 50%, and the mass percentage of Zn atoms is 50%.

[0083] The performance of the LOW-E glass prepared in the examples and comparative examples was tested according to the following methods: (1) Through color The measurements were conducted according to GB / T 36142-2018, "Methods for Measurement of Color and Color Difference of Architectural Glass". A spectrophotometer was used. Under D65 standard light source and a 10° field of view, the samples were cleaned with anhydrous ethanol and allowed to air dry naturally. The spectral transmittance within the wavelength range of 380-780 nm was measured, and the a* and b* values ​​were calculated according to the CIELAB color space.

[0084] (2) Emissivity The measurements were conducted according to GB / T 2680-2021, "Determination of Visible Light Transmittance, Direct Solar Transmittance, Total Solar Transmittance, Ultraviolet Transmittance and Related Parameters of Architectural Glass". During the test, the hemispherical emissivity was measured in the far-infrared band with wavelengths of 4.5-25 μm at a temperature of 293 K.

[0085] (3) Oxidative discoloration properties The test was conducted according to GB / T 18915.2-2013 "LOW-E Glass Part 2: Low-emissivity LOW-E Glass". Under a D65 standard light source, the tempered LOW-E glass was placed in a color matching light box and observed at a 45° angle from a distance of about 1 m from the sample. If the LOW-E glass showed no oxidation change after tempering, its oxidation discoloration performance was qualified.

[0086] (4) Adhesion test The test was conducted according to GB / T 9286-2021 "Cross-cut Test for Paints and Varnishes". A 10×10 grid with a 1 mm spacing was drawn on the film surface using a cross-cutting tool. The cut depth must penetrate the film to the substrate glass 1. After gently brushing away any debris from the scratches with a soft brush, 3M 600 tape (adhesion strength approximately 10 N / 25 mm) was applied to the grid area. Air bubbles were removed by pressing with a finger or rubber roller. After standing for 1-2 minutes, the tape was quickly peeled off at a 60° angle. A pass was considered achieved when the test result was ISO 0 (completely smooth cut edges, no peeling of the squares) or ASTM 5B (0% peeling area).

[0087] Table 1 Performance Test Results

[0088] As shown in Table 1, the a* value of the LOW-E glass prepared in Examples 1-7 is reduced to -2 to +3.5, and the b* value is +1.2 to +4.8. Therefore, in this application, by adjusting the proportion of x in the chemical composition of the copper alloy tinting layer, a neutral tone can be achieved, eliminating the green tint of traditional silver-based low-emissivity LOW-E glass and meeting architectural aesthetic requirements.

[0089] Meanwhile, the LOW-E glass obtained in Examples 1-7 of this application has no oxidation discoloration, excellent emissivity and adhesion, which helps to overcome the technical problem that the LOW-E glass with copper alloy tinting layer can be tinted without oxidizing and failing, while maintaining low emissivity.

[0090] In Comparative Example 1, the Cu-Zn alloy target was replaced with a pure copper target, resulting in a pure copper toning layer. This caused the color to appear reddish before tempering and dark green after tempering, indicating obvious oxidation and visible black oxide spots on the surface.

[0091] In Comparative Example 2, due to the excessively low content of Cu atoms and excessively high content of Zn atoms in the Cu-Zn alloy target, the amount of zinc oxide that produces a dull or whitish color is excessive, affecting the hue of the copper alloy color layer, causing the transmitted color to be greenish, and the emissivity to be 0.18, which is too high, resulting in a decrease in low-emissivity performance.

[0092] The above description is merely an exemplary embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent structural transformations made using the contents of the present invention specification and drawings under the technical concept of the present invention, or direct / indirect applications in other related technical fields, are included within the patent protection scope of the present invention.

Claims

1. A LOW-E glass, characterized in that, The LOW-E glass comprises a substrate glass, a first low-emissivity layer and a copper alloy color-tuning layer arranged sequentially, wherein the first low-emissivity layer comprises a first silver layer. The copper alloy tinting layer includes: Cu x A 1-x The A includes at least one of Zn, Ta, and Nb.

2. The LOW-E glass as described in claim 1, characterized in that, 0.7≤x≤0.99。 3. The LOW-E glass as described in claim 1, characterized in that, The A includes Zn, where 0.7 ≤ x ≤ 0.

85.

4. The LOW-E glass as described in any one of claims 1 to 3, characterized in that, The first low-emissivity layer further includes a first dielectric layer and a first protective layer. The first dielectric layer is disposed between the substrate glass and the first silver layer, and the first protective layer is connected to the first silver layer and disposed on the side away from the substrate glass. And / or, the thickness of the copper alloy tinting layer is 1-15 nm.

5. The LOW-E glass as described in claim 4, characterized in that, The Low-E glass also includes a top dielectric layer, which is disposed on the side of the copper alloy tinting layer away from the first protective layer, and the top dielectric layer is the outermost layer of the Low-E glass.

6. The LOW-E glass as described in claim 5, characterized in that, The LOW-E glass further includes a second lower sub-dielectric layer and a second upper sub-dielectric layer, with the second lower sub-dielectric layer and the second upper sub-dielectric layer respectively disposed on both sides of the copper alloy tinting layer. The second lower sub-dielectric layer is located between the copper alloy tinting layer and the first protective layer, and the second upper sub-dielectric layer is disposed close to the top dielectric layer.

7. The LOW-E glass as described in claim 6, characterized in that, The LOW-E glass further includes a second low-emissivity layer, which includes a second silver layer and a second protective layer. The second silver layer and the second protective layer are sequentially disposed between the second upper sub-dielectric layer and the top dielectric layer. The second silver layer is located on the side of the second upper sub-dielectric layer closer to the top dielectric layer, and the second protective layer is located between the second silver layer and the top dielectric layer.

8. The LOW-E glass as described in claim 7, characterized in that, The first low-emissivity layer further includes a first transition layer located between the first dielectric layer and the first silver layer; The second low-emissivity layer also includes a second transition layer, which is located between the second protective layer and the top dielectric layer.

9. A method for preparing LOW-E glass, used to prepare LOW-E glass as described in any one of claims 1-8, characterized in that, Includes the following steps: A first low-emissivity layer and a copper alloy color layer are sequentially deposited on the surface of the cleaned substrate glass. The first silver layer is deposited during the deposition of the first low-emissivity layer to obtain an intermediate product. The intermediate product is tempered at 650-700℃ for 3-5 minutes, and then cooled to obtain LOW-E glass.

10. The method for preparing LOW-E glass as described in claim 9, characterized in that, The copper alloy tinting layer is deposited using at least one of the following methods: (1) Under working gas, a copper alloy color layer is obtained by magnetron sputtering using a Cu-A alloy target; wherein, A includes at least one of Zn, Ta and Nb; (2) Under working gas, magnetron sputtering is performed simultaneously using a pure Cu target and an A-containing target to obtain a copper alloy color layer; wherein, the A-containing target is a single metal target or a multi-element alloy target: the single metal target is any one of a pure Zn target, a pure Ta target, and a pure Nb target; the multi-element alloy target is an alloy target composed of any two or three elements of Zn, Ta, and Nb.

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