A Low-E coated glass tinting layer and its preparation method and use

Abstract

The present invention provides a tinting layer for Low-E coated glass, as well as a preparation method and use thereof. The coated glass comprises a glass substrate and a composite coating, wherein the composite coating comprises a first composite layer, a metal tinting layer, and a second composite layer sequentially laminated on the surface of the glass substrate, wherein the metal tinting layer comprises a single copper layer. The present invention adds a tinting layer to traditional double-silver Low-E glass, positioning it between a functional layer and a metal barrier layer. By selecting the material of the tinting layer, the transparent color after tempering can be maintained at a relatively neutral color. The multiple structural layers in the coated glass enable off-site processing, first coating and then tempering, thus avoiding the problem of the film layer being easily oxidized and detached after tempering heat treatment. The coated glass structural layers are rationally arranged, easy to process, effective, and have a wide range of applications.

Description

Technical Field

[0001] The invention belongs to the technical field of coated glass and relates to a Low-E coated glass color adjustment layer and a preparation method and application thereof. Background Art

[0002] Glass is an indispensable component in the field of architecture and undertakes many important functions, including beautifying buildings, providing lighting, and providing a broad field of vision. However, ordinary glass has a high sunlight transmittance and a low infrared reflectivity. Most of the sunlight passes through the glass and enters the room, thereby heating objects. The energy of indoor objects will be dissipated through the glass in the form of radiation. Therefore, it is necessary to coat the glass surface. By preparing coated glass, the optical properties of the glass can be changed and its thermal insulation performance can be improved.

[0003] Low-emissivity (Low-E) coated glass is a widely used type of coated glass. It can reduce the emissivity of the glass surface, improve the glass's spectral selectivity, and have a high reflectivity to infrared light, significantly reducing its heat transfer coefficient. Low-E coated glass can be divided into single-silver Low-E glass and double-silver Low-E glass. The former generally has a high visible light transmittance and excellent thermal insulation properties, but its solar energy blocking ability is relatively weak. To reduce solar energy transmittance, the only way is to increase the thickness of the Ag layer, which leads to a significant decrease in visible light transmittance. The latter generally combines the advantages of high visible light transmittance and low solar energy transmittance.

[0004] Low-E coated glass is typically produced by tempering before coating. However, this method produces double-silver Low-E coated glass with poor uniformity, severe edge effects, and high costs. Currently, there is also a method of coating first and then tempering to produce double-silver Low-E glass that can be processed remotely. This method offers advantages such as ease of processing, excellent energy-saving indicators, the ability to produce curved and tempered products, and ease of operation. However, compared to double-silver Low-E glass produced by traditional production methods, this remotely processed double-silver Low-E glass has a darker perspective color, with more negative red-green and yellow-blue values.

[0005] Cu thin films are widely used in offline Low-E coatings. Due to their inherent color and low-emissivity properties, they often play a role in color adjustment and improving the thermal insulation performance of glass. However, Cu thin films are very susceptible to oxidation when heated. According to relevant research reports, even coating the Cu thin films with sacrificial protective layers such as NiCr on both sides cannot prevent oxidation during heating. Therefore, Cu thin films cannot be used in temperable coated glass, and Cu-based temperable coating technology has not been widely used.

[0006] CN 202181260U discloses a double-silver temperable low-emissivity coated glass. The film layer structure of the coated glass comprises, from the glass outward, a glass substrate, a bottom dielectric combination layer, a first infrared-reflecting Ag layer, a first barrier layer, an intermediate dielectric combination layer, a second infrared-reflecting Ag layer, a second barrier layer, and a top dielectric combination layer. The coated glass is a conventional double-silver low-emissivity coated glass that can be tempered, but the color after tempering is not specified, that is, the perspective color of the coated glass is not adjusted.

[0007] CN 210481206U discloses ultra-low-reflection, low-transmittance, double-silver, low-emissivity (LE) coated glass. The coated glass comprises a glass substrate and, stacked outward from the surface of the glass substrate, a first dielectric film layer, an optical refractive film layer, a second dielectric film layer, a first functional film layer, a first functional protective film layer, a third dielectric film layer, a second functional film layer, a second functional protective film layer, and a fourth dielectric film layer. This coated glass is similar to conventional double-silver, low-emissivity (LE) coated glass, and its reflectivity is controlled by the arrangement of the film layers. However, the transparent color of the coated glass is not adjusted, and the requirement for neutral color cannot be guaranteed.

[0008] CN 218089368U discloses a neutral-colored double-silver low-emissivity glass that can be processed remotely. The low-emissivity glass comprises a glass substrate, on the surface of which a first composite layer, a non-metallic color-adjusting layer, and a second composite layer are sequentially laminated. The non-metallic color-adjusting layer comprises a silicon single-substance layer or a boron single-substance layer. The composite layers each comprise a dielectric layer, a functional layer, a metal barrier layer, etc. The outermost layer of the second composite layer is a protective layer. The non-metallic color-adjusting layer is provided to adjust the perspective color of the glass. However, the color-adjusting performance of the non-metallic layer is limited, making it difficult to form a good match with adjacent structural layers.

[0009] To sum up, for the setting of the film layer structure in Low-E coated glass, it is also necessary to set a suitable functional film layer according to the performance requirements of the coated glass, so that it can maintain the low radiation and high light transmittance characteristics of the coated glass while maintaining its neutral color. Summary of the Invention

[0010] In response to the problems existing in the prior art, the present invention aims to provide a Low-E coated glass tinting layer, a preparation method, and an application thereof. The coated glass adds a tinting layer to traditional double-silver Low-E glass, and arranges the tinting layer between the functional layer and the metal barrier layer. By selecting the material of the tinting layer, it can meet the requirements of first coating and then tempering heat treatment, and the perspective color after tempering heat treatment can also maintain a relatively neutral color.

[0011] To achieve this object, the present invention adopts the following technical solutions:

[0012] In a first aspect, the present invention provides a Low-E coated glass tinting layer, wherein the coated glass comprises a glass substrate and a composite coating, wherein the composite coating comprises a first composite layer, a metal tinting layer, and a second composite layer sequentially stacked on the surface of the glass substrate; the metal tinting layer comprises a copper single-element layer.

[0013] In the present invention, when Low-E coated glass is prepared by coating first and then tempering, the film layer is easily oxidized and demolded after the tempering heat treatment. The present invention can effectively avoid the problems of easy oxidation and easy falling off of the film layer after the tempering heat treatment by setting multiple structural layers in the composite coating, thereby achieving the effect of remote processing. By setting the copper compound-containing color adjustment layer, metallic Cu can be reduced after the tempering heat treatment to form a copper single-substance layer, which has a reddish-brown perspective effect, thereby improving the perspective color of the Low-E coated glass and enabling it to maintain a neutral color. The coated glass structural layers are reasonably arranged, easy to process, effective, and have a wide range of applications.

[0014] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. Through the following technical solutions, the technical objectives and beneficial effects of the present invention can be better achieved and realized.

[0015] As a preferred technical solution of the present invention, a composite coating is provided on one surface of the glass substrate, and the total thickness of the composite coating is 180 to 270 nm, for example, 180 nm, 200 nm, 210 nm, 220 nm, 230 nm, 240 nm, 250 nm, 260 nm or 270 nm, etc., but is not limited to the listed values, and other values ​​not listed within this numerical range are also applicable.

[0016] Preferably, the glass substrate is any one of transparent float glass, colored float glass or ultra-clear float glass, and the thickness of the glass substrate is 2 to 20 mm, for example, 2 mm, 4 mm, 6 mm, 8 mm, 10 mm, 12 mm, 15 mm, 18 mm or 20 mm, etc., but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0017] Preferably, the thickness of the metal coloring layer is 2-5 nm, for example, 2 nm, 2.5 nm, 3 nm, 3.5 nm, 4 nm, 4.5 nm or 5 nm, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0018] In a second aspect, the present invention provides a method for preparing the above-mentioned Low-E coated glass tinting layer, the preparation method comprising:

[0019] (1) After the first composite layer is plated on the glass substrate, CuN is obtained by using metallic copper as the raw material and vacuum magnetic sputtering technology and filling it with inert gas and nitrogen. x membrane layer;

[0020] (2) in step (1) the CuN x A second composite layer is plated on the basis of the film layer, and after the coating is completed, heat treatment is performed to obtain a coated glass containing a copper single substance coloring layer.

[0021] In the present invention, CuN x The characteristics of decomposition and reduction under heating conditions, CuN is added to the original double silver low-emissivity coated glass in a nitrogen atmosphere. x Film, using the temperature of glass tempering to x It is fully decomposed to improve the perspective color of Low-E coated glass.

[0022] As a preferred technical solution of the present invention, the target material for vacuum magnetic sputtering in step (1) is a copper target.

[0023] Preferably, before filling the inert gas and nitrogen in step (1), the vacuum is first evacuated to a pressure of 9×10 -6 mbar or less, for example 9×10 -6 mbar, 8×10 -6 mbar, 6×10 -6 mbar, 4×10 -6 mbar, 2×10 -6 mbar or 1×10 -6 mbar, etc., but are not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0024] Preferably, the inert gas includes any one of helium, neon or argon, or a combination of at least two of them. Typical but non-limiting examples of the combination include: a combination of helium and neon, a combination of neon and argon, a combination of helium, neon and argon, etc.

[0025] Preferably, after the inert gas and nitrogen are filled in step (1), the pressure is controlled to be 9×10 -4 ~7×10 -3 mbar, for example 9×10 -4 mbar, 1×10 -3 mbar, 2×10 -3 mbar, 3×10 -3 mbar, 4×10 -3 mbar, 5×10 -3 mbar, 6×10 - 3 mbar or 7×10-3 mbar, etc., but are not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0026] Preferably, the volume ratio of the inert gas to nitrogen in step (1) is 5:1 to 5:2, for example, 5:1, 5:1.2, 5:1.4, 5:1.5, 5:1.6, 5:1.8 or 5:2, etc., but is not limited to the listed values, and other unlisted values ​​within this numerical range are also applicable.

[0027] As a preferred technical solution of the present invention, the temperature of the heat treatment in step (2) is 650-720°C, for example, 650°C, 660°C, 670°C, 680°C, 690°C, 700°C, 710°C or 720°C, etc., but is not limited to the listed values, and other unlisted values ​​within this numerical range are also applicable.

[0028] Preferably, the heat treatment time in step (2) is 200 to 600 s, for example, 200 s, 240 s, 300 s, 360 s, 420 s, 480 s, 540 s or 600 s, etc., but is not limited to the listed values, and other unlisted values ​​within this numerical range are also applicable.

[0029] Preferably, during the heat treatment in step (2), CuN x The decomposition gradually transforms into Cu, and the generated N2 is discharged into the air.

[0030] Preferably, the heat treatment in step (2) is carried out in an air atmosphere.

[0031] In the present invention, CuN is selected x As the prerequisite material of Cu, a copper single layer is obtained by heating to achieve the purpose of color adjustment; x It is a non-thermally stable material. During heat treatment, CuN x Most of the nitrogen in the film will be stripped off, leaving the copper element, namely CuN x The phase will gradually transform into Cu phase, and the transformed Cu phase will not transform into CuO x Phase transition, thereby achieving the color adjustment function of the heated Low-E film through the metallic color of Cu.

[0032] In a third aspect, the present invention provides a use of the above-mentioned Low-E coated glass tinting layer, wherein the tinting layer is used for neutral color double-silver Low-E coated glass.

[0033] Preferably, the coated glass comprises a first composite layer, a metal coloring layer and a second composite layer in order from the glass substrate upwards.

[0034] Preferably, the first composite layer includes, from the glass substrate upward, a bottom dielectric combination layer and a first functional layer, and the second composite layer includes, from the metal coloring layer upward, a first metal barrier layer, an intermediate dielectric combination layer, a second functional layer, a second metal barrier layer, a top dielectric combination layer and a protective layer.

[0035] As a preferred technical solution of the present invention, the bottom dielectric combination layer includes a first dielectric layer and a second dielectric layer sequentially stacked on the surface of the glass substrate.

[0036] Preferably, the first dielectric layer comprises SiN x layer, ZnSnO x layer or ZrO x Any one of the layers, preferably SiN x layer.

[0037] Preferably, the second dielectric layer includes an AZO layer, a ZnSnO x layer or TiO x Any one of the layers is preferably an AZO layer.

[0038] In the present invention, the first dielectric layer is mainly made of a material that blocks glass impurities, and the second dielectric layer is mainly made of a silver seed layer material.

[0039] Preferably, the thickness of the first dielectric layer is 15 to 80 nm, for example, 15 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm or 80 nm, but is not limited to the listed values. Other unlisted values ​​within this numerical range are also applicable, preferably 20 to 50 nm.

[0040] The thickness of the second dielectric layer is 6 to 20 nm, for example, 6 nm, 8 nm, 10 nm, 12 nm, 14 nm, 16 nm, 18 nm or 20 nm, but is not limited to the listed values. Other values ​​not listed within the numerical range are also applicable, preferably 8 to 15 nm.

[0041] As a preferred technical solution of the present invention, the first functional layer and the second functional layer independently include any one of an Ag layer, an Au layer or an Ag alloy layer, preferably an Ag layer.

[0042] In the present invention, the functional layer is the main structural layer for achieving the low-emissivity effect of the coated glass, and the material thereof is mainly selected from the above-mentioned high infrared reflective material.

[0043] Preferably, the thickness of the first functional layer and the second functional layer are independently 6 to 15 nm, for example, 6 nm, 7 nm, 8 nm, 9 nm, 10 nm, 12 nm, 14 nm or 15 nm, etc., but are not limited to the listed values. Other unlisted values ​​within this numerical range are also applicable, preferably 6 to 12 nm.

[0044] As a preferred technical solution of the present invention, the first metal barrier layer and the second metal barrier layer independently include any one of a NiCr layer, a Cr layer, a Ni layer, a Ti layer or an Al layer.

[0045] In the present invention, the material of the metal barrier layer is mainly selected from an oxidized sacrificial material, and is mainly selected from a metal or an alloy.

[0046] Preferably, the thickness of the first metal barrier layer and the second metal barrier layer are independently 0.5 to 3 nm, for example, 0.5 nm, 1 nm, 1.5 nm, 2 nm, 2.5 nm or 3 nm, but are not limited to the listed values. Other unlisted values ​​within this numerical range are also applicable, preferably 0.7 to 1.5 nm.

[0047] As a preferred technical solution of the present invention, the intermediate dielectric combination layer includes a third dielectric layer, a fourth dielectric layer and a fifth dielectric layer sequentially stacked on the surface of the first metal barrier layer.

[0048] Preferably, the third dielectric layer includes an AZO layer, a ZnSnO x layer, TZO layer or TiO x Any of the layers.

[0049] Preferably, the fourth dielectric layer comprises SiN x layer, AZO layer, ZnSnO x layer, TZO layer or TiO x Any of the layers.

[0050] Preferably, the fifth dielectric layer includes an AZO layer, a ZnSnO x layer or TiO x Any of the layers.

[0051] Preferably, the thickness of the third dielectric layer is 6 to 20 nm, for example, 6 nm, 8 nm, 10 nm, 12 nm, 14 nm, 16 nm, 18 nm or 20 nm, but is not limited to the listed values. Other unlisted values ​​within this numerical range are also applicable, preferably 8 to 15 nm.

[0052] Preferably, the thickness of the fourth dielectric layer is 20 to 80 nm, for example, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm or 80 nm, but is not limited to the listed values. Other values ​​not listed within the numerical range are also applicable, preferably 50 to 70 nm.

[0053] Preferably, the thickness of the fifth dielectric layer is 6 to 20 nm, for example, 6 nm, 8 nm, 10 nm, 12 nm, 14 nm, 16 nm, 18 nm or 20 nm, but is not limited to the listed values. Other unlisted values ​​within this numerical range are also applicable, preferably 8 to 15 nm.

[0054] As a preferred technical solution of the present invention, the top dielectric combination layer includes a sixth dielectric layer and a seventh dielectric layer sequentially stacked on the surface of the second metal barrier layer.

[0055] Preferably, the sixth dielectric layer includes an AZO layer, a ZnSnO x layer, TZO layer or TiO x Any of the layers.

[0056] Preferably, the seventh dielectric layer comprises SiN x layer, AZO layer, ZnSnO x layer, TZO layer or TiO x Any of the layers.

[0057] Preferably, the thickness of the sixth dielectric layer is 6 to 20 nm, for example, 6 nm, 8 nm, 10 nm, 12 nm, 14 nm, 16 nm, 18 nm or 20 nm, but is not limited to the listed values. Other values ​​not listed within the numerical range are also applicable, preferably 8 to 15 nm.

[0058] Preferably, the thickness of the seventh dielectric layer is 15 to 80 nm, for example, 15 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm or 80 nm, but is not limited to the listed values. Other values ​​not listed within this numerical range are also applicable, preferably 20 to 50 nm.

[0059] As a preferred technical solution of the present invention, the protective layer includes ZrO x layer, TiO x Layer or CN x Any of the layers.

[0060] Preferably, the thickness of the protective layer is 5 to 10 nm, such as 5 nm, 6 nm, 7 nm, 8 nm, 9 nm or 10 nm, but is not limited to the listed values. Other unlisted values ​​within the numerical range are also applicable, preferably 5 to 8 nm.

[0061] In the present invention, the material of the protective layer is selected to have the characteristic of anti-oxidation, and plays a sacrificial role in the film to protect the main functional layer from being oxidized.

[0062] Compared with the prior art, the present invention has the following beneficial effects:

[0063] (1) The coated glass of the present invention adds a color-adjusting layer to the traditional double-silver Low-E glass, and arranges the color-adjusting layer between the functional layer and the metal barrier layer. Furthermore, by selecting the material of the color-adjusting layer, the perspective color can be kept relatively neutral after tempering and heat treatment;

[0064] (2) The arrangement of multiple structural layers in the coated glass of the present invention, especially the alternating arrangement of dielectric layers, functional layers, and barrier layers, effectively adjusts the absorption intensity of each layer to different wavelength bands, realizes a remote processing method of coating first and then tempering, and avoids the problem of easy oxidation and shedding of the film layer after tempering heat treatment;

[0065] (3) The coated glass structure layer of the present invention is reasonably arranged, easy to process, has significant effects, and has a wide range of applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0066] Figure 1 1 is a schematic structural diagram of the neutral-colored double-silver Low-E coated glass provided in Example 1 of the present invention;

[0067] Among them, 1-glass substrate, 2-bottom dielectric combination layer, 21-first dielectric layer, 22-second dielectric layer, 3-first functional layer, 4-color adjustment layer, 5-first metal barrier layer, 6-intermediate dielectric combination layer, 61-third dielectric layer, 62-fourth dielectric layer, 63-fifth dielectric layer, 7-second functional layer, 8-second metal barrier layer, 9-top dielectric combination layer, 91-sixth dielectric layer, 92-seventh dielectric layer, 10-protective layer. DETAILED DESCRIPTION

[0068] In order to better illustrate the present invention and facilitate understanding of the technical solution of the present invention, the present invention is further described in detail below. However, the following embodiments are merely simple examples of the present invention and do not represent or limit the scope of protection of the present invention. The scope of protection of the present invention shall be subject to the claims.

[0069] The following are typical but non-limiting examples of the present invention:

[0070] Example 1:

[0071] This embodiment provides a neutral color double silver Low-E coated glass. The structural diagram of the coated glass is as follows: Figure 1 As shown, it includes a glass substrate 1 and a composite coating, wherein the composite coating includes a first composite layer, a metal coloring layer 4 and a second composite layer sequentially stacked on the surface of the glass substrate 1, and the metal coloring layer 4 includes a copper single substance layer.

[0072] A composite coating is provided on one surface of the glass substrate 1 , and the total thickness of the composite coating is 184.5 nm.

[0073] The glass substrate 1 is transparent float glass, and the thickness of the glass substrate 1 is 10 mm.

[0074] The thickness of the metal coloring layer 4 is 5 nm.

[0075] The first composite layer includes, from the glass substrate 1 upward, a bottom dielectric combination layer 2 and a first functional layer 3, and the second composite layer includes, from the metal coloring layer 4 upward, a first metal barrier layer 5, an intermediate dielectric combination layer 6, a second functional layer 7, a second metal barrier layer 8, a top dielectric combination layer 9 and a protective layer 10.

[0076] The bottom dielectric combination layer 2 includes a first dielectric layer 21 and a second dielectric layer 22 sequentially stacked on the surface of the glass substrate 1 .

[0077] The first dielectric layer 21 is SiN x layer; the second dielectric layer 22 is an AZO layer.

[0078] The thickness of the first dielectric layer 21 is 19 nm, and the thickness of the second dielectric layer 22 is 12 nm.

[0079] The first functional layer 3 is an Ag layer, and the thickness of the first functional layer 3 is 7.9 nm.

[0080] The first metal barrier layer 5 is a NiCr layer, and the thickness of the first metal barrier layer 5 is 0.5 nm.

[0081] The intermediate dielectric combination layer 6 includes a third dielectric layer 61 , a fourth dielectric layer 62 and a fifth dielectric layer 63 sequentially stacked on the surface of the first metal barrier layer 5 .

[0082] The third dielectric layer 61 is an AZO layer; the fourth dielectric layer 62 is a SiN x layer; the fifth dielectric layer 63 is an AZO layer.

[0083] The thickness of the third dielectric layer 61 is 12 nm, the thickness of the fourth dielectric layer 62 is 65 nm, and the thickness of the fifth dielectric layer 63 is 12 nm.

[0084] The second functional layer 7 is an Ag layer, and the thickness of the second functional layer 7 is 10 nm.

[0085] The second metal barrier layer 8 is a NiCr layer, and the thickness of the second metal barrier layer 8 is 2.1 nm.

[0086] The top dielectric combination layer 9 includes a sixth dielectric layer 91 and a seventh dielectric layer 92 sequentially stacked on the surface of the second metal barrier layer 8 .

[0087] The sixth dielectric layer 91 is an AZO layer; the seventh dielectric layer 92 is a SiN x layer.

[0088] The thickness of the sixth dielectric layer 91 is 12 nm, and the thickness of the seventh dielectric layer 92 is 22 nm.

[0089] The protective layer 10 is ZrO x the thickness of the protective layer 10 is 5nm.

[0090] The method for preparing the tinting layer of the coated glass comprises the following steps:

[0091] (1) After the first composite layer is plated on the glass substrate 1, copper is used as the raw material and vacuum magnetic sputtering technology is used to first evacuate the glass substrate to a pressure of 9×10 -6 mbar, and then filled with argon and nitrogen with a volume ratio of 5:1, and the pressure was controlled at 1.32×10 -3 mbar, CuN x membrane layer;

[0092] (2) in step (1) the CuN x The second composite layer is plated on the basis of the film layer, and then subjected to heat treatment after the film is plated. The heat treatment temperature is 680℃, the time is 360s, the atmosphere is air, and the CuN x It decomposes and gradually transforms into Cu, obtaining a coated glass containing a copper elemental coloring layer.

[0093] The specific process parameters for preparing the composite coating in the double-silver Low-E coated glass in this embodiment are shown in Table 1.

[0094] Table 1

[0095]

[0096]

[0097]

[0098] The optical properties of the double-silver Low-E coated glass in Example 1 were tested before and after the tempering heat treatment. The results are shown in Table 2.

[0099] Table 2

[0100] Optical parameters T(％) at bt Rg(%) ag bg Before heat treatment 53 -3.6 -2 9.5 -1.1 -6.9 After heat treatment 59 -2.7 0.5 8.5 -1.4 -8.5

[0101] Among them, T represents the visible light transmittance of the glass (%), at represents the red and green values ​​of the glass's perspective color, bt represents the yellow and blue values ​​of the glass's perspective color, Rg represents the outdoor visible light reflectance of the glass (%), ag represents the red and green values ​​of the glass's outdoor visible light reflection color, and bg represents the yellow and blue values ​​of the glass's outdoor visible light reflection color.

[0102] Example 2:

[0103] This embodiment provides a neutral-colored double-silver Low-E coated glass, which includes a glass substrate 1 and a composite coating. The composite coating includes a first composite layer, a metallic coloring layer 4, and a second composite layer sequentially stacked on the surface of the glass substrate 1. The metallic coloring layer 4 includes a copper single-element layer.

[0104] A composite coating is provided on one surface of the glass substrate 1 , and the total thickness of the composite coating is 191.3 nm.

[0105] The glass substrate 1 is transparent float glass, and the thickness of the glass substrate 1 is 5 mm.

[0106] The thickness of the metal coloring layer 4 is 3.5 nm.

[0107] The first composite layer includes, from the glass substrate 1 upward, a bottom dielectric combination layer 2 and a first functional layer 3, and the second composite layer includes, from the metal coloring layer 4 upward, a first metal barrier layer 5, an intermediate dielectric combination layer 6, a second functional layer 7, a second metal barrier layer 8, a top dielectric combination layer 9 and a protective layer 10.

[0108] The bottom dielectric combination layer 2 includes a first dielectric layer 21 and a second dielectric layer 22 sequentially stacked on the surface of the glass substrate 1 .

[0109] The first dielectric layer 21 is ZnSnO x The second dielectric layer 22 is TiO x layer.

[0110] The thickness of the first dielectric layer 21 is 40 nm, and the thickness of the second dielectric layer 22 is 6 nm.

[0111] The first functional layer 3 is an Ag alloy layer, and the thickness of the first functional layer 3 is 11.5 nm.

[0112] The first metal barrier layer 5 is a Cr layer, and the thickness of the first metal barrier layer 5 is 1.5 nm.

[0113] The intermediate dielectric combination layer 6 includes a third dielectric layer 61 , a fourth dielectric layer 62 and a fifth dielectric layer 63 sequentially stacked on the surface of the first metal barrier layer 5 .

[0114] The third dielectric layer 61 is TiO x The fourth dielectric layer 62 is an AZO layer; the fifth dielectric layer 63 is a TiO x layer.

[0115] The thickness of the third dielectric layer 61 is 6 nm, the thickness of the fourth dielectric layer 62 is 40 nm, and the thickness of the fifth dielectric layer 63 is 20 nm.

[0116] The second functional layer 7 is an Ag alloy layer, and the thickness of the second functional layer 7 is 8 nm.

[0117] The second metal barrier layer 8 is a Cr layer, and the thickness of the second metal barrier layer 8 is 0.8 nm.

[0118] The top dielectric combination layer 9 includes a sixth dielectric layer 91 and a seventh dielectric layer 92 sequentially stacked on the surface of the second metal barrier layer 8 .

[0119] The sixth dielectric layer 91 is a TZO layer; the seventh dielectric layer 92 is a TiO x layer.

[0120] The thickness of the sixth dielectric layer 91 is 6 nm, and the thickness of the seventh dielectric layer 92 is 40 nm.

[0121] The protective layer 10 is CN x the thickness of the protective layer 10 is 8nm.

[0122] The method for preparing the tinting layer of the coated glass comprises the following steps:

[0123] (1) After the first composite layer is plated on the glass substrate 1, the metal copper is used as the raw material and vacuum magnetic sputtering technology is used to first evacuate the glass substrate to a pressure of 5×10 -6 mbar, and then filled with argon and nitrogen with a volume ratio of 5:2, and the pressure was controlled at 7×10 - 3 mbar, CuN x membrane layer;

[0124] (2) in step (1) the CuN xThe second composite layer is plated on the basis of the film layer, and then subjected to heat treatment after the film is plated. The heat treatment temperature is 720℃, the time is 200s, the atmosphere is air, and the CuN x It decomposes and gradually transforms into Cu, obtaining a coated glass containing a copper elemental coloring layer.

[0125] The optical properties of the double-silver Low-E coated glass in Example 2 were tested before and after the tempering heat treatment. The results are shown in Table 3.

[0126] Table 3

[0127] Optical parameters T(％) at bt Rg(%) ag bg Before heat treatment 55 -3.2 -1.5 9.2 -1.5 -7.5 After heat treatment 61 -2.2 1.5 8.3 -1.9 -9.8

[0128] The meanings of the various parameters are the same as those in Table 2.

[0129] Example 3:

[0130] This embodiment provides a neutral-colored double-silver Low-E coated glass, which includes a glass substrate 1 and a composite coating. The composite coating includes a first composite layer, a metallic coloring layer 4, and a second composite layer sequentially stacked on the surface of the glass substrate 1. The metallic coloring layer 4 includes a copper single-element layer.

[0131] The invention comprises a bottom dielectric combination layer 2, a first functional layer 3, a color adjustment layer 4, a first metal barrier layer 5, an intermediate dielectric combination layer 6, a second functional layer 7, a second metal barrier layer 8, a top dielectric combination layer 9 and a protective layer 10 which are sequentially stacked on the surface of a glass substrate 1; the color adjustment layer 4 comprises a copper compound layer.

[0132] A composite coating is provided on one surface of the glass substrate 1 , and the total thickness of the composite coating is 260 nm.

[0133] The glass substrate 1 is colored float glass, and the thickness of the glass substrate 1 is 10 mm.

[0134] The thickness of the metal coloring layer 4 is 2 nm.

[0135] The first composite layer includes, from the glass substrate 1 upward, a bottom dielectric combination layer 2 and a first functional layer 3, and the second composite layer includes, from the metal coloring layer 4 upward, a first metal barrier layer 5, an intermediate dielectric combination layer 6, a second functional layer 7, a second metal barrier layer 8, a top dielectric combination layer 9 and a protective layer 10.

[0136] The bottom dielectric combination layer 2 includes a first dielectric layer 21 and a second dielectric layer 22 sequentially stacked on the surface of the glass substrate 1 .

[0137] The first dielectric layer 21 is ZrO x The second dielectric layer 22 is ZnSnO xlayer.

[0138] The thickness of the first dielectric layer 21 is 75 nm, and the thickness of the second dielectric layer 22 is 20 nm.

[0139] The first functional layer 3 is an Au layer, and the thickness of the first functional layer 3 is 15 nm.

[0140] The first metal barrier layer 5 is a Ti layer, and the thickness of the first metal barrier layer 5 is 3 nm.

[0141] The intermediate dielectric combination layer 6 includes a third dielectric layer 61 , a fourth dielectric layer 62 and a fifth dielectric layer 63 sequentially stacked on the surface of the first metal barrier layer 5 .

[0142] The third dielectric layer 61 is ZnSnO x The fourth dielectric layer 62 is a TZO layer; the fifth dielectric layer 63 is ZnSnO x layer.

[0143] The thickness of the third dielectric layer 61 is 20 nm, the thickness of the fourth dielectric layer 62 is 20 nm, and the thickness of the fifth dielectric layer 63 is 6 nm.

[0144] The second functional layer 7 is an Au layer, and the thickness of the second functional layer 7 is 6 nm.

[0145] The second metal barrier layer 8 is a Ti layer, and the thickness of the second metal barrier layer 8 is 3 nm.

[0146] The top dielectric combination layer 9 includes a sixth dielectric layer 91 and a seventh dielectric layer 92 sequentially stacked on the surface of the second metal barrier layer 8 .

[0147] The sixth dielectric layer 91 is TiO x layer; the seventh dielectric layer 92 is an AZO layer.

[0148] The thickness of the sixth dielectric layer 91 is 20 nm, and the thickness of the seventh dielectric layer 92 is 60 nm.

[0149] The protective layer 10 is TiO x the thickness of the protective layer 10 is 10nm.

[0150] The method for preparing the tinting layer of the coated glass comprises the following steps:

[0151] (1) After the first composite layer is plated on the glass substrate 1, the metal copper is used as the raw material and vacuum magnetic sputtering technology is used to first evacuate the glass substrate to a pressure of 10 -6 mbar, and then filled with argon and nitrogen with a volume ratio of 5:1.5, and the pressure was controlled at 9×10 -4 mbar, CuN x membrane layer;

[0152] (2) in step (1) the CuN x The second composite layer is plated on the basis of the film layer, and then subjected to heat treatment after the film is plated. The heat treatment temperature is 650℃, the time is 600s, the atmosphere is air, and the CuN x It decomposes and gradually transforms into Cu, obtaining a coated glass containing a copper elemental coloring layer.

[0153] The optical properties of the double-silver Low-E coated glass in Example 3 were tested before and after the tempering heat treatment. The results are shown in Table 4.

[0154] Table 4

[0155] Optical parameters T(％) at bt Rg(%) ag bg Before heat treatment 50 -3.4 -1.3 9.2 -0.5 -6.1 After heat treatment 56 -2.4 1.6 8 -0.9 -7.8

[0156] The meanings of the various parameters are the same as those in Table 2.

[0157] Comparative Example 1:

[0158] This comparative example provides a double-silver Low-E coated glass. The structure of the coated glass refers to the coated glass in Example 1, with the only difference being that the metal coloring layer 4 is not included, and the thicknesses and preparation process parameters of the remaining structural layers are the same as those in Example 1.

[0159] The optical properties of the double-silver Low-E coated glass in this comparative example were also tested before and after the tempering heat treatment, and the results are shown in Table 5.

[0160] Table 5

[0161] Optical parameters T(％) at bt Rg(%) ag bg Before heat treatment 63 -3.8 -1.5 6 1.1 -10.6 After heat treatment 72 -4.5 0.5 6.5 -1.2 -5.6

[0162] The meanings of the various parameters are the same as those in Table 2.

[0163] As can be seen from Tables 2 and 5, adding a tinting layer to ordinary double-silver Low-E coated glass can effectively adjust the perspective color of the entire coating. Compared with Comparative Example 1, the red and green values ​​at of the perspective color of the coated glass in Example 1 are more neutral, and the perspective color is more neutral.

[0164] From the above embodiments and comparative examples, it can be seen that the coated glass of the present invention adds a tinting layer to the traditional double-silver Low-E glass, and arranges the tinting layer between the functional layer and the metal barrier layer. Furthermore, by selecting the material of the tinting layer, the transparent color can be maintained at a relatively neutral color after tempering and heat treatment. The arrangement of multiple structural layers in the coated glass, especially the alternating arrangement of dielectric layers, functional layers, and barrier layers, effectively adjusts the absorption intensity of each layer for different wavelength bands, realizes a remote processing method of first coating and then tempering, and avoids the problems of easy oxidation and shedding of the film layer after tempering and heat treatment. The coated glass has a reasonable arrangement of structural layers, is easy to process, has significant effects, and has a wide range of applications.

[0165] The applicant declares that the present invention uses the above-described embodiments to illustrate the detailed products and methods of the present invention. However, the present invention is not limited to the above-described detailed products and methods. This does not mean that the present invention must rely on the above-described detailed products and methods in order to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent replacements for the product structure of the present invention, additions of auxiliary structures, and selections of specific methods, etc., fall within the scope of protection and disclosure of the present invention.

Claims

1. A Low-E coated glass coloring layer, characterized in that: The coated glass comprises a glass substrate and a composite coating, wherein the composite coating comprises a first composite layer, a metal coloring layer, and a second composite layer sequentially stacked on the surface of the glass substrate, and the metal coloring layer comprises a copper single substance layer; The Low-E coated glass tinting layer is used for neutral double-silver Low-E coated glass. The first composite layer includes, from the glass substrate upward, a bottom dielectric combination layer and a first functional layer. The second composite layer includes, from the metal tinting layer upward, a first metal barrier layer, an intermediate dielectric combination layer, a second functional layer, a second metal barrier layer, a top dielectric combination layer, and a protective layer. The method for preparing the color-adjusting layer of the Low-E coated glass comprises: (1) After the first composite layer is plated on the glass substrate, metallic copper is used as the raw material, vacuum magnetic sputtering technology is adopted, and inert gas and nitrogen are filled in to obtain a CuNx film layer; (2) A second composite layer is plated on the CuNx film layer in step (1), and after the coating is completed, heat treatment is performed to obtain a coated glass containing a copper single substance color-adjusting layer.

2. The Low-E coated glass color adjustment layer according to claim 1, characterized in that: A composite coating is provided on one surface of the glass substrate, and the total thickness of the composite coating is 180-270 nm.

3. The Low-E coated glass color adjustment layer according to claim 1, characterized in that: The glass substrate is any one of transparent float glass, colored float glass or ultra-clear float glass, and the thickness of the glass substrate is 2 to 20 mm.

4. The Low-E coated glass color adjustment layer according to claim 1, characterized in that: The thickness of the metal coloring layer is 2-5 nm.

5. The method for preparing a tinting layer of Low-E coated glass according to any one of claims 1 to 4, characterized in that: The preparation method comprises: (1) After the first composite layer is plated on the glass substrate, CuN is obtained by using metallic copper as the raw material and vacuum magnetic sputtering technology and filling it with inert gas and nitrogen. x membrane layer; (2) in step (1) the CuN x A second composite layer is plated on the basis of the film layer, and after the coating is completed, heat treatment is performed to obtain a coated glass containing a copper single substance coloring layer.

6. The preparation method according to claim 5, characterized in that The target material for the vacuum magnetic sputtering in step (1) is a copper target.

7. The preparation method according to claim 5, characterized in that Step (1) Before filling with inert gas and nitrogen, first evacuate to a pressure of 9×10 -6 mbar or less.

8. The preparation method according to claim 5, characterized in that After filling inert gas and nitrogen in step (1), the pressure is controlled to 9×10 -4 ~7×10 -3 mbar.

9. The preparation method according to claim 5, characterized in that The volume ratio of the inert gas to nitrogen in step (1) is 5:1 to 5:

2.

10. The preparation method according to claim 5, characterized in that The temperature of the heat treatment in step (2) is 650-720°C.

11. The preparation method according to claim 5, characterized in that The heat treatment time in step (2) is 200 to 600 seconds.

12. The preparation method according to claim 5, characterized in that During the heat treatment process of step (2), CuN x Decomposes and gradually transforms into Cu.

13. The preparation method according to claim 5, characterized in that The heat treatment in step (2) is carried out in an air atmosphere.

14. The use of the Low-E coated glass tinting layer according to any one of claims 1 to 4, characterized in that: The color adjustment layer is used for neutral color double silver Low-E coated glass.

15. The use according to claim 14, characterized in that The coated glass comprises a first composite layer, a metal coloring layer and a second composite layer in order from the glass substrate upwards.

16. The use according to claim 14, characterized in that The first composite layer includes a bottom dielectric combination layer and a first functional layer in sequence from the glass substrate upward, and the second composite layer includes a first metal barrier layer, an intermediate dielectric combination layer, a second functional layer, a second metal barrier layer, a top dielectric combination layer and a protective layer in sequence from the metal coloring layer upward.

17. The use according to claim 16, characterized in that The bottom dielectric combination layer comprises a first dielectric layer and a second dielectric layer sequentially stacked on the surface of the glass substrate.

18. The use according to claim 17, characterized in that The first dielectric layer includes SiN x layer, ZnSnO x layer or ZrO x Any of the layers.

19. The use according to claim 17, characterized in that The second dielectric layer includes an AZO layer, a ZnSnO x layer or TiO x Any of the layers.

20. The use according to claim 17, characterized in that The thickness of the first dielectric layer is 15 to 80 nm, and the thickness of the second dielectric layer is 6 to 20 nm.

21. The use according to claim 16, characterized in that The first functional layer and the second functional layer independently include any one of an Ag layer, an Au layer or an Ag alloy layer.

22. The use according to claim 16, characterized in that The thickness of the first functional layer and the second functional layer are independently 6 to 15 nm.

23. The use according to claim 16, characterized in that The first metal barrier layer and the second metal barrier layer independently include any one of a NiCr layer, a Cr layer, a Ni layer, a Ti layer or an Al layer.

24. The use according to claim 16, characterized in that The thickness of the first metal barrier layer and the second metal barrier layer are independently 0.5-3 nm.

25. The use according to claim 16, characterized in that The intermediate dielectric combination layer comprises a third dielectric layer, a fourth dielectric layer and a fifth dielectric layer which are sequentially stacked on the surface of the first metal barrier layer.

26. The use according to claim 25, characterized in that The third dielectric layer includes an AZO layer, a ZnSnO x layer, TZO layer or TiO x Any of the layers.

27. The use according to claim 25, characterized in that The fourth dielectric layer includes SiN x layer, AZO layer, ZnSnO x layer, TZO layer or TiO x Any of the layers.

28. The use according to claim 25, characterized in that The fifth dielectric layer includes an AZO layer, a ZnSnO x layer or TiO x Any of the layers.

29. The use according to claim 25, characterized in that The thickness of the third dielectric layer is 6-20 nm, the thickness of the fourth dielectric layer is 20-80 nm, and the thickness of the fifth dielectric layer is 6-20 nm.

30. The use according to claim 16, characterized in that The top dielectric combination layer includes a sixth dielectric layer and a seventh dielectric layer sequentially stacked on the surface of the second metal barrier layer.

31. The use according to claim 30, characterized in that The sixth dielectric layer includes an AZO layer, a ZnSnO x layer, TZO layer or TiO x Any of the layers.

32. The use according to claim 30, characterized in that The seventh dielectric layer includes SiN x layer, AZO layer, ZnSnO x layer, TZO layer or TiO x Any of the layers.

33. The use according to claim 30, characterized in that The thickness of the sixth dielectric layer is 6-20 nm, and the thickness of the seventh dielectric layer is 15-80 nm.

34. The use according to claim 30, characterized in that The protective layer includes ZrO x layer, TiO x Layer or CN x Any of the layers.

35. The use according to claim 30, characterized in that The thickness of the protective layer is 5-10 nm.

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