Offline low-radiation coated glass and preparation method and use thereof

Abstract

The present invention provides an offline low-radiation coated glass and a preparation method and use thereof, wherein the offline low-radiation coated glass comprises a substrate layer and a low-radiation layer arranged on the surface of the substrate layer, wherein the low-radiation layer comprises a first dielectric layer, a transparent oxide conductive layer and a second dielectric layer arranged on the substrate layer from bottom to top. The offline low-radiation coated glass does not contain a conductive metal film layer such as Ag, Cu or Au, so that the glass has low-radiation performance after tempering heat treatment, and at the same time, achieves single-piece usability. The glass can be used for large areas such as interior decoration and outdoor curtain walls, and can be used in conjunction with hollow and interlayer products, so as to achieve safety and energy-saving effects while also having aesthetic effects.

Description

Technical Field

[0001] The invention belongs to the technical field of glass and relates to an offline low-radiation coated glass and a preparation method and application thereof. Background Art

[0002] At present, for offline low-e coated glass, its functional layer generally uses highly conductive metals such as Ag as infrared reflection layers to achieve low-emission performance. However, the low-e coated glass that uses metal as the low-emission functional layer is extremely easy to oxidize and scratch, and cannot achieve single-piece performance. It must be used in conjunction with insulating glass, which greatly limits the application scope of its products.

[0003] As for online low-e coated glass products, such as the online coated glass products disclosed in CN103562152A, the film layer structure used is: a first layer for neutralizing the reflected color; a second layer with low emissivity, which is basically composed of SnO2:F and has a thickness of 455-800nm; and a third layer basically composed of SiOx, where x is less than or equal to 2, and the thickness of this layer is 140-180nm. Although the performance of single-piece use can be achieved, its emissivity is higher than that of offline low-e, the product types are relatively single, the color uniformity, optical performance and thermal performance are poor, and it is impossible to make flexible adjustments according to customer and market needs, and it is difficult to meet market demand.

[0004] Therefore, it is of great research significance to provide an offline low-emissivity coated glass that can be used in a single piece. Summary of the invention

[0005] In view of the deficiencies in the prior art, the object of the present invention is to provide an offline low-radiation coated glass and a preparation method and use thereof. The offline low-radiation coated glass does not contain a conductive metal film layer such as Ag, Cu or Au, so that the glass has low radiation performance after tempering heat treatment, and at the same time, it can be used as a single piece. The glass can be used in large areas such as interior decoration and outdoor curtain walls, and can be used in conjunction with hollow and interlayer products, so as to achieve safety and energy-saving effects while also having an aesthetic effect.

[0006] To achieve this object, the present invention adopts the following technical solutions:

[0007] One of the purposes of the present invention is to provide an offline low-emissivity coated glass, comprising a substrate layer and a low-emissivity layer arranged on the surface of the substrate layer, wherein the low-emissivity layer comprises a first dielectric layer, a transparent oxide conductive layer and a second dielectric layer arranged on the substrate layer in sequence from bottom to top.

[0008] The offline low-emissivity coated glass has low-emissivity without containing conductive metal film layers such as Ag, Cu or Au, and can be used in a single piece. The glass can be used in large areas such as interior decoration and outdoor curtain walls, and can be used in conjunction with hollow and interlayer products, thereby achieving safety and energy-saving effects while also having an aesthetic effect.

[0009] An absorption layer is further arranged between the transparent oxide conductive layer and the second dielectric layer. The absorption layer can better adjust the performance parameters of the low-emissivity coated glass so that it can better meet different performance requirements.

[0010] Preferably, the absorption layer does not contain any one of Cu, Ag or Au or a combination of at least two of them, typical but non-limiting combinations are Cu and Ag, Cu and Au, Cu, Ag and Au. The low-emissivity layer does not contain metals such as Ag, Cu or Au with infrared reflection function, so that it can be used as a single piece.

[0011] Preferably, the absorption layer includes any one of a Ni layer, a Cr layer, a Ti layer, a Nb layer, a Zr layer, a Mo layer, a NiCr layer, a NiCrMo layer, a TiNb layer, a TiNi layer, a NbZr layer or a ZrTi layer, or a combination of at least two of them. Typical but non-limiting combinations include a Ni layer and a Cr layer, a Ti layer, a Nb layer and a Zr layer, a Mo layer, a NiCr layer and a NiCrMo layer, a TiNb layer, a TiNi layer, a NbZr layer and a ZrTi layer, and preferably a NiCr layer, a NiCrMo layer or a NbZr layer, or a combination of at least two of them.

[0012] Preferably, the absorption layer has a thickness of 0 to 20 nm, such as 2 nm, 5 nm, 8 nm, 10 nm, 12 nm, 15 nm or 18 nm, etc., and 0 is not included.

[0013] The first dielectric layer mainly blocks the precipitation of alkali metals in the substrate material and adjusts the optical properties. The first dielectric layer includes any one or a combination of at least two of a metal oxide layer, a nitride layer of a metal or metal alloy, and a nitride oxide layer of a metal or metal alloy. Typical but non-limiting combinations include a metal oxide layer and a metal nitride layer, a metal nitride layer and a nitride oxide layer of a metal alloy, a metal oxide layer, a metal nitride layer, a metal alloy nitride layer, a metal nitride oxide layer, and a metal alloy nitride oxide layer.

[0014] Preferably, the metal oxide includes any one or a combination of at least two of TiOx (1.3 < x < 2), NbOx (2.0 < x < 2.5), ZrOx (1 ≤ x ≤ 2), ZnSnOx (2.1 < x < 3), ZnO, or SnOx (1.3 < x < 2). Typical but non-limiting combinations are such as TiOx and NbOx, ZrOx and ZnSnOx, ZnO and SnOx, TiOx, NbOx, and ZrOx, ZnSnOx, ZnO, and SnOx.

[0015] Preferably, any one or a combination of at least two of the oxide layer of the metal or metalloid, the nitride layer of the metal or metalloid or metal alloy, and the oxynitride layer of the metal or metalloid or metal alloy. Typical but non-limiting combinations are such as TiNx (1.0 < x < 1.3) and SiNx (0.8 < x < 1.3), SiAlNx (1.2 ≤ x ≤ 2.3), SiBNx (1.2 ≤ x ≤ 2.3), and SiTiNx (1.3 ≤ x ≤ 4), TiNx, SiNx, and SiZrNx (1.3 ≤ x ≤ 4).

[0016] Preferably, the metal oxide layer includes any one or a combination of at least two of TiOx (1.3 < x < 2), NbOx (2.0 < x < 2.5), ZrOx (1 ≤ x ≤ 2), ZnSnOx (2.1 < x < 3), ZnO, or SnOx (1.3 < x < 2);

[0017] Preferably, the nitride layer of the metal or metalloid or metal alloy includes any one or a combination of at least two of TiNx (1.0 < x < 1.3), SiNx (0.8 < x < 1.3), SiAlNx (1.2 ≤ x ≤ 2.3), SiBNx (1.2 ≤ x ≤ 2.3), SiTiNx (1.3 ≤ x ≤ 4), or SiZrNx (1.3 ≤ x ≤ 4);

[0018] Preferably, the oxynitride of the metal or metalloid or metal alloy includes any one or a combination of at least two of SiNxOy (1.5 < x < 1.8, 0.2 < y < 0.5), SiAlNxOy (1 ≤ x ≤ 2, 1 ≤ y ≤ 2), SiBNxOy (1 ≤ x ≤ 2, 1 ≤ y ≤ 2), SiTiNxOy (1.6 ≤ x ≤ 2.8, 1.6 ≤ y ≤ 2.8), or SiZrNxOy (1.6 ≤ x ≤ 2.8, 1.6 ≤ y ≤ 2.8). Typical but non-limiting combinations are such as SiNxOy and SiAlNxOy, SiBNxOy, SiTiNxOy, and SiZrNxOy.

[0019] Preferably, the first dielectric layer includes any one or a combination of at least two of NbOx (2.0 < x < 2.5), ZrOx (1 ≤ x ≤ 2), SiNx (0.8 < x < 1.3), or SiNxOy (1.5 < x < 1.8, 0.2 < y < 0.5). Typical but non-limiting combinations are such as NbOx and ZrOx, SiNx and SiNxOy, NbOx, ZrOx and SiNx, ZrOx, SiNx and SiNxOy.

[0020] Preferably, the thickness of the first dielectric layer is 20 - 80 nm, such as 22 nm, 28 nm, 29 nm, 35 nm, 38 nm, 40 nm, 45 nm, 48 nm, 50 nm, 55 nm, 60 nm, 70 nm, or 75 nm, etc.

[0021] The main function of the transparent oxide conductive layer is infrared reflection, achieving a low-emissivity effect. The transparent oxide conductive layer includes any one or a combination of at least two of ITO, AZO, TZO, ATO, TNO, GZO, or FTO. Typical but non-limiting combinations are such as ITO and AZO, TZO, ATO and TNO, GZO and FTO. Preferably, it is any one or a combination of at least two of ITO, TZO, or ATO, such as ITO and ATO, ITO, TZO and ATO; further preferably ITO.

[0022] Preferably, the thickness of the transparent oxide conductive layer is 80 - 500 nm, such as 85 nm, 90 nm, 100 nm, 150 nm, 200 nm, 260 nm, 300 nm, 380 nm, 400 nm, or 480 nm, etc.

[0023] The second dielectric layer includes any one or a combination of at least two of a metal or metalloid oxide layer, a metal or metalloid or metal alloy nitride layer, and a metal or metalloid or metal alloy oxynitride layer. Typical but non-limiting combinations are such as a metal oxide layer and a non-metal oxide layer, a non-metal oxide layer and a metal or metal alloy nitride layer, a non-metal oxide layer, a metal or metal alloy nitride layer, and a metal or metal alloy oxynitride layer.

[0024] Preferably, the metal or metalloid oxide layer includes any one or a combination of at least two of SiOx, TiOx, NbOx, ZrOx, or SnOx. Typical but non-limiting combinations are such as TiOx and NbOx, ZrOx and SnOx, TiOx, NbOx and ZrOx, NbOx, ZrOx and SnOx.

[0025] Preferably, the metal or metalloid oxide layer includes an oxide layer of Si, SiAl, SiB, SiTi, or SiZr.

[0026] Preferably, the nitride of the metallic metal or metal alloy comprises any one of TiNx, SiNx, SiAlNx, SiBNx, SiTiNx or SiZrNx, or a combination of at least two thereof, typical but non-limiting combinations being TiNx and SiNx, SiAlNx, SiBNx and SiTiNx, TiNx, SiNx and SiZrNx, SiAlNx, SiBNx, SiTiNx and SiZrNx.

[0027] Preferably, the oxynitride of the metal or metalloid or metal alloy includes any one of SiNxOy, SiAlNxOy, SiBNxOy, SiTiNxOy or SiZrNxOy, or a combination of at least two thereof, typical but non-limiting combinations being SiNxOy and SiAlNxOy, SiBNxOy, SiTiNxOy and SiZrNxOy.

[0028] Preferably, the second dielectric layer comprises any one of ZrOx, SiNx or SiNxOy or a combination of at least two thereof, preferably SiNx or ZrOx; typical but non-limiting combinations include ZrOx and SiNx, SiNx and SiNxOy, and ZrOx, SiNx and SiNxOy.

[0029] Preferably, the thickness of the second dielectric layer is 30-100 nm, such as 40 nm, 50 nm, 60 nm, 80 nm, 85 nm, 90 nm, 92 nm or 98 nm.

[0030] The substrate layer includes a glass layer and / or an organic transparent plastic layer.

[0031] Preferably, the thickness of the base layer is 1 to 20 mm, such as 2 mm, 3 mm, 4 mm, 5 mm, 8 mm, 10 mm, 12 mm, 15 mm or 18 mm.

[0032] The thickness of the low-emissivity layer is 80 to 500 nm, for example, 100 nm, 150 nm, 180 nm, 200 nm, 250 nm, 280 nm, 300 nm, 350 nm, 380 nm, 400 nm, 430 nm, 450 nm, 480 nm, etc.

[0033] In the present invention, different materials have different low-radiation characteristics. For example, when ITO is 80 to 200 nm thick, its emissivity can reach 0.25 to 0.1, while when AZO is 400 nm to 500 nm thick, its emissivity can only reach about 0.25 to 0.2. Therefore, different thicknesses are selected according to different materials.

[0034] Preferably, the offline low-emissivity coated glass includes at least two low-emissivity layers, such as 2 layers, 3 layers, 5 layers, 8 layers, 9 layers, 15 layers or 20 layers.

[0035] Preferably, the offline low-emissivity coated glass is a single-piece structure or a hollow glass or a laminated glass structure.

[0036] Preferably, the offline low-emissivity coated glass comprises a substrate layer, and also comprises a low-emissivity layer arranged on the surface of the substrate layer, wherein the low-emissivity layer comprises a first dielectric layer, a transparent oxide conductive layer, an absorption layer and a second dielectric layer arranged on the substrate layer in sequence from bottom to top;

[0037] The first dielectric layer includes any one of NbOx, ZrOx, SiNx or SiNxOy or a combination of at least two thereof, with a thickness of 20 to 80 nm, for example, 25 nm, 28 nm, 30 nm, 35 nm, 38 nm, 40 nm, 45 nm, 50 nm, 55 nm, 60 nm, 65 nm, 70 nm, 75 nm, etc.

[0038] The transparent oxide conductive layer includes any one of ITO, TZO or ATO or a combination of at least two thereof, and has a thickness of 80 to 200 nm, such as 90 nm, 100 nm, 120 nm, 140 nm, 160 nm, 180 nm or 190 nm.

[0039] The absorption layer includes any one of Ti, NiCr, TiNi, TiNb, TiZr or NiCrMo or a combination of at least two thereof, and has a thickness of 2 to 5 nm, for example, 2.3 nm, 2.5 nm, 2.8 nm, 3 nm, 3.3 nm, 3.5 nm, 3.8 nm, 4 nm, 4.5 nm, 4.8 nm, etc.

[0040] The second dielectric layer includes any one of ZrOx, SiNx or SiNxOy or a combination of at least two thereof, and has a thickness of 40 to 80 nm, for example, 43 nm, 45 nm, 48 nm, 50 nm, 55 nm, 58 nm, 60 nm, 65 nm, 68 nm, 70 nm, 75 nm, 78 nm, etc.

[0041] The above-mentioned layers cooperate with each other to optimize the performance of low-emissivity coated glass.

[0042] The second object of the present invention is to provide a method for preparing the offline low-emissivity coated glass as described above, the method comprising: preparing at least one low-emissivity layer on a base layer, and obtaining the offline low-emissivity coated glass by tempering or bending tempering; wherein the low-emissivity layer comprises a first dielectric layer, a transparent oxide conductive layer, and a second dielectric layer arranged in sequence from near to far from the base layer.

[0043] The offline low-emissivity coated glass can be prepared by a simple method, and the final film structure, material, thickness and color performance can be adjusted according to customer requirements to meet customer performance requirements for the product. The low-emissivity layer can achieve tempered performance, and the product emissivity is optimal only after tempering. For infrared radiation film layers containing ITO, etc., there is no need to heat the substrate during the magnetron sputtering coating process. After coating each film layer, the composite film layer containing the substrate can be tempered or bent.

[0044] The method for preparing at least a low-emissivity layer on the substrate layer includes any one of magnetron sputtering, chemical vapor deposition, ion beam sputtering deposition or evaporation, or a combination of at least two of them. Typical but non-limiting combinations include magnetron sputtering and chemical vapor deposition, ion beam sputtering deposition and evaporation, magnetron sputtering, chemical vapor deposition and ion beam sputtering deposition.

[0045] Preferably, the temperature of the tempering treatment or the bending tempering treatment is 680-710°C, for example, 680°C, 685°C, 690°C, 695°C, 700°C, 705°C, 710°C, etc.

[0046] Preferably, the time of the tempering treatment or bending tempering treatment is 210 to 1200 s, for example, 210 s, 250 s, 300 s, 350 s, 400 s, 450 s, 500 s, 600 s, 800 s, 1000 s or 1200 s.

[0047] Preferably, the method further comprises a hollowing process and / or a sandwich process after the tempering process or the bending tempering process. The offline low-emissivity coated glass can be prepared into a hollow shape or a sandwich shape as required.

[0048] The third object of the present invention is to provide a use of the offline low-emissivity coated glass as described above, which is used for interior decoration or outdoor curtain wall glass. The offline low-emissivity coated glass can be produced in large quantities and in large sizes, with a maximum production size of 3.3m×12m, and can be cut into other small sizes. It has wear and scratch resistance, good acid and alkali corrosion resistance, and can be used in a single piece. Therefore, the offline low-emissivity coated glass can be widely used in interior decoration or outdoor curtain wall glass.

[0049] The numerical range described in the present invention not only includes the point values ​​listed above, but also includes any point values ​​between the above numerical ranges that are not listed. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0050] Compared with the prior art, the present invention has the following beneficial effects:

[0051] The visible light transmittance of the offline low-emissivity coated glass is adjustable within the range of 30 to 90%, the color is neutral, the emissivity E is within the range of 0.1 to 0.25, and the shading coefficient Sc is continuously adjustable within the range of 0.25 to 0.92, which can meet the needs of different performances and different areas.

[0052] The offline low-emissivity coated glass is formed by the cooperation of multiple layers of film, and in the absence of conductive metal film layers such as Ag, Cu or Au, a plurality of inorganic materials of different thicknesses are plated on the surface of the base layer, so that the low-emissivity performance can be achieved while also being temperable and usable as a single piece.

[0053] The offline low-emissivity coated glass preparation method is simple and can be produced in large quantities in large sizes, the production efficiency can be greatly improved, the product size is almost unlimited, and products of various sizes can be produced according to customer needs, effectively improving the effectiveness efficiency and yield rate;

[0054] The low-emissivity coated glass can be used in large areas such as interior decoration and outdoor curtain walls, and can be used in conjunction with hollow and laminated products, thereby achieving safety and energy-saving effects while also having an aesthetic effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0055] Figure 1 This is a schematic structural diagram of the offline low-emissivity coated glass provided in Example 1, wherein 1 is a substrate layer, 2 is a first dielectric layer, 3 is a transparent oxide conductive layer, and 4 is a second dielectric layer.

[0056] Figure 2 This is a schematic structural diagram of the offline low-emissivity coated glass provided in Example 2, wherein 1 is a substrate layer, 2 is a first dielectric layer, 3 is a transparent oxide conductive layer, 4 is a second dielectric layer, and 5 is a metal absorption layer.

[0057] Figure 3 This is a schematic structural diagram of the offline low-emissivity coated glass provided in Example 3, wherein 1 is a substrate layer, 2 is a first dielectric layer, 3 is a transparent oxide conductive layer, 4 is a second dielectric layer, and 5 is a metal absorption layer.

[0058] Figure 4 This is a schematic structural diagram of the offline low-emissivity coated glass provided in Example 4, wherein 1 is a substrate layer, 2 is a first dielectric layer, 3 is a transparent oxide conductive layer, 4 is a second dielectric layer, and 5 is a metal absorption layer.

[0059] Figure 5 This is a schematic structural diagram of the offline low-emissivity coated glass provided in Example 5, wherein 1 is a substrate layer, 2 is a first dielectric layer, 3 is a transparent oxide conductive layer, 4 is a second dielectric layer, and 5 is a metal absorption layer.

[0060] Figure 6This is a schematic structural diagram of the offline low-emissivity coated glass provided in Example 6, wherein 1 is a substrate layer, 2 is a first dielectric layer, 3 is a transparent oxide conductive layer, 4 is a second dielectric layer, and 5 is a metal absorption layer. DETAILED DESCRIPTION

[0061] The technical solution of the present invention is further described below with reference to the accompanying drawings and through specific implementation methods.

[0062] Example 1

[0063] A low-emissivity coated glass, such as Figure 1 As shown, it comprises a base layer (1) and a low-emissivity layer arranged on one side of the base layer, wherein the low-emissivity layer comprises, in order from near to far distance from the base layer, a first dielectric layer (2), a transparent oxide conductive layer (3) and a second dielectric layer (4);

[0064] The first dielectric layer is a SiNx layer, and its thickness is 28nm;

[0065] The transparent oxide conductive layer is an ITO layer, and its thickness is 141 nm;

[0066] The second dielectric layer is a SiNxOy layer, and its thickness is 65nm;

[0067] The base layer is a glass substrate with a thickness of 6 mm.

[0068] The method for preparing the low-emissivity coated glass comprises:

[0069] A SiNx layer is first deposited on a glass substrate by magnetron sputtering in an atmosphere of Ar / N2=600:600 Sccm, and then an ITO film is deposited on the SiNx layer in an atmosphere of Ar:O2=1500:30 Sccm. Thereafter, SiNxOy is deposited on the ITO layer in a gas ratio of Ar:N:O=600:140:560 Sccm. Tempering treatment is then performed to obtain the offline low-emissivity coated glass.

[0070] The product color performance and thermal performance are as follows:

[0071]

[0072] Example 2

[0073] A low-emissivity coated glass, such as Figure 2 As shown, it comprises a base layer (1) and a low-emissivity layer arranged on one side of the base layer, wherein the low-emissivity layer comprises, in order from near to far distance from the base layer, a first dielectric layer (2), a transparent oxide conductive layer (3) and a second dielectric layer (4);

[0074] The first dielectric layer is a metal or metalloid nitride or oxide, such as a SiNx layer and a SiOx layer, and the thicknesses thereof are 20 nm and 18 nm respectively;

[0075] The transparent oxide conductive layer is an ITO layer, and its thickness is 120nm;

[0076] The second dielectric layer is a SiOx layer and a SiNx layer, and the thicknesses thereof are 19 nm and 30 nm respectively;

[0077] The base layer is a glass substrate with a thickness of 6 mm.

[0078] The method for preparing the low-emissivity coated glass comprises:

[0079] A first dielectric layer is plated on a clean glass surface by magnetron sputtering, wherein the dielectric composite layer comprises a SiNx layer and a SiOx layer, wherein the SiNx atmosphere is Ar:N2=600:600sccm, and the SiOx atmosphere is Ar:O2=600:800sccm; an ITO film layer is plated on the first dielectric layer, and the atmosphere is Ar:O2=1500:30sccm; and then a second dielectric layer is plated on the infrared reflection functional layer ITO layer, wherein the second dielectric layer comprises SiOx and SiNx, and SiNx is located on the outer layer of SiOx, and the atmosphere is Ar:N2=600:800sccm; after the film layer plating is completed, tempering treatment is performed to obtain the low-emissivity coated glass.

[0080] The performance of the low-emissivity coated glass is shown in the following table.

[0081]

[0082] Example 3

[0083] A low-emissivity coated glass, such as Figure 3 As shown, it comprises a base layer (1) and a low-emissivity layer arranged on one side of the base layer, wherein the low-emissivity layer comprises, in order from near to far distance from the base layer, a first dielectric layer (2), a transparent oxide conductive layer (3), a metal absorption layer (5) and a second dielectric layer (4);

[0084] The first dielectric layer is a SiNx layer, a SiOx layer and a SiNx layer in order of distance from the substrate layer, and the thicknesses thereof are 20 nm, 34 nm and 18 nm respectively;

[0085] The transparent oxide conductive layer is an ITO layer, and its thickness is 119 nm;

[0086] The metal absorption layer is a NiCr layer with a thickness of 8 nm;

[0087] The second dielectric layer is a SiNx layer, and its thickness is 37nm;

[0088] The base layer is a glass substrate with a thickness of 6 mm.

[0089] The method for preparing the low-emissivity coated glass comprises:

[0090] The first dielectric layer is plated on the clean glass surface by magnetron sputtering. The first dielectric layer is SiNx layer, SiOx layer and SiNx layer in order of distance from the substrate layer from near to far, wherein the SiNx atmosphere is Ar:N2=600:600sccm, and the SiOx atmosphere is Ar:O2=600:800sccm. Then, the ITO layer is plated on the first dielectric layer, and the atmosphere is Ar:O2=1500:30sccm. Then, the absorption layer NiCr layer is plated on the infrared reflection functional layer ITO. Pure Ar sputtering is used to plate the second dielectric layer SiNx on the absorption layer, and the atmosphere is Ar:N2=600:800sccm. The film coating is completed, and then tempered to obtain low-emissivity coated glass. Its performance is as shown in the following table:

[0091]

[0092] Example 4

[0093] A low-emissivity coated glass, such as Figure 4 As shown, it comprises a base layer (1) and a low-emissivity layer arranged on one side of the base layer, wherein the low-emissivity layer comprises, in order from near to far distance from the base layer, a first dielectric layer (2), a transparent oxide conductive layer (3), a metal absorption layer (5) and a second dielectric layer (4);

[0094] The first dielectric layer is one or a combination of a SiTiNxOy layer, a SiBNxOy layer or a SiAlNxOy layer, and has a thickness of 33 nm;

[0095] The transparent oxide conductive layer is an ITO layer, and its thickness is 108 nm;

[0096] The metal absorption layer is a NiCr layer with a thickness of 5 nm;

[0097] The second dielectric layer is a SiNx layer, and its thickness is 31 nm;

[0098] The base layer is a glass substrate with a thickness of 6 mm.

[0099] The method for preparing the low-emissivity coated glass comprises:

[0100] The first dielectric layer is plated on the clean glass surface by magnetron sputtering: one or several combinations of SiTiNxOy, SiBNxOy, SiAlNxOy, etc., wherein SiTi, SiB, and SiAl are doped with Si targets, and sputtering is performed under nitrogen or nitrogen-oxygen atmosphere conditions, wherein the atmosphere is Ar:N2=600:600sccm, or the atmosphere is Ar:N2:O2=600:120:500sccm, an ITO layer is plated on the first dielectric layer, wherein the atmosphere is Ar:O2=1500:30sccm, and then an absorption layer NiCr is plated on the infrared reflection functional layer ITO, and an outer dielectric protective layer SiNx and an outer dielectric protective layer are plated on the absorption layer by pure Ar sputtering, wherein the atmosphere is Ar:N2=600:800sccm, and the film plating is completed, and then tempering treatment is performed to obtain the low-emissivity coated glass. Its performance is shown in the following table.

[0101]

[0102] Example 5

[0103] A low-emissivity coated glass, such as Figure 5 As shown, it comprises a base layer (1) and a low-emissivity layer arranged on one side of the base layer, wherein the low-emissivity layer comprises, in order from near to far distance from the base layer, a first dielectric layer (2), a transparent oxide conductive layer (3), a metal absorption layer (5) and a second dielectric layer (4);

[0104] The first dielectric layer is a SiNx layer, and its thickness is 27nm;

[0105] The transparent oxide conductive layer is a TZO layer, and its thickness is 490nm;

[0106] The metal absorption layer is a Ti layer with a thickness of 4 nm;

[0107] The second dielectric layer is a SiNx layer, and its thickness is 31 nm;

[0108] The base layer is a glass substrate with a thickness of 6 mm.

[0109] The method for preparing the low-emissivity coated glass comprises:

[0110] The first dielectric layer is plated on the clean glass surface by magnetron sputtering, and the film is formed by sputtering under nitrogen or nitrogen-oxygen atmosphere, the atmosphere is Ar:N2=600:600sccm, the TZO film layer is plated on the first dielectric layer, the atmosphere is Ar:O2=1500:50sccm, and then the absorption layer Ti layer is plated on the infrared reflection function layer TZO layer, and the second dielectric layer SiNx layer is plated on the absorption layer by pure Ar gas sputtering, the atmosphere is Ar:N2=600:600sccm, and then tempered to obtain the low-emissivity coated glass. Its performance is as shown in the following table:

[0111]

[0112] Example 6

[0113] A low-emissivity coated glass, such as Figure 6 As shown, it comprises a base layer (1) and a low-emissivity layer arranged on one side of the base layer, wherein the low-emissivity layer comprises, in order from near to far distance from the base layer, a first dielectric layer (2), a transparent oxide conductive layer (3), a metal absorption layer (5) and a second dielectric layer (4);

[0114] The first dielectric layer is a SiNxOy layer, and its thickness is 56nm;

[0115] The transparent oxide conductive layer is an ITO layer, and its thickness is 81 nm;

[0116] The metal absorption layer is one or a combination of TiNi layer, TiNb layer, TiZr layer or NiCrMo layer, and its thickness is 2nm;

[0117] The second dielectric layer is a SiNx layer, and its thickness is 35nm;

[0118] The base layer is a glass substrate with a thickness of 6 mm.

[0119] The method for preparing the low-emissivity coated glass comprises:

[0120] The magnetron sputtering method is used to plate the first dielectric layer: SiNxOy on the clean glass surface, and the sputtering film is formed under the conditions of nitrogen and oxygen atmosphere, and the atmosphere is Ar:N2:O2=600:120:500sccm. The ITO layer is plated on the first dielectric layer, and the atmosphere is Ar:O2=1500:50sccm. Then, a metal absorption layer is plated on the infrared reflection functional layer ITO layer. The absorption layer can be one or a combination of TiNi, TiNb, TiZr, NiCrMo, and pure Ar gas sputtering is used to plate the second dielectric protection layer SiNx layer on the metal absorption layer. The atmosphere is Ar:N2=600:600sccm. Its performance is shown in the following table:

[0121]

[0122] Example 7

[0123] A low-emissivity coated glass comprises a substrate layer and a low-emissivity layer arranged on one side of the substrate layer, wherein the low-emissivity layer comprises a first dielectric layer, a transparent oxide conductive layer, a metal absorption layer and a second dielectric layer in order from near to far from the substrate layer;

[0124] The method for preparing the low-emissivity coated glass comprises:

[0125] Preparation method: Use large-scale magnetron sputtering coating equipment to coat the first dielectric layer, low-emissivity functional layer, metal absorption layer and second dielectric layer on the glass surface cleaned by a cleaning machine. The background vacuum value of the coating equipment is required to be 5×10 -6 mbar or less, the vacuum degree of the sputtering process atmosphere is (3~8)×10 -3 mbar range, and the coating equipment is not allowed to have any form of water vapor or gas leakage, and the background leakage rate is required to be less than 5×10 -9 mbar l / s. First, the first dielectric layer ZnSnOx is plated on the glass surface, and a metal ZnSn target is used to pass the reaction gas for sputtering film formation, wherein the Ar gas and O2 gas flow rates are 600sccm and 800sccm respectively, and a medium frequency power supply is used for control, and the power supply power is 40kw.

[0126] The first dielectric layer includes a ZnSnOx layer having a thickness of 20 nm;

[0127] AZO film layers are sequentially plated on the surface of ZnSnOx, using multiple AZO ceramic targets, introducing Ar gas and O2 gas, the gas flow rates are 1500sccm and 30sccm respectively, the total power of the power supply is 90kw, the transparent oxide conductive layer is an AZO layer, and its thickness is 200nm;

[0128] Metal absorption layers were plated on the AZO surface in sequence, using a DC pulse power supply, and a metal plane target as the target material. The metal absorption layers included a Cr layer, a Mo layer, and a Nb layer in order from near to far from the substrate layer. The power used by the power supply was 1kw, 2kw, and 1kw, respectively, and the thickness of the plated films was 2nm, 3nm, and 1nm, respectively.

[0129] A second dielectric layer is sequentially plated on the surface of the metal absorption layer, wherein the second dielectric layer is a ZrOx layer, a ceramic ZrOx target is used, a medium frequency power supply is used, Ar gas and O2 gas are introduced, the gas flow rates are 1500sccm and 50sccm respectively, the total power used by the power supply is 100kw, and the thickness of the plated ZrOx film layer is 100nm;

[0130] The base layer is a glass substrate with a thickness of 20 mm.

[0131] Its performance is shown in the following table:

[0132]

[0133] Example 8

[0134] A low-emissivity coated glass comprises a substrate layer and a low-emissivity layer arranged on one side of the substrate layer, wherein the low-emissivity layer comprises a first dielectric layer, a transparent oxide conductive layer, a metal absorption layer and a second dielectric layer in order from near to far from the substrate layer;

[0135] The first dielectric layer includes TiNx layers in order from near to far from the substrate layer, and the thickness of the layers is 66 nm;

[0136] The transparent oxide conductive layer includes an ATO layer and a TNO layer in terms of distance from the substrate layer from near to far, and the thicknesses thereof are 200 nm and 300 nm respectively;

[0137] The metal absorption layer includes a Ni layer, a Cr layer, a Ti layer and a Nb layer in order from near to far from the substrate layer, and the thickness of each layer is 5 nm;

[0138] The second dielectric layer is a SiNxOy layer, and its thickness is 30nm;

[0139] The base layer is a glass substrate with a thickness of 10 mm.

[0140] The method for preparing the low-emissivity coated glass comprises: coating a first dielectric layer, a transparent oxide conductive composite layer, a metal absorption layer and a second dielectric layer on the glass surface in sequence. The first dielectric layer uses a metal Ti rotating target, uses a medium frequency power supply, and introduces Ar and N2, the gas flow rates are 200sccm and 1400sccm respectively, and the total power of the power supply is 180kw.

[0141] A transparent conductive oxide ATO layer and a TNO layer are plated on the surface of the first dielectric layer in sequence. The targets used are ATO and TNO ceramic targets. Ar and O2 are introduced into ATO and TNO, and the gas flow rates are 1500sccm and 40sccm, respectively. The power used is 80kw and 120kw, respectively. A metal absorption composite layer is plated on the surface of the transparent conductive layer, and metal Ni, Cr, Ti and Nb planar targets are used. A DC pulse power supply is used for the power supply, and pure Ar gas is introduced. The gas flow rate is 1200sccm, and the power used by the power supply is 2kw, 2kw, 2.5kw and 1.5kw, respectively. The thickness used is 5nm.

[0142] The second dielectric absorption layer is plated on the surface of the metal absorption composite layer. The target material used is a silicon target material. The reaction gas is introduced to sputter and form a film. Ar, O2 and N2 gases are introduced, and the gas flow rates are 600sccm, 150sccm and 600sccm. The power supply uses a medium frequency power supply with a power of 50kw, and the film thickness is 30nm.

[0143] Its performance is shown in the following table:

[0144]

[0145] Example 9

[0146] A low-emissivity coated glass comprises a substrate layer and a low-emissivity layer arranged on one side of the substrate layer, wherein the low-emissivity layer comprises a first dielectric layer, a transparent oxide conductive layer, a metal absorption layer and a second dielectric layer in order from near to far from the substrate layer;

[0147] The first dielectric layer includes a NbOx layer and a ZrOx layer in order from near to far from the substrate layer, and the thicknesses thereof are 40 nm and 40 nm respectively;

[0148] The transparent oxide conductive layer includes a TNO layer and a GZO layer in order from near to far from the substrate layer, and the thickness of each layer is 150 nm;

[0149] The metal absorption layer includes a NiCr layer, a NiCrMo layer and a TiNb layer in order from near to far from the substrate layer, and the thicknesses thereof are 2 nm, 3 nm and 5 nm respectively;

[0150] The second dielectric layer includes a TiNx layer, a SiTiNxOy layer and a SiZrNxOy layer in order from near to far from the substrate layer, and the thicknesses thereof are 35 nm, 40 nm and 50 nm respectively;

[0151] The base layer is a glass substrate with a thickness of 2 mm.

[0152] The method for preparing the low-emissivity coated glass comprises:

[0153] The first dielectric layer was plated on the glass surface. The target materials were ceramic NbOx and ceramic ZrOx. Medium frequency power was used. The power was 40kw and 30kw respectively. Ar and O2 gas were introduced. The gas flow rate of ZrOx target was Ar:O2=1500sccm:50sccm, and the gas flow rate of NbOx was 1200sccm:200sccm. The thickness of the plated film was 40nm.

[0154] A transparent conductive oxide TNO layer and a GZO layer are successively plated on the surface of the first dielectric layer. The targets used are TNO and GZO ceramic targets. Ar and O2 are introduced into TNO and GZO with gas flow rates of 1500sccm and 40sccm, and the power used is 60kw and 70kw respectively.

[0155] A metal alloy absorption composite layer, a NiCr layer, a NiCrMo layer and a TiNb layer are plated on the surface of the transparent conductive layer and a metal alloy flat target is used. A DC pulse power supply is used as the power source, and pure Ar gas is introduced. The gas flow rate is 1200sccm. The power used by the power source is 1.5kw, 2kw, and 4kw respectively, and the thickness used is 2nm, 3nm and 5nm respectively;

[0156] The second dielectric layer is plated on the surface of the metal absorption composite layer. The targets used are metal Ti target, ceramic SiTi and SiZr target, and the reaction gas is introduced to sputter and form a film. Among them, Ar and O2 are introduced into the Ti target, and the gas flow rate is 200:1400sccm. Ar, O2 and N2 are introduced into SiTi and SiZr, and the gas flow rates are 600sccm, 150sccm and 600sccm respectively. The power supply uses a medium frequency power supply, and the power used is 100kw, 45kw and 60kw respectively. The film thickness is 35nm, 40nm and 50nm respectively.

[0157] Its performance is shown in the following table:

[0158]

[0159] Example 10

[0160] An offline low-emissivity coated glass comprises a substrate layer, and also comprises a low-emissivity layer arranged on the surface of the substrate layer, wherein the low-emissivity layer comprises a first dielectric layer, a transparent oxide conductive layer, an absorption layer, and a second dielectric layer arranged on the substrate layer in sequence from bottom to top;

[0161] The first dielectric layer includes a NbOx layer with a thickness of 40 nm;

[0162] The transparent oxide conductive layer includes a TZO layer with a thickness of 100 nm.

[0163] The absorption layer includes a TiNb layer with a thickness of 3 nm;

[0164] The second dielectric layer includes a SiNxOy layer with a thickness of 50 nm.

[0165] The method for preparing the low-emissivity coated glass comprises:

[0166] Its performance is shown in the following table:

[0167]

[0168] Embodiment 11

[0169] An offline low-emissivity coated glass comprises a substrate layer, and also comprises a low-emissivity layer arranged on the surface of the substrate layer, wherein the low-emissivity layer comprises a first dielectric layer, a transparent oxide conductive layer, an absorption layer, and a second dielectric layer arranged on the substrate layer in sequence from bottom to top;

[0170] The first dielectric layer includes a ZrOx layer and a SiNx layer, each having a thickness of 70 nm;

[0171] The transparent oxide conductive layer includes an ATO layer with a thickness of 80 nm.

[0172] The absorption layer includes a NiCrMo layer with a thickness of 5 nm;

[0173] The second dielectric layer includes a SiNxOy layer with a thickness of 80 nm.

[0174] The method for preparing the low-emissivity coated glass comprises:

[0175] Its performance is shown in the following table:

[0176]

[0177] Example 12

[0178] An offline low-emissivity coated glass comprises a substrate layer, and also comprises a low-emissivity layer arranged on the surface of the substrate layer, wherein the low-emissivity layer comprises a first dielectric layer, a transparent oxide conductive layer, an absorption layer, and a second dielectric layer arranged on the substrate layer in sequence from bottom to top;

[0179] The first dielectric layer includes a NbOx layer, a ZrOx layer, a SiNx layer and a SiNxOy layer in order from near to far from the substrate layer, and the thicknesses are 20nm, 30nm, 30nm and 40nm respectively;

[0180] The transparent oxide conductive layer includes an ITO layer, a TZO layer and an ATO layer in order from near to far from the substrate layer, and has a thickness of 200 nm;

[0181] The absorption layer includes a TiNb layer, a TiZr layer and a NiCrMo layer in order from near to far from the substrate layer, and the thickness is 2nm;

[0182] The second dielectric layer includes a ZrOx layer, a SiNx layer and a SiNxOy layer in order from near to far from the substrate layer, and has a thickness of 40 nm.

[0183] The method for preparing the low-emissivity coated glass comprises:

[0184] Its performance is shown in the following table:

[0185]

[0186] Example 13

[0187] An offline low-emissivity coated glass comprises a substrate layer, and also comprises two low-emissivity layers arranged on the surface of the substrate layer, each of the low-emissivity layers comprises a first dielectric layer, a transparent oxide conductive layer, an absorption layer, and a second dielectric layer arranged on the substrate layer in sequence from bottom to top;

[0188] The first dielectric layer includes a ZrOx layer and a SiNx layer, with thicknesses of 20nm and 60nm;

[0189] The transparent oxide conductive layer includes an ATO layer with a thickness of 100 nm.

[0190] The absorption layer includes a NiCrMo layer with a thickness of 5 nm;

[0191] The second dielectric layer includes a SiNxOy layer with a thickness of 50 nm.

[0192] The method for preparing the low-emissivity coated glass comprises:

[0193] Its performance is shown in the following table:

[0194]

[0195] Comparative Example 1

[0196] A method for preparing low-emissivity coated glass is the same as the preparation method described in Example 6 except that the tempering treatment is not performed.

[0197] The performance of the obtained low-emissivity coated glass is shown in the following table:

[0198]

[0199] Comparative Example 2

[0200] A coated glass, which is the same as Example 13 except that the absorption layer is replaced by a SiNx layer.

[0201] The performance of the obtained low-emissivity coated glass is shown in the following table:

[0202]

[0203] The applicant declares that the above is only a specific implementation mode of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention shall fall within the protection scope and disclosure scope of the present invention.

Claims

1. An offline low-emissivity coated glass, comprising a substrate layer, characterized in that: It also includes a low-emissivity layer disposed on the surface of the substrate layer, wherein the low-emissivity layer includes a first dielectric layer, a transparent oxide conductive layer, and a second dielectric layer disposed on the substrate layer in sequence from bottom to top; The second dielectric layer comprises any one or a combination of at least two of a metal or metalloid oxide layer, a metal or metalloid or metal alloy nitride layer, and a metal or metalloid or metal alloy oxynitride layer; The low-emissivity layer does not contain Ag, Cu or Au conductive metal film layer; The offline low-emissivity coated glass is prepared by the following method: at least one low-emissivity layer is prepared on a substrate layer, and the offline low-emissivity coated glass is obtained by tempering or bending the glass.

2. The offline low-emissivity coated glass according to claim 1, characterized in that: An absorption layer is also arranged between the transparent oxide conductive layer and the second dielectric layer.

3. The offline low-emissivity coated glass according to claim 2, characterized in that: The absorption layer includes any one of a Ni layer, a Cr layer, a Ti layer, a Nb layer, a Zr layer, a Mo layer, a NiCr layer, a NiCrMo layer, a TiNb layer, a TiNi layer, a NbZr layer or a ZrTi layer, or a combination of at least two of them.

4. The offline low-emissivity coated glass according to claim 3, characterized in that: The absorption layer is one of a NiCr layer, a NiCrMo layer or a NbZr layer, or a combination of at least two of them.

5. The offline low-emissivity coated glass according to claim 2, characterized in that: The thickness of the absorption layer is 0 to 20 nm, excluding 0.

6. The offline low-emissivity coated glass according to claim 1, characterized in that: The first dielectric layer includes any one of a metal or metalloid oxide layer, a metal or metalloid or metal alloy nitride layer, and a metal or metalloid or metal alloy oxynitride layer, or a combination of at least two of them.

7. The offline low-emissivity coated glass according to claim 6, characterized in that: The metal oxide layer of the first dielectric layer includes any one of TiOx, NbOx, ZrOx, ZnSnOx, ZnO or SnOx, or a combination of at least two thereof.

8. The offline low-emissivity coated glass according to claim 6, characterized in that: The metal or metalloid or metal alloy nitride layer of the first dielectric layer includes any one of TiNx, SiNx, SiAlNx, SiBNx, SiTiNx or SiZrNx, or a combination of at least two thereof.

9. The offline low-emissivity coated glass according to claim 6, characterized in that: The metal or metalloid or metal alloy oxynitride layer of the first dielectric layer includes any one of SiNxOy, SiAlNxOy, SiBNxOy, SiTiNxOy or SiZrNxOy, or a combination of at least two thereof.

10. The off-line low-emissivity coated glass according to claim 6, characterized in that: The first dielectric layer includes any one of NbOx, ZrOx, SiNx or SiNxOy, or a combination of at least two of them.

11. The offline low-emissivity coated glass according to claim 1, characterized in that: The thickness of the first dielectric layer is 20-80 nm.

12. The off-line low-emissivity coated glass according to claim 1, characterized in that: The transparent oxide conductive layer includes any one of ITO, AZO, TZO, ATO, TNO, GZO or FTO, or a combination of at least two thereof.

13. The off-line low-emissivity coated glass according to claim 12, characterized in that: The transparent oxide conductive layer is any one of ITO, TZO or ATO, or a combination of at least two of them.

14. The off-line low-emissivity coated glass according to claim 13, characterized in that: The transparent oxide conductive layer is ITO.

15. The offline low-emissivity coated glass according to claim 1, characterized in that: The thickness of the transparent oxide conductive layer is 80-500 nm.

16. The offline low-emissivity coated glass according to claim 1, characterized in that: The metal or metalloid oxide layer of the second dielectric layer includes any one of SiOx, TiOx, NbOx, ZrOx or SnOx, or a combination of at least two thereof.

17. The offline low-emissivity coated glass according to claim 1, characterized in that: The metal or metalloid oxide layer of the second dielectric layer includes an oxide layer of Si, SiAl, SiB, SiTi or SiZr.

18. The offline low-emissivity coated glass according to claim 1, characterized in that: The metal or metalloid or metal alloy nitride layer of the second dielectric layer includes any one of TiNx, SiNx, SiAlNx, SiBNx, SiTiNx or SiZrNx, or a combination of at least two thereof.

19. The offline low-emissivity coated glass according to claim 1, characterized in that: The metal or metalloid or metal alloy oxynitride layer of the second dielectric layer includes any one of SiNxOy, SiAlNxOy, SiBNxOy, SiTiNxOy or SiZrNxOy, or a combination of at least two thereof.

20. The offline low-emissivity coated glass according to claim 1, characterized in that: The second dielectric layer includes any one of ZrOx, SiNx or SiNxOy or a combination of at least two of them.

21. The off-line low-emissivity coated glass according to claim 20, characterized in that: The second dielectric layer is SiNx or ZrOx.

22. The offline low-emissivity coated glass according to claim 1, characterized in that: The thickness of the second dielectric layer is 30-100 nm.

23. The offline low-emissivity coated glass according to claim 1, characterized in that: The substrate layer includes a glass layer and / or an organic transparent plastic layer.

24. The off-line low-emissivity coated glass according to claim 1, characterized in that: The thickness of the base layer is 1 to 20 mm.

25. The offline low-emissivity coated glass according to claim 1, characterized in that: The thickness of the low-emissivity layer is 80-500 nm.

26. The offline low-emissivity coated glass according to claim 1, characterized in that: The off-line low-emissivity coated glass comprises at least one low-emissivity layer.

27. The offline low-emissivity coated glass according to claim 1, characterized in that: The offline low-emissivity coated glass is a single-piece structure or a hollow glass or a laminated glass structure.

28. The offline low-emissivity coated glass according to claim 1, characterized in that: The offline low-emissivity coated glass comprises a base layer and a low-emissivity layer arranged on the surface of the base layer, wherein the low-emissivity layer comprises a first dielectric layer, a transparent oxide conductive layer, an absorption layer and a second dielectric layer arranged on the base layer in sequence from bottom to top; The first dielectric layer includes any one of a NbOx layer, a ZrOx layer, a SiNx layer or a SiNxOy layer or a combination of at least two thereof, and has a thickness of 20 to 80 nm; The transparent oxide conductive layer includes any one of ITO, TZO or ATO or a combination of at least two thereof, and has a thickness of 80 to 200 nm; The absorption layer comprises any one of Ti, NiCr, TiNi, TiNb, TiZr or NiCrMo or a combination of at least two thereof, and has a thickness of 2 to 5 nm; The second dielectric layer includes any one of ZrOx, SiNx or SiNxOy or a combination of at least two thereof, and has a thickness of 40-80 nm.

29. The method for preparing off-line low-emissivity coated glass according to any one of claims 1 to 28, characterized in that: The method comprises: preparing at least one low-emissivity layer on a substrate layer, and subjecting the layer to tempering or bending tempering to obtain the offline low-emissivity coated glass; wherein the low-emissivity layer comprises a first dielectric layer, a transparent oxide conductive layer and a second dielectric layer which are arranged in sequence from near to far from the substrate layer.

30. The preparation method according to claim 29, characterized in that: The method for preparing at least a low-emissivity layer on the substrate layer includes any one of a magnetron sputtering method, a chemical vapor deposition method, an ion beam sputtering deposition method or an evaporation method.

31. The off-line low-emissivity coated glass according to claim 29, characterized in that: The temperature of the tempering treatment or bending tempering treatment is 680-710°C.

32. The off-line low-emissivity coated glass according to claim 29, characterized in that: The time of the tempering treatment or bending tempering treatment is 210 to 1200 seconds.

33. The off-line low-emissivity coated glass according to claim 29, characterized in that: The method further comprises a hollowing process and / or a sandwich process after the tempering process or the bending tempering process.

34. Use of the off-line low-emissivity coated glass according to any one of claims 1 to 28, which is used for interior decoration or outdoor curtain wall glass.

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