CN110642529B

CN110642529B - Window glass with silver alloy functional layer

Info

Publication number: CN110642529B
Application number: CN201911021283.7A
Authority: CN
Inventors: 曹晖; 何立山; 陈国富; 卢国水; 黄凤珠; 福原康太
Original assignee: Fuyao Glass Industry Group Co Ltd
Current assignee: Fuyao Glass Industry Group Co Ltd
Priority date: 2019-10-25
Filing date: 2019-10-25
Publication date: 2021-08-10
Anticipated expiration: 2039-10-25
Also published as: CN110642529A

Abstract

The invention relates to the field of glass products, in particular to glass installed on automobiles, and particularly provides a window glass with a silver alloy functional layer. The window glass comprises at least one glass substrate, wherein a silver alloy functional layer is deposited on at least one surface of the glass substrate, the silver alloy functional layer comprises at least one silver alloy layer and at least two dielectric layers, the silver alloy layer comprises metal silver and a first doped metal element, the first doped metal element is selected from at least one of copper, gold and platinum, and the mass percentage content of the first doped metal element is 0.5-2.5 mass%. The invention has excellent conductive performance and heat insulation performance, the change rate of the sheet resistance of the invention relative to the sheet resistance of the equivalent metal silver functional layer is less than or equal to 5% no matter before or after the high-temperature heat treatment at least 500 ℃, and the invention can be stored for at least 15 days in the atmospheric environment with the humidity of more than or equal to 60% and the temperature of more than or equal to 25 ℃, thereby ensuring the appearance quality.

Description

Window glass with silver alloy functional layer

The technical field is as follows:

the invention relates to the field of glass products, in particular to glass installed on automobiles, and particularly provides a window glass with a silver alloy functional layer.

Background art:

increasingly, single-silver coated glass, double-silver coated glass, triple-silver coated glass, and even silver-based coated glass including more silver layers are mounted on automobiles, and the glass panes on the automobiles have an electrical heating function and/or a heat insulating function due to the good electrical conductivity and infrared ray reflecting property of the silver layers. At the same time, since silver layers are susceptible to oxidation and corrosion, it is common to provide silver layers between at least two dielectric layers for protection, for example, patent US4017661A, CN86108656A, CN1093346A and CN1489556A, etc.

In the actual production process, even if a plurality of dielectric layers protect the silver layer, the silver-based coated glass is subjected to subsequent high-temperature heat treatment at least 500 ℃ in time after the coating is finished, for example, the silver-based coated glass is subjected to bending treatment at least 600 ℃ so as to prevent the silver-based coated glass from being oxidized and corroded in the atmospheric environment. Generally, the main sources of these oxidation and corrosion defects are: the main reasons for oxidation and corrosion defects caused by temperature, humidity, oxygen, sulfur, chlorine and the like are that the silver-based coated glass is stored in the atmospheric environment for too long time after coating is finished, for example, due to production orders, equipment failures, even off-site processing and transportation and the like, the silver-based coated glass cannot be subjected to high-temperature heat treatment in time after coating is finished, but needs to be stored in the atmospheric environment for a week or even longer, so that the silver-based coated glass is easily oxidized and corroded, and after being subjected to bending treatment at least 600 ℃, more oxidation and corrosion defects invisible to naked eyes are presented before. In order to solve the problem of the silver-based coated glass being easily oxidized and corroded in atmospheric environment, patent CN107709264A discloses a glazing comprising a functional coating based on silver and indium, to which is added 1.0% to 5.0% of indium, even further 0.05% to 1.0% of tin, in a silver-based metallic functional coating, in order to improve the chemical resistance of the glazing without damaging the thermal and energy properties and without significantly increasing the emissivity.

The invention content is as follows:

the technical problem to be solved by the invention is to provide a window glass with a silver alloy functional layer, which has excellent electrical property, oxidation resistance and corrosion resistance and can withstand heat treatment at a high temperature of at least 500 ℃, aiming at the defects that silver-based coated glass is easy to oxidize and corrode in the atmospheric environment.

The technical scheme adopted by the invention for solving the technical problems is as follows: a glazing having a functional layer of a silver alloy comprising at least one glass substrate, said functional layer of a silver alloy being deposited on at least one surface of the glass substrate, said functional layer of a silver alloy comprising at least one layer of a silver alloy and at least two dielectric layers, each layer of a silver alloy being located between two dielectric layers; the method is characterized in that: the silver alloy layer comprises metal silver and a first doped metal element, the first doped metal element is selected from at least one of copper, gold and platinum, the mass percentage content of the first doped metal element is 0.5-2.5 mass%, and the change rate of the sheet resistance of the silver alloy functional layer relative to the sheet resistance of the equivalent metal silver functional layer is less than or equal to 5%.

Preferably, the silver alloy layer further comprises a second doped rare earth element, the second doped rare earth element is selected from at least one of erbium, ytterbium, neodymium, samarium, lanthanum and cerium, and the mass percentage content of the second doped rare earth element is 0.3-1.0 mass%.

More preferably, the silver alloy layer further includes a third doping metal element, the third doping metal element is at least one selected from nickel, chromium, indium, tin, titanium, aluminum, zirconium, molybdenum, tungsten, manganese and magnesium, and the mass percentage of the third doping metal element is 0.2 to 1.0 mass%. And furthermore, the sum of the mass percentages of the first doped metal element, the second doped rare earth element and the third doped metal element is 1.0-3.0 mass%, the mass percentage of the second doped rare earth element is less than that of the first doped metal element, and the mass percentage of the third doped metal element is less than or equal to that of the second doped rare earth element.

Preferably, the silver alloy functional layer further comprises a bottom protective layer and a top protective layer, the silver alloy functional layer comprises 1-5 silver alloy layers, the bottom protective layer is located between the dielectric layer closest to the glass substrate and the glass substrate, and the top protective layer is located above the dielectric layer farthest from the glass substrate.

More preferably, the film system structure of the silver alloy functional layer deposited from the surface of the glass substrate to the outside in sequence is as follows: glass substrate/bottom protective layer/first dielectric layer/silver alloy layer/second dielectric layer/top protective layer.

More preferably, the film system structure of the silver alloy functional layer deposited from the surface of the glass substrate to the outside in sequence is as follows: glass substrate/bottom protective layer/first dielectric layer/first silver alloy layer/second dielectric layer/second silver alloy layer/third dielectric layer/top protective layer.

More preferably, the film system structure of the silver alloy functional layer deposited from the surface of the glass substrate to the outside in sequence is as follows: glass substrate/bottom protective layer/first dielectric layer/first silver alloy layer/second dielectric layer/second silver alloy layer/third dielectric layer/third silver alloy layer/fourth dielectric layer/top protective layer.

More preferably, the film system structure of the silver alloy functional layer deposited from the surface of the glass substrate to the outside in sequence is as follows: glass substrate/bottom protective layer/first dielectric layer/first silver alloy layer/second dielectric layer/second silver alloy layer/third dielectric layer/third silver alloy layer/fourth dielectric layer/fourth silver alloy layer/fifth dielectric layer/top protective layer.

More preferably, the material of the bottom protective layer or the top protective layer is selected from at least one of SiOx (1.5. ltoreq. x.ltoreq.2), SiOyNz (0.5. ltoreq. y.ltoreq.2, 0.5. ltoreq. z.ltoreq.1), SiOmCN (0.5. ltoreq. m.ltoreq.2, 0.5. ltoreq. n.ltoreq.1). Further, the Si is doped with at least one of Zr, Al, Mg, Ti and Bi.

More preferably, at least one of the dielectric layers comprises a high refractive index layer and a medium refractive index layer, the refractive index of the high refractive index layer is 2.2-2.6, and the refractive index of the medium refractive index layer is 1.8-2.1.

Further, the high refractive index layer has a refractive index at least 0.2 greater than the refractive index of the medium refractive index layer and the thickness of the medium refractive index layer is at least 2 times the thickness of the high refractive index layer.

Further, the material of the high refractive index layer is selected from at least one of oxides and oxynitrides of titanium, and the material of the medium refractive index layer is selected from at least one of oxides of metals such as zinc, tin, magnesium, titanium, tantalum, niobium, bismuth, zirconium, manganese and alloys thereof, and/or at least one of nitrides of metals such as silicon, zirconium, titanium, aluminum and alloys thereof. Further, the titanium in the high refractive index layer is doped with at least one of zinc, tin, silicon, aluminum, zirconium, niobium, tantalum, bismuth, nickel, and chromium.

Preferably, the glazing comprises two glass substrates and a thermoplastic interlayer sandwiched between the two glass substrates, the functional layer of silver alloy being deposited on a surface of at least one of the glass substrates adjacent to the thermoplastic interlayer.

Due to the adoption of the technical scheme, the invention has the following beneficial effects:

the window glass with the silver alloy functional layer has excellent electric conductivity and heat insulation performance, the change rate of the sheet resistance of the window glass relative to the sheet resistance of the equivalent metal silver functional layer is less than or equal to 5% no matter before or after the window glass is subjected to high-temperature heat treatment at least at 500 ℃, the window glass can be stored in an atmospheric environment with the humidity of more than or equal to 60% and the temperature of more than or equal to 25 ℃ for at least 15 days, and the appearance quality is guaranteed.

Description of the drawings:

FIG. 1 is a schematic diagram of a film system structure of a silver alloy functional layer comprising a silver alloy layer according to the present invention;

fig. 2 is a schematic diagram of a film system structure of a silver alloy functional layer comprising two silver alloy layers according to the present invention;

fig. 3 is a schematic structural diagram of a film system of a silver alloy functional layer comprising three silver alloy layers according to the present invention;

fig. 4 is a schematic structural diagram of a film system of a silver alloy functional layer comprising four silver alloy layers according to the present invention;

fig. 5 is a schematic view of a laminated glass glazing according to the present invention.

The specific implementation mode is as follows:

the invention will be further explained with reference to the accompanying drawings.

As shown in fig. 1, 2, 3 and 4, a glazing according to the invention having functional layers of silver alloys capable of performing an electrical heating function and/or a thermal insulating function comprises at least one glass substrate 100, said functional layers of silver alloys being deposited on at least one surface of the glass substrate 100, said functional layers of silver alloys comprising at least one layer of silver alloys and at least two dielectric layers, each layer of silver alloys being located between two dielectric layers; the glass window comprises a glass window body, a glass window body and a silver alloy functional layer, wherein the glass window body comprises a glass window body, the glass window body is provided with a glass window glass, the glass window body is provided with a silver alloy functional layer, a silver alloy layer and a silver alloy layer, the silver alloy layer comprises a silver alloy layer and a first doped metal element, the first doped metal element is selected from at least one of copper (Cu), gold (Au) and platinum (Pt), the mass percentage of the first doped metal element is 0.5% -2.5%, and the change rate of the sheet resistance of the silver alloy functional layer relative to the equivalent sheet resistance of the metal silver functional layer is less than or equal to 5%, so that the glass window glass has excellent electrical performance and heat insulation performance. Preferably, the silver alloy layer further comprises a second doped rare earth element, the second doped rare earth element is selected from at least one of erbium (Er), ytterbium (Yb), neodymium (Nd), samarium (Sm), lanthanum (La) and cerium (Ce), and the mass percentage of the second doped rare earth element is 0.3-1.0 mass%; by adding the second doped rare earth element, the vulcanization resistance of the window glass can be improved. More preferably, the silver alloy layer further comprises a third doping metal element, the third doping metal element is selected from at least one of nickel (Ni), chromium (Cr), indium (In), tin (Sn), titanium (Ti), aluminum (Al), zirconium (Zr), molybdenum (Mo), tungsten (W), manganese (Mn), and magnesium (Mg), and the mass percentage of the third doping metal element is 0.2 mass% to 1.0 mass%; the third doped metal element is added, so that the vulcanization resistance and the chlorination resistance of the window glass can be further improved; therefore, the electrical performance of the silver alloy functional layer is not affected, the change rate of the sheet resistance of the silver alloy functional layer relative to the sheet resistance of an equivalent metal silver functional layer is less than or equal to 5% no matter before or after the silver alloy functional layer is subjected to high-temperature heat treatment at least 500 ℃, the oxidation resistance and the corrosion resistance of the window glass can be improved, the window glass can be stored in an atmospheric environment with the humidity of more than or equal to 60% and the temperature of more than or equal to 25 ℃ for at least 15 days, and the appearance quality of the window glass can be ensured.

In the present invention, the term "equivalent" means that the film system structure and the film system thickness are the same when the silver alloy layer is substituted for the metallic silver layer, for example, the silver alloy functional layer is a silver alloy tri-film system having a structure and a thickness of 10 nm./silver alloy layer 15 nm./silver alloy layer 13nm.. so that the equivalent metallic silver functional layer is a silver tri-film system having a structure and a thickness of 10 nm./metallic silver layer 15 nm./metallic silver layer 13nm.. so.

The silver alloy functional layer may be deposited on at least one surface of the glass substrate 100 by a vapor deposition method, for example, by a magnetron sputtering process. In particular, the silver alloy functional layer is a layer comprising an alloy of silver and a first doping metal element, even a layer further comprising an alloy of a second doping rare earth element and/or a third doping metal element, which can be obtained by co-deposition of at least two metal targets (for example one silver and a first doping metal element) or by deposition from targets already comprising an alloy of silver and a first doping metal element. Furthermore, the sum of the mass percentages of the first doped metal element, the second doped rare earth element and the third doped metal element is 1.0-3.0 mass%, the mass percentage of the second doped rare earth element is less than the mass percentage of the first doped metal element, and the mass percentage of the third doped metal element is less than or equal to the mass percentage of the second doped rare earth element. Wherein the thickness of the silver alloy layer is preferably 5 to 20 nm.

In the invention, the silver alloy functional layer further comprises a bottom protective layer and a top protective layer, the silver alloy functional layer comprises 1-5 silver alloy layers, the bottom protective layer is positioned between the dielectric layer closest to the glass substrate and the glass substrate, and the top protective layer is positioned above the dielectric layer farthest from the glass substrate. Specifically, in fig. 1, the silver alloy functional layer comprises a silver alloy layer, and the film system structure sequentially deposited from the surface of the glass substrate 100 to the outside is as follows: glass substrate 100/bottom protective layer 11/first dielectric layer 12/silver alloy layer 13/second dielectric layer 14/top protective layer 15. In fig. 2, the silver alloy functional layer comprises two silver alloy layers, and the film system structure sequentially deposited from the surface of the glass substrate 100 to the outside is as follows: the glass substrate 100/the bottom protective layer 21/the first dielectric layer 22/the first silver alloy layer 23/the second dielectric layer 24/the second silver alloy layer 25/the third dielectric layer 26/the top protective layer 27; it will be appreciated that the first silver alloy layer 23 or the second silver alloy layer 25 may be replaced by a metallic silver layer, i.e. the silver alloy functional layer comprises one silver alloy layer and one metallic silver layer. In fig. 3, the silver alloy functional layer comprises three silver alloy layers, and the film system structure sequentially deposited from the surface of the glass substrate 100 to the outside is as follows: glass substrate 100/bottom protective layer 31/first dielectric layer 32/first silver alloy layer 33/second dielectric layer 34/second silver alloy layer 35/third dielectric layer 36/third silver alloy layer 37/fourth dielectric layer 38/top protective layer 39; it will be appreciated that one or both of the first silver alloy layer 33, the second silver alloy layer 35 or the third silver alloy layer 37 may be replaced by a metallic silver layer, i.e. the silver alloy functional layer comprises one silver alloy layer and two metallic silver layers, or comprises two silver alloy layers and one metallic silver layer. In fig. 4, the silver alloy functional layer comprises four silver alloy layers, and the film system structure sequentially deposited from the surface of the glass substrate 100 to the outside is as follows: glass substrate 100/bottom protective layer 41/first dielectric layer 42/first silver alloy layer 43/second dielectric layer 44/second silver alloy layer 45/third dielectric layer 46/third silver alloy layer 47/fourth dielectric layer 48/fourth silver alloy layer 49/fifth dielectric layer 50/top protective layer 51; it will be appreciated that one, two or three of the first silver alloy layer 43, the second silver alloy layer 45, the third silver alloy layer 47 or the fourth silver alloy layer 49 may be replaced by metallic silver layers, i.e. the silver alloy functional layer comprises one silver alloy layer and three metallic silver layers, or comprises two silver alloy layers and two metallic silver layers, or comprises three silver alloy layers and one metallic silver layer.

The bottom

protective layers

11, 21, 31, 41 can reduce the pollution of residual organic matters or acid and alkali on the silver alloy layer caused by unclean cleaning, reduce defects in high-temperature heat treatment at least 500 ℃, and improve the oxidation resistance and corrosion resistance of the window glass, and preferably the materials are at least one selected from SiOx (1.5 ≦ x ≦ 2), SiOyNz (0.5 ≦ y < 2, 0.5 ≦ z ≦ 1), SiOmCN (0.5 ≦ m < 2, 0.5 ≦ n ≦ 1); more preferably, the silicon (Si) in the bottom

protective layer

11, 21, 31, 41 may be doped with at least one of zirconium (Zr), aluminum (Al), magnesium (Mg), titanium (Ti), and bismuth (Bi). The thicknesses of the

bottom protection layers

11, 21, 31 and 41 are preferably 5-20 nm. It is understood that the bottom

protective layer

11, 21, 31, 41 may also be a multi-layer structure, such as SiOx/SiOyNz, SiOx/SiOmCn, SiOx/SiOyNz/SiOx, etc.

At least one of the

dielectric layers

12, 14, 22, 24, 26, 32, 34, 36, 38, 42, 44, 46, 48, 50 includes a high refractive index layer and a medium refractive index layer, the refractive index of the high refractive index layer is 2.2-2.6, the refractive index of the medium refractive index layer is 1.8-2.1, the refractive index of the high refractive index layer is at least 0.2 greater than the refractive index of the medium refractive index layer, and the thickness of the medium refractive index layer is at least 2 times the thickness of the high refractive index layer. Preferably, the material of the high refractive index layer is selected from at least one of an oxide of titanium (Ti), an oxynitride; the material of the middle refractive index layer is at least one of oxides of metals such as zinc (Zn), tin (Sn), magnesium (Mg), titanium (Ti), tantalum (Ta), niobium (Nb), bismuth (Bi), zirconium (Zr) and manganese (Mn) and alloys thereof, and/or at least one of nitrides of metals such as silicon (Si), zirconium (Zr), titanium (Ti) and aluminum (Al) and alloys thereof. More preferably, the titanium (Ti) in the high refractive index layer may be doped with at least one of zinc (Zn), tin (Sn), silicon (Si), aluminum (Al), zirconium (Zr), niobium (Nb), tantalum (Ta), bismuth (Bi), nickel (Ni), and chromium (Cr). The thicknesses of the

dielectric layers

12, 14, 22, 24, 26, 32, 34, 36, 38, 42, 44, 46, 48 and 50 are preferably 15-80 nm. Specifically, the structures of the high refractive index layer and the medium refractive index layer in the

dielectric layers

12, 14, 22, 24, 26, 32, 34, 36, 38, 42, 44, 46, 48, 50 may be exemplified by a high refractive index layer/medium refractive index layer, a medium refractive index layer/high refractive index layer, a high refractive index layer/medium refractive index layer/high refractive index layer, a medium refractive index layer/high refractive index layer/medium refractive index layer, and the like. Optionally, other layers, such as a nickel layer (Ni), a chromium layer (Cr), a nickel-chromium alloy layer (NiCr), a titanium layer (Ti), etc., may be further added to the

dielectric layers

12, 14, 22, 24, 26, 32, 34, 36, 38, 42, 44, 46, 48, 50 as needed.

The top

protective layers

15, 27, 39 and 51 can reduce the water vapor invasion in the atmospheric environment, reduce the pollution of organic matters or acid and alkali remained on the glass substrate to the silver alloy layer, reduce the defects in the high-temperature heat treatment at least 500 ℃, and improve the oxidation resistance and corrosion resistance of the window glass, and preferably, the materials are selected from at least one of SiOx (1.5 ≤ x ≤ 2), SiOyNz (0.5 ≤ y < 2, 0.5 ≤ z ≤ 1), SiOmCN (0.5 ≤ m < 2, 0.5 ≤ n ≤ 1); more preferably, the silicon (Si) in the top

protective layer

15, 27, 39, 51 may be doped with at least one of zirconium (Zr), aluminum (Al), magnesium (Mg), titanium (Ti), and bismuth (Bi). The thickness of the top

protective layer

15, 27, 39, 51 is preferably 5-20 nm. It is understood that the top

protective layer

15, 27, 39, 51 may also be a multi-layer structure, such as SiOx/SiOyNz, SiOx/SiOmCn, SiOx/SiOyNz/SiOx, etc.

Wherein the glazing is capable of withstanding a high temperature heat treatment of at least 500 ℃, such as a tempering or bending process for automotive glass. The window glass can be single-piece toughened glass, and the silver alloy functional layer is deposited on the surface of the single-piece toughened glass in the vehicle; the glazing may also be a multiple pane laminated glass, such as the glazing structure shown in fig. 4, comprising two glass substrates 100 and a thermoplastic interlayer 101 sandwiched between the two glass substrates 100, the silver alloy functional layer 102 being deposited on the surface of either glass substrate 100 adjacent to the thermoplastic interlayer 101, i.e. the silver alloy functional layer 102 being deposited on the second or third face of the laminated glass.

Examples and comparative examples

The method is characterized in that soda-lime-silicate glass with the thickness of 2.1mm produced by Fuyao group is taken as a substrate, and after the processes of cutting, edging, washing, drying and the like, the substrate enters a coating line for coating deposition, and a film layer is deposited on the glass substrate according to the following film system structure.

Comparative example 1 and examples 1 to 3

Comparative example 1: glass substrate/SiOyNz 10nm/TiOx 8nm/Zn₂SnO₄23nm/AZO 10 nm/metal Ag 11.5nm/TiOx5nm/Zn₂SnO₄ 30nm/TiOx 4nm/SiO₂ 10nm

Example 1: glass substrate/SiOyNz 10nm/TiOx 8nm/Zn₂SnO₄23nm/AZO 10nm/Ag alloy 11.5nm/TiOx5nm/Zn₂SnO₄ 30nm/TiOx 4nm/SiO₂ 10nm

The Ag alloy is: 98.7% Ag-1.3% Cu (mass percentage)

Example 2: glass substrate/SiOyNz 18nm/TiOx 8nm/Zn₂SnO₄23nm/AZO 10nm/Ag alloy 11.5nm/TiOx5nm/Zn₂SnO₄ 30nm/TiOx 4nm/SiO₂ 10nm

The Ag alloy is: 97.7% Ag-1.8% Cu-0.5% Er (mass percentage)

Example 3: glass substrate/SiO₂ 15nm/TiOx 8nm/Zn₂SnO₄23nm/AZO 10nm/Ag alloy 11.5nm/TiOx5nm/Zn₂SnO₄ 30nm/TiOx 4nm/SiO₂ 15nm

The Ag alloy is: 97.2% Ag-2.0% Cu-0.5% Er-0.3% Al (mass percentage)

After the deposition of the film layer is finished, the glass substrate with the film coating obtained in the comparative example 1 and the examples 1-3 is stored for 15 days in an atmospheric environment with the humidity of more than or equal to 60% and the temperature of more than or equal to 25 ℃, then, the soda-lime-silicate glass with the thickness of 2.1mm produced by another Fumao group is taken as a matching sheet, bending forming is carried out according to the baking and bending forming process of the automobile glass, then, the sheet resistance and the haze of the film system are measured, the surface appearance of the film layer is observed, whether the appearance quality meets the requirements of QC/T985-.

Table 1: sheet resistance, haze and appearance quality of comparative example 1 and examples 1 to 3

As can be seen from table 1: compared with the square resistor of the comparative example 1, the square resistor of the examples 1 to 3 has the change rate of less than 5% both before and after bending by baking; after being stored for 15 days in an atmospheric environment with the humidity of more than or equal to 60% and the temperature of more than or equal to 25 ℃, the examples 1-3 before being baked and bent have no haze and the appearance quality meets the requirement, the comparative example 1 after being baked and bent has haze and appearance defects such as white spots, opacification and the like which do not meet the requirement, and the examples 1-3 after being baked and bent still have no haze and the appearance quality meets the requirement; thus, the silver alloy layer of examples 1 to 3, which includes a silver alloy layer, still maintains excellent electrical properties after being stored in an atmospheric environment with a humidity of 60% or more and a temperature of 25 ℃ or more for 15 days, and is capable of resisting oxidation and corrosion and undergoing a high-temperature heat treatment at least 500 ℃.

Comparative example 2 and examples 4 to 6

Comparative example 2: glass substrate/SiO₂ 15nm/SiOyNz 5nm/Zn₂SnO₄25nm/AZO 8nm/Ag 11.5nm/NiCr 1nm/Zn₂SnO₄60.6nm/TiOx 5nm/AZO 10 nm/metal Ag 11.5nm/ZnO 8nm/Si₃N₄21nm/SiOyNz 5nm/SiO₂ 3nm

Example 4: glass substrate/SiO₂ 15nm/SiOyNz 5nm/Zn₂SnO₄25nm/AZO 8nm/Ag alloy 11.5nm/NiCr 1nm/Zn₂SnO₄60.6nm/TiOx 5nm/AZO 10nm/Ag alloy 11.5nm/ZnO 8nm/Si₃N₄21nm/SiOyNz 5nm/SiO₂ 3nm

The Ag alloy is: 98.2% Ag-1.1% Au-0.7% Cu (mass percentage)

Example 5: glass substrate/SiOyNz 5nm/SiO₂ 10nm/Zn₂SnO₄25nm/AZO 8nm/Ag alloy 11.5nm/NiCr 1nm/Zn₂SnO₄60.6nm/TiOx 5nm/AZO 10nm/Ag alloy 11.5nm/ZnO 8nm/Si₃N₄21nm/SiOyNz 5nm/SiO₂ 3nm

The Ag alloy is: 97.8% Ag-1.7% Cu-0.5% Nb (mass percentage)

Example 6: glass substrate/SiO₂ 15nm/Zn₂SnO₄25nm/AZO 8nm/Ag alloy 11.5nm/NiCr 1nm/Zn₂SnO₄60.6nm/TiOx 5nm/AZO 10nm/Ag alloy 11.5nm/ZnO 8nm/Si₃N₄ 21nm/SiOyNz 5nm/SiO₂ 3nm

The Ag alloy is: 97.3% Ag-1.5% Au-0.8% Yb-0.4% Ni (mass percentage)

After the deposition of the film layer is finished, the glass substrate with the film coating obtained in the comparative example 2 and the examples 4-6 is stored for 15 days in an atmospheric environment with the humidity of more than or equal to 60% and the temperature of more than or equal to 25 ℃, then, the soda-lime-silicate glass with the thickness of 2.1mm produced by another Fumao group is taken as a matching sheet, bending forming is carried out according to the baking and bending forming process of the automobile glass, then, the sheet resistance and the haze of the film system are measured, the surface appearance of the film layer is observed, whether the appearance quality meets the requirements of QC/T985-.

Table 2: sheet resistance, haze and appearance quality of comparative example 2 and examples 4-6

As can be seen from table 2: compared with the square resistor of the comparative example 2, the square resistors of the examples 4 to 6 have the change rate of less than 5% both before and after bending by baking; after being stored for 15 days in an atmospheric environment with the humidity of more than or equal to 60% and the temperature of more than or equal to 25 ℃, the examples 4-6 before being baked and bent and the comparative example 2 have no haze and meet the requirement of appearance quality, the comparative example 2 after being baked and bent has haze and appearance defects such as white spots, opacification and the like which do not meet the requirement, and the examples 4-6 after being baked and bent still have no haze and meet the requirement of appearance quality; therefore, the examples 4-6 containing two silver alloy layers still maintain excellent electrical properties after being stored for 15 days in an atmospheric environment with humidity of more than or equal to 60% and temperature of more than or equal to 25 ℃, and can resist oxidation and corrosion and undergo high-temperature heat treatment at least 500 ℃.

Comparative example 3 and examples 7 to 9

Comparative example 3: glass substrate/SiOyNz 5nm/SiO₂ 10nm/TiOx 4nm/Zn₂SnO₄22nm/TiOx 8nm/AZO 10 nm/metal Ag 13.5nm/AZO 10nm/SiZrNx 55nm/AZO 10 nm/metal Ag 14.5nm/ZnO 8nm/TiOx 8nm/Zn₂SnO₄49nm/AZO 10 nm/metal Ag 13.5nm/TiOx 5nm/AZO 10nm/SiZrNx 21nm/SiOyNz 5nm/SiO₂ 10nm

Example 7: glass substrate/SiOyNz 5nm/SiO₂ 10nm/TiOxNy 4nm/Zn₂SnO₄22nm/TiOx 8nm/AZO 10nm/Ag alloy 13.5nm/AZO 10nm/SiZrNx 55nm/AZO 10nm/Ag alloy 14.5nm/ZnO 8nm/TiOx 8nm/Zn₂SnO₄49nm/AZO 10nm/Ag alloy 13.5nm/TiOx 5nm/AZO 10nm/SiZrNx 21nm/SiO₂8nm

The Ag alloy is: 98.1% Ag-1.9% Cu (mass percentage)

Example 8: glass substrate/SiOyNz 5nm/SiO₂ 10nm/TiOx 4nm/Zn₂SnO₄22nm/TiOx 8nm/AZO 10nm/Ag alloy 13.5nm/AZO 10nm/SiZrNx 55nm/AZO 10nm/Ag alloy 14.5nm/ZnO 8nm/TiOx 8nm/Zn₂SnO₄49nm/AZO 10nm/Ag alloy 13.5nm/TiOx 5nm/AZO 10nm/SiZrNx 21nm/SiOyNz 5nm/SiO₂ 10nm

The Ag alloy is: 98.0% Ag-1.5% Cu-0.5% Ce (mass percent)

Example 9: glass substrate/SiO₂ 8nm/TiOx 4nm/Zn₂SnO₄22nm/TiOx 8nm/AZO 10nm/Ag alloy 13.5nm/AZO 10nm/SiZrNx 55nm/AZO 10nm/Ag alloy 14.5nm/ZnO 8nm/TiOx 8nm/Zn₂SnO₄49nm/AZO 10nm/Ag alloy 13.5nm/TiOx 5nm/AZO 10nm/SiZrNx 21nm/SiO₂ 8nm

The Ag alloy is: 98.2% Ag-0.5% Au-0.8% Cu-0.3% Nd-0.2% Ti (mass percentage)

After the deposition of the film layer is finished, the glass substrate with the film coating obtained in the comparative example 3 and the examples 7-9 is stored for 15 days in an atmospheric environment with the humidity of more than or equal to 60% and the temperature of more than or equal to 25 ℃, then, the soda-lime-silicate glass with the thickness of 2.1mm produced by another Fumao group is taken as a matching sheet, bending forming is carried out according to the baking and bending forming process of the automobile glass, then, the sheet resistance and the haze of the film system are measured, the surface appearance of the film layer is observed, whether the appearance quality meets the requirements of QC/T985-.

Table 3: sheet resistance, haze and appearance quality of comparative example 3 and examples 7-9

As can be seen from table 3: compared with the square resistor of the comparative example 3, the square resistors of the examples 7 to 9 have the change rate of less than 5% both before and after bending by baking; after being stored for 15 days in an atmospheric environment with the humidity of more than or equal to 60% and the temperature of more than or equal to 25 ℃, the examples 7-9 and the comparative example 3 before being bent by baking have no haze and meet the requirement of appearance quality, the comparative example 3 after being bent by baking has haze and appearance defects such as white spots, opacification and the like which do not meet the requirement, and the examples 7-9 after being bent by baking still have no haze and meet the requirement of appearance quality; therefore, the examples 7-9 containing three silver alloy layers still maintain excellent electrical properties after being stored for 15 days in an atmospheric environment with humidity of more than or equal to 60% and temperature of more than or equal to 25 ℃, and can resist oxidation and corrosion and undergo high-temperature heat treatment at least 500 ℃.

Comparative example 4 and examples 10 to 12

Comparative example 4: glass substrate/SiO₂ 15nm/Zn₂SnO₄30nm/AZO 10nm/Ag metal 11.1nm/AZO 10nm/SiZrNx 68.5nm/AZO 10nm/Ag metal 12.6nm/ZnO 12nm/Zn₂SnO₄60nm/AZO 10 nm/metal Ag 11.0nm/AZO 10nm/Zn₂SnO₄63nm/AZO 10 nm/metal Ag 14nm/ZnO 12nm/SiNx 45nm/SiO₂15nm

Example 10: glass substrate/SiO₂ 15nm/Zn₂SnO₄30nm/AZO 10nm/Ag alloy 11.1nm/AZO 10nm/SiZrNx 68.5nm/AZO 10nm/Ag alloy 12.6nm/ZnO 12nm/Zn₂SnO₄60nm/AZO 10nm/Ag alloy 11.0nm/AZO 10nm/Zn₂SnO₄63nm/AZO 10nm/Ag alloy 14nm/ZnO 12nm/SiNx 45nm/SiO₂ 15nm

The Ag alloy is: 98.0% Ag-2.0% Pt (mass percentage)

Example 11: glass substrate/SiO₂ 15nm/Zn₂SnO₄30nm/AZO 10nm/Ag alloy 11.1nm/AZO 10nm/SiZrNx 68.5nm/AZO 10nm/Ag alloy 12.6nm/ZnO 12nm/Zn₂SnO₄60nm/AZO 10nm/Ag alloy 11.0nm/AZO 10nm/Zn₂SnO₄63nm/AZO 10nm/Ag alloy 14nm/ZnO 12nm/SiNx 45nm/SiO₂ 15nm

The Ag alloy is: 98.0% Ag-1.5% Pt-0.5% Ce (mass percent)

Example 12: glass substrate/SiO₂ 15nm/Zn₂SnO₄30nm/AZO 10nm/Ag alloy 11.1nm/AZO 10nm/SiZrNx 68.5nm/AZO 10nm/Ag alloy 12.6nm/ZnO 12nm/Zn₂SnO₄60nm/AZO 10nm/Ag alloy 11.0nm/AZO 10nm/Zn₂SnO₄63nm/AZO 10nm/Ag alloy 14nm/ZnO 12nm/SiNx 45nm/SiO₂ 15nm

The Ag alloy is: 98.1% Ag-0.5% Pt-0.8% Cu-0.3% Nd-0.3% Ti (mass percentage)

After the deposition of the film layer is finished, the glass substrate with the film coating obtained in the comparative example 4 and the examples 10-12 is stored for 15 days in an atmospheric environment with the humidity of more than or equal to 60% and the temperature of more than or equal to 25 ℃, then, the soda-lime-silicate glass with the thickness of 2.1mm produced by another Fumao group is taken as a matching sheet, bending forming is carried out according to the baking and bending forming process of the automobile glass, then, the sheet resistance and the haze of the film system are measured, the surface appearance of the film layer is observed, whether the appearance quality meets the requirements of QC/T985-2014 is judged, and relevant results are shown in a table 4.

Table 4: sheet resistance, haze and appearance quality of comparative example 4 and examples 10 to 12

As can be seen from table 4: compared with the sheet resistance of the comparative example 4, the sheet resistance of the examples 10 to 12 has a change rate of less than 5% both before and after bending; after being stored for 15 days in an atmospheric environment with the humidity of more than or equal to 60% and the temperature of more than or equal to 25 ℃, the examples 10-12 before being baked and bent and the comparative example 4 have no haze and meet the requirement of appearance quality, the comparative example 4 after being baked and bent has haze and appearance defects such as white spots, opacification and the like which do not meet the requirement, and the examples 10-12 after being baked and bent still have no haze and meet the requirement of appearance quality; thus, the examples 10 to 12 including the four silver alloy layers still maintain excellent electrical properties after being stored in an atmospheric environment with humidity of 60% or more and temperature of 25 ℃ or more for 15 days, and are capable of resisting oxidation and corrosion and undergoing high-temperature heat treatment at least 500 ℃.

The above-mentioned embodiments of the present invention are all described in the description of the film structure and the corresponding film material, and the specific deposition process, parameters, and the specific process and parameters of the laminated glass are not described, it is understood that these non-described portions are well known to those skilled in the art, and therefore the non-described portions do not affect the scope of the present invention.

The above description specifically describes a window glass having a functional layer of silver alloy according to the present invention, but the present invention is not limited to the above-described embodiments, and therefore, any improvements, equivalent modifications, substitutions and the like made in accordance with the technical gist of the present invention are within the scope of the present invention.

Claims

1. A glazing having a functional layer of a silver alloy comprising at least one glass substrate, said functional layer of a silver alloy being deposited on at least one surface of the glass substrate, said functional layer of a silver alloy comprising at least one layer of a silver alloy and at least two dielectric layers, each layer of a silver alloy being located between two dielectric layers; the method is characterized in that: the silver alloy layer comprises metal silver and a first doped metal element, the first doped metal element is selected from at least one of copper, gold and platinum, the mass percentage content of the first doped metal element is 0.5-2.5 mass%, and the change rate of the sheet resistance of the silver alloy functional layer relative to the sheet resistance of an equivalent metal silver functional layer is less than or equal to 5% after the silver alloy functional layer is subjected to high-temperature heat treatment at least 500 ℃;

the silver alloy layer also comprises a second doped rare earth element, and the second doped rare earth element is selected from at least one of erbium, ytterbium, neodymium, samarium, lanthanum and cerium;

the silver alloy layer also comprises a third doped metal element, the third doped metal element is selected from at least one of nickel, chromium, indium, tin, titanium, zirconium, molybdenum, tungsten, manganese and magnesium, and the mass percentage of the third doped metal element is 0.2-1.0 mass%;

the sum of the mass percentages of the first doped metal element, the second doped rare earth element and the third doped metal element is 1.0-3.0 mass%, the mass percentage of the second doped rare earth element is less than that of the first doped metal element, and the mass percentage of the third doped metal element is less than or equal to that of the second doped rare earth element.

2. A glazing having a functional layer of silver alloy according to claim 1 characterised in that: the mass percentage content of the second doped rare earth element is 0.3 to 1.0mass percent.

3. A glazing having a functional layer of silver alloy according to claim 1 characterised in that: the silver alloy functional layer further comprises a bottom protective layer and a top protective layer, the silver alloy functional layer comprises 1-5 silver alloy layers, the bottom protective layer is located between the dielectric layer closest to the glass substrate and the glass substrate, and the top protective layer is located above the dielectric layer farthest from the glass substrate.

4. A glazing having a functional layer of silver alloy according to claim 3 characterised in that: the film system structure of the silver alloy functional layer which is deposited from the surface of the glass substrate to the outside in sequence is as follows: glass substrate/bottom protective layer/first dielectric layer/silver alloy layer/second dielectric layer/top protective layer.

5. A glazing having a functional layer of silver alloy according to claim 3 characterised in that: the film system structure of the silver alloy functional layer which is deposited from the surface of the glass substrate to the outside in sequence is as follows: glass substrate/bottom protective layer/first dielectric layer/first silver alloy layer/second dielectric layer/second silver alloy layer/third dielectric layer/top protective layer.

6. A glazing having a functional layer of silver alloy according to claim 3 characterised in that: the film system structure of the silver alloy functional layer which is deposited from the surface of the glass substrate to the outside in sequence is as follows: glass substrate/bottom protective layer/first dielectric layer/first silver alloy layer/second dielectric layer/second silver alloy layer/third dielectric layer/third silver alloy layer/fourth dielectric layer/top protective layer.

7. A glazing having a functional layer of silver alloy according to claim 3 characterised in that: the film system structure of the silver alloy functional layer which is deposited from the surface of the glass substrate to the outside in sequence is as follows: glass substrate/bottom protective layer/first dielectric layer/first silver alloy layer/second dielectric layer/second silver alloy layer/third dielectric layer/third silver alloy layer/fourth dielectric layer/fourth silver alloy layer/fifth dielectric layer/top protective layer.

8. A glazing having a functional layer of silver alloy according to claim 3 characterised in that: the bottom protective layer or the top protective layer is made of at least one of SiOx, SiOyNz and SiOmCN, wherein x is more than or equal to 1.5 and less than or equal to 2, y is more than or equal to 0.5 and less than or equal to 2, z is more than or equal to 0.5 and less than or equal to 1, m is more than or equal to 0.5 and less than or equal to 2, and n is more than or equal to 0.5 and less than or equal to 1.

9. A glazing having a functional layer of silver alloy according to claim 8 characterised in that: the SiOx, SiOyNz or SiOmCN is doped with at least one of Zr, Al, Mg, Ti and Bi.

10. A glazing having a functional layer of silver alloy according to claim 3 characterised in that: at least one of the medium layers comprises a high-refractive-index layer and a medium-refractive-index layer, the refractive index of the high-refractive-index layer is 2.2-2.6, and the refractive index of the medium-refractive-index layer is 1.8-2.1.

11. A glazing having a functional layer of silver alloy according to claim 10 characterised in that: the high refractive index layer has a refractive index at least 0.2 greater than the refractive index of the medium refractive index layer and the medium refractive index layer has a thickness at least 2 times greater than the thickness of the high refractive index layer.

12. A glazing having a functional layer of silver alloy according to claim 10 characterised in that: the material of the high refractive index layer is selected from at least one of oxides and oxynitrides of titanium, and the material of the medium refractive index layer is selected from at least one of oxides of zinc, tin, magnesium, titanium, tantalum, niobium, bismuth, zirconium and manganese, and/or at least one of nitrides of silicon, zirconium, titanium and aluminum.

13. A glazing having a functional layer of silver alloy according to claim 12 characterised in that: the oxide or oxynitride of titanium in the high refractive index layer is doped with at least one of zinc, tin, silicon, aluminum, zirconium, niobium, tantalum, bismuth, nickel, and chromium.

14. A glazing having a functional layer of silver alloy according to claim 1 characterised in that: the glazing comprises two glass substrates and a thermoplastic interlayer sandwiched between the two glass substrates, the functional layer of silver alloy being deposited on the surface of at least one of the glass substrates adjacent to the thermoplastic interlayer.