CN114538792B - Low-emissivity coated glass with double infrared reflecting layers, laminated glass and vehicle - Google Patents
Low-emissivity coated glass with double infrared reflecting layers, laminated glass and vehicle Download PDFInfo
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- CN114538792B CN114538792B CN202210109286.1A CN202210109286A CN114538792B CN 114538792 B CN114538792 B CN 114538792B CN 202210109286 A CN202210109286 A CN 202210109286A CN 114538792 B CN114538792 B CN 114538792B
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- 239000011521 glass Substances 0.000 title claims abstract description 136
- 239000005340 laminated glass Substances 0.000 title claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 38
- 239000000758 substrate Substances 0.000 claims abstract description 22
- 239000000956 alloy Substances 0.000 claims abstract description 13
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 13
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- 230000004888 barrier function Effects 0.000 claims description 49
- 230000009977 dual effect Effects 0.000 claims description 33
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 18
- 229910044991 metal oxide Inorganic materials 0.000 claims description 17
- 150000004706 metal oxides Chemical class 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 12
- 150000004767 nitrides Chemical class 0.000 claims description 12
- 239000012790 adhesive layer Substances 0.000 claims description 10
- 229910052727 yttrium Inorganic materials 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 229910003087 TiOx Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical group CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
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- 238000002834 transmittance Methods 0.000 claims description 2
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- 238000005260 corrosion Methods 0.000 abstract description 12
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- 239000002356 single layer Substances 0.000 description 2
- 239000003981 vehicle Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
- B60J1/00—Windows; Windscreens; Accessories therefor
- B60J1/001—Double glazing for vehicles
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3639—Multilayers containing at least two functional metal layers
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3644—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the metal being silver
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3657—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having optical properties
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
- C03C2218/154—Deposition methods from the vapour phase by sputtering
- C03C2218/156—Deposition methods from the vapour phase by sputtering by magnetron sputtering
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
The application provides a low-emissivity coated glass of two infrared reflection layers, laminated glass and vehicle, low-emissivity coated glass of two infrared reflection layers, it includes the glass substrate and at the interior dielectric layer, first infrared reflection layer, intermediate medium layer, second infrared reflection layer and the outer dielectric layer of laminating the setting in proper order on at least one surface of glass substrate, the outer dielectric layer includes first outer sublayer, the material of first outer sublayer includes SiN x O y The SiN is x O y The mass fraction of N in the alloy is 40-50%, and the mass fraction of O is 12-20%. The material selected by the film layer in contact with air in the outer medium layer has good optical color effect, good thermal stability and mechanical property, relatively small film layer stress and can improve the mechanical strength and corrosion resistance of the low-radiation coated glass with the double infrared reflection layers.
Description
Technical Field
The application relates to the field of glass coating, in particular to low-emissivity coated glass with double infrared reflecting layers, laminated glass and a vehicle.
Background
At present, most of transparent glass windows used in vehicles are low-emissivity coated glass, and the film system structure of the low-emissivity coated glass is glass substrate/inner medium layer/first silver layer/middle medium layer/second silver layer/outermost medium layer. For low-emissivity coated glass applied to vehicles, the outermost dielectric layer needs to have enough geometric thickness to ensure mechanical strength and corrosion resistance, but in common materials of the outermost dielectric layer, when the geometric thickness is too thick, the stress of the thickened film layer is too large, so that the haze of the film layer is increased after hot bending processing, or the thermal stability of the material is poor.
Disclosure of Invention
The application provides a low-emissivity coated glass, laminated glass and vehicle of two infrared reflection layer, low-emissivity coated glass of two infrared reflection layer, the optical color effect of the selected material of rete with the air contact in its outer dielectric layer is good, thermal stability and mechanical properties are good, and rete stress is less relatively, can promote low-emissivity coated glass's of two infrared reflection layer mechanical strength and corrosion resistance.
The embodiment of the application provides low-emissivity coated glass with double infrared reflection layers, which comprises a glass substrate, an inner dielectric layer, a first infrared reflection layer, an intermediate dielectric layer, a second infrared reflection layer and an outer dielectric layer, wherein the inner dielectric layer, the first infrared reflection layer, the intermediate dielectric layer, the second infrared reflection layer and the outer dielectric layer are sequentially laminated on at least one surface of the glass substrate, the outer dielectric layer comprises a first outer sub-layer, and the first outer sub-layer comprises SiN x O y The SiN is x O y The mass fraction of N in the alloy is 40-50%, and the mass fraction of O is 12-20%.
On the low-emissivity coated glass with the double infrared reflecting layers, the refractive index of the first outer sub-layer needs to be matched with that of the glass body, and the refractive index of the first outer sub-layer needs to be controlled to be between 1.7 and 1.85 so as to avoid adverse influence on the optical effect of the glass; the mass fraction of the first outer sub-layer is regulated and controlled O, N, so that the refractive index of the first outer sub-layer is between 1.7 and 1.85, the thermal stability of the first outer sub-layer is better, the mechanical strength is improved, and the film stress is reduced less, so that the thermal processing is more convenient; in practical application, the first outer sub-layer can better protect the first infrared reflection layer and the second infrared reflection layer inside the low-radiation coated glass of the double infrared reflection layer, and the first outer sub-layer with high mechanical strength is convenient for better protecting the low-radiation coated glass of the double infrared reflection layer in the transportation and processing processes, so that loss is reduced. When the mass fraction of N in the first outer sub-layer is less than 40% and the mass fraction of O is more than 20%, the physicochemical property of the first outer sub-layer is close to that of the SiO compound, at the moment, the film stress of the first outer sub-layer is small, the problems of haze increase, adhesion force deterioration and the like cannot occur after hot processing, but the thermal stability is poor, the problems of sheet resistance increase and the like can occur after high-temperature treatment, and the optical effect and the like of the first outer sub-layer are influenced; when the mass fraction of N in the first outer sub-layer is more than 50% and the mass fraction of O is less than 12%, the physicochemical property of the first outer sub-layer is close to that of SiN compound, the film stress is larger, the problem of film haze increase easily occurs after glass is thermally bent, the binding force between the first outer sub-layer and other film layers is reduced after the first outer sub-layer is thermally bent, and when the first outer sub-layer is applied to the preparation of laminated glass, the film structure of the low-radiation coated glass of the double-infrared reflecting layer and the laminated glass bonding layer are broken or separated.
Wherein the geometric thickness of the first outer sublayer is 7nm to 100nm.
Wherein the material of the first outer sublayer further comprises at least one of a metal oxide or an oxynitride of Al, ni, zr, hf, ti.
The outer dielectric layer further comprises a second outer sub-layer, and the second outer sub-layer is arranged between the second infrared reflecting layer and the first outer sub-layer; the material of the second outer sublayer comprises SnO x And the mass fraction of Sn in the second outer sub-layer is more than or equal to 50%.
Wherein the geometric thickness of the second outer sub-layer is 40nm to 140nm.
Wherein the material of the second outer sub-layer further comprises at least one of the metal oxides of Zn, ti, al, sb, mg, ni, Y.
The outer dielectric layer further comprises a third outer sub-layer, and the third outer sub-layer is positioned between the second infrared reflecting layer and the second outer sub-layer; the material of the third outer sub-layer comprises ZnO, and the mass fraction of Zn in the third outer sub-layer is 50-98%.
Wherein the geometric thickness of the third outer sublayer is 5nm to 60nm.
Wherein the material of the third outer sublayer further comprises at least one of Sn, al, ga, mo, mg, in, nb, ti metal oxides.
The geometric thickness of the outer dielectric layer is 120nm to 175nm, and the refractive indexes of the first outer sub-layer, the second outer sub-layer and the third outer sub-layer are all 1.7 to 2.6.
The low-radiation coated glass of the double infrared reflecting layers further comprises a first barrier layer and/or a second barrier layer;
the first barrier layer is positioned between the first infrared reflecting layer and the intermediate medium layer, the geometric thickness of the first barrier layer is 0.5nm to 10nm, and the first barrier layer is selected from at least one of Ni, cr, ti, zn, nb, hf, zr, al metal and metal, incomplete oxide and incomplete nitride of alloy thereof;
wherein the first infrared reflecting layer and the second infrared reflecting layer are selected from at least one of Ag, au, cu, al and alloys thereof.
The second barrier layer is positioned between the second infrared reflecting layer and the outer dielectric layer, the geometric thickness of the second barrier layer is 0.5nm to 10nm, and the second barrier layer is at least one of Ni, cr, ti, zn, nb, hf, zr, al metal and metal, incomplete oxide and incomplete nitride of the alloy thereof.
Wherein the geometric thickness of the inner dielectric layer is 15nm to 45nm, and the inner dielectric layer is selected from at least one of Zn, si, sn, ti, nb, zr, hf, mg, ni, in, al, ga, W, bi metal oxide and a mixture thereof, or from at least one of Si, al, zr, ti, Y, hf, nb, ta metal nitride or oxynitride and a mixture thereof.
Wherein the geometric thickness of the intermediate dielectric layer is 50nm to 100nm, and the intermediate dielectric layer is selected from at least one of Zn, si, sn, ti, nb, zr, hf, mg, ni, in, al, ga, W, bi metal oxide and a mixture thereof, or from at least one of Si, al, zr, ti, Y, hf, nb, ta metal nitride or oxynitride and a mixture thereof.
The embodiment of the application also provides laminated glass, which comprises:
a glass plate;
an adhesive layer provided on a surface of the glass plate; and
the application low-emissivity coated glass with double infrared reflection layers, the low-emissivity coated glass with the double infrared reflection layers is arranged on the surface of the bonding layer, which is away from the glass plate, and the outer medium layer is close to the bonding layer compared with the glass substrate.
The application the laminated glass comprises the low-emissivity coated glass with the double infrared reflection layers, and the low-emissivity coated glass with the double infrared reflection layers has high mechanical strength, so that the laminated glass also has higher mechanical strength.
Wherein, the glass board is the low-emissivity coated glass with the double infrared reflecting layers.
The embodiment of the application also provides a vehicle, which comprises:
a vehicle body; and
the door window, the door window set up in the vehicle body, the door window includes the low-emissivity coated glass of two infrared reflection stratum of this application.
The vehicle comprises the low-emissivity coated glass with the double infrared reflection layers, the surface of the low-emissivity coated glass with the double infrared reflection layers has an outermost dielectric layer with high mechanical strength and is thickened, the inner film layer of the low-emissivity coated glass is well protected, and when the low-emissivity coated glass is applied to the vehicle, the vehicle window is more scratch-resistant and is not easy to scratch; the infrared light can be prevented from being directly injected into the vehicle, and the discomfort of temperature felt by personnel in the vehicle can be avoided; the vehicle window can also have good optical effect, so that the vehicle has good appearance. The Vehicle in this application may be, but is not limited to, a sedan, a utility Vehicle (MPV), a Sport utility Vehicle (Sport/Suburban Utility Vehicle, SUV), an Off-Road Vehicle (ORV), a pick-up, a minibus, a passenger car, a van, etc.
Drawings
In order to more clearly illustrate the technical solutions of the examples of the present application, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic diagram of a film structure of a low-emissivity coated glass with dual infrared reflection layers according to an embodiment of the disclosure;
fig. 2 is a schematic structural view of a laminated glass according to an embodiment of the present application;
fig. 3 is a schematic structural view of another laminated glass according to an embodiment of the present application;
fig. 4 is a schematic structural diagram of a vehicle according to an embodiment of the present application.
Reference numerals illustrate:
100-low-emissivity coated glass; 1-a glass substrate; 2-an inner dielectric layer; 3-a first infrared reflective layer; 4-a first barrier layer; 5-an intermediate dielectric layer; 6-a second infrared reflecting layer; 7-a second barrier layer; 8-an outer dielectric layer; 81-a first outer sublayer; 82-a second outer sublayer; 83-a third outer sublayer; 200-laminated glass; 210-glass plate; 220-an adhesive layer; 300-vehicle; 310-vehicle body; 320-vehicle window.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all, of the embodiments of the present application. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments herein without undue burden, are within the scope of the present application.
The terms first, second and the like in the description and in the claims of the present application and in the above-described figures, are used for distinguishing between different objects and not for describing a particular sequential order. Furthermore, the terms "comprise" and "have," as well as any variations thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, system, article, or apparatus that comprises a list of steps or elements is not limited to only those listed steps or elements but may include other steps or elements not listed or inherent to such process, method, article, or apparatus.
Reference herein to "an embodiment" or "an implementation" means that a particular feature, structure, or characteristic described in connection with the embodiment or implementation may be included in at least one embodiment of the present application. The appearances of such phrases in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. Those of skill in the art will explicitly and implicitly appreciate that the embodiments described herein may be combined with other embodiments.
The following describes the invention further with reference to the accompanying drawings, wherein the thickness of the film layers is geometric in the case of no brightness; the refractive index value of the film layer is the refractive index value at the wavelength of 550nm, the geometric thickness of the film layer is the physical thickness of the film layer, and the optical thickness of the film layer is the product of the refractive index at the wavelength of 550nm and the geometric thickness of the film layer.
As shown in fig. 1, an embodiment of the present application provides a low-emissivity coated glass 100 with dual infrared reflection layers, which includes a glass substrate 1, and an inner dielectric layer 2, a first infrared reflection layer 3, an intermediate dielectric layer 5, a second infrared reflection layer 6, and an outer dielectric layer 8 sequentially stacked on at least one surface of the glass substrate 1, wherein the outer dielectric layer 8 includes a first outer sub-layer 81, and the first outer sub-layer 81 includes SiN x O y The SiN is x O y The mass fraction of N in the alloy is 40-50%, and the mass fraction of O is 12-20%.
The mass fraction of N in the first outer sublayer 81 is 40% to 50%, specifically, the mass fraction of N in the first outer sublayer 81 may be, but is not limited to, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%; when the mass fraction of O in the first outer sublayer 81 is 12% to 20%, specifically, the mass fraction of O in the first outer sublayer 81 may be, but is not limited to, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%.
On the low-emissivity coated glass 100 with the dual infrared reflection layer, the refractive index of the first outer sub-layer 81 needs to be matched with that of the glass body, and the refractive index of the first outer sub-layer needs to be controlled to be between 1.7 and 1.85 so as to avoid adverse influence on the optical effect of the glass; the mass fraction of the first outer sublayer 81 is regulated and controlled O, N, so that the refractive index of the first outer sublayer 81 is between 1.7 and 1.85, the thermal stability of the first outer sublayer 81 is better, the mechanical strength is improved, and the film stress is relatively reduced, so that the thermal processing is more convenient; in practical applications, the first outer sub-layer 81 can better protect the first infrared reflection layer 3 and the second infrared reflection layer 6 inside the low-emissivity coated glass 100 with double infrared reflection layers, and the first outer sub-layer 81 with high mechanical strength is convenient for better protecting the low-emissivity coated glass 100 with double infrared reflection layers in the transportation and processing processes, so that the loss is reduced. When the mass fraction of N in the first outer sub-layer 81 is less than 40% and the mass fraction of O is more than 20%, the physicochemical property of the first outer sub-layer 81 is close to that of the SiO compound, at the moment, the film stress of the first outer sub-layer 81 is small, the problems of haze increase, adhesion force deterioration and the like cannot occur after hot working, but the thermal stability is poor, the problems of sheet resistance increase and the like occur after high-temperature treatment, and the optical effect and the like of the first outer sub-layer 81 are influenced; when the mass fraction of N in the first outer sub-layer is greater than 50% and the mass fraction of O is less than 12%, the physicochemical property of the first outer sub-layer 81 is close to that of SiN compound, the film stress is larger, the problem of film haze increase easily occurs after glass is thermally bent, the binding force between the first outer sub-layer 81 and other films is reduced after the glass is thermally bent, and when the film structure is applied to the preparation of laminated glass, the film structure of the low-radiation coated glass 100 with double infrared reflection layers is broken or separated from the laminated glass.
In some embodiments, the inner dielectric layer 2 has a single-layer structure; in some embodiments, the inner dielectric layer comprises two or more sub-layers, optionally the inner dielectric layer 2 comprises a first inner sub-layer, a second inner sub-layer, and a third inner sub-layer.
In some embodiments, the intermediate dielectric layer 5 is a single layer structure; in some embodiments, the intermediate dielectric layer 5 comprises two or more sub-layers, optionally the intermediate dielectric layer 5 comprises a first sub-layer, a second sub-layer, a third sub-layer.
In some embodiments, the first outer sublayer 81 further comprises at least one of a metal oxide or oxynitride of Al, ni, zr, hf, ti. The first outer sub-layer 81 is used for providing protection for the low emissivity coated glass 100 of the infrared reflection layer, and the first outer sub-layer 81 has a gain effect on the deposition of the first outer sub-layer 81 and the mechanical strength and corrosion resistance of the film layer when the metal oxide or the oxynitride of Al, ni, zr, hf, ti is doped or otherwise added.
In some embodiments, the geometric thickness of the first outer sublayer 81 is 7nm to 100nm. In particular, the geometric thickness of the first outer sublayer 81 may be, but is not limited to, 7nm, 8nm, 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm; the thickness of the first outer sub-layer 81 can be designed to be 100nm, so that the optical effect of the low-emissivity coated glass 100 with the double infrared reflection layers is not affected, and the mechanical strength and corrosion resistance of the low-emissivity coated glass 100 with the double infrared reflection layers can be improved to the greatest extent. When the geometric thickness of the first outer sub-layer 81 is higher than 100nm, the film layer will have excessive stress, and the production cost will be too high, and the process control difficulty will be too high; when the geometric thickness of the first outer sublayer 81 is less than 7nm, the mechanical strength and thermal stability of the dual infrared reflecting layer low emissivity coated glass 100 may be significantly reduced. Further, the geometric thickness of the first outer sublayer 81 is 20nm to 60nm.
In some embodiments, the outer dielectric layer 8 further comprises a second outer sub-layer 82, the second outer sub-layer 82 being disposed between the second infrared reflective layer 6 and the first outer sub-layer 81; the second outer sublayer 82 comprises SnO x The mass fraction of Sn in the second outer sublayer 82 is equal to or greater than 50%. Specifically, the mass fraction of Sn in the second outer sublayer 82 may be, but is not limited to, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%; the second outer sub-layer 82 provides an attractive light reflection effect for the dual infrared reflective low emissivity coated glass 100, which has a light blue, light green, light blue green, etc. appearanceThe color and the increase of the SnOx thickness can further improve the environmental corrosion resistance of the film. When the mass fraction of Sn in the second outer sublayer 82 is less than 50%, the environmental resistance of the film layer is not good, and point defects may occur during processing.
In some embodiments, the second outer sublayer 82 further comprises at least one of Zn, ti, al, sb, mg, ni, Y metal oxides. The second outer sub-layer 82 is used for providing a color effect to the ir-reflecting layer low-emissivity coated glass 100, but the second outer sub-layer 82 also has a certain protection effect on the mechanical strength and corrosion resistance of the ir-reflecting layer low-emissivity coated glass 100, and the second outer sub-layer 82 has a gain effect on the mechanical strength and corrosion resistance of the second outer sub-layer 82 when the second outer sub-layer 82 is doped or otherwise added with Zn, ti, al, sb, mg, ni, Y metal oxide.
In some embodiments, the geometric thickness of the second outer sublayer 82 is 40nm to 140nm. In particular, the geometric thickness of the second outer sublayer 82 may be, but is not limited to, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 110nm, 120nm, 130nm, 140nm; in some possible embodiments, the geometric thickness of the second outer sublayer 82 is 50nm to 130nm; in some possible embodiments, the geometric thickness of the second outer sublayer 82 is 90nm to 120nm; when the geometric thickness of the second outer sub-layer 82 is smaller than 40nm, the improvement effect of the durability of the film layer is not high, and when the geometric thickness of the second outer sub-layer 82 is larger than 140nm, the color effect brought by the second outer sub-layer 82 can show the visual effects of dark blue, dark green, dark purple and the like which are not attractive.
In some embodiments, the outer dielectric layer 8 further comprises a third outer sub-layer 83, the third outer sub-layer 83 being located between the second infrared reflecting layer 6 and the second outer sub-layer 82; the third outer sublayer 83 comprises ZnO, and the mass fraction of Zn in the third outer sublayer 83 is 50% to 98%. Specifically, the mass fraction of Zn in the third outer sublayer 83 may be, but is not limited to, 51%, 53%, 55%, 57%, 59%, 61%, 63%, 65%, 67%, 69%, 71%, 73%, 75%, 77%, 79%, 81%, 83%, 85%, 87%, 89%, 91%, 92%, 93%, 95%, 97%, 98%; in some possible embodiments, the mass fraction of Zn in the third outer sublayer 83 is 90% to 98%; when the coating method is magnetron sputtering, the third outer sub-layer 83 is beneficial to improving the stability of the film, and is not beneficial to achieving the expected effect when the mass fraction of Zn is too high or too low.
In some embodiments, the third outer sublayer 83 further comprises at least one of Sn, al, ga, mo, mg, in, nb, ti metal oxides. Doping other elements in the ZnO film is beneficial to improving the sputtering stability of the ZnO film and reducing the defects of the film. Optionally, the third outer sub-layer 83 includes ZnO doped with Al (AZO), which acts as a barrier layer for the ir reflecting layer to protect stability during sputtering of the ir reflecting layer.
In some embodiments, the third outer sublayer 83 further comprises Al 2 O 3 、TiO 2 、SiO 2 、ZrO 2 、WO 3 、Bi 2 O 3 、HfO 2 And Nb (Nb) 2 O 5 At least one of them.
In some embodiments, the geometric thickness of the third outer sublayer 83 is 5nm to 60nm. In particular, the geometric thickness of the third outer sublayer 83 may be, but is not limited to, 5nm, 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm, 55nm, 60nm; when the geometric thickness of the third outer sub-layer 83 is greater than 60nm, since the third outer sub-layer 83 is too thick, it is disadvantageous to improve chemical resistance and mechanical properties of the film layer because of low corrosion resistance and mechanical strength of ZnO; when the geometric thickness of the third outer sub-layer 83 is less than 5nm, it is not beneficial to improve the stability of the film sputtering process.
In some embodiments, the geometric thickness of the outer dielectric layer 8 is preferably 120nm to 175nm, and by reasonably designing the geometric thickness of the outer dielectric layer 8, the thermal stability, chemical stability and mechanical stability of the film system can be improved, thereby achieving high durability, and enabling the final laminated glass product to have a reflective appearance of neutral color. In particular, the geometric thickness of the outer dielectric layer 8 may be, but is not limited to, 120nm, 125nm, 130nm, 135nm, 140nm, 145nm, 150nm, 155nm, 160nm, 165nm, 170nm, 175nm; the refractive index of each of the first outer sub-layer 81, the second outer sub-layer 82 and the third outer sub-layer 83 is 1.7 to 2.6. Specifically, the refractive indexes of the first outer sub-layer 81, the second outer sub-layer 82, and the third outer sub-layer 83 may be, but are not limited to, 1.7, 1.75, 1.8, 1.85, 1.9, 1.95, 2.0, 2.05, 2.1, 2.15, 2.2, 2.25, 2.3, 2.35, 2.4, 2.45, 2.5, 2.55, and 2.6; the outer dielectric layer 8 comprises a first outer sub-layer 81, a second outer sub-layer 82 and a third outer sub-layer 83, and the physicochemical property of the first outer sub-layer 81 has the advantages of SiN compounds and SiO compounds by regulating and controlling the mass fraction of N, O in the first outer sub-layer 81, so that the first outer sub-layer 81 with good thermal stability, small film stress, convenient thermal processing and high mechanical strength is obtained. Through the reasonable design of the geometric thickness of the first outer sublayer 81, the second outer sublayer 82 and the third outer sublayer 83, the geometric thickness of the outer medium layer 8 can reach 120nm to 175nm, and in practical application, the mechanical strength and corrosion resistance of the low-radiation coated glass 100 with double infrared reflection layers can be greatly improved, and the higher visible light transmittance of more than or equal to 70% and the better neutral reflection color effect can be obtained.
In some embodiments, the dual infrared reflecting layer low emissivity coated glass 100 further comprises: the first barrier layer 4 and/or the second barrier layer 7, optionally the low-emissivity coated glass 100 with double infrared reflection layers further comprises the first barrier layer 4; the low-emissivity coated glass 100 with the double infrared reflection layers further comprises a second barrier layer 7; the dual infrared reflecting layer low emissivity coated glass 100 further comprises a first barrier layer 4 and a second barrier layer 7.
Optionally, the first barrier layer 4 is located between the first infrared reflecting layer 3 and the intermediate dielectric layer 5; the geometric thickness of the first barrier layer 4 is 0.5nm to 10nm, and the first barrier layer 4 is at least one of Ni, cr, ti, zn, nb, hf, zr, al metal and metal of alloy thereof, incomplete oxide and incomplete nitride; specifically, the geometric thickness of the first barrier layer 4 is 0.5nm to 10nm; in particular, the geometric thickness of the first barrier layer 4 may be, but is not limited to, 0.5nm, 1nm, 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm, 10nm.
Optionally, the second barrier layer 7 is located between the second infrared reflecting layer 6 and the outer dielectric layer 8. The geometric thickness of the second barrier layer 7 is 0.5nm to 10nm, and the second barrier layer 7 is selected from at least one of Ni, cr, ti, zn, nb, hf, zr, al metal and metal of its alloy, incomplete oxide and incomplete nitride. The geometric thickness of the second barrier layer 7 is 0.5nm to 10nm, and in particular, the geometric thickness of the second barrier layer 7 may be, but is not limited to, 0.5nm, 1nm, 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm, 10nm.
The first barrier layer 4 and the second barrier layer 7 are used for protecting the first infrared reflection layer 3 and the second infrared reflection layer 6 from oxidation damage during the deposition process of a film sputtering subsequent medium layer, preventing metal elements in the first infrared reflection layer 3 and the second infrared reflection layer 6 from being damaged, and improving the adhesion force of the interface between the first infrared reflection layer 3 and the inner medium layer 2 and the interface between the second infrared reflection layer 6 and the intermediate medium layer 5.
Optionally, when the first barrier layer or the second barrier layer is TiOx, the value range of x is: 0 < x < 2, and the geometric thickness of the first barrier layer or the second barrier layer is 2nm to 10nm.
In some embodiments, the geometric thickness of the inner dielectric layer 2 is 15nm to 45nm, and the inner dielectric layer 2 is selected from at least one of Zn, si, sn, ti, nb, zr, hf, mg, ni, in, al, ga, W, bi metal oxide and mixtures thereof, or from at least one of Si, al, zr, ti, Y, hf, nb, ta metal nitride or oxynitride and mixtures thereof. In particular, the geometric thickness of the inner dielectric layer 2 may be, but is not limited to, 15nm, 18nm, 21nm, 24nm, 27nm, 30nm, 33nm, 36nm, 39nm, 42nm, 45nm; the inner dielectric layer 2 can reduce reflection in a visible light region, provide a proper growth basis for the first infrared reflecting layer 3 and keep high-temperature stability of the first infrared reflecting layer, and the inner dielectric layer 2 is in contact with the glass substrate 1, so that infiltration of Na, O and other impurity atoms in the glass substrate 1 to the first infrared reflecting layer 3 can be blocked, and all film layers are fixed on the surface of the glass substrate 1 through adhesion with the glass substrate 1.
In some embodiments, the intermediate dielectric layer has a geometric thickness of 50nm to 100nm, and is selected from at least one of Zn, si, sn, ti, nb, zr, hf, mg, ni, in, al, ga, W, bi metal oxide and mixtures thereof, or from at least one of Si, al, zr, ti, Y, hf, nb, ta metal nitride or oxynitride and mixtures thereof. In particular, the geometric thickness of the intermediate dielectric layer 5 may be, but is not limited to, 50nm, 55nm, 60nm, 65nm, 70nm, 75nm, 80nm, 85nm, 90nm, 95nm, 100nm; the intermediate dielectric layer 5 described herein serves to reduce reflection in the visible region, provide a suitable growth basis for the second infrared reflecting layer 6, and maintain its high temperature stability.
In some embodiments, the first infrared reflective layer 3 is selected from at least one of Ag, au, cu, al and alloys thereof; the second infrared reflecting layer 6 is selected from at least one of Ag, au, cu, al and its alloys. The materials of the first infrared reflecting layer 3 and the second infrared reflecting layer 6 may be materials capable of reflecting or absorbing infrared rays, and the primary functions of the first infrared reflecting layer 3 and the second infrared reflecting layer 6 are to reflect infrared rays and block the transmission of infrared rays from the low-emissivity coated glass 100 of the dual infrared reflecting layers.
In some embodiments, the geometric thickness of the first infrared reflecting layer 3 is 7nm to 16nm; in particular, the geometric thickness of the first infrared reflecting layer 3 may be, but is not limited to, 7nm, 8nm, 9nm, 10nm, 11nm, 12nm, 13nm, 14nm, 15nm, 16nm; the geometric thickness of the second infrared reflecting layer 6 is 7nm to 16nm; in particular, the geometric thickness of the second infrared reflecting layer 6 may be, but is not limited to, 7nm, 8nm, 9nm, 10nm, 11nm, 12nm, 13nm, 14nm, 15nm, 16nm; the thickness of each film layer is designed, so that the thermal stability, chemical stability and mechanical stability of each film layer on the low-emissivity coated glass 100 with the double infrared reflection layers are improved, the high durability of the low-emissivity coated glass 100 with the double infrared reflection layers is realized, and the low-emissivity coated glass with the double infrared reflection layers has a reflection appearance with neutral colors.
Referring to fig. 2 and 3, an embodiment of the present application further provides a laminated glass 200, which includes:
a glass plate 210;
an adhesive layer 220, wherein the adhesive layer 220 is arranged on the surface of the glass plate;
and the low-emissivity coated glass 100 with double infrared reflection layers, wherein the low-emissivity coated glass 100 with double infrared reflection layers is arranged on the surface of the bonding layer 220, which is away from the glass plate 210, and the outer dielectric layer 8 is arranged close to the bonding layer 220 compared with the glass substrate 1.
The laminated glass 200 comprises the low-emissivity coated glass 100 with the double infrared reflection layers, and the low-emissivity coated glass 100 with the double infrared reflection layers has high mechanical strength, so that the laminated glass also has high mechanical strength.
In some embodiments, the glass sheet 210 is a dual infrared reflecting layer low emissivity coated glass 100 as described herein. In one possible embodiment, the laminated glass 200 of the present application may include two pieces of the low-emissivity coated glass 100 with dual infrared reflection layers and an adhesive layer 220, where the two pieces of the low-emissivity coated glass 100 with dual infrared reflection layers are laminated and adhered together by the adhesive layer 220, and the outer dielectric layers 8 of the two pieces of the low-emissivity coated glass 100 with dual infrared reflection layers are disposed closer to the adhesive layer 220 than the glass substrate 1; at this time, since the mechanical strength of the low-emissivity coated glass 100 with the dual infrared reflection layer is high, when two pieces of the low-emissivity coated glass 100 with the dual infrared reflection layer are selected to form the laminated glass 200, the mechanical strength of the laminated glass 200 is further improved.
Referring to fig. 4, an embodiment of the present application further provides a vehicle 300, including:
a vehicle body 310;
and a window 320, the window 320 being disposed on the vehicle body 310, the window 320 comprising the dual infrared reflective layer low emissivity coated glass 100 described herein.
The vehicle 300 in the application comprises the low-emissivity coated glass 100 with the double infrared reflection layers, wherein the surface of the low-emissivity coated glass 100 with the double infrared reflection layers has the thickened outermost dielectric layer 8 with high mechanical strength, has a good protection effect on the inner film layer, and is more scratch-resistant for the vehicle window 320 and difficult to scratch when the vehicle is applied to the vehicle 300; the infrared light can be prevented from being directly injected into the vehicle, and the discomfort of temperature felt by personnel in the vehicle can be avoided; the window 320 may also have a good optical effect, giving the vehicle 300 a good appearance. The Vehicle in this application may be, but is not limited to, a sedan, a utility Vehicle (MPV), a Sport utility Vehicle (Sport/Suburban Utility Vehicle, SUV), an Off-Road Vehicle (ORV), a pick-up, a minibus, a passenger car, a van, etc.
In order to describe and more competitively support the inventive aspects of the present invention in more detail, a detailed description of some embodiments will now be presented.
In examples 1 to 3 and comparative examples 1 to 4, a soda lime silicate float glass having a thickness of 2.1mm was used as a glass substrate 1, and after cutting, edging, washing, drying and the like, the glass substrate was subjected to a magnetron sputtering coating line to perform coating deposition, and a film layer was sequentially deposited on the surface of the glass substrate 1, comprising:
inner dielectric layer 2: the geometric thickness is 22nm, and the material is SnOx;
first infrared reflecting layer 3: the geometric thickness is 12nm, and the material is Ag;
first barrier layer 4: the geometric thickness is 5nm, and the material is TiOx;
intermediate dielectric layer 5: the geometric thickness is 63nm, and the material is SnOx;
second infrared reflecting layer 6: the geometric thickness is 10.5nm, and the material is Ag;
a second barrier layer 7: the geometric thickness is 5nm, and the material is TiOx;
an outer dielectric layer 8, the outer dielectric layer 8 includes a first outer sub-layer 81, a second outer sub-layer 82, and a third outer sub-layer 83, wherein:
third outer sublayer 83: the geometric thickness is 10nm, and the material is ZnO;
second outer sublayer 82: the geometric thickness is 90nm, and the material is SnO x ；
First outer sublayer 81: the material is SiN x O y ；
Comparative example 5 is exemplified by a conventional dual silver film system, comprising, sequentially deposited film layers on the surface of the glass substrate 1:
inner dielectric layer 2: the geometric thickness is 22nm, and the material is SnOx;
first infrared reflecting layer 3: the geometric thickness is 12nm, and the material is Ag;
first barrier layer 4: the geometric thickness is 5nm, and the material is TiOx;
intermediate dielectric layer 5: the geometric thickness is 63nm, and the material is SnOx;
second infrared reflecting layer 6: the geometric thickness is 10.5nm, and the material is Ag;
a second barrier layer 7: the geometric thickness is 5nm, and the material is TiOx;
an outer dielectric layer 8, the outer dielectric layer 8 includes a first outer sub-layer 81, a second outer sub-layer 82, and a third outer sub-layer 83, wherein:
third outer sublayer 83: the geometric thickness is 10nm, and the material is ZnO;
second outer sublayer 82: the geometric thickness is 20nm, and the material is SnOx;
first outer sublayer 81: the material is Si 3 N 4 ；
As shown in table 1 below, the weight fraction of N, O in the first outer sublayer 81 and its geometric thickness are as shown in examples 1 to 3, and comparative examples 1 to 5.
Table 1: examples 1-3 and comparative examples 1-5 first outer sublayers material and geometric thickness
| N, O mass fraction | Geometric thickness | |
| EXAMPLE 1 SiNxOy | N：45％，O：14％； | 50nm |
| EXAMPLE 2 SiNxOy | N：47％，O：12％； | 50nm |
| EXAMPLE 3 SiNxOy | N：40％，O：20％； | 50nm |
| Comparative example 1 SiNxOy | N：52％，O：8％； | 50nm |
| Comparative example 2 SiNxOy | N：30％，O：30％； | 50nm |
| Comparative example 3 SiO 2 | N：0％，O：53％； | 50nm |
| Comparative example 4 Si 3 N 4 | N：40％，O：0％； | 50nm |
| Comparative example 5 Si 3 N 4 | N：40％，O：0％； | 8nm |
Next, mechanical properties, thermal stability, and thermal processing conditions of examples 1 to 3, and comparative examples 1 to 5 were evaluated, and the obtained results were recorded in table 2.
In terms of mechanical properties, the ability of the film layer to withstand frictional losses is mainly examined. The abrasion instrument is wrapped with clean nylon cloth dipped with alcohol, and is provided with 5N/cm 2 The abrasion of the film surface before heat treatment and the abrasion of the film surface after heat treatment of the film layer after abrasion were evaluated by naked eyes and a magnifying glass scale, and the abrasion of the film surface was recorded as 1 time for one back and forth abrasion and 15 times for the subsequent abrasion. And scoring the scratch condition after friction:
1, the method comprises the following steps: the width of the obvious scratch is more than 0.2mm, and the number of the obvious scratch is more than or equal to 10;
2, the method comprises the following steps: the width of the slight scratch is more than 0.2mm, and the number of the slight scratch is 5-10;
3, the method comprises the following steps: the width of the slight scratch of the scratch is 0.1-0.2mm, and the number of the slight scratch is less than or equal to 8;
4, the following steps: the width of the scratch, namely the fine scratch, is less than or equal to 0.1mm, and the number is less than or equal to 5;
5, the method comprises the following steps: the width of scratch or scratch is less than or equal to 0.08mm and the number is less than or equal to 3 when observed by naked eyes.
Thermal stability the low emissivity coated glass 100 of examples 1 to 3 and comparative examples 1 to 5 was observed for changes in sheet resistance under the same heat treatment process conditions from table 2.
Hot workability in table 2, the low-emissivity coated glasses 100 of examples 1 to 3 and comparative examples 1 to 5 were subjected to the same heat treatment, and the haze change of the film was observed.
Environmental resistance from table 2, the low-emissivity coated glasses 100 of examples 1 to 3, and comparative examples 1 to 5 were left in an environment where they were exposed to high temperature and high humidity (temperature 50 ℃/humidity 90%) for a certain period of time, and how long corrosion spots or oxidation spots began to appear was evaluated.
Impact test of sandwich product: adhesion of the low-emissivity film layer to PVB, a steel ball impact test of 227g was performed on the laminated glass 200 product with the low-emissivity film layer according to the safety standard of laminated automobile glass, and the detachment of glass fragments with the low-emissivity film from PVB was observed (national standard: GB/T5137.1-2020).
Table 2: evaluation results of examples 1 to 3 and comparative examples 1 to 5
As can be seen from table 2, wherein comparative example 5 is a material and a geometric thickness selected in the related art, with respect to mechanical properties, the environmental corrosion resistance and the abrasion resistance of examples 1 to 3, and comparative examples 1 to 4 are significantly improved as compared with the conventional film system comparative example 5.
In embodiments 1 to 3 of the present application, the mass fraction of N and O of the first outer sublayer 81 is adjusted and controlled, so that the first intermediate sublayer not only obtains better wear resistance, but also ensures thermal stability and hot workability. In comparative example 1, the mass fraction of N in the first outer sub-layer 81 is > 50%, the mass fraction of O is < 12%, and in comparative example 4, the mass fraction of O is < 12%, at this time, the physicochemical properties of the first outer sub-layers 81 of comparative examples 1 and 4 are close to those of SiN compound, the film stress is large, the film haze is easily increased after glass is thermally bent, and the adhesion property between the heat-treated film and PVB is poor. In comparative examples 2 and 3, when the mass fraction of N in the first outer sublayer 81 is < 40% and the mass fraction of O is > 20%, the physicochemical properties of the first outer sublayer 81 are similar to those of SiO compound, andthe film layer of the first outer sub-layer 81 has small stress, and the problems of increased haze, poor adhesion and the like do not occur after heat processing. But has poor thermal stability, increases the sheet resistance after high temperature treatment, and the like. As can be seen from Table 2, the geometric thickness of the first outer sublayer 81 in the conventional dual silver film system of comparative example 4 is increased as compared to that of comparative example 5, and the mechanical strength after plating is also significantly improved, but comparative example 5 shows thinner Si 3 N 4 The problem of poor adhesion of the film layer to PVB is not easy to occur.
As can be seen from table 2, examples 1 to 3 of the technical scheme of the present invention all show better thermal stability; in combination with comparative examples 1 to 5, it can be seen that the first dielectric sublayer of the third dielectric layer can possess good thermal stability and mechanical properties using the ratio of N to O as defined herein.
After the low-emissivity coated glasses 100 of examples 1 to 3 and comparative examples 1 to 5 were subjected to a high-temperature bending forming heat treatment, laminated glass 200 was obtained by an automotive glass production process together with another bent glass sheet 210 of 2.1mm and PVB of 0.76mm thickness, and the laminated glass 200 thus obtained was subjected to a standard GB/T5137.1-2020 impact test, and the adhesion between the low-emissivity coated film layer and the adhesive layer 220 (PVB) was evaluated, and as a result, from table 2, the mass fraction of N in the first outer sub-layer 81 of comparative example 1 was > 50%, the mass fraction of O in the first outer sub-layer 81 of comparative example 4 was < 12%, at which time the physicochemical properties of the first outer sub-layers 81 of comparative examples 1 and 4 were close to SiN compounds, and the adhesion was evaluated as unacceptable after the impact test of the laminated glass 200 formed of comparative examples 1 and comparative example 4.
Compared with comparative examples 1 and 4, it can be seen that by adopting the technical scheme of the present invention, the low-emissivity coated glass 100 of which the mass fraction of N in the first outer sub-layer 81 is controlled to be 40-50% and the mass fraction of O is controlled to be 12-20% has not only good thermal stability, chemical stability and mechanical properties, but also good adhesion between the low-emissivity coated film and the adhesive layer 220 (PVB) after heat treatment, and the laminated glass 200 formed in examples 1 to 3 has good impact resistance.
While embodiments of the present application have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the present application, and that variations, modifications, alternatives and alterations of the above embodiments may be made by those skilled in the art within the scope of the present application, which are also to be regarded as being within the scope of the protection of the present application.
Claims (16)
1. The low-emissivity coated glass with the double infrared reflection layers is characterized by comprising a glass substrate, an inner dielectric layer, a first infrared reflection layer, an intermediate dielectric layer, a second infrared reflection layer and an outer dielectric layer, wherein the inner dielectric layer, the first infrared reflection layer, the intermediate dielectric layer, the second infrared reflection layer and the outer dielectric layer are sequentially laminated on at least one surface of the glass substrate, the outer dielectric layer comprises a first outer sub-layer, a second outer sub-layer and a third outer sub-layer, and the material of the first outer sub-layer comprises SiN x O y The SiN is x O y The mass fraction of N in the alloy is 40 to 50 percent, and the mass fraction of O is 12 to 20 percent; the refractive index of the first outer sublayer ranges from 1.7 to 1.85;
the second outer sublayer is arranged between the second infrared reflecting layer and the first outer sublayer, and the material of the second outer sublayer comprises SnO x The mass fraction of Sn in the second outer sub-layer is more than or equal to 50%;
the third outer sublayer is positioned between the second infrared reflecting layer and the second outer sublayer, the material of the third outer sublayer comprises ZnO, and the mass fraction of Zn in the third outer sublayer is 50-98%;
the low emissivity coated glass has a visible light transmittance of greater than or equal to 70%.
2. The dual infrared reflecting layer low emissivity coated glass of claim 1, wherein said first outer sub-layer has a geometric thickness of 7nm to 100nm.
3. The dual infrared reflecting layer low emissivity coated glass of claim 1, wherein said first outer sub-layer material further comprises at least one of a metal oxide or oxynitride of Al, ni, zr, hf, ti.
4. The dual infrared reflecting layer low emissivity coated glass of claim 1, wherein said second outer sub-layer has a geometric thickness of 40nm to 140nm.
5. The dual infrared reflective layer low emissivity coated glass of claim 1, wherein said second outer sub-layer material further comprises at least one of the metal oxides of Zn, ti, al, sb, mg, ni, Y.
6. The dual infrared reflecting layer low emissivity coated glass of claim 1, wherein said third outer sub-layer has a geometric thickness of 5nm to 60nm.
7. The dual infrared reflecting layer low emissivity coated glass of claim 1, wherein said third outer sub-layer material further comprises at least one of Sn, al, ga, mo, mg, in, nb, ti metal oxides.
8. The dual infrared reflecting layer low emissivity coated glass of claim 1, wherein said outer dielectric layer has a geometric thickness of greater than 120nm and less than or equal to 175nm.
9. The dual infrared reflecting layer low emissivity coated glass of claim 1, wherein said third outer sub-layer has a refractive index of 1.7 to 2.6, and wherein said second outer sub-layer has a refractive index of 1.7 to 2.6.
10. The dual infrared reflecting layer low emissivity coated glass of claim 1, further comprising a first barrier layer and/or a second barrier layer;
the first barrier layer is positioned between the first infrared reflecting layer and the intermediate medium layer, the geometric thickness of the first barrier layer is 0.5-nm-10 nm, and the first barrier layer is at least one of Ni, cr, ti, zn, nb, hf, zr, al metal and metal of its alloy, incomplete oxide and incomplete nitride;
the second barrier layer is positioned between the second infrared reflecting layer and the outer dielectric layer, the geometric thickness of the second barrier layer is 0.5-nm-10 nm, and the second barrier layer is at least one of Ni, cr, ti, zn, nb, hf, zr, al metal and metal of its alloy, incomplete oxide and incomplete nitride.
11. The dual infrared reflecting layer low emissivity coated glass of claim 10, wherein when said first barrier layer or said second barrier layer is TiOx, wherein x has a value in the range of: 0 < x < 2, and the geometric thickness of the first barrier layer or the second barrier layer is 2nm to 10nm.
12. The dual infrared reflective layer low emissivity coated glass of claim 1, wherein said inner dielectric layer has a geometric thickness of 15nm to 45nm, said inner dielectric layer being selected from at least one of Zn, si, sn, ti, nb, zr, hf, mg, ni, in, al, ga, W, bi metal oxides and mixtures thereof, or from at least one of Si, al, zr, ti, Y, hf, nb, ta metal nitrides or oxynitrides and mixtures thereof.
13. The dual infrared reflective layer low emissivity coated glass of claim 1, wherein said intermediate dielectric layer has a geometric thickness of 50nm to 100nm, said intermediate dielectric layer being selected from at least one of Zn, si, sn, ti, nb, zr, hf, mg, ni, in, al, ga, W, bi metal oxides and mixtures thereof, or from at least one of Si, al, zr, ti, Y, hf, nb, ta metal nitrides or oxynitrides and mixtures thereof.
14. A laminated glass, comprising:
a glass plate;
an adhesive layer; and
the dual infrared reflecting layer low emissivity coated glass of any one of claims 1-13, wherein the adhesion layer is disposed between the dual infrared reflecting layer low emissivity coated glass and the glass sheet, and the outer dielectric layer is disposed closer to the adhesion layer than the glass substrate.
15. The laminated glass of claim 14, wherein the glass sheet is a low emissivity coated glass having a dual infrared reflecting layer according to any one of claims 1 to 13.
16. A vehicle, characterized by comprising:
a vehicle body; and
a vehicle window provided in the vehicle body, the vehicle window comprising the low emissivity coated glass of the dual infrared reflecting layer of any one of claims 1-13.
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| CN202210109286.1A CN114538792B (en) | 2022-01-28 | 2022-01-28 | Low-emissivity coated glass with double infrared reflecting layers, laminated glass and vehicle |
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