WO2023143064A1 - 天窗玻璃及车辆 - Google Patents

天窗玻璃及车辆 Download PDF

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Publication number
WO2023143064A1
WO2023143064A1 PCT/CN2023/071636 CN2023071636W WO2023143064A1 WO 2023143064 A1 WO2023143064 A1 WO 2023143064A1 CN 2023071636 W CN2023071636 W CN 2023071636W WO 2023143064 A1 WO2023143064 A1 WO 2023143064A1
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WO
WIPO (PCT)
Prior art keywords
layer
glass
skylight
refractive index
visible light
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Application number
PCT/CN2023/071636
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English (en)
French (fr)
Inventor
鲁岳闽
林军
陈志新
Original Assignee
福建省万达汽车玻璃工业有限公司
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Publication of WO2023143064A1 publication Critical patent/WO2023143064A1/zh

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    • 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
    • C03C17/3605—Coatings of the type glass/metal/inorganic compound
    • 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
    • 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
    • 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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • B60J7/00—Non-fixed roofs; Roofs with movable panels, e.g. rotary sunroofs
    • 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
    • C03C17/366—Low-emissivity or solar control coatings
    • 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
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/23—Mixtures
    • C03C2217/231—In2O3/SnO2
    • 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
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/24—Doped oxides
    • 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
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/24—Doped oxides
    • C03C2217/241—Doped oxides with halides
    • 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
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/73—Anti-reflective coatings with specific characteristics
    • C03C2217/734—Anti-reflective coatings with specific characteristics comprising an alternation of high and low refractive indexes

Definitions

  • the present application relates to the technical field of vehicles, in particular to a sunroof glass and a vehicle.
  • the present application provides a sunroof glass and a vehicle, which can reduce the visible light reflectance of the surface of the sunroof glass facing the interior of the vehicle, so that passengers can have a better visual experience when looking out from the interior of the vehicle.
  • the present application provides a skylight glass
  • the skylight glass includes a glass substrate, a metal absorption layer and an anti-reflection layer
  • the glass substrate includes an outer surface and an inner surface, and the inner surface is far away from the glass
  • the metal absorption layer and the anti-reflection layer are sequentially stacked in the direction of the substrate.
  • the skylight glass further includes a first protective layer, and the first protective layer is disposed on the inner surface and located between the inner surface and the metal absorption layer.
  • the skylight glass further includes a second protective layer, and the second protective layer is provided on a surface of the anti-reflection layer away from the metal absorption layer.
  • the anti-reflection layer includes at least one laminated layer of high refractive index layer/low refractive index layer, the refractive index of the high refractive index layer is greater than or equal to 1.7, and the refractive index of the low refractive index layer is The refractive index is less than 1.7.
  • the skylight glass further includes a low-emissivity layer, and the low-emission layer is arranged between the first protective layer and the metal absorption layer.
  • the low-radiation layer includes one or more of an indium tin oxide layer, a fluorine-doped tin oxide layer, a tin antimony oxide layer, or an aluminum-doped zinc oxide layer.
  • a barrier layer is further included, and the barrier layer is arranged between the low-emissivity layer and the metal absorption layer.
  • the glass substrate is laminated glass
  • the laminated glass includes an inner glass, an outer glass, and an interlayer connected between the outer glass and the inner glass
  • the The inner layer of glass includes a first surface and a second surface opposite to each other, wherein the first surface is the inner surface
  • the outer layer of glass includes a third surface and a fourth surface opposite to each other, wherein the first Four surfaces are the outer surfaces.
  • the glass substrate further includes an infrared reflection layer, and the infrared reflection layer is located on the second surface and/or the third surface.
  • the visible light transmittance of the skylight glass is in the range of 1%-20%, and the visible light reflectance of the skylight glass measured from the inner surface side is less than or equal to 4%, Among the Lab values of the reflected color of the skylight glass measured from the inner surface side, the a value ranges from -6 to 2, and the b value ranges from -12 to 0.
  • the visible light transmittance of the outer glass is greater than or equal to 70%
  • the visible light transmittance of the inner glass is greater than or equal to 70%
  • the visible light transmittance of the intermediate layer is The range is between 1% and 30%.
  • the visible light transmittance of the outer glass is less than or equal to 50%
  • the visible light transmittance of the inner glass is less than or equal to 50%
  • the visible light transmittance of the intermediate layer is Greater than or equal to 70%.
  • a dimming element is further arranged between the second surface and the third surface, and the dimming element includes a polymer dispersed liquid crystal dimming film, a polymer network liquid crystal dimming film , suspended particle dimming film or electrochromic dimming film.
  • the glass substrate is a single piece of tempered glass, and the thickness of the single piece of tempered glass is greater than or equal to 5mm.
  • the single piece of tempered glass is colored glass, and the total iron content of the colored glass calculated as Fe 2 O 3 ranges from 0.5% to 2.0%.
  • the present application provides a vehicle, which includes a vehicle body and the above-mentioned sunroof glass, the sunroof glass being connected to the vehicle body.
  • FIG. 1 is a schematic structural view of a vehicle using sunroof glass provided by an embodiment of the present application
  • Fig. 2 is a first structural schematic diagram of the skylight glass provided by the embodiment of the present application.
  • Fig. 3 is a second structural schematic diagram of the skylight glass provided by the embodiment of the present application.
  • Fig. 4 is a third structural schematic diagram of the skylight glass provided by the embodiment of the present application.
  • Fig. 5 is a fourth structural schematic view of the skylight glass provided by the embodiment of the present application.
  • Fig. 6 is a schematic diagram of the fifth structure of the skylight glass provided by the embodiment of the present application.
  • Fig. 7 is a schematic diagram of the sixth structure of the skylight glass provided by the embodiment of the present application.
  • Fig. 8 is a schematic diagram of the seventh structure of the skylight glass provided by the embodiment of the present application.
  • Fig. 9 is a schematic diagram of an eighth structure of the skylight glass provided by the embodiment of the present application.
  • Embodiments of the present application provide a sunroof glass 10 and a vehicle 100, which can reduce the visible light reflectance of the sunroof glass 10 measured from the side inside the car, thereby eliminating the need for sunroof glass when viewed from the inside of the car.
  • the mirror effect enables passengers to have a better visual experience when looking out from the inside of the car.
  • a vehicle 100 includes a sunroof glass 10 and a vehicle body 20 , and the sunroof glass 10 is connected to the vehicle body 20 .
  • the sunroof glass 10 may be a panoramic sunroof glass.
  • the visible light transmittance of the skylight glass 10 may be less than or equal to 30%, preferably less than or equal to 20%, specifically 19%, 18%, 17%, 16%, 15%, 14%, 13%, 12%, 11% %, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, the visible light reflectance of the sunroof glass 10 measured from the side of the car is less than or equal to 4% , preferably less than or equal to 3%, more preferably less than or equal to 2%.
  • the skylight glass 10 includes a glass substrate 11 and a metal absorption layer 12 and an anti-reflection layer 13 sequentially stacked on the glass substrate 11 .
  • FIG. 2 is only to schematically describe the connection relationship between the glass substrate 11 , the metal absorption layer 12 and the anti-reflection layer 13 , but not to specifically limit the connection position, specific structure and quantity of each device.
  • the structure shown in the embodiment of the present application does not constitute a specific limitation on the skylight glass 10 .
  • the sunroof glass 10 may include more or less components than those shown in the illustrations, or combine some components, or separate some components, or arrange different components.
  • the illustrated components can be realized in hardware, software or a combination of software and hardware.
  • the glass substrate 11 includes an inner surface 11a and an outer surface 11b oppositely arranged, the inner surface 11a is the surface of the sunroof glass 10 facing the interior side of the vehicle, and the outer surface 11b is the side of the sunroof glass 10 facing the side outside the vehicle .
  • a metal absorption layer 12 and an anti-reflection layer 13 are sequentially stacked on the inner surface 11 a along a direction away from the glass substrate 11 .
  • the glass substrate 11 may be transparent or colored.
  • the material of the glass substrate 11 may be soda lime silicate glass, borosilicate glass, aluminosilicate glass or plexiglass, and the plexiglass may be polymethyl methacrylate or polycarbonate, for example.
  • the glass substrate 11 used as the skylight glass 10 is generally in a curved shape, and the shape of the glass substrate 11 is not limited to the shape described above, and it can be any shape that meets the requirements for the use of the skylight glass 10, such as the glass substrate 11 It can also be in the shape of a flat plate, and the embodiment of the present application does not impose strict requirements on the shape of the glass substrate 11 .
  • the glass substrate 11 can be a single piece of tempered glass, the thickness of the single piece of tempered glass is greater than or equal to 5mm, for example, 5.1mm, 5.5mm, 5.8mm, 6mm, 6.5mm, 7mm, 7.5mm, 8mm, etc., the single piece of tempered glass It may be colored glass, the total iron content of which is calculated as Fe 2 O 3 is 0.5%-2.0%, such as green glass, blue glass, gray glass and the like.
  • the glass substrate 11 may be laminated glass, and the laminated glass includes an inner glass 111 , an outer glass 112 and an intermediate layer 113 connected between the outer glass 112 and the inner glass 111 .
  • the inner glass 111 includes a first surface 1111 and a second surface 1112 oppositely disposed, wherein the first surface 1111 is the inner surface 11 a of the glass substrate 11 .
  • the outer glass 112 includes a third surface 1121 and a fourth surface 1122 oppositely disposed, wherein the fourth surface 1122 is the outer surface 11 b of the glass substrate 11 .
  • the intermediate layer 113 is used to connect the outer layer of glass 112 and the inner layer of glass 111, so that the sunroof glass 10 as a whole presents a sandwich structure, so as to improve the strength of the glass body, making it not easy to break, and its impact resistance is better than that of a single layer.
  • the glass has been improved, and the improvement of impact resistance can improve the safety performance of the vehicle, and can make the glass body not easy to damage, reducing the maintenance cost.
  • the sunroof glass 10 also includes a dimming element (not shown), the dimming element is arranged between the second surface and the third surface, and the dimming element may include a polymer dispersed liquid crystal dimming film (PDLC), a polymer network liquid crystal dimming film One or more of optical film (PNLC), suspended particle (SPD) dimming film or electrochromic (EC) dimming film.
  • PDLC polymer dispersed liquid crystal dimming film
  • PNLC polymer network liquid crystal dimming film
  • SPD suspended particle dimming film
  • EC electrochromic
  • the glass substrate 11 may further include an infrared reflection layer 14 .
  • the infrared reflective layer 14 is disposed on the second surface 1112 of the inner glass 111 and/or the third surface 1121 of the outer glass 112 .
  • the infrared reflective layer 14 includes at least one metal functional layer and a plurality of Medium layer
  • the metal functional layer can be exemplified as gold layer, silver layer, copper layer, silver-copper alloy layer, silver-indium alloy layer, silver-gold alloy layer, etc.
  • the infrared reflection layer 14 can be a single silver Coating (comprising one silver layer), double silver coating (comprising two silver layers), triple silver coating (comprising three silver layers), quadruple silver coating (comprising four silver layers), etc.
  • the infrared reflective layer 14 can reflect most of the infrared rays in the wavelength range of 780nm-2500nm, so that the sunroof glass 10 has sun protection and heat insulation performance, improves the thermal comfort in the car, and makes the sunroof glass 10 adapt to the development trend of panoramic glass.
  • the outer layer of glass 112 is arranged parallel to the inner layer of glass 111 . Under this setting, the thickness of the middle layer 113 is uniform.
  • the extending direction of the outer layer of glass 112 intersects the extending direction of the inner layer of glass 111 .
  • the thickness of the middle layer 113 is not uniform, and it may present a structural configuration with a gradually changing thickness.
  • the middle layer 113 may be wedge-shaped.
  • the thickness of the intermediate layer 113 can be flexibly adjusted according to the actual application scenarios of the sunroof glass 10 , which is beneficial to meet the multi-scenario application requirements of the sunroof glass 10 .
  • both the inner glass 111 and the outer glass 112 can be 2.1mm transparent glass (ordinary white glass), specifically, the thickness of the inner glass 111 and the outer glass 112 is in the range of 0.7mm-4.0mm All meet the requirements (including endpoint values 0.7mm and 4.0mm). In order to meet the requirement of light weight, preferably the thickness of the outer glass 112 is 1.6mm-4.0mm, the thickness of the inner glass 111 is 0.7mm-2.1mm, and the thickness of the outer glass 112 is greater than or equal to the thickness of the inner glass 111.
  • the visible light transmittance of the outer glass 112 is greater than or equal to 70%, preferably greater than or equal to 80%, or even greater than or equal to 90%; the visible light transmittance of the inner glass 111 is greater than or equal to 70%, preferably greater than or equal to 80%, even greater than or equal to 90%; the inner glass 111 and the outer glass 112 are made of ordinary white glass, which can greatly reduce the product cost and improve the market competitiveness of the product.
  • the visible light transmittance of the skylight glass 10 is adjusted by selecting intermediate layers 113 with different visible light transmittances.
  • the visible light transmittance of the intermediate layer 113 is 1% to 30%, for example 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17% , 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, etc.
  • the material of the middle layer 113 can be polyethylene Alcohol butyral (PVB), ethylene vinyl acetate (EVA), ionomer film (SGP), etc.
  • the visible light transmittance of the outer glass 112 is less than or equal to 50%, preferably less than or equal to 40%, more preferably less than or equal to 30%, even less than or equal to 20%; the inner layer The visible light transmittance of the glass 111 is less than or equal to 50%, preferably less than or equal to 40%, more preferably less than or equal to 30%, even less than or equal to 20%; the visible light transmittance of the intermediate layer 113 is greater than or equal to 70% Specifically, it may be greater than or equal to 70%, greater than or equal to 75%, greater than or equal to 80%, greater than or equal to 85%, greater than or equal to 90%, and the like.
  • an ordinary transparent intermediate layer such as standard transparent PVB, the product cost can be greatly reduced and the market competitiveness of the product can be improved.
  • the metal absorption layer 12 is connected to the first surface 1111 of the inner glass 111 . It can be understood that by disposing the metal absorbing layer 12 on the glass substrate 11 , on the one hand, the absorption of light can be adjusted through the metal absorbing layer 12 , and the radiation performance and appearance color of the skylight glass 10 can be improved. On the other hand, the metal absorbing layer 12 can absorb visible light to a certain extent, and reduce the visible light reflectance of the inner surface 11a of the sunroof glass 10 facing the inside of the car, so that the user can better see the outside world through the sunroof, and reduce the amount of light from the sunroof. The inner surface 11a of the glass 10 reflects the influence of light on the users in the vehicle, so as to improve the user experience.
  • the metal absorption layer 12 may be a metal film layer, and the material of the film layer may be a combination of one or more materials among Ni, Cr, Fe, Ti, Mo, Zr, Si, Nb and the like.
  • the thickness of the metal absorption layer 12 may be 1 nm-15 nm, preferably 3 nm-12 nm, more preferably 5-10 nm.
  • the metal absorption layer 12 with a moderate thickness can not only absorb visible light, but also cooperate with the anti-reflection layer 13 to further reduce the visible light reflectance of the glass substrate 11 .
  • the anti-reflection layer 13 is disposed on a side of the metal absorption layer 12 away from the inner glass 111 .
  • the anti-reflection layer 13 can be coated using a magnetron sputtering process. It can be understood that the anti-reflection layer 13 can reduce the visible light reflectance of the glass substrate 11 .
  • the anti-reflection layer 13 cooperates with the metal absorption layer 12 to further reduce the visible light reflectance of the inner surface 11a of the glass substrate 11, so that the skylight glass 10 can adapt to the application trend of panoramic glass.
  • the synergistic effect of the anti-reflection layer 13 and the metal absorption layer 12 can greatly reduce the visible light reflectance of the inner surface 11a of the glass substrate 11, eliminate the mirror effect of the sunroof glass 10 when viewed from the inside of the vehicle, and improve user experience.
  • the antireflection layer 13 includes at least one stack of high refractive index layer 131 /low refractive index layer 132 .
  • the high refractive index layer 131 is connected to the metal absorption layer 12
  • the low refractive index layer 132 is connected to the high refractive index layer 131 and away from the metal absorption layer 12 .
  • the refractive index of the high refractive index layer 131 is greater than or equal to 1.7, and the refractive index of the low refractive index layer 132 is less than 1.7.
  • the lamination of high refractive index layer 131/low refractive index layer 132 means that the high refractive index layer 131 and the low refractive index layer 132 are sequentially stacked and formed, for example, a stack of high refractive index layer 131/low refractive index layer 132 is included.
  • the layers are a high refractive index layer 131 and a low refractive index layer 132 in sequence, and the laminate comprising two high refractive index layers 131/low refractive index layer 132 is sequentially a high refractive index layer 131, a low refractive index layer 132, and a high refractive index layer. 131.
  • Low-refractive-index layer 132 comprising three high-refractive-index layers 131/low-refractive-index layers 132 stacked in turn: high-refractive-index layer 131, low-refractive-index layer 132, high-refractive-index layer 131, low-refractive-index layer 132 , a high refractive index layer 131 , and a low refractive index layer 132 .
  • the thickness of the high-refractive index layer 131 may range from 1 nm to 70 nm (inclusive of endpoints 1 nm and 70 nm).
  • the high-refractive index layer 131 may also include at least two high-refractive-index sub-layers, for example, the laminate of the high-refractive-index layer 131/low-refractive-index layer 132 may specifically be the first high-refractive-index sub-layer , the second high refractive index sublayer, and the low refractive index layer 132, wherein the refractive index of the first high refractive index sublayer is smaller than the refractive index of the second high refractive index sublayer.
  • the thickness range of the low refractive index layer 132 can be between 20nm-150nm (including the endpoint value of 20nm and 150nm).
  • the refractive index of the high refractive index layer 131 can be in the range of 1.7-2.5 (including the endpoint value 1.7 and 2.5), and the refractive index of the low refractive index layer 132 can be in the range of 1.4-1.69 (including the endpoint value of 1.4 and 1.69).
  • the material of the high refractive index layer 131 may include oxides or alloy oxides of Zn, Sn, Nb, Ti, Ni, Cr, Ta, such as zinc tin oxide (ZnSnO x ), titanium oxide (TiO x ), niobium oxide (NbO x ), etc., or nitrides or alloy nitrides including Si, Zr, and Al, such as silicon nitride (SiN x ), silicon-based aluminum nitride (SiAlN x ), silicon-based zirconium nitride (SiZrN x ), etc.
  • oxides or alloy oxides of Zn, Sn, Nb, Ti, Ni, Cr, Ta such as zinc tin oxide (ZnSnO x ), titanium oxide (TiO x ), niobium oxide (NbO x ), etc.
  • nitrides or alloy nitrides including Si, Zr, and Al such
  • the material of the low refractive index layer 132 may include oxides or alloy oxides of Si, Zr, and Al, such as silicon oxide (SiO x ), silicon-based aluminum oxide (SiAlO x ), silicon-based zirconia (SiZrO x ), and the like. Wherein, the value of x is determined according to the stoichiometric, sub-stoichiometric or super-stoichiometric deposition in the magnetron sputtering process.
  • the anti-reflection layer 13 may include a stack of high refractive index layer 131/low refractive index layer 132, or may include at least two stacked layers, specifically, the anti-reflection layer 13 may include two layers. One stack, three stacks, or four stacks, etc. Based on considerations such as process manufacturing and cost, it is preferable that the anti-reflection layer 13 only includes a stack of high refractive index layer 131/low refractive index layer 132.
  • the embodiment of the application uses metal absorption layer 12 and anti-reflection
  • the synergistic effect of the layer 13, the antireflection effect of the antireflection layer 13 comprising only one laminated layer can achieve the same level of antireflection as that of the traditional antireflective layer comprising two laminated layers, three laminated layers or even four laminated layers. reflection effect.
  • the antireflection layer 13 only includes a stack of high refractive index layer 131/low refractive index layer 132 layer, and from the inner surface 11a of the glass substrate 11 toward the interior of the vehicle, it is arranged according to the high refractive index layer 131-low refractive index layer 132 structure.
  • the anti-reflection layer 13 includes a high-refractive-index layer 131 and a low-refractive-index layer that are sequentially stacked on the side of the metal absorption layer 12 away from the inner glass 111 132.
  • the high-refractive-index layer 131 in the anti-reflection layer 13 includes two high-refractive-index sub-layers, and from the inner surface 11a to the direction away from the inner glass 111, according to the first high-refractive-index sub-layer Structural arrangement of layer 1311 -second high refractive index sublayer 1312 -low refractive index 132 .
  • the laminated structure in the direction from the inner surface 11 a to the inner surface 11 a away from the inner glass 111 , includes a first layer that is sequentially stacked on the side of the metal absorbing layer 12 away from the inner glass 111 .
  • the refractive index of the first high refractive index sublayer 1311 is smaller than the refractive index of the second high refractive index sublayer 1312 .
  • the antireflection layer 13 includes a stack of two high refractive index layers 131/low refractive index layers 132, and along the direction away from the inner surface 11a of the inner glass 111, according to the high refractive index layer 131 —the low refractive index layers 132 are periodically arranged alternately, and the outermost layer (that is, the layer farthest from the first surface 1111 of the inner glass 111 ) is the low refractive index layer 132 .
  • the outermost layer that is, the layer farthest from the first surface 1111 of the inner glass 111
  • the anti-reflection layer 13 includes a first high-refractive index layer 131a, a first low-refractive-index layer 132a, a second high-refractive-index layer 131b and a first Two low refractive index layers 132b.
  • the material and thickness of the first high refractive index layer 131a and the material and thickness of the second high refractive index layer 131b may be the same or different; the material and thickness of the first low refractive index layer 132a are the same as those of the second low refractive index layer
  • the material and thickness of 132b may be the same or different.
  • an appropriate glass substrate 11 can be selected, and by adjusting the material and thickness of the metal absorption layer 12 and the anti-reflection layer 13, the Lab of the reflection color of the skylight glass 10 can be measured from the inner surface 11a side.
  • the value of a in the value ranges between -6 and 2 (including the endpoint value -6 and 2), and the value of b ranges between -12 and 0 (including -12 and 0), so that the sunroof glass can be observed from the side of the car
  • the color of 10 is preferably neutral, so that passengers have a better visual effect in the car.
  • the sunroof glass 10 may further include a first protective layer 15, and the first protective layer 15 is directly provided on the first surface 1111 of the inner glass 111, that is, the first The protective layer 15 is provided between the inner surface 11 a of the glass substrate 11 and the metal absorption layer 12 .
  • the first protective layer 15 can block the damage and oxidation of the metal absorption layer 12 caused by the diffusion of alkali metal ions and oxygen on the surface of the inner glass 111 when the inner glass 111 is bent and formed at a high temperature of at least 500°C.
  • the thickness of the first protective layer 15 may be greater than or equal to 5 nm.
  • the material of the first protective layer 15 may include oxides or alloy oxides of Zn, Sn, Ti, Si, Al, Nb, Zr, Ni, Mg, Cr, Ta, etc., or include Si, Al, Zr, B, Ti Other nitrides or alloy oxynitrides.
  • alloy oxides and alloy oxynitrides refer to oxides and oxynitrides of at least two elements.
  • the sunroof glass 10 may further include a second protective layer 16, and the second protective layer 16 is disposed on the side of the anti-reflection layer 13 away from the metal absorption layer 12, that is, The second protective layer 16 is disposed on the outermost layer of the film structure of the skylight glass 10 .
  • the second protective layer 16 is beneficial to further improve the overall mechanical stability and thermal stability of the film layer.
  • the material of the second protective layer 16 may include nitrides or alloy oxynitrides of Si, Al, Zr, Ti, B, Ni, etc., such as SiN x , SiAlN x , SiZrN x , etc.
  • the thickness of the second protective layer 16 is greater than or equal to 3 nm. Considering the influence of the second protective layer 16 on the anti-reflection layer 13, the thickness of the second protective layer 16 is preferably less than or equal to 30 nm. In general, more preferably, the thickness of the second protective layer 16 is 5nm-20nm.
  • the sunroof glass 10 may further include a first protective layer 15 and a second protective layer 16 , the first protective layer 15 is disposed between the metal absorption layer 12 and the inner glass 111 In between, the second protection layer 16 is disposed on the surface of the anti-reflection layer 13 away from the metal absorption layer 12 .
  • the color of the skylight glass 10 can be adjusted by adjusting the film material and film thickness of the metal absorption layer 12 and the anti-reflection layer 13, but also by adjusting the color of the first protective layer 15 and the second protective layer 16.
  • the color of the skylight glass 10 is adjusted by the material and thickness of the film layer, which is not strictly limited in the embodiments of the present application.
  • the skylight glass 10 may further include a low-emissivity layer 17 disposed between the first protective layer 15 and the metal absorption layer 12 .
  • the low-E layer 17 is used to reduce the emissivity of the skylight glass 10 measured from the side of the inner surface 11a, and the range of the emissivity of the skylight glass 10 measured from the side of the inner surface 11a is between 0.01-0.25 (including the endpoint value 0.01 and 0.25), which can better block heat transfer inside and outside the car.
  • the low-emissivity layer 17 includes an ITO layer (indium tin oxide), an FTO layer (fluorine-doped tin oxide), an ATO layer (antimony tin oxide) or an AZO layer ( One or more of aluminum-doped zinc oxide), and a barrier layer 18 is also provided between the low-emissivity layer 17 and the metal absorption layer 12.
  • the first protective layer 15 , the low-emissivity layer 17 , the barrier layer 18 , the metal absorption layer 12 , the high refractive index layer 131 , the low refractive index layer 132 , and the second protective layer 16 can be sequentially disposed on the first surface 1111 .
  • the first protective layer 15 can be directly disposed on the first surface 1111 .
  • the low-emissivity layer 17 is disposed on the side of the first protective layer 15 away from the inner glass 111
  • the barrier layer 18 is disposed on the side of the low-emissivity layer 17 away from the first protective layer 15 .
  • setting the first protective layer 15 on the surface of the inner glass 111 can prevent the alkali metal ions in the inner glass 111 from entering the film structure, thereby protecting the first protective layer 15 and the second protective layer 16
  • the optical film layer in between, and the low-emissivity layer 17 is provided on the side of the first protective layer 15 away from the glass substrate 11, so that the skylight glass 10 has an excellent low-emissivity effect.
  • the barrier layer 18 is set on the side of the low-emissivity layer 17 away from the first protective layer 15, because the barrier layer 18 is located between the metal absorption layer 12 and the low-emission layer 17, and prevents the two from interacting to cause the metal absorption layer 12 Or the performance of the low-emissivity layer 17 decreases or even fails.
  • the present application also provides a method for preparing the skylight glass 10, wherein the specific structure of the skylight glass 10 can refer to FIGS. 1-9 and the above description. And in the description of the following method, the improvement of the skylight glass 10 can be applied to the above description of the skylight glass 10 under the condition of no conflict, the method includes:
  • S100 Provide an inner layer of glass 111, wherein the inner layer of glass 111 includes a first surface 1111 and a second surface 1112 opposite to each other.
  • S300 Prepare a glass substrate 11, wherein the glass substrate 11 includes an inner glass 111, an outer glass 112, and an intermediate layer 113 connected between the inner glass 111 and the outer glass 112, and the inner surface 11a of the glass substrate 11 is an inner The first surface 1111 of the layer glass 111 .
  • the metal absorption layer 12 and the anti-reflection layer 13 are sequentially stacked on the first surface 1111 of the inner glass 111 .
  • the metal absorption layer 12 and the anti-reflection layer 13 are deposited on the first surface 1111 by magnetron sputtering process.
  • the first protective layer 15, the low-emissivity layer 17, the barrier layer 18, the metal absorption layer 12, the high refractive index layer 131, the low refractive index layer 132, and the second protective layer 16 are sequentially stacked by magnetron sputtering process deposited on the first surface 1111 of the inner glass 111 .
  • the glass substrate 11 includes an inner glass 111, an outer glass 112, and an interlayer 113 connected between the inner glass 111 and the outer glass 112.
  • the inner surface 11a of the glass substrate 11 is the first surface 1111 of the inner glass 111.
  • the infrared reflective layer 14 is also deposited on the third surface 1121 of the outer layer glass 112, and the outer layer glass 112 and the inner layer glass 111 are subjected to high-temperature bending forming treatment, wherein the temperature range of the high-temperature bending forming treatment can be 550°C-700°C (Including endpoints 550°C and 700°C). Then connect the outer layer glass 112 and the inner layer glass 111 through the intermediate layer 113.
  • the visible light transmittance range of the intermediate layer 113 can be between 1% and 30%. and the interlayer 113 form a laminated glass structure.
  • the present application also provides five examples and four comparative examples to analyze and explore the performance of the skylight glass 10 .
  • the outer layer glass 112 and the inner layer glass 111 are ordinary white glass with a thickness of 2.1 mm.
  • the first protective layer 15 Si 3 N 4 layer
  • metal absorber layer 12 NiCr layer with a thickness of 6.5nm
  • high refractive index layer TiO2 layer with a thickness of 26nm
  • low refractive index layer SiO2 layer with a thickness of 36nm
  • TiO2 layer with a thickness of 26nm layer and a 36 nm thick SiO 2 layer constitute the antireflection layer 13 .
  • the outer glass 112 and the inner glass 111 are subjected to high-temperature bending treatment, and then a 0.76 mm thick gray PVB with a visible light transmittance of about 10% is prepared as the middle layer 113, which is formed by the automobile glass production process Laminated glass structure.
  • the outer layer glass 112 and the inner layer glass 111 are ordinary white glass with a thickness of 2.1 mm.
  • the metal absorption layer 12 (NiCr with a thickness of 6.5 nm) is sequentially deposited on the first surface 1111 of the inner layer glass 111.
  • High refractive index layer TiO2 layer with a thickness of 26nm
  • low refractive index layer SiO2 layer with a thickness of 32nm
  • second protective layer 16 Si3N4 layer with a thickness of 15nm
  • 26nm thick TiO2 layer and a 32 nm thick SiO 2 layer constitute the antireflection layer 13 .
  • the outer glass 112 and the inner glass 111 are subjected to high-temperature bending and molding treatment, and then a 0.76 mm thick PVB with a visible light transmittance of about 10% is prepared as the middle layer 113, and the interlayer is formed through the automobile glass production process glass structure.
  • the outer layer glass 112 and the inner layer glass 111 are ordinary white glass with a thickness of 2.1 mm.
  • the first protective layer 15 Si 3 N 4 layer
  • metal absorption layer 12 NiCr layer with a thickness of 6.5nm
  • high refractive index layer TiO2 layer with a thickness of 26nm
  • low refractive index layer SiO2 layer with a thickness of 34nm
  • the second protective layer 16 Si 3 N 4 layer with a thickness of 15 nm
  • a 26 nm thick TiO 2 layer and a 34 nm thick SiO 2 layer constitute the antireflection layer 13 .
  • the outer glass 112 and the inner glass 111 are subjected to high-temperature bending and molding treatment, and then a 0.76 mm thick PVB with a visible light transmittance of about 10% is prepared as the middle layer 113, and the interlayer is formed through the automobile glass production process glass structure.
  • the outer layer glass 112 and the inner layer glass 111 are ordinary white glass with a thickness of 2.1mm, and the first protective layer 15 (ZnSnO x layer with a thickness of 10nm) is sequentially deposited on the first surface 1111 of the inner layer glass 111 by magnetron sputtering , metal absorption layer 12 (NiCr layer with a thickness of 6.5nm), high refractive index layer (TiO 2 layer with a thickness of 26nm), low refractive index layer (SiO 2 layer with a thickness of 34nm), the second protective layer 16 (thickness 15nm Si 3 N 4 layers), 26 nm thick TiO 2 layer and 34 nm thick SiO 2 layer constitute the anti-reflection layer 13 .
  • the first protective layer 15 ZnSnO x layer with a thickness of 10nm
  • metal absorption layer 12 NiCr layer with a thickness of 6.5nm
  • high refractive index layer TiO 2 layer with a thickness of 26nm
  • the outer glass 112 and the inner glass 111 are subjected to high-temperature bending and molding treatment, and then a 0.76 mm thick PVB with a visible light transmittance of about 10% is prepared as the middle layer 113, and the interlayer is formed through the automobile glass production process glass structure.
  • the outer layer glass 112 and the inner layer glass 111 are ordinary white glass with a thickness of 2.1 mm.
  • the first protective layer 15 Si 3 N 4 layer
  • low-emissivity layer 17 ITO layer with a thickness of 138nm
  • barrier layer 18 Si 3 N 4 layer with a thickness of 10nm
  • metal absorber layer 12 NiCr layer with a thickness of 8.5nm
  • high refractive index layer TiO 2 layer with a thickness of 34nm
  • a low refractive index layer a SiO 2 layer with a thickness of 63nm
  • a second protective layer 16 a Si 3 N 4 layer with a thickness of 10nm
  • the SiO 2 layer constitutes the antireflection layer 13 .
  • the outer glass 112 and the inner glass 111 are subjected to high-temperature bending and molding treatment, and then a 0.76 mm thick PVB with a visible light transmittance of about 10% is prepared as the middle layer 113, and the interlayer is formed through the automobile glass production process glass structure.
  • Embodiment 6 is a diagrammatic representation of Embodiment 6
  • the outer layer of glass 112 and the inner layer of glass 111 are gray glass with a thickness of 2.1 mm and a transmittance of about 40%-50%.
  • the first protective layer 15 thinness 10nm SiN layer
  • metal absorber layer 12 NiCr layer with a thickness of 7.2nm
  • high refractive index layer TiO2 layer with a thickness of 26nm
  • low refractive index layer SiO2 layer with a thickness of 36nm
  • the second Two protective layers 16 (a Si 3 N 4 layer with a thickness of 15 nm), a 26 nm thick TiO 2 layer and a 36 nm thick SiO 2 layer constitute the antireflection layer 13 .
  • the outer glass 112 and the inner glass 111 are subjected to high-temperature bending and molding treatment, and then a 0.76mm thick PVB with a visible light transmittance of about 90% is prepared as the middle layer 113, and the interlayer is formed through the automobile glass production process glass structure.
  • the outer glass 112 and the inner glass 111 are ordinary white glass with a thickness of 2.1 mm, and without any film deposition, the outer glass 112 and the inner glass 111 are subjected to high-temperature bending and forming treatment, and then a 0.76 mm thick visible light transmission film is prepared. PVB with a rate of about 10% is used as the intermediate layer 113, and a laminated glass structure is formed through the automobile glass production process.
  • the outer layer glass 112 and the inner layer glass 111 are ordinary white glass with a thickness of 2.1mm, and the first surface 1111 of the inner layer glass 111 adopts the magnetron sputtering method to sequentially deposit high refractive index layers (thickness is 5nm TiO 2 layer), Low refractive index layer ( SiO2 layer with a thickness of 130nm), no metal absorber layer 12 deposited.
  • a 5nm thick TiO2 layer and a 130nm thick SiO2 layer constitute the antireflection layer 13.
  • the outer glass 112 and the inner glass 111 are subjected to high-temperature bending and molding treatment, and then a 0.76 mm thick PVB with a visible light transmittance of about 10% is prepared as the middle layer 113, and the interlayer is formed through the automobile glass production process glass structure.
  • the outer layer glass 112 and the inner layer glass 111 are ordinary white glass with a thickness of 2.1mm.
  • magnetron sputtering is used to deposit a high refractive index layer (thickness is 10nm TiO 2 layer), Low refractive index layer ( SiO2 layer with a thickness of 48nm), high refractive index layer ( TiO2 layer with a thickness of 106nm), low refractive index layer ( SiO2 layer with a thickness of 96nm), undeposited metal absorber layer 12.
  • a thick TiO 2 layer, a 48 nm thick SiO 2 layer, a 106 nm thick TiO 2 layer and a 96 nm thick SiO 2 layer constitute the antireflection layer 13 .
  • the outer glass 112 and the inner glass 111 are subjected to high-temperature bending and molding treatment, and then a 0.76 mm thick PVB with a visible light transmittance of about 10% is prepared as the middle layer 113, and the interlayer is formed through the automobile glass production process glass structure.
  • the outer layer glass 112 and the inner layer glass 111 are ordinary white glass with a thickness of 2.1 mm.
  • the first protective layer 15 Si 3 N 4 layer
  • a metal absorption layer 12 a NiCr layer with a thickness of 7.5 nm
  • a second protective layer 16 a Si 3 N 4 layer with a thickness of 58 nm
  • no anti-reflection layer 13 deposited.
  • the outer glass 112 and the inner glass 111 are subjected to high-temperature bending and molding treatment, and then a 0.76 mm thick PVB with a visible light transmittance of about 10% is prepared as the middle layer 113, and the interlayer is formed through the automobile glass production process glass structure.
  • measuring the visible light reflectance of the inner layer glass from the first surface side is: after the inner layer glass deposited with the film layer is subjected to high temperature bending and forming treatment, before forming the laminated glass structure, from the first surface to The visible light reflectance of a single piece of inner glass directly measured from the side; the visible light reflectance of the skylight glass measured from the inner surface side: the outer glass after high-temperature bending and the inner glass deposited with a film layer and the middle layer Visible light reflectance of sunroof glass measured from the inner surface side after the laminated glass structure is formed by the automotive glass production process.
  • the visible light reflectance of the inner glass 111 without depositing the metal absorption layer 12 and the anti-reflection layer 13 is greater than 8%, even if the laminated glass is formed with the intermediate layer 113 and the outer glass 112
  • the visible light reflectance of the skylight glass 10 measured from the side of the inner surface 11 a is still greater than 4%, and there is a relatively obvious mirror effect.
  • Comparative Example 2 by setting the antireflection layer 13, that is, a lamination of a high refractive index layer 131 and a low refractive index layer 132, the visible light reflectance of the first surface 1111 of the inner glass 111 is reduced to 5%-6 %, and then form a laminated glass with the intermediate layer 113 and the outer glass 112 as the sunroof glass 10.
  • the visible light reflectance of the sunroof glass 10 measured from the side of the inner surface 11a is less than 3%. Observe that the reflection color of the skylight glass 10 is reddish-purple, seriously deviates from the neutral color, and is not easily accepted by passengers.
  • Comparative Example 3 two laminated layers comprising a high-refractive-index layer 131 and a low-refractive-index layer 132 are provided. At this time, the visible light reflectance of the first surface 1111 of the inner layer glass 111 is reduced to 4%-5%.
  • the interlayer 113 and the outer glass 112 form a laminated glass as the skylight glass 10, and the visible light reflectance of the skylight glass 10 measured from the inner surface 11a side is less than 2%.
  • the reflection color of the sunroof glass 10 observed from the inside of the car is relatively neutral, but the total thickness of the film layer is 260nm, which is not conducive to the manufacturing process and the production cost is high.
  • a nickel-chromium alloy (NiCr) is used as the metal absorption layer 12.
  • NiCr nickel-chromium alloy
  • the visible light reflectance of the first surface 1111 of the inner layer glass 111 is less than 4%
  • an interlayer is formed with the intermediate layer 113 and the outer layer glass 112.
  • the glass is used as the skylight glass 10, and the visible light reflectance of the skylight glass 10 measured from the side of the inner surface 11a is less than 3%.
  • the Lab color test it is found through the Lab color test that the reflected color of the sunroof glass 10 when viewed from the inside of the car seriously deviates from the neutral color, which is not easily accepted by passengers.
  • the film layer structure of embodiment 3 can make the visible light reflectance of the first surface 1111 of the inner layer glass 111 less than 4%, and then form a laminated glass with the intermediate layer 113 and the outer layer glass 112 as the skylight glass 10, from the inside
  • the visible light reflectance of the sunroof glass 10 measured on the side of the surface 11a is less than 2%, and the reflection color of the sunroof glass 10 observed from the inside of the vehicle also meets the neutral color requirement.
  • the total thickness of the film layer in Example 3 is about one-third of that of Comparative Example 3, which has obvious advantages in terms of manufacturing process and cost.
  • the laminated glasses of Examples 1-6 were measured for visible light reflectance and reflected color, and the measurement results are listed in Table 2.
  • the visible light reflectance (before high-temperature heat treatment) of the inner layer glass measured from the first surface side is: after the inner layer glass is subjected to film deposition and before high-temperature bending and forming treatment, the unit directly measured from the first surface side
  • the visible light reflectance of the inner glass of the sheet; the visible light reflectance of the inner glass measured from the side of the first surface (after high-temperature heat treatment) is: after the inner glass deposited with the film layer is subjected to high-temperature bending and forming treatment, a laminated glass structure is formed
  • the visible light reflectance of a single piece of inner glass is directly measured from the first surface side;
  • the visible light reflectance of the skylight glass is measured from the inner surface side: the outer glass that has been subjected to high-temperature bending molding and the deposited film layer
  • the visible light reflectance of the skylight glass is measured from the inner surface side after the inner layer glass and the middle layer form a laminated glass structure through the automotive glass production process.
  • the visible light reflectance of the skylight glass 10 in Examples 1-6 is all less than 4%, or less than 3%, or even less than 2% when measured from the side of the inner surface 11a, and from the side of the inner surface 11a
  • the a value range in the Lab value of the reflected color of the skylight glass 10 in Examples 1-6 is between -6 and 2 (including the endpoint values -6 and 2), and the b value range is between -12 and 0 ( Including power-off value -12 and 0), that is, the sunroof glass 10 in the embodiment 1-6 can eliminate the mirror effect inside the car, and also has an excellent neutral color for viewing inside the car.
  • Example 6 uses gray glass as the outer glass and the inner glass, and adopts the technical solution of the present invention to still meet the requirements of visible light reflectance lower than 2% and neutral color.
  • the total thickness of the first protective layer 15, the metal absorption layer 12, the antireflection layer 13, and the second protective layer 16 is less than or equal to 200nm, preferably less than or equal to 150nm, even less than or equal to Equal to 100nm, it has obvious advantages in process manufacturing and cost.
  • the metal absorption layer 12 may be partially oxidized during the high-temperature bending process of the inner layer glass 111 after the deposition of the film layer, which eventually leads to high-temperature bending forming.
  • the visible light reflectance of the inner layer glass 111 measured from the first surface side is greatly increased, and then the laminated glass is formed with the intermediate layer 113 and the outer layer glass 112 as the skylight glass 10, and the skylight glass is measured from the side of the inner surface 11a
  • the visible light reflectance of 10 is less than 4%, and at this time, the reflected color of the sunroof glass 10 also meets the requirement of neutral color when viewed from the inside of the vehicle, but the reflected color Lab value is not as excellent as other embodiments.
  • Example 4 uses ZnSnOx as the material of the first protective layer 15, while Example 3 uses Si 3 N 4 as the material of the first protective layer 15, measured from the first surface side
  • the change of the visible light reflectance before and after the high-temperature bending molding treatment in Example 4 is greater than that of Example 3.
  • the material of the first protective layer 15 includes Si nitride, which is further beneficial Improve the thermal stability of the film layer and reduce the oxidation degree of the metal absorption layer 12 .
  • Embodiment 5 it can still maintain a very low reflectance of visible light and excellent neutral color.

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Abstract

本申请提供一种天窗玻璃及车辆，所述天窗玻璃包括玻璃基板、金属吸收层和减反射层，所述玻璃基板包括外表面和内表面，在所述内表面上沿远离所述玻璃基板的方向依次层叠设置所述金属吸收层和所述减反射层。本申请提供的天窗玻璃能够降低天窗玻璃朝向车内一侧的表面的可见光反射率，使乘客从车内向外看时有更好的视觉体验。

Description

天窗玻璃及车辆
本申请要求于2022年01月28日提交中国专利局、申请号为202210109009.0、申请名称为“天窗玻璃及车辆”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请涉及交通工具技术领域，具体涉及一种天窗玻璃及车辆。
背景技术
随着车辆行业的不断发展，越来越多的车辆通过对天窗玻璃的结构进行改进来提高车辆的采光和外观。但随着天窗玻璃的面积变大，进入车内的光线就会变得过多，不仅会影响乘客的视觉感官体验，还会提高车内温度而影响车内的热舒适性，现有技术通过降低天窗玻璃的可见光透过率来进行改善，例如采用着色玻璃、着色PVB或增设调光元件等。虽然降低了天窗玻璃的可见光透过率，但在车内一侧测量天窗玻璃的可见光反射率仍然较高，使天窗玻璃产生了明显的镜面效果，车内的中控台显示器或其他电子设备的显示器均可能在天窗玻璃上产生清晰的倒影，严重干扰了后排乘客。
发明内容
本申请提供了一种天窗玻璃及车辆，能够降低天窗玻璃朝向车内一侧的表面的可见光反射率，使乘客从车内向外看时有更好的视觉体验。
第一方面，本申请提供一种天窗玻璃，所述天窗玻璃包括玻璃基板、金属吸收层和减反射层，所述玻璃基板包括外表面和内表面，在所述内表面上沿远离所述玻璃基板的方向依次层叠设置有所述金属吸收层和所述减反射层。
一种可能的实施方式中，所述天窗玻璃还包括第一保护层，所述第一保护层设于所述内表面上，且位于所述内表面与所述金属吸收层之间。
一种可能的实施方式中，所述天窗玻璃还包括第二保护层，所述第二保护层设于所述减反射层远离所述金属吸收层的表面。
一种可能的实施方式中，所述减反射层包括至少一个高折射率层/低折射率层的叠层，所述高折射率层的折射率大于或等于1.7，所述低折射率层的折射率小于1.7。
一种可能的实施方式中，所述天窗玻璃还包括低辐射层，所述低辐射层设置在所述第一保护层和所述金属吸收层之间。
一种可能的实施方式中，所述低辐射层包括氧化铟锡层、掺氟氧化锡层、氧化锡锑层或掺铝氧化锌层的一种或多种。
一种可能的实施方式中，还包括阻隔层，所述阻隔层设于所述低辐射层和所述金属吸收层之间。
一种可能的实施方式中，所述玻璃基板为夹层玻璃，所述夹层玻璃包括内层玻璃、外层玻璃和连接在所述外层玻璃和所述内层玻璃之间的中间层，所述内层玻璃包括相对设置的第一表面和第二表面，其中，所述第一表面为所述内表面，所述外层玻璃包括相对设置的第三表面和第四表面，其中，所述第四表面为所述外表面。
一种可能的实施方式中，所述玻璃基板还包括红外反射层，所述红外反射层位于所述第二表面和/或所述第三表面上。
一种可能的实施方式中，所述天窗玻璃的可见光透过率范围在为1％-20％之间，从所述内表面一侧测量所述天窗玻璃的可见光反射率小于或等于4％，从所述内表面一侧测量所述天窗玻璃的反射颜色的Lab值中的a值的范围在-6～2之间、b值的范围在-12～0之间。
一种可能的实施方式中，所述外层玻璃的可见光透过率大于或等于70％，所述内层玻璃的可见光透过率大于或等于70％，所述中间层的可见光透过率的范围在1％～30％之间。
一种可能的实施方式中，所述外层玻璃的可见光透过率小于或者等于50％，所述内层玻璃的可见光透过率小于或等于50％，所述中间层的可见光透过率的大于或等于70％。
一种可能的实施方式中，在所述第二表面和所述第三表面之间还设置有调光元件，所述调光元件包括聚合物分散液晶调光膜、聚合物网络液晶调光膜、悬浮粒子调光膜或电致变色调光膜。
一种可能的实施方式中，所述玻璃基板为单片钢化玻璃，所述单片钢化玻璃的厚度大于或等于5mm。
一种可能的实施方式中，所述单片钢化玻璃为着色玻璃，所述着色玻璃的以Fe 2O 3计的总铁含量范围在0.5％-2.0％之间。
第二方面，本申请提供一种车辆，所述车辆包括车体与如上所述的天窗玻璃，所述天窗玻璃连接至所述车体。
附图说明
为了更清楚地说明本申请的技术方案，下面将对实施方式中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的一些实施方式，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以如这些附图获得其他的附图。
图1是本申请实施例提供的使用天窗玻璃的车辆的结构示意图；
图2是本申请实施例提供的天窗玻璃的第一种结构示意图；
图3是本申请实施例提供的天窗玻璃的第二种结构示意图；
图4是本申请实施例提供的天窗玻璃的第三种结构示意图；
图5是本申请实施例提供的天窗玻璃的第四种结构示意图；
图6是本申请实施例提供的天窗玻璃的第五种结构示意图；
图7是本申请实施例提供的天窗玻璃的第六种结构示意图；
图8是本申请实施例提供的天窗玻璃的第七种结构示意图；
图9是本申请实施例提供的天窗玻璃的第八种结构示意图。
具体实施方式
下面将参照附图更详细地描述本申请的具体实施方式。虽然附图中显示了本申请的示例性实施方式，但应当理解的是，还可以采用不同于在此描述的其他方式来实施本申请，因此，本申请不受下面这些实施方式的限制。
请结合参阅图1-图9，本申请的实施例提供一种天窗玻璃10及车辆100，能够降低从车内一侧测量天窗玻璃10的可见光反射率，从而消除了从车内观察时天窗玻璃的镜面效果，使乘客从车内向外看时有更好的视觉体验。
请参阅图1，车辆100包括天窗玻璃10和车体20，天窗玻璃10连接至车体20。示例性的，天窗玻璃10可以是全景天窗玻璃。天窗玻璃10的可见光透过率可以小于或等于30％，优选小于或等于20％，具体可以举例19％、18％、17％、16％、15％、14％、13％、12％、11％、10％、9％、8％、7％、6％、5％、4％、3％、2％、1％，从车内一侧测量天窗玻璃10的可见光反射率小于或等于4％，优选小于或等于3％，更优选小于或等于2％。
请参阅图2，天窗玻璃10包括玻璃基板11和依次层叠设置在玻璃基板11上的金属吸收层12和减反射层13。
需说明的是，图2的目的仅在于示意性的描述玻璃基板11、金属吸收层12和减反射层13的连接关系，并非是对各个设备的连接位置、具体构造及数量做具体限定。而本申请实施例示意的结构并不构成对天窗玻璃10的具体限定。在本申请另一些实施例中，天窗玻璃10可以包括比图示更多或更少的部件，或者组合某些部件，或者拆分某些部件，或者不同的部件布置。图示的部件可以以硬件，软件或软件和硬件的组合实现。
请继续参阅图2，玻璃基板11包括相对设置的内表面11a和外表面11b，内表面11a为天窗玻璃10朝向车内一侧的表面，外表面11b为天窗玻璃10朝向车外一侧的一面。在内表面11a上沿远离玻璃基板11的方向依次层叠设置有金属吸收层12和减反射层13。
玻璃基板11可以是透明的，也可以是着色的。玻璃基板11的材质可以是钠钙硅酸盐玻璃、硼硅酸盐玻璃、铝硅酸盐玻璃或有机玻璃，有机玻璃可以举例为聚甲基丙烯酸甲酯或聚碳酸酯等。
需说明的是，用作天窗玻璃10的玻璃基板11通常为弯曲形状，玻璃基板11的形状并不局限于前述描述的形状，其可以是满足天窗玻璃10使用要求的任何形状，例如玻璃基板11也可以呈平直板状，本申请的实施例对于玻璃基板11的形状不做严格要求。
玻璃基板11可以为单片钢化玻璃，单片钢化玻璃的厚度大于或等于5mm，可以举例为5.1mm、5.5mm、5.8mm、6mm、6.5mm、7mm、7.5mm、8mm等，单片钢化玻璃可以为着色玻璃，所述着色玻璃的以Fe 2O 3计的总铁含量为0.5％-2.0％，例如绿色玻璃、蓝色玻璃、灰色玻璃等。
请继续参阅图2，玻璃基板11可以为夹层玻璃，所述夹层玻璃包括内层玻璃111、外层玻璃112和连接在外层玻璃112和内层玻璃111之间的中间层113。内层玻璃111包括相对设置的第一表面1111和第二表面1112，其中，第一表面1111为玻璃基板11的内表面11a。外层玻璃112包括相对设置的第三表面1121和第四表面1122，其中，第四表面1122为玻璃基板11的外表面11b。
可以理解的是，中间层113用于连接外层玻璃112与内层玻璃111，使天窗玻璃10整体呈现夹层结构的设置，以提高玻璃本体的强度，使其不易破碎，抗冲击性能比单层玻璃有所提升， 抗冲击性能的提升可以使车辆安全性能有所提升，且可使玻璃本体不易损坏，降低了维修成本。
天窗玻璃10还包括调光元件(图未示)，调光元件设置在第二表面和第三表面之间，调光元件可以包括聚合物分散液晶调光膜(PDLC)、聚合物网络液晶调光膜(PNLC)、悬浮粒子(SPD)调光膜或电致变色(EC)调光膜中的一种或多种。
请参阅图3，一种可能的实施方式中，玻璃基板11还可以包括红外反射层14。红外反射层14设于内层玻璃111的第二表面1112和/或外层玻璃112的第三表面1121上。
可以理解的是，通过在外层玻璃112与中间层113之间和/或内层玻璃111与中间层113之间设置红外反射层14，所述红外反射层14包含至少一个金属功能层和多个介质层，所述金属功能层可以举例为金层、银层、铜层、银铜合金层、银铟合金层、银金合金层等；更具体地，所述红外反射层14可以为单银镀膜(包含一个银层)、双银镀膜(包含两个银层)、三银镀膜(包含三个银层)、四银镀膜(包含四个银层)等。红外反射层14能够反射大部分的780nm-2500nm波长范围内的红外线，使天窗玻璃10具有防晒隔热性能，提高车内的热舒适性，使天窗玻璃10能够适应全景玻璃的发展趋势。
一种可能的实施方式中，外层玻璃112与内层玻璃111平行设置。此设置下，中间层113的厚度均匀。
另一种可能的实施方式中，外层玻璃112的延伸方向与内层玻璃111的延伸方向相交。此设置下，中间层113的厚度不均匀，其可以呈现厚度渐变的结构设置。例如，中间层113可以呈楔形。
基于上述描述，应当理解，中间层113的厚度可以根据天窗玻璃10的实际应用场景进行灵活调整，有利于适应天窗玻璃10的多场景应用需求。
示例性的，内层玻璃111和外层玻璃112都可以是2.1mm的透明玻璃(普通白玻)，具体而言，内层玻璃111和外层玻璃112的厚度在0.7mm-4.0mm的范围内都符合要求(包括端点值0.7mm和4.0mm)。为了满足轻量化需求，优选外层玻璃112的厚度为1.6mm-4.0mm，内层玻璃111的厚度为0.7mm-2.1mm，且外层玻璃112的厚度大于或等于内层玻璃111的厚度。外层玻璃112的可见光透过率大于或等于70％，优选大于或等于80％，甚至大于或等于90％；所述内层玻璃111的可见光透过率大于或等于70％，优选大于或等于80％，甚至大于或等于90％；内层玻璃111和外层玻璃112选用普通白玻可以大幅降低产品成本，提高产品的市场竞争力。
一种可能的实施方式中，通过选择不同可见光透过率的中间层113来调节天窗玻璃10的可见光透过率，优选地所述中间层113的可见光透过率为1％～30％，例如1％、2％、3％、4％、5％、6％、7％、8％、9％、10％、11％、12％、13％、14％、15％、16％、17％、18％、19％、20％、21％、 22％、23％、24％、25％、26％、27％、28％、29％、30％等，中间层113的材质可以是聚乙烯醇缩丁醛(PVB)、乙烯醋酸乙烯酯(EVA)、离子型聚合物膜(SGP)等。
另一种可能的实施方式中，外层玻璃112的可见光透过率小于或等于50％，优选小于或等于40％，更优选小于或等于30％，甚至小于或等于20％；所述内层玻璃111的可见光透过率小于或等于50％，优选小于或等于40％，更优选小于或等于30％，甚至小于或等于20％；所述中间层113的可见光透过率大于或等于70％，具体可举例为大于或等于70％、大于或等于75％、大于或等于80％、大于或等于85％、大于或等于90％等。通过选用普通的透明的中间层，例如标准透明PVB，可以大幅降低产品成本，提高产品的市场竞争力。
请参阅图2，金属吸收层12连接于内层玻璃111的第一表面1111。可以理解的是，通过在玻璃基板11上设置金属吸收层12，一方面，可以通过金属吸收层12调整对光的吸收，改善天窗玻璃10的辐射性能和外观颜色。另一方面，金属吸收层12可以在一定程度上吸收可见光，降低天窗玻璃10朝向车内一侧的内表面11a的可见光反射率，使用户可以更好的透过天窗看到外界，并且减少天窗玻璃10的内表面11a反射光线对车内用户的影响，提升用户的使用体验。
示例性的，金属吸收层12可以是金属膜层，其膜层材质可以是Ni、Cr、Fe、Ti、Mo、Zr、Si、Nb等中一种或多种材质的组合。金属吸收层12的厚度可以为1nm-15nm，优选3nm-12nm，更优选5-10nm。厚度适中的金属吸收层12不仅可以起到吸收可见光的作用，还可以配合减反射层13进一步降低玻璃基板11的可见光反射率。
请继续参阅图2，减反射层13设于金属吸收层12远离内层玻璃111的一侧。例如，减反射层13可以使用磁控溅射工艺进行镀膜。可以理解的是，减反射层13可以降低玻璃基板11的可见光反射率。减反射层13与金属吸收层12相互配合可以进一步降低玻璃基板11内表面11a的可见光反射率，使得天窗玻璃10可以适应全景玻璃的应用趋势。
另外，减反射层13与金属吸收层12的协同作用可以使玻璃基板11的内表面11a的可见光反射率大幅降低，消除了从车内观察时天窗玻璃10的镜面效果，提升用户的使用体验。
本申请的实施例中，减反射层13包括至少一个高折射率层131/低折射率层132的叠层。高折射率层131连接于金属吸收层12，低折射率层132与高折射率层131连接且远离金属吸收层12。高折射率层131的折射率大于或等于1.7，低折射率层132的折射率小于1.7。
其中，高折射率层131/低折射率层132的叠层是指按照高折射率层131、低折射率层132依次叠加形成，例如包括一个高折射率层131/低折射率层132的叠层依次为高折射率层131、低折射率层132，包括两个高折射率层131/低折射率层132的叠层依次为高折射率层131、低折射率层132、高折射率层131、低折射率层132，包括三个高折射率层131/低折射率层132的叠层依次为高折射率层131、低折射率层132、高折射率层131、低折射率层132、高折射率层131、 低折射率层132。高折射率层131厚度的范围可以在1nm-70nm之间(包括端点值1nm和70nm)。在一具体的应用场景中，高折射率层131还可以包含至少两个高折射率子层，例如高折射率层131/低折射率层132的叠层可以具体为第一高折射率子层、第二高折射率子层、低折射率层132，其中第一高折射率子层的折射率小于第二高折射率子层的折射率。低折射率层132厚度范围可以在20nm-150nm之间(包括端点值20nm和150nm)。
示例性的，高折射率层131的折射率可以在1.7-2.5的范围内(包括端点值1.7和2.5)，低折射率层132的折射率可以在1.4-1.69的范围内(包括端点值1.4和1.69)。高折射率层131的材料可以包括Zn、Sn、Nb、Ti、Ni、Cr、Ta的氧化物或者合金氧化物，如氧化锌锡(ZnSnO x)、氧化钛(TiO x)、氧化铌(NbO x)等，或包括Si、Zr、Al的氮化物或合金氮化物，如氮化硅(SiN x)、硅基氮化铝(SiAlN x)、硅基氮化锆(SiZrN x)等。低折射率层132的材料可以包括Si、Zr、Al的氧化物或合金氧化物，如氧化硅(SiO x)、硅基氧化铝(SiAlO x)、硅基氧化锆(SiZrO x)等。其中，x取值根据磁控溅射工艺中以化学计量方式、亚化学计量方式或超化学计量方式沉积进行确定。
请结合参阅图2-图9，减反射层13可以包括一个高折射率层131/低折射率层132的叠层，也可以包括至少两个叠层，具体为，减反射层13可以包括两个叠层、三个叠层或四个叠层等。基于工艺制作和成本上具有明显的优势等方面考虑，优选减反射层13仅包括一个高折射率层131/低折射率层132的叠层，本申请的实施例通过金属吸收层12和减反射层13的协同作用，仅包括一个叠层的减反射层13的减反射效果就能够达到与传统的包括两个叠层、三个叠层甚至四个叠层的减反射层具有同等水平的减反射效果。
在一具体的应用场景中，如图2、图3、图6、图7、图8和图9所示，减反射层13中仅包括一个高折射率层131/低折射率层132的叠层，且从玻璃基板11内表面11a朝向车内的方向，按照高折射率层131-低折射率层132结构布置。具体而言，在从内表面11a向沿远离内表面11a方向上，减反射层13包括依次层叠设置在金属吸收层12远离内层玻璃111的一侧的高折射率层131和低折射率层132。
在又一具体的应用场景中，减反射层13中的高折射率层131包含两个高折射率子层，且从内表面11a向远离内层玻璃111的方向，按照第一高折射率子层1311-第二高折射率子层1312-低折射率132的结构布置。具体而言，如图4所示，在从内表面11a向远离内层玻璃111的内表面11a方向上，叠层结构包括依次层叠设置在金属吸收层12远离内层玻璃111的一侧的第一高折射率子层1311、第二高折射率子层1312和低折射率层132。第一高折射率子层1311的折射率小于第二高折射率子层1312的折射率。
在另一具体的应用场景中，减反射层13中包括两个高折射率层131/低折射率层132的叠层，且沿远离内层玻璃111的内表面11a方向，按照高折射率层131-低折射率层132呈周期 性交替布置，最外层(也即距离内层玻璃111的第一表面1111最远的层)为低折射率层132。具体而言，如图5所示，减反射层13包括依次层叠设置在内层玻璃111上的第一高折射率层131a、第一低折射率层132a、第二高折射率层131b和第二低折射率层132b。其中，第一高折射率层131a的材料、厚度与第二高折射率层131b的材料、厚度可以相同，也可以不同；第一低折射率层132a的材料、厚度与第二低折射率层132b的材料、厚度可以相同，也可以不同。
在本申请的实施例中，可以选择合适的玻璃基板11，以及通过调整金属吸收层12和减反射层13的材料和厚度，从内表面11a一侧测量所述天窗玻璃10的反射颜色的Lab值中的a值范围在-6～2之间(包括端点值-6和2)、b值范围在-12～0之间(包括-12和0)，实现从车内一侧观察天窗玻璃10的颜色优选为中性色，从而使乘客在车内具有更好的视觉效果。
一种可能的实施方式中，如图6所示，天窗玻璃10还可以包括第一保护层15，第一保护层15直接设于内层玻璃111的第一表面1111上，也即为第一保护层15设于玻璃基板11的内表面11a与金属吸收层12之间。第一保护层15可以在内层玻璃111经过至少500℃高温弯曲成型过程中阻挡内层玻璃111表面的碱金属离子以及氧的扩散造成金属吸收层12的破坏和氧化。
示例性的，第一保护层15的厚度可以大于或等于5nm。第一保护层15的材料可以包括Zn、Sn、Ti、Si、Al、Nb、Zr、Ni、Mg、Cr、Ta等的氧化物或合金氧化物，或包括Si、Al、Zr、B、Ti等的氮化物或合金氮氧化物。其中，合金氧化物、合金氮氧化物是指至少两种元素的氧化物、氮氧化物。
另一种可能的实施方式中，如图7所示，天窗玻璃10还可以包括第二保护层16，第二保护层16设于减反射层13远离金属吸收层12的一侧，也即为第二保护层16设于天窗玻璃10的膜层结构的最外层。第二保护层16有利于进一步提升膜层的整体机械稳定性和热稳定性能。
示例性的，第二保护层16的材料可以包括Si、Al、Zr、Ti、B、Ni等的氮化物或合金氮氧化物，例如SiN x、SiAlN x、SiZrN x等。第二保护层16的厚度大于或等于3nm，考虑到第二保护层16对减反射层13的影响，优选第二保护层16的厚度小于或等于30nm。综合更优选地，第二保护层16的厚度为5nm-20nm。
又一种可能的实施方式中，如图8所示，天窗玻璃10还可以包括第一保护层15和第二保护层16，第一保护层15设于金属吸收层12与内层玻璃111之间，第二保护层16设与减反射层13远离金属吸收层12的一侧表面。
需说明的是，不仅可以通过调整金属吸收层12和减反射层13的膜层材料和膜层厚度来调整天窗玻璃10的颜色，还可以通过调整第一保护层15和第二保护层16的膜层材料和膜层厚度来调整天窗玻璃10的颜色，本申请的实施例对此不做严格限制。
请参阅图9，本申请的实施例中，天窗玻璃10还可以包括低辐射层17，所述低辐射层17 设置在所述第一保护层15和所述金属吸收层12之间。所述低辐射层17用于降低从内表面11a一侧测量天窗玻璃10的辐射率，从内表面11a一侧测量所述天窗玻璃10的辐射率的范围在0.01-0.25之间(包括端点值0.01和0.25)，能够较好地阻隔车内外热量传递，所述低辐射层17包括ITO层(氧化铟锡)、FTO层(掺氟氧化锡)、ATO层(氧化锡锑)或AZO层(掺铝氧化锌)的一种或多种，在所述低辐射层17和所述金属吸收层12之间还设置有阻隔层18。第一表面1111上可以依次设有第一保护层15、低辐射层17、阻隔层18、金属吸收层12、高折射率层131、低折射率层132、第二保护层16。
具体而言，第一保护层15可以直接设于第一表面1111。低辐射层17设于第一保护层15远离内层玻璃111的一侧，阻隔层18设于低辐射层17远离第一保护层15的一侧。可以理解的是，在内层玻璃111的表面设置第一保护层15，可以阻挡内层玻璃111中的碱金属离子等进入膜层结构中，从而保护第一保护层15与第二保护层16之间的光学膜层，而在第一保护层15远离玻璃基板11的一侧设置低辐射层17，使天窗玻璃10具有优异的低辐射效果。而在低辐射层17远离第一保护层15的一侧设置阻隔层18，可以因阻隔层18位于金属吸收层12和低辐射层17之间，而防止二者互相影响所导致金属吸收层12或者低辐射层17的性能下降甚至失效。
本申请还提供一种天窗玻璃10的制备方法，其中天窗玻璃10具体结构可参阅图1-图9以及上文的描述。且如下方法的描述中，关于天窗玻璃10的改进，在不冲突的情况下，均可应用至上文的天窗玻璃10的描述，方法包括：
S100：提供内层玻璃111，其中，内层玻璃111包括相对的第一表面1111和第二表面1112。
S200：在内层玻璃111的第一表面1111上依次层叠设置金属吸收层12和减反射层13。
S300：制备玻璃基板11，其中，玻璃基板11包括内层玻璃111、外层玻璃112及连接在内层玻璃111和外层玻璃112之间的中间层113，玻璃基板11的内表面11a为内层玻璃111的第一表面1111。
如下将对S200和S300的具体步骤进行描述。
S200：在内层玻璃111的第一表面1111依次层叠设置金属吸收层12和减反射层13。
首先，将金属吸收层12与减反射层13通过磁控溅射工艺沉积于第一表面1111上。
示例性的，第一保护层15、低辐射层17、阻隔层18、金属吸收层12、高折射率层131、低折射率层132、第二保护层16分别通过磁控溅射工艺依次层叠沉积于内层玻璃111的第一表面1111上。
S300：制备玻璃基板11。
玻璃基板11包括内层玻璃111、外层玻璃112及连接在内层玻璃111和外层玻璃112之间的中间层113，玻璃基板11的内表面11a为内层玻璃111的第一表面1111。当内层玻璃111通过磁控溅射工艺沉积金属吸收层12、减反射层13之后，或进一步还沉积有第一保护层15、低辐射层 17、阻隔层18、第二保护层16等，以及外层玻璃112的第三表面1121上还沉积有红外反射层14，对外层玻璃112与内层玻璃111进行高温弯曲成型处理，其中，高温弯曲成型处理的温度范围可以在550℃-700℃(包括端点值550℃、700℃)之间。然后通过中间层113连接外层玻璃112与内层玻璃111，中间层113的可见光透过率范围可以在1％～30％之间，通过汽车玻璃生产工艺将外层玻璃112、内层玻璃111和中间层113形成夹层玻璃结构。
本申请还提供了五个实施例和四个对比例以对天窗玻璃10的性能进行分析和探究。
实施例1：
外层玻璃112与内层玻璃111为2.1mm厚的普通白玻，内层玻璃111的第一表面1111上采用磁控溅射法依次沉积第一保护层15(厚度为10nm的Si 3N 4层)、金属吸收层12(厚度为6.5nm的NiCr层)、高折射率层(厚度为26nm的TiO 2层)、低折射率层(厚度为36nm的SiO 2层)，26nm厚的TiO 2层和36nm厚的SiO 2层构成减反射层13。膜层沉积结束后，将外层玻璃112和内层玻璃111进行高温弯曲成型处理，然后准备0.76mm厚的可见光透过率为10％左右的灰色PVB作为中间层113，通过汽车玻璃生产工艺形成夹层玻璃结构。
实施例2：
外层玻璃112与内层玻璃111为2.1mm厚的普通白玻，内层玻璃111的第一表面1111上采用磁控溅射法依次沉积金属吸收层12(厚度为6.5nm的NiCr)层、高折射率层(厚度为26nm的TiO 2层)、低折射率层(厚度为32nm的SiO 2层)、第二保护层16(厚度为15nm的Si 3N 4层)，26nm厚的TiO 2层和32nm厚的SiO 2层构成减反射层13。膜层沉积结束后，将外层玻璃112和内层玻璃111进行高温弯曲成型处理，然后准备0.76mm厚的可见光透过率为10％左右的PVB作为中间层113，通过汽车玻璃生产工艺形成夹层玻璃结构。
实施例3：
外层玻璃112与内层玻璃111为2.1mm厚的普通白玻，内层玻璃111的第一表面1111上采用磁控溅射法依次沉积第一保护层15(厚度为10nm的Si 3N 4层)、金属吸收层12(厚度为6.5nm的NiCr层)、高折射率层(厚度为26nm的TiO 2层)、低折射率层(厚度为34nm的SiO 2层)、第二保护层16(厚度为15nm的Si 3N 4层)，26nm厚的TiO 2层和34nm厚的SiO 2层构成减反射层13。膜层沉积结束后，将外层玻璃112和内层玻璃111进行高温弯曲成型处理，然后准备0.76mm厚的可见光透过率为10％左右的PVB作为中间层113，通过汽车玻璃生产工艺形成夹层玻璃结构。
实施例4：
外层玻璃112与内层玻璃111为2.1mm厚的普通白玻，内层玻璃111的第一表面1111上采用磁控溅射法依次沉积第一保护层15(厚度为10nm的ZnSnO x层)、金属吸收层12(厚度为6.5nm的NiCr层)、高折射率层(厚度为26nm的TiO 2层)、低折射率层(厚度为34nm的SiO 2 层)、第二保护层16(厚度为15nm的Si 3N 4层)，26nm厚的TiO 2层和34nm厚的SiO 2层构成减反射层13。膜层沉积结束后，将外层玻璃112和内层玻璃111进行高温弯曲成型处理，然后准备0.76mm厚的可见光透过率为10％左右的PVB作为中间层113，通过汽车玻璃生产工艺形成夹层玻璃结构。
实施例5：
外层玻璃112与内层玻璃111为2.1mm厚的普通白玻，内层玻璃111的第一表面1111上采用磁控溅射法依次沉积第一保护层15(厚度为10nm的Si 3N 4层)、低辐射层17(厚度为138nm的ITO层)、阻隔层18(厚度为10nm的Si 3N 4层)、金属吸收层12(厚度为8.5nm的NiCr层)、高折射率层(厚度为34nm的TiO 2层)、低折射率层(厚度为63nm的SiO 2层)、第二保护层16(厚度为10nm的Si 3N 4层)，34nm厚的TiO 2层和63nm厚的SiO 2层构成减反射层13。膜层沉积结束后，将外层玻璃112和内层玻璃111进行高温弯曲成型处理，然后准备0.76mm厚的可见光透过率为10％左右的PVB作为中间层113，通过汽车玻璃生产工艺形成夹层玻璃结构。
实施例6：
外层玻璃112与内层玻璃111为2.1mm厚透过率约40％-50％灰玻，内层玻璃111的第一表面1111上采用磁控溅射法依次沉积第一保护层15(厚度为10nm的SiN层)、金属吸收层12(厚度为7.2nm的NiCr层)、高折射率层(厚度为26nm的TiO 2层)、低折射率层(厚度为36nm的SiO 2层)、第二保护层16(厚度为15nm的Si 3N 4层)，26nm厚的TiO 2层和36nm厚的SiO 2层构成减反射层13。膜层沉积结束后，将外层玻璃112和内层玻璃111进行高温弯曲成型处理，然后准备0.76mm厚的可见光透过率为90％左右的PVB作为中间层113，通过汽车玻璃生产工艺形成夹层玻璃结构。
对比例1：
外层玻璃112与内层玻璃111为2.1mm厚的普通白玻，不进行任何膜层沉积，将外层玻璃112和内层玻璃111进行高温弯曲成型处理，然后准备0.76mm厚的可见光透过率为10％左右的PVB作为中间层113，通过汽车玻璃生产工艺形成夹层玻璃结构。
对比例2：
外层玻璃112与内层玻璃111为2.1mm厚的普通白玻，内层玻璃111的第一表面1111上采用磁控溅射法依次沉积高折射率层(厚度为5nm的TiO 2层)、低折射率层(厚度为130nm的SiO 2层)，未沉积金属吸收层12。5nm厚的TiO 2层和130nm厚的SiO 2层构成减反射层13。膜层沉积结束后，将外层玻璃112和内层玻璃111进行高温弯曲成型处理，然后准备0.76mm厚的可见光透过率为10％左右的PVB作为中间层113，通过汽车玻璃生产工艺形成夹层玻璃结构。
对比例3：
外层玻璃112与内层玻璃111为2.1mm厚的普通白玻，内层玻璃111的第一表面1111上采用磁控溅射法依次沉积高折射率层(厚度为10nm的TiO 2层)、低折射率层(厚度为48nm的SiO 2层)、高折射率层(厚度为106nm的TiO 2层)、低折射率层(厚度为96nm的SiO 2层)，未沉积金属吸收层12。10nm厚的TiO 2层、48nm厚的SiO 2层、106nm厚的TiO 2层和96nm厚的SiO 2层构成减反射层13。膜层沉积结束后，将外层玻璃112和内层玻璃111进行高温弯曲成型处理，然后准备0.76mm厚的可见光透过率为10％左右的PVB作为中间层113，通过汽车玻璃生产工艺形成夹层玻璃结构。
对比例4：
外层玻璃112与内层玻璃111为2.1mm厚的普通白玻，内层玻璃111的第一表面1111上采用磁控溅射法依次沉积第一保护层15(厚度为16nm的Si 3N 4层)、金属吸收层12(厚度为7.5nm的NiCr层)、第二保护层16(厚度为58nm的Si 3N 4层)，未沉积减反射层13。膜层沉积结束后，将外层玻璃112和内层玻璃111进行高温弯曲成型处理，然后准备0.76mm厚的可见光透过率为10％左右的PVB作为中间层113，通过汽车玻璃生产工艺形成夹层玻璃结构。
将对比例1-4和实施例3的夹层玻璃进行可见光反射率、反射颜色的测量，测量结果计入表1中。
表1：对比例1-4和实施例3的夹层玻璃结构和测量结果
Figure PCTCN2023071636-appb-000001
Figure PCTCN2023071636-appb-000002
其中，从第一表面一侧测量内层玻璃的可见光反射率(高温热处理后)为：将沉积有膜层的内层玻璃进行高温弯曲成型处理后，形成夹层玻璃结构前，从第一表面一侧直接测量的单片内层玻璃的可见光反射率；从内表面一侧测量天窗玻璃的可见光反射率为：将经过高温弯曲成型处理的外层玻璃和沉积有膜层的内层玻璃与中间层通过汽车玻璃生产工艺形成夹层玻璃结构后，从内表面一侧测量的天窗玻璃的可见光反射率。
从表1可以看出，对比例1中，未沉积金属吸收层12和减反射层13的内层玻璃111的可见光反射率大于8％，即使再与中间层113和外层玻璃112形成夹层玻璃作为天窗玻璃10，从内表面11a一侧测量天窗玻璃10的可见光反射率仍然大于4％，存在较为明显的镜面效果。
对比例2中，通过设置减反射层13，也即为一个高折射率层131与低折射率层132的叠层，内层玻璃111的第一表面1111的可见光反射率降低至5％-6％，再与中间层113和外层玻璃112形成夹层玻璃作为天窗玻璃10，从内表面11a一侧测量天窗玻璃10的可见光反射率小于3％，但通过Lab色彩测试发现，此时从车内观察天窗玻璃10的反射颜色呈红紫色，严重偏离了中性色，不易被乘客接受。
对比例3中，设置了两个包括高折射率层131和低折射率层132的叠层，此时内层玻璃111的第一表面1111的可见光反射率降低至4％-5％，再与中间层113和外层玻璃112形成夹层玻璃作为天窗玻璃10，从内表面11a一侧测量天窗玻璃10的可见光反射率小于2％。此时从车内观察天窗玻璃10的反射颜色也较为中性色，但膜层总厚度为260nm，不利于制作工艺且生产成本较高。
对比例4中，采用了镍铬合金(NiCr)作为金属吸收层12，此时内层玻璃111的第一表面1111的可见光反射率小于4％，再与中间层113和外层玻璃112形成夹层玻璃作为天窗玻璃10，从内表面11a一侧测量天窗玻璃10的可见光反射率小于3％。但通过Lab色彩测试发现，此时从车内观察天窗玻璃10的反射颜色严重偏离了中性色，不易被乘客接受。
通过对比发现，实施例3的膜层结构可以使内层玻璃111的第一表面1111的可见光反射率小于4％，再与中间层113和外层玻璃112形成夹层玻璃作为天窗玻璃10，从内表面11a一侧测量天窗玻璃10的可见光反射率小于2％，且此时从车内观察天窗玻璃10的反射颜色也符合中性色要求。实施例3相比于对比例3而言，实施例3的膜层总厚度约为对比例3的三分之一，在工艺制作和成本上具有明显优势。
将实施例1-6的夹层玻璃进行可见光反射率、反射颜色的测量，测量结果计入表2中。
表2：实施例1-6的夹层玻璃结构和测量结果
Figure PCTCN2023071636-appb-000003
其中，从第一表面一侧测量内层玻璃的可见光反射率(高温热处理前)为：将内层玻璃进行膜层沉积后，进行高温弯曲成型处理前，从第一表面一侧直接测量的单片内层玻璃的可见光反射率；从第一表面一侧测量内层玻璃的可见光反射率(高温热处理后)为：将沉积有膜层的内层玻璃进行高温弯曲成型处理后，形成夹层玻璃结构前，从第一表面一侧直接测量的单片内层玻璃的可见光反射率；从内表面一侧测量天窗玻璃的可见光反射率为：将经过高温弯 曲成型处理的外层玻璃和沉积有膜层的内层玻璃与中间层通过汽车玻璃生产工艺形成夹层玻璃结构后，从内表面一侧测量的天窗玻璃的可见光反射率。
从表2可以看出，从内表面11a一侧测量实施例1-6中的天窗玻璃10的可见光反射率均小于4％，或小于3％，甚至小于2％，并且从内表面11a一侧测量实施例1-6中的天窗玻璃10的反射颜色的Lab值中的a值范围在-6～2之间(包括端点值-6和2)、b值范围在-12～0之间(包括断电值-12和0)，即实施例1-6中的天窗玻璃10能够在消除车内镜面效果的同时，还具有优异的车内观察中性色。实施例6使用灰色玻璃作为外层玻璃和内层玻璃，采用本发明的技术方案，依然可以获得低于2％的可见光反射率以及中性色的要求。
在实施例1-4和实施例6中，第一保护层15、金属吸收层12、减反射层13、第二保护层16的总厚度小于或等于200nm，优选小于或等于150nm，甚至小于或等于100nm，在工艺制作和成本上具有明显优势。
并且，从实施例2可以看出不设置第一保护层15时，膜层沉积后的内层玻璃111在高温弯曲成型处理过程中，金属吸收层12可能部分被氧化，最终导致经过高温弯曲成型处理后的从第一表面一侧测量内层玻璃111的可见光反射率大幅升高，再与中间层113和外层玻璃112形成夹层玻璃作为天窗玻璃10后，从内表面11a一侧测量天窗玻璃10的可见光反射率小于4％，且此时从车内观察天窗玻璃10的反射颜色也符合中性色要求，但反射颜色Lab值没有其他实施例优异。
实施例4与实施例3相比，由于采用了ZnSnO x作为第一保护层15的材料，而实施例3采用了Si 3N 4作为第一保护层15的材料，从第一表面一侧测量内层玻璃111的可见光反射率，实施例4在高温弯曲成型处理前后的可见光反射率变化大于实施例3的可见光反射率变化，优选第一保护层15的材料包含Si的氮化物，进一步有利于提高膜层的热稳定性和减少金属吸收层12的氧化程度。
从实施例5可以看出，即使增设了低辐射层17，使天窗玻璃10具有低辐射功能，而且仍然能够保持很低的可见光反射率和优异的中性色。
以上是本申请的示例性实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本申请原理的前提下，还可以对其做出若干改进和润饰，这些改进和润饰也视为本申请的保护范围。

Claims (16)

  1. 一种天窗玻璃，其特征在于，所述天窗玻璃包括玻璃基板、金属吸收层和减反射层，所述玻璃基板包括外表面和内表面，在所述内表面上沿远离所述玻璃基板的方向依次层叠设置所述金属吸收层和所述减反射层。
  2. 根据权利要求1所述的天窗玻璃，其特征在于，所述天窗玻璃还包括第一保护层，所述第一保护层设于所述内表面上，且位于所述内表面与所述金属吸收层之间。
  3. 根据权利要求1或2任一项所述的天窗玻璃，其特征在于，所述天窗玻璃还包括第二保护层，所述第二保护层设于所述减反射层远离所述金属吸收层的表面。
  4. 根据权利要求1-3任一项所述的天窗玻璃，其特征在于，所述减反射层包括至少一个高折射率层/低折射率层的叠层，所述高折射率层的折射率大于或等于1.7，所述低折射率层的折射率小于1.7。
  5. 根据权利要求2所述的天窗玻璃，其特征在于，所述天窗玻璃还包括低辐射层，所述低辐射层设置在所述第一保护层和所述金属吸收层之间。
  6. 根据权利要求5所述的天窗玻璃，其特征在于，所述低辐射层包括氧化铟锡层、掺氟氧化锡层、氧化锡锑层或掺铝氧化锌层的一种或多种。
  7. 根据权利要求6所述的天窗玻璃，其特征在于，还包括阻隔层，所述阻隔层设于所述低辐射层和所述金属吸收层之间。
  8. 根据权利要求1-7任一项所述的天窗玻璃，其特征在于，所述玻璃基板为夹层玻璃，所述夹层玻璃包括内层玻璃、外层玻璃和连接在所述外层玻璃和所述内层玻璃之间的中间层，所述内层玻璃包括相对设置的第一表面和第二表面，其中，所述第一表面为所述内表面，所述外层玻璃包括相对设置的第三表面和第四表面，其中，所述第四表面为所述外表面。
  9. 根据权利要求8所述的天窗玻璃，其特征在于，所述玻璃基板还包括红外反射层，所述红外反射层位于所述第二表面和/或所述第三表面上。
  10. 根据权利要求8所述的天窗玻璃，其特征在于，所述天窗玻璃的可见光透过率范围在1％-20％之间，从所述内表面一侧测量所述天窗玻璃的可见光反射率小于或等于4％，从所述内表面一侧测量所述天窗玻璃的反射颜色的Lab值中的a值的范围在-6～2之间、b值的范围在-12～0之间。
  11. 根据权利要求10所述的天窗玻璃，其特征在于，所述外层玻璃的可见光透过率大于或等于70％，所述内层玻璃的可见光透过率大于或等于70％，所述中间层的可见光透过率的范围在1％～30％之间。
  12. 根据权利要求10所述的天窗玻璃，其特征在于，所述外层玻璃的可见光透过率小于或者等于50％，所述内层玻璃的可见光透过率小于或等于50％，所述中间层的可见光透过率的大于或等于70％。
  13. 根据权利要求10所述的天窗玻璃，其特征在于，在所述第二表面和所述第三表面之间还设置有调光元件，所述调光元件包括聚合物分散液晶调光膜、聚合物网络液晶调光膜、悬浮粒子调光膜或电致变色调光膜中的一种或多种。
  14. 根据权利要求1所述的天窗玻璃，其特征在于，所述玻璃基板为单片钢化玻璃，所 述单片钢化玻璃的厚度大于或等于5mm。
  15. 根据权利要求14所述的天窗玻璃，其特征在于，所述单片钢化玻璃为着色玻璃，所述着色玻璃的以Fe 2O 3计的总铁含量范围在0.5％-2.0％之间。
  16. 一种车辆，其特征在于，所述车辆包括车体与如权利要求1-15任一项所述的天窗玻璃，所述天窗玻璃连接至所述车体。
PCT/CN2023/071636 2022-01-28 2023-01-10 天窗玻璃及车辆 WO2023143064A1 (zh)

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