Glass with a film and laminated glass

Abstract

The present invention provides a film-coated glass and a laminated glass, the film-coated glass comprising a first glass substrate, a low-emissivity layer, a metal absorbing layer, and a reflection-reducing layer. The low-emissivity layer is deposited on one surface of the first glass substrate, and comprises at least one transparent conductive oxide layer, the metal absorbing layer is deposited on the low-emissivity layer, and the reflection-reducing layer is deposited on the metal absorbing layer. The present invention provides a low-emissivity glass with a simple manufacturing process, low emissivity, low visible light reflectance, and neutral color, which can be used in the fields of architecture and automotive glass, and the laminated glass with the film-coated glass of the present application has both reduced emissivity and visible light reflectance, and the inner surface of the laminated glass with the low-emissivity layer has a beautiful color.

Description

[Technical field]

[0001] The present invention relates to the technology of glass coating, in particular to the technology of glass coating for automobile windows, and more particularly to coated glass and laminated glass. [Background technology]

[0002] At present, automotive glass insulation technology is receiving more and more attention, and by plating one or more layers of nano-order metal thin film on the windshield of an automobile, it is possible to reflect external heat and thereby block the intrusion of external heat (in summer) or the outflow of heat from inside the vehicle (in winter) while the vehicle is in operation. In particular, the panoramic roof glass of an automobile has a large surface area, so in winter the temperature inside the vehicle is most likely to radiate outside the vehicle and the heat retention effect inside the vehicle is poor due to heat conduction. Therefore, in order to reduce the heat conduction and radiation of the temperature inside the vehicle to the outside and to achieve a certain heat retention effect, it is necessary to place a layer of insulation coating on the roof glass, especially on the surface close to the interior surface of the vehicle.

[0003] At present, a common process method is to plate a transparent conductive oxide layer (TCO layer) on the glass surface. For example, a chemical vapor deposition (CVD) method is used to plate a fluorine-doped tin oxide (FTO) coating layer on a float production line, and the resulting glass is used as the inner substrate of the roof glass, with the FTO layer located on the contact surface between the glass and the interior air. The advantage of this method is that the FTO coating layer has strong mechanical properties and environmental resistance, but the disadvantage is that the reflectance of the FTO coating layer is high, usually greater than 10%, and the transmittance of the roof glass is usually low. When the reflectance is high, a certain mirror effect will occur, which will affect the riding comfort of passengers to a certain extent.

[0004] To solve the problem of reducing the high reflectance of TCO coatings, it is common to place a reflection-reducing layer on the TCO layer. If a lower reflectance is required, a complex multi-layer reflection-reducing film structure is required. However, the manufacturing process of four or more reflection-reducing layers unintentionally increases the cost and process difficulty of glass manufacturing. Summary of the Invention [Problem to be solved by the invention]

[0005] In order to overcome at least one of the deficiencies in the prior art, the present invention provides a filmed glass and a laminated glass, which has a simple manufacturing process, low emissivity, low visible light reflectance, neutral color, and can be used in the fields of architecture and automotive glass. [Means for solving the problem]

[0006] Specifically, the present invention provides a film-coated glass, the film-coated glass comprising a first glass substrate, a low-emissivity layer, a metal absorption layer, and a reflection-reducing layer, the low emissivity layer is deposited on one surface of the first glass substrate and comprises at least one transparent conductive oxide layer (TCO layer); the metal absorbing layer is deposited on the low emissivity layer; A coated glass is provided, in which the reflection reducing layer is deposited on the metal absorbing layer.

[0007] In an embodiment of the present invention, the low emissivity layer has a thickness of 100nm-500nm and an emissivity value of less than 0.3.

[0008] In an embodiment of the present invention, the transparent conductive oxide layer is made of indium-doped tin oxide. (ITO) layer , ATO Layer , Aluminum-doped zinc oxide (AZO) layer or Fluorine-doped tin oxide ( FTO )layer It is.

[0009] In an embodiment of the present invention, the reflection reduction layer includes at least one high refractive index layer and at least one low refractive index layer, the high refractive index layer and the low refractive index layer are alternately stacked, the refractive index of the high refractive index layer is 1.7 to 2.3, and the refractive index of the low refractive index layer is 1.4 to 1.7.

[0010] In an embodiment of the present invention, the material of the high refractive index layer is an oxide of at least one element selected from Zn, Sn, Nb, Ti, Ni, Cr, Ta, or a nitride or oxynitride of at least one element selected from Si, Zr, Al; The material of the low refractive index layer is an oxide of at least one element selected from the group consisting of Si, Al, and B, or a fluoride of at least one element selected from the group consisting of Mg, Al, and Ba.

[0011] In an embodiment of the present invention, the high refractive index layer has a thickness of 10 to 70 nm, and the low refractive index layer has a thickness of 20 to 150 nm.

[0012] In an embodiment of the present invention, the metal absorbing layer is for absorbing at least a part of visible light in the wavelength range of 380-780 nm, and the thickness of the metal absorbing layer is 3.5-10 nm.

[0013] In an embodiment of the present invention, the metal absorbing layer is in direct contact with the low emissivity layer, and the material of the metal absorbing layer is at least one selected from the following: Ni, Cr, Ti, Nb, Mo, Si.

[0014] In an embodiment of the present invention, an innermost barrier layer is further deposited between the low emissivity layer and one surface of the first glass substrate, the thickness of the innermost barrier layer is 3 nm or more, and the material of the innermost barrier layer is an oxide of at least one element selected from Zn, Sn, Ti, Si, Al, Nb, Zr, Ni, Mg, Cr, Ta, or a nitride or oxynitride of at least one element selected from Si, Al, Zr, B, Ti.

[0015] In an embodiment of the present invention, the film-coated glass further includes an outermost barrier layer deposited on the reflection-reduction layer, the material of the outermost barrier layer is a nitride or oxynitride of at least one element selected from Si, Al, Zr, Ti, B, and Ni, and the thickness of the outermost barrier layer is 30 nm or less.

[0016] In an embodiment of the present invention, the first glass substrate is a colored glass, and the visible light transmittance of the colored glass is less than or equal to 50%.

[0017] Furthermore, the present invention provides a laminated glass that can be installed in a vehicle, the laminated glass comprising the above-mentioned film-coated glass, a second glass substrate, and an adhesive layer, the second glass substrate being bonded to another surface of the first glass substrate via the adhesive layer, the film-coated glass being located inside the vehicle, The present invention further provides a laminated glass, wherein the laminated glass has a visible light transmittance of 20% or less, and a visible light reflectance of the laminated glass measured from the inside of a vehicle of 6% or less.

[0018] In an embodiment of the present invention, the visible light reflectance of the laminated glass measured from inside the vehicle is less than or equal to 2%.

[0019] In an embodiment of the present invention, the first glass substrate and / or the second glass substrate is a colored glass, and the visible light transmittance of the colored glass is less than or equal to 50%.

[0020] In an embodiment of the present invention, the first glass substrate and / or the second glass substrate is transparent glass, and the visible light transmittance of the transparent glass is greater than 70%.

[0021] In an embodiment of the present invention, the second glass substrate is a transparent glass, and an infrared reflective film is provided on a surface of the second glass substrate close to the adhesive layer, and the infrared reflective film includes at least one silver layer or a silver alloy layer.

[0022] In an embodiment of the present invention, the adhesive layer is a colored resin layer, and the visible light transmittance of the colored resin layer is not more than 30%.

[0023] In the embodiment of the present invention, the color standard (Lab) values ​​of the laminated glass measured from inside the vehicle are: a value is −6 to 3, and b value is −12 to 0.

[0024] In an embodiment of the present invention, the adhesive layer is a transparent PVB with a visible light transmittance of more than 90%.

[0025] In an embodiment of the present invention, a light control element is further provided between the film-coated glass and the second glass substrate, and the light control element is a PDLC light control thin film, an SPD light control thin film or an EC light control thin film.

[0026] The coated glass provided by the present invention comprises a low-emissivity layer, a metal absorbing layer, and a reflection-reducing layer. The low-emissivity layer effectively reduces the heat radiation from the glass to the interior, while at the same time blocking the heat radiation from the interior to the exterior, reducing the heat loss inside the room and providing a certain heat retention effect. The metal absorbing layer is disposed between the low-emissivity layer and the reflection-reducing layer, which further reduces the requirements for the reflectance of the glass substrate inside the vehicle due to the laminated glass. The layer It is favorable to further improve the overall mechanical performance and thermal stability of the laminated glass with a low-emissivity layer, thereby providing a low-emissivity glass with a simple manufacturing process, low emissivity, low visible light reflectance, and neutral color, which can be used in the fields of architecture and automotive glass. The laminated glass with the film-coated glass of the present application has both a reduced emissivity value and a reduced visible light reflectance, and the inner surface of the laminated glass with the low-emissivity layer has a beautiful color.

[0027] In order to make the above and other objects, features and advantages of the present invention more clearly understandable, preferred embodiments will be described in detail below in conjunction with the accompanying drawings.

[0028] In order to more clearly describe the embodiments of the present invention or the technical solutions in the prior art, the following will briefly describe the drawings that need to be used in the description of the embodiments or the prior art. Obviously, the drawings in the following description are only some embodiments of the present invention, and those skilled in the art can also obtain other drawings based on these drawings without exerting creative efforts. [Brief description of the drawings]

[0029] [Figure 1] Schematic diagram of the structure of the film-coated glass of the present invention. [Diagram 2] 1 is a schematic diagram of the structure of a laminated glass with a low-emissivity layer according to the present invention; [Diagram 3] 1 is a schematic diagram of the structure of another laminated glass provided with a low-emissivity layer according to the present invention; DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0030] Hereinafter, the technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the drawings in the embodiments of the present invention, and obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments obtained by those skilled in the art without any creative efforts based on the embodiments of the present invention belong to the scope of the present invention.

[0031] The present invention provides a film-coated glass and a laminated glass formed from the film-coated glass, which have a simple manufacturing process, low emissivity, low visible light reflectance, and neutral color, and can be used in the fields of architecture and automobile glass. The film-coated glass and the laminated glass are used as low emissivity glass, and are particularly applicable to automobile sunroof products.

[0032] As shown in FIG. 1, the film-coated glass provided by the present invention has the following features: A first glass substrate 2, a low-emissivity layer 4, a metal absorption layer 5, and a reflection reduction layer 6, the low-emissivity layer 4 is deposited on one surface of the first glass substrate 2 and comprises at least one transparent conductive oxide layer; A metallic absorbing layer 5 is deposited on the low emissivity layer 4, A reflection reducing layer 6 is deposited on the metal absorbing layer 5 .

[0033] In the coated glass provided by the present invention, the low-emissivity layer 4 on the surface of the first glass substrate can effectively reduce the thermal radiation from the glass and play a role in heat retention. The metal absorption layer 5 is disposed between the low-emissivity layer 4 and the reflection-reduction layer 6, which further reduces the reflectance of the glass.

[0034] The film-coated glass provided by the present invention can be installed in a vehicle as a window glass of an automobile, and thus the present invention further provides a laminated glass comprising a film-coated glass, a second glass substrate, and an adhesive layer, Here, the film-coated glass includes a first glass substrate, a low-emissivity layer, a metal absorption layer, and a reflection-reducing layer, the low emissivity layer is deposited on one surface of the first glass substrate and comprises at least one transparent conductive oxide layer; the metal absorbing layer is deposited on the low emissivity layer; The reflection reducing layer is deposited on a metal absorbing layer; The second glass substrate is bonded to the other surface of the first glass substrate via an adhesive layer, and the film-coated glass is located inside the vehicle; The laminated glass has a visible light transmittance of 20% or less, and a visible light reflectance of the laminated glass measured from inside the vehicle of 6% or less.

[0035] The laminated glass provided by the present invention can be a laminated glass for an automobile sunroof with a low-emissivity layer, and as shown in Fig. 2, the laminated glass provided by one embodiment of the present invention includes a second glass substrate 1, a first glass substrate 2, and an adhesive layer 3 between the two substrates, and includes a low-emissivity layer 4, a metal absorption layer 5, a reflection reduction layer 6, and an outermost barrier layer 7 on the first glass substrate 2. Here, the second glass substrate 1 is the outer glass substrate, and the first glass substrate 2 is the inner glass substrate.

[0036] In an embodiment of the present invention, the coated glass comprises a first glass substrate 2, a low-emissivity layer 4, a metal absorbing layer 5 and a reflection-reduction layer 6, where the low-emissivity layer 4 is deposited on one surface of the first glass substrate 2 and comprises at least one transparent conductive oxide layer, the metal absorbing layer 5 is deposited on the low-emissivity layer 4 and the reflection-reduction layer 6 is deposited on the metal absorbing layer 5.

[0037] As shown in FIG. 2, a low emissivity layer 4, a metal absorption layer 5, a reflection reducing layer 6, and an outermost barrier layer 7 are provided in this order on one surface of a first glass substrate 2 of the film-coated glass.

[0038] In the embodiment of the present invention, the glass substrate is a colorless transparent or colored low visible light Transmittance It is something that Silicates substrate , borate glass substrate or polymer organic glass substrate As a polymer organic glass substrate, , for example, PC, PMMA, etc.

[0039] Furthermore, the first glass substrate is made of colored glass, and the colored glass has a visible light transmittance of 50% or less.

[0040] In an embodiment of the present invention, the low emissivity layer 4 is a TCO transparent conductive film such as ITO, ATO, AZO or FTO. electric layer and the thickness is 100 nm or more.

[0041] Specifically, in one embodiment of the present invention, the low emissivity layer 4 has a thickness of 100 nm to 500 nm and an emissivity value of less than 0.3.

[0042] Furthermore, the metal absorbing layer 5 has a certain absorption characteristic for visible light, and is intended to absorb at least a part of visible light within the wavelength range of 380 to 780 nm.

[0043] The material of the metal absorption layer 5 is at least one selected from the group consisting of Ni, Cr, Ti, Nb, Mo, and Si.

[0044] The metal absorption layer 5 has a thickness of 10 nm or less. Specifically, the thickness of the metal absorption layer 5 is 3.5 to 10 nm, and preferably, the thickness of the metal absorption layer 5 is 5 nm or less. Further, the reflection reduction layer 6 may be at least a bilayer structure of a high and a low refractive index layer, that is, the reflection reduction layer 6 includes at least one high refractive index layer 6.1 and at least one low refractive index layer 6.2, and the high refractive index layer 6.1 and the low refractive index layer 6.2 are alternately laminated. Layer laminated Product It may have a layer structure, that is, the reflection reduction layer 6 includes at least one high refractive index layer 6.1 and at least one low refractive index layer 6.2, and the high refractive index layer 6.1 and the low refractive index layer 6.2 are alternately laminated.

[0045] The refractive index of the high refractive index layer 6.1 is n≧1.7. Specifically, the refractive index of the high refractive index layer 6.1 is 1.7 to 2.3. The high refractive index layer 6.1 is an oxide or a nitride. The material of the high refractive index layer 6.1 is an oxide of at least one element selected from Zn, Sn, Nb, Ti, Ni, Cr, Ta, or a nitride or oxynitride of at least one element selected from Si, Zr, Al. The thickness of the high refractive index layer 6.1 is 10 to 70 nm.

[0046] The refractive index of the low refractive index layer 6.2 is n<1.7. Specifically, the refractive index of the low refractive index layer 6.2 is 1.4 to 1.7. The material of the low refractive index layer 6.2 is an oxide of at least one element selected from Si, Al, B, or a fluoride of at least one element selected from Mg, Al, Ba. The thickness of the low refractive index layer 6.2 is 20 to 150 nm.

[0047] In an embodiment of the present invention, the coated glass further includes an outermost barrier layer 7 deposited on the reflection reduction layer 6. The material of the outermost barrier layer 7 is a nitride or oxynitride of at least one element selected from Si, Al, Zr, Ti, B, Ni. The thickness of the outermost barrier layer 7 is 30 nm or less, and preferably, the thickness of the outermost barrier layer 7 is 0 to 15 nm.

[0048] As shown in FIG. 3, in an embodiment of the present invention, an innermost barrier layer 8 is further deposited between the low-emissivity layer 4 of the film-coated glass and one surface of the first glass substrate 2, and the thickness of the innermost barrier layer 8 is 3 nm or more. Specifically, the material of the innermost barrier layer 8 is an oxide of at least one element selected from Zn, Sn, Ti, Si, Al, Nb, Zr, Ni, Mg, Cr, and Ta, or a nitride or oxynitride of at least one element selected from Si, Al, Zr, B, and Ti.

[0049] In an embodiment of the present invention, the first glass substrate of the film-coated glass is a colored glass, and the visible light transmittance of the colored glass is 50% or less.

[0050] The laminated glass provided by the embodiment of the present invention can be installed in a vehicle, and the film-coated glass is located inside the vehicle, and the second glass substrate 1 is bonded to the other surface of the first glass substrate 2 via the adhesive layer 3. Furthermore, the adhesive layer 3 can be a colorless transparent or colored low visible light Permeability of high molecular weight polymer layer and the polymer layer is For example, it may be PVB, PU, ​​EVA, SGP, etc.

[0051] In one embodiment of the present invention, the adhesive layer 3 is a colored resin layer, and the visible light transmittance of the colored resin layer is less than or equal to 30%.

[0052] In one embodiment of the present invention, the visible light reflectance of the laminated glass measured from the inside of a vehicle is 6% or less, specifically, it is preferably 5% or less, more preferably 4% or less, further preferably 3% or less, and most preferably 2% or less.

[0053] In one embodiment of the present invention, the first glass substrate 2 and / or the second glass substrate 1 are colored glass, and the visible light transmittance of the colored glass is less than or equal to 50%.

[0054] In one embodiment of the present invention, the first glass substrate 2 and / or the second glass substrate 1 are transparent glass, and the visible light transmittance of the transparent glass is greater than 70%.

[0055] In one embodiment of the present invention, in the color Lab value of the laminated glass measured from inside the vehicle, the a value is −6 to 3, and the b value is −12 to 0.

[0056] In one embodiment of the present invention, the adhesive layer 3 is transparent PVB with a visible light transmittance of greater than 90%.

[0057] In one embodiment of the present invention, a light control element is further provided between the film-coated glass and the second glass substrate 1, and the light control element is a PDLC light control thin film, an SPD light control thin film or an EC light control thin film.

[0058] Furthermore, the visible light transmittance of the sunroof laminated glass with the low emissivity layer 4 is Tl≦50%, preferably Tl≦20%, and more preferably Tl≦10%.

[0059] Furthermore, the visible light reflectance of the interior surface of the sunroof made of laminated glass with the low emissivity layer 4, that is, the visible light reflectance of the surface close to the interior of the vehicle, is R2≦6%, preferably the visible light reflectance is R2≦4%, and more preferably the visible light reflectance is R2≦2%.

[0060] Furthermore, the sheet resistance of the low emissivity layer 4 is R≦40Ω / m 2 and the preferred sheet resistance is R≦30Ω / m 2 and more preferably, the sheet resistance is R≦20Ω / m 2 It is.

[0061] Furthermore, the emissivity value of the low emissivity layer 4 is E≦0.4, preferably the emissivity value of the low emissivity layer 4 is E≦0.3, and more preferably the emissivity value of the low emissivity layer 4 is E≦0.2.

[0062] The present invention will be further described below with reference to specific examples.

[0063] The laminated glass provided in this embodiment is used as a window for an automobile. In this embodiment, the "outer glass substrate" refers to the glass substrate adjacent to the vehicle exterior air surface in the laminated glass, i.e., the second glass substrate, the "inner glass substrate" refers to the glass substrate adjacent to the vehicle interior air surface in the laminated glass, i.e., the first glass substrate, the "outer surface of the glass substrate" refers to the interface where the glass contacts the air surface, and the "inner surface of the glass substrate" refers to the interface where the glass contacts the adhesive layer.

[0064] As shown in FIG. 2, the low emissivity laminated glass according to the embodiment of the present invention includes an outer glass substrate 1, which may be transparent glass, and the visible light transmittance of the transparent glass is 70% or more. In order to further improve the heat insulating ability of the sunroof laminated glass and reduce the total solar energy transmittance of the sunroof laminated glass, preferably, an infrared reflective film is deposited on a surface of the outer glass substrate 1 close to the adhesive layer 3, and the infrared reflective film includes at least one silver layer or silver alloy layer, such as two silver layers or silver alloy layers, three silver layers or silver alloy layers, or four silver layers or silver alloy layers, and the infrared reflective film is used to reflect infrared rays in sunlight. More preferably, the visible light transmittance of the transparent glass is 90% or more.

[0065] The adhesive layer 3 is located between the outer glass substrate 1 and the inner glass substrate 2. On the outer surface of the inner glass substrate 2, a low-emission layer 4, a metal absorption layer 5, a reflection reducing layer 6, and an outermost barrier layer 7 are arranged in this order. The outermost barrier layer 7 is the layer furthest from the glass surface. Layer It is.

[0066] In order to meet the light control needs of the laminated glass and adapt to the needs of different scenes, a light control element is further provided between the outer glass substrate 1 and the inner glass substrate 2, and the light control element can be PDLC light control film, SPD light control film, EC light control film, etc.

[0067] The adhesive layer 3 according to the present invention is a colorless transparent or colored low visible lightTransmittance of organic polymer layer and , The organic polymer layer is For example, it may be PVB, PU, ​​EVA, SGP, etc., and for the sunroof laminated glass, when its transmittance is low, the visible light transmittance of the adhesive layer 3 is usually 0 to 30%.

[0068] In the embodiment of the present invention, the low emissivity layer 4 has a reflecting or absorbing effect on infrared radiation and at the same time has a high visible light transmittance. TCO layer and may be a material such as ITO, ATO, AZO, FTO, etc.

[0069] The low-emissivity layer 4 is applied to the outer surface of the inner glass substrate 2 by PVD or CVD. On this surface, the low-emissivity layer 4 of the present invention effectively reduces the heat radiation from the glass into the room, and at the same time blocks the heat radiation from the room to the outside, reducing the heat loss inside the room and providing a certain heat retention effect.

[0070] The thickness of the low-emissivity layer 4 according to the embodiment of the present invention is at least 100 nm or more, but in order to give the glass a low emissivity value, for example, emissivity value <0.3, even <0.2, the thickness of the low-emissivity layer 4 needs to be increased as much as possible, but as the thickness of the low-emissivity layer 4 increases, its visible light reflectance also increases accordingly, even to >10%, and the optical index such as color also changes accordingly, and may even deviate from the neutral color. Meanwhile, for automotive glass, high reflectance and deep color are not acceptable because they cause discomfort to passengers and affect the aesthetics of the vehicle. In order to further reduce the reflectance of the low-emissivity layer 4 and adjust the color, the present invention deposits a metal absorption layer 5 and a reflection reduction layer 6 in this order on the low-emissivity layer 4.

[0071] The reflection-reducing layer 6 in the embodiment of the present invention reduces the normal reflectance. Layer Generally, two or more layers of high and low refractive index are alternately formed. Layered structure A high refractive index is n1≧1.7, typically 1.7 to 2.3, and a low refractive index is n2<1.7, typically 1.4 to 1.7.

[0072] In the embodiment of the present invention, the material of the high / low refractive index layer is not limited. In the embodiment of the present invention, the material of the high refractive index layer is an oxide of at least one element selected from Zn, Sn, Nb, Ti, Ni, Cr, Ta, such as ZnSnO, TiO, NbO, etc., or a nitride or oxynitride of at least one element selected from Si, Zr, Al, such as Si3N4, SiAlN, SiZrN, etc., and the material of the low refractive index layer is an oxide of at least one element selected from Si, Al, B, or a fluoride of at least one element selected from Mg, Al, Ba.

[0073] The anti-reflection layer 6 in the present invention is preferably formed by plating using a magnetron sputtering method. In particular, in order to reduce production costs, the anti-reflection layer 6 in the embodiment of the present invention is formed by alternately depositing two layers of high and low refractive index. Lamination It is preferable to adopt a structure, that is, the reflection reduction layer 6 is arranged in an alternating manner. Lamination Structure One High refractive index layer 6.1 and One The high refractive index layer 6.1 has a thickness of 10 to 70 nm, preferably 10 to 50 nm, and the low refractive index layer 6.2 has a thickness of 20 to 150 nm, preferably 30 to 110 nm.

[0074] In order to further reduce the requirement for reflectance of the laminated glass in the vehicle interior, in the embodiment of the present invention, a metal absorbing layer 5 is deposited between the low emissivity layer 4 and the reflection-reducing layer 6, and the metal absorbing layer 5 may include one or more alloy combinations such as Ni, Cr, Ti, Nb, Mo, Si, etc., and the metal absorbing layer 5 has certain absorption and reflection characteristics for visible light, and its thickness should not be too thick, because the reflectance for visible light will obviously increase when the metal absorbing layer 5 is thick. Therefore, in the embodiment of the present invention, the thickness of the metal absorbing layer 5 is not more than 10 nm, preferably not more than 5 nm.

[0075] The glass including the low-emissivity layer 4 described in the embodiment of the present invention may be tempered or heat-bent, and the treatment temperature may be 500-700° C. In order to further improve the stability of the heat treatment of the low-emissivity layer 4, in the embodiment of the present invention, an outermost barrier layer 7 is further deposited on the reflection-reduction layer 6, and the material of the outermost barrier layer 7 is a nitride or oxynitride of at least one element selected from Si, Al, Zr, Ti, B, and Ni, preferably a silicon nitride layer doped with Al or Zr, such as Si3N4, SiAlN, SiZrN, etc., and the outermost barrier layer 7 is preferably a silicon nitride layer doped with Al or Zr, such as Si3N4, SiAlN, SiZrN, etc. The layer Although it is advantageous to further improve the overall mechanical properties and thermal stability, a thick outermost barrier layer 7 may affect the reflection reduction effect of the reflection reduction layer 6. Eh, layer Since it is disadvantageous to reduce the reflectance of the semiconductor laser, the thickness of the outermost barrier layer 7 is 30 nm or less, and preferably 15 nm or less.

[0076] By the above-mentioned method, the laminated glass with the low-emissivity layer 4 provided by the present invention has an emissivity value of <0.3, a visible light reflectance of the inner surface of the laminated glass with the low-emissivity layer 4 of <4% (test at 0 degree angle), and the inner surface of the laminated glass with the low-emissivity layer 4 has a beautiful color, for example, an a value of -6 to 3 and a b value of 0 to -12.

[0077] (Specific Examples) The present invention will now be described in more detail with reference to specific examples. Lamination A comparative test was carried out by selecting laminated glass with a low emissivity layer of this structure.

[0078] (Comparative Examples 1 to 4 and Example 1) Comparative Example 1 is a laminated sunroof glass with a low-emissivity layer. Both the outer glass substrate 1 and the inner glass substrate 2 are 2.1 mm transparent glass (white glass). On the inner surface of the inner glass substrate 2, a 10 nm Si3N4 innermost barrier layer, a 120 nm ITO low-emissivity layer, and a 35 nm Si3N4 outermost barrier layer are deposited in this order by magnetron sputtering. Both the outer glass substrate 1 and the inner glass substrate 2 after the deposition have been subjected to a heat bending process at 550°C to 650°C. Between the outer glass substrate 1 and the inner glass substrate 2, visible light It is attached via a grey PVB adhesive layer with a transmittance of 10±2%.

[0079] Comparative Example 2 is a laminated sunroof glass with a low-emissivity layer. Both the outer glass substrate 1 and the inner glass substrate 2 are 2.1 mm transparent glass (white glass). On the inner surface of the inner glass substrate 2, an 8 nm Si3N4 innermost barrier layer, a 130 nm ITO low-emissivity layer, a 5 nm NiCr metal absorption layer, and a 35 nm Si3N4 outermost barrier layer are deposited in this order by magnetron sputtering. Both the outer glass substrate 1 and the inner glass substrate 2 after the deposition have been subjected to a heat bending process at 550°C to 650°C. Between the outer glass substrate 1 and the inner glass substrate 2, visible light It is attached via a grey PVB adhesive layer with a transmittance of 10±2%.

[0080] Comparative Example 3 is a laminated sunroof glass with a low-emissivity layer. Both the outer glass substrate 1 and the inner glass substrate 2 are 2.1 mm transparent glass (white glass). On the inner surface of the inner glass substrate 2, an 8 nm Si3N4 innermost barrier layer, a 130 nm ITO low-emissivity layer, a 9 nm NiCr metal absorption layer, and a 35 nm Si3N4 outermost barrier layer are deposited in this order by magnetron sputtering. Both the outer glass substrate 1 and the inner glass substrate 2 after the deposition have been subjected to a heat bending process at 550°C to 650°C. Between the outer glass substrate 1 and the inner glass substrate 2, visible light It is attached via a grey PVB adhesive layer with a transmittance of 10±2%.

[0081] Comparative Example 4 is a laminated sunroof glass with a low-emissivity layer, in which the outer glass substrate 1 and the inner glass substrate 2 are both 2.1 mm transparent glass (white glass), and on the inner surface of the inner glass substrate 2, a 5 nm Si3N4 innermost barrier layer, a 118 nm ITO low-emissivity layer, an 8 nm Si3N4 high-refractive index layer, and a 180 nm SiO2 low-refractive index layer are deposited in this order by magnetron sputtering, and the Si3N4 high-refractive index layer and the SiO2 low-refractive index layer form a two-layered reflection reduction layer, and both the outer glass substrate 1 and the inner glass substrate 2 after film deposition have been subjected to a heat bending process at 550°C to 650°C, and between the outer glass substrate 1 and the inner glass substrate 2, visible light It is attached via a grey PVB adhesive layer with a transmittance of 10±2%.

[0082] Example 1 is a laminated sunroof glass with a low-emission layer, in which an outer glass substrate 1 and an inner glass substrate 2 are both 2.1 mm transparent glass (white glass), and on the inner surface of the inner glass substrate 2, an 8 nm Si3N4 innermost barrier layer, a 130 nm ITO low-emission layer, a 3.5 nm NiCr metal absorption layer, an 11 nm Si3N4 high refractive index layer, a 46 nm SiO2 low refractive index layer, and a 10 nm Si3N4 outermost barrier layer are deposited in this order by magnetron sputtering, and both the outer glass substrate 1 and the inner glass substrate 2 after the deposition have been subjected to a heat bending treatment at 550°C to 650°C, and between the outer glass substrate 1 and the inner glass substrate 2, visible light It is attached via a grey PVB adhesive layer with a transmittance of 10±2%.

[0083] Comparative Examples 1 to 4 and Example 1 Layer The film-coated glass and laminated glass obtained after deposition were subjected to measurements of visible light reflectance, vehicle interior reflection color, emissivity, etc., and the measurement results are shown in Table 1. Table 1 shows the measurement results of the film-coated glass and laminated glass of Comparative Examples 1 to 4 and Example 1.

[0084] (Table 1) TIFF0007682371000001.tif133145

[0085] As can be seen from Table 1, Comparative Example 1 ITO layer Since no metal absorbing layer and reflection reducing layer are deposited on the coated glass, the visible light reflectance of the coated glass is greater than 10%. Even after being combined with gray PVB to form laminated glass, the visible light reflectance of the laminated glass is still greater than 6%, which cannot meet the need to eliminate specular reflection in automobile roof glass.

[0086] Comparative Example 2 and Comparative Example 3 ITO layer However, no reflection-reducing layer is deposited on the coated glass, and the visible light reflectance of the coated glass is greater than 6%. After being combined with gray PVB to form a laminated glass, the visible light reflectance of the laminated glass is less than 6%, but still greater than 5%. Furthermore, with the increase in the thickness of the metal absorbing layer, the visible light reflectance also increases accordingly, and the reflective color is increasingly deviated from neutral color, and the appearance color cannot meet the need for good visual appearance.

[0087] Comparative Example 4 ITO layer A reflection-reducing layer is deposited on the glass, but no metal absorption layer is deposited on the glass. The visible light reflectance of the coated glass is greater than 6%. After combining with gray PVB to form a laminated glass, the visible light reflectance of the laminated glass is less than 3% and the reflected color is also neutral. However, the thickness of the reflection-reducing layer is about 2 to 3 times that of Example 1. Layer The deposition time is extended, which is disadvantageous for reducing production costs.

[0088] In comparison with Comparative Examples 1 to 4, Example 1 can achieve a visible light reflectance of less than 4% for the coated glass, a visible light reflectance of less than 2% for the laminated glass, and a neutral reflected color with high production efficiency and low cost by depositing a metal absorption layer and a reflection reduction layer of appropriate thickness.

[0089] (Examples 2 to 6) Example 2 is a laminated sunroof glass with a low-emission layer, in which an outer glass substrate 1 and an inner glass substrate 2 are both 2.1 mm transparent glass (white glass), and on the inner surface of the inner glass substrate 2, a 5 nm Si3N4 innermost barrier layer, a 160 nm ITO low-emission layer, a 4 nm NiCr metal absorption layer, a 23 nm Si3N4 high refractive index layer, a 60 nm SiO2 low refractive index layer, and a 5 nm Si3N4 outermost barrier layer are deposited in this order by magnetron sputtering, and both the outer glass substrate 1 and the inner glass substrate 2 after the deposition are subjected to a heat bending process at 550°C to 650°C, and between the outer glass substrate 1 and the inner glass substrate 2, visible light It is attached via a grey PVB adhesive layer with a transmittance of 10±2%.

[0090] Example 3 is a laminated sunroof glass with a low-emission layer, in which an outer glass substrate 1 and an inner glass substrate 2 are both 2.1 mm transparent glass (white glass), and on the inner surface of the inner glass substrate 2, a 9 nm Si3N4 innermost barrier layer, a 130 nm ITO low-emission layer, a 3.5 nm NiCr metal absorption layer, a 20 nm ZnSnOx high refractive index layer, and a 60 nm SiO2 low refractive index layer are deposited in this order by magnetron sputtering, and both the outer glass substrate 1 and the inner glass substrate 2 after the deposition have been subjected to a heat bending treatment at 550°C to 650°C, and between the outer glass substrate 1 and the inner glass substrate 2, visible light It is attached via a grey PVB adhesive layer with a transmittance of 10±2%.

[0091] Example 4 is a laminated sunroof glass with a low-emission layer, in which an outer glass substrate 1 and an inner glass substrate 2 are both 2.1 mm transparent glass (white glass), and on the inner surface of the inner glass substrate 2, a 9 nm Si3N4 innermost barrier layer, a 130 nm ITO low-emission layer, a 3.5 nm NiCr metal absorption layer, a 24 nm ZnSnOx high refractive index layer, a 55 nm SiO2 low refractive index layer, and an 8 nm Si3N4 outermost barrier layer are deposited in this order by magnetron sputtering, and both the outer glass substrate 1 and the inner glass substrate 2 after the deposition have been subjected to a heat bending treatment at 550°C to 650°C, and between the outer glass substrate 1 and the inner glass substrate 2, visible light It is attached via a grey PVB adhesive layer with a transmittance of 10±2%.

[0092] Example 5: A laminated sunroof glass with a low-emission layer, in which the outer glass substrate 1 and the inner glass substrate 2 are both 2.1 mm transparent glass (white glass), and on the inner surface of the inner glass substrate 2, a 10 nm Si3N4 innermost barrier layer, a 280 nm AZO low-emission layer, a 3.5 nm NiCr metal absorption layer, a 24 nm Si3N4 high refractive index layer, a 58 nm SiO2 low refractive index layer, and a 9 nm Si3N4 outermost barrier layer are deposited in this order by magnetron sputtering, and both the outer glass substrate 1 and the inner glass substrate 2 after the deposition have been subjected to a heat bending process at 550°C to 650°C, and between the outer glass substrate 1 and the inner glass substrate 2, visible light It is attached via a grey PVB adhesive layer with a transmittance of 10±2%.

[0093] Example 6 is a laminated sunroof glass with a low-emissivity layer, in which an outer glass substrate 1 and an inner glass substrate 2 are both 2.1 mm gray glass (gray glass, visible light transmittance 40%), and on the inner surface of the inner glass substrate 2, a 10 nm Si3N4 innermost barrier layer, a 120 nm ITO low-emissivity layer, a 7.5 nm NiCr metal absorption layer, a 38 nm TiOx high refractive index layer, a 64 nm SiO2 low refractive index layer, and a 9 nm Si3N4 outermost barrier layer are deposited in this order by magnetron sputtering, and both the outer glass substrate 1 and the inner glass substrate 2 after film deposition have been subjected to a heat bending process at 550°C to 650°C, and the outer glass substrate 1 and the inner glass substrate 2 are bonded via a transparent PVB adhesive layer with a visible light transmittance of more than 90%.

[0094] Working Example 2~6 layers The film-coated glass and the laminated glass obtained after deposition were subjected to measurements of visible light reflectance, vehicle interior reflection color, emissivity, etc., and the measurement results are shown in Table 2. Table 2 shows the examples. 2~6 The results are shown in Table 1.

[0095] (Table 2) TIFF0007682371000002.tif192157

[0096] As can be seen from Table 2, in Example 3, the ZnSnOx layer was used as the high refractive index layer, and the outermost barrier layer was not provided, and compared with the case where the Si3N4 layer was used as the high refractive index layer, the film-coated glass had a higher refractive index after the heat treatment. Layer Since the sheet resistance of the reflection-reduction layer is increased, the high refractive index layer in the reflection-reduction layer is preferably a nitride layer or an oxynitride layer containing Si. Layer This is advantageous in improving the heat treatment stability.

[0097] In Example 4, compared to Example 3, a ZnSnOx layer is used as a high refractive index layer, an outermost barrier layer is added, and after heat treatment, Layer This is advantageous in reducing the sheet resistance.

[0098] In Examples 2 and 5, the thickness ITO layer or AZO layer However, a metal absorption layer and a reflection-reducing layer are provided at the same time, and it is still possible to achieve a visible light reflectance of less than 4% for the coated glass, a visible light reflectance of less than 3% or less than 2% for the laminated glass, and a neutral reflected color.

[0099] In Example 6, a combination of gray glass and transparent PVB products is used, and a metal absorption layer and a reflection reduction layer are simultaneously provided, so that the visible light reflectance of the coated glass is less than 4%, the visible light reflectance of the laminated glass is less than 3%, and the reflected color is neutral.

[0100] Although the specific examples described in the present invention have been described above, the present invention is not limited to the content of the specific embodiments described above, and any improvements, equivalent modifications, and replacements made based on the technical gist of the present invention are all within the scope of the present invention. The above-mentioned examples all describe the structural composition of the film-coated glass and laminated glass, but do not describe the specific manufacturing process and parameters of the film-coated glass and laminated glass, and these undescribed parts are all well known to those skilled in the art, so it is understood that the undescribed parts do not affect the scope of the present application. [Explanation of symbols]

[0101] 1 Outer glass substrate (second glass substrate) 2 Inner glass substrate (first glass substrate) 3 Adhesive layer 4 Low emissivity layer 5 Metal Absorption Layer 6 Anti-reflection layer 6.1 High refractive index layer 6.2 Low refractive index layer 7 Outermost barrier layer 8 Innermost barrier layer

Claims

1. In the case of film-coated glass, a first glass substrate, a low emissivity layer, a metal absorbing layer, and a reflection reducing layer; the low emissivity layer is deposited on one surface of the first glass substrate and comprises at least one transparent conductive oxide layer, the transparent conductive oxide layer being an ITO layer, an ATO layer, an AZO layer or an FTO layer; the metal absorbing layer is deposited on the low emissivity layer; the reflection reduction layer is deposited on the metal absorption layer; The low emissivity layer has a thickness of 100 nm to 500 nm and an emissivity value of less than 0.3; The film-coated glass is characterized by the above-mentioned.

2. the reflection-reduction layer includes at least one high-refractive index layer and at least one low-refractive index layer, the high-refractive index layer and the low-refractive index layer are alternately laminated, the refractive index of the high-refractive index layer is 1.7 or more, and the refractive index of the low-refractive index layer is less than 1.7; the material of the high refractive index layer is an oxide of at least one element selected from Zn, Sn, Nb, Ti, Ni, Cr, and Ta, or a nitride or oxynitride of at least one element selected from Si, Zr, and Al; the material of the low refractive index layer is an oxide of at least one element selected from the group consisting of Si, Al, and B, or a fluoride of at least one element selected from the group consisting of Mg, Al, and Ba; The high refractive index layer has a thickness of 10 to 70 nm, and the low refractive index layer has a thickness of 20 to 150 nm.

2. The film-coated glass according to claim 1.

3. the metal absorbing layer is for absorbing at least a portion of visible light in a wavelength range of 380 to 780 nm, and the thickness of the metal absorbing layer is 3.5 to 10 nm, more preferably 5 nm or less; The metal absorbing layer is in direct contact with the low emissivity layer, and the material of the metal absorbing layer is at least one selected from Ni, Cr, Ti, Nb, Mo, and Si; 2. The film-coated glass according to claim 1.

4. An innermost barrier layer is further deposited between the low emissivity layer and one surface of the first glass substrate, the thickness of the innermost barrier layer is 3 nm or more, and the material of the innermost barrier layer is an oxide of at least one element selected from Zn, Sn, Ti, Si, Al, Nb, Zr, Ni, Mg, Cr, and Ta, or a nitride or oxynitride of at least one element selected from Si, Al, Zr, B, and Ti.

2. The film-coated glass according to claim 1.

5. The glass with film further includes an outermost barrier layer deposited on the reflection-reducing layer, the material of the outermost barrier layer being a nitride or oxynitride of at least one element selected from Si, Al, Zr, Ti, B, and Ni, and the thickness of the outermost barrier layer is 30 nm or less, and more preferably 15 nm or less.

2. The film-coated glass according to claim 1.

6. The first glass substrate is a colored glass, and the colored glass has a visible light transmittance of 50% or less; or The first glass substrate is a transparent glass, and the visible light transmittance of the transparent glass is greater than 70%.

2. The film-coated glass according to claim 1.

7. The reflection-reduction layer has a laminated structure including one high refractive index layer and one low refractive index layer, the high refractive index layer having a thickness of 10 to 50 nm, and the low refractive index layer having a thickness of 30 to 110 nm.

2. The film-coated glass according to claim 1.

8. The high refractive index layer is a nitride layer or an oxynitride layer containing Si.

8. The film-coated glass according to claim 7.

9. In laminated glass that can be installed in a vehicle, A glass having a film according to any one of claims 1 to 8, a second glass substrate, and an adhesive layer, the second glass substrate being adhered to another surface of the first glass substrate via the adhesive layer, the glass having a film being positioned inside a vehicle, The laminated glass has a visible light transmittance of 20% or less, and a visible light reflectance of the laminated glass measured from inside a vehicle of 6% or less, more preferably 4% or less, and even more preferably 3% or less. The laminated glass is characterized by the above-mentioned.

10. the second glass substrate is a colored glass, and the colored glass has a visible light transmittance of 50% or less; or The second glass substrate is a transparent glass, and the visible light transmittance of the transparent glass is greater than 70%.

10. The laminated glass according to claim 9.

11. The second glass substrate is a transparent glass, and an infrared reflective film is provided on a surface of the second glass substrate close to the adhesive layer, and the infrared reflective film includes at least one silver layer or a silver alloy layer.

10. The laminated glass according to claim 9.

12. The adhesive layer is a colored resin layer, and the visible light transmittance of the colored resin layer is 30% or less; or The adhesive layer is a transparent PVB having a visible light transmittance of greater than 90%.

10. The laminated glass according to claim 9.

13. In the color Lab value of the laminated glass measured from inside the vehicle, the a value is −6 to 3, and the b value is −12 to 0.

10. The laminated glass according to claim 9.

14. A light control element is further provided between the film-coated glass and the second glass substrate, and the light control element is a PDLC light control thin film, an SPD light control thin film, or an EC light control thin film; 10. The laminated glass according to claim 9.

Images