CN113682007A

CN113682007A - Laminated glass with transparent conductive layer and preparation method thereof

Info

Publication number: CN113682007A
Application number: CN202110969569.9A
Authority: CN
Inventors: 曹晖; 黄凤珠; 何立山; 曾东; 陈国富; 杨斌; 福原康太
Original assignee: Fuyao Glass Industry Group Co Ltd
Current assignee: Fuyao Glass Industry Group Co Ltd
Priority date: 2021-08-23
Filing date: 2021-08-23
Publication date: 2021-11-23

Abstract

The application provides laminated glass with a transparent conducting layer and a preparation method thereof. The laminated glass with the transparent conducting layer comprises a first transparent substrate; the transparent conducting layer is formed on the surface of the first transparent substrate and comprises five dielectric layers and four metal layers which are sequentially and alternately stacked, and two opposite surfaces of each metal layer are provided with the dielectric layers; at least one of the five dielectric layers comprises at least two sub-dielectric layers, the transparent conducting layer is subjected to heat treatment within a preset temperature range, the refractive index fluctuation delta n of each sub-dielectric layer after the heat treatment is less than 0.05, and the preset temperature range is 500-700 ℃; the bonding layer is arranged on the surface of the transparent conducting layer, which is far away from the first transparent substrate; and the second transparent substrate is arranged on the surface of the bonding layer, which is far away from the first transparent substrate. The laminated glass with the transparent conductive layer has uniform appearance color after high-temperature heat treatment.

Description

Laminated glass with transparent conductive layer and preparation method thereof

Technical Field

The application relates to the field of motor vehicles, in particular to laminated glass with a transparent conducting layer and a preparation method thereof.

Background

Currently, in order to make drivers safer and more comfortable when driving vehicles, the prior art forms a transparent conductive layer on a windshield of a vehicle by using Chemical Vapor Deposition (CVD) and Physical Vapor Deposition (PVD), and the like, wherein the transparent conductive layer comprises one or more metal layers, such as silver layers, so that the windshield can reflect infrared rays to have a heat insulation function, or the windshield is electrically heated to have a defrosting and defogging function after electric current is introduced, and the drivers are ensured to have a clear view.

The currently commonly used transparent conductive layer comprises one silver layer, two silver layers or three silver layers, i.e. a single silver product, a double silver product or a triple silver product, which can provide good heat insulation performance and/or electrical heating performance, but to further obtain more excellent heat insulation performance and/or electrical heating performance, the total thickness of the silver layers in the transparent conductive layer needs to be increased, which may cause the visible light transmittance of the windshield to be less than 70% and not meet the requirements of national standards, may also cause the mechanical properties and chemical properties of the transparent conductive layer to be reduced, and even cause the overall appearance color of the transparent conductive layer after high-temperature heat treatment to be uneven.

Disclosure of Invention

In view of the above problems, embodiments of the present application provide a laminated glass with a transparent conductive layer, in which the transparent conductive layer is subjected to a high-temperature heat treatment, so as to meet the thermal insulation requirements and/or the electrical heating requirements of vehicle glass, and have a relatively uniform appearance color.

The embodiment of the application provides a laminated glass with a transparent conducting layer, which comprises:

a first transparent substrate;

the transparent conducting layer is formed on the surface of the first transparent substrate and comprises five dielectric layers and four metal layers which are sequentially and alternately stacked, and the dielectric layers are arranged on two opposite surfaces of each metal layer; at least one of the five dielectric layers comprises at least two sub-dielectric layers, the transparent conducting layer is subjected to heat treatment within a preset temperature range, the refractive index fluctuation Deltan of each sub-dielectric layer after the heat treatment is less than 0.05, and the preset temperature range is 500-700 ℃;

the bonding layer is arranged on the surface, far away from the first transparent substrate, of the transparent conducting layer; and

and the second transparent substrate is arranged on the surface of the bonding layer, which is far away from the first transparent substrate.

The embodiment of the application also provides a preparation method of the laminated glass with the transparent conducting layer, which comprises the following steps:

providing a first transparent substrate; and

depositing a transparent conducting layer on the surface of the first transparent substrate, wherein the transparent conducting layer comprises a first medium layer, a first metal layer, a second medium layer, a second metal layer, a third medium layer, a third metal layer, a fourth medium layer, a fourth metal layer and a fifth medium layer which are sequentially stacked on the surface of the first transparent substrate, and at least one of the first medium layer, the second medium layer, the third medium layer, the fourth medium layer and the fifth medium layer comprises at least two sub-medium layers;

carrying out heat treatment on a first transparent substrate with a transparent conducting layer within a preset temperature range, wherein the preset temperature range is 500-700 ℃, and the refractive index fluctuation deltan of each sub-dielectric layer after the heat treatment is less than 0.05;

providing an adhesive layer and a second transparent substrate, arranging the adhesive layer on the surface of the transparent conductive layer far away from the first transparent substrate, and arranging the second transparent substrate on the surface of the adhesive layer far away from the first transparent substrate to form the laminated glass.

The transparent conducting layer of the laminated glass with the transparent conducting layer is subjected to heat treatment within a preset temperature range, the refractive index fluctuation delta n of each sub-medium layer is less than 0.05, wherein the preset temperature range is 500-700 ℃, and therefore the laminated glass with the transparent conducting layer is good in color uniformity of each position, small in color difference and good in appearance effect. Further, the laminated glass with the transparent conducting layer of the embodiment of the application alternately sets up five dielectric layers and four metal layers, so that the sheet resistance of the whole transparent conducting layer is lower, the conductivity is better, and the effects of better demisting, defrosting and snow removing are achieved.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.

Fig. 1 is a schematic structural diagram of a laminated glass having a transparent conductive layer according to an embodiment of the present application.

Fig. 2 is a schematic structural diagram of a transparent conductive layer according to an embodiment of the present application.

Fig. 3 is a perspective structural view of a laminated glass having a transparent conductive layer according to still another embodiment of the present application.

Fig. 4 is a perspective structural view of a laminated glass having a transparent conductive layer according to still another embodiment of the present application.

Fig. 5 is a schematic flow chart of a method for manufacturing a laminated glass with a transparent conductive layer according to an embodiment of the present disclosure.

Fig. 6 is a schematic structural diagram of a vehicle window according to an embodiment of the present application.

Fig. 7 is a schematic structural diagram of a vehicle according to an embodiment of the present application.

Detailed Description

In order to make the technical solutions of the present application better understood, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.

The terms "first," "second," and the like in the description and claims of the present application and in the above-described drawings are used for distinguishing between different objects and not for describing a particular order. Furthermore, the terms "include" and "have," as well as any variations thereof, are intended to cover non-exclusive inclusions. For example, a process, method, system, article, or apparatus that comprises a list of steps or elements is not limited to only those steps or elements listed, but may alternatively include other steps or elements not listed, or inherent to such process, method, article, or apparatus.

The technical solutions in the embodiments of the present application will be described below with reference to the accompanying drawings.

It should be noted that, for convenience of description, like reference numerals denote like parts in the embodiments of the present application, and a detailed description of the like parts is omitted in different embodiments for the sake of brevity.

Referring to fig. 1 and 2, an embodiment of the present application provides a laminated glass 100 with a transparent conductive layer, which is applied to heat insulation, defogging, defrosting or snow removal, and the laminated glass 100 with the transparent conductive layer includes: a first transparent substrate 10; the transparent conducting layer 30 is formed on the surface of the first transparent substrate 10, the transparent conducting layer 30 comprises five dielectric layers and four metal layers which are sequentially and alternately stacked, and the dielectric layers are arranged on two opposite surfaces of each metal layer; at least one of the five dielectric layers comprises at least two sub-dielectric layers 301, the transparent conducting layer 30 is subjected to heat treatment within a preset temperature range, and the refractive index fluctuation deltan of each sub-dielectric layer 301 is less than 0.05, wherein the preset temperature range is 500-700 ℃; an adhesive layer 50 disposed on a surface of the transparent conductive layer 30 away from the first transparent substrate 10; and a second transparent substrate 70 disposed on a surface of the adhesive layer 50 away from the first transparent substrate 10.

The laminated glass 100 with the transparent conductive layer in the embodiment of the application can be used as glass or doors and windows of vehicles, buildings and the like, and has better infrared reflection capability, so that the laminated glass 100 with the transparent conductive layer has better heat insulation effect. After voltage or current is loaded at the two ends of the transparent conducting layer, the four metal layers generate heat, the phenomena of fogging, frosting or snow accumulation and the like caused by large internal and external temperature difference or a cold environment on the surface of the laminated glass 100 with the transparent conducting layer can be well removed, and when the laminated glass is applied to an automobile windshield, even if the internal and external temperature difference is large or the cold environment is low, the windshield can also have clear sight lines, so that a driver has a clear visual field.

Alternatively, the refractive index fluctuation Δ n of each of the sub-medium layers 301 may be, but is not limited to, 0.049, 0.04, 0.03, 0.02, 0.01, 0.005, 0.001, etc. Alternatively, the preset temperature range may be, but is not limited to, 500 ℃, 550 ℃, 580 ℃, 600 ℃, 630 ℃, 650 ℃, 700 ℃, and the like.

After the transparent conductive layer 30 of the embodiment of the present application is subjected to heat treatment in a preset temperature range, the refractive index fluctuation Δ n of each sub-dielectric layer 301 is less than 0.05, wherein the preset temperature range is 500 ℃ to 700 ℃, so that the color uniformity of each position of the laminated glass 100 with the transparent conductive layer of the present application is good, the color difference is small, and a good appearance effect is achieved. Further, the laminated glass 100 with the transparent conducting layer of the embodiment of the present application alternately sets five dielectric layers and four metal layers, so that the sheet resistance of the whole transparent conducting layer 30 is lower, the conductivity is better, and better defogging, defrosting and snow removing effects are achieved.

Optionally, the extinction coefficient fluctuation Δ k of each of the sub-dielectric layers 301 is less than 0.001, and specifically, the extinction coefficient fluctuation of each of the sub-dielectric layers 301 may be, but is not limited to, 0.0009, 0.0008, 0.0006, 0.0005, 0.0004, 0.0002, 0.0001, 0.0005, 0.0001, and the like. This can make the appearance color of the produced laminated glass 100 having the transparent conductive layer more uniform.

The color difference delta E between any two points on the laminated glass 100 with the transparent conducting layer of the embodiment of the application is less than 3; more specifically, Δ E < 2. Specifically, the color difference between any two points on the laminated glass 100 having the transparent conductive layer may be, but is not limited to, 2.9, 2.7, 2.5, 2.3, 2.0, 1.8, 1.5, 1.2, 1.0, 0.8, 0.5, etc. Therefore, the laminated glass 100 with the transparent conducting layer has uniform color and good appearance effect.

Alternatively, the color difference between any two points on the laminated glass 100 having the transparent conductive layer (e.g., the color difference between position 1 and position 2) can be calculated by the following formula (1):

△E＝[(L₁-L₂)²+(a*1-a*2)²+(b*1-b*2)²]^1/2 (1)，

wherein L is₁Brightness of position 1, a 1 and b 1 are coordinates of position 1 color space, L₂For the luminance of position 2, a x 2 and b x 2 are the coordinates of the color space of position 2.

Alternatively, the laminated glass 100 having a transparent conductive layer according to the embodiment of the present application may be neutral, pale blue, or cyan, or the like. When visible light is perpendicularly incident on the laminated glass 100 having the transparent conductive layer (i.e., when the incident angle is 0), the color space coordinate value a of the laminated glass 100 having the transparent conductive layer ranges from-7 to 1; specifically, it can be, but is not limited to, -7, -6, -5, -4, -3, -2, -1, 0, 1, etc. The color space coordinate value b of the laminated glass 100 having the transparent conductive layer ranges from-13 to 1; specifically, it can be, but is not limited to, -13, -12, -11, -10, -9, -8, -7, -6, -5, -4, -3, -2, -1, 0, 1, etc.

Alternatively, the laminated glass 100 with the transparent conductive layer of the embodiment of the present application has a visible light transmittance of more than 70%, for example, but not limited to 71%, 75%, 80%, 85%, 90%, 95%, and the like. Optionally, the visible light reflectivity of the surface of the second transparent substrate away from the bonding layer is less than 15%; for example, but not limited to, 15%, 13%, 10%, 8%, 6%, 5%, 3%, 1%, etc. The infrared transmittance of the laminated glass with the transparent conductive layer is less than 3%; for example, but not limited to, 2.5%, 2%, 1%, 0.5%, etc. From this for when the laminated glass 100 with transparent conducting layer of this application was applied to vehicle windshield, its visible light transmissivity can satisfy the national standard requirement, and visible light reflectivity is low moreover makes the mirror surface effect weak, has improved driving safety nature, still has better thermal-insulated effect simultaneously, has improved the driving comfort.

Alternatively, the first transparent substrate 10 may be a transparent glass substrate, such as inorganic glass. The first transparent substrate 10 has a thickness of 1.0mm to 3.5mm, and specifically, may be, but not limited to, 1.1mm, 1.4mm, 1.5mm, 1.6mm, 1.8mm, 2.1mm, 2.3mm, 2.5mm, 2.8mm, 3.0mm, 3.5mm, and the like.

Alternatively, the second transparent substrate 70 may be a transparent glass substrate, such as inorganic glass. The thickness of the second transparent substrate 70 is 0.7mm to 2.5mm, and specifically, may be, but is not limited to, 0.7mm, 1.0mm, 1.2mm, 1.5mm, 1.8mm, 2.0mm, 2.2mm, 2.5mm, and the like.

Alternatively, when the laminated glass 100 having a transparent conductive layer is applied to a vehicle, a building, or the like, the first transparent substrate 10 may face the inside of the vehicle or the building, or may face the outside of the vehicle or the building.

Alternatively, the material of the adhesive layer 50 may be at least one of polyvinyl butyral (PVB), Ethylene Vinyl Acetate (EVA), an ionic interlayer (SGP), polyethylene terephthalate (PET), and polyvinyl chloride (PVC). The adhesive layer 50 has a thickness of 0.3mm to 2.28mm, and specifically, may be, but is not limited to, 0.38mm, 0.5mm, 0.6mm, 0.76mm, 0.8mm, 0.9mm, 1mm, 1.14mm, 1.52mm, 1.9mm, and the like.

Referring again to fig. 2, in some embodiments, the four metal layers include a first metal layer 32, a second metal layer 34, a third metal layer 36, and a fourth metal layer 38; the first metal layer 32, the second metal layer 34, the third metal layer 36 and the fourth metal layer 38 are sequentially arranged at intervals along the direction from the first transparent substrate 10 to the second transparent substrate 70.

Alternatively, the metal layer may be a silver layer or a silver alloy layer, and the silver alloy layer may be an alloy of silver and at least one of gold, copper, platinum, and aluminum. When the metal layer is a silver alloy layer, the weight fraction of silver in the silver alloy layer is greater than 90%.

Optionally, the sum of the thicknesses of the second metal layer 34 and the third metal layer 36 is greater than the sum of the thicknesses of the first metal layer 32 and the fourth metal layer 38. This can reduce the reflectance of the laminated glass 100 having the transparent conductive layer to visible light, thereby improving the transmittance of the laminated glass 100 having the transparent conductive layer to visible light. When the sum of the thicknesses of the second metal layer 34 and the third metal layer 36 is less than the sum of the thicknesses of the first metal layer 32 and the fourth metal layer 38, the reflectivity of the formed laminated glass 100 with the transparent conductive layer to visible light is increased, so that the transmittance of the laminated glass 100 with the transparent conductive layer to visible light is reduced.

Optionally, the sum of the thicknesses of the second metal layer 34 and the third metal layer 36 is 1.1 times to 1.8 times the sum of the thicknesses of the first metal layer 32 and the fourth metal layer 38. Specifically, the sum of the thicknesses of the second metal layer 34 and the third metal layer 36 may be, but is not limited to, 1.1 times, 1.2 times, 1.3 times, 1.4 times, 1.5 times, 1.6 times, 1.7 times, 1.8 times, etc. of the sum of the thicknesses of the first metal layer 32 and the fourth metal layer 38. When the sum of the thicknesses of the second metal layer 34 and the third metal layer 36 is less than 1.1 times of the sum of the thicknesses of the first metal layer 32 and the fourth metal layer 38, the reflectivity of the laminated glass 100 with the transparent conductive layer to visible light is increased, and the transmittance is reduced; when the sum of the thicknesses of the second metal layer 34 and the third metal layer 36 is greater than 1.8 times the sum of the thicknesses of the first metal layer 32 and the fourth metal layer 38, the absorption rate of visible light by the laminated glass 100 having a transparent conductive layer is increased, and the transmittance is decreased.

In some embodiments, the thickness of the second metal layer 34 is greater than the thickness of the first metal layer 32 and greater than the thickness of the fourth metal layer 38; the thickness of the third metal layer 36 is greater than the thickness of the first metal layer 32 and greater than the thickness of the fourth metal layer 38. Optionally, the thickness of the second metal layer 34 is 1.1 times to 1.8 times the thickness of the first metal layer 32; specifically, it may be, but not limited to, 1.1 times, 1.2 times, 1.3 times, 1.4 times, 1.5 times, 1.6 times, 1.7 times, 1.8 times, etc. The thickness of the second metal layer 34 is 1.1 times to 1.8 times that of the fourth metal layer 38; specifically, it may be, but not limited to, 1.1 times, 1.2 times, 1.3 times, 1.4 times, 1.5 times, 1.6 times, 1.7 times, 1.8 times, etc. Optionally, the thickness of the third metal layer 36 is 1.1 times to 1.8 times the thickness of the first metal layer 32; specifically, it may be, but not limited to, 1.1 times, 1.2 times, 1.3 times, 1.4 times, 1.5 times, 1.6 times, 1.7 times, 1.8 times, etc. The thickness of the third metal layer 36 is 1.1 times to 1.8 times that of the fourth metal layer 38; specifically, it may be, but not limited to, 1.1 times, 1.2 times, 1.3 times, 1.4 times, 1.5 times, 1.6 times, 1.7 times, 1.8 times, etc.

In some embodiments, the ratio of the thickness of the second metal layer 34 to the thickness of the third metal layer 36 is 0.85 to 1.15; specifically, it may be, but not limited to, 0.85, 0.9, 0.95, 1.0, 1.05, 1.1, 1.15, etc.

Optionally, the thickness of the first metal layer 32 is 5nm to 20 nm; specifically, it may be, but not limited to, 5nm, 8nm, 10nm, 12nm, 15nm, 18nm, 20nm, etc. The thickness of the first metal layer 32 is too thin, the film surface sheet resistance is large, the reflectivity to infrared rays is low, the heat insulation effect is poor, the electric heating power density cannot meet the requirement, and the defogging, defrosting and snow removing effects are poor; the first metal layer 32 has a too large thickness and a low visible light transmittance, and thus it is difficult to satisfy the requirement of 70% or more.

Optionally, the thickness of the second metal layer 34 is 5nm to 20 nm; specifically, it may be, but not limited to, 5nm, 8nm, 10nm, 12nm, 15nm, 18nm, 20nm, etc. The thickness of the second metal layer 34 is too thin, the film surface sheet resistance is large, the reflectivity to infrared rays is low, the heat insulation effect is poor, the electric heating power density cannot meet the requirement, and the defogging, defrosting and snow removing effects are poor; the thickness of the second metal layer 34 is too thick, and the visible light transmittance is low, so that it is difficult to satisfy the requirement of 70% or more.

Optionally, the thickness of the third metal layer 36 is 5nm to 20 nm; specifically, it may be, but not limited to, 5nm, 8nm, 10nm, 12nm, 15nm, 18nm, 20nm, etc. The thickness of the third metal layer 36 is too thin, the film surface sheet resistance is large, the reflectivity to infrared rays is low, the heat insulation effect is poor, the electric heating power density cannot meet the requirement, and the defogging, defrosting and snow removing effects are poor; the thickness of the third metal layer 36 is too thick, and the visible light transmittance is low, so that it is difficult to satisfy the requirement of 70% or more.

Optionally, the thickness of the fourth metal layer 38 is 5nm to 20 nm; specifically, it may be, but not limited to, 5nm, 8nm, 10nm, 12nm, 15nm, 18nm, 20nm, etc. The thickness of the fourth metal layer 38 is too thin, the film surface sheet resistance is large, the reflectivity to infrared rays is low, the heat insulation effect is poor, the electric heating power density cannot meet the requirements, and the defogging, defrosting and snow removing effects are poor; the thickness of the fourth metal layer 38 is too thick, and the visible light transmittance is low, so that it is difficult to satisfy the requirement of 70% or more.

Referring to fig. 2 again, in some embodiments, the five dielectric layers include a first dielectric layer 31, a second dielectric layer 33, a third dielectric layer 35, a fourth dielectric layer 37 and a fifth dielectric layer 39, and the first dielectric layer 31, the second dielectric layer 33, the third dielectric layer 35, the fourth dielectric layer 37 and the fifth dielectric layer 39 are sequentially disposed at intervals along a direction from the first transparent substrate 10 to the second transparent substrate 70. In other words, the transparent conductive layer 30 includes a first dielectric layer 31, a first metal layer 32, a second dielectric layer 33, a second metal layer 34, a third dielectric layer 35, a third metal layer 36, a fourth dielectric layer 37, a fourth metal layer 38, and a fifth dielectric layer 39, which are sequentially stacked; the first dielectric layer 31 is disposed closer to the first transparent substrate 10 than the fifth dielectric layer 39. The first dielectric layer 31 is used to prevent alkali metal ions (such as sodium ions), oxygen atoms and other impurity atoms in the glass from entering the first metal layer 32, so as to prevent the film layer of the first metal layer 32 from being damaged, avoid the lower electrical conductivity and optical performance, and improve the adhesion between the first transparent substrate 10 and the first metal layer 32.

In some embodiments, at least one of the first dielectric layer 31, the second dielectric layer 33, the third dielectric layer 35, the fourth dielectric layer 37, and the fifth dielectric layer 39 includes at least two sub-dielectric layers, and the material of each sub-dielectric layer 301 is selected from an oxide, a nitride, or an oxynitride of at least one of Zn, Ti, Si, Al, Sn, Se, Zr, Ni, In, Cr, W, Ca, Y, Nb, Cu, Sm. For example, the sub-dielectric layer 301 may be made of zinc tin oxide (ZnSnOx), aluminum-doped zinc oxide (AZO), titanium oxide (TiOx), silicon zirconium nitride (SiZrN), silicon aluminum nitride (SiALN), silicon aluminum oxide (SiAlO), or the like.

In some embodiments, the material of the sub-dielectric layer 301 farthest from the first transparent substrate 10 (i.e., the sub-dielectric layer 301 close to the second transparent substrate 70) of at least one of the first dielectric layer 31, the second dielectric layer 33, the third dielectric layer 35, and the fourth dielectric layer 37 is selected from an oxide of at least one of Zn, Ti, Si, Al, Sn, Se, Zr, Ni, In, Cr, W, Ca, Y, Nb, Cu, Sm, and may be, for example, zinc tin oxide, aluminum-doped zinc oxide, titanium oxide, silicon aluminum oxide, or the like. In one embodiment, the material of the sub-dielectric layer 301 farthest from the first transparent substrate 10 (i.e., the sub-dielectric layer 301 close to the second transparent substrate 70) In the first dielectric layer 31 is selected from an oxide of at least one of Zn, Ti, Si, Al, Sn, Se, Zr, Ni, In, Cr, W, Ca, Y, Nb, Cu, Sm; the material of the sub-dielectric layer 301 farthest from the first transparent substrate 10 In the second dielectric layer 33 (i.e., the sub-dielectric layer 301 close to the second transparent substrate 70) is selected from an oxide of at least one of Zn, Ti, Si, Al, Sn, Se, Zr, Ni, In, Cr, W, Ca, Y, Nb, Cu, Sm; the material of the sub-dielectric layer 301 farthest from the first transparent substrate 10 In the third dielectric layer 35 (i.e., the sub-dielectric layer 301 close to the second transparent substrate 70) is selected from an oxide of at least one of Zn, Ti, Si, Al, Sn, Se, Zr, Ni, In, Cr, W, Ca, Y, Nb, Cu, Sm; the material of the sub-dielectric layer 301 far from the first transparent substrate 10 (i.e., the sub-dielectric layer 301 near the second transparent substrate 70) In the fourth dielectric layer 37 is selected from oxides of at least one of Zn, Ti, Si, Al, Sn, Se, Zr, Ni, In, Cr, W, Ca, Y, Nb, Cu, Sm. The growth of the metal layer is facilitated, so that the metal layer has better adhesion on the dielectric layer, and the color and optical properties (such as visible light transmittance, visible light reflectance, infrared light reflectance and the like) of the film layer of the transparent conductive layer 30 can be better adjusted.

Optionally, the thickness of the fourth dielectric layer 37 is greater than the thickness of the second dielectric layer 33, and the thickness of the second dielectric layer 33 is greater than the thickness of the third dielectric layer 35. This allows the visible light reflectance spectrum to fall within the target curve, making the resulting laminated glass 100 with transparent conductive layers more aesthetically pleasing and better looking. When the thickness of the fourth dielectric layer 37 is reduced, the thicknesses of the second dielectric layer 33 and the third dielectric layer 35 are increased. The visible light reflection spectrum may shift toward a long wavelength (i.e., toward a red wavelength), causing the resulting laminated glass 100 having the transparent conductive layer to be out of specification.

Optionally, the thickness of the first dielectric layer 31 is 35nm to 55nm, and specifically, may be, but is not limited to, 35nm, 38nm, 40nm, 42nm, 45nm, 47nm, 50nm, 53nm, 55nm, and the like.

Optionally, the thickness of the second dielectric layer 33 is 75nm to 85nm, and specifically, may be, but is not limited to, 75nm, 78nm, 80nm, 82nm, 85nm, and the like.

Optionally, the thickness of the third dielectric layer 35 is 70nm to 80nm, and specifically, may be, but is not limited to, 70nm, 72nm, 74nm, 76nm, 78nm, 80nm, and the like.

Optionally, the thickness of the fourth dielectric layer 37 is 80nm to 90nm, and specifically, may be, but is not limited to, 80nm, 82nm, 84nm, 86nm, 88nm, 90nm, and the like.

Optionally, the thickness of the fifth dielectric layer 39 is 40nm to 80nm, and specifically, may be, but is not limited to, 40nm, 45nm, 50nm, 55nm, 60nm, 65nm, 70nm, 75nm, 80nm, and the like.

In some embodiments, each of the dielectric layers includes, but is not limited to, two, three, four, five, or six sub-dielectric layers 301.

In some embodiments, the first dielectric layer 31 and the fifth dielectric layer 39 each include at least two sub-dielectric layers 301. For example, the first dielectric layer 31 includes ZnSnOx, TiOx, and AZO stacked in this order, where ZnSnOx is disposed closer to the first transparent substrate 10 than AZO. For another example, the first dielectric layer 31 includes SiAlN and AZO sequentially stacked, wherein the SiAlN is disposed closer to the first transparent substrate 10 than the AZO. For another example, the first dielectric layer 31 includes ZnSnOx and AZO stacked in sequence, wherein the ZnSnOx is disposed closer to the first transparent substrate 10 than the AZO.

In some embodiments, the second dielectric layer 33, the third dielectric layer 35, and the fourth dielectric layer 37 each include at least three dielectric layers.

Referring to fig. 3 and 4, in some embodiments, a first bus bar 20 and a second bus bar 40 electrically connected to the transparent conductive layer 30 are further disposed between the first transparent substrate 10 and the second transparent substrate 70, and the transparent conductive layer 30 has at least 600W/m between the first bus bar 20 and the second bus bar 40²Heating power density of (1). When having a transparent conductive layer 30When the laminated glass is applied to a windshield of a vehicle, the first bus bar 20 and the second bus bar 40 may be respectively located on the left and right sides of the windshield (as shown in fig. 3), and may be respectively located on the upper and lower sides of the windshield (as shown in fig. 4). The term "heating power density" in this application refers to the heating power per unit area.

Optionally, the first bus bar 20 and the second bus bar 40 are respectively disposed on two opposite sides of the transparent conductive layer 30, and are used for accessing an external power source to the transparent conductive layer 30. Alternatively, the first bus bar 20 and the second bus bar 40 may be made of a conductive material such as copper foil, printed silver paste, or the like.

In some embodiments, the radius of curvature of the laminated glass with the transparent conductive layer 30 in the predetermined direction is at least 6000 mm. In other words, the curvature radius of the laminated glass with the transparent conductive layer 30 along the preset direction is greater than or equal to 6000 mm. When the laminated glass having the transparent conductive layer 30 is applied to a vehicle windshield, the predetermined direction is a direction between a lower edge and an upper edge of the windshield, and a radius of curvature in the predetermined direction is also referred to as a vertical radius of curvature.

In some embodiments, the sheet resistance of the transparent conductive layer 30 after the heat treatment is less than or equal to 0.6 Ω/□. Specifically, the sheet resistance of the transparent conductive layer 30 after the heat treatment may be, but is not limited to, 0.6 Ω/□, 0.5 Ω/□, 0.4 Ω/□, 0.3 Ω/□, 0.2 Ω/□, and the like.

At present, in order to enable a driver to have a good sight line under a large temperature difference between the inside and the outside or a cold environment and avoid influencing safe driving, a metal layer is generally arranged on a windshield of a vehicle, and dielectric layers are arranged on two sides of the metal layer. The front windshield of the vehicle is large in area and mostly has a curved surface structure, and hot bending processing is needed during preparation to form the curved surface structure. When the windshield is subjected to hot bending processing, different positions of the windshield are different from the furnace top heating wire, the radiation heating distance is different, the heating temperature close to the heating temperature is high, the heating temperature far away from the heating temperature is low, and different temperatures can cause the transparent conducting layer 30 (the dielectric layer and the metal layer) in the windshield to react in different degrees, so that different positions have different crystallinities, the reflectivity and the transmissivity of visible light are different, and the surface color of the prepared windshield is not uniform.

Referring to fig. 5, an embodiment of the present application further provides a method for preparing a laminated glass 100 with a transparent conductive layer, where the method can be used to prepare the laminated glass 100 with a transparent conductive layer according to the embodiment of the present application, and the method includes:

s201, providing a first transparent substrate 10; and

s202, depositing a transparent conducting layer on the surface of the first transparent substrate, wherein the transparent conducting layer comprises a first dielectric layer, a first metal layer, a second dielectric layer, a second metal layer, a third dielectric layer, a third metal layer, a fourth dielectric layer, a fourth metal layer and a fifth dielectric layer which are sequentially stacked on the surface of the first transparent substrate, and at least one of the first dielectric layer, the second dielectric layer, the third dielectric layer, the fourth dielectric layer and the fifth dielectric layer comprises at least two sub-dielectric layers;

optionally, the material of each sub-dielectric layer is selected from an oxide, a nitride, or an oxynitride of at least one of Zn, Ti, Si, Al, Sn, Se, Zr, Ni, In, Cr, W, Ca, Y, Nb, Cu, Sm. Optionally, when each sub-dielectric layer is deposited, flux ratio of argon and oxygen, or argon and nitrogen, or argon, oxygen and nitrogen is adjusted, so that after each sub-dielectric layer is subjected to heat treatment in a preset temperature range, refractive index fluctuation Δ n is less than 0.05, and extinction coefficient fluctuation Δ k is less than 0.001, wherein the preset temperature range is 500 ℃ to 700 ℃.

In some embodiments, the material of at least one of the sub-dielectric layers is ZnSnOx, when the sub-dielectric layer 301 is ZnSnOx, the deposition target material is a ZnSn alloy target when the sub-dielectric layer 301 is deposited, the deposition gas is argon and oxygen, and the flux ratio of argon to oxygen ranges from 0.15 to 0.5; specifically, it may be, but not limited to, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, etc. When the flux ratio of argon to oxygen is in this range, the peroxy sputtering can be better ensured, and complete oxide is formed, so that the prepared zinc tin oxide mainly performs the growth and crystallization of crystal grains in the heat treatment process, and no chemical reaction occurs, such as obtaining oxygen from the outside, thereby reducing the refractive index fluctuation and extinction coefficient fluctuation before and after the heat treatment of the zinc tin oxide, and further reducing the color difference delta E between any two points on the laminated glass 100 with the transparent conductive layer.

In some embodiments, the material of at least one of the sub-dielectric layers is AZO, when the sub-dielectric layer 301 is AZO, the deposition target material is an AZO ceramic target when the sub-dielectric layer 301 is deposited, the deposition gas is argon and oxygen, and the flux ratio of the argon to the oxygen is greater than 5; further, the argon to oxygen flux ratio is greater than 10; specifically, it may be, but is not limited to, 6, 10, 15, 20, 25, 30, 40, 50, 60, 70, 80, 90, 100, etc. Alternatively, in some embodiments, when the sub-dielectric layer 301 is aluminum-doped zinc oxide, only argon gas may be introduced, but not oxygen gas may be introduced when the sub-dielectric layer 301 is deposited. When the aluminum-doped zinc oxide is deposited, oxygen is not too much, and too much oxygen can cause target poisoning, so that the sputtering rate is reduced, the production efficiency is influenced, and the production cost is increased.

In some embodiments, the material of at least one of the sub-dielectric layers is TiOx, when the sub-dielectric layer 301 is titanium oxide, the deposition target material is a TiOx ceramic target when the sub-dielectric layer 301 is deposited, the deposition gas is argon and oxygen, and the flux ratio of argon to oxygen is greater than 20; further, the argon to oxygen flux ratio is greater than 50; specifically, it may be, but is not limited to, 20, 30, 40, 50, 60, 70, 80, 90, 100, etc.

In some embodiments, the material of at least one of the sub-dielectric layers is SiZrN or SiAlN, when the sub-dielectric layer 301 is SiZrN or SiAlN, the deposition target material is an SiZr alloy target or an SiAl alloy target when the sub-dielectric layer 301 is deposited, the deposition gas is argon and nitrogen, and the flux ratio of the argon to the nitrogen ranges from 0.2 to 1.5; specifically, it may be, but not limited to, 0.2, 0.3, 0.4, 0.5, 0.8, 1.0, 1.2, 1.4, 1.5, etc. When the flux ratio of the argon gas to the nitrogen gas is within the range, the nitrogen sputtering can be better ensured to form complete nitride, so that the prepared SiZrN or SiAlN mainly performs the growth and crystallization of crystal grains in the heat treatment process, and no chemical reaction occurs, such as obtaining nitrogen from the outside, thereby reducing the refractive index fluctuation and extinction coefficient fluctuation before and after the SiZrN or SiAlN heat treatment, and further reducing the color difference Delta E between any two points on the laminated glass 100 with the transparent conducting layer.

S203, performing heat treatment on a first transparent substrate with a transparent conducting layer within a preset temperature range, wherein the preset temperature range is 500-700 ℃, and the refractive index fluctuation Deltan of each sub-dielectric layer after the heat treatment is less than 0.05; and

optionally, the first transparent substrate is subjected to a hot bending treatment at a temperature of 500 ℃ to 700 ℃ to form a curved surface structure. Optionally, the refractive index fluctuation Δ n of each sub-dielectric layer after the heat treatment is less than 0.05. Optionally, the extinction coefficient fluctuation Δ k of each sub-dielectric layer after the heat treatment is less than 0.001.

S204, providing an adhesive layer and a second transparent substrate, arranging the adhesive layer on the surface of the transparent conducting layer far away from the first transparent substrate, and arranging the second transparent substrate on the surface of the adhesive layer far away from the first transparent substrate to form the laminated glass.

Optionally, providing a second transparent substrate 70, and laying an adhesive layer on the second transparent substrate 70; the first transparent substrate 10 is stacked on the adhesive layer, wherein the adhesive layer and the transparent conductive layer are disposed to face each other.

For the features of this embodiment that are the same as those of the above embodiment and are not described in detail, please refer to the description of the corresponding portions of the above embodiment, which is not described herein again.

According to the embodiment of the application, the flux ratio of argon and oxygen, or the flux ratio of argon and nitrogen when each sub-dielectric layer 301 is prepared is adjusted, so that each obtained sub-dielectric layer 301 forms complete oxide or nitride, when heat treatment is carried out in a preset temperature range, the oxide or nitride of each dielectric sub-layer mainly carries out growth and crystallization of crystal grains, chemical reaction does not occur, for example, oxygen or nitrogen is obtained from the outside, and further, after each sub-dielectric layer 301 is subjected to heat treatment in the preset temperature range, the refractive index fluctuation delta n is less than 0.05, and the extinction coefficient fluctuation delta k is less than 0.001, wherein the preset temperature range is 150-650 ℃. Therefore, the prepared laminated glass 100 with the transparent conductive layer has good color uniformity at each position, small color difference and good appearance effect.

The laminated glass 100 having a transparent conductive layer according to the embodiment of the present application will be further described below with reference to specific examples.

Examples 1 to 3 and comparative examples 1 to 3

The laminated glasses having transparent conductive layers of the following examples and comparative examples were prepared by the following steps:

1) providing a first transparent substrate;

2) depositing five dielectric layers and four metal layers which are alternately stacked on the surface of the first transparent substrate in sequence, wherein the dielectric layers are arranged on two opposite surfaces of each metal layer; each dielectric layer comprises at least two sub-dielectric layers, and the material of each sub-dielectric layer is selected from oxide, nitride or oxynitride of at least one of Zn, Ti, Si, Al, Sn, Se, Zr, Ni, In, Cr, W, Ca, Y, Nb, Cu and Sm;

3) performing hot bending treatment at 600 ℃;

4) providing a second transparent substrate, and coating and laying an adhesive layer on the second transparent substrate; and

5) and laminating a first transparent substrate on the bonding layer, wherein the bonding layer and the transparent conductive layer are arranged oppositely.

The compositions, thicknesses, etc. of the respective film layers of the examples and comparative examples are shown in tables 1 to 3 below.

The transparent heating substrates obtained in the above examples and comparative examples were subjected to film surface sheet resistance, refractive index fluctuation Δ n after high temperature treatment, extinction coefficient fluctuation Δ k after high temperature treatment, color difference Δ E, visible light transmittance TL% (measured by ISO 9050), infrared light transmittance Tir% (measured by ISO 9050), visible light reflectance RL% (measured by ISO 9050), and L a b color space coordinates (measured according to CIE 1976, D65 illuminant 10 degree angle). The test results are shown in tables 1 to 3 below.

As can be seen from tables 1 to 3 below, Ar/O of each sub-dielectric layer was controlled₂Flux ratio of (A) or Ar/N₂Flux ratio, when the transparent conductive layer is subjected to heat treatment in a preset temperature range, the refractive index fluctuation Delta n of each prepared sub-medium layer can be realized<0.05, the extinction coefficient of each sub-medium layer fluctuates by delta k<0.001, so that the color difference delta E of the prepared transparent heating base material is less than 3, and the transparent heating base material has better color uniformity and appearance effect. Meanwhile, the heat insulation material has higher visible light transmittance, lower visible light reflectivity and lower infrared light transmittance (the lower the infrared light transmittance, the better the heat insulation effect).

Table 1 parameters and test results of the transparent heating substrates of example 1 and comparative example 1

Table 2 parameters and test results of the transparent heating substrates of example 2 and comparative example 2

Table 3 respective parameters and test results of the transparent heating substrates of example 3 and comparative example 3

Referring to fig. 6, the present embodiment further provides a vehicle window 400, which includes: a housing body 410; the laminated glass 100 with the transparent conductive layer according to the embodiment of the present application, the laminated glass 100 with the transparent conductive layer is carried on the housing body 410.

Alternatively, the vehicle visible window 400 may be, but is not limited to, a sunroof, a windshield, a door window, etc. of the vehicle 500.

Alternatively, the housing body 410 may be an integral structure with the vehicle body, in other words, the housing body 410 may be a part of the vehicle body, or may be a separate structure, and then mounted on the vehicle body.

Referring to fig. 7, an embodiment of the present application further provides a vehicle 500, which includes: a vehicle body 510 for running; and the vehicle visible window 400 of the embodiment of the present application, the vehicle visible window 400 is mounted on the vehicle body 510.

Alternatively, the vehicle 500 may be, but is not limited to, a car, off-road vehicle, van, truck, etc.

Alternatively, the vehicle body 510 may be, but is not limited to, a car body, an off-road vehicle body, a truck body, and the like.

Reference herein to "an embodiment" or "an implementation" means that a particular feature, structure, or characteristic described in connection with the embodiment can be included in at least one embodiment of the application. The appearances of the phrase in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. It is explicitly and implicitly understood by one skilled in the art that the embodiments described herein can be combined with other embodiments.

Finally, it should be noted that the above embodiments are only for illustrating the technical solutions of the present application and not for limiting, and although the present application is described in detail with reference to the above preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present application without departing from the spirit and scope of the technical solutions of the present application.

Claims

1. A laminated glass having a transparent conductive layer, comprising:

a first transparent substrate;

2. The laminated glass with a transparent conductive layer according to claim 1, wherein the extinction coefficient fluctuation Δ k of each of the sub-dielectric layers after the heat treatment is less than 0.001.

3. The laminated glass with a transparent conductive layer according to claim 1, wherein the four metal layers comprise a first metal layer, a second metal layer, a third metal layer and a fourth metal layer; the first metal layer, the second metal layer, the third metal layer and the fourth metal layer are sequentially arranged at intervals along the direction from the first transparent substrate to the second transparent substrate; the sum of the thicknesses of the second metal layer and the third metal layer is greater than the sum of the thicknesses of the first metal layer and the fourth metal layer.

4. The laminated glass with a transparent conductive layer according to claim 3, wherein the sum of the thicknesses of the second metal layer and the third metal layer is 1.1 to 1.8 times the sum of the thicknesses of the first metal layer and the fourth metal layer, and the thickness of the first metal layer is 5 to 20 nm; the thickness of the second metal layer is 5nm to 20 nm; the thickness of the third metal layer is 5nm to 20 nm; the thickness of the fourth metal layer is 5nm to 20 nm.

5. The laminated glass with the transparent conducting layer according to claim 1, wherein the five dielectric layers comprise a first dielectric layer, a second dielectric layer, a third dielectric layer, a fourth dielectric layer and a fifth dielectric layer, and the first dielectric layer, the second dielectric layer, the third dielectric layer, the fourth dielectric layer and the fifth dielectric layer are sequentially arranged at intervals along the direction from the first transparent substrate to the second transparent substrate; the thickness of the fourth dielectric layer is larger than that of the second dielectric layer, and the thickness of the second dielectric layer is larger than that of the third dielectric layer.

6. The laminated glass having a transparent conductive layer according to claim 5, wherein a material of each of the sub-dielectric layers is selected from an oxide, a nitride, or an oxynitride of at least one of Zn, Ti, Si, Al, Sn, Se, Zr, Ni, In, Cr, W, Ca, Y, Nb, Cu, Sm.

7. The laminated glass having a transparent conductive layer according to claim 5, wherein a material of the sub dielectric layer farthest from the first transparent substrate of at least one of the first dielectric layer, the second dielectric layer, the third dielectric layer, and the fourth dielectric layer is selected from an oxide of at least one of Zn, Ti, Si, Al, Sn, Se, Zr, Ni, In, Cr, W, Ca, Y, Nb, Cu, Sm.

8. The laminated glass with a transparent conductive layer according to any one of claims 1 to 7, wherein the color difference Δ E between any two points on the laminated glass with a transparent conductive layer is < 3.

9. The laminated glass with a transparent conductive layer according to any one of claims 1 to 7, wherein the laminated glass with a transparent conductive layer has a visible light transmittance of more than 70% and an infrared light transmittance of less than 3%, and the visible light reflectance of the surface of the second transparent substrate away from the adhesive layer is less than 15%.

10. The laminated glass having a transparent conductive layer according to any one of claims 1 to 7, wherein a first bus bar and a second bus bar electrically connected to the transparent conductive layer are further provided between the first transparent substrate and the second transparent substrate, and the transparent conductive layer has at least 600W/m between the first bus bar and the second bus bar²Heating power density of (1).

11. The laminated glass with a transparent conductive layer according to any one of claims 1 to 7, wherein the radius of curvature of the laminated glass with a transparent conductive layer in a predetermined direction is at least 6000mm, and the sheet resistance of the transparent conductive layer after the heat treatment is 0.6 Ω/□ or less.

12. A method for preparing laminated glass with a transparent conductive layer is characterized by comprising the following steps:

providing a first transparent substrate; and

carrying out heat treatment on a first transparent substrate with a transparent conducting layer within a preset temperature range, wherein the preset temperature range is 500-700 ℃, and the refractive index fluctuation deltan of each sub-dielectric layer after the heat treatment is less than 0.05; and

13. The method for preparing laminated glass with a transparent conductive layer according to claim 12, wherein the extinction coefficient fluctuation Δ k of each of the sub-dielectric layers after the heat treatment is less than 0.001.

14. The method according to claim 12, wherein the material of each of the sub-dielectric layers is selected from an oxide, nitride, or oxynitride of at least one of Zn, Ti, Si, Al, Sn, Se, Zr, Ni, In, Cr, W, Ca, Y, Nb, Cu, Sm.

15. The method for producing a laminated glass having a transparent conductive layer according to claim 12, wherein a material of at least one of the sub-medium layers is ZnSnOx, and when the material of the sub-medium layer is ZnSnOx, the deposition target material is a ZnSn alloy target, the deposition gas is argon and oxygen, and a flux ratio of argon and oxygen is 0.15 to 0.5.

16. The method according to claim 12, wherein the material of at least one of the sub-dielectric layers is AZO, and when the material of the sub-dielectric layer is AZO, the deposition target is an AZO ceramic target, the deposition gas is argon and oxygen, and the flux ratio of argon and oxygen is greater than 5.

17. The method according to claim 12, wherein the material of at least one of the sub-medium layers is TiOx, and when the material of the sub-medium layer is TiOx, the deposition target material is a TiOx ceramic target, the deposition gas is argon and oxygen, and the flux ratio of argon and oxygen is greater than 20.

18. The method for preparing laminated glass having a transparent conductive layer according to claim 12, wherein at least one of the sub-dielectric layers is SiZrN or SiAlN, and when the sub-dielectric layer is SiZrN or SiAlN, the deposition target is a SiZr alloy target or a SiAl alloy target, the deposition gas is argon and nitrogen, and the flux ratio of argon and nitrogen is 0.2-1.5.