CN113896432A

CN113896432A - Coated automobile glass

Info

Publication number: CN113896432A
Application number: CN202111211559.5A
Authority: CN
Inventors: 季亚林
Original assignee: Membrane Technology Shanghai Co ltd
Current assignee: Shanghai Boguang Technology Partnership LP
Priority date: 2021-10-18
Filing date: 2021-10-18
Publication date: 2022-01-07
Anticipated expiration: 2041-10-18
Also published as: CN113896432B

Abstract

The invention relates to coated automobile glass, and belongs to the technical field of glass. The coated automobile glass comprises an inner piece of glass, an outer piece of glass arranged on the inner piece of glass, and an intermediate layer arranged between the inner piece of glass and the outer piece of glass; the inner surface of the outer glass is provided with a coating layer, and the coating layer comprises a first composite layer, a first metal functional layer, a first metal sacrificial layer, a second composite layer, a second metal functional layer and a second metal which are sequentially arranged on the outer glassThe composite structure comprises a sacrificial layer, a third composite layer, a third metal functional layer, a third metal sacrificial layer and a fourth composite layer. The coated automobile glass adopts a proper film layer material, a film system structure and a coating process, the coated glass can form standard windshield glass through general procedures of cleaning, hot bending or bending tempering and interlayer, and finally the finished windshield glass simultaneously realizes that the visible light transmittance is more than 70 percent and the T value is larger than the T value_TS≤40％。

Description

Coated automobile glass

Technical Field

The invention relates to the technical field of glass, in particular to coated automobile glass.

Background

With followingDue to social progress and concern of human beings on climate change, the replacement of fuel vehicles by new energy vehicles represented by electric vehicles has become a development trend in the future. No matter for a traditional fuel vehicle type or a new energy vehicle type, energy consumption saving is always a long-term and lasting pursuit target of the automobile industry. Since the conventional glass does not have a good function of isolating heat (near infrared) in sunlight, a large amount of heat can enter the vehicle through the glass, and therefore, the load of air conditioning refrigeration is an important aspect of the energy consumption of the vehicle. On the basis that similar to the traditional vehicle type, the fuel consumption needs to be saved so as to reduce the emission and the vehicle cost, the new energy vehicle, particularly the electric vehicle, needs to reduce the power consumption of an air conditioner by greatly reducing the solar energy entering the vehicle so as to realize longer driving mileage. A typical automotive windshield is formed by hot bending two thin glass plies, the solar energy total transmittance T of which_TSAbout 80%. Thus, a large amount of energy enters the vehicle through the glass, so that the load of the air conditioner for the vehicle is large, and the comfort of drivers and passengers is greatly sacrificed. Meanwhile, with the intelligent progress of automobiles, more and more electronic devices and chips are integrated on a center console directly exposed under the front windshield of the automobile, and a large amount of direct sunlight energy can greatly improve the temperature of the center console, so that a lot of electronic chips face a higher-temperature working environment and reduce or even lose performance.

In china, the reduction of energy consumption and the improvement of comfort are mainly achieved by sticking a heat-reflecting or heat-absorbing film on the inner side of automobile glass to reduce the total transmittance of solar energy. By sticking films of different grades, T of the windshield can be realized_TSReduce to 79-55%. For the front wind-shielding film pasting technology commonly adopted in China, if T is needed_TSStill further reduction will make the visible light transmittance of the front windshield of the film-coated glass fail to meet the mandatory safety standard of the windshield, which is also one of the reasons why the household automobiles in developed countries in europe and america generally do not adopt the film-coated. Another approach is to use a special coated heat reflective glass in one of the two sheets of glass that make up the windshield to achieve total solar transmission control. Patent CN200720190638.1 discloses the realization of 2-4 by plating 5 layers of metal, oxide and sulfide on glassOhmic surface resistance to achieve high infrared reflection and ultraviolet blocking. Patent CN200620059916.5 discloses a heat reflective coated glass containing nano-scale single and double silver layers suitable for automotive applications. T-shape of windshield by using such single silver layer and double silver layer_TSCan respectively reach 55 to 60 percent and 45 to 55 percent. However, the total solar transmittance in QC/T985-2014 cannot be achieved by one grade, namely T_TSLess than or equal to 40 percent. After the coated glass is processed into finished windshield glass, the service life of the coated glass is the same as that of common windshield glass, and is far longer than the common 5-year quality guarantee life of glass film sticking. However, before the coated glass is processed into a laminated windshield for practical use, since the coated glass generally realizes high infrared reflection by a silver layer having excellent optical properties, it is a so-called "soft film", and its processability is poor, limiting its use.

Disclosure of Invention

In order to solve the technical problem, the invention provides coated automobile glass. Coating a coating film layer on the inner surface of the outer glass by a vacuum magnetron sputtering technology to realize that the visible light transmittance is more than 70 percent and T is_TSLess than or equal to 40 percent so as to meet the energy consumption control requirement of new energy automobiles, particularly electric automobiles. Meanwhile, the coated glass has good processing resistance and can be easily processed into a standard hot bending sandwich automobile windshield.

A coated automobile glass comprises an inner glass sheet, an outer glass sheet arranged on the inner glass sheet and an intermediate layer arranged between the inner glass sheet and the outer glass sheet; the inner surface of the outer glass is provided with a coating layer, and the coating layer comprises a first composite layer, a first metal functional layer, a first metal sacrificial layer, a second composite layer, a second metal functional layer, a second metal sacrificial layer, a third composite layer, a third metal functional layer, a third metal sacrificial layer and a fourth composite layer which are sequentially arranged on the outer glass.

Further, the metal functional layer is 5-25nm thick silver or silver-aluminum alloy, and the content of aluminum in the silver-aluminum alloy is not more than 8 wt%.

Further, the metal sacrificial layer is titanium or titanium-based alloy with the thickness of 0.5-5 nm; the titanium-based alloy is a titanium-aluminum alloy, a titanium-zirconium alloy or a titanium-nickel alloy, wherein the contents of aluminum, zirconium and nickel are respectively not more than 20 wt%, 40 wt% and 80 wt%. The metal sacrificial layer has the main function of protecting the functional layer from being damaged in the subsequent coating and processing processes under severe conditions including high temperature, bending and the like, such as oxidation, water vapor attack and island-shaped aggregation of the functional layer.

Further, the fourth composite layer includes a fourth upper oxide protective layer of 0.5-5nm thick zirconium titanium oxide having a zirconium oxide content of not more than 40 wt%. The oxide protective layer may provide further protection of the overall film system structure during subsequent processing and use. The thin-layer zirconium titanium oxide has the characteristics of high hardness and low internal stress accumulation, and can improve the mechanical scratch resistance, high temperature resistance, bending resistance and oxidation resistance of the whole film system.

Further, the first composite layer comprises a first oxide layer, a first dielectric layer and a first upper oxide seed layer, the first oxide layer is adjacent to the outer glass, the first upper oxide seed layer is adjacent to the first metal functional layer, and the first dielectric layer is located between the first oxide layer and the first upper oxide seed layer.

Further, the first oxide layer is silicon dioxide or metal-doped silicon dioxide with the thickness of 50-2000 nm; the metal is one or more of aluminum, yttrium, cerium and lanthanum. Because the optical constant of the glass is almost consistent with that of the glass and the glass does not contain other metal impurities which can damage the functional layer, ions with small diameter in the glass and surface defects of the glass can be prevented from diffusing into a subsequent film layer when the glass is subjected to high-temperature hot bending and interlayer on the basis of not influencing any performance of a film system, so that the function of the film layer is prevented from being damaged, and the processing resistance of the glass during subsequent hot processing is improved.

Further, the second composite layer includes a second lower oxide seed layer, a second adjustment layer, and a second upper oxide seed layer, the second lower oxide seed layer is adjacent to the first metal sacrificial layer, the second upper oxide seed layer is adjacent to the second metal functional layer, and the second adjustment layer is located between the second lower oxide seed layer and the second upper oxide seed layer.

Further, the third composite layer includes a third lower oxide seed layer, a third adjustment layer, and a third upper oxide seed layer, the third lower oxide seed layer is adjacent to the second metal sacrificial layer, the third upper oxide seed layer is adjacent to the third metal functional layer, and the third adjustment layer is located between the third lower oxide seed layer and the third upper oxide seed layer.

Furthermore, the adjusting layer is zinc tin oxide with the thickness of 30-100nm, and the content of the zinc oxide is 30-60 wt%. The adjusting layer is used for optical interference adjustment, and in order to achieve a predetermined optical property, the thickness of the adjusting layer is typically 2 to 6 times the thickness of the dielectric layer.

Further, the fourth composite layer further includes a fourth lower oxide seed layer and a fourth dielectric layer, the fourth lower oxide seed layer is adjacent to the third metal sacrificial layer, the fourth upper oxide protective layer is adjacent to the intermediate layer, and the fourth dielectric layer is located between the fourth lower oxide seed layer and the fourth upper oxide protective layer.

Further, the oxide seed layer is 5-20nm thick aluminum-doped zinc oxide, and the content of aluminum in the zinc oxide is 1-5% wt. The oxide seed layer mainly functions to provide a better crystalline surface for the functional layer.

Further, the dielectric layer is silicon nitride or zinc tin oxide with the thickness of 10-60 nm. The dielectric layer is used for optical interference adjustment, and further prevents small-diameter metal atoms in the glass and water vapor, oxygen and the like on the top of the film layer from diffusing into the film layer at high temperature, so that the metal functional layer is protected from being damaged easily.

Further, the outer sheet of glass and the inner sheet of glass are automotive-grade float glass, and the thickness of the float glass is 1.2-2.5 mm.

Further, the interlayer is a PVB film.

Furthermore, each layer of the coating layer is sequentially coated by utilizing a magnetron sputtering technology; the metal functional layer is plated under the atmosphere of argon-krypton mixed gas; the content of krypton in the argon-krypton mixed gas is 10-100%. The metal functional layer is a key layer for realizing high infrared reflection of the film system, and in order to realize high visible light transmittance and high infrared reflectance of the whole glass, argon krypton mixed gas is used as sputtering process gas in the sputtering preparation process.

Compared with the prior art, the technical scheme of the invention has the following advantages:

(1) the metal functional layer of the coated automobile glass adopts silver or silver-aluminum alloy as the infrared reflection functional layer to realize low T simultaneously_TSAnd high visible light transmittance. Silver is an infrared reflecting material with excellent low resistivity, and comprises a single-layer or multi-layer nano-sized silver film which is widely applied to the field of building glass to realize the sun-shading effect. On the basis of patent ZL200620059916.5, lower T is to be realized_TSThe film containing more layers of silver is in one direction of course. The realization of a windscreen with electrically heatable properties by means of a coated windscreen comprising three silver layers is disclosed in patents CN101228098B and CN 1111761894A. However, thickening the silver layer inevitably brings about a decrease in visible light transmittance, and ensures the visible light transmittance>Achieving as low a T as possible on a 70% basis_TSSimply increasing the thickness of the silver layer is not sufficient. The invention adopts krypton gas or argon krypton mixed gas to further improve the crystallization performance of the silver film deposited by sputtering. A silver or silver alloy layer of thinner physical thickness but better crystallization can thereby be achieved to achieve better infrared reflection. A small amount of aluminum is doped in silver, so that the roughness of the functional layer with the nanometer-level thickness can be reduced on the basis of not sacrificing the function of the silver layer, and the processing resistance and the reflection of electromagnetic radiation of the whole film system are further improved.

(2) The metal functional layer of the coated automobile glass adopts silver or silver-aluminum alloy, but the silver film material is easy to oxidize and tends to an island-shaped growth mode on an oxide substrate, so that the silver layer loses the high infrared reflection function. The use of a NiCr alloy barrier layer to protect the Ag layer from being damaged during coating and subsequent processing is disclosed in patents CN1133336452A, CN112441751ABad, but NiCr or NiCrO formed after oxidation_xAbsorption of visible and infrared is such that it sacrifices visible light transmittance. Patent CN101597143B discloses protecting Ag layer with Ti as sacrificial layer, which has low optical absorption after oxidation but inferior processing resistance to film system using NiCr barrier layer. According to the invention, the titanium aluminum, the titanium zirconium and the titanium nickel alloy are used as the metal sacrificial layer to protect the metal functional layer, and the processing resistance of the coated glass is improved on the basis of ensuring the optical performance.

(3) The titanium zirconium oxide hardened protective layer used by the coated automobile glass can provide further protection for the coated glass in subsequent processing and use. Thin layer of TiZrO_xThe high-hardness and low-internal-stress-accumulation-type high-hardness anti-oxidation film has the characteristics of high hardness and low internal stress accumulation, and can improve the mechanical scratch resistance, high temperature resistance, bending resistance and oxidation resistance of the whole film system.

(4) The coated automobile glass is a structure comprising 3 layers of silver or silver alloy coated on a single piece of automobile-grade float glass, and adopts a proper film material, a film system structure and a coating process, so that the coated glass can form a standard windshield through general cleaning, hot bending or bending tempering and interlayer processes. The finally realized windshield simultaneously realizes the visible light transmittance of more than 70 percent and T_TS≤40％。

Drawings

In order that the present disclosure may be more readily and clearly understood, reference is now made to the following detailed description of the present disclosure taken in conjunction with the accompanying drawings, in which:

FIG. 1 is a schematic structural view of the coated automotive glass of the present invention.

FIG. 2 is a schematic view of the structure of a coating layer in the structure of the coated automotive glass of the present invention.

Description of reference numerals: 1-inner glass, 2-middle layer (PVB film), 3-coating layer, 3.1-first oxide layer, 3.2-first dielectric layer, 3.3-first upper oxide seed layer, 3.4-first metal functional layer, 3.5-first metal sacrificial layer, 3.6-second lower oxide seed layer, 3.7-second regulating layer, 3.8-second upper oxide seed layer, 3.9-a second metal functional layer, 3.10-a second metal sacrificial layer, 3.11-a third lower oxide seed layer, 3.12-a third adjusting layer, 3.13-a third upper oxide seed layer, 3.14-a third metal functional layer, 3.15-a third metal sacrificial layer, 3.16-a fourth lower oxide seed layer, 3.17-a fourth dielectric layer, 3.18-a fourth upper oxide protective layer and 4-outer glass.

Detailed Description

The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.

Referring to fig. 1, the coated automobile glass comprises an inner glass sheet 1, an outer glass sheet 4 arranged on the inner glass sheet 1 and an intermediate layer 2 arranged between the inner glass sheet 1 and the outer glass sheet 4, wherein a coated layer 3 is arranged on the inner surface of the outer glass sheet 4, and as shown in fig. 2, the coated layer 3 comprises a first composite layer, a first metal functional layer 3.4, a first metal sacrificial layer 3.5, a second composite layer, a second metal functional layer 3.9, a second metal sacrificial layer 3.10, a third composite layer, a third metal functional layer 3.14, a third metal sacrificial layer 3.15 and a fourth composite layer which are sequentially arranged on the outer glass sheet 4;

the first composite layer comprises a first oxide layer 3.1, a first dielectric layer 3.2 and a first upper oxide seed layer 3.3, the first oxide layer 3.1 is adjacent to the outer glass 4, the first upper oxide seed layer 3.3 is adjacent to the first metal functional layer 3.4, and the first dielectric layer 3.2 is positioned between the first oxide layer 3.1 and the first upper oxide seed layer 3.3;

the second composite layer comprises a second lower oxide seed layer 3.6, a second adjusting layer 3.7 and a second upper oxide seed layer 3.8, the second lower oxide seed layer 3.6 is adjacent to the first metal sacrificial layer 3.5, the second upper oxide seed layer 3.8 is adjacent to the second metal functional layer 3.9, and the second adjusting layer 3.7 is positioned between the second lower oxide seed layer 3.6 and the second upper oxide seed layer 3.8;

the third composite layer comprises a third lower oxide seed layer 3.11, a third adjusting layer 3.12 and a third upper oxide seed layer 3.13, the third lower oxide seed layer 3.11 is adjacent to the second metal sacrificial layer 3.10, the third upper oxide seed layer is adjacent to the third metal functional layer 3.14, and the third adjusting layer 3.12 is positioned between the third lower oxide seed layer 3.11 and the third upper oxide seed layer 3.13;

the fourth composite layer comprises a fourth lower oxide seed layer 3.16, a fourth dielectric layer 3.17 and a fourth upper oxide protective layer 3.18, the fourth lower oxide seed layer 3.16 is adjacent to the third metal sacrificial layer 3.15, the fourth upper oxide protective layer 3.18 is adjacent to the intermediate layer 2, and the fourth dielectric layer 3.17 is located between the fourth lower oxide seed layer 3.16 and the fourth upper oxide protective layer 3.18.

Example 1

A coated automobile glass is specifically as follows:

outer sheet glass 4: 2.1mm float glass;

coating a film layer 3: 150nm SiO is arranged from the outer glass sheet to the inner₂、28.7nm Si₃N₄、10nm AZO、12.1nm Ag、0.5nm Ti_0.9Al_0.1、10nm AZO、73.2nm ZnSnO_x、10nm AZO、12nm Ag、0.5nm Ti_0.9Al_0.1、10nm AZO、62.7nm ZnSnO_x、10nm AZO、11nm Ag、0.5nm Ti_0.9Al_0.1、10nm AZO、36nm Si₃N₄、2nm Ti_0.8Zr_0.2O₂；

Intermediate layer 2: 0.8mm PVB;

inner sheet glass 1: 1.8mm float glass.

The sputtering process of silver adopts Ar_0.8Kr_0.2Mixed gas, ZnSnO_xAnd AZO is sputtered from a ceramic zinc tin oxide target and a ceramic zinc aluminum oxide target. The Ag alloy and the Ti alloy are respectively obtained by sputtering corresponding alloy targets. The coated automobile glass can be prepared into a typical coated automobile glass structure through standard glass processing processes such as edge film removal, cleaning, hot bending, interlayer and the like. The optical test results were: the visible light transmittance is 71.2%; total solar transmittance T_TS38.9 percent; the visible light reflectivity is 15.9%; the ultraviolet transmittance is 0.15%; reflection color: a is-4.2 and b is-3.5.

Example 2

A coated automobile glass is specifically as follows:

outer sheet glass 4: 2.1mm float glass;

coating a film layer 3: 300nm SiO is arranged from the outer glass sheet to the inner₂(Al 2wt％，Y 0.1wt％)、29.6nm ZnSnO_x、10nm AZO、13nm Ag_0.96Al_0.04、1nm Ti_0.8Zr_0.2、10nm AZO、73.4nm ZnSnO_x、10nm AZO、12nm Ag_0.96Al_0.04、1nm Ti_0.8Zr_0.2、10nm AZO、62.2nm ZnSnO_x、10nm AZO、12nm Ag_0.96Al_0.04、2nm Ti_0.8Zr_0.2、10nm AZO、25.3nm Si₃N₄、4nm TiO₂；

Intermediate layer 2: 0.8mm PVB;

inner sheet glass 1: 1.8mm float glass.

SiO₂(Al 2 wt%, Y0.1 wt%) in Ar/O from SiAlY target₂Sputtering in atmosphere. The sputtering process of the silver-aluminum alloy adopts Ar_0.1Kr_0.9Mixed gas, ZnSnO_xAnd AZO is sputtered from a ceramic zinc tin oxide target and a ceramic zinc aluminum oxide target. The Ag alloy and the Ti alloy are respectively obtained by sputtering corresponding alloy targets. The coated automobile glass can be prepared into a typical coated automobile glass structure through standard glass processing processes such as edge film removal, cleaning, hot bending, interlayer and the like. The optical test results were: the visible light transmittance is 70.7%; total solar transmittance T_TS39.5%; the visible light reflectivity is 14.6%; the ultraviolet transmittance is 0.16%; reflection color: a is-6 and b is-4.

It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.

Claims

1. A coated automobile glass comprises an inner glass sheet, an outer glass sheet arranged on the inner glass sheet and an intermediate layer arranged between the inner glass sheet and the outer glass sheet; the inner surface of the outer glass is provided with a coating layer, and the coating layer is characterized by comprising a first composite layer, a first metal functional layer, a first metal sacrificial layer, a second composite layer, a second metal functional layer, a second metal sacrificial layer, a third composite layer, a third metal functional layer, a third metal sacrificial layer and a fourth composite layer which are sequentially arranged on the outer glass; the metal functional layer is silver or silver-aluminum alloy, and the content of aluminum in the silver-aluminum alloy is not more than 8 wt%; the metal sacrificial layer is titanium or titanium-based alloy; the titanium-based alloy is a titanium-aluminum alloy, a titanium-zirconium alloy or a titanium-nickel alloy, wherein the contents of aluminum, zirconium and nickel are respectively not more than 20 wt%, 40 wt% and 80 wt%; the fourth composite layer comprises a fourth upper oxide protective layer, the fourth upper oxide protective layer is zirconium titanium oxide, and the content of zirconium oxide is not more than 40 wt%.

2. The coated automotive glass of claim 1, wherein the first composite layer comprises a first oxide layer adjacent the outer sheet glass, a first dielectric layer adjacent the first metal functional layer, and a first upper oxide seed layer between the first oxide layer and the first upper oxide seed layer.

3. The coated automotive glass of claim 2, wherein the first oxide layer is silica or metal-doped silica having a thickness of 50-2000 nm; the metal is one or more of aluminum, yttrium, cerium and lanthanum.

4. The coated automotive glass of claim 1, wherein the second composite layer comprises a second lower oxide seed layer adjacent the first metal sacrificial layer, a second upper oxide seed layer adjacent the second metal functional layer, and a second adjustment layer between the second lower oxide seed layer and the second upper oxide seed layer.

5. The coated automotive glass of claim 1, wherein the third composite layer comprises a third lower oxide seed layer adjacent the second sacrificial metal layer, a third upper oxide seed layer adjacent the third functional metal layer, and a third upper oxide seed layer between the third lower oxide seed layer and the third upper oxide seed layer.

6. The coated automotive glass of claim 4 or 5, wherein the modifying layer is zinc tin oxide having a thickness of 30-100nm and a zinc oxide content of 30-60 wt%.

7. The coated automotive glass of claim 1, wherein the fourth composite layer further comprises a fourth lower oxide seed layer adjacent the third sacrificial metal layer, a fourth upper oxide protective layer adjacent the intermediate layer, and a fourth dielectric layer between the fourth lower oxide seed layer and the fourth upper oxide protective layer.

8. The coated automotive glass of any one of claims 4, 5 and 7, wherein the oxide seed layer is aluminum-doped zinc oxide with a thickness of 5-20nm, and the aluminum content in the zinc oxide is 1-5% wt.

9. The coated automotive glass of claim 2 or 7, wherein the dielectric layer is silicon nitride or zinc tin oxide having a thickness of 10-60 nm.

10. The coated automotive glass of claim 1, wherein each of the coating layers is sequentially coated using a magnetron sputtering technique; the metal functional layer is plated under the atmosphere of argon-krypton mixed gas; the content of krypton in the argon-krypton mixed gas is 10-100%.