CN113896432B

CN113896432B - Coated automobile glass

Info

Publication number: CN113896432B
Application number: CN202111211559.5A
Authority: CN
Inventors: 季亚林
Original assignee: Shanghai Boguang Technology Partnership LP
Current assignee: Shanghai Boguang Technology Partnership LP
Priority date: 2021-10-18
Filing date: 2021-10-18
Publication date: 2024-03-12
Anticipated expiration: 2041-10-18
Also published as: CN113896432A

Abstract

The invention relates to coated automotive glass, and belongs to the technical field of glass. The coated automotive glass comprises inner piece glass, outer piece glass arranged on the inner piece glass and an intermediate layer arranged between the inner piece glass and the outer piece glass; the inner surface of the outer piece of 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 piece of glass. The coated automobile glass adopts proper film materials, film system structures and coating processes, the coated glass can form a standard windshield through general cleaning, hot bending or bending tempering and interlayer working procedures, and finally the finally realized windshield can realize the visible light transmittance of more than 70 percent and T simultaneously _TS ≤40％。

Description

Coated automobile glass

Technical Field

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

Background

With the advancement of society and the attention of human beings to climate change, new energy vehicles represented by electric vehicles have become a future development trend to replace fuel vehicles. Whether for traditional fuel oil vehicle types or new energy vehicle types, saving energy consumption is always a long-lasting aim pursued by 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, so that the load of air conditioning refrigeration is an important aspect of energy consumption of the vehicle. On the basis that oil consumption is saved to reduce emission and vehicle cost like the traditional vehicle type, new energy vehicles, particularly electric vehicles, are more required to reduce the power consumption of an air conditioner by greatly reducing solar energy entering the vehicle so as to realize longer driving mileage. Typical automotive windshields are formed by hot bending two thin glass interlayers with a total solar energy transmittance T _TS About 80%. The large amount of energy is transmitted through the glass into the vehicle, so that not only is the air conditioning load of the vehicle very large, but also the comfort of drivers and passengers is greatly sacrificed. Meanwhile, along with the intelligent progress of automobiles, the automobile is directly exposed to the middle part of the front windshield of the automobileElectronic devices and chips integrated on consoles are more and more, and a large amount of direct sunlight energy can greatly improve the temperature of the center console, so that a plurality of electronic chips face a working environment with higher temperature to reduce or even lose performance.

In China, the reduction of energy consumption and the improvement of comfort are mainly realized by attaching a film for heat reflection or heat absorption to the inner side of automobile glass to reduce the total transmittance of the whole solar energy. T-shape of the windshield can be realized by sticking films with different grades _TS The temperature is reduced to 79 to 55 percent or so. For the front windshield film sticking technology commonly adopted in China, if T is needed _TS The further reduction can lead the visible light transmittance of the front windshield of the film to not reach the forced safety standard of the windshield, which is also one of the reasons why the film is not adopted in domestic automobiles in developed countries in Europe and America. Another approach is to use a special coated heat reflective glass for one of the two glass sheets that make up the windshield to achieve control of the total solar energy transmission. Patent CN200720190638.1 discloses that high infrared reflection and uv blocking are achieved by using 5 metal, oxide and sulfide layers plated on the glass to achieve a 2-4 ohm sheet resistance. Patent CN200620059916.5 discloses a thermally reflective coated glass containing a nano-sized single silver layer and a double silver layer suitable for automotive applications. T of a windshield by using such single and double silver layers _TS 55% -60% and 45% -55% can be achieved respectively. However, this still does not reach the first level of total solar transmittance in QC/T985-2014, namely T _TS Less than or equal to 40 percent. After the coated glass is processed into a finished windshield, the service life of the coated glass is the same as that of a common windshield and is far longer than the common quality assurance life of 5 years of glass film. However, before coated glass is processed into a laminated windshield for practical use, the coated glass is generally a so-called "soft film" because it is a silver layer excellent in optical properties to achieve high infrared reflection, and its processability resistance is poor, which limits its use.

Disclosure of Invention

In order to solve the technical problems, the invention provides coated automotive glass. Plating a coating film on the inner surface of the outer glass sheet by vacuum magnetron sputtering technologyA layer for realizing visible light transmittance of more than 70% and T _TS Less than or equal to 40 percent so as to meet the energy consumption control requirement of new energy automobiles, in particular electric automobiles. Meanwhile, the coated glass has good processing resistance and is easy to process into a standard hot-bending sandwich automobile windshield.

A coated automotive 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 piece of 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 piece of glass.

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

Further, the metal sacrificial layer is titanium or titanium-based alloy with the thickness of 0.5-5 nm; the titanium-based alloy is titanium-aluminum alloy, titanium-zirconium alloy or titanium-nickel alloy, wherein the contents of aluminum, zirconium and nickel are respectively not more than 20wt%, 40wt% and 80wt%. The main function of the metal sacrificial layer is to protect the functional layer from damage during subsequent coating and processing processes involving severe conditions such as high temperature, bending, etc., such as oxidation, water vapor attack and island aggregation of the functional layer.

Further, the fourth composite layer comprises a fourth upper oxide protection layer, the fourth upper oxide protection layer is 0.5-5nm thick titanium zirconium oxide, and the content of the zirconium oxide is not more than 40wt%. The oxide protective layer may provide further protection of the entire film structure during subsequent processing and use. The thin-layer titanium zirconium 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, wherein the first oxide layer is adjacent to the outer glass sheet, the first upper oxide seed layer is adjacent to the first metal functional layer, and the first dielectric layer is positioned between the first oxide layer and the first upper oxide seed layer.

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

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

Further, the regulating layer is zinc tin oxide with the thickness of 30-100nm, and the content of zinc oxide is 30-60wt%. The conditioning layer is used for optical interference conditioning and is typically 2-6 times the thickness of the dielectric layer in order to achieve the desired optical properties.

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

Further, the oxide seed layer is aluminum-doped zinc oxide with the thickness of 5-20nm, and the content of aluminum in the zinc oxide is 1-5%wt. The oxide seed layer primarily functions to provide a better crystallization 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 plays a role in preventing small-diameter metal atoms in glass and water vapor, oxygen and the like at 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.

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

Further, the interlayer is a PVB film.

Further, 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 a film system, and in order to realize high visible light transmittance and high infrared reflectivity 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 simultaneously realize low T _TS And high transmittance of visible light. Silver is an excellent low-resistivity infrared reflecting material, and silver films containing single-layer or multi-layer nano-size are widely used in the field of architectural glass to achieve sun shading effects. Based on the patent ZL200620059916.5, a lower T is realized _TS Films containing more layers of silver are of course oriented. Coated windshields using three silver films are disclosed in both patent CN101228098B and CN1111761894ATo realize a windshield having electrically heatable performance. However, the thickening of the silver layer inevitably brings about a decrease in visible light transmittance, while ensuring the transmittance of visible light>Achieving as low a T as possible on a 70% basis _TS It is not sufficient to simply increase the thickness of the silver layer. The invention adopts krypton or argon krypton mixed gas to further improve the crystallization performance of the silver film deposited by sputtering. Thus, a thinner physical thickness but better crystallization of the silver or silver alloy layer can be achieved to achieve better infrared reflection. By adding a small amount of aluminum into silver, the roughness of the functional layer with nano-scale thickness can be reduced on the basis of not sacrificing the function of the silver layer, and the processing resistance and the electromagnetic radiation reflection of the whole film system are further improved.

(2) The metal functional layer of the coated automotive glass adopts silver or silver-aluminum alloy, but the silver film material is easy to oxidize and tends to form an island growth mode on an oxide substrate, so that the silver layer loses the high infrared reflection function. In patent CN1133336452A, CN112441751A, protection of Ag layer from damage during plating and subsequent processing by a barrier layer of NiCr alloy is disclosed, but NiCr or NiCrO formed after oxidation _x Absorption of visible and infrared light is such that it sacrifices the transmission of visible light. In CN101597143B, ti is used as a sacrificial layer to protect the Ag layer, which has less optical absorption after oxidation but has inferior processability resistance to film systems using NiCr barrier layers. According to the invention, the titanium aluminum, titanium zirconium and 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 coated automotive glass provided by the invention can provide further protection for the coated glass in subsequent processing and use by using the titanium zirconium oxide hardened protective layer. Thin layer of TiZrO _x The high-hardness and low-internal stress accumulation plastic 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 integral film system.

(4) The invention relates to a coated automotive glass, which is formed by coating 3 layers of silver or silver alloy structures on single-piece automotive float glass, and adopts proper film materials, film system structures and coating processesThe glass may be formed into a standard windshield by a common cleaning, hot bending or bent tempering, interlayer process. The finally realized windshield realizes the visible light transmittance of more than 70% and T simultaneously _TS ≤40％。

Drawings

In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings, in which:

FIG. 1 is a schematic view of the structure of a coated automotive glass according to the present invention.

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

Reference numerals illustrate: 1-inner glass, 2-interlayer (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 adjusting layer, 3.8-second upper oxide seed layer, 3.9-second metal functional layer, 3.10-second metal sacrificial layer, 3.11-third lower oxide seed layer, 3.12-third adjusting layer, 3.13-third upper oxide seed layer, 3.14-third metal functional layer, 3.15-third metal sacrificial layer, 3.16-fourth lower oxide seed layer, 3.17-fourth dielectric layer, 3.18-fourth upper oxide protective layer, 4-outer glass.

Detailed Description

The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.

Referring to fig. 1, a coated automotive glass comprises an inner piece of glass 1, an outer piece of glass 4 arranged on the inner piece of glass 1, and an intermediate layer 2 arranged between the inner piece of glass 1 and the outer piece of glass 4, wherein a coating layer 3 is arranged on the inner surface of the outer piece of glass 4, and referring to fig. 2, the coating 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 piece of glass 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, wherein 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 regulating layer 3.7 and a second upper oxide seed layer 3.8, wherein 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 regulating 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 regulating layer 3.12 and a third upper oxide seed layer 3.13, wherein 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 regulating 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, a fourth upper oxide protection layer 3.18, the fourth lower oxide seed layer 3.16 being adjacent to the third metal sacrificial layer 3.15, the fourth upper oxide protection layer 3.18 being adjacent to the intermediate layer 2, the fourth dielectric layer 3.17 being located between the fourth lower oxide seed layer 3.16 and the fourth upper oxide protection layer 3.18.

Example 1

A coated automobile glass comprises the following concrete steps:

outer sheet glass 4:2.1mm float glass;

coating layer 3: from the outer glass sheet to the inside, 150nm SiO is sequentially arranged ₂ 、28.7nm Si ₃ N ₄ 、10nm AZO、12.1nm Ag、0.5nm Ti _0.9 Al _0.1 、10nm AZO、73.2nm ZnSnO _x 、10nm AZO、12nm Ag、0.5nm Ti _0.9 Al _0.1 、10nm AZO、62.7nm ZnSnO _x 、10nm AZO、11nm Ag、0.5nm Ti _0.9 Al _0.1 、10nm AZO、36nm Si ₃ N ₄ 、2nm Ti _0.8 Zr _0.2 O ₂ ；

Intermediate layer 2:0.8mm PVB;

inner sheet glass 1:1.8mm float glass.

Ar is adopted in the sputtering process of silver _0.8 Kr _0.2 Mixed gas, znSnO _x And AZO is sputtered by a ceramic zinc-tin-oxygen 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 automotive glass can be prepared into a typical coated automotive 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 _TS 38.9%; the visible light reflectance was 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 comprises the following concrete steps:

outer sheet glass 4:2.1mm float glass;

coating layer 3: 300nm SiO from the outer glass sheet to the inner glass sheet ₂ (Al 2wt％，Y 0.1wt％)、29.6nm ZnSnO _x 、10nm AZO、13nm Ag _0.96 Al _0.04 、1nm Ti _0.8 Zr _0.2 、10nm AZO、73.4nm ZnSnO _x 、10nm AZO、12nm Ag _0.96 Al _0.04 、1nm Ti _0.8 Zr _0.2 、10nm AZO、62.2nm ZnSnO _x 、10nm AZO、12nm Ag _0.96 Al _0.04 、2nm Ti _0.8 Zr _0.2 、10nm AZO、25.3nm Si ₃ N ₄ 、4nm TiO ₂ ；

Intermediate layer 2:0.8mm PVB;

inner sheet glass 1:1.8mm float glass.

SiO ₂ (Al 2wt%, Y0.1 wt%) in Ar/O from SiAlY target ₂ Sputtering in atmosphere. Ar is adopted in the sputtering process of the silver-aluminum alloy _0.1 Kr _0.9 Mixed gas, znSnO _x And AZO is sputtered by a ceramic zinc-tin-oxygen 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 automotive glass can be prepared into a typical coated automotive 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 _TS 39.5%; the visible light reflectance was 14.6%; the ultraviolet transmittance is 0.16%; reflection color: a is-6 and b is-4.

It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.

Claims

1. A coated automotive 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 piece of 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 piece of 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 8wt%; the metal sacrificial layer is 0.5nm thick titanium-based alloy; the titanium-based alloy is a titanium-aluminum alloy, wherein the content of aluminum is not more than 20wt%; the fourth composite layer comprises a fourth upper oxide protective layer, wherein the fourth upper oxide protective layer is titanium zirconium oxide, and the content of the zirconium oxide is not more than 40wt%;

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 10-90%;

the second composite layer comprises a second lower oxide seed layer, a second regulating layer and a second upper oxide seed layer, wherein 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 regulating layer is positioned between the second lower oxide seed layer and the second upper oxide seed layer;

the third composite layer comprises a third lower oxide seed layer, a third regulating 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 regulating layer is positioned between the third lower oxide seed layer and the third upper oxide seed layer;

the regulating layer is zinc tin oxide with the thickness of 30-100nm, and the content of zinc oxide is 30-60wt%;

the visible light transmittance of the coated automobile glass is more than 70 percent and the total solar energy transmittance T _TS ≤40%。

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

3. The coated automotive glass according to 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 fourth composite layer further comprises a fourth lower oxide seed layer adjacent the third metal sacrificial 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.

5. The coated automotive glass according to claim 4, wherein the oxide seed layer is aluminum-doped zinc oxide having a thickness of 5-20nm, and the zinc oxide has an aluminum content of 1-5wt%.

6. The coated automotive glass according to claim 2 or 4, wherein the dielectric layer is silicon nitride or zinc tin oxide having a thickness of 10-60 nm.