WO2021253549A1

WO2021253549A1 - Film-coated glass and manufacturing method therefor

Info

Publication number: WO2021253549A1
Application number: PCT/CN2020/101930
Authority: WO
Inventors: 曾小绵; 白振中
Original assignee: 广东旗滨节能玻璃有限公司; 深圳市新旗滨科技有限公司
Priority date: 2020-06-19
Filing date: 2020-07-14
Publication date: 2021-12-23
Also published as: CN111559875A

Abstract

A film-coated glass and a manufacturing method therefor. The glass comprises: a glass substrate; a functional film series layer, deposited on the surface of the glass substrate; a silicon-zirconium-aluminum nitride layer, deposited on the surface of the functional film series layer, where the silicon-zirconium-aluminum nitride layer is formed by magnetron sputtering deposition of a silicon-zirconium-aluminum ternary material as a target material in a nitrogen-containing atmosphere. The composition and weight percentage of the silicon-zirconium-aluminum ternary material are: 12-16% of Zr, 5-7% of Al, and the remainder being Si and unavoidable impurities. The silicon-zirconium-aluminum nitride layer is provided with excellent oxidation resistance, wear resistance, wipe resistance, and acid resistance at the same time, thus providing improved protection for the functional film series layer in the film-coated glass while the film-coated glass is being transported, stored, and processed. The present invention is applicable in protecting a double silver film-coated glass and a triple silver film-coated glass.

Description

Coated glass and preparation method thereof

This application claims: the priority of the Chinese patent application filed on June 19, 2020, with the application number 202010571822.0, and the title "a coated glass and its preparation method", which is hereby incorporated by reference.

Technical field

This application relates to the field of glass, in particular to a coated glass and a preparation method thereof.

Background technique

In the deep processing industry, the final use of traditional coated glass is insulating glass for building curtain walls. Coated glass is processed through multiple processes: usually including cutting, drilling, edging, tempering, film removal, hollowing, transfer between processes, etc. The film on the coated surface is usually impacted, wiped, exposed to moisture, and cleaned in the air. Water corrosion, long-term storage and oxidation, etc., are more or less severely damaged. Therefore, the outermost layer of coated glass is particularly important to enhance the protection against external corrosion. It must be improved, otherwise it will eventually affect the quality and production efficiency of the processed glass. cost.

There are reports in the related art using a _{mixture of SiN x} and ZrSiO _x N _y as the outermost film layer of the coated glass, and there are also reports using a silicon nitride zirconium aluminum layer as the outermost film layer of the coated glass.

However, in the process of implementing the embodiments of the present application, the applicant of the present application found that the above-mentioned technology has at least the following technical problems: the oxidation resistance, abrasion resistance, wipe resistance and acid resistance of the outermost film layer of the coated glass in the related art The performance needs to be improved. It cannot have excellent oxidation resistance, abrasion resistance, wipe resistance and acid resistance at the same time. These films can only be used to protect single silver coated glass, and cannot be used to protect double silver coated glass and triple silver coated glass. grass.

The above content is only used to assist the understanding of the technical solutions of this application, and does not mean that the above content is recognized as prior art.

The statements here only provide background information related to this application, and do not necessarily constitute prior art.

Technical solutions

This application proposes a coated glass and a preparation method thereof. The outermost layer of the coated glass is a silicon nitride zirconium aluminum layer. It is deposited by magnetron sputtering. The composition and weight percentage of the silicon-zirconium-aluminum ternary material are: Zr is 12-16%, Al is 5-7%, and the balance is Si and unavoidable impurities, so that The silicon nitride zirconium aluminum layer also has excellent oxidation resistance, abrasion resistance, wipe resistance and acid resistance, so that the coated glass can better protect the functional film system in the coated glass during transportation, storage and processing. Layer, can be used to protect double silver coated glass and triple silver coated glass.

This application is realized through the following technical solutions:

The first aspect of this application provides a coated glass, including:

Glass substrate

The functional film layer is deposited on the surface of the glass substrate;

The silicon-zirconium-aluminum layer is deposited on the surface of the functional film layer, wherein the silicon-zirconium-aluminum layer is deposited by magnetron sputtering in a nitrogen-containing atmosphere using a silicon-zirconium-aluminum ternary material as the target material The composition and weight percentage of the silicon-zirconium-aluminum ternary material are: Zr is 12-16%, Al is 5-7%, and the balance is Si and unavoidable impurities.

In one embodiment, the weight percentage of the unavoidable impurities is less than 3%.

In one embodiment, the thickness of the silicon nitride zirconium aluminum layer is 1-10 nm.

In one embodiment, the functional film layer is a low-emissivity film layer or a solar control film layer.

In one embodiment, the solar control film layer is composed of a dielectric layer and a functional layer; the low-emissivity film layer is composed of a dielectric layer, a barrier layer, and a functional layer.

In one embodiment, the functional layer in the solar control film layer is a single silver film layer, a double silver film layer, or a triple silver film layer; the functional layer in the low-E film layer is a single silver film layer, Double silver film layer or triple silver film layer.

According to another aspect of the present application, there is provided a method for preparing coated glass, including the following steps:

S1. Provide a glass substrate;

S2. Depositing a functional film layer on the surface of the glass substrate;

S3. Deposit a layer of silicon-zirconium-aluminum nitride on the surface of the functional film layer, wherein the layer of silicon-zirconium-aluminum nitride is a silicon-zirconium-aluminum ternary material as a target under a nitrogen-containing atmosphere by magnetron sputtering The composition and weight percentage of the silicon-zirconium-aluminum ternary material are: Zr is 12-16%, Al is 5-7%, and the balance is Si and unavoidable impurities.

In one embodiment, the vacuum degree of the nitrogen-containing atmosphere is 3×10 ^-3 to 5×10 ^-3 mbar, and the volume ratio of nitrogen and argon in the nitrogen-containing atmosphere is 1:1.2 to 1.5. The deposition power of magnetron sputtering is 50～70kW.

In one embodiment, a silicon nitride zirconium aluminum layer with a thickness of 1-10 nm is deposited on the surface of the functional film layer.

In one embodiment, the functional film layer is a solar control film layer or a low-emissivity film layer.

In one embodiment, when the functional film layer is a solar control film layer, the step of depositing the functional film layer on the surface of the glass substrate specifically includes: depositing a dielectric layer on the glass substrate, Functional layer; or, when the functional film layer is a low-emissivity film layer, the step of depositing a functional film layer on the surface of the glass substrate specifically includes: depositing a dielectric layer on the glass substrate, blocking Layer, functional layer.

In one embodiment, the target material is prepared by plasma spraying technology.

In this application, the outermost layer of the coated glass is a silicon nitride zirconium aluminum layer, and the silicon zirconium aluminum nitride layer is deposited by magnetron sputtering using silicon zirconium aluminum ternary material as the target material in a nitrogen-containing atmosphere The composition and weight percentage of the silicon-zirconium-aluminum ternary material are: Zr is 12-16%, Al is 5-7%, and the balance is Si and unavoidable impurities, so that the silicon nitride zirconium aluminum layer is simultaneously With excellent oxidation resistance, abrasion resistance, wipe resistance and acid resistance, the coated glass can better protect the functional film layer in the coated glass during transportation, storage and processing, and can be used to protect double silver Coated glass and triple silver coated glass.

Embodiments of the present invention

The raw materials and equipment used in this application, unless otherwise specified, are all commonly used raw materials and equipment in the field; the methods used in this application, unless otherwise specified, are all conventional methods in the field.

Unless otherwise specified, the meanings of terms in this specification are the same as those generally understood by those skilled in the art, but in case of conflict, the definitions in this specification shall prevail.

"Include", "include", "include", "include", "have" or other variations herein are intended to encompass non-closed inclusions, and no distinction is made between these terms. The term "comprising" means that other steps and ingredients that do not affect the final result can be added. The term "comprising" also includes the terms "consisting of" and "consisting essentially of". The compositions and methods/processes of the present application comprise, consist of, and consist essentially of the necessary elements and limitations described herein and any additional or optional ingredients, components, steps or limitations described herein.

All numerical values or expressions related to component amounts, process conditions, etc. used in the specification and claims should be understood to be modified by "about" in all cases. All ranges referring to the same components or properties include endpoints, which can be independently combined. Since these ranges are continuous, they include every value between the minimum and maximum values. It should also be understood that any numerical range cited in this application is intended to include all sub-ranges within that range.

As described in the background art, the oxidation resistance, abrasion resistance, wiping resistance and acid resistance of the outermost film layer of coated glass in the related art need to be improved, and they cannot have excellent oxidation resistance and abrasion resistance at the same time. , Wipe resistance and acid resistance. These films can only be used to protect single silver coated glass, but cannot be used to protect double silver coated glass and triple silver coated glass. However, the reason for this problem is not clear. Those skilled in the art have been committed to mixing multiple materials in the existing outermost layer, but did not realize that only the silicon nitride zirconium aluminum layer is used as the outermost layer of the coated glass. Controlling the weight ratio of the three components of silicon, zirconium, and aluminum in the silicon nitride zirconium aluminum layer will have a significant impact on the oxidation resistance, abrasion resistance, wipe resistance and acid resistance of the film. The applicant is surprised It is found that the silicon-zirconium-aluminum layer is used as the outermost film of the coated glass, and the silicon-zirconium-aluminum layer is deposited by magnetron sputtering using a silicon-zirconium-aluminum ternary material as a target in a nitrogen-containing atmosphere The composition and weight percentage of the silicon-zirconium-aluminum ternary material are: Zr is 12-16%, Al is 5-7%, and the balance is Si and unavoidable impurities, which overcomes this defect.

In the first aspect, this application provides a coated glass, including:

Glass substrate

The functional film layer is deposited on the surface of the glass substrate;

A silicon-zirconium-aluminum layer is deposited on the surface of the functional film system layer, wherein the silicon-zirconium-aluminum layer is deposited by magnetron sputtering in a nitrogen-containing atmosphere using a silicon-zirconium-aluminum ternary material as the target material The composition and weight percentage of the silicon-zirconium-aluminum ternary material are: Zr is 12-16%, Al is 5-7%, and the balance is Si and unavoidable impurities.

Although there are reports in the related art that the silicon nitride zirconium aluminum layer is used as the outermost film layer of the coated glass, the existing film layers do not specifically disclose the use of silicon zirconium aluminum ternary materials with a specific weight ratio as the target material. The silicon-zirconium-aluminum layer is deposited by magnetron sputtering in a nitrogen-containing atmosphere. The related technology does not record that only the silicon-zirconium-aluminum layer is used as the outermost film of the coated glass to control the silicon-zirconium-aluminum ternary material in the target material. The weight ratio will have a significant impact on the oxidation resistance, abrasion resistance, wipe resistance and acid resistance of the silicon nitride zirconium aluminum layer. However, the applicant of the present application has found through various research attempts that only the silicon nitride zirconium aluminum layer is used as the outermost film of the coated glass, and the silicon zirconium aluminum layer is based on the silicon zirconium aluminum ternary material as the target material. It is deposited by magnetron sputtering in a nitrogen-containing atmosphere. The composition and weight percentage of the silicon-zirconium-aluminum ternary material are: Zr is 12-16%, Al is 5-7%, and the balance is Si and unavoidable Impurities can control the weight ratio of the three components of silicon, zirconium, and aluminum in the silicon nitride zirconium aluminum layer to a specific range, resulting in complementary functions and synergy. The silicon nitride zirconium aluminum layer has higher permeability, It has good film compatibility with the functional film layer, and significantly improves the oxidation resistance, abrasion resistance, wipe resistance and acid resistance of the outermost film, so that the film has good oxidation resistance at the same time , Abrasion resistance, wipe resistance and acid resistance, and achieved unexpected technical effects.

In the embodiments of the present application, Zr is 12-16% by weight percentage, and typical but non-limiting weight percentages are 12%, 13%, 14%, 15%, or 16%.

In the embodiments of the present application, Al is 5 to 7% by weight percentage, and typical but non-limiting weight percentages are 5%, 5.5%, 6%, 6.5%, or 7%.

The applicant of this application has discovered in practice that zirconium Zr has a very sensitive ability to capture oxygen and nitrogen, and can form stable zirconium oxide wear resistance; the weight percentage of zirconium is less than 12%, which will affect silicon nitride, zirconium, aluminum The wear resistance of the layer; the weight percentage of zirconium is higher than 16%, which will change the refractive index of the silicon nitride zirconium aluminum layer, which is not conducive to the need for the refractive index of the film layer. Aluminum Al is conductive in the target material, which is good for sputtering of the target material, but aluminum Al is easy to combine with oxygen in the air, and this oxidation is not conducive to the stability of the film; the weight percentage of aluminum is less than 5%, which is not conducive to conductivity and affects the sputtering. Shot stability, the weight percentage of aluminum higher than 7% is not conducive to the stability of the film. In this application, the weight percentage of zirconium in the silicon-zirconium-aluminum ternary material is controlled to be higher than the weight percentage of aluminum, while the weight percentage of zirconium and the weight percentage of aluminum are controlled within a specific range, which can make silicon nitride zirconium aluminum The refractive index of the layer is moderate, the zirconium captures oxygen properly, the aluminum is conductive and easy to sputter, and the silicon nitride zirconium aluminum layer has good oxidation resistance, abrasion resistance, wipe resistance and acid resistance.

In addition, the silicon-zirconium-aluminum nitride layer described in the present application is deposited by magnetron sputtering in a nitrogen-containing atmosphere with a silicon-zirconium-aluminum ternary material as a target. In the present application, the silicon, zirconium, and zirconium in the target are controlled The weight ratio of aluminum also has an impact on the magnetron sputtering process. The weight ratio of silicon, zirconium, and aluminum in the target material is not within the scope of this application. During the sputtering process, if the power exceeds 50kW, the target material will easily drop slag, thus Affect the quality of the product film.

It should be noted that here, the unavoidable impurities refer to impurities that are inevitably mixed in the manufacturing process of each raw material even though they are not intentionally added. Examples of such impurities include B, etc., and their total sum is usually 0.3% by mass or less does not affect the effect of this application.

In the embodiment of the present application, the functional film layer is a low-emissivity film layer or a solar control film layer.

The solar control film layer is formed by depositing one or more layers of metal or compound thin films on the surface of the substrate. The main function is to control the reflection, transmission and absorption of direct solar radiation according to the required ratio, and to produce the required reflection color. It can effectively limit the incidence of solar radiation, and has obvious shading effect; it has colorful tones and satisfactory decorative effects; it has a good line of sight shielding function for indoor objects and building components; it has an ideal visible light transmission ratio and reflection Compare.

In the embodiments of the present application, the composition structure of the solar control film layer is not particularly limited, and the solar control film layer well known to those skilled in the art may be used. Preferably, the solar control film layer is composed of a dielectric layer, Functional layer stacking composition, the dielectric layer is generally metal oxide or metal nitride, or non-metal oxide or non-metal nitride, such as SiZrOx, TiO ₂ , ZnSnOx, SnO ₂ , ZnO, SiO ₂ , Ta ₂ O ₅ , SiNxOy, BiO ₂ , Al ₂ O ₃ , Nb ₂ O ₅ , Si ₃ N ₄ , AZO, etc., but not limited to this, it can also be other ones that are not listed in this embodiment but are used by the technology in the art Other dielectric materials well known to the person. The functional layer in the solar control film layer is a single silver film layer, a double silver film layer or a triple silver film layer; for a single silver film layer, it means that the functional layer contains only a single silver layer; for a double silver film layer, It means that the functional layer includes two silver layers; for the three-silver film layer, it means that the functional layer includes three silver layers; more specifically, the functional layer may contain a single layer of fine-grained silver, silver, aluminum, copper, or gold. The material can also contain a single layer of binary, or ternary, or quaternary materials composed of fine-grained silver, silver, aluminum, copper, gold and other materials, and can also contain double-layer fine-grained silver, silver, aluminum, copper, Or gold material, it can also contain two layers of binary, or ternary, or quaternary materials composed of fine-grained silver, silver, aluminum, copper, gold and other materials, and it can also contain three layers of fine-grained silver, silver, aluminum, Copper or gold materials may also contain three layers of binary, or ternary, or quaternary materials composed of fine-grained silver, silver, aluminum, copper, gold and other materials.

The low-emissivity film layer has a high reflectance of near-infrared and far-infrared with a wavelength range of 0.76μm-2.5μm (760nm-2500nm). The low-emissivity film layer can not only allow a large amount of solar energy and visible light to penetrate into the room, but also reflect more than 90% of the heat released by indoor objects and keep it indoors; it can also block ultraviolet rays from the outdoors and reduce the generation of indoor objects under sunlight. fade.

In the embodiments of the present application, there is no particular restriction on the composition structure of the low-e The barrier layer and the functional layer are superimposed. The dielectric layer, the barrier layer and the functional layer are respectively composed of one or more material film layers; the dielectric layer is generally metal oxide or metal nitride, or non-metallic Oxide or non-metallic nitride, such as SiZrO _x , TiO ₂ , ZnSnO _x , SnO ₂ , ZnO, SiO ₂ , Ta ₂ O ₅ , SiN _x O _y , BiO ₂ , Al ₂ O ₃ , Nb ₂ O ₅ , SiN _x, AZO and the like, but is not limited thereto, but may be other not listed but other dielectric materials are well known to those skilled in the embodiment in the present embodiment. The barrier layer material is NiCr, but is not limited to this, and can also be other barrier layer materials that are not listed in this embodiment but are well known to those skilled in the art. The functional layer in the low-e film system layer is a single silver film layer, a double silver film layer or a triple silver film layer; for a single silver film layer, it means that the functional layer contains only a single silver layer; for a double silver film layer, It means that the functional layer includes two silver layers; for the three-silver film layer, it means that the functional layer includes three silver layers; more specifically, the functional layer may contain a single layer of fine-grained silver, silver, aluminum, copper, or gold. The material can also contain a single layer of binary, or ternary, or quaternary materials composed of fine-grained silver, silver, aluminum, copper, gold and other materials, and can also contain double-layer fine-grained silver, silver, aluminum, copper, Or gold material, it can also contain two layers of binary, or ternary, or quaternary materials composed of fine-grained silver, silver, aluminum, copper, gold and other materials, and it can also contain three layers of fine-grained silver, silver, aluminum, Copper or gold materials may also contain three layers of binary, or ternary, or quaternary materials composed of fine-grained silver, silver, aluminum, copper, gold and other materials.

The present application does not have any special restrictions on the deposition method of the functional film layer, as long as it is a deposition method well known to those skilled in the art, for example: chemical or physical meteorological deposition method, vacuum ion number deposition method, sol-gel coating can be used Deposition method, magnetron sputtering method, online thermal spray decomposition method. Preferably, the functional film layer is deposited by magnetron sputtering.

In the second aspect, a method for preparing coated glass is provided, which includes the following steps:

S1. Provide a glass substrate;

S2. Depositing a functional film layer on the surface of the glass substrate;

In the embodiment of the present application, the target material is prepared by plasma spraying technology.

It should be noted that the composition and weight percentage of the target in this application are the same as the composition and weight percentage of the silicon-zirconium-aluminum ternary material in the finally formed silicon-zirconium-aluminum layer, so that when the target is used for magnetron sputtering , To obtain the required composition and weight percentage of the film layer.

In the related art, in the magnetron sputtering process, the weight ratio of each component in the target is usually not controlled, but by adjusting the magnetron sputtering process conditions, for example, by adjusting the installation angle of the target and/or the width of the baffle. Controlling the weight ratio of the components in the final formed film layer is complicated to operate, and the weight ratio of the components in the film layer is not easy to control. In this application, the silicon-zirconium-aluminum ternary material is creatively used as the target material to control the weight ratio of silicon, zirconium, and aluminum in the target material. There is no need to specially adjust the magnetron sputtering process conditions to deposit a specific weight ratio. The film layer, the weight ratio of each component in the film layer is easy to control.

Among them, the specific process and process parameters of the plasma spraying technology for preparing the target material are not particularly limited in the embodiments of the present application, and the treatment process well known to those skilled in the art can be used, and those skilled in the art can make selections and adjustments according to actual production conditions.

The specific process and process parameters of magnetron sputtering are not particularly limited in the embodiments of the present application, as long as the process is well known to those skilled in the art, and those skilled in the art can make selections and adjustments according to actual production conditions. Preferably, the vacuum degree of the nitrogen-containing atmosphere is 3×10 ^-3 to 5×10 ^-3 mbar, the volume ratio of nitrogen and argon in the nitrogen-containing atmosphere is 1:1.2 to 1.5, and the magnetron sputtering The deposition power of the jet is 50-70 kW, and a silicon nitride zirconium aluminum layer with a thickness of 1-10 nm is deposited on the surface of the functional film layer.

As mentioned above, the functional film layer is a solar control film layer or a low-emissivity film layer.

When the functional film layer is a solar control film layer, the step of depositing a functional film layer on the surface of the glass substrate specifically includes: depositing a dielectric layer and a functional layer on the glass substrate; or, when When the functional film layer is a low-emissivity film layer, the step of depositing a functional film layer on the surface of the glass substrate specifically includes: depositing a dielectric layer, a barrier layer, and a functional layer on the glass substrate.

In order to better understand the above-mentioned technical solutions, the above-mentioned technical solutions will be described in detail below in conjunction with specific examples. The examples are only preferred implementations of the present application and are not limited to the present application.

Example 1

A coated glass, including:

Glass substrate

The functional film layer is deposited on the surface of the glass substrate;

The silicon-zirconium-aluminum layer is deposited on the surface of the functional film layer, wherein the silicon-zirconium-aluminum layer is deposited by magnetron sputtering in a nitrogen-containing atmosphere using a silicon-zirconium-aluminum ternary material as the target material The composition and weight percentage of the silicon-zirconium-aluminum ternary material are: Zr is 14%, Al is 6%, and the balance is Si and unavoidable impurities.

The method for preparing the coated glass includes the following steps:

S1. Provide a glass substrate;

S2. Depositing a functional film layer on the surface of the glass substrate; the functional film layer includes a first dielectric layer, a first barrier layer, and a Functional layer, second barrier layer, second dielectric layer;

The material of the first dielectric layer is SiNx, and the thickness of the first dielectric layer is 36 nm;

The material of the first barrier layer is NiCr, and the thickness of the first barrier layer is 1.8 nm;

The material of the functional layer is Ag, and the thickness of the functional layer is 8 nm;

The material of the second barrier layer is NiCr, and the thickness of the second barrier layer is 2 nm;

The material of the second dielectric layer is SiNx, and the thickness of the second dielectric layer is 30 nm;

S3. Deposit a layer of silicon-zirconium-aluminum nitride on the surface of the functional film layer, wherein the layer of silicon-zirconium-aluminum nitride is a silicon-zirconium-aluminum ternary material as a target under a nitrogen-containing atmosphere by magnetron sputtering The vacuum degree of the nitrogen-containing atmosphere is 3×10 ^-3 to 5×10 ^-3 mbar, the volume ratio of nitrogen and argon in the nitrogen-containing atmosphere is 1:1.42, and the magnetron sputtering The deposition power of the jet is 60kW, the thickness of the silicon-zirconium-aluminum layer is 10nm; the composition and weight percentage of the silicon-zirconium-aluminum ternary material are: Zr is 14%, Al is 6%, and the balance is Si and Impurities that cannot be avoided.

Example 2

A coated glass, including:

Glass substrate

The functional film layer is deposited on the surface of the glass substrate;

The silicon-zirconium-aluminum layer is deposited on the surface of the functional film layer, wherein the silicon-zirconium-aluminum layer is deposited by magnetron sputtering in a nitrogen-containing atmosphere using a silicon-zirconium-aluminum ternary material as the target material The composition and weight percentage of the silicon-zirconium-aluminum ternary material are: Zr is 13%, Al is 5%, and the balance is Si and unavoidable impurities.

The method for preparing the coated glass includes the following steps:

S1. Provide a glass substrate;

S2. Depositing a functional film layer on the surface of the glass substrate; the functional film layer includes a first dielectric layer, a first barrier layer, and a The first functional layer, the second barrier layer, the second dielectric layer, the third barrier layer, the second functional layer, the fourth barrier layer, and the third dielectric layer;

The material of the first dielectric layer is SiN _x , and the thickness of the first dielectric layer is 45 nm;

The material of the first barrier layer is NiCr, and the thickness of the first barrier layer is 2 nm;

The material of the first functional layer is fine-grained silver AgNi10, and the thickness of the first functional layer is 6 nm;

The material of the second barrier layer is NiCr, and the thickness of the second barrier layer is 1 nm;

The material of the second dielectric layer is SiN _x /ZrO _x /SiN _x , wherein _{the thickness of each layer of SiN x} /ZrO _x /SiN _x is 65 nm, 10 nm, and 65 nm, respectively;

The material of the third barrier layer is NiCr, and the thickness of the third barrier layer is 2 nm;

The material of the second functional layer is fine-grained silver AgNi ₁₀ , and the thickness of the second functional layer is 13 nm;

The material of the fourth barrier layer is NiCr, and the thickness of the fourth barrier layer is 1 nm;

The material of the third dielectric layer is SiN _x , and the thickness of the third dielectric layer is 32 nm;

S3. Deposit a layer of silicon-zirconium-aluminum nitride on the surface of the functional film layer, wherein the layer of silicon-zirconium-aluminum nitride is a silicon-zirconium-aluminum ternary material as a target under a nitrogen-containing atmosphere by magnetron sputtering The vacuum degree of the nitrogen-containing atmosphere is 3×10 ^-3 to 5×10 ^-3 mbar, the volume ratio of nitrogen and argon in the nitrogen-containing atmosphere is 1:1.2, and the magnetron sputtering The deposition power of the jet is 50kW, the thickness of the silicon-zirconium-aluminum layer is 6nm; the composition and weight percentage of the silicon-zirconium-aluminum ternary material are: Zr is 13%, Al is 5%, and the balance is Si and Impurities that cannot be avoided.

Example 3

A coated glass, including:

Glass substrate

The functional film layer is deposited on the surface of the glass substrate;

A silicon-zirconium-aluminum layer is deposited on the surface of the functional film system layer, wherein the silicon-zirconium-aluminum layer is deposited by magnetron sputtering in a nitrogen-containing atmosphere using a silicon-zirconium-aluminum ternary material as the target material The composition and weight percentage of the silicon-zirconium-aluminum ternary material are as follows: Zr is 16%, Al is 7%, and the balance is Si and unavoidable impurities.

The method for preparing the coated glass includes the following steps:

S1. Provide a glass substrate;

S2. Depositing a functional film layer on the surface of the glass substrate; the functional film layer includes a first dielectric layer, a first barrier layer, and a The first functional layer, the second barrier layer, the second dielectric layer, the third barrier layer, the second functional layer, the fourth barrier layer, the third dielectric layer, the fifth barrier layer, the third functional layer, the sixth barrier layer, The fourth dielectric layer;

The material of the first barrier layer is NiCr, and the thickness of the first barrier layer is 1.2 nm;

The material of the first functional layer is silver copper AgCu, and the thickness of the first functional layer is 8 nm;

The material of the second barrier layer is NiCr, and the thickness of the second barrier layer is 0.8 nm;

The material of the second dielectric layer is SiN _x /ZrO _x /SiN _x , wherein _{the thickness of each layer of SiN x} /ZrO _x /SiN _x is 56 nm, 10 nm, and 56 nm, respectively;

The material of the third barrier layer is NiCr, and the thickness of the third barrier layer is 1.2 nm;

The material of the second functional layer is silver copper AgCu, and the thickness of the second functional layer is 14 nm;

The material of the fourth barrier layer is NiCr, and the thickness of the fourth barrier layer is 0.8 nm;

The material of the third dielectric layer is SiN _x /ZrO _x /SiN _x , wherein _{the thickness of each layer of SiN x} /ZrO _x /SiN _x is 67 nm, 10 nm, and 67 nm, respectively;

The material of the fifth barrier layer is NiCr, and the thickness of the fifth barrier layer is 1.3 nm;

The material of the third functional layer is silver copper AgCu, and the thickness of the third functional layer is 19 nm;

The material of the sixth barrier layer is NiCr, and the thickness of the sixth barrier layer is 1.3 nm;

The material of the fourth dielectric layer is SiN _x , and the thickness of the fourth dielectric layer is 32 nm;

S3. Deposit a layer of silicon-zirconium-aluminum nitride on the surface of the functional film layer, wherein the layer of silicon-zirconium-aluminum nitride is a silicon-zirconium-aluminum ternary material as a target under a nitrogen-containing atmosphere by magnetron sputtering The vacuum degree of the nitrogen-containing atmosphere is 3×10 ^-3 ～5×10 ^-3 mbar, the volume ratio of nitrogen and argon in the nitrogen-containing atmosphere is 1:1.5, and the magnetron sputtering The deposition power of the jet is 70kW, the thickness of the silicon-zirconium-aluminum nitride layer is 4nm; the composition and weight percentage of the silicon-zirconium-aluminum ternary material are: Zr is 16%, Al is 7%, and the balance is Si and Impurities that cannot be avoided.

Comparative example 1

Based on Example 2, the only difference is: in this comparative example 1, a layer of hyacinth-like mixed doped film is deposited on the surface of the functional film by magnetron sputtering, and the hyacinth-like mixed doped The film layer is a _{mixture of SiN x} and ZrSiO _x N _y , and the _{weight ratio of SiN x in} the mixture is 50-70%.

Comparative example 2

Based on Example 2, the only difference is: the composition and weight percentage of the silicon-zirconium-aluminum ternary material in this comparative example 2 are: Zr is 11%, Al is 5%, and the balance is Si and unavoidable impurities .

Comparative example 3

Based on Example 2, the only difference is: the composition and weight percentage of the silicon-zirconium-aluminum ternary material in this comparative example 3 are: Zr is 17%, Al is 5%, and the balance is Si and unavoidable impurities .

Comparative example 4

Based on Example 2, the only difference is: the composition and weight percentage of the silicon-zirconium-aluminum ternary material in this comparative example 4 are: Zr is 13%, Al is 4%, and the balance is Si and unavoidable impurities .

Comparative example 5

Based on Example 2, the only difference is: the composition and weight percentage of the silicon-zirconium-aluminum ternary material in this comparative example 5 are: Zr is 13%, Al is 8%, and the balance is Si and unavoidable impurities .

Test case

In order to verify the performance of the product of the present application, the coated glass prepared in Examples 1-3 and Comparative Examples 1-5 were respectively subjected to relevant performance tests, including, the specific methods are as follows:

Oxidation resistance test: see Table 1 for test results.

Table 1 Test results of oxidation resistance

室外暴露试验 Outdoor exposure test	试验放置时间 Test placement time	是否氧化 Is it oxidized	试验结果 test results
实施例1 Example 1	168小时 168 hours	否 no	合格 qualified
实施例2 Example 2	168小时 168 hours	否 no	合格 qualified
实施例3 Example 3	168小时 168 hours	否 no	合格 qualified
对比例1 Comparative example 1	76小时 76 hours	是 Yes	不合格 Unqualified
对比例2 Comparative example 2	76小时 76 hours	是 Yes	不合格 Unqualified
对比例3 Comparative example 3	76小时 76 hours	是 Yes	不合格 Unqualified
对比例4 Comparative example 4	76小时 76 hours	是 Yes	不合格 Unqualified
对比例5 Comparative example 5	76小时 76 hours	是 Yes	不合格 Unqualified

Abrasion resistance test: The test method is GB/T18915.1~2, the test results are shown in Table 2, where T represents the visible light transmittance, and △T is the absolute value of the difference between the visible light transmittance of the sample before and after the test (ie T0 and T1 The absolute value of the difference).

Table 2 Abrasion resistance test results

To	T0（研磨前） T0 (before grinding)	T1（研磨200圈） T1 (200 laps for grinding)	T2（研磨400圈） T2 (grinding 400 circles)	试验结果△T Test result△T
实施例1 Example 1	69.68 69.68	69.57 69.57	69.4 69.4	△T＜1 △T＜1
实施例2 Example 2	57.67 57.67	57.54 57.54	57.4 57.4	△T＜1 △T＜1
实施例3 Example 3	53.67 53.67	53.54 53.54	53.4 53.4	△T＜1 △T＜1
对比例1 Comparative example 1	67.23 67.23	67.35 67.35	62.34 62.34	△T＞4 △T＞4
对比例2 Comparative example 2	56.75 56.75	56.25 56.25	56.1 56.1	△T＜1 △T＜1
对比例3 Comparative example 3	57.78 57.78	57.35 57.35	53.2 53.2	△T＞4 △T＞4
对比例4 Comparative example 4	69.79 69.79	69.36 69.36	64.2 64.2	△T＞4 △T＞4
对比例5 Comparative example 5	53.78 53.78	53.35 53.35	49.2 49.2	△T＞4 △T＞4

Wipe resistance test: Wipe with an alcohol cloth, add 5 kg in weight, and observe whether there are pinhole scratches on the surface of the coated glass after wiping 50 times. See Table 3 for the test results.

Table 3 Wipe resistance test results

To	擦拭50下 Wipe 50 times	试验结果 test results	备注 Remark
实施例1 Example 1	无针孔划伤 No pinhole scratches	合格 qualified	食指加压力 Index finger pressure
实施例2 Example 2	无针孔划伤 No pinhole scratches	合格 qualified	食指加压力 Index finger pressure
实施例3 Example 3	无针孔划伤 No pinhole scratches	合格 qualified	食指加压力 Index finger pressure
对比例1 Comparative example 1	有针孔划伤 Pinhole scratches	不合格 Unqualified	食指加压力 Index finger pressure
对比例2 Comparative example 2	无针孔划伤 No pinhole scratches	合格 qualified	食指加压力 Index finger pressure
对比例3 Comparative example 3	有针孔划伤 Pinhole scratches	不合格 Unqualified	食指加压力 Index finger pressure
对比例4 Comparative example 4	有针孔划伤 Pinhole scratches	不合格 Unqualified	食指加压力 Index finger pressure
对比例5 Comparative example 5	有针孔划伤 Pinhole scratches	不合格 Unqualified	食指加压力 Index finger pressure

Acid resistance test: The test method is GB/T18915.1~2, the test results are shown in Table 4, where △T is the absolute value of the difference in visible light transmittance of the sample before and after the test.

Table 4 Acid resistance test results

To	膜层泡24小时 Membrane bubble for 24 hours	膜层泡48小时 Membrane soaking for 48 hours	膜层泡72小时 Membrane bubble for 72 hours	试验结果 test results
实施例1 Example 1	△T＜1 △T＜1	△T＜1.5 △T＜1.5	△T＜1.5 △T＜1.5	△T＜4（合格） △T＜4 (qualified)
实施例2 Example 2	△T＜1 △T＜1	△T＜1.5 △T＜1.5	△T＜1.5 △T＜1.5	△T＜4（合格） △T＜4 (qualified)
实施例3 Example 3	△T＜1 △T＜1	△T＜1.5 △T＜1.5	△T＜1.5 △T＜1.5	△T＜4（合格） △T＜4 (qualified)
对比例1 Comparative example 1	△T＞5 △T＞5	△T＞10 △T＞10	△T＞15变色 △T＞15 discoloration	不合格 Unqualified
对比例2 Comparative example 2	△T＞10 △T＞10	△T＞15 △T＞15	△T＞20变色 △T＞20 discoloration	不合格 Unqualified
对比例3 Comparative example 3	△T＜1 △T＜1	△T＜1.5 △T＜1.5	△T＜1.5 △T＜1.5	△T＜4（合格） △T＜4 (qualified)
对比例4 Comparative example 4	△T＜1 △T＜1	△T＜1.5 △T＜1.5	△T＜1.5 △T＜1.5	△T＜4（合格） △T＜4 (qualified)
对比例5 Comparative example 5	△T＞10 △T＞10	△T＞15 △T＞15	△T＞20变色 △T＞20 discoloration	不合格 Unqualified

In summary, the outermost layer of the coated glass is a silicon nitride zirconium aluminum layer, and at the same time, the silicon zirconium aluminum layer is deposited by magnetron sputtering using a silicon zirconium aluminum ternary material as a target in a nitrogen-containing atmosphere The composition and weight percentage of the silicon-zirconium-aluminum ternary material are: Zr is 12-16%, Al is 5-7%, and the balance is Si and unavoidable impurities, so that the silicon nitride zirconium aluminum layer At the same time, it has excellent oxidation resistance, abrasion resistance, wipe resistance and acid resistance, so that the coated glass can better protect the functional film layer in the coated glass during transportation, storage and processing, and can be used for protection. For protecting double silver coated glass and triple silver coated glass, unexpected technical effects have been achieved.

The above-mentioned embodiments only express the implementation of this application. The description is more specific and detailed, but it should not be understood as a limitation of the patent scope of this application. However, all technical solutions obtained by equivalent substitutions or equivalent transformations , Should fall within the protection scope of this application.

Claims

A coated glass, characterized in that it comprises:

Glass substrate

The functional film layer is deposited on the surface of the glass substrate;

A silicon-zirconium-aluminum layer is deposited on the surface of the functional film system layer, wherein the silicon-zirconium-aluminum layer is deposited by magnetron sputtering in a nitrogen-containing atmosphere using a silicon-zirconium-aluminum ternary material as the target material The composition and weight percentage of the silicon-zirconium-aluminum ternary material are: Zr is 12-16%, Al is 5-7%, and the balance is Si and unavoidable impurities.
3. The coated glass of claim 1, wherein the weight percentage of the unavoidable impurities is less than 3%.
The coated glass of claim 1, wherein the thickness of the silicon nitride zirconium aluminum layer is 1-10 nm.
The coated glass of claim 1, wherein the functional film layer is a solar control film layer or a low-emissivity film layer.
8. The coated glass of claim 4, wherein the solar control film layer is composed of a dielectric layer and a functional layer.
The coated glass of claim 5, wherein the dielectric layer comprises metal oxide or metal nitride, or non-metal oxide or non-metal nitride.
The coated glass according to claim 4, wherein the low-emissivity film layer is composed of a dielectric layer, a barrier layer, and a functional layer.
The coated glass according to claim 5, wherein the functional layer in the solar control film layer is a single silver film layer, a double silver film layer or a triple silver film layer.
8. The coated glass of claim 7, wherein the functional layer in the low-E film system layer is a single silver film layer, a double silver film layer or a triple silver film layer.
A method for preparing coated glass for preparing the coated glass according to any one of claims 1-9, characterized in that it comprises the following steps:

S1. Provide a glass substrate;

S2. Depositing a functional film layer on the surface of the glass substrate;

S3. Deposit a layer of silicon-zirconium-aluminum nitride on the surface of the functional film layer, wherein the layer of silicon-zirconium-aluminum nitride is a silicon-zirconium-aluminum ternary material as a target under a nitrogen-containing atmosphere by magnetron sputtering The composition and weight percentage of the silicon-zirconium-aluminum ternary material are: Zr is 12-16%, Al is 5-7%, and the balance is Si and unavoidable impurities.
The method for preparing coated glass according to claim 10, wherein the vacuum degree of the nitrogen-containing atmosphere is 3×10-3～5×10-3mbar, and the volume of nitrogen and argon in the nitrogen-containing atmosphere The ratio is 1: 1.2-1.5, and the deposition power of the magnetron sputtering is 50-70 kW.
9. The method for preparing coated glass according to claim 10, wherein a silicon nitride zirconium aluminum layer with a thickness of 1-10 nm is deposited on the surface of the functional film layer.
10. The method for preparing coated glass according to claim 10, wherein the functional film layer is a solar control film layer or a low-emissivity film layer.
The method for preparing coated glass according to claim 13, wherein when the functional film layer is a solar control film layer, the step of depositing a functional film layer on the surface of the glass substrate specifically includes : Depositing a dielectric layer and a functional layer on the glass substrate.
The method for preparing coated glass according to claim 13, wherein when the functional film layer is a low-emissivity film layer, the step of depositing a functional film layer on the surface of the glass substrate specifically includes : Depositing a dielectric layer, a barrier layer, and a functional layer on the glass substrate.