CN117567046A

CN117567046A - Coated glass, preparation method thereof and laminated glass

Info

Publication number: CN117567046A
Application number: CN202311587249.2A
Authority: CN
Inventors: 曹晖; 张洁林; 陈国富; 曾东; 游明希; 福原康太
Original assignee: Fuyao Glass Industry Group Co Ltd
Current assignee: Fuyao Glass Industry Group Co Ltd
Priority date: 2023-11-24
Filing date: 2023-11-24
Publication date: 2024-02-20

Abstract

The application provides coated glass, a preparation method thereof and laminated glass. The coated glass comprises a first glass substrate and a coating layer arranged on the surface of the first glass substrate. The coating layer comprises at least one functional lamination, a first protection layer, a second protection layer and a top protection layer which are laminated in sequence, each functional lamination comprises a metal layer and two medium layers, and the top protection layer is the layer of the coating layer farthest from the surface of the first glass substrate; the material of the top protective layer comprises SiAlOx, x is more than 1.5 and less than 2, the refractive index n of the top protective layer is 1.49-1.55, and the extinction coefficient k is 0.00001-0.003. According to the method, siAlOx is used as the top layer protection layer of the coating layer, so that the high temperature resistance, chemical stability and mechanical stability of the coating glass can be improved on the premise that the optical performance of the coating glass is not affected, and the processing resistance of the coating glass is improved.

Description

Coated glass, preparation method thereof and laminated glass

Technical Field

The application belongs to the technical field of glass, and particularly relates to coated glass, a preparation method thereof and laminated glass.

Background

Coated glass refers to the formation of a specially functional coating or film on the surface of a glass substrate using vapor deposition techniques. Coated glass can be used as insulating glass, electric heating glass, head-up display glass or other functions on motor vehicles. When coated glass is used in motor vehicles, it is also required to undergo a high temperature bending process of at least 500 ℃, such as a baking bending process, a press bending process, etc. of the automotive glass. This requires that the coating or film on the coated glass not only meet the requirements of optical properties and appearance quality, but also has higher mechanical properties, thermal stability and chemical stability. However, the coating or film layer of the coated glass in the related art has the defects of poor mechanical property, low hardness and the like, and is easily scratched by hard objects in the subsequent transportation, storage, transportation and processing processes, so that the processing resistance is poor.

Disclosure of Invention

In view of the above, a first aspect of the present application provides a coated glass, including a first glass substrate and a coating layer disposed on a surface of the first glass substrate;

the coating layer comprises at least one functional laminated layer, a first protective layer, a second protective layer and a top protective layer which are laminated in sequence, each functional laminated layer comprises a metal layer and two medium layers, the metal layer is positioned between the two medium layers, the top protective layer is the layer which is farthest from the surface of the first glass substrate in the coating layer, the first protective layer is positioned between the second protective layer and the at least one functional laminated layer, and the second protective layer is positioned between the first protective layer and the top protective layer in a direct contact manner;

the material of the top protective layer comprises SiAlOx, x is more than 1.5 and less than 2, the refractive index n value of the top protective layer is 1.49-1.55, and the extinction coefficient k value is 0.00001-0.003.

Wherein the refractive index of the first protective layer is larger than that of the second protective layer; and/or the physical thickness of the first protective layer is smaller than the physical thickness of the second protective layer.

The optical thickness of the first protective layer is 15-40 nm, the optical thickness of the second protective layer is 20-60 nm, and the ratio of the optical thickness of the first protective layer to the optical thickness of the second protective layer is 0.4-0.9.

Wherein the physical thickness of the top protective layer is 80 nm-300 nm.

Wherein, measured from one side of the coating layer, the pencil hardness of the coated glass is more than or equal to 9H.

Wherein, the coating layer satisfies one or more of the following conditions:

(1) The material of the first protective layer is selected from oxide of at least one element in Zn, mg, sn, ti, nb, zr;

(2) The physical thickness of the first protective layer is 5 nm-20 nm;

(3) The refractive index of the first protective layer is 2.0-2.75.

Wherein, the coating layer satisfies one or more of the following conditions:

(1) The material of the second protective layer is selected from oxide of at least one element in Zn, mg, sn, ti, nb, zr, al;

(2) The physical thickness of the second protective layer is 10 nm-40 nm;

(3) The refractive index of the second protective layer is 1.8-2.4.

Wherein, the coating layer satisfies one or more of the following conditions:

(1) The material of each metal layer is independently selected from any one metal or metal alloy of Ag, au, cu and Al;

(2) The physical thickness of each metal layer is independently 5 nm-20 nm;

(3) The material of each dielectric layer is independently selected from the oxides of at least one element in Zn, mg, sn, ti, nb, zr, ni, in, al, ce, W, mo, sb, bi;

(4) The physical thickness of each dielectric layer is independently 5 nm-30 nm.

The number of the functional laminated layers is at least two, a plurality of the functional laminated layers are arranged in a laminated mode, and an intermediate layer is arranged between every two adjacent functional laminated layers.

Wherein, the coating layer satisfies one or more of the following conditions:

(1) The material of each intermediate layer is independently selected from the group consisting of oxides, nitrides, or oxynitrides of at least one element in Si, zn, mg, sn, ti, nb, zr, ni, in, al, ce, W, mo, sb, bi;

(2) The physical thickness of each intermediate layer is independently 20nm to 100nm.

The coating layer further comprises an innermost adhesion layer arranged between the first glass substrate and the at least one functional laminated layer, and the innermost adhesion layer is in direct contact with the surface of the first glass substrate.

Wherein, the coating layer satisfies one or more of the following conditions:

(1) The material of the innermost adhesion layer is selected from oxide, nitride or oxynitride of at least one element in Si, zn, mg, sn, ti, nb, zr, ni, in, al, ce, W, mo, sb, bi;

(2) The physical thickness of the innermost adhesion layer is 10 nm-50 nm.

Wherein, the coating layer satisfies one or more of the following conditions:

(1) The sum of the physical thicknesses of the first protective layer and the second protective layer is smaller than the physical thickness of the top protective layer;

(2) The ratio of the physical thickness of the top protective layer to the physical thickness of the first protective layer is greater than or equal to 4;

(3) The ratio of the physical thickness of the top protective layer to the physical thickness of the first protective layer is 5 to 50, preferably 8 to 25;

(4) The ratio of the physical thickness of the top protective layer to the physical thickness of the second protective layer is greater than or equal to 3, preferably 4-15;

(5) The ratio of the physical thickness of the top protective layer to the total physical thickness of the first protective layer and the second protective layer is 1.5 to 15, preferably 3 to 10.

Wherein at least one of the functional stacks further comprises a barrier layer in direct contact with the metal layer, the physical thickness of the barrier layer being less than or equal to 5nm, the material of the barrier layer being selected from at least one metal or metal alloy of Ti, ni, cr, nb, W.

The second aspect of the application provides a preparation method of coated glass, which comprises the following steps:

providing a first glass substrate:

Providing a first glass substrate:

depositing a coating layer on at least one surface of the first glass substrate through a magnetron sputtering process; the coating layer comprises at least one functional laminated layer, a first protective layer, a second protective layer and a top protective layer which are laminated in sequence, each functional laminated layer comprises a metal layer and two medium layers, the metal layer is positioned between the two medium layers, the top protective layer is the layer which is farthest from the surface of the first glass substrate in the coating layer, the first protective layer is positioned between the second protective layer and the at least one functional laminated layer, and the second protective layer is positioned between the first protective layer and the top protective layer in a direct contact manner;

The sputtering target material of the top protective layer comprises a SiAl alloy target, wherein the SiAl alloy target comprises 45-92% of Si and 8-55% of Al in percentage by mass.

The target power supply of the top protection layer is a high-power pulse magnetron sputtering power supply, and the process parameters in the process of depositing the top protection layer meet one or more of the following conditions:

(1) The working voltage of the high-power pulse magnetron sputtering power supply is 550-1200V;

(2) The duty ratio of the high-power pulse magnetron sputtering power supply is 5% -15%;

(3) The working current of the high-power pulse magnetron sputtering power supply is 200A-1000A.

A third aspect of the present application provides a laminated glass comprising a second glass substrate, an adhesive layer and a coated glass as provided in the first aspect of the present application, wherein the adhesive layer is arranged between the coated glass and the second glass substrate, and the top protective layer in the coated layer is in direct contact with the adhesive layer.

Wherein, the absolute value of the difference between the refractive index of the top protective layer of the coating layer and the refractive index of the bonding layer is less than or equal to 0.03.

According to the coated glass, the preparation method thereof and the laminated glass, the SiAlOx is adopted as the top layer protection layer of the coated layer, and through the optimization design, the SiAlOx layer does not participate in the optical performance of the coated layer and is only used as the integral protection layer of the coated layer, so that the high temperature resistance, the chemical stability and the mechanical stability of the coated glass can be further improved on the premise that the optical performance of the coated glass is not affected, and the processing resistance of the coated glass is improved.

Drawings

In order to more clearly describe the technical solutions in the embodiments of the present application, the drawings that are required to be used in the embodiments of the present application will be described below.

Fig. 1 is a schematic structural diagram of a coated glass according to an embodiment of the present application.

Fig. 2 is a schematic structural diagram of a coated glass according to another embodiment of the present application.

Fig. 3 is a schematic structural view of a coated glass according to another embodiment of the present application.

Fig. 4 is a schematic structural view of a laminated glass according to an embodiment of the present application.

Description of the reference numerals: coated glass 10, first glass substrate 100, coated layer 200, innermost adhesion layer 201, first dielectric layer 202, first metal layer 203, second dielectric layer 204, first intermediate layer 205, third dielectric layer 206, second metal layer 207, fourth dielectric layer 208, second intermediate layer 209, fifth dielectric layer 210, third metal layer 211, sixth dielectric layer 212, third intermediate layer 213, seventh dielectric layer 214, fourth metal layer 215, eighth dielectric layer 216, first protective layer 220, second protective layer 230, top protective layer 240, laminated glass 20, adhesive layer 300, and second glass substrate 400.

Detailed Description

The following are preferred embodiments of the present application and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present application and are intended to be within the scope of the present application.

Unless otherwise indicated or contradicted, terms or phrases used in this application have the following meanings:

in this application, "first," "second," etc. are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature.

In this application, "one or more" refers to any one, any two, or any two or more of the listed items. Wherein "several" means any two or more.

The value of x in the chemical formula: there is a clear definition of the scope of definition. Not explicitly defined, it may be determined based on stoichiometric, sub-stoichiometric, or super-stoichiometric deposition, etc. in a magnetron sputtering process.

In this application, the refractive index is the refractive index at a wavelength of 550 nm.

In this application, the optical thickness is equal to the physical thickness of the film layer multiplied by its refractive index.

In the present application, the high temperature bending process may be a bake bending process or a press bending process of at least 500 ℃.

The application provides coated glass, which comprises a first glass substrate and a coating layer arranged on the surface of the first glass substrate.

The coating layer comprises at least one functional laminated layer, a first protective layer, a second protective layer and a top protective layer which are laminated in sequence, each functional laminated layer comprises a metal layer and two medium layers, the metal layer is positioned between the two medium layers, the top protective layer is the layer which is farthest from the surface of the first glass substrate in the coating layer, the first protective layer is positioned between the second protective layer and the at least one functional laminated layer, and the second protective layer is positioned between the first protective layer and the top protective layer in a direct contact manner; the material of the top protective layer comprises SiAlOx, x is more than 1.5 and less than 2, the refractive index n value of the top protective layer is 1.49-1.55, and the extinction coefficient k value is 0.00001-0.003.

The second protection layer is directly contacted between the first protection layer and the top protection layer, i.e. the second protection layer is directly contacted with the top protection layer, and the second protection layer is directly contacted with the first protection layer.

The first protective layer is used for isolating outside O ₂ Entering into the functional stack, and the compact film property is beneficial to improving the corrosion resistance of the film. The refractive index of the first protective layer is 2.0-2.75, and the refractive index of the first protective layer may be, but is not limited to, 2.0, 2.05, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.75 or a range composed of any two of these values. The material of the first protective layer is selected from oxide of at least one element in Zn, mg, sn, ti, nb, zr, and TiOx, nbOx, zrOx and the like can be exemplified. The physical thickness of the first protective layer is 5 nm-20 nm. Alternatively, the physical thickness of the first protective layer may be, but is not limited to, 5nm, 8nm, 10nm, 12nm, 14nm, 16nm, 18nm, 20nm, or a range consisting of any two of these values.

In view of the fact that the top protective layer does not participate in the optical properties of the plating layer and serves only as a protective layer of the plating layer, the ratio of the physical thickness of the top protective layer to the physical thickness of the first protective layer is preferably 4 or more, specifically, 5, 8, 10, 11, 12, 13, 14, 15, 20, 30, 35, 36, 40, 42, 50, 55, 60, 65, 70, 80, etc., more preferably 5 to 50, still more preferably 8 to 25.

The second protective layer is beneficial to enabling the coating layer to have better thermal expansion performance, and can ensure that the coating layer is not cracked, point-like defects are not generated in the high-temperature bending process. Meanwhile, when the second protective layer is used for laminated glass, the appearance color can be adjusted. The refractive index of the second protective layer is 1.8-2.4, and the refractive index of the second protective layer may be, but is not limited to, 1.8, 1.9, 2.0, 2.05, 2.1, 2.2, 2.3, 2.4 or a range composed of any two of these values. The material of the second protective layer is selected from oxide of at least one element of Zn, mg, sn, ti, nb, zr, al, and ZnO, znSnOx, znSnMgOx and the like are specifically exemplified. The physical thickness of the second protective layer is 10 nm-40 nm. Alternatively, the physical thickness of the second protective layer may be, but is not limited to, 10nm, 12nm, 14nm, 16nm, 18nm, 20nm, 22nm, 24nm, 26nm, 28nm, 30nm, 32nm, 34nm, 36nm, 38nm, 40nm, or a range consisting of any two of these values.

In view of the fact that the top protective layer does not participate in the optical properties of the plating layer and serves only as a protective layer of the plating layer, the ratio of the physical thickness of the top protective layer to the physical thickness of the second protective layer is preferably 3 or more, specifically, 3, 4, 5, 8, 10, 11, 12, 13, 14, 15, 20, etc., more preferably 4 to 15.

Optionally, the refractive index of the first protective layer is larger than that of the second protective layer in terms of optical performance, color adjustment and the like of the coating layer; and/or the physical thickness of the first protective layer is smaller than the physical thickness of the second protective layer.

Optionally, the optical thickness of the first protective layer is 15nm to 40nm, and the optical thickness of the first protective layer may be, but is not limited to, 15nm, 18nm, 20nm, 21nm, 22nm, 23nm, 24nm, 25nm, 26nm, 27nm, 28nm, 29nm, 30nm, 32nm, 35nm, 38nm, 40nm, or a range composed of any two of these values.

Optionally, the optical thickness of the second protective layer is 20nm to 60nm, and the optical thickness of the second protective layer may be, but is not limited to, 20nm, 24nm, 28nm, 32nm, 36nm, 40nm, 44nm, 48nm, 52nm, 55nm, 60nm or any two of these ranges.

Optionally, the ratio of the optical thickness of the first protective layer to the second protective layer is 0.4-0.9, specifically, a range consisting of 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9 or any two of these values may be exemplified.

Optionally, in terms of optical performance and color adjustment of the coating layer, and in favor of normal debugging of the film system and selection of richer colors, the sum of the optical thicknesses of the first protective layer and the second protective layer is 45 nm-80 nm, and specifically, the range can be exemplified by 45nm, 48nm, 50nm, 53nm, 55nm, 58nm, 60nm, 63nm, 65nm, 68nm, 70nm, 73nm, 75nm, 78nm, 80nm or any two of these values.

Alternatively, the refractive index n of the top protective layer may be, but is not limited to, 1.49, 1.50, 1.51, 1.52, 1.53, 1.54, 1.55, or any two of these values. Preferably, the refractive index n of the top protective layer is 1.50-1.54. More preferably, the refractive index n of the top protective layer is 1.50 to 1.53.

Alternatively, the extinction coefficient k value of the top protective layer may be, but is not limited to, a range of 0.00001, 0.00002, 0.00005, 0.00008, 0.0001, 0.0002, 0.0003, 0.0004, 0.0005, 0.0006, 0.0007, 0.0008, 0.0009, 0.001, 0.0011, 0.0012, 0.0013, 0.0014, 0.0015, 0.0016, 0.0018, 0.002, 0.0022, 0.0024, 0.0026, 0.0028, 0.003, or any two of these values. Preferably, the extinction coefficient k value of the top protective layer is 0.00005-0.0015. More preferably, the extinction coefficient k value of the top protective layer is 0.0001 to 0.001.

In one embodiment, the ratio of the refractive index n value of the top protective layer to the extinction coefficient k value is greater than or equal to 2000, which may be, but is not limited to, 2000, 2800, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 11000, 12000, 13000, 14000, 15000, 15500, or any two of these values. Preferably, the ratio is 2500 to 15000.

In one embodiment, the top protective layer has a physical thickness of 80nm to 300nm. Alternatively, the physical thickness of the top protective layer may be, but is not limited to, 80nm, 90nm, 100nm, 120nm, 150nm, 180nm, 200nm, 210nm, 240nm, 250nm, 280nm, 300nm, or a range of any two of these values. The physical thickness of the top protective layer is preferably 100nm to 200nm in terms of production cost, production convenience, and the like.

According to the coated glass provided by the embodiment, the SiAlOx is used as the top layer protection layer of the coated layer, and the SiAlOx layer does not participate in the optical performance of the coated layer through the optimization design and is only used as the whole protection layer of the coated layer, so that the high temperature resistance, the chemical stability and the mechanical stability of the coated glass can be further improved on the premise that the optical performance of the coated glass is not affected, and the processing resistance of the coated glass is improved. And the top protective layer is formed by deposition of a magnetron sputtering process, the sputtering target is a SiAl alloy target, the SiAl alloy target comprises 45-92% of Si and 8-55% of Al by mass percent, the addition of the Al improves the surface hardness and the hot ductility of the top protective layer, and the top protective layer is matched with the first protective layer and the second protective layer, so that the adaptability of the whole coating layer in the high-temperature bending process is improved, and the problems of film cracking, white point defects, film discoloration and the like caused by the high-temperature bending process are reduced.

Optionally, the sum of the physical thicknesses of the first protective layer and the second protective layer is less than the physical thickness of the top protective layer. Total physical thickness h0 of the first protective layer and the second protective layer=physical thickness h1 of the first protective layer+physical thickness H2 of the second protective layer. Preferably, the ratio of the physical thickness H3 of the top protective layer to the total physical thickness H0 of the first protective layer and the second protective layer is 1.5-15, i.e. h3/h0=1.2-15, specifically exemplified by 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or any two of these values, and more preferably h3/h0=3-10.

In one embodiment, the pencil hardness of the coated glass is greater than or equal to 9H as measured from the side of the coating.

In one embodiment, the coating layer satisfies one or several of the following conditions:

(2) The physical thickness of each metal layer is independently 5 nm-20 nm;

The metal layers have the characteristics of good infrared reflection, good electric conductivity and the like, and the materials of the metal layers are independently selected from any one metal or metal alloy of silver (Ag), gold (Au), copper (Cu) and aluminum (Al); specific examples thereof include Ag metal, agCu alloy, agIn alloy, agCuAl alloy, and the like. The coated glass has excellent heat insulation function due to the coated layer containing the metal layer, so that the energy consumption of the air conditioner is obviously reduced, and the thermal comfort of drivers and passengers is improved. Furthermore, the coating layer can also enable the coated glass to have an electric heating function after being electrified, and after the coated glass is manufactured into the laminated glass, the temperature of the laminated glass can be increased, so that the functions of preventing fog or defogging, defrosting, deicing and the like are realized, and the driving safety is improved. The energizing voltage of the laminated glass may be, for example, 12V to 380V.

Wherein the physical thickness of each metal layer is independently 5 nm-20 nm. For example, the physical thickness of each metal layer is independently 5nm, 8nm, 10nm, 12nm, 14nm, 16nm, 18nm, 20nm, or a range consisting of any two of these values.

Optionally, a barrier layer (not shown) may be further deposited between the metal layer and any dielectric layer, where the barrier layer is in direct contact with the metal layer, and the physical thickness of the barrier layer is less than or equal to 5nm, and the material of the barrier layer is selected from at least one metal or metal alloy in Ti, ni, cr, nb, W, and the barrier layer is mainly used for preventing the metal layer from contacting with oxidation reaction gas during the magnetron sputtering process, improving the optical performance of the coating layer, and the like.

The dielectric layers can enable the coating layer to bear a subsequent high-temperature bending process at least 500 ℃, so that the metal layer is protected from oxidation or corrosion and the like, the metal layer is deposited more densely, and the optical performance, mechanical performance and the like of the obtained coated glass can meet the use standard of the vehicle glass. The material of each dielectric layer is independently selected from the oxides of at least one element in Zn, mg, sn, ti, nb, zr, ni, in, al, ce, W, mo, sb, bi; specific examples thereof include AZO, nbOx, tiOx, znAlOx, znOx, snOx, znSnOx.

Wherein the physical thickness of each dielectric layer is independently 5 nm-30 nm. For example, the physical thickness of each dielectric layer is independently in the range of 5nm, 8nm, 10nm, 12nm, 14nm, 16nm, 18nm, 20nm, 24nm, 27nm, 30nm, or any two of these values.

In one embodiment, the number of the functional stacks is at least two, a plurality of the functional stacks are stacked, and an intermediate layer is further disposed between two adjacent functional stacks. Alternatively, the number of functional stacks is two, three, four or five.

Wherein each intermediate layer is respectively positioned between two adjacent functional stacks, so that the flatness of the coating layer can be improved, the reflection color can be improved, and the material of each intermediate layer is independently selected from oxide, nitride or oxynitride of at least one element in Si, zn, mg, sn, ti, nb, zr, ni, in, al, ce, W, mo, sb, bi; specific examples thereof include ZrNx, siOx, znOx, siOxNy, siAlZrNx, siAlNx, siZrNx, siNx, siZrOx, siAlZrOx, znSnOx, AZO, ITO, znAlOx, zrOx.

Wherein the physical thickness of each intermediate layer is independently 20 nm-100 nm; for example, each intermediate layer independently has a physical thickness in the range of 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm, 55nm, 60nm, 65nm, 70nm, 80nm, 85nm, 90nm, 95nm, 100nm, or any two of these values. Optionally, the physical thickness of each of the intermediate layers is independently 30nm to 70nm.

In one embodiment, the coating layer further comprises an innermost adhesion layer disposed between the first glass substrate and the at least one functional stack, the innermost adhesion layer being in direct contact with the first glass substrate surface.

The innermost adhesion layer is used for reducing or preventing alkali metal ions from diffusing into the coating layer from the glass, can also increase the innermost adhesion between the coating layer and the surface of the first glass substrate, and is beneficial to adjusting the mechanical property, optical property and high-temperature bending process property of the coating layer.

Wherein the material of the innermost adhesion layer is selected from oxide, nitride or oxynitride of at least one element in Si, zn, mg, sn, ti, nb, zr, ni, in, al, ce, W, mo, sb, bi; specific examples thereof include SiAlZrNx, nbOx, siNx, znSnOx, siZrNx, zrOx.

And/or the physical thickness of the innermost adhesion layer is 10 nm-50 nm. Alternatively, the physical thickness of the innermost attachment layer may be, but is not limited to, 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm, or a range of any two of these values.

Referring to fig. 1, as shown in fig. 1, the number of functional stacks is two. The coated glass 10 includes a first glass substrate 100 and a coating layer 200 disposed on a surface of the first glass substrate 100. The coating layer 200 includes an innermost adhesion layer 201, a first dielectric layer 202, a first metal layer 203, a second dielectric layer 204, a first intermediate layer 205, a third dielectric layer 206, a second metal layer 207, a fourth dielectric layer 208, a first protective layer 220, a second protective layer 230, and a top protective layer 240, which are sequentially stacked. Wherein the innermost adhesion layer 201 is directly deposited on the surface of the first glass substrate 100, the first dielectric layer 202, the first metal layer 203 and the second dielectric layer 204 constitute a first functional stack, the third dielectric layer 206, the second metal layer 207 and the fourth dielectric layer 208 constitute a second functional stack, and the first intermediate layer 205 is located between the first functional stack and the second functional stack.

Referring to fig. 2, as shown in fig. 2, the number of functional stacks is three. The coated glass 10 includes a first glass substrate 100 and a coating layer 200 disposed on a surface of the first glass substrate 100. The coating layer 200 includes an innermost adhesion layer 201, a first dielectric layer 202, a first metal layer 203, a second dielectric layer 204, a first intermediate layer 205, a third dielectric layer 206, a second metal layer 207, a fourth dielectric layer 208, a second intermediate layer 209, a fifth dielectric layer 210, a third metal layer 211, a sixth dielectric layer 212, a first protective layer 220, a second protective layer 230, and a top protective layer 240, which are sequentially stacked. Wherein the innermost adhesion layer 201 is directly deposited on the surface of the first glass substrate 100, the first dielectric layer 202, the first metal layer 203 and the second dielectric layer 204 constitute a first functional stack, the third dielectric layer 206, the second metal layer 207 and the fourth dielectric layer 208 constitute a second functional stack, the fifth dielectric layer 210, the third metal layer 211 and the sixth dielectric layer 212 constitute a third functional stack, the first intermediate layer 205 is located between the first functional stack and the second functional stack, and the second intermediate layer 209 is located between the second functional stack and the third functional stack.

Referring to fig. 3, as shown in fig. 3, the number of functional stacks is four. The coated glass 10 includes a first glass substrate 100 and a coating layer 200 disposed on a surface of the first glass substrate 100. The coating layer 200 includes an innermost adhesion layer 201, a first dielectric layer 202, a first metal layer 203, a second dielectric layer 204, a first intermediate layer 205, a third dielectric layer 206, a second metal layer 207, a fourth dielectric layer 208, a second intermediate layer 209, a fifth dielectric layer 210, a third metal layer 211, a sixth dielectric layer 212, a third intermediate layer 213, a seventh dielectric layer 214, a fourth metal layer 215, an eighth dielectric layer 216, a first protective layer 220, a second protective layer 230, and a top protective layer 240, which are sequentially stacked. Wherein the innermost adhesion layer 201 is directly deposited on the surface of the first glass substrate 100, the first dielectric layer 202, the first metal layer 203 and the second dielectric layer 204 form a first functional stack, the third dielectric layer 206, the second metal layer 207 and the fourth dielectric layer 208 form a second functional stack, the fifth dielectric layer 210, the third metal layer 211 and the sixth dielectric layer 212 form a third functional stack, the seventh dielectric layer 214, the fourth metal layer 215 and the eighth dielectric layer 216 form a fourth functional stack, the first intermediate layer 205 is located between the first functional stack and the second functional stack, the second intermediate layer 209 is located between the second functional stack and the third functional stack, and the third intermediate layer 213 is located between the third functional stack and the fourth functional stack.

The application also provides a preparation method of the coated glass, which comprises the following steps:

s100, providing a first glass substrate.

S200, depositing a coating layer on at least one surface of the first glass substrate through a magnetron sputtering process; the coating layer comprises at least one functional laminated layer, a first protective layer, a second protective layer and a top protective layer which are laminated in sequence, each functional laminated layer comprises a metal layer and two medium layers, the metal layer is positioned between the two medium layers, the top protective layer is the layer which is farthest from the surface of the first glass substrate in the coating layer, the first protective layer is positioned between the second protective layer and the at least one functional laminated layer, and the second protective layer is positioned between the first protective layer and the top protective layer in a direct contact manner;

In one embodiment, the sputter target of the top protective layer comprises a SiAl alloy target comprising, in mass percent, 45% to 92% Si and 8% to 55% Al.

Wherein the material of the top protective layer is SiAlOx (1.5 < x < 2), and the SiAl alloy targets O ₂ And performing magnetron sputtering deposition in Ar atmosphere.

Optionally, in the SiAl alloy target, si: the mass percentage of Al includes, but is not limited to, 92%:8%, 90%:10%, 85%:15%, 80%:20%, 75%:25%, 70%:30%, 65%:35%, 60%:40%, 55%:45%, 50%:50% or any two of these values.

The SiAlOx layer is prepared by adopting a SiAl alloy target containing 45 to 92 percent of Si and 8 to 55 percent of Al and is used as a top layer protection layer, and the refractive index n value is 1.74 to 1.76 relative to the Al ₂ O ₃ And SiO with refractive index less than 1.49 ₂ ，SiO ₂ Is a non-metal oxide, al ₂ O ₃ The refractive index of the SiAlOx layer can be improved by properly improving the Al content in the SiAl alloy target, the stress of the SiAlOx layer is changed, and the thermal stability and the thermal ductility of the coating layer are improved; meanwhile, the conductivity of the SiAl alloy target can be improved, so that the sputtering rate of SiAlOx is improved, and the production cost is reduced.

In one embodiment, the medium layer, the intermediate layer, the first protective layer and the second protective layer in the film coating layer can respectively and independently adopt an intermediate frequency magnetron sputtering power supply (MF power supply) as a target power supply, and the duty ratio of the MF power supply is 100%.

In one embodiment, the top protective layer uses a high power pulsed magnetron sputtering power supply (HiPIMS power supply) as the target power supply. The HiPIMS power supply can supply hundreds of kilowatts or even megawatts of instantaneous high power to the sputtering target material in the sputtering deposition process, so that the ionization rate of the sputtering target material is improved, the SiAlOx layer has more chemical bond bonding, the innermost attachment of the top protective layer is enhanced, and the surface hardness of the top protective layer is improved; meanwhile, the SiAlOx layer is deposited more densely, and the refractive index n value of the top protective layer is properly improved. The process parameters during the deposition of the top protective layer satisfy one or several of the following conditions: the working voltage of the high-power pulse magnetron sputtering power supply is 550-1200V. And/or the duty ratio of the high-power pulse magnetron sputtering power supply is 5% -15%. And/or the working current of the high-power pulse magnetron sputtering power supply is 200A-1000A.

Optionally, the working voltage of the high-power pulse magnetron sputtering power supply includes, but is not limited to, 550V, 600V, 650V, 700V, 750V, 800V, 850V, 900V, 950V, 1000V, 1050V, 1100V, 1150V, 1200V or a range composed of any two of these values.

Optionally, the duty cycle of the high power pulsed magnetron sputtering power supply includes, but is not limited to, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15% or a range consisting of any two of these values.

Optionally, the working current of the high-power pulse magnetron sputtering power supply includes, but is not limited to, 200A, 300A, 400A, 500A, 600A, 700A, 800A, 900A, 1000A or a range formed by any two of these values.

When the HiPIMS power supply is used for depositing the SiAl alloy target, the content of Al is 8-55wt%, the refractive index n value of SiAlOx is 1.49-1.55, and the extinction coefficient k value is 0.0001-0.003. If the content of Al is less than 8wt%, the SiAlOx layer is poor in heat stability and heat ductility. When the physical thickness of the top protective layer is thicker, the problems of increased square resistance, punctiform defect and the like of the coating layer after a high-temperature bending process are easily caused. And, although the HiPIMS power supply is used for increasing current, the film layer can be more compact, and the refractive index n value of the SiAlOx layer is improved. However, if the Al content is too small, the refractive index of the SiAlOx layer does not reach 1.49, which affects the optical properties of the coating layer. Meanwhile, the content of Al is too small, so that the hardness of the SiAlOx layer is slightly improved, and the hardness of the film coating layer is also slightly improved. If the content of Al is more than 55wt%, the stress of the SiAlOx layer is overlarge, and when the physical thickness of the top protective layer is thicker, the haze of the coating layer after a high-temperature bending process is easy to cause. And, the refractive index of the SiAlOx layer is larger than 1.55, and the optical performance of the coating layer is also affected.

In another embodiment, the top protective layer uses an intermediate frequency magnetron sputtering power supply (MF power supply) as the target power supply. When an MF power source is used to deposit SiAl alloy targets, the content of Al is 15-55wt%, the refractive index n of SiAlOx ranges from 1.49 to 1.55, and the extinction coefficient k ranges from 0.00001 to 0.001.

According to the preparation method of the coated glass, the SiAlOx is used as the top layer protection layer of the coated layer, so that the high temperature resistance, the chemical stability and the mechanical stability of the coated glass can be further improved on the premise that the optical performance of the coated glass is not affected, and the processing resistance of the coated glass is improved.

Referring to fig. 4, the present application further provides a laminated glass 20, including a second glass substrate 400, an adhesive layer 300, and a coated glass 10 as provided in the foregoing application, where the adhesive layer 300 is disposed between the coated glass 10 and the second glass substrate 400, and the top protective layer 240 in the coated layer 200 is in direct contact with the adhesive layer 300.

In one embodiment, the refractive index n of the top protective layer 240 ranges from 1.49 to 1.55, the refractive index of the adhesive layer ranges from 1.50 to 1.54, and the refractive index of the top protective layer 240 is less different from, or even substantially identical to, the refractive index of the adhesive layer, so that the physical thickness of the top protective layer 240 can be increased to a greater extent without affecting the optical properties of the coated glass 10 and the laminated glass 20. Preferably, the absolute value of the difference between the refractive index of the top protective layer 240 of the coating layer 200 and the refractive index of the adhesive layer 300 is equal to or less than 0.03, more preferably equal to or less than 0.02, even more preferably equal to or less than 0.01, and even more preferably equal to 0.

In one embodiment, the refractive index of the first glass substrate 100 ranges from 1.52 to 1.54, and the refractive index of the second glass substrate 400 ranges from 1.52 to 1.54, which is advantageous for greatly increasing the physical thickness of the top protective layer 240 without affecting the optical properties of the coated glass 10 and the laminated glass 20. After the laminated glass 20 is mounted on the vehicle, the first glass substrate 100 may serve as an outer glass plate that is located on the outer side of the vehicle; alternatively, the first glass substrate 100 may serve as an inner glass plate that is located on the inner side of the vehicle.

In the present application, the laminated glass 20 may be mounted to a vehicle for use as a front windshield, a side window, a rear windshield, a sunroof glass, or the like.

Alternatively, the first glass substrate 100 may be transparent glass or ultra-transparent glass (ultra-white glass), and the second glass substrate 400 may be transparent glass, ultra-transparent glass, or colored glass. The total iron content of the transparent glass is less than or equal to 0.1%, and the visible light transmittance of the transparent glass is more than or equal to 80%. The total iron content of the ultra-transparent glass is less than or equal to 0.015 percent, and the visible light transmittance of the ultra-transparent glass is more than or equal to 90 percent. The total iron content of the colored glass is greater than or equal to 0.5%, and the visible light transmittance of the colored glass is less than or equal to 85%.

Optionally, the adhesive layer 300 is used to connect the coated glass 10 and the second glass substrate 400 to increase the structural strength of the laminated glass 20 so that it meets the safety standards and regulatory requirements of more scenes. The material of the adhesive layer 300 may be polyvinyl butyral (PVB), ethylene Vinyl Acetate (EVA), thermoplastic polyurethane elastomer (TPU), or an ionomer film (SGP), etc. The adhesive layer 300 may be a single-layer structure or a multi-layer structure, and the multi-layer structure may be exemplified by a double-layer structure, a three-layer structure, a four-layer structure, a five-layer structure, and the like. The adhesive layer may also have other functions, such as providing at least one colored region to act as a shadow band to reduce interference of sunlight with the human eye, or adding an infrared absorber to have a sun-screening or heat-insulating function, or adding an ultraviolet absorber to have an ultraviolet-blocking function, or at least one layer of the multi-layer structure having a higher plasticizer content to have a sound-insulating function.

In another embodiment, the coated glass 10 provided herein may also be manufactured as a hollow glass or a vacuum glass.

The hollow glass comprises a second glass substrate, a hollow layer, a fixed spacing frame and the coated glass 10 provided by the application, wherein the fixed spacing frame is used for supporting the coated glass and the second glass substrate and guaranteeing the sealing of the hollow layer, the frame body of the fixed spacing frame is circumferentially arranged along the edge of the hollow glass, the inner space of the fixed spacing frame is a sealed hollow layer, and the coated layer 200 faces the hollow layer. The hollow layer is filled with a drying gas, such as drying air or inert gas, and the hollow glass has good heat insulation and sound insulation properties.

The vacuum glass comprises a second glass substrate, a vacuum layer, support columns and the coated glass 10 provided by the application, wherein a closed space is formed between the coated glass 10 and the second glass substrate in a sealing mode, the vacuum layer is formed by vacuumizing the closed space, the support columns are located in the vacuum layer, the support columns are a plurality of equal-height columns and are used for supporting the coated glass 10 and the second glass substrate, and the coated layer 200 faces the vacuum layer. The material for the peripheral seal can be glass powder or metal. The material of the support column can be selected from metal, alloy, inorganic nonmetal or a mixture of metal and inorganic nonmetal, etc. The vacuum degree of the vacuum layer is less than or equal to 0.1Pa, and the vacuum glass has excellent heat insulation and sound insulation performances.

In order to make the objects and advantages of the present application more apparent, the effects of the coated glass and the laminated glass of the present application will be described in further detail with reference to the following specific examples.

Comparative examples 1-3 and examples 1-4:

a 2.1mm thick transparent glass substrate (white glass) was prepared, and the film layer structures of comparative examples 1 to 3 and examples 1 to 4 were deposited on the surface of the transparent glass substrate by a magnetron sputtering process, wherein the number of functional stacks of the film coating layers was two.

The refractive index n and extinction coefficient k of the top protective layer of examples 1-4 after the high temperature bending process were measured and the measurement results are shown in table 1.

Comparative examples 1, 3: the first glass substrate/the innermost adhesion layer/the functional stack/the intermediate layer/the functional stack/the first protective layer/the second protective layer/the third protective layer is not provided with a top protective layer.

Comparative example 2: the first glass substrate/innermost adhesion layer/functional stack/intermediate layer/functional stack/first protective layer/second protective layer, the third protective layer and the top protective layer were not provided.

Examples 1 to 4: the first glass substrate/the innermost adhesion layer/the functional stack/the intermediate layer/the functional stack/the first protective layer/the second protective layer/the top protective layer.

Table 1: performance parameter table of top protective layer in examples 1-4

As can be seen from Table 1, examples 1 to 4, in which SiAlOx layers were prepared as the top protective layer using SiAl alloy targets containing 45% to 92% Si and 8% to 55% Al, the refractive index n value of the top protective layer was 1.50 to 1.54, and the extinction coefficient k value was 0.0001 to 0.001.

The pencil hardness, alcohol wiping test, oxidation resistance duration, haze, appearance and sheet resistance of the coated glasses of comparative examples 1 to 3 and example 1 were measured, and the measurement results are shown in table 2.

Pencil hardness test: the pencil hardness test was carried out on the coating according to GB/T6739-2006.

Duration of antioxidation: the coated glass was exposed to a high temperature and high humidity environment (temperature 50 ℃ C./humidity 90%) and periodically inspected to count how long corrosion or oxidation points began to appear.

Haze: and measuring from one side of the coating layer by adopting a haze meter.

Square resistance: and measuring the coating layer by using a handheld square resistance meter.

Alcohol wiping test: and (3) using the dust-free cloth dipped with alcohol to press by two hands, forcefully wiping the coating layer, and observing whether the coating layer is separated in large pieces or in dot form.

Table 2: performance parameters of the coated glasses of comparative examples 1 to 3 and example 1

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The pencil hardness, alcohol wiping test, oxidation resistance duration, haze, appearance and sheet resistance of the coated glasses of examples 2 to 4 were measured and the measurement results are shown in table 3.

Table 3: performance parameter tables for coated glasses in examples 2 to 4

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As can be seen from tables 2 and 3, comparative examples 1 to 3 were not provided with SiAlOx as the outermost protective layer, and the pencil hardness of the coating layer was less than 7H before and after the high temperature bending process, and the haze was more than 0.35% after the high temperature bending process.

Specifically, in comparative example 2, the third protective layer is not provided and the top protective layer is not provided, so that the antioxidation duration of the coating layer before the high-temperature bending process is less than 200 hours, the pencil hardness of the coating layer after the high-temperature bending process is reduced to less than 4H, the haze is increased to more than 0.55%, and the problem of film fogging appears in appearance; the sheet resistance of the coating layer in comparative example 2 after the high temperature bending process was greater than that before the high temperature bending process, even greater than 3Ω/≡s, and was improved by 97% compared with that of the coating layer in comparative example 1 after the high temperature bending process.

Examples 1 to 4 each independently set SiAlOx as the outermost protective layer, and the Al content in the SiAl alloy target thereof was 8% or more, so that the pencil hardness of the coating layer thereof after the high temperature bending process was 9H or more, and the oxidation resistance duration of the coating layer thereof before the high temperature bending process was 350 hours or more, even 400 hours or more, and the haze of the coating layer thereof after the high temperature bending process was 0.3% or less, even 0.25% or less, and the square resistance of the coating layer thereof after the high temperature bending process was 1.70 Ω/≡.

Compared with comparative examples 1 and 3, examples 1 to 4 adopt a top protective layer to replace a third protective layer, and the physical thickness of the first protective layer and the second protective layer is increased, so that the mechanical strength of the first protective layer and the second protective layer can be improved, and the high temperature resistance, the chemical stability and the mechanical stability of the coated glass are improved; the optical thicknesses of the first protective layer and the second protective layer can be improved, so that the optical performance of the coated glass is not affected; further, the optical performance, color adjustment and the like of the coating layer are facilitated; the physical thickness of the first protective layer and the physical thickness of the second protective layer are properly increased, so that the protection of the metal layer can be further improved, the corrosion resistance of the metal layer is improved, the oxidation resistance duration is increased, and the defects of reduced haze, white spots and the like of the coated glass after the high-temperature bending process are reduced.

The physical thickness and optical thickness of the first protective layer, the second protective layer, and the third protective layer in the coated glasses of comparative examples 1 to 3 and examples 1 to 4 were measured, and the measurement results are shown in Table 4.

Table 4: performance parameter tables of the protective layers in comparative examples 1 to 3 and examples 1 to 4

As can be seen from Table 4, by adjusting the sum of the optical thicknesses of the first protective layer and the second protective layer of examples 1 to 4 to 45nm to 60nm, the ratio of the optical thicknesses of the first protective layer and the second protective layer to 0.6 to 0.9 was substantially equal to the sum of the optical thicknesses of the first protective layer, the second protective layer and the third protective layer of comparative example 1, and the optical properties of the coated glass of examples 1 to 4 were not substantially changed.

Meanwhile, coated glasses of comparative examples 1 to 3 and examples 1 to 4 were prepared, and a transparent PVB of 0.76mm was prepared as an adhesive layer, and another transparent glass substrate of 2.1mm thickness was prepared as a second glass substrate, and corresponding laminated glasses were manufactured in accordance with the automobile glass production process. The laminated glasses composed of the coated glasses of comparative examples 1 to 3 and examples 1 to 4 were measured for visible light transmittance T, visible light reflectance R, and reflection color Lab, and the measurement results are shown in Table 4.

Visible light transmittance T: in the wavelength range of 380nm to 780nm, measurements were carried out according to ISO 9050.

Visible light reflectance R: in the wavelength range of 380nm to 780nm, the measurement is carried out according to ISO 9050 from the side of the coated glass, on which the coating layer is not arranged.

Reflection color: and calculating an L value, an a value and a b value according to a CIE Lab color model under the condition of measuring an incidence angle of 8 degrees and based on a D65 light source and an angle of 10 degrees from the side of the coated glass where the coating layer is not arranged, wherein the L value represents brightness, the a value represents a red-green value, and the b value represents a yellow-blue value.

Table 5: measurement results of laminated glasses composed of the coated glasses of comparative examples 1 to 3 and examples 1 to 4

As can be seen from table 5, the laminated glass of the composition of the coated glass of comparative example 1 is used as a reference:

after the optical thickness of the third protective layer of comparative example 3 was greatly increased, the visible light reflectance R was increased by 11.6% (the variation range was greater than 100%), the L value of the reflection color was greatly increased by 15, the a value was decreased by 7, and the optical properties of the laminated glass were significantly changed.

In the laminated glass of examples 1 to 4, the difference between the refractive index (n=1.50 to 1.54) of the top protective layer SiAlOx and the refractive index (n=1.50 to 1.53) of PVB is less than 0.03, preferably less than or equal to 0.02, more preferably less than or equal to 0.01, and even equal, so that the optical parameters of the laminated glass of examples 1 to 4 are not greatly or almost identical to those of comparative example 1, and the optical properties of the laminated glass are not substantially changed.

Comparative examples 4-6 and examples 5-8:

a 2.1mm thick transparent glass substrate (white glass) was prepared, and the film layer structures of comparative examples 4 to 6 and examples 5 to 8 were deposited on the surface of the transparent glass substrate by a magnetron sputtering process, wherein the number of functional stacks of the film coating layers was three.

The refractive index n and extinction coefficient k of the top protective layer of examples 5-8 after the high temperature bending process were measured and the measurement results are shown in table 6.

Comparative examples 4, 6: the first glass substrate/innermost adhesion layer/functional stack/intermediate layer/functional stack/first protective layer/second protective layer/third protective layer, no top protective layer is provided.

Comparative example 5: the first glass substrate/innermost adhesion layer/functional stack/intermediate layer/functional stack/first protective layer/second protective layer, the third protective layer and the top protective layer were not provided.

Examples 5 to 8: the first glass substrate/the innermost adhesion layer/the functional stack/the intermediate layer/the functional stack/the first protective layer/the second protective layer/the top protective layer.

Table 6: performance parameter table of top protective layer in examples 5-8

As can be seen from Table 6, examples 5-8, which prepared SiAlOx layers as the top protective layer using SiAl alloy targets containing 45% -92% Si and 8% -55% Al, can obtain the top protective layer having refractive index n value of 1.50-1.54 and extinction coefficient k value of 0.0001-0.001.

The pencil hardness, alcohol wiping test, oxidation resistance duration, haze, appearance and sheet resistance of the coated glasses of comparative examples 4 to 6 and example 5 were measured, and the measurement results are shown in table 7.

Table 7: coated glass performance parameter tables in comparative examples 4 to 6 and example 5

The pencil hardness, alcohol wiping test, oxidation resistance duration, haze, appearance and sheet resistance of the coated glasses of examples 6 to 8 were measured and the measurement results are shown in table 8.

Table 8: performance parameter table for coated glass in examples 6-8

As can be seen from tables 7 and 8, comparative examples 4 to 6 were not provided with SiAlOx as the outermost protective layer, and the pencil hardness of the coating layer was less than 8H before and after the high temperature bending process, and the haze was more than 0.35% after the high temperature bending process.

Specifically, in comparative example 5, no third protective layer and no top protective layer are provided, so that the antioxidation duration of the coating layer before the high-temperature bending process is less than 200 hours, the pencil hardness of the coating layer after the high-temperature bending process is reduced to less than 5H, the haze is increased to more than 0.4%, and the problem of slight fogging of the coating layer appears; the sheet resistance of the coating layer in comparative example 5 after the high temperature bending process was greater than that before the high temperature bending process, even greater than 1.2 Ω/≡s, and was increased by 28% compared with that of the coating layer in comparative example 4 after the high temperature bending process.

Examples 5 to 8 each independently set SiAlOx as the outermost protective layer, and the Al content in the SiAl alloy target thereof was 8% or more, so that the pencil hardness of the coating layer thereof after the high temperature bending process was 9H or more, and the oxidation-resistant period of the coating layer thereof before the high temperature bending process was 250 hours or more, even 300 hours or more, and the haze of the coating layer thereof after the high temperature bending process was 0.3% or less, even 0.25% or less, and the square resistance thereof after the high temperature bending process was 0.95 Ω/≡.

Compared with comparative examples 4 and 6, the top protective layer is adopted to replace the third protective layer in examples 5-8, and the physical thickness of the first protective layer and the second protective layer is properly increased, so that the mechanical strength of the first protective layer and the second protective layer can be improved, and the high temperature resistance, the chemical stability and the mechanical stability of the coated glass are improved; the optical thicknesses of the first protective layer and the second protective layer can be improved, so that the optical performance of the coated glass is not affected; further, the optical performance, color adjustment and the like of the coating layer are facilitated; the physical thickness of the first protective layer and the physical thickness of the second protective layer are properly increased, so that the protection of the metal layer can be further improved, the corrosion resistance of the metal layer is improved, the oxidation resistance duration is increased, and the defects of reduced haze, white spots and the like of the coated glass after the high-temperature bending process are reduced.

The physical thickness and the optical thickness of the first protective layer, the second protective layer, and the third protective layer in the coated glasses of comparative examples 4 to 6 and examples 5 to 8 were measured, and the measurement results are shown in Table 9.

Table 9: performance parameter tables of the protective layers in comparative examples 4 to 6 and examples 5 to 8

As can be seen from Table 9, by adjusting the sum of the optical thicknesses of the first protective layer and the second protective layer of examples 5 to 8 to be 60nm to 70nm, the ratio of the optical thicknesses of the first protective layer and the second protective layer was 0.55 to 0.65, and the optical properties of the coated glass of examples 5 to 8 were not substantially changed.

The laminated glasses composed of the coated glasses of comparative examples 4 to 6 and examples 5 to 8 were measured for visible light transmittance T, visible light reflectance R, and reflection color Lab, and the measurement results were shown in Table 10.

Table 10: measurement results of laminated glasses composed of the coated glasses of comparative examples 4 to 6 and examples 5 to 8

As can be seen from table 10, the laminated glass of the composition of the coated glass of comparative example 4 is used as a reference:

after the optical thickness of the third protective layer of comparative example 6 was greatly increased, the visible light reflectance R was increased by 4.6% (the variation range was greater than 50%), the L value of the reflection color was greatly increased by 8.1, the a value was decreased by 2.8, and the b value was increased by 9.6, and the optical properties of the laminated glass were significantly changed.

In the laminated glass of examples 5 to 8, the difference between the refractive index (n=1.50 to 1.54) of the top protective layer SiAlOx and the refractive index (n=1.50 to 1.53) of PVB is less than 0.03, preferably less than or equal to 0.02, more preferably less than or equal to 0.01, and even equal, so that the optical parameters of the laminated glass of examples 5 to 8 are not greatly changed from those of comparative example 4, and the optical properties of the laminated glass are changed slightly.

Comparative examples 7 to 9 and examples 9 to 11:

a 2.1mm thick transparent glass substrate (white glass) was prepared, and the film layer structures of comparative examples 7 to 9 and examples 9 to 11 were deposited on the surface of the transparent glass substrate by a magnetron sputtering process, wherein the number of functional stacks of the film coating layers was four.

The refractive index n and extinction coefficient k of the top protective layer of examples 9-11 after the high temperature bending process were measured and the measurement results are shown in table 11.

Comparative examples 7, 9: the first glass substrate/innermost adhesion layer/functional stack/intermediate layer/functional stack/first protective layer/second protective layer/third protective layer, no top protective layer is provided.

Comparative example 8: the first glass substrate/innermost adhesion layer/functional stack/intermediate layer/functional stack/first protective layer/second protective layer, the third protective layer and the top protective layer were not provided.

Examples 9 to 11: the first glass substrate/the innermost adhesion layer/the functional stack/the intermediate layer/the functional stack/the first protective layer/the second protective layer/the top protective layer.

Table 11: performance parameter table of top protective layer in examples 9-11

As can be seen from Table 11, examples 9-11 prepared SiAlOx layers as top protective layers using SiAl alloy targets containing 45% -92% Si and 8% -55% Al gave refractive index n values of 1.50-1.54 and extinction coefficient k values of 0.0001-0.001.

The pencil hardness, alcohol wiping test, oxidation resistance duration, haze, appearance and sheet resistance of the coated glasses of comparative examples 7 to 9 and example 9 were measured, and the measurement results are shown in table 12.

Table 12: performance parameter tables for coated glasses in comparative examples 7 to 9 and example 9

The pencil hardness, alcohol wiping test, oxidation resistance time, haze, appearance and sheet resistance of the coated glasses of examples 10 to 11 were measured and the measurement results are shown in Table 13.

Table 13: performance parameter table for coated glass in examples 10-11

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As can be seen from tables 12 and 13, comparative example 7 was provided with only the third protective layer without the top protective layer, not only the oxidation resistance time of the coating layer before the high temperature bending process was less than 250 hours, but also the pencil hardness of the coating layer after the high temperature bending process was reduced to less than 7H and the haze was increased to more than 0.3%.

In the comparative example 8, the third protective layer is not arranged and the top protective layer is not arranged, so that the antioxidation time of the coating layer before the high-temperature bending process is less than 150 hours, the pencil hardness of the coating layer after the high-temperature bending process is reduced to be less than 4H, the haze is increased to be more than 0.4%, and the problem of slight fogging of the coating layer appears; the sheet resistance of the coating layer in comparative example 8 after the high temperature bending process was greater than that before the high temperature bending process, even greater than 1Ω/≡s, and was improved by 50% compared with that of the coating layer in comparative example 7 after the high temperature bending process.

Examples 9 to 11 each independently set SiAlOx as the outermost protective layer, and the Al content in the SiAl alloy target thereof was 8% or more, so that the pencil hardness of the coating layer thereof after the high temperature bending process was 9H or more, and the oxidation resistance duration of the coating layer thereof before the high temperature bending process was 250 hours or more, even 300 hours or more, and the haze of the coating layer thereof after the high temperature bending process was 0.3% or less, even 0.28% or less, and the square resistance of the coating layer thereof after the high temperature bending process was 0.8 Ω/≡.

Compared with comparative examples 7 and 9, examples 9 to 11 adopt a top protective layer to replace a third protective layer, and the physical thickness of the first protective layer and the second protective layer is increased, so that the mechanical strength of the first protective layer and the second protective layer can be improved, and the high temperature resistance, the chemical stability and the mechanical stability of the coated glass are improved; the optical thicknesses of the first protective layer and the second protective layer can be improved, so that the optical performance of the coated glass is not affected; further, the optical performance, color adjustment and the like of the coating layer are facilitated; the physical thickness of the first protective layer and the physical thickness of the second protective layer are properly increased, so that the protection of the metal layer can be further improved, the corrosion resistance of the metal layer is improved, the oxidation resistance duration is increased, and the defects of reduced haze, white spots and the like of the coated glass after the high-temperature bending process are reduced.

The physical thickness and the optical thickness of the first protective layer, the second protective layer, and the third protective layer in the coated glasses of comparative examples 7 to 9 and examples 9 to 11 were measured, and the measurement results are shown in Table 14.

Table 14: performance parameter tables of the protective layers in comparative examples 7 to 9 and examples 9 to 11

As can be seen from Table 14, by adjusting the sum of the optical thicknesses of the first protective layer and the second protective layer of examples 9 to 11 to be 60nm to 80nm, the ratio of the optical thicknesses of the first protective layer and the second protective layer to be 0.45 to 0.7 was similar to the sum of the optical thicknesses of the first protective layer, the second protective layer and the third protective layer in comparative example 1, and the optical properties of the coated glass were not substantially changed in examples 9 to 11.

The laminated glasses composed of the coated glasses of comparative examples 7 to 9 and examples 9 to 11 were measured for visible light transmittance T, visible light reflectance R, and reflection color Lab, and the measurement results were shown in Table 15.

Table 15: measurement results of laminated glasses composed of the coated glasses of comparative examples 7 to 9 and examples 9 to 11

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As can be seen from table 15, the laminated glass of the composition of the coated glass of comparative example 7 is used as a reference:

after the optical thickness of the third protective layer of comparative example 9 was greatly increased, the visible light reflectance R was increased by 3.8% (the variation range was greater than 40%), the L value of the reflection color was greatly increased by 8.6, the a value was increased by 5.2, and the b value was increased by 13.5, and the optical properties of the laminated glass were significantly changed.

In the laminated glass of examples 9 to 11, the difference between the refractive index (n=1.50 to 1.52) of the top protective layer SiAlOx and the refractive index (n=1.50 to 1.53) of PVB is less than 0.03, preferably less than or equal to 0.02, more preferably less than or equal to 0.01, and even equal, so that the optical parameters of the laminated glass of examples 9 to 11 are not greatly or almost identical to those of comparative example 7, and the optical properties of the laminated glass are not substantially changed.

The present application sputters SiAl alloy targets on Ar, O by using HiPIMS/MF power ₂ The SiAlOx film layer is deposited in the atmosphere and used as a top protective layer of the film coating layer, and the high temperature resistance, chemical stability and mechanical stability of the film coating layer are improved by adjusting the doping amount of Al in the SiAl alloy target to 8-55wt%, so that the processing resistance of the film coating glass is improved.

And the difference between the refractive index n value of the deposited top protective layer with the light-emitting refractive index n value of 1.49-1.55 and the extinction coefficient k value of 0.00001-0.003 and the refractive index n value of the bonding layer is less than or equal to 0.03, so that the physical thickness of the top protective layer is increased to a large extent without affecting the optical performance of coated glass and laminated glass.

The physical thickness of the top protective layer, the first protective layer and the second protective layer can be reasonably designed by canceling the third protective layer, so that the thermal stability, the chemical stability and the mechanical stability of the coating layer can be improved, the high durability is realized, and the appearance color of the final laminated glass product can be freely adjusted.

The foregoing has outlined rather broadly the more detailed description of the embodiments of the present application in order that the principles and embodiments of the present application may be explained and illustrated herein, the above description being provided for the purpose of facilitating the understanding of the method and core concepts of the present application; meanwhile, as those skilled in the art will have modifications in the specific embodiments and application scope in accordance with the ideas of the present application, the present description should not be construed as limiting the present application in view of the above.

Claims

1. The coated glass is characterized by comprising a first glass substrate and a coating layer arranged on the surface of the first glass substrate;

2. The coated glass according to claim 1, wherein the refractive index of the first protective layer is greater than the refractive index of the second protective layer; and/or the physical thickness of the first protective layer is smaller than the physical thickness of the second protective layer.

3. The coated glass according to claim 1, wherein the first protective layer has an optical thickness of 15nm to 40nm, the second protective layer has an optical thickness of 20nm to 60nm, and the ratio of the first protective layer to the second protective layer has an optical thickness of 0.4 to 0.9.

4. The coated glass according to claim 1, wherein the top protective layer has a physical thickness of 80nm to 300nm.

5. The coated glass according to claim 1, wherein the coated glass has a pencil hardness of 9H or more, measured from the side of the coating layer.

6. The coated glass according to any one of claims 1 to 5, wherein the coating layer satisfies one or more of the following conditions:

(2) The physical thickness of the first protective layer is 5 nm-20 nm;

(3) The refractive index of the first protective layer is 2.0-2.75.

7. The coated glass according to any one of claims 1 to 5, wherein the coating layer satisfies one or more of the following conditions:

(2) The physical thickness of the second protective layer is 10 nm-40 nm;

(3) The refractive index of the second protective layer is 1.8-2.4.

8. The coated glass according to any one of claims 1 to 5, wherein the coating layer satisfies one or more of the following conditions:

(2) The physical thickness of each metal layer is independently 5 nm-20 nm;

9. The coated glass according to any one of claims 1 to 5, wherein the number of the functional stacks is at least two, a plurality of the functional stacks are stacked, and an intermediate layer is further provided between two adjacent functional stacks.

10. The coated glass according to claim 9, wherein the coating layer satisfies one or more of the following conditions:

11. The coated glass of any one of claims 1-5, wherein the coating layer further comprises an innermost adhesion layer disposed between the first glass substrate and the at least one functional stack, the innermost adhesion layer being in direct contact with the first glass substrate surface.

12. The coated glass according to claim 11, wherein the coating layer satisfies one or more of the following conditions:

(2) The physical thickness of the innermost adhesion layer is 10 nm-50 nm.

13. The coated glass according to any one of claims 1 to 5, wherein the coating layer satisfies one or more of the following conditions:

14. The coated glass of any one of claims 1-5, wherein at least one of the functional stacks further comprises a barrier layer in direct contact with the metal layer, the barrier layer having a physical thickness of less than or equal to 5nm, the barrier layer being of a material selected from at least one metal or metal alloy of Ti, ni, cr, nb, W.

15. The preparation method of the coated glass is characterized by comprising the following steps of:

providing a first glass substrate:

16. The method of claim 15, wherein the sputter target of the top protective layer comprises a SiAl alloy target comprising, in mass percent, 45% -92% Si and 8% -55% Al.

17. The method for preparing coated glass according to claim 16, wherein the target power supply of the top protective layer is a high-power pulse magnetron sputtering power supply, and the process parameters in the process of depositing the top protective layer satisfy one or more of the following conditions:

18. A laminated glass comprising a second glass substrate, an adhesive layer, and the coated glass of any one of claims 1-14, the adhesive layer being disposed between the coated glass and the second glass substrate, the top protective layer in the coating layer being in direct contact with the adhesive layer.

19. The laminated glass according to claim 18, wherein an absolute value of a difference between a refractive index of the top protective layer of the coating layer and a refractive index of the adhesive layer is not more than 0.03.