Color-changeable and heat-insulating glass for vehicles and preparation method of color-changeable and heat-insulating glass

Abstract

The invention relates to the technical field of motor vehicle glass, in particular to color-changeable and heat-insulating vehicle glass and a preparation method of the color-changeable and heat-insulating vehicle glass. The heat-insulating composite film layer is positioned on the front surface of the glass main body; the color-changeable composite film layer is positioned on the rear surface of the glass main body; the heat-insulating composite film layer comprises a first base layer Si3N4, a medium matching layer TiO2, a first metal layer, a transition layer, a second metal layer and a first protective layer SiO2 from inside to outside; the color-changeable composite film layer comprises a second base coat PVD SiO2, a first ITO plating layer with an electrode, an electrochromic film layer, a second ITO plating layer with an electrode and a second protective layer CVD SiO2 from inside to outside; the invention also provides a preparation method of the glass. The heat-insulating composite film layer can achieve a good heat-insulating effect; according to the color-changeable composite film layer, the corresponding color changing speed is high, the surface reflection brightness is adjustable, and the cyclic reversibility is good.

Description

Technical Field

[0001] The invention relates to the technical field of motor vehicle glass, and in particular to a color-changing and heat-insulating vehicle glass and a preparation method thereof. Background Art

[0002] At present, the most commonly used method for motor vehicle glass is to paste heat insulation film to play the role of sunshade and heat insulation, commonly known as automobile solar film, with an infrared blocking rate of 50%-70%, a visible light transmittance of 30%-70%, and poor infrared blocking efficiency. At the same time, its substrate is an organic material backing adhesive and is pasted on the surface of automobile glass. During use, there is a phenomenon of corrosion and aging of organic materials and backing adhesive by ultraviolet rays, which leads to adverse consequences such as blistering, discoloration, shedding, and film falling, which in turn affects driving safety. Secondly, if a product with a darker color and poor visible light transmittance is selected, it will also affect the driver's vision at night or in an environment with poor light environment, forming a safety hazard. At the same time, its service life is short, and it is difficult to remove the residual adhesive of the original automobile film. The secondary film causes an increase in the cost of vehicle use, and its application is also subject to certain restrictions. Therefore, the development of a color-changing and heat-insulating automobile glass that changes the visible light transmittance under different light conditions can meet the needs of the existing automobile market. Summary of the invention

[0003] In order to solve the above technical problems, the present invention adopts a heat-insulating functional film coated on the front surface of the glass and an electrochromic functional film coated on the rear surface, so that the glass has the functions of color change and heat insulation.

[0004] To achieve the above-mentioned purpose, an embodiment of the present invention provides a color-changing and heat-insulating automotive glass, the automotive glass comprising a glass body, the glass comprising a heat-insulating composite film layer on the front surface of the glass body and a color-changing composite film layer on the rear surface: the heat-insulating composite film layer comprises, from inside to outside, a first primer layer, a dielectric matching layer, a first metal layer, a transition layer, a second metal layer, and a first protective layer; the first primer layer is made of Si3N4, the dielectric matching layer is made of TiO2, the first metal layer is made of metallic silver, the transition layer is made of ZnSnO3, and the first protective layer is made of SiO2 prepared by a vacuum coating CVD process;

[0005] The color-changing composite film layer includes, from the inside to the outside, a second base layer, a first ITO coating, an electrochromic film layer, a second ITO coating, and a second protective layer; the second base layer is made of SiO2 prepared by a vacuum coating PVD process, the electrochromic film layer is made of WO3, the second protective layer is SiO2 prepared by a vacuum coating CVD process, and the first ITO coating layer and the second ITO coating layer both have lead electrodes.

[0006] Preferably, the thickness of the first coating layer is 2-15nm, the thickness of the dielectric matching layer is 20-30nm, the thickness of the first metal layer is 5-15nm, the thickness of the transition layer is 60-120nm, the thickness of the second metal layer is 5-15nm, and the thickness of the first protective layer is 25-200nm.

[0007] Preferably, the first primer layer and the dielectric matching layer of the heat-insulating composite film layer can be continuously and alternately arranged in 1-3 groups.

[0008] Preferably, the thickness of the second primer layer is 80-180 nm, the thickness of the second protective layer is 100-200 nm, and the thickness of the electrochromic film layer is 50-300 nm.

[0009] Preferably, the first ITO coating layer and the second ITO coating layer have a transmittance of 45-85% and a resistance of 0.5-5.5Ω.

[0010] Preferably, the glass body is any one of tempered glass, tempered plus laminated glass, and multi-layer laminated glass.

[0011] The present invention also provides a method for preparing a color-changing and heat-insulating automotive glass, the method being used for preparing the above-mentioned color-changing and heat-insulating automotive glass, and the method comprising the following steps:

[0012] S1: First, a first bottom layer Si3N4 is plated on the front surface of the glass by a vacuum coating PVD process, and then a dielectric matching layer TiO2, a first metal layer Ag, a transition layer ZnSnO3, a second metal layer Ag are plated, and finally a first protective layer SiO2 is prepared by a chemical vapor deposition CVD method;

[0013] S2: A second base layer and a first ITO coating layer are coated on the rear surface of the glass from the inside to the outside by a vacuum coating PVD process, and an electrode is led out at the edge of the first ITO coating layer; then an electrochromic film layer WO3 is deposited, and then a second ITO coating layer is coated by a vacuum coating PVD process, and an electrode is led out, and finally a second protective layer SiO2 is coated by a chemical vapor deposition CVD process.

[0014] Beneficial effects:

[0015] The present invention sets a heat-insulating composite film layer and a color-changing composite film layer on both sides of the glass body, wherein the heat-insulating composite film layer is plated with a first primer layer, a dielectric matching layer, a first metal layer, a first transition layer, a second metal layer, a first protective layer and other materials in sequence, wherein the first metal layer and the transition layer can be alternately set to 1-3 groups, so that it has a visible light range transmittance greater than 70%; wherein the color-changing composite film layer adopts an electrochromic film layer combined with an ITO transparent conductive film layer, so that its color change response speed is fast, the surface reflection brightness is adjustable, and the cycle reversibility is good, which meets the durable use requirements of automobile products. The production process of the present invention adopts a vacuum coating PVD process and a chemical vapor deposition CVD process, and its process is stable, the cost is low, and it is suitable for large-scale promotion and application. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 It is a structural schematic diagram of the present invention;

[0017] Figure 2 A process flow chart of a method for preparing a color-changing and heat-insulating automotive glass provided by an embodiment of the present invention;

[0018] Figure 3 This is a comparison chart of the light transmittance of a color-changing and heat-insulating automotive glass provided in Example 1 of the present invention and ordinary automotive film glass.

[0019] Labeling instructions: glass body 1, glass rear surface 2, second base layer 3, first ITO coating layer 4, electrochromic film layer 5, second ITO coating layer 6, second protective layer 7, glass front surface 8, first base layer 9, dielectric matching layer 10, first metal layer 11, transition layer 12, second metal layer 13, first protective layer 14. DETAILED DESCRIPTION

[0020] In order to more clearly explain the technical content of the present invention, it is described in detail in conjunction with specific embodiments and drawings. Obviously, the enumerated embodiments are only preferred implementation schemes of the present technical solution, and other technical solutions that can be obviously derived by technicians in this field based on the disclosed technical content still belong to the protection scope of the present invention.

[0021] In the description of the present invention, it should be noted that the terms "inside" and "outside" indicate positions or positional relationships based on the positions or positional relationships shown in the accompanying drawings, which are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific position, be constructed and operated in a specific position, and therefore cannot be understood as a limitation of the present invention. In addition, the terms "first" and "second" are used only for descriptive purposes, mainly to distinguish similar objects, and are not used to describe a specific order or sequence.

[0022] like Figure 1-3As shown, a color-changing and heat-insulating automotive glass comprises a glass body, the glass comprises a heat-insulating composite film layer on the front surface of the glass body and a color-changing composite film layer on the rear surface: the heat-insulating composite film layer comprises a first primer layer, a dielectric matching layer, a first metal layer, a transition layer, a second metal layer, and a first protective layer from inside to outside; the first primer layer is made of Si3N4, the dielectric matching layer is made of TiO2, the first metal layer is made of metallic silver, the transition layer is made of ZnSnO3, and the first protective layer is made of SiO2 prepared by a vacuum coating CVD process;

[0023] The glass body is any one of tempered glass, tempered laminated glass and multi-layer laminated glass.

[0024] Among them, the thickness of the first base layer is 2-15nm, the thickness of the dielectric matching layer is 20-30nm, the thickness of the first metal layer is 5-15nm, the thickness of the transition layer is 60-120nm, the thickness of the second metal layer is 5-15nm, and the thickness of the first protective layer is 25-200nm.

[0025] Among them, the first metal layer and the transition layer of the heat-insulating composite film layer can be continuously and alternately arranged in 1-3 groups. For example, 2 groups of heat-insulating composite film layers continuously and alternately arranged include the first primer layer, the dielectric matching layer, the first metal layer, the transition layer, the first metal layer, the transition layer, the second metal layer, and the first protective layer. For example, 3 groups of heat-insulating composite film layers continuously and alternately arranged include the first primer layer, the dielectric matching layer, the first metal layer, the transition layer, the first metal layer, the transition layer, the first metal layer, the transition layer, the second metal layer, and the first protective layer.

[0026] In actual design, according to the different bandwidths of the infrared spectrum, 1-3 groups of first metal layers and transition layers can be continuously and alternately set. For example, in the spectral range of 850-1200nm, the transmittance T≤30%, 1 group of first metal layer and transition layer is set; in the spectral range of 850-2000nm, the transmittance T≤20%, 2 groups of first metal layers and transition layers are set; in the spectral range of 850-2500nm and above, the transmittance T≤15%, 3 groups of first metal layers and transition layers are set; the first protective layer is plated by CVD method, which is mainly used to improve the protective performance of metallic silver, make its film layer denser and have better barrier properties, and improve the service life of the thermal insulation coating.

[0027] The color-changing composite film layer includes the second base layer, the first ITO coating layer, the electrochromic film layer, the second ITO coating layer, and the second protective layer from the inside to the outside; the material of the second base layer is SiO 2， The material of the second protective layer is SiO2 ，The first ITO coating layer and the second ITO coating layer both have electrodes for connecting to an external circuit; the electrodes are connected to a vehicle power supply, the voltage is controlled at 3-12V, the thickness of the second base layer is 25-100nm, the thickness of the second protective layer is 25-100nm, the transmittance of the first ITO coating layer and the second ITO coating layer is 45-85%, and the resistance is 0.5-5.5Ω.

[0028] The present invention also provides a method for preparing color-changing and heat-insulating automotive glass, which is used for preparing the above-mentioned color-changing and heat-insulating automotive glass, and the method comprises the following steps:

[0029] S1: Glass body cleaning: Use 3D anisotropic glass ultrasonic cleaning machine to clean the surface of the glass body to achieve a surface finish of 40-20 level.

[0030] S2: firstly, a first base layer is plated on the front surface of the glass body by using a vacuum coating PVD process, then a dielectric matching layer, a first metal layer, a transition layer, a second metal layer, and finally a first protective layer is plated, and finally, a first protective layer is prepared by using a chemical vapor deposition CVD method;

[0031] S3: The second bottom layer is plated from the inside to the outside on the rear surface of the glass body through the vacuum coating PVD process 、 The first ITO coating is formed, and electrodes are drawn out from the edge of the first ITO coating; then, an electrochromic film is deposited on the surface, and then a second ITO coating is formed by a vacuum coating PVD process, and electrodes are drawn out, and finally a second protective layer is formed by a chemical vapor deposition CVD process;

[0032] S4: Vacuum drying process: Place the glass substrate that has been fully coated into a vacuum drying device for drying.

[0033] The following is a further description with reference to specific embodiments.

[0034] Example 1

[0035] Place the 1300mmX1500mmX20mm tempered laminated glass in a 13-stage cleaning machine. After heating, spraying with chemicals, brush cleaning, ultrasonic cleaning, rinsing, pure water washing, air knife drying and other glass surface cleaning processes, the glass surface finish reaches 20-10 cleanliness level. The cleaned glass is clamped to the coating machine fixture by a robot to coat the front surface of the glass with a heat-insulating coating. The coating layers from the inside to the outside are: the first base layer of silicon nitride (Si3N4) The film thickness is 12nm; the dielectric matching layer titanium dioxide (TiO2) film thickness is 24nm; the first metal layer (Ag) film thickness is 10nm; the transition layer zinc tin oxide (ZnSnO3) film thickness is 91nm; the second metal layer (Ag) film thickness is 10nm; the first protective layer is a silicon dioxide (SiO) film prepared by the CVD method with a thickness of 150nm; a low-radiation heat-insulating film layer that blocks the transmission of infrared rays is obtained, and its transmittance T is ≤20% in the spectral range of 850-2000nm, which has a good heat-insulating effect.

[0036] An electrochromic coating was prepared on the rear surface of tempered laminated glass by magnetron sputtering + chemical vapor deposition process, wherein the second bottom layer silicon dioxide (SiO2) film with a thickness of 100nm was magnetron sputtered, a first ITO coating was magnetron sputtered on the second bottom layer, the resistance of the first ITO coating was 5Ω, and electrodes were drawn out at the edge of the first ITO coating, and an electrochromic tungsten oxide (WO3) film with a thickness of 60nm was sputtered on the surface of the first ITO coating; then a second ITO coating was magnetron sputtered, the resistance of which was 5Ω, and electrodes were drawn out at its edge; finally, a second protective layer silicon dioxide (SiO2) with a thickness of 150nm was plated by chemical vapor deposition CVD process.

[0037] The processed glass substrate is placed in a vacuum drying device and vacuum pressure is applied to remove impurity gases between film layers generated during processing and residual water vapor adsorbed during transportation to obtain a color-changing and heat-insulating glass product.

[0038] A voltage of 12 volts was applied to the electrodes at both ends of the above-mentioned color-changing and heat-insulating glass to stimulate the color change of the electrochromic film layer, so that the color of the glass appearance was sensitive and changed accordingly. The specific data are shown in Table 1.

[0039] Table 1

[0040] Example 1 No power Powered by 12 volts Brightness L 50 40 a -1.2 -2.0 b -0.8 -1.5

[0041] Example 2

[0042] Place the 1200mmX1400mmX30mm tempered glass in the 3D glass cleaning machine, and go through multiple glass surface cleaning processes such as chemical washing, rinsing, pure water washing, and air knife drying to make the glass surface smoothness reach 20-10 cleanliness level. The cleaned glass is clamped onto the coating equipment by means of a clamp, and a heat-insulating coating is applied to the front surface of the glass. The coating layers are sequentially coated from the inside to the outside as follows: the first base layer silicon nitride (Si3N4) has a film thickness of 10nm; the dielectric matching layer titanium dioxide (TiO2) has a film thickness of 30nm; the first metal layer (Ag) has a film thickness of 9nm; the transition layer zinc tin oxide (ZnSnO3) has a film thickness of 95nm; the second metal layer (Ag) has a film thickness of 12nm; the protective layer is a silicon dioxide (SiO) film prepared by a CVD method with a film thickness of 180nm; a low-radiation heat-insulating film layer that blocks infrared transmission is obtained, and its transmittance T is ≤18% in the spectral range of 850-2000nm.

[0043] An electrochromic coating is prepared on the rear surface of the tempered glass by magnetron sputtering + chemical vapor deposition process, wherein the magnetron sputtered bottom silicon dioxide (SiO2) film thickness is 120nm, the resistance of the first ITO coating is 3Ω, and an electrode is drawn out at the edge of the ITO coating to obtain the first ITO coating; and an electrochromic tungsten oxide (WO3) film with a thickness of 100nm is sputtered on the surface of the first ITO coating; then a second ITO coating is magnetron sputtered, the resistance of which is 3Ω, and an electrode is drawn out at its edge; finally, a protective layer of silicon dioxide (SiO2) with a thickness of 180nm is plated by chemical vapor deposition process; the glass substrate that has been processed as a whole is placed in a vacuum drying device, and vacuum pressure is applied to remove impurity gases between film layers generated during the processing and residual water vapor adsorbed during the transportation process, so as to obtain a color-changing and heat-insulating glass product.

[0044] A voltage of 12 volts was applied to the two end electrodes of the above-mentioned highly reflective electrochromic glass to stimulate the color change of the electrochromic film layer, so that the color of the glass appearance was sensitive and changed accordingly. The specific data are shown in Table 2.

[0045] Table 2

[0046] Example 2 No power Powered by 12 volts Brightness L 48 35 a -1.5 -2.5 b -1.2 -2.0

[0047] It can be seen from the above two embodiments that the heat-insulating composite film layer of the present invention has a good heat-insulating effect, and the color-changing composite film layer can reduce the reflection brightness and color bias to a blue-green phase that is friendly to human eyes.

[0048] Comparative Example 1

[0049] After cleaning the back surface of 1400mmX1200mmX20mm tempered laminated glass, make the back surface finish of the glass reach 20-10 cleanliness level, and stick solar film or ordinary insulating glass on the back of the cleaned glass.

[0050] The light transmittance of ordinary heat-insulating glass is compared with that of the electrochromic and heat-insulating functional glass obtained in Example 1. Figure 3 As shown. It can be known that the ordinary heat-insulating glass has a transmittance of 50% in the visible light range of 420-680nm and a transmittance of 35% in the infrared band of 800-2500nm. The color-changing heat-insulating glass obtained in Example 1 has a transmittance of 80% in the visible light range of 420-680nm and a transmittance of 15% in the infrared band of 800-2500nm. In addition, the brightness of the two is measured. The brightness of the electrochromic glass is 35, and the brightness of the ordinary heat-insulating glass is 57.

[0051] That is, the color-changing insulating glass has obvious advantages over ordinary film glass in terms of light transmittance in the visible light region, thermal insulation performance in the infrared region, and brightness.

[0052] The embodiments described above are only preferred specific implementation modes of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical solutions and concepts of the present invention within the technical scope of the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A color-changing and heat-insulating automotive glass, comprising a glass body, characterized in that: The automotive glass further comprises a heat-insulating composite film layer on the front surface of the glass body and a color-changing composite film layer on the rear surface: the heat-insulating composite film layer comprises, from inside to outside, a first primer layer, a dielectric matching layer, a first metal layer, a transition layer, a second metal layer, and a first protective layer; the first primer layer is made of Si3N4, the dielectric matching layer is made of TiO2, the first metal layer is made of metallic silver, the transition layer is made of ZnSnO3, and the first protective layer is made of SiO2 prepared by a vacuum coating CVD process; The color-changing composite film layer includes, from the inside to the outside, a second base layer, a first ITO coating, an electrochromic film layer, a second ITO coating, and a second protective layer; the second base layer is made of SiO2 prepared by a vacuum coating PVD process, the electrochromic film layer is made of WO3, the second protective layer is SiO2 prepared by a vacuum coating CVD process, and the first ITO coating layer and the second ITO coating layer both have lead electrodes.

2. The color-changing and heat-insulating automotive glass according to claim 1, characterized in that: The thickness of the first primer layer is 2-15nm, the thickness of the dielectric matching layer is 20-30nm, the thickness of the first metal layer is 5-15nm, the thickness of the transition layer is 60-120nm, the thickness of the second metal layer is 5-15nm, and the thickness of the first protective layer is 25-200nm.

3. The color-changing and heat-insulating automotive glass according to claim 1, characterized in that: The first metal layer and the transition layer of the heat-insulating composite film layer can be continuously and alternately arranged in 1-3 groups.

4. The color-changing and heat-insulating automotive glass according to claim 1, characterized in that: The thickness of the second primer layer is 80-180 nm, the thickness of the second protective layer is 100-200 nm, and the thickness of the electrochromic film layer is 50-300 nm.

5. The color-changing and heat-insulating automotive glass according to claim 1, characterized in that: The first ITO coating layer and the second ITO coating layer have a transmittance of 45-85% and a resistance of 0.5-5.5Ω.

6. The color-changing and heat-insulating automotive glass according to claim 1, characterized in that: The glass body is any one of tempered glass, tempered laminated glass and multi-layer laminated glass.

7. A method for preparing color-changing and heat-insulating automotive glass, characterized in that: The preparation method is used for preparing the color-changing and heat-insulating automotive glass according to any one of claims 1 to 6, and the method comprises the following steps: S1: First, a first bottom layer Si3N4 is plated on the front surface of the glass by a vacuum coating PVD process, and then a dielectric matching layer TiO2, a first metal layer Ag, a transition layer ZnSnO3, a second metal layer Ag are plated, and finally a first protective layer SiO2 is prepared by a chemical vapor deposition CVD method; S2: A second base layer and a first ITO coating layer are coated on the rear surface of the glass from the inside to the outside by a vacuum coating PVD process, and an electrode is led out at the edge of the first ITO coating layer; then an electrochromic film layer WO3 is deposited, and then a second ITO coating layer is coated by a vacuum coating PVD process, and an electrode is led out, and finally a second protective layer SiO2 is coated by a chemical vapor deposition CVD process.

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