Anti-halation glass and vehicle

Abstract

The invention provides anti-halation glass and a vehicle. The anti-halation automobile glass comprises a glass plate; an anti-halation film is arranged on the surface of the glass plate, and a transition layer of the anti-halation film is arranged on the surface; the anti-halation film comprises a transition layer, a silicon-doped diamond-like layer and an oleophobic layer which are sequentially arranged, and the oleophobic layer is located in at least part of the area of the surface of the silicon-doped diamond-like layer; and the content of silicon atoms in the silicon-doped diamond-like carbon layer is 15-20 at%. The invention further provides a vehicle provided with the anti-halation glass. The anti-halation film of the anti-halation glass provided by the invention can eliminate halation defects and radial defects generated during imaging.

Description

Technical Field

[0001] This invention relates to an anti-glare glass and a vehicle, belonging to the field of automotive technology. Background Technology

[0002] Currently, the placement of automotive intelligent driving cameras mainly falls into two categories. One type is placed on the exterior of the vehicle (such as the roof area), which, although considered a fashionable feature of intelligent driving configurations, has a significant impact on wind resistance. The other type is installed inside the vehicle, collecting external information through the Advanced Driver Assistance System (ADAS) area on the windshield. With the continuous updates and iterations of intelligent driving technology, exterior cameras will no longer be used; instead, intelligent driving cameras will be installed inside the vehicle and concealed.

[0003] When intelligent driving cameras are installed inside the vehicle, they can collect external information in real time through the ADAS area of ​​the windshield. This gradually increases the requirements for the ADAS area of ​​the windshield, including optical distortion and cleanliness, because the glass quality of the ADAS area directly determines the image quality of the intelligent driving camera, thus affecting the reliability of intelligent driving. In particular, the glass quality of the ADAS area has a particularly serious impact on visual imaging in intelligent driving.

[0004] Therefore, it is crucial to develop a windshield that offers excellent performance in the ADAS area while ensuring that it does not affect the image quality of intelligent driving cameras.

[0005] In existing technologies, although attempts have been made to improve glass performance through coating, there are still significant shortcomings. For example, CN105152548B discloses a method for preparing diamond-like carbon (DLC) film glass, which involves alternating deposition of high SP (spline-dependent) coatings. 2 / Low SP 2 The hybrid diamond-like carbon (DLC) coating combined with an anti-fingerprint hydrophobic coating, although it solves the problem of interlayer bonding and improves the light transmittance (0.7 mm Corning glass substrate), abrasion resistance and aging resistance of the glass, has a water contact angle of only about 100°, and its anti-fingerprint and hydrophobic properties are insufficient.

[0006] CN115161601B discloses a processing method and equipment for ultrafast laser deposition of multi-layered structures including diamond-like carbon (DLC) film, anti-reflective film, and anti-fingerprint film. The method uses ultrafast laser deposition technology to prepare multi-layered structures (DLC film, anti-reflective film, and anti-fingerprint film). Although the water contact angle of the anti-fingerprint hydrophobic and oleophobic (AF) coating is increased to 110-120°, the anti-fingerprint coating is made of perfluoropolyether material, which has no siloxane groups at the end. It is only physically bonded to the silicon carbide layer through van der Waals forces and lacks chemical bond connection, resulting in weak coating adhesion.

[0007] CN117737681A discloses a method for preparing a highly transparent hydrophobic DLC film on the surface of aviation plexiglass. The method involves preparing a fluorine-doped DLC film on aviation plexiglass. Although the method achieves highly transparent hydrophobic properties on the surface of aviation plexiglass, the water contact angle is still below 110°.

[0008] Therefore, it is of great significance to develop a thin film that can enable the ADAS area of ​​glass to have good imaging quality, thereby ensuring the reliability of intelligent driving. Summary of the Invention

[0009] To address the aforementioned problems, the present invention provides an anti-halo glass and vehicle, wherein the anti-halo glass, through an anti-halo film, can effectively prevent the formation of radial defects while eliminating halo-like defects.

[0010] To achieve the above objectives, in a first aspect, the present invention also provides an anti-halo glass, wherein the anti-halo glass includes a glass plate; the surface of the glass plate has an anti-halo film, wherein a transition layer of the anti-halo film is disposed on the surface;

[0011] The anti-halo film comprises a transition layer, a silicon-doped diamond-like carbon (DLC) layer, and an oleophobic layer arranged sequentially, wherein the oleophobic layer is located in at least a portion of the surface of the silicon-doped DLC layer; the silicon content in the silicon-doped DLC layer is 15-20 at.

[0012] The inventors of this invention discovered that the oleophobic coating on the outer surface of automotive glass, located in the sliding or wiping area of ​​windshield wipers, is prone to failure. This is due to both photoaging and physical wear caused by hard dust particles in the air adhering to the glass surface and undergoing scraping and friction. When a camera captures images through such automotive glass, halo-like and radial defects will appear in the image. By using a silicon-doped diamond-like carbon (DLC) layer, which has a harder surface than a diamond-like carbon (DLC) layer, the problem of halo-like defects caused by scratches on the glass surface during sliding and wiping by windshield wipers can be solved. By adding an oleophobic coating to the surface of the silicon-doped DLC layer, the problem of radial defects in camera imaging caused by the oil film on the glass surface can be solved. By combining the silicon-doped DLC layer and the oleophobic coating, the shortcomings of the oleophobic coating on automotive glass, such as its short service life and difficulty in achieving long-term effectiveness, can be overcome, effectively improving the lifespan of the oleophobic coating and achieving a long-lasting effect. The anti-halo film provided by this invention can not only be applied to the outer surface of glass to solve the above-mentioned problems, but when applied to the inner surface of glass, it can also solve the problem of radial defects in camera imaging, smart glasses, etc. caused by oil film on the glass surface by means of an oleophobic layer.

[0013] The silicon-doped diamond-like carbon (DLC) layer used in this invention is a DLC layer doped with silicon atoms. The doped silicon atoms enable the generation of more Si-OH group active binding sites on the layer surface, thereby improving the adhesion between the silicon-doped DLC layer and the oleophobic layer. The silicon atom content in the silicon-doped DLC layer used in this invention is 15-20 at%. If the silicon atom content in the silicon-doped DLC layer is less than 15 at%, the adhesion of the oleophobic layer will be insufficient, affecting the overall light transmittance; if the silicon atom content in the silicon-doped DLC layer exceeds 20 at%, the hardness of the silicon-doped DLC layer will decrease, leading to poor wear resistance.

[0014] According to a specific embodiment of the present invention, preferably, the thickness of the silicon-doped diamond-like layer is 100-300 nm, more preferably 100-200 nm.

[0015] According to a specific embodiment of the present invention, preferably, the refractive index of the silicon-doped diamond-like carbon layer is 1.6-1.8. Ordinary diamond-like carbon layers have a refractive index greater than 2. The silicon-doped diamond-like carbon layer of the present invention has a lower refractive index, resulting in a smaller difference from the refractive index of glass (e.g., the bulk refractive index of soda-lime glass is about 1.5), thereby improving the overall light transmittance. This allows the present invention to use a thicker silicon-doped diamond-like carbon layer while maintaining an optical transmittance of >70%.

[0016] According to a specific embodiment of the present invention, the thickness of the silicon-doped diamond-like carbon layer is 100-300 nm. If the thickness of the silicon-doped diamond-like carbon layer is less than 100 nm, it will result in insufficient abrasion resistance; if the thickness of the silicon-doped diamond-like carbon layer is greater than 300 nm, the light transmittance will not meet the requirements of the present invention.

[0017] According to a specific embodiment of the present invention, preferably, the oleophobic layer contains a perfluoropolyether siloxane; more preferably, the perfluoropolyether siloxane has one of the structures shown in Formula I to Formula III:

[0018]

[0019] Formula I;

[0020]

[0021] Formula II;

[0022]

[0023] Formula III;

[0024] In equations I to III, m x1 +m x2 =15-30, mx1 Represents m 11 m 21 m 31 m x2 Represents m 12 m 22 m 32 ;

[0025] R x1 :R 11 R 21 R 31 Each is independently selected from C1-6 unbranched fluoroalkyl groups;

[0026] R x2 :R 22 R 32 Each is independently selected from C1-6 unbranched fluoroalkylene groups;

[0027] R x3 :R 23 R 33 Each is independently selected from C3-6 fluoroalkylene groups with cyclic structures;

[0028] R 34 Selected from C1-6 branched fluoroalkylene groups.

[0029] According to a specific embodiment of the present invention, preferably, R x1 R x2 R x3 R 34 Substituents having the following structure:

[0030] R x1 : ;

[0031] R x2 : , ;

[0032] R x3 : ;

[0033] R x4 : .

[0034] In the perfluoropolyether siloxane shown in Formula II, the molecular structure contains a hydrolyzable siloxane group at each end. This group can combine with the Si-OH group on the surface of silicon-doped diamond-like carbon (Si-DLC) layer to form Si-O-Si bonds, and can also combine with a small amount of SP 3Hybridized C-OH groups combine to form CO-Si bonds. Compared to the perfluoropolyether siloxane shown in Formula I, the perfluoropolyether siloxane shown in Formula II, due to the presence of both head- and tail-dual hydrolyzable groups, allows a single oleophobic molecule to form two binding sites with the Si-DLC surface, thereby enhancing the adhesion between the oleophobic layer and the Si-DLC layer. Compared to the perfluoropolyether siloxane shown in Formula III, the fluoroalkylene groups in the perfluoropolyether siloxane shown in Formula II are unbranched, resulting in a coating with a lower coefficient of friction. This leads to lower wiper resistance in the coated area, reducing wear and tear on the coating and improving its durability. The preferred embodiment of this invention uses the perfluoropolyether siloxane shown in Formula II. All perfluoropolyether siloxanes used in this invention are commercially available materials.

[0035] According to a specific embodiment of the present invention, preferably, the proportion of F replacing H in the perfluoropolyether siloxane is greater than or equal to 80%. If the proportion of F replacing H in the perfluoropolyether siloxane is less than 80%, it may result in insufficient oleophobicity, i.e., a low contact angle.

[0036] According to a specific embodiment of the present invention, preferably, the molecular weight of the perfluoropolyether siloxane is 5000-10000 g / mol.

[0037] According to a specific embodiment of the present invention, preferably, the thickness ratio of the silicon-doped diamond-like carbon (DLC) layer to the oleophobic layer is (15-20):1. By controlling the thickness ratio of the DLC layer to the oleophobic layer within the above range, both layers can fail simultaneously, avoiding premature degradation of a single function and preventing performance waste caused by the degradation or failure of one function before the other has degraded. If the thickness ratio of the silicon-doped DLC layer to the oleophobic layer exceeds the range of the present invention, the oleophobic layer will fail before the silicon-doped DLC layer, while the silicon-doped DLC layer retains its performance, resulting in underutilization of the performance (superhardness). If the thickness ratio of the silicon-doped DLC layer to the oleophobic layer is lower than the range of the present invention, both the silicon-doped DLC layer and the oleophobic layer will fail prematurely, failing to meet the usage requirements.

[0038] According to a specific embodiment of the present invention, preferably, the transition layer is a silicon dioxide transition layer.

[0039] According to a specific embodiment of the present invention, preferably, the thickness of the transition layer is 20-200 nm, more preferably 50-100 nm.

[0040] According to a specific embodiment of the present invention, preferably, the sum of the thicknesses of the silicon-doped diamond-like layer and the transition layer is 100-300 nm.

[0041] According to a specific embodiment of the present invention, preferably, the above-mentioned anti-halo film is prepared by a method comprising the following steps:

[0042] A transition layer is formed on the surface of the substrate, for example by magnetron sputtering deposition;

[0043] A silicon-doped diamond-like layer is formed on the surface of the transition layer, for example by magnetron sputtering deposition.

[0044] An oleophobic layer is formed in at least a portion of the surface of the silicon-doped diamond-like layer, for example by spraying.

[0045] According to a specific embodiment of the present invention, preferably, the light transmittance of the anti-halo glass is greater than 70%.

[0046] According to a specific embodiment of the present invention, preferably, the anti-halo glass has a lateral curvature ≥ 500 mm and a longitudinal curvature ≥ 1000 mm.

[0047] According to a specific embodiment of the present invention, preferably, the oil contact angle of the anti-halo glass is greater than 90°.

[0048] According to a specific embodiment of the present invention, preferably, the anti-glare glass is laminated glass, specifically including an inner glass plate, an intermediate interlayer, and an outer glass plate. The outer glass plate has a first surface facing outwards from the vehicle and a second surface facing inwards from the vehicle. The inner glass plate has a third surface facing outwards from the vehicle and a fourth surface facing inwards from the vehicle. The intermediate interlayer is disposed between the second surface and the third surface.

[0049] The first surface of the outer glass plate has an anti-halo film, and the transition layer of the anti-halo film is disposed on the first surface; or, the fourth surface of the inner glass plate has an anti-halo film, and the transition layer of the anti-halo film is disposed on the fourth surface.

[0050] According to a specific embodiment of the present invention, when the anti-halo film is disposed on the first surface of the outer glass plate, the layers from the first surface outward are a transition layer, a silicon-doped diamond-like layer, and an oleophobic layer.

[0051] Secondly, the present invention also provides a method for preparing the above-mentioned anti-halo glass, which includes the following steps:

[0052] A transition layer and a silicon-doped diamond-like layer are formed on the surface of the glass plate to obtain a glass plate with a pre-coated film.

[0053] An oleophobic layer is formed on the surface of a silicon-doped diamond-like layer, and after curing, anti-halo glass is obtained.

[0054] According to a specific embodiment of the present invention, when the anti-halo glass is laminated glass, the preparation method includes the following two methods:

[0055] The first type:

[0056] A transition layer and a silicon-doped diamond-like layer are formed on the first surface of the outer glass plate to obtain an outer glass plate with a pre-coated film.

[0057] The inner glass plate, the intermediate interlayer, and the outer glass plate with a pre-coated film are laminated together, wherein the intermediate interlayer is located between the second surface of the outer glass plate and the third surface of the inner glass plate.

[0058] An oleophobic layer is formed on the surface of a silicon-doped diamond-like layer, and after curing, anti-halo glass is obtained, that is, glass with an anti-halo film on the outer surface.

[0059] The second type:

[0060] A transition layer and a silicon-doped diamond-like layer are formed on the fourth surface of the inner glass plate to obtain an inner glass plate with a pre-coated film.

[0061] The inner glass plate with a pre-coated film, the intermediate interlayer, and the outer glass plate are laminated together, wherein the intermediate interlayer is located between the second surface of the outer glass plate and the third surface of the inner glass plate.

[0062] An oleophobic layer is formed on the surface of a silicon-doped diamond-like layer, and after curing, anti-halo glass is obtained, that is, glass with an anti-halo film on the inner surface.

[0063] According to a specific embodiment of the present invention, in the above preparation method, the transition layer can be prepared on one side of the glass plate without special selection. Specifically, when the anti-halo glass is glass with an anti-halo film on its outer surface, after the transition layer is formed, the surface of the glass plate with the transition layer becomes the first surface, i.e., the side with the pre-coated film, which is the air surface of the glass, while the other surface becomes the second surface. When the anti-halo glass is glass with an anti-halo film on its inner surface, after the transition layer is formed, the surface of the glass plate with the transition layer becomes the fourth surface, i.e., the side with the pre-coated film, which is the air surface of the glass, while the other surface becomes the third surface.

[0064] According to a specific embodiment of the present invention, in the above preparation method, when laminating the inner glass plate, a third surface, a fourth surface, or a first surface and a second surface can be pre-specified for the inner glass plate, and then the lamination can be performed directly, with one side surface of the inner glass plate in contact with the intermediate interlayer as the third surface or one side surface of the outer glass plate in contact with the intermediate interlayer as the second surface.

[0065] According to a specific embodiment of the present invention, the glass plate has a signal transmission area for optical signal transmission from the sensor, and the anti-halo film at least covers the signal transmission area. With this arrangement, the sensor (such as a camera) can capture external images through the signal transmission area, and the imaging will not exhibit problems such as halo-like defects or radial defects.

[0066] It should be noted that the optical signal of the sensor can be the optical signal emitted and / or received by the sensor. That is, all optical signals emitted and / or received by the sensor will pass through the signal transmission area on the glass plate.

[0067] According to a specific embodiment of the present invention, preferably, the transition layer is prepared by magnetron sputtering; during the magnetron sputtering deposition process, the argon gas flow rate is 60-80 sccm, the target material is a silicon dioxide target, and the sputtering power is 120-150 W. Specifically, it can be carried out as follows: using a silicon dioxide target material with a purity greater than 99.99%, the coating chamber is evacuated; argon gas is introduced and the flow rate is stabilized at a preset value, the RF power supply is turned on and maintained at the set power, and the deposition is carried out to a preset thickness to form a transition layer.

[0068] According to a specific embodiment of the present invention, preferably, the silicon-doped diamond-like carbon layer is prepared by magnetron sputtering; during the magnetron sputtering deposition process, the argon flow rate is 30-50 sccm, the methane flow rate is 10-20 sccm, and the deposition targets are graphite and silicon targets, with the sputtering power of the graphite target being 100-500 W and the sputtering power of the silicon target being 100-150 W. Specifically, it can be carried out as follows: using graphite and silicon targets with a purity greater than 99.99%, the coating chamber is evacuated; argon and methane are introduced, and after the chamber pressure stabilizes, the radio frequency current is turned on to deposit to the target thickness.

[0069] According to a specific embodiment of the present invention, preferably, the oleophobic layer is formed by spraying, wherein the spraying flow rate is 100-150 mL / min, the spraying atomization pressure is 0.15-0.2 MPa, the spraying height is 10-20 mm, and the spraying speed is 400-800 mm / s; more preferably, the spraying flow rate is 120 mL / min, the spraying atomization pressure is 0.2 MPa, the spraying height is 14 mm, and the spraying speed is 600 mm / s.

[0070] According to a specific embodiment of the present invention, preferably, the curing temperature is 60-100 ℃ and the curing time is 50-70 min; more preferably, the curing temperature is 80 ℃ and the curing time is 60 min.

[0071] According to a specific embodiment of the present invention, preferably, the preparation method further includes a step of plasma treatment of the surface of the silicon-doped diamond-like layer before forming the oleophobic layer. More preferably, compressed air plasma treatment is used to treat the glass surface (i.e., the surface on which the transition layer and the silicon-doped diamond-like layer are to be formed), with an air pressure of 0.3-0.6 MPa, an air flow rate of 10-30 L / min, a treatment power of 100-300 W, a treatment speed of 100-150 mm / s, and a treatment height of 10-15 mm; even more preferably, the air pressure is 0.45 MPa, the air flow rate is 10-30 L / min, the treatment power is 200 W, the treatment speed is 120 mm / s, and the treatment height is 15 mm. Specifically, it can be carried out as follows: the glass plate is sent into the coating chamber, the chamber is evacuated, and heated to 95-105 °C; argon gas with a flow rate of 20-30 sccm is introduced, and argon plasma is generated by turning on the radio frequency power supply to perform argon plasma cleaning on the glass surface.

[0072] Thirdly, the present invention also provides a vehicle, wherein the vehicle is equipped with the anti-glare glass provided by the present invention.

[0073] According to a specific embodiment of the present invention, preferably, the anti-glare glass can be used for the windshield, side windows, rear window, B-pillar glass, etc. of a vehicle. Furthermore, the anti-glare film of the anti-glare glass can be applied to the side of the vehicle glass facing outwards or to the side facing inwards.

[0074] According to a specific embodiment of the present invention, preferably, the windshield of the vehicle is the anti-halo glass, and the vehicle has a camera disposed inside the vehicle. The camera lens of the camera corresponds to the signal transmission area of ​​the windshield, and the anti-halo film at least covers the signal transmission area. With this arrangement, the camera can capture external images through the signal transmission area without exhibiting halo-like or radial defects in the image.

[0075] According to a specific embodiment of the present invention, when the windshield of a vehicle is anti-halo glass, when people inside the vehicle use smart glasses, camera phones, or other camera devices to take pictures or videos through the windshield, the presence of the anti-halo film can provide a good imaging effect, and there will be no halo-like defects or radial defects in the imaging.

[0076] According to a specific embodiment of the present invention, preferably, the vehicle is an automobile.

[0077] Compared with the prior art, the present invention has the following beneficial effects:

[0078] The anti-halo glass provided by the present invention is provided with an anti-halo film, which consists of a transition layer, a silicon-doped diamond-like carbon layer, and an oleophobic layer. The silicon-doped diamond-like carbon layer can improve surface hardness and enhance scratch resistance, thereby avoiding the generation of micro-scratches and eliminating halo-like defects when imaging through the anti-halo film. The transition layer can improve the adhesion between the silicon-doped diamond-like carbon layer and the glass, etc. The oleophobic layer is provided in at least a portion of the silicon-doped diamond-like carbon layer, which can effectively prevent radial defects when imaging through the anti-halo film. Attached Figure Description

[0079] Figure 1 These are two defects in the area through which the camera signal passes through the windshield.

[0080] Figure 2 This is an image captured by a camera through normal-quality glass.

[0081] Figure 3 An image captured by a camera through glass covered with tiny scratches.

[0082] Figure 4 This is an image captured by a camera through a tiny scratch in a fixed direction.

[0083] Figure 5 This is an image captured by a camera through a glass surface covered in oil stains.

[0084] Figure 6 This is a schematic diagram of the anti-halo glass of the present invention.

[0085] Figure 7 This is a cross-sectional schematic diagram of the anti-halo glass of the present invention. Detailed Implementation

[0086] In order to provide a clearer understanding of the technical features, objectives and beneficial effects of the present invention, the technical solution of the present invention will now be described in detail below, but it should not be construed as limiting the scope of implementation of the present invention.

[0087] The inventors of this invention discovered the following phenomenon while studying the imaging performance of a camera installed in a vehicle:

[0088] When a camera captures a light source through the signal-passing area of ​​the windshield, two imaging defects will occur (such as...). Figure 1 As shown): one type is a halo-like defect surrounding the light source, and the other is a linear, radial defect originating from the light source.

[0089] It should be noted that the signal transmission area refers to the signal transmission area of ​​the sensors inside the vehicle on the windshield. These sensors include, but are not limited to, cameras, infrared cameras, and LiDAR (Light Detection and Ranging) systems. This embodiment uses a camera as an example.

[0090] Furthermore, the present invention reproduces the two aforementioned defects through experiments:

[0091] (1) Normal imaging: The imaging effect of the camera when shooting through normal quality glass is as follows. Figure 2 As shown;

[0092] (2) Halo-like defects: The imaging effect of the camera when shooting through glass covered with tiny scratches is as follows. Figure 3 As shown, when there are many tiny scratches on the glass surface, the light source captured by the camera will show obvious halo, which is caused by the scratches scattering the light passing through the glass.

[0093] The image quality achieved by the camera through a tiny scratch in a fixed direction is as follows: Figure 4 As shown, it can be seen that when the scratch is distributed in a fixed direction, the long axis of the halo is perpendicular to the direction of the scratch. In combination with the actual use scenario, the wiper wipes in a fixed direction in the glass signal transmission area, so the glass is prone to producing halo-like defects in a fixed direction. The resulting directional micro scratches eventually make the halo-like defects elliptical, and the long axis is perpendicular to the working direction of the wiper (the direction of the scratch).

[0094] (3) Radial defects: The imaging effect of the camera when shooting through oil-stained glass is as follows. Figure 5 As shown, when oil stains adhere to the glass surface, the light source captured by the camera will produce linear radial defects.

[0095] Examples 1-6 each provide an anti-halo glass, the structure of which is as follows: Figure 7 As shown. The anti-halo glass includes: an inner glass plate 1, an intermediate bonding layer (i.e., an intermediate interlayer) 2, an outer glass plate 3, a transition layer 4, a silicon-doped diamond-like carbon layer 5, and an oleophobic layer 6; wherein, the dashed line represents the signal transmission area;

[0096] The inner glass panel 1 has a third surface facing outwards and a fourth surface facing inwards, the outer glass panel 3 has a first surface facing outwards and a second surface facing inwards, and the intermediate adhesive layer 2 bonds the second surface of the outer glass panel 3 and the third surface of the inner glass panel 1 together.

[0097] A transition layer 4 and a silicon-doped diamond-like layer 5 are provided on the first surface of the outer glass plate 3, and an oleophobic layer 6 is provided in a portion of the silicon-doped diamond-like layer 5 away from the surface of the outer glass plate 3.

[0098] The inner glass plate 1 is made of green glass with a thickness of 2.1 mm;

[0099] The intermediate adhesive layer 2 is a PVB film with a thickness of 0.76 nm;

[0100] The outer glass panel 3 is made of clear glass with a thickness of 2.1 mm;

[0101] Transition layer 4 is a silicon dioxide transition layer;

[0102] The oleophobic layer 6 is made of perfluoropolyether siloxane as shown in Formula II.

[0103] The anti-halo glass of Examples 1-6 can be used as the windshield of a car, and the anti-halo film covers the signal transmission area of ​​the windshield (e.g., Figure 6 As shown), specifically, the anti-halo film includes a transition layer 4, a silicon-doped diamond-like carbon layer 5, and an oleophobic layer 6 (as shown). Figure 7 (As shown).

[0104] It should be noted that the signal transmission area includes, but is not limited to, regular shapes such as trapezoids, circles, ellipses, polygons, or other irregular shapes, which can be flexibly adjusted and set according to actual needs.

[0105] The preparation method of the anti-halo glass provided in Examples 1-6 includes the following steps:

[0106] 1. Glass plate pretreatment

[0107] (1) Cleaning: Select 2.1 mm thick white glass as the outer glass plate 3. First, clean the outer glass plate 3 with deionized water, then clean it with isopropanol to remove oil, and blow dry the glass surface.

[0108] (2) Plasma treatment: The cleaned outer glass plate 3 is sent into the coating chamber, and the chamber is evacuated and heated to achieve a vacuum level of 5.0 × 10⁻⁶. -3 Pa, temperature 100±5℃; then argon gas was introduced, radio frequency power was turned on, and argon plasma cleaning was performed for 5 min to obtain the pretreated outer glass plate 3.

[0109] 2. Magnetron sputtering to deposit SiO2 transition layer

[0110] Using a SiO2 target with a purity greater than 99.99%, the cavity was evacuated again to 5.0 × 10⁻⁶. -3 Pa, argon gas is introduced, the flow rate is adjusted to stabilize the working gas pressure, and then the radio frequency power supply is turned on. The SiO2 transition layer is deposited according to the preset thickness. The specific parameters are shown in Table 1 and Table 2.

[0111] 3. Magnetron sputtering to deposit Si-DLC layer

[0112] Using graphite and silicon targets with a purity greater than 99.99%, the coating chamber was evacuated to a vacuum level of 5.0 × 10⁻⁶. -3 Pa, argon sputtering gas and methane reaction gas are introduced. After the chamber pressure stabilizes, the RF power supply is turned on, and a Si-DLC layer is deposited according to the preset thickness. Specific parameters are shown in Table 1 and Table 2.

[0113] 4. The outer glass plate 3, coated with SiO2 transition layer and Si-DLC layer, and the inner glass plate 1 are pressed together and formed. Then, the outer glass plate 3 and the inner glass plate 1 are bonded together through the intermediate adhesive layer 2. The outer glass plate 3 is bonded to the side surface that is not coated with SiO2 transition layer and Si-DLC layer to form a laminated glass. The specific structure is: inner glass plate 1, intermediate adhesive layer 2, outer glass plate 3, SiO2 transition layer, and Si-DLC layer.

[0114] 5. Preparation of oleophobic coating

[0115] (1) Cleaning: The laminated glass is cleaned and dried with water using a washing machine. The conveying speed is 7±1 m / min and the cleaning time is 35 s.

[0116] (2) Plasma activation: The surface of the Si-DLC layer of the outer glass plate 3 is treated with compressed air plasma equipment, wherein the air pressure is 0.45 MPa, the air flow rate is 22 L / min, the processing power is 200 W, the processing speed is 120 mm / s, and the processing height is 15 mm.

[0117] (3) Spraying: The perfluoropolyether siloxane coating shown in Type II is sprayed onto the Si-DLC layer using a pneumatic spray gun to form an oleophobic layer. The spraying flow rate is 120 mL / min, the spraying is done in a fan shape with a fan angle of 120°, the atomization pressure is 0.2 MPa, the spraying height is 14 mm, and the spraying speed is 600 mm / s.

[0118] In this embodiment, the perfluoropolyether siloxane represented by Formula II satisfies the following conditions:

[0119]

[0120] Formula II

[0121] R 22 for, ;

[0122] R 23 for ;

[0123] m 21 It is 21-25;

[0124] m 22 It is 1-5;

[0125] The molecular weight is 5500-6000 g / mol.

[0126] (4) Curing: Curing the sprayed glass at 80 °C for 60 min to complete the preparation of the oleophobic layer.

[0127] 6. The glass with the oleophobic layer formed is then bonded with accessories to obtain anti-halo glass. The parameters of the anti-halo glass are shown in Table 2.

[0128] Comparative Examples 1-5 provide a windshield, and the parameters of the preparation process are shown in Tables 1 and 2. The specific parameters of the windshield are shown in Tables 1 and 2, and the rest are the same as in Example 1.

[0129] Performance testing

[0130] 1. Rain and wiper performance

[0131] (1) Simulated wiper wiping experiment: The glass was placed horizontally, the wiper blade was cut into 10 cm segments, and the wiper blade was used to wipe the glass surface at a vertical angle. A load of 10 N was added to the wiper blade, the single stroke was 10 cm, and the round trip was counted as 1. The powder composition of the dust solution used in the experiment is shown in Table 3. The dust solution was prepared according to the mass ratio of powder:water = 3:97. Before the start of the experiment and after every 1000 wipes, 2 mL of dust solution was added between the glass and the wiper blade.

[0132] (2) Characterization of abrasion resistance: The abrasion resistance of glass is directly characterized by the rain-resistant wiper test; the number of times the sample is scraped when a halo-like defect appears is taken as the limit of the abrasion resistance of the sample.

[0133] (3) Test results: After 50,000 scratches, the anti-halo glass of Examples 1-5 of the present invention did not show obvious halo scattering defects or radial light scattering defects, and the oil contact angle was >70°, showing a very high rain-resistant scratching ability.

[0134] 2. Resistance to radial defects

[0135] The oil (diiodomethane) contact angle is used to characterize the sample's resistance to radial defects. The higher the oil contact angle, the stronger the sample's resistance to radial defects.

[0136] 3. Photoaging resistance

[0137] (1) Experimental method: UV aging test was conducted according to GB 9656-2021. The test conditions were UV resistance for 500 h.

[0138] (2) Test results: After 500 h of UV resistance test, the anti-halo automotive windshield (including Examples 1-6 and Comparative Examples 1-5) showed an oil contact angle of ≥80° after aging, indicating high resistance to light aging.

[0139] Table 1

[0140] Table 2

[0141]

[0142] Table 3

[0143] Based on the data in Tables 1 and 2, it can be seen that:

[0144] The SiO2 transition layer of the anti-halo glass in Examples 1-6 has a thickness of 50-100 nm, and no Si-DLC layer peeling off during the wear resistance test was observed due to poor bonding between the Si-DLC layer and the glass. A thicker SiO2 transition layer would affect the light transmittance of the glass; therefore, a thinner SiO2 transition layer is preferred for the glass plate.

[0145] The thickness of the Si-DLC layer in the anti-glare glass of Examples 1-5 is 150-200 nm, and all samples meet the requirements for automotive glass. The Si content of the Si-DLC layer is 15 at%-20 at%, and the oleophobic layer and the Si-DLC layer have good adhesion. The thickness of the Si-DLC layer affects both the light transmittance of the anti-glare windshield and the abrasion resistance of the oleophobic layer. For example, the thickness of the Si-DLC layer in Example 1 is 151 nm, and the thickness of the Si-DLC layer in Example 4 is 196 nm. As the thickness of the Si-DLC layer increases, the light transmittance of the anti-glare windshield glass in Example 4 decreases to 71.3%, but the increase in the thickness of the Si-DLC layer is beneficial to the improvement of the abrasion resistance of the oleophobic layer. In Example 4, after 50,000 scratch tests, the oil contact angle is the highest among the five examples, indicating a high resistance to the formation of radial defects.

[0146] In Example 6, the Si-DLC layer coating thickness is 273 nm. Although the thickness exceeds the preferred thickness range of 150-200 nm for the Si-DLC layer coating of the present invention and does not meet the specification requirement that the light transmittance of the windshield is less than 70%, it can be used in other positions where the light transmittance requirement is not so high.

[0147] Comparative Example 1, without a Si-DLC coating or an oleophobic layer, exhibited noticeable elliptical halo-like defects after 50,000 scratches (similar to...). Figure 4 Furthermore, the glass lacks oleophobic properties, making it prone to oil film buildup on the windshield, which can result in halo-like defects.

[0148] Comparative Example 2 has no Si-DLC coating but has an oleophobic layer. Although it does not affect the light transmittance of the glass, the oil contact angle of the oleophobic layer drops to 57° after 50,000 scratches due to the absence of the Si-DLC layer, which is judged as a layer failure.

[0149] In Comparative Example 3, the thickness of the Si-DLC layer is 52 nm. This Si-DLC layer is too thin. After 50,000 scratches, the glass surface is scratched and halo-like defects appear.

[0150] In Comparative Example 4, the doping amount of silicon atoms in the Si-DLC layer was reduced to only 10.2 at%, which led to a decrease in the bonding force between the oleophobic layer and the Si-DLC layer. After 50,000 scratches, the oleophobic layer on the glass surface failed.

[0151] In Comparative Example 5, the silicon atom doping level in the Si-DLC layer was relatively high, at 24.6 at%, exceeding the 15-20 at% range defined in this invention, which resulted in a decrease in the wear resistance of the Si-DLC layer and the appearance of halo-like defects after wear.

[0152] The comparison shows that: Examples 1-6 form a silicon-doped diamond-like layer on the surface of the glass plate, which can improve the surface hardness and enhance the scratch resistance, thereby avoiding the generation of micro-scratches and eliminating halo defects; at the same time, by forming an oleophobic layer on the surface of the silicon-doped diamond-like layer, the formation of radial defects can be effectively prevented; moreover, the bonding force between the silicon-doped diamond-like layer and the glass plate can be improved by means of a transition layer.

Claims

1. A type of anti-halo glass, wherein, The anti-halo glass includes a glass panel; The surface of the glass plate has an anti-halo film, wherein a transition layer of the anti-halo film is disposed on the surface; The anti-halo film comprises a transition layer, a silicon-doped diamond-like carbon (DLC) layer, and an oleophobic layer arranged sequentially, wherein the oleophobic layer is located in at least a portion of the surface of the silicon-doped DLC layer; the silicon content in the silicon-doped DLC layer is 15-20 at.

2. The anti-halo glass according to claim 1, wherein, The thickness of the silicon-doped diamond-like layer is 100-300 nm.

3. The anti-halo glass according to claim 1, wherein, The refractive index of the silicon-doped diamond-like layer is 1.6-1.

8.

4. The anti-halo glass according to claim 1, wherein, The oleophobic layer contains a perfluoropolyether siloxane, which has one of the structures shown in Formulas I to III: Formula I; Formula II; Formula III; In Equations I to III, m x1 +m x2 =15-30, m x1 Represents m 11 m 21 m 31 m x2 Represents m 12 m 22 m 32 ; R 11 R 21 R 31 Each is independently selected from C1-6 unbranched fluoroalkyl groups; R 22 R 32 Each is independently selected from C1-6 unbranched fluoroalkylene groups; R 23 R 33 Each is independently selected from C3-6 fluoroalkylene groups with cyclic structures; R 34 Selected from C1-6 branched fluoroalkylene groups.

5. The anti-halo glass according to claim 4, wherein, The proportion of F-substituted H in the perfluoropolyether siloxane is greater than or equal to 80%.

6. The anti-halo glass according to claim 4, wherein, The molecular weight of the perfluoropolyether siloxane is 5000-10000 g / mol.

7. The anti-halo glass according to claim 1, wherein, The thickness ratio of the silicon-doped diamond-like layer to the oleophobic layer is (15-20):

1.

8. The anti-halo glass according to claim 1, wherein, The transition layer is a silicon dioxide transition layer.

9. The anti-halo glass according to claim 1 or 8, wherein, The thickness of the transition layer is 20-200 nm.

10. The anti-halo glass according to claim 1, wherein, The light transmittance of the anti-halo glass is greater than 70%.

11. The anti-halo glass according to claim 1, wherein, The anti-halo glass has a lateral curvature ≥ 500 mm and a longitudinal curvature ≥ 1000 mm.

12. The anti-halo glass according to claim 11, wherein, The oil contact angle of the anti-halo glass is greater than 90°.

13. The anti-halo glass according to claim 1, wherein, The anti-glare glass includes an inner glass panel, an intermediate interlayer, and an outer glass panel. The outer glass panel has a first surface facing outwards from the vehicle and a second surface facing inwards from the vehicle. The inner glass panel has a third surface facing outwards from the vehicle and a fourth surface facing inwards from the vehicle. The intermediate interlayer is disposed between the second surface and the third surface. The first surface of the outer glass plate has an anti-halo film, wherein the transition layer of the anti-halo film is disposed on the first surface.

14. The anti-halo glass according to any one of claims 1-13, wherein, The glass plate has a signal transmission area for optical signal transmission from the sensor, and the anti-halo film at least covers the signal transmission area.

15. A vehicle, wherein, The vehicle is equipped with anti-glare glass as described in any one of claims 1-14.

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