Impact-resistant hardened film

Abstract

The utility model discloses an anti-impact hardened film which comprises a plurality of first film layers, second film layers and third film layers which are alternately stacked, the first film layers are high-refractive-index film layers, the second film layers and the third film layers are low-refractive-index film layers with refractive indexes smaller than that of the high-refractive-index film layers, and the third film layers are high-refractive-index film layers with refractive indexes smaller than that of the high-refractive-index film layers. The outermost layers of the impact-resistant hardened film are the first film layer and the third film layer respectively, the secondary outer layers of the impact-resistant hardened film are the second film layers respectively, and the total thickness of the impact-resistant hardened film is 500-1000 nm. The hardness and stress of the film layer can be guaranteed, meanwhile, the hydrophobicity of the film layer and good anti-reflection performance in a visible light region can be guaranteed, and the film layer has wide application prospects in the field of screen protection of vehicle-mounted and mobile equipment.

Description

Technical Field

[0001] The utility model belongs to the technical field of optical films, and in particular relates to an impact-resistant hard film. Background Art

[0002] With the development of assisted and autonomous driving, in-vehicle imaging has become increasingly demanding. The G1 lens of an automotive camera is typically the outermost lens. When used outdoors or in harsh environments, such as those impacted by wind, sand, dust, and rocks, traditional lens surfaces can become worn, scratched, or cracked, resulting in poor clarity and increased ghosting, seriously impacting the camera's lifespan and assisted driving safety. Therefore, the development of a hardened coating with high hardness, excellent optical properties, and friction resistance is a pressing market need. Utility Model Content

[0003] The purpose of the present invention is to address the above problems and to provide an impact-resistant hardened film, which not only has a high hardness and effectively prevents wear, scratches or cracks, but also helps to ensure good optical properties and surface hydrophobicity.

[0004] In order to achieve the above purpose, the technical solution adopted by the utility model is:

[0005] The utility model proposes an impact-resistant hardened film, comprising a plurality of alternately stacked first film layers, second film layers and third film layers, wherein the first film layer is a high-refractive-index film layer, the second film layer and the third film layer are both low-refractive-index film layers having a refractive index lower than that of the high-refractive-index film layer, and the outermost layers of the impact-resistant hardened film are the first film layer and the third film layer, respectively, and the next outermost layers are the second film layer, and the total thickness of the impact-resistant hardened film is 500nm to 1000nm.

[0006] Preferably, the thickness of the first film layer is 12 nm to 200 nm, the thickness of the second film layer is 12 nm to 150 nm, and the thickness of the third film layer is 5 nm to 20 nm.

[0007] Preferably, the refractive index of the first film layer is 1.95-2.10, and the refractive index of the second film layer and the third film layer are both 1.45-1.50.

[0008] Preferably, the total number of the first film layer, the second film layer and the third film layer is 10 to 50 layers.

[0009] Preferably, the first film layer is a silicon nitride layer, the second film layer is a silicon oxynitride layer, and the third film layer is a hydrophobic film.

[0010] Preferably, the first film layer accounts for 20%-80% of the thickness of the impact-resistant hard film.

[0011] Preferably, the impact-resistant hard film further comprises a substrate, which is attached to the outermost first film layer and arranged opposite to the third film layer.

[0012] Preferably, the first side of the substrate is convex.

[0013] Preferably, the substrate is a glass substrate or a plastic substrate.

[0014] Preferably, the glass substrate is a crown optical glass substrate, a lanthanide optical glass substrate, or a barium optical glass substrate, and the plastic substrate is a PMMA substrate or a PC substrate.

[0015] Compared with the prior art, the beneficial effects of the present invention are:

[0016] This application can effectively resist gravel impact and scratches, has high hardness, good hydrophobicity and excellent scratch resistance, long service life, maintains hardness while having small stress, prevents film cracking after being placed over time, and can ensure the hydrophobicity of the film layer and good anti-reflection performance in the visible light region, and has broad application prospects in the field of screen protection for vehicles and mobile devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 This is a schematic structural diagram of the utility model's impact-resistant hard film (excluding the substrate);

[0018] Figure 2 This is a schematic structural diagram of the impact-resistant hard film (including substrate) of the utility model;

[0019] Figure 3 This is a flow chart of the method for preparing the impact-resistant hard film of the utility model;

[0020] Figure 4 This is a graph showing the wear test results of different impact-resistant hard films (including substrates) using an 8H test pencil in this utility model;

[0021] Figure 5 This is a graph showing the test results of the drip angle of different impact-resistant hard films (including substrates) using an 8H test pencil in this utility model;

[0022] Figure 6 This is a graph showing the wear test results of different impact-resistant hard films (including substrates) using a 9H test pencil in this utility model;

[0023] Figure 7 This is a graph showing the test results of the drip angle of different impact-resistant hard films (including substrates) using a 9H test pencil in this utility model;

[0024] Figure 8 This is a graph showing the test results of the drip angle of different impact-resistant hard films (including substrates) using a bristle brush with a load of 20N.

[0025] Figure 9 This is a spectral curve of the reflectivity of the impact-resistant hard film (excluding the substrate) of the utility model between the wavelengths of 400nm and 700nm.

[0026] Explanation of the accompanying drawings: 1. first film layer; 2. second film layer; 3. third film layer; 4. substrate. DETAILED DESCRIPTION

[0027] The following will be combined with the drawings in the embodiments of this application to clearly and completely describe the technical solutions in the embodiments of this application. Obviously, the embodiments described are only part of the embodiments of this application, not all of the embodiments. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of this application.

[0028] It should be noted that, unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art in the art of this application. The terms used herein in the specification of this application are only for the purpose of describing specific embodiments and are not intended to limit this application.

[0029] like Figure 1 As shown, an impact-resistant hardened film includes several first film layers 1, second film layers 2 and third film layers 3 alternately stacked, the first film layer 1 is a high-refractive index film layer, the second film layer 2 and the third film layer 3 are both low-refractive index film layers with a refractive index lower than that of the high-refractive index film layer, and the outermost layers of the impact-resistant hardened film are the first film layer 1 and the third film layer 3, respectively, and the next outermost layers are the second film layer 2. The total thickness of the impact-resistant hardened film is 500nm to 1000nm.

[0030] The materials of the first and second film layers 1 and 2 serve as the primary hardening components, while the material of the third film layer 3 provides lubrication, reduces friction, and resists fingerprints. This impact-resistant hardened film enhances impact resistance and service life, exhibiting excellent anti-reflection properties in the visible light range. It demonstrates no scratches after 500 8H and 100 9H pencil scratch tests at a load of 1000g / cm², and a drip angle greater than 100°, demonstrating both high hardness and hydrophobicity. It is suitable for applications requiring high hardness, wear resistance, and hydrophobicity, such as automotive and mobile device displays.

[0031] In one embodiment, the thickness of the first film layer 1 is 12 nm to 200 nm, the thickness of the second film layer 2 is 12 nm to 150 nm, and the thickness of the third film layer 3 is 5 nm to 20 nm. This can maintain excellent spectral characteristics, effectively reduce reflectivity, increase transmittance, and maintain an excellent hardening effect.

[0032] In one embodiment, the refractive index of the first film layer 1 is 1.95 to 2.10, and the refractive indexes of the second film layer 2 and the third film layer 3 are both 1.45 to 1.50. When the refractive index of the first film layer 1 is 1.95 to 2.10, if the first film layer 1 is a silicon oxynitride layer, the nitridation effect is good and the hardness is excellent. The hardness of the silicon oxynitride layer obtained after nitriding the silicon oxide will also be improved, and the refractive index will be greater than the refractive index of the silicon oxide.

[0033] In one embodiment, the total number of layers of the first film layer 1, the second film layer 2, and the third film layer 3 is 10 to 50. The total number of layers is 10 to 50, which can achieve both manufacturing costs and anti-reflection effects.

[0034] In one embodiment, the first film layer 1 is a silicon nitride layer, the second film layer 2 is a silicon oxynitride layer, and the third film layer 3 is a hydrophobic film. The selection of the above materials can effectively reduce the reflectivity, maintain an excellent hardening effect, and also have an anti-fingerprint effect.

[0035] In one embodiment, the first film layer 1 accounts for 20% to 80% of the thickness of the impact-resistant hard film. The higher the thickness of the first film layer 1, the more pronounced the film hardening effect. Exceeding this range, if the thickness ratio is further increased, it becomes difficult to meet the requirements of optical film curves.

[0036] In one embodiment, the impact-resistant hard film further comprises a substrate 4, which is attached to the outermost first film layer 1 and is arranged opposite to the third film layer 3. Figure 2 As shown, the substrate 4 is generally an optical lens, a screen, etc., or can be adjusted according to actual needs.

[0037] In one embodiment, the first surface of the substrate 4 is a convex surface, that is, it is generally the lens exposed on the outside.

[0038] In one embodiment, the substrate 4 is a glass substrate or a plastic substrate.

[0039] In one embodiment, the glass substrate is a crown optical glass substrate, a lanthanide optical glass substrate, or a barium optical glass substrate, and the plastic substrate is a PMMA substrate or a PC substrate. It will be readily appreciated that the specific materials of the glass and plastic substrates can be adjusted according to actual needs, such as other materials commonly used by those skilled in the art.

[0040] Specifically, if Figure 3 As shown, the preparation process of the impact-resistant hard film is as follows:

[0041] S1. After pre-treatment, the optical substrate is mounted on the sample rack of the vacuum coating device. The pre-treatment is to perform ultrasonic cleaning and plasma cleaning in sequence, and then the substrate is mounted on the sample rack of the vacuum coating device to ensure the cleanliness and flatness of the substrate surface.

[0042] S2. Install a silicon target with a purity of 4N or 5N on a target holder of a vacuum coating device, preferably a silicon target with a purity of 5N.

[0043] S3. Evacuate the vacuum chamber of the vacuum coating device to 4.0E-4Pa to 8.0E-4Pa and maintain the temperature at 120°C to 320°C. Preferably, evacuate the vacuum chamber to 6.0E-4Pa and maintain the temperature at 150°C.

[0044] S4. Fill the vacuum chamber of the vacuum coating device with reactive gas, and alternately laminate the first film layer 1 and the second film layer 2 of the impact-resistant hard film on the first surface of the optical substrate. The reactive gas is one or more of oxygen, nitrogen, and argon, and the silicon target is sputtered by argon. The oxygen injection flow rate is 200-300 sccm, the nitrogen injection flow rate is 0-50 sccm, and the argon injection flow rate is 40-120 sccm. The sputtering power of the first film layer 1 and the second film layer 2 is 2-10 kW. Specifically, if the vacuum chamber of the vacuum coating device is filled with reactive gas, the first film layer and the second film layer of the impact-resistant hard film are alternately laminated on the first surface of the substrate 4. The low refractive index film layer is a silicon nitride layer filled with nitrogen, oxygen, and argon at different flow rates, and the high refractive index film layer is a silicon nitride layer filled with nitrogen and argon at different flow rates. When depositing the silicon oxynitride layer, the oxygen flow rate is 280 sccm, the nitrogen flow rate is 20 sccm, the argon flow rate is 80 sccm, and the sputtering power is 8 kW. When depositing the silicon nitride layer, the nitrogen flow rate is 300 sccm, the argon flow rate is 80 sccm, and the sputtering power is 8 kW. The sputtered atoms or molecules are ionized in the vacuum chamber, forming a high-energy ion beam, which is deposited on the surface of substrate 4, forming a silicon nitride layer and a silicon oxide layer.

[0045] S5. Deflate the vacuum chamber of the vacuum coating device and take out the semi-finished product.

[0046] S6. Depositing a third film layer 3 on the outermost film layer of the first surface of the semi-finished product away from the optical substrate to obtain an impact-resistant hard film.

[0047] Among them, the optical substrate can be a carrier for preparing an impact-resistant hard film, or directly a substrate 4. Each film layer is prepared using physical vapor deposition technology and the principles of optical reflection, absorption and refraction. For example, the first film layer 1 can be formed by magnetron sputtering a silicon target by a physical vapor deposition method to form a single silicon film layer and then oxidized; the second film layer 2 can be formed by magnetron sputtering a silicon target by a physical vapor deposition method and then nitrided; the third film layer 3 is formed by a physical vapor deposition method using an electron gun or a vapor barrier to evaporate a hydrophobic material. The first film layer 1 and the second film layer 2 are prepared by the same equipment, and the third film layer 3 is prepared by another equipment. The coating method of the vacuum coating device is one of ion beam sputtering vacuum coating and magnetron sputtering vacuum coating, or other coating methods well known to those skilled in the art can also be used, such as ion-assisted deposition evaporation vacuum coating. The magnetron sputtering method uses controlled reaction gas flow and target sputtering power to achieve both the hardness and stress of the impact-resistant hardened film. This allows for a balanced combination of hardness and stress, maintaining hardness while minimizing stress, preventing film cracking over time. This also helps ensure the film's hydrophobicity and excellent anti-reflection properties in the visible light region.

[0048] For example, a vacuum coating device, model NSC-15, is used, employing magnetron sputtering. The first side of the substrate is convex and made of H-ZLAF50E optical glass. A low-refractive-index layer of silicon oxide-nitride (silicon oxynitride) and a high-refractive-index layer of silicon-nitride (silicon nitride) are deposited sequentially to form an impact-resistant hard coating.

[0049] The impact-resistant hardened film of this embodiment is shown in Table 1 below, wherein the thickness ratio of the first film layer 1 accounts for 59.13% of the impact-resistant hardened film.

[0050] Table 1

[0051] Material Silicon nitride Silicon oxynitride Silicon nitride Silicon Oxynitride Silicon nitride Silicon Oxynitride film layer First film layer Second film layer First film layer Second film layer First film layer Second film layer Thickness / nm 21.48 13.65 165.95 19.89 50.97 15.32 Material Silicon nitride Silicon oxynitride Silicon nitride Silicon Oxynitride Silicon nitride Silicon oxynitride film layer First film layer Second film layer First film layer Second film layer First film layer Second film layer Thickness / nm 93.8 29.77 21.49 111.17 25.31 24.84 Material Silicon nitride Silicon Oxynitride hydrophobic materials film layer First film layer Second film layer The third film layer Thickness / nm 73.37 88.03 10

[0052] To further verify the advantages of this application, performance tests were conducted:

[0053] During the test, a test pencil is used to perform a wear test on the impact-resistant hard film containing the optical substrate (i.e., substrate 4, in this embodiment, substrate 4 is a lens), and a pig bristle brush is used to perform a drip angle test. Figure 4-Figure 8As shown. The exposed length of the test pencil lead is approximately 3mm to prevent breakage during testing. The angle between the test pencil and the impact-resistant hardened film (including the substrate) (the first lens on the vehicle, the exposed lens) is 90°. The specific angle can be adjusted according to actual needs. The contact surface is smooth (the tip of the pencil lead is ground and contacts the outer, convex surface of the impact-resistant hardened film). During the test, the pencil lead must not exceed the effective diameter of the impact-resistant hardened film. The test speed is 60 reciprocating strokes / min. The test pencil is a Mitsubishi 8H / 9H, and the test results are observed using a 20X microscope.

[0054] 1) Use an 8H test pencil to apply a force of 1000g / cm2 and scratch back and forth 500 times on the same position of the impact-resistant hard film. Use 2 pieces of impact-resistant hard film for each test. There is no appearance of scratches. The test results are as follows: Figure 4 As shown, the drip angle is ≥100°, and the test results are as follows Figure 5 shown.

[0055] 2) Use a 9H test pencil to apply a force of 1000g / cm2 and scratch back and forth 100 times on the same position of the impact-resistant hard film. No scratches are observed. Use two pieces of impact-resistant hard film for each test. The test results are as follows: Figure 6 As shown, the drip angle is ≥100°, and the test results are as follows Figure 7 shown.

[0056] 3) Use a bristle brush with a load of 20N, and use 2 pieces of impact-resistant hard film for the test each time. Scratch the same position of the impact-resistant hard film 500 times back and forth, with a drip angle of ≥100°. The test results are as follows: Figure 8 shown.

[0057] 4) Optical spectrometry requires 400nm-420nm, Rmax (maximum reflectivity) ≤ 1.0%, and the spectroscopic curve test results are as follows Figure 9 shown.

[0058] The technical features of the above-mentioned embodiments can be combined arbitrarily. In order to make the description concise, not all possible combinations of the technical features in the above-mentioned embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0059] The above-described embodiments merely represent specific and detailed examples of the present application and should not be construed as limiting the scope of the present application. It should be noted that a person skilled in the art may make various modifications and improvements without departing from the spirit of the present application, and such modifications and improvements fall within the scope of protection of the present application. Therefore, the scope of protection of the present application shall be determined by the appended claims.

Claims

1. An impact-resistant hard film, characterized in that: The impact-resistant hardened film comprises a plurality of alternately stacked first film layers (1), second film layers (2) and third film layers (3), wherein the first film layer (1) is a high-refractive-index film layer, and the second film layer (2) and the third film layer (3) are both low-refractive-index film layers having a refractive index lower than that of the high-refractive-index film layer. The outermost layers of the impact-resistant hardened film are the first film layer (1) and the third film layer (3), respectively, and the next outermost layers are the second film layer (2). The total thickness of the impact-resistant hardened film is 500 nm to 1000 nm.

2. The impact-resistant hard film according to claim 1, characterized in that: The thickness of the first film layer (1) is 12nm to 200nm, the thickness of the second film layer (2) is 12nm to 150nm, and the thickness of the third film layer (3) is 5nm to 20nm.

3. The impact-resistant hard film according to claim 1, characterized in that: The refractive index of the first film layer (1) is 1.95 to 2.10, and the refractive indexes of the second film layer (2) and the third film layer (3) are both 1.45 to 1.

50.

4. The impact-resistant hard film according to claim 1, wherein: The total number of layers of the first film layer (1), the second film layer (2) and the third film layer (3) is 10 to 50 layers.

5. The impact-resistant hard film according to claim 1, wherein: The first film layer (1) is a silicon nitride layer, the second film layer (2) is a silicon oxynitride layer, and the third film layer (3) is a hydrophobic film.

6. The impact-resistant hard film according to claim 1, characterized in that: The first film layer (1) accounts for 20%-80% of the thickness of the impact-resistant hardened film.

7. The impact-resistant hard film according to claim 1, wherein: The impact-resistant hardened film further comprises a substrate (4), wherein the substrate (4) is attached to the outermost first film layer (1) and is arranged opposite to the third film layer (3).

8. The impact-resistant hard film according to claim 7, characterized in that: The first surface of the substrate (4) is a convex surface.

9. The impact-resistant hard film according to claim 7, wherein: The substrate (4) is a glass substrate or a plastic substrate.

10. The impact-resistant hardened film according to claim 9, characterized in that: The glass substrate is a crown optical glass substrate, a lanthanide optical glass substrate, or a barium optical glass substrate, and the plastic substrate is a PMMA substrate or a PC substrate.

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