High-hardness scratch-resistant automobile film

Abstract

The invention relates to the field of automobile heat insulation films, in particular to a high-hardness scratch-resistant automobile film which comprises an automobile heat insulation film, the outer surface of the automobile heat insulation film is coated with a Ta-C coating, the Ta-C coating is prepared through a filtered cathode vacuum arc technology, and the Ta-C contains lithium niobate microcrystal particles. The ta-C is applied to the outer surface of the automobile heat insulation film, and the surface hardness of the heat insulation film is greatly improved from pencil hardness 2H to 6H; in a steel wool friction test, the friction frequency is increased from 200 times to 2000 times, and the scratch resistance of the automobile heat insulation film is greatly enhanced; the thermal insulation effect of the lithium niobate-containing ta-C is twice that of the lithium niobate-free ta-C, and the remarkable advantages of the lithium niobate-containing ta-C coating in the thermal insulation aspect are fully proved; when measured under the incident light wavelength of 550 nm, the light transmittance of the cold film without ta-C is 70%, the light transmittance of the cold film with ta-C is 69%, the influence of Ta-C on the light transmittance is very small and is within 1%, and the good light transmittance performance of the automobile heat insulation film is guaranteed.

Description

Technical Field

[0001] The present invention relates to the technical field of automotive heat insulation films, and particularly to an automotive film with high hardness and scratch resistance. Background Art

[0002] Currently, the outer surface of commercial automotive films usually uses polymer films such as TPU or PET. However, these polymer films have obvious defects. Their hardness is relatively low, and during daily use, for example, when encountering sandy weather and scratches during car washing, tiny scratches (scratches) will quickly appear on the surface of the film. This not only affects the aesthetics of the automotive film but may also have a certain negative impact on its heat insulation and other properties in the long run. Due to the low surface hardness of the polymer film on the outer surface of existing automotive films, they are not scratch-resistant and it is difficult to meet consumers' requirements for the durability and good performance of automotive films.

[0003] Therefore, those skilled in the art have provided an automotive film with high hardness and scratch resistance to solve the problems raised in the above background art. Summary of the Invention

[0004] To solve the above technical problems, the present invention provides an automotive film with high hardness and scratch resistance, which solves the problems of low surface hardness and poor scratch resistance of the polymer film on the outer surface of existing automotive films, and at the same time improves the heat insulation effect of the automotive film.

[0005] It includes an automotive heat insulation film, and a Ta-C coating is coated on the outer surface of the automotive heat insulation film. The Ta-C coating is prepared by filtered cathodic vacuum arc technology, and lithium niobate microcrystalline particles are contained in the Ta-C.

[0006] Preferably, the Ta-C coating is deposited by using graphite doped with lithium niobate as a target and filtered cathodic vacuum arc technology, and the content of lithium niobate is 1-10% by weight.

[0007] Preferably, the thickness of the Ta-C coating is 5-200 nanometers.

[0008] Preferably, the steps of the automotive film with high hardness and scratch resistance are as follows: Step 1: Provide a graphite target doped with lithium niobate, with the content of lithium niobate being 1-10% by weight, a magnetic filter, and an automotive heat insulation film with PET or TPU on the outermost surface as a substrate; Step 2: Place the automotive heat insulation film substrate in a vacuum chamber and evacuate to a low pressure, with the low pressure range being 10 -3 —10 - 7 Pa; Step 3: Use argon ions to bombard the surface of the substrate for pretreatment; Step 4: After the argon ion bombardment of the substrate ends, evacuate the vacuum to 10-4 The Pa magnitude, argon gas is introduced into the vacuum chamber, the working pressure is maintained, and the Ta-C film is deposited by using the filtered cathode vacuum arc technology. During the deposition process, the substrate temperature is controlled not to exceed 50 °C; Step Five: After the deposition is completed, stop the target arc discharge and the argon gas input, evacuate the vacuum to below 10 -4 Pa, introduce air to make the pressure in the coating chamber reach one atmosphere, take out the substrate, and obtain an automotive heat insulation film coated with a Ta-C coating containing lithium niobate.

[0009] Preferably, the argon gas flow rate in Step Three is 20 sccm, the extraction beam current is 20 mA, and the processing time is about 15 min.

[0010] Preferably, in Step Four, the pressure in the vacuum chamber during deposition is 10 -3 –10 -4 Pa, and the argon gas flow rate is 1 - 100 sccm.

[0011] Preferably, in Step Four, a negative bias voltage is applied to the substrate, the negative bias voltage is from -1 V to -800 V, and the target arc discharge current is 10 - 90 A.

[0012] Preferably, in Step Four, the magnetic field current of the magnetic filter tube is 1 - 15 A, and the deposition time is 5 - 200 min.

[0013] Preferably, the magnetic filter in Step One adopts a single-bend or S-shaped double-bend tube.

[0014] Preferably, the size of the substrate in Step One is a square with a length and width of 200 mm each.

[0015] The technical effects and advantages of the present invention: Hardness improvement effect: By applying ta-C to the outer surface of the automotive heat insulation film, the surface hardness of the heat insulation film is greatly increased from a pencil hardness of 2H to 6H; in the steel wool friction test, the number of friction times is increased from 200 times to 2000 times, greatly enhancing the scratch resistance of the automotive heat insulation film. Heat insulation effect improvement: The heat insulation effect of ta-C containing lithium niobate is twice that of ta-C without lithium niobate; in actual tests, a cold film is attached to the upper surface of the glass and exposed to sunlight for 10 min, and the temperature of the lower surface of the glass is measured with a laser temperature gun. The temperature of the glass without the cold film is 75 °C, the temperature of the glass with the cold film coated with ta-C containing lithium niobate is 30 °C, and the temperature of the glass with the cold film coated with ta-C without lithium niobate is 60 °C, fully demonstrating the significant advantage of the ta-C coating containing lithium niobate in heat insulation. Has little impact on light transmittance: Measured at an incident light wavelength of 550 nm, the light transmittance of the cold film without ta-C is 70%, and the light transmittance of the cold film with ta-C is 69%. The impact of Ta-C on the transmittance is very small, within 1%, ensuring good light transmittance performance of the automotive heat insulation film. Description of the Drawings

[0016] Figure 1 is the peak fitting analysis of the Raman spectrum of ta-C obtained in the present invention in a high-hardness and scratch-resistant automotive film provided by an embodiment of the present application; Figure 2 is the peak fitting analysis of the Raman spectrum of ta-C with 80% sp3 content in the PLespadeetal. (1982) literature in a high-hardness and scratch-resistant automotive film provided by an embodiment of the present application. Detailed Description of the Invention

[0017] The present invention will be further described in detail below in conjunction with the drawings and specific embodiments. The embodiments of the present invention are given for purposes of illustration and description, and are not intended to be exhaustive or to limit the invention to the disclosed form. Many modifications and variations will be apparent to those of ordinary skill in the art. The embodiments are selected and described in order to better illustrate the principles of the invention and its practical applications, and to enable those of ordinary skill in the art to understand the invention and design various embodiments with various modifications suitable for specific purposes. Embodiment

[0018] Please refer to Figures 1-2 , in this embodiment, a high-hardness and scratch-resistant automotive film is provided, including including an automotive heat insulation film, the outer surface of the automotive heat insulation film is coated with a Ta-C coating, the Ta-C coating is prepared by filtered cathodic vacuum arc technology, and the Ta-C contains lithium niobate microcrystalline particles.

[0019] The Ta-C coating is deposited by using graphite doped with lithium niobate as a target by filtered cathodic vacuum arc technology, wherein the content of lithium niobate is 1-10% by weight.

[0020] Target and substrate preparation: The target (also known as the cathode) uses graphite containing lithium niobate, and the content of lithium niobate is 1-10% (by weight), usually 5%. The magnetic filter uses a single-bend or s-shaped double-bend tube. The substrate is an automotive heat insulation film with PET or TPU on the outermost surface, and the substrate size is a square with a length and width of 200 mm each. Vacuum chamber treatment and substrate surface pretreatment: Place the substrate in the vacuum chamber and evacuate to a low pressure, and the low pressure range is 10 -3 –10-7 Pa, usually 10 -4 Pa. First, the substrate surface is bombarded with argon ions. The argon flow rate is 20sccm (standard state) and the extracted beam current is 20mA. The surface treatment of the sample is carried out for about 15 minutes. The substrate is pre-sputtered with argon ions to remove the oxide layer on the surface of the substrate and increase the adhesion between the film and the substrate. ta-C thin film deposition: After the argon ion bombardment, the ta-C film was deposited; the vacuum was pumped to 10 -4 Pa level, introduce argon gas, maintain the working pressure of argon gas at 5-8x10 -3 Pa range. First, use a bias voltage of -700V and a duty cycle of 50% to bombard carbon cations for a short time (~120 seconds). Then, according to the selected arc current, the ta-C film deposition is completed according to the predetermined coating time. Depending on the temperature rise of the target during deposition, you can choose a pulsed plating method of plating-stop-plating-stop; or adjust the cooling water temperature as low as possible, select a smaller arc current, and use a continuous plating method. Regardless of the method, the target surface must be kept at a low operating temperature. The process parameters during plating are as follows: The pressure of the vacuum chamber during deposition: 10 -3 –10 -4 Pa, usually 6x10 -3 Pa. The argon gas flow rate is 1-100 sccm, generally 4 sccm. A negative bias is applied to the substrate, the negative bias is -1V to -800V, generally -200V. The target arc discharge current is 10-90A, generally 40A. The magnetic field current of the magnetic filter tube is 1-15A, generally 2A. During the whole plating process, the substrate temperature does not exceed 50°C. The plating time is 5-200 minutes, usually 60 minutes. Post-processing: After the plating is completed, stop the target arc discharge, stop the argon gas input, and evacuate to 10 -4 When the pressure is below 100 Pa, open the air-breaking valve to introduce air into the coating chamber until the pressure in the coating chamber reaches one atmosphere. Open the chamber door and take out the substrate. The thickness of ta-C obtained on the substrate is 5-200 nanometers, generally 20 nanometers. Test Data Hardness measurement: Under 750g pressure, using a pencil hardness tester to test, the surface hardness of the cold film without ta-C is 2H, and the surface hardness of the cold film with ta-C is 6H. Wear resistance test: Tested under a pressure of 750 grams of steel wool, the cold film without ta-C showed scratches after 200 times of friction, while the cold film with ta-C showed scratches only after 2000 times of friction. Visible light transmittance: Measured at an incident light wavelength of 550 nm, the transmittance of the cold film without ta-C was 70%, and the transmittance of the cold film with ta-C was 69%. The influence of Ta-C on the transmittance was very small, within 1%. Cooling effect: Stick the cold film on the upper surface of the glass and expose it to sunlight for 10 minutes. Use a laser temperature measurement gun to measure the temperature of the lower surface of the glass. The temperature of the glass without the cold film was 75 °C, the temperature of the glass with the cold film coated with ta-C containing lithium niobate was 30 °C, and the temperature of the glass with the cold film coated with ta-C without lithium niobate was 60 °C; It can be seen that doping lithium niobate into ta-C can effectively improve the heat insulation effect of the cold film.

[0021] Raman spectroscopy analysis: Use a Raman spectrometer to analyze the structure of the ta-C film, with a laser wavelength of 514 nm, a laser input power of 20 mW, and a sampling time of 180 s; There are two types of bond valence of carbon atoms in ta-C, sp2 and sp3. Generally, the higher the content of sp3C, the higher the hardness of ta-C, which is reflected in the Raman spectrum. The ta-C was characterized using Raman spectroscopy and compared with the results in the literature.

[0022] In the deconvolution analysis of the Raman spectrum of ta-C obtained in the present invention, the peak height ratio of the D peak and the G peak (ID / IG) = 0.088, which is very close to the peak height ratio of the D peak and the G peak (ID / IG) = 0.093 in the deconvolution analysis of the Raman spectrum of ta-C with 80% sp3 content in the literature, indicating that the content of sp3C in the ta-C obtained by this method is relatively high. At the same time, the position of the G peak of the ta-C obtained by this method is very close to the position of the G peak reported in the literature with a high sp3C content, further proving that the content of sp3C in the ta-C obtained by this method is relatively high.

[0023] The literature cited in this scheme is PLespade et al. (1982).

[0024] Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. All other embodiments obtained by those of ordinary skill in the art and related fields based on the embodiments of the present invention without creative efforts shall fall within the scope of protection of the present invention. The structures, devices, and operation methods not specifically described and explained in the present invention shall be implemented according to the conventional means in the art without special instructions and limitations.

Claims

1. A high-hardness, scratch-resistant automotive film, characterized in that: The invention comprises an automobile heat insulation film, the outer surface of which is coated with a Ta-C coating, the Ta-C coating is prepared by a filtered cathode vacuum arc technology, and the Ta-C contains lithium niobate microcrystalline particles.

2. A high-hardness, scratch-resistant automotive film according to claim 1, characterized in that: The Ta-C coating is deposited by using graphite doped with lithium niobate as a target material using a filtered cathode vacuum arc technique, wherein the content of lithium niobate is 1-10% by weight.

3. The high-hardness, scratch-resistant automotive film according to claim 1, characterized in that: The thickness of the Ta-C coating is 5-200 nanometers.

4. The high-hardness, scratch-resistant automotive film according to claim 1, characterized in that: The following steps are involved: Step 1: providing a graphite target doped with lithium niobate, wherein the lithium niobate content is 1-10% by weight, a magnetic filter, and an automotive thermal insulation film with PET or TPU as the outermost surface as a substrate; Step 2: Place the automotive thermal insulation film substrate in a vacuum chamber and evacuate to the bottom pressure. The low pressure range is 10 -3 —10 -7 Pa; Step 3: Pre-treating the substrate surface by bombarding it with argon ions; Step 4: After the argon ion bombardment of the substrate is completed, the vacuum is pumped to 10 -4 Pa order of magnitude, argon gas is introduced into the vacuum chamber to maintain the working pressure, and Ta-C thin film is deposited using filtered cathode vacuum arc technology, and the substrate temperature is controlled not to exceed 50°C during the deposition process; Step 5: After the deposition is completed, stop the target arc discharge and argon gas input, and pump the vacuum to 10 -4 Pa, air is introduced to make the pressure in the coating chamber reach one atmosphere, and the substrate is taken out to obtain an automotive thermal insulation film coated with a Ta-C coating containing lithium niobate.

5. The high-hardness, scratch-resistant automotive film according to claim 4, characterized in that: In step three, the argon gas flow rate is 20 sccm, the extraction beam current is 20 mA, and the processing time is about 15 minutes.

6. The high-hardness, scratch-resistant automotive film according to claim 4, characterized in that: In step 4, the pressure of the vacuum chamber during deposition is 10 -3 –10 -4 Pa, argon flow rate 1-100sccm.

7. The high-hardness, scratch-resistant automotive film according to claim 4, characterized in that: In the step 4, a negative bias voltage is applied to the substrate, the negative bias voltage is -1V to -800V, and the target arc discharge current is 10-90A.

8. The high-hardness, scratch-resistant automotive film according to claim 4, characterized in that: In the step 4, the magnetic field current of the magnetic filtration tube is 1-15A, and the deposition time is 5-200min.

9. The high-hardness, scratch-resistant automotive film according to claim 4, characterized in that: The magnetic filter in step 1 adopts a single-bend or S-shaped double-bend pipe.

10. The high-hardness, scratch-resistant automotive film according to claim 4, characterized in that: The size of the substrate in the step 1 is a square with a length and a width of 200 mm.

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