Glass display panel protective film, preparation method thereof and product comprising glass display panel protective film

Abstract

The embodiment of the invention relates to a glass display panel protective film, a preparation method thereof and a product comprising the glass display panel protective film. The glass display panel protective film sequentially comprises an anti-reflection layer, a DLC layer, a doping transition layer and an anti-fingerprint layer which are overlapped with one another, the anti-reflection layer is in contact with a glass display panel, the DLC layer is formed by first hydrocarbon gas through a PECVD process, and the doping transition layer is formed by a doping element gas source or by the doping element gas source and second hydrocarbon gas through the PECVD process. According to the embodiment of the invention, the glass display panel protective film with improved surface hardness, scratch resistance and wear resistance and good anti-reflection performance and pollution resistance can be provided.

Description

Technical Field

[0001] The present invention relates to the field of coating, and particularly to a protective film for a glass display panel, a preparation method thereof, and a product including the same. Background Art

[0002] In recent years, with the rapid development of three types of electronic products, namely computers, communications, and consumer electronics (collectively referred to as 3C electronic products), and industries such as virtual reality (VR), the glass display panel that plays an outer protective role in these electronic products has become the focus of attention for researchers. Nowadays, high-quality glass display panels or protective covers have already become an important part of the competitiveness of such products. This not only requires the product to have high resolution, brightness, fingerprint resistance, etc., but also puts forward higher requirements for the surface hardness, scratch resistance, and wear resistance of the product.

[0003] Currently, the protective films on the glass display panels of mainstream electronic products on the market mainly combine an anti-reflection film and an anti-fingerprint film to achieve the effects of anti-reflection and increased transmittance, anti-fouling, and wear resistance. Among them, the anti-reflection film is mainly formed by alternately stacking high-reflectivity materials and low-reflectivity materials through optical thin film design to achieve the effect of anti-reflection and increased transmittance. However, most of the film layer materials are relatively soft oxynitrides, and the product is relatively easy to be scratched by hard particles during use, affecting the touch and appearance of the screen.

[0004] Diamond like carbon (DLC) film, as a film with excellent properties such as high hardness and low friction coefficient, can provide good protection for glass products, and will not affect the optical properties of the original glass at a certain thickness, and also has good adhesion on glass. However, the chemical inertness of DLC film makes it difficult to combine with the anti-fingerprint film, resulting in poor wear resistance of the final composite protective film and failing to achieve the expected effect of the protective film.

[0005] Patent Application No. CN1106929800 A provides a DLC composite film and a preparation method thereof. The composite film includes a SiO x N y film layer and a hydrogen-containing DLC film layer, which can achieve good optical properties, hardness, and wear resistance. However, in the field of glass covers, a layer of anti-fingerprint film is still required on the outermost layer of the commonly used protective film to provide good smoothness and anti-fouling properties in order to have better market applications.

[0006] Patent Application No. CN115113305 A provides an anti-reflection film, a preparation method thereof, and an application. Among them, by preparing Ti x Siy The N layer is applied between the antireflection layer and the fingerprint-proof layer, so that the protective film has better light absorption rate and surface resistance, and can be better applied to the touch display screen. However, the oxide used as the antireflection layer of this protective film has the disadvantages of low surface hardness and poor scratch resistance. Summary of the Invention

[0007] In order to solve the above technical problems, the present invention provides a glass display panel protective film with improved surface hardness, scratch resistance and wear resistance, good antireflection and antifouling properties, a preparation method thereof, and a product including the same.

[0008] For the above purposes, one aspect of the embodiments of the present invention relates to a glass display panel protective film, which sequentially includes an antireflection layer, a DLC layer, a doped transition layer and a fingerprint-proof layer stacked on each other. The antireflection layer is in contact with the glass display panel. The DLC layer is formed by a first hydrocarbon gas through a PECVD (Plasma Enhanced Chemical Vapor Deposition) process, and the doped transition layer is formed by a doped element gas source or by a doped element gas source and a second hydrocarbon gas through a PECVD process.

[0009] In some embodiments, each of the first hydrocarbon gas and the second hydrocarbon gas independently includes one or more of methane, ethane, propane, ethylene, acetylene, propylene, propyne, benzene vapor and toluene vapor.

[0010] In some embodiments, the doped element includes at least one of silicon and nitrogen.

[0011] In some embodiments, the doped element gas source includes at least one of silane, alkyl-substituted silane, siloxane, nitrogen gas and ammonia gas.

[0012] In some embodiments, the silane includes at least one of silane, disilane and trisilane.

[0013] In some embodiments, the alkyl-substituted silane includes at least one of methylsilane, dimethylsilane, trimethylsilane and tetramethylsilane.

[0014] In some embodiments, the siloxane includes hexamethyldisiloxane.

[0015] In some embodiments, the fingerprint-proof layer is formed by a vacuum evaporation process.

[0016] In some embodiments, the sum of the thicknesses of the DLC layer, the doped transition layer and the fingerprint-proof layer is less than 50 nm.

[0017] Another aspect of the embodiments of the present invention relates to a preparation method of a glass display panel protective film, which includes:

[0018] Step S1. Prepare an anti-reflection layer on the glass display panel;

[0019] Step S2. Deposit a DLC layer on the surface of the anti-reflection layer from a first hydrocarbon gas by PECVD process;

[0020] Step S3. Deposit a doped transition layer on the surface of the DLC layer from a doped element gas source or from a doped element gas source and a second hydrocarbon gas by PECVD process; and

[0021] Step S4. Prepare an anti-fingerprint layer on the surface of the doped transition layer, such that the anti-fingerprint layer and the doped transition layer overlap each other.

[0022] In some embodiments, Step S2 and / or Step S3 are carried out under a vacuum degree of 1 Pa - 5 Pa, a bias voltage of 100 V - 800 V, and a plasma source power of 100 W - 800 W.

[0023] In some embodiments, the method described in the present application includes Step S5. Clean the surface of the anti-reflection layer, and Step S5 is carried out before Step S2.

[0024] In some embodiments, the method described in the present application includes Step S6. Carry out plasma etching on the surface of the cleaned anti-reflection layer, and Step S6 is carried out before Step S2.

[0025] In some embodiments, the method described in the present application includes Step S7. Carry out plasma bombardment activation on the surface of the doped transition layer, and Step S7 is carried out before Step S4.

[0026] In some embodiments, Step S4 includes vacuum evaporating perfluoropolyether silicone on the surface of the plasma bombardment activated doped transition layer to form an anti-fingerprint layer.

[0027] In some embodiments, the method described in the present application includes Step S8. Let the glass display panel stand at room temperature for more than 120 min after Step S4.

[0028] In some embodiments, the first hydrocarbon gas and the second hydrocarbon gas each independently include one or more of methane, ethane, propane, ethylene, acetylene, propylene, propyne, benzene vapor, and toluene vapor.

[0029] In some embodiments, the doped element includes at least one of silicon and nitrogen.

[0030] In some embodiments, the doped element gas source includes at least one of silane, alkyl-substituted silane, siloxane, nitrogen gas, and ammonia gas.

[0031] In some embodiments, the silane includes at least one of silane, disilane, and trisilane.

[0032] In some embodiments, the alkyl-substituted silane includes at least one of methylsilane, dimethylsilane, trimethylsilane, and tetramethylsilane.

[0033] In some embodiments, the siloxane includes hexamethyldisiloxane.

[0034] In some embodiments, the sum of the thicknesses of the DLC layer, the doped transition layer, and the fingerprint-proof layer is less than 50 nm.

[0035] Another aspect of the embodiments of the present invention relates to a product, which includes a glass display panel and a glass display panel protection film as described in the present application that covers at least a part of the surface of the glass display panel.

[0036] The technical solutions of the embodiments of the present application can be beneficial to providing a glass display panel protection film with improved surface hardness, scratch resistance, wear resistance, good antireflection property, and antifouling property, etc.

[0037] Under the condition that technical conditions permit, the technical solutions of the embodiments in the present application can be combined arbitrarily.

[0038] The present application will be further described below in conjunction with the accompanying drawings. The same or similar reference numerals may be used in the drawings to refer to the same or similar elements, devices, shapes, structures, steps in different embodiments. The descriptions of the same or similar elements, devices, shapes, structures, steps, features, effects in different embodiments may also be omitted, as well as the descriptions of the same or similar elements, devices, shapes, structures, steps, features, effects as in the prior art. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 It is a schematic structural diagram of a glass display panel protection film and a product including the same according to an embodiment of the present invention.

[0040] DESCRIPTION OF REFERENCE NUMERALS:

[0041] 10: Glass display panel protection film;

[0042] 12: Glass display panel;

[0043] 14: Antireflection layer;

[0044] 16: DLC layer;

[0045] 18: Doped transition layer;

[0046] 20: Fingerprint-proof layer;

[0047] 100: Product. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0048] Figure 1Schematic diagram of a protective film for a glass display panel and a product including the same according to an embodiment of the present invention. As Figure 1 shown, one aspect of an embodiment of the present invention relates to a protective film 10 for a glass display panel, which sequentially includes an antireflection layer 14, a DLC layer 16, a doped transition layer 18, and an anti-fingerprint layer 20 that are stacked on each other. The antireflection layer 14 is in contact with the glass display panel 12. The DLC layer 16 is formed from a first hydrocarbon gas by a PECVD process. The doped transition layer 18 is formed from a doped element gas source or from a doped element gas source and a second hydrocarbon gas by a PECVD process.

[0049] In the embodiments of the present invention, "stacked" means meanings such as "stacked, combined", "superposed, combined", "stacked, synthesized into a whole", "layered, combined together".

[0050] The protective film 10 for a glass display panel can be any composite film formed by stacking the antireflection layer 14, the DLC layer 16, the doped transition layer 18, and the anti-fingerprint layer 20 on each other, as long as it is applicable to the present invention.

[0051] The glass display panel 12 can be any display glass panel or glass cover plate that serves as an outer protection, as long as it is applicable to the present invention.

[0052] The antireflection layer 14 can be any film having antireflection performance or light transmittance enhancement performance, as long as it is applicable to the present invention. For example, the antireflection layer 14 can be a multilayer stacked structure composed of silicon oxide and / or niobium oxide, etc.

[0053] The DLC layer 16 can be formed from a first hydrocarbon gas by a PECVD process, or can be formed from a first hydrocarbon gas and a plasma source gas by a PECVD process.

[0054] The doped transition layer 18 can be formed from a doped element gas source or from a doped element gas source and a second hydrocarbon gas by a PECVD process. Alternatively, the doped transition layer 18 can be formed from a doped element gas source and a plasma source gas or from a doped element gas source, a second hydrocarbon gas, and a plasma source gas by a PECVD process.

[0055] The plasma source gas can include, for example, an inert gas.

[0056] The first hydrocarbon gas and the second hydrocarbon gas can be the same or different from each other.

[0057] The anti-fingerprint layer 20 can be any film with slipperiness and stain resistance, as long as it is applicable to the present invention. In some specific embodiments, the raw material of the anti-fingerprint layer 20 is a fluorinated material. For example, the anti-fingerprint layer 20 can be composed of perfluoropolyether silicone. In some specific embodiments, the fluorinated material can be UF503, UD509, UD500 manufactured by Daikin Industries, Ltd., KY-178, KY-185, KY-1900, X-71-195, X-71-197 manufactured by Shin-Etsu Chemical Co., Ltd., and so on.

[0058] In the embodiment of the present application, the glass display panel protection film 10 includes a DLC layer 16 with excellent properties such as high hardness and low friction coefficient, which can be beneficial to improving the surface hardness of the glass display panel protection film 10.

[0059] In addition, by the PECVD process, the DLC layer 16 and the doped transition layer 18 are sequentially formed on the anti-reflection layer 14 in contact with the glass display panel 12, so that the anti-reflection layer 14, the DLC layer 16, and the doped transition layer 18 are superposed on each other. The doped transition layer 18 is also superposed on the anti-fingerprint layer 20, which can enable the DLC layer 16 and the anti-fingerprint layer 20 to be well combined through the doped transition layer 18. In this way, the anti-reflection layer 14, the DLC layer 16, the doped transition layer 18, and the anti-fingerprint layer 20 are superposed on each other, which can be beneficial to improving the scratch resistance and wear resistance of the glass display panel protection film 10.

[0060] In addition, the anti-reflection layer 14 in the glass display panel protection film 10 can endow it with good anti-reflection performance, and the anti-fingerprint film 20 can endow it with good anti-fouling performance.

[0061] Therefore, the technical solution of the embodiment of the present invention can be beneficial to providing a glass display panel protection film with improved surface hardness, scratch resistance, wear resistance, and good anti-reflection and anti-fouling properties.

[0062] In some embodiments, the first hydrocarbon gas and the second hydrocarbon gas each independently include one or more of methane, ethane, propane, ethylene, acetylene, propylene, propyne, benzene vapor, and toluene vapor.

[0063] For benzene and toluene that are not gaseous under normal pressure, they can be heated and evaporated or depressurized respectively to form benzene vapor and toluene vapor.

[0064] In some embodiments, the doping element includes at least one of silicon and nitrogen.

[0065] The doped transition layer 18 can bond with the perfluoropolyether silicone in the fingerprint-proof layer 20 through the doped elements silicon and / or nitrogen therein. For example, chemical bonds such as Si-O, Si-O-Si, and N-Si are formed, so as to be well combined with the fingerprint-proof layer 20. Furthermore, the DLC layer 16 laminated with the doped transition layer 18 can be well combined with the fingerprint-proof layer 20. In this way, it is beneficial to improve the scratch resistance and wear resistance of the protective film 10 of the glass display panel.

[0066] The doped element may also include any element other than silicon and nitrogen, as long as it is applicable to the present invention.

[0067] In some embodiments, the doped element gas source includes at least one of silane, alkyl-substituted silane, siloxane, nitrogen gas, and ammonia gas.

[0068] In the embodiments of the present application, unless otherwise specifically indicated, the doped element gas source refers to a gas source that can provide and / or contain the doped elements described in the present application.

[0069] If silicon is selected as the doped element, at least one of silane, alkyl-substituted silane, and siloxane can be selected as the doped element gas source. If nitrogen is selected as the doped element, at least one of nitrogen gas and ammonia gas can be selected as the doped element gas source. If silicon and nitrogen are selected as the doped elements, at least one can be selected from silane, alkyl-substituted silane, and siloxane respectively and nitrogen gas and ammonia gas respectively, and they can be used together as the doped element gas source.

[0070] In some embodiments, the silane includes at least one of silane, disilane, and trisilane.

[0071] For trisilane that is non-gaseous under normal pressure, it can be heated and evaporated or depressurized to form trisilane vapor.

[0072] In some embodiments, the alkyl-substituted silane includes at least one of methylsilane, dimethylsilane, trimethylsilane, and tetramethylsilane.

[0073] In some embodiments, the siloxane includes hexamethyldisiloxane.

[0074] The doped element gas source in the embodiments of the present application is not limited thereto, and may also include any other applicable doped element gas source.

[0075] In some embodiments, the fingerprint-proof layer 20 is formed by a vacuum evaporation process.

[0076] The fingerprint-proof layer 20 can be formed by any known vacuum evaporation process, and can also be formed by other known methods, such as magnetron sputtering, spraying, etc., as long as it is applicable to the present invention.

[0077] In some embodiments, the sum of the thicknesses of the DLC layer 16, the doped transition layer 18, and the fingerprint-proof layer 20 is less than 50 nm.

[0078] In the embodiments of the present application, unless otherwise specifically indicated, the numerical range may include any sub-range therein. For example, less than 50 nm may include 40 nm, 30 nm, 20 nm, 10 nm, and so on.

[0079] In some embodiments, the sum of the thicknesses of the DLC layer 16, the doped transition layer 18, and the fingerprint-proof layer 20 is above 30 nm.

[0080] Another aspect of the embodiments of the present invention relates to a method for preparing a protective film 10 for a glass display panel, which includes:

[0081] Step S1. Prepare an antireflection layer 14 on the glass display panel 12;

[0082] Step S2. Deposit a DLC layer 16 on the surface of the antireflection layer 14 from a first hydrocarbon gas by PECVD process;

[0083] Step S3. Deposit a doped transition layer 18 on the surface of the DLC layer 16 from a doped element gas source or from a doped element gas source and a second hydrocarbon gas by PECVD process; and

[0084] Step S4. Prepare a fingerprint-proof layer 20 on the surface of the doped transition layer 18, such that the fingerprint-proof layer 20 and the doped transition layer 18 overlap each other.

[0085] In the embodiments of the present application, the antireflection layer 14 can be prepared on the glass display panel 12 through step S1 first, so as to endow the protective film 10 for the glass display panel with good antireflection performance.

[0086] Then, a DLC layer 16 and a doped transition layer 18 are sequentially formed on the antireflection layer 14 through steps S2 and S3, such that the antireflection layer 14, the DLC layer 16, and the doped transition layer 18 overlap each other. Then, a fingerprint-proof layer 20 that overlaps with it is prepared on the surface of the doped transition layer 18 through step S4, so that the DLC layer 16 and the fingerprint-proof layer 20 can be well combined through the doped transition layer 18.

[0087] In this way, the antireflection layer 14, the DLC layer 16, the doped transition layer 18, and the fingerprint-proof layer 20 overlap each other, which is conducive to improving the scratch resistance and wear resistance of the protective film 10 for the glass display panel. At the same time, the protective film 10 for the glass display panel can also have good antireflection performance and stain resistance.

[0088] Steps S1 and S4 can be carried out in any known manner as long as it is applicable to the present invention.

[0089] In some embodiments, step S2 and / or step S3 are carried out under a vacuum degree of 1 Pa - 5 Pa, a bias voltage of 100 V - 800 V, and a plasma source power of 100 W - 800 W.

[0090] Step S2 and / or step S3 can be carried out by an ICP (Inductively Coupled Plasma) source.

[0091] In some embodiments, the method described in this application includes step S5. Cleaning the surface of the antireflection layer 14, and step S5 is carried out before step S2.

[0092] Specifically, step S5 can be carried out as follows: The glass display panel 12 formed with the antireflection layer 14 is sequentially placed in anhydrous ethanol and deionized water for ultrasonic cleaning for 10 min. After the ultrasonic cleaning is completed, it is taken out and wiped with a dust-free cloth, and then placed in a drying cabinet at about 25 °C for drying for more than 12 hours.

[0093] In some embodiments, the method described in this application includes step S6. Plasma etching the surface of the cleaned antireflection layer 14, and step S6 is carried out before step S2.

[0094] In this way, it is beneficial to increase the surface activity of the antireflection layer 14 and improve the bonding force between the antireflection layer 14 and the DLC layer 16.

[0095] Specifically, step S6 can be carried out as follows: The glass display panel 12 after completing step S5 is loaded on the sample turntable in the vacuum chamber, and the chamber base pressure is pumped down to below 6.0×10 -3 Pa, introduce an etching gas of 50 sccm - 200 sccm, control the vacuum degree at 1 Pa - 5 Pa, then apply a bias voltage of 100 V - 800 V on the turntable, set the plasma source power to 100 W - 800 W, and carry out plasma etching for 3 min - 20 min.

[0096] Here, the etching gas can include but is not limited to argon, helium, oxygen, neon, nitrogen.

[0097] In some embodiments, the method described in this application includes step S7. Plasma bombarding and activating the surface of the doped transition layer 18, and step S7 is carried out before step S4.

[0098] In this way, it is beneficial to increase the surface activity of the doped transition layer 18 and improve the bonding force between the doped transition layer 18 and the fingerprint-proof layer 20.

[0099] Specifically, step S7 can be carried out as follows: Place the glass display panel 12 formed with the doped transition layer 18 into the vacuum evaporation coating equipment for the anti-fingerprint layer 20. Pump the bottom pressure of the cavity to below 1 Pa, introduce argon gas at 500 sccm - 1200 sccm, control the vacuum degree at 1 Pa - 5 Pa, apply a bias voltage of 500 V - 800 V on the metal mesh electrode facing the sample holder, and conduct plasma bombardment activation for 60 s - 500 s.

[0100] In some embodiments, step S4 includes vacuum evaporating perfluoropolyether silicone on the surface of the doped transition layer 18 after plasma bombardment activation to form the anti-fingerprint layer 20.

[0101] Specifically, the cavity of the vacuum evaporation coating equipment can be evacuated to a bottom pressure of 7×10 -3 Pa, apply a current of 400 A - 600 A to the anti-fingerprint pill evaporation dish and conduct heating evaporation coating for 400 s - 600 s.

[0102] In some embodiments, the method described in this application includes step S8. After step S4, leave the glass display panel 12 at room temperature for more than 120 min.

[0103] In this way, it is beneficial for the anti-fingerprint layer 20 to fully age.

[0104] In some embodiments, the first hydrocarbon gas and the second hydrocarbon gas each independently include one or more of methane, ethane, propane, ethylene, acetylene, propylene, propyne, benzene vapor, and toluene vapor.

[0105] In some embodiments, the doping element includes at least one of silicon and nitrogen.

[0106] The doped transition layer 18 can bond with the perfluoropolyether silicone in the anti-fingerprint layer 20 through the doping elements silicon and / or nitrogen therein. For example, chemical bonds such as Si - O, Si - O - Si, and N - Si are formed, so as to be well combined with the anti-fingerprint layer 20. Furthermore, the DLC layer 16 laminated with the doped transition layer 18 can be well combined with the anti-fingerprint layer 20. In this way, it is beneficial to improve the scratch resistance and wear resistance of the protective film 10 of the glass display panel.

[0107] The doping element can also include any element other than silicon and nitrogen, as long as it is applicable to the present invention.

[0108] In some embodiments, the doping element gas source includes at least one of silane, alkyl-substituted silane, siloxane, nitrogen gas, and ammonia gas.

[0109] If silicon is selected as the doping element, at least one of silane, alkyl-substituted silane, and siloxane can be selected as the doping element gas source. If nitrogen is selected as the doping element, at least one of nitrogen gas and ammonia can be selected as the doping element gas source. If silicon and nitrogen are selected as the doping elements, at least one can be selected from silane, alkyl-substituted silane, and siloxane respectively and nitrogen gas and ammonia respectively, and they can be used together as the doping element gas source.

[0110] In some embodiments, the silane includes at least one of silane, disilane, and trisilane.

[0111] For trisilane which is non-gaseous under normal pressure, it can be heated and evaporated or depressurized to form trisilane vapor.

[0112] In some embodiments, the alkyl-substituted silane includes at least one of methylsilane, dimethylsilane, trimethylsilane, and tetramethylsilane.

[0113] In some embodiments, the siloxane includes hexamethyldisiloxane.

[0114] The doping element gas source in the embodiments of the present application is not limited thereto, and may also include any other applicable doping element gas source.

[0115] In some embodiments, the sum of the thicknesses of the DLC layer 16, the doped transition layer 18, and the fingerprint-proof layer 20 is less than 50 nm.

[0116] The sum of the thicknesses of the DLC layer 16, the doped transition layer 18, and the fingerprint-proof layer 20 can be 30 nm or more.

[0117] The Mohs hardness of the DLC layer 16, the doped transition layer 18, and the fingerprint-proof layer 20 can reach 7. After being rubbed with steel wool 15,000 times, the water contact angle is greater than 100°, and the oil contact angle is about 68°.

[0118] Another aspect of the embodiments of the present invention relates to a product 100, which includes a glass display panel 12 and a protective film 10 for the glass display panel 12 as described in the present application that covers at least a part of the surface of the glass display panel 12.

[0119] The product 100 may include various 3C products, virtual reality products, etc.

[0120] The technical solution of the embodiments of the present application can be beneficial to provide a product 100 with a protective film 10 for a glass display panel as the outer protection, which has improved surface hardness, scratch resistance, wear resistance, and good antireflection and antifouling properties, and can be beneficial to improving the surface hardness, scratch resistance, and wear resistance of the glass display panel 12 of the product 100.

[0121] The embodiments of the present invention will be described below through specific examples. These examples are only used to explain the present invention and are not intended to limit the protection scope of the present invention.

[0122] Example 1

[0123] 1) Cleaning: The glass display panel 12 formed with the antireflection layer 14 was successively placed in anhydrous ethanol and deionized water for ultrasonic cleaning for 10 min. After the ultrasonic cleaning was completed, it was taken out and wiped with a dust-free cloth, and then placed in a drying cabinet at 25°C for 13 hours.

[0124] 2) Preparation of the DLC layer 16 and the doped transition layer 18: The glass display panel 12 cleaned in step 1) was loaded on the sample turntable in the vacuum chamber, and the bottom pressure of the chamber was pumped to 6.0×10 -3 Pa, and 100 sccm of argon was introduced as the etching gas. The vacuum degree was controlled at 4 Pa, and then a 600 V bias voltage was applied to the turntable. The plasma source power was set to 600 W, and plasma etching was carried out for 3 min. Subsequently, the vacuum degree of the cavity was pumped to the base vacuum. Then, 50 sccm of acetylene and argon were introduced, the vacuum degree was controlled at 4 Pa, and then a 600 V bias voltage was applied to the turntable. The plasma source power was set at 600 W, and the duration was 5 min to prepare the DLC layer 16. After the preparation of the DLC layer 16 was completed, the cavity was pumped to the base vacuum. Then, 50 sccm of tetramethylsilane and 50 sccm of argon were introduced, the vacuum degree was controlled at 4 Pa, and then a 600 V bias voltage was applied to the turntable. The plasma source power was set at 200 W, and the duration was 3 min to prepare the doped transition layer 18.

[0125] 3) Preparation of the fingerprint-proof layer 20: The glass display panel 12 after step 2) was taken out and placed in a fingerprint-proof vacuum evaporation coating equipment. The bottom pressure of the chamber was pumped to 1 Pa, 800 sccm of argon was introduced, the vacuum degree was controlled at 3 Pa, and a 600 V bias voltage was applied to the metal mesh for 200 s of plasma bombardment activation. Subsequently, the chamber of the vacuum evaporation coating equipment was pumped to the bottom pressure, and a 500 A current was applied to the fingerprint-proof pill evaporation dish loaded with UD509 manufactured by Daikin Industries, Ltd. for 500 s of heating evaporation coating. After the evaporation coating was completed, the glass display panel 12 covered with the glass display panel protective film 10 on the surface was taken out and left standing at room temperature for 240 min.

[0126] Example 2

[0127] The glass display panel protective film 10 was prepared in the same manner as in Example 1, except that methane was used instead of acetylene in step 2).

[0128] Example 3

[0129] The glass display panel protective film 10 was prepared in the same manner as in Example 1, except that propane was used instead of acetylene in step 2).

[0130] Example 4

[0131] The glass display panel protective film 10 was prepared in the same manner as in Example 1, except that trimethylsilane was used instead of tetramethylsilane in step 2).

[0132] Example 5

[0133] The glass display panel protective film 10 was prepared in the same manner as in Example 1, except that silane and acetylene were used instead of tetramethylsilane in step 2).

[0134] Example 6

[0135] The glass display panel protective film 10 was prepared in the same manner as in Example 1, except that nitrogen and acetylene were used instead of tetramethylsilane in step 2).

[0136] Comparative Example 1

[0137] The glass display panel protective film 10 was prepared in the same manner as in Example 1, except that the preparation of the doped transition layer 18 in step 2) was omitted.

[0138] Comparative Example 2

[0139] The glass display panel protective film 10 was prepared in the same manner as in Example 1, except that the preparation of the DLC layer 16 and the doped transition layer 18 in step 2) was omitted.

[0140] Comparative Example 3

[0141] The glass display panel protective film 10 was prepared in the same manner as in Example 1, except that step 3) was omitted.

[0142] Comparative Example 4

[0143] The glass display panel protective film 10 was prepared in the same manner as in Example 1, except that the preparation of the DLC layer 16 in step 2) was omitted.

[0144] Comparative Example 5

[0145] The glass display panel protective film 10 was prepared in the same manner as in Example 1, except that steps 2) and 3) were omitted.

[0146] Test Example 1. Testing the stain resistance of the glass display panel protective film 10

[0147] The water contact angle and oil contact angle of the glass display panel protective film 10 prepared in Examples 1-6 and Comparative Examples 1-5 were tested using the SDC-100 water contact angle tester produced by Jiangsu Fevotech Nano Technology Co., Ltd. Among them, the oil contact angle was tested using n-hexadecane. The test results are summarized in Table 1 below.

[0148] Table 1. Test Results of the Glass Display Panel Protective Film 10

[0149]

[0150] Referring to Table 1, by comparing the water contact angle and oil contact angle of the glass display panel protective films in Examples 1-6 with those in Comparative Examples 3 and 5, it can be seen that the glass display panel protective film 10 of the present application includes an outermost fingerprint-proof layer 20, so it has a significantly improved water contact angle and oil contact angle, that is, it has good anti-fouling properties. The glass display panel protective films in Comparative Examples 3 and 5 do not include a fingerprint-proof layer, so the water contact angle and oil contact angle are lower, that is, the anti-fouling property is poor and the touch feeling is not good.

[0151] Test Example 2. Testing the Mohs hardness of the glass display panel protective film 10

[0152] The Mohs hardness of the glass display panel protective films in Examples 1-6 and Comparative Examples 1-5 was tested using the LX5608 electric pencil hardness tester of ASRUI Instruments.

[0153] Specifically, Mohs pens with different hardnesses were placed on the electric hardness tester, the load applied to the pen tip was 500 g, the Mohs hardness pen was pushed forward for a length of 2 cm, and it was scratched 3 times at different positions. The hardness of the glass display panel protective film was determined according to the presence or absence of scratches. The test results are summarized in Table 1 above.

[0154] Referring to Table 1, by comparing the Mohs hardness of the glass display panel protective films in Examples 1-6 with those in Comparative Examples 2, 4, and 5, it can be seen that the glass display panel protective film 10 of the present application includes a DLC layer 16, so it has a significantly improved Mohs hardness, that is, significantly improved surface hardness and scratch resistance.

[0155] Test Example 3. Testing the reflectivity of the glass display panel protective film 10

[0156] The reflectivity of the glass display panel protective films in Examples 1-6 and Comparative Examples 1-5 was tested using a SPECTROPHOTOMETER CM-5 spectrophotometer. The test results are summarized in Table 1 above.

[0157] By comparing the reflectivity of the glass display panel protective films in Examples 1-6 with that in Comparative Example 5, it can be seen that the anti-reflection property of the glass display panel protective film 10 of the present application has no obvious change.

[0158] Test Example 4. Abrasion Resistance Test of the Protective Film 10 for the Glass Display Panel

[0159] The wire wool abrasion test was carried out on the protective films for the glass display panels in Examples 1-6 and Comparative Examples 1-5 using the ZJ-339-GSR wire wool abrasion testing machine of Zhijia Instruments. The test conditions were as follows: Bonstar OOOO# wire wool, a load of 500 g, a stroke of 1 inch, a frequency of 60 cycle / min, and a grinding head of 10*10 mm. The water contact angle after 15,000 times of friction testing was measured. The test results are summarized in Table 1 above.

[0160] By comparing the changes in the water contact angle before and after friction of the protective films for the glass display panels in Examples 1-6 and Comparative Examples 1 and 4, it can be seen that the doped transition layer 18 in the protective film 10 for the glass display panel of the present application significantly improves the bonding between the DLC layer 16 and the fingerprint-resistant layer 20, thus significantly improving the abrasion resistance of the protective film 10 for the glass display panel.

[0161] From the test results in Table 1 above, it can be seen that the protective film 10 for the glass display panel of the present application has improved surface hardness, scratch resistance, abrasion resistance, as well as good antireflection and antifouling properties.

[0162] The various specific embodiments described above and shown in the drawings are only for illustrating the present invention and not all of the present invention. Any form of change made by those of ordinary skill in the relevant technical field to the present invention within the scope of the basic technical idea of the present invention is within the protection scope of the present invention.

Claims

1. A protective film for a glass display panel, characterized in that, The invention comprises an anti-reflection layer, a DLC layer, a doped transition layer and an anti-fingerprint layer which are stacked on each other in sequence, wherein the anti-reflection layer is in contact with the glass display panel, the DLC layer is formed by a first hydrocarbon gas through a PECVD process, and the doped transition layer is formed by a doped element gas source or by a doped element gas source and a second hydrocarbon gas through a PECVD process.

2. The protective film for a glass display panel according to claim 1, wherein, The first hydrocarbon gas and the second hydrocarbon gas each independently include one or more of methane, ethane, propane, ethylene, acetylene, propylene, propyne, benzene vapor, and toluene vapor.

3. The protective film for a glass display panel according to claim 1, wherein The doping element includes at least one of silicon and nitrogen.

4. The protective film for a glass display panel according to claim 3, wherein, The doping element gas source includes at least one of silane, alkyl-substituted silane, siloxane, nitrogen and ammonia.

5. The protective film for a glass display panel according to claim 4, wherein, The silane includes at least one of monosilane, disilane and trisilane.

6. The protective film for a glass display panel according to claim 4, wherein, The alkyl-substituted silane includes at least one of methylsilane, dimethylsilane, trimethylsilane and tetramethylsilane.

7. The protective film for a glass display panel according to claim 4, wherein The siloxane includes hexamethylsilyl ether.

8. The protective film for a glass display panel according to claim 1, wherein, The anti-fingerprint layer is formed by a vacuum evaporation process.

9. The protective film for a glass display panel according to any one of claims 1-8, characterized in that, The sum of the thicknesses of the DLC layer, the doped transition layer and the anti-fingerprint layer is less than 50 nm.

10. A preparation method of a protective film for a glass display panel, characterized in that, include: Step S1. Preparing an anti-reflection layer on a glass display panel; Step S2. Depositing a DLC layer on the surface of the anti-reflection layer by a first hydrocarbon gas through a PECVD process; Step S3. Depositing a doped transition layer on the surface of the DLC layer by a PECVD process using a doping element gas source or the doping element gas source and a second hydrocarbon gas; as well as Step S4. preparing an anti-fingerprint layer on the surface of the doped transition layer, so that the anti-fingerprint layer and the doped transition layer overlap each other.

11. The preparation method according to claim 10, characterized in that, The step S2 and / or the step S3 are performed under a vacuum degree of 1 Pa-5 Pa, a bias voltage of 100 V-800 V, and a plasma source power of 100 W-800 W.

12. The preparation method according to claim 10, characterized in that, The method comprises step S5 of cleaning the surface of the anti-reflection layer, wherein step S5 is performed before step S2.

13. The preparation method according to claim 12, characterized in that, The method comprises step S6. performing plasma etching on the surface of the cleaned anti-reflection layer, wherein step S6 is performed before step S2.

14. The preparation method according to claim 10, characterized in that, The method comprises step S7: performing plasma bombardment activation on the surface of the doped transition layer, and step S7 is performed before step S4.

15. The preparation method according to claim 14, characterized in that, The step S4 includes vacuum evaporating perfluoropolyether organic silicon on the surface of the doped transition layer after plasma bombardment activation to form the anti-fingerprint layer.

16. The preparation method according to claim 15, characterized in that, The method comprises step S8. After step S4, the glass display panel is left to stand at room temperature for more than 120 minutes.

17. The preparation method according to claim 10, characterized in that, The first hydrocarbon gas and the second hydrocarbon gas each independently include one or more of methane, ethane, propane, ethylene, acetylene, propylene, propyne, benzene vapor, and toluene vapor.

18. The preparation method according to claim 10, characterized in that, The doping element includes at least one of silicon and nitrogen.

19. The preparation method according to claim 18, wherein, The doping element gas source includes at least one of silane, alkyl-substituted silane, siloxane, nitrogen and ammonia.

20. The preparation method according to claim 19, characterized in that, The silane includes at least one of monosilane, disilane and trisilane.

21. The preparation method according to claim 19, characterized in that, The alkyl-substituted silane includes at least one of methylsilane, dimethylsilane, trimethylsilane and tetramethylsilane.

22. The preparation method according to claim 19, characterized in that, The siloxane includes hexamethylsilyl ether.

23. The preparation method according to any one of claims 10-22, characterized in that, The sum of the thicknesses of the DLC layer, the doped transition layer, and the fingerprint-proof layer is less than 50 nm.

24. A product, characterized in that, A glass display panel protection film including a glass display panel and covering at least a part of the surface of the glass display panel, which is as described in any one of claims 1-9.

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