AF film layer with high hardness and high wear resistance, glass product, preparation method and application

Abstract

The application discloses a high-hardness and high-wear-resistance AF film layer, a glass product, a preparation method and application, belongs to the AF film technical field, and relates to the AF film layer which comprises a silicon nitride layer arranged from bottom to top, and a hydrophobic antifouling and anti-fingerprint layer grafted on the surface of the silicon nitride layer; or the AF film layer comprises a silicon dioxide layer, a silicon nitride layer arranged from bottom to top, and a hydrophobic antifouling and anti-fingerprint layer grafted on the surface of the silicon nitride layer. The hydrophobic antifouling and anti-fingerprint layer is prepared by deiodization treatment of a perfluoropolyether substituted by single-end iodine or / and double-end iodine. The application solves the problem that the existing AF film layer is difficult to simultaneously have high hardness, high wear resistance and hydrophobic antifouling, has high mechanical strength, high hardness, hydrophobic antifouling and super wear resistance, and can meet the use requirements in the fields of train, automobile and windshield glass, 3C screens (such as mobile phones, tablets, vehicle-mounted display screens and digital cameras).

Description

TECHNICAL FIELD

[0001] The application relates to an AF film layer, in particular to a high-hardness and high-wear-resistance AF film layer, a glass product, a preparation method and application. BACKGROUND

[0002] With the improvement of living index, people's performance requirements for consumer goods such as glass screens, glass cover plates and camera lenses of electronic products used in daily life are increasingly strict, for example, high hardness, anti-reflection, hydrophobic and anti-fouling, anti-fingerprint and wear resistance are required.

[0003] In the prior art, a plurality of silicon dioxide composite coatings are usually plated on the surface of the glass, and then an AF coating is fixed on the outermost silicon dioxide to achieve the above technical effects. For example, a Chinese patent with the publication number CN113652641A discloses an anti-reflection film, which comprises an AR film layer and an AF film layer. The AR film layer comprises three SiO2 layers and two Nb2O5 layers, and the two Nb2O5 layers are respectively sandwiched between the three SiO2 layers. The SiO2 layer on one side is fixed on the base layer, and the AF film layer is fixed on the SiO2 layer on the other side. However, the multi-layer structure will increase the haze, and the presence of the SiO2 layer on the AF film layer side will reduce the hardness and mechanical strength.

[0004] In addition, another way is to directly plate an AF film layer on a silicon nitride layer. For example, a Chinese patent with the publication number CN214491874U discloses a fingerprint-resistant protective film, which comprises alternatingly stacked silicon dioxide layers and silicon nitride layers. Both the silicon dioxide layers and the silicon nitride layers are provided with at least 7 layers, and the two surface layers of the protective film are respectively a silicon dioxide layer and a silicon nitride layer. The fingerprint-resistant protective film comprises the protective film and an AF film layer, and the AF film layer is arranged on the surface of the protective film. The hardness of the fingerprint-resistant protective film is greater than 9H, and the initial hydrophobic angle is greater than 110°, which has good surface hardness and hydrophobic and anti-fouling effects. However, the AF film layer and the silicon nitride layer cannot be effectively combined, which leads to a water contact angle of about 90° after 5k times of steel wool rubbing, and poor wear resistance. A Chinese patent with the publication number CN221917819U discloses a hard AF film, which comprises an indirect layer, a hard layer and an AF layer on the surface of a substrate. The indirect layer is Al2O3 or SiO2 / Si, and the hard layer is silicon nitride. The overall film hardness is high, the Mohs hardness of the film is greater than or equal to 6, the nano indentation is greater than or equal to 15, and the Vickers hardness is greater than or equal to 1500. However, the silicon nitride layer and the AF layer cannot be effectively combined, which leads to poor friction resistance: the water contact angle is only about 90° after 4200 times of steel wool rubbing, and the water contact angle is only about 100° after 4200 times of rubber rubbing.

[0005] Therefore, it is necessary to develop an AF film layer with high hardness, high wear resistance, and hydrophobic and antifouling properties to meet the use requirements of electronic product AF film layers.

[0006] It should be noted that the information disclosed in the above background section is only used to strengthen the understanding of the background of the present disclosure, and therefore can include information that does not constitute prior art known to those of ordinary skill in the art. SUMMARY

[0007] The purpose of the present application is to provide a high-hardness and high-wear-resistance AF film layer, glass product, preparation method and application, which solves the problem that the existing AF film layer is difficult to have high hardness, high wear resistance and hydrophobic and antifouling properties at the same time, has high mechanical strength, high hardness, hydrophobic and antifouling properties, super wear resistance and other properties, and can meet the use requirements in the fields of train, automobile windshield, 3C screen and the like.

[0008] In order to achieve the above purpose, the present application provides a high-hardness and high-wear-resistance AF film layer, which comprises a layer of silicon nitride layer arranged from bottom to top, and a hydrophobic and antifouling anti-fingerprint layer grafted on the surface of the silicon nitride layer; or the AF film layer comprises a layer of silicon dioxide layer, a layer of silicon nitride layer arranged from bottom to top, and a hydrophobic and antifouling anti-fingerprint layer grafted on the surface of the silicon nitride layer.

[0009] The hydrophobic and antifouling anti-fingerprint layer is prepared by deiodization treatment of a single-end iodine-substituted or / and double-end iodine-substituted perfluoropolyether; the chemical structures of the single-end iodine-substituted and double-end iodine-substituted perfluoropolyether are shown in formula I and II respectively.

[0010]

[0011]

[0012] In formula I, Rf is a K-type perfluoropolyether with a molecular weight of 1100-1200.

[0013] Preferably, the thickness of the silicon dioxide layer is 0-80 nm; the thickness of the silicon nitride layer is 35-95 nm; and the thickness of the hydrophobic and antifouling anti-fingerprint layer is 18-39 nm.

[0014] The second purpose of the present application is to provide a preparation method of the high-hardness and high-wear-resistance AF film layer, which comprises the following steps:

[0015] (1) Preparation of the silicon dioxide layer and the silicon nitride layer

[0016] The silicon nitride layer is prepared on the surface of the substrate, or the silicon dioxide layer and the silicon nitride layer are prepared in sequence;

[0017] (2) Preparation of the hydrophobic anti-fouling and anti-fingerprint layer

[0018] A layer of perfluoropolyether iodide is applied on the surface of the silicon nitride layer by spraying, and the perfluoropolyether iodide is grafted on the surface of the silicon nitride layer after standing. The substrate is cleaned and dried to obtain the hydrophobic anti-fouling and anti-fingerprint layer.

[0019] (3) Deiodination treatment

[0020] The substrate is soaked in a reducing agent solution for deiodination treatment. After the treatment is completed, the substrate is taken out, cleaned, and heated and solidified to obtain the AF film layer with high hardness and high wear resistance.

[0021] Preferably, in step (1), a silicon target is used as a raw material to prepare a silicon nitride layer or sequentially prepare a silicon dioxide layer and a silicon nitride layer on the surface of the substrate by sputtering plating.

[0022] Preferably, in step (1), the substrate is sequentially cleaned with anhydrous ethanol and acetone, and then dried before preparing the silicon dioxide layer and the silicon nitride layer.

[0023] Preferably, in step (1), the silicon nitride layer or the silicon dioxide layer and the silicon nitride layer are prepared, and then sequentially cleaned with anhydrous ethanol and acetone and dried at room temperature after standing.

[0024] Preferably, in step (2), the standing time is 30-120 min.

[0025] Preferably, in step (2), the preparation method of the perfluoropolyether iodide comprises:

[0026] The perfluoropolyether iodide is obtained by performing an electrophilic addition reaction between perfluoropolyether acrylate and hydrogen iodide in chloroform under an inert atmosphere at room temperature, and then distilling and purifying the reaction product.

[0027] Preferably, in step (2), the cleaning is sequentially performed with hydrofluoroether and acetone.

[0028] Preferably, in step (3), the reducing agent solution is selected from at least one of sulfite, pyrosulfite, and thiosulfate solutions.

[0029] Preferably, in step (3), the concentration of the reducing agent solution is 0.3-0.8 mol / L.

[0030] Preferably, in step (3), the deiodination treatment is performed at 45-50°C.

[0031] More preferably, in step (3), the deiodination treatment time is 2-6 h.

[0032] Preferably, in step (3), the heating solidification is at a temperature of 60±5℃.

[0033] More preferably, in step (3), the heating solidification is for a time of 2-3h.

[0034] Preferably, in step (3), the cleaning is performed sequentially using anhydrous ethanol and acetone.

[0035] A third object of the present application is to provide a glass product having the high-hardness and high-wear-resistance AF film layer on the surface of the glass.

[0036] A fourth object of the present application is to provide the use of the high-hardness and high-wear-resistance AF film layer in the screen of an electronic product. Specifically, in the field of windshields of trains or cars, 3C screens (such as mobile phones, tablets, vehicle display screens, digital camera lenses), etc.

[0037] The high-hardness and high-wear-resistance AF film layer, the glass product, the preparation method and the use of the present application solve the problem that the existing AF film layer is difficult to simultaneously have high hardness, high wear resistance and hydrophobic and antifouling properties, and have the following advantages:

[0038] (1) The high-hardness and high-wear-resistance AF film layer of the present application drives the perfluoropolyether molecules to be directly grafted on the surface of the silicon nitride layer through the interaction between the iodine in the single-end iodine-substituted or / and double-end iodine-substituted perfluoropolyether and the lone pair electrons of nitrogen and oxygen atoms in the silicon nitride layer, avoiding the poor bonding performance and the easy peeling of the coating layer caused by the problem of interface compatibility between the perfluoropolyether compound and the silicon nitride layer;

[0039] (2) The high-hardness and high-wear-resistance AF film layer of the present application has high hardness, high mechanical strength, and durable hydrophobic and antifouling properties, with a pencil hardness greater than 8H and an initial water contact angle greater than 115°. After 25k times of steel wool rubbing, the water contact angle is still greater than 103°, meeting the use requirements in the field of windshields of trains, cars, etc., and 3C screens, etc.

[0040] (3) The technical solution adopted by the present application is simple and easy to implement, and since it does not need to attach a silica layer on the surface of the silicon nitride layer, the production cost is effectively reduced, and it is suitable for large-scale industrial production. BRIEF DESCRIPTION OF DRAWINGS

[0041] Figure 1 Nuclear magnetic resonance hydrogen spectrum of the perfluoropolyether iodine derivative prepared in Example 1 of the present application.

[0042] Figure 2 SEM spectrum of the cross section of part of the AF film layer prepared in Example 2 of the present application. DETAILED DESCRIPTION

[0043] The technical solutions in the embodiments of the present application will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present application, but not all the embodiments. Based on the embodiments in the present application, all the other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the present application.

[0044] It should be noted that, in the embodiments, the specific conditions not specified are carried out according to the conventional conditions or the conditions recommended by the manufacturer. The instruments used are all conventional products that can be obtained by market purchase, and the manufacturers are not specified. The raw materials and reagents used are all market goods or can be prepared by known methods, and the manufacturers are not specified.

[0045] In the present application, all the features defined in the form of numerical range or percentage range, such as numerical value, quantity, content and concentration, are only for the sake of brevity and convenience. Therefore, the description of numerical range or percentage range should be considered to have covered and specifically disclosed all possible sub-ranges and individual numerical values (including integers and fractions) within the range.

[0046] The features mentioned in the present application can be combined arbitrarily, as long as the combination of the features does not exist contradiction, all possible combinations should be considered as the scope disclosed in the specification. Each feature disclosed in the specification can be replaced by any alternative feature that can provide the same, equivalent or similar purpose. Therefore, unless otherwise specified, the disclosed features are only general examples of equivalent or similar features.

[0047] The present application provides a high-hardness and high-wear-resistance AF film layer, a glass product, a preparation method and an application. A silica layer and a silicon nitride layer are plated on the surface of a glass substrate in sequence, then a hydrophobic, antifouling and anti-fingerprint layer is coated on the surface of the silicon nitride layer by grafting, and finally the hydrophobic, antifouling and anti-fingerprint layer is treated by deiodination. The hydrophobic, antifouling and anti-fingerprint layer is prepared by deiodination of a perfluoropolyether substituted by single-end iodine or / and double-end iodine. The chemical structures of the perfluoropolyether substituted by single-end iodine and double-end iodine are shown in formula I and II respectively.

[0048]

[0049]

[0050] In the formula, Rf is a K-type perfluoropolyether, and the molecular weight is 1100-1200.

[0051] The key technology of the application is to utilize the interaction between iodine in the single-end iodine-substituted or / and double-end iodine-substituted perfluoropolyether and the lone pair electrons of nitrogen and oxygen atoms in the silicon nitride layer, so as to drive the perfluoropolyether molecules to graft on the surface of the silicon nitride layer, and then effectively improve the stability of the AF film layer through deiodination treatment, thereby avoiding the problems of yellowing, blistering and peeling of the AF coating on the outer surface caused by long-time ultraviolet irradiation. The AF film layer provided by the application has excellent mechanical properties, high mechanical strength, high hardness, super wear resistance, hydrophobicity and antifouling properties.

[0052] The conventional perfluoropolyether acrylate (such as the Chinese patent “Y-type perfluoropolyether modified acrylate, antifouling coating and preparation method and application” with publication number CN116217916A) cannot be effectively combined with silicon nitride, and all need to be plated with a layer of silicon oxide on the surface of the silicon nitride, and then grafted with a perfluoropolyether layer. However, since the hardness of the silicon oxide layer is not as good as that of the silicon nitride, part of the mechanical strength and wear resistance will be lost.

[0053] The perfluoropolyether iodide in the application can be at least one of single-end iodine-substituted and double-end iodine-substituted perfluoropolyether.

[0054] The silicon nitride and silicon oxide layers in the application are both designed as one layer, and the optical refractive indexes of the silicon nitride and silicon oxide layers are different, so it is difficult to control the overall light transmittance by setting multiple layers.

[0055] The high-hardness and high-wear-resistance AF film layer, glass product, preparation method and application provided by the application are described in detail through the following examples.

[0056] In the following examples and comparative examples, the single-end iodine-substituted or double-end iodine-substituted perfluoropolyether is referred to as perfluoropolyether iodide, and the perfluoropolyether iodide solution used is a mixture of perfluoropolyether iodide and hydrofluoroether (hydrofluoroether 3M 7100), with a solid content of 24%.

[0057] In the application, the room temperature is 25℃ unless otherwise specified.

[0058] Example 1

[0059] The perfluoropolyether iodide of the example has a structure as shown in formula II, and the preparation method is as follows:

[0060]

[0061] The perfluoropolyether acrylate is prepared according to the embodiment 1 of the Chinese patent with the publication number CN116217916A "Y-type perfluoropolyether modified acrylate, antifouling coating, and preparation method and application". The perfluoropolyether acrylate and hydrogen iodide are weighed and added into a reactor, chloroform is used as a solvent, inert gas is introduced, and an electrophilic addition reaction is carried out at room temperature, the reaction endpoint is determined by detecting the double bond content, and the perfluoropolyether iodide is obtained after distillation and purification, and the nuclear magnetic resonance hydrogen spectrum is as shown in Figure 1 .

[0062] Example 2

[0063] A glass with AF film layer with high hardness and high wear resistance, and a preparation method thereof, specifically comprising the following steps:

[0064] (1) The glass substrate is sequentially cleaned with anhydrous ethanol and acetone, and after being washed clean and dried, a silicon target is used as a raw material to prepare a silicon dioxide layer and a silicon nitride layer on the surface of the glass substrate by sputtering coating method, and the thicknesses thereof are set to be 18 nm and 35 nm respectively, and after reaching the specified thickness, the glass substrate is taken out, and after being placed for 10 min, the glass substrate is sequentially cleaned with anhydrous ethanol and acetone, and is air-dried at room temperature for treatment;

[0065] (2) A layer of perfluoropolyether iodide solution is precisely coated on the surface of the silicon nitride layer by spraying, and the perfluoropolyether iodide is grafted on the surface of the silicon nitride layer after being placed for 30 min, and the glass substrate is sequentially cleaned with hydrofluoroether and acetone and air-dried, and the coating thickness is 20.6 nm;

[0066] (3) The glass substrate is immersed in a sodium sulfite solution with a concentration of 0.3 mol / L, and is subjected to deiodination treatment at 45-50°C, and after 4 h, the glass substrate is taken out, and then cleaned with anhydrous ethanol and acetone, and is solidified at 60°C for 2 h, and as shown in Figure 2 , it is the SEM spectrum of the cross section of part of the AF film layer prepared in Example 2 of the present application.

[0067] Example 3

[0068] A glass with AF film layer with high hardness and high wear resistance, and a preparation method thereof, specifically comprising the following steps:

[0069] (1) The glass substrate is sequentially cleaned with anhydrous ethanol and acetone, and after being washed clean and dried, a silicon target is used as a raw material to prepare a silicon dioxide layer and a silicon nitride layer on the surface of the glass substrate by sputtering coating method, and the thicknesses thereof are set to be 30 nm and 50 nm respectively, and after reaching the specified thickness, the glass substrate is taken out, and after being placed for 10 min, the glass substrate is sequentially cleaned with anhydrous ethanol and acetone, and is air-dried at room temperature for treatment;

[0070] (2) A layer of perfluoropolyether iodide solution is precisely applied on the surface of the above-mentioned silicon nitride layer by spraying, and is allowed to stand for 30 min, so that the perfluoropolyether iodide is grafted on the surface of the silicon nitride layer. The silicon nitride layer is then cleaned with hydrofluoroether and acetone and is dried, and the coating thickness is 25.1 nm;

[0071] (3) The above-mentioned glass substrate is immersed in a sodium pyrosulfite solution with a concentration of 0.5 mol / L, and is subjected to deiodization treatment at 45-50°C. After 3 h, the glass substrate is taken out, cleaned with anhydrous ethanol and acetone, and solidified at 60°C for 2 h.

[0072] Example 4

[0073] A glass with an AF film layer having high hardness and high wear resistance, specifically comprising the following preparation steps:

[0074] (1) The glass substrate is sequentially cleaned with anhydrous ethanol and acetone, and is dried. Then, a silicon target is used as a raw material, and a silicon dioxide layer and a silicon nitride layer are sequentially prepared on the surface of the glass substrate by sputtering and plating. The thicknesses of the silicon dioxide layer and the silicon nitride layer are set to be 40 nm and 50 nm, respectively. After reaching the specified thickness, the glass substrate is taken out, sequentially cleaned with anhydrous ethanol and acetone, and dried at room temperature, and is prepared for the next step.

[0075] (2) A layer of perfluoropolyether iodide solution is precisely applied on the surface of the above-mentioned silicon nitride layer by spraying, and is allowed to stand for 30 min, so that the perfluoropolyether iodide is grafted on the surface of the silicon nitride layer. The silicon nitride layer is then cleaned with hydrofluoroether and acetone and is dried, and the coating thickness is 18.9 nm.

[0076] (3) The above-mentioned glass substrate is immersed in a sodium pyrosulfite solution with a concentration of 0.75 mol / L, and is subjected to deiodization treatment at 45-50°C. After 4 h, the glass substrate is taken out, cleaned with anhydrous ethanol and acetone, and solidified at 60°C for 2 h.

[0077] Example 5

[0078] A glass with an AF film layer having high hardness and high wear resistance, specifically comprising the following preparation steps:

[0079] (1) The glass substrate is sequentially cleaned with anhydrous ethanol and acetone, and is dried. Then, a silicon target is used as a raw material, and a silicon dioxide layer and a silicon nitride layer are sequentially prepared on the surface of the glass substrate by sputtering and plating. The thicknesses of the silicon dioxide layer and the silicon nitride layer are set to be 80 nm and 95 nm, respectively. After reaching the specified thickness, the glass substrate is taken out, sequentially cleaned with anhydrous ethanol and acetone, and dried at room temperature, and is prepared for the next step.

[0080] (2) A layer of perfluoropolyether iodide solution is precisely applied on the surface of the above-mentioned silicon nitride layer by spraying, and is left to stand for 30 min, so that the perfluoropolyether iodide is grafted on the surface of the silicon nitride layer. The silicon nitride layer is then cleaned with hydrofluoroether and acetone and is left to dry, and the coating thickness is 38.7 nm;

[0081] (3) The above-mentioned glass substrate is immersed in a potassium sulfite solution with a concentration of 0.8 mol / L, and is subjected to deiodization treatment at 45-50°C. After 5 h, the glass substrate is taken out, cleaned with anhydrous ethanol and acetone, and is left to solidify at 60°C for 2 h.

[0082] Example 6

[0083] A glass with an AF film layer having high hardness and high wear resistance, specifically comprising the following preparation steps:

[0084] (1) The glass substrate is sequentially cleaned with anhydrous ethanol and acetone, and is left to dry. A silicon nitride layer is then prepared on the surface of the glass substrate by sputtering with a silicon target as the raw material, and the thickness of the silicon nitride layer is set to 70 nm. After the silicon nitride layer reaches the specified thickness, the glass substrate is taken out, left to stand for 10 min, and is sequentially cleaned with anhydrous ethanol and acetone, and is left to dry at room temperature.

[0085] (2) A layer of perfluoropolyether iodide solution is precisely applied on the surface of the above-mentioned silicon nitride layer by spraying, and is left to stand for 30 min, so that the perfluoropolyether iodide is grafted on the surface of the silicon nitride layer. The silicon nitride layer is then cleaned with hydrofluoroether and acetone and is left to dry, and the coating thickness is 25.8 nm.

[0086] (3) The above-mentioned glass substrate is immersed in a sodium sulfite solution with a concentration of 0.3 mol / L, and is subjected to deiodization treatment at 45-50°C. After 4 h, the glass substrate is taken out, cleaned with anhydrous ethanol and acetone, and is left to solidify at 60°C for 2 h.

[0087] Comparative Example 1

[0088] The difference between this comparative example and Example 2 is that:

[0089] A layer of silicon dioxide with a thickness of 12 nm is further coated on the silicon nitride layer, and the subsequent step of applying perfluoropolyether iodide is performed, and the other preparation steps and conditions are the same.

[0090] Comparative Example 2

[0091] The difference between this comparative example and Example 2 is that:

[0092] The perfluoropolyether iodide was replaced with a conventional perfluoropolyether AF reagent (a mixture of perfluoropolyether acrylate, silane coupling agent and hydrofluoroether prepared in Example 1 of Chinese Patent Publication No. CN116217916A), with a solid content of 24%, and the remaining preparation steps and conditions were consistent.

[0093] Comparative Example 3

[0094] This comparative example is compared with Example 2, the difference being that:

[0095] No deiodination treatment was performed in step (3), and the remaining preparation steps and conditions were consistent.

[0096] The performance of Examples 2-6 and Comparative Examples 1-3 of the present application was verified by testing the light transmittance, pencil hardness, initial water contact angle, and water contact angle after steel wool rubbing of the glass substrate surface, and the specific experimental process was as follows:

[0097] (1) Light transmittance test method

[0098] The light transmittance was determined by a TH-110 type light transmittance and haze meter. The coated substrate was placed on the test platform, the HOLD key of the instrument was pressed, and the test could start after the instrument was calibrated by itself. The test results were recorded.

[0099] (2) Pencil hardness

[0100] Referring to GB / T 6739-2022 "Paint and Varnish - Pencil Method for Determining Paint Film Hardness": the pencil method was used to determine the hardness of the coating.

[0101] (3) Weather resistance test method

[0102] The test was performed in accordance with GB / T 23987-2009 "Paint and Varnish - Artificial Weathering Exposure of Coatings - Exposure to Fluorescent UV and Water". The test results were evaluated based on the criteria of no powdering, no blistering, no cracking, and no peeling of the film, and the exposure time of 24 h was considered as qualified.

[0103] (4) Water contact angle test method

[0104] The static contact angle of the coating was determined by a JGW-360a type contact angle meter. The test liquid volume was 2 microliters, the test environment was 24 ± 1 ℃, and the relative humidity was 45 ± 1 %. The water contact angle was measured for 5 points, and the average value was taken.

[0105] (5) Steel wool abrasion resistance test method

[0106] The steel wool abrasion resistance test was determined by ZJ-339-GSR abrasion tester, the coated substrate was fixed on the tester, the rubber type was MUNBANGSAWOO, the pressure was set to 1000g, the stroke was set to 40mm, the speed was 40 cycles / min, and the water contact angle test result of the substrate after the test was recorded.

[0107] Table 1 Performance test results

[0108]

[0109] As shown in Table 1, the AF film layers prepared by Examples 2-6 all have excellent light transmittance, high mechanical strength and hydrophobic and antifouling properties, the pencil hardness is more than 8H, the initial water contact angle is more than 115°, and the water contact angle after steel wool rubbing for 25k times is more than 103°. Example 6 has a decrease in abrasion resistance due to the lack of a layer of silicon dioxide.

[0110] In addition, the results of Comparative Example 1 show that the structure of the silicon dioxide layer-silicon nitride layer-silicon dioxide layer-anti-fingerprint layer is not conducive to the high hardness and high mechanical strength of the coating, so that the results of the pencil hardness and steel wool rubbing test are significantly reduced. The results of Comparative Example 2 further show that the conventional AF anti-fingerprint agent cannot be effectively combined with the silicon nitride layer, so that the hydrophobic and antifouling properties and the abrasion resistance are significantly reduced. Comparative Example 3 does not perform the deiodization treatment of the AF film layer, so that after long-term ultraviolet irradiation, the coating surface appears phenomena such as powdering and bubbling, which cannot meet the use requirements.

[0111] Although the content of the present application has been described in detail by the above preferred embodiments, it should be recognized that the above description should not be considered as a limitation of the present application. After reading the above content, various modifications and alternatives of the present application will be apparent to those skilled in the art. Therefore, the protection scope of the present application should be defined by the appended claims.

Claims

1. A high-hardness, high-wear-resistant AF film layer, characterized in that, The AF film layer is composed of a silicon nitride layer and a hydrophobic antifouling and anti-fingerprint layer grafted on the surface of the silicon nitride layer, which are sequentially arranged from bottom to top. Or, the AF film layer is composed of a silicon dioxide layer, a silicon nitride layer and a hydrophobic antifouling and anti-fingerprint layer grafted on the surface of the silicon nitride layer, which are sequentially arranged from bottom to top. The hydrophobic anti-fouling and anti-fingerprint layer is prepared by deiodization of a single-end iodine-substituted or double-end iodine-substituted perfluoropolyether, and the chemical structures of the single-end iodine-substituted and double-end iodine-substituted perfluoropolyether are respectively shown as formula I and II: , ; In formula I, Rf is a K-type perfluoropolyether with a molecular weight of 1100-1200.

2. The high hardness, high wear resistant AF film layer of claim 1, wherein, The thickness of the silicon dioxide layer is 0-80 nm. The thickness of the silicon nitride layer is 35-95 nm. The thickness of the hydrophobic antifouling and anti-fingerprint layer is 18-39 nm.

3. The method for preparing the high-hardness, high-wear-resistant AF film as described in claim 1 or 2, characterized in that, The method comprises the following steps: (1) Preparation of the silicon dioxide layer and the silicon nitride layer A silicon nitride layer or a silicon dioxide layer and a silicon nitride layer are prepared on the surface of the substrate. (2) Preparation of the hydrophobic antifouling and anti-fingerprint layer A layer of perfluoropolyether iodide is applied on the surface of the silicon nitride layer by spraying, and the perfluoropolyether iodide is grafted on the surface of the silicon nitride layer after standing. After cleaning and drying, the hydrophobic antifouling and anti-fingerprint layer is obtained. (3) Deiodination treatment The substrate is soaked in a reducing agent solution for deiodination treatment. After the treatment is completed, the substrate is taken out, cleaned and heated to solidify, thereby obtaining the AF film layer with high hardness and high wear resistance.

4. The production method according to claim 3, characterized by, In step (1), a silicon nitride layer or a silicon dioxide layer and a silicon nitride layer are prepared on the surface of the substrate by sputtering with a silicon target as raw material. In step (2), the standing time is 30-120 min. In step (2), the preparation method of the perfluoropolyether iodide comprises: The perfluoropolyether iodide is obtained by electrophilic addition reaction of perfluoropolyether acrylate and hydrogen iodide in chloroform under inert atmosphere at room temperature, and then purified by distillation. In step (3), the reducing agent solution is selected from at least one of sulfite, pyrosulfite and thiosulfate solutions. In step (3), the deiodination treatment is carried out at 45-50°C.

5. The preparation method according to claim 4, characterized in that, In step (3), the concentration of the reducing agent solution is 0.3-0.8 mol / L.

6. The preparation method according to claim 4, characterized in that, In step (3), the deiodination treatment time is 2-6 h.

7. The method of any one of claims 3-6, wherein the method further comprises, In step (3), the heating solidification is carried out at 60±5°C.

8. The preparation method according to claim 7, characterized in that, In step (3), the heating solidification is carried out for 2-3 h.

9. A glass product, characterized by, The glass surface contains the AF film layer with high hardness and high wear resistance as claimed in claim 1 or 2.

10. Application of the AF film layer with high hardness and high wear resistance as claimed in claim 1 or 2 in the screen of electronic products.

Images