A method and system for continuously preparing AG film, AR film and AF film

Abstract

The present invention relates to the technical field of cover glass manufacturing, and in particular to a method and system for continuously preparing AG film, AR film and AF film. The method comprises: (1) introducing a substrate to be coated into chamber A for first cleaning to obtain substrate I with a surface water drop angle of no more than 20°, and spraying an anti-glare coating on the surface of substrate I to obtain substrate II containing an AG film; (2) introducing substrate II into chamber B for curing treatment to obtain substrate III; (3) introducing substrate III into chamber C for second cleaning and drying treatment in sequence to obtain substrate IV; (4) introducing substrate IV into chamber D to form AR film and AF film. The method provided by the present invention can continuously prepare AG film, AR film and AF film on a glass cover, and the prepared product has the characteristics of high yield, stable performance and good uniformity.

Description

Technical Field

[0001] The present invention relates to the technical field of cover glass manufacturing, and in particular to a method and system for continuously preparing an AG film, an AR film and an AF film. Background Art

[0002] With the development of outdoor and car displays, the anti-glare layer (AG) + anti-reflection and anti-transmittance layer (AR) + anti-fingerprint layer (AF) cover plate with anti-glare, high light transmittance and anti-fingerprint is favored by people. At present, in the AG+AR+AF film structure, the new Cologne RAS sputtering coating machine is used to superimpose multiple layers of Si3N4 and SiO2 on the AG glass. The surface layer is SiO2, and then AF is vacuum evaporated. However, the hardness of the SiO2 film layer is not as good as that of glass, resulting in the wear resistance of AG+AR+AF not being as good as that of AG+AF.

[0003] The core of RAS coating technology is that the redox reaction of the coating process is controlled on the surface of the glass substrate, which can greatly improve the adhesion between the film layer and the substrate, and between the film layers, and can make the film layer in a microcrystalline state. The film layer has a hardness that cannot be matched by evaporation coating and ordinary magnetron sputtering coating. Controlling the redox reaction to occur on the substrate can only be achieved on batch-type single-chamber non-continuous coating equipment.

[0004] The glass substrate rotates at high speed with the drum, and the Si material coated on the substrate does not exceed one molecular layer per rotation. + or + Ions can completely oxidize it. In a continuous coating machine, the glass is transported in multiple chambers, and each cathode-plated material has several molecular layers (if it is controlled within one molecular layer, the production efficiency is extremely low), and it can no longer be completely N + or + Ion nitrogen / oxidation. Therefore, the RAS technology has a very low production capacity and cannot be applied to high-efficiency continuous coating lines.

[0005] In addition, there is another solution, which is to make the surface of AR super-hard by adding diamond film DLC or graphite on the surface SiO2 of AR. However, the components of diamond-like film DLC and graphite are carbon, and carbon and AF cannot be chemically bonded. The two can only be physically adsorbed, and AF is very easy to fall off during friction testing. The adhesion between AF and AR is very poor, and the wear test shows that AF falls off and the AR layer is not damaged. Therefore, although AR is wear-resistant, the fall-off of AF causes the glass surface to have a reduced anti-fouling ability and color change, and it has not been widely used so far.

[0006] Moreover, the production equipment and processing methods of the cover plate coated with three film layers in the prior art are not ideal. The anti-glare layer and the anti-reflection and anti-transmittance layer need to go through several major processes such as curing, cleaning and transportation. When processing products with anti-glare layer, anti-reflection and anti-transmittance layer and anti-fingerprint layer, the production efficiency and production yield are greatly reduced. Summary of the invention

[0007] The purpose of the present invention is to solve the problems of low production efficiency and yield rate in the prior art of preparing AG+AR+AF film layer cover plates.

[0008] In order to achieve the above object, the first aspect of the present invention provides a method for continuously preparing an AG film, an AR film and an AF film, the method comprising:

[0009] (1) introducing the substrate to be coated into chamber A for first cleaning to obtain substrate I with a surface water drop angle of no more than 20°, and spraying an anti-glare coating on the surface of substrate I to obtain substrate II containing an AG film;

[0010] (2) introducing the substrate II into the chamber B for curing treatment to obtain a substrate III;

[0011] (3) introducing the substrate III into the chamber C and sequentially performing a second cleaning and drying process to obtain a substrate IV;

[0012] (4) Introducing the substrate IV into the chamber D to form an AR film and an AF film; wherein the method for forming the AR film comprises: in the presence of a protective atmosphere, alternately depositing metal oxide layers and silicon oxide layers on the surface of the substrate IV, and the oxygen content in the metal oxide layer is lower than the oxygen content in the silicon oxide layer.

[0013] Preferably, in step (4), the oxygen content in the metal oxide layer is 40-60 volume % lower than the oxygen content in the silicon oxide layer.

[0014] Preferably, in step (4), the main component of the metal oxide layer is niobium pentoxide and / or titanium dioxide.

[0015] Preferably, in step (1), the conditions of the first cleaning are controlled so that the surface water drop angle of the substrate 1 is no greater than 10°.

[0016] Preferably, in step (1), the first cleaning is performed by plasma cleaning, and the power of the plasma cleaning is 500-1500W, preferably 700-1200W.

[0017] Preferably, in step (1), the method further comprises: before performing the first cleaning, preheating the substrate to be coated.

[0018] Preferably, in step (1), the preheat treatment conditions include at least: a temperature of 20-400° C., preferably 30-120° C.; and a time of 12-60 seconds.

[0019] Preferably, in step (1), the spraying is performed under the condition that the substrate 1 is rotating, and the surface linear speed of the substrate 1 is 300-1200 mm / s.

[0020] Preferably, in step (1), the spraying conditions include at least: a spraying distance of 80-150 mm, a temperature of 20-130° C., a spray gun atomization pressure of 0.1-0.6 MPa, a spray gun fan pressure of 0.1-0.6 MPa, a supply pressure of the anti-glare coating of 0.1-0.6 MPa, and a flow rate of the anti-glare coating of 1-30 g / min.

[0021] Preferably, in step (2), the curing treatment conditions at least include: a temperature of 130-400° C. and a time of 20-60 min.

[0022] Preferably, in step (3), the second cleaning includes cleaning I with a neutral detergent, cleaning II with water, and cleaning III with acetone.

[0023] Preferably, in step (3), the conditions for the drying treatment at least include: a temperature of 100-180° C. and a time of 10-30 min.

[0024] Preferably, in step (4), the AF film is formed by vacuum evaporation, and the conditions of the vacuum evaporation at least include: a temperature of 300-600°C.

[0025] A second aspect of the present invention provides a system for continuously preparing an AG film, an AR film and an AF film, the system comprising:

[0026] A fixture, which is used to fix the substrate to be coated;

[0027] Chamber A, wherein a plasma cleaning gun array and an anti-glare spray gun array are arranged side by side in the chamber A, wherein the plasma cleaning gun array includes at least two plasma cleaning guns, and the distance between two adjacent plasma cleaning guns is 40-80 mm; the anti-glare spray gun array includes at least two anti-glare spray guns, and the distance between two adjacent anti-glare spray guns is 60-100 mm, and the chamber A is used to perform a first cleaning on the substrate to be coated and to form an AG film;

[0028] Chamber B, wherein at least two heating tubes are evenly arranged inside the chamber B, and the distance between two adjacent heating tubes is 20-100 mm, and the chamber B is used to cure the AG film;

[0029] Chamber C, wherein a cleaning spray gun, a brush and a hot air knife are arranged in the chamber C, wherein the cleaning spray gun is vertically arranged on the inner wall of the chamber C, and the nozzle of the cleaning spray gun is arranged vertically toward the substrate III, the brush is arranged tangentially to the jig, the hot air knife is vertically arranged on the inner wall of the chamber C, and the hot air knife outlet is arranged toward the substrate III, and a liquid and gas recovery port is also arranged below the chamber C;

[0030] A chamber D is provided with a metal target, a silicon target and a tray for placing AF agents, and the chamber D is used to form an AR film and an AF film.

[0031] Preferably, the system further comprises a transport mechanism capable of transporting the jig between the chambers, and the transport mechanism is a robot.

[0032] The method provided by the present invention can continuously prepare AG film, AR film and AF film on a glass cover plate, and the prepared products have the characteristics of high yield, stable performance and good uniformity.

[0033] In particular, the method provided by the present invention can be used to integrally process AG film, AR film and AF film, thereby avoiding the problems of slow efficiency and low yield rate caused by loading and unloading materials and intermediate processes during production. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 It is a particularly preferred embodiment of the method for continuously preparing AG film, AR film and AF film provided by the present invention.

[0035] Description of Reference Numerals

[0036] 1. Fixture 2. Substrate to be coated

[0037] 3. Transfer mechanism 4. Plasma cleaning gun

[0038] 5. Anti-glare spray gun 6. Heating tube

[0039] 7. Clean the spray gun 8. Brush

[0040] 9. Hot air knife 10. Metal target

[0041] 11. Silicon target 12. Tray DETAILED DESCRIPTION

[0042] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0043] In the present invention, unless otherwise specified, the room temperature or normal temperature refers to 25±2°C.

[0044] As mentioned above, the first aspect of the present invention provides a method for continuously preparing an AG film, an AR film and an AF film, the method comprising:

[0045] (1) introducing the substrate to be coated into chamber A for first cleaning to obtain substrate I with a surface water drop angle of no more than 20°, and spraying an anti-glare coating on the surface of substrate I to obtain substrate II containing an AG film;

[0046] (2) introducing the substrate II into the chamber B for curing treatment to obtain a substrate III;

[0047] (3) introducing the substrate III into the chamber C and sequentially performing a second cleaning and drying process to obtain a substrate IV;

[0048] (4) Introducing the substrate IV into the chamber D to form an AR film and an AF film; wherein the method for forming the AR film comprises: in the presence of a protective atmosphere, alternately depositing metal oxide layers and silicon oxide layers on the surface of the substrate IV, and the oxygen content in the metal oxide layer is lower than the oxygen content in the silicon oxide layer.

[0049] Preferably, the average thickness of the AG film is 50nm-300nm.

[0050] Preferably, the average thickness of the AR film is 200-300 nm, preferably 230-270 nm.

[0051] Preferably, the average thickness of the AF film is 10-40 nm.

[0052] Preferably, in step (4), the oxygen content in the metal oxide layer is 40-60% lower by volume than the oxygen content in the silicon oxide layer. The inventors have found that in this preferred embodiment, a glass cover plate with better light transmittance and stable color value can be obtained.

[0053] Preferably, in step (4), the main component of the metal oxide layer is niobium pentoxide and / or titanium dioxide.

[0054] Preferably, in step (4), the main component of the silicon oxide layer is silicon dioxide.

[0055] According to a particularly preferred embodiment of the present invention, in step (4), the AR film is formed by magnetron sputtering.

[0056] According to a particularly preferred embodiment of the present invention, in step (1), the conditions of the first cleaning are controlled so that the surface water drop angle of the substrate I is not greater than 10°.

[0057] Preferably, in step (1), the first cleaning is plasma cleaning, and the power of the plasma cleaning is 500-1500 W, more preferably 700-1200 W. The inventors have found that the specific implementation of this preferred case can not only achieve a good cleaning effect, but also will not cause damage to the substrate surface.

[0058] The present invention has no particular limitation on the type of plasma cleaning, and any type known in the art may be used. Preferably, the first cleaning adopts rotary spray gun plasma cleaning or linear plasma cleaning.

[0059] It should be noted that when the first cleaning adopts rotary spray gun plasma cleaning, the vertical distance between the spray gun and the surface of the substrate to be coated is 5-30mm, preferably 10-20mm; when the first cleaning adopts linear plasma cleaning, the vertical distance between the linear plasma generator and the surface of the substrate to be coated is 1-5mm, preferably 2-3mm.

[0060] The present invention has no particular limitation on the type of carrier gas used in the plasma cleaning process, and any carrier gas known in the art may be used. For example, argon gas may be used.

[0061] Preferably, in step (1), the method further comprises: before performing the first cleaning, preheating the substrate to be coated.

[0062] Preferably, in step (1), the preheat treatment conditions include at least: a temperature of 20-400° C., preferably 30-120° C.; and a time of 12-60 seconds.

[0063] Preferably, in step (1), the spraying is performed under the condition that the substrate 1 is rotating, and the surface linear speed of the substrate 1 is 300-1200 mm / s.

[0064] Preferably, in step (1), the spraying conditions include at least: a spraying distance of 80-150 mm, a temperature of 20-130° C., a spray gun atomization pressure of 0.1-0.6 MPa, a spray gun fan pressure of 0.1-0.6 MPa, a supply pressure of the anti-glare coating of 0.1-0.6 MPa, and a flow rate of the anti-glare coating of 1-30 g / min.

[0065] In the present invention, the spraying distance in step (1) refers to the vertical distance from the spray gun nozzle to the surface of substrate 1.

[0066] Preferably, in step (2), the curing treatment conditions at least include: a temperature of 130-400° C. and a time of 20-60 min.

[0067] Preferably, in step (3), the second cleaning includes cleaning I with a neutral detergent, cleaning II with water, and cleaning III with acetone.

[0068] It should be noted that the present invention has no special requirements for the type of the neutral detergent, and any type of neutral detergent known in the art can be used. For example, the present invention uses a glass-specific detergent with a pH value of 6-8. The present invention has no special requirements for the amount of the neutral detergent, water and acetone, as long as the cleaning purpose can be achieved. The present invention has no special requirements for the conditions of the second cleaning, and the second cleaning can be performed according to actual conditions. For example, the time of the second cleaning is 2-5 minutes.

[0069] Preferably, in step (3), the conditions for the drying treatment at least include: a temperature of 100-180° C. and a time of 10-30 min.

[0070] Preferably, in step (4), the AF film is formed by vacuum evaporation, and the conditions of the vacuum evaporation at least include: a temperature of 300-600°C.

[0071] It should be noted that the present invention has no special requirements on the type of AF agent used to form the AF film, and any type of AF agent known in the art can be used. Exemplarily, the AF agent of the present invention is selected from a compound containing at least one of a polyfluoropolyether group, a polyfluoroalkyl group, and a polyfluoroalkylene group.

[0072] The present invention has no special requirements on the amount of AF agent used to form the AF film, which only needs to meet the needs of the present invention. For example, it only needs to make the average thickness of the formed AF film 10-40nm.

[0073] The present invention has no special requirements on the type of the substrate to be coated, and any substrate known in the art that needs to be coated can be used. Exemplarily, the substrate to be coated is selected from at least one of a white glass substrate, an ink-coated glass substrate, and a resin substrate.

[0074] As mentioned above, the second aspect of the present invention provides a system for continuously preparing an AG film, an AR film and an AF film, the system comprising:

[0075] A fixture 1, wherein the fixture 1 is used to fix a substrate 2 to be coated;

[0076] Chamber A, wherein a plasma cleaning gun array and an anti-glare spray gun array are arranged side by side in the chamber A, wherein the plasma cleaning gun array includes at least two plasma cleaning guns 4, and the spacing between two adjacent plasma cleaning guns 4 is 40-80 mm; the anti-glare spray gun array includes at least two anti-glare spray guns 5, and the spacing between two adjacent anti-glare spray guns 5 is 60-100 mm, and the chamber A is used to perform a first cleaning on the substrate 2 to be coated and to form an AG film;

[0077] Chamber B, wherein at least two heating tubes 6 are evenly arranged inside the chamber B, and the distance between two adjacent heating tubes 6 is 20-100 mm, and the chamber B is used to cure the AG film;

[0078] Chamber C, wherein a cleaning spray gun 7, a brush 8 and a hot air knife 9 are provided in the chamber C, wherein the cleaning spray gun 7 is vertically arranged on the inner wall of the chamber C, and the nozzle of the cleaning spray gun 7 is vertically arranged toward the substrate III, the brush 8 is arranged tangentially to the fixture 1, the hot air knife 9 is vertically arranged on the inner wall of the chamber C, and the air outlet of the hot air knife 9 is arranged toward the substrate III, and a liquid and gas recovery port is also provided at the bottom of the chamber C;

[0079] A chamber D is provided with a metal target 10, a silicon target 11 and a tray 12 for placing AF agents, and the chamber D is used to form an AR film and an AF film.

[0080] By adopting the aforementioned system provided by the present invention, AG film, AR film and AF film can be processed in one piece, completely avoiding the manual rotation rack anti-glare layer curing, manual rotation rack cleaning and manual rotation rack AR coating after the anti-glare layer is sprayed, reducing the time the substrate is exposed to the environment, and improving efficiency and yield rate.

[0081] It should be noted that, in the chamber A, the distance between two adjacent plasma cleaning guns and the distance between two adjacent anti-glare spray guns can be determined according to the spray area of ​​the spray guns; and the number of the above two types of spray guns can be increased or decreased according to the size of the cavity.

[0082] It should be noted that, in the chamber B, there are no special requirements for the length and diameter of the heating tube, as long as they can meet the requirements of the present invention. In order to ensure that the radiation covers the effective area and maintains a constant temperature in the chamber B, illustratively, relative to the chamber B with an inner cavity height of 900-1800mm and an inner cavity diameter of 800-1500mm, the length of each of the heating tubes 6 is 1000-1500mm, and the diameter of each of the heating tubes 6 is 10-30mm.

[0083] The specific operation method of forming the AR film is described in detail below in combination with the structure of the chamber D, including:

[0084] Oxygen and inert gas are introduced into the chamber D, and the metal target 10 is first energized to form metal oxide with the metal and oxygen, and is deposited on the surface of the substrate IV by bombardment of inert gas molecules. Then, the silicon target 11 is energized to form silicon dioxide with the silicon and oxygen, and is deposited on the surface of the substrate IV by bombardment of inert gas molecules. The above steps are repeated until the thickness of the AR film reaches 200-300nm.

[0085] Preferably, the power density of the metal target 10 and the silicon target 11 is independently 3-5 W / cm 2 .

[0086] It should be noted that, in actual operation, the AF agent is placed in the tray 12, and the active ingredients therein are evaporated and deposited onto the surface of the substrate IV by heating.

[0087] Preferably, the system further comprises a transport mechanism 3 capable of transporting the jig between the chambers, and the transport mechanism 3 is a robot.

[0088] The present invention has no particular limitation on the type of the manipulator. It only needs to be able to realize the transfer of the fixture between the chambers. Any manipulator known in the art can be used. No further description is given here. Those skilled in the art should not interpret this as limiting the present invention.

[0089] Preferably, the substrate 2 to be coated is adhered to the fixture 1 .

[0090] The present invention can paste multiple substrates 2 to be coated on the fixture 1 according to actual needs. Exemplarily, 20-100 substrates 2 to be coated are arranged on the fixture 1, and the distance between two adjacent substrates 2 to be coated is 20-40 mm.

[0091] The following combination Figure 1 A particularly preferred embodiment of the method for continuously preparing AG film, AR film and AF film provided by the present invention is described in detail:

[0092] (1) Pasting a substrate 2 to be coated on a jig 1, and introducing the jig 1 with the substrate 2 to be coated into a chamber A through a transfer mechanism 3, performing a first cleaning on the surface of the substrate 2 to be coated using a plasma cleaning gun 4 to obtain a substrate I with a surface water drop angle of no more than 20°, and spraying an anti-glare coating on the surface of the substrate I through an anti-glare spray gun 5 to obtain a substrate II containing an AG film;

[0093] (2) The substrate II is introduced into the chamber B by the transfer mechanism 3 and cured under the action of the heating tube 6 to obtain the substrate III;

[0094] (3) The substrate III is introduced into the chamber C through the transfer mechanism 3, and a second cleaning is performed by the cooperation of the cleaning spray gun 7 and the brush 8, and then a drying treatment is performed under the action of the hot air knife 9 to obtain the substrate IV;

[0095] (4) The substrate IV is introduced into the chamber D through the transfer mechanism 3, and oxygen and inert gas are introduced. The metal target 10 is first energized to form metal oxide with the metal and oxygen, and is deposited on the surface of the substrate IV by bombardment of inert gas molecules. Then, the silicon target 11 is energized to form silicon dioxide with the silicon and oxygen, and is deposited on the surface of the substrate IV by bombardment of inert gas molecules. The above steps are repeated until the thickness of the AR film reaches 230-270nm, and then the AF agent is placed in the tray 12, and the effective ingredients therein are evaporated and deposited on the surface of the substrate IV by heating; wherein the oxygen content in the metal oxide layer is lower than the oxygen content in the silicon oxide layer.

[0096] The present invention will be described in detail below by way of examples. In the following examples, unless otherwise specified, all the raw materials and instruments used are commercially available.

[0097] Substrate to be coated: Panda MN228 glass, from Sichuan Hongke Innovation Technology Co., Ltd.;

[0098] Anti-glare coating: brand AG180, purchased from PPG Coatings (Tianjin) Co., Ltd.;

[0099] AF agent: brand H6500D, purchased from Shengyuan Lubricating Materials Co., Ltd.;

[0100] Neutral detergent: brand L-1012, purchased from Shenzhen Nanxiang Environmental Protection Technology Co., Ltd.;

[0101] In the following examples, the inner diameters of chambers A, B, C, and D are all 1500 mm, and the inner heights are all 1800 mm;

[0102] In the chamber A, the distance between two adjacent plasma cleaning guns is 60 mm, and the distance between two adjacent anti-glare spray guns is 60 mm;

[0103] In the chamber B, the distance between two adjacent heating tubes is 40 mm, the length of each heating tube is 1200 mm, and the diameter of each heating tube is 20 mm;

[0104] In the following examples, the transport mechanism is a robot, and the power density of the metal target and silicon target is 5W / cm 2 .

[0105] Example 1

[0106] This embodiment provides a method for continuously preparing an AG film, an AR film, and an AF film, the method comprising:

[0107] (1) 80 substrates to be coated were pasted on a jig, and then the jig with the substrates to be coated was preheated (temperature was 80°C, time was 30s), and the jig with the substrates to be coated was introduced into chamber A through a transfer mechanism, and the surface of the substrate to be coated was first cleaned by a plasma cleaning gun to obtain a substrate I with a surface water drop angle of 5°, and an anti-glare coating was sprayed on the surface of the substrate I by an anti-glare spray gun to obtain a substrate II containing an AG film; the average thickness of the AG film was 120nm;

[0108] The first cleaning is performed by plasma cleaning with a rotary spray gun, and the conditions for the first cleaning are: the vertical distance between the spray gun and the surface of the substrate to be coated is 10 mm, the carrier gas is argon, and the power is 800 W;

[0109] The spraying conditions are as follows: the surface linear velocity of the substrate 1 is 1000 mm / s, the spraying distance is 80 mm, the temperature is 80° C., the spray gun atomization pressure is 0.4 MPa, the spray gun fan pressure is 0.4 MPa, the supply pressure of the anti-glare coating is 0.4 MPa, and the anti-glare coating flow rate is 10 g / min;

[0110] (2) introducing the substrate II into the chamber B through the transfer mechanism, and performing a curing treatment under the action of the heating tube to obtain a substrate III;

[0111] The curing conditions are as follows: temperature 150°C, time 60 min;

[0112] (3) introducing the substrate III into the chamber C through the transfer mechanism, spraying neutral detergent, deionized water and acetone in sequence with a cleaning spray gun, and cleaning the substrate III for 3 minutes, cleaning II for 5 minutes and cleaning III for 4 minutes in sequence, and continuously rotating the brush to wipe the surface of the substrate III during the above cleaning process, and then drying it under the action of a hot air knife to obtain a substrate IV;

[0113] The drying process was carried out under the following conditions: temperature of 100°C and time of 30 min.

[0114] (4) The substrate IV is introduced into the chamber D through the transfer mechanism, and oxygen and argon are introduced. The metal target is first energized to form metal oxide with oxygen, and then deposited on the surface of the substrate IV by bombardment of argon molecules. Then, the silicon target is energized to form silicon dioxide with oxygen, and then deposited on the surface of the substrate IV by bombardment of argon molecules. The above steps are repeated until the thickness of the AR film reaches 260 mm. Then, the AF agent is placed in a tray and placed under vacuum conditions (vacuum degree is 1×10 - 5 Pa), evaporating and depositing the active ingredients in the AF agent onto the surface of the substrate IV; wherein the average thickness of the AF film is 30nm, and the oxygen content in the metal oxide layer is 50 volume % lower than the oxygen content in the silicon oxide layer.

[0115] Example 2

[0116] This embodiment provides a method for continuously preparing an AG film, an AR film, and an AF film, the method comprising:

[0117] (1) 20 substrates to be coated were pasted on a jig, and then the jig with the substrates to be coated was preheated (temperature was 90°C, time was 60s), and the jig with the substrates to be coated was introduced into chamber A through a transfer mechanism, and the surface of the substrate to be coated was first cleaned by a plasma cleaning gun to obtain a substrate I with a surface water drop angle of 5°, and an anti-glare coating was sprayed on the surface of the substrate I by an anti-glare spray gun to obtain a substrate II containing an AG film; the average thickness of the AG film was 210nm;

[0118] The first cleaning is performed by plasma cleaning with a rotary spray gun, and the conditions for the first cleaning are: the vertical distance between the spray gun and the surface of the substrate to be coated is 15 mm, the carrier gas is argon, and the power is 1000 W;

[0119] The spraying conditions are as follows: the surface linear velocity of the substrate 1 is 800 mm / s, the spraying distance is 90 mm, the temperature is 90° C., the spray gun atomization pressure is 0.45 MPa, the spray gun fan pressure is 0.45 MPa, the supply pressure of the anti-glare coating is 0.4 MPa, and the anti-glare coating flow rate is 15 g / min;

[0120] (2) introducing the substrate II into the chamber B through the transfer mechanism, and performing a curing treatment under the action of the heating tube to obtain a substrate III;

[0121] The curing conditions are as follows: temperature 200°C, time 50 min;

[0122] (3) introducing the substrate III into the chamber C through the transfer mechanism, spraying the substrate III with a neutral detergent, deionized water and acetone in sequence with a cleaning spray gun, and sequentially cleaning the substrate III for 3 min, cleaning II for 5 min and cleaning III for 4 min, and continuously rotating the brush to wipe the surface of the substrate III during the above cleaning process, and then drying the substrate under the action of a hot air knife to obtain a substrate IV;

[0123] The drying process was carried out under the following conditions: temperature of 150°C and time of 20 min.

[0124] (4) The substrate IV is introduced into the chamber D through the transfer mechanism, and oxygen and argon are introduced. The metal target is first energized to form metal oxide with oxygen, and then deposited on the surface of the substrate IV by bombardment of argon molecules. Then, the silicon target is energized to form silicon dioxide with oxygen, and then deposited on the surface of the substrate IV by bombardment of argon molecules. The above steps are repeated until the thickness of the AR film reaches 240 mm. Then, the AF agent is placed in a tray and placed under vacuum conditions (vacuum degree is 1×10 - 5 Pa), evaporating and depositing the active ingredients in the AF agent onto the surface of the substrate IV; wherein the average thickness of the AF film is 30nm, and the oxygen content in the metal oxide layer is 40 volume % lower than that in the silicon oxide layer.

[0125] Example 3

[0126] This embodiment provides a method for continuously preparing an AG film, an AR film, and an AF film, the method comprising:

[0127] (1) 50 substrates to be coated were pasted on a jig, and then the jig with the substrates to be coated was preheated (temperature was 40°C, time was 0.8 min), and the jig with the substrates to be coated was introduced into chamber A through a transfer mechanism, and the surface of the substrate to be coated was first cleaned by a plasma cleaning gun to obtain a substrate I with a surface water drop angle of 8°, and an anti-glare coating was sprayed on the surface of the substrate I by an anti-glare spray gun to obtain a substrate II containing an AG film; the average thickness of the AG film was 300 nm;

[0128] The first cleaning is performed by plasma cleaning with a rotary spray gun, and the conditions for the first cleaning are: the vertical distance between the spray gun and the surface of the substrate to be coated is 20 mm, the carrier gas is argon, and the power is 700 W;

[0129] The spraying conditions are as follows: the surface linear velocity of the substrate 1 is 600 mm / s, the spraying distance is 110 mm, the temperature is 40° C., the spray gun atomization pressure is 0.5 MPa, the spray gun fan pressure is 0.5 MPa, the supply pressure of the anti-glare coating is 0.5 MPa, and the anti-glare coating flow rate is 20 g / min;

[0130] (2) introducing the substrate II into the chamber B through the transfer mechanism, and performing a curing treatment under the action of the heating tube to obtain a substrate III;

[0131] The curing conditions are as follows: temperature 350°C, time 30 min;

[0132] (3) introducing the substrate III into the chamber C through the transfer mechanism, spraying the substrate III with a neutral detergent, deionized water and acetone in sequence with a cleaning spray gun, and sequentially cleaning the substrate III for 3 min, cleaning II for 5 min and cleaning III for 4 min, and continuously rotating the brush to wipe the surface of the substrate III during the above cleaning process, and then drying the substrate under the action of a hot air knife to obtain a substrate IV;

[0133] The drying process was carried out under the following conditions: temperature of 180°C and time of 10 min.

[0134] (4) The substrate IV is introduced into the chamber D through the transfer mechanism, and oxygen and argon are introduced. The metal target is first energized to form metal oxide with oxygen, and then deposited on the surface of the substrate IV by bombardment of argon molecules. Then, the silicon target is energized to form silicon dioxide with oxygen, and then deposited on the surface of the substrate IV by bombardment of argon molecules. The above steps are repeated until the thickness of the AR film reaches 250 mm. Then, the AF agent is placed in a tray and placed under vacuum conditions (vacuum degree is 1×10 - 5Pa), evaporating and depositing the active ingredients in the AF agent onto the surface of the substrate IV; wherein the average thickness of the AF film is 30nm, and the oxygen content in the metal oxide layer is 60 volume % lower than the oxygen content in the silicon oxide layer.

[0135] Example 4

[0136] An AG film, an AR film and an AF film are continuously prepared according to the method of Example 1, except that in step (1), the conditions of the first cleaning are controlled so that the surface water drop angle of the substrate I is 15°.

[0137] Example 5

[0138] An AG film, an AR film and an AF film were continuously prepared according to the method of Example 1, except that in step (1), the power of the first cleaning was 500 W.

[0139] Example 6

[0140] An AG film, an AR film and an AF film are continuously prepared according to the method of Example 1, except that in step (4), the oxygen content in the metal oxide layer is 80 volume % lower than the oxygen content in the silicon oxide layer.

[0141] Comparative Example 1

[0142] An AG film, an AR film and an AF film are continuously prepared according to the method of Example 1, except that in step (1), the conditions of the first cleaning are controlled so that the surface water drop angle of the substrate I is 25°.

[0143] Comparative Example 2

[0144] An AG film, an AR film and an AF film are continuously prepared according to the method of Example 1, except that in step (4), the oxygen content in the metal oxide layer is the same as the oxygen content in the silicon oxide layer.

[0145] Comparative Example 3

[0146] An AG film, an AR film and an AF film are continuously prepared according to the method of Example 1, except that in step (4), the oxygen content in the metal oxide layer is 40 volume % higher than the oxygen content in the silicon oxide layer.

[0147] Test Example 1

[0148] Two substrates II containing AG films prepared in Example 1 were randomly selected for performance testing, and a control group was set up. The specific test results are shown in Table 1.

[0149] The setting method of the control group is as follows: This method is similar to step (1) in Example 1, except that, during the spraying of the anti-glare coating, the film substrate 1 is placed parallel to the ground, and then the anti-glare coating is sprayed on the surface of the substrate 1 using an anti-glare spray gun;

[0150] The test method for 60° gloss is: BYK 60° gloss meter, measuring 2 points on each sample;

[0151] The haze test method is: BYK4775 transmission haze meter, measuring 2 points on each sample;

[0152] The test method for AG film thickness is: Mitutoyo SJ-410 tester, free condition measurement, and 2 points for each sample.

[0153] Table 1

[0154]

[0155]

[0156] It can be seen from the results in Table 1 that the AG film obtained by the method provided by the present invention still maintains stable film thickness uniformity under different glossiness and haze.

[0157] Test Example 2

[0158] One substrate II containing an AG film prepared in Example 1, Example 2 and Example 3 was randomly selected for performance testing. Three measurement points were randomly selected on each substrate. The specific test results are shown in Table 2.

[0159] The test method for pencil hardness is as follows: Japanese Mitsubishi pencil, load 750g, 45° angle, the pencil to be tested for hardness scratches 5 2cm tracks, and ≤2 scratches are qualified;

[0160] The test method for friction resistance is: Eraser, load 500g, speed 40 times / min, 1500 times of friction, visual and microscope observation of film performance;

[0161] The test method for adhesion (100 grids) is as follows: on the surface of the AG layer, the engraving knife engraves 11 lines horizontally and vertically to form a square area containing 100 squares. The tape is repeatedly pasted 3 times. If there is no peeling on the surface, it is recorded as 5B.

[0162] Table 2

[0163]

[0164] It can be seen from the results in Table 2 that the hardness, friction resistance and adhesion (100 grids) tests of the AG film layer obtained by the method provided by the present invention all meet the standards, and the film layer has good stability.

[0165] Test Example 3

[0166] One AR film prepared in Example 1, Example 2 and Example 3 was randomly selected for performance testing, and two measurement points were randomly selected on each substrate. The specific test results are shown in Table 3.

[0167] Among them, the SCI method for testing L, a, b and y values ​​is as follows: SPECTROPHOTOMETER CM-26d colorimeter, testing two points on each sample, and recording SCI mode data;

[0168] The SCE method for testing L, a, b and y values ​​is as follows: SPECTROPHOTOMETER CM-26d colorimeter, testing two points on each sample, and recording SCE mode data.

[0169] Table 3

[0170]

[0171] It can be seen from the results in Table 3 that the AR film obtained by the method provided by the present invention has good stability in L, a, b and y values.

[0172] Test Example 4

[0173] The performance of the substrates containing the AG film, the AR film and the AF film prepared in the examples and comparative examples was tested. The specific test results are shown in Table 4.

[0174] The test method for pencil hardness is as follows: Japanese Mitsubishi pencil, load 750g, 45° angle, the pencil to be tested for hardness scratches 5 2cm tracks, and ≤2 scratches are qualified;

[0175] The test method for friction resistance is: LIBERON0000# steel wool, load 500g, speed 40 times / min, friction 1500 times, test the water drop angle before and after friction, before friction ≥110°, after friction ≥100°, it is qualified;

[0176] The test method for the water drop angle is: use the SINDIN water contact angle meter to measure the water drop angle at the same position before and after friction, and record the changes.

[0177] A product is considered good if it has ≤2 scratches using the pencil hardness test method and the water drop angle is ≥100° after the friction resistance test. The formula for calculating the good product rate is: (number of good products / total number of samples)×100%.

[0178] Table 4

[0179] Pencil hardness Water drop angle before friction,° Water drop angle after friction,° Yield, % Example 1 8H 112.7 103.5 100％ Example 2 8H 111.6 102.2 100％ Example 3 8H 112.7 103.4 100％ Example 4 7H 110.1 101.5 90％ Example 5 7H 110.3 101.4 90％ Example 6 6H 110.5 91.8 60％ Comparative Example 1 6H 110.9 90.1 50％ Comparative Example 2 5H 110.7 54.5 0 Comparative Example 3 4H 110.1 53.2 0

[0180] It can be seen from the results in Table 4 that the method provided by the present invention can continuously prepare AG film, AR film and AF film on the glass cover plate, and the prepared products have the characteristics of high yield, stable performance and good uniformity.

[0181] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A method for continuously preparing AG film, AR film and AF film, characterized in that: The method includes: (1) introducing the substrate to be coated into chamber A for first cleaning to obtain substrate I with a surface water drop angle of no more than 20°, and spraying an anti-glare coating on the surface of substrate I to obtain substrate II containing an AG film; (2) introducing the substrate II into the chamber B for curing treatment to obtain a substrate III; (3) introducing the substrate III into the chamber C and sequentially performing a second cleaning and drying process to obtain a substrate IV; (4) Introducing the substrate IV into the chamber D to form an AR film and an AF film; wherein the method for forming the AR film comprises: in the presence of a protective atmosphere, alternately depositing a metal oxide layer and a silicon oxide layer on the surface of the substrate IV, and the oxygen content in the metal oxide layer is 40-60 volume % lower than the oxygen content in the silicon oxide layer.

2. The method according to claim 1, characterized in that In step (4), the main components of the metal oxide layer are niobium pentoxide and / or titanium dioxide.

3. The method according to claim 1 or 2, characterized in that: In step (1), the conditions of the first cleaning are controlled so that the surface water drop angle of the substrate 1 is no greater than 10°.

4. The method according to claim 1 or 2, characterized in that: In step (1), the first cleaning is performed by plasma cleaning, and the power of the plasma cleaning is 500-1500W.

5. The method according to claim 4, characterized in that The power of the plasma cleaning is 700-1200W.

6. The method according to claim 1 or 2, characterized in that: In step (1), the method further includes: before performing the first cleaning, preheating the substrate to be coated.

7. The method according to claim 6, characterized in that The preheating conditions include at least: a temperature of 20-400° C. and a time of 12-60 seconds.

8. The method according to claim 7, characterized in that The preheating conditions at least include: a temperature of 30-120°C.

9. The method according to claim 1 or 2, characterized in that: In step (1), the spraying is performed under the condition that the substrate 1 is rotated, and the surface linear speed of the substrate 1 is 300-1200 mm / s.

10. The method according to claim 9, characterized in that The spraying conditions include at least: a spraying distance of 80-150 mm, a temperature of 20-130° C., a spray gun atomization pressure of 0.1-0.6 MPa, a spray gun fan pressure of 0.1-0.6 MPa, a supply pressure of the anti-glare coating of 0.1-0.6 MPa, and a flow rate of the anti-glare coating of 1-30 g / min.

11. The method according to claim 1 or 2, characterized in that: In step (2), the curing treatment conditions include at least: a temperature of 130-400° C. and a time of 20-60 min.

12. The method according to claim 1 or 2, characterized in that: In step (3), the second cleaning includes cleaning I with a neutral detergent, cleaning II with water, and cleaning III with acetone.

13. The method according to claim 1 or 2, characterized in that: In step (3), the drying conditions include at least: a temperature of 100-180° C. and a time of 10-30 min.

14. The method according to claim 1 or 2, characterized in that: In step (4), the AF film is formed by vacuum evaporation, and the conditions of the vacuum evaporation include at least a temperature of 300-600°C.

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