Methods of making coatings, coatings, and devices

Abstract

Embodiments of the present application relate to a method for preparing a coating, a coating, and a device. The method includes the following steps: placing a substrate in a plasma reaction chamber; and introducing a first raw material containing an isocyanate bond and a second raw material containing a hydroxyl group and an amino group into the plasma reaction chamber, and discharging plasma to form a coating on the surface of the substrate. Embodiments of the present application can facilitate the preparation of a coating with fewer types of materials, lower cost, and simpler process, etc.

Description

Technical Field

[0001] This application relates to the field of surface treatment, and more particularly to a method for preparing a coating, a coating, and a device. Background Technology

[0002] When saturated water vapor in the environment encounters devices with temperatures below the dew point, it easily forms adhering fog on the device's surface, commonly causing fogging phenomena in daily life. For example, fogging on bathroom windows, eyeglasses, swimming goggles, camera lenses, and car windows directly affects the clarity of the field of vision. If a car windshield fogs up rapidly at high speeds, it directly impacts visibility, posing a significant driving hazard. Furthermore, the application of precision equipment such as infrared microscopes and surgical endoscopes is also severely affected by fogging. In addition, with the rapid development of clean energy in recent years, the light transmittance and power generation efficiency of solar panels are closely related; fogging on the glass surface of solar panels directly affects transmittance and, consequently, power generation efficiency.

[0003] To address the fogging problem in various devices, extensive research has been conducted. One approach is to surface-treat the substrate to obtain devices with coatings on part or all of their surfaces. However, existing methods for preparing coatings are often less than ideal, requiring a variety of materials, incurring high costs, and involving complex processes, thus necessitating improvements. Summary of the Invention

[0004] One object of this application is to provide an improved method for preparing a coating, the coating itself, and a device thereof.

[0005] To achieve the above objectives, one aspect of this application relates to a method for preparing a coating, comprising the following steps: placing a substrate in a plasma reaction chamber; and introducing a first raw material containing isocyanate bonds and a second raw material containing hydroxyl and amino groups into the plasma reaction chamber, thereby causing plasma discharge to form a coating on the surface of the substrate.

[0006] In some embodiments, the first raw material has structural formula I:

[0007]

[0008] R1 and R2 are independently hydrogen atoms, fluorine atoms, alkyl groups or alkyl groups in which hydrogen atoms are partially or completely replaced by fluorine atoms, or alkyl groups linked to a benzene ring through an oxygen atom. R1 and R2 are in the ortho, para, or meta position, and R1 is in the ortho, para, or meta position with the isocyanate bond.

[0009] In some embodiments, the first raw material has structural formula II: Si(OR3)x(R4)y(R5)z, wherein R3 is a C1-C3 alkyl group, R4 is hydrogen or alkyl, R5 is an alkyl group with an isocyanate bond at the end, x+y+z=4, 1≤x≤3, 0≤y≤2, and 1≤z.

[0010] In some embodiments, the first raw material includes at least one of propyltriethoxysilane, propyltrimethoxysilane, m-methylphenyl isocyanate, methyl-(3-propylisocyanate)dimethylsilane, propyltrimethoxysilane, 10-decylisocyanatetrimethoxysilane, p-methoxyphenyl isocyanate, 3-methoxyphenyl isocyanate, phenyl 3-(trifluoromethyl)isocyanate, 2,4-difluorophenyl isocyanate, m-methylphenyl isocyanate, 3,5-dimethylphenyl isocyanate, 3,5-bis(trifluoromethyl)phenyl isocyanate, p-fluorophenyl isocyanate, and phenyl isocyanate.

[0011] In some embodiments, the first raw material includes at least one of propyltriethoxysilane 3-isocyanate, propyltrimethoxysilane 3-isocyanate, and m-methylphenyl isocyanate.

[0012] In some embodiments, the second raw material is a hydrophilic material.

[0013] In some embodiments, the second raw material has structural formula III: R6-X, wherein X is a hydroxyl or amino group, and R6 is a hydrocarbon group attached with at least one -OH or -NH2.

[0014] In some embodiments, R6 is an alkyl group in which some carbon atoms are replaced by secondary amines, tertiary amines, or oxygen atoms.

[0015] In some embodiments, the second raw material includes at least one of polyethylene glycol, Tween 20, diethanolamine, 1,4-butenediol, 1,3-butanediol, glycerol, 1,2,4-butanetriol, 2,3-butanediol, pentane-1,3-diol, 1,2,6-hexanetriol, triethylene glycol, N-butyldiethanolamine, N-(3-aminopropyl)diethanolamine, and N-ethyldiethanolamine.

[0016] In some embodiments, the second raw material includes at least one of polyethylene glycol, Tween 20, diethanolamine, 1,4-butenediol, and 1,3-butanediol.

[0017] In some embodiments, the molar ratio of the first raw material to the second raw material is in the range of 1:0.5 to 1:5.

[0018] In some embodiments, introducing a first raw material containing isocyanate bonds and a second raw material containing hydroxyl and amino groups into the plasma reaction chamber includes mixing and heating the first raw material and the second raw material, and then vaporizing the mixture of the first raw material and the second raw material.

[0019] In some embodiments, the substrate includes at least one of glass and plastic.

[0020] In some embodiments, the plastic includes at least one of polycarbonate, polymethyl methacrylate, polystyrene, and polyethylene terephthalate.

[0021] Another aspect of the embodiments of this application relates to a coating prepared by the method described in this application.

[0022] In some embodiments, the water contact angle of the coating is less than or equal to 12°.

[0023] In some embodiments, the water contact angle of the coating is less than or equal to 14° after being rubbed 100 times with an alcohol-soaked cloth under a load of 10 Newtons.

[0024] In some embodiments, the visible light transmittance of the coating is greater than or equal to 90%.

[0025] In some embodiments, the coating is an anti-fog coating.

[0026] Another aspect of the embodiments of this application relates to a device whose surface at least partially includes a coating as described in this application.

[0027] In some embodiments, the device includes at least one of bathroom glass, eyeglasses, swimming goggles, camera lens, automotive glass, infrared microscope, surgical endoscope, and solar panel.

[0028] Where technical conditions permit, the technical features of the various embodiments in this application can be arbitrarily combined to form new technical solutions within the scope of protection of this application.

[0029] The present application will be further described below with reference to embodiments and accompanying drawings. Attached Figure Description

[0030] Figure 1 The curve shows the transmittance of the sample in Example 6 as a function of time. Detailed Implementation

[0031] One aspect of this application relates to a method for preparing a coating, which includes the following steps: placing a substrate in a plasma reaction chamber; and introducing a first raw material containing isocyanate bonds and a second raw material containing hydroxyl and amino groups into the plasma reaction chamber, thereby causing plasma discharge to form a coating on the surface of the substrate.

[0032] The embodiments of this application can help to prepare coatings with fewer types of materials, lower costs, and simpler processes.

[0033] For example, the coating preparation method involved in this application mainly uses a first raw material containing isocyanate bonds and a second raw material containing hydroxyl and amino groups, which helps to form a hydrophilic coating, spreading condensed water droplets into a water film, thereby preventing fogging and solving the fogging problem. The required materials are relatively few, resulting in lower costs. Furthermore, the coating preparation method involved in this application does not require the use of organic solvents, photoinitiators, etc., making it environmentally friendly. In addition, the coating preparation method involved in this application mainly uses plasma discharge, eliminating the need for prolonged heating reactions, ultraviolet curing, etc., thus not affecting the inherent properties of the substrate. The first and second raw materials can be activated, reacted, and deposited at relatively low temperatures to form a coating. The process is relatively simple and low-cost, and the resulting coating is uniform, transparent, hydrophilic, anti-fogging, durable, and abrasion-resistant.

[0034] The method for preparing the coating involved in the embodiments of this application can be plasma-enhanced chemical vapor deposition (PECVD), which can be carried out at a lower pressure, for example, below ambient pressure.

[0035] The plasma reaction chamber can be evacuated and can be connected to the feed tank of the equipment for vaporizing the first raw material and the second raw material, and can receive the gaseous first raw material and the second raw material.

[0036] Under the same conditions, the coating prepared by the method of preparing the coating involved in the embodiments of this application using the first raw material and the second raw material has stronger hydrophilicity, better anti-fogging performance, better durability and better abrasion resistance compared with the coating prepared using the first raw material alone.

[0037] Under the same conditions, the coating prepared by the method of preparing the coating involved in the embodiments of this application using the first raw material and the second raw material will not fail due to dissolution in water, and will have better hydrophilicity and better abrasion resistance compared to the coating prepared using the second raw material alone.

[0038] Unless otherwise specified, the terms "first" and "second" used in this document are not intended to indicate order, importance, or priority, but are only used to distinguish the materials being modified and should not be construed as limiting the scope of protection.

[0039] The first raw material may include atoms or groups directly or indirectly connected to the isocyanate bond. In some embodiments, the first raw material has structural formula I:

[0040]

[0041] R1 and R2 are independently hydrogen atoms, fluorine atoms, alkyl groups or alkyl groups in which hydrogen atoms are partially or completely replaced by fluorine atoms, or alkyl groups linked to a benzene ring through an oxygen atom. R1 and R2 are in the ortho, para, or meta position, and R1 is in the ortho, para, or meta position with the isocyanate bond.

[0042] In some embodiments, the first raw material has structural formula II: Si(OR3)x(R4)y(R5)z, wherein R3 is a C1-C3 alkyl group, R4 is hydrogen or alkyl, R5 is an alkyl group with an isocyanate bond at the end, x+y+z=4, 1≤x≤3, 0≤y≤2, and 1≤z.

[0043] In some embodiments, the first raw material includes at least one of propyltriethoxysilane, propyltrimethoxysilane, m-methylphenyl isocyanate, methyl-(3-propylisocyanate)dimethylsilane, propyltrimethoxysilane, 10-decylisocyanatetrimethoxysilane, p-methoxyphenyl isocyanate, 3-methoxyphenyl isocyanate, phenyl 3-(trifluoromethyl)isocyanate, 2,4-difluorophenyl isocyanate, m-methylphenyl isocyanate, 3,5-dimethylphenyl isocyanate, 3,5-bis(trifluoromethyl)phenyl isocyanate, p-fluorophenyl isocyanate, and phenyl isocyanate.

[0044] The structural formula of 3-propylisocyanatetriethoxysilane can be:

[0045] The structural formula of 3-isocyanate-propyltrimethoxysilane can be

[0046] The structural formula of m-methylphenyl isocyanate can be The structural formula of methyl-(3-propyl isocyanate)dimethylsilane can be:

[0047] The structural formula of 3-propyl isocyanate methyl diethoxysilane can be

[0048] The structural formula of 10-isocyanodecyltrimethoxysilane can be

[0049] The structural formula of p-methoxyphenyl isocyanate can be

[0050] The structural formula of 3-methoxyphenyl isocyanate can be

[0051] The structural formula of 3-(trifluoromethyl)phenyl isocyanate can be

[0052] The structural formula of 2,4-difluorophenyl isocyanate can be

[0053] The structural formula of m-methylphenyl isocyanate can be

[0054] The structural formula of 3,5-dimethylphenyl isocyanate can be

[0055] The structural formula of 3,5-bis(trifluoromethyl)phenyl isocyanate can be

[0056] The structural formula of p-fluorophenyl isocyanate can be:

[0057] The structural formula of phenyl isocyanate can be

[0058] In some embodiments, the first raw material includes at least one of propyltriethoxysilane 3-isocyanate, propyltrimethoxysilane 3-isocyanate, and m-methylphenyl isocyanate.

[0059] In some embodiments, the second raw material is a hydrophilic material. A hydrophilic material can refer to a material that can be wetted by water when in contact with water.

[0060] The second raw material may include hydroxyl groups and / or amino groups, as well as atoms or groups directly or indirectly connected to the hydroxyl and / or amino groups. In some embodiments, the second raw material has structural formula III: R6-X, wherein X is a hydroxyl or amino group, and R6 is a hydrocarbon group connected to at least one -OH or -NH2 group.

[0061] In some embodiments of the present invention, the hydrocarbon group is a saturated alkyl group, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, etc. In other embodiments of the present invention, the hydrocarbon group is an unsaturated alkenyl, alkynyl, or aromatic group.

[0062] In some embodiments, R6 is an alkyl group in which some carbon atoms are replaced by secondary amines, tertiary amines, or oxygen atoms.

[0063] In some embodiments, the second raw material includes at least one of polyethylene glycol, Tween 20, diethanolamine, 1,4-butenediol, 1,3-butanediol, glycerol, 1,2,4-butanetriol, 2,3-butanediol, pentane-1,3-diol, 1,2,6-hexanetriol, triethylene glycol, N-butyldiethanolamine, N-(3-aminopropyl)diethanolamine, and N-ethyldiethanolamine.

[0064] The structural formula of polyethylene glycol can be The molecular weight of polyethylene glycol (PEG) can vary depending on the value of n. The molecular weight of PEG can range from 200 to 600. Examples of PEG include PEG200 (approximately 200 molecular weight), PEG400 (approximately 400 molecular weight), PEG300 (approximately 300 molecular weight), and so on.

[0065] Tween 20's chemical name can be polyethoxypalmitic acid menthol, and its structural formula can be...

[0066] The structural formula of diethanolamine can be...

[0067] The structural formula of 1,4-butenediol can be

[0068] The structural formula of 1,3-butanediol can be...

[0069] The structural formula of glycerol can be

[0070] The structural formula of 1,2,4-butanetriol can be...

[0071] The structural formula of 2,3-butanediol can be:

[0072] The structural formula of pentane-1,3-diol can be

[0073] The structural formula of 1,2,6-hexanetriol can be...

[0074] The structural formula of triethylene glycol can be...

[0075] The structural formula of N-butyldiethanolamine can be:

[0076] The structural formula of N-(3-aminopropyl)diethanolamine can be...

[0077] The structural formula of N-ethyldiethanolamine can be:

[0078] In some embodiments, the second raw material includes at least one of polyethylene glycol, Tween 20, diethanolamine, 1,4-butenediol, and 1,3-butanediol.

[0079] The ratio of the first raw material to the second raw material can be within the range required to produce the coating described in this application. In some embodiments, the molar ratio of the first raw material to the second raw material is in the range of 1:0.5 to 1:5.

[0080] Unless otherwise specified, the numerical values ​​in this document may include errors in measurement, accuracy, and metrology, such as errors within the range of ±5%. For example, 1 may include a value in the range of 0.95 to 1.05.

[0081] Unless otherwise specified, the numerical ranges in this article include any subranges therein. For example, 1:0.5 to 1:5 can include 1:0.6 to 1:1.2, 1:2 to 1:3, 1:3 to 1:4, 1:1.5 to 1:5, 1:4.8 to 1:5, and so on.

[0082] During plasma discharge, the first and second raw materials can be in a gaseous state. In some embodiments, introducing the first raw material containing isocyanate bonds and the second raw material containing hydroxyl and amino groups into the plasma reaction chamber includes mixing and heating the first and second raw materials, and then vaporizing the mixture of the first and second raw materials.

[0083] The first and second raw materials can be heated during the mixing process. The temperature and time of heating the first and second raw materials can be controlled to a temperature and time at which the first and second raw materials will not vaporize.

[0084] The vaporization temperature can be determined based on the specific types of the first and second raw materials.

[0085] The flow rates of the first and second raw materials introduced into the plasma reaction chamber, the power of the plasma discharge, and the duration can be determined based on the type of raw materials, coating thickness requirements, etc.

[0086] The plasma discharge after the first and second raw materials are input into the plasma reaction chamber can be carried out by outputting energy via radio frequency pulses.

[0087] While the first raw material and the second raw material are being input into the plasma reaction chamber, an auxiliary gas can be introduced into the plasma reaction chamber. The auxiliary gas may include an inert gas such as helium.

[0088] Before introducing the first and second raw materials, the substrate can be pretreated within the plasma reaction chamber using inert gases such as helium and low-pressure plasma discharge. During pretreatment, the plasma discharge can be performed by continuously outputting energy via radio frequency.

[0089] The substrate can be a material that requires and is capable of forming the coating described in this application on its surface. In some embodiments, the substrate includes at least one of glass and plastic.

[0090] In some embodiments, the plastic includes at least one of polycarbonate, polymethyl methacrylate, polystyrene, and polyethylene terephthalate.

[0091] Another aspect of the embodiments of this application relates to a coating prepared by the method described in this application.

[0092] The coating may be a hydrophilic coating. The coating is wettable when in contact with water. In some embodiments, the water contact angle of the coating is less than or equal to 12°.

[0093] The coating exhibits good abrasion resistance. After being rubbed, properties such as hydrophilicity are maintained or change negligibly. In some embodiments, after rubbing the coating 100 times with an alcohol-soaked cotton cloth under a load of 10 Newtons, the measured water contact angle is less than or equal to 14°.

[0094] The coating is light-transmitting. In some embodiments, the visible light transmittance of the coating is greater than or equal to 90%.

[0095] The coating is anti-fogging. In some embodiments, the coating is an anti-fogging coating. The transmittance change of the coating after immersion in water and exposure to humid air can be less than 20%. The coating does not fog after freezing at sub-zero temperatures.

[0096] Another aspect of the embodiments of this application relates to a device whose surface at least partially includes a coating as described in this application.

[0097] The device may be a surface-required device capable of forming the coating described in this application. In some embodiments, the device includes at least one of bathroom glass, eyeglasses, swimming goggles, camera lenses, automotive glass, infrared microscopes, surgical endoscopes, and solar panels.

[0098] The following examples are intended to help understand the implementation of the present invention and are not intended to limit the scope of protection.

[0099] Example 1

[0100] (1) Place the transparent glass plate (length: 13 cm, width: 6.5 cm, thickness: 1 mm) substrate sample into a 500-liter plasma vacuum reaction chamber. Continuously evacuate the reaction chamber to achieve a vacuum of 80 mTorr. The internal temperature of the reaction chamber is 50°C. Helium gas is introduced at a flow rate of 40 ml per minute under standard conditions.

[0101] (2) Pretreatment of the substrate sample: Maintain the gas pressure in the reaction chamber at 80 mTorr, maintain the helium flow rate at 40 mL / min at standard conditions, turn on the radio frequency plasma discharge, the radio frequency energy output mode is continuous discharge, the discharge time is 600 seconds, and the discharge power is 200 W.

[0102] (3) Mix 3-propyltriethoxysilane and polyethylene glycol 200 at a molar ratio of 1:1, stir at 60°C for 6 hours to obtain a mixture, load it into the equipment feed tank, vaporize the mixture at 110°C, and pass it into the reaction chamber at a flow rate of 100 μL / min, maintain the gas pressure in the reaction chamber at 80 mTorr, maintain the helium flow rate at 40 mL / min, turn on the radio frequency plasma discharge, the discharge time is 1800 seconds, the discharge power is 100 W, the radio frequency energy output mode is pulse, the pulse frequency is 50 Hz, and the pulse duty cycle is 45% to form a coating;

[0103] (4) After the coating preparation is completed, air is introduced to restore the reaction chamber to normal pressure. The reaction chamber is opened and the sample is taken out. The coating on its surface is uniform and transparent.

[0104] Example 2

[0105] Steps (1), (2), and (4) are the same as in Example 1. In step (3), 3-propyltriethoxysilane and polyethylene glycol 400 are mixed at a molar ratio of 3:2 and stirred at 60°C for 6 hours to obtain a mixture, which is then loaded into the equipment feed tank. Everything else is the same. The resulting coating is uniform and transparent.

[0106] Example 3

[0107] Steps (1), (2), and (4) are the same as in Example 1. In step (3), 3-propyltriethoxysilane and Tween 20 are mixed at a molar ratio of 1:1 and stirred at 60°C for 6 hours to obtain a mixture, which is then loaded into the equipment feed tank. Everything else is the same. The resulting coating is uniform and transparent.

[0108] Example 4

[0109] Steps (1), (2), and (4) are the same as in Example 1. In step (3), 3-propyltriethoxysilane and diethanolamine are mixed at a molar ratio of 1:3 and stirred at 60°C for 6 hours to obtain a mixture, which is then loaded into the equipment feed tank. Everything else is the same. The resulting coating is uniform and transparent.

[0110] Example 5

[0111] Steps (1), (2), and (4) are the same as in Example 1. In step (3), 3-propyltriethoxysilane and diethanolamine are mixed at a molar ratio of 1:1 and stirred at 60°C for 6 hours to obtain a mixture, which is then loaded into the equipment feed tank. Everything else is the same. The resulting coating is uniform and transparent.

[0112] Example 6

[0113] Steps (1), (2), and (4) are the same as in Example 1. In step (3), 3-propyltriethoxysilane and 1,4-butenediol are mixed at a molar ratio of 1:1 and stirred at 60°C for 6 hours to obtain a mixture, which is then loaded into the equipment feed tank. Everything else is the same. The resulting coating is uniform and transparent.

[0114] Example 7

[0115] Steps (1), (2), and (4) are the same as in Example 1. In step (3), 3-propyltriethoxysilane and 1,3-butanediol are mixed at a molar ratio of 1:1 and stirred at 60°C for 6 hours to obtain a mixture, which is then loaded into the equipment feed tank. Everything else is the same. The resulting coating is uniform and transparent.

[0116] Example 8

[0117] Steps (1), (2), and (4) are the same as in Example 1. In step (3), 3-isocyanate-propyltrimethoxysilane and polyethylene glycol 300 are mixed at a molar ratio of 1:1 and stirred at 60°C for 6 hours to obtain a mixture, which is then loaded into the equipment feed tank. Everything else is the same. The resulting coating is uniform and transparent.

[0118] Example 9

[0119] Steps (1), (2), and (4) are the same as in Example 1. In step (3), m-methylphenyl isocyanate and 1,4-butenediol are mixed at a molar ratio of 1:2 and stirred at 60°C for 6 hours to obtain a mixture, which is then loaded into the equipment feed tank. Everything else is the same. The resulting coating is uniform and transparent.

[0120] Example 10

[0121] In step (1), the transparent glass substrate sample was replaced with a transparent polycarbonate (PC) board (10 cm long, 5 cm wide, and 0.5 cm thick) substrate sample, and the rest was the same as in Example 9. The resulting coating was uniform and transparent.

[0122] Comparative Example 1

[0123] A blank transparent glass plate without coating (length: 13 cm, width: 6.5 cm, thickness: 1 mm) was used as the sample for Comparative Example 1.

[0124] Comparative Example 2

[0125] Steps (1), (2), and (4) are the same as in Example 1. In step (3), 3-propyltriethoxysilane is loaded into the equipment feed tank. Everything else is the same.

[0126] Comparative Example 3

[0127] Steps (1), (2), and (4) are the same as in Example 1. In step (3), polyethylene glycol 300 is loaded into the equipment feed tank. Everything else is the same.

[0128] Comparative Example 4

[0129] Steps (1), (2), and (4) are the same as in Example 1. In step (3), the 1,4-butenediol feed tank is used. Everything else is the same.

[0130] Test case

[0131] The performance of each sample was tested using the following equipment and methods, and the results are listed in Table 1:

[0132] ① Coating thickness

[0133] The film thickness was measured using a Filmetrics F20-UV thin film thickness testing device from the United States.

[0134] ② Visible light transmittance

[0135] Measurements were performed using a Perkin-Elmer-Lambda 950 UV-Vis spectrophotometer.

[0136] ③ Initial water contact angle

[0137] After the coating is prepared, it is tested according to GB / T 30447-2013 "Method for measuring contact angle of nanofilms".

[0138] ④ Durability

[0139] After the sample was left to stand at room temperature for 7 days, the water contact angle was measured according to GB / T 30447-2013 "Method for Measurement of Contact Angle of Nanofilms".

[0140] ⑤ Friction properties

[0141] The linear abrasion tester manufactured by Taber was used, with a load of 10 Newtons, the friction medium being cotton cloth soaked in alcohol, a thread length of 4 cm, a speed of 40 rpm, and 100 cycles of friction. The water contact angle value was tested before and after friction according to the standard GB / T30447-2013 "Method for Measurement of Contact Angle of Nanofilms".

[0142] ⑥ Water vapor anti-fogging

[0143] Tested according to GB / T 32166.2-2015 standard. Before testing, the sample was placed in distilled water at (23±5)℃ for 1-2 hours. After removal, the sample was gently patted dry with a cloth and placed in air at 23±5℃ and 50% humidity for at least 12 hours. Then, the sample was placed in the test port at (50±0.5℃), and the transmittance of the sample was recorded. If the transmittance was still higher than 80% of the value before fogging after 15 seconds, the anti-fogging test was passed and recorded as OK; otherwise, the test failed and was recorded as NG. The transmittance curve of the sample in Example 6 as a function of time is shown below. Figure 1 As shown, its coating has excellent anti-fog performance.

[0144] ⑦ Low-temperature anti-fogging

[0145] Place the sample in a -20°C freezer for 2 hours, then remove the sample and observe whether the surface is fogged. If it is clear, mark it as OK; if it is fogged, mark it as NG.

[0146] Table 1: Performance Test Results of Examples and Comparative Samples

[0147]

[0148] As can be seen from the experimental data in Table 1, compared with Comparative Example 1, Examples 1-10 all produced uniform, transparent, hydrophilic, durable and abrasion-resistant nano-coatings, which passed the water vapor anti-fogging test and the low temperature anti-fogging test.

[0149] In Examples 1-7, the first raw material containing isocyanate bonds is kept unchanged, while the type of the second raw material containing hydroxyl or amino groups or the ratio of the first and second raw materials is changed. In Examples 8 and 9, the type of the first raw material containing isocyanate bonds is relatively changed. In Example 10, the type of substrate is relatively changed. The resulting coatings all have ideal properties. It can be seen that the first raw material, the second raw material, the ratio of raw materials, and the substrate are not limited to one or more types.

[0150] Comparing the data of Examples 1-7 with Comparative Example 2, it can be seen that after the first raw material containing isocyanate bonds, which itself has poor hydrophilicity and anti-fogging properties, is combined with the second raw material containing hydroxyl and amino groups, the resulting coating has stronger hydrophilicity, better anti-fogging properties, better durability, and better abrasion resistance.

[0151] The samples of Comparative Examples 3 and 4 failed the water vapor anti-fogging test. Possible reasons include that the coatings dissolved in water and failed after being placed in distilled water at (23±5)℃ for 1 to 2 hours. Compared with Comparative Examples 3 and 4, Examples 8 and 9 show that after the second raw material containing hydroxyl and amino groups is combined with the first raw material containing isocyanate bonds, the coating does not fail due to dissolution in water, and has better anti-fogging performance, better hydrophilicity, and better abrasion resistance.

[0152] The various specific embodiments described above and shown in the accompanying drawings are for illustrative purposes only and do not represent the entirety of the invention. Any modifications made by those skilled in the art within the scope of the basic technical concept of this invention are within the protection scope of this invention.

Claims

1. A method for preparing an anti-fog coating, characterized in that, Includes the following steps: The substrate is placed inside the plasma reaction chamber; as well as A first raw material containing isocyanate bonds and a second raw material containing hydroxyl and / or amino groups are introduced into the plasma reaction chamber, and plasma discharge is performed to form an anti-fog coating on the surface of the substrate. The first raw material has structural formula I: ， Wherein R1 and R2 are independently hydrogen atoms, fluorine atoms, alkyl groups, or alkyl groups in which hydrogen atoms are partially or completely substituted with fluorine atoms, or alkyl groups linked to a benzene ring via an oxygen atom; R1 and R2 are ortho, para, or meta positions; R1 is ortho, para, or meta positions to the isocyanate bond; and / or The first raw material has the structural formula II: Si(OR3)x(R4)y(R5)z, wherein R3 is a C1-C3 alkyl group, R4 is hydrogen or alkyl group, R5 is an alkyl group with an isocyanate bond at the end, x+y+z=4, 1≤x≤3, 0≤y≤2, 1≤z; The second raw material has structural formula III: R6-X, wherein X is a hydroxyl or amino group, and R6 is a hydrocarbon group connected with at least one -OH or -NH2 group.

2. The method as described in claim 1, characterized in that, The first raw material includes at least one of propyltriethoxysilane, propyltrimethoxysilane, m-methylphenyl isocyanate, methyl-(3-propylisocyanate)dimethylsilane, propyltrimethoxysilane, 10-decylisocyanate, p-methoxyphenyl isocyanate, 3-methoxyphenyl isocyanate, phenyl 3-(trifluoromethyl)isocyanate, 2,4-difluorophenyl isocyanate, m-methylphenyl isocyanate, 3,5-dimethylphenyl isocyanate, 3,5-bis(trifluoromethyl)phenyl isocyanate, p-fluorophenyl isocyanate, and phenyl isocyanate.

3. The method as described in claim 1, characterized in that, The first raw material includes at least one of propyltriethoxysilane, propyltrimethoxysilane, and m-methylphenylisocyanate.

4. The method as described in claim 1, characterized in that, The second raw material is a hydrophilic material.

5. The method as described in claim 1, characterized in that, R6 is an alkyl group in which some carbon atoms are replaced by secondary amines, tertiary amines, or oxygen atoms.

6. The method as described in claim 1, characterized in that, The second raw material includes at least one of polyethylene glycol, Tween 20, diethanolamine, 1,4-butenediol, 1,3-butanediol, glycerol, 1,2,4-butanetriol, 2,3-butanediol, pentane-1,3-diol, 1,2,6-hexanetriol, triethylene glycol, N-butyldiethanolamine, N-(3-aminopropyl)diethanolamine, and N-ethyldiethanolamine.

7. The method as described in claim 1, characterized in that, The second raw material includes at least one of polyethylene glycol, Tween 20, diethanolamine, 1,4-butenediol, and 1,3-butanediol.

8. The method as described in claim 1, characterized in that, The molar ratio of the first raw material to the second raw material is in the range of 1:0.5 to 1:

5.

9. The method as described in claim 1, characterized in that, The process of introducing a first raw material containing isocyanate bonds and a second raw material containing hydroxyl and / or amino groups into the plasma reaction chamber includes mixing, heating the first raw material and the second raw material, and then vaporizing the mixture of the first raw material and the second raw material.

10. The method as described in claim 1, characterized in that, The substrate includes at least one of glass and plastic.

11. The method as described in claim 10, characterized in that, The plastic includes at least one of polycarbonate, polymethyl methacrylate, polystyrene, and polyethylene terephthalate.

12. An anti-fog coating, characterized in that, It is prepared by the method according to any one of claims 1-11.

13. The anti-fog coating as described in claim 12, characterized in that, The water contact angle of the anti-fog coating is ≤12°.

14. The anti-fog coating as described in claim 12, characterized in that, The water contact angle of the anti-fog coating is ≤14° after being rubbed 100 times with an alcohol-soaked cotton cloth under a load of 10 Newtons.

15. The anti-fog coating as described in claim 12, characterized in that, The visible light transmittance of the anti-fog coating is ≥90%.

16. A device, characterized in that, At least a portion of the surface of the device includes an anti-fog coating as described in any one of claims 12-15.

17. The device as claimed in claim 16, characterized in that, Including at least one of the following: bathroom glass, eyeglasses, swimming goggles, camera lenses, car windows, infrared microscopes, surgical endoscopes, and solar panels.

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