Water-repellent, anti-reflective glass for vehicles, its manufacturing method, and laminated glass

Abstract

The present invention provides a water-repellent, anti-reflective glass for vehicles, a manufacturing method thereof, and laminated glass. The water-repellent, anti-reflective glass includes a first glass plate and a water-repellent, anti-reflective coating layer applied to the side surface of the glass plate. The water-repellent, anti-reflective coating layer has a single layer structure formed by curing a water-repellent, anti-reflective paint. The raw materials for the water-repellent, anti-reflective paint include silicate ester, phenyl silane, and a fluorine-based surfactant. The refractive index of the water-repellent, anti-reflective coating layer is 1.20-1.30. The water-repellent, anti-reflective glass combines water repellency with anti-reflective performance.

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims priority based on a Chinese patent application filed with the China Patent Office on March 10, 2022, bearing application number 202210236924.6 and entitled "Water-repellent and anti-reflective glass for vehicles, its manufacturing method, and laminated glass," the entire contents of which are incorporated herein by reference.

[0002] The present invention relates to the field of glass manufacturing technology, and more particularly to a water-repellent, anti-reflective glass for vehicles, a manufacturing method thereof, and laminated glass. [Background technology]

[0003] With advances in science and technology, new requirements for automotive glass products have emerged, not only for safety and wind protection but also for comfort and functionality. In recent years, automotive glass products that fulfill the functions of functionality, comfort, and aesthetics have emerged one after another, including heat-shielding and UV-shielding glass, water-repellent glass, solar energy glass, anti-fog glass, HUD (Head-Up Display) glass, and tinted glass. Water-repellent glass effectively rolls off water droplets in rainy weather, maintaining good driver visibility and is widely used in the automotive glass industry. Anti-reflective coatings have long been used in the optical field and as display glass in malls and museums due to their ability to effectively reduce light reflection. However, anti-reflective glass has since been increasingly recognized in the automotive glass industry for its ability to effectively reduce nighttime reflections on the interior of the vehicle, thereby reducing visual interference and fatigue for the driver.

[0004] In the prior art, patents CN110776826A, CN109321131A, CN112094586A, CN111978861A, CN111925525A, CN112080716A, CN111892846A, CN107902918B, CN108027453A, CN108017290A, and CN108025962A disclose technologies related to water-repellent coatings or anti-reflective glass, but most of these patents separate the water-repellent and anti-reflective functions. Furthermore, CN108025962A and CN108312655A add an anti-fingerprint coating to the anti-reflective coating to improve the water-repellent properties of the coating, but there is no technology yet that can simultaneously impart water-repellent and anti-reflective properties to glass in one step. Summary of the Invention [Problem to be solved by the invention]

[0005] In order to solve the above problems, the present invention aims to provide a water-repellent, anti-reflective glass for vehicles, a manufacturing method thereof, and laminated glass. In this invention, by spraying a single layer of water-repellent, anti-reflective paint coating onto the glass surface, it is possible to provide the glass with both water-repellent and anti-reflective properties. [Means for solving the problem]

[0006] To achieve the above object, the present invention provides a water-repellent, anti-reflective glass for vehicles, comprising a first glass sheet and a water-repellent, anti-reflective coating layer applied to one side of the first glass sheet. The water-repellent, anti-reflective coating layer has a single-layer structure formed by curing a water-repellent, anti-reflective paint. The raw materials for the water-repellent, anti-reflective paint include silicate ester, phenylsilane, and a fluorine-based surfactant. The water-repellent, anti-reflective coating layer has a water contact angle of 110°-130° and a refractive index of 1.20-1.30.

[0007] In some specific embodiments, a bent glass sheet may be selected as the first glass sheet, and in this case, the first glass sheet may be referred to as a first bent glass sheet.

[0008] In some specific embodiments, the first bent glass sheet generally has a first concave surface and a first convex surface, and the water-repellent and anti-reflective coating layer is generally applied to the first convex surface or the first concave surface.

[0009] In some specific embodiments, the thickness of the water-repellent and anti-reflection coating layer is preferably 10 nm to 300 nm, for example, 50 nm to 250 nm.

[0010] In some specific embodiments, the water-repellent and anti-reflection coating layer preferably has a water contact angle of 120° or more.

[0011] In some specific embodiments, the refractive index of the water-repellent and anti-reflection coating layer is preferably 1.21-1.25.

[0012] In some specific embodiments, the porosity of the water-repellent and anti-reflective coating layer can reach 40% or more.

[0013] In some specific embodiments, the refractive index of the water-repellent and anti-reflective coating layer is 1.23-1.28.

[0014] In some specific embodiments, a flat abrasion test is performed using a flat abrasion meter with the water-repellent and anti-reflective coating layer of the water-repellent and anti-reflective glass for vehicles facing upward, and a flat abrasion test is performed for 100 revolutions at 2.45 N x 100 r. The measured contact angle after abrasion is 100° or more.

[0015] In some specific embodiments, the water-repellent and anti-reflective coating is obtained by mixing a first solution with a second solution, where the total mass of the raw materials of the water-repellent and anti-reflective coating is 100%, the first solution generally contains 3%-20% silicate ester, 2%-10% phenylsilane, 0.01%-0.5% fluorosurfactant, and a first organic solvent, and the second solution contains 0.5%-5% catalyst and a second organic solvent.

[0016] In some specific embodiments, the total mass ratio of the first organic solvent and the second organic solvent in the raw materials of the water-repellent and anti-reflective coating is 65%-90%.

[0017] In some specific embodiments, the total mass ratio of the fluorosurfactant and the phenylsilane in the raw materials of the water-repellent and anti-reflective coating is generally controlled to 3%-9%.

[0018] In some specific embodiments, the total mass ratio of the silicate ester and the phenylsilane in the raw materials of the water-repellent and anti-reflective coating is generally controlled to 5%-15%.

[0019] In some specific embodiments, the silicate ester may include one or a combination of two or more of tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate, and tetrabutyl orthosilicate.

[0020] In some specific embodiments, the phenylsilane comprises one or a combination of two or more of phenyltrimethoxysilane, phenyltriethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, and methylphenyldiethoxysilane.

[0021] In some specific embodiments, the fluorosurfactant comprises a nonionic fluorocarbon surfactant.

[0022] In some specific embodiments, the nonionic fluorocarbon surfactant may have a solids content of 50% or more.

[0023] In some specific embodiments, the fluorosurfactant comprises a perfluorooctyl polyether surfactant.

[0024] In some specific embodiments, the water-solubility of the perfluorooctyl polyether surfactant may be 90% or more.

[0025] In some specific embodiments, the first organic solvent and / or the second organic solvent comprises one or a combination of two or more of methanol, ethanol, propanol, butanol, and isopropanol.

[0026] In some specific embodiments, the catalyst comprises a basic catalyst or an acidic catalyst, wherein the basic catalyst may comprise one or a combination of two or more of sodium hydroxide, potassium hydroxide, aqueous ammonia, and sodium bicarbonate, and the acidic catalyst may comprise one or a combination of two or more of hydrochloric acid, nitric acid, and acetic acid.

[0027] The present invention further provides a method for producing the water-repellent, anti-reflective glass for vehicles, comprising the steps of: mixing and stirring 3%-20% silicate ester, 2%-10% phenylsilane, 0.01%-0.5% fluorine-based surfactant, and a first organic solvent to obtain a first solution, and mixing and stirring 0.5%-5% catalyst and a second organic solvent to obtain a second solution, mixing and stirring the second solution with the first solution to obtain the water-repellent, anti-reflective coating, and applying the water-repellent, anti-reflective coating to one surface of a first glass plate, curing it, and then forming a water-repellent, anti-reflective coating layer on the surface to obtain the water-repellent, anti-reflective glass for vehicles.

[0028] In some specific embodiments, the method includes: mixing and stirring 3%-20% silicate ester, 2%-10% phenylsilane, 0.01%-0.5% fluorine-based surfactant, and a first organic solvent to obtain a first solution, where the total mass of the raw materials for the water-repellent and anti-reflective coating is 100%; mixing and stirring 0.5%-5% catalyst and a second organic solvent to obtain a second solution, where the sum of the mass ratio of the first organic solvent in the raw materials for the water-repellent and anti-reflective coating and the mass ratio of the second organic solvent in the raw materials for the water-repellent and anti-reflective coating is 65%-90%; mixing and stirring the second solution with the first solution to obtain the water-repellent and anti-reflective coating; and applying the water-repellent and anti-reflective coating to one surface of a first glass plate and curing it to form a water-repellent and anti-reflective coating layer on the surface, thereby obtaining a water-repellent and anti-reflective glass for vehicles.

[0029] In some specific embodiments, when the first glass plate is a first bent glass plate, the water-repellent and anti-reflective coating is typically applied to the first convex surface or the first concave surface of the first bent glass plate and cured to form a water-repellent and anti-reflective layer on the first convex surface or the first concave surface.

[0030] In some specific embodiments, mixing and stirring the second solution with the first solution comprises adding the second solution dropwise to the first solution while stirring the first solution, the rate of the addition being controlled to typically 30-120 drops / min, preferably 50-80 drops / min.

[0031] In some specific embodiments, the mode of application comprises ultrasonic spraying.

[0032] In some specific embodiments, during the ultrasonic spraying process, the ultrasonic frequency is 50 kHz-120 kHz, the discharge amount during the spraying process is 0.5 mL / min-10 mL / min, and the spray movement speed is 300 mm / sec-800 mm / sec.

[0033] In some specific embodiments, the curing process may include sequentially performing a first cure and a second cure, wherein the temperature of the first cure is 50°C-100°C and the temperature of the second cure is 150°C-200°C.

[0034] In some specific embodiments, the first cure may be performed using an infrared lamp.

[0035] In some specific embodiments, the time for the first cure may be controlled to 10 min-50 min.

[0036] In some specific embodiments, the second cure may be performed using a blow dry box.

[0037] In some specific embodiments, the time for the second curing may be controlled to 30 min-120 min.

[0038] The present invention also provides a water-repellent, anti-reflective laminated glass for vehicles, comprising the above-mentioned water-repellent, anti-reflective glass for vehicles, a second glass plate, and a thermoplastic intermediate layer positioned between the first glass plate and the second glass plate of the water-repellent, anti-reflective glass for vehicles. The water-repellent, anti-reflective laminated glass for vehicles has an outer surface and an inner surface. The water-repellent, anti-reflective coating layer is positioned on the outer surface or the inner surface of the laminated glass.

[0039] In some specific embodiments, the water-repellent and anti-reflective coating layer is typically located on the surface of the first glass sheet facing away from the thermoplastic interlayer.

[0040] In some specific embodiments, after the laminated glass is installed in a vehicle, the first glass sheet may be located on the exterior side of the vehicle and the second glass sheet may be located on the interior side of the vehicle. Alternatively, the second glass sheet may be located on the exterior side of the vehicle and the first glass sheet may be located on the interior side of the vehicle.

[0041] In some specific embodiments, when the first glass sheet is a first bent glass sheet, the first convex surface of the first bent glass sheet is the outer surface of the laminated glass, or the first concave surface of the first bent glass sheet is the inner surface of the laminated glass. [Effects of the Invention]

[0042] The beneficial effects of the present invention are as follows: 1. In this invention, phenylsilane and a fluorine-based surfactant are added to the water-repellent and anti-reflective coating layer, and the synergistic effect of the two can give the glass both water-repellent and anti-reflective properties. The water-repellent and anti-reflective glass with the single-layer water-repellent and anti-reflective coating layer obtained in this way has a water contact angle of 110°-130°, providing good water-repellency, and the refractive index is effectively reduced to 1.20-1.30, providing good anti-reflective properties. 2. Compared with two- or multi-layer coatings that provide water-repellent or anti-reflective properties alone, the process conditions and techniques adopted in the manufacturing method for water-repellent and anti-reflective vehicle glass of the present invention are simple to operate and suitable for coating one or both sides of various curved automotive glass. It can also be applied to the manufacturing of water-repellent and anti-reflective laminated vehicle glass, and is expected to have a good future in the field of vehicle glass. [Brief explanation of the drawings]

[0043] [Figure 1] Schematic diagram of the structure of the water-repellent, anti-reflective glass for vehicles of the present invention [Figure 2] Schematic diagram of the structure of one water-repellent, anti-reflective laminated glass for vehicles of the present invention. [Figure 3] Schematic diagram of the structure of another water-repellent, anti-reflection laminated glass for vehicles according to the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0044] In order to make the technical features, objectives and beneficial effects of the present invention more clearly understood, the technical solutions of the present invention are described in detail below, but should not be understood as limiting the possible scope of the present invention.

[0045] The present invention provides a water-repellent, anti-reflective glass for vehicles, comprising a first glass sheet and a water-repellent, anti-reflective coating layer applied to one side of the first glass sheet. The water-repellent, anti-reflective coating layer has a single-layer structure formed by curing a water-repellent, anti-reflective paint, and the raw materials for the water-repellent, anti-reflective paint include silicate ester, phenylsilane, and a fluorine-based surfactant. The water-repellent, anti-reflective coating layer has a water contact angle of 110°-130° and a refractive index of 1.20-1.30.

[0046] As shown in FIG. 1, the water-repellent, anti-reflection glass for vehicles of the present invention specifically includes a first curved glass sheet 1 and a water-repellent, anti-reflection coating layer 2. The first curved glass sheet 1 has a first convex surface 11 and a first concave surface 12. The water-repellent, anti-reflection coating layer 2 is applied to the first convex surface 11 or the first concave surface 12. The water-repellent, anti-reflection coating layer 2 has a single-layer structure formed by curing a water-repellent, anti-reflection coating material. The raw materials for the water-repellent, anti-reflection coating material include silicate ester, phenylsilane, and a fluorine-based surfactant. The water contact angle of the water-repellent, anti-reflection coating layer 2 is 110°-130°, and the refractive index of the water-repellent, anti-reflection coating layer 2 is 1.20-1.30 (e.g., 1.21, 1.22, 1.23, 1.24, 1.25, 1.26, 1.27, 1.28, 1.29).

[0047] In the present invention, a single-layer water-repellent and anti-reflective coating layer is applied to one surface of a first glass sheet (e.g., a first curved glass sheet). The combination of a single-layer coating layer and a glass sheet alone can produce a water-repellent and anti-reflective glass that combines water repellency and a low refractive index. Furthermore, in conventional techniques, it is difficult to control the refractive index of a single-layer coating layer to 1.25 or less. To simultaneously achieve water repellency and a relatively low refractive index, a multi-layer coating layer is typically required. However, in some specific embodiments of the present invention, a single-layer water-repellent and anti-reflective coating layer can achieve a good refractive index of 1.21-1.25 while maintaining good water repellency. Specifically, the refractive index may be 1.21, 1.22, 1.23, 1.24, 1.25, etc., which is close to the refractive index of an ideal anti-reflective coating (1.23).

[0048] In some specific embodiments, the thickness of the water-repellent and anti-reflection coating layer 2 is preferably controlled to 10 nm-300 nm, for example, 50 nm-250 nm, more preferably 80 nm-200 nm.

[0049] In some specific embodiments, the water contact angle of the water-repellent and anti-reflection coating layer 2 is preferably 120° or more.

[0050] In some specific embodiments, the refractive index of the water-repellent and anti-reflective coating layer is 1.23-1.28.

[0051] In some specific embodiments, a flat abrasion test is performed using a flat abrasion meter with the water-repellent and anti-reflective coating layer 2 of the water-repellent and anti-reflective glass for vehicles facing upward, and a flat abrasion test is performed 100 times at 2.45 N x 100 r. The contact angle after abrasion is measured to be 100° or greater. Furthermore, the contact angle after abrasion may be 104° or greater, 105° or greater, 106° or greater, 107° or greater, 110° or greater, 111° or greater, 112° or greater, 113° or greater, 114° or greater, 115° or greater, 119° or greater, etc. Furthermore, the contact angle after abrasion may be specific values ​​such as 104°, 105°, 106°, 107°, 110°, 111°, 112°, 113°, 114°, 115°, or 119°, or may be a range defined by any two of the above specific values.

[0052] In some specific embodiments, the porosity of the water-repellent and anti-reflective coating layer 2 may be 40% or more.

[0053] In some specific embodiments, the water-repellent and anti-reflective coating is obtained by mixing a first solution with a second solution. The first solution typically contains 3%-20% silicate ester, 2%-10% phenylsilane, 0.01%-0.5% fluorosurfactant, and a first organic solvent, while the second solution contains 0.5%-5% catalyst and a second organic solvent, based on the total mass of the water-repellent and anti-reflective coating raw materials (100%). The combined mass ratio of the first organic solvent and the second organic solvent in the water-repellent and anti-reflective coating raw materials is 65%-90%. By controlling the amounts of the fluorosurfactant and phenylsilane added to the coating, a single-layer water-repellent and anti-reflective coating layer with excellent water-repellent and anti-reflective properties can be obtained, while ensuring that the abrasion resistance of the single-layer water-repellent and anti-reflective coating layer meets the requirements for use on automotive glass. Preferably, the combined mass ratio of the phenylsilane and the fluorosurfactant in the water-repellent and anti-reflective coating raw materials is 3%-9%.

[0054] In some specific embodiments, the total mass ratio of the silicate ester and the phenylsilane in the raw materials of the water-repellent and anti-reflective coating is generally controlled to 5%-15%. Controlling the amount of silicate ester and phenylsilane added within the above range is advantageous for the storage of the coating and can provide a coating layer with a good refractive index.

[0055] In some specific embodiments, the silicate ester may include one or a combination of two or more of tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate, and tetrabutyl orthosilicate.

[0056] In the present invention, the molecular chain of the phenylsilane contains one or more phenyl groups. Because phenyl groups have water-repellent properties, their incorporation into a coating can significantly improve the water-repellency of the coating formed from the coating. Specifically, the phenylsilane may be a phenylsiloxane. Compared to other types of molecular chains, siloxane molecular chains are more suitable as a carrier for the phenyl groups to hybridize with silicate esters in glass substrates, and phenylsiloxanes can enhance the bonding strength between the coating and glass. Furthermore, selecting a phenylsilane with a methoxy or ethoxy group is advantageous for the occurrence of the spring-back phenomenon, making it easier to prepare a coating with a low refractive index. Phenylsilanes suppress shrinkage of the coating film during drying, increase porosity, and reduce the refractive index. In some specific embodiments, the phenylsilane includes one or a combination of two or more of phenyltrimethoxysilane, phenyltriethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, and methylphenyldiethoxysilane.

[0057] In the present invention, the addition of a fluorosurfactant can improve the leveling property and leveling speed of the coating layer formed from the paint, and can also reduce the surface energy without affecting the abrasion resistance of the coating layer, thereby further improving the water repellency of the coating layer. In some specific embodiments, the fluorosurfactant includes a nonionic fluorocarbon surfactant, a perfluorooctyl polyether surfactant, or a combination of a nonionic fluorocarbon surfactant and a perfluorooctyl polyether surfactant.

[0058] In some specific embodiments, the solids content of the nonionic fluorocarbon surfactant may be 50% or greater, including 55%, 60%, 65%, 70%, 75%, 80%, and the like.

[0059] In some specific embodiments, the water solubility of the perfluorooctyl polyether surfactant is preferably 90% or more, which allows the fluorine-based surfactant to be better dispersed in the solvent system of the water-repellent and anti-reflective coating material.

[0060] In some specific embodiments, the first organic solvent and / or the second organic solvent comprises one or a combination of two or more of methanol, ethanol, propanol, butanol, and isopropanol.

[0061] According to specific embodiments of the present invention, by controlling the amount of fluorosurfactant used within an appropriate range, it is possible to improve the leveling and water repellency of the coating layer while avoiding adverse effects on the refractive index of the coating layer. In some specific embodiments, the mass ratio of the fluorosurfactant in the raw materials of the water-repellent and anti-reflective coating is generally controlled to 0.01%-0.5%. In some specific embodiments, the fluorosurfactant can be selected from one or a combination of two or more of GS-823 (Zi Cheng International Trading Co., Ltd.), WE-D9053R (Xinnuo Chemical Co., Ltd.), WE-D8950BR (Xinnuo Chemical Co., Ltd.), FCN-18 (Hangzhou Renshan Technology Co., Ltd.), etc.

[0062] In some specific embodiments, the catalyst comprises a basic catalyst or an acidic catalyst, wherein the basic catalyst may comprise one or a combination of two or more of sodium hydroxide, potassium hydroxide, aqueous ammonia, and sodium bicarbonate, and the acidic catalyst may comprise one or a combination of two or more of hydrochloric acid, nitric acid, and acetic acid.

[0063] The present invention provides a method for producing the above-mentioned water-repellent, anti-reflective glass for vehicles, which includes: mixing and stirring 3%-20% silicate ester, 2%-10% phenylsilane, 0.01%-0.5% fluorosurfactant, and a first organic solvent to obtain a first solution, and mixing and stirring 0.5%-5% catalyst and a second organic solvent to obtain a second solution (the sum of the mass ratio of the first organic solvent in the water-repellent, anti-reflective coating raw materials and the mass ratio of the second organic solvent in the water-repellent, anti-reflective coating raw materials is 65%-90%); mixing and stirring the second solution with the first solution to obtain the water-repellent, anti-reflective coating; and applying the water-repellent, anti-reflective coating to one surface of a first glass plate, curing it, and then forming a water-repellent, anti-reflective coating layer on the surface to obtain the water-repellent, anti-reflective glass for vehicles. The above-mentioned manufacturing method utilizes a sol-gel method, in which a coating layer having high water repellency is formed by adding phenylsilane and causing a hydrolysis polycondensation reaction together with a silicate ester.

[0064] In the present invention, when the first glass plate is a first bent glass plate, the above-mentioned manufacturing method typically involves applying a water-repellent and anti-reflective coating to the first convex surface or the first concave surface of the first bent glass plate, and then forming a water-repellent and anti-reflective coating layer on the first convex surface or the first concave surface after curing, thereby obtaining a water-repellent and anti-reflective glass for vehicles.

[0065] In the present invention, by adding a second solution containing a catalyst to a first solution containing a silicate ester, the problem of precipitation due to rapid hydrolysis and polycondensation of the silicate ester caused by a locally high concentration can be effectively avoided. In some specific embodiments, mixing and stirring the second solution and the first solution includes adding the second solution dropwise to the first solution while stirring the first solution. The rate of the dropwise addition is typically controlled at 30-120 drops / min, preferably 50-80 drops / min.

[0066] In some specific embodiments, the mode of application comprises ultrasonic spraying.

[0067] In the present invention, by controlling the parameters of the spraying process, it is possible to relatively accurately prepare a coating layer with a thickness on the order of nanometers, and obtain glass that can be applied to different curved surfaces, allowing for great flexibility in producing convex or concave coating layers. In some specific embodiments, in the ultrasonic spraying process, the ultrasonic frequency is 50 kHz-120 kHz, the outflow rate during the spraying process is 0.5 mL / min-10 mL / min, and the spray movement speed is 300 mm / sec-800 mm / sec.

[0068] In some specific embodiments, the curing process includes a first cure and a second cure performed sequentially, the first cure temperature is 50°C-100°C, and the second cure temperature is 150°C-200°C.

[0069] In some specific embodiments, the first curing may be performed using an infrared lamp, which can maximize the retention of the pore structure of the coating layer and ensure sufficient porosity of the coating layer, while also achieving the effect of rapidly drying the surface of the coating layer.

[0070] In some specific embodiments, the time for the first curing can be controlled to 10 min-50 min, for example, 10 min-30 min.

[0071] In some specific embodiments, the second cure may be performed using a blow dry box.

[0072] In some specific embodiments, the time for the second curing can be controlled to 30 min-120 min, for example, 30 min-90 min.

[0073] The present invention provides a water-repellent, anti-reflective laminated glass for vehicles, comprising the above-mentioned water-repellent, anti-reflective glass for vehicles, a second glass sheet, and a thermoplastic intermediate layer positioned between the first glass sheet and the second glass sheet. The water-repellent, anti-reflective laminated glass for vehicles has an outer surface and an inner surface. The water-repellent, anti-reflective coating layer is positioned on the outer surface or the inner surface of the laminated glass.

[0074] As shown in Figures 2 and 3, the water-repellent, anti-reflective laminated glass for vehicles of the present invention specifically comprises a water-repellent, anti-reflective glass for vehicles 10, a second curved glass sheet 30, and a thermoplastic interlayer 20. The thermoplastic interlayer 20 is located between the first curved glass sheet 1 and the second curved glass sheet 30 in the water-repellent, anti-reflective laminated glass for vehicles 10. The water-repellent, anti-reflective laminated glass for vehicles has an outer surface 51 and an inner surface 52. The first convex surface 11 of the first curved glass sheet is the outer surface 51 of the laminated glass, or the first concave surface 12 of the first curved glass sheet is the inner surface 52 of the laminated glass. The water-repellent, anti-reflective coating layer 2 is located on the outer surface 51 or the inner surface 52 of the laminated glass.

[0075] The second bent glass sheet 30 has a second convex surface and a second concave surface.

[0076] In Figure 2, the first curved glass sheet 1 is the inner glass sheet of the laminated glass, the second curved glass sheet 30 is the outer glass sheet of the laminated glass, the second convex surface of the second curved glass sheet 30 is the outer surface 51 of the laminated glass, the first concave surface of the first curved glass sheet 1 is the inner surface 52 of the laminated glass, and the water-repellent and anti-reflection coating layer 2 is located on the inner surface 52 of the laminated glass.

[0077] In Figure 3, the first curved glass sheet 1 is the outer glass sheet of the laminated glass, the second curved glass sheet 30 is the inner glass sheet of the laminated glass, the second concave surface of the second curved glass sheet 30 is the inner surface 52 of the laminated glass, the first convex surface of the first curved glass sheet 1 is the outer surface 51 of the laminated glass, and the water-repellent and anti-reflection coating layer 2 is located on the outer surface 51 of the laminated glass.

[0078] In the following examples and comparative examples, the silicate ester used is tetraethyl orthosilicate, the phenylsilane is phenyltriethoxysilane, the fluorine-based surfactant is GS-823 (a nonionic fluorocarbon surfactant manufactured by Zi Cheng International Trading Co., Ltd.), the first organic solvent and the second organic solvent are both absolute ethanol, the catalyst is aqueous ammonia, and the bent glass sheet used is obtained by subjecting an ordinary glass sheet to high-temperature heat treatment at 560°C or higher and bending, and the ordinary glass sheet has a TL of 90%.

[0079] In the following examples and comparative examples, the first curing was carried out at a temperature of 50°C-100°C using an infrared lamp, and the second curing was carried out at a temperature of 150°C-200°C using an air drying box.

[0080] Example 1 This embodiment provides a water-repellent and anti-reflective glass for vehicles, the manufacturing method of which includes the following: 1. Taking the total mass of the raw materials for the water-repellent and anti-reflective coating as 100%, 8% silicate ester, 3% phenylsilane, 0.03% fluorine-based surfactant and 46.00% first organic solvent were mixed and stirred to obtain a first solution, and 2% catalyst and 40.97% second organic solvent were mixed and stirred to obtain a second solution. 2. While the first solution was being stirred, the second solution was added dropwise to the first solution at a rate of 30-120 drops / minute to obtain a water-repellent and anti-reflective coating. 3. The water-repellent and anti-reflective coating material was applied to the first concave surface of the first curved glass plate, and the first and second curing processes were carried out sequentially to form a water-repellent and anti-reflective coating layer, thereby obtaining a water-repellent and anti-reflective glass for vehicles.

[0081] Example 2 This embodiment provides a water-repellent and anti-reflective glass for vehicles, the manufacturing method of which includes the following: 1. Taking the total mass of the raw materials for the water-repellent and anti-reflective coating as 100%, 8% silicate ester, 3% phenylsilane, 0.13% fluorine-based surfactant and 46.00% first organic solvent were mixed and stirred to obtain a first solution, and 2% catalyst and 40.87% second organic solvent were mixed and stirred to obtain a second solution. 2. While the first solution was being stirred, the second solution was added dropwise to the first solution at a rate of 30-120 drops / minute to obtain a water-repellent and anti-reflective coating. 3. The water-repellent and anti-reflective coating material was applied to the first concave surface of the first curved glass plate, and the first and second curing processes were carried out sequentially to form a water-repellent and anti-reflective coating layer, thereby obtaining a water-repellent and anti-reflective glass for vehicles.

[0082] Example 3 This embodiment provides a water-repellent and anti-reflective glass for vehicles, the manufacturing method of which includes the following: 1. Taking the total mass of the raw materials for the water-repellent and anti-reflective coating as 100%, 8% silicate ester, 3% phenylsilane, 0.40% fluorine-based surfactant and 46.00% first organic solvent were mixed and stirred to obtain a first solution, and 2% catalyst and 40.60% second organic solvent were mixed and stirred to obtain a second solution. 2. While the first solution was being stirred, the second solution was added dropwise to the first solution at a rate of 30-120 drops / minute to obtain a water-repellent and anti-reflective coating. 3. The water-repellent and anti-reflective coating material was applied to the first concave surface of the first curved glass plate, and the first and second curing processes were carried out sequentially to form a water-repellent and anti-reflective coating layer, thereby obtaining a water-repellent and anti-reflective glass for vehicles.

[0083] Example 4 This embodiment provides a water-repellent and anti-reflective glass for vehicles, the manufacturing method of which includes the following steps: 1. Taking the total mass of the raw materials for the water-repellent and anti-reflective coating as 100%, 6% silicate ester, 5.60% phenylsilane, 0.03% fluorine-based surfactant and 46.00% first organic solvent were mixed and stirred to obtain a first solution, and 2% catalyst and 40.37% second organic solvent were mixed and stirred to obtain a second solution. 2. While the first solution was being stirred, the second solution was added dropwise to the first solution at a rate of 30-120 drops / minute to obtain a water-repellent and anti-reflective coating. 3. The water-repellent and anti-reflective coating material was applied to the first concave surface of the first curved glass plate, and the first and second curing processes were carried out sequentially to form a water-repellent and anti-reflective coating layer, thereby obtaining a water-repellent and anti-reflective glass for vehicles.

[0084] Example 5 This embodiment provides a water-repellent and anti-reflective glass for vehicles, the manufacturing method of which includes the following: 1. Taking the total mass of the raw materials for the water-repellent and anti-reflective coating as 100%, 6% silicate ester, 5.60% phenylsilane, 0.13% fluorine-based surfactant and 46.00% first organic solvent were mixed and stirred to obtain a first solution, and 2% catalyst and 40.27% second organic solvent were mixed and stirred to obtain a second solution. 2. While the first solution was being stirred, the second solution was added dropwise to the first solution at a rate of 30-120 drops / minute to obtain a water-repellent and anti-reflective coating. 3. The water-repellent and anti-reflective coating material was applied to the first concave surface of the first curved glass plate, and the first and second curing processes were carried out sequentially to form a water-repellent and anti-reflective coating layer, thereby obtaining a water-repellent and anti-reflective glass for vehicles.

[0085] Example 6 This embodiment provides a water-repellent and anti-reflective glass for vehicles, the manufacturing method of which includes the following: 1. Taking the total mass of the raw materials for the water-repellent and anti-reflective coating as 100%, 6% silicate ester, 5.60% phenylsilane, 0.40% fluorine-based surfactant and 46.00% first organic solvent were mixed and stirred to obtain a first solution, and 2% catalyst and 40.00% second organic solvent were mixed and stirred to obtain a second solution. 2. While the first solution was being stirred, the second solution was added dropwise to the first solution at a rate of 30-120 drops / minute to obtain a water-repellent and anti-reflective coating. 3. The water-repellent and anti-reflective coating material was applied to the first concave surface of the first curved glass plate, and the first and second curing processes were carried out sequentially to form a water-repellent and anti-reflective coating layer, thereby obtaining a water-repellent and anti-reflective glass for vehicles.

[0086] Example 7 This embodiment provides a water-repellent and anti-reflective glass for vehicles, the manufacturing method of which includes the following: 1. Taking the total mass of the raw materials for the water-repellent and anti-reflective coating as 100%, 4% silicate ester, 8% phenylsilane, 0.03% fluorine-based surfactant and 46.00% first organic solvent were mixed and stirred to obtain a first solution, and 2% catalyst and 39.97% second organic solvent were mixed and stirred to obtain a second solution. 2. While the first solution was being stirred, the second solution was added dropwise to the first solution at a rate of 30-120 drops / minute to obtain a water-repellent and anti-reflective coating. 3. The water-repellent and anti-reflective coating material was applied to the first concave surface of the first curved glass plate, and the first and second curing processes were carried out sequentially to form a water-repellent and anti-reflective coating layer, thereby obtaining a water-repellent and anti-reflective glass for vehicles.

[0087] Example 8 This embodiment provides a water-repellent and anti-reflective glass for vehicles, the manufacturing method of which includes the following: 1. Taking the total mass of the raw materials for the water-repellent and anti-reflective coating as 100%, 4% silicate ester, 8% phenylsilane, 0.13% fluorine-based surfactant and 46.00% first organic solvent were mixed and stirred to obtain a first solution, and 2% catalyst and 39.70% second organic solvent were mixed and stirred to obtain a second solution. 2. While the first solution was being stirred, the second solution was added dropwise to the first solution at a rate of 30-120 drops / minute to obtain a water-repellent and anti-reflective coating. 3. The water-repellent and anti-reflective coating material was applied to the first concave surface of the first curved glass plate, and the first and second curing processes were carried out sequentially to form a water-repellent and anti-reflective coating layer, thereby obtaining a water-repellent and anti-reflective glass for vehicles.

[0088] Example 9 This embodiment provides a water-repellent and anti-reflective glass for vehicles, the manufacturing method of which includes the following: 1. Taking the total mass of the raw materials for the water-repellent and anti-reflective coating as 100%, 4% silicate ester, 8% phenylsilane, 0.40% fluorine-based surfactant and 46.00% first organic solvent were mixed and stirred to obtain a first solution, and 2% catalyst and 41.60% second organic solvent were mixed and stirred to obtain a second solution. 2. While the first solution was being stirred, the second solution was added dropwise to the first solution at a rate of 30-120 drops / minute to obtain a water-repellent and anti-reflective coating. 3. The water-repellent and anti-reflective coating material was applied to the first concave surface of the first curved glass plate, and the first and second curing processes were carried out sequentially to form a water-repellent and anti-reflective coating layer, thereby obtaining a water-repellent and anti-reflective glass for vehicles.

[0089] Example 10 This embodiment provides a water-repellent and anti-reflective glass for vehicles, the manufacturing method of which includes the following: 1. The total mass of the raw materials for the water-repellent and anti-reflective coating was taken as 100%, and 10% of silicate ester, 3% of phenylsilane, 0.13% of fluorine-based surfactant, and 46.00% of the first organic solvent were mixed and stirred to obtain a first solution, and 2% of the catalyst and 38.87% of the second organic solvent were mixed and stirred to obtain a second solution. 2. While the first solution was being stirred, the second solution was added dropwise to the first solution at a rate of 30-120 drops / minute to obtain a water-repellent and anti-reflective coating. 3. The water-repellent and anti-reflective coating material was applied to the first concave surface of the first curved glass plate, and the first and second curing processes were carried out sequentially to form a water-repellent and anti-reflective coating layer, thereby obtaining a water-repellent and anti-reflective glass for vehicles.

[0090] Example 11 This embodiment provides a water-repellent and anti-reflective glass for vehicles, the manufacturing method of which includes the following: 1. Taking the total mass of the raw materials for the water-repellent and anti-reflective coating as 100%, 12% silicate ester, 3% phenylsilane, 0.13% fluorine-based surfactant and 46.00% first organic solvent were mixed and stirred to obtain a first solution, and 2% catalyst and 36.87% second organic solvent were mixed and stirred to obtain a second solution. 2. While the first solution was being stirred, the second solution was added dropwise to the first solution at a rate of 30-120 drops / minute to obtain a water-repellent and anti-reflective coating. 3. The water-repellent and anti-reflective coating material was applied to the first concave surface of the first curved glass plate, and the first and second curing processes were carried out sequentially to form a water-repellent and anti-reflective coating layer, thereby obtaining a water-repellent and anti-reflective glass for vehicles.

[0091] (Comparative Example 1) This comparative example provides a glass having a coating layer. Compared with the glasses produced in Examples 1-6, no fluorine-based surfactant was added during the production process of the coating layer of the glass. Specifically, the production method of the glass of this comparative example includes the following: 1. The total mass of the paint raw materials was taken as 100%, and 10% of silicate ester, 1% of phenylsilane, and 43.50% of the first organic solvent were mixed and stirred to obtain a first solution, and 2% of the catalyst and 43.50% of the second organic solvent were mixed and stirred to obtain a second solution. 2. While the first solution was being stirred, the second solution was added dropwise to the first solution at a rate of 30-120 drops / minute to obtain a coating material. 3. The coating material prepared in step 2 was applied to the first concave surface of the first bent glass plate, and the first and second curing processes were carried out sequentially to form a coating layer, thereby obtaining glass having a coating layer.

[0092] (Comparative Example 2) This comparative example provides a glass having a coating layer. Compared with the glasses produced in Examples 1-6, the amount of phenylsilane added during the production process of the coating layer of this glass is less than 1%. Specifically, the production method of the glass of this comparative example includes the following: 1. The total mass of the paint raw materials was taken as 100%, and 10% of silicate ester, 0.7% of phenylsilane, 0.03% of fluorine-based surfactant, and 43.50% of the first organic solvent were mixed and stirred to obtain a first solution, and 2% of the catalyst and 43.77% of the second organic solvent were mixed and stirred to obtain a second solution. 2. While the first solution was being stirred, the second solution was added dropwise to the first solution at a rate of 30-120 drops / minute to obtain a coating material. 3. The coating material prepared in step 2 was applied to the first concave surface of the first bent glass plate, and the first and second curing processes were carried out sequentially to form a coating layer, thereby obtaining glass having a coating layer.

[0093] (Test Example 1) The glass having the coating layer obtained in Comparative Example 1 and Comparative Example 2 and the water-repellent and anti-reflective glass for vehicles obtained in Examples 1 to 9 were tested for coating layer thickness, water contact angle, refractive index, porosity, visible light transmittance (center wavelength 550 nm), and abrasion resistance, and the test results are shown in Table 1. The coating layer thickness was measured using a step gauge. The water contact angle was measured with a contact angle measuring instrument against the coating layer on the glass surface. The refractive index of the film layer was measured using an ellipsometer. The porosity of the film layer was calculated from the measured refractive index. The visible light transmittance was measured by measuring the transmission spectrum of each sample in the visible light wavelength range of 380 nm to 780 nm using a spectrophotometer, and the visible light transmittance of the coating layer at a center wavelength of 550 nm was obtained. Abrasion resistance was measured using a flat abrasion tester. The glass sample was placed in the equipment with the coating facing up and subjected to a 100-rotation flat abrasion test at 2.45N x 100r. The contact angle after abrasion was measured. The contact angle here is the water contact angle of the water-repellent and anti-reflective coating layer.

[0094] [Table 1]

[0095] In Table 1, the refractive index of the water-repellent and anti-reflective coating layers of Examples 1 to 11 was 1.23-1.28, and the porosity of the water-repellent and anti-reflective coating layers was within the range of 40%-60%, specifically 43%-54%. Measurements were taken using a flat abrasion tester. The water-repellent and anti-reflective coating layers of the water-repellent and anti-reflective glass for vehicles were placed facing upward and subjected to a flat abrasion test of 100 revolutions at 2.45N x 100r. After abrasion, the contact angle was 100° or greater, and even 105° or greater, and even 110° or greater.

[0096] The following was confirmed from Table 1. 1. By controlling the total amount of phenylsilane and fluorosurfactant added to be within a reasonable range (3%-9%), the resulting coating layer can have excellent water repellency, anti-reflection, and abrasion resistance. 2. The amount of phenylsilane added to the coating significantly affects the porosity of the coating layer. Specifically, as the amount of phenylsilane added increases, the abrasion resistance and water repellency of the coating layer are significantly improved, and the refractive index of the coating layer also increases. 3. Adjusting the amount of fluorosurfactant added to the coating affected the porosity, but not the abrasion resistance. Specifically, the higher the amount of fluorosurfactant added, the higher the water contact angle of the resulting coating layer and glass, but the lower the porosity of the coating layer and the higher the refractive index. [Explanation of symbols]

[0097] 1. First bent glass sheet 2 Water-repellent and anti-reflective coating layer 10 Water-repellent and anti-reflective glass for vehicles 11 First convex surface of first bent glass sheet 12 First concave surface of first bent glass sheet 20 Thermoplastic Interlayer 30 Second bent glass sheet 51 Outer surface of laminated glass 52 Inner surface of laminated glass

Claims

1. A water-repellent and anti-reflection glass for a vehicle, comprising: a first glass plate; and a water-repellent and anti-reflection coating layer applied to one surface of the first glass plate, the water-repellent and anti-reflective coating layer has a single layer structure formed by curing a water-repellent and anti-reflective coating material, and raw materials of the water-repellent and anti-reflective coating material include a silicate ester, a phenyl silane, and a fluorine-based surfactant; The water contact angle of the water-repellent and anti-reflective coating layer is 110°-130°, the refractive index of the water-repellent and anti-reflective coating layer is 1.20-1.30, and the porosity of the water-repellent and anti-reflective coating layer is 40% or more; the water-repellent and anti-reflection coating layer is formed by hydrolysis polycondensation of silicate ester and phenylsilane, The silicate ester includes one or a combination of two or more of tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate, and tetrabutyl orthosilicate; The phenylsilane includes one or a combination of two or more of phenyltrimethoxysilane, phenyltriethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, and methylphenyldiethoxysilane.

2. 2. The water-repellent and anti-reflection glass for vehicles according to claim 1, wherein the thickness of the water-repellent and anti-reflection coating layer is 10 nm to 300 nm.

3. The thickness of the water-repellent and anti-reflection coating layer is 50 nm to 250 nm, and the refractive index of the water-repellent and anti-reflection coating layer is 1.21 to 1.

25.

2. The water-repellent and anti-reflective glass for vehicles according to claim 1.

4. 2. The water-repellent and anti-reflection glass for vehicles according to claim 1, wherein the refractive index of the water-repellent and anti-reflection coating layer is 1.23 to 1.

28.

5. The water-repellent and anti-reflective coating is obtained by mixing a first solution and a second solution, and the first solution contains 3% to 20% of silicate ester, 2% to 10% of phenylsilane, 0.01% to 0.5% of a fluorine-based surfactant, and a first organic solvent, and the second solution contains 0.5% to 5% of a catalyst and a second organic solvent, where the total mass of the raw materials of the water-repellent and anti-reflective coating is 100%.

2. The water-repellent and anti-reflective glass for vehicles according to claim 1.

6. 6. The water-repellent and anti-reflective glass for vehicles according to claim 5, wherein the first organic solvent and the second organic solvent have a total mass ratio of 65% to 90% in the raw materials of the water-repellent and anti-reflective coating.

7. the total mass ratio of the fluorosurfactant and the phenylsilane in the raw materials of the water-repellent and anti-reflective coating is 3% to 9%; And / or, the total mass ratio of the silicate ester and the phenylsilane in the raw materials of the water-repellent and anti-reflective coating is 5% to 15%.

2. The water-repellent and anti-reflective glass for vehicles according to claim 1.

8. The fluorine-based surfactant includes a nonionic fluorocarbon surfactant, and the solid content of the nonionic fluorocarbon surfactant is 50% or more.

2. The water-repellent and anti-reflective glass for vehicles according to claim 1.

9. the fluorine-based surfactant contains a perfluorooctyl polyether-based surfactant, and the water-solubility of the perfluorooctyl polyether-based surfactant is 90% or more; 2. The water-repellent and anti-reflective glass for vehicles according to claim 1.

10. the first organic solvent and / or the second organic solvent includes one or a combination of two or more of methanol, ethanol, propanol, butanol, and isopropanol; the catalyst includes an alkaline catalyst or an acidic catalyst, the alkaline catalyst including one or a combination of two or more of sodium hydroxide, potassium hydroxide, aqueous ammonia, and sodium bicarbonate; and the acidic catalyst including one or a combination of two or more of hydrochloric acid, nitric acid, and acetic acid; 6. The water-repellent and anti-reflective glass for vehicles according to claim 5.

11. a step of mixing and stirring 3%-20% silicate ester, 2%-10% phenylsilane, 0.01%-0.5% fluorine-based surfactant and a first organic solvent to obtain a first solution, and mixing and stirring 0.5%-5% catalyst and a second organic solvent, with the total mass of the raw materials of the water-repellent and anti-reflective coating being 100%; a step of mixing and stirring the second solution and the first solution to obtain the water-repellent and anti-reflective coating material; applying the water-repellent and anti-reflective coating material to one surface of a first glass plate, curing the coating material, and then forming a water-repellent and anti-reflective coating layer on the surface to obtain a water-repellent and anti-reflective glass for a vehicle; Including, 2. The method for manufacturing a water-repellent, anti-reflection glass for a vehicle according to claim 1.

12. mixing and stirring the second solution and the first solution includes a step of adding the second solution dropwise to the first solution at a dropping rate of 30-120 drops / minute while the first solution is being stirred; and / or the application method includes ultrasonic spraying, and in the ultrasonic spraying process, the ultrasonic frequency is 50kHz-120kHz, the amount of solution discharged during the spraying process is 0.5mL / min-10mL / min, and the spray moving speed is 300mm / sec-800mm / sec; 12. The method for manufacturing a water-repellent, anti-reflection glass for a vehicle according to claim 11.

13. The curing process includes a first curing and a second curing which are performed sequentially, the temperature of the first curing is 50°C-100°C, and the temperature of the second curing is 150°C-200°C; and / or the first curing is performed by an infrared lamp, and the first curing time is 10 min to 50 min, and the second curing is performed by an air-blowing drying box, and the second curing time is 30 min to 120 min; 12. The method for manufacturing a water-repellent, anti-reflection glass for a vehicle according to claim 11.

14. A water-repellent and anti-reflection laminated glass for vehicles, comprising the water-repellent and anti-reflection glass for vehicles according to claim 1, a second glass plate, and a thermoplastic intermediate layer, the thermoplastic interlayer is located between the first glass sheet and the second glass sheet; The water-repellent, anti-reflective laminated glass for vehicles has an outer surface and an inner surface, The water-repellent and anti-reflection coating layer is located on the outer surface or the inner surface of the water-repellent and anti-reflection laminated glass for vehicles. A water-repellent, anti-reflective laminated glass for vehicles.

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