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 in particular to a water-repellent, anti-reflective glass for vehicles, a manufacturing method thereof, and laminated glass. [Background technology]

[0003] With the progress of science and technology, new requirements for automotive glass products are emerging, not only for safety and wind protection, but also for comfort and functionality. In recent years, automotive glass that plays the roles of functionality, comfort and beauty has appeared one after another, such as heat shielding and ultraviolet shielding glass, water repellent glass, solar energy glass, anti-fog glass, HUD head-up display glass, colored glass, etc. Water repellent glass can effectively roll off water droplets in rainy weather, maintain good visibility for the driver, and is widely used in the automotive glass field. Anti-reflective coating layer can effectively reduce light reflection, so it has been used for many years in the optical field and as exhibition glass in malls, museums, etc., while it was later discovered that anti-reflective glass can effectively reduce the reflection of the automotive glass into the interior of the car at night, reducing the visual interference and fatigue of the driver, and has attracted more and more attention in the automotive glass field.

[0004] In the prior art, patents CN110776826A, CN109321131A, CN112094586A, CN111978861A, CN111925525A, CN112080716A, CN111892846A, CN107902918B, CN108027453A, CN108017290A, and CN108025962A disclose technologies related to water-repellent coating layers or anti-reflective glass, but most of the patents have separate water-repellent and anti-reflective functions. In addition, CN108025962A and CN108312655A improve the water-repellent properties of the coating layer by adding an anti-fingerprint coating layer separately to the anti-reflective coating layer, but there is no technology that can simultaneously provide water-repellent and anti-reflective functions 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 a laminated glass. In the present invention, a single layer of water-repellent, anti-reflective paint coating layer is sprayed onto the glass surface, thereby making it possible to provide the glass with both water-repellent and anti-reflective properties. [Means for solving the problem]

[0006] In order to achieve the above object, the present invention provides a water-repellent, anti-reflective glass for vehicles, comprising a first glass plate and a water-repellent, anti-reflective coating layer applied to one surface of the first 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 of the water-repellent, anti-reflective paint include silicate ester, phenyl silane, 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, in which 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-300 nm, for example, 50 nm-250 nm.

[0010] In some specific embodiments, the water repellent and anti-reflective 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-reflective 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 water-repellent and anti-reflective coating layer has a refractive index of 1.23-1.28.

[0014] In some specific embodiments, a flat surface abrasion test is performed using a flat surface 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 surface 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 taken as 100%, the first solution generally contains 3%-20% silicate ester, 2%-10% phenylsilane, 0.01%-0.5% fluorine-based surfactant 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 perfluorooctyl polyether surfactant may have a water-solubility of 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 includes a basic catalyst or an acid catalyst, where the basic catalyst may include one or a combination of two or more of sodium hydroxide, potassium hydroxide, aqueous ammonia, and sodium bicarbonate, and the acid catalyst may include 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, mixing and stirring 0.5%-5% catalyst and a second organic solvent to obtain a second solution, mixing and stirring the second solution and 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 the coating, and 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, with the total mass of the raw materials of the water-repellent and anti-reflective coating being 100%, 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 raw materials of the water-repellent and anti-reflective coating and the mass ratio of the second organic solvent in the raw materials of the water-repellent and anti-reflective coating is 65%-90%); mixing and stirring the second solution and the first solution to obtain the water-repellent and anti-reflective coating; applying the water-repellent and anti-reflective coating to one surface of a first glass plate, curing it, and then forming a water-repellent and anti-reflective coating layer on the surface to obtain 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 a first convex surface or a 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 includes dropping the second solution into the first solution while the first solution is being stirred, the dropping speed being controlled to be 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, in the ultrasonic spraying process, the ultrasonic frequency is 50 kHz-120 kHz, the outflow rate in the spraying process is 0.5 mL / min-10 mL / min, and the spray moving 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, where 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 of 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 of the second cure 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 water-repellent, anti-reflective glass for vehicles, a second glass plate, and a thermoplastic intermediate layer located between the first glass plate and the second glass plate in 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 located 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 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, or 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 an outer surface of the laminated glass, or the first concave surface of the first bent glass sheet is an inner surface of the laminated glass. Effect of the Invention

[0042] The beneficial effects of the present invention are as follows: 1. The present invention adds phenylsilane and a fluorine-based surfactant 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 having a single-layer water-repellent and anti-reflective coating layer obtained in this way has a water contact angle of 110°-130°, good water repellency, and the refractive index is effectively reduced to 1.20-1.30, providing good anti-reflective effect. 2. Compared with two-layer or multi-layer coating layers that have water-repellent or anti-reflective effects alone, the process conditions and technology adopted in the manufacturing method of water-repellent and anti-reflective glass for vehicles of the present invention are easy 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 glass for vehicles, and is expected to have a good future in the field of vehicle glass. [Brief description of the drawings]

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

[0044] In order to make the technical features, objectives and beneficial effects of the present invention more clearly understandable, 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 and anti-reflective glass for vehicles, comprising a first glass plate and a water-repellent and anti-reflective coating layer applied to one side 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 paint, and the raw materials of the water-repellent and anti-reflective paint include silicate ester, phenyl silane and a fluorine-based surfactant. The water-repellent and 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 and anti-reflective glass for vehicles of the present invention specifically includes a first curved glass plate 1 and a water-repellent and anti-reflective coating layer 2. The first curved glass plate 1 has a first convex surface 11 and a first concave surface 12. The water-repellent and anti-reflective coating layer 2 is applied to the first convex surface 11 or the first concave surface 12. The water-repellent and anti-reflective coating layer 2 has a single-layer structure formed by curing a water-repellent and anti-reflective paint. The raw materials of the water-repellent and anti-reflective paint include silicate ester, phenyl silane, and fluorine-based surfactant. The water contact angle of the water-repellent and anti-reflective coating layer 2 is 110°-130°, and the refractive index of the water-repellent and anti-reflective coating layer 2 is 1.20-1.30 (for example, 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 plate (e.g., a first curved glass plate), and a water-repellent and anti-reflective glass having both water repellency and a low refractive index can be obtained by simply combining a single-layer coating layer and a glass plate. In addition, in the conventional technology, it is difficult to control the refractive index of a single-layer coating layer to 1.25 or less, and a multi-layer coating layer is usually required to simultaneously obtain water repellency and a relatively low refractive index, but in some specific embodiments of the present invention, the single-layer water-repellent and anti-reflective coating layer has good water repellency and can reach a good refractive index of 1.21-1.25. Specifically, it may be 1.21, 1.22, 1.23, 1.24, 1.25, etc., which is close to the refractive index (1.23) of an ideal anti-reflective film.

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

[0049] In some specific embodiments, the water-repellent and anti-reflective coating layer 2 preferably has a water contact angle of 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, the contact angle after abrasion is 100° or more when the water-repellent and anti-reflective coating layer 2 of the water-repellent and anti-reflective glass for vehicles is placed facing upward and a 100-rotation flat abrasion test is performed at 2.45N×100r using a flat abrasion meter. Furthermore, the contact angle after abrasion may be 104° or more, 105° or more, 106° or more, 107° or more, 110° or more, 111° or more, 112° or more, 113° or more, 114° or more, 115° or more, 119° or more, etc. Furthermore, the contact angle after abrasion may be specific values ​​such as 104°, 105°, 106°, 107°, 110°, 111°, 112°, 113°, 114°, 115°, 119°, etc., and may be a range having any two of the above specific values ​​as endpoints.

[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 and a second solution. The first solution generally contains 3%-20% silicate ester, 2%-10% phenyl silane, 0.01%-0.5% fluorine-based surfactant and a first organic solvent, and the second solution contains 0.5%-5% catalyst and a second organic solvent, with the total mass of the raw material of the water-repellent and anti-reflective coating being 100%. The total mass ratio of the first organic solvent and the second organic solvent in the raw material of the water-repellent and anti-reflective coating is 65%-90%. By controlling the amount of the fluorine-based surfactant and the phenyl silane added in the coating, a single-layer water-repellent and anti-reflective coating layer having excellent water-repellent and anti-reflective effects is obtained, and the wear resistance of the single-layer water-repellent and anti-reflective coating layer meets the requirements for use of automotive glass. Preferably, the total mass ratio of the phenyl silane and the fluorine-based surfactant in the raw material of the water-repellent and anti-reflective coating 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 material is generally controlled to 5%-15%. If the amount of silicate ester and phenylsilane added is controlled within the above range, it is advantageous for the storage of the coating material and a coating layer with a good refractive index can be obtained.

[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. Since the phenyl group has water repellency, the water repellency of the coating layer formed from the coating can be significantly improved after the phenyl group is introduced into the coating material. Specifically, the phenylsilane may be phenylsiloxane. Compared with other types of molecular chains, the molecular chain of siloxane is more suitable as a carrier of the phenyl group to hybridize with the silicate ester in the glass substrate, and the phenylsiloxane can increase the bonding strength between the coating layer and the glass. Furthermore, the selection of phenylsilane having methoxy or ethoxy is advantageous for the occurrence of the spring-back phenomenon, and it is easy to prepare a coating layer with a low refractive index. Phenylsilane suppresses the shrinkage of the coating film during the drying process, improves the porosity, and reduces 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 the 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 more, 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, so that the fluorosurfactant can 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 a specific embodiment of the present invention, the amount of the fluorosurfactant used can be controlled within an appropriate range to avoid adversely affecting the refractive index of the coating layer, on the premise of improving the leveling and water repellency of the coating layer. In some specific embodiments, the mass ratio of the fluorosurfactant in the raw material 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 (manufactured by Xinnou Chemical Co., Ltd.), WE-D8950BR (manufactured by Xinnou Chemical Co., Ltd.), FCN-18 (Hangzhou Renshan Technology Co., Ltd.), etc.

[0062] In some specific embodiments, the catalyst includes a basic catalyst or an acid catalyst, where the basic catalyst may include one or a combination of two or more of sodium hydroxide, potassium hydroxide, aqueous ammonia, and sodium bicarbonate, and the acid catalyst may include 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 water-repellent and anti-reflective glass for vehicles, which 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, 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 raw material for the water-repellent and anti-reflective coating and the mass ratio of the second organic solvent in the raw material 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, curing the coating, and forming a water-repellent and anti-reflective coating layer on the surface to obtain the water-repellent and anti-reflective glass for vehicles. The above-mentioned manufacturing method utilizes a sol-gel process, in which phenylsilane is added and a hydrolysis polycondensation reaction occurs together with a silicate ester to form a coating layer having high water repellency.

[0064] In the present invention, when the first glass plate is a first curved glass plate, the above-mentioned manufacturing method typically involves applying a water-repellent and anti-reflective paint to the first convex surface or the first concave surface of the first curved glass plate, and forming a water-repellent and anti-reflective coating layer on the first convex surface or the first concave surface after curing, to obtain 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 silicic acid ester, the problem of precipitation caused by rapid hydrolysis polycondensation of the silicic acid ester due to a local concentration being too high can be effectively avoided. In some specific embodiments, mixing and stirring the second solution and the first solution includes dropping the second solution into the first solution while the first solution is being stirred. The dropping speed is usually controlled to 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, the coating layer of the nanometer order thickness can be prepared relatively precisely, and the glass can be applied to different curved shapes, and has great freedom in manufacturing the convex coating layer or the concave coating layer. In some specific embodiments, in the ultrasonic spraying process, the ultrasonic frequency is 50kHz-120kHz, the outflow amount in the spraying process is 0.5mL / min-10mL / min, and the spray moving speed is 300mm / sec-800mm / 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 by using an infrared lamp. The infrared curing method can maximize the pore structure of the coating layer, ensure that the coating layer has sufficient porosity, and at the same time, can achieve the effect of quickly drying the surface of the coating layer.

[0070] In some specific embodiments, the time of the first cure 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 of the second cure 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 water-repellent, anti-reflective glass for vehicles, a second glass plate, and a thermoplastic intermediate layer located between the first glass plate and the second glass plate. 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 located on the outer surface or the inner surface of the laminated glass.

[0074] As shown in Fig. 2 and Fig. 3, the water-repellent, anti-reflective laminated glass for vehicles of the present invention specifically includes a water-repellent, anti-reflective glass for vehicles 10, a second curved glass plate 30, and a thermoplastic intermediate layer 20. The thermoplastic intermediate layer 20 is located between the first curved glass plate 1 and the second curved glass plate 30 in the water-repellent, anti-reflective 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 plate is the outer surface 51 of the laminated glass, or the first concave surface 12 of the first curved glass plate 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 curved glass sheet 30 has a second convex surface and a second concave surface.

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

[0077] In Figure 3, the first curved glass plate 1 is the outer glass plate of the laminated glass, the second curved glass plate 30 is the inner glass plate of the laminated glass, the second concave surface of the second curved glass plate 30 is the inner surface 52 of the laminated glass, the first convex surface of the first curved glass plate 1 is the outer surface 51 of the laminated glass, and the water-repellent and anti-reflective 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 (manufactured by Zi Cheng International Trading Co., Ltd., a nonionic fluorocarbon surfactant), the first organic solvent and the second organic solvent are both absolute ethanol, the catalyst is ammonia water, 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 forming, and the ordinary glass sheet has a TL of 90%.

[0079] In the following examples and comparative examples, the first curing was performed at a temperature of 50°C-100°C using an infrared lamp, and the second curing was performed 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% of the first organic solvent were mixed and stirred to obtain a first solution, and 2% catalyst and 40.97% 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 / min to obtain a water-repellent and anti-reflective coating material. 3. The water-repellent and anti-reflective paint was applied to the first concave surface of the first curved glass plate, and the first curing and second curing were performed 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% of the first organic solvent were mixed and stirred to obtain a first solution, and 2% catalyst and 40.87% 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 / min to obtain a water-repellent and anti-reflective coating material. 3. The water-repellent and anti-reflective paint was applied to the first concave surface of the first curved glass plate, and the first curing and second curing were performed 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 / min to obtain a water-repellent and anti-reflective coating material. 3. The water-repellent and anti-reflective paint was applied to the first concave surface of the first curved glass plate, and the first curing and second curing were performed 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: 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 / min to obtain a water-repellent and anti-reflective coating material. 3. The water-repellent and anti-reflective paint was applied to the first concave surface of the first curved glass plate, and the first curing and second curing were performed 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 / min to obtain a water-repellent and anti-reflective coating material. 3. The water-repellent and anti-reflective paint was applied to the first concave surface of the first curved glass plate, and the first curing and second curing were performed 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 / min to obtain a water-repellent and anti-reflective coating material. 3. The water-repellent and anti-reflective paint was applied to the first concave surface of the first curved glass plate, and the first curing and second curing were performed 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. The total mass of the raw materials for the water-repellent and anti-reflective coating was taken as 100%, and 4% of silicate ester, 8% of phenylsilane, 0.03% 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 39.97% 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 / min to obtain a water-repellent and anti-reflective coating material. 3. The water-repellent and anti-reflective paint was applied to the first concave surface of the first curved glass plate, and the first curing and second curing were performed 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. The total mass of the raw materials for the water-repellent and anti-reflective coating was taken as 100%, and 4% of silicate ester, 8% 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 39.70% 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 / min to obtain a water-repellent and anti-reflective coating material. 3. The water-repellent and anti-reflective paint was applied to the first concave surface of the first curved glass plate, and the first curing and second curing were performed 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. The total mass of the raw materials for the water-repellent and anti-reflective coating was taken as 100%, and 4% of silicate ester, 8% of phenylsilane, 0.40% 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 41.60% 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 / min to obtain a water-repellent and anti-reflective coating material. 3. The water-repellent and anti-reflective paint was applied to the first concave surface of the first curved glass plate, and the first curing and second curing were performed 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 / min to obtain a water-repellent and anti-reflective coating material. 3. The water-repellent and anti-reflective paint was applied to the first concave surface of the first curved glass plate, and the first curing and second curing were performed 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 / min to obtain a water-repellent and anti-reflective coating material. 3. The water-repellent and anti-reflective paint was applied to the first concave surface of the first curved glass plate, and the first curing and second curing were performed 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 glass produced in Examples 1-6, no fluorine-based surfactant was added in the manufacturing process of the coating layer of the glass. Specifically, the manufacturing 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 / min 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 curing and second curing were sequentially performed 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 glass produced in Examples 1-6, the amount of phenylsilane added in the production process of the coating layer of the glass is less than 1%. Specifically, the production method of the glass of this comparative example includes the following: 1. With the total mass of the paint raw materials taken as 100%, 10% silicate ester, 0.7% phenylsilane, 0.03% fluorine-based surfactant and 43.50% first organic solvent were mixed and stirred to obtain a first solution, and 2% catalyst and 43.77% 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 / min 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 curing and second curing were sequentially performed to form a coating layer, thereby obtaining glass having a coating layer.

[0093] (Test Example 1) The glasses having the coating layers obtained in Comparative Examples 1 and 2 and the water-repellent and anti-reflective glasses for vehicles obtained in Examples 1 to 9 were subjected to tests 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 for the coating layer on the glass surface using a contact angle measuring device. 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 central wavelength of 550 nm was obtained. Abrasion resistance was measured using a flat surface abrasion tester. A glass sample was placed on the equipment with the coating layer facing up, and a flat surface abrasion test was performed 100 times at 2.45N x 100r, and the contact angle after abrasion was measured. Here, the contact angle 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 layer of Examples 1 to 11 was 1.23-1.28, and the porosity of the water-repellent and anti-reflective coating layer was in the range of 40%-60%, specifically 43%-54%. Measurement was performed using a flat surface abrasion tester, and the water-repellent and anti-reflective coating layer of the water-repellent and anti-reflective glass for vehicles was placed facing upward and subjected to a flat surface abrasion test of 100 rotations at 2.45N x 100r, and the contact angle after abrasion was 100° or more, and even 105° or more, and even 110° or more.

[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 has a significant effect on 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 paint also affected the porosity, but did not affect 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-reflective glass for vehicles comprising a first glass plate and a water-repellent and anti-reflective 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°, and the refractive index of the water repellent and anti-reflective coating layer is 1.20-1.

30. A water-repellent, anti-reflective glass for vehicles.

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

3. The thickness of the water-repellent and anti-reflective coating layer is 50 nm to 250 nm, and the refractive index of the water-repellent and anti-reflective 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-reflective glass for vehicles according to claim 1, wherein the refractive index of the water-repellent and anti-reflective coating layer is 1.23 to 1.

28.

5. 2. The water-repellent and anti-reflective glass for vehicles according to claim 1, wherein the water-repellent and anti-reflective coating layer has a porosity of 40% or more.

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

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

7. 7. The water-repellent and anti-reflective glass for vehicles according to claim 6, 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.

8. The water-repellent and anti-reflective glass for vehicles according to any one of claims 1 to 6, characterized in that 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%.

9. The water-repellent and anti-reflective glass for vehicles according to any one of claims 1 to 6, characterized in that 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%.

10. 7. The water-repellent and anti-reflective glass for vehicles according to claim 1, wherein the silicate ester comprises one or a combination of two or more of tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate, and tetrabutyl orthosilicate.

11. 7. The water-repellent and anti-reflective glass for vehicles according to claim 1, wherein the phenyl silane includes one or a combination of two or more of phenyl trimethoxy silane, phenyl triethoxy silane, methyl phenyl dimethoxy silane, diphenyl dimethoxy silane, and methyl phenyl diethoxy silane.

12. The fluorosurfactant contains a nonionic fluorocarbon surfactant, and the solid content of the nonionic fluorocarbon surfactant is 50% or more.

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

13. the fluorosurfactant contains a perfluorooctyl polyether surfactant, and the water solubility of the perfluorooctyl polyether surfactant is 90% or more; 7. The water-repellent and anti-reflective glass for vehicles according to claim 1.

14. 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 preferably includes one or a combination of two or more of sodium hydroxide, potassium hydroxide, ammonia water, and sodium hydrogen carbonate; and the acidic catalyst preferably includes one or a combination of two or more of hydrochloric acid, nitric acid, and acetic acid.

7. The water-repellent and anti-reflective glass for vehicles according to claim 6.

15. 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, taking the total mass of the raw materials of the water-repellent and anti-reflective coating as 100%, to obtain a second solution; 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 vehicles; Including, A method for producing a water-repellent, anti-reflective glass for a vehicle according to any one of claims 1 to 14.

16. 16. The method for manufacturing a water-repellent and anti-reflective glass for vehicles according to claim 15, wherein the mixing and stirring of the second solution and the first solution includes a step of dripping the second solution into the first solution at a dripping speed of 30 to 120 drops / min while the first solution is being stirred.

17. The coating method includes ultrasonic spraying, and in the ultrasonic spraying process, the ultrasonic frequency is 50kHz-120kHz, the outflow amount in the spraying process is 0.5mL / min-10mL / min, and the spray moving speed is 300mm / sec-800mm / sec; 16. The method for producing a water-repellent and anti-reflective glass for vehicles according to claim 15.

18. 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.

16. The method for producing a water-repellent and anti-reflective glass for vehicles according to claim 15.

19. The first curing is performed by an infrared lamp, and the first curing time is preferably 10 min-50 min. The second curing is performed by an air drying box, and the second curing time is preferably 30 min-120 min.

19. A method for producing a water-repellent and anti-reflective glass for vehicles according to claim 18.

20. A water-repellent, anti-reflective laminated glass for vehicles comprising the water-repellent, anti-reflective glass for vehicles according to any one of claims 1 to 14, 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-reflective coating layer is located on the outer surface or the inner surface of the water-repellent and anti-reflective laminated glass for vehicles. The present invention relates to a water-repellent, anti-reflective laminated glass for vehicles.

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