Glass with coating and preparation method thereof

Abstract

The invention relates to glass with a coating and a preparation method thereof. The glass with the coating comprises a glass substrate and the coating attached to the glass substrate, the coating comprises the following components in percentage by mass: 2%-12% of zirconium oxide nanoparticles, 28%-40% of silicon dioxide, 10%-20% of titanium dioxide and 30%-50% of lithium silicate. The coating has the advantages of high hardness, high heat resistance, good hydrophilicity and self-cleaning capability.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of glass coating, in particular to a glass with coating and a preparation method thereof. BACKGROUND

[0002] At present, the research and development of automobile sunroof glass mainly focuses on the integration of atmosphere lamp and the optimization of heat insulation performance, but the improvement in self-cleaning function and surface hardness is still insufficient, and the related research is relatively scarce.

[0003] Due to the particularity of high installation of the sunroof, it is difficult for the owner to observe the surface state at all times and clean the dirt in time, so that dust, bird droppings, oil stains and other pollutants are easy to deposit on the surface. Especially, the adherent stains formed by mixing these pollutants with rainwater can significantly reduce the clarity and light transmittance of the glass, directly affecting the viewing line of sight of the rear passengers.

[0004] In addition, whether during or after the rain, the remaining water droplets will cause further interference. In the rain, small volume raindrops are limited by their own characteristics and are difficult to slide off with the inertia of the vehicle, staying on the surface of the sunroof to form tiny droplets, causing light path scattering, leading to light refraction distortion and glare interference, causing visual blurring and glare sensitivity of the rear passengers, and other viewing obstacles; after the rain, the dirt wrapped in the raindrops will be exposed on the surface of the glass and difficult to completely remove, causing secondary interference to the visual experience of the rear passengers. If the pollutants accumulate for a long time, the performance of the integrated module will be weakened, and the function of the vehicle intelligent system will be challenged.

[0005] However, in response to the anti-fouling needs of the sunroof glass, most car companies have not adapted a hydrophilic anti-fouling coating to the outer side thereof, and the traditional coating also cannot meet the actual requirements. The hydrophilic anti-fouling coating needs to be applied to the outer side of the sunroof glass to effectively play a role, so it must have high hardness to resist the influence of the external harsh environment, and the surface hardness requirement is strict. At the same time, limited by the coating process, the current technology cannot be used for roll coating on the curved glass, and the coating needs to be coated before the glass is formed (i.e. before the curved surface is formed), and then it is formed at a high temperature of 600 DEG C, which puts strict requirements on the high temperature resistance of the coating. The performance and appearance of the coating after high temperature forming must meet the application requirements. SUMMARY

[0006] Therefore, it is necessary to provide a glass with a coating having high hardness, high heat resistance, self-cleaning ability and hydrophilicity, and a preparation method thereof.

[0007] A glass with a coating, comprising a glass substrate and a coating attached to the glass substrate; the coating comprises the following components by mass fraction:

[0008] 3-17% zirconium oxide nanoparticles, 28-40% silicon dioxide, 12-17% titanium dioxide, and 30-50% lithium silicate.

[0009] In some embodiments, the coating comprises the following components by mass fraction:

[0010] 5-7% zirconium oxide nanoparticles, 29-32% silicon dioxide, 13-15% titanium dioxide, and 45-50% lithium silicate.

[0011] In some embodiments, the zirconium oxide nanoparticles have a particle size of 10-30 nm.

[0012] In some embodiments, the silicon dioxide has a particle size of 10-20 nm.

[0013] In some embodiments, the titanium dioxide has a particle size of 10-20 nm.

[0014] In some embodiments, the coating has a pencil hardness of 7H or higher.

[0015] In some embodiments, the coating has a water contact angle of 20-40°.

[0016] In some embodiments, the coating has a visible light transmittance of 85-98%.

[0017] A method for preparing the glass with the coating according to any one of the preceding embodiments, comprising the following steps:

[0018] providing a glass substrate;

[0019] coating a coating material on the glass substrate, the coating material comprising the following components by mass fraction: 1-5% zirconium oxide nanoparticles, 40-45% silicon dioxide sol, 15-20% titanium dioxide sol, 8-15% lithium silicate, 20-25% solvent, and a base, the coating material having a pH value of 9-10;

[0020] subjecting the coating material to a curing treatment to form a coating.

[0021] In some embodiments, the method for preparing the coating material comprises the following steps:

[0022] dissolving the base in the solvent to obtain a basic solution;

[0023] dispersing the zirconium oxide nanoparticles in the basic solution to obtain a zirconium oxide dispersion;

[0024] adding the silicon dioxide sol and the lithium silicate to the zirconium oxide dispersion to obtain a mixture.

[0025] The titanium dioxide sol is added to the mixed solution to obtain the coating.

[0026] In some embodiments, the temperature of the solidification process is 400-600°C.

[0027] Compared with the conventional technology, the glass with coating and the preparation method thereof have the following beneficial effects:

[0028] In the glass with coating, the coating comprises zirconia nanoparticles, silica, titanium dioxide and lithium silicate, etc. The silica sol and lithium silicate can bond to form a three-dimensional cross-linked network, which serves as the skeleton structure of the coating, and endows the coating with basic mechanical strength and thermal stability. The zirconia nanoparticles have high hardness and high melting point, etc., and can significantly improve the hardness and high-temperature resistance of the coating. Moreover, the zirconia nanoparticles are filled in the gaps of the three-dimensional cross-linked network as a reinforcing phase, forming a SiO2-ZrO2-Li2SiO3 synergistic system. The synergistic cooperation of the zirconia nanoparticles and the silica can enhance the hardness and wear resistance of the coating. The synergistic cooperation of the zirconia nanoparticles and the lithium silicate glass phase can form a stable structure, so that the coating has no softening and peeling phenomenon at a high temperature of 600°C. The SiO2-ZrO2-Li2SiO3 synergistic system can also effectively improve the compactness of the coating. The titanium dioxide is bonded with the silicon hydroxyl of the silica through titanium hydroxyl, and a hierarchical rough surface is constructed. The titanium hydroxyl on the surface of the titanium dioxide can also form a hydrogen bond with water molecules, which is conducive to the continuous spreading of the water film, and the coating can achieve good hydrophilic performance without the traditional fluorosilane modified coating. At the same time, the titanium dioxide has photocatalytic activity, which can effectively degrade surface pollutants and improve the self-cleaning performance of the coating. DETAILED DESCRIPTION

[0029] In order to make the above objectives, features and advantages of the present application more apparent and easy to understand, the specific embodiments of the present application are described in detail below. In the following description, a large number of specific details are set forth in order to fully understand the present application. However, the present application can be implemented in many other ways different from those described herein, and those skilled in the art can make similar improvements without departing from the spirit of the present application, so the present application is not limited by the specific embodiments disclosed below.

[0030] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in the description of the application herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items.

[0031] The glass with coating of one embodiment includes a glass substrate and a coating attached to the glass substrate.

[0032] The coating includes the following components by mass fraction:

[0033] 3% to 17% of zirconium oxide nanoparticles, 28% to 40% of silicon dioxide, 12% to 17% of titanium dioxide, and 30% to 50% of lithium silicate.

[0034] The silicon dioxide and the lithium silicate can be bonded to form a three-dimensional crosslinked network as a skeleton structure of the coating, endowing the coating with basic mechanical strength and thermal stability.

[0035] The experimental results show that the addition of the silicon dioxide is also beneficial to improving the acid and alkali resistance and the anti-fouling performance of the coating.

[0036] The mass fraction of the silicon dioxide in the coating is 28% to 40%. Further, in some examples, the mass fraction of the silicon dioxide in the coating is 29% to 32%. For example, the mass fraction of the silicon dioxide in the coating is, for example, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, and the like.

[0037] In some examples, the particle size of the silicon dioxide is 10 nm to 20 nm.

[0038] The mass fraction of the lithium silicate in the coating is 30% to 50%. Further, in some examples, the mass fraction of the lithium silicate in the coating is 45% to 50%. For example, the mass fraction of the lithium silicate in the coating is, for example, 30%, 32%, 34%, 36%, 38%, 40%, 42%, 44%, 46%, 48%, 50%, and the like.

[0039] The coating contains zirconium oxide nanoparticles as a reinforcing phase in a specific ratio, which has the characteristics of high hardness and high melting point, and can significantly improve the hardness and high-temperature resistance of the coating. Moreover, the zirconium oxide nanoparticles as a reinforcing phase fill the gaps in the above-mentioned three-dimensional crosslinked network, forming a SiO2-ZrO2-Li2SiO3 synergistic system. The synergistic cooperation of zirconium oxide nanoparticles and silicon dioxide can enhance the hardness and wear resistance of the coating. The synergistic cooperation of zirconium oxide nanoparticles and lithium silicate glass phase can form a stable structure, so that the coating has no softening and peeling phenomenon at a high temperature of 600°C. The SiO2-ZrO2-Li2SiO3 synergistic system can also effectively improve the compactness of the coating.

[0040] The mass fraction of the zirconium oxide nanoparticles in the coating is 3% to 17%. If the amount of the zirconium oxide nanoparticles is too small, the reinforcing effect is limited. If the amount of the zirconium oxide nanoparticles is too large, the scattering effect of the nanoparticles is enhanced, which reduces the light transmittance of the coating and affects the view of the passengers if the coating is used as a vehicle window. In addition, the increase of the content of the zirconium oxide nanoparticles reduces the hydrophilicity of the coating. Further, in some examples, the mass fraction of the zirconium oxide nanoparticles in the coating is 5% to 7%. For example, the mass fraction of the zirconium oxide nanoparticles in the coating is 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, etc.

[0041] In some examples, the particle size of the zirconium oxide nanoparticles is 10 nm to 30 nm. Within the above particle size range, the zirconium oxide nanoparticles can be more uniformly filled in the gaps of the three-dimensional cross-linked network, and the performance of the coating can be more effectively improved.

[0042] The coating also contains titanium dioxide in a specific ratio. The titanium dioxide is bonded to the silicon hydroxyl group (-Si-OH) of the silicon dioxide through the titanium hydroxyl group (-Ti-OH) of the titanium dioxide, including chemical bonds and hydrogen bonds, to construct a hierarchical rough surface. The titanium hydroxyl group on the surface of the titanium dioxide can also form a hydrogen bond with water molecules, which is conducive to the continuous spreading of the water film, and the coating does not need to be modified by fluorosilane to achieve good hydrophilicity. At the same time, the titanium dioxide has photocatalytic activity and can effectively degrade surface pollutants to improve the self-cleaning performance of the coating.

[0043] In some examples, the mass fraction of the titanium dioxide in the coating is 12% to 17%. Further, in some examples, the mass fraction of the titanium dioxide in the coating is 13% to 15%. For example, the mass fraction of the titanium dioxide in the coating is 12%, 13%, 14%, 15%, 16%, 17%, etc.

[0044] In some examples, the particle size of the titanium dioxide is 10 nm to 20 nm.

[0045] In some examples, the coating includes the following components in the following mass fractions:

[0046] 5% to 7% of zirconium oxide nanoparticles, 29% to 32% of silicon dioxide, 13% to 15% of titanium dioxide, and 45% to 50% of lithium silicate.

[0047] The above examples further optimize the ranges of the components of the coating to achieve better comprehensive performance of the light transmittance, water contact, and hardness of the coating.

[0048] It can be understood that the coating can also add pigments and functional additives such as ultraviolet absorbers as needed, and is not limited to only containing the aforementioned components.

[0049] Further, the present application also provides a method for preparing the glass with the coating of any of the above examples, comprising the following steps:

[0050] providing a glass substrate;

[0051] coating a coating material on the glass substrate, the coating material comprising the following mass fractions of components: 1%~5% of zirconium oxide nanoparticles, 40%~45% of silica sol, 15%~20% of titanium dioxide sol, 8%~15% of lithium silicate, 20%~25% of solvent, and alkali, the pH value of the coating material being 9~10;

[0052] subjecting the coating material to a curing treatment to form a coating layer.

[0053] wherein the silica sol and the lithium silicate can undergo a polycondensation reaction under alkaline conditions to form a three-dimensional cross-linked network as a skeleton structure of the coating layer, endowing the coating layer with basic mechanical strength and thermal stability.

[0054] The experimental results show that the addition of the silica sol is also beneficial to improving the acid and alkali resistance and the anti-fouling performance of the coating layer.

[0055] The mass fraction of the silica sol in the coating material is 40%~45%. Further, in some examples, the mass fraction of the silica sol in the coating material is 42%~44%. Specifically, the mass fraction of the silica sol in the coating material is, for example, 40%, 40.5%, 41%, 41.5%, 42%, 42.5%, 43%, 43.5%, 44%, 44.5%, 45%, etc.

[0056] In some examples, the colloidal particle size of the silica sol is 10nm~20nm, and this particle size range is more beneficial to the uniform dispersion of the colloidal particles in the solvent.

[0057] In some examples, the solid content of the silica sol is 20%~30%. Specifically, the solid content of the silica sol is, for example, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, etc.

[0058] For example, the silica sol can be one or more of JN-30 (Tianjin Zhonglian Chemical Reagent Co., Ltd.), JN-40 (Dezhou Jinghuo Technology Glass Co., Ltd.), silica sol (Henan Longda New Material Technology Co., Ltd.), and YC-Sl01S (Shanghai Yingcheng New Material Co., Ltd.).

[0059] The mass fraction of lithium silicate in the coating is 8% to 15%. Further, in some examples, the mass fraction of lithium silicate in the coating is 10% to 13%. For example, the mass fraction of lithium silicate in the coating is 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15%, and the like.

[0060] The coating described above adds zirconium oxide nanoparticles as a reinforcing phase, which has the characteristics of high hardness and high melting point, and can significantly improve the hardness and high-temperature resistance of the coating. Moreover, the zirconium oxide nanoparticles are filled in the gaps of the three-dimensional cross-linked network as a reinforcing phase, forming a SiO2-ZrO2-Li2SiO3 synergistic system. The synergistic cooperation of zirconium oxide nanoparticles and silicon dioxide can enhance the hardness and wear resistance of the coating. The synergistic cooperation of zirconium oxide nanoparticles and lithium silicate glass phase can form a stable structure, so that the coating has no softening and peeling phenomenon at a high temperature of 600°C. The SiO2-ZrO2-Li2SiO3 synergistic system can also effectively improve the compactness of the coating.

[0061] The mass fraction of zirconium oxide nanoparticles in the coating is 1% to 5%. If the amount of zirconium oxide nanoparticles added is too small, the reinforcing effect is limited, and if the amount is too large, the scattering effect of the nanoparticles is enhanced, resulting in a decrease in the light transmittance of the coating, which will affect the passenger's view as a vehicle window coating. In addition, the increase in the content of zirconium oxide nanoparticles will also reduce the hydrophilic performance of the coating. Further, in some examples, the mass fraction of zirconium oxide nanoparticles in the coating is 2% to 4%. For example, the mass fraction of zirconium oxide nanoparticles in the coating is 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, and the like.

[0062] In some examples, the particle size of the zirconium oxide nanoparticles is 10 nm to 30 nm. Within the above particle size range, the zirconium oxide nanoparticles can be more uniformly filled in the gaps of the three-dimensional cross-linked network, and the performance of the coating can be more effectively improved.

[0063] The coating described above also adds a specific proportion of titanium dioxide sol. The titanium dioxide sol is bonded to the silicon hydroxyl group (-Si-OH) of the silica sol through titanium hydroxyl group (-Ti-OH), including chemical bonds and hydrogen bonds, to construct a hierarchical rough surface. The titanium hydroxyl group on the surface of the titanium dioxide sol can also form a hydrogen bond with water molecules, which is conducive to the continuous spreading of the water film, and the coating does not need to be modified by fluorosilane to achieve good hydrophilic performance. At the same time, titanium dioxide has photocatalytic activity, which can effectively degrade surface pollutants and improve the self-cleaning performance of the coating.

[0064] In some examples, the mass fraction of the titanium dioxide sol in the coating is 15% to 20%. Further, in some examples, the mass fraction of the titanium dioxide sol in the coating is 17% to 19%. For example, the mass fraction of the titanium dioxide sol in the coating is, for example, 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, 19.5%, 20%, etc.

[0065] In some examples, the particle size of the titanium dioxide sol is 10 nm to 20 nm, which is more conducive to uniform dispersion of the particles in the solvent.

[0066] In some examples, the solid content of the titanium dioxide sol is 15% to 20%. For example, the solid content of the titanium dioxide sol is, for example, 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18%, 19.5%, 19%, 19.5%, 20%, etc.

[0067] For example, the titanium dioxide sol can be, for example, one or more of MTI-2081 (Qianhai Jishengya (Shenzhen) Technology Co., Ltd.), XFI22 (Jiangsu Xianfeng Nanometer Material Technology Co., Ltd.), SSTA10W (Hangzhou Jisheng New Material Co., Ltd.), and Brofos-TiRs (Boros Nanometer Technology (Ningbo) Co., Ltd.).

[0068] The mass fraction of the solvent in the coating is 20% to 25%. Further, in some examples, the mass fraction of the solvent in the coating is 21% to 24%. For example, the mass fraction of the solvent in the coating is, for example, 20%, 20.5%, 21%, 21.5%, 22%, 22.5%, 23%, 23.5%, 24%, 24.5%, 25%, etc.

[0069] Optionally, the solvent can be, but is not limited to, one or more of water, ethanol, and isopropanol.

[0070] In some examples, the solvent includes ethanol with a mass fraction of 70% to 75% and water with a mass fraction of 25% to 30%. The strong polarity of the water maintains the stability of the number of hydroxyl groups on the particle surface, and the appropriate amount of ethanol can reduce the risk of excessive electrostatic repulsion, thereby inhibiting the agglomeration of nanoparticles caused by van der Waals forces. The above-mentioned solvent is conducive to more uniform dispersion of the nanoparticles.

[0071] Optionally, the base can be, but is not limited to, one or more of sodium hydroxide and potassium hydroxide.

[0072] The amount of the base added in the coating is to make the pH value of the coating 9-10, for example, 9, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10, etc.

[0073] It can be understood that the above-mentioned coating can also add pigments, functional additives such as ultraviolet absorbers, etc. according to needs, and is not limited to containing only the aforementioned ingredients.

[0074] The above-mentioned coating can adapt to the roll coating preparation process of the automobile glass coating, the coating is uniform without precipitation, the process performance is good, and the coating appearance is good.

[0075] In some examples, the preparation method of the above-mentioned coating comprises the following steps:

[0076] Step S1, dissolving the base in the solvent to obtain a basic solution.

[0077] Step S2, dispersing the zirconia nanoparticles in the basic solution to obtain a zirconia dispersion.

[0078] Step S3, adding the silica sol and lithium silicate into the zirconia dispersion to obtain a mixed solution.

[0079] Step S4, adding the titanium dioxide sol into the mixed solution to obtain the coating.

[0080] The preparation method of the above-mentioned coating adds the silica sol and lithium silicate into the basic zirconia dispersion, and the silica sol and lithium silicate can occur condensation reaction under the basic condition to form a three-dimensional cross-linked network. The zirconia nanoparticles as a reinforcing phase are filled in the gap of the above-mentioned three-dimensional cross-linked network to form a SiO2-ZrO2-Li2SiO3 synergistic system. The zirconia nanoparticles have characteristics such as high hardness and high melting point, which can significantly improve the hardness and high-temperature resistance of the coating. The synergistic cooperation of the zirconia nanoparticles and the silica can enhance the hardness and wear resistance of the coating. The synergistic cooperation of the zirconia nanoparticles and the lithium silicate glass phase can form a stable structure, so that the coating has no softening and peeling phenomenon at a high temperature of 600°C. The SiO2-ZrO2-Li2SiO3 synergistic system can also effectively improve the compactness of the coating.

[0081] The titanium dioxide sol is added into the mixed solution, the titanium dioxide sol is bonded with the silicon hydroxyl of the silica sol through titanium hydroxyl, including chemical bond and hydrogen bond, to construct a hierarchical rough surface, which is beneficial to improve the stability of the hydrophilic coating surface. The titanium hydroxyl on the surface of the titanium dioxide sol can also form a hydrogen bond with water molecules, which is beneficial to the continuous spreading of the water film, and the coating without fluorosilane modification can also achieve good hydrophilic performance. At the same time, the titanium dioxide has photocatalytic activity, which can effectively degrade surface pollutants and improve the self-cleaning performance of the coating.

[0082] The curing temperature of the coating is, for example, 400-600°C, and is specifically, for example, 400°C, 450°C, 500°C, 550°C, 600°C, etc. The curing of the coating can be achieved in the process of thermoforming the glass substrate, i.e., after the coating is applied to the glass substrate, the glass substrate with the coating is subjected to thermoforming, and the curing of the coating is simultaneously completed in the process of thermoforming the glass substrate.

[0083] The glass with the coating can be, but is not limited to, an automotive glass. The automotive glass can be, but is not limited to, a sunroof glass.

[0084] The present application has the following advantages:

[0085] (1) The coating has excellent high-temperature resistance, and can be subjected to high-temperature forming along with the glass substrate, for example, at a temperature of 400-600°C. In the process of thermoforming the glass, the coating can be cured, and there is no need for an additional curing process, thereby reducing the production process and improving the production efficiency. Moreover, the coating does not soften or peel off at a high temperature of 600°C.

[0086] (2) The coating has good hydrophilicity. The coating can stably maintain the hydrophilicity for more than 6 months. The good hydrophilicity is conducive to the continuous spreading of the water film, and avoids the formation of small droplets of water on the surface of the coating. The presence of small droplets of water can cause light scattering, resulting in refraction distortion and glare. For the sunroof glass of an automobile, this can seriously affect the visual clarity, and cause visual blurring and glare sensitivity of the passengers in the back row. The good hydrophilicity can avoid this problem. The water contact angle of the coating can be 20-40°.

[0087] (3) The coating has high hardness. The coating with high hardness is not easily damaged by external force. The pencil hardness of the coating can be more than 7H, for example, 7H-9H.

[0088] (4) The coating has good wear resistance, and can pass the Taber abrasion test. The good wear resistance makes the coating not easily damaged by external force.

[0089] (5) The coating has high transparency. The coating with high transparency can reduce the adverse effects of the automotive glass on the visual line of sight of the passengers. The visible light transmittance of the coating can be 85-98%.

[0090] (6) The coating has good acid and alkali resistance, and can resist the erosion of acidic rainwater, bird droppings, oil stains, etc.

[0091] (7) The coating has good adhesion to the glass substrate, and can achieve an adhesion grade of 0 in the grid test.

[0092] (8) The coating has a certain self-cleaning ability, can degrade surface pollutants, and reduces the adhesion of dirt to affect the clarity and light transmittance of the automobile glass and the function of the vehicle-mounted intelligent system.

[0093] The following specific examples are provided to further illustrate the present application, but the present application is not limited to the following specific examples. The following specific examples are provided to better further understand the present application, and do not limit the scope of protection of the present application.

[0094] Example 1

[0095] The preparation method of the coating of the present embodiment includes the following steps:

[0096] Step 1, preparation of an ethanol-water mixed alkaline solution: measure 30 ml of ethanol and 10 ml of deionized water, mix and stir, then add 0.67 ml of sodium hydroxide solution (0.1 mol / l) and continue to stir uniformly for 30 min, control the pH value to be 10, and prepare an ethanol-water mixed alkaline solution.

[0097] Step 2, weigh 1.35 g of zirconium oxide nanoparticles with a particle size distribution of 10 nm~30 nm, add the above ethanol-water mixed alkaline solution, and perform ultrasonic dispersion for 60 min to obtain a zirconium oxide dispersion.

[0098] Step 3, weigh 53.87 g of silica sol (JN-30 type from Tianjin Zhonglian Chemical Reagent Co., Ltd.) and 18.18 g of lithium silicate solution with a concentration of 98%, slowly add the above zirconium oxide dispersion while stirring, and continue to stir magnetically for 30 min to prepare a mixed solution.

[0099] Step 4, take 26.94 g of titanium dioxide sol (MTI-2081 type from Qianhai Jisengya (Shenzhen) Technology Co., Ltd.), slowly drop into the above mixed solution, and prepare a coating.

[0100] The coating formed by curing the coating of the present embodiment includes the following mass fractions of components:

[0101] 3.4% of zirconium oxide nanoparticles, 33.9% of silica, 16.9% of titanium dioxide, and 45.5% of lithium silicate, and the rest is alkali and other residual substances.

[0102] Example 2

[0103] The preparation method of the coating of the present embodiment includes the following steps:

[0104] Step 1, preparation of an ethanol-water mixed alkaline solution: 30 ml of ethanol and 10 ml of deionized water were measured, mixed and stirred, 0.67 ml of sodium hydroxide solution (0.1 mol / l) was added and uniform stirring was continued for 30 min, and the pH value was controlled at 10 to prepare the ethanol-water mixed alkaline solution.

[0105] Step 2, 2.69 g of zirconium oxide nanoparticles with a particle size distribution of 10 nm-30 nm were weighed and added to the above ethanol-water mixed alkaline solution and ultrasonic dispersion was carried out for 60 min to obtain a zirconium oxide dispersion.

[0106] Step 3, 56.57 g of silica sol (JN-40 type from Dezhou Jinghuo Technology Glass Co., Ltd.) and 16.84 g of lithium silicate solution with a concentration of 98% were weighed and slowly added to the above zirconium oxide dispersion while stirring, and magnetic stirring was continued for 30 min to prepare a mixed solution.

[0107] Step 4, 24.24 g of titanium dioxide sol (XFI22 type from Jiangsu Xianfeng Nanometer Material Technology Co., Ltd.) was slowly added dropwise to the above mixed solution to prepare a coating.

[0108] The coating formed by curing the coating of this embodiment includes the following components by mass fraction:

[0109] 5.6% of zirconium oxide nanoparticles, 29.6% of silica, 14.1% of titanium dioxide, and 50.0% of lithium silicate, and the rest is alkali and other residual substances.

[0110] Example 3

[0111] The preparation method of the coating of this embodiment includes the following steps:

[0112] Step 1, preparation of an ethanol-water mixed alkaline solution: 30 ml of ethanol and 10 ml of deionized water were measured, mixed and stirred, 0.67 ml of sodium hydroxide solution (0.1 mol / l) was added and uniform stirring was continued for 30 min, and the pH value was controlled at 10 to prepare the ethanol-water mixed alkaline solution.

[0113] Step 2, 6.73 g of zirconium oxide nanoparticles with a particle size distribution of 10 nm-30 nm were weighed and added to the above ethanol-water mixed alkaline solution and ultrasonic dispersion was carried out for 60 min to obtain a zirconium oxide dispersion.

[0114] Step 3, 60.61 g of silica sol (YC-Sl01S type from Shanghai Yingcheng New Material Co., Ltd.) and 12.79 g of lithium silicate solution with a concentration of 98% were weighed and slowly added to the above zirconium oxide dispersion while stirring, and magnetic stirring was continued for 30 min to prepare a mixed solution.

[0115] Step 4, 20.20 g of titanium dioxide sol (Hangzhou Jibin New Material SSTA10W) was slowly added into the above mixture to prepare the coating.

[0116] The coating formed by curing the coating of this example comprises the following components by mass fraction:

[0117] 16.9% of zirconium oxide nanoparticles, 38.1% of silicon dioxide, 12.5% of titanium dioxide, and 32.2% of lithium silicate, with the rest being alkali and other residual substances.

[0118] Comparative Example 1

[0119] The difference between this comparative example and Example 1 is only that Step 2 is not performed, i.e., no zirconium oxide nanoparticles are added.

[0120] Comparative Example 2

[0121] The difference between this comparative example and Example 2 is only that in Step 3, no silicon dioxide sol is added.

[0122] Comparative Example 3

[0123] The difference between this comparative example and Example 3 is only that in Step 3, no lithium silicate is added.

[0124] Comparative Example 4

[0125] The difference between this comparative example and Example 3 is only that Step 4 is not performed, i.e., no titanium dioxide sol is added.

[0126] The coatings of the above examples and comparative examples were applied to automobile glass. Specifically, the preparation method of the automobile glass comprises the following steps:

[0127] Step 1, a glass substrate was provided, which was a common white glass with a size of 300 mm x 300 mm. The glass substrate was rinsed with ethanol and deionized water in turn, and then wiped dry with a dust-free cloth.

[0128] Step 2, the air side of the glass substrate was determined using a tin side meter. The air side of the glass substrate was pretreated using a plasma surface treatment device.

[0129] Step 3, the glass substrate after plasma pretreatment was placed on a roll coating machine. A coating rod with a specification of 10 pm was fixed at the front end of the glass substrate, and the prepared coating was uniformly added to the front end of the coating rod using a dropper. The parameters of the coating machine were set as follows: coating stroke was 250 mm, coating speed was 200 cm / min, and bottom plate heating temperature was 23.0°C. Then, coating was performed.

[0130] Step 4: The coated glass was transferred to a drying oven and heat treated at 180°C for 30 min. Then it was transferred to a muffle furnace for high temperature curing. The temperature ramping rate was set at 10°C / min, and the temperature was raised to 600°C in 60 min, and the holding time was 2 min. The sample was removed from the muffle furnace when the temperature dropped to 100°C, and a coating layer was formed on the glass substrate.

[0131] The performance of the coating layer prepared from the coating of the above examples and comparative examples was tested, including pencil hardness, water contact angle, light transmittance, Taber abrasion test, grid test, high temperature test, dirt resistance test, and acid and alkali resistance, etc. The test methods are as follows.

[0132] The test method of pencil hardness: the sample was fixed on the sample table of the hardness tester with the coating surface upward. The pencil clamp was adjusted to form a 45° angle between the pencil tip and the coating layer, and a standard pressure (usually 250g) was applied through the weight, and the pencil was slowly drawn along the coating surface at a constant speed for 3 cm. When a certain hardness pencil was damaged for 3 times or more in 5 times of drawing, the hardness of the pencil was the pencil hardness of the coating layer.

[0133] The test method of water contact angle: the surface of the sample was cleaned with ethanol to ensure that there was no oil or dust interference. The test liquid (ultra-pure water) was selected, 5 μL of liquid was sucked and the needle position was calibrated, the liquid drop was vertically dropped to the center of the sample, and the light source was adjusted by the instrument to clearly see the outline of the liquid drop. Then the automatic liquid drop release function was started, and the image was collected after the liquid drop was stable for 5 s, and the software would automatically fit the liquid drop outline based on the Young-Laplace equation and calculate the contact angle.

[0134] The test method of light transmittance: first, turn on the instrument power and preheat for 30 min to stabilize the light source, then take out the blackboard for calibration to ensure that the instrument is in the reference state. After selecting the "measurement" button in the main menu, the sample is fixed on the test port to ensure that the sample surface is bubble-free and tightly attached to the test port. After the instrument prompts, press the measurement key to trigger data collection, and the instrument automatically calculates the light transmittance. Repeat the measurement 3 times and take the average value.

[0135] The test method of Taber abrasion test: first, prepare a sample with a size of 100 mm x 100 mm, ensure that the surface is flat and free of scratches, and then fix the sample on the rotating disc with double-sided tape. Then select a matching material sand wheel for pre-grinding verification, install it to the balance arm and load the weight (250g) to set the load, adjust the instrument speed and set the test number of revolutions to 1000, start the equipment, and the abrasive wheel contacts and rubs the sample. During the process, the dust collector is used to remove debris, and the machine automatically stops when the preset number of revolutions is reached. The change of water contact angle before and after the sample test is less than 10°, which is qualified, otherwise it is unqualified.

[0136] The test method for adhesion (cross-hatch test): first, select a cross-hatch knife with a tooth spacing of 1 mm according to the test standard, fix the sample on a hard and flat substrate, ensure that the surface is free of oil stains, scratches and dry, hold the cross-hatch handle, cut at a vertical angle with uniform pressure and at a speed of 50 mm / s to penetrate the coating but not damage the substrate, and cover the cross-hatch area with a translucent pressure-sensitive adhesive tape, tear off the tape at an angle of about 60° within 5 minutes and observe the residual coating, and evaluate the adhesion grade according to the six-level (0, 1, 2, 3, 4 and 5) standard, for reference to the national standard GB / T 9286-2021 "Cross-hatch test for pigments and varnishes".

[0137] The test method for high temperature test: the sample was placed in a muffle furnace for high temperature test. The heating rate of the muffle furnace was 10℃ / min, and the temperature was raised to 600℃ in 60 min, and the holding time was 2 min, and the temperature began to decrease. When the muffle furnace was cooled to 100℃, the sample was taken out, and the appearance defects such as cracking and fogging of the sample were observed.

[0138] The test method for dirt resistance test: after the sample was placed outdoors for seven days, the surface of the sample was washed with deionized water, and then wiped clean with a dust-free cloth, and then observed whether there was dirt remaining on the surface of the sample by optical microscopy.

[0139] The test method for acid and alkali resistance: 0.1 mol / l H2SO4 solution and NaOH solution were prepared, and the sample was placed in the above solution, and at least half of the sample was immersed in the solution. After soaking at room temperature for 1 h, the sample was washed with deionized water, and the water film effect of the sample was observed to determine whether the hydrophilic property of the coating was invalid. If the hydrophilic property is not invalid, the acid and alkali resistance is qualified, otherwise it is unqualified.

[0140] The test method for water film effect test: the sample was placed outdoors and left for 6 months, and then the surface was washed and covered with deionized water. Within 15 s, if the water film on the surface of the sample does not shrink, the water film effect test is qualified, otherwise it is unqualified.

[0141] The test results are shown in Table 1.

[0142] Table 1

[0143]

[0144] From the test results of the light transmittance in Table 1, the light transmittance of Example 1, Example 2 and Example 3 is 93.50%, 92.00% and 88.30% respectively. The light transmittance of Example 1 is the highest, and that of Example 2 and Example 3 decreases in turn. This is mainly related to the amount of zirconium oxide nanoparticles added. With the increase of the amount of zirconium oxide nanoparticles added, the scattering effect of the nanoparticles increases, resulting in a decrease in the light transmittance of the coating.

[0145] From the test results of water contact angle in Table 1, the water contact angles of Example 1, Example 2 and Example 3 are 28.45°, 30.78° and 35.69° respectively. Comparative Example 1 does not add zirconia nanoparticles, and its water contact angle is 15.37°, which is lower than that of Example 1, indicating that the addition of zirconia nanoparticles can reduce the hydrophilic property, and the increase of the amount of addition reduces the hydrophilic property. This is mainly because the combination of silica sol and titanium dioxide sol is more conducive to the exposure of hydrophilic groups. The water contact angles of Comparative Examples 2, 3 and 4 are 41.89°, 47.02° and 46.79° respectively. The hydrophilic properties of Examples 1-3 are better than those of Comparative Examples 2-4. It is indicated that the application reduces the adverse effect of zirconia nanoparticles on the hydrophilic property of the coating through multi-component cooperation.

[0146] From the test results of pencil hardness in Table 1, Examples 1-3 obtain high-hardness coatings, and the hardness is 9H. Comparative Example 1 does not add zirconia nanoparticles, and its hardness is 4H, indicating that zirconia nanoparticles effectively improve the hardness of the coating. Although Comparative Examples 2-4 add zirconia nanoparticles, their hardness is 3H-5H, which is significantly lower than that of Examples 1-3, indicating that zirconia nanoparticles and other components in the application produce a synergistic effect, which makes the hardness of the coating jump.

[0147] From the test results of Taber abrasion test in Table 1, Examples 1-3 are qualified, and Comparative Examples 1-3 are unqualified, and Comparative Example 4 is qualified. It is indicated that any one of zirconia nanoparticles, silica sol and lithium silicate is missing, and high wear resistance cannot be obtained. The application forms a three-dimensional cross-linked network by the reaction of silica sol and lithium silicate under alkaline conditions, and fills zirconia nanoparticles as a reinforcing phase in the gap of the three-dimensional cross-linked network, forming a SiO2-ZrO2-Li2SiO3 synergistic system, which improves the compactness of the structure and effectively enhances the wear resistance of the coating.

[0148] From the test results of cross-hatch test in Table 1, the adhesion levels of Examples 1-3 are all 0 level, and Comparative Examples 1-4 are 1 level or 2 level, indicating that the synergistic cooperation of zirconia nanoparticles, silica sol, lithium silicate and titanium dioxide sol in the application enhances the adhesion performance of the coating on the glass substrate.

[0149] From the test results of high temperature test in Table 1, the coatings of Examples 1-3 are normal at 600℃, while the coatings of Comparative Examples 1-3 crack, indicating that the high temperature resistance of Examples 1-3 is better, which is due to the synergistic cooperation of zirconia nanoparticles and lithium silicate glass phase, which can form a stable structure.

[0150] As can be seen from the test results of the acid and alkali resistance test in Table 1, Examples 1-3 and Comparative Examples 1, 3 and 4 are qualified, while Comparative Example 2 is unqualified. This is because the formula of Comparative Example 2 omits the silica sol, resulting in a decrease in acid and alkali resistance. Zirconia itself also has certain acid and alkali resistance, but needs to be combined with other ingredients to achieve better results.

[0151] As can be seen from the test results of the dirt resistance test in Table 1, Examples 1-3 and Comparative Examples 1, 3 and 4 are qualified, while Comparative Example 2 is unqualified. This shows that the addition of silica sol plays a key role in improving the dirt resistance of the coating.

[0152] As can be seen from the test results of the water film effect test in Table 1, Examples 1-3 and Comparative Example 1 are qualified, while Comparative Examples 2-4 are unqualified. In Comparative Examples 2-4, the main reason is that the main component that provides hydroxyl groups such as silica sol or titanium dioxide sol is lost, resulting in a decrease in the number of hydrophilic groups and an inability to obtain stronger hydrophilic properties.

[0153] The technical features of the above-described embodiments can be combined in any manner. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described, but as long as the combinations of the technical features do not contradict each other, they should be considered within the scope of the present disclosure.

[0154] The above-described embodiments only express several implementation manners of the present application, and the description is relatively specific and detailed, but it should not be understood as a limitation on the scope of the patent application. It should be noted that for ordinary skilled persons in the art, without departing from the concept of the present application, a number of modifications and improvements can be made, which are within the scope of the present application. Therefore, the patent protection scope of the present application should be subject to the appended claims, and the description can be used to explain the content of the claims.

Claims

1. A glass having a coating, characterized in that, The glass substrate and a coating attached to the glass substrate; the coating comprises the following components by mass fraction: 3-17% of zirconium oxide nanoparticles, 28-40% of silicon dioxide, 12-17% of titanium dioxide, and 30-50% of lithium silicate.

2. The glass having a coating according to claim 1, wherein, The coating comprises the following components by mass fraction: 5-7% of zirconium oxide nanoparticles, 29-32% of silicon dioxide, 13-15% of titanium dioxide, and 45-50% of lithium silicate.

3. The glass having a coating of claim 1, wherein, The particle size of the zirconium oxide nanoparticles is 10-30 nm.

4. The glass having a coating of claim 1, wherein, The particle size of the silicon dioxide is 10-20 nm.

5. The glass having a coating of claim 1, wherein, The particle size of the titanium dioxide is 10-20 nm.

6. The glass having a coating according to any one of claims 1 to 5, wherein, The pencil hardness of the coating is 7H or more.

7. The glass having a coating according to any one of claims 1 to 5, wherein The water contact angle of the coating is 20-40°.

8. The glass having a coating according to any one of claims 1 to 5, wherein, The visible light transmittance of the coating is 85-98%.

9. A method of producing the glass with a coating according to any one of claims 1 to 8, characterized by, The method comprises the following steps: Providing a glass substrate; Coating a coating on the glass substrate, the coating comprising the following components by mass fraction: 1-5% of zirconium oxide nanoparticles, 40-45% of silicon dioxide sol, 15-20% of titanium dioxide sol, 8-15% of lithium silicate, 20-25% of solvent, and alkali, the pH value of the coating being 9-10; Curing the coating to form a coating.

10. The production method according to claim 9, wherein The preparation method of the coating comprises the following steps: Dissolving the alkali in the solvent to obtain an alkaline solution; Dispersing the zirconium oxide nanoparticles in the alkaline solution to obtain a zirconium oxide dispersion; Adding the silicon dioxide sol and the lithium silicate to the zirconium oxide dispersion to obtain a mixture; Adding the titanium dioxide sol to the mixture to obtain the coating.

11. The production method according to claim 10, wherein The curing temperature is 400-600°C.

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