A high-wear-resistant and high-hardness anti-glare coating for glass, and its preparation method and application

Abstract

This invention relates to the field of anti-glare coating technology, particularly to IPC C09D1, and more specifically to a high-wear-resistant, high-hardness glass anti-glare coating, its preparation method, and its application. The first aspect of this invention provides a high-wear-resistant glass anti-glare coating, the raw materials of which are 10-25 parts of a precursor, 1-10 parts of an additive, 1-5 parts of a catalyst, 5-20 parts of an inorganic solvent, and 50-80 parts of an organic solvent. This invention uses a sol-gel method to prepare the anti-glare optical coating liquid, which is simple, easy to operate, and uses environmentally friendly and low-cost materials. A high-precision spraying process is used to prepare the coating, resulting in an anti-glare coating with high wear resistance and high hardness.

Description

Technical Field

[0001] This invention relates to the field of anti-glare coating technology, particularly to IPC C09D1, and more specifically to a high wear-resistant and high-hardness glass anti-glare coating, its preparation method, and its application. Background Technology

[0002] Currently, the commonly used methods for manufacturing anti-glare glass in the market include etching, spraying, and film lamination. Compared to other manufacturing techniques, etching produces anti-glare glass with better mechanical properties and a longer service life, in addition to its superior anti-glare effect. However, the hydrofluoric acid used in the etching process is highly polluting to the environment, and the large-scale use of hydrofluoric acid and the subsequent wastewater treatment keep production costs high. Film lamination is also an effective method for providing anti-glare, but the anti-glare film has poor abrasion resistance, only reaching 500-700 cycles under a 1kg load abrasion test, far below the requirements for outdoor displays, and its manufacturing process is complex.

[0003] Existing patent CN201811486609.9 discloses a method for preparing a high-strength anti-glare coating. The formula includes seashells, methyl methacrylate, γ-methacryloyloxypropyltrimethoxysilane, ethanol solution, nano titanium dioxide, etc., which improves the hardness and substrate adhesion of the anti-glare coating. However, the haze value is too high, and the anti-glare effect and wear resistance need to be improved.

[0004] Existing patent CN202210527965.0 discloses a high-transparency adaptive emissivity modulation coating and its preparation method and application. It mainly consists of vanadium dioxide powder and has a certain "warm in winter and cool in summer" effect, but its wear resistance is questionable.

[0005] Existing patent CN112940489 A discloses an anti-glare self-healing mobile phone screen protector. The raw materials include self-healing polyurethane elastomer, low-density polyethylene, PMMA, nano-silica, ultraviolet absorber, surfactant, antioxidant, flame retardant, crosslinking agent, and leveling agent. It has excellent anti-glare and self-healing capabilities, but surface wear resistance, adhesion, and film hardness are not mentioned due to the large proportion of organic components in the material itself.

[0006] Existing patent CN105295719 B discloses a method for processing a wear-resistant anti-glare glass spray liquid and an anti-glare coating. The description of this patent is relatively simple and does not mention the hardness test results of the product. Due to the difference in the properties of the raw materials themselves, and the high amount of spraying required by this patent, which is about 4 times the amount of spraying required by this patent technology, the wear resistance is also slightly insufficient compared to the results of this patent technology.

[0007] Existing patent CN 110937820 A discloses an ultra-wear-resistant, anti-fingerprint, and anti-glare coating and its preparation method. The coating includes AG spray paint containing silica particles of 350nm-480nm. The particles of different sizes work together to produce an anti-glare effect. The thickness of the film is about 30-40μm, and a high thickness is required to achieve the corresponding anti-glare and wear-resistant effects. The raw materials are more expensive, resulting in higher costs.

[0008] Existing patent CN 111892306 A discloses a method for preparing anti-glare AG glass, which uses a vacuum evaporation method of barium fluoride. This method has a complex operation process, and the product test results do not mention its wear resistance. The results are open to discussion.

[0009] Existing patent CN 112327394 A discloses a high wear-resistant, low flash point anti-glare film with three layers containing anti-glare particles of different sizes. However, the particles contained in the coating are all organic particles (resin), resulting in high haze and failing to meet the automotive use standard (3-8). Furthermore, it has low pencil hardness, only 3H.

[0010] Spraying technology, as an efficient and low-cost anti-glare preparation technology, has also been overlooked due to poor adhesion. However, research has revealed that the chemical structure of the anti-glare coating formulation and its preparation process have a significant impact on its adhesion effect. Therefore, a high-wear-resistant anti-glare coating material and its spraying and preparation methods are proposed. Summary of the Invention

[0011] To address the problems in the prior art, the first aspect of this invention provides a high wear-resistant glass anti-glare coating, the raw materials for which are precursors, additives, catalysts, inorganic solvents, and organic solvents.

[0012] Preferably, the raw materials for preparation, by weight, consist of 10-25 parts of precursor, 1-10 parts of additive, 1-5 parts of catalyst, 5-20 parts of inorganic solvent and 50-80 parts of organic solvent.

[0013] Preferably, the precursor is one or more of tetraethyl silicate and tetramethyl silicate.

[0014] Preferably, the precursor is 10 to 20 parts by weight of tetraethyl silicate.

[0015] Preferably, the catalyst is 2 to 4 parts by weight.

[0016] Preferably, the weight ratio of the precursor to the catalyst is 10:2.

[0017] Preferably, the additive is diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, acetylacetone, ethyl acetate, and butyl acetate.

[0018] Preferably, the weight ratio of ethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and ethyl acetate is (3-8):(2-5):(1-2); more preferably, it is 3:3:2.

[0019] Preferably, the weight ratio of acetylacetone, ethyl acetate and butyl acetate is (1-2):(1-2):1; more preferably, it is 1:2:1.

[0020] Preferably, the weight ratio of ethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, ethyl acetate, butyl acetate, and acetylacetone is (3-8):(2-5):(1-2):(1-2):1; more preferably, it is 3:3:2:1:1.

[0021] In this invention, the interaction between the additives and the sol solution formed by tetraethyl orthosilicate is achieved by adding ethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, ethyl acetate, butyl acetate, and acetylacetone in a weight ratio of (3-8):(2-5):(1-2):(1-2):1. This adjusts the physical properties of the anti-glare optical coating solution, thereby controlling the viscosity and volatility of the sol solution. The applicant has discovered that adding ethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, ethyl acetate, butyl acetate, and acetylacetone can alter the physical properties of the sol solution, controlling the microstructure formed on the glass surface. This allows the sol to be uniformly dispersed and sprayed onto the glass substrate, forming an anti-glare coating with small particle size and low roughness. The sol forms chemical bonds with the abundant hydroxyl groups and silanes on the glass surface, achieving good bonding and resulting in excellent adhesion and wear resistance. Because the material is a pure inorganic material after high-temperature curing, the film layer has high hardness.

[0022] Preferably, the catalyst is one or more of hydrochloric acid, nitric acid, and acetic acid; more preferably, it is nitric acid.

[0023] Preferably, the nitric acid is a 68 wt% aqueous solution of nitric acid.

[0024] Preferably, the organic solvent is organic solvent 1 and organic solvent 2.

[0025] Preferably, organic solvent 1 and organic solvent 2 are one or more of methanol, ethanol, n-propanol, isopropanol, and n-butanol; more preferably, they are ethanol and n-butanol.

[0026] Preferably, the weight ratio of ethanol to n-butanol in the organic solvent 1 is 1:2.

[0027] Preferably, the inorganic solvent is deionized water.

[0028] This invention, by adding 10-25 parts of a precursor, 1-10 parts of an additive, 1-5 parts of a catalyst, 5-20 parts of an inorganic solvent, and 50-80 parts of an organic solvent, especially when the precursor is 10-20 parts of tetraethyl or tetraethyl silicate, can control the solid content of the compound in the anti-glare optical coating solution while improving the hardness and abrasion resistance of the anti-glare coating within the specific spraying parameters of this application. The inventors hypothesize that controlling the amount of the precursor can control the solid content of the compound in the sol solution within a suitable range. If the solid content of the compound is too low, the optical parameters of the coating are too low and do not meet application requirements, necessitating multiple repeated sprayings on a single plane. However, multiple repeated sprayings will form multiple overlapping layers, thereby reducing the abrasion resistance of the anti-glare coating. If the solid content is too high, overlapping layers are easily formed at the edges during spraying, and the coating is also prone to being too thick, resulting in poor film thickness uniformity and reducing the abrasion resistance of the anti-glare coating. Therefore, it is necessary to control the appropriate content of the precursor.

[0029] A second aspect of this invention provides a method for preparing a highly wear-resistant anti-glare coating for glass, the method being a sol-gel method, comprising the following steps:

[0030] S1 dissolves nitric acid in an inorganic solvent and mixes it with stirring to form solution 1;

[0031] S2: Mix the precursor and organic solvent 1 at a weight ratio of 1:1 to obtain solution 2;

[0032] S3: Add solution 1 to solution 2, which is being stirred continuously, at a constant speed. After the addition is complete, stir at a constant temperature for 60 minutes to obtain a sol solution.

[0033] S4: After the sol solution cools to room temperature, add organic solvent 2 and additives in sequence, stir and mix evenly to obtain anti-glare optical coating solution;

[0034] S5: Cleaning glass substrate;

[0035] S6: Set the temperature to 40-60℃ to preheat the glass substrate; use high-precision spraying equipment, set specific spraying parameters, and spray anti-glare optical coating liquid onto the clean glass surface.

[0036] S7: After high-temperature curing, an anti-glare optical coating with high wear resistance and high hardness is obtained.

[0037] Preferably, the specific steps for cleaning the glass substrate in S4 are as follows: using an alkaline cleaning agent with a mass fraction of 15%, controlling the temperature at 35-45°C, ultrasonically cleaning the glass substrate at a constant temperature, then rinsing off any residual cleaning agent with clean water and drying it to maintain a high level of cleanliness.

[0038] Preferably, the high temperature in S6 is 200-250°C; more preferably, it is 200°C.

[0039] Preferably, the spraying parameters are: air pressure 4-7 bar, flow rate 0.1-0.2 cc / s, spray gun moving speed 20-140 cm / s, and spray gun height 10-30 cm.

[0040] This invention employs a sol-gel method to prepare an anti-glare optical coating solution. Tetraethyl silicate is decomposed into silica sol under the action of a catalyst. Through high-precision spraying combined with high temperature, a functional nanoscale crater-shaped particle coating is formed on the surface of a glass substrate. The coating achieves excellent adhesion to the glass substrate through chemical bonds. After high-temperature curing, the coating itself is a pure inorganic material, providing excellent wear resistance and hardness for the anti-glare coating, and is environmentally friendly. The spraying process is also easy to control. The inventors have creatively discovered that using the sol-gel method to prepare silica sol results in a sol solution with good uniformity, uniform dispersion at the molecular level, accelerated reaction rate, and lower reaction temperature.

[0041] The wear resistance of high wear-resistant glass anti-glare coatings prepared in the prior art is usually determined by the coating thickness, surface roughness, coating material itself, and its bonding with the substrate. This invention sets the spraying parameters as follows: air pressure 4-7 bar, flow rate 0.1-0.2 cc / s, spray gun moving speed 20-140 cm / s, and spray gun height 10-30 cm, controlling the thickness of the high wear-resistant glass anti-glare coating (nanoscale) to form a surface with low roughness. In addition, the characteristics of the film layer as a pure inorganic material and its good bonding with the substrate provide high wear resistance and high hardness.

[0042] The third aspect of this invention provides an application of a high wear-resistant glass anti-glare coating, which is applied to automotive optical glass.

[0043] Beneficial effects

[0044] 1. This invention uses the sol-gel method to prepare an anti-glare optical coating liquid. The precursor (tetraethyl silicate) is decomposed into silica sol under the action of a catalyst. An anti-glare coating is prepared through a specific high-precision spraying process, which has excellent anti-glare effect, wear resistance and hardness, while reducing surface roughness.

[0045] 2. In this invention, additives are added to adjust the physicochemical properties of the sol itself, thereby complementing the spraying process. In particular, the interaction between the additives and the sol solution formed by tetraethyl silicate, and the addition of an additive mixture of ethylene glycol monomethyl ether and dipropylene glycol monomethyl ether in a weight ratio of (3-8):(2-5):(1-2):(1-2):1, adjusts the physical properties of the anti-glare optical coating solution, thereby controlling the viscosity and volatility of the sol solution to achieve the best particle spraying effect and excellent anti-glare properties. In addition, it also affects the coating preparation process, reduces the preheating temperature of the glass substrate, and reduces energy consumption.

[0046] 3. By adding 10-25 parts of precursor, 1-10 parts of additive, 1-5 parts of catalyst, 5-20 parts of inorganic solvent, and 50-80 parts of organic solvent, especially 10-20 parts of tetraethyl silicate as the precursor, the present invention can control the solid content of compounds in the anti-glare optical coating solution, control the stability of the sol, and form a coating with a suitable viscosity. In the specific spraying parameters of this application, the wear resistance, adhesion, hardness and surface roughness of the anti-glare coating are improved.

[0047] 4. The process of this invention is simple and easy to operate, and the materials used are green, environmentally friendly, and inexpensive. The formulation in this invention differs from typical coating systems that require the addition of silane coupling agents to achieve high wear resistance and high hardness. This invention reduces the use of silane coupling agents while maintaining high wear resistance and high hardness, thus reducing costs.

[0048] 5. In this invention, the spraying parameters are set as follows: air pressure 4–7 bar, flow rate 0.1–0.2 cc / s, spray gun moving speed 20–140 cm / s, and spray gun height 10–30 cm. This results in a nanoscale anti-glare film glass anti-glare coating with low surface roughness, high wear resistance, and high hardness. In this invention, a low preheating temperature will affect the anti-glare effect, while a high temperature will affect the wear resistance. Attached Figure Description

[0049] Figure 1 The image shows the result after the coating in Example 1 was subjected to a 750g load and 1000 rubs.

[0050] Figure 2 The images show the hardness test results of the coating in Example 1. The top left image shows the result of a pencil scratch test from 6H, repeated 5 times, with no obvious scratches. The top right image shows the result of a pencil scratch test from 7H, repeated 5 times, with no obvious scratches. The bottom left image shows the result of a pencil scratch test from 8H, repeated 5 times, with no obvious scratches. The bottom right image shows the result of a pencil scratch test from 9H, repeated 5 times, with no obvious scratches, indicating that the hardness of the coating is 9H.

[0051] Figure 3 The image shows the coating obtained in Comparative Example 2 (which appears liquid under light irradiation).

[0052] Figure 4 The image shows the coating obtained in Comparative Example 4 (showing white spots on the surface under light source illumination).

[0053] Figure 5 The image shows the result of applying a 750g load to the coating prepared in Comparative Example 2 and subjecting it to 1000 rubs.

[0054] Figure 6 The coating pattern prepared in Comparative Example 4 is shown in the image after being subjected to a 750g load and 500 rubs. Detailed Implementation

[0055] Example 1

[0056] The first aspect of this embodiment provides a high wear-resistant glass anti-glare coating, the raw materials for which, by weight, are 10 parts tetraethyl silicate, 3 parts diethylene glycol monomethyl ether, 3 parts dipropylene glycol monomethyl ether, 2 parts ethyl acetate, 1 part butyl acetate, 1 part acetylacetone, 2 parts 68wt% nitric acid aqueous solution, 10 parts deionized water, 26 parts ethanol and 37 parts n-butanol.

[0057] The second aspect of this embodiment provides a method for preparing a highly wear-resistant anti-glare coating for glass. The preparation method is a sol-gel method, comprising the following steps:

[0058] S1: Dissolve 68wt% nitric acid aqueous solution in deionized water and stir to mix evenly to obtain solution 1;

[0059] S2: Tetraethyl silicate and an ethanol-n-butanol mixture (ethanol-n-butanol weight ratio of 1:2, of which 3.33 parts of ethanol and 6.67 parts of n-butanol) are mixed at a weight ratio of 1:1 to obtain solution 2;

[0060] S3: Add solution 1 to solution 2 at a constant speed while stirring continuously. After the addition is complete, stir at a constant temperature for 60 minutes to obtain a sol solution.

[0061] S4: Turn off the temperature and cool the sol solution to 25°C while stirring. Add diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, ethyl acetate, butyl acetate, and acetylacetone in sequence while stirring. Then add the remaining ethanol-n-butanol mixture (22.67 parts of ethanol and 30.33 parts of n-butanol). Stir and mix evenly to obtain the anti-glare optical coating solution.

[0062] S5: Use an alkaline cleaning agent with a mass fraction of 15% (solute is sodium hydroxide, solvent is water and ethanol in a mass ratio of 1:1), control the temperature at 40℃, and use constant temperature ultrasonic cleaning to clean a 10*10cm*1mm glass substrate. Then rinse the surface with clean water to remove residual cleaning agent and dry it to maintain a high level of cleanliness.

[0063] S6: Set the temperature to 50℃ and preheat the glass substrate; use the spraying equipment and set the spraying parameters: air pressure 5 bar, flow rate 0.1 cc / s, spraying speed 140 cm / s, spray gun height 20 cm, and spray anti-glare optical coating liquid onto the clean glass surface.

[0064] S7: High-temperature curing at 200℃ for 30 minutes yields an anti-glare optical coating with high wear resistance and high hardness.

[0065] The third aspect of this embodiment provides an application of a high wear-resistant glass anti-glare coating, which is applied to automotive optical glass.

[0066] Example 2

[0067] The first aspect of this embodiment provides a high wear-resistant glass anti-glare coating, the raw materials for which, by weight, are 20 parts tetraethyl silicate, 3 parts diethylene glycol monomethyl ether, 3 parts dipropylene glycol monomethyl ether, 2 parts ethyl acetate, 1 part butyl acetate, 1 part acetylacetone, 4 parts 68wt% nitric acid aqueous solution, 20 parts deionized water, 36 parts ethanol and 37 parts n-butanol.

[0068] The second aspect of this embodiment provides a method for preparing a highly wear-resistant anti-glare coating for glass. The preparation method is a sol-gel method, comprising the following steps:

[0069] S1: Dissolve 68wt% nitric acid aqueous solution in deionized water and stir to mix evenly to obtain solution 1;

[0070] S2: Tetraethyl silicate and an ethanol-n-butanol mixture (ethanol-n-butanol weight ratio of 1:2, of which 6.66 parts of ethanol and 13.34 parts of n-butanol) are mixed at a weight ratio of 1:1 to obtain solution 2;

[0071] S3: Add solution 1 to solution 2 at a constant speed while stirring continuously. After the addition is complete, stir at a constant temperature for 60 minutes to obtain a sol solution.

[0072] S4: Turn off the temperature, stir the sol solution and cool it to 25°C. While stirring, add diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, ethyl acetate, butyl acetate and acetylacetone in sequence. Then add the remaining ethanol-n-butanol mixture (29.34 parts of ethanol and 23.66 parts of n-butanol). Stir and mix evenly to obtain the anti-glare optical coating solution.

[0073] S5: Use an alkaline cleaning agent with a mass fraction of 15% (solute is sodium hydroxide, solvent is water and ethanol in a mass ratio of 1:1), control the temperature at 40℃, and use constant temperature ultrasonic cleaning to clean a 10*10cm*1mm glass substrate. Then rinse the surface with clean water to remove residual cleaning agent and dry it to maintain a high level of cleanliness.

[0074] S6: Set the temperature to 50℃ and preheat the glass substrate; use the spraying equipment and set the spraying parameters: air pressure 5 bar, flow rate 0.1 cc / s, spraying speed 140 cm / s, spray gun height 20 cm, and spray anti-glare optical coating liquid onto the clean glass surface.

[0075] S7: High-temperature curing at 200℃ for 30 minutes yields an anti-glare optical coating with high wear resistance and high hardness.

[0076] The third aspect of this embodiment provides an application of a high wear-resistant glass anti-glare coating, which is applied to automotive optical glass.

[0077] Comparative Example 1

[0078] The first aspect of this comparative example provides a highly wear-resistant anti-glare glass coating, the raw materials for which, by weight, are 10 parts tetraethyl silicate, 2 parts 68wt% aqueous nitric acid solution, 20 parts deionized water, 26 parts ethanol and 37 parts n-butanol.

[0079] The second aspect of this comparative example provides a method for preparing a highly wear-resistant anti-glare coating for glass. The preparation method is a sol-gel method, comprising the following steps:

[0080] S1: Dissolve 68wt% nitric acid aqueous solution in deionized water and stir to mix evenly to obtain solution 1;

[0081] S2: Tetraethyl silicate and an ethanol-n-butanol mixture (the weight ratio of the mixture is 1:2, of which 3.33 parts are ethanol and 6.67 parts are n-butanol) are mixed at a weight ratio of 1:1 to obtain solution 2;

[0082] S3: Add solution 1 to solution 2 at a constant speed while stirring continuously. After the addition is complete, stir at a constant temperature for 60 minutes to obtain a sol solution.

[0083] S4: Turn off the temperature, stir the sol solution and cool it to 25°C. Add the remaining ethanol and n-butanol mixture (22.67 parts of ethanol and 30.33 parts of n-butanol) while stirring. After stirring and mixing evenly, the anti-glare optical coating solution is obtained.

[0084] S5: Use an alkaline cleaning agent with a mass fraction of 15% (solute is sodium hydroxide, solvent is water and ethanol in a mass ratio of 1:1), control the temperature at 40℃, and use constant temperature ultrasonic cleaning to clean a 10*10cm*1mm glass substrate. Then rinse the surface with clean water to remove residual cleaning agent and dry it to maintain a high level of cleanliness.

[0085] S6: Set the temperature to 50℃ and preheat the glass substrate; use the spraying equipment and set the spraying parameters: air pressure 5 bar, flow rate 0.1 cc / s, spraying speed 140 cm / s, spray gun height 20 cm, and spray the anti-glare optical coating liquid onto the clean glass surface; during the spraying process, control the surface temperature of the glass substrate to 40-60℃.

[0086] S7: High-temperature curing at 200℃ for 30 minutes yields an anti-glare optical coating with high wear resistance and high hardness.

[0087] The third aspect of this comparative example provides an application of a highly wear-resistant anti-glare coating for automotive optical glass.

[0088] Comparative Example 2

[0089] The first aspect of this comparative example provides a highly wear-resistant anti-glare glass coating, the raw materials for which, by weight, are 10 parts tetraethyl silicate, 3 parts diethylene glycol monomethyl ether, 3 parts dipropylene glycol monomethyl ether, 2 parts ethyl acetate, 1 part butyl acetate, 1 part acetylacetone, 2 parts 68wt% nitric acid aqueous solution, 10 parts deionized water, 26 parts ethanol and 37 parts n-butanol.

[0090] The second aspect of this comparative example provides a method for preparing a highly wear-resistant anti-glare coating for glass. The preparation method is a sol-gel method, comprising the following steps:

[0091] S1: Dissolve 68wt% nitric acid aqueous solution in deionized water and stir to mix evenly to obtain solution 1;

[0092] S2: Tetraethyl silicate and an ethanol-n-butanol mixture (ethanol-n-butanol weight ratio of 1:2, of which 3.33 parts of ethanol and 6.67 parts of n-butanol) are mixed at a weight ratio of 1:1 to obtain solution 2;

[0093] S3: Add solution 1 to solution 2 at a constant speed while stirring continuously. After the addition is complete, stir at a constant temperature for 60 minutes to obtain a sol solution.

[0094] S4: Turn off the temperature and cool the sol solution to 25°C while stirring. Add diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, ethyl acetate, butyl acetate, and acetylacetone in sequence while stirring. Then add the remaining ethanol-n-butanol mixture (22.67 parts of ethanol and 30.33 parts of n-butanol). Stir and mix evenly to obtain the anti-glare optical coating solution.

[0095] S5: Use an alkaline cleaning agent with a mass fraction of 15% (solute is sodium hydroxide, solvent is water and ethanol in a mass ratio of 1:1), control the temperature at 40℃, and use constant temperature ultrasonic cleaning to clean a 10*10cm*1mm glass substrate. Then rinse the surface with clean water to remove residual cleaning agent and dry it to maintain a high level of cleanliness.

[0096] S6: Set the temperature to 50℃ and preheat the glass substrate; use the spraying equipment and set the spraying parameters: air pressure 7 bar, flow rate 1.0 cc / s, spraying speed 140 cm / s, spray gun height 20 cm, and spray the anti-glare optical coating liquid onto the clean glass surface; during the spraying process, control the surface temperature of the glass substrate to 70-100℃.

[0097] S7: High-temperature curing at 200℃ for 30 minutes yields an anti-glare optical coating with high wear resistance and high hardness.

[0098] The third aspect of this comparative example provides an application of a highly wear-resistant anti-glare coating for automotive optical glass.

[0099] Comparative Example 3

[0100] The first aspect of this comparative example provides a high wear-resistant anti-glare glass coating, the raw materials for which, by weight, are 10 parts tetraethyl silicate, 2 parts silane coupling agent KH560, 3 parts diethylene glycol monomethyl ether, 3 parts dipropylene glycol monomethyl ether, 2 parts ethyl acetate, 1 part butyl acetate, 1 part acetylacetone, 2 parts 68wt% nitric acid aqueous solution, 10 parts deionized water, 26 parts ethanol and 37 parts n-butanol.

[0101] The second aspect of this comparative example provides a method for preparing a highly wear-resistant anti-glare coating for glass. The preparation method is a sol-gel method, comprising the following steps:

[0102] S1: Dissolve 68wt% nitric acid aqueous solution in deionized water and stir to mix evenly to obtain solution 1;

[0103] S2: Tetraethyl silicate, silane coupling agent KH560 and ethanol-n-butanol mixture (ethanol-n-butanol weight ratio of 1:2, of which 4 parts ethanol and 8 parts n-butanol) are mixed in a weight ratio of 10:2:12 to obtain solution 2.

[0104] S3: Add solution 1 to solution 2 at a constant speed while stirring continuously. After the addition is complete, stir at a constant temperature for 60 minutes to obtain a sol solution.

[0105] S4: Turn off the temperature, stir the sol solution and cool it to 25°C. While stirring, add diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, ethyl acetate, butyl acetate and acetylacetone in sequence. Then add the remaining ethanol-n-butanol mixture (22 parts of ethanol and 29 parts of n-butanol). Stir and mix evenly to obtain the anti-glare optical coating solution.

[0106] S5: Use an alkaline cleaning agent with a mass fraction of 15% (solute is sodium hydroxide, solvent is water and ethanol in a mass ratio of 1:1), control the temperature at 40℃, and use constant temperature ultrasonic cleaning to clean a 10*10cm*1mm glass substrate. Then rinse the surface with clean water to remove residual cleaning agent and dry it to maintain a high level of cleanliness.

[0107] S6: Set the temperature to 50℃ and preheat the glass substrate; use the spraying equipment and set the spraying parameters: air pressure 5 bar, flow rate 0.1 cc / s, spraying speed 140 cm / s, spray gun height 20 cm, and spray the anti-glare optical coating liquid onto the clean glass surface; during the spraying process, control the surface temperature of the glass substrate to 40-60℃.

[0108] S7: High-temperature curing at 200℃ for 30 minutes yields an anti-glare optical coating with high wear resistance and high hardness.

[0109] The third aspect of this comparative example provides an application of a highly wear-resistant anti-glare coating for automotive optical glass.

[0110] Comparative Example 4

[0111] The first aspect of this comparative example provides a highly wear-resistant anti-glare glass coating, the raw materials for which, by weight, are 10 parts tetraethyl silicate, 2 parts silica nano-dispersion, 3 parts diethylene glycol monomethyl ether, 3 parts dipropylene glycol monomethyl ether, 2 parts ethyl acetate, 1 part butyl acetate, 1 part acetylacetone, 2 parts 68wt% nitric acid aqueous solution, 10 parts deionized water, 26 parts ethanol and 37 parts n-butanol.

[0112] The second aspect of this comparative example provides a method for preparing a highly wear-resistant anti-glare coating for glass. The preparation method is a sol-gel method, comprising the following steps:

[0113] S1: Dissolve 68wt% nitric acid aqueous solution in deionized water and stir to mix evenly to obtain solution 1;

[0114] S2: Tetraethyl silicate and an ethanol-n-butanol mixture (ethanol-n-butanol weight ratio of 1:2, of which 3.33 parts of ethanol and 6.67 parts of n-butanol) are mixed at a weight ratio of 1:1 to obtain solution 2;

[0115] S3: While stirring, add the nano-silica dispersion to solution 2, and continue stirring for 10 minutes until it is evenly dispersed to form solution 3;

[0116] S4: Add solution 1 to solution 3 at a constant speed and stir continuously. After the addition is complete, stir at a constant temperature for 60 minutes to obtain a sol solution. After the sol solution cools to 25°C, mix and stir the two sols for 30 minutes.

[0117] S4: Add diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, ethyl acetate, butyl acetate, and acetylacetone in sequence while stirring. Then add the remaining ethanol-n-butanol mixture (22.67 parts of ethanol and 30.33 parts of n-butanol). Stir and mix evenly to obtain the anti-glare optical coating solution.

[0118] S5: Use an alkaline cleaning agent with a mass fraction of 15% (solute is sodium hydroxide, solvent is water and ethanol in a mass ratio of 1:1), control the temperature at 40℃, and use constant temperature ultrasonic cleaning to clean a 10*10cm*1mm glass substrate. Then rinse the surface with clean water to remove residual cleaning agent and dry it to maintain a high level of cleanliness.

[0119] S6: Set the temperature to 50℃ and preheat the glass substrate; use the spraying equipment and set the spraying parameters: air pressure 5 bar, flow rate 0.1 cc / s, spraying speed 140 cm / s, spray gun height 20 cm, and spray the anti-glare optical coating liquid onto the clean glass surface; during the spraying process, control the surface temperature of the glass substrate to 40-60℃.

[0120] S7: High-temperature curing at 200℃ for 30 minutes yields an anti-glare optical coating with high wear resistance and high hardness.

[0121] The third aspect of this comparative example provides an application of a highly wear-resistant anti-glare coating for automotive optical glass.

[0122] Performance testing

[0123] 1. Abrasion resistance test

[0124] Test standard: According to ISO 9211-4 Optics and photonics-Optical coating-Part 4:Specific test methods;

[0125] Test conditions: (1) 0000# steel wool, load 750g, friction cycle range 1000 times;

[0126] (2) 0000# steel wool, load 500g, friction cycle range greater than 5000 times;

[0127] Test method: Fix the prepared coating sample onto the wear resistance instrument, set the wear resistance parameters and measure them, and record the data in Table 1.

[0128] 2. Gloss and haze

[0129] Test standard: GB / T 2410-2008 Test method for light transmittance and haze of transparent plastics;

[0130] Test method: Place the coating material with the coated side facing up on a black matte background, place the instrument on the coating for measurement, and record the data in Table 1.

[0131] 3. Pencil Hardness Test

[0132] Test standard: GB / T 6739-2022 Standard for Hardness of Coated Pencils;

[0133] Test method: The test shall be conducted in accordance with the national standard test requirements, and the data shall be recorded in Table 1.

[0134] 4. Surface roughness test

[0135] Test Method: A handheld surface roughness instrument was used for measurement, and the results were recorded in Table 1. The instrument employs a stylus-based principle for testing, and the measurement parameters conform to the national standard GB / T 3505 "Product Geometric Specifications - Surface Structure Profile Method: Terminology, Definitions, and Parameters" and GB / T 6062 "Product Geometric Specifications (GPS) - Surface Structure Profile Method: Nominal Characteristics of Contact (Stylus) Instruments".

[0136] Table 1

[0137]

Claims

1. A method for preparing a high-wear-resistant, high-hardness anti-glare glass coating, characterized in that, The preparation method is a sol-gel method, including the following steps: S1 dissolves nitric acid in an inorganic solvent and mixes it with stirring to form solution 1; S2: Dissolve the precursor in organic solvent 1 and mix them at a weight ratio of 1:1 to obtain solution 2; S3: Add solution 1 to solution 2, which is being stirred continuously, at a constant speed. After the addition is complete, stir at a constant temperature for 60 minutes to obtain a sol solution. S4: After the sol solution cools to room temperature, add organic solvent 2 and additives one after another, stir and mix evenly to obtain anti-glare optical coating solution; S5: Cleaning glass substrate; S6: Set the temperature to 40-60℃ to preheat the glass substrate; use high-precision spraying equipment, set specific spraying parameters, and spray anti-glare optical coating liquid onto the clean glass surface. S7: After high-temperature curing, an anti-glare optical coating with high wear resistance and high hardness is obtained; The spraying parameters are: air pressure 5 bar, flow rate 0.1 cc / s, spraying speed 140 cm / s, and spray gun height 20 cm. The raw materials for preparing the high wear-resistant and high hardness glass anti-glare coating, by weight, are 10-20 parts of precursor, 1-10 parts of additives, 1-5 parts of catalyst, 5-20 parts of inorganic solvent and 50-80 parts of organic solvent; the precursor is tetraethyl silicate; the additives are diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, acetylacetone, ethyl acetate and butyl acetate. The weight ratio of ethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, ethyl acetate, butyl acetate, and acetylacetone is 3:3:2:1:

1.

2. The method for preparing the high wear-resistant and high hardness anti-glare glass coating according to claim 1, characterized in that, The catalyst is one or more of hydrochloric acid, nitric acid, and acetic acid.

3. The method for preparing the high wear-resistant and high-hardness anti-glare glass coating according to claim 1, characterized in that, The organic solvent is organic solvent 1 and organic solvent 2; organic solvent 1 and organic solvent 2 are one or more of methanol, ethanol, n-propanol, isopropanol, and n-butanol.

4. The method for preparing the high wear-resistant and high-hardness anti-glare glass coating according to claim 1, characterized in that, The inorganic solvent is deionized water.

5. The application of the method for preparing a high-wear-resistant and high-hardness anti-glare glass coating according to any one of claims 1 to 3, characterized in that, Used in automotive optical glass.

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