A production process for coated glass

Abstract

The present invention relates to the technical field of glass production, and specifically to a production process of coated glass. The coating solution comprises the following weight components: 20-40 parts of modified silica sol, 40-80 parts of isopropyl alcohol, 10-20 parts of n-butanol, 3-5 parts of 2-perfluorooctylethyl acrylate, 5-8 parts of 2-hydroxyethyl methacrylate, 8-10 parts of vinyl-terminated dimethyl polysiloxane, 4-7 parts of methyl methacrylate, 0.3-0.5 parts of benzoyl peroxide, 1-2 parts of acrylic acid, 20-30 parts of deionized water, 0.5-1.0 part of leveling agent, and 0.2-0.5 part of defoaming agent. The present invention prepares the coated glass by coating the coating solution on the surface of pretreated glass and drying it, which not only has excellent transmittance but also has excellent hydrophobic performance.

Description

Technical Field

[0001] The present invention relates to the technical field of glass production, and particularly to a production process of coated glass. Background Art

[0002] Coated glass is a process of coating a special film layer on the surface of ordinary glass, aiming to improve the optical and functional properties of the glass. This film layer can enhance the abrasion resistance, ultraviolet resistance, anti-reflection performance, etc. of the glass, enabling the glass to have a wider range of application fields.

[0003] However, there are still some problems to be solved in the existing coating technologies. First, the coating stability is poor, and some coated glasses may have problems such as peeling, discoloration or degradation during use, affecting their service life and performance. Second, the stain resistance and durability of the coating film layer are limited, and it is easily affected by daily use and cleaning operations, resulting in scratches and stains on the surface.

[0004] Therefore, we propose a production process of coated glass. Summary of the Invention

[0005] The purpose of the present invention is to provide a production process of coated glass to solve the problems raised in the above background art.

[0006] To solve the above technical problems, the present invention provides the following technical solutions:

[0007] A production process of coated glass includes the following steps:

[0008] Step S1: Pretreat the glass substrate to obtain a pretreated substrate;

[0009] Step S2: Under nitrogen protection, mix isopropyl alcohol and n-butanol evenly, heat up to 85 - 90 °C, add benzoyl peroxide, dropwise add 2-perfluorooctyl ethyl acrylate, 2-hydroxyethyl methacrylate, vinyl-terminated dimethyl polysiloxane and methyl methacrylate, and finish dropping in 1 - 2 h. At the same time, dropwise add modified silica sol and acrylic acid, and finish dropping in 1 - 2 h. React for 4 - 6 h, adjust the pH of the system to 8 - 9, add deionized water, leveling agent, and defoaming agent and mix evenly to obtain a coating solution;

[0010] Step S3: Coat the coating solution on the surface of the pretreated substrate, dry it, and form a coating to obtain coated glass.

[0011] Further, the preparation method of the pretreated substrate is as follows:

[0012] Immerse the glass substrate in deionized water, ultrasonically clean for 10 - 30 min, then immerse in absolute ethanol, ultrasonically treat for 10 - 30 min, after drying, perform ultraviolet ozone treatment for 10 - 30 min to obtain a hydroxylated substrate;

[0013] Mix 3 - glycidoxypropyltrimethoxysilane, deionized water and absolute ethanol evenly, add hydrochloric acid to adjust the pH of the system to 3 - 4 to obtain a mixed solution; immerse the hydroxylated substrate in the mixed solution, react for 2 - 4 h, after drying, obtain a pretreated substrate.

[0014] Furthermore, the mass ratio of the 3 - glycidoxypropyltrimethoxysilane, deionized water and absolute ethanol is 1:(2 - 4):(10 - 15).

[0015] Furthermore, the coating solution comprises the following weight components: 20 - 40 parts of modified silica sol, 40 - 80 parts of isopropanol, 10 - 20 parts of n - butanol, 3 - 5 parts of 2 - perfluorooctylethyl acrylate, 5 - 8 parts of 2 - hydroxyethyl methacrylate, 8 - 10 parts of vinyl - terminated dimethyl polysiloxane, 4 - 7 parts of methyl methacrylate, 0.3 - 0.5 parts of benzoyl peroxide, 1 - 2 parts of acrylic acid, 20 - 30 parts of deionized water, 0.5 - 1.0 part of leveling agent, 0.2 - 0.5 part of defoaming agent.

[0016] Furthermore, the preparation method of the modified silica sol is as follows:

[0017] Mix tetraethyl orthosilicate, absolute ethanol and deionized water evenly, add hydrochloric acid to adjust the pH of the system to 2 - 3, add a mixed solution of a modifier and absolute ethanol, react at 60 - 70 °C for 4 - 6 h, add a mixed solution of γ - methacryloxypropyltrimethoxysilane and absolute ethanol, stir for 3 - 5 h, and let stand overnight to obtain the modified silica sol.

[0018] Furthermore, the mass ratio of the tetraethyl orthosilicate, absolute ethanol and deionized water is 1:(3 - 4):(0.6 - 0.8).

[0019] Furthermore, the mass ratio of the modifier, tetraethyl orthosilicate and absolute ethanol is 1:(5 - 7):(15 - 20).

[0020] Furthermore, the mass ratio of the γ - methacryloxypropyltrimethoxysilane, tetraethyl orthosilicate and absolute ethanol is 1:(2 - 3):(5 - 10).

[0021] Furthermore, the preparation method of the modifier is as follows:

[0022] Step (1): Disperse nanocellulose in deionized water, add 2,2,6,6-tetramethylpiperidine-1-oxyl radical, sodium bromide and sodium hypochlorite solution, adjust the pH of the system to 10 - 11, after reacting for 1 - 2 h, through centrifugation, neutralization, and ultrasonic treatment, obtain a suspension;

[0023] Mix the suspension and Ce(NO 3 ) 3 ·6H 2 O aqueous solution evenly, react at 70 - 80 °C for 1 - 2 h, add sodium hydroxide solution, continue to react for 4 - 6 h, cool to room temperature, stir for 22 - 24 h, after centrifugation, washing, and drying, obtain a composite;

[0024] Step (2): Add the composite, 3-aminopropyltriethoxysilane, deionized water, and absolute ethanol, add hydrochloric acid to adjust the pH of the system to 3 - 4, react at 50 - 60 °C for 8 - 10 h, after centrifugation, washing, and drying, obtain an aminated composite;

[0025] Step (3): Mix trimethylolpropane triglycidyl ether, perfluoropolyether alcohol, and tetrabutylammonium bromide evenly, react at 70 - 75 °C for 3 - 5 h, cool down to 50 - 55 °C, add sodium hydroxide, continue to react for 2 - 3 h, through washing and vacuum distillation, obtain a fluorinated epoxy compound; Mix the fluorinated epoxy compound, aminated composite, and ethanol evenly, react for 2 - 4 h, after centrifugation, washing, and drying, obtain a modifier.

[0026] Further, in the step (1), the suspension includes the following weight components: 1 - 2 parts of nanocellulose, 100 - 200 parts of deionized water, 0.01 - 0.05 parts of 2,2,6,6-tetramethylpiperidine-1-oxyl radical, 0.1 - 0.2 parts of sodium bromide, and 15 - 30 parts of sodium hypochlorite solution.

[0027] Further, the sodium hypochlorite solution contains 6 - 14 wt% active chlorine.

[0028] Further, in the step (1), the mass ratio of nanocellulose to Ce(NO 3 ) 3 ·6H 2 O is 1:(3 - 5), and the concentration of Ce(NO 3 ) 3 ·6H 2 O aqueous solution is 3 - 5 wt%.

[0029] Further, in the step (1), the concentration of the sodium hydroxide solution is 1 mol / L, and its dosage is based on Ce(NO 3 ) 3 ·6H 20.8 - 1.0 times the mass of the aqueous solution.

[0030] Further, in the step (2), the mass ratio of the complex, 3 - aminopropyltriethoxysilane, deionized water, and absolute ethanol is 1:(1 - 2):(3 - 5):(15 - 20).

[0031] Further, in the step (3), the mass ratio of the trimethylolpropane triglycidyl ether, perfluoropolyether alcohol, tetrabutylammonium bromide, and sodium hydroxide is 1:(2 - 3):(0.1 - 0.3):(1.5 - 2.0).

[0032] Further, in the step (3), the mass ratio of the fluorinated epoxy compound, amino - modified complex, and ethanol is 1:(3 - 5):(10 - 15).

[0033] In the above - mentioned technical solution, using nanocellulose as the raw material, the primary alcohol hydroxyl group at the C6 position of nanocellulose is oxidized to a carboxyl group by the 2,2,6,6 - tetramethylpiperidine - 1 - oxyl (TEMPO) oxidation method. Based on the electrostatic interaction between the carboxylate ion and the cerium ion, CeO 2 with ultraviolet shielding performance is loaded on the surface of nanocellulose to obtain a complex. Then, through the hydrolysis of 3 - aminopropyltriethoxysilane, an amino - modified complex is prepared. Finally, through the ring - opening reaction of trimethylolpropane triglycidyl ether and perfluoropolyether alcohol, a fluorinated epoxy compound is obtained; the fluorinated epoxy compound and the amino - modified complex react to obtain a fluorinated modifier.

[0034] Further, the process conditions for drying are: drying at 100 - 120 °C for 0.5 - 1.5 h.

[0035] Further, the thickness of the coating film is 0.5 - 2.0 μm.

[0036] Further, the coating method is spin - coating, and the rotation speed is 2000 - 3000 rpm.

[0037] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0038] 1. In the production process of a coated glass of the present invention, the surface of the glass is first hydroxylated, which improves the wettability of the glass surface, and significantly increases the silanol groups on the glass surface, providing grafting sites for the silanization modification of the glass matrix. Then, silanization treatment is carried out to introduce epoxy groups, which can react with the remaining amino groups in the modifier. There is not only physical adhesion but also chemical bonding between the coating and the glass matrix, enhancing the bonding force between the coating and the matrix.

[0039] 2. A production process of coated glass according to the present invention grows cerium dioxide with ultraviolet shielding performance on the surface of nanocellulose in an in-situ growth manner. By utilizing the high specific surface area and porosity of nanocellulose, the ultraviolet shielding performance and stability of the material are improved. Subsequently, surface modification is carried out with 3-aminopropyltriethoxysilane to introduce amino groups, obtaining an aminated composite, which improves the dispersion performance of the material. Through the ring-opening reaction of trimethylolpropane triglycidyl ether and perfluoropolyether alcohol, a fluorinated epoxy compound is obtained. Then, the aminated composite is added to react with the remaining epoxy groups, preparing a fluorinated modifier with ultraviolet shielding effect and superhydrophobicity, achieving a self-cleaning effect.

[0040] 3. A production process of coated glass according to the present invention adds γ-methacryloxypropyltrimethoxysilane to silica sol to introduce double bonds, forming a modified silica sol with double bonds, which can carry out copolymerization reactions with 2-perfluorooctylethyl acrylate, 2-hydroxyethyl methacrylate, vinyl-terminated dimethylpolysiloxane, and methyl methacrylate to form a crosslinked structure, improving the adhesion of the material and making it adhere more firmly to the glass surface, thereby enhancing the wear resistance and weather resistance of the coating. At the same time, vinyl-terminated dimethylpolysiloxane has high transmittance, low refractive index, and hydrophobic properties, further improving the light transmittance and hydrophobicity of the coating. Detailed implementation manners

[0041] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of them. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0042] In this embodiment, the glass substrate is a transparent tempered glass sheet with a thickness of 1 mm, sourced from Dongguan Jiameite Glass Co., Ltd.; the nanocellulose is CNF, sourced from Wuhan Lana White Pharmaceutical Chemical Co., Ltd.; the vinyl-terminated dimethylpolysiloxane has a CAS number of 68083-19-2, sourced from Shanghai Macklin Biochemical Co., Ltd.; the perfluoropolyether alcohol has a model of Solvay FLUOROLINK D4000; the leveling agent has a model of Keying KYC-615; the defoaming agent has a model of BYK-028.

[0043] In the following examples and comparative examples, 1 part is equal to 10 g, and the thickness of the coating is 1 μm.

[0044] Example 1: A production process of coated glass includes the following processes:

[0045] Step S1: Immerse the glass substrate in deionized water and ultrasonically clean it for 10 min. Then immerse it in absolute ethanol and ultrasonically treat it for 10 min. After drying, perform ultraviolet ozone treatment for 10 min to obtain a hydroxylated substrate.

[0046] Mix 10 parts of 3-glycidoxypropyltrimethoxysilane, 20 parts of deionized water, and 100 parts of absolute ethanol evenly. Add hydrochloric acid to adjust the pH of the system to 3 to obtain a mixed solution. Immerse the hydroxylated substrate in the mixed solution and react for 2 h. After drying, obtain a pretreated substrate.

[0047] Step S2: Under nitrogen protection, mix 40 parts of isopropanol and 10 parts of n-butanol evenly, heat up to 85 °C, add 0.3 part of benzoyl peroxide, and dropwise add 3 parts of 2-perfluorooctyl ethyl acrylate, 5 parts of 2-hydroxyethyl methacrylate, 8 parts of vinyl-terminated dimethyl polysiloxane, and 4 parts of methyl methacrylate. Finish dropping in 1 h. At the same time, dropwise add 20 parts of modified silica sol and 1 part of acrylic acid. Finish dropping in 1 h. React for 4 h, adjust the pH of the system to 8, add 20 parts of deionized water, 0.5 part of leveling agent, and 0.2 part of defoaming agent and mix evenly to obtain a coating solution.

[0048] Step S3: Spin-coat the coating solution on the surface of the pretreated substrate (rotation speed is 2000 rpm), dry it at 100 °C for 1.5 h to form a coating and obtain coated glass.

[0049] The preparation method of the modified silica sol is as follows:

[0050] Mix 20 parts of tetraethyl orthosilicate, 60 parts of absolute ethanol, and 12 parts of deionized water evenly. Add hydrochloric acid to adjust the pH of the system to 2. Add a mixed solution of 4 parts of modifier and 60 parts of absolute ethanol, react at 60 °C for 4 h, add a mixed solution of 10 parts of γ-methacryloxypropyltrimethoxysilane and 50 parts of absolute ethanol, stir for 3 h, and let it stand overnight to obtain the modified silica sol.

[0051] The preparation method of the modifier is as follows:

[0052] Step (1): Disperse 1 part of nanocellulose in 100 parts of deionized water, add 0.01 part of 2,2,6,6-tetramethylpiperidine-1-oxyl radical, 0.1 part of sodium bromide, and 15 parts of sodium hypochlorite solution. Adjust the pH of the system to 10. After reacting for 1 h, perform centrifugation, neutralization, and ultrasonic treatment to obtain a suspension.

[0053] Mix the suspension with 100 parts of a 3 wt% Ce(NO 3 ) 3 ·6H 2Mix the O aqueous solution evenly, react at 70 °C for 1 h, add 80 parts of 1 mol / L sodium hydroxide solution, continue to react for 4 h, cool to room temperature, stir for 22 h, and then obtain the composite after centrifugation, washing, and drying;

[0054] Step (2): Add 3 parts of the composite, 3 parts of 3-aminopropyltriethoxysilane, 9 parts of deionized water, and 45 parts of absolute ethanol, adjust the pH of the system to 3 with hydrochloric acid, react at 50 °C for 8 h, and obtain the aminated composite after centrifugation, washing, and drying;

[0055] Step (3): Mix 1 part of trimethylolpropane triglycidyl ether, 2 parts of perfluoropolyether alcohol, and 0.1 part of tetrabutylammonium bromide evenly, react at 70 °C for 3 h, cool to 50 °C, add 1.5 parts of sodium hydroxide, continue to react for 2 h, and obtain the fluorinated epoxy compound after washing and vacuum distillation; Mix 1 part of the fluorinated epoxy compound, 3 parts of the aminated composite, and 10 parts of ethanol evenly, react for 2 h, and obtain the modifier after centrifugation, washing, and drying.

[0056] Example 2: A production process of coated glass includes the following processes:

[0057] Step S1: Immerse the glass substrate in deionized water, ultrasonically clean for 20 min, then immerse in absolute ethanol, ultrasonically treat for 20 min, dry, and then perform ultraviolet ozone treatment for 20 min to obtain a hydroxylated substrate;

[0058] Mix 10 parts of 3-glycidylpropyltrimethoxysilane, 30 parts of deionized water, and 120 parts of absolute ethanol evenly, add hydrochloric acid to adjust the pH of the system to 3.5 to obtain a mixed solution; Immerse the hydroxylated substrate in the mixed solution, react for 3 h, and dry to obtain a pretreated substrate;

[0059] Step S2: Under nitrogen protection, mix 60 parts of isopropanol and 15 parts of n-butanol evenly, heat up to 88 °C, add 0.4 part of benzoyl peroxide, dropwise add 4 parts of 2-perfluorooctyl ethyl acrylate, 6 parts of 2-hydroxyethyl methacrylate, 9 parts of vinyl-terminated dimethyl polysiloxane, and 5 parts of methyl methacrylate, finish dropping in 1.5 h, and at the same time dropwise add 30 parts of modified silica sol and 1.5 parts of acrylic acid, finish dropping in 1.5 h, react for 5 h, adjust the system pH to 8.5, add 25 parts of deionized water, 0.8 part of leveling agent, and 0.3 part of defoaming agent and mix evenly to obtain a coating solution;

[0060] Step S3: Spin-coat the coating solution on the surface of the pretreated substrate (rotation speed is 2500 rpm), dry at 110 °C for 1 h to form a coating, and obtain the coated glass;

[0061] The preparation method of the modified silica sol is as follows:

[0062] Mix 30 parts of tetraethyl orthosilicate, 105 parts of absolute ethanol, and 21 parts of deionized water evenly. Add hydrochloric acid to adjust the pH of the system to 2.5. Add a mixed solution of 5 parts of modifier and 40 parts of absolute ethanol, react at 65 °C for 5 h, add a mixed solution of 12 parts of γ-methacryloxypropyltrimethoxysilane and 90 parts of absolute ethanol, stir for 4 h, and let stand overnight to obtain modified silica sol;

[0063] The preparation method of the modifier is as follows:

[0064] Step (1): Disperse 1.5 parts of nanocellulose in 150 parts of deionized water, add 0.04 part of 2,2,6,6-tetramethylpiperidine-1-oxyl radical, 0.15 part of sodium bromide, and 20 parts of sodium hypochlorite solution, adjust the pH of the system to 10.5, after reacting for 1.5 h, obtain a suspension after centrifugation, neutralization, and ultrasonic treatment;

[0065] Mix the suspension and 150 parts of an aqueous solution of Ce(NO 3 ) 3 ·6H 2 O with a concentration of 4 wt% evenly, react at 75 °C for 1.5 h, add 135 parts of 1 mol / L sodium hydroxide solution, continue to react for 5 h, cool to room temperature, stir for 23 h, and obtain a complex after centrifugation, washing, and drying;

[0066] Step (2): Add 5 parts of the complex, 7.5 parts of 3-aminopropyltriethoxysilane, 20 parts of deionized water, and 90 parts of absolute ethanol, add hydrochloric acid to adjust the pH of the system to 3.5, react at 55 °C for 9 h, and obtain an aminated complex after centrifugation, washing, and drying;

[0067] Step (3): Mix 1.25 parts of trimethylolpropane triglycidyl ether, 3 parts of perfluoropolyether alcohol, and 0.25 part of tetrabutylammonium bromide evenly, react at 72 °C for 4 h, cool to 52 °C, add 2.25 parts of sodium hydroxide, and obtain a fluorinated epoxy compound after washing and vacuum distillation; Mix 1.25 parts of the fluorinated epoxy compound, 5 parts of the aminated complex, and 15 parts of ethanol evenly, react for 3 h, and obtain a modifier after centrifugation, washing, and drying.

[0068] Example 3: A production process of coated glass includes the following processes:

[0069] Step S1: Immerse the glass substrate in deionized water, ultrasonically clean for 30 min, then immerse it in absolute ethanol, ultrasonically treat for 30 min, dry, and perform ultraviolet ozone treatment for 30 min to obtain a hydroxylated substrate;

[0070] Mix 10 parts of 3-glycidylpropyltrimethoxysilane, 40 parts of deionized water and 150 parts of absolute ethanol evenly, add hydrochloric acid to adjust the pH of the system to 4 to obtain a mixed solution; immerse the hydroxylated substrate into the mixed solution, react for 4 h, and after drying, obtain a pretreated substrate.

[0071] Step S2: Under nitrogen protection, mix 80 parts of isopropanol and 20 parts of n-butanol evenly, heat up to 90 °C, add 0.5 part of benzoyl peroxide, dropwise add 5 parts of 2-perfluorooctyl ethyl acrylate, 8 parts of 2-hydroxyethyl methacrylate, 10 parts of vinyl-terminated dimethyl polysiloxane and 7 parts of methyl methacrylate, finish dropping in 2 h, at the same time dropwise add 40 parts of modified silica sol and 2 parts of acrylic acid, finish dropping in 2 h, react for 6 h, adjust the pH of the system to 9, add 30 parts of deionized water, 1.0 part of leveling agent and 0.5 part of defoaming agent and mix evenly to obtain a coating solution.

[0072] Step S3: Spin-coat the coating solution on the surface of the pretreated substrate (rotation speed is 3000 rpm), dry at 120 °C for 1.5 h to form a coating, and obtain coated glass.

[0073] The preparation method of the modified silica sol is as follows:

[0074] Mix 42 parts of tetraethyl orthosilicate, 168 parts of absolute ethanol and 33.6 parts of deionized water evenly, add hydrochloric acid to adjust the pH of the system to 3, add a mixed solution of 6 parts of modifier and 120 parts of absolute ethanol, react at 70 °C for 6 h, add a mixed solution of 14 parts of γ-methacryloxypropyltrimethoxysilane and 140 parts of absolute ethanol, stir for 5 h, stand overnight to obtain the modified silica sol.

[0075] The preparation method of the modifier is as follows:

[0076] Step (1): Disperse 2 parts of nanocellulose in 200 parts of deionized water, add 0.05 part of 2,2,6,6-tetramethylpiperidine-1-oxyl radical, 0.2 part of sodium bromide and 30 parts of sodium hypochlorite solution, adjust the pH of the system to 11, after reacting for 2 h, through centrifugation, neutralization and ultrasonic treatment, obtain a suspension.

[0077] Mix the suspension and 200 parts of an aqueous solution of 5 wt% Ce(NO 3 ) 3 ·6H 2 O evenly, react at 80 °C for 2 h, add 200 parts of 1 mol / L sodium hydroxide solution, continue to react for 6 h, cool to room temperature, stir for 24 h, and after centrifugation, washing and drying, obtain a complex.

[0078] Step (2): React 6 parts of the complex, 12 parts of 3-aminopropyltriethoxysilane, 30 parts of deionized water, and 120 parts of absolute ethanol at 60 °C for 10 h. After centrifugation, washing, and drying, an aminated complex is obtained.

[0079] Step (3): Mix 1.2 parts of trimethylolpropane triglycidyl ether, 3.6 parts of perfluoropolyether alcohol, and 0.36 part of tetrabutylammonium bromide evenly, react at 75 °C for 5 h, cool down to 55 °C, add 2.4 parts of sodium hydroxide, and continue to react for 3 h. After washing and vacuum distillation, a fluorinated epoxy compound is obtained; mix 1.2 parts of the fluorinated epoxy compound, 6 parts of the aminated complex, and 18 parts of ethanol evenly, react for 4 h, and after centrifugation, washing, and drying, a modifier is obtained.

[0080] Comparative Example 1: A production process of coated glass includes the following processes:

[0081] Compared with Example 2, Comparative Example 1 does not include Step S1, replaces the pretreated substrate in Step S3 with an unmodified glass substrate, and the other steps are the same as those in Example 2.

[0082] Comparative Example 2: A production process of coated glass includes the following processes:

[0083] The preparation method of the modified silica sol is as follows:

[0084] Mix 30 parts of tetraethyl orthosilicate, 105 parts of absolute ethanol, and 21 parts of deionized water evenly, add hydrochloric acid to adjust the pH of the system to 2.5, add a mixed solution of 5 parts of the modifier and 40 parts of absolute ethanol, react at 65 °C for 5 h, and let it stand overnight to obtain the modified silica sol;

[0085] Compared with Example 2, γ-methacryloxypropyltrimethoxysilane is not added to the modified silica sol in Comparative Example 2, and the other steps are the same as those in Example 2.

[0086] Comparative Example 3: A production process of coated glass includes the following processes:

[0087] The preparation method of the modified silica sol is as follows:

[0088] Mix 30 parts of tetraethyl orthosilicate, 105 parts of absolute ethanol, and 21 parts of deionized water evenly, add hydrochloric acid to adjust the pH of the system to 2.5, add a mixed solution of 12 parts of γ-methacryloxypropyltrimethoxysilane and 90 parts of absolute ethanol, stir for 4 h, and let it stand overnight to obtain the modified silica sol;

[0089] Compared with Example 2, the modifier is not added to the modified silica sol in Comparative Example 3, and the other steps are the same as those in Example 2.

[0090] Comparative Example 4: A production process of coated glass, including the following processes:

[0091] The preparation method of the modifier is as follows:

[0092] Step (1): Disperse 1.5 parts of nanocellulose in 150 parts of deionized water, add 0.04 part of 2,2,6,6-tetramethylpiperidine-1-oxyl radical, 0.15 part of sodium bromide and 20 parts of sodium hypochlorite solution, adjust the pH of the system to 10.5, after reacting for 1.5 h, after centrifugation, neutralization and ultrasonic treatment, a suspension is obtained;

[0093] Mix the suspension and 150 parts of an aqueous solution of Ce(NO 3 ) 3 ·6H 2 O with a concentration of 4 wt% uniformly, react at 75 °C for 1.5 h, add 135 parts of 1 mol / L sodium hydroxide solution, continue to react for 5 h, cool to room temperature, stir for 23 h, after centrifugation, washing and drying, a composite is obtained;

[0094] Step (2): Add 5 parts of the composite, 7.5 parts of 3-aminopropyltriethoxysilane, 20 parts of deionized water and 90 parts of absolute ethanol, add hydrochloric acid to adjust the pH of the system to 3.5, react at 55 °C for 9 h, after centrifugation, washing and drying, an amino-functionalized composite is obtained;

[0095] Step (3): Mix 1.25 parts of trimethylolpropane triglycidyl ether, 3 parts of perfluoropolyether alcohol and 0.25 part of tetrabutylammonium bromide uniformly, react at 72 °C for 4 h, cool to 52 °C, add 2.25 parts of sodium hydroxide, after washing and vacuum distillation, a fluorinated epoxy compound is obtained; Mix 1.25 parts of the fluorinated epoxy compound, 5 parts of the amino-functionalized composite and 15 parts of ethanol uniformly, react for 3 h, after centrifugation, washing and drying, a modifier is obtained;

[0096] Compared with Example 2, in step (3) of Comparative Example 4, the mass ratio of the fluorinated epoxy resin to the amino-functionalized composite is 1:1; other steps are the same as those in Example 2.

[0097] Experiment: Take the coated glass obtained in Examples 1-3 and Comparative Examples 1-4, prepare specimens, and detect their properties respectively and record the detection results:

[0098] According to the standard GB / T 6739-2006 "Paints and varnishes - Determination of film hardness by pencil test", the pencil hardness of the coating was tested; the light transmittance was tested using an ultraviolet-visible spectrophotometer within the wavelength range of 250 - 800 nm according to the standard GB / T 2410-2008 "Determination of light transmittance and haze of transparent plastics"; the coating adhesion test was carried out according to the standard GB / T 9286-2021 "Cross-cut test for paints and varnishes films"; Contact angle test: 5 μL of water droplets were dropped on the coated glass, and a HARKE-CA type static contact angle measuring instrument was used to measure the contact angle between different surfaces and water.

[0099] Test results

[0100] Hardness / H Transmittance / % Water contact angle / ° Adhesion Example 1 5 96.4 150.8 Level 1 Example 2 5 97.8 153.4 Level 1 Example 3 5 97.2 151.6 Level 1 Comparative Example 1 5 93.6 142.7 Level 2 Comparative Example 2 3 92.5 133.5 Level 3 Comparative Example 3 4 90.7 124.8 Level 2 Comparative Example 4 5 94.3 146.2 Level 2

[0101] According to the data in the above table, the following conclusions can be clearly obtained:

[0102] 1. Compared with Examples 1 - 3, the adhesion of the product obtained in Comparative Example 1 decreased, indicating that by pretreating the glass substrate, the present invention can effectively improve the bonding force between it and the coating.

[0103] 2. Compared with Examples 1 - 3, the products obtained in Comparative Examples 2 and 3 showed a decrease in hardness, transmittance, water contact angle and adhesion, which indicates that by adding γ-methacryloxypropyltrimethoxysilane to the modified silica sol to introduce double bonds, the present invention ensures the progress of subsequent reactions, thereby improving the comprehensive performance of the coating; at the same time, by adding a modifier to the modified silica sol, the hydrophobic, mechanical and optical properties of the coating are further improved.

[0104] 3. Compared with Examples 1 - 3, the adhesion and transmittance of the product obtained in Comparative Example 4 both decreased, indicating that the performance of the modifier prepared by the present invention is affected by the ratio of each reagent in its preparation process. By selecting the mass ratio within the said range, the prepared modifier has better transmittance, thereby enhancing the performance of the glass.

[0105] It should be noted that in this article, relational terms such as first and second are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variant thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements not only includes those elements, but also includes other elements not expressly listed, or also includes elements inherent to such process, method, article or device.

[0106] Finally, it should be noted that the above are only preferred embodiments of the present invention and are not used to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or perform equivalent replacements for some of the technical features. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A production process for coated glass, characterized in that: The steps include: Step S1: pre-treating a glass substrate to obtain a pre-treated substrate; Step S2: Under nitrogen protection, isopropanol and n-butanol are mixed evenly, the temperature is raised to 85-90° C., benzoyl peroxide is added, 2-perfluorooctyl ethyl acrylate, hydroxyethyl methacrylate, vinyl-terminated dimethylpolysiloxane and methyl methacrylate are added dropwise for 1-2 hours, modified silica sol and acrylic acid are added dropwise for 1-2 hours, the reaction is carried out for 4-6 hours, the pH value of the system is adjusted to 8-9, deionized water, leveling agent and defoaming agent are added and mixed evenly to obtain a coating solution; Step S3: coating the coating liquid on the surface of the pre-treated substrate, and drying it to form a coating to obtain coated glass; The preparation method of the modified silica sol is as follows: Mix ethyl orthosilicate, anhydrous ethanol and deionized water evenly, add hydrochloric acid to adjust the pH of the system to 2-3, add a mixed solution of a modifier and anhydrous ethanol, react at 60-70°C for 4-6h, add a mixed solution of γ-methacryloxypropyltrimethoxysilane and anhydrous ethanol, stir for 3-5h, and stand overnight to obtain a modified silica sol; The preparation method of the modifier is as follows: Step (1): dispersing nanocellulose in deionized water, adding 2,2,6,6-tetramethylpiperidin-1-oxyl free radical, sodium bromide and sodium hypochlorite solution, adjusting the system pH to 10-11, reacting for 1-2 hours, centrifuging, neutralizing and ultrasonicating to obtain a suspension; The suspension and Ce(NO3)3·6H2O aqueous solution are mixed evenly, reacted at 70-80°C for 1-2h, sodium hydroxide solution is added, the reaction is continued for 4-6h, cooled to room temperature, stirred for 22-24h, centrifuged, washed and dried to obtain a composite; Step (2): adding hydrochloric acid to the complex, 3-aminopropyltriethoxysilane, deionized water and anhydrous ethanol to adjust the pH of the system to 3-4, reacting at 50-60° C. for 8-10 hours, and obtaining an amino complex after centrifugation, washing and drying; Step (3): uniformly mix trimethylolpropane triglycidyl ether, perfluoropolyether alcohol and tetrabutylammonium bromide, react at 70-75°C for 3-5h, cool to 50-55°C, add sodium hydroxide, continue to react for 2-3h, wash and distill under reduced pressure to obtain a fluorine-containing epoxy compound; uniformly mix the fluorine-containing epoxy compound, the amino complex and ethanol, react for 2-4h, centrifuge, wash and dry to obtain a modifier.

2. The production process of coated glass according to claim 1, characterized in that: The preparation method of the pretreated substrate is as follows: The glass substrate is immersed in deionized water, ultrasonically cleaned for 10-30 minutes, then immersed in anhydrous ethanol, ultrasonically treated for 10-30 minutes, dried, and then subjected to ultraviolet ozone treatment for 10-30 minutes to obtain a hydroxylated substrate; 3-glycidylpropyltrimethoxysilane, deionized water and anhydrous ethanol are mixed evenly, and hydrochloric acid is added to adjust the pH of the system to 3-4 to obtain a mixed solution; the hydroxylated substrate is immersed in the mixed solution, reacted for 2-4 hours, and dried to obtain a pretreated substrate.

3. The production process of coated glass according to claim 1, characterized in that: In the step S2, the weight parts of each component are specifically: 20-40 parts of modified silica sol, 40-80 parts of isopropanol, 10-20 parts of n-butanol, 3-5 parts of 2-perfluorooctyl ethyl acrylate, 5-8 parts of hydroxyethyl methacrylate, 8-10 parts of vinyl-terminated dimethyl polysiloxane, 4-7 parts of methyl methacrylate, 0.3-0.5 parts of benzoyl peroxide, 1-2 parts of acrylic acid, 20-30 parts of deionized water, 0.5-1.0 parts of leveling agent, and 0.2-0.5 parts of defoaming agent.

4. The production process of coated glass according to claim 1, characterized in that: In the step (1), the weight proportions of the components are: 1-2 parts of nanocellulose, 100-200 parts of deionized water, 0.01-0.05 parts of 2,2,6,6-tetramethylpiperidin-1-oxyl free radical, 0.1-0.2 parts of sodium bromide, and 15-30 parts of sodium hypochlorite solution.

5. The production process of coated glass according to claim 1, characterized in that: In the step (2), the mass ratio of the composite, 3-aminopropyltriethoxysilane, deionized water and anhydrous ethanol is 1: (1-2): (3-5): (15-20).

6. The production process of coated glass according to claim 1, characterized in that: In the step (3), the mass ratio of trimethylolpropane triglycidyl ether to perfluoropolyether alcohol, tetrabutylammonium bromide and sodium hydroxide is 1:(2-3):(0.1-0.3):(1.5-2.0).

7. The production process of coated glass according to claim 1, characterized in that: The thickness of the coating is 0.5-2.0 μm.

8. A coated glass obtained by the production process according to any one of claims 1 to 7.