Anti-deformation and anti-fading aging-resistant glass film and preparation method thereof

Abstract

The application relates to the technical field of glass coating film, in particular to an anti-deformation, anti-fading and aging-resistant glass film and a preparation method thereof. The preparation method comprises the following steps: step 1: a pretreated glass sheet is immersed in an island silicon-titanium sol, and then is placed, pulled and lifted, and the pretreated glass sheet is removed, and post-treatment is carried out to obtain a pretreated glass film; and step 2: a modified anti-fading coating is coated on the surface of the pretreated glass film, pre-reaction is carried out, and heat curing is carried out, so that the anti-deformation, anti-fading and aging-resistant glass film is obtained.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of glass coating film, and particularly relates to an anti-deformation, anti-fading and anti-aging glass film and a preparation method thereof. BACKGROUND

[0002] The glass film is a commonly used functional material in the fields of buildings and automobiles, has the functions of heat insulation and protection, and becomes a hot spot for use at present. However, the glass film at the present stage has the following problems.

[0003] Firstly, the traditional glass film is easily deformed under the influence of external temperature change, mechanical stress and other factors due to the insufficient toughness and cross-linking density of the glass film itself, which affects the use effect of the product. Secondly, the glass film is exposed to sunlight for a long time, has poor anti-ultraviolet performance, and has the phenomenon of glass film fading, which is difficult to meet the long-term use requirement. In order to improve the anti-ultraviolet performance, titanium dioxide and other nanoparticles with the ability to absorb ultraviolet rays are usually introduced, but the agglomeration phenomenon also occurs, and the anti-ultraviolet performance cannot be improved. Thirdly, the glass film is easily subjected to mechanical performance decline and greatly reduced anti-aging performance due to long-term exposure to high ultraviolet, high temperature and high humidity environment, which limits the use of the glass film.

[0004] Therefore, it is of great significance to solve the above problems and prepare an anti-deformation, anti-fading and anti-aging glass film. SUMMARY

[0005] The present application aims to provide an anti-deformation, anti-fading and anti-aging glass film and a preparation method thereof to solve the problems in the background.

[0006] In order to solve the above technical problems, the present application provides the following technical scheme:

[0007] A preparation method of an anti-deformation, anti-fading and anti-aging glass film, comprising the following steps:

[0008] Step 1: immerse the pretreated glass sheet in the island silicon-titanium sol, stand, pull up, remove the pretreated glass sheet, post-treat, and obtain a pretreated glass film;

[0009] Step 2: coat the modified anti-fading coating on the surface of the pretreated glass film, pre-react, and heat-cure to obtain an anti-deformation, anti-fading and anti-aging glass film.

[0010] More preferably, in step 1, the standing time is 3-5 min; the pulling up is vertical upward pulling up, and the pulling up speed is 0.5-0.6 cm / s; the post-treatment temperature is 400-450 DEG C, and the time is 10-20 min.

[0011] More preferably, in step 2, the coating amount is 3-5 g / cm2 ; the pre-reaction process parameters: set the light intensity 15-20 mW / cm 2 , irradiation under UV light for 8-12 min; the heat curing temperature is 120-160℃, and the time is 20-40 min.

[0012] More preferably, the preparation process of the island silicon-titanium sol is as follows:

[0013] S1-1: tetraisopropyl titanate, vinyl silane coupling agent are added into 30-40 wt% ethanol aqueous solution, and reacted at 60-80℃ for 1-2 hours to obtain a titanium dioxide sol solution;

[0014] S1-2: polydimethylsiloxane, the titanium dioxide sol solution is ultrasonically dispersed at 45-55℃ for 20-30 min to obtain a premix solution;

[0015] S1-3: tetraethyl orthosilicate, dibutyltin dilaurate, the premix solution are added into 30-40 wt% ethanol aqueous solution, hydrochloric acid is added to adjust the pH to 4.0-5.0, and reacted at 60-80℃ for 2-4 hours to obtain an island silicon-titanium sol.

[0016] More preferably, in the raw materials of the island silicon-titanium sol, the following components are included: 2-4 parts of tetraethyl orthosilicate, 0.2-0.4 parts of dibutyltin dilaurate, 8-12 parts of the premix solution, and 30-40 parts of 30-40 wt% ethanol aqueous solution;

[0017] In the premix solution, the mass ratio of polydimethylsiloxane to the titanium dioxide sol solution is 5:10-20;

[0018] In the titanium dioxide sol solution, the mass ratio of tetraisopropyl titanate to vinyl silane coupling agent to 30-40 wt% ethanol aqueous solution is 1:0.5-1.5:60-70.

[0019] More preferably, the preparation process of the modified anti-fading paint is as follows:

[0020] S2-1: preparation of modified acrylic resin: (1) hydroxyethyl acrylate, dimethyldichlorosilane, dibutyltin dilaurate are added into butyl acetate, triethylamine is added to adjust the pH to 5.2-6.2, and reacted at 50-60℃ for 7-9 hours, then separated and eluted to obtain a silicone-containing block monomer; (2) under a nitrogen atmosphere, the silicone-containing block monomer, methyl methacrylate, butyl acrylate, 2-perfluorodecyl acrylate, and a free radical initiator are added into butyl acetate, and reacted at 80-100℃ for 8-10 hours, then cooled, separated, and a modified acrylic resin is obtained;

[0021] S2-2: Preparation of the cerium-doped TiO2 / SiO2 core-shell microspheres: (1) cerium nitrate hexahydrate is added to a nitric acid aqueous solution with a pH of 1.0-1.1, tetrabutyl titanate is added, stirring at a speed of 500-1000 r / min for 2-3 hours, followed by hydrothermal reaction at 130-150℃ for 12-18 hours, cooling, centrifugation, washing, drying, to obtain cerium-doped TiO2; (2) the cerium-doped TiO2 is added to an isopropanol aqueous solution, ammonia water is added to adjust the pH to 8.8-9.2, tetraethyl orthosilicate is added, reaction at 25-35℃ for 20-28 hours, washing and drying, calcination at 500-600℃ for 2-3 hours, after cooling to room temperature, it is added to a 30-40wt% ethanol aqueous solution, mercaptosilane coupling agent and fluorine-containing silane coupling agent are added, reaction at 60-80℃ for 1-2 hours, drying, to obtain cerium-doped TiO2 / SiO2 core-shell microspheres;

[0022] S2-3: the modified acrylic resin, cerium-doped TiO2 / SiO2 core-shell microspheres, heat-insulating anti-ultraviolet black color masterbatch, anti-photooxidant, isopropanol-ethanol solution, propylene glycol monolaurate, and photoinitiator are mixed and stirred uniformly to obtain the modified anti-fading coating.

[0023] More preferably, in the raw materials of the modified anti-fading coating, the following components are included: 40-50 parts of modified acrylic resin, 15-25 parts of cerium-doped TiO2 / SiO2 core-shell microspheres, 1-3 parts of heat-insulating anti-ultraviolet black color masterbatch, 1-2 parts of anti-photooxidant, 60-80 parts of isopropanol-ethanol solution, 3-5 parts of propylene glycol monolaurate, and 0.5-1.5 parts of photoinitiator, by mass fraction.

[0024] More preferably, in the raw materials of the modified acrylic resin, the following components are included: 4-5 parts of organosilicon block monomer, 1-2 parts of methyl methacrylate, 1.5-2.5 parts of butyl acrylate, 8-9 parts of 2-perfluorodecyl acrylate, 0.5-1 part of free radical initiator, and 80-100 parts of butyl acetate, by mass fraction.

[0025] In the raw materials of the organosilicon block monomer, the following components are included: 4-5 parts of hydroxyethyl acrylate, 2-3 parts of dimethyldichlorosilane, 0.2-0.5 parts of dibutyltin dilaurate, and 60-80 parts of butyl acetate.

[0026] More preferably, in the raw materials of the cerium-doped TiO2 / SiO2 core-shell microspheres, the following components are included: 4-6 parts of cerium-doped TiO2, 60-80 parts of isopropanol aqueous solution, 0.5-2 parts of tetraethyl orthosilicate, 1-1.5 parts of mercaptosilane coupling agent, and 0.2-0.5 parts of fluorine-containing silane coupling agent, by mass fraction.

[0027] The molar ratio of cerium nitrate hexahydrate and tetrabutyl titanate in the raw material of the cerium-doped TiO2 is 1:10-12.

[0028] In a further aspect, the free radical initiator includes one or more of azobisisobutyronitrile, benzoyl peroxide, and potassium persulfate.

[0029] In a further aspect, the photoinitiator includes one or more of 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone.

[0030] In a further aspect, the volume ratio of isopropyl alcohol to deionized water in the isopropyl alcohol aqueous solution is 1:2-3.

[0031] In a further aspect, the volume ratio of isopropyl alcohol to ethanol in the isopropyl alcohol-ethanol solution is 1:3-4.

[0032] In a further aspect, the vinyl silane coupling agent includes one or more of vinyltrimethoxysilane, vinyltriethoxysilane, and γ-methacryloyloxypropyltrimethoxysilane.

[0033] In a further aspect, the mercapto silane coupling agent includes one or more of 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, and 2-mercaptoethyltriethoxysilane.

[0034] In a further aspect, the fluorine-containing silane coupling agent includes one or more of heptadecafluorodecyltrimethoxysilane, trifluoropropyltrimethoxysilane, and perfluorooctylethyltrimethoxysilane.

[0035] In a further aspect, the anti-photooxidant includes one or more of 2,6-di-tert-butyl-4-methylphenol, 2-hydroxy-4-methoxybenzophenone, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, and pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

[0036] In an aspect, the island silicon-titanium sol is used in combination with the modified anti-fading coating to improve the anti-deformation, anti-fading, and aging resistance of the glass film.

[0037] The island silicon-titanium sol is used as the base layer of the glass film, and the island structure is used to enhance the mechanical properties of the glass film.

[0038] The modified anti-fading coating uses multiple components to improve the anti-fading and aging resistance.

[0039] In the modified thermosetting resin, the mercapto and organosilicon block are grafted through chlorination reaction, and the modified acrylic resin is formed through free radical copolymerization, which introduces soft segments, hard segments and organosilicon blocks to improve the anti-deformation ability; and the fluorine element is introduced to improve the weather resistance and chemical stability.

[0040] In order to improve the anti-ultraviolet ability, titanium dioxide is introduced, but agglomeration phenomenon is easy to occur, and single titanium dioxide cannot meet the light refraction; therefore, the cerium-doped TiO2 / SiO2 core-shell microspheres are introduced into the coating to improve the interface roughness and light refraction ability; the cerium-doped TiO2 can enhance the absorption of ultraviolet light in the visible light region, improve the anti-ultraviolet performance, and further improve the anti-fading and aging resistance of the glass film; on the other hand, the cerium ion has a positive charge, and the outer silica has a large number of hydroxyl groups with a negative charge, which can be moved directionally through electrostatic action to improve the compatibility and prevent agglomeration; in addition, the outer silica is grafted with fluorine-containing silane coupling agent to form-CF3 hydrophobic group, which improves the weather resistance and enhances the compatibility; the heat-insulating anti-ultraviolet black color masterbatch and the anti-photooxidant are used in cooperation, the former directly absorbs ultraviolet light and insulates heat, and the latter captures free radicals to inhibit oxidation reaction, which together prevent the film layer from fading and aging.

[0041] The vinyl group in the island silicon-titanium sol and the mercapto group introduced in the modified anti-fading coating undergo mercapto click reaction under the action of a photoinitiator to form a covalent bond connection, realize the chemical crosslinking between the film layers, and significantly improve the overall crosslinking density and bonding force.

[0042] Compared with the prior art, the present application has the following advantages:

[0043] The scheme realizes chemical cross-linking between film layers by using the thiol click reaction of vinyl and thiol through the synergy of island silicon titanium sol and modified anti-fading coating, significantly improves the anti-deformation ability of the glass film by combining the island structure of the sol and the flexibility of the organic silicon block in the coating, and constructs an ultraviolet absorption-refraction-radical inhibition system by means of the multiple effects of cerium-doped TiO2 / SiO2core-shell microspheres, fluorine elements, hindered phenol groups and heat-insulating anti-ultraviolet black color masterbatch, and finally the prepared glass film has good anti-deformation, anti-fading and anti-aging properties. DETAILED DESCRIPTION

[0044] The technical solutions in the embodiments of the present application will be clearly and completely described below. Obviously, the described embodiments are only some of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0045] It should be noted that the following parts are mass parts, and there is no special restriction on the purchase manufacturers of all raw materials involved in the present application. Exemplarily, in the following embodiments, the CAS number of tetraisopropyl titanate is 546-68-9; the CAS number of hydroxyethyl acrylate is 818-61-1; the CAS number of dimethyldichlorosilane is 75-78-5; the CAS number of mercaptopropyltrimethoxysilane is 4420-74-0; the CAS number of methyl methacrylate is 80-62-6; the CAS number of butyl acrylate is 141-32-2; the CAS number of 2-perfluorodecyl acrylate ethyl ester is 17741-60-5; the CAS number of cerium nitrate hexahydrate is 10294-41-4, and the article number is 04-24-14; the CAS number of tetrabutyl titanate is 5593-70-4; the CAS number of tetraethyl orthosilicate is 78-10-4; the CAS number of propylene glycol monolaurate is 142-55-2; the CAS number of 1-hydroxy-cyclohexyl-phenyl ketone is 947-19-3; the CAS number of vinyl triethoxysilane is 78-08-0; the CAS number of trifluoropropyltrimethoxysilane is 429-60-7; the CAS number of 2,6-di-tert-butyl-4-methylphenol is 128-37-0; the relative molecular mass of polydimethylsiloxane is 5000, and the CAS number is 107-46-0; the heat-insulating anti-ultraviolet black color masterbatch is purchased from Shenzhen Chenmei Pigment Masterbatch Co., Ltd.

[0046] The following embodiments are particularly described:

[0047] (1) In the isopropyl alcohol aqueous solution, the volume ratio of isopropyl alcohol to deionized water is 1:2.5.

[0048] (2) In the isopropyl alcohol-ethanol solution, the volume ratio of isopropyl alcohol to ethanol is 1:3.5.

[0049] (3) The molar ratio of cerium nitrate hexahydrate to tetrabutyl titanate in the raw material of cerium-doped TiO2 is 1:10.5.

[0050] Embodiment 1: A method for preparing a deformation-resistant, anti-fading and aging-resistant glass film, comprising the following steps:

[0051] Step 1: (1) Tetraisopropyl titanate and vinyltriethoxysilane are added to 35 wt% aqueous ethanol solution at a mass ratio of 1:1:65, and reacted at 70°C for 1.5 hours to obtain a titanium dioxide sol solution; (2) Polydimethylsiloxane and the titanium dioxide sol solution are ultrasonically dispersed at 50°C for 25 min at a mass ratio of 5:15 to obtain a premix; (3) 3 parts of tetraethyl orthosilicate, 0.3 parts of dibutyltin dilaurate, and 10 parts of the premix are added to 35 parts of 35 wt% aqueous ethanol solution, hydrochloric acid is added to adjust the pH to 4.5, and the mixture is reacted at 70°C for 3 hours to obtain an island silicon-titanium sol;

[0052] Step 2: S2-1: Preparation of modified acrylic resin: (1) Add 4.5 parts of hydroxyethyl acrylate, 2.5 parts of dimethyl dichlorosilane, and 0.3 parts of dibutyltin dilaurate to 70 parts of butyl acetate, add triethylamine to adjust the pH to 5.7, react at 55°C for 8 hours, separate, elute, and obtain the organosilicon block monomer; (2) Under nitrogen atmosphere, add 4.5 parts of organosilicon block monomer, 1.5 parts of methyl methacrylate, 2 parts of butyl acrylate, and 8 parts of butyl acetate. Two parts of ethyl 2-perfluorodecyl acrylate and 0.7 parts of azobisisobutyronitrile were added to 90 parts of butyl acetate and reacted at 90°C for 9 hours. After cooling and separation, modified acrylic resin was obtained. S2-2: Preparation of cerium-doped TiO2 / SiO2 core-shell microspheres: (1) Cerium nitrate hexahydrate was added to a nitric acid aqueous solution with pH 1.0, and tetrabutyl titanate was added and stirred at 800 r / min for 2.5 hours. Then, hydrothermal reaction was carried out at 140°C for 16 hours and cooled. (1) Centrifuge, wash, and dry to obtain cerium-doped TiO2; (2) Add 5 parts of cerium-doped TiO2 to 70 parts of isopropanol aqueous solution, add ammonia to adjust the pH to 9.0, add 1.2 parts of tetraethyl orthosilicate and react at 30°C for 24 hours, wash and dry, calcine at 550°C for 2.5 hours, cool to room temperature, add to 35wt% ethanol aqueous solution, add 1.2 parts of 3-mercaptopropyltrimethoxysilane and 0.35 parts of trifluoropropyltrimethoxysilane. The reaction was carried out at 70℃ for 1.5 hours, and then dried to obtain cerium-doped TiO2 / SiO2 core-shell microspheres; S2-3: 45 parts of modified acrylic resin, 20 parts of cerium-doped TiO2 / SiO2 core-shell microspheres, 2 parts of heat-insulating and UV-resistant black masterbatch, 1.5 parts of 2,6-di-tert-butyl-4-methylphenol, 70 parts of isopropanol-ethanol solution, 4 parts of propylene glycol monolaurate, and 1 part of 1-hydroxy-cyclohexyl-phenyl ketone were mixed and stirred evenly to obtain a modified anti-fading coating;

[0053] Step 3: Immerse the pretreated glass sheet in the island silicon titanium sol, let it stand for 5 minutes, and then lift it vertically upward at a speed of 0.55 cm / s to remove the pretreated glass sheet. Then, post-treat it at 420℃ for 15 minutes to obtain the pretreated glass film.

[0054] Step 4: Apply the modified anti-fading coating at a concentration of 4 g / cm³. 2 The amount of coating is applied to the surface of the pretreated glass film, with a light intensity of 17mW / cm². 2 Irradiate with ultraviolet light for 10 minutes, then heat-cur at 140℃ for 30 minutes to obtain a glass film that is resistant to deformation, fading, and aging.

[0055] Example 2: A method for preparing a deformation-resistant, fade-resistant, and aging-resistant glass film, comprising the following steps:

[0056] Step 1: (1) titanium isopropylate, vinyltriethoxysilane were added into 35 wt% aqueous ethanol solution at a mass ratio of 1:1:65, and reacted at 70°C for 1.5 hours to obtain a titanium dioxide sol solution; (2) polydimethylsiloxane, the titanium dioxide sol solution were ultrasonically dispersed at 50°C for 25 min at a mass ratio of 5:10 to obtain a premix solution; (3) 3 parts of tetraethyl orthosilicate, 0.3 parts of dibutyltin dilaurate, 10 parts of the premix solution were added into 35 parts of 35 wt% aqueous ethanol solution, hydrochloric acid was added to adjust the pH to 4.5, and the mixture was reacted at 70°C for 3 hours to obtain a sea-island silicon-titanium sol;

[0057] Step 2: S2-1: Preparation of modified acrylic resin: (1) 4.5 parts of hydroxyethyl acrylate, 2.5 parts of dimethyldichlorosilane, 0.3 parts of dibutyltin dilaurate were added into 70 parts of butyl acetate, triethylamine was added to adjust the pH to 5.7, and the mixture was reacted at 55°C for 8 hours to obtain a silicone-containing block monomer; (2) 4.5 parts of the silicone-containing block monomer, 1.5 parts of methyl methacrylate, 2 parts of butyl acrylate, 8.2 parts of 2-perfluorodecyl acrylate, 0.7 parts of azobis isobutyronitrile were added into 90 parts of butyl acetate, and the mixture was reacted at 90°C for 9 hours to obtain a modified acrylic resin; S2-2: Preparation of cerium-doped TiO2 / SiO2core-shell microspheres: (1) cerium nitrate hexahydrate was added into a nitric acid aqueous solution with a pH of 1.0, and tetrabutyl titanate was added to stir at a speed of 800 r / min for 2.5 hours, followed by hydrothermal reaction at 140°C for 16 hours, cooling, centrifugation, washing, and drying to obtain cerium-doped TiO2; (2) 5 parts of the cerium-doped TiO2was added into 70 parts of isopropanol aqueous solution, ammonia water was added to adjust the pH to 9.0, 1.2 parts of tetraethyl orthosilicate was added, and the mixture was reacted at 30°C for 24 hours, washed and dried, calcined at 550°C for 2.5 hours, and then cooled to room temperature, and then added into 35 wt% aqueous ethanol solution, 1.2 parts of 3-mercaptopropyltrimethoxysilane and 0.35 parts of trifluoropropyltrimethoxysilane were added, and the mixture was reacted at 70°C for 1.5 hours and dried to obtain cerium-doped TiO2 / SiO2core-shell microspheres; S2-3: 40 parts of the modified acrylic resin, 15 parts of the cerium-doped TiO2 / SiO2core-shell microspheres, 1 part of heat-resistant and ultraviolet-resistant black color masterbatch, 1 part of 2,6-di-tert-butyl-4-methylphenol, 60 parts of isopropanol-ethanol solution, 3 parts of propylene glycol monolaurate, and 0.5 parts of 1-hydroxy-cyclohexyl-phenyl ketone were mixed and stirred uniformly to obtain a modified anti-fading coating;

[0058] Step 3: The pretreated glass sheet was immersed in the sea-island silicon-titanium sol, and was vertically pulled up at a speed of 0.55 cm / s for 5 min, and the pretreated glass sheet was removed, and the pretreated glass film was post-treated at 420°C for 15 min to obtain a pretreated glass film;

[0059] Step 4: The modified anti-fading coating was applied on the surface of the pretreated glass film in an amount of 4 g / cm 2 at an illumination intensity of 17 mW / cm 2 for 10 min under UV light irradiation, followed by thermal curing at 140°C for 30 min to obtain the anti-deformation anti-fading and aging-resistant glass film.

[0060] Example 3: A method for preparing an anti-deformation anti-fading and aging-resistant glass film, comprising the following steps:

[0061] Step 1: (1) Tetraisopropyl titanate and vinyltriethoxysilane were added to 35 wt% aqueous ethanol solution at a mass ratio of 1:1:65, and reacted at 70°C for 1.5 hours to obtain a titanium dioxide sol solution; (2) Polydimethylsiloxane and the titanium dioxide sol solution were ultrasonically dispersed at 50°C for 25 min at a mass ratio of 5:20 to obtain a premix; (3) 3 parts of tetraethyl orthosilicate, 0.3 parts of dibutyltin dilaurate, and 10 parts of the premix were added to 35 parts of 35 wt% aqueous ethanol solution, and hydrochloric acid was added to adjust the pH to 4.5, and then reacted at 70°C for 3 hours to obtain an island silicon-titanium sol;

[0062] Step 2: S2-1: Preparation of modified acrylic resin: (1) 4.5 parts of hydroxyethyl acrylate, 2.5 parts of dimethyl dichlorosilane, 0.3 parts of dibutyl tin dilaurate were added into 70 parts of butyl acetate, triethylamine was added to adjust the pH to 5.7, and the reaction was carried out at 55°C for 8 hours, and then separated, washed and eluted to obtain a silicone-containing block monomer; (2) under a nitrogen atmosphere, 4.5 parts of the silicone-containing block monomer, 1.5 parts of methyl methacrylate, 2 parts of butyl acrylate, 8.2 parts of 2-perfluorodecyl acrylate, 0.7 parts of azobis isobutyronitrile were added into 90 parts of butyl acetate, and the reaction was carried out at 90°C for 9 hours, and then cooled, separated to obtain a modified acrylic resin; S2-2: Preparation of cerium-doped TiO2 / SiO2 core-shell microspheres: (1) cerium nitrate hexahydrate was added into a nitric acid aqueous solution with a pH of 1.0, and tetrabutyl titanate was added and stirred at a speed of 800 r / min for 2.5 hours, and then hydrothermal reaction was carried out at 140°C for 16 hours, and then cooled, centrifuged, washed and dried to obtain cerium-doped TiO2; (2) 5 parts of the cerium-doped TiO2 was added into 70 parts of isopropanol aqueous solution, and ammonia water was added to adjust the pH to 9.0, and then 1.2 parts of tetraethyl orthosilicate was added and the reaction was carried out at 30°C for 24 hours, and then washed and dried, and then calcined at 550°C for 2.5 hours, and then cooled to room temperature, and then added into 35 wt% ethanol aqueous solution, and then 1.2 parts of 3-mercaptopropyl trimethoxysilane and 0.35 parts of trifluoropropyl trimethoxysilane were added, and the reaction was carried out at 70°C for 1.5 hours, and then dried to obtain cerium-doped TiO2 / SiO2 core-shell microspheres; S2-3: 50 parts of the modified acrylic resin, 25 parts of the cerium-doped TiO2 / SiO2 core-shell microspheres, 3 parts of heat-resistant and ultraviolet-resistant black color masterbatch, 2 parts of 2,6-di-tert-butyl-4-methylphenol, 80 parts of isopropanol-ethanol solution, 5 parts of propylene glycol monolaurate, and 1.5 parts of 1-hydroxy-cyclohexyl-phenyl ketone were uniformly mixed and stirred to obtain a modified anti-fading coating.

[0063] Step 3: The pretreated glass sheet was immersed in the island-silicon-titanium sol, and was vertically pulled up at a speed of 0.55 cm / s for 5 min, and then post-treated at 420°C for 15 min, and then the pretreated glass sheet was removed to obtain a pretreated glass film;

[0064] Step 4: The modified anti-fading coating was coated on the surface of the pretreated glass film in an amount of 4 g / cm 2 , and then irradiated under ultraviolet light for 10 min at an illumination intensity of 17 mW / cm 2 , and then heat-cured at 140°C for 30 min to obtain a deformation-resistant anti-fading and aging-resistant glass film.

[0065] Comparative Example 1: Based on Example 1, the coating amount of the modified anti-fading coating was adjusted, and the rest of the process was unchanged, and the adjustment was as follows: Step 4: the modified anti-fading coating was coated on the surface of the pretreated glass film in an amount of 1.5 g / cm 2The modified anti-fading coating was prepared by mixing 45 parts of the modified acrylic resin, 20 parts of the cerium-doped TiO2 / SiO2core-shell microspheres, 2 parts of the heat-insulating anti-ultraviolet black color masterbatch, 1.5 parts of 2,6-di-tert-butyl-4-methylphenol, 70 parts of an isopropyl alcohol-ethanol solution, 4 parts of propylene glycol monolaurate, and 1 part of 1-hydroxy-cyclohexyl-phenyl ketone. 2 The modified anti-fading coating was prepared by mixing 45 parts of the modified acrylic resin, 20 parts of the cerium-doped TiO2 / SiO2core-shell microspheres, 2 parts of the heat-insulating anti-ultraviolet black color masterbatch, 1.5 parts of 2,6-di-tert-butyl-4-methylphenol, 70 parts of an isopropyl alcohol-ethanol solution, 4 parts of propylene glycol monolaurate, and 1 part of 1-hydroxy-cyclohexyl-phenyl ketone.

[0066] Comparative Example 2: Based on Example 1, no silicone block was introduced, and the rest of the process was unchanged, and was adjusted to:

[0067] Step 2: S2-1: Preparation of the modified acrylic resin: 2 parts of hydroxyethyl acrylate, 1.5 parts of methyl methacrylate, 2 parts of butyl acrylate, 8.2 parts of 2-perfluorodecyl acrylate, and 0.7 parts of azobisisobutyronitrile were added to 90 parts of butyl acetate under a nitrogen atmosphere, and reacted at 90°C for 9 hours, cooled, separated, and the modified acrylic resin was obtained; S2-2: Preparation of cerium-doped TiO2 / SiO2core-shell microspheres: (1) Cerium nitrate hexahydrate was added to a nitric acid aqueous solution with a pH of 1.0, and tetrabutyl titanate was added and stirred at a speed of 800 r / min for 2.5 hours, followed by hydrothermal reaction at 140°C for 16 hours, cooling, centrifugation, washing, and drying to obtain cerium-doped TiO2; (2) 5 parts of cerium-doped TiO2was added to 70 parts of an isopropyl alcohol aqueous solution, and ammonia water was added to adjust the pH to 9.0, and 1.2 parts of tetraethyl orthosilicate was added and reacted at 30°C for 24 hours, washed and dried, calcined at 550°C for 2.5 hours, and after cooling to room temperature, it was added to a 35 wt% ethanol aqueous solution, and 1.2 parts of 3-mercaptopropyltrimethoxysilane and 0.35 parts of trifluoropropyltrimethoxysilane were added and reacted at 70°C for 1.5 hours, and dried to obtain cerium-doped TiO2 / SiO2core-shell microspheres; S2-3: 45 parts of the modified acrylic resin, 20 parts of the cerium-doped TiO2 / SiO2core-shell microspheres, 2 parts of the heat-insulating anti-ultraviolet black color masterbatch, 1.5 parts of 2,6-di-tert-butyl-4-methylphenol, 70 parts of an isopropyl alcohol-ethanol solution, 4 parts of propylene glycol monolaurate, and 1 part of 1-hydroxy-cyclohexyl-phenyl ketone were mixed and stirred uniformly to obtain the modified anti-fading coating.

[0068] Comparative Example 3: Based on Example 1, the cerium-doped TiO2 / SiO2core-shell microspheres were adjusted to nano-titanium dioxide, and the rest of the process was unchanged, and was adjusted to:

[0069] Step 2: S2-2: 45 parts of the modified acrylic resin, 20 parts of the nano-titanium dioxide, 2 parts of the heat-insulating anti-ultraviolet black color masterbatch, 1.5 parts of 2,6-di-tert-butyl-4-methylphenol, 70 parts of an isopropyl alcohol-ethanol solution, 4 parts of propylene glycol monolaurate, and 1 part of 1-hydroxy-cyclohexyl-phenyl ketone were mixed and stirred uniformly to obtain the modified anti-fading coating.

[0070] The nano-titanium dioxide has a specification of 20 nm.

[0071] Comparative Example 4: Based on Example 1, no fluorine element was introduced, and the rest of the process was unchanged, and was adjusted to:

[0072] Step 2: (2) Under a nitrogen atmosphere, 4.5 parts of a silicone block monomer, 1.5 parts of methyl methacrylate, 2 parts of butyl acrylate, 1.5 parts of ethyl acrylate, and 0.7 parts of azobisisobutyronitrile were added to 90 parts of butyl acetate, and reacted at 90°C for 9 hours, cooled, and separated to obtain a modified acrylic resin; S2-2: Preparation of cerium-doped TiO2 / SiO2core-shell microspheres: (1) Cerium nitrate hexahydrate was added to a nitric acid aqueous solution with a pH of 1.0, and tetrabutyl titanate was added and stirred at a speed of 800 r / min for 2.5 hours, followed by hydrothermal reaction at 140°C for 16 hours, cooling, centrifugation, washing, and drying to obtain cerium-doped TiO2; (2) 5 parts of cerium-doped TiO2was added to 70 parts of an isopropanol aqueous solution, ammonia water was added to adjust the pH to 9.0, 1.2 parts of tetraethyl orthosilicate was added, and reacted at 30°C for 24 hours, washed and dried, and calcined at 550°C for 2.5 hours, after cooling to room temperature, it was added to a 35wt% ethanol aqueous solution, 1.3 parts of 3-mercaptopropyltrimethoxysilane was added, and reacted at 70°C for 1.5 hours, and dried to obtain cerium-doped TiO2 / SiO2core-shell microspheres.

[0073] Detection experiment: One of the anti-deformation, anti-fading, and aging-resistant glass films prepared by Examples 1-3 and Comparative Examples 1-4 was detected for its performance: (1) Tensile strength test: The glass films prepared by Examples 1-3 and Comparative Examples 1-4 were placed under ultraviolet light, the wavelength of the light source was set to 340 nm, and aged for 120 hours. The tensile strength before and after aging was tested according to GB / T1040.1-2018, and the results are shown in Table 1; (2) Anti-ultraviolet performance test: The glass films prepared by Examples 1-3 and Comparative Examples 1-4 were tested for ultraviolet absorption rate. The higher the ultraviolet absorption rate, the better the anti-ultraviolet performance, and the results are shown in Table 1;

[0074]

[0075]

[0076] Table 1

[0077] Result analysis: According to the data analysis of Table 1, it can be seen from the data of Comparative Example 1 that the bonding force between the island silicon-titanium sol and the modified paint decreases when the coating amount of the modified anti-fading paint is adjusted, the tensile strength decreases during the ultraviolet aging process, and the ultraviolet absorption rate decreases; it can be seen from the data of Comparative Example 2 that the elasticity of the resin decreases and the brittleness increases without introducing the organic silicon block, the tensile strength decreases, and the ultraviolet absorption rate is slightly higher than that of Comparative Example 1; it can be seen from the data of Comparative Example 3 that the light refraction rate decreases, the ultraviolet light absorption rate decreases significantly, and the tensile strength and aging resistance decrease when the cerium-doped TiO2 / SiO2 core-shell microspheres are adjusted to nano titanium dioxide, which is easy to produce agglomeration, has no core-shell structure, and has no addition of cerium ions; it can be seen from the data of Comparative Example 4 that the overall weather resistance and aging resistance decrease significantly without introducing fluorine elements.

[0078] It is apparent to those skilled in the art that the present application is not limited to the details of the foregoing exemplary embodiments, and that the present application can be implemented in other particular forms without departing from the spirit or essential characteristics of the present application. Therefore, the embodiments should be considered in all respects as illustrative and not restrictive, the scope of the present application being defined by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims

1. A method for preparing a deformation-resistant, fade-resistant, and aging-resistant glass film, characterized in that: Includes the following steps: Step 1: Immerse the pretreated glass sheet in the island silicon-titanium sol, let it stand, lift it out, remove the pretreated glass sheet, and perform post-processing to obtain the pretreated glass film; Step 2: Apply the modified anti-fading coating to the surface of the pretreated glass film, pre-react, and heat-cur to obtain an anti-deformation, anti-fading, and aging-resistant glass film; The preparation process of the island-of-sea silicon-titanium sol is as follows: S1-1: Tetraisopropyl titanate and vinylsilane coupling agent are added to a 30-40 wt% aqueous ethanol solution and reacted at 60-80°C for 1-2 hours to obtain titanium dioxide sol solution. S1-2: Disperse polydimethylsiloxane and titanium dioxide sol at 45~55℃ for 20~30 min to obtain a premixed solution; S1-3: Tetraethyl orthosilicate, dibutyltin dilaurate, and the premix were added to a 30-40 wt% ethanol aqueous solution, and hydrochloric acid was added to adjust the pH to 4.0-5.

0. The mixture was reacted at 60-80℃ for 2-4 hours to obtain island-type silicon-titanium sol. The raw materials of the island-based silicon-titanium sol include the following components: by mass, 2-4 parts of tetraethyl orthosilicate, 0.2-0.4 parts of dibutyltin dilaurate, 8-12 parts of premixed solution, and 30-40 parts of 30-40 wt% aqueous ethanol solution; In the premixed solution, the mass ratio of polydimethylsiloxane to titanium dioxide sol is 5:10~20; In the titanium dioxide sol solution, the mass ratio of tetraisopropyl titanate, vinylsilane coupling agent, and 30-40 wt% ethanol aqueous solution is 1:0.5-1.5:60-70. The modified anti-fading coating comprises the following components by weight: 40-50 parts modified acrylic resin, 15-25 parts cerium-doped TiO2 / SiO2 core-shell microspheres, 1-3 parts heat-insulating and UV-resistant black masterbatch, 1-2 parts anti-photooxidation agent, 60-80 parts isopropanol-ethanol solution, 3-5 parts propylene glycol monolaurate, and 0.5-1.5 parts photoinitiator.

2. The method for preparing an anti-deformation, anti-fading, and aging-resistant glass film according to claim 1, characterized in that: In step 1, the settling time is 3-5 minutes; the lifting is a vertical upward lifting at a speed of 0.5-0.6 cm / s; the post-treatment temperature is 400-450℃ and the time is 10-20 minutes.

3. The method for preparing an anti-deformation, anti-fading, and aging-resistant glass film according to claim 1, characterized in that: In step 2, the coating amount is 3~5 g / cm³. 2 The pre-reaction process parameters are set as follows: light intensity 15~20mW / cm². 2 Irradiate with ultraviolet light for 8-12 minutes; the temperature for heat curing is 120-160℃ and the time is 20-40 minutes.

4. The method for preparing an anti-deformation, anti-fading, and aging-resistant glass film according to claim 1, characterized in that: The preparation process of the modified anti-fading coating is as follows: S2-1: Preparation of modified acrylic resin: (1) Add hydroxyethyl acrylate, dimethyl dichlorosilane, and dibutyltin dilaurate to butyl acetate, add triethylamine to adjust the pH to 5.2~6.2, react at 50~60℃ for 7~9 hours, separate, and elute to obtain organosilicon block monomer; (2) Under nitrogen atmosphere, add organosilicon block monomer, methyl methacrylate, butyl acrylate, ethyl 2-perfluorodecyl acrylate, and free radical initiator to butyl acetate, react at 80~100℃ for 8~10 hours, cool, and separate to obtain modified acrylic resin; S2-2: Preparation of cerium-doped TiO2 / SiO2 core-shell microspheres: (1) Cerium nitrate hexahydrate was added to a nitric acid aqueous solution with a pH of 1.0-1.1, and tetrabutyl titanate was added and stirred at 500-1000 r / min for 2-3 hours. Then, the mixture was hydrothermally reacted at 130-150℃ for 12-18 hours. After cooling, centrifugation, washing, and drying, cerium-doped TiO2 was obtained. (2) Cerium-doped TiO2 was added to an isopropanol aqueous solution, and ammonia was added to adjust the pH to 8.8-9.

2. Tetrabutyl orthosilicate was added and reacted at 25-35℃ for 20-28 hours. After washing and drying, the mixture was calcined at 500-600℃ for 2-3 hours. After cooling to room temperature, it was added to a 30-40wt% ethanol aqueous solution, and mercaptosilane coupling agent and fluorinated silane coupling agent were added. The mixture was reacted at 60-80℃ for 1-2 hours and dried to obtain cerium-doped TiO2 / SiO2 core-shell microspheres. S2-3: Modified acrylic resin, cerium-doped TiO2 / SiO2 core-shell microspheres, heat-insulating and UV-resistant black masterbatch, anti-photooxidant, isopropanol-ethanol solution, propylene glycol monolaurate, and photoinitiator are mixed and stirred evenly to obtain a modified anti-fading coating.

5. The method for preparing an anti-deformation, anti-fading, and aging-resistant glass film according to claim 4, characterized in that: The modified acrylic resin raw materials include the following components: by mass, 4-5 parts containing organosilicon block monomers, 1-2 parts methyl methacrylate, 1.5-2.5 parts butyl acrylate, 8-9 parts ethyl 2-perfluorodecyl acrylate, 0.5-1 part free radical initiator, and 80-100 parts butyl acetate. The raw material containing organosilicon block monomers includes the following components: 4-5 parts hydroxyethyl acrylate, 2-3 parts dimethyldichlorosilane, 0.2-0.5 parts dibutyltin dilaurate, and 60-80 parts butyl acetate.

6. The method for preparing an anti-deformation, anti-fading, and aging-resistant glass film according to claim 4, characterized in that: The raw material for the cerium-doped TiO2 / SiO2 core-shell microspheres includes the following components by mass: 4-6 parts cerium-doped TiO2, 60-80 parts isopropanol aqueous solution, 0.5-2 parts tetraethyl orthosilicate, 1-1.5 parts mercaptosilane coupling agent, and 0.2-0.5 parts fluorinated silane coupling agent. In the raw material of cerium-doped TiO2, the molar ratio of cerium nitrate hexahydrate to tetrabutyl titanate is 1:10~12.

7. The anti-deformation, anti-fading, and anti-aging glass film prepared by the method according to any one of claims 1 to 6.

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