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

Abstract

The invention relates to the technical field of glass coating films, in particular to an anti-deformation, anti-fading and anti-aging glass film and a preparation method thereof. Comprising the following steps: 1, immersing a pretreated glass sheet into a sea island silicon-titanium sol, standing, pulling, removing the pretreated glass sheet, and carrying out post-treatment to obtain a pretreated glass film; 2, coating the surface of the pretreated glass film with a modified anti-fading coating, and carrying out pre-reaction and thermocuring; therefore, the anti-deformation, anti-fading and anti-aging glass film is obtained.

Description

Technical Field

[0001] The present invention relates to the field of glass coating films, and specifically to an anti-deformation, anti-fading and anti-aging glass film and a preparation method thereof. Background Art

[0002] As a common functional material in the fields of architecture, automobiles, etc., glass films have functions such as heat insulation and protection, and have become a hot spot in current use; however, the current glass films have the following problems at the same time:

[0003] First, under the influence of various factors such as external temperature changes and mechanical stress, due to the insufficient toughness and crosslinking density of the glass film itself, the glass film is prone to deformation, affecting the use effect of the product; second, due to the long-term exposure of the glass film to sunlight and poor ultraviolet resistance, the phenomenon of glass film fading will occur, making it difficult to meet the long-term use requirements; in order to improve the ultraviolet resistance, nanoparticles with the ability to absorb ultraviolet rays such as titanium dioxide are usually introduced, but at the same time, the phenomenon of agglomeration also occurs, and the ultraviolet resistance cannot be improved; third, due to the need for the glass film to be long-term exposed to an environment of high ultraviolet rays, high temperature and humidity, the mechanical properties are prone to decline, and the anti-aging performance will also be greatly reduced, restricting the use of the glass film.

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

[0005] The purpose of the present invention is to provide an anti-deformation, anti-fading and anti-aging glass film and a preparation method thereof 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 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 sea-island silicon-titanium sol, let it stand, lift it vertically upward, remove the pretreated glass sheet, and perform post-treatment to obtain a pretreated glass film;

[0009] Step 2: Coating the surface of the pretreated glass film with the modified anti-fading coating, pre-reacting, and thermally curing to obtain the anti-deformation, anti-fading and anti-aging glass film.

[0010] Preferably, in Step 1, the standing time is 3-5 min; the lifting is vertical upward lifting, and the lifting speed is 0.5-0.6 cm / s; the post-treatment temperature is 400-450 °C, and the time is 10-20 min.

[0011] Preferably, in Step 2, the coating amount is 3-5 g / cm2 ; Process parameters of the pre-reaction: set the light intensity at 15 - 20 mW / cm 2 , irradiate under ultraviolet light for 8 - 12 min; the temperature of the thermal curing is 120 - 160 °C, and the time is 20 - 40 min.

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

[0013] S1-1: Add tetra-isopropyl titanate and vinyl silane coupling agent into 30 - 40 wt% ethanol aqueous solution, react at 60 - 80 °C for 1 - 2 hours to obtain titanium dioxide sol solution;

[0014] S1-2: Ultrasonically disperse polydimethylsiloxane and titanium dioxide sol solution at 45 - 55 °C for 20 - 30 min to obtain a premixed solution;

[0015] S1-3: Add tetraethyl orthosilicate, dibutyltin dilaurate, and the premixed solution into 30 - 40 wt% ethanol aqueous solution, adjust the pH to 4.0 - 5.0 with hydrochloric acid, and react at 60 - 80 °C for 2 - 4 hours to obtain sea-island silicon-titanium sol.

[0016] Preferably, in the raw materials of the sea-island silicon-titanium sol, it includes the following components: by mass fraction, 2 - 4 parts of tetraethyl orthosilicate, 0.2 - 0.4 parts of dibutyltin dilaurate, 8 - 12 parts of the premixed solution, 30 - 40 parts of 30 - 40 wt% ethanol aqueous solution;

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

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

[0019] Preferably, the preparation process of the modified anti-fading coating is as follows:

[0020] S2-1: Preparation of modified acrylic resin: (1) Add hydroxyethyl acrylate, dimethyldichlorosilane, and dibutyltin dilaurate into butyl acetate, adjust the pH to 5.2 - 6.2 with triethylamine, react at 50 - 60 °C for 7 - 9 hours, separate and wash to obtain an organosilicon block monomer; (2) Under a nitrogen atmosphere, add the organosilicon block monomer, methyl methacrylate, butyl acrylate, 2-perfluorodecyl ethyl acrylate, and a radical initiator into butyl acetate, react at 80 - 100 °C for 8 - 10 hours, cool and separate to obtain the modified acrylic resin;

[0021] S2-2: Cerium-doped TiO 2 / SiO 2 Preparation of core-shell microspheres: (1) Cerium nitrate hexahydrate was added to a nitric acid aqueous solution with a pH of 1.0 - 1.1, tetrabutyl titanate was added, and the mixture was stirred at a speed of 500 - 1000 r / min for 2 - 3 hours. Subsequently, it was subjected to hydrothermal reaction at 130 - 150 °C for 12 - 18 hours, cooled, centrifuged, washed, and dried to obtain cerium-doped TiO 2 ; (2) The cerium-doped TiO 2 was added to an isopropyl alcohol aqueous solution, ammonia water was added to adjust the pH to 8.8 - 9.2, tetraethyl orthosilicate was added, and the reaction was carried out at 25 - 35 °C for 20 - 28 hours. After washing and drying, it was calcined at 500 - 600 °C for 2 - 3 hours. After cooling to room temperature, it was added to a 30 - 40 wt% ethanol aqueous solution, a mercapto silane coupling agent and a fluorine-containing silane coupling agent were added, and the reaction was carried out at 60 - 80 °C for 1 - 2 hours, followed by drying to obtain cerium-doped TiO 2 / SiO 2 core-shell microspheres;

[0022] S2-3: The modified acrylic resin, cerium-doped TiO 2 / SiO 2 core-shell microspheres, heat-insulating and ultraviolet-resistant black color masterbatch, light antioxidant, isopropanol-ethanol solution, propylene glycol monolaurate, and photoinitiator were mixed and stirred evenly to obtain a modified anti-fading coating.

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

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

[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 part of dibutyltin dilaurate, and 60 - 80 parts of butyl acetate.

[0026] Preferably, the cerium-doped TiO 2 / SiO 2Among the raw materials of the core-shell microspheres, the following components are included: by mass parts, 4 to 6 parts of cerium-doped TiO 2 , 60 to 80 parts of isopropyl alcohol aqueous solution, 0.5 to 2 parts of tetraethyl orthosilicate, 1 to 1.5 parts of mercapto silane coupling agent, 0.2 to 0.5 parts of fluorosilane coupling agent;

[0027] In the raw materials of the cerium-doped TiO 2 , the molar ratio of cerium nitrate hexahydrate to tetrabutyl titanate is 1:10 to 12.

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

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

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

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

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

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

[0034] In a further embodiment, the fluorosilane coupling agent includes one or more of heptadecafluorodecyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, and perfluorooctylethyltrimethoxysilane.

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

[0036] In the embodiment, the sea-island silicon-titanium sol and the modified anti-fading coating cooperate to improve the anti-deformation, anti-fading, and aging resistance of the glass film.

[0037] Among them, the sea-island silica-titania sol serves as the base layer of the glass film, enhancing the mechanical properties of the glass film through its sea-island structure. Tetraisopropyl titanate hydrolyzes and condenses to form titanium dioxide, which acts as the "island phase" to provide rigid support, effectively disperse stress, and improve the impact resistance of the film layer; tetraethyl orthosilicate hydrolyzes and crosslinks into a silicone network, wrapping polydimethylsiloxane molecules to form an elastic "sea phase", which absorbs external energy through deformation. Vinyl silane coupling agent hydrolyzes and grafts in the sol to form Si-O-Ti covalent bonds and introduce vinyl groups, not only enhancing the internal structural stability of the sol, but also providing active sites for subsequent covalent crosslinking with the coating, enabling the sol layer and the coating layer to form a firm bond.

[0038] Among them, the modified anti-fading coating uses multiple components to synergistically improve the anti-fading and aging resistance performance.

[0039] In terms of the modified thermosetting resin, mercapto groups and silicone blocks are grafted through chlorination reaction, and then modified acrylic resin is formed through free radical copolymerization, introducing soft segments, hard segments, and silicone blocks to improve the anti-deformation ability; fluorine elements are introduced to improve the weather resistance and chemical stability.

[0040] Ce-doped TiO 2 / SiO 2 In terms of the core-shell microspheres, in order to improve the anti-ultraviolet ability, titanium dioxide is introduced, but agglomeration is likely to occur, and single titanium dioxide cannot meet the light refraction requirements; therefore, Ce-doped TiO 2 / SiO 2 core-shell microspheres are introduced into the coating to increase the interface roughness and enhance the light refraction ability. Using Ce-doped TiO 2 On the one hand, it can enhance the absorption of ultraviolet light in the visible light region by titanium dioxide, improve the anti-ultraviolet performance, and further enhance the anti-fading and aging resistance ability of the glass film; on the other hand, cerium ions carry positive charges, and the outer layer of silica contains a large number of hydroxyl groups with negative charges, which can move directionally through electrostatic interaction to improve the compatibility and prevent agglomeration; in addition, the outer layer of silica is grafted with fluorosilane coupling agent to form -CF 3 hydrophobic groups, improving the weather resistance and enhancing the compatibility; the heat-insulating and anti-ultraviolet black color masterbatch and the anti-photooxidant work together. The former directly absorbs ultraviolet light and insulates heat, and the latter captures free radicals to inhibit oxidation reactions, jointly preventing the film layer from fading and aging.

[0041] The vinyl groups in the sea-island silica-titania sol and the mercapto groups introduced into the modified anti-fading coating undergo thiol click reaction under the action of a photoinitiator to form covalent bond connections, realizing chemical crosslinking between the film layers and significantly improving the overall crosslinking density and binding force.

[0042] Compared with the prior art, the beneficial effects of the present invention are:

[0043] Through the synergy of sea-island silica-titania sol and the modified anti-fading coating, the thiol-ene click reaction of vinyl and mercapto groups is used to achieve chemical cross-linking between the film layers. Combining the rigid-flexible sea-island structure of the sol and the flexibility of the silicone block in the coating, the anti-deformation ability of the glass film is significantly improved. At the same time, through the multiple effects of cerium-doped TiO 2 / SiO 2 core-shell microspheres, fluorine element, hindered phenol groups and heat-insulating and anti-ultraviolet black color masterbatch, a system of ultraviolet absorption-refraction-free radical inhibition is constructed, and the weather resistance is enhanced by the fluorine element. Finally, the prepared glass film has good anti-deformation, anti-fading and anti-aging properties. Specific embodiments

[0044] 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 the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0045] It should be noted that the following parts are parts by mass, and there are no special restrictions on the manufacturers of all raw materials involved in the present invention. Exemplarily, in the following embodiments, the CAS number of titanium tetraisopropoxide 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 ethyl acrylate is 17741-60-5; the CAS number of cerium nitrate hexahydrate is 10294-41-4, and the product 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-phenylmethanone is 947-19-3; the CAS number of vinyltriethoxysilane 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 and anti-ultraviolet black color masterbatch is purchased from Shenzhen Chenmei Pigment Masterbatch Co., Ltd.

[0046] The following examples are specifically described:

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

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

[0049] (3) In the raw materials of cerium-doped TiO 2 , the molar ratio of cerium nitrate hexahydrate to tetrabutyl titanate is 1:10.5.

[0050] Example 1: A preparation method of an anti-deformation, anti-fading and anti-aging glass film, comprising the following steps:

[0051] Step 1: (1) Add tetraisopropyl titanate and vinyltriethoxysilane to a 35 wt% ethanol aqueous solution according to a mass ratio of 1:1:65, and react at 70 °C for 1.5 hours to obtain a titanium dioxide sol solution; (2) Ultrasonically disperse polydimethylsiloxane and the titanium dioxide sol solution at a mass ratio of 5:15 at 50 °C for 25 min to obtain a premixed solution; (3) Add 3 parts of tetraethyl orthosilicate, 0.3 part of dibutyltin dilaurate, and 10 parts of the premixed solution to 35 parts of a 35 wt% ethanol aqueous solution, add hydrochloric acid to adjust the pH to 4.5, and react at 70 °C for 3 hours to obtain a sea-island silicon-titanium sol;

[0052] Step 2: S2-1: Preparation of a modified acrylic resin: (1) Add 4.5 parts of hydroxyethyl acrylate, 2.5 parts of dimethyldichlorosilane, and 0.3 part of dibutyltin dilaurate to 70 parts of butyl acetate, add triethylamine to adjust the pH to 5.7, and react at 55 °C for 8 hours, separate, wash, and obtain an organosilicon block monomer; (2) Under a nitrogen atmosphere, add 4.5 parts of the organosilicon block monomer, 1.5 parts of methyl methacrylate, 2 parts of butyl acrylate, 8.2 parts of 2-perfluorodecyl ethyl acrylate, and 0.7 part of azobisisobutyronitrile to 90 parts of butyl acetate, react at 90 °C for 9 hours, cool, and separate to obtain a modified acrylic resin; S2-2: Preparation of cerium-doped TiO 2 / SiO 2 core-shell microspheres: (1) Add cerium nitrate hexahydrate to a nitric acid aqueous solution with a pH of 1.0, add tetrabutyl titanate, and stir at 800 r / min for 2.5 hours, then carry out a hydrothermal reaction at 140 °C for 16 hours, cool, centrifuge, wash, and dry to obtain cerium-doped TiO 2 ; (2) Add 5 parts of cerium-doped TiO 2 to 70 parts of an isopropanol aqueous solution, add ammonia water 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, and after cooling to room temperature, add it to a 35 wt% ethanol aqueous solution, add 1.2 parts of 3-mercaptopropyltrimethoxysilane and 0.35 part of trifluoropropyltrimethoxysilane, react at 70 °C for 1.5 hours, and dry to obtain cerium-doped TiO 2 / SiO 2Core-shell microspheres; S2-3: Mix 45 parts of modified acrylic resin, 20 parts of cerium-doped TiO 2 / SiO 2 core-shell microspheres, 2 parts of heat-insulating and ultraviolet-resistant black color 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-phenylmethanone evenly to obtain a modified anti-fading coating;

[0053] Step 3: Immerse the pretreated glass sheet in the sea-island silicon titania sol, let it stand for 5 min, vertically lift it upward at a speed of 0.55 cm / s, remove the pretreated glass sheet, and post-treat it at 420 °C for 15 min to obtain a pretreated glass film;

[0054] Step 4: Coat the modified anti-fading coating on the surface of the pretreated glass film in an amount of 4 g / cm 2 and irradiate it under ultraviolet light with a light intensity of 17 mW / cm 2 for 10 min, and then thermally cure it at 140 °C for 30 min to obtain an anti-deformation, anti-fading, and aging-resistant glass film.

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

[0056] Step 1: (1) Add titanium tetraisopropoxide and vinyltriethoxysilane to a 35 wt% ethanol aqueous solution according to a mass ratio of 1:1:65, and react at 70 °C for 1.5 hours to obtain a titanium dioxide sol solution; (2) Ultrasonically disperse polydimethylsiloxane and the titanium dioxide sol solution according to a mass ratio of 5:10 at 50 °C for 25 min to obtain a premixed solution; (3) Add 3 parts of tetraethyl orthosilicate, 0.3 parts of dibutyltin dilaurate, and 10 parts of the premixed solution to 35 parts of a 35 wt% ethanol aqueous solution, add hydrochloric acid to adjust the pH to 4.5, and react at 70 °C for 3 hours to obtain a sea-island silicon titania sol;

[0057] Step 2: S2-1: Preparation of modified acrylic resin: (1) Add 4.5 parts of hydroxyethyl acrylate, 2.5 parts of dimethyldichlorosilane, and 0.3 parts of dibutyltin dilaurate to 70 parts of butyl acetate, add triethylamine to adjust the pH to 5.7, and react at 55 °C for 8 hours, separate and elute to obtain an organosilicon block monomer; (2) Under a nitrogen atmosphere, add 4.5 parts of the organosilicon block monomer, 1.5 parts of methyl methacrylate, 2 parts of butyl acrylate, 8.2 parts of 2-perfluorodecyl ethyl acrylate, and 0.7 parts of azobisisobutyronitrile to 90 parts of butyl acetate, react at 90 °C for 9 hours, cool and separate to obtain a modified acrylic resin; S2-2: Cerium-doped TiO 2 / SiO 2Preparation of core-shell microspheres: (1) Cerium nitrate hexahydrate was added to a nitric acid aqueous solution with a pH of 1.0, tetrabutyl titanate was added, and the mixture was stirred at a speed of 800 r / min for 2.5 hours. Subsequently, it was subjected to hydrothermal reaction at 140 °C for 16 hours, cooled, centrifuged, washed, and dried to obtain cerium-doped TiO 2 ; (2) 5 parts of cerium-doped TiO 2 was 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 the reaction was carried out at 30 °C for 24 hours. After washing and drying, it was calcined at 550 °C for 2.5 hours. After cooling to room temperature, it was added to a 35 wt% ethanol aqueous solution, 1.2 parts of 3-mercaptopropyltrimethoxysilane and 0.35 parts of trifluoropropyltrimethoxysilane were added, and the reaction was carried out at 70 °C for 1.5 hours, and then dried to obtain cerium-doped TiO 2 / SiO 2 core-shell microspheres; S2-3: 40 parts of modified acrylic resin, 15 parts of cerium-doped TiO 2 / SiO 2 core-shell microspheres, 1 part of heat-insulating and anti-ultraviolet 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 part of 1-hydroxy-cyclohexyl-phenyl ketone were mixed and stirred evenly to obtain a modified anti-fading coating;

[0058] Step 3: Immerse the pretreated glass sheet in the island silicon-titanium sol, let it stand for 5 min, pull it vertically upward at a speed of 0.55 cm / s, remove the pretreated glass sheet, and perform post-treatment at 420 °C for 15 min to obtain a pretreated glass film;

[0059] Step 4: Coat the modified anti-fading coating on the surface of the pretreated glass film in an amount of 4 g / cm 2 , and irradiate it under ultraviolet light with an illumination intensity of 17 mW / cm 2 for 10 min, and then thermally cure it at 140 °C for 30 min to obtain an 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) Add tetra-isopropyl titanate and vinyltriethoxysilane into 35 wt% ethanol aqueous solution according to a mass ratio of 1:1:65, and react at 70 °C for 1.5 hours to obtain a titanium dioxide sol solution; (2) Ultrasonically disperse polydimethylsiloxane and the titanium dioxide sol solution at 50 °C for 25 min according to a mass ratio of 5:20 to obtain a premixed solution; (3) Add 3 parts of tetraethyl orthosilicate, 0.3 part of dibutyltin dilaurate, and 10 parts of the premixed solution into 35 parts of 35 wt% ethanol aqueous solution, add hydrochloric acid to adjust the pH to 4.5, and react at 70 °C for 3 hours to obtain a sea-island silicon-titanium sol;

[0062] Step 2: S2-1: Preparation of modified acrylic resin: (1) Add 4.5 parts of hydroxyethyl acrylate, 2.5 parts of dimethyldichlorosilane, and 0.3 part of dibutyltin dilaurate into 70 parts of butyl acetate, add triethylamine to adjust the pH to 5.7, and react at 55 °C for 8 hours, then separate and wash to obtain an organosilicon block monomer; (2) Under a nitrogen atmosphere, add 4.5 parts of the organosilicon block monomer, 1.5 parts of methyl methacrylate, 2 parts of butyl acrylate, 8.2 parts of 2-perfluorodecyl ethyl acrylate, and 0.7 part of azobisisobutyronitrile into 90 parts of butyl acetate, react at 90 °C for 9 hours, cool and separate to obtain a modified acrylic resin; S2-2: Preparation of cerium-doped TiO 2 / SiO 2 core-shell microspheres: (1) Add cerium nitrate hexahydrate into a nitric acid aqueous solution with a pH of 1.0, add tetrabutyl titanate and stir at a speed of 800 r / min for 2.5 hours, then carry out a hydrothermal reaction at 140 °C for 16 hours, cool, centrifuge, wash, and dry to obtain cerium-doped TiO 2 ; (2) Add 5 parts of cerium-doped TiO 2 into 70 parts of isopropyl alcohol aqueous solution, add ammonia water 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, and after cooling to room temperature, add it into 35 wt% ethanol aqueous solution, add 1.2 parts of 3-mercaptopropyltrimethoxysilane and 0.35 part of trifluoropropyltrimethoxysilane, react at 70 °C for 1.5 hours, and dry to obtain cerium-doped TiO 2 / SiO 2 core-shell microspheres; S2-3: Mix 50 parts of the modified acrylic resin, 25 parts of cerium-doped TiO 2 / SiO 2 core-shell microspheres, 3 parts of heat-insulating 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 evenly to obtain a modified anti-fading coating;

[0063] Step 3: Immerse the pretreated glass slide in the sea-island silica-titania sol, let it stand for 5 min, vertically lift it upward at a speed of 0.55 cm / s, and post-treat it at 420 °C for 15 min. Remove the pretreated glass slide to obtain a pretreated glass film;

[0064] Step 4: Coat the surface of the pretreated glass film with the modified anti-fading coating in an amount of 4 g / cm 2 , and irradiate it under ultraviolet light with a light intensity of 17 mW / cm 2 for 10 min, and then thermally cure it at 140 °C for 30 min to obtain an anti-deformation, anti-fading and aging-resistant glass film.

[0065] Comparative Example 1: Based on Example 1, adjust the coating amount of the modified anti-fading coating, and keep the rest of the process unchanged. Adjustment: Step 4: Coat the surface of the pretreated glass film with the modified anti-fading coating in an amount of 1.5 g / cm 2 , and irradiate it under ultraviolet light with a light intensity of 17 mW / cm 2 for 10 min, and then thermally cure it at 140 °C for 30 min to obtain an anti-deformation, anti-fading and aging-resistant glass film.

[0066] Comparative Example 2: Based on Example 1, do not introduce the silicone block, and keep the rest of the process unchanged. Adjustment:

[0067] Step 2: S2-1: Preparation of the modified acrylic resin: Under a nitrogen atmosphere, add 2 parts of hydroxyethyl acrylate, 1.5 parts of methyl methacrylate, 2 parts of butyl acrylate, 8.2 parts of 2-perfluorodecyl ethyl acrylate, and 0.7 part of azobisisobutyronitrile to 90 parts of butyl acetate, and react at 90 °C for 9 hours. Cool, separate, and obtain the modified acrylic resin; S2-2: Preparation of cerium-doped TiO 2 / SiO 2 core-shell microspheres: (1) Add cerium nitrate hexahydrate to a nitric acid aqueous solution with a pH of 1.0, add tetrabutyl titanate, and stir at a speed of 800 r / min for 2.5 hours. Then, carry out a hydrothermal reaction at 140 °C for 16 hours. Cool, centrifuge, wash, and dry to obtain cerium-doped TiO 2 ; (2) Add 5 parts of cerium-doped TiO 2 to 70 parts of an isopropyl alcohol aqueous solution, add ammonia water 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, and calcine at 550 °C for 2.5 hours. After cooling to room temperature, add it to a 35 wt% ethanol aqueous solution, add 1.2 parts of 3-mercaptopropyltrimethoxysilane and 0.35 part of trifluoropropyltrimethoxysilane, and react at 70 °C for 1.5 hours. Dry to obtain cerium-doped TiO 2 / SiO 2 core-shell microspheres; S2-3: Add 45 parts of the modified acrylic resin and 20 parts of cerium-doped TiO2 / SiO 2 Core-shell microspheres, 2 parts of heat-insulating and ultraviolet-resistant black color 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-phenylmethanone are mixed and stirred evenly to obtain a modified anti-fading coating.

[0068] Comparative Example 3: Based on Example 1, replace the cerium-doped TiO 2 / SiO 2 core-shell microspheres with nano-titanium dioxide, and keep the rest of the process unchanged. The adjustment is as follows:

[0069] Step 2: S2-2: Mix 45 parts of modified acrylic resin, 20 parts of nano-titanium dioxide, 2 parts of heat-insulating and ultraviolet-resistant black color 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-phenylmethanone and stir evenly to obtain a modified anti-fading coating;

[0070] The specification of the above nano-titanium dioxide is 20 nm.

[0071] Comparative Example 4: Based on Example 1, without introducing fluorine element, and keep the rest of the process unchanged. The adjustment is as follows:

[0072] Step 2: (2) Under a nitrogen atmosphere, add 4.5 parts of organosilicon block monomer, 1.5 parts of methyl methacrylate, 2 parts of butyl acrylate, 1.5 parts of ethyl acrylate, and 0.7 part of azobisisobutyronitrile to 90 parts of butyl acetate, react at 90 °C for 9 hours, cool, separate, and obtain a modified acrylic resin; S2-2: Preparation of cerium-doped TiO 2 / SiO 2 core-shell microspheres: (1) Add cerium nitrate hexahydrate to a nitric acid aqueous solution with a pH of 1.0, add tetrabutyl titanate, and stir at a speed of 800 r / min for 2.5 hours, then carry out a hydrothermal reaction at 140 °C for 16 hours, cool, centrifuge, wash, and dry to obtain cerium-doped TiO 2 ; (2) Add 5 parts of cerium-doped TiO 2 to 70 parts of isopropyl alcohol aqueous solution, add ammonia water to adjust the pH to 9.0, add 1.2 parts of tetraethyl orthosilicate, react at 30 °C for 24 hours, wash and dry, calcine at 550 °C for 2.5 hours, and after cooling to room temperature, add it to a 35 wt% ethanol aqueous solution, add 1.3 parts of 3-mercaptopropyltrimethoxysilane, react at 70 °C for 1.5 hours, and dry to obtain cerium-doped TiO 2 / SiO 2 core-shell microspheres.

[0073] Detection experiment: A kind of anti-deformation, anti-fading and anti-aging glass film prepared in Examples 1 to 3 and Comparative Examples 1 to 4 was subjected to performance detection: (1) Tensile strength test: The glass films prepared in Examples 1 to 3 and Comparative Examples 1 to 4 were placed under ultraviolet light irradiation with the light source wavelength set at 340 nm and aged for 120 hours. The tensile strength tests before and after aging were carried out with reference to "GB / T 1040.1-2018", and the results are shown in Table 1; (2) Anti-ultraviolet performance test: The glass films prepared in Examples 1 to 3 and Comparative Examples 1 to 4 were subjected to ultraviolet absorption rate test. 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: It can be seen from the data analysis in Table 1 that from the data of Comparative Example 1, it is known that by adjusting the coating amount of the modified anti-fading coating, the bonding force between the sea-island silicon titania sol and the modified coating decreases. During the ultraviolet aging process, the tensile strength decreases and the ultraviolet absorption rate decreases; from the data of Comparative Example 2, it is known that without introducing the silicone block, the elasticity of the resin decreases, the brittleness increases, the tensile strength decreases, and compared with Comparative Example 1, the ultraviolet absorption rate increases slightly; from the data of Comparative Example 3, it is known that when the cerium-doped TiO 2 / SiO 2 core-shell microspheres are adjusted to nano-titanium dioxide, agglomeration is likely to occur, there is no core-shell structure, and no cerium ions are added, the refractive index of light decreases, the ultraviolet light absorption rate decreases significantly, and the tensile strength and anti-aging performance decrease; from the data of Comparative Example 4, it is known that without introducing fluorine elements, the overall weather resistance decreases and the anti-aging performance decreases significantly.

[0078] For those skilled in the art, it is obvious that the present invention is not limited to the details of the above exemplary embodiments, and without departing from the spirit or basic characteristics of the present invention, the present invention can be implemented in other specific forms. Therefore, from any point of view, the embodiments should be regarded as exemplary and non-limiting. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, it is intended to embrace all changes falling within the meaning and scope of the equivalent elements of the claims in the present invention.

Claims

1. A method for preparing an anti-deformation, anti-fading and anti-aging glass film, characterized in that: The following steps are involved: Step 1: immerse the pretreated glass sheet in the sea-island silica-titanium sol, let it stand, pull it, remove the pretreated glass sheet, and post-treat it to obtain a pretreated glass film; Step 2: Apply the modified anti-fading coating to the surface of the pre-treated glass film, pre-react, and heat-cure to obtain a deformation-resistant, anti-fading, and aging-resistant glass film.

2. The method for preparing a deformation-resistant, fading-resistant and aging-resistant glass film according to claim 1, characterized in that: In step 1, the standing time is 3 to 5 minutes; the pulling is vertically upward pulling, and the pulling speed is 0.5 to 0.6 cm / s; the post-treatment temperature is 400 to 450° C., and the time is 10 to 20 minutes.

3. The method for preparing a deformation-resistant, fading-resistant and aging-resistant glass film according to claim 1, characterized in that: In step 2, the coating amount is 3 to 5 g / cm 2 ; The process parameters of the pre-reaction: set the light intensity to 15-20mW / cm 2 , irradiated under ultraviolet light for 8 to 12 minutes; the temperature of the thermal curing is 120 to 160° C., and the time is 20 to 40 minutes.

4. The method for preparing a deformation-resistant, fading-resistant and aging-resistant glass film according to claim 1, characterized in that: The preparation process of the sea island silica-titanium sol is as follows: S1-1: adding tetraisopropyl titanate and vinyl silane coupling agent into a 30-40 wt % ethanol aqueous solution, reacting at 60-80° C. for 1-2 hours to obtain a titanium dioxide sol solution; S1-2: Ultrasonic dispersion of polydimethylsiloxane and titanium dioxide sol at 45-55° C. for 20-30 min to obtain a premixed solution; S1-3: Add ethyl orthosilicate, dibutyltin dilaurate and premixed liquid into 30-40 wt% ethanol aqueous solution, add hydrochloric acid to adjust the pH to 4.0-5.0, react at 60-80° C. for 2-4 hours to obtain sea island silica-titanium sol.

5. The method for preparing a deformation-resistant, fading-resistant and aging-resistant glass film according to claim 4, characterized in that: The raw materials of the sea island silicon titanium sol include the following components: by weight, 2 to 4 parts of ethyl orthosilicate, 0.2 to 0.4 parts of dibutyltin dilaurate, 8 to 12 parts of premixed liquid, and 30 to 40 parts of 30 to 40 wt% ethanol aqueous solution; In the premixed liquid, the mass ratio of polydimethylsiloxane to titanium dioxide sol liquid is 5:10-20; In the titanium dioxide sol solution, the mass ratio of tetraisopropyl titanate, vinyl silane coupling agent and 30-40wt% ethanol aqueous solution is 1:0.5-1.5:60-70.

6. The method for preparing a deformation-resistant, fading-resistant, and aging-resistant glass film according to claim 1, characterized in that: The preparation process of the modified anti-fading coating is: S2-1: Preparation of modified acrylic resin: (1) Add hydroxyethyl acrylate, dimethyldichlorosilane, and dibutyltin dilaurate to butyl acetate, add triethylamine to adjust the pH to 5.2-6.2, react at 50-60° C. for 7-9 hours, separate, and elute to obtain a silicone block monomer; (2) Under a nitrogen atmosphere, add a silicone block monomer, methyl methacrylate, butyl acrylate, 2-perfluorodecylethyl acrylate, and a free radical initiator to butyl acetate, react at 80-100° C. for 8-10 hours, cool, and separate to obtain a modified acrylic resin; S2-2: Preparation of cerium-doped TiO2 / SiO2 core-shell microspheres: (1) Add cerium nitrate hexahydrate to a nitric acid aqueous solution with a pH of 1.0 to 1.1, add tetrabutyl titanate and stir at a speed of 500 to 1000 r / min for 2 to 3 hours, then hydrothermally react at 130 to 150°C for 12 to 18 hours, cool, centrifuge, wash, and dry to obtain cerium-doped TiO2; (2) Add cerium-doped TiO2 to an isopropanol aqueous solution, add ammonia water to adjust the pH to 8.8 to 9.2, add tetraethyl orthosilicate and react at 25 to 35°C for 20 to 28 hours, wash and dry, calcine at 500 to 600°C for 2 to 3 hours, cool to room temperature, add it to a 30 to 40 wt% ethanol aqueous solution, add a mercaptosilane coupling agent and a fluorine-containing silane coupling agent, react at 60 to 80°C for 1 to 2 hours, and dry to obtain cerium-doped TiO2 / SiO2 core-shell microspheres; S2-3: The modified acrylic resin, cerium-doped TiO2 / SiO2 core-shell microspheres, heat-insulating anti-ultraviolet black masterbatch, anti-light oxidant, isopropyl alcohol-ethanol solution, propylene glycol monolaurate, and photoinitiator are mixed and stirred evenly to obtain a modified anti-fading coating.

7. The method for preparing a deformation-resistant, fading-resistant and aging-resistant glass film according to claim 6, characterized in that: The raw materials of the modified anti-fading coating include the following components: by mass, 40 to 50 parts of modified acrylic resin, 15 to 25 parts of cerium-doped TiO2 / SiO2 core-shell microspheres, 1 to 3 parts of heat-insulating and anti-ultraviolet black masterbatch, 1 to 2 parts of anti-light oxidant, 60 to 80 parts of isopropanol-ethanol solution, 3 to 5 parts of propylene glycol monolaurate, and 0.5 to 1.5 parts of photoinitiator.

8. The method for preparing a deformation-resistant, fading-resistant, and aging-resistant glass film according to claim 7, characterized in that: The raw materials of the modified acrylic resin include the following components: 4 to 5 parts of silicone block monomer, 1 to 2 parts of methyl methacrylate, 1.5 to 2.5 parts of butyl acrylate, 8 to 9 parts of 2-perfluorodecyl ethyl acrylate, 0.5 to 1 part of free radical initiator, and 80 to 100 parts of butyl acetate, by mass. The raw materials containing the organic silicon block monomer include the following components: 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.

9. The method for preparing a deformation-resistant, fading-resistant and aging-resistant glass film according to claim 7, characterized in that: The raw materials of the cerium-doped TiO2 / SiO2 core-shell microspheres include the following components: 4 to 6 parts of cerium-doped TiO2, 60 to 80 parts of isopropanol aqueous solution, 0.5 to 2 parts of tetraethyl orthosilicate, 1 to 1.5 parts of mercaptosilane coupling agent, and 0.2 to 0.5 parts of fluorine-containing silane coupling agent, by weight. In the raw material of cerium-doped TiO2, the molar ratio of cerium nitrate hexahydrate to tetrabutyl titanate is 1:10-12.

10. The anti-deformation, anti-fading and aging-resistant glass film prepared by the method for preparing the anti-deformation, anti-fading and aging-resistant glass film according to any one of claims 1 to 9.

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