CN114249545A - Coated glass with ultraviolet shielding function - Google Patents
Coated glass with ultraviolet shielding function Download PDFInfo
- Publication number
- CN114249545A CN114249545A CN202111492227.9A CN202111492227A CN114249545A CN 114249545 A CN114249545 A CN 114249545A CN 202111492227 A CN202111492227 A CN 202111492227A CN 114249545 A CN114249545 A CN 114249545A
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- CN
- China
- Prior art keywords
- glass
- zinc oxide
- ultraviolet shielding
- titanium dioxide
- coated
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- 239000011521 glass Substances 0.000 title claims abstract description 295
- 239000000758 substrate Substances 0.000 claims abstract description 113
- 239000010410 layer Substances 0.000 claims abstract description 105
- 239000011241 protective layer Substances 0.000 claims abstract description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 168
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 158
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 101
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 96
- 239000004408 titanium dioxide Substances 0.000 claims description 84
- 239000007788 liquid Substances 0.000 claims description 75
- 239000011787 zinc oxide Substances 0.000 claims description 66
- 239000002245 particle Substances 0.000 claims description 63
- 239000002096 quantum dot Substances 0.000 claims description 58
- 239000000377 silicon dioxide Substances 0.000 claims description 48
- 239000006185 dispersion Substances 0.000 claims description 47
- 235000012239 silicon dioxide Nutrition 0.000 claims description 46
- 238000000576 coating method Methods 0.000 claims description 43
- 238000001035 drying Methods 0.000 claims description 43
- 239000011248 coating agent Substances 0.000 claims description 37
- 238000003892 spreading Methods 0.000 claims description 37
- 230000007480 spreading Effects 0.000 claims description 37
- 229920000642 polymer Polymers 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 34
- 239000003085 diluting agent Substances 0.000 claims description 33
- 229920001558 organosilicon polymer Polymers 0.000 claims description 33
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 32
- 235000019441 ethanol Nutrition 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 238000005406 washing Methods 0.000 claims description 30
- -1 polysiloxane Polymers 0.000 claims description 28
- 239000002994 raw material Substances 0.000 claims description 28
- 238000005496 tempering Methods 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 26
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 26
- 238000010008 shearing Methods 0.000 claims description 26
- 238000001816 cooling Methods 0.000 claims description 25
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 24
- 229920001296 polysiloxane Polymers 0.000 claims description 24
- 239000003292 glue Substances 0.000 claims description 22
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 17
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 16
- 239000011592 zinc chloride Substances 0.000 claims description 16
- 235000005074 zinc chloride Nutrition 0.000 claims description 16
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000004108 freeze drying Methods 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 12
- 230000001681 protective effect Effects 0.000 claims description 12
- 238000007599 discharging Methods 0.000 claims description 10
- 239000013523 DOWSIL™ Substances 0.000 claims description 8
- 229920013731 Dowsil Polymers 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- 238000005507 spraying Methods 0.000 claims description 6
- 230000001680 brushing effect Effects 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920001709 polysilazane Polymers 0.000 claims description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- 229920002050 silicone resin Polymers 0.000 claims description 4
- 238000004528 spin coating Methods 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- LAQFLZHBVPULPL-UHFFFAOYSA-N methyl(phenyl)silicon Chemical compound C[Si]C1=CC=CC=C1 LAQFLZHBVPULPL-UHFFFAOYSA-N 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims 1
- 238000002834 transmittance Methods 0.000 abstract description 16
- 238000012360 testing method Methods 0.000 abstract description 5
- 230000032683 aging Effects 0.000 abstract description 3
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
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- 230000006872 improvement Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- 208000002177 Cataract Diseases 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 208000000453 Skin Neoplasms Diseases 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
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- 238000007772 electroless plating Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 238000010285 flame spraying Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
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- 239000011810 insulating material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- VBUBYMVULIMEHR-UHFFFAOYSA-N propa-1,2-diene;prop-1-yne Chemical compound CC#C.C=C=C VBUBYMVULIMEHR-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 201000000849 skin cancer Diseases 0.000 description 1
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- 238000000411 transmission spectrum Methods 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/44—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the composition of the continuous phase
- C03C2217/445—Organic continuous phases
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
- C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
- C03C2217/475—Inorganic materials
- C03C2217/477—Titanium oxide
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
- C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
- C03C2217/475—Inorganic materials
- C03C2217/478—Silica
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/74—UV-absorbing coatings
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/78—Coatings specially designed to be durable, e.g. scratch-resistant
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/112—Deposition methods from solutions or suspensions by spraying
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/116—Deposition methods from solutions or suspensions by spin-coating, centrifugation
Abstract
The invention provides coated glass with an ultraviolet shielding function, which comprises a glass substrate, an ultraviolet shielding layer and a surface protective layer, wherein the ultraviolet shielding layer is positioned between the glass substrate and the surface protective layer. The coated glass with the ultraviolet shielding function selectively shields light, the average light transmittance of an ultraviolet region is less than 5%, the average visible region transmittance is greater than 85%, the haze is 0, the surface hardness reaches 9H, the coated glass can resist scratch tests for more than 2 ten thousand times, and the performance is not attenuated after resisting 3000H ultraviolet accelerated aging.
Description
Technical Field
The invention belongs to the field of coated glass, and particularly relates to coated glass with an ultraviolet shielding function.
Background
Excessive ultraviolet radiation can cause the immunologic function of a human body to be reduced, the incidence rate of skin cancer and cataract is increased, the skin is accelerated to be dark, aged, speckled, wrinkled and the like, and the aging and fading of furniture and furnishings are accelerated. As the damage of human activities to the ozone layer is increased, the threat of ultraviolet rays to human beings is increased. Even in cloudy days the UV content is as high as 90% in sunny days. Therefore, daily shielding of ultraviolet rays becomes important.
Glass is used as an important component of building and automobile windows, and ensures high transmittance of incident light as far as possible. In order to achieve the ultraviolet shielding effect, one of the preferred methods is to block ultraviolet rays falling into incident light by glass. The common glass on the market has only a small part of barrier effect on ultraviolet rays, and the transmittance of the common glass on the ultraviolet rays is generally more than 70%. How to realize total blocking of ultraviolet rays by glass with high transmittance of other light rays without affecting the glass? In order to solve the problem, the glass needs to be functionalized, and a film with an ultraviolet barrier function is coated on the surface of the glass, and the original hardness and high permeability to other light rays of the glass are kept.
The glass surface coating process mainly comprises two types, namely dry coating and wet coating. Dry coating includes vacuum coating, sputtering coating, ion coating and the like, and the coating requires that a film material is prepared into a high-purity target material and then coated on the surface of a substrate material through a certain coating process. In order to obtain a transparent coated glass product, the requirement is that the particle size and thickness of the coating particles are maintained at a nanometer level, which greatly increases the cost and implementation difficulty of the dry coating process.
Wet plating includes electroless plating, electroplating, and chemical reduction, and such plating methods are performed in solution and are therefore referred to as wet plating. Such a plating method is often used for preparing a metal coating, for example, a chromium plating process for improving the surface hardness of a metal part, a chemical bluing process for improving the corrosion resistance of a part surface (forming a magnetite coating by chemical treatment in a steel-structured part), and the like. However, such wet coating often incurs significant environmental costs, such as waste water and liquid disposal, and often results in significant energy consumption.
Flame spraying is a non-traditional coating process, which uses fuel gas acetylene, propane, methyl acetylene-propadiene (MPS), hydrogen or natural gas and combustion-supporting gas oxygen to mix and burn as a heat source, and a spraying material enters flame in a certain transmission mode, is heated to a molten or softened state, and then is sprayed onto a substrate by means of gas or flame acceleration. When the sprayed film material impacts on the substrate, a lamellar deposition layer is formed. However, there are problems associated with the production of transparent insulating glass by this method. On the one hand, the insulating materials that can be used for coating are often inorganic ceramic materials with semiconducting properties, which materials generally have a high boiling point and which often require a high temperature for heating to a molten state. On the other hand, glass as a carrier material for spray coating can deform at high temperature. Therefore, how to prevent the glass from melting and deforming in the coating process is a problem of the process.
In conclusion, the development of a glass coating process with simple process and low cost is urgently needed in the current market.
Disclosure of Invention
In view of the above, the present invention provides a coated glass with an ultraviolet shielding function, which can completely shield ultraviolet light in incident light passing through the glass without affecting the transmittance of other incident light.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a coated glass with ultraviolet shielding function comprises a glass substrate, an ultraviolet shielding layer and a surface protection layer, wherein the ultraviolet shielding layer is positioned between the glass substrate and the surface protection layer;
the ultraviolet shielding layer is prepared from the following raw materials in parts by weight:
30-70 parts of titanium dioxide coated with silicon dioxide loaded with zinc oxide quantum dot particles,
the surface protection layer is prepared from the following raw materials in parts by weight:
30-70 parts of an organic silicon polymer,
0.1 to 10 portions of protective leveling agent,
30-70 parts of a protective diluent.
Preferably, the ultraviolet shielding layer is prepared from the following raw materials in parts by weight:
30-50 parts of titanium dioxide coated with silicon dioxide loaded with zinc oxide quantum dot particles,
further, the titanium dioxide loaded zinc oxide quantum dot particle coated with silicon dioxide is prepared by the following steps: ultrasonically dispersing titanium dioxide-loaded zinc oxide quantum dots, ammonia water and ethyl orthosilicate in an ethanol solution, continuously stirring for 6-14h in a water bath at 45-60 ℃, washing, drying, and then treating for 2-6h at 500 ℃ in an inert atmosphere to obtain the titanium dioxide-loaded zinc oxide quantum dot particles coated by silicon dioxide.
Further, the titanium dioxide loaded zinc oxide quantum dot is prepared by the method comprising the following steps: ultrasonically dispersing zinc chloride and tetrabutyl titanate in absolute ethyl alcohol, then placing the mixture in a high-pressure reaction kettle, preserving the heat for 6-48h at the temperature of 140-200 ℃, cooling to room temperature, and then carrying out freeze drying to obtain the titanium dioxide loaded zinc oxide quantum dot.
Further, the solid-liquid mass ratio of the zinc chloride to the tetrabutyl titanate to the absolute ethyl alcohol is as follows: 1-5:1-20: 50-100; the solid-liquid mass ratio of the titanium dioxide loaded zinc oxide quantum dots, ammonia water, ethyl orthosilicate and ethanol solution is 1-30:5-30:5-30: 50-100; the particle size of the titanium dioxide loaded zinc oxide quantum dot particles coated by the silicon dioxide is less than or equal to 10 nm.
Further, the high-temperature agglomeration-preventing auxiliary agent is at least one of micromolecular siloxane or micromolecular silica sol; the molecular weight of the micromolecular siloxane is 500-1000; the dispersant is at least one of DISPERBYK 110, DISPERBYK 180, DISPERBYK2080, MONENG 3035, MONENG 3063, EFKA PX4701 or KMT 3003;
the shielding leveling agent is at least one of BYK 333, Modarez MF AEX, DOWSIL FZ-2123, Coatosil 7500 or SKYTYPE LA 0520; the shielding diluent is at least one of ethanol, propylene glycol methyl ether acetate, ethyl acetate, dipropylene glycol dimethyl ether, butyl acetate or isoparaffin. The high-temperature agglomeration-preventing assistant is used for preventing zinc oxide from agglomerating and growing at high temperature.
Further, the protective leveling agent is at least one of BYK 333, Modarez MF AEX, DOWSIL FZ-2123, Coatosil 7500 or SKYTYPE LA 0520; the protective diluent is at least one of ethanol, propylene glycol methyl ether acetate, ethyl acetate, dipropylene glycol dimethyl ether, butyl acetate or isoparaffin;
the organic silicon polymer is at least one of methyl silicone resin, methyl phenyl silicone resin, silicon carbide hybrid polymer, polysiloxane polymer, polysilazane polymer or organic polyborosilazane polymer; preferably, the organic silicon polymer is at least one of silicon carbide hybrid polymer or polysilazane polymer; the molecular weight of the polysiloxane polymer was 2000-.
The preparation method of the coated glass with the ultraviolet shielding function comprises the following steps:
(1) coating an ultraviolet shielding layer: cleaning a glass substrate, uniformly mixing silicon dioxide-coated titanium dioxide loaded zinc oxide quantum dot particles, a dispersing agent, a high-temperature agglomeration-preventing auxiliary agent, a shielding leveling agent and a shielding diluent through high-speed shearing, uniformly spreading the obtained dispersion liquid on the surface of the glass substrate, putting the glass substrate into a high-temperature glue discharging furnace for glue discharging treatment, taking out the glass plate when the glass plate is hot after the glue discharging is finished, and finishing the coating of an ultraviolet shielding layer;
(2) coating a surface protection layer: and (2) uniformly mixing the organic silicon polymer, the protective leveling agent and the protective diluent through a high-speed shearing machine, uniformly spreading the obtained dispersion liquid to the outer surface of the ultraviolet shielding layer obtained in the step (1) to form a protective layer precursor, putting the protective layer precursor into a high-temperature tempering furnace for tempering, and then quickly cooling to obtain the coated glass with the ultraviolet shielding function.
Further, the spreading step in the step (1) is one of spraying, spin coating, brushing, flow coating or natural leveling; the spreading thickness of the dispersion liquid in the step (1) is 0.1-100 μm; the mass of the titanium dioxide loaded zinc oxide quantum dot particles coated by the silicon dioxide in the ultraviolet shielding layer is 0.1-10g/m2(ii) a The mass of the high-temperature agglomeration-preventing auxiliary agent in the ultraviolet shielding layer is 0.01-0.5g/m2(ii) a Preferably, the spreading thickness of the dispersion liquid in the step (1) is 0.1-30 μm; the mass of the titanium dioxide loaded zinc oxide quantum dot particles coated by the silicon dioxide in the ultraviolet shielding layer is 0.1-3g/m2(ii) a The glue discharging treatment in the step (1)The heating rate is 5-10 ℃/min, the temperature is 200-. The glue discharging treatment is used for discharging a diluent, a dispersing agent and a flatting agent in the dispersion liquid, and the residual zinc oxide nano particles and the high-temperature anti-agglomeration auxiliary agent are on the surface layer of the glass, so that good discreteness of the nano particles is ensured.
Further, the spreading step in the step (2) is one of spraying, spin coating, brushing, flow coating or natural leveling; the spreading thickness of the dispersion liquid in the step (2) is 0.1-100 μm; the mass of the organic silicon polymer in the surface protection layer is 1-100g/m2(ii) a Preferably, the spreading thickness of the dispersion liquid in the step (2) is 1-30 μm; the mass of the organic silicon polymer in the surface protection layer is 1-30g/m2(ii) a The temperature of the toughening step in the step (2) is 700-900 ℃, and the time is 30-300 s.
Further, the titanium dioxide loaded zinc oxide quantum dot particle coated with silicon dioxide is prepared by the following steps:
(1) ultrasonically dispersing zinc chloride and tetrabutyl titanate in absolute ethyl alcohol, then placing the mixture in a high-pressure reaction kettle, preserving the heat for 6-48h at the temperature of 140-200 ℃, cooling to room temperature, and then carrying out freeze drying to obtain the titanium dioxide loaded zinc oxide quantum dots;
(2) ultrasonically dispersing titanium dioxide-loaded zinc oxide quantum dots, ammonia water and ethyl orthosilicate in an ethanol solution, continuously stirring for 6-14h in a water bath at 45-60 ℃, washing, drying, and then treating for 2-6h at 500 ℃ in an inert atmosphere to obtain titanium dioxide-loaded zinc oxide quantum dot particles coated by silicon dioxide;
the solid-liquid mass ratio of the zinc chloride to the tetrabutyl titanate to the absolute ethyl alcohol is as follows: 1-5:1-20: 50-100; the solid-liquid mass ratio of the titanium dioxide loaded zinc oxide quantum dots, ammonia water, ethyl orthosilicate and ethanol solution is 1-30:5-30:5-30: 50-100; the particle size of the titanium dioxide loaded zinc oxide quantum dot particles coated by the silicon dioxide is less than or equal to 10 nm.
Compared with the prior art, the invention has the following advantages:
the coated glass with the ultraviolet shielding function selectively shields light, the average light transmittance of an ultraviolet region is less than 5%, the average visible region transmittance is greater than 85%, the haze is 0, the surface hardness reaches 9H, the coated glass can resist scratch tests for more than 2 ten thousand times, and the performance is not attenuated after resisting 3000H ultraviolet accelerated aging.
The coated glass with the ultraviolet shielding function has the advantages of low cost of raw materials, simple preparation method of the glass, no need of additional coating equipment and simple process, directly forms a coating along with the toughening process of the glass, is an improvement on the prior art, and is completely suitable for large-scale industrial production.
The ultraviolet shielding layer is coated with titanium dioxide loaded zinc oxide quantum dot particle slurry coated with silicon dioxide, and then is toughened along with a furnace to form a film layer, so that a coated glass product with high hardness, high wear resistance, long service life and high ultraviolet barrier property is obtained, the high transmittance of visible light is not influenced, and the visibility and the attractiveness of the coated glass are ensured.
Drawings
Fig. 1 is a transmittance spectrum of a conventional glass substrate and the ultraviolet shielding function coated glass according to example 1 of the present invention measured by a spectrophotometer.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to examples.
Example 1
A coated glass with ultraviolet shielding function comprises a glass substrate, an ultraviolet shielding layer and a surface protection layer, wherein the ultraviolet shielding layer is positioned between the glass substrate and the surface protection layer; the ultraviolet shielding layer is prepared from the following raw materials in parts by weight: 4g of titanium dioxide coated with silicon dioxide loaded with zinc oxide quantum dot particles, 4g of DISPERBYK 1101g, BYK 3331 g, 1g of siloxane with molecular weight of 500 and 3g of propylene glycol methyl ether acetate; the surface protection layer is prepared from the following raw materials in parts by weight: 4g of polysiloxane polymer with molecular weight of 2000, 3330.4 g of BYK and 5g of diluent.
A preparation method of coated glass with an ultraviolet shielding function comprises the following steps:
(1) weighing 3g of zinc chloride and 8g of tetrabutyl titanate, ultrasonically dispersing in 120mL of absolute ethyl alcohol, placing the solution in a high-pressure reaction kettle, preserving heat for 2h at 180 ℃, naturally cooling to room temperature, and freeze-drying the solution to obtain titanium dioxide-loaded zinc oxide quantum dots;
weighing 2g of titanium dioxide loaded zinc oxide quantum dots, ultrasonically dispersing the titanium dioxide loaded zinc oxide quantum dots in 80mL of absolute ethanol solution, then adding 5mL of ethyl orthosilicate and 5mL of ammonia water, stirring the mixed solution in a water bath at 45 ℃ for 10 hours at constant temperature, then washing with water, washing with alcohol, drying, and then adding N2Calcining for 3h at 400 ℃ under protection to obtain titanium dioxide loaded zinc oxide quantum dot particles coated with silicon dioxide;
(2) glass coating was performed as follows: selecting a common glass substrate with the size of 8cm by 8cm for cleaning treatment, carrying out ultrasonic treatment on the glass substrate for 5min, then respectively washing the glass substrate with clean water and ethanol, and naturally drying the glass substrate; weighing 4g of titanium dioxide loaded zinc oxide quantum dot particles coated with silicon dioxide, 1g of DISPERBYK 1101g, BYK 3331 g, 1g of siloxane with molecular weight of 500 and 3g of propylene glycol methyl ether acetate, putting the above ingredients into a high-speed shearing machine, mixing and stirring uniformly, then dropping a small amount of dispersion liquid on the surface of a glass substrate, then uniformly spreading the dispersion liquid on the surface of the glass by a spin coater, so that 0.03g of the dispersion liquid is finally left on the surface of the glass, naturally drying the glass in the air, then putting the glass in a muffle furnace at the temperature of 300 ℃ for glue discharge, wherein the heating rate is 5 ℃/min, the heat preservation time is 30min, and taking out the glass after completion;
(3) weighing 4g of polysiloxane polymer with molecular weight of 2000, 3330.4 g of BYK and 5g of diluent, putting the above ingredients into a high-speed shearing machine, mixing and stirring uniformly, dripping 0.3g of organic silicon polymer dispersion liquid on the surface of a glass substrate, uniformly spreading the organic silicon polymer dispersion liquid on the surface layer of the glass by a spin coater, naturally drying the glass in air, putting the glass with a protective layer precursor into a high-temperature tempering furnace at 750 ℃ for tempering for 30 seconds, and rapidly cooling to obtain the coated glass with the ultraviolet shielding function.
Example 2
A coated glass with ultraviolet shielding function comprises a glass substrate, an ultraviolet shielding layer and a surface protection layer, wherein the ultraviolet shielding layer is positioned between the glass substrate and the surface protection layer; the ultraviolet shielding layer is prepared from the following raw materials in parts by weight: 10g of titanium dioxide loaded zinc oxide quantum dot particles coated by silicon dioxide, 20803 g of DISPERBYK, 2g of DOWSIL FZ-21232 g of siloxane with the molecular weight of 500 and 30g of propylene glycol methyl ether acetate; the surface protection layer is prepared from the following raw materials in parts by weight: 10g of polysiloxane polymer with molecular weight of 2000, 3332 g of BYK and 20g of diluent.
A preparation method of coated glass with an ultraviolet shielding function comprises the following steps:
(1) weighing 10g of zinc chloride and 30g of tetrabutyl titanate, ultrasonically dispersing in 350mL of absolute ethyl alcohol, placing the solution in a high-pressure reaction kettle, preserving heat for 2h at 200 ℃, naturally cooling to room temperature, and freeze-drying the solution to obtain titanium dioxide-loaded zinc oxide quantum dots;
weighing 5g of titanium dioxide loaded zinc oxide quantum dots, ultrasonically dispersing the titanium dioxide loaded zinc oxide quantum dots in 200mL of absolute ethanol solution, then adding 15mL of ethyl orthosilicate and 15mL of ammonia water, stirring the mixed solution in a water bath at 45 ℃ for 10 hours at constant temperature, then washing with water, washing with alcohol, drying, and then adding N2Calcining for 3h at 400 ℃ under protection to obtain titanium dioxide loaded zinc oxide quantum dot particles coated with silicon dioxide;
(2) glass coating was performed as follows: selecting a common glass substrate with the size of 120cm x 80cm for cleaning treatment, carrying out ultrasonic treatment on the glass substrate for 5min, then respectively washing the glass substrate with clean water and ethanol, and naturally drying the glass substrate; weighing 10g of titanium dioxide loaded zinc oxide quantum dot particles coated by silicon dioxide, DISPERBYK 20803 g, DOWSIL FZ-21232 g, 2g of siloxane with molecular weight of 500 and 30g of propylene glycol methyl ether acetate, putting the above ingredients into a high-speed shearing machine, mixing and stirring uniformly, then dripping a small amount of dispersion liquid on the surface of a glass substrate, then uniformly spreading the dispersion liquid on the surface of the glass by a spin coater, so that 10g of the dispersion liquid is finally left on the surface of the glass, naturally drying the glass in the air, putting the glass substrate into a muffle furnace with the temperature of 400 ℃ for glue discharge, wherein the heating rate is 5 ℃/min, the heat preservation time is 30min, and taking out the glass substrate after the completion;
(3) weighing 10g of polysiloxane polymer with molecular weight of 2000, 3332 g of BYK and 20g of diluent, putting the above ingredients into a high-speed shearing machine, mixing and stirring uniformly, dripping 9g of organic silicon polymer dispersion liquid on the surface of a glass substrate, spreading the organic silicon polymer dispersion liquid on the surface layer of the glass by a spin coater, naturally drying the glass, putting the glass with a protective layer precursor into a high-temperature tempering furnace at 750 ℃ for tempering for 30 seconds, and then rapidly cooling to obtain the coated glass with the ultraviolet shielding function.
Example 3
A coated glass with ultraviolet shielding function comprises a glass substrate, an ultraviolet shielding layer and a surface protection layer, wherein the ultraviolet shielding layer is positioned between the glass substrate and the surface protection layer; the ultraviolet shielding layer is prepared from the following raw materials in parts by weight: 30g of titanium dioxide coated with silicon dioxide loaded zinc oxide quantum dot particles, DISPERBYK 208010 g, DOWSIL FZ-21235 g, 5g of siloxane with molecular weight of 500 and 60g of propylene glycol methyl ether acetate; the surface protection layer is prepared from the following raw materials in parts by weight: 30g of polysiloxane polymer with molecular weight of 2000, 3333 g of BYK and 50g of diluent.
A preparation method of coated glass with an ultraviolet shielding function comprises the following steps:
(1) weighing 50g of zinc chloride and 150g of tetrabutyl titanate, ultrasonically dispersing in 2000mL of absolute ethyl alcohol, placing the solution in a high-pressure reaction kettle, preserving the temperature for 2h at 180 ℃, naturally cooling to room temperature, and freeze-drying the solution to obtain titanium dioxide-loaded zinc oxide quantum dots;
weighing 20g of titanium dioxide loaded zinc oxide quantum dots, ultrasonically dispersing the titanium dioxide loaded zinc oxide quantum dots in 800mL of absolute ethanol solution, then adding 50mL of ethyl orthosilicate and 50mL of ammonia water, and stirring the mixed solution in a water bath at the temperature of 60 ℃ at constant temperature for 14h, then washing with water, washing with alcohol and drying, then in Ar2Calcining for 3h at 500 ℃ under protection to obtain titanium dioxide loaded zinc oxide quantum dot particles coated with silicon dioxide;
(2) glass coating was performed as follows: selecting a common glass substrate with the size of 120cm by 200cm for cleaning treatment, carrying out ultrasonic treatment on the glass substrate for 5min, then respectively washing the glass substrate with clean water and ethanol, and naturally drying the glass substrate; weighing 20g of titanium dioxide loaded zinc oxide quantum dot particles coated by silicon dioxide, DISPERBYK 208010 g, DOWSIL FZ-21235 g, 5g of siloxane with molecular weight of 500 and 60g of propylene glycol monomethyl ether acetate, putting the above ingredients into a high-speed shearing machine, mixing and stirring uniformly, then dripping a small amount of dispersion liquid on the surface of a glass substrate, then uniformly brushing the surface of the glass with a sponge brush to ensure that 30g of dispersion liquid is finally left on the surface of the glass, naturally drying the glass in the air, putting the glass substrate into a muffle furnace with the temperature of 400 ℃ for glue discharge, wherein the heating rate is 5 ℃/min, the heat preservation time is 30min, and taking out the glass substrate after completion;
(3) weighing 30g of polysiloxane polymer with molecular weight of 2000, 33 g of BYK 3333 g and 50g of diluent, putting the above ingredients into a high-speed shearing machine, mixing and stirring uniformly, dripping 60g of organic silicon polymer dispersion liquid on the surface of a glass substrate, spreading the organic silicon polymer dispersion liquid on the surface layer of the glass by a spin coater, naturally drying the glass, putting the glass with a protective layer precursor into a high-temperature tempering furnace at 750 ℃ for tempering for 30 seconds, and then rapidly cooling to obtain the coated glass with the ultraviolet shielding function.
Comparative example 1
A coated glass with ultraviolet shielding function comprises a glass substrate, an ultraviolet shielding layer and a surface protection layer, wherein the ultraviolet shielding layer is positioned between the glass substrate and the surface protection layer; the ultraviolet shielding layer is prepared from the following raw materials in parts by weight: 4g of commercially available silica-coated zinc oxide quantum dot particles, DISPERBYK 1101g, BYK 3331 g, 1g of siloxane with the molecular weight of 500 and 3g of propylene glycol methyl ether acetate; the surface protection layer is prepared from the following raw materials in parts by weight: 4g of polysiloxane polymer with molecular weight of 2000, 3330.4 g of BYK and 5g of diluent.
A preparation method of coated glass with an ultraviolet shielding function comprises the following steps:
(1) selecting a common glass substrate with the size of 8cm by 8cm for cleaning treatment, carrying out ultrasonic treatment on the glass substrate for 5min, then respectively washing the glass substrate with clean water and ethanol, and naturally drying the glass substrate; weighing 4g of commercially available silicon dioxide coated zinc oxide quantum dot particles, 1g of DISPERBYK 1101g, 3g of BYK 3331 g, 1g of siloxane with molecular weight of 500 and 3g of propylene glycol methyl ether acetate, putting the above ingredients into a high-speed shearing machine, mixing and stirring uniformly, then dripping a small amount of dispersion liquid on the surface of a glass substrate, then uniformly spreading the dispersion liquid on the surface of the glass by a spin coater, so that 0.03g of dispersion liquid is finally left on the surface of the glass, naturally drying the glass in the air, putting the glass in a muffle furnace at the temperature of 300 ℃ for glue discharge, wherein the heating rate is 5 ℃/min, the heat preservation time is 30min, and taking out the glass after completion;
(3) weighing 4g of polysiloxane polymer with molecular weight of 2000, 3330.4 g of BYK and 5g of diluent, putting the above ingredients into a high-speed shearing machine, mixing and stirring uniformly, dripping 0.3g of organic silicon polymer dispersion liquid on the surface of a glass substrate, uniformly spreading the organic silicon polymer dispersion liquid on the surface layer of the glass by a spin coater, naturally drying the glass in air, putting the glass with a protective layer precursor into a high-temperature tempering furnace at 750 ℃ for tempering for 30 seconds, and rapidly cooling to obtain the coated glass with the ultraviolet shielding function.
Comparative example 2
A coated glass with ultraviolet shielding function comprises a glass substrate, an ultraviolet shielding layer and a surface protection layer, wherein the ultraviolet shielding layer is positioned between the glass substrate and the surface protection layer; the ultraviolet shielding layer is prepared from the following raw materials in parts by weight: 4g of titanium dioxide-coated zinc oxide nanoparticles, 4g of DISPERBYK 1101g, BYK 3331 g, 1g of siloxane with the molecular weight of 500 and 3g of propylene glycol methyl ether acetate; the surface protection layer is prepared from the following raw materials in parts by weight: 4g of polysiloxane polymer with molecular weight of 2000, 3330.4 g of BYK and 5g of diluent.
A preparation method of coated glass with an ultraviolet shielding function comprises the following steps:
(1) weighing 3g of zinc chloride and 8g of tetrabutyl titanate, ultrasonically dispersing in 120mL of absolute ethyl alcohol, placing the solution in a high-pressure reaction kettle, preserving heat for 2h at 180 ℃, cooling to room temperature, and freeze-drying to obtain titanium dioxide-loaded zinc oxide quantum dot particles;
(2) glass coating was performed as follows: selecting a common glass substrate with the size of 8cm by 8cm for cleaning treatment, carrying out ultrasonic treatment on the glass substrate for 5min, then respectively washing the glass substrate with clean water and ethanol, and naturally drying the glass substrate; weighing 4g of titanium dioxide coated zinc oxide quantum dot particles, 1g of disperbYK 1101g, 3g of BYK 3331 g, 1g of siloxane with molecular weight of 500 and 3g of propylene glycol methyl ether acetate, putting the above ingredients into a high-speed shearing machine, mixing and stirring uniformly, then dripping a small amount of dispersion liquid on the surface of a glass substrate, then uniformly spreading on the surface of the glass by using a spin coater to ensure that 0.03g of dispersion liquid is finally left on the surface of the glass, naturally drying the glass in the air, then putting the glass substrate into a muffle furnace at the temperature of 300 ℃ for glue discharge, wherein the heating rate is 5 ℃/min, the heat preservation time is 30min, and taking out the glass substrate after completion;
(3) weighing 4g of polysiloxane polymer with molecular weight of 2000, 3330.4 g of BYK and 5g of diluent, putting the above ingredients into a high-speed shearing machine, mixing and stirring uniformly, dripping 0.3g of organic silicon polymer dispersion liquid on the surface of a glass substrate, uniformly spreading the organic silicon polymer dispersion liquid on the surface layer of the glass by a spin coater, naturally drying the glass in air, putting the glass with a protective layer precursor into a high-temperature tempering furnace at 750 ℃ for tempering for 30 seconds, and rapidly cooling to obtain the coated glass with the ultraviolet shielding function.
Comparative example 3
A coated glass with ultraviolet shielding function comprises a glass substrate, an ultraviolet shielding layer and a surface protection layer, wherein the ultraviolet shielding layer is positioned between the glass substrate and the surface protection layer; the ultraviolet shielding layer is prepared from the following raw materials in parts by weight: 4g of commercially available zinc oxide nanoparticles (the particle size is less than or equal to 100nm), 1101g of DISPERBYK, 3331 g of BYK, 1g of siloxane with the molecular weight of 500 and 3g of propylene glycol methyl ether acetate; the surface protection layer is prepared from the following raw materials in parts by weight: 4g of polysiloxane polymer with molecular weight of 2000, 3330.4 g of BYK and 5g of diluent.
A preparation method of coated glass with an ultraviolet shielding function comprises the following steps:
(1) selecting a common glass substrate with the size of 8cm by 8cm for cleaning treatment, carrying out ultrasonic treatment on the glass substrate for 5min, then respectively washing the glass substrate with clean water and ethanol, and naturally drying the glass substrate; weighing 4g of commercially available zinc oxide nanoparticles, 1g of DISPERBYK 1101g, 3g of BYK 3331 g, 1g of siloxane with molecular weight of 500 and 3g of propylene glycol methyl ether acetate, putting the above ingredients into a high-speed shearing machine, uniformly mixing and stirring, then dripping a small amount of dispersion liquid on the surface of a glass substrate, uniformly spreading the dispersion liquid on the surface of the glass by using a spin coater, and finally leaving 0.03g of dispersion liquid on the surface of the glass, naturally drying the glass in the air, putting the glass in a muffle furnace at the temperature of 300 ℃ for glue removal, wherein the heating rate is 5 ℃/min, the heat preservation time is 30min, and taking out the glass after the completion;
(2) weighing 4g of polysiloxane polymer with molecular weight of 2000, 3330.4 g of BYK and 5g of diluent, putting the above ingredients into a high-speed shearing machine, mixing and stirring uniformly, dripping 0.3g of organic silicon polymer dispersion liquid on the surface of a glass substrate, uniformly spreading the organic silicon polymer dispersion liquid on the surface layer of the glass by a spin coater, naturally drying the glass in air, putting the glass with a protective layer precursor into a high-temperature tempering furnace at 750 ℃ for tempering for 30 seconds, and rapidly cooling to obtain the coated glass with the ultraviolet shielding function.
Comparative example 4
A coated glass with ultraviolet shielding function comprises a glass substrate, an ultraviolet shielding layer and a surface protection layer, wherein the ultraviolet shielding layer is positioned between the glass substrate and the surface protection layer; the ultraviolet shielding layer is prepared from the following raw materials in parts by weight: DISPERBYK 1101g, BYK 3331 g, siloxane with molecular weight of 500 g and propylene glycol methyl ether acetate 3 g; the surface protection layer is prepared from the following raw materials in parts by weight: 4g of polysiloxane polymer with molecular weight of 2000, 3330.4 g of BYK and 5g of diluent.
A preparation method of coated glass with an ultraviolet shielding function comprises the following steps:
(1) selecting a common glass substrate with the size of 8cm by 8cm for cleaning treatment, carrying out ultrasonic treatment on the glass substrate for 5min, then respectively washing the glass substrate with clean water and ethanol, and naturally drying the glass substrate; weighing DISPERBYK 1101g, BYK 3331 g, siloxane 1g with the molecular weight of 500 and propylene glycol methyl ether acetate 3g, putting the above ingredients into a high-speed shearing machine, mixing and stirring uniformly, then dropping a small amount of dispersion liquid on the surface of a glass substrate, then uniformly spreading the dispersion liquid on the surface layer of the glass by using a spin coater, so that 0.03g of dispersion liquid is finally left on the surface of the glass, after the glass is naturally dried, putting the glass into a muffle furnace at the temperature of 300 ℃ for glue discharge, wherein the heating rate is 5 ℃/min, the heat preservation time is 30min, and taking out the glass after the glue discharge is finished;
(2) weighing 4g of polysiloxane polymer with molecular weight of 2000, 3330.4 g of BYK and 5g of diluent, putting the above ingredients into a high-speed shearing machine, mixing and stirring uniformly, dripping 0.3g of organic silicon polymer dispersion liquid on the surface of a glass substrate, uniformly spreading the organic silicon polymer dispersion liquid on the surface layer of the glass by a spin coater, naturally drying the glass in air, putting the glass with a protective layer precursor into a high-temperature tempering furnace at 750 ℃ for tempering for 30 seconds, and rapidly cooling to obtain the coated glass with the ultraviolet shielding function.
Comparative example 5
A coated glass with ultraviolet shielding function comprises a glass substrate, an ultraviolet shielding layer and a surface protection layer, wherein the ultraviolet shielding layer is positioned between the glass substrate and the surface protection layer; the ultraviolet shielding layer is prepared from the following raw materials in parts by weight: 4g of titanium dioxide coated with silicon dioxide loaded zinc oxide quantum dot particles, 4g of DISPERBYK 1101g, BYK 3331 g and 3g of propylene glycol methyl ether acetate; the surface protection layer is prepared from the following raw materials in parts by weight: 4g of polysiloxane polymer with molecular weight of 2000, 3330.4 g of BYK and 5g of diluent.
A preparation method of coated glass with an ultraviolet shielding function comprises the following steps:
(1) weighing 10g of zinc chloride and 30g of tetrabutyl titanate, ultrasonically dispersing in 350mL of absolute ethyl alcohol, placing the solution in a high-pressure reaction kettle, preserving the temperature for 2h at 200 ℃, naturally cooling to room temperature, and freeze-drying the solution to obtain the titanium dioxide loaded zinc oxide quantum dot particles.
5g of titanium dioxide are weighedUltrasonically dispersing the loaded zinc oxide quantum dots in 200mL of absolute ethanol solution, then adding 15mL of ethyl orthosilicate and 15mL of ammonia water, stirring the mixed solution in a water bath at 45 ℃ for 10h at constant temperature, then washing with water, washing with alcohol, drying, and then adding N2Calcining for 3h at 400 ℃ under protection to obtain the titanium dioxide loaded zinc oxide quantum dot particles coated by silicon dioxide. Weighing 10g of zinc oxide nanoparticles, 30mL of ammonia water and 30g of tetrabutyl titanate, ultrasonically dispersing in 500mL of absolute ethyl alcohol, stirring for 10 hours in a water bath at a constant temperature of 45 ℃, then washing with water and alcohol, and calcining for 3 hours at 400 ℃ under the protection of N2 to obtain titanium dioxide coated zinc oxide particles;
(2) glass coating was performed as follows: selecting a common glass substrate with the size of 8cm by 8cm for cleaning treatment, carrying out ultrasonic treatment on the glass substrate for 5min, then respectively washing the glass substrate with clean water and ethanol, and naturally drying the glass substrate; weighing 4g of titanium dioxide loaded zinc oxide quantum dot particles coated with silicon dioxide, DISPERBYK 1101g, BYK 3331 g and 3g of propylene glycol methyl ether acetate, putting the above ingredients into a high-speed shearing machine for mixing and stirring uniformly, then dropping a small amount of dispersion liquid on the surface of a glass substrate, then uniformly spreading the dispersion liquid on the surface layer of the glass by a spin coater, so that 0.03g of the dispersion liquid is finally left on the surface of the glass, naturally drying the glass in the air, putting the glass into a muffle furnace at the temperature of 300 ℃ for glue discharge, wherein the heating rate is 5 ℃/min, the heat preservation time is 30min, and taking out the glass after the completion;
(3) weighing 4g of polysiloxane polymer with molecular weight of 2000, 3330.4 g of BYK and 5g of diluent, putting the above ingredients into a high-speed shearing machine, mixing and stirring uniformly, dripping 0.3g of organic silicon polymer dispersion liquid on the surface of a glass substrate, uniformly spreading the organic silicon polymer dispersion liquid on the surface layer of the glass by a spin coater, naturally drying the glass in air, putting the glass with a protective layer precursor into a high-temperature tempering furnace at 750 ℃ for tempering for 30 seconds, and rapidly cooling to obtain the coated glass with the ultraviolet shielding function.
Comparative example 6
A coated glass with ultraviolet shielding function comprises a glass substrate, an ultraviolet shielding layer and a surface protection layer, wherein the ultraviolet shielding layer is positioned between the glass substrate and the surface protection layer; the ultraviolet shielding layer is prepared from the following raw materials in parts by weight: 4g of titanium dioxide coated with silicon dioxide loaded with zinc oxide quantum dot particles, 1g of siloxane with molecular weight of 500, and 3g of propylene glycol methyl ether acetate; the surface protection layer is prepared from the following raw materials in parts by weight: 4g of polysiloxane polymer with molecular weight of 2000, 3330.4 g of BYK and 5g of diluent.
A preparation method of coated glass with an ultraviolet shielding function comprises the following steps:
(1) weighing 10g of zinc chloride and 30g of tetrabutyl titanate, ultrasonically dispersing in 350mL of absolute ethyl alcohol, placing the solution in a high-pressure reaction kettle, preserving heat for 2h at 200 ℃, naturally cooling to room temperature, and freeze-drying the solution to obtain titanium dioxide-loaded zinc oxide quantum dot particles;
weighing 5g of titanium dioxide loaded zinc oxide quantum dots, ultrasonically dispersing the titanium dioxide loaded zinc oxide quantum dots in 200mL of absolute ethanol solution, then adding 15mL of ethyl orthosilicate and 15mL of ammonia water, stirring the mixed solution in a water bath at 45 ℃ for 10 hours at constant temperature, then washing with water, washing with alcohol, drying, and then adding N2Calcining for 3h at 400 ℃ under protection to obtain titanium dioxide loaded zinc oxide quantum dot particles coated with silicon dioxide;
(2) selecting a common glass substrate with the size of 8cm by 8cm for cleaning treatment, carrying out ultrasonic treatment on the glass substrate for 5min, then respectively washing the glass substrate with clean water and ethanol, and naturally drying the glass substrate; weighing 4g of titanium dioxide loaded zinc oxide quantum dot particles coated with silicon dioxide, 1g of DISPERBYK 1101g, 1g of siloxane with molecular weight of 500 and 3g of propylene glycol methyl ether acetate, putting the above ingredients into a high-speed shearing machine for mixing and stirring uniformly, then dropping a small amount of dispersion liquid on the surface of a glass substrate, then uniformly spreading the dispersion liquid on the surface of the glass by a spin coater, so that 0.03g of dispersion liquid is finally left on the surface of the glass, naturally drying the glass in the air, then putting the glass into a muffle furnace at the temperature of 300 ℃ for glue discharge, wherein the heating rate is 5 ℃/min, the heat preservation time is 30min, and taking out the glass after the completion;
(3) weighing 4g of polysiloxane polymer with molecular weight of 2000, 3330.4 g of BYK and 5g of diluent, putting the above ingredients into a high-speed shearing machine, mixing and stirring uniformly, dripping 0.3g of organic silicon polymer dispersion liquid on the surface of a glass substrate, uniformly spreading the organic silicon polymer dispersion liquid on the surface layer of the glass by a spin coater, naturally drying the glass in air, putting the glass with a protective layer precursor into a high-temperature tempering furnace at 750 ℃ for tempering for 30 seconds, and rapidly cooling to obtain the coated glass with the ultraviolet shielding function.
Comparative example 7
A coated glass with ultraviolet shielding function comprises a glass substrate, an ultraviolet shielding layer and a surface protection layer, wherein the ultraviolet shielding layer is positioned between the glass substrate and the surface protection layer; the ultraviolet shielding layer is prepared from the following raw materials in parts by weight: 4g of titanium dioxide coated with silicon dioxide loaded with zinc oxide quantum dot particles, 4g of DISPERBYK 1101g, BYK 3331 g, 1g of siloxane with molecular weight of 500 and 3g of propylene glycol methyl ether acetate; the surface protection layer is prepared from the following raw materials in parts by weight: 4g of polysiloxane polymer with molecular weight of 2000 and 5g of diluent.
A preparation method of coated glass with an ultraviolet shielding function comprises the following steps:
(1) weighing 10g of zinc chloride and 30g of tetrabutyl titanate, ultrasonically dispersing in 350mL of absolute ethyl alcohol, placing the solution in a high-pressure reaction kettle, preserving the temperature for 2h at 200 ℃, naturally cooling to room temperature, and freeze-drying the solution to obtain the titanium dioxide loaded zinc oxide quantum dot particles.
Weighing 5g of titanium dioxide loaded zinc oxide quantum dots, ultrasonically dispersing the titanium dioxide loaded zinc oxide quantum dots in 200mL of absolute ethanol solution, then adding 15mL of ethyl orthosilicate and 15mL of ammonia water, stirring the mixed solution in a water bath at 45 ℃ for 10 hours at constant temperature, then washing with water, washing with alcohol, drying, and then adding N2Calcining for 3h at 400 ℃ under protection to obtain titanium dioxide loaded zinc oxide quantum dot particles coated with silicon dioxide;
(2) glass coating was performed as follows: selecting a common glass substrate with the size of 8cm by 8cm for cleaning treatment, carrying out ultrasonic treatment on the glass substrate for 5min, then respectively washing the glass substrate with clean water and ethanol, and naturally drying the glass substrate; weighing 4g of titanium dioxide loaded zinc oxide quantum dot particles coated with silicon dioxide, 1g of DISPERBYK 1101g, BYK 3331 g, 1g of siloxane with molecular weight of 500 and 3g of propylene glycol methyl ether acetate, putting the above ingredients into a high-speed shearing machine, mixing and stirring uniformly, then dropping a small amount of dispersion liquid on the surface of a glass substrate, then uniformly spreading the dispersion liquid on the surface of the glass by a spin coater, so that 0.03g of the dispersion liquid is finally left on the surface of the glass, naturally drying the glass in the air, then putting the glass in a muffle furnace at the temperature of 300 ℃ for glue discharge, wherein the heating rate is 5 ℃/min, the heat preservation time is 30min, and taking out the glass after completion;
(3) weighing 4g of polysiloxane polymer with molecular weight of 2000 and 5g of diluent, putting the above ingredients into a high-speed shearing machine, mixing and stirring uniformly, dripping 0.3g of organic silicon polymer dispersion liquid on the surface of a glass substrate, spreading the organic silicon polymer dispersion liquid on the surface of the glass by a spin coater, naturally drying the glass, putting the glass with a protective layer precursor into a high-temperature tempering furnace at 750 ℃ for tempering for 30 seconds, and then quickly cooling to obtain the coated glass with the ultraviolet shielding function.
Comparative example 8
A coated glass with ultraviolet shielding function comprises a glass substrate, an ultraviolet shielding layer and a surface protection layer, wherein the ultraviolet shielding layer is positioned between the glass substrate and the surface protection layer; the ultraviolet shielding layer is prepared from the following raw materials in parts by weight: 4g of titanium dioxide coated with silicon dioxide loaded with zinc oxide quantum dot particles, 4g of DISPERBYK 1101g, BYK 3331 g, 1g of siloxane with molecular weight of 500 and 3g of propylene glycol methyl ether acetate; the surface protection layer is prepared from the following raw materials in parts by weight: BYK 3330.4 g, and diluent 5 g.
A preparation method of coated glass with an ultraviolet shielding function comprises the following steps:
(1) weighing 10g of zinc chloride and 30g of tetrabutyl titanate, ultrasonically dispersing in 350mL of absolute ethyl alcohol, placing the solution in a high-pressure reaction kettle, preserving the temperature for 2h at 200 ℃, naturally cooling to room temperature, and freeze-drying the solution to obtain the titanium dioxide loaded zinc oxide quantum dot particles.
Weighing 5g of titanium dioxide loaded zinc oxide quantum dots, ultrasonically dispersing the titanium dioxide loaded zinc oxide quantum dots in 200mL of absolute ethanol solution, then adding 15mL of ethyl orthosilicate and 15mL of ammonia water, stirring the mixed solution in a water bath at 45 ℃ for 10 hours at constant temperature, then washing with water, washing with alcohol, drying, and then adding N2Under protection at 400 DEG CCalcining for 3h to obtain titanium dioxide loaded zinc oxide quantum dot particles coated with silicon dioxide;
(2) glass coating was performed as follows: selecting a common glass substrate with the size of 8cm by 8cm for cleaning treatment, carrying out ultrasonic treatment on the glass substrate for 5min, then respectively washing the glass substrate with clean water and ethanol, and naturally drying the glass substrate; weighing 4g of titanium dioxide loaded zinc oxide quantum dot particles coated with silicon dioxide, 1g of DISPERBYK 1101g, BYK 3331 g, 1g of siloxane with molecular weight of 500 and 3g of propylene glycol methyl ether acetate, putting the above ingredients into a high-speed shearing machine, mixing and stirring uniformly, then dropping a small amount of dispersion liquid on the surface of a glass substrate, then uniformly spreading the dispersion liquid on the surface of the glass by a spin coater, so that 0.03g of the dispersion liquid is finally left on the surface of the glass, naturally drying the glass in the air, then putting the glass in a muffle furnace at the temperature of 300 ℃ for glue discharge, wherein the heating rate is 5 ℃/min, the heat preservation time is 30min, and taking out the glass after completion;
(3) weighing BYK 3330.4 g and 5g of diluent, putting the above ingredients into a high-speed shearing machine, mixing and stirring uniformly, dripping 0.3g of dispersion liquid on the surface of a glass substrate, uniformly spreading the dispersion liquid on the surface layer of the glass by using a spin coater, naturally drying the glass in the air, putting the glass with a protective layer precursor into a high-temperature tempering furnace at 750 ℃ for tempering for 30 seconds, and then quickly cooling to obtain the coated glass with the ultraviolet shielding function.
The test results of the optical transmittance measuring instrument on the forest of the common glass substrate and the coated glass after finishing coating and tempering are shown in table 1, the ultraviolet transmittance of the coated glass in the embodiments 1-3 is obviously reduced, a good ultraviolet shielding effect is achieved, the infrared transmittance and the visible light transmittance are not changed basically, and the selective light shielding effect is achieved. In comparative example 1, commercially available silica-coated zinc oxide quantum dot particles are directly used, no titanium dioxide is loaded, no haze is generated after glass coating is completed, ultraviolet light can be selectively shielded, and the shielding effect is weakened compared with that of example 1; in the comparative example 2, titanium dioxide-loaded zinc oxide quantum dot particles are directly used, silicon dioxide coating is not performed, haze is not generated after glass coating is completed, ultraviolet light can be selectively shielded, and the shielding effect is weakened compared with that of the example 1; the coated glass in the comparative example 3 uses zinc oxide nanoparticles having a particle size of 100nm or less, which are commercially available, and the ultraviolet shielding effect is reduced as compared with that of example 1, and the glass has slight haze; in the comparative example 4, titanium dioxide coated with silicon dioxide is not used to load zinc oxide quantum dot particles, and ultraviolet shielding effect is not generated after coating, which is basically the same as that of common substrate glass; in the comparative example 5, no high-temperature agglomeration-preventing assistant is added, the titanium dioxide coated with silicon dioxide loaded with zinc oxide quantum dot particles is slightly agglomerated in the toughening process, the ultraviolet shielding effect of the glass is influenced, and the visible light transmittance is reduced to some extent and the haze is slight compared with that in the example 1; comparative example 6 because no leveling agent was added during the coating of the uv-shielding layer, the dispersion was not completely spread flat, and the glass surface had slight wavy lines, which affected the aesthetics; comparative example 7 since no leveling agent was added during the coating of the protective layer, the organic silicon polymer dispersion was not completely spread flat, and the surface of the glass coated with the film had slight lines and was not smooth enough; comparative example 8 no silicone polymer was used and no dense protective layer was formed on the outer surface of the ultraviolet shielding layer, so the glass hardness did not meet the standard seriously.
TABLE 1 forest optical transmittance test results
FIG. 1 shows the transmittance spectra at 300-2000nm of a conventional glass substrate and the coated glass obtained in example 1, which were measured by a spectrophotometer, and the above results were further verified.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A coated glass with ultraviolet shielding function is characterized in that: the glass comprises a glass substrate, an ultraviolet shielding layer and a surface protection layer, wherein the ultraviolet shielding layer is positioned between the glass substrate and the surface protection layer;
the ultraviolet shielding layer is prepared from the following raw materials in parts by weight:
the surface protection layer is prepared from the following raw materials in parts by weight:
30-70 parts of an organic silicon polymer,
0.1 to 10 portions of protective leveling agent,
30-70 parts of a protective diluent.
2. The coated glass having an ultraviolet shielding function according to claim 1, characterized in that: the titanium dioxide loaded zinc oxide quantum dot particle coated with silicon dioxide is prepared by the following steps: ultrasonically dispersing titanium dioxide-loaded zinc oxide quantum dots, ammonia water and ethyl orthosilicate in an ethanol solution, continuously stirring for 6-14h in a water bath at 45-60 ℃, washing, drying, and then treating for 2-6h at 500 ℃ in an inert atmosphere to obtain the titanium dioxide-loaded zinc oxide quantum dot particles coated by silicon dioxide.
3. The coated glass having an ultraviolet shielding function according to claim 2, characterized in that: the titanium dioxide loaded zinc oxide quantum dot is prepared by the method comprising the following steps: ultrasonically dispersing zinc chloride and tetrabutyl titanate in absolute ethyl alcohol, then placing the mixture in a high-pressure reaction kettle, preserving the heat for 6-48h at the temperature of 140-200 ℃, cooling to room temperature, and then carrying out freeze drying to obtain the titanium dioxide loaded zinc oxide quantum dot.
4. The coated glass having an ultraviolet shielding function according to claim 3, characterized in that: the solid-liquid mass ratio of the zinc chloride to the tetrabutyl titanate to the absolute ethyl alcohol is as follows: 1-5:1-20: 50-100; the solid-liquid mass ratio of the titanium dioxide loaded zinc oxide quantum dots, ammonia water, ethyl orthosilicate and ethanol solution is 1-30:5-30:5-30: 50-100; the particle size of the titanium dioxide loaded zinc oxide quantum dot particles coated by the silicon dioxide is less than or equal to 10 nm.
5. The coated glass having an ultraviolet shielding function according to claim 1, characterized in that: the high-temperature agglomeration-preventing auxiliary agent is at least one of micromolecular siloxane or micromolecular silica sol; the molecular weight of the micromolecular siloxane is 500-1000; the dispersant is at least one of DISPERBYK 110, DISPERBYK 180, DISPERBYK2080, MONENG 3035, MONENG 3063, EFKA PX4701 or KMT 3003;
the shielding leveling agent is at least one of BYK 333, Modarez MF AEX, DOWSIL FZ-2123, Coatosil 7500 or SKYTYPE LA 0520; the shielding diluent is at least one of ethanol, propylene glycol methyl ether acetate, ethyl acetate, dipropylene glycol dimethyl ether, butyl acetate or isoparaffin.
6. The coated glass having an ultraviolet shielding function according to claim 1, characterized in that: the protective leveling agent is at least one of BYK 333, Modarez MF AEX, DOWSIL FZ-2123, Coatosil 7500 or SKYTYPE LA 0520; the protective diluent is at least one of ethanol, propylene glycol methyl ether acetate, ethyl acetate, dipropylene glycol dimethyl ether, butyl acetate or isoparaffin;
the organic silicon polymer is at least one of methyl silicone resin, methyl phenyl silicone resin, silicon carbide hybrid polymer, polysiloxane polymer, polysilazane polymer or organic polyborosilazane polymer; preferably, the organic silicon polymer is at least one of silicon carbide hybrid polymer or polysilazane polymer; the molecular weight of the polysiloxane polymer was 2000-.
7. The method for producing a coated glass having an ultraviolet-shielding function according to any one of claims 1 to 6, characterized in that: the method comprises the following steps:
(1) coating an ultraviolet shielding layer: cleaning a glass substrate, uniformly mixing silicon dioxide-coated titanium dioxide loaded zinc oxide quantum dot particles, a dispersing agent, a high-temperature agglomeration-preventing auxiliary agent, a shielding leveling agent and a shielding diluent through high-speed shearing, uniformly spreading the obtained dispersion liquid on the surface of the glass substrate, putting the glass substrate into a high-temperature glue discharging furnace for glue discharging treatment, taking out the glass plate when the glass plate is hot after the glue discharging is finished, and finishing the coating of an ultraviolet shielding layer;
(2) coating a surface protection layer: and (2) uniformly mixing the organic silicon polymer, the protective leveling agent and the protective diluent through a high-speed shearing machine, uniformly spreading the obtained dispersion liquid to the outer surface of the ultraviolet shielding layer obtained in the step (1) to form a protective layer precursor, putting the protective layer precursor into a high-temperature tempering furnace for tempering, and then quickly cooling to obtain the coated glass with the ultraviolet shielding function.
8. The method for producing a coated glass having an ultraviolet-shielding function according to claim 7, characterized in that: the spreading step in the step (1) is one of spraying, spin coating, brushing, flow coating or natural leveling; the spreading thickness of the dispersion liquid in the step (1) is 0.1-100 μm; the mass of the titanium dioxide loaded zinc oxide quantum dot particles coated by the silicon dioxide in the ultraviolet shielding layer is 0.1-10g/m2(ii) a The mass of the high-temperature agglomeration-preventing auxiliary agent in the ultraviolet shielding layer is 0.01-0.5g/m2(ii) a Preferably, the spreading thickness of the dispersion liquid in the step (1) is 0.1-30 μm; the mass of the titanium dioxide loaded zinc oxide quantum dot particles coated by the silicon dioxide in the ultraviolet shielding layer is 0.1-3g/m2(ii) a The temperature rising rate of the glue discharging treatment in the step (1) is 5-10 ℃/min, the temperature is 200-400 ℃, the heat preservation time is 30-60min, and then the glue is naturally cooled.
9. The method for producing a coated glass having an ultraviolet-shielding function according to claim 7, characterized in that: the spreading step in the step (2) is spraying, spin coating, brushing,One of flow coating or natural leveling; the spreading thickness of the dispersion liquid in the step (2) is 0.1-100 μm; the mass of the organic silicon polymer in the surface protection layer is 1-100g/m2(ii) a Preferably, the spreading thickness of the dispersion liquid in the step (2) is 1-30 μm; the mass of the organic silicon polymer in the surface protection layer is 1-30g/m2(ii) a The temperature of the toughening step in the step (2) is 700-900 ℃, and the time is 30-300 s.
10. The method for producing a coated glass having an ultraviolet-shielding function according to claim 7, characterized in that: the titanium dioxide loaded zinc oxide quantum dot particle coated with silicon dioxide is prepared by the following steps:
(1) ultrasonically dispersing zinc chloride and tetrabutyl titanate in absolute ethyl alcohol, then placing the mixture in a high-pressure reaction kettle, preserving the heat for 6-48h at the temperature of 140-200 ℃, cooling to room temperature, and then carrying out freeze drying to obtain the titanium dioxide loaded zinc oxide quantum dots;
(2) ultrasonically dispersing titanium dioxide-loaded zinc oxide quantum dots, ammonia water and ethyl orthosilicate in an ethanol solution, continuously stirring for 6-14h in a water bath at 45-60 ℃, washing, drying, and then treating for 2-6h at 500 ℃ in an inert atmosphere to obtain titanium dioxide-loaded zinc oxide quantum dot particles coated by silicon dioxide;
the solid-liquid mass ratio of the zinc chloride to the tetrabutyl titanate to the absolute ethyl alcohol is as follows: 1-5:1-20: 50-100; the solid-liquid mass ratio of the titanium dioxide loaded zinc oxide quantum dots, ammonia water, ethyl orthosilicate and ethanol solution is 1-30:5-30:5-30: 50-100; the particle size of the titanium dioxide loaded zinc oxide quantum dot particles coated by the silicon dioxide is less than or equal to 10 nm.
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