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CN-121991538-A - Ultraviolet-resistant corrosion-resistant antireflection film and preparation method thereof

CN121991538ACN 121991538 ACN121991538 ACN 121991538ACN-121991538-A

Abstract

The invention relates to an ultraviolet-resistant corrosion-resistant antireflection film and a preparation method thereof, the antireflection film is composed of a silicon oxide-titanium oxide composite film and a porous silicon oxide film, wherein the porous silicon oxide film contains cerium oxide as an ultraviolet protective agent. The preparation method comprises the steps of mixing silica sol and titanium oxide sol to form a composite film coating liquid, mixing the porous silica film coating liquid with co-precursor modified silica sol, hollow silica nano spherical particle dispersion liquid, silane coupling agent and ultraviolet protective agent to form the composite film coating liquid, coating glass serving as a coating substrate on the surface of the glass to form the composite film coating liquid, and curing the composite film coating liquid after coating the porous silica film coating liquid on the surface of the composite film. Under the combined action of the bottom layer composite film and the surface layer film added with the nano cerium oxide, the invention not only maintains the anti-reflection performance, but also obviously improves the ultraviolet resistance of the film layer, and simultaneously the hydrophobicity of the surface layer film L can greatly improve the corrosion resistance of the surface layer film L to water vapor, salt fog and the like.

Inventors

  • BAO TIAN
  • WANG DONG
  • LI GANG
  • TANG YONGKANG
  • LIU CHANG
  • Yan Rongkang

Assignees

  • 中建材玻璃新材料研究院集团有限公司

Dates

Publication Date
20260508
Application Date
20260214

Claims (6)

  1. 1. The ultraviolet-resistant corrosion-resistant antireflection film is characterized by comprising a silicon oxide-titanium oxide composite film H and a porous silicon oxide film L, wherein the composite film H is covered on the surface of glass, the porous silicon oxide film L is covered on the composite film H, and cerium oxide is contained in the porous silicon oxide film L as an ultraviolet protective agent.
  2. 2. The method for preparing the ultraviolet-resistant corrosion-resistant antireflection film according to claim 1, wherein the method comprises the following steps: the coating solution used in the composite film H is formed by mixing silica sol and titanium oxide sol according to the silicon-titanium molar ratio of (2-5): 1, wherein the silica sol is a dispersion system consisting of a silicon source precursor, water, an alcohol solvent and an acid catalyst according to the molar ratio of (2-5): 15-50): 0.0001-0.05, and is prepared by a hydrolysis and polycondensation step, and the titanium oxide sol is a dispersion body consisting of a titanium source precursor, water, an alcohol solvent, acetylacetone, N-dimethylformamide and an acid catalyst according to the molar ratio of (2-5): 30-60): 0.5-1.5): 0.5:0.0001-0.01, and is prepared by a hydrolysis and polycondensation step; The coating liquid of the porous silicon oxide film L is prepared by mixing (by mass ratio) 1 (0.8-2.5) (0.01-0.06) (0.015-0.1) of co-precursor modified silicon oxide sol, hollow silicon oxide nano spherical particle dispersion liquid, silane coupling agent and ultraviolet protective agent, wherein cerium oxide serving as the ultraviolet protective agent is added in the form of 1% -30% of aqueous dispersion liquid or ethanol dispersion liquid, the particle size of cerium oxide particles is 5 nm% -50 nm, and the mass fraction of uniformly dispersed cerium oxide particles in the coating liquid of the porous silicon oxide film L is 0.5% -3.0%.
  3. 3. The method for preparing the ultraviolet-resistant corrosion-resistant antireflection film according to claim 2, wherein the method comprises the following steps: The average particle diameter of the hollow silicon oxide nano spherical particles is 20-50 nm, the hollow silicon oxide nano spherical particles exist in the form of ethanol or isopropanol dispersion liquid with the mass fraction of 10% -30%, and the silane coupling agent is at least one of gamma-aminopropyl triethoxysilane, gamma-aminopropyl methyl diethoxysilane, vinyl triethoxysilane, gamma-methacryloxypropyl trimethoxysilane and gamma- (2, 3-epoxypropoxy) propyl trimethoxysilane.
  4. 4. A method for producing an anti-uv and anti-corrosion antireflection film according to claim 2 or 3, characterized in that: The silicon source precursor used in the coating liquid of the composite film H is at least one of tetraethoxysilane and tetramethoxysilane, and the titanium source precursor used is at least one of tetrabutyl titanate, tetraisobutyl titanate, tetraethyl titanate, tetra-n-propyl titanate and tetraisopropyl titanate; The silicon source precursor of the co-precursor modified silica sol used for the porous silica film L coating solution comprises at least one of tetraethoxysilane and tetramethoxysilane, and also comprises at least one of hydrophobic hydrocarbyl silane such as methyltriethoxysilane and isobutyltriethoxysilane.
  5. 5. A method for producing an anti-uv and anti-corrosion antireflection film according to claim 2 or 3, characterized in that: the alcohol solvent of the coating liquid used by the composite film H and the porous silicon oxide film L is at least one of ethanol, isopropanol, n-propanol and ethylene glycol, and the acid catalyst is at least one of hydrochloric acid, nitric acid and acetic acid.
  6. 6. The method for preparing the ultraviolet-resistant corrosion-resistant antireflection film according to claim 4, wherein the method comprises the following steps: the antireflection film is prepared by taking glass as a film coating substrate, coating the surface of a character glass with a film coating liquid of a composite film H, and curing the character glass at 200-350 ℃ for 2-10 min, and coating the surface of the composite film H with a film coating liquid of a porous silicon oxide film L, and curing the character glass at 450-700 ℃ for 2-60 min.

Description

Ultraviolet-resistant corrosion-resistant antireflection film and preparation method thereof Technical Field The invention relates to the field of glass surface antireflection films, in particular to an ultraviolet-resistant anti-corrosion antireflection film and a preparation method thereof. Background The Ultraviolet (UV) resistance and corrosion resistance of the anti-reflection film on the surface of the encapsulation glass of the photovoltaic module play an important role in ensuring the long-term reliable operation of the module. At present, an antireflection film taking silicon oxide as a main component is commonly adopted in the photovoltaic glass. The surface layer film of the single-layer antireflection film or the double-layer antireflection film is mainly a porous SiO 2 network structure, the refractive index is low (about 1.2-1.4, the refractive index can be adjusted by porosity), the chemical stability and bond energy are high, the body is not easy to damage by UV, but the porous structure can provide a channel for UV-induced aging, the porous structure means a larger specific surface area, and under long-term and high-intensity UV irradiation, UV photons can attack weak points (such as residual silicon hydroxyl groups, pore-forming agents or organic binders) in the film layer, so that the film layer structure is aged slowly, the binding force with a glass substrate is reduced, and the light transmittance is irreversibly attenuated to a certain degree. Under the corrosive environments such as high humidity, high salt fog and the like, hydrophilic silicon hydroxyl (-SiOH) of the antireflection film is easy to adsorb corrosive media such as water and salt fog and the like in the environment, and after a certain time of chemical action, the film layer can be corroded, and the glass substrate can be corroded further. Disclosure of Invention The invention aims to solve the defects of poor ultraviolet resistance and corrosion resistance of an anti-reflection film in the prior art, and provides an ultraviolet-resistant anti-corrosion anti-reflection film and a preparation method thereof. The technical scheme adopted by the invention is as follows: The ultraviolet-resistant corrosion-resistant antireflection film is characterized by comprising a silicon oxide-titanium oxide composite film H and a porous silicon oxide film L, wherein the composite film H is covered on the surface of glass, the porous silicon oxide film L is coated on the composite film H, and cerium oxide is contained in the porous silicon oxide film L as an ultraviolet protective agent. The invention also provides a preparation method of the ultraviolet-resistant corrosion-resistant antireflection film, which is characterized in that: The coating solution used in the composite film H is formed by mixing silica sol and titanium oxide sol according to the silicon-titanium molar ratio of (2-5): 1, wherein the silica sol is a dispersion system consisting of a silicon source precursor, water, an alcohol solvent and an acid catalyst according to the molar ratio of (2-5): 15-50): 0.0001-0.05, and is prepared by a hydrolysis and polycondensation step, and the titanium oxide sol is a dispersion system consisting of a titanium source precursor, water, an alcohol solvent, acetylacetone, N-dimethylformamide and an acid catalyst according to the molar ratio of (2-5): 30-60): 0.5-1.5): 0.5:0.0001-0.01, and is prepared by a hydrolysis and polycondensation step; The coating liquid of the porous silicon oxide film L is prepared by mixing (by mass) 1 (0.8-2.5) (0.01-0.06) (0.015-0.1) of co-precursor modified silicon oxide sol, hollow silicon oxide nano spherical particle dispersion liquid, silane coupling agent and ultraviolet protective agent, wherein cerium oxide serving as the ultraviolet protective agent is added in the form of 1% -30% of aqueous dispersion or ethanol dispersion liquid, the particle size of cerium oxide particles is 5 nm% -50 nm, the mass fraction of uniformly dispersed cerium oxide particles in the coating liquid of the porous silicon oxide film L is 0.5% -3.0%, and the mass fraction is the mass percentage. On the basis of the technical scheme, the following further technical scheme is provided: The average particle diameter of the hollow silicon oxide nano spherical particles is 20-50 nm, the hollow silicon oxide nano spherical particles exist in the form of ethanol or isopropanol dispersion liquid with the mass fraction of 10% -30%, and the silane coupling agent is at least one of gamma-aminopropyl triethoxysilane, gamma-aminopropyl methyl diethoxysilane, vinyl triethoxysilane, gamma-methacryloxypropyl trimethoxysilane and gamma- (2, 3-epoxypropoxy) propyl trimethoxysilane. The silicon source precursor used in the coating liquid of the composite film H is at least one of tetraethoxysilane and tetramethoxysilane, and the titanium source precursor used is at least one of tetrabutyl titanate, tetraisobutyl titanate, tetraethyl tita