WO2023074746A1 - 光学素子および撮像装置 - Google Patents

光学素子および撮像装置 Download PDF

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WO2023074746A1
WO2023074746A1 PCT/JP2022/039953 JP2022039953W WO2023074746A1 WO 2023074746 A1 WO2023074746 A1 WO 2023074746A1 JP 2022039953 W JP2022039953 W JP 2022039953W WO 2023074746 A1 WO2023074746 A1 WO 2023074746A1
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atoms
protective film
optical element
weather
mol
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French (fr)
Japanese (ja)
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信一 小川
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Hoya Corp
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Hoya Corp
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Priority to JP2023556600A priority Critical patent/JP7797521B2/ja
Priority to KR1020247014719A priority patent/KR20240095223A/ko
Priority to CN202280072442.XA priority patent/CN118176442A/zh
Publication of WO2023074746A1 publication Critical patent/WO2023074746A1/ja
Priority to US18/633,885 priority patent/US20240280731A1/en
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard 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
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
    • 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
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/25—Oxides by deposition from the liquid phase
    • 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
    • C03C17/3405—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of organic materials
    • 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
    • C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
    • 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
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus
    • C03C3/17—Silica-free oxide glass compositions containing phosphorus containing aluminium or beryllium
    • 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
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/23—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron
    • C03C3/247—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron containing fluorine and phosphorus
    • 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
    • C03C4/00—Compositions for glass with special properties
    • C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
    • 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
    • C03C4/00—Compositions for glass with special properties
    • C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
    • C03C4/082—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths for infrared absorbing glass
    • 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
    • C03C4/00—Compositions for glass with special properties
    • C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
    • C03C4/085—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths for ultraviolet absorbing glass
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/111—Anti-reflection coatings using layers comprising organic materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/113—Anti-reflection coatings using inorganic layer materials only
    • G02B1/115—Multilayers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/28—Interference filters
    • G02B5/281—Interference filters designed for the infrared light
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/28—Interference filters
    • G02B5/283—Interference filters designed for the ultraviolet
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F39/00—Integrated devices, or assemblies of multiple devices, comprising at least one element covered by group H10F30/00, e.g. radiation detectors comprising photodiode arrays
    • H10F39/10—Integrated devices
    • H10F39/12—Image sensors
    • 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
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/23—Mixtures
    • 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
    • C03C2217/73—Anti-reflective coatings with specific characteristics
    • 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

Definitions

  • the present invention relates to optical elements and imaging devices.
  • Imaging devices using solid-state imaging devices such as CCD and CMOS image sensors installed in digital still cameras (DSC: Digital Still Cameras) such as compact digital cameras and digital single-lens reflex cameras reproduce color tones well and provide sharp images.
  • DSC Digital Still Cameras
  • IRCF InfraRed Cut Filter
  • Patent Documents 1 see JP-A-2014-148567
  • FIG. 1A and 1B are schematic explanatory diagrams of a camera module that constitutes a DSC.
  • FIG. 1A is a schematic explanatory diagram of a camera module for a compact digital camera mounted on a smartphone or the like.
  • FIG. 2 is a schematic explanatory diagram of a camera module associated with a camera;
  • an infrared cut filter (IRCF) 1 selectively reflects ultraviolet light and near-infrared light to match human visibility characteristics. Only the combined visible light is selectively introduced into the module and taken into the image sensor IC.
  • IRCF infrared cut filter
  • the infrared cut filter (IRCF) 1 selectively reflects ultraviolet light and near-infrared light
  • the cover glass CG removes ⁇ -rays and suppresses the intrusion of dust, selectively introduces only light in the visible light region that matches human visibility characteristics into the module, and captures it into the image sensor IC.
  • An absorbing glass substrate that absorbs ultraviolet light and near-infrared light is adopted as a constituent substrate of the infrared cut filter (IRCF), and an antireflection film (AR film ), or by sequentially providing an absorption resin film that absorbs ultraviolet light or near-infrared light and an antireflection film (AR film) on the lower surface side (light emitting surface side) of the glass substrate, the ultraviolet light in the incident light is reduced. While effectively reducing light and near-infrared light, only light in the visible light region is transmitted downward under high incident characteristics.
  • phosphate-based glass, fluorophosphate-based glass, or the like is usually used as a constituent material of the absorbing glass substrate that absorbs ultraviolet light or near-infrared light.
  • These glasses tend to burn under high-temperature and high-humidity conditions, and when such glass burns occur, the optical characteristics change, and the anti-reflection coating or the like provided on the surface of the glass substrate tends to peel off. turned out to be.
  • the present invention provides an optical element capable of exhibiting excellent weather resistance in spite of having a glass substrate made of phosphate glass or fluorophosphate glass, and provides such an optical element. It is an object of the present invention to provide an imaging device having
  • the present inventors conducted extensive studies and found that, together with Si atoms, Ti atoms, Zr atoms and Al and one or more selected from atoms, and the ratio of the total number of Ti atoms, Zr atoms and Al atoms to the total number of Si atoms, Ti atoms, Zr atoms and Al atoms is more than 20.0 atomic% and 75
  • the present inventors have found that the above technical problems can be solved by an optical element provided with a weather-resistant protective film having a monolayer structure of 0.0 atomic % or less, and have completed the present invention based on this finding.
  • the present invention (1) On at least one main surface of a glass substrate made of phosphate-based glass or fluorophosphate-based glass, Including one or more selected from Ti atoms, Zr atoms and Al atoms together with Si atoms, A single layer structure in which the ratio of the total number of Ti atoms, Zr atoms and Al atoms to the total number of Si atoms, Ti atoms, Zr atoms and Al atoms is more than 20.0 atomic% and 75.0 atomic% or less.
  • the weather resistant protective film contains 8.3 to 27.5 atomic % of Si atoms, 6.6 to 28.5 atomic % of one or more selected from Ti atoms, Zr atoms and Al atoms, and 61.5 atomic % of oxygen atoms.
  • the weather resistant protective film is (I) one or more silicon compounds selected from alkoxysilanes, alkoxysilane derivatives, or oligomers composed of one or more polymers thereof; (IIa) an oligomer composed of alkoxytitanium, alkoxytitanium derivatives or polymers of one or more of these; (IIb) Oligomers composed of alkoxyzirconium, alkoxyzirconium derivatives or polymers of one or more of these and (IIc) one or more polyvalent metal compounds selected from oligomers composed of alkoxyaluminums, alkoxyaluminum derivatives or polymers of one or more of these
  • the following general formula (i) is applied to at least one main surface of a glass substrate made of phosphate glass or fluorophosphate glass.
  • an optical element capable of exhibiting excellent weather resistance in spite of having a glass substrate made of phosphate-based glass or fluorophosphate-based glass, and having such an optical element.
  • An imaging device can be provided.
  • FIG.1(a) is a schematic explanatory drawing of the camera module based on a compact digital camera
  • FIG.1(b) is a schematic explanatory drawing of the camera module based on a digital single-lens reflex camera.
  • FIG. 2 is a schematic explanatory diagram showing a form example of an optical element according to the present invention
  • FIG. 2 is a schematic explanatory diagram showing a form example of an optical element according to the present invention
  • the optical element according to the present invention on at least one main surface of a glass substrate made of phosphate glass or fluorophosphate glass, Including one or more selected from Ti atoms, Zr atoms and Al atoms together with Si atoms,
  • the ratio of the total number of atoms of Ti atoms, Zr atoms and Al atoms to the total number of Si atoms, Ti atoms, Zr atoms and Al atoms is more than 20.0 atomic% and 75.0 atomic% or less. It is characterized in that it is provided with a weather-resistant protective film.
  • the optical element according to the present invention has a glass substrate made of phosphate glass or fluorophosphate glass as a glass substrate.
  • the glass substrate preferably has a thickness of 0.01 to 1.50 mm, more preferably 0.01 to 0.70 mm, and more preferably 0.01 to 0.30 mm. is more preferred. By setting the thickness of the glass substrate within the above range, the thickness of the optical element can be easily reduced.
  • the glass substrate is made of phosphate glass or fluorophosphate glass.
  • the phosphate-based glass in the present invention is glass containing P and O as essential components and other optional components, and glass containing CuO is particularly preferable. By including CuO in the phosphate glass, near-infrared light can be absorbed more effectively.
  • Other optional components of the phosphate glass include Ca, Mg, Sr, Ba, Li, Na, K, Cs, and the like.
  • the fluorophosphate-based glass in the present invention is glass containing P, O, and F as essential components and other optional components, and those containing CuO are particularly preferable. By including CuO in the fluorophosphate glass, near-infrared light can be absorbed more effectively.
  • Other optional components of the fluorophosphate glass include, for example, Ca, Mg, Sr, Ba, Li, Na, K and Cs.
  • P 2 O 5 More than 0% by mass and 70% by mass or less, Al 2 O 3 0 to 40% by mass, BaO 0 to 40% by mass, CuO 0 to 40% by mass Those containing are preferred.
  • phosphate glass 20 to 60% by mass of P 2 O 5 , Al 2 O 3 0 to 10% by mass, BaO 0-10% by mass, CuO 0-10% by mass is more preferred.
  • phosphate glass 20 to 60% by mass of P 2 O 5 , Al 2 O 3 1 to 10% by mass, BaO 1 to 10% by mass, CuO 1 to 10% by mass is more preferred.
  • fluorophosphate glass P 2 O 5 More than 0% by mass and 70% by mass or less, Al 2 O 3 0 to 40% by mass, BaO 0 to 40% by mass, CuO 0 to 40% by mass and further containing more than 0% by mass and 40% by mass or less of fluoride.
  • fluorophosphate glass P 2 O 5 20 to 60% by mass, Al 2 O 3 0 to 10% by mass, BaO 0 to 10% by mass, CuO 0-10% by mass and more preferably 1 to 30% by mass of fluoride.
  • fluorophosphate glass P 2 O 5 20 to 60% by mass, Al 2 O 3 1 to 10% by mass, BaO 1 to 10% by mass, CuO 1 to 10% by mass and more preferably 2 to 30% by mass of fluoride.
  • Examples of the fluoride include one or more selected from MgF 2 , CaF 2 , SrF 2 and the like.
  • the glass substrate is preferably an absorption glass substrate that absorbs ultraviolet light or near-infrared light.
  • an absorbing glass substrate means a glass substrate used to absorb only ultraviolet light, only near-infrared light, or both ultraviolet light and near-infrared light, and specifically includes ultraviolet light ( When irradiated with irradiation light including visible light (wavelength range 200 to 400 nm) and visible light (wavelength range over 400 nm to 2500 nm), only ultraviolet light (wavelength range 200 to 400 nm) and near infrared light (wavelength range 700 to 2500 nm) It means a glass that selectively absorbs only or ultraviolet light and near-infrared light and selectively transmits light in the wavelength region of more than 400 nm and less than 700 nm.
  • An optical element according to the present invention is characterized in that a weather-resistant protective film having a single-layer structure is provided on at least one main surface of the glass substrate.
  • a weather-resistant protective film having a single-layer structure is provided on at least one main surface of the glass substrate.
  • the weather-resistant protective film together with Si atoms, Ti atoms, Zr atoms, Al atoms, Mg atoms, P atoms, Ca atoms, Y atoms, Hf atoms, Nb atoms, Ta atoms, W atoms, Zn atoms, Ga atoms , In atoms and La atoms.
  • Si atoms and at least one selected from Ti atoms, Zr atoms and Al atoms are included. Adopt what it contains.
  • the weather-resistant protective film contains Si atoms and at least one selected from Ti atoms, Zr atoms and Al atoms, and further includes Mg atoms, P atoms, Ca atoms, Y atoms, Hf atoms, It may contain one or more selected from Nb atoms, Ta atoms, W atoms, Zn atoms, Ga atoms, In atoms and La atoms.
  • the weather-resistant protective film includes, as will be described later, an alkoxide of each metal, a derivative thereof, or a hydrolysis or dehydration condensate of an oligomer composed of one or more polymers thereof. can be mentioned.
  • the weather-resistant protective film contains Si atoms and at least one selected from Ti atoms, Zr atoms and Al atoms, and further includes Mg atoms, P atoms, Ca atoms, Y atoms, Hf atoms, When it contains one or more selected from Nb atoms, Ta atoms, W atoms, Zn atoms, Ga atoms, In atoms and La atoms, the weather resistant protective film is yttrium aluminum-i-propoxide (Y[Al(O -iC 3 H 7 ) 4 ] 3 ), which includes hydrolysis and dehydration condensates of composite metal alkoxides containing multiple metals.
  • Y[Al(O -iC 3 H 7 ) 4 ] 3 yttrium aluminum-i-propoxide
  • the weather resistant protective film has a single layer structure containing Si atoms and at least one selected from Ti atoms, Zr atoms and Al atoms.
  • the single-layer structure means a measurement image (image contrast) obtained when measured by a scanning transmission electron microscope-energy dispersive X-ray spectrometer (STEM-EDX) or an element It means a layered structure specified by analysis results to consist of forming materials having the same composition.
  • STEM-EDX scanning transmission electron microscope-energy dispersive X-ray spectrometer
  • JED-2300T manufactured by JEOL Ltd.
  • Sample preparation focused ion beam processing (FIB) Accelerating voltage: 200 kV Elemental analysis: EDX mapping (resolution: 256 x 256)
  • the weather-resistant protective film preferably has a thickness of 1000 nm or less, more preferably 10 to 500 nm, even more preferably 30 to 300 nm.
  • the thickness of the weather-resistant protective film is 1000 nm or less, it becomes easy to suppress the occurrence of unevenness during the formation (during heating) of the weather-resistant protective film, and the film surface of the weather-resistant protective film can be easily made uniform.
  • the thickness of the weather-resistant protective film is 10 nm or more, the weather-resistant protective film can easily exhibit sufficient bonding strength, and the mechanical strength of the optical element can be easily improved.
  • the thickness of the weather-resistant protective film is measured at 50 points in the measurement image (image contrast) of the cross section of the optical element obtained when the above STEM-EDX is used. Means the arithmetic mean value when
  • the weather-resistant protective film contains Si atoms and at least one type selected from Ti atoms, Zr atoms and Al atoms.
  • the one or more selected from Ti atoms, Zr atoms and Al atoms contained together with Si atoms in the weather-resistant protective film are preferably Al atoms or Ti atoms, more preferably Al atoms.
  • the ratio ⁇ means a value calculated by the following method.
  • (1) Perform STEM-EDX measurement of the optical element under the above-described measurement conditions to obtain STEM-EDX lines (EDX-ray (K-line) detection intensity lines in the depth direction of each element constituting the optical element).
  • the k factor (correction coefficient that depends on the acceleration voltage and detection efficiency and differs for each atomic number.
  • the k factor of Si atoms is KSi and Ti atoms
  • KTi be the k factor of Zr atoms
  • KZr be the k factor of Zr atoms
  • KAl be the k factor of Al atoms.
  • the weight ratio ATi (% by weight) of Ti atoms forming the weather-resistant protective film can be calculated by the following formula.
  • the value obtained by multiplying the EDX ray integrated intensity X of each atom by the k factor and dividing the value by the atomic weight M of each atom can be regarded as corresponding to the atomic number ratio of each constituent element. Therefore, when the atomic weight of Si atoms is MSi, the atomic weight of Ti atoms is MTi, the atomic weight of Zr atoms is MZr, and the atomic weight of Al atoms is MAl, for example, the ratio ⁇ Ti (atomic %) can be calculated by the following formula. Also, the ratio ⁇ (atomic %) of the total number of atoms of Ti atoms, Zr atoms and Al atoms constituting the weather-resistant protective film can be calculated by the following formula.
  • the weather-resistant protective film contains Si atoms and Ti atoms but does not contain Zr atoms and Al atoms
  • the ratio of the total number of Ti atoms, Zr atoms, and Al atoms constituting the weather-resistant protective film ⁇ (atomic %) can be calculated by the following formula.
  • K Si 1.000
  • K Ti 1.033
  • K Zr 5.696
  • K Al 1.050.
  • the ratio of the total number of atoms of Si atoms, Ti atoms, Zr atoms and Al atoms to the total number of metal atoms constituting the weather-resistant protective film is 70.0 to 100.0 atomic%. preferably 80.0 to 100.0 atomic %, and even more preferably 90.0 to 100.0 atomic %.
  • the ratio (atomic%) of the total number of atoms of Si atoms, Ti atoms, Zr atoms and Al atoms to the total number of metal atoms constituting the weather-resistant protective film also constitutes the weather-resistant protective film.
  • the metal atoms constituting the weather-resistant protective film preferably include Si atoms and at least one selected from Ti atoms, Zr atoms and Al atoms.
  • Si atoms and one or more selected from Ti atoms, Zr atoms and Al atoms, which constitute the weather-resistant protective film are chemically separated between atoms of the same kind or between atoms of different kinds via oxygen atoms. It is preferable to be in a state of being bonded in a three-dimensional network by bonding.
  • atoms of the same kind that are chemically bonded via oxygen atoms are atoms of the same kind (Si atom and Si atom, Ti atom and Ti atom, Zr atom and Zr atom, or Al atom and Al atom) is attached by a chemical bond through an oxygen atom.
  • Si atom and Si atom Si atom and Ti atom, Ti atom and Ti atom, Zr atom and Zr atom, or Al atom and Al atom
  • Si atom and Si atom it means that adjacent Si atoms form a chemical bond represented by -Si-O-Si- through an oxygen atom.
  • heteroatoms are chemically bonded via oxygen atoms
  • heteroatoms Si atom and Ti atom, Si atom and Zr atom, Si atom and Al atom, Ti atom and Zr atom , a Ti atom and an Al atom or a Zr atom and an Al atom
  • the hetero atoms are Si atoms and Ti atoms
  • the adjacent Si atoms and Ti atoms form a chemical bond represented by -Si-O-Ti- through an oxygen atom.
  • the weather-resistant protective film includes, as will be described later, an alkoxide of each metal, a derivative thereof, or a hydrolysis or dehydration condensate of an oligomer composed of one or more polymers thereof.
  • the Si atom and one or more selected from Ti atom, Zr atom and Al atom are formed between the same kind of atoms or heteroatoms via oxygen atoms.
  • a three-dimensional mesh structure can be easily formed by chemical bonding.
  • Si atoms and one or more selected from Ti atoms, Zr atoms, and Al atoms, which constitute the weather-resistant protective film are chemically separated between homogeneous atoms or heteroatoms via oxygen atoms.
  • the three-dimensional network-like bonding state can be confirmed by vibrational spectroscopy (infrared spectroscopy, Raman spectroscopy).
  • the weather-resistant protective film contains Si atoms and at least one selected from Ti atoms, Zr atoms and Al atoms as essential components.
  • the weather-resistant protective film when the weather-resistant protective film is in a state in which a plurality of atoms of the same kind or different atoms are three-dimensionally bonded by chemical bonds via oxygen atoms, the weather-resistant protective film consists of Si atoms. preferably contains 8.3 to 27.5 atomic %, more preferably 13.3 to 26.8 atomic %, and even more preferably 16.6 to 26.0 atomic %.
  • the weather resistant protective film preferably contains 6.6 to 28.5 atomic %, more preferably 7.5 to 22.2 atomic %, of one or more selected from Ti atoms, Zr atoms and Al atoms. Those containing 8.3 to 18.1 atomic % are more preferable.
  • the weather resistant protective film preferably contains 61.9 to 66.6 atomic % oxygen atoms, more preferably 62.9 to 66.6 atomic %, and 63.6 to 66 atomic % oxygen atoms. More preferably, it contains 0.6 atomic %.
  • the content of Si atoms and the content of one or more selected from Ti atoms, Zr atoms and Al atoms, which constitute the weather-resistant protective film are determined by ICP (Inductively Coupled Plasma) spectroscopy. means a value determined by an analytical method.
  • the content of oxygen atoms constituting the weather-resistant protective film means a value measured by an inorganic elemental analysis method.
  • the weather resistant protective film is (I) an oligomer composed of an alkoxysilane, an alkoxysilane derivative, or a polymer of one or more of these; (IIa) an oligomer composed of alkoxytitanium, alkoxytitanium derivatives or polymers of one or more of these; Hydrolysis and dehydration of (IIb) alkoxyaluminums, alkoxyaluminum derivatives or oligomers consisting of one or more polymers thereof and (IIc) alkoxyaluminums, alkoxyaluminum derivatives or oligomers consisting of one or more polymers thereof. It preferably contains a condensate.
  • alkoxysilane which is a raw material for the weather-resistant protective film
  • examples of the alkoxysilane include one or more selected from tetramethyl silicate, tetraethyl silicate, tetrapropyl silicate, and tetrabutyl silicate. , tetramethyl silicate and tetraethyl silicate are preferred.
  • the alkoxysilane derivative which is a raw material for the weather-resistant protective film, is a compound derived from an alkoxysilane into which a functional group other than an alkoxy group has been introduced as a part or all of the substituents, which undergoes hydrolysis and dehydration condensation reactions.
  • a functional group capable of forming a bond by reacting with hydroxyl groups on the surface of the glass substrate, alkoxysilane derivatives, or other constituents constituting the weather-resistant protective film are preferred. can be mentioned.
  • the functional group is an alkyl group
  • the functional group is an aromatic group (phenyl group)) phenyltrimethoxysilane, phenyltriethoxysilane and the like.
  • the functional group is a vinyl group
  • vinyltrimethoxysilane vinyltriethoxysilane and the like.
  • the functional group is an epoxy group
  • 3-glycidoxypropyltriethoxysilane 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and the like.
  • the functional group is a styryl group
  • p-styryltrimethoxysilane and the like are styryl groups
  • the functional group is a methacryl group
  • the functional group is an acrylic group
  • 3-acryloxypropyltrimethoxysilane and the like is an acrylic group
  • the functional group is an amino group
  • 3-aminopropyltriethoxysilane N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3 - aminopropyltrimethoxysilane and the like.
  • the functional group is a ureido group
  • the functional group is a mercapto group
  • the functional group is an isocyanate group
  • Silicon tetrachloride (having a halogen functional group) Silicon tetrachloride and the like.
  • the oligomer composed of one or more polymers selected from alkoxysilanes and alkoxysilane derivatives, which is a raw material for the weather-resistant protective film includes an oligomer composed of a polymer of a monomer composed of one or more of the above-mentioned alkoxysilanes.
  • An oligomer comprising a polymer of a monomer comprising one or more alkoxysilane derivatives, an oligomer comprising a polymer comprising a monomer comprising one or more of the alkoxysilanes described above and a monomer comprising one or more of the alkoxysilane derivatives described above. can be mentioned.
  • Alkoxytitanium which is a raw material for the weather resistant protective film, includes titanium (IV) tetramethoxide, titanium (IV) tetraethoxide, titanium (IV) tetra-iso-propoxide, and titanium (IV) tetra-n-butoxide. etc. can be mentioned.
  • the alkoxytitanium derivative which is a raw material for the weather-resistant protective film, is a compound derived from an alkoxytitanium to which a functional group other than an alkoxy group has been introduced as a part or all of the substituents, which undergoes hydrolysis and dehydration condensation reactions.
  • alkoxytitanium derivatives include titanium diisopropoxybis (acetylacetonate), titanium diisopropoxybis (ethylacetoacetate), titanium octylene glycolate, titanium tetraacetylacetonate, titanium diisopropoxybis ( triethanolamine), titanyl chloride, titanium tetrachloride, and the like.
  • the oligomer composed of one or more polymers selected from alkoxytitanium and alkoxytitanium derivatives, which is the raw material for the weather-resistant protective film includes an oligomer composed of a polymer of monomers composed of one or more of the above-mentioned alkoxytitaniums. Oligomer consisting of a polymer of monomers consisting of any one or more alkoxytitanium derivatives, and a polymer consisting of a monomer consisting of any one or more of the above-mentioned alkoxytitanium derivatives and a monomer consisting of any one or more of the above-mentioned alkoxytitanium derivatives can be mentioned.
  • Alkoxyzirconium which is a raw material for the weather-resistant protective film, includes zirconium (IV) tetramethoxide, zirconium (IV) tetraethoxide, zirconium (IV) tetra-n-propoxide, and zirconium (IV) tetra-i-propoxy. zirconium (IV) tetra-n-butoxide and the like.
  • the alkoxyzirconium derivative which is a raw material for the weather-resistant protective film, is a compound derived from an alkoxyzirconium to which a functional group other than an alkoxy group has been introduced as a part or all of the substituents, and which undergoes hydrolysis and dehydration-condensation reactions.
  • a functional group capable of forming a bond by reacting with a hydroxyl group on the surface of the glass substrate, alkoxyzirconium derivatives, or other constituents constituting the weather-resistant protective film.
  • alkoxyzirconium derivative specifically, one or more selected from zirconium tributoxymonoacetylacetonate, zirconium butoxybis(ethylacetoacetate), (isopropoxy)tris(dipivaloylmethanato)zirconium, and the like can be mentioned. can.
  • the oligomer composed of one or more polymers selected from alkoxyzirconium and alkoxyzirconium derivatives, which is a raw material for the weather-resistant protective film includes an oligomer composed of a polymer of monomers composed of one or more of the above-mentioned alkoxyzirconiums. Oligomer consisting of a polymer of monomers consisting of any one or more alkoxyzirconium derivatives, and a polymer consisting of a monomer consisting of any one or more of the above-mentioned alkoxyzirconium derivatives and a monomer consisting of one or more of the above-mentioned alkoxyzirconium derivatives can be mentioned.
  • alkoxyaluminum raw material for the weather resistant protective film examples include aluminum (III) trimethoxide, aluminum (III) triethoxide, aluminum (III) tri-n-propoxide, aluminum tri-i-propoxide, aluminum (III) tri- -sec-butoxide, aluminum (III) di-i-propylate mono-sec-butyrate and the like.
  • the alkoxyaluminum derivative which is a raw material for the weather-resistant protective film, is a compound derived from an alkoxyaluminum into which a functional group other than an alkoxy group has been introduced as a part or all of the substituents, and which undergoes hydrolysis and dehydration-condensation reactions.
  • alkoxyaluminum derivatives include aluminum ethylacetoacetate diisopropylate, aluminum alkylacetoacetate diisopropylate, aluminum tris(acetylacetonate), aluminum tris(ethylacetoacetate), aluminum monoacetylacetonate bis(ethyl acetoacetate), cyclic aluminum oxide stearate, cyclic aluminum oxide octylate and the like.
  • the oligomer composed of one or more polymers selected from alkoxyaluminum and alkoxyaluminum derivatives, which is a raw material for the weather-resistant protective film includes an oligomer composed of a polymer of monomers composed of one or more of the above-mentioned alkoxyaluminums.
  • Oligomer consisting of a polymer of monomers consisting of any one or more alkoxyaluminum derivatives, and a polymer consisting of a monomer consisting of any one or more of the above-mentioned alkoxyaluminum derivatives and a monomer consisting of one or more of the above-mentioned alkoxyaluminum derivatives. can be mentioned.
  • the weather-resistant protective film contains 100.0 mol% of the total content of (I) the silicon compound and one or more polyvalent metal compounds selected from (IIa) to (IIc).
  • the (I) silicon compound is 25.0 mol% or more and less than 80.0 mol% and one or more metal alkoxides selected from the general formulas (IIa) to (IIc) are more than 20.0 mol%
  • the optical element according to the present invention has The following general formula (i) is applied to at least one main surface of a glass substrate made of phosphate-based glass or fluorophosphate-based glass.
  • Si( OR1 )( OR2 )( OR3 )( OR4 ) (i) (R 1 , R 2 , R 3 and R 4 are linear or branched hydrocarbon groups having 1 to 10 carbon atoms and may be the same or different.) and an alkoxysilane represented by the following general formula (iia) Ti (OR 5 ) (OR 6 ) (OR 7 ) (OR 8 ) (iia) (However, R 5 , R 6 , R 7 and R 8 are linear or branched hydrocarbon groups having 1 to 10 carbon atoms and may be the same or different.) , the following general formula (iib) Zr( OR9 )( OR10 )( OR11 )( OR12 ) (iib) (R 9 , R 10 , R 11 and R 12 are
  • R 1 , R 2 , R 3 and R 4 are a straight or branched hydrocarbon group having 1 to 10 carbon atoms, and a straight or branched chain having 1 to 4 carbon atoms.
  • a branched hydrocarbon group is preferable, and a straight or branched hydrocarbon group having 1 to 3 carbon atoms is more preferable.
  • R 1 , R 2 , R 3 and R 4 are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl groups. Examples include those selected from chain, branched, and cyclic hydrocarbon groups. R 1 , R 2 , R 3 and R 4 may be the same or different.
  • R 5 to R 15 R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 and R 15
  • R 5 to R 15 is a linear or branched hydrocarbon group having 1 to 10 carbon atoms, and A straight or branched hydrocarbon group having 2 to 9 carbon atoms is preferable, and a straight or branched hydrocarbon group having 3 to 8 carbon atoms is more preferable.
  • R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 or R 15 are specifically methyl group, ethyl group, propyl group, butyl group , a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group, which are linear, branched, or cyclic hydrocarbon groups.
  • R5 , R6 , R7 , R8 , R9 , R10 , R11 , R12 , R13 , R14 and R15 may be the same or different.
  • R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 and R 15 have 2 or more carbon atoms.
  • the reaction proceeds as follows to form silanol Si(OH) 4 .
  • the zirconium alkoxide represented by OR 12 ) and the aluminum alkoxide represented by the general formula (iic) Al(OR 13 )(OR 14 )(OR 15 ) are also hydrolyzed to form compounds having hydroxyl groups. is easily generated.
  • the hydrolyzate of the alkoxysilane represented by the general formula (i), the titanium alkoxide represented by the general formula (iia), the zirconium alkoxide represented by the general formula (iib), and the general formula ( iic) a dehydration condensation reaction with a hydrolyzate of one or more metal alkoxides selected from aluminum alkoxides, so that at least some of these components are bonded to each other, hydrolysates of alkoxysilanes, or metal alkoxides Together they form a weather resistant protective film.
  • the above dehydration condensation reaction is carried out on a glass substrate, at least part of the hydrolyzate of each of the above components reacts with the hydroxyl groups on the surface of the glass substrate and can be firmly bonded to the glass substrate.
  • the weather-resistant protective film comprises an alkoxysilane represented by the general formula (i) and one or more metal alkoxides selected from the general formulas (iia) to (iic).
  • the alkoxysilane (or partial hydrolyzate thereof) represented by the general formula (i) is 25.0 mol% or more and less than 80.0 mol% and the general formula (iia) to one or more metal alkoxides selected from general formula (iic) above 20.0 mol% and not more than 75.0 mol%.
  • the alkoxysilane represented by the general formula (i) (or a partial hydrolyzate thereof) and one or more metal alkoxides selected from the general formulas (iia) to (iic) is within the above range, a weather-resistant protective film exhibiting desired properties can be easily formed.
  • the weather-resistant protective film is (Si(OR 1 )(OR 2 )(OR 3 )OH obtained by partially hydrolyzing the alkoxysilane represented by the general formula (i) in advance). etc.) and one or more metal alkoxides selected from the general formulas (iia) to (iic) above.
  • the alkoxysilane represented by the general formula (i) and the metal alkoxide represented by the general formulas (iia) to (iic) are hydrolyzed in the presence of moisture to form silanol Si(OH). ) to give 4 and the corresponding metal hydroxides.
  • the metal alkoxides (Ti, Zr or Al alkoxides) represented by the general formulas (iia) to (iic) have a reaction to water as compared with the alkoxysilane represented by the general formula (i).
  • the metal alkoxide-derived metal hydroxide represented by the general formulas (iia) to (iic) is immediately produced, and the subsequent polycondensation reaction easily removes a precipitate. Homogeneous hydrolysis and polymerization reactions are less likely to occur.
  • a partial hydrolyzate represented by Si(OR 1 )(OR 2 )(OR 3 )OH etc.
  • a partial hydrolyzate represented by Si(OR 1 )(OR 2 )(OR 3 )OH etc.
  • Si(OR 1 )(OR 2 )(OR 3 )OH etc. obtained by partially hydrolyzing the alkoxysilane represented by the above general formula (i) and the above Mixing with one or more metal alkoxides selected from general formulas (iia) to general formula (iic) to form a homogeneous coating liquid, and subjecting this to hydrolysis and dehydration condensation to obtain homogeneous hydrolysis and dehydration condensation
  • the reaction can be easily carried out.
  • the hydrolyzates of the alkoxysilane represented by the above general formula (i) are bonded together by a dehydration condensation reaction, or the general formulas (iia) to (iic) Not only are the hydrolyzates of the metal alkoxide represented by the above bond by a dehydration condensation reaction, but the hydrolyzate of the alkoxysilane represented by the general formula (i) and the general formula (iia) to the general formula (iic ) and a hydrolyzate of one or more metal alkoxides selected from the compounds represented by the above are dehydrated and condensed, and at least some of these components are bonded to each other to form Si—O—Al bonds, Si—O— By forming bonds such as Ti bonds and Si--O--Zr bonds, the desired weather-resistant protective film can be easily formed.
  • the alkoxysilane represented by the general formula (i) (or a partial hydrolyzate thereof) and one or more metal alkoxides selected from the general formulas (iia) to (iic) is preferably stirred for a predetermined time in the presence of a catalyst and a suitable solvent to form a mixed solution (coating solution).
  • the catalyst may be one or more acids selected from hydrochloric acid, nitric acid, acetic acid, etc., ammonia, water, etc., in order to promote the sol-gel reaction (hydrolysis reaction, polycondensation reaction).
  • acids selected from hydrochloric acid, nitric acid, acetic acid, etc., ammonia, water, etc.
  • bases selected from sodium oxide and the like can be mentioned.
  • the solvent is not particularly limited as long as it can finally form a homogeneous coating liquid.
  • the solvent include one or more selected from alcohols such as methanol, ethanol, n-propanol, iso-propanol and n-butanol, alkoxy alcohols such as 2-methoxyethanol and 2-ethoxyethanol, and the like. can.
  • a solvent or a metal alkoxide stabilizer may be used during mixing.
  • the stabilizer one selected from ⁇ -diketones such as acetylacetone and ethyl acetoacetate, alkanolamines such as monoethanolamine, diethanolamine and triethanolamine, and glycols such as ethylene glycol, propylene glycol and diethylene glycol. The above can be mentioned.
  • the alkoxysilane represented by the general formula (i) (or a partial hydrolyzate thereof) and one or more metal alkoxides selected from the general formulas (iia) to (iic) are preferably mixed at a temperature of 0 to 200°C, more preferably at a temperature of 10 to 175°C, and even more preferably at a temperature of 15 to 150°C.
  • the alkoxysilane represented by the general formula (i) (or a partial hydrolyzate thereof) and one or more metal alkoxides selected from the general formulas (iia) to (iic) is preferably stirred and mixed for 1 minute to 24 hours to form a mixed solution, more preferably stirred and mixed for 1 minute to 12 hours to form a mixed solution, and stirred and mixed for 1 minute to 6 minutes to form a mixed solution. It is further preferred to form
  • the alkoxysilane represented by the general formula (i) (or a partial hydrolyzate thereof) and one or more metal alkoxides selected from the general formulas (iia) to (iic) are usually mixed together. It is subjected to hydrolysis and dehydration condensation reactions in the presence of the above catalyst and solvent.
  • the hydrolysis and dehydration condensation reactions are carried out by combining the alkoxysilane represented by the general formula (i) (or a partial hydrolyzate thereof) with one or more metal alkoxides selected from the general formulas (iia) to (iic). It is preferable to use the mixed solution in which the catalyst and the solvent used at the time of mixing with is used as it is as the coating solution (weather-resistant protective film-forming solution).
  • a coating liquid weather-resistant protective film-forming liquid
  • a coating liquid weather-resistant protective film-forming liquid
  • constituent elements M′ Si Metalloxane bonds MOM and/or M It is preferred to form a -OM' bond.
  • the method of applying the coating liquid is not particularly limited, but can be appropriately selected from spin coating method (spin method), nozzle flow method, spray method, dip method, roll method, brush coating, and the like.
  • the heating temperature when heating is particularly limited as long as it is above the temperature at which the solvent constituting the coating liquid volatilizes and below the glass transition point of the glass substrate.
  • a suitable temperature is, for example, 100 to 500°C.
  • the heating time for heating after applying a desired amount of the coating liquid to at least one main surface of the glass substrate is preferably 1 minute to 24 hours, more preferably 3 minutes to 12 hours, and 5 minutes to 6 hours. Time is more preferred.
  • the glass tends to soften.
  • the longer the heating time during the hydrolysis and dehydration condensation reaction the easier it is to form a weather-resistant protective film with excellent weather resistance improving effect, but if the heating time is too long, it becomes difficult to perform efficient heat treatment.
  • the hydrolysis and dehydration condensate obtained by the above reaction is an alkoxysilane represented by the above general formula (i) and one or more metal alkoxides selected from the above general formulas (iia) to general formulas (iic) are bonded to each other.
  • a coating film firmly bonded to the glass substrate and such a coating film is a protective film (weather resistant protection) that can highly suppress burning of the glass substrate even under high temperature and high humidity membrane).
  • the alkoxysilane represented by the above general formula (i) (or its partial hydrolyzate) on a glass substrate made of phosphate-based glass or fluorophosphate-based glass and subjecting it to hydrolysis and dehydration condensation polymerization
  • SiO.sub.2 film Si--O--P bonds are formed between the SiO.sub.2 film and the glass substrate.
  • the SiO 2 film is originally a film with high weather resistance, the Si—O—P bond formed between the glass substrate and the glass substrate has poor water resistance, and is hydrolyzed in the presence of water to transform into Si—OH. and tends to lose its bonding strength with the glass substrate.
  • a metal alkoxide represented by the general formulas (iia) to (iic) is hydrolyzed, dehydrated and condensation-polymerized on a glass substrate made of phosphate glass or fluorophosphate glass to form a metal oxide film.
  • a Ti--O--P bond, a Zr--O--P bond or an Al--O--P bond is formed between the metal oxide film and the glass substrate, and these bonds are water resistant. Since it is high and hardly causes a hydrolysis reaction, it is possible to easily maintain the bondability with the glass substrate.
  • the alkoxysilane represented by the general formula (i) (or a partial hydrolyzate thereof) is combined with one or more metal alkoxides selected from the general formulas (iia) to (iic), and It is believed that the hydrolysis and dehydration-condensation reaction can easily form a weather-resistant protective film with excellent weather resistance.
  • the alkoxyaluminum represented by the general formula (iic) is preferable.
  • Al has a tetra-coordinated structure or a 6-coordinated structure. (--O--), and all the oxygen atoms bound to P become bridging oxygen (--O--) to form a dense glass network structure and strengthen the glass structure. It is thought that the water resistance is improved.
  • the weather-resistant protective film preferably has a thickness of 1 nm to 5 ⁇ m, more preferably 10 nm to 2 ⁇ m, even more preferably 20 nm to 1 ⁇ m.
  • the thickness of the weather resistant protective film is measured with a spectroscopic ellipsometer (JA Woollam M-20000V-Te) for thicknesses of 1 ⁇ m or less, and with a stylus for thicknesses exceeding 1 ⁇ m. It means a value measured by a formula ultra-precision roughness/film thickness measuring machine (Dektak 6M manufactured by Veeco).
  • An optical element according to the present invention comprises a weather-resistant protective film having a single-layer structure provided on at least one main surface of a glass substrate made of phosphate-based glass or fluorophosphate-based glass. That is, as a form example of the optical element according to the present invention, (1) As illustrated in FIG. 2(a), an optical element 1 having a weather resistant protective film P provided on one main surface of a glass substrate G made of phosphate glass or fluorophosphate glass; , (2) As illustrated in FIG. 2(b), an optical element in which weather resistant protective films P, P are provided on both main surfaces of a glass substrate G made of phosphate glass or fluorophosphate glass. 1 can be mentioned.
  • optical element As a form example of the optical element according to the present invention, there can be mentioned one in which a resin film or an antireflection film is further provided on the weather resistant protective film.
  • a weather-resistant protective film P is provided on one main surface of a glass substrate G made of phosphate glass or fluorophosphate glass.
  • An optical element 1 further provided with an antireflection film AR on P;
  • a weather-resistant protective film P is provided on one main surface of a glass substrate G made of phosphate-based glass or fluorophosphate-based glass.
  • An optical element 1 in which a resin film R is further provided on P can be mentioned.
  • a resin film and an antireflection film are further provided in this order on the weather resistant protective film, or an antireflection film and a resin film are further provided in this order. What is provided can be mentioned.
  • a weather-resistant protective film P is provided on one main surface of a glass substrate G made of phosphate-based glass or fluorophosphate-based glass. an optical element 1 in which a resin film R and an antireflection film AR are further provided in this order on P; (6) As illustrated in FIG. 3(d), a weather-resistant protective film P is provided on one main surface of a glass substrate G made of phosphate-based glass or fluorophosphate-based glass. An optical element 1 in which an antireflection film AR and a resin film R are further provided in this order on P can be mentioned.
  • the upper main surface of the glass substrate P shown in each figure is the light entrance surface when arranged, and the lower main surface of the glass substrate P is the light exit surface when arranged.
  • the lower main surface of the glass substrate P is the light exit surface when arranged.
  • the upper main surface of the glass substrate G (the main surface opposite to the side on which the weather-resistant protective film P is provided) has: (7) No film may be formed (as illustrated in FIGS. 3(a) to 3(d)), (8) A weather-resistant protective film P may be further provided, (9) A resin film R or a weather-resistant protective film AR may be further provided with or without the weather-resistant protective film P, (10) The resin film R and the antireflection film AR may be further provided in this order with or without the weather-resistant protective film P interposed therebetween, (11) An antireflection film AR and a resin film R may be further provided in this order with or without the weather resistant protective film P interposed therebetween.
  • the resin film includes, for example, an absorption resin film that absorbs ultraviolet light or near-infrared light, a reflection amplification film, a protective film for preventing the glass from burning, and a reinforcing film for improving the strength of the glass.
  • a film, a water-repellent film, and the like can be mentioned.
  • the absorbing resin film that absorbs ultraviolet light or near-infrared light include those containing a near-infrared absorbing dye and a transparent resin, and the near-infrared absorbing dye is uniformly dissolved or dispersed in the transparent resin. Anything is preferred.
  • the near-infrared absorbing dye constituting the absorbing resin film conventionally known dyes can be employed, and cyanine dyes, polymethine dyes, squarylium dyes, porphyrin dyes, metal dithiol complex dyes, phthalocyanine dyes, At least one selected from diimmonium dyes and inorganic oxide particles is preferable, and at least one selected from squarylium dyes, cyanine dyes, and phthalocyanine dyes is more preferable.
  • conventionally known transparent resins can be employed, including acrylic resins, epoxy resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, and polyethersulfones.
  • the transparent resin preferably has a high glass transition point (Tg) from the viewpoint of transparency, solubility of the near-infrared absorbing dye in the transparent resin, and heat resistance.
  • Tg glass transition point
  • polyester resins, polycarbonate resins, and polyethers are preferred.
  • At least one selected from sulfone resins, polyarylate resins, polyimide resins, and epoxy resins is preferable, and at least one selected from polyester resins and polyimide resins is more preferable.
  • the polyester resin is preferably one or more selected from polyethylene terephthalate resin and polyethylene naphthalate resin.
  • the resin film further contains a color tone correcting dye, a leveling agent, an antistatic agent, a heat stabilizer, a light stabilizer, an antioxidant, and a Optional components such as dispersants, flame retardants, lubricants and plasticizers may be contained.
  • the resin film is formed by, for example, dissolving or dispersing a pigment, a transparent resin, and optional ingredients in a solvent to prepare a resin film-forming liquid, applying the liquid, drying it, and curing it as necessary.
  • a pigment for example, dissolving or dispersing a pigment, a transparent resin, and optional ingredients in a solvent to prepare a resin film-forming liquid, applying the liquid, drying it, and curing it as necessary.
  • the resin film-forming liquid may contain known surfactants such as cationic, anionic, and nonionic surfactants.
  • one or more coating methods selected from dip coating, cast coating, spray coating, spin coating, nozzle flow coating, roll coating, etc. can be employed.
  • a resin film can be formed by applying the resin film-forming liquid onto a substrate and then drying the substrate.
  • the antireflection film includes a single layer film using a low refractive index substance such as MgF2 , a multilayer film using SiO2 etc. as a low refractive index substance and TiO2 etc. as a high refractive index substance, One or more selected from a porous film or the like composed of SiO2 fine particles and a binder can be used.
  • a low refractive index substance such as MgF2
  • a multilayer film using SiO2 etc. as a low refractive index substance and TiO2 etc. as a high refractive index substance
  • the antireflection film can be formed by, for example, vapor phase methods such as vapor deposition, sputtering, and CVD, and liquid phase methods such as dip coating, cast coating, spray coating, spin coating, nozzle flow coating, and roll coating. It can be formed by any method selected from methods.
  • vapor phase methods such as vapor deposition, sputtering, and CVD
  • liquid phase methods such as dip coating, cast coating, spray coating, spin coating, nozzle flow coating, and roll coating. It can be formed by any method selected from methods.
  • optical elements examples include optical filters such as infrared cut filters (IRCF), as well as lenses, prisms, diffraction gratings, substrates, and the like that constitute various optical devices.
  • IRCF infrared cut filters
  • an optical element capable of exhibiting excellent weather resistance in spite of having a glass substrate made of phosphate glass or fluorophosphate glass.
  • An imaging apparatus is characterized by having the optical element according to the present invention as an optical filter together with a solid-state imaging device and an imaging lens.
  • solid-state imaging devices include image sensors such as CCD (Charge-Coupled Device) sensors and CMOS (Complementary Metal Oxide Semiconductor) sensors.
  • FIG. 1(a) is a schematic explanatory diagram of a camera module related to a compact digital camera mounted on a smartphone or the like.
  • the camera module shown in FIG. L (or lenses L1 . . . Ln), an optical filter 1 comprising optical elements according to the present invention, and an image sensor IC.
  • FIG. 1(b) is a schematic illustration of a camera module for a digital single-lens reflex camera.
  • the camera module shown in FIG. It has a cover glass CG and an image sensor IC.
  • an imaging device having an optical element as an optical filter that can exhibit excellent weather resistance in spite of having a glass substrate made of phosphate-based glass or fluorophosphate-based glass. .
  • Example 1 Preparation of coating liquid (1) 4.2 g of a 2.0 N (mol/L) HCl aqueous solution, 10.4 g of 2-propanol, and 17.8 g of 2-methoxyethanol were weighed into a container and mixed under a closed condition. (2) 24.4 g of tetraethyl orthosilicate (Si(OC 2 H 5 ) 4 ) was added to the above container and mixed at room temperature for 30 minutes under a closed condition. (3) 38.5 g of aluminum (III) tri-sec-butoxide (Al(OC 4 H 9 ) 3 ) was further added to the vessel and heated under reflux for 1.5 hours. Cooled to room temperature.
  • the solid content concentration of the obtained coating liquid that is, when tetraethyl orthosilicate and aluminum (III) tri-sec-butoxide in the coating liquid are converted to SiO 2 and Al 2 O 3 respectively.
  • the total content of tetraethyl orthosilicate and aluminum (III) tri-sec-butoxide was 5% by weight.
  • the coating liquid obtained in step 1 was applied to one main surface of an absorption glass substrate (CM500 manufactured by HOYA Corporation, thickness 0.59 mm) made of phosphate glass using a spin coater so that the concentration was 10 ⁇ L/cm 2 . It was applied by dropping into Then, the glass substrate coated with the coating liquid was placed on a hot plate heated to 135° C., heated for 3 minutes, and then cooled naturally. (2) After that, the coating liquid was applied by dripping it onto the main surface opposite to the main surface on which the coating liquid was applied so as to be 10 ⁇ L/cm 2 . Then, the glass substrate coated with the coating liquid was placed on a hot plate heated to 200° C. and heated for 10 minutes.
  • CM500 absorption glass substrate manufactured by HOYA Corporation, thickness 0.59 mm
  • the coating liquid was applied to both main surfaces, and the heat-treated absorption glass substrate was heat-treated in a muffle furnace at 280° C. for 10 minutes.
  • the heat treatment of (1) to (3) above the hydroxyl groups on the surface of the glass substrate and the hydroxyl groups of the components constituting the coating liquid, or the hydroxyl groups of the components constituting the coating liquid, are dehydrated and condensed, resulting in single crystals on both main surfaces.
  • a glass substrate (optical filter 1) having a protective film having a layered structure was produced.
  • the ratio of Al atoms to the total number of Al atoms and Si atoms is 57.1 atomic %, and the ratio of Si atoms to the total number of Al atoms and Si atoms is 42.9 atomic %.
  • the ratio of Al 2 O 3 to the total amount of Al 2 O 3 and SiO 2 is 40.0 mol%.
  • the ratio of SiO 2 to the total amount of Al 2 O 3 and SiO 2 is 60.0 mol %.
  • Example 2 Preparation of Coating Liquid (1) 3.1 g of 0.5 N (mol/L) HCl aqueous solution, 10.4 g of 2-propanol, and 13.2 g of 2-methoxyethanol were weighed in a container and mixed under a closed condition. (2) 36.0 g of tetraethyl orthosilicate (Si(OC 2 H 5 ) 4 ) was added to the container and mixed for 30 minutes at room temperature under a closed condition. (3) Further, 19.6 g of titanium (IV) tetra-n-butoxide (Ti(OC 4 H 9 ) 4 ) was added to the container and mixed for 30 minutes at room temperature under a closed condition.
  • Ti(OC 4 H 9 ) 4 titanium
  • the solid content concentration of the obtained coating liquid that is, the orthosilicic acid in the coating liquid when tetraethyl orthosilicate and titanium (IV) tetra-n-butoxide in the coating liquid are converted to SiO 2 and TiO 2 respectively
  • the total content of tetraethyl and titanium (IV) tetra-n-butoxide was 5% by weight.
  • the ratio of TiO2 to the total amount of TiO2 and SiO2 is 25.0 mol% when Ti atoms and Si atoms are converted to TiO2 and SiO2 , respectively.
  • the ratio of SiO2 to the total amount of SiO2 was 75.0 mol%.
  • Example 3 Preparation of coating liquid (1) 4.8 g of 1.0 N (mol/L) HCl aqueous solution and 20.2 g of 2-methoxyethanol were weighed into a container and mixed under a closed condition. (2) 27.7 g of tetraethyl orthosilicate (Si(OC 2 H 5 ) 4 ) was added to the above container and mixed at room temperature for 30 minutes under a closed condition. (3) 25.7 g of an 85% n-butanol solution of zirconium (IV) tetra-n-butoxide (Zr(OC 4 H 9 ) 4 ) was further added to the vessel and mixed for 30 minutes at room temperature under a closed condition. .
  • a mixed solution of 22.6 g of a 1.0N HCl aqueous solution and 199.0 g of 2-methoxyethanol was added to the above container with stirring, and mixed at room temperature for 30 minutes under a closed condition to obtain a transparent and homogeneous mixture.
  • a coating liquid (coating liquid composition) was obtained.
  • the resulting coating solution contained 70.0 mol % of tetraethyl orthosilicate and zirconium (IV) tetra-n-butoxide, when the total amount of tetraethyl orthosilicate and zirconium (IV) tetra-n-butoxide added was 100 mol %. - equivalent to a mixture with 30.0 mol % of butoxide.
  • the solid content concentration of the coating liquid obtained that is, the orthosilicic acid
  • the total content of tetraethyl and zirconium (IV) tetra-n-butoxide was 5% by weight.
  • the ratio of ZrO2 to the total amount of ZrO2 and SiO2 is 30.0 mol% when zirconium atoms and Si atoms are converted to ZrO2 and SiO2 , respectively.
  • the proportion of SiO2 in the total amount of SiO2 is 70.0 mol%.
  • Example 4 Preparation of Coating Liquid
  • coating liquid (2) of Example 1, 36.0 g of tetraethyl orthosilicate (Si(OC 2 H 5 ) 4 ) was replaced with tetraethyl orthosilicate (Si(OC 2 H 5 ) 4 ) 21.6 g and methyltriethoxysilane (CH 3 Si(OC 2 H 5 ) 3 ) 12.3 g were used in the same manner as in Example 1 to obtain a transparent homogeneous coating liquid (coating liquid composition) was obtained.
  • the resulting coating liquid contained tetraethyl orthosilicate and methyltriethoxysilane in total when the total amount of tetraethyl orthosilicate, methyltriethoxysilane and titanium (IV) tetra-n-butoxide added was 100 mol %. This corresponds to a mixture of 75.0 mol % and 25.0 mol % of titanium (IV) tetra-n-butoxide.
  • the solid content concentration of the obtained coating liquid that is, when tetraethyl orthosilicate and methyltriethoxysilane in the coating liquid are converted to SiO 2 and titanium (IV) tetra-n-butoxide is converted to TiO 2
  • the total content of tetraethyl orthosilicate, methyltriethoxysilane and titanium (IV) tetra-n-butoxide in the coating solution was 5% by weight.
  • the ratio of TiO2 to the total amount of TiO2 and SiO2 is 25.0 mol% when Ti atoms and Si atoms are converted to TiO2 and SiO2 , respectively.
  • the proportion of SiO2 in the total amount of SiO2 is 75.0 mol%.
  • Example 5 Preparation of Coating Liquid In "1. Preparation of coating liquid" (3) of Example 1, instead of 19.6 g of titanium (IV) tetra-n-butoxide (Ti(OC 4 H 9 ) 4 ), titanium (IV ) A transparent homogeneous coating liquid (coating liquid composition) was obtained in the same manner as in Example 1 except that 14.0 g of a tetramer of tetra-n-butoxide (Ti(OC 4 H 9 ) 4 ) was used. rice field.
  • the obtained coating liquid contained 75.0 mol % of tetraethyl orthosilicate and titanium ( IV) Corresponds to a mixture with 25.0 mol % of tetra-n-butoxide tetramer.
  • the solid content concentration of the coating liquid obtained that is, the coating liquid when the tetramers of tetraethyl orthosilicate and titanium (IV) tetra-n-butoxide in the coating liquid are converted to SiO 2 and TiO 2 respectively
  • the total content of tetraethyl orthosilicate and titanium (IV) tetra-n-butoxide tetramer in the powder was 5% by weight.
  • the ratio of TiO2 to the total amount of TiO2 and SiO2 is 25.0 mol% when Ti atoms and Si atoms are converted to TiO2 and SiO2 , respectively.
  • the proportion of SiO2 in the total amount of SiO2 is 75.0 mol%.
  • Example 6 Preparation of Coating Liquid In "1. Preparation of coating liquid” (2) of Example 1, 30.2 g of tetraethyl orthosilicate was used in place of 36.0 g of tetraethyl orthosilicate. (3) , titanium ( IV) tetra-n-butoxide (Ti(OC 4 H 9 ) 4 ) A transparent homogeneous coating liquid (coating liquid composition ).
  • the resulting coating solution had a tetraethyl orthosilicate content of 70.0% when the total amount of tetraethyl orthosilicate, titanium (IV) tetra-n-butoxide and zirconium (IV) tetra-n-butoxide added was 100 mol %. 15.0 mol % of titanium (IV) tetra-n-butoxide and 15.0 mol % of zirconium (IV) tetra-n-butoxide.
  • the solid content concentration of the obtained coating liquid that is, tetraethyl orthosilicate in the coating liquid was converted to SiO 2
  • titanium (IV) tetra-n-butoxide was converted to TiO 2
  • the total content of tetraethyl orthosilicate, titanium (IV) tetra-n-butoxide and zirconium (IV) tetra-n-butoxide in the coating solution was 5% by weight when n-butoxide was converted to ZrO2 . rice field.
  • the ratio of TiO 2 to the total amount of TiO 2 , ZrO 2 and SiO 2 is 15. .0 mol%
  • the proportion of ZrO2 in the total amount of TiO2 , ZrO2 and SiO2 is 15.0 mol%
  • the proportion of SiO2 in the total amount of TiO2 , ZrO2 and SiO2 is 70 .0 mol %.
  • Example 7 Preparation of Coating Liquid In "1. Preparation of coating liquid" (2) of Example 1, 27.6 g of tetraethyl orthosilicate was used in place of 36.0 g of tetraethyl orthosilicate. (3) , titanium ( IV) tetra-n-butoxide (Ti(OC 4 H 9 ) 4 ) A transparent homogeneous coating liquid (coating liquid composition) was obtained in the same manner as in Example 1, except that 30.0 g was used.
  • the resulting coating solution contained 60.0 mol % of tetraethyl orthosilicate and titanium (IV) tetra-n, when the total amount of tetraethyl orthosilicate and titanium (IV) tetra-n-butoxide added was 100 mol %. -corresponds to a mixture with 40.0 mol % of butoxide.
  • the solid content concentration of the coating liquid obtained that is, the orthosilicic acid
  • the total content of tetraethyl and titanium (IV) tetra-n-butoxide was 5% by weight.
  • the ratio of TiO2 to the total amount of TiO2 and SiO2 is 40.0 mol% when Ti atoms and Si atoms are converted to TiO2 and SiO2 , respectively.
  • the proportion of SiO2 in the total amount of SiO2 is 60.0 mol%.
  • Example 8 Preparation of Coating Liquid In "1. Preparation of coating liquid" (2) of Example 1, 22.3 g of tetraethyl orthosilicate was used in place of 36.0 g of tetraethyl orthosilicate. (3) , titanium ( IV) tetra-n-butoxide (Ti(OC 4 H 9 ) 4 ) A transparent homogeneous coating liquid (coating liquid composition) was obtained in the same manner as in Example 1, except that 36.5 g was used.
  • the obtained coating liquid contained 50.0 mol % of tetraethyl orthosilicate and titanium (IV) tetra-n-butoxide, when the total amount of tetraethyl orthosilicate and titanium (IV) tetra-n-butoxide added was 100 mol %. -corresponds to a mixture with 50.0 mol % of butoxide.
  • the solid content concentration of the obtained coating liquid that is, the orthosilicic acid
  • the total content of tetraethyl and titanium (IV) tetra-n-butoxide was 5% by weight.
  • the ratio of TiO2 to the total amount of TiO2 and SiO2 is 50.0 mol% when Ti atoms and Si atoms are converted to TiO2 and SiO2 , respectively.
  • the proportion of SiO2 in the total amount of SiO2 is 50.0 mol%.
  • Example 9 Preparation of Coating Liquid In "1. Preparation of coating liquid" (2) of Example 2, 17.0 g of tetraethyl orthosilicate was used in place of 27.7 g of tetraethyl orthosilicate. Preparation of (3), except that 36.9 g of an 85% butanol solution of zirconium (IV) tetra-n-butoxide was used instead of 25.7 g of an 85% butanol solution of zirconium (IV) tetra-n-butoxide. A transparent homogeneous coating liquid (coating liquid composition) was obtained in the same manner as in Example 2.
  • the resulting coating solution contained 50.0 mol % of tetraethyl orthosilicate and zirconium (IV) tetra-n, when the total amount of tetraethyl orthosilicate and zirconium (IV) tetra-n-butoxide added was 100 mol %. - equivalent to a mixture with 50.0 mol % of butoxide.
  • the solid content concentration of the coating liquid obtained that is, the orthosilicic acid
  • the total content of tetraethyl and zirconium (IV) tetra-n-butoxide was 5% by weight.
  • the ratio of ZrO2 to the total amount of ZrO2 and SiO2 is 50.0 mol% when Zr atoms and Si atoms are converted to ZrO2 and SiO2 , respectively .
  • the proportion of SiO2 in the total amount of SiO2 is 50.0 mol%.
  • Example 10 Preparation of Coating Liquid In "1. Preparation of coating liquid" (2) of Example 3, 36.0 g of tetraethyl orthosilicate was replaced with 36.5 g of tetraethyl orthosilicate, and 36.5 g of tetraethyl orthosilicate was used. in the same manner as in Example 3, except that 21.6 g of aluminum (III) tri-sec-butoxide was used instead of 38.5 g of aluminum (III) tri-sec-butoxide in (3). A transparent and uniform coating liquid (coating liquid composition) was obtained.
  • the resulting coating solution contained 66.7 mol % of tetraethyl orthosilicate and aluminum (III) tri-sec, when the total amount of tetraethyl orthosilicate and aluminum (III) tri-sec-butoxide added was 100 mol %. -butoxide with 33.3 mol %.
  • the solid content concentration of the obtained coating liquid that is, when tetraethyl orthosilicate and aluminum (III) tri-sec-butoxide in the coating liquid are converted to SiO 2 and Al 2 O 3 respectively,
  • the total content of tetraethyl orthosilicate and aluminum (III) tri-sec-butoxide was 5% by weight.
  • the ratio of Al 2 O 3 to the total amount of Al 2 O 3 and SiO 2 is 20.0 mol%. and the ratio of SiO 2 to the total amount of Al 2 O 3 and SiO 2 is 80.0 mol %.
  • Example 1 the glass substrate (CM500 manufactured by HOYA Corporation, thickness 0.59 mm) made of phosphate glass used in Example 1 was used as it was without forming a coating film. and
  • the resulting coating solution contained 90.0 mol % of tetraethyl orthosilicate and titanium (IV) tetra-n, when the total amount of tetraethyl orthosilicate and titanium (IV) tetra-n-butoxide added was 100 mol %. -corresponds to a mixture with 10.0 mol % of butoxide.
  • the solid content concentration of the coating liquid obtained that is, the orthosilicic acid
  • the total content of tetraethyl and titanium (IV) tetra-n-butoxide was 5% by weight.
  • the ratio of TiO2 to the total amount of TiO2 and SiO2 is 10.0 mol% when Ti atoms and Si atoms are converted to TiO2 and SiO2 , respectively.
  • the proportion of SiO2 in the total amount of 2 is 90.0 mol%.
  • the resulting coating solution contained 82.0 mol % of tetraethyl orthosilicate and titanium (IV) tetra-n, when the total amount of tetraethyl orthosilicate and titanium (IV) tetra-n-butoxide added was 100 mol %. -butoxide 18.0 mol %.
  • the solid content concentration of the obtained coating liquid that is, the orthosilicic acid
  • the total content of tetraethyl and titanium (IV) tetra-n-butoxide was 5% by weight.
  • the ratio of TiO2 to the total amount of TiO2 and SiO2 is 18.0 mol% when Ti atoms and Si atoms are converted to TiO2 and SiO2 , respectively.
  • the proportion of SiO2 in the total amount of SiO2 is 82.0 mol%.
  • ⁇ Weather resistance evaluation> The weather resistance of the optical filters obtained in the above Examples and Comparative Examples was evaluated based on the haze values shown below.
  • (Evaluation method) (1) Weather resistance life 1 A test piece cut out from each optical filter was exposed to an environment with a temperature of 65°C and a relative humidity of 90% in a constant temperature and humidity chamber. hours, 50 hours, 75 hours, 100 hours, 150 hours, 200 hours, 250 hours, 300 hours, 350 hours, 400 hours, 500 hours, 750 hours and 1000 hours The appearance of the surface on which the weather-resistant protective film was installed was visually observed and the cloudiness (haze value) was measured with a haze meter.
  • the haze value at which the optical filter becomes cloudy and begins to interfere with use is determined to be a haze value of 0.2.
  • (2) Weather resistance life 2 A test piece cut from each optical filter was evaluated in the same manner as in (1) Weather resistance life 1, except that it was exposed to an environment of 85° C. and 85% relative humidity in a constant temperature and humidity chamber. asked. Table 1 shows the results of each example and comparative example.
  • Example 11 Preparation of Coating Liquid
  • coating liquid (2) of Example 1, 30.1 g of tetraethyl orthosilicate was used in place of 24.4 g of tetraethyl orthosilicate.
  • (3) in the same manner as in Example 1, except that 30.5 g of aluminum (III) tri-sec-butoxide was used instead of 38.5 g of aluminum (III) tri-sec-butoxide.
  • a transparent and uniform coating liquid (coating liquid composition) was obtained.
  • the resulting coating liquid contained 53.8 mol % of tetraethyl orthosilicate and aluminum (III) tri-sec, when the total amount of tetraethyl orthosilicate and aluminum (III) tri-sec-butoxide added was 100 mol %. -butoxide with 46.2 mol %.
  • the solid content concentration of the obtained coating liquid that is, when tetraethyl orthosilicate and aluminum (III) tri-sec-butoxide in the coating liquid are converted to SiO 2 and Al 2 O 3 respectively,
  • the total content of tetraethyl orthosilicate and aluminum (III) tri-sec-butoxide was 5% by weight.
  • the ratio of Al 2 O 3 to the total amount of Al 2 O 3 and SiO 2 is 30.0 mol%. and the ratio of SiO 2 to the total amount of Al 2 O 3 and SiO 2 is 70.0 mol %.
  • Measurement mode Transmission mode Measurement area: 500 to 1000 cm -1 Accumulated times: 128 times Resolution: 4 cm -1 Scan speed: 5kHz (4) As a result of the FT-IR measurement according to (3) above, absorption peaks were observed at 555 cm ⁇ 1 , 852 cm ⁇ 1 and 911 cm ⁇ 1 . J Sol-Gel Sci Technol (2010) 56:47-52, by N. P.
  • Example 12 Preparation of Coating Liquid In "1. Preparation of coating liquid" (2) of Example 1, 33.2 g of tetraethyl orthosilicate was used in place of 24.4 g of tetraethyl orthosilicate. in the same manner as in Example 1, except that 26.2 g of aluminum (III) tri-sec-butoxide was used instead of 38.5 g of aluminum (III) tri-sec-butoxide in (3). A transparent and uniform coating liquid (coating liquid composition) was obtained.
  • the resulting coating solution contained 60.0 mol % of tetraethyl orthosilicate and aluminum (III) tri-sec, when the total amount of tetraethyl orthosilicate and aluminum (III) tri-sec-butoxide added was 100 mol %. -corresponds to a mixture with 40.0 mol % of butoxide.
  • the solid content concentration of the obtained coating liquid that is, when tetraethyl orthosilicate and aluminum (III) tri-sec-butoxide in the coating liquid are converted to SiO 2 and Al 2 O 3 respectively,
  • the total content of tetraethyl orthosilicate and aluminum (III) tri-sec-butoxide was 5% by weight. 2.
  • the ratio of Al 2 O 3 to the total amount of Al 2 O 3 and SiO 2 is 25.0 mol%. and the ratio of SiO 2 to the total amount of Al 2 O 3 and SiO 2 is 75.0 mol %.
  • Example 13 Preparation of Coating Liquid In "1. Preparation of coating liquid" (2) of Example 1, 19.3 g of tetraethyl orthosilicate was used in place of 24.4 g of tetraethyl orthosilicate. Preparation of Example 1, except that 45.6 g of aluminum (III) tri-sec-butoxide was used instead of 38.5 g of aluminum (III) tri-sec-butoxide in (3). A transparent and uniform coating liquid (coating liquid composition) was obtained.
  • the resulting coating liquid contained 33.3 mol % of tetraethyl orthosilicate and aluminum (III) tri-sec, when the total amount of tetraethyl orthosilicate and aluminum (III) tri-sec-butoxide added was 100 mol %. -butoxide 66.7 mol %.
  • the solid content concentration of the obtained coating liquid that is, when tetraethyl orthosilicate and aluminum (III) tri-sec-butoxide in the coating liquid are converted to SiO 2 and Al 2 O 3 respectively,
  • the total content of tetraethyl orthosilicate and aluminum (III) tri-sec-butoxide was 5% by weight. 2.
  • the ratio of Al 2 O 3 to the total amount of Al 2 O 3 and SiO 2 is 50.0 mol% when Al atoms and Si atoms are converted to Al 2 O 3 and SiO 2 respectively. and the ratio of SiO 2 to the total amount of Al 2 O 3 and SiO 2 is 50.0 mol %.
  • the solid concentration of the obtained coating liquid that is, the content of tetraethyl orthosilicate in the coating liquid when each tetraethyl orthosilicate in the coating liquid was converted to SiO 2 was 5% by weight.
  • a glass substrate CM500 manufactured by HOYA CORPORATION, thickness 0.59 mm
  • a glass substrate having a protective film having a single-layer structure was produced.
  • the ratio of Si atoms to the total number of Si atoms is 100.0 atomic %.
  • the ratio of SiO 2 is 100.0 mol % when Si atoms are converted to SiO 2 .
  • the optical filters obtained in Examples 1 to 13 had Si atoms and Ti atoms, Zr atoms, and Al atoms selected from Si atoms on the surface of the absorbing glass substrate made of phosphate glass.
  • the ratio of the total number of Ti atoms, Zr atoms and Al atoms to the total number of Si atoms, Ti atoms, Zr atoms and Al atoms is more than 20.0 atomic% and 75.0 atomic% or less
  • a weather resistant protective film having a single layer structure is provided, and the weather resistant life defined by the limit time showing a haze value of 0.2 or less (weather resistant life 1 and weather resistant life 2 ) is long enough from 200 hrs (200 hours) to 1000 hrs (1000 hours), and a homogeneous and transparent surface condition was maintained until the weather resistance life by visual observation, indicating excellent weather resistance.
  • Example 11 it was found that in the optical filters obtained in each of the above Examples, Si atoms and one or more selected from Ti atoms, Zr atoms and Al atoms, which constitute the weather-resistant protective film, It was thought that, because it has a specific structure in which atoms of the same kind or atoms of different kinds are bonded in a three-dimensional network by chemical bonds via oxygen atoms, it can exhibit excellent weather resistance.
  • the optical filter obtained in Comparative Example 1 had no protective film on the surface of the absorbing glass substrate made of phosphate-based glass. After 5 hours of exposure, the haze value exceeded 0.2, and visual observation revealed that the surface had deliquesced, became sticky, and deteriorated, indicating poor weather resistance.
  • the optical filter obtained in Comparative Example 2 shows that in the weather-resistant protective film provided on the surface of the absorbing glass substrate made of phosphate-based glass, the proportion of Ti atoms in the total number of Si atoms and Ti atoms is Since the ratio of the number of atoms is outside the predetermined range, the weather resistance life defined by the limit time for maintaining the haze value of 0.2 or less is as short as 50 hours (50 hours) or 10 hours (10 hours), and the weather resistance is poor. It turns out to be inferior.
  • the optical filter obtained in Comparative Example 3 has Ti atoms occupying the total number of Si atoms and Ti atoms in the weather-resistant protective film provided on the surface of the absorbing glass substrate made of phosphate glass. is outside the predetermined range, the weather resistance life defined by the limit time for maintaining a haze value of 0.2 or less is as short as 150 hr (150 hours) or 40 hr (40 hours).
  • Optical element, optical filter or infrared cut filter (IRCF) L Lens CG Cover glass IC Image sensor G Glass substrate P Weather resistant protective film AR Antireflection film R Resin film

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WO2025159034A1 (ja) * 2024-01-25 2025-07-31 ソニーグループ株式会社 親水性膜、反射防止膜、カメラ及び成膜方法

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JP2021089357A (ja) * 2019-12-03 2021-06-10 Hoya株式会社 近赤外線カットフィルタ及びそれを備える撮像装置

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WO2025159034A1 (ja) * 2024-01-25 2025-07-31 ソニーグループ株式会社 親水性膜、反射防止膜、カメラ及び成膜方法

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