WO2025009509A1 - フツリン酸ガラス、近赤外線カットフィルタ、光学デバイス - Google Patents

フツリン酸ガラス、近赤外線カットフィルタ、光学デバイス Download PDF

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WO2025009509A1
WO2025009509A1 PCT/JP2024/023839 JP2024023839W WO2025009509A1 WO 2025009509 A1 WO2025009509 A1 WO 2025009509A1 JP 2024023839 W JP2024023839 W JP 2024023839W WO 2025009509 A1 WO2025009509 A1 WO 2025009509A1
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Prior art keywords
glass
less
content
transmittance
wavelength
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English (en)
French (fr)
Japanese (ja)
Inventor
佳奈子 大口
貴尋 坂上
正理 渡邊
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AGC Inc
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Asahi Glass Co Ltd
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Priority to JP2025531549A priority Critical patent/JPWO2025009509A1/ja
Priority to CN202480044210.2A priority patent/CN121443566A/zh
Publication of WO2025009509A1 publication Critical patent/WO2025009509A1/ja
Priority to US19/395,517 priority patent/US20260070836A1/en
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    • 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
    • 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
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • 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
    • C03C4/082—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths for infrared absorbing glass
    • 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
    • G02B5/22—Absorbing filters
    • G02B5/226—Glass filters

Definitions

  • the present invention relates to fluorophosphate glass, which is used in color correction filters for digital still cameras, color video cameras, and the like, and which has excellent light transmittance in the visible range, excellent light absorption in the near-infrared range, and good weather resistance, as well as to near-infrared cut filters and optical devices that incorporate said glass.
  • Solid-state imaging elements such as CCDs and CMOSs used in PCs, digital still cameras, etc. have spectral sensitivity that ranges from the visible range to the near-infrared range around 1200 nm. Because solid-state imaging elements cannot provide good color reproduction as is, their visibility is corrected using near-infrared cut filter glass to which a specific substance that absorbs infrared light has been added.
  • the optical properties required for near-infrared cut filter glass are strong absorption in the near-infrared range (800 nm to 1200 nm) and high transmittance from the visible range to the red range (400 nm to 600 nm).
  • a sharper absorption shape (hereinafter also referred to as sharp cut properties) is required in the shape of the transmittance curve from the red transmission range to the near-infrared blocking range.
  • optical glass (hereinafter also referred to as copper phosphate glass) has been developed in which Cu components have been added to fluorine-free phosphate glass, as a near-infrared cut filter glass.
  • copper phosphate glass has issues with weather resistance.
  • optical glass (hereinafter also referred to as copper fluorophosphate glass or fluorophosphate glass containing Cu, or fluorophosphate glass) has been developed in which Cu components have been added to fluorophosphate glass (phosphate glass containing fluorine) to provide high weather resistance.
  • the compositions of these glasses are disclosed in Patent Documents 1 to 4.
  • JP 2016-60671 A JP 2004-83290 A WO2022/009558 CN-A-114455836
  • copper phosphate glass has high near-infrared absorption and excellent sharp cutting in the near-infrared range, but has issues with weather resistance.
  • copper fluorophosphate glass has high weather resistance, but has issues with near-infrared absorption and sharp cutting in the near-infrared range.
  • the present invention aims to provide fluorophosphate glass that combines optical properties such as high transmittance from the visible range to the red range, high absorption capacity in the near-infrared range, and high sharp-cutting ability in the near-infrared range with high weather resistance, as well as near-infrared cut filters, optical filters, and optical devices that include said glass.
  • the present invention is as follows.
  • a fluorophosphate glass essentially containing each of the components P, Al, K, Cu, F and R (R is one or more selected from Li, Na, Rb and Cs), the content of Al3 + being 2% to 20%, expressed by mass%, and the expected value of the ionic radius of the alkali metal components consisting of K and R being 80 pm to less than 133 pm.
  • the present invention provides fluorophosphate glass that combines excellent optical properties with high weather resistance, as well as near-infrared cut filters, optical filters, and optical devices that incorporate the glass.
  • FIG. 1 is a graph showing the transmittance of light having a wavelength of 300 nm to 1200 nm in the fluorophosphate glasses of Example 5 (embodiment) and Example 10 (comparative example).
  • the content of each component and the total content are expressed in "mass %.”
  • mass % as used in this specification indicates the percentage of the mass of each ion when the total mass of the cationic components is taken as 100.
  • the range “ ⁇ to ⁇ ” means “ ⁇ or more and ⁇ or less.”
  • “Less than ⁇ to ⁇ ” means “ ⁇ or more and less than ⁇ .”
  • the transmittance of the glass in this embodiment includes the reflective properties of the glass surface (i.e., it is not the internal transmittance of the glass).
  • a fluorophosphates glass according to an embodiment of the present invention (hereinafter also referred to as the fluorophosphates glass of the present embodiment, or simply as fluorophosphates glass, or glass) is characterized in that it essentially contains each of the components P, Al, K, Cu, F, and R (R is one or more selected from Li, Na, Rb, and Cs), has an Al 3+ content of 2% to 20%, and has an expected ionic radius of 80 pm (picometers) to less than 133 pm (picometers) of the alkali metal components consisting of K and R.
  • the glass according to an embodiment of the present invention is a copper fluorophosphate glass, the essential components of which are P, Al, K, Cu, F, and R (wherein R is one or more selected from Li, Na, Rb, and Cs).
  • Glass containing P as the main component has the effect of enhancing the absorption capacity in the near-infrared region and the sharp cutting ability in the near-infrared region.
  • F and Al in the glass can improve weather resistance.
  • the absorption capacity in the near-infrared region and the sharp cutting ability can be improved by adjusting the expected value of the ionic radius of the alkali metal components consisting of K and R to less than 80 pm to 133 pm, and the inclusion of K and R can improve weather resistance.
  • the alkali metal components are K + , Li + , Na + , Rb + and Cs + components, and the expected values of the ionic radii of these components are defined as follows:
  • the ionic radii of each alkali metal component are as follows: The ionic radius r Li of Li + is 60 pm, the ionic radius r Na of Na + is 95 pm, the ionic radius r K of K + is 133 pm, the ionic radius r Rb of Rb + is 148 pm, and the ionic radius r Cs of Cs + is 169 pm. These ionic radii are based on the literature of L. Pauling (1931-1933), THE NATURE OF THE CHEMICAL BOND (1963, translated by Masao Koizumi, Chemical Bond Theory, Kyoritsu Shuppan). "Cation %" is a unit that expresses the content of each cationic component in mole percentage when the total content of all cationic components contained in glass is 100 mole %.
  • the expected ionic radius of an alkali metal component is calculated using the following formula:
  • Expected ionic radius [ionic radius of each alkali metal component x total amount of cations of each component] / [total amount of cations of all alkali metal components], To be more specific, it is as follows.
  • the glass according to the embodiment of the present invention can maintain a high transmittance in the red region while maintaining a sharp absorption shape with enhanced absorption in the near infrared region by setting the expected value of the ionic radius of the alkali metal components ( Li + , Na+, K+, Rb+, Cs + ) to 80 pm or more. The reason for this is presumed to be as follows.
  • non-bridging oxygen is coordinated to Cu2 + to form a regular octahedron. If the symmetry of the non-bridging oxygen coordinated to Cu2 + is high, it has a sharp absorption peak in the near infrared region, but if the symmetry of these non-bridging oxygen decreases for reasons described below, the absorption peak of Cu2 + shifts, and the shape of the transmittance curve of the glass changes from a sharp absorption shape to a broad absorption shape. It has been reported in "Optical Properties of Glass II. by Kadono Kohei (2009) NEW GLASS Vol. 24 No. 2" that the absorption spectrum of transition metals including Cu is easily changed by changes in the coordination environment in glass.
  • Electronegativity is a property that indicates the strength of the force that the nucleus of an atom attracts the surrounding electrons.
  • the ionic radius is a value that indicates the distance from the nucleus to the outermost electron shell of an atom. In atoms of the same group, the electronegativity is smaller when the distance between the nucleus and the bonding electron pair is longer, so in other words, a component with a large ionic radius has a small electronegativity.
  • the symmetry of non-bridging oxygen coordinated to Cu2 + is not reduced, and high absorption ability in the near-infrared region and high sharp cutting ability in the near-infrared region can be achieved.
  • the weather resistance may decrease if the expected value of the ionic radius of the alkali metal components (Li + , Na + , K + , Rb + , Cs + ) is set to 133 pm or more. The reason for this is presumed to be as follows.
  • Weather resistance is evaluated based on the degree of deterioration of the glass surface caused when the glass is left standing for a long time under high temperature and high humidity.
  • H + present on the glass surface penetrates into the glass and attacks the -O-P-O- structure, causing hydrolysis.
  • H 3 PO 4 desorbed from the glass surface remains in liquid form and further reacts with the glass, causing the precipitation of foreign matter, which deteriorates the glass surface.
  • the expected ionic radius of the alkali metal component is between 80 pm and less than 133 pm. If it is 80 pm or more, the effect of high absorption ability in the near infrared range and improved sharp cutting properties can be fully obtained, and if it is less than 133 pm, problems such as reduced weather resistance are unlikely to occur. Therefore, it is more preferably 85 pm or more, even more preferably 90 pm or more, even more preferably 95 pm or more, most preferably 100 pm or more, and more preferably 130 pm or less, even more preferably 128 pm or less, even more preferably 125 pm or less, and most preferably 120 pm or less.
  • the glass of the present invention's embodiment essentially contains alkali metal components consisting of K and R.
  • alkali metal components consisting of K and R.
  • P phosphorus
  • P 5+ is the main component forming fluorophosphate glass and is an essential component for enhancing the sharp cut property in the near infrared region.
  • the content of P 5+ is preferably 20% to 70%. If the content of P 5+ is 20% or more, the effect is sufficiently obtained, and if it is 70% or less, problems such as glass becoming unstable and weather resistance decreasing are unlikely to occur. Therefore, it is more preferably 25% or more, even more preferably 30% or more, even more preferably 33% or more, and more preferably 60% or less, even more preferably 55% or less, even more preferably 50% or less, and most preferably 45% or less.
  • F fluorine
  • F- is an essential component for stabilizing the glass and improving weather resistance.
  • the content of F- contained in the glass is expressed as an exclusive percentage when the total amount of all cationic component elements contained in the glass is taken as 100 mass%.
  • the content of F- is preferably 3% to 60% by exclusive percentage.
  • the weather resistance effect is sufficient, and if it is 60% or less by external proportion, problems such as a decrease in the transmittance of light in the visible region, the absorption ability of light in the near-infrared region, and sharp cutting properties, a decrease in mechanical properties such as strength, hardness, and elastic modulus, and an increase in ultraviolet transmittance are unlikely to occur.
  • the content is more preferably 4% or more by external proportion, even more preferably 6% or more by external proportion, even more preferably 8% or more by external proportion, and most preferably 10% or more by external proportion, and also more preferably 50% or less by external proportion, even more preferably 40% or less by external proportion, even more preferably 30% or less by external proportion, and most preferably 20% or less by external proportion.
  • Cu copper
  • Cu + or Cu2 +
  • the contents described in this specification are all when present as Cu2 + .
  • Cu 2+ is an essential component for improving the absorption ability in the near infrared region.
  • Cu 2+ has the property of attracting phosphate chains in the glass to each other to form a crosslinked structure, so that the glass structure is strengthened, and the weather resistance and strength of the glass are improved.
  • the content of Cu 2+ is preferably 1% to 20%. If it is less than 1%, the absorption ability of the glass in the near infrared region may decrease. It is preferably 2% or more, more preferably 3% or more, even more preferably 4% or more, and even more preferably 5% or more. Moreover, if it exceeds 20%, the glass becomes unstable and the risk of devitrification increases. It is preferably 18% or less, more preferably 16% or less, even more preferably 15.2% or less, and even more preferably 14% or less.
  • the total Cu content is the total amount of Cu expressed in mass %, including monovalent, divalent, and other valences present, and when the content of all components of the glass of this embodiment (excluding the content of F- ) is taken as 100%, the content range of the total Cu content in the glass is preferably 1% to 20%.
  • the content of Cu + expressed in % can be determined in a range such that (Cu + /total Cu content) x 100 [%] is 0.01% to 4.0%.
  • Al (aluminum) is contained as Al 3+ .
  • Al 3+ is a component that forms glass and is an essential component for increasing the strength of glass, increasing the weather resistance of glass, and the like. If the content of Al 3+ is 2% or more, the effect is sufficiently obtained, and if it is 20% or less, problems such as glass becoming unstable, and reduction in absorption ability and sharp cut performance in the near infrared region are unlikely to occur.
  • the content of Al 3+ is preferably 2% to 20%.
  • it is 3.5% or more, even more preferably 4% or more, even more preferably 4.5% or more, and most preferably 5% or more, and more preferably 19% or less, even more preferably 18% or less, even more preferably 15% or less, and most preferably 13% or less.
  • AlF3 + As the raw material for Al3 + , AlF3 , Al2O3 , Al(OH) 3, etc. can be used. Among them, it is preferable to use AlF3 , since problems such as an increase in melting temperature, generation of unmelted matter, and instability of the glass due to a decrease in the amount of F- charged are unlikely to occur.
  • Li is a component for lowering the melting temperature of glass, lowering the liquidus temperature of glass, improving the weather resistance of glass, stabilizing glass, etc.
  • the content of Li + is preferably 0% to 30%. If the content of Li + is 30% or less, the glass is less likely to become unstable. If Li is contained, the absorption ability and sharp cut property in the near infrared region are reduced, so it is more preferably 28% or less, even more preferably 25% or less, even more preferably 20% or less, and most preferably 10% or less.
  • the alkali metal component is only Li + , the weather resistance is improved but the absorption ability and sharp cut property in the near infrared region are reduced, so it is necessary to further contain one or more alkali metal components with an ionic radius larger than Li + .
  • Na (sodium) is a component for lowering the melting temperature of glass, lowering the liquidus temperature of glass, stabilizing glass, and the like.
  • the content of Na + is preferably 0% to 40%. If the content of Na + is 40% or less, the glass is less likely to become unstable. It is more preferably 30% or less, even more preferably 25% or less, even more preferably 20% or less, and most preferably 10% or less. If the alkali metal component is only Na + , either one of the effects of improving weather resistance or improving high absorption ability and sharp cut ability in the near infrared region is obtained, and the characteristics improved differ depending on the composition system. However, it is difficult to improve both characteristics at the same time.
  • K potassium
  • K + is an essential component that has the effects of lowering the melting temperature of the glass, lowering the liquidus temperature of the glass, improving the absorption ability and sharp cut property in the near infrared region, and the like.
  • the content of K + is preferably 1% to 40%. If the content of K + is 40% or less, it is preferable because the glass is less likely to become unstable. More preferably, it is 2% or more, even more preferably, it is 5% or more, even more preferably, it is 8% or more, and most preferably, it is 10% or more.
  • the weather resistance decreases when K + is contained, it is preferably 30% or less, even more preferably, it is 25% or less, even more preferably, it is 20% or less, and most preferably, it is 14% or less. If the alkali metal component is only K + , the absorption ability and sharp cut property in the near infrared region are improved, but the weather resistance is decreased. Therefore, it is necessary to contain one or more alkali metal components other than K + in order to improve the weather resistance by the alkali mixing effect.
  • Rb (rubidium) is a component that has the effect of lowering the melting temperature of glass, lowering the liquidus temperature of glass, improving the absorption ability and sharp cut property in the near infrared region, etc.
  • the content of Rb + is preferably 0% to 20%. If the content of Rb + is 20% or less, it is preferable because the glass is less likely to become unstable. If Rb + is contained, the weather resistance decreases, so it is more preferably 15% or less, even more preferably 10% or less, and even more preferably 5% or less. If the alkali metal component is only Rb +, the absorption ability and sharp cut property in the near infrared region are improved, but the weather resistance is decreased. Therefore, it is necessary to contain one or more alkali metal components other than Rb + in order to improve the weather resistance by the alkali mixing effect.
  • Cs (cesium) is a component that has the effect of lowering the melting temperature of glass, lowering the liquidus temperature of glass, and improving high absorption and sharp cutting properties in the near infrared region.
  • the content of Cs + is preferably 0% to 20%. If the content of Cs + is 20% or less, it is preferable because the glass is less likely to become unstable. If Cs + is contained, weather resistance decreases, so it is more preferably 15% or less, even more preferably 10% or less, and even more preferably 5% or less. If the alkali metal component is only Cs + , the absorption and sharp cutting properties in the near infrared region are improved, but the weather resistance decreases. Therefore, it is necessary to contain one or more alkali metal components other than Cs + in order to improve weather resistance by the alkali mixing effect.
  • K + and R + are essential components for lowering the melting temperature of glass, lowering the liquidus temperature of glass, stabilizing glass, and the like. If the total amount of R + and K + , that is, the total amount of Li + , Na + , K + , Rb + and Cs + ( ⁇ R + +K + ) is 14% or more, the effect is sufficiently obtained, and if it is 42% or less, it is preferable because the glass is less likely to become unstable. Therefore, the content of ⁇ R + +K + is preferably 14% to 42%.
  • the content of ⁇ R + +K + is more preferably 14.5% or more, even more preferably 15% or more, even more preferably 17% or more, and most preferably 18% or more. Moreover, the content of ⁇ R + +K + is more preferably 35% or less, further preferably 30% or less, further preferably 28% or less, and most preferably 25% or less.
  • Mg manganesium
  • the content of Mg 2+ is preferably 0 to 20%. If the content of Mg 2+ is 20% or less, problems such as glass becoming unstable and reduced near-infrared cutoff properties are unlikely to occur. It is more preferably 15% or less, even more preferably 10% or less, and even more preferably 5% or less.
  • Ca (calcium) is a component for lowering the melting temperature of glass, lowering the liquidus temperature of glass, stabilizing glass, increasing the strength of glass, increasing the weather resistance of glass, etc.
  • the content of Ca2+ is preferably 0% to 20%. If the content of Ca2+ is 20% or less, problems such as glass becoming unstable and near-infrared cutoff properties decreasing are unlikely to occur. It is more preferably 1% or more, even more preferably 2% or more, and more preferably 18% or less, even more preferably 15% or less, even more preferably 10% or less, and most preferably 7% or less.
  • Sr (strontium) is a component for lowering the melting temperature of glass, lowering the liquidus temperature of glass, stabilizing glass, increasing the strength of glass, and increasing the weather resistance of glass.
  • the content of Sr 2+ is preferably 0% to 30%. If the content of Sr 2+ is 30% or less, problems such as glass becoming unstable and near-infrared cutoff properties decreasing are unlikely to occur. It is more preferably 1% or more, even more preferably 2% or more, even more preferably 4% or more, and most preferably 5% or more, and more preferably 25% or less, even more preferably 20% or less, even more preferably 16% or less, and most preferably 14% or less.
  • Ba (barium) is a component for lowering the melting temperature of glass, lowering the liquidus temperature of glass, stabilizing glass, increasing the light absorption ability in the near infrared region, increasing the sharp cut property in the near infrared region, etc.
  • the content of Ba 2+ is preferably 0% to 40%. If the content of Ba 2+ is 40% or less, problems such as glass instability are unlikely to occur. It is more preferably 1% or more, even more preferably 5% or more, even more preferably 10% or more, most preferably 13% or more, and more preferably 35% or less, even more preferably 30% or less, even more preferably 22% or less, and most preferably 19% or less.
  • R" 2+ (R" 2+ is one or more components selected from Mg 2+ , Ca 2+ , Sr 2+ , and Ba 2+ ) is a component for lowering the melting temperature of glass, lowering the liquidus temperature of glass, stabilizing glass, and the like.
  • R" 2+ i.e., the total amount of Mg 2+ , Ca 2+ , Sr 2+ , and Ba 2+ ( ⁇ R" 2+ ) is 14.5% or more, the effect is sufficiently obtained, and when it is 35% or less, the glass is less likely to become unstable.
  • the content of ⁇ R" 2+ is preferably 14.5% to 35%, more preferably 16.5% or more, even more preferably 18% or more, even more preferably 20% or more, most preferably 22% or more, and more preferably 34% or less, even more preferably 32.5% or less, even more preferably 30% or less, and most preferably 28% or less.
  • Zn (zinc) has the effect of lowering the melting temperature of glass, lowering the liquidus temperature of glass, etc.
  • the content of Zn 2+ is preferably 0% to 20%. If the content of Zn 2+ is 20% or less, problems such as glass becoming unstable, glass melting property being deteriorated, and near-infrared cutoff property being reduced are unlikely to occur.
  • Zn (zinc) is more preferably 15% or less, further preferably 10% or less, and even more preferably 5% or less. Most preferably, Zn (zinc) is not contained.
  • the content of P 5+ / ⁇ R'(R' is one or more components selected from Al 3+ , Mg 2+ and Li + , and ⁇ R' is the total amount of R') is preferably 3.0 to 7.7.
  • P5 + is a component that enhances the sharp cutting ability in the near infrared region, but also has the effect of reducing weather resistance, while Al3 + , Li + , and Mg + are each components that have the effect of improving weather resistance.
  • the ratio of the P 5+ content to ⁇ R' is more preferably 3.2 or more, even more preferably 3.5 or more, even more preferably 4.0 or more, and most preferably 4.5 or more.
  • the ratio of the P 5+ content to ⁇ R' is more preferably 7.5 or less, even more preferably 7.0 or less, even more preferably 6.3 or less, and most preferably 5.5 or less.
  • B boron
  • B3+ may be contained in the range of 20% or less in order to stabilize the glass. If the content of B3+ is 20% or less, problems such as deterioration of the weather resistance of the glass and deterioration of the near-infrared cutoff property are unlikely to occur. It is more preferably 15% or less, even more preferably 10% or less, even more preferably 8% or less, and most preferably 5% or less.
  • SiO2 , GeO2 , ZrO2 , SnO2 , TiO2 , CeO2 , WO3 , Y2O3 , La2O3 , Gd2O3 , Yb2O3 , and Nb2O5 may be contained in a range of 10% or less in order to increase the weather resistance of the glass. If the content of these components is 10% or less, problems such as the generation of devitrification in the glass and the deterioration of the near-infrared cutoff property are unlikely to occur. It is preferably 4% or less, more preferably 3% or less, even more preferably 2% or less, and even more preferably 1% or less.
  • Fe2O3 , Cr2O3 , Bi2O3 , NiO, V2O5 , MnO2 and CoO are all components that , when present in glass, reduce the transmittance of light in the visible region . Therefore, it is preferable that these components are not substantially contained in the glass.
  • substantially not contained in the glass means that they are not contained except for unavoidable impurities, and that the components are not actively added. Specifically, it means that the content of each of these components in the glass is about 100 mass ppm or less.
  • the glass of the embodiment of the present invention preferably has a Young's modulus of 48 GPa or more, more preferably 50 GPa or more, even more preferably 55 GPa or more, and even more preferably 60 GPa or more.
  • the glass of the present embodiment has an average thermal expansion coefficient in the range of 30°C to 300°C of preferably 60 ⁇ 10 -7 /°C to 180 ⁇ 10 -7 /°C, more preferably 65 ⁇ 10 -7 /°C to 165 ⁇ 10 -7 /°C, even more preferably 70 ⁇ 10 -7 /°C to 157 ⁇ 10 -7 /°C, still more preferably 70 ⁇ 10 -7 /°C to 150 ⁇ 10 -7 /°C, and most preferably 70 ⁇ 10 -7 /°C to 143 ⁇ 10 -7 /°C.
  • the glass of the embodiment of the present invention When the glass of the embodiment of the present invention is used as a color correction filter (near-infrared cut filter glass) for a solid-state imaging device, it may be directly bonded to the packaging material because it also functions as a cover glass for hermetically sealing the solid-state imaging device. In this case, if there is a large difference in the thermal expansion coefficient between the near-infrared cut filter glass and the packaging material, peeling or damage may occur at the joint, and the airtight state may not be maintained.
  • a color correction filter near-infrared cut filter glass
  • the glass of this embodiment it is preferable for the glass of this embodiment to have an average thermal expansion coefficient in the temperature range of 30°C to 300°C within the above range.
  • the spectral transmittance at a wavelength of 1200 nm is preferably 22% or less. In this way, glass with low transmittance of light in the near infrared range is obtained.
  • the above spectral transmittance is more preferably 21% or less, even more preferably 20% or less, and even more preferably 19% or less. The above spectral transmittance can be measured by the method described in the examples.
  • the glass of the embodiment of the present invention preferably has a spectral transmittance of 60% or more at a wavelength of 600 nm when converted into a sheet thickness such that the IR half value is 630 nm. In this way, a glass with high sharp cutting properties in the near infrared range is obtained.
  • the above spectral transmittance is more preferably 62% or more, even more preferably 64% or more, and even more preferably 66% or more.
  • the above spectral transmittance can be measured by the method described in the examples.
  • the glass of the embodiment of the present invention preferably has a spectral transmittance of 4.0% or less at a wavelength of 800 nm when converted into a sheet thickness such that the IR half value is 630 nm. In this way, glass with low transmittance of light in the near infrared range is obtained.
  • the above spectral transmittance is more preferably 3.8% or less, even more preferably 3.6% or less, and even more preferably 3.4% or less.
  • the above spectral transmittance can be measured by the method described in the examples.
  • the glass of the embodiment of the present invention preferably has a spectral transmittance of 75% or more at a wavelength of 420 nm when converted into a sheet thickness such that the IR half value is 630 nm. In this way, glass with high transmittance of light in the visible range is obtained.
  • the above spectral transmittance is more preferably 78% or more, even more preferably 80% or more, and particularly preferably 82% or more.
  • the above spectral transmittance can be measured by the method described in the examples.
  • the ratio of the spectral transmittance at a wavelength of 600 nm to the spectral transmittance at a wavelength of 800 nm is 20 or more. In this way, a glass with high sharp-cutting properties in the near-infrared range is obtained.
  • the above spectral transmittance ratio is more preferably 21 or more, even more preferably 21.5 or more, and particularly preferably 22 or more. The above spectral transmittance can be measured by the method described in the examples.
  • Ti1 is the internal transmittance of the target glass at a wavelength of 630 nm (data excluding reflection loss on the front and back surfaces)
  • t1 is the plate thickness of the target glass
  • Ti2 is the converted transmittance
  • t2 is the plate thickness to be converted (plate thickness at which the IR half value is 630 nm).
  • the conversion from transmittance to internal transmittance was performed using the following formula, assuming that the reflection losses Ref on the front and back surfaces of the glass were each 0.0454.
  • the glass of the embodiment of the present invention is used as a color correction filter for a solid-state imaging device, for example, it is often used at a thickness of 0.4 mm or less.
  • the thickness is preferably 0.4 mm or less, more preferably 0.3 mm or less, even more preferably 0.25 mm or less, and even more preferably 0.23 mm or less. From the viewpoint of ensuring the strength of the glass, a thickness of 0.05 mm or more is preferable.
  • the glass of the embodiment of the present invention can be produced, for example, as follows.
  • the raw materials are weighed and mixed to obtain the above composition range (mixing process).
  • This raw material mixture is placed in a platinum crucible and heated and melted in an electric furnace at a temperature of 750°C to 1000°C (melting process). After thorough stirring and clarification, it is cast into a metal mold, cut, polished and formed into a plate of the specified thickness (forming process).
  • the highest temperature of the glass during melting is 1000°C or less. If the highest temperature of the glass during melting exceeds the above temperature, the transmittance characteristics may deteriorate.
  • the above temperature is more preferably 950°C or less, even more preferably 930°C or less, and even more preferably 900°C or less.
  • the temperature in the melting process is too low, problems such as devitrification during melting and a long melt-through time may occur, so the temperature is preferably 800°C or higher, and more preferably 820°C or higher.
  • an optical multilayer film may be provided on at least one surface of the glass.
  • optical multilayer films include IR cut films (films that reflect near-infrared rays), UV/IR cut films (films that reflect ultraviolet rays and near-infrared rays), UV cut films (films that reflect ultraviolet rays), and anti-reflection films. These optical thin films can be formed by known methods such as vapor deposition and sputtering.
  • An adhesion-strengthening film may be provided between the glass of the embodiment of the present invention and the optical multilayer film.
  • an adhesion-strengthening film By providing an adhesion-strengthening film, the adhesion between the glass and the optical multilayer film is improved, and film peeling can be suppressed.
  • adhesion-strengthening films include silicon oxide (SiO 2 ), titanium oxide (TiO 2 ), lanthanum titanate (La 2 Ti 2 O 7 ), aluminum oxide (Al 2 O 3 ), a mixture of aluminum oxide and zirconium oxide (ZrO 2 ), magnesium fluoride (MgF 2 ), calcium fluoride (CaF 2 ), strontium fluoride (SrF 2 ), and fluorine silicone.
  • adhesion-strengthening films are particularly preferred as adhesion-strengthening films because they have higher adhesion to glass and films.
  • the adhesion-strengthening film may be a single layer or two or more layers. In the case of two or more layers, a combination of multiple substances may be used.
  • the near-infrared cut filter according to the embodiment of the present invention comprises the glass according to the embodiment of the present invention described above. This makes it possible to obtain a near-infrared cut filter that can keep the transmittance of light in the near-infrared region low while maintaining a high transmittance of light in the visible region (particularly blue light).
  • the near-infrared cut filter according to the embodiment of the present invention may comprise the following configuration in addition to the glass according to the embodiment of the present invention.
  • the near-infrared cut filter of the embodiment of the present invention may be provided with an absorption layer containing a near-infrared absorbing material having a maximum absorption wavelength in the near-infrared range on at least one of the main surfaces of the glass of the embodiment of the present invention.
  • the near-infrared cut filter according to an embodiment of the present invention is preferably made of a transparent resin selected from acrylic resin, epoxy resin, ene-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyparaphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, and polyester resin, and is preferably made of one of these resins alone or a mixture of two or more of these resins, to which a near-infrared absorbing dye is added and contained in the absorption layer.
  • a transparent resin selected from acrylic resin, epoxy resin, ene-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyparaphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamideimide resin
  • a near-infrared absorbing material consisting of at least one type selected from the group consisting of squarylium dyes, phthalocyanine dyes, cyanine dyes, and diimmonium dyes as the near-infrared absorbing dye.
  • the glass according to the embodiment of the present invention can be applied to optical devices.
  • An optical device is a device that uses light to record or transmit information.
  • Examples of optical devices include an imaging device for a digital still camera and an optical sensor that detects light and converts it into an electrical signal.
  • the glass of the embodiment of the present invention When the glass of the embodiment of the present invention is applied to an optical device, it can be used in combination with an optical filter having different light absorption characteristics from the glass of the embodiment of the present invention.
  • the light absorption characteristics of an optical filter include a characteristic of having an absorption ability in a wavelength range different from that of the glass of the embodiment of the present invention, and a characteristic of having a different absorption ability in the same near-infrared wavelength range as the glass of the embodiment of the present invention.
  • optical filters examples include an infrared cut filter provided near the imaging element of an imaging device, a cover glass that covers the opening of an optical device on the subject side, and a lens provided inside an optical device.
  • the glass of the embodiment of the present invention and the optical filter may also be used in a laminated state.
  • the present specification discloses the following: [1] Essentially containing each of the components P, Al, K, Cu, F, and R (R is one or more selected from Li, Na, Rb, and Cs), The content of Al3 + , expressed by mass%, is 2% to 20%; A fluorophosphate glass in which the expected value of the ionic radius of the alkali metal components consisting of K and R is 80 pm to less than 133 pm.
  • the total amount of ⁇ R + (wherein R + is one or more components selected from Li + , Na + , Rb + , and Cs + , and ⁇ R + is the total amount of R + ) and K + , expressed in mass%, is 14% to 42%;
  • the fluorophosphates glass according to [1], wherein ⁇ R′′ 2+ (R′′ 2+ is one or more components selected from Ba 2+ , Sr 2+ , Ca 2+ , and Mg 2+ , and ⁇ R′′ 2+ is the total amount of R′′ 2+ ) is 14.5% to 35%.
  • a fluorophosphate glass according to any one of [1] to [4], in which, when converted into a plate thickness so that the wavelength at which the transmittance in the near infrared region is 50% (IR half value) is 630 nm, the plate thickness is 0.4 mm or less, the spectral transmittance at a wavelength of 1200 nm is 22% or less, and the spectral transmittance at a wavelength of 600 nm is 60% or more.
  • [8] A fluorophosphate glass according to any one of [1] to [7], in which, when converted into a plate thickness so that the wavelength (IR half value) at which the transmittance in the near infrared region is 50% is 630 nm, the plate thickness is 0.4 mm or less, the spectral transmittance at a wavelength of 800 nm is 4% or less, and the spectral transmittance at a wavelength of 420 nm is 75% or more.
  • a near-infrared cut filter comprising the fluorophosphates glass according to any one of [1] to [9].
  • An optical device comprising the fluorophosphates glass according to any one of [1] to [10].
  • An optical device comprising the fluorophosphates glass according to any one of [1] to [11] and an optical filter having light absorption characteristics different from those of the fluorophosphates glass.
  • Tables 1 to 4 show examples and comparative examples of the fluorophosphate glass of the present invention. Examples 1 to 7 and Examples 19 to 32 are examples, and Examples 8 to 18 are comparative examples.
  • Example 10 shows the results of producing and evaluating glass having a glass composition equivalent to that of Example 9 described in Patent Document 1.
  • Glass preparation For the glasses of Examples 1 to 32, the raw materials were weighed and mixed so that the glass components after melting had the compositions shown in Tables 1 to 4 (mass%, F- is the external percentage, and only the alkali metal components are listed in cation %). The raw materials were charged into a platinum crucible with an internal volume of 1 L, and heated and melted in an electric furnace at the melting temperatures shown in each table for 1 to 100 hours.
  • the glass was clarified, stirred, and poured into a rectangular mold with a length of 100 mm, a width of 65 mm, and a height of 20 mm preheated to 50°C to 500°C, and then held at 300°C to 500°C for 2 hours or more, and then slowly cooled at about 1°C/min to obtain a plate-shaped sample glass with a length of 40 mm, a width of 40 mm, and a plate thickness of 0.1 mm to 0.5 mm, both sides of which were optically polished.
  • Li + LiF, LiNO3 were used.
  • MgO MgO
  • the glass contains O2- as an anion.
  • the content of O2- is not shown because it varies depending on the content of highly volatile F- , but all glasses in the Examples and Comparative Examples contain O2- .
  • the glass raw materials are not limited to those mentioned above, and any known raw materials can be used.
  • the transmittance was evaluated by the following procedure.
  • the optically polished glass thus produced was measured for the transmittance of light with wavelengths of 300 nm to 1200 nm in 1 nm increments using a spectrophotometer (V-570, manufactured by JASCO Corporation), and the plate thickness was converted so that the IR half-value (the wavelength at which the transmittance in the near-infrared region, including reflection losses on the front and back surfaces, is 50%) was 630 nm.
  • the conversion was performed by first converting the obtained transmittance into an internal transmittance and using the following formula.
  • the average thermal expansion coefficient was evaluated by the following procedure: The glass was processed into a rod shape, and the average thermal expansion coefficient was measured at 30 to 300° C. at a heating rate of 5° C./min by the thermal expansion method using a thermal analyzer (manufactured by Rigaku Corporation, product name: TMA8310).
  • Example 5 Example 5
  • Example 10 Comparative Example
  • Each embodiment of the present invention produced glass that had high near-infrared absorption and sharp cutting properties, did not suffer from devitrification (good solubility), and had good weather resistance.
  • Example 8 the expected ionic radius of the alkali metal component was less than 80 pm, resulting in glass with good weather resistance but low near-infrared absorption and sharp cut properties.
  • Example 9 contained only one type of alkali metal component, and the P5 + content/ ⁇ R'(R' is one or more components selected from Al3 + , Mg2 + , and Li + , and ⁇ R' is the total amount of R') was greater than 7.5, resulting in a glass with high absorption ability and sharp cut properties in the near-infrared range but reduced weather resistance.
  • Example 10 the P5 + content/ ⁇ R'(R' is one or more components selected from Al3 + , Mg2 + , and Li + , and ⁇ R' is the total amount of R') was less than 3.0, so the glass had good weather resistance but low near-infrared absorption ability and sharp cut ability.
  • Examples 11 to 14 contain only one type of alkali metal component, and the expected ionic radius of the alkali metal component is 133 pm or greater, so the glass has high near-infrared absorption and sharp cut properties but low weather resistance.
  • Examples 15 and 16 contain two types of alkali metal components, but because the expected ionic radius of the alkali metal components is 133 pm or greater, the glass has high near-infrared absorption and sharp cut properties but reduced weather resistance.
  • Example 17 since ⁇ R + was less than 14%, devitrification occurred and the glass had low solubility.
  • Example 17 suggests that the solubility is improved by setting the content of ⁇ R + within a predetermined range.
  • Example 18 since ⁇ R + was less than 14% and ⁇ R′′ + was more than 40%, devitrification occurred and the glass had low solubility.
  • Example 18 suggests that the solubility is improved by setting the ⁇ R + content and the ⁇ R′′ + content within a predetermined range.

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PCT/JP2024/023839 2023-07-04 2024-07-01 フツリン酸ガラス、近赤外線カットフィルタ、光学デバイス Ceased WO2025009509A1 (ja)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011071157A1 (ja) * 2009-12-11 2011-06-16 旭硝子株式会社 近赤外線カットフィルタガラス
JP2011162409A (ja) * 2010-02-12 2011-08-25 Asahi Glass Co Ltd 近赤外線カットフィルタガラスおよび近赤外線カットフィルタガラスの製造方法
JP2012148964A (ja) * 2010-12-23 2012-08-09 Schott Ag フッ化リン酸ガラス
JP2014012630A (ja) * 2012-06-22 2014-01-23 Schott Ag 着色ガラス
WO2018021222A1 (ja) * 2016-07-29 2018-02-01 旭硝子株式会社 光学ガラスおよび近赤外線カットフィルタ

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011071157A1 (ja) * 2009-12-11 2011-06-16 旭硝子株式会社 近赤外線カットフィルタガラス
JP2011162409A (ja) * 2010-02-12 2011-08-25 Asahi Glass Co Ltd 近赤外線カットフィルタガラスおよび近赤外線カットフィルタガラスの製造方法
JP2012148964A (ja) * 2010-12-23 2012-08-09 Schott Ag フッ化リン酸ガラス
JP2014012630A (ja) * 2012-06-22 2014-01-23 Schott Ag 着色ガラス
WO2018021222A1 (ja) * 2016-07-29 2018-02-01 旭硝子株式会社 光学ガラスおよび近赤外線カットフィルタ

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