WO2021132645A1 - 近赤外線吸収ガラスおよび近赤外線カットフィルタ - Google Patents

近赤外線吸収ガラスおよび近赤外線カットフィルタ Download PDF

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Publication number
WO2021132645A1
WO2021132645A1 PCT/JP2020/048961 JP2020048961W WO2021132645A1 WO 2021132645 A1 WO2021132645 A1 WO 2021132645A1 JP 2020048961 W JP2020048961 W JP 2020048961W WO 2021132645 A1 WO2021132645 A1 WO 2021132645A1
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ion
ions
glass
content
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PCT/JP2020/048961
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English (en)
French (fr)
Japanese (ja)
Inventor
将士 金子
塩田　勇樹
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Hoya Corp
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Hoya Corp
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Priority to JP2021567712A priority Critical patent/JP7662535B2/ja
Priority to CN202080090602.4A priority patent/CN114901606A/zh
Priority to KR1020227022054A priority patent/KR102849066B1/ko
Priority to CN202411197549.4A priority patent/CN118993534A/zh
Priority to US17/788,459 priority patent/US12297146B2/en
Publication of WO2021132645A1 publication Critical patent/WO2021132645A1/ja
Anticipated expiration legal-status Critical
Priority to JP2025061620A priority patent/JP2025102937A/ja
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • 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
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/16—Silica-free oxide glass compositions containing 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
    • 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
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus
    • C03C3/21—Silica-free oxide glass compositions containing phosphorus containing titanium, zirconium, vanadium, tungsten or molybdenum
    • 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
    • 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
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • 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
    • C03C2204/00—Glasses, glazes or enamels with special properties

Definitions

  • the present invention relates to a near-infrared absorbing glass and a near-infrared cut filter.
  • the near-infrared cut filter is an unnecessary near-infrared light (wavelength 700) in the sensitivity wavelength range of the image sensor in order to make the light entering the image sensor such as CCD or CMOS have an optical wavelength distribution corresponding to the human relative luminous efficiency curve. It has a function of cutting up to 1200 nm).
  • the near-infrared cut filter is generally provided immediately before the image sensor.
  • Near-infrared cut filters are widely used with near-infrared absorbing glass as the base material and polished on a flat plate.
  • Near-infrared absorbing glass generally contains Cu ions.
  • FIG. 1 shows an example of the spectral transmission characteristics of the near-infrared absorbing glass. Note that FIG. 1 does not limit the present invention in any way.
  • the light absorption characteristics near the wavelength of 700 to 1200 nm are expressed by Cu ions (Cu 2+) in the glass.
  • phosphate glass containing Cu ions is useful as a glass for a near-infrared cut filter because it can exhibit the near-infrared absorption characteristics of Cu ions (Cu 2+) in a wide wavelength range (for example, patented). Reference 1).
  • the wavelength at which the transmittance is 50% is called "half value" and is one of the main standards of the near-infrared cut filter.
  • the half price varies depending on the specifications of the filter, but is often set in the wavelength range of 600 nm to 650 nm.
  • As a general method of setting the half value to a desired value there is a method of adjusting either the plate thickness of the glass base material or the Cu ion (Cu 2+) concentration in the glass according to the Lambert-Beer law.
  • the near-infrared cut filter has an excellent ability to cut near-infrared rays (that is, has a desired half value but a low transmittance of near-infrared light), and also has a transmittance of visible light (wavelength 400 to 600 nm). It is also required to be expensive.
  • the image sensor module mounted on a smartphone or the like is required to have both miniaturization and high performance, and therefore, the plate thickness of the near-infrared cut filter is required to be thin.
  • the concentration of Cu ions (Cu 2+) in the glass In order to reduce the wall thickness while maintaining the ability to cut near infrared rays, it is necessary to increase the concentration of Cu ions (Cu 2+) in the glass.
  • Cu + Cu ions
  • the near-infrared cut filter has high chemical durability (that is, excellent weather resistance) in a high temperature and high humidity environment.
  • one aspect of the present invention provides a near-infrared absorbing glass having excellent near-infrared cutting ability, high visible light transmittance, and excellent weather resistance, and a near-infrared absorbing glass comprising such near-infrared absorbing glass.
  • the purpose is.
  • the present inventors examined the glass composition from the following two viewpoints in order to increase the visible light transmittance.
  • a glass composition capable of obtaining a desired half value and sufficient near-infrared ray cutting ability even with a smaller amount of Cu than before.
  • the present inventors assume a complex glass skeleton in which P 2 O 5 is arranged around Cu 2+ , and monovalent and divalent ions which are intermediate components other than these glass skeletons.
  • P 2 O 5 is arranged around Cu 2+
  • monovalent and divalent ions which are intermediate components other than these glass skeletons.
  • the present inventors can improve the meltability of the glass raw material batch by keeping the ratio of the network-forming components of glass such as Al and P to a certain level or less, and can melt and mold at a lower temperature than before. I found that
  • the present inventors can reduce the amount of Cu required to achieve the desired half value by setting the ratio of O and P in the entire glass to a certain level or higher, and further, POP having poor water resistance. It was found that it is possible to suppress the formation of cross-linked bonds and improve the weather resistance.
  • one aspect of the present invention is As a constituent ion P ion, Cu ion, O ion, One or more ions selected from the group consisting of Li ion, Na ion and K ion, and One or more ions selected from the group consisting of Mg ion, Ca ion, Sr ion and Ba ion, Including at least In the glass composition indicated by cation%,
  • the Cu ion content is 15.0 cation% or less
  • the content of P ions is 55.0 cation% or less
  • Cation ratio of total content of Al ion and P ion to total content of Mg ion, Ca ion, Sr ion, Ba ion, Zn ion and Cu ion ((Al ion + P ion) / (Mg ion + Ca ion + Sr ion) + Ba ion + Zn ion + Cu ion)) is 5.300 or less
  • a near-infrared absorbing glass having an O ion content of 85.0 anion% or more and a ratio of the O ion content to the P ion content (O ion / P ion) of 3.300 or more. (Hereafter, it is also simply referred to as "glass”.), Regarding.
  • the above-mentioned near-infrared absorbing glass can have excellent near-infrared ray cutting ability, high visible light transmittance, and excellent weather resistance and melting property.
  • a near-infrared absorbing glass having excellent near-infrared ray cutting ability, high visible light transmittance, and excellent weather resistance and melting property. Further, according to one aspect of the present invention, it is possible to provide a near-infrared cut filter made of such a near-infrared absorbing glass.
  • the near-infrared absorbing glass is a glass having a property of absorbing light of at least the entire region or a part of the near-infrared wavelength region (wavelength 700 to 1200 nm).
  • the near-infrared absorbing glass according to one aspect of the present invention can be an oxide glass because it contains O ions (oxygen ions) as constituent ions.
  • Oxide glass is glass in which the main network-forming component of glass is oxide.
  • the near-infrared absorbing glass according to one aspect of the present invention can be a phosphate glass because it contains P ions (phosphorus ions) as well as O ions (oxygen ions) as constituent ions.
  • cation% is a value calculated by "(number of cations of interest / total number of cations of glass component) x 100" and means a molar percentage of the amount of cations of interest to the total amount of cations. To do.
  • anion% is a value calculated by "(number of anions of interest / total number of anions of glass component) x 100" and means a molar percentage of the amount of anions of interest with respect to the total amount of anions. ..
  • the molar ratio of the content of the cations is equal to the ratio of the content of the cation of interest by the cation% indication, and the molar ratio of the content of the anions is the ratio of the content of the anion of interest by the anion% indication. equal.
  • the molar ratio of the cation content to the anion content is the ratio of the contents (in mol%) of the components of interest when the total amount of all cations and all anions is 100 mol%.
  • the content of each component is determined by a known method, for example, an inductively coupled plasma emission spectroscopic analysis method (ICP-AES), an inductively coupled plasma mass spectrometry method (ICP-MS), an ion chromatography method, or the like.
  • Content rate (% by mass of element) can be quantified. By dividing the content of this element (mass% of the element) by the atomic weight, the content of each element in mol% can be obtained, and the cation% and the anion% can be obtained from the values.
  • the content of the constituent component is 0% or not contained or introduced, which means that the constituent component is substantially not contained, and the constituent component is at an unavoidable impurity level. It is permissible to be included.
  • the unavoidable impurity level means, for example, less than 0.01%.
  • the formal valence of each cation is used to determine the average valence of the cations, which will be described in detail later.
  • the formal valence is the valence required for the oxide to maintain its electrical neutrality when the valence of the oxygen ions (anions) that make up the oxide is -2 for the oxide of the cation of interest. Yes, it can be uniquely obtained from the chemical formula of the oxide.
  • the valence of Cu is +2 in order to maintain the electrical neutrality between O 2- and Cu contained in the chemical formula of CuO oxide.
  • the valence of P is +5 in order to maintain the electrical neutrality between O2- and P contained in the chemical formula of oxide P2O5.
  • the form valence of the cation A X O Y is "+ 2X / Y". Therefore, when analyzing the glass composition, it is not necessary to analyze the valence of the cation.
  • the valence of the anion (for example, the valence of the oxygen ion is -2) is also a formal valence based on the idea that the oxygen ion accepts two electrons and has a closed shell structure. Therefore, when analyzing the glass composition, it is not necessary to analyze the valence of the anion. Further, as described above, a part of Cu 2+ can become Cu + at the time of melting, but since the amount thereof is small, the valence of Cu can be set to +2 when calculating the average valence.
  • P ions are network-forming components of glass.
  • the P ion content of the glass is 55.0% or less, preferably 53.0% or less, and more preferably 51.0% or less from the viewpoint of improving weather resistance and meltability. It is more preferably 50.0% or less, further preferably 49.0% or less, further preferably 48.0% or less, and even more preferably 47.0% or less. , 46.0% or less is even more preferable, 45.0% or less is even more preferable, and 44.0% or less is even more preferable. Since the glass contains P ions as constituent ions, the P ion content is more than 0%.
  • the P ion content is preferably 30.0% or more, more preferably 32.0% or more. , 34.0% or more, more preferably 36.0% or more, further preferably 38.0% or more, and even more preferably 39.0% or more. It is even more preferably 40.0% or more, and even more preferably 41.0% or more.
  • the formal valence of the P ion is +5.
  • the Cu ions are components that contribute to providing glass with the ability to cut near infrared rays.
  • the Cu ion content of the glass is 15.0% or less, preferably 13.0% or less, more preferably 11.0% or less, and 9 It is more preferably 0.0% or less. Since the glass contains Cu ions as constituent ions, the Cu ion content is more than 0%. In order to have a sufficient near-infrared ray cutting ability, the Cu ion content is preferably 0.5% or more, more preferably 1.5% or more, and preferably 2.5% or more. More preferred.
  • the glass can be used as a near-infrared cut filter glass having a thickness of 0.25 mm or less.
  • the Cu ion content is preferably 1.5% or more as a glass suitable for a near-infrared cut filter having a relatively thin thickness within the above thickness range (hereinafter, also referred to as “glass I”). 1.7% or more, 1.9% or more, 2.1% or more, 2.3% or more, 2.5% or more, 2.7% or more, 2.9% or more, 3.1% or more, 3. 3% or more, 3.5% or more, 3.7% or more, 3.9% or more, 4.1% or more, 4.5% or more, 4.7% or more, 4.9% or more, 5.1% The above order is preferable.
  • the Cu ion content of glass I is preferably 15.0% or less, preferably 13.0% or less and 11.0% or less. , 10.0% or less, 9.0% or less, 8.5% or less, 8.0% or less, 7.5% or less, 7.0% or less, 6.5% or less, 6.0% or less in that order. More preferred.
  • d is the thickness for which a preferable value of Cu ion is desired to be obtained, and the unit is mm.
  • the preferable range of Cu ions is set. It can be obtained by multiplying the above preferable range by (0.11 / d).
  • the Cu ion content is preferably 0.5% or more, 0.7% or more, 0.9% or more, 1.1% or more, 1.3%. Above, 1.5% or more, 1.7% or more, 1.9% or more, 2.1% or more, 2.3% or more, 2.5% or more are more preferable.
  • the Cu ion content of Glass II is preferably 10.0% or less, and 9.0% or less, 8 5.5% or less, 8.0% or less, 7.5% or less, 7.0% or less, 6.5% or less, 6.0% or less, 5.5% or less, 5.0% or less, 4.5 % Or less, 4.0% or less, and 3.5% or less are more preferable.
  • the formal valence of Cu ions is +2.
  • the Li ion content of the glass can be 0%, 0% or more, or more than 0%.
  • Li ion is a component having a function of improving devitrification resistance during melting and molding of glass.
  • the Li ion content is preferably 10.0% or more, more preferably 12.0% or more, still more preferably 13.0% or more. , 14.0% or more, more preferably 15.0% or more, further preferably 16.0% or more, and even more preferably 17.0% or more. It is even more preferably 18.0% or more, even more preferably 20.0% or more, even more preferably 20.5% or more, and even more preferably 21.0% or more.
  • the Li ion content is preferably 32.0% or less, preferably 31.0% or less. It is more preferably 30.5% or less, further preferably 30.0% or less, further preferably 29.5% or less, and 29.0% or less.
  • Li ion content> Na ion content it is preferable to set “Li ion content> K ion content”.
  • the Na ion content of the glass can be 0%, 0% or more, or more than 0%.
  • Na ion is also a component having a function of improving the meltability of glass.
  • the Na ion content is 30.0% or less. It is preferably 28.0% or less, more preferably 27.0% or less, further preferably 25.0% or less, and further preferably 23.0% or less.
  • the formal valence of Na ions is +1. In one form, from the above viewpoint, it is preferable that "Na ion content ⁇ Li ion content", and "Na ion content ⁇ K ion content” is preferable.
  • the K ion content of the glass can be 0%, 0% or more, or more than 0%.
  • K ion is also a component having a function of improving the meltability of glass and further improving the devitrification resistance during melting and molding.
  • the K ion content is preferably 3.0% or more, more preferably 4.0% or more, further preferably 5.0% or more, and 6.0%.
  • the above is even more preferable, 7.0% or more is even more preferable, 8.0% or more is even more preferable, and 9.0% or more is even more preferable. It is even more preferably 10.0% or more.
  • the K ion content is preferably 20.0% or less, preferably 19.0% or less. It is more preferably 17.0% or less, further preferably 15.0% or less, further preferably 14.5% or less, and 14.0% or less. It is even more preferably 13.5% or less, even more preferably 13.0% or less, even more preferably 12.5% or less, 12 It is particularly preferable that it is 0.3% or less.
  • the formal valence of the K ion is +1. In one form, from the above viewpoint, it is preferable that "K ion content ⁇ Li ion content" and "K ion content> Na ion content".
  • the glass contains one or more ions selected from the group consisting of Li ion, Na ion and K ion as constituent ions. That is, the glass can contain only Li ions in one form, can contain only Na ions in another form, can contain only K ions in another form, and can contain only K ions. Can contain Li and Na ions, another form can contain Li and K ions, another form can contain Na and K ions, and yet another form. Can include Li ions, Na ions and K ions.
  • the glass can also contain alkali metal ions other than Li ion, Na ion and K ion.
  • alkali metal ions include Cs ions.
  • the Cs ion content of the glass can be 0%, 0% or more or more than 0%.
  • the formal valence of the Cs ion is +1.
  • the total content of Li ion, Na ion and K ion is preferably 19.0% or more, and preferably 21.0% or more. More preferably, it is 23.0% or more, further preferably 25.0% or more, further preferably 27.0% or more, further preferably 28.0% or more. It is even more preferably 29.0% or more, even more preferably 30.0% or more, even more preferably 30.5% or more, and even more preferably 31.0% or more. Even more preferably, 32.0% or more, 32.5% or more, 33.0% or more, 33.5% or more, 34.0% or more, 34.5% or more, 35.
  • the total content of Li ion, Na ion and K ion is 56.0% or less. It is preferably 54.0% or less, more preferably 52.0% or less, further preferably 50.0% or less, and 48.0% or less.
  • the Mg ion content of the glass can be 0%, 0% or more, or more than 0%.
  • the Mg ion content is preferably 0.3% or more, preferably 0.5. % Or more is more preferable, 0.8% or more is further preferable, 1.1% or more is further preferable, and 1.3% or more is even more preferable.
  • the Mg ion content is preferably 7.0% or less, more preferably 6.0% or less.
  • Mg ion content ⁇ Ca ion content it is preferable that "Mg ion content ⁇ Ba ion content" is preferable.
  • the Ca ion content of the glass can be 0%, 0% or more, or more than 0%.
  • the Ca ion content is preferably 1.3% or more, preferably 1.5% or more. It is more preferably 1.7% or more, further preferably 1.9% or more, even more preferably 2.1% or more, and 2.3% or more. Even more preferably, it is even more preferably 2.5% or more, and particularly preferably 2.7% or more.
  • the Ca ion content is preferably 9.0% or less, more preferably 8.0% or less, and 7 It is more preferably 0.0% or less, further preferably 6.0% or less, further preferably 5.0% or less, further preferably 4.5% or less, 4 It is even more preferably 2.2% or less, even more preferably 3.9% or less, even more preferably 3.7% or less, and 3.5% or less. Especially preferable.
  • the formal valence of Ca ions is +2. In one form, from the above viewpoint, it is preferable to set “Ca ion content> Mg ion content”, and it is preferable to set “Ca ion content> Sr ion content”.
  • the Sr ion content of the glass can be 0%, 0% or more, or more than 0%.
  • the Sr ion content is preferably 0.2% or more, preferably 0.4% or more. It is more preferably 0.6% or more, further preferably 0.8% or more, and even more preferably 0.9% or more.
  • the Sr ion content is preferably 4.0% or less, more preferably 3.5% or less. 2.
  • Sr ion content ⁇ Ca ion content is preferable, and "Sr ion content ⁇ Ba ion content” is preferable.
  • the Ba ion content of the glass can be 0%, 0% or more, or more than 0%.
  • the Ba ion content is preferably 1.5% or more, preferably 2.5% or more. It is more preferably 2.9% or more, further preferably 3.1% or more, further preferably 3.3% or more, and 3.5% or more. Is even more preferable.
  • the Ba ion content is preferably 10.0% or less, more preferably 9.5% or less, and 9 It is more preferably 0.0% or less, further preferably 8.5% or less, further preferably 8.0% or less, even more preferably 7.5% or less, 7 It is even more preferably 0.0% or less, even more preferably 6.5% or less, even more preferably 6.0% or less, and still more preferably 5.6% or less. Even more preferably, it is even more preferably 5.3% or less, and even more preferably 5.0% or less, 4.7% or less, 4.5% or less, 4.3% or less. preferable.
  • the formal valence of the Ba ion is +2. In one form, from the above viewpoint, it is preferable to set "Ba ion content> Ca ion content", and it is preferable to set "Ba ion content> Sr ion content”.
  • the glass contains one or more ions selected from the group consisting of Mg ions, Ca ions, Sr ions and Ba ions. From the viewpoint of lowering the average valence and increasing the visible light transmittance, it is preferable that the total content of Mg ion, Ca ion, Sr ion and Ba ion is small.
  • the total content of Mg ion, Ca ion, Sr ion and Ba ion is preferably 20.0% or less, preferably 19.0% or less, from the above viewpoint and the viewpoint of further improving the meltability. It is more preferably 18.0% or less, further preferably 17.5% or less, further preferably 17.0% or less, and preferably 16.5% or less.
  • the total content of Mg ion, Ca ion, Sr ion and Ba ion is preferably 3.0% or more, preferably 4.0% or more, from the viewpoint of suppressing the decrease in liquid phase temperature and improving the weather resistance.
  • the above glass has Mg ions, with respect to the total content of Li ions, Na ions and K ions.
  • the cation ratio ((Mg ion + Ca ion + Sr ion + Ba ion) / (Li ion + Na ion + K ion)) of the total content of Ca ion, Sr ion and Ba ion is 0.100 or more, and 0.105 or more. It is preferably 0.110 or more, more preferably 0.115 or more, further preferably 0.120 or more, further preferably 0.125 or more, and 0.
  • the cation ratio ((Mg ion + Ca ion + Sr ion + Ba ion) / (Li ion + Na ion + K ion)) is 0.650 or less. It is preferably 0.620 or less, more preferably 0.590 or less, further preferably 0.560 or less, further preferably 0.530 or less, and 0.
  • .500 or less it is even more preferably .500 or less, even more preferably 0.460 or less, even more preferably 0.430 or less, even more preferably 0.400 or less, and 0. Even more preferably, it is 0.350 or less, 0.350 or less, 0.320 or less, 0.310 or less, 0.300 or less, 0.295 or less, 0.290 or less, 0.287 or less. , 0.285 or less, which is even more preferable.
  • the cation ratio is in the above range.
  • the Al ion content of the glass can be 0%, 0% or more or more than 0%.
  • the Al ion content is preferably 1.0% or more, more preferably 1.3% or more. 2. It is more preferably 5% or more, further preferably 1.7% or more, further preferably 1.9% or more, and even more preferably 2.1% or more. It is even more preferably 3% or more, and even more preferably 2.5% or more.
  • the Al ion content is preferably 8.0% or less, more preferably 7.0% or less.
  • the total content of Al ions and P ions (Al ions + P ions) of the glass is preferably 40.0% or more from the viewpoint of enhancing the thermal stability and mechanical strength of the glass. It is more preferably 0% or more, further preferably 42.0% or more, further preferably 42.5% or more, further preferably 43.0% or more, and 44.0. % Or more is even more preferable, 44.5% or more is even more preferable, and 45.0% or more is even more preferable. Further, from the viewpoint of further improving the meltability of the raw material and further suppressing the formation of Cu + , the total content (Al ion + P ion) is preferably 55.0% or less, preferably 54.0% or less.
  • the Zn ion content of the glass can be 0%, 0% or more, or more than 0%. From the viewpoint of lowering the Tg of the glass, the Zn ion content should be introduced in place of Mg and / or Ca and / or Sr and / or Ba as long as it does not significantly affect the action exerted by the various components. Can be done. However, from the viewpoint of improving weather resistance, the Zn ion content is preferably 8.7% or less, more preferably 8.5% or less, further preferably 8.3% or less, and 8 It is more preferably 0.0% or less, further preferably 7.7% or less, further preferably 7.5% or less, and even more preferably 7.3% or less.
  • the glass has a cation ratio of Zn ions to the total content of Mg ions, Ca ions, Sr ions, Ba ions and Zn ions (Zn ion / (Mg ion + Ca ion + Sr ion + Ba ion + Zn ion). )) Is preferably 0.600 or less, more preferably 0.580 or less, further preferably 0.570 or less, further preferably 0.560 or less, and further 0.
  • the order is .300 or less, 0.200 or less, 0.100 or less, 0.080 or less, 0.060 or less, 0.040 or less, and 0.020 or less.
  • the cation ratio Zn ion / (Mg ion + Ca ion + Sr ion + Ba ion + Zn ion)) may be 0 or 0.000.
  • the above glass is the sum of Al ion and P ion with respect to the total content of Mg ion, Ca ion, Sr ion, Ba ion, Zn ion and Cu ion.
  • the cation ratio of the content ((Al ion + P ion) / (Mg ion + Ca ion + Sr ion + Ba ion + Zn ion + Cu ion)) is 5.3 or less, preferably 5.1 or less, and preferably 4.9 or less.
  • the above-mentioned cation ratio ((Al ion + P ion) / (Mg ion + Ca ion + Sr ion + Ba ion + Zn ion + Cu ion)) is 1.
  • the glass can optionally contain one or more of the following cations as cations.
  • the weather resistance is further improved, the chemical resistance is improved, the decrease in the glass transition temperature is suppressed, and / Alternatively, it can contribute to suppressing the decrease in viscosity at the liquidus temperature.
  • the ion content of these rare earth atoms can be 0%, 0% or more or more than 0%, respectively, 3.0% or less, 2.0% or less, 1.0% or less or 0.5%, respectively. It can also be: The formal valence of Y ion, La ion, Gd ion and Yb ion is +3.
  • Ti, Zr, Nb, W and Bi are components that contribute to the improvement of weather resistance and chemical resistance of glass, the suppression of Tg decrease, and the suppression of liquid phase viscosity decrease by adding a small amount. ..
  • the Ti ion content can be 0%, 0% or more or more than 0%, preferably 3.0% or less, more preferably 2.0% or less, and 1.0% or less. Is more preferable, and 0.5% or less is further preferable.
  • the formal valence of Ti ions is +4.
  • the Zr ion content can be 0%, 0% or more or more than 0%, preferably 3.0% or less, more preferably 2.0% or less, and 1.0% or less. Is more preferable, and 0.5% or less is further preferable.
  • the formal valence of the Zr ion is +4.
  • the Nb ion content can be 0%, 0% or more or more than 0%, preferably 3.0% or less, more preferably 2.0% or less, and 1.0% or less. Is more preferable, and 0.5% or less is further preferable.
  • the formal valence of Nb ions is +5.
  • the W ion content can be 0%, 0% or more or more than 0%, preferably 3.0% or less, more preferably 2.0% or less, and 1.0% or less. Is more preferable, and 0.5% or less is further preferable.
  • the formal valence of W ions is +6.
  • the Bi ion content can be 0%, 0% or more or more than 0%, preferably 3.0% or less, more preferably 2.0% or less, and 1.0% or less. Is more preferable, and 0.5% or less is further preferable.
  • the formal valence of Bi ions is +3.
  • the glass has an average valence of less than 1.500, preferably 1.490 or less, preferably 1.480 or less, except for Cu ions and P ions. It is more preferably 1.470 or less, further preferably 1.460 or less, further preferably 1.450 or less, and further preferably 1.440 or less. It is more preferably 1.430 or less, and further preferably 1.420 or less, 1.410 or less, 1.400 or less, 1.390 or less, 1.380 or less, 1.370 or less, 1.360. Hereinafter, it is even more preferable in the order of 1.350 or less.
  • the average valence of cations excluding Cu ions and P ions is preferably 1.100 or more, and more preferably 1.1500 or more, from the viewpoint of suppressing a decrease in viscosity at the liquid phase temperature. It is preferably 1.200 or more, more preferably 1.250 or more, further preferably 1.270 or more, further preferably 1.280 or more, and even more preferably 1.290. The above is even more preferable, and the value of 1.300 or more is even more preferable. For example, when changing the Cu concentration when adjusting the wavelength at which the thickness of the glass and the transmittance are 50%, the composition can be readjusted with reference to the above average valence.
  • the above average valence is the sum of "content of each cation in cation% x formal valence of the cation" for cations excluding Cu and P ions, in% of cations excluding Cu and P. It is calculated as the value divided by the total content of. For example, in addition to Cu and P ions, A cation (formal value a, content A% in% cation), B cation (formal value b, content B% in% cation) and C cation ( The above average valence is calculated as "(A ⁇ a + B ⁇ b + C ⁇ c) / (A + B + C)" for the glass containing the formal value c and the total content C% in% of the cations.
  • the above glass can also refer to the average valence containing Cu ions when changing the Cu concentration when adjusting the wavelength at which the thickness and transmittance of the glass are 50%.
  • the average valence of cations obtained in the same manner as above shall be 1.550 or less from the viewpoint of further improving the visible light transmittance. It is more preferably 1.540 or less, further preferably 1.530 or less, further preferably 1.520 or less, and even more preferably 1.510 or less. It is even more preferably 500 or less, and further preferably 1.490 or less, 1.480 or less, 1.470 or less, 1.460 or less, 1.450 or less, 1.440 or less, 1.430 or less.
  • the average valence of cations excluding only P ions is preferably 1.300 or more, more preferably 1.310 or more. It is more preferably 1.320 or more, further preferably 1.330 or more, further preferably 1.340 or more, even more preferably 1.350 or more, and 1.360 or more. Is even more preferable.
  • the glass contains O ions as constituent ions.
  • the O ion content is 85.0% or more, preferably 90.0% or more, and preferably 95.0% or more, from the viewpoint of facilitating homogenization during melting of the glass and increasing productivity. More preferably, it is more preferably 98.0% or more, and even more preferably 99.0% or more.
  • the content of O ions is preferably 100%.
  • the formal valence of O ion is -2.
  • the glass can contain only O ions in one form as anions, and can contain one or more other anions together with O ions in another form.
  • examples of other anions include F ion, Cl ion, Br ion, I ion and the like.
  • the formal valence of F ion, Cl ion, Br ion, and I ion is -1.
  • the content of F ions is preferably 15.0% or less, more preferably 10.0% or less, and more preferably 5.0% or less, from the viewpoint of improving the homogeneity and strength of the glass. Is even more preferable, 2.0% or less is further preferable, and 1.0% or less is even more preferable. In particular, from the viewpoint of suppressing volatilization during glass melting, increasing productivity and suppressing generation of harmful gas during production, F ions may not be contained.
  • the glass has a ratio of O ion content (O ion / P ion) to P ion content of 3.300 or more, preferably 3.310 or more. It is more preferably .320 or more, further preferably 3.330 or more, and further preferably 3.340 or more, 3.350 or more, 3.360 or more, 3.370 or more, 3.380 or more, 3 More preferably, in the order of .390 or more, 3.400 or more, 3.410 or more, 3.420 or more, 3.430 or more, 3.440 or more, 3.450 or more, 3.460 or more.
  • the above ratio (O ion / P ion) is preferably 3.580 or less. It is more preferably 570 or less, further preferably 3.560 or less, further preferably 3.550 or less, further preferably 3.540 or less, and 3.530 or less. Is even more preferable, and even more preferably, in the order of 3.520 or less, 3.510 or less, 3.500 or less, 3.490 or less.
  • the glass is basically composed of the above components, but it is also possible to contain other components as long as the effects of the above components are not impaired. In addition, the glass does not exclude the inclusion of unavoidable impurities.
  • the glass does not contain these as glass components.
  • U, Th, and Ra are all radioactive elements. Therefore, it is preferable that the glass does not contain these as glass components.
  • the content of these elements in terms of oxide based on the oxide glass is preferably 10 mass ppm or less in total, and it is more preferable that these elements are not contained as a glass component.
  • Ge, Ta, and Gd are expensive raw materials. Therefore, it is preferable that the glass does not contain these as a glass component.
  • Sb (Sb 2 O 3 ), Sn (SnO 2 ), Ce (CeO 2 ), and SO 3 are optionally additive elements that act as clarifying agents.
  • Sb (Sb 2 O 3 ) is a clarifying agent having a large clarifying effect.
  • Sn (SnO 2 ) and Ce (CeO 2 ) have a smaller clarification effect than Sb (Sb 2 O 3).
  • Sb (Sb 2 O 3) it is preferable to add Sb (Sb 2 O 3) while considering the influence of coloring due to the addition.
  • the content of Sb 2 O 3 is indicated by external division. That is, when the total content of all glass components other than Sb 2 O 3 , SnO 2 , CeO 2 and SO 3 as oxides is 100.0% by mass, the content of Sb 2 O 3 is, in one form, , Less than 1.0% by mass, less than 0.5% by mass, less than 0.3% by mass, less than 0.2% by mass, less than 0.15% by mass, less than 0.1% by mass or less than 0.1% by mass There can be. In one form, the content of Sb 2 O 3 can be 0% by weight. In another form, the content of Sb 2 O 3 can be more than 0% by mass.
  • the content of Sb 2 O 3 is preferably more than 0% by mass, preferably 0.01% by mass. % Or more, 0.03% by mass or more, 0.05% by mass or more, 0.08% by mass or more, and 0.10% by mass or more are more preferable.
  • the content of SnO 2 is also indicated by external division. That is, the content of SnO 2 is preferably 2.0 when the total content of all glass components other than SnO 2 , Sb 2 O 3 , CeO 2 and SO 3 as oxides is 100.0% by mass. It is in the range of less than mass%, more preferably less than 1.0% by mass, still more preferably less than 0.5% by mass, still more preferably less than 0.1% by mass.
  • the content of SnO 2 may be 0% by mass.
  • the content of CeO 2 is also indicated by external division. That is, the content of CeO 2 is preferably 2.0 when the total content of all glass components other than CeO 2 , Sb 2 O 3 , SnO 2 and SO 3 as oxides is 100.0% by mass. It is in the range of less than mass%, more preferably less than 1.0% by mass, still more preferably less than 0.5% by mass, still more preferably less than 0.1% by mass.
  • the content of CeO 2 may be 0% by mass. By setting the content of CeO 2 in the above range, the clarity of the glass can be improved.
  • the content of SO 3 is also indicated by external division. That is, the content of SO 3 is preferably 2.0 when the total content of all glass components other than SO 3, Sb 2 O 3 , SnO 2 , and CeO 2 as oxides is 100.0% by mass. It is in the range of less than mass%, more preferably less than 1.0% by mass, still more preferably less than 0.5% by mass, still more preferably less than 0.1% by mass.
  • the content of SO 3 may be 0% by mass.
  • the above glass is suitable as a glass for a near infrared cut filter.
  • a half value which is a wavelength at which the spectral transmittance becomes 50% at a wavelength of 600 nm or more can be used as an index, and a transmittance T1200 at a wavelength of 1200 nm can be used as an index.
  • the glass can also exhibit high visible light transmittance.
  • the transmittance T400 at a wavelength of 400 nm can be used as an index.
  • the glass can be used as a near-infrared cut filter glass having a thickness of 0.25 mm or less in one form.
  • the half value is preferably 650 nm or less, and further, 647 nm or less and 645 nm as the transmittance characteristic in terms of thickness 0.11 mm.
  • the transmittance characteristic in terms of thickness of 0.11 mm is preferably 600 nm or more, and more preferably 610 nm or more, 613 nm or more, 615 nm or more, 617 nm or more, 620 nm or more, 623 nm or more, 625 nm or more, and 628 nm or more.
  • the transmittance T1200 at a wavelength of 1200 nm is preferably 42.0% or less, and further 41.0% or less, 40.0% or less, 39 as the transmittance characteristic in terms of thickness 0.11 mm.
  • the transmittance T1200 at a wavelength of 1200 nm can be, for example, 10.0% or more, 12.0% or more, or 14.0% or more. Since it can be said that a lower rate means that the near-infrared ray cutting ability is superior, it is also preferable that the rate is lower than the above-exemplified value.
  • the transmission T400 at a wavelength of 400 nm is preferably 68.0% or more, more preferably 70.0% or more, and further. 71.0% or more, 72.0% or more, 73.0% or more, 74.0% or more, 75.0% or more, 76.0% or more, 77.0% or more, 78.0% or more, It is more preferable in the order of 79.0% or more and 80.0% or more.
  • the transmittance T400 at a wavelength of 400 nm can be, for example, 98.0% or less, 97.0% or less, or 96.0% or less. Since it can be said that a higher rate means better visible light transmittance, it is also preferable to exceed the above-exemplified value.
  • the half value is preferably 650 nm or less, and further, 647 nm or less as the transmittance characteristic in terms of thickness 0.21 mm.
  • the transmittance characteristic in terms of thickness 0.11 mm is preferably 600 nm or more, and more preferably 610 nm or more, 613 nm or more, 615 nm or more, 617 nm or more, 620 nm or more, 623 nm or more, 625 nm or more, and 628 nm or more.
  • the transmittance T1200 at a wavelength of 1200 nm is preferably 42.0% or less, and further 41.0% or less, 40.0% or less, 39 as the transmittance characteristic in terms of thickness 0.21 mm. 0.0% or less, 38.5% or less, 38.0% or less, 37.5% or less, 37.0% or less, 36.5% or less, 36.0% or less, 35.5% or less, 35.0 It is more preferable in the order of% or less.
  • the transmittance T1200 at a wavelength of 1200 nm can be, for example, 10.0% or more, 12.0% or more, or 14.0% or more.
  • the transmission T400 at a wavelength of 400 nm is preferably 68.0% or more, more preferably 70.0% or more, and further. 71.0% or more, 72.0% or more, 73.0% or more, 74.0% or more, 75.0% or more, 76.0% or more, 77.0% or more, 78.0% or more, It is more preferable in the order of 79.0% or more and 80.0% or more.
  • the transmittance T400 at a wavelength of 400 nm can be, for example, 98.0% or less, 97.0% or less, or 96.0% or less. Since it can be said that a higher rate means better visible light transmittance, it is also preferable to exceed the above-exemplified value.
  • the above transmittance characteristics are values obtained by the following methods. Glass samples are processed to have planes parallel to each other and optically polished, and the external transmittance at a wavelength of 200 to 1200 nm is measured. The external transmittance also includes the reflection loss of light rays on the sample surface.
  • the spectral transmittance B / A is calculated, where the intensity of the light beam perpendicularly incident on one plane that has been optically polished is the intensity A and the intensity of the light beam emitted from the other plane is the intensity B.
  • the wavelength at which the spectral transmittance is 50% at a wavelength of 600 nm or more is defined as the half value ⁇ T 50.
  • the spectral transmittance at a wavelength of 400 nm is T400, and the spectral transmittance at a wavelength of 1200 nm is T1200. If the glass to be measured is not a glass of a conversion thickness, the transmittance at each wavelength ⁇ is converted by the following formula, where d is the thickness of the glass, and the transmittance obtained by the conversion is calculated. From the characteristics, the converted values of the half values ⁇ T 50, T 400 and T 1200 can be obtained.
  • T ( ⁇ ) (1-R ( ⁇ )) 2 ⁇ exp (log e ((T 0 ( ⁇ ) / 100) / (1-R ( ⁇ )) 2 ) ⁇ d / d 0 ) ⁇ 100
  • T ( ⁇ ) converted transmission rate (%) at wavelength ⁇
  • T 0 ( ⁇ ) measured transmission rate (%) at wavelength ⁇
  • d glass thickness (mm)
  • d 0 converted thickness (Mm)
  • R ( ⁇ ) ((n ( ⁇ ) -1) / (n ( ⁇ ) +1)) 2 is the reflectance at wavelength ⁇
  • n ( ⁇ ) the refractive index at wavelength ⁇ . is there.
  • the glass can exhibit excellent weather resistance by having the composition described above.
  • the evaluation result of the weather resistance evaluated by the method described in Examples described later can be used as an index, and the evaluation result is preferably ⁇ or ⁇ , and is preferably ⁇ . More preferred.
  • the glass can also exhibit excellent meltability by having the composition described above.
  • the evaluation result of the meltability evaluated by the method described in Examples described later can be used as an index, and the evaluation result is preferably ⁇ .
  • the glass transition temperature of the glass is not particularly limited, but from the viewpoint of imparting processability and / or heat resistance in a subsequent process, Tg is preferably 300 ° C. or higher, and more preferably 310 ° C. Above, 320 ° C. or higher, 330 ° C. or higher, 340 ° C. or higher, and 350 ° C. or higher are more preferable. On the other hand, from the viewpoint of reducing the burden on the annealing furnace and the molding apparatus, the Tg is preferably 500 ° C. or lower, and further, 490 ° C. or lower, 480 ° C. or lower, 470 ° C.
  • Tm is preferably 870 ° C. or lower, and further, 860 ° C. or lower, 850 ° C. or lower, 840 ° C.
  • the temperature is more preferably °C or less, 780 °C or less, 770 °C or less, 760 °C or less, 750 °C or less.
  • the light weight of the near-infrared cut filter is preferable because it leads to the weight reduction of the element or device in which the filter is incorporated.
  • the specific gravity of the glass is preferably 3.50 or less, and further, 3.45 or less, 3.40 or less, 3.35 or less, 3.30 or less, 3.25 or less, 3. It is more preferably 20 or less, 3.15 or less, 3.10 or less, and 3.05 or less in that order.
  • the specific gravity can be, for example, 2.5 or more or 2.6 or more, but from the above viewpoint, it is preferable that the specific density is low, and therefore it is also preferable that the specific gravity is lower than the value exemplified here.
  • the glass can be obtained by blending, melting, and molding various glass raw materials.
  • the description described later can also be referred to.
  • the near-infrared absorbing glass is suitable as a glass for a near-infrared cut filter. Further, the near-infrared absorbing glass can be applied to optical elements (lenses, etc.) other than the near-infrared cut filter, and can be applied to various glass products and various deformations. It is possible.
  • Near infrared cut filter One aspect of the present invention relates to a near-infrared cut filter (hereinafter, also simply referred to as “filter”) made of the near-infrared absorbing glass.
  • the glass constituting the above filter is as described above.
  • the molten glass is appropriately used with glass raw materials such as phosphates, oxides, carbonates, nitrates, sulfates, and fluorides, and the raw materials are weighed and mixed so as to have a desired composition, and then a platinum crucible or the like is used. It is melted in a melting container at, for example, 800 ° C. to 1000 ° C. At that time, a lid made of platinum or the like can be used to suppress the volatilization of the volatile component. Further, the melting can be performed in the atmosphere, and in order to suppress the change in the valence of Cu, an oxygen atmosphere can be created or oxygen can be bubbled in the molten glass.
  • the molten glass becomes a homogenized molten glass in which bubbles are reduced (preferably free of bubbles) by stirring and clarification.
  • the glass After stirring and clarifying the molten glass, the glass is poured out and molded into a desired shape.
  • a glass forming method known methods such as casting, pipe outflow, roll, and pressing can be used.
  • the molded glass is transferred to an annealing furnace preheated near the transition point of the glass and slowly cooled to room temperature. In this way, the near-infrared cut filter can be manufactured.
  • a mold composed of a flat and horizontal bottom surface, a pair of side walls that oppose each other in parallel across the bottom surface, and a weir plate that closes one opening located between the pair of side walls is prepared.
  • molten glass is cast into this mold at a constant outflow rate.
  • the cast molten glass spreads in the mold and is formed into a glass plate regulated to a certain width by a pair of side walls.
  • the molded glass plate is continuously pulled out from the opening of the mold.
  • molding conditions such as the shape and dimensions of the mold and the outflow speed of the molten glass, a large-sized and thick glass block can be molded.
  • the molded glass molded body is transferred to an annealing furnace previously heated near the glass transition temperature and slowly cooled to room temperature.
  • the glass molded body whose strain has been removed by slow cooling is subjected to machining such as slicing, grinding, and polishing.
  • machining such as slicing, grinding, and polishing.
  • a near-infrared cut filter having a shape suitable for various purposes such as a plate shape and a lens shape.
  • a method of molding a preform made of the above glass, heating and softening the preform, and press-molding (particularly, a precision press for press-molding the final product without performing machining such as grinding or polishing on the optical functional surface). Molding method) etc.
  • An optical multilayer film may be formed on the surface of the filter, if necessary.
  • the near-infrared cut filter can have both excellent near-infrared cut ability and high visible light transmittance. According to such a near-infrared cut filter, the color sensitivity of the semiconductor image sensor can be satisfactorily corrected.
  • the near-infrared cut filter can be applied to an imaging device by combining it with a semiconductor image sensor.
  • a semiconductor image sensor is a device in which a semiconductor image sensor such as a CCD or CMOS is mounted in a package, and a light receiving portion is covered with a translucent member.
  • the translucent member can also serve as a near-infrared cut filter, or the translucent member can be separate from the near-infrared cut filter.
  • the image pickup device may also be provided with an optical element such as a lens or a prism for forming an image of a subject on a light receiving surface of a semiconductor image sensor.
  • an optical element such as a lens or a prism for forming an image of a subject on a light receiving surface of a semiconductor image sensor.
  • the near-infrared cut filter it is possible to provide an image pickup apparatus in which color sensitivity correction is performed well and an image having excellent image quality can be obtained.
  • the near-infrared cut filter can be a near-infrared cut filter having a thickness of 0.25 mm or less.
  • the thickness of the camera of the image sensor has been remarkably decreasing, and along with this, it is desired that the near-infrared cut filter also exhibits the performance with a thinner thickness.
  • the above-mentioned near-infrared cut filter is also suitable.
  • the thickness of the near infrared cut filter is 0.24 mm or less, 0.23 mm or less, 0.22 mm or less, 0.21 mm or less, 0.20 mm or less, 0.19 mm or less, 0.18 mm or less, 0.17 mm or less, 0.
  • the thickness of the near-infrared cut filter can be, for example, 0.21 mm or 0.11 mm. Further, the thickness of the near-infrared cut filter can be, for example, 0.50 or more, but is not limited to this.
  • the “thickness” refers to the thickness of the sample in the region where the transmittance is measured, and can be measured by a thickness gauge, a micrometer, or the like. For example, the thickness of the substantially central portion of the position through which the transmitted light passes may be measured, or the thickness of a plurality of points in the spot of the transmitted light may be measured and the average value thereof may be taken.
  • the value calculated as "thickness x Cu concentration" is 0.2000 mol / m from the viewpoint of making the near-infrared cut filter exhibiting even more excellent near-infrared cutting ability. It is preferably 2 or more, and more preferably 0.2100 mol / m 2 or more, 0.2200 mol / m 2 or more, 0.2300 mol / m 2 or more, 0.2400 mol / m 2 or more, 0.2500 mol / m 2 or more.
  • the value calculated as "thickness x Cu concentration" is preferably 1.000 mol / m 2 or less, and further 0.
  • Thickness x Cu concentration (Specific gravity of the composition) / (Molecular weight of the composition) ⁇ (Cation% of Cu ion / 100) ⁇ d / 10 ⁇ 10 4 The unit is mol / m 2 , and d is the thickness (mm).
  • the calculation method for (the molecular weight of the composition) of the above formula will be described.
  • (Molecular weight of the composition) is for all the components that make up the composition.
  • a calculation method will be described for the above (molecular weight of each component based on the cation).
  • (Molecular weight of each component based on cation) (Atomic weight of the element forming the cation) + (Atomic weight of oxygen x Coefficient according to valence)
  • the coefficients according to the valence are as follows. If the formal value is +1 then the coefficient is 0.5 If the formal value is +2, the coefficient is 1.0. If the formal value is +3, the coefficient is 1.5. If the formal value is +4, the coefficient is 2.0. If the formal value is +5, the coefficient is 2.5. If the formal value is +6, the coefficient is 3.0.
  • the above description regarding glass I and glass II can be referred to. Further, regarding the physical properties of the near-infrared cut filter, the above-mentioned description regarding the near-infrared absorbing glass can be referred to.
  • Examples 1 to 81, Comparative Examples A to F As a glass raw material, phosphate, fluoride, carbonate, nitrate, oxide, etc. are weighed and mixed so that 150 g to 300 g of glass having the composition shown in Table 1 can be obtained, and the mixture is placed in a platinum crucible or a quartz crucible. The mixture was charged, melted at 800 ° C. to 1000 ° C. for 60 to 180 minutes, stirred to defoam and homogenize, and then poured into a preheated mold to form a predetermined shape. The obtained glass compact was transferred to an annealing furnace heated to near the glass transition temperature and slowly cooled to room temperature. A test piece was cut out from the obtained glass, and both sides were mirror-polished to a thickness of about 0.2 mm, and then various evaluations were performed by the following methods.
  • ⁇ Weather resistance> Each test piece was kept in a constant temperature and humidity chamber having a temperature of 85 ° C. and a relative humidity of 85% for 168 hours. After that, each test piece was visually evaluated under a fluorescent lamp. From the evaluation results, the weather resistance was evaluated according to the following criteria. ⁇ : No deterioration is observed on the surface. ⁇ : Spiders were found on the surface, but there was no deliquescent. ⁇ : Deliquescent.
  • Table 1 Table 1-1 to Table 1-6
  • Table 2 Table 2-1 to Table 2-6)
  • Table 3 Table 3-1 to Table 3-6
  • the unit of (total) content of cations is cation%
  • the unit of (total) content of anions is anion%.
  • glass raw material 150 g of glass having a composition of phosphate, fluoride, carbonate, nitrate, oxide, etc., and 0.080% by mass of Sb 2 O 3 in the composition of Example 64 in Table 1 in an externally divided manner. Weigh and mix to obtain ⁇ 300 g, put into a platinum crucible or quartz crucible, melt under the same melting conditions as in Example 64, stir to defoam, homogenize, and then preheat the mold. It was poured into a glass and molded into a predetermined shape. The obtained glass compact was transferred to an annealing furnace heated to near the glass transition temperature and slowly cooled to room temperature.
  • a test piece was cut out from the obtained glass, and both sides were mirror-polished to a thickness of about 0.2 mm, and then the transmittance characteristics were evaluated by the above method.
  • the transmittance T1200 at a wavelength of 1200 nm was 27.9% and the transmittance T400 at a wavelength of 400 nm was 87.4% as values at a thickness of 0.11 mm (converted). From the comparison between the above evaluation result and the evaluation result of Example 64, it can be confirmed that the addition of Sb 2 O 3 can suppress the coloring and increase the visible light transmittance.
  • the constituent ions include one or more ions selected from the group consisting of P ion, Cu ion, O ion, Li ion, Na ion and K ion, and Mg ion, Ca ion, Sr ion and It contains at least one or more ions selected from the group consisting of Ba ions, and in the glass composition indicated by cation%, the Cu ion content is 15.0 cation% or less, and the P ion content is 55.0.
  • the cation ratio of the total content of Al ion and P ion to the total content of Mg ion, Ca ion, Sr ion, Ba ion, Zn ion and Cu ion ((Al ion + P ion) / ( Mg ion + Ca ion + Sr ion + Ba ion + Zn ion + Cu ion)) is 5.300 or less, and the total content of Mg ion, Ca ion, Sr ion and Ba ion with respect to the total content of Li ion, Na ion and K ion.
  • the O ion content is 85.0 anion% or more, and the ratio of the O ion content to the P ion content (O ion / P ion) is 3.
  • Near infrared absorbing glass of 300 or more is provided.
  • the above glass can be a near-infrared absorbing glass having excellent near-infrared ray cutting ability, high visible light transmittance, and excellent weather resistance and melting property.
  • the content of P ions can be 30.0 cation% or more and 50.0 cation% or less in the glass composition indicated by cation% of the glass.
  • the Li ion content can be 10.0 cation% or more in the glass composition indicated by cation% of the glass.
  • the Cu ion content can be 2.1 cation% or more and 15.0 cation% or less in the glass composition indicated by cation% of the glass.
  • the above ratio (O ion / P ion) can be 3.400 or more.
  • the ratio of Zn ions to the total content of Mg ions, Ca ions, Sr ions, Ba ions and Zn ions in the glass composition of the glass in terms of cation% can be 0.600 or less.
  • the content of O ions can be 90.0% or less in the glass composition indicated by the anion% of the glass.
  • the glass can have a transmittance T1200 at a wavelength of 1200 nm of 42.0% or less as a transmittance characteristic in terms of a thickness of 0.11 mm.
  • the glass can have a transmittance T400 of 68.0% or more at a wavelength of 400 nm as a transmittance characteristic in terms of a thickness of 0.11 mm.
  • the glass can have a transmittance T1200 at a wavelength of 1200 nm of 42.0% or less as a transmittance characteristic in terms of thickness 0.21 mm.
  • the glass can have a transmittance T400 of 68.0% or more at a wavelength of 400 nm as a transmittance characteristic in terms of thickness 0.21 mm.
  • a near-infrared cut filter made of the above-mentioned near-infrared absorbing glass is provided.
  • the thickness of the near-infrared cut filter can be 0.25 mm or less.
  • the near-infrared cut filter can have a wavelength in the range of 600 nm to 650 nm, which has a transmittance of 50% at a wavelength of 600 nm or more, as a transmittance characteristic in terms of thickness of 0.11 mm.
  • the near-infrared cut filter can have a transmittance T1200 at a wavelength of 1200 nm of 42.0% or less as a transmittance characteristic in terms of a thickness of 0.11 mm.
  • the near-infrared cut filter can have a transmittance T400 at a wavelength of 400 nm of 68.0% or more as a transmittance characteristic in terms of a thickness of 0.11 mm.
  • the near-infrared cut filter can have a wavelength in the range of 600 nm to 650 nm, which has a transmittance of 50% at a wavelength of 600 nm or more, as a transmittance characteristic in terms of thickness of 0.21 mm.
  • the near-infrared cut filter can have a transmittance T1200 at a wavelength of 1200 nm of 42.0% or less as a transmittance characteristic in terms of a thickness of 0.21 mm.
  • the near-infrared cut filter can have a transmittance T400 at a wavelength of 400 nm of 68.0% or more as a transmittance characteristic in terms of thickness 0.21 mm.
  • the near-infrared absorbing glass according to one aspect of the present invention can be obtained by adjusting the composition described in the specification with respect to the above-exemplified glass composition.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Glass Compositions (AREA)
  • Optical Filters (AREA)
PCT/JP2020/048961 2019-12-27 2020-12-25 近赤外線吸収ガラスおよび近赤外線カットフィルタ Ceased WO2021132645A1 (ja)

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JP2021567712A JP7662535B2 (ja) 2019-12-27 2020-12-25 近赤外線吸収ガラスおよび近赤外線カットフィルタ
CN202080090602.4A CN114901606A (zh) 2019-12-27 2020-12-25 近红外线吸收玻璃及近红外线截止滤光片
KR1020227022054A KR102849066B1 (ko) 2019-12-27 2020-12-25 근적외선 흡수 유리 및 근적외선 컷 필터
CN202411197549.4A CN118993534A (zh) 2019-12-27 2020-12-25 近红外线吸收玻璃及近红外线截止滤光片
US17/788,459 US12297146B2 (en) 2019-12-27 2020-12-25 Near-infrared absorbing glass and near-infrared cutoff filter
JP2025061620A JP2025102937A (ja) 2019-12-27 2025-04-03 近赤外線吸収ガラスおよび近赤外線カットフィルタ

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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
JP2011168455A (ja) * 2010-02-19 2011-09-01 Asahi Glass Co Ltd 近赤外線カットフィルタガラス
KR20110102658A (ko) * 2010-03-11 2011-09-19 한국세라믹기술원 근적외선 필터용 유리조성물 및 이를 이용한 근적외선 필터용 유리의 제조방법
WO2012018026A1 (ja) * 2010-08-03 2012-02-09 旭硝子株式会社 近赤外線カットフィルタガラスおよびその製造方法
JP2013053058A (ja) * 2011-08-11 2013-03-21 Hoya Corp フツリン酸ガラス及びその製造方法並びに近赤外光吸収フィルター
JP2014125395A (ja) * 2012-12-27 2014-07-07 Nippon Electric Glass Co Ltd ガラス
JP2019038719A (ja) * 2017-08-25 2019-03-14 日本電気硝子株式会社 近赤外線吸収ガラス

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JPS57149845A (en) * 1981-03-09 1982-09-16 Ohara Inc Filter glass for absorbing near infrared ray
JPH11209144A (ja) * 1998-01-21 1999-08-03 Hoya Corp 近赤外吸収フィルター用ガラスおよびそれを用いた近赤外吸収フィルター
JP2017014044A (ja) * 2015-06-30 2017-01-19 Hoya株式会社 近赤外線吸収ガラスおよびフィルター

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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
JP2011168455A (ja) * 2010-02-19 2011-09-01 Asahi Glass Co Ltd 近赤外線カットフィルタガラス
KR20110102658A (ko) * 2010-03-11 2011-09-19 한국세라믹기술원 근적외선 필터용 유리조성물 및 이를 이용한 근적외선 필터용 유리의 제조방법
WO2012018026A1 (ja) * 2010-08-03 2012-02-09 旭硝子株式会社 近赤外線カットフィルタガラスおよびその製造方法
JP2013053058A (ja) * 2011-08-11 2013-03-21 Hoya Corp フツリン酸ガラス及びその製造方法並びに近赤外光吸収フィルター
JP2014125395A (ja) * 2012-12-27 2014-07-07 Nippon Electric Glass Co Ltd ガラス
JP2019038719A (ja) * 2017-08-25 2019-03-14 日本電気硝子株式会社 近赤外線吸収ガラス

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KR20220110776A (ko) 2022-08-09
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JPWO2021132645A1 (https=) 2021-07-01
CN118993534A (zh) 2024-11-22
US20230057228A1 (en) 2023-02-23
JP7662535B2 (ja) 2025-04-15
TWI899131B (zh) 2025-10-01
US12297146B2 (en) 2025-05-13
TW202140396A (zh) 2021-11-01
JP2025102937A (ja) 2025-07-08

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