WO2010038597A1 - Verre optique et procédé de suppression de la détérioration de la transmittance spectrale - Google Patents

Verre optique et procédé de suppression de la détérioration de la transmittance spectrale Download PDF

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Publication number
WO2010038597A1
WO2010038597A1 PCT/JP2009/065920 JP2009065920W WO2010038597A1 WO 2010038597 A1 WO2010038597 A1 WO 2010038597A1 JP 2009065920 W JP2009065920 W JP 2009065920W WO 2010038597 A1 WO2010038597 A1 WO 2010038597A1
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component
glass
optical glass
content
optical
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PCT/JP2009/065920
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English (en)
Japanese (ja)
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進 上原
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株式会社オハラ
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Priority to CN2009801381370A priority Critical patent/CN102164866A/zh
Publication of WO2010038597A1 publication Critical patent/WO2010038597A1/fr

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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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B13/00—Optical objectives specially designed for the purposes specified below
    • G02B13/18—Optical objectives specially designed for the purposes specified below with lenses having one or more non-spherical faces, e.g. for reducing geometrical aberration
    • 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
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • 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
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
    • 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
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
    • 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
    • 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
    • C03C3/14—Silica-free oxide glass compositions containing boron
    • 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
    • C03C3/14—Silica-free oxide glass compositions containing boron
    • C03C3/145—Silica-free oxide glass compositions containing boron 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
    • C03C3/14—Silica-free oxide glass compositions containing boron
    • C03C3/15—Silica-free oxide glass compositions containing boron containing rare earths
    • 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
    • C03C3/14—Silica-free oxide glass compositions containing boron
    • C03C3/15—Silica-free oxide glass compositions containing boron containing rare earths
    • C03C3/155—Silica-free oxide glass compositions containing boron containing rare earths containing zirconium, titanium, tantalum or niobium
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements

Definitions

  • the present invention relates to optical glass and a method for suppressing deterioration of spectral transmittance.
  • Such optical elements can be produced by grinding and polishing molded glass obtained by heating and softening a glass material (reheat press molding), or by grinding and polishing a gob or glass block.
  • a method precision press molding is used in which a material or a preform material formed by known flotation molding is heat-softened and pressure-molded with a mold having a highly accurate molding surface.
  • Patent Document 1 discloses an optical glass having a refractive index (n d ) of 1.63 to 1.75 and an Abbe number ( ⁇ d ) of 23 to 35.
  • Patent Document 2 discloses an optical glass having a refractive index (n d ) of 1.80 or more and an Abbe number ( ⁇ d ) of 30 or less.
  • the glasses disclosed in Patent Documents 1 and 2 have a problem of solarization in which the spectral transmittance is reduced by ultraviolet rays contained in sunlight or the like. Since the glass having a large solarization is colored by being irradiated with ultraviolet rays for a long time, it has been difficult to maintain a desired spectral transmittance at the beginning of manufacture.
  • the object of the present invention has been made in view of the above-mentioned problems, and the object of the present invention is to provide an optical glass and a method for suppressing deterioration of spectral transmittance in which deterioration of spectral transmittance with time is suppressed. There is to get.
  • the present inventors have conducted intensive test studies, and as a result, the content of the Sb 2 O 3 component contained in the optical glass is reduced, and more preferably Pt mixed in the optical glass.
  • the content of the component and / or Fe component it was found that solarization of the optical glass was reduced, and the present invention was completed.
  • the present invention provides the following.
  • the content of the Sb 2 O 3 component is 0.5% or less by mass% with respect to the total glass mass of the oxide equivalent composition, and solarization (amount of degradation of spectral transmittance at a wavelength of 450 nm) is 5.
  • Optical glass that is 0% or less.
  • the optical glass according to any one of (1) to (8) which has a glass transition point (Tg) of 400 ° C. or higher and 650 ° C. or lower.
  • the present invention by reducing the content of Sb 2 O 3 component contained in the optical glass, more preferably by adjusting the content of Pt component and / or Fe component mixed in the optical glass, It is possible to obtain an optical glass in which the solarization of the optical glass due to long-time irradiation is reduced and a method for suppressing the deterioration of spectral transmittance.
  • Sb 2 O 3 ingredient content is a diagram showing the relationship between content and solarization of Pt component. It is a figure which shows the relationship between content of Fe component, and solarization.
  • the content of Sb 2 O 3 component is 0.5% or less by mass% with respect to the total mass of the glass having an oxide equivalent composition, and solarization (amount of degradation of spectral transmittance at a wavelength of 450 nm). ) Is 5.0% or less.
  • degradation suppression method of the spectral transmittance of the glass of the present invention is to reduce the content of Sb 2 O 3 component contained in the glass.
  • Sb 2 O 3 component contained in the glass solarization of the optical glass is reduced. For this reason, it is possible to more reliably produce a lens preform or an optical element in which deterioration of the spectral transmittance over time is suppressed.
  • optical glass First, components and physical properties of the optical glass of the present invention will be described.
  • the glass used in the spectral transmittance deterioration suppressing method of the present invention is not particularly limited as long as the content of the Sb 2 O 3 component is not more than a predetermined glass, but among them, optical glass as described below is used. Preferably there is.
  • the composition range of each component constituting the optical glass of the present invention will be described below.
  • the contents of the respective components are all expressed in mass% with respect to the total glass mass of the oxide conversion composition.
  • the “oxide equivalent composition” means that the oxide, composite salt, metal fluoride, etc. used as the raw material of the glass component of the present invention are all decomposed and changed into oxides when melted.
  • the composition represents each component contained in the glass, with the total mass of the generated oxide being 100% by mass.
  • the Sb 2 O 3 component is a component having a defoaming effect when the glass is melted, but it contributes to the enhancement of solarization of the optical glass by irradiation with ultraviolet rays.
  • the content of the Sb 2 O 3 component with respect to the total glass mass of the oxide-converted composition is preferably 0.5%, more preferably 0.3%, and most preferably 0.2%.
  • the content of Sb 2 O 3 component is not particularly disadvantageous technically Within this range, as shown in FIG.
  • the content of the Sb 2 O 3 component greater than 0% thus, solarization can be reduced as compared with the case where no Sb 2 O 3 component is contained. Therefore, the content of the Sb 2 O 3 component with respect to the total glass mass of the oxide equivalent composition is preferably more than 0%, more preferably 0.0001%, and most preferably 0.001%.
  • the Sb 2 O 3 component for example, Sb 2 O 3 , Sb 2 O 5 , Na 2 H 2 Sb 2 O 7 ⁇ 5H 2 O, or the like can be used as a raw material.
  • the Pt component is a component that is mixed into the optical glass from a member such as a platinum crucible when the optical glass is manufactured, which contributes to an increase in solarization of the optical glass by irradiation with ultraviolet rays.
  • a member such as a platinum crucible when the optical glass is manufactured
  • the content of the Pt component of the optical glass is preferably 15 ppm, more preferably 10 ppm, and most preferably 7 ppm.
  • the Pt component is a component contained in the optical glass by elution from a member containing platinum, such as a platinum crucible, even if the Pt component is not included as a material. Therefore, for example, by shortening the melting time of the glass in the platinum crucible or lowering the melting temperature of the glass, the mixing amount into the optical glass can be reduced. As shown in FIG. 2, in addition to the suppression of the content of the Pt component, the suppression of the content of the Sb 2 O 3 component is simultaneously performed, so that the solarization of the optical glass is more easily reduced. Also at this time, by making the content of the Sb 2 O 3 component more than 0%, solarization can be lowered as compared with the case where the Sb 2 O 3 component is not contained.
  • the Fe component is a component mixed into the optical glass, for example, as an impurity of the raw material of the optical glass when the optical glass is manufactured, and contributes to the enhancement of solarization of the optical glass by irradiation with ultraviolet rays.
  • the upper limit of the content of the Fe component with respect to the total glass mass of the oxide conversion composition is preferably 50 ppm, more preferably 10 ppm, and most preferably 5 ppm.
  • the Fe component for example, by selecting a raw material for optical glass having a small amount of Fe component, the amount mixed into the optical glass can be reduced. In addition to suppression of the content of the Fe component, simultaneous suppression of the contents of the Sb 2 O 3 component and the Pt component makes it easier to reduce the solarization of the optical glass.
  • the SiO 2 component is an oxide that forms glass, and is a useful component for forming a glass skeleton.
  • the content of the SiO 2 component is 1.0% or more, the glass network structure increases to such an extent that a stable glass can be obtained, so that the devitrification resistance of the glass can be improved.
  • the content of SiO 2 component is preferably below 60.0%, the refractive index of the glass is hardly lowered, it is possible to easily obtain an optical glass having a desired refractive index.
  • the content of the SiO 2 component with respect to the total glass mass of the oxide conversion composition is preferably 1.0%, more preferably 5.0%, and most preferably 10.0% as the lower limit, preferably 60.0. %, More preferably 50.0%, and most preferably 40.0%.
  • SiO 2 component may be contained in the glass by using as a raw material such as SiO 2, K 2 SiF 6, Na 2 SiF 6 or the like.
  • the Nb 2 O 5 component is a component that decreases the partial dispersion ratio ( ⁇ g, F) of the glass and increases the refractive index of the glass.
  • the content of the Nb 2 O 5 component with respect to the total glass mass of the oxide conversion composition is preferably 65.0%, more preferably 60.0%, and most preferably 55.0%.
  • the desired refractive index and partial dispersion ratio ( ⁇ g, F) can be easily obtained by making the content of the Nb 2 O 5 component 10.0% or more.
  • the content of the Nb 2 O 5 component with respect to the total glass mass of the oxide conversion composition is preferably 10.0%, more preferably 15.0%, and most preferably 20.0%.
  • the Nb 2 O 5 component can be contained in the glass using, for example, Nb 2 O 5 as a raw material.
  • TiO 2 component increases the refractive index of the glass, a component to lower the Abbe number of the glass, an optional component of the optical glass of the present invention.
  • the content of the TiO 2 component is preferably 40.0%, more preferably 30.0%, and most preferably 20.0%.
  • the content of the TiO 2 component with respect to the total glass mass of the oxide conversion composition is preferably more than 0%, more preferably 0.1%, and most preferably 1.0%.
  • TiO 2 component may be contained in the glass by using as the starting material for example TiO 2 or the like.
  • the B 2 O 3 component is an oxide that forms glass, is a component useful for forming a glass skeleton, and is an optional component in the optical glass of the present invention.
  • the content of the B 2 O 3 component is 40.0% or less, the refractive index of the glass is hardly lowered, and the internal transmittance in a short wavelength region of visible light is hardly deteriorated. Therefore, the content of the B 2 O 3 component with respect to the total glass mass of the oxide conversion composition is preferably 40.0%, more preferably 20.0%, and most preferably 10.0%.
  • the B 2 O 3 component can be contained in the glass using, for example, H 3 BO 3 , Na 2 B 4 O 7 , Na 2 B 4 O 7 .10H 2 O, BPO 4 or the like as a raw material.
  • an optical glass with reduced solarization can be produced without containing the B 2 O 3 component, but the content of the B 2 O 3 component is 0.1% or more. By doing so, the optical glass with improved devitrification resistance can be obtained more easily. Therefore, the content of the B 2 O 3 component with respect to the total glass mass of the oxide-converted composition is preferably 0.1%, more preferably 0.5%, and most preferably 1.0%.
  • the GeO 2 component is a component that increases the refractive index of the glass and stabilizes the glass to reduce devitrification during molding, and is an optional component in the optical glass of the present invention.
  • the content of the GeO 2 component is preferably 30.0%, more preferably 20.0%, and most preferably 10.0%.
  • the GeO 2 component can be contained in the glass using, for example, GeO 2 as a raw material.
  • the Al 2 O 3 component is a component that improves the chemical durability of the glass, and is an optional component in the optical glass of the present invention. Therefore, the upper limit of the content of the Al 2 O 3 component with respect to the total glass mass of the oxide conversion composition is preferably 15.0%, more preferably 10.0%, and most preferably 5.0%.
  • the Al 2 O 3 component can be contained in the glass using, for example, Al 2 O 3 , Al (OH) 3 , AlF 3 or the like as a raw material.
  • the ZrO 2 component is a component that has the effect of lowering the liquidus temperature of the glass to increase the devitrification resistance, improving the chemical durability of the glass, and lowering the partial dispersion ratio ( ⁇ g, F) of the glass.
  • the chemical durability of the glass can be increased by setting the content of the ZrO 2 component to 20.0% or less. Therefore, the content of the ZrO 2 component with respect to the total glass mass of the oxide conversion composition is preferably 20.0%, more preferably 15.0%, and most preferably 11.0%.
  • the ZrO 2 component can be contained in the glass using, for example, ZrO 2 , ZrF 4 or the like as a raw material.
  • the Ta 2 O 5 component is a component that increases the refractive index of the glass and decreases the devitrification temperature of the glass, and is an optional component in the optical glass of the present invention.
  • the devitrification resistance of the glass can be maintained by setting the content of the Ta 2 O 5 component to 20.0% or less. Therefore, the content of the Ta 2 O 5 component with respect to the total glass mass of the oxide conversion composition is preferably 20.0%, more preferably 15.0%, and most preferably 10.0%.
  • the Ta 2 O 5 component can be contained in the glass using, for example, Ta 2 O 5 as a raw material.
  • the WO 3 component is a component that increases the refractive index of the glass and decreases the devitrification temperature of the glass, and is an optional component in the optical glass of the present invention.
  • the content of the WO 3 component is preferably 20.0%, more preferably 15.0%, and most preferably 10.0%.
  • the WO 3 component can be contained in the glass using, for example, WO 3 as a raw material.
  • the ZnO component is a component that lowers the devitrification temperature of the glass and lowers the glass transition point (Tg), and is an optional component in the optical glass of the present invention.
  • the chemical durability of the glass can be enhanced by setting the content of the ZnO component to 30.0% or less.
  • the content of the ZnO component with respect to the total glass mass of the oxide conversion composition is preferably 30.0%, more preferably 20.0%, and most preferably 10.0%.
  • the ZnO component can be contained in the glass using, for example, ZnO, ZnF 2 or the like as a raw material.
  • the MgO component is a component that lowers the melting temperature of the glass and is an optional component in the optical glass of the present invention.
  • the chemical durability of the glass can be increased by setting the content of the MgO component to 20.0% or less. Therefore, the content of the MgO component with respect to the total glass mass of the oxide conversion composition is preferably 20.0%, more preferably 15.0%, and most preferably 10.0%.
  • the MgO component can be contained in the glass using, for example, MgO, MgCO 3 , MgF 2 or the like as a raw material.
  • the CaO component is a component that lowers the devitrification temperature of the glass and is an optional component in the optical glass of the present invention.
  • the devitrification resistance of the glass can be improved by setting the content of the CaO component to 30.0% or less. Therefore, the content of the CaO component with respect to the total glass mass of the oxide conversion composition is preferably 30.0%, more preferably 20.0%, and most preferably 10.0%.
  • the CaO component can be contained in the glass using, for example, CaCO 3 , CaF 2 or the like as a raw material.
  • the SrO component is a component that lowers the devitrification temperature of the glass and adjusts the refractive index of the glass, and is an optional component in the optical glass of the present invention.
  • the devitrification resistance of the glass can be enhanced by setting the content of the SrO component to 30.0% or less. Therefore, the content of the SrO component with respect to the total glass mass of the oxide conversion composition is preferably 30.0%, more preferably 20.0%, and most preferably 10.0%.
  • the SrO component can be contained in the glass using, for example, Sr (NO 3 ) 2 , SrF 2 or the like as a raw material.
  • the BaO component is a component that lowers the devitrification temperature of the glass and adjusts the optical constant of the glass.
  • the devitrification resistance of the glass can be improved by setting the content of the BaO component to 30.0% or less. Therefore, the content of the BaO component with respect to the total glass mass of the oxide-converted composition is preferably 30.0%, more preferably 20.0%, and most preferably 10.0%.
  • the BaO component can be contained in the glass using, for example, BaCO 3 , Ba (NO 3 ) 2 or the like as a raw material.
  • the RO component (wherein R is one or more selected from the group consisting of Zn, Mg, Ca, Sr, and Ba) lowers the devitrification temperature of the glass as described above, and is refracted.
  • R is one or more selected from the group consisting of Zn, Mg, Ca, Sr, and Ba
  • the total content of the RO component with respect to the total glass mass of the oxide conversion composition is preferably 30.0%, more preferably 20.0%, and most preferably 10.0%.
  • the optical glass of the present invention it is possible to produce an optical glass with reduced solarization without containing an RO component, but by making the total content of RO components 1.0% or more, Adjustment of the optical constant of the glass can be facilitated. Therefore, the total content of the RO component with respect to the total glass mass of the oxide conversion composition is preferably 0.1%, more preferably 0.5%, and most preferably 1.0%.
  • the Li 2 O component is a component that lowers the partial dispersion ratio ( ⁇ g, F) of the glass, lowers the devitrification temperature of the glass, and lowers the glass transition point (Tg), and is an optional component in the optical glass of the present invention. It is. In particular, when the content of the Li 2 O component is 20.0% or less, solarization becomes difficult to increase, so that an optical glass with reduced solarization can be easily obtained. Therefore, the content of the Li 2 O component with respect to the total glass mass of the oxide conversion composition is preferably 20.0%, more preferably 15.0%, and most preferably 10.0%.
  • the total content of Li 2 O component above 0.1%
  • the glass transition point (Tg) becomes low, it is possible to obtain a glass that is easy to press-mold. Therefore, the total content of the Li 2 O component with respect to the total glass mass of the oxide conversion composition is preferably 0.1%, more preferably 0.5%, and most preferably 1.0%.
  • the Li 2 O component can be contained in the glass using, for example, Li 2 CO 3 , LiNO 3 , LiF or the like as a raw material.
  • Na 2 O component is a component for glass transition point (Tg) lower, are optional components of the optical glass of the present invention.
  • Tg glass transition point
  • the content of the Na 2 O component with respect to the total glass mass of the oxide conversion composition is preferably 30.0%, more preferably 20.0%, and most preferably 15.0%.
  • the total Na 2 O content component in the optical glass of the present invention, although it is possible even without containing Na 2 O component to produce a reduced optical glass solarization, the total Na 2 O content component than 0.1% By doing so, since the glass transition point (Tg) becomes low, it is possible to obtain a glass that is easy to press-mold. Therefore, the total content of the Na 2 O component with respect to the total glass mass of the oxide conversion composition is preferably 1.0%, more preferably 2.0%, and most preferably 3.0%.
  • the Na 2 O component can be contained in the glass using, for example, Na 2 CO 3 , NaNO 3 , NaF, Na 2 SiF 6 or the like as a raw material.
  • K 2 O component is a component for glass transition point (Tg) lower, are optional components of the optical glass of the present invention.
  • Tg glass transition point
  • the content of the K 2 O component with respect to the total glass mass of the oxide conversion composition is preferably 20.0%, more preferably 10.0%, and most preferably 2.0%.
  • the K 2 O component can be contained in the glass using, for example, K 2 CO 3 , KNO 3 , KF, KHF 2 , K 2 SiF 6 or the like as a raw material.
  • the mass sum of the contents of the Rn 2 O component (wherein Rn is one or more selected from the group consisting of Li, Na, and K) is 20.0% or less. preferable. By making this mass sum 20.0% or less, an increase in the devitrification temperature of the glass can be suppressed, so that vitrification can be facilitated. Therefore, the mass sum of the content of the Rn 2 O component with respect to the total glass mass of the oxide conversion composition is preferably 20.0%, more preferably 17.0%, and most preferably 15.0%. In the optical glass of the present invention, it is possible to produce an optical glass with reduced solarization without containing the Rn 2 O component, but the total content of the Rn 2 O component is 1.0% or more.
  • the total content of the Rn 2 O component with respect to the total glass mass of the oxide conversion composition is preferably 1.0%, more preferably 2.0%, and most preferably 5.0%.
  • the La 2 O 3 component is a component that increases the Abbe number of the glass while increasing the refractive index of the glass, and is an optional component in the optical glass of the present invention.
  • the devitrification resistance of the glass can be improved by setting the content of the La 2 O 3 component to 50.0% or less. Therefore, the content of the La 2 O 3 component with respect to the total glass mass of the oxide conversion composition is preferably 50.0%, more preferably 20.0%, and most preferably 5.0%.
  • the La 2 O 3 component for example, La 2 O 3 , La (NO 3 ) 3 .XH 2 O (X is an arbitrary integer) or the like can be used as a raw material.
  • the Gd 2 O 3 component is a component that increases the Abbe number of the glass while increasing the refractive index of the glass, and is an optional component in the optical glass of the present invention.
  • the devitrification resistance of the glass can be enhanced by setting the content of the Gd 2 O 3 component to 30.0% or less. Therefore, the content of the Gd 2 O 3 component with respect to the total glass mass of the oxide conversion composition is preferably 30.0%, more preferably 10.0%, and most preferably 5.0%.
  • the Gd 2 O 3 component for example, Gd 2 O 3 , GdF 3 or the like can be used as a raw material.
  • the Y 2 O 3 component while increasing the refractive index of the glass, or to enhance the devitrification resistance of the glass, an optional component of the optical glass of the present invention.
  • the content of the Y 2 O 3 component 30.0% or less, an increase in the liquidus temperature of the glass can be suppressed, so that it is difficult to devitrify the glass when the glass is produced from a molten state. Can do. Therefore, the content of the Y 2 O 3 component with respect to the total glass mass of the oxide conversion composition is preferably 30.0%, more preferably 15.0%, and most preferably 5.0%.
  • the Y 2 O 3 component for example, Y 2 O 3 , YF 3 or the like can be used as a raw material.
  • the mass sum of the contents of the Ln 2 O 3 component (wherein Ln is one or more selected from the group consisting of La, Y, and Gd) is 30.0% or less. Is preferred. By making this mass sum 30.0% or less, the devitrification resistance of the glass can be enhanced. Therefore, the mass sum of the content of the Ln 2 O 3 component with respect to the total glass mass of the oxide conversion composition is preferably 30.0%, more preferably 15.0%, and most preferably 5.0%. .
  • Ga 2 O 3 component is a component that raises the refractive index of the glass, an optional component of the optical glass of the present invention.
  • the content of the Ga 2 O 3 component with respect to the total glass mass of the oxide-converted composition is preferably 20.0%, more preferably 15.0%, and most preferably 10.0%.
  • the Ga 2 O 3 component can be contained in the glass using, for example, Ga 2 O 3 as a raw material.
  • TeO 2 component increases the refractive index of the glass is a component of glass transition point (Tg) lower, are optional components of the optical glass of the present invention.
  • Tg glass transition point
  • the content of the TeO 2 component with respect to the total glass mass of the oxide conversion composition is preferably 50.0%, more preferably 30.0%, still more preferably 15.0%, and most preferably 10. Less than 0%.
  • the TeO 2 component can be contained in the glass using, for example, TeO 2 as a raw material.
  • Bi 2 O 3 component increasing the refractive index of the glass is a component of glass transition point (Tg) lower, are optional components of the optical glass of the present invention.
  • Tg glass transition point
  • the content of the Bi 2 O 3 component with respect to the total glass mass of the oxide conversion composition is preferably 50.0%, more preferably 30.0%, and even more preferably 15.0%, and most preferably It is less than 10.0%.
  • the Bi 2 O 3 component can be contained in the glass using, for example, Bi 2 O 3 as a raw material.
  • the CeO 2 component is a component that adjusts the optical constant of the glass and improves the solarization of the glass, and is an optional component in the optical glass of the present invention.
  • the CeO 2 component content with respect to the total glass mass of the oxide conversion composition is preferably 10.0%, more preferably 5.0%, and most preferably 1.0%.
  • the CeO 2 component is not substantially contained in terms of coloring of the glass.
  • the CeO 2 component can be contained in the glass using, for example, CeO 2 as a raw material.
  • components of the fining defoaming of glass is not limited to the above Sb 2 O 3 ingredients may be used known refining agents and defoamers in the field of glass production, or a combination thereof .
  • optical glass of the present invention other components can be added as necessary within a range not impairing the properties of the glass.
  • the transition metal components such as V, Cr, Mn, Co, Ni, Cu, Ag, and Mo, excluding Ti, Zr, and Nb, are colored in the glass even when each of them is contained alone or in combination. Since there is a property of causing absorption at a specific wavelength in the visible region, it is preferable that the optical glass using the wavelength in the visible region does not substantially contain.
  • lead compounds such as PbO and arsenic compounds such as As 2 O 3 and components of Th, Cd, Tl, Os, Be and Se have been refraining from being used as harmful chemical substances in recent years.
  • Environmental measures are required not only in the manufacturing process but also in the processing process and disposal after commercialization. Therefore, when importance is placed on the environmental impact, it is preferable not to substantially contain them except for inevitable mixing.
  • the optical glass is substantially free of substances that pollute the environment. Therefore, the optical glass can be manufactured, processed, and discarded without taking any special environmental measures.
  • the glass that is preferably used as the optical glass of the present invention cannot be expressed directly in the description of mol% because the composition is represented by mass% with respect to the total mass of the glass in terms of oxide composition, but is required in the present invention.
  • the composition expressed by mol% of each component present in the glass composition satisfying various properties generally takes the following values in terms of oxide conversion.
  • the optical glass of the present invention preferably has a solarization of 5.0% or less.
  • the device incorporating the optical glass is unlikely to deteriorate in color balance even after long-term use.
  • the optical glass of the present invention is particularly effective when used at a high temperature as in a vehicle.
  • the upper limit of solarization of the optical glass of the present invention is preferably 5.0%, more preferably 4.8%, and most preferably 4.5%.
  • “solarization” refers to the amount of degradation of spectral transmittance at 450 nm when glass is irradiated with ultraviolet rays, and specifically, Japanese Optical Glass Industry Standard JOGIS 04-1994 “ According to “Measurement method of solarization of optical glass”, the spectral transmittance before and after irradiation with light from a high-pressure mercury lamp is measured.
  • the optical glass of the present invention has a desired partial dispersion ratio ( ⁇ g, F) in the relational expression with the Abbe number ( ⁇ d ), and can correct the chromatic aberration of the lens with higher accuracy. More specifically, the partial dispersion ratio ( ⁇ g, F) of the optical glass of the present invention is ( ⁇ 1.60 ⁇ 10 ⁇ 3 ⁇ ) in the range of ⁇ d ⁇ 25 with respect to the Abbe number ( ⁇ d ). ⁇ d +0.6346) ⁇ ( ⁇ g, F) ⁇ ( ⁇ 4.21 ⁇ 10 ⁇ 3 ⁇ ⁇ d +0.7207) and ( ⁇ 2.50 ⁇ 10 ⁇ 10) in the range of ⁇ d > 25.
  • the partial dispersion ratio ( ⁇ g, F) of the optical glass at ⁇ d ⁇ 25 is preferably ( ⁇ 1.60 ⁇ 10 ⁇ 3 ⁇ ⁇ d +0.6346), more preferably ( ⁇ 1.60 ⁇ 10 6).
  • the partial dispersion ratio ( ⁇ g, F) of the optical glass at ⁇ d > 25 is preferably ( ⁇ 2.50 ⁇ 10 ⁇ 3 ⁇ ⁇ d +0.6571), more preferably ( ⁇ 2.50 ⁇ 10 ⁇ ). 3 ⁇ ⁇ d +0.6591), and most preferably ( ⁇ 2.50 ⁇ 10 ⁇ 3 ⁇ ⁇ d +0.6611) is set as the lower limit.
  • the upper limit of the partial dispersion ratio ( ⁇ g, F) of the optical glass is preferably ( ⁇ 4.21 ⁇ 10 ⁇ 3 ⁇ ⁇ d +0.7207), more preferably ( ⁇ 4.21 ⁇ 10 ⁇ 3 ⁇ ). ( ⁇ d +0.7187), more preferably ( ⁇ 4.21 ⁇ 10 ⁇ 3 ⁇ ⁇ d +0.7177), and most preferably ( ⁇ 4.21 ⁇ 10 ⁇ 3 ⁇ ⁇ d +0.7172).
  • the partial dispersion ratio ( ⁇ g, F) of general glass is higher than that of the normal line, and the partial dispersion ratio ( ⁇ g, F) of general glass is high.
  • the optical glass of the present invention preferably has a glass transition point (Tg) of 400 ° C. or higher and 650 ° C. or lower.
  • Tg glass transition point
  • the glass transition point (Tg) is 400 ° C. or higher, adverse effects due to frictional heat generated when polishing the glass can be reduced.
  • the glass transition point (Tg) is 650 ° C. or lower, press molding at a lower temperature becomes possible, so that the oxidation of the mold used for mold press molding is reduced to extend the life. Can do.
  • the glass transition point (Tg) of the optical glass of the present invention is preferably 400 ° C., more preferably 450 ° C., most preferably 500 ° C., preferably 650 ° C., more preferably 620 ° C., most preferably The upper limit is 600 ° C.
  • the optical glass of the present invention preferably has a yield point (At) of 450 ° C. or higher and 700 ° C. or lower.
  • the yield point (At) is one of indices indicating the softening property of glass, and is an index indicating a temperature close to the press molding temperature. Therefore, by using a glass having a yield point (At) of 450 ° C. or higher, adverse effects due to frictional heat generated when polishing the glass can be reduced. Further, by using a glass having a yield point (At) of 700 ° C. or lower, press molding at a lower temperature becomes possible, so that press molding can be performed more easily.
  • the yield point (At) of the optical glass of the present invention is preferably 450 ° C., more preferably 500 ° C., most preferably 540 ° C., preferably 700 ° C., more preferably 670 ° C., most preferably 650.
  • C is the upper limit.
  • the optical glass of the present invention preferably has a predetermined refractive index and dispersion (Abbe number). More specifically, the refractive index (n d ) of the optical glass of the present invention is preferably 1.78, more preferably 1.80, most preferably 1.82, and preferably 1.95. The upper limit is preferably 1.92, and most preferably 1.90.
  • the Abbe number ( ⁇ d ) of the optical glass of the present invention is preferably 18, more preferably 20, most preferably 22, the lower limit, preferably 30, more preferably 28, and most preferably 27. . Accordingly, the degree of freedom in optical design can be expanded, and a large amount of light refraction can be obtained even if the device is made thinner.
  • the means for reducing the content of Sb 2 O 3 component is, for example, means for reducing the content of Sb 2 O 3 component contained in the raw material used, but is not limited thereto. Further, it is more effective to use a method for reducing the Pt component and the Fe component together.
  • the optical glass of the present invention and the glass used in the spectral transmittance degradation suppressing method of the present invention are produced, for example, as follows. That is, the raw materials are uniformly mixed so that each component is within a predetermined content range. The prepared mixture is put into a quartz crucible and roughly melted, and then put into a platinum crucible or a platinum alloy crucible, melted in a predetermined temperature range for a predetermined time, homogenized by stirring, and subjected to foam breakage or the like. Next, the temperature of the molten glass is lowered, cast into a mold, and slowly cooled to produce optical glass.
  • the melting temperature of the glass is preferably 1400 ° C., more preferably 1300 ° C., most preferably 1200 ° C., and the melting time of the glass is preferably 6 hours. More preferably 4 hours, and most preferably 2 hours.
  • a glass molded body can be produced from the produced optical glass using means such as reheat press molding or precision press molding. That is, a lens preform for mold press molding is prepared from optical glass, and after reheat press molding is performed on the lens preform, polishing can be performed to prepare a glass molded body. Further, a glass molded body can be produced by precision press molding the lens preform produced by polishing. In addition, the means for producing the glass molded body is not limited to these means.
  • the glass molded body produced in this manner is useful for various optical elements, and among them, it is particularly preferable to use for optical elements such as lenses and prisms. Thereby, since the temporal degradation of the spectral transmittance of the optical element is suppressed, the color balance of the optical element can be hardly deteriorated even after long-term use.
  • compositions of Examples (No. 1 to No. 159) and Comparative Examples (No. 1 to No. 2) of the present invention concentrations of Pt component and Fe component of these glasses, refractive index ( nd ), Tables 1 to 5 show the Abbe number ( ⁇ d ), spectral transmittance at a wavelength of 450 nm before and after light irradiation, solarization, partial dispersion ratio ( ⁇ g, F), glass transition point (Tg), and yield point (At). 22 shows.
  • ⁇ d Abbe number
  • ⁇ g, F partial dispersion ratio
  • Tg glass transition point
  • At yield point 22 shows.
  • the following examples are merely for illustrative purposes, and are not limited to these examples.
  • the glass of Examples (No. 1 to No. 159) and Comparative Examples (No. 1 to No. 2) of the present invention are all oxides, hydroxides, carbonates corresponding to the raw materials of the respective components, High-purity raw materials used for ordinary optical glass such as nitrates, fluorides, hydroxides, metaphosphoric acid compounds, etc. are selected, and the composition ratios of the respective examples and comparative examples shown in Tables 1 to 22 are obtained. And weighed uniformly. Thereafter, the mixture was put into a platinum crucible, melted in an electric furnace at a temperature range of 1200 to 1350 ° C. for 2 to 4 hours according to the difficulty of melting the glass composition, and homogenized by stirring to remove bubbles. Thereafter, the temperature of the molten glass was lowered to 1100 to 1200 ° C., homogenized by stirring, cast into a mold, and slowly cooled to produce a glass.
  • High-purity raw materials used for ordinary optical glass such as nitrates, fluorides, hydrox
  • the contents of the Pt component and Fe component of the glasses of the examples (No. 1 to No. 159) and the comparative examples (No. 1 to No. 2) are the same as those of the glasses having the compositions of the examples and comparative examples.
  • the solution obtained by powdering and treating with an acid was measured using an ICP emission spectrometer (Vista-PRO manufactured by Seiko Instruments Inc.).
  • the solarization of the glass of the examples (No. 1 to No. 159) and the comparative examples (No. 1 to No. 2) is described in Japan Optical Glass Industry Association Standard JOGIS04-1994 “Measurement Method of Solarization of Optical Glass”.
  • the change (%) in light transmittance at a wavelength of 450 nm before and after light irradiation was measured.
  • the light irradiation was performed by heating an optical glass sample to 100 ° C. and irradiating light with a wavelength of 450 nm for 4 hours using an ultrahigh pressure mercury lamp.
  • the glass used in this measurement was a glass that had been treated in a slow cooling furnace at a slow cooling rate of ⁇ 25 ° C./hr.
  • the glass transition point (Tg) and the yield point (At) of the glass of the examples (No. 1 to No. 159) and the comparative examples (No. 1 to No. 2) were measured with a differential heat measuring device (manufactured by Netchgeletebau). It was determined by performing measurement using STA 409 CD).
  • the sample particle size at the time of measurement was 425 to 600 ⁇ m, and the temperature elevation rate was 10 ° C./min.
  • the optical glass of the example of the present invention has a partial dispersion ratio ( ⁇ g, F) of ( ⁇ 1.60 ⁇ 10 ⁇ 3 ⁇ ⁇ d +0.6346) or more when ⁇ d ⁇ 25, more specifically ( ⁇ 1.60 ⁇ 10 ⁇ 3 ⁇ ⁇ d +0.6497) or more.
  • the partial dispersion ratio ( ⁇ g, F) is ( ⁇ 2.50 ⁇ 10 ⁇ 3 ⁇ ⁇ d +0.6571) or more, more specifically ( ⁇ 2.50 ⁇ 10 ⁇ 3).
  • the partial dispersion ratio ( ⁇ g, F) of the optical glass of the example of the present invention is ( ⁇ 4.21 ⁇ 10 ⁇ 3 ⁇ ⁇ d +0.7207) or less, more specifically ( ⁇ 4.21 ⁇ 10 ⁇ 3 ⁇ ⁇ d +0.7187) or less. Therefore, it was found that these partial dispersion ratios ( ⁇ g, F) are within a desired range.
  • the glasses of the comparative examples of the present invention all had a partial dispersion ratio ( ⁇ g, F) exceeding ( ⁇ 4.21 ⁇ 10 ⁇ 3 ⁇ ⁇ d +0.7187). Therefore, it was clarified that the optical glass of the example of the present invention has a smaller partial dispersion ratio ( ⁇ g, F) in the relational expression with the Abbe number ( ⁇ d ) than the glass of the comparative example.
  • the optical glasses of the examples of the present invention all have a refractive index (n d ) of 1.78 or more, more specifically 1.82 or more, and the refractive index (n d ) of 1.95 or less. More specifically, it was 1.90 or less, and was within a desired range.
  • the optical glasses of the examples of the present invention all have an Abbe number ( ⁇ d ) of 18 or more, more specifically 22 or more, and this Abbe number ( ⁇ d ) of 30 or less, more specifically 27. And within the desired range.
  • the optical glasses of the examples of the present invention all have a glass transition point (Tg) of 400 ° C. or higher, more specifically 500 ° C. or higher, and this glass transition point (Tg) is 650 ° C. or lower. It was 600 degrees C or less, and was in the desired range.
  • Tg glass transition point
  • the optical glasses of the examples of the present invention all have a yield point (At) of 450 ° C. or higher, more specifically 540 ° C. or higher, and the yield point (At) is 700 ° C. or lower, more specifically. It was 650 degrees C or less, and was in the desired range.
  • the optical glass of the example of the present invention After performing reheat press molding using the optical glass of the example of the present invention, grinding and polishing were performed and processed into the shape of a lens and a prism to obtain a glass molded body. Further, a lens preform for precision press molding was formed using the optical glass of the example of the present invention, and this lens preform was precision press molded to obtain a glass molded body.
  • the content of the Sb 2 O 3 component is not more than a predetermined amount, and the obtained glass molded body has little solarization, and has a predetermined spectral transmission as a lens and a prism over a long period of time.
  • the glass molded object which can have a rate was able to be obtained.
  • the glass of the comparative example contained a predetermined or higher Sb 2 O 3 component, and the obtained glass molded body was easily colored by ultraviolet rays. Therefore, the glass molded body produced from the optical glass of the example of the present invention has a reduced solarization as compared with the glass molded body produced from the glass of the comparative example, and the spectral transmittance is deteriorated over time. It became clear that was suppressed.

Abstract

L'invention concerne un verre optique qui conserve une transmittance spectrale élevée même au bout d'une longue durée et un procédé de suppression de la détérioration de la transmittance optique du verre. Le verre optique a une teneur en composants Sb2O3 inférieure ou égale à 0,5 % en masse par rapport à la masse totale du verre en termes d'oxyde et une solarisation (détérioration de la transmittance spectrale à une longueur d'onde de 450 nm) inférieure ou égale à 5,0 %. Le procédé de suppression de la détérioration de la transmittance optique du verre comprend la réduction de la teneur en composants Sb2O3 dans le verre.
PCT/JP2009/065920 2008-09-30 2009-09-11 Verre optique et procédé de suppression de la détérioration de la transmittance spectrale WO2010038597A1 (fr)

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CN106587599A (zh) 2017-04-26

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