WO2019031095A1 - Verre optique, élément optique et dispositif optique - Google Patents

Verre optique, élément optique et dispositif optique Download PDF

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Publication number
WO2019031095A1
WO2019031095A1 PCT/JP2018/024515 JP2018024515W WO2019031095A1 WO 2019031095 A1 WO2019031095 A1 WO 2019031095A1 JP 2018024515 W JP2018024515 W JP 2018024515W WO 2019031095 A1 WO2019031095 A1 WO 2019031095A1
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component
glass
optical
still
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PCT/JP2018/024515
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English (en)
Japanese (ja)
Inventor
桃野浄行
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株式会社 オハラ
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Priority to JP2019535019A priority Critical patent/JP7126505B2/ja
Publication of WO2019031095A1 publication Critical patent/WO2019031095A1/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
    • C03C3/062—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
    • 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 an optical glass, an optical element and an optical apparatus.
  • optical glasses for producing an optical element an Abbe number of 40 or more and 60 or less, which has a refractive index (n d ) of 1.70 or more, capable of achieving weight reduction and miniaturization of the entire optical system.
  • n d refractive index
  • the demand for high refractive index, low dispersion glasses with ⁇ d ) is very high.
  • glass compositions represented by Patent Documents 1 to 3 are known.
  • a method of producing an optical element from optical glass for example, a method of obtaining a shape of an optical element by grinding and polishing a gob or glass block formed of optical glass, a gob or glass formed of optical glass
  • reheat press molding reheat press molding
  • a method of obtaining the shape of an optical element by (precise mold press molding) is known.
  • it is required that stable glass be obtained when forming a gob or a glass block from a molten glass material when the stability to devitrification (the devitrification resistance) of the glass constituting the gob or glass block obtained is reduced and crystals are generated inside the glass, a glass suitable as an optical element is no longer obtained.
  • the stability to devitrification the devitrification resistance
  • the present invention has been made in view of the above-mentioned problems, and the object of the present invention is at the time of glass molding while the refractive index (n d ) and the Abbe number (v d ) are within the desired ranges. It is to obtain a glass with high stability, high resistance to devitrification, difficulty in coloring, and reduced material cost.
  • the present inventor combined B 2 O 3 components, La 2 O 3 components, and RO components, and used SiO 2 / B 2 O 3 . By finding it within the predetermined range, it is found that the material cost of the glass is reduced, the stability in forming the glass is high, the color is difficult to be formed, and the liquidus temperature of the glass is lowered, and the present invention is completed. It reached. Specifically, the present invention provides the following.
  • Optical glass containing not more than 0% and having a mass ratio SiO 2 / B 2 O 3 of 0.5 or less (wherein R is one or more selected from the group consisting of Mg, Ca, Sr, and Ba).
  • Weight ratio (TiO 2 + Nb 2 O 5 + WO 3 + Ta 2 O 5) / (Y 2 O 3 + ZrO 2) is 1.00 or less (1), wherein the optical glass.
  • (3) has 1.70 or more of refractive index (n d), 40 or more 60 or less Abbe number ([nu d), 1300 ° C. with the following liquid phase temperature (1) or according to any one of (2) Optical glass.
  • An optical apparatus comprising the optical element according to (4).
  • the refractive index (n d) and Abbe number ([nu d) is within the desired range, high stability during glass forming, and devitrification resistance is high, a colored hard glass You can get it.
  • the optical glass of the present invention from 10.5 to 50.5% of B 2 O 3 component in wt.%, La 2 O 3 component from 18.0 to 60.0%, 15.0% of ZnO component, and
  • the RO component is contained at 5.0% or less, and the mass ratio SiO 2 / B 2 O 3 is at most 0.5.
  • the B 2 O 3 component, the La 2 O 3 component and the RO component in combination, and making the SiO 2 / B 2 O 3 within a predetermined range it has an Abbe number ( ⁇ d ) of 40 or more.
  • the liquidus temperature tends to be low. Therefore, while the refractive index (n d) and Abbe number ([nu d) is within the desired range, and high optical glass devitrification resistance, it is possible to obtain an optical device using the same more expensive.
  • Glass composition The composition range of each component which comprises the optical glass of this invention is described below. In the present specification, unless otherwise specified, the contents of the respective components are all represented by mass% relative to the total mass of the glass in the oxide conversion composition.
  • oxide conversion composition is assumed that all oxides, composite salts, metal fluorides, etc. used as raw materials of the glass component of the present invention are decomposed at the time of melting and converted into oxides, It is the composition which described each ingredient contained in glass on the basis of 100 mass% of gross mass of the generated oxide concerned.
  • the B 2 O 3 component is an essential component indispensable as a glass forming oxide.
  • the devitrification resistance of the glass can be enhanced and the dispersion of the glass can be reduced by containing the B 2 O 3 component at 10.5% or more.
  • the lower limit of the content of the B 2 O 3 component is preferably 10.5% or more, more preferably 11.8% or more, more preferably 16.8% or more, still more preferably 19.3% or more Preferably, it is 21.3% or more, more preferably 24.3% or more.
  • the content of the B 2 O 3 component to 50.5% or less, a larger refractive index can be easily obtained, and the deterioration of the chemical durability can be suppressed.
  • the upper limit of the content of the B 2 O 3 component is preferably 50.5% or less, more preferably 45.5% or less, still more preferably 43.0% or less, still more preferably 40.5% or less Preferably, it is 38.0% or less.
  • the B 2 O 3 component H 3 BO 3 , Na 2 B 4 O 7 , Na 2 B 4 O 7 ⁇ 10H 2 O, BPO 4 or the like can be used as a raw material.
  • the La 2 O 3 component is an essential component that raises the refractive index of the glass and reduces the dispersion (increases the Abbe number).
  • the lower limit of the content of the La 2 O 3 component is preferably 18.0% or more, more preferably 20.5% or more, still more preferably 23.0% or more, and further preferably 25.5% or more.
  • the devitrification resistance of the glass can be enhanced by setting the content of the La 2 O 3 component to 60.0% or less.
  • the upper limit of the content of the La 2 O 3 component is preferably 60.0% or less, more preferably 57.5% or less, still more preferably 55.0% or less, still more preferably 52.5% or less .
  • the La 2 O 3 component 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 Y 2 O 3 component is an optional component capable of suppressing the material cost of the glass and reducing the specific gravity while maintaining the high refractive index and the high Abbe number by containing more than 0%. Therefore, the lower limit of the content of the Y 2 O 3 component is preferably more than 0%, more preferably 1.0% or more, still more preferably 1.5% or more, and still more preferably 2.5% or more. When the content of the Gd 2 O 3 component is 3.0% or less, the content of the Y 2 O 3 component is preferably 6.85% or more. By doing so, it is possible to obtain a glass excellent in devitrification resistance while reducing the specific gravity.
  • the lower limit of the content of the Y 2 O 3 component is preferably 6.85% or more, more preferably 7.85% or more, still more preferably 8.85% or more, and still more preferably 9.85% or more.
  • the upper limit of the content of the Y 2 O 3 component is preferably 38.0% or less, more preferably 33.0% or less, still more preferably 30.5% or less, still more preferably 23.3% or less, and further preferably Preferably, it is 20.8% or less.
  • the content of Y 2 O 3 component when containing Gd 2 O 3 component, the content of Y 2 O 3 component preferably set to 9.5% or less. By doing so, the deterioration of the devitrification resistance due to the excessive content can be suppressed. Therefore, the upper limit of the content of the Y 2 O 3 component is preferably 9.5% or less, more preferably 8.5% or less, still more preferably 7.5% or less, still more preferably 6.5% or less .
  • the Y 2 O 3 component Y 2 O 3 , YF 3 or the like can be used as a raw material.
  • the ZnO component is an optional component capable of lowering the glass transition point and enhancing the chemical durability when the content is more than 0%. Therefore, the lower limit of the content of the ZnO component may be preferably more than 0%, more preferably 0.1% or more, and still more preferably 0.3% or more.
  • the content of the ZnO component may 15.0% or less, a decrease in the refractive index of the glass and a decrease in the devitrification resistance can be suppressed.
  • production of the striation to glass can be reduced.
  • the upper limit of the content of the ZnO component is preferably 15.0% or less, more preferably less than 10.0%, still more preferably less than 5.0%, still more preferably 2.5% or less, further preferably 1 .23% or less, more preferably less than 1.0%.
  • ZnO component ZnO, ZnF 2 or the like can be used as a raw material.
  • the MgO component, the CaO component, the SrO component, and the BaO component are optional components that can enhance the meltability of the glass material, when they are contained in excess of 0%.
  • the content of each of the MgO component, the CaO component, the SrO component and the BaO component is preferably less than 5.0%, more preferably less than 4.0%, still more preferably 2.0% or less, more preferably Is less than 1.0%.
  • MgO component, CaO component, SrO component and BaO components MgCO 3 as raw materials, MgF 2, CaCO 3, CaF 2, Sr (NO 3) 2, SrF 2, BaCO 3, Ba (NO 3) 2, BaF 2 and the like Can be used.
  • the total (mass sum) of the content of the RO component (wherein R is one or more selected from the group consisting of Mg, Ca, Sr, and Ba) is preferably 5.0% or less.
  • R is one or more selected from the group consisting of Mg, Ca, Sr, and Ba
  • the upper limit of the mass sum of the RO component is preferably 5.0% or less, more preferably 4.0% or less, still more preferably 2.0% or less, and still more preferably 1.0% or less.
  • the mass ratio of the sum of the content of the RO component (wherein R is one or more selected from the group consisting of Mg, Ca, Sr, and Ba) to the sum of the content of the B 2 O 3 component and the SiO 2 component is 0.50 or less is preferable.
  • the upper limit of the mass ratio RO / (B 2 O 3 + SiO 2 ) is preferably 0.50 or less, more preferably 0.30 or less, still more preferably 0.10 or less, and still more preferably 0.07 or less. .
  • RO component (wherein R is one or more selected from the group consisting of Mg, Ca, Sr, and Ba) relative to the sum of the contents of the Y 2 O 3 component, the Gd 2 O 3 component and the La 2 O 3 component
  • the mass ratio of the sum of the contents is preferably 0.500 or less.
  • the upper limit of the mass ratio RO / (Y 2 O 3 + Gd 2 O 3 + La 2 O 3 ) is preferably 0.500 or less, more preferably 0.250 or less, still more preferably 0.100 or less, still more preferably It is set to 0.060 or less, more preferably 0.045 or less, and further preferably 0.030 or less.
  • the ratio of the content of the SiO 2 component to the B 2 O 3 component is preferably 0.500 or less.
  • the upper limit of the mass ratio SiO 2 / B 2 O 3 is preferably 0.500 or less, more preferably 0.400 or less, still more preferably 0.300 or less, further preferably 0.200 or less, more preferably 0 .110 or less.
  • the SiO 2 component is an optional component capable of increasing the viscosity of the molten glass, reducing the coloration of the glass, and enhancing the devitrification resistance, when it is contained in excess of 0%. Therefore, the lower limit of the content of the SiO 2 component is preferably more than 0%, more preferably 0.3% or more, still more preferably 0.6% or more, and still more preferably 1.0% or more. On the other hand, by setting the content of the SiO 2 component to 18.3% or less, the rise of the glass transition point can be suppressed and the decrease of the refractive index can be suppressed.
  • the upper limit of the content of the SiO 2 component is preferably 18.3% or less, more preferably 13.3% or less, still more preferably 10.8% or less, still more preferably less than 7.5%, still more preferably It is 4.51% or less, more preferably less than 4.0%.
  • SiO 2 component SiO 2 , K 2 SiF 6 , Na 2 SiF 6 or the like can be used as a raw material.
  • the Gd 2 O 3 component is an optional component that can increase the refractive index of the glass and increase the Abbe number when it contains more than 0%.
  • the content of the Gd 2 O 3 component is preferably 5.4% or more. By doing so, glass excellent in devitrification resistance can be obtained. Therefore, the lower limit of the content of the Gd 2 O 3 component is preferably 5.4% or more, more preferably 7.9% or more, and still more preferably 10.4% or more.
  • the particularly expensive Gd 2 O 3 component of the rare earth elements to less than 10.0%, the specific gravity of the glass can be suppressed to a low level, and the material cost of the glass can be suppressed.
  • the upper limit of the content of the Gd 2 O 3 component is preferably less than 10.0%, more preferably 5.0% or less, still more preferably 3.0% or less, still more preferably 1.0% or less It is preferably 0.1% or less, and may not be substantially contained in view of reducing material cost. Further, Y 2 O 3 content component in the case of less than 10.0%, it is impossible to obtain desired refractive index and Abbe number. Therefore, the upper limit of the content of the Gd 2 O 3 component is preferably 35.0% or less, more preferably 32.5% or less, still more preferably 23.0% or less, still more preferably 18.3% or less, and further Preferably, it is not more than 15.8%. As the Gd 2 O 3 component, Gd 2 O 3 , GdF 3 or the like can be used as a raw material.
  • the Ta 2 O 5 component is an optional component capable of enhancing the refractive index of the glass, enhancing the devitrification resistance, and enhancing the viscosity of the molten glass when it contains more than 0%.
  • the content of the expensive Ta 2 O 5 component is 10.0% or less, the material cost of the glass is reduced, and therefore, it is possible to manufacture a cheaper optical glass.
  • the upper limit of the content of the Ta 2 O 5 component is preferably 10.0% or less, more preferably less than 5.0%, still more preferably less than 3.0%, and still more preferably less than 1.0%. From the viewpoint of reducing the material cost, it may not be substantially included.
  • Ta 2 O 5 component Ta 2 O 5 or the like can be used as a raw material.
  • the Li 2 O component is an optional component that can improve the meltability of the glass and lower the glass transition point when it contains more than 0%.
  • the content of the Li 2 O component is 10.0% or less, the viscosity of the glass can be increased, and therefore the striae of the glass can be reduced.
  • the refractive index of glass can be made hard to fall by this, chemical durability of glass can be improved, and devitrification resistance can be improved. Therefore, the upper limit of the content of the Li 2 O component is preferably 10.0% or less, more preferably less than 5.0%, still more preferably less than 3.0%, still more preferably less than 2.0% Preferably, it is less than 1.0%, more preferably less than 0.2%, and it may not be substantially contained.
  • the Li 2 O component Li 2 CO 3 , LiNO 3 , Li 2 CO 3 or the like can be used as a raw material.
  • the Na 2 O component, the K 2 O component and the Cs 2 O component contain more than 0%, any component which can improve the meltability of the glass, enhance the devitrification resistance of the glass, and lower the glass transition temperature It is.
  • the content of each of the Na 2 O component, the K 2 O component and the Cs 2 O component 10.0% or less it becomes difficult to reduce the refractive index of the glass, and the devitrification resistance Be enhanced.
  • the upper limit of the content of each of the Na 2 O component, the K 2 O component, and the Cs 2 O component is preferably 10.0% or less, more preferably less than 5.0%, still more preferably 3.0% or less More preferably, it is less than 2.0%, more preferably less than 1.0%, and it may not be substantially contained.
  • the Na 2 O component, the K 2 O component and the Cs 2 O component are, as raw materials, NaNO 3 , NaF, Na 2 SiF 6 , K 2 CO 3 , KNO 3 , KF, KHF 2 , K 2 SiF 6 , Cs 2 CO 3 , CsNO 3 etc. can be used.
  • the total amount of the Rn 2 O components (wherein, Rn is one or more selected from the group consisting of Li, Na, K, and Cs) is preferably 15.0% or less. Thereby, the decrease in the refractive index of the glass can be suppressed and the devitrification resistance can be enhanced. Therefore, the mass sum of the Rn 2 O component is preferably 15.0%, more preferably 10.0%, still more preferably less than 6.0%, still more preferably less than 3.0%, still more preferably 1.0. The upper limit is less than%.
  • the ZrO 2 component is an optional component that can contribute to the increase in the refractive index and the decrease in the dispersion of the glass when it contains more than 0%, and can improve the devitrification resistance of the glass. Therefore, the lower limit of the content of the ZrO 2 component is preferably more than 0%, more preferably 0.5% or more, still more preferably more than 1.0%, and still more preferably more than 1.5%. On the other hand, by setting the ZrO 2 component to 15.0% or less, it is possible to suppress the decrease in the devitrification resistance of the glass due to the excessive inclusion of the ZrO 2 component.
  • the upper limit of the content of the ZrO 2 component is preferably 15.0% or less, more preferably 12.5% or less, still more preferably 10.0% or less, still more preferably 8.0% or less, more preferably It is less than 6.0%, preferably less than 5.0%.
  • ZrO 2 component ZrO 2 , ZrF 4 or the like can be used as a raw material.
  • the Al 2 O 3 component is an optional component having an effect of improving the devitrification resistance and the chemical durability. Therefore, the lower limit of the content of the Al 2 O 3 component is preferably more than 0%, more preferably 0.5% or more, still more preferably 1.0% or more, still more preferably 1.5% or more, more preferably More than 2.0%, most preferably more than 3.0%.
  • the Al 2 O 3 component is preferably 1.0% or more. By doing so, it is possible to suppress the crystallization due to the SiO 2 component and to obtain a glass excellent in devitrification resistance.
  • the upper limit of the content of the Al 2 O 3 component is preferably 20.0% or less, more preferably less than 15.0%, still more preferably 10.0% or less, still more preferably 8.0% or less Preferably, it is 5.0% or less.
  • Al 2 O 3 component Al 2 O 3 , Al (OH) 3 , AlF 3 , Al (PO 3 ) 3 or the like can be used as a raw material.
  • the ratio of the sum of the contents of the Al 2 O 3 component and the ZnO component to the B 2 O 3 component is preferably 1.00 or less.
  • the upper limit of the mass ratio (Al 2 O 3 + ZnO) / B 2 O 3 is preferably 1.00 or less, more preferably 0.50 or less, still more preferably 0.10 or less, still more preferably 0.08 or less More preferably, it is 0.05 or less, more preferably 0.03 or less.
  • the Yb 2 O 3 component is an optional component that can increase the refractive index of the glass and reduce the dispersion when it is contained in excess of 0%.
  • the upper limit of the content of the Yb 2 O 3 component is preferably 20.0% or less, more preferably less than 10.0%, still more preferably less than 5.0%, still more preferably less than 3.0%, and further preferably Preferably, it is less than 1.0% and may not be substantially contained.
  • Yb 2 O 3 component Yb 2 O 3 or the like can be used as a raw material.
  • the sum (mass sum) of the contents of Ln 2 O 3 components (wherein, Ln is one or more selected from the group consisting of La, Gd, Y, Yb) is 40.5% or more and 75.0% or less Is preferred.
  • the dispersion of glass can be reduced by setting the sum to 40.5% or more. Therefore, the lower limit of the mass sum of the Ln 2 O 3 component is preferably 40.5% or more, more preferably 43.0% or more, still more preferably 45.0% or more, still more preferably 47.5% or more Preferably, it is 50.5% or more, more preferably 52.5% or more.
  • the upper limit of the mass sum of the Ln 2 O 3 component is preferably 75.0% or less, more preferably less than 70.0%, still more preferably less than 65.0%, still more preferably 62.5% or less .
  • the TiO 2 component is an optional component capable of enhancing the refractive index of the glass, adjusting the Abbe number to a low value, and enhancing the devitrification resistance when the TiO 2 component is contained more than 0%.
  • the upper limit of the content of the TiO 2 component is preferably less than 15.0%, more preferably 10.0% or less, still more preferably 5.0% or less, still more preferably 3.0% or less, more preferably Less than 1.0%.
  • TiO 2 component can be used such as TiO 2 as a raw material.
  • the Nb 2 O 5 component is an optional component capable of enhancing the refractive index of the glass and enhancing the devitrification resistance when the Nb 2 O 5 content is more than 0%.
  • the content of the Nb 2 O 5 component is set to 20.0% or less, the decrease in the devitrification resistance of the glass due to the excessive content of the Nb 2 O 5 component, and the decrease in the visible light transmittance It can be suppressed.
  • the upper limit of the content of the Nb 2 O 5 component is preferably 20.0% or less, more preferably 15.0% or less, still more preferably 10.0% or less, still more preferably 8.0% or less Preferably, it is less than 5.0%, more preferably 3.0% or less, further preferably less than 1.5%, and even more preferably less than 1.0%.
  • Nb 2 O 5 or the like can be used as a raw material.
  • the WO 3 component is an optional component that can increase the refractive index while reducing the coloration of the glass due to other high refractive index components and can improve the devitrification resistance of the glass when it contains more than 0%.
  • the WO 3 component is also a component that can lower the glass transition temperature.
  • the upper limit of the content of the WO 3 component is preferably 20.0% or less, more preferably 10.0% or less, still more preferably less than 5.0%, still more preferably 3.0% or less, more preferably Less than 1.0%.
  • WO 3 components it is possible to use WO 3 or the like as a raw material.
  • the ratio of the sum of the contents of the TiO 2 component, the Nb 2 O 5 component, the Ta 2 O 5 component and the WO 3 component to the sum of the Y 2 O 3 component and the ZrO 2 component content is preferably 1.00 or less.
  • the upper limit of the mass ratio (TiO 2 + Nb 2 O 5 + Ta 2 O 5 + WO 3 ) / (Y 2 O 3 + ZrO 2 ) is preferably 1.00 or less, more preferably 0.80 or less, still more preferably 0. Or less, more preferably 0.26 or less, further preferably 0.15 or less, and further preferably 0.10 or less.
  • the Ga 2 O 3 component is an optional component that can increase the refractive index of the glass and improve the devitrification resistance when it contains more than 0%.
  • the upper limit of the content of the Ga 2 O 3 component is preferably 10.0% or less, more preferably 5.0% or less, further preferably 3.0% or less, still more preferably 1.0% or less, and further Preferably, it is 0.1% or less. From the viewpoint of reducing the material cost, the Ga 2 O 3 component may not be contained.
  • Ga 2 O 3 component can be used Ga 2 O 3 or the like as raw materials.
  • the ratio of the sum of the content of TiO 2 component, Nb 2 O 5 component, Ta 2 O 5 component, ZrO 2 component and WO 3 component to the sum of the content of B 2 O 3 component and SiO 2 component is 1.00, The following are preferred. Thereby, while improving the devitrification resistance, it is possible to reduce the coloration of the glass and to enhance the visible light transmittance. Furthermore, it is easy to easily obtain the desired refractive index.
  • the upper limit of the mass ratio (TiO 2 + Nb 2 O 5 + Ta 2 O 5 + ZrO 2 + WO 3 ) / (B 2 O 3 + SiO 2 ) is preferably 1.00 or less, more preferably 0.80 or less, and further preferably Is preferably 0.60 or less, more preferably 0.50 or less, and still more preferably 0.34 or less.
  • the mass ratio (Y 2 O 3 + ZnO + ZrO 2 ) / Y 2 O 3 is preferably 3.00, more preferably 2.00, still more preferably 1.75, further preferably 1.50, more preferably 1
  • the upper limit is preferably .36, more preferably 1.34.
  • Ratio of the sum of the content of TiO 2 component, Nb 2 O 5 component, Ta 2 O 5 component, and WO 3 component to the sum of the content of Y 2 O 3 component, Gd 2 O 3 component and La 2 O 3 component Is preferably 1.00 or less.
  • the upper limit of the mass ratio (TiO 2 + Nb 2 O 5 + Ta 2 O 5 + WO 3 ) / (Y 2 O 3 + Gd 2 O 3 + La 2 O 3 ) is preferably 1.00 or less, more preferably 0.80.
  • the following conditions are more preferably 0.60 or less, further preferably 0.50 or less, further preferably 0.34 or less, and further preferably 0.25 or less.
  • the P 2 O 5 component is an optional component capable of enhancing the devitrification resistance of the glass when it contains more than 0%.
  • the upper limit of the content of the P 2 O 5 component is preferably 10.0% or less, more preferably less than 5.0%, still more preferably 3.0% or less, and further preferably less than 1.0%.
  • Al (PO 3 ) 3 , Ca (PO 3 ) 2 , Ba (PO 3 ) 2 , BPO 4 , H 3 PO 4 and the like can be used as raw materials.
  • the GeO 2 component is an optional component that can increase the refractive index of the glass and improve the devitrification resistance when it contains more than 0%.
  • the upper limit of the content of the GeO 2 component is preferably less than 10.0%, more preferably less than 5.0%, still more preferably less than 2.5%, and still more preferably 1.0% or less. Does not contain.
  • the GeO 2 component can use GeO 2 etc. as a raw material.
  • the Bi 2 O 3 component is an optional component that can increase the refractive index and lower the glass transition temperature when it is contained in excess of 0%.
  • the content of the Bi 2 O 3 component is 10.0% or less, the devitrification resistance of the glass can be enhanced, and the coloration of the glass can be reduced to enhance the visible light transmittance. Therefore, the upper limit of the content of the Bi 2 O 3 component is preferably 10.0% or less, more preferably less than 5.0%, still more preferably 3.0% or less, and further preferably less than 1.0%.
  • Bi 2 O 3 component can be used Bi 2 O 3 and the like as raw materials.
  • the TeO 2 component is an optional component that can increase the refractive index and lower the glass transition point when it contains more than 0%.
  • TeO 2 has a problem that it can be alloyed with platinum when it melts a glass material in a crucible made of platinum or a melting tank in which a portion in contact with the molten glass is made of platinum. Therefore, the upper limit of the content of the TeO 2 component is preferably 20.0% or less, more preferably 10.0% or less, still more preferably 5.0% or less, further preferably 3.0% or less, more preferably Is less than 1.0% and may not be substantially contained.
  • TeO 2 component TeO 2 or the like can be used as a raw material.
  • TiO 2 component to the sum of the content of SiO 2 component and B 2 O 3 component, Nb 2 O 5 component, Y 2 O 3 component, Ta 2 O 5 component, ZrO 2 component, Al 2 O 3 component and WO 3 components
  • the ratio of the sum of the contents of is preferably 1.50 or less.
  • the upper limit of the mass ratio (TiO 2 + Nb 2 O 5 + Y 2 O 3 + Ta 2 O 5 + ZrO 2 + Al 2 O 3 + WO 3 ) / (SiO 2 + B 2 O 3 ) is preferably 1.50 or less, more preferably Is preferably 1.00 or less, more preferably 0.80 or less, still more preferably 0.60 or less, further preferably 0.50 or less, more preferably 0.34 or less.
  • the SnO 2 component is an optional component capable of reducing and clarifying the oxidation of the molten glass and enhancing the visible light transmittance of the glass when it contains more than 0%.
  • the content of the SnO 2 component is set to 1.0% or less, it is possible to reduce the coloration of the glass due to the reduction of the molten glass and the devitrification of the glass.
  • the upper limit of the content of the SnO 2 component is preferably 1.0% or less, more preferably 0.7% or less, and still more preferably 0.5% or less.
  • SnO, SnO 2 , SnF 2 , SnF 4 or the like can be used as a raw material.
  • the Sb 2 O 3 component is an optional component capable of degassing the molten glass when it contains more than 0%.
  • the upper limit of the content of the Sb 2 O 3 component is preferably 1.0% or less, more preferably 0.7% or less, and still more preferably 0.5% or less.
  • Sb 2 O 3 component can be used Sb 2 O 3, Sb 2 O 5, Na 2 H 2 Sb 2 O 7 ⁇ 5H 2 O and the like as raw materials.
  • the components for clarifying and degassing the glass are not limited to the above-mentioned Sb 2 O 3 components, and known clarifiers, defoamers or combinations thereof known in the field of glass production can be used.
  • each transition metal component such as Zn, Ta, Ti, Zr, Nb, W, La, Gd, Y, Yb, Lu excluding V, Cr, Mn, Fe, Co, Ni, Cu, Ag and Mo is
  • the glass is substantially colored even when each is contained singly or in combination, and causes absorption at a specific wavelength in the visible region.
  • the glass is substantially colored even when each is contained singly or in combination, and causes absorption at a specific wavelength in the visible region.
  • the glass is substantially colored even when each is contained singly or in combination, and causes absorption at a specific wavelength in the visible region.
  • the glass is substantially colored even when each is contained singly or in combination, and causes absorption at a specific wavelength in the visible region.
  • the glass is substantially colored even when each is contained singly or in combination, and causes absorption at a specific wavelength in the visible region.
  • lead compounds and As 2 O 3 or the like arsenic compound such as PbO because environmental load is highly components, it does not substantially contained, i.e., it is desirable not to contain any except inevitable contamination.
  • Th, Cd, Tl, Os, Be, and Se components tend to refrain from being used as harmful chemicals in recent years, and they are not only used in glass manufacturing processes but also in processing processes and disposal after productization. All environmental measures are needed. Therefore, when emphasizing environmental impact, it is preferable not to contain these substantially.
  • the optical glass of the present invention is produced, for example, as follows. That is, the above raw materials are uniformly mixed so that each component is within a predetermined content range, and the prepared mixture is put into a platinum crucible, and the melting point of the glass composition is 1100 to 1500 ° C. in an electric furnace. After melting, stirring and homogenizing in the temperature range of 2 to 5 hours, the temperature is lowered to a suitable temperature and then cast into a mold, followed by gradual cooling.
  • the optical glass of the present invention preferably has a high refractive index and a high Abbe number (low dispersion).
  • the lower limit of the refractive index (n d ) of the optical glass of the present invention is preferably 1.70 or more, more preferably 1.71 or more, and still more preferably 1.72 or more.
  • the upper limit of the refractive index may be preferably 1.85 or less, more preferably 1.82 or less, still more preferably 1.80 or less, and still more preferably 1.78 or less.
  • the lower limit of the Abbe number ( ⁇ d ) of the optical glass of the present invention is preferably 40 or more, more preferably 45 or more, and still more preferably 47 or more.
  • the upper limit is preferably 60 or less, more preferably 58 or less, More preferably, it is 55 or less.
  • the upper limit is preferably 60 or less, more preferably 58 or less, More preferably, it is 55 or less.
  • the optical glass of the present invention preferably has high devitrification resistance, more specifically, low liquidus temperature. That is, the upper limit of the liquidus temperature of the optical glass of the present invention is preferably 1300 ° C. or less, more preferably 1250 ° C. or less, still more preferably 1200 ° C. or less, further preferably 1150 ° C. or less, further preferably 1100 ° C. or less .
  • the lower limit of the liquidus temperature of the optical glass of the present invention is not particularly limited, but the lower limit of the liquidus temperature of the glass obtained by the present invention is preferably 500 ° C or more, more preferably 600 ° C or more, still more preferably It is good also as 700 ° C or more.
  • the “liquidus temperature” in this specification is as follows. A 5 cc cullet glass sample is put in a platinum crucible in a 50 ml platinum crucible, completely melted at 1350 ° C., and cooled to a predetermined temperature. The temperature is maintained for 12 hours, taken out of the furnace and immediately after cooling, the presence or absence of crystals on the glass surface and in the glass is observed, and the lowest temperature at which no crystals are observed is represented.
  • the predetermined temperature at which the temperature is lowered is a temperature in steps of 10.degree. C. up to 1300.degree.
  • the optical glass of the present invention preferably has a high visible light transmittance, particularly high light transmittance on the short wavelength side of visible light, whereby the coloration is low.
  • the upper limit of the wavelength ( ⁇ 80 ) showing a spectral transmittance of 80% for a sample with a thickness of 10 mm is preferably 500 nm or less, more preferably 450 nm or less Preferably, it is 420 nm or less.
  • the upper limit of the shortest wavelength ( ⁇ 5 ) showing a spectral transmittance of 5% for a sample with a thickness of 10 mm is preferably 380 nm or less, more preferably 360 nm or less, still more preferably 320 nm or less Preferably, it is 300 nm or less.
  • this optical glass can be preferably used for an optical element that transmits light such as a lens.
  • the optical glass of the present invention preferably has a small specific gravity. More specifically, the specific gravity of the optical glass of the present invention is preferably 5.50 [g / cm 3 ] or less. As a result, the mass of the optical element and the optical apparatus using the same is reduced, which can contribute to the weight reduction of the optical apparatus. Therefore, the upper limit of the specific gravity of the optical glass of the present invention is preferably 5.50 or less, more preferably 5.00 or less, still more preferably 4.70 or less, and still more preferably 4.50 or less. The lower limit of the specific gravity of the optical glass of the present invention is often about 3.00 or more, more specifically 3.40 or more, and further more specifically 3.80 or more. The specific gravity of the optical glass of the present invention is measured based on Japan Optical Glass Industrial Standard JOGIS 05-1975 “Method of measuring specific gravity of optical glass”.
  • a glass molded body can be produced from the produced optical glass, for example, by means of polishing or means of mold press molding such as reheat press molding or precision press molding. That is, mechanical processing such as grinding and polishing is performed on optical glass to produce a glass molded body, or reheat press molding is performed on a preform produced from optical glass, and then glass processing is performed by polishing. It is possible to produce a glass molded body by performing precision press molding on a preform manufactured by performing a body or by performing a polishing process, or a preform molded by known floating molding or the like. In addition, the means to produce a glass forming body is not limited to these means.
  • the glass molded object formed from the optical glass of this invention is useful for various optical elements and optical design, it is preferable to use for optical elements, such as a lens and a prism, especially among these.
  • optical elements such as a lens and a prism
  • compositions of Examples (No.1 ⁇ No.31) and comparative examples of the present invention, as well as the refractive index of these glasses (n d), Abbe number ([nu d), the liquidus temperature, the spectral transmittance of 5% And the wavelength ( ⁇ 5 and ⁇ 80 ) showing 80% and the specific gravity results are shown in Tables 1 to 6.
  • the following examples are for the purpose of illustration only, and are not limited to these examples.
  • the glasses of the examples and comparative examples of the present invention are ordinary optical glasses such as oxides, hydroxides, carbonates, nitrates, fluorides, hydroxides, metaphosphate compounds etc., each corresponding to the raw material of each component.
  • the high purity raw materials to be used for and weighing and uniformly mixing so as to become the ratio of the composition of each example shown in the table, it is put into a platinum crucible and is put according to the melting difficulty of the glass composition After melting in an electric furnace at a temperature range of 1100 to 1500 ° C. for 2 to 5 hours, the mixture was stirred and homogenized, then cast into a mold or the like and gradually cooled to prepare a glass.
  • the refractive index of the glass of the Examples and Comparative Examples (n d) and Abbe number ([nu d) showed a measure for the helium lamp d line (587.56 nm).
  • the Abbe number ([nu d), the refractive index with respect to the refractive index of the d line, hydrogen lamp F line (486.13nm) (n F), the refractive index for the C line (656.27nm) (n C) using the value, the Abbe number ( ⁇ d) calculated from the formula [(n d -1) / ( n F -n C)].
  • the transmittance of the glass of the example and the comparative example was measured according to Japan Optical Glass Industrial Standard JOGIS 02-2003.
  • the transmittance of glass was measured to determine the presence or absence and degree of coloring of the glass.
  • a spectral transmittance of 200 to 800 nm is measured according to JIS Z 8722, and a ⁇ 5 (wavelength at 5% transmittance), ⁇ 80 (transmittance)
  • the wavelength of 80% hour was determined.
  • the liquidus temperature of the glass of the example and the comparative example is as follows: put a 5 cc cullet glass sample in a platinum crucible in a 50 ml capacity platinum crucible and completely melt it at 1350 ° C., 1300 ° C. to 1160 ° C. The temperature is lowered to any temperature set in increments of 10 ° C and held for 12 hours, taken out of the furnace and cooled immediately to observe the presence of crystals on the glass surface and in the glass, and the lowest at which no crystals are observed The temperature was determined.
  • the specific gravity of the glass of the example and the comparative example was measured based on Japan Optical Glass Industrial Standard JOGIS 05-1975 “Method of measuring specific gravity of optical glass”.
  • the optical glasses of the examples of the present invention all had liquidus temperatures of 1300 ° C. or less, more specifically 1200 ° C. or less, and were within the desired range. For this reason, it was revealed that the optical glass of the example of the present invention has a low liquidus temperature and high devitrification resistance.
  • (lambda) 80 (wavelength at the time of the transmittance
  • (lambda) 5 (wavelength at 5% of transmittance
  • the optical glasses of the examples of the present invention all have a refractive index (n d ) of 1.70 or more, more specifically 1.71 or more, and this refractive index is 1.85 or less, more specifically Was 1.82 or less and was within the desired range.
  • the optical glasses according to the examples of the present invention each have an Abbe number ( ⁇ d ) of 40 or more, more specifically 44 or more, and this Abbe number is 60 or less, more specifically 57 or less, It was within the desired range.
  • optical glasses of the examples of the present invention all had a specific gravity of 5.50 or less, more specifically 5.10 or less, and were within a desired range.
  • the optical glass of the example of the present invention has the refractive index and the Abbe number within the desired range, high devitrification resistance, little coloration and small specific gravity.
  • a glass block was formed using the optical glass of the embodiment of the present invention, and this glass block was ground and polished to be processed into a lens and a prism shape. As a result, it was possible to stably process into various lens and prism shapes.

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  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
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Abstract

Le but de la présente invention est d'obtenir : un verre optique présentant un indice de réfraction (nd) et un nombre d'Abbe (νd) compris dans des plages appropriées, ainsi qu'une résistance à la dévitrification élevée ; et un élément optique. Le verre optique contient, sur une base massique, 10,5 à 50,5 % d'un composant B2O3, 18,0 à 60,0 % du composant La2O3 , 15,0 % ou moins d'un composant ZnO et 5,0 % ou moins d'un composant RO, et présente un rapport de masse SiO2/B2O3 de 0,5 ou moins. L'utilisation du composant B2O3, du composant La2O3 et du composant RO en combinaison et du rapport de masse SiO2/B2O3 dans la plage prédéterminée fournit un verre optique présentant un nombre d'Abbe (νd) de 40 ou plus. L'élément optique contient le verre optique en tant que matériau de base.
PCT/JP2018/024515 2017-08-11 2018-06-28 Verre optique, élément optique et dispositif optique WO2019031095A1 (fr)

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Cited By (3)

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US11802073B2 (en) 2020-09-10 2023-10-31 Corning Incorporated Silicoborate and borosilicate glasses with high refractive index and low density
US11976004B2 (en) 2020-09-10 2024-05-07 Corning Incorporated Silicoborate and borosilicate glasses having high refractive index and high transmittance to blue light
US11999651B2 (en) 2020-09-10 2024-06-04 Corning Incorporated Silicoborate and borosilicate glasses having high refractive index and low density

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