WO2014034623A1 - 光学ガラス、プリフォーム及び光学素子 - Google Patents

光学ガラス、プリフォーム及び光学素子 Download PDF

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WO2014034623A1
WO2014034623A1 PCT/JP2013/072779 JP2013072779W WO2014034623A1 WO 2014034623 A1 WO2014034623 A1 WO 2014034623A1 JP 2013072779 W JP2013072779 W JP 2013072779W WO 2014034623 A1 WO2014034623 A1 WO 2014034623A1
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component
glass
optical glass
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mass
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PCT/JP2013/072779
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French (fr)
Japanese (ja)
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哲也 津田
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株式会社オハラ
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Priority to CN201380044748.5A priority Critical patent/CN104583142B/zh
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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
    • C03C3/12—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

Definitions

  • the present invention relates to an optical glass, a preform, and an optical element.
  • Optical systems such as digital cameras and video cameras, although large and small, contain blurs called aberrations. This aberration is classified into monochromatic aberration and chromatic aberration. In particular, the chromatic aberration is strongly dependent on the material characteristics of the lens used in the optical system.
  • chromatic aberration is corrected by combining a low-dispersion convex lens and a high-dispersion concave lens, but this combination can only correct aberrations in the red region and the green region, and remains in the blue region.
  • This blue region aberration that cannot be removed is called a secondary spectrum.
  • the partial dispersion ratio ( ⁇ g, F) is used as an index of the optical characteristics to be noticed in the optical design.
  • an optical material having a large partial dispersion ratio ( ⁇ g, F) is used for the low dispersion side lens, and the partial dispersion ratio ( By using an optical material having a small ⁇ g, F), the secondary spectrum is corrected well.
  • the partial dispersion ratio ( ⁇ g, F) is expressed by the following equation (1).
  • ⁇ g, F (n g ⁇ n F ) / (n F ⁇ n C ) (1)
  • optical glass there is an approximately linear relationship between a partial dispersion ratio ( ⁇ g, F) representing partial dispersion in a short wavelength region and an Abbe number ( ⁇ d ).
  • the straight line representing this relationship plots the partial dispersion ratio and Abbe number of NSL7 and PBM2 on the Cartesian coordinates employing the partial dispersion ratio ( ⁇ g, F) on the vertical axis and the Abbe number ( ⁇ d ) on the horizontal axis. It is represented by a straight line connecting two points and is called a normal line (see FIG. 1).
  • Normal glass which is the standard for normal lines, differs depending on the optical glass manufacturer, but each company defines it with almost the same slope and intercept.
  • NSL7 and PBM2 are optical glasses manufactured by OHARA, Inc., and the Abbe number ( ⁇ d ) of PBM2 is 36.3, the partial dispersion ratio ( ⁇ g, F) is 0.5828, and the Abbe number ( ⁇ d ) of NSL7. Is 60.5, and the partial dispersion ratio ( ⁇ g, F) is 0.5436.
  • optical glasses as shown in Patent Documents 1 to 3 are known.
  • the glasses disclosed in Patent Documents 1 to 3 have a small partial dispersion ratio and are not sufficient for use as a lens for correcting the secondary spectrum. Further, the glasses disclosed in Patent Documents 1 to 3 are not highly transparent with respect to visible light, and are not sufficient for use in transmitting visible light. That is, there is a demand for an optical glass having a small Abbe number ( ⁇ d ), high dispersion, a small partial dispersion ratio ( ⁇ g, F), and high transparency to visible light.
  • ⁇ d Abbe number
  • ⁇ g, F small partial dispersion ratio
  • the present invention has been made in view of the above problems, and the object of the present invention is to have a small Abbe number ( ⁇ d ) and a partial dispersion while the refractive index (n d ) is within a desired range.
  • the object is to obtain an optical glass having a smaller ratio ( ⁇ g, F) and improved transparency to visible light, and a preform and an optical element using the optical glass.
  • the present inventors have conducted intensive test studies.
  • the ZrO 2 component is used in combination as necessary.
  • the glass has a high refractive index, but the glass has a desired partial dispersion ratio ( ⁇ g, F) between the Abbe number ( ⁇ d ).
  • ⁇ g, F partial dispersion ratio
  • the content of the B 2 O 3 component, the rare earth component and the ZrO 2 component are within a predetermined range, whereby the coloring of the glass is reduced while the stability of the glass is enhanced, and the present invention. It came to complete.
  • the present invention provides the following.
  • the B 2 O 3 component is 5.0% or more and 40.0% or less, and the Ln 2 O 3 component (wherein Ln is selected from the group consisting of La, Gd, Y, and Yb) More than 0% and less than 50.0% of Nb 2 O 5 component, and the partial dispersion ratio ( ⁇ g, F) is Abbe number ( ⁇ d) Satisfies the relationship of ( ⁇ 0.00162 ⁇ ⁇ d + 0.63822) ⁇ ( ⁇ g, F) ⁇ ( ⁇ 0.00275 ⁇ ⁇ d + 0.68125) in the range of ⁇ d ⁇ 31, and in the range of ⁇ d> 31 ( Optical glass satisfying the relationship of ⁇ 0.00162 ⁇ ⁇ d + 0.63822) ⁇ ( ⁇ g, F) ⁇ ( ⁇ 0.00162 ⁇ ⁇ d + 0.64622).
  • optical glass according to (1) which contains, by mass%, a ZrO 2 component of more than 0% and 15.0% or less.
  • the mass ratio (La 2 O 3 / Ln 2 O 3) is 0.5 or more (1) to (3) any description of the optical glass.
  • MgO component by mass% 0-10.0% CaO component 0-10.0% SrO component 0-20.0% BaO component 0-20.0% ZnO component 0-30.0% The optical glass according to any one of (1) to (11).
  • the mass sum of the RO component (wherein R is one or more selected from the group consisting of Mg, Ca, Sr, Ba, and Zn) is 30.0% or less (1) to (13) Any one of the optical glasses.
  • optical glass according to any one of (1) to (14), wherein the content of the SiO 2 component is 20.0% or less by mass.
  • the refractive index (n d ) is within a desired range
  • the Abbe number ( ⁇ d ) is small
  • the partial dispersion ratio ( ⁇ g, F) is small
  • the transparency to visible light is enhanced.
  • Optical glass, and a preform and an optical element using the optical glass can be obtained.
  • the B 2 O 3 component is 5.0% or more and 40.0% or less, and the Ln 2 O 3 component (wherein Ln is a group consisting of La, Gd, Y, and Yb). Selected from 15.0% to 60.0% by mass, and Nb 2 O 5 component more than 0% to 50.0%, and the partial dispersion ratio ( ⁇ g, F) is Abbe Satisfies the relationship of ( ⁇ 0.00162 ⁇ ⁇ d + 0.63822) ⁇ ( ⁇ g, F) ⁇ ( ⁇ 0.00275 ⁇ ⁇ d + 0.68125) in the range of ⁇ d ⁇ 31 with respect to the number ( ⁇ d), and ⁇ d> 31 In the range of ( ⁇ 0.00162 ⁇ ⁇ d + 0.63822) ⁇ ( ⁇ g, F) ⁇ ( ⁇ 0.00162 ⁇ ⁇ d + 0.64622).
  • the glass has a high refractive index. It is done.
  • the Nb 2 O 5 component is used and its content is within a predetermined range, whereby the glass is highly dispersed (lower Abbe number).
  • a rare-earth component such as La 2 O 3 component and Nb 2 O 5 component are used together with a ZrO 2 component as necessary, and the content thereof is within a predetermined range, whereby the partial dispersion ratio of the glass ( ⁇ g, F) has a desired relationship with the Abbe number ( ⁇ d ).
  • the B 2 O 3 component and the La 2 O 3 component are used in combination, and the content of these components is within a predetermined range, so that the color of the glass is reduced while the stability of the glass is enhanced. Therefore, an optical glass having a low Abbe number ( ⁇ d ), a small partial dispersion ratio ( ⁇ g, F), and a high transparency to visible light, while the refractive index (n d ) is within a desired range; A preform and an optical element using the same can be obtained.
  • the composition range of each component constituting the optical glass of the present invention is described below. Unless otherwise specified in the present specification, the contents of the respective components are all expressed in mass% with respect to the total mass of the glass in terms of oxide.
  • the “oxide equivalent composition” means that the oxide, composite salt, metal fluoride, etc. used as a raw material of the glass component of the present invention are all decomposed and changed into an oxide when melted. It is the composition which described each component contained in glass by making the total mass of the said production
  • the B 2 O 3 component is an essential component that is indispensable as a glass-forming oxide. Particularly, by containing 5.0% or more of the B 2 O 3 component, the devitrification resistance of the glass can be improved and the dispersion can be reduced. In addition, this makes it possible to reduce the specific gravity of the glass and reduce devitrification and coloring due to reheating. Therefore, the content of the B 2 O 3 component is preferably 5.0%, more preferably 10.0%, still more preferably 13.0%, still more preferably 14.0%, and even more preferably 17.0%. Is the lower limit.
  • the content of the B 2 O 3 component is preferably 40.0%, more preferably 35.0%, further preferably 30.0%, and further preferably 25.0%.
  • 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.
  • Sum (mass sum) of contents of Ln 2 O 3 components (wherein Ln is one or more selected from the group consisting of La, Gd, Y, and Yb) is 15.0% or more and 60.0% or less To.
  • the mass sum of the Ln 2 O 3 component is preferably 15.0%, more preferably 18.0%, still more preferably 21.0%, still more preferably 26.0%, and even more preferably 29.0%. Is the lower limit.
  • the upper limit of the mass sum of the Ln 2 O 3 component is preferably 60.0%, more preferably less than 52.0%, still more preferably less than 45.0%, and even more preferably less than 40.0%. .
  • the Nb 2 O 5 component is an essential component that can contain more than 0% to increase the refractive index of the glass, lower the Abbe number, reduce the specific gravity of the glass, and lower the partial dispersion ratio. Therefore, the content of the Nb 2 O 5 component is preferably more than 0%, more preferably more than 1.0%, still more preferably more than 5.0%, still more preferably more than 8.0%, still more preferably 11. Over 0%, more preferably over 15.0%, and even more preferably over 17.0%.
  • the content of the Nb 2 O 5 component 50.0% or less the deterioration of the devitrification resistance of the glass due to the excessive content of the Nb 2 O 5 component is suppressed, and the visible light of the glass is not affected.
  • the content of the Nb 2 O 5 component is preferably 50.0%, more preferably 45.0%, still more preferably 40.0%, and further preferably 37.0%.
  • Nb 2 O 5 component Nb 2 O 5 or the like can be used as a raw material.
  • the ZrO 2 component is an optional component that can increase the refractive index and reduce the partial dispersion ratio while increasing the devitrification resistance of the glass when it is contained in an amount of more than 0%. Moreover, this can reduce devitrification and coloring due to reheating of the glass. Therefore, the content of the ZrO 2 component is preferably more than 0%, more preferably more than 0.5%, still more preferably 2.1%, and even more preferably 3.7%. On the other hand, when the content of the ZrO 2 component below 15.0%, the devitrification resistance deteriorates conversely. Therefore, the upper limit of the content of the ZrO 2 component is preferably 15.0%, more preferably 12.0%, and still more preferably 9.0%. As the ZrO 2 component, ZrO 2 , ZrF 4 or the like can be used as a raw material.
  • the La 2 O 3 component is a component that can contain 10.0% or more to reduce the specific gravity and the partial dispersion ratio while achieving a high refractive index and high dispersion of the glass. Accordingly, the content of the La 2 O 3 component is preferably 10.0%, more preferably 13.0%, even more preferably 16.0%, still more preferably 18.0%, and even more preferably 20.0%. More preferably, the lower limit is 23.0%, more preferably 26.0%, and still more preferably 29.0%. In particular, by setting the content of the La 2 O 3 component to 60.0% or less, the stability of the glass can be improved, devitrification can be reduced, and an increase in the Abbe number can be suppressed.
  • the content of the La 2 O 3 component is preferably 60.0%, more preferably 50.0%, and still more preferably 40.0.
  • 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, the Gd 2 O 3 component, the Yb 2 O 3 component, and the Lu 2 O 3 component are optional components that can increase the refractive index of the glass when the content exceeds 0%.
  • the devitrification resistance of the glass can be increased, and It is difficult to increase the Abbe number of glass.
  • the material cost of glass can be reduced by reducing the content of each of the Gd 2 O 3 component, the Yb 2 O 3 component, and the Lu 2 O 3 component.
  • the content of the Y 2 O 3 component is preferably 20.0%, more preferably 15.0%, even more preferably 10.0%, and even more preferably 5.0%.
  • the content of the Gd 2 O 3 component is preferably 30.0%, more preferably 20.0%, more preferably less than 14.0%, still more preferably less than 10.0%.
  • the content of each of the Yb 2 O 3 component and the Lu 2 O 3 component is preferably 10.0%, more preferably 5.0%, still more preferably 1.0%, and still more preferably 0.00%. Less than 5%.
  • Y 2 O 3 component, Gd 2 O 3 component, Yb 2 O 3 component and Lu 2 O 3 component are Gd 2 O 3 , GdF 3 , Y 2 O 3 , YF 3 , Yb 2 O 3 , Lu 2 as raw materials. O 3 or the like can be used.
  • the ratio (mass ratio) of the content of the La 2 O 3 component to the total content of the Ln 2 O 3 component is preferably 0.5 or more.
  • the content of La 2 O 3 component which has a strong effect of reducing the partial dispersion ratio among the rare earth elements, is relatively increased, so that the partial dispersion ratio can be reduced while obtaining the desired high devitrification resistance.
  • the mass ratio La 2 O 3 / Ln 2 O 3 is preferably 0.5, more preferably 0.8, and still more preferably 0.93.
  • the upper limit of this ratio is not particularly limited, and may be 1.0.
  • the sum (mass sum) of the contents of the Nb 2 O 5 component, the ZrO 2 component, and the La 2 O 3 component is preferably 30.0% or more.
  • the mass sum (Nb 2 O 5 + ZrO 2 + La 2 O 3 ) is preferably 30.0%, more preferably 40.0%, still more preferably 47.0%, still more preferably 53.0%, Preferably, 57.0% is set as the lower limit.
  • the mass sum of these components is not limited as long as a stable glass can be obtained, but the solubility and devitrification resistance of the glass can be improved by, for example, 85.0% or less. Accordingly, the upper limit of the mass sum (Nb 2 O 5 + ZrO 2 + La 2 O 3 ) is preferably 85.0%, more preferably 80.0%, and even more preferably 75.0%.
  • the TiO 2 component is an optional component that can reduce the Abbe number and improve the devitrification resistance while increasing the refractive index of the glass when it contains more than 0%.
  • the content of the TiO 2 component is 20.0% or less, the coloration of the glass can be reduced, and the internal transmittance of the glass with respect to light having a visible short wavelength (500 nm or less) can be increased. Further, this can suppress an increase in the partial dispersion ratio.
  • the content of the TiO 2 component is preferably 20.0%, more preferably 15.0%, even more preferably 10.0%, still more preferably 5.0%, still more preferably 4.0%, Preferably, the upper limit is 3.0%.
  • TiO 2 component TiO 2 or the like can be used as a raw material.
  • the ratio (mass ratio) of the content of the TiO 2 component to the content of the Nb 2 O 5 component is preferably 1.00 or less.
  • the content of the TiO 2 component that raises the partial dispersion ratio is relative to the content of the Nb 2 O 5 component that lowers the partial dispersion ratio. Therefore, an optical glass having a lower partial dispersion ratio can be easily obtained while realizing a desired high refractive index. This also to reduce the content of TiO 2 component to color the glass, it is possible to obtain an optical glass that is preferably used in applications which transmits visible light.
  • the upper limit of the mass ratio (TiO 2 / Nb 2 O 5 ) is preferably 1.00, more preferably 0.50, still more preferably 0.30, and still more preferably 0.15.
  • the lower limit of the mass ratio is not particularly limited, and may be 0.
  • the WO 3 component is an optional component that can increase the refractive index of the glass to lower the Abbe number and increase the devitrification resistance of the glass when it contains more than 0%. Therefore, the content of the WO 3 component is preferably more than 0%, more preferably 0.3%, and even more preferably 0.5%. On the other hand, by making the content of the WO 3 component 20.0% or less, an increase in the partial dispersion ratio of the glass can be suppressed, and the transmittance of the glass with respect to visible light can be hardly lowered. Moreover, devitrification and coloring by reheating can be reduced thereby. Therefore, the content of the WO 3 component is preferably 20.0%, more preferably 15.0%, and still more preferably 10.0%. As the WO 3 component, WO 3 or the like can be used as a raw material.
  • the mass sum of the TiO 2 component and the WO 3 component is preferably 20.0% or less. Thereby, the raise of the partial dispersion ratio of glass can be suppressed, and the transmittance
  • the ratio of the sum of the contents of the TiO 2 component and the WO 3 component to the sum of the contents of the ZrO 2 component and the B 2 O 3 component is preferably 1.00 or less. Thereby, it is possible to easily obtain an optical glass having a higher transmittance for visible light. Therefore, the mass ratio (TiO 2 + WO 3 ) / (ZrO 2 + B 2 O 3 ) is preferably 1.00, more preferably 0.65, and still more preferably 0.40.
  • the ratio (mass ratio) of the content of WO 3 to the content of Nb 2 O 5 is preferably 0.50 or less.
  • the upper limit of the mass ratio (WO 3 / Nb 2 O 5 ) is preferably 0.50, more preferably 0.45, and still more preferably 0.40.
  • the MgO component, CaO component, SrO component, and BaO component are optional components that can adjust the refractive index, meltability, and devitrification of glass when the content exceeds 0%.
  • the content of the MgO component and the CaO component is set to 10.0% or less, respectively, or the content of the SrO component and the BaO component is set to 20.0% or less, respectively. Decline and devitrification can be reduced, and an increase in the partial dispersion ratio can be suppressed. Therefore, the content of each of the MgO component and the CaO component is preferably 10.0%, more preferably 5.0%, and still more preferably 3.0%.
  • each of the SrO component and the BaO component is preferably 20.0%, more preferably 10.0%, and still more preferably 6.0%.
  • MgCO 3 , 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 as raw materials.
  • the ZnO component is an optional component that lowers the glass transition point and lowers the melting temperature of the glass raw material when it exceeds 0%. Therefore, the content of the ZnO component is preferably more than 0%, more preferably 1.0%, still more preferably 3.0%, still more preferably 3.5%, still more preferably 4.5%, still more preferably The lower limit may be 5.6%. On the other hand, by setting the content of the ZnO component to 30.0% or less, devitrification of the glass can be reduced, the specific gravity of the glass can be reduced, and an increase in the partial dispersion ratio can be suppressed.
  • the upper limit of the content of the ZnO component is preferably 30.0%, more preferably 20.0%, still more preferably 15.0%, and still more preferably 14.0%.
  • ZnO component ZnO, ZnF 2 or the like can be used as a raw material.
  • the ratio (mass ratio) of the content of the B 2 O 3 component to the content of the ZnO component is preferably 0.01 or more. Thereby, the partial dispersion ratio of glass can be made lower. Therefore, the mass ratio (ZnO / B 2 O 3 ) is preferably 0.01, more preferably 0.10, and still more preferably 0.18.
  • the upper limit of the mass ratio (ZnO / B 2 O 3 ) may be a value obtained from the range of the content of the ZnO component and the B 2 O 3 component, for example, 1.00, specifically The upper limit may be 0.80, more specifically 0.70.
  • the total content (mass sum) of RO components (wherein R is one or more selected from the group consisting of Mg, Ca, Sr, Ba, and Zn) is preferably 30.0% or less.
  • R is one or more selected from the group consisting of Mg, Ca, Sr, Ba, and Zn
  • the upper limit of the mass sum of the RO component is preferably 30.0%, more preferably 20.0%, and still more preferably 14.0%.
  • the SiO 2 component is an optional component that can increase the viscosity of the molten glass, promote stable glass formation, and reduce devitrification (generation of crystals) when it is contained in an amount of more than 0%.
  • the content of the SiO 2 component is preferably 20.0%, more preferably less than 10.0%, even more preferably less than 6.0%, still more preferably less than 4.0%, and even more preferably 2.%. It is less than 0%, more preferably less than 0.5%.
  • SiO 2 component SiO 2 , K 2 SiF 6 , Na 2 SiF 6 or the like can be used as a raw material.
  • the ratio of the content of the SiO 2 component to the content of the B 2 O 3 component is preferably less than 1.00.
  • the content of the B 2 O 3 component for decreasing the specific gravity is increased relative to the content of the SiO 2 component for increasing the specific gravity of the glass.
  • Small optical glass can be obtained. Therefore, the mass ratio (SiO 2 / B 2 O 3 ) is preferably less than 1.00, more preferably less than 0.50, and still more preferably less than 0.30.
  • the Li 2 O component, the Na 2 O component, and the K 2 O component are optional components that can improve the meltability of the glass and lower the glass transition point when containing more than 0%.
  • the Li 2 O component is also a component that lowers the partial dispersion ratio of the glass.
  • Na 2 O component and K 2 O ingredients is also a component enhances devitrification resistance of the glass.
  • by reducing the content of each of the Li 2 O component, the Na 2 O component, and the K 2 O component it is difficult to lower the refractive index of the glass and the devitrification resistance can be improved.
  • the upper limit of the content of the Li 2 O component is preferably 20.0%, more preferably 10.0%, more preferably 5.0%, and even more preferably 3.0%.
  • the content of the Na 2 O component is preferably 15.0%, more preferably 10.0%, more preferably 5.0%, and still more preferably 3.0%.
  • the K 2 O component content is preferably 10.0%, more preferably 5.0%, and still more preferably 3.0%.
  • Li 2 O component, Na 2 O component, and K 2 O component are Li 2 CO 3 , LiNO 3 , LiF, Na 2 CO 3 , NaNO 3 , NaF, Na 2 SiF 6 , K 2 CO 3 , KNO 3 as raw materials. , KF, KHF 2 , K 2 SiF 6 or the like can be used.
  • the total amount of Rn 2 O components (wherein Rn is one or more selected from the group consisting of Li, Na, K, and Cs) is preferably 20.0% or less. Thereby, it is difficult to lower the refractive index of the glass, and devitrification at the time of glass formation can be reduced. Moreover, devitrification and coloring by reheating can be reduced thereby. Therefore, the upper limit of the mass sum of the content of the Rn 2 O component is preferably 20.0%, more preferably 10.0%, and still more preferably 5.0%.
  • the P 2 O 5 component when ultra containing 0%, which is an optional component that enhances devitrification resistance.
  • the content of the P 2 O 5 component is preferably 20.0%, more preferably 10.0%, and still more preferably 5.0%.
  • Al (PO 3 ) 3 , Ca (PO 3 ) 2 , Ba (PO 3 ) 2 , BPO 4 , H 3 PO 4 or the like can be used as a raw material.
  • the GeO 2 component is an optional component that can increase the refractive index of glass and increase the resistance to devitrification when it exceeds 0%.
  • the content of the GeO 2 component is preferably 10.0%, more preferably 5.0%, more preferably less than 3.0%, still more preferably 1.5%.
  • GeO 2 component GeO 2 or the like can be used as a raw material.
  • the Ta 2 O 5 component is an optional component that, when contained in excess of 0%, lowers the partial dispersion ratio while increasing the refractive index of the glass and increases the devitrification resistance of the glass.
  • the content of the Ta 2 O 5 component 15.0% or less, the amount of the Ta 2 O 5 component, which is a rare mineral resource, is reduced, and the glass is easily melted at a lower temperature. Glass material costs and production costs can be reduced. Moreover, it is easy to obtain an optical glass having a smaller specific gravity. Therefore, the content of the Ta 2 O 5 component is preferably 15.0%, more preferably 10.0%, still more preferably 5.0%, and further preferably 1.0%. In particular, from the viewpoint of further reducing the material cost of glass, it is most preferable not to contain a Ta 2 O 5 component. As the Ta 2 O 5 component, Ta 2 O 5 or the like can be used as a raw material.
  • the Bi 2 O 3 component is an optional component that can increase the refractive index of the glass to lower the Abbe number and lower the glass transition point when it contains more than 0%.
  • the content of the Bi 2 O 3 component is preferably 15.0%, more preferably 10.0%, and still more preferably 5.0%.
  • Bi 2 O 3 component Bi 2 O 3 or the like can be used as a raw material.
  • the TeO 2 component is an optional component that raises the refractive index of the glass to lower the partial dispersion ratio and lowers the glass transition point when it is contained in excess of 0%.
  • the content of TeO 2 components is preferably 20.0%, more preferably 15.0%, still more preferably 10.0%, and still more preferably 5.0%.
  • TeO 2 component can use TeO 2 or the like as a raw material.
  • the Al 2 O 3 component and the Ga 2 O 3 component are optional components that can increase the chemical durability of the glass and improve the devitrification resistance when the content exceeds 0%.
  • the content of each of the Al 2 O 3 component and the Ga 2 O 3 component is preferably 20.0%, more preferably 15.0%, still more preferably 10.0%, and even more preferably 5.0%. Is the upper limit.
  • Al 2 O 3 component and the Ga 2 O 3 component Al 2 O 3 , Al (OH) 3 , AlF 3 , Ga 2 O 3 , Ga (OH) 3 or the like can be used as a raw material.
  • the SnO 2 component is an optional component that can be refined by reducing the oxidation of the molten glass and can increase the visible light transmittance of the glass.
  • the content of the SnO 2 component is preferably 3.0%, more preferably 2.0%, and still more preferably 1.0%.
  • 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 that can degas the molten glass when it contains more than 0%.
  • the content of the Sb 2 O 3 component is preferably 3.0%, more preferably 2.0%, and still more preferably 1.0%.
  • Sb 2 O 3 component 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.
  • components defoamed fining glass is not limited to the above Sb 2 O 3 component, a known refining agents in the field of glass production, it is possible to use a defoamer or a combination thereof.
  • each transition metal component such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag and Mo, excluding Ti, Zr, Nb, W, La, Gd, Y, Yb, and Lu, is independent of each other. Or, even when it is contained in a small amount in combination, the glass is colored and has the property of causing absorption at a specific wavelength in the visible range. .
  • lead compounds such as PbO and arsenic compounds such as As 2 O 3 are components with high environmental loads, it is desirable that they are not substantially contained, that is, not contained at all except for inevitable mixing.
  • each component of Th, Cd, Tl, Os, Be, and Se has tended to be refrained from being used as a harmful chemical material in recent years, and not only in the glass manufacturing process, but also in the processing process and disposal after commercialization. Until then, environmental measures are required. Therefore, when importance is placed on the environmental impact, it is preferable that these are not substantially contained.
  • the glass composition of the present invention cannot be expressed directly in the description of mol% because the composition is expressed by mass% with respect to the total mass of the glass of oxide conversion composition, but various properties required in the present invention.
  • the composition expressed by mol% of each component present in the glass composition satisfying the above conditions generally takes the following values in terms of oxide conversion.
  • 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, a quartz crucible or an alumina crucible and roughly melted, then a gold crucible, a platinum crucible In a platinum alloy crucible or iridium crucible, melt in a temperature range of 1100-1500 ° C. for 2-5 hours, stir to homogenize, blow out bubbles, etc., then lower the temperature to 1000-1300 ° C. and then finish stirring This is done by removing the striae, casting into a mold and slow cooling.
  • 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 1.80, more preferably 1.83, still more preferably 1.85, and still more preferably 1.88. . On the other hand, the upper limit of the refractive index (n d ) of the optical glass of the present invention is preferably 2.00, more preferably 1.98, and even more preferably 1.96. Further, the Abbe number ( ⁇ d ) of the optical glass of the present invention is preferably 40, more preferably 38, and still more preferably 34.
  • Abbe number ( ⁇ d ) of the optical glass of the present invention is preferably 40, more preferably 38, and still more preferably 34.
  • the lower limit of the Abbe number ( ⁇ d ) of the optical glass of the present invention is preferably 20, more preferably 23, and even more preferably 26.
  • the degree of freedom in optical design is increased, and a large amount of light refraction can be obtained even if the device is made thinner.
  • the optical glass of the present invention has a low partial dispersion ratio ( ⁇ g, F). More specifically, the partial dispersion ratio ( ⁇ g, F) of the optical glass of the present invention is within the range of ⁇ d ⁇ 31 with respect to the Abbe number ( ⁇ d ) ( ⁇ 0.00162 ⁇ ⁇ d + 0.63822). ⁇ ( ⁇ g, F) ⁇ ( ⁇ 0.00275 ⁇ ⁇ d + 0.68125) is satisfied, and ( ⁇ 0.00162 ⁇ ⁇ d + 0.63822) ⁇ ( ⁇ g, F) ⁇ ( ⁇ in the range of ⁇ d > 31 0.00162 ⁇ ⁇ d + 0.64622).
  • the lower limit of the partial dispersion ratio ( ⁇ g, F) of the optical glass at ⁇ d ⁇ 31 is preferably ( ⁇ 0.00162 ⁇ ⁇ d + 0.63822), more preferably ( ⁇ 0.00162 ⁇ ⁇ d + 0.63922), More preferably ( ⁇ 0.00162 ⁇ ⁇ d + 0.64022).
  • the upper limit of the partial dispersion ratio ( ⁇ g, F) of the optical glass at ⁇ d ⁇ 31 is preferably ( ⁇ 0.00275 ⁇ ⁇ d + 0.68125), more preferably ( ⁇ 0.00275 ⁇ ⁇ d + 0.68025), More preferably ( ⁇ 0.00275 ⁇ ⁇ d + 0.67925).
  • the lower limit of the partial dispersion ratio ( ⁇ g, F) of the optical glass at ⁇ d > 31 is preferably ( ⁇ 0.00162 ⁇ ⁇ d + 0.63822), more preferably ( ⁇ 0.00162 ⁇ ⁇ d + 0.63922), Preferably, it is ( ⁇ 0.00162 ⁇ ⁇ d + 0.64022).
  • the upper limit of the partial dispersion ratio ( ⁇ g, F) of the optical glass at ⁇ d > 31 is preferably ( ⁇ 0.00162 ⁇ ⁇ d + 0.64622), more preferably ( ⁇ 0.00162 ⁇ ⁇ d + 0.64522). More preferably, it is ( ⁇ 0.00162 ⁇ ⁇ d + 0.64422).
  • 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 Abbe number ( ⁇ d ) are represented by curves.
  • the optical glass of this invention has little coloring.
  • the wavelength ( ⁇ 70 ) indicating a spectral transmittance of 70% in a sample having a thickness of 10 mm is 500 nm or less, more preferably 470 nm or less, and still more preferably. Is 450 nm or less, more preferably 430 nm or less.
  • a wavelength ( ⁇ 5 ) showing a spectral transmittance of 5% in a sample having a thickness of 10 mm is 420 nm or less, more preferably 400 nm or less, and further preferably 380 nm or less.
  • this optical glass can be preferably used as a material for an optical element 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 5.00 [g / cm 3 ] or less. Thereby, since the mass of an optical element and an optical apparatus using the same is reduced, it can contribute to the weight reduction of an optical apparatus. Therefore, the specific gravity of the optical glass of the present invention is preferably 5.00, more preferably 4.90, and preferably 4.80.
  • the specific gravity of the optical glass of the present invention is generally about 3.00 or more, more specifically 3.50 or more, and more specifically 4.00 or more in many cases.
  • the specific gravity of the optical glass of the present invention can be measured based on Japan Optical Glass Industry Association Standard JOGIS05-1975 “Method for Measuring Specific Gravity of Optical Glass”.
  • the optical glass of the present invention preferably has good press formability. That is, the optical glass of the present invention divides the transmittance of light (d-line) having a wavelength of 587.56 nm of the test piece after the reheating test (ii) by the transmittance of d-line of the test piece before the reheating test.
  • the measured value is preferably 0.95 or more.
  • a lambda 70 is a wavelength at which the transmittance of the reheating test (a) before the specimen is 70% and the difference between the lambda 70 of the test piece after the reheating test is 20nm or less.
  • the value obtained by dividing the transmittance of the light beam (d-line) having a wavelength of 587.56 nm of the test piece after the reheating test (ii) by the transmittance of the d-line of the test piece before the reheating test (ii) is The lower limit is preferably 0.95, more preferably 0.96, and still more preferably 0.97.
  • the difference between the lambda 70 of the test piece after the reheating test and lambda 70 of reheating test (a) prior to the test piece (b) is preferably 20 nm, more preferably 18 nm, more preferably the upper limit of the 16nm To do.
  • reheating test (A) a test piece 15 mm ⁇ 15 mm ⁇ 30 mm is reheated, and the temperature is raised from room temperature to a temperature 80 ° C. higher than the transition temperature (Tg) of each sample in 150 minutes.
  • the temperature can be kept at 30 ° C. higher than the transition temperature (Tg) for 30 minutes, then naturally cooled to room temperature, and the two opposing surfaces of the test piece are polished to a thickness of 10 mm and visually observed.
  • a glass molded body can be produced from the produced optical glass by means of mold press molding such as reheat press molding or precision press molding. That is, a preform for mold press molding is prepared from optical glass, and after performing reheat press molding on the preform, polishing is performed to prepare a glass molded body, or for example, polishing is performed.
  • the preform can be precision press-molded to produce a glass molded body.
  • the means for producing the glass molded body is not limited to these means.
  • the glass molded body produced in this way is useful for various optical elements, and among them, it is particularly preferable to use for optical elements such as lenses and prisms.
  • optical elements such as lenses and prisms.
  • color bleeding due to chromatic aberration in the transmitted light of the optical system provided with the optical element is reduced. Therefore, when this optical element is used in a camera, a photographing object can be expressed more accurately, and when this optical element is used in a projector, a desired image can be projected with higher definition.
  • the glasses of the examples and comparative examples of the present invention are ordinary optical glasses such as oxides, hydroxides, carbonates, nitrates, fluorides, hydroxides, and metaphosphate compounds corresponding to the raw materials of the respective components. After selecting the high-purity raw materials to be used in the above, weighing them so as to have the composition ratios of the examples and comparative examples shown in the table, mixing them uniformly, and then putting them into a platinum crucible, making it easy to melt the glass composition Depending on the temperature, melt in an electric furnace at a temperature range of 1100-1400 ° C for 3-5 hours, stir to homogenize, blow off bubbles, etc. The glass was prepared by casting and slowly cooling.
  • permeability of the glass of an Example and a comparative example was measured according to Japan Optical Glass Industry Association standard JOGIS02.
  • the presence / absence and degree of coloration of the glass were determined by measuring the transmittance of the glass.
  • a face parallel polished product having a thickness of 10 ⁇ 0.1 mm was measured for a spectral transmittance of 200 to 800 nm in accordance with JISZ8722, and ⁇ 5 (wavelength when the transmittance was 5%) and ⁇ 70 (transmittance). Wavelength at 70%).
  • the optical glass of the example of the present invention has a partial dispersion ratio ( ⁇ g, F) of ( ⁇ 0.00275 ⁇ ⁇ d + 0.68125) or less when ⁇ d ⁇ 31, more specifically ( ⁇ 0.00275 ⁇ ⁇ d + 0. 67840) or less.
  • the partial dispersion ratio ( ⁇ g, F) was ( ⁇ 0.00162 ⁇ ⁇ d + 0.64622) or less, more specifically, ( ⁇ 0.00162 ⁇ ⁇ d + 0.64280) or less.
  • the partial dispersion ratio ( ⁇ g, F) is ( ⁇ 0.00162 ⁇ ⁇ d + 0.63822) or more, more specifically ( ⁇ 0.00162 ⁇ ⁇ d + 0.64050) or more.
  • Met the relationship between the partial dispersion ratio ( ⁇ g, F) and the Abbe number ( ⁇ d ) for the glass of the example of the present application is as shown in FIG. Therefore, it was found that the optical glass of the example had a partial dispersion ratio ( ⁇ g, F) within a desired range.
  • the glasses of the comparative examples No. A, No. C to No.
  • E) of the present invention have ⁇ d > 31 and the partial dispersion ratio ( ⁇ g, F) is ( ⁇ 0.00162 ⁇ ⁇ d + 0.64622). ).
  • the glass of Comparative Example (No. B) of the present invention had ⁇ d ⁇ 31 and the partial dispersion ratio ( ⁇ g, F) exceeded ( ⁇ 0.00275 ⁇ ⁇ d + 0.68125). 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 1.80 or more, more specifically 1.90 or more, and this refractive index (n d ) is 2.00 or less. More specifically, it was 1.96 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 20 or more, more specifically 28 or more, and this Abbe number ( ⁇ d ) of 40 or less, more specifically 33. And within the desired range.
  • the optical glasses of the examples of the present invention each had a ⁇ 70 (wavelength at a transmittance of 70%) of 500 nm or less, more specifically 422 nm or less.
  • each of ⁇ 5 (wavelength at 5% transmittance) was 420 nm or less, more specifically 370 nm or less.
  • the optical glass of the example of the present invention has a high transmittance for visible light and a small chromatic aberration, while the refractive index (n d ) and the Abbe number ( ⁇ d ) are within the desired ranges. became.

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PCT/JP2013/072779 2012-08-30 2013-08-26 光学ガラス、プリフォーム及び光学素子 WO2014034623A1 (ja)

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EP3950620A4 (en) * 2019-04-05 2022-12-28 Nippon Electric Glass Co., Ltd. GLASS DECORATION ARTICLE

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JP6663177B2 (ja) * 2015-07-10 2020-03-11 株式会社オハラ 光学ガラス、プリフォーム及び光学素子
CN106927674A (zh) * 2015-11-11 2017-07-07 株式会社小原 一种光学玻璃、预制件以及光学元件
CN106915901A (zh) * 2015-12-25 2017-07-04 株式会社小原 一种光学玻璃、预制件以及光学元件
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CN109592898B (zh) * 2017-10-02 2023-09-19 株式会社小原 光学玻璃、预成型材及光学元件
JP7076981B2 (ja) * 2017-10-25 2022-05-30 キヤノン株式会社 光学ガラス、光学素子、光学機器および光学ガラスの製造方法
CN117105524A (zh) * 2018-03-27 2023-11-24 成都光明光电股份有限公司 光学玻璃
CN111217525A (zh) * 2018-11-27 2020-06-02 宜城市泳瑞玻璃科技有限公司 一种高折射、高色散透红外锗镓酸盐光学玻璃
US20220306517A1 (en) 2021-03-19 2022-09-29 Corning Incorporated High-Index Borate Glasses
NL2028260B1 (en) 2021-03-19 2022-09-29 Corning Inc High-Index Borate Glasses

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