WO2012133422A1 - Verre optique, préforme, et élément optique - Google Patents

Verre optique, préforme, et élément optique Download PDF

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Publication number
WO2012133422A1
WO2012133422A1 PCT/JP2012/057957 JP2012057957W WO2012133422A1 WO 2012133422 A1 WO2012133422 A1 WO 2012133422A1 JP 2012057957 W JP2012057957 W JP 2012057957W WO 2012133422 A1 WO2012133422 A1 WO 2012133422A1
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component
glass
optical glass
less
optical
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PCT/JP2012/057957
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English (en)
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 claimed from JP2011186050A external-priority patent/JP5748613B2/ja
Priority claimed from JP2011186053A external-priority patent/JP5748614B2/ja
Application filed by 株式会社オハラ filed Critical 株式会社オハラ
Priority to CN2012800158423A priority Critical patent/CN103459339A/zh
Publication of WO2012133422A1 publication Critical patent/WO2012133422A1/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
    • C03C3/12—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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/0092—Compositions for glass with special properties for glass with improved high visible transmittance, e.g. extra-clear glass

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 small ratio ( ⁇ g, F) and enhanced 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 ).
  • the glass coloring is reduced while the stability of the glass is enhanced. As a result, the present invention has been completed.
  • a ZrO 2 component is used in combination, and by making these contents within a predetermined range, coloring and devitrification hardly occur when the glass is reheated. I also found out. Specifically, the present invention provides the following.
  • the glass the total amount of substance of the oxide composition in terms of, B 2 O 3 component 55.0% 25.0% or more of the following in mol%, Ln 2 O 3 ingredient 6.0% or more 30.0 % or less (wherein, Ln is La, Gd, Y, 1 or more selected from the group consisting of Yb), and Nb 2 O 5 component contains less more 25.0% than 0%, the ZrO 2 component
  • the partial dispersion ratio ( ⁇ g, F) is in the range of ⁇ d ⁇ 31 with respect to the Abbe number ( ⁇ d), ( ⁇ 0.00162 ⁇ ⁇ d + 0.63822) ⁇ ( ⁇ g, F) ⁇ ( ⁇ 0.00275 ⁇ ⁇ d + 0.68125), and in the range of ⁇ d> 31, ( ⁇ 0.00162 ⁇ ⁇ d + 0.63822) ⁇ ( ⁇ g, F) ⁇ ( ⁇ 0.00162 ⁇ ⁇ d + 0.64622 ) Optical glass that satisfies the relationship.
  • any description of the optical glass of the molar sum to the glass the total amount of substance of the oxide composition in terms of (Nb 2 O 5 + ZrO 2 + La 2 O 3) is 15.0% or more (1) to (5).
  • the molar sum of the Rn 2 O component (wherein Rn is at least one selected from the group consisting of Li, Na, K, and Cs) with respect to the total amount of glass in an oxide equivalent composition is 30.0% or less.
  • the molar sum of the RO component (wherein R is one or more selected from the group consisting of Mg, Ca, Sr, Ba, Zn) with respect to the total amount of glass in an oxide equivalent composition is 35.0% or less
  • the B 2 O 3 component, the rare earth component, and the Nb 2 O 5 component are used in combination, and the content of these components and the content of the ZrO 2 component are within a predetermined range, whereby the high refractive index of the glass is obtained.
  • the partial dispersion ratio ( ⁇ g, F) of the glass has a desired relationship with the Abbe number ( ⁇ d ), and the coloring of the glass is reduced. Therefore, an optical glass having a low Abbe number ( ⁇ d ), a small partial dispersion ratio ( ⁇ g, F) and high transparency to visible light while having a refractive index (n d ) within a desired range, and A preform and an optical element using can be obtained.
  • the B 2 O 3 component is 25.0% or more and 55.0% or less, and the Ln 2 O 3 component is 6.0% in mol% with respect to the total amount of the glass having an oxide conversion composition. More than 30.0% (in the formula, Ln is one or more selected from the group consisting of La, Gd, Y, Yb), and Nb 2 O 5 component more than 0% and 25.0% or less,
  • the content of the ZrO 2 component is 10.0% or less
  • the partial dispersion ratio ( ⁇ g, F) 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 in the range of ⁇ d> 31, ( ⁇ 0.00162 ⁇ ⁇ d + 0.63822) ⁇ ( ⁇ g, F) ⁇ ( ⁇ 0.00162 X ⁇ 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.
  • each component constituting the optical glass of the present invention The composition range of each component constituting the optical glass of the present invention is described below. In the present specification, unless otherwise specified, the content of each component is expressed in mol% with respect to the total amount of glass in the oxide equivalent 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. It is the composition which described each component contained in glass by making the total substance amount of the said production
  • the B 2 O 3 component is an essential component that is indispensable as a glass-forming oxide in the optical glass of the present invention containing a large amount of rare earth oxides.
  • the content of the B 2 O 3 component is preferably 25.0%, more preferably 28.0%, still more preferably 32.0%, and most preferably 36.0%.
  • the content of the B 2 O 3 component is preferably 55.0%, more preferably 50.0%, and most preferably 48.0%.
  • 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.
  • the molar sum of the Ln 2 O 3 component (wherein Ln is one or more selected from the group consisting of La, Gd, Y, and Yb) is 6.0% or more and 30.0% or less. It is preferable that in particular, by setting the molar sum of the Ln 2 O 3 component to 6.0% or more, the glass has a low partial dispersion ratio while increasing the refractive index and Abbe number of the glass. It is possible to easily obtain a glass having a desired ratio between the partial dispersion ratio and the Abbe number. Accordingly, the lower limit of the molar sum of the Ln 2 O 3 component is preferably 6.0%, more preferably 10.0%, and most preferably 13.0%.
  • the molar sum of Ln 2 O 3 component is preferably 30.0%, more preferably 25.0%, and most preferably 22.0%.
  • the Nb 2 O 5 component is a component that increases the refractive index of the glass, decreases the Abbe number, and decreases the partial dispersion ratio.
  • the specific gravity of the glass can be reduced and the partial dispersion ratio of the glass can be reduced while increasing the refractive index of the glass and reducing the Abbe number.
  • the content of the Nb 2 O 5 component 25.0% 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 glass transmits visible light. Reduction in rate can be suppressed.
  • the content of the Nb 2 O 5 component is preferably more than 0%, more preferably 1.0%, still more preferably 2.0%, still more preferably 4.5%, and even more preferably 5.0. %, More preferably 5.5%, and most preferably 8.0%. Further, the content of this Nb 2 O 5 component is preferably 25.0%, more preferably 20.0%, and most preferably 17.0%.
  • Nb 2 O 5 or the like can be used as a raw material.
  • the ZrO 2 component is a component that lowers the partial dispersion ratio of the glass while increasing the refractive index of the glass to increase the devitrification resistance, and is an optional component in the optical glass of the present invention.
  • the content of the ZrO 2 component is preferably 15.0%, more preferably 12.0%, and still more preferably 10.0%.
  • the content of this ZrO 2 component is more preferably 9.0%, and even more preferably 8.0%.
  • ZrO 2 component is may not contain, by containing a ZrO 2 component, can easily lower the partial dispersion ratio while increasing the refractive index of the glass.
  • the content of the ZrO 2 component is preferably more than 0%, more preferably 0.5%, and most preferably 2.0%.
  • 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 increases the refractive index of the glass and decreases the partial dispersion ratio, and is an optional component in the optical glass of the present invention.
  • the content of the La 2 O 3 component is preferably 30.0%, more preferably 25.0%, still more preferably 22.0%, and most preferably 20.0%.
  • the La 2 O 3 component may not be contained, but by containing the La 2 O 3 component, a glass having a small specific gravity and a high refractive index and a small partial dispersion ratio can be obtained more easily. Therefore, the content of the La 2 O 3 component is preferably more than 0%, more preferably 7.0%, still more preferably 11.0%, and most preferably 14.0%.
  • 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, and the Yb 2 O 3 component are components that increase the refractive index of the glass, and are optional components in the optical glass of the present invention.
  • the devitrification resistance of the glass can be increased by setting the content of each of the Y 2 O 3 component, the Gd 2 O 3 component, and the Yb 2 O 3 component to 15.0% or less.
  • the number can be made difficult to increase.
  • the upper limit of each content of the Y 2 O 3 component, the Gd 2 O 3 component, and the Yb 2 O 3 component is preferably 15.0%, more preferably 10.0%, and most preferably 5.0%.
  • Gd 2 O 3 component, Gd 2 O 3 component, and Yb 2 O 3 component Gd 2 O 3 , GdF 3 , Y 2 O 3 , YF 3 , Yb 2 O 3 and the like can be used as raw materials.
  • the ratio of the content of the La 2 O 3 component to the content of the Ln 2 O 3 component is preferably 0.5 or more.
  • the content of the La 2 O 3 component which has a strong effect of reducing the partial dispersion ratio among rare earth elements, is relatively increased, so that the partial dispersion ratio is reduced while obtaining the desired devitrification resistance of the glass. can do. Therefore, the molar ratio La 2 O 3 / Ln 2 O 3 in the oxide equivalent composition is preferably 0.5, more preferably 0.7, and most preferably 0.8.
  • the upper limit of this ratio is not particularly limited, and may be 1.0.
  • the sum of the contents of the Nb 2 O 5 component and the ZrO 2 component is preferably more than 4.6% and not more than 30.0%.
  • the sum is more than 4.6%, the components that lower the partial dispersion ratio increase, so that an optical glass having a lower partial dispersion ratio can be obtained.
  • the solubility and devitrification resistance of the glass can be improved.
  • the molar sum (Nb 2 O 5 + ZrO 2 ) is preferably more than 4.6%, more preferably more than 5.0%, still more preferably more than 5.8%, most preferably 9 More than 0%.
  • the molar sum (Nb 2 O 5 + ZrO 2 ) is preferably 30.0%, more preferably 25.0%, and most preferably 20.0%.
  • the sum of the contents of the Nb 2 O 5 component, the ZrO 2 component, and the La 2 O 3 component is preferably 15.0% or more.
  • the molar sum (Nb 2 O 5 + ZrO 2 + La 2 O 3 ) is preferably 15.0%, more preferably 20.0%, still more preferably 23.0%, and most preferably 26.4%.
  • the sum of the total amount of these components is not limited as long as stable glass is obtained, the solubility and devitrification resistance of glass can be improved by making it 50.0% or less, for example.
  • this molar sum (Nb 2 O 5 + ZrO 2 + La 2 O 3 ) is preferably 50.0%, more preferably 45.0%, and most preferably 40.0%.
  • the TiO 2 component is a component that lowers the Abbe number and improves devitrification resistance while increasing the refractive index of the glass, and is an optional component in the optical glass of the present invention.
  • the content of the TiO 2 component is 20.0% or less, the coloring of the glass can be reduced, and the internal transmittance of the glass at a visible short wavelength (500 nm or less) can be increased.
  • the content of the TiO 2 component below 20.0%, because the partial dispersion ratio is hard to rise, it is possible to easily obtain a glass having a low partial dispersion ratio.
  • the upper limit of the content of the TiO 2 component is preferably 20.0%, more preferably 15.0%, still more preferably 9.0%, still more preferably 8.1%, and even more preferably 7.0%. And more preferably less than 5.0%, and most preferably 2.8%.
  • TiO 2 component TiO 2 or the like can be used as a raw material.
  • the sum of the contents of the Nb 2 O 5 component and the TiO 2 component is preferably more than 6.5% and 35.0% or less.
  • the lower limit of the molar sum (Nb 2 O 5 + TiO 2 ) is preferably more than 6.5%, more preferably 8.0%, and most preferably 9.0%.
  • the molar sum (Nb 2 O 5 + TiO 2 ) is preferably 35.0%, more preferably less than 30.0%, even more preferably 25.0%, and most preferably 20.0%. % Is the upper limit.
  • the ratio of the content of the TiO 2 component to the sum of the contents of the Nb 2 O 5 component and the ZrO 2 component is preferably 1.00 or less.
  • the content of the TiO 2 component that increases the partial dispersion ratio is relative to the content of the Nb 2 O 5 component and the ZrO 2 component that decrease the partial dispersion ratio. Therefore, an optical glass having a lower partial dispersion ratio can be obtained. 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 molar ratio TiO 2 / (Nb 2 O 5 + ZrO 2 ) of the oxide conversion composition is preferably 1.00, more preferably 0.80, and most preferably 0.70.
  • the lower limit of this molar ratio is not particularly limited, and may be 0.
  • the WO 3 component is a component that increases the refractive index of the glass to lower the Abbe number and increases the devitrification resistance of the glass, and is an optional component in the optical glass of the present invention.
  • the content of the WO 3 component 30.0% 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 made difficult to decrease.
  • devitrification and coloring by reheating can be reduced by reducing the WO 3 component.
  • the upper limit of the content of the WO 3 component is preferably 30.0%, more preferably 25.0%, and most preferably 20.0%.
  • the WO 3 component may not be contained, but by containing the WO 3 component, a glass having a desired high refractive index and a low Abbe number and having high devitrification resistance can be obtained. Therefore, the content of the WO 3 component is preferably more than 0%, more preferably 1.0%, still more preferably 1.7%, and most preferably 2.5%. As the WO 3 component, WO 3 or the like can be used as a raw material.
  • the molar sum of the TiO 2 component and the WO 3 component is preferably 35.0% or less.
  • the molar sum (TiO 2 + WO 3 ) is preferably 35.0%, more preferably less than 33.0%, still more preferably 25.0%, and most preferably 20.0%.
  • the molar sum may be 0% from the viewpoint of further increasing the visible light transmittance, but by increasing the molar sum, the refractive index can be further increased and the Abbe number can be further decreased.
  • the molar sum (TiO 2 + WO 3 ) is preferably more than 0%, more preferably 1.0%, still more preferably 3.0%, and most preferably 5.0%.
  • 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 0.700 or less.
  • the molar ratio (TiO 2 + WO 3 ) / (ZrO 2 + B 2 O 3 ) in the oxide equivalent composition is preferably 0.700, more preferably 0.600, and most preferably 0.500.
  • this ratio may be 0, it is possible to easily obtain a desired refractive index and dispersion by making this molar ratio larger than 0.
  • the molar ratio (TiO 2 + WO 3 ) / (ZrO 2 + B 2 O 3 ) in the oxide equivalent composition is preferably greater than 0, more preferably 0.050, and most preferably 0.100. .
  • the MgO component, CaO component, SrO component, and BaO component are components that adjust the refractive index, meltability, and devitrification of the glass, and are optional components in the optical glass of the present invention.
  • the content of MgO component 15.0% or less, or by making the content of CaO component, SrO component and / or BaO component 20.0% or less, the refractive index of these components can be reduced. Reduction and devitrification can be reduced. Further, this can suppress an increase in the partial dispersion ratio. Therefore, the content of the MgO component is preferably 15.0%, more preferably 10.0%, and most preferably 5.0%.
  • the content of the CaO component is preferably 20.0%, more preferably 15.0%, still more preferably 13.0%, still more preferably 10.0%, and most preferably 7.5%. To do.
  • the contents of the SrO component and the BaO component are each preferably 20.0%, more preferably 15.0%, still more preferably 9.0%, still more preferably 7.5%, and most preferably 4.8. % Is the upper limit.
  • 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 a component that lowers the glass transition point (Tg) and lowers the melting temperature of the glass raw material, and is an optional component in the optical glass of the present invention.
  • devitrification of the glass can be reduced by setting the content of the ZnO component to 35.0% or less. This can also reduce the specific gravity of the glass and suppress the increase in the partial dispersion ratio.
  • the upper limit of the content of the ZnO component is preferably 35.0%, more preferably 30.0%, further preferably 25.0%, further preferably 20.0%, and most preferably 15.0%. To do.
  • the content of the ZnO component is preferably more than 0%, more preferably 1.0%, still more preferably 5.0%, and most preferably 8.0%.
  • ZnO component ZnO, ZnF 2 or the like can be used 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) is a useful component for increasing the devitrification resistance of the glass.
  • R is one or more selected from the group consisting of Zn, Mg, Ca, Sr, and Ba
  • the total content of RO components is preferably 35.0%, more preferably 25.0%, and most preferably 20.0%.
  • the Li 2 O component is a component that lowers the glass transition point and lowers the partial dispersion ratio of the glass, and is an optional component in the optical glass of the present invention.
  • the upper limit of the content of the Li 2 O component is preferably 25.0%, more preferably 12.0%, and most preferably 7.0%.
  • Li 2 CO 3 , LiNO 3 , LiF, or the like can be used as a raw material.
  • the Na 2 O component and the K 2 O component are components that improve the meltability of the glass, lower the glass transition point, and increase the devitrification resistance of the glass, and are optional components in the optical glass of the present invention. .
  • the content of the Na 2 O component and / or the K 2 O component 25.0% or less, the refractive index of the glass is hardly lowered and the devitrification of the glass can be reduced. Therefore, the content of the Na 2 O component and the K 2 O component is preferably 25.0%, more preferably 12.0%, and most preferably 7.0%, respectively.
  • the Na 2 O component and the K 2 O component may use Na 2 CO 3 , NaNO 3 , NaF, Na 2 SiF 6 , K 2 CO 3 , KNO 3 , KF, KHF 2 , K 2 SiF 6, etc. as raw materials. it can.
  • Cs 2 O component is a component to lower the glass transition point, which is an optional component of the optical glass of the present invention.
  • devitrification of the glass can be reduced by setting the content of the Cs 2 O component to 10.0% or less.
  • the content of the Cs 2 O component is preferably 10.0%, more preferably 5.0%, and still more preferably 3.0%.
  • Cs 2 O component Cs 2 CO 3 , CsNO 3 or the like can be used as a raw material.
  • the sum of the contents of the Rn 2 O component (wherein Rn is one or more selected from the group consisting of Li, Na, K and Cs) is 30.0% or less. Is preferred.
  • the molar sum is 30.0% or less, the refractive index of the glass is hardly lowered, and devitrification at the time of glass formation can be reduced.
  • devitrification and coloring by reheating can be reduced by reducing the Rn 2 O component. Therefore, the upper limit of the molar sum of the content of the Rn 2 O component is preferably 30.0%, more preferably 20.0%, still more preferably 15.0%, and most preferably 10.0%.
  • the optical glass of the present invention it is preferable that (B 2 O 3 + ZrO 2 ) / (Ln 2 O 3 + WO 3 + Rn 2 O) is 0.70 or more.
  • B 2 O 3 component and the ZrO 2 component, Ln 2 O 3 component and WO 3 to increase devitrification or coloring at this time to reduce the devitrification or coloring when performing reheating the glass Since it increases relative to the component and the Rn 2 O component, devitrification and coloring during reheating hardly occur, and an optical glass having high press moldability can be easily obtained.
  • the molar ratio (B 2 O 3 + ZrO 2 ) / (Ln 2 O 3 + WO 3 + Rn 2 O) of the oxide equivalent composition is preferably 0.70, more preferably 0.90, and most preferably 1.00. Is the lower limit.
  • the upper limit of the molar ratio is not particularly limited, but the molar ratio of the optical glass of the present invention is generally 5.00 or less, more specifically 4.00 or less, and more specifically 3.00 or less. There are many cases.
  • the SiO 2 component is a component that increases the viscosity of the molten glass, promotes stable glass formation, and reduces devitrification (generation of crystal) that is not desirable as an optical glass, and is an optional component in the optical glass of the present invention. .
  • the content of SiO 2 component is preferably 20.0%, more preferably 13.0%, still more preferably 8.0%, still more preferably 6.0%, still more preferably 3.5%,
  • the upper limit is 3.3%.
  • the content of this SiO 2 component is 1.7% or less. Further, from the viewpoint of easily obtaining a lower partial dispersion ratio and a high refractive index, it is also preferable that no SiO 2 component is contained.
  • 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 0.50 or less.
  • the upper limit of the molar ratio (SiO 2 / B 2 O 3 ) in the oxide equivalent composition is preferably 0.50, more preferably 0.30, and most preferably 0.10.
  • P 2 O 5 component is a component which enhances the devitrification resistance, which is an optional component of the optical glass of the present invention.
  • the content of the P 2 O 5 component is preferably 30.0%, more preferably 20.0%, and most preferably 10.0%.
  • 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.
  • GeO 2 component increases the refractive index of the glass, or to enhance resistance to devitrification, which is an optional component of the optical glass of the present invention.
  • the content of the GeO 2 component is 20.0% or less, the amount of expensive GeO 2 component used is reduced, so that the material cost of the glass can be reduced.
  • the content of the GeO 2 component is preferably 20.0%, more preferably 10.0%, further preferably 4.0%, and most preferably 1.4%.
  • the GeO 2 component GeO 2 or the like can be used as a raw material.
  • the Ta 2 O 5 component is a component that increases the refractive index of the glass, decreases the partial dispersion ratio of the glass, and increases the devitrification resistance of the glass, and is an optional component in the optical glass of the present invention.
  • the content of Ta 2 O 5 component is 7.5% or less, the amount of Ta 2 O 5 component, which is a rare mineral resource, is reduced, and the glass is easily melted at a lower temperature. The production cost can be reduced. Further, it is possible to easily obtain an optical glass having a lower partial dispersion ratio and a lower specific gravity. Therefore, the content of the Ta 2 O 5 component is preferably 7.5%, more preferably 5.0%, still more preferably 3.0%, still more preferably 2.0%, still more preferably 1.0%. Is the upper limit. In particular, from the viewpoint of further reducing the glass production cost, 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 a component that raises the refractive index of the glass to lower the Abbe number and lowers the glass transition point (Tg), and is an optional component in the optical glass of the present invention.
  • an increase in the partial dispersion ratio of the glass can be suppressed by setting the content of the Bi 2 O 3 component to 15.0% or less.
  • the content of the Bi 2 O 3 component is preferably 15.0%, more preferably 10.0%, still more preferably 5.0%, still more preferably 3.0%, and most preferably 1.0%. Is the upper limit.
  • Bi 2 O 3 component Bi 2 O 3 or the like can be used as a raw material.
  • the TeO 2 component is a component that increases the refractive index of the glass, lowers the partial dispersion ratio of the glass, and lowers the glass transition point (Tg), and is an optional component in the optical glass of the present invention.
  • the content of the TeO 2 component is preferably 30.0%, more preferably 15.0%, and still more preferably 7.0%.
  • TeO 2 has a problem that it can be alloyed with platinum when melting a glass raw material in a crucible made of platinum or a melting tank in which a portion in contact with molten glass is formed of platinum. Therefore, particularly from the viewpoint of reducing alloying with platinum, the content of the TeO 2 component is most preferably less than 0.2%.
  • TeO 2 component can use TeO 2 or the like as a raw material.
  • the Al 2 O 3 component is a component that improves the chemical durability of the glass and improves the devitrification resistance of the glass, and is an optional component in the optical glass of the present invention.
  • the upper limit of the content of the Al 2 O 3 component is preferably 15.0%, more preferably 10.0%, and most preferably 5.0%.
  • Al 2 O 3 component Al 2 O 3 , Al (OH) 3 , AlF 3 or the like can be used as a raw material.
  • the Sb 2 O 3 component is a component that defoams the molten glass and is an optional component in the optical glass of the present invention. If sb 2 O 3 content is too high, the transmittance in the short wavelength region of the visible light region is deteriorated. Accordingly, the content of the Sb 2 O 3 component is preferably 1.0%, more preferably 0.5%, and most preferably 0.3%.
  • 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 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 needed 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 by the glass even when each of them is contained alone or in combination. Since it has a property of causing absorption at a specific wavelength in the visible range, it is preferable that the optical glass using the wavelength in the visible range does not substantially contain.
  • lead compounds such as PbO, 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 mass% because the composition is expressed in mol% with respect to the total amount of glass of oxide conversion composition.
  • the composition expressed by mass% of each component present in the glass composition satisfying various required properties generally takes the following values in terms of oxide composition.
  • composition expressed by mass% of the ZrO 2 component contained in the optical glass of the present invention may be generally 0 to 7.0 mass% in terms of oxide.
  • 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 to 1400 ° C. for 3 to 5 hours, stir and homogenize to blow out bubbles, etc., then lower the temperature to 1000 to 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, and most preferably 1.85. On the other hand, the upper limit of the refractive index (n d ) of the optical glass of the present invention is generally 2.00 or less, more specifically 1.97 or less, and more specifically 1.95 or less in many cases. Moreover, the Abbe number ( ⁇ d ) of the optical glass of the present invention is preferably 40, more preferably 38, more preferably 35, and most preferably less than 33.
  • the lower limit of the Abbe number ( ⁇ d ) of the optical glass of the present invention is generally 20 or more, more specifically 23 or more, and more specifically 25 or more in many cases.
  • 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), Most preferred 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 ( ⁇ 0.00275 ⁇ ⁇ d + 0.68125), more preferably ( ⁇ 0.00275 ⁇ ⁇ d + 0.68025), Most preferred is ( ⁇ 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), most preferably 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). Most preferred 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, and most preferably 430 nm or less.
  • the optical glass of the present invention has a wavelength ( ⁇ 80 ) of 560 nm or less, more preferably 540 nm or less, and most preferably, when the sample has a thickness of 10 mm and exhibits a spectral transmittance of 80%.
  • 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 most 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 is 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 most 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, and most preferably a maximum of 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. This is carried out by keeping the temperature at 80 ° C. higher than the transition temperature (Tg) for 30 minutes, then naturally cooling to room temperature, and polishing the two opposing surfaces of the test piece to a thickness of 10 mm and visually observing them.
  • Tg transition temperature
  • 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 manner 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.
  • the high-purity raw materials used in the above are selected, weighed so as to have the composition ratios of the examples and comparative examples shown in Tables 1 to 11, and mixed uniformly, and then put into a platinum crucible, and glass
  • 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 at a transmittance of 5%), ⁇ 70 (transmittance).
  • the wavelength at 70%) and ⁇ 80 (wavelength at 80% transmittance) were determined.
  • permeability before and after the reheating test (ii) of the glass of an Example and a comparative example was measured as follows.
  • 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 (b) by the d-line transmittance of the test piece before the reheating test is the reheating test (b).
  • the front and rear glasses were subjected to the Japan Optical Glass Industry Association Standard JOGIS02-2003.
  • the d-line spectral transmittance of a face-parallel polished product having a thickness of 10 ⁇ 0.1 mm was measured in accordance with JISZ8722, and (d-line transmittance after reheating test (ii)) / (reheated)
  • the d-line transmittance before the test (A) was determined, and the change in the maximum transmittance before and after the reheating test (A) was evaluated.
  • the difference between ⁇ 70 which is the wavelength at which the transmittance of the test piece before the reheating test (A) becomes 70%, and ⁇ 70 of the test piece after the reheating test is the same as before and after the reheating test (A).
  • the glass calculated lambda 70 (the wavelength when the transmittance of 70%) in the above test method, the test piece after the reheating test and lambda 70 of reheating test (a) prior to the test piece (a) lambda
  • Tg transition temperature
  • the optical glasses of the examples of the present invention have a partial dispersion ratio ( ⁇ g, F) of ( ⁇ 0.00275 ⁇ ⁇ d + 0.68125) or less when ⁇ d ⁇ 31. More specifically, it was ( ⁇ 0.00275 ⁇ ⁇ d + 0.68020) or less. In the case of ⁇ d > 31, the partial dispersion ratio ( ⁇ g, F) was ( ⁇ 0.00162 ⁇ ⁇ d + 0.64622) or less, more specifically, ( ⁇ 0.00162 ⁇ ⁇ d + 0.64538) 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 these partial dispersion ratios ( ⁇ g, F) are within a desired range.
  • the glasses of the comparative examples No. A, No. C to No.
  • 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 1.70 or more, more specifically 1.89 or more, and this refractive index (n d ) is 2.20 or less. More specifically, it was 1.94 or less, and was within a desired range.
  • the optical glasses of the examples of the present invention each have an Abbe number ( ⁇ d ) of 20 or more, more specifically 29 or more, and this Abbe number ( ⁇ d ) of 40 or less, more specifically 33. And within the desired range.
  • the glass of the comparative example of the present invention (No. D) is, [nu d was more than 34. Therefore, it has been clarified that the optical glass of the example of the present invention has a smaller Abbe number ( ⁇ d ) than the glass of the comparative example (No. D).
  • optical glasses of the examples of the present invention all had a specific gravity of 5.00 or less, more specifically 4.78 or less, and were within a desired range.
  • each of ⁇ 70 (wavelength at a transmittance of 70%) was 500 nm or less, more specifically, 434 nm or less.
  • the optical glasses of the examples of the present invention all had ⁇ 5 (wavelength at 5% transmittance) of 420 nm or less, more specifically 371 nm or less.
  • the optical glasses of the examples of the present invention each had a ⁇ 80 (wavelength at 80% transmittance) of 560 nm or less, more specifically 531 nm or less. For this reason, it became clear that the optical glass of the Example of this invention has the high transmittance
  • 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.
  • the optical glass of the Example of this invention is the value which divided
  • D) of the present invention has the d-line transmittance of the test piece after the reheating test (ii) and the d-line transmittance of the test piece before the reheating test.
  • the transmittance was less than 70% for all wavelengths of visible light. Therefore, it became clear that the optical glass of the example of the present invention is less likely to be colored or devitrified by reheating than the glass of the comparative examples (No. C, No. D).

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Abstract

Cette invention concerne un verre optique présentant une transparence améliorée vis-à-vis de la lumière visible et ayant un petit nombre d'Abbe (νd) et un bas taux de dispersion partielle (θg,F) tandis que son indice de réfraction (nd) est dans une plage recherchée. Le verre optique selon l'invention contient, en % en mol par rapport à la quantité totale du verre en termes d'oxydes, 25,0 à 55,0 % d'un composant de B2O3 et 6,0 à 30,0 % d'un composant de Ln2O3 (dans la formule, Ln représente un ou plusieurs éléments choisis parmi La, Gd, Y, et Yb), et plus de 0 % à 25,0 % ou moins d'un composant de Nb2O5, et a une teneur en composant ZrO2 de 15,0 % ou moins, le taux de dispersion partielle (θg,F) et le nombre d'Abbe (νd) satisfaisant la relation (-0,00162×νd+0,63822)≤(θg,F)≤(-0,00275×νd+0,68125) quand νd≤31 et satisfaisant la relation (-0,00162×νd+0,63822)≤(θg,F)≤(-0,00162×νd+0,64622) quand νd>31.
PCT/JP2012/057957 2011-03-29 2012-03-27 Verre optique, préforme, et élément optique WO2012133422A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3950620A4 (fr) * 2019-04-05 2022-12-28 Nippon Electric Glass Co., Ltd. Article de décoration en verre

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008254953A (ja) * 2007-04-03 2008-10-23 Ohara Inc 光学ガラス
WO2009096437A1 (fr) * 2008-01-31 2009-08-06 Hoya Corporation Verre optique
JP2011026185A (ja) * 2009-06-30 2011-02-10 Ohara Inc 光学ガラス、プリフォーム材及び光学素子

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008254953A (ja) * 2007-04-03 2008-10-23 Ohara Inc 光学ガラス
WO2009096437A1 (fr) * 2008-01-31 2009-08-06 Hoya Corporation Verre optique
JP2011026185A (ja) * 2009-06-30 2011-02-10 Ohara Inc 光学ガラス、プリフォーム材及び光学素子

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3950620A4 (fr) * 2019-04-05 2022-12-28 Nippon Electric Glass Co., Ltd. Article de décoration en verre

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