WO2011086855A1 - 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 PDFInfo
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- WO2011086855A1 WO2011086855A1 PCT/JP2010/073750 JP2010073750W WO2011086855A1 WO 2011086855 A1 WO2011086855 A1 WO 2011086855A1 JP 2010073750 W JP2010073750 W JP 2010073750W WO 2011086855 A1 WO2011086855 A1 WO 2011086855A1
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
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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
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
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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
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
- C03C3/19—Silica-free oxide glass compositions containing phosphorus containing boron
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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
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
- C03C3/21—Silica-free oxide glass compositions containing phosphorus containing titanium, zirconium, vanadium, tungsten or molybdenum
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
Definitions
- the present invention relates to an optical glass, 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, 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.
- the combination of these lenses can only correct the aberration in the red region and the green region, and the aberration in the blue region remains.
- 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.
- optical glasses having a specific partial dispersion ratio have a remarkable effect on correction of aberrations, and therefore various glasses have been developed in order to expand the degree of freedom in optical design.
- chromatic aberration can be corrected in a wide wavelength range from ultraviolet to infrared.
- 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 has 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 this straight line 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. 60.5, and the partial dispersion ratio ( ⁇ g, F) is 0.5436.) From this normal line, how far the plot of the partial dispersion ratio and Abbe number of the optical glass is in the vertical axis direction. It is an indicator of anomalous dispersion of optical glass.
- Patent Documents 1 to 5 disclose optical glasses in which the partial dispersion ratio ( ⁇ g, F) has a unique value.
- Patent Documents 1-3 A glass SiO 2 -B 2 O 3 -ZrO 2 -Nb 2 O 5 system and the SiO 2 -ZrO 2 -Nb 2 O 5 -Ta 2 O 5 system
- An optical glass having an Abbe number ( ⁇ d ) in the range of 28 to 55 and a partial dispersion ratio ( ⁇ g, F) in the range of 0.54 to 0.59 is disclosed.
- Patent Documents 4 and 5 describe SiO 2 —B 2 O 3 —TiO 2 —Al 2 O 3 and Bi 2 O 3 —B 2 O 3 based glasses having an Abbe number ( ⁇ d ) of 32.
- An optical glass having a partial dispersion ratio ( ⁇ g, F) in the range of 0.55 to 0.59 is disclosed.
- the partial dispersion ratios of the glasses disclosed in Patent Documents 1 to 5 remain as low as 0.59 or less. Therefore, in order to correct the chromatic aberration of the lens with higher accuracy, it is necessary to have a high partial dispersion ratio ( ⁇ g, F), but the value is insufficient to correct the chromatic aberration with high accuracy. there were.
- a glass having a high partial dispersion ratio has a lower transparency to visible light as the Abbe number ( ⁇ d ) is lower (the value of ⁇ 70 is larger), so it is colored yellow or orange, It is not suitable for applications that transmit light in the visible region.
- the glasses disclosed in Patent Documents 1 to 5 are all glasses having a high Abbe number ( ⁇ d ).
- the glasses disclosed in Patent Documents 1 to 5 often have a small difference ⁇ T between the glass transition point (Tg) and the crystallization start temperature (Tx), and the thermal stability of these glasses is low. there were. Therefore, when a preform material is produced from this glass and an optical element is produced by heat-softening and molding the preform material, the produced optical element is devitrified due to crystallization of the heat-softened glass. The optical characteristics of the element were affected.
- the present invention has been made in view of the above problems, and an object thereof is to correct the chromatic aberration of a lens with higher accuracy while the Abbe number ( ⁇ d ) is within a desired range. It is to obtain an optical glass, a preform and an optical element using the optical glass.
- the present invention provides an optical glass having a Abbe number ( ⁇ d ) within a desired range and capable of correcting chromatic aberration of a lens with higher accuracy, and having less coloring, a preform and an optical glass using the optical glass Another object is to obtain an element.
- the present invention also provides an optical glass having high thermal stability while having an Abbe number ( ⁇ d ) within a desired range and capable of correcting chromatic aberration of a lens with higher accuracy. Another object is to obtain a preform and an optical element.
- the present inventors have conducted intensive test studies. As a result, the P 2 O 5 component, the Nb 2 O 5 component and other components are used in combination, and the P 2 O 5 component and the Nb 2 O are used together. It was found that by setting the content of the five components within a predetermined range, the dispersion of the glass is within a desired range, and the partial dispersion ratio ( ⁇ g, F) of the glass is increased, and the present invention has been completed. It was.
- the inventors use a P 2 O 5 component, a Nb 2 O 5 component, and an alkali metal component in combination, and the contents of the P 2 O 5 component, the Nb 2 O 5 component, and the alkali metal component are within a predetermined range. It has also been found that the dispersion of the glass falls within a desired range, the partial dispersion ratio ( ⁇ g, F) of the glass is increased, and the transparency of the glass in the visible region is increased.
- the present inventors have used the P 2 O 5 component and the Nb 2 O 5 component in combination, and the Nb 2 O 5 component and the TiO 2 component are contained within a predetermined range, thereby dispersing the glass. It has also been found that it is within the desired range, the partial dispersion ratio ( ⁇ g, F) of the glass is increased, and the transparency of the glass in the visible range is increased.
- the present inventors use a P 2 O 5 component and a Nb 2 O 5 component in combination, and make the content of the P 2 O 5 component and the Nb 2 O 5 component within a predetermined range, thereby dispersing the glass. Is found that the partial dispersion ratio ( ⁇ g, F) of the glass is increased and the difference ⁇ T between the glass transition point (Tg) and the crystallization start temperature (Tx) is increased. It was.
- the present invention provides the following.
- the entire mass of the glass in terms of oxide composition the content of TiO 2 component in terms of mass% is less than 30.0% (3), wherein the optical glass.
- any description of the optical glass of the content of WO 3 component to the glass the total weight of the oxide basis the composition is not more than 30.0% (1) to (6).
- the mass ratio (SiO 2 + B 2 O 3 ) / (P 2 O 5 + SiO 2 + B 2 O 3 ) in the oxide equivalent composition is less than 0.200, according to any one of (1) to (12) Optical glass.
- the mass sum of the Ln 2 O 3 component (wherein Ln is one or more selected from the group consisting of Y, La, Gd and Yb) with respect to the total glass mass of the oxide equivalent composition is 15.0% or less
- the optical glass according to (14) is 15.0% or less.
- the mass sum of the Ln 2 O 3 component (wherein Ln is one or more selected from the group consisting of Y, La, Gd and Yb) with respect to the total glass mass of the oxide equivalent composition is 0.1% or more
- 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) with respect to the total glass mass of the oxide equivalent composition is 30.0% or less.
- 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) with respect to the total glass mass of the oxide equivalent composition is 15.0% or less
- the mass sum of the Rn 2 O component (wherein Rn is one or more selected from the group consisting of Li, Na, K and Cs) with respect to the total glass mass of the oxide equivalent composition is 30.0% or less.
- the oxide equivalent composition contains more than 0% of an Rn 2 O component (wherein Rn is one or more selected from the group consisting of Li, Na, K and Cs) (20) or (21 ) Optical glass as described.
- the mass sum of the Rn 2 O component (wherein Rn is one or more selected from the group consisting of Li, Na, K and Cs) with respect to the total glass mass of the oxide equivalent composition is 0.1% or more and 30 Optical glass in any one of (20) to (22) which is 0.0% or less.
- the mass sum of the Rn 2 O component (wherein Rn is one or more selected from the group consisting of Li, Na, K and Cs) with respect to the total glass mass of the oxide equivalent composition is more than 1.0%.
- the mass sum of the Rn 2 O component (wherein Rn is one or more selected from the group consisting of Li, Na, K and Cs) with respect to the total glass mass of the oxide equivalent composition is more than 7.0%
- the P 2 O 5 component, the Nb 2 O 5 component and other components are used in combination, and the content of the P 2 O 5 component and the Nb 2 O 5 component is set within a predetermined range. While the number ( ⁇ d ) is within the desired range, the chromatic aberration of the lens can be corrected with higher accuracy, and the glass has a high resistance to devitrification when formed from a molten state.
- An optical glass having a wide transmission wavelength range, a preform and an optical element using the optical glass can be obtained.
- a combination of P 2 O 5 component, Nb 2 O 5 component and the alkali metal component, P 2 O 5 component, within the content of a predetermined Nb 2 O 5 component and the alkali metal component can be corrected with higher accuracy while the Abbe number ( ⁇ d ) is within the desired range, and the devitrification resistance when the glass is formed from the molten state.
- a high optical glass having a wide transmission wavelength range in the visible range and little coloring, and a preform and an optical element using the optical glass can be obtained.
- the Abbe number ( ⁇ ) can be obtained by setting the contents of the Nb 2 O 5 component and the TiO 2 component within a predetermined range while using the P 2 O 5 component and the Nb 2 O 5 component together.
- d ) can correct the chromatic aberration of the lens with higher accuracy while being in a desired range, and has high resistance to devitrification when glass is formed from a molten state, and a transmission wavelength range in the visible range.
- optical glass having a wide color and little coloration, a preform and an optical element using the same can be obtained.
- the Abbe number While ⁇ d
- the chromatic aberration of the lens can be corrected with higher accuracy, and it has high thermal stability, and has a wide transmission wavelength range in the visible range, and coloring is possible. Less optical glass, preforms and optical elements using the same can be obtained.
- the optical glass of the present invention contains less than 75.0% of the Nb 2 O 5 component and less than 40.0% of the P 2 O 5 component in mass% with respect to the total glass mass of the oxide equivalent composition, It has a partial dispersion ratio ( ⁇ g, F) of 0.62 or more and 0.69 or less, and an Abbe number ( ⁇ d ) of 15 or more and 27 or less.
- ⁇ g, F partial dispersion ratio
- ⁇ d Abbe number
- the optical glass of the present invention the entire mass of the glass in terms of oxide composition, less than 75.0% of Nb 2 O 5 component in mass%, less than 40.0% of P 2 O 5 component, and, Rn 2 O component (wherein Rn is one or more selected from the group consisting of Li, Na, K and Cs), and a partial dispersion ratio [ ⁇ g, F] of 0.62 or more and 0.69 or less is included. And having an Abbe number ( ⁇ d ) of 15 or more and 27 or less.
- the P 2 O 5 component, the Nb 2 O 5 component, and the Rn 2 O component in combination, and setting the contents of the P 2 O 5 component, the Nb 2 O 5 component, and the Rn 2 O component within a predetermined range, glass is obtained.
- the partial dispersion ratio [ ⁇ g, F] of the glass is increased, and the transparency of the glass with respect to light having a wavelength in the visible range is increased. Therefore, it is possible to obtain an optical glass with less coloring that can correct the chromatic aberration of the lens with higher accuracy while the Abbe number ( ⁇ d ) is in the range of 15 to 27.
- the optical glass of the present invention contains less than 75.0% of Nb 2 O 5 component and less than 40.0% of P 2 O 5 component in mass% with respect to the total glass mass of the oxide equivalent composition.
- the content of the TiO 2 component is 30.0% or less, has a partial dispersion ratio [ ⁇ g, F] of 0.62 to 0.69, and has an Abbe number ( ⁇ d of 15 to 27 ). ) May be included.
- the P 2 O 5 component and the Nb 2 O 5 component in combination the Nb 2 O 5 component and the TiO 2 component are contained in a predetermined range, whereby the dispersion of the glass is within a desired range.
- the partial dispersion ratio [ ⁇ g, F] is increased, a decrease in the transparency of the glass with respect to light having a wavelength in the visible range due to the TiO 2 component can be suppressed. Therefore, it is possible to obtain an optical glass with less coloring that can correct the chromatic aberration of the lens with higher accuracy while the Abbe number ( ⁇ d ) is in the range of 15 to 27.
- the optical glass of the present invention contains less than 75.0% of Nb 2 O 5 component and less than 40.0% of P 2 O 5 component in mass% with respect to the total glass mass of the oxide equivalent composition. And having a partial dispersion ratio [ ⁇ g, F] of 0.62 or more and 0.69 or less, an Abbe number ( ⁇ d ) of 15 or more and 27 or less, a glass transition point (Tg) and a crystallization start temperature ( The difference ⁇ T with respect to Tx) may be 90 ° C. or more.
- the dispersion of the glass becomes within a desired range,
- the partial dispersion ratio [ ⁇ g, F] of the glass is increased, and the difference ⁇ T between the glass transition point (Tg) and the crystallization start temperature (Tx) is increased. Therefore, it is possible to obtain an optical glass that can correct the chromatic aberration of the lens with higher accuracy and has high thermal stability while the Abbe number ( ⁇ d ) is in the range of 15 to 27. .
- 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 this specification, unless there is particular notice, content of each component shall be displayed by the mass% with respect to the glass total mass of an oxide conversion composition.
- the “oxide equivalent composition” means that the oxide, composite salt, metal fluoride, etc. used as the raw material of the glass component of the present invention are all decomposed and changed into oxides when melted. It is the composition which described each component contained in glass by making the total mass of the said production
- Nb 2 O 5 component is a component for increasing the refractive index and dispersion of the glass.
- the refractive index and dispersion of the glass while increasing the partial dispersion ratio ( ⁇ g, F) of the glass and enhancing the transparency of the glass in the visible wavelength range. Can be increased.
- the content of the Nb 2 O 5 component with respect to the total glass mass of the oxide-converted composition is preferably 0.1%, more preferably 1.0%, still more preferably 10.0%, and most preferably 25.0. % Is the lower limit, preferably less than 75.0%, more preferably 70.0%, and most preferably 65.0%.
- the Nb 2 O 5 component can be contained in the glass using, for example, Nb 2 O 5 as a raw material.
- the P 2 O 5 component is a glass forming component and is a component that lowers the melting temperature of glass.
- the devitrification resistance of the glass can be enhanced while enhancing the transparency of the glass in the visible wavelength range.
- the content of the P 2 O 5 component less than 40.0%, it is possible to make it difficult to lower the partial dispersion ratio ( ⁇ g, F) of the glass. Therefore, the content of the P 2 O 5 component with respect to the total glass mass of the oxide conversion composition is preferably 0.1%, more preferably 5.0%, still more preferably 10.0%, and even more preferably 17.0.
- the P 2 O 5 component can be contained in the glass using, for example, Al (PO 3 ) 3 , Ca (PO 3 ) 2 , Ba (PO 3 ) 2 , BPO 4 , H 3 PO 4 or the like as a raw material.
- TiO 2 component is a component that raises the refractive index and dispersion of the glass, an optional component of the optical glass of the present invention.
- the content of the TiO 2 component with respect to the total glass mass of the oxide conversion composition is preferably 40.0%, more preferably 35.0%, and most preferably 30.0%.
- the content of the TiO 2 component with respect to the total glass mass of the oxide-converted composition is preferable in that the transparency to light with a wavelength in the visible range of the glass is particularly enhanced while a particularly high refractive index and dispersion are obtained. Is 25.0%, more preferably 22.0%, and most preferably 20.0%.
- the devitrification resistance of the glass can be improved by setting the content of the TiO 2 component to 30.0% or less. Therefore, the content of the TiO 2 component with respect to the total glass mass of the oxide conversion composition in this case is preferably 30.0%, more preferably 25.0%, and most preferably 20.0%.
- the content of the TiO 2 component with respect to the total glass mass of the oxide-converted composition is particularly high in terms of the transparency to light having a wavelength in the visible region of the glass while being particularly easy to obtain a high refractive index and dispersion.
- the upper limit is preferably 15.0%, more preferably 12.0%, and most preferably 10.0%.
- the optical glass of the present invention may not contain TiO 2 component, by containing a TiO 2 component of 0.1% or more, it is possible to increase the partial dispersion ratio of glass ([theta] g, F) and more . Therefore, in this case, the content of the TiO 2 component with respect to the total amount of the glass having the oxide conversion composition is preferably 0.1%, more preferably 2.0%, and most preferably 5.5%.
- the TiO 2 component can be contained in the glass using, for example, TiO 2 as a raw material.
- the WO 3 component is a component that increases the partial dispersion ratio ( ⁇ g, F) of the glass and increases the refractive index and dispersion of the glass, and is an optional component in the optical glass of the present invention.
- the content of the WO 3 component with respect to the total glass mass of the oxide conversion composition is preferably 30.0%, more preferably 20.0%, more preferably 13.0%, more preferably 12.0%, More preferably, the upper limit is 10.0%, most preferably 7.0%, and most preferably 5.0%.
- the WO 3 component can be contained in the glass using, for example, WO 3 as a raw material.
- the mass sum of the contents of the Nb 2 O 5 component, the TiO 2 component, and the WO 3 component is preferably 40.0% or more.
- the partial dispersion ratio ( ⁇ g, F) can be further increased, and an optical glass having a desired partial dispersion ratio ( ⁇ g, F) can be easily obtained.
- the devitrification resistance of glass can be improved by making this mass sum into 64.0% or less. Therefore, this mass sum (Nb 2 O 5 + TiO 2 + Bi 2 O 3 ) is preferably 40.0%, more preferably 45.0%, most preferably 50.0%, and preferably 64.0%. %, More preferably 63.5%, and most preferably 63.0%.
- the SiO 2 component is a component that widens the transmission wavelength range of the glass in the visible range, promotes stable glass formation and increases the devitrification resistance of the glass, and is an optional component in the optical glass of the present invention.
- the content of SiO 2 component 10.0% or less, it is possible to make it difficult to lower the partial dispersion ratio ( ⁇ g, F) and refractive index of the glass and to increase the glass transition point (Tg). Can be suppressed.
- the content of the SiO 2 component with respect to the total glass mass of the oxide conversion composition is preferably 10.0%, more preferably 7.0%, and most preferably 5.0%.
- SiO 2 component may be contained in the glass by using as a raw material such as SiO 2, K 2 SiF 6, Na 2 SiF 6 or the like.
- the B 2 O 3 component is a component that promotes stable glass formation 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 B 2 O 3 component 10.0% or less, it is possible to make it difficult to lower the partial dispersion ratio ( ⁇ g, F) and the refractive index of the glass, and the glass transition point (Tg). Can be suppressed. Therefore, the content of the B 2 O 3 component with respect to the total glass mass of the oxide conversion composition is preferably 10.0%, more preferably 7.0%, and most preferably 5.0%.
- the B 2 O 3 component can be contained in the glass using, for example, H 3 BO 3 , Na 2 B 4 O 7 , Na 2 B 4 O 7 .10H 2 O, BPO 4 or the like as a raw material.
- the mass sum of the contents of the P 2 O 5 component, the SiO 2 component, and the B 2 O 3 component is preferably 35.0% or less.
- the mass sum is preferably 35.0% or less.
- this mass sum (P 2 O 5 + SiO 2 + B 2 O 3 ) is preferably 35.0%, more preferably 32.0%, still more preferably 30.0%, still more preferably 29.0%,
- the upper limit is more preferably 27.0%, and most preferably 26.3%.
- the lower limit of the mass sum is not particularly limited, but is preferably 0.1%, more preferably 5.0%, and still more preferably from the viewpoint of promoting stable glass formation and increasing the devitrification resistance of the glass.
- the lower limit is 10.0%, most preferably 15.0%.
- the ratio of the mass sum (SiO 2 + B 2 O 3 ) to the mass sum (P 2 O 5 + SiO 2 + B 2 O 3 ) is preferably less than 0.200.
- the ratio of the SiO 2 component and B 2 O 3 component is a component for increasing the glass transition point (Tg) among glass-forming components is reduced, the glass transition point of the glass to be obtained as (Tg) starting crystallization
- the difference ⁇ T from the temperature (Tx) can be widened, and the thermal stability of the glass can be increased.
- the mass ratio (SiO 2 + B 2 O 3 ) / (P 2 O 5 + SiO 2 + B 2 O 3 ) in the oxide equivalent composition is preferably less than 0.200, more preferably less than 0.100, and even more preferably It is less than 0.080, most preferably less than 0.060.
- the Y 2 O 3 component increases the refractive index of the glass, or to enhance the chemical durability of the glass, an optional component of the optical glass of the present invention.
- the content of the Y 2 O 3 component is preferably 10.0%, more preferably 7.0%, and most preferably 5.0%.
- the Y 2 O 3 component can be contained in the glass using, for example, Y 2 O 3 , YF 3 or the like as a raw material.
- La 2 O 3 component increases the refractive index of the glass, or to enhance the chemical durability of the glass, an optional component of the optical glass of the present invention.
- the content of the La 2 O 3 component is preferably 10.0%, more preferably 7.0%, and most preferably 5.0%.
- the La 2 O 3 component can be contained in the glass using, for example, La 2 O 3 , La (NO 3 ) 3 .XH 2 O (X is an arbitrary integer) or the like as a raw material.
- the Gd 2 O 3 component is a component that increases the refractive index of the glass and increases the chemical durability of the glass, and is an optional component in the optical glass of the present invention.
- the content of the Gd 2 O 3 component 10.0% or less, it is possible to make it difficult to lower the dispersion of the glass and to reduce the devitrification resistance of the glass. Therefore, the content of the Gd 2 O 3 component with respect to the total glass mass of the oxide conversion composition is preferably 10.0%, more preferably 7.0%, and most preferably 5.0%.
- the Gd 2 O 3 component can be contained in the glass using, for example, Gd 2 O 3 , GdF 3 or the like as a raw material.
- Yb 2 O 3 component increases the refractive index of the glass, or to enhance the chemical durability of the glass, an optional component of the optical glass of the present invention.
- the content of the Yb 2 O 3 component 10.0% or less, it is possible to make it difficult to lower the dispersion of the glass and to reduce the devitrification resistance of the glass.
- the content of the Yb 2 O 3 component with respect to the total glass mass of the oxide-converted composition is preferably 10.0%, more preferably 7.0%, and most preferably 5.0%.
- the Yb 2 O 3 component can be contained in the glass using, for example, Yb 2 O 3 as a raw material.
- the mass sum of the contents of the Ln 2 O 3 component (wherein Ln is one or more selected from the group consisting of Y, La, Gd, and Yb) is 15.0% or less. Preferably there is.
- the mass sum is preferably 15.0%, more preferably 12.0%, and most preferably 10.0%. .
- Ln 2 O 3 component may or may not contain any, but by containing Ln 2 O 3 component of at least one of 0.1% or more, the partial dispersion ratio of glass ([theta] g, F) and more Can be increased. Therefore, in this case, the mass sum of the content of the RO component with respect to the total amount of glass in the oxide conversion composition is preferably 0.1%, more preferably 0.5%, and most preferably 1.0%. To do.
- the MgO component is a component that lowers the liquidus temperature 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 the MgO component is 25.0% or less, the refractive index and dispersion of the glass can be made difficult to decrease. Therefore, the content of the MgO component with respect to the total glass mass of the oxide conversion composition is preferably 25.0%, more preferably 20.0%, and most preferably 15.0%.
- the MgO component can be contained in the glass using, for example, MgCO 3 or MgF 2 as a raw material.
- the CaO component is a component that lowers the liquidus temperature 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 the CaO component is 25.0% or less, the refractive index and dispersion of the glass can be made difficult to decrease. Therefore, the content of the CaO component with respect to the total glass mass of the oxide conversion composition is preferably 25.0%, more preferably 20.0%, and most preferably 15.0%.
- the CaO component can be contained in the glass using, for example, CaCO 3 , CaF 2 or the like as a raw material.
- the SrO component is a component that lowers the liquidus temperature 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 the SrO component 25.0% or less, it is possible to make it difficult to lower the refractive index and dispersion of the glass while making it difficult to lower the partial dispersion ratio ( ⁇ g, F). Therefore, the content of the SrO component with respect to the total glass mass of the oxide conversion composition is preferably 25.0%, more preferably 20.0%, and most preferably 15.0%.
- the SrO component can be contained in the glass using, for example, Sr (NO 3 ) 2 , SrF 2 or the like as a raw material.
- the BaO component is a component that increases the refractive index and dispersion of the glass, and is an optional component in the optical glass of the present invention.
- the content of the BaO component is preferably 25.0%, more preferably 20.0%, and most preferably 15.0%.
- the BaO component can be contained in the glass using, for example, BaCO 3 , Ba (NO 3 ) 2 or the like as a raw material.
- the ZnO component is a component that lowers the liquidus temperature 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 the ZnO component is preferably 25.0%, more preferably 20.0%, and most preferably 15.0%.
- the ZnO component can be contained in the glass using, for example, ZnO, ZnF 2 or the like as a raw material.
- the mass sum of the content of the RO component (wherein Rn is one or more selected from the group consisting of Mg, Ca, Sr, Ba, Zn) is 30.0% or less. Is preferred. By setting the mass sum to 30.0% or less, the partial dispersion ratio ( ⁇ g, F) and the Abbe number ( ⁇ d ) are less likely to decrease. Therefore, the desired partial dispersion ratio ( ⁇ g, F) and the Abbe number ( ⁇ d ) can be easily obtained. Therefore, the mass sum of the RO component content is preferably 30.0%, more preferably 20.0%, even more preferably 15.0%, still more preferably 10.0%, and most preferably 8%. Less than 0%.
- the mass sum of the RO component content with respect to the total glass mass of the oxide conversion composition is preferably 0.1%, more preferably 0.2%, and still more preferably 0.5%.
- the mass sum of the RO component content with respect to the total glass mass of the oxide conversion composition is: More preferably, the lower limit is 1.0%, and most preferably more than 2.0%.
- the Li 2 O component is a component that lowers the glass transition point (Tg), increases the devitrification resistance of the glass, and increases the transparency of the glass with respect to light in the visible wavelength range, and is an optional component in the optical glass of the present invention. It is. In particular, by making the content of the Li 2 O component 10.0% or less, it is difficult to lower the partial dispersion ratio ( ⁇ g, F), and the devitrification resistance of the glass due to excessive inclusion of the Li 2 O component. Can be suppressed. Therefore, the content of the Li 2 O component with respect to the total glass mass of the oxide conversion composition is preferably 10.0%, more preferably 7.0%, and most preferably 5.0%.
- the Li 2 O component can be contained in the glass using, for example, Li 2 CO 3 , LiNO 3 , LiF or the like as a raw material.
- the Na 2 O component is a component that lowers the glass transition point (Tg), increases the devitrification resistance of the glass, and increases the transparency of the glass with respect to light in the visible wavelength range, and is an optional component in the optical glass of the present invention. It is. In particular, by making the content of the Na 2 O component 20.0% or less, it is difficult to lower the partial dispersion ratio ( ⁇ g, F), and the glass is devitrification resistant due to the excessive content of the Na 2 O component. Can be suppressed. Therefore, the content of the Na 2 O component with respect to the total glass mass of the oxide-converted composition is preferably 20.0%, more preferably 17.0%, and most preferably 15.0%.
- the Na 2 O component can be contained in the glass using, for example, Na 2 CO 3 , NaNO 3 , NaF, Na 2 SiF 6 or the like as a raw material.
- the K 2 O component is a component that lowers the glass transition point (Tg), increases the devitrification resistance of the glass, and increases the transparency of the glass with respect to light having a wavelength in the visible range, and is an optional component in the optical glass of the present invention. It is. In particular, by setting the content of the K 2 O component to 20.0% or less, it is difficult to lower the partial dispersion ratio ( ⁇ g, F), and the glass is devitrification resistant due to the excessive content of the K 2 O component. Can be suppressed. Therefore, the content of the K 2 O component with respect to the total glass mass of the oxide conversion composition is preferably 20.0%, more preferably 17.0%, and most preferably 15.0%.
- the K 2 O component can be contained in the glass using, for example, K 2 CO 3 , KNO 3 , KF, KHF 2 , K 2 SiF 6 or the like as a raw material.
- the Cs 2 O component is a component that lowers the glass transition point (Tg), increases the devitrification resistance of the glass, and increases the transparency of the glass with respect to light having a wavelength in the visible range, and is an optional component in the optical glass of the present invention. It is. In particular, by making the content of the Cs 2 O component 10.0% or less, it is difficult to lower the partial dispersion ratio ( ⁇ g, F), and the devitrification resistance of the glass due to the excessive content of the Cs 2 O component. Can be suppressed. Accordingly, the content of the Cs 2 O component with respect to the total glass mass of the oxide-converted composition is preferably 10.0%, more preferably 7.0%, and most preferably 5.0%. Cs 2 O component may be contained in the glass by using as the starting material for example Cs 2 CO 3, CsNO 3, and the like.
- the mass sum of the contents of the Rn 2 O component (wherein R is one or more selected from the group consisting of Li, Na, K, and Cs) is 30.0% or less. It is preferable. By setting the mass sum to 30.0% or less, the partial dispersion ratio ( ⁇ g, F) and the Abbe number ( ⁇ d ) are less likely to decrease. Therefore, the desired partial dispersion ratio ( ⁇ g, F) and the Abbe number ( ⁇ d ) can be easily obtained. Therefore, the mass sum of the contents of the Rn 2 O component in the oxide equivalent composition is preferably 30.0%, more preferably 25.0%, and most preferably 20.0%.
- the optical glass of the present invention may not contain Rn 2 O component, but by containing at least one of Rn 2 O components than 0.1%, while lowering the glass transition point (Tg), It is possible to increase the transparency of the glass with respect to light having a wavelength in the visible range and to improve the devitrification resistance of the glass. Therefore, the mass sum of the content of the Rn 2 O component with respect to the total glass mass of the oxide conversion composition is preferably 0.1%, more preferably 0.2%, and still more preferably 0.5%.
- the mass sum of the content of the Rn 2 O component with respect to the total glass mass of the oxide conversion composition is preferably 1.0%. More preferably, the lower limit is 5.0%, and most preferably more than 7.0%.
- the mass sum of the content of the Rn 2 O component with respect to the total glass mass of the oxide conversion composition is preferably more than 1.0%, more preferably 3.
- the lower limit is 0%, more preferably 5.0%, and most preferably more than 7.0%.
- the Bi 2 O 3 component is a component that increases the partial dispersion ratio ( ⁇ g, F) of the glass, increases the refractive index of the glass, and decreases the glass transition point (Tg), and is an optional component in the optical glass of the present invention. is there.
- the content of the Bi 2 O 3 component is preferably 20.0%, more preferably 15.0%, still more preferably 11.5%, and even more preferably 10.0. % Is the upper limit, more preferably less than 10.0%, and most preferably 9.0%.
- the Bi 2 O 3 component can be contained in the glass using, for example, Bi 2 O 3 as a raw material.
- TeO 2 component is a component that raises the refractive index of the glass, an optional component of the optical glass of the present invention.
- the content of the TeO 2 component with respect to the total glass mass of the oxide conversion composition is preferably 15.0%, more preferably 12.0%, and most preferably less than 10.0%.
- the TeO 2 component can be contained in the glass using, for example, TeO 2 as a raw material.
- the Al 2 O 3 component is a component that increases the chemical durability of the glass and increases the viscosity of the molten 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 with respect to the total glass mass of the oxide conversion composition is preferably 10.0%, more preferably 7.0%, and most preferably 5.0%.
- the Al 2 O 3 component can be contained in the glass using, for example, Al 2 O 3 , Al (OH) 3 , AlF 3 or the like as a raw material.
- the ZrO 2 component is a component that widens the transmission wavelength range of the glass in the visible range 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 ZrO 2 component 15.0% or less, it is possible to make it difficult to lower the refractive index of the glass. Therefore, the content of the ZrO 2 component with respect to the total glass mass of the oxide conversion composition is preferably 15.0%, more preferably 12.0%, and most preferably 10.0%.
- the ZrO 2 component can be contained in the glass using, for example, ZrO 2 , ZrF 4 or the like as a raw material.
- Ta 2 O 5 component is a component that raises the refractive index of the glass, an optional component of the optical glass of the present invention.
- the content of the Ta 2 O 5 component with respect to the total glass mass of the oxide conversion composition is preferably 15.0%, more preferably 10.0%, and most preferably 5.0%.
- the Ta 2 O 5 component can be contained in the glass using, for example, Ta 2 O 5 as a raw material.
- the CeO 2 component is a component that adjusts the optical constant of the glass and promotes defoaming of the glass, and is an optional component in the optical glass of the present invention.
- the CeO 2 component content with respect to the total glass mass of the oxide conversion composition is preferably 10.0%, more preferably 5.0%, and most preferably 1.0%.
- the CeO 2 component is not substantially contained in terms of coloring of the glass.
- the CeO 2 component can be contained in the glass using, for example, CeO 2 as a raw material.
- the material cost of glass can be reduced by setting the content of the GeO 2 component to 15.0% or less. Therefore, the content of the GeO 2 component with respect to the total glass mass of the oxide conversion composition is preferably 15.0%, more preferably 12.0%, and most preferably 10.0%.
- the GeO 2 component can be contained in the glass using, for example, GeO 2 as a raw material.
- the Sb 2 O 3 component is a component that increases the transmittance of the glass with respect to visible light having a short wavelength and has a defoaming effect when the glass is melted, and is an optional component in the optical glass of the present invention. .
- the content of the Sb 2 O 3 component is preferably 1.0%, more preferably 0.5%, still more preferably 0.3%, and even more preferably Less than 0.1%.
- the content of the Sb 2 O 3 component with respect to the total glass mass of the oxide conversion composition is preferably less than 0.1%, more preferably. Is 0.098%, and most preferably 0.096%.
- the glass can be defoamed and a desired optical glass can be obtained, but by making the content of the Sb 2 O 3 component 0.010% or more, The defoaming effect can be achieved regardless of the production method. Therefore, the content of the Sb 2 O 3 component with respect to the total glass mass of the oxide conversion composition is preferably 0.010%, more preferably 0.020%, and most preferably 0.025%.
- the Sb 2 O 3 component can be contained in the glass using, for example, Sb 2 O 3 , Sb 2 O 5 , Na 2 H 2 Sb 2 O 7 ⁇ 5H 2 O, or the like as a raw material.
- the glass has a partial dispersion ratio ( ⁇ g, F) increased by making the content of the Sb 2 O 3 component within a predetermined range while containing the Rn 2 O component, Rn Since the transmittance of glass with respect to short-wavelength visible light is enhanced by the 2 O component and a predetermined amount of Sb 2 O 3 component, the visible region is small in color while having a desired high partial dispersion ratio ( ⁇ g, F).
- ⁇ g, F partial dispersion ratio
- the components for clarifying and defoaming the glass are not limited to the above Sb 2 O 3 component and CeO 2 component, and well-known fining agents, defoaming agents or combinations thereof in the field of glass production are used. be able to.
- the F component is a component that has the effect of increasing the meltability of the glass and the effect of increasing the Abbe number, and is an optional component in the optical glass of the present invention.
- the F of the fluoride substituted with one or two or more of the above-mentioned metal elements the total amount of 5.0% by mass is included as an upper limit, thereby obtaining a desired optical constant.
- the number can be easily realized, the internal quality of the glass can be improved, and the devitrification inside the glass when heated and softened can be reduced. Therefore, the content of the F component with respect to the total glass mass of the oxide conversion composition is preferably 5.0%, more preferably 4.5%, and most preferably 4.0%.
- the F component is introduced into the glass when the raw material form is introduced as a fluoride.
- the notation “the total amount as F of fluoride substituted for one or more of one or more oxides of each metal element” representing the content of the F component means the present invention. Assuming that all oxides, composite salts, metal fluorides, etc. used as raw materials for glass components of the glass are decomposed and transformed into oxides upon melting, F actually contained in the total mass of the product oxide The mass of an atom is expressed as a mass percentage.
- optical glass of the present invention can be added to the optical glass of the present invention as necessary within a range not impairing the properties of the glass of the present invention.
- each transition metal component such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag, and Mo, except 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. .
- the optical glass is substantially free of substances that pollute the environment. Therefore, the optical glass can be manufactured, processed, and discarded without taking special environmental measures.
- 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.
- P 2 O 5 component 0.1-30.0% and Nb 2 O 5 component 0.1-45.0% And TiO 2 component 0 to 60.0% and / or WO 3 component 0 to 15.0% and / or SiO 2 component 0 to 25.0% and / or B 2 O 3 component 0 to 25.0% and / or Or Y 2 O 3 component 0 to 7.0% and / or La 2 O 3 component 0 to 7.0% and / or Gd 2 O 3 component 0 to 7.0% and / or Yb 2 O 3 component 0 to 7.0% and / or MgO component 0-60.0% and / or CaO component 0-50.0% and / or SrO component 0-40.0% and / or BaO component 0-25.0% and / or Or ZnO component 0-40.0% and / or Li 2 O component 0-40.0% and / or Na 2 O component 0-45.0% and / or K 2 O component 0-30.0% and / or Cs 2 O component from 0 to
- 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 poured into a platinum crucible, a quartz crucible or an alumina crucible and roughly melted, and then a platinum crucible, a platinum alloy Put in a crucible or iridium crucible and melt in the temperature range of 1100-1350 ° C for 3-4 hours, stir to homogenize, blow off bubbles, etc. Is removed, cast into a mold and slowly cooled.
- the optical glass of the present invention needs to have a desired dispersion (Abbe number).
- the Abbe number ( ⁇ d ) of the optical glass of the present invention is preferably 15, more preferably 16, most preferably 17, the lower limit, preferably 27, more preferably 25, and most preferably 23. .
- the freedom degree of an optical design when the optical glass of this invention is used for an optical element can be expanded significantly.
- the optical glass of the present invention has a high partial dispersion ratio ( ⁇ g, F). More specifically, the partial dispersion ratio ( ⁇ g, F) of the optical glass of the present invention is preferably 0.62, more preferably 0.625, and most preferably 0.63. As a result, an optical glass having a large abnormal partial dispersion ( ⁇ g, F) can be obtained, so that a remarkable effect can be obtained in correcting chromatic aberration of the optical element, and the degree of freedom in optical design can be expanded.
- the upper limit of the partial dispersion ratio ( ⁇ g, F) of the optical glass of the present invention is not particularly limited, but is generally about 0.69 or less, more specifically 0.68 or less, and more specifically 0.67 or less. There are often.
- the optical glass of the present invention has a desired partial dispersion ratio ( ⁇ g, F) in the relational expression with the Abbe number ( ⁇ d ), and can correct the chromatic aberration of the lens with higher accuracy. More specifically, the partial dispersion ratio ( ⁇ g, F) of the optical glass of the present invention is ( ⁇ 4.21 ⁇ 10 ⁇ 3 ⁇ ⁇ d +0.7207) ⁇ with respect to the Abbe number ( ⁇ d ). The relationship of ( ⁇ g, F) ⁇ ( ⁇ 4.21 ⁇ 10 ⁇ 3 ⁇ ⁇ d +0.7507) is satisfied. As a result, an optical glass having a desired anomalous dispersion can be obtained, so that the chromatic aberration of the lens in the optical apparatus can be corrected with high accuracy.
- the partial dispersion ratio ( ⁇ g, F) of the optical glass is preferably ( ⁇ 4.21 ⁇ 10 ⁇ 3 ⁇ ⁇ d +0.7207), more preferably (Abbe number ( ⁇ d )). ⁇ 4.21 ⁇ 10 ⁇ 3 ⁇ ⁇ d +0.7227), and most preferably ( ⁇ 4.21 ⁇ 10 ⁇ 3 ⁇ ⁇ d +0.7247).
- the partial dispersion ratio ( ⁇ g, F) of the optical glass is preferably ( ⁇ 4.21 ⁇ 10 ⁇ 3 ⁇ ⁇ d +0.7507), more preferably (Abbe number ( ⁇ d )).
- ⁇ 4.21 ⁇ 10 ⁇ 3 ⁇ ⁇ d +0.7487) and most preferably ( ⁇ 4.21 ⁇ 10 ⁇ 3 ⁇ ⁇ d +0.7467).
- the optical glass of the present invention has high thermal stability.
- the difference ⁇ T between the glass transition point (Tg) and the crystallization start temperature (Tx) is preferably 90 ° C., more preferably 95 ° C., and most preferably 100 ° C.
- ⁇ T of the optical glass of the present invention is not particularly limited, and the upper limit is appropriately set according to the technical level.
- ⁇ T of the glass obtained by the present invention is generally 300 ° C. or lower, specifically 250 ° C. or lower, more specifically 200 ° C. or lower in many cases.
- the optical glass of this invention has little coloring.
- the wavelength ( ⁇ 70 ) showing a spectral transmittance of 70% in a sample having a thickness of 10 mm is 500 nm or less, more preferably 480 nm or less, and most preferably. Is 450 nm or less.
- the wavelength ( ⁇ 5 ) exhibiting a spectral transmittance of 5% is 450 nm or less, more preferably 420 nm or less, and most preferably 400 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 glass transition point (Tg) of 750 ° C. or lower.
- Tg glass transition point
- the upper limit of the glass transition point (Tg) of the optical glass of the present invention is preferably 750 ° C., more preferably 740 ° C., and most preferably 730 ° C.
- the minimum of the glass transition point (Tg) of the optical glass of this invention is not specifically limited, The upper limit is set suitably according to a technical level.
- the glass transition point (Tg) of the glass obtained by the present invention is generally 100 ° C. or higher, specifically 150 ° C. or higher, and more specifically 200 ° C. or higher in many cases.
- the optical glass of the present invention preferably has a desired refractive index. More specifically, the refractive index (n d ) of the optical glass of the present invention is preferably 1.75, more preferably 1.77, and most preferably 1.80. As a result, the degree of freedom in optical design is widened, and a large amount of light refraction can be obtained even if the device is made thinner.
- the upper limit of the refractive index (n d ) of the optical glass of the present invention is not particularly limited, but is generally 2.20 or less, more specifically 2.15 or less, and more specifically 2.10 or less. There are many.
- the optical glass of the present invention is useful for various optical elements and optical designs. Among them, it is particularly preferable to produce optical elements such as lenses, prisms, mirrors and the like from the optical glass of the present invention using means such as precision press molding. As a result, when used in optical devices that transmit visible light to optical elements such as cameras and projectors, the optical system in these optical devices can be miniaturized while realizing high-definition and high-precision imaging characteristics. Can be planned. In addition, since the chromatic aberration is reduced by the optical element using the optical glass, correction with an optical element having a different partial dispersion ratio ( ⁇ g, F) is not required when used in an optical device such as a camera or a projector. High-definition and high-precision imaging characteristics can be realized.
- ⁇ g, F partial dispersion ratio
- a strip material (plate-like hot-formed product) formed from the optical glass or a polishing process formed by press-molding the strip material is used.
- the preform may be manufactured by cold working such as grinding and polishing, and molten glass is dropped from the outlet of an outflow pipe of platinum or the like for precision press molding such as spherical
- a preform may be produced and precision press molding may be performed on the precision press molding preform.
- devitrification due to reheating when the strip material is press-molded is reduced, so the preform for polishing is cold worked.
- an optical element suitable for an application that transmits visible light can be obtained.
- a preform for precision press molding from the optical glass of the present invention, devitrification due to reheating when this preform is precision press molded is reduced, so it is suitable for applications that transmit visible light.
- An optical element can be obtained.
- FIG. 2 shows the relationship between the Abbe number ( ⁇ d ) and the partial dispersion ratio ( ⁇ g, F) in the glasses of the examples (No. 1 to No. 36).
- the following examples are merely for illustrative purposes, and are not limited to these examples.
- optical glass of Examples (No. 1 to No. 36) of the present invention and the glass of Comparative Example (No. A) are all oxides, hydroxides, carbonates corresponding to the raw materials of the respective components, Select high-purity raw materials used in ordinary optical glass such as nitrates, fluorides, hydroxides, metaphosphate compounds, etc., and weigh them so that the composition ratios of the respective examples shown in Tables 1 to 8 are obtained.
- ⁇ T of the optical glass of the examples (No. 1 to No. 36) and the glass of the comparative example (No. A) was measured using a differential heat measuring apparatus (STA 409 CD manufactured by Netchgeletebau). It calculated
- the transmittances of the optical glasses of Examples (No. 1 to No. 36) and the glasses of Comparative Examples (No. A) were 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 ⁇ 70 (wavelength at 70% transmittance) and ⁇ 5 (transmittance). Wavelength at 5%).
- all of the optical glasses according to the examples of the present invention have an Abbe number ( ⁇ d ) of 15 or more, more specifically 18 or more, and this Abbe number ( ⁇ d ) was 27 or less, more specifically 23 or less, and was within the desired range.
- the optical glass of the example of the present invention has a partial dispersion ratio ( ⁇ g, F) of 0.62 or more, more specifically 0.63 or more, and this partial dispersion ratio ( ⁇ g, F). Was 0.69 or less, more specifically 0.66 or less, and was within a desired range.
- the partial dispersion ratio ( ⁇ g, F) is not less than ( ⁇ 4.21 ⁇ 10 ⁇ 3 ⁇ ⁇ d +0.7207) in relation to the Abbe number ( ⁇ d ). More specifically, ( ⁇ 4.21 ⁇ 10 ⁇ 3 ⁇ ⁇ d +0.725) or more, and this partial dispersion ratio ( ⁇ g, F) is all ( ⁇ 4.21 ⁇ 10 ⁇ 3 ⁇ ⁇ d). +0.7507), more specifically, ( ⁇ 4.21 ⁇ 10 ⁇ 3 ⁇ ⁇ d +0.735) or less, which was within the desired range.
- the optical glasses of the examples of the present invention all have a difference ⁇ T between the glass transition point (Tg) and the crystallization start temperature (Tx) of 90 ° C. or more, more specifically 100 ° C. or more, and are thermally stable. It became clear that the nature was high.
- ⁇ 70 (wavelength at 70% transmittance) was 500 nm or less, more specifically, 440 nm or less.
- the optical glasses except Examples (No. 1 and No. 3) of the present invention all have ⁇ 70 of 435 nm or less, and it has been clarified that coloring is less.
- optical glasses of the examples of the present invention all had a glass transition point (Tg) of 750 ° C. or lower, more specifically 725 ° C. or lower.
- the optical glasses of the examples of the present invention all have a refractive index (n d ) of 1.75 or more, more specifically 1.81 or more, and this refractive index (n d ) is 2.20 or less. More specifically, it was 1.95 or less.
- the optical glass of the example of the present invention has high thermal stability, little coloring, and small chromatic aberration, while the Abbe number ( ⁇ d ) is within a desired range. .
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Abstract
Description
θg,F=(ng-nF)/(nF-nC)・・・・・・(1)
SiO2成分 0~10.0%及び/又は
B2O3成分 0~10.0%
である(1)から(10)のいずれか記載の光学ガラス。
Y2O3成分 0~10.0%及び/又は
La2O3成分 0~10.0%及び/又は
Gd2O3成分 0~10.0%及び/又は
Yb2O3成分 0~10.0%
である(1)から(13)のいずれか記載の光学ガラス。
MgO成分 0~25.0%及び/又は
CaO成分 0~25.0%及び/又は
SrO成分 0~25.0%及び/又は
BaO成分 0~25.0%及び/又は
ZnO成分 0~25.0%
である(1)から(16)のいずれか記載の光学ガラス。
Li2O成分 0~10.0%及び/又は
Na2O成分 0~20.0%及び/又は
K2O成分 0~20.0%及び/又は
Cs2O成分 0~10.0%
である(1)から(19)のいずれか記載の光学ガラス。
Bi2O3成分 0~20.0%及び/又は
TeO2成分 0~15.0%
である(1)から(25)のいずれか記載の光学ガラス。
Al2O3成分 0~10.0%及び/又は
ZrO2成分 0~15.0%及び/又は
Ta2O5成分 0~15.0%及び/又は
CeO2成分 0~10.0%
である(1)から(26)のいずれか記載の光学ガラス。
本発明の光学ガラスを構成する各成分の組成範囲を以下に述べる。本明細書中において、各成分の含有量は特に断りがない場合は、全て酸化物換算組成のガラス全質量に対する質量%で表示されるものとする。ここで、「酸化物換算組成」とは、本発明のガラス構成成分の原料として使用される酸化物、複合塩、金属弗化物等が溶融時に全て分解され酸化物へ変化すると仮定した場合に、当該生成酸化物の総質量を100質量%として、ガラス中に含有される各成分を表記した組成である。
Nb2O5成分は、ガラスの屈折率及び分散を高める成分である。特に、Nb2O5成分の必須成分として含有することで、ガラスの部分分散比(θg,F)を高め、ガラスの可視域の波長の光に対する透明性を高めつつ、ガラスの屈折率及び分散を高めることができる。また、Nb2O5成分の含有量を75.0%未満にすることで、ガラスの耐失透性を高めることができる。従って、酸化物換算組成のガラス全質量に対するNb2O5成分の含有量は、好ましくは0.1%、より好ましくは1.0%、さらに好ましくは10.0%、最も好ましくは25.0%を下限とし、好ましくは75.0%未満とし、より好ましくは70.0%、最も好ましくは65.0%を上限とする。Nb2O5成分は、原料として例えばNb2O5等を用いてガラス内に含有することができる。
次に、本発明の光学ガラスに含有すべきでない成分、及び含有することが好ましくない成分について説明する。
P2O5成分 0.1~30.0%及び
Nb2O5成分 0.1~45.0%、
並びに
TiO2成分 0~60.0%及び/又は
WO3成分 0~15.0%及び/又は
SiO2成分 0~25.0%及び/又は
B2O3成分 0~25.0%及び/又は
Y2O3成分 0~7.0%及び/又は
La2O3成分 0~7.0%及び/又は
Gd2O3成分 0~7.0%及び/又は
Yb2O3成分 0~7.0%及び/又は
MgO成分 0~60.0%及び/又は
CaO成分 0~50.0%及び/又は
SrO成分 0~40.0%及び/又は
BaO成分 0~25.0%及び/又は
ZnO成分 0~40.0%及び/又は
Li2O成分 0~40.0%及び/又は
Na2O成分 0~45.0%及び/又は
K2O成分 0~30.0%及び/又は
Cs2O成分 0~12.0%及び/又は
Bi2O3成分 0~7.0%及び/又は
TeO2成分 0~15.0%及び/又は
Al2O3成分 0~15.0%及び/又は
ZrO2成分 0~17.0%及び/又は
Ta2O5成分 0~5.0%及び/又は
GeO2成分 0~20.0%及び/又は
Sb2O3成分 0~0.5%
本発明の光学ガラスは、例えば以下のように作製される。すなわち、上記原料を各成分が所定の含有量の範囲内になるように均一に混合し、作製した混合物を白金坩堝、石英坩堝又はアルミナ坩堝に投入して粗溶融した後、白金坩堝、白金合金坩堝又はイリジウム坩堝に入れて1100~1350℃の温度範囲で3~4時間溶融し、攪拌均質化して泡切れ等を行った後、1200℃以下の温度に下げてから仕上げ攪拌を行って脈理を除去し、金型に鋳込んで徐冷することにより作製される。
本発明の光学ガラスは、所望の分散(アッベ数)を有する必要がある。特に、本発明の光学ガラスのアッベ数(νd)は、好ましくは15、より好ましくは16、最も好ましくは17を下限とし、好ましくは27、より好ましくは25、最も好ましくは23を上限とする。これにより、本発明の光学ガラスを光学素子に用いたときの光学設計の自由度を大幅に広げることができる。
本発明の光学ガラスは、様々な光学素子及び光学設計に有用である。その中でも特に、本発明の光学ガラスから精密プレス成形等の手段を用いて、レンズやプリズム、ミラー等の光学素子を作製することが好ましい。これにより、カメラやプロジェクタ等のような光学素子に可視光を透過させる光学機器に用いたときに、高精細で高精度な結像特性を実現しつつ、これら光学機器における光学系の小型化を図ることができる。また、この光学ガラスを用いた光学素子によって色収差が低減されるため、カメラやプロジェクタ等の光学機器に用いたときに、異なる部分分散比(θg,F)を有する光学素子による補正を行わなくとも、高精細で高精度な結像特性を実現できる。
Claims (27)
- 酸化物換算組成のガラス全質量に対して、質量%でNb2O5成分を75.0%未満、及び、P2O5成分を40.0%未満含有し、0.62以上0.69以下の部分分散比(θg,F)を有し、15以上27以下のアッベ数(νd)を有する光学ガラス。
- 酸化物換算組成のガラス全質量に対するP2O5成分の含有量が17.0%以上である請求項1記載の光学ガラス。
- 酸化物換算組成のガラス全質量に対するTiO2成分の含有量が40.0%以下である請求項1又は2記載の光学ガラス。
- 酸化物換算組成のガラス全質量に対するTiO2成分の含有量が0.1%以上である請求項3記載の光学ガラス。
- 酸化物換算組成のガラス全質量に対するWO3成分の含有量が30.0%以下である請求項1から4のいずれか記載の光学ガラス。
- 酸化物換算組成のガラス全質量に対する質量和(Nb2O5+TiO2+WO3)が40.0%以上64.0%以下である請求項1から5のいずれか記載の光学ガラス。
- 酸化物換算組成のガラス全質量に対して、質量%で
SiO2成分 0~10.0%及び/又は
B2O3成分 0~10.0%
である請求項1から6のいずれか記載の光学ガラス。 - 酸化物換算組成のガラス全質量に対する質量和(P2O5+SiO2+B2O3)が35.0%以下である請求項1から7のいずれか記載の光学ガラス。
- 酸化物換算組成における質量比(SiO2+B2O3)/(P2O5+SiO2+B2O3)が0.200未満である請求項1から8のいずれか記載の光学ガラス。
- 酸化物換算組成のガラス全質量に対して、質量%で
Y2O3成分 0~10.0%及び/又は
La2O3成分 0~10.0%及び/又は
Gd2O3成分 0~10.0%及び/又は
Yb2O3成分 0~10.0%
である請求項1から9のいずれか記載の光学ガラス。 - 酸化物換算組成のガラス全質量に対するLn2O3成分(式中、LnはY、La、Gd及びYbからなる群より選択される1種以上)の質量和が15.0%以下である請求項10記載の光学ガラス。
- 酸化物換算組成のガラス全質量に対するLn2O3成分(式中、LnはY、La、Gd及びYbからなる群より選択される1種以上)の質量和が0.1%以上15.0%以下である請求項10又は11記載の光学ガラス。
- 酸化物換算組成のガラス全質量に対して、質量%で
MgO成分 0~25.0%及び/又は
CaO成分 0~25.0%及び/又は
SrO成分 0~25.0%及び/又は
BaO成分 0~25.0%及び/又は
ZnO成分 0~25.0%
である請求項1から12のいずれか記載の光学ガラス。 - 酸化物換算組成のガラス全質量に対するRO成分(式中、RはMg、Ca、Sr、Ba及びZnからなる群より選択される1種以上)の質量和が30.0%以下である請求項13記載の光学ガラス。
- 酸化物換算組成のガラス全質量に対して、質量%で
Li2O成分 0~10.0%及び/又は
Na2O成分 0~20.0%及び/又は
K2O成分 0~20.0%及び/又は
Cs2O成分 0~10.0%
である請求項1から14のいずれか記載の光学ガラス。 - 酸化物換算組成のガラス全質量に対するRn2O成分(式中、RnはLi、Na、K及びCsからなる群より選択される1種以上)の質量和が30.0%以下である請求項15記載の光学ガラス。
- 酸化物換算組成において、Rn2O成分(式中、RnはLi、Na、K及びCsからなる群より選択される1種以上)を0%より多く含有する請求項15又は16記載の光学ガラス。
- 酸化物換算組成のガラス全質量に対して、質量%で
Bi2O3成分 0~20.0%及び/又は
TeO2成分 0~15.0%
である請求項1から17のいずれか記載の光学ガラス。 - 酸化物換算組成のガラス全質量に対して、質量%で
Al2O3成分 0~10.0%及び/又は
ZrO2成分 0~15.0%及び/又は
Ta2O5成分 0~15.0%及び/又は
CeO2成分 0~10.0%
である請求項1から18のいずれか記載の光学ガラス。 - 酸化物換算組成のガラス全質量に対するGeO2成分の含有量が15.0%以下である請求項1から19のいずれか記載の光学ガラス。
- 酸化物換算組成のガラス全質量に対するSb2O3成分の含有量が1.0%以下である請求項1から20のいずれか記載の光学ガラス。
- ガラス転移点(Tg)と結晶化開始温度(Tx)との差ΔTが90℃以上である請求項21記載の光学ガラス。
- 部分分散比(θg,F)がアッベ数(νd)との間で(-4.21×10-3×νd+0.7207)≦(θg,F)≦(-4.21×10-3×νd+0.7507)の関係を満たす請求項1から22のいずれか記載の光学ガラス。
- 分光透過率が70%を示す波長(λ70)が500nm以下である請求項1から23のいずれか記載の光学ガラス。
- 請求項1から24のいずれか記載の光学ガラスからなる研磨加工用及び/又は精密プレス成形用のプリフォーム。
- 請求項25記載のプリフォームを研磨してなる光学素子。
- 請求項25記載のプリフォームを精密プレス成形してなる光学素子。
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US11472731B2 (en) | 2021-01-22 | 2022-10-18 | Corning Incorporated | Phosphate glasses with high refractive index and reduced dispersion |
US11802073B2 (en) | 2020-09-10 | 2023-10-31 | Corning Incorporated | Silicoborate and borosilicate glasses with high refractive index and low density |
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JP6927758B2 (ja) * | 2017-06-14 | 2021-09-01 | 光ガラス株式会社 | 光学ガラス、これを用いた光学素子、光学系、レンズ鏡筒、対物レンズ及び光学装置 |
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US11485676B2 (en) | 2021-01-22 | 2022-11-01 | Corning Incorporated | Phosphate glasses with high refractive index and low density |
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