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CN105948483B - Optical glass, preform and optical element - Google Patents

Optical glass, preform and optical element Download PDF

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Publication number
CN105948483B
CN105948483B CN201610284849.5A CN201610284849A CN105948483B CN 105948483 B CN105948483 B CN 105948483B CN 201610284849 A CN201610284849 A CN 201610284849A CN 105948483 B CN105948483 B CN 105948483B
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glass
mass
optical
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CN105948483A (en
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荻野道子
上原进
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Ohara Inc
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Ohara Inc
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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/062Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064Glass compositions containing silica with less than 40% silica by weight containing boron
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/062Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/068Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/062Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/066Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C3/00Glass compositions
    • C03C3/12Silica-free oxide glass compositions
    • C03C3/14Silica-free oxide glass compositions containing boron
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C3/00Glass compositions
    • C03C3/12Silica-free oxide glass compositions
    • C03C3/14Silica-free oxide glass compositions containing boron
    • C03C3/145Silica-free oxide glass compositions containing boron containing aluminium or beryllium
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C3/00Glass compositions
    • C03C3/12Silica-free oxide glass compositions
    • C03C3/14Silica-free oxide glass compositions containing boron
    • C03C3/15Silica-free oxide glass compositions containing boron containing rare earths
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C3/00Glass compositions
    • C03C3/12Silica-free oxide glass compositions
    • C03C3/14Silica-free oxide glass compositions containing boron
    • C03C3/15Silica-free oxide glass compositions containing boron containing rare earths
    • C03C3/155Silica-free oxide glass compositions containing boron containing rare earths containing zirconium, titanium, tantalum or niobium
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C3/00Glass compositions
    • C03C3/12Silica-free oxide glass compositions
    • C03C3/16Silica-free oxide glass compositions containing phosphorus
    • C03C3/19Silica-free oxide glass compositions containing phosphorus containing boron
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C3/00Glass compositions
    • C03C3/12Silica-free oxide glass compositions
    • C03C3/16Silica-free oxide glass compositions containing phosphorus
    • C03C3/21Silica-free oxide glass compositions containing phosphorus containing titanium, zirconium, vanadium, tungsten or molybdenum
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C3/00Glass compositions
    • C03C3/12Silica-free oxide glass compositions
    • C03C3/23Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C3/00Glass compositions
    • C03C3/12Silica-free oxide glass compositions
    • C03C3/23Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron
    • C03C3/247Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron containing fluorine and phosphorus
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/002Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of materials engineered to provide properties not available in nature, e.g. metamaterials

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Glass Compositions (AREA)

Abstract

The invention relates to an optical glass, a preform and an optical element. The optical glass contains 5.0-55.0% by mass of B based on the total mass of the glass in terms of oxide2O3Component (b), 5.0-55.0% La2O3Component (b), and 2.09-20.0% of Y2O3Composition, mass and F + Bi2O3+TiO2+WO3+Nb2O5+K2O is 8.0 to 60.0%, and the glass contains 5.0 to 30.0% of F component in an increased mass% based on the total mass of the glass based on oxides, and has a refractive index n of 1.57 or moredAnd Abbe number v of 39 or moredPartial dispersion ratio (θ g, F) to vdSatisfies (theta g, F) not less than (-0.00170 x nu)d+0.63750 or (θ g, F) ≥ 2.0 × 10‑3×νd+ 0.6498).

Description

Optical glass, preform and optical element
The present application is a divisional application of the invention entitled "optical glass, preform, and optical element" having an application date of 2011, 7/26, and an application number of 201110210679.3.
Technical Field
The invention relates to an optical glass, a preform and an optical element.
Background
Optical systems of digital cameras, video cameras, and the like, although varying in degree, all contain color bleeding, which is called aberration. The aberration is classified into monochromatic aberration and chromatic aberration, and particularly, chromatic aberration strongly depends on the material characteristics of a lens used in an optical system.
In general, chromatic aberration is corrected by combining a low-dispersion convex lens and a high-dispersion concave lens, but only the aberration in the red region and the aberration in the green region can be corrected by this combination, and the aberration in the blue region remains. The aberration of the blue region that cannot be completely removed is referred to as a secondary spectrum. The correction of the secondary spectrum requires an optical design that takes into account the dynamics of the g-line (435.835nm) in the blue region. In this case, the partial dispersion ratio (θ g, F) is used as an index of optical characteristics focused on in optical design. In the optical system in which the low dispersion lens and the high dispersion lens are combined, the second-order spectrum can be corrected well by using an optical material having a large partial dispersion ratio (θ g, F) for the low dispersion lens and an optical material having a small partial dispersion ratio (θ g, F) for the high dispersion lens.
The partial dispersion ratio (θ g, F) is represented by the following formula (1).
θg,F=(ng-nF)/(nF-nC)……(1)
(ngMeans the refractive index of the glass relative to a spectral line with mercury as a light source and a wavelength of 435.835nm, nFMeans the refractive index of the glass with respect to a spectral line with a light source of hydrogen and a wavelength of 486.13nm, nCRefers to the refractive index of the glass with respect to a spectral line with a light source of hydrogen and a wavelength of 656.27 nm. )
In the optical glass, the partial dispersion ratio (theta g, F) and Abbe number (v) representing the partial dispersion of the short wavelength regiond) Approximately linear relationship therebetween. Regarding the straight line showing this relationship, the partial dispersion ratio (θ g, F) is used as the vertical axis, and the Abbe number (v) is usedd) On a rectangular coordinate on the horizontal axis, a straight line connecting two points of the partial dispersion ratio and the abbe number of NSL7 and PBM2 is referred to as a standard line (see fig. 1). Standard glass as a reference of standard lineDepending on the individual optical glass manufacturer, but each company is defined with substantially the same slope and intercept. (NSL7 and PBM2 are optical glasses manufactured by Kagaku corporation, Abbe number (. nu.) of PBM2d) 36.3, a partial dispersion ratio (. theta.g, F) of 0.5828, and an Abbe number (. nu.) of NSL7d) 60.5, and the partial dispersion ratio (. theta.g, F) was 0.5436. )
Here, the refractive index (n) is 1.73 or mored) And glass having a high abbe number (low dispersion) of 45 or more, for example, optical glass shown in patent documents 1 to 3 is known.
Further, the refractive index (n) is 1.70 or mored) And glasses having a high Abbe number (low dispersion) of 39 or more and less than 52, and containing a large amount of La as shown in patent documents 4 to 6, for example2O3An optical glass containing a rare earth element component such as a component.
The refractive index (n) is 1.60 to 1.70 inclusived) And a high Abbe number (. nu.) of 50 or mored) Optical glasses such as those disclosed in patent documents 7 to 10 are known as the glass of (1).
Further, the refractive index (n) is 1.57 or mored) And a high Abbe number (. nu.) of 50 or mored) As the glass (D) of (A), for example, those disclosed in patent documents 11 to 19, which contain a large amount of La, are known2O3An optical glass containing a rare earth element component such as a component.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2007 & 261877
Patent document 2: japanese laid-open patent publication No. 2009-084059
Patent document 3: japanese patent laid-open publication No. 2009 and No. 242210
Patent document 4: japanese patent laid-open No. 2005-170782
Patent document 5: japanese patent laid-open publication No. 2006-016295
Patent document 6: international publication No. 2004/054937 pamphlet
Patent document 7: japanese laid-open patent publication No. 56-096747
Patent document 8: japanese laid-open patent publication No. 62-087433
Patent document 9: japanese laid-open patent publication No. 11-157868
Patent document 10: japanese patent laid-open publication No. 2006-117504
Patent document 11: japanese patent laid-open publication No. 2007 & 261877
Patent document 12: japanese laid-open patent publication No. 2009-084059
Patent document 13: japanese patent laid-open publication No. 2009 and No. 242210
Patent document 14: japanese patent application laid-open No. 2006-117503
Patent document 15: japanese laid-open patent publication No. 11-139844
Patent document 16: japanese laid-open patent publication No. 62-100449
Patent document 17: japanese patent laid-open No. 2005-170782
Patent document 18: japanese patent laid-open publication No. 2006-016295
Patent document 19: international publication No. 2004/054937 pamphlet
Disclosure of Invention
Problems to be solved by the invention
However, the optical glasses of patent documents 1 to 19 do not have a large partial dispersion ratio and are not sufficient for use as lenses for correcting the secondary spectrum. That is, an optical glass having low dispersion (high abbe number) and a large partial dispersion ratio (θ g, F) is required. More specifically, it is required to have a high refractive index (n)d) And a high Abbe number (v)d) And also has a large partial dispersion ratio (θ g, F).
In particular, the glasses disclosed in patent documents 5 to 13 have a problem that devitrification is likely to occur when the glass is manufactured. It is difficult to manufacture an optical element, particularly an optical element for controlling light in a visible region, from glass that has undergone devitrification.
The present invention has been made in view of the above problems, and an object thereof is to obtain a refractive index (n)d) And Abbe number (v)d) An optical glass which is within a desired range and can be preferably used for correcting chromatic aberration, and a lens preform using the same.
Means for solving the problems
The present inventors have conducted extensive experimental studies to solve the above problems, and as a result, have found that the combination of B and C2O3Component (A) and La2O3Components (A) and (B) are added to the glass composition so that the glass has a high refractive index and a low dispersion, and the glass has a partial dispersion ratio (theta g, F) and an Abbe number (v)d) Have a desired relationship therebetween, thereby completing the present invention. In particular, it has been found that by containing F component, even if La having a strong effect of reducing the partial dispersion ratio is contained2O3The rare earth element components such as the components can also make the partial dispersion ratio (theta g, F) and Abbe number (v) of the glassd) Have a desired relationship therebetween.
It has also been found that by using B in combination2O3Component (b) and component (F) can reduce the dispersion of the glass and can improve the partial dispersion ratio to obtain the Abbe number (. nu.)d) A desired relationship between them.
In addition, B is prepared by2O3Component (A) and La2O3Component (C) and Al2O3The combination of component (A) and component (F) can realize high refractive index and low dispersion of glass, and even if La having strong effect of reducing partial dispersion ratio is contained2O3The rare earth element component such as component can also be obtained by increasing the partial dispersion ratio to Abbe number (v)d) And the liquidus temperature of the glass can be increased.
Specifically, the present invention provides the following technical solutions.
(1) An optical glass comprising B2O3Component (b) having a refractive index (n) of 1.70 or mored) And Abbe number (v) of 39 or mored) Partial dispersion ratio (. theta.g, F) and Abbe number (. nu.)d) Satisfies (theta g, F) not less than (-0.00170 x nu)d+0.63750 or (θ g, F) ≥ 2.0 × 10-3×νd+ 0.6498).
(2) The optical glass according to (1), which further contains La2O3Component (b) having a refractive index (n) of 1.73 or mored) And 45 ofAbbe number (v) ofd) Partial dispersion ratio (. theta.g, F) and Abbe number (. nu.)d) Satisfies (theta g, F) not less than (-0.00170 x nu)d+ 0.63750).
(3) The optical glass according to (1), which further contains La2O3Component (b) and component (F) and having an Abbe number (v) of 39 or more and less than 52d) Partial dispersion ratio (. theta.g, F) and Abbe number (. nu.)d) Satisfies (theta g, F) ≥ 2.0X 10-3×νd+ 0.6498).
(4) The optical glass according to (1), which further comprises an F component in the presence of an Abbe number (. nu.) ofd) Is the x-axis and has a refractive index (n)d) In xy rectangular coordinates of the y axis, the abbe number and the refractive index of the range surrounded by points a (50, 1.70), B (60, 1.60), C (63, 1.60), and D (63, 1.70)4 are shown.
(5) The optical glass according to any one of (2) to (4), wherein B is in mass% based on the total mass of the glass in terms of oxide of the composition2O35.0-50.0% of La2O3The content of the component is 55.0% or less.
(6) The optical glass according to (5), which contains 5.0% or more of La based on the total mass of the glass in terms of oxide composition2O3And (3) components.
(7) The optical glass according to (5) or (6), which contains 10.0% or more of La based on the total mass of the glass in terms of oxide composition2O3And (3) components.
(8) The optical glass according to any one of (5) to (7), wherein La is contained in the total glass mass in terms of oxide composition2O3The content of the component is 50.0% or less.
(9) The optical glass according to any one of (1) to (8), which further contains Al in an oxide-converted composition2O3And (3) components.
(10) The optical glass according to any one of (1) to (9), wherein Al is contained in an amount of mass% based on the total mass of the glass in terms of oxide of the composition2O3The content of the component is 20.0% or less.
(11) The optical glass according to item (10), wherein the optical glass contains 0.1% to 20.0% by mass of Al in terms of oxides based on the total mass of the glass2O3And (3) components.
(12) The optical glass according to any one of (1) to (11), wherein the content of the F component is 30.0% or less in incremental mass% based on the total mass of the glass based on oxides.
(13) The optical glass according to (12), wherein the F component is contained in an amount of more than 0% in incremental mass% based on the total mass of the glass based on an oxide.
(14) The optical glass according to (12) or (13), wherein the F component is contained in an amount of 0.1% by mass or more in an increment of the total mass of the glass based on an oxide.
(15) The optical glass according to any one of (1) to (14), wherein SiO is contained in an amount of mass% based on the total mass of the glass in terms of oxide of the composition2The content of the component is 40.0% or less.
(16) The optical glass according to (15), wherein SiO is contained in an amount of mass% based on the total mass of the glass in terms of oxide of the composition2The content of the component is less than 25.0%.
(17) The optical glass according to (15) or (16), further comprising SiO in an amount of mass% based on the total mass of the glass in terms of oxide of the composition2And the content thereof is 25.0% or less.
(18) The optical glass according to any one of (1) to (17), wherein the sum of the mass and the mass of (SiO) is calculated with respect to the total mass of the glass in terms of oxide2+B2O3) 40.0% or less.
(19) The optical glass according to any one of (1) to (18), wherein the optical glass comprises, in mass%, based on the total mass of the glass in terms of oxide,
Gd2O3the component(s) is (are) 0-40.0% and/or
Y2O3The component(s) is (are) 0-20.0% and/or
Yb2O3The component(s) is (are) 0-20.0% and/or
Lu2O3The component is 0-20.0%.
(20) The optical glass according to (19), further comprising an antioxidant in an amount of mass% based on the total mass of the glass in terms of oxide
0~40.0%Gd2O3Component(s) and/or
0~20.0%Y2O3Component(s) and/or
0~20.0%Yb2O3Component(s) and/or
0~10.0%Lu2O3Each component of the composition.
(21) The optical glass according to (19) or (20), further comprising an antioxidant in an amount of mass% based on the total mass of the glass in terms of oxide composition
0~30.0%Gd2O3Component(s) and/or
0~20.0%Y2O3Component(s) and/or
0~20.0%Yb2O3Component(s) and/or
0~10.0%Lu2O3Each component of the composition.
(22) The optical glass according to any one of (1) to (21), wherein Gd is present in an amount of mass% based on the total mass of the glass in terms of oxide2O3The content of (B) is 29.5% or less.
(23) The optical glass according to any one of (1) to (22), wherein Ln is calculated based on the total mass of the glass in terms of oxide2O3The sum of the mass of the components (Ln is at least one selected from the group consisting of La, Gd, Y, Yb and Lu) is 80.0% or less.
(24) The optical glass according to (23), wherein Ln is represented by the total mass of the glass in terms of oxide2O3The sum of the mass of the components (Ln is more than one selected from the group consisting of La, Gd, Y, Yb and Lu) is more than 20.0%.
(25) The optical glass according to (23) or (24), wherein Ln is represented by the total mass of the glass in terms of oxide converted composition2O3The sum of the mass of the components (Ln is at least one selected from the group consisting of La, Gd, Y, Yb and Lu) is 20.0% to 80.0%.
(26) The optical glass according to any one of (1) to (25), wherein Ln is based on the total mass of the glass in terms of oxide composition2O3The sum of the mass of the component (Ln is at least one selected from the group consisting of La, Gd, Y, Yb and Lu) is more than 43.0% and 80.0% or less.
(27) The optical glass according to (26), wherein Ln is based on the total mass of the glass in terms of oxide converted composition2O3The sum of the mass of the components (Ln is at least one selected from the group consisting of La, Gd, Y and Yb) is 63.5% or less.
(28) The optical glass according to (26) or (27), wherein Ln is represented by the total mass of the glass in terms of oxide converted composition2O3The sum of the mass of the components (Ln is more than one selected from the group consisting of La, Gd, Y and Yb) is less than 53.0%.
(29) The optical glass according to any one of (1) to (28), wherein the sum of the mass and (Gd) is the total mass of the glass in terms of oxide2O3+Yb2O3) 26.0% or less.
(30) The optical glass according to any one of (1) to (29), wherein the mass ratio Ln in terms of oxide in the composition2O3/(Bi2O3+TiO2+WO3+Nb2O5+Ta2O5) Is 1.7 or more and 25.0 or less.
(31) The optical glass according to any one of (1) to (30), wherein the mass ratio Ln of the composition in terms of oxide2O3/(SiO2+B2O3) Is 1.00 or more (in the formula, Ln is one or more selected from the group consisting of La, Gd, Y, Yb and Lu).
(32) The optical glass according to any one of (1) to (31), further comprising an antioxidant in an amount of mass% based on the total mass of the glass in terms of oxide
0~10.0%Bi2O3Component(s) and/or
0~15.0%TiO2Component(s) and/or
0~20.0%Nb2O5Each component of the composition.
(33) The optical glass according to any one of (1) to (32), further comprising an antioxidant in an amount of mass% based on the total mass of the glass in terms of oxide
0~15.0%WO3Component(s) and/or
0~10.0%K2And (3) components of the O component.
(34) The optical glass according to any one of (1) to (33), wherein the sum of the mass and (F + Bi) is calculated with respect to the total mass of the glass in terms of oxide2O3+TiO2+WO3+Nb2O5+K2O) is 0.1% or more and 30.0% or less.
(35) The optical glass according to (34), wherein the sum of mass and (F + Bi) is based on the total mass of the glass in terms of oxide composition2O3+TiO2+WO3+Nb2O5+K2O) is 1.0% or more.
(36) The optical glass according to any one of (1) to (35), wherein the sum of the mass and the amount of (Bi) is calculated based on the total mass of the glass in terms of oxide2O3+TiO2+WO3+Nb2O5) Is 20.0% or less.
(37) The optical glass according to (36), wherein the sum of the mass and the mass (Bi) is calculated with respect to the total mass of the glass in terms of oxide2O3+TiO2+WO3+Nb2O5) Is 10.0% or less.
(38) The optical glass according to any one of (1) to (37), wherein the mass ratio F/(F + Bi) in terms of oxide is2O3+TiO2+WO3+Nb2O5+K2O) is 0.36 to 1.00 inclusive.
(39) The optical glass according to any one of (1) to (38), further comprising an antioxidant in an amount of mass% based on the total mass of the glass in terms of oxide
0~15.0%ZrO2Component(s) and/or
0~25.0%Ta2O5And (3) components.
(40) The optical glass according to (39), further comprising an antioxidant in an amount of mass% based on the total mass of the glass in terms of oxide
0~15.0%ZrO2Component(s) and/or
0~15.0%Ta2O5Each component of the composition.
(41) The optical glass according to any one of (1) to (40), wherein the sum of the total mass and the mass of the glass with respect to the oxide-converted composition (WO)3+La2O3+ZrO2+Ta2O5) Is 10.0% or more and 60.0% or less.
(42) The optical glass according to any one of (1) to (41), wherein the sum of the mass and the amount of (Bi) is calculated based on the total mass of the glass in terms of oxide2O3+TiO2+WO3+Nb2O5+Ta2O5) Greater than 0%.
(43) The optical glass according to any one of (1) to (42), wherein Li is contained in an amount of mass% based on the total mass of the glass in terms of oxide of the composition2The content of the O component is 15.0% or less.
(44) The optical glass according to (43), wherein Li is contained in mass% based on the total mass of the glass in terms of oxide composition2The content of the O component is 10.0% or less.
(45) The optical glass according to (44), wherein Li is contained in an amount of mass% based on the total mass of the glass in terms of oxide composition2The content of the O component is 5.0% or less.
(46) The optical glass according to any one of (1) to (45), wherein the composition is in terms of oxidesMass ratio of (Ta)2O5+ZrO2+Li2O)/(F+Bi2O3+TiO2+WO3+Nb2O5+K2O) is 2.00 or less.
(47) The optical glass according to any one of (1) to (46), wherein the mass ratio of the oxide-converted composition (F + Bi)2O3+TiO2+WO3+Nb2O5+K2O)/(Ta2O5+ZrO2+Li2O) is 0.50 or more.
(48) The optical glass according to (47), wherein the mass ratio of the oxide-converted composition (F + Bi)2O3+TiO2+WO3+Nb2O5+K2O)/(Ta2O5+ZrO2+Li2O) is 1.3 or more.
(49) The optical glass according to any one of (1) to (48), further comprising an antioxidant in an amount of mass% based on the total mass of the glass in terms of oxide
0 to 20.0% of MgO component and/or
0 to 40.0% of CaO component and/or
0 to 40.0% of SrO and/or
0 to 55.0% of BaO component.
(50) The optical glass according to (49), further comprising an antioxidant in an amount of mass% based on the total mass of the glass in terms of oxide composition
0 to 10.0% of MgO component and/or
0 to 25.0% of CaO component and/or
0 to 25.0% of SrO and/or
0 to 55.0% of BaO component.
(51) The optical glass according to (49) or (50), wherein the glass has a glass composition as defined in (1) or (50), wherein the glass composition is a glass composition having a glass composition in terms of oxides,
MgO component of 0-10.0% and/or
CaO component of 0-15.0% and/or
SrO content is 0-15.0% and/or
BaO content is 0-25.0%.
(52) The optical glass according to any one of (1) to (51), wherein a sum of the RO components (wherein R is at least one selected from the group consisting of Mg, Ca, Sr and Ba) is 55.0% or less by mass based on the total mass of the glass in terms of oxides.
(53) The optical glass according to item (52), wherein a sum of the RO components (wherein R is at least one member selected from the group consisting of Mg, Ca, Sr and Ba) is 25.0% or less by mass based on the total mass of the glass in terms of oxides.
(54) The optical glass according to the item (52) or (53), wherein a sum of the RO components (wherein R is at least one selected from the group consisting of Mg, Ca, Sr and Ba) is 20.0% or less by mass based on a total mass of the glass in terms of oxides.
(55) The optical glass according to any one of (1) to (54), wherein Na is contained in an amount of at least one of Na and Na in mass% based on the total mass of the glass in terms of oxide content2The content of the O component is 20.0% or less.
(56) The optical glass according to (55), wherein Na is contained in an amount of mass% based on the total mass of the glass in terms of oxide of the composition2The content of the O component is 10.0% or less.
(57) The optical glass according to any one of (1) to (56), wherein Rn is based on the total mass of the glass in terms of oxide composition2The sum of the mass of O components (Rn is at least one selected from the group consisting of Li, Na and K in the formula) is 25.0% or less.
(58) The optical glass according to (57), wherein Rn is based on the total mass of the glass in terms of oxide equivalent composition2The sum of the mass of O components (Rn is at least one selected from the group consisting of Li, Na and K in the formula) is 15.0% or less.
(59) The optical glass according to any one of (1) to (58), wherein the content of the ZnO component is 30.0% by mass or less with respect to the total mass of the glass in terms of oxide composition.
(60) The optical glass according to (59), wherein the content of the ZnO component is 25.0% by mass or less based on the total mass of the glass in terms of oxide.
(61) The optical glass according to the item (59) or (60), wherein the content of the ZnO component is 15.0% by mass or less with respect to the total mass of the glass in terms of oxide composition.
(62) The optical glass according to any one of (1) to (61), further comprising an antioxidant in an amount of mass% based on the total mass of the glass in terms of oxide composition
0~10.0%GeO2Component(s) and/or
0~10.0%P2O5Component(s) and/or
0~10.0%Ga2O3Component(s) and/or
0~10.0%TeO2Component(s) and/or
0~5.0%SnO2Component(s) and/or
0~1.0%Sb2O3Each component of the composition.
(63) The optical glass according to (62), wherein the glass has a composition as determined in terms of oxides,
GeO2the component(s) is (are) 0-10.0% and/or
P2O5The component(s) is (are) 0-10.0% and/or
Ga2O3The component(s) is (are) 0-10.0% and/or
TeO2The component(s) is (are) 0-10.0% and/or
SnO2The component(s) is (are) 0-1.0% and/or
Sb2O3The component is 0-1.0%.
(64) The optical glass according to any one of (1) to (63), which has a refractive index (n) of 1.57 or mored) And an Abbe number (v) of 45 or mored)。
(65) The optical glass according to any one of (1) to (64), wherein Abbe number (. nu.) isd) And refractive index (n)d) Meet the requirement of vd≥-100×nd+220 relationship.
(66) The optical glass according to any one of (1) to (65), wherein Abbe number (. nu.) isd) And refractive index (n)d) Meet the requirement of vd≥-125×ndA relation of + 265.
(67) A preform material comprising the optical glass according to any one of (1) to (66).
(68) An optical element produced by press-forming (67) the preform.
(69) An optical element comprising the optical glass according to any one of (1) to (66) as a base material.
(70) An optical device provided with the optical element described in any one of (68) and (69).
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, the refractive index (n) can be obtainedd) And Abbe number (v)d) An optical glass which is within a desired range and can be preferably used for correcting chromatic aberration, and a preform and an optical element using the same.
Drawings
FIG. 1 shows the Abbe number (. nu.d) with the partial dispersion ratio (. theta.g, F) as the vertical axisd) A graph of the standard line in rectangular coordinates of the horizontal axis.
Detailed Description
The optical glass of the present invention contains B2O3Composition, partial dispersion ratio (. theta.g, F) and Abbe number (. nu.)d) Satisfies (theta g, F) not less than (-0.00170 x nu)d+0.63750 or (θ g, F) ≥ 2.0 × 10-3×νd+ 0.6498). By making the partial dispersion ratio (theta g, F) and Abbe number (v)d) Satisfies a prescribed relationship therebetween, thereby reducing chromatic aberration of an optical element formed of the optical glass. Thus, the refractive index (n) can be obtainedd) And Abbe number (v)d) An optical glass which is within a desired range and can be preferably used for correcting chromatic aberration, and a preform and an optical element using the same.
In particular, the optical glass of the first embodiment (hereinafter referred to as a first optical glass) contains B2O3Component (A) La2O3Component (b) having a refractive index (n) of 1.73 or mored) And an Abbe number (v) of 45 or mored) Partial dispersion ratio (. theta.g, F) and Abbe number (. nu.)d) Satisfies (theta g, F) not less than (-0.00170 x nu)d+ 0.63750). In particular, the first optical glass contains B2O3Component (A) and La2O3The composition can increase the refractive index of the glass and reduce the dispersion. Further, the dispersion ratio (θ g, F) and Abbe number (v) are adjusted by the ratiod) Satisfying a predetermined relationship, chromatic aberration of an optical element formed of the optical glass can be reduced. Thus, the refractive index (n) can be obtainedd) And Abbe number (v)d) An optical glass which is less colored in a desired range and can be preferably used for correcting chromatic aberration, and a preform and an optical element using the same.
The optical glass of the second embodiment (hereinafter referred to as the second optical glass) contains B2O3Component (A) La2O3Component (n) and component (F) having a refractive index of 1.70 or mored) And an Abbe number (v) of 39 or more and less than 52d) Partial dispersion ratio (. theta.g, F) and Abbe number (. nu.)d) Satisfies (theta g, F) ≥ 2.0X 10-3×νd+ 0.6498). In particular, in the second optical glass, B is contained2O3Component (A) and La2O3The composition can increase the refractive index of the glass, reduce the dispersion, and improve the transparency to visible light. Further, by containing the F component, La having a strong effect of reducing the partial dispersion ratio is contained2O3The chromatic aberration of an optical element made of optical glass can be reduced by increasing the partial dispersion ratio (θ g, F) by a rare earth element component such as a component. Thus, the refractive index (n) can be obtainedd) And Abbe number (v)d) An optical glass which is less colored in a desired range and can be preferably used for correcting chromatic aberration.
The optical glass of the third embodiment (hereinafter referred to as the third optical glass) contains B2O3Component (d) and component (F) in the presence of Abbe number (. nu.)d) Is the x-axis and has a refractive index (n)d) In xy rectangular coordinates of the y axis, the Abbe number and refractive index in a range surrounded by points A (50, 1.70), B (60, 1.60), C (63, 1.60) and D (63, 1.70)4, and the partial dispersion ratio (. theta.g, F) and Abbe number (. nu.g)d) Satisfies the condition that (theta g, F) is not less than-0.00170 x nud+ 0.6375. In particular, in the third optical glass, B is used in combination2O3Component (b) and component (F) can reduce the dispersion of the glass and can improve the partial dispersion ratio to obtain the Abbe number (. nu.)d) A desired relationship between them. Thus, the refractive index (n) can be obtainedd) And Abbe number (v)d) An optical glass which is within a desired range and can be preferably used for correcting chromatic aberration, and a preform and an optical element using the same.
The optical glass of the fourth embodiment (hereinafter referred to as a fourth optical glass) contains 5.0 to 55.0% by mass of B2O3Component (b), 10.0 to 55.0% of La2O3Component (C) further contains Al2O3Ingredient (b) and ingredient (F). In particular, in the fourth optical glass, B is contained in a predetermined content range2O3Component (A) and La2O3The composition can increase the refractive index of the glass and reduce the dispersion, and can improve the transparency to visible light. In addition, B is prepared by2O3Component (A) and La2O3Component (C) and Al2O3Component (A) and component (F) are used in combination, even if La having a strong effect of reducing the partial dispersion ratio is contained2O3The rare earth element component such as the component can also increase the partial dispersion ratio (θ g, F) and increase the liquidus temperature of the glass. Thus, the refractive index (n) can be obtainedd) And Abbe number (v)d) The optical glass is preferably used for correcting chromatic aberration within a desired range and has high resistance to devitrification.
The optical glass of the present invention is obtained by the following steps, which are not intended to limit the scope of the present invention. Note that, although description of the parts to be described repeatedly may be omitted as appropriate, the invention is not limited to the embodiment.
Glass composition
The compositional ranges of the respective components constituting the optical glass of the present invention are described below. In the present specification, unless otherwise specified, the contents of the respective components are all expressed in mass% with respect to the total mass of the glass in terms of oxides. Here, the "composition in terms of oxides" refers to the composition of each component contained in the glass, which is expressed by assuming that all of the oxides, complex salts, metal fluorides, and the like used as the raw materials of the glass constituent components of the present invention are decomposed to become oxides during melting, and the total mass of the generated oxides is 100 mass%.
Essential ingredients, optional ingredients
B2O3The component (b) is a component which forms a network structure in the glass and promotes stable glass formation. In particular, by reacting B2O3The content of the component (A) is 5.0% or more, and thus, the glass is less likely to devitrify and stable glass can be easily obtained. On the other hand, by making B2O3The content of the component (A) is 55.0% or less, and a desired refractive index and dispersibility can be easily obtained. Thus, B is the total mass of the glass in terms of the oxide equivalent composition2O3The lower limit of the content of the component (b) is preferably 5.0%, more preferably 8.0%, further preferably 10.0%, further preferably 13.0%, most preferably 15.0%. On the other hand, the B2O3The upper limit of the content of the component (b) is preferably 55.0%, more preferably 50.0%, further preferably 45.0%, further preferably 40.0%, further preferably 35.0%. In particular, in the optical glass of the present invention, B is2O3The content of the component (C) may be 30.0% as an upper limit. B is2O3Component (C) may be, for example, H3BO3、Na2B4O7、Na2B4O7·10H2O、BPO4Etc. are contained in the glass as raw materials.
La2O3The component is a component that increases the refractive index of the glass and reduces the dispersion.
In particular, by subjecting La2O3The content of the component (B) is 55.0% or less, so that the phase separation of the glass can be suppressed and the glass is less likely to devitrify when the glass is produced. Therefore, La is added to the total mass of the glass in terms of oxide equivalent composition2O3The upper limit of the content of the component (b) is preferably 55.0%, more preferably 54.0%, further preferably 53.0%, further preferably 52.0%, further preferably 50.0%, most preferably 45.0%. Further, La2O3The lower limit of the content of the component(s) may be appropriately set within a range in which a glass having desired optical properties can be obtained, and La is used2O3The content of the component (a) is 5.0% or more, and a desired glass having a high refractive index and a high abbe number and having a high transmittance for visible light can be easily obtained. Thus, the La2O3The content of component (b) is preferably 5.0%, more preferably 10.0%, still more preferably more than 12.0%, still more preferably 13.0%, still more preferably 15.0%. The La2O3The content of the component (B) may be 20.0% or 25.0% as the lower limit. La2O3As the component (B), for example, La can be used2O3、La(NO3)3·XH2O (X is an arbitrary integer) or the like is contained in the glass as a raw material.
The component F is a component for increasing the partial dispersion ratio of the glass and a component for lowering the glass transition temperature (Tg). In particular, by setting the content of the component F to 30.0% or less, the stability of the glass can be improved and devitrification can be made less likely. Therefore, the content of the F component is preferably 30.0%, more preferably 25.0%, further preferably 20.0%, and most preferably 15.0% in incremental mass% based on the total mass of the glass based on the oxide. In particular, the third optical glass may contain the F component in an amount of 10.0% or less. Further, the optical glass of the present invention can obtain an optical glass having a desired high partial dispersion ratio even if the optical glass does not contain F component, and by containing F component, an optical glass having a high partial dispersion ratio and less coloring can be obtained. Therefore, the content of the F component is excellent in the incremental mass% based on the total mass of the glass based on oxidesPreferably greater than 0%, more preferably 0.1% as the lower limit, more preferably greater than 0.5%, further preferably 1.0% as the lower limit, further preferably greater than 1.0%, further preferably greater than 2.0%, further preferably 3.0% as the lower limit, and most preferably greater than 3.0%. In particular, in the first and fourth optical glasses, the content of the F component may be 5.0% as a lower limit, 6.2% as a lower limit, or 6.8% as a lower limit in the incremental mass% with respect to the total mass of the glass. In the fourth optical glass, the lower limit of the content of the F component may be preferably 6.0%, more preferably 7.0%, and most preferably 8.0%. ZrF can be used as the component F4、AlF3、NaF、CaF2、LaF3Etc. are contained in the glass as raw materials.
In the present specification, the content of the F component is based on the assumption that all the cationic components constituting the glass are formed of oxides bonded to oxygen having a well-balanced charge, and the mass of the F component is expressed as mass% (incremental mass% of the total mass of the glass based on the oxides) with the total mass of the glass formed of these oxides taken as 100%.
Al2O3The component is a component which makes it easy to form a stable glass, and is an optional component in the optical glass of the present invention. In particular, by using Al2O3The content of the component (B) is 20.0% or less, and the lowering of the Abbe number of the glass can be suppressed. Therefore, Al is contained in the glass in terms of the total mass of the glass in terms of oxides2O3The upper limit of the content of component (b) is preferably 20.0%, more preferably 15.0%, and still more preferably 10.0%. The Al2O3The upper limit of the content of the component (b) may be preferably 8.0%, more preferably 5.0%, and most preferably 2.0%. Here, Al may not be contained2O3Component (B), and particularly in the fourth optical glass, by containing Al2O3The component (B) can suppress a decrease in Abbe number of the glass. Therefore, Al is contained in the glass in terms of the total mass of the glass in terms of oxides2O3The content of the component (B) is preferably more than 0%, more preferably 0.1%, still more preferably 0.5%, still more preferably 1.0% as the lower limit, and still more preferably largeAt 3.0%, most preferably greater than 3.4%. Al (Al)2O3As the component (C), for example, Al can be used2O3、Al(OH)3、AlF3Etc. are contained in the glass as raw materials.
In particular, in the fourth optical glass, it is preferable that Al2O3The ratio of the content of the component to the content of the component F is more than 0 and 15.0 or less. When the ratio is within a predetermined range, the stability of the glass can be improved, and therefore, a glass having higher devitrification resistance can be obtained. Therefore, the mass ratio of the oxide-converted composition Al2O3The lower limit of/F is preferably greater than 0, more preferably 0.1, most preferably 0.3. On the other hand, the upper limit of the ratio is preferably 15.0, more preferably 10.0, further preferably 5.0, further preferably 4.0, most preferably 3.2. In the ratio of the content, the content of the F component means a content in incremental mass% with respect to the total mass of the glass based on oxides, and Al2O3The content of the component (b) is a content of the total mass of the glass in terms of oxide.
SiO2The component (b) is a component which promotes stable glass formation and suppresses devitrification (generation of crystals) during glass production, and is an optional component in the optical glass of the present invention. In particular, by using SiO2The content of the component (C) is 40.0% or less, and SiO can be easily removed2The components are dissolved in the molten glass, and the melting at a high temperature is avoided. SiO relative to the total mass of the glass of the composition converted from oxides2The content of the component (b) is preferably 40.0%, more preferably 30.0%, still more preferably less than 28.0%, still more preferably 25.0%, still more preferably less than 25.0%, still more preferably 24.0%, still more preferably 20.0%, and most preferably less than 20.0%. In particular, in the first, second and fourth optical glasses, the SiO2The upper limit of the content of the component (B) may be 15.0% or 10.0%. Furthermore, even if SiO is not contained2The composition can also give a glass having a desired high partial dispersion ratio, and by containing SiO2Component (b) can improve the devitrification resistance of the glass. Therefore, the conversion group to oxideTotal mass of glass formed, SiO2The content of the component (b) is preferably more than 0%, preferably 0.1%, more preferably 0.5%, and still more preferably 1.0% as a lower limit. Especially, in the third optical glass, the SiO2The content of the component (C) may be 4.0% or more as the lower limit, or may be more than 5.0%. SiO 22As the component, for example, SiO can be used2、K2SiF6、Na2SiF6Etc. are contained in the glass as raw materials.
In particular, the fourth optical glass is preferably SiO2Component (A) and (B)2O3The sum of the mass of the components is 40.0% or less. This can suppress a decrease in the refractive index of the glass, and thus can obtain an optical glass having a desired high refractive index. Therefore, the sum of the total mass and mass of the glass (SiO) relative to the oxide-converted composition2+B2O3) The upper limit is preferably 40.0%, more preferably 35.0%, most preferably 32.0%. The sum of the mass (SiO) and the mass (B) is considered from the viewpoint of obtaining a glass having high stability and high devitrification resistance2+B2O3) The lower limit is preferably 5.0%, more preferably 10.0%, most preferably 15.0%.
Gd2O3The component is a component that increases the refractive index of the glass and reduces the dispersion.
In particular, by using Gd2O3The content of the component (B) is 40.0% or less, so that the phase separation of the glass can be suppressed and the glass is less likely to devitrify when the glass is produced.
Thus, Gd represents the total mass of the glass in terms of oxide content2O3The content of the component (b) is preferably 40.0%, more preferably 35.0%, still more preferably 30.0%, most preferably 29.5% 2.
In particular, in the third optical glass, the Gd2O3The content of ingredients may preferably be less than 28.0%, more preferably less than 25.0%, most preferably less than 20.0%.
Furthermore, even if Gd is not contained2O3The composition can also be made into glass with desired high partial dispersion ratio by adding 0.1% or more of Gd2O3Ingredients, can be easily obtainedThe desired refractive index and dispersion are obtained. Thus, Gd represents the total mass of the glass in terms of oxide content2O3The lower limit of the content of component (b) is preferably 0.1%, more preferably 1.0%, and still more preferably 2.0%. In particular, in the first and fourth optical glasses, the Gd2O3The content of the component (B) may be 5.0% or 7.0% as the lower limit. Gd (Gd)2O3Gd may be used as the component (a)2O3、GdF3Etc. are contained in the glass as raw materials.
Y2O3Component Yb2O3Composition and Lu2O3The component is a component that increases the refractive index of the glass and reduces the dispersion. Herein, by making Y2O3Component Yb2O3Ingredient or Lu2O3The content of the component (B) is 20.0% or less, and the glass is less likely to devitrify. In particular, by making Yb2O3The content of the component (B) is 10.0% or less, and the glass is less likely to absorb light on the long wavelength side (near 1000nm wavelength), so that the resistance of the glass to infrared rays can be improved. Thus, Y is based on the total mass of the glass in terms of the oxide equivalent composition2O3Component (b) and Yb2O3The upper limit of the content of the component (b) is preferably 20.0%, more preferably 15.0%, still more preferably 10.0%, yet more preferably 8.0%, yet more preferably 5.0%, most preferably 4.0%. In addition, Lu is the total mass of glass in terms of oxide2O3The upper limit of the content of the component (b) is preferably 20.0%, more preferably 15.0%, still more preferably 10.0%, yet more preferably 8.0%, yet more preferably 5.0%, most preferably 3.0%. In particular, from the viewpoint of improving the resistance of the glass to infrared rays, Yb is calculated based on the total mass of the glass having an oxide-converted composition2O3The content of ingredients is preferably less than 3.0%, most preferably less than 1.0%. Y is2O3Component Yb2O3Composition and Lu2O3Component (C) may be, for example, Y2O3、YF3、Yb2O3、Lu2O3Wait forIs contained as a raw material in the glass.
Ln is preferable as the optical glass of the present invention2O3The sum of the contents of the components (Ln is at least one selected from the group consisting of La, Gd, Y, Yb and Lu) is 80.0% or less. This can reduce devitrification of glass during glass production.
Thus, Ln is calculated with respect to the total mass of the glass in terms of oxide2O3The sum of the contents of the components is preferably 80.0% by mass, more preferably 78.0% by mass, and most preferably 75.0% by mass. Especially, in the third optical glass, Ln is2O3The sum of the contents of the components may be preferably 63.5% by mass, more preferably 60.0% by mass, still more preferably 55.0% by mass, and most preferably less than 50.0% by mass. Furthermore, Ln2O3The lower limit of the total content of the components may be appropriately selected in the range of the optical glass that can obtain desired characteristics, and by making it larger than 10.0%, for example, desired high refractive index and abbe number, reduction in coloring, and reduction in photoelastic constant can be easily obtained. In particular, in the optical glass of the present invention, even if a large amount of rare earth elements is contained, the partial dispersion ratio is not easily lowered, and therefore, it is possible to easily achieve both a desired high partial dispersion ratio and a desired high refractive index and abbe number. Thus, Ln is calculated with respect to the total mass of the glass in terms of oxide2O3The sum of the contents of the components is preferably more than 10.0% by mass, more preferably more than 15.0% by mass, still more preferably more than 16.0% by mass, still more preferably with the lower limit of 20.0% being more preferred, and most preferably more than 20.0% by mass. Especially, in the first, second and fourth optical glasses, Ln2O3The sum of the contents of the components may be preferably 30.0% by mass, more preferably 40.0% by mass, still more preferably more than 43.0% by mass, yet more preferably 45.0% by mass, yet more preferably 50.0% by mass, and most preferably 55.0% by mass.
In particular, Gd is preferable as the third optical glass2O3Component Yb2O3The sum of the components is 26.0% or less. This enables control of Gd, which has a strong refractive index-increasing effect2O3Component (b) and Yb2O3Use of the component, therefore, partial dispersion ratio can be improvedAnd desired refractive index and dispersion are easily obtained. Therefore, the total mass, mass and (Gd) of the glass relative to the oxide-converted composition2O3+Yb2O3) The upper limit is preferably 26.0%, more preferably 23.0%, still more preferably 20.0%, most preferably 15.0%.
In addition, Ln is preferable as the optical glass of the present invention2O3Relative to the sum of mass of (Bi)2O3+TiO2+WO3+Nb2O5+Ta2O5) The mass ratio of (a) is 1.7 or more and 25.0 or less. Thereby, the Abbe number of Bi is reduced2O3Component (C), TiO2Component (I) and WO3Component (B) and Nb2O5Component (A) and Ta2O5Ln of total content of components for increasing Abbe number2O3Is within a prescribed range, a desired abbe number can be easily obtained, and a desired relationship between the partial dispersion ratio and the abbe number can be obtained. Therefore, the mass ratio Ln in the oxide-converted composition2O3/(Bi2O3+TiO2+WO3+Nb2O5+Ta2O5) The lower limit is preferably 1.7, more preferably 3.0, further preferably 5.0, the upper limit is preferably 25.0, more preferably 20.0, most preferably 16.8.
In addition, the fourth optical glass is preferably Ln2O3(wherein Ln is at least one selected from the group consisting of La, Gd, Y, Yb and Lu) based on SiO2Component (A) and (B)2O3The ratio of the sum of the masses of the components is 1.00 or more. By setting the ratio to 1.00 or more, even if Al is not contained2O3Since the refractive index of the component (a) can be further increased, an optical glass having a high partial dispersion ratio, and having both glass stability and a high refractive index can be obtained. Therefore, the mass ratio Ln of the oxide-converted composition2O3/(SiO2+B2O3) The lower limit is preferably 1.00, more preferably 1.25, most preferably 1.40. On the other hand, the upper limit of the ratio is not particularly limited as long as a stable glass can be obtainedIt is presumed that, for example, if the amount is more than 10.0, devitrification may easily occur. Therefore, the mass ratio Ln of the oxide-converted composition2O3/(SiO2+B2O3) The upper limit is preferably 10.00, more preferably 8.00, most preferably 5.00. At Ln2O3In the component (A), La2O3Since the component (A) has an action of further improving the stability of the glass, La is used particularly from the viewpoint of obtaining a glass having high devitrification resistance2O3/(SiO2+B2O3) Ratios of (a) to (b) within the above-mentioned range are more preferable. In addition, from the viewpoint of obtaining a glass having higher devitrification resistance, the mass ratio La of the oxide-equivalent composition2O3/B2O3The upper limit may be preferably 10.00, more preferably 5.00, further preferably 3.50, further preferably 2.30, and most preferably less than 2.00.
Bi2O3The component (A) is a component for increasing the partial dispersion ratio of the glass, and is an optional component in the optical glass of the present invention for increasing the refractive index of the glass and lowering the glass transition temperature. In particular, by reacting Bi2O3The content of the component (B) is 10.0% or less, and the transmittance of light having a short wavelength (500nm or less) can be made less likely to deteriorate. Therefore, Bi is contained in the glass in terms of the total mass of the glass in terms of oxide2O3The upper limit of the content of the component (B) is preferably 10.0%, more preferably 8.0%, most preferably 5.0%. Bi2O3Component (B) can be, for example, Bi2O3Etc. are contained in the glass as raw materials.
TiO2The component (A) is a component for increasing the partial dispersion ratio of the glass, and is an optional component in the optical glass of the present invention for increasing the refractive index and dispersion of the glass and improving the chemical durability of the glass. In particular, by making TiO2The content of the component (B) is 15.0% or less, a desired high Abbe number can be easily obtained, and the transmittance of light having a short wavelength (500nm or less) is not easily deteriorated. Thus, TiO is added to the total mass of the glass in terms of oxide equivalent composition2The content of the component is preferably 15.0%,The upper limit is more preferably 12.0%, still more preferably 10.0%, still more preferably 8.0%, still more preferably 7.0%, most preferably 5.0%. TiO 22As the component (B), for example, TiO can be used2Etc. are contained in the glass as raw materials.
Nb2O5The component (A) is a component for increasing the partial dispersion ratio of the glass, and is an optional component in the optical glass of the present invention for increasing the refractive index and dispersion of the glass and improving the chemical durability of the glass. In particular, by reacting Nb2O5The content of the component (B) is 20.0% or less, and a desired high Abbe number can be easily obtained. Therefore, Nb is added to the total mass of the glass in terms of oxide2O5The upper limit of the content of the component (B) is preferably 20.0%, more preferably 15.0%, most preferably 10.0%. Nb2O5Nb is used as the component2O5Etc. are contained in the glass as raw materials.
WO3The component (A) is a component for increasing the partial dispersion ratio of the glass, and is an optional component in the optical glass of the present invention for increasing the refractive index and dispersion of the glass and improving the chemical durability of the glass. In particular, by reacting WO3The content of the component (B) is 15.0% or less, a desired high Abbe number can be easily obtained, and the transmittance of light having a short wavelength (500nm or less) is not easily deteriorated. Thus, WO is based on the total mass of the glass in terms of the oxide equivalent composition3The upper limit of the content of the component (b) is preferably 15.0%, more preferably 12.0%, still more preferably 10.0%, yet more preferably 8.0%, most preferably 5.0%. Furthermore, even if WO is not contained3The composition also gives an optical glass having a desired high partial dispersion ratio, by subjecting WO3When the content of the component (B) is 0.1% or more, the partial dispersion ratio of the glass can be improved, and therefore, a glass having a desired high partial dispersion ratio can be easily obtained. Thus, WO is based on the total mass of the glass in terms of the oxide equivalent composition3The lower limit of the content of the component (B) is preferably 0.1%, more preferably 0.3%, most preferably 0.5%. WO3As the component, for example, WO can be used3Etc. are contained in the glass as raw materials.
K2The component O is a component for further increasing the partial dispersion ratio of the glass and is an optional component in the optical glass of the present invention for improving the meltability of the glass. In particular, by making K2The content of the O component is 10.0% or less, so that the refractive index of the glass is not easily lowered, the stability of the glass is improved, and devitrification is not easily caused. Thus, K is the total mass of the glass in terms of the oxide equivalent composition2The upper limit of the content of the O component is preferably 10.0%, more preferably 8.0%, most preferably 5.0%. K2The component O may be K2CO3、KNO3、KF、KHF2、K2SiF6Etc. are contained in the glass as raw materials.
In the optical glass of the present invention, it is preferably selected from the group consisting of F component and Bi2O3Component (C), TiO2Component (I) and WO3Component (B) and Nb2O5Component (A) and (B)2The sum of the contents of at least one of the O components is 0.1% or more. By making the sum 0.1% or more, it is necessary to contain a component for improving the partial dispersion ratio, and therefore a desired high partial dispersion ratio can be easily obtained. In addition, the partial dispersion ratio of the glass can be increased, and therefore, the partial dispersion ratio and the Abbe number can be brought into a desired relationship. Therefore, the sum of the contents of these components is preferably 0.1%, more preferably 1.0%, further preferably 3.0%, further preferably 4.0%, further preferably 5.0%, further preferably 6.2%, most preferably 8.0% by mass of the composition in terms of oxides. On the other hand, the upper limit of the sum of the contents of these components is not particularly limited as long as a stable glass can be obtained, but it is presumed that, for example, if it exceeds 60.0%, devitrification may easily occur. Therefore, the sum of the contents of these components is preferably 60.0%, more preferably 50.0%, and still more preferably 40.0% by mass in terms of the oxide composition. In particular, in the second and third optical glasses, the sum of the contents of these components may be set to an upper limit of preferably 30.0%, more preferably 25.0%, more preferably 20.0%, and most preferably 15.0% with respect to the mass of the composition in terms of oxides. Furthermore, inIn the sum of the contents, the content of the F component means the content in incremental mass% with respect to the total mass of the glass based on the oxide, Bi2O3Component (C), TiO2Component (I) and WO3Component (B) and Nb2O5Component (A) and (B)2The content of the O component is a content of the total mass of the glass in terms of oxides.
Of these components, K2The O component has a refractive index lowering action, and is preferably contained in a range selected from the group consisting of F component and Bi, particularly from the viewpoint of obtaining a glass having a high refractive index2O3Component (C), TiO2Component (I) and WO3Component (B) and Nb2O5One or more of the group consisting of ingredients. In addition, Nb2O5Since the component (B) has a strong effect of lowering the Abbe number, it is preferable to contain a component selected from the group consisting of F component and Bi, particularly from the viewpoint of obtaining a glass having a high Abbe number2O3Component (C), TiO2Component (I) and WO3Component (A) and (B)2At least one of the group consisting of O components. In addition, Bi2O3Component (C), TiO2Component (A) and WO3Since the component (A) strongly acts to color the glass, it is preferable to contain a component selected from the group consisting of F component and Nb, particularly from the viewpoint of obtaining a glass with little coloring2O5Component (A) and (B)2At least one of the group consisting of O components. Therefore, from the viewpoint of obtaining a glass having a high partial dispersion ratio, a high refractive index and abbe number, and little coloring, it is preferable to increase the content of the F component among these components.
Bi in these components is preferable for the optical glass of the present invention2O3Component (C), TiO2Component (I) and WO3Component (B) and Nb2O5The sum of the contents of the components is 20.0% or less. This can reduce components that cause an increase in dispersion, and thus can easily obtain glass having desired dispersion. In addition, since the decrease in stability of the glass due to the excessive content of these components can be suppressed, the devitrification resistance of the glass can be further improved. Therefore, the sum of the total mass, mass and (Bi) of the glass in terms of oxide2O3+TiO2+WO3+Nb2O5) The upper limit is preferably 20.0%, more preferably 15.0%, most preferably 10.0%. In particular, the mass sum in the third optical glass may be 8.0% or 5.0% as an upper limit. In addition, the sum of the masses may be less than 0.5%, particularly from the viewpoint of obtaining a glass having small dispersion. On the other hand, an optical glass having a desired high partial dispersion ratio can be obtained without containing any of these components, and the partial dispersion ratio of the glass can be improved by making the sum of the mass of these components 0.1% or more, so that a glass having a desired high partial dispersion ratio can be easily obtained. Therefore, from the viewpoint of obtaining a high partial dispersion ratio, the sum of the qualities (Bi)2O3+TiO2+WO3+Nb2O5) The lower limit may be preferably 0.1%, more preferably 0.5%, and still more preferably 0.8%.
In particular, the third optical glass is preferably such that the content of the F component is relative to the F component and Bi2O3Component (C), TiO2Component (I) and WO3Component (B) and Nb2O5Component (A) and (B)2The ratio of the sum of the contents of the O components is 0.36 or more. In particular, by setting the ratio to 0.36 or more, the partial dispersion ratio can be increased and a large amount of a component with less coloring can be contained, so that a transparent glass having a desired partial dispersion ratio can be obtained. Therefore, the mass ratio F/(F + Bi) in the oxide-converted composition2O3+TiO2+WO3+Nb2O5+K2O) is preferably 0.36, more preferably 0.40, and still more preferably 0.50 as a lower limit. Further, the mass ratio is most preferably 1.00, and may be less than 1.00 from the viewpoint of obtaining a more stable glass.
ZrO2The component (C) is an optional component in the optical glass of the present invention, and is a component for increasing the refractive index of the glass and for improving the devitrification resistance in the production of the glass. In particular, by reacting ZrO2The content of the component (B) is 15.0% or less, and the decrease of the partial dispersion ratio of the glass can be suppressed. In addition, by using ZrO2The content of the component (B) is 15.0% or less, and the lowering of the Abbe number of the glass can be suppressed and avoidedMelting at a high temperature during glass production reduces energy loss during glass production. Thus, ZrO based on the total mass of the glass of the oxide-converted composition2The content of the component (b) is preferably 15.0%, more preferably 10.0%, still more preferably 8.0%, yet more preferably 7.0%, yet more preferably 5.0%, and most preferably less than 4.0%. Furthermore, even if ZrO is not contained2The components can also give a glass having desired optical characteristics, and ZrO is added2The content of the component (B) is 0.1% or more, and devitrification resistance of the glass can be improved. Thus, in the presence of ZrO2In the case of the component (B), ZrO based on the total mass of the glass having the composition in terms of oxides2The lower limit of the content of the component (b) is 0.1%, more preferably 0.5%, and still more preferably 1.0%. ZrO (ZrO)2As the component, for example, ZrO can be used2、ZrF4Etc. are contained in the glass as raw materials.
Ta2O5The component (b) is a component for increasing the refractive index of the glass and stabilizing the glass, and is an optional component in the optical glass of the present invention. In particular, by reacting Ta2O5The content of the component (B) is 25.0% or less, and the partial dispersion ratio of the glass can be suppressed from lowering. In addition, by using Ta2O5The content of the component (B) is 25.0% or less, and the material cost of the glass can be reduced, and the energy loss during the glass production can be prevented from being reduced by melting at a high temperature. Therefore, Ta is the total mass of the glass in terms of the composition of oxides2O5The content of the component (b) is preferably 25.0% as an upper limit, more preferably less than 16.5%, still more preferably 15.0%, yet more preferably 10.0%, most preferably 5.0%. Ta2O5Component (D) may be Ta2O5Etc. are contained in the glass as raw materials.
Among the optical glasses of the present invention, WO is preferable3Component (A) La2O3Component (C) ZrO2Component (A) and Ta2O5The sum of the contents of (A) and (B) is 10.0% or more. When the sum is 10.0% or more, the refractive index can be further increased while reducing the coloring of the glass. Therefore, the composition is converted with respect to the oxideThe sum of the contents of these components is preferably 10.0%, more preferably 20.0%, still more preferably 25.0%, and most preferably 30.0% as the lower limit. On the other hand, the upper limit of the sum of the contents of these components is not particularly limited as long as a stable glass can be obtained, but it is presumed that, for example, if it exceeds 65.0%, devitrification may easily occur. Therefore, the sum of the contents of these components is preferably 65.0%, more preferably 60.0%, further preferably 55.0%, and most preferably 50.0% by mass in terms of the oxide composition.
In particular, in the second optical glass, it is preferable to be selected from Bi2O3Component (C), TiO2Component (I) and WO3Component (B) and Nb2O5Component (A) and Ta2O5The sum of the contents of more than one of the components is greater than 0%. This reduces the abbe number of the glass, and thus an optical glass having an abbe number in a desired range can be easily obtained. Therefore, the sum of the contents of these components is preferably more than 0%, more preferably 1.0%, and most preferably 2.0% by mass of the oxide-converted composition. On the other hand, the upper limit of the sum of the contents of these components is not particularly limited as long as a stable glass can be obtained, but it is presumed that, for example, if it exceeds 25.0%, devitrification may easily occur. Therefore, the sum of the contents of these components is preferably 25.0%, more preferably 15.0%, and most preferably 10.0% by mass in terms of oxide composition.
Li2The component O is a component for improving the meltability of the glass and is an optional component in the optical glass of the present invention. In particular, by reacting Li2When the content of the O component is 15.0% or less, the partial dispersion ratio of the glass can be suppressed from lowering, and the partial dispersion ratio and the Abbe number can be maintained in a desired relationship. In addition, by using Li2The content of the O component is 15.0% or less, and Li can be contained excessively while suppressing the decrease of the refractive index of the glass2Devitrification due to the O component does not easily occur. Therefore, Li represents the total mass of the glass in terms of the composition of oxides2The content of the O component is preferably 15.0%, more preferably 10.0%, further preferably 8.0%The upper limit is preferably 5.0%, more preferably 4.0%, still more preferably 3.0%, still more preferably less than 3.0%, and still more preferably 2.3%. In particular, the Li is advantageous from the viewpoint that an optical glass having a higher partial dispersion ratio can be easily obtained2The content of the O component may be 0.5% or less, may be 0.4% or less, may be less than 0.1%, or may be substantially absent. Li2As the O component, for example, Li can be used2CO3、LiNO3And LiF, etc. are contained in the glass as raw materials.
The optical glass of the present invention is preferably Ta2O5Component (C) ZrO2Component (A) and Li2Sum of contents of O component to F component and Bi component2O3Component (C), TiO2Component (I) and WO3Component (B) and Nb2O5Component (A) and (B)2The ratio of the sum of the contents of the O components is 2.00 or less. Thereby, the content of the component having the effect of reducing the partial dispersion ratio is made lower than that of the component having the effect of increasing the partial dispersion ratio, and therefore a glass having a higher partial dispersion ratio can be obtained. Therefore, the mass ratio (Ta) in the oxide-converted composition2O5+ZrO2+Li2O)/(F+Bi2O3+TiO2+WO3+Nb2O5+K2O) is preferably at an upper limit of 2.00, more preferably at 1.40, more preferably at 1.00, most preferably at 0.80. The mass ratio may be 0, and the devitrification resistance of the glass can be further improved by setting the mass ratio to 0.10 or more. Therefore, the mass ratio (Ta) in the oxide-converted composition2O5+ZrO2+Li2O)/(F+Bi2O3+TiO2+WO3+Nb2O5+K2O) is preferably 0.10, more preferably 0.20, most preferably 0.30.
In the optical glass of the present invention, (F + Bi) is preferably2O3+TiO2+WO3+Nb2O5+K2O) relative to (Ta)2O5+ZrO2+Li2O) is 0.50 or more. BySince the content of the component for increasing the partial dispersion ratio is larger than the content of the component for greatly decreasing the partial dispersion ratio, a desired high partial dispersion ratio can be easily obtained even when a larger amount of the rare earth element is added. That is, both a high partial dispersion ratio and a high abbe number can be easily achieved. Therefore, the mass ratio (F + Bi) in the oxide-converted composition2O3+TiO2+WO3+Nb2O5+K2O)/(Ta2O5+ZrO2+Li2O) is preferably 0.50, more preferably 1.00, further preferably 1.32, further preferably 1.70. In particular, in the first optical glass, the ratio of the content may be preferably 1.3, more preferably 1.5, most preferably 2.0 as a lower limit. On the other hand, the upper limit of the ratio of the content is not particularly limited, and may be infinite (that is, Ta)2O5+ZrO2+Li2O ═ 0%), and the ratio may be 100.0 or less from the viewpoint of further improving the stability of the glass.
The MgO component, CaO component, SrO component and BaO component are components for improving the melting property of the glass and for improving the devitrification resistance, and are optional components in the optical glass of the present invention. In particular, the refractive index of the glass can be made less likely to decrease by setting the content of the MgO component to 20.0% or less, the content of the CaO component or the SrO component to 40.0% or less, or the content of the BaO component to 55.0% or less. Therefore, the upper limit of the content of the MgO component is preferably 20.0%, more preferably 15.0%, further preferably 10.0%, further preferably 8.0%, and most preferably 5.0% with respect to the total mass of the glass in terms of oxides. The content of the CaO component is preferably 40.0%, more preferably 30.0%, further preferably 25.0%, further preferably 20.0%, further preferably 15.0%, further preferably 12.0%, further preferably 10.0% as an upper limit, and most preferably less than 10.0% with respect to the total glass mass in terms of oxides. The content of the SrO component is preferably 40.0%, more preferably 30.0%, further preferably 25.0%, further preferably 20.0%, further preferably less than 16.0%, further preferably 15.0% by weight of the total glass mass in terms of oxides.The upper limit of the content of the SrO component may be more preferably 12.0%, and still more preferably 10.0%. The content of the BaO component is preferably 55.0%, more preferably 45.0%, further preferably 40.0%, further preferably 35.0%, and further preferably less than 30.0% by mass of the total glass in terms of oxides. The upper limit of the content of the BaO component may be preferably 25.0%, more preferably 20.0%, and still more preferably 15.0%. In particular, the content of the BaO component in the second optical glass may be 10.0% as an upper limit, or may be less than 6.0%. MgCO, CaO, SrO and BaO can be used as the MgO component, CaO component, SrO component and BaO component3、MgF2、CaCO3、CaF2、Sr(NO3)2、SrF2、BaCO3、Ba(NO3)2Etc. are contained in the glass as raw materials.
In the optical glass of the present invention, the sum of the contents of RO components (in the formula, R is one or more selected from the group consisting of Mg, Ca, Sr, and Ba) is preferably 55.0% by mass or less. This makes it possible to reduce devitrification of the glass due to excessive RO component content and to prevent the refractive index of the glass from being lowered. Therefore, the sum of the contents of RO components is preferably 55.0% by mass, more preferably 45.0% by mass, still more preferably 40.0% by mass, and most preferably 35.0% by mass, based on the total mass of the glass in terms of oxides. The sum of the amounts by mass of the RO components may be preferably 25.0%, more preferably 20.0%, still more preferably 15.0%, and most preferably 10.0% as an upper limit.
Na2The component O is a component for improving the meltability of the glass and is an optional component in the optical glass of the present invention. In particular, by reacting Na2The content of the O component is 20.0% or less, and the refractive index of the glass is not easily lowered, and the stability of the glass is improved to prevent devitrification and the like. Therefore, Na represents the total mass of the glass in terms of the oxide equivalent composition2The upper limit of the content of the O component is preferably 20.0%, more preferably 15.0%, further preferably 10.0%, more preferably 8.0%, most preferably 5.0%. Na (Na)2As the O component, Na, for example, can be used2CO3、NaNO3、NaF、Na2SiF6Etc. are contained in the glass as raw materials.
Rn2The O component (where Rn is one or more selected from the group consisting of Li, Na, and K) is a component that improves the meltability of the glass, lowers the glass transition temperature, and reduces devitrification of the glass. Here, by making Rn2The content of the O component is 25.0% or less, and the refractive index of the glass is not easily lowered, and the stability of the glass is improved to reduce the occurrence of devitrification and the like. Rn is thus based on the total mass of the glass in terms of oxide-reduced composition2The sum of the mass of the O component is preferably 25.0%, more preferably 20.0%, most preferably 15.0% as an upper limit. In particular, in the fourth optical glass, the mass sum may be 10.0% or 5.0% as an upper limit.
The ZnO component is a component that improves the melting property of the glass, lowers the glass transition temperature, and makes it easy to form a stable glass, and is an optional component in the optical glass of the present invention.
In particular, by setting the content of the ZnO component to 30.0% or less, the photoelastic constant of the optical glass can be kept low. Therefore, the polarization characteristics of the transmitted light of the optical glass can be improved, and the color rendering properties in a projector or a camera can be improved.
Therefore, the content of the ZnO component is preferably 30.0%, more preferably 25.0%, further preferably 20.0%, further preferably 15.0%, further preferably 12.0%, further preferably 10.0%, further preferably 8.7%, further preferably 7.7% by weight of the total glass mass in terms of oxides. In particular, the content of the ZnO component in the first optical glass may be 5.0% as an upper limit. As the ZnO component, for example, ZnO or ZnF can be used2Etc. are contained in the glass as raw materials.
GeO2The component (b) is a component having the effect of increasing the refractive index of the glass and improving resistance to devitrification, and is an optional component in the optical glass of the present invention. However, GeO2Since the raw materials for the components are expensive, if the amount is large, the material cost becomes high, and the glass obtained becomes impractical.Thus, GeO is the amount of GeO relative to the total mass of the glass in terms of the oxide converted composition2The content of the component (b) is preferably 10.0%, more preferably 8.0%, still more preferably 5.0%, still more preferably 2.0%, as an upper limit, and most preferably less than 2.0%. GeO2As the component (B), GeO can be used2Etc. are contained in the glass as raw materials.
P2O5The component (b) is a component having an effect of lowering the liquidus temperature of the glass and improving resistance to devitrification, and is an optional component in the optical glass of the present invention. In particular, by making P2O5When the content of the component (B) is 10.0% or less, the chemical durability, particularly the water resistance of the glass can be suppressed from lowering. Thus, P is the total mass of the glass in terms of the oxide equivalent composition2O5The upper limit of the content of the component (b) is preferably 10.0%, more preferably 8.0%, still more preferably 5.0%, most preferably 2.0%. P2O5As the component (C), for example, Al (PO) can be used3)3、Ca(PO3)2、Ba(PO3)2、BPO4、H3PO4Etc. are contained in the glass as raw materials.
Ga2O3The component is a component which makes it easy to form a stable glass, and is an optional component in the optical glass of the present invention. In particular, by reacting Ga2O3The content of the component (B) is 10.0% or less, and the lowering of the Abbe number of the glass can be suppressed. Therefore, Ga is contained in the total mass of the glass in terms of oxide composition2O3The upper limit of the content of each component is preferably 10.0%, more preferably 8.0%, further preferably 5.0%, most preferably 2.0%. Ga2O3Component (C) is, for example, Ga2O3、Ga(OH)3Etc. are contained in the glass as raw materials.
TeO2The component (C) is a component for increasing the refractive index and lowering the glass transition temperature (Tg), and is an optional component in the optical glass of the present invention. However, TeO2There are the following problems: when a glass raw material is melted in a crucible made of platinum and a melting tank in which a portion contacting molten glass is made of platinum, the glass raw material is alloyed with platinum. Thus, TeO is the amount of the total mass of the glass in terms of oxide2The upper limit of the content of component (b) is preferably 10.0%, more preferably 8.0%, and most preferably 5.0%. TeO2As the component (C), for example, TeO can be used2Etc. are contained in the glass as raw materials.
SnO2The component (b) is a component which reduces oxidation of the molten glass, clarifies the molten glass, and hardly deteriorates the transmittance of the glass to light irradiation, and is an optional component in the optical glass of the present invention. In particular, by reacting SnO2When the content of the component is 5.0% or less, the glass is less likely to be colored or devitrified by reduction of the molten glass. In addition, SnO can be mitigated2The composition is alloyed with a melting apparatus (particularly, a noble metal such as Pt), and therefore, the life of the melting apparatus can be extended. Thus, SnO represents the total mass of glass in terms of oxide equivalent composition2The upper limit of the content of the component (b) is preferably 5.0%, more preferably 3.0%, still more preferably 1.0%, even more preferably 0.7%, most preferably 0.5%. SnO2As the component (C), SnO and SnO can be used2、SnF2、SnF4Etc. are contained in the glass as raw materials.
Sb2O3The component (B) is a component for degassing molten glass and is an optional component in the optical glass of the present invention. In particular, by reacting Sb2O3The content of the component (C) is 1.0% or less, so that excessive foaming during glass melting is less likely to occur, and Sb can be made to be Sb2O3The composition is less likely to be alloyed with melting equipment (particularly noble metals such as Pt). Therefore, Sb is calculated with respect to the total mass of the glass in terms of the oxide content2O3The upper limit of the content of the component (B) is preferably 1.0%, more preferably 0.8%, most preferably 0.5%. Sb2O3As the component (C), Sb may be used2O3、Sb2O5、Na2H2Sb2O7·5H2O and the like are contained in the glass as raw materials.
The content of the glass refining and degassing is not limited to Sb2O3As the component (b), a refining agent, a defoaming agent or a combination thereof known in the glass production field can be used.
With respect to components not to be contained
Next, components that should not be contained in the optical glass of the present invention and components that are contained therein are described.
In the optical glass of the present invention, other components may be added as necessary within a range not impairing the characteristics of the glass of the present invention. However, GeO2The component (B) is preferably substantially not contained because it improves the dispersibility of the glass.
Further, since each of the transition metal components of V, Cr, Mn, Fe, Co, Ni, Cu, Ag, Mo, and the like other than Ti, Zr, Nb, W, La, Gd, Y, Yb, and Lu has a property of coloring the glass and absorbing a specific wavelength in the visible region even when each is contained in a small amount singly or in a composite form, it is preferable that the transition metal component is not substantially contained particularly in the optical glass using the wavelength in the visible region.
Further, lead compounds such As PbO and As2O3In recent years, arsenic compounds such as these and components such as Th, Cd, Tl, Os, Be, and Se tend to Be used as harmful chemicals under control, and therefore, environmental measures are required not only in the glass production process but also in the processing process and the treatment after the production. Therefore, when importance is attached to the influence on the environment, it is preferable that these components are not substantially contained except for the case of unavoidable contamination. Therefore, the optical glass is basically free of substances which pollute the environment. Therefore, the optical glass can be manufactured, processed and discarded even without taking special measures for environmental management.
The composition of the glass composition of the present invention is expressed in mass% based on the total mass of the glass in terms of oxides, and therefore is not directly expressed in terms of mol%, but the composition in terms of mol% of each component present in the glass composition satisfying various characteristics required by the present invention is approximately the following value in terms of oxides.
10.0~75.0mol%B2O3Composition (I)
And
0~25.0mol%La2O3component(s) and/or
0~4.0mol%Bi2O3Component(s) and/or
0~30.0mol%TiO2Component(s) and/or
0~10.0mol%WO3Component(s) and/or
0~10.0mol%Nb2O5Component(s) and/or
0~15.0mol%K2O component and/or
0~10.0mol%Ta2O5Component(s) and/or
0~25.0mol%ZrO2Component(s) and/or
0~40.0mol%Li2O component and/or
0~20.0mol%Gd2O3Component(s) and/or
0~15.0mol%Y2O3Component(s) and/or
0~10.0mol%Yb2O3Component(s) and/or
0~10.0mol%Lu2O3Component(s) and/or
0 to 50.0 mol% of MgO component and/or
0 to 50.0 mol% of CaO component and/or
0 to 50.0 mol% of SrO component and/or
0 to 55.0 mol% of BaO component and/or
0~70.0mol%SiO2Component(s) and/or
0 to 30.0 mol% of ZnO component and/or
0~20.0mol%GeO2Component(s) and/or
0~10.0mol%P2O5Component(s) and/or
0~40.0mol%Al2O3Component(s) and/or
0~8.0mol%Ga2O3Component(s) and/or
0~25.0mol%Na2O component and/or
0~8.0mol%TeO2Component(s) and/or
0~5.0mol%SnO2Component(s) and/or
0~1.0mol%SnO2Component(s) and/or
0~0.5mol%Sb2O3Composition (I)
And 0 to 75.0 mol% of the total amount of F as fluoride substituted with a part or all of an oxide of one or more of the above metal elements.
In particular, the composition of the first optical glass in mol% is preferably, in terms of oxide-converted composition:
5.0~25.0mol%La2O3composition (I)
And
0~5.0mol%Ta2O5component(s) and/or
0~25.0mol%Li2O component and/or
0 to 35.0 mol% of MgO component and/or
0 to 35.0 mol% of CaO component and/or
0 to 25.0 mol% of SrO component and/or
0 to 25.0 mol% of BaO component and/or
0~60.0mol%SiO2Component(s) and/or
0~20.0mol%Al2O3Component(s) and/or
0~1.0mol%SnO2And (3) components.
In addition, the composition of the second optical glass in mol% is preferably:
5.0~25.0mol%La2O3composition (I)
And
0~30.0mol%Li2o component and/or
0~5.0mol%Lu2O3Component(s) and/or
0 to 35.0 mol% of MgO component and/or
0 to 35.0 mol% of CaO component and/or
0 to 25.0 mol% of SrO component and/or
0 to 25.0 mol% of BaO component and/or
0~60.0mol%SiO2Component(s) and/or
0~20.0mol%Al2O3Component(s) and/or
0~1.0mol%SnO2And (3) components.
In particular, the composition of the third optical glass in mol% is preferably, in terms of oxide-converted composition:
0~15.0mol%Gd2O3component(s) and/or
0~3.0mol%Ta2O5Component(s) and/or
0 to 25.0 mol% of ZnO component and/or
0~20.0mol%Al2O3Composition (I)
And a total amount of fluoride in terms of F which is greater than 0 mol% and not more than 75.0 mol% and which is substituted with a part or all of an oxide of one or two or more of the above-mentioned metal elements.
In addition, the composition of the fourth optical glass in mol% is preferably:
10.0~75.0mol%B2O3ingredients (A) and (B),
10.0~25.0mol%La2O3Components and
more than 0 mol% and 40.0 mol% or less of Al2O3Composition (I)
And
0~4.0mol%Ta2O5component(s) and/or
0~15.0mol%Li2O component and/or
0 to 35.0 mol% of MgO component and/or
0 to 50.0 mol% of CaO component and/or
0 to 35.0 mol% of SrO component and/or
0 to 50.0 mol% of BaO component and/or
0 to 25.0 mol% of ZnO component
And a total amount of fluoride in terms of F which is greater than 0 mol% and not more than 75.0 mol% and which is substituted with a part or all of an oxide of one or two or more of the above-mentioned metal elements.
Manufacturing method
The optical glass of the present invention can be produced, for example, as follows. That is, the raw materials are uniformly mixed so that each component is within a predetermined content range, the prepared mixture is put into a platinum crucible, a quartz crucible, or an alumina crucible to be roughly melted, then put into a gold crucible, a platinum alloy crucible, or an iridium crucible to be melted at a temperature of 900 to 1400 ℃ for 1 to 5 hours, stirred, homogenized, defoamed, and the like, and then cooled to a temperature of 1200 ℃ or lower, and finally stirred to remove the striae, and molded using a molding die. Here, as a method for obtaining a molded glass using a molding die, there are mentioned: a method of flowing down molten glass at one end of a molding die and simultaneously drawing out molded glass at the other end of the molding die; a method of forming a glass molding by so-called direct press; a method of forming a glass molded body by casting molten glass into a mold and annealing the glass, as in the so-called float molding.
Physical Properties
The optical glass of the present invention preferably has a predetermined refractive index and dispersion (abbe number).
Here, the refractive index (n) of the optical glass of the present inventiond) The lower limit is preferably 1.50, more preferably 1.51, and still more preferably 1.52. In particular, the refractive indices (n) of the first and second optical glassesd) The lower limit may be preferably 1.70, more preferably 1.73, further preferably 1.75, most preferably 1.77. In addition, the refractive index (n) of the fourth optical glassd) The lower limit may be preferably 1.57, more preferably 1.60, most preferably 1.65. On the other hand, the refractive index (n) to the optical glass of the present inventiond) The upper limit of (b) is not particularly limited, but is usually about 2.20 or less, more specifically 2.10 or less, and still more specifically 2.00 or less. In particular, the refractive index (n) of the third optical glassd) The upper limit of (b) may be preferably 1.70, more preferably less than 1.70, and most preferably 1.69.
Abbe number (v) of the optical glass of the present inventiond) Superior foodThe lower limit is selected from 39, more preferably 40, and still more preferably 41. In particular, the Abbe number (. nu.) of the first and fourth optical glassesd) The lower limit may be preferably 45, more preferably 47, most preferably 49. Further, the Abbe number (. nu.) of the third optical glassd) The lower limit may be preferably 50, more preferably 52, most preferably 53. On the other hand, Abbe number (. nu.) of the optical glass of the present inventiond) The upper limit of (b) is not particularly limited, but is usually about 63 or less, more specifically 61 or less, still more specifically 60 or less, yet more specifically 58 or less, yet more specifically 57 or less. In particular, the second optical glass of the present invention has an Abbe number (. nu.) ofd) The upper limit may be preferably 52, more preferably 51, most preferably 50.
Here, the second optical glass of the present invention has an Abbe number (. nu.) ofd) And refractive index (n)d) Preferably satisfies (v)d)≥(-125×nd+265), more preferably satisfies (v)d)≥(-125×nd+266), most preferably satisfies (v)d)≥(-125×nd+ 267).
Further, the Abbe number (. nu.) of the optical glass of the present inventiond) And refractive index (n)d) Preferably satisfies (v)d)≥(-100×nd+220), more preferably satisfies (v)d)≥(-100×nd+222), most preferably satisfies (v)d)≥(-100×nd+ 223). In particular, in the third optical glass, it is preferable that the Abbe number (v) is larger than the Abbe numberd) Is the x-axis and has a refractive index (n)d) In xy rectangular coordinates of the y axis, the abbe number and the refractive index of the range surrounded by points a (50, 1.70), B (60, 1.60), C (63, 1.60), and D (63, 1.70)4 are shown.
This increases the degree of freedom in optical design, and enables a large amount of light refraction to be obtained even when the element is further thinned.
In addition, the optical glass of the present invention has a high partial dispersion ratio (θ g, F). More specifically, the optical glass of the present invention has a partial dispersion ratio (. theta.g, F) and an Abbe number (. nu.d) Satisfies (theta g, F) not less than (-0.00170 x nu)d+0.6375) or(θg,F)≥(-2.0×10-3×νd+ 0.6498). The optical glass of the present invention can obtain an optical glass having a higher partial dispersion ratio (θ g, F) than the conventional known glass even when it contains a large amount of a rare earth element component. Therefore, it is possible to reduce chromatic aberration of an optical element formed of the optical glass while achieving high refractive index and low dispersion of the glass.
Here, the lower limit of the partial dispersion ratio (θ g, F) of the first optical glass is preferably (-0.00170 × ν)d+0.63750), more preferably (-0.00170 x ν)d+0.63950), most preferably (-0.00170 x ν)d+0.64150). On the other hand, the upper limit of the partial dispersion ratio (θ g, F) of the first optical glass is not particularly limited, but is usually, for example, (-0.00170 × ν)d+0.65750), more preferably (-0.00170 x ν)d+0.65550), most preferably (-0.00170 x ν)d+0.653750)。
In addition, the lower limit of the partial dispersion ratio (θ g, F) of the second optical glass is preferably (-2.0 × 10)-3×νd+0.6498), more preferably (-2.0X 10)-3×νd+0.6518), most preferably (-2.0X 10)-3×νd+0.6558). On the other hand, the upper limit of the partial dispersion ratio (θ g, F) of the second optical glass is not particularly limited, but is usually, for example, (-2.0X 10)-3×νd+0.6950), more preferably (-2.0X 10)-3×νd+0.6930), most preferably (-2.0X 10)-3×νd+0.6910). Further, the partial dispersion ratio of the second optical glass and the Abbe number (. nu.) are set to be equal to each otherd) When the relationship (c) is defined by a straight line parallel to the standard line, the partial dispersion ratio (θ g, F) is usually, for example (-1.7X 10)-3×νd+0.63450), more specifically (-1.7X 10)-3×νd+0.63750), more specifically (-1.7X 10)-3×νd+0.63950), more specifically (-1.7X 10)-3×νd+0.64150), typically (-1.7X 10)-3×νd+0.67750) or less, more specifically (-1.7X 10)-3×νd+0.67550) or less, more specifically (-1.7X 10)-3×νd+0.67350)The following.
In addition, the lower limit of the partial dispersion ratio (θ g, F) of the third optical glass is preferably (-0.00170 × ν)d+0.6375), more preferably (-0.00170 x ν)d+0.6395), most preferably (-0.00170 x ν)d+0.6415). On the other hand, the upper limit of the partial dispersion ratio (θ g, F) of the third optical glass is not particularly limited, and is usually about (-0.00170 × ν)d+0.6575), more particularly (-0.00170 x ν)d+0.6555), and further specifically (-0.00170 x ν)d+0.6535)。
In addition, the lower limit of the partial dispersion ratio (θ g, F) of the fourth optical glass is preferably (-0.00170 × ν)d+0.6375), more preferably (-0.00170 x ν)d+0.6395), most preferably (-0.00170 x ν)d+0.6415). On the other hand, the upper limit of the partial dispersion ratio (θ g, F) of the fourth optical glass is not particularly limited, and is usually about (-0.00170 × ν)d+0.6800), more particularly (-0.00170 x ν)d+0.6790), more specifically (-0.00170 x ν)d+0.6780) or less. The preferable range of the partial dispersion ratio of the present invention varies depending on the abbe number of the optical glass, and is represented by a straight line parallel to the standard line.
The partial dispersion ratio (. theta.g, F) of the optical glass of the present invention was measured based on the Japanese optical Nitri Industrial Standard JOGIS 01-2003. In addition, the glass used in this measurement was treated in an annealing furnace at an annealing temperature reduction rate of-25 ℃ per hour.
The optical glass of the present invention preferably has a glass transition temperature (Tg) of 650 ℃. This makes it possible to perform press molding at a lower temperature, and therefore, oxidation of the mold used for press molding can be reduced, and the life of the mold can be prolonged. Therefore, the glass transition temperature (Tg) of the optical glass of the present invention is preferably 650 ℃, more preferably 620 ℃ and most preferably 600 ℃. The lower limit of the glass transition temperature (Tg) of the optical glass of the present invention is not particularly limited, and the glass obtained according to the present invention generally has a glass transition temperature (Tg) of about 100 ℃ or higher, specifically 150 ℃ or higher, and more specifically 200 ℃ or higher.
The glass transition temperature (Tg) of the optical glass of the present invention is determined by using a differential thermal measurement device (NETZSCH-
Figure BDA0000978425210000421
STA 409 CD manufactured by GmbH). Here, the particle size of the sample is 425 to 600 μm and the temperature rise rate is 10 ℃/min.
In addition, the optical glass of the present invention is preferably less colored. When the optical glass of the present invention is expressed in terms of transmittance of glass, a sample having a thickness of 10mm shows a wavelength (. lamda.) of 70% spectral transmittance70) Is 500nm or less, more preferably 480nm or less, and most preferably 450nm or less. The optical glass of the present invention is particularly preferred in that a sample having a thickness of 10mm exhibits a wavelength (. lamda.) of 80% spectral transmittance80) Is 500nm or less, more preferably 480nm or less, and most preferably 450nm or less. In addition, a sample of the optical glass of the present invention having a thickness of 10mm shows a wavelength (. lamda.) of 5% spectral transmittance5) 450nm or less, more preferably 430nm or less, and most preferably 410nm or less. This makes it possible to improve the transparency of the glass in the visible region by locating the absorption edge of the glass in the vicinity of the ultraviolet region, and thus the optical glass can be used as a material for an optical element such as a lens.
The transmittance of the optical glass of the present invention is measured in accordance with the standard JOGIS02 of the Japan optical glass industry Association. Specifically, the spectral transmittance of a polished article having a thickness of 10. + -. 0.1mm and parallel to the opposing surface is measured at 200 to 800nm in accordance with JIS Z8722, and λ is determined80(wavelength at which transmittance is 80%), λ70(wavelength at which the transmittance is 70%) and λ5(wavelength at which the transmittance is 5%).
The optical glass of the present invention preferably has a small photoelastic constant, and particularly, the optical glass of the present invention has a photoelastic constant (β) of 2.0X 10 at a wavelength of 546.1nm-5nm·cm-1·Pa-1Hereinafter, more preferably 1.5 × 10-5nm·cm-1·Pa-1Hereinafter, more preferably 1.0 × 10-5nm·cm-1·Pa-1Hereinafter, the most preferable is 0.7X 10-5nm·cm-1·Pa-1The following. Accordingly, the partial dispersion ratio of the optical glass can be improved, and the polarization characteristics of the transmitted light can be improved, so that when the optical glass is used in an optical system of a projector or a camera (particularly, one having a polarization filter), chromatic aberration can be reduced, and scattering of light inside the optical element can be suppressed. That is, the color rendering properties of these projectors and cameras can be further improved.
The photoelastic constant (β) of the optical glass of the present invention was measured by using a wafer-shaped sample 25mm in diameter and 8mm in thickness, which had been polished on opposite sides, and applying F [ Pa ] in a predetermined direction]The optical path length difference delta [ nm ] of light having a wavelength of 546.1nm generated at the center of the glass under a compressive load of (1)]. Next, the values of F and delta obtained and the thickness d [ cm ] of the glass were used]The photoelastic constant β [10 ] was obtained from a relational expression of δ β × d × F-5nm·cm-1·Pa-1]. In addition, an ultra-high pressure mercury lamp was used as a light source for measurement having a wavelength of 546.1 nm.
The optical glass of the present invention is preferably high in devitrification resistance. In particular, the optical glass of the present invention preferably has a low liquidus temperature of 1200 ℃ or lower. More specifically, the liquidus temperature of the optical glass of the present invention is preferably 1200 ℃, more preferably 1180 ℃, and most preferably 1150 ℃. This can improve the stability of the glass and reduce crystallization, and therefore can improve resistance to devitrification when the glass is formed from a molten state, and can reduce the influence on the optical characteristics of an optical element using the glass. On the other hand, the lower limit of the liquidus temperature of the optical glass of the present invention is not particularly limited, and the liquidus temperature of the glass obtained according to the present invention is usually about 500 ℃ or more, specifically 550 ℃ or more, and more specifically 600 ℃ or more. In addition, the "heat retention test" in the present specification is performed to confirm whether or not the devitrification resistance of the glass is high as follows: the method comprises charging a glass raw material into a 30cc platinum crucible, melting the glass raw material for about 10 to 20 minutes in a furnace with a lid at 1200 to 1250 ℃, stirring the glass raw material for homogenization, holding the obtained glass in the furnace with a lid at 1000 to 1150 ℃ for 2 hours, and observing crystals precipitated on the surface and inside of the glass and on the contact surface with the inner wall of the crucible.
Preform and optical element
The glass molded body can be produced from the produced optical glass by a press molding method such as reheat press molding and precision press molding. That is, a preform for press molding can be produced from an optical glass, and a glass molded body can be produced by subjecting the preform to reheat press molding and then to polishing; alternatively, a preform produced by, for example, polishing may be precision press-molded to produce a glass molded body. The method for producing the glass molded product is not limited to these methods.
The glass molded article thus produced can be used for various optical elements, and is particularly preferably used for optical elements such as lenses and prisms. Thereby, it is possible to reduce color bleeding caused by chromatic aberration of transmitted light of an optical system provided with the optical element. Therefore, when the optical element is used in a camera, an object to be photographed can be displayed more accurately, and when the optical element is used in a projector, a desired screen can be projected with higher color.
Examples
Compositions of examples (No. A1 to No. A13, No. B1 to No. B23, No. C1 to No. C6, No. D1 to No. D36) and comparative examples (No. a1, No. c1, No. d1) of the present invention and refractive indexes (n) of glasses thereofd) And Abbe number (v)d) Partial dispersion ratios (θ g, F), glass transition temperatures (Tg) and a wavelength (λ) at which the transmittance is 80%80) And a wavelength (lambda) at which the transmittance is 5%5) And the values of the liquid phase temperature are shown in tables 1 to 11. The following examples are for illustrative purposes only, and the present invention is not limited to these examples.
The optical glasses of examples (No. A1 to No. A13, No. B1 to No. B23, No. C1 to No. C6, and No. D1 to No. D36) of the present invention and the glasses of comparative examples (No. a1, No. c1, and No. d1) were produced as follows: high-purity raw materials used for general optical glass, such as oxides, hydroxides, carbonates, nitrates, fluorides, hydroxides, metaphosphoric acid compounds, are selected as raw materials of the respective components, and the raw materials are weighed and mixed uniformly in the composition ratios of the respective examples and comparative examples shown in tables 1 to 11, and then put into a platinum crucible, melted in an electric furnace at a temperature range of 1000 to 1400 ℃ for 1 to 6 hours according to the melting difficulty of the glass composition, stirred, homogenized, defoamed, etc., and then cooled to 1200 ℃ and stirred, homogenized, poured into a mold, and annealed to produce glass.
Here, the refractive indices (n.sub.1, No.c1, No.d1) of the glasses of examples (No.A1 to No.A13, No.B1 to No.B23, No.C1 to No.C6, No.D1 to No.D36) and comparative examples (No.a1, No.c1, No.D1)d) And Abbe number (v)d) And the partial dispersion ratio (. theta.g, F) was determined based on the Japanese optical Nitri Industrial Standard JOGIS 01-2003. Then, the Abbe number (. nu.) obtained is subjected tod) And the value of the partial dispersion ratio (theta g, F), and obtaining the dispersion ratio in the relation (theta g, F) of-a x vdThe slope a in + b is the intercept b at 0.0017 and 0.0020. In addition, the refractive index (n) obtainedd) The value of (d) is obtained from the relation-100 XndA value of + 220. In addition, the glass used in this measurement was treated in an annealing furnace at an annealing temperature reduction rate of-25 ℃ per hour.
In addition, the glass transition temperatures (Tg) of the glasses of examples (No. D1 to No. D36) and comparative example (No. d1) were measured by using a differential thermal measurement device (NETZSCH-
Figure BDA0000978425210000451
STA 409 CD manufactured by GmbH). Here, the particle size of the sample is 425 to 600 μm and the temperature rise rate is 10 ℃/min.
Further, the transmittance of the glasses of examples (No. d1 to No. d36) and comparative example (No. d1) was measured in accordance with japanese optical glass industry standard JOGIS 02. In the present invention, the presence or absence and the degree of coloring of the glass are determined by measuring the transmittance of the glass. Specifically, the spectral transmittance at 200 to 800nm of a polished parallel to the counter surface with a thickness of 10. + -. 0.1mm is measured by JIS Z8722 to determine λ80(wavelength at which transmittance is 80%) and λ5(wavelength at which the transmittance is 5%).
Further, the liquidus temperatures of the glasses of examples (nos. d1 to d36) and comparative example (No. d1) were measured as follows: the crushed glass samples were placed on a platinum plate at intervals of 10mm, held in a furnace having a temperature gradient of 800 to 1200 ℃ for 3 minutes, then taken out, cooled, and then the presence or absence of crystals in the glass samples was observed under a microscope of 80-fold magnification to measure the crystals. At this time, the optical glass was pulverized into particles having a diameter of about 2mm to obtain a sample.
TABLE 1
Figure BDA0000978425210000461
TABLE 2
Figure BDA0000978425210000471
TABLE 3
Figure BDA0000978425210000481
TABLE 4
Figure BDA0000978425210000491
TABLE 5
Figure BDA0000978425210000501
TABLE 6
Figure BDA0000978425210000511
TABLE 7
Figure BDA0000978425210000521
TABLE 8
Figure BDA0000978425210000531
TABLE 9
Figure BDA0000978425210000541
Watch 10
Figure BDA0000978425210000551
TABLE 11
Figure BDA0000978425210000561
The optical glass of the examples of the present invention had a partial dispersion ratio (θ g, F) of (-0.00170X ν)d+0.6375), more specifically (-0.00170 x ν)d+0.6420) or higher. In particular, the optical glasses of examples (No. C1 to No. C6) had a partial dispersion ratio (θ g, F) of (-0.00170X ν)d+0.64486) or higher. The optical glasses of examples (No. A1 to No. A13) of the present invention also had a partial dispersion ratio (θ g, F) (-0.00170X ν)d+0.63750), which is presumed to have a desired high partial dispersion ratio. On the other hand, the optical glasses of examples (No. B1 to No. B23) of the present invention had a partial dispersion ratio (θ g, F) of (-0.00200X ν)d+0.64982) or higher. Therefore, it is clear that the optical glass of the embodiment of the present invention has an Abbe number (. nu.) ofd) The partial dispersion ratio (θ g, F) is large, and chromatic aberration is small when the optical element is formed.
Refractive index (n) of optical glass of example of the present inventiond) 1.57 or more, more specifically 1.65 or more, and the refractive index (n)d) All of them are 2.20 or less, more specifically 1.85 or less, and are within desired ranges. In particular, the refractive index (n) of the optical glasses of examples (No. A1 to No. A13) of the present inventiond) Are all 1.73 or more, and the refractive index (n)d) All are below 1.78. The refractive index (n) of the optical glasses of examples (No. B1 to No. B23) of the present inventiond) All of them are 1.70 or more, more specifically 1.75 or more. In addition, theRefractive index (n) of the optical glasses of examples (No. C1 to No. C6)d) 1.60 or more, more specifically 1.65 or more, and the refractive index (n)d) All are 1.70 or less. In addition, the refractive index (n) of the optical glasses of examples (No. D1 to No. D36)d) Are all 1.69 or more, and the refractive index (n)d) All are 1.81 or less.
In addition, the Abbe number (. nu.) of the optical glass of the example of the present inventiond) All 39 or more, more specifically 40.7 or more, and the Abbe number (. nu.)d) All are 63 or less, more specifically 61 or less, and are within desired ranges. In particular, the Abbe number (. nu.) of the optical glasses of examples (No. A1 to No. A13) of the present inventiond) All 45 or more, more specifically 49 or more, and the Abbe number (. nu.)d) All of them are 60 or less, more specifically 54 or less. In addition, the Abbe number (. nu.) of the optical glasses of examples (No. B1 to No. B23) of the present inventiond) All 39 or more, more specifically 40.7 or more, and the Abbe number (. nu.)d) All of which are less than 52, more specifically, 51.3 or less. In addition, Abbe number (. nu.) of the optical glasses of examples (No. C1 to No. C6) of the present inventiond) All of which are 50 or more, more specifically 54 or more, and the abbe number (v)d) Both are 57 or less. In addition, the Abbe number (. nu.) of the optical glasses of examples (No. D1 to No. D36) of the present inventiond) Are all 45 or more, and the Abbe number (. nu.) isd) All 63 or less, more specifically 61 or less.
Here, the optical glasses of the examples (No. C1 to No. C6) of the present invention satisfy Abbe number (. nu.) of the optical glass of the present inventiond) And refractive index (n)d) V isd)≥(-100×nd+ 220).
The glass transition temperature (Tg) of the optical glasses of examples (No. d1 to No. d36) of the present invention is 650 ℃ or lower, more specifically 620 ℃ or lower, within a desired range. It is also presumed that the optical glass of another embodiment of the present invention has a glass transition temperature (Tg) of 650 ℃ or lower.
In addition, λ of the optical glasses of examples (No. D1 to No. D36) of the present invention80(wavelength at which the transmittance is 80%) is 500nm or less, more specifically 410nm or less. In addition, λ of the optical glasses of examples (No. D1 to No. D36) of the present invention5(wavelength at a transmittance of 5%) is 450nm or less, more specifically 350nm or less, and is in a desired range. In addition, it is assumed that the optical glasses of other embodiments of the present invention are similar, λ70(wavelength at a transmittance of 70%) 500nm or less and lambda5(wavelength at a transmittance of 5%) 450nm or less.
The optical glasses of examples (No. d1 to No. d36) of the present invention all had liquid phase temperatures of 1200 ℃ or lower, more specifically 1100 ℃ or lower, and 500 ℃ or higher. On the other hand, the glass of comparative example (No. d1) had a liquidus temperature of 1200 ℃ or higher. It is thus clear that the optical glass of the example of the present invention has a lower liquidus temperature and is less likely to devitrify than the glass of the comparative example.
The photoelastic constant (β) at a wavelength of 546.1nm of the optical glasses of examples (No. A1 to No. A13) of the present invention is assumed to be 2.0X 10-5nm·cm-1·Pa-1The following.
Thus, it was clarified that the refractive index (n) of the optical glass of the example of the present inventiond) And Abbe number (v)d) Has a small chromatic aberration in a desired range, is easily press-molded, and has high transparency to light having a wavelength in the visible region. In particular, it is clear that the optical glasses of examples (No. D1 to No. D36) of the present invention have high devitrification resistance. The optical glasses of examples (nos. a1 to 13) are also considered to have small scattering in the optical glass.
Further, the optical glass obtained in the examples of the present invention was subjected to reheat press molding, and then ground and polished to be processed into the shapes of lenses and prisms. Further, a preform for precision press molding is formed using the optical glass of the embodiment of the present invention, and precision press molding is performed on the preform for precision press molding. In either case, the glass after heat softening does not cause problems such as opalescence and devitrification, and can be stably processed into various shapes of lenses and prisms.
Although the present invention has been described in detail for the purpose of illustration, it is to be understood that this embodiment is for illustrative purposes only and that various changes and modifications may be made by those skilled in the art without departing from the spirit and scope of the invention.

Claims (20)

1. An optical glass comprising 5.0-25.43% by mass of B based on the total mass of the glass in terms of oxide2O3Component (B), 10.0-55.0% La2O3Component (b), and 2.09% to 20.0% of Y2O3Component (B) of Bi2O3The content of the component is less than 10.0 percent, Sb2O3The content of component (B) is 1.0% or less, and the sum of the mass and F + Bi with respect to the total mass of the glass in terms of oxide2O3+TiO2+WO3+Nb2O5+K2O is 8.0% to 60.0%, and the glass contains 5.59% to 30.0% of F component by mass of the increased mass of the total mass of the glass based on oxides, and has a refractive index n of 1.57 or moredAnd Abbe number v of 39 or moredPartial dispersion ratio (θ g, F) and Abbe number vdSatisfies (theta g, F) not less than (-0.00170 x nu)d+0.63750 or (θ g, F) ≥ 2.0 × 10-3×νd+ 0.6498).
2. The optical glass according to claim 1, wherein the glass has an Abbe number vdIs the x-axis, and has a refractive index ndIn xy rectangular coordinates of the y axis, the abbe number and the refractive index of the range surrounded by points a (50, 1.70), B (60, 1.60), C (63, 1.60), and D (63, 1.70)4 are shown.
3. The optical glass according to claim 1, wherein Al is contained in mass% with respect to the total mass of the glass in terms of oxide of the composition2O30 to 20.0% of the component(s) and/or,
SiO20 to 40.0% of the component(s) and/or,
Gd2O30 to 40.0% of the component(s) and/or,
Yb2O30 to 20.0% of the component(s) and/or,
Lu2O30 to 20.0% of the component(s) and/or,
TiO20 to 15.0% of the component(s) and/or,
Nb2O50 to 20.0% of the component(s) and/or,
WO30 to 15.0% of the component(s) and/or,
Li20 to 15.0% of O and/or,
Na20 to 20.0% of O and/or,
K20 to 10.0% of O and/or,
ZrO20 to 15.0% of the component(s) and/or,
Ta2O50 to 25.0% of the component(s) and/or,
MgO component is 0-20.0% and/or,
CaO component is 0-40.0% and/or,
0 to 40.0% of SrO and/or,
BaO component is 0-55.0% and/or,
0 to 30.0% of ZnO and/or,
GeO20 to 10.0% of the component(s) and/or,
P2O50 to 10.0% of the component(s) and/or,
Ga2O30 to 10.0% of the component(s) and/or,
TeO20 to 10.0% of the component(s) and/or,
SnO2the component is 0-5.0%.
4. The optical glass according to claim 1, wherein the total mass, mass and SiO of the glass are calculated with respect to oxides2+B2O340.0% or less.
5. The optical glass according to claim 1, wherein Ln is a constituent of the total glass mass in terms of oxide equivalent composition2O3The sum of the mass of the components is less than 80.0 percent, wherein Ln is more than one selected from the group consisting of La, Gd, Y, Yb and Lu.
6. The optical glass according to claim 1, wherein the total mass, mass and Gd of the glass are contained in a composition in terms of oxides2O3+Yb2O326.0% or less.
7. The optical glass according to claim 1, wherein the mass ratio Ln in oxide equivalent composition2O3/(Bi2O3+TiO2+WO3+Nb2O5+Ta2O5) Is 1.7 or more and 25.0 or less.
8. The optical glass according to claim 1, wherein the mass ratio Ln of the oxide-converted composition2O3/(SiO2+B2O3) Is more than 1.00, wherein Ln is more than one selected from the group consisting of La, Gd, Y, Yb and Lu.
9. The optical glass according to claim 1, wherein the sum of the mass and Bi with respect to the total mass of the glass of the oxide-converted composition2O3+TiO2+WO3+Nb2O5Is 20.0% or less.
10. The optical glass according to claim 1, wherein the mass ratio F/(F + Bi) in oxide equivalent composition2O3+TiO2+WO3+Nb2O5+K2O) is 0.36 to 1.00 inclusive.
11. The optical glass according to claim 1, wherein the total mass, mass and WO of the glass are calculated with respect to oxides3+La2O3+ZrO2+Ta2O5Is 10.0% or more and 60.0% or less.
12. The optical glass according to claim 1, wherein the sum of the mass and Bi with respect to the total mass of the glass of the oxide-converted composition2O3+TiO2+WO3+Nb2O5+Ta2O5Greater than 0%.
13. The optical glass according to claim 1, wherein the mass ratio (Ta) in oxide equivalent composition2O5+ZrO2+Li2O)/(F+Bi2O3+TiO2+WO3+Nb2O5+K2O) is 2.00 or less.
14. The optical glass according to claim 1, wherein the mass ratio of (F + Bi) in terms of oxide composition2O3+TiO2+WO3+Nb2O5+K2O)/(Ta2O5+ZrO2+Li2O) is 0.50 or more.
15. The optical glass according to claim 1, wherein the sum of the masses of RO components is 55.0% or less with respect to the total mass of the glass in terms of oxides, wherein R is at least one member selected from the group consisting of Mg, Ca, Sr and Ba,
Rn2the sum of the mass of the O components is 25.0% or less, and Rn is at least one selected from the group consisting of Li, Na and K.
16. The optical glass according to claim 1, wherein Abbe number vdAnd refractive index ndMeet the requirement of vd≥-100×nd+220 relationship.
17. The optical glass according to claim 1, wherein Abbe number vdAnd refractive index ndMeet the requirement of vd≥-125×ndA relation of + 265.
18. A preform material formed of the optical glass according to claim 1.
19. An optical element comprising the optical glass according to claim 1 as a base material.
20. An optical device comprising the optical element according to claim 19.
CN201610284849.5A 2010-07-26 2011-07-26 Optical glass, preform and optical element Active CN105948483B (en)

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