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CN116332506B - Optical glass, preforms and optical components - Google Patents

Optical glass, preforms and optical components Download PDF

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Publication number
CN116332506B
CN116332506B CN202310219632.6A CN202310219632A CN116332506B CN 116332506 B CN116332506 B CN 116332506B CN 202310219632 A CN202310219632 A CN 202310219632A CN 116332506 B CN116332506 B CN 116332506B
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component
content
glass
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mass
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CN116332506A (en
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向川胜之
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Ohara Inc
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Ohara Inc
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus
    • C03C3/21—Silica-free oxide glass compositions containing phosphorus containing titanium, zirconium, vanadium, tungsten or molybdenum
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/18—Stirring devices; Homogenisation
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements

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

Abstract

本发明为光学玻璃、预成型坯和光学元件。本发明公开了一种光学玻璃，以质量％计，含有大于0％～45.0％的La2O3成分、大于0％～45.0％的TiO2成分、以及大于0％～40.0％的BaO成分，且SiO2成分与B2O3成分的总量为5.0％以上且30.0％以下，TiO2/(TiO2+BaO)的质量比为0.10以上且0.90以下，折射率(nd)为1.90以上，阿贝数(vd)为30.0以下，且显示光谱透射率5％的波长(λ5)为400nm以下。根据本发明，可提供一种具有高折射率和高色散的光学特性，且玻璃的制造成本低的光学玻璃。

The present invention is an optical glass, a preform and an optical element. The present invention discloses an optical glass, which contains, by mass %, more than 0% to 45.0% of La2O3 , more than 0% to 45.0% of TiO2 , and more than 0% to 40.0% of BaO, and the total amount of SiO2 and B2O3 is 5.0% to 30.0 %, the mass ratio of TiO2 /( TiO2 +BaO) is 0.10 to 0.90, the refractive index ( nd ) is 1.90 or more, the Abbe number ( vd ) is 30.0 or less, and the wavelength ( λ5 ) showing 5% of the spectral transmittance is 400nm or less. According to the present invention, an optical glass having optical characteristics of high refractive index and high dispersion and low manufacturing cost of the glass can be provided.

Description

Optical glass, preform and optical element
The present application is a divisional application of application number 201711251286.0, entitled "optical glass, preform, and optical element", having application date 2017, 12, 1.
Technical Field
The present invention relates to an optical glass, a preform, and an optical element.
Background
In recent years, digitization using an optical system apparatus or high definition of an image/video is rapidly advancing. In particular, high definition of images and videos is very prominent in optical devices such as digital cameras, video cameras, and projectors. In addition, in the optical system included in these optical instruments, the number of optical elements such as lenses and prisms is reduced, so that weight and size can be reduced.
In particular, in optical glass used for manufacturing optical elements, there is a high-refractive-index high-dispersion glass having a high refractive index (n d) of 1.90 or more and a low abbe number (v d) of 15 or more and 30 or less, which is required to be light and compact in the entire optical system. As such a high refractive index low dispersion glass, a glass composition represented by patent document 1 is known.
Prior art literature
Patent literature
Patent document 1 Japanese patent application laid-open No. 2011-178571
Disclosure of Invention
However, the glass described in patent document 1 contains a large amount of components having high material unit prices, such as GeO 2 component, nb 2O5 component, and Ta 2O5 component, in order to promote high refractive index and high dispersion, and this has a problem of high manufacturing cost. Therefore, an optical glass having a high refractive index and high dispersion, a wavelength (λ 5) exhibiting a spectral transmittance of 5% being short, and a low manufacturing cost is expected.
In view of the above problems, an object of the present invention is to provide an optical glass having a high refractive index and a short wavelength (λ 5) exhibiting a spectral transmittance of 5% and being low in manufacturing cost, and a preform and an optical element using the optical glass.
As a result of intensive studies to solve the above problems, the present inventors have found that a desired high refractive index and high dispersion can be obtained by adjusting the mass ratio of the total amount of the component SiO 2 and the component B 2O3 or Ti 2/(TiO2 +BaO while using the component La 2O3, the component TiO 2 and the component BaO in combination, and that the manufacturing cost is suppressed and the wavelength (lambda 5) exhibiting a spectral transmittance of 5% is shortened, thereby completing the present invention.
Specifically, the present invention provides the following.
(1) An optical glass comprising, in mass% based on oxides,
Comprises
0 To 45.0 percent of La 2O3 component,
More than 0% -45.0% of TiO 2 component and
More than 0% -40.0% of BaO component,
And the total amount of SiO 2 and B 2O3 components is 5.0% or more and 30.0% or less,
Ti 2/(TiO2 +BaO) is in mass ratio of 0.10 to 0.90,
The refractive index (n d) is 1.90 or more, the Abbe number (v d) is 30.0 or less, and the wavelength (lambda 5) showing a spectral transmittance of 5% is 400nm or less.
(2) The optical glass according to (1), wherein,
Calculated as mass% on an oxide basis,
SiO 2 is 0-30.0%, and
The content of B 2O3 is 0-30.0%.
(3) The optical glass according to (1) or (2), wherein,
Calculated as mass% on an oxide basis,
ZnO is 0-20.0%,
Y 2O3 is 0-15.0%,
Nb 2O5 is 0-25.0%,
Yb 2O3 is 0-15.0%, and
The Gd 2O3 component is 0-15.0%.
(4) The optical glass according to any one of (1) to (3), wherein,
Calculated as mass% on an oxide basis,
The sum of the masses of (La 2O3+Nb2O5+Gd2O3+Yb2O3) is more than 0% and 60.0% or less.
(5) The optical glass according to any one of (1) to (4), wherein,
Calculated as mass% on an oxide basis,
The total of Ln 2O3 components (wherein Ln is one or more selected from the group consisting of La, gd, Y, yb) is greater than 0% and 50.0% or less.
(6) The optical glass according to any one of (1) to (5), wherein,
Based on the basis of the oxides,
TiO 2/BaO is more than 0 and less than 3.00.
(7) The optical glass according to any one of (1) to (6), wherein,
Calculated as mass% on an oxide basis,
The sum of the mass of Rn 2 O components (wherein Rn is at least one selected from the group consisting of Li, na, and K) is 15.0% or less.
(8) The optical glass according to any one of (1) to (7), wherein,
Calculated as mass% on an oxide basis,
The sum of the masses of RO components (wherein R is one or more selected from the group consisting of Mg, ca, sr, ba, zn) is more than 0% and 35.0% or less.
(9) The optical glass according to any one of (1) to (8), wherein,
Contains, in mass% based on the oxide
ZrO 2 component 0-20.0%,
0 To 15.0% of Nb 2O5,
WO 3 component 0-10.0%,
Ta 2O5 component 0-10.0%,
MgO component 0-15.0%,
0 To 15.0% of CaO component,
0 To 15.0% of SrO component,
0 To 15.0% of Li 2 O component,
0 To 15.0% of Na 2 O,
0 To 15.0% of K 2 O,
0 To 10.0% of P 2O5 component,
0-10.0% Of GeO 2 component,
0 To 15.0% of Al 2O3,
0-15.0% Of Ga 2O3 component,
Bi 2O3 component 0-10.0%,
0-10.0% Of TeO 2 component,
0 To 3.0% of SnO 2, and
0-1.0% Of Sb 2O3.
(10) A preform comprising the optical glass of any one of (1) to (9).
(11) An optical element comprising the optical glass described in any one of (1) to (9).
(12) An optical instrument provided with the optical element according to (11).
According to the present invention, it is possible to provide an optical glass having a short wavelength (λ 5) exhibiting a spectral transmittance of 5% and low manufacturing cost while having a high refractive index and high dispersion, and a preform and an optical element using the optical glass.
Drawings
Embodiments of the present invention will be described in detail based on the following drawings, in which:
FIG. 1 is a schematic diagram showing a normal line expressed by rectangular coordinates having a partial dispersion ratio (θg, F) as a vertical axis and an Abbe number (v d) as a horizontal axis, and
Fig. 2 is a schematic diagram showing the relationship between the partial dispersion ratio (θg, F) and the abbe number (v d) of the glass according to the example of the present invention.
Detailed Description
The optical glass of the present invention contains, in mass%, 0 to 45.0% or more of La 2O3 component, 0 to 45.0% or more of TiO 2 component, and 0 to 40.0% or more of BaO component, the total amount of SiO 2 component and B 2O3 component is 5.0% or more and 30.0% or less, the mass ratio of TiO 2/(TiO2 +BaO is 0.10 or more and 0.90 or less, the refractive index (n d) is 1.90 or more, the Abbe number (v d) is 30.0 or less, and the wavelength (lambda 5) showing spectral transmittance of 5% is 400nm or less.
According to the present invention, by adjusting the content of each component while using the La 2O3 component, the TiO 2 component and the BaO component in combination, the glass can have a high refractive index and high dispersion, and the glass stability can be improved. Accordingly, an optical glass having a short wavelength (λ 5) exhibiting a spectral transmittance of 5% and low manufacturing cost, and a preform and an optical element using the optical glass can be provided while having a high refractive index and high dispersion.
[ Glass component ]
The following describes the composition ranges of the respective components constituting the optical glass of the present invention. In the present specification, unless otherwise specified, the content of each component is expressed as mass% relative to the total mass of the glass on an oxide basis. The term "oxide standard" as used herein refers to a composition of each component contained in the glass, assuming that all of the oxides, complex salts, metal fluorides, and the like used as raw materials of the glass constituent components of the present invention are decomposed into oxides at the time of melting, the total mass of the oxides is set to 100 mass%.
< Essential component, optional component >
The La 2O3 component is a component which can improve the refractive index of the glass and reduce the dispersion when the content is more than 0%. In particular, by containing more than 0% of La 2O3 component, a desired high refractive index can be obtained, which is an essential component. Therefore, the lower limit of the content of the La 2O3 component is preferably more than 0%, more preferably 3.0%, further preferably 15.0%, still more preferably 20.0%, still more preferably 25.0%, still more preferably 27.0%.
On the other hand, by setting the content of the La 2O3 component to 45.0% or less, the devitrification resistance of the glass can be improved, the increase in specific gravity of the glass can be suppressed, and the manufacturing cost can be reduced. Therefore, the upper limit of the content of the La 2O3 component is preferably 45.0%, more preferably 40.0%, further preferably 38.0%, and still further preferably 37.0%.
La 2O3、La(NO3)3·XH2 O (X is an arbitrary integer) or the like can be used as the La 2O3 component.
The TiO 2 component is an essential component whose content is more than 0% and which can improve the refractive index of the glass, reduce the Abbe number, improve the partial dispersion ratio, and improve the devitrification resistance. Therefore, the lower limit of the content of the TiO 2 component is preferably more than 0%, more preferably more than 5.0%, still more preferably more than 10.0%, still more preferably 15.0%, still more preferably 18.0%, still more preferably more than 20.0%.
On the other hand, by setting the content of the TiO 2 component to 45.0% or less, the coloring of the glass can be reduced and the visible light transmittance can be improved. In addition, devitrification due to excessive content of the TiO 2 component can be suppressed. Therefore, the upper limit of the content of the TiO 2 component is preferably 45.0%, more preferably 38.0%, further preferably 32.0%, still more preferably 27.0%, and still more preferably 25.0%.
The TiO 2 component may be TiO 2 or the like.
The BaO component is an essential component that can improve the refractive index and devitrification resistance of the glass and can improve the meltability of the glass raw material when the BaO component content is more than 0%. Therefore, the lower limit of the content of the BaO component is preferably more than 0%, more preferably 5.0%, further preferably 8.0%, and still further preferably 10.0%.
On the other hand, when the content of the BaO component is 40.0% or less, the refractive index of the glass is not easily lowered, and devitrification of the glass can be reduced. Therefore, the upper limit of the content of the BaO component is preferably 40.0%, more preferably 35.0%, further preferably 28.0%, still more preferably 23.0%, and still more preferably 20.0%.
BaO component may be BaCO 3、Ba(NO3)2 or the like as a raw material.
The sum (mass sum) of the contents of the B 2O3 component and the SiO 2 component is preferably 5.0% or more and 30.0% or less.
In particular, by setting the sum to 5.0% or more, the decrease in devitrification resistance due to the shortage of the B 2O3 component or the SiO 2 component can be suppressed. Therefore, the lower limit of the mass sum (B 2O3+SiO2) is preferably 5.0%, more preferably 7.0%, and further preferably 9.0%.
On the other hand, by setting the sum to 30.0% or less, a decrease in refractive index due to excessive content of these components can be suppressed, and a desired high refractive index can be easily obtained. Therefore, the upper limit of the mass sum (B 2O3+SiO2) is preferably 30.0%, more preferably 23.0%, further preferably 18.0%, still further preferably 16.5%.
Here, the ratio (mass ratio) of the content of TiO 2 to the sum of the contents of TiO 2 component and BaO component is preferably 0.10 or more. Thus, a high partial dispersion ratio can be obtained while maintaining a high refractive index and high dispersion. Therefore, the lower limit of the mass ratio TiO 2/(TiO2 +bao) is preferably 0.10, more preferably 0.30, further preferably 0.40, and still further preferably 0.45.
On the other hand, by setting the mass ratio to 0.90 or less, coloring of the glass can be reduced, visible light transmittance can be improved, and devitrification can be suppressed. Therefore, the upper limit of the mass ratio TiO 2/(TiO2 +bao) is preferably 0.90, more preferably 0.80, further preferably 0.73, and still further preferably 0.68.
The SiO 2 component is any component whose content is more than 0% and which can improve the devitrification resistance. Therefore, the lower limit of the content of the SiO 2 component is preferably more than 0%, more preferably more than 0.5%, further preferably more than 1.0%, further preferably more than 2.0%.
On the other hand, when the content of the SiO 2 component is 30.0% or less, the SiO 2 component can be easily melted in the molten glass, and melting at a high temperature can be avoided. The upper limit of the content of the SiO 2 component is preferably 30.0%, more preferably 23.0%, further preferably 16.0%, still more preferably 11.0%, and still more preferably 9.0%.
SiO 2、K2SiF6、Na2SiF6 and the like can be used as the SiO 2 component.
The B 2O3 component is any component which can form a network structure in the glass when the content is more than 0%, promote stable glass formation and improve devitrification resistance. Therefore, the lower limit of the content of the B 2O3 component is preferably more than 0%, more preferably more than 0.5%, still more preferably more than 1.0%, still more preferably more than 2.0%.
On the other hand, by setting the content of the B 2O3 component to 30.0% or less, it is possible to suppress a decrease in refractive index, reduce the abbe number, and suppress deterioration in chemical durability. Therefore, the upper limit of the content of the B 2O3 component is preferably 30.0% or less, more preferably 20.0%, further preferably less than 15.0%, further preferably 12.0%, and further preferably less than 10.0%.
As the component B 2O3, H3BO3、Na2B4O7、Na2B4O7·10H2O、BPO4 and the like can be used as a raw material.
The ZnO component is any component whose content is more than 0% and which can improve the meltability of glass, lower the glass transition temperature, and reduce devitrification. Therefore, the lower limit of the content of the ZnO component is preferably more than 0%, more preferably more than 0.5%, further preferably more than 1.0%, and still further preferably more than 1.5%.
On the other hand, by setting the content of the ZnO component to 20.0% or less, the refractive index or devitrification can be reduced. In addition, since the viscosity of the molten glass can be improved, the occurrence of streaks of glass can be reduced. Therefore, the upper limit of the content of the ZnO component is preferably 20.0%, more preferably 15.0%, further preferably 11.0%, and still further preferably 8.0%.
As the ZnO component, znO, znF 2, or the like can be used as a raw material.
The Y 2O3 component is any component whose content is more than 0% and which can suppress an increase in the material cost of the glass.
By setting the content of the Y 2O3 component to 15.0% or less, the reduction in refractive index of the glass can be suppressed, the abbe number can be reduced, and the devitrification resistance of the glass can be improved. Therefore, the upper limit of the content of the Y 2O3 component is preferably 15.0%, more preferably 10.0%, and even more preferably 5.0%.
The Y 2O3 component may be Y 2O3、YF3 or the like.
The Nb 2O5 component is an optional component whose content is more than 0% and which can improve the refractive index of the glass and can improve the devitrification resistance. Therefore, the lower limit of the content of the Nb 2O5 component is preferably more than 0%, more preferably 2.0%, and even more preferably 4.0%.
On the other hand, by setting the content of the Nb 2O5 component to 25.0% or less, a decrease in devitrification resistance or a decrease in transmittance of visible light of the glass due to excessive content of the Nb 2O5 component can be suppressed, and an increase in material cost of the glass can be suppressed. Accordingly, the upper limit of the content of the Nb 2O5 component is preferably 25.0%, more preferably 20.0%, further preferably 16.0%, and still further preferably 13.0%.
As the Nb 2O5 component, nb 2O5 and the like can be used as raw materials.
The Yb 2O3 component is any component that can increase the refractive index of the glass when the content thereof is more than 0%.
On the other hand, by setting the content of the Yb 2O3 component to 15.0% or less, the devitrification resistance of the glass can be improved, and the abbe number can be reduced. Therefore, the upper limit of the content of the Yb 2O3 component is preferably 15.0%, more preferably 10.0%, and even more preferably 5.0%.
Yb 2O3 and the like can be used as the Yb 2O3 component.
The Gd 2O3 component is an optional component whose content is more than 0% and which can increase the refractive index of the glass and the abbe number.
On the other hand, by reducing the content of Gd 2O3, which is particularly expensive in rare earth elements, to 15.0% or less, the material cost of the glass can be reduced, and thus a cheaper optical glass can be produced. In addition, the rise in the abbe number of the glass more than necessary can be suppressed. Therefore, the upper limit of the content of Gd 2O3 component is preferably 15.0%, more preferably 10.0%, even more preferably 5.0%.
Gd 2O3、GdF3 and the like can be used as the Gd 2O3 component.
In the optical glass of the present invention, the sum (mass sum) of the contents of La 2O3 component, nb 2O5 component, gd 2O3 component, and Yb 2O3 component is preferably 60.0% or less. This can reduce the content of these expensive components, thereby reducing the material cost of the glass and reducing the abbe number. Therefore, the upper limit of the mass sum (La 2O3+Nb2O5+Gd2O3+Yb2O3) is preferably 60.0%, more preferably 57.0%, further preferably 53.0%, still more preferably 49.0%, still more preferably 47.0%.
On the other hand, by containing the mass sum of these components more than 0%, a desired high refractive index can be obtained. Therefore, the lower limit of the mass sum (La 2O3+Nb2O5+Gd2O3+Yb2O3) is preferably more than 0%, more preferably 10.0%, further preferably 20.0%, still more preferably 25.0%, still more preferably 30.0%, still more preferably 35.0%.
The sum (mass sum) of the contents of Ln 2O3 components (Ln is one or more selected from the group consisting of La, gd, Y, yb) is preferably more than 0% to 50.0%.
In particular, by setting the mass sum to be larger than 0%, the refractive index of the glass can be increased, and a high refractive index glass can be easily obtained. In addition, the coloring of the glass can be reduced thereby. Therefore, the lower limit of the sum of the mass of the contents of Ln 2O3 components is preferably more than 0%, more preferably 1.0%, still more preferably 3.0%, still more preferably 5.0%.
On the other hand, by setting the mass sum to 50.0% or less, the devitrification resistance can be improved, and the abbe number can be reduced. Therefore, the upper limit of the sum of the mass of the contents of Ln 2O3 components is preferably 50.0%, more preferably less than 40.0%, further preferably 30.0%, still further preferably 25.0%.
Here, the ratio (mass ratio) of the content of TiO 2 to the sum of the contents of La 2O3 component, nb 2O5 component, gd 2O3 component, and Yb 2O3 component is preferably greater than 0. This can achieve a high partial dispersion ratio while maintaining a high refractive index and high dispersion, and can reduce manufacturing costs. Therefore, the lower limit of the mass ratio TiO2/(La2O3+Nb2O5+Gd2O3+Yb2O3) is preferably more than 0, more preferably 0.10, still more preferably 0.20, still more preferably 0.40.
On the other hand, by setting the mass ratio to 2.00 or less, the coloring of the glass can be reduced, the visible light transmittance can be improved, and devitrification can be suppressed. Therefore, the upper limit of the mass ratio TiO2/(La2O3+Nb2O5+Gd2O3+Yb2O3) is preferably 2.00, more preferably 1.00, further preferably 0.80, further preferably 0.66.
Here, the ratio (mass ratio) of the content of the TiO 2 component to the content of the BaO component is preferably greater than 0. Thus, a high partial dispersion ratio can be obtained while maintaining a high refractive index and high dispersion. The lower limit of the mass ratio TiO 2/BaO is preferably more than 0, more preferably 0.10, still more preferably 0.40, still more preferably 0.60.
On the other hand, by setting the mass ratio to 3.00 or less, the coloring of the glass can be reduced, the visible light transmittance can be improved, and devitrification can be suppressed. Therefore, the upper limit of the mass ratio TiO 2/BaO is preferably 3.00, more preferably 2.00, and further preferably 1.60.
Here, the ratio (mass ratio) of the sum of the contents of the TiO 2 component and the WO 3 component to the content of the BaO component is preferably greater than 0. This can obtain a high partial dispersion ratio while maintaining a high refractive index and high dispersion, and can improve the devitrification resistance. Therefore, the lower limit of the mass ratio (TiO 2+WO3)/BaO is preferably more than 0, more preferably 0.30, still more preferably 0.60, still more preferably 0.80, still more preferably 1.00.
On the other hand, by setting the mass ratio to 3.00 or less, the coloring of the glass can be reduced, the visible light transmittance can be improved, and devitrification can be suppressed. Therefore, the upper limit of the mass ratio (TiO 2+WO3)/BaO is preferably 3.00, more preferably 2.50, and further preferably 1.90.
The sum (mass sum) of the contents of the TiO 2 component and the Nb 2O5 component is preferably greater than 0%. This can increase refractive index and dispersion, and can improve devitrification resistance. Therefore, the lower limit of the mass sum (TiO 2+Nb2O5) is preferably more than 0%, more preferably more than 10.0%, still more preferably more than 15.0%, still more preferably more than 20.0%, still more preferably more than 25.0%.
On the other hand, by setting the content of the sum to 60.0% or less, the coloring of the glass can be reduced, the visible light transmittance can be improved, and devitrification can be suppressed. Therefore, the upper limit of the content of the above mass sum is preferably 60.0%, more preferably 50.0%, further preferably 45.0%, still more preferably 40.0%, still more preferably 35.0%, still more preferably 33.0%.
The total amount of the Rn 2 O component (in the formula, rn is one or more selected from the group consisting of Li, na, K, cs) is preferably 15.0% or less. This can suppress a decrease in refractive index of the glass and can improve the devitrification resistance. Therefore, the upper limit of the sum of the mass of the Rn 2 O components is preferably 15.0%, more preferably 10.0%, even more preferably less than 5.0%, and still even more preferably less than 1.0%.
The sum (mass sum) of the contents of RO components (wherein R is one or more selected from the group consisting of Mg, ca, sr, ba) is preferably 35.0% or less. This can reduce devitrification due to excessive RO component content, and can suppress a decrease in refractive index. Therefore, the upper limit of the sum of the mass of the RO components is preferably 35.0%, more preferably 30.0%, further preferably 27.0%, still more preferably less than 23.0%, still more preferably 20.0%.
On the other hand, by setting the sum to be more than 0%, the meltability of the glass raw material or the stability of the glass can be improved. Therefore, the lower limit of the total content of RO components is preferably more than 0%, more preferably 4.0%, further preferably 7.0%, and still further preferably more than 9.0%.
When the content of the ZrO 2 component is more than 0%, the glass can contribute to a higher refractive index and lower dispersion, and the devitrification resistance of the glass can be improved. Therefore, the lower limit of the content of the ZrO 2 component is preferably more than 0%, more preferably 0.5%, still more preferably 1.0%.
On the other hand, by setting the ZrO 2 content to 20.0% or less, the decrease in devitrification resistance of the glass or the increase in Abbe number or more necessary due to the excessive content of the ZrO 2 content can be suppressed. Therefore, the upper limit of the content of the ZrO 2 component is preferably 20.0%, more preferably 16.0%, further preferably 12.0%, still more preferably 9.0%, still more preferably less than 6.5%.
As the ZrO 2 component, zrO 2、ZrF4 and the like can be used as a raw material.
The WO 3 component is any component whose content is more than 0% that can improve the refractive index, improve the partial dispersion ratio, and improve the devitrification resistance of the glass while reducing the coloration of the glass due to other high refractive index components. In addition, the component WO 3 is a component capable of lowering the glass transition temperature. Therefore, the lower limit of the content of the WO 3 component is preferably more than 0%, more preferably 0.1%, still more preferably 0.2%, still more preferably 0.3%.
On the other hand, when the content of the WO 3 component is 10.0% or less, the coloring of the glass due to the WO 3 component can be reduced and the visible light transmittance can be improved. Therefore, the upper limit of the content of the WO 3 component is preferably 10.0%, more preferably 5.0%, and even more preferably 3.0%.
As the component WO 3, WO 3 and the like can be used as a raw material.
The Ta 2O5 component is any component whose content is more than 0% and which can improve the refractive index of the glass and can improve the devitrification resistance.
On the other hand, by setting the expensive Ta 2O5 component to 10.0% or less, the material cost of the glass can be reduced, and thus a cheaper optical glass can be produced. In addition, by setting the content of the Ta 2O5 component to 10.0% or less, the melting temperature of the raw material can be reduced, and the energy required for melting the raw material can be reduced, thereby reducing the manufacturing cost of the optical glass. Therefore, the upper limit of the content of the Ta 2O5 component is preferably 10.0%, more preferably 8.0%, and even more preferably 5.0%. In particular, from the viewpoint of producing a cheaper optical glass, the upper limit of the content of the Ta 2O5 component is preferably 4.0%, more preferably 3.0%, still more preferably less than 1.0%, and most preferably not contained.
The Ta 2O5 component may use Ta 2O5 or the like as a raw material.
The MgO component is any component whose content is more than 0% and which can improve the meltability of the glass raw material or the devitrification resistance of the glass.
On the other hand, by setting the content of the MgO component to 15.0% or less, a decrease in refractive index or a decrease in devitrification resistance due to excessive content of these components can be suppressed. Therefore, the upper limit of the content of the MgO component is preferably 15.0%, more preferably 10.0%, and even more preferably 5.0%.
As the MgO component, mgCO 3、MgF2 or the like can be used as a raw material.
The CaO component is any component whose content is more than 0% and which can improve the refractive index and devitrification resistance of the glass and can improve the meltability of the glass raw material. Therefore, the lower limit of the content of the CaO component is preferably more than 0%, more preferably 0.5%, even more preferably 1.5%, and still more preferably 3.0%.
On the other hand, by setting the CaO content to 15.0% or less, the refractive index of the glass is not easily lowered, and devitrification of the glass can be reduced. Therefore, the upper limit of the content of the CaO component is preferably 15.0%, more preferably 10.0%, and even more preferably 5.0%.
As the CaO component, caCO 3、CaF2 or the like can be used as a raw material.
The SrO component is any component whose content is more than 0% and which can improve the refractive index and devitrification resistance of the glass and can improve the meltability of the glass raw material. Therefore, the lower limit of the content of the SrO component is preferably more than 0%, more preferably 0.5%, further preferably 1.5%, and still further preferably 3.0%.
On the other hand, by setting the content of the SrO component to 15.0% or less, the refractive index of the glass is not easily lowered, and devitrification of the glass can be reduced. Therefore, the upper limit of the content of the SrO component is preferably 15.0%, more preferably 10.0%, and even more preferably 5.0%.
SrO component may be SrCO 3、SrF2 or the like as a raw material.
The Li 2 O component, the Na 2 O component, and the K 2 O component are any components that can improve the meltability of the glass when the content of at least any one of them is more than 0%. In particular, the K 2 O component is also a component capable of further increasing the partial dispersion ratio of the glass.
On the other hand, by reducing the content of the Li 2 O component, the Na 2 O component, or the K 2 O component, the decrease in refractive index of the glass can be suppressed, and devitrification can be reduced. In particular, by reducing the content of the Li 2 O component, the decrease in the partial dispersion ratio of the glass can be suppressed. Therefore, the content of at least one of the Li 2 O component, the Na 2 O component, and the K 2 O component is preferably 15.0%, more preferably less than 10.0%, further preferably less than 5.0%, and still further preferably less than 1.0%.
As the Li 2 O component, na 2 O component, and K 2 O component, Li2CO3、LiNO3、LiF、Na2CO3、NaNO3、NaF、Na2SiF6、K2CO3、KNO3、KF、KHF2、K2SiF6 and the like can be used as raw materials.
The P 2O5 component is any component which can improve the devitrification resistance of the glass when the content thereof is more than 0%. In particular, by setting the content of the P 2O5 component to 10.0% or less, the decrease in chemical durability of the glass, particularly the decrease in water resistance, can be suppressed. Therefore, the upper limit of the content of the P 2O5 component is preferably 10.0%, more preferably 5.0%, and even more preferably 3.0%.
The P 2O5 component may be Al(PO3)3、Ca(PO3)2、Ba(PO3)2、BPO4、H3PO4 or the like.
The GeO 2 component is any component that can increase the refractive index of the glass and improve the devitrification resistance of the glass when the content thereof is more than 0%. However, since GeO 2 is expensive in terms of raw materials, a large amount of GeO 2 is used to increase the cost of the materials, and thus the cost reduction effect due to the reduction of Gd 2O3 component or Ta 2O5 component is impaired. Therefore, the upper limit of the content of GeO 2 component is preferably 10.0%, more preferably 5.0%, further preferably 1.0%, and most preferably not contained.
As the GeO 2 component, geO 2 or the like can be used as a raw material.
The Al 2O3 component and the Ga 2O3 component are any components whose content is more than 0% that can improve the chemical durability of the glass and improve the devitrification resistance of the glass.
On the other hand, by setting the content of each of the Al 2O3 component and the Ga 2O3 component to 15.0% or less, it is possible to suppress a decrease in devitrification resistance of the glass due to excessive content of these components. Therefore, the upper limit of the content of each of the Al 2O3 component and the Ga 2O3 component is preferably 15.0%, more preferably 8.0%, and even more preferably 3.0%.
As the Al 2O3 component and the Ga 2O3 component, al 2O3、Al(OH)3、AlF3、Ga2O3、Ga(OH)3 and the like can be used as raw materials.
The Bi 2O3 component is any component whose content is more than 0% and which can increase the refractive index and lower the glass transition temperature.
On the other hand, when the content of the Bi 2O3 component is 10.0% or less, the devitrification resistance of the glass can be improved, and the coloring of the glass can be reduced to improve the visible light transmittance. Therefore, the upper limit of the content of Bi 2O3 component is preferably 10.0%, more preferably 5.0%, and even more preferably 3.0%.
As the Bi 2O3 component, bi 2O3 and the like can be used as raw materials.
The TeO 2 component is any component whose content is more than 0% that can raise the refractive index and lower the glass transition temperature.
However, when a glass raw material is charged into a platinum crucible or a portion in contact with molten glass is melted in a melting tank made of platinum, there is a problem in that the TeO 2 component may be alloyed with platinum. Therefore, the upper limit of the content of the TeO 2 component is preferably 10.0%, more preferably 5.0%, still more preferably 3.0%, and still more preferably no content.
TeO 2 component may be TeO 2 or the like as a raw material.
The SnO 2 component is any component whose content is more than 0% and which can reduce oxidation of the molten glass to make the molten glass clear and can make the light transmittance of the glass less likely to be deteriorated.
On the other hand, when the content of SnO 2 component is 3.0% or less, coloring of the glass or devitrification of the glass due to reduction of the molten glass is less likely to occur. In addition, since the alloying of the SnO 2 component with the melting equipment (particularly, noble metal such as Pt) is reduced, the life of the melting equipment can be prolonged. Therefore, the content of SnO 2 component is preferably 3.0% or less, more preferably less than 2.0%, still more preferably less than 1.0%, and even more preferably no component is contained.
As the SnO 2 component, snO 2、SnO2、SnF2、SnF4 or the like can be used as a raw material.
The Sb 2O3 component is any component which can defoam the molten glass when the content thereof is more than 0%.
On the other hand, by setting the content of the Sb 2O3 component to 1.0% or less, excessive foaming can be prevented from occurring, and alloying with melting equipment (particularly, noble metals such as Pt) can be reduced. Therefore, the content of the Sb 2O3 component is preferably 1.0% or less, more preferably less than 0.5%, further preferably less than 0.3%, and still further preferably less than 0.1%.
As the Sb 2O3 component, sb 2O3、Sb2O5、Na2H2Sb2O7·5H2 O or the like can be used as a raw material.
The component for refining and defoaming glass is not limited to the Sb 2O3 component described above, and a refining agent, a defoaming agent, or a combination thereof, which are known in the glass manufacturing field, may be used.
The F component is any component whose content is more than 0% and which can increase the abbe number of the glass, lower the glass transition temperature, and improve the devitrification resistance.
However, if the content of the F component, that is, the total amount of F which is a fluoride substituted by a part or all of one or two or more oxides of the above-mentioned respective metal elements is more than 10.0%, the volatilization amount of the F component increases, and thus it is difficult to obtain a stable optical constant, and it is difficult to obtain a homogeneous glass. In addition, the abbe number may rise to an extent exceeding that necessary.
Therefore, the content of the F component is preferably 10.0% or less, more preferably less than 5.0%, further preferably less than 3.0%, still more preferably less than 1.0%, and still more preferably no F component.
< Concerning the component to be not contained >
Next, the components not to be contained and the components not to be contained preferably in the optical glass of the present invention will be described.
In the optical glass of the present application, other components may be added as needed as long as the properties of the glass of the present application are not impaired. However, the GeO 2 component is preferably substantially not contained because it improves the dispersion of the glass.
In addition, since various transition metal components other than Ti, zr, nb, W, la, gd, Y, yb, lu, for example, hf, n, cr, mn, fe, co, ni, cu, ag, mo, ce, nd, etc. have properties such that if they are contained individually or in combination, even a small amount of the transition metal components will color the glass and absorb light of a specific wavelength in the visible light region, they are preferably not substantially contained in the optical glass, particularly in which wavelengths in the visible light region are used.
In addition, lead compounds such As PbO, arsenic compounds such As 2O3, and Th, cd, tl, os, be, se have been recently used As harmful chemicals and have been prevented from being used, and environmental measures are required not only for the glass manufacturing process but also for the processing process and the post-production treatment. Therefore, in the case of focusing on environmental influences, these components are preferably not substantially contained except for unavoidable mixing. Thus, the optical glass contains substantially no environmental pollution. Therefore, the optical glass can be manufactured, processed, and discarded without taking special measures against the environment.
[ Method of production ]
The optical glass of the present invention can be produced, for example, as follows. That is, the above raw materials are uniformly mixed so that the respective components fall within a predetermined content range, the prepared mixture is put into a platinum crucible, a quartz crucible or an alumina crucible to be coarsely melted, and then put into a gold crucible, a platinum alloy crucible or an iridium crucible to be melted for 1 to 5 hours at a temperature range of 900 to 1400 ℃, and after the steps of homogenizing by stirring and defoaming, the temperature is lowered to 1300 ℃ or less, and then the final-stage stirring is performed to remove streaks, and molding is performed by using a molding die. Here, as a method for obtaining glass molded by using a molding die, there is a method in which a molten glass is flowed into one end of the molding die and the molded glass is pulled out from the other end of the molding die, or a method in which the molten glass is cast into a die and then gradually cooled.
Physical Properties
The optical glass of the present invention preferably has a high refractive index and high dispersion.
In particular, the lower limit of the refractive index (n d) of the optical glass of the present invention is preferably 1.90, more preferably 1.95, and further preferably 1.98. The upper limit of the refractive index is preferably 2.20, more preferably 2.15, and further preferably 2.10. The lower limit of the Abbe number (v d) of the optical glass of the present invention is preferably 15.0, more preferably 18.0, further preferably 20.0, and the upper limit thereof is preferably 30.0, more preferably 28.0, further preferably 27.0.
By having such a high refractive index, a large light refractive index can be obtained even when the optical element is thinned. In addition, by having such high dispersion, for example, when combined with an optical element having low dispersion (high abbe number), high imaging characteristics and the like can be achieved.
Therefore, the optical glass of the present invention is useful for optical design, and particularly, can realize miniaturization of an optical system while seeking high imaging characteristics and the like, and can expand the degree of freedom of optical design.
The optical glass of the present invention preferably has high visible light transmittance, particularly high transmittance of light on the short wavelength side among visible light, and thus is less colored.
In particular, the optical glass of the present invention preferably has an upper limit of a wavelength (λ 70) at which the spectral transmittance is 70% in a sample having a thickness of 10mm, as represented by the transmittance of the glass, of 500nm, more preferably 490nm, and still more preferably 480nm.
In the optical glass of the present invention, the upper limit of the shortest wavelength (. Lamda. 5) showing a spectral transmittance of 5% in a sample having a thickness of 10mm is preferably 400nm, more preferably 390nm.
Thus, the absorption edge of the glass is positioned in the vicinity of the ultraviolet region, and the transparency of the glass to visible light can be improved, so that the optical glass can be preferably used for an optical element such as a lens that transmits light.
The optical glass of the present invention preferably has a high partial dispersion ratio (θg, F). More specifically, the lower limit of the partial dispersion ratio (θg, F) of the optical glass of the invention is preferably 0.570, more preferably 0.580, further preferably 0.595, further preferably 0.605, further preferably 0.612.
In addition, the relationship between the partial dispersion ratio (θg, F) and the abbe number (v d) of the optical glass of the present invention preferably satisfies the relationship (-0.00162 v d+0.645)≤(θg,F)≤(-0.00162vd +0.680). Thus, since an optical glass having a small partial dispersion ratio (θg, F) can be obtained, making the optical glass conducive to reducing chromatic aberration of an optical element or the like can be achieved.
Therefore, the lower limit of the partial dispersion ratio (θg, F) of the optical glass of the invention is preferably (-0.00162 v d +0.645), more preferably (-0.00162 v d +0.650).
On the other hand, the upper limit of the partial dispersion ratio (θg, F) of the optical glass of the invention is preferably (-0.00162 v d +0.675), more preferably (-0.00162 v d +0.670).
In rectangular coordinates having a vertical axis of the partial dispersion ratio and a horizontal axis of the abbe number, the relationship between the partial dispersion ratio (θg, F) and the abbe number (v d) is represented by a straight line parallel to the normal line. The normal line represents a linear relationship observed between the partial dispersion ratio (θg, F) and the abbe number (v d) of the conventionally known glass, and is represented by a straight line obtained by connecting two points of the partial dispersion ratio and the abbe number obtained by plotting NSL7 and PBM2 on a rectangular coordinate having the vertical axis and the abbe number (v d) as the horizontal axis (see fig. 1). Further, the relationship between the partial dispersion ratio and the abbe number of the conventionally known glass is substantially the same as that of the normal line.
Here, NSL7 and PBM2 are optical glasses manufactured by small corporation, the abbe number (v d) of PBM2 is 36.3, the partial dispersion ratio (θg, F) is 0.5828, the abbe number (v d) of NSL7 is 60.5, and the partial dispersion ratio (θg, F) is 0.5436.
Preform and optical element
The glass molded body can be produced from the optical glass produced by a polishing method, a press molding method such as reheat press molding or precision press molding, or the like. That is, the glass molded body may be produced by mechanically working such as grinding and polishing an optical glass, or by producing a glass molded body by performing hot press molding on a preform made of an optical glass and then polishing, or by producing a glass molded body by performing precision press molding on a preform produced by polishing or a preform molded by known float molding or the like. It should be noted that the method of producing the glass molded body is not limited to the above method.
As described above, the glass molded body formed of the optical glass of the present invention is useful for various optical elements and optical designs, and is particularly preferably used for optical elements such as lenses and prisms. Since the glass can be formed into a glass molded body having a large diameter by improving the stability of the glass, the imaging characteristics and the projection characteristics can be realized with high definition and high precision when an optical device such as a camera or a projector is used while the optical element is enlarged.
Examples
The glass compositions of examples (No. 1 to No. 52) of the present invention are shown in tables 1 to 10, respectively, with respect to the refractive index (n d), abbe number (v d), transmittance (. Lamda. 5、λ70) and partial dispersion ratio (. Theta.g, F) of these glasses. It should be noted that the following examples are for illustrative purposes only, and the present invention is not limited to these examples.
In the glass of the examples, as raw materials of each component, high-purity raw materials used for general optical glass such as oxide, hydroxide, carbonate, nitrate, fluoride, hydroxide, metaphosphoric acid compound and the like are selected, weighed and uniformly mixed, and then put into a platinum crucible, and the glass raw materials are melted for 2.5 hours in an electric furnace at a temperature range of 1280 to 1340 ℃, and when the glass raw materials are melted, the melted glass raw materials are defoamed by stirring, cooled to 1180 to 1250 ℃, stirred again to be uniform, and then cast into a mold, and slowly cooled to obtain the glass.
The refractive index (n d) and Abbe number (v d) of the glass of the example are expressed as measured values with respect to the d-line (587.56 nm) of a helium lamp. The Abbe number (v d) was calculated from the numerical expression of Abbe number (v d)＝[(nd-1)/(nF-nC) using the values of the refractive index of d-line, the refractive index (n F) of F-line (486.13 nm) and the refractive index (n C) of C-line (656.27 nm).
The refractive index n C in the C line (wavelength 656.27 nm), the refractive index n F in the F line (wavelength 486.13 nm), and the refractive index n g in the g line (wavelength 435.835 nm) were measured, and the partial dispersion ratio was calculated from the equation of (θg, F) = (n g-nF)/(nF-nC).
The transmittance of the glass of the examples was measured according to JOGIS02-2003, a Japanese optical nitroprusside Industrial Association standard. In the present invention, the presence or absence of glass coloration and the degree of coloration are determined by measuring the transmittance of glass. Specifically, according to JISZ8722, spectral transmittance of 200 to 800nm was measured for an opposite parallel polished article having a thickness of 10±0.1mm, and λ 5 (wavelength at 5% transmittance) and λ 70 (wavelength at 70% transmittance) were obtained.
The glass used in the measurement was treated in a slow cooling furnace at a slow cooling rate of-25 ℃.
TABLE 1
wt% 1 2 3 4 5 6
SiO2 6.01 6.01 6.01 5.43 5.01 5.01
B2O3 6.95 6.95 6.95 7.60 6.95 6.95
La2O3 31.99 32.00 33.27 31.72 32.00 33.98
Y2O3
Gd2O3
Yb2O3
ZrO2 6.39 6.39 6.39 6.37 6.39 4.39
TiO2 21.70 21.70 21.70 21.89 22.70 21.70
Nb2O5 7.31 7.31 7.31 8.78 7.31 8.31
WO3 0.77 0.77 0.77 0.77 0.77 0.77
ZnO 1.27 1.27 1.27 1.27
Li2O
Na2O
K2O
MgO
CaO
SrO
BaO 17.60 17.60 17.60 17.45 17.60 17.60
Sb2O3 0.01 0.00 0.00 0.00 0.00 0.02
Totalizing 100.00 100.00 100.00 100.00 100.00 100.00
Si+B 12.96 12.96 12.96 13.03 11.96 11.96
Ti/(Ti+Ba) 0.55 0.55 0.55 0.56 0.56 0.55
La+Nb+Gd+Yb 39.30 39.31 40.58 40.50 39.31 42.29
Ti/Ba 1.23 1.23 1.23 1.25 1.29 1.23
Rn2O 0.00 0.00 0.00 0.00 0.00 0.00
RO 17.60 17.60 17.60 17.45 17.60 17.60
Ln 31.99 32.00 33.27 31.72 32.00 33.98
Ti+Nb 29.01 29.01 29.01 30.66 30.01 30.01
(Ti+W)/Ba 1.28 1.28 1.28 1.30 1.33 1.28
La/(Nb+Gd+Yb) 4.38 4.38 4.55 3.62 4.38 4.09
nd 2.012 2.012 2.012 2.018 2.025 2.020
vd 24.9 24.9 25.0 24.5 24.4 24.7
θg,F 0.6156 0.6155 0.6138 0.6168 0.6167 0.6150
λ70 447 448 447 459 451 454
λ5 373 372 372 375 373 374
TABLE 2
wt% 7 8 9 10 11 12
SiO2 5.01 5.51 5.51 5.51 5.51 5.51
B2O3 6.95 7.45 7.45 7.45 7.45 7.45
La2O3 32.48 29.48 30.08 30.08 30.08 29.58
Y2O3
Gd2O3
Yb2O3
ZrO2 5.89 5.89 5.89 5.89 5.89 5.79
TiO2 21.70 21.70 21.70 21.70 21.70 21.70
Nb2O5 8.31 10.31 10.31 10.61 10.61 10.31
WO3 0.77 0.77 0.77 0.77 0.77 0.77
ZnO 1.27 1.27 0.67 0.67 3.67 1.27
Li2O
Na2O
K2O
MgO
CaO
SrO
BaO 17.60 17.60 17.60 17.30 14.30 17.60
Sb2O3 0.02 0.02 0.02 0.02 0.02 0.02
Totalizing 100.00 100.00 100.00 100.00 100.00 100.00
Si+B 11.96 12.96 12.96 12.96 12.96 12.96
Ti/(Ti+Ba) 0.55 0.55 0.55 0.56 0.60 0.55
La+Nb+Gd+Yb 40.79 39.79 40.39 40.69 40.69 39.89
Ti/Ba 1.23 1.23 1.23 1.25 1.52 1.23
Rn2O 0.00 0.00 0.00 0.00 0.00 0.00
RO 17.60 17.60 17.60 17.30 14.30 17.60
Ln 32.48 29.48 30.08 30.08 30.08 29.58
Ti+Nb 30.01 32.01 32.01 32.31 32.31 32.01
(Ti+W)/Ba 1.28 1.28 1.28 1.30 1.57 1.28
La/(Nb+Gd+Yb) 3.91 2.86 2.92 2.84 2.84 2.87
nd 2.022 2.021 2.021 2.023 2.027 2.020
vd 24.6 24.2 24.2 24.1 24.0 24.2
θg,F 0.6157
λ70 468 459 457.5 463 462 467
λ5 376 377 377 377.5 378 378
TABLE 3 Table 3
wt% 13 14 15
SiO2 5.51 5.51 5.51
B2O3 7.45 7.45 7.45
La2O3 31.48 29.48 33.48
Y2O3
Gd2O3
Yb2O3
ZrO2 5.89 5.89 5.89
TiO2 21.70 21.70 21.70
Nb2O5 10.31 10.31 10.31
WO3 0.77 0.77 0.77
ZnO 1.27 1.27 1.27
Li2O
Na2O
K2O
MgO
CaO
SrO
BaO 15.60 17.60 13.60
Sb2O3 0.02 0.02 0.02
Totalizing 100.00 100.00 100.00
Si+B 12.96 12.96 12.96
Ti/(Ti+Ba) 0.58 0.55 0.61
La+Nb+Gd+Yb 41.79 39.79 43.79
Ti/Ba 1.39 1.23 1.60
Rn2O 0.00 0.00 0.00
RO 15.60 17.60 13.60
Ln 31.48 29.48 33.48
Ti+Nb 32.01 32.01 32.01
(Ti+W)/Ba 1.44 1.28 1.65
La/(Nb+Gd+Yb) 3.05 2.86 3.25
nd 2.026 2.021 2.031
vd 24.2 24.2 24.2
θg,F
λ70 467 467 470
λ5 379 378 380
TABLE 4 Table 4
wt% 16 17 18 19 20 21
SiO2 6.01 6.01 6.01 6.01 6.01 6.01
B2O3 7.70 7.70 7.70 7.70 7.70 7.70
La2O3 33.03 33.03 33.03 32.53 33.53 33.03
Y2O3
Gd2O3
Yb2O3
ZrO2 6.39 6.39 6.39 6.89 5.89 6.39
TiO2 20.90 20.90 20.90 20.90 20.90 20.90
Nb2O5 6.91 7.31 6.71 6.71 6.71 6.91
WO3 0.77 0.77 0.77 0.77 0.77 0.77
ZnO 1.27 1.27 1.27 1.27 1.27 1.27
Li2O
Na2O
K2O
MgO
CaO
SrO
BaO 17.00 16.60 17.20 17.20 17.20 17.00
Sb2O3 0.02 0.02 0.02 0.02 0.02 0.02
Totalizing 100.00 100.00 100.00 100.00 100.00 100.00
Si+B 13.71 13.71 13.71 13.71 13.71 13.71
Ti/(Ti+Ba) 0.55 0.56 0.55 0.55 0.55 0.55
La+Nb+Gd+Yb 39.94 40.34 39.74 39.24 40.24 39.94
Ti/Ba 1.23 1.26 1.22 1.22 1.22 1.23
Rn2O 0.00 0.00 0.00 0.00 0.00 0.00
RO 17.00 16.60 17.20 17.20 17.20 17.00
Ln 33.03 33.03 33.03 32.53 33.53 33.03
Ti+Nb 27.81 28.21 27.61 27.61 27.61 27.81
(Ti+W)/Ba 1.27 1.31 1.26 1.26 1.26 1.27
La/(Nb+Gd+Yb) 4.78 4.52 4.92 4.85 5.00 4.78
nd 2.001 2.003 2.000 2.001 1.999 2.001
vd 25.4 25.3 25.5 25.4 25.5 25.4
θg,F 0.6141 0.6137 0.6133 0.6132 0.6133 0.6136
λ70 446 450 458 451 450 449
λ5 373 374 374 373 373 373
TABLE 5
wt% 22 23 24 25 26 27
SiO2 6.01 6.01 6.01 6.01 6.01 6.01
B2O3 7.70 7.70 7.70 7.70 7.70 7.70
La2O3 33.03 33.03 33.03 33.03 33.03 38.03
Y2O3
Gd2O3
Yb2O3
ZrO2 6.39 6.39 6.39 6.39 6.39 6.39
TiO2 20.90 20.90 20.90 20.90 20.90 20.90
Nb2O5 6.91 6.91 6.91 6.91 6.91 6.91
WO3 0.77 0.77 0.77 0.77 0.77 0.77
ZnO 6.27 0.77 2.27 4.27 1.27
Li2O
Na2O
K2O
MgO
CaO
SrO
BaO 18.27 12.00 17.50 16.00 14.00 12.00
Sb2O3 0.02 0.02 0.02 0.02 0.02 0.02
Totalizing 100.00 100.00 100.00 100.00 100.00 100.00
Si+B 13.71 13.71 13.71 13.71 13.71 13.71
Ti/(Ti+Ba) 0.53 0.64 0.54 0.57 0.60 0.64
La+Nb+Gd+Yb 39.94 39.94 39.94 39.94 39.94 44.94
Ti/Ba 1.14 1.74 1.19 1.31 1.49 1.74
Rn2O 0.00 0.00 0.00 0.00 0.00 0.00
RO 18.27 12.00 17.50 16.00 14.00 12.00
Ln 33.03 33.03 33.03 33.03 33.03 38.03
Ti+Nb 27.81 27.81 27.81 27.81 27.81 27.81
(Ti+W)/Ba 1.19 1.81 1.24 1.35 1.55 1.81
La/(Nb+Gd+Yb) 4.78 4.78 4.78 4.78 4.78 5.50
nd 1.998 2.009 2.000 2.003 2.006 2.014
vd 25.5 25.2 25.5 25.4 25.3 25.4
θg,F 0.6133 0.6153 0.6132 0.6138 0.6136 0.6130
λ70 462 459 451 459 453 454
λ5 375 375 373 375 374 375
TABLE 6
wt% 28 29 30 31 32 33
SiO2 6.01 6.01 6.01 6.01 6.01 6.01
B2O3 7.70 7.70 7.70 7.70 7.70 7.70
La2O3 34.03 36.03 34.83 34.83 34.83 34.83
Y2O3
Gd2O3
Yb2O3
ZrO2 6.39 6.39 6.39 6.39 6.39 6.39
TiO2 20.90 20.90 20.10 20.10 20.10 20.10
Nb2O5 6.91 6.91 6.91 5.91 6.91 5.91
WO3 0.77 0.77 0.77 1.77 0.77 1.77
ZnO 1.27 1.27 1.27 1.27 1.27 1.27
Li2O
Na2O
K2O
MgO
CaO
SrO
BaO 16.00 14.00 16.00 16.00 16.00 16.00
Sb2O3 0.02 0.02 0.02 0.02 0.02 0.02
Totalizing 100.00 100.00 100.00 100.00 100.00 100.00
Si+B 13.71 13.71 13.71 13.71 13.71 13.71
Ti/(Ti+Ba) 0.57 0.60 0.56 0.56 0.56 0.56
La+Nb+Gd+Yb 40.94 42.94 41.74 40.74 41.74 40.74
Ti/Ba 1.31 1.49 1.26 1.26 1.26 1.26
Rn2O 0.00 0.00 0.00 0.00 0.00 0.00
RO 16.00 14.00 16.00 16.00 16.00 16.00
Ln 34.03 36.03 34.83 34.83 34.83 34.83
Ti+Nb 27.81 27.81 27.01 26.01 27.01 26.01
(Ti+W)/Ba 1.35 1.55 1.30 1.37 1.30 1.37
La/(Nb+Gd+Yb) 4.92 5.21 5.04 5.89 5.04 5.89
nd 2.003 2.008 1.999 1.999 1.999 1.999
vd 25.4 25.4 25.8 25.8 25.8 25.8
θg,F 0.6137 0.6137 0.6124 0.6124 0.6119 0.6118
λ70 453 451 442 445
λ5 374 374 372 372
TABLE 7
wt% 34 35 36 37 38 39
SiO2 6.01 6.01 6.01 6.01 6.01 6.01
B2O3 7.70 7.70 7.70 7.70 7.70 7.70
La2O3 34.84 34.84 34.84 34.14 33.64 34.64
Y2O3
Gd2O3
Yb2O3
ZrO2 6.39 6.39 6.39 6.39 6.89 5.89
TiO2 20.10 20.10 20.10 20.80 20.80 20.80
Nb2O5 6.91 6.91 6.91 6.91 6.91 6.91
WO3 0.77 0.77 0.77 0.77 0.77 0.77
ZnO 1.27 1.27 1.27 1.27 1.27 1.27
Li2O
Na2O
K2O
MgO
CaO
SrO
BaO 16.00 16.00 16.00 16.00 16.00 16.00
Sb2O3 0.01 0.01 0.01 0.01 0.01 0.01
Totalizing 100.00 100.00 100.00 100.00 100.00 100.00
Si+B 13.71 13.71 13.71 13.71 13.71 13.71
Ti/(Ti+Ba) 0.56 0.56 0.56 0.57 0.57 0.57
La+Nb+Gd+Yb 41.75 41.75 41.75 41.05 40.55 41.55
Ti/Ba 1.26 1.26 1.26 1.30 1.30 1.30
Rn2O 0.00 0.00 0.00 0.00 0.00 0.00
RO 16.00 16.00 16.00 16.00 16.00 16.00
Ln 34.84 34.84 34.84 34.14 33.64 34.64
Ti+Nb 27.01 27.01 27.01 27.71 27.71 27.71
(Ti+W)/Ba 1.30 1.30 1.30 1.35 1.35 1.35
La/(Nb+Gd+Yb) 5.04 5.04 5.04 4.94 4.87 5.01
nd 1.999 1.999 1.999 2.003 2.003 2.002
vd 25.8 25.8 25.8 25.5 25.4 25.5
θg,F 0.6116 0.6116 0.6119 0.6139 0.6137 0.6131
λ70 444.5 454 448.5
λ5 371.5 373 372
TABLE 8
wt% 40 41 42 43 44 45
SiO2 6.21 6.01 6.01 6.01 6.01 6.01
B2O3 7.85 8.02 7.70 8.02 8.02 8.02
La2O3 33.33 33.82 34.34 33.83 33.83 33.83
Y2O3
Gd2O3
Yb2O3
ZrO2 6.39 6.39 6.19 6.39 6.39 6.39
TiO2 20.90 21.10 20.80 21.10 21.10 21.10
Nb2O5 6.91 6.61 6.91 6.61 6.61 6.61
WO3 0.77 0.77 0.77 0.77 0.77 0.77
ZnO 1.27 1.27 1.27 1.27 1.27 1.27
Li2O
Na2O
K2O
MgO
CaO
SrO
BaO 16.35 16.00 16.00 16.00 16.00 16.00
Sb2O3 0.02 0.01 0.01 0.00 0.00 0.00
Totalizing 100.00 100.00 100.00 100.00 100.00 100.00
Si+B 14.06 14.03 13.71 14.03 14.03 14.03
Ti/(Ti+Ba) 0.56 0.57 0.57 0.57 0.57 0.57
La+Nb+Gd+Yb 40.24 40.43 41.25 40.44 40.44 40.44
Ti/Ba 1.28 1.32 1.30 1.32 1.32 1.32
Rn2O 0.00 0.00 0.00 0.00 0.00 0.00
RO 16.35 16.00 16.00 16.00 16.00 16.00
Ln 33.33 33.82 34.34 33.83 33.83 33.83
Ti+Nb 27.81 27.71 27.71 27.71 27.71 27.71
(Ti+W)/Ba 1.33 1.37 1.35 1.37 1.37 1.37
La/(Nb+Gd+Yb) 4.82 5.12 4.97 5.12 5.12 5.12
nd 1.999 2.001 2.002 2.000 2.001 2.001
vd 25.5 25.4 25.5 25.4 25.4 25.4
θg,F 0.6138 0.6131 0.6128 0.6135 0.6126 0.6132
λ70 460 447 447 450 452
λ5 375 372 372 372 373
TABLE 9
wt% 46 47 48 49 50 51
SiO2 6.21 6.12 6.63 7.87 6.55 8.14
B2O3 7.85 8.02 10.10 10.02 9.98 10.43
La2O3 33.41 33.73 41.27 37.39 31.49 36.13
Y2O3
Gd2O3
Yb2O3
ZrO2 6.39 6.39 6.37 6.68 5.51 6.85
TiO2 20.83 21.08 16.68 18.48 14.30 16.76
Nb2O5 6.91 6.61 6.34 5.56 13.88 2.39
WO3 0.77 0.77 0.82 5.19 2.48
ZnO 1.27 1.27 1.36 1.61 1.34 2.20
Li2O
Na2O
K2O
MgO
CaO
SrO
BaO 16.35 16.00 10.43 12.38 11.75 14.61
Sb2O3 0.01 0.01 0.01 0.01 0.01 0.01
Totalizing 99.99 100.00 100.00 100.00 100.00 100.00
Si+B 14.06 14.14 16.73 17.89 16.53 18.57
Ti/(Ti+Ba) 0.56 0.57 0.62 0.60 0.55 0.53
La+Nb+Gd+Yb 40.32 40.34 47.61 42.96 45.36 38.52
Ti/Ba 1.27 1.32 1.60 1.49 1.22 1.15
Rn2O 0.00 0.00 0.00 0.00 0.00 0.00
RO 16.35 16.00 10.43 12.38 11.75 14.61
Ln 33.41 33.73 41.27 37.39 31.49 36.13
Ti+Nb 27.74 27.69 23.02 24.04 28.18 19.15
(Ti+W)/Ba 1.32 1.37 1.68 1.49 1.66 1.32
La/(Nb+Gd+Yb) 4.83 5.10 6.51 6.72 2.27 15.10
nd 1.999 2.000 1.968 1.961 1.976 1.934
vd 25.5 25.5 27.8 27.4 26.1 28.8
θg,F 0.6131 0.6134 0.6053 0.6081 0.6115 0.6040
λ70 455 444 440 428 436 420
λ5 375 372 369 369 373 367
Table 10
wt% 52
SiO2 6.21
B2O3 7.85
La2O3 33.41
Y2O3
Gd2O3
YbO3
ZrO2 6.39
TiO2 20.83
Nb2O5 6.91
WO3 0.77
ZnO 1.27
Li2O 0.10
Na2O
K2O
MgO
CaO
SrO
BaO 16.35
Sb2O3
Totalizing 100.08
Si+B 14.06
Ti/(Ti+Ba) 0.56
La+Nb+Gd+Yb 40.32
Ti/Ba 1.27
Rn2O 0.10
RO 16.35
Ln 33.41
Ti+Nb 27.74
(Ti+W)/Ba 1.32
La/(Nb+Gd+Yb) 4.83
nd 1.999
vd 25.5
θg,F 0.6130
λ70 449
λ5 372
As shown in the table, the optical glasses of the examples of the present invention each have a refractive index (n d) of 1.90 or more, and the refractive index (n d) of 2.20 or less, more specifically, 2.10 or less, within the desired range.
The optical glasses of the examples of the present invention have an abbe number (v d) of 30.0 or less, more specifically 28.0 or less, and an abbe number (v d) of 15.0 or more, more specifically 20.0 or more, both of which fall within a desired range.
In addition, λ 70 (wavelength at 70% transmittance) of the optical glass of the example of the present invention is 500nm or less, more specifically 490nm or less. In addition, λ 5 (wavelength at 5% transmittance) of the optical glass of the example of the present invention is 400nm or less, more specifically 390nm or less.
The optical glass of the embodiment of the present invention has a partial dispersion ratio (θg, F) of (-0.00162 v d +0.645) or more, more specifically (-0.00162 v d +0.650) or more. In contrast, the optical glass according to the embodiment of the present invention has a partial dispersion ratio of (-0.00162 v d +0.680) or less, more specifically (-0.00162 v d +0.670) or less. From this, it is found that these partial dispersion ratios (θg, F) fall within the desired range.
Therefore, it is clear that the optical glass of the embodiment of the present invention is easy to manufacture and less colored while the refractive index and abbe number thereof are within the desired ranges.
Further, using the optical glass obtained in the examples of the present invention, after the hot press molding was performed again, grinding and polishing were performed, and processing into lens and prism shapes was performed. Further, using the optical glass according to the embodiment of the present invention, a preform for precision press molding was formed, and precision press molding was performed on the preform for precision press molding. In either case, the glass after heat softening does not cause problems such as occurrence of emulsion whitening and devitrification, and can be stably processed into various lens and prism shapes.
While the invention has been described in detail and with reference to the embodiments thereof, it will be understood by those skilled in the art that the foregoing is illustrative only and that various changes in form and detail may be made therein without departing from the spirit and scope of the invention.

Claims (11)

1.一种光学玻璃，其特征在于，1. An optical glass, characterized in that: 以氧化物基准的质量％计，含有In terms of mass % based on oxides, 大于0％～45.0％的La2O3成分、More than 0% to 45.0% La 2 O 3 component, 大于0％～45.0％的TiO2成分、 TiO2 content greater than 0% to 45.0%, 大于0％～40.0％的BaO成分、以及BaO content greater than 0% to 40.0%, and 0～6.01％的SiO2成分，0～6.01% SiO2 content, 且SiO2成分与B2O3成分的总量为5.0％以上且30.0％以下，The total amount of SiO2 and B2O3 is 5.0% or more and 30.0% or less. RO成分的质量和为大于0％且14.30％以下，The mass sum of RO components is greater than 0% and less than 14.30%, 其中，R是选自由Mg、Ca、Sr、Ba组成的组中的一种以上，wherein R is one or more selected from the group consisting of Mg, Ca, Sr, and Ba, TiO2/(TiO2+BaO)的质量比为0.60以上且0.90以下，The mass ratio of TiO 2 /(TiO 2 +BaO) is 0.60 or more and 0.90 or less, TiO2/(La2O3+Nb2O5+Gd2O3+Yb2O3)的质量比为0.52以上，The mass ratio of TiO 2 /(La 2 O 3 +Nb 2 O 5 +Gd 2 O 3 +Yb 2 O 3 ) is 0.52 or more, 折射率(nd)为1.90以上，阿贝数(vd)为30.0以下，且显示光谱透射率5％的波长(λ5)为400nm以下。The refractive index (n d ) is 1.90 or more, the Abbe number (ν d ) is 30.0 or less, and the wavelength (λ 5 ) showing a spectral transmittance of 5% is 400 nm or less. 2.根据权利要求1所述的光学玻璃，其特征在于，2. The optical glass according to claim 1, characterized in that: 以氧化物基准的质量％计，Measured in mass % based on oxides, B2O3成分为0～30.0％。The B 2 O 3 component is 0 to 30.0%. 3.根据权利要求1或2所述的光学玻璃，其特征在于，3. The optical glass according to claim 1 or 2, characterized in that: 以氧化物基准的质量％计，Measured in mass % based on oxides, ZnO成分为0～20.0％，The ZnO content is 0 to 20.0%, Y2O3成分为0～15.0％， Y2O3 content is 0～15.0%, Nb2O5成分为0～25.0％， Nb2O5 content is 0～25.0%, Yb2O3成分为0～15.0％，以及 Yb2O3 content is 0 to 15.0%, and Gd2O3成分为0～15.0％。The Gd 2 O 3 component is 0 to 15.0%. 4.根据权利要求1或2所述的光学玻璃，其特征在于，4. The optical glass according to claim 1 or 2, characterized in that: 以氧化物基准的质量％计，Measured in mass % based on oxides, (La2O3+Nb2O5+Gd2O3+Yb2O3)的质量和为大于0％且60.0％以下。The mass sum of (La 2 O 3 +Nb 2 O 5 +Gd 2 O 3 +Yb 2 O 3 ) is more than 0% and 60.0% or less. 5.根据权利要求1或2所述的光学玻璃，其特征在于，5. The optical glass according to claim 1 or 2, characterized in that: 以氧化物基准的质量％计，Measured in mass % based on oxides, Ln2O3成分的合计为大于0％且50.0％以下，The total amount of Ln2O3 components is greater than 0% and less than 50.0%, 其中，Ln为选自由La、Gd、Y、Yb组成的组中的一种以上。Here, Ln is one or more selected from the group consisting of La, Gd, Y, and Yb. 6.根据权利要求1或2所述的光学玻璃，其特征在于，以氧化物基准计，6. The optical glass according to claim 1 or 2, characterized in that, based on oxides, TiO2/BaO为大于0且3.00以下。TiO 2 /BaO is greater than 0 and less than or equal to 3.00. 7.根据权利要求1或2所述的光学玻璃，其特征在于，以氧化物基准的质量％计，7. The optical glass according to claim 1 or 2, characterized in that, in terms of mass % based on oxides, Rn2O成分的质量和为15.0％以下，The mass sum of Rn2O components is 15.0% or less, 其中，Rn为选自由Li、Na、K组成的组中的一种以上。Here, Rn is one or more selected from the group consisting of Li, Na, and K. 8.根据权利要求1或2所述的光学玻璃，其特征在于，以氧化物基准的质量％计，含有ZrO2成分0～20.0％、8. The optical glass according to claim 1 or 2, characterized in that it contains 0 to 20.0% ZrO2 in terms of mass % based on oxides. WO3成分0～10.0％、 WO3 content 0～10.0%, Ta2O5成分0～10.0％、 Ta2O5 content 0～ 10.0 %, MgO成分0～15.0％、MgO content 0～15.0%, CaO成分0～15.0％、CaO content 0～15.0%, SrO成分0～15.0％、SrO content 0～15.0%, Li2O成分0～15.0％、 Li2O content 0～15.0%, Na2O成分0～15.0％、 Na2O content 0～15.0%, K2O成分0～15.0％、 K2O content 0～15.0%, P2O5成分0～10.0％、 P2O5 content 0～ 10.0 %, GeO2成分0～10.0％、 GeO2 content 0～10.0%, Al2O3成分0～15.0％、 Al2O3 content 0～ 15.0 %, Ga2O3成分0～15.0％、 Ga2O3 content 0～ 15.0 %, Bi2O3成分0～10.0％、 Bi2O3 content 0～10.0%, TeO2成分0～10.0％、 TeO2 content 0～10.0%, SnO2成分0～3.0％、以及 SnO2 content 0-3.0%, and Sb2O3成分0～1.0％。Sb 2 O 3 content: 0-1.0%. 9.一种预成型坯，其特征在于，9. A preform, characterized in that: 包括权利要求1至8中任一项所述的光学玻璃。The optical glass comprising any one of claims 1 to 8. 10.一种光学元件，其特征在于，10. An optical element, characterized in that: 包括权利要求1至8中任一项所述的光学玻璃。The optical glass comprising any one of claims 1 to 8. 11.一种光学仪器，其特征在于，11. An optical instrument, characterized in that: 具备权利要求10所述的光学元件。A method of manufacturing the optical element according to claim 10.
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