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CN108129018B - Optical glass, preform and optical element - Google Patents

Optical glass, preform and optical element Download PDF

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Publication number
CN108129018B
CN108129018B CN201711251286.0A CN201711251286A CN108129018B CN 108129018 B CN108129018 B CN 108129018B CN 201711251286 A CN201711251286 A CN 201711251286A CN 108129018 B CN108129018 B CN 108129018B
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CN108129018A (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
    • C03C3/04—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
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • 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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  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (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 invention discloses an optical glass, which comprises more than 0-45.0% of La by mass percent 2 O 3 Component (I), tiO 0-45.0% 2 A component of BaO in an amount of more than 0% to 40.0%, and SiO 2 Component (A) and (B) 2 O 3 The total amount of the components is more than 5.0% and less than 30.0%, tiO 2 /(TiO 2 A mass ratio of + BaO) of 0.10 to 0.90, a refractive index (n) d ) Is 1.90 or more, and has an Abbe number (v) d ) A wavelength (lambda) of 30.0 or less and a spectral transmittance of 5% 5 ) Is 400nm or less. According to the present invention, an optical glass having optical characteristics of high refractive index and high dispersion and low production cost of the glass can be provided.

Description

Optical glass, preform and optical element
Technical Field
The present invention relates to an optical glass, a preform and an optical element.
Background
In recent years, digitization using optical system instruments or high definition of images/videos is rapidly advancing. In particular, the high definition of images and videos is prominent in optical devices such as digital cameras, video cameras, and projectors. In addition, in the optical systems included in these optical instruments, the number of optical elements such as lenses and prisms is reduced, thereby achieving weight reduction and size reduction.
The optical glass for manufacturing optical elements has a high refractive index (n) of 1.90 or more, particularly for reducing the weight and size of the whole optical system d ) And a low Abbe number (v) of 15 to 30 inclusive d ) The demand for high refractive index and high dispersion glass of (2) is increasing. As such a high-refractive-index low-dispersion glass, a glass composition represented by patent document 1 is known.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2011-178571
Disclosure of Invention
However, the glass described in patent document 1 contains a large amount of GeO to promote high refractive index and high dispersion 2 Component (B) and Nb 2 O 5 Component (a) and Ta 2 O 5 The problem is that the production cost is increased by the high unit price of the material such as the component. Therefore, a wavelength (λ) exhibiting a spectral transmittance of 5% while having a high refractive index/high dispersion is expected to appear 5 ) Short and low in manufacturing cost.
In view of the above problems, an object of the present invention is to provide a wavelength (λ) having a high refractive index and a spectral transmittance of 5% 5 ) Short and low in production cost, and a preform and an optical element using the optical glass.
The present inventors have conducted extensive experimental studies to solve the above problems, and as a result, have found that La can be used in combination 2 O 3 Component (C), tiO 2 Adjusting SiO in conjunction with BaO component 2 Component (A) and (B) 2 O 3 Total amount of ingredients or TiO 2 /(TiO 2 + BaO mass ratio, a desired high refractive index and high dispersion, a suppressed manufacturing cost, and a wavelength (λ) of 5% spectral transmittance 5 ) Shortened, and the present invention has been completed.
Specifically, the present invention provides the following.
(1) An optical glass comprising, in mass% on an oxide basis,
comprises
More than 0 to 45.0 percent of La 2 O 3 Ingredients (A) and (B),
TiO more than 0-45.0% 2 Component (a) and
more than 0 to 40.0 percent of BaO,
and contains SiO 2 Component (A) and (B) 2 O 3 The total amount of the components is 5.0-30.0%,
TiO 2 /(TiO 2 + BaO) is 0.10 or more and 0.90 or less,
refractive index (n) d ) Is 1.90 or more, and has an Abbe number (v) d ) A wavelength (lambda) of 30.0 or less and a spectral transmittance of 5% 5 ) Is 400nm or less.
(2) The optical glass according to (1), wherein,
in terms of mass% based on the oxide,
SiO 2 0 to 30.0% of a component, and
B 2 O 3 the components are 0-30.0%.
(3) The optical glass according to (1) or (2), wherein,
in terms of mass% based on the oxide,
0 to 20.0 percent of ZnO,
Y 2 O 3 the components are 0 to 15.0 percent,
Nb 2 O 5 the components are 0 to 25.0 percent,
Yb 2 O 3 the component (a) is0 to 15.0%, and
Gd 2 O 3 the components are 0-15.0%.
(4) The optical glass according to any one of (1) to (3),
in terms of mass% based on the oxide,
(La 2 O 3 +Nb 2 O 5 +Gd 2 O 3 +Yb 2 O 3 ) The sum of the mass of (a) is more than 0% and 60.0% or less.
(5) The optical glass according to any one of (1) to (4),
in terms of mass% based on the oxide,
Ln 2 O 3 the total amount of the component (Ln is at least one selected from the group consisting of La, gd, Y and Yb) is more than 0% and 50.0% or less.
(6) The optical glass according to any one of (1) to (5),
based on the standard of the oxide,
TiO 2 the ratio of/BaO is more than 0 and less than 3.00.
(7) The optical glass according to any one of (1) to (6),
in terms of mass% based on the oxide,
Rn 2 the sum of the masses of O components (Rn represents 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),
in terms of mass% based on the oxide,
the sum of the mass of RO components (wherein R is at least one selected from the group consisting of Mg, ca, sr, ba and Zn) is more than 0% and 35.0% or less.
(9) The optical glass according to any one of (1) to (8),
contains, in mass% based on the oxide
ZrO 2 0 to 20.0 percent of component,
Nb 2 O 5 0 to 15.0 percent of component,
WO 3 0 to 10.0 percent of component,
Ta 2 O 5 0 to 10.0 percent of component,
0 to 15.0 percent of MgO component,
0 to 15.0 percent of CaO component,
0 to 15.0 percent of SrO,
Li 2 0 to 15.0 percent of O component,
Na 2 0 to 15.0 percent of O component,
K 2 0 to 15.0 percent of O component,
P 2 O 5 0 to 10.0 percent of component,
GeO 2 0 to 10.0 percent of component,
Al 2 O 3 0 to 15.0 percent of component,
Ga 2 O 3 0 to 15.0 percent of component,
Bi 2 O 3 0 to 10.0 percent of component,
TeO 2 0 to 10.0 percent of component,
SnO 2 0 to 3.0% of the component (A), and
Sb 2 O 3 0 to 1.0 percent of the components.
(10) A preform comprising the optical glass described in 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 comprising the optical element according to (11).
According to the present invention, it is possible to provide a wavelength (λ) exhibiting a spectral transmittance of 5% while having a high refractive index and a high dispersion 5 ) Short and inexpensive optical glass, 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 shows the partial dispersion ratio (. Theta.g, F) as the vertical axis and the Abbe number (v) d ) A schematic diagram of a normal line expressed by rectangular coordinates of a horizontal axis; and
FIG. 2 shows the partial dispersion ratio (. Theta.g, F) and Abbe number (. V.) of a glass of an example of the present invention d ) Schematic diagram of the relationship of (a).
Detailed Description
The optical glass of the present invention contains, in mass%, more than 0% to 45.0% of La 2 O 3 Component (I), tiO 0-45.0% 2 A component and more than 0 to 40.0% of BaO component, siO 2 Component (A) and (B) 2 O 3 The total amount of the components is 5.0-30.0%, and TiO 2 /(TiO 2 A mass ratio of + BaO of 0.10 to 0.90, a refractive index (n) d ) Is 1.90 or more, abbe number (v) d ) A wavelength (lambda) of 30.0 or less and a spectral transmittance of 5% 5 ) Is 400nm or less.
According to the invention, by using La together 2 O 3 Component (C) TiO 2 And BaO component, and the content of each component is adjusted to achieve high refractive index and high dispersion of the glass and to improve the stability of the glass. Thus, canCapable of providing a wavelength (lambda) exhibiting a spectral transmittance of 5% while having a high refractive index and a high dispersion 5 ) Short and inexpensive optical glass, and a preform and an optical element using the optical glass.
[ glass composition ]
The compositional ranges of the respective components constituting the optical glass of the present invention are described below. In this specification, unless otherwise specified, the contents of the respective components are expressed in mass% with respect to the total mass of the glass based on oxides. Here, "oxide basis" means that the composition of each component contained in the glass is represented by assuming that all of 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 during melting, with the total mass of the oxides being 100 mass%.
< essential Components, optional Components >
La 2 O 3 The component is a component which can increase the refractive index of the glass and reduce the dispersion when the content thereof is more than 0%. In particular by containing more than 0% of La 2 O 3 The component (b) is an essential component for obtaining a desired high refractive index. Thus, la 2 O 3 The lower limit of the content of the component (b) is preferably more than 0%, more preferably 3.0%, further preferably 15.0%, further preferably 20.0%, further preferably 25.0%, further more preferably 27.0%.
On the other hand, by mixing La 2 O 3 The content of the component (b) is 45.0% or less, whereby the devitrification resistance of the glass can be improved, the increase in the specific gravity of the glass can be suppressed, and the production cost can be reduced. Thus, la 2 O 3 The upper limit of the content of the component (b) is preferably 45.0%, more preferably 40.0%, still more preferably 38.0%, and still more preferably 37.0%.
La 2 O 3 La may be used as the component 2 O 3 、La(NO 3 ) 3 ·XH 2 O (X is an arbitrary integer), and the like as a raw material.
TiO 2 The component (A) can be contained in an amount of more than 0%The glass has a high refractive index, a low Abbe number, a high partial dispersion ratio, and a high devitrification resistance. Thus, tiO 2 The lower limit of the content of the component (b) is preferably more than 0%, preferably 5.0%, more preferably more than 10.0%, further preferably 15.0%, further preferably 18.0%, and further preferably more than 20.0%.
On the other hand, by mixing TiO 2 The content of the component (b) is 45.0% or less, and the coloring of the glass can be reduced and the visible light transmittance can be improved. In addition, the effect of TiO can be suppressed 2 Devitrification due to excessive content of the ingredient. Thus, tiO 2 The upper limit of the content of the component (b) is preferably 45.0%, more preferably 38.0%, still more preferably 32.0%, yet more preferably 27.0%, and yet more preferably 25.0%.
TiO 2 The component (C) may be TiO 2 And the like as a raw material.
The BaO component is an essential component which can improve the refractive index or devitrification resistance of the glass when the content thereof is more than 0%, and can improve the meltability of the glass raw material. 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 further preferably 10.0%.
On the other hand, by setting the content of the BaO component to 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%, further preferably 23.0%, and further preferably 20.0%.
BaCO can be used as BaO component 3 、Ba(NO 3 ) 2 And the like as a raw material.
B 2 O 3 Component (B) and SiO 2 The sum (mass sum) of the contents of the components is preferably 5.0% or more and 30.0% or less.
In particular, by setting the sum to 5.0% or more, B can be suppressed 2 O 3 Component (B) or SiO 2 The resistance to devitrification is reduced due to the shortage of the component. Therefore, mass sum of (B) 2 O 3 +SiO 2 ) Under (2) isThe limit is preferably 5.0%, more preferably 7.0%, and still more preferably 9.0%.
On the other hand, by setting the sum to 30.0% or less, a decrease in refractive index due to excessive contents of these components can be suppressed, and a desired high refractive index can be easily obtained. Therefore, mass sum of (B) 2 O 3 +SiO 2 ) The upper limit of (b) is preferably 30.0%, more preferably 23.0%, still more preferably 18.0%, and still more preferably 16.5%.
Here, tiO is 2 In relation to TiO 2 The ratio (mass ratio) of the sum of the contents of the component and the BaO component is preferably 0.10 or more. Thereby, a high partial dispersion ratio can be obtained while maintaining a high refractive index and a high dispersion. Therefore, mass ratio of TiO 2 /(TiO 2 The lower limit of + BaO) is preferably 0.10, more preferably 0.30, still more preferably 0.40, and still more preferably 0.45.
On the other hand, by setting the mass ratio to 0.90 or less, the coloring of the glass can be reduced, the visible light transmittance can be improved, and devitrification can be suppressed. Therefore, mass ratio of TiO 2 /(TiO 2 The upper limit of + BaO) is preferably 0.90, more preferably 0.80, still more preferably 0.73, and still more preferably 0.68.
SiO 2 The component (C) is an optional component which can improve the devitrification resistance when the content thereof is more than 0%. Thus, siO 2 The lower limit of the content of the component (b) is preferably more than 0%, more preferably more than 0.5%, still more preferably more than 1.0%, and still more preferably more than 2.0%.
On the other hand, by mixing SiO 2 The content of the component (C) is 30.0% or less, and SiO can be formed 2 The components are easily melted in the molten glass and are prevented from melting at high temperatures. SiO 2 2 The upper limit of the content of the component (b) is preferably 30.0%, more preferably 23.0%, still more preferably 16.0%, yet more preferably 11.0%, and yet more preferably 9.0%.
SiO 2 SiO may be used as the component 2 、K 2 SiF 6 、Na 2 SiF 6 And the like as a raw material.
B 2 O 3 The component (b) is an optional component which can form a network structure in the glass when the content thereof is more than 0%, promote stable glass formation, and improve resistance to devitrification. Thus, B 2 O 3 The lower limit of the content of the component (b) is preferably more than 0%, more preferably more than 0.5%, still more preferably more than 1.0%, and still more preferably more than 2.0%.
On the other hand, by mixing B 2 O 3 The content of the component (b) is 30.0% or less, and thus the decrease in refractive index, the abbe number, and the deterioration in chemical durability can be suppressed. Thus, B 2 O 3 The upper limit of the content of the component (b) is preferably 30.0% or less, more preferably 20.0%, even more preferably less than 15.0%, even more preferably 12.0%, and even more preferably less than 10.0%.
B 2 O 3 Component (b) may be H 3 BO 3 、Na 2 B 4 O 7 、Na 2 B 4 O 7 ·10H 2 O、BPO 4 And the like as a raw material.
The ZnO component is an optional component whose content is more than 0% and which can improve the meltability of the 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%, still more preferably more than 1.0%, and still more 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 increased, the occurrence of striae in the glass can be reduced. Therefore, the upper limit of the content of the ZnO component is preferably 20.0%, more preferably 15.0%, still more preferably 11.0%, and still more preferably 8.0%.
ZnO or ZnF can be used as the ZnO component 2 And the like as a raw material.
Y 2 O 3 The component (b) is an arbitrary component whose content is more than 0% and can suppress an increase in material cost of the glass.
By mixing Y 2 O 3 The content of the component is 15.0% or less, and the glass can be inhibitedThe lowering of the refractive index can reduce the abbe number and improve the devitrification resistance of the glass. Thus, Y 2 O 3 The upper limit of the content of the component (b) is preferably 15.0%, more preferably 10.0%, and still more preferably 5.0%.
Y 2 O 3 Component (B) may be Y 2 O 3 、YF 3 And the like as a raw material.
Nb 2 O 5 The component (b) is an arbitrary component whose content is more than 0% and can increase the refractive index of the glass and can improve resistance to devitrification. Thus, nb 2 O 5 The lower limit of the content of the component (b) is preferably more than 0%, more preferably 2.0%, and still more preferably 4.0%.
On the other hand, by adding Nb 2 O 5 The content of the component is 25.0% or less, and Nb can be prevented 2 O 5 The reduction in devitrification resistance or the reduction in visible light transmittance of the glass due to the excessive content of the component can be suppressed, and the increase in material cost of the glass can be suppressed. Thus, nb 2 O 5 The upper limit of the content of the component (b) is preferably 25.0%, more preferably 20.0%, still more preferably 16.0%, and yet more preferably 13.0%.
Nb 2 O 5 Nb is used as a component 2 O 5 And the like as a raw material.
Yb 2 O 3 The component (b) is an arbitrary component which can increase the refractive index of the glass when the content thereof is more than 0%.
On the other hand, by mixing Yb 2 O 3 When the content of the component (C) is 15.0% or less, the glass can have improved resistance to devitrification and a small Abbe number. Thus, yb 2 O 3 The upper limit of the content of the component (b) is preferably 15.0%, more preferably 10.0%, and still more preferably 5.0%.
Yb 2 O 3 Yb may be used as the component 2 O 3 And the like as a raw material.
Gd 2 O 3 The component (b) is an arbitrary component whose content is more than 0% and which can increase the refractive index of the glass and can increase the Abbe number.
On the other hand, by mixing rare earthGd, a particularly expensive element 2 O 3 The component is reduced to below 15.0%, the material cost of the glass can be reduced, and the optical glass with lower cost can be manufactured. In addition, this can suppress an increase in the abbe number of the glass more than necessary. Thus, gd 2 O 3 The upper limit of the content of the component (b) is preferably 15.0%, more preferably 10.0%, and still more preferably 5.0%.
Gd 2 O 3 Gd may be used as the component 2 O 3 、GdF 3 And the like as a raw material.
Further, in the optical glass of the present invention, la 2 O 3 Component (B) and Nb 2 O 5 Component (c) Gd 2 O 3 Component (b) and Yb 2 O 3 The sum (mass sum) of the contents of (c) 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, mass sum (La) 2 O 3 +Nb 2 O 5 +Gd 2 O 3 +Yb 2 O 3 ) The upper limit of (b) is preferably 60.0%, more preferably 57.0%, even more preferably 53.0%, even more preferably 49.0%, and even more preferably 47.0%.
On the other hand, by containing the sum of the mass of these components in an amount of more than 0%, a desired high refractive index can be obtained. Therefore, mass sum (La) 2 O 3 +Nb 2 O 5 +Gd 2 O 3 +Yb 2 O 3 ) The lower limit of (b) is preferably more than 0%, more preferably 10.0%, further preferably 20.0%, further preferably 25.0%, still further preferably 30.0%, still further preferably 35.0%.
Ln 2 O 3 The sum (mass sum) of the contents of the 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 sum of the masses to more 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. Thus, ln 2 O 3 The lower limit of the mass sum of the contents of the components is preferably more than 0%, more preferably 1.0%, further preferably 3.0%, and further preferably 5.0%.
On the other hand, by setting the sum of the masses to 50.0% or less, the devitrification resistance can be improved and the abbe number can be reduced. Thus, ln 2 O 3 The upper limit of the sum of the contents of the components is preferably 50.0% by mass, more preferably less than 40.0% by mass, still more preferably 30.0% by mass, and yet more preferably 25.0% by mass.
Here, tiO is 2 Content of (A) and La 2 O 3 Component (B) and Nb 2 O 5 Component (b) Gd 2 O 3 Component (b) and Yb 2 O 3 The ratio (mass ratio) of the sum of the contents of the components is preferably greater than 0. Thus, a high partial dispersion ratio can be obtained while maintaining a high refractive index and high dispersion, and the manufacturing cost can be reduced. Therefore, mass ratio of TiO 2 /(La 2 O 3 +Nb 2 O 5 +Gd 2 O 3 +Yb 2 O 3 ) The lower limit of (b) is preferably more than 0, more preferably 0.10, still more preferably 0.20, and 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, mass ratio of TiO 2 /(La 2 O 3 +Nb 2 O 5 +Gd 2 O 3 +Yb 2 O 3 ) The upper limit of (b) is preferably 2.00, more preferably 1.00, still more preferably 0.80, and still more preferably 0.66.
Here, tiO is 2 The ratio (mass ratio) of the content of the component to the content of the BaO component is preferably more than 0. Thereby, a high partial dispersion ratio can be obtained while maintaining a high refractive index and a high dispersion. Mass ratio of TiO 2 The lower limit of/BaO is preferably more than 0, more preferably 0.10, still more preferably 0.40, and 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, mass ratio of TiO 2 The upper limit of/BaO is preferably 3.00, more preferably 2.00, and further preferably 1.60.
Here, tiO is 2 Component (A) and WO 3 The ratio (mass ratio) of the sum of the contents of the components to the content of the BaO component is preferably greater than 0. This makes it possible to obtain a high partial dispersion ratio while maintaining a high refractive index and high dispersion, and to improve resistance to devitrification. Therefore, mass ratio (TiO) 2 +WO 3 ) The lower limit of/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, mass ratio (TiO) 2 +WO 3 ) The upper limit of/BaO is preferably 3.00, more preferably 2.50, and further preferably 1.90.
TiO 2 Component (B) and Nb 2 O 5 The sum (mass sum) of the contents of the components is preferably more than 0%. This can increase the refractive index/dispersion and improve the resistance to devitrification. Thus, mass sum of (TiO) 2 +Nb 2 O 5 ) The lower limit of (b) 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, when the content of the sum is 60.0% or less, the coloring of the glass can be reduced, the visible light transmittance can be improved, and the devitrification can be suppressed. Therefore, the upper limit of the sum of mass content is preferably 60.0%, more preferably 50.0%, even more preferably 45.0%, even more preferably 40.0%, even more preferably 35.0%, even more preferably 33.0%.
Rn 2 The total amount of the O component (in the formula, rn is one or more selected from the group consisting of Li, na, K, and Cs) is preferably 15.0% or less. This can suppress a decrease in the refractive index of the glass and improve resistance to devitrification. Thus, rn 2 The upper limit of the sum of the O contents is preferably 15.0%, more preferably 10.0%, still more preferably less than 5.0%, and yet more preferably less than 1%.0％。
The sum (mass sum) of the contents of RO components (in the formula, 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 RO components by mass is preferably 35.0%, more preferably 30.0%, even more preferably 27.0%, even more preferably less than 23.0%, and even more preferably 20.0%.
On the other hand, when the sum is more than 0%, the meltability of the glass raw material and the stability of the glass can be improved. Therefore, the lower limit of the total content of the RO component is preferably more than 0%, more preferably 4.0%, further preferably 7.0%, and further preferably more than 9.0%.
ZrO 2 When the content of the component (b) is more than 0%, the glass can have a high refractive index and a low dispersion, and the glass can have improved devitrification resistance. Thus, zrO 2 The lower limit of the content of the component (b) is preferably more than 0%, more preferably 0.5%, and still more preferably 1.0%.
On the other hand, by reacting ZrO 2 The component is 20.0% or less, and ZrO due to ZrO can be inhibited 2 The excessive content of the component(s) lowers the devitrification resistance of the glass and increases the Abbe number more than necessary. Thus, zrO 2 The upper limit of the content of the component (b) is preferably 20.0%, more preferably 16.0%, even more preferably 12.0%, even more preferably 9.0%, and even more preferably less than 6.5%.
ZrO 2 ZrO may be used as the component 2 、ZrF 4 And the like as a raw material.
WO 3 When the content of the component is more than 0%, the refractive index can be increased while reducing coloring of the glass by other high refractive index components, the partial dispersion ratio can be increased, and the devitrification resistance of the glass can be improved. In addition, WO 3 The component (c) is also a component capable of lowering the glass transition temperature. Thus, WO 3 The lower limit of the content of the component (b) is preferably more than 0%, more preferably 0.1%, still more preferably 0.2%, and yet more preferably 0.3％。
On the other hand, by mixing WO 3 The content of component (A) is 10.0% or less, and WO can be reduced 3 The coloring of the glass by the component improves the visible light transmittance. Thus, WO 3 The upper limit of the content of the component (b) is preferably 10.0%, more preferably 5.0%, and still more preferably 3.0%.
WO 3 The components can be WO 3 And the like as a raw material.
Ta 2 O 5 The component (b) is an arbitrary component whose content is more than 0% and can increase the refractive index of the glass and can improve resistance to devitrification.
On the other hand, by mixing expensive Ta 2 O 5 The composition is 10.0% or less, and the material cost of the glass can be reduced, so that the optical glass can be produced at a lower cost. In addition, by mixing Ta 2 O 5 The content of the component (b) is 10.0% or less, and the melting temperature of the raw material can be lowered, and the energy required for melting the raw material can be reduced, thereby reducing the production cost of the optical glass. Thus, ta 2 O 5 The upper limit of the content of the component (b) is preferably 10.0%, more preferably 8.0%, and still more preferably 5.0%. In particular, ta is used from the viewpoint of producing a more inexpensive optical glass 2 O 5 The upper limit of the content of the component (b) is preferably 4.0%, more preferably 3.0%, even more preferably less than 1.0%, and most preferably not contained.
Ta 2 O 5 Ta may be used as the component 2 O 5 And the like as a raw material.
The MgO component is an arbitrary component that can improve the melting property of the glass raw material or the devitrification resistance of the glass when the content thereof is more than 0%.
On the other hand, by setting the content of the MgO component to 15.0% or less, it is possible to suppress a decrease in refractive index and a decrease in devitrification resistance due to excessive content of these components. Therefore, the upper limit of the content of the MgO component is preferably 15.0%, more preferably 10.0%, and still more preferably 5.0%.
MgCO may be used as MgO component 3 、MgF 2 And the like as a raw material.
The CaO component is an arbitrary component that can improve the refractive index or devitrification resistance of the glass when the content thereof is more than 0%, 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%, further preferably 1.5%, and further preferably 3.0%.
On the other hand, by setting the content of the CaO 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 CaO component is preferably 15.0%, more preferably 10.0%, and further preferably 5.0%.
CaCO may be used as CaO component 3 、CaF 2 And the like as a raw material.
The SrO component is an arbitrary component that can improve the refractive index or devitrification resistance of the glass when the content thereof is more than 0%, and can improve the meltability of the glass raw material. Therefore, the lower limit of the SrO content is preferably more than 0%, more preferably 0.5%, still more preferably 1.5%, and still more 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 still more preferably 5.0%.
SrCO can be used as SrO component 3 、SrF 2 And the like as a raw material.
Li 2 O component and Na 2 O component and K 2 The content of at least one of the components O is an arbitrary component which can improve the meltability of the glass when it is more than 0%. In particular, K 2 The O component is also a component capable of further improving the partial dispersion ratio of the glass.
On the other hand, by reducing Li 2 O component and Na 2 O component or K 2 The content of the O component can suppress a decrease in the refractive index of the glass and can reduce devitrification. In particular, by reducing Li 2 The content of the O component can suppress a decrease in the partial dispersion ratio of the glass. Thus, li 2 O component and Na 2 O component and K 2 At least one of O componentsThe content of the element is preferably 15.0%, more preferably less than 10.0%, still more preferably less than 5.0%, and still more preferably less than 1.0%.
Li 2 O component and Na 2 O component and K 2 Li may be used as the O component 2 CO 3 、LiNO 3 、LiF、Na 2 CO 3 、NaNO 3 、NaF、Na 2 SiF 6 、K 2 CO 3 、KNO 3 、KF、KHF 2 、K 2 SiF 6 And the like as a raw material.
P 2 O 5 The component (b) is an optional component which can improve the devitrification resistance of the glass when the content is more than 0%. In particular, by reacting P 2 O 5 When the content of the component (B) is 10.0% or less, the deterioration of chemical durability, particularly the deterioration of water resistance of the glass can be suppressed. Thus, P 2 O 5 The upper limit of the content of the component (b) is preferably 10.0%, more preferably 5.0%, and still more preferably 3.0%.
P 2 O 5 Al (PO) can be used as the component 3 ) 3 、Ca(PO 3 ) 2 、Ba(PO 3 ) 2 、BPO 4 、H 3 PO 4 And the like as a raw material.
GeO 2 The component (b) is an arbitrary component whose content is more than 0% and can increase the refractive index of the glass and improve the devitrification resistance of the glass. However, due to GeO 2 The raw material (A) is expensive, and if the amount of the raw material (A) is large, the material cost is increased, and the Gd reduction is impaired 2 O 3 Component (A) or Ta 2 O 5 Cost reduction effect due to the components. Thus, geO 2 The upper limit of the content of the component (b) is preferably 10.0%, more preferably 5.0%, even more preferably 1.0%, and most preferably not contained.
GeO 2 GeO may be used as the component 2 And the like as a raw material.
Al 2 O 3 Component (A) and Ga 2 O 3 The component (b) is an optional component whose content is more than 0% and which can improve the chemical durability of the glass and the devitrification resistance of the glass.
On the other hand, by mixing Al 2 O 3 Component (A) and Ga 2 O 3 The content of each component is 15.0% or less, and the decrease in devitrification resistance of the glass due to excessive content of these components can be suppressed. Thus, al 2 O 3 Component (A) and Ga 2 O 3 The upper limit of the content of each component is preferably 15.0%, more preferably 8.0%, and still more preferably 3.0%.
Al 2 O 3 Component (A) and Ga 2 O 3 Al as the component 2 O 3 、Al(OH) 3 、AlF 3 、Ga 2 O 3 、Ga(OH) 3 And the like as a raw material.
Bi 2 O 3 The component (b) is an arbitrary component which can increase the refractive index and lower the glass transition temperature when the content thereof is more than 0%.
On the other hand, by adding Bi 2 O 3 When the content of the component (b) is 10.0% or less, the devitrification resistance of the glass can be improved, and the visible light transmittance can be improved by reducing the coloring of the glass. Thus, bi 2 O 3 The upper limit of the content of the component (b) is preferably 10.0%, more preferably 5.0%, and still more preferably 3.0%.
Bi 2 O 3 Bi as component (c) may be used 2 O 3 And the like as a raw material.
TeO 2 The component (b) is an arbitrary component which can increase the refractive index and lower the glass transition temperature when the content thereof is more than 0%.
However, when a glass raw material is charged into a platinum crucible or a melting tank in which a portion in contact with molten glass is made of platinum and melted, teO exists 2 The composition may be alloyed with platinum. Thus, teO 2 The upper limit of the content of the component (b) is preferably 10.0%, more preferably 5.0%, even more preferably 3.0%, and even more preferably not contained.
TeO 2 The component can be TeO 2 And the like as a raw material.
SnO 2 When the content of the component (B) is more than 0%, oxidation of the molten glass can be reducedAnd an optional component which makes the molten glass clear and makes the light transmittance of the glass less likely to deteriorate.
On the other hand, by reacting SnO 2 When the content of the 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, because of SnO 2 The alloying of the components with melting equipment (particularly noble metals such as Pt) is reduced, and the service life of the melting equipment can be prolonged. Thus, snO 2 The content of the component (b) is preferably 3.0% or less, more preferably less than 2.0%, even more preferably less than 1.0%, and even more preferably not contained.
SnO 2 SnO can be used as a component 2 、SnO 2 、SnF 2 、SnF 4 And the like as a raw material.
Sb 2 O 3 The component (b) is an arbitrary component capable of defoaming the molten glass when the content thereof is more than 0%.
On the other hand, by mixing Sb 2 O 3 The content of the component (c) is 1.0% or less, so that excessive foaming can be prevented from occurring and the alloying with a melting apparatus (particularly, a noble metal such as Pt) can be reduced. Thus, sb 2 O 3 The content of the component (b) is preferably 1.0% or less, more preferably less than 0.5%, still more preferably less than 0.3%, and still more preferably less than 0.1%.
Sb 2 O 3 Sb as a component 2 O 3 、Sb 2 O 5 、Na 2 H 2 Sb 2 O 7 ·5H 2 O and the like as raw materials.
Further, the component for refining and defoaming the glass is not limited to the above-mentioned Sb 2 O 3 As the component (b), a clarifier, a defoaming agent or a combination thereof known in the glass production field can be used.
The component F is an optional component which, when the content thereof is more than 0%, can increase the Abbe number of the glass, lower the glass transition temperature, and improve resistance to devitrification.
However, if the content of the F component, that is, the total amount of F which is a fluoride partially or entirely substituted with one or two or more oxides of each of the above metal elements, is more than 10.0%, the amount of volatilization of the F component increases, and therefore it is difficult to obtain a stable optical constant, and it is difficult to obtain a homogeneous glass. In addition, the abbe number increases more than necessary.
Therefore, the content of the F component is preferably 10.0% or less, more preferably less than 5.0%, even more preferably less than 3.0%, even more preferably less than 1.0%, and even more preferably not contained.
< ingredients not to be contained >
Next, components that should not be contained in the optical glass of the present invention and components that are not preferably contained therein will be described.
In the optical glass of the present invention, other components may be added as necessary as long as the characteristics of the glass of the present invention are not impaired. However, geO 2 The component (B) is preferably not substantially contained because it improves the dispersibility of the glass.
In addition, since various transition metal components other than Ti, zr, nb, W, la, gd, Y, yb, lu, for example, hf, Ν, cr, mn, fe, co, ni, cu, ag, mo, ce, nd, and the like have properties of coloring the glass and absorbing light of a specific wavelength in the visible light region when contained individually or in combination, even a small amount thereof is preferable that they are not substantially contained in optical glass using a wavelength in the visible light region.
Further, lead compounds such As PbO and As 2 O 3 In recent years, arsenic compounds such as these and components such as Th, cd, tl, os, be, and Se tend to Be avoided as harmful chemical substances, 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 of the glass. Therefore, when attention is paid to the influence on the environment, it is preferable that these components are not substantially contained except for unavoidable mixing. Thus, the optical glass does not substantially contain substances contaminating the environment. Therefore, the optical glass can be manufactured, processed and discarded without taking special measures for environmental measures.
[ production 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 the respective components are 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, and 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, after the steps of stirring to be uniform and defoaming, the temperature is lowered to 1300 ℃ or less, and then stirring at the final stage is performed to remove streaks, and molding is performed using a molding die, thereby producing the alloy. Here, as a method of obtaining glass molded by using a molding die, there are a method of flowing molten glass into one end of the molding die and simultaneously drawing out molded glass from the other end of the molding die, and a method of casting molten glass into a die and slowly cooling the same.
[ Properties ]
The optical glass of the present invention preferably has a high refractive index and a high dispersion.
In particular, the refractive index (n) of the optical glass of the present invention d ) The lower limit of (b) 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. Further, the Abbe number (v) of the optical glass of the present invention d ) The lower limit of (b) 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 amount of light refraction can be obtained even if the optical element is thinned. In addition, by having such a high dispersion, when combined with an optical element having a low dispersion (high abbe number), for example, high imaging characteristics and the like can be achieved.
Therefore, the optical glass of the present invention is useful in 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 a high visible light transmittance, and particularly has a high transmittance of light on the short wavelength side of visible light, and is less colored.
In particular, the optical glass of the present invention exhibits a wavelength (. Lamda.) of a spectral transmittance of 70% in a sample having a thickness of 10mm, as represented by the transmittance of the glass 70 ) The upper limit of (B) is preferably 500nm, more preferably 490nm, and still more preferably 480nm.
In addition, in the optical glass of the present invention, the shortest wavelength (. Lamda.) showing a spectral transmittance of 5% in a sample having a thickness of 10mm 5 ) The upper limit of (B) is preferably 400nm, more preferably 390nm.
Accordingly, 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, and therefore, the optical glass can be preferably used for an optical element that transmits light, such as a lens.
The optical glass of the present invention preferably has a high partial dispersion ratio (θ g, F). More specifically, the lower limit of the partial dispersion ratio (θ g, F) of the optical glass of the present invention is preferably 0.570, more preferably 0.580, still more preferably 0.595, still more preferably 0.605, and yet still more preferably 0.612.
In addition, the optical glass of the present invention has a partial dispersion ratio (θ g, F) and an Abbe number (v) d ) The relationship between them preferably satisfies (-0.00162 v) d +0.645)≤(θg，F)≤(-0.00162v d + 0.680). Thus, since optical glass having a small partial dispersion ratio (θ g, F) can be obtained, the optical glass can contribute to the reduction of chromatic aberration of an optical element or the like.
Therefore, the lower limit of the partial dispersion ratio (θ g, F) of the optical glass of the present 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 (θ g, F) of the optical glass of the present invention is preferably (-0.00162 v) d + 0.675), more preferably (-0.00162 v) d +0.670)。
In a rectangular coordinate with the vertical axis of the partial dispersion ratio and the horizontal axis of the Abbe number, the above-mentioned partial dispersion ratio (. Theta.g, F) and Abbe number (. V) d ) Is represented by a straight line parallel to the normal. The normal line represents the partial dispersion ratio (. Theta.g, F) and Abbe of a conventional glassNumber (v) d ) The linear relationship is observed in the form of Abbe number (v) with partial dispersion ratio (θ g, F) as vertical axis d ) On a rectangular coordinate on the abscissa, the line obtained by connecting two points obtained by plotting the partial dispersion ratio and the abbe number of NSL7 and PBM2 is shown (see fig. 1). Further, the relationship between the partial dispersion ratio and the abbe number of the conventionally known glass substantially overlaps with the normal line.
Here, NSL7 and PBM2 are optical glasses manufactured by Korea, inc., and the Abbe number (v) of PBM2 d ) Is 36.3, the partial dispersion ratio (. Theta.g, F) is 0.5828, and the Abbe number (v) of NSL7 d ) Is 60.5, and the partial dispersion ratio (θ g, F) is 0.5436.
[ preform and optical element ]
The glass shaped body can be produced from the optical glass produced by, for example, grinding or press molding such as reheat press molding or precision press molding. That is, the glass molded body can be produced by subjecting the optical glass to mechanical processing such as grinding and polishing, or by subjecting a preform made of the optical glass to reheat press molding and then to polishing, or by subjecting a preform made by polishing or a preform molded by known float molding or the like to precision press molding. It should be noted that the method for producing the glass shaped body is not limited to the above-described 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 a glass molded body having a large diameter can be formed by improving the stability of the glass, it is possible to realize high-definition and high-precision imaging characteristics and projection characteristics when an optical device such as a camera or a projector is used while increasing the size of the optical device.
Examples
Glass compositions of examples (Nos. 1 to 52) of the present invention and refractive indices (n) of these glasses d ) Abbe number (v) d ) Transmittance (λ) 5 、λ 70 ) And partial colorThe values of the scattering ratios (. Theta.g, F) are shown in tables 1 to 10. 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 glasses of the examples, as the raw materials of the respective components, high-purity raw materials used for general optical glasses such as oxides, hydroxides, carbonates, nitrates, fluorides, hydroxides, metaphosphoric acid compounds, etc. corresponding to the respective raw materials were selected, weighed and uniformly mixed, put into a platinum crucible, melted for 2.5 hours at a temperature ranging from 1280 to 1340 ℃ by an electric furnace, and when the glass raw materials were melted, the melted glass raw materials were defoamed by stirring, cooled to 1180 to 1250 ℃, stirred again to be uniform, and then cast into a mold, slowly cooled, and made into glasses.
Refractive index (n) of glasses of examples d ) And Abbe number (v) d ) Expressed as a measurement of the d-line (587.56 nm) relative to a helium lamp. Further, the refractive index (n) of the d-line with respect to the F-line (486.13 nm) of the hydrogen lamp was used F ) Refractive index (n) with respect to C line (656.27 nm) C ) According to Abbe number (v) d )＝[(n d -1)/(n F -n C )]To calculate the Abbe number (v) d )。
Measurement of refractive index n in C line (wavelength 656.27 nm) C Refractive index n in F line (wavelength 486.13 nm) F Refractive index n in g line (wavelength 435.835 nm) g According to (θ g, F) = (n) g -n F )/(n F -n C ) The partial dispersion ratio is calculated by the equation of (a).
The transmittance of the glass of the examples was measured according to the Japanese optical Nitri Industrial Standard JOGIS 02-2003. In the present invention, the presence or absence of coloring 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 was measured for a parallel-faced polished article having a thickness of 10. + -. 0.1mm by JIS Z8722, and the value of λ was determined 5 (wavelength at 5% transmittance) and λ 70 (wavelength at which the transmittance is 70%).
The glass used in the measurement was treated in a slow cooling furnace at a slow cooling rate of-25 ℃/hr.
TABLE 1
wt％ 1 2 3 4 5 6
SiO 2 6.01 6.01 6.01 5.43 5.01 5.01
B 2 O 3 6.95 6.95 6.95 7.60 6.95 6.95
La 2 O 3 31.99 32.00 33.27 31.72 32.00 33.98
Y 2 O 3
Gd 2 O 3
Yb 2 O 3
ZrO 2 6.39 6.39 6.39 6.37 6.39 4.39
TiO 2 21.70 21.70 21.70 21.89 22.70 21.70
Nb 2 O 5 7.31 7.31 7.31 8.78 7.31 8.31
WO 3 0.77 0.77 0.77 0.77 0.77 0.77
ZnO 1.27 1.27 1.27 1.27
Li 2 O
Na 2 O
K 2 O
MgO
CaO
SrO
BaO 17.60 17.60 17.60 17.45 17.60 17.60
Sb 2 O 3 0.01 0.00 0.00 0.00 0.00 0.02
Total up to 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
Rn 2 O 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
n d 2.012 2.012 2.012 2.018 2.025 2.020
v d 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
λ 70 447 448 447 459 451 454
λ 5 373 372 372 375 373 374
TABLE 2
wt％ 7 8 9 10 11 12
SiO 2 5.01 5.51 5.51 5.51 5.51 5.51
B 2 O 3 6.95 7.45 7.45 7.45 7.45 7.45
La 2 O 3 32.48 29.48 30.08 30.08 30.08 29.58
Y 2 O 3
Gd 2 O 3
Yb 2 O 3
ZrO 2 5.89 5.89 5.89 5.89 5.89 5.79
TiO 2 21.70 21.70 21.70 21.70 21.70 21.70
Nb 2 O 5 8.31 10.31 10.31 10.61 10.61 10.31
WO 3 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
Li 2 O
Na 2 O
K 2 O
MgO
CaO
SrO
BaO 17.60 17.60 17.60 17.30 14.30 17.60
Sb 2 O 3 0.02 0.02 0.02 0.02 0.02 0.02
Total up to 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
Rn 2 O 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
n d 2.022 2.021 2.021 2.023 2.027 2.020
v d 24.6 24.2 24.2 24.1 24.0 24.2
θg,F 0.6157
λ 70 468 459 457.5 463 462 467
λ 5 376 377 377 377.5 378 378
TABLE 3
wt％ 13 14 15
SiO 2 5.51 5.51 5.51
B 2 O 3 7.45 7.45 7.45
La 2 O 3 31.48 29.48 33.48
Y 2 O 3
Gd 2 O 3
Yb 2 O 3
ZrO 2 5.89 5.89 5.89
TiO 2 21.70 21.70 21.70
Nb 2 O 5 10.31 10.31 10.31
WO 3 0.77 0.77 0.77
ZnO 1.27 1.27 1.27
Li 2 O
Na 2 O
K 2 O
MgO
CaO
SrO
BaO 15.60 17.60 13.60
Sb 2 O 3 0.02 0.02 0.02
Total up to 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
Rn 2 O 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
n d 2.026 2.021 2.031
v d 24.2 24.2 24.2
θg,F
λ 70 467 467 470
λ 5 379 378 380
TABLE 4
wt％ 16 17 18 19 20 21
SiO 2 6.01 6.01 6.01 6.01 6.01 6.01
B 2 O 3 7.70 7.70 7.70 7.70 7.70 7.70
La 2 O 3 33.03 33.03 33.03 32.53 33.53 33.03
Y 2 O 3
Gd 2 O 3
Yb 2 O 3
ZrO 2 6.39 6.39 6.39 6.89 5.89 6.39
TiO 2 20.90 20.90 20.90 20.90 20.90 20.90
Nb 2 O 5 6.91 7.31 6.71 6.71 6.71 6.91
WO 3 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
Li 2 O
Na 2 O
K 2 O
MgO
CaO
SrO
BaO 17.00 16.60 17.20 17.20 17.20 17.00
Sb 2 O 3 0.02 0.02 0.02 0.02 0.02 0.02
Total up to 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
Rn 2 O 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
n d 2.001 2.003 2.000 2.001 1.999 2.001
v d 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
λ 70 446 450 458 451 450 449
λ 5 373 374 374 373 373 373
TABLE 5
wt％ 22 23 24 25 26 27
SiO 2 6.01 6.01 6.01 6.01 6.01 6.01
B 2 O 3 7.70 7.70 7.70 7.70 7.70 7.70
La 2 O 3 33.03 33.03 33.03 33.03 33.03 38.03
Y 2 O 3
Gd 2 O 3
Yb 2 O 3
ZrO 2 6.39 6.39 6.39 6.39 6.39 6.39
TiO 2 20.90 20.90 20.90 20.90 20.90 20.90
Nb 2 O 5 6.91 6.91 6.91 6.91 6.91 6.91
WO 3 0.77 0.77 0.77 0.77 0.77 0.77
ZnO 6.27 0.77 2.27 4.27 1.27
Li 2 O
Na 2 O
K 2 O
MgO
CaO
SrO
BaO 18.27 12.00 17.50 16.00 14.00 12.00
Sb 2 O 3 0.02 0.02 0.02 0.02 0.02 0.02
Total up to 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
Rn 2 O 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
n d 1.998 2.009 2.000 2.003 2.006 2.014
v d 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
λ 70 462 459 451 459 453 454
λ 5 375 375 373 375 374 375
TABLE 6
wt％ 28 29 30 31 32 33
SiO 2 6.01 6.01 6.01 6.01 6.01 6.01
B 2 O 3 7.70 7.70 7.70 7.70 7.70 7.70
La 2 O 3 34.03 36.03 34.83 34.83 34.83 34.83
Y 2 O 3
Gd 2 O 3
Yb 2 O 3
ZrO 2 6.39 6.39 6.39 6.39 6.39 6.39
TiO 2 20.90 20.90 20.10 20.10 20.10 20.10
Nb 2 O 5 6.91 6.91 6.91 5.91 6.91 5.91
WO 3 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
Li 2 O
Na 2 O
K 2 O
MgO
CaO
SrO
BaO 16.00 14.00 16.00 16.00 16.00 16.00
Sb 2 O 3 0.02 0.02 0.02 0.02 0.02 0.02
Total up to 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
Rn 2 O 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
n d 2.003 2.008 1.999 1.999 1.999 1.999
v d 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
λ 70 453 451 442 445
λ 5 374 374 372 372
TABLE 7
wt％ 34 35 36 37 38 39
SiO 2 6.01 6.01 6.01 6.01 6.01 6.01
B 2 O 3 7.70 7.70 7.70 7.70 7.70 7.70
La 2 O 3 34.84 34.84 34.84 34.14 33.64 34.64
Y 2 O 3
Gd 2 O 3
Yb 2 O 3
ZrO 2 6.39 6.39 6.39 6.39 6.89 5.89
TiO 2 20.10 20.10 20.10 20.80 20.80 20.80
Nb 2 O 5 6.91 6.91 6.91 6.91 6.91 6.91
WO 3 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
Li 2 O
Na 2 O
K 2 O
MgO
CaO
SrO
BaO 16.00 16.00 16.00 16.00 16.00 16.00
Sb 2 O 3 0.01 0.01 0.01 0.01 0.01 0.01
Total up to 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
Rn 2 O 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
n d 1.999 1.999 1.999 2.003 2.003 2.002
v d 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
λ 70 444.5 454 448.5
λ 5 371.5 373 372
TABLE 8
wt％ 40 41 42 43 44 45
SiO 2 6.21 6.01 6.01 6.01 6.01 6.01
B 2 O 3 7.85 8.02 7.70 8.02 8.02 8.02
La 2 O 3 33.33 33.82 34.34 33.83 33.83 33.83
Y 2 O 3
Gd 2 O 3
Yb 2 O 3
ZrO 2 6.39 6.39 6.19 6.39 6.39 6.39
TiO 2 20.90 21.10 20.80 21.10 21.10 21.10
Nb 2 O 5 6.91 6.61 6.91 6.61 6.61 6.61
WO 3 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
Li 2 O
Na 2 O
K 2 O
MgO
CaO
SrO
BaO 16.35 16.00 16.00 16.00 16.00 16.00
Sb 2 O 3 0.02 0.01 0.01 0.00 0.00 0.00
Total up to 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
Rn 2 O 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
n d 1.999 2.001 2.002 2.000 2.001 2.001
v d 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
λ 70 460 447 447 450 452
λ 5 375 372 372 372 373
TABLE 9
wt％ 46 47 48 49 50 51
SiO 2 6.21 6.12 6.63 7.87 6.55 8.14
B 2 O 3 7.85 8.02 10.10 10.02 9.98 10.43
La 2 O 3 33.41 33.73 41.27 37.39 31.49 36.13
Y 2 O 3
Gd 2 O 3
Yb 2 O 3
ZrO 2 6.39 6.39 6.37 6.68 5.51 6.85
TiO 2 20.83 21.08 16.68 18.48 14.30 16.76
Nb 2 O 5 6.91 6.61 6.34 5.56 13.88 2.39
WO 3 0.77 0.77 0.82 5.19 2.48
ZnO 1.27 1.27 1.36 1.61 1.34 2.20
Li 2 O
Na 2 O
K 2 O
MgO
CaO
SrO
BaO 16.35 16.00 10.43 12.38 11.75 14.61
Sb 2 O 3 0.01 0.01 0.01 0.01 0.01 0.01
Total up to 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
Rn 2 O 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
n d 1.999 2.000 1.968 1.961 1.976 1.934
v d 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
λ 70 455 444 440 428 436 420
λ 5 375 372 369 369 373 367
Watch 10
wt％ 52
SiO 2 6.21
B 2 O 3 7.85
La 2 O 3 33.41
Y 2 O 3
Gd 2 O 3
YbO3
ZrO 2 6.39
TiO 2 20.83
Nb 2 O 5 6.91
WO 3 0.77
ZnO 1.27
Li 2 O 0.10
Na 2 O
K 2 O
MgO
CaO
SrO
BaO 16.35
Sb 2 O 3
Total up to 100.08
Si+B 14.06
Ti/(Ti+Ba) 0.56
La+Nb+Gd+Yb 40.32
Ti/Ba 1.27
Rn 2 O 0.10
RO 16.35
Ln 33.41
Ti+Nb 27.74
(Ti+W)/Ba 1.32
La/(Nb+Gd+Yb) 4.83
n d 1.999
v d 25.5
θg,F 0.6130
λ 70 449
λ 5 372
As shown in the table, the optical glasses of the examples of the present invention are all the ones having the refractive index (n) d ) Is 1.90 or more, and the refractive index (n) d ) Is 2.20 or less, more specifically 2.10 or less, and is within a desired range.
In addition, the optical glasses of the examples of the present invention all have the Abbe number (v) d ) Is 30.0 or less, more specifically 28.0 or less, and the Abbe number (v) d ) Is 15.0 or more, more specifically 20.0 or more, all of which are within a desired range.
In addition, λ of the optical glass of the embodiment of the present invention 70 (wavelength at a transmittance of 70%) is 500nm or less, more specifically 490nm or less. Further, λ of the optical glass of the embodiment of the present invention 5 (wavelength at a transmittance of 5%) is 400nm or less, more specifically 390nm or less.
In addition, the optical glasses of the examples of the present invention all had a partial dispersion ratio (θ g, F) (-0.00162 v) d + 0.645), more particularly (-0.00162 v) d + 0.650) or more. In contrast, the optical glass of the examples of the present invention had a partial dispersion ratio of (-0.00162 v) d + 0.680), more particularly (-0.00162 v) d + 0.670) or less. From this, it is understood that these partial dispersion ratios (θ g, F) are within desired ranges.
Therefore, it is clear that the optical glass according to the embodiment of the present invention is easy to manufacture and is less colored while the refractive index and the abbe number thereof are within desired ranges.
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 lens and prism shapes. Further, a precision press-molding preform was formed using the optical glass of the embodiment of the present invention, and the precision press-molding preform was subjected to precision press-molding. In either case, the glass after heat softening is free from problems such as opalescence and devitrification, and can be stably processed into various lens and prism shapes.
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 may be made therein by those skilled in the art without departing from the spirit and scope of the invention.

Claims (10)

1. An optical glass characterized in that,
contains, in mass% based on the oxide
30.08 to 34.64 percent of La 2 O 3 Components (a),
TiO more than 20.0-45.0% 2 Ingredients (A) and (B),
More than 0 to 40.0 percent of BaO component,
0.77-10.0% of WO 3 Components (a),
6.95 to 30.0 percent of B 2 O 3 Ingredients (A) and (B),
0 to 6.63% of SiO 2 Ingredients (A) and (B),
0 to 10.61 percent of Nb 2 O 5 Ingredients (A) and (B),
0 to 2.27% of ZnO component,
0 to less than 1.0% of Ta 2 O 5 Component (a) and
ZrO of 0 to less than 6.5% 2 The components of the components are mixed and stirred,
and contains SiO 2 Component (A) and (B) 2 O 3 The total amount of the components is more than 7.0% and less than 30.0%, ln 2 O 3 The total content of the components is more than 30.08% and less than 50.0%, wherein Ln is selected from La, gd and YAnd Yb,
TiO 2 /(TiO 2 a mass ratio of + BaO) of 0.10 or more and 0.90 or less,
TiO 2 /(La 2 O 3 +Nb 2 O 5 +Gd 2 O 3 +Yb 2 O 3 ) The mass ratio of (A) is 0.5 or more,
refractive index (n) d ) Is 1.98 or more, abbe number (v) d ) A wavelength (lambda) of 27.0 or less and a spectral transmittance of 5% 5 ) Is 400nm or less.
2. The optical glass according to claim 1,
in terms of mass% based on the oxide,
Y 2 O 3 the components are 0 to 15.0 percent,
Yb 2 O 3 the component (a) is0 to 15.0%, and
Gd 2 O 3 the components are 0-15.0%.
3. The optical glass according to any of claims 1 or 2,
in terms of mass% based on the oxide,
(La 2 O 3 +Nb 2 O 5 +Gd 2 O 3 +Yb 2 O 3 ) The sum of the mass ratios of (a) and (b) is 35.0% to 60.0%.
4. The optical glass according to any of claims 1 or 2,
based on the oxide, the content of the oxide,
TiO 2 the ratio of/BaO is 0.60 to 3.00.
5. The optical glass according to any one of claims 1 or 2, wherein the glass composition is characterized in that, in mass% on an oxide basis,
Rn 2 the sum of the mass of the O components is 15.0% or less,
wherein Rn is one or more selected from the group consisting of Li, na, and K.
6. The optical glass according to any one of claims 1 or 2, wherein the glass composition is characterized in that, in mass% on an oxide basis,
the sum of the RO components is more than 0% and 35.0% or less by mass,
wherein R is one or more selected from the group consisting of Mg, ca, sr, ba, zn.
7. The optical glass according to any one of claims 1 or 2, comprising, in mass% on an oxide basis
0 to 15.0 percent of MgO component,
0 to 15.0 percent of CaO component,
0 to 15.0 percent of SrO,
Li 2 0 to 15.0 percent of O component,
Na 2 0 to 15.0 percent of O component,
K 2 0 to 15.0 percent of O component,
P 2 O 5 0 to 10.0 percent of component,
GeO 2 0 to 10.0 percent of component,
Al 2 O 3 0 to 15.0 percent of component,
Ga 2 O 3 0 to 15.0 percent of component,
Bi 2 O 3 0 to 10.0 percent of component,
TeO 2 0 to 10.0 percent of component,
SnO 2 0 to 3.0% of the component (A), and
Sb 2 O 3 0 to 1.0 percent of the components.
8. A preform, characterized in that it comprises,
comprising the optical glass according to any one of claims 1 to 7.
9. An optical element characterized in that it comprises, in a first state,
comprising the optical glass according to any one of claims 1 to 7.
10. An optical instrument, characterized in that,
an optical element according to claim 9.
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JPS5950048A (en) * 1982-09-16 1984-03-22 Ohara Inc Optical glass
JP2005179142A (en) * 2002-12-27 2005-07-07 Hoya Corp Optical glass, glass gob for press molding and optical device
CN101289276A (en) * 2008-06-19 2008-10-22 成都光明光电股份有限公司 High-refraction and high- dispersion optical glass and method of manufacture
CN101318769A (en) * 2008-07-08 2008-12-10 成都光明光电股份有限公司 Environment friendly heavy-lanthanide flint optical glass
CN101333072A (en) * 2007-06-29 2008-12-31 上海新沪玻璃有限公司 High-refractivity lanthanide optical glass NLaSF010 and method for manufacturing same
JP2011153048A (en) * 2010-01-28 2011-08-11 Konica Minolta Opto Inc Optical glass

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Publication number Priority date Publication date Assignee Title
JPS5950048A (en) * 1982-09-16 1984-03-22 Ohara Inc Optical glass
JP2005179142A (en) * 2002-12-27 2005-07-07 Hoya Corp Optical glass, glass gob for press molding and optical device
CN101333072A (en) * 2007-06-29 2008-12-31 上海新沪玻璃有限公司 High-refractivity lanthanide optical glass NLaSF010 and method for manufacturing same
CN101289276A (en) * 2008-06-19 2008-10-22 成都光明光电股份有限公司 High-refraction and high- dispersion optical glass and method of manufacture
CN101318769A (en) * 2008-07-08 2008-12-10 成都光明光电股份有限公司 Environment friendly heavy-lanthanide flint optical glass
JP2011153048A (en) * 2010-01-28 2011-08-11 Konica Minolta Opto Inc Optical glass

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