CN108117257B - Optical glass, preform and optical element - Google Patents

Optical glass, preform and optical element Download PDF

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Publication number
CN108117257B
CN108117257B CN201711241970.0A CN201711241970A CN108117257B CN 108117257 B CN108117257 B CN 108117257B CN 201711241970 A CN201711241970 A CN 201711241970A CN 108117257 B CN108117257 B CN 108117257B
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component
glass
optical
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CN108117257A (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
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/14—Silica-free oxide glass compositions containing boron
    • C03C3/15—Silica-free oxide glass compositions containing boron containing rare earths
    • C03C3/155—Silica-free oxide glass compositions containing boron containing rare earths containing zirconium, titanium, tantalum or niobium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • 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

Abstract

The invention relates to an optical glass, a preform and an optical element. The invention discloses an optical glass, which comprises more than 0-35.0% of La by mass percent 2 O 3 Component (I), tiO 0-45.0% 2 A component and more than 0 to 45.0% 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 + BaO mass ratio of 0.10-0.90, and refractive index (n) d ) Has an Abbe number (v) of 1.80 or more d ) An optical constant of 35.0 or less and a partial dispersion ratio (θ g, F) of 0.57 or more. According to the present invention, an optical glass having high refractive index and high dispersion, high partial dispersion ratio, 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 progressing. 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 1.80 or more, particularly for reducing the weight and size of the whole optical system d ) A low Abbe number (v) of 15.0 to 35.0 inclusive d ) The demand for high refractive index and high dispersion glass of (2) is increasing. As such a high-refractive-index, high-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. 2010-215503
Patent document 2: japanese patent laid-open publication No. 2011-178571
Disclosure of Invention
However, the glass described in patent document 1 contains a large amount of Nb in order to promote high refractive index and high dispersion 2 O 5 Component (A) or La 2 O 3 Rare earth elements such as components have a problem of increasing the production cost. Therefore, an optical glass having a high refractive index/high dispersion and a low production cost has been desired.
On the other hand, for correction of aberration (secondary spectrum) in the blue region in chromatic aberration, a partial dispersion ratio (θ g, F) is used as an index of optical characteristics that are important in optical design. The partial dispersion ratio (θ g, F) is represented by the following formula (1).
θg，F＝(n g -n F )/(n F -n c ) (1)
Here, in an optical system that performs chromatic aberration correction by combining a low-dispersion convex lens and a high-dispersion concave lens, an optical material having a small partial dispersion ratio (θ g, F) is used for the low-dispersion lens, and an optical material having a large dispersion ratio (θ g, F) is used for the high-dispersion lens, and by combining these optical materials, the secondary spectrum can be corrected.
However, the glass described in patent document 2, even though having a high refractive index and a high dispersion, needs to have Ta 2 O 5 The composition of the components increases the manufacturing cost, and the partial dispersion ratio is small, so that the lens for correcting the secondary spectrum is insufficient. That is, a high refractive index (n) is desired d ) And low Abbe number (v) d ) Meanwhile, the partial dispersion ratio (theta g, F) of the optical glass is larger.
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 high dispersion property and being manufactured at a low cost, and a preform and an optical element using the optical glass.
Further, an object of the present invention is to provide an optical glass having a high refractive index and a high dispersion and preferably used for chromatic aberration correction, and a preform and an optical element using the optical glass.
As a result of extensive and intensive studies by the inventors of the present invention to solve the above-mentioned problems, it was found that La was 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) to achieve a desired high refractive index and high dispersion, and to achieve a desired partial dispersion ratio while suppressing the manufacturing cost, thereby completing the present invention.
Specifically, the present invention provides the following.
(1) An optical glass comprising, in mass% on an oxide basis,
comprises
More than 0 to 35.0 percent of La 2 O 3 Ingredients (A) and (B),
TiO more than 0-45.0% 2 Component (a) and
more than 0 to 45.0 percent of BaO,
SiO 2 component (A) and (B) 2 O 3 The total amount of the components is 5.0-30.0%,
TiO 2 /(TiO 2 a mass ratio of + BaO) of 0.10 or more and 0.90 or less,
and has a refractive index (n) d ) Is 1.80 or more, and has an Abbe number (v) d ) 35.0 or less, and a partial dispersion ratio (θ g, F) of 0.57 or more.
(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 30.0 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 components are 0 to 15.0 percent,
Gd 2 O 3 0 to 15.0% of a component, and
Bi 2 O 3 the components are 0-10.0%.
(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 40.0% 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 /(La 2 O 3 +Nb 2 O 5 +Gd 2 O 3 +Yb 2 O 3 ) The mass ratio of (b) is more than 0 and 5.00 or less.
(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 mass of O components (Rn is at least one selected from the group consisting of Li, na and K in the formula) is 15.0% or less.
(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 and Ba) is more than 0% and 45.0% 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,
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 30.0 percent of CaO component,
0 to 30.0 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,
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 an optical glass having a high refractive index and a high dispersion and being manufactured at a low cost, and a preform and an optical element using the optical glass.
Further, according to the present invention, it is possible to provide an optical glass having a high refractive index and a high dispersion and preferably used for chromatic aberration correction, 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 ratios (. Theta.g, F) and Abbe numbers (v) of glasses of examples of the present invention d ) Schematic representation of the relationship of (a).
Detailed Description
The optical glass of the present invention contains, by mass%, more than 0% to 35.0% of La 2 O 3 Component (I), tiO 0-45.0% 2 A component and more than 0 to 45.0% 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 + BaO mass ratio of 0.10-0.90, and refractive index (n) d ) Is 1.80 or more, and has an Abbe number (v) d ) An optical glass having an optical constant with a partial dispersion ratio (θ g, F) of not less than 35.0 and not less than 0.57.
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. Therefore, it is possible to provide an optical glass having a high refractive index and a high dispersion and being manufactured at a low cost, and a preform and an optical element using the optical glass.
Further, by adjusting the content of each component, the partial dispersion ratio of the glass can be further improved while achieving a high refractive index and a high dispersion. Therefore, it is possible to provide an optical glass having a high refractive index and a high dispersion and preferably used for chromatic aberration correction, 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 the present specification, unless otherwise specified, the content of each component is 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 1.0%, even more preferably 2.0%, even more preferably 3.0%, and even more preferably 4.5%.
On the other hand, by mixing La 2 O 3 The content of the component (b) is 35.0% or less, whereby the devitrification resistance of the glass can be improved, the abbe number can be reduced, 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 35.0%, more preferably 24.0%, still more preferably 21.0%, and yet more preferably 18.0%.
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 When the content of the component (A) is more than 0%, the refractive index of the glass can be increased, the Abbe number can be decreased, the partial dispersion ratio can be increased, and the devitrification resistance can be improved. Thus, tiO 2 Composition (I)The lower limit of the content of (b) is preferably more than 0%, preferably 10.0%, more preferably more than 17.0%, further preferably 21.5%, and further preferably 23.5%.
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, tiO can be inhibited 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 35.0%, and still more preferably 32.0%.
TiO 2 The component (C) may be TiO 2 And the like as a raw material.
The BaO component is an essential component capable of improving the refractive index or devitrification resistance of the glass when the content thereof is more than 0%, and capable of improving 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 45.0% 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 45.0%, more preferably 35.0%, further preferably 32.0%, and further preferably 30.0%.
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 A decrease in resistance to devitrification due to an insufficient amount of the component. Therefore, mass sum of (B) 2 O 3 +SiO 2 ) The lower limit of (b) is preferably 5.0%, more preferably 10.0%, still more preferably 13.0%, and still more preferably 15.0%.
On the other hand, by setting the sum to 30.0% or less, it is possible to suppress the occurrence of an excessive content of these componentsThe resulting decrease in refractive index, so that a desired high refractive index can be easily obtained. Therefore, mass and (B) 2 O 3 +SiO 2 ) The upper limit of (b) is preferably 30.0%, more preferably 24.0%, and still more preferably 22.0%.
Here, tiO is 2 Content of component (C) and 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. This makes it possible to increase the partial dispersion ratio while maintaining a high refractive index and 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, and further preferably 0.75.
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 (A) is 30.0% or less, and SiO can be obtained 2 The components are easily melted in the molten glass and are prevented from melting at high temperatures. Thus, siO 2 The upper limit of the content of the component (b) is preferably 30.0%, more preferably 28.0%, still more preferably 23.0%, still more preferably 18.0%, and yet more preferably 16.0%.
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 than0.5%, more preferably more than 1.0%, 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%, more preferably 28.0%, still more preferably 25.0%, yet more preferably 23.0%, and yet more preferably 20.0%.
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 2.0%.
On the other hand, by setting the content of the ZnO component to 30.0% 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 30.0%, more preferably 23.0%, still more preferably 17.0%, and still more preferably 14.0%.
ZnO or ZnF can be used as the ZnO component 2 And the like as a raw material.
Y 2 O 3 When the content of the component (b) is more than 0%, the increase in the material cost of the glass can be suppressed, and the refractive index can be increased.
By mixing Y 2 O 3 The content of the component (b) is 15.0% or less, and thus the glass can be inhibited from lowering in refractive index, reduced in abbe number, and improved in devitrification resistance. 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, increase the partial dispersion ratio of the glass, and 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 0.5%, and still more preferably 1.0%.
On the other hand, by mixing Nb 2 O 5 The content of the component is 25.0% or less, and Nb can be prevented 2 O 5 The excessive content of the component can reduce the devitrification resistance of the glass or the transmittance of visible light, and the abbe number. Thus, nb 2 O 5 The upper limit of the content of the component (b) is preferably 25.0%, more preferably 18.0%, still more preferably 13.0%, and still more preferably 10.0%.
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 whose content is more than 0% and which can increase the refractive index of the glass and reduce the dispersion.
On the other hand, by mixing Yb 2 O 3 The content of the component (A) is 15.0% or less, whereby the devitrification resistance of the glass can be improved and the production cost can be suppressed. 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 using Gd, which is particularly expensive among rare earth elements 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 the need for the heat exchanger to be increased more than necessaryThe Abbe number of the glass (2) is increased. 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.
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, the production cost can be suppressed, and the coloring of the glass can be reduced to improve the visible light transmittance. In addition, this can suppress an increase in the abbe number of the glass more than necessary. 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.
Further, in the optical glass of the present invention, 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 sum (mass sum) of the contents of (c) is preferably 40.0% or less. This can reduce the content of these expensive components, and can suppress the material cost of the glass. 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 40.0%, more preferably 30.0%, still more preferably 25.0%, and still more preferably 23.0%.
On the other hand, by containing the sum of the mass of these components more than 0%, a desired high refractive index can be obtained. Therefore, mass sum of (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 5.0%, and still more preferably 8.0%.
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% and 50.0% or less.
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, the production cost can be suppressed, and the increase in the abbe number of the glass more than necessary can be suppressed. Thus, ln 2 O 3 The upper limit of the mass sum of the contents of the components is preferably 50.0%, more preferably less than 40.0%, further preferably 31.0%, further preferably 26.0%, and still further preferably 21.0%.
Here, tiO is used 2 Content of component (A) and La 2 O 3 Component (B) 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 manufacturing cost 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 lower limit of (b) is preferably more than 0, more preferably 0.50, still more preferably 0.80, and still more preferably 1.00.
On the other hand, by setting the mass ratio to 5.0 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 5.00, more preferably 4.00, still more preferably 3.00, and still more preferably 2.80.
Rn 2 O component (wherein Rn isOne or more selected from the group consisting of Li, na, and K) is preferably 15.0% or less in total. 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 mass of the O components is preferably 15.0%, more preferably 10.0%, and still more preferably 5.0%.
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 more than 0% and 45.0% 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 45.0%, more preferably less than 40.0%, even more preferably 38.0%, even more preferably less than 35.0%, and even more preferably 32.0%.
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 5.0%, further preferably 15.0%, and further preferably more than 20.0%.
ZrO 2 The component (b) is an arbitrary component which contributes to an increase in refractive index and a decrease in dispersion of the glass when the content thereof is more than 0%, and can improve devitrification resistance of the glass. 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 causes the deterioration of devitrification resistance of the glass. Thus, zrO 2 The upper limit of the content of the component (b) is preferably 20.0%, more preferably 15.0%, and still more preferably 10.0%.
ZrO 2 ZrO may be used as the component 2 、ZrF 4 And the like as a raw material.
WO 3 The component is an arbitrary component whose content is more than 0% and which can increase the refractive index, increase the partial dispersion ratio, and improve the devitrification resistance of the glass. In addition, WO 3 The component (A) is also a component capable of lowering the glass transition temperatureAnd (4) dividing. 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 0.3%, and still more preferably more than 0.5%.
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 optional component which can improve the meltability of the glass raw material or the devitrification resistance of the glass when the content is more than 0%.
On the other hand, by setting the content of the MgO component to 15.0% or less, a decrease in refractive index and a decrease in resistance to devitrification due to excessive contents 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 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 whose content is more than 0% and which can improve the refractive index or 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%, further preferably 1.5%, and further preferably 3.0%.
On the other hand, by setting the content of the CaO component to 30.0% 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 30.0%, more preferably 25.0%, further preferably 20.0%, further preferably 16.0%, and further more preferably 13.0%.
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%, and still more preferably 1.5%.
On the other hand, by setting the content of the SrO component to 30.0% 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 30.0%, more preferably 25.0%, even more preferably 20.0%, even more preferably 17.0%, and even more preferably 15.0%.
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 O component is an optional component which can improve the meltability of the glass when the content of at least one of the O components 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 O component can be suppressedAnd the devitrification can be reduced. 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 The content of at least one of the O components is preferably 15.0% or less, more preferably less than 10.0%, and still more preferably less than 5.0%.
Li 2 O component and Na 2 O component and K 2 Li as 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 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.
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 charged into 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.
The component F is an optional component which can increase the Abbe number of the glass, lower the glass transition temperature and improve the resistance to devitrification when the content thereof is more than 0%.
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.
SnO 2 The component (b) is an arbitrary 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 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, since 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 may be used as 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 component (c) 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 Sb described above 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.
< 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, and Lu, for example, hf, Ν, cr, mn, fe, co, ni, cu, ag, mo, ce, and Nd, if contained individually or in combination, may cause coloring of the glass even in a small amount and absorb light having a specific wavelength in the visible light region, it is preferable that the glass is substantially not 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 homogenize and defoam, the temperature is lowered to 1200 ℃ 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 is a method of drawing out molded glass from one end of the molding die while flowing molten glass into the other end of the molding die, or a method of casting molten glass into a die and slowly cooling the same.
[ Properties ]
The optical glass of the present invention 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 1.80, more preferably 1.85, and further preferably 1.90. The upper limit of the refractive index is preferably 2.20 or less, more preferably 2.10 or less, and further preferably less than 2.05.
Further, the Abbe number (v) of the optical glass of the present invention d ) The lower limit of (b) is preferably 15.0 or more, more preferably 20.0 or more, further preferably 21.0 or more, and further preferably 22.0 or more, and the upper limit thereof is preferably 35.0 or less, more preferably 30.0 or less, and further preferably less than 27.0.
The optical glass of the present invention has such a refractive index and abbe number, and is useful in optical design, and particularly, can realize miniaturization of an optical system while achieving 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 520nm, more preferably 510nm, still more preferably 500nm, still more preferably 490nm.
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, and still more preferably 380nm.
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.
Further, the optical glass of the present invention has a partial dispersion ratio (. Theta.g, F) and an Abbe number (. V) d ) The relationship between (θ g, F) ≧ 0.00162 xv d + 0.6450).
Thus, the optical glass of the present invention has a higher partial dispersion ratio (θ g, F) than the conventionally known glass containing a large amount of rare earth element component. Therefore, an optical element formed of the optical glass can be preferably used for correction of chromatic aberration while achieving high refractive index and high dispersion of the glass.
Here, 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 + 0.6450), more preferably (-0.00162 × v) d + 0.6470), more preferably (-0.00162 xv) d +0.6500). On the other hand, the upper limit of the partial dispersion ratio (θ g, F) of the optical glass of the present invention is not particularly limited, but is generally (-0.00162 × v) d + 0.6800) or less, more specifically (-0.00162 × v) d +0.6700 or less, more specifically (-0.00162 xv) d + 0.6650) or less. In glasses having specific compositions according to the invention, provided that the partial dispersion ratio (. Theta.g, F) and the Abbe number (. V.) are d ) By satisfying this relationship, stable glass can be obtained.
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.) are expressed d ) Is represented by a straight line parallel to the normal. The normal lines represent the partial dispersion ratios (θ g, F) and Abbe numbers (v) of conventionally known glasses d ) The linear relationship observed between the two is adopted at a partial dispersion ratio (theta)g, F) is the vertical axis, and Abbe number (v) 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). Furthermore, 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 ) It was 60.5, and the partial dispersion ratio (. Theta.g, F) was 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, the size of the optical element is increased, and high-definition and high-precision imaging characteristics and projection characteristics can be realized when an optical instrument such as a camera is used.
Further, since the optical element can be usefully used for correction of chromatic aberration in an optical system by increasing the partial dispersion ratio, for example, when the optical element is used for a camera, an object to be photographed can be more accurately expressed, and when the optical element is used for a projector, a desired image can be more excellently projected.
Examples
Glass compositions of examples (Nos. 1 to 55) of the present invention and refractive indices (n) of these glasses d ) Abbe number (v) d ) Transmittance (λ) 5 、λ 70 ) And the values of the partial dispersion 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, and then charged into a platinum crucible, the glass raw materials were melted for 2 hours at a temperature ranging from 1250 to 1300 ℃ by an electric furnace, and when the glass raw materials were melted, the melted glass raw materials were defoamed by stirring, then cooled to 1080 to 1180 ℃, stirred again to be uniform, and then cast into a mold, and slowly cooled to prepare glasses.
Refractive index (n) of glasses of examples d ) Abbe number (v) d ) And the partial dispersion ratio (thetag, F) is expressed as a measurement relative to the d-line (587.56 nm) of the 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) relative 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, according to JISZ8722, the thickness is 10 ± 0.The spectral transmittance of the 1mm parallel polished article at 200 to 800nm was measured to determine λ 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 7.17 7.17 7.17 7.17 7.17 7.17
B 2 O 3 11.39 11.39 11.39 11.39 11.39 11.39
La 2 O 3 19.83 15.83 15.83 15.83 15.83 15.83
Y 2 O 3
Gd 2 O3
Yb 2 O 3
ZrO 2 6.10 6.10 4.10 6.10 6.10 6.10
TiO 2 24.56 26.56 26.56 26.56 26.56 26.56
Nb 2 O 5 2.00 2.00 2.00 2.00
WO 3 0.78 0.78 0.78 0.78 0.78 0.78
ZnO 5.58 5.58 5.58 5.58 5.58 5.58
Li 2 O
Na 2 O
K 2 O
MgO
CaO 5.00 10.00
SrO
BaO 24.60 26.60 26.60 24.60 19.60 14.60
Sb 2 O 3
SnO 2
Total up to 100.00 100.00 100.00 100.00 100.00 100.00
Si+B 18.56 18.56 18.56 18.56 18.56 18.56
Ti/(Ti+Ba) 0.50 0.50 0.50 0.52 0.58 0.65
La+Nb+Gd+Yb 19.83 15.83 17.83 17.83 17.83 17.83
Ln 2 O 3 19.83 15.83 15.83 15.83 15.83 15.83
Ti/(La+Nb+Gd+Yb) 1.24 1.68 1.49 1.49 1.49 1.49
Rn 2 O 0.00 0.00 0.00 0.00 0.00 0.00
RO 24.60 26.60 26.60 24.60 24.60 24.60
Refractive index (n) d ) 1.940 1.946 1.949 1.955 1.947 1.938
Abbe number (v) d ) 25.8 24.9 24.6 24.5 25.0 25.6
Partial dispersion ratio (θ g, F) 0.6155 0.6178 0.6207 0.6212 0.6183 0.6142
λ 70 435 448 459 463 448 447
λ 5 372 374 375 376 373 372
TABLE 2
wt％ 7 8 9 10 11 12
SiO 2 7.17 7.17 7.17 6.17 6.17 6.17
B 2 O 3 11.39 11.39 11.39 11.39 11.39 11.39
La 2 O 3 12.83 9.83 9.83 10.83 10.83 10.83
Y 2 O 3
Gd 2 O 3
Yb 2 O 3
ZrO 2 6.10 6.10 6.10 6.10 6.10 6.10
TiO 2 29.56 29.56 28.06 28.06 28.06 28.06
Nb 2 O 5 2.00 5.00 6.50 6.50 5.00 5.00
WO 3 0.78 0.78 0.78 0.78 0.78 0.78
ZnO 5.58 5.58 5.58 5.58 7.08 7.08
Li 2 O
Na 2 O
K 2 O
MgO
CaO 10.00 10.00 10.00 10.00 10.00 8.00
SrO 2.00 2.00 2.00 2.00
BaO 14.60 14.60 12.60 12.60 12.60 14.60
Sb 2 O 3
SnO 2
Total up to 100.00 100.00 100.00 100.00 100.00 100.00
Si+B 18.56 18.56 18.56 17.56 17.56 17.56
Ti/(Ti+Ba) 0.67 0.67 0.69 0.69 0.69 0.66
La+Nb+Gd+Yb 14.83 14.83 16.33 17.33 15.83 15.83
Ln 2 O 3 12.83 9.83 9.83 10.83 10.83 10.83
Ti/(La+Nb+Gd+Yb) 1.99 1.99 1.72 1.62 1.77 1.77
Rn 2 O 0.00 0.00 0.00 0.00 0.00 0.00
RO 24.60 24.60 24.60 24.60 24.60 24.60
Refractive index (n) d ) 1.953 1.960 1.956 1.963 1.958 1.961
Abbe number (V) d ) 24.4 23.9 24.1 24.1 24.3 24.1
Partial dispersion ratio (θ g, F) 0.6200 0.6237 0.6205 0.6203 0.6193 0.6199
λ 70 463 474 465 455 443 454
λ 5 375 376 376 375 373 375
TABLE 3
wt％ 13 14 15 16 17 18
SiO 2 6.17 6.17 6.17 6.17 6.17 6.17
B 2 O 3 11.39 11.39 11.39 11.39 11.39 11.39
La 2 O 3 11.33 6.33 13.83 14.83 13.83 13.83
Y 2 O 3
Gd 2 O 3
Yb 2 O 3
ZrO 2 5.60 5.60 5.60 5.60 5.60 5.60
TiO 2 28.06 28.06 28.06 28.06 28.06 28.06
Nb 2 O 5 5.00 5.00 5.00 5.00 5.00 5.00
WO 3 0.78 0.78 0.78 0.78 0.78 0.78
ZnO 7.08 12.08 4.58 3.58
Li 2 O
Na 2 O
K 2 O
MgO
CaO 8.00 8.00 8.00 8.00 8.00 11.00
SrO 2.00 2.00 2.00 2.00 2.00 2.00
BaO 14.60 14.60 14.60 14.60 19.18 16.18
Sb 2 O 3
SnO 2
Total up to 100.00 100.00 100.00 100.00 100.00 100.00
Si+B 17.56 17.56 17.56 17.56 17.56 17.56
Ti/(Ti+Ba) 0.66 0.66 0.66 0.66 0.59 0.63
La+Nb+Gd+Yb 16.33 11.33 18.83 19.83 18.83 18.83
Ln 2 O 3 11.33 6.33 13.83 14.83 13.83 13.83
Ti/(La+Nb+Gd+Yb) 1.72 2.48 1.49 1.42 1.49 1.49
Rn 2 O 0.00 0.00 0.00 0.00 0.00 0.00
RO 24.60 24.60 24.60 24.60 29.18 29.18
Refractive index (n) d ) 1.961 1.956 1.963 1.964 1.957 1.951
Abbe number (V) d ) 24.1 24.0 24.2 24.1 24.4 24.7
Partial dispersion ratio (θ g, F) 0.6209 0.6203 0.6197 0.6202 0.6193 0.6172
λ 70 453 461 458 460 444 438
λ 5 375 375 375 375 374 372
TABLE 4
wt％ 19 20 21 22 23 24
SiO 2 6.17 6.17 6.17 6.17 6.17 6.17
B 2 O 3 11.39 11.39 11.39 11.39 11.39 11.39
La 2 O 3 13.83 13.83 13.83 13.83 13.83 13.83
Y 2 O 3
Gd 2 O 3
Yb 2 O 3
ZrO 2 5.60 5.60 5.60 5.60 5.60 5.60
TiO 2 28.06 28.06 28.06 28.06 28.06 28.06
Nb 2 O 5 5.00 5.00 5.00 5.00 5.00 5.00
WO 3 0.78 0.78 0.78 0.78 0.78 0.78
ZnO
Li 2 O
Na 2 O
K 2 O
MgO
CaO 10.00 8.00 6.00 6.00 11.00
SrO 10.00 2.00 4.00
BaO 19.18 21.18 19.18 21.18 19.18 18.18
Sb 2 O 3
SnO 2
Is totaled 100.00 100.00 100.00 100.00 100.00 100.00
Si+B 17.56 17.56 17.56 17.56 17.56 17.56
Ti/(Ti+Ba) 0.59 0.57 0.59 0.57 0.59 0.61
La+Nb+Gd+Yb 18.83 18.83 18.83 18.83 18.83 18.83
Ln 2 O 3 13.83 13.83 13.83 13.83 13.83 13.83
Ti/(La+Nb+Gd+Yb) 1.49 1.49 1.49 1.49 1.49 1.49
Rn 2 O 0.00 0.00 0.00 0.00 0.00 0.00
RO 29.18 29.18 29.18 29.18 29.18 29.18
Refractive index (n) d ) 1.955 1.959 1.967 1.961 1.960 1.953
Abbe number (V) d ) 24.6 24.3 23.6 24.1 24.2 24.7
Partial dispersion ratio (θ g, F) 0.6190 0.6200 0.6236 0.6206 0.6204 0.6182
λ 70 442 454 474 451 457 439
λ 5 373 375 377 375 375 372
TABLE 5
wt％ 25 26 27 28 29 30
SiO 2 6.17 6.17 6.17 6.17 6.17
B 2 O 3 11.39 11.39 11.39 11.39 11.39 17.56
La 2 O 3 13.83 13.83 13.83 13.83 13.83 13.83
Y 2 O 3
Gd 2 O 3
Yb 2 O 3
ZrO 2 5.60 5.60 5.60 5.60 5.60 5.60
TiO 2 28.06 28.06 28.06 28.06 28.06 28.06
Nb 2 O 5 5.00 5.00 5.00 5.00 5.00 5.00
WO 3 0.78 0.78 0.78 0.78 0.78 0.78
ZnO
Li 2 O
Na 2 O
K 2 O
MgO
CaO 5.00 9.00 7.00 8.00 6.00 6.00
SrO 2.00
BaO 24.18 20.18 22.18 21.18 23.18 21.18
Sb 2 O 3
SnO 2
Is totaled 100.00 100.00 100.00 100.00 100.00 100.00
Si+B 17.56 17.56 17.56 17.56 17.56 17.56
Ti/(Ti+Ba) 0.54 0.58 0.56 0.57 0.55 0.57
La+Nb+Gd+Yb 18.83 18.83 18.83 18.83 18.83 18.83
Ln 2 O 3 13.83 13.83 13.83 13.83 13.83 13.83
Ti/(La+Nb+Gd+Yb) 1.49 1.49 1.49 1.49 1.49 1.49
Rn 2 O 0.00 0.00 0.00 0.00 0.00 0.00
RO 29.18 29.18 29.18 29.18 29.18 29.18
Refractive index (n) d ) 1.965 1.957 1.961 1.959 1.963 1.960
Abbe number (V) d ) 23.9 24.4 24.2 24.3 24.0 24.1
Partial dispersion ratio (θ g, F) 0.6221 0.6194 0.6201 0.6201 0.6211 0.6217
λ 70 471 447 460 447 460 471
λ 5 376 374 376 374 376 377
TABLE 6
wt％ 31 32 33 34 35 36
SiO 2 11.17 3.17 13.17 8.17 9.17 7.17
B 2 O 3 6.39 14.39 4.39 9.39 8.39 10.39
La 2 O 3 13.83 13.83 13.83 13.83 13.83 13.83
Y 2 O 3
Gd 2 O 3
Yb 2 O 3
ZrO 2 5.60 5.60 5.60 5.60 5.60 5.60
TiO 2 28.06 28.06 28.06 28.06 28.06 28.06
Nb 2 O 5 5.00 5.00 5.00 5.00 5.00 5.00
WO 3 0.78 0.78 0.78 0.78 0.78 0.78
ZnO
Li 2 O
Na 2 O
K 2 O
MgO
CaO 6.00 6.00 6.00 6.00 6.00 6.00
SrO 2.00 2.00 2.00 2.00 2.00 2.00
BaO 21.18 21.18 21.18 21.18 21.18 21.18
Sb 2 O 3
SnO 2
Total up to 100.00 100.00 100.00 100.00 100.00 100.00
Si+B 17.56 17.56 17.56 17.56 17.56 17.56
Ti/(Ti+Ba) 0.57 0.57 0.57 0.57 0.57 0.57
La+Nb+Gd+Yb 18.83 18.83 18.83 18.83 18.83 18.83
Ln 2 O 3 13.83 13.83 13.83 13.83 13.83 13.83
Ti/(La+Nb+Gd+Yb) 1.49 1.49 1.49 1.49 1.49 1.49
Rn 2 O 0.00 0.00 0.00 0.00 0.00 0.00
RO 29.18 29.18 29.18 29.18 29.18 29.18
Refractive index (n) d ) 1.961 1.961 1.961 1.961 1.961 1.962
Abbe number (V) d ) 24.2 24.1 24.2 24.1 24.1 24.1
Partial dispersion ratio (θ g, F) 0.6204 0.6213 0.6195 0.6206 0.6196 0.6203
λ 70 447 478 440 454 451 454
λ 5 375 379 374 375 375 375
TABLE 7
wt％ 37 38 39 40
SiO 2 5.17 6.17 7.17 9.17
B 2 O 3 12.39 11.39 10.39 8.39
La 2 O 3 13.83 13.83 13.83 13.83
Y 2 O 3
Gd 2 O 3
Yb 2 O 3
ZrO 2 5.60 5.60 5.60 5.60
TiO 2 28.06 28.04 28.04 28.04
Nb 2 O 5 5.00 5.00 5.00 5.00
WO 3 0.78 0.78 0.78 0.78
ZnO
Li 2 O
Na 2 O
K 2 O
MgO
CaO 6.00 6.00 6.00 6.00
SrO 2.00 2.00 2.00 2.00
BaO 21.18 21.18 21.18 21.18
Sb 2 O 3 0.02 0.02 0.02
SnO 2
Total up to 100.00 100.00 100.00 100.00
Si+B 17.56 17.56 17.56 17.56
Ti/(Ti+Ba) 0.57 0.57 0.57 0.57
La+Nb+Gd+Yb 18.83 18.83 18.83 18.83
Ln 2 O 3 13.83 13.83 13.83 13.83
Ti/(La+Nb+Gd+Yb) 1.49 1.49 1.49 1.49
Rn 2 O 0.00 0.00 0.00 0.00
RO 29.18 29.18 29.18 29.17
Refractive index (n) d ) 1.962 1.961 1.962 1.961
Abbe number (V) d ) 24.1 24.1 24.1 24.2
Partial dispersion ratio (θ g, F) 0.6210 0.6212 0.6203 0.6201
λ 70 462 455 457 454
λ 5 375 377 377 377
TABLE 8
wt％ 41 42 43 44 45 46
SiO 2 8.17 6.81 6.24 6.13 6.88 7.11
B 2 O 3 9.39 9.71 9.59 9.43 11.04 11.40
La 2 O 3 13.83 20.15 25.25 30.61 26.85 26.33
Y 2 O 3
Gd 2 O 3
Yb 2 O 3
ZrO 2 5.60 5.80 4.78 4.69 4.94 5.10
TiO 2 28.05 24.71 22.62 21.16 20.65 19.23
Nb 2 O 5 5.00 5.17 9.16 9.00 13.42 10.40
WO 3 0.78 0.82 0.74 0.73 2.12
ZnO 3.16
Li 2 O
Na 2 O
K 2 O
MgO
CaO 6.00 5.78 3.86 3.80 4.00
SrO 2.00 2.06 1.89 1.33 1.39 1.44
BaO 21.18 18.97 15.85 13.10 10.81 13.69
Sb 2 O 3 0.02 0.02 0.03 0.02 0.02 0.02
SnO 2
Total up to 100.01 100.00 100.00 100.00 100.00 100.00
Si+B 17.56 16.52 15.83 15.56 17.92 18.51
Ti/(Ti+Ba) 0.57 0.57 0.59 0.62 0.66 0.58
La+Nb+Gd+Yb 18.83 25.32 34.41 39.61 40.27 36.73
Ln 2 O 3 13.83 20.15 25.25 30.61 26.85 26.33
Ti/(La+Nb+Gd+Yb) 1.49 0.98 0.66 0.53 0.51 0.52
Rn 2 O 0.00 0.00 0.00 0.00 0.00 0.00
RO 29.18 26.81 21.60 18.23 16.20 15.13
Refractive index (n) d ) 1.96079 1.95679 1.97750 1.97964 1.974 1.962
Abbe number (V) d ) 24.17 25.36 25.01 25.63 25.1 25.5
Partial dispersion ratio (θ g, F) 0.62036 0.61547 0.61602 0.61341 0.6154 0.6153
λ 70 451 442 448 447 452 455
λ 5 376.5 372 375 373 376 377
TABLE 9
wt％ 47 48 49 50 51 52
SiO 2 9.20 9.72 8.99 8.32 9.62 7.84
B 2 O 3 9.37 9.15 11.71 10.85 12.54 6.97
La 2 O 3 8.10 8.93 12.18 20.37 13.46 11.32
Y 2 O 3
Gd 2 O 3
Yb 2 O 3
ZrO 2 6.98 6.23 5.98 5.55 6.41 6.54
TiO 2 21.41 23.56 18.67 19.27 16.50 26.17
Nb 2 O 5 20.35 16.12 6.88 6.38 8.23 9.32
WO 3 1.33 1.46 5.89 2.69 2.39
ZnO 11.41 7.27 16.81
Li 2 O
Na 2 O
K 2 O
MgO
CaO 4.18 4.60 5.01 5.56
SrO 1.05 5.18 2.17 3.44
BaO 19.05 19.17 13.09 12.13 14.02 22.82
Sb 2 O 3 0.03 0.03 0.02 0.02 0.02 0.02
SnO 2
Total up to 100.00 100.00 100.00 100.00 100.00 100.00
Si+B 18.57 18.86 20.70 19.16 22.16 14.80
Ti/(Ti+Ba) 0.53 0.55 0.59 0.61 0.54 0.53
La+Nb+Gd+Yb 28.45 25.04 19.06 26.74 21.69 20.64
Ln 2 O 3 8.10 8.93 12.18 20.37 13.46 11.32
Ti/(La+Nb+Gd+Yb) 0.75 0.94 0.98 0.72 0.76 1.27
Rn 2 O 0.00 0.00 0.00 0.00 0.00 0.00
RO 23.22 24.82 18.28 19.30 14.02 31.83
Refractive index (n) d ) 1.977 1.970 1.911 1.926 1.900 1.977
Abbe number (V) d ) 22.8 23.1 26.3 27.0 27.2 23.9
Partial dispersion ratio (θ g, F) 0.6245 0.6243 0.6124 0.6090 0.6096 0.6194
λ 70 489 459 443 441 442 453
λ 5 386 382 375 371 374 375
Watch 10
wt％ 54 55
SiO 2 9.59 9.46
B 2 O 3 7.23 7.98
La 2 O 3 5.51 8.81
Y 2 O 3
Gd 2 O 3
Yb 2 O 3
ZrO 2 6.79 8.28
TiO 2 27.14 15.02
Nb 2 O 5 9.68 24.83
WO 3
ZnO
Li 2 O
Na 2 O
K 2 O
MgO
CaO 2.98 5.48
SrO 18.02 3.99
BaO 13.06 16.13
Sb 2 O 3 0.02 0.02
SnO 2
Is totaled 100.00 100.00
Si+B 16.82 17.44
Ti/(Ti+Ba) 0.68 0.48
La+Nb+Gd+Yb 15.18 33.64
Ln 2 O 3 5.51 8.81
Ti/(La+Nb+Gd+Yb) 1.79 0.45
Rn 2 O 0.00 0.00
RO 34.06 25.60
Refractive index (n) d ) 1.959 1.960
Abbe number (V) d ) 23.7 24.7
Partial dispersion ratio (θ g, F) 0.6201 0.6156
λ 70 447 448
λ 5 377 374
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 1.80 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 had Abbe numbers (v) d ) 35.0 or less, more specifically 30.0 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.
The optical glass of the examples of the present invention has a partial dispersion ratio (θ g, F) of 0.570 or more, more specifically 0.605 or more, and has a high numerical value.
In addition, in the optical glass of the embodiment of the present invention, the partial dispersion ratio (θ g, F) and the abbe number (v) d ) Satisfies (theta g, F) ≥ 0.00122v d + 0.6450), more specifically, satisfies the relation (θ g, F) ≧ 0.00122v d + 0.6500). Further, the glass of examples of the present application has a partial dispersion ratio (θ g, F) and an Abbe number (v) d ) The relationship of (a) is shown in FIG. 2.
As is apparent from the above description, the optical glass of the embodiment of the present invention has a large partial dispersion ratio (θ g, F), and the optical element obtained from the optical glass is useful for correction of chromatic aberration.
Therefore, it is clear that the optical glass of the embodiment of the present invention has high refractive index and high dispersion, and high partial dispersion ratio, and is preferably used for correction of chromatic aberration.
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
More than 0 to 14.83 percent of La 2 O 3 Ingredients (A) and (B),
23.5 to 35.0 percent of TiO 2 Ingredients (A) and (B),
More than 0 to 45.0 percent of BaO component,
Exceed0.5 to 10.0 percent of WO 3 Ingredients (A) and (B),
9.37 to 30.0 percent of B 2 O 3 Ingredients (A) and (B),
0 to 8.32% of SiO 2 Ingredients (A) and (B),
More than 0 to 6.50 percent of Nb 2 O 5 Ingredients (A) and (B),
0 to 5.0% of Y 2 O 3 Ingredients (A) and (B),
0 to 5.0% of Yb 2 O 3 Ingredients (A) and (B),
0 to 5.0 percent of Gd 2 O 3 Ingredients (A) and (B),
0 to 5.58% of ZnO component
0 to less than 1.0% of Ta 2 O 5 Component (a) and
0 to 6.10% of ZrO 2 The components of the components are mixed and stirred,
SiO 2 component (A) and (B) 2 O 3 The total amount of the components is 10.0-30.0%,
TiO 2 /(TiO 2 a mass ratio of + BaO) of 0.1 to 0.9,
TiO 2 /(La 2 O 3 +Nb 2 O 5 +Gd 2 O 3 +Yb 2 O 3 ) Is 1.27 or more and 3.00 or less,
and has a refractive index (n) d ) Has an Abbe number (v) of 1.960 or more d ) An optical constant having a partial dispersion ratio (θ g, F) of not more than 24.2 and not less than 0.57.
2. The optical glass according to claim 1,
in terms of mass% based on the oxide,
Bi 2 O 3 the components are 0-10.0%.
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 of (a) is more than 0% and 25.0% or less.
4. The optical glass according to any of claims 1 or 2,
in terms of mass% based on the oxide,
Ln 2 O 3 the total amount of the components is more than 0% and less than 26.0%,
wherein Ln is one or more selected from the group consisting of La, gd, Y and Yb.
5. The optical glass according to any one of claims 1 or 2, wherein the glass composition is characterized by comprising, in mass% on an oxide basis,
Rn 2 the sum of the O content is 15.0% or less by mass,
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 45.0% or less by mass,
wherein R is one or more selected from the group consisting of Mg, ca, sr, ba.
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 30.0 percent of CaO component,
0 to 30.0 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,
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 embodiment,
comprising the optical glass according to any one of claims 1 to 7.
10. An optical instrument, characterized in that it comprises,
an optical element according to claim 9.
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CN109437556B (en) * 2018-12-07 2022-05-03 成都光明光电股份有限公司 Heavy lanthanum flint glass and prefabricated member, optical element and optical instrument thereof
CN111285602B (en) * 2018-12-07 2022-03-08 成都光明光电股份有限公司 Heavy lanthanum flint glass and prefabricated member, optical element and optical instrument thereof
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CN109665714B (en) * 2019-02-28 2021-06-29 成都光明光电股份有限公司 Optical glass, glass preform, optical element and optical instrument
CN109650717B (en) * 2019-02-28 2021-10-26 成都光明光电股份有限公司 Optical glass
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