U.S. patent application number 11/451421 was filed with the patent office on 2006-10-19 for optical glass for precision press molding, preform for precission press molding, and process for the production thereof.
This patent application is currently assigned to HOYA CORPORATION. Invention is credited to Kazutaka Hayashi, Xuelu Zou.
Application Number | 20060234850 11/451421 |
Document ID | / |
Family ID | 28035296 |
Filed Date | 2006-10-19 |
United States Patent
Application |
20060234850 |
Kind Code |
A1 |
Hayashi; Kazutaka ; et
al. |
October 19, 2006 |
Optical glass for precision press molding, preform for precission
press molding, and process for the production thereof
Abstract
A high-refractivity high-dispersion optical glass for producing
an optical element, which requires no machining, such as polishing
or lapping, of an optical-function surface after precision press
molding, containing B.sub.2O.sub.3, SiO.sub.2, La.sub.2O.sub.3,
Gd.sub.2O.sub.3, ZnO, Li.sub.2O, ZrO.sub.2 and Ta.sub.2O.sub.5 as
essential components, containing 0 to 1 mol % of Sb.sub.2O.sub.3 as
an optional component, substantially containing none of PbO and
Lu.sub.2O.sub.3, having a glass transition temperature of
630.degree. C. or lower, and (1) having a refractive index nd and
an Abbe's number .nu.d which satisfy all of the following
relational expressions, 1.80<nd.ltoreq.1.90,
35.ltoreq..nu.d.ltoreq.50, and nd.gtoreq.2.025-(0.005.times..nu.d)
or (2) having an nd of greater than 1.85 and a .nu.d of greater
than 35.
Inventors: |
Hayashi; Kazutaka; (Tokyo,
JP) ; Zou; Xuelu; (Tokyo, JP) |
Correspondence
Address: |
NIXON & VANDERHYE, PC
901 NORTH GLEBE ROAD, 11TH FLOOR
ARLINGTON
VA
22203
US
|
Assignee: |
HOYA CORPORATION
Tokyo
JP
|
Family ID: |
28035296 |
Appl. No.: |
11/451421 |
Filed: |
June 13, 2006 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
10386102 |
Mar 12, 2003 |
|
|
|
11451421 |
Jun 13, 2006 |
|
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Current U.S.
Class: |
501/78 ; 65/66;
65/75 |
Current CPC
Class: |
C03B 2215/72 20130101;
C03B 11/084 20130101; C03B 11/005 20130101; B29C 43/361 20130101;
C03B 2215/07 20130101; B29L 2011/0016 20130101; C03C 3/068
20130101; C03B 11/08 20130101; B29C 43/021 20130101; C03B 2215/66
20130101; B29C 2043/3618 20130101 |
Class at
Publication: |
501/078 ;
065/075; 065/066 |
International
Class: |
C03C 3/068 20060101
C03C003/068; C03B 11/00 20060101 C03B011/00; C03B 7/00 20060101
C03B007/00 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 18, 2002 |
JP |
2002-74322 |
Claims
1. An optical glass for precision press molding, comprising
B.sub.2O.sub.3, SiO.sub.2, La.sub.2O.sub.3, Gd.sub.2O.sub.3, ZnO,
Li.sub.2O, ZrO.sub.2 and Ta.sub.2O.sub.5 as essential components,
containing 0 to 1 mol % of Sb.sub.2O.sub.3 as an optional
component, substantially containing none of PbO and
Lu.sub.2O.sub.3, having a glass transition temperature of
630.degree. C. or lower, and having a refractive index nd and an
Abbe's number .nu.d which satisfy all of the following relational
expressions, 1.80<nd.ltoreq.1.90 35<.nu.d.ltoreq.50, and
nd.gtoreq.2.025-(0.005.times..nu.d).
2. An optical glass for precision press molding, comprising
B.sub.2O.sub.3, SiO.sub.2, La.sub.2O.sub.3, Gd.sub.2O.sub.3, ZnO,
Li.sub.2O, ZrO.sub.2 and Ta.sub.2O.sub.5 as essential components,
containing 0 to 1 mol % of Sb.sub.2O.sub.3 as an optional
component, substantially containing none of PbO and
Lu.sub.2O.sub.3, having a glass transition temperature of
630.degree. C. or lower, and having a refractive index nd of
greater than 1.85 and an Abbe's number .nu.d of greater than
35.
3. An optical glass comprising, as essential components and by mol
%, 15 to 40% of B.sub.2O.sub.3, 3 to 25% of SiO.sub.2, 5 to 20% of
La.sub.2O.sub.3, 5 to 20% of Gd.sub.2O.sub.3, 2 to 35% of ZnO, 0.5
to 15% of Li.sub.2O, 0.5 to 15% of ZrO.sub.2 and 0.2 to 10% of
Ta.sub.2O.sub.5, containing 0 to 15% of WO.sub.3, 0 to 8% of
Y.sub.2O.sub.3, O to 8% of Yb.sub.2O.sub.3 and 0 to 1% of
Sb.sub.2O.sub.3 as optional components, and further containing
Nb.sub.2O.sub.5, BaO and GeO.sub.2 as optional components, the
total content of the above components being at least 95%, the
optical glass substantially containing none of PbO and
Lu.sub.2O.sub.3, having a glass transition temperature of
630.degree. C. or lower, and having a refractive index nd and an
Abbe's number .nu.d which satisfy all of the following relational
expressions, 1.80<nd.ltoreq.1.90 35<.nu.d.ltoreq.50, and
nd.gtoreq.2.025-(0.005.times..nu.d).
4. An optical glass as recited in claim 1, which contains
La.sub.2O.sub.3, Gd.sub.2O.sub.3, Yb.sub.2O.sub.3, Y.sub.2O.sub.3
and Sc.sub.2O.sub.3, the total content of La.sub.2O.sub.3,
Gd.sub.2O.sub.3, Yb.sub.2O.sub.3, Y.sub.2O.sub.3 and
Sc.sub.2O.sub.3 being 12 to 32 mol %, the molar ratio of the
content of La.sub.2O.sub.3 to said total content being 0.35 to
0.66.
5. A preform for precision press molding which is made of the
optical glass recited in claim 1.
6. An optical element which is made of the optical glass recited in
any one of claim 1.
7. A process for the production of a preform for precision press
molding, which comprises flowing a molten glass made of the optical
glass recited in any one of claim 1 from a flow pipe, isolating
molten glass having a predetermined weight, and shaping the
isolated molten glass having the predetermined weight while the
isolated molten glass is in a softened state.
8. A process for the production of an optical element which
comprises heating a preform made of an optical glass to soften the
preform and producing the optical element from the softened preform
by precision press molding, said preform being the preform recited
in claim 5.
9. A process for the production of an optical element which
comprises heating a preform made of an optical glass to soften the
preform and producing the optical element from the softened preform
by precision press molding, said preform being the preform produced
by the method recited in claim 7.
Description
TECHNICAL BACKGROUND
[0001] 1. Field of the Invention
[0002] The present invention relates to an optical glass for
precision press molding, a preform for precision press molding, an
optical element, and processes for the production of the preform
and the optical element. More specifically, the present invention
relates to a high-refractivity low-dispersion optical glass which
does not require machining of an optical-function surface such as
polishing or lapping after precision press molding thereof and
which is used for producing an optical element such as an
ultra-precision aspherical lens, a precision press molding preform
made of the optical glass, an optical element made of the same, and
processes for the production of the above preform and optical
element.
[0003] 2. Prior Art
[0004] In recent years, digital cameras have appeared, and as the
integration and function of machines and devices using an optical
system are rapidly enhanced, it is increasingly demanded to enhance
the precision of the optical system and to decrease the optical
system in weight and size. For materializing the above demands,
optical designing using an aspherical lens is coming to be a
mainstream. For stably supplying a large volume of aspherical
lenses made of a high-functional glass at a low cost, therefore,
attention is actively paid to a mold shaping technique of directly
forming an optical surface by press molding without polishing and
lapping, and demands for an optical glass having high functionality
(e.g., high refractivity and low-dispersion/high refractivity and
high-dispersion) and being suitable for mold-shaping are increasing
year after year.
[0005] Precision press molding of glass is a technique of shaping a
glass preform under pressure at a high temperature into a glass
shaped article having a form and a surface accuracy of an end
article or a form and a surface accuracy very close to those of an
end article. The above precision press molding enables the highly
productive production of shaped articles (molded articles) having a
desired form. At present, therefore, the precision press molding is
employed to produce optical parts such as spherical lenses,
aspherical lenses and diffraction gratings, and the like. For
producing an optical glass part by precision press-molding,
naturally, it is required to shape a glass preform under pressure
at a high temperature as described above, so that a mold used for
the pressing is exposed to a high temperature and that a high
pressure is applied thereto. It is therefore suppressing the damage
that is may be caused on the mold itself and a release film
provided on an inner surface of the mold by the high-temperature
environment of the press molding, it is desired to decrease the
glass transition temperature Tg and sag temperature Ts of a gob
preform for glass molding such that they are as low as
possible.
[0006] As an optical glass having high-refractivity low-dispersion
(refractive index nd>1.8 and Abbe's number .nu.d>35) optical
constants, various glasses containing B.sub.2O.sub.3 and
La.sub.2O.sub.3 are conventionally known. For example, such glasses
are disclosed in JP-A-8-217484, JP-A-54-90218 and
JP-A-62-100449.
[0007] However, the above optical glasses aim at an improvement in
devitrification resistance, and there is therefore involved a
problem that expensive components such as Lu.sub.2O.sub.3, etc.,
are essential, or that a large amount of Sb.sub.2O.sub.3 that is a
harmful component is essentially incorporated, for improving such
optical glasses in stability. Further, of glass compositions
disclosed in the above Publications, compositions that can attain a
refractive index nd>1.8 and an Abbe's number .nu.d>35 very
useful for optical designing contain almost no ZnO or Li.sub.2O
that is said to be effective for decreasing the glass transition
temperature, so that they have poor suitability to press
molding.
[0008] As described above, there has not been proposed any optical
glass which attains a refractive index nd>1.8 and an Abbe's
number .nu.d>35 (provided that a range surrounded by three
points (nd, .nu.d)=(1.85, 35), (1.8, 45) and (1.8, 35) is
excluded), or particularly, there has not yet been proposed any
optical glass for precision press molding which has optical
constants, a refractive index nd>1.85 and an Abbe's number
.nu.d>35.
[0009] The reason therefor is presumably as follows. Generally, a
glass having such optical constants has a large content of rare
earth metal oxide component and has a low degree of stabilization
against devitrification, so that it has been difficult to develop a
composition that makes it possible to decrease the glass transition
temperature to a region in which the glass can be press molded
economically.
SUMMARY OF THE INVENTION
[0010] Under the circumstances, it is an object of the present
invention to provide a high-refractivity low-dispersion optical
glass which does not require machining of an optical-function
surface, such as polishing or lapping, after precision press
molding thereof and which is used for producing an optical element,
a precision press molding preform made of the above optical glass,
an optical element made of the above glass, and processes for the
production of the above preform and the above optical element.
[0011] For achieving the above object, the present inventors have
made diligent studies and as a result, it has been found that the
above object can be achieved by an optical glass containing
specific components as essential components and having a glass
transition temperature of a specific value or smaller and specific
optical constants. On the basis of the finding, the present
invention has been completed.
[0012] That is, the present invention provides
[0013] (1) an optical glass for precision press molding (to be
referred to as "optical glass I" hereinafter) comprising
B.sub.2O.sub.3, SiO.sub.2, La.sub.2O.sub.3, Gd.sub.2O.sub.3, ZnO,
Li.sub.2O, ZrO.sub.2 and Ta.sub.2O.sub.5 as essential components,
containing 0 to 1 mol % of Sb.sub.2O.sub.3 as an optional
component, substantially containing none of PbO and
Lu.sub.2O.sub.3, having a glass transition temperature of
630.degree. C. or lower, and having a refractive index nd and an
Abbe's number .nu.d which satisfy all of the following relational
expressions,
[0014] 1.80<nd.ltoreq.1.90
[0015] 35<.nu.d.ltoreq.50, and
[0016] nd.gtoreq.2.025-(0.005.times..nu.d),
[0017] (2) an optical glass for precision press molding (to be
referred to as "optical glass II" hereinafter) comprising
B.sub.2O.sub.3, SiO.sub.2, La.sub.2O.sub.3, Gd.sub.2O.sub.3, ZnO,
Li.sub.2O, ZrO.sub.2 and Ta.sub.2O.sub.5 as essential components,
containing 0 to 1 mol % of Sb.sub.2O.sub.3 as an optional
component, substantially containing none of PbO and
Lu.sub.2O.sub.3, having a glass transition temperature of
630.degree. C. or lower, and having a refractive index nd of
greater than 1.85 and an Abbe's number .nu.d of greater than
35,
[0018] (3) an optical glass (to be referred to as "optical glass
III" hereinafter) comprising, as essential components and by mol %,
15 to 40% of B.sub.2O.sub.3, 3 to 25% of SiO.sub.2, 5 to 20% of
La.sub.2O.sub.3, 5 to 20% of Gd.sub.2O.sub.3, 2 to 35% of ZnO, 0.5
to 15% of Li.sub.2O, 0.5 to 15% of ZrO.sub.2 and 0.2 to 10% of
Ta.sub.2O.sub.5, containing 0 to 15% of WO.sub.3, 0 to 8% of
Y.sub.2O.sub.3, 0 to 8% of Yb.sub.2O.sub.3 and 0 to 1% of
Sb.sub.2O.sub.3 as optional components, and further containing
Nb.sub.2O.sub.5, BaO and GeO.sub.2 as optional components, the
total content of the above components being at least 95%, the
optical glass substantially containing none of PbO and
Lu.sub.2O.sub.3, having a glass transition temperature of
630.degree. C. or lower, and having a refractive index nd and an
Abbe's number .nu.d which satisfy all of the following relational
expressions,
[0019] 1.80<nd.ltoreq.1.90
[0020] 35<.nu.d.ltoreq.50, and
[0021] nd.gtoreq.2.025-(0.005.times..nu.d),
[0022] (4) an optical glass as recited in the above (1), (2) or
(3), which contains La.sub.2O.sub.3, Gd.sub.2O.sub.3,
Yb.sub.2O.sub.3, Y.sub.2O.sub.3 and Sc.sub.2O.sub.3, the total
content of La.sub.2O.sub.3, Gd.sub.2O.sub.3, Yb.sub.2O.sub.3,
Y.sub.2O.sub.3 and Sc.sub.2O.sub.3 being 12 to 32 mol %, the molar
ratio of the content of La.sub.2O.sub.3 to said total content being
0.35 to 0.66,
[0023] (5) a preform for precision press molding which is made of
the optical glass recited in any one of the above (1) to (4),
[0024] (6) an optical element which is made of the optical glass
recited in any one of the above (1) to (4),
[0025] (7) a process for the production of a preform for precision
press molding, which comprises flowing a molten glass made of the
optical glass recited in any one of the above (1) to (4) from a
flow pipe, isolating molten glass having a predetermined weight,
and shaping the isolated molten glass having the predetermined
weight while the isolated molten glass is in a softened state,
and
[0026] (8) a process for the production of an optical element which
comprises heating a preform made of an optical glass to soften the
preform and producing the optical element from the softened preform
by precision press molding, said preform being the preform recited
in the above (5) or the preform produced by the method recited in
the above (7).
BRIEF DESCRIPTION OF DRAWINGS
[0027] FIG. 1 is a graph showing a range of the refractive index nd
and Abbe's number .nu.d that one embodiment of the optical glass of
the present invention has.
[0028] FIG. 2 is a schematic cross-sectional view of one example of
a precision press molding apparatus used in Examples.
DETAILED DESCRIPTION OF THE INVENTION
[0029] The "press molding" in the present invention refers to a
press molding method in which a glass material is heated to bring
it into a press-moldable state, and press-shaping the glass
material into a product by means of a press mold thereby to
precisely transfer a molding surface of the press mold to the glass
material that is in the above state, whereby the product (end
article) can be produced without applying machining such as
polishing and lapping, etc., to the molded product after the press
molding. The press molding is generally applied to the formation of
optical elements (e.g., a lens, prism, and the like). In the
precision press molding of an optical element, for example, the
molding surface of a press mold is precisely transferred thereby to
form an optical-function surface (a surface that performs an
optical function like a surface which transmits or reflects light
(beam) to be controlled in an optical element), so that the
thus-formed optical-function surface can be allowed to exhibit
performances as an optical-function surface without machining the
optical-function surface after the press molding. The method of
press-molding an optical element by the above method is generally
called "mold optics shaping", and the method of precision press
molding of an aspherical lens is particularly an excellently
productive method since it is not required to polish or lap an
optical-function surface into an aspherical surface.
[0030] The precision press molding is a method in which an article
required to have a high surface accuracy and internal quality such
as an optical element can be mass-produced highly productively.
However, the glass to which the above method can be applied is
limited to a glass that can undergo plastic deformation at a
relatively low temperature. When a glass having a high glass
transition temperature is used, the molding surface of a
press-shaping mold is exposed to a high temperature during the
precision press molding, so that the above molding surface is
intensely worn or broken. In the precision press molding, even a
fine flaw that occurs on the molding surface of a press-shaping
mold is transferred to the optical-function surface of an optical
element that is an end article, which means that the function of
the optical element is impaired. The glass transition temperature
of the glass that is usable is therefore limited to 630.degree. C.
or lower.
[0031] The optical glass of the present invention includes three
embodiments, the optical glass I, the optical glass II and the
optical glass III. The optical glass I will be explained first.
[0032] The optical glass I of the present invention is an optical
glass containing B.sub.2O.sub.3, SiO.sub.2, La.sub.2O.sub.3,
Gd.sub.2O.sub.3, ZnO, Li.sub.2O, ZrO.sub.2 and Ta.sub.2O.sub.5 as
essential components, containing 0 to 1 mol % of Sb.sub.2O.sub.3 as
an optional component, substantially containing none of PbO and
Lu.sub.2O.sub.3, having a glass transition temperature of
630.degree. C. or lower, and having a refractive index nd and an
Abbe's number .nu.d which satisfy all of the following relational
expressions,
[0033] 1.80<nd.ltoreq.1.90
[0034] 35<.nu.d.ltoreq.50, and
[0035] nd.gtoreq.2.025-(0.005.times..nu.d),
[0036] The reason why the glass transition temperature of the
optical glass I is limited to 630.degree. C. or lower is as already
explained. Further, the optical glass I is required to be a
high-refractivity low-dispersion optical glass having a refractive
index nd and an Abbe's number .nu.d which satisfy all of the above
three relational expressions. When the above requirement is
illustrated in FIG. 1, nd and .nu.d exist in a region that is
indicated by slanting lines but does not include nd 1.80 and .nu.d
35. In FIG. 1, the axis of abscissas shows Abbe's number .nu.d, and
the axis of ordinates shows a refractive index nd.
[0037] The contents of the essential components in the above
optical glass I are not specially limited so long as there can be
obtained an optical glass having a glass transition temperature of
630.degree. C. or lower and having an refractive index nd and an
Abbe's number .nu.d which satisfy all of the above three relational
expressions. However, the contents of the essential components are
preferably the same as those in the optical glass III to be
described later. The function of each essential component will be
explained later with regard to the optical glass III.
[0038] In the optical glass I, Sb.sub.2O.sub.3 as an optional
component is used as an refining agent, and when it is used in an
amount of 1 mol % or less, a sufficient effect can be obtained.
Further, when the content of Sb.sub.2O.sub.3 is large, the molding
surface of the press-shaping mold may be damaged during precision
press molding. The content of Sb.sub.2O.sub.3 is therefore limited
to 1 mol % or less.
[0039] Further, the optical glass I substantially contains none of
PbO and Lu.sub.2O.sub.3. The above "substantially containing none
of PbO and Lu.sub.2O.sub.3" means that the optical glass I contains
none of these substances that are intentionally incorporated other
than those included as impurities. Generally, the precision press
molding is carried out in a non-oxidizing atmosphere such as a
nitrogen atmosphere for protecting the molding surface of a
press-shaping mold. PbO is a component that can be easily reduced,
so that the surface of a molded product comes to be cloudy due to a
deposit formed by reduction during the precision press. Further,
since PbO is environmentally detrimental, PbO is excluded.
Lu.sub.2O.sub.3 is not generally frequently used as a component for
a glass as compared with other components. Further, Lu.sub.2O.sub.3
is a substance having a high scarcity value and is expensive for a
raw material for an optical glass, so that it is not any component
whose use is desirable. The optical glass I of the present
invention has stability as a glass having the above properties, so
that an unnecessary Lu.sub.2O.sub.3 is excluded.
[0040] The optical glass II of the present invention is a glass
containing B.sub.2O.sub.3, SiO.sub.2, La.sub.2O.sub.3,
Gd.sub.2O.sub.3, ZnO, Li.sub.2O, ZrO.sub.2 and Ta.sub.2O.sub.5 as
essential components, containing 0 to 1 mol % of Sb.sub.2O.sub.3 as
an optional component, substantially containing none of PbO and
Lu.sub.2O.sub.3, having a glass transition temperature of
630.degree. C. or lower, and having a refractive index nd of
greater than 1.85 and an Abbe's number .nu.d of greater than
35.
[0041] The reason why the glass transition temperature of the
optical glass II is limited to 630.degree. C. or lower is as
already explained. Further, the optical glass II is required to be
a high-refractivity low-dispersion glass having a refractive index
nd of greater than 1.85 and an Abbe's number .nu.d of greater than
35.
[0042] The contents of the essential components in the above
optical glass II are not specially limited so long as there can be
obtained an optical glass having a glass transition temperature of
630.degree. C. or lower and having an refractive index nd of
greater than 1.85 and an Abbe's number .nu.d of greater than 35.
However, the contents of the essential components are preferably
the same as those in the optical glass III to be described later.
The function of each essential component will be explained later
with regard to the optical glass III.
[0043] Sb.sub.2O.sub.3 as an optional component in the optical
glass II is as explained with regard to the above optical glass
I.
[0044] Further, the optical glass II substantially contains none of
PbO and Lu.sub.2O.sub.3. These components are also as explained
with regard to the above optical glass I.
[0045] The optical glass III of the present invention is an optical
glass containing, as essential components and by mol %, 15 to 40%
of B.sub.2O.sub.3, 3 to 25% of SiO.sub.2, 5 to 20% of
La.sub.2O.sub.3, 5 to 20% of Gd.sub.2O.sub.3, 2 to 35% of ZnO, 0.5
to 15% of Li.sub.2O, 0.5 to 15% of ZrO.sub.2 and 0.2 to 10% of
Ta.sub.2O.sub.5, containing 0 to 15% of WO.sub.3, 0 to 8% of
Y.sub.2O.sub.3, 0 to 8% of Yb.sub.2O.sub.3 and 0 to 1% of
Sb.sub.2O.sub.3 as optional components, further containing
Nb.sub.2O.sub.5, BaO and GeO.sub.2 as optional components, the
total content of the above components being at least 95%, the
optical glass substantially containing none of PbO and
Lu.sub.2O.sub.3, having a glass transition temperature of
630.degree. C. or lower, and having a refractive index nd and an
Abbe's number .nu.d which satisfy all of the following relational
expressions,
[0046] 1.80<nd.ltoreq.1.90
[0047] 35<.nu.d.ltoreq.50, and
[0048] nd.gtoreq.2.025-(0.005.times..nu.d).
[0049] The reason why the glass transition temperature of the
optical glass III is limited to 630.degree. C. or lower is as
already explained. Further, the optical glass III is required to be
a high-refractivity low-dispersion glass having optical constants,
refractive index nd and Abbe's number .nu.d, which satisfy all of
the above three relational expressions.
[0050] The above composition has been found on the basis of
experimental chemistry. The unit of the contents (%) to be
discussed below is mol %.
[0051] B.sub.2O.sub.3 is a network-forming oxide and an essential
component in the optical glass (I, II and III) of the present
invention. Particularly when a high-refractivity component such as
La.sub.2O.sub.3 or Gd.sub.2O.sub.3 is incorporated in a large
amount, it is required to use B.sub.2O.sub.3 as a main
network-forming component for forming a glass. However, the content
of B.sub.2O.sub.3 exceeds 40%, the refractive index of the glass is
decreased, and the glass obtained is not suitable for obtaining a
high-refractivity glass. When it is less than 15%, the glass has no
sufficient stability against devitrification, and the meltability
of the glass decreases, so that the content of B.sub.2O.sub.3 is
preferably 15 to 40%, more preferably 20 to 37%.
[0052] SiO.sub.2 is a component for forming a glass network like
B.sub.2O.sub.3, and when a small amount of SiO.sub.2 is
incorporated into a glass containing a large amount of
La.sub.2O.sub.3 and Gd.sub.2O.sub.3 as a substitute for part of
B.sub.2O.sub.3 that is a main component, SiO.sub.2 causes the
liquidus temperature of the glass to decrease, improves the glass
in high-temperature viscosity and greatly improves the glass in
stability. When the content of SiO.sub.2 is less than 3%, the above
effects are hardly produced. When the content of SiO.sub.2 exceeds
25%, the refractive index of the glass decreases, and further, the
glass transition temperature increases, so that precision press
molding of the glass is difficult. The content of SiO.sub.2 is
therefore preferably in the range of 3 to 25%, more preferably in
the range of 5 to 20%.
[0053] As described already, La.sub.2O.sub.3 is an essential
component that causes the refractive index to increase and improves
the chemical durability of the glass without decreasing the
stability of the glass against devitrification and without
increasing the dispersion. However, when the content of
La.sub.2O.sub.3 is less than 5%, no sufficient effect is produced,
and when it exceeds 20%, the glass is greatly deteriorated in
stability against devitrification. The content of La.sub.2O.sub.3
is therefore preferably in the range of 5 to 20%, more preferably
in the range of 7 to 18%.
[0054] Like La.sub.2O.sub.3, Gd.sub.2O.sub.3 works to improve the
glass in refractivity and chemical durability without deteriorating
the stability of the glass against devitrification and the low
dispersion of the glass. However, when the content of
Gd.sub.2O.sub.3 is less than 5%, no sufficient effect can be
obtained. When it exceeds 20%, the stability of the glass against
devitrification is deteriorated, and the glass transition
temperature increases, so that the precision press molding of the
glass is difficult. The content of Gd.sub.2O.sub.3 is therefore
preferably in the range of 5 to 20%, more preferably 6 to 18%,
still more preferably 7 to 18%.
[0055] In the glass of
B.sub.2O.sub.3--SiO.sub.2--La.sub.2O.sub.3--Gd.sub.2O.sub.3--ZnO--Li.sub.-
2O--ZrO.sub.2--Ta.sub.2O.sub.5, generally, the total content of
La.sub.2O.sub.3+Gd.sub.2O.sub.3 is adjusted preferably to at least
12%, more preferably to 12 to 32%, for maintaining high
functionality of high-refractivity and low-dispersion (refractive
index nd>1.8 and Abbe's number .nu.d>35).
[0056] The amount ratio of the content of La.sub.2O.sub.3 by mol %
to the total content of lanthanoid oxides Ln.sub.2O.sub.3 (Ln=La,
Gd, Yb, Y, Sc) by mol % in the glass,
La.sub.2O.sub.3/.SIGMA.Ln.sub.2O.sub.3, is preferably in the range
of 0.35 to 0.66, more preferably 0.45 to 0.66. The reason therefor
will be explained below.
[0057] In the glass for precision press molding, it is required to
incorporate Li.sub.2O and the like, components that impart the
glass with precision press molding suitability, i.e., a low glass
transition temperature but destabilize the glass. When the content
of the lanthanoid oxides essential for high refractivity and low
dispersion is increased, molding of the glass comes to be
impossible. Generally, the amount (.SIGMA.Ln.sub.2O.sub.3) is
therefore limited.
[0058] However, the present inventors have found the following.
Lanthanoid oxides other than La.sub.2O.sub.3 are added such that
the ratio of the content of La.sub.2O.sub.3 to the total content of
lanthanoid oxides Ln.sub.2O.sub.3 is 0.35 to 0.66, whereby a stable
glass can be obtained while increasing the amount of the lanthanoid
oxides, and the glass containing Li.sub.2O, etc., components that
decrease the stability of the glass can be molded as a glass.
Further, it has been found that maintaining the above ratio serves
to decrease the liquidus temperature and to improve the
high-temperature viscosity. That is, when the ratio of
La.sub.2O.sub.3/.SIGMA.Ln.sub.2O.sub.3 is in the range of 0.35 to
0.66, a remarkably stable glass can be obtained as compared with a
case where the total content .SIGMA.Ln.sub.2O.sub.3 is constant and
the ratio of La.sub.2O.sub.3/.SIGMA.Ln.sub.2O.sub.3 is larger. For
the above reason, further, it is preferred to adjust the total
content (.SIGMA.Ln.sub.2O.sub.3) of La.sub.2O.sub.3,
Gd.sub.2O.sub.3, Yb.sub.2O.sub.3, Y.sub.2O.sub.3 and
Sc.sub.2O.sub.3 to 12 to 32%.
[0059] ZnO is an essential component that decreases the melting
temperature, liquidus temperature and glass transition temperature
of the glass and is indispensable for the adjustment of a
refractive index. When the content of ZnO is less than 2%, the
expected results above cannot be obtained. When the content thereof
exceeds 35%, the dispersion is large, the stability against
devitrification deteriorates, and the chemical durability
decreases. The content of ZnO is preferably in the range of 2 to
35%, more preferably in the range of 5 to 32%.
[0060] Li.sub.2O is a component that decreases the glass transition
temperature to a great extent without involving a great decrease in
refractive index or a decrease in chemical durability, as compared
with any other alkali metal oxide component. Particularly, when
Li.sub.2O is incorporated in a small amount, the effect thereof is
large for its amount, and it is effective for adjusting thermal
properties of the glass. When the content of Li.sub.2O is less than
0.5%, it produces little effect. When it exceeds 15%, the stability
of the glass against devitrification sharply decreases, and the
liquidus temperature of the glass also increases. The content of
Li.sub.2O is therefore preferably in the range of 0.5 to 15%, more
preferably 1 to 12%, still more preferably 2 to 12%.
[0061] Both ZnO and Li.sub.2O are components that decrease the
glass transition temperature, so that the total content of
ZnO+Li.sub.2O is preferably adjusted to at least 10 mol %, more
preferably to at least 15 mol %.
[0062] ZrO.sub.2 is incorporated as a component for attaining
high-refractivity and low-dispersion properties. When a small
amount of ZrO.sub.2 is incorporated, it has the effect of improving
the high-temperature viscosity and the stability against
devitrification, so that it is preferred to incorporate a small
amount of ZrO.sub.2. When the content of ZrO.sub.2 is less than
0.5%, it produces little effect. When the content thereof exceeds
15%, the liquidus temperature sharply increases, and the stability
against devitrification is deteriorated. Therefore, the content of
ZrO.sub.2 is preferably in the range of 0.5 to 15%, more preferably
1 to 10%.
[0063] Ta.sub.2O.sub.5 is incorporated as a component for attaining
high-refractivity and low-dispersion properties. When a small
amount of Ta.sub.2O.sub.5 is incorporated, it has the effect of
improving the glass in high-temperature viscosity and stability
against devitrification, so that it is preferred to incorporate a
small amount of Ta.sub.2O.sub.5. When the content of
Ta.sub.2O.sub.5 is less than 0.2%, it produces no effect. When it
exceeds 10%, the liquidus temperature sharply increases, and the
dispersion becomes large. Therefore, the content of Ta.sub.2O.sub.5
is preferably in the range of 0.2 to 10%, more preferably 1 to
8%.
[0064] WO.sub.3 is a component that is incorporated as required for
improving the glass in stability and meltability and improving the
glass in refractivity. When the content of WO.sub.3 exceeds 15%,
the dispersion becomes large, and the necessary low-dispersion
property can be no longer obtained. Therefore, the content of
WO.sub.3 is preferably 15% or less, more preferably 12% or
less.
[0065] Y.sub.2O.sub.3, Yb.sub.2O.sub.3 and BaO are incorporated as
component for attaining high-refractivity and low-dispersion
properties. When it is incorporated in a small amount, it improves
the glass in stability and chemical durability. When the content of
each of individual components exceeds 8%, any one of these impairs
the stability of the glass against devitrification to a great
extent and increases the glass transition temperature and sag
temperature. Each component is therefore preferably controlled such
that the content thereof is 8% or less, more preferably, 7% or
less.
[0066] Nb.sub.2O.sub.5 is a component that is incorporated as
required for improving the glass in stability and refractivity.
When the content thereof exceeds 8%, the dispersion becomes large,
and the necessary low-dispersion property can be no longer
obtained. Therefore, the content of Nb.sub.2O.sub.5 is preferably
8% or less, more preferably 5% or less.
[0067] GeO.sub.2 is a component that stabilizes the glass like
SiO.sub.2 and imparts the glass with a higher refractive index than
SiO.sub.2 does. However, GeO.sub.2 is expensive and increases the
dispersion, so that the content of GeO.sub.2 is preferably 8% or
less.
[0068] Further, Sb.sub.2O.sub.3, PbO and Lu.sub.2O.sub.3 are as
explained with regard to the above optical glass I.
[0069] When the optical glass has a composition containing the
above optional components in the above amounts as required, there
can be obtained an optical glass having qualities and properties
that are explained to be preferred. Above all, the optical glass
more preferably has a glass composition containing 20 to 37% of
B.sub.2O.sub.3, 5 to 20% of SiO.sub.2, 7 to 18% of La.sub.2O.sub.3,
6 to 18% of Gd.sub.2O.sub.3, 5 to 32% of ZnO, 1 to 12% of
Li.sub.2O, 1 to 10% of ZrO.sub.2, 1 to 8% of Ta.sub.2O.sub.5, 0 to
12% of WO.sub.3, 0 to 7% of Y.sub.2O.sub.3, 0 to 7% of
Yb.sub.2O.sub.3, 0 to 5% of Nb.sub.2O.sub.5, 0 to 7% of BaO, 0 to
8% of GeO.sub.2 and 0 to 1% of Sb.sub.2O.sub.3, the total content
of La.sub.2O.sub.3 and Gd.sub.2O.sub.3 being 12 to 32%,
La.sub.2O.sub.3/.SIGMA.Ln.sub.2O.sub.3 being 0.45 to 0.66. the
optical glass more preferably has a glass composition containing 20
to 37% of B.sub.2O.sub.3, 5 to 20% of SiO.sub.2, 7 to 18% of
La.sub.2O.sub.3, 7 to 18% of Gd.sub.2O.sub.3, 5 to 32% of ZnO, 2 to
12% of Li.sub.2O, 1 to 10% of ZrO.sub.2, 1 to 8% of
Ta.sub.2O.sub.5, 0 to 12% of WO.sub.3, 0 to 7% of Y.sub.2O.sub.3, 0
to 7% of Yb.sub.2O.sub.3, 0 to 5% of Nb.sub.2O.sub.5, 0 to 7% of
BaO, 0 to 8% of GeO.sub.2 and 0 to 1% of Sb.sub.2O.sub.3, the total
content of La.sub.2O.sub.3 and Gd.sub.2O.sub.3 being 12 to 32%,
La.sub.2O.sub.3/.SIGMA.Ln.sub.2O.sub.3 being 0.45 to 0.66.
[0070] In the above composition, the above more preferred
composition and the above particularly preferred composition, it is
important that the total content of the above components is at
least 95% for obtaining the desired optical properties and at the
same time for maintaining the stability of the glass. The optical
glass may contain other components such as Na.sub.2O, K.sub.2O,
CaO, SrO, TiO.sub.2, Al.sub.2O.sub.3, Ga.sub.2O.sub.3, and the like
in a total content of 5% or less for adjusting properties of the
glass.
[0071] In the above glass composition and the above more preferred
composition, preferably, the total content of B.sub.2O.sub.3,
SiO.sub.2, ZnO, Li.sub.2O, La.sub.2O.sub.3, Gd.sub.2O.sub.3,
ZrO.sub.2, Ta.sub.2O.sub.5, WO.sub.3, Y.sub.2O.sub.3 and
Yb.sub.2O.sub.3 is at least 95%, and more preferably, the above
total content is at least 99%. Still more preferably, the above
total content is 100%.
[0072] Desirably, the optical glass (any one of the optical glasses
I, II and III) of the present invention does not contain any
environmentally detrimental elements such as cadmium, radioactive
elements such as thorium or toxic elements such as arsenic.
Further, desirably, they do not contain any fluorine in view of
volatilization during melting of the glass.
[0073] The optical glass (any one of the optical glasses I, II and
III) of the present invention can be produced, for example, by
formulating material compounds and melting, refining, stirring and
homogenizing the formulated glass material according to a
conventional method.
[0074] Further, a glass melt that gives any one of the optical
glasses (I, II and III) of the present invention is allowed to flow
into a 40.times.70.times.15 mm mold made of carbon, allowed to
gradually cool to a glass transition temperature, then annealed at
the glass transition temperature for 1 hour and allowed to cool to
room temperature to obtain a glass. In this case, there is
precipitated no crystal that is observable through a microscope. As
described above, the optical glass (any one of the optical glasses
I, II and III) of the present invention is excellent in
stability.
[0075] The optical glass of the present invention is transparent in
a visible light region and suitable for producing a lens, a prism
and other optical elements.
[0076] A precision press molding preform made of the optical glass
(any one of the optical glasses I, II and III) of the present
invention and a method of preparing the same will be explained
below.
[0077] The precision press molding preform refers to a pre-shaped
glass material to be precision press molded under heat. As is
already explained, the precision press molding is a method in which
an optical-function surface is formed by press molding, whereby an
optical element as an end article (final product) is produced
without any polishing or lapping. When no removing processing like
polishing and lapping is not carried out in any other portion than
the optical-function surface of a precision press molded article,
the weight of the preform is adjusted such that it is equivalent to
the weight of an end article (final product). The weight of a
precision press molded article is also equivalent to this weight.
When the weight of a preform is smaller than the weight of an end
precision press molded article, the glass is not fully charged in
the molding surface of a press-shaping mold during its precision
press molding, and there is caused a problem that no intended
surface accuracy can be obtained or that the thickness of a molded
article is smaller than an intended thickness. Further, when the
weight of a preform is larger than the weight of an end precision
press molded article, there is caused a problem that excess glass
penetrate gaps of precision press mold members to form burrs, or
that a molded article has a larger thickness than an intended
thickness. It is therefore required to control the weight of a
precision press molding preform more accurately than the weight of
any general press molding glass material that is finished by
polishing or lapping after press molded. In the precision press
molding preform, further, the surface of the preform is left on an
end article as a press molded article surface, so that the surface
of the preform is required to be free of a flaw and soiling.
[0078] The method for producing the above precision press molding
preform includes a method in which a molten glass is allowed to
flow, a molten glass gob having a predetermined weight is
separated, and the molten glass gob is shaped into a preform (to be
referred to as "hot shaping method" hereinafter) and a method in
which a molten glass is cast into a mold, a shaped glass is cooled,
and the obtained glass gob is machined to a predetermined size (to
be referred to as "cold shaping method" hereinafter).
[0079] In the hot shaping method, a molten glass which is prepared
by melting, clarification and homogenization and which has, for
example, a temperature of approximately 1,000 to 1,400.degree. C.
and a viscosity of approximately 0.1 to 5 dPas is prepared, the
temperature of the above molten glass is adjusted such that the
molten glass has a viscosity of approximately 3 to 60 dPas, and the
molten glass is allowed to flow out of a flow nozzle or a flow
pipe, to shape it into a preform. The method of adjusting the above
temperature includes, for example, a method in which the
temperature of the flow nozzle or the flow pipe is controlled. The
flow nozzle or flow pipe is desirably made of platinum or a
platinum alloy. The method of shaping the molten glass into a
preform specifically includes a method in which molten glass is
dropped from the flow nozzle as a molten glass drop having a
predetermined weight and the molten glass drop is received with a
receiving member and shaped into a preform, a method in which the
above molten glass drop having a predetermined weight is dropped
from the above flow nozzle into liquid nitrogen and shaped into a
preform, and a method in which a molten glass flow is allowed to
flow down from the flow pipe made of platinum or a platinum alloy,
a forward end portion of the molten glass flow is received with a
receiving member, a constricted portion is formed in a molten glass
flow portion between the nozzle and the receiving member, molten
glass flow is separated in the constricted portion, and a molten
glass gob having a predetermined weight is received with the
receiving member and shaped into a preform. When the molten glass
is dropped, the glass preferably has a viscosity of 3 to 30 dPas.
When the molten glass is flowed down as a molten glass flow, the
glass preferably has a viscosity of 2 to 60 dPas.
[0080] The form of the preform can be determined by taking account
of the form of precision press molded article. Examples of the form
of the preform preferably include a spherical form and an oval
form. In the hot shaping method, a preform having a smooth surface
can be easily obtained since the surface of the preform is formed
when the glass has a softening temperature or higher. Particularly,
in a method in which a molten glass gob is shaped into a preform
while floated above a shaping mold with air pressure, or a method
in which a molten glass gob is placed into, and shaped into a
preform in, a medium prepared by cooling a substance that is a gas
at an ordinary temperature under ordinary pressure into a liquid,
there can be easily produced a preform having a smooth surface free
of flaws, soling and surface alteration, for example, a preform
having a free surface.
[0081] In the cold shaping method, for example, the above molten
glass prepared by melting, refining and homogenization is cast into
a casting mold, shaped into the form of a glass block, the glass
block is gradually cooled to decrease strain of the glass, then,
the glass block is machined or cut to prepare a glass gob having
predetermined dimensions and a predetermined weight, and the glass
gob is surface-smoothened to give a preform.
[0082] The method of precision press molding the above preform to
produce an optical element will be explained below.
[0083] The precision press molding uses a press-shaping mold having
a molding surface that is accurately processed beforehand so as to
have a desired form, and a release film may be formed on the
molding surface for preventing the fusion of the glass during
pressing. The precision press molding can be carried out by a known
method including precision press molding in an atmosphere of a
non-oxidizing gas such as nitrogen gas for preventing damage of the
molding surface, such as damage by oxidation.
[0084] In the above manner, various lenses such as a spherical
lens, an aspherical lens, a micro lens, a lens array, a micro lens
array, etc., and optical elements such as a prism, a polygonal
mirror, etc., can be produced from the optical glass (any one of
the optical glasses I, II, and III) of the present invention
without machining their optical-function surfaces.
EXAMPLES
[0085] The present invention will be explained more specifically
with reference to Examples hereinafter, while the present invention
shall not be limited to these Examples.
Examples 1-64
[0086] Oxides, carbonates, sulfates, nitrates, hydroxides, etc.,
such as SiO.sub.2, H.sub.3BO.sub.3, La.sub.2O.sub.3, ZnO,
ZnCO.sub.3, ZrO.sub.2, Li.sub.2CO.sub.3, etc., as raw materials
were provided, and 250 to 300 g of each of these components was
weighed so as to form compositions shown in Tables 1 to 7. These
raw materials in each Example were fully mixed to prepare a
formulated batch, the formulated batch was placed in a platinum
crucible, and the formulated batch was melted in air in an electric
furnace maintained at 1,200 to 1,450.degree. C., with stirring for
2 to 4 hours. After melted, the glass melt was allowed to flow into
a 40.times.70.times.15 mm mold made of carbon and allowed to cool
to a glass transition temperature, and immediately thereafter, the
glass was placed in an annealing furnace and annealed in a glass
transition temperature range for about 1 hour. Then, the glass in
the furnace was allowed to cool to room temperature, to give an
optical glass. In the thus-obtained optical glasses, there was
precipitated no crystal that was observable through a
microscope.
[0087] Each optical glass was measured for properties according to
the following methods. Tables 1 to 7 shows the results.
[0088] (1) Refractive Index (nd) and Abbe's Number (.nu.d)
[0089] An optical glass held at a temperature between Tg and Ts was
temperature-decreased at a temperature decrease rate of -30.degree.
C./hour, and the optical glass was measured for a refractive index
(nd) and an Abbe's number (.nu.d).
[0090] (2) Glass Transition Temperature (Tg) and Sag Temperature
(Ts)
[0091] An optical glass was measured at a temperature elevation
rate of 4.degree. C./minute with a thermomechanical analyzer
supplied by Rigaku Denki K.K. TABLE-US-00001 TABLE 1 Example 1 2 3
4 5 6 7 8 9 10 Glass B.sub.2O.sub.3 32.28 35.48 33.86 33.33 35.20
34.65 35.48 35.63 30.28 31.62 com- SiO.sub.2 9.45 9.68 9.45 9.52
9.60 9.45 9.68 9.72 9.56 9.49 position La.sub.2O.sub.3 9.06 9.27
7.87 9.13 9.20 9.06 8.06 8.10 10.36 9.49 (mol %) Gd.sub.2O.sub.3
9.06 9.27 7.87 9.13 9.20 9.06 8.06 8.10 10.36 9.49 ZnO 28.35 24.19
28.35 28.57 25.60 28.35 22.58 22.67 22.31 23.72 Li.sub.2O 3.94 4.03
3.94 3.97 4.00 2.36 5.65 5.67 5.58 5.53 ZrO.sub.2 4.72 4.84 4.72
3.17 4.80 4.72 6.45 5.67 3.98 3.95 Ta.sub.2O.sub.5 3.15 3.23 3.15
3.17 2.40 2.36 4.03 3.64 2.79 1.98 WO.sub.3 0.00 0.00 0.00 0.00
0.00 0.00 0.00 0.00 4.78 4.74 Y.sub.2O.sub.3 0.00 0.00 0.00 0.00
0.00 0.00 0.00 0.00 0.00 0.00 Yb.sub.2O.sub.3 0.00 0.00 0.00 0.00
0.00 0.00 0.00 0.00 0.00 0.00 Nb.sub.2O.sub.5 0.00 0.00 0.79 0.00
0.00 0.00 0.00 0.81 0.00 0.00 BaO 0.00 0.00 0.00 0.00 0.00 0.00
0.00 0.00 0.00 0.00 TiO.sub.2 0.00 0.00 0.00 0.00 0.00 0.00 0.00
0.00 0.00 0.00 (.SIGMA.Ln.sub.2O.sub.3) (18.12) (18.54) (15.74)
(18.26) (18.40) (18.12) (16.12) (16.20) (20.72) (18.98)
(La.sub.2O.sub.3/.SIGMA.Ln.sub.2O.sub.3) (0.50) (0.50) (0.50)
(0.50) (0.50) (0.50) (0.50) (0.50) (0.50) (0.50) (Li.sub.2O + ZnO)
(32.28) (28.23) (32.28) (32.54) (29.60) (30.71) (28.23) (28.34)
(27.89) (29.25) (La.sub.2O.sub.3 + Gd.sub.2O.sub.3) (18.12) (18.54)
(15.74) (18.26) (18.40) (18.12) (16.12) (16.20) (20.72) (18.98)
Total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0
Properties Tg(TMA)(.degree. C.) 566 573 556 564 570 577 562 561 565
556 Ts(.degree. C.) 616 623 606 614 620 627 612 611 615 606 nd
1.81751 1.81014 1.81033 1.81032 1.81040 1.80680 1.80756 1.81001
1.84150 1.82528 .nu.d 43.95 44.51 43.26 44.40 44.50 44.97 43.77
43.20 40.85 41.79 Specific gravity 5.08 5.00 4.92 5.05 5.01 4.99
4.91 4.87 5.30 5.13 Note) (La.sub.2O.sub.3/.SIGMA.Ln.sub.2O.sub.3)
= ratio of molar amounts
[0092] TABLE-US-00002 TABLE 2 Example 11 12 13 14 15 16 17 18 19 20
Glass B.sub.2O.sub.3 30.83 30.28 31.08 30.52 25.29 24.90 31.33
31.58 31.08 25.68 com- SiO.sub.2 9.49 9.56 9.56 9.64 18.39 16.60
9.64 9.72 9.56 15.56 position La.sub.2O.sub.3 9.88 9.96 9.96 10.44
11.11 15.77 10.84 11.74 11.55 12.06 (mol %) Gd.sub.2O.sub.3 9.88
9.96 9.96 10.44 11.11 9.54 10.84 11.74 11.55 12.06 ZnO 22.13 22.31
20.72 20.88 19.92 8.30 20.88 17.81 20.72 20.23 Li.sub.2O 5.53 5.58
5.58 5.62 2.30 9.96 4.02 4.05 2.39 2.33 ZrO.sub.2 4.74 3.98 5.58
4.02 3.83 3.32 4.02 4.05 3.98 3.89 Ta.sub.2O.sub.5 1.98 3.59 2.79
3.61 3.45 4.15 3.61 2.83 2.79 3.50 WO.sub.3 5.53 4.78 4.78 4.82
4.60 5.81 4.82 6.48 6.37 4.67 Y.sub.2O.sub.3 0.00 0.00 0.00 0.00
0.00 1.66 0.00 0.00 0.00 0.00 Yb.sub.2O.sub.3 0.00 0.00 0.00 0.00
0.00 0.00 0.00 0.00 0.00 0.00 Nb.sub.2O.sub.5 0.00 0.00 0.00 0.00
0.00 0.00 0.00 0.00 0.00 0.00 BaO 0.00 0.00 0.00 0.00 0.00 0.00
0.00 0.00 0.00 0.00 TiO.sub.2 0.00 0.00 0.00 0.00 0.00 0.00 0.00
0.00 0.00 0.00 (.SIGMA.Ln.sub.2O.sub.3) (19.76) (19.92) (19.92)
(20.88) (22.22) (26.97) (21.69) (23.48) (23.10) (24.12)
(La.sub.2O.sub.3/.SIGMA.Ln.sub.2O.sub.3) (0.50) (0.50) (0.50)
(0.50) (0.50) (0.58) (0.50) (0.50) (0.50) (0.50) (Li.sub.2O + ZnO)
(27.67) (27.89) (26.29) (26.51) (22.22) (18.26) (24.90) (21.86)
(23.11) (22.57) (La.sub.2O.sub.3 + Gd.sub.2O.sub.3) (19.76) (19.92)
(19.92) (20.88) (22.22) (25.31) (21.68) (23.48) (23.10) (24.12)
100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0
Properties Tg(TMA)(.degree. C.) 560 563 565 569 612 592 578 589 597
616 Ts(.degree. C.) 610 613 615 619 662 647 628 639 647 669 nd
1.83660 1.84383 1.84096 1.84685 1.84905 1.83226 1.85065 1.85595
1.85922 1.86308 .nu.d 41.46 40.45 40.92 40.52 40.72 39.97 40.53
40.15 40.02 40.50 Specific gravity 5.21 5.31 5.24 5.34 5.41 5.43
5.39 5.45 5.48 5.55 Note) (La.sub.2O.sub.3/.SIGMA.Ln.sub.2O.sub.3)
= ratio of molar amounts
[0093] TABLE-US-00003 TABLE 3 Example 21 22 23 24 25 26 27 28 29 30
Glass B.sub.2O.sub.3 26.88 23.35 24.90 24.03 23.94 23.62 25.00
24.19 24.90 24.31 com- SiO.sub.2 12.65 18.68 16.06 15.50 15.44
15.75 16.13 16.13 16.06 15.69 position La.sub.2O.sub.3 12.65 12.45
12.85 12.79 11.97 12.99 12.90 12.90 12.85 12.55 (mol %)
Gd.sub.2O.sub.3 12.65 12.45 12.85 12.79 11.97 12.99 12.90 12.90
12.85 12.55 ZnO 20.55 17.12 14.46 20.16 20.08 17.32 12.90 12.90
14.46 14.12 Li.sub.2O 2.37 3.89 6.43 2.33 2.32 3.94 6.45 7.26 6.43
6.27 ZrO.sub.2 3.95 3.98 4.02 3.88 5.41 4.72 4.84 4.84 4.02 3.92
Ta.sub.2O.sub.5 3.56 3.50 3.61 3.88 4.25 3.94 4.03 4.03 2.81 1.18
WO.sub.3 4.74 4.67 4.82 4.65 4.63 4.72 4.84 4.84 4.82 4.71
Y.sub.2O.sub.3 0.00 0.00 0.00 0.00 0.00 1.66 0.00 0.00 0.00 0.00
Yb.sub.2O.sub.3 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Nb.sub.2O.sub.5 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
BaO 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 TiO.sub.2
0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 4.71
(.SIGMA.Ln.sub.2O.sub.3) (25.30) (24.90) (25.70) (25.58) (23.94)
(25.98) (25.80) (25.80) (25.70) (25.10)
(La.sub.2O.sub.3/.SIGMA.Ln.sub.2O.sub.3) (0.50) (0.50) (0.50)
(0.50) (0.50) (0.50) (0.50) (0.50) (0.50) (0.50) (Li.sub.2O + ZnO)
(22.92) (21.01) (20.88) (22.48) (22.39) (21.26) (19.35) (20.16)
(20.88) (20.39) (La.sub.2O.sub.3 + Gd.sub.2O.sub.3) (25.30) (24.90)
(25.70) (25.58) (23.94) (25.98) (25.80) (25.80) (25.70) (25.10)
Total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0
Properties Tg(TMA)(.degree. C.) 617 612 597 617 623 620 605 604 600
599 Ts(.degree. C.) 665 662 652 671 673 670 659 663 655 655 nd
1.87132 1.86218 1.86398 1.88085 1.87673 1.87726 1.86734 1.86865
1.86405 1.86841 .nu.d 39.97 40.29 40.51 39.82 39.19 39.64 40.04
39.92 40.10 38.82 Specific gravity 5.63 5.55 5.55 5.65 5.65 5.68
5.57 5.58 5.49 5.34 Note) (La.sub.2O.sub.3/.SIGMA.Ln.sub.2O.sub.3)
= ratio of molar amounts
[0094] TABLE-US-00004 TABLE 4 Example 31 32 33 34 35 36 37 38 39 40
Glass B.sub.2O.sub.3 24.90 24.51 24.90 24.90 24.10 24.10 25.51
24.49 24.69 24.49 com- SiO.sub.2 16.06 15.81 16.06 16.06 16.06
16.06 16.46 16.33 16.46 16.33 position La.sub.2O.sub.3 12.85 11.86
12.05 12.05 12.85 12.85 12.35 12.24 12.35 12.24 (mol %)
Gd.sub.2O.sub.3 12.85 11.86 12.05 12.05 12.85 12.85 12.35 12.24
12.35 12.24 ZnO 14.46 14.23 14.46 14.46 14.46 14.46 9.88 11.43 9.88
9.80 Li.sub.2O 6.43 6.32 6.43 6.43 6.43 6.43 9.05 8.98 9.05 8.98
ZrO.sub.2 4.02 3.95 4.02 4.02 4.02 4.02 4.12 4.08 4.12 4.08
Ta.sub.2O.sub.5 3.61 3.56 3.61 3.61 3.61 3.61 3.70 3.67 4.53 3.67
WO.sub.3 0.00 4.74 4.82 4.82 4.82 4.82 4.94 4.90 4.94 6.53
Y.sub.2O.sub.3 0.00 0.00 1.61 0.00 0.80 0.00 1.65 1.63 1.65 1.63
Yb.sub.2O.sub.3 0.00 0.00 0.00 1.61 0.00 0.80 0.00 0.00 0.00 0.00
Nb.sub.2O.sub.5 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
BaO 0.00 3.16 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 TiO.sub.2
4.82 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
(.SIGMA.Ln.sub.2O.sub.3) (25.70) (23.72) (25.71) (25.71) (26.50)
(26.50) (26.35) (26.11) (26.35) (26.11)
(La.sub.2O.sub.3/.SIGMA.Ln.sub.2O.sub.3) (0.50) (0.50) (0.47)
(0.47) (0.48) (0.48) (0.47) (0.47) (0.47) (0.47) (Li.sub.2O + ZnO)
(20.88) (20.55) (20.88) (20.88) (20.88) (20.88) (18.93) (20.41)
(18.93) (18.78) (La.sub.2O.sub.3 + Gd.sub.2O.sub.3) (25.70) (23.72)
(24.10) (24.10) (25.70) (25.70) (24.70) (24.48) (24.70) (24.48)
Total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0
Properties Tg(TMA)(.degree. C.) 604 596 603 603 608 609 595 594 600
595 Ts(.degree. C.) 662 653 659 660 665 664 651 652 657 652 nd
1.86574 1.85564 1.86200 1.86258 1.86818 1.86809 1.85642 1.85949
1.86360 1.86420 .nu.d 40.42 40.40 40.32 40.25 40.27 40.19 40.82
40.60 40.01 39.68 Specific gravity 5.40 5.50 5.50 5.60 5.57 5.63
5.44 5.47 5.51 5.50 Note) (La.sub.2O.sub.3/.SIGMA.Ln.sub.2O.sub.3)
= ratio of molar amounts
[0095] TABLE-US-00005 TABLE 5 Example 41 42 43 44 45 46 47 48 49 50
Glass B.sub.2O.sub.3 25.10 24.69 24.49 24.20 24.49 24.59 25.00
25.10 25.51 25.10 com- SiO.sub.2 16.74 16.46 16.33 16.13 16.33
16.39 16.39 16.19 16.46 16.19 position La.sub.2O.sub.3 12.55 12.35
12.24 15.32 17.14 15.57 15.57 15.38 15.64 14.57 (mol %)
Gd.sub.2O.sub.3 12.55 12.35 12.24 8.87 7.35 9.43 9.02 8.91 9.05
11.34 ZnO 5.05 9.88 9.80 9.68 9.80 9.84 9.84 12.96 9.88 12.96
Li.sub.2O 11.72 9.05 8.98 8.87 8.98 9.02 9.02 7.29 9.05 7.29
ZrO.sub.2 4.18 4.12 4.08 4.03 4.08 3.28 3.28 3.24 3.29 4.05
Ta.sub.2O.sub.5 3.77 4.53 3.67 3.63 3.67 3.69 3.69 3.64 3.70 3.64
WO.sub.3 6.69 4.94 6.53 6.45 6.53 6.56 6.56 5.67 5.76 4.86
Y.sub.2O.sub.3 1.67 0.00 0.00 2.81 1.63 1.64 0.00 1.62 1.65 0.00
Yb.sub.2O.sub.3 0.00 1.65 1.63 0.00 0.00 0.00 1.64 0.00 0.00 0.00
Nb.sub.2O.sub.5 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
BaO 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 TiO.sub.2
0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 .00
(.SIGMA.Ln.sub.2O.sub.3) (26.79) (26.35) (26.11) (27.00) (26.12)
(26.64) (26.23) (25.91) (26.34) (25.91)
(La.sub.2O.sub.3/.SIGMA.Ln.sub.2O.sub.3) (0.47) (0.47) (0.47)
(0.57) (0.66) (0.58) (0.59) (0.59) (0.59) (0.56) (Li.sub.2O + ZnO)
(16.74) (18.93) (18.78) (18.55) (18.78) (18.85) (18.85) (20.24)
(18.93) (20.24) (La.sub.2O.sub.3 + Gd.sub.2O.sub.3) (25.10) (24.70)
(24.48) (24.19) (24.49) (25.00) (24.59) (24.29) (24.69) (25.91)
Total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0
Properties Tg(TMA)(.degree. C.) 597 599 597 598 591 594 590 594 589
597 Ts(.degree. C.) 640 655 653 655 646 649.6 647 651 645 654 nd
1.85901 1.86382 1.86456 1.86702 1.86545 1.86435 1.86180 1.86093
1.85775 1.86212 .nu.d 39.92 40.10 39.60 39.68 39.57 39.83 39.86
40.17 40.31 40.44 Specific gravity 5.45 5.60 5.60 5.43 5.39 5.44
5.41 5.42 5.38 5.48 Note) (La.sub.2O.sub.3/.SIGMA.Ln.sub.2O.sub.3)
= ratio of molar amounts
[0096] TABLE-US-00006 TABLE 6 Example 51 52 53 54 55 56 57 58 Glass
B.sub.2O.sub.3 25.10 25.10 25.10 24.70 24.80 24.90 28.24 26.29
composition SiO.sub.2 16.19 16.19 16.19 15.94 16.00 16.06 12.55
15.94 (mol %) La.sub.2O.sub.3 12.96 14.57 15.38 14.34 14.40 14.46
10.20 11.16 Gd.sub.2O.sub.3 11.34 9.72 8.91 9.56 9.60 9.64 10.20
11.16 ZnO 12.96 12.96 12.96 14.34 13.60 12.85 23.53 19.12 Li.sub.2O
7.29 7.29 7.29 7.17 7.60 8.03 5.49 7.17 ZrO.sub.2 3.24 3.24 3.24
3.19 3.20 3.21 5.49 3.98 Ta.sub.2O.sub.5 3.64 3.64 3.64 3.59 3.60
3.61 2.74 3.59 WO.sub.3 5.67 5.67 5.67 5.58 5.60 5.62 1.57 1.59
Y.sub.2O.sub.3 0.81 0.81 0.81 0.80 0.80 0.80 0.00 0.00
Yb.sub.2O.sub.3 0.81 0.81 0.81 0.80 0.80 0.80 0.00 0.00
Nb.sub.2O.sub.5 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 BaO 0.00
0.00 0.00 0.00 0.00 0.00 0.00 0.00 TiO.sub.2 0.00 0.00 0.00 0.00
0.00 0.00 0.00 0.00 (.SIGMA.Ln.sub.2O.sub.3) (25.92) (25.91)
(25.91) (25.50) (25.60) (25.70) (20.40) (22.31)
(La.sub.2O.sub.3/.SIGMA.Ln.sub.2O.sub.3) (0.50) (0.56) (0.59)
(0.56) (0.56) (0.56) (0.50) (0.50) (Li.sub.2O + ZnO) (20.24)
(20.24) (20.24) (21.51) (21.20) (20.88) (29.02) (26.29)
(La.sub.2O.sub.3 + Gd.sub.2O.sub.3) (24.30) (24.29) (24.29) (23.90)
(24.00) (24.10) (20.40) (22.32) Total 100.0 100.0 100.0 100.0 100.0
100.0 100.0 100.0 Properties Tg(TMA)(.degree. C.) 598 594 595 592
592 589 579 567 Ts(.degree. C.) 656 650 650 648 648 644 635 621 nd
1.86083 1.86147 1.86156 1.86164 1.86078 1.85964 1.83553 1.83327
.nu.d 40.19 40.22 40.15 40.04 40.32 40.11 42.80 42.78 Specific
gravity 5.52 5.49 5.47 5.49 5.48 5.47 5.29 5.25 Note)
(La.sub.2O.sub.3/.SIGMA.Ln.sub.2O.sub.3) = ratio of molar
amounts
[0097] TABLE-US-00007 TABLE 7 Example 59 60 61 62 63 64 Glass
B.sub.2O.sub.3 31.33 30.28 30.16 29.92 29.92 30.95 composition (mol
%) SiO.sub.2 9.64 11.16 11.11 11.02 11.02 9.52 ZnO 20.88 20.72
21.43 22.05 22.05 22.22 Li.sub.2O 4.02 3.98 3.97 3.94 3.94 3.97
La.sub.2O.sub.3 13.25 13.94 13.49 12.99 12.99 13.10 Gd.sub.2O.sub.3
8.43 7.57 7.14 6.69 6.69 6.75 ZrO.sub.2 4.02 3.98 3.97 3.94 4.72
4.76 Ta.sub.2O.sub.5 3.61 3.59 3.97 3.94 3.94 3.97 Nb.sub.2O.sub.5
0.00 0.00 0.00 0.00 0.00 0.00 TiO.sub.2 0.00 0.00 0.00 0.00 0.00
0.00 WO.sub.3 4.82 4.78 4.76 5.51 4.72 4.76 Y.sub.2O.sub.3 0.00
0.00 0.00 0.00 0.00 0.00 Yb.sub.2O.sub.3 0.00 0.00 0.00 0.00 0.00
0.00 BaO 0.00 0.00 0.00 0.00 0.00 0.00 (.SIGMA.Ln.sub.2O.sub.3)
(21.69) (21.51) (20.63) (19.69) (19.69) (19.84)
(La.sub.2O.sub.3/.SIGMA.Ln.sub.2O.sub.3) (0.61) (0.65) (0.65)
(0.66) (0.66) (0.66) (Li.sub.2O + ZnO) (24.90) (24.70) (25.40)
(25.98) (25.98) (26.19) Total 100.0 100.0 100.0 100.0 100.0 100.0
Properties Tg(TMA)(.degree. C.) 586 586 583 581 580 579 Ts(.degree.
C.) 637 636 634 631 632 630 nd 1.85171 1.84790 1.84788 1.84739
1.84838 1.85052 .nu.d 40.50 40.45 40.18 39.76 40.17 40.01 Density
5.34 5.29 5.29 5.27 5.26 528 Note)
(La.sub.2O.sub.3/.SIGMA.Ln.sub.2O.sub.3) = ratio of molar
amounts
[0098] As shown above, there can be obtained optical glasses for
precision press molding, comprising B.sub.2O.sub.3, SiO.sub.2,
La.sub.2O.sub.3, Gd.sub.2O.sub.3, ZnO, Li.sub.2O, ZrO.sub.2 and
Ta.sub.2O.sub.5, having a glass transition temperature of
630.degree. C. or lower and having a refractive index nd and an
Abbe's number .nu.d which satisfy all of the following relational
expressions,
[0099] 1.80<nd.ltoreq.1.90
[0100] 35<.nu.d.ltoreq.50, and
[0101] nd.gtoreq.2.025-(0.005.times..nu.d).
Example 65
[0102] Precision press molding preforms were produced from the
optical glasses obtained in Examples 1 to 64 as follows. First,
melting, refining and homogenization were carried out to obtain a
molten glass that was to give one of the above optical glasses, the
molten glass was dripped from a flow nozzle made of a platinum
alloy toward a receiving member, and in a concave portion of the
receiving member, the received molten glass drop was floated and
rolled while a gas was ejected upward from a gas ejection port
formed in a bottom of the concave portion, to shape the molten
glass into a preform (Method 1). The thus-formed preforms from the
above optical glasses had a weight equivalent to the weight of an
intended end product, underwent no devitrification and had a smooth
surface free of defects such as a flaw, soiling and alteration.
[0103] Separately, the same molten glass drop as above was dropped
from the flow nozzle in the same manner as above into liquid
nitrogen and shaped into a preform (Method 2). Like the above
preforms, each of the thus-obtained preforms underwent no
devitrification, had high weight accuracy and had a smooth surface
free of defects.
[0104] Further, the same molten glass as above was allowed to flow
down from a flow pipe to form a molten glass flow, a lower end
portion was received with a receiving mold member, a constricted
portion was formed somewhere in the molten glass flow, and when a
glass lower than the constricted portion came to have a
predetermined weight value, the glass was separated in the
constricted portion. The separated molten glass gob having the
above weight was shaped into a preform with a receiving mold member
(Method 3). Like the preforms obtained by the above Methods 1 and
2, each of the thus-obtained preforms underwent no devitrification,
had high weight accuracy and had a smooth surface free of
defects.
Example 66
[0105] Each of the spherical preforms made of the optical glasses
of Examples 1 to 64 obtained by Method 1 in Example 65 was heated
and precision press molded (aspherical-precision pressed) with an
apparatus shown in FIG. 2, to give aspherical lenses.
[0106] Particulars of the precision press molding were as follows.
The preform 4 was placed between a lower mold member 2 and an upper
mold member 1 which had an aspherical form and were made of SiC,
then the atmosphere inside a quartz tube 11 was replaced with a
nitrogen atmosphere inside, and an electric current was applied to
heater 12 to heat the inside of the quartz tube 11. The temperature
inside the shaping mold was set at a temperature between a sag
temperature of the glass +20.degree. C. and the sag temperature of
the glass +80.degree. C., and while this temperature was
maintained, a press rod 13 was moved downward to press the upper
mold member 1 thereby to press-mold the preform (molding glass gob)
in the shaping mold. The press-molding was carried out under a
molding pressure of 8 MPa for a molding time period of 30 seconds.
After the press-molding, the molding pressure was decreased, and
while the press-molded glass molded product was in contact with the
lower mold member 2 and the upper mold member 1, the molded product
was gradually cooled to a temperature that was the glass transition
temperature -30.degree. C. Then, the molded product was rapidly
cooled to room temperature. Then, the glass molded as an aspherical
lens was taken out of the shaping mold, and subjected to
measurement of a form and inspection of an appearance. The
thus-obtained aspherical lenses from the optical glasses in
Examples 1 to 64 had remarkably high accuracy.
[0107] In FIG. 2, numeral 3 indicates a sleeve, numeral 9 indicates
a support rod, numeral 10 indicates a support bed, and numeral 14
indicates a thermocouple.
[0108] Aspherical lenses made of the optical glasses in Examples 1
to 64 were obtained from the preforms prepared by Methods 2 and 3
in the same manner as above. Like the above spherical lenses, the
thus-obtained spherical lenses had remarkably high accuracy. While
the preforms used in this Example had the form of a sphere and had
a diameter of 2 to 30 mm, the form and dimensions of the preform
can be determined as required depending upon the form, etc., of a
precision press molded product (article).
[0109] A press-shaping mold having a form suitable for producing an
end product can give other lens or an optical element such as a
prism or a polygonal mirror.
[0110] An anti-reflection film or an optical multi-layered film
such as a high reflection film can be formed on the
optical-function surface of the thus-obtained optical element as
required.
Effect of the Invention
[0111] According to the present invention, there can be provided a
precision press molding optical glass that has high-refractivity
and low-dispersion properties and which is usable for the
production of an optical element such as an ultra-precision
aspherical lens without any machining, polishing or lapping, of the
optical-function surface thereof after precision press molding.
[0112] According to the present invention, further, there can be
also provided a precision press molding preform made of the above
optical glass and a process for the production thereof, and there
can be further provided an optical element made of the above
optical glass and a process for the production of an optical
element such as an aspherical lens, or the like, highly
productively from the above preform by precision press molding.
* * * * *