U.S. patent application number 13/171082 was filed with the patent office on 2011-12-01 for preforms for precision press molding, optical elements, and methods of manufacturing the same.
This patent application is currently assigned to HOYA CORPORATION. Invention is credited to Yasuhiro Fujiwara, Yoshiko Kasuga, Xuelu Zou.
Application Number | 20110289970 13/171082 |
Document ID | / |
Family ID | 33436465 |
Filed Date | 2011-12-01 |
United States Patent
Application |
20110289970 |
Kind Code |
A1 |
Zou; Xuelu ; et al. |
December 1, 2011 |
PREFORMS FOR PRECISION PRESS MOLDING, OPTICAL ELEMENTS, AND METHODS
OF MANUFACTURING THE SAME
Abstract
Preforms for precision press molding made of optical glass,
optical elements, and methods of manufacturing the same are
provided. The preforms are suited to precision press molding having
a broad range of dispersion characteristics, a low glass transition
temperature, a low sag point, and good resistance to
devitrification while containing no PbO. The optical element is
obtained by precision press molding the preform. One example of the
preform has a refractive index (nd) of greater than or equal to 1.7
and an Abbe number (.nu.d) of less than or equal to 32. The other
example of the preform has an Abbe number (.nu.d) exceeding 32.
Inventors: |
Zou; Xuelu; (Tokyo, JP)
; Kasuga; Yoshiko; (Tokyo, JP) ; Fujiwara;
Yasuhiro; (Tokyo, JP) |
Assignee: |
HOYA CORPORATION
Tokyo
JP
|
Family ID: |
33436465 |
Appl. No.: |
13/171082 |
Filed: |
June 28, 2011 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
10878618 |
Jun 29, 2004 |
7994082 |
|
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13171082 |
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Current U.S.
Class: |
65/102 ; 501/45;
501/46; 501/47; 501/73; 501/77; 501/79; 65/126 |
Current CPC
Class: |
C03C 3/21 20130101; C03C
3/16 20130101; C03C 3/062 20130101 |
Class at
Publication: |
65/102 ; 501/46;
501/73; 501/77; 501/79; 501/47; 501/45; 65/126 |
International
Class: |
G02B 1/00 20060101
G02B001/00; C03C 3/062 20060101 C03C003/062; C03C 3/064 20060101
C03C003/064; C03B 23/00 20060101 C03B023/00; C03C 3/19 20060101
C03C003/19; C03C 3/16 20060101 C03C003/16; C03B 7/00 20060101
C03B007/00; C03C 3/21 20060101 C03C003/21; C03C 3/066 20060101
C03C003/066 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 30, 2003 |
JP |
2003-188455 |
Aug 29, 2003 |
JP |
2003-306126 |
Claims
1. A preform for precision press molding, characterized by being
comprised of an optical glass the components of which are:
P.sub.2O.sub.5: 15 to 70 molar percent, Nb.sub.2O.sub.5: 1 to 30
molar percent TiO.sub.2: 0 to 20 molar percent (excluding 0 molar
percent), Bi.sub.2O.sub.3: 6 to 30 molar percent (excluding 6 molar
percent and exceeding 4 weight percent), B.sub.2O.sub.3: 0 to 30
molar percent, WO.sub.3: 1 to 20 molar percent, BaO: 0 to 15 molar
percent, Li.sub.2O: 3 to 15 weight percent (excluding 3 weight
percent), SiO.sub.2: 0 to 5 weight percent (excluding 5 weight
percent), ZnO: 0 to 10 weight percent (excluding 10 weight
percent), which has a refractive index (nd) of greater than or
equal to 1.7 and an Abbe number (.nu.d) of less than or equal to
32.
2. A preform for precision press molding, characterized by being
comprised of an optical glass the components of which are:
P.sub.2O.sub.5: 15 to 70 molar percent, Nb.sub.2O.sub.5: 1 to 30
molar percent TiO.sub.2: 0 to 20 molar percent (excluding 0 molar
percent), Bi.sub.2O.sub.3: 6 to 30 molar percent (excluding 6 molar
percent), B.sub.2O.sub.3: 0 to 30 molar percent (excluding 0 molar
percent), WO.sub.3: 1 to 20 molar percent, BaO: 0 to 15 molar
percent, Li.sub.2O: 3 to 15 weight percent (excluding 3 weight
percent), SiO.sub.2: 0 to 5 weight percent (excluding 5 weight
percent), ZnO: 0 to 10 weight percent (excluding 10 weight
percent), which has a refractive index (nd) of greater than or
equal to 1.7 and an Abbe number (.nu.d) of less than or equal to
32.
3. A preform for precision press molding, characterized by being
comprised of an optical glass the components of which are:
P.sub.2O.sub.5: 15 to 70 molar percent, Nb.sub.2O.sub.5: 1 to 30
molar percent TiO.sub.2: 0 to 20 molar percent (excluding 0 molar
percent), Bi.sub.2O.sub.3: 6 to 30 molar percent (excluding 6 molar
percent), B.sub.2O.sub.3: 0 to 30 molar percent, WO.sub.3: 1 to 15
molar percent (less than 15 weight percent), BaO: 0 to 15 molar
percent, Li.sub.2O: 3 to 15 weight percent (excluding 3 weight
percent), SiO.sub.2: 0 to 5 weight percent (excluding 5 weight
percent), ZnO: 0 to 10 weight percent (excluding 10 weight
percent), which has a refractive index (nd) of greater than or
equal to 1.7 and an Abbe number (.nu.d) of less than or equal to
32.
4. A preform for precision press molding, characterized by being
comprised of an optical glass the components of which are:
P.sub.2O.sub.5: 15 to 70 molar percent, Nb.sub.2O.sub.5: 1 to 30
molar percent TiO.sub.2: 0 to 20 molar percent (excluding 0 molar
percent), Bi.sub.2O.sub.3: 6 to 30 molar percent (excluding 6 molar
percent and exceeding 4 weight percent), B.sub.2O.sub.3: 0 to 30
molar percent, WO.sub.3: 1 to 20 molar percent, BaO: 0 to 15 molar
percent, Li.sub.2O: 3 to 15 weight percent (excluding 3 weight
percent), SiO.sub.2: 0 to 5 weight percent (excluding 5 weight
percent), where the Li.sub.2O, Na.sub.2O, and K.sub.2O content is 0
to 15 percent (excluding 15 weight percent), which has a refractive
index (nd) of greater than or equal to 1.7 and an Abbe number
(.nu.d) of less than or equal to 32.
5. A preform for precision press molding, characterized by being
comprised of an optical glass the components of which are:
P.sub.2O.sub.5: 15 to 70 molar percent, Nb.sub.2O.sub.5: 1 to 30
molar percent TiO.sub.2: 0 to 20 molar percent (excluding 0 molar
percent), Bi.sub.2O.sub.3: 6 to 30 molar percent (excluding 6 molar
percent), B.sub.2O.sub.3: 0 to 30 molar percent (excluding 0 molar
percent), WO.sub.3: 1 to 20 molar percent, BaO: 0 to 15 molar
percent, Li.sub.2O: 3 to 15 weight percent (excluding 3 weight
percent), SiO.sub.2: 0 to 5 weight percent (excluding 5 weight
percent), where the Li.sub.2O, Na.sub.2O, and K.sub.2O content is 0
to 15 percent (excluding 15 weight percent), which has a refractive
index (nd) of greater than or equal to 1.7 and an Abbe number
(.nu.d) of less than or equal to 32.
6. A preform for precision press molding, characterized by being
comprised of an optical glass the components of which are:
P.sub.2O.sub.5: 15 to 70 molar percent, Nb.sub.2O.sub.5: 1 to 30
molar percent TiO.sub.2: 0 to 20 molar percent (excluding 0 molar
percent), Bi.sub.2O.sub.3: 6 to 30 molar percent (excluding 6 molar
percent), B.sub.2O.sub.3: 0 to 30 molar percent, WO.sub.3: 0 to 15
molar percent (less than 15 weight percent), BaO: 0 to 15 molar
percent, Li.sub.2O: 3 to 15 weight percent (excluding 3 weight
percent), SiO.sub.2: 0 to 5 weight percent (excluding 5 weight
percent), where the Li.sub.2O, Na.sub.2O, and K.sub.2O content is 0
to 15 percent (excluding 15 weight percent), which has a refractive
index (nd) of greater than or equal to 1.7 and an Abbe number
(.nu.d) of less than or equal to 32.
7. A preform for precision press molding, characterized by being
comprised of an optical glass the components of which are:
P.sub.2O.sub.5: 15 to 70 molar percent, Nb.sub.2O.sub.5: 1 to 30
molar percent TiO.sub.2: 0 to 20 molar percent (excluding 0 molar
percent), Bi.sub.2O.sub.3: 0 to 30 molar percent (excluding 0 molar
percent and exceeding 4 weight percent), B.sub.2O.sub.3: 0 to 30
molar percent, WO.sub.3: 1 to 20 molar percent, BaO: 0 to 15 molar
percent, Li.sub.2O: 3 to 15 weight percent (excluding 3 weight
percent), SiO.sub.2: 0 to 5 weight percent (excluding 5 weight
percent), ZnO: 0 to 10 weight percent (excluding 10 weight
percent), where the weight ratio of (TiO.sub.2
content/Bi.sub.2O.sub.3 content) is less than 0.5, which has a
refractive index (nd) of greater than or equal to 1.7 and an Abbe
number (.nu.d) of less than or equal to 32.
8. A preform for precision press molding, characterized by being
comprised of an optical glass the components of which are:
P.sub.2O.sub.5: 15 to 70 molar percent, Nb.sub.2O.sub.5: 1 to 30
molar percent TiO.sub.2: 0 to 20 molar percent (excluding 0 molar
percent), Bi.sub.2O.sub.3: 0 to 30 molar percent (excluding 0 molar
percent), B.sub.2O.sub.3: 0 to 30 molar percent (excluding 0 molar
percent), WO.sub.3: 1 to 20 molar percent, BaO: 0 to 15 molar
percent, Li.sub.2O: 3 to 15 weight percent (excluding 3 weight
percent), SiO.sub.2: 0 to 5 weight percent (excluding 5 weight
percent), ZnO: 0 to 10 weight percent (excluding 10 weight
percent), where the weight ratio of (TiO.sub.2
content/Bi.sub.2O.sub.3 content) is less than 0.5, which has a
refractive index (nd) of greater than or equal to 1.7 and an Abbe
number (.nu.d) of less than or equal to 32.
9. A preform for precision press molding, characterized by being
comprised of an optical glass the components of which are:
P.sub.2O.sub.5: 15 to 70 molar percent, Nb.sub.2O.sub.5: 1 to 30
molar percent TiO.sub.2: 0 to 20 molar percent (excluding 0 molar
percent), Bi.sub.2O.sub.3: 0 to 30 molar percent (excluding 0 molar
percent), B.sub.2O.sub.3: 0 to 30 molar percent, WO.sub.3: 0 to 15
molar percent (less than 15 molar percent), BaO: 0 to 15 molar
percent, Li.sub.2O: 3 to 15 weight percent (excluding 3 weight
percent), SiO.sub.2: 0 to 5 weight percent (excluding 5 weight
percent), ZnO: 0 to 10 weight percent (excluding 10 weight
percent), where the weight ratio of (TiO.sub.2
content/Bi.sub.2O.sub.3 content) is less than 0.5, which has a
refractive index (nd) of greater than or equal to 1.7 and an Abbe
number (.nu.d) of less than or equal to 32.
10. A preform for precision press molding, characterized by being
comprised of an optical glass the components of which are:
P.sub.2O.sub.5: 15 to 70 molar percent, Nb.sub.2O.sub.5: 1 to 30
molar percent TiO.sub.2: 0 to 20 molar percent (excluding 0 molar
percent), Bi.sub.2O.sub.3: greater than 4 weight percent and less
than or equal to 30 molar percent, B.sub.2O.sub.3: 0 to 30 molar
percent, WO.sub.3: 1 to 20 molar percent, BaO: 0 to 15 molar
percent, Li.sub.2O: 3 to 15 weight percent (excluding 3 weight
percent), SiO.sub.2: 0 to 5 weight percent (excluding 5 weight
percent), where the Li.sub.2O, Na.sub.2O, and K.sub.2O content is 0
to 15 percent (excluding 15 weight percent) and the weight ratio of
(TiO.sub.2 content/BiO.sub.2 content) is less than 0.5, which has a
refractive index (nd) of greater than or equal to 1.7 and an Abbe
number (.nu.d) of less than or equal to 32.
11. A preform for precision press molding, characterized by being
comprised of an optical glass the components of which are:
P.sub.2O.sub.5: 15 to 70 molar percent, Nb.sub.2O.sub.5: 1 to 30
molar percent TiO.sub.2: 0 to 20 molar percent (excluding 0 molar
percent), Bi.sub.2O.sub.3: 0 to 30 molar percent (excluding 0 molar
percent), B.sub.2O.sub.3: 0 to 30 molar percent (excluding 0 molar
percent), WO.sub.3: 1 to 20 molar percent, BaO: 0 to 15 molar
percent, Li.sub.2O: 3 to 15 weight percent (excluding 3 weight
percent), SiO.sub.2: 0 to 5 weight percent (excluding 5 weight
percent), where the Li.sub.2O, Na.sub.2O, and K.sub.2O content is 0
to 15 percent (excluding 15 weight percent) and the weight ratio of
(TiO.sub.2 content/BiO.sub.2 content) is less than 0.5, which has a
refractive index (nd) of greater than or equal to 1.7 and an Abbe
number (.nu.d) of less than or equal to 32.
12. A preform for precision press molding, characterized by being
comprised of an optical glass the components of which are:
P.sub.2O.sub.5: 15 to 70 molar percent, Nb.sub.2O.sub.5: 1 to 30
molar percent TiO.sub.2: 0 to 20 molar percent (excluding 0 molar
percent), Bi.sub.2O.sub.3: 0 to 30 molar percent (excluding 0 molar
percent), B.sub.2O.sub.3: 0 to 30 molar percent, WO.sub.3: 0 to 15
molar percent (excluding 15 weight percent), BaO: 0 to 15 molar
percent, Li.sub.2O: 3 to 15 weight percent (excluding 3 weight
percent), SiO.sub.2: 0 to 5 weight percent (excluding 5 weight
percent), where the Li.sub.2O, Na.sub.2O, and K.sub.2O content is 0
to 15 percent (excluding 15 weight percent) and the weight ratio of
(TiO.sub.2 content/Bi.sub.2O.sub.3 content) is less than 0.5, which
has a refractive index (nd) of greater than or equal to 1.7 and an
Abbe number (.nu.d) of less than or equal to 32.
13. A preform for precision press molding, characterized by being
comprised of an optical glass the components of which are:
P.sub.2O.sub.5: 15 to 70 molar percent, Bi.sub.2O.sub.3: 0.1 to 7
molar percent (excluding 7 molar percent), Na.sub.2O: 0 to 30 molar
percent, K.sub.2O: 0 to 30 molar percent, where the combined
content of Li.sub.2O, Na.sub.2O, and K.sub.2O is less than 40 molar
percent, ZnO: 0 to 35 molar percent, CaO: 0 to 35 molar percent,
BaO: 0 to 50 molar percent, Nb.sub.2O.sub.5: 0 to 35 molar percent
WO.sub.3: 0 to 25 molar percent, where the combined content of
Nb.sub.2O.sub.5 and WO.sub.3 exceeds 0 molar percent, SiO.sub.2: 0
to 5 weight percent (excluding 5 weight percent), where 0 to 1
weight percent of Sb.sub.2O.sub.3 is added to the total content of
glass components, which has an Abbe number (.nu.d) exceeding
32.
14. A preform for precision press molding, characterized by being
comprised of an optical glass the components of which are:
P.sub.2O.sub.5: 15 to 70 molar percent, Bi.sub.2O.sub.3: 0.1 to 7
molar percent (excluding 7 molar percent), Lip: 10 to 40 molar
percent (excluding 10 molar percent and 40 molar percent),
Na.sub.2O: 0 to 30 molar percent, K.sub.2O: 0 to 30 molar percent,
where the combined content of Li.sub.2O, Na.sub.2O, and K.sub.2O is
less than 40 molar percent, ZnO: 0 to 35 molar percent, CaO: 0 to
35 molar percent, BaO: 0 to 50 molar percent, Nb.sub.2O.sub.5: 0 to
35 molar percent WO.sub.3: 0 to 25 molar percent, SiO.sub.2: 0 to 5
weight percent (excluding 5 weight percent), where 0 to 1 weight
percent of Sb.sub.2O.sub.3 is added to the total content of glass
components, which has an Abbe number (.nu.d) exceeding 32.
15. A preform for precision press molding, characterized by being
comprised of an optical glass the components of which are:
P.sub.2O.sub.5: 15 to 70 molar percent, Bi.sub.2O.sub.3: 0.1 to 7
molar percent (excluding 7 molar percent), Na.sub.2O: 0 to 30 molar
percent, K.sub.2O: 0 to 30 molar percent, where the combined
content of Li.sub.2O, Na.sub.2O, and K.sub.2O is less than 40 molar
percent, ZnO: 0 to 35 molar percent, CaO: 0 to 35 molar percent,
BaO: 20 to 50 molar percent (excluding 20 molar percent),
Nb.sub.2O.sub.5: 0 to 35 molar percent WO.sub.3: 0 to 25 molar
percent, SiO.sub.2: 0 to 5 weight percent (excluding 5 weight
percent), where 0 to 1 weight percent of Sb.sub.2O.sub.3 is added
to the total content of glass components, which has an Abbe number
(.nu.d) exceeding 32.
16. A preform for precision press molding, characterized by being
comprised of an optical glass comprising essential components in
the form of 15 to 70 molar percent of P.sub.2O.sub.5, more than 4
weight percent and less than or equal to 30 molar percent of
Bi.sub.2O.sub.3, a quantity of TiO.sub.2 of less than 0.5 times the
content by weight of Bi.sub.2O.sub.3, and 0 to 5 weight percent
(excluding 5 weight percent) of SiO.sub.2, and having an Abbe
number (.nu.d) of less than or equal to 32; and by being formed by
solidifying glass the entire surface of which is in a molten
state.
17. A preform for precision press molding, characterized by being
comprised of an optical glass comprising essential components in
the form of 15 to 70 molar percent of P.sub.2O.sub.5,
Bi.sub.2O.sub.3, and B.sub.2O.sub.3, a quantity of TiO.sub.2 of
less than 0.5 times the content by weight of Bi.sub.2O.sub.3, and 0
to 5 weight percent (excluding 5 weight percent) of SiO.sub.2, and
having an Abbe number (.nu.d) of less than or equal to 32; and by
being formed by solidifying glass the entire surface of which is in
a molten state.
18. A preform for precision press molding, characterized by being
comprised of an optical glass comprising essential components in
the form of 15 to 70 molar percent of P.sub.2O.sub.5 and
Bi.sub.2O.sub.3, optional components in the form of 0 to 15 weight
percent (excluding 15 weight percent) of WO.sub.3, a quantity of
TiO.sub.2 of less than 0.5 times the content by weight of
Bi.sub.2O.sub.3, and 0 to 5 weight percent (excluding 5 weight
percent) of SiO.sub.2, and having an Abbe number (.nu.d) of less
than or equal to 32; and by being formed by solidifying glass the
entire surface of which is in a molten state.
19. A preform for precision press molding, characterized by being
comprised of an optical glass comprising essential components in
the form of 15 to 70 molar percent of P.sub.2O.sub.5 and
Bi.sub.2O.sub.3, a quantity of TiO.sub.2 of less than 0.5 times the
content by weight of Bi.sub.2O.sub.3, and 0 to 5 weight percent
(excluding 5 weight percent) of SiO.sub.2, and having an Abbe
number (.nu.d) of less than or equal to 32; and by being formed by
solidifying glass the entire surface of which is in a molten
state.
20. A preform for precision press molding, characterized by being
comprised of an optical glass comprising essential components in
the form of 15 to 70 molar percent of P.sub.2O.sub.5, more than 4
weight percent and less than or equal to 30 molar percent of
Bi.sub.2O.sub.3, a quantity of TiO.sub.2 of less than 0.5 times the
content by weight of Bi.sub.2O.sub.3, and 0 to 5 weight percent
(excluding 5 weight percent) of SiO.sub.2; and by being formed by
solidifying glass the entire surface of which is in a molten
state.
21. A preform for precision press molding, characterized by being
comprised of an optical glass comprising essential components in
the form of 15 to 70 molar percent of P.sub.2O.sub.5,
Bi.sub.2O.sub.3, and Bi.sub.2O.sub.3, a quantity of TiO.sub.2 of
less than 0.5 times the content by weight of Bi.sub.2O.sub.3, and 0
to 5 weight percent (excluding 5 weight percent) of SiO.sub.2; and
in that the entire surface thereof is a free surface.
22. A preform for precision press molding, characterized by being
comprised of an optical glass comprising essential components in
the form of 15 to 70 molar percent of P.sub.2O.sub.5 and
Bi.sub.2O.sub.3, optional components in the form of 0 to 15 weight
percent (excluding 15 weight percent) of WO.sub.3, a quantity of
TiO.sub.2 of less than 0.5 times the content by weight of
Bi.sub.2O.sub.3, and 0 to 5 weight percent (excluding 5 weight
percent) of SiO.sub.2; and in that the entire surface thereof is a
free surface.
23. A preform for precision press molding, characterized by being
comprised of an optical glass comprising essential components in
the form of 15 to 70 molar percent of P.sub.2O.sub.5 and
Bi.sub.2O.sub.3, a quantity of TiO.sub.2 of less than 0.5 times the
content by weight of Bi.sub.2O.sub.3, and 0 to 5 weight percent
(excluding 5 weight percent) of SiO.sub.2, and having an Abbe
number (.nu.d) of less than or equal to 32; and in that the entire
surface thereof is a free surface.
24. A method of manufacturing a preform for precision press
molding, characterized in that a glass melt gob of prescribed
weight is separated from a glass melt flowing out of a flow pipe
and up to solidification of the glass melt gob, a preform according
to any of claim 1 to 23 with a weight equal to the above prescribed
weight is formed.
25. An optical element obtained by precision press molding the
preform according to any of claim 1 to 23 above or a preform
manufactured by the manufacturing method according to claim 24.
26. A method of manufacturing an optical element characterized in
that in a method of manufacturing an optical element by heating a
glass preform and conducting precision press molding, the preform
according to any of claim 1 to 23 or a preform manufactured by the
manufacturing method according to claim 24 above is heated and
precision press molded with a pressing mold.
27. The method of manufacturing an optical element according to
claim 26 wherein the preform and pressing mold are both heated and
precision press molding is conducted.
28. The method of manufacturing an optical article according to
claim 26, wherein a heated preform is introduced into a pressing
mold that has been preheated separately from said preform and
precision press molding is conducted.
Description
[0001] This is a Continuation of application Ser. No. 10/878,618
filed Jun. 29, 2004, claiming priority based on Japanese Patent
Application Nos. 2003-188455 filed on Jun. 30, 2003 and 2003-306126
filed on Aug. 29, 2003, the contents of all of which are
incorporated herein by reference in their entirety.
TECHNICAL FIELD
[0002] The present invention relates to preforms for precision
press molding made of optical glass, optical elements, and methods
of manufacturing the same.
BACKGROUND ART
[0003] Since precision press-molded aspherical lenses and the like
that are made with optical glass having broad dispersion
characteristics (for example, an Abbe number, vd, of 17 to 72) are
extremely useful in optical design, the demand for the optical
glass used in such precision press molding is increasing. However,
large quantities of lead oxide have been incorporated into the
optical glass compositions of many of the glasses and the pressing
temperature has been reduced to increase the service life of the
pressing mold employed in precision press molding. For example,
Japanese Unexamined Patent Publication (KOKAI) Heisei No. 1-308843
discloses an optical glass for precision pressing comprised of
(denoted as weight percentages): SiO.sub.2: 15 to 50 percent, PbO:
30 to 58 percent, Li.sub.2O: 0.1 to 7 percent, Na.sub.2O: 0 to 15
percent, K.sub.2O: 0 to 15 percent, where
Li.sub.2O+Na.sub.2O+K.sub.2O: 3 to 25 percent; La.sub.2O.sub.3: 0
to 15 percent, MgO: 0 to 10 percent, TiO.sub.2: 0 to 10 percent,
where La.sub.2O.sub.3+MgO+TiO.sub.2: 0.1 to 20 percent, ZrO.sub.2:
0 to 5 percent, Al.sub.2O.sub.3: 0 to 10 percent, where
ZrO.sub.2+Al.sub.2O.sub.3: 0.1 to 10 percent; ZnO: 0 to 20 percent,
B.sub.2O.sub.3: 0 to 15 percent, Y.sub.2O.sub.3: 0 to 5 percent,
Gd.sub.2O.sub.3: 0 to 5 percent, CaO: 0 to 10 percent, SrO: 0 to 10
percent, BaO: 0 to 9 percent; Nb.sub.2O.sub.5: 0 to 15 percent,
Ta.sub.2O.sub.5: 0 to 5 percent, WO.sub.3: 0 to 5 percent,
P.sub.2O.sub.5: 0 to 5 percent, As.sub.2O.sub.3: 0 to 1 percent,
Sb.sub.2O.sub.3: 0 to 5 percent.
[0004] However, precision press molding is normally conducted in a
nonreactive or weakly reducing atmosphere to prevent oxidation of
the pressing mold. When precision press molding the above-described
glass containing a large amount of lead oxide among the glass
components, lead oxide at the surface of the glass is reduced,
precipitating out as metallic lead on the surface of the lens. This
then adheres to the mold material used to mold precision
press-molded lenses, compromising the precision of the transfer
surface of lenses that are precision press molded and requiring
maintenance to remove the metallic lead adhering to the mold, which
is not suited to mass production. Further, the melting of the
glasses containing large quantities of lead oxide disclosed in the
above-cited patent publication presents major problems in terms of
environmental pollution. Thus, the glass disclosed in above-cited
patent publication is unsuited to precision press molding.
[0005] The present invention, devised to solve the above-stated
problems, has for its object to provide preforms for precision
press molding comprised of optical glass imparting broad dispersion
characteristics, permitting a low pressing temperature suited to
precision press molding, and affording high stability; a method of
manufacturing such preforms; optical elements obtained by precision
press molding this preform; and a method of manufacturing such
optical elements.
SUMMARY OF THE INVENTION
[0006] The present invention provides:
[0007] (1) a preform for precision press molding, characterized by
being comprised of an optical glass the components of which are:
[0008] P.sub.2O.sub.5: 15 to 70 molar percent, [0009]
Nb.sub.2O.sub.5: 1 to 30 molar percent [0010] TiO.sub.2: 0 to 20
molar percent (excluding 0 molar percent), [0011] Bi.sub.2O.sub.3:
6 to 30 molar percent (excluding 6 molar percent and exceeding 4
weight percent), [0012] B.sub.2O.sub.3: 0 to 30 molar percent,
[0013] WO.sub.3: 1 to 20 molar percent, [0014] BaO: 0 to 15 molar
percent, [0015] Li.sub.2O: 3 to 15 weight percent (excluding 3
weight percent), [0016] SiO.sub.2: 0 to 5 weight percent (excluding
5 weight percent), [0017] ZnO: 0 to 10 weight percent (excluding 10
weight percent), which has a refractive index (nd) of greater than
or equal to 1.7 and an Abbe number (.nu. d) of less than or equal
to 32;
[0018] (2) a preform for precision press molding, characterized by
being comprised of an optical glass the components of which are:
[0019] P.sub.2O.sub.5: 15 to 70 molar percent, [0020]
Nb.sub.2O.sub.5: 1 to 30 molar percent [0021] TiO.sub.2: 0 to 20
molar percent (excluding 0 molar percent), [0022] Bi.sub.2O.sub.3:
6 to 30 molar percent (excluding 6 molar percent), [0023]
B.sub.2O.sub.3: 0 to 30 molar percent (excluding 0 molar percent),
[0024] WO.sub.3: 1 to 20 molar percent, [0025] BaO: 0 to 15 molar
percent, [0026] Li.sub.2O: 3 to 15 weight percent (excluding 3
weight percent), [0027] SiO.sub.2: 0 to 5 weight percent (excluding
5 weight percent), [0028] ZnO: 0 to 10 weight percent (excluding 10
weight percent), which has a refractive index (nd) of greater than
or equal to 1.7 and an Abbe number (.nu. d) of less than or equal
to 32;
[0029] (3) a preform for precision press molding, characterized by
being comprised of an optical glass the components of which are:
[0030] P.sub.2O.sub.5: 15 to 70 molar percent, [0031]
Nb.sub.2O.sub.5: 1 to 30 molar percent [0032] TiO.sub.2: 0 to 20
molar percent (excluding 0 molar percent), [0033] Bi.sub.2O.sub.3:
6 to 30 molar percent (excluding 6 molar percent), [0034]
B.sub.2O.sub.3: 0 to 30 molar percent, [0035] WO.sub.3: 1 to 15
molar percent (less than 15 weight percent), [0036] BaO: 0 to 15
molar percent, [0037] Li.sub.2O: 3 to 15 weight percent (excluding
3 weight percent), [0038] SiO.sub.2: 0 to 5 weight percent
(excluding 5 weight percent), [0039] ZnO: 0 to 10 weight percent
(excluding 10 weight percent), which has a refractive index (nd) of
greater than or equal to 1.7 and an Abbe number (.nu. d) of less
than or equal to 32;
[0040] (4) a preform for precision press molding, characterized by
being comprised of an optical glass the components of which are:
[0041] P.sub.2O.sub.5: 15 to 70 molar percent, [0042]
Nb.sub.2O.sub.5: 1 to 30 molar percent [0043] TiO.sub.2: 0 to 20
molar percent (excluding 0 molar percent), [0044] Bi.sub.2O.sub.3:
6 to 30 molar percent (excluding 6 molar percent and exceeding 4
weight percent), [0045] B.sub.2O.sub.3: 0 to 30 molar percent,
[0046] WO.sub.3: 1 to 20 molar percent, [0047] BaO: 0 to 15 molar
percent, [0048] Li.sub.2O: 3 to 15 weight percent (excluding 3
weight percent), [0049] SiO.sub.2: 0 to 5 weight percent (excluding
5 weight percent), where the Li.sub.2O, Na.sub.2O, and K.sub.2O
content is 0 to 15 percent (excluding 15 weight percent), which has
a refractive index (nd) of greater than or equal to 1.7 and an Abbe
number (.nu. d) of less than or equal to 32;
[0050] (5) a preform for precision press molding, characterized by
being comprised of an optical glass the components of which are:
[0051] P.sub.2O.sub.5: 15 to 70 molar percent, [0052]
Nb.sub.2O.sub.5: 1 to 30 molar percent [0053] TiO.sub.2: 0 to 20
molar percent (excluding 0 molar percent), [0054] Bi.sub.2O.sub.3:
6 to 30 molar percent (excluding 6 molar percent), [0055]
B.sub.2O.sub.3: 0 to 30 molar percent (excluding 0 molar percent),
[0056] WO.sub.3: 1 to 20 molar percent, [0057] BaO: 0 to 15 molar
percent, [0058] Li.sub.2O: 3 to 15 weight percent (excluding 3
weight percent), [0059] SiO.sub.2: 0 to 5 weight percent (excluding
5 weight percent), where the Li.sub.2O, Na.sub.2O, and K.sub.2O
content is 0 to 15 percent (excluding 15 weight percent), which has
a refractive index (nd) of greater than or equal to 1.7 and an Abbe
number (.nu. d) of less than or equal to 32;
[0060] (6) a preform for precision press molding, characterized by
being comprised of an optical glass the components of which are:
[0061] P.sub.2O.sub.5: 15 to 70 molar percent, [0062]
Nb.sub.2O.sub.5: 1 to 30 molar percent [0063] TiO.sub.2: 0 to 20
molar percent (excluding 0 molar percent), [0064] Bi.sub.2O.sub.3:
6 to 30 molar percent (excluding 6 molar percent), [0065]
B.sub.2O.sub.3: 0 to 30 molar percent, [0066] WO.sub.3: 0 to 15
molar percent (less than 15 weight percent), [0067] BaO: 0 to 15
molar percent, [0068] Li.sub.2O: 3 to 15 weight percent (excluding
3 weight percent), [0069] SiO.sub.2: 0 to 5 weight percent
(excluding 5 weight percent), where the Li.sub.2O, Na.sub.2O, and
K.sub.2O content is 0 to 15 percent (excluding 15 weight percent),
which has a refractive index (nd) of greater than or equal to 1.7
and an Abbe number (.nu.d) of less than or equal to 32;
[0070] (7) a preform for precision press molding, characterized by
being comprised of an optical glass the components of which are:
[0071] P.sub.2O.sub.5: 15 to 70 molar percent, [0072]
Nb.sub.2O.sub.5: 1 to 30 molar percent [0073] TiO.sub.2: 0 to 20
molar percent (excluding 0 molar percent), [0074] Bi.sub.2O.sub.3:
0 to 30 molar percent (excluding 0 molar percent and exceeding 4
weight percent), [0075] B.sub.2O.sub.3: 0 to 30 molar percent,
[0076] WO.sub.3: 1 to 20 molar percent, [0077] BaO: 0 to 15 molar
percent, [0078] Li.sub.2O: 3 to 15 weight percent (excluding 3
weight percent), [0079] SiO.sub.2: 0 to 5 weight percent (excluding
5 weight percent), [0080] ZnO: 0 to 10 weight percent (excluding 10
weight percent), where the weight ratio of (TiO.sub.2
content/Bi.sub.2O.sub.3 content) is less than 0.5, which has a
refractive index (nd) of greater than or equal to 1.7 and an Abbe
number (.nu.d) of less than or equal to 32;
[0081] (8) a preform for precision press molding, characterized by
being comprised of an optical glass the components of which are:
[0082] P.sub.2O.sub.5: 15 to 70 molar percent, [0083]
Nb.sub.2O.sub.5: 1 to 30 molar percent [0084] TiO.sub.2: 0 to 20
molar percent (excluding 0 molar percent), [0085] Bi.sub.2O.sub.3:
0 to 30 molar percent (excluding 0 molar percent), [0086]
B.sub.2O.sub.3: 0 to 30 molar percent (excluding 0 molar percent),
[0087] WO.sub.3: 1 to 20 molar percent, [0088] BaO: 0 to 15 molar
percent, [0089] Li.sub.2O: 3 to 15 weight percent (excluding 3
weight percent), [0090] SiO.sub.2: 0 to 5 weight percent (excluding
5 weight percent), [0091] ZnO: 0 to 10 weight percent (excluding 10
weight percent), where the weight ratio of (TiO.sub.2
content/Bi.sub.2O.sub.3 content) is less than 0.5, which has a
refractive index (nd) of greater than or equal to 1.7 and an Abbe
number (.nu.d) of less than or equal to 32;
[0092] (9) a preform for precision press molding, characterized by
being comprised of an optical glass the components of which are:
[0093] P.sub.2O.sub.5: 15 to 70 molar percent, [0094]
Nb.sub.2O.sub.5: 1 to 30 molar percent [0095] TiO.sub.2: 0 to 20
molar percent (excluding 0 molar percent), [0096] Bi.sub.2O.sub.3:
0 to 30 molar percent (excluding 0 molar percent), [0097]
B.sub.2O.sub.3: 0 to 30 molar percent, [0098] WO.sub.3: 0 to 15
molar percent (less than 15 molar percent), [0099] BaO: 0 to 15
molar percent, [0100] Li.sub.2O: 3 to 15 weight percent (excluding
3 weight percent), [0101] SiO.sub.2: 0 to 5 weight percent
(excluding 5 weight percent), [0102] ZnO: 0 to 10 weight percent
(excluding 10 weight percent), where the weight ratio of (TiO.sub.2
content/Bi.sub.2O.sub.3 content) is less than 0.5, which has a
refractive index (nd) of greater than or equal to 1.7 and an Abbe
number (.nu.d) of less than or equal to 32;
[0103] (10) a preform for precision press molding, characterized by
being comprised of an optical glass the components of which are:
[0104] P.sub.2O.sub.5: 15 to 70 molar percent, [0105]
Nb.sub.2O.sub.5: 1 to 30 molar percent [0106] TiO.sub.2: 0 to 20
molar percent (excluding 0 molar percent), [0107] Bi.sub.2O.sub.3:
greater than 4 weight percent and less than or equal to 30 molar
percent, [0108] B.sub.2O.sub.3: 0 to 30 molar percent, [0109]
WO.sub.3: 1 to 20 molar percent, [0110] BaO: 0 to 15 molar percent,
[0111] Li.sub.2O: 3 to 15 weight percent (excluding 3 weight
percent), [0112] SiO.sub.2: 0 to 5 weight percent (excluding 5
weight percent), where the Li.sub.2O, Na.sub.2O, and K.sub.2O
content is 0 to 15 percent (excluding 15 weight percent) and the
weight ratio of (TiO.sub.2 content/BiO.sub.2 content) is less than
0.5, which has a refractive index (nd) of greater than or equal to
1.7 and an Abbe number (.nu.d) of less than or equal to 32;
[0113] (11) a preform for precision press molding, characterized by
being comprised of an optical glass the components of which are:
[0114] P.sub.2O.sub.5: 15 to 70 molar percent, [0115]
Nb.sub.2O.sub.5: 1 to 30 molar percent [0116] TiO.sub.2: 0 to 20
molar percent (excluding 0 molar percent), [0117] Bi.sub.2O.sub.3:
0 to 30 molar percent (excluding 0 molar percent), [0118]
B.sub.2O.sub.3: 0 to 30 molar percent (excluding 0 molar percent),
[0119] WO.sub.3: 1 to 20 molar percent, [0120] BaO: 0 to 15 molar
percent, [0121] Li.sub.2O: 3 to 15 weight percent (excluding 3
weight percent), [0122] SiO.sub.2: 0 to 5 weight percent (excluding
5 weight percent), where the Li.sub.2O, Na.sub.2O, and K.sub.2O
content is 0 to 15 percent (excluding 15 weight percent) and the
weight ratio of (TiO.sub.2 content/BiO.sub.2 content) is less than
0.5, which has a refractive index (nd) of greater than or equal to
1.7 and an Abbe number (.nu.d) of less than or equal to 32;
[0123] (12) a preform for precision press molding, characterized by
being comprised of an optical glass the components of which are:
[0124] P.sub.2O.sub.5: 15 to 70 molar percent, [0125]
Nb.sub.2O.sub.5: 1 to 30 molar percent [0126] TiO.sub.2: 0 to 20
molar percent (excluding 0 molar percent), [0127] Bi.sub.2O.sub.3:
0 to 30 molar percent (excluding 0 molar percent), [0128]
B.sub.2O.sub.3: 0 to 30 molar percent, [0129] WO.sub.3: 0 to 15
molar percent (excluding 15 weight percent), [0130] BaO: 0 to 15
molar percent, [0131] Li.sub.2O: 3 to 15 weight percent (excluding
3 weight percent), [0132] SiO.sub.2: 0 to 5 weight percent
(excluding 5 weight percent), where the Li.sub.2O, Na.sub.2O, and
K.sub.2O content is 0 to 15 percent (excluding 15 weight percent)
and the weight ratio of (TiO.sub.2 content/Bi.sub.2O.sub.3 content)
is less than 0.5, which has a refractive index (nd) of greater than
or equal to 1.7 and an Abbe number (.nu. d) of less than or equal
to 32;
[0133] (13) A preform for precision press molding, characterized by
being comprised of an optical glass the components of which are:
[0134] P.sub.2O.sub.5: 15 to 70 molar percent, [0135]
Bi.sub.2O.sub.3: 0.1 to 7 molar percent (excluding 7 molar
percent), [0136] Na.sub.2O: 0 to 30 molar percent, [0137] K.sub.2O:
0 to 30 molar percent, where the combined content of Li.sub.2O,
Na.sub.2O, and K.sub.2O is less than 40 molar percent, [0138] ZnO:
0 to 35 molar percent, [0139] CaO: 0 to 35 molar percent, [0140]
BaO: 0 to 50 molar percent, [0141] Nb.sub.2O.sub.5: 0 to 35 molar
percent [0142] WO.sub.3: 0 to 25 molar percent, where the combined
content of Nb.sub.2O.sub.5 and WO.sub.3 exceeds 0 molar percent,
[0143] SiO.sub.2: 0 to 5 weight percent (excluding 5 weight
percent), where 0 to 1 weight percent of Sb.sub.2O.sub.3 is added
to the total content of glass components, which has an Abbe number
(.nu.d) exceeding 32;
[0144] (14) A preform for precision press molding, characterized by
being comprised of an optical glass the components of which are:
[0145] P.sub.2O.sub.5: 15 to 70 molar percent, [0146]
Bi.sub.2O.sub.3: 0.1 to 7 molar percent (excluding 7 molar
percent), [0147] Li.sub.2O: 10 to 40 molar percent (excluding 10
molar percent and 40 molar percent), [0148] Na.sub.2O: 0 to 30
molar percent, [0149] K.sub.2O: 0 to 30 molar percent, where the
combined content of Li.sub.2O, Na.sub.2O, and K.sub.2O is less than
40 molar percent,
[0150] ZnO: 0 to 35 molar percent,
[0151] CaO: 0 to 35 molar percent, [0152] BaO: 0 to 50 molar
percent, [0153] Nb.sub.2O.sub.5: 0 to 35 molar percent [0154]
WO.sub.3: 0 to 25 molar percent, [0155] SiO.sub.2: 0 to 5 weight
percent (excluding 5 weight percent), where 0 to 1 weight percent
of Sb.sub.2O.sub.3 is added to the total content of glass
components, which has an Abbe number (.nu.d) exceeding 32;
[0156] (15) A preform for precision press molding, characterized by
being comprised of an optical glass the components of which are:
[0157] P.sub.2O.sub.5: 15 to 70 molar percent, [0158]
Bi.sub.2O.sub.3: 0.1 to 7 molar percent (excluding 7 molar
percent), [0159] Na.sub.2O: 0 to 30 molar percent, [0160] K.sub.2O:
0 to 30 molar percent, where the combined content of Li.sub.2O,
Na.sub.2O, and K.sub.2O is less than 40 molar percent, [0161] ZnO:
0 to 35 molar percent, [0162] CaO: 0 to 35 molar percent, [0163]
BaO: 20 to 50 molar percent (excluding 20 molar percent), [0164]
Nb.sub.2O.sub.5: 0 to 35 molar percent [0165] WO.sub.3: 0 to 25
molar percent, [0166] SiO.sub.2: 0 to 5 weight percent (excluding 5
weight percent), where 0 to 1 weight percent of Sb.sub.2O.sub.3 is
added to the total content of glass components, which has an Abbe
number (.nu.d) exceeding 32;
[0167] (16) a preform for precision press molding, characterized by
being comprised of an optical glass comprising essential components
in the form of 15 to 70 molar percent of P.sub.2O.sub.5, more than
4 weight percent and less than or equal to 30 molar percent of
Bi.sub.2O.sub.3, a quantity of TiO.sub.2 of less than 0.5 times the
content by weight of Bi.sub.2O.sub.3, and 0 to 5 weight percent
(excluding 5 weight percent) of SiO.sub.2, and having an Abbe
number (.nu.d) of less than or equal to 32; and by being formed by
solidifying glass the entire surface of which is in a molten
state;
[0168] (17) a preform for precision press molding, characterized by
being comprised of an optical glass comprising essential components
in the form of 15 to 70 molar percent of P.sub.2O.sub.5,
Bi.sub.2O.sub.3, and B.sub.2O.sub.3, a quantity of TiO.sub.2 of
less than 0.5 times the content by weight of Bi.sub.2O.sub.3, and 0
to 5 weight percent (excluding 5 weight percent) of SiO.sub.2, and
having an Abbe number (.nu.d) of less than or equal to 32; and by
being formed by solidifying glass the entire surface of which is in
a molten state;
[0169] (18) a preform for precision press molding, characterized by
being comprised of an optical glass comprising essential components
in the form of 15 to 70 molar percent of P.sub.2O.sub.5 and
Bi.sub.2O.sub.3, optional components in the form of 0 to 15 weight
percent (excluding 15 weight percent) of WO.sub.3, a quantity of
TiO.sub.2 of less than 0.5 times the content by weight of
Bi.sub.2O.sub.3, and 0 to 5 weight percent (excluding 5 weight
percent) of SiO.sub.2, and having an Abbe number (.nu.d) of less
than or equal to 32; and by being formed by solidifying glass the
entire surface of which is in a molten state;
[0170] (19) a preform for precision press molding, characterized by
being comprised of an optical glass comprising essential components
in the form of 15 to 70 molar percent of P.sub.2O.sub.5 and
Bi.sub.2O.sub.3, a quantity of TiO.sub.2 of less than 0.5 times the
content by weight of Bi.sub.2O.sub.3, and 0 to 5 weight percent
(excluding 5 weight percent) of SiO.sub.2, and having an Abbee
number (.nu.d) of less than or equal to 32; and by being formed by
solidifying glass the entire surface of which is in a molten
state;
[0171] (20) a preform for precision press molding, characterized by
being comprised of an optical glass comprising essential components
in the form of 15 to 70 molar percent of P.sub.2O.sub.5, more than
4 weight percent and less than or equal to 30 molar percent of
Bi.sub.2O.sub.3, a quantity of TiO.sub.2 of less than 0.5 times the
content by weight of Bi.sub.2O.sub.3, and 0 to 5 weight percent
(excluding 5 weight percent) of SiO.sub.2; and by being formed by
solidifying glass the entire surface of which is in a molten
state;
[0172] (21) a preform for precision press molding, characterized by
being comprised of an optical glass comprising essential components
in the form of 15 to 70 molar percent of P.sub.2O.sub.5,
Bi.sub.2O.sub.3, and Bi.sub.2O.sub.3, a quantity of TiO.sub.2 of
less than 0.5 times the content by weight of Bi.sub.2O.sub.3, and 0
to 5 weight percent (excluding 5 weight percent) of SiO.sub.2; and
in that the entire surface thereof is a free surface;
[0173] (22) a preform for precision press molding, characterized by
being comprised of an optical glass comprising essential components
in the form of 15 to 70 molar percent of P.sub.2O.sub.5 and
Bi.sub.2O.sub.3, optional components in the form of 0 to 15 weight
percent (excluding 15 weight percent) of WO.sub.3, a quantity of
TiO.sub.2 of less than 0.5 times the content by weight of
Bi.sub.2O.sub.3, and 0 to 5 weight percent (excluding 5 weight
percent) of SiO.sub.2; and in that the entire surface thereof is a
free surface;
[0174] (23) a preform for precision press molding, characterized by
being comprised of an optical glass comprising essential components
in the form of 15 to 70 molar percent of P.sub.2O.sub.5 and
Bi.sub.2O.sub.3, a quantity of TiO.sub.2 of less than 0.5 times the
content by weight of Bi.sub.2O.sub.3, and 0 to 5 weight percent
(excluding 5 weight percent) of SiO.sub.2, and having an Abbe
number (.nu.d) of less than or equal to 32; and in that the entire
surface thereof is a free surface;
[0175] (24) a method of manufacturing a preform for precision press
molding, characterized in that a glass melt gob of prescribed
weight is separated from a glass melt flowing out of a flow pipe
and up to solidification of the glass melt gob, a preform according
to any of (1) to (23) above with a weight equal to the above
prescribed weight is formed.
[0176] (25) an optical element obtained by precision press molding
the preform according to any of (1) to (23) above or a preform
manufactured by the manufacturing method according to (24).
[0177] (26) A method of manufacturing an optical element
characterized in that in a method of manufacturing an optical
element by heating a glass preform and conducting precision press
molding, the preform according to any of (1) to (23) above or a
preform manufactured by the manufacturing method according to (24)
above is heated and precision press molded with a pressing
mold.
[0178] (27) The method of manufacturing an optical element
according to (26) above wherein the preform and pressing mold are
both heated and precision press molding is conducted.
[0179] (28) The method of manufacturing an optical article
according to (26) above, wherein a heated preform is introduced
into a pressing mold that has been preheated separately from said
preform and precision press molding is conducted.
BRIEF DESCRIPTION OF THE FIGURES
[0180] FIG. 1 demonstrates the results of tests conducted to
confirm the effect of introducing Bi.sub.2O.sub.3. In contrast to
the glass (left) containing Bi.sub.2O.sub.3 of Embodiment 25, which
is transparent, the glass (right) obtained by removing
Bi.sub.2O.sub.3 from the composition crystallized, losing
transparency completely.
[0181] FIG. 2 shows the results of wetting angle tests conducted
for the glass of Embodiment 29 and a glass obtained by removing
Bi.sub.2O.sub.3 from the composition thereof.
[0182] FIG. 3 is a schematic drawing descriptive of a precision
press-molding device.
[0183] The present invention provides preforms for precision press
molding made of glass suited to precision press molding having a
broad range of dispersion characteristics, a low glass transition
temperature, a low sag point, and good resistance to
devitrification while containing no PbO, and a method of
manufacturing the same.
[0184] The present invention further provides an optical element
obtained by precision press molding the above preform, and a method
of manufacturing by precision press molding a good optical element
employing the above preform.
BEST MODE OF IMPLEMENTING THE INVENTION
[0185] To achieve the above-stated objects, the present inventors
conducted various tests, resulting in the discovery that by
incorporating Bi.sub.2O.sub.3 into P.sub.2O.sub.5-based glass of a
prescribed composition not containing PbO, it was possible to
increase the thermal stability of the glass production range and
set a wide range of refractive indexes (nd) and Abbe numbers
(.nu.d). It was also possible to develop preforms for precision
press molding permitting the precision press molding of optical
elements with good stability and mass production properties. The
present invention was devised on that basis.
[0186] In the present invention, the term "precision press molding"
refers to a press molding method in which a glass preform is heated
into a state permitting press molding and a pressing mold is used
to press mold the preform to precisely transfer to the preform in
the above state the molding surface of the pressing mold, thereby
producing a desired article (final product) without mechanical
processing such as polishing or grinding of the molded article
following press molding. This molding method is normally employed
to mold optical elements (for example, lenses and prisms). In the
precision press molding of optical elements, for example, an
optically functional surface (a surface of the optical element
performing an optical function such as passing or reflecting the
optical axis to be controlled) is formed by precise transfer of the
molding surface of the pressing mold, permitting performance as an
optically functional surface at least without mechanical processing
of the optically functional surface following press molding.
Generally, methods of press molding optical elements by such a
method are referred to as mold optics molding. Since neither
grinding nor polishing of the optically functional surface into an
aspherical surface is required, this method is particularly suited
to production in the precision press molding of aspherical
lenses.
[0187] Precision press molding is capable of the highly efficient
mass production of products requiring high surface precision and
internal quality, such as optical elements. However, the adapted
preform is limited to glass capable of plastic deformation at
relatively low temperatures. When a preform having a high glass
transition temperature is employed, the molding surface of the
pressing mold also increases in temperature during precision press
molding, causing extreme abrasion and even damaging the molding
surface. In precision press molding, when even microdefects are
generated in the molding surface of the pressing mold, they are
transferred to the optically functional surface of the optical
element that is the final product, and the optical element loses
its optical properties. Thus, the preform that is employed must be
made of glass with a low glass transition temperature.
[0188] The word "preform" is used here to mean a body that has been
premolded to a prescribed shape. The term "preform for precision
press molding" comprised of optical glass refers to a premolded
body of optical glass that is supplied to precision press molding
in a heat-softened state. In the present Specification below,
unless specifically stated otherwise, the term "preform" refers to
a preform for precision press molding.
[0189] In particular, in the "preform for precision press molding"
of the present invention, what is meant is a preform the weight of
which has been set to precisely match the weight of a precision
press-molded article. Based on the weight of the desired precision
press-molded article, when the weight of the preform is excessively
low, the glass does not adequately fill the molding surface of the
pressing mold during precision press molding, precluding desired
surface precision. There is also a problem in that the thickness of
the molded article is less than desired. When the weight of the
preform is excessively high, the excess glass enters the crack
between the pressing molds, resulting in molding burrs or a molded
article that is undesirably thick. Accordingly, the weight of the
preform used in precision press molding must be controlled more
precisely than for glass materials employed in general press
molding where the optically functional surface or the like is
finished by grinding or polishing following press molding.
[0190] The shape of the preform is set based on the shape of the
precision press-molded article. The optical element is often an
item such as a lens having rotational symmetry. Thus, the shape of
the preform is desirably one having an axis of rotational symmetry,
especially, is one having symmetry with respect to rotary of a
certain angle around an axis of rotational symmetry. Specific
examples are spheres and items having one axis of rotational
symmetry. Examples of shapes having one axis of rotational symmetry
are shapes having smooth contour lines without angles or
indentations in the cross-section containing the axis of rotational
symmetry, such as shapes having elliptical contour lines in which
the minor axis in the cross-section corresponds to the axis of
rotational symmetry. The shape is desirably one in which, when the
angle of one of the angles formed between the line connecting a
point on the contour line of the preform in the above-mentioned
cross-section with the center of gravity of the preform on the
rotational axis of symmetry and the tangent touching the contour
line at a point on the above-mentioned contour line is denoted as
.theta., and when that point is moved from some point on the
rotational axis of symmetry along the contour line, .theta.
increases monotonically from 90.degree., decreases monotonically,
and then increases monotonically, and a 90.degree. angle is formed
at the other point of intersection with the rotational axis of
symmetry.
[0191] Due to the characteristics of precision press molding, the
preform desirably does not have defects such as striae, cracks,
clouding, or devitrification, either internally or on the surface.
The surface of the preform is also desirably smooth. This is
because the surface of the preform remains on the final product as
the surface of the precision press-molded article.
[0192] The preform of the present invention will be described in
detail next. The preform of the present invention can be classified
into the nine types sequentially described below, and each of these
types can be more finely classified.
[0193] The first preform (referred to as "Preform 1" below) is
characterized by being comprised of an optical glass the components
of which are: [0194] P.sub.2O.sub.5: 15 to 70 molar percent, [0195]
Nb.sub.2O.sub.5: 1 to 30 molar percent [0196] TiO.sub.2: 0 to 20
molar percent (excluding 0 molar percent), [0197] Bi.sub.2O.sub.3:
6 to 30 molar percent (excluding 6 molar percent), [0198]
B.sub.2O.sub.3: 0 to 30 molar percent, [0199] WO.sub.3: 1 to 20
molar percent, [0200] SiO.sub.2: 0 to 5 weight percent (excluding 5
weight percent), and [0201] ZnO: 0 to 10 weight percent (excluding
10 weight percent), which has a refractive index (nd) of greater
than or equal to 1.7 and an Abbe number (.nu. d) of less than or
equal to 32.
[0202] Preform 1 can be more specifically divided into Preforms 1-1
to 1-3.
[0203] Preform 1-1 is Preform 1 in which the optical glass contains
more than 4 weight percent of Bi.sub.2O.sub.3 and from 3 to 15
weight percent of Li.sub.2O (excluding 3 weight percent).
[0204] Preform 1-2 is Preform 1 in which the optical glass contains
essential components in the form of B.sub.2O.sub.3 and Li.sub.2O,
and Li.sub.2O is contained in a proportion of 3 to 15 weight
percent (excluding 3 weight percent).
[0205] Preform 1-3 is Preform 1 in which the optical glass contains
less than 15 weight percent of WO.sub.3 (where this quantity is 0
to 15 molar percent) and from 3 to 15 weight percent of Li.sub.2O
(excluding 3 weight percent).
[0206] Each of Preforms 1-1 to 1-3 desirably contains an optional
component in the form of 0 to 15 molar percent of BaO, less than 10
weight percent of Na.sub.2O and K.sub.2O combined, and less than 5
weight percent of TiO.sub.2, with from 0 to 1 weight percent of
Sb.sub.2O.sub.3 relative to the combined quantity of all glass
components also desirably being added.
[0207] The second preform (referred to as "Preform 2" below) is
characterized by being comprised of an optical glass the components
of which are: [0208] P.sub.2O.sub.5: 15 to 70 molar percent, [0209]
Nb.sub.2O.sub.5: 1 to 30 molar percent [0210] TiO.sub.2: 0 to 20
molar percent (excluding 0 molar percent), [0211] Bi.sub.2O.sub.3:
6 to 30 molar percent (excluding 6 molar percent), [0212]
B.sub.2O.sub.3: 0 to 30 molar percent, [0213] WO.sub.3: 1 to 20
molar percent, [0214] SiO.sub.2: 0 to 5 weight percent (excluding 5
weight percent), where the combined Li.sub.2O, Na.sub.2O, and
K.sub.2O content is 0 to 15 percent (excluding 15 weight percent);
which has a refractive index (nd) of greater than or equal to 1.7
and an Abbe number (.nu.d) of less than or equal to 32;
[0215] Preform 2 can be more specifically divided into Preforms 2-1
to 2-3.
[0216] Preform 2-1 is Preform 2 in which the optical glass contains
more than 4 weight percent of Bi.sub.2O.sub.3 and 3 to 15 weight
percent of Li.sub.2O (excluding 3 weight percent).
[0217] Preform 2-2 is Preform 2 in which the optical glass contains
essential components in the form of B.sub.2O.sub.3 and Li.sub.2O,
with the proportion of Li.sub.2O being 3 to 15 weight percent
(excluding 3 weight percent).
[0218] Preform 2-3 is Preform 2 in which the optical glass contains
less than 15 weight percent of WO.sub.3 (from 0 to 15 molar
percent) and 3 to 15 weight percent (excluding 3 weight percent) of
Li.sub.2O.
[0219] Each of Preforms 2-1 to 2-3 desirably contains an optional
component in the form of 0 to 15 molar percent of BaO, less than 10
weight percent of Na.sub.2O and K.sub.2O combined, and less than 5
weight percent of TiO.sub.2, with and from 0 to 1 weight percent of
Sb.sub.2O.sub.3 relative to the combined quantity of all glass
components also desirably being added. Further, the weight ratio of
(TiO.sub.2 content/Bi.sub.2O.sub.3 content) is also desirably less
than 0.5.
[0220] The third preform (referred to as "Preform 3" below) is
characterized by being comprised of an optical glass the components
of which are: [0221] P.sub.2O.sub.5: 15 to 70 molar percent, [0222]
Nb.sub.2O.sub.5: 1 to 30 molar percent [0223] TiO.sub.2: 0 to 20
molar percent (excluding 0 molar percent), [0224] Bi.sub.2O.sub.3:
0 to 30 molar percent (excluding 0 molar percent), [0225]
B.sub.2O.sub.3: 0 to 30 molar percent, [0226] WO.sub.3: 1 to 20
molar percent, [0227] SiO.sub.2: 0 to 5 weight percent (excluding 5
weight percent), [0228] ZnO: 0 to 10 weight percent (excluding 10
weight percent); where the weight ratio of (TiO.sub.2
content/BiO.sub.2 content) is less than 0.5; which has a refractive
index (nd) of greater than or equal to 1.7 and an Abbe number
(.nu.d) of less than or equal to 32.
[0229] Preform 3 can be more specifically divided into Preforms 3-1
to 3-3.
[0230] Preform 3-1 is Preform 3 in which the optical glass contains
more than 4 weight percent of Bi.sub.2O.sub.3 and 3 to 15 weight
percent of Li.sub.2O (excluding 3 weight percent).
[0231] Preform 3-2 is Preform 3 in which the optical glass contains
essential components in the form of B.sub.2O.sub.3 and Li.sub.2O,
with the proportion of Li.sub.2O being 3 to 15 weight percent
(excluding 3 weight percent).
[0232] Preform 3-3 is Preform 3 in which the optical glass contains
less than 15 weight percent of WO.sub.3 (from 0 to 15 molar
percent) and 3 to 15 weight percent (excluding 3 weight percent) of
Li.sub.2O.
[0233] Each of Preforms 3-1 to 3-3 desirably contains an optional
component in the form of 0 to 15 molar percent of BaO, contains
less than 10 weight percent of Na.sub.2O and K.sub.2O combined,
contains Nb.sub.2O.sub.5, and contains less than 5 weight percent
of TiO.sub.2, with the weight ratio of (TiO.sub.2
content/Nb.sub.2O.sub.5 content) being less than 0.1. From 0 to 1
weight percent of Sb.sub.2O.sub.3 relative to the combined quantity
of all glass components is also desirably added.
[0234] The fourth (referred to as "Preform 4" below) is
characterized by being comprised of an optical glass the components
of which are: [0235] P.sub.2O.sub.5: 15 to 70 molar percent, [0236]
Nb.sub.2O.sub.5: 1 to 30 molar percent [0237] TiO.sub.2: 0 to 20
molar percent (excluding 0 molar percent), [0238] Bi.sub.2O.sub.3:
0 to 30 molar percent (excluding 0 molar percent), [0239]
B.sub.2O.sub.3: 0 to 30 molar percent, [0240] WO.sub.3: 1 to 20
molar percent, [0241] SiO.sub.2: 0 to 5 weight percent (excluding 5
weight percent), 0 to 15 weight percent (excluding 15 weight
percent) of Li.sub.2O, Na.sub.2O, and K.sub.2O, and a weight ratio
of (TiO.sub.2 content/Bi.sub.2O.sub.3 content) of less than 0.5;
which has a refractive index (nd) of greater than or equal to 1.7
and an Abbe number (.nu.d) of less than or equal to 32.
[0242] Preform 4 can be more specifically divided into Preforms 4-1
to 4-3.
[0243] Preform 4-1 is Preform 4 in which the optical glass contains
more than 4 weight percent of Bi.sub.2O.sub.3 and 3 to 15 weight
percent of Li.sub.2O (excluding 3 weight percent).
[0244] Preform 4-2 is Preform [1 sic, 4] in which the optical glass
contains essential components in the form of B.sub.2O.sub.3 and
Li.sub.2O, with the proportion of Li.sub.2O being 3 to 15 weight
percent (excluding 3 weight percent).
[0245] Preform 4-3 is Preform 4 in which the optical glass contains
less than 15 weight percent of WO.sub.3 (from 0 to 15 molar
percent) and 3 to 15 weight percent (excluding 3 weight percent) of
Li.sub.2O.
[0246] Each of Preforms 4-1 to 4-3 desirably contains an optional
component in the form of 0 to 15 molar percent of BaO. The optical
glass contains Nb.sub.2O.sub.5, contains less than 10 weight
percent of Na.sub.2O and K.sub.2O combined, and contains less than
5 weight percent of TiO.sub.2, with the weight ratio of (TiO.sub.2
content/Nb.sub.2O.sub.5 content) being less than 0.1. From 0 to 1
weight percent of Sb.sub.2O.sub.3 relative to the combined quantity
of all glass components is also desirably added. The content of
Bi.sub.2O.sub.3 desirably exceeds 6 weight percent.
[0247] The reasons for the compositional limits to the glasses
comprising Preforms 1 to 4 are described below. [0248]
P.sub.2O.sub.5 is a constituent component of the network structure
of the glass, and is an essential component for imparting to the
glass the stability required for manufacturing. However, when the
content of P.sub.2O.sub.5 exceeds 70 molar percent, the glass
transition temperature and sag point rise and weatherability
deteriorates. At less than 15 molar percent, the tendency of the
glass to devitrify becomes strong and the glass is unstable. Thus,
the P.sub.2O.sub.5 content is set to from 15 to 70 molar percent.
The P.sub.2O.sub.5 content desirably falls within a range of 17 to
67 percent.
[0249] Nb.sub.2O.sub.5 is an optional component that is desirably
incorporated to impart characteristics to the glass such as a high
refractive index and high dispersion without adding PbO. However,
when incorporated in excessively high quantity, the glass
transition temperature and sag point rise, stability deteriorates,
and high-temperature melt properties deteriorate. Further, the
problems of foaming and coloration also occur during precision
press molding of the glass. Thus, the content is desirably limited
to a range of 1 to 30 molar percent, preferably a range of 5 to 25
molar percent, and more preferably a range of 5 to 20 molar
percent. From the perspective of obtaining a high refractive index,
high dispersion characteristics, enhanced devitrification
stability, good high temperature melt properties, a low glass
transition temperature, and a low sag point while preventing
foaming and coloration during precision press molding, the quantity
of Nb.sub.2O.sub.5 incorporated is set along with the quantity of
TiO.sub.2 incorporated to achieve a weight ratio of (TiO.sub.2
content/Nb.sub.2O.sub.5 content) of less than 0.1.
[0250] TiO.sub.2, an essential component, has the effects of
enhancing the refractive index and dispersion property of the glass
and improving devitrification stability. Thus, it is incorporated
more than 0 (zero) molar percent. However, when the content exceeds
20 molar percent, the devitrification stability and transmittance
of the glass deteriorate, the sag point and liquid-phase
temperature rise sharply, and the glass tends to discolor during
precision press molding. Thus, the content is limited to 0 to 20
molar percent (excluding 0 molar percent). The desired range of the
TiO.sub.2 content is from 0.5 to 20 molar percent, the preferred
range is from 0.5 to 15 molar percent, and the more preferred range
is from 0.5 to 12 molar percent.
[0251] In particular, when a preform for precision press molding is
manufactured by forming a glass melt gob, if the glass stability is
low, the resulting preform devitrifies. If the glass melt flowing
temperature sets to a higher temperature, it is hard to prepare a
preform for precision press molding with high quality due to low
glass viscosity. In order to solve these problems, TiO.sub.2 is
also an essential component. Within the above listed ranges, the
TiO.sub.2 content is more preferably from 1 to 10 molar percent,
still more preferably from 2 to 8 molar percent from the
perspective of imparting a high refractive index and a high
dispersion property and preparing a preform for precision press
molding by forming a glass melt gob.
[0252] Bi.sub.2O.sub.3, another essential component, imparts a high
refractive index and a high dispersion property to the glass.
Bi.sub.2O.sub.3 greatly broadens the glass production range both at
high and low P.sub.2O.sub.5 contents, and has a stabilizing effect.
It is also a component that increases the weatherability of the
glass. Bi.sub.2O.sub.3 increases the wetting angle of platinum and
platinum alloys by the glass in a molten state, and enhances the
suppression of wetting when forming preforms for precision pressing
by the drip method or drop-cut method, described further below,
where a glass melt is caused to flow out of a platinum or
gold-containing platinum alloy pipe. Thus, it plays important roles
in increasing the weight precision of the preform and preventing
surface striae. However, when the content exceeds 30 molar percent,
the glass tends to devitrify and color.
[0253] The standard for setting lower limits to the Bi.sub.2O.sub.3
content is different for Preforms 1 and 2 than for Preforms 3 and
4. To render Preforms 1 and 2 more stable and impart better preform
characteristics, Bi.sub.2O.sub.3 is incorporated in a quantity
exceeding 6 molar percent, desirably greater than or equal to 6.5
molar percent. For the above-stated reasons, Bi.sub.2O.sub.3 is
incorporated into Preforms 1 and 2 in a proportion of greater than
6 molar percent but less than or equal to 30 molar percent,
desirably 6.5 to 30 molar percent, preferably 6.5 to 25 molar
percent, more preferably 6.5 to 15 molar percent, and still more
preferably 6.5 to 10 molar percent.
[0254] To impart greater glass stability and better preform
characteristics to Preforms 3 and 4, Bi.sub.2O.sub.3 is
incorporated within a range of 0 to 30 molar percent (excluding 0
molar percent), and the lower limit of the Bi.sub.2O.sub.3 content
is established in relation to the quantity of TiO.sub.2 present.
That is, the quantities of TiO.sub.2 and Bi.sub.2O.sub.3 are set so
that the weight ratio of (TiO.sub.2 content/Bi.sub.2O.sub.3
content) is less than 0.5. The preferred range of this weight ratio
is greater than 0 and less than or equal to 0.4. Both TiO.sub.2 and
Bi.sub.2O.sub.3 are components that impart a high refractive index
and a high dispersion property to the glass. Comparing [0255]
TiO.sub.2 and Bi.sub.2O.sub.3, the incorporation of a larger
quantity of Bi.sub.2O.sub.3 is desirable from the perspective of
increasing the stability of the glass and improving the wetting
property of the glass melt to achieve the above-stated optical
characteristics. A detailed examination of the quantities of
TiO.sub.2 and Bi.sub.2O.sub.3 introduced was conducted from this
perspective, revealing that it sufficed to specify the quantities
incorporated of these two components by the above weight ratio. The
content of Bi.sub.2O.sub.3 is desirably 0.5 to 30 molar percent,
preferably 0.5 to 25 molar percent, more preferably 0.5 to 15 molar
percent, still more preferably 1 to 15 molar percent, further more
preferably more than 2 molar percent to less than or equal to 15
molar percent, still further more preferably more than 2 molar
percent to less than or equal to 10 molar percent.
[0256] In Preforms 1-1, 2-1, 3-1, and 4-1, the quantity of
Bi.sub.2O.sub.3 incorporated is set to greater than 4 weight
percent, desirably greater than or equal to 4.5 weight percent, and
preferably greater than or equal to 5 weight percent. This further
increases the stability and weatherability of the glass and
heightens the inhibitory effect on increased wetting by the glass
as well as the following effects. When a glass melt is caused to
flow out of a flowing pipe such as a platinum or gold-containing
platinum alloy pipe for a long time period, the internal surface of
the pipe is roughened to form minute uneven, resulting in disorder
of glass flow. When a preform for precision press molding is
prepared from flowing out glass melt, the glass flow with disorder
results in preparation of poor products with striae. If a glass
melt containing Bi.sub.2O.sub.3 is caused to flow out of the
flowing pipe for a long time period, the inter surface of the pipe
is kept smooth and does not lose its gloss. If a glass melt
containing Bi.sub.2O.sub.3 is caused to flow out of a flowing pipe
with uneven internal surface, metallic gloss of the pipe surface is
recovered. While suppressing occasion of striae by using this
effect, it is possible to prepare a preform for precision press
molding with high quality in high productivity. In addition, as
mentioned above, a glass melt containing Bi.sub.2O.sub.3 has a
property preventing wetting a flow pipe. The glass wetted to the
pipe deteriorates and the deteriorated glass is incorporated into a
glass melt flowed out, resulting in lowering quality of a preform.
However, wetting of glass melt is reduced by incorporation of
Bi.sub.2O.sub.3 and lowering of a preform quality can be prevented.
When forming preforms by dripping a glass melt from a pipe, wetting
of glass melt may deteriorate weight accuracy of preforms. However,
wetting of glass melt is reduced by incorporation of
Bi.sub.2O.sub.3 and preforms can be prepared while keeping high
weight accuracy. [0257] B.sub.2O.sub.3 is an optional component. A
component that both improves the molten properties of the glass and
is extremely effective at homogenizing the glass, the addition of a
small quantity of B.sub.2O.sub.3 changes the bonding properties of
OH groups in the glass and is extremely effective at preventing
foaming of the glass during precision press molding. Accordingly,
B.sub.2O.sub.3 is incorporated into Preforms 1-2, 2-2, 3-2, and 4-2
as an essential component to improve these effects. However, when
30 molar percent is exceeded, the weatherability of the glass
deteriorates and the glass becomes unstable. Thus, the content is
limited to within the range of from 0 to less than or equal to 30
molar percent. The B.sub.2O.sub.3 content is desirably 1 to 30
molar percent, preferably 1 to 25 molar percent. [0258] WO.sub.3 is
a component that reduces the glass transition temperature without
the use of PbO and imparts a high refractive index and high
dispersion properties to the glass. WO.sub.3 has the effect of
lowering the glass transition temperature and sag point in the same
manner as alkali metal oxides, and increases the refractive index.
It also suppresses the wetting property of the pressing mold by the
preform, thus decreasing in the adhesion of the glass to the mold
during precision press molding. It has and effect of suppressing
glass foaming during precision press molding as well. However, when
incorporated in excessively large quantity, the preform tends to
color and the high-temperature viscosity of the glass tends to
drop, making it difficult to mold preforms for precision press
molding from a glass melt flowing out of a flow pipe. In addition,
it tends to occur radial micro-scratching defects on the surface of
the precision press molded products. Accordingly, the content is
set to 1 to 20 molar percent. The content of WO.sub.3 desirably
falls within a range of 2 to 20 molar percent, more preferably
within a range of 2.5 to 20 molar percent.
[0259] To achieve an adequate WO.sub.3 incorporation effect, the
ratio of W to the combined quantity of Nb, W, Ti, and Bi in the
cationic ratio (W/(Nb+W+Ti+Bi)) is desirably greater than or equal
to 0.035, preferably greater than or equal to 0.04, more preferably
greater than or equal to 0.045, and still more preferably greater
than or equal to 0.05. The upper limit of the W/(Nb+W+Ti+Bi) is
about 0.2.
[0260] In Preforms 1-3, 2-3, 3-3, and 4-3, the quantity of WO.sub.3
incorporated is less than 15 weight percent (0 to 15 molar
percent), desirably less than or equal to 14.5 weight percent, and
preferably less than or equal to 14 weight percent. In these cases,
incorporation of WO.sub.3 is preferred, and the quantity of
WO.sub.3 incorporated sets to more preferably from 1 to 15 molar
percent in Preforms 1-3, 2-3, 3-3, and 4-3.
[0261] In Preforms 1-1, 1-2, 2-1, 2-2, 3-1, 3-2, 4-1, and 4-2, the
quantity of WO.sub.3 incorporated is less than 15 weight percent (0
to 15 molar percent), desirably less than or equal to 14.5 weight
percent, and preferably less than or equal to 14 weight
percent.
[0262] SiO.sub.2, an optional component, increases the glass
transition temperature and sag point and makes it difficult to
achieve desired optical characteristics when incorporated in
excessively high quantity. Thus, the content is set to 0 to 5
weight percent (excluding 5 weight percent). The desired range of
SiO.sub.2 is from 0 to 4 weight percent, preferably 0 to 2 weight
percent. Its absence is even more preferred. As denoted in moral
percent, the desired range of SiO.sub.2 is from 0 to 2 molar
percent, preferably 0 to 1 molar percent.
[0263] ZnO is a component optionally incorporated to raise the
refractive index and dispersion of the glass. When incorporated in
small quantity, it also has the effect of lowering the glass
transition temperature and sag point. However, when incorporated in
large quantity, it compromises the devitrification stability of the
glass and sometimes causes the liquid phase temperature to rise.
Accordingly, in Preforms 1 and 3, the quantity of ZnO is set to 0
to 10 weight percent (10 weight percent excluded). In Preforms 2
and 4, when adding ZnO, a desirable content is 0 to 10 weight
percent (excluding 10 weight percent). The preferred content of ZnO
in all of Preforms 1 to 4 is 0 to 9 weight percent, more preferably
0.2 to 9 weight percent. As denoted in moral percent, the desired
range of ZnO is from 0 to 12 molar percent, preferably 1 to 10
molar percent, more preferably 2 to 8 molar percent. [0264]
Li.sub.2O, Na.sub.2O, and K.sub.2O are all components incorporated
to lower the glass transition temperature, sag point, and
liquid-phase temperature and improve the high-temperature melt
properties of the glass. However, the incorporation of excessive
quantities of Li.sub.2O, Na.sub.2O, and K.sub.2O causes
deterioration of glass stability and tends to cause deterioration
of glass weatherability and durability.
[0265] Thus, in Preforms 2 and 4, the combined quantity of
Li.sub.2O, Na.sub.2O, and K.sub.2O is set to 0 to 15 weight percent
(excluding 15 weight percent). For Preforms 1 and 3, as well, the
combined quantity of Li.sub.2O, Na.sub.2O, and K.sub.2O is
desirably set to 0 to 15 weight percent (excluding 15 weight
percent).
[0266] In all of Preforms 1 to 4, the combined quantity of
Li.sub.2O, Na.sub.2O, and K.sub.2O is desirably set to 0 to 14
weight percent, preferably to 5 to 14 weight percent. As denoted in
moral percent, the desired range of the combined quantity is less
than 42 molar percent, preferably less than or equal to 38 molar
percent.
[0267] In all of Preforms 1 to 4, the combined quantity of
Na.sub.2O and K.sub.2O is desirably set to less than 10 weight
percent from the perspective of improving glass stability,
weatherability, and durability.
[0268] Among the alkali metal oxides, Li.sub.2O is the most
effective to lower the glass transition temperature and sag point,
and to increase the refractive index. Thus, in the present
invention, Li.sub.2O is predominantly incorporated element. The
quantity of Li.sub.2O incorporated is set to 3 to 15 weight percent
(excluding 3 weight percent), desirably more than 3 weight percent
and less than 15 weight percent, and preferably from 3.1 to 14.9
weight percent for all of Preforms 1 to 4. Still more preferably,
the quantity incorporated falls within a range of less than or
equal to 30 molar percent, more preferably less than or equal to 25
molar percent. It is particularly preferable for the quantity
incorporated to satisfy the above range while constituting less
than 5 weight percent. In order to impart high refractive index
property and low-temperature softening prosperity at the same time,
while WO.sub.3 plays important roles in the high refractive index
property imparting components, Li.sub.2O plays important roles in
the alkali metal oxides. That is, while keeping the glass
stability, in order to impart the above mentioned two properties,
co-incorporation of WO.sub.3 and Li.sub.2O is particularly
preferred. As denoted in moral percent, the range of Li.sub.2O
content is preferably from 2 to 30 molar percent, more preferably 2
to 25 molar percent, still more preferably 4 to 25 molar percent,
and still further preferably 5 to 20 molar percent.
[0269] The quantity of Na.sub.2O incorporated is desirably set to
within a range of 0 to 30 molar percent, preferably more than 0
percent and less than or equal to 30 molar percent, and still more
preferably, 1 to 20 molar percent. It is particularly preferable
for the quantity incorporated to satisfy the above range while
constituting less than 5 weight percent.
[0270] The quantity of K.sub.2O incorporated desirably falls within
a range of from 0 to 30 molar percent, preferably 0 to 25 molar
percent, and more preferably, 0.1 to 10 molar percent. To enhance
the above-described effect of incorporating Li.sub.2O, the molar
proportion of Li.sub.2O in the alkali metal oxides in the glass,
denoted as Li.sub.2O/(Li.sub.2O+Na.sub.2O+K.sub.2O), is desirably
greater than or equal to 0.4, preferably greater than or equal to
0.44, and more preferably greater than or equal to 0.50.
[0271] BaO, an optional component, is effective at increasing the
refractive index of the glass, increasing devitrification stability
(resistance to devitrification), and lowering the liquid-phase
temperature. In particular, when a large quantity of WO.sub.3 is
incorporated, the incorporation of BaO prevents coloration of the
glass and enhances devitrification stability. When little
P.sub.2O.sub.5 is incorporated, BaO has the effect of increasing
the weatherability of the glass. However, when the quantity of BaO
exceeds 15 molar percent, the glass becomes unstable and the glass
transition temperature and sag point increase. Thus, when
incorporating BaO, the content is desirably kept to 0 to 15 molar
percent, preferably 0 to 12 molar percent, more preferably 0 to 11
molar percent, and even more preferably, 0 to 10 molar percent.
[0272] MgO, CaO, and SrO are optional components that can be added
to adjust glass stability and weatherability. When added in
excessively large quantity, the glass becomes highly unstable.
Thus, the content of each of these components is desirably from 0
to 25 molar percent, and preferably from 0 to 15 molar percent.
More preferably, the combined quantity of MgO, CaO, and Sr is
desirably from 0 to 10 molar percent.
[0273] Al.sub.2O.sub.3, La.sub.2O.sub.3, Gd.sub.2O.sub.3,
Yb.sub.2O.sub.3, ZrO.sub.2, and Ta.sub.2O.sub.5 are optional
components used to adjust the stability and optical constants of
the glass. However, these components all raise the glass transition
temperature and render precision press molding difficult. Thus, the
quantities added are desirably kept to 0 to 15 molar percent of
Al.sub.2O.sub.3, 0 to 10 molar percent of La.sub.2O.sub.3, 0 to 10
molar percent of Gd.sub.2O.sub.3, 0 to 10 molar percent of
Yb.sub.2O.sub.3, 0 to 10 molar percent of ZrO.sub.2, and 0 to 10
molar percent of Ta.sub.2O.sub.5. Preferably, the quantity of
Al.sub.2O.sub.3 is set to 0 to 12 molar percent and that of each of
La.sub.2O.sub.3, Gd.sub.2O.sub.3, Yb.sub.2O.sub.3, ZrO.sub.2, and
Ta.sub.2O.sub.5 is set to 0 to 8 molar percent. Still further, the
combined quantity of Al.sub.2O.sub.3, La.sub.2O.sub.3,
Gd.sub.2O.sub.3, Yb.sub.2O.sub.3, ZrO.sub.2, and Ta.sub.2O.sub.5 is
preferably kept to less than 5 molar percent, more preferably to
less than 2 molar percent.
[0274] Sb.sub.2O.sub.3 is an effective glass clarifying agent.
However, when added in excessively large quantity, the glass tends
to foam during precision press molding. Thus, the content is
desirably kept to 0 to 1 weight percent (excluding 1 weight
percent), preferably 0 to 0.9 weight percent, of the total quantity
of all glass components.
[0275] The glasses used to form Preforms 1 to 4 do not contain
Ag.sub.2O, Tl.sub.2O, or PbO. The term "do not contain" means that
these components are not employed as starting materials when
preparing the glass. When these components are contained as
unavoidable impurities in the starting materials of other
components, the term "do not contain" is satisfied. Ag.sub.2O tends
to reduce readily, precipitating in the glass as microparticles of
metallic silver and causing optical scattering. Thus, it is a
non-essential component for achieving the object of the present
invention and is not contained in Preforms 1 to 4. In particular,
Ag.sub.2O tends to precipitate out during precision press molding
in nonoxidizing atmospheres such as nitrogen. Tl.sub.2O is scarce
and toxic, and is thus not contained in Preforms 1 to 4. The same
holds true for PbO and As.sub.2O; they reduce during precision
press molding and precipitate out as metal salts on the surface of
the precision press-molded product. They also adhere to the molds
used to mold lenses in precision press molding, making it
impossible to maintain the precision of the surface transferred to
the precision press-molded lens and requiring maintenance to remove
the metal salts adhering to the mold. This precludes mass
production. There is also the problem of environmental pollution.
Thus, PbO is not incorporated into Preforms 1 to 4.
[0276] The introduction of As.sub.2O.sub.3 CdO, and the like is to
be avoided in consideration of the environment. The incorporation
of highly volatile components is undesirable when directly forming
preforms from glass melt. Accordingly, fluorine is desirably not
incorporated. TeO.sub.2, which is toxic, and GeO.sub.2, which is
expensive, and the like are also desirably not incorporated.
[0277] In the glasses used to mold Preforms 1 to 4, the combining
of the individual components in any quantities falling within their
above-stated desirable ranges yields a desirable combination range.
However, examples of several desirable combination ranges will be
given.
Examples of desirable composition ranges of Preforms 1 and 2
[0278] In Preforms 1-1 to 1-4 and 2-1 to 2-4, desirable examples
are:
(1) compositions where the combined content of Na.sub.2O and
K.sub.2O is less than 10 weight percent, the content of TiO.sub.2
is less than 5 weight percent, and the content of Sb.sub.2O.sub.3
is from 0 to 1 weight percent of the combined quantities of all the
glass components; (2) compositions where the combined content of
Na.sub.2O and K.sub.2O is less than 10 weight percent, the weight
ratio of the (TiO.sub.2 content/Bi.sub.2O.sub.3 content) is less
than 0.5, and the content of Sb.sub.2O.sub.3 is 0 to 1 weight
percent of the combined quantities of all glass components; and (3)
compositions where the glass components are: [0279] P.sub.2O.sub.5:
17 to 67 molar percent, [0280] Nb.sub.2O.sub.5: 1 to 30 molar
percent (more preferably 5 to 20 molar percent) [0281] TiO.sub.2:
0.5 to 12 molar percent, [0282] Bi.sub.2O.sub.3: 6.5 to 25 molar
percent, [0283] B.sub.2O.sub.3: 1 to 25 molar percent, [0284]
WO.sub.3: 1 to 20 molar percent, [0285] SiO.sub.2: 0 to 4 weight
percent, [0286] ZnO: 0.2 to 9 weight percent, [0287] Li.sub.2O: 1
to 25 weight percent (but less than 5 weight percent), [0288]
Na.sub.2O: 1 to 20 molar percent, [0289] K.sub.2O: 0.1 to 10 molar
percent where the combined quantity of Li.sub.2O, Na.sub.2O, and
K.sub.2O is 5 to 14 weight percent, [0290] BaO: 0 to 11 molar
percent, and where the weight ratio of (TiO.sub.2
content/Nb.sub.2O.sub.5 content) is less than 0.1 and the quantity
of Sb.sub.2O.sub.3 added is 0 to 0.9 weight percent of the combined
quantity of all glass components; and (4) compositions combining
(1) and (2) above; compositions combining (2) and (3) above;
compositions combining (1) and (3) above; compositions combining
(1), (2), and (3) above. Examples of desirable composition ranges
of Preforms 3 and 4
[0291] In Preforms 3-1 to 3-4 and 4-1 to 4-4, desirable examples
are:
(5) compositions where the combined content of Na.sub.2O and
K.sub.2O is less than 10 weight percent, the content of TiO.sub.2
is less than 5 weight percent, Nb.sub.2O.sub.5 is incorporated, the
weight ratio of (TiO.sub.2 content/Nb.sub.2O.sub.5 content) is less
than 0.1, and the quantity of Sb.sub.2O.sub.3 added is 0 to 1
weight percent of the combined quantities of all of the glass
components; (6) compositions where the Bi.sub.2O.sub.3 content
exceeds 6 weight percent, the combined quantity of Na.sub.2O and
K.sub.2O is less than 10 weight percent, the quantity of TiO.sub.2
is less than 5 weight percent, and the quantity of Sb.sub.2O.sub.3
added is from 0 to 1 weight percent of the combined quantities of
all glass components; (7) compositions where the glass components
are: [0292] P.sub.2O.sub.5: 17 to 67 molar percent, [0293]
Nb.sub.2O.sub.5: 5 to 20 molar percent [0294] TiO.sub.2: 0.5 to 12
molar percent, [0295] B.sub.2O.sub.3: 1 to 25 molar percent, [0296]
WO.sub.3: 1 to 20 molar percent, [0297] SiO.sub.2: 0 to 4 weight
percent, [0298] ZnO: 0.2 to 9 weight percent, [0299] Li.sub.2O,
Na.sub.2O, and K.sub.2O: 5 to 14 weight percent, [0300] Li.sub.2O:
1 to 25 molar percent (less than 5 weight percent) [0301]
Na.sub.2O: 1 to 20 molar percent, [0302] K.sub.2O: 0.1 to 10 molar
percent [0303] BaO: 0 to 11 molar percent, and where
Bi.sub.2O.sub.3 is incorporated in a weight ratio of (TiO.sub.2
content/Bi.sub.2O.sub.3 content) of greater than 0 and less than or
equal to 0.4, the weight ratio of (TiO.sub.2
content/Nb.sub.2O.sub.5 content) is less than 0.1, and
Sb.sub.2O.sub.3 is added in a quantity of 0 to 0.9 weight percent
of the combined quantities of all glass components. Examples of
desirable composition ranges of Preforms 1 to 4
[0304] In Preforms 1 to 4, desirable examples are:
(8) compositions where the Na.sub.2O content is less than 5 weight
percent; (9) compositions where the SiO.sub.2 content is 0 to 2
weight percent (it being preferred that SiO.sub.2 not be
incorporated at all); (10) the combined contents of P.sub.2O.sub.5,
Nb.sub.2O.sub.5, TiO.sub.2, Bi.sub.2O.sub.3, B.sub.2O.sub.3,
WO.sub.3, SiO.sub.2, ZnO, Li.sub.2O, Na.sub.2O, K.sub.2O, and BaO
exceed 95 molar percent; (11) the combined contents of
P.sub.2O.sub.5, Nb.sub.2O.sub.5, TiO.sub.2, Bi.sub.2O.sub.3,
B.sub.2O.sub.3, WO.sub.3, SiO.sub.2, ZnO, Li.sub.2O, Na.sub.2O,
K.sub.2O, and BaO exceed 98 molar percent; (12) the combined
contents of P.sub.2O.sub.5, Nb.sub.2O.sub.5, TiO.sub.2,
Bi.sub.2O.sub.3, B.sub.2O.sub.3, WO.sub.3, SiO.sub.2, ZnO,
Li.sub.2O, Na.sub.2O, K.sub.2O, and BaO exceed 99 molar percent;
and (13) the combined contents of P.sub.2O.sub.5, Nb.sub.2O.sub.5,
TiO.sub.2, Bi.sub.2O.sub.3, B.sub.2O.sub.3, WO.sub.3, SiO.sub.2,
ZnO, Li.sub.2O, Na.sub.2O, K.sub.2O, and BaO constitute 100 molar
percent and Sb.sub.2O.sub.3 is added in a quantity of 0 to 0.9
weight percent of the combined quantities of all glass
components.
[0305] To achieve greater glass stability, a lower glass transition
temperature, and less coloration, the refractive index (nd) is
desirably set to 1.7 to 2.0 and the Abbe number (.nu.d) to within
the range of 20 to 32 in Preforms 1 to 4. In glasses having the
glass compositions of the ranges specified in the claims, the
refractive index (nd) is basically 1.7 to 2.0 and the Abbe number
(.nu.d) 20 to 32. The glass composition can be adjusted within the
ranges specified in the claims to obtain glass preforms that have a
refractive index and Abbe number falling within the above-stated
ranges and achieve glass stability, a low glass transition
temperature, and low coloration. The glasses of the above mentioned
preforms have not only high refractive index but also
low-temperature softening property suited for precision press
molding and the excellent stability enabling formation of a preform
directly from a glass gob in the melt state. Thus, the refractive
index (nd) of more than or equal to 1.80 is more effective and that
of more than or equal to 1.83 is further more effective.
[0306] In Preforms 1 to 4, to lower the temperature of the pressing
mold in precision press molding, the glass transition temperature
(Tg) is desirably kept to less than or equal to 600.degree. C.,
preferably less than or equal to 550.degree. C., and more
preferably less than or equal to 500.degree. C. The sag point (Ts)
is desirably kept to less than or equal to 650.degree. C.,
preferably less than or equal to 600.degree. C., and more
preferably to less than or equal to 550.degree. C.
[0307] Glasses having glass compositions falling within the ranges
specified in the claims basically have glass transition
temperatures and sag points falling within the above-stated ranges.
Glass preforms having glass transition temperatures and sag points
falling within the above-stated ranges can be obtained by adjusting
the glass compositions within the ranges stated in the claims.
[0308] The wavelength within the range of 280 to 700 nm at which
spectral transmittance reaches 80 percent (denoted as .lamda.80
below), when converted to a glass thickness of 10.0 +0.1 mm, is
desirably less than or equal to 570 nm, preferably less than or
equal to 550 nm, and more preferably less than or equal to 520 nm.
The wavelength at which this spectral transmittance reaches 5
percent (denoted below as .lamda.5) is desirably less than or equal
to 400 nm, preferably less than or equal to 390 nm.
[0309] Glasses having glass compositions falling within the ranges
specified in the claims basically have the above-stated .lamda.80
and .lamda.5 ranges. Glass preforms having .lamda.80 and .lamda.5
values falling within the above-stated ranges can be obtained by
adjusting the glass compositions within the ranges stated in the
claims.
[0310] Plate-shaped samples 10.0+0.1 mm in thickness comprised of
the same optical glass as is used to mold the preforms, two sides
of which have been optically ground, can be used to test the above
spectral transmittance. The spectral transmittance is the ratio of
the amount of light transmitted by the sample to the amount of
perpendicular incident light on the sample surface (amount of
transmitted light/amount of incident light). Losses such as
reflection loss on the sample surface, absorption within the
sample, and scattering are included in the difference between the
amount of incident light and the amount of transmitted light. When
the thickness of the sample is not 10.0+0.1 mm, it suffices to
convert the spectral transmittance of the sample to that
corresponding to a thickness of 10.0+0.1 mm by the known
method.
[0311] The above glass exhibits a spectral transmittance value of
greater than or equal to 5 percent as converted to a thickness of
10.0+0.1 mm over the range of .lamda.5 to 700 nm and a spectral
transmittance value of greater than or equal to 80 percent as
converted to a thickness of 10.0+0.1 mm over the range of .lamda.80
to 700.
[0312] The liquid-phase (LT) temperature of the above-described
glass is desirably less than 1,000.degree. C., preferably less than
960.degree. C., to mold high-quality preforms from glass melt.
[0313] Glasses having glass compositions falling within the ranges
specified in the claims basically have a liquid-phase temperature
(LT) within the stated range. Glass preforms having a liquid-phase
temperature (LT) falling within the above-stated range can be
obtained by adjusting the glass composition within the ranges
specified in the claims.
[0314] The preferred specific gravity falls within a range of from
3.4 to 4.5. The preferred range of the average coefficient of
linear expansion (.alpha.) from 100 to 300.degree. C. is from 90 to
140.times.10.sup.-7/.degree. C. Glasses having glass compositions
falling within the ranges specified in the claims basically have
specific gravity values and average coefficients of linear
expansion falling within the above-stated ranges. Preforms having
specific gravity values and average coefficients of linear
expansion falling within the above-stated ranges can be obtained by
adjusting the glass composition within the ranges specified in the
claims.
[0315] The methods used to measure various physical properties are
described in the embodiments.
[0316] Preforms comprised of optical glass having an Abbe number
(.nu.d) exceeding 32 will be described next.
[0317] The fifth preform (referred to hereinafter as "Preform 5")
is characterized by being comprised of an optical glass the
components of which are: [0318] P.sub.2O.sub.5: 15 to 70 molar
percent, [0319] Bi.sub.2O.sub.3: 0.1 to 7 molar percent (excluding
7 molar percent), [0320] Na.sub.2O: 0 to 30 molar percent, [0321]
K.sub.2O: 0 to 30 molar percent where the combined content of
Li.sub.2O, Na.sub.2O, and K.sub.2O is less than 40 molar percent,
[0322] ZnO: 0 to 35 molar percent, [0323] CaO: 0 to 35 molar
percent, [0324] BaO: 0 to 50 molar percent, [0325] Nb.sub.2O.sub.5:
0 to 35 molar percent [0326] WO.sub.3: 0 to 25 molar percent, where
the combined content of Nb.sub.2O.sub.5 and WO.sub.3 exceeds 0
molar percent, [0327] SiO.sub.2: 0 to 5 weight percent (excluding 5
weight percent), where 0 to 1 weight percent of Sb.sub.2O.sub.3 is
added to the total content of glass components; which has an Abbe
number (.nu.d) exceeding 32.
[0328] The sixth preform (referred to hereinafter as "Preform 6")
is characterized by being comprised of an optical glass the
components of which are: [0329] P.sub.2O.sub.5: 15 to 70 molar
percent, [0330] Bi.sub.2O.sub.3: 0.1 to 7 molar percent (excluding
7 molar percent), [0331] Li.sub.2O: 10 to 40 molar percent
(excluding 10 molar percent and 40 molar percent),
[0332] Na.sub.2O: 0 to 30 molar percent,
[0333] K.sub.2O: 0 to 30 molar percent,
where the combined content of Li.sub.2O, Na.sub.2O, and K.sub.2O is
less than 40 molar percent, [0334] ZnO: 0 to 35 molar percent,
[0335] CaO: 0 to 35 molar percent, [0336] BaO: 0 to 50 molar
percent, [0337] Nb.sub.2O.sub.5: 0 to 35 molar percent [0338]
WO.sub.3: 0 to 25 molar percent, [0339] SiO.sub.2: 0 to 5 weight
percent (excluding 5 weight percent), where 0 to 1 weight percent
of Sb.sub.2O.sub.3 is added to the total content of glass
components; which has an Abbe number (.nu.d) exceeding 32;
[0340] The seventh preform (referred to hereinafter as "Preform 7")
is characterized by being comprised of an optical glass the
components of which are: [0341] P.sub.2O.sub.5: 15 to 70 molar
percent, [0342] Bi.sub.2O.sub.3: 0.1 to 7 molar percent (excluding
7 molar percent), [0343] Na.sub.2O: 0 to 30 molar percent, [0344]
K.sub.2O: 0 to 30 molar percent, where the combined content of
Li.sub.2O, Na.sub.2O, and K.sub.2O is less than 40 molar percent,
[0345] ZnO: 0 to 35 molar percent, [0346] CaO: 0 to 35 molar
percent, [0347] BaO: 20 to 50 molar percent (excluding 20 molar
percent), [0348] Nb.sub.2O.sub.5: 0 to 35 molar percent [0349]
WO.sub.3: 0 to 25 molar percent, [0350] SiO.sub.2: 0 to 5 weight
percent (excluding 5 weight percent), where 0 to 1 weight percent
of Sb.sub.2O.sub.3 is added to the total content of glass
components; which has an Abbe number (.nu.d) exceeding 32.
[0351] In each of Preforms 5 to 7, the optical glass desirably
comprises more than 0 weight percent of Nb.sub.2O.sub.5, the weight
ratio (TiO.sub.2 content/Bi.sub.2O.sub.3 content) is desirably less
than 0.5, and the weight ratio (TiO.sub.2 content/Nb.sub.2O.sub.5
content) is desirably less than 0.1. The optical glass also
desirably comprises 0 to 5 weight percent (excluding 5 weight
percent) of TiO.sub.2 and 0 to 30 weight percent (excluding 30
weight percent) of Nb.sub.2O.sub.5.
[0352] The reasons for the composition limits of the glasses from
which Preforms 5 to 7 are formed will be given below.
[0353] P.sub.2O.sub.5 is a constituent component of the network
structure of the glass, and is an essential component for imparting
to the glass the stability required for manufacturing. To lower the
glass transition temperature and sag point, increase
weatherability, and enhance devitrification stability, the content
of P.sub.2O.sub.5 is set within a range of 15 to 70 molar percent,
preferably 17 to 67 molar percent.
[0354] Bi.sub.2O.sub.3 is an essential component that greatly
increases the glass production range and imparts stability both
when large and small P.sub.2O.sub.5 contents are employed. It is
also a component that increases the weatherability of the glass.
Bi.sub.2O.sub.3 increases the platinum wetting angle of the glass
in a molten state, and helps prevent wetting when forming preforms
for precision pressing by the dripping method or drop-cut method,
described further below, where a glass melt is caused to flow out
of a platinum or gold-containing platinum alloy pipe. Thus, it
plays important roles in increasing the weight precision of the
preform and suppressing surface striae. Thus, Bi.sub.2O.sub.3 is
incorporated in a quantity of greater than or equal to 0.1 molar
percent. However, when the content exceeds 7 molar percent, the
glass ends to devitrify and discolor. Thus, the content is limited
to 0.1 to 7 molar percent (excluding 7 molar percent), desirably
0.1 to 6 molar percent, and preferably 0.2 to 6 molar percent.
[0355] Li.sub.2O, Na.sub.2O, and K.sub.2O are components introduced
to improve the resistance to devitrification of the glass, lower
the glass transition temperature, lower the sag point, lower the
liquid-phase temperature, and improve the high-temperature melt
properties of the glass.
[0356] However, when Na.sub.2O, and K.sub.2O are respectively
contained in a quantity greater than 30 molar percent each, or when
the combined quantity of Li.sub.2O, Na.sub.2O, and K.sub.2O exceeds
40 molar percent, the stability, weatherability, and durability of
the glass tend to deteriorate. Thus, the content of Na.sub.2O is
set to 0 to 30 molar percent, the content of K.sub.2O is set to 0
to 30 molar percent, and the combined quantity of Li.sub.2O,
Na.sub.2O, and K.sub.2O is set to less than 40 molar percent.
[0357] The content of Na.sub.2O is desirably from 1 to 30 molar
percent, preferably from 1 to 20 molar percent. In addition to
falling within this range, the quantity is also desirably less than
5 weight percent.
[0358] The content of K.sub.2O is desirably 0 to 25 molar percent,
preferably 0.1 to 10 molar percent.
[0359] The combined content of Li.sub.2O, Na.sub.2O, and K.sub.2O
is desirably from 12 to 39 molar percent, preferably from 12 to 38
molar percent.
[0360] In Preform 6, the content of Li.sub.2O is 10 to 40 molar
percent (excluding 10 molar percent and 40 molar percent),
preferably 10.1 to 35 molar percent.
[0361] ZnO has the effect of lowering the glass transition
temperature, sag point, and liquid-phase temperature when
incorporated in small quantity. However, when incorporated in large
quantity, there is a risk of sharp deterioration of the
devitrification stability of the glass and an increased
liquid-phase temperature. Accordingly, the ZnO content is set to 0
to 35 molar percent, desirably 1 to 20 molar percent, and
preferably 2 to 20 molar percent.
[0362] CaO is an optional component that is incorporated to adjust
glass stability and weatherability. When incorporated in excessive
quantity, the glass becomes extremely unstable. Thus, the content
is desirably set to 0 to 35 molar percent, preferably 0 to 10 molar
percent, and more preferably 0 to 5 molar percent.
[0363] BaO is a component that effectively improves devitrification
stability (resistance to devitrification) and lowers the
liquid-phase temperature. When the P.sub.2O.sub.5 content is low,
BaO has the effect of increasing the weatherability of the glass.
However, when 50 molar percent is exceeded, the glass becomes
unstable and the glass transition temperature and sag point rise.
Thus, the BaO content is set to less than or equal to 50 molar
percent.
[0364] In Preforms 5 and 6, the BaO content is set to 0 to 50 molar
percent. In Preform 7, the BaO content is set to 20 to 50 molar
percent (excluding 20 molar percent). In Preforms 5 and 6, the BaO
content is desirably from 20 to 50 molar percent (excluding 20
molar percent). In Preforms 5 to 7, the BaO content is desirably
from 20 to 40 molar percent (excluding 20 percent), and preferably
from 20 to 30 molar percent (excluding 20 molar percent).
[0365] Nb.sub.2O.sub.5 is an optional component that can be
incorporated to impart desired optical characteristics without
employing PbO. However, when incorporated in excessive quantity,
the glass transition temperature and sag point increase, stability
deteriorates, and high-temperature melt properties deteriorate.
Further, there is a problem in that the glass tends to foam and
discolor during precision press molding. Thus, the content is set
to 0 to 35 molar percent, desirably 0 to 15 molar percent, and
preferably 0 to 10 molar percent. The quantity of Nb.sub.2O.sub.5
is desirably 0 to 30 weight percent (excluding 30 weight percent),
preferably 0 to 20 weight percent, and more preferably 0 to 10
weight percent.
[0366] WO.sub.3 is an optional component that can decrease the
glass transition temperature without using PbO. WO.sub.3 exhibits
the same effect of reducing the glass transition temperature and
sag point as alkali metal oxides, and also has the effect of
inhibiting wetting of the pressing mold by the preform. Thus, it
has the effect of improving the mold separation of the glass in
precision press molding. However, when employed in excessive
quantity, the preform tends to develop color and the
high-temperature viscosity of the glass decreases, making it
difficult to mold preforms for precision press molding. Thus, the
content is set to 0 to 25 molar percent, desirably 0 to 10 molar
percent, and preferably 0 to 7 molar percent.
[0367] In Preform 5, the combined quantity of Nb.sub.2O.sub.5 and
WO.sub.3 is set to greater than 0 to facilitate achieving desired
optical constants and improve mold separation during precision
press molding.
[0368] SiO.sub.2 is an optional component that, in excessive
quantity, raises the glass transition temperature and sag point.
Thus, the content is set to 0 to 5 weight percent (excluding 5
weight percent). The content of SiO.sub.2 is desirably 0 to 4
weight percent, preferably 0 to 2 weight percent, with no
incorporation at all being even more preferred.
[0369] B.sub.2O.sub.3 is an optional component extremely effective
at improving glass melt properties and homogeneity. When
incorporated in small quantity, it changes the bonding property of
the OH in the glass and is extremely effective at preventing
foaming of the glass during precision press molding. However, when
incorporated in a quantity greater than 10 molar percent, glass
weatherability deteriorates and the glass becomes unstable. Thus,
the content is desirably set to 0 to 10 molar percent, preferably 0
to 5 molar percent.
[0370] Al.sub.2O.sub.3, La.sub.2O.sub.3, Gd.sub.2O.sub.3,
Y.sub.2O.sub.3, ZrO.sub.2, and Ta.sub.2O.sub.5 are optional
components that adjust glass stability and optical constants. Since
all of these components raise the glass transition temperature, the
content thereof is desirably kept to 0 to 15 molar percent of
Al.sub.2O.sub.3, 0 to 10 molar percent of La.sub.2O.sub.3, 0 to 10
molar percent of Gd.sub.2O.sub.3, 0 to 10 molar percent of
Y.sub.2O.sub.3, 0 to 10 molar percent of ZrO.sub.2, and 0 to 10
molar percent of Ta.sub.2O.sub.5, with the quantity of
Al.sub.2O.sub.3 preferably being 0 to 10 molar percent and the
quantity of each of La.sub.2O.sub.3, Gd.sub.2O.sub.3,
Y.sub.2O.sub.3, ZrO.sub.2, and Ta.sub.2O.sub.5 preferably being 0
to 8 molar percent. The combined quantity of Al.sub.2O.sub.3,
La.sub.2O.sub.3, Gd.sub.2O.sub.3, Y.sub.2O.sub.3, ZrO.sub.2, and
Ta.sub.2O.sub.5 is desirably kept to 0 to 6 molar percent
(excluding 6 molar percent), preferably 0 to 5 molar percent
(excluding 5 molar percent). [0371] TiO.sub.2 is an optional
component that effectively increases glass dispersion properties
and enhances devitrification stability. However, when incorporated
in excessive quantity, glass devitrification stability and
transmittance sharply deteriorate, the sag point and liquid-phase
temperature rise sharply, and the glass tends to develop color
during precision press molding. Thus, the quantity is desirably set
to 0 to 5 weight percent (excluding 5 weight percent), preferably 0
to 4 weight percent (excluding 4 weight percent), more preferably 0
to 1 weight percent (excluding 1 weight percent), and still more
preferably, none at all.
[0372] The weight ratio (TiO.sub.2 content/Bi.sub.2O.sub.3 content)
is desirably less than 0.5, preferably 0 to 0.45. When
Nb.sub.2O.sub.5 is incorporated, the weight ratio (TiO.sub.2
quantity/Nb.sub.2O.sub.5 quantity) is desirably less than 0.1,
preferably 0 to 0.09. When Nb.sub.2O.sub.5 is not incorporated,
TiO.sub.2 is desirably not incorporated.
[0373] MgO and SrO are optional components incorporated to adjust
the weatherability and stability of the glass. When incorporated in
excessive quantity, the glass becomes extremely unstable. Thus, the
content is desirably set to 0 to 10 molar percent each, preferably
0 to 8 molar percent each.
[0374] Sb.sub.2O.sub.3 is effective as a glass clarifying agent.
However, when added in excessive quantity, the glass tends to foam
during precision press molding. Thus, the quantity added is set to
0 to 1 weight percent of the combined quantity of all glass
components. The desirable range of addition is 0 to 0.9 weight
percent.
[0375] For the same reasons as for Preforms 1 to 4, Preforms 5 to 7
contain neither Ag.sub.2O, Tl.sub.2O, nor PbO, and the
incorporation of As.sub.2O.sub.3, CdO, and the like is to be
avoided. Further, to directly form preforms out of glass melt, the
incorporation of volatile components is undesirable. Accordingly,
the incorporation of fluorine is undesirable. Since TeO.sub.2 is
toxic and GeO.sub.2 is expensive, these compounds are desirably not
incorporated as starting materials.
[0376] In the glass used to mold Preforms 5 to 7, the desirable
ranges of the various components given above can be combined as
desired to achieve desirable composition ranges. Of these, the
following are examples of desirable composition ranges.
Examples of desirable composition ranges of Preforms 5 to 7
[0377] In Preforms 5 to 7, desirable examples are:
(1) glass compositions where more than 0 weight percent of
Nb.sub.2O.sub.5 is incorporated, the weight ratio (TiO.sub.2
quantity/Bi.sub.2O.sub.3 quantity) is less than 0.5, and the weight
ratio (TiO.sub.2 quantity/Nb.sub.2O.sub.5 quantity) is less than
0.1; (2) glass compositions where 0 to 5 weight percent (excluding
5 weight percent) of TiO.sub.2 and 0 to 30 weight percent
(excluding 30 weight percent) of Nb.sub.2O.sub.5 are incorporated;
(3) compositions where the glass components are: [0378]
P.sub.2O.sub.5: 17 to 67 molar percent, [0379] Bi.sub.2O.sub.3: 0.2
to 6 molar percent, [0380] Na.sub.2O: 1 to 20 molar percent, [0381]
K.sub.2O: 0.1 to 10 molar percent, where the combined quantity of
Li.sub.2O, Na.sub.2O, and K.sub.2O is 12 to 38 molar percent,
[0382] ZnO: 2 to 20 molar percent, [0383] CaO: 0 to 5 molar
percent, [0384] BaO: 20 to 50 molar percent (excluding 20 molar
percent), [0385] Nb.sub.2O.sub.5: 0 to 10 molar percent (0 to 10
weight percent), [0386] WO.sub.3: 0 to 7 molar percent, [0387]
SiO.sub.2: 0 to 4 weight percent, [0388] B.sub.2O.sub.3: 0 to 5
molar percent, [0389] TiO.sub.2: 0 to 5 weight percent (excluding 5
molar percent), where the weight ratio of (TiO.sub.2
content/Bi.sub.2O.sub.3 content) is less 0 to 0.45 and
Sb.sub.2O.sub.3 is added in a quantity of 0 to 0.9 weight percent
of the combined content of all glass components; (4) compositions
where the glass components are: [0390] P.sub.2O.sub.5: 17 to 67
molar percent, [0391] Bi.sub.2O.sub.3: 0.2 to 6 molar percent,
[0392] Na.sub.2O: 1 to 20 molar percent, [0393] K.sub.2O: 0.1 to 10
molar percent, where the combined quantity of Li.sub.2O, Na.sub.2O,
and K.sub.2O is 12 to 38 molar percent, [0394] ZnO: 2 to 20 molar
percent, [0395] CaO: 0 to 5 molar percent, [0396] BaO: 20 to 40
molar percent (excluding 20 molar percent), [0397] Nb.sub.2O.sub.5:
0 to 10 molar percent (0 to 10 weight percent), [0398] WO.sub.3: 0
to 7 molar percent, [0399] SiO.sub.2: 0 to 2 weight percent, [0400]
B.sub.2O.sub.3: 0 to 5 molar percent, [0401] TiO.sub.2: 0 to 4
weight percent (excluding 4 weight percent), where the weight ratio
of (TiO.sub.2 content/Bi.sub.2O.sub.3 content) is less 0 to 0.45
and Sb.sub.2O.sub.3 is added in a quantity of 0 to 0.9 weight
percent of the combined content of all glass components; (5) glass
compositions where 0 to 1 weight percent (excluding 1 weight
percent) of TiO.sub.2 is incorporated; (6) glass compositions where
no TiO.sub.2 is incorporated; (7) glass compositions where 0 to 2
weight percent (excluding 2 weight percent) of SiO.sub.2 is
incorporated; (8) glass compositions where no SiO.sub.2 is
incorporated; (9) glass compositions where Nb.sub.2O.sub.5 is
incorporated and the weight ratio of (TiO.sub.2
quantity/Nb.sub.2O.sub.5 quantity) is 0 to 0.09; (10) glass
compositions where the combined contents of P.sub.2O.sub.5,
Bi.sub.2O.sub.3, Li.sub.2O, Na.sub.2O, K.sub.2O, ZnO, CaO, BaO,
Nb.sub.2O.sub.5, WO.sub.3, B.sub.2O.sub.3, Gd.sub.2O.sub.3, and
Y.sub.2O.sub.3 exceed 95 molar percent and Sb.sub.2O.sub.3 is added
in a quantity of 0 to 0.09 weight percent of the combined contents
of all the glass components; (11) glass compositions where the
combined contents of P.sub.2O.sub.5, Bi.sub.2O.sub.3, Li.sub.2O,
Na.sub.2O, K.sub.2O, ZnO, CaO, BaO, Nb.sub.2O.sub.5, WO.sub.3,
B.sub.2O.sub.3, Gd.sub.2O.sub.3, and Y.sub.2O.sub.3 exceed 98 molar
percent and Sb.sub.2O.sub.3 is added in a quantity of 0 to 0.09
weight percent of the combined contents of all the glass
components; (12) glass compositions where the combined contents of
P.sub.2O.sub.5, Bi.sub.2O.sub.3, Li.sub.2O, Na.sub.2O, K.sub.2O,
ZnO, CaO, BaO, Nb.sub.2O.sub.5, WO.sub.3, B.sub.2O.sub.3,
Gd.sub.2O.sub.3, and Y.sub.2O.sub.3 exceed 99 molar percent and
Sb.sub.2O.sub.3 is added in a quantity of 0 to 0.09 weight percent
of the combined contents of all the glass components; and (13)
glass compositions where the combined contents of P.sub.2O.sub.5,
Bi.sub.2O.sub.3, Li.sub.2O, Na.sub.2O, K.sub.2O, ZnO, CaO, BaO,
Nb.sub.2O.sub.5, WO.sub.3, B.sub.2O.sub.3, Gd.sub.2O.sub.3, and
Y.sub.2O.sub.3 comprise 100 molar percent and Sb.sub.2O.sub.3 is
added in a quantity of 0 to 0.09 weight percent of the combined
contents of all the glass components;
[0402] In Preforms 5 to 7, a refractive index (nd) of 1.45 to 2.0
and an Abbe number (.nu.d) exceeding 32 and less than 95 are
desirable to achieve high glass stability, a low glass transition
temperature, and little coloration. The glass composition can be
adjusted within the ranges specified in the claims to obtain glass
preforms that have a refractive index (nd) of 1.45 to 2.0 and Abbe
number (.nu.d) falling within the above-stated ranges and achieve
glass stability, a low glass transition temperature, and low
coloration.
[0403] To lower the temperature of the pressing mold in precision
press molding, the glass transition temperature (Tg) is desirably
kept to less than or equal to 600.degree. C., preferably less than
or equal to 550.degree. C., and more preferably less than or equal
to 500.degree. C. The sag point (Ts) is desirably kept to less than
or equal to 650.degree. C., preferably less than or equal to
600.degree. C., and more preferably to less than or equal to
550.degree. C.
[0404] The ranges of greatest preference are a glass transition
temperature (Tg) of less than or equal to 360.degree. C. and a sag
point (Ts) of less than or equal to 400.degree. C.
[0405] To mold high-quality preforms from glass melt, the
liquid-phase temperature of the glass is desirably less than
1,000.degree. C., preferably less than 900.degree. C., more
preferably less than 850.degree. C., and still more preferably less
than 800.degree. C. Glasses having glass compositions falling
within the ranges specified in the claims basically have a
liquid-phase temperature (LT) falling within the above-stated
range. The glass composition can be adjusted within the ranges
specified in the claims to obtain glass preforms having a
liquid-phase temperature (LT) falling within the above range.
[0406] In Preforms 5 to 7, the desirable specific gravity range is
from 2.9 to 3.8. The haze value is desirably less than or equal to
10 percent, preferably less than or equal to 8.5 percent, and more
preferably less than or equal to 3 percent. The mass loss rate (Dw)
when immersed in pure water (100.degree. C.) is desirably less than
0.3 weight percent, preferably less than or equal to 0.25 weight
percent. The average coefficient of linear expansion (.alpha.) is
desirably 140 to 200.times.10.sup.-7/.degree. C.
[0407] Glasses having glass compositions falling within the ranges
specified in the claims basically have a specific gravity, haze
value, mass loss rate (Dw) when immersed in pure water, and average
coefficient of linear expansion (.alpha.) falling within the
above-stated ranges. The glass composition can be adjusted within
the ranges specified in the claims to obtain glass preforms having
a specific gravity, haze value, mass loss rate (Dw) when immersed
in pure water, and average coefficient of linear expansion
(.alpha.) falling within the above-stated ranges.
[0408] The method of measuring the various physical properties are
described in the embodiments.
[0409] The eighth preform (referred to hereinbelow as "Preform 8")
is characterized by being comprised of optical glass containing
essential components in the form of 15 to 70 molar percent of
P.sub.2O.sub.5 and Bi.sub.2O.sub.3 as well as a quantity of
TiO.sub.2 of less than 0.5 times the content of Bi.sub.2O.sub.3 by
weight, and 0 to 5 weight percent (excluding 5 weight percent) of
SiO.sub.2, and characterized in that glass, the entire surface of
which is molten, is solidified and molded.
[0410] Preform 8 can be divided into Preforms 8-1 to 8-4.
[0411] Preform 8-1 is Preform 8 in which the optical glass has an
Abbe number (.nu.d) of less than or equal to 32 and comprises more
than 4 weight percent and less than or equal to 30 molar percent,
desirably greater than or equal to 4.5 weight percent and less than
or equal to 30 molar percent, and preferably greater than or equal
to 5 weight percent and less than or equal to 30 molar percent of
Bi.sub.2O.sub.3.
[0412] Preform 8-2 is Preform 8 with an Abbe number (.nu.d) of less
than or equal to 32 containing B.sub.2O.sub.3 as an essential
component.
[0413] Preform 8-3 is Preform 8 with an Abbe number (.nu.d) of less
than or equal to 32 containing WO.sub.3 in a quantity of 0 to 15
weight percent (excluding 15 weight percent), desirably less than
or equal to 14.5 weight percent, and preferably less than or equal
to 14 weight percent.
[0414] Preform 8-4 is Preform 8 with an Abbe number (.nu.d)
exceeding 32, preferably greater than or equal to 32.1.
[0415] The ninth preform (referred to as "Preform 9" hereinafter)
is characterized by being comprised of optical glass containing 15
to 70 molar percent of P.sub.2O.sub.5 and Bi.sub.2O.sub.3 as
essential components, less than 0.5 times the content of
Bi.sub.2O.sub.3 by weight of TiO.sub.2, and from 0 to 5 weight
percent (excluding 5 weight percent) of SiO.sub.2, with the entire
surface being a free surface.
[0416] Preform 9 can be divided into Preforms 9-1 to 9-4.
[0417] Preform 9-1 is Preform 9 with an Abbe number (.nu.d) of less
than or equal to 32 comprising Bi.sub.2O.sub.3 in a quantity of
greater than 4 weight percent and less than or equal to 30 molar
percent, desirably greater than or equal to 4.5 weight percent and
less than or equal to 30 molar percent, and preferably greater than
or equal to 5 molar percent and less than or equal to 30 molar
percent.
[0418] Preform 9-2 is Preform 9 with an Abbe number (.nu.d) of less
than or equal to 32 containing B.sub.2O.sub.3 as an essential
component.
[0419] Preform 9-3 is Preform 9 with an Abbe number (.nu.d) of less
than or equal to 32 comprising WO.sub.3 in a quantity of 0 to 15
weight percent (excluding 15 weight percent), desirably less than
or equal to 14.5 weight percent, and preferably less than or equal
to 14 weight percent.
[0420] Preform 9-4 is Preform 9 with an Abbe number (.nu.d)
exceeding 32, preferably greater than or equal to 32.5.
[0421] Preforms consisting of any combination of limits falling
within the composition ranges of any of the forms of Preforms 1-1
to 1-4, 2-1 to 2-4, 3-1 to 3-4, 4-1 to 4-4, 8-1 to 8-3, and 9-1 to
9-3 are also possible in the present invention.
[0422] Preforms consisting of any combination of limits falling
within the composition ranges of any of the forms of Preforms 5-1
to 5-4, 6-1 to 6-4, 7-1 to 7-4, 8-4, and 9-4 are also possible in
the present invention.
[0423] In Preforms 8 and 9, P.sub.2O.sub.5 is a constituent
component of the network structure of the glass that is essential
to imparting stability permitting manufacturing to the glass. From
the perspectives of lowering the glass transition temperature and
sag point, enhancing weatherability, and increasing devitrification
stability, the content of P.sub.2O.sub.5 is set to 15 to 70 molar
percent, preferably 17 to 67 molar percent. [0424] Bi.sub.2O.sub.3
is an essential component that greatly broadens the glass
production range, has a stabilizing effect, and increases the
weatherability of the glass. It is also a component that increases
the weatherability of the glass. Bi.sub.2O.sub.3 increases the
wetting angle of platinum and platinum alloys by the glass in a
molten state, and enhances the suppression of wetting when forming
preforms for precision pressing by the drip method or drop-cut
method, described further below, where a glass melt is caused to
flow out of a platinum or gold-containing platinum alloy pipe.
Thus, it plays important roles in increasing the weight precision
of the preform and suppressing surface striae. TiO.sub.2 is an
optional component improving the dispersion of the glass and
enhancing devitrification stability. Setting the glass composition
so that content of Bi.sub.2O.sub.3 and TiO.sub.2 relative to
P.sub.2O.sub.5 yields a weight ratio (TiO.sub.2
content/Bi.sub.2O.sub.3 content) of less than 0.5 permits the
providing of a preform suited to precision press molding the
surface of which is formed by solidifying glass the entire surface
of which is in a molten state or the entire surface of which is a
free surface, free of devitrification, striae, and the like. That
is, to obtain a structure in the form of a surface formed by
solidification of glass the entire surface of which is in a molten
state or a structure where the entire surface is a free surface, a
glass melt gob equivalent to one preform must be separated from a
glass melt and molded into a preform while within a temperature
range permitting plastic deformation. It is also necessary to apply
wind pressure to the glass melt gob (including both glass melt gobs
and glass gobs in the form of glass melt gobs being cooled) and
mold the glass gob as it is being floated. Bi.sub.2O.sub.3 and
TiO.sub.2 increase the refractive index. Between Bi.sub.2O.sub.3
and TiO.sub.2, Bi.sub.2O.sub.3 has the better glass stabilizing
effect, better wetting preventive effect, and better striae
reducing effect. Thus, since a prescribed relation of the weight
ratio (TiO.sub.2 content/Bi.sub.2O.sub.3 content) exists in the
above preform, these effects can be achieved while obtaining
prescribed optical characteristics, and a higher quality preform
can be provided. The weight ratio (TiO.sub.2
content/Bi.sub.2O.sub.3 content) is desirably 0 to 0.09. In
Preforms 8-1 and 9-2, the above-stated quantity of Bi.sub.2O.sub.3
is incorporated. The phrase "a surface formed by solidifying glass
the entire surface of which is in a molten state" refers to the
surface of a glass gob, that is, preform, that has been formed
without mechanically processing following cooling and
solidification of the glass gob while in a molten state.
[0425] SiO.sub.2 is an optional component. When introduced in
excessive quantity, the glass transition temperature and sag point
rise. Thus, the content is set to 0 to 5 weight percent (excluding
5 weight percent), desirably 0 to 4 weight percent, preferably 0 to
2 weight percent, and more preferably, none at all.
[0426] In Preforms 8-2 and 9-2, B.sub.2O.sub.3 is incorporated as
an essential component for the same reasons as in Preforms 1-2,
2-2, 3-2, and 4-2. In Preforms 8-3 and 9-3, WO.sub.3 is
incorporated in a prescribed quantity for the same reasons as in
Preforms 1-3, 2-3, 3-3, and 4-3.
[0427] The limits of the composition ranges of forms 8-1 to 8-3 of
Preform 8 above may be combined as desired to obtain the preform of
the present invention. Similarly, the limits of the composition
ranges of forms 9-1 to 9-3 of Preform 9 above may be combined as
desired to obtain the preform of the present invention.
[0428] Further, in Preforms 8 and 9, the optical glass desirably
contains 3 to 15 weight percent (excluding 3 weight percent) of
Li.sub.2O. The reason for this and the quantity incorporated are
identical to those in Preforms 1 to 4.
[0429] In Preforms 8 and 9, the optical glass desirably contains
BaO as an optional component. In particular, when the Abbe number
(.nu.d) is less than or equal to 32, the quantity of BaO is
desirably 0 to 15 molar percent, and when the Abbe number (.nu.d)
exceeds 32, the quantity of BaO is desirably 0 to 50 molar
percent.
[0430] For the same reasons as in Preforms 1 to 7, Ag.sub.2O,
Tl.sub.2O, and PbO are excluded from the glass. As.sub.2O.sub.3, F,
CdO, TeO.sub.2, and GeO.sub.2 are also desirably not incorporated
for the same reasons as in Preforms 1 to 7.
[0431] Preforms 8 and 9 desirably comprise glass to which
Sb.sub.2O.sub.3 is added in a quantity of from 0 to 1 weight
percent (excluding 1 weight percent), preferably 0 to 0.9 weight
percent, of the combined quantity of all glass components. In this
glass, the glass transition temperature (Tg) is also desirably less
than or equal to 600.degree. C. and the sag point (Ts) desirably
less than or equal to 650.degree. C. The liquid-phase temperature
(LT) is also desirably less than or equal to 1,000.degree. C.
[0432] Preforms for precision press molding desirably have free
surfaces formed by solidification of glass the entire surface of
which is in a molten state.
[0433] Specifically, in Preforms 1 to 7it is desirable for the
surface of the preform to be a surface formed by solidifying glass
the entire surface of which is in a molten state, for the entire
surface of the preform to be a free surface, or for the surface of
the preform to be a free surface formed by solidifying glass the
entire surface of which is in a molten state. In Preform 8, it is
desirable for the entire surface to be a free surface.
[0434] The phrase "a surface formed by solidifying glass the entire
surface of which is in a molten state" allows for spots where a
metal mold surface is transferred by contact with a metal mold for
molding, while the phrase "entire surface . . . to be a free
surface" excludes the presence of spots where a metal mold surface
has been transferred by contact with a metal mold for molding.
[0435] Imparting such a surface to the preform prevents even minute
polishing scratches, yielding a smooth, clean surface and
permitting the manufacturing of better optical elements by
precision press molding of preforms.
[0436] The method of manufacturing preforms for precision press
molding will be described next.
[0437] As starting materials for optical glass, H.sub.3PO.sub.4,
metaphosphate, diphosphorus pentachloride, and the like may be
employed for P.sub.2O.sub.5; H.sub.3BO.sub.3, B.sub.2O.sub.3, and
the like may be employed for B.sub.2O.sub.3; and carbonates,
nitrates, and oxides may be suitably employed for the other
components. These starting materials are weighed out in prescribed
proportions and mixed to obtain a blended starting material. This
is then heated to 1,000 to 1,250.degree. C. and placed in a melting
furnace, melted, clarified, stirred, and homogenized to obtain an
optical glass melt free of bubbles.
[0438] The glass melt thus prepared is made to flow out of a flow
pipe, a prescribed weight of glass melt is separated from the glass
melt flowing out of the flow pipe, and one of Preforms 1 to 9 with
the same weight as above is molded before solidifying the glass
melt gob. That is, while the glass melt gob is still soft and
moldable and is not in contact with any solid, it is molded into a
desired shape.
[0439] The glass melt is caused to flow out of the melt pipe at a
temperature equivalent to a viscosity of 3 to 60 dPas. Here, the
term "flow out" refers both to the case where a glass melt flow
flows out of the flow pipe and the case where the glass melt drips
out of the flow pipe. The temperature of the flow pipe is adjusted,
for example, by controlling the temperature of the flow pipe. The
flow pipe is desirably made of platinum or a platinum alloy.
Specific molding methods include causing glass melt to flow out of
the flow pipe as a glass melt drop of prescribed weight, receiving
the drop in a receiving member, and molding it into a preform; the
method of similarly causing a glass melt drop of prescribed weight
to drip out of the flow pipe into liquid nitrogen or the like, and
molding it into a preform (referred to as "drip methods"); causing
a glass melt flow to drip from a flow pipe of platinum or a
platinum alloy, receiving the front end of the glass melt flow on a
receiving member, forming a constriction in the glass melt flow
between the flow pipe and the receiving member, and then separating
the glass melt flow at the constriction to receive a gob of glass
melt of prescribed weight in the receiving member, and molding this
into a preform (referred to as the "drop-cut" method). When
dripping a glass melt, the viscosity of the glass is desirably 3 to
30 dPas. When causing the glass melt to flow as a glass melt flow,
the viscosity of the glass is desirably 2 to 60 dPas.
[0440] Any of Preforms 1 to 7 having a smooth surface without
scratches, contamination, or surface anomalies, or having a surface
formed by solidification of glass the entire surface of which is in
a molten state, and any of Preforms 1 to 7 the entire surface of
which is a free surface, may be produced by molding a glass melt
gob while floating it by wind pressure on a pressing mold, or by
introducing a glass melt drop into a medium in the form of a liquid
obtained by cooling a gas substance at ordinary temperature and
pressure, such as liquid nitrogen, and molding it into a
preform.
[0441] Examples of preform shapes are the preform shapes given
above.
[0442] A carbon-containing film or the like may be provided on the
surface of the preform of the present invention. This film is
desirably provided over the entire surface of the preform. This
film facilitates separation of the precision press-molded article
from the mold and facilitates good extension of the glass at the
surface contacting the pressing mold during precision press
molding. Examples of carbon-containing films are carbon films
formed by vapor deposition, hydrogenated carbon films formed by
chemical vapor deposition, and the like.
[0443] The optical element of the present invention will be
described next. The optical element of the present invention is
obtained by precision press molding any of Preforms 1 to 9 or a
preform manufactured by one of the above-described manufacturing
methods. The optical element obtained has the various optical
characteristics of the preform. The optical element is made of
glass. As needed, an antireflective film, reflective film,
partially reflective film reflecting certain wavelengths of light,
film absorbing certain wavelengths of light, or the like can be
provided on the surface. Specific examples of the optical element
are spherical lenses, aspherical lenses, microlenses, lens arrays,
lenses with diffraction gratings, various other lenses, diffraction
gratings, prisms, prisms with lenses, and polygonal mirrors. These
optical elements are precision press-molded articles molded from
the above-described preforms. Thus, the optically functional
surfaces thereof are free of microscratches and the like produced
by processing such as grinding and polishing. Since they are
comprised of glass not containing PbO, they are extremely good
optical elements from the perspectives of the environment and
cost.
[0444] The method of manufacturing optical elements of the present
invention will be described next. In the method of manufacturing
optical elements of the present invention, any of the Preforms of 1
to 9 or a preform manufactured by one of the above-described
methods is heated and then precision press molded in a pressing
mold to manufacturing an optical element.
[0445] In precision press molding, a pressing mold with a molding
surface that has been processed with high precision into a desired
shape in advance is employed. To prevent adhesion of the glass
during pressing, a mold separation film may be formed on the
molding surface. To prevent damage due to oxidization of the
molding surface of the pressing mold, precision press molding may
be conducted in a non-oxidizing gas atmosphere, such as nitrogen,
employing known methods.
[0446] Examples of the method of manufacturing optical elements of
the present invention are the method of introducing a preform for
precision press molding into a pressing mold, heating both the
pressing mold and the preform, and conducting precision press
molding; and the method of introducing a preform for precision
press molding that has been preheated to a temperature greater than
that of the pressing mold into the pressing mold and conducting
precision press molding.
[0447] The precision press molding conditions can be suitably set
based on known ranges of the shape and size of precision
press-molded articles.
[0448] It is thus possible to manufacture optical articles such as
spherical lenses, aspherical lenses, microlenses, lens arrays,
lenses with diffraction gratings, various other lenses, diffraction
gratings, prisms, prisms with lenses, and polygonal mirrors with
optically functional surfaces that are not mechanically
processed.
EMBODIMENTS
[0449] The present invention is further described below through
embodiments.
[0450] The embodiments and Preforms 1 to 9 are related as
follows.
[0451] Embodiments 1 to 9: Preforms 3, 4, 8, 9
[0452] Embodiments 10 to 12: Preforms 1-4, 8, 9
[0453] Embodiments 13 to 17: Preforms 3, 4, 8, 9
[0454] Embodiments 18 to 21, 26, 28: Preforms 5 to 9
[0455] Embodiments 22 to 25, 27: Preforms 6 to 9
[0456] Embodiment 29: Preform 6, 8, 9
Embodiments 1 to 29
[0457] Table 1 gives the composition, refractive index (nd), Abbe
number (.nu.d), glass transition temperature (Tg), sag point (Ts),
and liquid-phase temperature (LT) of the glasses used to make the
preforms of Embodiments 1 to 17. Table 2 gives the composition,
refractive index (nd), Abbe number (.nu.d), glass transition
temperature (Tg), sag point (Ts), and liquid-phase temperature (LT)
of the glasses used to make the preforms of Embodiments 18 to 39.
In these glasses, corresponding oxides, hydroxides, carbonates, and
nitrates were employed as starting materials for the various
components. They were weighed out and blended so as to yield the
proportions of the composition given in Table 1 following
vitrification, thoroughly mixed, placed in a platinum crucible,
melted at a temperature range of from 1,050 to 1,200.degree. C. in
an electric furnace, clarified, and homogenized by stirring to
obtain a glass melt. This glass melt was cast into a preheated
metal mold, cooled to the glass transition temperature, immediately
annealed, and gradually cooled to room temperature.
[0458] The various characteristics of the optical glasses obtained
were measured. The refractive index (nd), Abbe number (.nu.d),
liquid-phase temperature (LT), glass transition temperature (Tg),
sag point (Ts), .lamda.80, .lamda.5, specific gravity, and average
modulus of linear expansion (.alpha.) were measured in Embodiments
1 to 17 as follows. The refractive index (nd), Abbe number (.nu.d),
liquid-phase temperature (LT), glass transition temperature (Tg),
sag point (Ts), specific gravity, haze value, mass loss rate (Dw)
when immersed in pure water, and average modulus of linear
expansion (.alpha.) were measured in Embodiments 18 to 29 as
follows.
(1) The refractive index (nd) and Abbe number (.nu.d):
[0459] Measured for optical glasses obtained at a gradual
temperature reduction rate of -30.degree. C./hour.
(2) The liquid-phase temperature (LT)
[0460] The sample was placed for 1 hour in a devitrification test
furnace with a temperature gradient of from 400 to 1,150.degree.
C., the presence of crystals was checked with a microscope at
80-fold magnification, and the liquid-phase temperature was
measured.
(3) Glass transition temperature (Tg) and sag point (Ts)
[0461] Measured at a heating rate of 4.degree. C./min with a
thermomechanical analyzer made by Rigaku Denki K. K.
(4).lamda.80, .lamda.5
[0462] The spectral transmittance was measured at wavelengths of
280 to 700 nm for a sample 10.0.+-.0.1 mm in thickness and the
values were calculated.
(4) Specific gravity
[0463] Measured by Archimedes' method.
(5) Haze value
[0464] Measured based on the standard, "Method of measuring the
chemical durability of optical glass (surface method) 07" of the
Japan Optical Glass Industrial Association.
(6) Mass loss rate (Dw) when immersed in pure water
[0465] Measured based on the standard, "Method of measuring the
chemical durability of optical glass (surface method) 06" of the
Japan Optical Glass Industrial Association.
(7) Average coefficient of linear expansion (.alpha.)
[0466] The average coefficient of linear expansion was measured at
100 to 300.degree. C.
TABLE-US-00001 TABLE 1 Embodiment P.sub.2O.sub.5 TiO.sub.2
Bi.sub.2O.sub.3 TiO.sub.2/Bi.sub.2O.sub.3 B.sub.2O.sub.3
Nb.sub.2O.sub.5 TiO.sub.2/Nb.sub.2O.sub.5 1 Molar % 24.00 5.00 2.00
2.50 4.00 19.00 0.26 wt % 24.31 2.85 6.65 0.43 1.99 36.04 0.08 2
Molar % 23.00 5.00 6.00 0.83 4.00 19.00 0.26 wt % 21.28 2.60 18.23
0.14 1.82 32.93 0.08 3 Molar % 23.00 5.00 4.00 1.25 4.00 19.00 0.26
wt % 22.47 2.75 12.83 0.21 1.92 34.76 0.08 4 Molar % 23.00 5.00
5.00 1.00 4.00 18.00 0.28 wt % 22.77 2.79 16.25 0.17 1.94 33.37
0.08 5 Molar % 24.00 5.00 6.00 0.83 4.00 18.00 0.28 wt % 22.90 2.69
18.80 0.14 1.87 32.17 0.08 6 Molar % 24.00 6.00 4.00 1.50 4.00
18.00 0.33 wt % 24.28 3.42 13.28 0.26 1.98 34.09 0.10 7 Molar %
24.00 5.00 4.00 1.25 4.00 19.00 0.26 wt % 23.96 2.81 13.11 0.21
1.96 35.52 0.08 8 Molar % 26.00 5.00 4.00 1.25 4.00 19.00 0.26 wt %
25.86 2.80 13.06 0.21 1.95 35.40 0.08 9 Molar % 27.00 5.00 4.00
1.25 4.00 19.00 0.26 wt % 26.75 2.79 13.01 0.21 1.94 35.25 0.08 10
Molar % 24.00 6.00 8.00 0.75 4.00 19.00 0.32 wt % 21.23 2.99 23.23
0.13 1.74 31.47 0.10 11 Molar % 24.00 5.00 8.00 0.63 4.00 20.00
0.25 wt % 21.22 2.49 23.22 0.11 1.73 33.12 0.08 12 Molar % 24.00
6.00 9.00 0.67 4.00 18.00 0.33 wt % 21.20 2.98 26.10 0.11 1.73
29.78 0.10 13 Molar % 25.00 5.00 4.00 1.25 4.00 19.00 0.26 wt %
24.77 2.79 13.01 0.21 1.94 35.25 0.08 14 Molar % 24.00 5.00 3.00
1.67 6.00 18.00 0.28 wt % 25.00 2.93 10.26 0.29 3.07 35.11 0.08 15
Molar % 25.00 5.00 3.00 1.67 5.00 18.00 0.28 wt % 25.90 2.92 10.20
0.29 2.54 34.93 0.08 16 Molar % 24.00 5.50 4.00 1.38 6.00 19.00
0.29 wt % 24.13 3.11 13.20 0.24 2.96 35.78 0.09 17 Molar % 25.00
5.50 4.00 1.38 4.00 19.00 0.29 wt % 25.03 3.10 13.15 0.24 1.96
35.63 0.09 Embodiment WO.sub.3 ZnO Li.sub.2O Na.sub.2O K.sub.2O
R.sub.2O(*) Na.sub.2O + K.sub.2O 1 Molar % 8.00 2.00 20.00 11.00
2.00 33.00 13.00 wt % 13.24 1.16 4.26 4.87 1.34 10.47 6.21 2 Molar
% 8.00 2.00 18.00 13.00 2.00 33.00 15.00 wt % 12.09 1.06 3.51 5.25
1.23 9.99 6.48 3 Molar % 8.00 2.00 18.00 15.00 2.00 35.00 17.00 wt
% 12.77 1.12 3.70 6.40 1.30 11.40 7.70 4 Molar % 5.00 2.00 18.00
18.00 0.00 36.00 18.00 wt % 8.08 1.14 3.75 7.78 0.00 11.53 7.78 5
Molar % 6.00 2.00 18.00 15.00 2.00 35.00 17.00 wt % 9.35 1.09 3.62
6.25 1.27 11.14 7.52 6 Molar % 5.00 2.00 20.00 13.00 2.00 35.00
15.00 wt % 8.26 1.16 4.26 5.74 1.34 11.34 7.08 7 Molar % 5.00 2.00
20.00 13.00 2.00 35.00 15.00 wt % 8.15 1.14 4.20 5.67 1.32 11.19
6.99 8 Molar % 5.00 1.00 20.00 13.00 2.00 35.00 15.00 wt % 8.12
0.57 4.19 5.65 1.32 11.16 6.97 9 Molar % 5.00 0.00 20.00 13.00 2.00
35.00 15.00 wt % 8.09 0.00 4.17 5.62 1.31 11.10 6.93 10 Molar %
6.00 0.00 18.00 11.00 2.00 31.00 13.00 wt % 8.67 0.00 3.35 4.25
1.17 8.77 5.42 11 Molar % 6.00 0.00 18.00 13.00 2.00 33.00 15.00 wt
% 8.67 0.00 3.35 5.02 1.17 9.54 6.19 12 Molar % 6.00 0.00 18.00
13.00 2.00 33.00 15.00 wt % 8.66 0.00 3.35 5.02 1.17 9.54 6.19 13
Molar % 6.00 1.00 21.00 12.00 2.00 35.00 14.00 wt % 9.71 0.57 4.38
5.19 1.32 10.89 6.51 14 Molar % 5.00 2.00 20.00 13.00 2.00 35.00
15.00 wt % 8.51 1.19 4.39 5.91 1.38 11.68 7.29 15 Molar % 5.00 2.00
20.00 13.00 2.00 35.00 15.00 wt % 8.46 1.19 4.36 5.88 1.38 11.62
7.26 16 Molar % 5.00 1.00 20.50 12.00 2.00 34.50 14.00 wt % 8.21
0.58 4.34 5.27 1.33 10.94 6.60 17 Molar % 5.00 1.50 21.00 12.00
2.00 35.00 14.00 wt % 8.18 0.86 4.43 5.25 1.33 11.01 6.58
Embodiment BaO CaO SiO.sub.2 Sum 1 Molar % 3.00 0.00 0.00 100.00 wt
% 3.28 0.00 0.00 100.00 2 Molar % 0.00 0.00 0.00 100.00 wt % 0.00
0.00 0.00 100.00 3 Molar % 0.00 0.00 0.00 100.00 wt % 0.00 0.00
0.00 100.00 4 Molar % 2.00 0.00 0.00 100.00 wt % 2.14 0.00 0.00
100.00 5 Molar % 0.00 0.00 0.00 100.00 wt % 0.00 0.00 0.00 100.00 6
Molar % 2.00 0.00 0.00 100.00 wt % 2.19 0.00 0.00 100.00 7 Molar %
2.00 0.00 0.00 100.00 wt % 2.16 0.00 0.00 100.00 8 Molar % 1.00
0.00 0.00 100.00 wt % 1.07 0.00 0.00 100.00 9 Molar % 1.00 0.00
0.00 100.00 wt % 1.07 0.00 0.00 100.00 10 Molar % 2.00 0.00 0.00
100.00 wt % 1.91 0.00 0.00 100.00 11 Molar % 0.00 0.00 0.00 100.00
wt % 0.00 0.00 0.00 100.00 12 Molar % 0.00 0.00 0.00 100.00 wt %
0.00 0.00 0.00 100.00 13 Molar % 1.00 0.00 0.00 100.00 wt % 1.07
0.00 0.00 100.00 14 Molar % 2.00 0.00 0.00 100.00 wt % 2.25 0.00
0.00 100.00 15 Molar % 2.00 0.00 0.00 100.00 wt % 2.24 0.00 0.00
100.00 16 Molar % 1.00 0.00 0.00 100.00 wt % 1.09 0.00 0.00 100.00
17 Molar % 1.00 0.00 0.00 100.00 wt % 1.08 0.00 0.00 100.00 LT Tg
Ts .lamda.80 .lamda.5 Embodiment nd .nu.d (.degree. C.) (.degree.
C.) (.degree. C.) (nm) (nm) 1 1.84541 23.15 920.gtoreq. 466 519 506
378 2 1.88863 21.73 920.gtoreq. 448 497 543 386 3 1.86137 22.37
920.gtoreq. 453 504 515 381 4 1.85136 21.86 920.gtoreq. 443 492 517
381 5 1.86026 22.61 920.gtoreq. 442 493 525 382 6 1.84594 23.2
910.gtoreq. 445 500 497 378 7 1.84979 23.1 900.gtoreq. 452 504 500
378 8 1.83979 23.3 900.gtoreq. 456 508 508 376 9 1.83435 23.46
900.gtoreq. 466 516 514 376 10 1.90015 21.51 900.gtoreq. 461 510
563 388 11 1.89836 21.41 900.gtoreq. 455 507 567 388 12 1.89648
21.48 900.gtoreq. 454 505 564 390 13 1.84980 22.95 890.gtoreq. 457
506 511 379 14 1.82732 23.92 880.gtoreq. 450 503 499 376 15 1.82485
24.02 870.gtoreq. 453 506 494 375 16 1.84976 22.96 890.gtoreq. 455
507 512 379 17 1.85316 22.94 890.gtoreq. 456 508 521 379 Embodiment
Specific Gravity .alpha. (.times.10.sup.-7/.degree. C.) 1 3.803
113.0 2 4.086 115.0 3 3.913 119.0 4 3.938 127.0 5 3.981 123.0 6
3.835 125.0 7 3.851 118.5 8 3.783 121.0 9 3.757 119.0 10 4.194
124.0 11 4.152 129.0 12 4.208 127.0 13 3.83 117.2 14 3.727 119.0 15
3.721 119.0 16 3.803 112.0 17 3.808 116.0 (*)R.sub.2O: Combined
amount of Li.sub.2O, Na.sub.2O, and K.sub.2O
TABLE-US-00002 TABLE 2 Embodiment P.sub.2O.sub.5 Bi.sub.2O.sub.3
Li.sub.2O Na.sub.2O K.sub.2O R.sub.2O(*) ZnO 18 Molar % 36.01 0.70
10.48 11.49 4.38 26.35 13.97 wt % 44.2 2.8 2.7 6.2 3.6 12.5 9.8 19
Molar % 33.48 0.72 14.36 12.57 4.50 31.43 10.77 wt % 41.2 2.9 3.7
6.8 3.7 14.2 7.6 20 Molar % 36.03 0.70 11.87 13.58 4.38 29.83 10.48
wt % 43.6 2.8 3.0 7.2 3.5 13.7 7.3 21 Molar % 33.48 0.72 14.36
12.57 4.5 31.43 10.77 wt % 41.2 2.9 3.7 6.8 3.7 14.2 7.6 22 Molar %
36.00 0.70 10.40 10.40 4.00 24.80 14.00 wt % 44.3 2.8 2.7 5.6 3.3
11.6 9.9 23 Molar % 36.00 0.70 15.00 5.80 4.00 24.80 14.00 wt %
44.9 2.9 3.9 3.2 3.3 10.4 10.0 24 Molar % 36.00 0.70 14.40 10.40
0.00 24.80 14.00 wt % 45.3 2.9 3.8 5.7 0.0 9.5 10.1 25 Molar %
36.00 0.70 12.40 10.40 4.00 26.80 12.00 wt % 44.7 2.9 3.2 5.7 3.3
12.2 8.5 26 Molar % 36.00 0.35 10.40 10.40 4.00 24.80 14.00 wt %
44.5 1.4 2.7 5.6 3.3 11.6 9.9 27 Molar % 36.00 0.70 10.40 10.40
4.00 24.80 12.00 wt % 44.5 2.9 2.7 5.6 3.3 11.6 8.5 28 Molar %
34.50 1.20 13.80 13.00 4.50 31.30 9.50 wt % 41.3 4.7 3.5 6.8 3.6
13.9 6.5 29 Molar % 38.71 1.46 16.64 9.53 3.63 29.8 11.58 wt % 48.3
6.0 4.4 5.2 3.0 12.6 8.3 Nb.sub.2O.sub.5 + Embodiment CaO BaO
Nb.sub.2O.sub.5 WO.sub.3 WO.sub.3 SiO.sub.2 B.sub.2O.sub.3 18 Molar
% 0.00 20.17 1.40 0.00 1.40 0.00 1.40 wt % 0.0 26.7 3.2 0.0 3.2 0.0
0.8 19 Molar % 0.00 20.73 2.87 0.00 2.87 0.00 0.00 wt % 0.0 27.5
6.6 0.0 6.6 0.0 0.0 20 Molar % 0.00 20.17 2.79 0.00 2.79 0.00 0.00
wt % 0.0 26.3 6.3 0.0 6.3 0.0 0.0 21 Molar % 0.00 20.73 2.87 0.00
2.87 0.00 0.00 wt % 0.0 27.5 6.6 0.0 6.6 0.0 0.0 22 Molar % 0.00
23.00 0.00 0.00 0.00 0.00 1.50 wt % 0.0 30.5 0.0 0.0 0.0 0.0 0.9 23
Molar % 0.00 23.00 0.00 0.00 0.00 0.00 1.50 wt % 0.0 30.9 0.0 0.0
0.0 0.0 0.9 24 Molar % 0.00 23.00 0.00 0.00 0.00 0.00 1.50 wt % 0.0
31.2 0.0 0.0 0.0 0.0 1.0 25 Molar % 0.00 23.00 0.00 0.00 0.00 0.00
1.50 wt % 0.0 30.8 0.0 0.0 0.0 0.0 0.9 26 Molar % 0.00 22.65 0.35
0.35 0.70 0.00 1.50 wt % 0.0 30.2 0.8 0.7 1.5 0.0 0.9 27 Molar %
2.00 23.00 0.00 0.00 0.00 0.00 1.50 wt % 1.0 30.6 0.0 0.0 0.0 0.0
0.9 28 Molar % 0.00 20.00 3.50 0.00 3.50 0.00 0.00 wt % 0.0 25.8
7.8 0.0 7.8 0.0 0.0 29 Molar % 0.00 18.45 0.00 0.00 0.00 0.00 0.00
wt % 0.0 24.8 0.0 0.0 0.0 0.0 0.0 TiO.sub.2/ Embodiment
Gd.sub.2O.sub.3 Y.sub.2O.sub.3 TiO.sub.2 TiO.sub.2/Bi.sub.2O.sub.3
Nb.sub.2O.sub.5 Sum 18 Molar % 0.00 0.00 0.00 0.00 0.00 100.00 wt %
0.0 0.0 0.0 0.0 0.0 100.0 19 Molar % 0.00 0.00 0.00 0.00 0.00
100.00 wt % 0.0 0.0 0.0 0.0 0.0 100.0 20 Molar % 0.00 0.00 0.00
0.00 0.00 100.00 wt % 0.0 0.0 0.0 0.0 0.0 100.0 21 Molar % 0.00
0.00 0.00 0.00 0.00 100.00 wt % 0.0 0.0 0.0 0.0 0.0 100.0 22 Molar
% 0.00 0.00 0.00 0.00 0.00 100.00 wt % 0.0 0.0 0.0 0.0 0.0 100.0 23
Molar % 0.00 0.00 0.00 0.00 0.00 100.00 wt % 0.0 0.0 0.0 0.0 0.0
100.0 24 Molar % 0.00 0.00 0.00 0.00 0.00 100.00 wt % 0.0 0.0 0.0
0.0 0.0 100.0 25 Molar % 0.00 0.00 0.00 0.00 0.00 100.00 wt % 0.0
0.0 0.0 0.0 0.0 100.0 26 Molar % 0.00 0.00 0.00 0.00 0.00 100.00 wt
% 0.0 0.0 0.0 0.0 0.0 100.0 27 Molar % 0.00 0.00 0.00 0.00 0.00
100.00 wt % 0.0 0.0 0.0 0.0 0.0 100.0 28 Molar % 0.00 0.00 0.00
0.00 0.00 100.00 wt % 0.0 0.0 0.0 0.0 0.0 100.0 29 Molar % 0.00
0.00 0.00 0.00 0.00 100.00 wt % 0.0 0.0 0.0 0.0 0.0 100.0 Ts
Specific Embodiment nd .nu.d LT (.degree. C.) Tg (.degree. C.)
(.degree. C.) Gravity 18 1.59059 55.5 770 331 359 3.395 19 1.60551
50.79 750 332 371 3.435 20 1.59768 51.92 700 329 364 3.385 21
1.60551 50.79 700 332 371 3.435 22 1.58397 59.28 750 330 367 3.445
23 1.58899 59.37 750 335 370 3.443 24 1.59167 59.34 770 334 365
3.478 25 1.5819 59.43 750 322 359 3.414 26 1.58373 59.44 750 331
367 3.418 27 1.58366 59.67 750 328 371 3.431 28 1.61292 48.56 700
331 375 3.448 29 1.55796 63.54 750 293 331 3.14 Embodiment Haze
value (%) Dw (wt %) .alpha. (.times.10.sup.-7/.degree. C.) 18 4.6
0.023 182.1 19 0.3 0.03 184.0 20 2.7 0.03 182.0 21 0.3 0.03 184.0
22 5.2 0.029 179.0 23 9.5 0.033 167.0 24 2.9 0.03 166.7 25 8.1
0.036 169.0 26 5.9 0.023 173.0 27 3.3 0.035 181.0 28 0.3 0.027
164.0 29 1.2 0.011 175.0 (*)R.sub.2O: Combined amount of Li.sub.2O,
Na.sub.2O, and K.sub.2O
[0467] To confirm the effect of introducing Bi.sub.2O.sub.3, glass
melts were prepared having the glass composition of Embodiment 25
and the same composition without Bi.sub.2O.sub.3. FIG. 1 shows
these glasses after they had been cast into preheated metal molds,
cooled to the glass transition temperature, immediately annealed,
and gradually cooled to room temperature. A transparent glass was
obtained from the glass composition of Embodiment 25, but the
composition without Bi.sub.2O.sub.3 crystallized, completely losing
transparency.
[0468] The above-described glass melts were made to flow
continuously at a constant flow rate from a flow nozzle made of
platinum alloy. A glass melt gob of prescribed weight was separated
from the glass melt flow by the drop-cut method, molded into a
sphere while being supported by wind pressure with nitrogen gas on
a forming mold, and annealed to manufacture a spherical
preform.
[0469] Next, the glass melt was continuously dripped from a flow
nozzle made of platinum alloy and the glass drops were molded into
spheres while being supported by wind pressure with nitrogen gas on
a forming mold and annealed to manufacture spherical preforms.
[0470] In this manner, spherical preforms ranging from 2 to 30 mm
in diameter were molded. Spherical shapes are not the only shapes
into which preforms can be molded: various shapes having a single
rotational axis of symmetry can be molded. The weight precision of
the preforms obtained was kept to within 1 percent. In the above
preforms, the entire surface of the preform was formed by
solidification of glass in a molten state, and the entire surface
was a free surface.
[0471] No bubbles, striae, devitrification, or damaged spots were
found in any of the preforms; they had smooth, unscratched
surfaces.
[0472] To evaluate the degree of wetting of the outer circumference
of the tip of the platinum or platinum alloy flow nozzle, a flat
sheet of platinum alloy comprised of 95 atomic percent Pt and 5
atomic percent Au was prepared and employed in wetting angle
evaluation. The planar dimensions of the platinum alloy plate were
10.times.10 mm. The surface was mirror polished. The Rz of the
surface was 50 to 1,000 nm. Glass of the composition of Embodiment
45 and glass of the same composition without Bi.sub.2O.sub.3 were
formed into cubes 4 mm.sup.3, positioned in the center of plates
positioned horizontally, heated to a temperature 20.degree. C.
higher than the liquid-phase temperature, and maintained for 30
min. The glass samples were remelted in this manner a second time,
annealed, maintained for 1 hour at a temperature below the glass
transition temperature, and then cooled at a rate of -30.degree.
C./hour to room temperature. As shown in FIG. 2, the wetting angles
of the glass of Embodiment 29 and the glass of that composition
without the Bi.sub.2O.sub.3 were measured.
[0473] In Embodiment 29, the wetting angle was 29.degree., while in
the composition without Bi.sub.2O.sub.3, the wetting angle was
17.degree.. Although the wetting angle of glass containing
P.sub.2O.sub.5 was low, the incorporation of Bi.sub.2O.sub.3
increased the wetting angle for platinum alloys. Thus, it was
possible to reduce wetting by the glass melt of the outer
circumference of the tip of the flow pipe in the course of causing
glass melt to flow out of a flow pipe made of platinum or a
platinum alloy, and prevent the generation of striae in the preform
and a decrease in weight precision.
Embodiment 30
[0474] Aspherical lenses were obtained by precision press molding
the preforms for precision press molding obtained in Embodiments 1
to 29 in the precision pressing mold shown in FIG. 3.
[0475] The precision press molding was conducted in the following
manner. First, a preform from the above embodiments was placed
between a lower mold 2 and an upper mold 1. The interior of a
quartz tube 11 was filled with a nitrogen atmosphere and a heater
12 was operated to heat the interior of quartz tube 11. The
temperature within the pressing mold was set 20 to 60.degree. C.
higher than the sag point of the glass. Maintaining this
temperature, a pressing rod 13 was lowered, pressing against upper
mold 1 and pressing the preform within the pressing mold. The
pressing mold employed here was made of SiC with a carbon mold
separation film formed on the molding surface to which the glass
sometimes adheres. The pressing pressure was 8 MPa applied for 30
seconds. The pressure was then released, the precision press-molded
glass was gradually cooled to a temperature 30.degree. C. lower
than the glass transition temperature while still in contact with
lower mold 2 and upper mold 1, the glass was rapidly cooled to room
temperature and removed from the pressing mold, and an aspherical
lens was removed. The aspherical lens obtained was of extremely
high precision.
[0476] A preform that had been preheated to a temperature 20 to
60.degree. C. higher than the sag point of the glass constituting
the preform was introduced into a pressing mold that had been
preheated to a temperature lower than that to which the preform had
been preheated and precision press molded to obtain an aspherical
lens.
[0477] The use of the preform of any of Embodiments 1 to 29
comprised of glass with a low glass transition temperature
permitted the use of a stainless steel pressing mold with a mold
separation film in the form of a nickel film provided on the
molding surface as needed.
[0478] In the above-described embodiments, a description is given
for the example of aspherical lenses. However, various optical
elements such as spherical lenses, microlenses, lens arrays, lenses
with diffraction gratings, various other lenses, diffraction
gratings, prisms, prisms with lenses, and polygonal mirrors can be
manufactured without mechanical processing optically functional
surfaces.
[0479] The present disclosure relates to the subject matter
contained in Japanese Patent Application No. 2003-188455 filed on
Jun. 30, 2003 and Japanese Patent Application No. 2003-306126 filed
on Aug. 29, 2003, which is expressly incorporated herein by
reference in its entirety.
* * * * *