U.S. patent application number 13/841268 was filed with the patent office on 2013-08-15 for glass for chemical tempering, chemically tempered glass, and glass plate for display device.
This patent application is currently assigned to ASAHI GLASS COMPANY, LIMITED. The applicant listed for this patent is ASAHI GLASS COMPANY, LIMITED. Invention is credited to Shusaku Akiba, Jun Endo, Tetsuya Nakashima, Kazutaka Ono.
Application Number | 20130209773 13/841268 |
Document ID | / |
Family ID | 45892926 |
Filed Date | 2013-08-15 |
United States Patent
Application |
20130209773 |
Kind Code |
A1 |
Endo; Jun ; et al. |
August 15, 2013 |
GLASS FOR CHEMICAL TEMPERING, CHEMICALLY TEMPERED GLASS, AND GLASS
PLATE FOR DISPLAY DEVICE
Abstract
To provide glass to be used for chemically tempered glass, of
which the strength is less likely to be reduced even when
indentations are formed thereon. Glass for chemical tempering,
which comprises, as represented by mole percentage based on oxides,
from 62 to 68% of SiO.sub.2, from 6 to 12% of Al.sub.2O.sub.3, from
7 to 13% of MgO, from 9 to 17% of Na.sub.2O, and from 0 to 7% of
K.sub.2O, wherein the difference obtained by subtracting the
content of Al.sub.2O.sub.3 from the total content of Na.sub.2O and
K.sub.2O is less than 10%, and when ZrO.sub.2 is contained, its
content is at most 0.8%. Chemically tempered glass obtained by
chemically tempering such glass for chemical tempering. Such
chemically tempered glass has a compressive stress layer formed on
the glass surface, which has a thickness of at least 30 .mu.m and a
surface compressive stress of at least 550 MPa.
Inventors: |
Endo; Jun; (Chiyoda-ku,
JP) ; Akiba; Shusaku; (Chiyoda-ku, JP) ; Ono;
Kazutaka; (Chiyoda-ku, JP) ; Nakashima; Tetsuya;
(Chiyoda-ku, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ASAHI GLASS COMPANY, LIMITED; |
|
|
US |
|
|
Assignee: |
ASAHI GLASS COMPANY,
LIMITED
Chiyoda-ku
JP
|
Family ID: |
45892926 |
Appl. No.: |
13/841268 |
Filed: |
March 15, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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PCT/JP2011/071901 |
Sep 26, 2011 |
|
|
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13841268 |
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Current U.S.
Class: |
428/220 ;
428/332; 501/69; 501/70 |
Current CPC
Class: |
Y10T 428/26 20150115;
C03C 3/087 20130101; Y10T 428/315 20150115; G02F 2001/133302
20130101; C03C 3/085 20130101; C03C 21/002 20130101; C03C 21/001
20130101; C03C 3/091 20130101; C03C 3/085 20130101; C03C 21/002
20130101; C03C 21/00 20130101 |
Class at
Publication: |
428/220 ; 501/69;
501/70; 428/332 |
International
Class: |
C03C 3/085 20060101
C03C003/085; C03C 21/00 20060101 C03C021/00; C03C 3/087 20060101
C03C003/087 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 27, 2010 |
JP |
2010-215982 |
Dec 24, 2010 |
JP |
2010-288255 |
Claims
1. Glass for chemical tempering, which comprises, as represented by
mole percentage based on oxides, from 62 to 68% of SiO.sub.2, from
6 to 12% of Al.sub.2O.sub.3, from 7 to 13% of MgO, from 9 to 17% of
Na.sub.2O, and from 0 to 7% of K.sub.2O, wherein the difference
obtained by subtracting the content of Al.sub.2O.sub.3 from the
total content of Na.sub.2O and K.sub.2O is less than 10%, and when
ZrO.sub.2 is contained, its content is at most 0.8%.
2. The glass for chemical tempering according to claim 1, which
contains from 64 to 67% of SiO.sub.2, and from 6 to 7.5% of
Al.sub.2O.sub.3, wherein the total content of SiO.sub.2 and
Al.sub.2O.sub.3 is from 69 to 73%.
3. Glass for chemical tempering, which comprises, as represented by
mole percentage based on oxides, from 62 to 66% of SiO.sub.2, from
6 to 12% of Al.sub.2O.sub.3, from 7 to 13% of MgO, from 9 to 17% of
Na.sub.2O, and from 0 to 7% of K.sub.2O, wherein the difference
obtained by subtracting the content of Al.sub.2O.sub.3 from the
total content of Na.sub.2O and K.sub.2O is less than 10%, and when
ZrO.sub.2 is contained, its content is at most 0.8%.
4. The glass for chemical tempering according to claim 3, wherein
the total content of SiO.sub.2 and Al.sub.2O.sub.3 is more than
72%.
5. The glass for chemical tempering according to claim 1, wherein
the total content of Na.sub.2O and K.sub.2O is from 14 to 22%.
6. Glass for chemical tempering, which comprises, as represented by
mole percentage based on oxides, from 64 to 68% of SiO.sub.2, from
6 to 11% of Al.sub.2O.sub.3, from 7 to 12% of MgO, from 12 to 17%
of Na.sub.2O, and from 0 to 6% of K.sub.2O, wherein the difference
obtained by subtracting the content of Al.sub.2O.sub.3 from the
total content of Na.sub.2O and K.sub.2O is less than 10%, and when
ZrO.sub.2 is contained, its content is at most 0.8%.
7. The glass for chemical tempering according to claim 6, which
contains from 65 to 68% of SiO.sub.2, from 7 to 10% of
Al.sub.2O.sub.3, and from 0 to 2.5% of K.sub.2O, wherein the total
content of SiO.sub.2 and Al.sub.2O.sub.3 is from 73.5 to 76%.
8. The glass for chemical tempering according to claim 6, wherein
the content of SiO.sub.2 is at most 66%.
9. The glass for chemical tempering according to claim 6, wherein
the total content of Na.sub.2O and MgO is from 21 to 25%.
10. The glass for chemical tempering according to claim 6, wherein
the total content of Na.sub.2O and K.sub.2O is at most 18%.
11. The glass for chemical tempering according to claim 1, wherein
the total content of Na.sub.2O, K.sub.2O and MgO is from 24 to
28%.
12. The glass for chemical tempering according to claim 6, wherein
R calculated by the following formula by using the contents of the
respective components of SiO.sub.2, Al.sub.2O.sub.3, MgO, CaO,
ZrO.sub.2, Na.sub.2O and K.sub.2O is at least 0.66:
R=0.029.times.SiO.sub.2+0.021.times.Al.sub.2O.sub.3+0.016.times.MgO-0.004-
.times.CaO+0.016.times.ZrO.sub.2+0.029.times.Na.sub.2O+0.times.K.sub.2O-2.-
002
13. The glass for chemical tempering according to claim 1, wherein
the content of K.sub.2O is at least 0.5%.
14. The glass for chemical tempering according to claim 1, wherein
the total content of SiO.sub.2, Al.sub.2O.sub.3, MgO, Na.sub.2O and
K.sub.2O is at least 98%.
15. The glass for chemical tempering according to claim 1, which
has a glass transition point of at least 600.degree. C.
16. The glass for chemical tempering according to claim 1, which
has a temperature of at most 1650.degree. C. at which the viscosity
becomes to be 10.sup.2 dPas.
17. The glass for chemical tempering according to claim 1, which is
to be used for obtaining glass, of which a compressive stress layer
formed on the glass surface by chemical tempering has a thickness t
of at least 30 .mu.m and a surface compressive stress S of at least
550 MPa.
18. The glass for chemical tempering according to claim 17, wherein
F1/F0 can be made to be at least 0.9, where F0 is a flexural
strength of a chemically tempered glass plate which is obtained by
chemically tempering a glass plate made of the glass for chemical
tempering and having a thickness of 1 mm and a size of 5
mm.times.40 mm and which has t of at least 30 .mu.m and S of at
least 550 MPa, and F1 is a flexural strength of such a chemically
tempered glass plate having a Vickers indenter impressed thereinto
with a force of 9.8N.
19. The glass for chemical tempering according to claim 17, wherein
F2/F0 can be made to be at least 0.7, where F0 is a flexural
strength of a chemically tempered glass plate which is obtained by
chemically tempering a glass plate made of the glass for chemical
tempering and having a thickness of 1 mm and a size of 5
mm.times.40 mm and which has t of at least 30 .mu.m and S of at
least 550 MPa, and F2 is a flexural strength of such a chemically
tempered glass plate having a Vickers indenter impressed thereinto
with a force of 19.6N.
20. The glass for chemical tempering according to claim 18, wherein
the t is from 45 to 55 .mu.m and the S is from 750 to 850 MPa.
21. Chemically tempered glass, which is obtained by chemically
tempering the glass for chemical tempering as defined in claim
1.
22. The chemically tempered glass according to claim 21, of which a
compressive stress layer formed on the glass surface has a
thickness t of at least 30 .mu.m, and a surface compressive stress
S of at least 550 MPa.
23. A chemically tempered glass plate which is a glass plate made
of the chemically tempered glass as defined in claim 22 and having
a thickness of from 0.4 to 1.2 mm, wherein F1/F0 is at least 0.9,
where F0 is its flexural strength and F1 is a flexural strength of
the glass plate having a Vickers indenter impressed thereinto with
a force of 9.8N.
24. A chemically tempered glass plate which is a glass plate made
of the chemically tempered glass as defined in claim 22 and having
a thickness of from 0.4 to 1.2 mm, wherein F2/F0 is at least 0.7,
where F0 is its flexural strength and F2 is a flexural strength of
the glass plate having a Vickers indenter impressed thereinto with
a force of 19.6N.
25. A glass plate for a display device, which is made of the
chemically tempered glass as defined in claim 21.
26. A glass plate for a display device, which is made of the
chemically tempered glass plate as defined in claim 23.
27. A display device, which has a cover glass comprising the glass
plate for a display device as defined in claim 25.
28. A mobile device, which has a cover glass comprising the glass
plate for a display device as defined in claim 25.
29. A touch panel, which has a cover glass comprising the glass
plate for a display device as defined in claim 25.
30. A flat screen television with a size of at least 20 inches,
which has a cover glass comprising the glass plate for a display
device as defined in claim 25.
Description
TECHNICAL FIELD
[0001] The present invention relates to a display device for e.g. a
mobile device such as a cell phone or a personal digital assistance
(PDA), a large-sized flat screen television such as a large-sized
liquid crystal television or a large-sized plasma television and a
touch panel, a glass plate for a display device suitable for e.g. a
cover glass for a display device, and chemically tempered glass or
glass for chemical tempering suitable for such a glass plate for a
display device.
BACKGROUND ART
[0002] In recent years, for display devices such as mobile devices,
liquid crystal televisions, touch panels, etc., a cover glass
(protective glass) has been used in many cases to protect a display
and to improve appearance.
[0003] For such display devices, weight reduction and thickness
reduction are required for differentiation by a flat design or for
reduction of the load for transportation. Therefore, a cover glass
to be used for protecting a display is also required to be made
thin. However, if the thickness of the cover glass is made to be
thin, the strength is lowered, and there has been a problem such
that the cover glass itself is broken by e.g. a shock due to a
falling or flying object in the case of an installed type or by
dropping during the use in the case of a portable device, and the
cover glass cannot perform the essential role to protect the
display device.
[0004] In order to solve the above problem, it is conceivable to
improve the strength of the cover glass, and as such a method, a
method to form a compressive stress layer on a glass surface is
commonly known.
[0005] The method to form a compressive stress layer on a glass
surface, may typically be an air quenching tempering method
(physical tempering method) wherein a surface of a glass plate
heated to near the softening point is quenched by air cooling or
the like, or a chemical tempering method wherein alkali metal ions
having a small ion radius (typically Li ions or Na ions) at a glass
plate surface are exchanged with alkali ions having a larger ion
radius (typically K ions) by ion exchange at a temperature lower
than the glass transition point.
[0006] As mentioned above, the thickness of the cover glass is
required to be thin. However, if the air quenching tempering method
is applied to a thin glass plate having a thickness of less than 2
mm, as required for a cover glass, the temperature difference
between the surface and the inside tends not to arise, and it is
thereby difficult to form a compressive stress layer, and the
desired property of high strength cannot be obtained. Therefore, a
cover glass tempered by the latter chemical tempering method is
usually used.
[0007] As such a cover glass, one having soda lime glass chemically
tempered is widely used (e.g. Patent Document 1).
[0008] Soda lime glass is inexpensive and has a feature that the
surface compressive stress S of a compressive stress layer formed
at the surface of the glass by the chemical tempering can be made
to be at least 550 MPa, but there has been a problem that it has
been difficult to make the thickness t of the compressive stress
layer to be at least 30 .mu.m.
[0009] Therefore, one having SiO.sub.2--Al.sub.2O.sub.3--Na.sub.2O
type glass different from soda lime glass, chemically tempered, has
been proposed for such a cover glass (e.g. Patent Document 2).
[0010] Such SiO.sub.2--Al.sub.2O.sub.3--Na.sub.2O type glass has a
feature that it is possible not only to make the above S to be at
least 550 MPa but also to make the above t to be at least 30
.mu.m.
PRIOR ART DOCUMENTS
Patent Documents
[0011] Patent Document 1: JP-A-2007-11210
[0012] Patent Document 2: US Patent Application Publication No.
2009/0298669
DISCLOSURE OF INVENTION
Technical Problem
[0013] It is highly possible that a mobile device is dropped from
the user's hand, pocket or bag and its cover glass gets flaws
(indentations), or the dropped mobile device may be stepped on or
the user may sit on the mobile device put in the pocket, and a
heavy load may thereby be applied to the cover glass in many
cases.
[0014] A flat screen television such as a liquid crystal television
or a plasma television, particularly a large-sized flat screen
television having a size of at least 20 inches, is likely to have
flaws since its cover glass has a large size, and as the screen is
large, the probability of breakage from the flaws as the breakage
origin is high. Further, when a flat screen television is used as
hung on the wall, it may fall down, and in such a case, a large
load may be applied to the cover glass.
[0015] A touch panel is likely to have flaws such as scratches at
the time of its use.
[0016] As such large or small display devices are used more widely
now, the number of incidences of breakage of the cover glass itself
is increased as compared with the past when the number of use was
small or limited.
[0017] Whereas, with a cover glass having glass chemically tempered
as disclosed in Patent Document 2, the strength is likely to be
lowered, once an indentation is imparted to the cover glass during
its use, and there has been a problem such that the cover glass is
likely to be broken if a load such as a shock or static load is
imparted thereto. In the present invention, "get flaws" and "get
indentations" are used in the same meaning and include a case where
cracking is not yet observed.
[0018] It is an object of the present invention to provide
chemically tempered glass, of which the strength is less likely to
be lowered, as compared with the conventional one, even if
indentations are formed thereon, and glass to be used therefor.
Solution to Problem
[0019] The present invention provides glass for chemical tempering,
which comprises, as represented by mole percentage based on oxides,
from 62 to 68% of SiO.sub.2, from 6 to 12% of Al.sub.2O.sub.3, from
7 to 13% of MgO, from 9 to 17% of Na.sub.2O, and from 0 to 7% of
K.sub.2O, wherein the difference (R.sub.2O-Al.sub.2O.sub.3)
obtained by subtracting the content of Al.sub.2O.sub.3 from the
total content of R.sub.2O i.e. Na.sub.2O and K.sub.2O, is less than
10%, and when ZrO.sub.2 is contained, its content is at most 0.8%.
Here, for example "from 62 to 68%" means at least 62% and at most
68%.
[0020] The present invention further provides the above glass for
chemical tempering, which contains from 64 to 67% of SiO.sub.2, and
from 6 to 7.5% of Al.sub.2O.sub.3, wherein the total content of
SiO.sub.2 and Al.sub.2O.sub.3 is from 69 to 73%.
[0021] The present invention further provides glass for chemical
tempering, which comprises, as represented by mole percentage based
on oxides, from 62 to 66% of SiO.sub.2, from 6 to 12% of
Al.sub.2O.sub.3, from 7 to 13% of MgO, from 9 to 17% of Na.sub.2O,
and from 0 to 7% of K.sub.2O, wherein (R.sub.2O-Al.sub.2O.sub.3) is
less than 10%, and when ZrO.sub.2 is contained, its content is at
most 0.8% (hereinafter this glass for chemical tempering will
sometimes be referred to as glass A).
[0022] The present invention further provides glass for chemical
tempering, which comprises, as represented by mole percentage based
on oxides, from 64 to 68% of SiO.sub.2, from 6 to 11% of
Al.sub.2O.sub.3, from 7 to 12% of MgO, from 12 to 17% of Na.sub.2O,
and from 0 to 6% of K.sub.2O, wherein (R.sub.2O-Al.sub.2O.sub.3) is
less than 10%, and when ZrO.sub.2 is contained, its content is at
most 0.8% (hereinafter this glass for chemical tempering will
sometimes be referred to as glass B).
[0023] The present invention further provides the above glass for
chemical tempering, which contains from 65 to 68% of SiO.sub.2,
from 7 to 10% of Al.sub.2O.sub.3, and from 0 to 2.5% of K.sub.2O,
wherein the total content of SiO.sub.2 and Al.sub.2O.sub.3 is from
73.5 to 76%.
[0024] The present invention further provides the above glass for
chemical tempering, wherein the content of SiO.sub.2 is at most
66%.
[0025] The present invention further provides the above glass for
chemical tempering, which is to be used for obtaining glass, of
which a compressive stress layer formed on the glass surface by
chemical tempering has a thickness t of at least 30 .mu.m and a
surface compressive stress S of at least 550 MPa.
[0026] The present invention further provides the above glass for
chemical tempering, wherein F1/F0 can be made to be at least 0.9,
where F0 is a flexural strength of a chemically tempered glass
plate which is obtained by chemically tempering a glass plate made
of the glass for chemical tempering and having a thickness of 1 mm
and a size of 5 mm.times.40 mm and which has t of at least 30 .mu.m
and S of at least 550 MPa, and F1 is a flexural strength of such a
chemically tempered glass plate having a Vickers indenter impressed
thereinto with a force of 9.8N. Here, typically the above t is from
45 to 55 .mu.m and the above S is from 750 to 850 MPa.
[0027] The present invention further provides the above glass for
chemical tempering, wherein F2/F0 can be made to be at least 0.7,
where F0 is a flexural strength of a chemically tempered glass
plate which is obtained by chemically tempering a glass plate made
of the glass for chemical tempering and having a thickness of 1 mm
and a size of 5 mm.times.40 mm and which has t of at least 30 .mu.m
and S of at least 550 MPa, and F2 is a flexural strength of such a
chemically tempered glass plate having a Vickers indenter impressed
thereinto with a force of 19.6N. Here, typically the above t is
from 45 to 55 .mu.m and the above S is from 750 to 850 MPa.
[0028] The present invention further provides chemically tempered
glass, which is obtained by chemically tempering the above glass
for chemical tempering.
[0029] The present invention further provides a chemically tempered
glass plate which is a glass plate made of the above chemically
tempered glass and having a thickness of from 0.4 to 1.2 mm,
wherein F1/F0 is at least 0.9, where F0 is its flexural strength
and F1 is a flexural strength of the glass plate having a Vickers
indenter impressed thereinto with a force of 9.8N.
[0030] The present invention further provides a chemically tempered
glass plate which is a glass plate made of the above chemically
tempered glass and having a thickness of from 0.4 to 1.2 mm,
wherein F2/F0 is at least 0.7, where F0 is its flexural strength
and F2 is a flexural strength of the glass plate having a Vickers
indenter impressed thereinto with a force of 19.6N.
[0031] The present invention further provides a glass plate for a
display device, which is made of the above chemically tempered
glass or the above chemically tempered glass plate.
[0032] The present invention further provides a display device,
which has a cover glass comprising the above glass plate for a
display device.
[0033] The present invention further provides the above display
device, which is a mobile device, a touch panel or a flat screen
television with a size of at least 20 inches.
[0034] The present inventors have found that SiO.sub.2 and
Al.sub.2O.sub.3 in glass prevent lowering of the strength which
takes place when an indentation is imparted to the glass even if
the glass is chemically tempered, while ZrO.sub.2 promotes lowering
of the strength and that if it is attempted to reduce ZrO.sub.2 in
order to prevent lowering of the strength, the glass transition
point Tg tends to decrease thus leading to such a problem that
stress relaxation is likely to occur. However, even in such a case,
it has been found possible to prevent lowering of Tg by adjusting
the above (R.sub.2O-Al.sub.2O.sub.3) to be less than 10%, whereby
the present invention has been accomplished.
Advantageous Effects of Invention
[0035] According to the present invention, the strength of glass is
less likely to be lowered even if indentations are imparted to
chemically tempered glass during its use, whereby it is possible to
obtain chemically tempered glass which is less likely to be broken
even if a load such as a shock or static load is imparted to the
glass, and glass for chemical tempering, which is suitable for such
chemically tempered glass.
[0036] Further, it is possible to obtain a display device for e.g.
a mobile device, a touch panel, a flat screen television, etc.,
wherein such chemically tempered glass is used as a glass plate for
the display device, such as a cover glass.
BRIEF DESCRIPTION OF DRAWING
[0037] FIG. 1 is a graph showing the relation between R obtained by
calculation from the glass composition and the decrease ratio r of
the surface compressive stress due to an increase of the Na
concentration in the molten potassium salt.
DESCRIPTION OF EMBODIMENTS
[0038] The chemically tempered glass, the chemically tempered glass
plate and the glass plate for a display device of the present
invention are each obtained by chemically tempering the glass for
chemical tempering of the present invention (hereinafter referred
to as the glass of the present invention), and hereinafter they
will generally be referred to as the tempered glass of the present
invention.
[0039] The above S of the tempered glass of the present invention
is preferably at least 550 MPa, more preferably more than 700 MPa.
Further, S is typically at most 1,200 MPa.
[0040] The above t of the tempered glass of the present invention
is preferably at least 30 .mu.m, more preferably exceeds 40 .mu.m.
Further, t is typically at most 70 .mu.m.
[0041] The method of chemical tempering treatment to obtain the
tempered glass of the present invention is not particularly limited
so long as Na.sub.2O in the glass surface layer can be ion
exchanged with K.sub.2O in the molten salt, and it may, for
example, be a method of immersing the glass in a heated potassium
nitrate (KNO.sub.3) molten salt. This KNO.sub.3 molten salt may be
one which contains e.g. NaNO.sub.3 in an amount of at most about
5%, in addition to KNO.sub.3.
[0042] Chemical tempering treatment conditions to form a chemically
tempered layer (compressive stress layer) having a desired surface
compressive stress on the glass may vary depending upon e.g. the
thickness in the case of a glass plate. However, it is typical to
immerse a glass substrate in a KNO.sub.3 molten salt at from 350 to
550.degree. C. for from 2 to 20 hours. From the economical
viewpoint, the immersion is carried out preferably under conditions
of from 350 to 500.degree. C. and from 2 to 16 hours, and more
preferably, the immersion time is from 2 to 10 hours.
[0043] A glass plate obtained by chemically tempering a glass plate
made of the glass of the present invention and having a thickness
of from 0.4 to 1.2 mm, is preferably one wherein F1/F0 is at least
0.9, where F0 is its flexural strength and F1 is a flexural
strength of the glass plate having a Vickers indenter impressed
thereinto with a force of 9.8N. If F1/F0 is not at least 0.9, the
glass tends to be readily broken when an indentation is formed on
the surface of the glass plate with a force of 9.8N. More
preferably, F1/F0 is at least 0.95.
[0044] A glass plate obtained by chemically tempering a glass plate
made of the glass of the present invention and having a thickness
of from 0.4 to 1.2 mm, is preferably one wherein F2/F0 is at least
0.7, where F0 is its flexural strength and F2 is a flexural
strength of the glass plate having a Vickers indenter impressed
thereinto with a force of 19.6N. If F2/F0 is not at least 0.7, the
glass tends to be readily broken when an indentation is formed on
the surface of the glass plate with a force of 19.6N. F2/F0 is more
preferably at least 0.8, particularly preferably at least 0.9.
[0045] A compressive stress layer of such a glass plate obtained by
chemically tempering a glass plate made of the glass of the present
invention and having a thickness of from 0.4 to 1.2 mm, preferably
has a thickness t of at least 30 .mu.m and a surface compressive
stress S of at least 550 MPa. Typically, t is from 40 to 60 .mu.m,
and S is from 650 to 820 MPa.
[0046] The glass plate for a display device of the present
invention is usually obtained by chemically tempering a glass plate
obtained by processing a glass plate made of the glass of the
present invention by e.g. cutting, hole making, polishing, etc.
[0047] The thickness of the glass plate for a display device of the
present invention is typically from 0.3 to 2 mm, usually from 0.4
to 1.2 mm.
[0048] The glass plate for a display device of the present
invention is typically a cover glass.
[0049] A method for producing a glass plate made of the above glass
of the present invention is not particularly limited, and for
example, various raw materials are mixed in proper amounts, heated
and melted at from about 1,400 to 1,700.degree. C. and then
homogenized by deforming, stirring or the like and formed into a
plate by a well-known float process, downdraw method or press
method, which is annealed and then cut into a desired size to
obtain the glass plate.
[0050] The glass transition point Tg of the glass of the present
invention is preferably at least 400.degree. C. If it is lower than
400.degree. C., the surface compressive stress is likely to be
relaxed during the ion exchange, and no adequate stress may be
obtained. It is typically at least 570.degree. C., preferably at
least 600.degree. C.
[0051] The temperature T2 at which the viscosity of the glass of
the present invention becomes 10.sup.2 dPas is preferably at most
1,650.degree. C. If T2 exceeds 1,650.degree. C., melting of the
glass tends to be difficult.
[0052] The temperature T4 at which the viscosity of the glass of
the present invention becomes 10.sup.4 dPas is preferably at most
1,250.degree. C. If T4 exceeds 1,250.degree. C., molding of the
glass tends to be difficult.
[0053] The specific gravity d of the glass of the present invention
is preferably at most 2.60, more preferably at most 2.55.
[0054] In a case where it is desired to lower T2 or T4 in order to
facilitate melting or molding of the glass, the glass of the
present invention is preferably glass A.
[0055] In a case where it is desired to make the strength less
likely to be lowered even when an indentation is formed, the glass
of the present invention is preferably glass B.
[0056] Now, the composition of the glass of the present invention
will be described by using contents represented by mole percentage
unless otherwise specified.
[0057] SiO.sub.2 is a component to constitute a glass matrix and is
essential. If the SiO.sub.2 content is less than 62%, lowering of
the strength tends to occur when an indentation is formed, cracking
tends to occur when scratch is formed, the weather resistance tends
to be low, the specific gravity tends to increase, or the glass
tends to be unstable when the liquid phase temperature is raised.
SiO.sub.2 is preferably at least 63%, and in glass B, it is at
least 64%, preferably at least 65%. If SiO.sub.2 exceeds 68%, T2 or
T4 tends to increase, whereby melting or molding of the glass tends
to be difficult. SiO.sub.2 is preferably at most 66%, more
preferably at most 65.5%, and in glass A, it is at most 66%. In
glass A, in a case where it is desired to more certainly prevent
lowering of the strength when an indentation is formed on the glass
surface, SiO.sub.2 is typically from 63 to 65%, and the SiO.sub.2
content as represented by mole percentage is typically less than
64%.
[0058] Al.sub.2O.sub.3 is a component to improve the ion exchange
performance and the weather resistance, and is essential. If it is
less than 6%, lowering of the strength tends to occur when an
indentation is formed, or it tends to be difficult to obtain the
desired surface compressive stress S or compressive stress layer
thickness t by ion exchange. Al.sub.2O.sub.3 is preferably at least
6.5%, more preferably at least 7%, particularly preferably at least
7.5%. If Al.sub.2O.sub.3 exceeds 12%, T2 or T4 tends to increase,
whereby melting or molding of the glass tends to be difficult, or
the liquid phase temperature tends to be high to cause
devitrification. It is preferably at most 11.5%, and in glass B, it
is preferably at most 10%.
[0059] The total content of SiO.sub.2 and Al.sub.2O.sub.3 is
preferably at least 71%. If the total content is less than 71%,
lowering of the strength tends to occur when an indentation is
formed, and it is typically more than 72%. In glass B, the total
content is typically from 73.5 to 76%.
[0060] MgO is a component which may decrease the ion exchange rate,
but it is a component to prevent cracking or to improve the melting
property, and thus is essential. If MgO is less than 7%, T2 or T4
tends to increase, whereby melting or molding of the glass tends to
be difficult, and it is preferably at least 7.5%, more preferably
at least 8%. If MgO exceeds 13%, the liquid phase temperature tends
to increase to cause devitrification, or lowering of the strength
tends to occur when an indentation is formed, and it is preferably
at most 12.5%, more preferably at most 12%. In glass B, it is at
most 12%. In a case where it is desired to more certainly prevent
lowering of the strength when an indentation is formed on the glass
surface, MgO is typically from 8 to 11%.
[0061] Na.sub.2O is a component to form a surface compressive
stress layer by ion exchange and to improve the melting property of
the glass, and is essential. If the Na.sub.2O content is less than
9%, it tends to be difficult to form a desired surface compressive
stress layer by ion exchange, and it is preferably at least 9.5%,
more preferably at least 10%, particularly preferably at least
10.5%. In glass B, it is at least 12%. If Na.sub.2O exceeds 17%,
the weather resistance tends to decrease, or cracking is likely to
be formed from an indentation. It is preferably at most 16%.
[0062] The total content of Na.sub.2O and MgO is preferably from 21
to 25%. If the total content is less than 21%, T2 or T4 tends to
increase, whereby melting or molding of the glass tends to be
difficult. If the total content exceeds 25%, cracking tends to be
formed from an indentation, or lowering of the strength tends to
occur when an indentation is formed.
[0063] K.sub.2O is not essential but is a component to increase the
ion exchange rate, and thus, it may be contained up to 7%. If
K.sub.2O exceeds 7%, lowering of the strength tends to occur when
an indentation is formed, or cracking tends to be formed from an
indentation, and it is preferably at most 6.5%, more preferably at
most 6%. In glass B, it is at most 6%, preferably at most 2.5%.
When K.sub.2O is contained, its content is preferably at least
0.5%.
[0064] When K.sub.2O is contained, the total content of R.sub.2O
i.e. Na.sub.2O and K.sub.2O is preferably at most 22%. If R.sub.2O
exceeds 22%, the weather resistance tends to be low, or cracking
tends to be formed from an indentation. It is preferably at most
21%, more preferably at most 20%, and in glass B, it is preferably
at most 18%. Further, R.sub.2O is preferably at least 14%,
typically at least 15%.
[0065] In the glass of the present invention, particularly glass B,
the total content of Na.sub.2O, K.sub.2O and MgO is preferably from
24 to 28%. If the total content is less than 24%, T2 or T4 tends to
increase, whereby melting or molding of the glass tends to be
difficult, and if it exceeds 28%, cracking tends to be formed from
an indentation, or lowering of the strength tends to occur when an
indentation is formed. It is typically at most 27%.
[0066] In a case where it is desired to certainly prevent lowering
of the strength when an indentation is formed on the glass surface,
typically Na.sub.2O is from 11 to 16% or from 12 to 16%, K.sub.2O
is from 0 to 5%, R.sub.2O is from 15 to 17%, and in a case where
the K.sub.2O content is less than 3%, Na.sub.2O is typically from
13.5 to 16%.
[0067] In a case where it is desired to increase Tg, the difference
(R.sub.2O-Al.sub.2O.sub.3) obtained by subtracting Al.sub.2O.sub.3
from R.sub.2O, is preferably less than 10%. If said difference is
at least 10%, Tg tends to be low, or stress relaxation tends to
occur during the chemical tempering.
[0068] ZrO.sub.2 is not essential, but may be contained within a
range of up to 0.8% in order to lower the viscosity at a high
temperature or to increase the surface compressive stress. If
ZrO.sub.2 exceeds 0.8%, lowering of the strength tends to occur, or
chipping is likely to occur. It is preferably at most 0.7%, more
preferably at most 0.6%, particularly preferably at most 0.55%, and
in glass B, it is preferably at most 0.5%.
[0069] The glass of the present invention is preferably one wherein
R calculated by the following formula by using the contents of the
respective components of SiO.sub.2, Al.sub.2O.sub.3, MgO, CaO,
ZrO.sub.2, Na.sub.2O and K.sub.2O is at least 0.66:
R=0.029.times.SiO.sub.2+0.021.times.Al.sub.2O.sub.3+0.016.times.MgO-0.00-
4.times.CaO+0.016.times.ZrO.sub.2+0.029.times.Na.sub.2O+0.times.K.sub.2O-2-
.002
[0070] In the following, the technical significance of R being at
least 0.66 will be described.
[0071] Usually, the ion exchange treatment for chemical tempering
is carried out by immersing glass containing sodium (Na) in a
molten potassium salt, and as the potassium salt, potassium nitrate
or a mixed salt of potassium nitrate and sodium nitrate is
used.
[0072] In such ion exchange treatment, ion exchange of Na in the
glass with potassium (K) in the molten salt is carried out.
Therefore, if the ion exchange treatment is repeated by using the
same molten salt, the Na concentration in the molten salt
increases.
[0073] If the Na concentration in the molten salt increases, the
surface compressive stress S of the chemically tempered glass
decreases, and therefore, there has been a problem that it is
necessary to strictly watch the Na concentration in the molten salt
and to frequently carry out replacement of the molten salt, so that
S of the chemically tempered glass will not become lower than the
desired value.
[0074] It is desired to reduce the frequency of such replacement of
the molten salt, and glass B wherein R is at least 0.66, is one of
embodiments of the present invention suitable to solve such a
problem.
[0075] The present inventors have considered that there may be a
relation between the composition of Na-containing glass and such a
phenomenon that by repeating ion exchange treatment of immersing
the Na-containing glass in a molten potassium salt many times to
obtain chemically tempered glass, the Na concentration in the
molten potassium salt increases and at the same time, the surface
compressive stress of the chemically tempered glass becomes small,
and have conducted the following experiment.
[0076] Firstly, 29 types of glass plates were prepared which had
compositions as represented by mole percentage in Tables 1 to 3 and
each of which had a thickness of 1.5 mm and a size of 20
mm.times.20 mm and had both sides mirror-polished with cerium
oxide. The glass transition points Tg (unit: .degree. C.) of these
glasses are shown in the same Tables. Here, those provided with *
are ones calculated from the compositions.
[0077] These 29 types of glass plates were subjected to ion
exchange of immersing for 10 hours in a molten potassium salt
having a KNO.sub.3 content of 100% and having a temperature of
400.degree. C. to obtain chemically tempered glass plates,
whereupon their surface compressive stresses CS1 (unit: MPa) were
measured. Here, glass A27 is glass used for a cover glass for a
mobile device.
[0078] Further, these 29 types of glass plates were subjected to
ion exchange of immersing for 10 hours in a molten potassium salt
having a KNO.sub.3 content of 95% and a NaNO.sub.3 content of 5%
and having a temperature of 400.degree. C. to obtain chemically
tempered glass plates, whereupon their surface compressive stresses
CS2 (unit: MPa) were measured.
[0079] CS1 and CS2 are shown together with their ratio r=CS2/CS1 in
the corresponding rows in Tables 1 to 3. r of conventional cover
glass A27 is 0.65.
TABLE-US-00001 TABLE 1 Glass .alpha.1 .alpha.2 A1 A2 A3 A4 A5 A6 A7
A8 SiO.sub.2 73.0 72.0 64.3 64.3 64.3 64.3 63.8 63.8 64.3 64.3
Al.sub.2O.sub.3 7.0 6.0 6.5 7.0 6.5 7.0 7.0 7.5 6.0 6.0 MgO 6.0
10.0 11.0 11.0 11.0 11.0 11.0 11.0 11.5 12.0 CaO 0 0 0.1 0.1 0.1
0.1 0.1 0.1 0.1 0.1 SrO 0 0 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 BaO 0 0
0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 ZrO.sub.2 0 0 2.0 1.5 1.5 1.0 1.5
1.0 2.0 1.5 Na.sub.2O 14.0 12.0 12.0 12.0 12.5 12.5 12.5 12.5 12.0
12.0 K.sub.2O 0 0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Tg 617 647 615
617 608 603 614 610 615 609 CS1 888 900 1049 1063 1035 1047 1063
1046 1020 1017 CS2 701 671 589 593 601 590 601 599 588 579 r 0.79
0.75 0.56 0.56 0.58 0.56 0.57 0.57 0.58 0.57 R 0.76 0.72 0.55 0.56
0.56 0.56 0.56 0.56 0.55 0.55
TABLE-US-00002 TABLE 2 Glass A9 A10 A11 A12 A13 A14 A15 A16 A17 A18
SiO.sub.2 64.3 64.3 64.3 64.3 64.3 65.3 64.3 60.3 56.3 64.3
Al.sub.2O.sub.3 7.2 7.0 6.0 6.0 8.0 7.0 10.0 11.5 15.5 8.0 MgO 11.0
11.0 12.5 13.0 11.0 11.0 8.5 11.0 11.0 10.5 CaO 0.1 0.1 0.1 0.1 0.1
0.1 0.1 0.1 0.1 0.1 SrO 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 BaO
0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 ZrO.sub.2 0.5 1.5 1.0 0.5
0.5 0.5 0 0 0 0.5 Na.sub.2O 12.7 11.5 12.0 12.0 12.0 12.0 13.0 13.0
13.0 12.5 K.sub.2O 4.0 4.5 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Tg 597
612* 610* 610* 614 610* 620* 630* 670* 608 CS1 1003 1013 984 963
954 983 1072 1145 1221 1024 CS2 588 564 561 546 576 574 640 641 647
582 r 0.59 0.56 0.57 0.57 0.60 0.58 0.60 0.56 0.53 0.57 R 0.57 0.54
0.55 0.55 0.56 0.57 0.59 0.54 0.51 0.57
TABLE-US-00003 TABLE 3 Glass A19 A20 A21 A22 A23 A24 A25 A26 A27
SiO.sub.2 64.3 63.5 66.0 64.5 65.0 63.5 64.3 71.3 66.7
Al.sub.2O.sub.3 8.5 10.5 9.0 9.0 5.0 5.0 6.0 2.0 10.8 MgO 10.5 9.0
8.0 12.0 12.0 8.0 11.0 10.4 6.2 CaO 0.1 0 0 0 0.5 4.0 0.1 0.3 0.6
SrO 0.1 0 0 0 0 0 0.1 0.03 0 BaO 0.1 0 0 0 0 0 0.1 0.02 0 ZrO.sub.2
0 0 0 0 0 1.3 2.5 0.5 0 Na.sub.2O 12.5 15.0 15.0 11.5 11.0 9.4 12.0
10.8 13.2 K.sub.2O 4.0 2.0 2.0 3.0 6.5 8.9 4.0 4.6 2.4 Tg 610* 630*
610* 650* 570* 580* 620 580* 595 CS1 985 1190 1054 919 746 668 1019
664 1039 CS2 577 752 722 516 382 240 571 407 679 r 0.59 0.63 0.69
0.56 0.51 0.36 0.56 0.61 0.65 R 0.57 0.64 0.66 0.58 0.50 0.35 0.55
0.59 0.64
[0080] From these results, it has been found that there is a high
correlation between R calculated by the above formula (shown in the
bottom rows in Tables 1 to 3) and the above r. FIG. 1 is a scatter
graph to make this point clear wherein the abscissa represents R
and the ordinate represents r, and the straight line in the Fig.
represents r=1.027.times.R-0.0017. The correlation coefficient is
0.97.
[0081] From the above correlation found by the present inventors,
the following is evident. That is, in order to reduce the frequency
of replacement of the molten salt, glass having a less degree of
decrease in S due to an increase of the Na concentration in the
molten salt i.e. glass having the above r being large, may be used,
and for such a purpose, the above R of the glass may be made to be
large.
[0082] By making R being at least 0.66, the above r can be made to
be at least 0.66 and as a result, it is possible to ease controls
of the Na concentration in the molten salt as compared with
conventional one, or it is possible to reduce the frequency of
replacement of the molten salt. R is preferably at least 0.68.
[0083] The glass of the present invention essentially comprises the
above-described components, but may contain other components within
a range not to impair the object of the present invention. In a
case where such other components are contained, the total content
of such components is preferably at most 5%, typically at most 3%.
The total content of SiO.sub.2, Al.sub.2O.sub.3, MgO, Na.sub.2O and
K.sub.2O is particularly preferably at least 98%. Now, such other
components will be exemplified.
[0084] CaO, SrO and BaO may be contained in order to improve the
melting property at a high temperature or to prevent
devitrification, but they may lower the ion exchange rate or
resistance against cracking. In a case where at least one of CaO,
SrO and BaO is contained, the content of each component is
preferably at most 1%, more preferably at most 0.5%. Further, in
such a case, the total content of these three components is
preferably at most 1%, more preferably at most 0.5%.
[0085] ZnO may be contained in a certain case, in order to improve
the melting property of glass at a high temperature, but its
content in such a case is preferably at most 1%. In a case of
production by a float process, ZnO is preferably at most 0.5%. If
ZnO exceeds 0.5%, it is likely to be reduced during the float
forming to form a product defect. Typically no ZnO is
contained.
[0086] B.sub.2O.sub.3 may be contained within a range of e.g. less
than 1% in some cases, in order to improve the melting property of
glass at a high temperature. If B.sub.2O.sub.3 is at least 1%,
homogeneous glass tends to be hardly obtainable, and the glass
forming may be difficult, or the chipping resistance may
deteriorate. Typically no B.sub.2O.sub.3 is contained.
[0087] TiO.sub.2 is likely to deteriorate the visible light
transmittance and to color glass to be brown when it is coexistent
with Fe ions in the glass, and therefore, its content is preferably
at most 1% if contained, and typically, it is not contained.
[0088] Li.sub.2O is a component to lower the strain point and to
bring about a stress relaxation thereby to make it difficult to
stably obtain a surface compressive stress layer and therefore it
is preferably not contained, and even if contained, its content is
preferably less than 1%, more preferably at most 0.05%,
particularly preferably less than 0.01%.
[0089] As a clarifying agent at the time of melting glass,
SO.sub.3, a chloride, a fluoride or the like may suitably be
contained. However, in order to increase the visibility of display
devices such as touch panels, it is preferred to reduce components
which may be included as impurities in raw materials such as
Fe.sub.2O.sub.3, NiO, Cr.sub.2O.sub.3, etc. having an absorption in
a visible light range as far as possible, and the content of each
of them is preferably at most 0.15%, more preferably at most 0.1%,
particularly preferably at most 0.05%, as represented by mass
percentage.
[0090] In the glass of the present invention,
R.sub.2O-Al.sub.2O.sub.3 is less than 10%, and also in the case of
the following glass C, the object of the present invention can be
accomplished, and yet, the above-mentioned r can be made large.
Here, with respect to glass C, the description relating to the
glass of the present invention is applicable as it is, except for
R.sub.2O-Al.sub.2O.sub.3 being less than 10%, and in glass C, it is
preferred that R.sub.2O-Al.sub.2O.sub.3 is made to be less than
10%.
[0091] Glass C: Glass for chemical tempering, which comprises, as
represented by mole percentage based on oxides, from 63 to 66% of
SiO.sub.2, from 7 to 10% of Al.sub.2O.sub.3, from 8 to 12% of MgO,
from 12 to 17% of Na.sub.2O, and from 0 to 3% of K.sub.2O, wherein
when ZrO.sub.2 is contained, its content is at most 0.5%, and
wherein R calculated by the following formula by using the contents
of the respective components of SiO.sub.2, Al.sub.2O.sub.3, MgO,
CaO, ZrO.sub.2, Na.sub.2O and K.sub.2O is at least 0.66:
R=0.029.times.SiO.sub.2+0.021.times.Al.sub.2O.sub.3+0.016.times.MgO-0.00-
4.times.CaO+0.016.times.ZrO.sub.2+0.029.times.Na.sub.2O+0.times.K.sub.2O-2-
.002
EXAMPLES
[0092] In Tables 4 to 6, Ex. 1 to 9 are Working Examples of the
present invention and Ex. 10 to 20 are Comparative Examples. Among
them, glass in Ex. 11 is similar to Example 19 in the
above-mentioned Patent Document 2, and glasses in Ex. 20, 13 and 21
are, respectively, the same as Example 1, Example 14 and
Comparative Example 54 in the same Document. The glass compositions
in Tables 4 to 6 are compositions as represented by mole
percentage, while in Tables 7 to 9, compositions as represented by
mass percentage of glasses in Ex. 1 to 21 are shown.
[0093] With respect to glasses in Ex. 1 to 8 and 10 to 14, raw
materials for the respective components were mixed to have
compositions as represented by mol % in columns for SiO.sub.2 to
BaO in Tables, and melted at a temperature of from 1550 to
1650.degree. C. for from 3 to 5 hours by means of a platinum
crucible. At the time of melting, a platinum stirrer was inserted
in molten glass, and stirring was carried out for two hours to
homogenize the glass. Then, molten glass was cast to form a plate
and annealed to room temperature at a cooling rate of 1.degree.
C./min. R.sub.2O represents the total of the respective contents
(unit: mol %) of Na.sub.2O and K.sub.2O.
[0094] With respect to these glasses, the specific gravity d, the
average linear expansion coefficient .alpha. (unit:
.sup.-7/.degree. C.), the glass transition point Tg (unit: .degree.
C.), the temperature T2 (unit: .degree. C.) at which the viscosity
becomes to be 10.sup.2 dPas, and the temperature T4 (unit: .degree.
C.) at which the viscosity becomes to be 10.sup.4 dPas, are shown
in Tables. Measurements thereof were carried out as follows.
[0095] d: Measured by Archimedes' method using from 20 to 50 g of
foamless glass.
[0096] .alpha.: By means of a differential dilatometer and using
quartz glass as a reference sample, the expansion rate of glass at
the time of raising the temperature from room temperature at a rate
of 5.degree. C./min, was measured to a temperature at which the
glass was softened so that its expansion was no longer observed
i.e. to the yield point, whereupon from the thermal expansion curve
thereby obtained, the average linear expansion coefficient at from
50 to 350.degree. C. was calculated.
[0097] Tg: By means of a differential dilatometer and using quartz
glass as a reference sample, the expansion rate of glass at the
time of raising the temperature from room temperature at a rate of
5.degree. C./min, was measured to the yield point, whereby in the
thermal expansion curve thereby obtained, a temperature
corresponding to a folding point was taken as the glass transition
point.
[0098] T2, T4: Measured by a rotational viscometer.
[0099] Both surfaces of each glass plate having a thickness of 1 mm
and a size of 5 mm.times.40 mm obtained as described above in Ex. 1
to 8 and 10 to 14, was mirror-polished with cerium oxide and then
subjected to the following chemical tempering treatment. That is,
such a glass plate was immersed in a molten potassium salt at
450.degree. C. for 270 minutes in Ex. 1, 2 or 7, for 120 minutes in
Ex. 3, for 300 minutes in Ex. 4, 180 minutes in Ex. 5, for 320
minutes in Ex. 6, for 210 minutes in Ex. 8, for 195 minutes in Ex.
10, for 330 minutes in Ex. 11, for 300 minutes in Ex. 12, for 450
minutes in Ex. 13, or for 1380 minutes in Ex. 14, for tempering
treatment to obtain a chemically tempered glass plate. In the
molten potassium salt, the KNO.sub.3 content was from 95 to 100%,
and the NaNO.sub.3 content was from 0 to 5%. The specific KNO.sub.3
content was 99% in Ex. 1, 2 or 11, 100% in Ex. 3, 10 or 13, 95% in
Ex. 4, 5 or 14, 99.3% in Ex. 6, 97% in Ex. 7 or 8, or 99.5% in Ex.
12.
[0100] With respect to these chemically tempered glass plates, the
surface compressive stress S (unit: MPa) and the compressive stress
layer depth t (unit: .mu.m) were measured by means of a surface
stress meter FSM-6000 manufactured by Orihara Manufacturing Co.,
Ltd. The results are shown in the corresponding rows in Tables.
[0101] With respect to 20 sheets each of these 13 types of
chemically tempered glass plates, the flexural strength was
measured, and an average value F0 (unit: MPa) of flexural strength
was obtained. Here, the accuracy of flexural strength measurement
was .+-.30 MPa, and the measurement of the flexural strength was
carried out by a three point flexural test under conditions of a
span of 30 mm and a crosshead speed of 0.5 mm/min.
[0102] Further, with respect to 20 sheets each of these 13 types of
chemically tempered glass plates, by means of a Vickers hardness
meter, a Vickers indenter was pressed with a force of 1 kgf=9.8N
against the center of each glass plate under conditions of a
temperature of from 20 to 28.degree. C. and a humidity of from 40
to 60%, to form an indentation. With respect to 20 sheets each of 4
types of chemically tempered glass plates having an indentation
thus formed with a force of 1 kgf, the flexural strength was
measured, and an average value F1 (unit: MPa) of flexural strength
was obtained.
[0103] Further, with respect to 20 sheets each of these 13 types of
chemically tempered glass plates, by means of a Vickers hardness
meter, a Vickers indenter was pressed with a force of 2 kgf=9.8N
against the center of each glass plate under conditions of a
temperature of from 20 to 28.degree. C. and a humidity of from 40
to 60%, to form an indentation. With respect to 20 sheets each of 4
types of chemically tempered glass plates having an indentation
thus formed with a force of 2 kgf, the flexural strength was
measured, and an average value F2 (unit: MPa) of flexural strength
was obtained. F0, F1 and F2 are shown together with F1/F0 and F2/F0
in the corresponding rows in Tables. Here, in Ex. 1 and 2, F1/F0
exceeds 1, which is attributable to an accidental error in
measurement of F0 or F1.
[0104] With those obtained by chemically tempering glasses in Ex.
11 to 14, F1 is lower than F0, while with those obtained by
chemically tempering glasses in Ex. 1 to 8, F1 has the same or
substantially the same value as F0. Further, with those obtained by
chemically tempering glasses in Ex. 1 to 8, the difference between
F0 and F2 is smaller as compared with those obtained by chemically
tempering glasses in Ex. 11 to 14. With those obtained by
chemically tempering glasses in Ex. 4 and 8, F2 is also the same or
substantially the same as F0, which shows that the advantageous
effects of the present invention are particularly high. Further,
with one obtained by chemically tempering glass in Ex. 10, F1 has
substantially the same value as F0, but Tg is low.
[0105] In Ex. 9 and Ex. 15 to 21, with respect to chemically
tempered glasses having S of 800 MPa and t of 50 .mu.m, their F0,
F1 and F2 were estimated from the respective glass
compositions.
TABLE-US-00004 TABLE 4 Ex. 1 2 3 4 5 6 7 SiO.sub.2 64.3 64.3 65.3
64.0 63.0 64.3 63.5 Al.sub.2O.sub.3 8.0 8.0 7.0 11.0 12.0 8.5 10.5
MgO 10.9 10.4 11.2 9.0 7.0 10.5 9.0 Na.sub.2O 12.0 12.5 9.0 15.0
17.0 12.5 15.0 K.sub.2O 4.0 4.0 7.0 1.0 1.0 4.0 2.0 ZrO.sub.2 0.5
0.5 0.5 0 0 0 0 CaO 0.1 0.1 0 0 0 0.1 0 SrO 0.1 0.1 0 0 0 0.1 0 BaO
0.1 0.1 0 0 0 0.1 0 R.sub.2O 16.0 16.5 16.0 16.0 18.0 16.8 17.0
R.sub.2O--Al.sub.2O.sub.3 8.0 8.5 9.0 5.0 6.0 8.3 6.5 R 0.56 0.57
0.49 0.66 0.68 0.57 0.64 d 2.48 2.48 2.46 2.46 2.46 2.47 2.46
.alpha. 98 98 102 91 98 104 99 Tg 614 608 611 637 631 596 619 T2
1612 1605 1633 1669 1667 1617 1638 T4 1187 1181 1201 1211 1203 1183
1195 S 761 789 710 813 839 831 850 t 53 50 49 49 46 49 50 F0 601
613 667 721 742 681 664 F1 609 617 666 714 717 634 663 F2 457 456
646 664 649 545 579 F1/F0 1.01 1.01 1.00 0.99 0.97 0.93 1.00 F2/F0
0.76 0.74 0.97 0.92 0.88 0.80 0.87
TABLE-US-00005 TABLE 5 Ex. 8 9 10 11 12 13 14 SiO.sub.2 66.0 64.3
65.0 64.3 64.3 66.7 61.0 Al.sub.2O.sub.3 9.0 8.5 5.0 6.0 7.0 3.6
11.0 MgO 8.0 10.7 12.0 10.9 10.9 12.1 13.0 Na.sub.2O 15.0 12.5 11.0
12.0 12.5 11.0 14.2 K.sub.2O 2.0 4.0 6.5 4.0 4.0 4.2 0 ZrO.sub.2 0
0 0 2.5 1.0 0.7 0.8 CaO 0 0 0.5 0.1 0.1 1.1 0 SrO 0 0 0 0.1 0.1 0.6
0 BaO 0 0 0 0.1 0.1 0 0 R.sub.2O 17.0 16.5 18.0 16.0 16.5 15.2 14.2
R.sub.2O--Al.sub.2O.sub.3 8.0 8.0 13.0 10.0 9.5 11.6 3.2 R 0.66
0.57 0.50 0.55 0.56 0.53 0.63 d 2.45 2.47 2.47 2.52 2.50 2.50 2.50
.alpha. 99 98 109 91 98 97 83 Tg 599 612 558 620 603 569 678 T2
1662 1618 1544 1566 1588 1529 1597 T4 1200 1184 1128 1167 1164 1121
1193 S 770 800 680 780 833 746 828 t 50 50 53 51 51 50 53 F0 585
600 574 584 653 637 744 F1 613 600 543 415 520 457 499 F2 584 500
429 280 412 207 377 F1/F0 1.05 1.00 0.95 0.71 0.80 0.72 0.67 F2/F0
1.00 0.83 0.75 0.48 0.63 0.33 0.51
TABLE-US-00006 TABLE 6 Ex. 15 16 17 18 19 20 21 SiO.sub.2 66.0 68.0
60.0 64.3 68.5 67.4 64.8 Al.sub.2O.sub.3 6.0 5.0 13.0 6.2 7.4 3.7
5.3 MgO 7.2 6.0 14.0 13.0 7.9 12.2 12.1 Na.sub.2O 14.0 15.8 13.0
8.0 12.2 8.1 11.0 K.sub.2O 6.0 4.2 0 8.0 4.0 6.3 6.3 ZrO.sub.2 0.8
1.0 0 0.5 0 0.7 0 CaO 0 0 0 0 0 1.0 0.5 SrO 0 0 0 0 0 0.6 0 BaO 0 0
0 0 0 0 0 R.sub.2O 20.0 20.0 13.0 16.0 16.2 14.4 17.3
R.sub.2O--Al.sub.2O.sub.3 14.0 15.0 0 3.0 8.8 10.7 12.0 R 0.57 0.65
0.61 0.44 0.62 0.47 0.50 d 2.48 2.47 2.49 2.47 2.43 2.59 2.46
.alpha. 111 109 86 99 95 90 100 Tg 541 539 705 624 603 579 568 T2
1591 1589 1634 1596 1693 1575 1548 T4 1148 1137 1224 1181 1213 1158
1132 S 800 800 800 800 800 800 800 t 50 50 50 50 50 50 50 F0 600
600 600 600 600 600 600 F1 550 350 450 400 600 450 500 F2 450 250
300 300 550 300 350 F1/F0 0.92 0.58 0.75 0.67 1.00 0.75 0.83 F2/F0
0.75 0.42 0.50 0.50 0.92 0.50 0.58
TABLE-US-00007 TABLE 7 Ex. 1 2 3 4 5 6 7 SiO.sub.2 61.0 60.9 61.6
60.5 58.8 61.0 59.9 Al.sub.2O.sub.3 12.9 12.9 11.2 17.7 19.0 13.7
16.8 MgO 6.9 6.6 7.1 5.7 4.4 6.7 5.7 Na.sub.2O 11.7 12.2 8.8 14.6
16.4 12.2 14.6 K.sub.2O 6.0 5.9 10.4 1.5 1.5 5.9 3.0 ZrO.sub.2 1.0
1.0 1.0 0 0 0 0 CaO 0.1 0.1 0 0 0 0.1 0 SrO 0.2 0.2 0 0 0 0.2 0 BaO
0.2 0.2 0 0 0 0.2 0
TABLE-US-00008 TABLE 8 Ex. 8 9 10 11 12 13 14 SiO.sub.2 62.7 61.2
62.8 60.6 61.1 65.2 58.3 Al.sub.2O.sub.3 14.5 13.7 8.2 9.6 11.3 6.0
17.8 MgO 5.1 6.8 7.8 6.9 6.9 7.9 8.3 Na.sub.2O 14.7 12.3 11.0 11.7
12.3 11.1 14.0 K.sub.2O 3.0 6.0 9.8 5.9 6.0 6.4 0 ZrO.sub.2 0 0 0
4.8 1.9 1.4 1.6 CaO 0 0 0.5 0.1 0.1 1.0 0 SrO 0 0 0 0.2 0.2 1.0 0
BaO 0 0 0 0.2 0.2 0 0
TABLE-US-00009 TABLE 9 Ex. 15 16 17 18 19 20 21 SiO.sub.2 61.9 64.5
57.2 61.0 65.1 65.1 62.5 Al.sub.2O.sub.3 9.5 8.0 21.0 10.0 11.9 6.1
8.7 MgO 4.4 3.8 9.0 8.3 5.0 7.9 7.8 Na.sub.2O 13.5 15.5 12.8 7.8
12.0 8.1 11.0 K.sub.2O 9.1 6.2 0 11.9 6.0 9.5 9.5 ZrO.sub.2 1.5 1.9
0 1.0 0 1.4 0 CaO 0 0 0 0 0 0.9 0.5 SrO 0 0 0 0 0 1.0 0 BaO 0 0 0 0
0 0 0
INDUSTRIAL APPLICABILITY
[0106] The present invention is useful for e.g. a cover glass for a
display device. Further, it is useful also for e.g. a solar cell
substrate or a window glass for aircrafts.
[0107] This application is a continuation of PCT Application No.
PCT/JP2011/071901, filed on Sep. 26, 2011, which is based upon and
claims the benefit of priority from Japanese Patent Application No.
2010-215982 filed on Mar. 27, 2010 and Japanese Patent Application
No. 2010-288255 filed on Dec. 24, 2010. The contents of those
applications are incorporated herein by reference in its
entirety.
* * * * *