U.S. patent number RE46,763 [Application Number 14/879,713] was granted by the patent office on 2018-03-27 for liquid crystal composition and liquid crystal display device.
This patent grant is currently assigned to JNC CORPORATION, JNC PETROCHEMICAL CORPORATION. The grantee listed for this patent is JNC CORPORATION, JNC PETROCHEMICAL CORPORATION. Invention is credited to Masayuki Saito.
United States Patent |
RE46,763 |
Saito |
March 27, 2018 |
**Please see images for:
( Certificate of Correction ) ** |
Liquid crystal composition and liquid crystal display device
Abstract
Described is a liquid crystal composition which satisfies at
least one of such characteristics as high upper limit temperature
of the nematic phase, low lower limit temperature of the nematic
phase, low viscosity, adequate optical anisotropy, large negative
dielectric anisotropy, high resistivity, high stability to
ultraviolet light and high stability to heat, or which has an
adequate balance between at least two of the above-mentioned
characteristics. Also described is an AM element having a short
response time, high voltage holding ratio, high contrast ratio,
long life and the like. The liquid crystal composition contains a
specific compound having a large negative dielectric anisotropy and
a low lower limit temperature as a first component, a specific
compound having a low viscosity or a high upper limit temperature
as a second component, and a specific compound having a
polymerizable group as a third component. The AM element contains
the composition.
Inventors: |
Saito; Masayuki (Ichihara,
JP) |
Applicant: |
Name |
City |
State |
Country |
Type |
JNC CORPORATION
JNC PETROCHEMICAL CORPORATION |
Tokyo
Tokyo |
N/A
N/A |
JP
JP |
|
|
Assignee: |
JNC CORPORATION (Tokyo,
JP)
JNC PETROCHEMICAL CORPORATION (Tokyo, JP)
|
Family
ID: |
42355877 |
Appl.
No.: |
14/879,713 |
Filed: |
October 9, 2015 |
PCT
Filed: |
January 15, 2010 |
PCT No.: |
PCT/JP2010/050374 |
371(c)(1),(2),(4) Date: |
July 22, 2011 |
PCT
Pub. No.: |
WO2010/084823 |
PCT
Pub. Date: |
July 29, 2010 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
Reissue of: |
13145791 |
Jan 15, 2010 |
8535768 |
Sep 17, 2013 |
|
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Foreign Application Priority Data
|
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|
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Jan 22, 2009 [JP] |
|
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2009-011507 |
Aug 4, 2009 [JP] |
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2009-181775 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C09K
19/44 (20130101); C09K 19/3001 (20130101); C09K
19/46 (20130101); C09K 19/062 (20130101); C09K
19/3402 (20130101); C09K 19/42 (20130101); C09K
19/44 (20130101); C09K 19/322 (20130101); C09K
19/3402 (20130101); C09K 19/42 (20130101); C09K
19/062 (20130101); C09K 19/46 (20130101); C09K
19/12 (20130101); C09K 19/3001 (20130101); C09K
19/12 (20130101); C09K 2019/0407 (20130101); C09K
2019/3078 (20130101); C09K 2019/122 (20130101); C09K
2019/3009 (20130101); C09K 2019/3021 (20130101); C09K
2019/3078 (20130101); C09K 2019/3004 (20130101); C09K
2323/00 (20200801); C09K 2019/3025 (20130101); C09K
2019/123 (20130101); C09K 2019/3425 (20130101); C09K
2019/3016 (20130101); C09K 2019/301 (20130101); C09K
2019/3015 (20130101); Y10T 428/10 (20150115); C09K
2019/301 (20130101); C09K 2019/123 (20130101); C09K
2019/3027 (20130101); C09K 2019/3004 (20130101); C09K
2019/3015 (20130101); C09K 2019/3016 (20130101); C09K
2019/3425 (20130101); C09K 2019/3025 (20130101); C09K
2019/3009 (20130101); C09K 2019/3422 (20130101); C09K
2019/0407 (20130101); C09K 2323/00 (20200801); C09K
2019/3021 (20130101); C09K 2019/122 (20130101); C09K
2019/0448 (20130101); C09K 2019/3422 (20130101); C09K
2019/0448 (20130101) |
Current International
Class: |
C09K
19/30 (20060101); C09K 19/44 (20060101); C09K
19/46 (20060101); C09K 19/42 (20060101); C09K
19/32 (20060101); C09K 19/34 (20060101); C09K
19/06 (20060101); C09K 19/20 (20060101); C09K
19/12 (20060101); C09K 19/04 (20060101) |
References Cited
[Referenced By]
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WO |
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Other References
Decision of the Invalidity Trial, Patent No. 201080005115.X, dated
Aug. 13, 2015. cited by applicant.
|
Primary Examiner: Diamond; Alan
Attorney, Agent or Firm: Hogan Lovells US LLP
Claims
What is claimed is:
.[.1. A liquid crystal composition, containing at least one
compound selected from the group of compounds represented by
formula (1) as a first component, at least one compound selected
from the group of compounds represented by formula (2) as a second
component and at least one compound selected from the group of
compounds represented by formula (3) as a third component:
##STR00044## wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are
independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12
carbons or alkenyl having 2 to 12 carbons, or alkenyl having 2 to
12 carbons in which arbitrary hydrogen is replaced by fluorine;
R.sup.5 and R.sup.6 are independently alkyl having 1 to 12 carbons,
alkoxy having 1 to 12 carbons or alkenyl having 2 to 12 carbons, or
alkenyl having 2 to 12 carbons in which arbitrary hydrogen is
replaced by fluorine, acrylate, methacrylate, vinyloxy,
propenylether, oxirane, oxetane or vinylketone, and at least one of
R.sup.5 and R.sup.6 is acrylate, methacrylate, propenylether,
oxirane, oxetane or vinylketone; ring A is independently
1,4-cyclohexylene or 1,4-phenylene; ring B and ring C are
independently 1,4-cyclohexylene, 1,4-phenylene,
2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene or
2,5-difluoro-1,4-phenylene; ring D and ring E are independently
1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene,
3-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene,
2,5-difluoro-1,4-phenylene, 3,5-difluoro-1,4-phenylene,
2-methyl-1,4-phenylene, 3-methyl-1,4-phenylene or 2,6-naphthalene;
Z.sup.1 is independently a single bond, ethylene, methyleneoxy or
carbonyloxy; Z.sup.2 and Z.sup.3 are independently a single bond,
alkylene having 1 to 12 carbons, or alkylene having 1 to 12 carbons
in which arbitrary --CH.sub.2-- is replaced by --O--; k and j are
independently 1, 2 or 3; and m is 0, 1 or 2, and wherein the at
least one compound as the second component comprises arbitrary one
of compounds 2-HH-3 and V-HH-3 shown below: ##STR00045## .].
.[.2. The liquid crystal composition according to claim 1, wherein
the first component is at least one compound selected from the
group of compounds represented by formula (1-1) to formula (1-7):
##STR00046## wherein R.sup.1 and R.sup.2 are independently alkyl
having 1 to 12 carbons, alkoxy having 1 to 12 carbons or alkenyl
having 2 to 12 carbons, or alkenyl having 2 to 12 carbons in which
arbitrary hydrogen is replaced by fluorine..].
.[.3. The liquid crystal composition according to claim 1, wherein
the second component further comprises at least one compound
selected from the group of compounds represented by formula (2-1)
to formula (2-12) other than the compounds 2-HH-3 and V-HH-3:
##STR00047## wherein R.sup.3 and R.sup.4 are independently alkyl
having 1 to 12 carbons, alkoxy having 1 to 12 carbons or alkenyl
having 2 to 12 carbons, or alkenyl having 2 to 12 carbons in which
arbitrary hydrogen is replaced by fluorine..].
.[.4. The liquid crystal composition according to claim 1, wherein
the third component is at least one compound selected from the
group of compounds represented by formula (3-1) to formula (3-23):
##STR00048## ##STR00049## ##STR00050## wherein R.sup.5 and R.sup.6
are independently alkyl having 1 to 12 carbons, alkoxy having 1 to
12 carbons or alkenyl having 2 to 12 carbons, or alkenyl having 2
to 12 carbons in which arbitrary hydrogen is replaced by fluorine,
acrylate, methacrylate, vinyloxy, propenylether, oxirane, oxetane
or vinylketone, and at least one of R.sup.5 and R.sup.6 is
acrylate, methacrylate, propenylether, oxirane, oxetane or
vinylketone; and Z.sup.2 and Z.sup.3 are independently a single
bond, alkylene having 1 to 12 carbons, or alkylene having 1 to 12
carbons in which arbitrary --CH.sub.2-- is replaced by
--O--..].
.[.5. The liquid crystal composition according to claim 4, wherein
the third component is at least one compound selected from the
group of compounds represented by formula (3-2)..].
.[.6. The liquid crystal composition according to claim 4, wherein
the third component is at least one compound selected from the
group of compounds represented by formula (3-3)..].
.[.7. The liquid crystal composition according to claim 4, wherein
the third component is at least one compound selected from the
group of compounds represented by formula (3-4)..].
.[.8. The liquid crystal composition according to claim 1, wherein
a ratio of the first component is in the range of 10% by weight to
60% by weight, a ratio of the second component is in the range of
5% by weight to 50% by weight, based on the weight of the liquid
crystal composition excluding the third component, and a ratio of
the third component is in the range of 0.05 part by weight to 10
parts by weight, relative to 100 parts by weight of the liquid
crystal composition excluding the third component..].
.[.9. The liquid crystal composition according to claim 1, further
containing at least one compound selected from the group of
compounds represented by formula (4-1) to formula (4-3) as a fourth
component: ##STR00051## wherein R.sup.1 and R.sup.2 are
independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12
carbons or alkenyl having 2 to 12 carbons, or alkenyl having 2 to
12 carbons in which arbitrary hydrogen is replaced by fluorine;
ring A and ring G are independently 1,4-cyclohexylene or
1,4-phenylene; ring F is independently tetrahydropyran-2,5-diyl,
1,4-cyclohexylene, 1,4-phenylene or 2,3-difluoro-1,4-phenylene;
Z.sup.1 and Z.sup.4 are independently a single bond, ethylene,
methyleneoxy or carbonyloxy; X.sup.1 and X.sup.2 are fluorine for
either one or chlorine for the other one; X.sup.3 is hydrogen or
methyl, and when X.sup.3 is hydrogen, at least one of ring F is
tetrahydropyran-2,5-diyl or 2,3-difluoro-1,4-phenylene; r and t are
independently 1, 2 or 3; and p and q are independently 0, 1, 2 or
3, and a sum of p and q is 3 or less..].
.[.10. The liquid crystal composition according to claim 9, wherein
the fourth component is at least one compound selected from the
group of compounds represented by formula (4-1-1) to formula
(4-1-3), formula (4-2-1) to formula (4-2-15) and formula (4-3-1) to
formula (4-3-4): ##STR00052## ##STR00053## ##STR00054## wherein
R.sup.1 and R.sup.2 are independently alkyl having 1 to 12 carbons,
alkoxy having 1 to 12 carbons or alkenyl having 2 to 12 carbons, or
alkenyl having 2 to 12 carbons in which arbitrary hydrogen is
replaced by fluorine; ring A.sup.1, ring A.sup.2, ring G.sup.1 and
ring G.sup.2 are independently 1,4-cyclohexylene or 1,4-phenylene;
and Z.sup.1 and Z.sup.4 are independently a single bond, ethylene,
methyleneoxy or carbonyloxy..].
.[.11. The liquid crystal composition according to claim 1, further
containing a polymerization initiator..].
.[.12. The liquid crystal composition according to claim 1, further
containing a polymerization inhibitor..].
.[.13. The liquid crystal composition according to claim 1, wherein
a maximum temperature of a nematic phase is 70.degree. C. or
higher, an optical anisotropy (25.degree. C.) at a wavelength of
589 nanometers is 0.08 or more, and a dielectric anisotropy
(25.degree. C.) at a frequency of 1 kHz is -2 or less..].
.[.14. A liquid crystal display device, containing the liquid
crystal composition according to claim 1..].
.[.15. The liquid crystal display device according to claim 14,
wherein an operating mode in the liquid crystal display device is a
VA mode, an IPS mode or a PSA mode, and a driving mode in the
liquid crystal display device is an active matrix mode..].
.[.16. The liquid crystal composition according to claim 2, wherein
the second component further comprises at least one compound
selected from the group of compounds represented by formula (2-1)
to formula (2-12) other than the compounds 2-HH-3 and V-HH-3:
##STR00055## wherein R.sup.3 and R.sup.4 are independently alkyl
having 1 to 12 carbons, alkoxy having 1 to 12 carbons or alkenyl
having 2 to 12 carbons, or alkenyl having 2 to 12 carbons in which
arbitrary hydrogen is replaced by fluorine..].
.[.17. The liquid crystal composition according to claim 16,
wherein the third component is at least one compound selected from
the group of compounds represented by formula (3-1) to formula
(3-23): ##STR00056## ##STR00057## ##STR00058## wherein R.sup.5 and
R.sup.6 are independently alkyl having 1 to 12 carbons, alkoxy
having 1 to 12 carbons or alkenyl having 2 to 12 carbons, or
alkenyl having 2 to 12 carbons in which arbitrary hydrogen is
replaced by fluorine, acrylate, methacrylate, vinyloxy,
propenylether, oxirane, oxetane or vinylketone, and at least one of
R.sup.5 and R.sup.6 is acrylate, methacrylate, propenylether,
oxirane, oxetane or vinylketone; and Z.sup.2 and Z.sup.3 are
independently a single bond, alkylene having 1 to 12 carbons, or
alkylene having 1 to 12 carbons in which arbitrary --CH.sub.2-- is
replaced by --O--..].
.[.18. The liquid crystal composition according to claim 17,
wherein the third component is at least one compound selected from
the group of compounds represented by formula (3-2)..].
.[.19. The liquid crystal composition according to claim 17,
wherein the third component is at least one compound selected from
the group of compounds represented by formula (3-3)..].
.[.20. The liquid crystal composition according to claim 17,
wherein the third component is at least one compound selected from
the group of compounds represented by formula (3-4)..].
.Iadd.21. A liquid crystal composition, containing at least one
compound selected from the group of compounds represented by
formula (1) as a first component, at least one compound selected
from the group of compounds represented by formula (2) as a second
component and at least one compound selected from the group of
compounds represented by formula (3) as a third component:
##STR00059## wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are
independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12
carbons or alkenyl having 2 to 12 carbons, or alkenyl having 2 to
12 carbons in which arbitrary hydrogen is replaced by fluorine;
R.sup.5 and R.sup.6 are independently alkyl having 1 to 12 carbons,
alkoxy having 1 to 12 carbons or alkenyl having 2 to 12 carbons, or
alkenyl having 2 to 12 carbons in which arbitrary hydrogen is
replaced by fluorine, acrylate, methacrylate, vinyloxy,
propenylether, oxirane, oxetane or vinylketone, and at least one of
R.sup.5 and R.sup.6 is acrylate, methacrylate, propenylether,
oxirane, oxetane or vinylketone; ring A is independently
1,4-cyclohexylene or 1,4-phenylene; ring B and ring C are
independently 1,4-cyclohexylene, 1,4-phenylene,
2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene or
2,5-difluoro-1,4-phenylene; ring D and ring E are independently
1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene,
3-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene,
2,5-difluoro-1,4-phenylene, 3,5-difluoro-1,4-phenylene,
2-methyl-1,4-phenylene, 3-methyl-1,4-phenylene or 2,6-naphthalene;
Z.sup.1 is independently a single bond, ethylene, methyleneoxy or
carbonyloxy; Z.sup.2 and Z.sup.3 are independently a single bond,
alkylene having 1 to 12 carbons, or alkylene having 1 to 12 carbons
in which arbitrary --CH.sub.2-- is replaced by --O--; k is 1, 2 or
3; j is 1; and m is 0, 1 or 2, wherein the at least one compound as
the first component is a compound 3-HB(2F,3F)-O2 shown below:
##STR00060## 3-HB(2F,3F)-O2, and wherein the at least one compound
as the second component comprises arbitrary one of compounds 2-HH-3
and V-HH-3 shown below: ##STR00061## wherein the at least one
compound as the second component is V-HH-3: ##STR00062## and
wherein the ratio of V-HH-3 is at least 20% by weight.
.Iaddend.
.Iadd.22. The liquid crystal composition according to claim 21,
wherein the first component is at least one compound selected from
the group of compounds represented by formula (1-1) to formula
(1-7): ##STR00063## wherein R.sup.1 and R.sup.2 are independently
alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or
alkenyl having 2 to 12 carbons, or alkenyl having 2 to 12 carbons
in which arbitrary hydrogen is replaced by fluorine. .Iaddend.
.Iadd.23. The liquid crystal composition according to claim 21,
wherein R.sup.2 is alkoxy having 1 to 12 carbons. .Iaddend.
.Iadd.24. The liquid crystal composition according to claim 21,
wherein the second component further comprises at least one
compound selected from the group of compounds represented by
formula (2-1) to formula (2-3) other than the compound V-HH-3:
##STR00064## wherein R.sup.3 and R.sup.4 are independently alkyl
having 1 to 12 carbons, alkoxy having 1 to 12 carbons or alkenyl
having 2 to 12 carbons, or alkenyl having 2 to 12 carbons in which
arbitrary hydrogen is replaced by fluorine. .Iaddend.
.Iadd.25. The liquid crystal composition according to claim 21,
wherein the third component is at least one compound selected from
the group of compounds represented by formula (3-1) to formula
(3-23): ##STR00065## ##STR00066## ##STR00067## wherein R.sup.5 and
R.sup.6 are independently alkyl having 1 to 12 carbons, alkoxy
having 1 to 12 carbons or alkenyl having 2 to 12 carbons, or
alkenvl having 2 to 12 carbons in which arbitrary hydrogen is
replaced by fluorine, acrylate, methacrylate, propenylether,
oxirane, oxetane or vinylketone, and at least one of R.sup.5 and
R.sup.6 is acrylate, methacrylate, propenylether, oxirane, oxetane
or vinylketone; and Z.sup.2 and Z.sup.3 are independently a single
bond, alkylene having 1 to 12 carbons, or alkylene having 1 to 12
carbons in which arbitrary --CH.sub.2-- is replaced by --O--.
.Iaddend.
.Iadd.26. The liquid crystal composition according to claim 25,
wherein the third component is at least one compound selected from
the group of compounds represented by formula (3-2). .Iaddend.
.Iadd.27. The liquid crystal composition according to claim 21,
wherein the third component is at least one compound selected from
the group of compounds represented by formula (3-1) to formula
(3-23): ##STR00068## ##STR00069## ##STR00070## wherein R.sup.5 and
R.sup.6 are independently alkyl having 1 to 12 carbons, alkoxy
having 1 to 12 carbons or alkenyl having 2 to 12 carbons, or
alkenyl having 2 to 12 carbons in which arbitrary hydrogen is
replaced by fluorine, acrylate, methacrylate, propenylether,
oxirane, oxetane or vinylketone, and at least one of R.sup.5 and
R.sup.6 is methacrylate; and Z.sup.2 and Z.sup.3 are independently
a single bond, alkylene having 1 to 12 carbons, or alkylene having
1 to 12 carbons in which arbitrary --CH.sub.2-- is replaced by
--O--. .Iaddend.
.Iadd.28. The liquid crystal composition according to claim 21,
wherein a ratio of the first component is in the range of 10% by
weight to 60% by weight, a ratio of the second component is in the
range of 20% by weight to 50% by weight, based on the weight of the
liquid crystal composition excluding the third component, and a
ratio of the third component is in the range of 0.05 part by weight
to 10 parts by weight, relative to 100 parts by weight of the
liquid crystal composition excluding the third component.
.Iaddend.
.Iadd.29. The liquid crystal composition according to claim 21,
further containing at least one compound selected from the group of
compounds represented by formula (4-1) to formula (4-3) as a fourth
component: ##STR00071## wherein R.sup.1 and R.sup.2 are
independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12
carbons or alkenyl having 2 to 12 carbons, or alkenyl having 2 to
12 carbons in which arbitrary hydrogen is replaced by fluorine;
ring A and ring G are independently 1,4-cyclohexylene or
1,4-phenylene; ring F is independently tetrahydropyran-2,5-diyl,
1,4-cyclohexylene, 1,4-phenylene or 2,3-difluoro-1,4-phenylene;
Z.sup.1 and Z.sup.4 are independently a single bond, ethylene,
methyleneoxy or carbonyloxy; X.sup.1 and X.sup.2 are fluorine or
chlorine, wherein one is fluorine, the other is chlorine; X.sup.3
is hydrogen or methyl, and when X.sup.3 is hydrogen, at least one
of ring F is tetrahydropyran-2,5-diyl or
2,3-difluoro-1,4-phenylene; r and t are independently 1, 2 or 3;
and p and q are independently 0, 1, 2 or 3, and a sum of p and q is
3 or less. .Iaddend.
.Iadd.30. The liquid crystal composition according to claim 29,
wherein the fourth component is at least one compound selected from
the group of compounds represented by formula (4-1-1) to formula
(4-1-3), formula (4-2-1) to formula (4-2-15) and formula (4-3-1) to
formula (4-3-4): ##STR00072## ##STR00073## ##STR00074## wherein
R.sup.1 and R.sup.2 are independently alkyl having 1 to 12 carbons,
alkoxy having 1 to 12 carbons or alkenyl having 2 to 12 carbons, or
alkenyl having 2 to 12 carbons in which arbitrary hydrogen is
replaced by fluorine; ring A.sup.1, ring A.sup.2, ring G.sup.1 and
ring G.sup.2 are independently 1,4-cyclohexylene or 1,4-phenylene;
and Z.sup.1 and Z.sup.4 are independently a single bond, ethylene,
methyleneoxy or carbonyloxy. .Iaddend.
.Iadd.31. The liquid crystal composition according to claim 21,
further containing a polymerization initiator. .Iaddend.
.Iadd.32. The liquid crystal composition according to claim 21,
further containing a polymerization inhibitor. .Iaddend.
.Iadd.33. The liquid crystal composition according to claim 21,
wherein a maximum temperature of a nematic phase is 70.degree. C.
or higher, an optical anisotropy (25.degree. C.) at a wavelength of
589 nanometers is 0.08 or more, and a dielectric anisotropy
(25.degree. C.) at a frequency of 1 kHz is -2 or less.
.Iaddend.
.Iadd.34. A liquid crystal display device comprising the liquid
crystal composition according to claim 21, wherein an operating
mode in the liquid crystal display device is a PSA mode, and a
driving mode in the liquid crystal display device is an active
matrix mode. .Iaddend.
Description
CROSS-REFERENCE TO RELATED APPLICATION
This .[.application claims.]. .Iadd.is a reissue application of
U.S. Pat. No. 8,535,768, which issued on Sep. 17, 2013, which was
filed as U.S. application Ser. No. 13/145,791 on Jul. 22, 2011,
which claimed .Iaddend.the priority benefit of the International
Patent Application No. PCT/JP2010/050374 filed on Jan. 15, 2010,
which claims the priority benefit of Japan application no.
2009-011507, filed on Jan. 22, 2009 and the priority benefit of
Japan application no. 2009-181775 filed on Aug. 4, 2009. The
entirety of the above-mentioned patent applications is hereby
incorporated by reference herein and made a part of this
specification.
TECHNICAL FIELD
The invention relates to a liquid crystal composition mainly
suitable for use in an active matrix (AM) device and so forth, and
an AM device and so forth containing the composition. More
specifically, the invention relates to a liquid crystal composition
having a negative dielectric anisotropy, and a device that contains
the composition and has a mode such as an in-plane switching (IPS)
mode, a vertical alignment (VA) mode or a polymer sustained
alignment (PSA) mode.
BACKGROUND ART
In a liquid crystal display device, a classification based on an
operating mode for liquid crystals includes a phase change (PC)
mode, a twisted nematic (TN) mode, a super twisted nematic (STN)
mode, an electrically controlled birefringence (ECB) mode, an
optically compensated bend (OCB) mode, an in-plane switching (IPS)
mode, a vertical alignment (VA) and a polymer sustained alignment
(PSA) mode. A classification based on a driving mode in the device
includes a passive matrix (PM) and an active matrix (AM). The PM is
further classified into static, multiplex and so forth, and the AM
is classified into a thin film transistor (TFT), a metal insulator
metal (MIM) and so forth. The TFT is further classified into
amorphous silicon and polycrystal silicon. The latter is classified
into a high temperature type and a low temperature type according
to a production process. A classification based on a light source
includes a reflective type utilizing a natural light, a
transmissive type utilizing a backlight and a transreflective type
utilizing both the natural light and the backlight.
The device contains a liquid crystal composition having suitable
characteristics. The liquid crystal composition has a nematic
phase. General characteristics of the composition should be
improved to obtain an AM device having good general
characteristics. Table 1 below summarizes a relationship between
two of the general characteristics. The general characteristics of
the composition will be explained further based on a commercially
available AM device. A temperature range of the nematic phase
relates to a temperature range in which the device can be used. A
preferred maximum temperature of the nematic phase is 70.degree. C.
or higher and a preferred minimum temperature of the nematic phase
is 10.degree. C. or lower. A viscosity of the composition relates
to a response time in the device. A short response time is
preferred for displaying moving images on the device. Accordingly,
a small viscosity in the composition is preferred. A small
viscosity at a low temperature is further preferred.
TABLE-US-00001 TABLE 1 General Characteristics of Composition and
AM Device General Characteristics General Characteristics No. of
Composition of AM Device 1 wide temperature range of wide usable
temperature range a nematic phase 2 small viscosity.sup.1) short
response time 3 suitable optical anisotropy large contrast ratio 4
large positive or negative low threshold voltage and small
dielectric anisotropy electric power consumption large contrast
ratio 5 large specific resistance large voltage holding ratio and
large contrast ratio 6 high stability to ultraviolet long service
life light and heat .sup.1)A liquid crystal composition can be
injected into a liquid crystal cell in a shorter period of
time.
An optical anisotropy of the composition relates to a contrast
ratio in the device. A product (.DELTA.n.times.d) of the optical
anisotropy (.DELTA.n) of the composition and a cell gap (d) in the
device is designed so as to maximize the contrast ratio. A suitable
value of the product depends on a type of the operating mode. The
suitable value is in the range of 0.30 micrometer to 0.40
micrometer in a device having the VA mode or the PSA mode, and in
the range of 0.20 micrometer to 0.30 micrometer in a device having
the IPS mode. In the above case, a composition having a large
optical anisotropy is preferred for a device having a small cell
gap. A large absolute value of a dielectric anisotropy in the
composition contributes to a low threshold voltage, a small
electric power consumption and a large contrast ratio in the
device. Accordingly, the large absolute value of the dielectric
anisotropy is preferred. A large specific resistance in the
composition contributes to a large voltage holding ratio and a
large contrast ratio in the device. Accordingly, a composition
having a large specific resistance, at room temperature and also at
a high temperature in an initial stage, is preferred. A composition
having a large specific resistance, at room temperature and also at
a high temperature after using the device for a long time, is
preferred. Stability of the composition to ultraviolet light and
heat relates to a service life of the liquid crystal display
device. In the case where the stability is high, the device has a
long service life. Such characteristics are preferred for an AM
device used in a liquid crystal projector, a liquid crystal
television and so forth.
A composition having a positive dielectric anisotropy is used for
an AM device having the TN mode. On the other hand, a composition
having a negative dielectric anisotropy is used for an AM device
having the VA mode. A composition having a positive or negative
dielectric anisotropy is used for an AM device having the IPS mode.
A composition having a positive or negative dielectric anisotropy
is used for an AM device having the PSA mode. Examples of the
liquid crystal composition having the negative dielectric
anisotropy are disclosed in the following patent literatures No. 1
to No. 4.
CITATION LIST
Patent Literature
Patent literature No. 1: JP-A-2003-307720. Patent literature No. 2:
JP-A-2004-131704. Patent literature No. 3: JP-A-2006-133619. Patent
literature No. 4: EP-A-1889894.
A desirable AM device has characteristics such as a wide
temperature range in which a device can be used, a short response
time, a large contrast ratio, a low threshold voltage, a large
voltage holding ratio and a long service life. A shorter response
time even by one millisecond is desirable. Thus, desirable
characteristics of a composition include a high maximum temperature
of a nematic phase, a low minimum temperature of the nematic phase,
a small viscosity, a suitable optical anisotropy, a large positive
or negative dielectric anisotropy, a large specific resistance, a
high stability to ultraviolet light and a high stability to
heat.
SUMMARY OF INVENTION
Technical Problem
One of the aims of the invention is to provide a liquid crystal
composition satisfying at least one of characteristics such as a
high maximum temperature of a nematic phase, a low minimum
temperature of the nematic phase, a small viscosity, a suitable
optical anisotropy, a large negative dielectric anisotropy, a large
specific resistance, a high stability to ultraviolet light and a
high stability to heat. Another aim 1s to provide a liquid crystal
composition having a suitable balance regarding at least two of the
characteristics. A further aim is to provide a liquid crystal
display device containing such a composition. An additional aim 1s
to provide a composition having a suitable optical anisotropy to be
a small optical anisotropy or a large optical anisotropy, a large
negative dielectric anisotropy, a high stability to ultraviolet
light and so forth, and is to provide an AM device having a short
response time, a large voltage holding ratio, a large contrast
ratio, a long service life and so forth.
Solution to Problem
The invention concerns a liquid crystal composition containing at
least one compound selected from the group of compounds represented
by formula (1) as a first component, at least one compound selected
from the group of compounds represented by formula (2) as a second
component and at least one compound selected from the group of
compounds represented by formula (3) as a third component, and
concerns a liquid crystal display device containing the
composition:
##STR00001## wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are
independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12
carbons or alkenyl having 2 to 12 carbons, or alkenyl having 2 to
12 carbons in which arbitrary hydrogen is replaced by fluorine;
R.sup.5 and R.sup.6 are independently alkyl having 1 to 12 carbons,
alkoxy having 1 to 12 carbons or alkenyl having 2 to 12 carbons, or
alkenyl having 2 to 12 carbons in which arbitrary hydrogen is
replaced by fluorine, acrylate, methacrylate, vinyloxy,
propenylether, oxirane, oxetane or vinylketone, and at least one of
R.sup.5 and R.sup.6 is acrylate, methacrylate, vinyloxy,
propenylether, oxirane, oxetane or vinylketone; ring A is
independently 1,4-cyclohexylene or 1,4-phenylene; ring B and ring C
are independently 1,4-cyclohexylene, 1,4-phenylene,
2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene or
2,5-difluoro-1,4-phenylene; ring D and ring E are independently
1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene,
3-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene,
2,5-difluoro-1,4-phenylene, 3,5-difluoro-1,4-phenylene,
2-methyl-1,4-phenylene, 3-methyl-1,4-phenylene or 2,6-naphthalene;
Z.sup.1 is independently a single bond, ethylene, methyleneoxy or
carbonyloxy; Z.sup.2 and Z.sup.3 are independently a single bond,
alkylene having 1 to 12 carbons, or alkylene having 1 to 12 carbons
in which arbitrary --CH.sub.2-- is replaced by --O--; k and j are
independently 1, 2 or 3; and m is 0, 1 or 2.
Advantegeous Effects of Invention
An advantage of the invention is a liquid crystal composition
satisfying at least one of characteristics such as a high maximum
temperature of a nematic phase, a low minimum temperature of the
nematic phase, a small viscosity, a suitable optical anisotropy, a
large negative dielectric anisotropy, a large specific resistance,
a high stability to ultraviolet light and a high stability to heat.
One aspect of the invention is a liquid crystal composition having
a suitable balance regarding at least two of the characteristics.
Another aspect is a liquid crystal display device containing such a
composition. A further aspect is a composition having a suitable
optical anisotropy, a large negative dielectric anisotropy, a high
stability to ultraviolet light and so forth, and is an AM device
having a short response time, a large voltage holding ratio, a
large contrast ratio, a long service life and so forth.
DESCRIPTION OF EMBODIMENTS
Usage of terms in the specification and claims is as described
below. A liquid crystal composition or a liquid crystal display
device of the invention may be abbreviated as "composition" or
"device," respectively. The liquid crystal display device is a
generic term for a liquid crystal display panel and a liquid
crystal display module. "Liquid crystal compound" means a compound
having a liquid crystal phase such as a nematic phase or a smectic
phase, or a compound having no liquid crystal phase but being
useful as a component of the composition. Such a useful compound
has a six-membered ring such as 1,4-cyclohexylene and
1,4-phenylene, and a rod-like molecular structure. An optically
active compound and a polymerizable compound may occasionally be
added to the composition. Even in the case where the compound is
liquid crystalline, the compound is classified as an additive
herein. At least one compound selected from the group of compounds
represented by formula (1) may be abbreviated as "compound (1)."
"Compound (1)" means one compound or two or more compounds
represented by formula (1). A same rule applies to any other
compound represented by any other formula. A term "arbitrary" is
used not only in the case where a position is arbitrary but also in
the case where the number is arbitrary. However, the term is not
used in the case where the number is 0 (zero).
A higher limit of a temperature range of the nematic phase may be
abbreviated as "maximum temperature." A lower limit of the
temperature range of the nematic phase may be abbreviated as
"minimum temperature." An expression "a specific resistance is
large" means that the composition has a large specific resistance
at room temperature and also at a temperature close to the maximum
temperature of the nematic phase in an initial stage, and that the
composition has a large specific resistance at room temperature and
also at a temperature close to the maximum temperature of the
nematic phase even after using the device for a long time. An
expression "a voltage holding ratio is large" means that the device
has a large voltage holding ratio at room temperature and also at a
high temperature in an initial stage, and that the device has a
large voltage holding ratio at room temperature and also at a
temperature close to the maximum temperature of the nematic phase
even after using the device for a long time. When characteristics
such as an optical anisotropy are explained, values obtained
according to the measuring methods described in Examples will be
used. A first component includes one compound or two or more
compounds. A term "a ratio of the first component" is expressed as
weight percent (% by weight) of the first component based on the
weight of the liquid crystal composition excluding a third
component. A same rule applies to a ratio of the second component
and so forth. A ratio of the additive mixed with the composition is
expressed as weight percent (% by weight) or weight parts per
million (ppm) based on the total weight of the liquid crystal
composition.
A symbol R.sup.1 is used for a plurality of compounds in chemical
formulas of component compounds. Meaning of R.sup.1 may be
identical or different in two arbitrary compounds among a plurality
of the compounds. In one case, for example, R.sup.1 of compound
(1-1) is ethyl and R.sup.1 of compound (1-2) is ethyl. In another
case, R.sup.1 of compound (1-1) is ethyl and R.sup.1 of compound
(1-2) is propyl. A same rule applies to a symbol R.sup.2, Z.sup.1
or the like.
The invention includes the items described below. Item 1. A liquid
crystal composition that has a negative dielectric anisotropy and
contains at least one compound selected from the group of compounds
represented by formula (1) as a first component, at least one
compound selected from the group of compounds represented by
formula (2) as a second component and at least one compound
selected from the group of compounds represented by formula (3) as
a third component:
##STR00002## wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are
independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12
carbons or alkenyl having 2 to 12 carbons, or alkenyl having 2 to
12 carbons in which arbitrary hydrogen is replaced by fluorine;
R.sup.5 and R.sup.6 are independently alkyl having 1 to 12 carbons,
alkoxy having 1 to 12 carbons or alkenyl having 2 to 12 carbons, or
alkenyl having 2 to 12 carbons in which arbitrary hydrogen is
replaced by fluorine, acrylate, methacrylate, vinyloxy,
propenylether, oxirane, oxetane or vinylketone, and at least one of
R.sup.5 and R.sup.6 is acrylate, methacrylate, vinyloxy,
propenylether, oxirane, oxetane or vinylketone; ring A is
independently 1,4-cyclohexylene or 1,4-phenylene; ring B and ring C
are independently 1,4-cyclohexylene, 1,4-phenylene,
2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene or
2,5-difluoro-1,4-phenylene; ring D and ring E are independently
1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene,
3-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene,
2,5-difluoro-1,4-phenylene, 3,5-difluoro-1,4-phenylene,
2-methyl-1,4-phenylene, 3-methyl-1,4-phenylene or 2,6-naphthalene;
Z.sup.1 is independently a single bond, ethylene, methyleneoxy or
carbonyloxy; Z.sup.2 and Z.sup.3 are independently a single bond,
alkylene having 1 to 12 carbons, or alkylene having 1 to 12 carbons
in which arbitrary --CH.sub.2-- is replaced by --O--; k and j are
independently 1, 2 or 3; and m is 0, 1 or 2. Item 2. The liquid
crystal composition according to item 1, wherein the first
component is at least one compound selected from the group of
compounds represented by formula (1-1) to formula (1-7):
##STR00003## wherein R.sup.1 and R.sup.2 are independently alkyl
having 1 to 12 carbons, alkoxy having 1 to 12 carbons or alkenyl
having 2 to 12 carbons, or alkenyl having 2 to 12 carbons in which
arbitrary hydrogen is replaced by fluorine. Item 3. The liquid
crystal composition according to item 2, wherein the first
component is at least one compound selected from the group of
compounds represented by formula (1-1). Item 4. The liquid crystal
composition according to item 2, wherein the first component is at
least one compound selected from the group of compounds represented
by formula (1-4). Item 5. The liquid crystal composition according
to item 2, wherein the first component is at least one compound
selected from the group of compounds represented by formula (1-7).
Item 6. The liquid crystal composition according to item 2, wherein
the first component is a mixture of at least one compound selected
from the group of compounds represented by formula (1-1) and at
least one compound selected from the group of compounds represented
by formula (1-4). Item 7. The liquid crystal composition according
to item 2, wherein the first component is a mixture of at least one
compound selected from the group of compounds represented by
formula (1-1) and at least one compound selected from the group of
compounds represented by formula (1-7). Item 8. The liquid crystal
composition according to item 2, wherein the first component is a
mixture of at least one compound selected from the group of
compounds represented by formula (1-1), at least one compound
selected from the group of compounds represented by formula (1-4)
and at least one compound selected from the group of compounds
represented by formula (1-7). Item 9. The liquid crystal
composition according to item 1, wherein the second component is at
least one compound selected from the group of compounds represented
by formula (2-1) to formula (2-12):
##STR00004## ##STR00005## wherein R.sup.3 and R.sup.4 are
independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12
carbons or alkenyl having 2 to 12 carbons, or alkenyl having 2 to
12 carbons in which arbitrary hydrogen is replaced by fluorine.
Item 10. The liquid crystal composition according to item 9,
wherein the second component is at least one compound selected from
the group of compounds represented by formula (2-1). Item 11. The
liquid crystal composition according to item 9, wherein the second
component is a mixture of at least one compound selected from the
group of compounds represented by formula (2-1) and at least one
compound selected from the group of compounds represented by
formula (2-5). Item 12. The liquid crystal composition according to
item 9, wherein the second component is a mixture of at least one
compound selected from the group of compounds represented by
formula (2-1) and at least one compound selected from the group of
compounds represented by formula (2-7). Item 13. The liquid crystal
composition according to item 9, wherein the second component is a
mixture of at least one compound selected from the group of
compounds represented by formula (2-1), at least one compound
selected from the group of compounds represented by formula (2-5)
and at least one compound selected from the group of compounds
represented by formula (2-7). Item 14. The liquid crystal
composition according to any one of items 1 to 13, wherein the
third component is at least one compound selected from the group of
compounds represented by formula (3-1) to formula (3-23):
##STR00006## ##STR00007## ##STR00008## wherein R.sup.5 and R.sup.6
are independently alkyl having 1 to 12 carbons, alkoxy having 1 to
12 carbons or alkenyl having 2 to 12 carbons, or alkenyl having 2
to 12 carbons in which arbitrary hydrogen is replaced by fluorine,
acrylate, methacrylate, vinyloxy, propenylether, oxirane, oxetane
or vinylketone, and at least one of R.sup.5 and R.sup.6 is
acrylate, methacrylate, vinyloxy, propenylether, oxirane, oxetane
or vinylketone; and Z.sup.2 and Z.sup.3 are independently a single
bond, alkylene having 1 to 12 carbons, or alkylene having 1 to 12
carbons in which arbitrary --CH.sub.2-- is replaced by --O--. Item
15. The liquid crystal composition according to item 14, wherein
the third component is at least one compound selected from the
group of compounds represented by formula (3-2). Item 16. The
liquid crystal composition according to item 14, wherein the third
component is at least one compound selected from the group of
compounds represented by formula (3-3). Item 17. The liquid crystal
composition according to item 14, wherein the third component is at
least one compound selected from the group of compounds represented
by formula (3-4). Item 18. The liquid crystal composition according
to item 14, wherein the third component is at least one compound
selected from the group of compounds represented by formula (3-7).
Item 19. The liquid crystal composition according to item 14,
wherein the third component is at least one compound selected from
the group of compounds represented by formula (3-9). Item 20. The
liquid crystal composition according to item 14, wherein the third
component is at least one compound selected from the group of
compounds represented by formula (3-10). Item 21. The liquid
crystal composition according to any one of items 1 to 20, wherein
a ratio of the first component is in the range of 10% by weight to
60% by weight, a ratio of the second component is in the range of
5% by weight to 50% by weight, based on the weight of the liquid
crystal composition excluding the third component, and a ratio of
the third component is in the range of 0.05 part by weight to 10
parts by weight, relative to 100 parts by weight of the liquid
crystal composition excluding the third component. Item 22. The
liquid crystal composition according to any one of items 1 to 21,
further containing at least one compound selected from the group of
compounds represented by formula (4-1) to formula (4-3) as a fourth
component:
##STR00009## wherein R.sup.1 and R.sup.2 are independently alkyl
having 1 to 12 carbons, alkoxy having 1 to 12 carbons or alkenyl
having 2 to 12 carbons, or alkenyl having 2 to 12 carbons in which
arbitrary hydrogen is replaced by fluorine; ring A and ring G are
independently 1,4-cyclohexylene or 1,4-phenylene; ring F is
independently tetrahydropyran-2,5-diyl, 1,4-cyclohexylene,
1,4-phenylene or 2,3-difluoro-1,4-phenylene; Z.sup.1 and Z.sup.4
are independently a single bond, ethylene, methyleneoxy or
carbonyloxy; X.sup.1 and X.sup.2 are fluorine for either one or
chlorine for the other one; X.sup.3 is hydrogen or methyl, and when
X.sup.3 is hydrogen, at least one of ring F is
tetrahydropyran-2,5-diyl or 2,3-difluoro-1,4-phenylene; r and t are
independently 1, 2 or 3; and p and q are independently 0, 1, 2 or
3, and a sum of p and q is 3 or less. Item 23. The liquid crystal
composition according to item 22, wherein the fourth component is
at least one compound selected from the group of compounds
represented by formula (4-1-1) to formula (4-1-3), formula (4-2-1)
to formula (4-2-15) and formula (4-3-1) to formula (4-3-4):
##STR00010## ##STR00011## ##STR00012## wherein R.sup.1 and R.sup.2
are independently alkyl having 1 to 12 carbons, alkoxy having 1 to
12 carbons or alkenyl having 2 to 12 carbons, or alkenyl having 2
to 12 carbons in which arbitrary hydrogen is replaced by fluorine;
ring A.sup.1, ring A.sup.2, ring G.sup.1 and ring G.sup.2 are
independently 1,4-cyclohexylene or 1,4-phenylene; and Z.sup.1 and
Z.sup.4 are independently a single bond, ethylene, methyleneoxy or
carbonyloxy. Item 24. The liquid crystal composition according to
item 23, wherein the fourth component is at least one compound
selected from the group of compounds represented by formula
(4-1-2). Item 25. The liquid crystal composition according to item
23, wherein the fourth component is at least one compound selected
from the group of compounds represented by formula (4-2-1). Item
26. The liquid crystal composition according to item 23, wherein
the fourth component is at least one compound selected from the
group of compounds represented by formula (4-2-4). Item 27. The
liquid crystal composition according to item 23, wherein the fourth
component is at least one compound selected from the group of
compounds represented by formula (4-2-7). Item 28. The liquid
crystal composition according to item 23, wherein the fourth
component is at least one compound selected from the group of
compounds represented by formula (4-2-13). Item 29. The liquid
crystal composition according to item 23, wherein the fourth
component is at least one compound selected from the group of
compounds represented by formula (4-2-14). Item 30. The liquid
crystal composition according to any one of items 22 to 29, wherein
a ratio of the fourth component is in the range of 5% by weight to
50% by weight, based on the weight of the liquid crystal
composition excluding the third component. Item 31. The liquid
crystal composition according to any one of items 1 to 30, further
containing a polymerization initiator. Item 32. The liquid crystal
composition according to any one of items 1 to 31, further
containing a polymerization inhibitor. Item 33. The liquid crystal
composition according to any one of items 1 to 32, wherein a
maximum temperature of a nematic phase is 70.degree. C. or higher,
an optical anisotropy (25.degree. C.) at a wavelength of 589
nanometers is 0.08 or more, and a dielectric anisotropy (25.degree.
C.) at a frequency of 1 kHz is -2 or less. Item 34. A liquid
crystal display device, containing the liquid crystal composition
according to any one of items 1 to 33. Item 35. The liquid crystal
display device according to item 34, wherein an operating mode in
the liquid crystal display device is a VA mode, an IPS mode or a
PSA mode, and a driving mode in the liquid crystal display device
is an active matrix mode.
The invention further includes the following items: (1) the
composition, further containing the optically active compound; (2)
the composition, further containing the additive such as an
antioxidant, an ultraviolet light absorber or an antifoaming agent;
(3) an AM device containing the composition; (4) a device
containing the composition, and having a TN, ECB, OCB, IPS, VA or
PSA mode; (5) a transmissive device, containing the composition;
(6) use of the composition as the composition having the nematic
phase; and (7) use as an optically active composition prepared by
addition of the optically active compound to the composition.
The composition of the invention will be explained in the following
order. First, a constitution of the component compounds in the
composition will be explained. Second, main characteristics of the
component compounds and main effects of the compounds on the
composition will be explained. Third, a combination of components
in the composition, a preferred ratio of the component compounds
and the basis thereof will be explained. Fourth, a preferred
embodiment of the component compounds will be explained. Fifth,
specific examples of the component compounds will be shown. Sixth,
the additive that may be mixed with the composition will be
explained. Seventh, methods for synthesizing the component
compounds will be explained. Last, an application of the
composition will be explained.
First, the constitution of the component compounds in the
composition will be explained. The composition of the invention is
classified into composition A and composition B. Composition A may
further contain any other liquid crystal compound, the additive and
an impurity. "Any other liquid crystal compound" means a liquid
crystal compound different from compound (1), compound (2),
compound (3), compound (4-1), compound (4-2) and compound (4-3).
Such a compound is mixed with the composition for the purpose of
further adjusting the characteristics. Of any other liquid crystal
compounds, a cyano compound is preferred to be small in view of
stability to heat or ultraviolet light. A further preferred ratio
of the cyano compound is 0% by weight. The additive includes the
optically active compound, the antioxidant, the ultraviolet light
absorber, a coloring matter, the antifoaming agent, the
polymerizable compound and the polymerization initiator. The
impurity includes a compound mixed in a process such as preparation
of the component compounds. Even in the case where the compound is
liquid crystalline, the compound is classified as the impurity
herein.
Composition B consists essentially of compounds selected from the
group of compound (1), compound (2), compound (3), compound (4-1),
compound (4-2) and compound (4-3). A term "essentially" means that
the composition may also contain the additive and the impurity, but
does not contain any liquid crystal compound different from the
compounds. Composition B has a smaller number of components than
composition A has. Composition B is preferred to composition A in
view of cost reduction. Composition A is preferred to composition
Bin view of capability of further adjusting physical properties by
mixing any other liquid crystal compound.
Second, the main characteristics of the component compounds and the
main effects of the compounds on the characteristics of the
composition will be explained. The main characteristics of the
component compounds are summarized in Table 2 on the basis of
advantageous effects of the invention. In Table 2, a symbol L
stands for "large" or "high," a symbol M stands for "medium," and a
symbol S stands for "small" or "low." The symbols L, M and S are
classified according to a qualitative comparison among the
component compounds, and 0 (zero) means that "a value is nearly
zero."
TABLE-US-00002 TABLE 2 Characteristics of Compounds Compound
Compound (4-1) Compound Compound Compound (4-2) (1) (2) Compound
(4-3) Maximum Temerature S-L S-L S-L Viscosity M S-M M-L Optical
Anisotropy M-L S-L M-L Dielectric Anisotropy S-L.sup.1) 0
M-L.sup.1) Specific Resistance L L L .sup.1)A value of the
dielectric anisotropy is negative, and the symbol shows small and
large of an absolute value.
Upon mixing the component compounds with the composition, the main
effects of the component compounds on the characteristics of the
composition are as described below. Compound (1) increases an
absolute value of the dielectric anisotropy and decreases the
minimum temperature. Compound (2) decreases the viscosity or
increases the maximum temperature. Compound (4-1), compound (4-2)
and compound (4-3) increase the absolute value of the dielectric
anisotropy.
Third, the combination of the components in the composition, the
preferred ratio of the component compounds and the basis thereof
will be explained. The combination of the components in the
composition includes a combination of the first component, the
second component and the third component, and a combination of the
first component, the second component, the third component and the
fourth component.
A preferred ratio of the first component is 10% by weight or more
for increasing the absolute value of the dielectric anisotropy, and
60% by weight or less for decreasing the minimum temperature. A
further preferred ratio is in the range of 10% by weight to 55% by
weight. A particularly preferred ratio is in the range of 15% by
weight to 50% by weight.
A preferred ratio of the second component is 5% by weight or more
for decreasing the viscosity or increasing the maximum temperature,
and 50% by weight or less for increasing the absolute value of the
dielectric anisotropy. A further preferred ratio is in the range of
10% by weight to 45% by weight. A particularly preferred ratio is
in the range of 10% by weight to 40% by weight.
A preferred ratio of the third component is 0.05 part by weight or
more for achieving the effect thereof, and 10 parts by weight or
less for preventing a poor display, relative to 100 parts by weight
of the liquid crystal composition excluding the third component. A
further preferred ratio is in the range of 0.1 part by weight to 2
parts by weight.
A preferred ratio of the fourth component is 5% by weight or more
for increasing the absolute value of the dielectric anisotropy, and
50% by weight or less for decreasing the viscosity. A further
preferred ratio is in the range of 5% by weight to 45% by weight. A
particularly preferred ratio is in the range of 5% by weight to 40%
by weight.
Fourth, the preferred embodiment of the component compounds will be
explained. R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are independently
alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or
alkenyl having 2 to 12 carbons, or alkenyl having 2 to 12 carbons
in which arbitrary hydrogen is replaced by fluorine. Preferred
R.sup.1 or R.sup.2 is alkyl having 1 to 12 carbons for increasing
the stability to ultraviolet light or heat, or the like, or alkyoxy
having 1 to 12 carbons for increasing the absolute value of the
dielectric anisotropy. Preferred R.sup.3 or R.sup.4 is alkyl having
1 to 12 carbons for increasing the stability to ultraviolet light
or heat, or the like, or alkenyl having 2 to 12 carbons for
decreasing the minimum temperature. R.sup.5 and R.sup.6 are
independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12
carbons or alkenyl having 2 to 12 carbons, or alkenyl having 2 to
12 carbons in which arbitrary hydrogen is replaced by fluorine,
acrylate, methacrylate, vinyloxy, propenylether, oxirane, oxetane
or vinylketone, and at least one of R.sup.5 and R.sup.6 is
acrylate, methacrylate, vinyloxy, propenylether, oxirane, oxetane
or vinylketone. Preferred R.sup.5 or R.sup.6 is acrylate or
methacrylate.
Preferred alkyl is methyl, ethyl, propyl, butyl, pentyl, hexyl,
heptyl or octyl. Further preferred alkyl is ethyl, propyl, butyl,
pentyl or heptyl for decreasing the viscosity.
Preferred alkoxy is methoxy, ethoxy, propoxy, butoxy, pentyloxy,
hexyloxy or heptyloxy. Further preferred alkoxy is methoxy or
ethoxy for decreasing the viscosity.
Preferred alkenyl is vinyl, 1-propenyl, 2-propenyl, 1-butenyl,
2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl,
4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl or
5-hexenyl. Further preferred alkenyl is vinyl, 1-propenyl,
3-butenyl or 3-pentenyl for decreasing the viscosity. A preferred
configuration of --CH.dbd.CH-- in the alkenyl depends on a position
of a double bond. Trans is preferred in the alkenyl such as
1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl and
3-hexenyl for decreasing the viscosity, for instance. Cis preferred
in the alkenyl such as 2-butenyl, 2-pentenyl and 2-hexenyl. In the
alkenyl, straight-chain alkenyl is preferred to branched-chain
alkenyl.
Preferred examples of alkenyl in which arbitrary hydrogen is
replaced by fluorine include 2,2-difluorovinyl,
3,3-difluoro-2-propenyl, 4,4-difluoro-3-butenyl,
5,5-difluoro-4-pentenyl and 6,6-difluoro-5-hexenyl. Further
preferred examples include 2,2-difluorovinyl or
4,4-difluoro-3-butenyl for decreasing the viscosity.
Ring A and ring G are independently 1,4-cyclohexylene or
1,4-phenylene, and arbitrary two of ring A when k, r or p is 2 or 3
may be identical or different, and arbitrary two of ring G when q
is 2 or 3 may be identical or different. Preferred ring A or ring G
is 1,4-cyclohexylene for decreasing the viscosity. Ring B and ring
C are independently 1,4-cyclohexylene, 1,4-phenylene,
2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene or
2,5-difluoro-1,4-phenylene, and arbitrary two of ring B when j is 2
or 3 may be identical or different. Preferred ring B or ring C is
1,4-cyclohexylene for decreasing the viscosity. Ring D and ring E
are independently 1,4-cyclohexylene, 1,4-phenylene,
2-fluoro-1,4-phenylene, 3 -fluoro-1,4-phenylene,
2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene,
3,5-difluoro-1,4-phenylene, 2-methyl-1,4-phenylene,
3-methyl-1,4-phenylene or 2,6-naphthalene, and two of ring D when m
is 2 may be identical or different. Preferred ring D or ring E is
1,4-phenylene for increasing the optical anisotropy. Ring F is
tetrahydropyran-2,5-diyl, 1,4-cyclohexylene, 1,4-phenylene or
2,3-difluoro-1,4-phenylene, and arbitrary two of ring F when t is 2
or 3 may be identical or different. Preferred ring F is
tetrahydropyran-2,5-diyl for increasing the absolute value of the
dielectric anisotropy. Tetrahydropyran-2,5-diyl is:
##STR00013## preferably,
##STR00014##
Z.sup.1 and Z.sup.4 are independently a single bond, ethylene,
methyleneoxy or carbonyloxy, arbitrary two of Z.sup.1 when k, j, r,
t or p is 2 or 3 may be identical or different, two of Z.sup.1 when
m is 2 may be identical or different, and arbitrary two of Z.sup.4
when q is 2 or 3 may be identical or different. Preferred Z.sup.1
is a single bond for decreasing the viscosity, and methyleneoxy for
increasing the absolute value of the dielectric anisotropy.
Preferred Z.sup.4 each is a single bond for decreasing the
viscosity. Z.sup.2 and Z.sup.3 are independently a single bond,
alkylene having 1 to 12 carbons, or alkylene having 1 to 12 carbons
in which arbitrary --CH.sub.2-- is replaced by --O--. Preferred
Z.sup.2 or Z.sup.3 is a single bond for decreasing the
viscosity.
X.sup.1 and X.sup.2 are fluorine for either one or chlorine for the
other one. As for preferred X.sup.1 and X.sup.2, X.sup.1 is
fluorine and X.sup.2 is chlorine for decreasing the minimum
temperature. X.sup.3 is hydrogen or methyl, and when X.sup.3 is
hydrogen, at least one of ring F is tetrahydropyran-2,5-diyl or
2,3-difluoro-1,4-phenylene. Preferred X.sup.1 is hydrogen for
increasing the absolute value of the dielectric anisotropy.
Then, k, j, r and t are independently 1, 2 or 3. Preferred k is 1
for increasing the absolute value of the dielectric anisotropy.
Preferred j is 1 for decreasing the viscosity. Preferred r and t
each are 2 for decreasing the minimum temperature. Then m is 0, 1
or 2. Preferred m is 1 for decreasing the minimum temperature.
Thus, p and q are independently 1, 2 or 3, and a sum of p and q is
3 or less. Preferred p is 2 for increasing the maximum temperature.
Preferred q is 0 for decreasing the minimum temperature.
Fifth, the specific examples of the component compounds will be
shown. In the preferred compounds described below, R.sup.7 is
straight-chain alkyl having 1 to 12 carbons or straight-chain
alkoxy having 1 to 12 carbons. R.sup.8 and R.sup.9 are
independently straight-chain alkyl having 1 to 12 carbons or
straight-chain alkenyl having 2 to 12 carbons. Z.sup.2 and Z.sup.3
are independently a single bond, alkylene having 1 to 12 carbons,
or alkylene having 1 to 12 carbons in which arbitrary --CH.sub.2--
is replaced by --O--. With regard to a configuration of
1,4-cyclohexylene in the compounds, trans is preferred to cis for
increasing the maximum temperature. R.sup.10 and R.sup.11 are
independently acrylate or methacrylate.
Preferred compound (1) includes compound (1-1-1) to compound
(1-7-1). Further preferred compound (1) includes compound (1-1-1),
compound (1-3-1), compound (1-4-1), compound (1-6-1) and compound
(1-7-1). Particularly preferred compound (1) includes compound
(1-1-1), compound (1-4-1) and compound (1-7-1). Preferred compound
(2) includes compound (2-1-1) to compound (2-12-1). Further
preferred compound (2) includes compound (2-1-1), compound (2-3-1),
compound (2-5-1), compound (2-7-1), compound (2-8-1), compound
(2-9-1) and compound (2-12-1). Particularly preferred compound (2)
includes compound (2-1-1), compound (2-5-1), compound (2-7-1) and
compound (2-12-1). Preferred compound (3) includes compound (3-1-1)
to compound (3-23-1). Further preferred compound (3) includes
compound (3-2-1), compound (3-3-1), compound (3-4-1), compound
(3-5-1), compound (3-6-1), compound (3-7-1), compound (3-8-1),
compound (3-9-1), compound (3-10-1), compound (3-11-1) and compound
(3-19-1). Particularly preferred compound (3) includes compound
(3-2-1), compound (3-6-1), compound (3-7-1), compound (3-8-1),
compound (3-9-1) and compound (3-10-1). Preferred compound (4-1)
includes compound (4-1-1-1) to compound (4-1-3-1). Further
preferred compound (4-1) includes compound (4-1-2-1). Preferred
compound (4-2) includes compound (4-2-1-1) to compound (4-2-15-1).
Further preferred compound (4-2) includes compound (4-2-1-1),
compound (4-2-3-1), compound (4-2-5-1), compound (4-2-6-1),
compound (4-2-7-1), compound (4-2-13-1), compound (4-2-14-1) and
compound (4-2-15-1). Particularly preferred compound (4-2) includes
compound (4-2-1-1), compound (4-2-5-1) and compound (4-2-7-1).
Preferred compound (4-3) includes compound (4-3-1-1) to compound
(4-3-1-4), compound (4-3-2-1) to compound (4-3-2-2), compound
(4-3-3-1) to compound (4-3-3-5) and compound (4-3-4-1) to compound
(4-3-4-2). Further preferred compound (4-3) includes compound
(4-3-1-1), compound (4-3-1-3), compound (4-3-3-1), compound
(4-3-3-3) and compound (4-3-4-1). Particularly preferred compound
(4-3) includes compound (4-3-1-3) and compound
##STR00015## ##STR00016## ##STR00017## ##STR00018## ##STR00019##
##STR00020## ##STR00021## ##STR00022## ##STR00023##
Sixth, the additive that may be mixed with the composition will be
explained. Such an additive includes the optically active compound,
the antioxidant, the ultraviolet light absorber, the coloring
matter, the antifoaming agent, the polymerization initiator and the
polymerization inhibitor. The optically active compound is mixed
with the composition for the purpose of inducing a helical
structure and giving a twist angle in liquid crystals. Examples of
such a compound include compound (5-1) to compound (5-4). A
preferred ratio of the optically active compound is 5% by weight or
less, and a further preferred ratio is in the range of 0.01% by
weight to 2% by weight.
##STR00024##
The antioxidant is mixed with the composition for the purpose of
preventing a decrease in specific resistance caused by heating in
air, or maintaining a large voltage holding ratio at room
temperature and also at a high temperature after using the device
for a long time.
##STR00025##
Preferred examples of the antioxidant include compound (6) where n
is an integer from 1 to 9. In compound (6), preferred n is 1, 3, 5,
7 or 9. Further preferred n is 1 or 7. Compound (6) where n is 1 is
effective in preventing a decrease in specific resistance caused by
heating in air because the compound (6) has a large volatility.
Compound (6) where n is 7 is effective in maintaining a large
voltage holding ratio at room temperature and also at a high
temperature after using the device for a long time because the
compound (6) has a small volatility. A preferred ratio of the
antioxidant is 50 ppm or more for achieving the effect thereof, and
600 ppm or less for avoiding a decrease in maximum temperature or
avoiding an increase in minimum temperature. A further preferred
ratio is in the range of 100 ppm to 300 ppm.
Preferred examples of the ultraviolet light absorber include a
benzophenone derivative, a benzoate derivative and a triazole
derivative. A light stabilizer such as an amine having steric
hindrance is also preferred. A preferred ratio of the ultraviolet
light absorber or the stabilizer is 50 ppm or more for achieving
the effect thereof, and 10,000 ppm or less for avoiding a decrease
in maximum temperature or avoiding an increase in minimum
temperature. A further preferred ratio is in the range of 100 ppm
to 10,000 ppm.
A dichroic dye such as an azo dye or an anthraquinone dye is mixed
with the composition to be adapted for a device having a guest host
(GH) mode. A preferred ratio of the coloring matter is in the range
of 0.01% by weight to 10% by weight.
The antifoaming agent such as dimethyl silicone oil or methyl
phenyl silicone oil is mixed with the composition for preventing
foam formation. A preferred ratio of the antifoaming agent is 1 ppm
or more for achieving the effect thereof, and 1,000 ppm or less for
avoiding a poor display. A further preferred ratio is in the range
of 1 ppm to 500 ppm.
As a substance that easily generates a radical or ion, and is
necessary for initiating a chain polymerization reaction, the
polymerization initiator is mixed. For example, Irgacure 651
(registered trademark), Irgacure 184 (registered trademark) or
Darocure 1173 (registered trademark) (Ciba Japan K. K.), each being
the photopolymerization initiator, is suitable for radical
polymerization. The polymerizable compound includes the
photopolymerization initiator, preferably, in the range of 0.1% by
weight to 5% by weight, and particularly preferably, in the range
of 1% by weight to 3% by weight.
In a radical polymerization system, the polymerization inhibitor is
mixed for the purpose of quickly reacting with the radial generated
from the polymerization initiator or a monomer to change into a
stable radical or a neutral compound, as a result, to terminate the
polymerization reaction. The polymerization inhibitor is
structurally classified into two forms. One of the forms is a
radical that is stable in itself, such as tri-p-nitrophenylmethyl
or di-p-fluorophenylamine, and the other is a compound that easily
reacts with the radical present in a polymerization system to
change into the stable radical, such as a nitro, nitroso, amino or
polyhydroxy compound as the representative thereof. A preferred
ratio of the polymerization inhibitor is 5 ppm or more for
achieving the effect thereof and 1,000 ppm or less for avoiding a
poor display. A further preferred ratio is in the range of 5 ppm to
500 ppm.
Seventh, the methods for synthesizing the component compounds will
be explained. The compounds can be prepared according to known
methods. The methods for synthesizing the compounds will be
exemplified. Compound (1-4-1) is prepared by the method described
in JP-A-H02-503441 (1990). Compound (2-1-1) and compound (2-5-1)
are prepared by the method described in JP-A-S59-176221 (1984).
Compound (3-18-1) is prepared by the method described in
JP-A-H07-101900 (1995). Compound (4-3-2-1) is prepared by the
method described in JP-A-2005-35986. The antioxidant is
commercially available. Compound (6) represented by formula (6)
where n is 1 is available from Sigma-Aldrich Corporation. Compound
(6) where n is 7 and so forth is prepared according to the method
described in U.S. Pat. No. 3,660,505.
Any compounds whose synthetic methods are not described above can
be prepared according to the methods described in books such as
Organic Syntheses (John Wiley & Sons, Inc.), Organic Reactions
(John Wiley & Sons, Inc.), Comprehensive Organic Synthesis
(Pergamon Press), New Experimental Chemistry Course (Shin Jikken
Kagaku Koza in Japanese) (Maruzen Co., Ltd.). The composition is
prepared according to known methods using the compounds thus
obtained. For example, the component compounds are mixed and
dissolved in each other by heating.
Last, the application of the composition will be explained. Most of
the compositions have a minimum temperature of -10.degree. C. or
lower, a maximum temperature of 70.degree. C. or higher, and an
optical anisotropy in the range of 0.07 to 0.20. The device
containing the composition has a large voltage holding ratio. The
composition is suitable for use in the AM device. The composition
is particularly suitable for use in a transmissive AM device. The
composition having an optical anisotropy in the range of 0.08 to
0.25 may be prepared by adjusting the ratio of the component
compounds or by mixing with any other liquid crystal compound. The
composition can be used as the composition having the nematic phase
and as the optically active composition by adding the optically
active compound.
The composition can be used for the AM device, and also for a PM
device. The composition can also be used for an AM device and a PM
device having a mode such as PC, TN, STN, ECB, OCB, IPS, VA or PSA.
Use for the AM device having the PSA mode is particularly
preferred. The device may be of a reflective type, a transmissive
type or a transreflective type. Use for the transmissive device is
preferred. The composition can be also used for an amorphous
silicon-TFT device or a polycrystal silicon-TFT device. The
composition can be also used for a nematic curvilinear aligned
phase (NCAP) device prepared by microencapsulating the composition,
and for a polymer dispersed (PD) device in which a
three-dimensional network-polymer is formed in the composition.
EXAMPLES
In order to evaluate characteristics of a composition and a
compound to be contained in the composition, the composition and
the compound were made as a measurement object. When the
measurement object was the composition, the measurement object was
measured as is, and values obtained were described. When the
measurement object was the compound, a sample for measurement was
prepared by mixing the compound (15% by weight) into mother liquid
crystals (85% by weight). Characteristic values of the compound
were calculated from values obtained by measurement, according to
an extrapolation method: (extrapolated value)=[(measured value of a
sample for measurement)-0.85.times.(measured value of mother liquid
crystals)]/0.15. When a smectic phase (or crystals) precipitated at
the ratio thereof at 25.degree. C., a ratio of the compound to the
mother liquid crystals was changed step by step in the order of
(10% by weight:90% by weight), (5% by weight:95% by weight) and (1%
by weight:99% by weight). Values of a maximum temperature, an
optical anisotropy, viscosity and a dielectric anisotropy with
regard to the compound were obtained by the extrapolation
method.
Components of mother liquid crystals and the ratios thereof were as
described below.
##STR00026##
Characteristics were measured according to the methods described
below. Most of the methods are applied as described in EIAJ
ED-2521A of the Standard of Electronic Industries Association of
Japan, or modified thereon.
Maximum Temperature of a Nematic Phase (NI; .degree. C.): A sample
was placed on a hot plate in a melting point apparatus equipped
with a polarizing microscope and was heated at a rate of 1.degree.
C. per minute. A temperature when a part of the sample began to
change from a nematic phase to an isotropic liquid was measured. A
higher limit of a temperature range of the nematic phase may be
abbreviated as "maximum temperature."
Minimum Temperature of a Nematic Phase (T.sub.c; .degree. C.): A
sample having a nematic phase was put in glass vials and kept in
freezers at temperatures of 0.degree. C., -10.degree. C.,
-20.degree. C., -30.degree. C. and -40.degree. C. for 10 days, and
then liquid crystal phases were observed. For example, when the
sample maintained the nematic phase at -20.degree. C. and changed
to crystals or a smectic phase at -30.degree. C., T.sub.c was
expressed as T.sub.c.ltoreq.-20.degree. C. A lower limit of a
temperature range of the nematic phase may be abbreviated as
"minimum temperature."
Viscosity (bulk viscosity; .eta.; measured at 20.degree. C.; mPas):
A cone-plate (E type) viscometer was used for measurement.
Optical Anisotropy (refractive index anisotropy; .DELTA.n; measured
at 25.degree. C.): Measurement was carried out by means of an Abbe
refractometer with a polarizing plate mounted on an ocular, using
light at a wavelength of 589 nanometers. A surface of a main prism
was rubbed in one direction, and then a sample was added dropwise
onto the main prism. A refractive index (n.parallel.) was measured
when the direction of polarized light was parallel to the direction
of rubbing. A refractive index (n.perp.) was measured when the
direction of polarized light was perpendicular to the direction of
rubbing. A value of optical anisotropy was calculated from an
equation: .DELTA.n=n.parallel.-n.perp..
Dielectric Anisotropy (.DELTA..di-elect cons.; measured at
25.degree. C.): A value of dielectric anisotropy was calculated
from an equation: .DELTA..di-elect cons.=.di-elect
cons..parallel.-.di-elect cons..perp.. A dielectric constant
(.di-elect cons..parallel. and .di-elect cons..perp.) was measured
as described below. 1) Measurement of dielectric constant
(.di-elect cons..parallel.): An ethanol (20 mL) solution of
octadecyl triethoxysilane (0.16 mL) was applied to a well-washed
glass substrate. After rotating the glass substrate with a spinner,
the glass substrate was heated at 150.degree. C. for 1 hour. A
sample was put in a VA device in which a distance (cell gap)
between two glass substrates was 4 micrometers, and the device was
sealed with an ultraviolet-curable adhesive. Sine waves (0.5 V, 1
kHz) were applied to the device, and after 2 seconds, a dielectric
constant (.di-elect cons..parallel.) in the major axis direction of
liquid crystal molecules was measured. 2) Measurement of dielectric
constant (.di-elect cons..perp.): A polyimide solution was applied
to a well-washed glass substrate. After calcining the glass
substrate, rubbing treatment was applied to the alignment film
obtained. A sample was put in a TN device in which a distance (cell
gap) between two glass substrates was 9 micrometers and a twist
angle was 80 degrees. Sine waves (0.5V, 1 kHz) were applied to the
device, and after 2 seconds a dielectric constant (.di-elect
cons..perp.) in the minor axis direction of the liquid crystal
molecules was measured.
Threshold Voltage (Vth; measured at 25.degree. C.; V): An LCD-5100
luminance meter made by Otsuka Electronics Co., Ltd. was used for
measurement. A light source was a halogen lamp. A sample was put in
a VA device having a normally black mode, in which a distance (cell
gap) between two glass substrates was 4 micrometers and a rubbing
direction was anti-parallel, and the device was sealed with an
ultraviolet-curable adhesive. A voltage to be applied to the device
(60 Hz, rectangular waves) was stepwise increased from 0 V to 20 V
at an increment of 0.02 V. On the occasion, the device was
irradiated with light in a perpendicular direction, and the amount
of light passing through the device was measured. A
voltage-transmittance curve was prepared, in which the maximum
amount of light corresponds to 100% transmittance and the minimum
amount of light corresponds to 0% transmittance. A threshold
voltage is a voltage at 10% transmittance.
Voltage Holding Ratio (VHR-1; measured at 25.degree. C.; %): A TN
device used for measurement had a polyimide-alignment film, and a
distance (cell gap) between two glass substrates was 5 micrometers.
A sample was put in the device, and then the device was sealed with
an ultraviolet-curable adhesive. A pulse voltage (60 microseconds
at 5 V) was applied to the TN device and the device was charged. A
decreasing voltage was measured for 16.7 milliseconds with a
high-speed voltmeter, and area A between a voltage curve and a
horizontal axis in a unit cycle was obtained. Area B is an area
without a decrease. A voltage holding ratio is a percentage of area
A to area B.
Voltage Holding Ratio (VHR-2; measured at 80.degree. C.; %): A TN
device used for measurement had a polyimide-alignment film, and a
distance (cell gap) between two glass substrates was 5 micrometers.
A sample was put in the device, and then the device was sealed with
an ultraviolet-curable adhesive. A pulse voltage (60 microseconds
at 5 V) was applied to the TN device and the device was charged. A
decreasing voltage was measured for 16.7 milliseconds with a
high-speed voltmeter and area A between a voltage curve and a
horizontal axis in a unit cycle was obtained. Area B is an area
without a decrease. A voltage holding ratio is a percentage of area
A to area B.
Voltage Holding Ratio (VHR-3; measured at 25.degree. C.; %):
Stability to ultraviolet light was evaluated by measuring a voltage
holding ratio after irradiation with ultraviolet light. A
composition having a large VHR-3 has a high stability to
ultraviolet light. A TN device used for measurement had a
polyimide-alignment film and a cell gap was 5 micrometers. A sample
was poured into the device, and then the device was irradiated with
light for 20 minutes. A light source was an ultra high-pressure
mercury lamp USH-500D (made by Ushio, Inc.), and a distance between
the device and the light source was 20 centimeters. In measuring
VHR-3, a decreasing voltage was measured for 16.7 milliseconds. A
value of VHR-3 is, preferably, in the range of 90% or more, and
further preferably, 95% or more.
Voltage Holding Ratio (VHR-4; measured at 25.degree. C.; %): A TN
device into which a sample was poured was heated in a
constant-temperature bath at 80.degree. C. for 500 hours, and then
stability to heat was evaluated by measuring a voltage holding
ratio. A composition having a large VHR-4 has a high stability to
heat. In measuring VHR-4, a decreasing voltage was measured for
16.7 milliseconds.
Response Time (.tau.; measured at 25.degree. C.; millisecond): An
LCD-5100 luminance meter made by Otsuka Electronics Co., Ltd. was
used for measurement. A light source was a halogen lamp. A low-pass
filter was set at 5 kHz. A sample was put in a PVA device having a
normally black mode, in which a cell gap between two glass
substrates was 3.2 micrometers and a rubbing direction was
anti-parallel. The device was sealed with an ultraviolet-curable
adhesive. A voltage just over a threshold voltage was applied to
the device for about one minute, next, while applying a voltage of
5.6 V, the device was irradiated with ultraviolet light at 23.5
mW/cm.sup.2 for about 8 minutes. Rectangular waves (60 Hz, 10 V,
0.5 second) were applied to the device. On the occasion, the device
was irradiated with light in a perpendicular direction, and the
amount of light passing through the device was measured. The
maximum amount of light corresponds to 100% transmittance, and the
minimum amount of light corresponds to 0% transmittance. A response
time is time required for a change from 0% transmittance to 90%
transmittance (rise time; millisecond).
Specific Resistance (.rho.; measured at 25.degree. C.; .OMEGA.cm):
A sample of 1.0 milliliter was put in a vessel equipped with
electrodes. A DC voltage (10V) was applied to the vessel, and a DC
current after 10 seconds was measured. A specific resistance was
calculated from the following equation: (specific
resistance)=[(voltage).times.(electric capacity of vessel)]/[(DC
current).times.(dielectric constant in vacuum)].
Gas Chromatographic Analysis: GC-14B gas chromatograph made by
Shimadzu Corporation was used for measurement. A carrier gas was
helium (2 mL per minute). A sample injector and a detector (FID)
were set to 280.degree. C. and 300.degree. C., respectively. A
capillary column DB-1 (length 30 m, bore 0.32 mm, film thickness
0.25 .mu.m; dimethylpolysiloxane as a stationary phase, non-polar)
made by Agilent Technologies, Inc. was used for separation of
component compounds. After the column was kept at 200.degree. C.
for 2 minutes, the column was further heated to 280.degree. C. at a
rate of 5.degree. C. per minute. A sample was dissolved in an
acetone solution (0.1% by weight), and then 1 microliter of the
solution was injected into the sample injector. A recorder used was
C-R5A Chromatopac made by Shimadzu Corporation or the equivalent
thereof. The resulting gas chromatogram showed a retention time of
a peak and a peak area corresponding to each of the component
compounds.
As a solvent for diluting a sample, chloroform, hexane and so forth
may also be used. The following capillary columns may also be used
for separating component compounds: HP-1 (length 30 m, bore 0.32
mm, film thickness 0.25 .mu.m) made by Agilent Technologies Inc.,
Rtx-1 (length 30 m, bore 0.32 mm, film thickness 0.25 .mu.m) made
by Restek Corporation, and BP-1 (length 30 m, bore 0.32 mm, film
thickness 0.25 .mu.m) made by SGE International Pty. Ltd. A
capillary column CBP1-M50-025 (length 50 m, bore 0.25 mm, film
thickness 0.25 .mu.m) made by Shimadzu Corporation may also be used
for the purpose of avoiding an overlap of peaks of the
compounds.
A ratio of liquid crystal compounds included in a composition may
be calculated according to the method described below. The liquid
crystal compounds can be detected by means of a gas chromatograph.
A ratio of peak areas in the gas chromatogram corresponds to a
ratio (in the number of moles) of the liquid crystal compounds.
When the capillary columns described above were used, a correction
coefficient of each of the liquid crystal compounds may be regarded
as 1 (one). Accordingly, a ratio (% by weight) of the liquid
crystal compounds was calculated from the ratio of the peak
areas.
The invention will be explained in detail by way of Examples. The
invention is not limited by the Examples described below. The
compounds described in Comparative Example and Examples were
expressed as symbols according to definitions in Table 3 below. In
Table 3, a configuration of 1,4-cyclohexylene is trans. A
parenthesized number next to a symbolized compound in Examples
corresponds to the number of the compound. A symbol (-) means any
other liquid crystal compound. A ratio (percentage) of liquid
crystal compounds means weight percent (% by weight) based on the
total weight of the liquid crystal composition. The liquid crystal
composition further includes an impurity in addition thereto. Last,
the characteristic values of the composition were summarized.
TABLE-US-00003 TABLE 3 Method for Description of Compounds using
Symbols R--(A.sub.1)--Z.sub.1 . . . --Z.sub.n--(A.sub.n)--R' 1)
Left-terminal Group R-- Symbol C.sub.nH.sub.2n+1-- n-
C.sub.nH.sub.2n+1O-- nO-- C.sub.mH.sub.2m+1OC.sub.nH.sub.2n-- mOn-
CH.sub.2.dbd.CH-- V-- C.sub.nH.sub.2n+1--CH.dbd.CH-- nV--
CH.sub.2.dbd.CH--C.sub.nH.sub.2n-- Vn-
C.sub.mH.sub.2m+1--CH.dbd.CH--C.sub.nH.sub.2n-- mVn-
CF.sub.2.dbd.CH-- VFF-- CF.sub.2.dbd.CH--C.sub.nH.sub.2n-- VFFn-
CH.sub.2.dbd.CHCOO-- AC-- CH.sub.2.dbd.C(CH.sub.3)COO-- MAC-- 2)
Right-terminal Group --R' Symbol --C.sub.nH.sub.2n+1 -n
--OC.sub.nH.sub.2n+1 --On --CH.dbd.CH.sub.2 --V
--CH.dbd.CH--C.sub.nH.sub.2n+1 --Vn
--C.sub.nH.sub.2n--CH.dbd.CH.sub.2 -nV --CH.dbd.CF.sub.2 --VFF
--COOCH.sub.3 --EMe --OCOCH.dbd.CH.sub.2 --AC
--OCOC(CH.sub.3).dbd.CH.sub.2 --MAC 3) Bonding Group --Z.sub.n--
Symbol --C.sub.2H.sub.4-- 2 --COO-- E --CH.dbd.CH-- V --C.ident.C--
T --CF.sub.2O-- X --CH.sub.2O-- 1O --SiH.sub.2-- Si 4) Ring
Structure --A.sub.n-- Symbol ##STR00027## H ##STR00028## Dh
##STR00029## B ##STR00030## B(F) ##STR00031## B(2F) ##STR00032##
B(2F,5F) ##STR00033## B(2F,3F) ##STR00034## B(2F,3F,6Me)
##STR00035## B(2F,3Cl) ##STR00036## B(Me) ##STR00037## B(2Me)
##STR00038## Cro(7F,8F) ##STR00039## Np 5) Examples of Description
##STR00040## Example 1 V2-BB(F)B-1 ##STR00041## Example 2
3-HB(2F,3F)-O2 ##STR00042## Example 3 3-HHB-l ##STR00043## Example
4 AC-BB-AC
Comparative Example 1
The composition was a liquid crystal composition that has a
negative dielectric anisotropy and does not contain the third
component of the invention. The components and characteristics of
the composition were as described below.
TABLE-US-00004 V-HB(2F,3F)-O2 (1-1-1) 15% V-HB(2F,3F)-O4 (1-1-1)
10% 2-HBB(2F,3F)-O2 (1-7-1) 1% 3-HBB(2F,3F)-O2 (1-7-1) 10%
5-HBB(2F,3F)-O2 (1-7-1) 10% 2-HH-3 (2-1-1) 27% 3-HB-O2 (2-2-1) 2%
3-HHB-1 (2-5-1) 6% 3-HHB-3 (2-5-1) 5% 3-HHB-O1 (2-5-1) 3%
2-HHB(2F,3Cl)-O2 (4-1-2-1) 2% 3-HHB(2F,3Cl)-O2 (4-1-2-1) 3%
4-HHB(2F,3Cl)-O2 (4-1-2-1) 3% 5-HHB(2F,3Cl)-O2 (4-1-2-1) 3%
NI=74.7.degree. C.; Tc.ltoreq.-20.degree. C.; .DELTA.n=0.090;
.DELTA..di-elect cons.=-2.9; Vth=2.16 V; .tau.=7.7 ms; VHR-1=99.1%;
VHR-2=98.1%; VHR-3=98.1%.
Example 1
TABLE-US-00005 V-HB(2F,3F)-O2 (1-1-1) 15% V-HB(2F,3F)-O4 (1-1-1)
10% 2-HBB(2F,3F)-O2 (1-7-1) 1% 3-HBB(2F,3F)-O2 (1-7-1) 10%
5-HBB(2F,3F)-O2 (1-7-1) 10% 2-HH-3 (2-1-1) 27% 3-HB-O2 (2-2-1) 2%
3-HHB-1 (2-5-1) 6% 3-HHB-3 (2-5-1) 5% 3-HHB-O1 (2-5-1) 3%
2-HHB(2F,3Cl)-O2 (4-1-2-1) 2% 3-HHB(2F,3Cl)-O2 (4-1-2-1) 3%
4-HHB(2F,3Cl)-O2 (4-1-2-1) 3% 5-HHB(2F,3Cl)-O2 (4-1-2-1) 3%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. MAC-BB-MAC (3-2-1) NI=75.2.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.093; .DELTA..di-elect
cons.=-2.9; Vth=2.18 V; .tau.=4.4 ms; VHR-1=99.1%; VHR-2=98.1%.
Example 2
TABLE-US-00006 3-H2B(2F,3F)-O2 (1-2-1) 17% 5-H2B(2F,3F)-O2 (1-2-1)
16% 3-HBB(2F,3F)-O2 (1-7-1) 12% 4-HBB(2F,3F)-O2 (1-7-1) 6%
5-HBB(2F,3F)-O2 (1-7-1) 10% 2-HH-3 (2-1-1) 20% 3-HH-4 (2-1-1) 4%
5-HB-O2 (2-2-1) 4% 3-HHB-1 (2-5-1) 4% 5-HBB(F)B-2 (2-12-1) 7%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. AC-BB-AC (3-2-1) NI=79.0.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.108; .DELTA..di-elect
cons.=-3.1; Vth=2.35 V; .tau.=4.6 ms; VHR-1=99.1%; VHR-2=98.1%.
Example 3
TABLE-US-00007 V-HB(2F,3F)-O2 (1-1-1) 11% V-HB(2F,3F)-O4 (1-1-1)
10% 3-H2B(2F,3F)-O2 (1-2-1) 15% 5-H2B(2F,3F)-O2 (1-2-1) 5%
3-HBB(2F,3F)-O2 (1-7-1) 10% 4-HBB(2F,3F)-O2 (1-7-1) 6%
5-HBB(2F,3F)-O2 (1-7-1) 6% 3-HH-4 (2-1-1) 14% 3-HHB-1 (2-5-1) 4%
3-HHB-3 (2-5-1) 5% 3-HHB-O1 (2-5-1) 3% 5-HBB(F)B-2 (2-12-1) 6%
5-HBB(F)B-3 (2-12-1) 5%
To 100 parts by weight of the composition above, 0.5 part by weight
of the following compound as the third component of the invention
was added. MAC-B-MAC (3-1-1) NI=85.9.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.117; .DELTA..di-elect
cons.=-3.6; Vth=2.20 V; .tau.=5.4 ms; VHR-1=99.0%; VHR-2=98.1%.
Example 4
TABLE-US-00008 V-HB(2F,3F)-O2 (1-1-1) 13% V-HB(2F,3F)-O4 (1-1-1)
13% 3-HBB(2F,3F)-O2 (1-7-1) 10% 4-HBB(2F,3F)-O2 (1-7-1) 6%
5-HBB(2F,3F)-O2 (1-7-1) 8% 2-HH-5 (2-1-1) 8% 3-HH-4 (2-1-1) 14%
5-HB-O2 (2-2-1) 8% 3-HHB-1 (2-5-1) 3% 3-HHB-3 (2-5-1) 4% 3-HHB-O1
(2-5-1) 2% 3-HHEBH-3 (2-9-1) 2% 3-HHEBH-5 (2-9-1) 2% 5-HBB(F)B-2
(2-12-1) 2% 3-HH1OCro(7F,8F)-5 (4-3-3-3) 5%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. AC-BB(2F,3F)-AC (3-5-1) NI=85.1.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.102; .DELTA..di-elect
cons.=-3.2; Vth=2.33 V; .tau.=5.3 ms; VHR-1=99.1%; VHR-2=98.1%.
Example 5
TABLE-US-00009 V-HB(2F,3F)-O2 (1-1-1) 10% V-HB(2F,3F)-O4 (1-1-1)
10% 3-H2B(2F,3F)-O2 (1-2-1) 13% 5-H2B(2F,3F)-O2 (1-2-1) 12%
3-HBB(2F,3F)-O2 (1-7-1) 11% 4-HBB(2F,3F)-O2 (1-7-1) 4%
5-HBB(2F,3F)-O2 (1-7-1) 9% 3-HH-4 (2-1-1) 2% 3-HHEH-3 (2-4-1) 2%
3-HHEH-5 (2-4-1) 2% 4-HHEH-3 (2-4-1) 2% 4-HHEH-5 (2-4-1) 2% 3-HHB-1
(2-5-1) 4% 3-HHB-3 (2-5-1) 7% 3-HHB-O1 (2-5-1) 4% 3-HHEBH-3 (2-9-1)
3% 3-HHEBH-5 (2-9-1) 3%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. MAC-B(2F)B-MAC (3-3-1) NI=91.2.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.108; .DELTA..di-elect
cons.=-4.4; Vth=2.04 V; .tau.=5.8 ms; VHR-1=99.1%; VHR-2=98.0%.
Example 6
TABLE-US-00010 V-HB(2F,3F)-O2 (1-1-1) 11% V-HB(2F,3F)-O4 (1-1-1)
10% 3-HBB(2F,3F)-O2 (1-7-1) 11% 4-HBB(2F,3F)-O2 (1-7-1) 4%
5-HBB(2F,3F)-O2 (1-7-1) 7% 2-HH-3 (2-1-1) 17% 3-HH-4 (2-1-1) 8%
3-HH-5 (2-1-1) 4% 5-HB-O2 (2-2-1) 6% 3-HHB-1 (2-5-1) 5% 3-HHB-3
(2-5-1) 6% 3-HHB-O1 (2-5-1) 3% 3-HH1OCro(7F,8F)-5 (4-3-3-3) 8%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. MAC-B(2Me)B-MAC (3-12-1) NI=79.3.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.093; .DELTA..di-elect
cons.=-2.9; Vth=2.30 V; T=4.1 ms; VHR-1=99.2%; VHR-2=98.2%.
Example 7
TABLE-US-00011 V-HB(2F,3F)-O2 (1-1-1) 13% V-HB(2F,3F)-O4 (1-1-1)
13% 3-HBB(2F,3F)-O2 (1-7-1) 6% 4-HBB(2F,3F)-O2 (1-7-1) 6%
5-HBB(2F,3F)-O2 (1-7-1) 6% 2-HH-3 (2-1-1) 26% 5-HB-O2 (2-2-1) 5%
3-HHB-1 (2-5-1) 4% 3-HHB-3 (2-5-1) 7% 3-HHB-O1 (2-5-1) 4%
5-HBB(F)B-2 (2-12-1) 5% 3-HH1OCro(7F,8F)-5 (4-3-3-3) 5%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. AC-B(F)B-AC (3-4-1) NI=75.1.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.096; .DELTA..di-elect
cons.=-2.7; Vth=2.29 V; .tau.=3.8 ms; VHR-1=99.1%; VHR-2=98.1%.
Example 8
TABLE-US-00012 V-HB(2F,3F)-O2 (1-1-1) 14% V-HB(2F,3F)-O4 (1-1-1)
13% 3-HBB(2F,3F)-O2 (1-7-1) 10% 4-HBB(2F,3F)-O2 (1-7-1) 4%
5-HBB(2F,3F)-O2 (1-7-1) 5% 2-HH-3 (2-1-1) 26% 4-HHEH-3 (2-4-1) 3%
4-HHEH-5 (2-4-1) 3% 3-HHB-1 (2-5-1) 6% 3-HHB-3 (2-5-1) 6% 3-HHB-O1
(2-5-1) 3% 3-HH1OCro(7F,8F)-5 (4-3-3-3) 7%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. AC-B(Me)B-AC (3-13-1) NI=75.2.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.088; .DELTA..di-elect
cons.=-3.1; Vth=2.06 V; .tau.=4.3 ms; VHR-1=99.2%; VHR-2=98.1%.
Example 9
TABLE-US-00013 3-H2B(2F,3F)-O2 (1-2-1) 15% 5-H2B(2F,3F)-O2 (1-2-1)
15% 2-HBB(2F,3F)-O2 (1-7-1) 3% 3-HBB(2F,3F)-O2 (1-7-1) 9%
5-HBB(2F,3F)-O2 (1-7-1) 9% 2-HH-5 (2-1-1) 3% 3-HH-4 (2-1-1) 15%
3-HH-5 (2-1-1) 4% 3-HB-O2 (2-2-1) 12% 3-HHB-1 (2-5-1) 3% 3-HHB-3
(2-5-1) 4% 3-HHB-O1 (2-5-1) 3% 3-HHB(2F,3Cl)-O2 (4-1-2-1) 5%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. MAC-B(2F)B(2F)-MAC (3-6-1) NI=75.7.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.096; .DELTA..di-elect
cons.=-2.8; Vth=2.38 V; .tau.=4.4 ms; VHR-1=99.1%; VHR-2=98.1%.
Example 10
TABLE-US-00014 3-H2B(2F,3F)-O2 (1-2-1) 17% 5-H2B(2F,3F)-O2 (1-2-1)
17% V-HH-3 (2-1-1) 27% V-HHB-1 (2-5-1) 10% 2-BB(F)B-3 (2-7-1) 2%
3-HHB(2F,3Cl)-O2 (4-1-2-1) 4% 4-HHB(2F,3Cl)-O2 (4-1-2-1) 3%
5-HHB(2F,3Cl)-O2 (4-1-2-1) 3% 3-HBB(2F,3Cl)-O2 (4-1-3-1) 8%
5-HBB(2F,3Cl)-O2 (4-1-3-1) 9%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. MAC-B(2Me)B(2Me)-MAC (3-14-1) NI=70.0.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.093; .DELTA..di-elect
cons.=-2.8; Vth=2.33 V; .tau.=4.4 ms; VHR-1=99.2%; VHR-2=98.0%.
Example 11
TABLE-US-00015 V-HB(2F,3F)-O2 (1-1-1) 10% V-HHB(2F,3F)-O2 (1-4-1)
15% V2-HHB(2F,3F)-O2 (1-4-1) 15% V-HH-3 (2-1-1) 25% 1V-HH-3 (2-1-1)
8% V-HHB-1 (2-5-1) 5% 2-BB(F)B-3 (2-7-1) 10% 3-HCro(7F,8F)-5
(4-3-1-1) 3% 2O-Cro(7F,8F)H-3 (4-3-2) 3% 3-HHCro(7F,8F)-5 (4-3-3-1)
3% 2O-Cro(7F,8F)HH-5 (4-3-4) 3%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. MAC-B(2F)B(F)-MAC (3-7-1) NI=76.0.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.094; .DELTA..di-elect
cons.=-3.1; Vth=2.26 V; .tau.=6.0 ms; VHR-1=99.0%; VHR-2=98.3%.
Example 12
TABLE-US-00016 V2-HB(2F,3F)-O2 (1-1-1) 15% V-HBB(2F,3F)-O2 (1-7-1)
12% V-HH-3 (2-1-1) 30% V2-HHB-1 (2-5-1) 10% 3-BB(F)B-2V (2-7-1) 8%
3-H1OCro(7F,8F)-5 (4-3-1-3) 5% 5-H1OCro(7F,8F)-4 (4-3-1-3) 5%
3-HH1OCro(7F,8F)-5 (4-3-3-3) 4% 5-HH1OCro(7F,8F)-5 (4-3-3-3) 6%
3-BBCro(7F,8F)-5 (4-3-3-5) 5%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. MAC-B(2Me)B(Me)-MAC (3-15-1) NI=78.4.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.112; .DELTA..di-elect
cons.=-3.0; Vth=2.30 V; .tau.=6.1 ms; VHR-1=99.1%; VHR-2=98.3%.
Example 13
TABLE-US-00017 V-HB(2F,3F)-O2 (1-1-1) 10% V-HHB(2F,3F)-O2 (1-4-1)
10% 1V-HHB(2F,3F)-O2 (1-4-1) 5% 1V2-HHB(2F,3F)-O2 (1-4-1) 5%
V2-HBB(2F,3F)-O2 (1-7-1) 10% 2-HH-3 (2-1-1) 22% 3-HH-O1 (2-1-1) 3%
7-HB-1 (2-2-1) 5% 3 -HHEH-5 (2-4-1) 3% V-HHB-1 (2-5-1) 7%
V2-BB(F)B-1 (2-7-1) 5% 5-HBB(F)B-3 (2-12-1) 5% 3-H2Cro(7F,8F)-5
(4-3-1-2) 5% 2-Cro(7F,8F)2H-3 (4-3-2-2) 5%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. MAC-B(F)B(2F)-MAC (3-8-1) NI=81.2.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.101; .DELTA..di-elect
cons.=-2.7; Vth=2.43 V; .tau.=4.4 ms; VHR-1=99.2%; VHR-2=98.0%.
Example 14
TABLE-US-00018 3-HB(2F,3F)-O2 (1-1-1) 5% V-HB(2F,3F)-O2 (1-1-1) 11%
V-HB(2F,3F)-O4 (1-1-1) 12% V-HHB(2F,3F)-O2 (1-4-1) 10%
V-HHB(2F,3F)-O4 (1-4-1) 10% 3-HBB(2F,3F)-O2 (1-7-1) 5% V-HH-3
(2-1-1) 25% V2-BB-1 (2-3-1) 6% 1V-HBB-2 (2-6-1) 4% 5-HBBH-3
(2-10-1) 5% 3-BCro(7F,8F)-5 (4-3-1 4) 3% 3-HBCro(7F,8F)-5 (4-3-3-4)
4%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. MAC-B(Me)B(2Me)-MAC (3-16-1) NI=70.1.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.102; .DELTA..di-elect
cons.=-3.1; Vth=2.21 V; .tau.=4.3 ms; VHR-1=99.1%; VHR-2=98.1%.
Example 15
TABLE-US-00019 V-HB(2F,3F)-O2 (1-1-1) 16% 1V-HB(2F,3F)-O4 (1-1-1)
6% 3-H2B(2F,3F)-O2 (1-2-1) 3% 3-HHB(2F,3F)-O2 (1-4-1) 3%
V-HHB(2F,3F)-O2 (1-4-1) 10% V2-HHB(2F,3F)-O2 (1-4-1) 7%
V-HBB(2F,3F)-O2 (1-7-1) 10% V-HH-3 (2-1-1) 20% 1V-HH-3 (2-1-1) 7%
5-HHEBH-3 (2-9-1) 4% 5-HB(F)BH-3 (2-11-1) 4% 3-HH2Cro(7F,8F)-3
(4-3-3-2) 3% 3-HH2Cro(7F,8F)-5 (4-3-3-2) 4% 3-Cro(7F,8F)2HH-5
(4-3-4-2) 3%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. MAC-B(2F)B(2F,3F)-MAC (3-9-1) NI=90.1.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.097; .DELTA..di-elect
cons.=-3.6; Vth=1.92 V; .tau.=5.5 ms; VHR-1=99.0%; VHR-2=98.1%.
Example 16
TABLE-US-00020 V-HB(2F,3F)-O2 (1-1-1) 15% V-HB(2F,3F)-O4 (1-1-1) 7%
3-HBB(2F,3F)-O2 (1-7-1) 3% V-HBB(2F,3F)-O2 (1-7-1) 10%
V2-HBB(2F,3F)-O2 (1-7-1) 10% 2-HH-3 (2-1-1) 29% 3-HHB-1 (2-5-1) 6%
3-HHB-3 (2-5-1) 6% 3-HHB-O1 (2-5-1) 6% 3-HH1OCro(7F,8F)-5 (4-3-3-3)
8%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. MAC-B(F)B(2F,3F)-MAC (3-10-1) NI=80.9.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.094; .DELTA..di-elect
cons.=-3.1; Vth=2.26 V; .tau.=4.7 ms; VHR-1=99.2%; VHR-2=98.3%.
Example 17
TABLE-US-00021 3-HB(2F,3F)-O2 (1-1-1) 5% 5-HB(2F,3F)-O2 (1-1-1) 5%
3-HHB(2F,3F)-O2 (1-4-1) 5% 3-HH2B(2F,3F)-O2 (1-5-1) 7% 3-HH-VFF
(2-1) 3% V-HH-3 (2-1-1) 28% 1V2-BB-1 (2-3-1) 4% 3-HHEH-3 (2-4-1) 3%
V2-BB(F)B-1 (2-7-1) 4% 3-HB(F)HH-5 (2-8-1) 5% 5-HBB(2F,3Cl)-O2
(4-1-3-1) 5% 3-DhBB(2F,3F)-O2 (4-2) 5% 5-DhBB(2F,3F)-O2 (4-2) 4%
3-DhB(2F,3F)-O2 (4-2-1-1) 6% 5-DhB(2F,3F)-O2 (4-2-1-1) 6%
3-DH1OB(2F,3F)-O2 (4-2-3-1) 5%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. AC-B(2F,3F)B(2F,3F)-AC (3-11-1) NI=72.1.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.096; .DELTA..di-elect
cons.=-2.4; .tau.=3.7 ms; VHR-1=99.0%; VHR-2=98.1%.
Example 18
TABLE-US-00022 3-H1OB(2F,3F)-O2 (1-3-1) 5% 5-H1OB(2F,3F)-O2 (1-3-1)
5% 3-HH1OB(2F,3F)-O2 (1-6-1) 5% 5-HH1OB(2F,3F)-O2 (1-6-1) 5%
3-BB(2F,5F)B-2 (2) 3% V-HH-3 (2-1-1) 37% 1V-HH-3 (2-1-1) 6% 3-HHB-1
(2-5-1) 4% 3-HHB-O1 (2-5-1) 4% 5-HBB(2F,3Cl)-O2 (4-1-3-1) 6%
3-DhHB(2F,3F)-O2 (4-2-4-1) 6% 3-HDhB(2F,3F)-O2 (4-2-5-1) 10%
1O1-HBBH-5 (--) 4%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. MAC-BBB-MAC (3-18-1) NI=92.1.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.086; .DELTA..di-elect
cons.=-2.4; .tau.=3.5 ms; VHR-1=99.1%; VHR-2=98.1%.
Example 19
TABLE-US-00023 3-HH1OB(2F,3F)-O2 (1-6-1) 6% 3-HBB(2F,3F)-O2 (1-7-1)
6% 5-HBB(2F,3F)-O2 (1-7-1) 6% V-HH-3 (2-1-1) 32% 1V-HH-3 (2-1-1) 7%
3-HB-O2 (2-2-1) 3% 1V-HBB-2 (2-6-1) 4% 2-BB(F)B-3 (2-7-1) 5%
3-Dh2B(2F,3F)-O2 (4 2-2-1) 9% 3-Dh1OB(2F,3F)-O2 (4-2-3-1) 6%
3-DhH1OB(2F,3F)-O2 (4-2-6-1) 6% 3-H2Cro(7F,8F)-5 (4-3-1-2) 3%
3-H1OCro(7F,8F)-5 (4-3-1-3) 4% 3-HHCro(7F,8F)-5 (4-3-3-1) 3%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. MAC-BB(F)B-MAC (3-19-1) NI=72.0.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.093; .DELTA..di-elect
cons.=-2.9; .tau.=3.6 ms; VHR-1=99.0%; VHR-2=98.1%.
Example 20
TABLE-US-00024 3-HB(2F,3F)-O2 (1-1-1) 5% 5-HB(2F,3F)-O2 (1-1-1) 5%
V-H1OB(2F,3F)-O2 (1-3-1) 4% V2-H1OB(2F,3F)-O2 (1-3-1) 4%
V-HH2B(2F,3F)-O2 (1-5-1) 5% V2-HH2B(2F,3F)-O2 (1-5-1) 5%
3-HH1OB(2F,3F)-O2 (1-6-1) 5% 4-HH1OB(2F,3F)-O2 (1-6-1) 3%
5-HH1OB(2F,3F)-O2 (1-6-1) 5% V-HH-3 (2-1-1) 28% 3-HH-4 (2-1-1) 10%
V2-BB-1 (2-3-1) 4% 5-HBB(F)B-2 (2-12-1) 4% 5-HBB(F)B-3 (2-12-1) 3%
3-HB(2F,3Cl)-O2 (4-1-1-1) 5% 3-HBB(2F,3Cl)-O2 (4-1-3-1) 2%
5-HBB(2F,3Cl)-O2 (4-1-3-1) 3%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. MAC-BB(Me)B-MAC (3-23-1) NI=74.6.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.089; .DELTA..di-elect
cons.=-3.4; .tau.=4.1 ms; VHR-1=99.0%; VHR-2=98.1%.
Example 21
TABLE-US-00025 V-HB(2F,3F)-O2 (1-1-1) 3% 5-HHB(2F,3F)-O2 (1-4-1) 8%
V-HHB(2F,3F)-O2 (1-4-1) 10% V-HHB(2F,3F)-O4 (1-4-1) 4% V-HH-5
(2-1-1) 20% 1V2-BB-1 (2-3-1) 10% V-HHB-1 (2-5-1) 5% V2-BB(F)B-1
(2-7-1) 3% V2-BB(F)B-2 (2-7-1) 7% 5-HBB(F)B-2 (2-12-1) 5%
3-H1OB(2F,3F,6Me)-O2 (4-2-10-1) 5% 5-H1OB(2F,3F,6Me)-O2 (4-2-10-1)
5% 3-HH1OB(2F,3F,6Me)-O2 (4-2-13-1) 5% 5-HH1OB(2F,3F,6Me)-O2
(4-2-13-1) 5% 3-HEB(2F,3F)B(2F,3F)-O2 (4-2-15-1) 5%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. MAC-BB(2F,5F)B-MAC (3-22-1) NI=92.3.degree. C.;
Tc.ltoreq.-30.degree. C.; .DELTA.n=0.132; .DELTA..di-elect
cons.=-3.1; .tau.=5.8 ms; VHR-1=99.1%; VHR-2=98.1%.
Example 22
TABLE-US-00026 2-HBB(2F,3F)-O2 (1-7-1) 5% 3-HBB(2F,3F)-O2 (1-7-1)
12% 5-HBB(2F,3F)-O2 (1-7-1) 4% V-HH-4 (2-1-1) 15% V-HH-5 (2-1-1)
23% 1V-HH-3 (2-1-1) 6% V-HHB-1 (2-5-1) 5% V2-HHB-1 (2-5-1) 3%
3-H2B(2F,3F,6Me)-O2 (4-2-9-1) 4% 3-H1OB(2F,3F,6Me)-O2 (4-2-10-1) 5%
5-H1OB(2F,3F,6Me)-O2 (4-2-10-1) 3% 3-HH2B(2F,3F,6Me)-O2 (4-2-12-1)
5% 3-HH1OB(2F,3F,6Me)-O2 (4-2-13-1) 6% 3-HH1OCro(7F,8F)-5 (4-3-3-3)
4%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. AC-BB(2F,3F)B-AC (3-21-1) NI=85.4.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.093; .DELTA..di-elect
cons.=-2.8; .tau.=5.4 ms; VHR-1=99.2%; VHR-2=98.1%.
Example 23
TABLE-US-00027 3-HB(2F,3F)-O2 (1-1-1) 8% 3-HHB(2F,3F)-O2 (1-4-1)
10% 3-HBB(2F,3F)-O2 (1-7-1) 11% 5-HBB(2F,3F)-O2 (1-7-1) 5% V-HH-3
(2-1-1) 40% 3-HHEBH-3 (2-9-1) 4% 3-HHEBH-4 (2-9-1) 3%
3-HB(2F,3F,6Me)-O2 (4-2-8-1) 4% 3-H2B(2F,3F,6Me)-O2 (4-2-9-1) 4%
3-HHB(2F,3F,6Me)-O2 (4-2-11-1) 5% 3-HH1OB(2F,3F,6Me)-O2 (4-2-13-1)
6%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. MAC-BBB(2F)-MAC (3-20-1) NI=82.9.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.089; .DELTA..di-elect
cons.=-3.0; .tau.=4.3 ms; VHR-1=99.0%; VHR-2=98.1%.
Example 24
TABLE-US-00028 V-HB(2F,3F)-O2 (1-1-1) 12% V-HB(2F,3F)-O4 (1-1-1)
10% 3-H2B(2F,3F)-O2 (1-2-1) 15% 3-HBB(2F,3F)-O2 (1-7-1) 10%
4-HBB(2F,3F)-O2 (1-7-1) 6% 5-HBB(2F,3F)-O2 (1-7-1) 6% 3-HH-4
(2-1-1) 14% 3-HHB-1 (2-5-1) 4% 3-HHB-3 (2-5-1) 5% 3-HHB-O1 (2-5-1)
3% 5-HBB(F)B-2 (2-12-1) 6% 5-HBB(F)B-3 (2-12-1) 5%
4O-B(2F,3F)B(2F,3F)-O6 (4-2-14) 4%
To 100 parts by weight of the composition above, 0.5 part by weight
of the following compound as the third component of the invention
was added. MAC-Np-MAC (3-17-1) NI=85.5.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.119; .DELTA..di-elect
cons.=-3.8; Vth=2.16 V; .tau.=5.7 ms; VHR-1=99.0%; VHR-2=98.0%.
Example 25
TABLE-US-00029 3-H2B(2F,3F)-O2 (1-2-1) 18% 5-H2B(2F,3F)-O2 (1-2-1)
17% 3-HBB(2F,3F)-O2 (1-7-1) 9% 4-HBB(2F,3F)-O2 (1-7-1) 3%
5-HBB(2F,3F)-O2 (1-7-1) 9% 2-HH-3 (2-1-1) 18% 3-HH-4 (2-1-1) 2%
3-HHB-1 (2-5-1) 5% 3-HHB-3 (2-5-1) 5% 3-HHB-O1 (2-5-1) 4%
3-HHB(2F,3Cl)-O2 (4-1-2-1) 4% 4-HHB(2F,3Cl)-O2 (4-1-2-1) 3%
5-HHB(2F,3Cl)-O2 (4-1-2-1) 3%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. MAC-BB-MAC (3-2-1) NI=80.7.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.095; .DELTA..di-elect
cons.=-3.4; .tau.=5.4 ms; VHR-1=99.0%; VHR-2=98.0%.
Example 26
TABLE-US-00030 3-H2B(2F,3F)-O2 (1-2-1) 18% 5-H2B(2F,3F)-O2 (1-2-1)
17% 3-HBB(2F,3F)-O2 (1-7-1) 9% 4-HBB(2F,3F)-O2 (1-7-1) 3%
5-HBB(2F,3F)-O2 (1-7-1) 9% 2-HH-3 (2-1-1) 18% 3-HH-4 (2-1-1) 2%
3-HHB-1 (2-5-1) 5% 3-HHB-3 (2-5-1) 5% 3-HHB-O1 (2-5-1) 4%
3-HHB(2F,3Cl)-O2 (4-1-2-1) 4% 4-HHB(2F,3Cl)-O2 (4-1-2-1) 3%
5-HHB(2F,3Cl)-O2 (4-1-2-1) 3%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. MAC-B(2F)B-MAC (3-3-1) NI=80.5.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.094; .DELTA..di-elect
cons.=-3.5; .tau.=5.3 ms; VHR-1=99.1%; VHR-2=98.1%.
Example 27
TABLE-US-00031 3-H2B(2F,3F)-O2 (1-2-1) 18% 5-H2B(2F,3F)-O2 (1-2-1)
17% 3-HBB(2F,3F)-O2 (1-7-1) 9% 4-HBB(2F,3F)-O2 (1-7-1) 3%
5-HBB(2F,3F)-O2 (1-7-1) 9% 2-HH-3 (2-1-1) 18% 3-HH-4 (2-1-1) 2%
3-HHB-1 (2-5-1) 5% 3-HHB-3 (2-5-1) 5% 3-HHB-O1 (2-5-1) 4%
3-HHB(2F,3Cl)-O2 (4-1-2-1) 4% 4-HHB(2F,3Cl)-O2 (4-1-2-1) 3%
5-HHB(2F,3Cl)-O2 (4-1-2-1) 3%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. MAC-B(F)B-MAC (3-4-1) NI=80.5.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.094; .DELTA..di-elect
cons.=-3.5; .tau.=5.3 ms; VHR-1=99.1%; VHR-2=98.1%.
Example 28
TABLE-US-00032 3-H2B(2F,3F)-O2 (1-2-1) 18% 5-H2B(2F,3F)-O2 (1-2-1)
17% 3-HBB(2F,3F)-O2 (1-7-1) 10% 4-HBB(2F,3F)-O2 (1-7-1) 6%
5-HBB(2F,3F)-O2 (1-7-1) 6% 2-HH-3 (2-1-1) 14% 3-HH-4 (2-1-1) 8%
3-HHB-1 (2-5-1) 5% 3-HHB-3 (2-5-1) 6% 3-HHB-O1 (2-5-1) 4%
3-HH1OCro(7F,8F)-5 (4-3-3-3) 6%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. MAC-BB-MAC (3-2-1) NI=79.4.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.095; .DELTA..di-elect
cons.=-3.4; .tau.=5.4 ms; VHR-1=99.0%; VHR-2=98.0%.
Example 29
TABLE-US-00033 3-H2B(2F,3F)-O2 (1-2-1) 18% 5-H2B(2F,3F)-O2 (1-2-1)
17% 3-HBB(2F,3F)-O2 (1-7-1) 10% 4-HBB(2F,3F)-O2 (1-7-1) 6%
5-HBB(2F,3F)-O2 (1-7-1) 6% 2-HH-3 (2-1-1) 14% 3-HH-4 (2-1-1) 8%
3-HHB-1 (2-5-1) 5% 3-HHB-3 (2-5-1) 6% 3-HHB-O1 (2-5-1) 4%
3-HH1OCro(7F,8F)-5 (4-3-3-3) 6%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. MAC-B(2F)B-MAC (3-3-1) NI=79.1.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.094; .DELTA..di-elect
cons.=-3.5; .tau.=5.3 ms; VHR-1=99.1%; VHR-2=98.2%.
Example 30
TABLE-US-00034 3-H2B(2F,3F)-O (1-2-1) 18% 5-H2B(2F,3F)-O2 (1-2-1)
17% 3-HBB(2F,3F)-O2 (1-7-1) 10% 4-HBB(2F,3F)-O2 (1-7-1) 6%
5-HBB(2F,3F)-O2 (1-7-1) 6% 2-HH-3 (2-1-1) 14% 3-HH-4 (2-1-1) 8%
3-HHB-1 (2-5-1) 5% 3-HHB-3 (2-5-1) 6% 3-HHB-O1 (2-5-1) 4%
3-HH1OCro(7F,8F)-5 (4-3-3-3) 6%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. MAC-B(F)B-MAC (3-4-1) NI=79.1.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.094; .DELTA..di-elect
cons.=-3.5; .tau.=5.3 ms; VHR-1=99.1%; VHR-2=98.2%.
Example 31
TABLE-US-00035 3-H2B(2F,3F)-O2 (1-2-1) 18% 5-H2B(2F,3F)-O2 (1-2-1)
17% 3-HHB(2F,3F)-O2 (1-4-1) 5% 3-HBB(2F,3F)-O2 (1-7-1) 9%
4-HBB(2F,3F)-O2 (1-7-1) 3% 5-HBB(2F,3F)-O2 (1-7-1) 9% 2-HH-3
(2-1-1) 18% 3-HH-4 (2-1-1) 2% 3-HHB-1 (2-5-1) 5% 3-HHB-3 (2-5-1) 5%
3-HHB-O1 (2-5-1) 4% 3-HHB(2F,3Cl)-O2 (4-1-2-1) 3% 5-HHB(2F,3Cl)-O2
(4-1-2-1) 2%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. MAC-B(2F)B-MAC (3-3-1) NI=81.5.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.095; .DELTA..di-elect
cons.=-3.5; .tau.=5.2 ms; VHR-1=99.1%; VHR-2=98.2%.
Example 32
TABLE-US-00036 3-H2B(2F,3F)-O2 (1-2-1) 18% 5-H2B(2F,3F)-O2 (1-2-1)
17% 3-HHB(2F,3F)-O2 (1-4-1) 5% 3-HBB(2F,3F)-O2 (1-7-1) 9%
4-HBB(2F,3F)-O2 (1-7-1) 3% 5-HBB(2F,3F)-O2 (1-7-1) 9% 2-HH-3
(2-1-1) 18% 3-HH-4 (2-1-1) 2% 3-HHB-1 (2-5-1) 5% 3-HHB-3 (2-5-1) 5%
3-HHB-O1 (2-5-1) 4% 3-HHB(2F,3Cl)-O2 (4-1-2-1) 3% 5-HHB(2F,3Cl)-O2
(4-1-2-1) 2%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. MAC-B(F)B-MAC (3-4-1) NI=81.5.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.095; .DELTA..di-elect
cons.=-3.5; .tau.=5.2 ms; VHR-1=99.1%; VHR-2=98.2%.
Example 33
TABLE-US-00037 3-H2B(2F,3F)-O2 (1-2-1) 18% 5-H2B(2F,3F)-O2 (1-2-1)
17% 3-HBB(2F,3F)-O2 (1-7-1) 9% 4-HBB(2F,3F)-O2 (1-7-1) 3%
5-HBB(2F,3F)-O2 (1-7-1) 9% 2-HH-3 (2-1-1) 18% 3-HH-4 (2-1-1) 2%
3-HHB-1 (2-5-1) 5% 3-HHB-3 (2-5-1) 5% 3-HHB-O1 (2-5-1) 4%
3-HHB(2F,3Cl)-O2 (4-1-2-1) 3% 5-HHB(2F,3Cl)-O2 (4-1-2-1) 2%
3-HDhB(2F,3F)-O2 (4-2-5-1) 5%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. MAC-B(2F)B-MAC (3-3-1) NI=80.3.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.094; .DELTA..di-elect
cons.=-3.6; .tau.=5.3 ms; VHR-1=99.1%; VHR-2=98.2%.
Example 34
TABLE-US-00038 3-H2B(2F,3F)-O2 (1-2-1) 18% 5-H2B(2F,3F)-O2 (1-2-1)
17% 3-HBB(2F,3F)-O2 (1-7-1) 9% 4-HBB(2F,3F)-O2 (1-7-1) 3%
5-HBB(2F,3F)-O2 (1-7-1) 9% 2-HH-3 (2-1-1) 18% 3-HH-4 (2-1-1) 2%
3-HHB-1 (2-5-1) 5% 3-HHB-3 (2-5-1) 5% 3-HHB-O1 (2-5-1) 4%
3-HHB(2F,3Cl)-O2 (4-1-2-1) 3% 5-HHB(2F,3Cl)-O2 (4-1-2-1) 2%
3-HDhB(2F,3F)-O2 (4-2-5-1) 5%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. MAC-B(F)B-MAC (3-4-1) NI=80.3.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.094; .DELTA..di-elect
cons.=-3.6; .tau.=5.3 ms; VHR-1=99.1%; VHR-2=98.2%.
Example 35
TABLE-US-00039 3-H2B(2F,3F)-O2 (1-2-1) 18% 5-H2B(2F,3F)-O2 (1-2-1)
17% 3-HHB(2F,3F)-O2 (1-4-1) 5% 5-HHB(2F,3F)-O2 (1-4-1) 5%
3-HBB(2F,3F)-O2 (1-7-1) 9% 4-HBB(2F,3F)-O2 (1-7-1) 3%
5-HBB(2F,3F)-O2 (1-7-1) 9% 2-HH-3 (2-1-1) 18% 3-HH-4 (2-1-1) 2%
3-HHB-1 (2-5-1) 5% 3-HHB-3 (2-5-1) 5% 3-HHB-O1 (2-5-1) 4%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. MAC-B(2F)B-MAC (3-3-1) NI=82.3.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.096; .DELTA..di-elect
cons.=-3.6; .tau.=5.1 ms; VHR-1=99.2%; VHR-2=98.2%.
Example 36
TABLE-US-00040 3-H2B(2F,3F)-O2 (1-2-1) 18% 5-H2B(2F,3F)-O2 (1-2-1)
17% 3-HHB(2F,3F)-O2 (1-4-1) 5% 5-HHB(2F,3F)-O2 (1-4-1) 5%
3-HBB(2F,3F)-O2 (1-7-1) 9% 4-HBB(2F,3F)-O2 (1-7-1) 3%
5-HBB(2F,3F)-O2 (1-7-1) 9% 2-HH-3 (2-1-1) 18% 3-HH-4 (2-1-1) 2%
3-HHB-1 (2-5-1) 5% 3-HHB-3 (2-5-1) 5% 3-HHB-O1 (2-5-1) 4%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. MAC-B(F)B-MAC (3-4-1) NI=82.3.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.096; .DELTA..di-elect
cons.=-3.6; .tau.=5.1 ms; VHR-1=99.2%; VHR-2=98.2%.
Example 37
TABLE-US-00041 3-H2B(2F,3F)-O2 (1-2-1) 18% 5-H2B(2F,3F)-O2 (1-2-1)
17% 3-HBB(2F,3F)-O2 (1-7-1) 9% 4-HBB(2F,3F)-O2 (1-7-1) 3%
5-HBB(2F,3F)-O2 (1-7-1) 9% 2-HH-3 (2-1-1) 18% 3-HH-4 (2-1-1) 2%
3-HHB-1 (2-5-1) 5% 3-HHB-3 (2-5-1) 5% 3-HHB-O1 (2-5-1) 4%
3-HDhB(2F,3F)-O2 (4-2-5-1) 5% 5-HDhB(2F,3F)-O2 (4-2-5-1) 5%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. MAC-B(2F)B-MAC (3-3-1) NI=80.0.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.094; .DELTA..di-elect
cons.=-3.7; .tau.=5.2 ms; VHR-1=99.2%; VHR-2=98.2.
Example 38
TABLE-US-00042 3-H2B(2F,3F)-O2 (1-2-1) 18% 5-H2B(2F,3F)-O2 (1-2-1)
17% 3-HBB(2F,3F)-O2 (1-7-1) 9% 4-HBB(2F,3F)-O2 (1-7-1) 3%
5-HBB(2F,3F)-O2 (1-7-1) 9% 2-HH-3 (2-1-1) 18% 3-HH-4 (2-1-1) 2%
3-HHB-1 (2-5-1) 5% 3-HHB-3 (2-5-1) 5% 3-HHB-O1 (2-5-1) 4%
3-HDhB(2F,3F)-O2 (4-2-5-1) 5% 5-HDhB(2F,3F)-O2 (4-2-5-1) 5%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. MAC-B(F)B-MAC (3-4-1) NI=80.0.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.094; .DELTA..di-elect
cons.=-3.7; .tau.=5.2 ms; VHR-1=99.2%; VHR-2=98.2%.
Example 39
TABLE-US-00043 3-H2B(2F,3F)-O2 (1-2-1) 18% 5-H2B(2F,3F)-O2 (1-2-1)
17% 3-HHB(2F,3F)-O2 (1-4-1) 5% 3-HBB(2F,3F)-O2 (1-7-1) 9%
4-HBB(2F,3F)-O2 (1-7-1) 3% 5-HBB(2F,3F)-O2 (1-7-1) 9% 2-HH-3
(2-1-1) 18% 3-HH-4 (2-1-1) 2% 3-HHB-1 (2-5-1) 5% 3-HHB-3 (2-5-1) 5%
3-HHB-O1 (2-5-1) 4% 3-HDhB(2F,3F)-O2 (4-2-5-1) 5%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. MAC-B(2F)B-MAC (3-3-1) NI=81.9.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.096; .DELTA..di-elect
cons.=-3.6; .tau.=5.2 ms; VHR-1=99.1%; VHR-2=98.2%.
Example 40
TABLE-US-00044 3-H2B(2F,3F)-O2 (1-2-1) 18% 5-H2B(2F,3F)-O2 (1-2-1)
17% 3-HHB(2F,3F)-O2 (1-4-1) 5% 3-HBB(2F,3F)-O2 (1-7-1) 9%
4-HBB(2F,3F)-O2 (1-7-1) 3% 5-HBB(2F,3F)-O2 (1-7-1) 9% 2-HH-3
(2-1-1) 18% 3-HH-4 (2-1-1) 2% 3-HHB-1 (2-5-1) 5% 3-HHB-3 (2-5-1) 5%
3-HHB-O1 (2-5-1) 4% 3-HDhB(2F,3F)-O2 (4-2-5-1) 5%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. MAC-B(F)B-MAC (3-4-1) NI=81.9.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.096; .DELTA..di-elect
cons.=-3.6; .tau.=5.2 ms; VHR-1=99.1%; VHR-2=98.2%.
Example 41
TABLE-US-00045 3-H2B(2F,3F)-O2 (1-2-1) 20% 5-H2B(2F,3F)-O2 (1-2-1)
20% 3-HBB(2F,3F)-O2 (1-7-1) 10% 4-HBB(2F,3F)-O2 (1-7-1) 6%
5-HBB(2F,3F)-O2 (1-7-1) 3% 2-HH-3 (2-1-1) 6% 3-HH-4 (2-1-1) 17%
3-HHB-O1 (2-5-1) 3% 3-HHEBH-3 (2-9-1) 4% 3-HHEBH-4 (2-9-1) 3%
3-HH10Cro(7F,8F)-5 (4-3-3-3) 8%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. MAC-B(2F)B-MAC (3-3-1) NI=80.6.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.090; .DELTA..di-elect
cons.=-3.9; .tau.=5.3 ms; VHR-1=99.1%; VHR-2=98.1%.
Example 42
TABLE-US-00046 3-H2B(2F,3F)-O2 (1-2-1) 20% 5-H2B(2F,3F)-O2 (1-2-1)
20% 3-HBB(2F,3F)-O2 (1-7-1) 10% 4-HBB(2F,3F)-O2 (1-7-1) 6%
5-HBB(2F,3F)-O2 (1-7-1) 3% 2-HH-3 (2-1-1) 6% 3-HH-4 (2-1-1) 17%
3-HHB-O1 (2-5-1) 3% 3-HHEBH-3 (2-9-1) 4% 3-HHEBH-4 (2-9-1) 3%
3-HH10Cro(7F,8F)-5 (4-3-3-3) 8%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. MAC-B(F)B-MAC (3-4-1) NI=80.6.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.090; .DELTA..di-elect
cons.=-3.9; .tau.=5.3 ms; VHR-1=99.1%; VHR-2=98.1%.
Example 43
TABLE-US-00047 3-H2B(2F,3F)-O2 (1-2-1) 20% 5-H2B(2F,3F)-O2 (1-2-1)
14% 3-HBB(2F,3F)-O2 (1-7-1) 9% 4-HBB(2F,3F)-O2 (1-7-1) 3% 2-HH-3
(2-1-1) 19% 3-HH-4 (2-1-1) 7% 3-HHB-1 (2-5-1) 3% 3-HHB-3 (2-5-1) 4%
3-HHEBH-3 (2-9-1) 4% 3-HHEBH-4 (2-9-1) 4% 3-HDhB(2F,3F)-O2
(4-2-5-1) 8% 3-HH1OCro(7F,8F)-5 (4-3-3-3) 5%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. MAC-B(2F)B-MAC (3-3-1) NI=80.1.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.084; .DELTA..di-elect
cons.=-3.6; .tau.=5.3 ms; VHR-1=99.1%; VHR-2=98.1%.
Example 44
TABLE-US-00048 3-H2B(2F,3F)-O2 (1-2-1) 20% 5-H2B(2F,3F)-O2 (1-2-1)
14% 3-HBB(2F,3F)-O2 (1-7-1) 9% 4-HBB(2F,3F)-O2 (1-7-1) 3% 2-HH-3
(2-1-1) 19% 3-HH-4 (2-1-1) 7% 3-HHB-1 (2-5-1) 3% 3-HHB-3 (2-5-1) 4%
3-HHEBH-3 (2-9-1) 4% 3-HHEBH-4 (2-9-1) 4% 3-HDhB(2F,3F)-O2
(4-2-5-1) 8% 3-HH10Cro(7F,8F)-5 (4-3-3-3) 5%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. MAC-B(F)B-MAC (3-4-1) NI=80.1.degree. C.; Tc
.ltoreq.-20.degree. C.; .DELTA.n=0.084; .DELTA..di-elect
cons.=-3.6; .tau.=5.3 ms; VHR-1=99.1%; VHR-2=98.1%.
Example 45
TABLE-US-00049 3-H2B(2F,3F)-O2 (1-2-1) 20% 5-H2B(2F,3F)-O2 (1-2-1)
13% 3-HBB(2F,3F)-O2 (1-7-1) 10% 2-HH-3 (2-1-1) 19% 3-HH-4 (2-1-1)
7% 3 -HHB- 1 (2-5-1) 4% 3-HHB-3 (2-5-1) 5% 3-HHB-O1 (2-5-1) 4%
3-HHEBH-3 (2-9-1) 5% 3-HDhB(2F,3F)-O2 (4-2-5-1) 8%
3-HH10Cro(7F,8F)-5 (4-3-3-3) 5%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. MAC-B(2F)B-MAC (3-3-1) NI=80.0.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.084; Asd=-3.4; .tau.=5.3 ms;
VHR-1=99.1%; VHR-2=98.1%.
Example 46
TABLE-US-00050 3-H2B(2F,3F)-O2 (1-2-1) 20% 5-H2B(2F,3F)-O2 (1-2-1)
13% 3-HBB(2F,3F)-O2 (1-7-1) 10% 2-HH-3 (2-1-1) 19% 3-HH-4 (2-1-1)
7% 3 -HHB- 1 (2-5-1) 4% 3-HHB-3 (2-5-1) 5% 3-HHB-O1 (2-5-1) 4%
3-HHEBH-3 (2-9-1) 5% 3-HDhB(2F,3F)-O2 (4-2-5-1) 8%
3-HH1OCro(7F,8F)-5 (4-3-3-3) 5%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. MAC-B(F)B-MAC (3-4-1) NI=80.0.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.084; .DELTA..di-elect
cons.=-3.4; .tau.=5.3 ms; VHR-1=99.1%; VHR-2=98.1%.
Example 47
TABLE-US-00051 3-H2B(2F,3F)-O2 (1-2-1) 20% 5-H2B(2F,3F)-O2 (1-2-1)
12% 3-HBB(2F,3F)-O2 (1-7-1) 10% 4-HBB(2F,3F)-O2 (1-7-1) 3% 2-HH-3
(2-1-1) 21% 3-HH-4 (2-1-1) 8% 3 -HHB- 1 (2-5-1) 4% 3-HHB-3 (2-5-1)
4% 3-HHB-O1 (2-5-1) 4% 3-HHEBH-3 (2-9-1) 5% 3-HDhB(2F,3F)-O2
(4-2-5-1) 4% 3-HH1OCro(7F,8F)-5 (4-3-3-3) 5%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. MAC-B(2F)B-MAC (3-3-1) NI=79.2.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.083; .DELTA..di-elect
cons.=-3.0; T=5.2 ms; VHR-1=99.1%; VHR-2=98.1%.
Example 48
TABLE-US-00052 3-H2B(2F,3F)-O2 (1-2-1) 20% 5-H2B(2F,3F)-O2 (1-2-1)
12% 3-HBB(2F,3F)-O2 (1-7-1) 10% 4-HBB(2F,3F)-O2 (1-7-1) 3% 2-HH-3
(2-1-1) 21% 3-HH-4 (2-1-1) 8% 3-HHB-1 (2-5-1) 4% 3-HHB-3 (2-5-1) 4%
3-HHB-O1 (2-5-1) 4% 3-HHEBH-3 (2-9-1) 5% 3-HDhB(2F,3F)-O2 (4-2-5-1)
4% 3-HH1OCro(7F,8F)-5 (4-3-3-3) 5%
To 100 parts by weight of the composition above, 0.3 part by weight
of the following compound as the third component of the invention
was added. MAC-B(F)B-MAC (3-4-1) NI=79.2.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.083; .DELTA..di-elect
cons.=-3.0; .tau.=5.2 ms; VHR-1=99.1%; VHR-2=98.1%.
Example 49
TABLE-US-00053 3-H2B(2F,3F)-O2 (1-2-1) 15% 5-H2B(2F,3F)-O2 (1-2-1)
10% 3-HHB(2F,3F)-O2 (1-4-1) 6% 3-HBB(2F,3F)-O2 (1-7-1) 11%
4-HBB(2F,3F)-O2 (1-7-1) 10% 5-HBB(2F,3F)-O2 (1-7-1) 7% 2-HH-3
(2-1-1) 22% 3-HB-O2 (2-2-1) 7% 5-HB-O2 (2-2-1) 6% 5-HBB(F)B-2
(2-12-1) 6%
To 100 parts by weight of the composition above, 0.2 part by weight
of the following compound as the third component of the invention
was added. MAC-B(2F)B-MAC (3-3-1) NI=73.2.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.106; .DELTA..di-elect
cons.=-3.0; .tau.=5.2 ms; VHR-1=99.2%; VHR-2=98.2%.
Example 50
TABLE-US-00054 3-H2B(2F,3F)-O2 (1-2-1) 15% 5-H2B(2F,3F)-O2 (1-2-1)
10% 3-HHB(2F,3F)-O2 (1-4-1) 6% 3-HBB(2F,3F)-O2 (1-7-1) 11%
4-HBB(2F,3F)-O2 (1-7-1) 10% 5-HBB(2F,3F)-O2 (1-7-1) 7% 2-HH-3
(2-1-1) 22% 3-HB-O2 (2-2-1) 7% 5-HB-O2 (2-2-1) 6% 5-HBB(F)B-2
(2-12-1) 6%
To 100 parts by weight of the composition above, 0.2 part by weight
of the following compound as the third component of the invention
was added. MAC-B(F)B-MAC (3-4-1) NI=73.2.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.106; .DELTA..di-elect
cons.=-3.0; .tau.=5.2 ms; VHR-1=99.2%; VHR-2=98.2%.
Example 51
TABLE-US-00055 3-H2B(2F,3F)-O2 (1-2-1) 15% 5-H2B(2F,3F)-O2 (1-2-1)
7% 3-HBB(2F,3F)-O2 (1-7-1) 11% 4-HBB(2F,3F)-O2 (1-7-1) 10%
5-HBB(2F,3F)-O2 (1-7-1) 7% 2-HH-3 (2-1-1) 22% 3-HH-4 (2-1-1) 3%
3-HB-O2 (2-2-1) 7% 5-HB-O2 (2-2-1) 6% 5-HBB(F)B-2 (2-12-1) 6%
3-HDhB(2F,3F)-O2 (4-2-5-1) 6%
To 100 parts by weight of the composition above, 0.2 part by weight
of the following compound as the third component of the invention
was added. MAC-B(2F)B-MAC (3-3-1) NI=74.7.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.104; .DELTA..di-elect
cons.=-3.0; .tau.=5.2 ms; VHR-1=99.1%; VHR-2=98.2%.
Example 52
TABLE-US-00056 3-H2B(2F,3F)-O2 (1-2-1) 15% 5-H2B(2F,3F)-O2 (1-2-1)
7% 3-HBB(2F,3F)-O2 (1-7-1) 11% 4-HBB(2F,3F)-O2 (1-7-1) 10%
5-HBB(2F,3F)-O2 (1-7-1) 7% 2-HH-3 (2-1-1) 22% 3-HH-4 (2-1-1) 3%
3-HB-O2 (2-2-1) 7% 5-HB-O2 (2-2-1) 6% 5-HBB(F)B-2 (2-12-1) 6%
3-HDhB(2F,3F)-O2 (4-2-5-1) 6%
To 100 parts by weight of the composition above, 0.2 part by weight
of the following compound as the third component of the invention
was added. MAC-B(F)B-MAC (3-4-1) NI=74.7.degree. C.;
Tc.ltoreq.-20.degree. C.; .DELTA.n=0.104; .DELTA..di-elect
cons.=-3.0; .tau.=5.2 ms; VHR-1=99.1%; VHR-2=98.2%.
The compositions according to Examples 1 to 52 have a shorter
response time in comparison with the composition according to
Comparative Example 1. Thus, the liquid crystal composition of the
invention is so much superior in characteristics to the composition
shown in Comparative Example 1.
Industrial Applicability
The invention provides a liquid crystal composition satisfying at
least one of characteristics such as a high maximum temperature of
a nematic phase, a low minimum temperature of the nematic phase, a
small viscosity, a suitable optical anisotropy, a large negative
dielectric anisotropy, a large specific resistance, a high
stability to ultraviolet light and a high stability to heat, or
having a suitable balance regarding at least two of the
characteristics. A liquid crystal display device containing such a
liquid crystal composition is applied as an AM device having a
short response time, a large voltage holding ratio, a large
contrast ratio, a long service life and so forth, and thus can be
used for a liquid crystal projector, a liquid crystal television
and so forth.
* * * * *