U.S. patent application number 15/598379 was filed with the patent office on 2017-11-23 for polymerizable compound, mixture, polymerizable liquid crystal composition, polymer, optical film, optically anisotropic product, polarizing plate, flat panel display device, organic electroluminescence display device, and anti-reflection film.
This patent application is currently assigned to ZEON CORPORATION. The applicant listed for this patent is ZEON CORPORATION. Invention is credited to Satoshi KIRIKI, Kumi OKUYAMA, Kei SAKAMOTO.
Application Number | 20170335193 15/598379 |
Document ID | / |
Family ID | 57582177 |
Filed Date | 2017-11-23 |
United States Patent
Application |
20170335193 |
Kind Code |
A1 |
SAKAMOTO; Kei ; et
al. |
November 23, 2017 |
POLYMERIZABLE COMPOUND, MIXTURE, POLYMERIZABLE LIQUID CRYSTAL
COMPOSITION, POLYMER, OPTICAL FILM, OPTICALLY ANISOTROPIC PRODUCT,
POLARIZING PLATE, FLAT PANEL DISPLAY DEVICE, ORGANIC
ELECTROLUMINESCENCE DISPLAY DEVICE, AND ANTI-REFLECTION FILM
Abstract
Disclosed is a mixture containing polymerizable compounds having
Formulas (III) and (IV) wherein Ar.sup.1 and Ar.sup.2 are divalent
aromatic hydrocarbon or heteroaromatic ring group having D1 or D2
as a substituent; D.sup.1 and D.sup.2 are C1-C20 organic group
having at least one aromatic ring selected from the group
consisting of aromatic hydrocarbon ring and heteroaromatic ring;
A.sup.11-A.sup.22 and B.sup.11-B.sup.22 are alicyclic or aromatic
group which may have a substituent, Y.sup.11-Y.sup.22 and
L.sup.11-L.sup.22 are single bond, --O--, --CO--, --C0--O--,
--O--CO--, --NR.sup.21--CO--, --CO--NR.sup.22--, --O--CO--O--,
--NR.sup.23--CO--O--, --O--CO--NR.sup.24-- or
--NR.sup.25--CO--NR.sup.26-- where R.sup.21-R.sup.26 are hydrogen
or C1-C6 alkyl group; R.sup.4-R.sup.9 are hydrogen, methyl group or
chlorine; one of f and k is integer of 1 to 3 with the other being
integer of 0 to 3; g, j, m and q are integer of 1 to 20; and h, i,
n and p are 0 or 1. ##STR00001## ##STR00002##
Inventors: |
SAKAMOTO; Kei; (Tokyo,
JP) ; OKUYAMA; Kumi; (Tokyo, JP) ; KIRIKI;
Satoshi; (Tokyo, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ZEON CORPORATION |
Tokyo |
|
JP |
|
|
Assignee: |
ZEON CORPORATION
Tokyo
JP
|
Family ID: |
57582177 |
Appl. No.: |
15/598379 |
Filed: |
May 18, 2017 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08F 222/24 20130101;
G02B 5/30 20130101; C07D 277/82 20130101; C07C 69/75 20130101; C09K
19/3861 20130101; G02F 1/13363 20130101; C07C 2601/14 20170501;
H01L 51/5281 20130101; C07C 69/67 20130101; G02F 2001/133541
20130101; H01L 51/0043 20130101; C09K 2019/0448 20130101; G02B
5/3016 20130101; H01L 51/004 20130101; C08F 238/00 20130101; C09K
19/3497 20130101; G02F 2001/133638 20130101; G02F 1/133528
20130101 |
International
Class: |
C09K 19/38 20060101
C09K019/38; H01L 51/00 20060101 H01L051/00; G02F 1/1335 20060101
G02F001/1335; G02B 5/30 20060101 G02B005/30; C09K 19/34 20060101
C09K019/34; C08F 238/00 20060101 C08F238/00; C08F 222/24 20060101
C08F222/24; H01L 51/52 20060101 H01L051/52; C07D 277/82 20060101
C07D277/82 |
Foreign Application Data
Date |
Code |
Application Number |
May 18, 2016 |
JP |
2016-100009 |
Claims
1-7. (canceled)
8. A polymerizable compound having the following Formula (III):
##STR00090## where Ar.sup.1 represents divalent aromatic
hydrocarbon ring group having D.sup.1 as a substituent, or divalent
heteroaromatic ring group having D.sup.1 as a substituent, D.sup.1
represents C1-C20 organic group having at least one aromatic ring
selected from the group consisting of an aromatic hydrocarbon ring
and a heteroaromatic ring, Z.sup.11 and Z.sup.12 represent each
independently --CO--O--, --O--CO--, --NR.sup.31--CO-- or
--CO--NR.sup.32--, where R.sup.31 and R.sup.32 represent each
independently hydrogen or C1-C6 alkyl group, A.sup.11, A.sup.12,
B.sup.11 and B.sup.12 represent each independently alicyclic group
which may have a substituent, or aromatic group which may have a
substituent, Y.sup.11, Y.sup.12, L.sup.11 and L.sup.12 represent
each independently single bond, --O--, --CO--, --CO--O--,
--O--CO--, --NR.sup.21--CO--, --CO--NR.sup.22--, --O--CO--O--,
--NR.sup.23--CO--O--, --O--CO--NR.sup.24-- or
--NR.sup.25--CO--NR.sup.26--, where R.sup.21 to R.sup.26 represent
each independently hydrogen or C1-C6 alkyl group, R.sup.4 to
R.sup.7 represent each independently hydrogen, methyl group or
chlorine, one of f and k is an integer of 1 to 3 with the other
being an integer of 0 to 3, g and j represent each independently an
integer of 1 to 20, and h and i are each independently 0 or 1.
9. The polymerizable compound of claim 8, wherein Ar.sup.1-D.sup.1
is a divalent group having the following Formula (V): ##STR00091##
where Ax represents C2-C20 organic group having at least one
aromatic ring selected from the group consisting of an aromatic
hydrocarbon ring and a heteroaromatic ring, and Ra represents
hydrogen or C1-C20 organic group which may have a substituent.
10. The polymerizable compound of claim 9, wherein Ax is a group
having the following Formula (VI): ##STR00092## where RX represents
hydrogen, halogen, C1-C6 alkyl group, cyano group, nitro group,
C1-C6 fluoroalkyl group, C1-C6 alkoxy group, or
--C(.dbd.O)--O--R.sup.b, where R.sup.b represents C1-C20 alkyl
group which may have a substituent, C2-C20 alkenyl group which may
have a substituent, C3-C12 cycloalkyl group which may have a
substituent, or C5-C12 aromatic hydrocarbon ring group which may
have a substituent, each Rx may be the same or different, and at
least one CRx constituting the ring may be replaced by
nitrogen.
11. The polymerizable compound of claim 9, wherein Ra is C1-C20
alkyl group which may have a substituent, C2-C20 alkenyl group
which may have a substituent, C2-20 alkynyl group which may have a
substituent, or C6-C18 aromatic group which may have a
substituent.
12. A mixture comprising: the polymerizable compound of claim 8;
and a polymerizable compound having the following Formula (IV):
##STR00093## where Ar.sup.2 represents divalent aromatic
hydrocarbon ring group having D.sup.2 as a substituent, or divalent
heteroaromatic ring group having D.sup.2 as a substituent, D.sup.2
represents C1-C20 organic group having at least one aromatic ring
selected from the group consisting of an aromatic hydrocarbon ring
and a heteroaromatic ring, Z.sup.21 and Z.sup.22 represent each
independently --CO--O--, --O--CO--, --NR.sup.31--CO-- or
--CO--NR.sup.32--, where R.sup.31 and R.sup.32 represent each
independently hydrogen or C1-C6 alkyl group, A.sup.21, A.sup.22,
B.sup.21 and B.sup.22 represent each independently alicyclic group
which may have a substituent, or aromatic group which may have a
substituent, Y.sup.21, Y.sup.22, L.sup.21 and L.sup.22 represent
each independently single bond, --O--, --CO--, --CO--O--,
--O--CO--, --NR.sup.21--CO--, --CO--NR.sup.22--, --O--CO--O--,
--NR.sup.23--CO--O--, --O--CO--NR.sup.24-- or --NR.sup.2513
CO--NR.sup.26--, where R.sup.21 to R.sup.26 represent each
independently hydrogen or C1-C6 alkyl group, R.sup.8 and R.sup.9
represent each independently hydrogen, methyl group or chlorine, m
and q represent each independently an integer of 1 to 20, and n and
p are each independently 0 or 1.
13. The mixture of claim 12, wherein Ar.sup.1-D.sup.1 is a divalent
group having the following Formula (V): ##STR00094## where Ax
represents C2-C20 organic group having at least one aromatic ring
selected from the group consisting of an aromatic hydrocarbon ring
and a heteroaromatic ring, and Ra represents hydrogen or C1-C20
organic group which may have a substituent, and wherein
Ar.sup.2-D.sup.2 is a divalent group having the following Formula
(VII): ##STR00095## where Ay represents C2-C20 organic group having
at least one aromatic ring selected from the group consisting of an
aromatic hydrocarbon ring and a heteroaromatic ring, and Rc
represents hydrogen or C1-C20 organic group which may have a
substituent.
14. The mixture of claim 13, wherein Ax and Ay are each
independently a group having the following Formula (VI):
##STR00096## where R.sup.x represents hydrogen, halogen, C1-C6
alkyl group, cyano group, nitro group, C1-C6 fluoroalkyl group,
C1-C6 alkoxy group, or --C(.dbd.O)--O--R.sup.b, where R.sup.b
represents C1-C20 alkyl group which may have a substituent, C2-C20
alkenyl group which may have a substituent, C3-C12 cycloalkyl group
which may have a substituent, or C5-C12 aromatic hydrocarbon ring
group which may have a substituent, each R.sup.x may be the same or
different, and at least one C--R.sup.x constituting the ring may be
replaced by nitrogen.
15. The mixture of claim 13, wherein Ra is C1-C20 alkyl group which
may have a substituent, C2-C20 alkenyl group which may have a
substituent, C2-20 alkynyl group which may have a substituent, or
C6-C18 aromatic group which may have a substituent, and Rc is
C1-C20 alkyl group which may have a substituent, C2-C20 alkenyl
group which may have a substituent, C2-20 alkynyl group which may
have a substituent, or C6-C18 aromatic group which may have a
substituent.
16. The mixture of claim 12, wherein a mass ratio of the
polymerizable compound having Formula (III) to the polymerizable
compound having Formula (IV) (polymerizable compound having Formula
(III): polymerizable compound having Formula (IV)) is 1:1,000 to
20:100.
17. A polymerizable liquid crystal composition comprising: the
mixture of claim 12; and a polymerization initiator.
18. A polymer obtainable by polymerization of the mixture of claim
12.
19. A polymer obtainable by polymerization of the polymerizable
liquid crystal composition of claim 17.
20. An optical film comprising the polymer of claim 18 as a
constituent material.
21. An optically anisotropic product comprising a layer which
comprises the polymer of claim 18 as a constituent material.
22. A polarizing plate comprising: the optically anisotropic
product of claim 21; and a polarizing film.
23. A flat panel display device comprising: the polarizing plate of
claim 22; and a liquid crystal panel.
24. An organic electroluminescence display device comprising: the
polarizing plate of claim 22; and an organic electroluminescence
panel.
25. An anti-reflection film comprising the polarizing plate of
claim 22.
Description
TECHNICAL FIELD
[0001] The present disclosure is directed to optical films and
optically anisotropic products capable of uniform polarized light
conversion over a wide wavelength range, and to polarizing plates,
flat panel display devices, organic electroluminescence display
devices and anti-reflection films which include the optically
anisotropic product.
[0002] The present disclosure is also directed to polymers which
may be used for the preparation of the optical films and optically
anisotropic products, polymerizable compounds which may be used for
the preparation of the polymers, mixtures and polymerizable liquid
crystal compositions containing the polymerizable compounds, and
compounds which may be used for the preparation of the
polymerizable compounds and mixtures containing the compounds.
BACKGROUND
[0003] Phase difference plates used in flat panel display devices
and other like devices include quarter-wave plates that convert
linearly polarized light into circularly polarized light, and
half-wave plates that rotate the plane of vibration of linearly
polarized light by 90 degrees. These phase difference plates can
achieve exact .lamda./4 or .lamda./2 phase difference for
particular monochromatic light.
[0004] However, the conventional phase difference plates have the
drawback of undesirably converting the polarized light emitting
from the phase difference plate into colored one. The cause of this
is that the material of the phase difference plate has wavelength
dispersion of phase difference and white light, or composite waves
which include different rays in the visible range, shows a
distribution of polarization states at different wavelengths and
hence incident light cannot be converted into polarized light
having its phase retarded by exactly .lamda./4 or .lamda./2 over
the entire wavelength range.
[0005] To address such a drawback, studies have been made for
wide-band phase difference plates which may provide uniform phase
difference over a wide wavelength range, i.e., phase difference
plates having reversed wavelength dispersion.
[0006] Improvements in the function of portable information
terminals such as mobile PCs and cellular phones and their
widespread use are increasingly requiring that flat panel display
devices be thinned as much as possible. Correspondingly, it is also
required to make thinner the phase difference plates which
constitute the flat panel display devices.
[0007] The method of making thinner phase difference plates which
is deemed most effective in recent years involves applying
polymerizable compositions containing low-molecular weight
polymerizable compounds on film substrates to form optical films.
This led to many developments of polymerizable compounds or
polymerizable compositions containing the polymerizable compounds
that allow for the manufacture of optical films that have superior
reverse wavelength dispersion.
[0008] PTL 1 and PTL 2, for example, propose polymerizable
compounds and polymerizable compositions that not only allow for
the manufacture of optical films with superior reverse wavelength
dispersion but can be easily applied on substrates for their low
melting points suitable for processing, as well as show a wide
temperature range of liquid crystallinity and can be synthesized at
low costs.
CITATION LIST
Patent Literature
[0009] PTL 1: WO2014/010325A [0010] PTL 2: JP2015200877A
SUMMARY
[0011] Manufacture of optical films or optically anisotropic
products (hereinafter occasionally collectively referred to as
"optical film, etc.") on an industrial scale using polymerizable
compositions containing polymerizable compounds requires a wide
process margin.
[0012] In particular, it is difficult to completely make uniform
the temperature in the drying furnace and time conditions when
polymerizable compositions are applied over large areas for the
manufacture of optical film etc. Thus, a margin for the
manufacturing conditions such as temperature and time greatly
affects the yield of optical film etc.
[0013] The conventional polymerizable compounds and polymerizable
compositions, however, are not sufficient in terms of process
margin as optical film etc. cannot be obtained which can retain
liquid crystal phase more stably over long periods of time.
Accordingly, there has been a need in the art to provide
polymerizable liquid crystal compositions containing polymerizable
compounds which allow for the formation of optical film etc. which
can retain liquid crystal phase more stably over long periods of
time.
[0014] The present disclosure was made in light of the foregoing
drawbacks pertinent in the art. It would therefore be helpful to
provide polymerizable liquid crystal compositions which have low
melting points suitable for practical use, can be produced at low
costs, and allow for the formation of optical film etc. which are
capable of uniform polarized light conversion over a wide
wavelength range and of retaining crystal phase more stably over
long periods of time.
[0015] It would also be helpful to provide polymerizable compounds
useful for the preparation of the polymerizable liquid crystal
compositions and mixtures containing the polymerizable compounds,
and compounds useful for the preparation of the polymerizable
compounds and mixtures containing the compounds.
[0016] The inventors made extensive studies to address the
foregoing drawback and completed the present disclosure by
establishing that the use of a mixture of specific polymerizable
compounds having Formulas (III) and (IV) given below results in
polymerizable liquid crystal compositions at low costs which allow
for the formation of optical film etc. which can retain liquid
crystal phase more stably over long periods of time, have less
coating unevenness, and have superior reverse wavelength
dispersion.
[0017] The present disclosure thus provides the compounds,
polymerizable compounds, mixtures, polymerizable liquid crystal
compositions, polymers, optical film, optically anisotropic
product, polarizing plate, flat panel display device, organic
electroluminescence display device, and anti-reflection film given
below.
[0018] [1] A compound having the following Formula (I):
##STR00003##
[0019] where A.sup.1 and B.sup.1 represent each independently
alicyclic group which may have a substituent, or aromatic group
which may have a substituent,
[0020] Y.sup.1 and L.sup.1 represent each independently single
bond, --O--, --CO--, --CO--O--, --O--CO--, --NR.sup.21--CO--,
--CO--NR.sup.22--, --O--CO--O--, --NR.sup.23--CO--O--,
--O--CO--NR.sup.24-- or --NR.sup.25--CO--NR.sup.26--, where
R.sup.21 to R.sup.26 represent each independently hydrogen or C1-C6
alkyl group,
[0021] R.sup.1 and R.sup.2 represent each independently hydrogen,
methyl group or chlorine,
[0022] FG.sup.1 represents hydroxyl group, carboxyl group or amino
group,
[0023] a represents an integer of 1 to 3,
[0024] b represents an integer of 1 to 20, and
[0025] c is 0 or 1.
[0026] [2] The compound of [1], wherein FG.sup.1 is hydroxyl group,
and c is 0.
[0027] [3] The compound of [1], wherein FG.sup.1 is carboxyl group,
and c is 1.
[0028] [4] A mixture including:
[0029] the compound of any one of [1] to [3]; and
[0030] a compound having the following Formula (II):
##STR00004##
[0031] where A.sup.2 and B.sup.2 represent each independently
alicyclic group which may have a substituent, or aromatic group
which may have a substituent,
[0032] Y.sup.2 and L.sup.2 represent each independently single
bond, --O--, --CO--, --CO--O--, --O--CO--, --NR.sup.21--CO--,
--CO--NR.sup.22, --O--CO--O--, --NR.sup.23--CO--O--,
--O--CO--NR.sup.24-- or --NR.sup.25--CO--NR.sup.26--, where
R.sup.21 to R.sup.26 represent each independently hydrogen or C1-C6
alkyl group,
[0033] R.sup.3 represents hydrogen, methyl group or chlorine,
[0034] FG.sup.2 represents hydroxyl group, carboxyl group or amino
group,
[0035] d represents an integer of 1 to 20, and
[0036] e is 0 or 1.
[0037] [5] The mixture of [4], wherein FG.sup.1 and FG.sup.2 are
hydroxyl groups, and c and e are 0.
[0038] [6] The mixture of [4], wherein FG.sup.1 and FG.sup.2 are
carboxyl groups, and c and e are 1.
[0039] [7] The mixture of any one of [4] to [6], wherein a mass
ratio of the compound having Formula (I) to the compound having
Formula (II) (compound having Formula (I):compound having Formula
(II)) is 1:1,000 to 20:100.
[0040] [8] A polymerizable compound having the following Formula
(III):
##STR00005##
[0041] where Ar.sup.1 represents divalent aromatic hydrocarbon ring
group having D.sup.1 as a substituent, or divalent heteroaromatic
ring group having D.sup.1 as a sub stituent,
[0042] D.sup.1 represents C1-C20 organic group having at least one
aromatic ring selected from the group consisting of an aromatic
hydrocarbon ring and a heteroaromatic ring,
[0043] Z.sup.11 and Z.sup.12 represent each independently
--CO--O--, --O--CO--, --NR.sup.31--CO-- or --CO--NR.sup.32--, where
R.sup.31 and R.sup.32 represent each independently hydrogen or
C1-C6 alkyl group,
[0044] A.sup.11, A.sup.12, B.sup.11 and B.sup.12 represent each
independently alicyclic group which may have a substituent, or
aromatic group which may have a substituent,
[0045] Y.sup.11, Y.sup.12, L.sup.11 and L.sup.12 represent each
independently single bond, --O--, --CO--, --CO--O--, --O--CO--,
--NR.sup.21--CO--, --CO--NR.sup.22--, --O--CO--O--,
--NR.sup.23--CO--O--, --O--CO--NR.sup.24-- or
--NR.sup.25--CO--NR.sup.26--, where R.sup.21 to R.sup.26 represent
each independently hydrogen or C1-C6 alkyl group,
[0046] R.sup.4 to R.sup.7 represent each independently hydrogen,
methyl group or chlorine,
[0047] one of f and k is an integer of 1 to 3 with the other being
an integer of 0 to 3,
[0048] g and j represent each independently an integer of 1 to 20,
and
[0049] h and i are each independently 0 or 1.
[0050] [9] The polymerizable compound of [8], wherein
Ar.sup.1-D.sup.1 is a divalent group having the following Formula
(V):
##STR00006##
[0051] where Ax represents C2-C20 organic group having at least one
aromatic ring selected from the group consisting of an aromatic
hydrocarbon ring and a heteroaromatic ring, and
[0052] Ra represents hydrogen or C1-C20 organic group which may
have a substituent.
[0053] [10] The polymerizable compound of [9], wherein Ax is a
group having the following Formula (VI):
##STR00007##
[0054] where R.sup.x represents hydrogen, halogen, C1-C6 alkyl
group, cyano group, nitro group, C1-C6 fluoroalkyl group, C1-C6
alkoxy group, or --C(.dbd.O)--O--R.sup.b, where R.sup.b represents
C1-C20 alkyl group which may have a substituent, C2-C20 alkenyl
group which may have a substituent, C3-C12 cycloalkyl group which
may have a substituent, or C5-C12 aromatic hydrocarbon ring group
which may have a substituent, each R.sup.x may be the same or
different, and at least one C--R.sup.x constituting the ring may be
replaced by nitrogen.
[0055] [11] The polymerizable compound of [9] or [10], wherein Ra
is C1-C20 alkyl group which may have a substituent, C2-C20 alkenyl
group which may have a substituent, C2-20 alkynyl group which may
have a substituent, or C6-C18 aromatic group which may have a
substituent.
[0056] [12] A mixture including:
[0057] the polymerizable compound of any one of [8] to [11];
and
[0058] a polymerizable compound having the following Formula
(IV):
##STR00008##
[0059] where Ar.sup.2 represents divalent aromatic hydrocarbon ring
group having D.sup.2 as a substituent, or divalent heteroaromatic
ring group having D.sup.2 as a substituent,
[0060] D.sup.2 represents C1-C20 organic group having at least one
aromatic ring selected from the group consisting of an aromatic
hydrocarbon ring and a heteroaromatic ring,
[0061] Z.sup.21 and Z.sup.22 represent each independently
--CO--O--, --O--CO--, --NR.sup.31--CO--, or --CO--NR.sup.32--,
where R.sup.31 and R.sup.32 represent each independently hydrogen
or C1-C6 alkyl group,
[0062] A.sup.21, A.sup.22, B.sup.21 and B.sup.22 represent each
independently alicyclic group which may have a substituent, or
aromatic group which may have a substituent,
[0063] Y.sup.21, Y.sup.22, L.sup.21 and L.sup.22 represent each
independently single bond, --O--, --CO--, --CO--O--, --O--CO--,
--NR.sup.21--CO--, --CO--NR.sup.22--, --O--CO--O--,
--NR.sup.23--CO--O--, --O--CO--NR.sup.24-- or
--NR.sup.25--CO--NR.sup.26--, where R.sup.21 to R.sup.26 represent
each independently hydrogen or C1-C6 alkyl group,
[0064] R.sup.8 and R.sup.9 represent each independently hydrogen,
methyl group or chlorine,
[0065] m and q represent each independently an integer of 1 to 20,
and
[0066] n and p are each independently 0 or 1.
[0067] [13] The mixture of [12], wherein Ar.sup.1-D.sup.1 is a
divalent group having the following Formula (V):
##STR00009##
[0068] where Ax represents C2-C20 organic group having at least one
aromatic ring selected from the group consisting of an aromatic
hydrocarbon ring and a heteroaromatic ring, and
[0069] Ra represents hydrogen or C1 -C20 organic group which may
have a sub stituent, and wherein
[0070] Ar.sup.2-D.sup.2 is a divalent group having the following
Formula (VII):
##STR00010##
[0071] where Ay represents C2-C20 organic group having at least one
aromatic ring selected from the group consisting of an aromatic
hydrocarbon ring and a heteroaromatic ring, and
[0072] Rc represents hydrogen or C1-C20 organic group which may
have a substituent.
[0073] [14] The mixture of [13], wherein Ax and Ay are each
independently a group having the following Formula (VI):
##STR00011##
[0074] where R.sup.x represents hydrogen, halogen, C1-C6 alkyl
group, cyano group, nitro group, C1-C6 fluoroalkyl group, C1-C6
alkoxy group, or --C(.dbd.O)--O--R.sup.b, where R.sup.b represents
C1-C20 alkyl group which may have a substituent, C2-C20 alkenyl
group which may have a substituent, C3-C12 cycloalkyl group which
may have a substituent, or C5-C12 aromatic hydrocarbon ring group
which may have a substituent, each R.sup.x may be the same or
different, and at least one C--R.sup.x constituting the ring may be
replaced by nitrogen.
[0075] [15] The mixture of [13] or [14], wherein Ra is C1-C20 alkyl
group which may have a substituent, C2-C20 alkenyl group which may
have a substituent, C2-20 alkynyl group which may have a
substituent, or C6-C18 aromatic group which may have a substituent,
and
[0076] Rc is C1-C20 alkyl group which may have a substituent,
C2-C20 alkenyl group which may have a substituent, C2-20 alkynyl
group which may have a substituent, or C6-C18 aromatic group which
may have a substituent.
[0077] [16] The mixture of any one of [12] to [15], wherein a mass
ratio of the polymerizable compound having Formula (III) to the
polymerizable compound having Formula (IV) (polymerizable compound
having Formula (III): polymerizable compound having Formula (IV))
is 1:1,000 to 20:100.
[0078] [17] A polymerizable liquid crystal composition
including:
[0079] the mixture of any one of [12] to [16]; and
[0080] a polymerization initiator.
[0081] [18] A polymer obtainable by polymerization of the mixture
of any one of [12] to [16].
[0082] [19] A polymer obtainable by polymerization of the
polymerizable liquid crystal composition of [17].
[0083] [20] An optical film including the polymer of [18] or [19]
as a constituent material.
[0084] [21] An optically anisotropic product including a layer
which comprises the polymer of [18] or [19] as a constituent
material.
[0085] [22] A polarizing plate including:
[0086] the optically anisotropic product of [21]; and
[0087] a polarizing film.
[0088] [23] A flat panel display device including:
[0089] the polarizing plate of [22]; and
[0090] a liquid crystal panel.
[0091] [24] An organic electroluminescence display device
including:
[0092] the polarizing plate of [22]; and
[0093] an organic electroluminescence panel.
[0094] [25] An anti-reflection film including the polarizing plate
of [22].
[0095] The present disclosure provides polymerizable liquid crystal
compositions which can retain liquid crystal phase more stably over
long periods of time, have low melting points suitable for
practical use, and allow for low-cost manufacture of optical film
etc. which are capable of uniform polarized light conversion over a
wide wavelength range with a wide process margin.
[0096] The present disclosure also provides polymerizable compounds
useful for the preparation of the polymerizable liquid crystal
compositions and mixtures containing the polymerizable compounds,
and compounds useful for the preparation of the polymerizable
compounds and mixtures containing the compounds.
[0097] The present disclosure further provides optical films and
optically anisotropic products capable of uniform polarized light
conversion over a wide wavelength range, and polarizing plates,
flat panel display devices, organic electroluminescence (EL)
display devices and anti-reflection films including the optical
film or optically anisotropic product.
BRIEF DESCRIPTION OF THE DRAWINGS
[0098] In the accompanying drawings:
[0099] FIGS. 1A and 1B illustrate a configuration of a laminate
used for a stability evaluation test of a liquid crystal phase,
where FIG. 1A is a cross sectional schematic of the laminate, and
FIG. 1B is an explanatory schematic of the relationship between
absorption axis and slow axis; and
[0100] FIGS. 2A and 2B are pictures of laminates used for a
stability evaluation test of a liquid crystal phase, taken from the
side opposite to a light box, where FIG. 2A is a picture of a
laminate having an optically anisotropic product without coating
unevenness (evaluation index: 5), and FIG. 2B is a picture of a
laminate having an optically anisotropic product with coating
unevenness (evaluation index: 1).
DETAILED DESCRIPTION
[0101] The present disclosure will now be described in detail. By
the phrase "may have a substituent" as used herein is meant
"substituted or unsubstituted." Further, it is defined herein that
when organic groups such as alkyl group and aromatic hydrocarbon
ring group in the general formula have a substituent, the number of
carbon atoms of the organic groups having a substituent excludes
the number of carbon atoms of the substituent. For example, when a
C6-C20 aromatic hydrocarbon ring group has a substituent, the
number of carbon atoms of the C6-C20 aromatic hydrocarbon ring
group excludes the number of carbon atoms of such a
substituent.
[0102] The disclosed compound and mixture containing the compound
can be used in any application, e.g., for the preparation of the
disclosed polymerizable compound.
[0103] The disclosed polymerizable compound and mixture containing
the polymerizable compound can be used in any application, e.g.,
for the preparation of the disclosed polymerizable liquid crystal
composition.
[0104] The disclosed polymerizable liquid crystal composition can
be used in any application, e.g., for the preparation of the
disclosed polymer.
[0105] The disclosed polymer can be used in any application, e.g.,
as the constituent material of the disclosed optical film and as
the constituent material of a layer of the disclosed optically
anisotropic product. The disclosed optically anisotropic product
can be used in any application, e.g., for the disclosed polarizing
plate. The disclosed polarizing plate can be used in any
application, e.g., for the disclosed flat panel display device,
organic electroluminescence display device and anti-reflection
film.
[0106] (1) Compound
[0107] The disclosed compound has Formula (I) given below
(hereinafter occasionally referred to as "compound (I)") and is
useful as an intermediate for the production of polymerizable
compound (III) later described.
##STR00012##
[0108] In Formula (I), a is an integer of 1 to 3, b is an integer
of 1 to 20, preferably an integer of 2 to 12, more preferably an
integer of 4 to 8, and c is 0 or 1.
[0109] FG.sup.1 is hydroxyl group, carboxyl group or amino group.
When c is 0, FG.sup.1 is preferably hydroxyl group, and when c is
1, FG.sup.1 is preferably carboxyl group.
[0110] A.sup.1 is alicyclic group which may have a substituent or
aromatic group which may have a substituent. In particular, when c
is 0, A.sup.1 is preferably aromatic group which may have a
substituent, and when c is 1, A.sup.1 is preferably alicyclic group
which may have a substituent.
[0111] The alicyclic group which may have a substituent is a
substituted or unsubstituted divalent alicyclic group, where the
divalent alicyclic group is a divalent aliphatic group having
cyclic structure and typically having 5 to 20 carbon atoms.
[0112] Specific examples of the divalent alicyclic group include
C5-C20 cycloalkanediyl group such as cyclopentane-1.3-diyl,
cyclohexane-1,4-diyl, 1,4-cycloheptane-1,4-diyl, and
cycloctane-1,5-diyl; and C5-C20 bicycloalkanediyl group such as
decahydronaphthalene-1,5-diyl and
decahydronaphthalene-2,6-diyl.
[0113] The aromatic group which may have a substituent is a
substituted or unsubstituted divalent aromatic group, where the
divalent aromatic group is a divalent aromatic group having
aromatic ring structure and typically having 2 to 20 carbon
atoms.
[0114] Specific examples of the divalent aromatic group include
C6-C20 divalent aromatic hydrocarbon ring group such as
1,4-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group,
2,6-naphthylene group, and 4,4'-biphenylene group; and C2-C20
divalent heteroaromatic ring group such as furan-2,5 -diyl, thi
ophene-2,5 -diyl, pyridine-2,5-diyl, and pyrazine-2,5 -diyl.
[0115] Examples of the substituents on the divalent alicyclic group
and divalent aromatic group described above include halogens such
as fluorine, chlorine and bromine; C1-C6 alkyl group such as methyl
group and ethyl group; C1-C5 alkoxy group such as methoxy group and
isopropoxy group; nitro group; and cyano group. The alicyclic group
and aromatic group may have at least one substituent selected from
the substituents described above. When more than one substituent
occurs, each substituent may be the same or different.
[0116] When c is 1, L.sup.1 is single bond, --O--, --CO--,
--CO--O--, --O--CO--, --NR.sup.21--CO--, --CO--NR.sup.22--,
--O--CO--O--, --NR.sup.23--CO--O--, --O--CO--NR.sup.24-- or
--NR.sup.25--CO--NR.sup.26--, where R.sup.21 to R.sup.26 represent
each independently hydrogen or C1-C6 alkyl group. In particular,
L.sup.1 is preferably --O--, --CO--O-- or --O--CO--.
[0117] Examples of the C1-C6 alkyl group for R.sup.21 to R.sup.26
include methyl group, ethyl group, propyl group, and isopropyl
group.
[0118] When c is 1, B.sup.1 is alicyclic group which may have a
substituent or aromatic group which may have a substituent. In
particular, B.sup.1 is preferably aromatic group which may have a
substituent.
[0119] The alicyclic group which may have a substituent is a
substituted or unsubstituted divalent alicyclic group, where the
divalent alicyclic group is a divalent aliphatic group having
cyclic structure and typically having 5 to 20 carbon atoms.
[0120] Specific examples of the divalent alicyclic group for
B.sup.1 are the same as those exemplified for A.sup.1.
[0121] The aromatic group which may have a substituent is a
substituted or unsubstituted divalent aromatic group, where the
divalent aromatic group is a divalent aromatic group having
aromatic ring structure and typically having 2 to 20 carbon
atoms.
[0122] Specific examples of the divalent aromatic group for B.sup.1
are the same as those exemplified for A.sup.1.
[0123] Examples of the substituents on the divalent alicyclic group
and divalent aromatic group for B.sup.1 are the same as those
exemplified for the divalent alicyclic group and divalent aromatic
group for A.sup.1.
[0124] Y.sup.1 is single bond, --O--, --CO--, --CO--O--, --O--CO--,
--NR.sup.21--CO--, --CO--NR.sup.22--, --O--CO--O--,
--NR.sup.23--CO--O--, --O--CO--NR.sup.24-- or
--NR.sup.25--CO--NR.sup.26--, where R.sup.21 to R.sup.26 represent
each independently hydrogen or C1-C6 alkyl group. In particular,
Y.sup.1 is preferably --O--, --CO--O-- or --O--CO--.
[0125] Examples of the C1-C6 alkyl group for R.sup.21 to R.sup.26
include methyl group, ethyl group, propyl group, and isopropyl
group.
[0126] R.sup.2 is hydrogen, methyl group or chlorine, preferably
hydrogen or methyl group.
[0127] R.sup.1 is hydrogen, methyl group or chlorine, preferably
hydrogen or methyl group. More preferably, R.sup.1 and R.sup.2 are
the same, and even more preferably, R.sup.1 and R.sup.2 are
hydrogen.
[0128] Compound (I) described above can be synthesized by combining
synthesis reactions known in the art. Specifically, compound (I)
can be synthesized with reference to methods described in various
literatures, e.g., March's Advanced Organic Chemistry (Wiley), and
S. R. Sandler and W. Karo "Organic Functional Group
Preparations."
[0129] A preferred example of compound (I) where c is 0 includes,
but not limited to, a compound having the following Formula (Ia)
(hereinafter occasionally referred to as "compound (Ia)":
##STR00013##
where R.sup.1, R.sup.2, a and b are as defined above in Formula
(I).
[0130] Compound (Ia) can be produced by any method, e.g., by the
method described below.
##STR00014##
where R.sup.1, R.sup.2, a and b are as defined above in Formula
(I), and L represents leaving group.
[0131] More specifically, first, hydroquinone having Formula (1)
and a compound having Formula (2) (hereinafter referred to as
"compound (2)") are reacted to give a monoether compound having
Formula (3) (hereinafter referred to as "monoether compound
(3)).
[0132] In Formula (2), the leaving group represented by L is any
leaving group commonly used in organic chemistry. Examples of L
include halogens such as chlorine, bromine, and iodine.
[0133] As regards the amounts of hydroquinone and compound (2)
used, typically 1.0 to 5.0 moles, preferably 1.2 to 1.5 moles of
hydroquinone is used per 1 mole of compound (2).
[0134] The use of too little hydroquinone results in increased
production of the by-product diether compound and therefore the
yield and purity of monoether compound (3) tend to decrease. On the
other hand, the use of too much hydroquinone tends to make it
difficult to perform efficient purification treatment after
completion of the reaction.
[0135] The reaction between hydroquinone and compound (2) may be
carried out in inert solvent in the presence of a base, or in a
two-phase solvent system of alkaline aqueous solution/hydrophobic
organic solvent. The latter method is preferred because the target
product can be obtained in higher yield.
[0136] Examples of inert solvents used in this reaction include
amide solvents such as N-methylpyrrolidone, and
N,N-dimethylformamide; ether solvents such as tetrahydrofuran,
1,3-dimethoxyethane, and anisole; sulfur-containing solvents such
as dimethyl sulfoxide; aliphatic hydrocarbon solvents such as
n-pentane, n-hexane, n-heptane, and cyclohexane; aromatic
hydrocarbon solvents such as benzene, toluene, and xylene; and
mixture solvents of two or more of the foregoing.
[0137] Any amount of solvent can be used and the amount can be
determined as appropriate in light of, for example, the types of
compounds used or reaction scale. Typically, 1 to 50 parts by mass
of solvent are used per 1 part by mass of compound (2).
[0138] Examples of bases used include organic bases such as
pyridine, trimethylamine, tri ethyl ami ne, aniline, picoline,
1,8-diazabicyclo[5.4.0]-7-undecene, 1,4-diazabicyclo[2.2.2]octane,
imidazole, and N,N-diisopropylethylamine; metal alcoholates such as
sodium methoxide, sodium ethoxide, and potassium t-butoxide; metal
hydrides such as sodium hydride and calcium hydride; metal
hydroxides such as sodium hydroxide, potassium hydroxide, and
calcium hydroxide; and metal carbonates such as sodium carbonate,
potassium carbonate, and magnesium carbonate.
[0139] Typically, 1 to 5 equivalents, preferably 1 to 2 equivalents
of base are used with respect to compound (2).
[0140] The alkaline aqueous solution used in the latter method can
be obtained by dissolving an inorganic base in water.
[0141] Examples of the inorganic base include alkali metal
carbonates such as sodium carbonate and potassium carbonate; alkali
earth metal carbonates such as magnesium carbonate and calcium
carbonate; alkali metal hydrogen carbonates such as sodium hydrogen
carbonate and potassium hydrogen carbonate; alkali earth metal
hydrogen carbonates such as magnesium hydrogen carbonate and
calcium hydrogen carbonate; alkali metal hydroxides such as sodium
hydroxide and potassium hydroxide; and alkali earth metal
hydroxides such as magnesium hydroxide and calcium hydroxide.
[0142] The inorganic bases can be used alone or in combination.
[0143] The amount of inorganic base in the alkaline aqueous
solution is typically 1.00 to 2.00 moles, preferably 1.05 to 1.50
moles, per 1 mole of compound (2). When the inorganic base content
is too small, there are concerns of reduced yield of the monoether
compound, low reaction rate, or high abundance of residual compound
(2). On the other hand, when too much inorganic base is used, an
additional neutralization step is required after the reaction.
[0144] Any amount of alkaline aqueous solution can be used so long
as hydroquinone and compound (2) are dissolved therein.
[0145] The alkaline aqueous solution is used at an amount of
typically 1 to 10 parts by mass, preferably 3 to 6 parts by mass,
per 1 part by mass of compound (2). When too much alkaline aqueous
solution is used, there are concerns of low reaction rate or low
productivity. On the other hand, when too little alkaline aqueous
solution is used, there are concerns of precipitation of source
compounds, or reduced reaction rate due to increased level of
solution viscosity.
[0146] Hydrophobic organic solvents refer to organic solvents
having a solubility of 10 g or less in 100 g of water at 25.degree.
C.
[0147] Examples of the hydrophobic organic solvent include aromatic
hydrocarbon solvents such as benzene, toluene, xylene, and
mesitylene;
[0148] aliphatic hydrocarbon solvents such as n-pentane, n-hexane,
n-heptane, and cyclohexane; ether solvents such as anisole,
cyclopentyl methyl ether (CPME), diethyl ether, and diisopropyl
ether; C4 or higher alcohol solvents such as 1-butanol and
1-hexanol; and halogenated hydrocarbon solvents such as
dichloromethane, dichloroethane, and chlorobenzene.
[0149] Of these hydrophobic organic solvents, preferred are
aromatic hydrocarbon solvents, ether solvents or C4 or higher
alcohol solvents for example because of their high azeotropic
points with water that enable reactions at high temperatures and
selective production of the target monoether compound (3) is
facilitated, with toluene, xylene, anisole, cyclopentyl methyl
ether, or 1-hexanol being more preferred.
[0150] The hydrophobic organic solvents can be used alone or in
combination.
[0151] The hydrophobic organic solvent is used at an amount of
typically 0.2 to 10 parts by mass, preferably 0.5 to 2 parts by
mass, per 1 part by mass of compound (2). When too much hydrophobic
organic solvent is used, there are concerns of low reaction rate or
low productivity. On the other hand, when too little hydrophobic
organic solvent is used, there are concerns that the monoether
compound can be selectively synthesized only with difficulty
because the effect of using the hydrophobic organic solvent is not
easily obtained.
[0152] The reaction between hydroquinone and compound (2) is
carried out in inert gas atmosphere such as in nitrogen or argon
gas.
[0153] The reaction can be carried out at any temperature, and
reaction temperature is typically 20.degree. C. to 200.degree. C.,
preferably 60.degree. C. to 150.degree. C., more preferably
80.degree. C. to 120.degree. C.
[0154] Reaction time is typically 1 to 24 hours, although it
depends on the reaction temperature and other conditions.
[0155] After completion of the reaction, the reaction solution can
be cooled to precipitate crystals of target monoether compound
(3).
[0156] The purity of monoether compound (3) (ratio of the monoether
compound to the total of the monoether compound and diether
compound) is typically 70mass % or higher, preferably 80mass % or
higher.
[0157] The resulting crystals of monoether compound (3) can be
directly used in the subsequent step without purification or, where
necessary, can be purified by column chromatography,
re-crystallization, re-precipitation or other methods known in the
art to give a more pure monoether compound for use in the
subsequent step.
[0158] The structure of monoether compound (3) can be determined by
NMR spectroscopy, IR spectroscopy, mass spectroscopy, or elemental
analysis.
[0159] Next, the resulting monoether compound (3) and a carboxylic
compound having Formula (4) (hereinafter referred to as "compound
(4)") are subjected to a dehydration condensation reaction to give
target compound (Ia).
[0160] The dehydration condensation reaction is carried out in
proper solvent in the presence of an acid catalyst.
[0161] Examples of acid catalysts used include, but not limited to,
mineral acids such as hydrochloric acid, sulfuric acid, phosphoric
acid, and nitric acid; heteropoly acids such as phosphotungstic
acid; and organic acids such as p-toluenesulfonic acid.
[0162] The acid catalyst is used at an amount of typically 0.01 to
20mass %, preferably 0.05 to 10mass %, more preferably 0.1 to 5mass
%, with respect to monoether compound (3). Alternatively, the acid
catalyst is used at an amount of typically 0.01 to 1.0 mole,
preferably 0.01 to 0.5 moles, per 1 mole of monoether compound
(3).
[0163] Examples of solvents used include ether solvents such as
tetrahydrofuran, 1,3-dimethoxyethane, and anisole; aliphatic
hydrocarbon solvents such as n-pentane, n-hexane, n-heptane, and
cyclohexane; aromatic hydrocarbon solvents such as benzene,
toluene, and xylene; and mixture solvents of two or more of the
foregoing.
[0164] Of these solvents, preferred are aromatic hydrocarbon
solvents, with toluene being more preferred.
[0165] For a better yield of the target compound, the dehydration
condensation reaction is preferably carried out while removing the
generated water out of the system. One exemplary method for that
purpose is to use a Dean-Stark trap or other like device to remove
the generated water out of the system during reaction.
[0166] Further, the dehydration condensation reaction may be
carried out in the presence of an antioxidant to stabilize the
ether compound. Examples of antioxidants used include
2,6-di-(t-butyl)-4-methylphenol (BHT),
2,2'-methylenebis(6-t-butyl-p-cresol), and triphenyl phosphite.
[0167] When an antioxidant is used, it is used at an amount of
typically 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by
mass, per 100 parts by mass of the ether compound.
[0168] The dehydration condensation reaction can be carried out at
any temperature, and reaction temperature is typically 20.degree.
C. to 200.degree. C., preferably 40.degree. C. to 150.degree. C.,
more preferably 60.degree. C. to 150.degree. C.
[0169] Reaction time is typically 1 to 24 hours, although it
depends on the reaction temperature and other conditions.
[0170] After completion of the reaction, post-treatment operations
commonly used in synthetic organic chemistry are performed, and
where desired, the reaction product can be purified by
isolation/purification methods known in the art, such as
distillation, column chromatography, re-crystallization or
re-precipitation, for efficient isolation of the target compound
(Ia).
[0171] The structure of the target compound can be identified by
NMR spectroscopy, IR spectroscopy, mass spectroscopy or other
analysis methods.
[0172] Compound (4) can be obtained by dimerization, trimerization
and tetrameriztion of acrylic acid. In this case, compound (4) is
typically obtained as a mixture containing, in addition to
2-carboxyethyl acrylate (dimer), acrylic acid itself and a trimer
or higher oligomer of acrylic acid.
[0173] Compound (4) can be used as a separate compound isolated by
purifying the mixture obtained in this way.
[0174] Further, as will be described later, when the resulting
mixture contains acrylic acid and compound (4), this mixture
(hereinafter occasionally referred to as "mixture (D)") can be used
instead of compound (4). Mixture (D) preferably contains 0.01 to
20mass % of compound (4).
[0175] A commercially available compound can also be directly used
as compound (4).
[0176] A preferred example of compound (I) where c is 1 includes,
but not limited to, a compound having the following Formula (Ma)
(hereinafter occasionally referred to as "compound (IIIa)":
##STR00015##
where R.sup.1, R.sup.2, a and b are as defined above in Formula
(I).
[0177] Compound (IIIa) can be produced by any method, e.g., by the
method described below where compound (Ia) is reacted with
trans-1,4-cyclohexanedicarboxylic acid having the following Formula
(5):
##STR00016##
where R.sup.1, R.sup.2, a and b are as defined above in Formula
(I), and R.sup.d represents C1-C6 alkyl group such as methyl group
and ethyl group, or C6-C20 aromatic hydrocarbon ring group which
may have a substituent, such as phenyl group, 4-methyl phenyl group
and 4-methoxy phenyl group.
[0178] More specifically, first, compound (5) is reacted with a
sulfonyl chloride having Formula (6) in proper solvent in the
presence of a first base.
[0179] To the resulting reaction mixture are added compound (Ia)
and a second base for further reaction.
[0180] The sulfonyl chloride compound is used at an amount of
typically 0.5 to 2.1 equivalents, preferably 0.5 to 1.1
equivalents, per 1 equivalent of compound (5).
[0181] Compound (Ia) is used at an amount of typically 0.5 to 1.0
equivalent per 1 equivalent of compound (5).
[0182] The first and second bases are used at amounts of typically
0.5 to 2.1 equivalents, preferably 0.5 to 1.1 equivalents, per 1
equivalent of compound (5).
[0183] Examples of the first and second bases include
triethylamine, N,N-diisopropylethylamine, and
4-(dimethylamino)pyridine.
[0184] Reaction temperature can range from -10.degree. C. to
30.degree. C., and reaction time can be several minutes to several
hours, although it depends on the reaction scale and other
conditions.
[0185] Examples of solvents used in the reaction described above
include the same solvents as those exemplified for the production
of compound (Ia), and halogenated solvents such as methylene
chloride and chloroform. Of these solvents, preferred are ether
solvents.
[0186] Any amount of solvent can be used and the amount can be
determined as appropriate in light of, for example, the types of
compounds used or reaction scale. Typically, 1 to 50 parts by mass
of solvent are used per 1 part by mass of compound (Ia).
[0187] After completion of the reaction, post-treatment operations
commonly used in synthetic organic chemistry are performed, and
where desired, the reaction product can be purified by
isolation/purification methods known in the art, such as column
chromatography, re-crystallization, distillation or
re-precipitation, for isolation of the target compound.
[0188] The structure of the target compound can be identified by
NMR spectroscopy, IR spectroscopy, mass spectroscopy, elemental
analysis or other analysis methods.
[0189] (2) Mixture Containing Compounds
[0190] The disclosed mixture is a mixture containing compound (I)
and a compound having the following Formula (II) (hereinafter
referred to as "compound (II)") and can be used for example for the
production of polymerizable compound (III) described later.
[0191] From the perspective of enhancing reverse wavelength
dispersion of the resulting optical film etc. while broadening the
process margin upon formation of the optical film etc. using a
mixture or polymerizable liquid crystal composition containing
polymerizable compound (III) prepared using the mixture, the mass
ratio of compound (I) to compound (II) (compound (I):compound (II))
in the mixture is preferably 1:1,000 to 20:100, more preferably
1:100 to 20:100.
##STR00017##
[0192] In Formula (II) d is an integer of 1 to 20, preferably an
integer of 2 to 12, more preferably an integer of 4 to 8, and e is
0 or 1.
[0193] FG.sup.2 is hydroxyl group, carboxyl group or amino group.
When e is 0, FG.sup.2 is preferably hydroxyl group, and when e is
1, FG.sup.2 is preferably carboxyl group.
[0194] A.sup.2 is alicyclic group which may have a substituent or
aromatic group which may have a substituent. In particular, when e
is 0, A.sup.2 is preferably aromatic group which may have a
substituent, and when e is 1, A.sup.2 is preferably alicyclic group
which may have a substituent.
[0195] The alicyclic group which may have a substituent is a
substituted or unsubstituted divalent alicyclic group, where the
divalent alicyclic group is a divalent aliphatic group having
cyclic structure and typically having 5 to 20 carbon atoms.
[0196] Specific examples of the divalent alicyclic group for
A.sup.2 are the same as those exemplified for A.sup.1.
[0197] The aromatic group which may have a substituent is a
substituted or unsubstituted divalent aromatic group, where the
divalent aromatic group is a divalent aromatic group having
aromatic ring structure and typically having 2 to 20 carbon
atoms.
[0198] Specific examples of the divalent aromatic group for A.sup.2
are the same as those exemplified for A.sup.1.
[0199] Examples of the substituents on the divalent alicyclic group
and divalent aromatic group for A.sup.2 are the same as those
exemplified for the divalent alicyclic group and divalent aromatic
group for A.sup.1.
[0200] When e is 1, L.sup.2 is single bond, --O--, --CO--,
--CO--O--, --O--CO--, --NR.sup.21--CO--, --CO--NR.sup.22--,
--O--CO--O--, --NR.sup.23--CO--O--, --O--CO--NR.sup.24-- or
--NR.sup.25--CO--NR.sup.26--, where R.sup.21 to R.sup.26 represent
each independently hydrogen or C1-C6 alkyl group. In particular,
L.sup.2 is preferably --O--, --CO--O-- or --O--CO--.
[0201] Examples of the C1-C6 alkyl group for R.sup.21 to R.sup.26
include methyl group, ethyl group, propyl group, and isopropyl
group.
[0202] When c is 1, B.sup.2 is alicyclic group which may have a
substituent or aromatic group which may have a substituent. In
particular, B.sup.2 is preferably aromatic group which may have a
substituent.
[0203] The alicyclic group which may have a substituent is a
substituted or unsubstituted divalent alicyclic group, where the
divalent alicyclic group is a divalent aliphatic group having
cyclic structure and typically having 5 to 20 carbon atoms.
[0204] Specific examples of the divalent alicyclic group for
B.sup.2 are the same as those exemplified for A.sup.1.
[0205] The aromatic group which may have a substituent is a
substituted or unsubstituted divalent aromatic group, where the
divalent aromatic group is a divalent aromatic group having
aromatic ring structure and typically having 2 to 20 carbon
atoms.
[0206] Specific examples of the divalent aromatic group for B.sup.2
are the same as those exemplified for A.sup.1.
[0207] Examples of the substituents on the divalent alicyclic group
and divalent aromatic group for B.sup.2 are the same as those
exemplified for the divalent alicyclic group and divalent aromatic
group for A.sup.1.
[0208] Y.sup.2 is single bond, --O--, --CO--, --CO--O--, --O--CO--,
--NR.sup.21--CO--, --CO--NR.sup.22--, --O--CO--O--,
--NR.sup.23--CO--O--, --O--CO--NR.sup.24-- or
--NR.sup.25--CO--NR.sup.26--, where R.sup.21 to R.sup.26 are each
independently hydrogen or C1-C6 alkyl group. In particular, Y.sup.2
is preferably --O--, --CO--O-- or --O--CO--.
[0209] Examples of the C1-C6 alkyl group for R.sup.21 to R.sup.26
include methyl group, ethyl group, propyl group, and isopropyl
group.
[0210] R.sup.3 is hydrogen, methyl group or chlorine, preferably
hydrogen or methyl group.
[0211] Compound (II) described above can be synthesized by
combining synthesis methods known in the art. Specifically,
compound (II) can be synthesized with reference to methods
described in various literatures, e.g., March's Advanced Organic
Chemistry (Wiley), and S. R. Sandler and W. Karo "Organic
Functional Group Preparations."
[0212] From the perspective of enhancing reverse wavelength
dispersion of optical film etc., in the disclosed mixture,
FG.sup.1, A.sup.1, L.sup.1, B.sup.1, Y.sup.1, R.sup.1, b and c of
compound (I) are preferably the same as FG.sup.2, A.sup.2, L.sup.2,
B.sup.2, Y.sup.2, R.sup.3, d and e of compound (II), respectively.
Specifically, compound (II) preferably has the same structure as
compound (I) except for the absence of
--(CH.sub.2CHR.sup.1COO).sub.a-- between CH.sub.2CR.sup.1COO-- and
--(CH.sub.2).sub.b--.
[0213] The mixture can be prepared for example by mixing compounds
(I) and (II) at desired ratios.
[0214] Further, a mixture of compound (I) where c is 0 and compound
(II) where e is 0 can be obtained by any method, e.g., by reacting
mixture (D) with a compound having the following formula:
HO--(CH.sub.2).sub.b--Y.sup.1-A.sup.1-FG.sup.1
where Y.sup.1, A.sup.1, FG.sup.1 and b are as defined in Formula
(I).
[0215] Further, a mixture of compound (I) where c is 1 and compound
(II) where e is 1 can be obtained by any method, e.g., by reacting
a mixture containing compound (I) where c is 0 and compound (II)
where e is 0 with a compound having the following formula:
L.sup.3-A.sup.1-FG.sup.3
where L.sup.3 represent a group which may form --O--, --CO--,
--CO--O--, --O--CO--, --NR.sup.21--CO--, --CO--NR.sup.22,
--O--CO--O--, --NR.sup.23CO--O--, --O--CO--NR.sup.24-- or
--NR.sup.25--CO--NR.sup.26-- by reaction with FG.sup.1 of compound
(I) where c is 0 and FG.sup.2 of compound (II) where e is 0, with
the proviso that R.sup.21 to R.sup.26 are each independently
hydrogen or C1-C6 alkyl group; A.sup.1 is as defined in Formula
(I); and FG.sup.3 represents hydroxyl group, carboxyl group or
amino group.
[0216] The mixture of compound (I) where c is 1 and compound (II)
where e is 1 may further contain a compound having Formula
(.alpha.) shown below. The amount of the compound having Formula
(.alpha.) is 0.05 to 60 mass %, preferably 0.05 to 50 mass %, more
preferably 0.05 to 35 mass %, of the total amount of compound (I)
where c is 1 and compound (II) where e is 1.
##STR00018##
where Y.sup.1, B.sup.1, L.sup.1, A.sup.1, R.sup.1, R.sup.2 and b
are as defined in Formula (I), and x and y represent each
independently an integer of 0 to 3.
[0217] A preferred example of compound (II) where e is 0 includes,
but not limited to, a compound having the following Formula (IIa)
(hereinafter occasionally referred to as "compound (IIa)"):
##STR00019##
where R.sup.3 and d are as defined in Formula (II).
[0218] Compound (IIa) can be produced by any of the methods known
in the art, e.g., by the method described in PTL 1.
[0219] The mixture containing compounds (Ia) and (IIa) can be
prepared for example by mixing compounds (Ia) and (IIa) at desired
ratios.
[0220] The mixture containing compounds (Ia) and (IIa) can also be
obtained for example by replacing compound (4) by mixture (D) in
the above-described method of producing compound (Ia) as shown
below.
##STR00020##
where R.sup.1, R.sup.2, a and b are as defined in Formula (I), and
R.sup.3 and d(=b) are as defined in Formula (II).
[0221] A preferred example of compound (II) where e is 1 includes,
but not limited to, a compound having the following Formula (IVa)
(hereinafter occasionally referred to as "compound (IVa)"):
##STR00021##
where R.sup.3 and d are as defined in Formula (II).
[0222] Compound (IVa) can be produced by any of the methods known
in the art, e.g., by the method described in PTL 1.
[0223] The mixture containing compounds (IIIa) and (IVa) can be
prepared for example by mixing compounds (IIIa) and (IVa) at
desired ratios.
[0224] The mixture containing compounds (IIIa) and (IVa) can also
be obtained for example by replacing compound (Ia) with the mixture
containing compounds (Ia) and (IIa) in the above-described method
of producing compound (IIIa) as shown below.
##STR00022##
where R.sup.1, R.sup.2, a and b are as defined in Formula (I),
R.sup.3 and d are as defined in Formula (II), and R.sup.d is as
defined in Formula (6).
[0225] (3) Polymerizable Compound
[0226] The disclosed polymerizable compound is a compound having
Formula (III) shown below (hereinafter occasionally referred to as
"polymerizable compound (III)") and can be advantageously used for
the preparation of a polymer, an optical film and an optically
anisotropic product which are described later.
##STR00023##
[0227] As will be described later, the use of a mixture of
polymerizable compound (III) and polymerizable compound (IV)
(compound having Formula (IV)) to be described in detail later
makes it possible to obtain a polymerizable liquid crystal
composition which can retain liquid crystal phase more stably over
long periods of time, has a wide process margin, has a low melting
point suitable for practical use, has superior solubility in common
solvents, and allows for the low-cost manufacture of optical film
etc. which are capable of uniform polarized light conversion over a
wide wavelength range.
[0228] A possible but still uncertain reason for this is that
polymerizable compound (III) has a moiety represented by
--(CH.sub.2CHR.sup.5COO).sub.f-- and/or a moiety represented by
--(OCOCHR.sup.6CH.sub.2).sub.k-- and hence the use of a mixture of
polymerizable compounds (III) and (IV) results in the formation of
a liquid crystal layer that easily turns into liquid crystal phase
at lower temperatures (i.e., easily becomes supercooling state at
room temperature) compared to cases where only polymerizable
compound (IV) is used while ensuring optical characteristics
(especially reverse wavelength dispersion), so that optical film
etc. having a polymer as the constituent material can be
obtained.
[0229] It should be noted that polymerizable compound (III) also
can be used alone for the preparation of polymerizable liquid
crystal compositions, polymers, and optical film etc. containing
the polymer as the constituent material, without being mixed with
polymerizable compound (IV).
[0230] In Formula (III), one of f and k is an integer of 1 to 3 and
the other is an integer of 0 to 3, g and j are each independently
an integer of 1 to 20, preferably an integer of 2 to 12, more
preferably an integer of 4 to 8, and h and i are each independently
0 or 1, preferably 1.
[0231] Ar.sup.1 is divalent aromatic hydrocarbon ring group having
D.sup.1 as a substituent or divalent heteroaromatic ring group
having D.sup.1 as a substituent. D.sup.1 is C1-C20 organic group
having at least one aromatic ring selected from the group
consisting of an aromatic hydrocarbon ring and a heteroaromatic
ring.
[0232] The divalent aromatic hydrocarbon ring group having D.sup.1
as a substituent or divalent heteroaromatic ring group having
D.sup.1 as a substituent refers to a group obtained by removing,
from the ring moiety of the aromatic hydrocarbon ring or
heteroaromatic ring to which D.sup.1 is bound, two hydrogens
attached to carbon atoms other than the carbon atom to which
D.sup.1 is bound.
[0233] Examples of the divalent aromatic hydrocarbon ring group for
Ar.sup.1 include 1,4-phenylene group, 1,3-phenylene group,
1,4-naphthylene group, 2,6-naphthylene group, 1,5-naphthylene
group, anthracenyl-9,10-diyl group, anthracenyl-1,4-diyl group, and
anthracenyl-2,6-diyl group.
[0234] Of these divalent aromatic hydrocarbon ring groups,
preferred is 1,4-phenylene group, 1,4-naphthylene group or
2,6-naphthylene group.
[0235] Examples of the divalent heteroaromatic ring group for
Ar.sup.1 include benzothiazole-4,7-diyl group,
1,2-benzisothiazole-4,7-diyl group, benzoxazole-4,7-diyl group,
indonyl-4,7-diyl group, benzimidazole-4,7-diyl group,
benzopyrazole-4,7-diyl group, 1-benzofuran-4,7-diyl group,
2-benzofuran-4,7-diyl group,
benzo[1,2-d:4,5-d']dithiazolyl-4,8-diyl group,
benzo[1,2-d:5,4-d']dithiazolyl-4,8-diyl group,
benzothiophenyl-4,7-diyl group, 1H-isoindole-1,3(2H)-dione-4,7-diyl
group, benzo[1,2-b:5,4-b']dithiophenyl-4,8-diyl group, benzo[1,2-b
:4,5-b']dithiophenyl-4,8-diyl group,
benzo[1,2-b:5,4-b']difuranyl-4,8-diyl group,
benzo[1,2-b:4,5-b']difuranyl-4,8-diyl group,
benzo[2,1-b:4,5-b']dipyrrole-4,8-diyl group, benzo[1,2-b:5,4-b'
dipyrrole-4,8-diyl group, and
benzo[1,2-d:4,5-d']diimidazole-4,8-diyl group.
[0236] Of these divalent heteroaromatic ring groups, preferred is
benzothiazole-4,7-diyl group, benzoxazole-4,7-diyl group,
1-benzofuran-4,7-diyl group, 2-benzofuran-4,7-diyl group,
benzo[1,2-d:4,5-d']dithiazolyl-4,8-diyl group,
benzo[1,2-d:5,4-d']dithiazolyl-4,8-diyl group,
benzothiophenyl-4,7-diyl group, 1H-isoindole-1,3(2H)-dione-4,7-diyl
group, benzo[1,2-b:5,4-b' dithiophenyl-4,8-diyl group, benzo[1,2
-b:4,5-b']dithiophenyl-4,8-diyl group, benzo[1,2
-b:5,4-b']difuranyl-4,8-diyl group or
benzo[1,2-b:4,5-b']difuranyl-4,8-diyl group.
[0237] The divalent aromatic hydrocarbon ring group and divalent
heteroaromatic ring group for Ar.sup.1 may have, in addition to
D.sup.1, at least one substituent selected from C1-C6 alkyl group
such as methyl group, ethyl group, propyl group, isopropyl group,
butyl group, sec-butyl group, and tert-butyl group. When more than
one substituent occurs, each substituent may be the same or
different. Preferred for the divalent aromatic hydrocarbon ring
group and divalent heteroaromatic ring group other than D.sup.1 is
at least one substituent selected from methyl group, ethyl group,
propyl group, sec-butyl group, and tert-butyl group.
[0238] By the term "aromatic ring" used in "C1-C20 organic group
having at least one aromatic ring selected from the group
consisting of an aromatic hydrocarbon ring and a heteroaromatic
ring" for D.sup.1 is meant a cyclic structure that has aromaticity
in a broad sense following Huckel's rule, i.e., a cyclic conjugated
structure having (4n+2) .pi. electrons, as well as a cyclic
structure that exhibits aromaticity due to involvement of a lone
electron pair of a hetero atom such as sulfur, oxygen or nitrogen
with the .pi. electron system, as represented by the cyclic
structure of thiophene, furan, benzothiazole or the like.
[0239] The aromatic ring of D1 may have one or more
substituents.
[0240] The total number of .pi. electrons in Ar.sup.1 and D.sup.1
is typically 12 or more, preferably 12 to 22, more preferably 12 to
20.
[0241] Examples of the aromatic hydrocarbon ring for D.sup.1
include benzene ring, naphthalene ring, anthracene ring,
phenanthrene ring, pyrene ring, and fluorine ring.
[0242] Of these aromatic hydrocarbon rings, preferred are benzene
ring and naphthalene ring.
[0243] Examples of the heteroaromatic ring for D.sup.1 include
1H-isoindole-1,3(2H)-dione ring, 1-benzofuran ring, 2-benzofuran
ring, acridine ring, isoquinoline ring, imidazole ring, indole
ring, oxadiazole ring, oxazole ring, oxazolopyrazine ring,
oxazolopyridine ring, oxazolopyridazyl ring, oxazolopyrimidine
ring, quinazoline ring, quinoxaline ring, quinoline ring, cinnoline
ring, thiadiazole ring, thiazole ring, thiazolopyrazine ring,
thiazolopyridine ring, thiazolopyridazine ring, thiazolopyrimidine
ring, thiophene ring, triazine ring, triazole ring, naphthyridine
ring, pyrazine ring, pyrazole ring, pyranone ring, pyran ring,
pyridine ring, pyridazine ring, pyrimidine ring, pyrrole ring,
phenanthridine ring, phthalazine ring, furan ring,
benzo[c]thiophene ring, benzisoxazole ring, benzisothiazole ring,
benzimidazole ring, benzoxadiazole ring, benzoxazole ring,
benzothiadiazole ring, benzothiazole ring, benzothiophene ring,
benzotriazine ring, benzotriazole ring, benzopyrazole ring,
benzopyranone ring, dihydropyran ring, tetrahydropyran ring,
dihydrofuran ring, and tetrahydrofuran ring.
[0244] Of these heteroaromatic rings, preferred are benzothiazole
ring, benzoxazole ring, 1-benzofuran ring, 2-benzofuran ring,
benzothiophene ring, 1H-isoindole-1,3(2H)-dione ring, thiophene
ring, furan ring, benzo[c]thiophene ring, oxazole ring, thiazole
ring, oxadiazole ring, pyran ring, benzisoxazole ring, thiadiazole
ring, benzoxadiazole ring, and benzothiadiazole ring.
[0245] Examples of the C1-C20 organic group having at least one
aromatic ring selected from the group consisting of an aromatic
hydrocarbon ring and a heteroaromatic ring for D.sup.1 include, but
not limited to, an aromatic hydrocarbon ring group which may have a
substituent, a heteroaromatic ring group which may have a
substituent, and a group having the formula
--R.sup.fC(.dbd.N--NR.sup.gR.sup.h).
[0246] In the formula, R.sup.f represents hydrogen or C1-C6 alkyl
group such as methyl group, ethyl group, propyl group or isopropyl
group.
[0247] In the formula, R.sup.g represents hydrogen or C1-C20
organic group which may have a substituent. Specific examples of
the C1-C20 organic group and substituents thereon for R.sup.g are
the same as those exemplified for Ra described later.
[0248] In the formula, R.sup.h represents C2-C20 organic group
having at least one aromatic ring selected from the group
consisting of an aromatic hydrocarbon ring and a heteroaromatic
ring. Specific examples of the C2-C20 organic group and
substituents thereon for R.sup.h are the same as those exemplified
for Ax described later.
[0249] More specifically, examples of the aromatic hydrocarbon ring
group which serves as D.sup.1 include phenyl group, naphthyl group,
anthracenyl group, phenanthrenyl group, pyrenyl group, and
fluorenyl group.
[0250] Of these aromatic hydrocarbon ring groups, preferred are
phenyl group and naphthyl group.
[0251] Examples of the heteroaromatic ring group which serves as
D.sup.1 include phthalimide group, 1-benzofuranyl group,
2-benzofuranyl group, acrydinyl group, isoquinolinyl group,
imidazolyl group, indolinyl group, furazanyl group, oxazolyl group,
oxazolopyrazinyl group, oxazolopyridinyl group, oxazolopyridazinyl
group, oxazolopyrimidinyl group, quinazolinyl group, quinoxalinyl
group, quinolyl group, cinnolinyl group, thiadiazolyl group,
thiazolyl group, thiazolopyrazinyl group, thiazolopyridyl group,
thiazolopyridazinyl group, thiazolopyrimidinyl group, thienyl
group, triazinyl group, triazolyl group, naphthyridinyl group,
pyrazinyl group, pyrazolyl group, pyranonyl group, pyranyl group,
pyridyl group, pyridazinyl group, pyrimidinyl group, pyrrolyl
group, phenanthridinyl group, phthalazinyl group, furanyl group,
benzo[c]thienyl group, benzisoxazolyl group, benzisothiazolyl
group, benzimidazolyl group, benzoxazolyl group, benzothiadiazolyl
group, benzothiazolyl group, benzothienyl group, benzotriadinyl
group, benzotriazolyl group, benzopyrazolyl group, benzopyranonyl
group, dihydropyranyl group, tetrahydropyranyl group,
dihydrofuranyl group, and tetrahydrofuranyl group.
[0252] Of these heteroaromatic ring groups, preferred are furanyl
group, thienyl group, oxazolyl group, thiazolyl group,
benzothiazolyl group, benzoxazolyl group, 1-benzofuranyl group,
2-benzofuranyl group, benzothienyl group, and thiazolopyridyl
group.
[0253] The aromatic hydrocarbon ring group and heteroaromatic ring
group which serve as D.sup.1 may have at least one substituent
selected from C1-C20 aliphatic hydrocarbon group such as methyl
group, ethyl group, propyl group, isopropyl group, butyl group, and
sec-butyl group; halogens such as fluorine and chlorine; cyano
group; substituted-amino group such as dimethylamino group; C1-C6
alkoxy group such as methoxy group, ethoxy group, and isopropoxy
group; nitro group; C3-C8 cycloalkyl group such as cyclopentyl
group and cyclohexyl group; C 1-C6 halogenated alkyl group such as
trifluoromethyl group; --C(.dbd.O)--R.sup.b;
--C(.dbd.O)--OR.sup.b'; --SR.sup.b'; --SO.sub.2R.sup.d'; and
hydroxyl group, where R.sup.b' represents C1-C20 alkyl group which
may have a substituent, C2-C20 alkenyl group which may have a
substituent, C3-C12 cycloalkyl group which may have a substituent,
or C5-C12 aromatic hydrocarbon ring group which may have a
substituent, and R.sup.d' represents C1-C6 alkyl group such as
methyl group and ethyl group; or C6-C20 aromatic hydrocarbon ring
group which may have a substituent, such as phenyl group, 4-methyl
phenyl group and 4-methoxyphenyl group. When the aromatic
hydrocarbon ring group and heteroaromatic ring group have more than
one substituent, each substituent may be the same or different.
[0254] Examples of the substituents on the C1-C20 alkyl, C2-C20
alkenyl and C5-C12 aromatic hydrocarbon ring groups which may have
a substituent for R.sup.b' include halogens such as fluorine and
chlorine; cyano group; C1-C20 alkoxy group such as methoxy group,
ethoxy group, isopropoxy group, and butoxy group; nitro group;
C6-C20 aromatic hydrocarbon ring group such as phenyl group and
naphthyl group; C2-20 heteroaromatic ring group such as furanyl
group and thiophenyl group; C3-C8 cycloalkyl group such as
cyclopropyl group, cyclopentyl group, and cyclohexyl group; and
C1-C12 fluoroalkyl group at least one hydrogen of which is replaced
by fluorine, such as trifluoromethyl group, pentafluoroethyl group,
and --CH.sub.2CF.sub.3. The C1-20 alkyl group, C2-C20 alkenyl group
and C5-C12 aromatic hydrocarbon ring group for R.sup.b' may have
one or more sub stituents selected from those described above. When
they have more than one substituent, each substituent may be the
same or different.
[0255] Examples of the substituent on the C3-C12 cycloalkyl group
for R.sup.b' include halogens such as fluorine and chlorine; cyano
group; C1-C6 alkyl group such as methyl group, ethyl group and
propyl group; C1-C6 alkoxy group such as methoxy group, ethoxy
group and isopropoxy group; nitro group; and C6-C20 aromatic
hydrocarbon group such as phenyl group and naphthyl group. The
C3-C12 cycloalkyl group for R.sup.b' may have one or more
substituents selected from those described above. When it has more
than one substituent, each substituent may be the same or
different.
[0256] Examples of combinations of Ar.sup.1 and D.sup.1
(Ar.sup.1-D.sup.1) include phenylene group substituted with a group
having the formula --R.sup.fC(.dbd.N--NR.sup.gR.sup.h),
benzothiazole-4,7-diyl group substituted with 1-benzofuran-2-yl
group, benzothiazole-4,7-diyl group substituted with
5-(2-butyl)-1-benzofuran-2-yl group, benzothiazole-4,7-diyl group
sub stituted with 4,6-dimethyl-1-benzofuran-2-yl group,
benzothiazole-4,7-diyl group substituted with
6-methyl-1-benzofuran-2-yl group, benzothiazole-4,7-diyl group
substituted with 4,6,7-trimethyl-1-benzofuran-2-yl group,
benzothiazole-4,7-diyl group sub stituted with
4,5,6-trimethyl-1-benzofuran-2-yl group, benzothiazole-4,7-diyl
group substituted with 5-methyl-1-benzofuran-2-yl group,
benzothiazole-4,7-diyl group substituted with
5-propyl-1-benzofuran-2-yl group, benzothiazole-4,7-diyl group
substituted with 7-propyl-1-benzofuran-2-yl group,
benzothiazole-4,7-diyl group sub stituted with
5-fluoro-1-benzofuran-2-yl group, benzothiazole-4,7-diyl group
substituted with phenyl group, benzothiazole-4,7-diyl group
substituted with 4-fluorophenyl group, benzothiazole-4,7-diyl group
substituted with 4-nitrophenyl group, benzothiazole-4,7-diyl group
substituted with 4-trifluoromethylphenyl group,
benzothiazole-4,7-diyl group substituted with 4-cyanophenyl group,
benzothiazole-4,7-diyl group substituted with
4-methanesulfonylphenyl group, benzothiazole-4,7-diyl group
substituted with thiophene-2-yl group, benzothiazole-4,7-diyl group
substituted with thiophene-3-yl group, benzothiazole-4,7-diyl group
substituted with 5-methylthiophene-2-yl group,
benzothiazole-4,7-diyl group substituted with
5-chlorothiophene-2-yl group, benzothiazole-4,7-diyl group
substituted with thieno[3,2-b]thiophene-2-yl group,
benzothiazole-4,7-diyl group substituted with 2-benzothiazolyl
group, benzothiazole-4,7-diyl group substituted with 4-biphenyl
group, benzothiazole-4,7-diyl group substituted with
4-propylbiphenyl group, benzothiazole-4,7-diyl group substituted
with 4-thiazolyl group, benzothiazole-4,7-diyl group substituted
with 1-phenylethylene-2-yl group, benzothiazole-4,7-diyl group
substituted with 4-pyridyl group, benzothiazole-4,7-diyl group
substituted with 2-furyl group, benzothiazole-4,7-diyl group
substituted with naphtho[1,2-b]furan-2-yl group,
1H-isoindole-1,3(2H)-dione-4,7-diyl group sub stituted with
5-methoxy-2-benzothiazolyl group, 1H-i
soindole-1,3(2H)-dione-4,7-diyl group substituted with phenyl
group, 1H-isoindole-1,3(2H)-dione-4,7-diyl group substituted with
4-nitrophenyl group, and 1H-isoindole-1,3(2H)-dione-4,7-diyl group
substituted with 2-thiazolyl group. R.sup.f, R.sup.g and R.sup.h in
the formula --R.sup.fC(.dbd.N--NR.sup.gR.sup.h) are as defined
above.
[0257] Ar.sup.1-D.sup.1 is preferably a divalent group having the
following Formula (V):
##STR00024##
where Ax represents C2-C20 organic group having at least one
aromatic ring selected from the group consisting of an aromatic
hydrocarbon ring and a heteroaromatic ring, and Ra represents
hydrogen or C1-C20 organic group which may have a substituent.
[0258] In the present disclosure, a moiety having the following
Formula (i) refers to a moiety having the following Formula (ia)
and/or Formula (iib).
##STR00025##
[0259] By the term "aromatic ring" used in "C2-C20 organic group
having at least one aromatic ring selected from the group
consisting of an aromatic hydrocarbon ring and a heteroaromatic
ring" for Ax is meant a cyclic structure that has aromaticity in a
broad sense following Huckel's rule, i.e., a cyclic conjugated
structure having (4n+2) .pi. electrons, as well as a cyclic
structure that exhibits aromaticity due to involvement of a lone
electron pair of a hetero atom such as sulfur, oxygen or nitrogen
with the .pi. electron system, as represented by the cyclic
structure of thiophene, furan, benzothiazole or the like.
[0260] The C2-C20 organic group having at least one aromatic ring
selected from the group consisting of an aromatic hydrocarbon ring
and a heteroaromatic ring for Ax may have more than aromatic ring
or may have an aromatic hydrocarbon ring and a heteroaromatic
ring.
[0261] Examples of the aromatic hydrocarbon ring for Ax include
benzene ring, naphthalene ring, anthracene ring, phenanthrene ring,
pyrene ring, fluorene ring.
[0262] Of these aromatic hydrocarbon rings, preferred are benzene
ring and naphthalene ring.
[0263] Examples of the heteroaromatic ring for Ax include
1H-isoindole-1,3(2H)-dione ring, 1-benzofuran ring, 2-benzofuran
ring, acridine ring, isoquinoline ring, imidazole ring, indole
ring, oxadiazole ring, oxazole ring, oxazolopyrazine ring,
oxazolopyridine ring, oxazolopyridazyl ring, oxazolopyrimidine
ring, quinazoline ring, quinoxaline ring, quinoline ring, cinnoline
ring, thiadiazole ring, thiazole ring, thiazolopyrazine ring,
thiazolopyridine ring, thiazolopyridazine ring, thiazolopyrimi dine
ring, thiophene ring, triazine ring, triazole ring, naphthyridine
ring, pyrazine ring, pyrazole ring, pyranone ring, pyran ring,
pyridine ring, pyridazine ring, pyrimidine ring, pyrrole ring,
phenanthridine ring, phthalazine ring, furan ring,
benzo[c]thiophene ring, benzisoxazole ring, benzisothiazole ring,
benzimidazole ring, benzoxadiazole ring, benzoxazole ring,
benzothiadiazole ring, benzothiazole ring, benzothiophene ring,
benzotriazine ring, benzotriazole ring, benzopyrazole ring,
benzopyranone ring, dihydropyran ring, tetrahydropyran ring,
dihydrofuran ring, and tetrahydrofuran ring.
[0264] Of these heteroaromatic rings, preferred are monocyclic
heteroaromatic rings such as furan ring, thiophene ring, oxazole
ring, and thiazole ring; and condensed heteroaromatic rings such as
benzothiazole ring, benzoxazole ring, quinoline ring, 1-benzofuran
ring, 2-benzofuran ring, benzothiophene ring, thiazolopyridine
ring, and thiazolopyrazine ring.
[0265] The aromatic ring of Ax may have a substituent. Examples of
the substituent include halogens such as fluorine and chlorine;
cyano group; C1-C6 alkyl group such as methyl group, ethyl group,
and propyl group; C2-C6 alkenyl group such as vinyl group and allyl
group; C1-C6 halogenated alkyl group such as trifluoromethyl group;
substituted amino group such as dimethylamino group; C1-C6 alkoxy
group such as methoxy group, ethoxy group, and isopropoxy group;
nitro group; C6-C20 aromatic hydrocarbon ring group such as phenyl
group and naphthyl group; --C(.dbd.O)--R.sup.b;
--C(.dbd.O)--OR.sup.b; and --SO.sub.2R.sup.d, where R.sup.b
represents C1-C20 alkyl group which may have a substituent, C2-C20
alkenyl group which may have a substituent, C3-C12 cycloalkyl group
which may have a substituent, or C5-C12 aromatic hydrocarbon ring
group which may have a substituent, and R.sup.d represents C1-C6
alkyl group such as methyl group and ethyl group, or C6-C20
aromatic hydrocarbon ring group which may have a substituent, such
as phenyl group, 4-methyl phenyl group, and 4-methoxyphenyl group.
Of these sub stituents on the aromatic ring of Ax, preferred are
halogens, cyano group, C1-C6 alkyl group, and C1-C6 alkoxy
group.
[0266] Ax may have more than one substituent selected from those
described above. When Ax has more than one substituent, each
substituent may be the same or different.
[0267] Examples of the C1-C20 alkyl group of the C1-C20 alkyl group
which may have a substituent for R.sup.b include methyl group,
ethyl group, n-propyl group, isopropyl group, n-butyl group,
isobutyl group, 1-methylpentyl group, 1-ethylpentyl group,
sec-butyl group, t-butyl group, n-pentyl group, isopentyl group,
neopentyl group, n-hexyl group, isohexyl group, n-heptyl group,
n-octyl group, n-nonyl group, n-decyl group, n-undecyl group,
n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl
group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group,
n-nonadecyl group, and n-icosyl group. The C1-C20 alkyl group which
may have a substituent preferably has 1 to 12 carbon atoms, more
preferably 4 to 10 carbon atoms.
[0268] Examples of the C2-C20 alkenyl group of the C2-C20 alkenyl
group which may have a substituent for R.sup.b include vinyl group,
propenyl group, isopropenyl group, butenyl group, isobutenyl group,
pentenyl group, hexenyl group, heptenyl group, octenyl group,
decenyl group, undecenyl group, dodecenyl group, tridecenyl group,
tetradecenyl group, pentadecenyl group, hexadecenyl group,
heptadecenyl group, octadecenyl group, nonadecenyl group, and
icocenyl group.
[0269] The C2-C20 alkenyl group which may have a substituent
preferably has 2 to 12 carbon atoms.
[0270] Examples of the substituents on the C1-C20 alkyl group and
C2-20 alkenyl group for R.sup.b include halogens such as fluorine
and chlorine; cyano group; substituted amino group such as
dimethylamino group; C1-C20 alkoxy group such as methoxy group,
ethoxy group, isopropoxy group, and butoxy group; C1-C12 alkoxy
group substituted with C1-C12 alkoxy group, such as methoxymethoxy
group and methoxyethoxy group; nitro group; C6-C20 aromatic
hydrocarbon ring group such as phenyl group and naphthyl group;
C2-C20 heteroaromatic ring group such as triazolyl group, pyrrolyl
group, furanyl group, and thiophenyl group; C3-C8 cycloalkyl group
such as cyclopropyl group, cyclopentyl group, and cyclohexyl group;
C3-C8 cycloalkyloxy group such as cyclopentyloxy group and
cyclohexyloxy group; C2-C12 cyclic ether group such as
tetrahydrofuranyl group, tetrahydropyranyl group, dioxolanyl group,
and dioxanyl group; C6-C14 aryloxy group such as phenoxy group and
naphthoxy group; C1-C12 fluoroalkyl group at least one hydrogen of
which is replaced by fluorine, such as trifluoromethyl group,
pentafluoroethyl group, and --CH.sub.2CF.sub.3; benzofuryl group;
benzopyranyl group; benzodioxolyl group; and benzodioxanyl group.
Of these substituents on the C1-C20 alkyl group and C2-C20 alkenyl
group for R.sup.b, preferred are halogens such as fluorine and
chlorine; cyano group; C1-C20 alkoxy group such as methoxy group,
ethoxy group, isopropoxy group, and butoxy group; nitro group;
C6-C20 aromatic hydrocarbon ring group such as phenyl group and
naphthyl group; C2-C20 heteroaromatic ring group such as furanyl
group and thiophenyl group; C3-C8 cycloalkyl group such as
cyclopropyl group, cyclopentyl group, and cyclohexyl group; and
C1-C12 fluoroalkyl group at least one hydrogen of which is replaced
by fluorine, such as trifluoromethyl group, pentafluoroethyl group,
and --CH.sub.2CF.sub.3.
[0271] The C1-C20 alkyl group and C2-C20 alkenyl group for R.sup.b
may have more than one substituent selected from those described
above. When the C1-C20 alkyl group and C2-C20 alkenyl group for
R.sup.b have more than one substituent, each substituent may be the
same or different.
[0272] Examples of the C3-C12 cycloalkyl group of the C3-C12
cycloalkyl group which may have a substituent for R.sup.b include
cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl
group, and cyclooctyl group. Of these cycloalkyl groups, preferred
are cyclopentyl group and cyclohexyl group.
[0273] Examples of the substituent on the C3-C12 cycloalkyl group
for R.sup.b include halogens such as fluorine and chlorine; cyano
group; substituted amino group such as dimethylamino group; C1-C6
alkyl group such as methyl group, ethyl group, and propyl group; C1
-C6 alkoxy group such as methoxy group, ethoxy group, and
isopropoxy group; nitro group; and C6-C20 aromatic hydrocarbon
group such as phenyl group and naphthyl group. Of these
substituents on the C3-C12 cycloalkyl group for R.sup.b, preferred
are halogens such as fluorine and chlorine; cyano group; C1-C6
alkyl group such as methyl group, ethyl group, and propyl group;
C1-C6 alkoxy group such as methoxy group, ethoxy group, and
isopropoxy group; nitro group; and C6-C20 aromatic hydrocarbon
group such as phenyl group and naphthyl group.
[0274] The C3-C12 cycloalkyl group for R.sup.b may have more than
one substituent. When it has more than one substituent, each
substituent may be the same or different.
[0275] Examples of the C5-C12 aromatic hydrocarbon ring group of
the C5-C12 aromatic hydrocarbon ring group which may have a sub
stituent for R.sup.b include phenyl group, 1-naphthyl group, and
2-naphthyl group, with phenyl group being preferred.
[0276] Examples of the substituent on the C5-C12 aromatic
hydrocarbon ring group which may have a substituent include
halogens such as fluorine and chlorine; cyano group; substituted
amino group such as dimethylamino group; C1-C20 alkoxy group such
as methoxy group, ethoxy group, isopropoxy group, and butoxy group;
C1-C12 alkoxy group substituted with C1-C12 alkoxy group, such as
methoxymethoxy group and methoxyethoxy group; nitro group; C6-C20
aromatic hydrocarbon ring group such as phenyl group and naphthyl
group; C2-C20 heteroaromatic ring group such as triazolyl group,
pyrrolyl group, furanyl group, and thiophenyl group; C3-C8
cycloalkyl group such as cyclopropyl group, cyclopentyl group, and
cyclohexyl group; C3-C8 cycloalkyloxy group such as cyclopentyloxy
group and cyclohexyloxy group; C2-C12 cyclic ether group such as
tetrahydrofuranyl group, tetrahydropyranyl group, dioxolanyl group,
and dioxanyl group; C6-C14 aryloxy group such as phenoxy group and
naphthoxy group; C1-C12 fluoroalkyl group at least one hydrogen of
which is replaced by fluorine, such as trifluoromethyl group,
pentafluoroethyl group, and --CH.sub.2CF.sub.3; benzofuryl group;
benzopyranyl group; benzodioxolyl group; and benzodioxanyl group.
Of these substituents on the C5-C12 aromatic hydrocarbon ring
group, preferred is at least one substituent selected from halogens
such as fluorine and chlorine; cyano group; C 1 -C20 alkoxy group
such as methoxy group, ethoxy group, isopropoxy group, and butoxy
group; nitro group; C6-C20 aromatic hydrocarbon ring group such as
phenyl group and naphthyl group; C2-C20 heteroaromatic ring group
such as furanyl group and thiophenyl group; C3-C8 cycloalkyl group
such as cyclopropyl group, cyclopentyl group, and cyclohexyl group;
and C1-C12 fluoroalkyl group at least one hydrogen of which is
replaced by fluorine, such as trifluoromethyl group,
pentafluoroethyl group, and --CH.sub.2CF.sub.3.
[0277] The C5-C12 aromatic hydrocarbon ring group may have more
than one substituent. When it has more than one substituent, each
substituent may be the same or different.
[0278] The aromatic ring of Ax may have two or more substituents
which may be the same or different, and two adjacent sub stituents
may be joined together to form a ring which may be a monocyclic,
condensed polycyclic, unsaturated or saturated ring.
[0279] The number of carbon atoms of the C2-C20 organic group for
Ax refers to a total number of carbon atoms of the whole organic
group excluding the carbon atom(s) of the substituent(s).
[0280] Examples of the C2-C20 organic group having at least one
aromatic ring selected from the group consisting of an aromatic
hydrocarbon ring and a heteroaromatic ring for Ax include C6-C20
aromatic hydrocarbon ring group such as phenyl group, naphthyl
group, anthracenyl group, phenanthrenyl group, pyrenyl group, and
fluorenyl group; C2-C20 heteroaromatic ring such as phthalimide
group, 1-benzofuranyl group, 2-benzofuranyl group, acrydinyl group,
isoquinolinyl group, imidazolyl group, indolinyl group, furazanyl
group, oxazolyl group, oxazolopyrazinyl group, oxazolopyridinyl
group, oxazolopyridazinyl group, oxazolopyrimidinyl group,
quinazolinyl group, quinoxalinyl group, quinolyl group, cinnolinyl
group, thiadiazolyl group, thiazolyl group, thiazolopyrazinyl
group, thiazolopyridinyl group, thiazolopyridazinyl group,
thiazolopyrimidinyl group, thienyl group, triazinyl group,
triazolyl group, naphthyridinyl group, pyrazinyl group, pyrazolyl
group, pyranonyl group, pyranyl group, pyridyl group, pyridazinyl
group, pyrimidinyl group, pyrrolyl group, phenanthridinyl group,
phthalazinyl group, furanyl group, benzo[c]thienyl group,
benzisoxazolyl group, benzisothiazolyl group, benzimidazolyl group,
benzoxazolyl group, benzothiadiazolyl group, benzothiazolyl group,
benzothiophenyl group, benzotriadinyl group, benzotriazolyl group,
benzopyrazolyl group, benzopyranonyl group, dihydropyranyl group,
tetrahydropyranyl group, dihydrofuranyl group, and
tetrahydrofuranyl group; hydrocarbon ring group having at least one
aromatic ring selected from the group consisting of an aromatic
hydrocarbon ring and a heteroaromatic ring; heterocyclic group
having at least one aromatic ring selected from the group
consisting of an aromatic hydrocarbon ring and a heteroaromatic
ring; C3-C20 alkyl group having at least one aromatic ring selected
from the group consisting of an aromatic hydrocarbon ring and a
heteroaromatic ring; C4-C20 alkenyl group having at least one
aromatic ring selected from the group consisting of an aromatic
hydrocarbon ring and a heteroaromatic ring; and C4-C20 alkynyl
having at least one aromatic ring selected from the group
consisting of an aromatic hydrocarbon ring and a heteroaromatic
ring.
[0281] Specific examples of the aromatic hydrocarbon ring and
heteroaromatic ring of the hydrocarbon ring group, heterocyclic
group, C3-C20 alkyl group, C4-C20 alkenyl group and C4-C20 alkynyl
group which have at least one aromatic ring selected from the group
consisting of an aromatic hydrocarbon ring and a heteroaromatic
ring are the same as those exemplified for D.sup.1.
[0282] The organic group may have one or more substituents. When it
has more than one substituent, each substituent may be the same or
different.
[0283] Examples of the substituent include halogens such as
fluorine and chlorine; cyano group; C1-C6 alkyl group such as
methyl group, ethyl group, and propyl group; C2-C6 alkenyl group
such as vinyl group and allyl group; C1-C6 halogenated alkyl group
such as trifluoromethyl group; substituted amino group such as
dimethylamino group; C1-C6 alkoxy group such as methoxy group,
ethoxy group, and isopropoxy group; nitro group; C6-C20 aromatic
hydrocarbon ring group such as phenyl group and naphthyl group;
--C(.dbd.O)--R.sup.b; --C(.dbd.O)--OR.sup.b; and --SO.sub.2R.sup.d,
where R.sup.b and R.sup.d are as defined above.
[0284] Of these substituents on the organic group of Ax, preferred
is at least one substituent selected from halogens, cyano group,
C1-C6 alkyl group, and C1-C6 alkoxy group.
[0285] Preferred but non-limiting specific examples of the C2-C20
organic group having at least one aromatic ring selected from the
group consisting of an aromatic hydrocarbon ring and a
heteroaromatic ring as Ax are shown below. In each structural
formula represents a bond at any position on the ring, which binds
with nitrogen (i.e., nitrogen which binds with Ax in Formula
(V)).
[0286] 1) Aromatic hydrocarbon ring groups:
##STR00026##
[0287] 2) Heteroaromatic ring groups:
##STR00027##
where E represents --NR.sup.z--, oxygen or sulfur, where R.sup.z
represents hydrogen or C1-C6 alkyl group such as methyl group,
ethyl group, and propyl group.
##STR00028##
where X and Y represent each independently --NR.sup.z--, oxygen,
sulfur, --SO-- or --SO.sub.2--, where R.sup.z represents hydrogen
or C1-C6 alkyl group such as methyl group, ethyl group, and propyl
group.
##STR00029##
where X is as defined above.
[0288] 3) Hydrocarbon ring groups having at least one aromatic
ring:
##STR00030##
[0289] 4) Heterocyclic groups having at least one aromatic
ring:
##STR00031##
where X and Y are as defined above and Z represents --NR.sup.z--,
oxygen or sulfur where R.sup.z is as defined above, with the
proviso that oxygen, sulfur, --SO-- and --SO.sub.2-- are not
adjacent to one another.
[0290] 5) Alkyl groups having at least one aromatic ring selected
from the group consisting of an aromatic hydrocarbon ring and a
heteroaromatic ring:
##STR00032##
[0291] 6) Alkenyl groups having at least one aromatic ring selected
from the group consisting of an aromatic hydrocarbon ring and a
heteroaromatic ring:
##STR00033##
[0292] 7) Alkynyl groups having at least one aromatic ring selected
from the group consisting of an aromatic hydrocarbon ring and a
heteroaromatic ring:
##STR00034##
[0293] The rings of the above preferred specific examples of Ax may
have one or more substituents which may be the same or different.
Examples of the substituents include halogens such as fluorine and
chlorine; cyano group; C1-C6 alkyl group such as methyl group,
ethyl group, and propyl group; C2-C6 alkenyl group such as vinyl
group and allyl group; C1-C6 halogenated alkyl group such as
trifluoromethyl group; substituted amino group such as
dimethylamino group; C1-C6 alkoxy group such as methoxy group,
ethoxy group, and isopropoxy group; nitro group; C6-C20 aromatic
hydrocarbon ring group such as phenyl group and naphthyl group;
--C(.dbd.O)--R.sup.b; --C(.dbd.O)--OR.sup.b; and --SO.sub.2R.sup.d,
where R.sup.b and R.sup.d are as defined above.
[0294] Of these substituents on the rings of Ax, preferred are
halogens, cyano group, C1-C6 alkyl group, and C1-C6 alkoxy
group.
[0295] More preferred but non-limiting specific examples of Ax are
shown below.
##STR00035##
where X is as defined above.
[0296] As described above, these rings may also have one or more
substituents which may be the same or different. Examples of the
substituents include halogens such as fluorine, chlorine, and
bromine; C1-C6 alkyl group such as methyl group, ethyl group, and
propyl group; cyano group; C2-C6 alkenyl group such as vinyl group
and allyl group; C1-C6 halogenated alkyl group such as
trifluoromethyl group and pentafluoroethyl group; substituted amino
group such as dimethylamino group; C1-C6 alkoxy group such as
methoxy group, ethoxy group, and isopropoxy group; nitro group;
C6-C20 aromatic hydrocarbon ring group such as phenyl group and
naphthyl group; --C(.dbd.O)--R.sup.b; --C(.dbd.O)--OR.sup.b; and
--SO.sub.2R.sup.d, where R.sup.b and R.sup.d are as defined
above.
[0297] Of these substituents on the rings, preferred are halogens,
cyano group, C1-C6 alkyl group, and C1-C6 alkoxy group.
[0298] Ax is even more preferably a group having the following
Formula (VI):
##STR00036##
[0299] In Formula (VI), R.sup.x represents hydrogen; halogen such
as fluorine, chlorine, and bromine; C1-C6 alkyl group such as
methyl group, ethyl group, and propyl group; cyano group; nitro
group; C1-C6 fluoroalkyl group such as trifluoromethyl group and
pentafluoroethyl group; C1-C6 alkoxy group such as methoxy group,
ethoxy group, and isopropoxy group; or --C(.dbd.O)--O--R.sup.b,
where R.sup.b represents, as described above, C1-C20 alkyl group
which may have a substituent, C2-C20 alkenyl group which may have a
substituent, C3-C12 cycloalkyl group which may have a substituent,
or C5-C12 aromatic hydrocarbon ring group which may have a
substituent.
[0300] Each R.sup.x may be the same or different, and any of
C--R.sup.x constituting the ring may be replaced by nitrogen.
[0301] Specific but non-limiting examples of the group having
Formula (VI) where one or more of CRx are replaced by nitrogen are
shown below.
##STR00037##
where R.sup.x is as defined above.
[0302] Of these examples of Ax, preferred is a group having Formula
(VI) where all of Rx are hydrogen.
[0303] Examples of the C1-C20 organic group which may have a
substituent for Ra of the divalent group having Formula (V)
include, but not limited to, C1-C20 alkyl group which may have a
substituent, C2-C20 alkenyl group which may have a substituent,
C2-20 alkynyl group which may have a substituent; C3-C12 cycloalkyl
group which may have a substituent, --C(.dbd.O)--R.sup.b,
--SO.sub.2--R.sup.d, --C(.dbd.S)NH--R.sup.i, C6-C20 aromatic
hydrocarbon ring group which may have a substituent, and C2-C20
heteroaromatic ring group which may have a substituent.
[0304] R.sup.b and R.sup.d are as defined above, and R.sup.i
represents C1-C20 alkyl group which may have a substituent, C2-C20
alkenyl group which may have a substituent, C3-C12 cycloalkyl group
which may have a substituent; C5-C20 aromatic hydrocarbon ring
group which may have a substituent, or C5-C20 heteroaromatic ring
group which may have a substituent.
[0305] Examples of the C1-C20 alkyl group and substituents thereon
of the C1-C20 alkyl group which may have a sub stituent, examples
of the C2-C20 alkenyl group and substituents thereon of the C2-C20
alkenyl group which may have a substituent, and examples of the
C3-C12 cycloalkyl group and substituents thereon of the C3-C12
cycloalkyl group which may have a substituent for R.sup.i are the
same as specific examples of the C1-C20 alkyl group and
substituents thereon, C2-C20 alkenyl group and substituents
thereon, and C3-C12 cycloalkyl group and substituents thereon for
R.sup.b. Examples of the C5-C20 aromatic hydrocarbon ring group
which may have a substituent for R.sup.i include phenyl group,
1-naphthyl group, and 2-naphthyl group, and examples of the C5-C20
heteroaromatic ring group which may have a substituent include
pyridinyl group and quinolyl group. Examples of substituents on
these aromatic hydrocarbon ring groups and heteroaromatic ring
groups are the same as those exemplified for Ax.
[0306] Examples of the C1-C20 alkyl group of the C1-C20 alkyl group
which may have a substituent for Ra include methyl group, ethyl
group, n-propyl group, isopropyl group, n-butyl group, isobutyl
group, 1-methylpentyl group, 1-ethylpentyl group, sec-butyl group,
t-butyl group, n-pentyl group, isopentyl group, neopentyl group,
n-hexyl group, isohexyl group, n-heptyl group, n-octyl group,
n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group,
n-tridecyl group, n-tetradecyl group, n-pentadecyl group,
n-hexadecyl group, n-heptadecyl group, n-octadecyl group,
n-nonadecyl group, and n-icosyl group. The C1-C20 alkyl group which
may have a substituent preferably has 1 to 12 carbon atoms, more
preferably 1 to 10 carbon atoms.
[0307] Examples of the C2-C20 alkenyl group of the C2-C20 alkenyl
group which may have a substituent for Ra include vinyl group,
propenyl group, isopropenyl group, butenyl group, isobutenyl group,
pentenyl group, hexenyl group, heptenyl group, octenyl group,
decenyl group, undecenyl group, dodecenyl group, tridecenyl group,
tetradecenyl group, pentadecenyl group, hexadecenyl group,
heptadecenyl group, octadecenyl group, nonadecenyl group, and
icocenyl group.
[0308] The C2-C20 alkenyl group which may have a substituent
preferably has 2 to 12 carbon atoms.
[0309] Examples of the C2-C20 alkynyl group of the C2-C20 alkynyl
group which may have a substituent for Ra include ethynyl group,
propynyl group, 2-propynyl group (propargyl group), butynyl group,
2-butynyl group, 3-butynyl group, pentynyl group, 2-pentynyl group,
hexynyl group, 5-hexynyl group, heptynyl group, octynyl group,
2-octynyl group, nonanyl group, decanyl group, and 7-decanyl
group.
[0310] Examples of the C3-C12 cycloalkyl group of the C3-C12
cycloalkyl group which may have a substituent for Ra include
cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl
group, and cyclooctyl group.
[0311] Examples of the substituents on the C1-C20 alkyl group,
C2-C20 alkenyl group and C2-C20 alkynyl group for Ra include
halogens such as fluorine and chlorine; cyano group; substituted
amino group such as dimethylamino group; C1-C20 alkoxy group such
as methoxy group, ethoxy group, isopropoxy group, and butoxy group;
C1-C12 alkoxy group substituted with C1-C12 alkoxy group, such as
methoxymethoxy group and methoxyethoxy group; nitro group; C6-C20
aromatic hydrocarbon ring group such as phenyl group and naphthyl
group; C2-C20 heteroaromatic ring group such as triazolyl group,
pyrrolyl group, furanyl group, and thiophenyl group; C3-C8
cycloalkyl group such as cyclopropyl group, cyclopentyl group, and
cyclohexyl group; C3-C8 cycloalkyloxy group such as cyclopentyloxy
group and cyclohexyloxy group; C2-C12 cyclic ether group such as
tetrahydrofuranyl group, tetrahydropyranyl group, dioxolanyl group,
and dioxanyl group; C6-C14 aryloxy group such as phenoxy group and
naphthoxy group; C1-C12 fluoroalkyl group at least one hydrogen of
which is replaced by fluorine, such as trifluoromethyl group,
pentafluoroethyl group, and --CH.sub.2CF.sub.3; benzofuryl group;
benzopyranyl group; benzodioxolyl group; benzodioxanyl group;
--C(.dbd.O)--R.sup.b; --C(.dbd.O)--OR.sup.b; --SO.sub.2R.sup.d;
--SR.sup.b; C1-C12 alkoxy group substituted with SR.sup.b; and
hydroxyl group, where R.sup.b and R.sup.d are as defined above.
[0312] The C1-C20 alkyl group, C2-C20 alkenyl group and C2-C20
alkynyl group for Ra may have two or more of the substituents
described above, which may be the same or different.
[0313] Examples of the substituent on the C3-C12 cycloalkyl group
for Ra include halogens such as fluorine and chlorine; cyano group;
substituted amino group such as dimethylamino group; C1-C6 alkyl
group such as methyl group, ethyl group, and propyl group; C1-C6
alkoxy group such as methoxy group, ethoxy group, and isopropoxy
group; nitro group; C6-C20 aromatic hydrocarbon ring group such as
phenyl group and naphthyl group; C3-C8 cycloalkyl group such as
cyclopropyl group, cyclopentyl group, and cyclohexyl group; C6-C20
aromatic hydrocarbon ring group such as phenyl group and naphthyl
group; --C(.dbd.O)--R.sup.b; --C(.dbd.O)--OR.sup.b;
--SO.sub.2R.sup.d; and hydroxyl group, where R.sup.b and R.sup.d
are as defined above.
[0314] The C3-C12 cycloalkyl group for Ra may have two or more of
the substituents described above, which may be the same or
different.
[0315] Examples of the C6-C20 aromatic hydrocarbon ring group and
C2-C20 heteroaromatic ring group as well as substituents thereon
for Ra are the same as those exemplified for Ax.
[0316] Of these groups described above, preferred as Ra are
hydrogen, C1-C20 alkyl group which may have a substituent, C2-C20
alkenyl group which may have a substituent, C2-20 alkynyl group
which may have a substituent, C5-C20 cycloalkyl group which may
have a substituent, C6-C18 aromatic hydrocarbon ring group which
may have a substituent, and C5-C18 heteroaromatic ring group which
may have a substituent, more preferably hydrogen, C1-C10 alkyl
group which may have a substituent, C2-C10 alkenyl group which may
have a substituent, C2-C10 alkynyl group which may have a
substituent, C5-C10 cycloalkyl group which may have a substituent,
and C6-C12 aromatic hydrocarbon ring group.
[0317] In Formula (III) above, Z.sup.11 and Z.sup.12 are each
independently COO, --O--CO--, --NR.sup.31--CO-- or
--CO--NR.sup.32--, where R.sup.31 and R.sup.32 are each
independently hydrogen or C1-C6 alkyl group. In particular,
Z.sup.11 is preferably --CO--O--, and Z.sup.12 is preferably
--O--CO--.
[0318] A.sup.11 and A.sup.12 are each independently alicyclic group
which may have a substituent or aromatic group which may have a
substituent. In particular, A.sup.11 and A.sup.12 are each
independently preferably alicyclic group which may have a
substituent.
[0319] The alicyclic group which may have a substituent is a
substituted or unsubstituted divalent alicyclic group, where the
divalent alicyclic group is a divalent aliphatic group having
cyclic structure and typically having 5 to 20 carbon atoms.
[0320] Specific examples of the divalent alicyclic group for
A.sup.11 and A.sup.12 are the same as those exemplified for A.sup.1
in Formula (I) above.
[0321] The aromatic group which may have a substituent is a
substituted or unsubstituted divalent aromatic group, where the
divalent aromatic group is a divalent aromatic group having
aromatic ring structure and typically having 2 to 20 carbon
atoms.
[0322] Specific examples of the divalent aromatic group for
A.sup.11 and A.sup.12 are the same as those exemplified for A.sup.1
in Formula (I) above.
[0323] Examples of the substituents on the divalent alicyclic group
and divalent aromatic group for A.sup.11 and A.sup.12 are the same
as those exemplified for the divalent alicyclic group and divalent
aromatic group for A.sup.1 in Formula (I) above.
[0324] When h and/or i is 1, L.sup.11 and L.sup.12 are each
independently single bond, --O--, --CO--, --CO--O--, --O--CO--,
--NR.sup.21--CO--, --CO--NR.sup.22--, --O--CO--O--,
--NR.sup.23CO--O--, --O--CO--NR.sup.24-- or
--NR.sup.25--CO--NR.sup.26--, where R.sup.21 to R.sup.26 are each
independently hydrogen or C1-C6 alkyl group. In particular,
L.sup.11 and L.sup.12 are each independently preferably --O--,
--CO--O-- or --O--CO--.
[0325] Examples of the C1-C6 alkyl group for R.sup.21 to R.sup.26
include methyl group, ethyl group, propyl group, and isopropyl
group.
[0326] When h and/or i is 1, B.sup.11 and B.sup.12 are each
independently alicyclic group which may have a substituent or
aromatic group which may have a substituent. In particular,
B.sup.11 and B.sup.12 are each independently preferably aromatic
group which may have a substituent.
[0327] The alicyclic group which may have a substituent is a
substituted or unsubstituted divalent alicyclic group, where the
divalent alicyclic group is a divalent aliphatic group having
cyclic structure and typically having 5 to 20 carbon atoms.
[0328] Specific examples of the divalent alicyclic group for
B.sup.11 and B.sup.12 are the same as those exemplified for A.sup.1
in Formula (I) above.
[0329] The aromatic group which may have a substituent is a
substituted or unsubstituted divalent aromatic group, where the
divalent aromatic group is a divalent aromatic group having
aromatic ring structure and typically having 2 to 20 carbon
atoms.
[0330] Specific examples of the divalent aromatic group for
B.sup.11 and B.sup.12 are the same as those exemplified for A.sup.1
in Formula (I) above.
[0331] Examples of the substituents on the divalent alicyclic group
and divalent aromatic group for B.sup.11 and B.sup.12 are the same
as those exemplified for the divalent alicyclic group and divalent
aromatic group for A.sup.1 in Formula (I) above.
[0332] Y.sup.11 and Y.sup.12 are each independently single bond,
--O--, --CO--, --CO--O--, --O--CO--, --NR.sup.21--CO--,
--CO--NR.sup.22--, --O--CO--O--, --NR.sup.23--CO--O--,
--O--CO--NR.sup.24-- or --NR.sup.25--CO--NR.sup.26--, where
R.sup.21 to R.sup.26 are each independently hydrogen or C1-C6 alkyl
group. In particular, Y.sup.11 and Y.sup.12 are each independently
preferably --O--, --CO--O-- or --O--CO--.
[0333] Examples of the C1-C6 alkyl group for R.sup.21 to R.sup.26
include methyl group, ethyl group, propyl group, and isopropyl
group.
[0334] R.sup.4 to R.sup.7 are each independently hydrogen, methyl
group or chlorine, preferably hydrogen or methyl group. All of
R.sup.4 to R.sup.7 are preferably the same, and all of R.sup.4 to
R.sup.7 are more preferably hydrogen.
[0335] From the perspective of obtaining optical film etc. which
exhibit superior reverse wavelength dispersion, polymerizable
compound (III) preferably has generally symmetric structure about
Ar.sup.1-D.sup.1. More specifically, it is preferred that in
polymerizable compound (III), R.sup.4, g and h are the same as
R.sup.7, j and i, respectively, and that
--Y.sup.11--[B.sup.11-L.sup.11].sub.h-A.sup.11-Z.sup.11-(*) and
(*)-Z.sup.12-A.sup.12-[L.sup.12-B.sup.12].sub.i--Y.sup.12-- are
symmetrical to each other about (*), a side for binding with
Ar.sup.1.
[0336] By the phrase "symmetrical to each other about (*)" is meant
to have such pairs of structures as --CO--O--(*) and (*)--O--CO--,
--O--(*) and (*)--O--, or --O--CO--(*) and (*)--CO--O--.
[0337] Polymerizable compound (III) described above can be
synthesized by combining the synthesis reactions known in the art.
Specifically, polymerizable compound (III) can be synthesized with
reference to methods described in various literatures, e.g.,
March's Advanced Organic Chemistry (Wiley), and S. R. Sandler and
W. Karo "Organic Functional Group Preparations."
[0338] A preferred example of polymerizable compound (III) where h
and i are 1 includes, but not limited to, a compound having the
following Formula (Va) (hereinafter occasionally referred to as
"polymerizable compound (Va)"):
##STR00038##
where R.sup.4 to R.sup.7, Ra, R.sup.x, f, g, j and k are as defined
above.
[0339] Any method can be used for the production of polymerizable
compound (Va). One exemplary method involves sequentially reacting
2,5-dihydroxybenzaldehyde having the following Formula (7) with a
compound having the following Formula (b) (hereinafter referred to
as "compound (b)") and a compound having the following Formula (c)
(hereinafter referred to as "compound (c)") to give a compound
having the following Formula (9) (hereinafter referred to as
"compound (9)"), and reacting the resulting compound (9) with a
hydrazine compound having the following Formula (10) to give
polymerizable compound (Va).
##STR00039##
where R.sup.4 to R.sup.7, f, g, j, k, Ra and Rx are as defined
above, and L represent leaving group as in Formula (2) above.
[0340] Compounds (b) and (c) (hereinafter occasionally collectively
referred to as "compound (b) etc.") where L is halogen (i.e., acid
halide) can be obtained by reacting compound (Ma) with a
halogenating agent such as thionyl chloride in the presence of an
activator.
[0341] Examples of activators used include N,N-dimethylformamide,
and quaternary ammonium salts such as benzyltriethylammonium
chloride and benzyltrimethylammonium chloride.
[0342] The activator is used at an amount of typically 0.1 to 3
moles per 1 mole of compound (b) etc.
[0343] Compound (b) etc. where L is alkyl(aryl)sulfonyloxy group
such as methanesulfonyloxy or p-toluenesulfonyloxy group (i.e.,
mixed-anhydride) can be obtained by reacting compound (Ma) with a
sulfonyl chloride compound having the formula R.sup.dSO.sub.2Cl
(where R.sup.d is as defined in Formula (6) above) in suitable
solvent in the presence of a base.
[0344] The base can be triethylamine, N,N-diisopropylethylamine,
4-(dimethylamino)pyridine or the like.
[0345] The suitable solvent can be any of the solvents exemplified
above as being usable for the production of compound (Ia) and
halogen solvents such as methylene chloride and chloroform, with
ether solvents being preferred.
[0346] Examples of solvents used for the reaction between
2,5-dihydroxybenzaldehyde having Formula (7) with compound (b) etc.
include chlorine solvents such as chloroform and methylene
chloride; amide solvents such as N-methylpyrrolidone,
N,N-dimethylformamide, N,N-dimethylacetamide, and
hexamethylphosphoric triamide; ether solvents such as 1,4-dioxane,
cyclopentyl methyl ether, tetrahydrofuran, tetrahydropyran, and
1,3-dioxofuran; sulfur-containing solvents such as dimethyl
sulfoxide and sulfolane; aromatic hydrocarbon solvents such as
benzene, toluene, and xylene; aliphatic hydrocarbon solvents such
as n-pentane, n-hexane, n-octane, cyclopentane, and cyclohexane;
and mixture solvents of two or more of the foregoing.
[0347] Any amount of solvent can be used and the amount can be
determined as appropriate in light of, for example, the types of
compounds used or reaction scale. Typically, 1 to 50 g of solvent
is used per 1 g of compound (b) etc.
[0348] The target polymerizable compound (Va) can be produced
highly selectively in high yield by reacting compound (9) with
hydrazine compound (10) at a mole ratio (compound (9):hydrazine
compound (10)) of 1:2 to 2:1, preferably 1:1.5 to 1.5 to 1.
[0349] This reaction can be performed with the addition of an acid
catalyst such as an organic acid (e.g., (.+-.)-10-camphorsulfonic
acid or p-toluenesulfonic acid) or an inorganic acid (e.g.,
hydrochloric acid or sulfuric acid). The addition of acid catalyst
shortens the reaction time and may increase yield. The acid
catalyst is added at an amount of typically 0.001 to 1 mole per 1
mole of compound (9). The acid catalyst may be added directly as it
is or as a solution in suitable solvent.
[0350] Any solvent can be for the reaction between compound (9) and
hydrazine compound (10) as long it is inert to the reaction.
Examples thereof include alcohol solvents such as methyl alcohol,
ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl
alcohol, and isobutyl alcohol; ether solvents such as diethylether,
tetrahydrofuran, 1,4-dioxane, and cyclopentyl methyl ether; ester
solvents such as ethyl acetate and propyl acetate; aromatic
hydrocarbon solvents such as benzene, toluene, and xylene;
aliphatic hydrocarbon solvents such as n-pentane, n-hexane, and
n-heptane; amide solvents such as N,N-dimethylformamide and
N-methylpyrrolidone; sulfur-containing solvents such as dimethyl
sulfoxide and sulfolane; chlorine solvents such as chloroform and
methylene chloride; and mixture solvents of two or more of the
foregoing.
[0351] Of these solvents, preferred are alcohol solvents, chlorine
solvents, ether solvents, and mixture solvents of two or more of
the foregoing.
[0352] Any amount of solvent can be used and the amount can be
determined as appropriate in light of, for example, the types of
compounds used or reaction scale. Typically, 1 to 100 g of solvent
is used per 1 g of hydrazine compound (10).
[0353] The reaction proceeds smoothly in a temperature range from
10.degree. C. up to the boiling point of solvent used. Reaction
time is several minutes to several hours although it depends on the
reaction scale.
[0354] (4) Mixture Containing Polymerizable Compounds
[0355] The disclosed mixture is a mixture containing polymerizable
compound (III) and a polymerizable compound having the following
Formula (IV) (polymerizable compound (IV)) and can be used for the
production of a polymerizable liquid crystal composition and a
polymer which are described later.
[0356] From the perspective of enhancing reverse wavelength
dispersion of the resulting optical film etc. while broadening the
process margin upon formation of the optical film etc. using the
mixture or polymerizable liquid crystal composition prepared using
the mixture, the mass ratio of polymerizable compound (III) to
polymerizable compound (IV) (polymerizable compound
(III):polymerizable compound (IV)) in the mixture is preferably
1:1,000 to 20:100, more preferably 1:100 to 20:100.
##STR00040##
[0357] The use of the mixture of polymerizable compound (III) and
polymerizable compound (IV) makes it possible to obtain a
polymerizable liquid crystal composition which can retain liquid
crystal phase more stably over long periods of time, has a wide
process margin, has a low melting point suitable for practical use,
has superior solubility in common solvents, and allows for low-cost
manufacture of optical film etc. which are capable of uniform
polarized light conversion over a wide wavelength range.
[0358] A possible but still uncertain reason for this is that
polymerizable compound (III) has a moiety represented by
--(CH.sub.2CHR.sup.5COO).sub.f-- and/or a moiety represented by
--(OCOCHR.sup.6CH.sub.2).sub.k-- and hence the use of the mixture
of polymerizable compounds (III) and (IV) results in the formation
of a liquid crystal layer that easily turns into liquid crystal
phase at lower temperatures (i.e., easily becomes supercooling
state at room temperature) compared to cases where only
polymerizable compound (IV) is used while ensuring optical
characteristics (especially reverse wavelength dispersion), so that
optical film etc. having a polymer as the constituent material can
be obtained.
[0359] In Formula (IV), m and q are each independently an integer
of 1 to 20, preferably an integer of 2 to 12, more preferably an
integer of 4 to 8, and n and p are each independently 0 or 1,
preferably 1.
[0360] Ar.sup.2 is divalent aromatic hydrocarbon ring group having
D.sup.2 as a substituent or divalent heteroaromatic ring group
having D.sup.2 as a substituent. D.sup.2 is C1-C20 organic group
having at least one aromatic ring selected from the group
consisting of an aromatic hydrocarbon ring and a heteroaromatic
ring.
[0361] The divalent aromatic hydrocarbon ring group having D.sup.2
as a substituent or divalent heteroaromatic ring group having
D.sup.2 as a substituent refers to a group obtained by removing,
from the ring moiety of the aromatic hydrocarbon ring or
heteroaromatic ring to which D.sup.2 is bound, two hydrogens
attached to carbon atoms other than the carbon atom to which
D.sup.2 is bound.
[0362] Examples of the divalent aromatic hydrocarbon ring group for
Ar.sup.2 are the same as those exemplified for A.sup.1 of
polymerizable compound (III).
[0363] Examples of the divalent heteroaromatic ring group for
Ar.sup.2 are the same as those exemplified for A.sup.1 of
polymerizable compound (III).
[0364] The divalent aromatic hydrocarbon ring group and divalent
heteroaromatic ring group for Ar.sup.2 may have at least one
substituent in addition to D.sup.2, as with Ar.sup.1 of
polymerizable compound (III). Examples of the substituents on the
divalent aromatic hydrocarbon ring group and divalent
heteroaromatic ring group for Ar.sup.2 are the same as those
exemplified for the divalent aromatic hydrocarbon ring group and
divalent heteroaromatic ring group for Ar.sup.1.
[0365] Examples of the C1-C20 organic group having at least one
aromatic group selected from the group consisting of an aromatic
hydrocarbon ring and a heteroaromatic ring for D.sup.2 are the same
as those exemplified for D.sup.1 of polymerizable compound
(III).
[0366] Examples of combinations of Ar.sup.2 and D.sup.2
(Ar.sup.2-D.sup.2) include phenylene group substituted with a group
having the formula --R.sup.fC(.dbd.N--NR.sup.gR.sup.h),
benzothiazole-4,7-diyl group substituted with 1-benzofuran-2-yl
group, benzothiazole-4,7-diyl group substituted with
5-(2-butyl)-1-benzofuran-2-yl group, benzothiazole-4,7-diyl group
substituted with 4,6-dimethyl-1-benzofuran-2-yl group,
benzothiazole-4,7-diyl group substituted with
6-methyl-1-benzofuran-2-yl group, benzothiazole-4,7-diyl group
substituted with 4,6,7-trimethyl-1-benzofuran-2-yl group,
benzothiazole-4,7-diyl group substituted with 4,5,6-tri methyl -1
-b enzofuran-2-yl group, benzothiazole-4,7-diyl group substituted
with 5-methyl-1-benzofuran-2-yl group, benzothiazole-4,7-diyl group
substituted with 5-propyl-1-benzofuran-2-yl group,
benzothiazole-4,7-diyl group substituted with
7-propyl-1-benzofuran-2-yl group, benzothiazole-4,7-diyl group
substituted with 5-fluoro-1-benzofuran-2-yl group,
benzothiazole-4,7-diyl group substituted with phenyl group,
benzothiazole-4,7-diyl group substituted with 4-fluorophenyl group,
benzothiazole-4,7-diyl group substituted with 4-nitrophenyl group,
benzothiazole-4,7-diyl group substituted with
4-trifluoromethylphenyl group, benzothiazole-4,7-diyl group
substituted with 4-cyanophenyl group, benzothiazole-4,7-diyl group
substituted with 4-methanesulfonylphenyl group,
benzothiazole-4,7-diyl group substituted with thiophene-2-yl group,
benzothiazole-4,7-diyl group substituted with thiophene-3-yl group,
benzothiazole-4,7-diyl group substituted with
5-methylthiophene-2-yl group, benzothiazole-4,7-diyl group
substituted with 5-chlorothiophene-2-yl group,
benzothiazole-4,7-diyl group substituted with
thieno[3,2-b]thiophene-2-yl group, benzothiazole-4,7-diyl group
substituted with 2-benzothiazolyl group, benzothiazole-4,7-diyl
group substituted with 4-biphenyl group, benzothiazole-4,7-diyl
group substituted with 4-propylbiphenyl group,
benzothiazole-4,7-diyl group substituted with 4-thiazolyl group,
benzothiazole-4,7-diyl group substituted with 1-phenylethylene-2-yl
group, benzothiazole-4,7-diyl group substituted with 4-pyridyl
group, benzothiazole-4,7-diyl group substituted with 2-furyl group,
benzothiazole-4,7-diyl group substituted with
naphtho[1,2-b]furan-2-yl group, 1H-isoindole-1,3(2H)-dione-4,7-diyl
group substituted with 5-methoxy-2-benzothiazolyl group,
1H-isoindole-1,3(2H)-dione-4,7-diyl group substituted with phenyl
group, 1H-isoindole-1,3(2H)-dione-4,7-diyl group substituted with
4-nitrophenyl group, and 1H-isoindole-1,3(2H)-dione-4,7-diyl group
substituted with 2-thiazolyl group. R.sup.f, R.sup.g and R.sup.h in
the formula --R.sup.fC(.dbd.N--NR.sup.gR.sup.h) are as defined
above.
[0367] Of these combinations, Ar.sup.2-D.sup.2 is preferably a
group having the following Formula (VII):
##STR00041##
where Ay represents C2-C20 organic group having at least one
aromatic ring selected from the group consisting of an aromatic
hydrocarbon ring and a heteroaromatic ring, and Rc represents
hydrogen or C1-C20 organic group which may have a substituent.
[0368] Examples of the C2-C20 organic group having at least one
aromatic ring selected from the group consisting of an aromatic
hydrocarbon ring and a heteroaromatic ring for Ay are the same as
those exemplified for Ax in Formula (V).
[0369] In particular, Ay is preferably a group having the following
Formula (VI) as with Ax of Formula (V), more preferably a group
having Formula (VI) where all of Rx are hydrogen.
##STR00042##
where R.sup.x are as defined above.
[0370] Examples of the C1-C20 organic group which may have a
substituent for Rc are the same as those exemplified for Ra in
Formula (V).
[0371] In Formula (IV) above, Z.sup.21 and Z.sup.22 are each
independently --CO--O--, --O--CO--, --NR.sup.31--CO-- or
--CO--NR.sup.32--, where R.sup.31 and R.sup.32 are each
independently hydrogen or C1-C6 alkyl group. In particular,
Z.sup.21 is preferably --CO--O--, and Z.sup.22 is preferably
--O--CO--.
[0372] A.sup.21 and A.sup.22 are each independently alicyclic group
which may have a substituent, or aromatic group which may have a
substituent. In particular, A.sup.21 and A.sup.22 are each
independently preferably alicyclic group which may have a sub
stituent.
[0373] Examples of the alicyclic and aromatic groups which may have
a substituent for A.sup.21 and A.sup.22 are the same as those
exemplified for A.sup.11 and A.sup.11 of polymerizable compound
(III).
[0374] When n and/or p is 1, L.sup.21 and L.sup.22 are each
independently single bond, --O--, --CO--, --CO--O--, --O--CO--,
--NR.sup.21--CO--, --CO--NR.sup.22--, --O--CO--O--,
--NR.sup.23--CO--O--, --O--CO--NR.sup.24-- or
--NR.sup.25--CO--NR.sup.26--, where R.sup.21 to R.sup.26 are each
independently hydrogen or C1-C6 alkyl group. In particular,
L.sup.21 and L.sup.22 are each independently preferably --O--,
--CO--O-- or --O--CO--.
[0375] Examples of the C1-C6 alkyl group for R.sup.21 to R.sup.26
include methyl group, ethyl group, propyl group, and isopropyl
group.
[0376] When n and/or p is 1, B.sup.21 and B.sup.22 are each
independently alicyclic group which may have a substituent, or
aromatic group which may have a substituent. In particular,
B.sup.21 and B.sup.22 are each independently preferably aromatic
group which may have a substituent.
[0377] Examples of the alicyclic and aromatic groups which may have
a substituent for B.sup.21 and B.sup.22 are the same as those
exemplified for B.sup.11 and B.sup.11 of polymerizable compound
(III).
[0378] Y.sup.21 and Y.sup.22 are each independently single bond,
--O--, --CO--, --CO--O--, --O--CO--, --NR.sup.21--CO--,
--CO--NR.sup.22--, --O--CO--O--, --NR.sup.23--CO--O--,
--O--CO--NR.sup.24-- or --NR.sup.25--CO--NR.sup.26--, where
R.sup.21 to R.sup.26 are each independently hydrogen or C1-C6 alkyl
group. In particular, Y.sup.21 and Y.sup.22 are each independently
preferably --O--, --CO--O-- or --O--CO--.
[0379] Examples of the C1-C6 alkyl group for R.sup.21 to R.sup.26
include methyl group, ethyl group, propyl group, and isopropyl
group.
[0380] R.sup.8 and R.sup.9 are each independently hydrogen, methyl
group or chlorine, preferably hydrogen or methyl group. R.sup.8 and
R.sup.9 are preferably the same, and both of R.sup.8 and R.sup.9
are more preferably hydrogen.
[0381] From the perspective of obtaining optical film etc. which
exhibit superior reverse wavelength dispersion, polymerizable
compound (IV) preferably has symmetric structure about
Ar.sup.2-D.sup.2. More specifically, it is preferred that in
polymerizable compound (IV), R.sup.8, m and n are the same as
R.sup.9, q and p, respectively, and that
--Y.sup.21--[B.sup.21-L.sup.2l].sub.n-A.sup.21-Z.sup.21-(*) and
(*)-Z.sup.22-A.sup.22-[L.sup.22-B.sup.22].sub.p--Y.sup.22-- are
symmetrical to each other about (*), a side for binding with
Ar.sup.2.
[0382] By the phrase "symmetrical to each other about (*)" is meant
to have such pairs of structures as --CO--O--(*) and (*)--O--CO--,
--O--(*) and (*)--O--, or --O--CO--(*) and (*)--CO--O--.
[0383] Polymerizable compound (IV) described above can be
synthesized by combining synthesis reactions known in the art.
Specifically, polymerizable compound (IV) can be synthesized with
reference to methods described in various literatures, e.g.,
March's Advanced Organic Chemistry (Wiley), and S. R. Sandler and
W. Karo "Organic Functional Group Preparations."
[0384] From the perspective of enhancing reverse wavelength
dispersion of optical film etc., in the disclosed mixture,
Ar.sup.1, Z.sup.11, Z.sup.12, A.sup.11, A.sup.12, B.sup.11,
B.sup.12, Y.sup.11, Y.sup.12, L.sup.11, L.sup.12, R.sup.4, R.sup.7,
g, j, h and i of polymerizable compound (III) are preferably the
same as Ar.sup.2, Z.sup.21, Z.sup.22, A.sup.21, A.sup.22, B.sup.21,
B.sup.22, Y.sup.21, Y.sup.22, L.sup.21, L.sup.22, R.sup.8, R.sup.9,
m, q, n and p of polymerizable compound (IV), respectively. D.sup.1
and D.sup.2 may be the same or different.
[0385] Specifically, the structure of polymerizable compound (III)
exclusive of D.sup.1 is preferably the same as the structure of
polymerizable compound (IV) exclusive of D.sup.2 except for the
presence of --(CH.sub.2CHR.sup.5COO).sub.f-- between
CH.sub.2CR.sup.4COO-- and --(CH.sub.2).sub.g-- and the presence of
--(OCOCHR.sup.6CH.sub.2).sub.k-- between --OCOCR.sup.7CH.sub.2 and
--(CH.sub.2).sub.j--.
[0386] The mixture can be prepared for example by mixing
polymerizable compounds (III) and (IV) at desired ratios.
[0387] The mixture can also be obtained by any method, e.g., by
reacting the mixture containing compounds (I) and (II) with a
compound having the following formula followed by conversion of
L.sup.5 into D.sup.1:
##STR00043##
where L.sup.4 represent a group which may form --CO--O--,
--O--CO--, --NR.sup.31--CO-- or --CO--NR.sup.32-- by reaction with
FG.sup.1 of compound (I) or FG.sup.2 of compound (II) with the
proviso that R.sup.31 and R.sup.32 are each independently hydrogen
or C1-C6 alkyl group; L.sup.5 represents a group which can be
converted into D.sup.1; and Ar.sup.1 is as defined in Formula
(III).
[0388] A preferred example of polymerizable compound (IV) where n
and p are 1 includes, but not limited to, a compound having the
following Formula (VIa) (hereinafter occasionally referred to as
"compound (VIa)"):
##STR00044##
where R.sup.8, R.sup.9, Rc, R.sup.x, m and q are as defined above,
and all of R.sup.x are preferably hydrogen.
[0389] Compound (VIa) can be produced by any of the methods known
in the art, e.g., by the method described in PTL 1.
[0390] The mixture containing compounds (Va) and (VIa) can be
prepared for example by mixing compounds (Va) and (VIa) at desired
ratios.
[0391] The mixture containing compounds (Va) and (VIa) can also be
obtained for example by replacing compounds (b) and (c) by the
mixture containing compounds (IIIa) and (IVa) in the
above-described method of producing compound (Va).
[0392] (5) Polymerizable Liquid Crystal Composition
[0393] The disclosed polymerizable liquid crystal composition
contains a mixture containing the polymerizable compounds described
above (i.e., a mixture containing polymerizable compounds (III) and
(IV)) and a polymerization initiator.
[0394] As will be described later, the disclosed polymerizable
liquid crystal composition is useful as the raw material for the
manufacture of disclosed polymers, optical films and optically
anisotropic product. The disclosed polymerizable liquid crystal
composition can retain liquid crystal phase more stably over long
periods of time, has a wide process margin, has a low melting point
suitable for practical use, has superior solubility in common
solvents, and allows for low-cost manufacture of optical film etc.
which are capable of uniform polarized light conversion over a wide
wavelength range.
[0395] The polymerization initiator is blended in the polymerizable
liquid crystal composition for more efficient polymerization
reaction of the polymerizable compounds contained in the
composition.
[0396] Examples of polymerization initiators used include radical
polymerization initiators, anion polymerization initiators, and
cation polymerization initiators.
[0397] For radical polymerization initiators, both of thermal
radical generators (compounds that on heating generate active
species that may initiate polymerization of polymerizable
compounds) and photo-radical generators (compounds that on exposure
to exposure light such as visible ray, ultraviolet ray (e.g., i
line), far-ultraviolet ray, electron ray or X ray generate active
species that may initiate polymerization of polymerizable
compounds) can be used, with photo-radical generators being
suitable.
[0398] Examples of the photo-radical generators include
acetophenone compounds, biimidazole compounds, triazine compounds,
O-acyloxime compounds, onium salt compounds, benzoin compounds,
benzophenone compounds, .alpha.-diketone compounds, polynuclear
quinone compounds, xanthone compounds, diazo compounds, and
imidesulfonate compounds. These compounds are components that on
exposure to light generate one or both of active radicals and
active acid. These photo-radical generators can be used alone or in
combination.
[0399] Specific examples of the acetophenone compounds include
2-hydroxy-2-methyl-1-phenylpropane-1-one,
2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one,
2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one,
1-hydroxycyclohexyl phenyl ketone,
2,2-dimethoxy-1,2-diphenylethane-1-one, 1,2-octanedione, and
2-benzyl-2-dimethylamino-4'-morpholinobutyrophenone.
[0400] Specific examples of the biimidazole compounds include
2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'--
biimidazole,
2,2'-bis(2-bromophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-b-
iimidazole,
2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole,
2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole,
2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole,
2,2'-bis(2-bromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole,
2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole,
and
2,2'-bis(2,4,6-tribromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole.
[0401] When biimidazole compounds are used as photopolymerization
initiators (photo-radical generators) in the present disclosure, it
is preferable to use hydrogen donors in combination for further
improvement in sensitivity.
[0402] By "hydrogen donor" is meant a compound that can donate
hydrogen to a radical generated on exposure to light from a
biimidazole compound. Preferred hydrogen donors are mercaptan
compounds and amine compounds defined below.
[0403] Examples of the mercaptan compounds include
2-mercaptobenzothiazole, 2-mercaptobenzoxazole,
2-mercaptobenzimidazole, 2,5-dimercapto-1,3,4-thiadiazole, and
2-mercapto-2,5-dimethylaminopyridine. Examples of amine compounds
include 4,4'-bis(dimethylamino)benzophenone,
4,4'-bis(diethylamino)benzophenone, 4-diethylaminoacetophenone,
4-dimethylaminopropiophenone, ethyl-4-dimethylaminobenzoate,
4-dimethylamino benzoic acid, and 4-dimethylaminobenzonitrile.
[0404] Examples of the triazine compounds include triazine
compounds having a halomethyl group, such as
2,4,6-tris(trichloromethyl)-s-triazine,
2-methyl-4,6-bis(trichloromethyl)-s-triazine,
2-[2-(5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine,
2-[2-(furan-2-ypethenyl]-4,6-bis(trichloromethyl)-s-triazine,
2-[2-(4-diethylamino-2-methylphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-t-
riazine,
2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-tri-
azine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine,
2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, and
2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine.
[0405] Specific examples of the O-acyloxime compounds include
1-[4-(phenylthio)phenyl]-heptane-1,2-dione2-(O-benzoyloxime),
1-[4-(phenylthio)phenyl]-octane-1,2-dione2-(O-benzoyloxime),
1-[4-(benzoyl)phenyl]-octane-1,2-dione2-(O-benzoyloxime),
1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbozole-3-yl]-ethanonel-(O-acetyloxim-
e),
1-[9-ethyl-6-(3-methylbenzoyl)-9H-carbozole-3-yl]-ethanonel-(O-acetylo-
xime),
1-(9-ethyl-6-benzoyl-9H-carbozole-3-yl)-ethanonel-(O-acetyloxime),
ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzoyl)-9H-carbozole--
3-yl]-1-(O-acetyloxime),
ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzoyl)-9H-carbozole--
3-yl]-1-(O-acetyloxime),
ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzoyl)-9H-carbozole--
3-yl]-1-(O-acetyloxime),
ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylbenzoyl)-9H-carbozole--
3-yl]-1-(O-acetyloxime),
ethanone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)benzoyl}-9-
H-carbozole-3-yl]-1-(O-acetyloxime),
ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxybenzoyl)-9H-car-
bozole-3-yl]-1-(O-acetyloxime),
ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylmethoxybenzoyl)-9H-car-
bozole-3-yl]-1-(O-acetyloxime),
ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylmethoxybenzoyl)-9H-car-
bozole-3-yl]-1-(O-acetyloxime),
ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbozole-3-yl]-1-(O-acetyloxi-
me),
ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylmethoxybenzoyl)-9H-
-carbozole-3-yl]-1-(O-acetyloxime), and
ethanone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxyben-
zoyl}-9H-carbozole-3-yl]-1-(O-acetyloxime).
[0406] Commercially available photo-radical generators can be used
directly. Specific examples include Irgacure 907, Irgacure 184,
Irgacure 369, Irgacure 651, Irgacure 819, Irgacure 907 and Irgacure
OXE02 (BASF), and ADEKA OPTOMER N1919 (ADEKA Corporation).
[0407] Examples of the anion polymerization initiators include
alkyllithium compounds; monolithium or monosodium salts of
biphenyl, naphthalene, pyrene and the like; and polyfunctional
initiators such as dilithium salts and trilithium salts.
[0408] Examples of the cation polymerization initiators include
protonic acids such as sulfuric acid, phosphoric acid, perchloric
acid, and trifluoromethanesulfonic acid; Lewis acids like boron
trifluoride, aluminum chloride, titanium tetrachloride, and tin
tetrachloride; and aromatic onium salts or combinations of onium
salts with reducing agents.
[0409] These polymerization initiators can be used alone or in
combination.
[0410] In the disclosed polymerizable liquid crystal composition,
the polymerization initiator is blended at an amount of typically
0.1 to 30 parts by mass, preferably 0.5 to 10 parts by mass, per
100 parts by mass of the above-described mixture of polymerizable
compounds.
[0411] The disclosed polymerizable liquid crystal composition is
preferably blended with surfactants for adjustment of surface
tension. Any surfactant can be used, but nonionic surfactants are
generally preferred. Commercially available nonionic surfactants
will suffice, e.g., nonionic surfactants made of oligomers with a
molecular weight on the order of several thousands, such as
Ftergent 208G (NEOS).
[0412] In the disclosed polymerizable liquid crystal composition,
the surfactant is blended at an amount of typically 0.01 to 10
parts by mass, preferably 0.1 to 2 parts by mass, per 100 parts by
mass of the total polymerizable compounds.
[0413] In addition to a mixture containing polymerizable compounds,
a polymerization initiator and a surfactant, the disclosed
polymerizable liquid crystal composition may further contain
optional additives at amounts that do not compromise the effect of
the present disclosure. Examples of the optional additives include
metals, metal complexes, dyes, pigments, fluorescent materials,
phosphorescent materials, leveling agents, thixotropic agents,
gelling agents, polysaccharides, ultraviolet absorbers, infrared
absorbers, antioxidants, ion-exchange resins, and metal oxides such
as titanium oxide.
[0414] Other examples of the optional additives include other
copolymerizable mononomers. Specific examples include, but not
limited to, 4'-methoxyphenyl 4-(2-methacryloyloxyethyloxy)benzoate,
biphenyl 4-(6-methacryloyloxyhexyloxy)benzoate, 4'-cyanobiphenyl
4-(2-acryloyloxyethyl oxy)benzoate, 4'-cyanobiphenyl
4-(2-methacryloyloxyethyloxy)benzoate, 3',4'-difluorophenyl
4-(2-methacryloyloxyethyloxy)benzoate, naphthyl
4-(2-methacryloyloxyethyloxy)benzoate,
4-acryloyloxy-4'-decylbiphenyl, 4-acryloyloxy-4'-cyanobiphenyl,
4-(2-acryloyloxyethyloxy)-4'-cyanobiphenyl,
4-(2-methacryloyloxyethyloxy)-4'-methoxybiphenyl,
4-(2-methacryloyloxyethyloxy)-4'-(4''-fluorobenzyloxy)-biphenyl,
4-acryloyloxy-4'-propylcyclohexylphenyl,
4-methacryloyl-4'-butylbicyclohexyl, 4-acryloyl-4'-amyltolane,
4-acryloyl-4'-(3,4-difluorophenyl)bicyclohexyl, (4-amylphenyl)
4-(2-acryloyloxyethyl)benzoate, (4-(4'-propylcyclohexyl)phenyl)
4-(2-acryloyloxyethyl)benzoate, a commercially available product
"LC-242" (BASF), and compounds disclosed in JP-A Nos. 2007-002208,
2009-173893, 2009-274984, 2010-030979, 2010-031223, 2011-006360 and
2010-24438.
[0415] These optional additives are blended at amounts of typically
0.1 to 20 parts by mass per 100 parts by mass of the total
polymerizable compounds.
[0416] The disclosed polymerizable liquid crystal composition can
be typically prepared by mixing and dissolving given amounts of a
mixture containing polymerizable compounds, a polymerization
initiator, and optional additive(s) in suitable organic
solvent.
[0417] In this case, polymerizable compounds (III) and (IV) as a
mixture may be added in the form of pre-mix or may be added
separately.
[0418] Examples of organic solvents used include ketones such as
cyclopentanone, cyclohexanone, and methyl ethyl ketone; acetates
such as butyl acetate and amyl acetate; halogenated hydrocarbons
such as chloroform, dichloromethane, and dichloroethane; and ethers
such as 1,4-dioxane, cyclopentyl methyl ether, tetrahydrofuran,
tetrahydropyran, and 1,3-dioxolane.
[0419] (6) Polymer
[0420] The disclosed polymer can be obtained by polymerizing a
mixture containing the polymerizable compounds described above
(i.e., a mixture containing polymerizable compounds (III) and (IV))
or the polymerizable liquid crystal composition.
[0421] By the term "polymerization" herein is meant a chemical
reaction in a broad sense including a crosslinking reaction as well
as a normal polymerization reaction.
[0422] The disclosed polymer typically includes the following
monomer unit derived from polymerizable compound (III) (repeat unit
(III)') and the following monomer unit derived from polymerizable
compound (IV) (repeat unit (IV)'):
##STR00045##
where Ar.sup.1, D.sup.1, Z.sup.11, Z.sup.12, A.sup.11, A.sup.12,
B.sup.11, B.sup.12, Y.sup.11, Y.sup.12, L.sup.11, L.sup.12, R.sup.4
to R.sup.7, f, g, h, i, j and k are as defined in Formula
(III).
##STR00046##
where Ar.sup.2, D.sup.2, Z.sup.21, Z.sup.22, A.sup.21, A.sup.22,
B.sup.21, B.sup.22, Y.sup.21, Y.sup.22, L.sup.21, L.sup.22,
R.sup.8, R.sup.9, m, n, p and q are as defined in Formula (IV).
[0423] Because the disclosed polymer is prepared using the mixture
containing polymerizable compounds (III) and (IV), it can be
advantageously used as the constituent material for optical film
etc.
[0424] Further, the disclosed polymer can be used in any shape or
form according to its intended use, including film, powder or layer
made of an aggregation of powder.
[0425] Specifically, films made of the polymer can be suitably used
as the constituent material for optical films and optically
anisotropic products described later; powders made of the polymer
can be utilized for paints, anti-forgery items, security items and
the like; and layers made of the polymer powder can be suitably
used as the constituent material for the optically anisotropic
products.
[0426] The disclosed polymer can be suitably produced for example
by (.alpha.) polymerizing the mixture containing polymerizable
compounds or polymerizable liquid crystal composition in suitable
organic solvent, isolating the target polymer, dissolving the
polymer in suitable organic solvent to prepare a solution, applying
the solution on a suitable substrate to form thereon a coating
film, and drying the coating film followed by optional heating, or
(.beta.) dissolving the mixture containing polymerizable compounds
or polymerizable liquid crystal composition in organic solvent to
prepare a solution, applying the solution on a substrate by
coatings methods known in the art, removing the solvent, and
effecting polymerization by heating or actinic radiation.
[0427] Any organic solvent can be used for the polymerization by
method (.alpha.) above as long as it is inert. Examples of the
organic solvent include aromatic hydrocarbons such as toluene,
xylene, and mesitylene; ketones such as cyclohexanone,
cyclopentanone, and methyl ethyl ketone; acetates such as butyl
acetate and amyl acetate; halogenated hydrocarbons such as
chloroform, dichloromethane, and dichloroethane; and ethers such as
cyclopentyl methyl ether, tetrahydrofuran, and tetrahydropyran.
[0428] Of these organic solvents, preferred are those having a
boiling point of 60.degree. C. to 250.degree. C., more preferably
those having a boiling point of 60.degree. C. to 150.degree. C.,
from the viewpoint of handling capability.
[0429] Examples of organic solvents used to dissolve the isolated
polymer in method (.alpha.) and organic solvents used in method
(.beta.) include ketone solvents such as acetone, methyl ethyl
ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone;
ester solvents such as butyl acetate and amyl acetate; halogenated
hydrocarbon solvents such as dichloromethane, chloroform, and
dichloroethane; ether solvents such as tetrahydrofuran,
tetrahydropyran, 1,2-dimethoxyethane, 1,4-dioxane, cyclopentyl
methyl ether, and 1,3-dioxolane; and aprotic polar solvents such as
N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide,
y-butyrolactone, and N-methylpyrrolidone. Of these organic
solvents, preferred are those having a boiling point of 60.degree.
C. to 200.degree. C. from the viewpoint of handling capability.
These solvents can be used alone or in combination.
[0430] Substrates made of any of organic or inorganic materials
known in the art can be used in methods (.alpha.) and (.beta.).
Examples of the organic material include polycycloolefins such as
Zeonex.RTM. and Zeonor.RTM. (Zeonex and Zeonor are registered
trademarks in Japan, other countries, or both) available from Zeon
Corporation, Arton.RTM. (Arton is a registered trademark in Japan,
other countries, or both) available from JSR Corporation, and
Apel.RTM. (Apel is a registered trademark in Japan, other
countries, or both) available from by Mitsui Chemicals Inc.;
polyethylene terephthalates; polycarbonates; polyimides;
polyamides; polymethyl methacrylates; polystyrenes; polyvinyl
chlorides; polytetrafluoroethylene, celluloses; cellulose
triacetate; and polyethersulfones. Examples of the inorganic
material include silicon, glass, and calcite.
[0431] The substrate may be monolayer or laminate.
[0432] The substrate is preferably made of organic material, more
preferably a resin film formed of organic material.
[0433] Additional examples of the substrate include those used for
the manufacture of an optically anisotropic product later
described.
[0434] Coating methods known in the art can be used for applying
the polymer solution on the substrate in method (.alpha.) and for
applying the solution for polymerization reaction on the substrate
in method (.beta.). Specific examples of usable coating methods
include curtain coating, extrusion coating, roll coating, spin
coating, dip coating, bar coating, spray coating, slide coating,
print coating, gravure coating, die coating, and cap coating.
[0435] Drying or solvent removal in methods (.alpha.) and (.beta.)
can be effected by natural drying, drying by heating, drying under
reduced pressure, drying by heating under reduced pressure, or the
like.
[0436] Polymerization of the mixture or polymerizable liquid
crystal composition can be effected for example by irradiation with
actinic radiation or by thermal polymerization, with irradiation
with actinic radiation being preferred as heating is unnecessary so
that the reaction proceeds at room temperature. Irradiation with UV
or other like light is particularly preferred because the operation
is simple.
[0437] Temperature during irradiation is preferably set to
30.degree. C. or below. Irradiation intensity is typically 1
W/m.sup.2 to 10 kW/m.sup.2, preferably 5 W/m.sup.2 to 2
kW/m.sup.2.
[0438] The polymer obtained as described above can be transferred
from the substrate for use, removed from the substrate for single
use, or used as it is as the constituent material for optical film
etc. without being removed from the sub strate.
[0439] The polymer removed from the substrate can also be made into
powder form by grinding methods known in the art before use.
[0440] The number-average molecular weight of the disclosed polymer
is preferably 500 to 500,000, more preferably 5,000 to 300,000.
When the number-average molecular weight falls within any of these
ranges, the resulting film advantageously exhibits high hardness as
well as high handling capability. The number-average molecular
weight of the polymer can be determined by gel permeation
chromatography (GPC) using monodisperse polystyrene as a standard
(eluant: tetrahydrofuran).
[0441] The disclosed polymer can retain liquid crystal phase more
stably over long periods of time, has a wide process margin, has a
low melting point suitable for practical use, has superior
solubility in common solvents, and allows for low-cost manufacture
of high performance optical film etc. which are capable of uniform
polarized light conversion over a wide wavelength range.
[0442] (7) Optical Film
[0443] The disclosed optical film is formed using the disclosed
polymer and comprises a layer having an optical function. By
"optical function" as used herein is meant simple transmittance,
reflection, refraction, birefringence, or the like.
[0444] The disclosed optical film may be used in any of the
following arrangements: (1) "alignment substrate/(alignment
film)/optical film" where the optical film remains formed on an
alignment substrate which may have an alignment film; (2)
"transparent substrate film/optical film" where the optical film
has been transferred to a transparent substrate film or the like
which is different from the alignment substrate; and (3) single
optical film form when the optical film is self-supportive.
[0445] Usable alignment films and alignment substrates are the same
as those exemplified for the optically anisotropic product
described later.
[0446] The disclosed optical film can be produced by (A) applying
on an alignment substrate a solution of the mixture containing
polymerizable comounds or of the polymerizable liquid crystal
composition, drying the resulting coating film, subjecting the film
to heat treatment (for alignment of liquid crystals), and
irradiation and/or heating treatment (for polymerization); or (B)
applying on an alignment substrate a solution of a liquid crystal
polymer obtained by polymerization of the mixture containing
polymerizable compounds or liquid crystal composition, and
optionally drying the resulting coated film.
[0447] The disclosed optical film can be used for optically
anisotropic products, alignment films for liquid crystal display
devices, color filters, low-pass filters, polarization prisms, and
various optical filters.
[0448] The disclosed optical film preferably has .alpha. and .beta.
values that fall within given ranges, which can be calculated as
follows based on phase differences at 449.9 nm, 548.5 nm and 650.2
nm measured with an ellipsometer. Specifically, .alpha. value is
preferably 0.70 to 0.99, more preferably 0.75 to 0.90, and .beta.
value is preferably 1.00 to 1.25, more preferably 1.01 to 1.20.
[0449] .alpha.=(phase difference at 449.9 nm)/(phase difference at
548.5 nm)
[0450] .beta.=(phase difference at 650.2 nm)/(phase difference at
548.5 nm)
[0451] (8) Optically Anisotropic Product
[0452] The disclosed optically anisotropic product has a layer
having the disclosed polymer as the constituent material.
[0453] The disclosed optically anisotropic product can be obtained
for example by forming an alignment film on a substrate and forming
a layer made of the disclosed polymer (liquid crystal layer) on the
alignment film.
[0454] The disclosed optically anisotropic product may be obtained
by directly forming a layer made of the disclosed polymer (liquid
crystal layer) on a substrate or may consist only of a layer made
of the disclosed polymer (liquid crystal layer).
[0455] The layer made of the disclosed polymer may be formed of a
polymer film or may be an aggregate of powdery polymer.
[0456] The alignment film is formed on the surface of the substrate
to regulate molecules of the polymerizable liquid crystal compounds
to align in one direction in the plane.
[0457] The alignment film can be obtained for example by applying a
solution containing a polymer such as polyimide, polyvinyl alcohol,
polyester, polyarylate, polyamideimide, or polyetherimide
(alignment film composition) on the substrate to form a film,
drying the film, and rubbing the film in one direction.
[0458] The thickness of the alignment film is preferably 0.001 to 5
.mu.m, more preferably 0.001 to 1 .mu.m.
[0459] Any method can be used for the rubbing treatment. For
example, the alignment film may be rubbed in a given direction
using a roll around which a cloth or felt formed of synthetic fiber
(e.g., nylon) or natural fiber (e.g., cotton) is wound. It is
preferable to wash the alignment film with isopropyl alcohol or the
like after completion of the rubbing treatment in order to remove
fine powder (foreign substance) formed during the rubbing treatment
to clean the surface of the alignment film.
[0460] Alternative to the rubbing treatment, the alignment film can
be provided with a function of in-plane one-direction alignment by
irradiation with polarized UV light on the surface.
[0461] Examples of substrates on which the alignment film is to be
formed include glass substrates and substrates formed of synthetic
resin films.
[0462] Examples of synthetic resins include thermoplastic resins
such as acrylic resins, polycarbonate resins, polyethersulfone
resins, polyethylene terephthlate resins, polyimide resins,
polymethyl methacrylate resins, polysulfone resins, polyarylate
resins, polyethylene resins, polystyrene resins, polyvinyl chloride
resins, cellulose diacetate, cellulose triacetate, and alicyclic
olefin polymers.
[0463] Examples of the alicyclic olefin polymers include cyclic
olefin random multi-component copolymers described in JP-A No.
H05-310845 and U.S. Pat. No. 5,179,171; hydrogenated polymers
described in JP-A No. H05-97978 and U.S. Pat. No. 5,202,388; and
thermoplastic dicyclopentadiene open-ring polymers and hydrogenated
products thereof described in JP-A No. H11-124429 (W099/20676).
[0464] In this disclosure, examples of methods of forming a liquid
crystal layer made of the disclosed polymer on the alignment film
are the same as those described in the above chapter for the
disclosed polymer (methods (.alpha.) and (.beta.)).
[0465] The resulting liquid crystal layer may be of any thickness
and typically has a thickness of 1 to 10 .mu.m.
[0466] The disclosed optically anisotropic product can be used as
any desired product, e.g., as a phase difference film, a
viewing-angle enhancing film or the like.
[0467] The disclosed optically anisotropic product preferably has
.alpha. and .beta. values that fall within given ranges, which can
be calculated as follows based on phase differences at 449.9 nm,
548.5 nm and 650.2 nm measured with an ellipsometer. Specifically,
.alpha. value is preferably 0.70 to 0.99, more preferably 0.75 to
0.90, and .beta. value is preferably 1.00 to 1.25, more preferably
1.01 to 1.20.
[0468] .alpha.=(phase difference at 449.9 nm)/(phase difference at
548.5 nm)
[0469] .beta.=(phase difference at 650.2 nm)/(phase difference at
548.5 nm)
[0470] (9) Polarizing Plate etc.
[0471] The disclosed polarizing plate includes the disclosed
optically anisotropic product and a polarizing film.
[0472] A specific example of the disclosed polarizing plate is
obtained by laminating the disclosed optically anisotropic product
on a polarizing film either directly or with other layer(s) (e.g.,
glass plate)) disposed between the optically anisotropic product
and the polarizing film.
[0473] Any method can be used for the manufacture of the polarizing
film. Examples of methods of manufacturing a PVA polarizing film
include a method wherein iodine ions are adsorbed onto a PVA film
followed by uniaxial stretching of the PVA film; a method wherein a
PVA film is uniaxially stretched followed by adsorption of iodine
ions; a method wherein adsorption of iodine ions to a PVA film and
uniaxial stretching are simultaneously performed; a method wherein
a PVA film is dyed with dichroic dye followed by uniaxial
stretching; a method wherein a PVA film is uniaxially stretched
followed by dying with dichroic dye; and a method wherein dying of
a PVA film with dichroic dye and uniaxial stretching are
simultaneously performed. Examples of methods of manufacturing a
polyene polarizing film include known methods in the art, e.g., a
method wherein a PVA film is uniaxially stretched followed by
heating and dehydration in the presence of a dehydration catalyst,
and a method wherein a polyvinyl chloride film is uniaxially
stretched followed by heating and dechlorination in the presence of
a dechlorination catalyst.
[0474] In the disclosed polarizing plate, the polarizing film and
disclosed optically anisotropic product may be bonded with an
adhesive layer consisting of an adhesive (including tackifier). The
average thickness of the adhesive layer is typically 0.01 to 30
.mu.m, preferably 0.1 to 15 .mu.m. The adhesive layer preferably
has a tensile fracture strength of 40 MPa or less as measured in
accordance with JIS K7113.
[0475] Examples of adhesives for the adhesive layer include acrylic
adhesives, urethane adhesives, polyester adhesives, polyvinyl
alcohol adhesives, polyolefin adhesives, modified polyolefin
adhesives, polyvinyl alkyl ether adhesives, rubber adhesives, vinyl
chloride-vinyl acetate adhesives, styrene-butadiene-styrene
copolymer (SBS copolymer) adhesives and their hydrogenated product
(SEBS copolymer) adhesives, ethylene adhesives such as
ethylene-vinyl acetate copolymers and ethylene-styrene copolymers,
and acrylate adhesives such as ethylene-methyl methacrylate
copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl
methacrylate copolymer, and ethylene-ethyl acrylate copolymer.
[0476] The disclosed polarizing plate includes the disclosed
optically anisotropic product and therefore can be manufactured at
low costs as well as has such superior performance as low reflected
luminance and capability of polarized light conversion over a wide
wavelength range.
[0477] Using the disclosed polarizing plate, it is possible to
suitably manufacture flat panel display devices that include a
liquid crystal panel, organic electroluminescence display devices
that include an organic electroluminescence panel, and
anti-reflection films.
EXAMPLES
[0478] The present disclosure will now be described in detail with
reference to Examples, which however shall not be construed as
limiting the scope of the present disclosure in any way.
Synthesis Example 1
Synthesis of Compound 1
##STR00047##
[0480] Step 1: Synthesis of intermediate A
##STR00048##
[0481] A three-necked reactor equipped with a thermometer was
charged with 17.98 g (104.42 mmol) of
trans-1,4-cyclohexanedicarboxylic acid and 180 ml of
tetrahydrofuran (THF) under a nitrogen stream. 6.58 g (57.43 mmol)
of methanesulfonyl chloride was added, and the reactor was immersed
in a water bath to adjust the reaction solution temperature to
20.degree. C. 6.34 g (62.65 mmol) of triethylamine was added
dropwise over 10 minutes while retaining the reaction solution
temperature to 20.degree. C. to 30.degree. C. After the dropwise
addition, the entire mass was further stirred at 25.degree. C. for
2 hours.
[0482] To the resulting reaction solution were added 0.64 g (5.22
mmol) of 4-(dimethylamino)pyridine and 13.80 g (52.21 mmol) of
4-(6-acryloyloxy-hex-1-yloxy)phenol (available from DKSH Japan
K.K.), and the reactor was again immersed in the water bath to
adjust the reaction solution temperature to 15.degree. C. 6.34 g
(62.65 mmol) of triethylamine was added dropwise over 10 minutes
while retaining the reaction solution temperature to 20.degree. C.
to 30.degree. C. After the dropwise addition, the entire mass was
further stirred at 25.degree. C. for 2 hours. After completion of
the reaction, 1,000 ml of distilled water and 100 ml of saturated
brine were added to the reaction solution and extracted twice with
400 ml of ethyl acetate. The organic phases were combined and dried
over sodium sulfate anhydrous, and sodium sulfate was filtered off.
The solvent was evaporated from the filtrate using a rotary
evaporator, and the residue was purified by silica gel column
chromatography (THF:toluene=1:9 (volume ratio; hereinafter the
same)). Purification by silica gel column chromatography was
repeated until purity of 99.5% was detected by high performance
liquid chromatography. As a consequence, 14.11 g of intermediate A
was obtained as a white solid (yield: 65 mol %).
[0483] The structure of the target compound was identified by
.sup.1H-NMR. The result is given below.
[0484] .sup.1H-NMR (500 MHz, DMSO-d.sub.6, TMS, .delta. ppm):
12.12(s,1H), 6.99(d,2H,J=9.0 Hz), 6.92(d,2H,J=9.0 Hz),
6.32(dd,1H,J=1.5 Hz,17.5 Hz), 6.17(dd,1H,J=10.0 Hz,17.5 Hz),
5.93(dd,1H,J=1.5 Hz,10.0 Hz), 4.11(t,2H,J=6.5 Hz), 3.94(t,2H,J=6.5
Hz), 2.48-2.56(m,1H), 2.18-2.26(m,1H), 2.04-2.10(m,2H),
1.93-2.00(m,2H), 1.59-1.75(m,4H), 1.35-1.52(m,8H)
[0485] Step 2: Synthesis of Intermediate B
##STR00049##
[0486] A three-necked reactor equipped with a thermometer was
charged with 4.00 g (9.56 mmol) of intermediate A synthesized in
Step 1 and 60 ml of THF under a nitrogen stream to prepare a
homogenous solution. 1.12 g (9.78 mmol) of methanesulfonyl chloride
was added, and the reactor was immersed in a water bath to adjust
the reaction solution temperature to 20.degree. C. 1.01 g (9.99
mmol) of triethylamine was added dropwise over 5 minutes while
retaining the reaction solution temperature to 20.degree. C. to
30.degree. C. After the dropwise addition, the entire mass was
further stirred at 25.degree. C. for 2 hours. To the resulting
reaction solution were added 0.11 g (0.87 mmol) of
4-(dimethylamino)pyridine and 0.60 g (4.35 mmol) of
2,5-dihydroxybenzaldehyde, and the reactor was again immersed in
the water bath to adjust the reaction solution temperature to
15.degree. C. 1.10 g (10.87 mmol) of triethylamine was added
dropwise over 5 minutes while retaining the reaction solution
temperature to 20.degree. C. to 30.degree. C. After the dropwise
addition, the entire mass was further stirred at 25.degree. C. for
2 hours. After completion of the reaction, 400 ml of distilled
water and 50 ml of saturated brine were added to the reaction
solution and extracted twice with 750 ml of ethyl acetate. The
organic phases were combined and dried over sodium sulfate
anhydrous, and sodium sulfate was filtered off. The solvent was
evaporated from the filtrate using a rotary evaporator, and the
residue was dissolved in 100 ml of THF. 500 ml of methanol was
added to the solution to precipitate crystals and the crystals were
filtered off. The crystals obtained were washed with methanol and
dried in vacuo to give 2.51 g of intermediate B as a white solid
(yield: 62 mol %).
[0487] The structure of the target compound was identified by
.sup.1H-NMR. The result is given below.
[0488] .sup.1H-NMR(500 MHz,DMSO-d.sub.6,TMS,.delta.
ppm):10.02(s,1H), 7.67(d,1H,J=3.0 Hz), 7.55(dd,1H,J=3.0 Hz,8.5 Hz),
7.38(d,1H,J=8.5 Hz), 6.99-7.04(m,4H), 6.91-6.96(m,4H),
6.32(dd,2H,J=1.5 Hz,17.5 Hz), 6.17(dd,2H,J=10.0 Hz,17.5 Hz), 5.93
(dd,2H,J=1.5 Hz,10.0 Hz), 4.11(t,4H,J=6.5 Hz), 3.95(t,4H,J=6.5 Hz),
2.56-2.81(m,4H), 2.10-2.26(m,8H), 1.50-1.76(m,16H),
1.33-1.49(m,8H)
[0489] Step 3: Synthesis of Compound 1
[0490] A three-necked reactor equipped with a thermometer was
charged with 2.30 g (2.45 mmol) of intermediate B synthesized in
Step 2 and 25 ml of THF under a nitrogen stream to prepare a
homogeneous solution to which 0.49 ml (0.25 mmol) of concentrated
hydrochloric acid was added. 0.40 g (2.45 mmol) of
2-hydrazinobenzothiazole in 5 ml of THF was added dropwise to the
solution over 15 minutes. After the dropwise addition, the entire
mass was further stirred at 25.degree. C. for 1 hour. After
completion of the reaction, the reaction solution was charged into
400 ml of methanol, and the precipitated solid was filtered off.
The solid was dried using a vacuum drier to give 2.4 g of compound
1 as a pale yellow solid (yield: 90 mol %).
[0491] The structure of the target compound was identified by
.sup.1H-NMR. The result is given below.
[0492] .sup.1H-NMR(500 MHz,DMSO-d.sub.6,TMS,.delta.
ppm):12.63(s,1H), 8.10(s,1H), 7.80(d,1H,J=5.0 Hz), 7.60(d,1H,J=3.0
Hz), 7.48(s,1H), 7.21 -7.35(m,3H), 7.14(t,1H,J=7.5 Hz),
6.98-7.05(m,4H), 6.91-6.97(m,4H), 6.32(dd,2H,J=1.5 Hz,17.5 Hz),
6.18(dd,2H,J=10.0 Hz,17.5 Hz), 5.93 (dd,2H,J=1.5 Hz,10.0 Hz),
4.12(t,4H,J=6.5 Hz), 3.95(t,4H,J=6.5 Hz), 2.56-2.83(m,4H),
2.11-2.30(m,8H), 1.52-1.80(m,16H), 1.33-1.49(m,8H)
Synthesis Example 2
Synthesis of Compound 2
##STR00050##
[0494] Step 1: Synthesis of intermediate C
##STR00051##
[0495] A four-necked reactor equipped with a thermometer was
charged with 2.00 g (12.1 mmol) of 2-hydrazinobenzothiazole under a
nitrogen stream, which was then dissolved in 20 ml of
N,N-dimethylformamide (DMF). To the solution were added 8.36 g
(60.5 mmol) of potassium carbonate and 3.08 g (14.5 mmol) of
1-iodohexane, and stirred at 50.degree. C. for 7 hours. After
completion of the reaction, the reaction solution was cooled to
20.degree. C., charged into 200 ml of water, and extracted with 300
ml of ethyl acetate. The ethyl acetate phase was dried over sodium
sulfate anhydrous. After filtering off sodium sulfate, ethyl
acetate was distilled off under reduced pressure using a rotary
evaporator to give a yellow solid, which was purified by silica gel
column chromatography (hexane:ethyl acetate=75:25) to give 2.10 g
of intermediate C as a white solid (yield: 69.6 mol %).
[0496] The structure of the target compound was identified by
.sup.1H-NMR. The result is given below.
[0497] .sup.1H-NMR(500 MHz,CDCl.sub.3, TMS,.delta. ppm):
7.60(dd,1H,J=1.0 Hz,8.0 Hz), 7.53(dd,1H,J=1.0 Hz,8.0 Hz),
7.27(ddd,1H,J=1.0 Hz,8.0 Hz,8.0 Hz), 7.06(ddd,1H,J=1.0 Hz, 8.0 Hz,
8.0 Hz), 4.22(s,2H), 3.74(t,2H,J=7.5 Hz), 1.69-1.76(m,2H),
1.29-1.42(m,6H), 0.89(t,3H,J=7.0 Hz)
[0498] Step 2: Synthesis of Compound 2
[0499] A four-necked reactor equipped with a thermometer was
charged with 697 mg (2.37 mmol) of intermediate C synthesized in
Step 1 and 2.00 g (2.13 mmol) of intermediate B synthesized in Step
2 of Synthesis Example 1 under a nitrogen stream, which were then
dissolved in a mixture solvent of 3 ml ethanol and 20 ml THF. To
the solution was added 55.1 mg (0.237 mmol) of
(.+-.)-10-camphorsulfonic acid and stirred at 40.degree. C. for 5
hours. After completion of the reaction, the reaction solution was
charged into 150 ml of water and extracted with 300 ml of ethyl
acetate. The ethyl acetate phase was dried over sodium sulfate
anhydrous. After filtering off sodium sulfate, ethyl acetate was
distilled off under reduced pressure using a rotary evaporator to
give a white solid, which was purified by silica gel column
chromatography (toluene:ethyl acetate=90:10) to give 2.24 g of
compound 2 as a white solid (yield: 86.4 mol %).
[0500] The structure of the target compound was identified by
.sup.1H-NMR. The result is given below.
[0501] .sup.1H-NMR(400 MHz,CDCl.sub.3,TMS,.delta.
ppm):7.75(d,1H,J=2.5 Hz), 7.67-7.70(m,3H), 7.34(ddd,1H,J=1.0 Hz,7.0
Hz,7.5 Hz), 7.17(ddd,1H,J=1.0 Hz,7.5 Hz,7.5 Hz), 7.12(d,1H,J=9.0
Hz), 7.10(dd,1H,J=2.5 Hz,9.0 Hz), 6.99(d,2H,J=9.0 Hz),
6.98(d,2H,J=9.0 Hz), 6.88(d,4H,J=9.0 Hz), 6.40(dd,2H,J=1.5 Hz,17.0
Hz), 6.13 (dd,2H,J=10.5 Hz,17.5 Hz), 5.82(dd,2H,J=1.5 Hz,10.5 Hz),
4.30(t,2H,J=8.0 Hz), 4.18(t,4H,J=6.5 Hz), 3.95(t,4H,J=6.5 Hz),
2.58-2.70(m,4H), 2.31-2.35(m,8H), 1.66-1.82(m,18H),
1.31-1.54(m,14H), 0.90(t,3H,J=7.0 Hz)
Synthesis Example 3
Synthesis of Compound 3
##STR00052##
[0503] Step 1: Synthesis of Intermediate D
##STR00053##
[0504] A three-necked reactor equipped with a thermometer was
charged with 3.00 g (17.69 mmol) of 2-chlorobenzothiazole and 7.65
g (70.74 mmol) of phenylhydrazine under a nitrogen stream, which
were then dissolved in 30 ml of ethylene glycol. The solution was
heated to 140.degree. C. for reaction for 5 hours. 300 ml of
distilled water was then added to the reaction solution and
extracted twice with 100 ml of ethyl acetate. The combined organic
phase was dried over sodium sulfate, concentrated using a rotary
evaporator, and dissolved in 15 ml of THF. The solution was charged
into 300 ml of distilled water. The precipitated solid was filtered
off, washed with distilled water, and dried in vacuo to give a
yellow solid. The yellow solid was placed in a flask, 50 ml of
toluene was added, and stirred for 30 minutes. The solution was
filtered to remove solid components which were insoluble in
toluene. The filtrate was concentrated using a rotary evaporator
and purified by silica gel column chromatography (THF:toluene=2:50)
to give 0.94 g of intermediate D as a yellow oil (yield: 22 mol
%).
[0505] The structure of the target compound was identified by
.sup.1H-NMR. The result is given below.
[0506] .sup.1H-NMR(500 MHz,DMSO-d.sub.6, TMS,.delta. ppm):
8.01(dd,2H,J=1.0 Hz,9.0 Hz), 7.78(dd,1H,J=1.0 Hz,8.0 Hz),
7.51(dd,1H,J=1.0 Hz,8.0 Hz), 7.43(dd,2H,J=7.5 Hz, 8.5 Hz), 7.28(dt,
1H,J=1.0 Hz,7.5 Hz), 7.08-7.16(m,2H), 6.26(s,2H)
[0507] Step 2: Synthesis of Compound 3
[0508] A three-necked reactor equipped with a thermometer was
charged with 1.00 g (1.06 mmol) of intermediate B synthesized in
Step 2 for synthesis of compound 1 in Synthesis Example 1 under a
nitrogen stream, which was then dissolved in 30 ml of THF. To the
solution were added 0.22 ml (0.22 mmol) of 1N hydrochloric acid and
0.38 g (1.60 mmol) of intermediate D synthesized in Step 1, and
reacted at 40.degree. C. for 2 hours. The reaction solution was
then concentrated using a rotary evaporator and purified by silica
gel column chromatography (chloroform:THF=40:1) to give 1.14 g of
compound 3 as a pale yellow solid (yield: 95 mol %).
[0509] The structure of the target compound was identified by
.sup.1H-NMR. The result is given below.
[0510] .sup.1H-NMR(500 MHz,CDCl.sub.3,TMS,.delta.
ppm):7.82(d,1H,J=2.5 Hz), 7.73 (dd,1H,J=1.0 Hz, 8.0 Hz),
7.64-7.70(m,2H), 7.60(d,2H,J=7.5 Hz), 7.35-7.42(m,3H),
7.30(dt,1H,J=1.0 Hz,7.5 Hz), 7.18(dt, 1H,J=1.0 Hz,7.5 Hz), 7.03
-7.12(m,2H), 7.00(d,2H,J=9.0 Hz), 6.99(d,2H,J=9.0 Hz),
6.90(d,2H,J=9.0 Hz), 6.89(d,2H,J=9.0 Hz), 6.41(dd,1H,J=1.5 Hz,17.5
Hz), 6.41(dd,1H,J=1.5 Hz,17.5 Hz), 6.13(dd,1H,J=10.5 Hz,17.5 Hz),
6.13(dd,1H,J=10.5 Hz,17.5 Hz), 5.82(dd,1H,J=1.5 Hz,10.5 Hz),
5.82(dd,1H,J=1.5 Hz,10.5 Hz), 4.18(t,2H,J=6.5 Hz), 4.18(t,2H,J=6.5
Hz), 3.92-3.98(m,4H), 2.56-2.71(m,2H), 2.41-2.50(m,1H),
2.27-2.40(m,5H), 2.12-2.22(m,2H), 1.64-1.91(m,14H),
1.41-1.56(m,10H), 1.19-1.31(m,2H)
Synthesis Example 4
Synthesis of Compound 4
##STR00054##
[0512] Step 1: Synthesis of Intermediate E
##STR00055##
[0513] A four-necked reactor equipped with a thermometer was
charged with 2.50 g (16.6 mmol) of cyclohexylhydrazine
hydrochloride under a nitrogen stream, which was then dissolved in
8 ml of triethylamine. To the solution was added 5.63 g (33.2 mmol)
of 2-chlorobenzothiazole and stirred at 80.degree. C. for 5 hours.
After completion of the reaction, the reaction solution was cooled
to 20.degree. C., charged into 150 ml of saturated sodium hydrogen
carbonate aqueous solution, and extracted with 300 ml of ethyl
acetate. The ethyl acetate phase was dried over sodium sulfate
anhydrous. After filtering off sodium sulfate, ethyl acetate was
distilled off under reduced pressure using a rotary evaporator to
give a yellow solid, which was purified by silica gel column
chromatography (hexane:ethyl acetate=75:25) to give 1.02 g of
intermediate E as a white solid (yield: 22.3 mol %).
[0514] The structure of the target compound was identified by
.sup.1H-NMR. The result is given below.
[0515] .sup.1H-NMR(400 MHz,CDCl.sub.3,TMS,.delta.
ppm):7.58(d,1H,J=7.8 Hz), 7.52(d,1H,J=8.2 Hz), 7.26(dd,1H,J=7.4
Hz,8.2 Hz), 7.05(dd,1H,J=7.4 Hz,7.8 Hz), 4.25-4.32(m,1H),
4.04(s,2H), 1.84-1.88(m,4H), 1.68-1.73(m,1H), 1.43-1.59(m,4H),
1.08-1.19(m,1H)
[0516] Step 2: Synthesis of Compound 4
[0517] A three-necked reactor equipped with a thermometer was
charged with 1.40 g (1.49 mmol) of intermediate B synthesized in
step 2 for synthesis of compound 1 in Synthesis Example 1, 456 mg
(1.84 mmol) of intermediate E synthesized in Step 1, 38.6 mg (0.166
mmol) of (.+-.)-10-camphorsulfonic acid, 16 ml of THF and 4 ml of
ethanol under a nitrogen stream to prepare a homogenous solution.
Thereafter, reaction was performed at 40.degree. C. for 5 hours.
After completion of the reaction, the reaction solution was charged
into 100 ml of water and extracted with 200 ml of ethyl acetate.
The ethyl acetate phase was dried over sodium sulfate anhydrous and
sodium sulfate was filtered off. Ethyl acetate was distilled off
from the filtrate under reduced pressure using a rotary evaporator
to give a yellow solid, which was purified by silica gel column
chromatography (chloroform:THF=97:3) to give 1.24 g of compound 4
as a pale yellow solid (yield: 71.4 mol %).
[0518] The structure of the target compound was identified by
.sup.1H-NMR. The result is given below.
[0519] .sup.1H-NMR(500 MHz,CDCl.sub.3,TMS,.delta. ppm):8.15(s,1H),
7.72(d,1H,J=1.5 Hz), 7.68(dd,1H,J=1.5 Hz,8.0 Hz), 7.66(dd,1H,J=1.5
Hz,8.0 Hz), 7.31-7.35(m,1H), 7.14-7.18(m,1H), 7.13(d,1H,J=9.0 Hz),
7.10(dd,1H,J=1.5 Hz,9.0 Hz), 6.96-7.00(m,4H), 6.86-6.90(m,4H),
6.40(dd,2H,J=1.5 Hz,17.0 Hz), 6.13 (dd,2H,J=10.0 Hz,17.0 Hz),
5.82(dd,2H,J=1.5 Hz,10.0 Hz), 4.62-4.70(m,1H), 4.17(t,4H,J=6.5 Hz),
3.94(t,4H,J=6.5 Hz), 2.55-2.74(m,4H), 2.27-2.47(m,10H),
1.90-2.00(m,4H), 1.65-1.85(m,16H), 1.42-1.55(m,10H),
1.24-1.33(m,2H)
Synthesis Example 5
Synthesis of Compound 5
##STR00056##
[0521] Step 1: Synthesis of Intermediate F
##STR00057##
[0522] A three-necked reactor equipped with a thermometer was
charged with 2.00 g (12.1 mmol) of 2-hydrazinobenzothiazole under a
nitrogen stream, which was then dissolved in 30 ml of DMF. To the
solution was added 7.88 g (24.2 mol) of cesium carbonate and the
solution was cooled to 0.degree. C., and 1.98 g (14.5 mmol) of
butyl 2-chloroethyl ether was added dropwise over 5 minutes. The
reaction solution was then warmed back to room temperature
(23.degree. C.; hereinafter the same) and stirred for 3 hours.
After completion of the reaction, 200 ml of water was added to the
reaction solution and extracted twice with 100 ml of ethyl acetate.
The combined organic phase was dried over sodium sulfate anhydrous
and sodium sulfate was filtered off. After condensation using a
rotary evaporator, purification was performed by silica gel column
chromatography (n-hexane:ethyl acetate=75:25) to give 1.70 g of
intermediate F as a white solid (yield: 53.0 mol %).
[0523] The structure of the target compound was identified by
.sup.1H-NMR. The result is given below.
[0524] .sup.1H-NMR(500 MHz,CDCl.sub.3, TMS,.delta.
ppm):7.61(dd,1H,J=1.0 Hz,8.0 Hz), 7.50(dd,1H,J=1.0 Hz,8.0 Hz),
7.27-7.29(m,1H), 7.04-7.08(m,1H), 4.70(s,2H), 4.01(t,2H,J=5.0 Hz),
3.82(t,2H,J=5.0 Hz), 3.44(t,2H,J=7.0 Hz), 1.52-1.57(m,2H),
1.31-1.39(m,2H), 0.90(t,3H,J=7.0 Hz)
[0525] Step 2: Synthesis of Compound 5
[0526] A three-necked reactor equipped with a thermometer was
charged with 1.50 g (1.60 mmol) of intermediate B synthesized in
Step 2 of Synthesis Example 1, 396 mg (1.78 mmol) of intermediate F
synthesized in Step 1, 41.4 mg (0.178 mmol) of
(.+-.)-10-camphorsulfonic acid, 16 ml of THF and 4 ml of ethanol
under a nitrogen stream to prepare a homogenous solution.
Thereafter, reaction was performed at 40.degree. C. for 5 hours.
After completion of the reaction, the reaction solution was charged
into 100 ml of water and extracted with 200 ml of ethyl acetate.
The ethyl acetate phase was dried over sodium sulfate anhydrous and
sodium sulfate was filtered off. Ethyl acetate was distilled off
from the filtrate under reduced pressure using a rotary evaporator
to give a yellow solid, which was purified by silica gel column
chromatography (toluene:ethyl acetate=9:1) to give 1.31 g of
compound 5 as a pale yellow solid (yield: 69.4 mol %).
[0527] The structure of the target compound was identified by
.sup.1H-NMR. The result is given below.
[0528] .sup.1H-NMR(500 MHz,CDCl.sub.3, TMS,.delta. ppm):
8.03(s,1H), 7.76(d,1H,J=1.5 Hz), 7.65-7.71(m,2H), 7.34(ddd,1H,J=1.5
Hz,8.0 Hz,8.0 Hz), 7.17(ddd,1H,J=1.5 Hz, 8.0 Hz, 8.0 Hz),
7.09-7.12(m,2H), 6.96-7.00(m,4H), 6.87-6.90(m,4H), 6.40(dd,2H,J=1.5
Hz,17.5 Hz), 6.13(dd,2H,J=10.5 Hz,17.5 Hz), 5.82(dd,2H,J=1.5
Hz,10.5 Hz), 4.45(t,2H,J=5.5 Hz), 4.18(t,4H,J=7.0 Hz),
3.95(t,4H,J=7.0 Hz), 3.79(t,2H,J=5.5 Hz), 3.44(t,2H,J=7.0 Hz),
2.55-2.74(m,4H), 2.28-2.40(m,8H), 1.65-1.83(m,16H),
1.42-1.55(m,10H), 1.25-1.34(m,2H), 0.85(t,3H,J=7.0 Hz)
Synthesis Example 6
Synthesis of Compound 6
##STR00058##
[0530] Step 1: Synthesis of Intermediate G
##STR00059##
[0531] A four-necked reactor equipped with a thermometer was
charged with 5.04 g (30.5 mmol) of 2-hydrazinobenzothiazole under a
nitrogen stream, which was then dissolved in 50 ml of DMF. To the
solution was added 14.9 g (45.8 mmol) of cesium carbonate and 4.94
g (36.6 mmol) of 4-bromo-1-butene, and stirred at room temperature
for 7 hours. After completion of the reaction, the reaction
solution was charged into 200 ml of water and extracted with 300 ml
ethyl acetate. The ethyl acetate phase was dried over sodium
sulfate anhydrous. After filtering off sodium sulfate, ethyl
acetate was distilled off under reduced pressure using a rotary
evaporator to give a yellow solid, which was purified by silica gel
column chromatography (n-hexane:ethyl acetate=70:30) to give 4.40 g
of intermediate G as a white solid (yield: 49.5 mol %).
[0532] The structure of the target compound was identified by
.sup.1H-NMR. The result is given below.
[0533] .sup.1H-NMR(500 MHz,CDCl.sub.3, TMS,.delta. ppm):
7.60(dd,1H,J=1.0 Hz,8.0 Hz), 7.54(dd,1H,J=1.0 Hz,8.0 Hz),
7.28(ddd,1H,J=1.0 Hz,7.5 Hz,8.0 Hz), 7.06(ddd,1H,J=1.0 Hz,7.5
Hz,8.0 Hz), 5 .89(ddt, 1H,J=7.0 Hz,10.5 Hz,17.0 Hz),
5.17(ddt,1H,J=1.5 Hz,3.0 Hz,17.0 Hz), 5.09(ddt,1H,J=1.0 Hz,3.0
Hz,10.5 Hz), 4.26(s,2H), 3.85(t,2H,J=7.0 Hz), 2.52(dddt,2H,J=1.0
Hz,1.5 Hz,7.0 Hz,7.0 Hz)
[0534] Step 2: Synthesis of Compound 6
[0535] A four-necked reactor equipped with a thermometer was
charged with 195 mg (1.77 mmol) of intermediate G synthesized in
Step 1 and 1.50 g (1.60 mmol) of intermediate B synthesized in Step
2 for synthesis of compound 1 in Synthesis Example 1 under a
nitrogen stream, which were then dissolved in a mixture solvent of
3 ml ethanol and 15 ml THF. To the solution was added 41.2 mg
(0.177 mmol) of (.+-.)-10-camphorsulfonic acid and stirred at
40.degree. C. for 8 hours. After completion of the reaction, the
reaction solution was charged into 150 ml of water and extracted
with 300 ml of ethyl acetate. The ethyl acetate phase was dried
over sodium sulfate anhydrous. After filtering off sodium sulfate,
ethyl acetate was distilled off under reduced pressure using a
rotary evaporator to give a yellow solid, which was purified by
silica gel column chromatography (toluene:ethyl acetate=90:10) to
give 1.26 g of compound 6 as a white solid (yield: 69.3 mol %).
[0536] The structure of the target compound was identified by
.sup.1H-NMR. The result is given below.
[0537] .sup.1H-NMR(500 MHz,CDCl.sub.3,TMS,.delta.
ppm):7.76(d,1H,J=2.5 Hz), 7.67-7.70(m,3H), 7.35(ddd,1H,J=1.5 Hz,7.5
Hz,8.0 Hz), 7.18(ddd,1H,J=1.5 Hz,7.5 Hz,8.0 Hz), 7.10-7.14(m,2H),
6.99(d,2H,J=9.5 Hz), 6.98(d,2H,J=9.5 Hz), 6.88(d,4H,J=9.5 Hz),
6.40(dd,2H,J=1.5 Hz,17.5 Hz), 6.13(dd,2H,J=10.5 Hz,17.5 Hz),
5.89(ddt,1H,J=6.5 Hz,10.5 Hz,17.0 Hz), 5.82(dd,2H,J=1.5 Hz,10.5
Hz), 5.18(dd,1H,J=1.5 Hz,17.0 Hz), 5.15(dd,1H,J=1.5 Hz,10.5 Hz),
4.38(t,2H,J=7.0 Hz), 4.18(t,4H,J=6.5 Hz), 3.95(t,4H,J=6.5 Hz),
2.58-2.68(m,4H), 2.51(dt,2H,J=6.5 Hz,7.0 Hz), 2.31-2.35(m,8H),
1.76-1.85(m,4H), 1.65-1.74(m,12H), 1.41-1.54(m,8H)
Synthesis Example 7
Synthesis of Compound 7
##STR00060##
[0539] Step 1: Synthesis of Intermediate H
##STR00061##
[0540] A three-necked reactor equipped with a thermometer was
charged with 2.00 g (12.1 mmol) of 2-hydrazinobenzothiazole under a
nitrogen stream, which was then dissolved in 30 ml of DMF. To the
solution was added 7.88 g (24.2 mol) of cesium carbonate and the
solution was cooled to 0.degree. C., and 2.39 g(14.5 mmol) of
2-bromohexane was added dropwise over 5 minutes. The reaction
solution was then warmed back to room temperature and stirred for 3
hours. After completion of the reaction, 200 ml of water was added
to the reaction solution and extracted twice with 100 ml of ethyl
acetate. The combined organic phase was dried over sodium sulfate
anhydrous and sodium sulfate was filtered off. After condensation
using a rotary evaporator, purification was performed by silica gel
column chromatography (n-hexane:ethyl acetate=93:7) to give 1.61 g
of intermediate H as a white solid (yield: 53.4 mol %).
[0541] The structure of the target compound was identified by
.sup.1H-NMR. The result is given below.
[0542] .sup.1H-NMR(400 MHz,CDCl.sub.3,TMS,oppm):7.59(dd,1H,J=1.0
Hz,8.0 Hz), 7.52(dd,1H,J=1.0 Hz,8.0 Hz), 7.24 -7.30(m,1H),
7.05(ddd,1H,J=1.0 Hz,8.0 Hz,8.0 Hz), 3.97(s,2H), 1.47-1.74(m,3H),
1.20-1.41(m,7H), 0.89(t,3H,J=5.5 Hz)
[0543] Step 2: Synthesis of Compound 7
[0544] A three-necked reactor equipped with a thermometer was
charged with 1.50 g (1.60 mmol) of intermediate B synthesized in
Step 2 for synthesis of compound 1 in Synthesis Example 1, 444 mg
(1.78 mmol) of intermediate H synthesized in Step 1, 41.4 mg (0.178
mmol) of (.+-.)-10-camphorsulfonic acid, 16 ml of THF and 4 ml of
ethanol under a nitrogen stream to prepare a homogenous solution.
Thereafter, reaction was performed at 40.degree. C. for 5 hours.
After completion of the reaction, the reaction solution was charged
into 100 ml of water and extracted with 200 ml of chloroform. The
organic phase was dried over sodium sulfate anhydrous and sodium
sulfate was filtered off. After condensation using a rotary
evaporator, purification was performed by silica gel column
chromatography (toluene:ethyl acetate=92:8) to give 1.35 g of
compound 7 as a pale yellow solid (yield: 72.4 mol %).
[0545] The structure of the target compound was identified by
.sup.1H-NMR. The result is given below.
[0546] .sup.1-NMR(500 MHz,CDCl.sub.3, TMS,.delta. ppm): 8.04(s,1H),
7.73(d,1H,J=1.5 Hz), 7.69(dd,1H,J=1.5 Hz,7.8 Hz), 7.65(dd,1H,J=1.5
Hz,7.8 Hz), 7.33(ddd,1H,J=1.5 Hz,7.8 Hz,7.8 Hz), 7.07-7.19(m,3H),
6.95-7.01(m,4H), 6.85-6.91(m,4H), 6.40(dd,2H,J=1.5 Hz,17.5 Hz),
6.13(dd,2H,J=10.5 Hz,17.5 Hz), 5.82(dd,2H,J=1.5 Hz,10.5 Hz),
4.18(t,4H,J=6.5 Hz), 3.95(t,4H,J=6.5 Hz), 2.54-2.73(m,4H),
2.25-2.40(m,8H), 1.65-1.83(m,16H), 1.60-1.62(m,2H), 1.57(d,3H,J=7.5
Hz), 1.24-1.55(m,13H), 0.87(t,3H,J=7.5 Hz)
Synthesis Example 8
Synthesis of 8
##STR00062##
[0548] Step 1: Synthesis of Intermediate I
##STR00063##
[0549] A four-necked reactor equipped with a thermometer was
charged with 2.00 g (12.1 mmol) of 2-hydrazinobenzothiazole under a
nitrogen stream, which was then dissolved in 30 ml of DMF. To the
solution was added 7.88 g (24.2 mol) of cesium carbonate and 1.93
g(14.5 mmol) of 1-bromo-2-butyne and stirred at room temperature
for 20 hours. After completion of the reaction, the reaction
solution was charged into 200 ml of water and extracted with 300 ml
of ethyl acetate. The ethyl acetate phase was dried over sodium
sulfate anhydrous. After filtering off sodium sulfate, ethyl
acetate was distilled off under reduced pressure using a rotary
evaporator to give a brown solid, which was purified by silica gel
column chromatography (n-hexane:ethyl acetate=85:15) to give 1.25 g
of intermediate I as a white solid (yield: 47.5 mol %).
[0550] The structure of the target compound was identified by
.sup.1H-NMR. The result is given below.
[0551] .sup.1-H-NMR(500 MHz,CDCl.sub.3, TMS,.delta. ppm):
7.63(dd,1H,J=1.3 Hz,7.8 Hz), 7.58(dd,1H,J=1.3 Hz,7.8 Hz),
7.29(ddd,1H,J=1.3 Hz,7.8 Hz,7.8 Hz), 7.10(ddd,1H,J=1.3 Hz,7.8
Hz,7.8 Hz), 4.56(q, 2H,J=2.5 Hz), 4.36(s,2H), 1.84(t,3H,J=2.5
Hz)
[0552] Step 2: Synthesis of Compound 8
[0553] A three-necked reactor equipped with a thermometer was
charged with 1.50 g (1.60 mmol) of intermediate B synthesized in
Step 2 for synthesis of compound 1 in Synthesis Example 1, 387 mg
(1.78 mmol) of intermediate I synthesized in Step 1, 41.4 mg (0.178
mmol) of (.+-.)-10-camphorsulfonic acid, 16 ml of THF and 4 ml of
ethanol under a nitrogen stream to prepare a homogenous solution.
Thereafter, reaction was performed at 40.degree. C. for 5 hours.
After completion of the reaction, the reaction solution was charged
into 100 ml of water and extracted with 200 ml of chloroform. The
organic phase was dried over sodium sulfate anhydrous and sodium
sulfate was filtered off. After condensation using a rotary
evaporator, purification was performed by silica gel column
chromatography (toluene:ethyl acetate=9:1) to give 1.54 g of
compound 8 as a pale yellow solid (yield: 84.9 mol %).
[0554] The structure of the target compound was identified by
.sup.1H-NMR. The result is given below.
[0555] .sup.1H-NMR(500 MHz,CDCl.sub.3,TMS,.delta. ppm):7.90(s,1H),
7.78(d,1H,J=1.3 Hz), 7.67-7.73(m,2H), 7.35(ddd,1H,J=1.3 Hz,7.5
Hz,7.5 Hz), 7.18(ddd,1H,J=1.3 Hz,7.5 Hz,7.5 Hz), 7.09-7.15(m,2H),
6.95-7.01(m,4H), 6.85-6.91(m,4H), 6.40(dd,2H,J=1.5 Hz,17.0 Hz),
6.13(dd,2H,J=10.5 Hz,17.0 Hz), 5.82(dd,2H,J=1.5 Hz,10.5 Hz),
5.06(d,2H,J=2.0 Hz), 4.18(t,4H,J=6.0 Hz), 3.95(t,4H,J=6.0 Hz),
2.55-2.76(m,4H), 2.26-2.43(m,8H), 1.64-1.83(m,19H),
1.41-1.55(m,8H)
Synthesis Example 9
Synthesis of Compound 9
##STR00064##
[0557] Step 1: Synthesis of Intermediate J
##STR00065##
[0558] A four-necked reactor equipped with a thermometer was
charged with 5.00 g (30.3 mmol) of 2-hydrazinobenzothiazole under a
nitrogen stream, which was then dissolved in 100 ml of DMF. To the
solution was added 20.9 g (152 mmol) of potassium carbonate and
5.17 g (30.3 mmol) of 5-bromovaleronitrile and stirred at
60.degree. C. for 8 hours. After completion of the reaction, the
reaction solution was cooled to 20.degree. C., charged into 500 ml
of water, and extracted with 500 ml of ethyl acetate. The ethyl
acetate phase was dried over sodium sulfate anhydrous. After
filtering off sodium sulfate, ethyl acetate was distilled off under
reduced pressure using a rotary evaporator to give a yellow solid,
which was purified by silica gel column chromatography
(n-hexane:ethyl acetate=60:40) to give 3.41 g of intermediate J as
a white solid (yield: 45.7 mol %).
[0559] The structure of the target compound was identified by
.sup.1H-NMR. The result is given below.
[0560] .sup.1H-NMR(400 MHz,CDCl.sub.3, TMS,.delta. ppm):
7.60(d,1H,J=7.8 Hz), 7.51(d,1H,J=8.1 Hz), 7.28(dd,1H,J=7.3, 8.1
Hz), 7.07(dd,1H,J=7.3 Hz,7.8 Hz), 4.23(s,2H), 3.81(t,2H,J=6.9 Hz),
2.46(t,2H,J=7.1 Hz), 1.88-1.95(m,2H), 1.71-1.79(m,2H)
[0561] Step 2: Synthesis of Compound 9
[0562] A three-necked reactor equipped with a thermometer was
charged with 1.50 g (1.60 mmol) of intermediate B synthesized in
Step 2 for synthesis of compound 1 in Synthesis Example 1, 438 mg
(1.78 mmol) of intermediate J synthesized in Step 1, 41.4 mg (0.178
mmol) of (.+-.)-10-camphorsulfonic acid, 16 ml of THF and 4 ml of
ethanol under a nitrogen stream to prepare a homogenous solution.
Thereafter, reaction was performed at 40.degree. C. for 5 hours.
After completion of the reaction, the reaction solution was charged
into 100 ml of water and extracted with 200 ml of ethyl acetate.
The ethyl acetate phase was dried over sodium sulfate anhydrous and
sodium sulfate was filtered off. Ethyl acetate was distilled off
from the filtrate under reduced pressure using a rotary evaporator
to give a yellow solid, which was purified by silica gel column
chromatography (toluene:ethyl acetate=85:15) to give 1.31 g of
compound 9 as a pale yellow solid (yield: 70.2mo1%).
[0563] The structure of the target compound was identified by
.sup.1H-NMR. The result is given below.
[0564] .sup.1H-NMR(500 MHz,CDCl.sub.3,TMS,.delta.
ppm):7.74(d,1H,J=1.5 Hz), 7.64-7.72(m,3H), 7.35(ddd,1H,J=1.5 Hz,8.0
Hz,8.0 Hz), 7.19(ddd,1H,J=1.5 Hz,8.0 Hz,8.0 Hz), 7.10-7.14(m,2H),
6.96-7.01(m,4H), 6.86-6.91(m,4H), 6.40(dd,2H,J=1.5 Hz,17.0 Hz),
6.12(dd,2H,J=10.5 Hz,17.0 Hz), 5.82(dd,2H,J=1.5 Hz,10.5 Hz),
4.22(t,2H,J=6.5 Hz), 4.18(t,4H,J=6.5 Hz), 3.95(t,4H,J=6.5 Hz),
2.58-2.75(m,4H), 2.55(t,2H,J=6.5 Hz), 2.26-2.40(m,8H),
1.96(tt,2H,J=6.5 Hz,6.5 Hz), 1.66-1.83(m,18H), 1.42-1.55(m,8H)
Example 1
Synthesis of Compound X
##STR00066##
[0566] Step 1: Synthesis of Intermediate K
##STR00067##
[0567] A three-necked reactor equipped with a condenser and a
thermometer was charged with 104.77 g (0.9515 mol) of hydroquinone,
100 g (0.7320 mol) of 6-chlorohexanol, 500 g of distilled water and
100 g of o-xylene under a nitrogen stream. 35.15 g (0.8784 mol) of
sodium hydroxide was further added gradually with stirring over 20
minutes so that the temperature of the reaction mass does not
exceed 40.degree. C. After addition of sodium hydroxide the
reaction mass was heated and further reacted at reflux (96.degree.
C.) for 12 hours.
[0568] After completion of the reaction, the temperature of the
reaction solution was lowered to 80.degree. C., 200 g of distilled
water was added, and the reaction solution was cooled to 10.degree.
C. allowing crystals to precipitate. The precipitated crystals were
isolated by filtration, washed with 500 g of distilled water, and
dried in vacuo to give 123.3 g of brown crystals.
[0569] High-performance liquid chromatography of the brown crystals
revealed that the mole ratio of the abundance of compounds in the
brown crystals was hydroquinone/intermediate K/by-product
K=1.3/90.1/8.1. The mixture was directly used in Step 2 without
purification.
[0570] Step 2: Synthesis of Intermediate L
##STR00068##
[0571] A three-necked reactor equipped with a thermometer and a
condenser with a Dean-Stark trap was charged with 10.00 g of the
brown crystals containing intermediate K synthesized in Step 1, 100
g of toluene and 0.105 g (0.476 mmol) of 2,6-di-t-butyl-p-cresol
under a nitrogen stream, and the entire mass was stirred. The
solution was heated to 80.degree. C., 20.56 g (0.1427 mol) of
2-carboxyethyl acrylate and 1.37 g (14.3 mmol) of methanesulfonic
acid were added, and dehydration reaction was performed at reflux
(110.degree. C.) for 2 hours with generated water removed out of
the system. The reaction solution was then cooled to 30.degree. C.
and 500 g of distilled water was added. After stirring, the entire
mass was allowed to stand. The organic phase was separated and 500
g of 5% brine was added for phase separation. The organic phase was
separated and dried over sodium sulfate anhydrous, and sodium
sulfate was filtered off. After condensation using a rotary
evaporator, purification was performed by silica gel column
chromatography (toluene:ethyl acetate=8:1) to give a total of 7.93
g of intermediate L as a white solid in Steps 1 and 2 (yield: 40
mol %).
[0572] The structure of the target compound was identified by
.sup.1H-NMR. The result is given below.
[0573] .sup.1H-NMR(500 MHz,CDCl.sub.3, TMS,.delta. ppm):
6.77(d,2H,J=9.0 Hz), 6.76(d,2H,J=9.0 Hz), 6.41(dd,1H,J=1.5 Hz,17.5
Hz), 6.11(dd,1H,J=10.5 Hz,17.5 Hz), 5.83(dd,1H,J=1.5 Hz,10.5 Hz),
4.83(s,1H), 4.44(t,2H,J=6.5 Hz), 4.13(t,2H,J=6.5 Hz),
3.89(t,2H,J=6.5 Hz), 2.69(t,2H,J=6.5 Hz), 1.71-1.80(m,2H),
1.62-1.70(m,2H), 1.36-1.52(m,4H)
[0574] Step 3: Synthesis of Intermediate M
##STR00069##
[0575] A three-necked reactor equipped with a thermometer was
charged with 3.58 g (0.0208 mol) of
trans-1,4-cyclohexanedicarboxylic acid and 25 ml of THF under a
nitrogen stream. 1.25 g (0.0109 mol) of methanesulfonyl chloride
was added, and the reactor was immersed in a water bath to adjust
the reaction solution temperature to 5.degree. C. 1.15 g (0.0114
mol) of triethylamine was added dropwise over 15 minutes so that
the reaction solution temperature becomes 15.degree. C. or below.
After stirring the reaction solution at 5.degree. C. for 1 hour,
0.127 g (1.04 mmol) of 4-(dimethylamino)pyridine and 3.51 g (0.0104
mol) of intermediate L were added, and 1.15 g (0.0114 mol) of
triethylamine was added dropwise over 15 minutes so that the
reaction solution temperature becomes 15.degree. C. or below. The
reaction solution was reacted at 25.degree. C. for 2 hours. After
completion of the reaction, 300 ml of distilled water and 30 ml of
saturated brine were added to the reaction solution and extracted
twice with 200 ml of chloroform. The combined organic phase was
dried over sodium sulfate anhydrous and sodium sulfate was filtered
off. After condensation using a rotary evaporator, purification was
performed by silica gel column chromatography (chloroform:THF=95:5)
to give 2.41 g of intermediate M as a white solid
(yield:47mo1%).
[0576] The structure of the target compound was identified by
.sup.1H-NMR. The result is given below.
[0577] .sup.1H-NMR(500 MHz,CDCl.sub.3,TMS,.delta.
ppm):6.96(d,2H,J=9.0 Hz), 6.86(d,2H,J=9.0 Hz), 6.41(dd,1H,J=1.5
Hz,17.5 Hz), 6.11(dd,1H,J=10.5 Hz,17.5 Hz), 5 .83(dd,1H,J=1.5
Hz,10.5 Hz), 4.44(t,2H,J=6.5 Hz), 4.13(t,2H,J=6.5 Hz),
3.93(t,2H,J=6.5 Hz), 2.69(t,2H,J=6.5 Hz), 2.47-2.57(m,1H),
2.34-2.43(m,1H), 2.12-2.28(m,4H), 1.73-1.82(m,2H),
1.36-1.71(m,10H)
[0578] Sten 4: Synthesis of Intermediate N
##STR00070##
[0579] A three-necked reactor equipped with a thermometer was
charged with 3.90 g (8.85 mmol) of intermediate A synthesized in
Step 1 of Synthesis Example 1, 0.52 g (7.1 mmol) of DMF and 39 g of
toluene under a nitrogen stream. The solution was cooled to
5.degree. C. and 1.10 g (9.3 mmol) of thionyl chloride was added
dropwise over 10 minutes, and reaction was performed at 5.degree.
C. for 1 hour. The reaction solution was then condensed using a
rotary evaporator and dried in vacuo to give a white solid.
[0580] Further, a three-necked reactor equipped with a thermometer
was charged with 6.10 g (0.0443 mol) of 2,5-dihydroxybenzaldehyde
and 0.985 g (9.7 mmol) of triethylamine under a nitrogen stream,
which were then dissolved in 35 g of THF. The solution was cooled
to 5.degree. C., and the white solid obtained above was added and
reacted for 30 minutes. 200 ml of distilled water and 10 ml of
saturated brine were then added to the reaction solution and
extracted twice with 100 ml of ethyl acetate. The combined organic
phase was dried over sodium sulfate anhydrous and sodium sulfate
was filtered off. After condensation using a rotary evaporator,
purification was performed by silica gel column chromatography
(toluene:THF=95:5) to give 1.53 g of intermediate N as a white
solid (yield: 32 mol %).
[0581] The structure of the target compound was identified by
.sup.1H-NMR. The result is given below.
[0582] .sup.1H-NMR(500 MHz,CDCl.sub.3,TMS,.delta. ppm):10.91(s,1H),
9.86(s,1H), 7.32(d,1H,J=3.0 Hz), 7.24(dd,1H,J=3.0 Hz,9.0 Hz),
7.01(d,1H,J=9.0 Hz), 6.97(d,2H,J=9.0 Hz), 6.87(d,2H,J=9.0 Hz),
6.40(dd,1H,J=1.5 Hz,17.5 Hz), 6.12(dd,1H,J=10.5 Hz,17.5 Hz), 5
.82(dd,1H,J=1.5 Hz,10.5 Hz), 4.17(t,2H,J=6.5 Hz), 3.94(t,2H,J=6.5
Hz), 2.51-2.65(m,2H), 2.20-2.35(m,4H), 1.75-1.83(m,2H),
1.63-1.75(m,6H), 1.36-1.55(m,4H)
[0583] Step 6: Synthesis of Intermediate P
##STR00071##
[0584] A three-necked reactor equipped with a thermometer was
charged with 1.00 g (2.04 mmol) of intermediate M synthesized in
Step 3 under a nitrogen stream, which was then dissolved in 15 ml
of THF. 0.234 g (2.04 mmol) of methanesulfonyl chloride was added,
the reaction solution was cooled to 5.degree. C., and 0.236 g (2.33
mmol) of triethylamine was added dropwise over 10 minutes. After
reacting the reaction solution at 5.degree. C. for 1 hour, 0.018 g
(0.15 mmol) of 4-dimethylaminopyridine and 0.786 g (1.46 mmol) of
intermediate N synthesized in Step 4 were added, and 0.177 g (1.75
mmol) of triethylamine was added dropwise over 10 minutes. After
reacting the reaction solution at 25.degree. C. for 2 hours, 200 ml
of distilled water and 20 ml of saturated brine were added to the
reaction solution and extracted twice with 100 ml of chloroform.
The combined organic phase was dried over sodium sulfate anhydrous
and sodium sulfate was filtered off. After condensation using a
rotary evaporator, purification was performed by silica gel column
chromatography (chloroform:THF=99:1) to give 1.15 g of intermediate
P as a white solid (yield: 78mo1%).
[0585] The structure of the target compound was identified by
.sup.1H-NMR. The result is given below.
[0586] .sup.1H-NMR(500 MHz,DMSO-d.sub.6,TMS,.delta.
ppm):10.08(s,1H), 7.61(d,1H,J=3.0 Hz), 7.37(dd,1H,J=3.0 Hz,9.0 Hz),
7.20(d,1H,J=9.0 Hz), 6.98(d,2H,J=9.0 Hz), 6.97(d,2H,J=9.0 Hz),
6.88(d,2H,J=9.0 Hz), 6.88(d,2H,J=9.0 Hz), 6.41(dd,1H,J=1.5 Hz,17.5
Hz), 6.40(dd,1H,J=1.5 Hz,17.5 Hz), 6.13(dd,1H,J=10.5 Hz,17.5 Hz),
6.11(dd,1H,J=10.5 Hz,17.5 Hz), 5.83(dd,1H,J=1.5 Hz,10.5 Hz),
5.82(dd,1H,J=1.5 Hz,10.5 Hz), 4.44(t,2H,J=6.5 Hz), 4.17(t,2H,J=6.5
Hz), 4.13 (t,2H,J=6.5 Hz), 3.94(t,2H,J=6.5 Hz), 3.94(t,2H,J=6.5
Hz), 2.53-2.74(m,6H), 2.20-2.39(m,8H), 1.60-1.83(m,16H),
1.34-1.56(m,8H)
[0587] Step 7: Synthesis of Compound X
[0588] A three-necked reactor equipped with a thermometer was
charged with 0.944 g (0.934 mmol) of intermediate P synthesized in
Step 6, 0.279 g (1.12 mmol) of intermediate C synthesized in Step 1
of Synthesis Example 2 and 0.02 g of 2,6-di-t-butyl-p-cresol under
a nitrogen stream, which were then dissolved in 15 ml of THF. To
the solution were added 44 mg (0.189 mmol) of
(.+-.)-10-camphorsulfonic acid and 2 ml of ethanol and heated to
40.degree. C. for reaction for 5 hours. After completion of the
reaction, 100 ml of distilled water and 15 ml of saturated brine
were added to the reaction solution and extracted twice with 100 ml
of ethyl acetate. The combined organic phase was dried over sodium
sulfate anhydrous and sodium sulfate was filtered off. After
condensation using a rotary evaporator, the resulting solid was
dissolved in 10 ml of chloroform. To the solution was added 150 ml
of methanol to precipitate crystals, which were filtered off,
washed with methanol and dried in vacuo to give 0.986 g of compound
X as a pale yellow solid (yield: 80 mol %).
[0589] The structure of the target compound was identified by
.sup.1H-NMR. The result is given below.
[0590] .sup.1H-NMR(500 MHz,DMSO-d.sub.6,TMS,.delta.
ppm):7.75(d,1H,J=2.5 Hz), 7.65-7.71(m,3H), 7.34(dd,1H,J=1.0 Hz,7.5
Hz), 7.17(dd, 1H,J=1.0 Hz,7.5 Hz), 7.07-7.14(m,2H), 6.99(d,2H,J=9.0
Hz), 6.98(d,2H,J=9.0 Hz), 6.88(d,2H,J=9.0 Hz), 6.88(d,2H,J=9.0 Hz),
6.41(dd,1H,J=1.5 Hz,17.5 Hz), 6.40(dd,1H,J=1.5 Hz,17.5 Hz),
6.13(dd,1H,J=10.5 Hz,17.5 Hz), 6.11(dd,1H,J=10.5 Hz,17.5 Hz),
5.83(dd,1H,J=1.5 Hz,10.5 Hz), 5.82(dd,1H,J=1.5 Hz,10.5 Hz),
4.44(t,2H,J=6.5 Hz), 4.30(t,2H,J=7.5 Hz), 4.18(t,2H,J=6.5 Hz),
4.13(t,2H,J=6.5 Hz), 3.95(t,2H,J=6.5 Hz), 3.94(t,2H,J=6.5 Hz),
2.54-2.74(m,6H), 2.25-2.40(m,8H), 1.62-1.84(m,18H),
1.28-1.56(m,14H), 0.90(t,3H,J=7.0 Hz)
Example 2
Synthesis of Mixture X
##STR00072##
[0592] Step 1: Synthesis of Intermediate Mixture Q
##STR00073##
[0593] A three-necked reactor equipped with a thermometer and a
condenser with a Dean-Stark trap was charged with 10.00 g of the
brown crystals containing intermediate K synthesized in Step 1 in
Example 1, 100 g of toluene and 0.105 g (0.476 mmol) of
2,6-di-t-butyl-p-cresol under a nitrogen stream, and the entire
mass was stirred. The solution was heated to 80.degree. C., 5.14 g
(71.3 mmol) of acrylic acid and 0.91 g (9.51 mmol) of
methanesulfonic acid were added, and dehydration reaction was
performed at reflux (110.degree. C.) for 3 hours with generated
water removed out of the system. The reaction solution was then
cooled to 30.degree. C., and 500 g of distilled water was added.
After stirring, the entire mass was allowed to stand. The organic
phase was separated and 500 g of 5% brine was added for phase
separation. The organic phase was separated and dried over sodium
sulfate anhydrous, and sodium sulfate was filtered off. After
condensation using a rotary evaporator, purification was performed
by silica gel column chromatography (toluene:ethyl acetate=8:1) to
give 8.2 g of mixture Q as a white solid. High-performance liquid
chromatography of the white solid revealed that the mole ratio of
the abundance of compounds in the white solid was as shown below.
The mixture was directly used in Step 2 without purification.
##STR00074##
[0594] Step 2: Synthesis of Intermediate Mixture R
##STR00075##
[0595] A three-necked reactor equipped with a thermometer was
charged with 10.68 g (62.0 mmol) of
trans-1,4-cyclohexanedicarboxylic acid and 90 ml of THF under a
nitrogen stream. 3.9 g (34.1 mmol) of methanesulfonyl chloride was
added and the reactor was immersed in a water bath to adjust the
reaction solution temperature to 20.degree. C. 3.79 g (37.5 mmol)
of triethylamine was added dropwise over 10 minutes while retaining
the reaction solution temperature to 20.degree. C. to 30.degree. C.
After the dropwise addition, the entire mass was further stirred at
25.degree. C. for 2 hours.
[0596] To the resulting reaction solution were added 0.38 g (3.12
mmol) of 4-(dimethylamino)pyridine and 8.2 g of mixture Q
synthesized in Step 1, and the reactor was again immersed in the
water bath to adjust the reaction solution temperature to
15.degree. C. 3.79 g (37.5 mmol) of triethylamine was added
dropwise over 10 minutes while retaining the reaction solution
temperature to 20.degree. C. to 30.degree. C. After the dropwise
addition, the entire mass was further stirred at 25.degree. C. for
2 hours. After completion of the reaction, 1,000 ml of distilled
water and 100 ml of saturated brine were added to the reaction
solution and extracted twice with 400 ml of ethyl acetate. The
organic phases were combined and dried over sodium sulfate
anhydrous, and sodium sulfate was filtered off. The solvent was
evaporated from the filtrate using a rotary evaporator, and the
residue was purified by silica gel column chromatography
(THF:toluene=1:9) to give 7.1 g of mixture R as a white solid.
High-performance liquid chromatography of the white solid revealed
that mole ratio of the abundance of compounds in the white solid
was as shown below. The mixture was directly used in Step 3 without
purification.
##STR00076##
[0597] Step 3: Synthesis of Mixture S
##STR00077##
[0598] A three-necked reactor equipped with a thermometer was
charged with 7.1 g of mixture R synthesized in Step 2 and 100 ml of
THF under a nitrogen stream to prepare a homogenous solution. 2.39
g (20.9 mmol) of methanesulfonyl chloride was added and the reactor
was immersed in a water bath to adjust the reaction solution
temperature to 20.degree. C. 2.16 g (21.3 mmol) of triethylamine
was added dropwise over 5 minutes while retaining the reaction
solution temperature to 20.degree. C. to 30.degree. C. After the
dropwise addition, the entire mass was further stirred at
25.degree. C. for 2 hours. To the resulting reaction solution were
added 0.19 g (1.54 mmol) of 4-(dimethylamino)pyridine and 1.07 g
(7.72 mmol) of 2,5-dihydroxybenzaldehyde, and the reactor was again
immersed in the water bath to adjust the reaction solution
temperature to 15.degree. C. 1.95 g (19.3 mmol) of triethylamine
was added dropwise over 5 minutes while retaining the reaction
solution temperature to 20.degree. C. to 30.degree. C. After the
dropwise addition, the entire mass was further stirred at
25.degree. C. for 2 hours. After completion of the reaction, 400 ml
of distilled water and 50 ml of saturated brine were added to the
reaction solution and extracted twice with 750 ml of ethyl acetate.
The organic phases were combined and dried over sodium sulfate
anhydrous, and sodium sulfate was filtered off. The solvent was
evaporated from the filtrate using a rotary evaporator, and the
residue was dissolved in 150 ml of THF. 750 ml of methanol was
added to the solution to precipitate crystals and the crystals were
filtered off. The crystals obtained were washed with methanol and
dried in vacuo to give 4.5 g of mixture S as a white solid.
High-performance liquid chromatography of the white solid revealed
that the mole ratio of the abundance of compounds in the white
solid was as shown below. The mixture was directly used in Step 4
without purification.
##STR00078##
[0599] Step 4: Synthesis of Mixture X
[0600] A three-necked reactor equipped with a thermometer was
charged with 4.5 g of mixture S synthesized in Step 3 and 50 ml of
THF under a nitrogen stream to prepare a homogenous solution to
which 0.93 ml (0.48 mmol) of concentrated hydrochloric acid was
added. To the solution was dropwise added 1.25 g (5.0 mmol) of
intermediate C synthesized in Step 1 of Synthesis Example 2 in 10
ml THF over 15 minutes. After the dropwise addition, the entire
mass was further stirred at 25.degree. C. for 1 hour. After
completion of the reaction, the reaction solution was charged into
800 ml of methanol, and the precipitated solid was filtered off.
The solid was dried using a vacuum drier to give 4.2 g of mixture X
as a pale yellow solid. High-performance liquid chromatography of
the pale yellow solid revealed that the mole ratio of the abundance
of compounds in the pale yellow solid was as shown below.
##STR00079##
[0601] <Measurement of Phase Transition Temperature>
[0602] 10 mg of each of compounds 1 to 9 and compound X was weighed
and placed in solid state between two glass substrates with rubbed
polyimide alignment films (product name: alignment treated glass
substrate (E.H.C Co.,
[0603] Ltd.)). The obtained assembly was placed on a hot plate and
the temperature was raised from 40.degree. C. to 200.degree. C.,
and then lowered to 40.degree. C. Structural changes of the
compound during temperature rise and fall were observed with a
polarized optical microscope (ECLIPSELV100POL, NIKON) and the phase
transition temperature was measured.
[0604] Measured phase transition temperatures are shown in Table 1
below.
[0605] In Table 1, "C" denotes Crystal, "N" Nematic, and "I"
Isotropic. "Crystal" means that the test compound is in solid
phase, "Nematic" means that the test compound is in nematic liquid
crystal phase, and "Isotropic" means that the test compound is in
isotropic liquid phase.
TABLE-US-00001 TABLE 1 Phase transition Compound No. temperature
Compound 1 ##STR00080## Compound 2 ##STR00081## Compound 3
##STR00082## Compound 4 ##STR00083## Compound 5 ##STR00084##
Compound 6 ##STR00085## Compound 7 ##STR00086## Compound 8
##STR00087## Compound 9 ##STR00088## Compound X ##STR00089##
Examples 3 to 11
[0606] 0.99 g of each of compounds 1 to 9 obtained in Synthesis
Examples 1 to 9, 10 mg of compound X obtained in Example 1, 30 mg
of photopolymerization initiator (Irgacure OXE02 (BASF)) and 100 mg
of 1% cyclopentanone solution of surfactant (Ftergent 208G (NEOS))
were dissolved in a mixture solvent of 0.3 g 1,3-dioxolane and 2.0
g cyclopentanone. The solutions were filtrated through 0.45 .mu.m
pore disposable filters to provide polymerizable compositions
(polymerizable liquid crystal compositions) 1 to 9.
Examples 12 to 20
[0607] 0.90 g of each of compounds 1 to 9 obtained in Synthesis
Examples 1 to 9, 100 mg of compound X obtained in Example 1, 30 mg
of photopolymerization initiator (Irgacure OXE02 (BASF)) and 100 mg
of 1% cyclopentanone solution of surfactant (Ftergent 208G (NEOS))
were dissolved in a mixture solvent of 0.3 g 1,3-dioxolane and 2.0
g cyclopentanone. The solutions were filtrated through 0.45 .mu.m
pore disposable filters to provide polymerizable compositions
(polymerizable liquid crystal compositions) 10 to 18.
Example 21
[0608] 1.0 g of mixture X obtained in Example 2, 30 mg of
photopolymerization initiator (Irgacure OXE02 (BASF)) and 100 mg of
1% cyclopentanone solution of surfactant (Ftergent 208G (NEOS))
were dissolved in a mixture solvent of 0.3 g 1,3-dioxolane and 2.0
g cyclopentanone. The solution was filtrated through a 0.45 .mu.m
pore disposable filter to provide polymerizable composition
(polymerizable liquid crystal composition) 19.
Comparative Examples 1 to 9
[0609] 1.0 g of each of compounds 1 to 9 obtained in Synthesis
Examples 1 to 9, 30 mg of photopolymerization initiator (Irgacure
OXE02 (BASF)) and 100 mg of 1% cyclopentanone solution of
surfactant (Ftergent 208G (NEOS)) were dissolved in a mixture
solvent of 0.3 g 1,3-dioxolane and 2.0 g cyclopentanone. The
solutions were filtrated through 0.45 .mu.m pore disposable filters
to provide polymerizable liquid crystal compositions 1r to 9r.
[0610] <Stability Evaluation of Liquid Crystal Phase>
(i) Formation of Liquid Crystal Layer Using Polymerizable Liquid
Crystal Composition
[0611] Using a #4 wire bar coater, each of polymerizable liquid
crystal compositions 1 to 19 and 1r to 9r was applied to a
transparent glass substrate with a rubbed polyimide alignment film
(product name: alignment treated glass substrate (E.H.C Co.,
Ltd.)). The coating films were dried for 1 minute at temperatures
shown in Table 2 and subjected to alignment treatment for 1 minute
at temperatures shown in Table 2 to form liquid crystal layers
(thickness: approx. 2.5 .mu.m).
(ii) Formation of Optically Anisotropic Product
[0612] The liquid crystal layers manufactured in section (i) above
were allowed to stand for 1 minute or 15 minutes at temperatures
shown in Table 2. Subsequently, the liquid crystal layers were
directly irradiated with UV light at a dose of 1,500 mJ/cm.sup.2 to
effect polymerization to provide optically anisotropic products
with transparent glass substrates.
(iii) Determination of Stability of Liquid Crystal Phase
[0613] The optically anisotropic products with transparent glass
substrates obtained in section (ii) above were each arranged as
illustrated in FIGS. 1A and 1B to provide laminates and the state
of the surface was visually observed. The surface free from
unevenness is good. The degree of unevenness was evaluated on the
scale of 1 to 5 with no unevenness being 5 and the presence of
unevenness being 1. The evaluation results are summarized in Table
2.
[0614] The polarizing films illustrated in FIGS. 1A and 1B are PVA
polarizing films (Sumitomo Chemical Co., Ltd.). A picture of
surface without unevenness (evaluation index: 5) and a picture of
surface with unevenness (evaluation index: 1) are given in FIGS. 2A
and 2B, respectively.
[0615] <Measurement of Optical Characteristics>
[0616] The optically anisotropic products with transparent glass
substrates obtained in section (ii) above were measured for phase
differences at wavelengths from 245.9 nm to 998.4 nm using an
ellipsometer (M2000U, J.A. Woollam). Wavelength dispersion was also
evaluated based on .alpha. and .beta. values calculated as
described below using the measured phase differences. The results
are shown in Table 3.
[0617] .alpha.=(phase difference at 449.9 nm)/(phase difference at
548.5 nm)
[0618] .beta.=(phase difference at 650.2 nm)/(phase difference at
548.5 nm)
[0619] When the optically anisotropic product shows ideal
wavelength dispersion showing a broad band property, i.e., reverse
wavelength dispersion, .alpha. value becomes less than 1 and .beta.
value becomes greater than 1. When the optically anisotropic
product shows flat wavelength dispersion .alpha. value and .beta.
values are similar. When the optically anisotropic product shows
general (typical) wavelength dispersion, .alpha. value becomes
greater than 1 and .beta. value becomes less than 1. Namely, flat
wavelength dispersion where .alpha. value and .beta. value are
similar is preferred, and reverse wavelength dispersion where
.alpha. value becomes less than 1 and .beta. value becomes greater
than 1 is particularly preferred.
[0620] The thickness of the optically anisotropic product was
measured as follows: the surface of the optically anisotropic
product with a transparent glass substrate was scratched using a
needle and the step height was measured by DEKTAK 150 surface
profilometer (ULVAC, Inc.).
TABLE-US-00002 TABLE 2 Light Evaluation Evaluation Polymerizable
Alignment Reten- expo- of of Polymerizable compound (IV) Drying
treatment tion sure unevenness unevenness Polymerizable compound
(III) Ratio temp. temp. temp. temp. after 1 min after 15 min
composition Compoud used Ratio (%) Compoud used (%) (.degree. C.)
(.degree. C.) (.degree. C.) (.degree. C.) retention retention
Example 3 1 Compound X 1 Compound 1 99 180 23 23 23 4 4 Example 4 2
Compound X 1 Compound 2 99 120 23 23 23 5 5 Example 5 3 Compound X
1 Compound 3 99 120 23 23 23 5 5 Example 6 4 Compound X 1 Compound
4 99 120 23 23 23 5 5 Example 7 5 Compound X 1 Compound 5 99 120 23
23 23 5 5 Example 8 6 Compound X 1 Compound 6 99 130 70 65 65 4 4
Example 9 7 Compound X 1 Compound 7 99 130 23 23 23 5 5 Example 10
8 Compound X 1 Compound 8 99 130 23 23 23 4 4 Example 11 9 Compound
X 1 Compound 9 99 130 23 23 23 5 5 Example 12 10 Compound X 10
Compound 1 90 170 23 23 23 5 4 Example 13 11 Compound X 10 Compound
2 90 100 23 23 23 5 5 Example 14 12 Compound X 10 Compound 3 90 100
23 23 23 5 5 Example 15 13 Compound X 10 Compound 4 90 100 23 23 23
5 5 Example 16 14 Compound X 10 Compound 5 90 100 23 23 23 5 5
Example 17 15 Compound X 10 Compound 6 90 110 70 65 65 5 4 Example
18 16 Compound X 10 Compound 7 90 120 23 23 23 5 5 Example 19 17
Compound X 10 Compound 8 90 120 23 23 23 5 4 Example 20 18 Compound
X 10 Compound 9 90 120 23 23 23 5 5 Example 21 19 Compound X 98.8
Compound 2 1.2 120 23 23 23 5 5 Comparative 1r -- -- Compound 1 100
180 23 23 23 4 2 Example 1 Comparative 2r -- -- Compound 2 100 120
23 23 23 5 4 Example 2 Comparative 3r -- -- Compound 3 100 120 23
23 23 5 4 Example 3 Comparative 4r -- -- Compound 4 100 120 23 23
23 5 4 Example 4 Comparative 5r -- -- Compound 5 100 120 23 23 23 5
4 Example 5 Comparative 6r -- -- Compound 6 100 130 70 65 65 4 2
Example 6 Comparative 7r -- -- Compound 7 100 130 23 23 23 5 4
Example 7 Comparative 8r -- -- Compound 8 100 130 23 23 23 4 2
Example 8 Comparative 9r -- -- Compound 9 100 130 23 23 23 5 4
Example 9
[0621] From Table 2, it can be seen that the polymerizable liquid
crystal compositions containing compound X can provide coating
films which can retain liquid crystal phase more stably over long
periods of time and have less coating unevenness. It can also been
from Table 2 that when compound X is added at an amount of 10%
(Examples 12 to 20), it is possible to lower drying temperature and
thus to provide liquid crystal compositions which are more easy to
handle.
TABLE-US-00003 TABLE 3 Polymerizable Polymerizable Polymerizable
compound (III) compound (IV) Film thickness Re composition Compound
used Ratio (%) Compound used Ratio (%) (.mu.m) (548.5 nm) .alpha.
.beta. Example 3 1 Compound X 1 Compound 1 99 1.568 93.49 0.791
1.043 Example 4 2 Compound X 1 Compound 2 99 1.612 118.82 0.842
1.045 Example 5 3 Compound X 1 Compound 3 99 1.489 116.19 0.880
1.031 Example 6 4 Compound X 1 Compound 4 99 1.599 123.24 0.835
1.027 Example 7 5 Compound X 1 Compound 5 99 1.673 124.28 0.847
1.035 Example 8 6 Compound X 1 Compound 6 99 1.524 122.65 0.854
1.032 Example 9 7 Compound X 1 Compound 7 99 1.495 113.73 0.836
1.020 Example 10 8 Compound X 1 Compound 8 99 1.503 129.09 0.888
1.004 Example 11 9 Compound X 1 Compound 9 99 1.624 124.59 0.845
1.057 Example 12 10 Compound X 10 Compound 1 90 1.567 93.39 0.795
1.041 Example 13 11 Compound X 10 Compound 2 90 1.606 118.36 0.837
1.035 Example 14 12 Compound X 10 Compound 3 90 1.519 118.53 0.884
1.032 Example 15 13 Compound X 10 Compound 4 90 1.612 124.28 0.832
1.029 Example 16 14 Compound X 10 Compound 5 90 1.657 123.11 0.844
1.033 Example 17 15 Compound X 10 Compound 6 90 1.487 119.71 0.850
1.030 Example 18 16 Compound X 10 Compound 7 90 1.471 111.92 0.831
1.022 Example 19 17 Compound X 10 Compound 8 90 1.526 131.04 0.887
1.022 Example 20 18 Compound X 10 Compound 9 90 1.623 124.53 0.845
1.057 Example 21 19 Compound X 98.8 Compound 2 1.2 1.601 117.99
0.841 1.044 Comparative 1r -- -- Compound 1 100 1.557 92.83 0.792
1.044 Example 1 Comparative 2r -- -- Compound 2 100 1.613 118.86
0.837 1.039 Example 2 Comparative 3r -- -- Compound 3 100 1.492
116.42 0.890 1.042 Example 3 Comparative 4r -- -- Compound 4 100
1.588 122.44 0.832 1.023 Example 4 Comparative 5r -- -- Compound 5
100 1.678 124.62 0.845 1.032 Example 5 Comparative 6r -- --
Compound 6 100 1.528 122.96 0.852 1.029 Example 6 Comparative 7r --
-- Compound 7 100 1.474 112.17 0.831 1.014 Example 7 Comparative 8r
-- -- Compound 8 100 1.494 128.32 0.893 1.009 Example 8 Comparative
9r -- -- Compound 9 100 1.632 125.24 0.847 1.057 Example 9
[0622] It can be seen from Table 3 that also in Examples 1 to 21,
.alpha. value becomes less than 1 and .beta. value becomes greater
than 1. Thus, it can be seen that even when compound X is added,
ideal wavelength dispersion showing a broad band property, i.e.,
reverse wavelength dispersion was ensured.
INDUSTRIAL APPLICABILITY
[0623] The present disclosure provides compositions which can
retain liquid crystal phase more stably over long periods of time,
have low melting points suitable for practical use, and allow for
low-cost manufacture of optical film etc. which are capable of
uniform polarized light conversion over a wide wavelength range
with a wide process margin.
[0624] The present disclosure also provides polymerizable compounds
useful for the preparation of the polymerizable liquid crystal
compositions and mixtures containing the polymerizable compounds,
and compounds useful for the preparation of the polymerizable
compounds and mixtures containing the compounds.
[0625] The present disclosure further provides optical films and
optically anisotropic products capable of uniform polarized light
conversion over a wide wavelength range, and polarizing plates,
flat panel display devices, organic electroluminescence (EL)
display devices and anti-reflection films that include the optical
film or optically anisotropic product.
* * * * *