U.S. patent application number 16/298586 was filed with the patent office on 2019-07-04 for polymerizable compound, polymerizable composition, polymer, and optical anisotropic body.
This patent application is currently assigned to ZEON CORPORATION. The applicant listed for this patent is ZEON CORPORATION. Invention is credited to Kei SAKAMOTO.
Application Number | 20190202948 16/298586 |
Document ID | / |
Family ID | 52483569 |
Filed Date | 2019-07-04 |
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United States Patent
Application |
20190202948 |
Kind Code |
A1 |
SAKAMOTO; Kei |
July 4, 2019 |
POLYMERIZABLE COMPOUND, POLYMERIZABLE COMPOSITION, POLYMER, AND
OPTICAL ANISOTROPIC BODY
Abstract
The present invention relates to: a polymerizable compound
represented by a formula (I), wherein each of Y.sup.1 to Y.sup.8
independently represents --O--, --O--C(.dbd.O)--, --C(.dbd.O)--O--
or the like; each of A.sup.2, A.sup.3, G.sup.1, and G.sup.2
independently represents a divalent linear aliphatic group having 1
to 20 carbon atoms or the like; each of Z.sup.1 and Z.sup.2
independently represents an alkenyl group having 2 to 10 carbon
atoms or the like; A.sup.x represents an organic group having 2 to
30 carbon atoms that includes at least one aromatic ring; A.sup.y
represents a hydrogen atom, an alkyl group having 1 to 20 carbon
atoms or the like; A.sup.1 represents a trivalent aromatic group or
the like; each of A.sup.4 and A.sup.5 independently represents a
divalent aromatic group having 6 to 30 carbon atoms or the like;
and Q.sup.1 represents a hydrogen atom, an alkyl group having 1 to
6 carbon atoms or the like; and others. According to the present
invention, it becomes possible to provide: a polymerizable compound
that have a practical low melting point, exhibit excellent
solubility in a general-purpose solvent, can be produced
inexpensively, can be dried at a lower temperature, has excellent
energy efficiency, and can produce an optical film that achieves
uniform conversion of polarized light over a wide wavelength band;
and others. ##STR00001##
Inventors: |
SAKAMOTO; Kei; (Tokyo,
JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ZEON CORPORATION |
Tokyo |
|
JP |
|
|
Assignee: |
ZEON CORPORATION
Tokyo
JP
|
Family ID: |
52483569 |
Appl. No.: |
16/298586 |
Filed: |
March 11, 2019 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14913233 |
Feb 19, 2016 |
10273322 |
|
|
PCT/JP2014/071428 |
Aug 14, 2014 |
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16298586 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08F 122/24 20130101;
C08F 222/102 20200201; C08F 220/30 20130101; C08F 222/1025
20200201; C07D 277/82 20130101; C08F 122/12 20130101; C08F 222/1025
20200201; C08F 222/102 20200201; C08F 222/1025 20200201; C08F
222/102 20200201; C08F 222/102 20200201; C08F 222/10 20130101; C08F
222/1006 20130101; C08F 222/1025 20200201 |
International
Class: |
C08F 122/24 20060101
C08F122/24; C07D 277/82 20060101 C07D277/82; C08F 122/12 20060101
C08F122/12; C08F 222/10 20060101 C08F222/10 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 22, 2013 |
JP |
2013-172739 |
Claims
1. A compound represented by a formula (7),
Z.sup.1--Y.sup.7-G.sup.1-Y.sup.5-A.sup.4-Y.sup.3-A.sup.2-Y.sup.11--C(.dbd-
.O)L.sup.1 (7) wherein, Y.sup.11 represents a chemical single bond,
--O--, or --NR.sup.1-- each of Y.sup.3, Y.sup.5 and Y.sup.7
independently represents a chemical single bond, --O--, --S--,
--O--C(.dbd.O)--, --C(.dbd.O)--O--, --O--C(.dbd.O)--O--,
--NR.sup.1--C(.dbd.O)--, --C(.dbd.O)--NR.sup.1--,
--O--C(.dbd.O)--NR.sup.1--, --NR.sup.1--C(.dbd.O)--O--,
--NR.sup.1--C(.dbd.O)--NR.sup.1--, --O--NR.sup.1--, or
--NR.sup.1--O--, R.sup.1 represents a hydrogen atom or an alkyl
group having 1 to 6 carbon atoms, each of A.sup.2 and G.sup.1
independently represents a substituted or unsubstituted divalent
linear aliphatic group having 1 to 20 carbon atoms that optionally
includes --O--, --S--, --O--C(.dbd.O)--, --C(.dbd.O)--O--,
--O--C(.dbd.O)--O--, --NR.sup.2--C(.dbd.O)--,
--C(.dbd.O)--NR.sup.2--, --NR.sup.2--, or --C(.dbd.O)-- provided
that a case where the linear aliphatic group includes two or more
contiguous --O-- or --S-- is excluded, R.sup.2 represents a
hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Z.sup.1
represents an alkenyl group having 2 to 10 carbon atoms that is
substituted with a halogen atom, or unsubstituted, A.sup.4
represents a substituted or unsubstituted divalent aromatic group
having 6 to 30 carbon atoms, and L.sup.1 represents a leaving
group.
2. The compound according to claim 1, wherein the compound is
represented by a formula (7'), ##STR00042## wherein, Y.sup.11
represents a chemical single bond, --O--, or --NR.sup.1-- Y.sup.12
represents a chemical single bond, --O--, or --NR.sup.1-- each of
Y.sup.5 and Y.sup.7 independently represents a chemical single
bond, --O--, --S--, --O--C(.dbd.O)--, --C(.dbd.O)--O--,
--O--C(.dbd.O)--O--, --NR.sup.1--C(.dbd.O)--,
--C(.dbd.O)--NR.sup.1--, --O--C(.dbd.O)--NR.sup.1--,
--NR.sup.1--C(.dbd.O)--O--, --NR.sup.1--C(.dbd.O)--NR.sup.1--,
--O--NR.sup.1--, or --NR.sup.1--O--, R.sup.1 represents a hydrogen
atom or an alkyl group having 1 to 6 carbon atoms, each of A.sup.2
and G.sup.1 independently represents a substituted or unsubstituted
divalent linear aliphatic group having 1 to 20 carbon atoms that
optionally includes --O--, --S--, --O--C(.dbd.O)--,
--C(.dbd.O)--O--, --O--C(.dbd.O)--O--, --NR.sup.2--C(.dbd.O)--,
--C(.dbd.O)--NR.sup.2--, --NR.sup.2--, or --C(.dbd.O)-- provided
that a case where the linear aliphatic group includes two or more
contiguous --O-- or --S-- is excluded, R.sup.2 represents a
hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Z.sup.1
represents an alkenyl group having 2 to 10 carbon atoms that is
substituted with a halogen atom, or unsubstituted, and A.sup.4
represents a substituted or unsubstituted divalent aromatic group
having 6 to 30 carbon atoms.
3. A compound represented by a formula (4), ##STR00043## wherein,
each of Y.sup.1 to Y.sup.8 independently represents a chemical
single bond, --O--, --S--, --O--C(.dbd.O)--, --C(.dbd.O)--O--,
--O--C(.dbd.O)--O--, --NR.sup.1--C(.dbd.O)--,
--C(.dbd.O)--NR.sup.1--, --O--C(.dbd.O)--NR.sup.1--,
--NR.sup.1--C(.dbd.O)--O--, --NR.sup.1--C(.dbd.O)--NR.sup.1--,
--O--NR.sup.1, or --NR.sup.1--O--, R.sup.1 represents a hydrogen
atom or an alkyl group having 1 to 6 carbon atoms, each of A.sup.2,
A.sup.3, G.sup.1 and G.sup.2 independently represents a substituted
or unsubstituted divalent linear aliphatic group having 1 to 20
carbon atoms that optionally includes --O--, --S--,
--O--C(.dbd.O)--, --C(.dbd.O)--O--, --O--C(.dbd.O)--O--,
--NR.sup.2--C(.dbd.O)--, --C(.dbd.O)--NR.sup.2--, --NR.sup.2--, or
--C(.dbd.O)-- provided that a case where the linear aliphatic group
includes two or more contiguous --O-- or --S-- is excluded, R.sup.2
represents a hydrogen atom or an alkyl group having 1 to 6 carbon
atoms, each of Z.sup.1 and Z.sup.2 represents an alkenyl group
having 2 to 10 carbon atoms that is substituted with a halogen
atom, or unsubstituted, A.sup.1 represents a substituted or
unsubstituted trivalent aromatic group, each of A.sup.4 and A.sup.5
independently represents a substituted or unsubstituted divalent
aromatic group having 6 to 30 carbon atoms, Q.sup.1 represents a
hydrogen atom, or a substituted or unsubstituted alkyl group having
1 to 6 carbon atoms.
4. A mixture including the compound according to claim 1, and a
solvent selected from the group consisting of a chlorine-based
solvent, an amide-based solvent, an ether-based solvent, a
sulfur-containing solvent, an aromatic hydrocarbon-based solvent,
an aliphatic hydrocarbon-based solvent, an alicyclic
hydrocarbon-based solvent and a mixed solvent including two or more
solvents among these solvents.
5. A method for producing a polymerizable compound represented by
formula (I), comprising: reacting a compound represented by a
formula (3) with a compound represented by a formula (4),
##STR00044## wherein, each of Y.sup.1 to Y.sup.8 independently
represents a chemical single bond, --O--, --S--, --O--C(.dbd.O)--,
--C(.dbd.O)--O--, --O--C(.dbd.O)--O--, --NR.sup.1--C(.dbd.O)--,
--C(.dbd.O)--NR.sup.1--, --O--C(.dbd.O)--NR.sup.1--,
--NR.sup.1--C(.dbd.O)--O--, --NR.sup.1--C(.dbd.O)--NR.sup.1--,
--O--NR.sup.1--, or --NR.sup.1--O--, R.sup.1 represents a hydrogen
atom or an alkyl group having 1 to 6 carbon atoms, A.sup.x
represents an organic group having 2 to 30 carbon atoms that
includes at least one aromatic ring selected from a group
consisting of an aromatic hydrocarbon ring and a heteroaromatic
ring, A.sup.y represents a hydrogen atom, a substituted or
unsubstituted alkyl group having 1 to 20 carbon atoms, a
substituted or unsubstituted alkenyl group having 2 to 20 carbon
atoms, a substituted or unsubstituted cycloalkyl group having 3 to
12 carbon atoms, a substituted or unsubstituted alkynyl group
having 2 to 20 carbon atoms, --C(.dbd.O)--R.sup.3,
--SO.sub.2--R.sup.4, --C(.dbd.S)NH--R.sup.5, or an organic group
having 2 to 30 carbon atoms that includes at least one aromatic
ring selected from the group consisting of an aromatic hydrocarbon
ring and a heteroaromatic ring, R.sup.3 represents a substituted or
unsubstituted alkyl group having 1 to 20 carbon atoms, a
substituted or unsubstituted alkenyl group having 2 to 20 carbon
atoms, or a substituted or unsubstituted cycloalkyl group having 3
to 12 carbon atoms, R.sup.4 represents an alkyl group having 1 to
20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a
phenyl group, or a 4-methylphenyl group, R.sup.5 represents a
substituted or unsubstituted alkyl group having 1 to 20 carbon
atoms, a substituted or unsubstituted alkenyl group having 2 to 20
carbon atoms, a substituted or unsubstituted cycloalkyl group
having 3 to 12 carbon atoms, or a substituted or unsubstituted
aromatic group having 5 to 20 carbon atoms, provided that the
aromatic ring included in A.sup.x and the aromatic ring optionally
included in A.sup.y are either substituted or unsubstituted, and
A.sup.x and A.sup.y are optionally bonded to each other to form a
ring, each of A.sup.2, A.sup.3, G.sup.1 and G.sup.2 independently
represents a substituted or unsubstituted divalent linear aliphatic
group having 1 to 20 carbon atoms that optionally includes --O--,
--S--, --O--C(.dbd.O)--, --C(.dbd.O)--O--, --O--C(.dbd.O)--O--,
--NR.sup.2--C(.dbd.O)--, --C(.dbd.O)--NR.sup.2--, --NR.sup.2--, or
--C(.dbd.O)-- provided that a case where the linear aliphatic group
includes two or more contiguous --O-- or --S-- is excluded, R.sup.2
represents a hydrogen atom or an alkyl group having 1 to 6 carbon
atoms, each of Z.sup.1 and Z.sup.2 represents an alkenyl group
having 2 to 10 carbon atoms that is substituted with a halogen
atom, or unsubstituted, A.sup.1 represents a substituted or
unsubstituted trivalent aromatic group, each of A.sup.4 and A.sup.5
independently represents a substituted or unsubstituted divalent
aromatic group having 6 to 30 carbon atoms, and Q.sup.1 represents
a hydrogen atom, or a substituted or unsubstituted alkyl group
having 1 to 6 carbon atoms.
6. The method for producing a polymerizable compound according to
claim 5, wherein A.sup.x represents a group having any one of
following structures, ##STR00045## wherein, X represents NR.sup.8,
an oxygen atom, a sulfur atom, --SO--, or --SO.sub.2-- (provided
that a case where oxygen atoms, sulfur atoms, --SO--, or
--SO.sub.2-- are situated at adjacent positions is excluded) and
R.sup.8 represents a hydrogen atom or an alkyl group having 1 to 6
carbon atoms, the aromatic ring included in A.sup.x may be
substituted with a halogen atom, a cyano group, an alkyl group
having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon
atoms, an alkyl halide group having 1 to 6 carbon atoms, a
substituted amino group, an alkoxy group having 1 to 6 carbon
atoms, a nitro group, an aryl group, --C(.dbd.O)--R.sup.6,
--C(.dbd.O)--OR.sup.6, --SO.sub.2R.sup.7, R.sup.6 represents an
alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2
to 20 carbon atoms, or a cycloalkyl group having 3 to 12 carbon
atoms, and R.sup.7 represents an alkyl group having 1 to 20 carbon
atoms, an alkenyl group having 2 to 20 carbon atoms, a phenyl
group, or a 4-methylphenyl group.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a Continuation of copending application
Ser. No. 14/913,233, filed on Feb. 19, 2016, which is a national
phase of PCT International Application No. PCT/JP2014/071428, filed
on Aug. 14, 2014, which claims priority under 35 U.S.C. .sctn.
119(a) to Patent Application No. 2013-172739, filed in Japan on
Aug. 22, 2013, all of which are hereby expressly incorporated by
reference into the present application.
TECHNICAL FIELD
[0002] The present invention relates to a polymerizable compound, a
polymerizable composition, and a polymer that can produce an
optical film that achieves uniform conversion of polarized light
over a wide wavelength band, and also relates to an optically
anisotropic article.
BACKGROUND ART
[0003] A flat panel display (FPD) that utilizes an optical film
(e.g., polarizer and retardation film) can achieve high-resolution
display, and has been widely used as a display device that exhibits
excellent performance.
[0004] A quarter-wave plate that converts linearly polarized light
into circularly polarized light, a half-wave plate that changes the
plane of vibration of linearly polarized light by 90.degree., and
the like are known as the retardation film. Such a retardation film
can achieve accurate conversion of specific monochromatic light so
that 1/4.lamda. or 1/2.lamda. retardation occurs.
[0005] However, a known retardation film has a problem in that
polarized light that passes through is converted into colored
polarized light. Specifically, since a material that forms the
retardation film has wavelength dispersion with respect to
retardation, and a polarization state distribution corresponding to
each wavelength occurs with respect to white light that includes
different light rays in the visible region, it is impossible to
achieve accurate 1/4.lamda. or 1/2.lamda. retardation over the
entire wavelength band.
[0006] In order to solve the above problem, various types of
wideband retardation films that can achieve uniform retardation
with respect to light over a wide wavelength band (i.e.,
retardation films having reverse wavelength dispersion) have been
studied (see Patent Literature 1 to 6, for example).
[0007] It has been desired to reduce the thickness of the flat
panel display as much as possible along with an improvement in
performance and a reduction in weight of mobile information
terminals (e.g., mobile personal computer and mobile phone).
Therefore, a reduction in thickness of the retardation film has
also been desired.
[0008] It has been considered that it is most effective to produce
a retardation film by applying a polymerizable composition that
includes a low-molecular-weight polymerizable compound to a film
substrate in order to reduce the thickness of the retardation film.
Various types of low-molecular-weight polymerizable compounds
having excellent wavelength dispersion, and polymerizable
compositions using such polymerizable compounds have been developed
(see Patent Literature 7 to 24, for example).
[0009] However, the low-molecular-weight polymerizable compounds or
the polymerizable compositions disclosed in Patent Literature 7 to
24 have a number of problems in that reverse wavelength dispersion
may be insufficient, or it may be difficult to apply the
low-molecular-weight polymerizable compounds or the polymerizable
compositions to a film due to a high melting point that is not
suitable for an industrial process, or the temperature range in
which liquid crystallinity is obtained may be very narrow, or
solubility in a solvent generally used for an industrial process
may be low. Moreover, since these low-molecular-weight
polymerizable compounds and the like are synthesized by performing
a plurality of steps using a synthesis method that utilizes an
expensive reagent, the production cost increases.
CITATION LIST
Patent Literature
[0010] Patent Literature 1: JP-A-10-68816 [0011] Patent Literature
2: JP-A-10-90521 [0012] Patent Literature 3: JP-A-11-52131 [0013]
Patent Literature 4: JP-A-2000-284126 (US20020159005A1) [0014]
Patent Literature 5: JP-A-2001-4837 [0015] Patent Literature 6:
WO2000/026705 [0016] Patent Literature 7: JP-A-2002-267838 [0017]
Patent Literature 8: JP-A-2003-160540 (US20030102458A1) [0018]
Patent Literature 9: JP-A-2005-208414 [0019] Patent Literature 10:
JP-A-2005-208415 [0020] Patent Literature 11: JP-A-2005-208416
[0021] Patent Literature 12: JP-A-2005-289980 (US20070176145A1)
[0022] Patent Literature 13: JP-A-2006-330710 (US20090072194A1)
[0023] Patent Literature 14: JP-A-2009-179563 (US20090189120A1)
[0024] Patent Literature 15: JP-A-2010-31223 [0025] Patent
Literature 16: JP-A-2011-6360 [0026] Patent Literature 17:
JP-A-2011-6361 [0027] Patent Literature 18: JP-A-2011-42606 [0028]
Patent Literature 19: JP-T-2010-537954 (US20100201920A1) [0029]
Patent Literature 20: JP-T-2010-537955 (US20100301271A1) [0030]
Patent Literature 21: WO2006/052001 (US20070298191A1) [0031] Patent
Literature 22: U.S. Pat. No. 6,139,771 [0032] Patent Literature 23:
U.S. Pat. No. 6,203,724 [0033] Patent Literature 24: U.S. Pat. No.
5,567,349
SUMMARY OF INVENTION
Technical Problem
[0034] The invention was conceived in view of the above situation.
An object of the invention is to provide a polymerizable compound,
a polymerizable composition, and a polymer that have a practical
low melting point, exhibit excellent solubility in a
general-purpose solvent, can be produced inexpensively, and can
produce an optical film that achieves uniform conversion of
polarized light over a wide wavelength band, and an optically
anisotropic article.
Solution to Problem
[0035] The inventors of the invention conducted extensive studies
in order to solve the above problem. As a result, the inventors
found that an optical film that achieves uniform conversion of
polarized light over a wide wavelength band, and exhibits
satisfactory performance can be produced inexpensively by utilizing
an optically anisotropic article that is produced using a polymer
that is obtained by polymerizing a polymerizable compound
represented by the following formula (I), or polymerizing a
polymerizable composition that includes the polymerizable compound
and an initiator. This finding has led to the completion of the
invention.
[0036] Several aspects of the invention provide the following
polymerizable compound (see (1) to (7)), polymerizable composition
(see (8) and (9)), polymer (see (10) and (11)), and optically
anisotropic article (see (12)).
(1) A polymerizable compound represented by the following formula
(I),
##STR00002##
wherein each of Y.sup.1 to Y.sup.8 independently represents a
chemical single bond, --O--, --S--, --O--C(.dbd.O)--,
--C(.dbd.O)--O--, --O--C(.dbd.O)--O--, --NR.sup.1--C(.dbd.O)--,
--C(.dbd.O)--NR.sup.1--, --O--C(.dbd.O)--NR.sup.1--,
--NR.sup.1--C(.dbd.O)--O--, --NR.sup.1--C(.dbd.O)--NR.sup.1--,
--O--NR.sup.1--, or --NR.sup.1--O--, R.sup.1 is a hydrogen atom or
an alkyl group having 1 to 6 carbon atoms, each of A.sup.2,
A.sup.3, G.sup.1, and G.sup.2 independently represents a
substituted or unsubstituted divalent linear aliphatic group having
1 to 20 carbon atoms that optionally includes --O--, --S--,
--O--C(.dbd.O)--, --C(.dbd.O)--O--, --O--C(.dbd.O)--O--,
--NR.sup.2--C(.dbd.O)--, --C(.dbd.O)--NR.sup.2--, --NR.sup.2--, or
--C(.dbd.O)--, provided that a case where the linear aliphatic
group includes two or more contiguous --O-- or --S-- is excluded,
R.sup.2 is a hydrogen atom or an alkyl group having 1 to 6 carbon
atoms, each of Z.sup.1 and Z.sup.2 independently represents an
alkenyl group having 2 to 10 carbon atoms that is substituted with
a halogen atom, or unsubstituted, A.sup.x is an organic group
having 2 to 30 carbon atoms that includes at least one aromatic
ring selected from the group consisting of an aromatic hydrocarbon
ring and an aromatic heterocyclic ring, A.sup.y is a hydrogen atom,
a substituted or unsubstituted alkyl group having 1 to 20 carbon
atoms, a substituted or unsubstituted alkenyl group having 2 to 20
carbon atoms, a substituted or unsubstituted cycloalkyl group
having 3 to 12 carbon atoms, a substituted or unsubstituted alkynyl
group having 2 to 20 carbon atoms, --C(.dbd.O)--R.sup.3,
--SO.sub.2--R.sup.4, --C(.dbd.S)NH--R.sup.5, or an organic group
having 2 to 30 carbon atoms that includes at least one aromatic
ring selected from the group consisting of an aromatic hydrocarbon
ring and an aromatic heterocyclic ring, R.sup.3 is a substituted or
unsubstituted alkyl group having 1 to 20 carbon atoms, a
substituted or unsubstituted alkenyl group having 2 to 20 carbon
atoms, or a substituted or unsubstituted cycloalkyl group having 3
to 12 carbon atoms, R.sup.4 is an alkyl group having 1 to 20 carbon
atoms, an alkenyl group having 2 to 20 carbon atoms, a phenyl
group, or a 4-methylphenyl group, R.sup.5 is a substituted or
unsubstituted alkyl group having 1 to 20 carbon atoms, a
substituted or unsubstituted alkenyl group having 2 to 20 carbon
atoms, a substituted or unsubstituted cycloalkyl group having 3 to
12 carbon atoms, or a substituted or unsubstituted aromatic group
having 5 to 20 carbon atoms, provided that the aromatic ring
included in A.sup.x and the aromatic ring optionally included in
A.sup.y are either substituted or unsubstituted, and A.sup.x and
A.sup.y are optionally bonded to each other to form a ring, A.sup.1
is a substituted or unsubstituted trivalent aromatic group, each of
A.sup.4 and A.sup.5 independently represents a substituted or
unsubstituted divalent aromatic group having 6 to 30 carbon atoms,
and Q.sup.1 is a hydrogen atom, or a substituted or unsubstituted
alkyl group having 1 to 6 carbon atoms. (2) The polymerizable
compound according to (1), wherein the total number of .pi.
electrons included in A.sup.x and A.sup.y is 4 to 24. (3) The
polymerizable compound according to (1) or (2), wherein A.sup.1 is
a substituted or unsubstituted trivalent benzene ring group, or a
substituted or unsubstituted trivalent naphthalene ring group. (4)
The polymerizable compound according to any one of (1) to (3),
wherein each of Y.sup.1 to Y.sup.8 independently represents a
chemical single bond, --O--, --O--C(.dbd.O)--, --C(.dbd.O)--O--, or
--O--C(.dbd.O)--O--. (5) The polymerizable compound according to
any one of (1) to (4), wherein each of Z.sup.1 and Z.sup.2
independently represents CH.sub.2.dbd.CH--,
CH.sub.2.dbd.C(CH.sub.3)--, or CH.sub.2.dbd.C(Cl)--. (6) The
polymerizable compound according to any one of (1) to (5), wherein
each of A.sup.2, A.sup.3, G.sup.1, and G.sup.2 independently
represents a substituted or unsubstituted divalent linear aliphatic
group having 1 to 20 carbon atoms that optionally includes --O--,
--O--C(.dbd.O)--, --C(.dbd.O)--O--, or --C(.dbd.O)--, provided that
a case where the linear aliphatic group includes two or more
contiguous --O-- is excluded. (7) The polymerizable compound
according to any one of (1) to (6), wherein each of G.sup.1 and
G.sup.2 independently represents an alkylene group having 1 to 12
carbon atoms. (8) A polymerizable composition including at least
one type of the polymerizable compound according to any one of (1)
to (7). (9) A polymerizable composition including at least one type
of the polymerizable compound according to any one of (1) to (7),
and an initiator. (10) A polymer obtained by polymerizing the
polymerizable compound according to any one of (1) to (7), or
polymerizing the polymerizable composition according to (8) or (9).
(11) The polymer according to (10), the polymer being a liquid
crystalline polymer. (12) An optically anisotropic article
including the polymer according to (11).
Advantageous Effects of Invention
[0037] The polymerizable compound, the polymerizable composition,
and the polymer according to the aspects of the invention make it
possible to inexpensively produce an optically anisotropic article
that achieves uniform conversion of polarized light over a wide
wavelength band, and exhibits satisfactory performance. Since the
drying temperature employed when forming a liquid crystal layer can
be reduced by utilizing the polymerizable composition that includes
the polymerizable compound, it is possible to improve the energy
efficiency, and reduce the cost required to produce a liquid
crystal polymer film.
[0038] Since the optically anisotropic article according to one
aspect of the invention is produced using the polymer according to
one aspect of the invention, the optically anisotropic article can
be produced inexpensively, can achieve uniform conversion of
polarized light over a wide wavelength band, and exhibits
satisfactory performance.
[0039] An antireflective film can be produced by combining the
optically anisotropic article according to one aspect of the
invention (that is formed in the shape of a film) with a polarizer.
The antireflective film may suitably be used to prevent reflection
from a touch panel, an organic electroluminescence device, and the
like.
DESCRIPTION OF EMBODIMENTS
[0040] A polymerizable compound, a polymerizable composition, a
polymer, and an optically anisotropic article according to the
exemplary embodiments of the invention are described in detail
below.
1) Polymerizable Compound
[0041] A polymerizable compound according to one embodiment of the
invention is a compound represented by the formula (I).
[0042] each of Y.sup.1 to Y.sup.8 in the formula (I) independently
represents a chemical single bond, --O--, --S--, --O--C(.dbd.O)--,
--C(.dbd.O)--O--, --O--C(.dbd.O)--O--, --NR.sup.1--C(.dbd.O)--,
--C(.dbd.O)--NR.sup.1--, --O--C(.dbd.O)--NR.sup.1--,
--NR.sup.1--C(.dbd.O)--O--, --NR.sup.1--C(.dbd.O)--NR.sup.1--,
--O--NR.sup.1--, or --NR.sup.1--O--.
[0043] R.sup.1 is a hydrogen atom or an alkyl group having 1 to 6
carbon atoms.
[0044] Examples of the alkyl group having 1 to 6 carbon atoms
represented by R.sup.1 include a methyl group, an ethyl group, an
n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl
group, a t-butyl group, an n-pentyl group, an n-hexyl group, and
the like.
[0045] R.sup.1 is preferably a hydrogen atom or an alkyl group
having 1 to 4 carbon atoms.
[0046] It is preferable that Y.sup.1 to Y.sup.8 included in the
polymerizable compound according to one embodiment of the invention
be each independently a chemical single bond, --O--,
--O--C(.dbd.O)--, --C(.dbd.O)--O--, or --O--C(.dbd.O)--O--.
[0047] Each of A.sup.2, A.sup.3, G.sup.1, and G.sup.2 independently
represents a substituted or unsubstituted divalent linear aliphatic
group having 1 to 20 carbon atoms. Note that the expression
"substituted or unsubstituted" used herein in connection with a
group or the like means that the group or the like is
unsubstituted, or substituted with a substituent (hereinafter the
same).
[0048] Examples of the divalent linear aliphatic group having 1 to
20 carbon atoms include an alkylene group having 1 to 20 carbon
atoms, such as a methylene group, an ethylene group, a trimethylene
group, a propylene group, a tetramethylene group, a pentamethylene
group, a hexamethylene group, an octamethylene group, and a
decamethylene group (--(CH.sub.2).sub.10--); an alkenylene group
having 2 to 20 carbon atoms, such as a vinylene group, a
1-methylvinylene group, a propenylene group, a 1-butenylene group,
a 2-butenylene group, a 1-pentenylene group, and a 2-pentenylene
group; and the like.
[0049] Examples of a substituent that may substitute the divalent
linear aliphatic group represented by A.sup.2, A.sup.3, G.sup.1,
and G.sup.2 include a halogen atom such as a fluorine atom, a
chlorine atom, a bromine atom, and an iodine atom; an alkoxy group
having 1 to 6 carbon atoms, such as a methoxy group, an ethoxy
group, an n-propoxy group, an isopropoxy group, an n-butoxy group,
a sec-butoxy group, a t-butoxy group, an n-pentyloxy group, and an
n-hexyloxy group; and the like. Among these, a fluorine atom, a
methoxy group, and an ethoxy group are preferable.
[0050] The linear aliphatic group optionally includes --O--, --S--,
--O--C(.dbd.O)--, --C(.dbd.O)--O--, --O--C(.dbd.O)--O--,
--NR.sup.2--C(.dbd.O)--, --C(.dbd.O)--NR.sup.2--, --NR.sup.2--, or
--C(.dbd.O)-- (provided that a case where the linear aliphatic
group includes two or more contiguous --O-- or --S-- is excluded).
R.sup.2 is a hydrogen atom or an alkyl group having 1 to 6 carbon
atoms similar to that represented by R.sup.1, and is preferably a
hydrogen atom or a methyl group.
[0051] --O--, --O--C(.dbd.O)--, --C(.dbd.O)--O--, and --C(.dbd.O)--
are preferable as the group that is optionally included in the
linear aliphatic group.
[0052] Specific examples of the linear aliphatic group that
includes the above group include
--CH.sub.2--CH.sub.2--O--CH.sub.2--CH.sub.2--,
--CH.sub.2--CH.sub.2--S--CH.sub.2--CH.sub.2--,
--CH.sub.2--CH.sub.2--O--C(.dbd.O)--CH.sub.2--CH.sub.2--,
--CH.sub.2--CH.sub.2--C(.dbd.O)--O--CH.sub.2--CH.sub.2--,
--CH.sub.2--CH.sub.2--C(.dbd.O)--O--CH.sub.2--,
--CH.sub.2--O--C(.dbd.O)--O--CH.sub.2--CH.sub.2--,
--CH.sub.2--CH.sub.2--NR.sup.2--C(.dbd.O)--CH.sub.2--CH.sub.2--,
--CH.sub.2--CH.sub.2--C(.dbd.O)--NR.sup.2--CH.sub.2--,
--CH.sub.2--NR.sup.2--CH.sub.2--CH.sub.2--,
--CH.sub.2--C(.dbd.O)--CH.sub.2--, and the like.
[0053] It is preferable that each of A.sup.2 and A.sup.3
independently represent a divalent linear aliphatic group such as
an alkylene group having 1 to 20 carbon atoms or an alkenylene
group having 2 to 20 carbon atoms, more preferably an alkylene
group having 1 to 12 carbon atoms, and particularly preferably a
tetramethylene group (--(CH.sub.2).sub.4--), a hexamethylene group
(--(CH.sub.2).sub.6--), an octamethylene group
(--(CH.sub.2).sub.8--), or a decamethylene group
(--(CH.sub.2).sub.10--), in order to more advantageously achieve
the intended effects of the invention.
[0054] It is preferable that each of G.sup.1 and G.sup.2
independently represent a substituted or unsubstituted divalent
linear aliphatic group having 1 to 12 carbon atoms (that optionally
includes --O--, --O--C(.dbd.O)--, --C(.dbd.O)--O--, or
--C(.dbd.O)--, provided that a case where the aliphatic group
includes two or more contiguous --O-- is excluded), more preferably
a divalent linear aliphatic group such as an alkylene group having
1 to 12 carbon atoms or an alkenylene group having 2 to 20 carbon
atoms, still more preferably an alkylene group having 1 to 12
carbon atoms, and particularly preferably a tetramethylene group
(--(CH.sub.2).sub.4--), a hexamethylene group
(--(CH.sub.2).sub.6--), an octamethylene group
(--(CH.sub.2).sub.8--), or a decamethylene group
(--(CH.sub.2).sub.10--).
[0055] Each of Z.sup.1 and Z.sup.2 independently represents an
alkenyl group having 2 to 10 carbon atoms that is substituted with
a halogen atom, or unsubstituted.
[0056] The number of carbon atoms of the alkenyl group is
preferably 2 to 6. Examples of the halogen atom that may substitute
the alkenyl group represented by Z.sup.1 and Z.sup.2 include a
fluorine atom, a chlorine atom, a bromine atom, and the like. Among
these, a chlorine atom is preferable.
[0057] Specific examples of the alkenyl group having 2 to 10 carbon
atoms represented by Z.sup.1 and Z.sup.2 include CH.sub.2.dbd.CH--,
CH.sub.2.dbd.C(CH.sub.3)--, CH.sub.2.dbd.CH--CH.sub.2--,
CH.sub.3--CH.dbd.CH--, CH.sub.2.dbd.CH--CH.sub.2--CH.sub.2--,
CH.sub.2.dbd.C(CH.sub.3)--CH.sub.2--CH.sub.2--,
(CH.sub.3).sub.2C.dbd.CH--CH.sub.2--,
(CH.sub.3).sub.2C.dbd.CH--CH.sub.2--CH.sub.2--,
CH.sub.2.dbd.C(Cl)--, CH.sub.2.dbd.C(CH.sub.3)--CH.sub.2--,
CH.sub.3--CH.dbd.CH--CH.sub.2--, and the like.
[0058] It is preferable that each of Z.sup.1 and Z.sup.2
independently represent CH.sub.2.dbd.CH--,
CH.sub.2.dbd.C(CH.sub.3)--, CH.sub.2.dbd.C(Cl)--,
CH.sub.2.dbd.CH--CH.sub.2--, CH.sub.2.dbd.C(CH.sub.3)--CH.sub.2--,
or CH.sub.2.dbd.C(CH.sub.3)--CH.sub.2--CH.sub.2--, more preferably
CH.sub.2.dbd.CH--, CH.sub.2.dbd.C(CH.sub.3)--, or
CH.sub.2.dbd.C(Cl)--, and still more preferably CH.sub.2.dbd.CH--,
in order to more advantageously achieve the intended effects of the
invention.
[0059] A.sup.x is an organic group having 2 to 30 carbon atoms that
includes at least one aromatic ring selected from the group
consisting of an aromatic hydrocarbon ring and an aromatic
heterocyclic ring.
[0060] The term "aromatic ring" used herein refers to a cyclic
structure that exhibits aromaticity in a broad sense according to
Huckel's rule (i.e., a cyclic conjugated structure that includes
(4n+2) .pi. electrons, and a structure that exhibits aromaticity in
which a lone electron pair of a hetero atom (e.g., sulfur, oxygen,
or nitrogen) is involved in the .pi. electron system (e.g.,
thiophene, furan, and benzothiazole)).
[0061] The organic group having 2 to 30 carbon atoms represented by
A.sup.x that includes at least one aromatic ring selected from the
group consisting of an aromatic hydrocarbon ring and an aromatic
heterocyclic ring, may include a plurality of aromatic rings, and
may include an aromatic hydrocarbon ring and an aromatic
heterocyclic ring.
[0062] Examples of the aromatic hydrocarbon ring include a benzene
ring, a naphthalene ring, an anthracene ring, and the like.
Examples of the aromatic heterocyclic ring include a monocyclic
aromatic heterocyclic ring such as a pyrrole ring, a furan ring, a
thiophene ring, a pyridine ring, a pyridazine ring, a pyrimidine
ring, a pyrazine ring, a pyrazole ring, an imidazole ring, an
oxazole ring, and a thiazole ring; a fused aromatic heterocyclic
ring such as a benzothiazole ring, a benzoxazole ring, a quinoline
ring, a phthalazine ring, a benzimidazole ring, a benzopyrazole
ring, a benzofuran ring, a benzothiophene ring, a thiazolopyridine
ring, an oxazolopyridine ring, a thiazolopyrazine ring, an
oxazolopyrazine ring, a thiazolopyridazine ring, an
oxazolopyridazine ring, a thiazolopyrimidine ring, and an
oxazolopyrimidine ring; and the like.
[0063] The aromatic ring included in A.sup.x may be substituted
with a substituent. Examples of the substituent include a halogen
atom such as a fluorine atom and a chlorine atom; a cyano group; an
alkyl group having 1 to 6 carbon atoms, such as a methyl group, an
ethyl group, and a propyl group; an alkenyl group having 2 to 6
carbon atoms, such as a vinyl group and an allyl group; an alkyl
halide group having 1 to 6 carbon atoms, such as a trifluoromethyl
group; a substituted amino group such as a dimethylamino group; an
alkoxy group having 1 to 6 carbon atoms, such as a methoxy group,
an ethoxy group, and an isopropoxy group; a nitro group; an aryl
group such as a phenyl group and a naphthyl group;
--C(.dbd.O)--R.sup.6; --C(.dbd.O)--OR.sup.6; --SO.sub.2R.sup.7; and
the like. R.sup.6 is an alkyl group having 1 to 20 carbon atoms, an
alkenyl group having 2 to 20 carbon atoms, or a cycloalkyl group
having 3 to 12 carbon atoms, and R.sup.7 is an alkyl group having 1
to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a
phenyl group, or a 4-methylphenyl group similar to that represented
by R.sup.4.
[0064] The aromatic ring included in A.sup.x may be substituted
with a plurality of identical or different substituents, and two
adjacent substituents may be bonded to each other to form a ring. A
ring formed by two adjacent substituents may be either a monocyclic
ring or a fused polycyclic ring, and may be either an unsaturated
ring or a saturated ring.
[0065] Note that the number of carbon atoms (i.e., 2 to 30) of the
organic group represented by A.sup.x refers to the total number of
carbon atoms of the organic group excluding the number of carbon
atoms of a substituent. This also applies to the number of carbon
atoms of the organic group that may be represented by A.sup.y.
[0066] Examples of the organic group having 2 to 30 carbon atoms
represented by A.sup.x (that includes at least one aromatic ring
selected from the group consisting of an aromatic hydrocarbon ring
and an aromatic heterocyclic ring) include an aromatic hydrocarbon
ring group; an aromatic heterocyclic group; an alkyl group having 3
to 30 carbon atoms that includes at least one aromatic ring
selected from the group consisting of an aromatic hydrocarbon ring
and an aromatic heterocyclic ring; an alkenyl group having 4 to 30
carbon atoms that includes at least one aromatic ring selected from
the group consisting of an aromatic hydrocarbon ring and an
aromatic heterocyclic ring; an alkynyl group having 4 to 30 carbon
atoms that includes at least one aromatic ring selected from the
group consisting of an aromatic hydrocarbon ring and an aromatic
heterocyclic ring; and the like.
[0067] Specific examples of the organic group represented by
A.sup.x are as follows. Note that the organic group represented by
A.sup.x is not limited to the following groups. "--" in the
following formulas is a bond from the ring (hereinafter the
same).
(1) Aromatic Hydrocarbon Ring Group
##STR00003##
[0068] (2) Aromatic Heterocyclic Ring Group
##STR00004##
[0069] wherein E is NR.sup.8, an oxygen atom, or a sulfur atom, and
R.sup.8 is a hydrogen atom, or an alkyl group having 1 to 6 carbon
atoms (e.g., methyl group, ethyl group, or propyl group).
##STR00005##
wherein each of X, Y, and Z independently represents NR.sup.8, an
oxygen atom, a sulfur atom, --SO--, or --SO.sub.2-- (provided that
a case where oxygen atoms, sulfur atoms, --SO--, or --SO.sub.2--
are situated at adjacent positions is excluded) and R.sup.8 is the
same as defined above.
##STR00006##
wherein X is the same as defined above. (3) Alkyl group that
includes at least one aromatic ring selected from the group
consisting of an aromatic hydrocarbon ring group and an aromatic
heterocyclic ring group
##STR00007##
(4) Alkenyl group that includes at least one aromatic ring selected
from the group consisting of an aromatic hydrocarbon ring group and
an aromatic heterocyclic ring group
##STR00008##
(5) Alkynyl group that includes at least one aromatic ring selected
from the group consisting of an aromatic hydrocarbon ring group and
an aromatic heterocyclic ring group
##STR00009##
[0070] It is preferable that A.sup.x be an aromatic hydrocarbon
group having 4 to 30 carbon atoms or an aromatic heterocyclic ring
group having 4 to 30 carbon atoms. It is more preferable that
A.sup.x be a group among the groups respectively having the
following structures.
##STR00010##
It is still more preferable that A.sup.x be a group among the
groups respectively having the following structures.
##STR00011##
[0071] The ring included in A.sup.x may be substituted with a
substituent. Examples of the substituent include a halogen atom
such as a fluorine atom and a chlorine atom; a cyano group; an
alkyl group having 1 to 6 carbon atoms, such as a methyl group, an
ethyl group, and a propyl group; an alkenyl group having 2 to 6
carbon atoms, such as a vinyl group and an allyl group; an alkyl
halide group having 1 to 6 carbon atoms, such as a trifluoromethyl
group; a substituted amino group such as a dimethylamino group; an
alkoxy group having 1 to 6 carbon atoms, such as a methoxy group,
an ethoxy group, and an isopropoxy group; a nitro group; an aryl
group such as a phenyl group and a naphthyl group;
--C(.dbd.O)--R.sup.9; --C(.dbd.O)--OR.sup.9; --SO.sub.2R.sup.9; and
the like. R.sup.9 is an alkyl group having 1 to 6 carbon atoms
(e.g., methyl group or ethyl group), or an aryl group having 6 to
14 carbon atoms (e.g., phenyl group). Among these, a halogen atom,
a cyano group, an alkyl group having 1 to 6 carbon atoms, and an
alkoxy group having 1 to 6 carbon atoms are preferable.
[0072] The ring included in A.sup.x may be substituted with a
plurality of identical or different substituents, and two adjacent
substituents may be bonded to each other to form a ring. The ring
formed by two adjacent substituents may be either a monocyclic ring
or a fused polycyclic ring.
[0073] Note that the number of carbon atoms (i.e., 2 to 30) of the
organic group represented by A.sup.x refers to the total number of
carbon atoms of the organic group excluding the number of carbon
atoms of a substituent. This also applies to the number of carbon
atoms of the organic group that may be represented by A.sup.y.
[0074] A.sup.y is a hydrogen atom, a substituted or unsubstituted
alkyl group having 1 to 20 carbon atoms, a substituted or
unsubstituted alkenyl group having 2 to 20 carbon atoms, a
substituted or unsubstituted cycloalkyl group having 3 to 12 carbon
atoms, a substituted or unsubstituted alkynyl group having 2 to 20
carbon atoms, --C(.dbd.O)--R.sup.3, --SO.sub.2--R.sup.4,
--C(.dbd.S)NH--R.sup.5, or an organic group having 2 to 30 carbon
atoms that includes at least one aromatic ring selected from the
group consisting of an aromatic hydrocarbon ring and an aromatic
heterocyclic ring. R.sup.3 is a substituted or unsubstituted alkyl
group having 1 to 20 carbon atoms, a substituted or unsubstituted
alkenyl group having 2 to 20 carbon atoms, a substituted or
unsubstituted cycloalkyl group having 3 to 12 carbon atoms, or an
aromatic hydrocarbon group having 5 to 12 carbon atoms, R.sup.4 is
an alkyl group having 1 to 20 carbon atoms, an alkenyl group having
2 to 20 carbon atoms, a phenyl group, or a 4-methylphenyl group,
and R.sup.5 is a substituted or unsubstituted alkyl group having 1
to 20 carbon atoms, a substituted or unsubstituted alkenyl group
having 2 to 20 carbon atoms, a substituted or unsubstituted
cycloalkyl group having 3 to 12 carbon atoms, or a substituted or
unsubstituted aromatic group having 5 to 20 carbon atoms.
[0075] Examples of the alkyl group having 1 to 20 carbon atoms
(that is substituted or unsubstituted) represented by A.sup.y
include a methyl group, an ethyl group, an n-propyl group, an
isopropyl group, an n-butyl group, an isobutyl group, a
1-methylpentyl group, a 1-ethylpentyl group, a sec-butyl group, a
t-butyl group, an n-pentyl group, an isopentyl group, a neopentyl
group, an n-hexyl group, an isohexyl group, an n-heptyl group, an
n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl
group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl
group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl
group, an n-octadecyl group, an n-nonadecyl group, an n-icosyl
group, and the like. The number of carbon atoms of the substituted
or unsubstituted alkyl group having 1 to 20 carbon atoms is
preferably 1 to 12, and more preferably 4 to 10.
[0076] Examples of the alkenyl group having 2 to 20 carbon atoms
(that is substituted or unsubstituted) represented by A.sup.y
include a vinyl group, a propenyl group, an isopropenyl group, a
butenyl group, an isobutenyl group, a pentenyl group, a hexenyl
group, a heptenyl group, an octenyl group, a decenyl group, an
undecenyl group, a dodecenyl group, a tridecenyl group, a
tetradecenyl group, a pentadecenyl group, a hexadecenyl group, a
heptadecenyl group, an octadecenyl group, a nonadecenyl group, an
icosenyl group, and the like.
[0077] The number of carbon atoms of the substituted or
unsubstituted alkenyl group having 2 to 20 carbon atoms is
preferably 2 to 12.
[0078] Examples of the cycloalkyl group having 3 to 12 carbon atoms
(that is substituted or unsubstituted) represented by A.sup.y
include a cyclopropyl group, a cyclobutyl group, a cyclopentyl
group, a cyclohexyl group, a cyclooctyl group, and the like.
[0079] Examples of the alkynyl group having 2 to 20 carbon atoms
(that is substituted or unsubstituted) represented by A.sup.y
include an ethynyl group, a propynyl group, a 2-propynyl group
(propargyl group), a butynyl group, a 2-butynyl group, a 3-butynyl
group, a pentynyl group, a 2-pentynyl group, a hexynyl group, a
5-hexynyl group, a 2-heptynyl group, an octan-2-yn-1-yl group, a
nonan-2-yn-1-yl group, a decan-2-yn-1-yl group, a decan-7-yn-1-yl
group, and the like.
[0080] Examples of a substituent that may substitute the
substituted or unsubstituted alkyl group having 1 to 20 carbon
atoms and the substituted or unsubstituted alkenyl group having 2
to 20 carbon atoms that may be represented by A.sup.y include a
halogen atom such as a fluorine atom and a chlorine atom; a cyano
group; a substituted amino group such as a dimethylamino group; an
alkoxy group having 1 to 20 carbon atoms, such as a methoxy group,
an ethoxy group, an isopropoxy group, and a butoxy group; an alkoxy
group having 1 to 12 carbon atoms that is substituted with an
alkoxy group having 1 to 12 carbon atoms, such as a methoxymethoxy
group and a methoxyethoxy group; a nitro group; an aryl group such
as a phenyl group and a naphthyl group; a cycloalkyl group having 3
to 8 carbon atoms, such as a cyclopropyl group, a cyclopentyl
group, and a cyclohexyl group; a cycloalkyloxy group having 3 to 8
carbon atoms, such as a cyclopentyloxy group and a cyclohexyloxy
group; a cyclic ether group having 2 to 12 carbon atoms, such as a
tetrahydrofuranyl group, a tetrahydropyranyl group, a dioxoranyl
group, and a dioxanyl group; an aryloxy group having 6 to 14 carbon
atoms, such as a phenoxy group and a naphthoxy group; a fluoroalkyl
group having 1 to 12 carbon atoms in which at least one hydrogen
atom is substituted with a fluorine atom, such as a trifluoromethyl
group, a pentafluoroethyl group, and a 2,2,2-trifluoroethyl group;
a benzofuryl group; a benzopyranyl group; a benzodioxolyl group; a
benzodioxanyl group; --C(.dbd.O)--R.sup.10; --C(.dbd.O)--OR.sup.10;
--SO.sub.2R.sup.4; --SR.sup.10; an alkoxy group having 1 to 12
carbon atoms that is substituted with --SR.sup.10; a hydroxyl
group; and the like. R.sup.10 is an alkyl group having 1 to 20
carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a
cycloalkyl group having 3 to 12 carbon atoms, or an aromatic
hydrocarbon group having 6 to 12 carbon atoms, and R.sup.4 is the
same as defined above.
[0081] Examples of a substituent that may substitute the
substituted or unsubstituted cycloalkyl group having 3 to 12 carbon
atoms that may be represented by A.sup.y include a halogen atom
such as a fluorine atom and a chlorine atom; a cyano group; a
substituted amino group such as a dimethylamino group; an alkyl
group having 1 to 6 carbon atoms, such as a methyl group, an ethyl
group, and a propyl group; an alkoxy group having 1 to 6 carbon
atoms, such as a methoxy group, an ethoxy group, and an isopropoxy
group; a nitro group; an aryl group such as a phenyl group and a
naphthyl group; a cycloalkyl group having 3 to 8 carbon atoms, such
as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl
group; --C(.dbd.O)--R.sup.3; --C(.dbd.O)--OR.sup.3;
--SO.sub.2R.sup.4; a hydroxyl group; and the like. Note that
R.sup.3 and R.sup.4 are the same as defined above.
[0082] Examples of a substituent that may substitute the
substituted or unsubstituted alkynyl group having 2 to 20 carbon
atoms that may be represented by A.sup.y include those mentioned
above in connection with the substituted or unsubstituted alkyl
group having 1 to 20 carbon atoms, and the substituted or
unsubstituted alkenyl group having 2 to 20 carbon atoms.
[0083] Examples of the organic group having 2 to 30 carbon atoms
represented by A.sup.y that includes at least one aromatic ring
selected from the group consisting of an aromatic hydrocarbon ring
and an aromatic heterocyclic ring, include those mentioned above in
connection with A.sup.x.
[0084] A.sup.y is preferably a hydrogen atom, a substituted or
unsubstituted alkyl group having 1 to 20 carbon atoms, a
substituted or unsubstituted alkenyl group having 2 to 20 carbon
atoms, a substituted or unsubstituted cycloalkyl group having 3 to
12 carbon atoms, a substituted or unsubstituted alkynyl group
having 2 to 20 carbon atoms, --C(.dbd.O)--R.sup.3,
--SO.sub.2--R.sup.4, or an organic group having 2 to 30 carbon
atoms that includes at least one aromatic ring selected from the
group consisting of an aromatic hydrocarbon ring and an aromatic
heterocyclic ring, and more preferably a hydrogen atom, a
substituted or unsubstituted alkyl group having 1 to 20 carbon
atoms, a substituted or unsubstituted alkenyl group having 2 to 20
carbon atoms, a substituted or unsubstituted cycloalkyl group
having 3 to 12 carbon atoms, a substituted or unsubstituted alkynyl
group having 2 to 20 carbon atoms, a substituted or unsubstituted
aromatic hydrocarbon group having 6 to 12 carbon atoms, a
substituted or unsubstituted aromatic heterocyclic ring group
having 3 to 9 carbon atoms, --C(.dbd.O)--R.sup.3, or
--SO.sub.2--R.sup.4. Note that R.sup.3 and R.sup.4 are the same as
defined above.
[0085] Examples of a preferable substituent that may substitute the
substituted or unsubstituted alkyl group having 1 to 20 carbon
atoms, the substituted or unsubstituted alkenyl group having 2 to
20 carbon atoms, and the substituted or unsubstituted alkynyl group
having 2 to 20 carbon atoms, include a halogen atom, a cyano group,
an alkoxy group having 1 to 20 carbon atoms, an alkoxy group having
1 to 12 carbon atoms that is substituted with an alkoxy group
having 1 to 12 carbon atoms, a phenyl group, a cyclohexyl group, a
cyclic ether group having 2 to 12 carbon atoms, an aryloxy group
having 6 to 14 carbon atoms, a hydroxyl group, a benzodioxanyl
group, and --SR.sup.10. Note that R.sup.10 is the same as defined
above.
[0086] Examples of a preferable substituent that may substitute the
substituted or unsubstituted cycloalkyl group having 3 to 12 carbon
atoms, the substituted or unsubstituted aromatic hydrocarbon group
having 6 to 12 carbon atoms, and the substituted or unsubstituted
aromatic heterocyclic ring group having 3 to 9 carbon atoms,
include a fluorine atom, an alkyl group having 1 to 6 carbon atoms,
an alkoxy group having 1 to 6 carbon atoms, and a cyano group.
[0087] A.sup.x and A.sup.y may be bonded to each other to form a
ring. Examples of the ring formed by A.sup.x and A.sup.y include a
substituted or unsubstituted unsaturated heterocyclic ring having 4
to 30 carbon atoms, and a substituted or unsubstituted unsaturated
carbocyclic ring having 6 to 30 carbon atoms.
[0088] The unsaturated heterocyclic ring having 4 to 30 carbon
atoms and the unsaturated carbocyclic ring having 6 to 30 carbon
atoms are not particularly limited, and may or may not have
aromaticity. Examples of the unsaturated heterocyclic ring having 4
to 30 carbon atoms and the unsaturated carbocyclic ring having 6 to
30 carbon atoms are shown below.
##STR00012##
[0089] Note that the rings shown below correspond to the above part
in the formula (I).
##STR00013## ##STR00014## ##STR00015##
wherein X, Y, and Z are the same as defined above.
[0090] These rings may be substituted with a substituent. Examples
of the substituent include those mentioned above in connection with
a substituent that may substitute the aromatic ring included in
A.sup.x.
[0091] The total number of t electrons included in A.sup.x and
A.sup.y is preferably 4 to 24, and more preferably 6 to 18, in
order to more advantageously achieve the intended effects of the
invention.
[0092] Examples of a preferable combination of A.sup.x and A.sup.y
include a combination in which A.sup.x is an aromatic hydrocarbon
group having 4 to 30 carbon atoms or
an aromatic heterocyclic ring group having 4 to 30 carbon atoms,
and A.sup.y is a hydrogen atom, a cycloalkyl group having 3 to 8
carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon
atoms (that is optionally substituted with a halogen atom, a cyano
group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group
having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 8
carbon atoms), an aromatic heterocyclic ring group having 3 to 9
carbon atoms (that is optionally substituted with a halogen atom,
an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1
to 6 carbon atoms, or a cyano group), a substituted or
unsubstituted alkyl group having 1 to 20 carbon atoms, a
substituted or unsubstituted alkenyl group having 1 to 20 carbon
atoms, or a substituted or unsubstituted alkynyl group having 2 to
20 carbon atoms, the alkyl group, the alkenyl group, and the
alkynyl group being optionally substituted with a halogen atom, a
cyano group, an alkoxy group having 1 to 20 carbon atoms, an alkoxy
group having 1 to 12 carbon atoms that is substituted with an
alkoxy group having 1 to 12 carbon atoms, a phenyl group, a
cyclohexyl group, a cyclic ether group having 2 to 12 carbon atoms,
an aryloxy group having 6 to 14 carbon atoms, a hydroxyl group, a
benzodioxanyl group, or --SR.sup.10, and a combination in which
A.sup.x and A.sup.y form an unsaturated heterocyclic ring or an
unsaturated carbocyclic ring. Note that R.sup.10 is the same as
defined above.
[0093] Examples of a more preferable combination of A.sup.x and
A.sup.y include a combination in which A.sup.x is a group among the
groups respectively having the following structures, and A.sup.y is
a hydrogen atom, a cycloalkyl group having 3 to 8 carbon atoms, an
aromatic hydrocarbon group having 6 to 12 carbon atoms (that is
optionally substituted with a halogen atom, a cyano group, an alkyl
group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6
carbon atoms, or a cycloalkyl group having 3 to 8 carbon atoms), an
aromatic heterocyclic ring group having 3 to 9 carbon atoms (that
is optionally substituted with a halogen atom, an alkyl group
having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon
atoms, or a cyano group), a substituted or unsubstituted alkyl
group having 1 to 20 carbon atoms, a substituted or unsubstituted
alkenyl group having 1 to 20 carbon atoms, or a substituted or
unsubstituted alkynyl group having 2 to 20 carbon atoms, the alkyl
group, the alkenyl group, and the alkynyl group being optionally
substituted with a halogen atom, a cyano group, an alkoxy group
having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon
atoms that is substituted with an alkoxy group having 1 to 12
carbon atoms, a phenyl group, a cyclohexyl group, a cyclic ether
group having 2 to 12 carbon atoms, an aryloxy group having 6 to 14
carbon atoms, a hydroxyl group, a benzodioxanyl group, or
--SR.sup.10. Note that R.sup.10 is the same as defined above.
##STR00016##
wherein X and Y are the same as defined above.
[0094] Examples of a particularly preferable combination of A.sup.x
and A.sup.y include a combination in which A.sup.x is a group among
the groups respectively having the following structures, and
A.sup.y is a hydrogen atom, a cycloalkyl group having 3 to 8 carbon
atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms
(that is optionally substituted with a halogen atom, a cyano group,
an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1
to 6 carbon atoms, or a cycloalkyl group having 3 to 8 carbon
atoms), an aromatic heterocyclic ring group having 3 to 9 carbon
atoms (that is optionally substituted with a halogen atom, an alkyl
group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6
carbon atoms, or a cyano group), a substituted or unsubstituted
alkyl group having 1 to 20 carbon atoms, a substituted or
unsubstituted alkenyl group having 1 to 20 carbon atoms, or a
substituted or unsubstituted alkynyl group having 2 to 20 carbon
atoms, the alkyl group, the alkenyl group, and the alkynyl group
being optionally substituted with a halogen atom, a cyano group, an
alkoxy group having 1 to 20 carbon atoms, an alkoxy group having 1
to 12 carbon atoms that is substituted with an alkoxy group having
1 to 12 carbon atoms, a phenyl group, a cyclohexyl group, a cyclic
ether group having 2 to 12 carbon atoms, an aryloxy group having 6
to 14 carbon atoms, a hydroxyl group, a benzodioxanyl group, or
--SR.sup.10. Note that X is the same as defined above, and R.sup.10
is the same as defined above.
##STR00017##
[0095] A.sup.1 is a substituted or unsubstituted trivalent aromatic
group. The trivalent aromatic group may be a trivalent carbocyclic
aromatic group, or may be a trivalent heterocyclic aromatic group.
It is preferable that the trivalent aromatic group be a trivalent
carbocyclic aromatic group, more preferably a trivalent benzene
ring group or a trivalent naphthalene ring group, and still more
preferably a trivalent benzene ring group or a trivalent
naphthalene ring group represented by the following formulas, in
order to more advantageously achieve the intended effects of the
invention.
[0096] Note that the substituents Y.sup.1 and Y.sup.2 are also
included in the following formulas so that the bonding state can be
easily understood (Y.sup.1 and Y.sup.2 are the same as defined
above; hereinafter the same).
##STR00018##
[0097] A.sup.1 is more preferably a group among the groups
respectively represented by the following formulas (A11) to (A25),
still more preferably a group among the groups respectively
represented by the formulas (A11), (A13), (A15), (A19), and (A23),
and particularly preferably the group represented by the formula
(A11) or the group represented by the formula (A23).
##STR00019## ##STR00020##
[0098] Examples of a substituent that may substitute the trivalent
aromatic group represented by A.sup.1 include those mentioned above
in connection with a substituent that may substitute the aromatic
ring included in A.sup.x. It is preferable that A.sup.1 be
unsubstituted.
[0099] Each of A.sup.4 and A.sup.5 independently represents a
substituted or unsubstituted divalent aromatic group having 6 to 30
carbon atoms.
[0100] The aromatic group represented by A.sup.4 and A.sup.5 may be
a monocyclic aromatic group, or may be a polycyclic aromatic
group.
[0101] Specific examples of a preferable aromatic group represented
by A.sup.4 and A.sup.5 include the groups respectively represented
by the following formulas.
##STR00021##
[0102] The divalent aromatic group represented by A.sup.4 and
A.sup.5 may be substituted with a substituent at an arbitrary
position. Examples of the substituent include a halogen atom, a
cyano group, a hydroxyl group, an alkyl group having 1 to 6 carbon
atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group,
--C(.dbd.O)--OR (wherein R is an alkyl group having 1 to 6 carbon
atoms), and the like. Among these, a halogen atom, an alkyl group
having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6
carbon atoms are preferable. A fluorine atom is preferable as the
halogen atom. A methyl group, an ethyl group, and a propyl group
are preferable as the alkyl group having 1 to 6 carbon atoms. A
methoxy group and an ethoxy group are preferable as the alkoxy
group having 1 to 6 carbon atoms.
[0103] It is preferable that each of A.sup.4 and A.sup.5
independently represent a group among the groups respectively
represented by the following formulas (A41), (A42), and (A43) that
are optionally substituted with a substituent, and particularly
preferably the group represented by the formula (A41) that is
optionally substituted with a substituent, in order to more
advantageously achieve the intended effects of the invention.
##STR00022##
[0104] Q.sup.1 is a hydrogen atom, or a substituted or
unsubstituted alkyl group having 1 to 6 carbon atoms.
[0105] Examples of the substituted or unsubstituted alkyl group
having 1 to 6 carbon atoms include those mentioned above in
connection with A.sup.x.
[0106] Q.sup.1 is preferably a hydrogen atom or an alkyl group
having 1 to 6 carbon atoms, and more preferably a hydrogen atom or
a methyl group.
[0107] The polymerizable compound according to one embodiment of
the invention may be produced by effecting the following reaction,
for example.
##STR00023##
wherein Y.sup.1 to Y.sup.8, G.sup.1, G.sup.2, Z.sup.1, Z.sup.2,
A.sup.x, A.sup.y, A.sup.1 to A.sup.5, and Q.sup.1 are the same as
defined above.
[0108] Specifically, the polymerizable compound represented by the
formula (I) can be produced with high selectivity in high yield by
reacting the hydrazine compound represented by the formula (3)
(hydrazine compound (3)) with the carbonyl compound represented by
the formula (4) (carbonyl compound (4)) in a molar ratio (hydrazine
compound (3):carbonyl compound (4)) of 1:2 to 2:1 (preferably 1:1.5
to 1.5:1).
[0109] The above reaction may be effected in the presence 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 the acid catalyst may reduce the reaction time, and
improve the yield. The acid catalyst is normally added in an amount
of 0.001 to 1 mol based on 1 mol of the carbonyl compound (4). The
acid catalyst may be added directly, or a solution prepared by
dissolving the acid catalyst in an appropriate solvent may be
added.
[0110] A solvent used for the above reaction is not particularly
limited as long as the solvent is inert to the reaction. Examples
of the solvent include an alcohol-based solvent such as methyl
alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol,
n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, and t-butyl
alcohol; an ether-based solvent such as diethyl ether,
tetrahydrofuran, 1,2-dimethoxyethane, 1,4-dioxane, and cyclopentyl
methyl ether; an ester-based solvent such as ethyl acetate, propyl
acetate, and methyl propionate; an aromatic hydrocarbon-based
solvent such as benzene, toluene, and xylene; an aliphatic
hydrocarbon-based solvent such as n-pentane, n-hexane, and
n-heptane; an amide-based solvent such as N,N-dimethylformamide,
N-methylpyrrolidone, and hexamethylphosphoric acid triamide; a
sulfur-containing solvent such as dimethyl sulfoxide and sulfolane;
a mixed solvent including two or more solvents among these
solvents; and the like.
[0111] Among these, an alcohol-based solvent, an ether-based
solvent, and a mixed solvent including an alcohol-based solvent and
an ether-based solvent are preferable.
[0112] The solvent may be used in an appropriate amount taking
account of the type of each compound, the reaction scale, and the
like. The solvent is normally used in an amount of 1 to 100 g per
gram of the hydrazine compound (3).
[0113] The reaction proceeds smoothly when the reaction temperature
is within the range from -10.degree. C. to the boiling point of the
solvent. The reaction time is selected taking account of the
reaction scale, but is normally several minutes to several
hours.
[0114] The hydrazine compound (3) may be produced as described
below.
##STR00024##
wherein A.sup.x and A.sup.y are the same as defined above, and X is
a leaving group (e.g., halogen atom, methanesulfonyloxy group, or
p-toluenesulfonyloxy group).
[0115] Specifically, the compound represented by the formula (2a)
is reacted with the hydrazine (1) in an appropriate solvent in a
molar ratio (compound (2a):hydrazine (1)) of 1:1 to 1:20
(preferably 1:2 to 1:10) to obtain the corresponding hydrazine
compound (3a), and the hydrazine compound (3a) is reacted with the
compound represented by the formula (2b) to obtain the hydrazine
compound (3).
[0116] Hydrazine monohydrate is normally used as the hydrazine (1).
A commercially available product may be used directly as the
hydrazine (1).
[0117] A solvent used for the above reaction is not particularly
limited as long as the solvent is inert to the reaction. Examples
of the solvent include an alcohol-based solvent such as methyl
alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol,
n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, and t-butyl
alcohol; an ether-based solvent such as diethyl ether,
tetrahydrofuran, 1,2-dimethoxyethane, 1,4-dioxane, and cyclopentyl
methyl ether; an aromatic hydrocarbon-based solvent such as
benzene, toluene, and xylene; an aliphatic hydrocarbon-based
solvent such as n-pentane, n-hexane, and n-heptane; an amide-based
solvent such as N,N-dimethylformamide, N-methylpyrrolidone, and
hexamethylphosphoric acid triamide; a sulfur-containing solvent
such as dimethyl sulfoxide and sulfolane; a mixed solvent including
two or more solvents among these solvents; and the like.
[0118] Among these, an alcohol-based solvent, an ether-based
solvent, and a mixed solvent including an alcohol-based solvent and
an ether-based solvent are preferable.
[0119] The solvent may be used in an appropriate amount taking
account of the type of each compound, the reaction scale, and the
like. The solvent is normally used in an amount of 1 to 100 g per
gram of hydrazine.
[0120] The reaction proceeds smoothly when the reaction temperature
is within the range from -10.degree. C. to the boiling point of the
solvent. The reaction time is selected taking account of the
reaction scale, but is normally several minutes to several
hours.
[0121] The hydrazine compound (3) may also be produced by reducing
the diazonium salt (5) (see below) using a known method.
##STR00025##
wherein A.sup.x and A.sup.y are the same as defined above, and
X.sup.- is an anion that is a counter ion for diazonium. Examples
of the anion represented by X.sup.- include an inorganic anion such
as a hexafluorophosphoric acid ion, a fluoroboric acid ion, a
chloride ion, and a sulfuric acid ion; an organic anion such as a
polyfluoroalkylcarboxylic acid ion, a polyfluoroalkylsulfonic acid
ion, a tetraphenylboric acid ion, an aromatic carboxylic acid ion,
and an aromatic sulfonic acid ion; and the like.
[0122] Examples of a reducing agent used for the above reaction
include a metal salt reducing agent.
[0123] The term "metal salt reducing agent" normally refers to a
compound that includes a metal having a small valence, or a
compound that includes a metal ion and a hydride source (see "Yuki
Gosei Jikkenhou Handbook (Handbook of Organic Synthesis
Experiments)", 1990, edited by The Society of Synthetic Organic
Chemistry, Japan, published by Maruzen Co., Ltd., p. 810).
[0124] Examples of the metal salt reducing agent include
NaAlH.sub.4, NaAlH.sub.p(Or).sub.q (wherein each of p and q
independently represents an integer from 1 to 3, provided that
p+q=4, and r is an alkyl group having 1 to 6 carbon atoms),
LiAlH.sub.4, iBu.sub.2AlH, LiBH.sub.4, NaBH.sub.4, SnCl.sub.2,
CrCl.sub.2, TiCl.sub.3, and the like.
[0125] The reduction reaction may be effected under known reaction
conditions. For example, the reduction reaction may be effected
under the reaction conditions described in JP-A-2005-336103,
"Shin-Jikken Kagaku Koza (New Experimental Chemistry Course)",
1978, Vol. 14, published by Maruzen Co., Ltd., "Jikken Kagaku Koza
(Experimental Chemistry Course)", 1992, Vol. 20, published by
Maruzen Co., Ltd., or the like.
[0126] The diazonium salt (5) may be produced from aniline or the
like using a known method.
[0127] The carbonyl compound (4) may be produced by appropriately
bonding and modifying a plurality of known compounds having the
desired structure by arbitrarily combining an ether linkage
(--O--)-forming reaction, an ester linkage (--C(.dbd.O)--O-- or
--O--C(.dbd.O)--)-forming reaction, a carbonate linkage
(--O--C(.dbd.O)--O--)-forming reaction, and an amide linkage
(--C(.dbd.O)--NH-- or --NH--C(.dbd.O)--)-forming reaction.
[0128] An ether linkage may be formed as described below.
(i) A compound represented by D1-hal (wherein hal is a halogen
atom; hereinafter the same) and a compound represented by D2-OMet
(wherein Met is an alkali metal (mainly sodium); hereinafter the
same) are mixed and condensed (Williamson synthesis). Note that D1
and D2 are an arbitrary organic group (hereinafter the same). (ii)
A compound represented by D1-hal and a compound represented by
D2-OH are mixed and condensed in the presence of a base (e.g.,
sodium hydroxide or potassium hydroxide). (iii) A compound
represented by D1-J (wherein J is an epoxy group) and a compound
represented by D2-OH are mixed and condensed in the presence of a
base (e.g., sodium hydroxide or potassium hydroxide). (iv) A
compound represented by D1-OFN (wherein OFN is a group that
includes an unsaturated bond) and a compound represented by D2-OMet
are mixed and subjected to an addition reaction in the presence of
a base (e.g., sodium hydroxide or potassium hydroxide). (v) A
compound represented by D1-hal and a compound represented by
D2-OMet are mixed and condensed in the presence of copper or
cuprous chloride (Ullmann condensation).
[0129] An ester linkage and an amide linkage may be formed as
described below.
(vi) A compound represented by D1-COOH and a compound represented
by D2-OH or D2-NH.sub.2 are subjected to dehydration and
condensation in the presence of a dehydration-condensation agent
(e.g., N,N-dicyclohexylcarbodiimide). (vii) A compound represented
by D1-COOH is reacted with a halogenating agent to obtain a
compound represented by D1-CO-hal, and the compound represented by
D1-CO-hal is reacted with a compound represented by D2-OH or
D2-NH.sub.2 in the presence of a base. (viii) A compound
represented by D1-COOH is reacted with an acid anhydride to obtain
a mixed acid anhydride, and the mixed acid anhydride is reacted
with a compound represented by D2-OH or D2-NH.sub.2. (ix) A
compound represented by D1-COOH and a compound represented by D2-OH
or D2-NH.sub.2 are subjected to dehydration and condensation in the
presence of an acid catalyst or a base catalyst.
[0130] More specifically, the carbonyl compound (4) may be produced
using the following method (see the following reaction
formula).
##STR00026##
wherein Y.sup.1 to Y.sup.8, G.sup.1, G.sup.2, Z.sup.1, Z.sup.2,
A.sup.1 to A.sup.5, and Q.sup.1 are the same as defined above,
L.sup.1 and L.sup.2 are a leaving group (e.g., hydroxyl group,
halogen atom, methanesulfonyloxy group, or p-toluenesulfonyloxy
group), --Y.sup.1a is a group that reacts with -L.sup.1 to form
--Y.sup.1--, and --Y.sup.2a is a group that reacts with -L.sup.2 to
form --Y.sup.2--.
[0131] Specifically, the carbonyl compound (4) according to one
embodiment of the invention may be produced by sequentially
reacting the compound represented by the formula (7a) and the
compound represented by the formula (7b) with the compound
represented by the formula (6d) using an ether linkage
(--O--)-forming reaction, an ester linkage (--C(.dbd.O)--O-- or
--O--C(.dbd.O)--)-forming reaction, or a carbonate linkage
(--O--C(.dbd.O)--O--)-forming reaction known in the art.
[0132] The carbonyl compound (4') wherein Y.sup.1 is a group
represented by Y.sup.11--C(.dbd.O)--O--, and the group represented
by
Z.sup.2--Y.sup.8-G.sup.2-Y.sup.6-A.sup.5-Y.sup.4-A.sup.3-Y.sup.2--
is identical with the group represented by
Z.sup.1--Y.sup.7-G.sup.1-Y.sup.5-A.sup.4-Y.sup.3-A.sup.2-Y.sup.1--
(hereinafter referred to as "compound (4')") may be produced as
shown below.
##STR00027##
wherein Y.sup.3, Y.sup.5, Y.sup.7, G.sup.1, Z.sup.1, A.sup.1,
A.sup.2, A.sup.4, Q.sup.1, and L.sup.1 are the same as defined
above, Y.sup.11 is a group whereby Y.sup.1 is represented by
Y.sup.11--C(.dbd.O)--O--, and Y.sup.1 is the same as defined
above.
[0133] Specifically, the dihydroxy compound represented by the
formula (6) (compound (6)) is reacted with the compound represented
by the formula (7) (compound (7)) in a molar ratio (compound
(6):compound (7)) of 1:2 to 1:4 (preferably 1:2 to 1:3) to produce
the target compound (4') with high selectivity in high yield.
[0134] When the compound (7) is a compound (carboxylic acid)
represented by the formula (7) wherein L.sup.1 is a hydroxyl group,
the target product may be obtained by effecting the reaction in the
presence of a dehydration-condensation agent (e.g.,
1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride or
dicyclohexylcarbodiimide).
[0135] The dehydration-condensation agent is normally used in an
amount of 1 to 3 mol based on 1 mol of the compound (7).
[0136] When the compound (7) is a compound (carboxylic acid)
represented by the formula (7) wherein L.sup.1 is a hydroxyl group,
the target product may also be obtained by effecting the reaction
in the presence of a sulfonyl halide (e.g., methanesulfonyl
chloride or p-toluenesulfonyl chloride) and a base (e.g.,
triethylamine, diisopropylethylamine, pyridine, or
4-(dimethylamino)pyridine).
[0137] The sulfonyl halide is normally used in an amount of 1 to 3
mol based on 1 mol of the compound (7).
[0138] The base is normally used in an amount of 1 to 3 mol based
on 1 mol of the compound (7).
[0139] In this case, a compound (mixed acid anhydride) represented
by the formula (7) wherein L.sup.1 is a sulfonyloxy group may be
isolated, and subjected to the subsequent reaction.
[0140] When the compound (7) is a compound (acid halide)
represented by the formula (7) wherein L.sup.1 is a halogen atom,
the target product may be obtained by effecting the reaction in the
presence of a base.
[0141] Examples of the base include an organic base such as
triethylamine and pyridine; and an inorganic base such as sodium
hydroxide, sodium carbonate, and sodium hydrogen carbonate.
[0142] The base is normally used in an amount of 1 to 3 mol based
on 1 mol of the compound (7).
[0143] Examples of a solvent used for the above reaction include a
chlorine-based solvent such as chloroform and methylene chloride;
an amide-based solvent such as N-methylpyrrolidone,
N,N-dimethylformamide, N,N-dimethylacetamide, and
hexamethylphosphoric acid triamide; an ether-based solvent such as
1,4-dioxane, cyclopentyl methyl ether, tetrahydrofuran,
tetrahydropyran, and 1,3-dioxolane; a sulfur-containing solvent
such as dimethyl sulfoxide and sulfolane; an aromatic
hydrocarbon-based solvent such as benzene, toluene, and xylene; an
aliphatic hydrocarbon-based solvent such as n-pentane, n-hexane,
and n-octane; an alicyclic hydrocarbon-based solvent such as
cyclopentane and cyclohexane; a mixed solvent including two or more
solvents among these solvents; and the like.
[0144] The solvent may be used in an appropriate amount taking
account of the type of each compound, the reaction scale, and the
like. The solvent is normally used in an amount of 1 to 50 g per
gram of the hydroxy compound (6).
[0145] Many of the compounds (6) are known compounds, and may be
produced using a known method.
[0146] For example, the compound (6) may be produced using the
following method (see the following reaction formula) (see
WO2009/042544 and The Journal of Organic Chemistry, 2011, 76,
8082-8087). A commercially available product may be used as the
compound (6) either directly or after purification.
##STR00028##
wherein A.sup.1 and Q.sup.1 are the same as defined above, A.sup.1a
is a divalent aromatic group that forms A.sup.1 through formylation
or acylation, and R' is a protecting group for a hydroxyl group,
such as an alkyl group having 1 to 6 carbon atoms (e.g., methyl
group or ethyl group), or an alkoxyalkyl group having 2 to 6 carbon
atoms (e.g., methoxymethyl group).
[0147] Specifically, the target compound (6) may be produced by
alkylating the hydroxyl groups of the dihydroxy compound
represented by the formula (6a) (e.g., 1,4-dihydroxybenzene or
1,4-dihydroxynaphthalene) to obtain the compound represented by the
formula (6b), effecting formylation or acylation at the ortho
position with respect to the OR' group using a known method to
obtain the compound represented by the formula (6c), and
deprotecting (dealkylating) the compound represented by the formula
(6c).
[0148] A commercially available product may be used as the compound
(6) either directly or after purification.
[0149] Most of the compounds (7) are known compounds. The carbonyl
compound (7) may be produced by appropriately bonding and modifying
a plurality of known compounds having a desired structure by
arbitrarily combining an ether linkage (--O--)-forming reaction, an
ester linkage (--C(.dbd.O)--O-- or --O--C(.dbd.O)--)-forming
reaction, a carbonate linkage (--O--C(.dbd.O)--O--)-forming
reaction, and an amide linkage (--C(.dbd.O)--NH-- or
--NH--C(.dbd.O)--)-forming reaction.
[0150] For example, when the compound (7) is a compound represented
by the following formula (7') (compound (7')), the compound (7) may
be produced as shown below using a dicarboxylic acid represented by
the formula (9') (compound (9')).
##STR00029##
wherein Y.sup.5, Y.sup.7, G.sup.1, Z.sup.1, A.sup.2, A.sup.4, and
Y.sup.11 are the same as defined above, Y.sup.12 is a group whereby
Y.sup.3 is represented by --O--C(.dbd.O)--Y.sup.12, and R is an
alkyl group such as a methyl group or an ethyl group, or a
substituted or unsubstituted aryl group such as a phenyl group or a
p-methylphenyl group.
[0151] Specifically, the sulfonyl chloride represented by the
formula (10) is reacted with the compound (9') in the presence of a
base (e.g., triethylamine or 4-(dimethylamino)pyridine).
[0152] The compound (8) and a base (e.g., triethylamine or
4-(dimethylamino)pyridine) are added to the reaction mixture to
effect a reaction.
[0153] Sulfonyl chloride is normally used in an amount of 0.5 to
0.7 equivalents based on 1 equivalent of the compound (9').
[0154] The compound (8) is normally used in an amount of 0.5 to 0.6
equivalents based on 1 equivalent of the compound (9').
[0155] The base is normally used in an amount of 0.5 to 0.7
equivalents based on 1 equivalent of the compound (9').
[0156] The reaction temperature is 20 to 30.degree. C. The reaction
time is selected taking account of the reaction scale and the like,
but is normally several minutes to several hours.
[0157] Examples of a solvent used for the above reaction include
those mentioned above in connection with the solvent that may be
used when producing the compound (4'). It is preferable to use an
ether as the solvent.
[0158] The solvent may be used in an appropriate amount taking
account of the type of each compound, the reaction scale, and the
like. The solvent is normally used in an amount of 1 to 50 g per
gram of the compound (9').
[0159] The target product is isolated by performing a
post-treatment operation normally employed in synthetic organic
chemistry after completion of the reaction, optionally followed by
a known purification/separation means such as column
chromatography, recrystallization, or distillation.
[0160] The structure of the target product may be identified by
measurement/elemental analysis (e.g., NMR spectrometry, IR
spectrometry, or mass spectrometry), and the like.
[0161] The polymerizable compound according to one embodiment of
the invention is useful as a raw material for producing the polymer
and the optically anisotropic article according to the embodiments
of the invention (described below), and is particularly useful as a
raw material for producing a polymer having reverse wavelength
dispersion. Specifically, when producing a copolymer using the
polymerizable compound according to one embodiment of the invention
and a monomer that is copolymerizable with the polymerizable
compound according to one embodiment of the invention, it is
possible to produce a copolymer having reverse wavelength
dispersion by copolymerizing the polymerizable compound according
to one embodiment of the invention with a monomer that produces a
polymer that has reverse wavelength dispersion when polymerized. In
this case, since the drying temperature employed when forming a
liquid crystal layer can be reduced while maintaining the reverse
wavelength dispersion, it is possible to improve the energy
efficiency, and reduce the cost required to produce a liquid
crystal polymer film.
2) Polymerizable Composition
[0162] A polymerizable composition according to one embodiment of
the invention includes the polymerizable compound according to one
embodiment of the invention, and an initiator. The initiator is
used to more efficiently polymerize the polymerizable compound
according to one embodiment of the invention.
[0163] The initiator may be appropriately selected taking account
of the type of the polymerizable group included in the
polymerizable compound. For example, a radical initiator may be
used when the polymerizable group is a radically polymerizable
group, an anionic initiator may be used when the polymerizable
group is an anionically polymerizable group, and a cationic
initiator may be used when the polymerizable group is a
cationically polymerizable group.
[0164] Examples of the radical initiator include a thermal radical
generator (compound) that generates active species that initiate
the polymerization of the polymerizable compound upon heating, and
a photo-radical generator (compound) that generates active species
that initiate the polymerization of the polymerizable compound upon
exposure to exposure light (e.g., visible rays, ultraviolet rays
(e.g., i-line), deep ultraviolet rays, electron beams, or X-rays).
It is preferable to use the photo-radical generator.
[0165] Examples of the photo-radical generator include an
acetophenone-based compound, a biimidazole-based compound, a
triazine-based compound, an O-acyloxime-based compound, an onium
salt-based compound, a benzoin-based compound, a benzophenone-based
compound, an .alpha.-diketone-based compound, a polynuclear
quinone-based compound, a xanthone-based compound, a diazo-based
compound, an imidosulfonate-based compound, and the like. These
compounds generate either or both of active radicals and an active
acid upon exposure. These photo-radical generators may be used
either alone or in combination.
[0166] Specific examples of the acetophenone-based compound include
2-hydroxy-2-methyl-1-phenylpropan-1-one,
2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one,
2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one,
1-hydroxycyclohexyl phenyl ketone,
2,2-dimethoxy-1,2-diphenylethan-1-one, 1,2-octanedione,
2-benzyl-2-dimethylamino-4'-morpholinobutyrophenone, and the
like.
[0167] Specific examples of the biimidazole-based compound 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,
2,2'-bis(2,4,6-tribromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole,
and the like.
[0168] When using a biimidazole-based compound as a photoinitiator,
it is preferable to use a hydrogen donor in combination with the
biimidazole-based compound in order to further improve
sensitivity.
[0169] The term "hydrogen donor" used herein refers to a compound
that can donate a hydrogen atom to radicals generated by the
biimidazole-based compound upon exposure. A mercaptan-based
compound, an amine-based compound, and the like are preferable as
the hydrogen donor.
[0170] Examples of the mercaptan-based compound include
2-mercaptobenzothiazole, 2-mercaptobenzoxazole,
2-mercaptobenzimidazole, 2,5-dimercapto-1,3,4-thiadiazole,
2-mercapto-2,5-dimethyl aminopyridine, and the like. Examples of
the amine-based compound include
4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethyl
amino)benzophenone, 4-diethyl aminoacetophenone,
4-dimethylaminopropiophenone, ethyl-4-dimethyl aminobenzoate,
4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile, and the
like.
[0171] Specific examples of the triazine-based compound include a
triazine-based compound that includes 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-yl)ethenyl]-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.
[0172] Specific examples of the O-acyloxime-based compound include
1-[4-(phenylthio)phenyl]-heptane-1,2-dione-2-(O-benzoyloxime),
1-[4-(phenylthio)phenyl]-octane-1,2-dione-2-(O-benzoyloxime),
1-[4-(benzoyl)phenyl]-octane-1,2-dione-2-(O-benzoyloxime),
1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethanone-1-(O-acetyloxim-
e),
1-[9-ethyl-6-(3-methylbenzoyl)-9H-carbazol-3-yl]-ethanone-1-(O-acetylo-
xime),
1-(9-ethyl-6-benzoyl-9H-carbazol-3-yl)-ethanone-1-(O-acetyloxime),
ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzoyl)-9H-carbazol-3-
-yl]-1-(O-acetyloxime),
ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzoyl)-9H-carbazol-3-
-yl]-1-(O-acetyloxime),
ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzoyl)-9H-carbazol-3-
-yl]-1-(O-acetyloxime),
ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylbenzoyl)-9H-carbazol-3-
-yl]-1-(O-acetyloxime),
ethanone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)benzoyl}-9-
H-carbazol-3-yl]-1-(O-acetyloxime),
ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxybenzoyl)-9H-car-
bazol-3-yl]-1-(O-acetyloxime),
ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylmethoxybenzoyl)-9H-car-
bazol-3-yl]-1-(O-acetyloxime),
ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylmethoxybenzoyl)-9H-car-
bazol-3-yl]-1-(O-acetyloxime),
ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxim-
e),
ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylmethoxybenzoyl)-9H--
carbazol-3-yl]-1-(O-acetyloxime),
ethanone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxyben-
zoyl}-9H-carbazol-3-yl]-1-(O-acetyloxime), and the like.
[0173] A commercially available product may be used directly as the
photo-radical generator. Specific examples of a commercially
available product that may be used as the photo-radical generator
include Irgacure 907, Irgacure 184, Irgacure 369, Irgacure 651,
Irgacure 819, Irgacure 907, and Irgacure OXE02 (manufactured by
BASF); Adekaoptomer N1919 (manufactured by Adeka Corporation); and
the like.
[0174] Examples of the anionic initiator include an alkyllithium
compound; a monolithium salt or a monosodium salt of biphenyl,
naphthalene, pyrene, and the like; a polyfunctional initiator such
as a dilithium salt and a trilithium salt; and the like.
[0175] Examples of the cationic initiator include a proton acid
such as sulfuric acid, phosphoric acid, perchloric acid, and
trifluoromethanesulfonic acid; a Lewis acid such as boron
trifluoride, aluminum chloride, titanium tetrachloride, and tin
tetrachloride; an aromatic onium salt or a combination of an
aromatic onium salt and a reducing agent; and the like.
[0176] These initiators may be used either alone or in
combination.
[0177] The polymerizable composition according to one embodiment of
the invention normally includes the initiator in an amount of 0.1
to 30 parts by weight, and preferably 0.5 to 10 parts by weight,
based on 100 parts by weight of the polymerizable compound.
[0178] It is preferable to add a surfactant to the polymerizable
composition according to one embodiment of the invention in order
to adjust the surface tension of the polymerizable composition. The
surfactant is not particularly limited, but is preferably a
nonionic surfactant. A commercially available product may be used
as the nonionic surfactant. Examples of a commercially available
product that may be used as the nonionic surfactant include an
oligomer having a molecular weight of about several thousand (e.g.,
"KH-40" manufactured by AGC Seimi Chemical Co., Ltd.), and the
like. The surfactant is normally added to the polymerizable
composition according to one embodiment of the invention in an
amount of 0.01 to 10 parts by weight, and preferably 0.1 to 2 parts
by weight, based on 100 parts by weight of the polymerizable
compound.
[0179] The polymerizable composition according to one embodiment of
the invention may further include an additional additive such as an
additional copolymerizable monomer, a metal, a metal complex, a
dye, a pigment, a fluorescent material, a phosphorescent material,
a leveling agent, a thixotropic agent, a gelling agent, a
polysaccharide, a UV absorber, an IR (infrared) absorber, an
antioxidant, an ion-exchange resin, and a metal oxide (e.g.,
titanium oxide). Each additional additive is normally added to the
polymerizable composition according to one embodiment of the
invention in an amount of 0.1 to 20 parts by weight based on 100
parts by weight of the polymerizable compound.
[0180] The polymerizable composition according to one embodiment of
the invention may be prepared by mixing and dissolving given
amounts of the polymerizable compound according to one embodiment
of the invention, the initiator, and an optional additive in an
appropriate organic solvent.
[0181] Examples of the organic solvent include a ketone such as
cyclopentanone, cyclohexanone, and methyl ethyl ketone; an acetate
such as butyl acetate and amyl acetate; a halogenated hydrocarbon
such as chloroform, dichloromethane, and dichloroethane; an ether
such as 1,4-dioxane, cyclopentyl methyl ether, tetrahydrofuran,
tetrahydropyran, and 1,3-dioxolane; and the like.
[0182] The polymerizable composition thus obtained is useful as a
raw material for producing the polymer and the optically
anisotropic article according to the embodiments of the invention
(described below).
3) Polymer
[0183] A polymer according to one embodiment of the invention is
(1) a polymer obtained by polymerizing the polymerizable compound
according to one embodiment of the invention, or (2) a polymer
obtained by polymerizing the polymerizable composition according to
one embodiment of the invention.
[0184] The term "polymerization" used herein refers to a chemical
reaction in a broad sense including a normal polymerization
reaction and a crosslinking reaction.
(1) Polymer Obtained by Polymerizing Polymerizable Compound
[0185] The polymer obtained by polymerizing the polymerizable
compound according to one embodiment of the invention may be a
homopolymer of the polymerizable compound according to one
embodiment of the invention, a copolymer of two or more types of
the polymerizable compound according to one embodiment of the
invention, or a copolymer of the polymerizable compound according
to one embodiment of the invention and an additional
copolymerizable monomer.
[0186] Examples of the additional copolymerizable monomer include a
commercially available product such as LC-242 (manufactured by
BASF), the compounds disclosed in JP-A-2007-002208,
JP-A-2009-173893, JP-A-2009-274984, JP-A-2010-030979,
JP-A-2010-031223, JP-A-2011-006360, PCT/JP2012/060011
(WO2012/141245), PCT/JP2012/061321 (WO2012/147904),
PCT/JP2012/064111 (WO2012/169424), PCT/JP2012/065202
(WO2012/176679), and PCT2012/067906, and the like.
[0187] Further examples of the additional copolymerizable monomer
include 4'-methoxyphenyl 4-(2-methacryloyloxyethyloxy)benzoate,
biphenyl 4-(6-methacryloyloxyhexyloxy)benzoate, 4'-cyanobiphenyl
4-(2-acryloyloxyethyloxy)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, and the like.
[0188] A polyfunctional monomer that includes a plurality of
polymerizable unsaturated groups (e.g., acryloyl group,
methacryloyl group, vinyl group, and allyl group) may also be used
as the additional copolymerizable monomer.
[0189] Examples of such a polyfunctional monomer include an
alkanediol diacrylate such as 1,2-butanediol diacrylate,
1,3-butanediol diacrylate, 1,4-butanediol diacrylate,
neopentanediol diacrylate, and 1,6-hexanediol diacrylate; an
alkanediol dimethacrylate such as 1,2-butanediol dimethacrylate,
1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate,
neopentanediol dimethacrylate, and 1,6-hexanediol dimethacrylate; a
polyethylene glycol diacrylate such as ethylene glycol diacrylate,
diethylene glycol diacrylate, triethylene glycol diacrylate, and
tetraethylene glycol diacrylate; a polypropylene glycol diacrylate
such as propylene glycol diacrylate, dipropylene glycol diacrylate,
tripropylene glycol diacrylate, and tetrapropylene glycol
diacrylate; a polyethylene glycol dimethacrylate such as ethylene
glycol dimethacrylate, diethylene glycol dimethacrylate,
triethylene glycol dimethacrylate, and tetraethylene glycol
dimethacrylate; a polypropylene glycol dimethacrylate such as
propylene glycol dimethacrylate, dipropylene glycol dimethacrylate,
tripropylene glycol dimethacrylate, and tetrapropylene glycol
dimethacrylate; a polyethylene glycol divinyl ether such as
ethylene glycol divinyl ether, diethylene glycol divinyl ether,
triethylene glycol divinyl ether, and tetraethylene glycol divinyl
ether; a polyethylene glycol diallyl ether such as ethylene glycol
diallyl ether, diethylene glycol diallyl ether, triethylene glycol
diallyl ether, and tetraethylene glycol diallyl ether; bisphenol F
ethoxylate diacrylate; bisphenol F ethoxylate dimethacrylate;
bisphenol A ethoxylate diacrylate; bisphenol A ethoxylate
dimethacrylate; trimethylolpropane triacrylate; trimethylolpropane
trimethacrylate; trimethylolpropane ethoxylate triacrylate;
trimethylolpropane ethoxylate trimethacrylate; trimethylolpropane
propoxylate triacrylate; trimethylolpropane propoxylate
trimethacrylate; isocyanuric acid ethoxylate triacrylate; glycerol
ethoxylate triacrylate; glycerol propoxylate triacrylate;
pentaerythritol ethoxylate tetraacrylate; ditrimethylolpropane
ethoxylate tetraacrylate; dipentaerythritol ethoxylate hexacrylate;
and the like.
[0190] The polymerizable compound according to one embodiment of
the invention may be (co)polymerized optionally together with the
additional copolymerizable monomer in the presence of an
appropriate initiator. The initiator may be used in an amount
similar to that of the initiator included in the polymerizable
composition.
[0191] When the polymer according to one embodiment of the
invention is a copolymer of the polymerizable compound according to
one embodiment of the invention and the additional copolymerizable
monomer, the content of constituent units derived from the
polymerizable compound according to one embodiment of the invention
is not particularly limited, but is preferably 0.1 to 50 wt %, and
more preferably 1 to 40 wt %, based on the total constituent units.
When the content of structural units derived from the polymerizable
compound is within the above range, a polymer that has a high glass
transition temperature (Tg) and high hardness can be obtained.
[0192] The polymer (1) may be produced by (A) (co)polymerizing the
polymerizable compound optionally together with the additional
copolymerizable monomer in an appropriate organic solvent in the
presence of an appropriate initiator, isolating the target polymer,
dissolving the polymer in an appropriate organic solvent to prepare
a solution, applying the solution to an appropriate substrate to
obtain a film, and drying the film, followed by optional heating,
or (B) applying a solution prepared by dissolving the polymerizable
compound and an initiator in an organic solvent optionally together
with the additional copolymerizable monomer to a substrate using a
known coating method, removing the solvent, and effecting
polymerization by applying heat or activated energy rays, for
example.
[0193] Examples of the initiator include those mentioned above in
connection with the initiator included in the polymerizable
composition.
[0194] The organic solvent used for polymerization when
implementing the method (A) is not particularly limited as long as
the organic solvent is inert. Examples of the organic solvent
include an aromatic hydrocarbon such as toluene, xylene, and
mesitylene; a ketone such as cyclohexanone, cyclopentanone, and
methyl ethyl ketone; an acetate such as butyl acetate and amyl
acetate; a halogenated hydrocarbon such as chloroform,
dichloromethane, and dichloroethane; an ether such as cyclopentyl
methyl ether, tetrahydrofuran, and tetrahydropyran; and the like.
Among these, a compound having a boiling point of 60 to 250.degree.
C. is preferable, and a compound having a boiling point of 60 to
150.degree. C. is more preferable, from the viewpoint of handling
capability.
[0195] Examples of the organic solvent used to dissolve the polymer
when implementing the method (A), and the organic solvent used for
the method (B), include a ketone-based solvent such as acetone,
methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and
cyclohexanone; an ester-based solvent such as butyl acetate and
amyl acetate; a halogenated hydrocarbon-based solvent such as
dichloromethane, chloroform, and dichloroethane; an ether-based
solvent such as tetrahydrofuran, tetrahydropyran,
1,2-dimethoxyethane, 1,4-dioxane, cyclopentyl methyl ether,
1,3-dioxolane; an aprotic polar solvent such as
N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide,
gamma-butyrolactone, and N-methylpyrrolidone; and the like. Among
these, a compound having a boiling point of 60 to 200.degree. C. is
preferable from the viewpoint of handling capability. These
solvents may be used either alone or in combination.
[0196] A substrate formed of a known organic or inorganic material
may be used as the substrate. Examples of the organic material
include a polycycloolefin (e.g., Zeonex and Zeonor (registered
trademark; manufactured by Zeon Corporation); Arton (registered
trademark; manufactured by JSR Corporation); and Apel (registered
trademark; manufactured by Mitsui Chemicals Inc.)), polyethylene
terephthalate, a polycarbonate, a polyimide, a polyamide,
polymethyl methacrylate, polystyrene, polyvinyl chloride,
polytetrafluoroethylene, cellulose, cellulose triacetate,
polyethersulfone, and the like. Examples of the inorganic material
include silicon, glass, calcite, and the like. It is preferable to
use a substrate formed of an organic material.
[0197] The substrate may be a single-layer substrate, or may be a
laminate.
[0198] The substrate is preferably a substrate formed of an organic
material, and more preferably a resin film that is formed of the
organic material.
[0199] The polymer solution (method (A)) or the solution subjected
to polymerization (method (B)) may be applied to the substrate
using a known coating method. Examples of the coating method
include a curtain coating method, an extrusion coating method, a
roll coating method, a spin coating method, a dip coating method, a
bar coating method, a spray coating method, a slide coating method,
a print coating method, and the like.
(2) Polymer Obtained by Polymerizing Polymerizable Composition
[0200] The polymer according to one embodiment of the invention can
be easily obtained by polymerizing the polymerizable composition
according to one embodiment of the invention. It is preferable to
use the polymerizable composition that includes the initiator
(particularly a photoinitiator) in order to more efficiently effect
polymerization.
[0201] Specifically, it is preferable to produce the polymer
according to one embodiment of the invention using the method (B)
that applies the polymerizable composition according to one
embodiment of the invention to a substrate, and polymerizes the
applied polymerizable composition. Examples of the substrate
include a substrate used to produce an optically anisotropic
article (described later), and the like.
[0202] The polymerizable composition according to one embodiment of
the invention may be applied to the substrate using a known coating
method (e.g., bar coating method, spin coating method, roll coating
method, gravure coating method, spray coating method, die coating
method, cap coating method, or dipping method). A known organic
solvent may be added to the polymerizable composition according to
one embodiment of the invention in order to improve the
applicability of the polymerizable composition. In this case, it is
preferable to remove the organic solvent by natural drying, drying
by heating, drying under reduced pressure, drying by heating under
reduced pressure, or the like, after applying the polymerizable
composition to the substrate.
[0203] The polymerizable compound according to one embodiment of
the invention or the polymerizable composition according to one
embodiment of the invention may be polymerized by applying
activated energy rays, or utilizing a thermal polymerization
method, for example. It is preferable to polymerize the
polymerizable compound or the polymerizable composition by applying
activated energy rays since heating is unnecessary (i.e., the
reaction can be effected at room temperature). It is preferable to
apply light (e.g., ultraviolet rays) to the polymerizable compound
or the polymerizable composition since the operation is simple.
[0204] The temperature during application is preferably set to
30.degree. C. or less. The irradiance is normally 1 W/m.sup.2 to 10
kW/m.sup.2, and preferably 5 W/m.sup.2 to 2 kW/m.sup.2.
[0205] A polymer obtained by polymerizing the polymerizable
compound according to one embodiment of the invention or the
polymerizable composition according to one embodiment of the
invention may be removed from the substrate, and used alone, or may
be used directly as an optical film organic material or the like
without removing the polymer from the substrate.
[0206] The number average molecular weight of the polymer according
to one embodiment of the invention thus obtained is preferably 500
to 500,000, and more preferably 5,000 to 300,000. When the number
average molecular weight of the polymer is within the above range,
the resulting film exhibits high hardness and an excellent handling
capability. The number average molecular weight of the polymer may
be determined by gel permeation chromatography (GPC) using
monodisperse polystyrene as a standard (eluent:
tetrahydrofuran).
[0207] It is considered that the polymer according to one
embodiment of the invention has a structure in which crosslinking
points are uniformly present within the molecule, and exhibits a
high crosslinking efficiency and excellent hardness.
[0208] The polymer according to one embodiment of the invention
makes it possible to inexpensively produce an optical film that
achieves uniform conversion of polarized light over a wide
wavelength band, and exhibits satisfactory performance.
4) Optically Anisotropic Article
[0209] An optically anisotropic article according to one embodiment
of the invention includes (is produced using) the polymer according
to one embodiment of the invention.
[0210] The optically anisotropic article according to one
embodiment of the invention may be obtained by forming an alignment
film on a substrate, and forming a polymer film on the alignment
film using the polymer according to one embodiment of the
invention.
[0211] The alignment film is formed on the surface of the substrate
in order to achieve the in-plane alignment of an organic
semiconductor compound in one direction.
[0212] The alignment film may be obtained by applying a solution
(alignment film composition) that includes a polymer (e.g.,
polyimide, polyvinyl alcohol, polyester, polyallylate,
polyamideimide, or polyetherimide) to the substrate to form a film,
drying the film, and subjecting the film to a rubbing treatment in
one direction, for example.
[0213] The thickness of the alignment film is preferably 0.001 to 5
.mu.m, and more preferably 0.001 to 1 .mu.m.
[0214] The rubbing treatment may be performed on the alignment
film, or may be performed on the substrate. The rubbing treatment
may be implemented using an arbitrary method. For example, the
alignment film may be rubbed in a given direction using a roll
around which a cloth or felt formed of synthetic fibers (e.g.,
nylon) or natural fibers (e.g., cotton) is wound. It is preferable
to wash (clean) the alignment film with isopropyl alcohol or the
like after completion of the rubbing treatment in order to remove a
fine powder (foreign substance) formed during the rubbing
treatment, and clean the surface of the alignment film.
[0215] The alignment film may be provided with a function of
achieving in-plane alignment in one direction by applying polarized
UV rays to the surface of the alignment film.
[0216] A liquid crystal layer may be formed on the alignment film
using the polymer according to one embodiment of the invention by
utilizing the method described above in connection with the polymer
according to one embodiment of the invention.
[0217] Since the optically anisotropic article according to one
embodiment of the invention is produced using the polymer according
to one embodiment of the invention, the optically anisotropic
article can be produced inexpensively, achieves uniform conversion
of polarized light over a wide wavelength band, and exhibits
satisfactory performance.
[0218] The optically anisotropic article according to one
embodiment of the invention may be applied as a retardation film,
an alignment film for a liquid crystal display device (liquid
crystal display), a polarizer, a viewing angle-improving film, a
color filter, a low-pass filter, an optical polarization prism, an
optical filter, and the like.
EXAMPLES
[0219] The invention is further described below by way of examples.
Note that the invention is not limited to the following
examples.
Example 1: Synthesis of Compound 1
##STR00030##
[0220] Step 1: Synthesis of Intermediate A
##STR00031##
[0222] A three-necked reactor equipped with a thermometer was
charged with 18.0 g (123 mmol) of adipic acid and 250 ml of
tetrahydrofuran (THF) under a nitrogen stream to prepare a
homogeneous solution. The reactor was immersed in an ice bath to
adjust the temperature inside the reactor to 0.degree. C. 10.0 g
(77.4 mmol) of N,N-diisopropylethylamine was slowly added dropwise
to the solution, and a solution prepared by dissolving 4.23 g (36.9
mmol) of methanesulfonyl chloride in 50 ml of THF was slowly added
dropwise to the mixture. After the dropwise addition, the mixture
was stirred for 45 minutes. 9.5 g (35.9 mmol) of
4-(6-acryloyloxyhex-1-yloxy)phenol (manufactured by DKSH Japan
K.K.) was added to the resulting reaction mixture to prepare a
solution. 6.0 g (46.4 mmol) of N,N-diisopropylethylamine was slowly
added dropwise to the solution. After the dropwise addition, 0.38 g
(3.1 mmol) of 4-(dimethylamino)pyridine was added to the mixture.
The reaction mixture was returned to room temperature (23.degree.
C.), and stirred for 4 hours.
[0223] After completion of the reaction, the reaction mixture was
added to 1 l of dilute hydrochloric acid, followed by extraction
twice with 300 ml of ethyl acetate. The organic layer was collected
and dried over anhydrous sodium sulfate, and sodium sulfate was
filtered off. The solvent was removed from the filtrate using a
rotary evaporator to obtain a light yellow oil. The light yellow
oil was purified by silica gel column chromatography (toluene:ethyl
acetate=5:5 (volume ratio)), and purified by silica gel column
chromatography (chloroform:methanol=95:5 (volume ratio)) to obtain
4.0 g of an intermediate A as a white solid (yield: 28.4%).
[0224] The structure of the target product was identified by
.sup.1H-NMR.
[0225] .sup.1H-NMR (500 MHz, CDCl.sub.3, TMS, .delta. ppm):
12.2-10.0 (br, 1H), 6.97 (d, 2H, J=9.0 Hz), 6.86 (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), 3.93
(t, 2H, J=6.5 Hz), 2.57 (t, 2H, J=7.0 Hz), 2.43 (t, 2H, J=7.0 Hz),
1.85-1.67 (m, 8H), 1.55-1.40 (m, 4H)
##STR00032##
Step 2: Synthesis of Intermediate B
[0226] A three-necked reactor equipped with a thermometer was
charged with 4.0 g (10.2 mmol) of the intermediate A, 100 ml of
THF, and 1 ml of N,N-dimethylformamide (DMF) under a nitrogen
stream to prepare a homogeneous solution. The reactor was immersed
in an ice water bath to adjust the temperature inside the reactor
to 10.degree. C. A solution prepared by dissolving 13.6 g (0.11
mol) of oxalyl chloride in 50 ml of THF was slowly added to the
solution contained in the reactor while maintaining the temperature
of the reaction mixture at 10 to 20.degree. C. The reaction mixture
was then returned to room temperature (23.degree. C.), and stirred
at 23.degree. C. for 6 hours. After completion of the reaction, the
reaction mixture was concentrated using a rotary evaporator to
obtain a yellow oil. The yellow oil was used directly for the
subsequent reaction without purification.
[0227] Another three-necked reactor equipped with a thermometer was
charged with 0.5 g (3.6 mmol) of 2,5-dihydroxybenzaldehyde, 1.2 g
(9.3 mmol) of N,N-diisopropylethylamine, 0.2 g (1.6 mmol) of
4-(dimethyl amino)pyridine, and 100 ml of THF under a nitrogen
stream to prepare a homogeneous solution. A solution prepared by
dissolving the yellow oil in 80 ml of THF was slowly added dropwise
to the solution in an ice bath. After the dropwise addition, the
reaction mixture was returned to room temperature (23.degree. C.),
and stirred for 6 hours. After completion of the reaction, the
reaction mixture was added to 500 ml of dilute hydrochloric acid,
and extracted twice with 150 ml of ethyl acetate. The organic layer
was collected and dried over anhydrous sodium sulfate, and sodium
sulfate was filtered off. The solvent was removed from the filtrate
using a rotary evaporator to obtain a yellow oil. The yellow solid
was purified by silica gel column chromatography (toluene:ethyl
acetate=8:2 (volume ratio)) to obtain 1.8 g of an intermediate B as
a white solid (yield: 56.4%).
[0228] The structure of the target product was identified by
.sup.1H-NMR.
[0229] .sup.1H-NMR (500 MHz, CDCl.sub.3, TMS, .delta. ppm): 10.06
(s, 1H), 7.63 (d, 1H, J=2.5 Hz), 7.37 (dd, 1H, J=2.5 Hz, 9.0 Hz),
7.21 (d, 1H, J=9.0 Hz), 6.99 (d, 4H, J=9.0 Hz), 6.87 (d, 4H, J=9.0
Hz), 6.40 (dd, 2H, J=1.5 Hz, 17.5 Hz), 6.12 (dd, 2H, J=10.5 Hz,
17.5 Hz), 5.82 (dd, 2H, J=1.5 Hz, 10.5 Hz), 4.17 (t, 4H, J=6.5 Hz),
3.93 (t, 4H, J=6.5 Hz), 2.75-2.59 (m, 8H), 1.95-1.64 (m, 16H),
1.55-1.40 (m, 8H)
Step 3: Synthesis of Intermediate C
##STR00033##
[0231] A four-necked reactor equipped with a thermometer was
charged with 2.00 g (12.1 mmol) of 2-hydrazinobenzothiazole and 20
ml of DMF under a nitrogen stream to prepare a solution. After the
addition of 8.36 g (60.5 mmol) of potassium carbonate and 3.08 g
(14.5 mmol) of 1-iodohexane to the solution, the mixture was
stirred at 50.degree. C. for 7 hours. The resulting reaction
mixture was cooled to 20.degree. C., added to 200 ml of water, and
extracted with 300 ml of ethyl acetate. After drying the ethyl
acetate layer over anhydrous sodium sulfate, sodium sulfate was
filtered off. Ethyl acetate was evaporated from the filtrate under
reduced pressure using a rotary evaporator to obtain a yellow
solid. The yellow solid was purified by silica gel column
chromatography (n-hexane:ethyl acetate=75:25 (volume ratio)) to
obtain 2.10 g of an intermediate C as a white solid (yield:
69.6%).
[0232] The structure of the target product was identified by
.sup.1H-NMR.
[0233] .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)
Step 4: Synthesis of Compound 1
[0234] A four-necked reactor equipped with a thermometer was
charged with 1.5 g (1.69 mmol) of the intermediate B synthesized in
the step 2, 0.464 g (1.86 mmol) of the intermediate C synthesized
in the step 3, and 50 ml of THF under a nitrogen stream to prepare
a solution. After the addition of 39.3 mg (0.17 mmol) of
(.+-.)-10-camphorsulfonic acid to the solution, the mixture was
stirred at room temperature (23.degree. C.) for 7 hours. After
completion of the reaction, the reaction mixture was added to 300
ml of diluted sodium bicarbonate water, and extracted twice with
150 ml of ethyl acetate. The ethyl acetate layer was collected and
dried over anhydrous sodium sulfate, and sodium sulfate was
filtered off. Ethyl acetate was evaporated from the filtrate under
reduced pressure using a rotary evaporator to obtain a light yellow
oil. The light yellow oil was purified by silica gel column
chromatography (toluene:ethyl acetate=80:20 (volume ratio)) to
obtain 1.2 g of a compound 1 as a light yellow oil (yield:
63.5%).
[0235] The structure of the target product was identified by
.sup.1H-NMR.
[0236] .sup.1H-NMR (500 MHz, CDCl.sub.3, TMS, .delta. ppm): 7.74
(d, 1H, J=3.0 Hz), 7.67-7.60 (m, 3H), 7.35-7.31 (m, 1H), 7.15-7.09
(m, 3H), 7.00-6.96 (m, 4H), 6.85 (d, 4H, J=9.0 Hz), 6.40 (dd, 2H,
J=1.5 Hz, 17.5 Hz), 6.12 (dd, 2H, J=10.5 Hz, 17.5 Hz), 5.81 (dd,
2H, J=1.5 Hz, 10.5 Hz), 4.28 (t, 2H, J=7.5 Hz), 4.17 (t, 2H, J=6.5
Hz), 4.16 (t, 2H, J=6.5 Hz), 3.911 (t, 2H, J=6.5 Hz), 3.909 (t, 2H,
J=6.5 Hz), 2.72-2.61 (m, 8H), 1.93-1.67 (m, 16H), 1.52-1.27 (m,
16H), 0.89 (t, 3H, J=7.0 Hz)
Synthesis Example 1: Synthesis of Compound .alpha.
##STR00034##
[0237] Step 1: Synthesis of Intermediate X
##STR00035##
[0239] 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 THF under a
nitrogen stream. After the addition of 6.58 g (57.43 mmol) of
methanesulfonyl chloride to the mixture, the reactor was immersed
in a water bath to adjust the temperature inside the reactor to
20.degree. C. 6.34 g (62.65 mmol) of triethylamine was added
dropwise to the reaction mixture over 10 minutes while maintaining
the temperature inside the reactor at 20 to 30.degree. C. After the
dropwise addition, the water bath was removed, and the mixture was
stirred at room temperature (23.degree. C.) for 2 hours. After the
addition of 0.64 g (5.22 mmol) of 4-(dimethylamino)pyridine and
13.80 g (52.21 mmol) of 4-(6-acryloyloxyhex-1-yloxy)phenol to the
reaction mixture, the reactor was immersed in a water bath to
adjust the temperature inside the reactor to 15.degree. C. 6.34 g
(62.65 mmol) of triethylamine was added dropwise to the reaction
mixture over 10 minutes while maintaining the temperature inside
the reactor at 20 to 30.degree. C. After the dropwise addition, the
mixture was stirred at room temperature (23.degree. C.) for 2
hours. After completion of the reaction, 1,000 ml of distilled
water and 100 ml of a saturated sodium chloride solution were added
to the reaction mixture, followed by extraction twice with 400 ml
of ethyl acetate. The organic layer was collected and dried over
anhydrous sodium sulfate, and sodium sulfate was filtered off. The
filtrate was concentrated using a rotary evaporator, and the
concentrate was purified by silica gel column chromatography
(THF:toluene=1:9 (volume ratio)) to obtain 14.11 g of an
intermediate X (yield: 65%).
[0240] The structure of the target product was identified by
.sup.1H-NMR.
[0241] .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)
Step 2: Synthesis of Intermediate Y
##STR00036##
[0243] A three-necked reactor equipped with a thermometer was
charged with 4.00 g (9.56 mmol) of the intermediate X and 60 ml of
THF under a nitrogen stream to prepare a solution. After the
addition of 1.12 g (9.78 mmol) of methanesulfonyl chloride to the
solution, the reactor was immersed in a water bath to adjust the
temperature inside the reactor to 20.degree. C. 1.01 g (9.99 mmol)
of triethylamine was added dropwise to the reaction mixture over 5
minutes while maintaining the temperature inside the reactor at 20
to 30.degree. C. After removing the water bath, the mixture was
stirred at room temperature (23.degree. C.) for 2 hours. After the
addition of 0.11 g (0.87 mmol) of 4-(dimethylamino)pyridine and
0.60 g (4.35 mmol) of 2,5-dihydroxybenzaldehyde to the reaction
mixture, the reactor was immersed in a water bath to adjust the
temperature inside the reactor to 15.degree. C. 1.10 g (10.87 mmol)
of triethylamine was added dropwise to the reaction mixture over 5
minutes while maintaining the temperature inside the reactor at 20
to 30.degree. C. After the dropwise addition, the mixture was
stirred at room temperature (23.degree. C.) for 2 hours. After
completion of the reaction, 400 ml of distilled water and 50 ml of
a saturated sodium chloride solution were added to the reaction
mixture, followed by extraction twice with 750 ml of ethyl acetate.
The organic layer was collected and dried over anhydrous sodium
sulfate, and sodium sulfate was filtered off. The filtrate was
concentrated using a rotary evaporator to obtain a solid. The solid
was dissolved in 100 ml of THF. 500 ml of methanol was added to the
solution to precipitate crystals, which were filtered off. The
crystals were washed with methanol, and dried under vacuum to
obtain 2.51 g of an intermediate Y (yield: 62%).
[0244] The structure of the target product was identified by
.sup.1H-NMR.
[0245] .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)
Step 3: Synthesis of Intermediate Z
##STR00037##
[0247] A three-necked reactor equipped with a thermometer was
charged with 2.00 g (12.1 mmol) of 2-hydrazinobenzothiazole and 30
ml of DMF under a nitrogen stream to prepare a solution, and 7.88 g
(24.2 mmol) of cesium carbonate was added to the solution. 1.98 g
(14.5 mmol) of butyl 2-chloroethyl ether was added dropwise to the
mixture at 0.degree. C. over 5 minutes. After the dropwise
addition, the reaction mixture was returned to room temperature
(23.degree. C.), and stirred for 3 hours. After completion of the
reaction, 200 ml of water was added to the reaction mixture,
followed by extraction twice with 100 ml of ethyl acetate. The
organic layer was collected and dried over anhydrous sodium
sulfate, and sodium sulfate was filtered off. The filtrate was
concentrated using a rotary evaporator, and the concentrate was
purified by silica gel column chromatography (n-hexane:ethyl
acetate=75:25 (volume ratio)) to obtain 1.70 g of an intermediate Z
as a white solid (yield: 53.0%).
[0248] The structure of the target product was identified by
.sup.1H-NMR.
[0249] .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)
Step 4: Synthesis of Compound .alpha.
[0250] A three-necked reactor equipped with a thermometer was
charged with 1.50 g (1.60 mmol) of the intermediate Y synthesized
in the step 2, 369 mg (1.78 mmol) of the intermediate Z synthesized
in the step 3, 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 homogeneous solution. The solution was stirred at
40.degree. C. for 5 hours. After completion of the reaction, the
reaction mixture was added to 100 ml of water, and extracted with
200 ml of ethyl acetate. After drying the ethyl acetate layer over
anhydrous sodium sulfate, sodium sulfate was filtered off. Ethyl
acetate was evaporated from the filtrate under reduced pressure
using a rotary evaporator to obtain a yellow solid. The yellow
solid was purified by silica gel column chromatography
(toluene:ethyl acetate=9:1 (volume ratio)) to obtain 1.31 g of a
compound .alpha. as a light yellow solid (yield: 69.4%).
[0251] The structure of the target product was identified by
.sup.1H-NMR.
[0252] .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)
[0253] The phase transition temperature was measured by the
following method using the compound 1 obtained in Example 1, the
compound .alpha. obtained in Synthesis Example 1, and the compound
1r ("LC242" manufactured by BASF) of Reference Example 1 that was
used in Comparative Examples 1 and 2.
##STR00038##
Measurement of Phase Transition Temperature
[0254] 10 mg of each compound (compounds 1, .alpha., and 1r) was
weighed, and placed in a solid state between two glass substrates
provided with a polyimide alignment film subjected to a rubbing
treatment (manufactured by E.H.C. Co., Ltd.). The substrates were
placed on a microscope cooling-heating device ("10036" manufactured
by Japan High Tech Co., Ltd.), heated from -10.degree. C. to
+200.degree. C., and cooled to 23.degree. C. A change in structure
during a change in temperature was observed using a polarizing
optical microscope ("ECLIPSE LV100POL" manufactured by Nikon
Corporation).
[0255] The phase transition temperature measurement results are
shown in Table 1.
[0256] In Table 1, "C" refers to "crystal", "N" refers to
"nematic", and "I" refers to "isotropic". The term "crystal" means
that the test compound was in a solid phase, the term "nematic"
means that the test compound was in a nematic liquid crystal phase,
and the term "isotropic" means that the test compound was in an
isotropic liquid phase.
TABLE-US-00001 TABLE 1 Compound Phase transition temperature
Example 1 Compound 1 ##STR00039## Synthesis Example 1 Compound
.alpha. ##STR00040## Reference Example 1 Compound 1r
##STR00041##
Example 2
[0257] 0.3 g of the compound 1 obtained in Example 1, 0.7 g of the
compound .alpha. obtained in Synthesis Example 1, 30 mg of a
photoinitiator ("Adekaoptomer N-1919" manufactured by Adeka
Corporation), and 100 mg of a 1% cyclopentanone solution of a
surfactant ("KH-40" manufactured by AGC Seimi Chemical Co., Ltd.)
were dissolved in 2.3 g of cyclopentanone. The solution was
filtered through a disposable filter having a pore size of 0.45
.mu.m to prepare a polymerizable composition 1.
Reference Examples 1 and 2
[0258] A polymerizable composition 2 was prepared in the same
manner as in Example 2, except that 1.0 g of the compound .alpha.
obtained in Synthesis Example 1 was used instead of using 0.3 g of
the compound 1 and 0.7 g of the compound .alpha..
Comparative Example 1
[0259] A polymerizable composition 3 was prepared in the same
manner as in Example 2, except that 0.3 g of the compound 1r was
used instead of 0.3 g of the compound 1.
Comparative Example 2
[0260] A polymerizable composition 4 was prepared in the same
manner as in Example 2, except that 1.0 g of the compound 1r was
used instead of using 0.3 g of the compound 1 and 0.7 g of the
compound .alpha..
[0261] Each of the polymerizable compositions 1 to 4 was
polymerized using the following method to obtain a polymer. The
retardation and the wavelength dispersion were measured and
evaluated using the resulting polymer.
Measurement of Retardation and Evaluation of Wavelength
Dispersion
(i) Formation of Liquid Crystal Layer Using Polymerizable
Composition
[0262] Each of the polymerizable compositions 1 to 4 was applied to
a transparent glass substrate provided with a polyimide alignment
film subjected to a rubbing treatment (manufactured by E.H.C. Co.,
Ltd.) using a #4 wire bar. The resulting film was dried for 1
minute at the temperature shown in Table 2, and subjected to an
alignment treatment for 1 minute at the temperature shown in Table
2 to form a liquid crystal layer. UV rays were applied (directly)
to the liquid crystal layer at a dose of 2,000 mJ/cm.sup.2 to
effect polymerization to prepare a wavelength dispersion
measurement sample.
(ii) Measurement of Retardation
[0263] The retardation of the sample between 400 nm and 800 nm was
measured using an ellipsometer ("M2000U" manufactured by J. A.
Woollam).
(iii) Evaluation of Wavelength Dispersion
[0264] The wavelength dispersion was evaluated based on the values
.alpha. and .beta. that were calculated by the following
expressions using the measured retardation.
.alpha.=(retardation at 449.9 nm)/(retardation at 548.5 nm)
.beta.=(retardation at 650.2 nm)/(retardation at 548.5 nm)
[0265] The value .alpha. is smaller than 1, and the value .beta. is
larger than 1 when ideal wideband wavelength dispersion (reverse
wavelength dispersion) is achieved. The value .alpha. and the value
.beta. are almost identical to each other when flat wavelength
dispersion is achieved. The value .alpha. is larger than 1, and the
value .beta. is smaller than 1 when normal dispersion is
achieved.
[0266] Flat wavelength dispersion in which the value .alpha. and
the value .beta. are almost identical to each other is preferable,
and reverse wavelength dispersion in which the value .alpha. is
smaller than 1, and the value .beta. is larger than 1, is
particularly preferable.
[0267] Table 2 shows the thickness (.mu.m) of the polymer film, the
retardation (Re) at a wavelength of 548.5 nm, and the values
.alpha. and .beta.. Note that "NA" in Table 2 means that the
corresponding value was not measured.
TABLE-US-00002 TABLE 2 Polymerizable Polymerizable Drying Alignment
treatment Polymerizable compound 1 compound 2 temperature
temperature composition Compound Ratio (%) Compound Ratio (%)
(.degree. C.) (.degree. C.) Example 2 1 Compound .alpha. 70
Compound 1 30 110 23 Reference 2 Compound .alpha. 100 -- -- 120 23
Example 1 Reference 2 Compound .alpha. 100 -- -- 110 23 Example 2
Comparative 3 Compound .alpha. 70 Compound 1r 30 70 23 Example 1
Comparative 4 Compound 1r 100 -- -- 80 23 Example 2 Thickness Re
State of film (.mu.m) (548.5 nm) .alpha. .beta. Example 2
Transparent 1.435 105.43 0.839 1.030 Reference Transparent 1.669
123.98 0.841 1.027 Example 1 Reference Cloudy NA NA NA NA Example 2
Comparative Transparent 1.533 155.66 1.022 0.985 Example 1
Comparative Transparent 1.479 222.9 1.086 0.970 Example 2
[0268] The following were confirmed from the results shown in Table
2.
[0269] The polymer obtained by polymerizing the compound .alpha.
had reverse wavelength dispersion in which the value .alpha. was
smaller than 1, and the value .beta. was larger than 1 (see the
results for the value .alpha. and the value .beta. of Reference
Example 1). The value .alpha. and the value .beta. of the polymer
(Example 2) obtained by polymerizing the mixture including the
compound .alpha. and the compound 1 were almost identical to those
of the polymer (Reference Example 1) obtained by polymerizing the
compound .alpha..
[0270] It was confirmed from the results of Reference Example 2
that the drying temperature can be reduced by producing a polymer
by polymerizing a mixture including the compound .alpha. and the
compound 1 (Example 2) as compared with the case of polymerizing
only the compound .alpha..
[0271] On the other hand, the polymer obtained by polymerizing the
compound 1r had normal dispersion (see the results for the value
.alpha. and the value .beta. of Comparative Example 2). The polymer
(Comparative Example 1) obtained by polymerizing the mixture
including the compound .alpha. and the compound 1r had normal
dispersion in which the value .alpha. was larger than 1, and the
value .beta. was smaller than 1. It was thus confirmed that a
polymer obtained by polymerizing the compound 1 of Example 1 has
the same wavelength dispersion as that of the polymer obtained by
polymerizing the compound .alpha..
[0272] Specifically, a polymer obtained by polymerizing the
compound 1 has reverse wavelength dispersion, and the compound 1 is
useful as a raw material for producing a polymer having wavelength
dispersion. Since the drying temperature employed when forming a
liquid crystal layer can be reduced while maintaining the reverse
wavelength dispersion, it is possible to improve the energy
efficiency, and reduce the cost required to produce a liquid
crystal polymer film.
* * * * *