U.S. patent application number 15/358732 was filed with the patent office on 2017-05-25 for liquid crystal composition.
The applicant listed for this patent is Sumitomo Chemical Company, Limited. Invention is credited to Noriyuki HIDA, Haruki OKAWA.
Application Number | 20170145312 15/358732 |
Document ID | / |
Family ID | 58719586 |
Filed Date | 2017-05-25 |
United States Patent
Application |
20170145312 |
Kind Code |
A1 |
HIDA; Noriyuki ; et
al. |
May 25, 2017 |
LIQUID CRYSTAL COMPOSITION
Abstract
A liquid crystal composition is provided containing a first
liquid crystal compound represented by formula (1): ##STR00001##
and a second liquid crystal compound represented by formula (2):
##STR00002## Also provided is a method for producing the liquid
crystal composition having a desired wavelength dispersion
characteristic.
Inventors: |
HIDA; Noriyuki; (Osaka,
JP) ; OKAWA; Haruki; (Niihama-shi, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Sumitomo Chemical Company, Limited |
Tokyo |
|
JP |
|
|
Family ID: |
58719586 |
Appl. No.: |
15/358732 |
Filed: |
November 22, 2016 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C09K 19/34 20130101;
C09K 2219/03 20130101; C08F 222/24 20130101; H01L 51/5281 20130101;
H01L 51/0076 20130101; G02B 5/3016 20130101; H01L 27/3232 20130101;
H01L 51/0073 20130101; C09D 133/14 20130101; H01L 51/004 20130101;
C09K 2019/0448 20130101; H01L 51/0071 20130101; C09K 19/3861
20130101 |
International
Class: |
C09K 19/38 20060101
C09K019/38; H01L 51/52 20060101 H01L051/52; G02B 5/30 20060101
G02B005/30; H01L 27/32 20060101 H01L027/32; C08F 222/24 20060101
C08F222/24; H01L 51/00 20060101 H01L051/00 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 25, 2015 |
JP |
2015-230054 |
Claims
1. A liquid crystal compound comprising a first liquid crystal
compound represented by formula (1) and a second liquid crystal
compound represented by formula (2): ##STR00300## wherein Ar is a
divalent aromatic group, and at least one atom selected from the
group consisting of a nitrogen atom, an oxygen atom and a sulfur
atom may be contained in the aromatic group; G represents a
divalent alicyclic hydrocarbon group, where a hydrogen atom
contained in the alicyclic hydrocarbon group is optionally
substituted with a halogen atom, an alkyl group having 1 to 4
carbon atoms, a fluoro alkyl group having 1 to 4 carbon atoms, an
alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro
group, and --CH.sub.2-- contained in the alicyclic hydrocarbon
group is optionally substituted with --O--, --S-- or --NH--; B
represents a single bond or a divalent linking group; A represents
a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms
or a divalent aromatic hydrocarbon group having 6 to 20 carbon
atoms, the hydrogen atom contained in the alicyclic hydrocarbon
group and the aromatic hydrocarbon group is optionally substituted
with an alkyl group having 1 to 4 carbon atoms optionally
substituted with a halogen atom, an alkoxy group having 1 to 4
carbon atoms optionally substituted with a fluorine atom, a cyano
group or a nitro group, --CH.sub.2-- contained in the alicyclic
hydrocarbon group is optionally substituted with --O--, --S--, or
--NR.sup.1--, and --CH(-)-contained in the alicyclic hydrocarbon
group is optionally substituted with --N(-)-; R.sup.1 represents a
hydrogen atom or an alkyl group having 1 to 4 carbon atoms; k
represents an integer of 0 to 3, where when k is an integer of 2 or
more, a plurality of As and Bs may be the same or different from
each other, E represents an alkanediyl group having 1 to 17 carbon
atoms, where the hydrogen atom contained in an alkanediyl group is
optionally substituted with a halogen atom, and --CH.sub.2--
contained in the alkanediyl group is optionally substituted with
--O-- or --CO--; and P represents a polymerizable group.
2. The liquid crystal composition according to claim 1, wherein G,
A, B, E, P and k in the formula (1) are the same as G, A, B, E, P
and k in the formula (2), respectively.
3. The liquid crystal composition according to claim 1, wherein an
optical film obtained by orienting the first liquid crystal
compound exhibits a reverse wavelength dispersion
characteristic.
4. The liquid crystal composition according to claim 1, wherein an
optical film obtained by orienting the second liquid crystal
compound exhibits a positive wavelength dispersion
characteristic.
5. The liquid crystal composition according to claim 1, wherein the
aromatic group in Ar has 10 to 30 n electrons.
6. The liquid crystal composition according to claim 1, wherein a
maximum absorption wavelength (.lamda..sub.max) of the first liquid
crystal compound is from 300 to 400 nm.
7. The liquid crystal composition according to claim 1, wherein an
optical film obtained by orienting the liquid crystal composition
has a degree of wavelength dispersion Re(450 nm)/Re(550 nm) of 0.65
or more and less than 1.
8. The liquid crystal composition according to claim 1, wherein Ar
is an aromatic group having a heterocyclic ring.
9. The liquid crystal composition according to claim 8, wherein the
aromatic group having a heterocyclic ring is an aromatic group
having a benzothiazole ring.
10. The liquid crystal composition according to claim 1, wherein a
content of the second liquid crystal compound in the liquid crystal
composition is in a range of 0.1 to 70 parts by mass relative to
100 parts by mass of the first liquid crystal compound.
11. An optical film comprising a polymer of the liquid crystal
composition as defined in claim 1.
12. The optical film according to claim 11, wherein a retardation
value (Re(550)) of the optical film at a wavelength of 550 nm is
from 113 to 163 nm.
13. A circularly polarizing plate comprising the optical film as
defined in claim 11 and a polarizing film.
14. An organic electro-luminescence (EL) display device comprising
an organic electro-luminescence panel containing the circularly
polarizing plate as defined in claim 13.
15. A method for producing a liquid crystal composition comprising
a first liquid crystal compound represented by formula (1):
##STR00301## and a second liquid crystal compound represented by
formula (2): ##STR00302## the method comprising a step of allowing
a first alcohol compound represented by formula (3): P-E B-A
.sub.kOH (3) and a dicarboxylic acid compound represented by
formula (4): ##STR00303## to react with each other to thereby
obtain a mixture containing a carboxylic acid compound represented
by formula (5): ##STR00304## and the second liquid crystal
compound.
16. The method according to claim 15, comprising a step of allowing
the mixture containing the carboxylic acid compound and the second
liquid crystal compound to react with a second alcohol compound (6)
represented by formula (6): HO--Ar--OH (6) to thereby obtain a
liquid crystal composition containing the first and second liquid
crystal compounds.
17. The method according to claim 15, wherein an amount of the
dicarboxylic acid compound used is from 1 to 50 moles, relative to
1 mole of the first alcohol compound.
18. The method according to claim 15, wherein a reaction of the
first alcohol compound and the dicarboxylic acid compound, and/or a
reaction of the mixture containing the carboxylic acid compound and
the second liquid crystal compound with the second alcohol compound
is/are conducted in the presence of a condensing agent.
Description
BACKGROUND OF THE INVENTION
[0001] Field of the Invention
[0002] The present invention relates to a liquid crystal
composition, an optical film, and a method for producing the
optical film.
[0003] Description of the Related Art
[0004] A flat panel display device (FPD) includes a member using an
optical film such as a polarizing plate and a retardation plate.
Examples of the optical film include an optical film obtained by
applying to a supporting substrate a solution which is prepared by
dissolving a polymerizable compound in a solvent, followed by
polymerization. It is known that the retardation (Re(.lamda.)) of
the optical film which light having a wavelength of .lamda. nm
generates is determined by the product of a birefringence index
.DELTA.n and a film thickness d (Re(.lamda.)=.DELTA.n.times.d).
Furthermore, it is known that the wavelength dispersion
characteristic is usually expressed as the value
(Re(.lamda.)/Re(550)) obtained by dividing the retardation value
Re(.lamda.) at a wavelength .lamda. by the retardation value Re
(550) at 550 nm, and that uniform conversion of polarized light is
possible over the wavelength band where the quotient of
(Re(.lamda.)/Re (550)) is near 1 or over the wavelength band which
exhibits a reverse wavelength dispersion characteristic satisfying
the following relations: [Re 450)/Re(550)]<1 and
[Re(650)/Re(550)]>1.
[0005] For example, LC242 (manufactured by BASF A.G.) is
commercially available as the polymerizable compound (Non Patent
Literature 1).
PRIOR ART DOCUMENTS
Non Patent Literature
[0006] Non Patent Literature 1: Cordula Mock-Knoblauch, Olivier S.
Enger, Ulrich D. Schalkowsky, "L-7 Novel Polymerisable Liquid
Crystalline Acrylates fortheManufacturingofUltrathinOptical Films",
SID Symposium Digest of Technical Papers, 2006, vol. 37, p.
1673
SUMMARY OF THE INVENTION
Problems to be Solved
[0007] The wavelength dispersion characteristic of the optical film
varies depending on the compounds which compose the film.
Therefore, in order to produce an optical film having a desired
wavelength dispersion characteristic, it is necessary to synthesize
a compound which yields the desired wavelength dispersion
characteristic. However, synthesis of a compound often involves too
much labor and requires repeated experiments. Furthermore, even if
the synthesis is repeatedly conducted, such desirable compound may
not be obtained in some cases. Therefore, it is not economically or
technically easy to produce a film having a desired wavelength
dispersion characteristic.
[0008] An object of the present invention is to provide a liquid
crystal composition which yields a desired wavelength dispersion
characteristic. Another object of the present invention is to
provide a production method capable of easily producing such liquid
crystal composition.
Means for Solving the Problem
[0009] The present invention provides the following preferred
embodiments [1] to [18].
[1] A liquid crystal compound containing a liquid crystal compound
(1) represented by formula (1) and a liquid crystal compound (2)
represented by formula (2).
##STR00003##
[wherein Ar is a divalent aromatic group, and at least one atom
selected from the group consisting of a nitrogen atom, an oxygen
atom and a sulfur atom may be contained in the aromatic group;
[0010] G represents a divalent alicyclic hydrocarbon group, where a
hydrogen atom contained in the alicyclic hydrocarbon group is
optionally substituted with a halogen atom, an alkyl group having 1
to 4 carbon atoms, a fluoro alkyl group having 1 to 4 carbon atoms,
an alkoxy group having 1 to 4 carbon atoms, a cyano group or a
nitro group, and --CH.sub.2-- contained in the alicyclic
hydrocarbon group is optionally substituted with --O--, --S-- or
--NH--;
[0011] B represents a single bond or a divalent linking group;
[0012] A represents a divalent alicyclic hydrocarbon group having 3
to 20 carbon atoms or a divalent aromatic hydrocarbon group having
6 to 20 carbon atoms, the hydrogen atom contained in the alicyclic
hydrocarbon group and the aromatic hydrocarbon group is optionally
substituted with an alkyl group having 1 to 4 carbon atoms
optionally substituted with a halogen atom, an alkoxy group having
1 to 4 carbon atoms optionally substituted with a fluorine atom, a
cyano group or a nitro group, --CH.sub.2-- contained in the
alicyclic hydrocarbon group is optionally substituted with --O--,
--S--, or --NR.sup.1--, and --CH(-)-contained in the alicyclic
hydrocarbon group may be substituted with --N(-)-;
[0013] R.sup.1 represents a hydrogen atom or an alkyl group having
1 to 4 carbon atoms;
[0014] k represents an integer of 0 to 3, where when k is an
integer of 2 or more, a plurality of As and Bs may be the same or
different from each other;
[0015] E represents an alkanediyl group having 1 to 17 carbon
atoms, where the hydrogen atom contained in an alkanediyl group is
optionally substituted with a halogen atom, and --CH-- contained in
the alkanediyl group is optionally substituted with --O-- or
--CO--; and
[0016] P represents a polymerizable group.]
[2] The liquid crystal composition according to [1], in which G, A,
B, E, P and k in the formula (1) are the same as G, A, B, E, P and
k in the formula (2), respectively. [3] The liquid crystal
composition according to [1] or [2], in which the optical film
obtained by orienting the liquid crystal compound (i) exhibits a
reverse wavelength dispersion characteristic. [4] The liquid
crystal composition according to any of [1] to [3], in which the
optical film obtained by orienting the liquid crystal compound (2)
exhibits a positive wavelength dispersion characteristic. [5] The
liquid crystal composition according to any of [1] to [4], in which
the aromatic group in Ar has 10 to 30 .pi. electrons. [6] The
liquid crystal composition according to any of [1] to [5], in which
the maximum absorption wavelength (.lamda..sub.max) of the liquid
crystal compound (1) is from 300 to 400 nm. [7] The liquid crystal
composition according to any of [1] to [6], in which the optical
film obtained by orienting the liquid crystal composition has a
degree of wavelength dispersion Re (450 nm)/Re(550 nm) of 0.65 or
more and less than 1. [8] The liquid crystal composition according
to any of [1] to [7], in which Ar is an aromatic group having a
heterocyclic ring. [9] The liquid crystal composition according to
[8], in which the aromatic group having a heterocyclic ring is an
aromatic group having a benzothiazole ring. [10] The liquid crystal
composition according to any of [1] to [9], in which the content of
the liquid crystal compound (2) in the liquid crystal composition
is in the range of 0.1 to 70 parts by mass relative to 100 parts by
mass of the liquid crystal compound (1). [11] An optical film
comprising a polymer of the liquid crystal composition as defined
in any of [1] to [10]. [12] The optical film according to (11), in
which the retardation value (Re(550)) at a wavelength of 550 nm is
from 113 to 163 nm. [13] A circularly polarizing plate comprising
the optical film as defined in [11] or [12] and a polarizing film.
[14] An organic electro-luminescence (EL) display device comprising
an organic electro-luminescence panel containing the circularly
polarizing plate as defined in [13]. [15] A method for producing a
liquid crystal composition comprising a liquid crystal compound (1)
represented by formula (1):
##STR00004##
and a liquid crystal compound (2) represented by formula (2):
##STR00005##
including a step of allowing an alcohol compound (3) represented by
formula (3):
[Chem. 4]
P-E B-A .sub.kOH (3)
and a dicarboxylic acid compound (4) represented by formula
(4):
##STR00006##
to react each other to thereby obtain a mixture containing a
carboxylic acid compound (5) represented by formula (5):
##STR00007##
and the liquid crystal compound (2). [16] The method according to
[15], including a step of allowing the mixture containing the
carboxylic acid compound (5) and the liquid crystal compound (2) to
react with an alcohol compound (6) represented by formula (6):
[Chem. 7]
HO--Ar--OH (6)
to thereby obtain a liquid crystal composition containing liquid
crystal compounds (1) and (2). [17] The method according to [15] or
[16], in which the amount of dicarboxylic acid compound (4) used is
from 1 to 50 moles, relative to 1 mole of the alcohol compound (3).
[18] The method according to any of [15] to [17], in which a
reaction of the alcohol compound (3) and the dicarboxylic acid
compound (4), and/or a reaction of the mixture containing the
carboxylic acid compound (5) and the liquid crystal compound (2)
with the alcohol compound (6) is/are conducted in the presence of a
condensing agent.
Effect of the Invention
[0017] According to the present invention, it is possible to
provide a liquid crystal composition which yields a desired
wavelength dispersion characteristic. Further, according to the
present invention, it is possible to provide a production method
capable of easily producing such liquid crystal composition.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
<Liquid Crystal Compound>
[0018] The liquid crystal composition of the present invention
contains a liquid crystal compound (1) represented by formula
(1):
##STR00008##
and a liquid crystal compound (2) represented by formula (2):
##STR00009##
[0019] In formulae (1) and (2), Ar is a divalent aromatic group,
and at least one atom selected from the group consisting of a
nitrogen atom, an oxygen atom and a sulfur atom can be contained in
the aromatic group.
[0020] G represents a divalent alicyclic hydrocarbon group, where a
hydrogen atom contained in the alicyclic hydrocarbon group is
optionally substituted with a halogen atom, an alkyl group having 1
to 4 carbon atoms, a fluoro alkyl group having 1 to 4 carbon atoms,
an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a
nitro group, and --CH.sub.2-- (methylene group) contained in the
alicyclic hydrocarbon group is optionally substituted with --O--,
--S--, or --NH--.
[0021] B represents a single bond or a divalent linking group.
[0022] A represents a divalent alicyclic hydrocarbon group having 3
to 20 carbon atoms or a divalent aromatic hydrocarbon group having
6 to 20 carbon atoms; the hydrogen atom contained in the alicyclic
hydrocarbon group and the aromatic hydrocarbon group is optionally
substituted with an alkyl group having 1 to 4 carbon atoms
optionally substituted with a halogen atom, an alkoxy group having
1 to 4 carbon atoms optionally substituted with a fluorine atom, a
cyano group or a nitro group; and --CH.sub.2-- contained in the
alicyclic hydrocarbon group is optionally substituted with --O--,
--S--, or --NR.sup.1--. The group --CH(-)-contained in the
alicyclic hydrocarbon group may be substituted with --N(-)- (amino
group).
[0023] R.sup.1 represents a hydrogen atom or an alkyl group having
1 to 4 carbon atoms.
[0024] k represents an integer of 0 to 3, where when k is an
integer of 2 or more, a plurality of As and Bs may be the same or
different from each other.
[0025] E represents an alkanediyl group having 1 to 17 carbon
atoms, where the hydrogen atom contained in an alkanediyl group is
optionally substituted with a halogen atom, and --CH.sub.2--
contained in the alkanediyl group is optionally substituted with
--O-- or --CO--.
[0026] P represents a polymerizable group.
[0027] The divalent aromatic group represented by Ar herein refers
to a divalent group which has at least one aromatic ring like the
example to be described later. Examples of the divalent group may
has a substituent. Examples of the substituent include the groups
or atoms to be described later.
[0028] In formula (1), the divalent aromatic group represented by
Ar preferably contains at least one atom selected from the group
consisting of a nitrogen atom, an oxygen atom, and a sulfur atom.
This means that these hetero atoms are contained in Ar, and Ar may
or may not have a heterocyclic ring. The divalent aromatic group
represented by Ar is preferably an aromatic group having a
heterocyclic ring, from the viewpoint of exhibiting a reverse
wavelength dispersion characteristic. The aromatic group having a
heterocyclic ring implies that the divalent group to be bonded to
two oxygen atom (--O--) bonding to Ar of the liquid crystal
compound may be a heterocyclic ring and the substituent of the
divalent group may be a heterocyclic ring. Examples of the
heterocyclic ring include a furan ring, a benzofuran ring, a
pyrrole ring, a thiophene ring, a pyridine ring, a thiazole ring, a
benzothiazole ring, and a phenanthroline ring. That is, examples of
the aromatic group having a heterocyclic ring include a compound in
which the divalent group to be bonded to two oxygen atom (--O--)
bonding to Ar of the liquid crystal compound is the above-mentioned
heterocyclic ring, and a compound in which the substituent of the
divalent group is the above-mentioned heterocyclic ring. Of these
compounds, the aromatic group having a heterocyclic ring is more
preferably an aromatic group having a thiazole ring and a
benzothiazole ring, and even more preferably an aromatic group
having a benzothiazole ring. Further, of these compounds, the
divalent group to be bonded to two oxygen atom (--O--) bonding to
Ar of the liquid crystal compound is more preferably a thiazole
ring and a benzothiazole ring, and even more preferably a
benzothiazole ring.
[0029] When the aromatic ring in Ar has a nitrogen atom, the
nitrogen atom contained in the aromatic ring in Ar preferably has a
.pi. electron.
[0030] When Ar is a divalent aromatic group having a heterocyclic
ring as an aromatic ring, Ar may bond to the one of or both two
oxygen atoms (--O--) bonding to Ar via the heterocyclic ring or may
bond to the one of or both two oxygen atoms (--O--) bonding to Ar
via an atom other than the atom comprising the heterocyclic
ring.
[0031] A total number N.sub..pi. of then electron contained in the
aromatic ring in Ar is preferably 10 or more, more preferably 12 or
more, and even more preferably 14 or more; preferably 30 or less,
and more preferably 25 or less, from the viewpoint of exhibiting a
reverse wavelength dispersion characteristic.
[0032] Examples of the divalent group in Ar to be bonded to two
oxygen atom (--O--) bonding to Ar of the liquid crystal compound
include the following groups represented by formulae (Ar-1) to
(Ar-22).
##STR00010## ##STR00011## ##STR00012## ##STR00013##
[0033] [In formulae (Ar-1) to (Ar-22), * represents a linking unit,
Z.sup.0, Z.sup.1, and Z.sup.2 each independently represent a
hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon
atoms, a cyano group, a nitro group, an alkylsulfinyl group having
1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon
atoms, a carboxyl group, a fluoroalkyl group having 1 to 6 carbon
atoms, an alkoxy group having 1 to 6 carbon atoms, a fluoroalkyl
group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6
carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an
N-alkylamino group having 1 to 6 carbon atoms, an N,N-dialkylamino
group having 2 to 12 carbon atoms, an N-alkylsulfamoyl group having
1 to 6 carbon atoms, or an N,N-dialkylsulfamoyl group having 2 to
12 carbon atoms.
[0034] Q.sup.1, Q.sup.2, and Q.sup.3 each independently represent
--CR.sup.2R.sup.3--, --S--, --NR.sup.2--, --CO--, or --O--.
[0035] R.sup.2 and R.sup.3 each independently represent a hydrogen
atom or an alkyl group having 1 to 4 carbon atoms.
[0036] Y.sup.1, Y.sup.2, and Y.sup.3 each independently represent
an aromatic hydrocarbon group or an aromatic heterocyclic group,
which is optionally substituted.
[0037] W.sup.1 and W.sup.2 each independently represent a hydrogen
atom, a cyano group, a methyl group, or a halogen atom.
[0038] m represents an integer of 0 to 6.]
[0039] Examples of the halogen atom include a fluorine atom, a
chlorine atom, a bromine atom, and an iodine atom. Of these, a
fluorine atom, a chlorine atom, or a bromine atom is
preferable.
[0040] Examples of the alkyl group having 1 to 6 carbon atoms
include a methyl group, an ethyl group, a propyl group, an
isopropyl group, a butyl group, an isobutyl group, sec-butyl group,
tert-butyl group, a pentyl group, and a hexyl group. Of these, an
alkyl group having 1 to 4 carbon atoms is preferable, an alkyl
group having 1 to 2 carbon atoms is more preferable, and a methyl
group is especially preferable.
[0041] Examples of the alkylsulfinyl group having 1 to 6 carbon
atoms include a methyl sulfinyl group, an ethyl sulfinyl group, a
propyl sulfinyl group, an isopropyl sulfinyl group, a butyl
sulfinyl group, an iso-butyl sulfinyl group, a sec-butyl sulfinyl
group, a tert-butyl sulfinyl group, a pentyl sulfinyl group, and a
hexyl sulfinyl group. Of these, an alkylsulfinyl group having 1 to
4 carbon atoms is preferable, an alkylsulfinyl group having 1 or 2
carbon atoms is more preferable, and a methylsulfinyl group is
especially preferable.
[0042] Examples of the alkylsulfonyl group having 1 to 6 carbon
atoms include a methylsulfonyl group, an ethylsulfonyl group, a
propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl
group, an isobutylsulfonyl group, a sec-butylsulfonyl group, a
tert-butylsulfonyl group, a pentyl sulfonyl group, and a hexyl
sulfonyl group. Of these, an alkylsulfonyl group having 1 to 4
carbon atoms is preferable, an alkylsulfonyl group having 1 to 2
carbon atoms is more preferable, and a methylsulfonyl group is
especially preferable.
[0043] Examples of the fluoroalkyl group having 1 to 6 carbon atoms
include a fluoromethyl group, a trifluoromethyl group, a
fluoroethyl group, a pentafluoroethyl group, a heptafluoropropyl
group, and a nonafluorobutyl group. Of these, a fluoroalkyl group
having 1 to 4 carbon atoms is preferable, a fluoroalkyl group
having 1 to 2 carbon atoms is more preferable, and a
trifluoromethyl group is especially preferable.
[0044] Examples of the alkoxy group having 1 to 6 carbon atoms
include a methoxy group, an ethoxy group, a propoxy group, an
isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy
group, a tert-butoxy group, a pentyloxy group, and a hexyloxy
group. Of these, an alkoxy group having 1 to 4 carbon atoms is
preferable, an alkoxy group having 1 to 2 carbon atoms is more
preferable, and a methoxy group is especially preferable.
[0045] Examples of the alkylthio group having 1 to 6 carbon atoms
include a methylthio group, an ethylthio group, a propylthio group,
an isopropylthio group, a butylthio group, an isobutylthio group, a
sec-butylthio group, a tert-butylthio group, a pentylthio group,
and a hexylthio group. Of these, an alkylthio group having 1 to 4
carbon atoms is preferable, an alkylthio group having 1 to 2 carbon
atoms is more preferable, and a methylthio group is especially
preferable.
[0046] Examples of the N-alkylamino group having 1 to 6 carbon
atoms include an N-methylamino group, an N-ethylamino group, an
N-propylamino group, an N-isopropylamino group, an N-butylamino
group, an N-isobutylamino group, an N-sec-butylamino group, an
N-tert-butylamino group, an N-pentylamino group, and an
N-hexylamino group. Of these, an N-alkylamino group having 1 to 4
carbon atoms is preferable, N-alkylamino group having 1 to 2 carbon
atoms is more preferable, and an N-methylamino group is especially
preferable.
[0047] Examples of the N,N-dialkylamino group having 2 to 12 carbon
atoms include an N,N-dimethylamino group, an N-methyl-N-ethylamino
group, an N,N-diethylamino group, an N,N-dipropylamino group, an
N,N-diisopropylamino group, an N,N-dibutylamino group, an
N,N-diisobutylamino group, an N,N-dipentylamino group, and an
N,N-dihexylamino group. Of these, an N,N-dialkylamino group having
2 to 8 carbon atoms is preferable, an N, N-dialkylamino group
having 2 to 4 carbon atoms is more preferable, and an
N,N-dimethylamino group is especially preferable.
[0048] Examples of the N-alkylsulfamoyl group having 1 to 6 carbon
atoms include an N-methylsulfamoyl group, an N-ethylsulfamoyl
group, an N-propylsulfamoyl group, an N-isopropylsulfamoyl group,
an N-butylsulfamoyl group, an N-isobutyl sulfamoyl group, an
N-sec-butylsulfamoyl group, an N-tert-butylsulfamoyl group, an
N-pentylsulfamoyl group, and N-hexylsulfamoyl group. Of these, an
N-alkylsulfamoyl group having 1 to 4 carbon atoms is preferable, an
N-alkylsulfamoyl group having 1 to 2 carbon atoms is more
preferable, and an N-methylsulfamoyl group is especially
preferable.
[0049] Examples of the N,N-dialkylsulfamoyl group having 2 to 12
carbon atoms include an N,N-dimethylsulfamoyl group, an
N-methyl-N-ethylsulfamoyl group, an N, N-diethylsulfamoyl group, an
N,N-dipropylsulfamoyl group, an N,N-diisopropylsulfamoyl group, an
N,N-dibutylsulfamoyl group, an N,N-diisobutylsulfamoyl group, an
N,N-dipentylsulfamoyl group, and an N,N-dihexylsulfamoyl group. Of
these, an N,N-dialkylsulfamoyl group having 2 to 8 carbon atoms is
preferable, an N,N-dialkylsulfamoyl group having 2 to 4 carbon
atoms is more preferable, and an N,N-dimethylsulfamoyl group is
especially preferable.
[0050] It is preferable that Z.sup.0, Z.sup.1, and Z.sup.7 are each
independently a hydrogen atom, a halogen atom, a methyl group, a
cyano group, a nitro group, a carboxyl group, a methylsulfonyl
group, a trifluoromethyl group, a methoxy group, a methylthio
group, an N-methylamino group, an N,N-dimethylamino group, an
N-methylsulfamoyl group, or a N,N-dimethylsulfamoyl group.
[0051] Examples of the alkyl group having 1 to 4 carbon atoms in
R.sup.1 and R.sup.3 include a methyl group, an ethyl group, a
propyl group, an isopropyl group, a butyl group, an isobutyl group,
and a tert-butyl group. Of these, an alkyl group having 1 to 2
carbon atoms is preferable, and a methyl group is more
preferable.
[0052] Q.sup.1 and Q.sup.2 are each independently preferably --S--,
--CO--, --NH--, or --N(CH.sub.3)--, and Q.sup.3 is preferably --S--
or --CO--.
[0053] Examples of the aromatic hydrocarbon group in Y.sup.1,
Y.sup.2, and Y.sup.3 include an aromatic hydrocarbon group having 6
to 20 carbon atoms such as a phenyl group, a naphthyl group, an
anthryl group, a phenanthryl group, and a biphenyl group. Of these,
a phenyl group and a naphthyl group are preferable, and a phenyl
group is more preferable. The aromatic heterocyclic group contains
at least one of hetero atoms such as nitrogen atom, oxygen atom,
and sulfur atom, including a furyl group, a pyrrolyl group, a
thienyl group, a pyridinyl group, a thiazolyl group, and a
benzothiazolyl group. Examples thereof include aromatic
heterocyclic group having 4 to 20 carbon atoms, and a furyl group,
a pyrrolyl group, a thienyl group, a pyridinyl group, and a
thiazolyl group are preferable.
[0054] The aromatic hydrocarbon group and the aromatic heterocyclic
group optionally have at least one substituent, and examples of the
substituent include a halogen atom, an alkyl group having 1 to 6
carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group
having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6
carbon atoms, a carboxyl group, a fluoroalkyl group having 1 to 6
carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an
alkylthio group having 1 to 6 carbon atoms, an N-alkylamino group
having 1 to 6 carbon atoms, an N,N-dialkylamino group having 2 to
12 carbon atoms, an N-alkylsulfamoyl group having 1 to 6 carbon
atoms, and an N, N-dialkylsulfamoyl group having 2 to 12 carbon
atoms. Of these, a halogen atom, an alkyl group having 1 to 2
carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group
having 1 to 2 carbon atoms, a fluoroalkyl group having 1 to 2
carbon atoms, an alkoxy group having 1 to 2 carbon atoms, an
alkylthio group having 1 to 2 carbon atoms, an N-alkylamino group
having 1 to 2 carbon atoms, an N,N-dialkylamino group having 2 to 4
carbon atoms, and an N-alkylsulfamoyl group having 1 to 2 carbon
atoms are preferable.
[0055] Examples of the halogen atom, alkyl group having 1 to 6
carbon atoms, cyano group, nitro group, alkylsulfinyl group having
1 to 6 carbon atoms, alkylsulfonyl group having 1 to 6 carbon
atoms, carboxyl group, fluoroalkyl group having 1 to 6 carbon
atoms, alkoxy group having 1 to 6 carbon atoms, alkylthio group
having 1 to 6 carbon atoms, N-alkylamino group having 1 to 6 carbon
atoms, N,N-dialkylamino group having 2 to 12 carbon atoms,
N-alkylsulfamoyl group having 1 to 6 carbon atoms, and
N,N-dialkylsulfamoyl group having 2 to 12 carbon atoms include the
same groups as those described above.
[0056] In formula (Ar-14), Y.sup.1 may form an aromatic
heterocyclic group together with the nitrogen atom to which Y.sup.1
bonds and Z.sup.0. Examples of the aromatic heterocyclic group
include a pyrrole ring, an imidazole ring, a pyridine ring, a
pyrimidine ring, an indole ring, a quinoline ring, an isoquinoline
ring, a purine ring, a pyrrolidine ring, and a piperidine ring.
Such aromatic heterocyclic group optionally has a substituent.
Further, Y.sup.1 may be a polycyclic aromatic hydrocarbon group or
a polycyclic aromatic heterocyclic group which is optionally
substituted, to be described later, together with the nitrogen atom
to which Y.sup.1 bonds, and Z.sup.0.
[0057] Y.sup.1, Y.sup.2, and Y.sup.3 may be each independently a
polycyclic aromatic hydrocarbon group or a polycyclic aromatic
heterocyclic group which is optionally substituted. The polycyclic
aromatic hydrocarbon group refers to a group derived from a fused
polycyclic aromatic hydrocarbon group or an aromatic ring assembly.
The polycyclic aromatic heterocyclic group refers to a group
derived from a fused polycyclic aromatic heterocyclic group or an
aromatic ring assembly. For example, Y.sup.1, Y.sup.2 and Y.sup.3
are each independently preferably any of the groups represented by
formulae (Y.sup.1-1) to (Y.sup.1-7), and more preferably any of the
groups represented by formulae (Y.sup.1-1) to (Y.sup.1-4).
##STR00014##
[0058] [In formulae (Y.sup.1-1) to (Y.sup.1-7), * represents a
linking unit, and Z.sup.3 independently represents a halogen atom,
an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro
group, a nitroxide group, a sulfone group, a sulfoxide group, a
carboxyl group, a fluoroalkyl group having 1 to 6 carbon atoms, an
alkoxy group having 1 to 6 carbon atoms, a thioalkyl group having 1
to 6 carbon atoms, an N, N-dialkylamino group having 2 to 8 carbon
atoms, or an N-alkylamino group having 1 to 4 carbon atoms.
[0059] V.sup.1 and V.sup.2 each independently represent --CO--,
--S--, --NR.sup.4--, --O--, --Se-- or --SO.sub.2--.
[0060] W.sup.1 to W.sup.5 each independently represent --C.dbd. or
--N.dbd., where at least one of V.sup.2, V.sup.2, and W.sup.1 to
W.sup.5 represents a group containing S, N, O or Se.
[0061] R.sup.4 represents a hydrogen atom or an alkyl group having
1 to 4 carbon atoms.
[0062] a independently represents an integer of 0 to 3.
[0063] b independently represents an integer of 0 to 2.
[0064] Any of the groups represented by formulae (Y.sup.1-1) to
(Y.sup.1-7) is preferably any of the groups represented by formulae
(Y.sup.2-1) to (Y.sup.2-16), and more preferably any of the groups
represented by formulae (Y.sup.3-1) to (Y.sup.3-6), and especially
preferably the group represented by formula (Y.sup.3-1) or formula
(Y.sup.3-3).
##STR00015## ##STR00016##
[0065] [In formulae (Y.sup.2-1) to (Y.sup.2-16), Z.sup.3, a, b,
V.sup.1, V.sup.2 and W.sup.1 to W.sup.5 are the same as defined
above.]
##STR00017##
[0066] [In formulae (Y.sup.3-1) to (Y.sup.3-6), Z.sup.3, a, b,
V.sup.1, V.sup.2 and W.sup.1 are the same as defined above.]
[0067] Examples of Z.sup.3 include a halogen atom, an alkyl group
having 1 to 6 carbon atoms, a cyano group, a nitro group, an
alkylsulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl
group having 1 to 6 carbon atoms, a carboxyl group, a fluoroalkyl
group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6
carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an
N-alkylamino group having 1 to 6 carbon atoms, an N,N-dialkylamino
group having 2 to 12 carbon atoms, an N-alkylsulfamoyl group having
1 to 6 carbon atoms, and an N,N-dialkylsulfamoyl group having 2 to
12 carbon atoms. Of these, a halogen atom, a methyl group, an ethyl
group, an isopropyl group, a sec-butyl group, a cyano group, a
nitro group, a sulfone group, a nitroxide group, a carboxyl group,
a trifluoromethyl group, a methoxy group, a thiomethyl group, an
N,N-dimethylamino group, and an N-methylamino group are preferable;
a halogen atom, a methyl group, an ethyl group, an isopropyl group,
a sec-butyl group, a cyano group, a nitro group, a trifluoromethyl
group are more preferable; and a methyl group, an ethyl group, an
isopropyl group, a sec-butyl group, a pentyl group, and a hexyl
group are especially preferable.
[0068] Examples of the halogen atom, alkyl group having 1 to 6
carbon atoms, alkylsulfinyl group having 1 to 6 carbon atoms,
alkylsulfonyl group having 1 to 6 carbon atoms, fluoroalkyl group
having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon
atoms, alkylthio group having 1 to 6 carbon atoms, N-alkylamino
group having 1 to 6 carbon atoms, N,N-dialkylamino group having 2
to 12 carbon atoms, N-alkylsulfamoyl group having 1 to 6 carbon
atoms, and N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms
include the same groups as those described above.
[0069] It is preferable that V.sup.1 and V.sup.2 are each
independently --S--, --NR.sup.4-- or --O--.
[0070] It is preferable that W.sup.1 to W.sup.5 are each
independently --C-- or --N.dbd..
[0071] It is preferable that at least one of V.sup.1, V.sup.2, and
W.sup.1 to W.sup.5 represents a group containing S, N or O.
[0072] It is preferable that a is 0 or 1. It is preferable that b
is 0.
[0073] Specific examples of Y.sup.1 to Y.sup.3 include the groups
represented by formulae (ar-1) to (ar-840).
##STR00018## ##STR00019## ##STR00020## ##STR00021## ##STR00022##
##STR00023## ##STR00024## ##STR00025## ##STR00026## ##STR00027##
##STR00028## ##STR00029## ##STR00030## ##STR00031## ##STR00032##
##STR00033## ##STR00034## ##STR00035## ##STR00036## ##STR00037##
##STR00038## ##STR00039## ##STR00040## ##STR00041## ##STR00042##
##STR00043## ##STR00044## ##STR00045## ##STR00046## ##STR00047##
##STR00048## ##STR00049## ##STR00050## ##STR00051## ##STR00052##
##STR00053## ##STR00054## ##STR00055## ##STR00056## ##STR00057##
##STR00058## ##STR00059## ##STR00060##
##STR00061## ##STR00062## ##STR00063## ##STR00064## ##STR00065##
##STR00066## ##STR00067## ##STR00068## ##STR00069## ##STR00070##
##STR00071## ##STR00072## ##STR00073## ##STR00074## ##STR00075##
##STR00076## ##STR00077## ##STR00078## ##STR00079## ##STR00080##
##STR00081## ##STR00082## ##STR00083## ##STR00084## ##STR00085##
##STR00086## ##STR00087## ##STR00088## ##STR00089## ##STR00090##
##STR00091## ##STR00092## ##STR00093## ##STR00094## ##STR00095##
##STR00096## ##STR00097## ##STR00098## ##STR00099## ##STR00100##
##STR00101## ##STR00102## ##STR00103## ##STR00104## ##STR00105##
##STR00106## ##STR00107## ##STR00108##
##STR00109## ##STR00110## ##STR00111## ##STR00112## ##STR00113##
##STR00114## ##STR00115## ##STR00116## ##STR00117## ##STR00118##
##STR00119## ##STR00120## ##STR00121## ##STR00122## ##STR00123##
##STR00124## ##STR00125## ##STR00126## ##STR00127## ##STR00128##
##STR00129## ##STR00130## ##STR00131## ##STR00132## ##STR00133##
##STR00134## ##STR00135## ##STR00136## ##STR00137## ##STR00138##
##STR00139## ##STR00140## ##STR00141## ##STR00142## ##STR00143##
##STR00144##
[0074] In formulae (1) and (2), G is a divalent alicyclic
hydrocarbon group, and the number of carbon atoms thereof is, for
example, from 3 to 30, preferably from 3 to 20, more preferably
from 4 to 15, and even more preferably from 5 to 10. Examples of
the divalent alicyclic hydrocarbon group include a cycloalkanediyl
group. The hydrogen atom contained in the alicyclic hydrocarbon
group is optionally substituted with a halogen atom, an alkyl group
having 1 to 4 carbon atoms, a fluoro alkyl group having 1 to 4
carbon atoms, an alkoxy group, a cyano group, or a nitro group
having 1 to 4 carbon atoms, and --CH.sub.2-(methylene group)
contained in the alicyclic hydrocarbon group is optionally
substituted with --O--, --S--, or --NH--.
[0075] Examples of the alkyl group having 1 to 4 carbon atoms
include a methyl group, an ethyl group, a propyl group, an
isopropyl group, a butyl group, an isobutyl group, a sec-butyl
group, and a tert-butyl group. Of these, an alkyl group having 1 to
3 carbon atoms is preferable, an alkyl group having 1 to 2 carbon
atoms is more preferable, and a methyl group is especially
preferable.
[0076] Examples of the fluoroalkyl group having 1 to 4 carbon atoms
include a fluoromethyl group, a trifluoromethyl group, a
fluoroethyl group, a pentafluoroethyl group, a heptafluoropropyl
group, and a nonafluorobutyl group. Of these, a fluoroalkyl group
having 1 to 3 carbon atoms is preferable, a fluoroalkyl group
having 1 to 2 carbon atoms is more preferable, and a
trifluoromethyl group is especially preferable.
[0077] Examples of the alkoxy group having 1 to 4 carbon atoms
include a methoxy group, an ethoxy group, a propoxy group, an
isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy
group, and a tert-butoxy group. Of these, an alkoxy group having 1
to 3 carbon atoms is preferable, an alkoxy group having 1 to 2
carbon atoms, and a methoxy group is especially preferable.
[0078] Examples of the divalent alicyclic hydrocarbon group include
the groups represented by formulae (g-1) to (g-4). Examples of the
divalent alicyclic hydrocarbon group in which --CH.sub.2--
contained in the alicyclic hydrocarbon group is replaced by --O--,
--S--, or --N(R.sup.5)-- include the groups represented by formulae
(g-5) to (g-8). R.sup.5 represents a hydrogen atom or an alkyl
group having 1 to 4 carbon atoms. Examples of the divalent
alicyclic hydrocarbon group in which the methine group (--CH(-)-)
contained in the alicyclic hydrocarbon group is replaced by an
amino group include the groups represented by formulae (g-9) to
(g-10). Of these, a 5- or 6-membered alicyclic hydrocarbon group is
preferable.
##STR00145##
[0079] The divalent alicyclic hydrocarbon group is preferably a
group represented by formula (g-1), more preferably a
1,4-cyclohexanediyl group, and especially preferably a
trans-1,4-cyclohexanediyl group.
[0080] In formulae (1) and (2), B is a single bond or a divalent
linking group. Examples of the divalent linking group include
--O--, --S--, --CO--O--, --O--CO--, --C(S)--O--, --O--C(S)--,
--CR.sup.6R.sup.7, --CR.sup.6R.sup.7--CR.sup.8R.sup.9--,
--O--CR.sup.6R.sup.7--, --CR.sup.6R.sup.7--O--,
--CR.sup.6R.sup.7--O--CR.sup.8R.sup.9--,
--CR.sup.6R.sup.7--O--CO--, --O--CO--CR.sup.6R.sup.7--,
--CR.sup.6R.sup.7--O--CO--CR.sup.8R.sup.9--,
--CR.sup.6R.sup.7--CO--O--CR.sup.8R.sup.9--,
--NR.sup.10--CR.sup.6R.sup.7--, --CR.sup.6R.sup.7--NR.sup.10--,
--CO--NR.sup.10--, --NR.sup.10--CO--, --O--, --S--, --NR.sup.10--,
and --CR.sup.6.dbd.CR.sup.7--. R.sup.6, R.sup.7, R.sup.8 and
R.sup.9 each independently represent a hydrogen atom, a fluorine
atom, or an alkyl group having 1 to 4 carbon atoms. R.sup.10
represents a hydrogen atom or an alkyl group having 1 to 4 carbon
atoms.
[0081] B is preferably --O--, --S--, --O--CO--, --O--C(.dbd.S)--,
--O--CR.sup.6R.sup.7--, --NR.sup.10--CR.sup.6R.sup.7--, or
--NR.sup.10--CO--. D.sup.1 and D.sup.2 are each more preferably
--O--, --S--, --O--CO--, --O--C(.dbd.S)-- or --NR.sup.10--CO--.
R.sup.6, R.sup.7, R.sup.8 and R.sup.9 are each independently
preferably a hydrogen atom or an alkyl group having 1 to 4 carbon
atoms, and more preferably a hydrogen atom, a methyl group or an
ethyl group. R.sup.10 is preferably a hydrogen atom, a methyl group
or an ethyl group.
[0082] In formulae (1) and (2), A represents a divalent alicyclic
hydrocarbon group having 3 to 20 carbon atoms or a divalent
aromatic hydrocarbon group having 6 to 20 carbon atoms, preferably
a divalent alicyclic hydrocarbon group having 4 to 15 carbon atoms
or a divalent aromatic hydrocarbon group having 6 to 15 carbon
atoms, more preferably a divalent alicyclic hydrocarbon group
having 5 to 12 carbon atoms or a divalent aromatic hydrocarbon
group having 6 to 12 carbon atoms, and even more preferably a
divalent alicyclic hydrocarbon group having 6 to 10 carbon atoms or
a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms.
Of these, a 5- or 6-membered alicyclic hydrocarbon group is
preferable.
[0083] The hydrogen atom contained in the alicyclic hydrocarbon
group and the aromatic hydrocarbon group is optionally substituted
with a halogen atom such as a fluorine atom, a chlorine atom, a
bromine atom, and an iodine atom; an alkyl group having 1 to 4
carbon atoms such as a methyl group, an ethyl group, an isopropyl
group, and a tert-butyl group; a fluoroalkyl group having 1 to 4
carbon atoms such as a trifluoromethyl group; a cyano group; or a
nitro group. --CH.sub.2-- contained in the alicyclic hydrocarbon
group is optionally substituted with --O--, --S--, or
--NR.sup.11--, and the methine group (--CH(-)-) contained in the
alicyclic hydrocarbon group is optionally replaced by --N(-)-,
where R.sup.11 represents a hydrogen atom or an alkyl group having
1 to 4 carbon atoms.
[0084] Examples of the divalent alicyclic hydrocarbon group include
the groups represented by the above formulae (g-1) to (g-10).
[0085] The divalent alicyclic hydrocarbon group is preferably a
group represented by formula (g-1), more preferably
1,4-cyclohexanediyl group, and especially preferably
trans-1,4-cyclohexanediyl group.
[0086] Examples of the divalent aromatic hydrocarbon group include
the groups represented by formulae (a-1) to (a-8).
##STR00146##
[0087] The divalent aromatic hydrocarbon group is preferably
1,4-phenylene group.
[0088] In formulae (1) and (2), k represents an integer of 0 to 3,
preferably 1 or 2, and more preferably 1. When k is an integer of 2
or more, a plurality of As and Bs may be the same or different from
each other. From the viewpoint of industrially easily producing
liquid compounds (1) and (2), it is preferable that a plurality of
As and Bs are the same as each other.
[0089] In formulae (1) and (2), E represents an alkanediyl group
having 1 to 17 carbon atoms, preferably 2 to 15 carbon atoms, more
preferably 3 to 12 carbon atoms, and even more preferably 4 to 10
carbon atoms. The hydrogen atom contained in the alkanediyl group
is optionally substituted with a halogen atom, and --CH.sub.2--
contained in the alkanediyl group is optionally substituted with
--O-- or --CO--.
[0090] In formulae (1) and (2), P is a polymerizable group. The
polymerizable group contains a group capable of being involved in
polymerization reaction. Examples thereof include a vinyl group, a
p-(2-phenylethenyl) phenyl group, an acryloyl group, an acryloyloxy
group, a methacryloyl group, a methacryloyloxy group, a carboxy
group, a methylcarboxy group, a hydroxyl group, a carbamoyl group,
an alkylamino group having 1 to 4 carbon atoms, an amino group, a
formyl group, --N.dbd.C.dbd.O, --N.dbd.C.dbd.S, an oxiranyl group,
and an oxetanyl group.
[0091] Of these, the polymerizable group is preferably a radical
polymerizable group or a cationic polymerizable group from the
viewpoint of suitability for photo polymerization; preferably an
acryloyl group, an acryloyloxy group, a methacryloyl group, and a
methacryloyloxy group, from the viewpoint of easy handling and easy
production; and more preferably an acryloyl group and an
acryloyloxy group from the viewpoint of high polymerizing
ability.
<Liquid Crystal Composition and Method for Producing the
Same>
[0092] The liquid crystal composition of the present invention
contains the liquid crystal compounds (1) and (2). G, A, B, E, P
and k in formula (1) representing liquid crystal compound (1) may
be different from or the same as G, A, B, E, P and k in the formula
(2) representing liquid crystal compound (2), respectively. In the
preferred embodiment of the present invention, G, A, B, E, P and k
in the formula (1) are the same as G, A, B, E, P and k in the
formula (2), respectively. In this case, it is possible to
simultaneously prepare liquid crystal compounds (1) and (2)
contained in the liquid crystal composition of the present
invention in one pot. Therefore, it is possible to prepare the
liquid crystal composition of the present invention very
conveniently, which is economically advantageous.
[0093] The optical film obtained by orienting the liquid crystal
compound (1) preferably exhibits a reverse wavelength dispersion
characteristic. When it exhibits such characteristic, uniform
conversion of polarized light is possible over a wide range of
wavelength region, which is preferable. In the case of satisfying
the relation: [Re(450)/Re(550)]<1, a reverse wavelength
dispersion characteristic is exhibited while in the case of
satisfying the relation: [Re(450)/Re(550)].gtoreq.1, a positive
wavelength dispersion characteristic is exhibited. The optical film
obtained by orienting the liquid crystal compound refers to an
optical film formed from oriented liquid crystal compounds.
[0094] The maximum absorption wavelength (.lamda..sub.max) of the
liquid crystal compound (1) is preferably from 300 to 400 nm, more
preferably from 315 to 385 nm, and even more preferably from 330 to
360 nm. When the maximum absorption wavelength (.lamda..sub.max) of
the liquid crystal compound (1) is not less than the lower limit,
the optical film obtained by orienting liquid crystal compound (1)
tends to exhibit a reverse wavelength dispersion characteristic.
When it is not more than the upper limit, light absorption in the
visible light region is suppressed and coloring of the film can be
avoided, which is preferable.
[0095] Examples of the liquid crystal compound (1) include the
following compounds.
##STR00147## ##STR00148## ##STR00149## ##STR00150## ##STR00151##
##STR00152## ##STR00153## ##STR00154## ##STR00155## ##STR00156##
##STR00157## ##STR00158## ##STR00159## ##STR00160## ##STR00161##
##STR00162## ##STR00163## ##STR00164## ##STR00165## ##STR00166##
##STR00167## ##STR00168## ##STR00169## ##STR00170## ##STR00171##
##STR00172## ##STR00173## ##STR00174## ##STR00175## ##STR00176##
##STR00177## ##STR00178## ##STR00179## ##STR00180## ##STR00181##
##STR00182## ##STR00183## ##STR00184## ##STR00185## ##STR00186##
##STR00187## ##STR00188## ##STR00189## ##STR00190## ##STR00191##
##STR00192## ##STR00193## ##STR00194## ##STR00195## ##STR00196##
##STR00197## ##STR00198## ##STR00199## ##STR00200## ##STR00201##
##STR00202## ##STR00203## ##STR00204## ##STR00205## ##STR00206##
##STR00207## ##STR00208## ##STR00209## ##STR00210## ##STR00211##
##STR00212## ##STR00213## ##STR00214## ##STR00215## ##STR00216##
##STR00217## ##STR00218## ##STR00219## ##STR00220## ##STR00221##
##STR00222## ##STR00223## ##STR00224## ##STR00225## ##STR00226##
##STR00227## ##STR00228## ##STR00229## ##STR00230## ##STR00231##
##STR00232## ##STR00233## ##STR00234## ##STR00235## ##STR00236##
##STR00237## ##STR00238## ##STR00239## ##STR00240## ##STR00241##
##STR00242##
##STR00243## ##STR00244## ##STR00245## ##STR00246## ##STR00247##
##STR00248## ##STR00249## ##STR00250## ##STR00251## ##STR00252##
##STR00253## ##STR00254## ##STR00255## ##STR00256## ##STR00257##
##STR00258## ##STR00259## ##STR00260## ##STR00261## ##STR00262##
##STR00263## ##STR00264## ##STR00265## ##STR00266## ##STR00267##
##STR00268## ##STR00269## ##STR00270## ##STR00271## ##STR00272##
##STR00273## ##STR00274## ##STR00275## ##STR00276## ##STR00277##
##STR00278## ##STR00279## ##STR00280## ##STR00281## ##STR00282##
##STR00283## ##STR00284## ##STR00285## ##STR00286##
[0096] The optical film obtained by orienting the liquid crystal
compound (2) preferably exhibits a positive wavelength dispersion
characteristic. When it exhibits, the wavelength dispersion of the
optical film containing the polymer of the liquid crystal
composition can be controlled by changing the ratio of liquid
crystal compound (2) to liquid crystal compound (1) in the liquid
crystal composition, which is preferable.
[0097] Examples of the liquid crystal compound (2) include the
following compounds.
##STR00287##
[0098] When the optical film obtained by orienting liquid crystal
compound (1) exhibits a reverse wavelength dispersion
characteristic and the optical film obtained by orienting liquid
crystal compound (2) exhibits a positive wavelength dispersion
characteristic, it is possible to arbitrarily control the optical
characteristics of the optical film produced using the liquid
crystal composition of the present invention, that is, the optical
film containing a polymer of the liquid crystal composition of the
present invention, by adjusting the contents of liquid crystal
compounds (1) and (2) in the liquid crystal composition.
[0099] The content of the liquid crystal compound (2) in the liquid
crystal composition of the present invention is in the range of
preferably 0.1 to 70 parts by mass, more preferably 1 to 50 parts
by mass, and even more preferably 5 to 30 parts by mass, relative
to 100 parts by mass of the liquid crystal compound (1). Further,
the content of the liquid crystal compound (2) can be 8 parts by
mass or more, further 12 parts by mass or more, and furthermore 17
parts by mass or more. The content of the liquid crystal compound
(2) in the liquid crystal composition of the present invention is
in the range of preferably 0.1 to 70% by mass, more preferably 1 to
50% by mass, and even more preferably 5 to 30% by mass, relative to
100 parts by mass of the liquid crystal compound (1) at ratio of
mass.
[0100] When the content of the liquid crystal compound (2) in the
liquid crystal composition is not less than the lower limit, it is
easy to adjust the wavelength dispersion characteristic of the
optical film, which is preferable. When the content thereof is not
more than the upper limit, it is possible to exhibit the wavelength
dispersion characteristic of the optical film, which is
preferable.
[0101] The optical film obtained by orienting the liquid crystal
composition of the present invention has a degree of wavelength
dispersion Re (450 nm)/Re (550 nm) of preferably 0.65 or more and
less than 1, more preferably 0.75 or more and 0.95 or less, and
even more preferably 0.80 or more and 0.90 or less. When the degree
of wavelength dispersion Re(450 nm)/Re(550 nm) is not less than the
lower limit, conversion of circularly polarized light is possible
in a short wavelength region around 450 nm. When the degree is not
more than the upper limit, the resulting optical film exhibits a
reverse wavelength dispersion characteristic, which is
preferable.
[0102] The liquid crystal composition of the present invention
containing the liquid crystal compounds (1) and (2) can be produced
by a method including, for example, the following steps:
[0103] step (a) of allowing an alcohol compound (3) represented by
formula (3):
[Chem. 204]
P-E B-A.sub.k OH (3)
and a dicarboxylic acid compound (4) represented by formula
(4):
##STR00288##
to react each other to thereby obtain a mixture containing a
carboxylic acid compound (5) represented by formula (5):
##STR00289##
and the liquid crystal compound (2); and
[0104] step (b) of allowing the mixture containing the carboxylic
acid compound (5) and the liquid crystal compound (2) to react with
an alcohol compound (6) represented by formula (6):
[Chem. 207]
HO--Ar--OH (6)
to thereby obtain a liquid crystal composition containing liquid
crystal compounds (1) and (2). Here, the carboxylic acid compound
(5) is a precursor of the liquid crystal compound (1). A, B, P, E,
G and Ar in formulae (3) to (6) are the same as those defined
above.
[0105] Specific examples of the alcohol compound (3) include
compounds represented by the following formulae (3-1-1) to
(3-36-e).
##STR00290## ##STR00291## ##STR00292## ##STR00293## ##STR00294##
##STR00295##
[0106] Examples of the dicarboxylic acid compound (4) include
compound (4-1) represented by the following formula (4-1).
##STR00296##
[wherein the hydrogen atom contained in the alicyclic hydrocarbon
group is optionally substituted with a halogen atom, an alkyl group
having 1 to 4 carbon atoms that is optionally substituted with a
halogen atom, an alkoxy group having 1 to 4 carbon atoms that is
optionally substituted with a halogen atom, a cyano group, or a
nitro group. --CH.sub.2-- contained in the alicyclic hydrocarbon
group is optionally replaced by --O--, --S--, or --N(R.sup.12)--,
and the carbon atom of a methylene group or a methine group
contained in the alicyclic hydrocarbon group may be a nitrogen
atom. R.sup.12 represents a hydrogen atom or an alkyl group having
1 to 4 carbon atoms.
[0107] p represents 0 or 1.]
[0108] Dicarboxylic acid compound (4) is preferably a compound
(4-2) represented by formula (4-2), and more preferably a compound
(4-3) represented by formula (4-3).
##STR00297##
[wherein m represents an integer of 0 to 3; and p represents 0 or
1.]
[0109] Specific examples of the dicarboxylic acid compound (4)
include 1, 2-cyclopentanedicarboxylic acid,
1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic
acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic
acid, 3-methyl-1,2-cyclopentanedicarboxylic acid,
2-methyl-1,3-cyclopentanedicarboxylic acid,
3,4-dimethyl-1,2-cyclohexanedicarboxylic acid,
2-methyl-1,4-cyclohexanedicarboxylic acid, 2,
5-dimethyl-1,4-cyclohexanedicarboxylic acid, 2,6-dimethyl-,
4-cyclohexanedicarboxylic acid, 1,3-adamantanedicarboxylic acid,
1,1'-cyclobutanedicarboxylic acid, 1,1'-cycloproropanedicarboxylic
acid, epoxysuccinic acid, and 4-cyclohexene-1,2-dicarboxylic acid.
Of these, 1,4-cyclohexanedicarboxylic acid is preferable, and
trans-1,4-cyclohexanedicarboxylic acid is more preferable.
[0110] Alcohol compound (6) may be a compound in which two hydroxyl
groups are bonded to an aromatic group of Ar. The aromatic group of
Ar is the same as defined above, and examples thereof include
compounds in which two * portions each refer to a hydroxyl group in
the above formulae (Ar-1) to (Ar-14).
[0111] <Step (a)>
[0112] In step (a), the alcohol compound (3) and the dicarboxylic
acid compound (4) are subjected to esterification reaction. The
esterification reaction is conducted in the presence of a
condensing agent. The esterification reaction in the presence of a
condensing agent can realize efficient and prompt esterification
reaction.
[0113] Examples of the condensing agent include carbodiimide
compounds such as 1-cyclohexyl-3-(2-morpholinioethyl) carbodiimide
metho-p-toluenesulfonate, dicyclohexylcarbodiimide, diisopropyl
carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide,
1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloric acid
salt (water-soluble carbodiimide: commercially available as WSC),
bis(2, 6-diisopropylphenyl) carbodiimide and bis(trimethylsilyl)
carbodiimide; 2-methyl-6-nitrobenzoic anhydride,
2,2'-carbonylbis-1H-imidazole, 1,1'-oxalyldimidazole,
diphenylphosphoryl azide,
1(4-nitrobenzenesulfonyl)-1H-1,2,4-triazole,
1H-benzotriazol-1-yloxytripyrrolidinophosphpnium
hexafluorophosphate,
1H-benzotriazol-1-yloxytris(dimethylamino)phosphonium
hexafluorophosphate, N, N,N',N'-tetramethyl-O--(N-succinimidyl)
uronium tetrafluoroborate, N-(1,2,2,2-tetrachloroethoxycarbonyloxy)
succinimide, N-carbobenzoxysuccinimide,
O-(6-chlorobenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium
tetrafluoroborate,
O-(6-chlorobenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium
hexafluorophosphate, 2-bromo-1-ethylpyridinium tetrafluoroborate,
2-chloro-1, 3-dimethylimidazolinium chloride, 2-chloro-1,
3-dimethylimidazolinium hexafluorophosphate,
2-chloro-1-methylpyridinium iodide, 2-chloro-1-methylpyridinium
p-toluenesulfonate, 2-fluoro-1-methylpyridinium p-toluenesulfonate
and pentachlorophenyl trichloroacetate.
[0114] Of these, preferable are carbodiimide compounds,
2,2'-carbonylbis-1H-imidazole, 1, 1'-oxalyldimidazole,
diphenylphosphoryl azide,
1H-benzotriazol-1-yloxytripyrrolidinophosphpnium
hexafluorophosphate,
1H-benzotriazol-1-yloxytris(dimethylamino)phosphonium
hexaflurophosphate, N,N,N',N'-tetramethyl-O--(N-succinimidyl)
uronium tetrafluoroborate, N-(1,2,2,2-tetrachloroethoxycarbonyloxy)
succinimide,
O-(6-chlorobenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium
tetrafluoroborate, 2-chloro-1,3-dimethylimidazolinium chloride,
2-chloro-1,3-dimethylimidazolinium hexafluorophosphate,
2-chloro-1-methylpyridinium iodide, and 2-chloro-1-methylpyridinium
p-toluenesulfonate.
[0115] More preferable are carbodiimide compounds,
2,2'-carbonylbis-1H-imidazole,
1H-benzotriazol-1-yloxytripyrrolidinophosphpnium hexa
fluorophosphate,
1H-benzotriazol-1-yloxytris(dimethylamino)phosphonium
hexafluorophosphate,
N,N,N',N'-tetramethyl-O--(N-succinimidyl)uronium tetrafluoroborate,
O-(6-chlorobenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium
tetrafluoroborate, 2-chloro-1,3-dimethylimidazolinium chloride, and
2-chloro-1-methylpyridinium iodide; and even more preferable are
carbodiimide compounds from the viewpoint of economic
advantages.
[0116] Of the carbodiimide compounds, preferable are
dicyclohexylcarbodiimide, diisopropylcarbodiimide,
1-ethyl-3-(3-dimethylaminopropyl)carbodiimide,
l-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloric acid
salt (water-soluble carbodiimide: commercially available as WSC),
and bis(2,6-diisopropylphenyl)carbodiimide.
[0117] The amount of the condensing agent used is usually from 1 to
3 moles relative to 1 mole of alcohol compound (3).
[0118] In the esterification reaction, further,
N-hydroxysuccinimide, benzotriazole, p-nitrophenol,
3,5-dibutyl-4-hydroxytoluene, or the like may be added as an
additive and then mixed. The amount of the additive used is
preferably from 0.03 to 1.2 moles relative to 1 mole of the
condensing agent.
[0119] The esterification reaction may be conducted in the presence
of a catalyst. Examples of the catalyst include
N,N-dimethylaminopyridine, N,N-dimethylaniline, and
dimethylammonium pentafluorobenzenesulfonate. Of these,
N,N-dimethylaminopyridine and N,N-dimethylaniline are preferable,
and N,N-dimethylaminopyridine is more preferable. The amount of the
catalyst used is preferably from 0.01 to 0.5 moles relative to 1
mole of alcohol compound (3).
[0120] The esterification reaction is usually conducted in a
solvent. Examples of the solvent include ketone solvents such as
acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl
amyl ketone, and methyl isobutyl ketone; aliphatic hydrocarbon
solvents such as pentane, hexane, and heptane; aromatic hydrocarbon
solvents such as toluene, xylene, benzene, and chlorobenzene;
nitrile solvents such as acetonitrile; ether solvents such as
tetrahydrofuran, and dimethoxyethane; ester solvents such as ethyl
lactate; halogenated hydrocarbon solvents such as chloroform and
chlorobenzene; nonprotic polar solvents such as dimethyl sulfoxide,
N-methyl-2-pyrrolidone, N,N-dimethylformamide,
N,N-dimethylacetamide, and hexamethylphosphoric triamide. These
organic solvents may be used alone or in combination.
[0121] Of these, the solvent is preferably a hydrophilic organic
solvent such as acetone, acetonitrile, tetrahydrofuran,
dimethoxyethane, ethyl lactate, dimethyl sulfoxide,
N-methyl-2-pyrrolidone, N,N-dimethylformamide,
N,N-dimethylacetamide, or hexamethylphosphoric triamide; and more
preferably a nonprotic polar solvents such as dimethyl sulfoxide,
N-methyl-2-pyrrolidone, N,N-dimethyiformamide,
N,N-dimethyiacetamide, or hexamethylphosphoric triamide.
[0122] The amount of dicarboxylic acid compound (4) used is
preferably from 1 to 50 moles, more preferably from 3 to 50 moles,
even more preferably from 4 to 40 moles, and especially preferably
from 5 to 20 moles, relative to 1 mole of alcohol compound (3).
When the amount of dicarboxylic acid compound (4) used is not less
than the lower limit, the yield of liquid crystal compound (1) is
good. When the amount thereof is not more than the upper limit, the
posttreatment work for removing unreacted dicarboxylic acid
compound (4) can be easily performed, so that productivity tends to
be enhanced.
[0123] The amount of the solvent used is preferably from 0.5 to 50
parts by mass, more preferably from 1 to 20 parts by mass, and even
more preferably from 2 to 10 parts by mass, relative to 1 part by
mass of the total amount of alcohol compound (3) and dicarboxylic
acid compound (4).
[0124] In step (a), the esterification reaction temperature is
preferably from -20 to 120.degree. C., more preferably from 20 to
80.degree. C., and even more preferably from 30 to 60.degree. C.
The esterification reaction time is preferably from 1 minute to 72
hours, more preferably from 1 to 48 hours, and even more preferably
from 1 to 24 hours. There is a tendency that the reaction yield is
improved and the productivity is further enhanced by performing the
esterification reaction in the above-mentioned temperature and time
ranges.
[0125] After the esterification reaction, an unreacted dicarboxylic
acid compound (4) can be removed as required. As the method of
removing the unreacted dicarboxylic acid compound (4), the
following method may be used. The reaction mixture obtained in step
(a), a basic compound, and water are mixed to prepare a suspension.
In the suspension, the unreacted dicarboxylic acid compound (4) is
ionized and then dissolved therein, so that unreacted dicarboxylic
acid compound (4) can be removed, and a mixture containing
carboxylic acid compound (5) and liquid crystal compound (2) can be
precipitated.
[0126] The basic compound may be a compound capable of undergoing
an acid-base reaction with dicarboxylic acid compound (4).
Preferable is a basic compound having alkali metal or
alkaline-earth metal such as hydride of alkali metal, hydride of
alkaline earth metal, hydroxide of alkali metal, hydroxide of
alkaline earth metal, alkoxide of alkali metal, and alkoxide of
alkaline-earth metal. A basic compound having alkali metal or
alkaline-earth metal such as hydride of alkali metal, hydride of
alkaline earth metal, hydroxide of alkali metal, and hydroxide of
alkaline earth metal is more preferable. Specific examples thereof
include lithium hydride, sodium hydride, potassium hydride, lithium
hydroxide, sodium hydroxide, potassium hydroxide, calcium
hydroxide, t-butoxysodium, and t-butoxypotassium.
[0127] The amount of the basic compound used is preferably from
0.05 to 50 moles, more preferably from 0.1 to 10 moles, and even
more preferably from 0.2 to 2 moles, relative to 1 mole of
dicarboxylic acid compound (4). When the amount of the basic
compound used is not less than the lower limit, dicarboxylic acid
compound (4) is easily dissolved, so that it tends to be easily
removed. When the amount thereof is not more than the upper limit,
it is possible to reduce the amount of carboxylic acid compound (5)
that generates salts and to conveniently operate the subsequent
treatment, so that productivity can be enhanced.
[0128] The amount of water used is preferably from 20 to 10000
parts by mass, more preferably from 50 to 5000 parts by mass, or
even more preferably from 100 to 1000 parts by mass, relative to
100 parts by mass of the reaction mixture. By mixing the basic
compound and water in the above-mentioned amount ranges, it becomes
easier to dissolve the substances such as unreacted dicarboxylic
acid compound (4) in water and to precipitate the mixture
containing carboxylic acid compound (5) and liquid crystal compound
(2), which is preferable.
[0129] As a method of obtaining solids containing carboxylic acid
compound (5) and liquid crystal compound (2) from the resulting
suspension, filtration, decantation, or the like may be used.
Filtration is preferably used.
[0130] According to such method, solids containing carboxylic acid
compound (5) and liquid crystal compound (2) can be obtained.
Relative to 1 part by mass of the solids obtained in step (a), the
content of dicarboxylic acid compound (4) in the solids is
preferably 0.01 parts by mass or less, more preferably 0.005 parts
by mass or less, and even more preferably 0.001 parts by mass or
less.
[0131] <Step (b)>
[0132] In step (b), the mixture containing carboxylic acid compound
(5) and liquid crystal compound (2) obtained in step (a) is allowed
to react with alcohol compound (6). In this reaction, an
esterification reaction of carboxylicacid compound (5) and alcohol
compound (6) occurs. The esterification reaction is preferably
conducted in the presence of a condensing agent. Further, it is
possible to conduct the esterification reaction in step (b) in the
presence of a catalyst. Usually, such esterification reaction is
conducted in a solvent. As the condensing agent, catalyst and
solvent, for example, those used in step (a) may be used. The
esterification reaction in step (b) can be conducted in the same
manner as in step (a).
[0133] The amount of alcohol compound (6) used is preferably from
0.2 to 0.7 moles, more preferably from 0.3 to 0.6 moles, even more
preferably from 0.4 to 0.5 moles and especially preferably from
0.42 to 0.45 moles, relative to 1 mole of carboxylic acid compound
(5). When the amount of the alcohol compound (6) used is not less
than the lower limit, the amount of unreacted carboxylic acid
compound is reduced, which facilitates purification. When the
amount thereof is not more than the upper limit, a shortage of
carboxylic acid compounds is suppressed and the yield can be
improved.
[0134] The amount of the solvent used is preferably from 0.5 to 50
parts by mass, more preferably from 0.1 to 20 parts by mass, and
even more preferably from 2 to 10 parts by mass, relative to 1 part
by mass of the total amount of carboxylic acid compound (5), liquid
crystal compound (2) and alcohol compound (6).
[0135] In step (b), the esterification reaction temperature is
preferably from -20 to 100.degree. C., more preferably from -10 to
50.degree. C., and even more preferably from 0 to 30.degree. C. The
esterification reaction time is preferably from 1 minute to 72
hours, more preferably from 1 to 48 hours, and even more preferably
from 1 to 24 hours. There is a tendency that the reaction yield is
improved and the productivity is further enhanced by performing the
esterification reaction in the above-mentioned temperature and time
ranges.
[0136] As a result of the reaction described above, a liquid
crystal composition containing liquid crystal compounds (1) and (2)
can be obtained. The liquid crystal composition can be purified by
filtration, decantation, or the like.
[0137] It is preferable that the liquid crystal composition of the
present invention further contains a polymerization initiator.
Examples of the polymerization initiator include a
photo-polymerization initiator and a thermal polymerization
initiator. In the present invention, a photo-polymerization
initiator is preferable as the polymerization initiator.
[0138] Examples of the photo-polymerization initiator include
benzoins, benzophenones, benzyl ketals, .alpha.-hydroxyketones,
.alpha.-aminoketones, iodonium salts and sulfonium salts. More
specific examples thereof include Irgacure 907, 184, 651, 819, 250
and 369 (hereinabove all manufactured by Ciba Japan K.K.); Seikuol
BZ, Z, BEE (hereinabove all manufactured by Seiko Chemical Co.,
Ltd.); Kayacure BP100 (manufactured by Nippon Kayaku Co., Ltd.);
Cyracure UVI-6992 (manufactured by the Dow Chemical Company); and
Adeka Optomer SP-152 or SP-170 (hereinabove all manufactured by
Adeka Corporation).
[0139] The content of the polymerization initiator is, for example,
from 0.1 to 30 parts by mass, and preferably from 0.5 to 10 parts
by mass, relative to 100 part by mass of the total amount of liquid
crystal compounds (1) and (2). When the content thereof is within
the above range, liquid crystal compounds (1) and (2) can be
polymerized without disturbing the orientation of the liquid
crystal compounds.
[0140] In the present invention, an optical film refers to a film
which is capable of transmitting light and has an optical function.
The optical function means refraction, birefringence, or the like.
A retardation film, which is a type of optical film, is used for
converting linearly polarized light into circularly polarized light
or elliptically polarized light, and vice versa. The optical film
of the present invention contains a polymer of the liquid crystal
composition of the present invention. That is, the optical film of
the present invention contains a polymer composed of a structural
unit derived from liquid crystal compound (1) and a structural unit
derived from liquid crystal compound (2).
[0141] The wavelength dispersion characteristic of the optical film
according to the present invention can be arbitrarily controlled by
adjusting the content of the structural unit derived from liquid
crystal compound (1) and the structural unit derived from liquid
crystal compound (2) in the above-mentioned polymer which composes
the optical film. When the content of the structural unit derived
from liquid crystal compound (1) among the structural units in the
polymer which composes the optical film is increased, the optical
film exhibits a flatter wavelength dispersion characteristic and
reverse wavelength dispersion characteristic. For example, when the
content of the structural unit derived from liquid crystal compound
(1) among them is increased, it is possible to lower the numerical
value of Re(450 nm)/Re(550 nm), and when the content of the
structural unit derived from liquid crystal compound (2) is
increased, it is possible to increase the numerical value of Re(450
nm)/Re(550 nm).
[0142] The content of the structural units derived from liquid
crystal compounds (1) and (2) in the above-mentioned polymer which
composes the optical film can be adjusted by selecting the contents
of the liquid crystal compounds, and the following method is
preferably used.
[0143] In the production method of the present invention, it is
possible to adjust the content of liquid crystal compounds (1) and
(2) in the formed liquid crystal composition by selecting the
amounts of the alcohol compound (3) and the dicarboxylic acid
compound (4) used as raw materials. By adjusting the content
thereof, the wavelength dispersion characteristic of the optical
film obtained from the liquid crystal composition can be selected.
Specifically, the following method is used. First, two or more
kinds of liquid crystal compositions each having different content
of the structural units derived from liquid crystal compounds (1)
and (2) are prepared, and with these liquid crystal compositions,
optical films each having the same film thickness are produced as
described later. Next, the retardation values of the optical films
thus produced are calculated, and the correlation between the
content of the structural units derived from liquid crystal
compounds (1) and (2) and the retardation value of the optical film
is obtained from the results. Then, from the obtained correlation,
the content of the structural units derived from liquid crystal
compound (1) and (2) which are necessary to impart a desired
wavelength dispersion characteristic to the optical film having the
above-mentioned film thickness is determined. Further, in order to
obtain the determined content of the structural units derived from
liquid crystal compounds (1) and (2), the amounts of the above
alcohol compound (3) and the above dicarboxylic acid compound (4)
used are selected, so that an optical film having a desired
wavelength dispersion characteristic can be conveniently produced.
According to the production method of the present invention, it is
not necessary to independently produce the liquid crystal
compounds, and without conducting a complicated operation such as a
terminal capping step, it is possible to simultaneously produce the
liquid crystal compounds in one pot, which enables the production
step to be significantly shortened. Therefore, the production
method of the present invention is highly economically
advantageous.
<Production Method of Optical Film>
[0144] The production method of the optical film of the present
invention will be described below.
[0145] First, an additive such as an organic solvent, the
polymerization initiator mentioned above, a polymerization
inhibitor, a photosensitizer or a leveling agent is added to the
liquid crystal composition containing liquid crystal compounds (1)
and (2) as required, to prepare a mixing solution. In particular,
the mixing solution preferably contains an organic solvent because
it facilitates formation of layers at the time, and a
polymerization initiator because it serves to cure the resulting
optical film.
[0146] [Polymerization Inhibitor]
[0147] A polymerization inhibitor may be used for preparing the
optical film of the present invention. Examples of the
polymerization inhibitor include hydroquinone or hydroquinones
having a substituent such as alkyl ether; catechols having a
substituent including alkyl ether such as butyl catechol;
pyrogallols; a radical scavenger such as
2,2,6,6-tetramethyl-1-piperidinyloxy radical; thiophenols;
.beta.-naphthylamines and .beta.-naphthols.
[0148] The use of the polymerization inhibitor allows the
polymerization of liquid crystal compounds (1) and (2) to be
controlled, so that the stability of the resulting optical film can
be improved. The amount of the polymerization inhibitor used is,
for example, from 0.1 to 30 parts by mass, and preferably from 0.5
to 10 parts by mass, relative to 100 parts by mass of the total
amount of liquid crystal compounds (1) and (2). When the amount
thereof is within the above range, liquid crystal compounds (1) and
(2) can be polymerized without disturbing the orientation of the
liquid crystal compounds.
[0149] [Photosensitizer]
[0150] A photosensitizer may also be used for preparing the optical
film of the present invention. Examples of the photosensitizer
include xanthones such as xanthone and thioxanthone; anthracene or
anthracenes having a substituent such as alkyl ether;
phenothiazine; and rubrene.
[0151] The use of the photosensitizer can make the polymerization
of liquid crystal compounds (1) and (2) highly sensitive. The
amount of the photosensitizer used is, for example, from 0.1 to 30
parts by mass, and preferably from 0.5 to 10 parts by mass,
relative to 100 parts by mass of the total amount of liquid crystal
compounds (1) and (2). When the amount thereof is within the above
range, liquid crystal compounds (1) and (2) can be polymerized
without disturbing the orientation of the liquid crystal
compounds.
[0152] [Leveling Agent]
[0153] A leveling agent may further be used for preparing the
optical film of the present invention. Examples of the leveling
agent include additives for radiation-curable coating (manufactured
by BYK Japan KK: BYK-352, BYK-353 and BYK-361N), coating additives
(manufactured by Dow Corning Toray Co., Ltd.: SH28PA, DC11PA and
ST80PA), coating additives (manufactured by Shin-Etsu Chemical Co.,
Ltd.: KP321, KP323, X22-161A and KF6001), and fluorine-based
additives (manufactured by DIC Co., F-445, F-470 and F-479).
[0154] The use of the leveling agent allows the optical film to be
smoothed. Further, by using the leveling agent, in the step of
producing the optical film, it is possible to control the fluidity
of the mixing solution containing liquid crystal compounds and to
adjust the crosslinkage density of the optical film which is
obtained by polymerizing liquid crystal compounds (1) and (2). The
specific numerical value of the amount of the leveling agent used
is, for example, from 0.1 to 30 parts by mass, and preferably from
0.5 to 10 parts by mass, relative to 100 parts by mass of the total
amount of liquid crystal compounds (1) and (2). When the amount
thereof is within the above range, liquid crystal compounds (1) and
(2) can be polymerized without disturbing the orientation of the
liquid crystal compounds.
[0155] [Organic Solvent]
[0156] An organic solvent to be used for preparation of the mixing
solution containing the liquid crystal composition of the present
invention is capable of dissolving liquid crystal compounds (1),
(2) or the like and may be inert to polymerization reaction.
Examples of the organic solvent include alcohols such as methanol,
ethanol, ethylene glycol, isopropyl alcohol, propylene glycol,
methyl cellosolve, butyl cellosolve, and propylene glycol
monomethyl ether; ester solvents such as ethyl acetate, butyl
acetate, ethylene glycol methyl ether acetate,
.gamma.-butyrolactone, propylene glycol methyl ether acetate and
ethyl lactate; ketone solvents such as acetone, methyl ethyl
ketone, cyclopentanone, cyclohexanone, methyl amyl ketone and
methyl isobutyl ketone; non-chlorinated aliphatic hydrocarbon
solvents such as pentane, hexane and heptane; non-chlorinated
aromatic hydrocarbon solvents such as toluene, xylene and phenol;
nitrile solvents such as acetonitrile; ether solvents such as
tetrahydrofuran and dimethoxyethane; and chlorinated hydrocarbon
solvents such as chloroform and chlorobenzene. These organic
solvents may be used alone or in combination. Since the liquid
crystal composition of the present invention has excellent
compatibility and can also be dissolved in alcohols, ester
solvents, ketone solvents, non-chlorinated aliphatic hydrocarbon
solvents, and non-chlorinated aromatic hydrocarbon solvents, it can
be dissolved for coating without using chlorinated hydrocarbon
solvents such as chloroform.
[0157] It is preferable that the viscosity of the mixing solution
containing the liquid crystal composition of the present invention
is adjusted, for example, to 10 Pas or less, and preferably to 0.1
to 7 Pas or so for ease of coating.
[0158] The concentration of the solids in the mixing solution is,
for example, from 5 to 50% by mass. When the concentration of the
solids is not less than 5%, there is a tendency that the optical
film does not become excessively thin and the birefringence index
required for optical compensation for liquid crystal panels is
given thereto. When the concentration thereof is not more than 50%,
there is a tendency that unevenness does not easily occur in the
thickness of the optical film because of the low viscosity of the
mixing solution.
[0159] The mixing solution containing the liquid crystal
composition is then applied onto a supporting substrate and dried
to form a liquid crystal layer. When the liquid crystal layer
exhibits a liquid crystal phase such as a nematic phase, the
obtained optical film has a birefringence characteristic due to
monodomain orientation. Since the liquid crystal layer is oriented
at a low temperature of 0 to 120.degree. C. or so, and preferably
25 to 80.degree. C., a supporting substrate which is not always
satisfactory in the heat resistance as exemplified above can be
used as an orientation layer. In addition, even when the liquid
crystal layer is further cooled to 30 to 10.degree. C. or so after
the orientation, it is not crystallized, so that the liquid crystal
layer is easily handled.
[0160] By appropriately adjusting the coating amount and the
concentration of the mixing solution, the thickness of the layer
can be adjusted so as to provide a desired retardation. In the case
of the mixing solution having a constant amount of liquid crystal
compounds (1) and (2), the retardation value (retardation value Re
(.lamda.) of the obtained optical film is determined as formula
(I). Therefore, in order to obtain a desired Re(.lamda.), a film
thickness d may be adjusted.
Re(.lamda.)=d.times..DELTA.n(.lamda.) (1)
(wherein Re(.lamda.) represents a retardation value at a wavelength
of .lamda. nm; d represents a film thickness; and .DELTA.n
(.lamda.) represents a birefringence index at a wavelength of
.lamda. nm.)
[0161] Examples of a method for applying the mixing solution to the
supporting substrate include an extrusion coating method, a direct
gravure coating method, a reverse gravure coating method, a CAP
coating method, and a die coating method. Examples thereof also
include a method for coating by using a coater such as a dip
coater, a bar coater or a spin coater.
[0162] Examples of the above-mentioned supporting substrate include
glass, plastic sheets, plastic films, or translucent films.
Examples of the translucent film include polyolefin films such as
polyethylene, polypropylene and norbornene-based polymers;
polyvinyl alcohol films; polyethylene terephthalate films;
polymethacrylate films; polyacrylate films; cellulose ester films;
polyethylene naphthalate films; polycarbonate films; polysulfone
films; polyethersulfone films; polyetherketone films;
polyphenylenesulfide films; and polyphenylene oxide films.
[0163] By using the supporting substrate, the optical film of the
present invention can be easily handled without breakage, even in
the steps requiring strength of the optical film, such as a bonding
step, a conveying step, and a storing step of the optical film.
[0164] It is preferable that the orientation layer is formed on the
supporting substrate and the mixing solution containing the liquid
crystal composition of the present invention is applied onto the
orientation layer. It is preferable that the orientation layer has
solvent resistance so as not tobe dissolved in the mixing solution
containing the liquid crystal composition of the present invention
when the mixing solution is applied thereonto; has heat resistance
at the time of removal of the solvent or of heat-treatment of the
liquid crystal orientation; and does not generate peeling due to
friction at the time of rubbing. It is also preferable that the
orientation layer is composed of a polymer or a composition
containing a polymer.
[0165] Examples of the above-mentioned polymer include polyamides
and gelatins having amide bonds in the molecule, polyimides having
imide bonds in the molecule and polyamic acids which are the
hydrolysate thereof, polyvinyl alcohol, alkyl-modified polyvinyl
alcohols, polyacrylamide, polyoxazoles, polyethylene imine,
polystyrene, polyvinylpyrrolidone, polyacrylic acid, and
polyacrylic acid esters. These polymers may be used alone, in
combination of two or more kinds, or copolymerized. These polymers
can be easily obtained by a polycondensation based on dehydration,
deamination or the like, a chain polymerization such as radical
polymerization, anion polymerization or cation polymerization,
coordination polymerization, ring-opening polymerization or some
other polymerization.
[0166] These polymers can also be dissolved in a solvent and then
applied. The solvent is not particularly limited, and specific
examples thereof include water; alcohol solvents such as methanol,
ethanol, ethylene glycol, isopropyl alcohol, propylene glycol,
methylcellosolve, butylcellosolve and propylene glycol monomethyl
ether; ester solvents such as ethyl acetate, butyl acetate,
ethylene glycol methyl ether acetate, .gamma.-butyrolactone,
propylene glycol methyl ether acetate and ethyl lactate; ketone
solvents such as acetone, methyl ethyl ketone, cyclopentanone,
cyclohexanone, methyl amyl ketone and methyl isobutyl ketone;
non-chlorinated aliphatic hydrocarbon solvents such as pentane,
hexane and heptane; non-chlorinated aromatic hydrocarbon solvents
such as toluene and xylene; nitrile solvents such as acetonitrile;
ether solvents such as tetrahydrofuran and dimethoxyethane; and
chlorinated hydrocarbon solvents such as chloroform and
chlorobenzene. These organic solvents may be used alone or in
combination.
[0167] In order to form the orientation layer, a commercially
available material for orientation layers may be used as it is.
Examples of the commercially available material for orientation
layers include SUNEVER (registered trademark, manufactured by
Nissan Chemical Industries ltd.) and OPTMER (registered trademark,
manufactured by JSR Corporation).
[0168] The use of such orientation layer can eliminate the need of
controlling refractive index by drawing, so that in-plane
dispersion of birefringence can be reduced. For this reason, there
is exhibited an effect that a large optical film which can meet the
requirements of upsizing of a flat panel display device (FPD) can
be provided on a supporting substrate.
[0169] As a method for forming the orientation layer on the
supporting substrate, for example, a commercially available
material for orientation layers or a compound serving as an
orientation layer material is converted into a solution, the
resulting solution is applied thereonto, followed by annealing, to
thereby form an orientation layer on the supporting substrate.
[0170] The thickness of the orientation layer thus obtained is, for
example, from 10 nm to 10000 nm, and preferably from 10 nm to 1000
nm. When the thickness thereof is within the above range, liquid
crystal compounds (1) and (2) or the like can be oriented to a
desired angle on the orientation layer.
[0171] Further, these orientation layers can be subjected to
rubbing or polarized UV irradiation as required. By forming the
orientation layer, liquid crystal compounds (1) and (2) or the like
can be oriented to a desired direction.
[0172] As a method for rubbing the orientation layer, for example,
a method in which a rotating rubbing roll wrapped with a rubbing
cloth is brought into contact with the orientation layer which is
being conveyed on a stage may be used.
[0173] As described above, in the step of preparing the liquid
crystal layer, a liquid crystal layer may be laminated on the
orientation layer which is laminated on any supporting substrate.
In such case, production cost can be reduced as compared with a
method in which a liquid crystal cell is produced and a liquid
crystal composition is injected into the liquid crystal cell.
Further, it is possible to produce a film in the form of a roll
film.
[0174] The solvent may be dried as the polymerization proceeds.
Most of the solvent is, however, preferably dried before the
polymerization from the viewpoint of layer formability.
[0175] Examples of a method for drying the solvent include natural
drying, air drying, and vacuum drying. The specific heating
temperature is preferably from 10 to 120.degree. C., and more
preferably from 25 to 80.degree. C. The heating time is preferably
from 10 seconds to 60 minutes, and more preferably from 30 seconds
to 30 minutes. When the heating temperature and the heating time
are within the above ranges, a supporting substrate which is not
always satisfactory in the heat resistance can be used as the
above-mentioned supporting substrate.
[0176] Next, the liquid crystal layer obtained above is polymerized
and then cured. This produces a film in which the orientation of
liquid crystal compounds (1) and (2) is fixed, that is, a film (an
optical film) containing a polymer of the liquid crystal
composition of the present invention. Accordingly, an optical film
in which a change in refractive index is small in a film-plane
direction and is large in a film normal line direction can be
produced.
[0177] The method for polymerizing the liquid crystal layer is
determined depending on the type of liquid crystal compounds (1)
and (2). The above-mentioned liquid crystal layer can be
polymerized by photopolymerization when the polymerizable group
contained in liquid crystal compounds (1) and (2) is
photo-polymerizable or by thermal polymerization when the
polymerizable group is thermally polymerizable. In the present
invention, it is preferable that the liquid crystal layer is
polymerized, in particular, by photopolymerization. According to
the photo polymerization, it is possible to polymerize the liquid
crystal layer at low temperature, so that a selection range for
heat resistance of the supporting substrate is enhanced. In
addition, photo polymerization makes the production industrially
easier. From the viewpoint of layer formability, photo
polymerization is preferable. Photo polymerization is performed by
irradiating the liquid crystal layer with visible light,
ultraviolet light or laser light. From the viewpoint of
handleability, irradiation of ultraviolet light which is especially
preferable, may be performed with warming at a temperature at which
liquid crystal compounds (1) and (2) are in liquid crystal phase.
At this time, the optical film can be patterned by masking or the
like.
[0178] Further, the optical film of the present invention is a thin
layer as compared with a drawn film in which a polymer is drawn to
cause retardation.
[0179] The method for producing the optical film of the present
invent ion may further include a step of separating the supporting
substrate. From such structure, the resulting laminated body
becomes a film composed of an orientation layer and an optical
film. In addition to the above-mentioned step of separating the
supporting substrate, a step of separating the orientation layer
may further be included. From such structure, an optical film can
be produced.
[0180] The optical film thus produced is excellent in transparency
and can be used as various display films. The thickness of the
optical film varies depending on the retardation values and desired
thickness of the produced optical film as described above. In the
present invention, the thickness thereof is preferably from 0.1 to
10 .mu.m, and more preferably from 0.5 to 3 .mu.m in view of
reducing photoelasticity.
[0181] When the optical film has birefringence using the
orientation layer, the retardation value is, for example, from 50
to 500 nm or so, and preferably from 100 to 300 nm.
[0182] The film, which is of a thin layer and is capable of uniform
conversion of polarized light over a wider wavelength band, can be
used as an optical compensation film in all the FPDs including
crystal liquid panels and organic ELs.
[0183] In order to use the optical film of the present invention as
a wide band .lamda./4 plate or .lamda./2 plate, the content of the
structural unit derived from liquid crystal compound (1) and the
structural unit derived from liquid crystal compound (2) in the
polymer which composes the optical film of the present invention is
appropriately selected. When the optical film of the present
invention is used as a .lamda./4 plate, the content of the
structural units derived from liquid crystal compounds (1) and (2)
in the above-mentioned polymer and the film thickness may be
adjusted so that the retardation value (Re(550)) at a wavelength of
550 nm of the resulting optical film is preferably from 113 to 163
nm, more preferably from 135 to 140 nm, and especially preferably
from about 137.5 nm. When the optical film is used as a .lamda./2
plate, such content and the film thickness may be adjusted so that
Re(550) of the resulting optical film is preferably from 250 to 300
nm, more preferably from 273 to 277 nm, and especially preferably
from about 275 nm. According to the present invention, Re(550) can
be controlled by adjusting the content of the structural units
derived from liquid crystal compounds (1) and (2) in the
above-mentioned polymer alone. Therefore, it is possible to select
a desired film thickness.
[0184] In order to use the optical film of the present invention as
an optical film of VA (vertical alignment) mode, the content of the
structural units derived from liquid crystal compounds (1) and (2)
is appropriately selected. The content of the structural units
derived from liquid crystal compounds (1) and (2) in the
above-mentioned polymer and the film thickness may be adjusted so
that Re(550) is preferably from about 40 to 100 nm and more
preferably from about 60 to 80 nm.
[0185] In order to adjust the content of the structural units
derived from liquid crystal compounds (1) and (2) in the
above-mentioned polymer which composes the optical film of the
present invention, the content of liquid crystal compounds (1) and
(2) in the liquid crystal composition of the present invention may
be adjusted. To do so, the amounts of alcohol compound (3) and
dicarboxylic acid compound (4) used may be adjusted.
[0186] The wavelength dispersion characteristic of the optical film
can be varied by selecting the contents of liquid crystal compounds
(1) and (2) in the liquid crystal composition which is used when
the optical film is produced, that is, the amounts of alcohol
compound (3) and dicarboxylic acid compound (4) used. Therefore,
the wavelength dispersion characteristic thereof can be controlled
to a desired one by a convenient method.
[0187] The optical film of the present invention can be used as an
antireflective film such as an antireflection (AR) film, a
polarizing film, a retardation film, an elliptically polarizing
film, a viewing angle expansion film or an optical compensation
film for viewing angle compensation of a translucent liquid crystal
display. Even one sheet of the optical film of the present
invention exhibits excellent optical characteristics, but two or
more sheets thereof may be laminated.
[0188] The optical film may also be combined with another film.
Specifically, an elliptically polarizing plate and a circularly
polarizing plate containing the optical film and the polarizing
film of the present invention are provided in the present
invention. In these plates, the optical film of the present
invention is bonded to the polarizing film. Further, in the present
invention, it is possible to provide a wide-band circularly
polarizing plate in which the optical film of the present invention
is bonded to the elliptically polarizing plate or the circularly
polarizing plate as a wide-band .lamda./4 plate.
[0189] The optical film of the present invention can be used for a
retardation plate of a reflective liquid crystal display and an
organic electro-luminescence (EL) display, and for an FPD having
the retardation plate and the optical film. The above FPD is not
particularly limited, and examples thereof include a liquid crystal
display (LCD) device and an organic EL display device.
[0190] In the present invention, the flat panel display device has
the optical film of the present invention, and examples thereof
include a liquid crystal display device having a bonded product
obtained by bonding the polarizing film of the present invention
and a liquid crystal panel to each other, and an organic EL display
device having an organic EL panel in which the polarizing film of
the present invention and a light emitting layer are bonded to each
other.
[0191] [Organic EL Display Device]
[0192] In the present invention, an organic electro-luminescence
(EL) display device including an organic EL panel containing the
circularly polarizing plate of the present invention is also
provided. The organic EL display device comprises an organic EL
panel, and the organic EL panel is formed by bonding the optical
film of the present invention and a light emitting layer through an
adhesive layer as required. In the organic EL panel, the optical
film serves as a circularly polarizing plate. The light emitting
layer is of at least one layer made of a conductive organic
compound.
EXAMPLES
[0193] The present invention will, hereinafter, be illustrated
using Examples further in detail. The units, "%" and "part(s)",
presented in the examples are % by mass and part(s) by mass, unless
otherwise specified therein.
[0194] The liquid chromatography (LC) analysis conditions are
indicated below.
<LC Analysis Conditions>
[0195] Measuring apparatus: LC-10AT (manufactured by Shimadzu
Corp.)
[0196] Column: Kinetex (registered trademark) ODS (5 .mu.m, 4.6
mm.phi..times.15 cm)
[0197] Column temperature: 40.degree. C.
[0198] Mobile phase: A: 0.1% trifluoroacetic acid aqueous solution
[0199] B: 0.1% trifluoroacetic acid-containing acetonitrile
solution
[0200] Gradient: 0 min B=2% [0201] 30 min B=100% [0202] 35 min
B=100% [0203] 35.1 min B=2% [0204] 45 min STOP Total analysis time
45 min
[0205] Flow rate: 1.0 mL/min
[0206] Detection: UV absorption (wavelength: 220 nm)
Example 1
[0207] A mixture of liquid crystal compound (1) having a reverse
wavelength dispersion characteristic represented by formula (1) and
liquid crystal compound (2) having a positive wavelength dispersion
characteristic represented by formula (2) was synthesized according
to the following scheme.
##STR00298##
[0208] Mixed were 36 g (210 mmol) of the
trans-cyclohexanedicarboxylic acid represented by the above formula
(4) and 72 g of N-methyl-2-pyrrolidone, to obtain a solution. To
the solution thus obtained, 9.9 g (42 mmol) of monoalcohol compound
represented by the above formula (3), 0.7 g (2.9 mmol) of
3,5-dibutyl-4-hydroxytoluene, and 0.055 g (0.4 mmol) of
N,N-dimethylaminopyridine were added, and the temperature of the
resulting mixture was kept at 45.degree. C. To the mixture, 6.9 g
(55 mmol) of diisopropylcarbodiimide was added dropwise in over 1
hour, and the added mixture was then subjected to esterification
reaction by stirring for 15 hours.
[0209] On the other hand, 2.1 g (53 mmol) of sodium hydroxide and
145 g of water were mixed. The resulting mixture was added dropwise
to the above-mentioned reaction mixture and the added mixture was
stirred for 2 hours to obtain a suspension. The suspension thus
obtained was filtered to give solids. The solids were washed 6
times with a mixed solvent of methanol and water (mass ratio 1:1),
further followed by drying under reduced pressure, to thereby
obtain 12.6 g of white solids.
[0210] Added were 12.6 g of the white solids, 4.25 g (14 mmol) of
the alcohol compound represented by the above formula (6), 0.033 g
(0.3 mmol) of N,N-dimethylaminopyridine, and 60 g of chloroform,
and the temperature of the mixture was kept at 0.degree. C. To the
resulting mixture, 4.3 g (34 mmol) of diisopropylcarbodiimide was
added dropwise in over 1 hour, and the added mixture was then
subjected to esterification reaction by stirring for 15 hours. The
reaction mixture thus obtained was filtered to remove insoluble
fractions, the filtrate was added dropwise to heptane, and
precipitated solids were filtered. The solids thus obtained were
washed 3 times with heptane, further followed by drying under
reduced pressure, to thereby obtain 16.4 g of mixture A of liquid
crystal compound (1) having a reverse wavelength dispersion
characteristic represented by formula (1) and liquid crystal
compound (2) having a positive wavelength dispersion characteristic
represented by formula (2).
[0211] Mixture A was analyzed using the LC analysis conditions
described above. The mixture A contained 7 parts by mass of liquid
crystal compound (2) relative to 100 parts by mass of liquid
crystal compound (1). Thus, the content of the liquid crystal
compound (2) is 7% by mass relative to 100% by mass of liquid
crystal compound (1). The measurement with spectrophotometer
(chloroform solution) indicated that the maximum absorption
wavelength (.lamda..sub.max) of liquid crystal compound (1) was 350
nm.
[Preparation of Composition for Forming Photo-orientation
Layer]
[0212] The following components were mixed, and the resulting
mixture was stirred at 80.degree. C. for 1 hour to obtain a
composition for forming a photo-orientation layer. The following
photo-orientation materials were synthesized by the method
disclosed in JP-A-2013-33248.
[0213] Photo-orientation material (5 parts)
##STR00299##
[0214] Solvent (95 parts): Cyclopentanone
[Production of Optical Film]
[0215] The optical film obtained by polymerizing the above mixture
A was produced as follows:
[0216] A polyethylene terephthalate film (PET) (DIAFOIL T140E25
manufactured by Mitsubishi Plastics, Inc.) was treated once using a
Corona generator (AGF-B10, manufactured by Kasuga Denki Inc.) under
the conditions of an output of 0.3 kW and a treatment rate of 3
m/min. The composition for forming a photo-orientation layer was
applied to the corona-treated surface using a bar coater, and dried
at 80.degree. C. for 1 minute, followed by exposure to polarized UV
radiation using a polarized UV irradiation device (SPOT CURE SP-7;
manufactured by Ushio Inc.) at an integrated light intensity of 100
mJ/cm.sup.2. The thickness of the obtained orientation layer was
measured using an ellipsometer. The result was 122 nm.
Subsequently, a coating solution composed of 1.0 g of mixture A,
0.060 g of Irg369, and 10.7 g of N-methylpyrrolidone was applied
onto the orientation layer using a bar coater, and then dried at
120.degree. C. for 1 minute, followed by exposure to ultraviolet
radiation (in a nitrogen atmosphere, wavelength: 365 nm, integrated
light intensity at a wavelength of 365 nm: 1000 mJ/cm.sup.2) using
a high-pressure mercury lamp (UNICURE VB-15201 BY-A, manufactured
by Ushio Inc.). Thus, an optical film was produced. A
pressure-sensitive adhesive was applied to the optical film thus
produced, and the optical film was bonded to a Cyclo-olefin Polymer
(COP) (ZF-14, manufactured by Zeon Corporation) which was treated
once using a Corona generator (AGF-B1.0, manufactured by Kasuga
Denki Inc.) under the conditions of an output of 0.3 kW and a
treatment rate of 3 m/min. Thereafter, the PET film as a substrate
was separated therefrom to produce optical film (1).
[0217] The optical film thus produced had a thickness of 2.0 .mu.m,
a retardation value (Re (550)) of 140 nm, and a degree of
wavelength dispersion Re(450 nm)/Re(550 nm) of 0.84.
Examples 2 to 4
[0218] Optical films (2) to (4) were each produced in the same
manner as in Example 1, except that before mixture A was applied
onto a polarizing layer, the liquid crystal compound having a
positive wavelength dispersion characteristic represented by
formula (2), which was synthesized according to the method
disclosed in JP-B-05451176, was added to mixture A and then mixed
so as to obtain the concentration of the liquid crystal compound
(2) shown in Table 1. The degrees of wavelength dispersion Re(450
nm)/Re(550 nm) of the optical films (2) to (4) thus produced were
measured. The results were shown in Table 1.
Reference Example 1
[0219] An optical film (5) was produced in the same manner as in
Example 1, except that liquid crystal compound (1) represented by
formula (1), which was synthesized according to the method
disclosed in JP-A-2009-173893, was used alone instead of using
mixture A. The degree of wavelength dispersion Re(450 nm)/Re (550
nm) of the optical film (5) thus produced was measured. The results
were shown in Table 1.
Example 5
[0220] An optical film (6) was produced in the same manner as in
Example 1, except that liquid crystal compound (1) represented by
formula (1), which was synthesized according to the method
disclosed in JP-A-2009-173893, and liquid crystal compound (2)
(content of liquid crystal compound (2) to liquid crystal compound
(1): 7.0 parts by mass) represented by formula (2), which was
synthesized according to the method disclosed in JP-B-05451176,
were used. The degree of wavelength dispersion Re (450 nm)/Re(550
nm) of the optical film (6) thus produced was measured. The results
were shown in Table 1.
TABLE-US-00001 TABLE 1 Content of Compound (2) Degree of Relative
to 100 Parts by Wavelength Mass of Compound (1) Dispersion Example
No. [pts. mass] Re (450 nm/550 nm) Example 1 7 0.84 Example 2 10
0.85 Example 3 15 0.86 Example 4 20 0.87 Example 5 7 0.84 Reference
0 0.82 Example 1
Example 6
[0221] A mixture B of a liquid crystal compound (1) having a
reverse wavelength dispersion characteristic represented by formula
(1) and a liquid crystal compound (2) having a positive wavelength
dispersion characteristic represented by formula (2) was obtained
in the same manner as in Example 1, except that the amount of
trans-cyclohexanedicarboxylic acid used was changed to 21.6 g (126
mmol) and the amount of sodium hydroxide used was changed to 1.1 g
(28 mmol).
[0222] Next, an optical film (7) was produced in the same manner as
in Example 1, except that mixture B was used instead of mixture A.
Because of high content of liquid crystal compound (2), the optical
film (7) showed higher degree of wavelength dispersion than the
optical film (1).
Example 7
[0223] A mixture C of a liquid crystal compound (1) having a
reverse wavelength dispersion characteristic represented by formula
(1) and a liquid crystal compound (2) having a positive wavelength
dispersion characteristic represented by formula (2) was obtained
in the same manner as in Example 1, except that the amount of
trans-cyclohexanedicarboxylic acid used was changed to 50.4 g (294
mmol) and the amount of sodium hydroxide used was changed to 4.2 g
(105 mmol).
[0224] Next, an optical film (8) was produced in the same manner as
in Example 1, except that mixture C was used instead of mixture A.
Because of low content of liquid crystal compound (2), the optical
film (8) showed lower degree of wavelength dispersion than the
optical film (I).
[0225] In view of these results, according to the present
invention, it is possible to easily produce an optical film having
a desired wavelength dispersion characteristic by selecting the
contents of liquid crystal compounds (1) and (2). Further,
according to the production method of the present invention, since
the wavelength dispersion characteristic of the optical film
finally produced can be controlled by selecting the amounts of
alcohol compound (3) and dicarboxylic acid compound (4) used, a
desired wavelength dispersion characteristic can be very
conveniently produced.
* * * * *