U.S. patent application number 10/400634 was filed with the patent office on 2005-11-24 for optical alignment method and liquid crystal display element.
This patent application is currently assigned to JSR CORPORATION. Invention is credited to Kimura, Masayuki, Yokoyama, Hiroshi.
Application Number | 20050259203 10/400634 |
Document ID | / |
Family ID | 28457606 |
Filed Date | 2005-11-24 |
United States Patent
Application |
20050259203 |
Kind Code |
A1 |
Kimura, Masayuki ; et
al. |
November 24, 2005 |
Optical alignment method and liquid crystal display element
Abstract
An optical alignment method which develops a pretilt angle by
batch plane exposure without tilting a substrate. This optical
alignment method provides liquid crystal aligning capability to the
surface of a polymer film by exposing the surface of the polymer
film through a slit exposure mask while the surface of the polymer
film and the slit exposure mask are moved relative to each other
substantially at a fixed rate. Alternatively, liquid crystal
aligning capability is provided to the surface of the polymer film
by exposing the surface of the polymer film through an optical
exposure pattern while the optical exposure pattern having a
plurality of lines with a certain width at certain intervals is
formed on the surface of the polymer film continuously.
Inventors: |
Kimura, Masayuki; (Tokyo,
JP) ; Yokoyama, Hiroshi; (Tukuba-shi, JP) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND, MAIER & NEUSTADT, P.C.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Assignee: |
JSR CORPORATION
Tokyo
JP
NATL. INST. OF ADV. INDUSTRIAL SCI. & TECH.
Tokyo
JP
|
Family ID: |
28457606 |
Appl. No.: |
10/400634 |
Filed: |
March 28, 2003 |
Current U.S.
Class: |
349/124 |
Current CPC
Class: |
G02F 1/133742 20210101;
G02F 1/133788 20130101 |
Class at
Publication: |
349/124 |
International
Class: |
G02F 001/1337 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 29, 2002 |
JP |
2002-093952 |
Oct 24, 2002 |
JP |
2002-309261 |
Oct 25, 2002 |
JP |
2002-311733 |
Claims
1. An optical alignment method comprising providing liquid crystal
aligning capability to the surface of a polymer film by exposing
the surface of the polymer film to radiation with an irradiation
intensity distribution while the surface of the polymer film and
radiation are moved relative to each other substantially at a fixed
rate without inclination of the surface of the polymer film.
2. The optical alignment method of claim 1, wherein liquid crystal
aligning capability is provided to the surface of the polymer film
by exposing the surface of the polymer film to radiation through a
slit exposure mask while the surface of the polymer film and the
slit exposure mask are moved relative to each other substantially
at a fixed rate.
3. The optical alignment method of claim 1, wherein the exposure of
the surface of the polymer film to radiation with an irradiation
intensity distribution is carried out by forming a projection
pattern on the polymer film by a projector and by exposing the
polymer film to radiation while the surface of the polymer film and
the projection pattern are moved relative to each other
substantially at a fixed rate.
4. The optical alignment method of claim 1, wherein liquid crystal
aligning capability and the developability of a pretilt angle of
80.degree. or more are provided to the surface of the polymer
film.
5. The optical alignment method of claim 4, wherein the polymer
film is made from a polymer having (A) a structure crosslinkable by
light and (B) at least one group selected from the group consisting
of a fluorine-containing organic group, alkyl group having 10 to 30
carbon atoms and alicylic organic group having 10 to 30 carbon
atoms.
6. The optical alignment method of claim 1, wherein the polymer
film provided with liquid crystal aligning capability on the
surface is a liquid crystal alignment film.
7. A liquid crystal display element comprising a liquid crystal
alignment film formed by the optical alignment method of claim
1.
8-26. (canceled)
27. The optical alignment method of claim 5, wherein recurring
units of structure (A) account for 10-95 percent of the total of
all recurring units, and recurring units having structure (B)
account for 5-50 percent of the total of all recurring units.
28. The optical alignment method of claim 1, wherein said surface
of the polymer film is exposed to radiation through a slit exposure
mask, and wherein said polymer film remain stationary and said slit
exposure mask is moved relative to the surface of the polymer film
during exposure.
29. The optical alignment method of claim 1, wherein said polymer
film is located on a transparent conductive film side of a
substrate.
30. The optical alignment method of claim 1, wherein the thickness
of the polymer film is 0.001-1 .mu.m.
31. The optical alignment method of claim 1, wherein said substrate
is transparent glass or a transparent plastic film.
32. The optical alignment method of claim 1, wherein the surface of
the polymer film and radiation are moved relative to each other at
a rate of 5 .mu.m/sec to 1 mm/sec.
33. The optical alignment method of claim 1, wherein said polymer
film is at a temperature ranging from its glass transition
temperature to a temperature 100 degrees centigrade higher than its
glass transition temperature during exposure.
34. The optical alignment method of claim 1, wherein said radiation
is polarized light.
35. The optical alignment method of claim 1, wherein said radiation
is non-polarized light.
36. The optical alignment method of claim 1, wherein said radiation
is polarized ultraviolet radiation having a wavelength of 320 to
450 nm.
37. The optical alignment method of claim 1, wherein the thickness
of the polymer film is 0.001-1 .mu.m, the surface of the polymer
film and radiation are moved relative to each other at a rate of 5
.mu.m/sec to 1 mm/sec, and the radiation is polarized light.
38. The optical alignment method of claim 28, wherein the thickness
of the polymer film is 0.001-1 .mu.m, the surface of the polymer
film and radiation are moved relative to each other at a rate of 5
.mu.m/sec to 1 mm/sec, and the radiation is polarized light.
39. The optical alignment method of claim 38, wherein said
radiation is polarized ultraviolet radiation having a wavelength of
320 to 450 nm.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to an optical alignment method
and to a liquid crystal display element formed by the same.
DESCRIPTION OF THE PRIOR ART
[0002] Liquid crystal display elements are widely used in monitors
for notebook personal computers and image display devices for
portable telephones and portable information terminals.
[0003] The liquid crystal display elements are divided into (1)
display type liquid crystal elements in which pixels are turned on
and off by optical switching through the selective application of a
voltage to liquid crystal molecules on a desired electrode formed
in the pixels after a panel having a large number of pixels is
constructed by sandwiching a liquid crystal material between glass
substrates at least one of which has a transparent electrode formed
thereon and (2) display type liquid crystal elements in which
desired pixels are turned on and off by selecting an active element
after a liquid crystal panel is constructed with a substrate having
an active element for selecting an electrode for each pixel and
another substrate having a pair of electrodes formed thereon. The
former is called "multiplex drive type" and the latter is called
"active drive type". To optimize the electro-optic display
characteristics of the liquid crystal display elements, liquid
crystal molecules must be aligned uniformly on a substrate having
an electrode.
[0004] To align the liquid crystals of an alignment film, "rubbing"
and light exposure are used. The alignment of liquid crystals by
rubbing is carried out by rubbing the surface of an alignment film
formed on a substrate with cotton, rayon or nylon and is widely
used for the production of a liquid crystal display element.
However, since the surface of an alignment film is directly rubbed
with cloth, the alignment film is chipped or static electricity is
generated by rubbing.
[0005] When the alignment film is chipped, dust is produced or the
surface of the alignment film is scratched, thereby causing the
marked deterioration of display quality when the above multiplex
drive type liquid crystal display element is turned on. In the
active drive type liquid crystal display element, the generation of
static electricity leads to the destruction of a TFT element as an
active element. In either case, rubbing causes reductions in the
contrast and productivity of the liquid crystal display
element.
[0006] Meanwhile, since the alignment of liquid crystals by light
exposure can be carried out without contacting the surface of an
alignment film unlike rubbing, the production of dust and the
generations of abrasion and static electricity are prevented. In
this method, the alignment film formed on a substrate is exposed to
polarized light from a desired direction to provide the alignment
controllability of liquid crystals in the polarization
direction.
[0007] As means of developing a pretilt angle in the above optical
alignment method, an oblique exposure method in which the surface
of a substrate having an optical alignment layer formed thereon is
exposed to ultraviolet radiation obliquely has been considered as
effective. For oblique exposure, the surface of an optical
alignment film must be exposed to light by setting the irradiation
angle to any angle from 1 to 90.degree.. To develop a pretilt angle
by oblique exposure, a substrate having an optical alignment layer
formed thereon must be inclined from a horizontal direction to
90.degree. with respect to ultraviolet radiation from the normal
direction (see FIG. 1), or a beam of light must be inclined from
the horizontal plane to the normal direction with respect to a
substrate placed horizontally for exposure (see FIG. 2). In
general, the former method is widely employed. In FIGS. 1 and 2,
reference numeral 8 denotes a filter, 9 denotes a polarizer and
other numerals denote the same elements as in FIG. 3.
[0008] However, this oblique exposure involves the following
problems.
[0009] (1) An error in the setting of the angle of the substrate
causes a great variation in pretilt angle.
[0010] (2) Since the substrate is inclined, irradiation energy
varies within the plane, which causes a variation in pretilt angle
within the plane.
[0011] (3) In the case of oblique exposure, the pretilt angle is
changed by the complicated secondary influences of light first
applied to the optical alignment layer and reflected light produced
while the above light passes through the layer.
[0012] (4) When the method of FIG. 1 is used with an oblique
exposure device and, for example, a 1 m.times.1 m glass substrate
is inclined at 45.degree. from the horizontal direction, the height
of the glass storage section of the exposure device must be 50 cm
or more, thereby greatly increasing the size of the device.
[0013] (5) When the method of FIG. 2 is used with an oblique
exposure device, it is very difficult in the design of the exposure
device to change the irradiation angle arbitrarily while a 1
m.times.1 m exposure area is ensured. That is, the structure of the
exposure device becomes complex by making variable the irradiation
angle of ultraviolet radiation in the exposure device due to the
control of the optical axis of an optical element and the like.
[0014] (6) It is difficult to develop a pretilt angle large enough
to be used in a homeotropic alignment mode.
SUMMARY OF THE INVENTION
[0015] It is an object of the present invention to provide a novel
optical alignment method which can solve the above problems.
[0016] It is another object of the present invention to provide an
optical alignment method which eliminates the need for the
inclination of a substrate in the method of developing a pretilt
angle in the optical alignment method and develops a pretilt angle
by batch plane exposure.
[0017] It is still another object of the present invention to
provide an optical alignment method which eliminates the need for
the inclination of a substrate in the method of developing a
pretilt angle in the optical alignment method and develops a
pretilt angle large enough to be used in a homeotropic alignment
mode by batch plane exposure.
[0018] It is a further object of the present invention to provide a
liquid crystal display element having a liquid crystal alignment
film formed by the optical alignment method of the present
invention.
[0019] Other objects and advantages of the present invention will
become apparent from the following description.
[0020] According to the present invention, firstly, the above
objects and advantages of the present invention are attained by an
optical alignment method comprising providing liquid crystal
aligning capability to the surface of a polymer film by exposing
the surface of the polymer film to radiation with an irradiation
intensity distribution while the surface of the polymer film and
radiation are moved relative to each other substantially at a fixed
speed (to be referred to as "first optical alignment method"
hereinafter).
[0021] According to the present invention, secondly, the above
objects and advantages of the present invention are attained by an
optical alignment method comprising providing liquid crystal
aligning capability to the surface of a polymer film by exposing
the surface of the polymer film to radiation through an optical
exposure pattern while the optical exposure pattern having a
plurality of lines with a certain width at certain intervals is
formed on the surface of the polymer film continuously in such a
manner that the lines form around a certain virtual base point on
the surface of the polymer film, expand concentrically toward the
periphery and disappear at the periphery, or that they start from
the periphery away from the virtual point, converge concentrically
on the virtual base point and disappear at the virtual base point
(to be referred to as "second optical alignment method"
hereinafter).
[0022] According to the present invention, thirdly, the above
objects and advantages of the present invention are attained by an
optical alignment method comprising providing liquid crystal
aligning capability to the surface of a polymer film by exposing
the surface of the polymer film to radiation through an optical
exposure pattern while the optical exposure pattern having a
plurality of lines with a certain width at certain intervals is
formed on the surface of the polymer film continuously in such a
manner that two areas sandwiching a certain virtual base line on
the surface of the polymer film differ from each other in at least
one of the pattern and the moving direction of the pattern, wherein
the lines of the optical exposure pattern are formed in the two
areas of the surface of the polymer film continuously in such a
manner that they start from the respective areas, move to cover the
respective areas and disappear in the respective areas.
[0023] (to be referred to as "third optical alignment method"
hereinafter).
[0024] According to the present invention, in the fourth place, the
above objects and advantages of the present invention are attained
by a liquid crystal display element having a liquid crystal
alignment film formed by the above optical alignment method of the
present invention.
[0025] Other objects and advantages of the present invention will
become apparent from the following description.
BRIEF DESCRIPTION OF THE DRAWINGS
[0026] FIG. 1 is a schematic diagram (side view) for explaining the
optical alignment method of the prior art;
[0027] FIG. 2 is a schematic diagram (side view) for explaining
another optical alignment method of the prior art;
[0028] FIG. 3 is a diagram (side view) for explaining an example of
the optical alignment method of the present invention;
[0029] FIG. 4 is a diagram (side view) for explaining another
example of the optical alignment method of the present
invention;
[0030] FIG. 5 is a diagram showing an example of the formation of
an optical exposure pattern in the optical alignment method of the
present invention;
[0031] FIG. 6 is a diagram (perspective view) for explaining an
example of the optical alignment method of the present
invention;
[0032] FIG. 7 is a diagram of an exposure mask pattern (slit
exposure mask) used in Examples of the present invention;
[0033] FIG. 8 is a diagram showing the relationship between the
moving rate of a movable stage and pretilt angle in Examples;
[0034] FIG. 9 is a diagram for explaining an example of the optical
alignment method of the present invention reference numeral 21
denotes UV source, reference numeral 22 denotes slit mask and
reference numeral 23 denotes projection lens; and
[0035] FIG. 10 is a diagram of the view field of the element of the
liquid crystal element obtained by Example 4.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0036] The polymer (may be referred to as "specific polymer"
hereinafter) used to form a liquid crystal alignment film in the
present invention is not limited to a particular kind but
preferably has a structure excited by light such as a structure
which can be crosslinked by light or decomposed by light. Out of
these, a polymer having a structure which can be crosslinked by
light is preferred.
[0037] The skeleton of the polymer used in the present invention is
not particularly limited. Examples of the polymer include polyamic
acid, polyamic acid ester, polyimide, polymaleimide, polystyrene,
maleimide/styrene copolymer, polyester, polyamide,
poly(meth)acrylate, polysiloxane and copolymers thereof. Polyamic
acid, polyamic acid ester, polyimide, polystyrene and
maleimide/styrene copolymer are preferred because they have
excellent thermal resistance and electric properties. These
polymers preferably have a glass transition temperature lower than
200.degree. C. because polymer molecules can be easily made mobile
without a risk of thermal deterioration.
[0038] The polymer used in the present invention is preferably a
polymer having (A) a structure which can be crosslinked by light
(to be referred to as "structure (A)" hereinafter) and/or (B) at
least one group selected from the group consisting of a
fluorine-containing organic group, alkyl group having 10 to 30
carbon atoms and alicyclic organic group having 10 to 30 carbon
atoms (to be referred to as "structure (B)" hereinafter).
[0039] As for the proportion of the structure (A) to the structure
(B) in the specific polymer, the recurring unit having the
structure (A) accounts for preferably 10 to 95%, more preferably 50
to 90% of the total of all the recurring units and the recurring
unit having the structure (B) accounts for preferably 5 to 50%,
more preferably 10 to 25% of the total of all the recurring
units.
[0040] The specific polymer may further have (C) a structure which
is crosslinked by heat (may be referred to as "structure (C)"
hereinafter). The structure (C) is an epoxy structure or the
like.
[0041] Structure (A)
[0042] The structure (A) is not particularly limited if it is an
optically crosslinkable structure. It is preferably at least one
conjugated enone structure selected from the group consisting of
structures represented by the following formulas (I), (II), (III),
(IV) and (V).
--P.sup.1--CR.sup.1.dbd.CR.sup.2--CO-Q.sup.1- (I)
P.sup.2--CR.sup.3.dbd.CR.sup.4--CO-Q.sup.2- (II)
P.sup.3--CR.sup.5.dbd.CR.sup.6--CO-Q.sup.3- (III)
--P.sup.4--CR.sup.7.dbd.CR.sup.8--CO-Q.sup.3- (IV)
--P.sup.5--CR.sup.9.dbd.CR.sup.10--CO-Q.sup.5 (V)
[0043] In the above formulas, P.sup.1, P.sup.4, Q.sup.1 and Q.sup.3
are each a divalent organic group having an aromatic ring, P.sup.2,
P.sup.3, Q.sup.4 and Q.sup.5 are each a monovalent organic group
having an aromatic ring, and P.sup.5 and Q.sup.2 are a trivalent
organic group having an aromatic ring. R.sup.1, R.sup.2, R.sup.3,
R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9 and R.sup.10
are each a hydrogen atom or alkyl group.
[0044] The organic group having an aromatic ring represented by
P.sup.1, P.sup.2, P.sup.3, P.sup.4, P.sup.5, Q.sup.1, Q.sup.2,
Q.sup.3, Q.sup.4 and Q.sup.5 is preferably an organic group having
6 to 20 carbon atoms.
[0045] The organic group may contain a halogen atom. Examples of
the organic group represented by P.sup.2, P.sup.3, Q.sup.4 and
Q.sup.5 include phenyl group, 4-methoxyphenyl group, 4-ethoxyphenyl
group, 4-cryanophenyl group, 4-pentylphenyl group, 4-fluorophenyl
group, 3,4-difluorophenyl group, 3,4,5-trifluorophenyl group,
4-(trifluoromethyl)phenyl group, 3,5-bis(trifluoromethyl)phenyl
group, 4-octylphenyl group, 4-pentylbiphenyl group, 4-octylbiphenyl
group, 4-fluorobiphenyl group, 3,4-difulorobiphenyl group,
3,4,5-trifluorobiphenyl group, 4-octyl-1-naphthyl group,
5-pentyl-1-naphthyl group, 6-octyl-2-naphthyl group, 9-anthracenyl
group and 10-pentyl-9-anthracenyl group.
[0046] Of these, examples of the organic group for a polymer having
a large pretilt angle are preferably 4-pentylphenyl group,
4-fluorophenyl group, 3,4-difluorophenyl group,
3,4,5-trifluorophenyl group, 4-octylphenyl group, 4-pentylbiphenyl
group, 4-octylbiphenyl group, 4-fluorobiphenyl group,
3,4-difluorobiphenyl group, 3,4,5-trfluorobiphenyl group,
4-octyl-1-naphtyl group, 5-pentyl-1-naphtyl group,
6-octyl-2-naphtyl group, 9-anthryl group, 10-pentyl-9-antyryl
group.
[0047] Examples of the organic group represented by P.sup.1,
P.sup.4, Q.sup.1 and Q.sup.3 include 1,2-phenylene group,
1,3-phenylene group, 1,4-phenylene group and 4,4'-biphenylene
group.
[0048] Examples of the organic group represented by P.sup.5 and
Q.sup.2 include trivalent skeletons such as benzene skeleton,
biphenyl skeleton, naphthalene skeleton and anthracene
skeleton.
[0049] These groups may be the same or different.
[0050] In the above formulas, R.sup.1, R.sup.2, R.sup.3, R.sup.4,
R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9 and R.sup.10 are each a
hydrogen atom or alkyl group, preferably a hydrogen atom or alkyl
group having 1 to 6 carbon atoms. These alkyl groups may be linear
or branched and the same or different.
[0051] In the present invention, out of the structures represented
by the above formula (IV), a chalcone structure represented by the
following formula (IV)-4 is particularly preferred:
--P.sup.41--CR.sup.7.dbd.CR.sup.8--CO-Q.sup.4 (IV)-4
[0052] wherein Q.sup.4, R.sup.7 and R.sup.8 are as defined in the
above formula (IV), and P.sup.41 is represented by the following
formula (IV)-4' or (IV)-4": 1
[0053] wherein T is a single bond or a divalent organic group
having 1 to 15 carbon atoms which may contain an oxygen atom.
[0054] In the formula (IV)-4', T is a single bond or a divalent
organic group having 1 to 15 carbon atoms which may contain an
oxygen atom. The divalent organic group having 1 to 15 carbon atoms
which may contain an oxygen atom is, for example, an organic group
represented by the following formula (IV)-4'": 2
[0055] wherein S.sup.1, S.sup.2 and S.sup.3 are each independently
an alkylene group having 1 to 15 carbon atoms or cycloalkylene
group, A.sup.1 and A.sup.2 are each independently a divalent
organic group represented by 3
[0056] and a, b, c, d and e are each independently 0 or 1, with the
proviso that at least one of a to e is 1.
[0057] Examples of the divalent organic group represented by the
formula (IV)-4' include 4,4'-bisphenylene group and organic groups
represented by the following formulas. 45
[0058] Other examples of the structure (A) include cinnamic acid
derivative structures, stilbene derivative structures, benzophenone
derivative structures and cinnamoyl structures. These structures
may be linear or part of a cyclic structure like a coumarin
structure. These structures (A) may be used alone or in combination
in the polymer component.
[0059] Structure (B)
[0060] The structure (B) is at least one selected from the group
consisting of fluorine-containing organic group, alkyl group having
10 to 30 carbon atoms and alicyclic organic group having 10 to 30
carbon atoms. It has the function of providing a pretilt angle to a
liquid crystal alignment film obtained from the liquid crystal
aligning agent of the present invention.
[0061] Examples of the fluorine-containing organic group include
trifluoromethyl group, pentafluoroethyl group, 4-fluorocyclohexyl
group, pentafluorocyclohexyl group, 4-fluorophenyl group and
pentafluorophenyl group. Examples of the alkyl group having 10 to
30 carbon atoms include n-decyl group, n-dodecyl group,
n-tetradecyl group, n-pentadecyl group, n-hexadecyl group,
n-octadecyl group and n-eicosyl group. Examples of the alicyclic
organic group having 10 to 30 carbon atoms include cholesteryl
group and cholestanyl group. The above fluorine-containing organic
group and alkyl group may be bonded by a bond group such as --O--,
--CO--, --COO--, --OCO--, --NHCO--, --CONH-- or --S-- in the
structure (B).
[0062] Specific Polymer
[0063] The above polyamic acid and polyimide which are examples of
the specific polymer are obtained by reacting (a) a tetracarboxylic
dianhydride with (b) a diamine compound to produce a polyamic acid
and by dehydrating and closing the ring of the polyamic acid to
produce a polyimide, respectively. In the production of the
polyamic acid and polyimide, a compound having the structure (A)
and/or a compound having the structure (B) are/is used as at least
one of the above components (a) and (b). Further, the polyamic acid
ester is obtained by reacting the above polymeric acid with a
halide, alcohol or phenol. In the production of the polyamic acid
ester, it is preferable that a compound having the structure (B) is
used as at least one of the above components (a) and (b) used in
the production of polyamic acid and a compound having the structure
(A) is used as a halide, alcohol or phenol.
[0064] Examples of the tetracarboxylic dianhydride having the
structure (A) include (a) 3,3'4,4'-chalconetetracarboxylic
dianhydride, 4,4',5,5'-chalconetetracarboxylic dianhydride,
3,3'4,5'-chalconetetracarb- oxylic dianhydride,
4,4'-dihydroxychalconebistrimellitate,
3,4'-dihydroxychalconebistrimellitate,
3',5'-dihydroxychalconebistrimelli- tate,
2,4-dihydroxychalconebistrimellitate,
2,2'-bis(4-(4-chalconyl)phenox-
y)-3,3',4,4'-biphenyltetracarboxylic dianhydride,
3,3'-bis(4-(4-chalconyl)-
phenoxy)-4,4',5,5'-biphenyltetracarboxylic dianhydride,
2,2'-bis(4-(4-chalconyl)phenoxy)-4,4',5,5'-biphenyltetracarboxylic
dianhydride,
4,4'-bis(4-(4-chalconyl)phenoxy)-2,2',3,3'-biphenyltetracarb-
oxylic dianhydride,
6,6'-bis(4-(4-chalconyl)phenoxy)-2,2',3,3'-biphenyltet-
racarboxylic dianhydride,
5,5'-bis(4-(4-chalconyl)phenoxy)-2,2',3,3'-biphe-
nyltetracarboxylic dianhydride,
2,2'-bis(4-(4-chalconyl)phenoxy)-3,3',4,4'- -diphenylether
tetracarboxylic dianhydride, 3,3'-bis(4-(4-chalconyl)phenox-
y)-4,4',5,5'-diphenylether tetracarboxylic dianhydride,
2,2'-bis(4-(4-chalconyl)phenoxy)-4,4',5,5'-diphenylether
tetracarboxylic dianhydride,
4,4'-bis(4-(4-chalconyl)phenoxy)-2,2',3,3'-diphenylether
tetracarboxylic dianhydride,
6,6'-bis(4-(4-chalconyl)phenoxy)-2,2',3,3'-d- iphenylether
tetracarboxylic dianhydride, 5,5'-bis(4-(4-chalconyl)phenoxy)-
-2,2',3,3'-diphenylether tetracarboxylic dianhydride, compounds
represented by the following formulas (1) to (10). 67
[0065] (b)
2,2'-bis(4-chalconyloxy)-3,3',4,4'-biphenyltetracarboxylic
dianhydride,
3,3'-bis(4-chalconyloxy)-4,4',5,5'-biphenyltetracarboxylic
dianhydride,
2,2'-bis(4-chalconyloxy)-4,4',5,5'-biphenyltetracarboxylic
dianhydride,
4,4'-bis(4-chalconyloxy)-2,2',3,3'-biphenyltetracarboxylic
dianhydride,
6,6'-bis(4-chalconyloxy)-2,2',3,3'-biphenyltetracarboxylic
dianhydride,
5,5'-bis(4-chalconyloxy)-2,2',3,3'-biphenyltetracarboxylic
dianhydride, 2,2'-bis(4-chalconyloxy)-3,3',4,4'-diphenylether
tetracarboxylic dianhydride,
3,3'-bis(4-chalconyloxy)-4,4',5,5'-diphenyle- ther tetracarboxylic
dianhydride, 2,2'-bis(4-chalconyloxy)-4,4',5,5'-diphe- nylether
tetracarboxylic dianhydride, 4,4'-bis(4-chalconyloxy)-2,2',3,3'-d-
iphenylether tetracarboxylic dianhydride,
6,6'-bis(4-chalconyloxy)-2,2',3,- 3'-diphenylether tetracarboxylic
dianhydride, 5,5'-bis(4-chalconyloxy)-2,2- ',3,3'-diphenylether
tetracarboxylic dianhydride, 2,2'-bis(6-(4-chalconylo-
xy)hexyloxy)-3,3',4,4'-biphenyltetracarboxylic dianhydride,
2,2'-bis(6-(4'-fluoro-4-chalconyloxy)hexyloxy)-3,3',4,4'-biphenyltetracar-
boxylic dianhydride,
3,3'-bis(6-(4-chalconyloxy)hexyloxy)-4,4',5,5'-biphen-
yltetracarboxylic dianhydride,
3,3'-bis(6-(4'-fluoro-4-chalconyloxy)hexylo-
xy)-4,4',5,5'-biphenyltetracarboxylic dianhydride,
2,2'-bis(6-(4-chalconyl-
oxy)hexyloxy)-4,4',5,5'-biphenyltetracarboxylic dianhydride,
2,2'-bis(6-(4'-fluoro-4-chalconyloxy)hexyloxy)-4,4',5,5'-biphenyltetracar-
boxylic dianhydride,
4,4'-bis(6-(4-chalconyloxy)hexyloxy)-2,2',3,3'-biphen-
yltetracarboxylic dianhydride,
4,4'-bis(6-(4'-fluoro-4-chalconyloxy)hexylo-
xy)-2,2',3,3'-biphenyltetracarboxylic dianhydride,
6,6'-bis(6-(4-chalconyl-
oxy)hexyloxy)-2,2',3,3'-biphenyltetracarboxylic dianhydride,
6,6'-bis(6-(4'-fluoro-4-chalconyloxy)hexyloxy)-2,2',3,3'-biphenyltetracar-
boxylic dianhydride,
5,5'-bis(6-(4-chalconyloxy)hexyloxy)-2,2',3,3'-biphen-
yltetracarboxylic dianhydride,
5,5'-bis(6-(4'-fluoro-4-chalconyloxy)hexylo-
xy)-2,2',3,3'-biphenyltetracarboxylic dianhydride,
2,2'-bis(6-(4-chalconyl- oxy)hexyloxy)-3,3',4,4'-diphenylether
tetracarboxylic dianhydride,
2,2'-bis(6-(4'-fluoro-4-chalconyloxy)hexyloxy)-3,3',4,4'-diphenylether
tetracarboxylic dianhydride,
3,3'-bis(6-(4-chalconyloxy)hexyloxy)-4,4',5,- 5'-diphenylether
tetracarboxylic dianhydride, 3,3'-bis(6-(4'-fluoro-4-chal-
conyloxy)hexyloxy)-4,4',5,5'-diphenylether tetracarboxylic
dianhydride,
2,2'-bis(6-(4-chalconyloxy)hexyloxy)-4,4',5,5'-diphenylether
tetracarboxylic dianhydride,
2,2'-bis(6-(4'-fluoro-4-chalconyloxy)hexylox-
y)-4,4',5,5'-diphenylether tetracarboxylic dianhydride,
4,4'-bis(6-(4-chalconyloxy)hexyloxy)-2,2',3,3'-diphenylether
tetracarboxylic dianhydride,
4,4'-bis(6-(4'-fluoro-4-chalconyloxy)hexylox-
y)-2,2',3,3'-diphenylether tetracarboxylic dianhydride,
6,6'-bis(6-(4-chalconyloxy)hexyloxy)-2,2',3,3'-diphenylether
tetracarboxylic dianhydride,
6,6'-bis(6-(4'-fluoro-4-chalconyloxy)hexylox-
y)-2,2',3,3'-diphenylether tetracarboxylic dianhydride,
5,5'-bis(6-(4-chalconyloxy)hexyloxy)-2,2',3,3'-diphenylether
tetracarboxylic dianhydride,
5,5'-bis(6-(4'-fluoro-4-chalconyloxy)hexylox-
y)-2,2',3,3'-diphenylether tetracarboxylic dianhydride,
2,2'-bis(6-(4-chalconyloxy)hexyloxy)-3,3',4,4'-benzophenonetetracarboxyli-
c dianhydride,
2,2'-bis(6-(4'-fluoro-4-chalconyloxy)hexyloxy)-3,3',4,4'-be-
nzophenonetetracarboxylic dianhydride,
3,3'-bis(6-(4-chalconyloxy)hexyloxy-
)-4,4',5,5'-benzophenonetetracarboxylic dianhydride,
3,3'-bis(6-(4'-fluoro-4-chalconyloxy)hexyloxy)-4,4',5,5'
-benzophenonetetracarboxylic dianhydride,
2,2'-bis(6-(4-chalconyloxy)hexy-
loxy)-4,4',5,5'-benzophenonetetracarboxylic dianhydride,
2,2'-bis(6-(4'-fluoro-4-chalconyloxy)hexyloxy)-4,4',5,5'-benzophenonetetr-
acarboxylic dianhydride,
4,4'-bis(6-(4-chalconyloxy)hexyloxy)-2,2',3,3'-be-
nzophenonetetracarboxylic dianhydride,
4,4'-bis(6-(4'-fluoro-4-chalconylox-
y)hexyloxy)-2,2',3,3'-benzophenonetetracarboxylic dianhydride,
6,6'-bis(6-(4-chalconyloxy)hexyloxy)-2,2',3,3'-benzophenonetetracarboxyli-
c dianhydride,
6,6'-bis(6-(4'-fluoro-4-chalconyloxy)hexyloxy)-2,2',3,3'-be-
nzophenonetetracarboxylic dianhydride,
5,5'-bis(6-(4-chalconyloxy)hexyloxy-
)-2,2',3,3'-benzophenonetetracarboxylic dianhydride,
5,5'-bis(6-(4'-fluoro-4-chalconyloxy)hexyloxy)-2,2',3,3'-benzophenonetetr-
acarboxylic dianhydride, 3(6-(4-chalconyloxy)hexyloxy)-pyromellitic
dianhydride, 3(6-(4'-fluoro-4-chalconyloxy)hexyloxy)-pyromellitic
dianhydride, 3,6-bis(6-(4-chalconyloxy)hexyloxy)-pyromellitic
dianhydride,
3,6-bis(6-(4'-fluoro-4-chalconyloxy)hexyloxy)-pyromellitic
dianhydride, compounds represented by the following formulas (11)
to (32): 891011
[0066]
2,2'-bis(4-(4-chalconyl)phenoxy)-3,3',4,4'-biphenyltetracarboxylic
dianhydride,
3,3'-bis(4-(4-chalconyl)phenoxy)-4,4',5,5'-biphenyltetracarb-
oxylic dianhydride,
2,2'-bis(4-(4-chalconyl)phenoxy)-4,4',5,5'-biphenyltet-
racarboxylic dianhydride,
4,4'-bis(4-(4-chalconyl)phenoxy)-2,2'3,3'-biphen- yltetracarboxylic
dianhydride, 6,6'-bis(4-(4-chalconyl)phenoxy)-2,2',3,3'--
biphenyltetracarboxylic dianhydride,
5,5'-bis(4-(4-chalconyl)phenoxy)-2,2'-
,3,3'-biphenyltetracarboxylic dianhydride,
2,2'-bis(4-(4-chalconyl)phenoxy- )-3,3',4,4'-diphenylether
tetracarboxylic dianhydride,
3,3'-bis(4-(4-chalconyl)phenoxy)-4,4',5,5'-diphenylether
tetracarboxylic dianhydride,
2,2'-bis(4-(4-chalconyl)phenoxy)-4,4',5,5'-diphenylether
tetracarboxylic dianhydride,
4,4'-bis(4-(4-chalconyl)phenoxy)-2,2',3,3'-d- iphenylether
tetracarboxylic dianhydride, 6,6'-bis(4-(4-chalconyl)phenoxy)-
-2,2',3,3'-diphenylether tetracarboxylic dianhydride and
5,5'-bis(4-(4-chalconyl)phenoxy)-2,2',3,3'-diphenylether
tetracarboxylic dianhydride. They may be used alone or in
combination of two or more.
[0067] The above compounds listed in (b) are preferably used to
obtain a polymer which provides a large pretilt angle.
[0068] Examples of the diamine compound having the structure (A)
include (C) 3,3'-diaminochalcone, 4,4'-diaminochalcone,
3,4'-diaminochalcone, 3,4-diaminochalcone,
4-(3,5-diaminophenoxy)chalcone, 4'-(2,4-diaminophenoxy)chalcone,
4-(4-(2,4-diaminophenoxy)phenyl)chalcone- ,
4-(4-(2-(2,4-diaminophenoxy)ethoxy)phenyl)chalcone,
4-(4-(6-(2,4-diaminophenoxy)hexanoxy)phenyl)chalcone,
4-(2-(2,4-diaminophenoxy)ethyl)chalcone carboxylate,
4-(6-(2,4-diaminophenoxy)hexyl)chalcone carboxylate,
4-(4-(2,4-diaminophenoxy)bezoyloxy)chalcone,
4-(4-(2,4-diaminophenoxy)phe- nyl)chalcone carboxylate,
4-(4-(2-(2,4-diaminophenoxy)ethoxy)benzoyloxy)ch- alcone,
4-(4-(2-(2,4-diaminophenoxy)ethoxy)phenyl)chalcone carboxylate,
4-(4-(6-(2,4-diaminophenoxy)hexanoxy)benzoyloxy)chalcone,
4-(4-(6-(2,4-diaminophenoxy)hexanoxy)phenyl)chalcone carboxylate,
4-(4-(3,5-diaminobenzoyloxy)phenyl)chalcone,
4-(4-(2-(3,5-diaminobenzoylo- xy)ethoxy)phenyl)chalcone,
4-(4-(6-(3,5-diaminobenzoyloxy)hexanoxy)phenyl)- chalcone,
4-(2-(3,5-diaminobenzoyloxy)ethyl)chalcone carboxylate,
4-(6-(3,5-diaminobenzoyloxy)hexyl)chalcone carboxylate,
4-(4-(3,5-diaminobenzoyloxy)benzoyloxy)chalcone,
4-(4-(3,5-diaminobenzoyl- oxy)phenyl)chalcone carboxylate,
4-(4-(2-(3,5-diaminobenzoyloxy)ethoxy)ben- zoyloxy)chalcone,
4-(4-(2-(3,5-diaminobenzoyloxy)ethoxy)phenyl)chalcone carboxylate,
4-(4-(6-(3,5-diaminobenzoyloxy)hexanoxy)benzoyloxy)chalcone,
4-(4-(6-(3,5-diaminobenzoyloxy)hexanoxy)phenyl)chalcone
carboxylate, compounds represented by the following formulas (41)
to (46). 1213
[0069] and a compound represented by the following formula (VI):
14
[0070] wherein A.sup.1 and A.sup.2 are each a divalent aromatic
group, and n is an integer of 1 to 10.
[0071] In the above formula (VI), the alkyl group represented by
C.sub.nH.sub.2n+1-- may be linear or branched, preferably linear.
Examples of the divalent aromatic group represented by A.sup.1 and
A.sup.2 include phenylene group, biphenylene group, naphthylene
group, binaphthylene group, anthrylene group and phenanthrylene
group, and organic groups obtained by excluding two hydrogen atoms
from a polycyclic aromatic compound such as pyrene, chrysene or
naphthacene.
[0072] Examples of the compound represented by the above formula
(VI) include 4-isopropyl-4'-(3,5-diaminophenoxy)chalcone,
4-amyl-4"-(3,5-diaminophenoxy)chalcone,
4-pentyl-4'-(3,5-diaminophenoxy)c- halcone,
4-octyl-4'-(3,5-diaminophenoxy)chalcone, 4-pentyl-2-methyl-4'-(2,-
4-diaminophenoxy)chalcone,
4-pentyl-2,5-dimethyl-4'-(3,5-diaminophenoxy)ch- alcone,
4-octyl-2-methyl-4'-(3,5-diaminophenoxy)chalcone,
4-pentyl-4'-(2,4-diaminophenoxy)chalcone,
4-octyl-4'-(2,4-diaminophenoxy)- chalcone,
4-pentyl-4'-(3,5-diaminobenzoyloxy)chalcone,
4-octyl-4'-(3,5-diaminobenzoyloxy)chalcone,
4-pentyl-3'-(2,4-diaminobenzo- yloxy)chalcone and
4-octyl-3'-(2,4-diaminobenzoyloxy)chalcone.
[0073] Other examples of the diamine compound having the structure
(A) include (d) 4-(3,5-diaminophenoxy)-4'-isopropylchalcone,
4-(3,5-diaminophenoxy)-4'-pentylchalcone,
4-(3,5-diaminophenoxy)-4'-octyl- chalcone,
4-(2,4-diaminophenoxy)-4'-pentylchalcone,
4-(2,4-diaminophenoxy)-4'-octylchalcone,
4-(3,5-diaminobenzoyloxy)-4'-pen- tylchalcone,
4'-(4-pentylphenyl)-4-(3,5-diaminophenoxy)chalcone,
6-(4-chalconyloxy)hexyloxy(2,4-diaminobenzene),
6-(4'-fluoro-4-chalconylo- xy)hexyloxy(2,4-diaminobenzene),
8-(4-chalconyloxy)octyloxy(2,4-diaminoben- zene),
8-(4'-fluoro-4-chalconyloxy)octyloxy(2,4-diaminobenzene),
10-(4-chalconyloxy)decyloxy(2,4-diaminobenzene),
10-(4'-fluoro-4-chalcony- loxy)decyloxy(2,4-diaminobenzene),
2-(2-(4-chalconyloxy)ethoxy)ethyl(3,5-d- iaminobenzoate),
2-(2-(4'-fluoro-4-chalconyloxy)ethoxy)ethyl(3,5-diaminobe- nzoate),
2-(2-(4-chalconyloxy)ethoxy)ethoxy(2,4-diaminobenzene),
2-(2-(4'-fluoro-4-chalconyloxy)ethoxy)ethoxy(2,4-diaminobenzene),
1-((4-chalconyloxy)ethoxy)-2-((2,4-diaminophenoxy)ethoxy)ethane,
1-((4'-fluoro-4-chalconyloxy)ethoxy)-2-((2,4-diaminophenoxy)ethoxy)ethane-
,
1-((4-chalconyloxy)ethoxy)-2-((3,5-diaminobenzoyloxy)ethoxy)ethane,
1-((4'-fluoro-4-chalconyloxy)ethoxy)-2-((3,5-diaminobenzoyloxy)ethoxy)eth-
ane, 6-(4-chalconyloxy)hexyloxy(3,5-diaminobenzoyl),
6-(4'-fluoro-4-chalconyloxy)hexyloxy(3,5-diaminobenzoyl),
8-(4-chalconyloxy)octyloxy(3,5-diaminobenzoyl),
8-(4'-fluoro-4-chalconylo- xy)octyloxy(3,5-diaminobenzoyl),
10-(4-chalconyloxy)decyloxy(3,5-diaminobe- nzoyl),
10-(4'-fluoro-4-chalconyloxy)decyloxy(3,5-diaminobenzoyl),
6-(4-chalconyloxy)hexanoic acid (2,4-diaminophenyl),
6-(4'-fluoro-4-chalconyloxy)hexanoic acid (2,4-diaminophenyl),
8-(4-chalconyloxy)-octanoic acid-(2,4-diaminophenyl),
8-(4'-fluoro-4-chalconyloxy)-octanoic acid-(2,4-diaminophenyl),
10-(4-chalconyloxy)-decanoic acid-(2,4-diaminophenyl),
10-(4'-fluoro-4-chalconyloxy)-decanoic acid-(2,4-diaminophenyl),
mono(4-chalconyl)mono(2,4-diaminophenyl)adipate,
mono(4'-fluoro-4-chalcon- yl)mono(2,4-diaminophenyl)adipate,
mono(4-chalconyl)mono(2,4-diaminophenyl- )suberate,
mono(4'-fluoro-4-chalconyl)mono(2,4-diaminophenyl)suberate,
mono(4-chalconyl)mono(2,4-diaminophenyl)sebacate,
mono(4'-fluoro-4-chalco- nyl)mono(2,4-diaminophenyl)sebacate,
bis-1,1-(4-aminophenyl)-6-(4-chalcony- loxy)hexane,
bis-1,1-(4-aminophenyl)-6-(4'-fluoro-4-chalconyloxy)hexane,
bis-1,1-(4-aminophenyl)-8-(4-chalconyloxy)octane,
bis-1,1-(4-aminophenyl)- -8-(4'-fluoro-4-chalconyloxy)octane,
bis-1,1-(4-aminophenyl)-10-(4-chalcon- yloxy)decane,
bis-1-(4-aminophenyl)-10-(4'-fluoro-4-chalconyloxy)decane,
bis-N,N-(4-aminophenyl)-N-(6-(4-chalconyloxy)hexanoxyphenyl)amine,
bis-N,N-(4-aminophenyl)-N-(6-(4'-fluoro-4-chalconyloxy)hexanoxyphenyl)ami-
ne,
bis-N,N-(4-aminophenyl)-N-(8-(4-chalconyloxy)octanoxyphenyl)amine,
bis-N,N-(4-aminophenyl)-N-(8-(4'-fluoro-4-chalconyloxy)octanoxyphenyl)ami-
ne,
bis-N,N-(4-aminophenyl)-N-(10-(4-chalconyloxy)decanoxyphenyl)amine,
bis-N,N-(4-aminophenyl)-N-(10-(4'-fluoro-4-chalconyloxy)decanoxyphenyl)am-
ine,
bis-N,N-(4-aminophenyl)-N-(2-(2-(4-chalconyloxy)ethoxy)ethoxyphenyl)a-
mine,
bis-N,N-(4-aminophenyl)-N-(4-(2-(2-(4'-fluoro-4-chalconyloxy)ethoxy)-
ethoxy)phenyl)amine, 4-(4-(2,4-diaminophenoxy)phenyl)chalcone,
4-(4-(2-(2,4-diaminophenoxy)ethoxy)phenyl)chalcone,
4-(4-(6-(2,4-diaminophenoxy)hexanoxy)phenyl)chalcone,
4-(2-(2,4-diaminophenoxy)ethyl)chalcone carboxylato,
4-(6-(2,4-diaminophenoxy)hexyl)chalcone carboxylato,
4-(4-(2,4-diaminophenoxy)benzoyloxy)chalcone,
4-(4-(2,4-diaminophenoxy)ph- enyl)chalcone carboxylato,
4-(4-(2-(2,4-diaminophenoxy)ethoxy)benzoyloxy)c- halcone,
4-(4-(2-(2,4-diaminophenoxy)ethoxy)phenyl)chalcone carboxylato,
4-(4-(6-(2,4-diaminophenoxy)hexanoxy)benzoyloxy)chalcone,
4-(4-(6-(2,4-diaminophenoxy)hexanoxy)phenyl)chalcone carboxylato,
4-(4-(3,5-diaminobenzoyloxy)phenyl)chalcone,
4-(4-(2-(3,5-diaminobenzoylo- xy)ethoxy)phenyl)chalcone,
4-(4-(6-(3,5-diaminobenzoyloxy)hexanoxy)phenyl)- chalcone,
4-(2-(3,5-diaminobenzoyloxy)ethyl)chalcone carboxylato,
4-(6-(3,5-diaminobenzoyloxy)hexyl)chalcone carboxylato,
4-(4-(3,5-diaminobenzoyloxy)benzoyloxy)chalcone,
4-(4-(3,5-diaminobenzoyl- oxy)phenyl)chalcone carboxylato,
4-(4-(2-(3,5-diaminobenzoyloxy)ethoxy)ben- zoyloxy) chalcone,
4-(4-(2-(3,5-diaminobenzoyloxy)ethoxyl)phenyl) chalcone
carboxylato, 4-(4-(6-(3,5-diaminobenzoyloxy)hexanoxy)benzoyloxy)
chalcone, and
4-(4-(6-(3,5-diaminobenzoyloxy)hexanoxy)phenyl)chalcone
carboxylato.
[0074] These diamine compounds may be used alone or in combination
of two or more.
[0075] The compounds (d) are preferably used to obtain a polymer
which provides a large pretilt angle.
[0076] Examples of the tetracarboxylic dianhydride having the
structure (B) include compounds represented by the following
formulas (51) to (64). They may be used alone or in combination of
two or more. 151617
[0077] Examples of the diamine compound having the structure (B)
include 1-dodecanoxy-2,4-diaminobenzene,
1-tetradecanoxy-2,4-diaminobenzene,
1-pentadecanoxy-2,4-diaminobenzene,
1-hexadecanoxy-2,4-diaminobenzene,
1-octadecanoxy-2,4-diaminobenzene,
1-cholesteryloxy-2,4-diaminobenzene,
1-cholestanyloxy-2,4-diaminobenzene,
dodecanoxy(3,5-diaminobenzoyl), tetradecanoxy(3,5-diaminobenzoyl),
pentadecanoxy(3,5-diaminobenzoyl),
hexadecanoxy(3,5-diaminobenzoyl), octadecanoxy(3,5-diaminobenzoyl),
cholesteryloxy(3,5-diaminobenzoyl),
cholestanyloxy(3,5-diaminobenzoyl), (2,4-diaminophenoxy)palmitate,
(2,4-diaminophenoxy)stearate,
(2,4-diaminophenoxy)-4-trifluoromethyl benzoate and compound
represented by the following formula (65). 18
[0078] The polyimide used in the present invention may be used in
conjunction with another tetracarboxylic dianhydride and/or diamine
compound in limits that do not impair the effect of the present
invention. These components are preferably used in a total amount
of 80 mol % or less based on the total of the compound having the
above structure (A) and/or the compound having the structure (B).
Particularly when a polymer having a large pretilt angle is to be
obtained, the amount is more preferably 60 mol % or less, much more
preferably 20 mol % or less.
[0079] Examples of the other tetracarboxylic dianhydride include
aliphatic and alicyclic tetracarboxylic dianhydrides such as
2,3,5-tricarboxycyclopentylacetic dianhydride,
butanetetracarboxylic dianhydride,
1,2,3,4-cyclobutanetetracarboxylic dianhydride,
1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride,
1,2,3,4-cyclopentanetetracarboxylic dianhydride,
3,5,6-tricarboxynorborna- ne-2-acetic dianhydride,
2,3,4,5-tetrahydrofurantetracarboxylic dianhydride,
1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-n-
aphtho[1,2-c]-furan-1,3-dione,
5-(2,5-dioxotetrahydrofural)-3-methyl-3-cyc-
lohexene-1,2-dicarboxylic dianhydride and
bicyclo[2.2.2]-oct-7-ene-2,3,5,6- -tetracarboxylic dianhydride; and
aromatic tetracarboxylic dianhydrides such as pyromellitic
dianhydride, 3,3',4,4'-biphenylsulfonetetracarboxyli- c
dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride,
2,3,6,7-naphthalenetetracarboxylic dianhydride,
3,3',4,4'-biphenyletherte- tracarboxylic dianhydride,
3,3',4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride,
3,3',4,4'-tetraphenylsilanetetracarboxylic dianhydride,
1,2,3,4-furantetracarboxylic dianhydride,
4,4'-bis(3,4-dicarboxyphenoxy)d- iphenylsulfide dianhydride,
4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride,
4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride,
3,3',4,4'-perfluoroisopropylidenetetracarboxylic dianhydride, 3,3',
4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic
acid)phenylphosphine oxide dianhydride,
p-phenylene-bis(triphenylphthalic acid)dianhydride,
m-phenylene-bis(triphenylphthalic acid)dianhydride,
bis(triphenylphthalic acid)-4,4'-diphenylether dianhydride and
bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride.
[0080] Out of these, preferred are
2,3,5-tricarboxycyclopentylacetic dianhydride,
butanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cycl-
obutanetetracarboxylic dianhydride,
1,2,3,4-cyclobutanetetracarboxylic dianhydride, pyromellitic
dianhydride, 3,3',4,4'-biphenylsulfonetetracarb- oxylic
dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride,
2,3,6,7-naphthalenetetracarboxylic dianhydride,
3,3',4,4'-biphenyletherte- tracarboxylic dianhydride. They may be
used alone or in combination of two or more.
[0081] Examples of the other diamine compounds include aromatic
diamines such as p-phenylenediamine, m-phenylenediamine,
4,4'-diaminodiphenylmetha- ne, 4,4'-diaminodiphenylethane,
4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylsulfone,
3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide,
4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene,
3,3-dimethyl-4,4'-diaminobiphenyl,
5-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane,
6-amino-1-(4'-aminophen- yl)-1,3,3-trimethylindane,
3,4'-diaminodiphenyl ether, 2,2-bis(4-aminophenoxy)propane,
2,2-bis[4-(4-aminophenoxy)phenyl]propane,
2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane,
2,2-bis(4-aminophenyl)hexafluoropropane,
2,2-bis[4-(4-aminophenoxy)phenyl- ]sulfone,
1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene,
1,3-bis(3-aminophenoxy)benzene,
9,9-bis(4-aminophenyl)-10-hydroanthracene- , 2,7-diaminofluorene,
9,9-bis(4-aminophenyl)fluorene,
4,4'-methylene-bis(2-chloroaniline),
2,2',5,5'-tetrachloro-4,4'-diaminobi- phenyl,
2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl,
3,3'-dimethoxy-4,4'-diaminobiphenyl,
4,4'-(p-phenyleneisopropylidene)bisa- niline,
4,4'-(m-phenyleneisopropylidene)bisaniline,
2,2'-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane,
4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl and
4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl;
aromatic diamines having a hetero atom such as diaminotetraphenyl
thiophene; aliphatic and alicyclic diamines such as
1,1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine,
pentamethylenediamine, hexamethylenediamine, heptamethylenediamine,
octamethylenediamine, nonamethylenediamine,
4,4-diaminoheptamethylenediamine, 1,4-diaminocyclohexane,
isophoronediamine, tetrahydrodicyclopentadienylen- ediamine,
hexahydro-4,7-metanoindanylenedimethylenediamine,
tricyclo[6.2.1.0.sup.2.7]-undecylenedimethyldiamine and
4,4'-methylenebis(cyclohexylamine); and diaminoorganosiloxanes such
as diaminohexamethyldisiloxane.
[0082] Of these, preferred are p-phenylenediamine,
4,4'-diaminodiphenylmet- hane, 1,5-diaminonaphthalene,
2,7-diaminofluorene, 4,4'-diaminodiphenyl ether,
4,4'-(p-phenyleneisopropylidene)bisaniline,
2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane,
2,2'-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane,
4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl,
4,4'-bis[(4-amino-2-trifl- uoromethyl)phenoxy]-octafluorobiphenyl.
They may be used alone or in combination of two or more.
[0083] The polyimide used in the present invention is obtained by
polycondensing the above tetracarboxylic dianhydride component (A)
with the above diamine component (B) to obtain a polyamic acid and
heating the polyamic acid, if necessary, in the presence of a
dehydrating agent and an imidizing catalyst to imidize it. The
reaction temperature for imidization by heating is preferably 60 to
300.degree. C., more preferably 100 to 170.degree. C. When the
reaction temperature is lower than 60.degree. C., the reaction
proceeds slowly and when the reaction temperature is higher than
300.degree. C., the molecular weight of the polyamic acid may
greatly lower. The reaction for imidization in the presence of a
dehydrating agent and an imidizing catalyst may be carried out in
an organic solvent. The reaction temperature is preferably 0 to
180.degree. C., more preferably 60 to 150.degree. C. The
dehydrating agent is an acid anhydride such as acetic anhydride,
propionic anhydride or trifluoroacetic anhydride. The imidizing
catalyst is a tertiary amine such as pyridine, collidine, lutidine
or triethylamine. The amount of the dehydrating agent is preferably
1.6 to 20 mols based on 1 mol of the recurring unit of the polyamic
acid. The amount of the imidizing catalyst is preferably 0.5 to 10
mols based on 1 mol of the dehydrating agent used. The content of
the amic acid residue in the polyimide can be adjusted by the
amounts of the imidizing catalyst and the dehydrating agent.
[0084] Examples of the halide having the structure (A) used in the
production of polymaic acid ester include
1-bromo-3-(4-chalconyloxy)propa- ne,
1-bromo-3-(4'-chalconyloxy)propane,
1-bromo-4-(4-chalconyloxy)butane,
1-bromo-4-(4'-chalconyloxy)butane,
1-bromo-6-(4-chalconyloxy)hexane,
1-bromo-6-(4'-chalconyloxy)hexane,
1-chloro-3-(4-chalconyloxy)propane,
1-chloro-3-(4'-chalconyloxy)propane,
1-chloro-4-(4-chalconyloxy)butane,
1-chloro-4-(4'-chalconyloxy)butane,
1-chloro-6-(4-chalconyloxy)hexane,
1-chloro-6-(4'-chalconyloxy)hexane,
1-bromo-3-(4'-fluoro-4-chalconyloxy)p- ropane,
1-bromo-3-(4-fluoro-4'-chalconyloxy)propane,
1-bromo-4-(4'-fluoro-4-chalconyloxy)butane,
1-bromo-4-(4-fluoro-4'-chalco- nyloxy)butane,
1-bromo-6-(4'-fluoro-4-chalconyloxy)hexane,
1-bromo-6-(4-fluoro-4'-chalconyloxy)hexane,
1-chloro-3-(4'-fluoro-4-chalc- onyloxy)propane,
1-chloro-3-(4-fluoro-4'-chalconyloxy)propane,
1-chloro-4-(4'-fluoro-4-chalconyloxy)butane,
1-chloro-4-(4-fluoro-4'-chal- conyloxy)butane,
1-chloro-6-(4'-fluoro-4-chalconyloxy)hexane and
1-chloro-6-(4-fluoro-4'-chalconyloxy)hexane. They may be used alone
or in combination of two or more.
[0085] Out of these, 1-bromo-6-(4-chalconyloxy)hexane and
1-bromo-6-(4'-fluoro-4-chalconyloxy)hexane are preferred.
[0086] Examples of the alcohol having the structure (A) include
3-(4-chalconyloxy)-1-propanol, 3-(4'-chalconyloxy)-1-propanol,
1-4-(4-chalconyloxy)-1-butanol, 4-(4'-chalconyloxy)-1-butanol,
6-(4-chalconyloxy)-1-hexanol, 6-(4'-chalconyloxy)-1-hexanol,
3-(4'-fluoro-4-chalconyloxy)-1-propanol,
3-(4-fluoro-4'-chalconyloxy)-1-p- ropanol,
4-(4'-fluoro-4-chalconyloxy)-1-butanol, 4-(4-fluoro-4'-chalconylo-
xy)-1-butanol, 6-(4'-fluoro-4-chalconyloxy)-1-hexanol and
6-(4-fluoro-4'-chalconyloxy)-1-hexanol. They may be used alone or
in combination of two or more. Out of these,
6-(4-chalconyloxy)-1-hexanol and
6-(4'-fluoro-4-chalconyloxy)-1-hexanol are preferred.
[0087] Examples of the phenol having the structure (A) include
4-hydroxychalcone, 4'-hydroxychalcone, 4'-hydroxyfluoro-4-chalcone
and 4-fluoro-4'-hydroxychalcone. They may be used alone or in
combination of two or more.
[0088] For the production of the polyamic acid ester used in the
present invention, a halide, alcohol or phenol containing no
structure (A) may also be used.
[0089] Examples of the above other halide include cetyl bromide,
stearyl bromide, methyl bromide, ethyl bromide, propyl bromide,
cetyl chloride, stearyl chloride, methyl chloride, ethyl chloride,
propyl chloride and 1,1,1-trifluoro-2-iodoethane. Out of these,
stearyl bromide, 1,1,1-trifluoro-2-iodoethane, cetyl chloride and
stearyl chloride are preferred. They may be used alone or in
combination of two or more.
[0090] Examples of the other alcohol include cetyl alcohol, stearyl
alcohol, 1,1,1-trifluoroethanol, methanol, ethanol, isopropanol and
normal propanol. Out of these, cetyl alcohol, stearyl alcohol and
1,1,1-trifluoroethanol are preferred. They may be used alone or in
combination of two or more.
[0091] Examples of the other phenol include phenol, cresol,
4-cetyloxyphenol, 4-cetylphenol, 4-stearyloxyphenol,
4-stearylphenol and 4-trifluoromethylphenol. They may be used alone
or in combination of two or more.
[0092] The polyamic acid ester used in the present invention is
prepared by obtaining polyamic acid by polycondensing (a) the
tetracarboxylic dianhydride component and (b) the diamine component
as described above and then reacting the polyamic acid with a
halide, an alcohol or a phenol in the presence of a catalyst as
required.
[0093] Examples of the catalyst used in the reaction between the
polyamic acid and the halide as required include basic catalysts
such as lithium hydroxide, sodium hydroxide, potassium hydroxide,
lithium carbonate, sodium carbonate, potassium carbonate, sodium
methoxide, potassium methoxide, sodium ethoxide, potassium
ethoxide, sodium propoxide, potassium propoxide, sodium butoxide,
potassium butoxide, trimethylamine, triethylamine and pyridine.
[0094] Example of the catalyst used in the reaction between the
polyamic acid and the alcohol or phenol as required is a
dehydrating catalyst such as dicyclohexyl carbodimide and methyl
chloroformate. The dehydrating catalyst may be used in combination
with a cocatalyst such as dimethylamino pyridine as required.
[0095] The polymaleimide, polystyrene and maleimide/styrene
copolymer as other examples of the specific polymer are polymers
having a chalcone structure represented by the following formula
(IV)-2 having the above structure (IV): 19
[0096] wherein P.sup.4, Q.sup.4, R.sup.7 and R.sup.8 are as defined
in the above formula (IV), S.sup.1 is a hydrogen atom or monovalent
organic group, and X.sup.1 is a divalent bond group or single bond,
and/or a chalcone structure represented by the following formula
(IV)-3 having the above structure (IV): 20
[0097] wherein P.sup.4, Q.sup.4, R.sup.7 and R.sup.8 are as defined
in the above formula (IV), and X.sup.2 is a divalent bond group or
single bond, as the polymers having the structure (A).
[0098] That is, they are a styrene polymer having a chalcone
structure represented by the above formula (IV)-2, a maleimide
polymer having a chalcone structure represented by the above
formula (IV)-3 and a copolymer having chalcone structures
represented by the above formulas (IV)-2 and (IV)-3,
respectively.
[0099] X.sup.1 and X.sup.2 in the above formulas (IV)-2 and (IV)-3
are each a divalent bond group or single bond. The divalent bond
group is preferably an organic group containing an ether bond
and/or an ester bond, more preferably an organic group having 6 to
24 carbon atoms and containing an ether bond and/or an ester bond.
It is particularly preferably an organic group containing an ether
bond and/or an ester bond and a linear alkylene structure having 6
or more carbon atoms. S.sup.1 is a hydrogen atom or monovalent
organic group, preferably a hydrogen atom or methyl group.
[0100] The above polymers are obtained by radically polymerizing
monomer components containing at least one monomer selected from
the group consisting of a styrene derivative having a conjugated
enone structure (A) represented by the following formula (IV)-2M
and a maleimide derivative having a conjugated enone structure (A)
represented by the following formula (IV)-3M in the presence of an
initiator. 21
[0101] Examples of the styrene derivative having the structure (A)
include 4-(4-chalconyloxy)styrene,
4-(4-chalconyloxy).alpha.-methylstyrene,
4-(2-(4-chalconyloxy)ethoxy)styrene,
4-(2-(4-chalconyloxy)ethoxy).alpha.-- methylstyrene,
4-(4-(4-chalconyloxy)butoxy)styrene,
4-(4-(4-chalconyloxy)butoxy).alpha.-methylstyrene,
4-(6-(4-chalconyloxy)hexanoxy)styrene,
4-(6-(4-chalconyloxy)hexanoxy).alp- ha.-methylstyrene,
4-(8-(4-chalconyloxy)octanoxy)styrene,
4-(8-(4-chalconyloxy)octanoxy).alpha.-methylstyrene,
4-(4-chalconylcarboxy)styrene,
4-(4-chalconylcarboxy).alpha.-methylstyren- e,
4-(2-(4-chalconylcarboxy)ethoxy)styrene,
4-(2-(4-chalconylcarboxy)ethox- y).alpha.-methylstyrene,
4-(4-(4-chalconylcarboxy)butoxy)styrene,
4-(4-(4-chalconylcarboxy)butoxy).alpha.-methylstyrene,
4-(6-(4-chalconylcarboxy)hexanoxy)styrene,
4-(6-(4-chalconylcarboxy)hexan- oxy).alpha.-methylstyrene,
4-(8-(4-chalconylcarboxy)octanoxy)styrene,
4-(8-(4-chalconylcarboxy)octanoxy).alpha.-methylstyrene,
4-(2-(4-chalconyl)ethoxy)styrene,
4-(2-(4-chalconyl)ethoxy).alpha.-methyl- styrene,
4-(4-(4-chalconyl)butoxy)styrene, 4-(4-(4-chalconyl)butoxy).alpha-
.-methylstyrene, 4-(6-(4-chalconyl)hexanoxy)styrene,
4-(6-(4-chalconyl)hexanoxy).alpha.-methylstyrene,
4-(8-(4-chalconyl)octan- oxy)styrene,
4-(8-(4-chalconyl)octanoxy).alpha.-methylstyrene,
4-(2-(4-chalconyloxy)ethyl)styrene,
4-(2-(4-chalconyloxy)ethyl).alpha.-me- thylstyrene,
4-(4-(4-chalconyloxy)butyl)styrene, 4-(4-(4-chalconyloxy)buty-
l).alpha.-methylstyrene, 4-(6-(4-chalconyloxy)hexyl)styrene,
4-(6-(4-chalconyloxy)hexyl).alpha.-methylstyrene,
4-(8-(4-chalconyloxy)oc- tyl)styrene,
4-(8-(4-chalconyloxy)octyl).alpha.-methylstyrene,
4-(2-(4-chalconylcarboxy)ethyl)styrene,
4-(2-(4-chalconylcarboxy)ethyl).a- lpha.-methylstyrene,
4-(4-(4-chalconylcarboxy)butyl)styrene,
4-(4-(4-chalconylcarboxy)butyl).alpha.-methylstyrene,
4-(6-(4-chalconylcarboxy)hexyl)styrene,
4-(6-(4-chalconylcarboxy)hexyl).a- lpha.-methylstyrene,
4-(8-(4-chalconylcarboxy)octyl)styrene,
4-(8-(4-chalconylcarboxy)octyl).alpha.-methylstyrene,
4-(2-(4-chalconyl)ethyl)styrene,
4-(2-(4-chalconyl)ethyl).alpha.-methylst- yrene,
4-(4-(4-chalconyl)butyl)styrene,
4-(4-(4-chalconyl)butyl).alpha.-me- thylstyrene,
4-(6-(4-chalconyl)hexyl)styrene, 4-(6-(4-chalconyl)hexyl).alp-
ha.-methylstyrene, 4-(8-(4-chalconyl)octyl)styrene,
4-(8-(4-chalconyl)octyl).alpha.-methylstyrene,
4-(4-chalconyloxymethyl)st- yrene,
4-(4-chalconyloxymethyl).alpha.-methylstyrene,
4-(2-(4-chalconyloxy)ethoxymethyl)styrene,
4-(2-(4-chalconyloxy)ethoxymet- hyl).alpha.-methylstyrene,
4-(4-(4-chalconyloxy)butoxymethyl)styrene,
4-(4-(4-chalconyloxy)butoxymethyl).alpha.-methylstyrene,
4-(6-(4-chalconyloxy)hexanoxymethyl)styrene,
4-(6-(4-chalconyloxy)hexanox- ymethyl).alpha.-methylstyrene,
4-(8-(4-chalconyloxy)octanoxymethyl)styrene- ,
4-(8-(4-chalconyloxy)octanoxymethyl).alpha.-methylstyrene,
4-(4-chalconylcarboxymethyl)styrene,
4-(4-chalconylcarboxymethyl).alpha.-- methylstyrene,
4-(2-(4-chalconylcarboxy)ethoxymethyl)styrene,
4-(2-(4-chalconylcarboxy)ethoxymethyl).alpha.-methylstyrene,
4-(4-(4-chalconylcarboxy)butoxymethyl)styrene,
4-(4-(4-chalconylcarboxy)b- utoxymethyl).alpha.-methylstyrene,
4-(6-(4-chalconylcarboxy)hexanoxymethyl- )styrene,
4-(6-(4-chalconylcarboxy)hexanoxymethyl).alpha.-methylstyrene,
4-(8-(4-chalconylcarboxy)octanoxymethyl)styrene,
4-(8-(4-chalconylcarboxy- )octanoxymethyl).alpha.-methylstyrene,
4-(2-(4-chalconyl)ethoxymethyl)styr- ene,
4-(2-(4-chalconyl)ethoxymethyl).alpha.-methylstyrene,
4-(4-(4-chalconyl)butoxymethyl)styrene,
4-(4-(4-chalconyl)butoxymethyl).a- lpha.-methylstyrene,
4-(6-(4-chalconyl)hexanoxymethyl)styrene,
4-(6-(4-chalconyl)hexanoxymethyl).alpha.-methylstyrene,
4-(8-(4-chalconyl)octanoxymethyl)styrene,
4-(8-(4-chalconyl)octanoxymethy- l).alpha.-methylstyrene,
4-(4'-fluoro-4-chalconyloxy)styrene,
4-(4'-fluoro-4-chalconyloxy).alpha.-methylstyrene,
4-(2-(4'-fluoro-4-chalconyloxy)ethoxy)styrene,
4-(2-(4'-fluoro-4-chalcony- loxy)ethoxy).alpha.-methylstyrene,
4-(4-(4'-fluoro-4-chalconyloxy)butoxy)s- tyrene,
4-(4-(4'-fluoro-4-chalconyloxy)butoxy).alpha.-methylstyrene,
4-(6-(4'-fluoro-4-chalconyloxy)hexanoxy)styrene,
4-(6-(4'-fluoro-4-chalco- nyloxy)hexanoxy).alpha.-methylstyrene,
4-(8-(4'-fluoro-4-chalconyloxy)octa- noxy)styrene,
4-(8-(4'-fluoro-4-chalconyloxy)octanoxy).alpha.-methylstyren- e,
4-(4'-fluoro-4-chalconylcarboxy)styrene,
4-(4'-fluoro-4-chalconylcarbox- y).alpha.-methylstyrene,
4-(2-(4'-fluoro-4-chalconylcarboxy)ethoxy)styrene- ,
4-(2-(4'-fluoro-4-chalconylcarboxy)ethoxy).alpha.-methylstyrene,
4-(4-(4'-fluoro-4-chalconylcarboxy)butoxy)styrene,
4-(4-(4'-fluoro-4-chalconylcarboxy)butoxy).alpha.-methylstyrene,
4-(6-(4'-fluoro-4-chalconylcarboxy)hexanoxy)styrene,
4-(6-(4'-fluoro-4-chalconylcarboxy)hexanoxy).alpha.-methylstyrene,
4-(8-(4'-fluoro-4-chalconylcarboxy)octanoxy)styrene,
4-(8-(4'-fluoro-4-chalconylcarboxy)octanoxy).alpha.-methylstyrene,
4-(2-(4'-fluoro-4-chalconyl)ethoxy)styrene,
4-(2-(4'-fluoro-4-chalconyl)e- thoxy).alpha.-methylstyrene,
4-(4-(4'-fluoro-4-chalconyl)butoxy)styrene,
4-(4-(4'-fluoro-4-chalconyl)butoxy).alpha.-methylstyrene,
4-(6-(4'-fluoro-4-chalconyl)hexanoxy)styrene,
4-(6-(4'-fluoro-4-chalconyl- )hexanoxy).alpha.-methylstyrene,
4-(8-(4'-fluoro-4-chalconyl)octanoxy)styr- ene,
4-(8-(4'-fluoro-4-chalconyl)octanoxy).alpha.-methylstyrene,
4-(2-(4'-fluoro-4-chalconyloxy)ethyl)styrene,
4-(2-(4'-fluoro-4-chalconyl- oxy)ethyl).alpha.-methylstyrene,
4-(4-(4'-fluoro-4-chalconyloxy)butyl)styr- ene,
4-(4-(4'-fluoro-4-chalconyloxy)butyl).alpha.-methylstyrene,
4-(6-(4'-fluoro-4-chalconyloxy)hexyl)styrene,
4-(6-(4'-fluoro-4-chalconyl- oxy)hexyl).alpha.-methylstyrene,
4-(8-(4'-fluoro-4-chalconyloxy)octyl)styr- ene,
4-(8-(4'-fluoro-4-chalconyloxy)octyl).alpha.-methylstyrene,
4-(2-(4'-fluoro-4-chalconylcarboxy)ethyl)styrene,
4-(2-(4'-fluoro-4-chalc- onylcarboxy)ethyl).alpha.-methylstyrene,
4-(4-(4'-fluoro-4-chalconylcarbox- y)butyl)styrene,
4-(4-(4'-fluoro-4-chalconylcarboxy)butyl).alpha.-methylst- yrene,
4-(6-(4'-fluoro-4-chalconylcarboxy)hexyl)styrene,
4-(6-(4'-fluoro-4-chalconylcarboxy)hexyl).alpha.-methylstyrene,
4-(8-(4'-fluoro-4-chalconylcarboxy)octyl)styrene,
4-(8-(4'-fluoro-4-chalc- onylcarboxy)octyl).alpha.-methylstyrene,
4-(2-(4'-fluoro-4-chalconyl)ethyl- )styrene,
4-(2-(4'-fluoro-4-chalconyl)ethyl).alpha.-methylstyrene,
4-(4-(4'-fluoro-4-chalconyl)butyl)styrene,
4-(4-(4'-fluoro-4-chalconyl)bu- tyl).alpha.-methylstyrene,
4-(6-(4'-fluoro-4-chalconyl)hexyl)styrene,
4-(6-(4'-fluoro-4-chalconyl)hexyl).alpha.-methylstyrene,
4-(8-(4'-fluoro-4-chalconyl)octyl)styrene,
4-(8-(4'-fluoro-4-chalconyl)oc- tyl).alpha.-methylstyrene,
4-(4'-fluoro-4-chalconyloxymethyl)styrene,
4-(4'-fluoro-4-chalconyloxymethyl).alpha.-methylstyrene,
4-(2-(4'-fluoro-4-chalconyloxy)ethoxymethyl)styrene,
4-(2-(4'-fluoro-4-chalconyloxy)ethoxymethyl).alpha.-methylstyrene,
4-(4-(4'-fluoro-4-chalconyloxy)butoxymethyl)styrene,
4-(4-(4'-fluoro-4-chalconyloxy)butoxymethyl).alpha.-methylstyrene,
4-(6-(4'-fluoro-4-chalconyloxy)hexanoxymethyl)styrene,
4-(6-(4'-fluoro-4-chalconyloxy)hexanoxymethyl).alpha.-methylstyrene,
4-(8-(4'-fluoro-4-chalconyloxy)octanoxymethyl)styrene,
4-(8-(4'-fluoro-4-chalconyloxy)octanoxymethyl).alpha.-methylstyrene,
4-(2-(4'-fluoro-4-chalconyl)ethoxymethyl)styrene,
4-(2-(4'-fluoro-4-chalc- onyl)ethoxymethyl).alpha.-methylstyrene,
4-(4'-fluoro-4-carchonylcarboxyme- thyl)styrene,
4-(4'-fluoro-4-carchonylcarboxymethyl).alpha.-methylstyrene,
4-(2-(4'-fluoro-4-carchonylcarboxy)ethoxymethyl)styrene,
4-(2-(4'-fluoro-4-carchonylcarboxy)ethoxymethyl).alpha.-methylstyrene,
4-(4-(4'-fluoro-4-chalconylcarboxy)butoxymethyl)styrene,
4-(4-(4'-fluoro-4-chalconylcarboxy)butoxymethyl).alpha.-methylstyrene,
4-(6-(4'-fluoro-4-chalconylcarboxy)hexanoxymethyl) styrene,
4-(6-(4'-fluoro-4-chalconylcarboxy)hexanoxymethyl).alpha.-methylstyrene,
4-(8-(4'-fluoro-4-chalconylcarboxy)octanoxymethyl) styrene,
4-(8-(4'-fluoro-4-chalconylcarboxy)octanoxymethyl).alpha.-methylstyrene,
4-(2-(4'-fluoro-4-carchonyl)ethoxymethyl)styrene,
4-(2-(4'-fluoro-4-carch- onyl)ethoxymethyl).alpha.-methylstyrene,
4-(4-(4'-fluoro-4-chalconyl)butox- ymethyl)styrene,
4-(4-(4'-fluoro-4-chalconyl)butoxymethyl).alpha.-methylst- yrene,
4-(6-(4'-fluoro-4-chalconyl)hexanoxymethyl)styrene,
4-(6-(4'-fluoro-4-chalconyl)hexanoxymethyl).alpha.-methylstyrene,
4-(8-(4'-fluoro-4-chalconyl)octanoxymethyl)styrene,
4-(8-(4'-fluoro-4-chalconyl)octanoxymethyl).alpha.-methylstyrene,
4-((3-(4-vinylphenyl)propionyloxy)-4'-fluorochalcone,
4-((3-(4-vinylphenyl)propionyloxy)chalcone and compounds
represented by the following formulas (71) to (78); 2223
[0102] 4-(8-(4-chalconyloxy)octanoxy)styrene,
4-(8-(4-chalconyloxy)octanox- y).alpha.-methylstyrene,
4-(10-(4-chalconyloxy)decyloxy)styrene,
4-(10-(4-chalconyloxy)decyloxy).alpha.-methylstyrene,
4-(12-(4-chalconyloxy)lauryloxy)styrene,
4-(12-(4-chalconyloxy)lauryloxy)- .alpha.-methylstyrene,
4-(18-(4-chalconyloxy)stearyloxy)styrene,
4-(18-(4-chalconyloxy)stearyloxy).alpha.-methylstyrene,
4-(8-(4-chalconylcarboxy)octanoxy)styrene,
4-(8-(4-chalconylcarboxy)octan- oxy).alpha.-methylstyrene,
4-(10-(4-chalconylcarboxy)decyloxy)styrene,
4-(10-(4-chalconylcarboxy)decyloxy).alpha.-methylstyrene,
4-(12-(4-chalconylcarboxy)lauryloxy)styrene,
4-(12-(4-chalconylcarboxy)la- uryloxy).alpha.-methylstyrene,
4-(18-(4-chalconylcarboxy)stearyloxy)styren- e,
4-(18-(4-chalconylcarboxy)stearyloxy).alpha.-methylstyrene,
4-(8-(4-chalconyl)octanoxy)styrene,
4-(8-(4-chalconyl)octanoxy).alpha.-me- thylstyrene,
4-(10-(4-chalconyl)decyloxy)styrene, 4-(10-(4-chalconyl)decyl-
oxy).alpha.-methylstyrene, 4-(12-(4-chalconyl)lauryloxy)styrene,
4-(12-(4-chalconyl)lauryloxy).alpha.-methylstyrene,
4-(18-(4-chalconyl)stearyloxy)styrene,
4-(18-(4-chalconyl)stearyloxy).alp- ha.-methylstyrene,
4-(8-(4-chalconyloxy)octyl)styrene,
4-(8-(4-chalconyloxy)octyl).alpha.-methylstyrene,
4-(10-(4-chalconyloxy)d- ecyl)styrene,
4-(10-(4-chalconyloxy)decyl).alpha.-methylstyrene,
4-(12-(4-chalconyloxy)lauryl)styrene,
4-(12-(4-chalconyloxy)lauryl).alpha- .-methylstyrene,
4-(18-(4-chalconyloxy)stearyl)styrene,
4-(18-(4-chalconyloxy)stearyl).alpha.-methylstyrene,
4-(8-(4-chalconylcarboxy)octyl)styrene,
4-(8-(4-chalconylcarboxy)octyl).a- lpha.-methylstyrene,
4-(10-(4-chalconylcarboxy)decyl)styrene,
4-(10-(4-chalconylcarboxy)decyl).alpha.-methylstyrene,
4-(12-(4-chalconylcarboxy)lauryl)styrene,
4-(12-(4-chalconylcarboxy)laury- l).alpha.-methylstyrene,
4-(18-(4-chalconylcarboxy)stearyl)styrene,
4-(18-(4-chalconylcarboxy)stearyl).alpha.-methylstyrene,
4-(8-(4-chalconyl)octyl)styrene,
4-(8-(4-chalconyl)octyl).alpha.-methylst- yrene,
4-(10-(4-chalconyl)decyl)styrene,
4-(10-(4-chalconyl)decyl).alpha.-- methylstyrene,
4-(12-(4-chalconyl)lauryl)styrene, 4-(12-(4-chalconyl)laury-
l).alpha.-methylstyrene, 4-(18-(4-chalconyl)stearyl)styrene,
4-(18-(4-chalconyl)stearyl).alpha.-methylstyrene,
4-(8-(4-chalconyloxy)oc- toxymethyl)styrene,
4-(8-(4-chalconyloxy)octoxymethyl).alpha.-methylstyren- e,
4-(10-(4-chalconyloxy)decyloxymethyl)styrene,
4-(10-(4-chalconyloxy)dec- yloxymethyl).alpha.-methylstyrene,
4-(12-(4-chalconyloxy)lauryloxymethyl)s- tyrene,
4-(12-(4-chalconyloxy)lauryloxymethyl).alpha.-methylstyrene,
4-(18-(4-chalconyloxy)stearyloxymethyl)styrene,
4-(18-(4-chalconyloxy)ste- aryloxymethyl).alpha.-methylstyrene,
4-(8-(4-chalconylcarboxy)octoxymethyl- )styrene,
4-(8-(4-chalconylcarboxy)octoxymethyl).alpha.-methylstyrene,
4-(10-(4-chalconylcarboxy)decyloxymethyl)styrene,
4-(10-(4-chalconylcarbo- xy)decyloxymethyl).alpha.-methylstyrene,
4-(12-(4-chalconylcarboxy)laurylo- xymethyl)styrene,
4-(12-(4-chalconylcarboxy)lauryloxymethyl).alpha.-methyl- styrene,
4-(18-(4-chalconylcarboxy)stearyloxymethyl)styrene,
4-(18-(4-chalconylcarboxy)stearyloxymethyl).alpha.-methylstyrene,
4-(8-(4-chalconyl)octoxymethyl)styrene,
4-(8-(4-chalconyl)octoxymethyl).a- lpha.-methylstyrene,
4-(10-(4-chalconyl)decyloxymethyl)styrene,
4-(10-(4-chalconyl)decyloxymethyl).alpha.-methylstyrene,
4-(12-(4-chalconyl)lauryloxymethyl)styrene,
4-(12-(4-chalconyl)lauryloxym- ethyl).alpha.-methylstyrene,
4-(18-(4-chalconyl)stearyloxymethyl)styrene,
4-(18-(4-chalconyl)stearyloxymethyl).alpha.-methylstyrene,
4-(8-(4'-fluoro-4-chalconyloxy)octoxy)styrene,
4-(8-(4'-fluoro-4-chalcony- loxy)octoxy).alpha.-methylstyrene,
4-(10-(4'-fluoro-4-chalconyloxy)decylox- y)styrene,
4-(10-(4'-fluoro-4-chalconyloxy)decyloxy).alpha.-methylstyrene,
4-(12-(4'-fluoro-4-chalconyloxy)lauryloxy)styrene,
4-(12-(4'-fluoro-4-chalconyloxy)lauryloxy).alpha.-methylstyrene,
4-(18-(4'-fluoro-4-chalconyloxy)stearyloxy)styrene,
4-(18-(4'-fluoro-4-chalconyloxy)stearyloxy).alpha.-methylstyrene,
4-(8-(4'-fluoro-4-chalconylcarboxy)octoxy)styrene,
4-(8-(4'-fluoro-4-chalconylcarboxy)octoxy).alpha.-methylstyrene,
4-(10-(4'-fluoro-4-chalconylcarboxy)decyloxy)styrene,
4-(10-(4'-fluoro-4-chalconylcarboxy)decyloxy).alpha.-methylstyrene,
4-(12-(4'-fluoro-4-chalconylcarboxy)lauryloxy)styrene,
4-(12-(4'-fluoro-4-chalconylcarboxy)lauryloxy).alpha.-methylstyrene,
4-(18-(4'-fluoro-4-chalconylcarboxy)stearyloxy)styrene,
4-(18-(4'-fluoro-4-chalconylcarboxy)stearyloxy).alpha.-methylstyrene,
4-(8-(4'-fluoro-4-chalconyl)octoxy)styrene,
4-(8-(4'-fluoro-4-chalconyl)o- ctoxy).alpha.-methylstyrene,
4-(10-(4'-fluoro-4-chalconyl)decyloxy)styrene- ,
4-(10-(4'-fluoro-4-chalconyl)decyloxy).alpha.-methylstyrene,
4-(12-(4'-fluoro-4-chalconyl)lauryloxy)styrene,
4-(12-(4'-fluoro-4-chalco- nyl)lauryloxy).alpha.-methylstyrene,
4-(18-(4'-fluoro-4-chalconyl)stearylo- xy)styrene,
4-(18-(4'-fluoro-4-chalconyl)stearyloxy).alpha.-methylstyrene,
4-(8-(4'-fluoro-4-chalconyloxy)octyl)styrene,
4-(8-(4'-fluoro-4-chalconyl- oxy)octyl).alpha.-methylstyrene,
4-(10-(4'-fluoro-4-chalconyloxy)decyl)sty- rene,
4-(10-(4'-fluoro-4-chalconyloxy)decyl).alpha.-methylstyrene,
4-(12-(4'-fluoro-4-chalconyloxy)lauryl)styrene,
4-(12-(4'-fluoro-4-chalco- nyloxy)lauryl).alpha.-methylstyrene,
4-(18-(4'-fluoro-4-chalconyloxy)stear- yl)styrene,
4-(18-(4'-fluoro-4-chalconyloxy)stearyl).alpha.-methylstyrene,
4-(8-(4'-fluoro-4-chalconylcarboxy)octyl)styrene,
4-(8-(4'-fluoro-4-chalc- onylcarboxy)octyl).alpha.-methylstyrene,
4-(10-(4'-fluoro-4-chalconylcarbo- xy)decyl)styrene,
4-(10-(4'-fluoro-4-chalconylcarboxy)decyl).alpha.-methyl- styrene,
4-(12-(4'-fluoro-4-chalconylcarboxy)lauryl)styrene,
4-(12-(4'-fluoro-4-chalconylcarboxy)lauryl).alpha.-methylstyrene,
4-(18-(4'-fluoro-4-chalconylcarboxy)stearyl)styrene,
4-(18-(4'-fluoro-4-chalconylcarboxy)stearyl).alpha.-methylstyrene,
4-(8-(4'-fluoro-4-chalconyl)octyl)styrene,
4-(8-(4'-fluoro-4-chalconyl)oc- tyl).alpha.-methylstyrene,
4-(10-(4'-fluoro-4-chalconyl)decyl)styrene,
4-(10-(4'-fluoro-4-chalconyl)decyl).alpha.-methylstyrene,
4-(12-(4'-fluoro-4-chalconyl)lauryl)styrene,
4-(12-(4'-fluoro-4-chalconyl- )lauryl).alpha.-methylstyrene,
4-(18-(4'-fluoro-4-chalconyl)stearyl)styren- e,
4-(18-(4'-fluoro-4-chalconyl)stearyl).alpha.-methylstyrene,
4-(8-(4'-fluoro-4-chalconyloxy)octoxymethyl)styrene,
4-(8-(4'-fluoro-4-chalconyloxy)octoxymethyl).alpha.-methylstyrene,
4-(10-(4'-fluoro-4-chalconyloxy)decyloxymethyl)styrene,
4-(10-(4'-fluoro-4-chalconyloxy)decyloxymethyl).alpha.-methylstyrene,
4-(12-(4'-fluoro-4-chalconyloxy)lauryloxymethyl)styrene,
4-(12-(4'-fluoro-4-chalconyloxy)lauryloxymethyl).alpha.-methylstyrene,
4-(18-(4'-fluoro-4-chalconyloxy)stearyloxymethyl)styrene,
4-(18-(4'-fluoro-4-chalconyloxy)stearyloxymethyl).alpha.-methylstyrene,
4-(8-(4'-fluoro-4-chalconyl)octoxymethyl)styrene,
4-(8-(4'-fluoro-4-chalc- onyl)octoxymethyl).alpha.-methylstyrene,
4-(8-(4'-fluoro-4-chalconylcarbox- y)octoxymethyl)styrene,
4-(8-(4'-fluoro-4-chalconylcarboxy)octoxymethyl).a-
lpha.-methylstyrene,
4-(10-(4'-fluoro-4-chalconylcarboxy)decyloxymethyl)st- yrene,
4-(10-(4'-fluoro-4-chalconylcarboxy)decyloxymethyl).alpha.-methylst-
yrene, 4-(12-(4'-fluoro-4-chalconylcarboxy)lauryloxymethyl)styrene,
4-(12-(4'-fluoro-4-chalconylcarboxy)lauryloxymethyl).alpha.-methylstyrene-
, 4-(18-(4'-fluoro-4-chalconylcarboxy)stearyloxymethyl)styrene,
4-(18-(4'-fluoro-4-chalconylcarboxy)stearyloxymethyl).alpha.-methylstyren-
e, 4-(8-(4'-fluoro-4-chalconyl)octoxymethyl)styrene,
4-(8-(4'-fluoro-4-chalconyl)octoxymethyl).alpha.-methylstyrene,
4-(10-(4'-fluoro-4-chalconyl)decyloxymethyl)styrene,
4-(10-(4'-fluoro-4-chalconyl)decyloxymethyl).alpha.-methylstyrene,
4-(12-(4'-fluoro-4-chalconyl)lauryloxymethyl)styrene,
4-(12-(4'-fluoro-4-chalconyl)lauryloxymethyl).alpha.-methylstyrene,
4-(18-(4'-fluoro-4-chalconyl)stearyloxymethyl)styrene,
4-(18-(4'-fluoro-4-chalconyl)stearyloxymethyl).alpha.-methylstyrene,
and compounds represented by the following formulas (79) to (86).
2425
[0103] Out of these 4-(6-(4-chalconyloxy)hexanoxy)sytrene,
compounds represented by the above formulas (71) to (78),
4-(10-(4-chalconyloxy)dec- yloxy)styrene and compounds represented
by the above formulas (79) to (86) are preferred. They may be used
alone or in combination of two or more.
[0104] Examples of the maleimide derivative having the structure
(A) include 4-(4-chalconyloxy)phenylmaleimide,
4-(2-(4-chalconyloxy)ethoxy)ph- enylmaleimide,
4-(4-(4-chalconyloxy)butoxy)phenylmaleimide,
4-(6-(4-chalconyloxy)hexanoxy)phenylmaleimide,
4-(8-(4-chalconyloxy)octan- oxy)phenylmaleimide,
4-(4-chalconylcarboxy)phenylmaleimide,
4-(2-(4-chalconylcarboxy)ethoxy)phenylmaleimide,
4-(4-(4-chalconylcarboxy- )butoxy)phenylmaleimide,
4-(6-(4-chalconylcarboxy)hexanoxy)phenylmaleimide- ,
4-(8-(4-chalconylcarboxy)octanoxy)phenylmaleimide,
4-(2-(4-chalconyl)ethoxy)phenylmaleimide,
4-(4-(4-chalconyl)butoxy)phenyl- maleimide,
4-(6-(4-chalconyl)hexanoxy)phenylmaleimide,
4-(8-(4-chalconyl)octanoxy)phenylmaleimide,
4-(2-(4-chalconyloxy)ethyl)ph- enylmaleimide,
4-(4-(4-chalconyloxy)butyl)phenylmaleimide,
4-(6-(4-chalconyloxy)hexyl)phenylmaleimide,
4-(8-(4-chalconyloxy)octyl)ph- enylmaleimide,
4-(2-(4-chalconylcarboxy)ethyl)phenylmaleimide,
4-(4-(4-chalconylcarboxy)butyl)phenylmaleimide,
4-(6-(4-chalconylcarboxy)- hexyl)phenylmaleimide,
4-(8-(4-chalconylcarboxy)octyl)phenylmaleimide,
4-(2-(4-chalconyl)ethyl)phenylmaleimide,
4-(4-(4-chalconyl)butyl)phenylma- leimide,
4-(6-(4-chalconyl)hexyl)phenylmaleimide, 4-(8-(4-chalconyl)octyl)-
phenylmaleimide, 4-(4'-fluoro-4-chalconyloxy)phenylmaleimide,
4-(2-(4'-fluoro-4-chalconyloxy)ethoxy)phenylmaleimide,
4-(4-(4'-fluoro-4-chalconyloxy)butoxy)phenylmaleimide,
4-(6-(4'-fluoro-4-chalconyloxy)hexanoxy)phenylmaleimide,
4-(8-(4'-fluoro-4-chalconyloxy)octanoxy)phenylmaleimide,
4-(4'-fluoro-4-chalconylcarboxy)phenylmaleimide,
4-(2-(4'-fluoro-4-chalco- nylcarboxy)ethoxy) phenylmaleimide,
4-(4-(4'-fluoro-4-chalconylcarboxy)but- oxy) phenylmaleimide,
4-(6-(4'-fluoro-4-chalconylcarboxy)hexanoxy) phenylmaleimide,
4-(8-(4'-fluoro-4-chalconylcarboxy)octanoxy) phenylmaleimide,
4-(2-(4'-fluoro-4-chalconyl)ethoxy)phenylmaleimide,
4-(4-(4'-fluoro-4-chalconyl)butoxy)phenylmaleimide,
4-(6-(4'-fluoro-4-chalconyl)hexanoxy)phenylmaleimide,
4-(8-(4'-fluoro-4-chalconyl)octanoxy)phenylmaleimide,
4-(2-(4'-fluoro-4-chalconyloxy)ethyl)phenylmaleimide,
4-(4-(4'-fluoro-4-chalconyloxy)butyl)phenylmaleimide,
4-(6-(4'-fluoro-4-chalconyloxy)hexyl)phenylmaleimide,
4-(8-(4'-fluoro-4-chalconyloxy)octyl)phenylmaleimide,
4-(2-(4'-fluoro-4-chalconylcarboxy)ethyl)phenylmaleimide,
4-(4-(4'-fluoro-4-chalconylcarboxy)butyl)phenylmaleimide,
4-(6-(4'-fluoro-4-chalconylcarboxy)hexyl)phenylmaleimide,
4-(8-(4'-fluoro-4-chalconylcarboxy)octyl)phenylmaleimide,
4-(2-(4'-fluoro-4-chalconyl)ethyl)phenylmaleimide,
4-(4-(4'-fluoro-4-chalconyl)butyl)phenylmaleimide,
4-(6-(4'-fluoro-4-chalconyl)hexyl)phenylmaleimide,
4-(8-(4'-fluoro-4-chalconyl)octyl)phenylmaleimide,
4-(8-(4'-fluoro-4-chalconyloxy)octanoxymethyl)phenylmaleimide,
4-(8-(4'-fluoro-4-chalconylcarboxy)octanoxymethyl)phenylmaleimide,
4-(2-(4'-fluoro-4-chalconyl)ethoxymethyl)phenylmaleimide,
4-(4-(4'-fluoro-4-chalconyl)butoxymethyl)phenylmaleimide,
4-(6-(4'-fluoro-4-chalconyl)hexanoxymethyl) phenylmaleimide,
4-(8-(4'-fluoro-4-chalconyl)octanoxymethyl)phenylmaleimide and
compounds represented by the following formulas (91) to (94).
26
[0105] 4-(8-(4-chalconyloxy)octoxy)phenylmaleimide,
4-(10-(4-chalconyloxy)decyloxy)phenylmaleimide,
4-(12-(4-chalconyloxy)lau- ryloxy)phenylmaleimide,
4-(18-(4-chalconyloxy)stearyloxy)phenylmaleimide,
4-(8-(4-chalconylcarboxy)octoxy)phenylmaleimide,
4-(10-(4-chalconylcarbox- y)decyloxy)phenylmaleimide,
4-(12-(4-chalconylcarboxy)lauryloxy)phenylmale- imide,
4-(18-(4-chalconylcarboxy)stearyloxy)phenylmaleimide,
4-(8-(4-chalconyl)octoxy)phenylmaleimide,
4-(10-(4-chalconyl)decyloxy)phe- nylmaleimide,
4-(12-(4-chalconyl)lauryloxy)phenylmaleimide,
4-(18-(4-chalconyl)stearyloxy)phenylmaleimide,
4-(8-(4-chalconyloxy)octyl- )phenylmaleimide,
4-(10-(4-chalconyloxy)decyl)phenylmaleimide,
4-(12-(4-chalconyloxy)lauryl)phenylmaleimide,
4-(18-(4-chalconyloxy)stear- yl)phenylmaleimide,
4-(8-(4-chalconylcarboxy)octyl)phenylmaleimide,
4-(10-(4-chalconylcarboxy)decyl)phenylmaleimide,
4-(12-(4-chalconylcarbox- y)lauryl)phenylmaleimide,
4-(18-(4-chalconylcarboxy)stearyl)phenylmaleimid- e,
4-(8-(4-chalconyl)octyl)phenylmaleimide,
4-(10-(4-chalconyl)decyl)pheny- lmaleimide,
4-(12-(4-chalconyl)lauryl)phenylmaleimide,
4-(18-(4-chalconyl)stearyl)phenylmaleimide,
4-(8-(4'-fluoro-4-chalconylox- y)octoxy)phenylmaleimide,
4-(10-(4'-fluoro-4-chalconyloxy)decyloxy)phenylm- aleimide,
4-(12-(4'-fluoro-4-chalconyloxy)lauryloxy)phenylmaleimide,
4-(18-(4'-fluoro-4-chalconyloxy)stearyloxy)phenylmaleimide,
4-(8-(4'-fluoro-4-chalconylcarboxy)octoxy)phenylmaleimide,
4-(10-(4'-fluoro-4-chalconylcarboxy)decyloxy)phenylmaleimide,
4-(12-(4'-fluoro-4-chalconylcarboxy)lauryloxy)phenylmaleimide,
4-(18-(4'-fluoro-4-chalconylcarboxy)stearyloxy)phenylmaleimide,
4-(8-(4'-fluoro-4-chalconyl)octoxy)phenylmaleimide,
4-(10-(4'-fluoro-4-chalconyl)decyloxy)phenylmaleimide,
4-(12-(4'-fluoro-4-chalconyl)lauryloxy)phenylmaleimide,
4-(18-(4'-fluoro-4-chalconyl)stearyloxy)phenylmaleimide,
4-(8-(4'-fluoro-4-chalconyloxy)octyl)phenylmaleimide,
4-(10-(4'-fluoro-4-chalconyloxy)decyl)phenylmaleimide,
4-(12-(4'-fluoro-4-chalconyloxy)lauryl)phenylmaleimide,
4-(18-(4'-fluoro-4-chalconyloxy)stearyl)phenylmaleimide,
4-(8-(4'-fluoro-4-chalconylcarboxy)octyl)phenylmaleimide,
4-(10-(4'-fluoro-4-chalconylcarboxy)decyl)phenylmaleimide,
4-(12-(4'-fluoro-4-chalconylcarboxy)lauryl)phenylmaleimide,
4-(18-(4'-fluoro-4-chalconylcarboxy)stearyl)phenylmaleimide,
4-(8-(4'-fluoro-4-chalconyl)octyl)phenylmaleimide,
4-(10-(4'-fluoro-4-chalconyl)decyl)phenylmaleimide,
4-(12-(4'-fluoro-4-chalconyl)lauryl)phenylmaleimide,
4-(18-(4'-fluoro-4-chalconyl)stearyl)phenylmaleimide,
4-(8-(4'-fluoro-4-chalconyloxy)octanoxymethyl)phenylmaleimide,
4-(8-(4'-fluoro-4-chalconylcarboxy)octanoxymethyl)phenylmaleimide,
4-(8-(4'-fluoro-4-chalconyl)octoxymethyl)phenylmaleimide,
4-(10-(4'-fluoro-4-chalconyl)decyloxymethyl)phenylmaleimide,
4-(12-(4'-fluoro-4-chalconyl)lauryloxymethyl)phenylmaleimide,
4-(18-(4'-fluoro-4-chalconyl)stearyloxymethyl)phenylmaleimide, and
compounds represented by the following formulas (95) to (98).
27
[0106] Out of these, preferred are
4-(6-(4-chalconyloxy)hexyloxy)phenylmal- eimide,
4-(8-(4-chalconyloxy)octyloxy)phenylmaleimide,
4-(6-(4'-fluoro-4-chalconyloxy)hexyl)phenylmaleimide,
4-(8-(4'-fluoro-4-chalconyloxy)octyl)phenylmaleimide, compounds
represented by the above formulas (91) to (94),
4-(12-(4-chalconyloxy)lau- ryloxy)phenylmaleimide,
4-(18-(4-chalconyloxy)stearyloxy)phenylmaleimide,
4-(12-(4'-fluoro-4-chalconyloxy)lauryl)phenylmaleimide,
4-(18-(4'-fluoro-4-chalconyloxy)stearyl)phenylmaleimide, and
compounds represented by the above formulas (95) to (98). They may
be used alone or in combination of two or more. They may also be
used in conjunction with the above styrene derivative.
[0107] Examples of the styrene derivative having the structure (B)
include p-trifluoromethylstyrene,
p-trifluoromethyl-.alpha.-methylstyrene, p-trifluoromethoxystyrene,
p-trifluoromethoxy-.alpha.-methylstyrene,
4-(2,2,2-trifluoroethoxy)styrene,
4-(2,2,2-trifluoroethoxy)-.alpha.-methy- lstyrene,
p-cetyloxystyrene, p-cetyloxy-.alpha.-methylstyrene,
p-palmitoyloxystyrene, p-palmitoyloxy-.alpha.-methylstyrene,
p-stearyloxystyrene, p-stearyloxy-.alpha.-methylstyrene,
p-stearoyloxystyrene, p-stearoyloxy-.alpha.-methylstyrene,
p-cholesteryloxystyrene, p-cholesteryloxy-.alpha.-methylstyrene,
p-cholestanyloxystyrene and
p-cholestanyloxy-.alpha.-methylstyrene.
[0108] Examples of the maleimide derivative having the structure
(B) include 4-trifluoromethylphenylmaleimide,
4-trifluoromethoxyphenylmaleimi- de,
4-(2,2,2-trifluoroethoxy)phenylmaleimide,
4-cetyloxyphenylmaleimide, 4-palmitoyloxyphenylmaleimide,
4-stearyloxyphenylmaleimide, 4-stearoyloxyphenylmaleimide,
4-cholesteryloxyphenylmaleimide and
4-cholestanyloxyphenylmaleimide.
[0109] The polymaleimide, polystyrene and styrene/maleimide
copolymer used in the present invention may be a copolymer having
the structures (A), (B) and (C) obtained by copolymerizing a
monomer having the structure (C).
[0110] Examples of the monomer having the structure (C) include
glycidyl acrylate, glycidyl methacrylate, glycidyl
.alpha.-ethylacrylate, glycidyl .alpha.-n-propylacrylate, glycidyl
.alpha.-n-butylacrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl
methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl
methacrylate, 6,7-epoxyheptyl .alpha.-ethylacrylate, o-vinylbenzyl
glycidyl ether, m-vinylbenzyl glycidyl ether and p-vinylbenzyl
glycidyl ether. These monomers may be used alone or in
combination.
[0111] The polymaleimide, polystyrene and styrene/maleimide
copolymer used in the present invention may be used in conjunction
with another radically polymerizable monomer in limits that do not
impair the effect of the present invention. The another radically
polymerizable monomer is preferably used in an amount of 50 mol %
based on maleimide in the case of a polymaleimide, styrene in the
case of a polystyrene or the total of styrene and maleimide in the
case of a styrene/maleimide copolymer.
[0112] Examples of the another radically polymerizable monomer
include aliphatic(meth)acrylate compounds such as
methyl(meth)acrylate, ethyl(meth)acrylate, n-butyl(meth)acrylate,
i-butyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate,
2-hydroxypopyl(meth)acrylate, 2-ethylhexyl(meth)acrylate,
polyethylene glycol mono(meth)acrylate and trimethylolpropane
tri(meth)acrylate; alicyclic(meth)acrylate compounds such as
tetrahydrofurfuryl(meth)acrylate, cyclohexyl(meth)acrylate,
glycidyl(meth)acrylate, dicyclopentadiene(meth)acrylate,
dicyclopentanyl(meth)acrylate, tricyclodecanyl(meth)acrylate and
isobornyl(meth)acrylate; aromatic(meth)acrylate compounds such as
4-(meth)acryloyloxychalcone, 4-(meth)acryloyloxy-4'-phenylchalcone,
4-(meth)acryloyloxy-4'-pentylchalcone,
4-(meth)acryloyloxy-4'-(4-pentylph- enyl)chalcone, benzyl
(meth)acrylate, 2-hydroxy-3-phenyloxypropyl(meth)acr- ylate and
tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate; vinyl compounds
such as ethylene, propylene, butene, styrene, p-methylstyrene,
p-trifluoromethylstyrene, .alpha.-methylstyrene,
p-trifluoromethyl-.alpha- .-methylstyrene,
4(4-trifluoromethylbenzoyloxy)styrene, p-cetyloxystyrene,
p-palmitoyloxystyrene,
4-trifluoromethylphenyl-3(4-vinylphenyl)propionate- ,
4-cetyl-3(4-vinylphenyl)propionate,
4-stearyl-3(4-vinylphenyl)propionate- , vinyl chloride, vinyl
acetate and acrylonitrile; maleic acid derivatives such as maleic
anhydride and phenylmaleimide; and dienes such as butadiene,
isoprene and chloroprene.
[0113] Out of these, styrene, p-methylstyrene and
.alpha.-methylstyrene are preferred. They may be used alone or in
combination of two or more.
[0114] The polymaleimide, polystyrene and styrene/maleimide
copolymer used in the present invention are obtained by
polymerizing the above styrene derivative and/or maleimide
derivative optionally in the presence of a catalyst, e.g., an azo
compound such as azobisisobutyronitrile or a perchloride such as
benzoyl peroxide. These polymers may be used alone or in
combination of two or more.
[0115] As an alternative method of obtaining the polymaleimide,
polystyrene and styrene/maleimide copolymer used in the present
invention, an acetoxy-substituted styrene derivative and/or
acetoxy-substituted phenylmaleimide derivative are/is radically
polymerized with a monomer having the structure (B) and a monomer
having the structure (C), and then the above acetyl group is
substituted by a functional group having the structure (A).
[0116] The polyester which is still another example of the specific
polymer is obtained by reacting (c) a dicarboxylic acid
(dicarboxylic acid, dicarboxylic acid ester or dicarboxylic acid
halide) with (d) a diol compound. The polyester used in the present
invention is obtained by using a compound having the structure (A)
and/or the structure (B) as at least one of (c) a dicarboxylic acid
component and (d) a diol compound.
[0117] Examples of the dicarboxylic acid having the structure (A)
include ester compounds such as chalcone-3,3'-dicarboxylic acid,
chalcone-3,4'-dicarboxylic acid, chalcone-4,4'-dicarboxylic acid
and alkyl esters thereof, and
4-(4-(3,5-dicarboxyphenoxy)phenyl)chalcone,
4-(4-(2-(3,5-dicarboxyphenoxy)ethoxy)phenyl)chalcone,
4-(4-(6-(3,5-dicarboxyphenoxy)hexanoxy)phenyl)chalcone,
4-(2-(3,5-dicarboxyphenoxy)ethyl)chalcone carboxylato,
4-(6-(3,5-dicarboxyphenoxy)hexyl)chalcone carboxylato,
4-(4-(3,5-dicarboxyphenoxy)benzoyloxy)chalcone,
4-(4-(3,5-dicarboxyphenox- y)phenyl)chalcone carboxylato,
4-(4-(2-(3,5-dicarboxyphenoxy)ethoxy)benzoy- loxy)chalcone,
4-(4-(2-(3,5-dicarboxyphenoxy)ethoxy)phenyl)chalcone carboxylato,
4-(4-(6-(3,5-dicarboxyphenoxy)hexanoxy)benzoyloxy)chalcone,
4-(4-(6-(3,5-dicarboxyphenoxy)hexanoxy)phenyl)chalcone carboxylato
and alkyl esters thereof, and carboxylic acid halides such as
carboxylic acid chloride.
[0118] Examples of the diol compound having the structure (A)
include 3,3'-dihydroxychalcone, 4,4'-dihydroxychalcone,
3,4'-dihydroxychalcone, 4-(4-(3,5-dihydroxyphenoxy)phenyl)chalcone,
4-(4-(2-(3,5-dihydroxyphenoxy- )ethoxy)phenyl)chalcone,
4-(4-(6-(3,5-dihydroxyphenoxy)hexanoxy)phenyl)cha- lcone,
4-(2-(3,5-dihydroxyphenoxy)ethyl)chalcone carboxylato,
4-(6-(3,5-dihydroxyphenoxy)hexyl)chalcone carboxylato,
4-(4-(3,5-dihydroxyphenoxy)benzoyloxy)chalcone,
4-(4-(3,5-dihydroxyphenox- y)phenyl)chalcone carboxylato,
4-(4-(2-(3,5-dihydroxyphenoxy)ethoxy)benzoy- loxy)chalcone,
4-(4-(2-(3,5-dihydroxyphenoxy)ethoxy)phenyl)chalcone carboxylato,
4-(4-(6-(3,5-dihydroxyphenoxy)hexanoxy)benzoyloxy)chalcone and
4-(4-(6-(3,5-dihydroxyphenoxy)hexanoxy)phenyl)chalcone
carboxylato.
[0119] Out of these, chalcone-4,4'-dicarboxylic acid and
4,4'-dihydroxychalcone are preferred. They may be used alone or in
combination of two or more. Another dicarboxylic acid and/or diol
compound are/is preferably used in a total amount of 80 mol % or
less based on the total of the dicarboxylic acid having the
structure (A) and/or the structure (B) and the diol having the
structure (A) and/or the structure (B).
[0120] The polyester used in the present invention may be used in
conjunction with another dicarboxylic acid and/or diol compound in
limits that do not impair the effect of the present invention.
[0121] Examples of the another dicarboxylic acid include aliphatic
carboxylic acids such as oxalic acid, malonic acid, difluoromalonic
acid, alkylmalonic acid, succinic acid, tetrafluorosuccinic acid,
alkylsuccinic acid, (i)-malic acid, meso-tartaric acid, itaconic
acid, maleic acid, methylmaleic acid, fumaric acid, methylfumaric
acid, acetylenedicarboxylic acid, glutaric acid, hexafluoroglutaric
acid, methylglutaric acid, glutaconic acid, adipic acid,
dithioadipic acid, methyladipic acid, dimethyladipic acid,
tetramethyladipic acid, methyleneadipic acid, muconic acid,
galactaric acid, pimelic acid, suberic acid, perfluorosuberic acid,
3,3,6,6-tetramethylsuberic acid, azelaic acid, sebacic acid,
perfluorosebacic acid, brassylic acid, dodecyldicarboxylic acid,
tridecyldicarboxylic acid and tetradecyldicarboxylic acid;
alicyclic carboxylic acids such as cycloalkyldicarboxylic acid,
adipic acid, hexahydrophthalic acid, 1,4-(norbornene)dicarboxylic
acid, bicyclcoalkyldicarboxylic acid, adamantanedicarboxylic acid
and spyroheptanedicarboxylic acid; aromatic dicarboxylic acids such
as phthalic acid, isophthalic acid, dithioisophthalic acid,
methylisophthalic acid, dimethylisophthalic acid, chloroisophthalic
acid, dichloroisophthalic acid, terephthalic acid,
methylterephthalic acid, dimethylterephthalic acid,
chloroterephthalic acid, bromoterephthalic acid,
naphthalenedicarboxylic acid, oxofluorenedicarboxylic acid,
anthracenedicarboxylic acid, biphenyldicarboxylic acid,
biphenylenedicarboxylic acid, dimethylbiphenylenedicarboxylic acid,
4,4"-p-terphenylenedicarboxylic acid,
4,4'"-p-quaterphenyldicarboxylic acid, bibenzyldicarboxylic acid,
azobenzenedicarboxylic acid, homophthalic acid, phenylenediacetic
acid, phenylenedipropionic acid, naphthalenedicarboxylic acid,
naphthalenedipropionic acid, biphenyldiacetic acid,
biphenyldipropionic acid,
3,3'-[4,4'-(methylenedi-p-biphenylene)dipropionic acid,
4,4'-bibenzyldiacetic acid, 3,3'-(4,4'-bibenzyl)dipropionic acid
and oxydi-p-phenylenediacetic acid; ester compounds such as alkyl
esters of the above dicarboxylic acids, and carboxylic acid halides
such as carboxylic acid chloride. They may be used alone or in
combination of two or more.
[0122] Examples of the another diol compound include polyphenols
such as catechol, alkyl catechol and hydroquinone; and bisphenols
such as methylene bisphenol, isopropylidene bisphenol, butylidene
bisphenol, thiobisphenol, sulfinyl bisphenol, sulfonyl bisphenol
and oxybisphenol. They may be used alone or in combination of two
or more.
[0123] The polyester used in the present invention is obtained by
polycondensing (c) the above dicarboxylic acid component and (d)
the above diol compound, if necessary, under heating in the
presence of a catalyst. For polycondensation between a dicarboxylic
acid and a diol compound, sulfuric acid, protonic acid such as
p-toluenesulfonic acid, oxide or salt of a heavy metal, or organic
metal compound of titanium, tin or lead is used as the catalyst.
For a reaction between a dicarboxylic acid ester and a diol
compound, an acetate or carbonate compound of lead, zinc,
manganese, calcium, cobalt or cadmium, metal magnesium, or oxide of
zinc, lead, antimony or germanium may be used as the catalyst. For
a reaction between a dicarboxylic acid halide and a diol compound,
a basic catalyst such as pyridine or triethylamine is used as the
catalyst.
[0124] The polyamide as still another example of the specific
polymer is obtained by reacting (e) a dicarboxylic acid
(dicarboxylic acid, dicarboxylic acid ester or dicarboxylic acid
halide) with (f) a diamine compound. The polyamide used in the
present invention is obtained by using a compound having the
structure (A) and/or the structure (B) as at least one of (e) a
dicarboxylic acid component and (f) a diamine compound
component.
[0125] Examples of the dicarboxylic acid having the structure (A)
are the dicarboxylic acids (c) listed above. Examples of the
diamine compound having the structure (A) are the diamine compounds
(b) listed above. They may be used alone or in combination of two
or more.
[0126] The polyamide used in the present invention may be used in
conjunction with another dicarboxylic acid compound or diamine
compound in limits that do not impair the effect of the present
invention. Examples of the another dicarboxylic acid compound and
diamine compound are the dicarboxylic acid compounds and diamine
compounds listed above. They may be used alone or in combination of
two or more. The another dicarboxylic acid and/or the another
diamine compound are/is preferably used in a total amount of 80 mol
% or less based on the total of the dicarboxylic acid having the
structure (A) and/or the structure (B) and the diamine compound
having the structure (A) and/or the structure (B).
[0127] The polyamide used in the present invention is obtained by
polycondensing (e) the above dicarboxylic acid component and (f)
the above diamine component, if necessary, in the presence of an
acid catalyst such as paratoluenesulfonic acid, sulfuric acid or
hydrochloric acid.
[0128] The poly(meth)acrylate which is still another example of the
specific polymer is obtained by polymerizing (g) a (meth)acrylate
compound. The poly(meth)acrylate used in the present invention is
obtained by using a compound having the structure (A) and/or the
structure (B) as (g) the (meth)acrylate compound.
[0129] Examples of the (meth)acrylate compound having the structure
(A) include 4'-(meth)acryloyloxychalcone,
4-phenyl-4'-(meth)acryloyloxychalco- ne,
4-pentyl-4'-(meth)acryloyloxychalcone,
4-(4-pentylphenyl)-4'-(meth)acr- yloyloxychalcone,
4-(4-(methy)acryloyloxyphenyl)chalcone,
4-(4-(2-(meth)acryloyloxyethoxy)phenyl)chalcone,
4-(4-(6-(meth)acryloylox- yhexanoxy)phenyl)chalcone,
4-(2-(meth)acryloyloxyethyl)chalcone carboxylato,
4-(6-(meth)acryloyloxyhexyl)chalcone carboxylato,
4-(4-(meth)acryloyloxybenzoyloxy)chalcone,
4-(4-(meth)acryloyloxyphenyl)c- halcone carboxylato,
4-(4-(2-(meth)acryloyloxyethoxy)benzoyloxy)chalcone,
4-(4-(2-(meth)acryloyloxyethoxy)phenyl)chalcone carboxylato,
4-(4-(6-(meth)acryloyloxyhexanoxy)benzoyloxy)chalcone,
4-(4-(6-(meth)acryloyloxyhexanoxy)phenyl)chalcone carboxylato, and
compounds represented by the following formulas (101) to (103).
They may be used alone or in combination of two or more. 28
[0130] The above poly(meth)acrylate may be used in conjunction with
another (meth)acrylate compound in limits that do not impair the
effect of the present invention. The another (meth)acrylate
compound is preferably used in an amount of 300 mol % or less based
on the methacrylate compound having the structure (A) and/or the
structure (B).
[0131] Examples of the another (meth)acrylate compound include
aliphatic(meth)acrylate compounds such as methyl(meth)acrylate,
ethyl(meth)acrylate, n-butyl(meth)acrylate, i-butyl(meth)acrylate,
2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate,
2-ethylhexyl(meth)acrylate, polyethylene glycol mono(meth)acrylate
and trimethylolpropane tri(meth)acrylate; alicyclic (meth)acrylate
compounds such as tetrahydrofurfuryl(meth)acrylate,
cyclohexyl(meth)acrylate, glycidyl(meth)acrylate,
dicyclopentadiene(meth)acrylate, dicyclopentanyl(meth)acrylate,
tricyclodecanyl(meth)acrylate and isobornyl(meth)acrylate; and
aromatic(meth)acrylate compounds such as benzyl(meth)acrylate,
2-hydroxy-3-phenyloxypropyl(meth)acrylate and
tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate. They may be
used alone or in combination of two or more.
[0132] The polysiloxane which is still another example of the
specific polymer has a chalcone structure represented by the
following formula (III)-1 having the above structure (III): 29
[0133] wherein P.sup.3, Q.sup.3, R.sup.15 and R.sup.6 are as
defined in the above formula (III), and Z.sup.1 is a hydroxyl group
or methyl group, and/or the following formula (IV)-1 having the
above structure (IV): 30
[0134] wherein P.sup.4, Q.sup.4, R.sup.8 and R.sup.8 are as defined
in the above formula (IV), and Z.sup.2 is a hydroxyl group or
methyl group.
[0135] The above polysiloxane is obtained by ring opening
polymerizing a cyclic oligosiloxane derivative in the presence of
an acid or basic catalyst or by hydrolyzing a dichlorosilane
derivative. The polysiloxane used in the present invention is
obtained by using a compound having the above structure (A) as at
least part of the cyclic oligosiloxane derivative or the
dichlorosilane derivative. Alternative means of obtaining the
polysiloxane used in the present invention is to react a
polysiloxane derivative having an Si--H bond with a compound having
the above structure (A) and an allyl group in the presence of a
catalyst such as platinum chloride.
[0136] Examples of the cyclic oligosiloxane derivative having the
structure (A) include
1,3,5,7-tetra(4-chalconyl)-1,3,5,7-tetramethylcyclo- tetrasiloxane,
1,3,5,7-tetra(4'-chalconyl)-1,3,5,7-tetramethylcyclotetrasi-
loxane, 1,3,5,7-tetra(3-(4-chalconyloxy)propyl)-1,3,5,7
-tetramethylcyclotetrasiloxane,
1,3,5,7-tetra(3-(4'-chalconyloxy)propyl)--
1,3,5,7-tetramethylcyclotetrasiloxane,
1,3,5,7-tetra(3-(4-chalconyl)propyl-
)-1,3,5,7-tetramethylcyclotetrasiloxane,
1,3,5,7-tetra(3-(4'-chalconyl)pro-
pyl)-1,3,5,7-tetramethylcyclotetrasiloxane,
1,3,5,7-tetra(6-(4-chalconylox-
y)hexyl)-1,3,5,7-tetramethylcyclotetrasiloxane,
1,3,5,7-tetra(6-(4'-chalco-
nyloxy)hexyl)-1,3,5,7-tetramethylcyclotetrasiloxane,
1,3,5,7-tetra(6-(4-chalconyl)hexyl)-1,3,5,7-tetramethylcyclotetrasiloxane
and
1,3,5,7-tetra(6-(4'-chalconyl)hexyl)-1,3,5,7-tetramethylcyclotetrasil-
oxane. They may be used alone or in combination of two or more.
[0137] The cyclic oligosiloxane derivative having the structure (A)
is obtained by reacting a cyclic oligosiloxane such as
1,3,5,7-tetramethylcyclotetrasiloxane with a compound having the
structure (A) such as 4-allyloxychalcone in the presence of a
platinum catalyst.
[0138] Examples of the dichlorosilane derivative having the
structure (A) include monomethyl mono(4-chalconyl)dichlorosilane,
monomethyl mono(4'-chalconyl)dichlorosilane, monomethyl
mono(3-(4-chalconyloxy)propy- l)dichlorosilane, monomethyl
mono(3-(4'-chalconyloxy)propyl)dichlorosilane- , monomethyl
mono(3-(4-chalconyl)propyl)dichlorosilane and monomethyl
mono(3-(4'-chalconyl)propyl)dichlorosilane. They may be used alone
or in combination of two or more.
[0139] The dichlorosilane derivative having the structure (A) is
obtained by reacting a dichlorosilane such as dichloromethylsilane
with a compound having a specific structure such as
4-allyloxychalcone in the presence of a platinum catalyst.
[0140] Out of these, a polymer derived from
1,3,5,7-tetra(3-(4-chalconylox-
y)propyl)-1,3,5,7-tetramethylcyclotetrasiloxane is preferred.
[0141] The polysiloxane used in the present invention may be used
in conjunction with another cyclic oligosiloxane derivative or
another dichlorosilane derivative in limits that do not impair the
effect of the present invention.
[0142] Examples of the another cyclic oligosiloxane derivative
include 1,1,3,3,5,5,7,7-octamethylcyclotetrasiloxane,
1,3,5,7-tetrahydroxy-1,3,5,- 7-tetramethylcyclotetrasiloxane,
1,1,3,3,5,5,7,7-octahydroxycyclotetrasilo- xane,
1,1,3,3,5,5,7,7-octaphenylcyclotetrasiloxane and
1,3,5,7-tetrahydroxy-1,3,5,7-tetraphenylcyclotetrasiloxane.
[0143] Out of these, 1,1,3,3,5,5,7,7-octamethylcyclotetrasiloxane
is preferred. They may be used alone or in combination of two or
more.
[0144] Examples of the another dichlorosilane derivative include
dichlorodimethylsilane, dichlorodiphenylsilane,
dichloromethylphenylsilan- e and dichlorodiethylsilane.
[0145] Out of these, dichlorodimethylsilane is preferred. They may
be used alone or in combination of two or more.
[0146] The weight average molecular weight in terms of polystyrene
(may be referred to as "Mw" hereinafter) of the polysiloxane
polymer used in the present invention is generally 5,000 to
100,000.
[0147] Liquid Crystal Aligning Agent
[0148] The polymer film used in the present invention is generally
obtained by applying a liquid crystal aligning agent prepared by
dissolving a polymer, preferably the above-described specific
polymer in a solvent to a substrate and drying it. Any organic
solvent may be used if it can dissolve the polymer. When a polyamic
acid, polyamic acid ester or polyimide is used, an aprotic polar
solvent such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide,
N,N-dimethylformamide, dimethylsulfoxide, .gamma.-butyrolactone,
tetramethylurea or hexamethylphosphortriamide; or phenol-based
solvent such as m-cresol, xylenol, phenol or halogenated phenol is
used. They may be used alone or in combination of two or more.
[0149] When the polymer is, for example, a polymaleimide,
polystyrene or maleimide/styrene copolymer, an aprotic polar
solvent such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide,
N,N-dimethylformamide, dimethylsulfoxide, .gamma.-butyrolactone,
tetramethylurea, dimethylimidazolidinone or
hexamethylphosphortriamide; ester-based solvent such as butyl
cellosolve acetate, propyl acetate, isopropyl acetate, butyl
acetate, isobutyl acetate, pentyl acetate or isopentyl acetate;
ketone-based solvent such as methyl ethyl ketone, methyl butyl
ketone, methyl isobutyl ketone, cyclohexanone or methyl
cyclohexanone; halogen-based solvent such as chlorobenzene,
orthodichlorobenzene, tetrachloroethylene or 1,1,1-trichloroethane;
or phenol-based solvent such as m-cresol, xylenol, phenol or
halogenated phenol may be used. They may be used alone or in
combination of two or more. A poor solvent for the used polymer may
be used in conjunction with the above solvent in limits that the
polymer does not separate out.
[0150] The solid content of the liquid crystal aligning agent in
the present invention is preferably 1 to 20 wt %.
[0151] Other Additives
[0152] The liquid crystal aligning agent used in the present
invention may contain a polymer other than the specific polymer in
limits that do not impair the effect of the present invention. The
polymer other than the specific polymer is a polyimide, polyamic
acid, polyamide, polyester, poly(meth)acrylate, polysiloxane,
polystyrene or polymaleimide. Out of these, a polyimide and
polyamic acid are preferred because they have excellent heat
resistance.
[0153] The liquid crystal aligning agent used in the present
invention may contain a thermosetting crosslinking agent to improve
the stability of a pretilt angle and the strength of a coating
film. As the thermosetting crosslinking agent is effective a
polyfunctional epoxy-containing compound such as bisphenol A epoxy
resin, phenolic novolak epoxy resin, cresol novolak epoxy resin,
alicyclic epoxy resin, glycidyl ester-based epoxy resin, glycidyl
diamine-based epoxy resin, heterocyclic epoxy resin or epoxy
group-containing acrylic resin. Commercially available products of
the thermosetting crosslinking agent include Epolite 400E and 3002
(of Kyoeisha Chemical Co., Ltd.) and Epicoat 828 and 152 and Epoxy
Novolak 180S (of Yuka Shell Epoxy Co., Ltd.).
[0154] Further, when the above polyfunctional epoxy-containing
compound is used, a basic catalyst such as
1-benzyl-2-methylimidazole may be added to cause a crosslinking
reaction efficiently.
[0155] The liquid crystal aligning agent of the present invention
may contain a functional silane-containing compound to improve
adhesion to a substrate. Examples of the functional
silane-containing compound include 3-aminopropyltrimethoxysilane,
3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane,
2-aminopropyltriethoxysilane,
N-(2-aminoethyl)-3-aminopropyltrimethoxysilane,
N-(2-aminoethyl)-3-aminop- ropylmethyldimethoxysilane,
3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane,
N-ethoxycarbonyl-3-aminopropyltrimethoxysi- lane,
N-ethoxycarbonyl-3-aminopropyltriethoxysilane,
N-triethoxysilylpropyltriethylenetriamine,
N-trimethoxysilylpropyltriethy- lenetriamine,
10-trimethoxysilyl-1,4,7-triazadecane,
10-triethoxysilyl-1,4,7-triazadecane,
9-trimethoxysilyl-3,6-diazanonylace- tate,
9-triethoxysilyl-3,6-diazanonylacetate,
N-benzyl-3-aminopropyltrimet- hoxysilane,
N-benzyl-3-aminopropyltrimethoxysilane,
N-phenyl-3-aminopropyltriethoxysilane,
N-phenyl-3-aminopropyltriethoxysil- ane,
N-bis(oxyethylene)-3-aminopropyltrimethoxysilane,
N-bis(oxyethylene)-3-aminopropyltriethoxysilane and a reaction
product of a tetracarboxylic dianhydride and an amino
group-containing silane compound disclosed in JP-A 63-291922.
[0156] The liquid crystal aligning agent of the present invention
preferably contains the above polymer having a chalcone structure
in an amount of 50 wt % or more based on the total solid
content.
[0157] Optical Alignment Method
[0158] The feature of the first optical alignment method of the
present invention is that the surface of a polymer film is exposed
to radiation with an irradiation intensity distribution while the
surface of the polymer film and radiation are moved relative to
each other substantially at a fixed rate. In order to provide the
irradiation intensity distribution, after a linear exposure pattern
is formed on the polymer film using a slit exposure mask or
projector, the polymer film is exposed to radiation while the
surface of the polymer film and the exposure pattern are moved
relative to each other substantially at a fixed rate. A preferred
concrete method will be detailed hereinbelow.
[0159] To provide liquid crystal aligning capability to the surface
of the polymer film by the present invention, a polymer solution is
first applied to a substrate to prepare the substrate having the
polymer film formed thereon. Then, a slit exposure mask is
positioned substantially in parallel to the surface of the polymer
film on the substrate, and the surface of the polymer film is
exposed to radiation through the slit exposure mask while the
surface of the polymer film and the slit exposure mask are moved
relative to each other substantially at a fixed rate. To move the
polymer film and the slit exposure mask relative to each other, (i)
one of the substrate having the polymer film and the slit exposure
mask is fixed and the other is moved, (ii) both of them are moved
in the same direction at different rates, or (iii) both of them are
moved in different directions. Since the relative rate is easily
controlled, the above method (i) is preferred. It is particularly
preferred that the substrate be fixed and the slit board be
moved.
[0160] When the relative movement is not carried out substantially
at a fixed rate, liquid crystal aligning capability provided to the
surface of the polymer film does not become uniform
disadvantageously.
[0161] The method of the present invention is typically carried out
as a method of forming a liquid crystal alignment film from a
liquid crystal aligning agent. The following method will be
described as an example of the method of the present invention. The
liquid crystal aligning agent of the present invention is first
applied to the transparent conductive film side of a substrate
having the transparent conductive film by roll coating, spinner
coating or printing and heated at 40 to 200.degree. C. to form a
coating film. The thickness of the coating film is preferably 0.001
to 1 .mu.m, more preferably 0.005 to 0.5 .mu.m.
[0162] The above substrate is, for example, a transparent substrate
made from glass such as float glass or soda glass, or a plastic
film of polyethylene terephthalate, polybutylene terephthalate,
polyether sulfone or polycarbonate.
[0163] The above transparent conductive film is, for example, an
NESA film of SnO.sub.2 or ITO film of In.sub.2O.sub.3--SnO.sub.2. A
photo-etching technique or masking technique is used for the
patterning of the transparent conductive film.
[0164] Before the application of the liquid crystal aligning agent,
to further improve adhesion between the substrate/transparent
conductive film and the coating film, a functional
silane-containing compound or titanate may be applied to the
substrate/transparent conductive film.
[0165] The method of the present invention is for the linear
exposure of the surface of the film through the slit exposure mask
by irradiating the coating film formed on the substrate with
radiation to provide liquid crystal aligning capability as
described above.
[0166] FIG. 3 is a diagram for explaining an example of the first
optical alignment method of the present invention. FIG. 3 is a side
view showing that a slit exposure mask 3 is fixed and a substrate 5
having an optical alignment film 4 is moved in the right direction.
The optical alignment film 4 and the substrate 5 fixed on a movable
stage 6 are moved at a rate of 5 .mu.m/sec to 1 mm/sec. A large
number of slits having line and space widths of 1 .mu.m to 1 mm,
for example, are formed parallel to one another in the slit
exposure mask. The distance between the slit exposure mask and the
surface of the coating film is preferably maintained at about 18
.mu.m so that 7 .mu.m-wide radiation is projected onto the surface
of the optical alignment film through slits having a width of 7
.mu.m. Reference numeral 1 denotes an irradiating unit, and 2
denotes radiation. In figures other than FIG. 3, the same numerals
represent the same elements.
[0167] FIG. 4 is a diagram for explaining another example of the
first optical alignment method of the present invention. FIG. 4 is
a side view showing that the substrate 5 having the optical
alignment film 4 is fixed on a fixed stage 7 and the slit exposure
mask 3 is moved in the right direction.
[0168] At the time of exposure, it is preferred that the polymer
having the structure (A) and/or the structure (B) should be heated
at a temperature ranging from its glass transition temperature to a
temperature 100.degree. C. higher than the glass transition
temperature or that a solvent should be contained in an amount of 1
to 20 wt % based on the polymer. The solvent used to dissolve the
above liquid crystal aligning agent may be directly used as the
above solvent. According to the present invention, as optical
alignment is carried out while the substrate having the coating
film formed thereon is kept horizontal, a heater for heating the
substrate at a temperature equal to or higher than the glass
transition temperature of the polymer can be easily installed.
[0169] The radiation (light) used for exposure may be polarized or
nonpolarized light. After exposure, the substrate is optionally
further heated at a temperature of 150 to 250.degree. C. The
radiation may be ultraviolet or visible radiation having a
wavelength of 150 to 800 nm, preferably ultraviolet radiation
having a wavelength of 320 to 450 nm.
[0170] The light source of the above radiation is, for example, a
low-pressure mercury lamp, high-pressure mercury lamp, deuterium
lamp, metal halide lamp, argon resonance lamp, xenon lamp, excimer
laser or the like.
[0171] The ultraviolet radiation having the above preferred
wavelength range can be obtained by combining a filter or
diffraction grating with the above light source. It can be simply
obtained by using a Pyrex (registered trademark) glass polarizer
which does not transmit ultraviolet light having a wavelength
shorter than 320 nm in conjunction with the above light source.
[0172] The first optical alignment method of the present invention
makes it possible to improve the view field characteristics of a
liquid crystal display element by carrying out partial optical
alignment through exposure using a slit exposure mask and by moving
the above mask to align the liquid crystal alignment film in a
different direction from that of the above partial alignment so as
to change the liquid crystal aligning capability of the liquid
crystal alignment film. In this method, it is particularly
preferred that a linear exposure pattern be formed on the polymer
by a projection method using a projector.
[0173] A description is subsequently given of the second optical
alignment method and the third optical alignment method of the
present invention.
[0174] According to the second optical alignment method of the
present invention, an optical exposure pattern is formed on the
surface of the polymer film by forming a plurality of lines having
a certain width on the surface of the polymer film continuously or
repeatedly in such a manner that (i) the lines form around an
arbitrary virtual base point on the surface of the polymer film,
expand concentrically from the virtual base point toward the
periphery and disappear at the periphery, or conversely that (ii)
they start from the periphery away from the virtual base point on
the surface of the polymer film, converge concentrically on the
virtual base point and disappear at the virtual base point. That
is, it can be said that the optical exposure pattern continues to
move in such a manner that it starts from the virtual base point as
the center and disappears, or that it starts from the periphery and
disappears at the virtual base point. While the optical exposure
pattern which continues to move as described above is formed on the
surface of the polymer film, the surface of the polymer film is
exposed through this optical exposure pattern.
[0175] FIG. 5 is a diagram for explaining the formation of the
optical exposure pattern on the surface of the polymer film. In
this example, the optical exposure pattern having circular lines
starting from the virtual base point is moved in such a manner that
the lines expand concentrically toward the periphery.
[0176] The optical exposure pattern may be a projection pattern
projected by a projector, interference fringe or a combination
thereof formed on the surface of the polymer film. The projection
pattern can be easily moved as described above by the operation of
the projector, and the interference fringe can be moved by shifting
the phase of the interference fringe.
[0177] The lines having a certain width of the optical exposure
pattern may be circular, oval or polygonal (such as rectangular or
diamond-shaped).
[0178] According to the second optical alignment method, exposure
can be carried out while a plurality of the above optical exposure
patterns are formed adjacent to one another. When the obtained
polymer film provided with liquid crystal aligning capability is a
liquid crystal alignment film and exposed through a plurality of
adjacent optical exposure patterns, a polymer film area exposed
through each of the exposure patterns corresponds to one pixel. In
this case, as easily understood, as for liquid crystal aligning
capability in each area corresponding to one pixel, each area has a
different liquid crystal aligning axis in the entire
circumferential direction. Preferably, the lines of the optical
exposure pattern disappear or start at the end of one pixel. More
specifically, it is preferred that the lines should disappear or
start from an area 1 mm or less away from the virtual base
point.
[0179] According to the third optical alignment method of the
present invention, an optical exposure pattern having a plurality
of lines with a certain width formed at certain intervals is formed
on the surface of the polymer film continuously in such a manner
that two areas sandwiching a virtual base line on the surface of
the polymer film differ from each other in at least one of the
pattern and the moving direction of the pattern. That is, the lines
of the optical exposure patterns in the above two areas are
continuously formed in the two areas on the above surface of the
polymer film in such a manner that they start in the respective
areas, move to cover the respective areas and disappear in the
respective areas.
[0180] When the two areas sandwiching the virtual base line are
made different from each other in at least one of the optical
exposure pattern and the moving direction of the pattern, the
directions of the liquid crystal aligning axes in the above two
areas can be made different from each other.
[0181] When the two areas differ from each other in the
pattern,
[0182] (i) a pattern in one of the areas has a plurality of
parallel straight lines with a certain width and a pattern in the
other area has a plurality of parallel curved line with a certain
width, or (ii) patterns in the both areas have a plurality of
parallel straight lines with a certain width but differ from each
other in the interval between adjacent straight lines and/or the
number of lines.
[0183] When the two areas differ from each other in the moving
direction of the pattern, (i) the patterns in the both areas have a
plurality of parallel straight lines with a certain width but move
in opposite directions away from the virtual base line in the both
areas, (ii) the patterns in the both areas have a plurality of
parallel straight lines with a certain width but move toward the
virtual base line in the both areas, and (iii) the patterns in the
both areas have a plurality of parallel straight lines with a
certain width but the straight lines of the pattern in one area
move in a direction perpendicular to the virtual base line and the
straight lines of the pattern in the other area move in parallel to
or at an angle smaller than 90.degree. from the virtual base
line.
[0184] According to the third optical alignment method, liquid
crystal aligning capability can be provided to the surface of the
polymer film by exposing the surface of the polymer film through
the exposure pattern. When the polymer film provided with liquid
crystal aligning capability is a liquid crystal alignment film, the
above two areas can correspond to one pixel. In this case, each of
the two areas corresponds to a half of one pixel. Similarly, four
different areas can be formed by combining together above two areas
of the polymer film in such a manner that the two virtual straight
lines of the polymer films become perpendicular to each other. In
this case, it should be understood that each of the above two areas
consists of two sub-areas. In this case, it should also be
understood that each of the four areas differs from at least two
areas adjacent thereto in at least one of the pattern and the
moving direction of the pattern.
[0185] Preferably, the third optical alignment method of the
present invention is characterized by providing liquid crystal
aligning capability to the surface of the polymer film by exposing
the surface of the polymer film through an optical exposure pattern
having a plurality of lines with a certain width at certain
intervals while the optical exposure pattern is formed on the
surface of the polymer film continuously in such a manner that the
lines start from a certain virtual base line on the surface of the
polymer film, move in two right and left directions from the
virtual base line and disappear at right and left positions, or
that they start from the right and left positions away from the
virtual base line, move toward the virtual base line from the right
and left directions and disappear on the virtual base line.
[0186] According to this preferred mode, the optical exposure
pattern is formed on the surface of the polymer film by forming the
plurality of lines having a certain width of the optical exposure
pattern on the surface of the polymer film continuously or
repeatedly in such a manner that (i) the lines start from a certain
virtual base line on the surface of the polymer film, move in two
right and left directions from the virtual base line and disappear
at right and left positions or, conversely, that (ii) they start
from the right and left positions away from the certain virtual
base line on the surface of the polymer film, move toward the
virtual base line from the left and right directions and disappear
on the virtual base line. Thus, the optical exposure pattern is
formed on the surface of the polymer film.
[0187] The optical exposure pattern may be a projection pattern
projected by a projector, an interference fringe or a combination
thereof formed on the surface of the polymer film. The projection
pattern can be easily moved by the operation of the projector, and
the interference fringe can be moved by shifting the phase of the
interference fringe. The lines having a certain width of the
optical exposure pattern may be, for example, straight lines,
broken lines or curved lines.
[0188] According to the third optical alignment method, exposure
can be carried out while a plurality of the above optical exposure
patterns are formed adjacent to one another. When the polymer film
provided with liquid crystal aligning capability is a liquid
crystal alignment film and exposed through a plurality of adjacent
optical exposure patterns, a polymer film area exposed through each
of the exposure patterns corresponds to one pixel. In this case, as
easily understood, as for liquid crystal aligning capability in the
areas corresponding to one pixel, the two areas sandwiching the
virtual base line differ from each other in liquid crystal aligning
direction. Preferably, the lines of the optical exposure pattern
disappear or start at the end of one pixel or another virtual base
line. More specifically, it is preferred that the lines should
disappear or start from an area 1 mm or less away from the virtual
base line.
[0189] FIG. 6 is a diagram for explaining an example of the third
optical alignment method of the present invention. FIG. 6 is a
perspective view showing that an optical alignment film is formed
by projecting an optical exposure pattern from a projector 11,
scanning the pattern having parallel straight lines in right and
left directions from a virtual base line and exposing the surface
of the polymer film through the pattern.
[0190] At the time of exposure, it is preferred that the polymer
film should be heated at a temperature ranging from the glass
transition temperature of the polymer to a temperature 100.degree.
C. higher than the glass transition temperature or that a solvent
should be contained in an amount of 1 to 20 wt % based on the
polymer. The solvent used to dissolve the above liquid crystal
aligning agent may be directly used as the above solvent. According
to the method of the present invention, as optical alignment is
carried out while the substrate having the coating film formed
thereon is kept horizontal, a heater for heating the substrate at a
temperature equal to or higher than the glass transition
temperature of the polymer can be easily installed.
[0191] The radiation (light) used for exposure may be polarized or
nonpolarized light. After exposure, the substrate is optionally
further heated at a temperature of 100 to 300.degree. C. The
radiation may be ultraviolet or visible radiation having a
wavelength of 150 to 800 nm, preferably ultraviolet radiation
having a wavelength of 320 to 450 nm.
[0192] The light source of the above radiation is, for example, a
low-pressure mercury lamp, high-pressure mercury lamp, deuterium
lamp, metal halide lamp, argon resonance lamp, xenon lamp, excimer
laser or the like.
[0193] The ultraviolet radiation having the above preferred
wavelength range can be obtained by combining a filter or
diffraction grating with the above light source. It can be simply
obtained by using a Pyrex (registered trademark) glass polarizer
which does not transmit ultraviolet light having a wavelength
shorter than 320 nm in conjunction with the above light source.
[0194] According to the present invention, it is possible to
develop a liquid crystal pretilt angle of 1 to 10.degree..
[0195] For instance, when a polyamic acid or polyimide having the
structure (A) or a polymer having the structure (B) obtained by
using at least one of a compound belonging to the examples (a) as a
tetracarboxylic dianhydride and a compound belonging to the
examples (d) as a diamine compound is used, a liquid crystal
pretilt angle of 80.degree. or more, for example, 80 to 90.degree.
can be developed.
[0196] Liquid Crystal Display Element
[0197] The liquid crystal display element formed by using a liquid
crystal aligning agent and produced by the method of the present
invention is constructed as follows. Two substrates having the
above liquid crystal alignment film are opposed to each other in
such a manner that the polarization directions of linearly
polarized radiations irradiated onto the liquid crystal alignment
films form a predetermined angle, a peripheral portion between the
substrates was sealed with a sealer, liquid crystals are filled
into a gap between the substrates, and a filling hole is sealed to
construct a liquid crystal cell.
[0198] Thereafter, it is desired that flow-induced alignment at the
time of filling liquid crystals should be removed by heating the
liquid crystal cell at a temperature at which the used liquid
crystals take an isotropic phase and then cooling it to room
temperature.
[0199] A polarizer is affixed to the both sides of the cell in such
a manner that the polarization directions of the polarizers have a
predetermined angle from the polarization directions of the
respective linearly polarized radiations projected onto the liquid
crystal alignment films of the substrates to construct a liquid
crystal display element. A liquid crystal display element having
TN, STN, VA or horizontally or vertically hybrid liquid crystal
cells can be obtained by adjusting the projection direction of the
projected nonpolarized light or the angle formed by the
polarization directions of the linearly polarized radiations and
the angle between each of the substrates and each of the
polarizers.
[0200] As the above sealer may be used an epoxy resin containing
aluminum oxide spheres as a curing agent and spacer.
[0201] The above liquid crystals are, for example, nematic or
smectic liquid crystals. In the case of a VA liquid crystal cell,
the liquid crystals are preferably what form nematic liquid
crystals, such as Schiff based liquid crystals, azoxy-based liquid
crystals, biphenyl-based liquid crystals, phenylcyclohexane-based
liquid crystals, ester-based liquid crystals, terphenyl-based
liquid crystals, biphenylcyclohexane-based liquid crystals,
pyrimidine-based liquid crystals, dioxane-based liquid crystals,
bicyclooctane-based liquid crystals or cubane-based liquid
crystals. What are obtained by adding cholesteric liquid crystals
such as cholestyl chloride, cholesteryl nonanoate or cholesteryl
carbonate, or a chiral agent marketed under the trade name of C-15
or CB-15 (of Merk Co., Ltd.) to the above liquid crystals may be
used. Further, ferroelectric liquid crystals such as
p-desiloxybenzilidene-p-amino-2-methylbutyl cinnamate may also be
used.
[0202] The polarizer affixed to the exterior sides of the liquid
crystal cell is a polarizer manufactured by sandwiching a
polarizing film called "H film" which absorbs iodine while
polyvinyl alcohol is stretched and aligned between cellulose
acetate protective films, or the H film itself.
EXAMPLES
[0203] The following examples are provided for the purpose of
further illustrating the present invention but are in no way to be
taken as limiting.
Example 1
[0204] Optical alignment was carried out as shown in FIG. 3.
[0205] A polymer (may be called to "PMI-15" hereinafter) prepared
by introducing a chalcone group as a side chain into a
phenylmaleimide-styrene alternating copolymer through a methylene
group was dissolved in .gamma.-butyrolactone in an amount of 3%,
and the obtained solution was applied to a quartz glass substrate 5
by spin coating and dried to form a polymer film having a thickness
of 70 nm. Thereafter, the surface of the polymer film was exposed
to polarized UV having a central wavelength of 350 nm from a
polarization irradiating unit 1 through a slit exposure mask 3
while a movable stage 6 mounting the formed substrate was moved
parallel to the X-axis direction (right direction) at a rate of
several tens of micrometers per second so as to exposure the slit
pattern. The irradiation energy was 2 J/cm.sup.2. A slit exposure
mask pattern having line and space widths of 7 .mu.m as shown in
FIG. 7 was used in this example. Thereafter, two exposed substrates
were used to manufacture a TN cell having a thickness of 4.5 .mu.m.
The ZLI-5081 liquid crystal cells (of Merk Co., Ltd.) were used. It
was confirmed in this example that a pretilt angle could be
developed stably by the optical alignment method of the present
invention without inclining the optical alignment film formed
substrate. The pretilt angle became 0.degree. until the stage
moving rate was 4 .mu.m/sec as shown in FIG. 8. A pretilt angle of
0.3.degree. or more was developed when the stage moving rate was
8.5 to 34 .mu.m/sec as shown in FIG. 8. Thus, a slight increase in
the pretilt angle was seen. When the stage moving rate was further
accelerated to 64 .mu.m/sec, it was confirmed that the pretilt
angle greatly increased to 2.6.degree..
[0206] As a result, the optical alignment strength parameter which
indicates the effect of optical alignment is an exposure frequency
which is determined by irradiation energy J, the width L of the
slit mask and the substrate moving rate u. The exposure frequency
Fp is represented by the following equation.
Fp=(u/2L).times.J
[0207] In this example, when irradiation energy J=1.1 J/cm.sup.2,
2L=1.66 (sec) and u=8.425 .mu.m/sec, exposure frequency Fp=0.6
Hz.
[0208] In other experiments on the optical alignment method using
PMI-15, when the exposure frequency was changed from 0.66 Hz to 2.4
Hz, a pretilt angle of 0.5.degree. which was characteristic of the
material was obtained.
Synthesis Example 1
[0209] Polymerization of Polyamic Acid
[0210] 0.1 mol (22.4 g) of 2,3,5-tricarboxycyclopentylacetic
dianhydride, 0.09 mol (9.73 g) of p-phenylenediamine and 0.01 mol
(5.22 g) of cholestanyloxy(3,5-diaminobenzoyl) were dissolved in
350 g of N-methyl-2-pyrrolidone and reacted at 60.degree. C. for 6
hours. Thereafter, the reaction mixture was added to an excessive
amount of methanol to precipitate a reaction product. The
precipitate was then washed with methanol and dried at 40.degree.
C. under reduced pressure for 15 hours to produce 34.2 g of
polyamic acid (to be referred to as "polymer a" hereinafter).
[0211] Synthesis of Specific Polymer
[0212] 300 g of N-methyl-2-pyrrolidone, 41.3 g of
1-bromo-8-(4-chalconylox- y)octane and 13.8 g of potassium
carbonate were added to 14.9 g of the obtained polymer a to carry
out a reaction at 120.degree. C. for 4 hours. Thereafter, the
reaction mixture solution was added to water to precipitate a
reaction product. The obtained precipitate was washed with water
and dried under reduced pressure for 15 hours to produce 43.9 g of
polyamic acid ester (to be referred to as "polymer b"
hereinafter).
Example 2
[0213] The polymer "b" obtained in Synthesis Example 1 was
dissolved in .gamma.-butyrolactone to prepare a 3 wt % solution,
and the obtained solution was applied to a surface polished
non-alkali glass substrate by spin coating and dried by heating at
180.degree. C. for 5 minutes to form a polymer film having a
thickness of 80 nm. The surface of the polymer film was exposed to
polarized UV having a central wavelength of 350 nm through a slit
exposure mask while a movable stage mounting the substrate was
moved parallel to the surface of the polymer film at a rate of 100
.mu.m/sec. The irradiation energy was 5 J/cm.sup.2, and the
polarization direction of the polarized UV was the same as the
moving direction. The slit width of the exposure mask was 7 .mu.m.
Thereafter, the exposed substrate was used to construct a
non-parallel cell having a thickness of 18 .mu.m, and the MLC6608
liquid crystals of Merk Co., Ltd. were filled to obtain a liquid
crystal display element. The alignability of the liquid crystals
was excellent, and the pretilt angle was 89.degree.. A crystal
rotation method was used for the evaluation of the pretilt
angle.
Example 3
[0214] A liquid crystal display element was obtained in the same
manner as in Example 2 except that the irradiation energy was
changed to 10 J/cm.sup.2. The alignability of the liquid crystals
was excellent, and the pretilt angle was 89.degree..
Synthesis Example 2
[0215] 26.2 g of 4-(8-(4-chalconyloxy)octanoxy)phenylmaleimide,
22.7 g of 4-(8-(4-chalconyloxy)octanoxy)styrene and 3.0 g of
azobisisobutyronitrile were dissolved in 500 ml of dimethyl
acetamide to carry out a reaction in a nitrogen atmosphere at
80.degree. C. for 10 hours. A viscous reaction mixture was added to
methanol to precipitate a polymer which was then dried to obtain 49
g of a 4-(8-(4-chalconyloxy)octanoxy)phenylmaleimide/4-
-(8-(4-chalconyloxy)octanoxy)styrene alternating copolymer. This
polymer was designated as polymer "c".
Example 4
[0216] The polymer "c" obtained in Synthesis Example 2 was
dissolved in .gamma.-butyrolactone to prepare a solution having a
solid content of 2.5 wt % which was then applied to a
surface-polished non-alkali glass substrate by spin coating and
dried by heating at 180.degree. C. for 5 minutes to form a polymer
film having a thickness of 80 nm. Thereafter, as shown in FIG. 9, a
four-domain-divided mask 24 (3 mm.times.3 mm pixels were divided
into four sections each having an area of 1.5 mm.times.1.5 mm) was
placed above the substrate with aligned film 25 with a 20 .mu.m
space therebewteen, and a polarization pattern having a periodical
intensity distribution with a pitch of 7 .mu.m was projected onto
the substrate to expose a 1/4 area of the pixels through the slit
pattern while the substrate and the domain-divided mask 24 were
moved parallel at a rate of 100 .mu.m/sec. Subsequently, the above
exposure was carried out four times by turning the substrate at
90.degree. each time to obtain the substrate with aligned film 25
having four areas which differed from one another in aligning
direction. Two substrates with aligned film 25 of this kind were
prepared to manufacture a TN cell having a thickness of 4.5 .mu.m.
The ZLI-5081 liquid crystals (of Merk Co., Ltd.) were used. The
alignability of the liquid crystals of the obtained element was
excellent and the view field of the element was wide as shown in
FIG. 10.
Example 5
[0217] The polymer "c" obtained in Synthesis Example 2 was
dissolved in .gamma.-butyrolactone to prepare a 2.5 wt % solution,
and the obtained solution was applied to a surface polished
non-alkali glass substrate by spin coating and dried by heating at
180.degree. C. for 5 minutes to form a polymer film having a
thickness of 80 nm. A polarization pattern 12 having a periodical
intensity distribution with a pitch of 7 .mu.m shown in FIG. 6 was
projected onto the substrate for exposure by scanning from the base
line in two right and left directions 13 at aerate of 100
.mu.m/sec. Polarized light had a central wavelength of 350 nm and
an irradiation energy of 24 mW. A non-parallel cell having a
thickness of 18 .mu.m was manufactured using the exposed substrate
5, and the K15 liquid crystals of Merk Co., Ltd. were filled to
obtain a liquid crystal display element aligned and divided to two
domains. The alignability of the liquid crystals was excellent and
the pretilt angle of each domain was 1.0.degree.. The crystal
rotation method was used for the evaluation of the pretilt angle.
In FIG. 6, reference numeral 14 denotes the polarization direction
of the polarized light having a periodical intensity
distribution.
[0218] As described above, according to the optical alignment
method of the present invention, optical alignment can be effected
by moving a glass substrate 1 mm to 10 mm in a fixed direction even
when the exposure frequency Fp is 0.2 to 1 Hz without being
restricted by the polarized UV exposure area of the same size as
the glass substrate to be optically aligned, by the size of a slit
exposure mask of the same size as the glass substrate and by the
size of the glass substrate whether it is A4-sized or 1 m.times.1
m. That is, in this optical alignment method, the glass substrate
does not need to be moved parallel a distance almost double as its
size unlike the current optical alignment method, thereby making it
possible to prevent a large increase in the size of an exposure
device.
[0219] Further, according to the present invention, a liquid
crystal display element which can be used in a homeotropic
alignment mode and has been difficult to be provided with aligning
capability by optical alignment can be formed.
* * * * *