U.S. patent application number 12/450314 was filed with the patent office on 2010-04-15 for photoreactive polymer and method for preparing the same.
Invention is credited to Dai-Seung Choi, Sung-Ho Chun, Sung-Don Hong, Hye-Young Jung, Heon Kim, Dong-Woo Yoo.
Application Number | 20100093955 12/450314 |
Document ID | / |
Family ID | 39766086 |
Filed Date | 2010-04-15 |
United States Patent
Application |
20100093955 |
Kind Code |
A1 |
Choi; Dai-Seung ; et
al. |
April 15, 2010 |
PHOTOREACTIVE POLYMER AND METHOD FOR PREPARING THE SAME
Abstract
The present invention relates to a photoreactive polymer that
comprises a multi-cyclic compound in a main chain, and a
polymerization method thereof. Since the photoreactive polymer
according to the present invention comprises a multi-cyclic
compound having a high glass transition temperature as a main
chain, the thermal stability is excellent, and since the mobility
of the main chain is relatively high as compared to that of an
additional polymer, a photoreactive group can be freely moved in
the main chain of the polymer. Accordingly, it is possible to
overcome a slow photoreactive rate that is considered a
disadvantage of a polymer material used to prepare an alignment
film for known liquid crystal display devices.
Inventors: |
Choi; Dai-Seung; (Daejeon
Metropolitan City, KR) ; Jung; Hye-Young; (Daejeon
Metropolitan City, KR) ; Chun; Sung-Ho; (Daejeon
Metropolitan City, KR) ; Kim; Heon; (Daejeon
Metropolitan City, KR) ; Hong; Sung-Don; (Daejeon
Metropolitan City, KR) ; Yoo; Dong-Woo; (Daejeon
Metropolitan City, KR) |
Correspondence
Address: |
MCKENNA LONG & ALDRIDGE LLP
1900 K STREET, NW
WASHINGTON
DC
20006
US
|
Family ID: |
39766086 |
Appl. No.: |
12/450314 |
Filed: |
March 21, 2008 |
PCT Filed: |
March 21, 2008 |
PCT NO: |
PCT/KR2008/001608 |
371 Date: |
September 21, 2009 |
Current U.S.
Class: |
526/123.1 ;
526/131; 526/134; 526/266; 526/326; 526/90; 549/283; 560/8 |
Current CPC
Class: |
C08F 290/14 20130101;
C08F 210/02 20130101; C08F 210/02 20130101; C08F 297/06 20130101;
C08F 232/00 20130101; C08F 2500/25 20130101; C08F 290/00 20130101;
C08F 297/00 20130101; C08F 2500/26 20130101 |
Class at
Publication: |
526/123.1 ;
526/90; 526/131; 526/134; 526/266; 526/326; 549/283; 560/8 |
International
Class: |
C08F 4/44 20060101
C08F004/44; C08F 4/00 20060101 C08F004/00; C08F 4/06 20060101
C08F004/06; C08F 24/00 20060101 C08F024/00; C08F 18/02 20060101
C08F018/02; C07D 311/02 20060101 C07D311/02; C07C 69/00 20060101
C07C069/00 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 22, 2007 |
KR |
10-2007-0028104 |
Mar 22, 2007 |
KR |
10-2007-0028114 |
Claims
1. A multi-cyclic compound that is represented by the following
Formula 1: ##STR00017## wherein P is an integer in the range of 0
to 4, at least one of R.sub.1, R.sub.2, R.sub.3, and R.sub.4 is a
radical that is selected from the group consisting of the following
Formulae 1a, 1b, and 1c, the remains of R.sub.1, R.sub.2, R.sub.3,
and R.sub.4 are each independently selected from the group
consisting of hydrogen; halogen; substituted or unsubstituted
C1-C20 alkyl; substituted or unsubstituted C2-C20 alkenyl;
substituted or unsubstituted saturated or unsaturated C5-C12
cycloalkyl; substituted or unsubstituted C6-C40 aryl; substituted
or unsubstituted C7-C15 aralkyl; substituted or unsubstituted
C2-C20 alkynyl; and a non-hydrocarbonaceous polar group that
comprises one or more elements selected from the group consisting
of oxygen, nitrogen, phosphorus, sulfur, silicon, and boron,
R.sub.1 and R.sub.2 or R.sub.3 and R.sub.4 may be bonded to each
other to form a C1-C10 alkylidene group, or R.sub.1 or R.sub.2 may
be bonded to any one of R.sub.3 and R.sub.4 to form a saturated or
unsaturated C4-C12 ring or an aromatic ring having 6 to 24 carbon
atoms, ##STR00018## wherein A is substituted or unsubstituted
C1-C20 alkylene, carbonyl, carboxy, substituted or unsubstituted
C6-40 arylene, or a simple bond; B is oxygen, sulfur, --NH--, or a
simple bond; X is oxygen or sulfur; R.sub.9 is a simple bond,
substituted or unsubstituted C1-C20 alkylene; substituted or
unsubstituted C2-C20 alkenylene; substituted or unsubstituted
C5-C12 cycloalkylene; substituted or unsubstituted C6-C40 arylene;
substituted or unsubstituted C7-C15 aralkylene; or substituted or
unsubstituted C2-C20 alkynylene; R.sub.10, R.sub.11, R.sub.12, and
R.sub.13 are each independently substituted or unsubstituted C1-C20
alkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or
unsubstituted C6-C30 aryloxy, or substituted or unsubstituted
C6-C40 aryl; C is C6-C40 aryl; or C6-C40 hetero aryl that comprises
Group 14, 15 or 16 hetero elements, and the aryl or hetero aryl is
substituted with substituted or unsubstituted C1-C20 alkoxy or
substituted or unsubstituted C6-C30 aryloxy; in Formula 1c, at
least one of R'.sub.10, R'.sub.11, R'.sub.12, R'.sub.13, and
R'.sub.14 is necessarily substituted or unsubstituted C1-C20 alkoxy
or substituted or unsubstituted C6-C30 aryloxy, and the remains are
each independently hydrogen, substituted or unsubstituted C1-C20
alkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or
unsubstituted C6-C30 aryloxy, or substituted or unsubstituted
C6-C40 aryl; the non-hydrocarbonaceous polar group is --OR.sub.6,
--OC(O)OR.sub.6, --R.sub.5OR.sub.6, --R.sub.5OC(O)OR.sub.6,
--C(O)OR.sub.6, --R.sub.5C(O)OR.sub.6, --C(O)R.sub.6,
--R.sub.5C(O)R.sub.6, --OC(O)R.sub.6, --R.sub.5OC(O)R.sub.6,
--(R.sub.5O).sub.p--OR.sub.6 (p is an integer in the range of 1 to
10), --(OR.sub.5).sub.p--OR.sub.6 (p is an integer in the range of
1 to 10), --C(O)--O--C(O)R.sub.6, --R.sub.5C(O)--O--C(O)R.sub.6,
--SR.sub.6, --R.sub.5SR.sub.6, --SSR.sub.6, --R.sub.5SSR.sub.6,
--S(.dbd.O)R.sub.6, --R.sub.5S(.dbd.O)R.sub.6,
--R.sub.5C(.dbd.S)R.sub.6, --R.sub.6C(.dbd.S)SR.sub.6,
--R.sub.5SO.sub.3R.sub.6, --SO.sub.3R.sub.6,
--R.sub.5N.dbd.C.dbd.S, --N.dbd.C.dbd.S, --NCO, --R.sub.5--NCO,
--CN, --R.sub.5CN, --NNC(.dbd.S)R.sub.6,
--R.sub.5NNC(.dbd.S)R.sub.6, --NO.sub.2, --R.sub.5NO.sub.2,
##STR00019## ##STR00020## ##STR00021## in the non-hydrocarbonaceous
polar group, R.sub.5 may be selected from the group consisting of
substituted or unsubstituted C1-C20 alkylene; substituted or
unsubstituted C2-C20 alkenylene; substituted or unsubstituted
saturated or unsaturated (5-C12 cycloalkylene; substituted or
unsubstituted C6-C40 arylene; substituted or unsubstituted C7-C15
aralkylene; and substituted or unsubstituted C2-C20 alkynylene, and
R.sub.6, R.sub.7 and R.sub.8 may be selected from the group
consisting of each independently hydrogen; halogen; substituted or
unsubstituted C1-C20 alkyl; substituted or unsubstituted C2-C20
alkenyl; substituted or unsubstituted saturated or unsaturated
C5-C12 cycloalkyl; substituted or unsubstituted C6-C40 aryl;
substituted or unsubstituted C7-C15 aralkyl; and substituted or
unsubstituted C2-C20 alkynyl.
2. The multi-cyclic compound as set forth in claim 1, wherein in
Formulae 1a or 1b, C is any one selected from the group consisting
of compounds represented by the following Formulae: ##STR00022##
##STR00023## wherein at least one of R'.sub.10, R'.sub.11,
R'.sub.12, R'.sub.13, R'.sub.14, R'.sub.15, R'.sub.16, R'.sub.17,
and R'.sub.18 is necessarily substituted or unsubstituted C1-C20
alkoxy or substituted or unsubstituted C6-C30 aryloxy, and the
remains are each independently hydrogen, substituted or
unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20
alkoxy, substituted or unsubstituted C6-C30 aryloxy, or substituted
or unsubstituted C6-C40 aryl.
3. A photoreactive polymer comprising the compound of claim 1 as a
monomer in a main chain and a repeating unit that is represented by
the following Formula 3: ##STR00024## wherein n is in the range of
50 to 5,000, and P, R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are the
same as those defined in Formula 1.
4. The photoreactive polymer as set forth in claim 3, wherein in
Formulae 1a or 1b, C is any one selected from the group consisting
of compounds represented by the following Formulae: ##STR00025##
##STR00026## wherein at least one of R'.sub.10, R'.sub.11,
R'.sub.12, R'.sub.13, R'.sub.14, R'.sub.15, R'.sub.16, R'.sub.17,
and R'.sub.18 is necessarily substituted or unsubstituted C1-C20
alkoxy or substituted or unsubstituted C6-C30 aryloxy, and the
remains are each independently hydrogen, substituted or
unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20
alkoxy, substituted or unsubstituted C6-C30 aryloxy, or substituted
or unsubstituted C6-C40 aryl.
5. The photoreactive polymer as set forth in claim 3, further
comprising one or more of the multi-cyclic compounds that are
represented by the following Formula 4 as a monomer: ##STR00027##
wherein P' is an integer in the range of 0 to 4, R'.sub.1,
R'.sub.2, R'.sub.3, and R'.sub.4 are each independently selected
from the group consisting of hydrogen; halogen; substituted or
unsubstituted C1-C20 alkyl, substituted or unsubstituted C2-C20
alkenyl; substituted or unsubstituted C5-C12 cycloalkyl;
substituted or unsubstituted C6-C40 aryl; substituted or
unsubstituted C7-C15 aralkyl; substituted or unsubstituted C2-C20
alkynyl; and a non-hydrocarbonaceous polar group that comprises one
or more elements selected from the group consisting of oxygen,
nitrogen, phosphorus, sulfur, silicon, and boron, if R'.sub.1,
R'.sub.2, R'.sub.3, and R'.sub.4 are not hydrogen, halogen, or a
polar functional group, R'.sub.1 and R'.sub.2, or R'.sub.3 and
R'.sub.4 may be bonded to each other to form a C1-C10 alkylidene
group, or R'.sub.1 or R'.sub.2 may be bonded to any one of R'.sub.3
and R'.sub.4 to form a saturated or unsaturated C4-C12 ring or an
aromatic ring having 6 to 24 carbon atoms, the
non-hydrocarbonaceous polar group is --OR.sub.6, --OC(O)OR.sub.6,
--R.sub.5OR.sub.6, --R.sub.5OC(O)OR.sub.6, --C(O)OR.sub.6,
--R.sub.5C(O)OR.sub.6, --C(O)R.sub.6, --R.sub.5C(O)R.sub.6,
--OC(O)R.sub.6, --R.sub.5OC(O)R.sub.6, --(R.sub.5O).sub.p--OR.sub.6
(p is an integer in the range of 1 to 10),
--(OR.sub.5).sub.p--OR.sub.6 (p is an integer in the range of 1 to
10), --C(O)--O--C(O)R.sub.6, --R.sub.5C(O)--O--C(O)R.sub.6,
--SR.sub.6, --R.sub.5SR.sub.6, --SSR.sub.6, --R.sub.5SSR.sub.6,
--S(.dbd.O)R.sub.6, --R.sub.5S(.dbd.O)R ,
--R.sub.5C(.dbd.S)R.sub.6, --R.sub.5C(.dbd.S)SR.sub.6,
--R.sub.6SO.sub.3R.sub.6, --SO.sub.3R.sub.6,
--R.sub.5N.dbd.C.dbd.S, --N.dbd.C.dbd.S, --NCO, --R.sub.5--NCO,
--CN, --R.sub.5CN, --NNC(.dbd.S)R.sub.6,
--R.sub.5NNC(.dbd.S)R.sub.6, --NO.sub.2, --R.sub.5NO.sub.2,
##STR00028## ##STR00029## ##STR00030## R.sub.5 of each of the
functional groups is substituted or unsubstituted C1-C20 alkylene;
substituted or unsubstituted C2-C20 alkenylene; substituted or
unsubstituted C5-C12 cycloalkylene; substituted or unsubstituted
C6-C40 arylene; substituted or unsubstituted C7-C15 aralkylene; or
substituted or unsubstituted C2-C20 alkynylene, and R.sub.6,
R.sub.7 and R.sub.8 are each hydrogen; halogen; substituted or
unsubstituted C1-C20 alkyl; substituted or unsubstituted C2-C20
alkenyl; substituted or unsubstituted C5-C12 cycloalkyl;
substituted or unsubstituted C6-C40 aryl; substituted or
unsubstituted C7-C15 aralkyl; or substituted or unsubstituted
C2-C20 alkynyl.
6. A method of preparing a photoreactive polymer, the method
comprising: polymerizing the multi-cyclic compound of claim 1 in
the presence of a catalyst mixture that comprises a procatalyst
including Group 4, Group 6, and Group 8 transition metals, a
occatalyst that provides a Lewis base capable of being weakly
coordinate bonded to the metal of the procatalyst, and selectively
activators including neutral Group 15 and Group 16 elements that
may improve the activity of the procatalyst metal, at a temperature
in the range of 10 to 200.degree. C. while linear alkene, which is
capable of controlling a size of a molecular weight, is added; and
adding a catalyst that comprises Group 4 or Group 8 to Group 10
transition metals to add hydrogen to a double bond remaining on a
main chain at a temperature in the range of 10 to 250.degree.
C.
7. The method of preparing a photoreactive polymer as set forth in
claim 6, wherein the catalyst mixture comprises 1 to 100,000 mole
of the cocatalyst, and selectively 1 to 100 mole of the activators
that comprises neutral Group 15 and Group 16 elements improving the
activity of the procatalyst metal based on 1 mole of the
procatalyst.
8. The method of preparing a photoreactive polymer as set forth in
claim 6, wherein the procatalyst is selected from the group
consisting of TiCl.sub.4, WCl.sub.6, MoCl.sub.5, RuCl.sub.3, and
ZrCl.sub.4.
9. The method of preparing a photoreactive polymer as set forth in
claim 6, wherein the cocatalyst is selected from the group
consisting of substituents comprising borane, borate,
alkylaluminum, alkyl aluminoxane, alkylaluminum halide, aluminum
halide, lithium, magnesium, germanium, lead, zinc; tin, and
silicon.
10. The method of preparing a photoreactive polymer as set forth in
claim 6, wherein the catalyst mixture comprises linear alkene,
which is capable of controlling the size of the molecular weight,
in an amount of 1 to 100 mol % based on the monomer that is the
multi-cyclic compound.
11. The method of preparing a photoreactive polymer as set forth in
claim 6, wherein the catalyst that comprises the Group 4, Group 8,
Group 9, or Group 10 transition metals used during the
hydrogenation reaction is present in a homogeneous form that can be
immediately mixed with a solvent or a substance in which the metal
catalyst complex compound is carried in a fine supporting material,
and the fine supporting material is silica, titania,
silica/chromia, silica/chromia/titania, silica/alumina, aluminum
phosphate gel, silanized silica, silica hydrogel, montmorilonite
clay, or zeolite.
12. A photoreactive polymer that is represented by the following
Formula 5: ##STR00031## wherein n is the degree of polymerization
in the range of 50 to 5000, the content of the repeating unit of
cycloolefin that is represented by x is in the range of 0.1 to 99.9
mol %, the content of the repeating unit of linear olefin that is
represented by y is in the range of 0.1 to 99.9 mol %, the content
of the repeating unit of cycloolefin that is represented by z is in
the range of 0.1 to 99.9 mol %, the order of the repeatition of
noncycloolefin and cycloolefin is random, P, R.sub.1, R.sub.2,
R.sub.3, and R.sub.4 are the same as those defined in Formula 1, Ra
is a hydrogen atom or a C1-C20 hydrocarbon group, and P', R.sub.1',
R.sub.2', R.sub.3', and R.sub.4' are the same as those defined in
Formula 4.
13. The photoreactive polymer as set forth in claim 12, wherein in
Formulae 1a or 1b, C is any one selected from the group consisting
of compounds represented by the following Formulae: ##STR00032##
wherein at least one of R'.sub.10, R'.sub.11, R'.sub.12, R'.sub.13,
R'.sub.14, R'.sub.15, R'.sub.16, R'.sub.17, and R'.sub.18 is
necessarily substituted or unsubstituted C1-C20 alkoxy or
substituted or unsubstituted C6-C30 aryloxy, and the remains are
each independently selected from the group consisting of hydrogen,
substituted or unsubstituted C1-C20 alkyl, substituted or
unsubstituted C1-C20 alkoxy, substituted or unsubstituted C6-C30
aryloxy, and substituted or unsubstituted C6-C40 aryl.
14. A method of preparing the photoreactive polymer of claim 12,
the method comprising: polymerizing a noncycloolefin monomer and a
cycloolefin monomer that comprises a photoactive functional group
in the presence of a catalyst mixture that consists of a
procatalyst comprising a metallocene catalyst and a cocatalyst
comprising aluminoxane at a temperature in the range of 10 to
200.degree. C. under polymerization pressure in the range of 1 to
69 bar.
15. The method of preparing the photoreactive polymer as set forth
in claim 14, wherein the catalyst mixture comprises 10.sup.-4 to
10.sup.-2 mole of the procatalyst based on 1 mole of the
occatalyst.
16. The method of preparing the photoreactive polymer as set forth
in claim 14, wherein the procatalyst is selected from the group
consisting of rac-ethylene-bis-(1-indenyl)-zirconiumdichloride,
isopropylene-(9-fluorenyl)-cyclopentadienyl-zirconiumdichloride,
rac-dimethylsilyl-bis-(1-indenyl)-zirconium dichloride,
phenylmethyl-(9-fluorenyl)-cyclopentadienyl zirconium dichloride,
rac-dimethylgermyl-bis-(1-indenyl)-zirconium dichloride,
rac-phenyl-methylsilyl-bis-(1-indenyl)-zirconium dichloride, and
rac-phenylvinylsilyl-bis-(1-indenyl)-zirconium dichloride.
17. The method of preparing the photoreactive polymer as set forth
in claim 14, wherein the aluminoxane is selected from the group
consisting of methyl aluminoxane, ethyl aluminoxane, isobutyl
aluminoxane, and butyl aluminoxane.
18. The method of preparing the photoreactive polymer as set forth
in claim 14, wherein the transition metal compound (catalyst and
occatalyst) is activated in a solution for 15 to 60 minutes and the
temperature is previously set to a range of 15 to 70.degree. C.
Description
TECHNICAL FIELD
[0001] The present invention relates to a photoreactive polymer,
and more particularly to a photoreactive polymer that has an
alignment property due to a photoreaction and includes a
multi-cyclic compound in a main chain, thus having the excellent
thermal stability and allowing the photoreaction to be rapid.
[0002] This application claims priority from Korea Patent
Application Nos. 10-2007-0028114 and 10-2007-0028104 filed on Mar.
22, 2007 in the KIPO, the disclosure of which is incorporated
herein by reference in its entirety.
BACKGROUND ART
[0003] In recent years, a liquid crystal display that has a light
weight and consumes a small amount of electric power has been used
as a most competitive display that can be used instead of a cathode
ray tube. In particular, since a thin film transistor liquid
crystal display (TFT-LCD) that is driven by using a thin film
transistor independently drives each of pixels, a response speed of
the liquid crystal is very high, thus, a high-quality dynamic image
can be realized. Accordingly, currently, the thin film transistor
liquid crystal display is applied to a notebook computer, a
wall-mounted television and the like, and the application range
thereof is expanded.
[0004] During the production of a typical color thin film
transistor-liquid crystal display, a thin film transistor driving
device and an ITO transparent electrode are layered on a glass
substrate, and an alignment film is then layered thereon to form a
lower substrate of a cell. Spacers are formed by using a silant in
order to inject a liquid crystal material between inner surfaces of
a pair of upper and lower substrates, polarized films are provided
on outer surfaces of the glass substrates, and the liquid crystal
material is injected between a pair of substrates and aired to
produce a liquid crystal display cell.
[0005] In the TFT-LCD, in order to use the liquid crystal as an
optical switch, it is required that the liquid crystal is initially
aligned on the layer on which the thin film transistor is formed at
the innermost part of the display cell in a predetermined
direction. In order to achieve this, a liquid crystal alignment
film is used.
[0006] As a method of preparing the alignment film, a rubbing
treatment method of unidirectionally rubbing a polymer resin film
made of a polyimide or the like formed on a substrate by using
clothes or a method of inclinedly depositing silicon dioxide
(SiO.sub.2) is known. In the use of the alignment film that is
prepared by using the rubbing treatment method, there are problems
in that the contamination is caused by the impurity that may be
generated due to contact during the rubbing, the yield of the
products is reclined due to the occurrence of static electricity,
and contrast is reduced. In the case of the method of inclinedly
depositing silicon dioxide, there are problems in that the
preparing cost is increased and it is difficult to form the film
having a large area, thus, the film is not suitable to be applied
to a large liquid crystal display.
[0007] In order to solve this, an alignment method by a non-rubbing
process using a photopolymerizable alignment material is developed
to perform a photopolymerization by using the radiation of light so
that the alignment of polymer is inclined to align liquid crystals.
A representative example of the non-rubbing process is an optical
alignment using photopolymerization that is announced by M. Schadt,
et al. (Jpn. J. Appl. Phys., Vol 31, 1992, 2155), Dae S. Kang, et
al. (U.S. Pat. No. 5,464,669), and Yuriy Reznikov (Jpn. J. Appl.
Phys. Vol. 34, 1995, L1000). The optical alignment is a mechanism
in which a photoreaction of a photosensitive group that is
connected to the polymer occurs due to linearly polarized
ultraviolet rays, and in this procedure, a main chain of the
polymer is unidirectionally aligned, thereby aligning the liquid
crystals.
[0008] The poly cinnamate-based polymer such as PVCN (poly(vinyl
cinnamate)) and PVMC (poly(vinyl methoxycinnamate)) has been mainly
used as a representative material of the photopolymerizable
alignment film. However, the poly cinnamate-based polymer has a
problem in that the optical alignment property of the polymer is
excellent but the thermal stability is poor. That is, the thermal
stability of the alignment film depends on the thermal stability of
the polymer, and since the main chain of the polymer of polyvinyl
cinnamate has a glass transition temperature of 100.degree. C. or
less, there is a problem in that the thermal stability of the
alignment film is reduced.
[0009] Meanwhile, Japanese Unexamined Patent Application
Publication No. 11-181127 discloses a method of producing a polymer
type of alignment film that has a main chain such as acrylate and
methacrylate and a side chain having a photosensitive group such as
a cinnamate group, and an alignment film that is produced by using
the method. However, the patent is disadvantageous in that since
the mobility of the polymer is poor, even though the polymer is
exposed to light for a long time, it is difficult to obtain the
desired alignment property. The reason for this is that since the
photo-sensitive group which is present in the polymer is restricted
by the main chain of the polymer, the group is difficult to rapidly
react with the radiated polarized light. Accordingly, since a long
time is required to obtain a network polymer, a process efficiency
is reduced, and if an alignment treatment process is finished after
an in-sufficient time, since the alignment of the liquid crystals
is insufficient in the prepared liquid crystal display, there are
problems in that a dichroic ratio is low and contrast is
reduced.
[0010] Korean Unexamined Patent Application Publication Nos.
2006-0029068 and 2004-0102862 disclose that polarized UV is
radiated on a coated liquid crystal material without using a
rubbing process to determine an alignment direction of liquid
crystal. However, as described in the above patent, in the case of
when the polarized UV is radiated on a curable liquid crystal
material to align the liquid crystal, since the curing of the
liquid crystal maws in an alignment direction, the insufficient
curing (pairs, thus reducing the surface strength and easily
causing the deformation due to external impact or heat.
[0011] Accordingly, a demand for a novel photoreactive polymer that
has the excellent thermal stability and the improved surface
strength and photoreaction rate is growing.
DISCLOSURE OF INVENTION
Technical Problem
[0012] The present invention has been made keeping in mind the
above problems occurring in the related art, and it is an object of
the present invention to provide a compound that has the excellent
thermal stability and the improved photoreaction rate and is
capable of being used as a monomer of the photoreactive
polymer.
[0013] It is another object of the present invention to provide a
photoreactive polymer that includes the compound.
[0014] It is still another object of the present invention to
provide a method of preparing the photoreactive polymer.
Technical Solution
[0015] In order to accomplish the above objects, the present
invention provides a multi-cyclic compound that includes a
photoactive functional group in a main chain.
[0016] Additionally, the present invention provides a ring-opened
hydrogenated polymer that includes the multi-cyclic compound as a
monomer.
[0017] Additionally, the present invention provides a photoreactive
polymer that includes a cycloolefin-noncycloolefin in a main
chain.
[0018] Additionally, the present invention provides a method of
preparing a ring-opened hydrogenated polymer that includes the
multi-cyclic compound as a monomer. The method includes
polymerizing the multi-cyclic compound in the presence of a
catalyst mixture that includes a procatalyst including Group 4,
Group 6, and Group 8 transition metals, a cocatalyst that provides
a Lewis base capable of being weakly coordinate bonded to the metal
of the procatalyst, and activators including neutral Group 15 and
Group 16 elements that selectively improve the activity of the
procatalyst metal at a temperature in the range of 10 to
200.degree. C. while linear alkene, which is capable of controlling
a size of a molecular weight, is added, and adding a catalyst that
includes Group 4 or Group 8 to Group 10 transition metals to add
hydrogen to a double bond remaining on a main chain.
[0019] Additionally, the present invention provides a method of
preparing a polymer that includes a cycloolefin-noncycloolefin in a
main chain. The method includes copolymerizing a cycloolefin
monomer and a noncycloolefin monomer in conjunction with the
noncyclic monomer by using a metallocene catalyst while a ring of
the cyclic monomer is not opened. The copolymerizing is performed
in the presence of a catalyst mixture that consists of a
procatalyst including a metallocene catalyst and a cocatalyst
including aluminoxane at a temperature in the range of 10 to
200.degree. C. under polymerization pressure in the range of 1 to
60 bar.
Advantageous Effects
[0020] Since a photoreactive polymer according to the present
invention includes a multi-cyclic compound having a high glass
transition temperature as a main chain, the thermal stability is
excellent, and since the mobility of the main chain is relatively
high as compared to that of an additional polymer, a photoreactive
group can be freely moved in the main chain of the polymer.
Accordingly, it is possible to overcome a slow photoreactive rate
that is considered a disadvantage of a polymer material used to
prepare an alignment film for known liquid crystal display devices.
In addition, in the case of the photoreactive polymer that includes
the cycloolefin-noncycloolefin, the surface strength that cannot be
improved by using the multi-cyclic compound can be improved by
introducing the noncycloolefin compound into the main chain.
BRIEF DESCRIPTION OF THE DRAWINGS
[0021] FIG. 1 is a graph that illustrates the measurement of light
leakage of a liquid crystal retardation film that is prepared in
Preparation Example 1 and Comparative Example 2; and
[0022] FIG. 2 is a graph that illustrates the measurement of light
leakage of a retardation film that is prepared in Preparation
Example 4 and Comparative Example 3.
BEST MODE FOR CARRYING OUT THE INVENTION
[0023] Hereinafter, a detailed description will be given of the
present invention.
[0024] A multi-cyclic compound having a photoactive functional
group according to the present invention is a compound that is
represented by the following Formula 1.
##STR00001##
[0025] In the above Formula 1, P is an integer in the range of 0 to
4, and
[0026] at least one of R.sub.1, R.sub.2, R.sub.3, and R.sub.4 is a
radical that is selected from the group consisting of the following
Formulae 1a, 1b, and 1c and the remains are each independently
selected from the group consisting of hydrogen; halogen;
substituted or unsubstituted C1-C20 alkyl; substituted or
unsubstituted C2-C20 alkenyl; substituted or un-substituted C5-C12
cycloalkyl; substituted or unsubstituted C6-C40 aryl; substituted
or unsubstituted C7-C15 aralkyl; substituted or unsubstituted
C2-C20 alkynyl; and a non-hydrocarbonaceous polar group that
includes one or more elements selected from the group consisting of
oxygen, nitrogen, phosphorus, sulfur, silicon, and boron,
[0027] if R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are not hydrogen,
halogen, or a polar functional group, R.sub.1 and R.sub.2 or
R.sub.3 and R.sub.4 may be bonded to each other to form a C1-C10
alkylidene group, or R.sub.1 or R.sub.2 may be bonded to any one of
R.sub.3 and R.sub.4 to form a saturated or unsaturated C4-C12 ring
or an aromatic ring having 6 to 24 carbon atoms,
[0028] specific examples of the non-hydrocarbonaceous polar group
include, but are not limited to --OR.sub.6, --R.sub.5OR.sub.6,
--OC(O)OR.sub.6, --R.sub.5OC(O)OR.sub.6, --C(O)OR.sub.6,
--R.sub.5C(O)OR.sub.6, --C(O)R.sub.6, --R.sub.5C(O)R.sub.6,
--OC(O)R.sub.6, --R.sub.5OC(O)R.sub.6,
--(R.sub.5O).sub.p--OR.sub.6, (p is an integer in the range of 1 to
10), --(OR.sub.5).sub.p--OR.sub.6 (p is an integer in the range of
1 to 10), --C(O)--O--C(O)R.sub.6, --R.sub.5C(O)--O--C(O)R.sub.6,
--SR.sub.6, --R.sub.5SR.sub.6, --SSR.sub.6, --R.sub.5SSR.sub.6,
--S(.dbd.O)R.sub.6, --R.sub.5S(.dbd.O)R.sub.6,
--R.sub.5C(.dbd.S)R.sub.6, --R.sub.5C(.dbd.S)SR.sub.6,
--R.sub.5SO.sub.3R.sub.6, --SO.sub.3R.sub.6,
--R.sub.5N.dbd.C.dbd.S, --N.dbd.C.dbd.S, --NCO, --R.sub.5--NCO,
--CN, --R.sub.5CN, --NNC(.dbd.S)R.sub.6,
--R.sub.5NNC(.dbd.S)R.sub.6, --NO.sub.2, --R.sub.5NO.sub.2,
##STR00002## ##STR00003## ##STR00004##
[0029] R.sub.5 of each of the functional groups is substituted or
unsubstituted C1-C20 alkylene; substituted or unsubstituted C2-C20
alkenylene; substituted or unsubstituted C5-C12 cycloalkylene;
substituted or unsubstituted C6-C40 arylene; substituted or
unsubstituted C7-C15 aralkylene; or substituted or unsubstituted
C2-C20 alkynylene, and
[0030] R.sub.6, R.sub.7 and R.sub.8 are each independently
hydrogen; halogen; substituted or unsubstituted C1-C20 alkyl;
substituted or unsubstituted C2-C20 alkenyl; substituted or
unsubstituted C5-C12 cycloalkyl; substituted or unsubstituted
C6-C40 aryl; substituted or unsubstituted C7-C15 aralkyl; or
substituted or unsubstituted C2-C20 alkynyl,
##STR00005##
[0031] in Formulae 1a, 1b, and 1c,
[0032] A is substituted or unsubstituted C1-C20 alkylene, carbonyl,
carboxy, substituted or unsubstituted C6-C40 arylene, or a simple
bond;
[0033] B is oxygen, sulfur, --NH--, or a simple bond;
[0034] X is oxygen or sulfur;
[0035] R.sub.9 is a simple bond, substituted or unsubstituted
C1-C20 alkylene; substituted or unsubstituted C2-C20 alkenylene;
substituted or unsubstituted C5-C12 cycloalkylene; substituted or
unsubstituted C6-C40 arylene; substituted or unsubstituted C7-C15
aralkylene; or substituted or unsubstituted C2-C20 alkynylene;
[0036] R.sub.10, R.sub.11, R.sub.12, and R.sub.13 are each
independently selected from the group consisting of substituted or
unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20
alkoxy, substituted or unsubstituted C6-C30 aryloxy, and
substituted or unsubstituted C6-C40 aryl; and
[0037] C is C6-C40 aryl; or C6-C40 hetero aryl that includes Group
14, 15 or 16 hetero elements (S, O, N or the like), and the aryl or
hetero aryl is substituted with substituted or unsubstituted C1-C20
alkoxy or substituted or unsubstituted C6-C30 aryloxy.
Representative examples of C include, but are not limited to,
compounds that are represented by the following Formula 2.
##STR00006## ##STR00007##
[0038] In Formulae 1c and 2, at least one of R'.sub.10, R'.sub.11,
R'.sub.12, R'.sub.13, R'.sub.14, R'.sub.15, R'.sub.16, R'.sub.17,
and R'.sub.18 is necessarily substituted or unsubstituted C1-C20
alkoxy or substituted or unsubstituted C6-C30 aryloxy, and the
remains are each independently hydrogen, substituted or
unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20
alkoxy, substituted or unsubstituted C6-C30 aryloxy, or substituted
or unsubstituted C6-C40 aryl.
[0039] In the present invention, an experiment in which a polarizer
is disposed in front of a UV lamp to directly radiate the polarized
UV to the alignment film is performed. In respects to the spectrum
of the polarized UV, the intensity of light is significantly
reduced at 300 nm or less, and the peak at around 365 nm is highest
among the peaks that are most close to ultraviolet rays. Meanwhile,
the UV absorption of the polymers that are aryl or heteroaryl in
which C is substituted with the alkoxy group or the aryloxy group
is red-shifted as compared to the polymers that are aryl in which C
is substituted with hydrogen or the alkyl group. Accordingly, it is
expected that the photoreaction rapidly occurs in the case of the
polymers having the absorption spectrum that is close to the
highest peak of UV in comparison with the cases of the other
polymers.
[0040] In addition, the polymers that are aryl or heteroaryl in
which C is substituted with the alkoxy group or the aryloxy group
have increased compatibility in respects to the liquid crystals,
thus directly affecting the alignment of the liquid crystals and
significantly affecting the quality of the liquid crystal
retardation film finally obtained.
[0041] The photoreactive ring-opened hydrogenated polymer that
includes the multi-cyclic compound according to the present
invention as the monomer in the main chain may include a repeating
unit that is represented by the following Formula 3.
##STR00008##
[0042] In Formula 3,
[0043] n is in the range of 50 to 5,000, and
[0044] P, R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are the same as
those defined in the above.
[0045] In addition, the ring-opened hydrogenated polymer that
includes the multi-cyclic compound according to the present
invention as a monomer may further include one or more of the
multi-cycle compounds that are represented by the following Formula
4 as the monomer:
##STR00009##
[0046] In Formula 4,
[0047] P' is an integer in the range of 0 to 4,
[0048] R'.sub.1, R'.sub.2, R'.sub.3, and R'.sub.4 are each
independently selected from the group consisting of hydrogen;
halogen; substituted or unsubstituted C1-C20 alkyl, substituted or
unsubstituted C2-C20 alkenyl; substituted or unsubstituted C5-C12
cycloalkyl; substituted or unsubstituted C6-C40 aryl; substituted
or unsubstituted C7-C15 aralkyl; substituted or unsubstituted
C2-C20 alkynyl; and a non-hydrocarbonaceous polar group that
includes one or more elements selected from the group consisting of
oxygen, nitrogen, phosphorus, sulfur, silicon, and boron,
[0049] if R'.sub.1, R'.sub.2, R'.sub.3, and R'.sub.4 are not
hydrogen, halogen, or a polar functional group, R'.sub.1 and
R'.sub.2, or R'.sub.3 and R'.sub.4 may be bonded to each other to
form a C1-C10 alkylidene group, or R'.sub.1 or R'.sub.2 may be
bonded to any one of R'.sub.3 and R'.sub.4 to form a saturated or
unsaturated C4-C12 ring or an aromatic ring having 6 to 24 carbon
atoms,
[0050] specific examples of the non-hydrocarbonaceous polar group
include, but are not limited to --OR.sub.6, --R.sub.5OR.sub.6,
--OC(O)OR.sub.6, --R.sub.5OC(O)OR.sub.6, --C(O)OR.sub.6,
--R.sub.5C(O)OR.sub.6, --C(O)R.sub.6, --R.sub.5C(O)R.sub.6,
--OC(O)R.sub.6, --R.sub.5OC(O)R.sub.6, --(R.sub.5O).sub.pOR.sub.6
(p is an integer in the range of 1 to 10),
--(OR.sub.5).sub.p--OR.sub.6 (p is an integer in the range of 1 to
10), --C(O)--O--C(O)R.sub.6, --R.sub.5C(O)--O--C(O)R.sub.6,
--SR.sub.6, --R.sub.5SR.sub.6, --SSR.sub.6, --R.sub.5SSR.sub.6,
--S(.dbd.O)R.sub.6, --R.sub.5S(.dbd.O)R.sub.6,
--R.sub.5C(.dbd.S)R.sub.6, --R.sub.5C(.dbd.S)SR.sub.6,
--R.sub.5SO.sub.3R.sub.6, --SO.sub.3R.sub.6,
--R.sub.5N.dbd.C.dbd.S, --N.dbd.C.dbd.S, --NCO, --R.sub.5--NCO,
--CN, --R.sub.5CN, --NNC(.dbd.S)R.sub.6,
--R.sub.5NNC(.dbd.S)R.sub.6, --NO.sub.2, --R.sub.5NO.sub.2,
##STR00010## ##STR00011## ##STR00012##
[0051] R.sub.5 of each of the functional groups is substituted or
unsubstituted C1-C20 alkylene; substituted or unsubstituted C2-C20
alkenylene; substituted or unsubstituted C5-C12 cycloalkylene;
substituted or unsubstituted C6-C40 arylene; substituted or
unsubstituted C7-C15 aralkylene; or substituted or unsubstituted
C2-C20 alkynylene, and
[0052] R.sub.6, R.sub.7 and R.sub.8 are each hydrogen; halogen;
substituted or unsubstituted C1-C20 alkyl; substituted or
unsubstituted C2-C20 alkenyl; substituted or unsubstituted C5-C12
cycloalkyl; substituted or unsubstituted C6-C40 aryl; substituted
or unsubstituted C7-C15 aralkyl; or substituted or unsubstituted
C2-C20 alkynyl.
[0053] The definition of the above-mentioned substituent groups
will be described in detail.
[0054] The term "alkyl" means a straight- or branched-chained
saturated monovalent hydrocarbon portion having 1 to 20 carbon
atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6
carbon atoms. The alkyl group may be arbitrarily substituted with
one or more halogen substituents. Examples of the alkyl group
include methyl, ethyl, propyl, 2-propyl, n-butyl, iso-butyl,
tert-butyl, pentyl, hexyl, dodecyl, fluoromethyl, difluoromethyl,
trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl,
iodomethyl, bromomethyl and the like.
[0055] The term "alkenyl" means a straight- or branched-chained
monovalent hydrocarbon portion having 2 to 20 carbon atoms,
preferably 2 to 10 carbon atoms, and more preferably 2 to 6 carbon
atoms having one or more carbon-carbon double bonds. The alkenyl
group may be bonded through the carbon atoms having the
carbon-carbon double bonds or the saturated carbon atoms. The
alkenyl group may be arbitrarily substituted with one or more
halogen substituents. Examples of the alkenyl group may include
ethenyl, 1-propenyl, 2-propenyl, 2-butenyl, 3-butenyl, pentenyl,
5-hexenyl, dodecenyl and the like.
[0056] The term "cycloalkyl" means a saturated or unsaturated
nonaromatic monovalent monocyclic, bicyclic or tricyclic
hydrocarbon portion having 5 to 12 cyclic carbons, and may be
arbitrarily substituted with one or more halogen substituents.
Examples of the cycloalkyl may include cyclopropyl, cyclobutyl,
cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl,
cyclooctyl, decahydronaphthalenyl, adamantyl, norbornyl (that is,
bicyclo[2.2.1]hept-5-enyl) or the like.
[0057] The term "aryl" means a monovalent monocyclic bicyclic or
tricyclic aromatic hydrocarbon portion having 6 to 20 ring atoms,
and preferably 6 to 12 ring atoms, and may be arbitrarily
substituted with one or more halogen substituents and the like. The
aromatic portion of the aryl group includes only a carbon atom.
Examples of the aryl group may include phenyl, naphthalenyl,
fluorenyl and the like.
[0058] The term "alkoxyaryl" means one or more hydrogen atoms of
the aryl group defined as described above, which are substituted
with the alkoxy group. Examples of the alkoxyaryl group may include
methoxyphenyl, ethoxyphenyl, propoxyphenyl, butoxyphenyl,
pentoxyphenyl, hetoxy phenyl, heptoxy phenyl, octoxyphenyl,
nanoxyphenyl, methoxybiphenyl, ethoxybiphenyl, propoxybiphenyl,
methoxy-naphthalenyl, ethoxynaphthalenyl, propoxynaphthalenyl,
methoxyanthracenyl, ethoxyanthracenyl, propoxyanthracenyl,
methoxyfluorenyl and the like.
[0059] The term "araryl" means one or more hydrogen atoms of the
alkyl group defined as described above, which are substituted with
the aryl group. The aralkyl may be arbitrarily substituted with one
or more halogen substituents. Examples of the aralkyl may include
benzyl, benzhydril, tritile and the like.
[0060] The term "alkynyl" means a straight- or branched-chained
monovalent hydrocarbon portion having 2 to 20 carbon atoms,
preferably 2 to 10 carbon atoms, more preferably 2 to 6 carbon
atoms having one or more carbon-carbon triple bonds. The alkynyl
group may be bonded through the carbon atoms having the
carbon-carbon triple bonds or the saturated carbon atoms. The
alkynyl group may be arbitrarily substituted with one or more
halogen substituents. Examples of the alkynyl group may include
ethynyl, propynyl and the like.
[0061] The term "alkylene" means a straight- or branched-chained
divalent saturated hydrocarbon portion having 1 to 20 carbon atoms,
preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon
atoms. The alkylene group may be arbitrarily substituted with one
or more halogen substituents. Examples of the alkyl group may
include methylene, ethylene, propylene, butylene, hexylene and the
like.
[0062] The term "alkenylene" means a straight- or branched-chained
divalent hydrocarbon portion having 2 to 20 carbon atoms,
preferably 2 to 10 carbon atoms, more preferably 2 to 6 carbon
atoms having one or more carbon-carbon double bonds. The alkenylene
group may be bonded through the carbon atoms having the
carbon-carbon double bonds and/or the saturated carbon atoms. The
alkenylene group may be arbitrarily substituted with one or more
halogen substituents.
[0063] The term "cycloalkylene" means a saturated or unsaturated
nonaromatic divalent monocyclic, bicyclic or tricyclic hydrocarbon
portion having 5 to 12 cyclic carbons, and may be arbitrarily
substituted with one or more halogen substituents. Examples of the
cycloalkylene may include cyclopropylene, cyclobutylene and the
like.
[0064] The term "arylene" means a divalent monocyclic, bicyclic or
tricyclic aromatic hydrocarbon portion having 6 to 20 cyclic atoms
and preferably 6 to 12 cyclic atoms, and may be arbitrarily
substituted with one or more halogen substituents. The aromatic
portion of the aryl group includes only the carbon atoms. Examples
of the arylene group may include phenylene and the like.
[0065] The term "aralkylene" means a divalent portion in which one
or more hydrogen atoms of the alkyl group defined as described
above are substituted with the aryl group, and may be arbitrarily
substituted with one or more halogen substituents. Examples of the
aralkylene may include benzylene and the like.
[0066] The term "alkynylene" means a straight- or branched-chained
divalent hydrocarbon portion having 2 to 20 carbon atoms,
preferably 2 to 10 carbon atoms, more preferably 2 to 6 carbon
atoms having one or more carbon-carbon triple bonds. The alkynylene
group may be bonded through the carbon atoms having the
carbon-carbon triple bonds or the saturated carbon atoms. The
alkynylene group may be arbitrarily substituted with one or more
halogen substituents. Examples of the alkynylene group may include
ethynylene, propynylene and the like.
[0067] The term "bond" means a bonding portion while no substituent
group is inserted.
[0068] In respects to the multi-cyclic compound ring-opened
hydrogenated polymer that includes the photoactive functional
group, linear alkene such as 1-alkene, 2-alkene and the like, which
is capable of controlling a size of a molecular weight, is added in
an amount of 1 to 100 mol % based on the monomer in the presence of
a catalyst mixture that consists of a procatalyst including Group 4
(for example, Ti, Zr, HO, Group 6 (for example, Mo, W), and Group 8
(for example, Ru, Os) transition metal, a ccratalyst that provides
a Lewis base capable of being weakly coordinate bonded to the metal
of the procatalyst, and neutral Group 15 and Group 16 activators
that selectively improve the activity of the procatalyst metal, the
polymerization is performed at a temperature in the range of 10 to
200.degree. C. After that, a catalyst that includes Group 4 (for
example, Ti, Zr) or Group 8 to Group 10 (for example, Ru, Ni, Pd)
transition metals is added in an amount of 1 to 30% by weight based
on the monomer to add hydrogen to the double bond remaining on the
main chain at the temperature in the range of 10 to 253.degree.
C.
[0069] In the case of when the reaction temperature is lower than
10.degree. C., there is a problem in that the polymerization
activity is very low. In the case of when the reaction temperature
is higher than 200.degree. C., the catalyst may be decomposed,
which is undesirable. In the case of when the hydrogenation
reaction temperature is lower than 10.degree. C., there is a
problem in that the activity of the hydrogenation reaction is very
low. In the case of when the hydrogenation reaction temperature is
higher than 250.degree. C., the catalyst may be decomposed, which
is undesirable.
[0070] The catalyst mixture includes 1 to 100,000 mole of the
cocatalyst that provides a Lewis base capable of being weakly
coordinate bonded to the metal of the procatalyst based on 1 mole
of the procatalyst that includes Group 4 (for example, Ti, Zr, Hf),
Group 6 (for example, Mo, W), and Group 8 (for example, Ru, Os)
transition metals, and selectively 1 to 100 mole of the activator
that includes neutral Group 15 and Group 16 elements improving the
activity of the procatalyst metal based on 1 mole of the
procatalyst.
[0071] In the case of when the content of the cocatalyst is less
than 1 mole, there is a problem in that the activation of the
catalyst is not ensured. In the case of when the content of the
cocatalyst is more than 100,000 mole, the activity of the catalyst
is reduced, which is undesirable. The activator may not be used
according to the type of the procatalyst. In the case of when the
content of activator is less than 1 mole, there is a problem in
that the activation of the catalyst is not ensured. In the case of
when the content of the activator is more than 100 mole, the
molecular weight is reduced, which is undesirable.
[0072] In the case of when the content of the catalyst that
includes the Group 4 (for example, Ti, Zr) or Groups 8 to 10 (for
example, Ru, Ni, Pd) transition metals which are used during the
hydrogenation reaction is less than 1% by weight based on the
monomer, there is a problem in that the hydrogenation is not
desirably performed. In the case of when the content of the
catalyst is more than 30% by weight, the polymer may be discolored,
which is undesirable.
[0073] The procatalyst that includes the Group 4 (for example, Ti,
Zr, Hf), Group 6 (for example, Mo, W), and Group 8 (for example,
Ru, Os) transition metals means a transition metal such as
TiCl.sub.4, WCl.sub.6, MoCl.sub.6, or RuCl.sub.3 having the
functional group that easily participates in the Lewis acid-base
reaction to be separated from the central metal while the metal is
easily separated by the cocatalyst providing the Lewis acid so that
the central transition metal is converted into the catalyst active
species.
[0074] In addition, the a catalyst providing the Lewis base that is
capable of being weakly coordination bonded to the metal of the
procatalyst may use borane or borate such as B(C.sub.6
F.sub.5).sub.3, methyl aluminoxane (MAO), or alkylaluminum,
alkylaluminum halide, or aluminum halide such as
Al(C.sub.2H.sub.5).sub.3 and Al(CH.sub.3)Cl.sub.2. Instead of
aluminum, a substituent such as lithium, magnesium, germanium,
lead, zinc, tin, silicon and the like may be used. The cocatalyst
easily reacts with the Lewis base to form a vacancy of the
transition metal, and provides a compound that is weakly
coordination bonded to the transition metal compound or a compound
providing the same in order to stabilize the generated transition
metal.
[0075] The activator for polymerization may be added, but may not
be used according to the type of the procatalyst. Examples of the
activator that includes the neutral Group 15 and Group 16 elements
capable of improving the activity of the procatalyst metal include
water, methanol, ethanol, isopropyl alcohol, benzyl alcohol,
phenol, ethyl mercaptan, 2-chloroethanol, trimethylamine,
triethylamine, pyridine, ethylene oxide, benzoyl peroxide, t-butyl
peroxide and the like.
[0076] The catalyst that includes the Group 4 (for example, Ti, Zr)
or Groups 8 to 10 (for example, Ru, Ni, Pd) transition metals used
during the hydrogenation reaction may be present in a homogeneous
form that can be immediately mixed with a solvent or a substance in
which the metal catalyst complex compound is carried in a fine
supporting material. Preferable examples of the fine supporting
material include silica, titania, silica/chromia,
silica/chromia/titania, the silica/alumina, an aluminum phosphate
gel, silanized silica, silica hydrogel, montmorilonite clay, and
zeolite.
[0077] According to an embodiment of the present invention, the
catalyst mixture that consists of a procatalyst including Group 4,
Group 6, and Group 8 transition metals, a cocatalyst that provides
a Lewis base capable of being weakly coordinate bonded to the metal
of the procatalyst, and neutral Group 15 and Group 16 activators
that selectively improve the activity of the procatalyst metal is
prepared. Additionally, linear alkene may be further added to
control the size of the molecular weight. Next, the monomer
solution that includes the multi-cyclic compound having the
photoactive functional group is subjected to the ring-opened
polymerization in the presence of the organic solvent and the
catalyst mixture and then subjected to the hydrogenation reaction.
However, the order of the addition of the catalyst, the monomer,
and the solvent is not limited.
[0078] A photoreactive polymer awarding to another embodiment of
the present invention is a cycloolefin-noncycloolefin polymer that
includes a repeating unit represented by the following Formula
5.
##STR00013##
[0079] In Formula 5,
[0080] n is the degree of polymerization in the range of 50 to
5000,
[0081] the content of the repeating unit of cycloolefin that is
represented by x is in the range of 0.1 to 99.9 mol %,
[0082] the content of the repeating unit of linear olefin that is
represented by y is in the range of 0.1 to 99.9 mol %,
[0083] the content of the repeating unit of cycloolefin that is
represented by z is in the range of 0.1 to 99.9 mol %,
[0084] the order of the repeatition of noncycloolefin and
cycloolefin is random,
[0085] P, R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are the same as
those defined in Formula 1,
[0086] Ra is a hydrogen atom or a C1-C20 hydrocarbon group, and
[0087] P', R.sub.1', R.sub.2', R.sub.3', and R.sub.4' are the same
as those defined in Formula 4.
[0088] The "hydrocarbon group in Ra" includes alkyl, cycloalkyl,
alkylene, and cycloalkylene as defined above, for example,
.alpha.-olefin, butadiene, and pentadiene, and definitions of the
other substituent groups are the same as those of the case of the
photoreactive ring-opened hydrogenated polymer.
[0089] Hereinafter, a method of preparing the polymer that is used
to form the alignment film will be described.
[0090] The cycloolefin-noncycloolefin polymer that includes the
photoactive functional group is prepared by performing the
polymerization in the presence of a catalyst mixture that consists
of a procatalyst including the metallocene catalyst and a
cocatalyst including aluminoxane at a temperature in the range of
10 to 200.degree. C. under polymerization pressure in the range of
1 to 60 bar.
[0091] In the case of when the reaction temperature is less than
10.degree. C., there is a problem in that the polymerization
activity is very low. In the case of when the reaction temperature
is higher than 200.degree. C., the catalyst may be decomposed,
which is undesirable.
[0092] Preferable examples of the procatalyst include the
metallocene catalyst. Examples of the metallocene catalyst include
a metallocene catalyst such as
rac-ethylene-bis-(1-indenyl)-zirconiumdichloride,
isopropylene-(9-fluorenyl)-cyclopentadienyl-zirconiumdichloride,
rac-dimethylsilyl-bis-(1-indenyl)-zirconium dichloride,
phenylmethyl-(9-fluorenyl)-cyclopentadienyl zirconium dichloride,
rac-dimethylgermyl-bis-(1-indenyl)-zirconium dichloride,
rac-phenyl-methylsilyl-bis-(1-indenyl)-zirconium dichloride, and
rac-phenylvinylsilyl-bis-(1-indenyl)-zirconium dichloride.
[0093] In addition, preferable examples of the cocatalyst include
aluminoxane, and examples of aluminoxane include methyl
aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, butyl
aluminoxane and the like.
[0094] In general, the transition metal compound (catalyst and
cocatalyst) is previously activated in a solution. The
concentration of aluminoxane that is present in a solution state is
generally in the range of 1 wt % to the saturation concentration.
Metallocene may be used at the same concentration, but it is
preferable to use 10.sup.-4 to 10.sup.-2 mol of metallocene based
on 1 mole of aluminoxane. The previous activation time is
preferably in the range of 15 to 60 min, and at this time, the
temperature is in the range of 15 to 70.degree. C. In addition, it
is preferable that the metallocene compound be generally used in an
amount of 10.sup.-4 to 10.sup.-6 mole per 1 L of the volume of the
reactor based on the transition metal. It is preferable that
aluminoxane be used in an amount of 10.sup.-4 mole per 1 L of the
volume of the reactor based on the aluminum (Al). The incorporation
ratio of the monomers depends on the polymerization conditions such
as the reaction temperature, the reaction pressure, the
concentration of the catalyst, the concentration of the cocatalyst
and the like. It is preferable that the incorporation ratio of the
cyclic monomer be in the range of 10 to 80 mol %.
[0095] The photoreactive polymer according to the present invention
may be used to prepare an alignment film for liquid crystal display
devices by applying the solution of the monomer on a substrate
having a transparent electrode, removing a solvent to form a film,
and radiating ultraviolet rays polarized in a predetermined
direction thereon to provide an anisotropic property on the surface
of the film.
MODE FOR THE INVENTION
[0096] A better understanding of the present invention may be
obtained in light of the following Examples which are set forth to
illustrate, but are not to be construed to limit the present
invention.
[0097] In addition, in the following Examples, all the operations
in which the compounds that were sensitive to air or water were
treated were performed by using the standard Schlenk technique or
the dry box technique. The nuclear magnetic resonance (NMR)
spectrum was obtained by using the Bruker 300 spectrometer. In
connection with this, the .sup.1H NMR was measured at 300 MHz and
the .sup.13C NMR was measured at 75 MHz. The molecular weight and
the molecular weight distribution of the ring-opened hydrogenated
polymer were measured by using the GPC (gel permeation
chromatography). In connection with this, the polystyrene sample
was used as the standard sample.
[0098] Toluene was subjected to the distillation in
potassium/benzophenone to be purified, and dichloromethane was
subjected to the purification in CaH.sub.2 by the distillation.
<Preparing of the Photoreactive Ring-Opened Hydrogenated Polymer
Including the Multi-Cyclic Compound>
Example 1
Synthesis of 5-norbornene-2-methyl-4'-methoxy cinnamate ring-opened
hydrogenated polymer
(1) Synthesis of 5-norbornene-2-methanol
[0099] DCPD (dicyclopentadiene, Aldrich, 397 g, 3 mol), and aryl
alcohol (Aldrich, 331 g, 5.7 mol) were put into the high pressure
reactor having the volume of 2 L and then heated to 210.degree. C.
The agitation was performed at 300 rpm to conduct the reaction for
1 hour. When the reaction was finished, the reactant was cooled and
then moved to the distillation device. The distillation was
performed twice under reduced pressure of 1 torr by using the
vacuum pump to obtain the product at 56.degree. C. (yield:
52%).
[0100] 1H-NMR (300 MHz, CDCl3): .delta.6.17.about.5.91 (m, 2H),
3.71.about.3.19 (m, 2H), 2.91.about.2.75 (m, 2H), 2.38 (m, 1H),
1.83 (m, 1H), 1.60.about.1.12 (m, 2H), 0.52 (m, 1H)
(2) The Ring Opening Metathesis Polymerization and the
Hydrogenation Reaction of 5-norbornene-2-methanol
[0101] 6.20 g 150 mmol) of 5-norbornene-2-methanol that was
synthesized in (1) was punt into the Schlenk flask having the
volume of 250 ml under an Ar atmosphere, and 34 g of toluene that
was purified by using the solvent was added thereto. 11.4 mg (1.0
mmol) of triethyl aluminum (TEA) that was the cocatalyst was first
added thereto while the flask was maintained at the polymerization
temperature of 80.degree. C. Subsequently, 1 ml of the 0.01 M
(mol/L) toluene solution (WCl.sub.6 0.01 mmol, ethanol 0.03 mmol)
in which tungsten hexachloride (WCl.sub.6) and ethanol were mixed
with each other at a ratio in the range of 1:3 was added to the
flask. Finally, 0.84 g of 1-octene (7.5 mmol) that was the
molecular weight controlling agent was added to the flask and then
reacted at 80.degree. C. for 18 hours while the agitation was
performed. After the reaction was finished, ethyl vinyl ether that
was the polymerization terminator was dropped on the polymerization
solution in a small amount and the agitation was then performed for
5 minutes.
[0102] The polymerization solution was transported to the high
pressure reactor having the volume of 300 mL, and 0.06 ml of
triethyl aluminum (TEA) was added thereto. Subsequently, 0.50 g of
grace raney Nickel (slurry phase in water) was added thereto, and
the reaction was performed while the pressure of hydrogen was
maintained at 80 atm and the agitation was performed at 150.degree.
C. for 2 hours. After the reaction was finished, the polymerization
solution was dropped on acetone to perform the precipitation, and
the precipitate was filtered and then dried in a vacuum oven at
70.degree. C. for 15 hours to obtain 5.62 g of ring-opened
hydrogenated polymer of 5-norbornene-2-methanol (yield=90.6%,
Mw=69,900, Mw/Mn=4.92).
(3) Synthesis of 4-methoxy cinnamoyl chloride
[0103] 25 g of the 4-methoxy benzoic acid) (166.5 mmol) and 69.35 g
of SOCl.sub.2 082.8 mmol) were put into the round-bottomed flask
having the volume of 250 ml, and then agitated at normal
temperature for 18 hours. After the reaction was finished, the
reduced pressure was applied to remove an excessive amount of
SOCl.sub.2, and the reactant was diluted with 150 ml of toluene and
neutralized by using the NaHCO.sub.3 solution (100 ml.times.3).
Water was removed from the neutralized toluene solution by using
MgSO4 and the solvent was removed under reduced pressure to obtain
31.1 g of 4-methoxy cinnamoyl chloride that was the white solid
(yield=95%).
(4) Synthesis of 5-norbornene-2-methyl-4'-methoxy cinnamate
Ring-Opened Hydrogenated Polymer
[0104] The ring-opened hydrogen additional polymer (15 g, 0.121
mol) of 5-norbornene-2-methanol that was synthesized in (2),
triethylamine (Aldrich, 61.2 g, 0.605 mol), 50 ml of THF were put
into the 2-neck flask having the volume of 250 ml, and then
agitated in the 0.degree. C. ice-water bath. 4-methoxy cinnamoyl
chloride (22.1 g, 0.133 mol) that was synthesized in (3) was
dissolved in 60 ml of THF, and slowly added by using the additional
flask. After 10 minutes, the temperature of the reactant was
increased to normal temperature and the additional agitation was
performed for 18 hours. The solution was diluted with ethyl
acetate, transported to the separatory funnel, and washed several
times by using water and NaHCO.sub.3. The reaction solution was
dropped in acetone to perform the precipitation, and the
precipitate was filtered and then dried in a vacuum oven at
70.degree. C. for 15 hours (yield: 94%).
Example 2
Synthesis of the 5-norbornene-2-(4'-hydroxy-4-methoxychalcone)ester
Ring-Opened Hydrogenated Polymer
(1) Synthesis of the Ring-Opened Hydrogenated Polymer of the
5-norbornene-2-carboxylic Acid
[0105] 11.0 g (79.64 mmol) of the 5-norbornene-2-carboxylic acid
was put into the Schlenk flask having the volume of 250 ml under an
Ar atmosphere, and 55 g of toluene that was purified by using the
solvent was added thereto. 18.2 mg (1.6 mmol) of triethyl aluminum
(TEA) that was the cocatalyst was first added thereto while the
flask was maintained at the polymerization temperature of
80.degree. C. Subsequently, 1.6 ml of the 0.01 M (mol/L) toluene
solution (WCl.sub.6 0.016 mmol, ethanol 0.048 mmol) in which
tungsten hexachloride (WCl.sub.6) and ethanol were mixed with each
other at a ratio in the range of 1:3 was added to the flask.
Finally, 1.34 g of 1-octene (11.95 mmol) that was the molecular
weight controlling agent was added to the flask and then reacted at
80.degree. C. for 18 hours while the agitation was performed. After
the reaction was finished, ethyl vinyl ether that was the
polymerization terminator was dropped on the polymerization
solution in a small amount and the agitation was then performed for
5 minutes.
[0106] The polymerization solution was transported to the high
pressure reactor having the volume of 300 mL, and 0.38 ml of
triethyl aluminum (TEA) was added thereto. Subsequently, 3.20 g of
grace raney Nickel (slurry phase in water) was added thereto, and
the reaction was performed while the pressure of hydrogen was
maintained at 80 atm and the agitation was performed at 150.degree.
C. for 2 hours. After the reaction was finished, the polymerization
solution was dropped on acetone to perform the precipitation, and
the precipitate was filtered and then dried in a vacuum oven at
70.degree. C. for 15 hours to obtain 10.1 g of ring-opened
hydrogenated polymer of 5-norbornene-2-carboxylic acid (yield=92%,
Mw=71,500, Mw/Mn=4.51).
(2) Synthesis of the
5-norbornene-2-(4'-hydroxy-4-methoxychalcone)ester Ring-Opened
Hydrogenated Polymer
[0107] 10.1 g of the ring-opened hydrogenated polymer of the
5-norbornene-2-carboxylic acid that was synthesized in (1) (71.55
mmol), 16.52 g of 4'-hydroxy-4-methoxychalcone) (65.0 mmol), 19.9 g
of EDC (N-ethyl-N'-(3-dimethylaminopropyl)carbodiimide
hydrochloride) (Aldrich, 104.2 mmol), and 13.2 g of HOBT
(1-Hydroxybenzotriazole hydrate) (Aldrich, 97.52 mmol) were
sequentially put into the two-neck flask having the volume of 250
ml, and then dissolved in 100 ml of DMF. After the temperature was
reduced to 0.degree. C., triethylamine (Aldrich, 45 ml, 325 mmol)
was slowly dropped. After the temperature was increased to normal
temperature and maintained overnight. When the reaction was
finished, the extraction was performed by using a great amount of
ethyl acetate. The resulting substance was washed by using
NaHCO.sub.3 and H.sub.2O, the reaction solution was dropped on
acetone to perform the precipitation, and the precipitate was
filtered and then dried in a vacuum oven at 70.degree. C. for 15
hours to obtain 9.4 g of ring-opened hydrogenated polymer of
5-norbornene-2-(4'-hydroxy-4-methoxychalcone) ester
(yield=93%).
Example 3
Synthesis of the 5-norbornene-2-(7-hydroxy-6-methoxy
coumarine)ester Ring-Opened Hydrogenated Polymer
[0108] 10.1 g of the ring-opened hydrogenated polymer of the
5-norbornene-2-carboxylic acid that was synthesized in (1) of
Example 2 (71.55 mmol), 12.49 g of 7-hydroxy-6-methoxycoumarin
(Aldrich, 65.0 mmol), 19.9 g of EDC
(N-ethyl-N'-(3-dimethylaminopropyl)carbodiimide hydrochloride)
(Aldrich, 104.2 mmol), and 13.2 g of HOBT (1-Hydroxybenzotriazole
hydrate) (Aldrich, 97.52 mmol) were sequentially put into the
two-neck flask having the volume of 250 ml, and then dissolved in
100 ml of DMF. After the temperature was reduced to 0.degree. C.,
triethylamine (Aldrich, 45 ml, 325 mmol) was slowly dropped. After
the temperature was increased to normal temperature and maintained
overnight. When the reaction was finished, the extraction was
performed by using a great amount of ethyl acetate. The resulting
substance was washed by using NaHCO.sub.3 and H.sub.2O, the
reaction solution was dropped on acetone to perform the
precipitation, and the precipitate was filtered and then dried in a
vacuum oven at 70.degree. C. for 15 hours to obtain 9.4 g of
ring-opened hydrogenated polymer of
5-norbornene-2-(7-hydroxy-6-methoxy coumarine)ester
(yield=93%).
Example 4
Synthesis of the Ring-Opened Hydrogenated Polymer to which the
4-propoxy cinnamoyl Group was Introduced
(1) The Ring-Opened Polymerization and the Hydrogenation Reaction
of METCD
[0109] 13.2 g of 8-methoxy-carbonyl
tetracyclo[4,4,0,12,5,17,10]dode-3-cene (METCD) (0.1 mol) as the
monomer, 1.1 g of 1-octene (10 mmol), and 10 ml of toluene that was
purified by using the solvent were put into the schlenk flask
having the volume of 253 ml. 0.02 mmol of WCl.sub.6 that was
dissolved in 1 ml of toluene and 0.14 mmol of triethylaluminum were
put into the flask as the catalyst, and the reaction was performed
while the agitation was performed at 80.degree. C. for 18 hours.
After the reaction was performed for 18 hours, the reactant was
added to an excessive amount of acetone to obtain a ring-opened
polymer precipitate. The ring-opened polymer that was obtained by
filtering the precipitate using the glass funnel was dried in a
vacuum oven at 70.degree. C. for 24 hours to obtain 11.8 g of the
METCD ring-opened polymer (yield: 90%).
[0110] 15 g of the synthesized METCD ring-opened polymer, and 150
ml of toluene as the solvent were added to the high pressure
reactor having the volume of 300 ml. 70 ppm of
[RuHCl(CO)(PCy.sub.3).sub.3] was added as the catalyst to the
reactor, the hydrogen pressure of 10 Mpa was applied, and the
agitation was performed at 165.degree. C. for 4 hours to perform
the hydrogenation reaction. After the reaction was finished, the
hydrogen pressure was removed, and the reactant was added to an
excessive amount of ethanol to obtain a ring-opened hydrogenated
polymer precipitate. The polymer that was obtained by filtering the
precipitate using the glass funnel was dried in a vacuum oven at
70.degree. C. for 24 hours to obtain the ring-opened hydrogenated
polymer (hydrogenation ratio: 99.7%, Mw=76,800, Mw/Mn=4.38).
(2) The Reduction Reaction of the METCD Ring-Opened Hydrogenated
Polymer
[0111] The METCD ring-opened hydrogenated polymer (22 g, 0.1 mol)
that was synthesized in (1), and 100 ml of THF were put into the
2-neck flask having the volume of 250 ml, and then agitated in the
0.degree. C. ice-water bath. Lithiumaluminum hydride (LiAlH4)
(Aldrich, 4.2 g, 0.11 mol) was dissolved in 10 ml of THF, and
slowly added to the reactant by using the additional flask. After 2
hours, the temperature of the reactant was increased to normal
temperature and the additional agitation was performed for 3 hours.
The reaction solution was precipitated in a large amount of ethanol
to obtain 15.4 g of the ring-opened hydrogenated polymer
(ring-opened hydrogenated polymer of TCD-CH.sub.2OH) in which the
ester functional group of METCD was reduced to alcohol (yield:
70%).
(3) Synthesis of the Ring-Opened Hydrogenated Polymer to which the
4-propoxy Cinnamoyl Group was Introduced (Esterification of the
Ring-Opened Hydrogenated Polymer of TCD-CH.sub.2OH)
[0112] The TCD-CH.sub.2OH ring-opened hydrogenated polymer (2.3 g,
12.1 mmol) that was synthesized in (2), 4-propoxy cinnamic acid
(2.49 g, 12.1 mmol), EDC
[1-(3-dimethylaminopropyl)-3-ethylcarboimide hydrochloride]
(Aldrich, 3.7 g, 19.4 mmol), and HOBT (1-hydroxybenzotriazole
hydrate) (Aldrich, 2.45 g, 18.2 mmol) were put into the 2-neck
flask having the volume of 25) ml, and then dissolved in 100 ml of
DMF. Triethylamine (Aldrich, 75 ml, 0.605 mol) was slowly dropped
on the reaction solution. After the agitation for 3 hours, when the
reaction was finished, the reaction solution was precipitated in a
large amount of acetone to obtain the ring-opened hydrogenated
polymer to which the 4-propoxy cinnamoyl group was introduced
(yield: 97%).
Preparation Example 1
Preparation of the Alignment Film by using the
5-norbornene-2-methyl-4'-methoxy Cinnamate Ring-Opened Hydrogenated
Polymer
[0113] The 5-norbornene-2-methyl-4'-methoxy cinnamate ring-opened
hydrogenated polymer that was synthesized in Example 1 was
dissolved in the c-pentanone solvent in a concentration of 2% by
weight, and applied on the polyethylene terephthalate substrate
(commercial name: SH71, prepared by SKC Co., Ltd. in Korea) having
the thickness of 80 micron by using the roll coating process so
that the thickness of the polyethylene terephthalate substrate was
1000 .ANG. after the drying. Next, the substrate was heated in an
oven at 80.degree. C. for 3 minutes to remove the solvent in the
inside of the coating film and to form the coating film.
[0114] The exposing was performed by using a high pressure mercury
lamp having the intensity of 200 mW/cm.sup.2 as a light source
while polarized UV that was perpendicular to the proceeding
direction of the film was radiated on the coating film by using a
Wire-grid polarizer prepared by Moxtek, Co., Ltd. for 5 sec, so
that the alignment was provided to form the alignment film.
[0115] Next, the solid in which 95.0% by weight of cyanobiphenyl
acrylate that was polymerizable by UV and 5.0% by weight of Irgaure
907 (prepared by Ciba-Geigy, Co., Ltd. in Switzerland) as the
photoinitiator were mixed with each other was dissolved in toluene
so that the content of the liquid crystal was 25 parts by weight
based on 100 parts by weight of the liquid crystal solution to
prepare the polymerizable reactive liquid crystal solution.
[0116] The prepared liquid crystal solution was applied on the
photo-alignment film that was formed by using a roll coating
process so that the thickness of the film after the drying was 1
.mu.m, and the drying was performed at 80.degree. C. for 2 minutes
to align the molecules of the liquid crystal. The nonpolarized UV
was radiated on the aligned liquid crystal film by using a
high-pressure mercury lamp having the intensity of 200 mW/cm.sup.2
as a light source to fix the alignment state of the liquid crystal,
thereby preparing the retardation film.
[0117] The alignment properties in respects to the prepared
retardation film were compared to each other by measuring the light
leakage between the polarizing plates by the transmittance, and the
quantitative retardation value was measured by using Axoscan
(prepared by Axomatrix, Co., Ltd.).
Preparation Example 2
Preparation of the Alignment Film by using the
5-norbornene-2-(7-hydroxy-6-methoxy coumarine)ester Ring-Opened
Hydrogenated Polymer
[0118] The retardation film was prepared by using the same method
as Preparation Example 1, except that the 5-norbornene-2-
(7-hydroxy-6-methoxy coumarine)ester ring-opened hydrogenated
polymer prepared in Example 3 was used instead of the polymer
prepared in Example 1.
Preparation Example 3
Preparation of the Alignment Film by using the Ring-Opened
Hydrogenated Polymer to which the 4-propoxy cinnamoyl Group was
Introduced
[0119] The retardation film was prepared by using the same method
as Preparation Example 1, except that the ring-opened hydrogenated
polymer to which the 4-propoxy cinnamoyl group was introduced
prepared in Example 4 was used instead of the polymer prepared in
Example 1.
Comparative Example 1
[0120] The alignment film was prepared by using the same method as
Preparation Example 1, except that the compound of the following
Formula was used instead of the 5-norbornene-2-methyl-4-methoxy
cinnamate ring-opened hydrogenated polymer used in Preparation
Example 1.
##STR00014##
[0121] Cel=cellulose
Comparative Example 2
[0122] The alignment film was prepared by using the same method as
Preparation Example 1, except that the
5-norbornene-2-methyl-cinnamate ring-opened hydrogenated polymer
having no methoxy substituent of the following Formula was used
instead of the 5-norbornene-2-methyl-4-methoxy cinnamate
ring-opened hydrogenated polymer used in Preparation Example 1.
##STR00015##
Experimental Example 1
[0123] Photoreactive Property Evaluation--FT-IR Spectrum
[0124] In order to obtain the photoreactive property of the
alignment film, the FT-IR spectrum of each of the liquid crystal
alignment films that were obtained in Preparation Examples 1 to 3
was observed, and the photoreactive properties were compared to
each other based on the time (t.sub.1/2) required until the
intensity of the stretching mode of the C.dbd.C bond of the
Formulae 1a to 1c of the polymer during the exposure (the mercury
lamp having the intensity of 20 mW/cm.sup.2 was used) was reduced
by half and the energy value (E.sub.1/2=20 mW/cm.sup.2, t.sub.1/2).
The results are described in the following Table 1.
[0125] From the comparison of t.sub.1/2 values, it could be seen
that in the case of Preparation Examples 1 to 3, the time was
reduced by about 1/10 or more as compared to the case of
Comparative Example 1 and thus the liquid crystal alignment film
awarding to the present invention had the desirable photoreactive
rate.
[0126] Table 1
TABLE-US-00001 TABLE 1 T.sub.1/2 (min) E.sub.1/2 (J/cm.sup.2)
Preparation Example 1 0.9 1.1 Preparation Example 2 1.0 1.2
Preparation Example 3 0.8 1.0 Comparative Example 1 9.3 11.2
Experimental Example 2
[0127] Evaluation of the alignment property (evaluation of the
degree of light leakage)
[0128] In order to evaluate the alignment property of the alignment
film, the liquid crystal retardation film that was prepared in
Preparation Example 1 and Comparative Example 2 was observed
between two polarizers that were perpendicular to each other by
using a polarizing microscope, and the transmittance thereof is
shown in FIG. 1. That is, in order to evaluate the transmittance,
based on polyethylene terephthalate having a thickness of 80
microns (trademark: SH71, prepared by SKC, Co., Ltd. in Korea), the
liquid crystal retardation film that was prepared in Preparation
Example 1 and Comparative Example 2 was provided between the
polarizers that were perpendicular to each other and the degree of
transmittance of incident light through the polarizing plate and
the retardation film was checked by using the polarizing microscope
to measure the degree of light leakage, which is shown in FIG. 1.
As shown in FIG. 1, in the retardation film of Preparation Example
1 according to the present invention, the alignment direction of
liquid crystal was uniform regardless of the wavelength of incident
light, but in the case of when the alignment film of Comparative
Example 2 was applied, it could be seen that the alignment strength
was reduced and the alignment direction of liquid crystal was not
uniform.
Preparation of the Photoactive Polymer Including the
Cycloolefin-Noncycloolefin Copolymer Compound>
Example 5
Synthesis of the
5-norbornene-2-methyl-(4-methoxycinnamate)/ethylene copolymer
(1) Protection of 5-norbornene-2-methanol
[0129] 29.75 g of TiBAL (Triisobutyl aluminium, 0.15 mol) was put
into the batch reactor having the volume of 250 ml that was dried
in the ice bath while the agitation was performed, and 12.42 g of
5-norbornene-2-methanol (0.1 mole) was slowly added thereto and the
agitation was performed for 20 minutes.
(2) Synthesis of the Protected Copolymer of 5-norbornene-2-methanol
and ethylene
[0130] After the dried batch reactor having the volume of 250 ml
was prepared under an Ar atmosphere, 7.92 g of the protected
5-norbornene-2-methanol solution (30 mmol) and 50 ml of purified
toluene were added thereto. After the temperature of the reactor
was increased to 70.degree. C., 0.3 .mu.mol of
isopropylene-(9-fluorenyl)-cyclopentadienyl-zirconium dichloride
used as the catalyst and 1.2 mmol of MAO used as the cocatalyst
were added thereto, and the polymerization was performed for 20
minutes while the pressure of ethylene was maintained at 75 psi.
Next, ethylene was removed under excessive pressure, and the
reaction solution was dropped on a large amount of
methanol/hydrochloric acid aqueous solution (volume ratio 1/1) to
obtain the polymer precipitate. The polymer that was obtained by
filtering the precipitate by using the glass funnel was dried in a
vacuum oven at 70.degree. C. for 24 hours to obtain the
5-norbornene-2-methanol/ethylene copolymer (yield: 56.8%, Mw=74363,
PDI=1.73).
(3) The Modification of the Cycloolefin Copolymer (Synthesis of the
5-norbornene-2-methyl-(4-methoxy cinnamate)/ethylene copolymer)
[0131] The 5-norbornene-2-methanol/ethylene copolymer (18.4 g,
0.121 mol) that was polymerized in (2), 4-methoxy cinnamic acid
(Aldrich, 21.5 g, 0.121 mol), EDC
[1-(3-dimethylaminopropyl)-3-ethylcarboimide hydrochloride]
(Aldrich, 37 g, 0.194 mol), and HOBT (1-hydroxybenzotriazole
hydrate) (Aldrich, 24.5 g, 0.182 mol) were put into the 2-neck
flask having the volume of 250 ml, and then dissolved in 100 ml of
DMF. After the temperature was reduced to 0.degree. C.,
triethylamine (Aldrich, 75 ml, 0.605 mol) was slowly dropped on the
reaction solution. After the temperature was increased to normal
temperature and maintained for 3 hours, when the reaction was
finished, the reaction solution was dropped on a large amount of
methanol to precipitate the polymer, and the polymer was filtered
to obtain the 5-norbornene-2-methyl-(4-methoxy cinnamate)/ethylene
copolymer to which the 4-methoxy cinnamoyl functional group was
introduced (yield: 90.5%).
Example 6
Synthesis of 5-norbornene-2-(4'-hydroxy-4-methoxy
chalcone)ester/ethylene copolymer
(1) The protection of the 5-norbornene-2-carboxylic acid
[0132] 69.42 g of TiBAL (triisobutyl aluminium, 0.35 mol) was put
into the batch reactor that was dried in the ice bath and had the
volume of 250 ml, 13.8 g of the 5-norbornene-2-carboxylic acid
(Aldrich, 0.1 mole) was slowly added thereto while the agitation
was performed, and the additional agitation was performed for 20
minutes.
(2) Synthesis of the Protected Copolymer of the
5-norbornene-2-carboxylic acid and ethylene
[0133] After the dried batch reactor having the volume of 250 ml
was prepared under an Ar atmosphere, 8.35 g of the protected
5-norbornene-2-carboxylic acid solution (30 mmol) and 50 ml of
purified toluene were added thereto. After the temperature of the
reactor was increased to 70.degree. C., 0.3 .mu.mol of
isopropylene-(9-fluorenyl)-cyclopentadienyl-zirconium dichloride
used as the catalyst and 1.2 mmol of MAO used as the cocatalyst
were added thereto, and the polymerization was performed for 20
minutes while the pressure of ethylene was maintained at 75 psi.
Next, ethylene was removed under excessive pressure, and the
reaction solution was dropped on a large amount of
methanol/hydrochloric and aqueous solution (volume ratio 1/1) to
obtain the polymer precipitate. The polymer that was obtained by
filtering the precipitate by using the glass funnel was dried in a
vacuum oven at 70.degree. C. for 24 hours to obtain the
5-norbornene-2-carboxylic acid/ethylene copolymer (yield: 22.7%,
Mw=65543, PDI=1.65).
(3) The Modification of the Cycloolefin Copolymer (Synthesis of the
5-norbornene-2-(4'-hydroxy-4-methoxy chalcone) ester/ethylene
copolymer)
[0134] The 5-norbornene-2-carboxylic acid/ethylene copolymer (13.2
g, 79.64 mmol) that was polymerized in (2), 4'-hydroxy-4-methoxy
chalcone (Aldrich, 18.4 g, 72.4 mmol), EDC (Aldrich, 22.2 g, 115.84
mmol), and HOBT (Aldrich, 14.7 g, 108.6 mmol) were put into the
2-neck flask having the volume of 250 ml, and then dissolved in 100
ml of DMF. After the temperature was reduced to 0.degree. C.,
triethylamine (Aldrich, 50 ml, 362 mmol) was slowly dropped on the
reaction solution. After the temperature was increased to normal
temperature and maintained for 3 hours, when the reaction was
finished, the reaction solution was dropped on a large amount of
methanol to precipitate the polymer, and the polymer was filtered
to obtain the 5-norbornene-2-(4'-hydroxy-4-methoxy
chalcone)ester/ethylene copolymer to which the 1-(3-methoxy
phenyl)-3-(2-hydroxyphenyl)-2-propenone functional group was
introduced (yield: 82.5%).
Example 7
Modification of Cycloolefin Copolymer: Synthesis of
5-norbornene-2-(7-hydroxy 6-methoxy coumarine)ester/ethylene
copolymer
[0135] The 5-norbornene-2-carboxylic acid/ethylene copolymer (13.2
g, 79.64 mmol) that was polymerized in (2) of Example 6, 7-hydroxy
6-methoxy coumarine (Aldrich, 13.0 g, 72.4 mmol), EDC (Aldrich,
22.2 g, 115.84 mmol), and HOBT (Aldrich, 14.7 g, 108.6 mmol) were
put into the 2-neck flask having the volume of 250 ml, and then
dissolved in 100 ml of DMF. After the temperature was reduced to
0.degree. C., triethylamine (Aldrich, 50 ml, 362 mmol) was slowly
dropped on the reaction solution. After the temperature was
increased to normal temperature and maintained for 3 hours, when
the reaction was finished, the reaction solution was dropped on a
large amount of methanol to precipitate the polymer, and the
polymer was filtered to obtain the 5-norbornene-2-(7-hydroxy
6-methoxy coumarine) ester/ethylene copolymer to which the
7-hydroxy 6-methoxy coumarine functional group was introduced
(yield: 73%).
Example 8
Preparation of the phenylnorbornene/ethylene Copolymer to which the
Cinnamoyl Functional Group was Introduced
(1) Polymerization of the Cycloolefin Copolymer: Polymerization of
the copolymer of Phenyl NB and Ethylene
[0136] 5.1 g of phenylnorbornene (30 mmol) as the monomer and 50 ml
of toluene purified by the solvent were added to the dried batch
reactor having the volume of 250 ml. After the temperature of the
reactor was increased to 70.degree. C., 0.3 .mu.mol of
[PhCH(fluorenyl)(Cp)]ZrCl.sub.2 used as the catalyst and 1.2 mmol
of MAO were added thereto, and the polymerization was performed for
20 minutes while the pressure of ethylene was maintained at 75 psi.
Next, ethylene was removed under excessive pressure, and the
reaction solution was dropped on a large amount of
methanol/hydrochloric acid aqueous solution (volume ratio 1/1) to
obtain the polymer precipitate. The polymer that was obtained by
filtering the precipitate by using the glass funnel was dried in a
vacuum oven at 70.degree. C. for 24 hours to obtain the
phenylnorbornene/ethylene copolymer (yield: 55%, Mw=89125,
PDI=1.51).
(2) Synthesis of 4-methoxy cinnamoyl chloride
[0137] 53.5 g of the 4-methoxy cinnamic add (Aldrich 0.3 mol)) and
124.9 g of SOCl.sub.2 (Thionyl Chloride, 1.05 mol) were put into
the two-neck flask having the volume of 250 ml, and then reacted
with each other at normal temperature for 24 hours. After the
reaction was finished, the distillation was performed to remove an
excessive amount of SOCl.sub.2, and the reactant was diluted with
100 ml of toluene and neutralized by using the NaHCO.sub.3
solution. After the neutralization, the resulting substance was
dried by using anhydrous MgSO.sub.4, and filtered, and the solvent
was removed by using the rotary evaporator. Next, the substance was
passed through the silica gel to remove the impurity, thus
obtaining 36.5 g of the white solid (yield: 62%).
(3) Friedel-Crafts Acylation Reaction (Preparation of the
phenylnorbornene/ethylene Copolymer to which the Cinnamoyl
Functional Group was Introduced)
[0138] 19.8 g of the phenylnorbornene/ethylene copolymer (0.1 mol)
that was polymerized in (1), 29.4 g of 4-methoxy cinnamoyl chloride
(0.15 mol) that was synthesized in (2), and 150 ml of CH.sub.3CN
used as the solvent were added to the two-neck flask having the
volume of 250 ml. 10 mol % Cu(OTf).sub.2 was added to the rewtion
solution as the catalyst, and the reaction was performed at
80.degree. C. for 8 hours. Next, the reaction solution was dropped
on a large amount of methanol to precipitate the polymer, the
polymer was filtered to obtain the phenylnorbornene/ethylene
copolymer to which the cinnamoyl functional group was introduced
(yield: 87%).
Preparation Example 4
Preparation of the Alignment Film by using the
5-norbornene-2-methyl-(4-methoxy cinnamate)/ethylene copolymer
Polymer
[0139] The 5-norbornene-2-methyl-(4-methoxy cinnamate)/ethylene
copolymer polymer that was synthesized in Example 5 was dissolved
in the c-pentanone solvent in a concentration of 2% by weight, and
applied on the polyethylene terephthalate substrate (commercial
name: SH71, prepared by SKC Co., Ltd. in Korea) having the
thickness of 80 micron by using the roll coating process so that
the thickness of the polyethylene terephthalate substrate was 1000
.ANG. after the drying. Next, the substrate was heated in an oven
at 80.degree. C. for 3 minutes to remove the solvent in the inside
of the coating film and to form the coating film. The exposing was
performed by using a high pressure mercury lamp having the
intensity of 200 mW/cm.sup.2 as a light source while polarized UV
that was perpendicular to the proceeding direction of the film was
radiated on the coating film by using a Wire-grid polarizer
prepared by Moxtek, Co., Ltd. for 5 sec, so that the alignment was
provided to form the alignment film. Next, the solid in which 95.0%
by weight of cyanobiphenyl acrylate that was polymeriiable by UV
and 5.0% by weight of Irgaure 907 (prepared by Ciba-Geigy, Co.,
Ltd. in Switzerland) as the photoinitiator were mixed with each
other was dissolved in toluene so that the content of the liquid
crystal was 25 parts by weight based on 100 parts by weight of the
liquid crystal solution to prepare the polymerizable reactive
liquid crystal solution. The prepared liquid crystal solution was
applied on the photo-alignment film that was formed by using a roll
coating process so that the thickness of the film after the drying
was 1 .mu.m, and the drying was performed at 80.degree. C. for 2
minutes to align the molecules of the liquid crystal. The
nonpolarized UV was radiated on the aligned liquid crystal film by
using a high-pressure mercury lamp having the intensity of 200
mW/cm.sup.2 as a light source to fix the alignment state of the
liquid crystal, thereby preparing the retardation film.
Preparation Example 5
Preparation of the Alignment Film by using the
5-norbornene-2-(4'-hydroxy-4-methoxy chalcone)ester/ethylene
copolymer
[0140] The retardation film was prepared by using the same method
as Preparation Example 4, except that the polymer prepared in
Example 6 was used instead of the polymer prepared in Example
5.
Preparation Example 6
5-norbornene-2-(7-hydroxy 6-methoxy coumarine)ester/ethylene
copolymer
[0141] The retardation film was prepared by using the same method
as Preparation Example 4, except that the polymer prepared in
Example 7 was used instead of the polymer prepared in Example
5.
Preparation Example 7
Phenylnorbornene/ethylene copolymer to which the Cinnamoyl
Functional Group was Introduced
[0142] The retardation film was prepared by using the same method
as Preparation Example 4, except that the polymer prepared in
Example 8 was used instead of the polymer prepared in Example
5.
Comparative Example 3
[0143] The alignment film was prepared by using the same method as
Preparation Example 4, except that the compound of Comparative
Example 1 was used.
Comparative Example 4
[0144] The alignment film was prepared by using the same method as
Preparation Example 4, except that the
5-norbornene-2-methyl-cinnamate/ethylene copolymer having no
methoxy substituent, which was represented by the following
Formula, was used instead of the 5-norbornene-2-methyl-(4-methoxy
cinnamate)/ethylene copolymer of Preparation Example 4.
##STR00016##
Experimental Example 1
Photoreactive Property Evaluation--FT-IR Spectrum
[0145] In order to obtain the photoreactive property of the
alignment film, the FT-IR spectrum of each of the liquid crystal
alignment films that were obtained in Preparation Examples 4 to 7
and Comparative Example 2 was observed, and the photoreactive
properties were compared to each other based on the time
(t.sub.1/2) required until the intensity of the stretching mode of
the C.dbd.C bond of the Formulae 1a to 1c of the polymer during the
exposure (the mercury lamp having the intensity of 20 mW/cm.sup.2
was used) was reduced by half and the energy value (E.sub.1/2=20
mW/cm.sup.2, t.sub.1/2). The results are described in the following
Table 2. From the comparison of t.sub.1/2 values, it could be seen
that in the case of Preparation Examples 4 to 7, the time was
reduced by about 1/10 to 1/4 as compared to the case of Comparative
Example 2 and thus the liquid crystal alignment film according to
the present invention had the desirable photoreactive rate.
[0146] Table 2
TABLE-US-00002 TABLE 2 T.sub.1/2 (min) E.sub.1/2 (J/cm.sup.2)
Preparation Example 4 1.0 1.1 Preparation Example 5 1.3 1.4
Preparation Example 6 1.5 1.8 Preparation Example 7 1.6 1.9
Comparative Example 2 9.3 11.2
Experimental Example 4
[0147] Evaluation of the Alignment Property (Evaluation of the
Degree of Light Leakage)
[0148] In order to evaluate the alignment property of the alignment
film, the liquid crystal retardation film that was prepared in
Preparation Example 4 and Comparative Example 3 was observed
between two polarizers that were perpendicular to each other by
using a polarizing microscope, and the transmittance thereof is
shown in FIG. 2. That is, in order to evaluate the transmittance,
based on polyethylene terephthalate having a thickness of 80
microns (trademark: SH71, prepared by SKC, Co., Ltd. in Korea), the
liquid crystal retardation film that was prepared in Preparation
Example 4 and Comparative Example 3 was provided between the
polarizers that were perpendicular to each other and the degree of
transmittance of incident light through the polarizing plate and
the retardation film was checked by using the polarizing microscope
to measure the degree of light leakage, which is shown in FIG. 2.
As shown in FIG. 2, in the retardation film of Preparation Example
4 according to the present invention, the alignment direction of
liquid crystal was uniform regardless of the wavelength of incident
light, but in the case of when the alignment film of Comparative
Example 3 was applied, it could be seen that the alignment strength
was reduced and the alignment direction of liquid crystal was not
uniform, thus, the transmittance was increased.
* * * * *