U.S. patent application number 15/664331 was filed with the patent office on 2017-11-16 for liquid crystal aligning agents for forming photo-aligning liquid crystal alignment layers, liquid crystal alignment layers and liquid crystal display devices using the same.
The applicant listed for this patent is JNC CORPORATION, JNC PETROCHEMICAL CORPORATION. Invention is credited to Rika HISADA, Keisuke IZAWA, Yuko KATANO, Tomoyuki MATSUDA, Youichiro OOKI.
Application Number | 20170327744 15/664331 |
Document ID | / |
Family ID | 49383422 |
Filed Date | 2017-11-16 |
United States Patent
Application |
20170327744 |
Kind Code |
A1 |
OOKI; Youichiro ; et
al. |
November 16, 2017 |
LIQUID CRYSTAL ALIGNING AGENTS FOR FORMING PHOTO-ALIGNING LIQUID
CRYSTAL ALIGNMENT LAYERS, LIQUID CRYSTAL ALIGNMENT LAYERS AND
LIQUID CRYSTAL DISPLAY DEVICES USING THE SAME
Abstract
A photo-aligning liquid crystal alignment layer formed by using
a photo-aligning liquid crystal aligning agent containing polyamic
acid or a derivative thereof which is synthesized by using
tetracarboxylic acid dianhydride having no photoreactive structure
having a specific structure and diamine having no photoreactive
structure having a specific structure together with at least one of
tetracarboxylic acid dianhydride having a photoreactive structure
and diamine having a photoreactive structure can reduce storage of
residual DC in a liquid crystal display device. Further, the above
alignment layer can shorten the relaxation time and can prevent
afterimages from being generated.
Inventors: |
OOKI; Youichiro; (Chiba,
JP) ; KATANO; Yuko; (Chiba, JP) ; MATSUDA;
Tomoyuki; (Chiba, JP) ; IZAWA; Keisuke;
(Chiba, JP) ; HISADA; Rika; (Chiba, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
JNC CORPORATION
JNC PETROCHEMICAL CORPORATION |
Tokyo
Tokyo |
|
JP
JP |
|
|
Family ID: |
49383422 |
Appl. No.: |
15/664331 |
Filed: |
July 31, 2017 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14394540 |
Oct 15, 2014 |
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PCT/JP2013/060841 |
Apr 10, 2013 |
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15664331 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08G 73/1096 20130101;
C08G 73/1046 20130101; G02F 1/133788 20130101; C08K 5/544 20130101;
Y10T 428/10 20150115; C08K 5/3417 20130101; C09K 19/56 20130101;
C09K 2323/00 20200801; C08K 5/5419 20130101; C09K 2323/02 20200801;
C08G 73/10 20130101; C09K 2323/027 20200801; C08K 5/353 20130101;
Y10T 428/1005 20150115; Y10T 428/1023 20150115 |
International
Class: |
C09K 19/56 20060101
C09K019/56; C08K 5/544 20060101 C08K005/544; C08K 5/5419 20060101
C08K005/5419; C08K 5/3417 20060101 C08K005/3417; C08G 73/10
20060101 C08G073/10; C08G 73/10 20060101 C08G073/10; C08K 5/353
20060101 C08K005/353; C08G 73/10 20060101 C08G073/10 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 16, 2012 |
JP |
2012-092708 |
Mar 27, 2013 |
JP |
2013-065979 |
Claims
1-21. (canceled)
22. A photo-aligning liquid crystal aligning agent containing a
polyamic acid or derivative thereof having a photoreactive
structure originating in at least one of a tetracarboxylic acid
dianhydride having a photoreactive structure and a diamine having a
photoreactive structure in a structural unit, wherein the polyamic
acid or derivative thereof is synthesized by using a
tetracarboxylic acid dianhydride having no photoreactive structure
and a diamine having no photoreactive structure together with at
least one of the tetracarboxylic acid dianhydride having a
photoreactive structure and the diamine having a photoreactive
structure; the tetracarboxylic acid dianhydride having no
photoreactive structure comprises at least one selected from the
group of compounds represented by the following Formula (AN-a); the
diamine having no photoreactive structure comprises at least one
selected from the group of compounds represented by the following
Formulas (DI-a) and (DI-c): ##STR00114## wherein in Formula (AN-a),
X.sup.1 is a single bond or alkylene having 1 to 20 carbon atoms;
and in Formula (DI-a), groups in which bonding positions are not
fixed to any of carbon atoms constituting the rings show that the
bonding positions thereof in the rings are optional.
23. The photo-aligning liquid crystal aligning agent as described
in claim 22, wherein at least one of the tetracarboxylic acid
dianhydride having a photoreactive structure and the diamine having
a photoreactive structure is at least one selected from the group
of compounds represented by the following Formulas (I) to (VII):
R.sup.2--C.ident.C--R.sup.3 (I)
R.sup.2--C.ident.C--C.ident.C--R.sup.3 (II)
R.sup.2--C.ident.C--CH.dbd.CH--R.sup.3 (III)
R.sup.2--C.ident.C--R.sup.4--C.ident.C--R.sup.3 (IV)
R.sup.2--C.ident.C--R.sup.4--CH.dbd.CH--R.sup.3 (V)
R.sup.2--CH.dbd.CH--R.sup.3 (VI) R.sup.2--N.dbd.N--R.sup.3 (VII)
wherein in Formulas (I) to (VII), R.sup.2 and R.sup.3 each are
independently a monovalent organic group having NH.sub.2 or a
monovalent organic group having --CO--O--CO--, and R.sup.4 is a
divalent organic group having an aromatic ring.
24. The photo-aligning liquid crystal aligning agent as described
in claim 22, wherein the photoreactive structure is located in a
principal chain of the polyamic acid or derivative thereof.
25. The photo-aligning liquid crystal aligning agent as described
in claim 22, wherein at least one of the tetracarboxylic acid
dianhydride having a photoreactive structure and the diamine having
a photoreactive structure is at least one selected from the group
of compounds represented by the following Formulas (I-1), (II-1),
(III-1), (IV-1), (IV-2), (V-1), (VI-1) and (VII-1) to (VII-3):
##STR00115## wherein in Formulas (I-1), (II-1), (III-1), (IV-1),
(V-1), (VI-1), (VII-1) and (VII-2), groups in which bonding
positions are not fixed to any of carbon atoms constituting the
rings show that the bonding positions thereof in the rings are
optional; and in Formula (VII-1), plural R.sup.5 each are
independently --CH.sub.3, --OCH.sub.3, --CF.sub.3 or --COOCH.sub.3;
and b is an integer of 0 to 2.
26. The photo-aligning liquid crystal aligning agent as described
in claim 25, wherein at least one of the tetracarboxylic acid
dianhydride having a photoreactive structure and the diamine having
a photoreactive structure is at least one selected from the group
of compounds represented by the following Formulas (VI-1-1),
(VII-1-1) and (VII-3): ##STR00116##
27. The photo-aligning liquid crystal aligning agent as described
in claim 22, wherein an other tetracarboxylic acid dianhydride
having no photoreactive structure which is used together with the
at least one selected from the group of the compounds represented
by Formula (AN-a) is at least one selected from the group of
compounds represented by the following Formulas (AN-I) to (AN-VII):
##STR00117## wherein in Formulas (AN-I), (AN-IV) and (AN-V), plural
X each are independently a single bond or --CH.sub.2--; in Formula
(AN-II), G is a single bond, alkylene having 1 to 20 carbon atoms,
--CO--, --O--, --S--, --SO.sub.2--, --C(CH.sub.3).sub.2-- or
--C(CF.sub.3).sub.2--; in Formulas (AN-II) to (AN-IV), plural Y
each are independently one selected from the group of the following
trivalent groups: ##STR00118## wherein at least one hydrogen of the
above trivalent groups may be substituted with methyl, ethyl or
phenyl; in Formula (AN-II), when Y is 2-azapropane-1,2,3-triyl, G
described above is not an alkylene having 1 to 20 carbon atoms, and
when Y is benzene-1,2,4-triyl, G described above is not an alkylene
having 1 to 8 carbon atoms or --O--; in Formulas (AN-III) to
(AN-V), a ring A is a monocyclic hydrocarbon group having 3 to 10
carbon atoms or a condensed polycyclic hydrocarbon group having 6
to 30 carbon atoms; wherein at least one hydrogen of the above
group may be substituted with methyl, ethyl or phenyl; an atomic
bonding coupled with the ring is connected with optional carbon
constituting the ring, and two atomic bondings may be connected
with the same carbon; in Formula (AN-VI), X.sup.10 is alkylene
having 2 to 6 carbon atoms; Me is methyl; and Ph is phenyl; and in
Formula (AN-VII), plural G.sup.10 each are independently --O--,
--COO-- or --OCO--; and plural r each are independently 0 or 1.
28. The photo-aligning liquid crystal aligning agent as described
in claim 27, wherein the other tetracarboxylic acid dianhydride
having no photoreactive structure which is used together with the
at least one selected from the group of the compounds represented
by Formula (AN-a) is at least one selected from the group of
compounds represented by the following Formulas (AN-1-1), (AN-2-1),
(AN-3-1), (AN-3-2), (AN-5-1) and (AN-16-1): ##STR00119##
29. The photo-aligning liquid crystal aligning agent as described
in claim 22, wherein an other diamine having no photoreactive
structure which is used together with the at least one selected
from the group of the compounds represented by Formulas (DI-a) and
(DI-c) is at least one selected from the group of compounds
represented by the following Formulas (DI-1) and (DI-3) to (DI-17):
##STR00120## wherein in Formula (DI-1), m is an integer of 1 to 12;
in Formulas (DI-3), (DI-6) and (DI-7), plural G.sup.21 each are
independently a single bond, --O--, --S--, --S--S--, --SO.sub.2--,
CO--, --CONH--, --NHCO--, --C(CH.sub.3).sub.2--,
--C(CF.sub.3).sub.2--, --C(CH.sub.2).sub.m'--,
--O--(CH.sub.2).sub.m'--O-- or --S--(CH.sub.2).sub.m'--S--, and
plural m' each are independently an integer of 1 to 12; in Formula
(DI-5), G.sup.21 is a single bond, --NH--, --O--, --S--, --S--S--,
--SO.sub.2--, --CO--, --CONH--, --NHCO--, --C(CH.sub.3).sub.2--,
--C(CF.sub.3).sub.2--, --C(CH.sub.2).sub.m''--,
--O--(CH.sub.2).sub.m'--O--,
--N--C(CH.sub.3)--(CH.sub.2).sub.k--N(CH.sub.3)-- or
--S--(CH.sub.2).sub.m'--S--; m' is an integer of 1 to 12, and m''
is an integer of 6 to 12; and k is an integer of 1 to 5; in
Formulas (DI-6) and (DI-7), plural G.sup.22 each are independently
a single bond, --O--, --S--, CO--, --C(CH.sub.3).sub.2--,
--C(CF.sub.3).sub.2-- or alkylene having 1 to 10 carbon atoms; at
least one hydrogen of a cyclohexane ring and a benzene ring in
Formulas (DI-3) to (DI-7) may be substituted with --F, --CH.sub.3,
--OH, --CF.sub.3, --CO.sub.2H--, --CONH.sub.2 or benzyl, and in
addition thereto, in Formula (DI-4), at least one hydrogen of a
benzene ring may be substituted with at least one group represented
the following Formulas (DI-4-a) to (DI-4-c): ##STR00121## wherein
in Formulas (DI-4-a) and (DI-4-b), plural R.sup.20 each are
independently hydrogen or --CH.sub.3; in Formulas (DI-3) to (DI-7),
groups in which bonding positions are not fixed to any of carbon
atoms constituting the rings show that the bonding positions
thereof in the rings are optional; and the bonding position of
--NH.sub.2 to the cyclohexane ring or the benzene ring is an
optional position excluding the bonding position of G.sup.21 or
G.sup.22: ##STR00122## wherein in Formula (DI-8), R.sup.21 and
R.sup.22 each are independently alkyl having 1 to 3 carbon atoms or
phenyl; plural G.sup.23 each are independently alkylene having 1 to
6 carbon atoms, phenylene or phenylene substituted with alkyl; and
w is an integer of 1 to 10; in Formula (DI-9), plural R.sup.23 each
are independently alkyl having 1 to 5 carbon atoms, alkoxy having 1
to 5 carbon atoms or Cl; plural p each are independently an integer
of 0 to 3, and q is an integer of 0 to 4; and p and q are not 0 at
the same time; in Formula (DI-10), R.sup.24 is alkyl having 1 to 4
carbon atoms, phenyl or benzyl; in Formula (DI-11), G.sup.24 is
--CH.sub.2-- or --NH--; in Formula (DI-12), G.sup.25 is a single
bond, alkylene having 2 to 6 carbon atoms or 1,4-phenylene; and r
is 0 or 1; in Formula (DI-12), groups in which bonding positions
are not fixed to any of carbon atoms constituting the rings show
that the bonding positions thereof in the rings are optional; in
Formulas (DI-9), (DI-11) and (DI-12), the bonding positions of
--NH.sub.2 bonded to the benzene rings are optional positions:
##STR00123## wherein in Formula (DI-13), G.sup.26 is a single bond,
--O--, --COO--, --OCO--, --CO--, --CONH--, --CH.sub.2O--,
--OCH.sub.2--, --CF.sub.2O--, --OCF.sub.2-- or
--O--(CH.sub.2).sub.m'--, and m' is an integer of 1 to 12; R.sup.25
is alkyl having 3 to 20 carbon atoms, phenyl, cyclohexyl, a group
having a steroid skeleton or a group represented by the following
Formula (DI-13-a); wherein in the above alkyl, at least one
hydrogen may be substituted with --F, and at least one --CH.sub.2--
may be substituted with --O--; hydrogen of the above phenyl may be
substituted with --F, --CH.sub.3, --OCH.sub.3, --OCH.sub.2F,
--OCHF.sub.2, --OCF.sub.3, alkyl having 3 to 20 carbon atoms or
alkoxy having 3 to 20 carbon atoms; hydrogen of the above
cyclohexyl may be substituted with alkyl having 3 to 20 carbon
atoms or alkoxy having 3 to 20 carbon atoms; and the bonding
position of --NH.sub.2 bonded to the benzene ring shows that it is
an optional position in the above ring: ##STR00124## wherein in
Formula (DI-13-a), G.sup.27, G.sup.28 and G.sup.29 represent a
bonding group, and they each are independently a single bond or
alkylene having 1 to 12 carbon atoms; wherein at least one
--CH.sub.2-- in the above alkylene may be substituted with --O--,
--COO--, --OCO--, --CONH-- or --CH.dbd.CH--; a ring B.sup.21, a
ring B.sup.22, a ring B.sup.23 and a ring B.sup.24 each are
independently 1,4-phenylene, 1,4-cyclohexylene,
1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl,
naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-2,6-diyl,
naphthalene-2,7-diyl or anthracene-9,10-diyl; in the ring B.sup.21,
the ring B.sup.22, the ring B.sup.23 and the ring B.sup.24, at
least one hydrogen may be substituted with --F or --CH.sub.3; s, t
and u each are independently an integer of 0 to 2, and a total
thereof is 1 to 5; when s, t or u is 2, two bonding groups in each
parenthesis may be the same or different, and two rings may be the
same or different; R.sup.26 is --F, --OH, alkyl having 1 to 30
carbon atoms, fluorine-substituted alkyl having 1 to 30 carbon
atoms, alkoxy having 1 to 30 carbon atoms, --CN, --OCH.sub.2F,
--OCHF.sub.2 or --OCF.sub.3, and at least one --CH.sub.2-- in the
above alkyl having 1 to 30 carbon atoms may be substituted with a
divalent group represented by the following Formula (DI-13-b):
##STR00125## wherein in Formula (DI-13-b), R.sup.27 and R.sup.28
each are independently alkyl having 1 to 3 carbon atoms; and v is
an integer of 1 to 6: ##STR00126## wherein in Formulas (DI-14) and
(DI-15), plural G.sup.30 each are independently a single bond,
--CO-- or --CH.sub.2--; plural R.sup.29 each are independently
hydrogen or --CH.sub.3; R.sup.30 is hydrogen, alkyl having 1 to 20
carbon atoms or alkenyl having 2 to 20 carbon atoms; and one
hydrogen of a benzene ring in Formula (DI-15) may be substituted
with alkyl having 1 to 20 carbon atoms or phenyl; in Formulas
(DI-14) and (DI-15), groups in which bonding positions are not
fixed to any of carbon atoms constituting the rings show that the
bonding positions thereof in the rings are optional; and --NH.sub.2
bonded to the benzene ring shows that the bonding position thereof
in the ring is optional: ##STR00127## wherein in Formulas (DI-16)
and (DI-17), plural G.sup.31 each are independently --O-- or
alkylene having 1 to 6 carbon atoms; G.sup.32 is a single bond or
alkylene having 1 to 3 carbon atoms; R.sup.31 is hydrogen or alkyl
having 1 to 20 carbon atoms, and at least one --CH.sub.2-- of the
above alkyl may be substituted with --O--; R.sup.32 is alkyl having
6 to 22 carbon atoms; R.sup.33 is hydrogen or alkyl having 1 to 22
carbon atoms; a ring B.sup.25 is 1,4-phenylene or
1,4-cyclohexylene; r is 0 or 1; and --NH.sub.2 bonded to the
benzene ring shows that the bonding position thereof in the ring is
optional.
30. The photo-aligning liquid crystal aligning agent as described
in claim 29, wherein the other diamine having no photoreactive
structure which is used together with the at least one selected
from the group of the compounds represented by Formulas (DI-a) and
(DI-c) is at least one selected from the group of compounds
represented by the following Formulas (DI-4-1), (DI-5-9),
(DI-5-12), (DI-5-27), (DI-5-30) and (DI-7-3): ##STR00128## wherein
in Formula (DI-5-12) and (DI-7-3), m is an integer of 1 to 12; in
Formula (DI-5-30), k is an integer of 1 to 5; and in Formula
(DI-7-3), n is 1 or 2.
31. The photo-aligning liquid crystal aligning agent as described
in claim 22, further comprising at least one selected from the
group of compounds consisting of alkenyl-substituted nadiimide
compounds, compounds having a radically polymerizable unsaturated
double bond, oxazine compounds, oxazoline compounds, epoxy
compounds and silane coupling agents.
32. The photo-aligning liquid crystal aligning agent as described
in claim 31, wherein the alkenyl-substituted nadiimide compound is
at least one selected from the group of compounds consisting of
bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenyl}methane,
N,N'-m-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)
and
N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide).
33. The photo-aligning liquid crystal aligning agent as described
in claim 31, wherein the epoxy compound is at least one selected
from the group of compounds consisting of
N,N,N',N'-tetraglycidyl-m-xylylenediamine,
1,3-bis(N,N-diglycidylaminomethyl)cyclohexane,
N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane,
2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-([2,3-epoxypropoxy]phenyl]-
ethyl]phenyl]propane,
3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate and
N-phenylmaleimide-glycidyl methacrylate copolymers.
34. The photo-aligning liquid crystal aligning agent as described
in claim 31, wherein the silane coupling agent is at least one
selected from the group of compounds consisting of
2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,
paraaminophenyltrimethoxysilane and
3-aminopropyltriethoxysilane.
35. A photo-aligning liquid crystal alignment layer formed by the
photo-aligning liquid crystal aligning agent as described in claim
22.
36. A photo-aligning liquid crystal alignment layer formed by a
step of coating the photo-aligning liquid crystal aligning agent as
described in claim 22 on a substrate, a step of heating and drying
the substrate coated with the aligning agent to achieve a dried
layer and a step of irradiating the dried layer with a polarized UV
ray.
37. A photo-aligning liquid crystal alignment layer formed by a
step of coating the photo-aligning liquid crystal aligning agent as
described in claim 22 on a substrate, a step of heating and drying
the substrate coated with the aligning agent to achieve a dried
layer, a step of irradiating the dried layer with a polarized UV
ray and then a step of heating and baking the layer.
38. A photo-aligning liquid crystal alignment layer formed by a
step of coating the photo-aligning liquid crystal aligning agent as
described in claim 22 on a substrate, a step of heating and drying
the substrate coated with the aligning agent to achieve a dried
layer, a step of heating and baking the dried layer and then a step
of irradiating the layer with a polarized UV ray.
39. A liquid crystal display device comprising the photo-aligning
liquid crystal alignment layer as described in claim 35.
Description
BACKGROUND OF THE INVENTION
[0001] The present invention relates to a photo-aligning liquid
crystal aligning agent used for a photo-aligning method, a
photo-alignment layer and a liquid crystal display device prepared
by using the same.
RELATED ART
[0002] Display devices prepared by using nematic liquid crystals
are mainly used for liquid crystal display devices which are
produced in an industrial scale at present and usually distributed,
including various display devices such as monitors for personal
computers, liquid crystal televisions, view finders of video
cameras, projection type displays and the like,
optoelectronics-related devices such as optical printer heads,
optical Fourier transform, light valves and the like. A TN (twisted
nematic) mode and a STN (super twisted nematic) mode are known well
as a display mode of a nematic liquid crystal display device. In
recent years, TN type liquid crystal display devices prepared by
using an optical compensation film, an MVA (multi-domain vertical
alignment) mode in which vertical alignment and a technique of a
projection structure are used in combination, an IPS (in-plane
switching) mode of a lateral electric field system, an FFS (fringe
field switching) mode and the like are proposed in order to improve
a narrow viewing angle which is one of the problems of the above
modes, and they are put into practical use.
[0003] The development of the technologies of liquid crystal
display devices have been achieved not only merely by improving the
above drive methods and device structures but also by improving
constitutional members used for the devices. Among the
constitutional members used for the devices, particularly a liquid
crystal alignment layer is one of important materials related to
the display quality, and it has come to be important as liquid
crystal display devices are provided with a higher quality that the
performances of the alignment layers are enhanced.
[0004] Photo-alignment layers are formed by liquid crystal aligning
agents. Liquid crystal aligning agents which are mainly used at
present are solutions (vanishes) prepared by dissolving polyamic
acid or soluble polyimide in organic solvents. The above solutions
are applied on a substrate, and then layers are formed therefrom by
means such as heating and the like to form polyimide base liquid
crystal alignment layers.
[0005] A rubbing method which is simple and makes it possible to
carry out high speed treatment in a large area is widely used as an
alignment treating method in an industrial scale. The rubbing
method is treatment in which a cloth made of fibers comprising
nylons, rayons, polyesters and the like is used to rub the surface
of a liquid crystal alignment layer in a single direction, and this
treatment makes it possible to obtain uniformly aligned liquid
crystal molecules. However, problems such as dusts, static
electricity and the like which are involved in the rubbing method
are pointed out, and in recent years, alignment treating methods in
place of the rubbing method are actively tried to be developed.
[0006] A photo-alignment treating method in which light is radiated
to carry out aligning treatment is paid attentions as an alignment
treating method in place of the rubbing method. Many aligning
mechanisms such as a photodecomposition method, a
photoisomerization method, a photodimerization method, a
photocrosslinking method and the like are proposed for the
photo-alignment treating method (refer to, for example, a
non-patent document 1 and patent documents 1 and 2). The
photo-alignment treating method is a non-contact photo-alignment
treating method having a high uniformity of alignment as compared
with the rubbing method, and therefore it involves the advantages
that the layer is prevented from being scratched and can be reduced
in a cause of bringing about inferior display of the liquid crystal
display devices by dusts, a static electricity and the like.
[0007] The present inventors have continued to investigate liquid
crystal alignment layers having a photoreactive group which brings
about photoisomerization or photodimerization in a polyamic acid
structure (refer to, for example, patent documents 3 to 5). The
above photo-alignment layers have had a large anchoring energy and
a good aligning property and have been excellent in electrical
characteristics such as a voltage holding ratio and the like.
However, a reduction in a residual voltage (residual DC) which is
one of characteristics required to liquid crystal alignment layers
has not sufficiently been investigated and evaluated. The residual
DC is a voltage which remains when a voltage is returned to 0 V
after applying a voltage to operate a liquid crystal. It is known
that when a liquid crystal display device is caused to display
optional images for a long time and then changed so as to display
another images, a phenomenon in which the previous images remain as
afterimages is brought about to deteriorate a display quality of
the images, and the above afterimages can be reduced by inhibiting
the storage of residual DC and shortening the relaxation time
(refer to, for example, a patent document 6).
PRIOR ARTS
Patent Documents
[0008] Patent document 1: JP 1997-297313 A [0009] Patent document
2: JP 1998-251646 A [0010] Patent document 3: JP 2005-275364 A
[0011] Patent document 4: JP 2007-248637 A [0012] Patent document
5: JP 2009-069493 A [0013] Patent document 6: JP 2008-233713 A
Non-Patent Document
[0013] [0014] Non-patent document 1: Liquid Crystal, vol. 3, No. 4,
p. 262, 1999
DISCLOSURE OF THE INVENTION
[0015] An object of the present invention is to provide a
photo-aligning liquid crystal aligning agent for obtaining a liquid
crystal alignment layer capable of providing a liquid crystal
display device which can decrease storage of residual DC and
shorten a relaxation time and which can prevent afterimages from
being generated.
[0016] The present inventors have developed a photo-aligning liquid
crystal aligning agent containing polyamic acid or a derivative
thereof having a photoreactive structure originating in at least
one of tetracarboxylic acid dianhydride having a photoreactive
structure and diamine having a photoreactive structure, wherein the
polyamic acid or a derivative thereof is synthesized by using
tetracarboxylic acid dianhydride having no photoreactive structure
having a specific structure and diamine having no photoreactive
structure having a specific structure together with at least one of
the tetracarboxylic acid dianhydride having a photoreactive
structure and the diamine having a photoreactive structure. Then,
they have found that a liquid crystal display device which can
satisfy the required characteristics described above is obtained by
using a liquid crystal alignment layer formed by the above liquid
crystal aligning agent, and they have completed the present
invention.
[0017] The present invention comprises the following
constitutions.
[1] A photo-aligning liquid crystal aligning agent containing
polyamic acid or a derivative thereof having a photoreactive
structure originating in at least one of tetracarboxylic acid
dianhydride having a photoreactive structure and diamine having a
photoreactive structure in a structural unit, wherein the above
polyamic acid or a derivative thereof is synthesized by using
tetracarboxylic acid dianhydride having no photoreactive structure
and diamine having no photoreactive structure together with at
least one of tetracarboxylic acid dianhydride having a
photoreactive structure and diamine having a photoreactive
structure; the tetracarboxylic acid dianhydride having no
photoreactive structure includes at least one selected from the
group of compounds represented by the following Formulas (AN-a) to
(AN-c); the diamine having no photoreactive structure includes at
least one selected from the group of compounds represented by the
following Formulas (DI-a) to (DI-c):
##STR00001##
in Formula (AN-a), X.sup.1 is a single bond or alkylene having 1 to
20 carbon atoms; in Formula (AN-b), X.sup.2 is alkylene having 1 to
8 carbon atoms; in Formula (DI-b), R.sup.2 is hydrogen or
--CH.sub.3, and a is an integer of 1 to 5; and in Formulas (DI-a)
and (DI-b), groups in which bonding positions are not fixed to any
of carbon atoms constituting the rings show that the bonding
positions thereof in the rings are optional. [2] The photo-aligning
liquid crystal aligning agent as described in the above item [1],
wherein at least one of the tetracarboxylic acid dianhydride having
a photoreactive structure and the diamine having a photoreactive
structure is at least one selected from the group of compounds
represented by the following Formulas (I) to (VII):
R.sup.2--C.ident.C--R.sup.3 (I)
R.sup.2--C.ident.C--C.ident.C--R.sup.3 (II)
R.sup.2--C.ident.C--CH.dbd.CH--R.sup.3 (III)
R.sup.2--C.ident.C--R.sup.4--C.ident.C--R.sup.3 (IV)
R.sup.2--C.ident.C--R.sup.4--CH.dbd.CH--R.sup.3 (V)
R.sup.2--CH.dbd.CH--R.sup.3 (VI)
R.sup.2--N.dbd.N--R.sup.3 (VII)
in Formulas (I) to (VII), R.sup.2 and R.sup.3 each are
independently a monovalent organic group having NH.sub.2 or a
monovalent organic group having --CO--O--CO--, and R.sup.4 is a
divalent organic group having an aromatic ring. [3] The
photo-aligning liquid crystal aligning agent as described in the
above item [1] or [2], wherein the photoreactive structure is
located in a principal chain of the polyamic acid or the derivative
thereof. [4] The photo-aligning liquid crystal aligning agent as
described in any one of the above items [1] to [3], wherein at
least one of the tetracarboxylic acid dianhydride having a
photoreactive structure and the diamine having a photoreactive
structure is at least one selected from the group of compounds
represented by the following Formulas (I-1), (II-1), (III-1),
(IV-1), (IV-2), (V-1), (VI-1) and (VII-1) to (VII-3):
##STR00002##
in Formulas (I-1), (II-1), (III-1), (IV-1), (V-1), (VI-1), (VII-1)
and (VII-2), groups in which bonding positions are not fixed to any
of carbon atoms constituting the rings show that the bonding
positions thereof in the rings are optional; in Formula (VII-1),
plural R.sup.5 each are independently --CH.sub.3, --OCH.sub.3,
--CF.sub.3 or --COOCH.sub.3; and b is an integer of 0 to 2. [5] The
photo-aligning liquid crystal aligning agent as described in the
above item [4], wherein at least one of the tetracarboxylic acid
dianhydride having a photoreactive structure and the diamine having
a photoreactive structure is at least one selected from the group
of compounds represented by the following Formulas (VI-1-1),
(VII-1-1) and (VII-3):
##STR00003##
[6] The photo-aligning liquid crystal aligning agent as described
in any one of the above items [1] to [5], wherein the
tetracarboxylic acid dianhydride having no photoreactive structure
is at least one selected from the group of the compounds
represented by the following Formulas (AN-b) and (AN-c):
##STR00004##
in Formula (AN-b), X.sup.2 is alkylene having 1 to 8 carbon atoms.
[7] The photo-aligning liquid crystal aligning agent as described
in any one of the above items [1] to [6], wherein the diamine
having no photoreactive structure is at least one selected from the
group of compounds represented by the following Formulas (DI-b-1)
and (DI-b-2):
##STR00005##
[8] The photo-aligning liquid crystal aligning agent as described
in any one of the above items [1] to [7], wherein the
tetracarboxylic acid dianhydride having no photoreactive structure
is the compound represented by the following Formula (AN-b), and
the diamine having no photoreactive structure is the compound
represented by the following Formula (DI-b-2):
##STR00006##
in Formula (AN-b), X.sup.2 is alkylene having 1 to 8 carbon atoms.
[9] The photo-aligning liquid crystal aligning agent as described
in any one of the above items [1] to [8], wherein the
tetracarboxylic acid dianhydride having no photoreactive structure
which is used together with at least one selected from the group of
the compounds represented by Formulas (AN-a) to (AN-c) is at least
one selected from the group of compounds represented by the
following Formulas (AN-I) to (AN-VII):
##STR00007##
in Formulas (AN-I), (AN-1V) and (AN-V), plural X each are
independently a single bond or --CH.sub.2--; in Formula (AN-II), G
is a single bond, alkylene having 1 to 20 carbon atoms, --CO--,
--O--, --S--, --SO.sub.2--, --C(CH.sub.3).sub.2-- or
--C(CF.sub.3).sub.2--; in Formulas (AN-II) to (AN-1V), plural Y
each are independently one selected from the group of the following
trivalent groups:
##STR00008##
at least one hydrogen of the above groups may be substituted with
methyl, ethyl or phenyl; in Formula (AN-II), when Y is
2-azapropane-1,2,3-triyl, G described above is not alkylene having
1 to 20 carbon atoms, and when Y is benzene-1,2,4-triyl, G
described above is not alkylene having 1 to 8 carbon atoms and
--O--; in Formulas (AN-III) to (AN-V), a ring A is a monocyclic
hydrocarbon group having 3 to 10 carbon atoms or a condensed
polycyclic hydrocarbon group having 6 to 30 carbon atoms; at least
one hydrogen of the above group may be substituted with methyl,
ethyl or phenyl; an atomic bonding coupled with the ring is
connected with optional carbon constituting the ring, and two
atomic bondings may be connected with the same carbon; in Formula
(AN-VI), X.sup.10 is alkylene having 2 to 6 carbon atoms; Me is
methyl; and Ph is phenyl; in Formula (AN-VII), plural G.sup.10 each
are independently --O--, --COO-- or --OCO--; and plural r each are
independently 0 or 1. [10] The photo-aligning liquid crystal
aligning agent as described in the above item [9], wherein the
tetracarboxylic acid dianhydride having no photoreactive structure
which is used together with at least one selected from the group of
the compounds represented by Formulas (AN-a) to (AN-c) is at least
one selected from the group of compounds represented by the
following Formulas (AN-1-1), (AN-2-1), (AN-3-1), (AN-3-2), (AN-5-1)
and (AN-16-1):
##STR00009##
[11] The photo-aligning liquid crystal aligning agent as described
in any one of the above items [1] to [10], wherein the diamine
having no photoreactive structure which is used together with at
least one selected from the group of the compounds represented by
Formulas (DI-a) to (DI-c) is at least one selected from the group
of compounds represented by the following Formulas (DI-1) to
(DI-17):
##STR00010##
in Formula (DI-1), m is an integer of 1 to 12; in Formulas (DI-3),
(DI-6) and (DI-7), plural G.sup.21 each are independently a single
bond, --O--, --S--, --S--S--, --SO.sub.2--, CO--, --CONH--,
--NHCO--, --C(CH.sub.3).sub.2--, --C(CF.sub.3).sub.2--,
--C(CH.sub.2).sub.m'--, --O--(CH.sub.2).sub.m'--O-- or
--S--(CH.sub.2).sub.m'--S--, and plural m' each are independently
an integer of 1 to 12; in Formula (DI-5), G.sup.21 is a single
bond, --NH--, --O--, --S--, --S--S--, --SO.sub.2--, --CO--,
--CONH--, --NHCO--, --C(CH.sub.3).sub.2--, --C(CF.sub.3).sub.2--,
--C(CH.sub.2).sub.m--, --O--(CH.sub.2).sub.m'--O--,
--N--C(CH.sub.3)--(CH.sub.2).sub.k--N(CH.sub.3)-- or
--S--(CH.sub.2).sub.m'--S--; m' is an integer of 1 to 12, and m''
is an integer of 6 to 12; and k is an integer of 1 to 5; in
Formulas (DI-6) and (DI-7), plural G.sup.22 each are independently
a single bond, --O--, --S--, CO--, --C(CH.sub.3).sub.2--,
--C(CF.sub.3).sub.2-- or alkylene having 1 to 10 carbon atoms; at
least one hydrogen of a cyclohexane ring and a benzene ring in
Formulas (DI-3) to (DI-7) may be substituted with --F, --CH.sub.3,
--OH, --CF.sub.3, --CO.sub.2H--, --CONH.sub.2 or benzyl, and in
addition thereto, in Formula (DI-4), at least one hydrogen of the
benzene ring may be substituted with at least one of groups
represented the following Formulas (DI-4-a) to (DI-4-c):
##STR00011##
in Formulas (DI-4-a) and (DI-4-b), plural R.sup.20 each are
independently hydrogen or --CH.sub.3; in Formulas (DI-2) to (DI-7),
groups in which bonding positions are not fixed to any of carbon
atoms constituting the rings show that the bonding positions
thereof in the rings are optional; and the bonding position of
--NH.sub.2 in the cyclohexane ring or the benzene ring is an
optional position excluding the bonding position of G.sup.21 or
G.sup.22;
##STR00012##
in Formula (DI-8), R.sup.21 and R.sup.22 each are independently
alkyl having 1 to 3 carbon atoms or phenyl; plural G.sup.23 each
are independently alkylene having 1 to 6 carbon atoms, phenylene or
phenylene substituted with alkyl; w is an integer of 1 to 10; in
Formula (DI-9), plural R.sup.23 each are independently alkyl having
1 to 5 carbon atoms, alkoxy having 1 to 5 carbon atoms or Cl;
plural p each are independently an integer of 0 to 3, and q is an
integer of 0 to 4; and p and q are not 0 at the same time; in
Formula (DI-10), R.sup.24 is alkyl having 1 to 4 carbon atoms,
phenyl or benzyl; in Formula (DI-11), G.sup.24 is --CH.sub.2-- or
--NH--; in Formula (DI-12), G.sup.25 is a single bond, alkylene
having 2 to 6 carbon atoms or 1,4-phenylene; and r is 0 or 1; in
Formula (DI-12), groups in which bonding positions are not fixed to
any of carbon atoms constituting the rings show that the bonding
positions thereof in the rings are optional; in Formulas (DI-9),
(DI-11) and (DI-12), the bonding positions of --NH.sub.2 bonded to
the benzene rings are optional positions:
##STR00013##
in Formula (DI-13), G.sup.26 is a single bond, --O--, --COO--,
--OCO--, --CO--, --CONH--, --CH.sub.2O--, --OCH.sub.2--,
--CF.sub.2O--, --OCF.sub.2-- or --O--(CH.sub.2).sub.m'--, and m' is
an integer of 1 to 12; R.sup.25 is alkyl having 3 to 20 carbon
atoms, phenyl, cyclohexyl, a group having a steroid skeleton or a
group represented by the following Formula (DI-13-a); in the above
alkyl, at least one hydrogen may be substituted with --F, and at
least one --CH.sub.2-- may be substituted with --O--; hydrogen of
the above phenyl may be substituted with --F, --CH.sub.3,
--OCH.sub.3, --OCH.sub.2F, --OCHF.sub.2, --OCF.sub.3, alkyl having
3 to 20 carbon atoms or alkoxy having 3 to 20 carbon atoms;
hydrogen of the above cyclohexyl may be substituted with alkyl
having 3 to 20 carbon atoms or alkoxy having 3 to 20 carbon atoms;
the bonding position of --NH.sub.2 bonded to the benzene ring shows
that it is an optional position in the above ring:
##STR00014##
in Formula (DI-13-a), G.sup.27, G.sup.28 and G.sup.29 represent a
bonding group, and they each are independently a single bond or
alkylene having 1 to 12 carbon atoms; at least one --CH.sub.2-- in
the above alkylene may be substituted with --O--, --COO--, --OCO--,
--CONH-- or --CH.dbd.CH--; a ring B.sup.21, a ring B.sup.22, a ring
B.sup.23 and a ring B.sup.24 each are independently 1,4-phenylene,
1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl,
pyridine-2,5-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl,
naphthalene-2,6-diyl, naphthalene-2,7-diyl or anthracene-9,10-diyl;
in the ring B.sup.21, the ring B.sup.22, the ring B.sup.23 and the
ring B.sup.24, at least one hydrogen may be substituted with --F or
--CH.sub.3; s, t and u each are independently an integer of 1 to 5,
and a total thereof is 1 to 5; when s, t or u is 2, two bonding
groups in each parenthesis may be the same or different, and two
rings may be the same or different; R.sup.26 is --F, --OH, alkyl
having 1 to 30 carbon atoms, fluorine-substituted alkyl having 1 to
30 carbon atoms, alkoxy having 1 to 30 carbon atoms, --CN,
--OCH.sub.2F, --OCHF.sub.2 or --OCF.sub.3, and at least one
--CH.sub.2-- in the above alkyl having 1 to 30 carbon atoms may be
substituted with a divalent group represented by the following
Formula (DI-13-b):
##STR00015##
in Formula (DI-13-b), R.sup.27 and R.sup.28 each are independently
alkyl having 1 to 3 carbon atoms; and v is an integer of 1 to
6;
##STR00016##
in Formulas (DI-14) and (DI-15), plural G.sup.30 each are
independently a single bond, --CO-- or --CH.sub.2--; plural
R.sup.29 each are independently hydrogen or --CH.sub.3; R.sup.30 is
hydrogen, alkyl having 1 to 20 carbon atoms or alkenyl having 2 to
20 carbon atoms; one hydrogen of a benzene ring in Formula (DI-15)
may be substituted with alkyl having 1 to 20 carbon atoms or
phenyl; in Formulas (DI-14) and (DI-15), groups in which bonding
positions are not fixed to any of carbon atoms constituting the
rings show that the bonding positions thereof in the rings are
optional; --NH.sub.2 bonded to the benzene ring shows that the
bonding position thereof in the ring is optional:
##STR00017##
in Formulas (DI-16) and (DI-17), plural G.sup.31 each are
independently --O-- or alkylene having 1 to 6 carbon atoms;
G.sup.32 is a single bond or alkylene having 1 to 3 carbon atoms;
R.sup.31 is hydrogen or alkyl having 1 to 20 carbon atoms, and at
least one --CH.sub.2-- of the above alkyl may be substituted with
--O--; R.sup.32 is alkyl having 6 to 22 carbon atoms; R.sup.33 is
hydrogen or alkyl having 1 to 22 carbon atoms; a ring B.sup.25 is
1,4-phenylene or 1,4-cyclohexylene; r is 0 or 1; and --NH.sub.2
bonded to the benzene ring shows that the bonding position thereof
in the ring is optional. [12] The photo-aligning liquid crystal
aligning agent as described in the above item [11], wherein the
diamine having no photoreactive structure which is used together
with at least one selected from the group of the compounds
represented by Formulas (DI-a) to (DI-c) is at least one selected
from the group of compounds represented by the following Formulas
(DI-4-1), (DI-5-9), (DI-5-12), (DI-5-27), (DI-5-30) and
(DI-7-3):
##STR00018##
in Formula (DI-5-12) and (DI-7-3), m is an integer of 1 to 12; in
Formula (DI-5-30), k is an integer of 1 to 5; and
in Formula (DI-7-3), n is 1 or 2.
[0018] [13] The photo-aligning liquid crystal aligning agent as
described in any one of the above items [1] to [12], further
comprising at least one selected from the group of compounds
consisting of alkenyl-substituted nadiimide compounds, compounds
having a radically polymerizable unsaturated double bond, oxazine
compounds, oxazoline compounds, epoxy compounds and silane coupling
agents. [14] The photo-aligning liquid crystal aligning agent as
described in the above item [13], wherein the alkenyl-substituted
nadiimide compound is at least one selected from the group of
compounds consisting of
bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenyl}methane,
N,N'-m-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)
and
N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide).
[15] The photo-aligning liquid crystal aligning agent as described
in the above item [13], wherein the epoxy compound is at least one
selected from the group of compounds consisting of
N,N,N',N'-tetraglycidyl-m-xylylenediamine,
1,3-bis(N,N-diglycidylaminomethyl)cyclohexane,
N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane,
2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-([2,3-epoxypropoxy]phenyl]-
ethyl]phenyl]propane,
3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate and
N-phenylmaleimide-glycidyl methacrylate copolymers. [16] The
photo-aligning liquid crystal aligning agent as described in the
above item [13], wherein the silane coupling agent is at least one
selected from the group of compounds consisting of
2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,
paraaminophenyltrimethoxysilane and 3-aminopropyltriethoxysilane.
[17] A photo-aligning liquid crystal alignment layer formed by the
photo-aligning liquid crystal aligning agent as described in any
one of the above items [1] to [16]. [18] A photo-aligning liquid
crystal alignment layer formed by passing through a step of coating
the photo-aligning liquid crystal aligning agent as described in
any one of the above items [1] to [16] on a substrate, a step of
heating and drying the substrate coated with the aligning agent and
a step of irradiating the dried layer with a polarized UV ray. [19]
A photo-aligning liquid crystal alignment layer formed by passing
through a step of coating the photo-aligning liquid crystal
aligning agent as described in any one of the above items [1] to
[16] on a substrate, a step of heating and drying the substrate
coated with the aligning agent, a step of irradiating the dried
membrane with a polarized UV ray and then a step of heating and
baking the layer. [20] A photo-aligning liquid crystal alignment
layer formed by passing through a step of coating the
photo-aligning liquid crystal aligning agent as described in any
one of the above items [1] to [16] on a substrate, a step of
heating and drying the substrate coated with the aligning agent, a
step of heating and baking the dried layer and then a step of
irradiating the layer with a polarized UV ray. [21] A liquid
crystal display device comprising the photo-aligning liquid crystal
alignment layer as described in any one of the above items [17] to
[20].
[0019] Use of the photo-aligning liquid crystal alignment layer
formed by the photo-aligning liquid crystal aligning agent of the
present invention makes it possible to reduce storage of residual
DC in the liquid crystal display device and shorten a relaxation
time thereof and makes it possible to prevent afterimages from
being generated therein.
[0020] The terms used in the present invention shall be explained.
The term "optional" used in defining chemical structural formulas
shows that not only the positions but also the numbers are
optional. In the chemical structural formulas, groups in which
characters (for example, A or B.sup.21 to B.sup.26) are surrounded
by circles mean groups (A or B.sup.21 to B.sup.26) of a ring
structure. Groups in which characters (for example, A or B.sup.21
to B.sup.26) are surrounded by hexagons mean groups (A or B.sup.21
to B.sup.26) of a six-membered ring structure.
<Photo-Aligning Liquid Crystal Aligning Agent>
[0021] The photo-aligning liquid crystal aligning agent of the
present invention contains polyamic acid or a derivative thereof
which is a reaction product of tetracarboxylic acid dianhydride
with diamine. The derivative of the polyamic acid described above
is a component dissolved in the solvent when a liquid crystal
aligning agent containing a solvent is prepared, and it is a
component from which a liquid crystal alignment layer comprising
polyimide as a principal component can be formed when a liquid
crystal alignment layer described later is prepared by the liquid
crystal aligning agent. The above derivative of the polyamic acid
includes, for example, soluble polyimide, polyamic acid esters,
polyamic acid amides and the like, and it includes, to be more
specific, 1) polyimides prepared by subjecting all aminos and
carboxyls of polyamic acid to dehydration cyclization, 2) partial
polyamides prepared by partially subjecting them to dehydration
cyclization, 3) polyamic acid esters obtained by converting
carboxyls of polyamic acid to esters, 4) polyamic acid-polyamide
copolymers obtained by replacing a part of dianhydride contained in
tetracarboxylic acid dianhydride by organic dicarboxylic acid and
reacting it with diamine and 5) polyimides prepared by subjecting a
part or a whole part of the above polyamic acid-polyamide
copolymers to dehydration cyclization. The polyamic acid or the
derivative thereof described above may comprise a single compound
or two or more compounds.
[0022] The term "tetracarboxylic acid dianhydride" used in the
present specification shows a tetracarboxylic acid dianhydride
single substance in a certain case and shows a mixture of plural
tetracarboxylic acids dianhydride in another case. Similarly, the
term "diamine" used therein shows a single substance in a certain
case and shows a mixture of plural diamines in another case.
[0023] The polyamic acid or derivative thereof used for the
photo-aligning liquid crystal aligning agent of the present
invention has a photoreactive structure in a constitutional unit
thereof. The above photoreactive structure is brought about by
using at least one of tetracarboxylic acid dianhydride having a
photoreactive structure and diamine having a photoreactive
structure for the raw material. The above polyamic acid or
derivative thereof is characterized by being obtained by reacting
tetracarboxylic acid dianhydride having no photoreactive structure
including at least one selected from the compounds represented by
the following Formulas (AN-a) to (AN-c) and diamine having no
photoreactive structure including at least one selected from the
compounds represented by the following Formulas (DI-a) to (DI-c)
together with at least one of tetracarboxylic acid dianhydride
having a photoreactive structure and diamine having a photoreactive
structure;
##STR00019##
in Formula (AN-a), X.sup.2 is a single bond or alkylene having 1 to
20 carbon atoms; in Formula (AN-b), X.sup.2 is alkylene having 1 to
8 carbon atoms; in Formula (DI-b), R.sup.2 is hydrogen or --CH3,
and a is an integer of 1 to 5; and in Formulas (DI-a) and (DI-b),
groups in which bonding positions are not fixed to any of carbon
atoms constituting the rings show that the bonding positions
thereof in the rings are optional.
<Photoreactive Structure>
[0024] The photoreactive structure can be selected from all
publicly known photoreactive structures which bring about
isomerization, photodecomposition, dimerization reaction and the
like by irradiation with light. Photosensitive groups causing
photoisomerization or dimerization reaction are preferably used
from the viewpoint of a photosensitivity.
[0025] The tetracarboxylic acid dianhydride having a photoreactive
structure or the diamine having a photoreactive structure each
described above is preferably at least one selected from the group
of compounds having a good photosensitivity which are represented
by the following Formulas (I) to (VII):
R.sup.2--C.ident.C--R.sup.3 (I)
R.sup.2--C.ident.C--C.ident.C--R.sup.3 (II)
R.sup.2--C.ident.C--CH.dbd.CH--R.sup.3 (III)
R.sup.2--C.ident.C--R.sup.4--C.ident.C--R.sup.3 (IV)
R.sup.2--C.ident.C--R.sup.4--CH.dbd.CH--R.sup.3 (V)
R.sup.2--CH.dbd.CH--R.sup.3 (VI)
R.sup.2--N.dbd.N--R.sup.3 (VII)
in Formulas (I) to (VII), R.sup.2 and R.sup.3 each are
independently a monovalent organic group having NH.sub.2 or a
monovalent organic group having --CO--O--CO--, and R.sup.4 is a
divalent organic group having an aromatic ring.
[0026] The photoreactive structure may be incorporated into either
a principal chain or a side chain of the polyamic acid or the
derivative thereof in the present invention, and it can suitably be
used for liquid crystal devices of a lateral electric field by
incorporating the structure into the principal chain.
[0027] Capable of being used as the material having the
photoreactive structure described above is at least one selected
from the group of compounds represented by the following Formulas
(I-1), (II-1), (III-1), (IV-1), (IV-2), (V-1), (VI-1) and (VII-1)
to (VII-3):
##STR00020##
in Formulas (I-1), (II-1), (III-1), (IV-1), (V-1), (VI-1), (VII-1)
and (VII-2), groups in which bonding positions are not fixed to any
of carbon atoms constituting the rings show that the bonding
positions thereof in the rings are optional; in Formula (VII-1),
plural R.sup.5 each are independently --CH.sub.3, --OCH.sub.3,
--CF.sub.3 or --COOCH.sub.3; and b is an integer of 0 to 2.
[0028] The compounds represented by Formulas (VI-1), (VII-1) and
(VII-3) can particularly suitably be used from the viewpoint of a
photosensitivity. The compounds in which a bonding position of an
amino group is a para position in Formulas (VI-1) and (VII-1) and
the compounds in which b is 0 in Formula (VII-1) can more suitably
be used from the viewpoint of the aligning property.
[0029] In an embodiment in which the tetracarboxylic acid
dianhydride having no photoreactive structure (non-photosensitive)
and the tetracarboxylic acid dianhydride having a photoreactive
structure (photosensitive) are used in combination, the
photosensitive tetracarboxylic acid dianhydride accounts for
preferably 0 to 70 mole %, particularly preferably 0 to 50 mole %
based on a whole amount of the tetracarboxylic acids dianhydride
used as the raw material in producing the polyamic acid or
derivative thereof according to the present invention in order to
prevent the alignment layer from being reduced in a sensitivity to
light. Also, in order to improve the foregoing various
characteristics such as the sensitivity to light, the electric
characteristics, the afterimage characteristic and the like, two or
more tetracarboxylic acids dianhydride may be used in
combination.
[0030] In an embodiment in which the diamine having no
photoreactive structure (non-photosensitive) and the diamine having
a photoreactive structure (photosensitive) are used in combination,
the photosensitive diamine accounts for preferably 20 to 100 mole
%, particularly preferably 50 to 100 mole % based on a whole amount
of the diamines used as the raw material in producing the polyamic
acid or derivative thereof according to the present invention in
order to prevent the alignment layer from being reduced in a
sensitivity to light. Also, in order to improve the foregoing
various characteristics such as the sensitivity to light, the
afterimage characteristic and the like, two or more diamines may be
used in combination. As described above, a case in which the
non-photosensitive tetracarboxylic acid dianhydride accounts for a
whole amount of the tetracarboxylic acids dianhydride is included
in the embodiment of the present invention, and in the above case,
the photosensitive diamine is required to account for minimum 20
mole % based on a whole amount of the diamines.
[0031] In order to improve the foregoing various characteristics
such as the sensitivity to light, the afterimage characteristic and
the like, the photosensitive tetracarboxylic acid dianhydride and
the photosensitive diamine may be used in combination, and two or
more compounds thereof may be used in combination respectively.
<Non-Photosensitive Tetracarboxylic Acid Dianhydride>
[0032] In the non-photosensitive tetracarboxylic acids dianhydride
represented by Formulas (AN-a) to (AN-c), the compounds represented
by Formulas (AN-a) and (AN-b) are preferably used when further
improvement in an aligning property of the liquid crystal is
regarded as important; the compound represented by Formula (AN-a)
is preferably used when further improvement in a VHR of the liquid
crystal display device is regarded as important; the compounds
represented by Formulas (AN-a) and (AN-b) are preferably used when
an inhibition in storage of a residual DC of the liquid crystal
alignment layer is regarded as important; and the compounds
represented by Formulas (AN-b) and (AN-c) are preferably used when
shortening a relaxation time in a residual DC of the liquid crystal
alignment layer is regarded as important. Preferably used is the
compound represented by Formula (AN-b) which can satisfy the
various characteristics described above in a good balance can more
suitably be used.
[0033] In Formula (AN-b) described above, X.sub.2 is particularly
preferably alkylene having 4 to 8 carbon atoms.
[0034] The tetracarboxylic acids dianhydride represented by
Formulas (AN-a) to (AN-c) account for preferably 50 to 100 mole %,
more preferably 70 to 100 mole % based on a whole amount of the
tetracarboxylic acids dianhydride used as the raw material in
producing the polyamic acid or derivative thereof according to the
present invention in order to satisfy the various characteristics
described above.
<Non-Photosensitive Diamine>
[0035] In the non-photosensitive diamines represented by Formulas
(DI-a) to (DI-c), the compounds represented by Formulas (DI-b) and
(DI-c) are preferably used when further improvement in an aligning
property of the liquid crystal is regarded as important; the
compounds represented by Formulas (DI-a) and (DI-c) are preferably
used when further improvement in a VHR of the liquid crystal
display device is regarded as important; the compounds represented
by Formulas (DI-a) and (DI-c) are preferably used when an
inhibition in storage of a residual DC of the liquid crystal
alignment layer is regarded as important; and the compound
represented by Formula (DI-b) is preferably used when shortening a
relaxation time in a residual DC of the liquid crystal alignment
layer is regarded as important. The compound represented by Formula
(DI-b) which can satisfy the various characteristics described
above in a good balance can more preferably be used.
[0036] In Formula (DI-b), a is preferably 2 or 4, more preferably
4.
[0037] The diamines represented by Formulas (DI-a) to (DI-c)
account for preferably 20 to 100 mole %, more preferably 20 to 50
mole % based on a whole amount of the diamines used as the raw
material in producing the polyamic acid or derivative thereof
according to the present invention in order to satisfy the various
characteristics described above.
[0038] In the combinations of the tetracarboxylic acids dianhydride
represented by Formulas (AN-a) to (AN-c) and the diamines
represented by Formulas (DI-a) to (DI-c), the tetracarboxylic acid
dianhydride represented by Formula (AN-b) and the diamine
represented by Formula (DI-b) can suitably be used for satisfying
the various characteristics described above. The compound in which
X.sup.2 is alkylene having 4 to 8 carbon atoms in Formula (AN-b)
and the compound in which a is 6, in which R.sup.2 is hydrogen and
in which a bonding position of amine is a para position in Formula
(DI-b) can particularly suitably be used.
<Other Tetracarboxylic Acids Dianhydride>
[0039] In producing the polyamic acid or derivative thereof
according to the present invention, "other tetracarboxylic acids
dianhydride" other than the photosensitive tetracarboxylic acids
dianhydride described above and the non-photosensitive
tetracarboxylic acids dianhydride represented by Formulas (AN-a) to
(AN-c) can be used. The other tetracarboxylic acids dianhydride can
be selected from publicly known tetracarboxylic acids dianhydride
without being limited. Such tetracarboxylic acids dianhydride may
be compounds belonging to either group of aromatic compounds
(including heteroaromatic compounds) in which dicarboxylic acid
anhydride is bonded directly to an aromatic ring and aliphatic
compounds (including heteroaromatic compounds) in which
dicarboxylic acid anhydride is not bonded directly to an aromatic
ring.
[0040] The suitable examples of the other tetracarboxylic acids
dianhydride include tetracarboxylic acids dianhydride represented
by (AN-I) to (AN-VII) from the viewpoints of an availability of the
raw materials, easiness in producing the polymer and the electric
characteristics of the layer:
##STR00021##
in Formulas (AN-I), (AN-1V) and (AN-V), plural X each are
independently a single bond or --CH.sub.2--; in Formula (AN-II), G
is a single bond, alkylene having 1 to 20 carbon atoms, --CO--,
--O--, --S--, --SO.sub.2--, --C(CH.sub.3).sub.2-- or
--C(CF.sub.3).sub.2--; in Formulas (AN-II) to (AN-1V), plural Y
each are independently one selected from the group of the following
trivalent groups, and the atomic bondings are connected with
optional carbons; at least one hydrogen of the above groups may be
substituted with methyl, ethyl or phenyl; in Formula (AN-II), when
Y is 2-azapropane-1,2,3-triyl, G described above is not alkylene
having 1 to 20 carbon atoms, and when Y is benzene-1,2,4-triyl, G
described above is not alkylene having 1 to 8 carbon atoms and
--O--;
##STR00022##
in Formulas (AN-III) to (AN-V), a ring A is a monocyclic
hydrocarbon group having 3 to 10 carbon atoms or a condensed
polycyclic hydrocarbon group having 6 to 30 carbon atoms; at least
one hydrogen of the above group may be substituted with methyl,
ethyl or phenyl; an atomic bonding coupled with the ring is
connected with optional carbon constituting the ring, and two
atomic bondings may be connected with the same carbon; in Formula
(AN-VI), X.sup.10 is alkylene having 2 to 6 carbon atoms; Me is
methyl; and Ph is phenyl; in Formula (AN-VII), plural G.sup.10 each
are independently --O--, --COO-- or --OCO--; and plural r each are
independently 0 or 1.
[0041] To be more specific, tetracarboxylic acids dianhydride
represented by Formulas (AN-1) to (AN-16-14) are listed:
##STR00023##
in Formula (AN-1), G.sup.11 is a single bond, alkylene having 1 to
12 carbon atoms, 1,4-phenylene or 1,4-cyclohexylene; plural
X.sup.11 each are independently a single bond or --CH.sub.2--;
plural G.sup.12 each are independently >CH-- or >N--; when
G.sup.12 is >CH--, hydrogen of >CH-- may be substituted with
--CH.sub.3; when G.sup.12 is >N--, G.sup.11 is not a single bond
and --CH.sub.2--, and X.sup.11 is not a single bond; and R.sup.11
is hydrogen or --CH.sub.3. Compounds represented by the following
formulas can be listed as the examples of the tetracarboxylic acid
dianhydride represented by Formula (AN-1):
##STR00024## ##STR00025##
in Formulas (AN-1-2) and (AN-1-3), m is an integer of 1 to 12.
##STR00026##
in Formula (AN-2), plural R.sup.11 each are independently hydrogen,
--CH.sub.3, --CH.sub.2CH.sub.3 or phenyl. Compounds represented by
the following formulas can be listed as the examples of the
tetracarboxylic acid dianhydride represented by Formula (AN-2):
##STR00027##
in Formula (AN-3), a ring A.sup.11 is a cyclohexene ring or a
benzene ring. Compounds represented by the following formulas can
be listed as the examples of the tetracarboxylic acid dianhydride
represented by Formula (AN-3):
##STR00028##
in Formula (AN-4), G.sup.13 is a single bond, --CH.sub.2--,
--CH.sub.2CH.sub.2--, --O--, --S--, --C(CH.sub.3).sub.2--,
--SO.sub.2--, --CO-- or --C(CF.sub.3).sub.2--; plural rings
A.sup.11 each are independently a cyclohexane ring or a benzene
ring; G.sup.13 may be bonded to an optional position of the ring
A.sup.11. Compounds represented by the following formulas can be
listed as the examples of the tetracarboxylic acid dianhydride
represented by Formula (AN-4):
##STR00029## ##STR00030## ##STR00031## ##STR00032##
in Formula (AN-5), R.sup.11 is hydrogen or --CH.sub.3; and R.sup.11
in which a bonding position is not fixed to carbon atoms
constituting the benzene ring shows that the bonding position
thereof in the benzene ring is optional. Compounds represented by
the following formulas can be listed as the examples of the
tetracarboxylic acid dianhydride represented by Formula (AN-5):
##STR00033##
in Formula (AN-6), plural X.sup.11 each are independently a single
bond or --CH.sub.2--; plural X.sup.12 each are independently
--CH.sub.2--, --CH.sub.2CH.sub.2-- or --CH.dbd.CH--; and n is 1 or
2. Compounds represented by the following formulas can be listed as
the examples of the tetracarboxylic acid dianhydride represented by
Formula (AN-6):
##STR00034## ##STR00035##
in Formula (AN-7), X.sup.11 is a single bond or --CH.sub.2--.
Compounds represented by the following formulas can be listed as
the examples of the tetracarboxylic acid dianhydride represented by
Formula (AN-7):
##STR00036##
in Formula (AN-8), X.sup.11 is a single bond or --CH.sub.2--;
R.sup.12 is hydrogen, --CH.sub.3, --CH.sub.2CH.sub.3 or phenyl; and
a ring A.sup.12 is a cyclohexane ring or a cyclohexene ring.
Compounds represented by the following formulas can be listed as
the examples of the tetracarboxylic acid dianhydride represented by
Formula (AN-8):
##STR00037##
in Formula (AN-9), plural r each are independently 0 or 1.
Compounds represented by the following formulas can be listed as
the examples of the tetracarboxylic acid dianhydride represented by
Formula (AN-9):
##STR00038##
[0042] Formula (AN-10) represents the following tetracarboxylic
acid dianhydride:
##STR00039##
in Formula (AN-11), plural rings A.sup.11 each are independently a
cyclohexane ring or a benzene ring. Compounds represented by the
following formulas can be listed as the examples of the
tetracarboxylic acid dianhydride represented by Formula
(AN-11):
##STR00040##
in Formula (AN-12), plural rings A.sup.11 each are independently a
cyclohexane ring or a benzene ring. Compounds represented by the
following formulas can be listed as the examples of the
tetracarboxylic acid dianhydride represented by Formula
(AN-12):
##STR00041##
in Formula (AN-13), X.sup.13 is alkylene having 2 to 6 carbon
atoms, and Ph represents phenyl. Compounds represented by the
following formulas can be listed as the examples of the
tetracarboxylic acid dianhydride represented by Formula
(AN-13):
##STR00042##
in Formula (AN-14), plural G.sup.14 each are independently --O--,
--COO-- or --OCO--, and plural r each are independently 0 or 1.
Compounds represented by the following formulas can be listed as
the examples of the tetracarboxylic acid dianhydride represented by
Formula (AN-14):
##STR00043##
in Formula (AN-15), w is an integer of 1 to 10. Compounds
represented by the following formulas can be listed as the examples
of the tetracarboxylic acid dianhydride represented by Formula
(AN-15):
##STR00044##
[0043] Tetracarboxylic acids dianhydride other than the compounds
described above include the following compounds:
##STR00045## ##STR00046##
[0044] When further improvement in an aligning property of the
liquid crystal is regarded as important, among the tetracarboxylic
acids dianhydride described above, more preferred are the compounds
represented by Formulas (AN-1-1), (AN-1-3), (AN-2-1), (AN-3-2),
(AN-4-5), (AN-5-1), (AN-7-2), (AN-8-1), (AN-11-3), (AN-16-3) and
(AN-16-14), and the compounds represented by Formulas (AN-1-1),
(AN-3-2), (AN-11-3) and (AN-16-14) are particularly preferred.
[0045] When further improvement in a VHR of the liquid crystal
display device is regarded as important, among the tetracarboxylic
acids dianhydride described above, more preferred are the aliphatic
compounds represented by Formulas (AN-1-1), (AN-1-4), (AN-2-1),
(AN-3-1), (AN-5-1), (AN-6-3), (AN-7-1), (AN-7-2), (AN-8-1),
(AN-9-3), (AN-10), (AN-13-1), (AN-16-1), (AN-16-3) and (AN-16-4),
and the compounds represented by Formulas (AN-1-4), (AN-2-1),
(AN-3-1), (AN-7-2), (AN-10), (AN-13-1) and (AN-16-1) are
particularly preferred.
[0046] When an inhibition in storage of a residual DC of the liquid
crystal alignment layer is regarded as important, among the
tetracarboxylic acids dianhydride described above, the compounds
represented by Formulas (AN-3-2) and (AN-11-3) are more
preferred.
[0047] When shortening a relaxation time in a residual DC of the
liquid crystal alignment layer is regarded as important, among the
tetracarboxylic acids dianhydride described above, the compounds
represented by Formulas (AN-3-2) and (AN-16-14) are more
preferred.
[0048] The compounds represented by Formulas (AN-1-1), (AN-2-1) and
(AN-3-2) which satisfy the various characteristics described above
in a good balance can more suitably be used.
<Other Diamines>
[0049] In producing the polyamic acid or derivative thereof
according to the present invention, "other diamines" other than the
photosensitive diamines described above and the non-photosensitive
diamines represented by Formulas (DI-a) to (DI-c) each can be used.
The other diamines can be selected from publicly known diamines
without being limited.
[0050] In this connection, the structures of the other diamines
shall be explained. The other diamines can be divided into two
kinds according to the structures thereof. That is, assuming that a
skeleton connecting two amino groups is regarded as a principal
chain, one is diamine having a group branching from the principal
chain, that is, a side chain group, and the other is diamine having
no side chain group. The above side chain group has an effect of
increasing the pre-tilt angle. The side chain group having the
above effect has to be a group having 3 or more carbon atoms, and
the specific examples thereof include alkyl having 3 or more carbon
atoms, alkoxy having 3 or more carbon atoms and a group having a
steroid skeleton. Groups which have at least one ring and in which
a ring at an end thereof has any one of alkyl having one or more
carbon atoms, alkoxy having one or more carbon atoms and
alkoxyalkyl having two or more carbon atoms as a substituent have
as well the effect of the side chain group. In the following
explanations, diamines having the above side chain group shall be
referred to as side chain type diamines, and diamines having no
such side chain group shall be referred to as non-side chain type
diamines.
[0051] Proper use of the non-side chain type diamines and the side
chain type diamines makes it possible to meet the pre-tilt angles
necessary for the respect compounds. The side chain type diamines
are preferably used in combination as long as the characteristics
of the present invention are not damaged. Also, the side chain type
diamines and the non-side chain type diamines are preferably
selected and used for the purpose of improving the vertical
aligning property to liquid crystal, the voltage holding property,
the yellowing characteristic and the photo-aligning property.
<Non-Side Chain Type Diamine>
[0052] Diamines represented by the following Formulas (DI-1) and
(DI-3) to (DI-12) can be listed as publicly known diamines having
no side chains:
##STR00047##
in Formula (DI-1), m is an integer of 1 to 12; in Formulas (DI-3),
(DI-6) to (DI-7), plural G.sup.21 each are independently a single
bond, --O--, --S--, --S--S--, --SO.sub.2--, CO--, --CONH--,
--NHCO--, --C(CH.sub.3).sub.2--, --C(CF.sub.3).sub.2--,
--C(CH.sub.3).sub.m'--, --O--(CH.sub.2).sub.m'--O-- or
--S--(CH.sub.2).sub.m'--S--, and plural m' each are independently
an integer of 1 to 12; in Formula (DI-5), G.sup.21 is a single
bond, --NH--, --O--, --S--, --S--S--, --SO.sub.2--, --CO--,
--CONH--, --NHCO--, --C(CH.sub.3).sub.2--, --C(CF.sub.3).sub.2--,
--C(CH.sub.2).sub.m''--, --O--(CH.sub.3).sub.m'--O--,
--N--C(CH.sub.3)--(CH.sub.3).sub.k--N(CH.sub.3)-- or
--S--(CH.sub.2).sub.m'--S--; m' an integer of 1 to 12, and m'' is
an integer of 6 to 12; and k' is an integer of 1 to 5; in Formulas
(DI-6) and (DI-7), plural G.sup.22 each are independently a single
bond, --O--, --S--, CO--, --C(CH.sub.3).sub.2--,
--C(CF.sub.3).sub.2-- or alkylene having 1 to 10 carbon atoms; at
least one hydrogen of a cyclohexane ring and a benzene ring in
Formulas (DI-3) to (DI-7) may be substituted with --F, --CH.sub.3,
--OH, --CF.sub.3, --CO.sub.2H--, --CONH.sub.2 or benzyl, and in
addition thereto, in Formula (DI-4), at least one hydrogen of a
benzene ring may be substituted with groups represented by the
following Formulas (DI-4-a) to (DI-4-c); in Formulas (DI-2) to
(DI-7), groups in which bonding positions are not fixed to any of
carbon atoms constituting the rings show that the bonding positions
thereof in the rings are optional; and the bonding position of
--NH.sub.2 in the cyclohexane ring or the benzene ring is an
optional position excluding the bonding position of G.sup.21 or
G.sup.22:
##STR00048##
in Formulas (DI-4-a) and (DI-4-b), plural R.sup.20 each are
independently hydrogen or --CH.sub.3:
##STR00049##
in Formula (DI-8), plural R.sup.21 and R.sup.22 each are
independently alkyl having 1 to 3 carbon atoms or phenyl; plural
G.sup.23 each are independently alkylene having 1 to 6 carbon
atoms, phenylene or phenylene substituted with alkyl; w is an
integer of 1 to 10; in Formula (DI-9), plural R.sup.23 each are
independently alkyl having 1 to 5 carbon atoms, alkoxy having 1 to
5 carbon atoms or Cl; plural p each are independently an integer of
0 to 3, and q is an integer of 0 to 4; and p and q are not 0 at the
same time; in Formula (DI-10), R.sup.24 is hydrogen, alkyl having 1
to 4 carbon atoms, phenyl or benzyl; in Formula (DI-11), G.sup.24
is --CH.sub.2-- or --NH--; in Formula (DI-12), G.sup.25 is a single
bond, alkylene having 2 to 6 carbon atoms or 1,4-phenylene; and r
is 0 or 1; groups in which bonding positions are not fixed to any
of carbon atoms constituting the rings show that the bonding
positions thereof in the rings are optional; in Formulas (DI-9),
(DI-11) and (DI-12), the bonding positions of --NH.sub.2 bonded to
the benzene rings are optional positions.
[0053] Compounds represented by the following Formulas (DI-1-1) to
(DI-12-1) can be listed as the specific examples of the diamines
having no side chain groups represented by Formulas (DI-1) to
(DI-12) described above.
[0054] The examples of the diamines represented by Formulas (DI-1)
to (DI-3) are shown below:
##STR00050##
[0055] The examples of the diamine represented by Formula (DI-4)
are shown below:
##STR00051## ##STR00052##
[0056] The examples of the diamine represented by Formula (DI-5)
are shown below:
##STR00053##
in Formula (DI-5-12), m is an integer of 1 to 12;
##STR00054##
in Formula (DI-5-15), v is an integer of 1 to 6;
##STR00055##
in Formula (DI-5-30), k is an integer of 1 to 5.
[0057] The examples of the diamine represented by Formula (DI-6)
are shown below:
##STR00056##
[0058] The examples of the diamine represented by Formula (DI-7)
are shown below:
##STR00057##
in Formula (DI-7-3) and (DI-7-4), m is an integer of 1 to 12, and
plural n each are independently 1 or 2;
##STR00058##
[0059] The example of the diamine represented by Formula (DI-8) is
shown below:
##STR00059##
[0060] The examples of the diamine represented by Formula (DI-9)
are shown below:
##STR00060## ##STR00061##
[0061] The examples of the diamine represented by Formula (DI-10)
are shown below:
##STR00062##
[0062] The examples of the diamine represented by Formula (DI-11)
are shown below:
##STR00063##
[0063] The example of the diamine represented by Formula (DI-12) is
shown below:
##STR00064##
[0064] The above non-side chain type diamines have the effect of
improving the electric characteristics such as a reduction in an
ion density of the liquid crystal display device. When the non-side
chain type diamine is used for producing the polyamic acid or
polyimide used for the liquid crystal aligning agent of the present
invention, a proportion thereof based on a whole amount of the
diamines is preferably 0 to 80 mole %, more preferably 0 to 50 mole
%.
<Side Chain Type Diamine>
[0065] The following groups can be listed as the side chain group
of the side chain type diamine.
[0066] The side chain includes alkyl, alkyloxy, alkyloxyalkyl,
alkylcarbonyl, alkylcarbonyloxy, alkyloxycarbonyl,
alkylaminocarbonyl, alkenyl, alkenyloxy, alkenylcarbonyl,
alkenylcarbonyloxy, alkenyloxycarbonyl, alkenylaminocarbonyl,
alkynyl, alkynyloxy, alkynylcarbonyl, alkynylcarbonyloxy,
alkynyloxycarbonyl, alkynylaminocarbonyl and the like. All of
alkyl, alkenyl and alkynyl in the above groups are groups having 3
or more carbon atoms. In a case of alkyloxyalkyl, the group may
have 3 or more carbon atoms in total. The above groups may be
either linear or branched.
[0067] Next, on the condition that the ring at the end has alkyl
having one or more carbon atoms, alkoxy having one or more carbon
atoms or alkyloxyalkyl having 2 or more carbon atoms as a
substituent, capable of being listed are groups of a ring
structure, such as phenyl, phenylalkyl, phenylalkyloxy,
phenylcarbonyl, phenylcarbonyloxy, phenyloxycarbonyl,
phenylaminocarbonyl, phenylcyclohexyloxy, cycloalkyl having 3 or
more carbon atoms, cyclohexylalkyl, cyclohexyloxy,
cycloxexyloxycarbonyl, cyclohexylphenyl, cyclohexylphenylalkyl,
cyclohexylphenyloxy, bis(cyclohexyl)oxy, bis(cyclohexyl)alkyl,
bis(cyclohexyl)phenyl, bis(cyclohexyl)phenylalkyl,
bis(cyclohexyl)oxycarbonyl, bis(cyclohexyl)phenyloxycarbonyl,
cyclohexylbis(phenyl)oxycarbonyl and the like.
[0068] Further, capable of being listed are ring-condensed groups
which are a group having 2 or more benzene rings, a group having 2
or more cyclohexane rings or a bicyclic or more group constituted
by a benzene ring and a cyclohexane ring, wherein plural bonding
groups each are independently a single bond, --O--, --COO--,
--OCO--, --CONH-- or alkylene having 1 to 3 carbon atoms, and the
ring at the end has alkyl having one or more carbon atoms,
fluorine-substituted alkyl having one or more carbon atoms or
alkyloxyalkyl having 2 or more carbon atoms as a substituent.
Groups having a steroid skeleton are also effective as the side
chain group.
[0069] Diamines represented by the following Formulas (DI-13) to
(DI-17) can be listed as the diamines having side chains:
##STR00065##
in Formula (DI-13), G.sup.26 is a single bond, --O--, --COO--,
--OCO--, --CO--, --CONH--, --CH.sub.2O--, --OCH.sub.2--,
--CF.sub.2O--, --OCF.sub.2-- or --O--(CH.sub.2).sub.m'--, and m' is
an integer of 1 to 12; the preferred examples of G.sup.26 are a
single bond, --O--, --COO--, --OCO--, --CH.sub.2O-- and alkylene
having 1 to 3 carbon atoms, and the particularly preferred examples
are a single bond, --O--, --COO--, --OCO--, --CH.sub.2O--,
--CH.sub.2-- and --CH.sub.2CH.sub.2--; R.sup.25 is alkyl having 3
to 30 carbon atoms, phenyl, a group having a steroid skeleton or a
group represented by the following Formula (DI-13-a); in the above
alkyl, at least one hydrogen may be substituted with --F, and at
least one --CH.sub.2-- may be substituted with --O--, --CH.dbd.CH--
or --C.ident.CH--; hydrogen of the above phenyl may be substituted
with --F, --CH.sub.3, --OCH.sub.3, --OCH.sub.2F, --OCHF.sub.2,
--OCF.sub.3, alkyl having 3 to 30 carbon atoms or alkoxy having 3
to 30 carbon atoms; hydrogen of the above cyclohexyl may be
substituted with alkyl having 3 to 30 carbon atoms or alkoxy having
3 to 30 carbon atoms; the bonding position of --NH.sub.2 bonded to
the benzene ring shows that it is an optional position in the above
ring, and the bonding position thereof is preferably meta or para;
that is, assuming that the bonding position of a group of
"R.sup.25-G.sup.24-" is a 1-position, the two bonding positions are
preferably a 3-position and a 5-position or a 2-position and a
5-position;
##STR00066##
in Formula (DI-13-a), G.sup.27, G.sup.28 and G.sup.29 are a bonding
group, and they each are independently a single bond or alkylene
having 1 to 12 carbon atoms; at least one --CH.sub.2-- in the above
alkylene may be substituted with --O--, --COO--, --OCO--, --CONH--
or --CH.dbd.CH--; a ring B.sup.21, a ring B.sup.22, a ring B.sup.23
and a ring B.sup.24 each are independently 1,4-phenylene,
1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl,
pyridine-2,5-diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl or
anthracene-9,10-diyl; in the ring B.sup.21, the ring B.sup.22, the
ring B.sup.23 and the ring B.sup.24, at least one hydrogen may be
substituted with --F or --CH.sub.3; s, t and u each are
independently an integer of o to 2, and a total thereof is 1 to 5;
when s, t or u is 2, two bonding groups in each parenthesis may be
the same or different, and two rings may be the same or different;
R.sup.26 is --F, --OH, alkyl having 1 to 30 carbon atoms,
fluorine-substituted alkyl having 1 to 30 carbon atoms, alkoxy
having 1 to 30 carbon atoms, --CN, --OCH.sub.2F, --OCHF.sub.2 or
--OCF.sub.3, and at least one --CH.sub.2-- of the above alkyl
having 1 to 30 carbon atoms may be substituted with a divalent
group represented by the following Formula (DI-13-b):
##STR00067##
in Formula (DI-13-b), R.sup.27 and R.sup.28 each are independently
alkyl having 1 to 3 carbon atoms; v is an integer of 1 to 6; and
the preferred examples of R.sup.26 are alkyl having 1 to 30 carbon
atoms and alkoxy having 1 to 30 carbon atoms;
##STR00068##
in Formulas (DI-14) and (DI-15), plural G.sup.30 each are
independently a single bond, --CO-- or --CH.sub.2--; plural
R.sup.29 each are independently hydrogen or --CH.sub.3; R.sup.30 is
hydrogen, alkyl having 1 to 20 carbon atoms or alkenyl having 2 to
20 carbon atoms; at least one hydrogen of a benzene ring in Formula
(DI-15) may be substituted with alkyl having 1 to 20 carbon atoms
or phenyl; groups in which bonding positions are not fixed to any
of carbon atoms constituting the rings show that the bonding
positions thereof in the rings are optional; one of two groups
"-phenylene-G.sup.30-O--" in Formula (DI-14) is bonded preferably
to a 3-position of a steroid nucleus, and the other is bonded
preferably to a 6-position thereof; the bonding position of two
groups "-phenylene-G.sup.30-O--" in Formula (DI-15) is preferably a
meta position or a para position respectively to the bonding
position of the steroid nucleus; in Formulas (DI-14) and (DI-15),
--NH.sub.2 bonded to a benzene ring shows that the bonding position
thereof in the ring is optional:
##STR00069##
in Formulas (DI-16) and (DI-17), plural G.sup.31 each are
independently --O-- or alkylene having 1 to 6 carbon atoms;
G.sup.32 is a single bond or alkylene having 1 to 3 carbon atoms;
R.sup.31 is hydrogen or alkyl having 1 to 20 carbon atoms, and at
least one --CH.sub.2-- of the above alkyl may be substituted with
--O--, --CH.dbd.CH-- or --C.ident.CH--; R.sup.32 is alkyl having 6
to 22 carbon atoms; R.sup.33 is hydrogen or alkyl having 1 to 22
carbon atoms; a ring B.sup.25 is 1,4-phenylene or
1,4-cyclohexylene; r is 0 or 1; --NH.sub.2 bonded to a benzene ring
shows that the bonding position thereof in the ring is optional,
and plural bonding positions thereof each are independently
preferably a meta position or a para position to the bonding
position of G.sup.31.
[0070] The specific examples of the side chain type diamines are
shown below.
[0071] Diamines represented by the following Formulas (DI-13-1) to
(DI-17-3) can be listed as the diamines having side chains
represented by the Formulas (DI-13) to (DI-17) described above.
[0072] The examples of the compounds represented by Formula (DI-13)
are shown below:
##STR00070## ##STR00071##
[0073] In Formulas (DI-13-1) to (DI-13-11), R.sup.34 is alkyl
having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms,
preferably alkyl having 5 to 25 carbon atoms or alkoxy having 5 to
25 carbon atoms. R.sup.35 is alkyl having 1 to 30 carbon atoms or
alkoxy having 1 to 30 carbon atoms, preferably alkyl having 3 to 25
carbon atoms or alkoxy having 3 to 25 carbon atoms.
##STR00072##
[0074] In Formulas (DI-13-12) to (DI-13-17), R.sup.36 is alkyl
having 4 to 30 carbon atoms, preferably alkyl having 6 to 25 carbon
atoms. R.sup.37 is alkyl having 6 to 30 carbon atoms, preferably
alkyl having 8 to 25 carbon atoms.
##STR00073## ##STR00074## ##STR00075## ##STR00076##
[0075] In Formulas (DI-13-18) to (DI-13-43), R.sup.38 is alkyl
having 1 to 20 carbon atoms or alkoxy having 1 to 20 carbon atoms,
preferably alkyl having 3 to 20 carbon atoms or alkoxy having 3 to
20 carbon atoms. R.sup.39 is hydrogen, --F, alkyl having 1 to 30
carbon atoms, alkoxy having 1 to 30 carbon atoms, --CN,
--OCH.sub.2F, --OCHF.sub.2 or --OCF.sub.3, preferably alkyl having
3 to 25 carbon atoms or alkoxy having 3 to 25 carbon atoms.
G.sup.33 is alkylene having 1 to 20 carbon atoms.
##STR00077## ##STR00078## ##STR00079##
[0076] The examples of the compound represented by Formula (DI-14)
are shown below:
##STR00080##
[0077] The examples of the compound represented by Formula (DI-15)
are shown below:
##STR00081## ##STR00082##
[0078] The examples of the compound represented by Formula (DI-16)
are shown below:
##STR00083## ##STR00084##
[0079] In Formulas (DI-16-1) to (DI-16-12), R.sup.40 is hydrogen or
alkyl having 1 to 20 carbon atoms, preferably hydrogen or alkyl
having 1 to 10 carbon atoms, and R.sup.41 is hydrogen or alkyl
having 1 to 12 carbon atoms.
[0080] The examples of the compound represented by Formula (DI-17)
are shown below:
##STR00085##
[0081] In Formulas (DI-17-1) to (DI-17-3), R.sup.37 is alkyl having
6 to 22 carbon atoms, and R.sup.41 is hydrogen or alkyl having 1 to
12 carbon atoms.
[0082] Diamines other than the diamines represented by Formulas
(DI-1-1) to (DI-17-3) can also be used as the other diamines in the
present invention.
[0083] The above diamines include, for example, diamines having
side chain structures other than the diamines represented by
Formulas (DI-13-1) to (DI-17-3), and they include, for example,
compounds represented by the following Formulas (DI-18-1) to
(DI-18-8):
##STR00086## ##STR00087##
[0084] In Formulas (DI-18-1) to (DI-18-8), plural R.sup.42 each
represent independently alkyl having 3 to 30 carbon atoms.
[0085] Also, diamines represented by Formulas (DI-18-9) to
(DI-18-13) can be listed:
##STR00088##
[0086] In Formulas (DI-18-9) to (DI-18-11), e is an integer of 2 to
10; in Formula (DI-18-12), plural R.sup.43 each are independently
hydrogen, --NHBoc or --N(Boc).sub.2; at least one of R.sup.43 is
--NHBoc or --N(Boc).sub.2; in Formula (DI-18-13), R.sup.44 is
--NHBoc or --N(Boc).sub.2; and m is an integer of 1 to 12. In the
above formulas, Boc is t-butoxycarbonyl.
[0087] When a large pre-tilt angle is required for the liquid
crystal display device produced by using the liquid crystal
aligning agent of the present invention, particularly when a
pre-tilt angle of 2 degrees or more is caused to be exerted, a
proportion of the side chain type diamine based on a whole amount
of the diamines is controlled to preferably 5 to 70% by mole, more
preferably to 10 to 50% by mole in producing the polyamic acid and
derivative thereof which are used for the liquid crystal aligning
agent of the present invention.
[0088] In the respective diamines, a part of the diamines may be
substituted with monoamines in a range in which a proportion of the
monoamines based on the diamines is 40% by mole or less. Such
substitution makes it possible to bring about termination of
polymerization reaction in preparing polyamic acid to inhibit
polymerization reaction from proceeding further more. Accordingly,
the above substitution makes it possible to readily control a
molecular weight of the resulting polymer (polyamic acid and a
derivative thereof) and makes it possible to improve a coating
characteristic of the liquid crystal aligning agent without
damaging, for example, the effects of the present invention. One or
more diamines may be substituted with the monoamines as long as the
effects of the present invention are not damaged. The monoamines
include, for example, aniline, 4-hydroxyaniline, cyclohexylamine,
n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine,
n-octylamine, n-nonylamine, n-decylamine, n-undecylamine,
n-dodecylamine, n-tridecylamine, n-tetradecylamine,
n-pentadecylamine, n-hexadecylamine, n-heptadecylamine,
n-octadecylamine and n-eicocylamine. In particular, aniline can
suitably be used.
[0089] When it is regarded as important to further improve an
aligning property of the liquid crystal, among the specific
examples of the diamines described above, preferably used are the
diamines represented by Formulas (DI-1-3), (DI-4-1), (DI-5-12),
(DI-5-28), (DI-5-29), (DI-5-30), (DI-5-31), (DI-6-1), (DI-6-5),
(DI-6-7), (DI-7-3), (DI-7-5), (DI-7-9), (DI-11-1), (DI-12-1),
(DI-13-2), (DI-13-4), (DI-13-6), (DI-16-1), (DI-16-2), (DI-16-4),
(DI-16-5), (DI-16-7) and (DI-16-8). The diamines represented by
Formulas (DI-1-3), (DI-4-1), (DI-5-28), (DI-5-29), (DI-5-31),
(DI-7-3), (DI-13-2) and (DI-13-4) to (DI-13-6) are more preferably
used. Also, in Formula (DI-5-12), the compounds in which m is 2 to
4 are particularly preferred. In Formula (DI-5-30), the compound in
which k is 2 is particularly preferred. In Formula (DI-7-3), the
compounds in which m is 3 or 6 and in which n is 1 are particularly
preferred.
[0090] When it is regarded as important to provide the liquid
crystal alignment layer with a high VHR, among the specific
examples of the diamines described above, preferably used are the
diamines represented by Formulas (DI-5-30), (DI-7-1), (DI-7-3),
(DI-11-1), (DI-12-1), (DI-13-1), (DI-13-2), (DI-13-4), (DI-13-6),
(DI-16-1), (DI-16-2), (DI-16-4), (DI-16-5), (DI-16-7) and
(DI-16-8). The diamines represented by Formulas (DI-5-1), (DI-5-2),
(DI-5-21), (DI-5-30), (DI-13-4), (DI-13-5), (DI-16-1), (DI-16-2),
(DI-16-4) and (DI-16-7) are more preferably used. In Formula
(DI-5-30), the compound in which k is 2 is particularly preferred.
In Formula (DI-7-3), the compound in which m is 3 and in which n is
1 is particularly preferred. In Formulas (DI-13-4) and (DI-13-5),
the compounds in which R.sup.35 is alkyl having 3 to 25 carbon
atoms are particularly preferred. In Formulas (DI-16-1) and
(DI-16-2), the compounds in which Roo has 1 to 10 carbon atoms are
particularly preferred. In Formulas (DI-16-4) and (DI-16-7), the
compounds in which R.sup.41 has 1 to 10 carbon atoms are
particularly preferred.
[0091] When it is regarded as important to further reduce a volume
resistance value of the liquid crystal alignment layer, among the
specific examples of the diamines described above, preferably used
are the diamines represented by Formulas (DI-4-12), (DI-4-14),
(DI-5-9), (DI-5-15), (DI-5-27), (DI-5-31), (DI-6-3) to (DI-6-5),
(DI-11-1) and (DI-12-1). The diamines represented by Formulas
(DI-5-1), (DI-5-2), (DI-5-9) to (DI-5-11), (DI-5-21), (DI-5-27) and
(DI-5-30) are more preferably used. In Formula (DI-5-30), the
compound in which k is 2 is particularly preferred.
<Polyamic Acid or a Derivative Thereof>
[0092] The polyamic acid used for the liquid crystal aligning agent
of the present invention is obtained by reacting the mixture of the
acid anhydrides described above with diamine in a solvent. In the
above synthetic reaction, the specific conditions other than
selection of the raw materials are not required, and conditions in
conventional synthesis of polyamic acid can be applied as they are.
Solvents to be used shall be described later.
<Other Components>
[0093] The liquid crystal aligning agent of the present invention
may further contain other components in addition to the polyamic
acid or derivative thereof. The other components may comprise a
single kind of a compound or two or more kinds of compounds.
[0094] The liquid crystal aligning agent of the present invention
may further contain, for example, an alkenyl-substituted nadimide
compound for the purpose of stabilizing the electric
characteristics of the liquid crystal display device over a long
period of time. The alkenyl-substituted nadimide compound may be
used alone or in combination of two or more kinds thereof. From the
viewpoint of the purpose described above, a content of the
alkenyl-substituted nadimide compound is preferably 1 to 100% by
weight, more preferably 1 to 70% by weight and further preferably 1
to 50% by weight based on the polyamic acid or derivative
thereof.
<Alkenyl-Substituted Nadimide Compound>
[0095] The alkenyl-substituted nadimide compound shall specifically
be explained below.
[0096] The alkenyl-substituted nadimide compound is preferably a
compound which can be dissolved in a solvent dissolving the
polyamic acid or derivative thereof used in the present invention.
The examples of the above alkenyl-substituted nadimide compound
includes compounds represented by the following Formula (NA):
##STR00089##
in Formula (NA), L.sub.1 and L.sub.2 each are independently
hydrogen, alkyl having 1 to 12 carbon atoms, alkenyl having 3 to 6
carbon atoms, cycloalkyl having 5 to 8 carbon atoms, aryl having 6
to 12 carbon atoms or benzyl, and n is 1 or 2.
[0097] When n is 1 in Formula (NA), W is alkyl having 1 to 12
carbon atoms, alkenyl having 2 to 6 carbon atoms, cycloalkyl having
5 to 8 carbon atoms, aryl having 6 to 12 carbon atoms, benzyl, a
group represented by
--Z.sup.1--(O).sub.r--(Z.sup.2O).sub.k--Z.sup.3--H (wherein
Z.sup.4, Z.sup.2 and Z.sup.3 each are independently alkylene having
2 to 6 carbon atoms; r is 0 or 1; and k is an integer of 1 to 30),
a group represented by --(Z.sup.4).sub.r--B--Z.sup.5--H (wherein
Z.sup.4 and Z.sup.5 each are independently alkylene having 1 to 4
carbon atoms or cycloalkylene having 5 to 8 carbon atoms; B is
phenylene; and r is 0 or 1), a group represented by --B-T-B--H
(wherein B is phenylene; and T is --CH.sub.2,
--C(CH.sub.3).sub.2--, --O--, --CO--, --S-- or --SO.sub.2--) or
groups obtained by substituting 1 to 3 hydrogens of the above
groups with --OH.
[0098] In the above case, preferred W is alkyl having 1 to 8 carbon
atoms, alkenyl having 3 to 4 carbon atoms, cyclohexyl, phenyl,
benzyl, poly(ethyleneoxy)ethyl having 4 to 10 carbon atoms,
phenyloxyphenyl, phenylmethylphenyl, phenylisopropylidenephenyl and
groups obtained by substituting 1 or 2 hydrogens of the above
groups with --OH.
[0099] When n is 2 in Formula (NA), W is alkylene having 2 to 20
carbon atoms, cycloalkylene having 5 to 8 carbon atoms, arylene
having 6 to 12 carbon atoms, a group represented by
--Z.sup.1--O--(Z.sup.2O).sub.k--Z.sup.3-- (wherein Z.sup.1 to
Z.sup.3 and k mean the same as described above), a group
represented by --Z.sup.4--B--Z.sup.5-- (wherein Z.sup.4, Z.sup.3
and B mean the same as described above), a group represented by
--B--(O--B).sub.r-T-B--(B--O).sub.r--B-- (wherein B is phenylene; T
is alkylene having 1 to 3 carbon atoms, --O-- or --SO.sub.2--; and
r means the same as described above) or groups obtained by
substituting 1 to 3 hydrogens of the above groups with --OH.
[0100] In the above case, preferred W is alkylene having 2 to 12
carbon atoms, cyclohexylene, phenylene, tolylene, xylylene, a group
represented by
--C.sub.3H.sub.6--O--(Z.sup.2--O).sub.n--O--C.sub.3H.sub.6--
(wherein Z.sup.2 is alkylene having 2 to 6 carbon atoms, and n is 1
or 2), a group represented by --B-T-B-- (wherein B is phenylene;
and T is --CH.sub.2, --O-- or --SO.sub.2--), a group represented by
--B--O--B--C.sub.3H.sub.6--B--O--B-- (wherein B is phenylene) and
groups obtained by substituting 1 or 2 hydrogens of the above
groups with --OH.
[0101] Compounds obtained by holding, as described in Japanese
Patent No. 2729565, an alkenyl-substituted nadic anhydride
derivative and diamine at a temperature of 80 to 220.degree. C. for
0.5 to 20 hours and commercially available compounds can be used as
the above alkenyl-substituted nadimide compound. The specific
examples of the alkenyl-substituted nadimide compound include the
following compounds.
[0102] N-methyl-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,
N-methyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,
N-methyl-methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,
N-methyl-methallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,
N-(2-ethylhexyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,
[0103]
N-(2-ethylhexyl)-allyl(methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarbox-
yimide, N-allyl-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,
N-allyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,
N-allyl-methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,
N-isopropenyl-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,
N-isopropenyl-allyl(methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,
N-isopropenyl-methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,
N-cyclohexyl-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,
N-cyclohexyl-allyl(methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,
N-cyclohexyl-methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,
N-phenyl-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,
[0104]
N-phenyl-allyl(methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,
N-benzyl-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,
N-benzyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,
N-benzyl-methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,
N-(2-hydroxyethyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,
N-(2-hydroxyethyl)-allyl(methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimi-
de,
N-(2-hydroxyethyl)-methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimid-
e,
[0105]
N-(2,2-dimethyl-3-hydroxypropyl)-allylbicyclo[2.2.1]hept-5-ene-2,3--
dicarboxyimide,
N-(2,2-dimethyl-3-hydroxypropyl)-allyl(methyl)bicyclo[2.2.1]hept-5-ene-2,-
3-dicarboxyimide,
N-(2,3-dihydroxypropyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,
N-(2,3-dihydroxypropyl)-allyl(methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarbo-
xyimide,
N-(3-hydroxy-1-propenyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarb-
oxyimide,
N-(4-hydroxycyclohexyl)-allyl(methyl)bicyclo[2.2.1]hept-5-ene-2,-
3-dicarboxyimide,
[0106]
N-(4-hydroxyphenyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimid-
e,
N-(4-hydroxyphenyl)-allyl(methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy-
imide,
N-(4-hydroxyphenyl)-methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy-
imide,
N-(4-hydroxyphenyl)-methallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dic-
arboxyimide,
N-(3-hydroxyphenyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,
N-(3-hydroxyphenyl)-allyl(methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyim-
ide,
N-(p-hydroxybenzyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,
N-{2-(2-hydroxyethoxy)ethyl}-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyi-
mide,
[0107]
N-{2-(2-hydroxyethoxy)ethyl}-allyl(methyl)bicyclo[2.2.1]hept-5-ene--
2,3-dicarboxyimide,
N-{2-(2-hydroxyethoxy)ethyl}-methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarb-
oxyimide,
N-{2-(2-hydroxyethoxy)ethyl}-methallylmethylbicyclo[2.2.1]hept-5-
-ene-2,3-dicarboxyimide,
N-[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]-allylbicyclo[2.2.1]hept-5-ene-2,3--
dicarboxyimide,
N-[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]-allyl(methyl)bicyclo[2.2.1]hept-5--
ene-2,3-dicarboxyimide,
N-[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]-methallylbicyclo[2.2.1]hept-5-ene--
2,3-dicarboxyimide,
N-{4-(4-hydroxyphenylisopropylidene)phenyl}-allylbicyclo[2.2.1]hept-5-ene-
-2,3-dicarboxyimide,
N-{4-(4-hydroxyphenylisopropylidene)phenyl}-allyl(methyl)bicyclo[2.2.1]he-
pt-5-ene-2,3-dicarboxyimide,
N-{4-(4-hydroxyphenylisopropylidene)phenyl}-methallylbicyclo[2.2.1]hept-5-
-ene-2,3-dicarboxyimide, and oligomer thereof,
[0108]
N,N'-ethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)-
,
N,N'-ethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide-
),
N,N'-ethylene-bis(methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)-
,
N,N'-trimethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide),
N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide),
N,N'-hexamethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyi-
mide),
N,N'-dodecamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarbox-
yimide),
N,N'-dodecamethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3--
dicarboxyimide),
N,N'-cyclohexylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide),
N,N'-cyclohexylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyi-
mide),
[0109]
1,2-bis{3'-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)propox-
y}ethane,
1,2-bis{3'-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimi-
de)propoxy}ethane,
1,2-bis{3'-(methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)propoxy}-
ethane,
bis[2'-{3'-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)propo-
xy}ethyl] ether,
bis[2'-{3'-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)propox-
y}ethyl]ether, 1,
4-bis{3'-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)propoxy}butane-
, 1,
4-bis{3'-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)prop-
oxy}butane,
[0110]
N,N'-p-phenylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-diccarboxyim-
ide),
N,N'-p-phenylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarbo-
xyimide),
N,N'-m-phenylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy-
imide),
N,N'-m-phenylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicar-
boxyimide),
N,N'-{(1-methyl)-2,4-phenylene}-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dic-
arboxyimide),
N,N'-p-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide),
N,N'-p-xylylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimid-
e),
N,N'-m-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide),
N,N'-m-xylylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimid-
e),
[0111]
2,2-bis[4-{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phen-
oxy}phenyl]propane,
2,2-bis[4-{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phen-
oxy}phenyl]propane,
2,2-bis[4-{4-(methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenox-
y}phenyl]propane,
bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenyl]methane,
bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenyl]meth-
ane,
[0112]
bis{4-(methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenyl}-
methane,
bis{4-(methallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide-
)phenyl}methane,
bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenyl}
ether,
bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenyl}ethe-
r,
bis{4-(methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenyl}ethe-
r,
bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenyl}sulfone,
bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenyl}sulf-
one,
[0113]
bis{4-(methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenyl}-
sulfone, 1,6-bis
(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)-3-hydroxy-hexane,
1,12-bis (methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)-3,
6-dihydroxy-dodecane, 1,3-bis
(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)-5-hydroxy-cyclohexane,
1,5-bis{3'-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)propoxy}-3-h-
ydroxy-pentane, 1,4-bis
(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)-2-hydroxy-benzene,
[0114] 1,4-bis
(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)-2,5-dihydroxy-be-
nzene,
N,N'-p-(2-hydroxy)xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-di-
carboxyimide),
N,N'-p-(2-hydroxy)xylylene-bis(allylmethylcyclo[2.2.1]hept-5-ene-2,3-dica-
rboxyimide),
N,N'-m-(2-hydroxy)xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarbox-
yimide),
N,N'-m-(2-hydroxy)xylylene-bis(methallylbicyclo[2.2.1]hept-5-ene--
2,3-dicarboxyimide),
N,N'-p-(2,3-hydroxy)xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarb-
oxyimide),
[0115]
2,2-bis[4-{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)-2-h-
ydroxy-phenoxy}phenyl]propane,
bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)-2-hydroxy--
phenyl}methane,
bis{3-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)-4-hydroxy-phenyl-
}ether,
bis{3-(methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)-5-hyd-
roxy-phenyl}sulfone,
1,1,1-tri{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)}phen-
oxymethylpropane,
N,N',N''-tri(ethylenemethallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide-
) isocyanate, oligomer thereof and the like.
[0116] Further, the alkenyl-substituted nadimide compound used in
the present invention may be compounds represented the following
formulas containing an asymmetric alkylene.phenylene group:
##STR00090##
[0117] Among the alkenyl-substituted nadimide compounds, the
preferred compounds are shown below:
[0118]
N,N'-ethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)-
,
N,N'-ethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide-
),
N,N'-ethylene-bis(methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)-
,
N,N'-trimethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide),
N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide),
N,N'-hexamethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyi-
mide),
N,N'-dodecamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarbox-
yimide),
N,N'-dodecamethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3--
dicarboxyimide),
N,N'-cyclohexylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide),
N,N'-cyclohexylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyi-
mide),
[0119]
N,N'-p-phenylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimi-
de),
N,N'-p-phenylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarbox-
yimide),
N,N'-m-phenylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyi-
mide),
N,N'-m-phenylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarb-
oxyimide),
N,N'-{(1-methyl)-2,4-phenylene}-bis(allylbicyclo[2.2.1]hept-5-e-
ne-2,3-dicarboxyimide),
N,N'-p-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide),
N,N'-p-xylylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimid-
e),
N,N'-m-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide),
N,N'-m-xylylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimid-
e),
2,2-bis[4-{4-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenoxy}-
phenyl]propane,
2,2-bis[4-{4-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)pheno-
xy}phenyl]propane,
2,2-bis[4-{4-methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenoxy-
}phenyl]propane,
bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenyl}methane,
bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenyl}meth-
ane,
[0120]
bis{4-(methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenyl}-
methane,
bis{4-(methallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide-
)phenyl}methane,
bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenyl}
ether,
bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenyl}
ether,
bis{4-(methallybicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenyl}
ether,
bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenyl}sul-
fone,
bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenyl-
}sulfone,
bis{4-(methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phen-
yl}sulfone,
[0121] The further preferred alkenyl-substituted nadimide compounds
are shown below:
[0122]
N,N'-ethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)-
,
N,N'-ethylene-bis(allylmetylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)-
,
N,N'-ethylene-bis(methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide),
N,N'-trimethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide),
N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide),
N,N'-hexamethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyi-
mide),
N,N'-dodecamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarbox-
yimide),
N,N'-dodecamethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3--
dicarboxyimide),
N,N'-cyclohexylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide),
N,N'-cyclohexylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyi-
mide),
[0123]
N,N'-p-phenylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimi-
de),
N,N'-p-phenylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarbox-
yimide),
N,N'-m-phenylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyi-
mide),
N,N'-m-phenylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarb-
oxyimide),
N,N'-{(1-methyl)-2,4-phenylene}-bis(allylbicyclo[2.2.1]hept-5-e-
ne-2,3-dicarboxyimide),
N,N'-p-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide),
N,N'-p-xylylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimid-
e),
N,N'-m-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide),
N,N'-m-xylylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimid-
e),
[0124]
2,2-bis[4-{4-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)pheno-
xy}phenyl]propane,
2,2-bis[4-{4-allylmethyllbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phen-
oxy}phenyl]propane,
2,2-bis[4-{4-methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenoxy-
}phenyl]propane,
bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenyl}methane,
bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenyl}meth-
ane,
bis{4-(methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenyl}me-
thane and
bis{4-(methallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimid-
e)phenyl}methane.
[0125] The particularly preferred alkenyl-substituted nadimide
compounds include
bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenyl}me-
thane represented by the following Formula (NA-1),
N,N'-m-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)
represented by Formula (NA-2) and
N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)
represented by Formula (NA-3).
##STR00091##
<Compound Having a Radically Polymerizable Unsaturated Double
Bond>
[0126] The liquid crystal aligning agent of the present invention
may further contain, for example, a compound having a radically
polymerizable unsaturated double bond for the purpose of
stabilizing the electric characteristics of the liquid crystal
display device over a long period of time. The compound having a
radically polymerizable unsaturated double bond may comprise a
single kind of a compound or two or more kinds of compounds. The
alkenyl-substituted nadimide compound is not included in the
compound having a radically polymerizable unsaturated double bond.
From the viewpoint of the purpose described above, a content of the
compound having a radically polymerizable unsaturated double bond
is preferably 1 to 100% by weight, more preferably 1 to 70% by
weight and further preferably 1 to 50% by weight based on the
polyamic acid or derivative thereof.
[0127] A proportion of the compound having a radically
polymerizable unsaturated double bond to the alkenyl-substituted
nadimide compound is preferably 0.1 to 10, more preferably 0.5 to 5
in terms of a weight ratio in order to reduce an ion density of the
liquid crystal display device, inhibit the ion density from
increasing with the passage of time and inhibit the afterimages
from being generated.
[0128] The compound having a radically polymerizable unsaturated
double bond shall specifically be explained below. The compound
having a radically polymerizable unsaturated double bond includes
(meth)acrylic acid derivatives such as (meth)acrylic esters,
(meth)acrylic acid amides and the like, and bismaleimide. The
compound having a radically polymerizable unsaturated double bond
is more preferably (meth)acrylic acid derivatives having two or
more radically polymerizable unsaturated double bonds.
[0129] The specific examples of the (meth)acrylic esters include,
for example, cyclohexyl (meth)acrylate, 2-methylcyclohexyl
(meth)acrylate, dicyclopentanyl (meth)acrylate,
dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate,
phenyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl
(meth)acrylate, and 2-hydroxypropyl (meth)acrylate.
[0130] The specific examples of difunctional (meth)acrylic esters
include, for example, ethylenebisacrylate, Aronix M-210, Aronix
M-240 and Aronix M-6200 which are products of Toagosei Co., Ltd.,
KAYARAD HDDA, KAYARAD HX-220, KAYARAD R-604, and KAYARAD R-684
which are products of Nippon Kayaku Co., Ltd., V260, V312 and
V335HP which are products of Osaka Organic Industry Ltd. and Light
Acrylate BA-4EA, Light Acrylate BP-4PA, and Light Acrylate BP-2PA
which are products of Kyoeisha Chemical Co., Ltd.
[0131] The specific examples of trifunctional or more (meth)acrylic
esters include, for example,
4,4'-methylenebis(N,N-dihydroxyethyleneacrylateaniline), Aronix
M-400, Aronix M-405, Aronix M-450, Aronix M-7100, Aronix M-8030,
and Aronix M-8060 which are products of Toagosei Co., Ltd., KAYARAD
TMPTA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, and
KAYARAD DPCA-120 which are products of Nippon Kayaku Co., Ltd.,
VGPT which is a product of Osaka Organic Industry Ltd.
[0132] The specific examples of the (meth)acrylic acid amide
derivatives include, for example, N-isopropylacrylamide,
N-isopropylmethacrylamide, N-n-propylacrylamide,
N-n-propylmethacrylamide, N-cyclopropylacrylamide,
N-cyclopropylmethacrylamide, N-ethoxyethylacrylamide,
N-ethoxyethylmethacrylamide, N-tetrahydrofurfurylacrylamide,
N-tetrahydrofurfurylmethacrylamide, N-ethylacrylamide,
N-ethyl-N-methylacrylamide, N,N-diethylacrylamide,
N-methyl-N-n-propylacrylamide, N-methyl-N-isopropylacrylamide,
N-acryloylpiperidine, N-acryloylpyrrolidine,
N,N'-methylenebisacrylamide, N,N'-ethylenbisacrylamide,
N,N'-dihydroxyethylenebisacrylamide,
N-(4-hydroxyphenyl)methacrylamide, N-phenylmethacrylamide,
N-butylmethacrylamide, N-(iso-butoxymethyl)methacrylamide,
N-[2-(N,N-dimethylamino)ethyl]methacrylamide,
N,N-dimethylmethacrylamide,
N-[3-(dimethylamino)propyl]methacrylamide,
N-(methoxymethyl)methacrylamide,
N-(hydroxymethyl)-2-methacrylamide, N-benzyl-2-methacrylamide, and
N,N'-methylenebismethacrylamide.
[0133] Among the (meth)acrylic acid derivatives described above,
N,N'-methylenebisacryamide, N,N'-dihydroxyethylene-bisacryamide,
ethylenebisacrylate, and
4,4'-methylenebis(N,N-dihydroxyethyleneacrylateaniline) are
particularly preferred.
[0134] The bismaleimide includes, for example, BMI-70 and BMI-80
manufactured by KI Chemical Industry Co., Ltd., and BMI-1000,
BMI-3000, BMI-4000, BMI-5000, and BMI-7000 manufactured by
Daiwakasei Industry Co., Ltd.
<Oxazine Compound>
[0135] The liquid crystal aligning agent of the present invention
may further contain, for example, an oxazine compound for the
purpose of stabilizing the electric characteristics of the liquid
crystal display device over a long period of time. The oxazine
compound may comprise a single kind of a compound or two or more
kinds of compounds. From the viewpoint of the purpose described
above, a content of the oxazine compound is preferably 0.1 to 50%
by weight, more preferably 1 to 40% by weight and further
preferably 1 to 20% by weight based on the polyamic acid or
derivative thereof.
[0136] The oxazine compound shall specifically be explained
below.
[0137] The oxazine compound is soluble in a solvent dissolving the
polyamic acid or derivative thereof, and in addition thereto, the
oxazine compounds having a ring-opening polymerizability are
preferred.
[0138] The number of an oxazine structure in the oxazine compound
shall not specifically be restricted.
[0139] Various structures of the oxazine compound are known. In the
present invention, the structure of the oxazine compound shall not
specifically be restricted, and the oxazine structure in the
oxazine compound includes the structures of oxazines having an
aromatic group including a condensed polycyclic aromatic group such
as benzoxazine, naphthoxazine and the like.
[0140] The oxazine compound includes, for example, compounds
represented by the following Formulas (OX-1) to (OX-6). In the
following formulas, bondings shown toward the center of the rings
show that they are bonded to any carbons which constitute the rings
and to which substituents can be bonded:
##STR00092##
in Formulas (OX-1) to (OX-3), L.sup.3 and L.sup.4 are an organic
group having 1 to 30 carbon atoms; in (OX-1) to (OX-6), L.sup.5 to
L.sup.8 are hydrogen or a hydrocarbon group having 1 to 6 carbon
atoms; in Formulas (OX-3), (OX-4) and (OX-6), Q.sup.1 is a single
bond, --O--, --S--, --S--S--, --SO.sub.2--, --CO--, --CONH--,
--NHCO--, --C(CH.sub.3).sub.2--, --C(CF.sub.3).sub.2--,
--C(CH.sub.2).sub.v--, --O--(CH.sub.3).sub.v--O-- or
--S--(CH.sub.2).sub.v--S--, wherein v is an integer of 1 to 6; in
Formulas (OX-5) and (OX-6), plural Q.sup.2 each are independently a
single bond, --O--, --S--, --CO--, --C(CH.sub.3).sub.2--,
--C(CF.sub.3).sub.2-- or alkylene having 1 to 3 carbon atoms; and
hydrogens bonded to a benzene ring and a naphthalene ring in
Q.sup.2 each may be substituted independently with --F, --CH.sub.3,
--OH, --COOH, --SO.sub.3H and --PO.sub.3H.sub.2.
[0141] Oligomers and polymers each having an oxazine structure on
side chains and oligomers and polymers each having an oxazine
structure on principal chains are included in the oxazine
compounds.
[0142] The oxazine compound represented by Formula (OX-1) includes,
for example, the following oxazine compounds:
##STR00093##
[0143] In Formula (OX-2), L.sup.3 is preferably alkyl having 1 to
30 carbon atoms, more preferably alkyl having 1 to 20 carbon
atoms.
[0144] The oxazine compound represented by Formula (OX-2) includes,
for example, the following oxazine compounds:
##STR00094## ##STR00095##
[0145] In the formulas, L.sup.3 is preferably alkyl having 1 to 30
carbon atoms, more preferably alkyl having 1 to 20 carbon
atoms.
[0146] The oxazine compound represented by Formula (OX-3) includes,
for example, an oxazine compound represented by the following
Formula (OX-3-1):
##STR00096##
in Formula (OX-3-1), L.sup.3 and L.sup.4 are an organic group
having 1 to 30 carbon atoms; L.sup.5 to L.sup.8 are hydrogen or a
hydrocarbon group having 1 to 6 carbon atoms; and Q.sup.1 is a
single bond, --CH.sub.2--, --C(CH.sub.3).sub.2--, --CO--, --O--,
--SO.sub.2--, --C(CH.sub.3).sub.2-- or --C(CF.sub.3).sub.2--. The
oxazine compound represented by Formula (OX-3-1) includes, for
example, the following oxazine compounds:
##STR00097## ##STR00098##
[0147] In the formulas, L.sup.3 and L.sup.4 are preferably alkyl
having 1 to 30 carbon atoms, more preferably alkyl having 1 to 20
carbon atoms.
[0148] The oxazine compound represented by Formula (OX-4) includes,
for example, the following oxazine compounds:
##STR00099## ##STR00100##
[0149] The oxazine compound represented by Formula (OX-5) includes,
for example, the following oxazine compounds:
##STR00101##
[0150] The oxazine compound represented by Formula (OX-6) includes,
for example, the following oxazine compounds:
##STR00102##
[0151] Among them, more preferably listed are the oxazine compound
represented by Formulas (OX-2-1), (OX-3-1), (OX-3-3), (OX-3-5),
(OX-3-7), (OX-3-9), (OX-4-1) to (OX-4-6), (OX-5-3), (OX-5-4) and
(OX-6-2) to (OX-6-4).
[0152] The oxazine compound can be produced by the same methods as
those described in International Publication 2004/009708, JP-A
1999-12258 and JP-A 2004-352670.
[0153] The oxazine compound represented by Formula (OX-6) is
obtained by reacting a phenol compound and primary amine with
aldehyde (refer to International Publication 2004/009708).
[0154] The oxazine compound represented by Formula (OX-2) is
obtained by gradually adding primary amine to formaldehyde to react
them and then adding a naphthol base compound having a hydroxyl
group to react them (refer to International Publication
2004/009708).
[0155] The oxazine compound represented by Formula (OX-3) is
obtained by reacting 1 mole of a phenol compound, at least 2 mole
or more of aldehyde based on one phenolic hydroxyl group of the
phenol compound and 1 mole of primary amine in an organic solvent
under the presence of secondary aliphatic amine, tertiary aliphatic
amine or a basic nitrogen-containing heterocyclic compound (refer
to International Publication 2004/009708 and JP-A 1999-12258).
[0156] The oxazine compounds represented by Formula (OX-4) to
(OX-6) are obtained by subjecting to dehydration condensation
reaction, diamine having plural benzene rings and organic groups
combining them, such as 4,4'-diaminodiphenylmethane and the like,
aldehyde such as formalin and the like, and phenol at a temperature
of 90 C or higher in n-butanol (refer to JP-A 2004-352670).
[0157] <Oxazoline Compound>
[0158] The liquid crystal aligning agent of the present invention
may further contain, for example, an oxazoline compound for the
purpose of stabilizing the electric characteristics of the liquid
crystal display device over a long period of time. The oxazoline
compound is a compound having an oxazoline structure. The oxazoline
compound may comprise a single kind of a compound or two or more
kinds of compounds. From the viewpoint of the purpose described
above, a content of the oxazoline compound is preferably 0.1 to 50%
by weight, more preferably 1 to 40% by weight and further
preferably 1 to 20% by weight based on the polyamic acid or
derivative thereof. Or, when an oxazoline structure of the
oxazoline compound is reduced to oxazoline, a content of the
oxazoline compound is preferably 0.1 to 40% by weight based on the
polyamic acid or derivative thereof from the viewpoint of the
purpose described above.
[0159] The oxazoline compound shall specifically be explained
below.
[0160] The oxazoline compound may have either one oxazoline
structure or two or more oxazoline structures in one compound, and
it has preferably two or more structures. Also, the oxazoline
compound may be either a polymer or a copolymer having an oxazoline
structure on a side chain. The polymer having an oxazoline
structure on a side chain may be a homopolymer of a monomer having
an oxazoline structure on a side chain or a copolymer of a monomer
having an oxazoline structure on a side chain with a monomer having
no oxazoline structure. The copolymer having an oxazoline structure
on a side chain may be a copolymer of two or more kinds of monomers
having an oxazoline structure on a side chain or a copolymer of two
or more kinds of monomers having an oxazoline structure on a side
chain with monomers having no oxazoline structure.
[0161] The oxazoline structure is preferably a structure which is
present in the oxazoline compound so that one or both of oxygen and
nitrogen in the oxazoline structure can be reacted with a carbonyl
group of the polyamic acid.
[0162] The oxazoline compound includes, for example,
2,2'-bis(2-oxazoline), 1,2,4-tris(2-oxazolynyl-2)-benzene,
4-furan-2-ylmethylene-2-phenyl-4H-oxazole-5-one,
1,4-bis(4,5-dihydro-2-oxazolyl)benzene,
1,3-bis(4,5-dihydro-2-oxazolyl)benzene,
2,3-bis(4-isopropenyl-2-oxazoline-2-yl)butane,
2,2'-bis-4-benzyl-2-oxazoline,
2,6-bis(isopropyl-2-oxazoline-2-yl)pyridine,
2,2'-isopropylidenebis(4-tert-butyl-2-oxazoline),
2,2'-isopropylidenebis(4-phenyl-2-oxazoline),
2,2'-methylenebis(4-tert-butyl-2-oxazoline) and
2,2'-methylenebis(4-phenyl-2-oxazoline). In addition to them, it
includes polymers and oligomers having oxazolyl, such as EPOCROS
(trade name, manufactured by Nippon Shokubai Co., Ltd.). Among
them, 1,3-bis(4,5-dihydro-2-oxazolyl)benzene is more preferred.
<Epoxy Compound>
[0163] The liquid crystal aligning agent of the present invention
may further contain, for example, an epoxy compound for the purpose
of stabilizing the electric characteristics of the liquid crystal
display device over a long period of time. The epoxy compound may
comprise a single kind of a compound or two or more kinds of
compounds. From the viewpoint of the purpose described above, a
content of the epoxy compound is preferably 0.1 to 50% by weight,
more preferably 1 to 40% by weight and further preferably 1 to 20%
by weight based on the polyamic acid or derivative thereof.
[0164] The epoxy compound shall specifically be explained
below.
[0165] The epoxy compound includes various compounds having at
least one epoxy ring in a molecule. Compounds having one epoxy ring
in a molecule include, for example, phenyl glycidyl ether, butyl
glycidyl ether, 3,3,3-trifluoromethylpropylene oxide, styrene
oxide, hexafluoropropylene oxide, cyclohexene oxide,
3-glycidoxypropyltrimethoxysilane,
2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,
N-glycidylphthalimide, (nonafluoro-N-butyl) epoxide, perfluoroethyl
glycidyl ether, epichlorohydrin, epibromohydrin,
N,N-diglycidylaniline and
3-[2-(perfluorohexyl)ethoxy]-1,2-epoxypropane.
[0166] Compounds having two epoxy rings in a molecule include, for
example, ethylene glycol diglycidyl ether, polyethylene glycol
diglycidyl ether, propylene glycol diglycidyl ether, tripropylene
glycol diglycidyl ether, polypropylene glycol diglycidyl ether,
neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether,
glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl
ether,
3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate and
3-(N,N-diglycidyl)aminopropyltrimethoxysilane.
[0167] Compounds having three epoxy rings in a molecule include,
for example,
2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-([2,3-epoxypropox-
y]phenyl)]ethyl]phenyl]propane (trade name: .left brkt-top.TECHMORE
VG3101L.right brkt-bot., manufactured by Mitsui Chemicals,
Inc.).
[0168] Compounds having 4 epoxy rings in a molecule include, for
example, 1,3,5,6-tetraglycidyl-2,4-hexanediol,
N,N,N',N'-tetraglycidyl-m-xylenediamine,
1,3-bis(N,N-diglycidylaminomethyl)cyclohexane,
N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane and
3-(N-allyl-N-glycidyl)aminopropyltrimethoxysilane.
[0169] In addition to the compounds described above, the examples
of compounds having epoxy rings in a molecule include as well
oligomers and polymers having epoxy rings. Monomers having epoxy
rings include, for example, glycidyl (meth)acrylate,
3,4-epoxycyclohexyl (meth)acrylate and methylglycidyl
(meth)acrylate.
[0170] Other monomers copolymerized with the monomers having epoxy
rings include, for example, (meth)acrylic acid, methyl
(meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate,
butyl (meth)acrylate, iso-butyl (meth)acrylate, t-butyl
(meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate,
2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate,
styrene, methylstyrene, chloromethylstyrene,
(3-ethyl-3-oxetanyl)methyl (meth)acrylate, N-cyclohexylmaleimide
and N-phenylmaleimide.
[0171] The preferred specific examples of the polymers of the
monomers having epoxy rings include polyglycidyl methacrylate and
the like. Also, the preferred specific examples of the copolymers
of the monomers having epoxy rings with other monomers include
N-phenylmaleimide-glycidyl methacrylate copolymers,
N-cyclohexylmaleimide-glycidyl methacrylate copolymers, benzyl
methacrylate-glycidyl methacrylate copolymers, butyl
methacrylate-glycidyl methacrylate copolymers, 2-hydoxyethyl
methacrylate-glycidyl methacrylate copolymers,
(3-ethyl-3-oxetanyl)methyl methacrylate-glycidyl methacrylate
copolymers, and styrene-glycidyl methacrylate copolymers.
[0172] Among the above examples, particularly preferred are
N,N,N',N'-tetraglycidyl-m-xylenediamine,
1,3-bis(N,N-diglycidylaminomethyl)cyclohexane,
N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, trade name:
"TECHMORE VG3101L",
3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate,
N-phenylmaleimide-glycidyl methacrylate copolymers, and 2-(3,
4-epoxycyclohexyl)ethyltrimethoxysilane.
[0173] To be more systematic, the epoxy compound includes, for
example, glycidyl ethers, glycidyl esters, glycidylamines, epoxy
group-containing acryl base resins, glycidylamides, glycidyl
isocyanurates, linear aliphatic epoxy compounds, and cyclic
aliphatic epoxy compounds. The epoxy compounds mean compounds
having an epoxy group, and the epoxy resins mean resins having an
epoxy group.
[0174] The epoxy compound includes, for example, glycidyl ethers,
glycidyl esters, glycidylamines, epoxy group-containing acryl base
resins, glycidylamides, glycidyl isocyanurates, linear aliphatic
epoxy compounds and cyclic aliphatic epoxy compounds.
[0175] The glycidyl ethers include, for example, bisphenol A type
epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type
epoxy compounds, bisphenol type epoxy compounds, hydrogenated
bisphenol A type epoxy compounds, hydrogenated bisphenol F type
epoxy compounds, hydrogenated bisphenol S type epoxy compounds,
hydrogenated bisphenol type epoxy compounds, brominated bisphenol A
type epoxy compounds, brominated bisphenol F type epoxy compounds,
phenol novolac type epoxy compounds, cresol novolac type epoxy
compounds, brominated phenol novolac type epoxy compounds,
brominated cresol novolac type epoxy compounds, bisphenol A novolac
type epoxy compounds, naphthalene skeleton-containing epoxy
compounds, aromatic polyglycidyl ether compounds, dicyclopentadiene
phenol type epoxy compounds, alicyclic diglycidyl ether compounds,
aliphatic polyglycidyl ether compounds, polysulfide type diglycidyl
ether compounds, and biphenol type epoxy compounds.
[0176] The glycidyl esters include, for example, diglycidyl ester
compounds and glycidyl ester epoxy compounds.
[0177] The glycidylamines include, for example, polyglycidylamine
compounds and glycidylamine type epoxy resins.
[0178] The epoxy group-containing acryl base compounds include, for
example, homopolymer and copolymers of monomers having
oxyranyl.
[0179] The glycidylamides include, for example, glycidylamide type
epoxy compounds.
[0180] The linear aliphatic epoxy compounds include, for example,
compounds containing an epoxy group which are obtained by oxidizing
a carbon-carbon double bond of alkene compounds.
[0181] The cyclic aliphatic epoxy compounds include, for example,
compounds containing an epoxy group which are obtained by oxidizing
a carbon-carbon double bond of cycloalkene compounds.
[0182] The bisphenol A type epoxy compounds include, for example,
jER828, jER1001, jER1002, jER1003, jER1004, jER1007 and jER1010
(all manufactured by Mitsubishi Chemical Corporation), Epotohto
YD-128 (manufactured by Tohto Kasei Co., Ltd.), jER-331, DER-332
and DER-334 (all manufactured by The Dow Chemical Company), EPICLON
840, EPICLON 850 and EPICLON 1050 (all manufactured by DIC
Corporation), and EPMIC R-140, EPMIC R-301, and EPMIC R-304 (all
manufactured by Mitsui Chemicals, Inc.).
[0183] The bisphenol F type epoxy compounds include, for example,
jER806, jER807 and jER4004P (all manufactured by Mitsubishi
Chemical Corporation), Epotohto YDF-170, Epotohto YDF-175S and
Epotohto YDF-2001 (all manufactured by Tohto Kasei Co., Ltd.),
DER-354 (manufactured by The Dow Chemical Company), and EPICLON 830
and EPICLON 835 (all manufactured by DIC Corporation).
[0184] The bisphenol type epoxy compounds include, for example,
epoxy compounds of
2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane.
[0185] The hydrogenated bisphenol A type epoxy compounds include,
for example, Santohto ST-3000 (manufactured by Tohto Kasei Co.,
Ltd.), RIKARESIN HBE-100 (manufactured by New Japan Chemical Co.,
Ltd.), and Denacol EX-252 (manufactured by Nagase ChemteX
Corporation).
[0186] The hydrogenate bisphenol type epoxy compounds include, for
example, epoxy compounds of hydrogenate
2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane.
[0187] The brominated bisphenol A type epoxy compounds include, for
example, jER5050 and jER5051 (all manufactured by Mitsubishi
Chemical Corporation), Epotohto YDB-360 and Epotohto YDB-400 (all
manufactured by Tohto Kasei Co., Ltd.), DER-530 and DER-538 (all
manufactured by The Dow Chemical Company), and EPICLON 152 and
EPICLON 153 (all manufactured by DIC Corporation).
[0188] The phenol novolac type epoxy compounds include, for
example, jER152 and jER154 (all manufactured by Mitsubishi Chemical
Corporation), YOPN-638 (manufactured by Tohto Kasei Co., Ltd.),
DEN-431 and DEN-438 (all manufactured by The Dow Chemical Company),
EPICLON N-770 (manufactured by DIC Corporation), and EPPN-201 and
EPPN-202 (all manufactured by Nippon Kayaku Co., Ltd.).
[0189] The cresol novolac type epoxy compounds include, for
example, jER180S75 (manufactured by Mitsubishi Chemical
Corporation), YDCN-701 and YDCN-702 (all manufactured by Tohto
Kasei Co., Ltd.), EPICLON N-665 and EPICLON N-695 (all manufactured
by DIC Corporation), and EOCN-102S, EOCN-103S, EOCN-104S,
EOCN-1020, EOCN-1025, and EOCN-1027 (all manufactured by Nippon
Kayaku Co., Ltd.).
[0190] The bisphenol A novolac type epoxy compounds include, for
example, jER157S70 (manufactured by Mitsubishi Chemical
Corporation) and EPICLON N-880 (manufactured by DIC
Corporation).
[0191] The naphthalene skeleton-containing epoxy compounds include,
for example, EPICLON HP-403, EPICLON HP-4700 and EPICLON HP-4770
(manufactured by DIC Corporation), and NC-7000 (manufactured by
Nippon Kayaku Co., Ltd.).
[0192] The aromatic polyglycidyl ether compounds include, for
example, hydroquinone diglycidyl ether (following Formula EP-1),
catechol diglycidyl ether (following Formula EP-2), resorcinol
diglycidyl ether (following Formula EP-3),
2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-([2,3-epoxypropoxy]phenyl)-
]ethyl]phenyl]propane (following Formula EP-4),
tris(4-glycidyloxyphenyl)methane (following Formula EP-5), 1031S
and 1032H60 (all manufactured by Mitsubishi Chemical Corporation),
TACTIX-742 (manufactured by The Dow Chemical Company), Denacol
EX-201 (manufactured by Nagase ChemteX Corporation), DPPN-503,
DPPN-502H, DPPN-501H, and NC6000 (all manufactured by Nippon Kayaku
Co., Ltd.), TECHMORE VG3101L (manufactured by Mitsui Chemicals,
Inc.), a compound represented by the following Formula EP-6, and a
compound represented by the following Formula EP-7:
##STR00103##
[0193] The dicyclopentadiene phenol type epoxy compounds include,
for example, TACTIX-556 (manufactured by The Dow Chemical Company)
and EPICLON HP-7200 (manufactured by DIC Corporation).
[0194] The alicyclic diglycidyl ether compounds include, for
example, cyclohexanedimethanol diglycidyl ether compounds and
RIKARESIN DME-100 (manufactured by New Japan Chemical Co.,
Ltd.).
[0195] The aliphatic polyglycidyl ether compounds include, for
example, ethylene glycol diglycidyl ether (following Formula EP-8),
diethylene glycol diglycidyl ether (following Formula EP-9),
polyethylene glycol diglycidyl ether and polypropylene glycol
diglycidyl ether (following Formula EP-10), tripropylene glycol
diglycidyl ether (following Formula EP-11), polypropylene glycol
diglycidyl ether and neopentyl glycol diglycidyl ether (following
Formula EP-12), 1,4-butandiol diglycidyl ether (following Formula
EP-13), 1,6-hexandiol diglycidyl ether (following Formula EP-14),
dibromoneopentyl glycol diglycidyl ether (following Formula EP-15),
Denacol EX-810, Denacol EX-851, Denacol EX-8301, Denacol EX-911,
Denacol EX-920, Denacol EX-931, Denacol EX-211, Denacol EX-212, and
Denacol EX-313 (all manufactured by Nagase ChemteX Corporation),
DD-503 (manufactured by ADEKA CORPORATION), RIKARESIN W-100
(manufactured by New Japan Chemical Co., Ltd.),
1,3,5,6-tetraglycidyl-2,4-henxanediol (following Formula EP-16),
glycerin polyglycidyl ether, sorbitol polyglycidyl ethers,
trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl
ether, and Denacol EX-313, Denacol EX-611, Denacol EX-321, and
Denacol EX-411 (all manufactured by Nagase ChemteX
Corporation):
##STR00104##
[0196] The polysulfide type diglycidyl ether compounds include, for
example, FLDP-50 and FLDP-60 (all manufactured by Toray Thiokol
Co., Ltd.).
[0197] The biphenol type epoxy compounds include, for example,
YX-4000 and YL-6121H (all manufactured by Mitsubishi Chemical
Corporation), and NC-3000P and NC3000S (all manufactured by Nippon
Kayaku Co., Ltd.).
[0198] The diglycidyl ester compounds include, for example,
diglycidyl terephthalate (following Formula EP-17), diglycidyl
phthalate (following Formula EP-18), bis(2-methyloxyranylmethyl)
phthalate (following Formula EP-19), diglycidyl hexahydrophthalate
(following Formula EP-20), a compound represented by the following
Formula EP-21, a compound represented by the following Formula
EP-22, and a compound represented by the following Formula
EP-23:
##STR00105##
[0199] The glycidyl ester epoxy compounds include, for example, 871
and 872 (all manufactured by Mitsubishi Chemical Corporation),
EPICLON 200 and EPICLON 400 (all manufactured by DIC Corporation),
and Denacol EX-711 and Denacol EX-721 (all manufactured by Nagase
ChemteX Corporation).
[0200] The polyglycidylamine compounds include, for example,
N,N-diglycidylaniline (following Formula EP-24),
N,N-diglycidyl-o-toluidine (following Formula EP-25),
N,N-diglycidyl-m-toluidine (following Formula EP-26),
N,N-diglycidyl-2,4,6-tribromoaniline (following Formula EP-27),
3-(N,N-diglycidyl)aminopropyltrimethoxysilane (following Formula
EP-28), N,N,O-triglycidyl-p-aminophenol (following Formula EP-29),
N,N,O-triglycidyl-m-aminophenol (following Formula EP-30),
N,N,N',N',-tetraglycidyl-4,4'-diaminodiphenylmethane (following
Formula EP-31), N,N,N',N',-tetraglycidyl-m-xylylenediamine
(TETRAD-X (manufactured by Mitsubishi Chemical Corporation),
following Formula EP-32),
1,3-bis(N,N-diglycidylaminomethyl)cyclohexane (TETRAD-C
(manufactured by Mitsubishi Chemical Corporation), following
Formula EP-33), 1,4-bis(N,N-diglycidylaminomethyl)cyclohexane
(following Formula EP-34), 1,3-bis(N,N-diglycidylamino)cyclohexane
(following Formula EP-35), 1,4-bis(N,N-diglycidylamino)cyclohexane
(following Formula EP-36), 1,3-bis(N,N-diglycidylamino)benzene
(following Formula EP-37), 1,4-bis(N,N-diglycidylamino)benzene
(following Formula EP-38),
2,6-bis(N,N-diglycidylaminomethyl)bicyclo[2.2.1]heptane (following
Formula EP-39),
N,N,N',N'-tetraglycidyl-4,4'-diaminodicyclohexylmethane (following
Formula EP-40),
2,2'-dimethyl-(N,N,N',N'-tetraglycidyl)-4,4'-diaminobiphenyl
(following Formula EP-41),
N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenyl ether (following
Formula EP-42), 1,3,5-tris(4-(N,N-diglycidyl)aminophenoxy)benzene
(following Formula EP-43), 2,4,4'-tris(N,N-diglycidylamino)diphenyl
ether (following Formula EP-44),
tris(4-(N,N-diglycidyl)aminophenyl)methane (following Formula
EP-45), 3,4,3',4'-tetrakis(N,N-diglycidylamino)biphenyl (following
Formula EP-46), 3,4,3',4'-tetrakis(N,N-diglycidylamino)diphenyl
ether (following Formula EP-47), a compound represented by the
following Formula EP-48, and a compound represented by the
following Formula EP-49:
##STR00106## ##STR00107## ##STR00108## ##STR00109##
[0201] The homopolymers of the monomers having oxyranyl include,
for example, polyglycidyl methacrylate. The copolymers of the
monomers having oxyranyl include, for example,
N-phenylmaleimide-glycidyl methacrylate copolymers,
N-cyclohexylmaleimide-glycidyl methacrylate copolymers, benzyl
methacrylate-glycidyl methacrylate copolymers, butyl
methacrylate-glycidyl methacrylate copolymers, 2-hydoxyethyl
methacrylate-glycidyl methacrylate copolymers,
(3-ethyl-3-oxetanyl)methyl methacrylate-glycidyl methacrylate
copolymers, and styrene-glycidyl methacrylate copolymers.
[0202] The monomers having oxyranyl include, for example, glycidyl
(meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, and
methylglycidyl (meth)acrylate.
[0203] Other monomers than the monomers having oxyranyl in the
copolymers of the monomers having oxyranyl include, for example,
(meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate,
isopropyl (meth)acrylate, butyl (meth)acrylate, iso-butyl
(meth)acrylate, t-butyl (meth)acrylate, cyclohexyl (meth)acrylate,
benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate,
2-hydroxypropyl (meth)acrylate, styrene, methylstyrene,
chloromethylstyrene, (3-ethyl-3-oxetanyl)methyl (meth)acrylate,
N-cyclohexylmaleimide, and N-phenylmaleimide.
[0204] Glycidyl isocyanurate includes, for example,
1,3,5-triglycidyl-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione (following
Formula EP-50),
1,3-diglycidyl-5-allyl-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione
(following Formula EP-51), and glycidyl isocyanurate type epoxy
resins:
##STR00110##
[0205] The linear aliphatic epoxy compounds include, for example,
epoxidized polybutadiene and EPOLEAD PB3600 (manufactured by DAICEL
CORPORATION).
[0206] The cyclic aliphatic epoxy compounds include, for example,
3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate
(CELLOXIDE 2021 (manufactured by DAICEL CORPORATION), following
Formula EP-52),
2-methyl-3,4-epoxycyclohexenylmethyl-2'-methyl-3',4'-epoxycyclohexylcarbo-
xylate (following Formula EP-53),
2,3-epoxycyclopentane-2',3'-epoxycyclopentaneether (following
Formula EP-54), .epsilon.-caprolactone-modified
3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate,
1,2:8,9-diepoxylimonene (CELLOXIDE 3000 (manufactured by DAICEL
CORPORATION), following Formula EP-55), a compound represented by
the following Formula EP-56, CY-175, CY-177 and CY-179 (all
manufactured by The Ciba-Geigy Chemical Corp. (available from
Huntsman Japan Inc.)), EHPD-3150 (manufactured by DAICEL
CORPORATION), and cyclic aliphatic epoxy resins:
##STR00111##
[0207] The epoxy compound is preferably at least one of the
polyglycidylamine compounds, the bisphenol A novolac type epoxy
compounds, the cresol novolac type epoxy compounds, and the cyclic
aliphatic epoxy compounds, and it is preferably at least one of
N,N,N',N'-tetraglycidyl-m-xylenediamine,
1,3-bis(N,N-diglycidylaminomethyl)cyclohexane,
N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, trade name:
"TECHMORE VG3101L",
3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate, the
N-phenylmaleimide-glycidyl methacrylate copolymers,
N,N,O-triglycidyl-p-aminophenol, the bisphenol A novolac type epoxy
compounds, and the cresol novolac type epoxy compounds.
<Other Polymers>
[0208] The liquid crystal aligning agent of the present invention
may further contain, for example, polymers other than the polyamic
acid and derivative thereof for the purpose of controlling the
electric characteristics and an aligning property of the liquid
crystal display device. The above polymers include polymers soluble
in organic solvents. The above polymers may be used alone or in
combination of two or more kinds thereof. From the viewpoint of the
purpose described above, a content of the above polymers is
preferably 0.01 to 100% by weight, more preferably 0.1 to 70% by
weight and further preferably 0.1 to 50% by weight based on the
polyamic acid or derivative thereof. The above polymers include,
for example, polyamides, polyurethanes, polyureas, polyesters,
polyepoxides, polyesterpolyols, silicone-modified polyurethanes,
silicone-modified polyesters, polyacrylic acid alkyl esters,
polymethacrylic acid alkyl esters, acrylic acid alkyl esters and
methacrylic acid alkyl esters copolymers, polyoxyethylene glycol
diacrylate, polyoxyethylene glycol dimethacrylate, polyoxypropylene
glycol diacrylate, and polyoxypropylene glycol dimethacrylate.
<Low Molecular Weight Compound>
[0209] The liquid crystal aligning agent of the present invention
may further contain, for example, a low molecular weight compound.
The low molecular weight compound includes, for example, 1) when
the coating property is desired to be enhanced, a surfactant which
meets the above purpose, 2) when the antistatic property is
required to be enhanced, an antistatic agent, 3) when the adhesive
property with the substrate and the rubbing resistance are desired
to be enhanced, a silane coupling agent and a titanium base
coupling agent, and 4) when the imidization is promoted at low
temperature, an imidization catalyst. From the viewpoints described
above, a content of the low molecular weight compound is preferably
0.1 to 50% by weight, more preferably 0.1 to 40% by weight and
further preferably 0.1 to 20% by weight based on the polyamic acid
or derivative thereof.
[0210] The silane compounds having an epoxy group which are listed
as the examples of the epoxy compounds are included as well in the
silane coupling agent. For the purpose of stabilizing the electric
characteristics over a long period of time in addition to enhancing
the adhesive property with the substrate and the rubbing
resistance, the silane coupling agent having an epoxy group may be
added to the liquid crystal aligning agent of the present
invention.
[0211] The silane coupling agent includes, for example,
vinyltrimethoxysilane, vinyltriethoxysilane,
N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane,
N-(2-aminoethyl)-3-aminopropylmethyltrimethoxysilane,
paraaminophenyltrimethoxysilane, paraaminophenyltriethoxysilane,
metaaminophenyltrimethoxysilane, metaaminophenyltriethoxysilane,
3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,
3-chloropropylmethyl-dimethoxysilane,
3-chloropropyltrimethoxysilane,
3-methacryloxypropyltrimethoxysilane,
3-mercaptopropyltrimethoxysilane,
N-(1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propylamine, and
N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine. The silane
coupling agent having an epoxy group includes
3-glycidoxypropyltrimethoxysilane,
3-glycidoxypropylmethyldimethoxysilane, and
2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.
[0212] The preferred silane coupling agent includes
3-glycidoxypropyltrimethoxysilane,
2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,
paraaminophenyltrimethoxysilane, and
3-aminopropyltriethoxysilane.
[0213] The imidization catalyst includes, for example, aliphatic
amines such as trimethylamine, triethylamine, tripropylamine,
tributylamine, and the like; aromatic amines such as
N,N-dimethylaniline, N,N-diethylaniline, methyl-substituted
aniline, hydroxy-substituted aniline, and the like; and cyclic
amines such as pyridine, methyl-substituted pyridine,
hydroxy-substituted pyridine, quinoline, methyl-substituted
quinoline, hydroxy-substituted quinoline, isoquinoline,
methyl-substituted isoquinoline, hydroxy-substituted isoquinoline,
imidazole, methyl-substituted imidazole, hydroxy-substituted
imidazole, and the like. The imidization catalyst is preferably at
least one selected from N,N-dimethylaniline, o-hydroxyaniline,
m-hydroxyaniline, p-hydroxyaniline, o-hydroxypyridine,
m-hydroxypyridine, p-hydroxypyridine, and isoquinoline.
<Liquid Crystal Aligning Agent>
[0214] The liquid crystal aligning agent of the present invention
is a photo-aligning liquid crystal aligning agent containing the
polyamic acid or derivative thereof which is obtained by reacting
at least one tetracarboxylic acid dianhydride or a mixture thereof
selected from the compounds represented by Formulas (AN-a) to
(AN-c) described above and at least one diamine or a mixture
thereof selected from the compounds represented by Formulas (DI-a)
to (DI-c) described above, wherein at least one of the
tetracarboxylic acid dianhydride having a photoreactive structure
and the diamine having a photoreactive structure is an essential
component, and other polyamic acids or derivatives thereof may be
used in a mixture. In the liquid crystal aligning agent of the
present invention, polymers other than polyamic acid or a
derivative thereof which is obtained by reacting acid anhydride
with diamine, for example, polyesters and epoxy resins can be used
in combination. However, when the above other polymers are used in
combination, a proportion thereof is preferably 30% by weight or
less based on a whole weight of the polymers.
<Solvent>
[0215] The aligning agent of the present invention is a solution
obtained by dissolving the polyamic acid in a solvent. The solvent
can suitably be selected from solvents used in producing and using
publicly known polyamic acids according to the use purposes. The
examples of the above solvents are shown below.
[0216] The examples of aprotic organic solvents include
N-methyl-2-pyrrolidone (NMP), dimethylimidazolidinone,
N-methylcaprolactam, N-methylpropionamide, N,N-dimethylacetamide,
dimethyl sulfoxide, N,N-dimethylformamide (DMF),
N,N-diethylformamide, N,N-diethylacetamide (DMAc), and lactones
such as .gamma.-butyrolactone (GBL) and the like.
[0217] The preferred examples of solvents which are solvents other
than those described above and which are used for the purpose of
improving the coating property and the like include alkyl butyrate,
3-methyl-3-methoxybutanol, tetralin, isophorone, ethylene glycol
monoalkyl ethers (examples: ethylene glycol monobutyl ether (BCS)),
diethylene glycol monoalkyl ethers (examples: diethylene glycol
monoethyl ether), ethylene glycol monophenyl ether, triethylene
glycol monoalkyl ethers, propylene glycol monoalkyl ethers
(examples: propylene glycol monobutyl ether), dialkyl malonate
(examples: diethyl malonate), dipropylene glycol monoalkyl ethers
(examples: dipropylene glycol monomethyl ether), and ester
compounds of the above glycol monoethers. Among them, MMP,
dimethylimidazolidinone, GBL, BCS, diethylene glycol monoethyl
ether, propylene glycol monobutyl ether, and dipropylene glycol
monomethyl ether are particularly preferred.
[0218] A concentration of the polymers in the aligning agent of the
present invention is preferably 0.1 to 40% by weight, more
preferably 1 to 10% by weight. When a layer thickness thereof has
to be controlled in coating the aligning agent on the substrate, a
concentration of the polymers contained can be controlled in
advance by diluting it with a solvent.
[0219] A viscosity of the aligning agent of the present invention
is varied in a preferred range according to a coating method, a
concentration of the polyamic acid or derivative thereof, the kind
of the polyamic acid or derivative thereof used, and the kind and a
proportion of the solvent. When coating it by means of, for
example, a printing machine, the viscosity is 5 to 100 mPas (more
preferably 10 to 80 mPas). If it is smaller than 5 mPas, it is
difficult to obtain the sufficiently large layer thickness, and if
it exceeds 100 mPas, unevenness in printing is increased in a
certain case. In a case of coating by spin coating, the viscosity
is suitably 5 to 200 mPas (more preferably 10 to 100 mPas). When
coating by means of an ink jet coating equipment, the viscosity is
suitably 5 to 50 mPas (more preferably 5 to 20 mPas). A viscosity
of the liquid crystal aligning agent is measured by a rotation
viscosity measuring method, and it is measured (measuring
temperature: 25.degree. C.) by means of, for example, a rotational
viscometer (model TVE-20L, manufactured by Toki Sangyo Co.,
Ltd.).
<Liquid Crystal Alignment Layer>
[0220] The liquid crystal alignment layer of the present invention
can be formed, as is the case with preparing conventional liquid
crystal alignment layers, by coasting the liquid crystal aligning
agent of the present invention on a substrate in the liquid crystal
display device. The substrate described above includes a glass-made
substrate on which an electrode such as ITO (indium tin oxide), IZO
(In.sub.2O.sub.3--ZnO), IGZO (In--Ga--ZnO.sub.4) electrodes and the
like, a color filter and the like may be provided. Also, a spinner
method, a printing method, a dipping method, a dropping method, an
ink jet method and the like are known as a method for coating the
liquid crystal aligning agent.
<Production Step for Liquid Crystal Alignment Layer>
[0221] A method for carrying out heating treatment in an oven or an
infrared furnace, a method for carrying out heating treatment on a
hot plate, and the like are usually known as the heating and drying
step described above. The heating and drying step is carried out
preferably at temperature falling in a range in which the solvent
can be vaporized, and it is carried out more preferably at a
relatively low temperature as compared with temperature in the
heating and incinerating step. To be specific, the heating and
drying temperature falls in a range of preferably 30 to 150.degree.
C., more preferably 50 to 120.degree. C.
[0222] The heating and baking step described above can be carried
out on a condition which is required for the polyamic acid or
derivative thereof described above to be subjected to dehydrating
cyclization. A method for carrying out heating treatment in an oven
or an infrared furnace, a method for carrying out heating treatment
on a hot plate, and the like are usually known as the method for
baking the coating layer described above. The above methods can be
applied as well in the present invention. In general, the heating
and baking step is carried out preferably at a temperature of 100
to 300.degree. C. for 1 minute to 3 hours, more preferably 120 to
280.degree. C. and further preferably 150 to 250.degree. C.
[0223] A method for forming the liquid crystal alignment layer of
the present invention by a photo-aligning method shall specifically
be explained. The liquid crystal alignment layer of the present
invention can be formed by the photo-aligning method, wherein the
coating layer is dried using by heating and then irradiated with a
linearly polarized or non-polarized radial ray to thereby provide
the coating layer with anisotropy, and the layer is heated and
baked. Or, it can be formed by heating and drying the coating
layer, heating and baking and then irradiating it with a linearly
polarized or non-polarized radial ray. From the viewpoint of the
aligning property, the step of irradiating with a radial ray is
carried out preferably before the heating and baking step.
[0224] Further, in order to enhance a liquid crystal aligning
ability of the liquid crystal alignment layer, the coating layer
can be irradiated as well with a linearly polarized or
non-polarized radial ray while heating it. Irradiation of the
coating layer with a radial ray may be carried out in the step of
heating and drying the coating layer or the step of heating and
baking it, or it may be carried out between the heating and drying
step and the heating and baking step. A heating and drying
temperature in the above step falls in a range of preferably 30 to
150.degree. C., more preferably 50 to 120.degree. C. Also, a
heating and baking temperature in the above step falls in a range
of preferably 30 to 300.degree. C., more preferably 50 to
250.degree. C.
[0225] A UV ray or a visible light containing light having a
wavelength of, for example, 150 to 800 nm can be used as the radial
ray, and a UV ray containing light having a wavelength of 300 to
400 nm is preferred. Also, a linearly polarized or non-polarized
ray can be used. The above rays shall not specifically be
restricted as long as they can provide the coating layer with a
liquid crystal aligning ability, and when a strong aligning
regulation force is desired to be exerted on the liquid crystal, a
linearly polarized ray is preferred.
[0226] The liquid crystal alignment layer of the present invention
can show a high liquid crystal aligning ability even by irradiating
with a ray having a low energy. A dose of the linearly polarized
ray in the radial ray irradiation step described above is
preferably 0.05 to 20 J/cm.sup.2, more preferably 0.5 to 10
J/cm.sup.2. Also, a wavelength of the linearly polarized ray is
preferably 200 to 400 nm, more preferably 300 to 400 nm. An
irradiation angle of the linearly polarized ray to the surface of
the layer shall not specifically be restricted, and when the strong
aligning regulation force is desired to be exerted on the liquid
crystal, it is preferably as vertical to the surface of the layer
as possible from the viewpoint of shortening the aligning treatment
time. Also, the liquid crystal alignment layer of the present
invention can align the liquid crystal in a direction vertical to a
polarizing direction of the linearly polarized ray by irradiating
with the linearly polarized ray.
[0227] When a pre-tilt angle is desired to be exerted, a ray
irradiated on the layer described above may be either a linearly
polarized ray or a non-polarized ray as described above. A dose of
the ray irradiated on the layer when a pre-tilt angle is desired to
be exerted is preferably 0.05 to 20 J/cm.sup.2, particularly
preferably 0.5 to 10 J/cm.sup.2, and a wavelength thereof is
preferably 250 to 400 nm, particularly preferably 300 to 380 nm. An
irradiation angle of the ray irradiated on the layer when a
pre-tilt angle is desired to be exerted shall not specifically be
restricted, and it is preferably 30 to 60 degrees from the
viewpoint of shortening the aligning treatment time.
[0228] An ultrahigh pressure mercury lamp, a high pressure mercury
lamp, a low pressure mercury lamp, a Deep UV lamp, a halogen lamp,
a metal halide lamp, a high power metal halide lamp, a xenon lamp,
a mercury xenon lamp, an excimer lamp, a KrF excimer laser, a
fluorescent lamp, an LED lamp, a sodium lamp, a microwave-excited
electrodeless lamp and the like can be used for a light source used
in the step of irradiating with a linearly polarized or
non-polarized radial ray without limitations.
[0229] The liquid crystal alignment layer of the present invention
is suitably obtained by a method further including other steps than
the steps described above. For example, a step of rinsing the layer
with a cleaning solution after baking or irradiating with a radial
ray is not essential in the liquid crystal alignment layer of the
present invention, but the rinsing step can be provided due to
convenience of the other steps.
[0230] The rinsing method with a cleaning solution includes
brushing, jet spraying, steam cleaning, ultrasonic cleaning and the
like. The above methods may be carried out alone or in combination.
Capable of being used as the cleaning solution are purified water
or various alcohols such as methyl alcohol, ethyl alcohol,
isopropyl alcohol and the like, aromatic hydrocarbons such as
benzene, xylene, toluene and the like, halogenated solvents such as
methylene chloride and the like, ketones such as acetone, methyl
ethyl ketone and the like, but it shall not be restricted to them.
It is a matter of course that solutions which are sufficiently
refined and which contain fewer impurities are used for the above
cleaning solutions. The above rinsing method can be applied as well
to the rinsing step described above in forming the liquid crystal
alignment layer of the present invention.
[0231] In order to enhance a liquid crystal aligning ability of the
liquid crystal alignment layer of the present invention, annealing
treatment by heat or light can be used before and after the heating
and baking step, the rubbing step or the step of irradiating with a
polarized or non-polarized radial ray. In the above annealing
treatment, an annealing temperature is 30 to 180.degree. C.,
preferably 50 to 150.degree. C., and an annealing time is
preferably 1 minute to 2 hours. An annealing light used for the
annealing treatment includes a UV lamp, a fluorescent lamp, an LED
lamp and the like. A dose of the light is preferably 0.3 to 10
J/cm.sup.2.
[0232] A layer thickness of the liquid crystal alignment layer of
the present invention shall not specifically be restricted and is
preferably 10 to 300 nm, more preferably 30 to 150 nm. A layer
thickness of the liquid crystal alignment layer of the present
invention can be measured by means of publicly known layer
thickness-measuring devices such as a step gauge, an ellipsometer
and the like.
[0233] The liquid crystal alignment layer of the present invention
is characterized by having a particularly large aligning
anisotropy. A size of the above anisotropy can be evaluated by a
method using polarized IR described in JP-A 2005-275364 and the
like. Also, it can be evaluated as well by a method using an
ellipsometry as shown in the following examples. When the alignment
layer of the present invention is used as an alignment layer for a
liquid crystal composition, it is considered that a material having
a larger anisotropy of the layer has a large aligning regulation
force to the liquid crystal composition.
[0234] The liquid crystal alignment layer of the present invention
can be used for controlling alignment of optical compensation
materials and other all liquid crystal materials in addition to
uses of aligning liquid crystal compositions for liquid crystal
displays. Also, the liquid crystal alignment layer of the present
invention has a large anisotropy and therefore can be used alone
for uses in optical compensation materials.
<Liquid Crystal Display Device>
[0235] The liquid crystal display device of the present invention
comprises a pair of substrates, a liquid crystal layer containing
liquid crystal molecules and formed between a pair of the
substrates described above, an electrode for applying a voltage to
the liquid crystal layer and a liquid crystal alignment layer for
aligning the liquid crystal molecules described above to a
prescribed direction. The liquid crystal alignment layer of the
present invention is used for the liquid crystal alignment layer
described above.
[0236] The glass-made substrate described above in the liquid
crystal alignment layer of the present invention can be used for
the substrate, and as described in the liquid crystal alignment
layer of the present invention, the ITO, IZO and IGZO electrodes
formed on the glass-made substrate can be used for the electrode
described above.
[0237] The liquid crystal layer is formed by the liquid crystal
composition tightly sealed in a space between a pair of the
substrates, wherein the substrates are provided oppositely so that
a face on which the liquid crystal alignment layer is formed in one
substrate of a pair of the substrates described above is faced to
the other substrate.
[0238] The liquid crystal shall not specifically be restricted, and
various liquid crystal compositions having a positive or negative
dielectric anisotropy can be used. The preferred liquid crystal
compositions having a positive dielectric anisotropy include liquid
crystal compositions disclosed in Japanese Patent No. 3086228,
Japanese Patent No. 2635435, JP-A (through PCT) 1993-501735, JP-A
1996-157826, JP-A 1996-231960, JP-A 1997-241644 (EP885272A1), JP-A
1997-302346 (EP806466A1), JP-A 1996-199168 (EP722998A1), JP-A
1997-235552, JP-A 1997-2555956, JP-A 1997-241643 (EP885271A1), JP-A
1998-204016 (EP844229A1), JP-A 1998-204436, JP-A 1998-231482, JP-A
2000-087040, JP-A 2001-48822 and the like.
[0239] The preferred liquid crystal compositions having a negative
dielectric anisotropy include liquid crystal compositions disclosed
in JP-A 1982-114532, JP-A 1990-4725, JP-A 1992-224885, JP-A
1996-104869, JP-A 1998-168076, JP-A 1998-168453, JP-A 1998-236989,
JP-A 1998-236990, JP-A 1998-236992, JP-A 1998-236993, JP-A
1998-236994, JP-A 1998-237000, JP-A 1998-237004, JP-A 1998-237024,
JP-A 1998-237035, JP-A 1998-237075, JP-A 1998-237076, JP-A
1998-237448 (EP967261A1), JP-A 1998-287874, JP-A 1998-287875, JP-A
1998-291945, JP-A 1999-029581, JP-A 1999-080049, JP-A 2000-256307,
JP-A 2001-019965, JP-A 2001-072626, JP-A 2001-192657 and the
like
[0240] It is no matter to add at least one optically active
compound to the liquid crystal composition having a positive or
negative dielectric anisotropy.
[0241] The liquid crystal display device of the present invention
is obtained by forming the liquid crystal alignment layer of the
present invention on at least one of a pair of the substrates,
providing oppositely a pair of the substrates via spacers so that
the liquid crystal alignment layer is turned to an inside and
sealing the liquid crystal composition in a space formed between
the substrates to form a liquid crystal layer. An additional step
of sticking a polarizing layer on the substrate may be included, if
necessary, in the production step of the liquid crystal aligning
device of the present invention.
[0242] In the liquid crystal display device of the present
invention, liquid crystal display devices for various electric
field systems can be formed. The above liquid crystal display
devices for electric field systems include liquid crystal display
devices of a lateral electric field system in which a voltage is
applied to the liquid crystal layer by the electrode in a
horizontal direction toward the surface of the substrate and liquid
crystal display devices of a vertical electric field system in
which a voltage is applied to the liquid crystal layer by the
electrode in a vertical direction toward the surface of the
substrate.
[0243] The liquid crystal alignment layer prepared by using the
liquid crystal aligning agent of the present invention as the raw
material can be applied to liquid crystal display devices of
various display drive systems by suitably selecting the polymers
which are the raw material thereof.
[0244] The liquid crystal display device of the present invention
may further comprise factors other than the constitutional factors.
Constitutional factors usually used for liquid crystal display
devices, such as a polarizing plate (polarizing layer), a
wavelength plate, a light diffusion layer, a driving circuit and
the like may be mounted as the above other constitutional factors
in the liquid crystal display device of the present invention.
EXAMPLES
[0245] The present invention shall be explained below with
reference to examples. Evaluating methods and compounds used in the
examples are shown below.
<Evaluating Method of Liquid Crystal Display Device>
1. Residual DC:
[0246] A DC voltage of 5 V was applied to a liquid crystal display
device described later for 15 minutes, and then the device was
short-circuited for 1 second. After it was released for 15 minutes,
a residual DC thereof was measured, and the values in the beginning
and after relaxed for 15 minutes were obtained respectively. The
measuring temperature was 60.degree. C. A liquid crystal physical
property-measuring system, model 6254 manufactured by TOYO
Corporation was used for the measuring device. It is shown that the
smaller the initial value of the residual DC is and the more
largely the value after relaxed for 15 minutes is reduced from the
initial value, the more the storage of residual DC is decreased and
the relaxation time can be shortened and that afterimages can be
prevented from being generated.
2. Aligning Property:
[0247] A liquid crystal display device described later was
interposed between polarizing plates in which cross Nichol prisms
were disposed, and it was visually confirmed whether or not the
phenomenon that when liquid crystal was injected into the cell, the
liquid crystal molecules were fixed in a direction in which the
liquid crystal molecules flowed, so-called flow aligning was
observed.
<Tetracarboxylic Acid Dianhydride>
[0248] Acid dianhydride (A1): ehtylenediaminetetraacetic acid
dianhydride: a compound in which X.sup.1 is --CH.sub.2CH.sub.2-- in
(AN-a) Acid dianhydride (A2): 1,8-bis(3,4-phenyl
dicarboxylate)octane dianhydride: a compound in which X.sup.2 is
--(CH.sub.2).sub.8-- in (AN-b) Acid dianhydride (A3):
3,3',4,4'-diphenylethertetracarboxylic acid dianhydride: (An-c)
Acid dianhydride (A4): 1,2,4,5-cyclohexanetetracarboxylic acid
dianhydride: (An-3-1) Acid dianhydride (A5):
azobenznene-3,3',4,4'-tetracarboxylic acid dianhydride: (VII-3)
Acid dianhydride (A6):
5,5'-p-phenylenebis(isobenzofuran-1,3-dione): (AN-16-14)
<Diamine>
[0249] Diamine (D1): 4,4'-diaminoazobenznene: (VII-1-1) Diamine
(D2): 4,4'-diaminostilbene: (VI-1-1) Diamine (D3):
4,4'-diaminodiphenyl-1,4-butadiyne: compound in which both of two
amino groups are bonded to a para position in (II-1-1) Diamine
(D4): 1,4-cyclohexanediamine: compound in which both of two amino
groups are bonded to a para position in (DI-a) Diamine (D5):
3,3'-dimethyl-4,4'-diaminodiphenylmethane: compound in which a is
1, in which both of R.sup.1 are methyl bonded to a meta position
and in which both of two amino groups are bonded to a para position
in (DI-b) Diamine (D6): 4,4'-diaminodiphenylethane: compound in
which a is 2, in which both of R.sup.1 are hydrogen and in which
both of two amino groups are bonded to a para position in (DI-b)
Diamine (D7): 4,4'-diaminodiphenylbutane: compound in which a is 4,
in which both of R.sup.1 are hydrogen and in which both of two
amino groups are bonded to a para position in (DI-b) Diamine (D8):
4,4'-N,N'-bis(4-aminophenyl)piperazine: (DI-c) Diamine (D9):
4,4'-diaminodiphenyloctane: (DI-5-31) Diamine (D10):
4,4'-diaminodiphenylhexane: (DI-5-29) Diamine (D11):
1,8-diaminooctane: (DI-1-3) Diamine (D12):
1,1-bis(4-((aminophenyl)methyl)phenyl)-4-butylcyclohexane: compound
in which R.sup.40 is --C.sub.4H.sub.9 in (DI-16-2) Diamine (D13):
1,1-bis((aminophenoxy)phenyl)-4-(n-hexylcyclohexyl)cyclohexane:
compound in which R.sup.44 is --C.sub.7H.sub.15 in (DI-16-4)
Diamine (D14):
1,1-bis((aminophenoxy)phenyl)-4-((n-pentylcyclohexyl)ethyl)cyclohexane:
compound in which R.sup.44 is --C.sub.5H.sub.11 in (DI-16-7)
Diamine (D15): 3,5-diamino-N-((dihydroxymethyl)methyl)benzamide:
(DI-4-12) Diamine (D16):
3,5-diamino-N-((trihydroxymethyl)methyl)benzamide: (DI-4-13)
<Solvent>
[0250] N-methyl-2-pyrrolidone: NMP Butyl cellosolve (ethylene
glycol monobutyl ether): BC
<Additives>
[0251] Additive (Ad1):
bis[4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)phenyl]methane
Additive (Ad2): 1,3-bis(4,5-dihydro-2-oxazolyl)benzene Additive
(Ad3): 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane Additive (Ad4):
3-aminopropyltriethoxysilane
1. Synthesis of Polyamic Acid
Synthetic Example 1
[0252] A four neck flask of 100 mL equipped with a thermometer, a
stirrer, a raw material-charging port and a nitrogen
gas-introducing port was charged with 2.27 g of diamine (D1), 0.31
g of diamine (D4) and 50 g of dehydrated NMP, and the mixture was
dissolved by stirring under dry nitrogen flow. Then, 3.42 g of acid
dianhydride (A1) and 24 g of dehydrated NMP were added thereto, and
the mixture was continued to be stirred at room temperature for 24
hours. BC 20 g was added to the above reaction solution to obtain a
polyamic acid solution having a polymer solid concentration of 6%
by weight. This polyamic acid solution is designated as PA1. The
polyamic acid contained in PA1 had a weight average molecular
weight of 39,000.
[0253] The weight average molecular weight of polyamic acid was
determined by measuring a molecular weight by means of a 2695
separation module.2414 differential refractometer (manufactured by
Waters Corporation) according to a GPC method and reducing it to
polystyrene. The polyamic acid thus obtained was diluted by a
phosphoric acid-DMF mixed solution (phosphoric acid/DMF=0.6/100:
weight ratio) so that a concentration of the polyamic acid was
about 2% by weight. HSPgel RT MB-M (manufactured by Waters
Corporation) was used for the column, and the mixed solution
described above was used for the developer to carry out the
measurement on the conditions of a column temperature of 50.degree.
C. and a flow rate of 0.40 ml/minute. TSK standard polystyrene
manufactured by Tosoh Corp. was used for standard polystyrene.
Synthetic Examples 2 to 17
[0254] Polyamic acid solutions (PA2) to (PA17) having a polymer
solid concentration of 6% by weight were prepared according to
Synthetic Example 1, except that the tetracarboxylic acid
dianhydride and the polyamic acid were changed as shown in Table 1.
The measured results of a weight average molecular weight of the
polyamic acid obtained including the result obtained in Synthetic
Example 1 were summarized in Table 1.
TABLE-US-00001 TABLE 1 Polyamic acid Tetracarboxylic acid Synthetic
solution dianhydride (mol %) Diamine (mol %) Example No. A1 A2 A3
A4 A5 A6 D1 D2 D3 D4 D5 D6 1 PA1 100 80 20 2 PA2 100 50 50 3 PA3 70
30 50 50 4 PA4 100 50 5 PA5 100 50 6 PA6 70 30 50 7 PA7 50 50 8 PA8
100 50 9 PA9 100 50 10 PA10 100 50 40 11 PA11 70 30 70 15 12 PA12
50 50 90 13 PA13 50 50 80 14 PA14 50 50 80 10 15 PA15 100 100 16
PA16 100 100 17 PA17 100 20 Weight average Synthetic Diamine (mol
%) molecular Example D7 D8 D9 D10 D11 D12 D13 D14 D15 D16 weight 1
39,000 2 41,000 3 42,000 4 50 52,000 5 50 67,000 6 50 45,000 7 100
34,000 8 20 30 56,000 9 20 30 42,000 10 10 55,000 11 15 82,000 12 5
5 66,000 13 10 10 94,000 14 10 89,000 15 45,000 16 74,000 17 80
28,000
2. Preparation of Liquid Crystal Display Device
Example 1
[0255] A mixed solvent of NMP/BC=4/1 (weight ratio) was added to
the polyamic acid solution (PA1) having a polymer solid
concentration of 6% by weight which was prepared in Synthetic
Example 1 to dilute the solution to a polymer solid concentration
of 4% by weight, whereby a liquid crystal aligning agent was
prepared. The liquid crystal aligning agent thus obtained was used
to prepare a liquid crystal display device as shown below.
<Preparing Method of Liquid Crystal Display Device>
[0256] The liquid crystal aligning agent was coated on two glass
substrates provided with ITO electrodes by means of a spinner (spin
coater (1H-DX2), manufactured by Mikasa Co., Ltd.). After coated,
the layer was dried by heating at 70.degree. C. for about 1 minute
on a hot plate (EC Hot Plate (EC-1200N), manufactured by AS ONE
Corporation), and then it was irradiated with a linearly polarized
UV ray via a polarizing plate from a direction vertical to the
substrate by means of Multilight ML-501C/B, manufactured by USHO
INC. In the above case, the luminous energy was measured by means
of a UV ray integration actinometer UIT-150 (optical receiver
UVD-5365), and the exposure time was controlled so that the
exposure energy was 5.0.+-.0.1 J/cm.sup.2 at a wavelength of 365
nm. Then, the layer was subjected to heat treatment at 230.degree.
C. for 15 minutes in a clean oven (Clean Oven (PVHC-231),
manufactured by ESPEC Corp.) to form an alignment layer having a
layer thickness of 100.+-.10 nm.
[0257] The faces on which the alignment layers were formed in two
substrates having the alignment layers formed on the ITO electrodes
were oppositely disposed to form a gap for injecting a liquid
crystal composition into the gap between the opposite substrates so
that the polarization directions of UV rays irradiated onto the
respective alignment layers were parallel, and the substrates were
stuck together to prepare a vacant cell having a cell thickness of
4 .mu.m. An injection port for injecting liquid crystal into the
above vacant cell was provided in such a position that a direction
in which the liquid crystal flowed in injection was almost parallel
to a polarization direction of a UV ray irradiated onto the
alignment layer.
[0258] A liquid crystal composition A shown below was injected into
the vacant cell prepared above under vacuum to prepare a liquid
crystal display device.
<Liquid Crystal Composition A>
##STR00112## ##STR00113##
[0259] Physical property values: NI 100.1.degree. C.;
.DELTA..di-elect cons.5.1; .DELTA.n 0.093; .eta. 25.6 mPas
[0260] The liquid crystal display device prepare above was used to
measure residual DC by the method described above to find that an
initial value of the residual DC was 785 mV and that the value
thereof after relaxed for 15 minutes was 59 mV. Also, flow aligning
was not confirmed, and the aligning property was good.
Examples 2 to 14
[0261] The mixed solvent of NMP/BC=4/1 (weight ratio) was added to
the respective polyamic acid solutions (PA2 to PA14) having a
polymer solid concentration of 6% by weight which were prepared in
Synthetic Examples 2 to 14 to dilute the solutions to a polymer
solid concentration of 4% by weight, whereby liquid crystal
aligning agents were prepared. The liquid crystal aligning agents
thus obtained were used to prepare vacant cells by the method
according to Example 1. Then, the liquid crystal composition A was
injected into the above vacant cells under vacuum to prepare liquid
crystal display devices to measure residual DC and confirm an
aligning property in the same manners as in Example 1.
Example 15
[0262] The additive (Ad1) was added in a proportion of 20% by
weight based on a weight of the polymer to the polyamic acid
solution (PA4) having a polymer solid concentration of 6% by weight
which was prepared in Synthetic Example 4. The above polyamic acid
solution is designated as PA18. The polyamic acid contained in PA18
had a weight average molecular weight of 52,000. Then, the mixed
solvent of NMP/BC=4/1 (weight ratio) was added thereto to dilute
the solution to a polymer solid concentration of 4% by weight,
whereby a liquid crystal aligning agent was prepared. The liquid
crystal aligning agent thus obtained was used to prepare a vacant
cell by the method according to Example 1. Then, the liquid crystal
composition A was injected into the above vacant cell under vacuum
to prepare a liquid crystal display device to measure residual DC
and confirm an aligning property in the same manners as in Example
1.
Example 16
[0263] The additive (Ad2) was added in a proportion of 20% by
weight based on a weight of the polymer to the polyamic acid
solution (PA4) having a polymer solid concentration of 6% by weight
which was prepared in Synthetic Example 4. The above polyamic acid
solution is designated as PA19. The polyamic acid contained in PA19
had a weight average molecular weight of 52,000. Then, the mixed
solvent of NMP/BC=4/1 (weight ratio) was added thereto to dilute
the solution to a polymer solid concentration of 4% by weight,
whereby a liquid crystal aligning agent was prepared. The liquid
crystal aligning agent thus obtained was used to prepare a vacant
cell by the method according to Example 1. Then, the liquid crystal
composition A was injected into the above vacant cell under vacuum
to prepare a liquid crystal display device to measure residual DC
and confirm an aligning property in the same manners as in Example
1.
Example 17
[0264] The additive (Ad3) was added in a proportion of 20% by
weight based on a weight of the polymer to the polyamic acid
solution (PA4) having a polymer solid concentration of 6% by weight
which was prepared in Synthetic Example 4. The above polyamic acid
solution is designated as PA20. The polyamic acid contained in PA20
had a weight average molecular weight of 52,000. Then, the mixed
solvent of NMP/BC=4/1 (weight ratio) was added thereto to dilute
the solution to a polymer solid concentration of 4% by weight,
whereby a liquid crystal aligning agent was prepared. The liquid
crystal aligning agent thus obtained was used to prepare a vacant
cell by the method according to Example 1. Then, the liquid crystal
composition A was injected into the above vacant cell under vacuum
to prepare a liquid crystal display device to measure residual DC
and confirm an aligning property in the same manners as in Example
1.
Example 18
[0265] The additive (Ad4) was added in a proportion of 10% by
weight based on a weight of the polymer to the polyamic acid
solution (PA4) having a polymer solid concentration of 6% by weight
which was prepared in Synthetic Example 4. The above polyamic acid
solution is designated as PA21. The polyamic acid contained in PA21
had a weight average molecular weight of 52,000. Then, the mixed
solvent of NMP/BC=4/1 (weight ratio) was added thereto to dilute
the solution to a polymer solid concentration of 4% by weight,
whereby a liquid crystal aligning agent was prepared. The liquid
crystal aligning agent thus obtained was used to prepare a vacant
cell by the method according to Example 1. Then, the liquid crystal
composition A was injected into the above vacant cell under vacuum
to prepare a liquid crystal display device to measure residual DC
and confirm an aligning property in the same manners as in Example
1. The measured results of residual DC in Examples 1 to 18 are
shown in Table 2-1.
TABLE-US-00002 TABLE 2-1 Polyamic Ex- acid Residual DC ample
solution Initial After relaxed for Aligning No. No. value (mV) 15
minutes (mV) property 1 PA1 785 59 .largecircle. 2 PA2 534 115
.largecircle. 3 PA3 574 142 .largecircle. 4 PA4 536 111
.largecircle. 5 PA5 689 74 .largecircle. 6 PA6 746 151
.largecircle. 7 PA7 591 63 .largecircle. 8 PA8 673 129
.largecircle. 9 PA9 631 134 .largecircle. 10 PA10 530 120
.largecircle. 11 PA11 582 106 .largecircle. 12 PA12 559 118
.largecircle. 13 PA13 642 105 .largecircle. 14 PA14 583 86
.largecircle. 15 PA18 737 166 .largecircle. 16 PA19 670 128
.largecircle. 17 PA20 678 135 .largecircle. 18 PA21 610 133
.largecircle.
Example 19
[0266] The mixed solvent of NMP/BC=4/1 (weight ratio) was added to
the polyamic acid solution (PA1) having a polymer solid
concentration of 6% by weight which was prepared in Synthetic
Example 1 to dilute the solution to a polymer solid concentration
of 4% by weight, whereby a liquid crystal aligning agent was
prepared. The liquid crystal aligning agent thus obtained was used
to prepare a liquid crystal display device as shown below.
<Preparing Method of Liquid Crystal Display Device>
[0267] The liquid crystal aligning agent was coated on two glass
substrates provided with ITO electrodes by means of the spinner
(spin coater (1H-DX2), manufactured by Mikasa Co., Ltd.). After
coated, the layer was dried by heating at 70.degree. C. for about 1
minute on the hot plate (EC Hot Plate (EC-1200N), manufactured by
AS ONE Corporation), and then it was irradiated (exposure energy:
5.0.+-.0.1 J/cm.sup.2 at a wavelength of 365 nm) with a linearly
polarized UV ray via a polarizing plate from a direction vertical
to the substrate by means of a UV lamp (UVL-1500M2-N1) manufactured
by USHO INC. The conditions of irradiating with a UV ray and the
method for controlling the exposure energy were based on those in
Example 1. Then, the layer was subjected to heat treatment at
230.degree. C. for 15 minutes in the clean oven (Clean Oven
(PVHC-231), manufactured by ESPEC Corp.) to form an alignment layer
having a layer thickness of 100.+-.10 nm. Finally, the substrate
after heated was heated and annealed at 120.degree. C. for 30
minutes in the clean oven.
[0268] The faces on which the alignment layers were formed in two
substrates having the alignment layers formed on the ITO electrodes
were oppositely disposed to form a gap for injecting a liquid
crystal composition into the gap between the opposite substrates so
that the polarization directions of UV rays irradiated onto the
alignment layers were parallel, and the substrates were stuck
together to prepare a vacant cell having a cell thickness of 4
.mu.m. An injection port for injecting liquid crystal into the
above vacant cell was provided in such a position that a direction
in which the liquid crystal flowed in injection was almost parallel
to a polarization direction of a UV ray irradiated onto the
alignment layer.
[0269] The liquid crystal composition A described above was
injected into the vacant cell prepared above under vacuum to
prepare a liquid crystal display device.
[0270] The liquid crystal display device prepare above was used to
measure residual DC by the method described above to find that an
initial value of the residual DC was 728 mV and that the value
thereof after relaxed for 15 minutes was 51 mV. Also, flow aligning
was not confirmed, and the aligning property was good.
Examples 20 to 24
[0271] The mixed solvent of NMP/BC=4/1 (weight ratio) was added to
the respective polyamic acid solutions (PA4, PA6, PA11, PA13 and
PA19) having a polymer solid concentration of 6% by weight to
dilute the solutions to a polymer solid concentration of 4% by
weight, whereby liquid crystal aligning agents were prepared. The
liquid crystal aligning agents thus obtained were used to prepare
vacant cells by the method according to Example 19. Then, the
liquid crystal composition A was injected into the above vacant
cells under vacuum to prepare liquid crystal display devices to
measure residual DC and confirm an aligning property in the same
manners as in Example 1. The measured results of the residual DC in
Examples 19 to 24 are shown in Table 2-2.
TABLE-US-00003 TABLE 2-2 Polyamic Ex- acid Residual DC ample
solution Initial After relaxed for Aligning No. No. value (mV) 15
minutes (mV) property 19 PA1 728 51 .largecircle. 20 PA4 563 120
.largecircle. 21 PA6 700 132 .largecircle. 22 PA11 549 99
.largecircle. 23 PA13 640 101 .largecircle. 24 PA19 658 106
.largecircle.
Example 25
[0272] The mixed solvent of NMP/BC=4/1 (weight ratio) was added to
the polyamic acid solution (PA1) having a polymer solid
concentration of 6% by weight which was prepared in Synthetic
Example 1 to dilute the solution to a polymer solid concentration
of 4% by weight, whereby a liquid crystal aligning agent was
prepared. The liquid crystal aligning agent thus obtained was used
to prepare a liquid crystal display device as shown below.
<Preparing Method of Liquid Crystal Display Device>
[0273] The liquid crystal aligning agent was coated on two glass
substrates provided with ITO electrodes by means of the spinner
(spin coater (1H-DX2), manufactured by Mikasa Co., Ltd.). After
coated, the layer was dried by heating at 70.degree. C. for about 1
minute on the hot plate (EC Hot Plate (EC-1200N), manufactured by
AS ONE Corporation), and then it was irradiated (exposure energy:
5.0.+-.0.1 J/cm.sup.2 at a wavelength of 365 nm) with a linearly
polarized UV ray via a polarizing plate from a direction vertical
to the substrate by means of Multilight ML-501C/B, manufactured by
USHO INC. The substrate was heated and maintained at a temperature
of 50.degree. C. during exposure to a UV ray. The conditions of
irradiating with a UV ray and the method for controlling the
exposure energy were based on those in Example 1. Then, the layer
was subjected to heat treatment at 230.degree. C. for 15 minutes in
the clean oven (Clean Oven (PVHC-231), manufactured by ESPEC Corp.)
to form an alignment layer having a layer thickness of 100.+-.10
nm.
[0274] The faces on which the alignment layers were formed in two
substrates having the alignment layers formed on the ITO electrodes
were oppositely disposed to form a gap for injecting a liquid
crystal composition into the gap between the opposite substrates so
that the polarization directions of UV rays irradiated onto the
alignment layers were parallel, and the substrates were stuck
together to prepare a vacant cell having a cell thickness of 4
.mu.m. An injection port for injecting liquid crystal into the
above vacant cell was provided in such a position that a direction
in which the liquid crystal flowed in injection was almost parallel
to a polarization direction of a UV ray irradiated onto the
alignment layer.
[0275] The liquid crystal composition A described above was
injected into the vacant cell prepared above under vacuum to
prepare a liquid crystal display device.
[0276] The liquid crystal display device prepare above was used to
measure residual DC by the method described above to find that an
initial value of the residual DC was 764 mV and that the value
thereof after relaxed for 15 minutes was 44 mV. Also, flow aligning
was not confirmed, and the aligning property was good.
Examples 26 to 30
[0277] The mixed solvent of NMP/BC=4/1 (weight ratio) was added to
the respective polyamic acid solutions (PA4, PA6, PA11, PA13 and
PA19) having a polymer solid concentration of 6% by weight to
dilute the solutions to a polymer solid concentration of 4% by
weight, whereby liquid crystal aligning agents were prepared. The
liquid crystal aligning agents thus obtained were used to prepare
vacant cells by the method according to Example 25. The liquid
crystal composition A was injected into the above vacant cells
under vacuum to prepare liquid crystal display devices to measure
residual DC and confirm an aligning property in the same manners as
in Example 1. The measured results of the residual DC in Examples
25 to 30 are shown in Table 2-3.
TABLE-US-00004 TABLE 2-3 Polyamic Ex- acid Residual DC ample
solution Initial After relaxed for Aligning No. No. value (mV) 15
minutes (mV) property 25 PA1 764 44 .largecircle. 26 PA4 528 106
.largecircle. 27 RA6 693 129 .largecircle. 28 PA11 564 95
.largecircle. 29 PA13 601 97 .largecircle. 30 PA19 629 105
.largecircle.
Comparative Examples 1 to 3
[0278] The mixed solvent of NMP/BC=4/1 (weight ratio) was added to
the respective polyamic acid solutions (PA15 to PA17) having a
polymer solid concentration of 6% by weight to dilute the solutions
to a polymer solid concentration of 4% by weight, whereby liquid
crystal aligning agents were prepared. The liquid crystal aligning
agents thus obtained were used to prepare vacant cells by the
method according to Example 1. The liquid crystal composition A was
injected into the above vacant cells under vacuum to prepare liquid
crystal display devices to measure residual DC and confirm an
aligning property in the same manners as in Example 1. The measured
results of the residual DC in Comparative Examples 1 to 3 are shown
in Table 3.
TABLE-US-00005 TABLE 3 Compar- ative Polyamic Ex- acid Residual DC
ample solution Initial After relaxed for Aligning No. No. value
(mV) 15 minutes (mV) property 1 PA15 871 316 .largecircle. 2 PA16
1172 458 .largecircle. 3 PA17 1283 531 .largecircle.
[0279] It can be found from the results obtained in Examples 1 to
30 and Comparative Examples 1 to 3 that use of the liquid crystal
alignment layer of the present invention for liquid crystal display
devices makes it possible to control residual DC to a small initial
value while maintaining an aligning property and makes it possible
to shorten a relaxation time because of a small value of the
residual DC after relaxation for 15 minutes.
[0280] As described above, when the liquid crystal alignment layer
of the present invention is applied to an alignment layer for
liquid crystal display devices, afterimages can be inhibited from
being generated, and the aligning property is good. Accordingly, it
can be found that the liquid crystal alignment layer of the present
invention has satisfactory characteristics which can stand
practical use.
INDUSTRIAL APPLICABILITY
[0281] Use of the liquid crystal aligning agent of the present
invention makes it possible to provide a photo-aligning liquid
crystal alignment layer which can decrease storage of residual DC
and shorten a relaxation time and which can prevent afterimages
from being generated. Further, capable of being provided is a
liquid crystal display device which comprises the above liquid
crystal alignment layer and which is excellent in display
characteristics.
* * * * *