JP3498456B2 - Liquid crystal display device - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to a liquid crystal display device.
You. More specifically, the display electrodes and
And / or the counter display electrode is partially removed
Liquid crystal display with alignment control window formed
Liquid crystal display device having excellent alignment of liquid crystal molecules
About. [0002] 2. Description of the Related Art Conventionally, a transparent electrode has been used as a liquid crystal display element.
Made of polyimide, etc. on the surface of the substrate on which is provided
A liquid crystal alignment film is formed and used as a substrate for a liquid crystal display element.
Two sheets are arranged facing each other and have positive dielectric anisotropy in the gap.
Forming a liquid crystal layer consisting of a nematic liquid crystal
Apply an electric field to the liquid crystal molecules,
A liquid crystal display element to be driven is known. On the other hand, recently, a display electrode is provided.
Liquid crystal alignment film is formed on one surface of the
A liquid crystal alignment film is formed on one surface of the opposing substrate provided with
A liquid crystal layer is sandwiched between the substrate and the counter substrate,
In the display pixel, the number of display electrodes and counter display electrodes is small.
At least one of the electrodes is partially removed
A liquid crystal display device having an alignment control window
Below, the liquid crystal display element with such a configuration is referred to as “enclosing electrode type liquid crystal”.
An electrode with an orientation control window is called a `` display element ''.
It is called "enclosure electrode". ) Is introduced (for example, the second
Please refer to the 1st Liquid Crystal Symposium Proceedings, p. 290. ). This liquid crystal table
The display device improves the viewing angle dependence of the conventional liquid crystal display device.
It was developed primarily for the purpose of The liquid crystal in the enclosure electrode type liquid crystal display device
Molecular orientation is formed on the substrate and counter substrate respectively
Liquid crystal alignment film,
The crystal orientation film is, for example, a resin film made of polyimide or the like.
It is formed by performing a rubbing treatment on the surface. Soshi
In this case, the surrounding electrode type liquid crystal display element has a liquid crystal layer.
Constituent liquid crystal molecules are constant at the interface with the liquid crystal alignment film
(Pre-tilt angle)
You. However, the above-mentioned enclosure electrode type liquid crystal display
The device has a pretilt in which the liquid crystal molecules at the interface are constant.
Because they are arranged with corners, they are not affected by the electric field from the surrounding electrode.
Therefore, it is necessary to reliably control the rising direction of the liquid crystal molecules.
There is a problem that can not be. In addition, the pre-
Depending on the tilt angle, the surrounding electrode type liquid crystal display element is
There is a case where the effect of improving the field angle dependence does not appear. like this
In order to solve the problem
Small pretilt angle of liquid crystal molecules
Is preferably such that the pretilt angle is 0 °. I
However, the liquid crystal alignment in the enclosure electrode type liquid crystal display device
Whether the film is a conventionally known organic material (for example, a known polyimide)
Rubbing treatment on the surface of the resin film
When formed, a pretilt angle of about 1 ° is inevitable
Occurs. For this reason, the conventional enclosure electrode type liquid crystal display element
, The above problem has not been solved yet. [0006] The first object of the present invention
The liquid crystal molecules at the interface between the liquid crystal alignment film and the liquid crystal layer.
Enclosure that can be arranged without retilt angle
To provide an electrode-type liquid crystal display device. Of the present invention
The second object is to provide an enclosure electrode type liquid having excellent alignment of liquid crystal molecules.
An object of the present invention is to provide a crystal display element. [0007] A liquid crystal display device according to the present invention.
Indicates one surface (1) of the substrate (1) provided with the display electrode (2).
A) A liquid crystal alignment film (3) is formed on
Liquid is applied to one surface (4A) of the opposite substrate (4) provided with (5).
Crystal orientation film (6) is formed, substrate (1) and counter substrate
With (4), the liquid crystal layer (7) is sandwiched between the display pixels.
Here, the number of the display electrodes (2) and the number of the opposite display electrodes (5) are small.
At least one of the electrodes is partially removed
The formed orientation control window (8) is provided and the substrate (1)
Liquid crystal alignment film (3) formed on one surface (1A) and facing
Liquid crystal alignment film formed on one surface (4A) of substrate (4)
(6) is a tetracarboxylic acid represented by the following general formula (I)
Acid dianhydride and diamine represented by the following general formula (II)
And / or diamido represented by the following general formula (III)
Polyamic acids obtained by reacting
Imi obtained by dehydration and ring-opening of these polyamic acids
At least one polymer selected from the group consisting of
It is characterized by that. [0008] Embedded image [In the general formula (I), R¹Represents a tetravalent organic group
Show. ] [0010] Embedded image [In the general formula (II), R^Two, R^Five, R⁶And
And R⁷Are the same or different alkyl groups,
Represents a alkoxyl group or a halogen atom, a, d, e and
And f are each an integer of 0 to 4;^Two, R^Five, R
⁶Or R⁷Are the same when there are multiple
May be different, may be different, R^ThreeAnd R^Four
Represents the same or different divalent organic groups,
b and c are each 0 or 1; ] [0012] Embedded image[In the general formula (III), R⁸, R¹¹, R¹²And
And R¹³Are the same or different alkyl groups,
Represents a rcoxyl group or a halogen atom, and represents g, j, k or
And l are each an integer of 0 to 4;⁸, R¹¹, R
¹²Or R¹³Are the same when there are multiple
May be different, may be different, R⁹And R^Ten
Represents the same or different divalent organic groups,
h and i are each 0 or 1. ] [0014] DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a liquid crystal display device of the present invention will be described.
And will be described in detail. FIG. 1 shows a liquid crystal display device of the present invention.
FIG. 2 is a schematic diagram illustrating a configuration of a main part (one display pixel). In FIG. 1, reference numeral 1 denotes a substrate and 2 denotes a substrate.
The display electrode 3 provided on the surface 1A is on one surface 1A side of the substrate 1.
The liquid crystal alignment film 4 formed on the substrate is disposed so as to face the substrate 1.
The opposing substrate 5 is provided on one surface 4A of the opposing substrate 4.
The counter display electrode 6 is formed on one surface 4A of the counter substrate 4.
Liquid crystal alignment film 7 sandwiched between substrate 1 and counter substrate 4
The liquid crystal layer 8 has a part of the display electrode 2 removed.
The formed alignment control window 9 is formed on the other surface 1B side of the substrate 1.
Polarizing plate 10 is formed on the other surface 4B side of the counter substrate 4.
The polarizing plate, p, is a liquid crystal molecule. Here, the substrate 1 and the counter substrate 4
Is a glass such as float glass, soda glass, etc.
Polyethylene terephthalate, polybutylene tereph
Tartrate, polyether sulfone, polycarbonate
Any plastic transparent substrate can be used
You. Display electrode 2 provided with alignment control window 8
Functions as an enclosure electrode. Here, the liquid crystal layer 7
When a voltage is applied, the display electrode 2, the counter display electrode 5,
An electric field E as shown by a chain line is generated by the alignment control window 8.
Then, the action of the electric field E causes the liquid crystal
The child p rises in a plurality of directions. Thus, the liquid crystal
Due to the presence of a plurality of rising directions of the molecule p, the liquid
It is possible to reduce the dependency of the crystal display element on the visual sense.
You. Liquid crystal alignment film 3 and opposing group on substrate 1
The liquid crystal alignment film 6 of the plate 4 is formed of a liquid crystal constituting the liquid crystal layer 7.
This is a film having a function of aligning molecules. Liquid crystal alignment film 3
Is a liquid crystal display on one surface 1A of the substrate 1 on which the display electrodes 2 are provided.
Apply a directing agent to form a resin film, and on the surface of the resin film,
To perform alignment treatment by rubbing, ultraviolet irradiation, etc.
Can be formed. The liquid crystal alignment film 6 is
A liquid crystal is provided on one surface 4A of the counter substrate 4 on which the display electrodes 5 are provided.
An alignment agent is applied to form a resin film, and the surface of the resin film is
It can be formed by performing an orientation treatment. What
In addition, the liquid crystal alignment film may be formed by a uniaxial stretching method,
To obtain resin film by Ngmuir-Blodgett method
It can also be formed. The polarizing plate 9 provided on the other surface 1B side of the substrate 1
And the polarizing plate 10 provided on the other surface 4B side of the counter substrate 4.
As, for example, polyvinyl alcohol is stretched and oriented
Polarizing plate formed by absorbing iodine while
H film), the H film is protected by the cellulose acetate protective film.
Examples thereof include a polarizing plate formed to be sandwiched therebetween. side
The light plate 9 has a polarization direction formed on one surface 1A of the electrode substrate 1.
Coincides with or perpendicular to the alignment processing direction of the aligned liquid crystal alignment film 3.
So that the polarization direction of the polarizing plate 10 is
Alignment of liquid crystal alignment film 6 formed on one surface 4A of counter substrate 4
It is pasted so that it matches or is orthogonal to the processing direction.
You. In this liquid crystal display device, a liquid crystal alignment film
3 and the alignment process in the liquid crystal alignment film 6.
Facing the substrate 1 so that the processing direction is orthogonal or antiparallel
The substrate 4 is disposed so as to face, and the substrate 1 and the counter substrate 4
The liquid crystal layer 7 is sandwiched. The liquid crystal constituting the liquid crystal layer 7 is nematic.
To name liquid crystal liquid crystal and smectic liquid crystal
Of which nematic liquid crystal is preferable.
For example, Schiff base liquid crystal, azoxy liquid crystal, biphenyl
Liquid crystal, phenylcyclohexane liquid crystal, ester liquid
Crystal, terphenyl liquid crystal, biphenylcyclohexane
Liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclo
It is possible to use octane liquid crystal, cuban liquid crystal, etc.
Wear. In addition, for example, cholesterol
Id, Cholesteryl Nonaate, Cholesteryl Carbonate
Cholesteric liquid crystal such as a liquid crystal and product name "C-15"
It is sold as "CB-15" (Merck)
Such a chiral agent may be added for use.
Further, p-decyloxybenzylidene-p-amino-2
-Uses ferroelectric liquid crystal such as methylbutyl cinnamate
can do. The liquid crystal display device having the above-described configuration is, for example,
If it can be manufactured by the following method. (1) Patterning at regular intervals
Driving display electrode having alignment control window in display pixel
2 is provided on one surface 1A of the substrate 1 provided with
Liquid crystal by a method such as
Applying an alignment agent and heating the coating surface to form a resin film
Form. Here, the heating temperature is 80 to 250 ° C.,
Preferably it is 120-200 degreeC. Resin formed
The thickness of the film is usually 0.001 to 1 μm, preferably
Is 0.005 to 0.5 μm. Table of resin film formed on one surface 1A of substrate 1
The surface is made of fiber such as nylon, rayon, cotton, etc.
Rubbing in a certain direction with a roll wrapped with a cloth made of
Performing the logging process. As a result, the alignment ability of liquid crystal molecules is
To form a liquid crystal alignment film 3. The rubbing process
Clean surface by removing fine powder (foreign matter) generated at the time
Liquid crystal alignment film formed by isopropyl
Washing with alcohol or the like is preferred. (2) In the same manner as in (1) above, facing display
A liquid crystal aligning agent is applied to one surface 4A of the opposite substrate 4 on which the electrode 5 is provided.
Is applied, and the coated surface is dried by heating to form a resin film.
The liquid crystal alignment film 6 is formed by rubbing the film surface.
Form. (3) The substrate 1 and the counter substrate 4 are aligned with a liquid crystal.
The alignment direction in the film 3 and the liquid crystal alignment film 6, that is,
Make sure that the gap (Sergi) is
And the peripheral portions of the two substrates are sealed.
Bonding using an adhesive agent, the inner surface of the substrate (1A, 1A
Cell gap defined by surface 4A) and sealant
Liquid crystal is injected and filled into the inside, and the injection hole is sealed to form a liquid crystal cell.
To achieve. Then, the outer surfaces of the liquid crystal cell (other surface 1B, other surface 4)
B), the polarization direction of the liquid crystal alignment film of each substrate (liquid crystal
The rubbing direction of the alignment film 3 or the liquid crystal alignment film 6)
Attach polarizing plates (polarizing plate 9 and polarizing plate 10) so as to be orthogonal
A liquid crystal display element is obtained by combining them. here,
Examples of the sealant include a curing agent and a spacer.
Epoxy resin containing all aluminum oxide spheres
Can be used. The liquid crystal display device of the present invention has a shape formed on one surface of a substrate.
The formed liquid crystal alignment film (liquid crystal alignment film 3 in FIG. 1) and
Liquid crystal alignment film formed on one side of the counter substrate (see FIG. 1)
Liquid crystal alignment film 6) represented by the above general formula (I)
Tetracarboxylic dianhydride, represented by the above general formula (II)
Diamine compound represented by the general formula (III) and / or
Polya obtained by reacting with the represented diamine compound
Acid, the above-mentioned polyamic acid (hereinafter referred to as “polyamic acid”).
Imidized compound obtained by dehydration and ring-opening of
(Hereinafter also referred to as “imidized polymer B”)
It is characterized by comprising at least one polymer. A resin film is formed from such a polymer.
Alignment treatment such as rubbing treatment on the surface of the resin film
To form a liquid crystal alignment film,
Pretilt angle of liquid crystal molecules at the interface between the facing film and the liquid crystal layer
It is possible to arrange (initial molecular arrangement) without having
become. <Polyamic Acid A> Constituting Liquid Crystal Alignment Film
Polyamic acid A used as a resin
A tetracarboxylic dianhydride represented by the formula (I),
Represented by the general formula (II) and / or the general formula (III)
Diamine compound (hereinafter also referred to as “specific diamine compound”)
)). Tet used for synthesis of polyamic acid A
Examples of the lacarboxylic dianhydride include butanetetraca
Rubonic dianhydride, 1,2,3,4-cyclobutane tet
Lacarboxylic dianhydride, 1,3-dimethyl-1,2,2
3,4-cyclobutanetetracarboxylic dianhydride, 1,
3-dichloro-1,2,3,4-cyclobutanetetraca
Rubonic dianhydride, 1,2,3,4-cyclopentane
Tracarboxylic dianhydride, 1,2,4,5-cyclohexyl
Suntetracarboxylic dianhydride, 3,3 ', 4,4'-
Dicyclohexyltetracarboxylic dianhydride, 2,3
5-tricarboxycyclopentylacetic acid dianhydride, 3,
5,6-tricarboxynorbornane-2-acetic acid dianhydride
Substance, 2,3,4,5-tetrahydrofuran tetracarbo
Dianhydride, 5- (2,5-dioxotetrahydrofuran)
Ral) -3-methyl-3-cyclohexene-1,2-di
Carboxylic acid dianhydride, bicyclo [2,2,2] -oct
-7-ene-2,3,5,6-tetracarboxylic dianhydride
Aliphatic or alicyclic tetracarboxylic dianhydride
object; 1,3,3a, 4,5,9b-hexahydride
B-5- (Tetrahydro-2,5-dioxo-3-fura
Nyl) -naphtho [1,2-c] furan-1,3-dio
1,3,3a, 4,5,9b-Hexahydro-5-
Methyl-5- (tetrahydro-2,5-dioxo-3-
Furanyl) -naphtho [1,2-c] furan-1,3-di
ON, 1,3,3a, 4,5,9b-Hexahydro-5
-Ethyl-5- (tetrahydro-2,5-dioxo-3
-Furanyl) -naphtho [1,2-c] furan-1,3-
Dione, 1,3,3a, 4,5,9b-hexahydro-
7-methyl-5- (tetrahydro-2,5-dioxo-
3-furanyl) -naphtho [1,2-c] furan-1,3
-Dione, 1,3,3a, 4,5,9b-hexahydro
-7-ethyl-5- (tetrahydro-2,5-dioxo
-3-furanyl) -naphtho [1,2-c] furan-1,
3-dione, 1,3,3a, 4,5,9b-hexahydride
B-8-Methyl-5- (tetrahydro-2,5-dioxy
So-3-furanyl) -naphtho [1,2-c] furan-
1,3-dione, 1,3,3a, 4,5,9b-hexa
Hydro-8-ethyl-5- (tetrahydro-2,5-di
Oxo-3-furanyl) -naphtho [1,2-c] furan
-1,3-dione, 1,3,3a, 4,5,9b-hex
Sahydro-5,8-dimethyl-5- (tetrahydro-
2,5-dioxo-3-furanyl) -naphtho [1,2-
c] having a benzene ring such as furan-1,3-dione
Aliphatic tetracarboxylic dianhydride; Pyromellitic dianhydride, 3,3 ', 4
4'-benzophenonetetracarboxylic dianhydride, 3,
3 ', 4,4'-biphenylsulfonetetracarboxylic acid
Dianhydride, 1,4,5,8-naphthalenetetracarboxylic
Acid dianhydride, 2,3,6,7-naphthalenetetracarbo
Dianhydride, 3,3 ', 4,4'-biphenylate
Letetracarboxylic dianhydride, 3,3 ', 4,4'-di
Methyldiphenylsilanetetracarboxylic dianhydride,
3,3 ', 4,4'-tetraphenylsilanetetracal
Boronic acid dianhydride, 1,2,3,4-furantetracarbo
Acid dianhydride, 4,4'-bis (3,4-dicarboxy)
Phenoxy) diphenyl sulfide dianhydride, 4,4 '
-Bis (3,4-dicarboxyphenoxy) diphenyl
Sulfone dianhydride, 4,4'-bis (3,4-dicarbo
Xyphenoxy) diphenylpropane dianhydride, 3,
3 ', 4,4'-Perfluoroisopropylidene diphthal
Luic dianhydride, 3,3 ', 4,4'-biphenyltetra
Carboxylic anhydride, bis (phthalic acid) phenylphosphine
Quinoxide dianhydride, p-phenylene-bis (tri
Phenylphthalic acid) dianhydride, m-phenylene-bis
(Triphenylphthalic acid) dianhydride, bis (triphenylene)
Ruphthalic acid) -4,4'-diphenyl ether dianhydride
, Bis (triphenylphthalic acid) -4,4'-dife
Aromatic tetracarboxylic acids such as nylmethane dianhydride
Waters can be mentioned. These tetracarboxylic acids
Dianhydrides are used alone or in combination of two or more.
be able to. Of these, butanetetracarboxylic acid
Anhydride, 1,2,3,4-cyclobutanetetracarboxylic
Acid dianhydride, 1,3-dimethyl-1,2,3,4-cyc
Lobutanetetracarboxylic dianhydride, 1,2,3,4-
Cyclopentanetetracarboxylic dianhydride, 2,3,5
-Tricarboxycyclopentylacetic acid dianhydride, 3,4
-Dicarboxy-1,2,3,4-tetrahydro-1-
Naphthalene succinic anhydride, 3,4-dicarboxy-6
-Methyl-1,2,3,4-tetrahydro-1-naphtha
Lensuccinic anhydride, 3,4-dicarboxy-7-methyl
1,2,3,4-tetrahydro-1-naphthaleneco
Succinic anhydride, 5- (2,5-dioxotetrahydrof
Ral) -3-methyl-3-cyclohexene-1,2-di
Carboxylic dianhydride; 1,3,3a, 4,5,9b-f
Xahydro-8-methyl-5- (tetrahydro-2,5
-Dioxo-3-furanyl) -naphtho [1,2-c] fu
Run-1,3-dione, bicyclo [2,2,2] -oct
To-7-ene-2,3,5,6-tetracarboxylic acid
Water, 1,3,3a, 4,5,9b-hexahydro-5
-(Tetrahydro-2,5-dioxo-3-furanyl)
-Naphtho [1,2-c] furan-1,3-dione, 1,
3,3a, 4,5,9b-Hexahydro-8-methyl-
5- (tetrahydro-2,5-dioxo-3-furani
Le) -naphtho [1,2-c] furan-1,3-dione,
1,3,3a, 4,5,9b-Hexahydro-5,8-
Dimethyl-5- (tetrahydro-2,5-dioxo-3
-Furanyl) -naphtho [1,2-c] furan-1,3-
Dione; pyromellitic dianhydride, 3,3 ', 4,4'
-Benzophenonetetracarboxylic dianhydride, 3,
3 ', 4,4'-biphenylsulfonetetracarboxylic acid
Dianhydride and 1,4,5,8-naphthalenetetracar
Boronic dianhydride is used as a liquid crystal aligning agent containing these.
Therefore, the liquid crystal alignment film formed
Preferred because it will have a liquid crystal orientation, especially
Preferably, 1,2,3,4-cyclobutanetetracar
Boric acid dianhydride, 1,3-dimethyl-1,2,3,4-
Cyclobutanetetracarboxylic dianhydride, and 2,
3,5-tricarboxycyclopentylacetic acid dianhydride,
1,3,3a, 4,5,9b-Hexahydro-5- (te
Trahydro-2,5-dioxo-3-furanyl) -naph
[1,2-c] furan-1,3-dione, 1,3,3
a, 4,5,9b-Hexahydro-8-methyl-5-
(Tetrahydro-2,5-dioxo-3-furanyl)-
Naphtho [1,2-c] furan-1,3-dione, 1,
3,3a, 4,5,9b-Hexahydro-5,8-dimethyl
Tyl-5- (tetrahydro-2,5-dioxo-3-f
Ranyl) -naphtho [1,2-c] furan-1,3-dio
And pyromellitic dianhydride. The above-mentioned compound used for the synthesis of polyamic acid A
Specific diamine compounds represented by the general formula (II) include:
In the following chemical formula (1), chemical formula (2) and chemical formula (5)
The compounds represented can be exemplified as preferred ones.
Wear. Among them, chemical formula (1) and chemical formula (5)
A liquid crystal aligning agent comprising a compound represented by
Liquid crystal alignment film formed by
Is particularly preferable because it has excellent liquid crystal orientation.
No. The above-mentioned compound used for the synthesis of polyamic acid A
As the specific diamine compound represented by the general formula (III),
In the following chemical formulas (3), (4) and (6)
The compounds represented can be exemplified as preferred ones.
Wear. Among them, the compound represented by the chemical formula (3)
Is formed by a liquid crystal aligning agent containing these.
Liquid crystal alignment film has good liquid crystal alignment
It is particularly preferable because it can be used. [0036] Embedded image These specific diamine compounds may be used alone or
Can be used in combination of two or more. When synthesizing polyamic acid A,
Diamine compound subjected to reaction with lacarboxylic dianhydride
Diamine compounds other than the specified diamine compound
They can be used together. As a diamine compound that can be used in combination,
For example, 1,2-phenylenediamine, 3-methyl
-1,2-phenylenediamine, 4-methyl-1,2-
Phenylenediamine, 4,5-dimethyl-1,2-fe
Nilendiamine, 3-ethyl-1,2-phenylenediaia
Min, 3-methyl-1,2-phenylenediamine, 4-
Ethyl-1,2-phenylenediamine, 4,5-diethyl
Ru-1,2-phenylenediamine, 3-methoxy-1,
2-phenylenediamine, 4-methoxy-1,2-fe
Nilendiamine, 4,5-dimethoxy-1,2-phenyl
Diamine, 3-ethoxy-1,2-phenylenedia
Min, 4-ethoxy-1,2-phenylenediamine, 3
-Chloro-1,2-phenylenediamine, 4-chloro-
1,2-phenylenediamine, 3-fluoro-1,2-
Phenylenediamine, 4-fluoro-1,2-phenylene
Diamine, 1,3-phenylenediamine, 2-methyl
-1,3-phenylenediamine, 4-methyl-1,3-
Phenylenediamine, 5-methyl-1,3-phenylene
Diamine, 2-ethyl-1,3-phenylenediamine,
4-ethyl-1,3-phenylenediamine, 5-ethyl
-1,3-phenylenediamine, 2-methoxy-1,3
-Phenylenediamine, 4-methoxy-1,3-phenyl
Diamine, 5-methoxy-1,3-phenylenedia
Min, 4-ethoxy-1,3-phenylenediamine, 5
-Ethoxy-1,3-phenylenediamine, 4-chloro
-1,3-phenylenediamine, 5-chloro-1,3-
Phenylenediamine, 4-fluoro-1,3-phenylene
Diamine, 5-fluoro-1,3-phenylenediamine
1,4-phenylenediamine, 2-methyl-1,4
-Phenylenediamine, 2,3-dimethyl-1,4-phenyl
Enylenediamine, 2,5-dimethyl-1,4-phenyl
Diamine, 2,6-dimethyl-1,4-phenylene
Diamine, 2,3-diethyl-1,4-phenylenedia
Min, 2,5-diethyl-1,4-phenylenediamine
2,6-ethyl-1,4-phenylenediamine, 2
-Methoxy-1,4-phenylenediamine, 2-ethoxy
1,4-phenylenediamine, 2-chloro-1,4
Phenylenediamine, 2,3-dichloro-1,4-phenyl
Enylenediamine, 2,5-dichloro-1,4-phenyl
Diamine, 2,6-dichloro-1,4-phenylene
Diamine, 2-fluoro-1,4-phenylenediamine
, 2,3-difluoro-1,4-phenylenediamine
, 2,5-difluoro-1,4-phenylenediamine
, 2,6-difluoro-1,4-phenylenediamine
1,5-diaminonaphthalene, 3,3'-dimethyl
-4,4'-diaminobiphenyl, 2,2 ', 5,5'
-Tetrachloro-4,4'-diaminobiphenyl, 2,
2'-dichloro-4,4'-diamino-5,5'-dimethyl
Toxiphenyl, 3,3'-dimethoxy-4,4'-
Diaminobiphenyl, 4,4'-diamino-2,2'-
Bis (trifluoromethyl) biphenyl, 4,4'-di
Aminodiphenylmethane, 4,4'-diaminodiphenyl
Ether, 4,4 '-(p-phenyleneisopropylate
Den) bisaniline, 4,4 '-(m-phenyleneiso
Propylidene) bisaniline, 2,2-bis [4- (4
-Aminophenoxy) phenyl] propane, 4,4'-
Diaminodiphenylethane, 4,4'-diaminodife
Nyl sulfone, 4,4'-diaminodiphenyl sulfy
4,4'-diaminobenzanilide, 3,4'-di
Aminodiphenyl ether, 3,3'-diaminobenzo
Phenone, 3,4'-diaminobenzophenone, 4,
4'-diaminobenzophenone, 2,2-bis [4-
(4-aminophenoxy) phenyl] hexafluorop
Lopan, 2,2-bis (4-aminophenyl) hexaf
Fluoropropane, 2,2-bis [4- (4-aminophen
Noxy) phenyl] sulfone, 1,4-bis (4-amido
Nophenoxy) benzene, 1,3-bis (4-aminophen)
Enoxy) benzene, 1,3-bis (3-aminopheno)
Xy) benzene, 4,4'-methylene-bis (2-chloro
Roaniline), 2,2'-bis [4- (4-amino-2
-Trifluoromethylphenoxy) phenyl] hexaf
Fluoropropane, 4,4'-bis [(4-amino-2-
Trifluoromethyl) phenoxy] -octafluorobi
Phenyl, 2,7-diaminofluorene, 5-amino-
1- (4'-aminophenyl) -1,3,3-trimethyl
Ruindane, 6-amino-1- (4'-aminopheni
Le) -1,3,3-trimethylindane
Can be. These diamine compounds may be used alone or
Two or more kinds can be used in combination. Of these, 1,4-phenylenediamine
4,4'-diaminodiphenylmethane, 4,4'-
Diaminodiphenyl ether, 2,2-bis [4- (4
-Aminophenoxy) phenyl] propane, 4,4'-
(P-phenylenediisopropylidene) bisaniline
Is formed by a liquid crystal aligning agent containing these.
Liquid crystal alignment film has good liquid crystal alignment
This is preferred because The reaction with tetracarboxylic dianhydride
Of the specified diamine compound among the diamine compounds
From the viewpoint of ensuring the effects of the present invention
To 50 to 100 mol%, preferably 70 to 10 mol%.
0 mol%. [0042] The material used for the synthesis reaction of polyamic acid A
Use ratio of tracarboxylic dianhydride and diamine compound
Is a diamine compound (specific diamine compound and other
Of the amino group contained in the diamine compound)
The acid anhydride group of the tetracarboxylic dianhydride is 0.2 to
A ratio of 2 equivalents is preferred, and more preferably 0.3 equivalent.
It is a ratio that becomes .about.1.2 equivalents. Compound of tetracarboxylic dianhydride and diamine
Synthesis reaction of polyamic acid A with an organic solvent in an organic solvent
At 0 to 150 ° C., preferably 0 to 100 ° C.
For 1 to 48 hours. The reaction conditions
By imidation of a part of polyamic acid A
In some cases, the liquid crystal alignment film constituting the present invention is formed.
There is no problem in using it as a formed resin. this
The organic solvent used in the reaction is a reaction product
There is no particular limitation as long as it can dissolve polyamic acid A.
No, for example, N-methyl-2-pyrrolidone, N, N-di
Methylacetamide, N, N-dimethylformamide,
Dimethyl sulfoxide, γ-butyrolactone, tetrame
Non-pros such as tyl urea and hexamethylphosphortriamide
Roton polar solvent; m-cresol, xylenol,
Phenolic solvents such as phenols and halogenated phenols
Medium can be mentioned. The amount of the organic solvent used is
Usually, tetracarboxylic dianhydride and diamine compounds
Is from 0.1 to 30% by weight based on the total amount of the reaction solution.
Preferably, the amount is such that The organic solvent includes polyamic acid.
Alcohols, ketones, esters that are poor solvents for A
, Ethers, halogenated hydrocarbons, hydrocarbons
To the extent that the resulting polyamic acid A does not precipitate
Can be used together. Such poor solvents include, for example,
Methyl alcohol, ethyl alcohol, isopropyl
Alcohol, cyclohexanol, ethylene glycol
Propylene glycol, 1,4-butanediol,
Triethylene glycol, ethylene glycol monomethyl
Ether, acetone, methyl ethyl ketone, methyl ether
Sobutyl ketone, cyclohexanone, methyl acetate, acetic acid
Ethyl, butyl acetate, diethyl oxalate, malonic acid die
Chill, diethyl ether, ethylene glycol methyl ether
-Tel, ethylene glycol ethyl ether, ethylene
Glycol-n-propyl ether, ethylene glycol
Ru-i-propyl ether, ethylene glycol-n-
Butyl ether, ethylene glycol-n-hexyl
-Tel, ethylene glycol dimethyl ether, ethyl
Glycol ethyl ether acetate, diethylene glycol
Recol dimethyl ether, diethylene glycol die
Tyl ether, diethylene glycol monomethyl ether
, Diethylene glycol monoethyl ether, diethyl
Len glycol monobutyl ether, diethylene glyco
Monomethyl ether acetate, diethylene glyco
Monoethyl ether acetate, ethylene glycol
Methyl ether acetate, ethylene glycol ethyl
Ruthel acetate, ethylene glycol-n-pro
Pill ether acetate, ethylene glycol-i-p
Propyl ether acetate, ethylene glycol-n-
Butyl ether acetate, ethylene glycol-n-
Hexyl ether acetate, 4-hydroxy-4-me
Tyl-2-pentanone, 2-hydroxypropionic acid
Tyl, 2-hydroxy-2-methylpropionate
, Ethyl 2-hydroxy-2-methylpropionate,
Ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydrido
Roxy-3-methylbutanoate methyl, 3-methoxypro
Methyl pionate, ethyl 3-methoxypropionate, 3
-Ethyl ethoxypropionate, 3-ethoxypropion
Methyl ester, 3-methyl-3-methoxybutanol, 3
-Ethyl-3-methoxybutanol, tetrahydrofura
, Dichloromethane, 1,2-dichloroethane, 1,4
-Dichlorobutane, trichloroethane, chlorbenze
, O-dichlorobenzene, hexane, heptane, octane
Name tan, benzene, toluene, xylene, etc.
Can be. These may be used alone or in combination of two or more.
Can be used. <Imidated Polymer B> Constituting Liquid Crystal Alignment Film
The imidized polymer B used as a resin is prepared by the following method
It can be prepared by (1) or method (2).
This imidized polymer B is usually a polyimide or a polyimide.
Soimide. Method (1): Addition of the above polyamic acid A
heat. The reaction temperature in this method is usually from 60 to 25.
The temperature is set to 0 ° C, preferably 100 to 170 ° C. Anti
When the reaction temperature is lower than 60 ° C., the imidization reaction proceeds sufficiently.
The imidization weight obtained when the reaction temperature exceeds 250 ° C.
The molecular weight of the coalescence may decrease. Method (2): Using polyamic acid A in an organic solvent
And a dehydrating agent and a dehydration ring-opening catalyst are added to the solution.
Addition and heating if necessary, dehydration ring closure (imine
Reaction). In this method, as a dehydrating agent
Is, for example, acetic anhydride, propionic anhydride, triflic anhydride
Acid anhydrides such as oloacetic acid can be used. Dehydrating agent
Is used per mole of the repeating unit of polyamic acid A.
Preferably, it is 1.5 to 20 mol. Also,
Water ring-opening catalysts include, for example, pyridine, collidine,
Use tertiary amines such as gin and triethylamine.
However, the present invention is not limited to these. dehydration
The amount of the ring-opening catalyst used is based on 1 mole of the dehydrating agent used.
Preferably it is 0.5 to 10 mol. In addition, dehydration ring closure
As the organic solvent used for the reaction, polyamic acid A
The organic solvents exemplified as those used in the synthesis of
Can be The reaction temperature of the dehydration ring closure reaction is usually 0 to
The temperature is set to 180 ° C, preferably 60 to 150 ° C. In addition,
To control the reaction conditions of the above imidation reaction
Therefore, the imidization ratio can be adjusted arbitrarily. The polyamic acid A or the like constituting the liquid crystal alignment film
And the imidized polymer B is a terminal-modified type
Good. Terminal-modified polyamic acid A and imidized polymer
In the case of B, the molecular weight is adjusted to a suitable range, and
By including a decorative polymer, the effect of the present invention is improved.
Improve liquid crystal aligning agent coating properties without loss
be able to. Such end-modified polymers are
When synthesizing an amic acid or its imidized polymer,
Add acid monoanhydride or monoamine compound to the reaction system
Can be synthesized. Where acid monoanhydride
As, for example, maleic anhydride, phthalic anhydride,
Itaconic acid, n-decyl succinic anhydride, n-do
Decyl succinic anhydride, n-tetradecyl succinate
Nickic anhydride, n-hexadecyl succinic anhydride
Products, n-octadecylsuccinic anhydride, etc.
Monoamine compounds include, for example,
Phosphorus, cyclohexylamine, n-butylamine, n-
Pentylamine, n-hexylamine, n-heptylua
Min, n-octylamine, n-nonylamine, n-de
Silamine, n-undecylamine, n-dodecylamido
N-tridecylamine, n-tetradecylamine,
n-pentadecylamine, n-hexadecylamine, n
-Heptadecylamine, n-octadecylamine, n-
Eicosylamine and the like can be mentioned. The polyamic acid A or the like constituting the liquid crystal alignment film
And the imidized polymer B has a value of its logarithmic viscosity (ηln).
Is preferably 0.05 to 10 dl / g.
And preferably 0.05 to 5 dl / g. In addition, this
Of the logarithmic viscosity (ηln) in the specification of
Using 2-pyrrolidone as a solvent, the concentration is 0.5 g.
/ Viscosity at 30 ° C. for a solution that is 100 ml
Is determined by the following formula.
You. [0050] (Equation 1) <Liquid crystal aligning agent> On substrate and counter substrate
The liquid crystal alignment film is coated with a liquid crystal alignment agent on one side of each substrate.
Apply and heat dry the coated surface to form a resin film,
It can be formed by rubbing the surface.
Wear. Such a liquid crystal aligning agent is a polyamic compound described in detail above.
At least one selected from acid A and imidized polymer B
Prepared by dissolving certain polymers in organic solvent
be able to. As an organic solvent for dissolving the above polymer,
Is particularly limited as long as it can dissolve them.
But not for polyamic acid A, for example.
Examples of the solvent include the solvents exemplified above.
You. Also used together during the synthesis reaction of polyamic acid A
By appropriately selecting the poor solvent exemplified as being able to
Can be used together. The concentration of the polymer in the liquid crystal aligning agent is usually
0.1 to 20% by weight, preferably 0.5 to 10 weights
%. When the polymer concentration is less than 0.1% by weight
Has good liquid crystal because the film thickness of the coating film (resin film) is too small
An alignment film could not be obtained and the polymer concentration was 20% by weight.
If it exceeds, the film thickness of the coating film becomes excessive and good liquid crystal
An alignment film could not be obtained, and the viscosity of the liquid crystal alignment agent was
As a result, the coating properties become poor. Further, the liquid crystal aligning agent includes a liquid crystal alignment to be formed.
The aim is to further improve the adhesion of the film to the substrate.
May contain a functional silane-containing compound
No. Such functional silane-containing compounds include, for example, 3
-Aminopropyltrimethoxysilane, 3-aminopro
Piltriethoxysilane, 2-aminopropyltrimeth
Xysilane, 2-aminopropyltriethoxysilane,
N- (2-aminoethyl) -3-aminopropyl trime
Toxisilane, N- (2-aminoethyl) -3-amino
Propylmethyldimethoxysilane, 3-ureidoprop
Rutrimethoxysilane, 3-ureidopropyltriet
Xysilane, N-ethoxycarbonyl-3-aminopro
Pyrtrimethoxysilane, N-ethoxycarbonyl-3
-Aminopropyltriethoxysilane, N-triethoxy
Sisilylpropyltriethylenetriamine, N-trime
Toxisilylpropyltriethylenetriamine, 10-
Trimethoxyisyl-1,4,7-triazadecane,
10-triethoxysilyl-1,4,7-triazadeca
, 9-trimethoxysilyl-3,6-diazanonylua
Acetate, 9-triethoxysilyl-3,6-diazano
Nyl acetate, N-benzyl-3-aminopropyl
Limethoxysilane, N-benzyl-3-aminopropyl
Triethoxysilane, N-phenyl-3-aminopropyl
Lutrimethoxysilane, N-phenyl-3-aminopro
Piltriethoxysilane, N-bis (oxyethylene)
-3-aminopropyltrimethoxysilane, N-bis
(Oxyethylene) -3-aminopropyltriethoxy
Silane and the like can be mentioned. Hereinafter, the present invention will be described in more detail with reference to Examples.
The present invention is limited to these examples.
Not something. In addition, according to the following Examples and Comparative Examples
To the manufactured liquid crystal display element (enclosure electrode type liquid crystal display element)
Then, measure the pretilt angle of the liquid crystal molecules, and
The orientation of the crystal molecules was evaluated. Measurement method and evaluation
The method is as follows. [Pretilt Angle of Liquid Crystal Molecule] "TJS
chffer, et al. , J. et al. Appl. Phys
s. , Vol. 19, 2013 (1980) "
Measured according to the method. If the pretilt angle is small,
It is possible to reliably regulate the rising direction of liquid crystal molecules.
In this case, the viewing angle dependency of the liquid crystal display element is small. [Orientation of Liquid Crystal Molecules]
In the liquid crystal cell when is turned on (applied) / off (released)
Observe the presence or absence of abnormal domains in
If no domain is found, it is judged as “good”
A case where a normal domain was recognized was judged as "poor". [Synthesis Example 1] 2,3,5-tricarboxy
44.83 g of cyclopentylacetic dianhydride (0.20 mol
) And the specific diamine compound represented by the above chemical formula (1)
69.69 g (0.20 mol) and γ-butyrolactone
565 g, and the solution is reacted at 60 ° C. for 6 hours.
I let you. Next, the obtained reaction solution was subjected to a large excess of methyl alcohol.
The reaction product was precipitated by pouring into a coal. Then settling
The product is separated, washed with methyl alcohol, and
For 15 hours, the logarithmic viscosity (ηln)
Is 1.22 dl / g polyamic acid [this is referred to as “Po
REAMIC ACID (A-1) ". ] 112.3 g was obtained.
Was. [Synthesis Example 2] The polyamide obtained in Synthesis Example 1
Acid (A-1) 40.0 g was converted to γ-butyrolactone 80
0 g, pyridine 35.2 g and acetic anhydride 27.2.
6 g and imidation reaction at 110 ° C. for 4 hours.
Was. Then, the reaction product was precipitated in the same manner as in Synthesis Example 1.
・ By performing separation, washing and drying, the logarithmic viscosity (ηl
n) is an imidized polymer having 1.23 dl / g [this is
It is referred to as "imidated polymer (B-1)". 38.5 g
Obtained. [Synthesis Example 3] Identification represented by chemical formula (1)
In place of the diamine compound, represented by the above chemical formula (2)
Using 75.29 g (0.20 mol) of the specified diamine compound
The logarithmic viscosity (η
ln) is 1.08 dl / g.
Is referred to as “polyamic acid (A-2)”. ] 107.8
g was obtained. Then, instead of the polyamic acid (A-1)
Because 40.0 g of polyamic acid (A-2) was used
Except that the logarithmic viscosity (ηln) was 1.
13 dl / g of imidized polymer [this
Polymer (B-2) ". 37.5 g was obtained. [Synthesis Example 4] Identification represented by chemical formula (1)
Instead of the diamine compound, represented by the above chemical formula (3)
Using 72.49 g (0.20 mol) of the specific diamine compound
The logarithmic viscosity (η
ln) is 1.10 dl / g.
Is referred to as “polyamic acid (A-3)”. ] 104.8
g was obtained. Then, instead of the polyamic acid (A-1)
Because 40.0 g of polyamic acid (A-3) was used.
Except that the logarithmic viscosity (ηln) was 1.
16 dl / g of imidized polymer [this
Polymer (B-3) ". 38.4 g was obtained. [Synthesis Example 5] Identification represented by chemical formula (1)
Instead of the diamine compound, represented by the above chemical formula (4)
Using 78.09 g (0.20 mol) of the specific diamine compound
The logarithmic viscosity (η
ln) is 1.15 dl / g.
Is referred to as "polyamic acid (A-4)". ] 110.2
g was obtained. Then, instead of the polyamic acid (A-1)
Because 40.0 g of polyamic acid (A-4) was used
Except that the logarithmic viscosity (ηln) was 1.
26 dl / g imidized polymer [this
Polymer (B-4) ". 38.3 g were obtained. [Synthesis Example 6] Identification represented by chemical formula (1)
Instead of the diamine compound, represented by the above chemical formula (5)
106.49 g (0.20 mol) of the specific diamine compound
Logarithmic viscosity was obtained in the same manner as in Synthesis Example 1 except for using
Polyamic acid having (ηln) of 1.02 dl / g
[This is referred to as “polyamic acid (A-5)”. ] 13
5.0 g were obtained. Then, the polyamic acid (A-1)
Instead, 40.0 g of polyamic acid (A-5) was used.
Except for this, the logarithmic viscosity (ηln) was the same as in Synthesis Example 2.
Is 1.21 dl / g [this is referred to as “I”
Imidized polymer (B-5) ". 38.2 g was obtained.
Was. Synthesis Example 7 2,3,5-Tricarboxy
Butanetetracaral instead of cyclopentylacetic dianhydride
Using 39.62 g (0.20 mol) of boric dianhydride
Logarithmic viscosity (ηln) in the same manner as in Synthesis Example 1 except that
Is 0.79 dl / g polyamic acid [this is referred to as
REAMIC ACID (A-6) ". ] 97.0 g were obtained.
Was. Next, a polyamic acid was used instead of the polyamic acid (A-1).
Except that 40.0 g of the mixic acid (A-6) was used,
Logarithmic viscosity (ηln) is 0.96 d in the same manner as in Example 2.
l / g imidized polymer [this is referred to as "imidized polymer"
(B-6) ". 36.2 g was obtained. Synthesis Example 8 2,3,5-Tricarboxy
1,2,3,4-in place of cyclopentylacetic acid dianhydride
39.22 g of butanetetracarboxylic dianhydride (0.2
0 mol) in the same manner as in Synthesis Example 1 except that
Polyamid having a number viscosity (ηln) of 1.12 dl / g
Citric acid [this is referred to as "polyamic acid (A-7)". ]
105.1 g were obtained. Synthesis Example 9 2,3,5-Tricarboxy
1,3-dimethyl instead of cyclopentylacetic acid dianhydride
-1,2,3,4-butanetetracarboxylic dianhydride 4
Synthesized except that 4.82 g (0.20 mol) was used
As in Example 1, the logarithmic viscosity (ηln) was 0.86 dl /
g of polyamic acid [this is referred to as “polyamic acid (A
-8) ". 108.1 g were obtained. Synthesis Example 10 2,3,5-Tricarboxy
1,3,3a, instead of cycyclopentylacetic acid dianhydride
4,5,9b-Hexahydro-5- (tetrahydro-
2,5-dioxo-3-furanyl) -naphtho [1,2-
c] 60.05 g of furan-1,3-dione (0.20 mol
Logarithmic viscosity in the same manner as in Synthesis Example 1 except that
Polyamic acid having a degree (ηln) of 0.81 dl / g
[This is referred to as “polyamic acid (A-9)”. ] 11
7.0 g were obtained. Then, the polyamic acid (A-1)
Instead, 40.0 g of polyamic acid (A-9) was used.
Except for this, the logarithmic viscosity (ηln) was the same as in Synthesis Example 2.
Is 0.94 dl / g [imidized polymer
Imidized polymer (B-9) ". 36.1 g was obtained.
Was. Synthesis Example 11 2,3,5-Tricarboxy
1,3,3a, instead of cycyclopentylacetic acid dianhydride
4,5,9b-Hexahydro-8-methyl-5- (tetra
Lahydro-2,5-dioxo-3-furanyl) -naphtho
[1,2-c] furan-1,3-dione 62.85 g
(Synthesis example 1) except that (0.20 mol) was used
And the logarithmic viscosity (ηln) is 0.79 dl / g.
Riamic acid [this is called "polyamic acid (A-10)"
And ] 119.7 g was obtained. Then, polyamic
Polyamic acid (A-10) 4 in place of acid (A-1)
Except that 0.0 g was used, the same as in Synthesis Example 2,
Imidation with a logarithmic viscosity (ηln) of 0.93 dl / g
Polymer [this is referred to as “imidized polymer (B-10)”
You. 36.0 g was obtained. [Comparative Synthesis Example 1] represented by the chemical formula (1)
1,4-phenylenediamine in place of the specific diamine compound
Except that 21.63 g (0.20 mol) was used.
Logarithmic viscosity (ηln) was 1.23 in the same manner as in Synthesis Example 1.
dl / g of polyamic acid [this is referred to as "polyamic acid".
Acid (a-1) ". 60.7 g was obtained. Then
Instead of the polyamic acid (A-1), the polyamic acid (a
-1) Same as Synthesis Example 2 except that 40.0 g was used
And the logarithmic viscosity (ηln) is 1.34 dl / g.
Imidized polymer [this is referred to as "imidized polymer (b-1)"
And 38.0 g were obtained. <Example 1> (1) Preparation of liquid crystal aligning agent: polyamide obtained in Synthesis Example 1
5.0 g of carboxylic acid (A-1) was added to N-methyl-2-pyrrolidone.
90% by weight of don and 3-methyl-3-methoxybutanol
Dissolved in a mixed solvent consisting of 10% by weight
A 4% by weight solution was obtained, and this solution was filtered with a 1 μm pore size filter.
A liquid crystal aligning agent was prepared by filtration with a filter. (2) Production of liquid crystal display element:   Enclosure electrodes patterned at regular intervals (display image
Display electrode having an orientation control window in the element)
On one surface of a substrate made of soda glass,
Apply the prepared liquid crystal alignment agent using a coating press.
And dried at 180 ° C. for 1 hour to obtain a dry film thickness of 0.1.
A resin film of 05 μm was formed. Then, the formed resin
The surface of the membrane is equipped with a roll wrapped with rayon cloth
Rubbing using a rubbing machine
A liquid crystal alignment film was formed. Here, the rubbing process
Roll rotation speed 500rpm, stage moving speed 1c
m / sec. After the rubbing treatment,
The liquid crystal alignment film is washed with isopropyl alcohol.
Was. Opposition patterned at regular intervals
Of a counter substrate made of soda glass provided with display electrodes
On one side, in the same manner as above, application of a liquid crystal alignment agent and
The coating film is dried to obtain a resin film, and the surface of the resin film is rubbed.
A liquid crystal alignment film was formed by performing a bing process. The liquid crystal alignment film is formed as described above.
The outer edge of each of the substrate and the counter substrate has a diameter of 6 mm.
Epoxy resin system containing μm aluminum oxide spheres
After applying the adhesive by screen printing method,
The liquid crystal alignment films on the substrates face each other, and
Pair the substrate so that the rubbing direction of the liquid crystal alignment film is orthogonal.
Opposite substrates are placed facing each other with a gap between them, and the outer edges contact each other.
Then, the adhesive was cured by pressing. The inner surface of the substrate (one of each substrate
Surface) and within the cell gap defined by the sealant
The nematic liquid crystal "MLC-6012" (Merck
Injection-filled, then epoxy-bonded injection hole
A liquid crystal cell was formed by sealing with an agent. After that, the liquid crystal cell
On the outer surface (the other surface of each substrate), the polarization direction is
Matches the rubbing direction of the liquid crystal alignment film formed on one side of the plate
By attaching a polarizing plate so that the
Type liquid crystal display device (the liquid crystal display device of the present invention) was produced. (3) Evaluation of liquid crystal display element:
In the liquid crystal display device manufactured by
The tilt angle is 0 °, and this liquid crystal display element depends on the viewing angle.
The nature was small. Also, this liquid crystal display element is
Abnormal domains are recognized when pressure is turned on and off
And the orientation of the liquid crystal molecules was also good. Below are the evaluation results
It is shown in Table 1. <Examples 2 to 11> The formulations shown in Table 1 below were used.
Therefore, Synthesis Example 2 instead of polyamic acid (A-1)
Polyamic acid A and imidized polymer obtained in 11
Liquid crystal alignment in the same manner as in Example 1 except that B was used.
A liquid crystal aligning agent is prepared, and a substrate is prepared using each of the prepared liquid crystal aligning agents.
Liquid crystal alignment films are formed on one side of the
A liquid crystal display of the present invention was prepared in the same manner as in Example 1 except that the liquid crystal display was formed.
An indicator device was produced. Of the present invention thus produced.
Measurement of pretilt angle of liquid crystal molecules for liquid crystal display devices
Table 1 below shows the values and the evaluation results of the orientation of liquid crystal molecules.
Shown. Comparative Example 1 Polyamic acid (A-1)
Instead, the imidized polymer (b-
Except that 1) was used, the liquid crystal distribution was the same as in Example 1.
A liquid crystal aligning agent is prepared, and one surface of the substrate is
And liquid crystal alignment film formed on one side of the counter substrate
A liquid crystal display device for comparison was prepared in the same manner as in Example 1 except for the above.
Made. About the liquid crystal display device thus manufactured,
The measured value of the pretilt angle of the liquid crystal molecules and the
The evaluation results of the orientation are also shown in Table 1 below. [0078] [Table 1][0079] The liquid crystal display device of the present invention has a liquid crystal alignment film and
The liquid crystal molecules at the interface with the liquid crystal layer have a pretilt angle
Liquid crystal molecules can be aligned without
The rising direction can be reliably regulated in the expected direction.
And the viewing angle dependency is small,
Thus, a favorable display state can be ensured. Only
In addition, the liquid crystal display device of the present invention also has excellent alignment of liquid crystal molecules.
Have been. The liquid constituting the liquid crystal display device of the present invention
For example, JP-A-6-222366 discloses a crystal orientation film.
And Japanese Patent Application Laid-Open No. 6-281937.
Pre-tilt angle changes by irradiating
The processing described in JP-A-5-107544 is disclosed.
Rubbed liquid crystal alignment film surface
A resist film is formed partially on the rubbing process.
Remove the resist film after performing rubbing treatment in the direction
Process to change the alignment ability of the liquid crystal alignment film.
To increase the viewing angle dependence of the liquid crystal display device.
It is possible to make it smaller. The liquid crystal display device of the present invention is useful for various devices.
Can be used for example, desktop calculators, watches,
Table clock, counting display board, word processor, personal computer
Suitable for liquid crystal display devices such as computers and liquid crystal televisions
Can be used.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram showing a configuration of a main part of a liquid crystal display device of the present invention. [Description of Signs] 1 Substrate 2 Display electrode 3 Liquid crystal alignment film 4 Counter substrate 5 Counter display electrode 6 Liquid crystal alignment film 7 Liquid crystal layer 8 Alignment control window 9 Polarizer 10 Polarizer

Continuing from the front page (72) Inventor Yasuaki Rokka 2--11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (72) Inventor Yasuo Matsuki 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (56) References JP-A-62-292836 (JP, A) JP-A-63-295633 (JP, A) JP-A-1-239525 (JP, A) JP-A-4-340521 (JP) JP-A-6-51316 (JP, A) JP-A-8-43830 (JP, A) JP-A-8-122793 (JP, A) JP-A-8-169954 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 73/00-73/26

Claims (1)

(57) [Claim 1] A substrate (1) provided with a display electrode (2)
A liquid crystal alignment film (3) is formed on one surface (1A), and a liquid crystal alignment film (6) is formed on one surface (4A) of a counter substrate (4) provided with a counter display electrode (5). ) And the opposing substrate (4) sandwich the liquid crystal layer (7). In the display pixel, at least one of the display electrode (2) and the opposing display electrode (5) is partially removed. A liquid crystal alignment film (3) formed on one surface (1A) of the substrate (1) and a liquid crystal alignment film formed on one surface (4A) of the counter substrate (4). The film (6) is made of a tetracarboxylic dianhydride represented by the following general formula (I) and a diamine compound represented by the following general formula (II) and / or a diamine compound represented by the following general formula (III) And the polyamic acids obtained by reacting The liquid crystal display element characterized by comprising at least one polymer selected from the imidized polymer obtained an acid by dehydration ring-opening. Embedded image [In the general formula (I), R ¹ represents a tetravalent organic group. [Chemical formula 2] [In the general formula (II), R ² , R ⁵ , R ⁶ and R ⁷ each represent the same or different alkyl group, alkoxyl group or halogen atom, and a, d, e and f each represent 0 to 4 An integer, R ² , R ⁵ , R ⁶ or R ⁷
May be the same or different, and R ³ and R ⁴ represent the same or different divalent organic groups, respectively, and b and c
Is 0 or 1 respectively. [Chemical formula 3] [In the general formula (III), R ⁸ , R ¹¹ , R ¹² and R ¹³ each represent the same or different alkyl group, alkoxyl group or halogen atom, and g, j, k and l each represent 0 to 4 An integer, R ⁸ , R ¹¹ , R ¹² or R ¹³
May be the same or different, and R ⁹ and R ¹⁰ each represent the same or different divalent organic group, and h and i
Is 0 or 1 respectively. ]