JP3050480B2 - Liquid crystal alignment film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal alignment film having a portion where the alignment of liquid crystal molecules is partially different.

[0002]

2. Description of the Related Art In general, a liquid crystal alignment film is used for a liquid crystal display device, and aligns liquid crystal molecules in a certain direction.
That is, it is provided because it needs to be oriented.
2. Description of the Related Art Liquid crystal display devices have been conventionally used for displays such as watches, calculators, computers, and word processors. As a basic structure of a liquid crystal display element, it is common that two substrates having an alignment film provided on a transparent electrode are arranged with the alignment film inside, and a liquid crystal is sealed between them.

As such a liquid crystal display element, a display in a twisted nematic (TN) mode in which a nematic liquid crystal has a twisted structure or a super twisted nematic (STN) mode is known. As the driving of the liquid crystal display element, there is known a matrix display in which electrodes are formed in a display pattern such as a stripe shape or a grid shape on a substrate, and a device using a thin film transistor (TFT). Something comparable to a normal CRT has been realized. However, such a liquid crystal display element has a disadvantage that the viewing angle is narrow.

Several methods have been proposed to improve the viewing angle. For example, page 94 of the latest 94 LCD Technology discloses a two-rubbing method in which an alignment film is rubbed, patterned with a resist, and then rubbed in the opposite direction, or a method of forming the alignment film into a two-layer structure. However, these methods involve a patterning step using a resist, so that there are problems such as an increase in production cost and a problem that the conventional alignment film material has poor solvent resistance.

[0005]

The present invention solves the above-mentioned problems of the prior art and relates to a liquid crystal alignment film having a portion in which the surface of the alignment film is irradiated with light to change the pretilt angle of liquid crystal molecules. .

[0006]

The liquid crystal alignment film of the present invention has the general formula (I)

[0007]

Embedded image [Wherein, in the general formula (I), A represents a tetravalent residue of tetracarboxylic dianhydride excluding a cyclobutane ring , and R represents a divalent organic group]. 1 output from a low-pressure mercury lamp at a predetermined location on the polyimide surface
The liquid crystal molecules have portions with different orientations formed by irradiating light in the range of ３０30 J / cm ² .

The liquid crystal alignment film is formed of ITO (Indium Tin Oxi).
The substrate is formed on an electrode substrate such as a glass plate provided with a transparent electrode such as de), and a pair of the substrates is opposed to each other, and a liquid crystal is sandwiched between the electrode substrates to form a liquid crystal sandwiching substrate. In this case, the liquid crystal alignment film formed on one electrode substrate of the liquid crystal holding substrate may have no change in the pretilt angle. Further, a liquid crystal display device having a liquid crystal holding substrate can be obtained by a known method using the liquid crystal holding substrate.

The liquid crystal alignment film can be manufactured using a liquid crystal alignment film material containing a polyamic acid which is a precursor of polyimide. This polyamic acid is
General formula (II) of

Embedded image [However, in the general formula (II), A and R are the same as those in the general formula (I)].

The liquid crystal alignment film can be manufactured using a liquid crystal alignment film material containing a polyimide resin described below. The polyimide resin is a general term for the above-mentioned polyimide and its precursor. Examples of the polyimide precursor include the above-mentioned polyamic acid and a partially imidized polyamic acid.

The above-mentioned polyimide resin can be produced by reacting a tetracarboxylic dianhydride (including a derivative) and a diamine compound (including a derivative).

[0012] Examples of the general formula (III) tetracarboxylic acid dianhydride represented by, butane-1,2,3,4-tetracarboxylic dianhydride, shea Kuropentan 1,2,3,4 Carboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,4,3 ', 4'-bicyclohexyltetracarboxylic dianhydride, bis [bicyclo (2,2, 1) Hepta-2,3-dicarboxylic anhydride] sulfone, 1,3-di (3,4-dicarboxycyclohexyl) cyclohexanol dianhydride, bicyclo (2,2,1) hepta-2,3,5 , 6-tetracarboxylic dianhydride, bicyclo (2,2,2) oct-7-ene-2,3
5,6-tetracarboxylic dianhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydro Naphthalene-1,2,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride.

Ethylene glycol bis (trimellitic anhydride), 1,3-propanediol bis (trimellitic anhydride), 1,4-butanediol bis (trimellitic anhydride), 1,5-pentanediol Bis (trimellitic anhydride), 1,6-hexanediol bis (trimellitic anhydride), 1,8-octanediol bis (trimellitic anhydride), 1,10-decanediol bis (trimellitic acid) Anhydride), 1,16-hexadecanediol bis (trimellitic anhydride) pyromellitic anhydride, 3,3 ′, 4,4′-diphenyltetracarboxylic dianhydride, 1,2,5,6 -Naphthalenetetracarboxylic dianhydride, 2,3,6,7, -naphthalenetetracarboxylic dianhydride, 2,2 ', 3,3'-diphenyltetracarboxylic acid Dianhydride, 2,2-bis (3,4, -dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,4,9,10-perylenetetracarboxylic Acid dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic acid Dianhydride, 2,6-dichloronaphthalene-
1,4,5,8-tetracarboxylic dianhydride, 2,7-
Dichloronaphthalene-1,4,5,8, tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1, 8,9,10-tetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride , 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-
Dicarboxyphenyl) methane dianhydride, bis (3,4
-Dicarboxyphenyl) methane dianhydride, bis (3,
4-dicarboxyphenyl) sulfone dianhydride,

Benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3 ', 4'-benzophenonetetracarboxylic dianhydride, 2,3,2', 3-benzophenonetetracarboxylic Acid dianhydride, 2,3,3 ', 4'
-Benzonephenone tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride,
Ethylene tetracarboxylic dianhydride, 2,3,3 ',
4′-biphenyltetracarboxylic dianhydride, 3,4
3 ′, 4′-biphenyltetracarboxylic dianhydride,
2,3,2 ', 3'-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) methylphenylsilane dianhydride , Bis (3,4-dicarboxyphenyl) diphenylsilane dianhydride, bis (2,3-dicarboxyphenyl) dimethylsilane dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene Dianhydride, 1,3-bis (3,4
-Dicarboxyphenyl) -1,1,3,3-tetramethyldisiloxane dianhydride, p-phenylbis (trimellitic acid monoester acid anhydride), 4,4′-bis (3,4-dicarboxy) Phenoxy) diphenylsulfide dianhydride, 2,2-bis (2,3-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] hexafluoropropane dianhydride, 1,4-bis (2-hydroxyhexafluoropropyl) benzenebistrimellitic dianhydride,
1,3-bis (2-hydroxyhexafluoropropyl) benzenebistrimellitic dianhydride,

(Trifluoromethyl) pyromellitic dianhydride, bis (trifluoromethyl) pyromellitic dianhydride, 5,5'-bis (trifluoromethyl) -3,
3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 5,5'-tetrakis (trifluoromethyl) -3,3 ', 4,4'-biphenyltetracarboxylic dianhydride , 5,5'-bis (trifluoromethyl)-
3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride, 5,5'-bis (trifluoromethyl)
-3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, bis {(trifluoromethyl) dicarboxyphenoxy} benzene dianhydride, bis {(trifluoromethyl) dicarboxyphenoxy} biphenyl dianhydride , Bis {(trifluoromethyl) dicarboxyphenoxy} (trifluoromethyl) benzene dianhydride, bis {(trifluoromethyl) dicarboxyphenoxy} bis (trifluoromethyl) biphenyl dianhydride, bis {(trifluoromethyl) ) Dicarboxyphenoxy diphenylether dianhydride, bis (dicarboxyphenoxy) (trifluoromethyl) benzene dianhydride, bis
(Dicarboxyphenoxy) bis (trifluoromethyl) benzene dianhydride, bis (dicarboxyphenoxy) tetrakis (trifluoromethyl) benzene dianhydride, bis (dicarboxyphenoxy) bis (trifluoromethyl) biphenyl dianhydride, Bis (dicarboxyphenoxy) tetrakis (trifluoromethyl) biphenyl dianhydride; These derivatives include ester compounds such as dimethyl ester and diethyl ester, and acid halides such as acid chloride bromide. These may be used in combination of two or more.

As the diamine compound, 4- (4-
Aminophenyl) -3-aminobenzoic acid, 2,2-bis (4-aminophenyl) propane, 2,6-diaminopyridine, bis (4-aminophenyl) diethylsilane,
Bis- (4-aminophenyl) diphenylsilane, bis- (4-aminophenyl) ethylphosphine oxide, bis- (4-aminophenyl) -N-butylamine, bis- (4-aminophenyl) -N-methylamine, N- (3-aminophenyl) -4-aminobenzamide, 3,3'-diaminodiphenylmethane, 3,3 '
-Diaminodiphenyl ether, 3,3'-diaminodiphenylsulfone, 3,3'-diaminodiphenylpropane, 3,3'-diaminodiphenylsulfide, 2,
3,5,6-tetramethyl-p-phenylenediamine p
-Phenylenediamine, 2,5-dimethyl-p-phenylenediamine m-phenylenediamine, m-xylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, 4,4'-diaminodiphenylpropane,
4,4'-diaminodiphenylmethane, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone,
4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene 2,2-bis (4-
(Aminofexiphenyl)) propane

2,4-bis (β-amino-t-butyl)
Toluene, bis (p-β-amino-t-butyl-phenyl) ether, bis (p-β-methyl-γ-amino-pentyl) benzene, bis-p- (1,1-dimethyl-5)
-Aminopentyl) benzene, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis {4- (2-aminophenoxy) phenyl} hexafluoropropane, 2,2-bis {4- ( 3-aminophenoxy) phenyl {hexafluoropropane, 2,2-bis} 4-
(4-aminophenoxy) phenyl} hexafluoropropane, 2,2-bis (3-carbamoyl-4-aminophenyl) hexafluoropropane, 2,2-bis {4- (3
-Carbamoyl-4-aminophenoxy) phenyl} hexafluoropropane, 2,2-bis (3-sulfamoyl-4-aminophenyl) hexafluoropropane, 2,
2-bis {4- (3-sulfamoyl-4-aminophenoxy) phenyl} hexafluoropropane, 2,2-
Bis (3-carboxy-4-aminophenyl) hexafluoropropane, 2,2-bis {4- (3-carboxy-
4-aminophenoxy) phenyl @ hexafluoropropane,

1,3-bis [2- {4- (4-aminophenoxy) phenyl} hexafluoroisopropyl] benzene p-bis (3-carboxy-4-aminophenoxy) tetrafluorobenzene, 4,4'-bis (3-carboxy-4-aminophenoxy) octafluorobiphenyl, 4,4′-diaminooctafluorobiphenyl, 1,2-bis (3-carboxy-4-aminophenyl) tetrafluoroethane, 1,3-bis (3 -Carboxy-4-aminophenyl) hexafluoropropane,
1,5-bis (3carboxy-4-aminophenyl) decafluoropentane, diaminobenzotrifluoride, bis (trifluoromethyl) phenylenediamine,
Diaminotetra (trifluoromethyl) benzene, diamino (pentafluoroethyl) benzene, 2,2′-bis (trifluoromethyl) benzidine, 2,2′-bis (trifluoromethyl) -4,4′-diaminodiphenyl ether, Bis (aminophenoxy) di (trifluoromethyl) benzene, bis (aminophenoxy) tetrakis (trifluoromethyl) benzene, bis [(trifluoromethyl) aminophenoxy] benzene, bis [(trifluoromethyl) aminophenoxy] biphenyl, Bis {[(trifluoromethyl) aminophenoxy] phenyl} hexafluoropropanehexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, tetramethylenediamine, Ropi diamine, 3
-Methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine,

2,12-diaminododecane, 1,2-bis (3-aminopropoxy) ethane, 2,2-dimethylpropylenediamine, 3-methoxy-hexamethylenediamine, 2,5-dimethylhexamethylenediamine,
2,5-dimethylheptamethyldiamine, 5-methylnonamethylenediamine, 2,17-diaminoicosadecane, 1,4-diaminocyclohexane, 1,10-diamino-1,10-dimethyldecane, 1,12-diamino Octadecane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-
Diaminodiphenylmethane, 3,3'-dimethoxy-
4,4'-diaminodiphenylmethane, 3,3'diethoxy-4,4'-diaminodiphenylmethane, 3,3 '
-Difluoro-4,4'-diaminodiphenylmethane,
3,3'-dichloro-4,4'diaminodiphenylmethane, 3,3'-dibromo-4,4'-diaminodiphenylmethane, 3,3'-di (trifluoromethyl) -4,
4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenyl ether, 3,3'-
Diisopropyl-4,4'-diaminodiphenylether, 3,3'-dimethoxy-4,4'-diaminodiphenylether, 3,3'-diethoxy-4,4'-diaminodiphenylether, 3,3'-difluoro-4,
4'-diaminodiphenyl ether, 3,3'-dichloro-4,4'-diaminodiphenyl ether, 3,3 '
-Dibromo-4,4'-diaminodiphenyl ether,
3,3′-di (trifluoromethyl) -4,4′-diaminodiphenyl ether,

3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 3,3'-dimethoxy-4,4 '
-Diaminodiphenylsulfone, 3,3'-diethoxy-4,4'-diaminodiphenylsulfone, 3,3'-
Difluoro-4,4'-diaminodiphenyl sulfone,
3,3'-dichloro-4,4'-diaminodiphenylsulfone, 3,3'-dibromo-4,4'-diaminodiphenylsulfone, 3,3'-di (trifluoromethyl)
-4,4'-diaminodiphenylsulfone, 3,3'-
Dimethyl-4,4'-diaminodiphenylpropane,
3,3'-dimethoxy-4,4'-diaminodiphenylpropane, 3,3'-diethoxy-4,4'-diaminodiphenylpropane, 3,3'-difluoro-4,4 '
-Diaminodiphenylpropane, 3,3'-dichloro-
4,4′-diaminodiphenylpropane, 3,3′-dibromo-4,4′-diaminodiphenylpropane,
3'-di (trifluoromethyl) -4,4'-diaminodiphenylpropane, 3,3'-dimethyl-4,4'diaminodiphenyl sulfide, 3,3'-dimethoxy-
4,4 ′ diaminodiphenyl sulfide, 3,3′-diethoxy-4,4′-diaminodiphenyl sulfide,
3,3'-difluoro-4,4'-diaminodiphenyl sulfide, 3,3'-dichloro-4,4'-diaminodiphenyl sulfide, 3,3'-dibutomo-4,4 '
-Diaminodiphenyl sulfide, 3,3'-di (trifluoromethyl) -4,4'-diaminodiphenyl sulfide,

3,3'-dimethyl-4,4'-diaminodiphenylhexafluoropropane, 3,3'-dimethoxy-4,4'-diaminodiphenylhexafluoropropane, 3,3'-diethoxy-4,4 ' -Diaminodiphenylhexafluoropropane, 3,3'-difluoro-4
4'-diaminodiphenylhexafluoropropane,
3,3'-dichloro-4,4'-diaminodiphenylhexafluoropropane, 3,3'-dibromo-4,4 '
-Diaminodiphenylhexafluoropropane, 3,
3'-di (trifluoromethyl) -4,4'-diaminodiphenylhexafluoropropane, 3,3'-dimethyl-4,4'-diaminobenzophenone, 3,3'-dimethoxy-4,4'-diaminobenzophenone , 3,
3'-diethoxy-4,4'-diaminobenzophenone, 3,3'-difluoro-4,4'-diaminobenzophenone, 3,3'-dichloro-4,4'-diaminobenzophenone, 3,3'-dibromo- 4,4′-diaminobenzophenone, 3,3′-di (trifluoromethyl) -4,4′-diaminobenzophenone, 3,3′-
Dimethylbenzidine, 3,3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenylmethane, 3,3 ′,
5,5′-tetraisopropyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetramethoxy-4,4′-diaminodiphenylmethane, 3,3 ′,
5,5'-tetraethoxy-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetrafluoro-
4,4'-diaminodiphenylmethane, 3,3 ', 5
5'-tetrachloro-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetrabromo-4,4'-
Diaminodiphenylmethane, 3,3 ′, 5,5′-tetra (trifluoromethyl) -4,4′-diaminodiphenylmethane,

3,3 ', 5,5'-tetramethyl-4,
4'-diaminodiphenyl ether, 3,3 ', 5
5'-tetraethyl-4,4'-diaminodiphenyl ether, 3,3 ', 5,5'-tetramethoxy-4,4'
-Diaminodiphenyl ether, 3,3 ', 5,5'-tetraethoxy-4,4'-diaminodiphenyl ether,
3,3 ', 5,5'-tetrafluoro-4,4'-diaminodiphenyl ether, 3,3', 5,5'-tetrachloro-4,4'-diaminodiphenyl ether, 3,3 ', 5,5 '-Tetrafluoro-4,4'-diaminodiphenyl ether, 3,3',
5,5'-tetra (trifluoromethyl) -4,4'-diaminodiphenyl ether, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylsulfone, 3,3', 5,5 '-Tetramethoxy-
4,4′-diaminodiphenyl sulfone, 3,3 ′,
5,5'-tetraethoxy-4,4'-diaminodiphenylsulfone, 3,3 ', 5,5'-tetrafluoro-4
4'-diaminodiphenyl sulfone, 3,3 ', 5
5'-tetrachloro-4,4'-diaminodiphenylsulfone, 3,3 ', 5,5'-tetrabromo-4,4'
-Diaminodiphenyl sulfone, 3,3 ', 5,5'-
Tetra (trifluoromethyl) -4,4′-diaminodiphenylsulfone, 3,3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenylpropane, 3,3 ′,
5,5'-tetramethoxy-4,4'-diaminodiphenylpropane, 3,3 ', 5,5'-tetraethoxy-4
4'-diaminodiphenylpropane, 3,3 ', 5
5'-tetrafluoro-4,4'-diaminodiphenylpropane, 3,3 ', 5,5'-tetrachloro-4,4'
-Diaminodiphenylpropane, 3,3 ', 5,5'-
Tetrabromo-4,4′-diaminodiphenylpropane, 3,3 ′, 5,5′-tetra (trifluoromethyl) -4,4′-diaminodiphenylpropane,

3,3 ', 5,5'-tetramethyl-4
4'-diaminodiphenyl sulfide, 3,3 ', 5
5'-tetramethoxy-4,4'-diaminodiphenyl sulfide, 3,3 ', 5,5'-tetraethoxy-
4,4′-diaminodiphenyl sulfide, 3,3 ′,
5,5′-tetrafluoro-4,4′-diaminodiphenyl sulfide, 3,3 ′, 5,5′-tetrachloro-
4,4'-diaminodiphenyl sulfide, 3,3 ', 5,5'-
Tetrabromo-4,4'-diaminodiphenyl sulfide, 3,3 ', 5,5'-tetra (trifluoromethyl) -4,4'-diaminodiphenyl sulfide, 3,
3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenylhexafluoropropane, 3,3 ′, 5,5 ′
-Tetramethoxy-4,4'-diaminodiphenylhexafluoropropane, 3,3 ', 5,5'-tetraethoxy-4,4'-diaminodiphenylhexafluoropropane, 3,3', 5,5'-tetra Fluoro-4,
4'-diaminodiphenylhexafluoropropane,
3,3 ′, 5,5′-tetrachloro-4,4′-diaminodiphenylhexafluoropropane, 3,3 ′, 5
5′-tetrabromo-4,4′-diaminodiphenylhexafluoropropane, 3,3 ′, 5,5′-tetra (trifluoromethyl) -4,4′-diaminodiphenylhexafluoropropane,

3,3 ', 5,5'-tetramethyl-4,
4'-diaminobenzophenone, 3,3 ', 5,5'-
Tetramethoxy-4,4′-diaminobenzophenone,
3,3 ′, 5,5′-tetraethoxy-4,4′-diaminobenzophenone, 3,3 ′, 5,5′-tetrafluoro-4,4′-diaminobenzophenone, 3,3 ′,
5,5'-tetrachloro-4,4'-diaminobenzophenone, 3,3 ', 5,5'-tetrabromo-4,4'
-Diaminobenzophenone, 3,3 ', 5,5'-tetra (trifluoromethyl) -4,4'-diaminobenzophenone, 3,3', 5,5'-tetraisopropyl-
4,4'-diaminodiphenylmethane, 3,3'-diisopropyl-5,5'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diisopropyl-5
5'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-diisopropyl-5,5'-dimethyl-
4,4'-diaminodiphenyl ether, 3,3'-diisopropyl-5,5'-diethyl-4,4'-diaminodiphenyl ether, 3,3'-diisopropyl-
5,5′-dimethyl-4,4′-diaminodiphenylpropane, 3,3′-diisopropyl-5,5′-diethyl-4,4′-diaminodiphenylpropane, 3,3 ′
-Diisopropyl-5,5'-dimethyl-4,4'-diaminodiphenylsulfone, 3,3'-diisopropyl-5,5'-diethyl-4,4'-diaminodiphenylsulfone, 3,3'-bis (tri Fluoromethyl) benzidine, 2,2′-bis (trifluoromethyl) -4,
4'-diaminodiphenyl ether, 3,3'-bis (trifluoromethyl) -4,4'-diaminodiphenyl ether, 3,3 ', 5,5'-tetrakis (trifluoromethyl) -4,4'-diaminodiphenyl ether , 3,3'-bis (trifluoromethyl) -4,4 '
-Diaminobenzophenone and the like, and two or more of these may be used in combination.

Further, as a part of the diamine, silicon diamine may be used. As the silicon diamine, 1,3-bis (3-aminopropyl) -1,1,1
-Tetraphenyldisiloxane, 1,3-bis (3-aminopropyl) -1,1,1-tetramethyldisiloxane, 1,3-bis (4-aminobutyl) -1,1,1-
And tetramethyldisiloxane. When using silicon diamines, these are preferably used in an amount of 0.1 to 10 mol% based on the total amount of the diamines. By using silicon diamine, the resulting polyimide resin has improved adhesion. Examples of the tetracarboxylic dianhydride include butane-1,2,3,4-tetracarboxylic dianhydride, cyclobutane-1,2,3,4-tetracarboxylic dianhydride, cyclopentane-1, 2,3,4-
Tetracarboxylic dianhydride, cyclohexane-1,2,2
4,5-tetracarboxylic dianhydride, 3,4,3 ',
4'-bicyclohexyltetracarboxylic dianhydride, bis [bicyclo (2,2,1) hepta-2,3-dicarboxylic anhydride] sulfone, 1,3-di (3,4-dicarboxycyclohexyl) cyclo Hexanol dianhydride, bicyclo (2,2,1) hepta-2,3,5,6-tetracarboxylic dianhydride, bicyclo (2,2,2) oct-7-
Ene-2,3,5,6-tetracarboxylic dianhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5 6,
Preferred are 7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride and 2,3,5-tricarboxycyclopentyl acetic acid dianhydride.

In producing the polyimide resin,
The tetracarboxylic dianhydride and the diamine are reacted at an appropriate temperature. In this reaction, the degree of imidization can be appropriately adjusted by selecting appropriate conditions. For example, to produce a completely or almost completely imidized polyimide by reacting at 100 ° C. or higher, particularly 120 ° C. or higher, if necessary, in the presence of a catalyst such as tributylamine, triethylamine, and triphenyl phosphite. (The catalyst is preferably used in an amount of 0 to 15% by weight based on the total amount of the reaction components, and more preferably 0.1 to 15% by weight.
When the reaction is carried out at 80 ° C. or less, particularly at 50 ° C. or less, it is a precursor of the polyimide and is completely or almost not imidized.
Polyamic acid can be produced. Further, a polyimide precursor in which imidization has partially progressed can be produced.

The above-mentioned polyamic acid or the polyimide precursor partially imidized is further heated at 100 ° C.
Above, particularly a method of imidization by heating to 120 ° C. or higher, acetic anhydride, propionic anhydride, acid anhydrides such as benzoic anhydride, ring-closing agents such as carbodiimides such as dicyclohexylcarbodiimide, and pyridine and isoquinoline as needed. Chemical ring closure (imidization) in the presence of a ring closure catalyst such as trimethylamine, aminopyridine, imidazole, etc.
(Preferably, the ring-closing agent and the ring-closing catalyst are used in a range of 1 to 8 mol per 1 mol of the acid anhydride) to produce a polyimide in which imidation is almost or completely completed. it can. These reactions are preferably performed in the presence of an organic solvent.

The organic polar solvents usable in the above reaction include N, N-dimethylformamide, N, N-
Dimethylacetamide, N-methyl-2-pyrrolidone,
Dimethyl sulfoxide, hexamethylphosphoramide,
There are phenol, m-cresol, chlorobenzene and the like, and two or more kinds thereof may be used as a mixture as long as they are compatible with each other. In addition, along with these organic polar solvents, toluene,
General-purpose solvents such as xylene, cellosolve acetate, and methyl cellosolve can be used in combination as long as the solubility of the polyimide resin or its precursor is not reduced. There is no particular limitation on the order in which the reactants are added. When using two or more kinds of raw materials as acid dianhydride and diamine,
Depending on the method of adding the reaction raw materials, the obtained polymer may be a random copolymer, a block copolymer or the like, but any of these polymers is not particularly limited.

In the polyimide resin thus obtained, a polyimide precursor, particularly a polyamic acid,
It is dissolved in N, N-dimethylacetamide at a concentration of 0.1 g / dl and has a reduced viscosity of 0.1 d when measured at 30 ° C.
It is preferably at least 1 / g.

The material for the liquid crystal alignment film contains the polyimide resin, and is preferably a material (varnish) obtained by dissolving the polyimide resin in an organic solvent. As the organic solvent, those exemplified above as those which can be used in the production of the polyimide resin can be used. The selection of the organic solvent to be used is determined in consideration of the solubility of the polyimide-based resin. Among the polyimide-based resins, a polyimide precursor such as polyamic acid has good solubility in the organic solvent.

In addition to the polyimide resin or the polyamic acid resin, additives can be used for the liquid crystal alignment film material. Examples of the additives used herein include benzophenones such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, Michler's ketone, chloroacetophenone, diethoxyacetophenone, 4-phenoxydichloroacetophenone and 4-benzophenone. t-butyldichloroacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- ( Acetophenones such as 4-methylthiophenyl) -morpholinopropan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoy Isopropyl ether,
Benzoins such as benzylmethyl ketal, thioxanthone such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone and isopropylthioxanthone; Dimethyl 2,2'-azobisisobutyrate, 1,1'-azobis- (cyclohexane-1
Azo compounds such as 2,2 -'- azobis (2,4-dimethylvaleronitrile), azobisisobutyronitrile, 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile), 2,2- Bis-((4-stearylamino) phenoxyphenyl)
There are compounds having a long aliphatic chain such as propane and 2,2-bis-((4-laurylamino) phenoxyphenyl) propane, and these may be used in combination of two or more. The amount of the additive to be used is set at 0.1 to the weight of the polyimide resin or the polyamic acid resin in the liquid crystal alignment film material.
01 to 60% by weight. If the amount is less than 0.01% by weight, the effect of changing the pretilt is small.

The liquid crystal alignment film material is applied on a suitable substrate such as a glass substrate on which a transparent electrode such as ITO (Indium Tin Oxide) is formed in advance, and dried to form a polyimide layer. As a coating method, a spin core
, A dipping method, a printing method, a spraying method, and the like. The drying temperature is 100 to 250 ° C, preferably 150 to
Although it is selected in the range of 230 ° C., when a polyimide precursor such as polyamic acid is used as the polyimide resin, the temperature is set to a temperature equal to or higher than the temperature at which ring closure occurs.
C. or higher is preferable, and particularly 180.degree. C. or higher is preferable. The heating time is preferably from 1 minute to 6 hours, particularly preferably from 1 minute to 3 hours. In order to improve the adhesion between the substrate and the polyimide layer, a coupling agent such as a silane coupling agent or a titanium coupling agent may be used between them.

In the present invention, a predetermined surface of the resin layer containing polyimide and polyamic acid is irradiated with light output from a low-pressure mercury lamp to be used as a liquid crystal alignment film. Also,
A liquid crystal display device can be obtained by a known method using the liquid crystal holding substrate having the liquid crystal alignment film.

The low-pressure mercury lamp encloses mercury in a transparent high-purity quartz tube, applies an electric current between tungsten electrodes at both ends, generates an arc, and irradiates light. The low-pressure mercury lamp has an internal mercury vapor pressure of 10 ^-2 to 10 ^-3 mmH
g at an internal temperature of 40 ° C. and a dominant wavelength of 185 n
m, 253.7 nm. Further, an ozone-less lamp absorbing short-wavelength ultraviolet rays of 200 nm or less to suppress generation of ozone can be used. The amount of light to be applied is not particularly limited, but is applied in the range of 0.1 to 30 joules / cm 2. If the amount is less than this, the change in the orientation is small, and if it is large, the alignment film is deteriorated, causing a problem in reliability and the like. Normally, the liquid crystal alignment film is manufactured by applying the liquid crystal alignment film material to a glass substrate, sequentially performing preliminary drying and main curing, and then performing a rubbing treatment.Light irradiation is performed in any case after these steps. Although good, irradiation after rubbing is particularly preferable since the pretilt angle change is large. The pre-drying temperature is 50C to 150C and the time is 10 seconds to 5 minutes. The main curing conditions are as follows: 150 ° C.
Performed at 300 ° C. for 1 minute to 3 hours. The rubbing treatment is a treatment of rubbing the surface of the alignment film using a roller wrapped with a cloth made of nylon or rayon, whereby the alignment of liquid crystal molecules is obtained.

[0035]

EXAMPLES The present invention will be described below with reference to examples, but the scope of the present invention is not limited by these examples. Synthesis Example 1 In a four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a drying tube, 8 g of N, N-dimethylacetamide and
1.08 g (10 mmol) of phenylenediamine were added and stirred until a homogeneous solution was obtained. After the diamine is dissolved, 1.12 g (5 mmol) of cyclohexane-1,2,4,5-tetracarboxylic dianhydride and 2.61 g of 1,10-decanediol bis (trimellitic anhydride)
(5 mmol) was added in small portions. After the addition was completed, stirring was performed for 5 hours to obtain a polyamic acid solution.

Synthesis Example 2 N-methylpyrrolidone (8 g) and p-phenylenediamine (1.08 g (10 mmol)) were placed in a four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a drying tube to obtain a homogeneous solution. Stir until it is. After the diamine is dissolved, 1.47 g (7 mmol) of cyclopentane-1,2,3,4-tetracarboxylic dianhydride and 1.57 g (3 mmol) of 1,10-decanediol bis (trimellitic anhydride) Was added in small portions. After the addition was completed, stirring was performed for 5 hours to obtain a polyamic acid solution.

Synthesis Example 3 N-methylpyrrolidone (8 g) and p-phenylenediamine (1.08 g (10 mmol)) were placed in a four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a drying tube to obtain a homogeneous solution. Stir until it is. After the diamine has dissolved,
1.84 g (6 mmol) of 3,4,3 ', 4'-bicyclohexyltetracarboxylic dianhydride and 2.09 g of 1,10-decanediol bis (trimellitic anhydride)
(4 mmol) was added in small portions. After the addition was completed, stirring was performed for 5 hours to obtain a polyamic acid solution.

Synthesis Example 4 In a four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a drying tube, 8 g of N, N-dimethylacetamide and p
1.08 g (10 mmol) of phenylenediamine were added and stirred until a homogeneous solution was obtained. After the diamine is dissolved, 1.58 g (8 mmol) of 1,2,3,4-butanetetracarboxylic dianhydride and 0.99 g (2 mmol) of 1,10-octanediol bis (trimellitic anhydride) Was added in small portions. After the addition was completed, stirring was performed for 5 hours to obtain a polyamic acid solution.

Synthesis Example 5 N-methylpyrrolidone (8 g) and p-phenylenediamine (1.05 g, 9.7 mmol) were added to a four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a drying tube. −
0.075 (0.3 mmol) of bis (aminopropyl) -tetramethyldisiloxane was added and stirred until a homogeneous solution was obtained. After the diamine is dissolved,
1.84 g (6 mmol) of 3 ', 4'-bicyclohexyltetracarboxylic dianhydride and 2.09 g (4 mmol) of 1,10-decanediol bis (trimellitic anhydride) were added little by little. After the addition was completed, stirring was performed for 5 hours to obtain a polyamic acid solution.

Synthesis Example 6 N-methylpyrrolidone (8 g) and m-phenylenediamine (0.86 g (8 mmol), 4,4′-) were placed in a four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a drying tube. 0.4 g (2 mmol) of diaminodiphenylmethane was added and stirred until a homogeneous solution was obtained. After the diamine was dissolved, 1.53 g (5 mmol) of 3,4,3 ', 4'-bicyclohexyltetracarboxylic dianhydride, 1,10
-Decanediol bis (trimellitic anhydride) 2.6
1 g (5 mmol) was added in small portions. After the addition,
Stirring was performed for 5 hours to obtain a polyamic acid solution.

Synthesis Example 7 N-methylpyrrolidone (8 g) and p-phenylenediamine (0.97 g, 9 mmol) and 1,4-cyclohexane were placed in a four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a drying tube. 0.11 g (1 mmol) of diamine was added,
Stir until a homogeneous solution is obtained. After the diamine was dissolved, 1.83 g (6 mmol) of 3,4,3 ', 4'-bicyclohexyltetracarboxylic dianhydride and 1,09-decanediol bis (trimellitic anhydride) 2.09
g (4 mmol) was added in small portions. After the addition was completed, stirring was performed for 5 hours to obtain a polyamic acid solution.

Synthesis Example 8 In a four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a drying tube, 20 g of tricresole and 0.81 g (7.5 mmol) of p-phenylenediamine, 4,4′- 0.5 g (2.5 mmol) of diaminodiphenylmethane was added and stirred until a homogeneous solution was obtained. After dissolution of the diamine, 1.19 g of butanetetracarboxylic dianhydride,
(6 mmol) and 2.1 g (4 mmol) of 1,10-decanediol bis (trimellitic anhydride) were added little by little. After completion of the addition, stirring was carried out for 5 hours, and then the reaction solution was heated to 195 ° C.
After an hour, the reaction was carried out. The reaction solution was poured into acetone, and the precipitated resin was separated, washed and dried to obtain a polyimide resin.

Examples 1 to 10 The polyamic acid or polyimide solutions obtained in Synthesis Examples 1 to 7 were diluted with N-methylpyrrolidone so that the solid content was 5% by weight. The solution was spin-coated on two glass substrates with ITO transparent electrodes. Then 100 ° C, 1
Pre-drying, main curing and rubbing at 200 ° C. for 30 minutes. Light irradiation using a low-pressure mercury lamp was performed after the steps shown in Tables 1 and 2. Next, the two substrates were combined with their polyimide layers facing each other so that the rubbing direction was antiparallel, and the surroundings were sealed with a room temperature-curable epoxy adhesive. The liquid crystal ZLI was added to these test liquid crystal cells at room temperature.
-4792 (trade name, manufactured by Merck) was enclosed. After heating the obtained liquid crystal cell at 130 ° C. for 1 hour, the pretilt angle was measured. Tables 1 and 2 show the results.

[0044]

[Table 1] 量 Light irradiation amount of light irradiation used Pretilt angle (Degree) Polyimide Timing J / cm ² Unirradiated area Irradiated area ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example 1 Synthesis example 1 After rubbing 1 14.7 8.3 ──────────────────────────────────── Example 2 Synthesis Example 2 After main curing 5 8.7 5.2 ─ Example 3 Synthesis Example 3 After rubbing 3 12.1 8.4──────────────────────────────────── Example 4 Synthesis Example 4 After Rubbing 1 8.3 5.0 ────────── Example 5 Synthesis Example 5 After rubbing 10 7.3 0.2 ━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━━━━━━━━

[0045]

[Table 2] 量 Light irradiation amount of light irradiation used Pretilt angle (Degree) Polyimide Timing J / cm ² Unirradiated area Irradiated area ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example 6 Synthesis Example 6 After full curing 3 5.3 1.3 ── Example 7 Synthesis Example 7 After main curing 5 9.7 2.3 ── Example 8 Synthesis Example 3 After pre-drying 3 12.1 4.3 Example 9 Synthesis Example 5 After predrying 2 7.8 2.5 ─────────── Example 10 Synthesis Example 7 After rubbing 3 13.5 3.1────────────────────────── Example 11 Synthesis Example 8 After rubbing 5 7.8 1.5 ━━━━━━━━━━━ Here, in Examples 3 and 7, an ozone-less lamp was used, and in other cases, an ozone generating lamp was used.

The change in surface tension before and after light irradiation was measured using a polymer obtained by applying the used polymer on a glass substrate. The surface tension was calculated from the contact angle with water and iodine methane. The measurement results of the surface tension (erg / cm 2) are as follows: Example 1 Unirradiated part 42.3 Irradiated part 67.3 Example 2 Unirradiated part 45.4 Irradiated part 54.7 5.5 Irradiated section 69.4 Example 4 Unirradiated section 42.7 Irradiated section 70.3 Example 5 Unirradiated section 45.5 Irradiated section 69.6 Example 6 Unirradiated section 43.7 Irradiated section 71.8 Performed Example 7 Unirradiated part 42.3 Irradiated part 63.1 Example 8 Unirradiated part 41.8 Irradiated part 72.3 Example 9 Unirradiated part 45.1 Irradiated part 65.3 Example 10 Unirradiated part 44.3 Irradiated part 69.5 Since the surface tension was increased by irradiating light, it was considered that a polar group was generated on the surface by light irradiation, and the pre-tilt angle was changed due to improved wettability of the surface.

[0047]

According to the liquid crystal alignment film of the present invention, by irradiating the surface with light, portions having different pretilt angles of liquid crystal molecules can be formed.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yasuhisa Odagawa No. 48, Wadai, Tsukuba, Ibaraki Prefecture Within Hitachi Chemical Co., Ltd.Tsukuba Development Laboratory Co., Ltd. (72) Inventor Yuichi Kanaya 4-3-1-1, Higashicho, Hitachi City, Ibaraki Prefecture Hitachi Chemical Co., Ltd. Ibaraki Research Laboratory (56) References JP-A-63-158526 (JP, A) JP-A-7-36047 (JP, A) JP-A-52-70619 (JP, A) JP-A-63-314714 (JP, A) JP-A-63-266835 (JP, A) A) (58) Field surveyed (Int. Cl. ⁷ , DB name) G02F 1/1337 525 C09K 19/56

Claims (3)

(57) [Claims] 1. A liquid crystal alignment film for aligning liquid crystal molecules used in a liquid crystal display element, wherein the liquid crystal alignment film is provided at a predetermined location on its surface at 1 to 30 J / cm2 output from a low-pressure mercury lamp.
Liquid crystal molecules formed by irradiating light in the range of cm ² have portions with different pretilt angles, and the alignment film is a polymer of a repeating unit represented by the general formula (I).
A liquid crystal alignment film comprising: Embedded image (However, in the general formula (I), A is a tetravalent residue of tetracarboxylic dianhydride except for a cyclobutane ring , and R is a divalent organic group.) 2. A liquid crystal alignment film for aligning liquid crystal molecules used in a liquid crystal display device, wherein the liquid crystal alignment film is provided at a predetermined position on its surface at 1 to 30 J / cm2 output from a low-pressure mercury lamp.
Liquid crystal molecules formed by irradiating light in the range of cm ² have portions with different pretilt angles, and the alignment film is a polymer of a repeating unit represented by the general formula (II).
A liquid crystal alignment film comprising: Embedded image (However, in the general formula (II), A is a tetravalent residue of tetracarboxylic dianhydride excluding a cyclobutane ring , and R is a divalent organic group.) 3. The general formula according to claim 1 or claim 2.
(I) or the repeating unit represented by the general formula (II)
A material for a liquid crystal alignment film containing a limmer .