JP2000319510A - Liquid crystal alignment agent and liquid crystal alignment treatment method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a liquid crystal alignment agent capable of giving a liquid crystal alignment layer having an angle of pre-tilt produced by irradiation of radioactive rays without any rubbing treatment, by compounding plural kinds of compounds selected from a group comprising a specific polyimide, a polymer having a specified structure and a compound having a specified structure. SOLUTION: This liquid crystal alignment agent contains at least two kinds of compounds selected from the group consisting of (A) a polyimide having a structure of the formula: P1-CH=CH-CO-Q1 (P1 and Q1 are each a divalent organic radical having one or more aromatic rings) in the main chain, (B) a polymer having at least one structure selected from a group of structures of the formulae: P2-CH=CH-CO-Q2 (P2 is a divalent organic radical having one or more aromatic rings; Q2 is a monovalent organic radical having one or more aromatic rings) and P3-CH=CH-CO-Q3 (P3 is a trivalent organic radical having one or more aromatic rings; Q3 is a monovalent organic radical having one or more aromatic rings), and (C) a compound having a structure of the formula: P4-CH=CH-CO-Q4 (P4 and Q4 are each a monovalent organic radical having one or more aromatic rings).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a liquid crystal alignment agent and a liquid crystal alignment treatment method. More particularly, the present invention relates to a liquid crystal alignment agent and a liquid crystal alignment processing method capable of imparting a liquid crystal alignment ability having a pretilt angle by irradiating radiation without performing a rubbing treatment.

[0002]

2. Description of the Related Art Conventionally, a nematic liquid crystal having a positive dielectric anisotropy has a sandwich structure with a substrate having a transparent electrode having a liquid crystal alignment film, and a long axis of liquid crystal molecules is continuously twisted by 90 ° or more between the substrates. TN (Twisted Nem
Liquid crystal display devices having an (atic) type or STN (Super Twisted Nematic) type liquid crystal cell are known.

As means for aligning the liquid crystal in the liquid crystal cell, an organic film is formed on the surface of the substrate, and then the surface of the organic film is rubbed in one direction with a cloth material such as rayon to impart the liquid crystal alignment ability ( Rubbing treatment), oblique deposition of silicon oxide on the substrate surface, Langmuir
Although there is a method of forming a monomolecular film having a long-chain alkyl group using the Blodgett method (LB method), the size of a substrate to be processed is restricted, and the uniformity of liquid crystal alignment is insufficient. Industrially, the orientation of liquid crystal by rubbing is advantageous in terms of processing time and processing cost.

However, when the liquid crystal is aligned by a rubbing process, there is a problem that dust or static electricity is easily generated during the process. When static electricity is generated, dust adheres to the surface of the alignment film, causing display defects, and a thin film transistor (TFT).
r) In the case of a substrate having an element, the generated static electricity causes a circuit breakage of the TFT element, which causes a reduction in yield. Furthermore, in a liquid crystal display device that is increasingly sophisticated in the future, the uniformity of the rubbing treatment poses a problem due to the unevenness of the substrate surface accompanying the increase in the density of pixels.

Therefore, in order to solve these problems, a method of performing an orientation treatment without using a rubbing treatment, for example, an organic film such as polyvinyl cinnamate or poly (4′-methacryloyloxy chalcone) formed on the substrate surface is used. It has been studied to impart liquid crystal alignment ability by irradiating linearly polarized ultraviolet rays. However, there is a problem that the sensitivity to polarized ultraviolet light composed of long wavelength light of 320 nm or more, the stability of liquid crystal alignment ability, and the heat resistance are not sufficient. The sensitivity referred to here is the minimum amount of ultraviolet irradiation energy necessary for imparting liquid crystal alignment ability, and it is generally desirable that the minimum necessary amount of ultraviolet energy be small.

The problem of insufficient sensitivity to polarized ultraviolet light is industrially disadvantageous in terms of processing time and processing cost, and the problems of stability of liquid crystal alignment ability and heat resistance significantly deteriorate display quality as a liquid crystal display device. Will be.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to eliminate the need for a rubbing treatment which causes product defects such as display defects and device destruction, and to provide excellent sensitivity, stability of liquid crystal alignment ability, heat resistance, and productivity. Another object of the present invention is to provide a liquid crystal alignment agent used for forming a liquid crystal alignment film which is excellent.

Another object of the present invention is to provide a liquid crystal alignment treatment method comprising irradiating a liquid crystal alignment film obtained from the liquid crystal alignment agent with radiation. Still other objects and advantages of the present invention will become apparent from the following description.

[0009]

According to the present invention, the above objects and advantages of the present invention are as follows: (A) The following formula (I): -P ¹ -CH = CH-CO-Q ^1-. ... (I) wherein P ¹ and Q ¹ are the same or different and are divalent organic groups having an aromatic ring (hereinafter, referred to as specific structure 1) in the main chain. Polyimide (hereinafter,
(Also referred to as “polyimide (A)”), (B) the following formula (II) —P ² —CH ＝ CH—CO—Q ² ( ² ) where P ² is an aromatic ring-containing 2 Wherein Q ² is a monovalent organic group containing an aromatic ring, and a compound represented by the following formula (III): Here, P ³ is a trivalent organic group containing an aromatic ring, and Q ³ is a monovalent organic group containing an aromatic ring, and at least one structure selected from the group consisting of Hereinafter, a polymer having a specific structure 2) (hereinafter, also referred to as “polymer (B)”) and (C) the following general formula (IV): P ⁴ —CH ＝ CH—CO—Q ^4. (IV) Here, P ⁴ and Q ⁴ are the same or different and are a monovalent organic group having an aromatic ring.
This is achieved by a liquid crystal aligning agent characterized by containing at least two kinds selected from the group consisting of compounds having a specific structure 3 (hereinafter also referred to as “compound (C)”).

Secondly, the above objects and advantages of the present invention are achieved by a liquid crystal alignment treatment method comprising irradiating a liquid crystal alignment film obtained from the liquid crystal alignment agent with radiation.

Hereinafter, the present invention will be described in detail. Liquid crystal aligning agent The liquid crystal aligning agent of the present invention comprises: (i) polyimide (A) and polymer (B) (ii) polyimide (A) and compound (C) (iii) polymer (B) and compound (C) (Iv) It contains the polyimide (A) and any one of the polymer (B) and the compound (C).

Further, preferred embodiments of (i), (iii) and (iv) are (i-1) polyimide (A) and polymer (B) having a structure other than polyimide. (Iii-1) polyimide A polymer (B) having a structure;
Polymer (B) and compound (C) having a structure other than polyimide (iv-1) Combinations of polyimide (A) and polymer (B) and compound (C) having a structure other than polyimide can be given. .

First, the embodiment (i) will be described. In the polyimide (A), the specific structure 1 is a structure that is sensitive to radiation. The term “responsive” as used herein means that when irradiated with radiation, the energy level is increased by a photoexcitation reaction, and then energy is released to return to a stable state. In the formula (I), P ¹ and Q ¹ are the same or different and are a divalent organic group having an aromatic ring. The organic group containing an aromatic ring is preferably an organic group having 6 to 20 carbon atoms. These organic groups may contain a halogen atom. Specifically, 1,2
-Phenylene group, 1,3-phenylene group, 1,4-phenylene group, 4,4′-biphenylene group, 4-pentylphenyl group, 4-fluorophenyl group, 3,4-difluorophenyl group, 3,4, 5-trifluorophenyl group, 4-
Octylphenyl group, 4-pentylbiphenyl group, 4-
Octylbiphenyl group, 4-fluorobiphenyl group,
3,4-difluorobiphenyl group, 3,4,5-trifluorobiphenyl group, 4-octyl-1-naphthyl group, 5
-Pentyl-1-naphthyl group, 6-octyl-2-naphthyl group, 9-anthracenyl group, 10-pentyl-9-
And an anthracenyl group.

The polyimide (A) used in the present invention comprises:
It has the specific structure 1 in the main chain, and is obtained by reacting (a) tetracarboxylic dianhydride with (b) a diamine compound, and via an intermediate polyamic acid. Such a polyimide (A) is produced by using the compound having the specific structure 1 in at least one of (a) a tetracarboxylic dianhydride component and (b) a diamine component. In addition, the polyimide (A) includes those having a low imidization ratio in which the polyamic acid is not completely imidized.

Examples of the tetracarboxylic dianhydride having the specific structure 1 include 3,3 ', 4,4'-chalconetetracarboxylic dianhydride, 4,4', 5,5'-chalconetetracarboxylic acid Examples include dianhydride, 3,3 ′, 5,5′-chalconetetracarboxylic dianhydride, 4,4′-dihydroxychalcone bistrimellitate, and 3,4′-dihydroxychalcone bistrimellitate. As the diamine compound having the specific structure 1, for example, 3,
Examples include 3′-diaminochalcone, 4,4′-diaminochalcone, 3,4′-diaminochalcone, and 3 ′, 4-diaminochalcone. These can be used alone or 2
More than one species can be used in combination.

The polyimide (A) used in the present invention can be produced by using another tetracarboxylic dianhydride and / or a diamine compound in such an amount that the effects of the present invention are not impaired.

Other tetracarboxylic dianhydrides include:
For example, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, butanetetracarboxylic dianhydride, 1,2,
3,4-cyclobutanetetracarboxylic dianhydride, 1,3
-Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride Anhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a, 4,5,
9b-Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 5- (2,5-dioxotetrahydrofural)- 3-methyl-3-cyclohexene-1,2
Aliphatic and alicyclic tetracarboxylic dianhydrides such as dicarboxylic dianhydride, bicyclo [2.2.2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride ;

Pyromellitic dianhydride, 3,3 ', 4,
4'-biphenylsulfonetetracarboxylic dianhydride,
1,4,5,8-naphthalenetetracarboxylic dianhydride,
2,3,6,7-naphthalenetetracarboxylic dianhydride,
3,3 ', 4,4'-biphenylethertetracarboxylic dianhydride, 3,3', 4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ', 4,4'-tetra Phenylsilanetetracarboxylic dianhydride, 1,2,
3,4-furantetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfone Dianhydride, 4,4'-
Bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ′, 4,4′-perfluoroisopropylidenetetracarboxylic dianhydride, 3,3 ′, 4,
4'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-
Phenylene-bis (triphenylphthalic acid) dianhydride,
m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid)
And aromatic tetracarboxylic dianhydrides such as -4,4'-diphenylmethane dianhydride.

Of these, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, butanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride 1,2,3,4-cyclobutanetetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8 -Naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylethertetracarboxylic dianhydride are preferred. These can be used alone or in combination of two or more.

As other diamine compounds, for example, p-
Phenylenediamine, m-phenylenediamine, 4,
4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,
3'-dimethyl-4,4'-diaminobiphenyl, 4,
4'-diaminobenzanilide, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 3,3
-Dimethyl-4,4'-diaminobiphenyl, 5-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4'-aminophenyl) -1, 3,3-trimethylindane, 3,4′-diaminodiphenyl ether, 2,2-bis (4-aminophenoxy) propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2- Screw [4-
(4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl)
-10-hydroanthracene, 2,7-diaminofluorene, 9,9-bis (4-aminophenyl) fluorene, 4,4'-methylene-bis (2-chloroaniline), 2,2 ', 5,5'-Tetrachloro-4,4'-diaminobiphenyl,2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl,3,3'-dimethoxy-4,4'-diaminobiphenyl, , 4.4'-
(P-phenyleneisopropylidene) bisaniline,
4,4 '-(m-phenyleneisopropylidene) bisaniline, 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-diamino-2, Aromatic diamines such as 2'-bis (trifluoromethyl) biphenyl, 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl; and heteroatoms such as diaminotetraphenylthiophene An aromatic diamine having;

1,1-methaxylylenediamine, 1,3-
Propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine,
1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine,
Aliphatic and alicyclic diamines such as hexahydro-4,7-methanoindanylene dimethylene diamine, tricyclo [6.2.1.0 ^2,7 ] -undecylene dimethyl diamine, 4,4'-methylene bis (cyclohexylamine) ;
And diaminoorganosiloxanes such as diaminohexamethyldisiloxane.

Of these, p-phenylenediamine,
4,4′-diaminodiphenylmethane, 1,5-diaminonaphthalene, 2,7-diaminofluorene, 4,4′-diaminodiphenylether, 4,4 ′-(p-phenyleneisopropylidene) bisaniline, 2,2-bis [ 4
-(4-Aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl Hexafluoropropane, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl preferable. These can be used alone or in combination of two or more.

The polyimide (A) used in the present invention is obtained by polycondensing the above-mentioned (a) tetracarboxylic dianhydride component and (ii) diamine component to obtain a polyamic acid, and if necessary, a dehydrating agent and It is obtained by heating and imidizing in the presence of an imidization catalyst. The reaction temperature for imidization by heating is usually 60 to 3
00 ° C, preferably 100 to 170 ° C. When the reaction temperature is lower than 60 ° C., the progress of the reaction is delayed, and when it exceeds 300 ° C., the molecular weight of the polyamic acid may be greatly reduced. Further, the reaction for imidization in the presence of a dehydrating agent and an imidization catalyst can be performed in an organic solvent.
The reaction temperature is generally 0 to 180 ° C, preferably 60 to 15 ° C.
0 ° C. Acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used as the dehydrating agent. As the imidation catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, and triethylamine can be used. However, it is not limited to these. The amount of the dehydrating agent used is preferably 1.6 to 20 mol per 1 mol of the repeating unit of the polyamic acid. The amount of the imidization catalyst used is preferably 0.5 to 10 mol per 1 mol of the dehydrating agent used. The content of the amic acid residue in the polyimide can be adjusted by the amount of the imidization catalyst and the dehydrating agent used.

Specific Structure 2 Constituting Liquid Crystal Alignment Agent of the Present Invention
Is a polymer having the specific structure 2, and the skeleton of the polymer is not particularly limited.
Those selected from (1) polyimide, (2) polyester, (3) polyamide, and (4) poly (meth) acrylate are preferred.

The specific structure 2 is sensitive to radiation and is represented by the above formula (II) or the above formula (III). In the formula (II), P ² is a divalent organic group having an aromatic ring, and Q ² is a monovalent organic group having an aromatic ring. Also, the formula (I
In II), P ³ is a trivalent organic group having an aromatic ring, and Q ³ is a monovalent organic group having an aromatic ring. Examples of these organic groups include the same groups and groups having the same skeleton as the organic groups described for the specific structure 1.

The polyimide is obtained by reacting (a) a tetracarboxylic dianhydride with a (b) diamine compound in the same manner as the polyimide (A), and via an intermediate polyamic acid. Such a polyimide is produced by using the compound having the specific structure 2 as at least one of the (a) tetracarboxylic dianhydride component and the (b) diamine component. Further, when the polymer (B) is a polyimide, as in the case of the polyimide (A), those in which the polyamic acid is not completely imidized and which has a low imidization ratio are also included. Examples of the tetracarboxylic dianhydride having the specific structure 2 include 2,2′-bis (4-chalconyloxy) -3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3'-bis (4-chaconyloxy) -4,4 ', 5,5'-biphenyltetracarboxylic dianhydride, 2,2'-bis (4-chaconyloxy)-
4,4 ', 5,5'-biphenyltetracarboxylic dianhydride, 4,4'-bis (4-chalconyloxy) -2,
2 ', 3,3'-biphenyltetracarboxylic dianhydride,
6,6′-bis (4-chalconyloxy) -2,2 ′, 3,
3′-biphenyltetracarboxylic dianhydride, 5,5 ′
-Bis (4-chalconyloxy) -2,2 ', 3,3'-
Biphenyltetracarboxylic dianhydride, 2,2'-bis (4-chalconyloxy) -3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride, 3,3'-bis (4-chalcone Nyloxy) -4,4 ′, 5,5′-diphenylethertetracarboxylic dianhydride, 2,2′-
Bis (4-chalconyloxy) -4,4 ', 5,5'-diphenylethertetracarboxylic dianhydride, 4,4'
-Bis (4-chalconyloxy) -2,2 ', 3,3'-
Diphenyl ether tetracarboxylic dianhydride, 6,
6'-bis (4-chalconyloxy) -2,2 ', 3,
3′-diphenyl ether tetracarboxylic dianhydride,
5,5'-bis (4-chalconyloxy) -2,2 ', 3,
3'-diphenyl ether tetracarboxylic dianhydride and the like. Examples of the diamine compound having the specific structure 2 include 2,3-diaminochalcone, 2,4-diaminochalcone, 3,4-diaminochalcone, 3,5-diaminochalcone, and 4- (2,4-diaminophenoxy).
Examples include chalcone, 4- (3,5-diaminophenoxy) chalcone, and a compound represented by the following formula (V).

[0027]

Embedded image

The polyester is obtained by reacting (c) a dicarboxylic acid (dicarboxylic acid, dicarboxylic acid ester or dicarboxylic acid halide) with (d) a diol compound. Such a polyester is produced by using a compound having the specific structure 2 as at least one component of (c) a dicarboxylic acid and (d) a diol compound.

The dicarboxylic acids having the specific structure 2 include, for example, 2,3-chalcone dicarboxylic acid, 2,4-chalcone dicarboxylic acid, 3,4-chalcone dicarboxylic acid,
3,4-chalcone dicarboxylic acid, 3,5-chalcone dicarboxylic acid, 1- (4-chalconyloxy) -2,4-benzenedicarboxylic acid, 1- (4-chalconyloxy)-
2,5-benzenedicarboxylic acid, 1- (4-chalconyloxy) -2,6-benzenedicarboxylic acid and 1-
Examples thereof include ester compounds such as alkyl esters of (4-chalconyloxy) -3,5-benzenedicarboxylic acid, and carboxylic acid halides such as carboxylic acid chloride. Examples of the diol compound having the specific structure 2 include 2,3-dihydroxychalcone, 2,4-dihydroxychalcone, 3,4-dihydroxychalcone,
3,4-dihydroxychalcone, 3,5-dihydroxychalcone, 1- (4-chalconyloxy) -2,4-benzenediol, 1- (4-chalconyloxy) -2,5
-Benzenediol, 1- (4-chalconyloxy)-
Examples include 2,6-benzenediol and 1- (4-chalconyloxy) -3,5-benzenediol. Of these, 1- (4-chalconyloxy)-
3,5-benzenedicarboxylic acid and 1- (4-chalconyloxy) -3,5-benzenediol are preferred.
These can be used alone or in combination of two or more.

The above polyester can be produced by using other dicarboxylic acids and / or diol compounds in such an amount that the effects of the present invention are not impaired.

Other dicarboxylic acid compounds include, for example, oxalic acid, malonic acid, difluoromalonic acid, alkylmalonic acid, succinic acid, tetrafluorosuccinic acid, alkylsuccinic acid, (±) -malic acid, meso-tartaric acid, itacone Acid, maleic acid, methyl maleic acid, fumaric acid,
Methyl fumaric acid, acetylenedicarboxylic acid, glutaric acid, hexafluoroglutaric acid, methyl glutaric acid, glutaconic acid, adipic acid, dithioadipic acid, methyl adipic acid, dimethyl adipic acid, tetramethyl adipic acid, methylene adipic acid, muconic acid, galactal Acid, pimelic acid, suberic acid, perfluorosuberic acid, 3,
Aliphatic carboxylic acids such as 3,6,6-tetramethylsuberic acid, azelaic acid, sebacic acid, perfluorosebacic acid, brassic acid, dodecyldicarboxylic acid, tridecyldicarboxylic acid and tetradecyldicarboxylic acid;

Cycloalkyldicarboxylic acid, adipic acid, hexahydrophthalic acid, 1,4- (norbornene)
Alicyclic carboxylic acids such as dicarboxylic acid, bicycloalkyldicarboxylic acid, adamantanedicarboxylic acid, spiroheptanedicarboxylic acid;

Phthalic acid, isophthalic acid, dithioisophthalic acid, methyl isophthalic acid, dimethyl isophthalic acid, chloroisophthalic acid, dichloroisophthalic acid, terephthalic acid, methyl terephthalic acid, dimethyl terephthalic acid, chloroterephthalic acid, bromoterephthalic acid, naphthalene dicarboxylic acid Acid, oxo fluorenedicarboxylic acid, anthracene dicarboxylic acid, biphenyl dicarboxylic acid, biphenylenedicarboxylic acid, dimethyl biphenylenedicarboxylic acid,
4,4 ″ -p-terephenylenedicarboxylic acid, 4,
4 '''-p-quaterylphenyldicarboxylic acid, bibenzyldicarboxylic acid, azobenzenedicarboxylic acid, homophthalic acid, phenylenediacetic acid, phenylenedipropionic acid, naphthalenedicarboxylic acid, naphthalenedipropionic acid, biphenyldiacetic acid, biphenyldipropion acid,
3,3 ′-[4,4 ′-(methylenedi-p-biphenylene) dipropionic acid, 4,4′-bibenzyldiacetic acid,
Examples include aromatic dicarboxylic acids such as 3 ′-(4,4′-bibenzyl) dipropionic acid and oxydi-p-phenylene diacetate, and ester compounds such as alkyl esters thereof, and carboxylic acid halides such as carboxylic acid chloride. . These can be used alone or in combination of two or more.

Other diol compounds include, for example, polyphenols such as catechol, alkyl catechol and hydroquinone; methylene bisphenol, isopropylidene bisphenol, butylidene bisphenol, thiobisphenol, sulfinyl bisphenol, sulfonylun bisphenol, oxybisphenol and the like. Bisphenols. These can be used alone or in combination of two or more.

Such a polyester is obtained by heating and polycondensing the above-mentioned (c) dicarboxylic acid component and (d) diol compound component in the presence of a catalyst, if necessary. In the case of polycondensation between a dicarboxylic acid and a diol compound, as a catalyst, a protic acid such as sulfuric acid or p-toluenesulfonic acid, an oxide or salt of a heavy metal, or an organic metal compound such as titanium, tin, or lead is used. In the case of a reaction between a dicarboxylic acid ester and a diol compound, lead,
Acetate and carbonate compounds such as zinc, manganese, calcium, cobalt, and cadmium, metallic magnesium, zinc,
An oxide such as lead, antimony, or germanium is used. In the case of a reaction between a dicarboxylic acid halide and a diol compound, a basic catalyst such as pyridine or triethylamine is used as a catalyst.

The polyamide is obtained by reacting (e) dicarboxylic acids (dicarboxylic acid, dicarboxylic acid ester, dicarboxylic acid halide) with (f) a diamine compound. Such a polyamide is produced by using a compound having the specific structure 2 as at least one of the (e) dicarboxylic acid component and the (f) diamine compound component.

As the dicarboxylic acids having the specific structure 2, the above-mentioned dicarboxylic acids (c) are used. Examples of the diamine compound having the specific structure 2 include a compound represented by the following formula (V) in addition to the diamine compound (b) described above.

[0038]

Embedded image Wherein A ¹ and A ² represent a divalent aromatic group and n
Represents an integer of 1 to 10. )

Of these, compounds represented by the above formula (V) are preferred. In the formula (V), the alkyl group represented by C _n H _{2n + 1-} may be linear or branched, and a linear one is more preferable. Examples of the divalent aromatic group represented by A ¹ and A ² include a phenylene group, a biphenylene group, a naphthylene group, a binaphthylene group,
Hydrogen atoms from polycyclic aromatic compounds such as pyrene, chrysene, and naphthacene;
And organic groups excluding individual groups. Specific examples of the compound represented by the above formula (V) include 4-isopropyl-
4 ′ (3,5-diaminophenoxy) chalcone, 4-amyl-4 ′ (3,5-diaminophenoxy) chalcone,
4-pentyl-4 '(3,5-diaminophenoxy) chalcone, 4-octyl-4' (3,5-diaminophenoxy) chalcone, 4-pentyl-2-methyl-4 '
(2,4-diaminophenoxy) chalcone, 4-pentyl-2,5dimethyl-4 ′ (3,5-diaminophenoxy) chalcone, 4-octyl-2-methyl-4 ′ (3,
5-diaminophenoxy) chalcone, 4-pentyl-
4 '(2,4-diaminophenoxy) chalcone, 4-octyl-4' (2,4-diaminophenoxy) chalcone, 4-pentyl-4 '(3,5-diaminobenzoyloxy) chalcone, 4-octyl- 4 '(3,5-diaminobenzoyloxy) chalcone, 4-pentyl-3'
(2,4-diaminobenzoyloxy) chalcone, 4-octyl-3 ′ (2,4-diaminobenzoyloxy) chalcone and the like, among which 4-pentyl-4 ′ (3,
5-diaminophenoxy) chalcone, 4-octyl-
4 '(3,5-diaminophenoxy) chalcone is particularly preferred. These can be used alone or in combination of two or more.

Such a polyamide may be used in combination with other dicarboxylic acid compounds and diamine compounds to such an extent that the effects of the present invention are not impaired. As the other dicarboxylic acid compounds and diamine compounds, the above-mentioned other dicarboxylic acid compounds and diamine compounds are used. These can be used alone or in combination of two or more.

Such a polyamide can be obtained by combining the above-mentioned (e) dicarboxylic acid component and (f) diamine component, if necessary.
It is obtained by polycondensation in the presence of an acidic catalyst such as paratoluenesulfonic acid, sulfuric acid, hydrochloric acid and the like.

The poly (meth) acrylate is (g)
It is obtained by polymerizing a (meth) acrylate compound. As such a poly (meth) acrylate, a compound having a specific structure 2 is used as the (g) (meth) acrylate compound.

Examples of the (meth) acrylate compound having the specific structure 2 include 4- (meth) acryloyloxychalcone, 4- (meth) acryloyloxy-4'-phenylchalcone, and 4- (meth) acryloyloxy-4'-pentyl. Chalcone, 4- (meth) acryloyloxy-4'-
(4-pentylphenyl) chalcone and the like.
These can be used alone or in combination of two or more.

The poly (meth) acrylate used in the present invention can be produced in combination with other (meth) acrylate compounds to such an extent that the effects of the present invention are not impaired. Other (meth) acrylate compounds include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy Aliphatic (meth) acrylate compounds such as propyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, and trimethylolpropane tri (meth) acrylate; tetrahydrofurfuryl (meth) acrylate, cyclohexyl ( (Meth) acrylate, glycidyl (meth) acrylate, dicyclopentadiene (meth) acrylate, dicyclopentanyl (meth) acrylate, tricyclodecanyl (meth) acrylate, isobornyl Meth) cycloaliphatic, such as acrylates (meth) acrylate; benzyl (meth)
Aromatic (meth) acrylate compounds such as acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, and tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate are exemplified. These can be used alone or in combination of two or more.

The poly (meth) acrylate can be obtained by converting the above (g) (meth) acrylate compound, if necessary,
It is obtained by polymerization in the presence of a catalyst such as an azo compound such as azobisisobutyronitrile and a peroxide such as benzoyl peroxide.

Next, the embodiment (ii) will be described.
As the polyimide (A), the same polyimide as described above can be used. Compound (C) has the general formula
It is a compound having a structure sensitive to radiation represented by (IV). In the formula (IV), P ⁴ and Q ⁴ are organic groups containing an aromatic ring, and preferably are organic groups having 6 to 20 carbon atoms. These organic groups may contain a halogen atom. Specifically, a phenyl group, a 4,4′-biphenylene group, a 4-pentylphenyl group, a 4-fluorophenyl group, a 3,4-difluorophenyl group, a 3,4,5-trifluorophenyl group, a 4-octyl Phenyl group, 4-pentylbiphenyl group, 4-octylbiphenyl group, 4-
Fluorobiphenyl group, 3,4-difluorobiphenyl group, 3,4,5-trifluorobiphenyl group, 4-octyl-1-naphthyl group, 5-pentyl-1-naphthyl group,
A 6-octyl-2-naphthyl group, a 9-anthracenyl group, a 10-pentyl-9-anthracenyl group and the like. These may be the same or different from each other.

Finally, the embodiments (iii) and (iv) will be understood from the description of the embodiments (i) and (ii). In the present invention, the mixing ratio of the polyimide (A), the polymer (B) and the compound (C) is such that when the polyimide (A) is used, the polyimide (A) is mixed with the polymer (B) and / or the compound (C). ) Is preferably 1: 0.8 to 0.001, more preferably 1: 0.3 to 0.01. When the polyimide (A) is not used, the mixing weight ratio of the polymer (B) to the compound (C) is preferably 1: 0.8 to 0.001, more preferably 1: 0.3. ~ 0.01.

Solvent The liquid crystal aligning agent of the present invention comprises a solution of the composition containing the above-mentioned radiation-sensitive organic compound. The solvent used at this time is not particularly limited as long as it is an organic solvent capable of dissolving the composition, and can be used alone or in combination of two or more solvents.

Other Additives The liquid crystal aligning agent of the present invention may contain various thermosetting crosslinking agents for stabilizing the pretilt angle and increasing the strength of the coating film. As the thermosetting crosslinking agent, a polyfunctional epoxy-containing compound is effective, and bisphenol A type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, cycloaliphatic epoxy resin, glycidyl ester epoxy resin, glycidyl diamine A series epoxy resin, a heterocyclic epoxy resin, an epoxy group-containing acrylic resin and the like can be used. Commercial products include, for example, Epolite 400E and Epolite 3002 (manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.), Epikote 828, and 152.
Epoxy novolak 180S (manufactured by Yuka Shell Epoxy Co., Ltd.) and the like can be mentioned. Furthermore, when using the above-mentioned polyfunctional epoxy-containing compound, a base catalyst such as 1-benzyl-2-methylimidazole can be added for the purpose of efficiently causing a crosslinking reaction.

Further, the liquid crystal aligning agent of the present invention may contain a functional silane-containing compound for the purpose of improving the adhesion to the substrate. As the functional silane-containing compound,
For example, 3-aminopropyltrimethoxysilane, 3-aminopropyl
Aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl)-
3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-
Aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-
Triethoxysilylpropyltriethylenetriamine,
N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxyisyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-dia Zanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-amino Propyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-
Bis (oxyethylene) -3-aminopropyltriethoxysilane and the like can be mentioned. Furthermore, Japanese Unexamined Patent Publication No.
A reaction product of a tetracarboxylic dianhydride and an amino group-containing silane compound described in JP-A-3-291922 can also be used.

[0051] As a method for forming a liquid crystal alignment film using the liquid crystal aligning agent of the liquid crystal alignment film present invention include, for example, the following method. First, the liquid crystal aligning agent of the present invention is applied to the transparent conductive film side of the substrate provided with the transparent conductive film by a roll coater method, a spinner method, a printing method or the like, and heated at a temperature of 40 to 200 ° C. to form a coating film. Is formed. The thickness of the coating film is usually 0.001 to 1 μm, preferably 0.005 to 0.5 μm. As the substrate, for example, float glass, glass such as soda glass,
A transparent substrate made of a plastic film such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, or polycarbonate can be used. The transparent conductive film is made of N ₂ made of SnO _2.
ESA film, can be used In ₂ O ₃ -SnO ₂ made of an ITO film or the like, the patterning of the transparent conductive film, photo-etching method, a method of using a pre-mask is used. In applying the liquid crystal aligning agent, a functional silane-containing compound, titanate, or the like may be applied on the substrate and the transparent conductive film in advance to further improve the adhesion between the substrate and the transparent conductive film. it can.

Next, the coating film is irradiated with radiation, and in some cases, is further subjected to a heat treatment at a temperature of 150 to 250 ° C. to provide a liquid crystal alignment ability having a pretilt angle. The radiation used may be polarized or unpolarized, UV and visible light having a wavelength between 150 nm and 800 nm may be used, but 320 nm
Ultraviolet light having a wavelength of -450 nm is particularly preferred. Examples of the light source include a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, and an excimer laser.

The ultraviolet light in the above preferred wavelength range can be obtained by using a filter, a diffraction grating, or the like in combination with the light source. For convenience, a polarizing plate having a wavelength shorter than 320 nm, such as a polarizing plate made of Pyrex glass, is used. A material that does not transmit ultraviolet light may be used together with the light source. Irradiation of ultraviolet light having a polarization component to the liquid crystal alignment film can be achieved by passing a light beam emitted from the light source through a polarizing plate or a polarizer disposed between the liquid crystal alignment film and the light source. Even if unpolarized ultraviolet light is irradiated obliquely instead of polarized light, the same effect as when polarized light is irradiated can be obtained. Non-polarized ultraviolet light obliquely applied to the object shows a relatively high reflectance. This reflectivity differs depending on the polarization component. Generally, it has the property that the reflectance of the s component, which is a polarization component perpendicular to the incident surface, is higher than the p component, which is a polarization component in the light incident surface. This means that the p component, which is a polarization component having a low reflectance, is selectively incident on the object.

The liquid crystal alignment film is irradiated with the ultraviolet light having the polarization component a plurality of times by changing the direction of the polarization axis of the ultraviolet light having the polarization component, the angle of the ultraviolet light having the polarization component, and the irradiation intensity. By doing so, it is possible to control the orientation direction and pretilt angle of the liquid crystal molecules.

Liquid crystal display device A liquid crystal display device formed by using the liquid crystal alignment agent of the present invention is characterized in that the two substrates on which the liquid crystal alignment film is formed are formed by irradiating the two substrates with the azimuthal direction of the alignment direction given by the irradiation of ultraviolet rays. Are set to have a predetermined angle via a gap (cell gap), a peripheral portion between the substrates is sealed with a sealant, liquid crystal is filled, and the filling hole is sealed to form a liquid crystal cell. . Then, a polarizing plate is attached to both surfaces of the polarizing plate such that the polarizing direction of the polarizing plate forms a predetermined angle with the azimuthal direction of the orientation direction of the substrate, thereby obtaining a liquid crystal display device. By adjusting the azimuthal direction of the alignment direction and the angle between each substrate and the polarizing plate in the two substrates on which the liquid crystal alignment film is formed, a liquid crystal display device having a TN type or STN type liquid crystal cell can be arbitrarily set. Obtainable. As the sealant, for example, an epoxy resin containing a hardening agent and aluminum oxide spheres as a spacer can be used.

As the liquid crystal, a nematic liquid crystal,
A smectic liquid crystal or the like can be used. TN
In the case of a liquid crystal cell, a liquid crystal cell that forms a nematic liquid crystal is preferable. Liquid crystals, dioxane-based liquid crystals, bicyclooctane-based liquid crystals, cubane-based liquid crystals, and the like are used. In the case of an STN type liquid crystal cell, the liquid crystal may be a cholesteric liquid crystal such as cholesteryl chloride, cholesteryl nonaate or cholesteryl carbonate, or a chiral agent sold under the trade names C-15 and CB-15 (manufactured by Merck). Etc. can be further added for use. Furthermore, ferroelectric liquid crystals such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate can be used. As a polarizing plate used outside the liquid crystal cell, a polarizing plate in which a polarizing film called an H film absorbing iodine is sandwiched by a cellulose acetate protective film while stretching and aligning polyvinyl alcohol, or a polarizing film composed of the H film itself. Plates and the like can be mentioned.

If a liquid crystal alignment film is formed by the above method using the liquid crystal alignment agent and liquid crystal alignment treatment method of the present invention, rubbing treatment which causes a product defect such as display defect or device destruction is unnecessary, and sensitivity, liquid crystal alignment A liquid crystal alignment film having excellent stability and heat resistance can be formed with high yield.

[0058]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

Synthesis Example 1 (Synthesis of Polyimide (A)) Polymerization of Polyamic Acid 0.1 mol (22.4 g) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride and 3 ′, 4-diaminochalcone 0.1 mol. One mole (23.8 g) was dissolved in 400 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours. The reaction mixture was then poured into a large excess of methanol, causing the reaction product to precipitate. Thereafter, the resultant was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain 65 g of a polyamic acid. Imidation reaction N-methyl-2- was added to 15.0 g of the obtained polyamic acid.
300 g of pyrrolidone, 8.2 g of pyridine and 9.
6 g was added, and an imidization reaction was performed at 120 ° C. for 4 hours. The reaction mixture was then poured into a large excess of methanol,
The reaction product precipitated. Thereafter, the resultant was washed with methanol and dried under reduced pressure for 15 hours to obtain a polyimide (A) (hereinafter, referred to as polyimide (A)).
11.5 g of "polymer (A-1)" was obtained.

Synthesis Example 2 (Synthesis of polymer (B)) Polymerization of polyamic acid 0.1 mol (22.4 g) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 0.1 mol of p-phenylenediamine
0.05 mol (5.4 g) and 0.05 mol (16.5 g) of 4- (3,5-diaminophenoxy) chalcone were dissolved in 350 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours. The reaction mixture was then poured into a large excess of methanol, causing the reaction product to precipitate. Thereafter, it was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain 43 g of a polymer (B) (hereinafter, referred to as “polymer (B-1)”).
I got

Synthesis Example 3 (Synthesis of polymer (B)) Synthesis of polymethacrylate 2.5 g of 4-methacryloyloxychalcone and 20 mg of azobisisobutyronitrile were added to 7.5 ml of diglyme.
And reacted at 60 ° C. for 10 hours under a nitrogen atmosphere. The viscous reaction mixture is poured into methanol to precipitate the polymer,
The polymer (B) (hereinafter referred to as “polymer (B-
2.5 g).

Synthesis Example 4 (Synthesis of Compound (C)) 10.0 g of 4-hydroxychalcone and sodium acetate 1
0 g was stirred in 100 ml of acetic anhydride at room temperature for 3 hours. The reaction solution was poured into water, and the precipitate was separated by filtration, washed with water, and dried under vacuum to obtain 9.6 g of compound (C) (hereinafter, referred to as "compound (C-1)").

Comparative Synthesis Example 1 Polymerization of Polyamic Acid 22.42 g of 2,3,5-tricarboxycyclopentylacetic acid dianhydride and 10.81 g of p-phenylenediamine were added to N
-Methyl-2-pyrrolidone dissolved in 300 g, 60 ° C
For 6 hours. The reaction mixture was then poured into a large excess of methanol, causing the reaction product to precipitate. Thereafter, the resultant was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain a polyamic acid (27.44 g). Imidation reaction N-methyl-2 was added to 20.00 g of the obtained polyamic acid.
-380 g of pyrrolidone, 9.52 g of pyridine and 12.29 g of acetic anhydride were added, and an imidization reaction was performed at 120 ° C for 4 hours. The reaction mixture was then poured into a large excess of methanol, causing the reaction product to precipitate. Thereafter, it was washed with methanol and dried under reduced pressure for 15 hours to obtain 15.27 g of a comparative polyimide (hereinafter, referred to as “polymer (a-1)”).

Reference Example 1 The polymer (A-1) obtained in Synthesis Example 1 was dissolved in γ-butyrolactone to obtain a solution having a solid concentration of 4% by weight, and this solution was filtered through a filter having a pore size of 1 μm. A liquid crystal aligning agent was prepared. This solution was applied on a transparent electrode surface using a spinner on a glass substrate with a transparent electrode made of an ITO film so as to have a thickness of 0.1 μm, and dried at 180 ° C. for 1 hour to form a thin film. A rubbing machine having a roll around which a nylon cloth is wound,
Roll rotation speed 500rpm, stage moving speed 1c
Rubbing was performed at m / sec. Next, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 17 μm is screen-printed and applied to each outer edge of the pair of rubbed substrates having the liquid crystal alignment film, and then the pair of substrates face each other. As described above, the rubbing directions were overlapped with each other so as to be antiparallel, and the pressure was applied to cure the adhesive. Next, a nematic liquid crystal (ZLI-1565, manufactured by Merck) is filled between the pair of substrates from the liquid crystal inlet, and the liquid crystal inlet is sealed with an epoxy-based adhesive. Were bonded so that the polarization direction of the polarizing plate coincided with the rubbing direction of the liquid crystal alignment film of each substrate, to produce a liquid crystal display device.

Example 1 The polymer (A-1) obtained in Synthesis Example 1 and the polymer (B-2) obtained in Synthesis Example 3 were mixed at a weight mixing ratio of (B-2) /
Comparative Example 1 after mixing so that (A-1) = 0.1
A thin film was formed on a substrate in the same manner as described above. Next, the surface of the thin film formed on the substrate surface was irradiated with ultraviolet rays. In the ultraviolet irradiation of Example 1, a Hg-Xe lamp was used as a light source, and a visible ultraviolet polarizing filter SPF-50C-32 (manufactured by Sigma Koki) was used to convert linearly polarized light having a wavelength of 365 nm as a main component and a wavelength shorter than 320 nm. 0.2 from the normal direction of the substrate
J / cm ^{2 was} irradiated. A liquid crystal display device was manufactured in the same manner as in Comparative Example 1, except that the direction in which the liquid crystal alignment films were superposed was not the rubbing direction but the azimuthal direction of the alignment direction given by ultraviolet irradiation.

Example 2 In place of the polymer (B-2) used in Example 1, Synthesis Example 2
A liquid crystal display device was produced in the same manner as in Example 1 except that the polymer (B-1) obtained in was used.

Example 3 Synthesis Example 4 in place of the polymer (B-2) used in Example 1
A liquid crystal display device was produced in the same manner as in Example 1, except that the compound (C-1) obtained in was used.

Example 4 A liquid crystal display device was manufactured in the same manner as in Example 1 except that the irradiated ultraviolet energy was 0.5 J / cm ² . Next, the manufactured liquid crystal display element was heated in a clean oven at 150 ° C. for 30 minutes, and then cooled to room temperature.

Example 5 A thin film was formed on a substrate in the same manner as in Example 1, and two irradiations of ultraviolet light (first irradiation and second irradiation) were performed. In the first irradiation, non-polarized ultraviolet light excluding a wavelength component shorter than 320 nm from the normal direction of the substrate was irradiated. The unpolarized ultraviolet light excluding the wavelength component shorter than 320 nm was obtained by disposing a short wavelength cut filter between the light source and the substrate. The irradiation energy of the first irradiation was 0.2 J / cm ² . Next, the second irradiation was performed in the same manner as in the ultraviolet irradiation performed in Example 1, and a liquid crystal display element was manufactured in the same manner as in Example 1. The manufactured liquid crystal display element was heated in a clean oven at 150 ° C. for 30 minutes, and then cooled to room temperature.

Example 6 A liquid crystal display device was manufactured in the same manner as in Example 5 except that the order of the first irradiation and the second irradiation in Example 5 was changed.
Heating and cooling were performed.

Example 7 After forming a thin film on a substrate in the same manner as in Example 1,
UV irradiation was performed twice. The positional relationship between the irradiation light and the substrate will be described using xyz coordinates as shown in FIG. As shown in FIG. 1, the incident position of the ultraviolet rays is set as the origin, the substrate surface is defined as the xy plane, and the normal direction of the substrate is defined as the z axis. In the figure, only one incident light beam is shown,
The entire film on the substrate is irradiated. At a position on each substrate, the positional relationship between the first irradiation light and the second irradiation light indicates the positional relationship described below.

As shown in FIG. 1, the first irradiation light a is a linearly polarized light having a polarization direction aα in the y-axis direction. The first irradiation light a was applied to the thin film 2 on the substrate 1 by 0.5 J / cm ² from the normal direction, that is, the z-axis direction.

Next, as shown in FIG. 2, the second irradiation light b was irradiated to the two surfaces of the thin film at an incident angle θ = 60 degrees and 0.1 J / cm ² . Here, the angle of incidence refers to the angle between the optical axis and the normal to the substrate. The second irradiation light b has a polarization direction bβ in an xz plane orthogonal to the polarization direction of the first irradiation light. The incident surface of the second irradiation light is also on the xz plane orthogonal to the polarization direction of the first irradiation light.

A liquid crystal display device was manufactured in the same manner as in Comparative Example 1, except that the direction in which the liquid crystal alignment films were overlapped was not the rubbing direction but the azimuthal direction of the alignment direction given by the irradiation of ultraviolet rays.

The liquid crystal alignment of the liquid crystal display devices obtained in Reference Example 1 and Examples 1 to 7 was good. Voltage 5
When V was applied, a change in brightness of the liquid crystal display element was observed in response to ON / OFF of the applied voltage.

The liquid crystal molecules in the liquid crystal display devices obtained in Reference Example 1 and Example 7 can be given an alignment having a uniform pretilt angle over the entire cell as shown in FIG. Was.

[0077]

According to the method for forming a liquid crystal alignment film using the liquid crystal alignment agent of the present invention, the adhesion of dust due to static electricity generated during the conventional rubbing treatment, the destruction of the TFT element circuit, and the liquid crystal alignment method do not occur. A liquid crystal alignment film having excellent alignment stability and heat resistance can be formed with a high yield. Further, the liquid crystal alignment film formed using the liquid crystal alignment agent of the present invention was used for display of TN type, STN type, etc. because the alignment control having a pretilt angle was easy and the in-plane uniformity was excellent. In such a case, a liquid crystal display element having a high display quality is obtained, and can be effectively used for various devices.For example, a desk calculator, a wristwatch, a clock, a coefficient display plate, a word processor, a personal computer, and a display device such as a liquid crystal television are suitably used. Can be

[Brief description of the drawings]

FIG. 1 is a schematic perspective view showing light irradiation conditions in an example.

FIG. 2 is a schematic perspective view showing light irradiation conditions in an example.

FIG. 3 is a cross-sectional view of the liquid crystal display device showing that liquid crystal molecules are uniformly aligned with a pretilt angle in the liquid crystal display device.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Minoru Makita 2-11-24 Tsukiji, Chuo-ku, Tokyo Inside JSR Co., Ltd. (72) Inventor Masayuki Kimura 2-11-11 Tsukiji 2-chome, Chuo-ku, Tokyo JSR Inside (72) Inventor Nobuo Bessho 2--11-24 Tsukiji, Chuo-ku, Tokyo Inside JSR Co., Ltd. (72) Inventor Shinichi Kimura 2-11-11 Tsukiji 2-chome, Chuo-ku, Tokyo Inside JSR Co., Ltd. 72) Inventor Yasumasa Takeuchi 2--11-24 Tsukiji, Chuo-ku, Tokyo FSR in JSR Co., Ltd.

Claims (2)

[Claims] (A) The following formula (I): -P ¹ -CH = CH-CO-Q ^1- (I) wherein P ¹ and Q ¹ are the same or different and each has an aromatic ring. polyimide having a divalent organic group having, in the structure represented by the main chain, (B) the following formula ^{(II) -P 2 -CH = CH} -CO-Q 2 ····· (II) wherein Wherein P ² is a divalent organic group containing an aromatic ring and Q ² is a monovalent organic group containing an aromatic ring, and a compound represented by the following formula (III): Here, P ³ is a trivalent organic group containing an aromatic ring, and Q ³ is a monovalent organic group containing an aromatic ring, wherein at least one structure selected from the group consisting of Having (C) the following general formula (IV) P ⁴
—CH ＝ CH—CO—Q ⁴ ... (IV) wherein P ⁴ and Q ⁴ are the same or different and are monovalent organic groups having an aromatic ring. A liquid crystal aligning agent comprising at least two members selected from the group consisting of: 2. A liquid crystal alignment treatment method comprising irradiating a liquid crystal alignment film obtained from the liquid crystal alignment agent according to claim 1 with radiation.