JPH09304777A - Liquid crystal orienting agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain excellent orienting property for a liquid crystal by incorporating a polymer obtd. by the reaction of each specified tetracarboxylic acid dianhydride, a diamine compd. and a hydroxyl compd., and a specified imidized polymer. SOLUTION: This agent contains a polymer (A) obtd. by the reaction of a tetracarboxylic acid dianhydride expressed by formula, a diamine compd. expressed by H2 N-R<2> -NH2 , and a hydroxyl group-contg. compd. expressed by HO-R<3> -OH or HO-R<4> -NH2 , and at least one kind of polymer selected from imidized polymers (B) having a structure obtd. by dehydration and ring-closing reaction of the polymer (A). In formula, R<1> is a quadrivalent org. group and R<2> to R<4> are bivalent org. groups. Thereby, even when the calculation temp. is low to form a resin film, the obtd. orienting film for a liquid crystal has enough orienting performance for liquid crystal molecules and shows excellent orienting property for a liquid crystal.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a liquid crystal aligning agent for forming a liquid crystal aligning film of a liquid crystal display device. More specifically, the present invention relates to a liquid crystal aligning agent that has a good liquid crystal aligning property and can form a liquid crystal aligning film that exhibits a high pretilt angle even by low temperature firing.

[0002]

2. Description of the Related Art At present, as a liquid crystal display element, a liquid crystal alignment film is formed on the surface of a substrate on which a transparent conductive film is provided to form a substrate for a liquid crystal display element. A nematic liquid crystal layer having a positive dielectric anisotropy is formed in the gap to form a sandwich cell, and the major axis of the liquid crystal molecules is continuously twisted 90 degrees from one substrate toward the other substrate. The so-called TN (Tw
TN having isted Nematic type liquid crystal cell
2. Description of the Related Art Liquid crystal display elements are known. The liquid crystal alignment in the TN type liquid crystal display element or the like is usually exhibited by the liquid crystal alignment film formed by subjecting the surface of the resin film formed on the substrate to an alignment treatment such as a rubbing treatment. Here, as the resin forming the resin film,
Polyimide, polyamide, polyester, etc. are known, and among these resins, polyimide is particularly excellent in heat resistance, affinity with liquid crystals, mechanical strength, etc. It is widely used as a material.

[0003]

However, when a conventional liquid crystal aligning agent containing polyimide or the like is coated on a substrate and the coating film is baked under a low temperature condition of about 150 to 170 ° C. to form a resin film. In this case, a liquid crystal alignment film having a good liquid crystal alignment property cannot be obtained even if the surface of the resin film to be formed is subjected to an alignment treatment, and a substrate on which such a liquid crystal alignment film is formed is mounted. There is a problem that a display defect occurs in the liquid crystal display element. In addition, a liquid crystal alignment film obtained by baking a coating film using a conventional liquid crystal alignment agent under low temperature conditions cannot exhibit a high pretilt angle (for example, 3 ° or more), and thus has a high brightness of a recent liquid crystal display device. It cannot fully meet the demand for higher resolution and higher definition.
The present invention has been made to solve the above technical problems.

The first object of the present invention is to ensure that the alignment ability of liquid crystal molecules is imparted by the alignment treatment of the resin film even when the firing temperature for forming the resin film is low. A liquid crystal aligning agent capable of forming a liquid crystal aligning film and exhibiting excellent liquid crystal aligning property in a liquid crystal display device including the liquid crystal aligning film. A second object of the present invention is to form a liquid crystal alignment film that exhibits a high pretilt angle by aligning the resin film even when the baking temperature when forming the resin film is low. It is to provide a liquid crystal aligning agent that can be used.

[0005]

Means for Solving the Problems The liquid crystal aligning agent of the present invention comprises:
Tetracarboxylic dianhydride represented by the following formula (1),
A polymer obtained by reacting a diamine compound represented by the following formula (2) with a hydroxyl group-containing compound represented by the following formula (3) or the following formula (4) [hereinafter "polymer (A)" Also referred to as], and at least one polymer selected from imidized polymers having a structure obtained by subjecting the polymer to dehydration ring closure [hereinafter, also referred to as “polymer (B)”]. To do.

[0006]

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[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. <Tetracarboxylic acid dianhydride> Examples of the tetracarboxylic acid dianhydride used in the synthesis reaction of the polymer (A) include butanetetracarboxylic acid dianhydride and 1,2,3,4-cyclobutanetetracarboxylic acid. Dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1, 2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5
-Cyclohexanetetracarboxylic dianhydride, 3,
3 ', 4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3 , 4,5-Tetrahydrofuran tetracarboxylic acid dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, bicyclo [2.
2,2] -Oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydrides or other aliphatic or cycloaliphatic tetracarboxylic acid dianhydrides;

Pyromellitic dianhydride, 3,3 ', 4
4'-benzophenone tetracarboxylic 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'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) ) Diphenyl sulfide dianhydride, 4,4 '
-Bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,
3 ', 4,4'-perfluoroisopropylidene diphthalic 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 (tri Phenylphthalic acid) -4,4′-diphenylmethane dianhydride, ethylene glycol-bis (anhydrotrimellitate), propylene glycol-bis (anhydrotrimellitate), 1,4-butanediol-bis (anhydrotrimeritate) Trimellitate), 1,6-hexanediol-bis (anhydrotrimellitate),
1,8-octanediol-bis (anhydrotrimellitate), 2,2-bis (4-hydroxyphenyl) propane-bis (anhydrotrimellitate), represented by the following formulas (5) to (8) A tetracarboxylic dianhydride containing a steroid skeleton, an aromatic tetracarboxylic dianhydride such as a tetracarboxylic dianhydride represented by the following formulas (9) to (11);

1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1 , 3,3a, 4,5,9b-hexahydro-5-
Methyl-5- (tetrahydro-2,5-dioxo-3-
Furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5
-Ethyl-5- (tetrahydro-2,5-dioxo-3
-Furanyl) -naphtho [1,2-c] furan-1,3-
Dione, 1,3,3a, 4,5,9b-hexahydro-
7-methyl-5- (tetrahydro-2,5-dioxo-
3-furanyl) -naphtho [1,2-c] furan-1,3
-Dione, 1,3,3a, 4,5,9b-hexahydro-7-ethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,
3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-
1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-ethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan- 1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5- (tetrahydro-
2,5-dioxo-3-furanyl) -naphtho [1,2-
c] furan-1,3-dione;

An aliphatic tetracarboxylic acid dianhydride having an aromatic ring, such as a compound represented by the following formula (12) and a compound represented by the following formula (13), can be mentioned. These tetracarboxylic dianhydrides can be used alone or in combination of two or more.

[0011]

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[0012]

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[0013]

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[In the formulas (9) to (11), R ⁵ , R ⁶ and R
⁸ , R ⁹ , R ¹² and R ¹³ are each independently an oxy group and a carbonyloxy group (—COO—, —OCO—).
A divalent group selected from R ⁷ , R ¹⁰ , R ¹¹ and R ¹⁴
And R ¹⁵ are each independently selected from a linear or branched alkyl group having 1 to 12 carbon atoms, a linear or branched alkoxyl group having 1 to 12 carbon atoms, a phenyl group, a halogen atom and a trifluoromethyl group. Indicates a valence group.
a, b, and c each independently represent an integer of 0 to 4, and d
And e each independently represent an integer of 0 to 3. ]

[0015]

[Chemical 6]

(In the formula, R ¹⁶ represents a divalent organic group having an aromatic ring, and R ¹⁷ represents a hydrogen atom or an alkyl group.)

[0017]

[Chemical 7]

(In the formula, R ¹⁸ represents a divalent organic group having an aromatic ring, and R ¹⁹ represents a hydrogen atom or an alkyl group.)

Of these, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride Anhydrous, 1,2,3,4-
Cyclopentanetetracarboxylic dianhydride, 2,3,5
-Tricarboxycyclopentylacetic dianhydride, 5-
(2,5-Dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-8-
Methyl-5- (tetrahydro-2,5-dioxo-3-
Furanyl) -naphtho [1,2-c] furan-1,3-dione, bicyclo [2,2,2] -oct-7-ene-
2,3,5,6-tetracarboxylic dianhydride, 1,3
3a, 4,5,9b-Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,
2-c] furan-1,3-dione, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetra Carboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, the following formula (14)-
The compound represented by (20), the following formulas (21) to (22)
From the viewpoint that the compound represented by the formula (1), the compound represented by the following formulas (23) to (24), and the compound represented by A01 to A04 of the following formula (25) can exhibit good liquid crystal alignment. Preferably, particularly preferably, 1, 2,
3,4-cyclobutanetetracarboxylic dianhydride, 1,
3-Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a, 4,5,9b-
Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,
3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-
Examples thereof include 1,3-dione, pyromellitic dianhydride, and a compound represented by A01 of the following formula (25).

[0020]

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[0021]

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[0022]

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[0023]

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<Diamine Compound> Examples of the diamine compound used in the synthesis reaction of the polymer (A) include p-phenylenediamine, m-phenylenediamine and 4,4′-.
Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane,
3,5-diaminobenzoic acid, 4,4′-diaminodiphenylethane, 4,4′-diaminodiphenyl sulfone,
4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 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, 4,4'-diaminobenzanilide, 3,4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,
4'-diaminobenzophenone, 2,7-diaminofluorene, 2,2-bis (4-aminophenyl) hexafluoropropane, 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'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-amino) Phenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) -biphenyl, 1,3-bis (4-aminophenoxy) benzene, 1,3 -Bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl)
-10-hydroanthracene, 9,9-bis (4-aminophenyl) fluorene, 4,4 '-(p-phenylenediisopropylidene) bisaniline, 4,4'-(m-
Phenylenediisopropylidene) bisaniline, 2,
2′-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane,
Aromatic diamines such as 4,4′-bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl;

Diaminotetraphenylthiophene, 2,
6-diaminopyridine, 3,4-diaminopyridine,
2,4-diaminopyridine, 2,6-diaminopurine,
1,4-bis (3-aminopropyl) piperazine, 1,
An aromatic diamine having two amino groups bonded to an aromatic ring such as 4-diaminopiperazine and 3,6-diaminoacridine and a hetero atom other than the nitrogen atom of the amino group;

1,1-metaxylylenediamine, 1,3
-Bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1,2-ethylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylene Diamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine, 1,4-diaminocyclohexane,
1,2-diaminocyclohexane, 1,3-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7
-Methanoindanylene dimethylenediamine, tricyclo [6,2,1,0 ^2.7 ] -undecylenedimethyldiamine, 4,4'-methylenebis (cyclohexylamine)
Aliphatic or cycloaliphatic diamines such as;

Mono-substituted phenylenediamines represented by the following formula (26); Diaminoorganosiloxane represented by the following formula (27);

Examples thereof include compounds represented by B01 to B05 of the following formula (28). These diamine compounds may be used alone or in combination of two or more.

[0029]

[Chemical 12]

(In the formula, R ²⁰ is —O—, —COO—, —
OCO-, -NHCO-, -CONH- and -CO-
R ²¹ represents a monovalent organic group having a steroid skeleton or a trifluoromethyl group. )

[0031]

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(In the formula, R ²² represents a hydrocarbon group having 1 to 12 carbon atoms, p is an integer of 1 to 3, and q is an integer of 1 to 20.)

[0033]

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Of these, p-phenylenediamine,
m-phenylenediamine, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,
3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 1,5-diaminonaphthalene,
2,7-diaminofluorene, 4,4'-diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2- Bis [4- (4-aminophenoxy) phenyl] hexafluoropropane,
2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '-(p-phenylenediisopropylidene) bisaniline, 4,4'-(m-phenylenediisopropylidene) bisaniline, 2,2-bis [4- (4
-Aminophenoxy) phenyl] sulfone, 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine), 1,4-bis (4-aminophenoxy) benzene, 4,4 ' -Bis (4-aminophenoxy) -biphenyl, m-xylylenediamine, B0 of the above formula (28)
Compounds represented by 1 to B05 and compounds represented by B06 to B10 of the following formula (29) are preferable. These diamines may be commercially available products or may be re-reduced before use.

[0035]

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<Hydroxyl Group-Containing Compound> The hydroxyl group-containing compound used in the synthesis reaction of the polymer (A) has a hydroxyl group (eg, alcoholic hydroxyl group, phenolic hydroxyl group) in the molecule of 2
Or a compound containing one hydroxyl group and one amino group in the molecule. The above formula (3) and the above formula (4) representing this hydroxyl group-containing compound
Among the divalent organic groups represented by R ³ and R ⁴ ,
For example, a divalent organic group containing a hydrocarbon group having 2 to 30 carbon atoms, an ethylene glycol group having 2 to 30 carbon atoms and / or a propylene glycol group can be exemplified as a preferable example.

By using a compound containing a hydroxyl group,
A polymer (A) and / or a polymer obtained by introducing a structural unit represented by the following formula (30) into the obtained polymer (A) and synthesizing using the hydroxyl group-containing compound. According to the liquid crystal aligning agent prepared by containing at least one selected from the combination (B)], low temperature firing (150 to
Even when the resin film is formed at 170 ° C., the liquid crystal alignment film having good liquid crystal alignment property and exhibiting a high pretilt angle can be formed by aligning the surface of the resin film. In this specification, "baking" means a step of removing the solvent in the coating film by heating after applying the liquid crystal aligning agent,
In this step, the polymer (A) constituting the resin film may be dehydrated and ring-closed by heating to form a partially imidized or completely imidized resin film.

[0038]

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Among the hydroxyl group-containing compounds, examples of the dihydroxy compound represented by the above formula (3) include 1,4-butanediol, 1,5-pentanediol,
3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,10-decanediol, 1,12
-Alkanediol having 2 to 30 carbon atoms such as dodecanediol and 1,20-eicosanediol, ethylene glycol, propylene glycol, neopentyl glycol, hydroxy-terminated polybutadiene, polyethylene glycol, polypropylene glycol, 1,2-polybutylene glycol, poly Aliphatic diol compounds such as tetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, polydecamethylene glycol, polydimethylsiloxane terminal diol compounds, polydimethylsiloxane carbitol modified diols; 2,2-bis (4-hydroxy) Cyclohexyl) propane, 2,2-bis (4-hydroxycyclohexyl) hexafluoropropane, 2,2-bis (4-hydroxycyclohexyl) Tan, 2,2-bis (4-hydroxycyclohexyl) sulfone, 2,2-bis [4
-(2-hydroxyethoxy) cyclohexyl] propane, 2,2-bis [4- (2-hydroxyethoxy) cyclohexyl] hexafluoropropane, 2,2-bis [4- (2-hydroxyethoxy) cyclohexyl] methane, 2 , 2-bis [4- (2-hydroxyethoxy)
Cyclohexyl] sulfone, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4
-Bis (2-hydroxyethoxy) cyclohexane, dicyclopentadienedimethanol, tricyclodecanedimethanol, pentacyclopentadecanedimethanol,
Alicyclic diols such as compounds represented by C01 to C02 of the following formula (31); 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2 , 2-bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) sulfone, 2,2-bis [4- (2-hydroxyethoxy) phenyl] propane, 2,2-bis [4 -(2-hydroxyethoxy) phenyl] hexafluoropropane, 2,2-bis [4- (2-hydroxyethoxy) phenyl] methane, 2,2-bis [4- (2
-Hydroxyethoxy) phenyl] sulfone, hydroquinone, hydroquinone alkylene oxide addition diol, naphthoquinone alkylene oxide addition diol,
An alkylene oxide addition diol of anthraquinone, an aromatic diol such as a compound represented by C03 to C06 of the following formula (32); and a polyether diol obtained by ring-opening copolymerization of two or more ion-polymerizable cyclic compounds. be able to.

[0040]

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[0041]

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Examples of the ion-polymerizable cyclic compound used to obtain the above polyether diol include ethylene oxide, propylene oxide, butene-1-oxide, isobutene oxide, 3,3-bischloromethyloxetane, tetrahydrofuran and 2-methyl. Tetrahydrofuran, 3-methyltetrahydrofuran, dioxane, trioxane, tetraoxane, cyclohexene oxide, styrene oxide, epichlorohydrin, glycidyl methacrylate, allyl glycidyl ether, allyl glycidyl carbonate, butadiene monooxide, isoprene monooxide, vinyl oxetane, vinyl tetrahydrofuran, vinyl cyclohexene oxide, Phenyl glycidyl ether, butyl glycidyl ether, glyceryl benzoate Cyclic ethers such as Gilles esters. In addition, the above-mentioned ion-polymerizable cyclic compound and at least one compound selected from cyclic imines such as ethyleneimine, cyclic lacnic acids such as β-propiolactone and glycolic lactide and dimethylcyclopolysiloxanes are opened. A polyether diol obtained by copolymerization can also be used. The bonding mode of the structural units in these polyether diols is not particularly limited, and may be any of a random bond, a block bond, and a graft bond.

Among these dihydroxy compounds, alkanediol having 2 to 20 carbon atoms, ethylene glycol,
Propylene glycol, polyethylene glycol, polypropylene glycol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-
Hydroxyphenyl) methane, C01 of the above formula (31)
To C02, and the aromatic diols represented by C03 to C06 of the above formula (32) are preferable.

Examples of the compound represented by the above (4) include 4-aminobutanol, 5-aminopentanol, 3-methyl-5-aminopentanol, 6-aminohexanol, 7-aminoheptanol, Aliphatic compounds such as 8-aminooctanol, 10-aminodecanol, 12-aminododecanol, 20-aminoeicosanol; 2- (4-aminocyclohexyl) -2-
(4'-hydroxycyclohexyl) propane, 2-
(4-Aminocyclohexyl) -2- (4'-hydroxycyclohexyl) hexafluoropropane, 2- [4
-(2-Aminoethoxy) cyclohexyl] -2-
[4 ′-(2′-hydroxyethoxy) cyclohexyl] propane, 2- [4- (2-aminoethoxy) cyclohexyl] -2- [4 ′-(2′-hydroxyethoxy) cyclohexyl] hexafluoropropane, 2-
[4- (2-aminoethoxy) cyclohexyl] -2-
[4 ′-(2′-hydroxyethoxy) cyclohexyl] methane, 2- [4- (2-aminoethoxy) cyclohexyl] -2- [4 ′-(2′-hydroxyethoxy) cyclohexyl] sulfone, 4-aminocyclo Hexanol, 4-aminocyclohexanemethanol, 1-
(2-Aminoethoxy) -4- (2-hydroxyethoxy) cyclohexane, aminodicyclopentadienemethanol, aminotricyclodecanemethanol, aminopentacyclopentadecanemethanol, compounds represented by C07 to C08 of the following formula (33), etc. Alicyclic compounds of
2- (4-aminophenyl) -2- (4'-hydroxyphenyl) propane, 2- (4-aminophenyl) -2
-(4'-hydroxyphenyl) hexafluoropropane, 2- (4-aminophenyl) -2- (4'-hydroxyphenyl) methane, 2- (4-aminophenyl)-
2- (4'-hydroxyphenyl) sulfone, 2- [4
-(2-Aminoethoxy) phenyl] -2- [4'-
(2'-hydroxyethoxy) phenyl] propane, 2
-[4- (2-aminoethoxy) phenyl] -2-
[4 ′-(2′-hydroxyethoxy) phenyl] hexafluoropropane, 2- [4- (2-aminoethoxy) phenyl] -2- [4 ′-(2′-hydroxyethoxy) phenyl] methane, 2- [4- (2-aminoethoxy) phenyl] -2- [4 ′-(2′-hydroxyethoxy) phenyl] sulfone, 4-aminophenol,
An aromatic compound such as a compound represented by C09 to C12 of the following formula (33) can be given.

[0045]

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<Polymer (A)> The polymer (A) constituting the liquid crystal aligning agent of the present invention is synthesized by reacting the tetracarboxylic dianhydride with the diamine compound and the hydroxyl group-containing compound. To be done.

The proportion of the tetracarboxylic dianhydride, diamine compound and hydroxyl group-containing compound used in the synthesis reaction of the polymer (A) is the same as the number of acid anhydride groups contained in the tetracarboxylic dianhydride. Where a is the diamine compound and the equivalent number of the amino group contained in the hydroxyl group-containing compound represented by the above formula (4) is b, and the equivalent number of the hydroxyl group contained in the hydroxyl group-containing compound is c, the following conditions are satisfied. It is preferably a ratio, more preferably a ratio satisfying the following conditions. By defining the use ratio in such a range, the polymer (A) having a suitable molecular weight can be obtained, and thereby the liquid crystal aligning agent prepared can exhibit excellent coatability. The relative use ratio of the diamine compound and the hydroxyl group-containing compound is preferably a ratio satisfying the following conditions, and more preferably a ratio satisfying the following conditions.

[0048]

[Formula 1] Condition: 0.2 ≦ a / (b + c) ≦ 2 Condition: 0.3 ≦ a / (b + c) ≦ 1.4 Condition: 99/1 ≦ (b / c) ≦ 50/50 Condition: 95 / 5 ≦ (b / c) ≦ 60/40

The synthesis reaction of the polymer (A) is carried out in an organic solvent at a temperature of usually 0 to 150 ° C, preferably 0 to 100 ° C. When the reaction temperature is less than 0 ° C,
The solubility of the reaction raw materials (tetracarboxylic dianhydride, diamine compound and hydroxyl group-containing compound) tends to decrease, and when the reaction temperature exceeds 150 ° C., the molecular weight of the resulting polymer (A) tends to decrease. is there. The bonding form of each component constituting the polymer (A) may be random or block.

The organic solvent used in the synthesis of the polymer (A) is not particularly limited as long as it can dissolve the above-mentioned reaction raw materials and the polymer (A) to be produced, and for example, γ-butyrolactone and N-methyl. -2-Pyrrolidone, 1,3-
Aprotic polar solvents such as dimethyl-2-imidazolidinone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, tetramethylurea, hexamethylphosphotriamide; m-cresol, xylenol, phenol, Mention may be made of phenolic solvents such as halogenated phenols. The amount of the organic solvent used is preferably such that the concentration of the reaction raw materials (tetracarboxylic dianhydride, diamine compound and hydroxyl group-containing compound) in the reaction solution is 0.1 to 30% by weight.

The organic solvent includes alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, etc., which are poor solvents for the polymer (A),
The polymer (A) can be used in combination as long as it does not precipitate. Specific examples of such a poor solvent include, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, acetone, methyl ethyl ketone, methyl isobutyl. Ketone, cyclohexanone, methyl acetate, ethyl acetate,
Butyl acetate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether,
Ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-
Propyl ether, ethylene glycol-n-butyl ether, ethylene glycol-n-hexyl ether,
Ethylene glycol monophenyl ether, ethylene glycol methyl phenyl ether, ethylene glycol ethyl phenyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether Ether acetate, ethylene glycol methyl ether acetate,
Ethylene glycol ethyl ether acetate, 4-hydroxy-4-methyl-2-pentanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate , Ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3
-Methyl methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, 3-methyl-3-methoxybutanol, 3-ethyl-3-methoxybutanol, 2
-Methyl-2-methoxybutanol, 2-ethyl-2-
Methoxybutanol, 3-methyl-3-ethoxybutanol, 3-ethyl-3-ethoxybutanol, 2-methyl-2-methoxybutanol, 2-ethyl-2-ethoxybutanol, tetrahydrofuran, dichloromethane,
Examples thereof include 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene and xylene. These may be used alone or in combination of two or more.

By the above synthetic reaction, a reaction solution obtained by dissolving the polymer (A) is obtained. Then, the reaction solution is poured into a large amount of a poor solvent to obtain a precipitate, and the precipitate is dried under reduced pressure to obtain the polymer (A). Further, the polymer (A) can be purified by repeating the step of dissolving the polymer (A) again in an organic solvent and then precipitating it with a poor solvent once or several times.

<Polymer (B)> The polymer (B) constituting the liquid crystal aligning agent of the present invention is an imidized polymer obtained by subjecting the polymer (A) to dehydration ring closure. Dehydration ring closure
(I) by heating the polymer (A), or (i
i) Polymer (A) is dissolved in an organic solvent, a dehydrating agent and a dehydration ring-closing catalyst are added to this solution, and heating is carried out if necessary.

The reaction temperature in the above method (i) is usually 60 to 200 ° C, preferably 100 to 170 ° C.
It is said. If the reaction temperature is lower than 60 ° C, the dehydration ring closure does not proceed sufficiently, and if the reaction temperature exceeds 200 ° C, the molecular weight of the polymer (B) obtained tends to decrease.

On the other hand, in the above method (ii), as the dehydrating agent, acid anhydrides such as acetic anhydride, propionic anhydride and trifluoroacetic anhydride can be used.
The amount of the dehydrating agent used is preferably 1.6 to 20 mol per 1 mol of the repeating unit of the polymer (A). Also,
As the dehydration ring-closing catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, and triethylamine can be used, but not limited thereto. The amount of the dehydration ring-closing catalyst used is preferably 0.5 to 10 mol per 1 mol of the dehydrating agent used. Examples of the organic solvent used for the dehydration ring closure include the organic solvents exemplified as those used for the synthesis of the polymer (A). The reaction temperature of the dehydration ring closure is usually 0 to 180 ° C, preferably 60 to 150 ° C. Further, the polymer (B) can be purified by performing the same operation as in the method for purifying the polymer (A) on the reaction solution thus obtained.

<End-Modified Polymer> The polymer (polymer (A) and / or polymer (B)) constituting the liquid crystal aligning agent of the present invention is a terminal-modified type polymer having a controlled molecular weight. It may be. By using the terminal-modified polymer, the coating characteristics of the liquid crystal aligning agent can be improved without impairing the effects of the present invention. Such a terminal-modified type can be synthesized by adding an acid monoanhydride, a monoamine compound, a monoisocyanate compound or the like to the reaction system when the polymer (A) is synthesized.

Here, examples of the acid monoanhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, and n-tetradecylsuccinic anhydride. Acid anhydride, n-
Hexadecyl succinic anhydride may be mentioned. Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, and n-butylamine.
Pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine,
n-pentadecylamine, n-hexadecylamine, n
-Heptadecylamine, n-octadecylamine, n-
Eicosylamine and the like can be mentioned. In addition, examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

<Logarithmic Viscosity of Polymer> The polymer (A) and the polymer (B) obtained as described above have a logarithmic viscosity (ηln) of 0.05 to 10 dl / g. It is more preferably 0.05 to 5 dl / g. The value of the logarithmic viscosity (ηln) of the polymer in this specification was measured at 30 ° C. for a solution having a concentration of 0.5 g / 100 ml using N-methyl-2-pyrrolidone as a solvent. , Which is obtained by the following mathematical formula.

[0059]

[Equation 2]

<Liquid Crystal Alignment Agent> The liquid crystal alignment agent of the present invention is constituted by dissolving and containing at least one polymer selected from the polymer (A) and the polymer (B) in an organic solvent. As the organic solvent constituting the liquid crystal aligning agent of the present invention,
The solvents exemplified as those used for the synthesis of the polymer (A) can be mentioned. Moreover, the poor solvent exemplified as the one that can be used together during the synthesis of the polymer (A) can be appropriately selected and used together.

The concentration of the polymer (polymer (A) and / or polymer (B)) constituting the liquid crystal aligning agent of the present invention is selected in consideration of viscosity, volatility and the like, but preferably 1
The range is from 10 to 10% by weight. That is, the liquid crystal aligning agent of the present invention is applied to the surface of a substrate and a coating film is baked to form a resin film which becomes a liquid crystal aligning film, but when the concentration of the polymer is less than 1% by weight. In some cases, the resin film may be too thin to obtain a good liquid crystal alignment film. On the other hand, when the concentration of the polymer exceeds 10% by weight, the thickness of the resin film becomes excessively large, and it is difficult to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent increases to apply the liquid crystal. The characteristics may be inferior.

The liquid crystal aligning agent of the present invention may contain a functional silane-containing compound from the viewpoint of improving the adhesion of the polymer (A) and / or the polymer (B) to the substrate surface. Examples of such a functional silane-containing compound include 3-aminopropyltrimethoxysilane and 3
-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-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-
Triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,
6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-
Aminopropyltrimethoxysilane, N-phenyl-3
-Aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane and the like can be mentioned.

<Liquid Crystal Display Device> A liquid crystal display device obtained by using the liquid crystal aligning agent of the present invention can be manufactured, for example, by the following method.

(1) The liquid crystal aligning agent of the present invention is applied to one surface of a substrate provided with a patterned transparent conductive film by, for example, a printing method, and then the coating film is baked to remove the organic solvent. To form a resin film. here,
As the substrate, for example, glass such as float glass and soda glass; a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone and polycarbonate can be used. As a transparent conductive film provided on one surface of the substrate, a NESA film made of tin oxide (SnO ₂ ) (US P
PG registered trademark), indium oxide-tin oxide (In ₂
An ITO film made of O ₃ —SnO ₂ ) or the like can be used, and a photo-etching method or a method using a mask in advance is used for patterning these transparent conductive films. As a method of applying the liquid crystal aligning agent, a roll coater method, a spinner method, or the like can be applied in addition to the printing method.

In applying the liquid crystal aligning agent, in order to further improve the adhesiveness of the resin film to the substrate surface and the transparent conductive film, a functional silane-containing compound, a functional titanium-containing compound or the like is applied to the surface of the substrate. It can also be applied in advance. Heating temperature (film baking temperature) is 100 to 250
° C, preferably 150 to 200 ° C, but under the firing conditions of about 150 to 170 ° C, the advantageous effects of the liquid crystal aligning agent of the present invention are exhibited. The thickness of the formed resin film is usually 0.001 to 1 μm, preferably 0.005 to 0.5 μm. The liquid crystal aligning agent of the present invention containing the polymer (A) forms a resin film to be a liquid crystal aligning film by removing the organic solvent after coating, but as described above, the resin film is further heated. By performing (calcination), dehydration ring closure can proceed to form an imidized resin film.

(2) The resin film surface formed on the substrate surface is
For example, rubbing is performed by rubbing in a certain direction with a roll around which a cloth made of synthetic fiber such as nylon or rayon is wound. Thereby, the alignment ability of the liquid crystal molecules is imparted to the resin film to form a liquid crystal alignment film. In addition to the method using a rubbing treatment, a liquid crystal alignment film is formed by irradiating the surface of the resin film with polarized ultraviolet rays to impart alignment ability, a uniaxial stretching method, a method of obtaining a resin film by a Langmuir-Blodgett method, or the like. You can also.

The liquid crystal alignment film formed as described above is partially irradiated with ultraviolet rays to change the pretilt angle (for example, Japanese Patent Laid-Open No. 6-22).
No. 2,366, JP-A-6-281937), a resist film is partially formed on the surface of the liquid crystal alignment film, and the rubbing treatment is performed in a direction different from the previous rubbing treatment. The viewing angle characteristics of the liquid crystal display device can be improved by performing a process for changing the alignment ability of the liquid crystal alignment film (see Japanese Patent Application Laid-Open No. 5-107544).

(3) Two substrates each having the liquid crystal alignment film formed thereon as described above are prepared, and two substrates are arranged so that the rubbing directions of the respective liquid crystal alignment films, that is, the alignment treatment directions are orthogonal or antiparallel. The two substrates are arranged to face each other with a gap (cell gap) therebetween, the peripheral portions of the two substrates are bonded together with a sealant, and liquid crystal is injected and filled into the cell gap defined by the substrate surface and the sealant. , The injection hole is sealed to form a liquid crystal cell. Then, a polarizing plate is provided on the outer surface of the liquid crystal cell, that is, on the other surface side of each substrate constituting the liquid crystal cell, and the polarization direction thereof coincides with or is orthogonal to the rubbing direction of the liquid crystal alignment film formed on one surface of the substrate. Thus, a liquid crystal display element is obtained.

Here, as the sealant, for example, a curing agent and an epoxy resin containing aluminum oxide spheres as a spacer can be used. Examples of the liquid crystal include a nematic liquid crystal and a smectic liquid crystal. Among them, a nematic liquid crystal is preferable. For example, a Schiff base liquid crystal, an azoxy liquid crystal,
Biphenyl-based liquid crystal, phenylcyclohexane-based liquid crystal, ester-based liquid crystal, terphenyl-based liquid crystal, biphenylcyclohexane-based liquid crystal, pyrimidine-based liquid crystal, dioxane-based liquid crystal, bicyclooctane-based liquid crystal, cubane-based liquid crystal, and the like can be used. In addition, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonaate, and cholesteryl carbonate, and chiral agents such as those sold under the trade names "C-15" and "CB-15" (manufactured by Merck & Co.) It can also be used by adding it. Further, p-decyloxybenzylidene-p
Ferroelectric liquid crystals such as -amino-2-methylbutyl cinnamate can also be used. Further, as a polarizing plate to be bonded to the outer surface of the liquid crystal cell, a polarizing plate or an H film 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. A polarizing plate composed of itself can be mentioned.

[0070]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. Each of the liquid crystal display elements manufactured in the following examples and comparative examples was evaluated for liquid crystal orientation, and the pretilt angle of liquid crystal molecules was measured. Here, the liquid crystal orientation was evaluated by observing the presence or absence of an abnormal domain in the liquid crystal display element when a voltage was turned on and off with a polarizing microscope, and when there was no abnormal domain, it was determined as “good”. In addition, the measurement of the pretilt angle of liquid crystal molecules is performed according to "T.
J. Schffer, et al. , J. et al. Appl. P
hys. , Vol. 19, 2013 (1980) ”in accordance with the method described in“ Crystal rotation method using He—Ne laser light ”.

[Synthesis Example 1] Pyromellitic dianhydride 2
1.81 g (0.10 mol) and 2,2-bis [4- (4
-Aminophenoxy) phenyl] propane 36.95 g
(0.09 mol) and 2,2-bis (4-hydroxyphenyl) propane 2.28 g (0.01 mol) were dissolved in N-methyl-2-pyrrolidone 549 g, and room temperature was adjusted to 24
Allowed to react for hours. Then, the reaction solution was poured into a large excess of pure water to precipitate the reaction product. Then, the precipitate was separated, washed with pure water, and dried under reduced pressure at 40 ° C. for 15 hours to give a polymer (A) having an inherent viscosity (ηln) of 1.16 dl / g [the polymer (A- 1). ] 54.9
g was obtained.

[Synthesis Example 2] The amount of 2,2-bis [4- (4-aminophenoxy) phenyl] propane used was 32.
Change to 84 g (0.08 mol) and 2,2-bis (4-
The amount of hydroxyphenyl) propane used is 4.57 g
A polymer (A) having a logarithmic viscosity (ηln) of 1.09 dl / g was obtained in the same manner as in Synthesis Example 1 except that the polymer (A-2) was used. ] 53.3g
I got

Synthesis Example 3 Instead of 2,2-bis (4-hydroxyphenyl) propane, C0 of the above formula (32)
A polymer (A) having an inherent viscosity (ηln) of 1.10 dl / g was prepared in the same manner as in Synthesis Example 1 except that 5.58 g (0.01 mol) of the aromatic diol represented by 6 was used. Let it be a polymer (A-3). ] 56.3g was obtained.

[Synthesis Example 4] The same as Synthesis Example 1 except that 2.02 g (0.01 mol) of 1,12-dodecanediol was used in place of 2,2-bis (4-hydroxyphenyl) propane. And logarithmic viscosity (ηln) 1.08
Polymer (A) of dl / g [This is referred to as polymer (A-4). ] 53.0g was obtained.

Synthesis Example 5 Instead of 2,2-bis (4-hydroxyphenyl) propane, C0 of the above formula (31)
Polymer (A) having an inherent viscosity (ηln) of 1.04 dl / g in the same manner as in Synthesis Example 1 except that 4.05 g (0.01 mol) of the alicyclic diol represented by 2 was used. Is a polymer (A-5). ] 55.3g was obtained.

[Synthesis Example 6] The same procedure as in Synthesis Example 1 was repeated except that 2.82 g (0.01 mol) of hexaethylene glycol was used instead of 2,2-bis (4-hydroxyphenyl) propane. Logarithmic viscosity (ηln) 1.01d
1 / g of polymer (A) [This will be referred to as polymer (A-6). ] 53.3g was obtained.

[Synthesis Example 7] 22.42 g (0.10 mol) of 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride was used in place of pyromellitic dianhydride. A polymer (A) having a logarithmic viscosity (ηln) of 0.87 dl / g is obtained in the same manner as in Synthesis Example 1 except that the above is used as a polymer (A-7). ] 55.5g was obtained.

Synthesis Example 8 In place of pyromellitic dianhydride, 22.42 g (0.10 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride was used.
Instead of 2-bis [4- (4-aminophenoxy) phenyl] propane, 9.73 g of p-phenylenediamine
A polymer (A) having a logarithmic viscosity (ηln) of 0.97 dl / g was obtained in the same manner as in Synthesis Example 1 except that (0.09 mol) was used [this is referred to as polymer (A-8)]. ] 32.5g
I got 30.0 g of the obtained polymer (A-8) was dissolved in 570 g of γ-butyrolactone, and pyridine 2 was added to this solution.
1.6 g and 16.7 g of acetic anhydride were added, and dehydration ring closure was carried out by heating at 110 ° C. for 3 hours. Then, in the same manner as in Synthesis Example 1, precipitation / separation / washing /
By drying, logarithmic viscosity (ηln) 0.78d
1 / g of polymer (B) [This is referred to as "polymer (B-8)". ] 28.8g was obtained.

[Synthesis Example 9] 1,3,3a, instead of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride
4,5,9b-Hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione 31.43 g
A polymer (A) having a logarithmic viscosity (ηln) of 0.77 dl / g was obtained in the same manner as in Synthesis Example 8 except that (0.10 mol) was used (this will be referred to as polymer (A-9)). ] 58.8g
I got The dehydration ring closure of the polymer (A) and the reaction product were conducted in the same manner as in Synthesis Example 8 except that 30.0 g of the obtained polymer (A-9) was used instead of the polymer (A-8). The logarithmic viscosity (ηl
n) 0.61 dl / g of polymer (B) [This is referred to as "polymer (B-9)". ] 28.7g was obtained.

[Synthesis Example 10] The same as Synthesis Example 1 except that 1.09 g (0.01 mol) of 4-aminophenol was used in place of 2,2-bis (4-hydroxyphenyl) propane. , Logarithmic viscosity (ηln) 0.76dl
/ G of polymer (A) [this will be referred to as polymer (A-10). ] 51.2g was obtained.

Comparative Synthesis Example 1 22.81 g (0.10 mol) of pyromellitic dianhydride and 2,2-bis [4-
(4-Aminophenoxy) phenyl] propane 41.0
5 g (0.10 mol) was dissolved in 734 g of N-methyl-2-pyrrolidone and reacted at room temperature for 24 hours. Then, the reaction solution was poured into a large excess of pure water to precipitate the reaction product. Then, the precipitate was separated, washed with pure water, and dried under reduced pressure at 40 ° C. for 15 hours to give a comparative polymer having a logarithmic viscosity (ηln) of 1.98 dl / g [the polymer (a- 1). ] 60.7g was obtained.

[Example 1] [1] Preparation of liquid crystal aligning agent: mixed solution of γ-butyrolactone and ethyl 3-ethoxypropionate (mixing weight ratio =
90:10), the polymer (A-1) obtained in Synthesis Example 1 was dissolved into a solution having a solid content concentration of 4% by weight, and the solution was filtered through a filter having a pore size of 1 μm to align the liquid crystal of the present invention. The agent was prepared.

[2] Fabrication of liquid crystal display element: ITO provided on one surface of a glass substrate having a thickness of 1 mm
The liquid crystal aligning agent of the present invention prepared in the above [1] is applied onto a transparent conductive film formed of a film by using a printing machine for coating, and the coating film is baked at 160 ° C. for 1 hour to obtain a dry film. A resin film having a thickness of 0.05 μm was formed.

The surface of the formed resin film is subjected to a rubbing treatment using a rubbing machine having a roll around which a cloth made of rayon is wound to give the resin film an aligning ability of liquid crystal molecules to form a liquid crystal aligning film. Formed. here,
The rubbing treatment conditions were a roll speed of 500 rpm and a stage moving speed of 1 cm / sec.

Two substrates with the liquid crystal alignment film formed as described above were prepared, and an epoxy resin adhesive containing aluminum oxide spheres with a diameter of 17 μm was applied to the outer edge of each substrate by screen printing. After that, the two substrates were arranged to face each other with a gap so that the rubbing directions of the respective liquid crystal alignment films were orthogonal to each other, and the outer edges were brought into contact with each other and pressure-bonded to cure the adhesive.

Nematic liquid crystal “MLC-2003” (manufactured by Merck Japan Co., Ltd.) was injected and filled in the cell gap defined by the adhesive on the surface and the outer edge of the substrate, and then the injection hole was filled with an epoxy adhesive. A liquid crystal cell was constructed by sealing with. Thereafter, a polarizing plate was attached to the outer surface of the liquid crystal cell such that the polarization direction coincided with the rubbing direction of the liquid crystal alignment film formed on one surface of the substrate, thereby producing a liquid crystal display element. The liquid crystal display device manufactured as described above had no abnormal domain when the operating voltage was turned on and off, and had excellent liquid crystal orientation. The pretilt angle of liquid crystal molecules in this liquid crystal display element was as high as 4.0 °.

[Examples 2-10, Comparative Example 1] Polymers (A-1) obtained in accordance with the formulations shown in Table 1 below instead of the polymer (A-1) were synthesized (A). ),
In the same manner as in Example 1 [1] except that each of the polymer (B) obtained in Synthesis Examples 8 to 9 and the polymer (a-1) obtained in Comparative Example Synthesis Example 1 was used. A liquid crystal aligning agent was prepared. Then, using each of the liquid crystal aligning agents thus obtained, a liquid crystal display device was produced in the same manner as in Example 1 [2]. In each of the produced liquid crystal display elements, the liquid crystal orientation was evaluated, and the pretilt angle of liquid crystal molecules was measured. These results are shown together with the results of Example 1.

[0088]

[Table 1]

[0089]

【The invention's effect】

(1) According to the liquid crystal aligning agent of the present invention, even if the baking temperature at the time of forming the resin film is low, the aligning treatment of the resin film surely imparts the aligning ability of the liquid crystal molecules. A liquid crystal alignment film can be formed, and excellent liquid crystal alignment can be exhibited in a liquid crystal display device including the liquid crystal alignment film. (2) According to the liquid crystal aligning agent of the present invention, a liquid crystal aligning film capable of exhibiting a high pretilt angle can be obtained by aligning the resin film even when the baking temperature for forming the resin film is low. Can be formed.

The liquid crystal alignment film formed by the liquid crystal aligning agent of the present invention is applicable not only to TN type liquid crystal display elements but also to STN (Su
per Twisted Nematic (SHT) type liquid crystal display device, SH (Super Homeotropic) type liquid crystal display device, IPS (In-Plane-Switch)
(hing) type liquid crystal display element, ferroelectric liquid crystal display element, antiferroelectric liquid crystal display element and various other liquid crystal display elements. Further, the liquid crystal display device provided with the liquid crystal alignment film has excellent liquid crystal alignment and reliability, and can be effectively used for various devices. For example, a desk calculator, a wristwatch, a clock, a counting display, a word processor It can be suitably used as a display device such as a personal computer and a liquid crystal television.

Front page continuation (72) Inventor Yasushi Rokuka 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (72) Inventor Yasushi Matsuki 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd.

Claims (1)

[Claims] 1. A tetracarboxylic dianhydride represented by the following formula (1), a diamine compound represented by the following formula (2), and a diamine compound represented by the following formula (3) or (4). A liquid crystal containing at least one polymer selected from a polymer obtained by reacting with a hydroxyl group-containing compound, and an imidized polymer having a structure obtained by dehydration ring closure of the polymer. Alignment agent. Embedded image