JP2003049069A - Liquid crystal-orienting agent and liquid crystal display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a liquid crystal-orienting agent that has excellent printability without occurrence of uneven printing and pinholes, when print-coated on a substrate and provide a liquid crystal display element equipped with a liquid crystal orientation film obtained from the liquid crystal orientation agent. SOLUTION: The liquid crystal orientation agent comprises (A) a polymer bearing at least one of recurring units selected from an amic acid structure and an imide structure, preferably a polyamic acid and an imide polymer and (B) a silicon-including compound having polyether bonds.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a liquid crystal aligning agent and a liquid crystal display device. More specifically, it relates to a liquid crystal aligning agent having excellent printability and a liquid crystal display device obtained from the liquid crystal aligning agent.

[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 liquid crystal display element substrate. A layer of a nematic liquid crystal having a positive dielectric anisotropy is formed into a cell having a sandwich structure, and the long axes of the liquid crystal molecules are continuously aligned from one substrate to the other substrate.
The so-called TN type (Twist)
A TN liquid crystal display device having a d Nematic liquid crystal cell is known. Further, by using a liquid crystal added with a chiral agent which is an optically active substance, a state in which the long axis of the liquid crystal molecule is continuously twisted between the substrates over 180 degrees or more is achieved, and the birefringence effect produced by this is utilized.
TN (Super Twisted Nematic)
Type liquid crystal display elements are also known. Furthermore, IPS (In-Pl), which has less viewing angle dependency than TN type liquid crystal display elements,
Ane switching type liquid crystal display elements and vertical alignment type liquid crystal display elements have been developed.

Polyimide, polyamide, polyester and the like are conventionally known as materials for the liquid crystal alignment film in these liquid crystal display elements.
It has excellent heat resistance, affinity for liquid crystals, and mechanical strength, and is used in many liquid crystal display devices. A liquid crystal alignment film made of polyimide is usually obtained by coating a substrate with a liquid crystal aligning agent which is a polyimide precursor such as polyamic acid or a solution of soluble polyimide in an organic solvent, and is imidized by heating. A silane coupling agent may be added to the liquid crystal aligning agent for the purpose of improving the leveling property with respect to the substrate.

However, although the liquid crystal aligning agent to which the silane coupling agent is added improves the leveling property with respect to the substrate, bubbles are apt to be generated at the time of coating, and the bubbles cause pinholes in the liquid crystal aligning film, which causes the liquid crystal. Orientation of
There is a problem that the electric characteristics of the obtained liquid crystal display element are deteriorated.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a liquid crystal aligning agent which does not generate bubbles during coating on a substrate and has good coatability. Other objects and advantages of the present invention will be apparent from the following description.

[0006]

According to the present invention, the above objects and advantages of the present invention are represented by (A) the repeating unit represented by the following formula (I-1) and the following formula (I-2): And a polymer having at least one type of repeating unit selected from the repeating units described above, and (B) a silicon-containing compound having a polyether bond.

[0007]

[Chemical 6]

(In the formula, P ¹ is a tetravalent organic group, and Q ^{1 is}
Is a divalent organic group. )

[0009]

[Chemical 7]

(In the formula, P ² is a tetravalent organic group, and Q ²
Is a divalent organic group. )

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. (A) Polymer The polymer used in the present invention contains at least one repeating unit selected from the repeating unit represented by the above formula (I-1) and the repeating unit represented by the above formula (I-2). Have. Examples thereof include a polyamic acid and / or an imidized polymer having a structure obtained by dehydration ring closure (imidization) of the polyamic acid. The "imidized polymer" in the present invention includes those in which all of its repeating units are imidized and those in which they are partially imidized. Further, a part of the imide ring may be an isoimide ring.

The preferred polymer in the present invention is the repeating unit represented by the above formula (I-1) and the above formula (I-
It is a polymer having a repeating unit represented by 2). As a liquid crystal aligning agent having such a polymer, for example,
The following polymers are mentioned. A liquid crystal aligning agent containing both a polyamic acid and an imidized polymer. A liquid crystal aligning agent containing a block copolymer obtained from a prepolymer having an amic acid structure and a prepolymer having an imide structure. A liquid crystal aligning agent containing an imidized polymer obtained by partially dehydrating and ring-closing a polyamic acid. Of these, and are preferred, and especially preferred.

Polyamic Acid The polyamic acid used in the present invention is obtained by reacting a tetracarboxylic dianhydride and a diamine.

[Tetracarboxylic acid dianhydride] Examples of the tetracarboxylic acid dianhydride used in the synthesis of the above polyamic acid include butanetetracarboxylic acid dianhydride.
1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3, Four
-Cyclobutanetetracarboxylic acid dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-
Cyclobutane tetracarboxylic acid 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, 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, Three
a, 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, 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 dianhydride, the following formulas (I) and (II)
An aliphatic or alicyclic tetracarboxylic acid dianhydride such as a compound represented by:

[0015]

[Chemical 8]

(Where R is¹ And R³ Has an aromatic ring
Represents a divalent organic group, R² And R ^Four Is a hydrogen atom
Or an alkyl group, and a plurality of R² And R^Four 
May be the same or different. )

Pyromellitic dianhydride 3,3 ', 4,
4'-benzophenone tetracarboxylic dianhydride, 3,
3 ', 4,4'-biphenylsulfone tetracarboxylic acid dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 3 , 3 ', 4,4'-biphenyl ether tetracarboxylic acid dianhydride 3,3', 4,4'-dimethyldiphenylsilane tetracarboxylic acid 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) diphenyl sulfone dianhydride,
4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoroisopropylidene diphthalic acid 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'-diphenylether dianhydride, bis ( Triphenylphthalic acid) -4,4'-diphenylmethane dianhydride, ethylene glycol-bis (anhydrotrimellitate), propylene glycol-bis (anhydrotrimellitate), 1,4-butanediol-bis (an) Hydrotrimeritate), 1,6-hexanediol-bis (anhydrotrimeritate), 1,8-octanediol-
Bis (anhydrotrimellitate) 2,2-bis (4
Aromatic tetracarboxylic dianhydrides such as -hydroxyphenyl) propane-bis (anhydrotrimellitate) and compounds represented by the following formulas (1) to (4) can be given. These may be used alone or in combination of two or more.

[0018]

[Chemical 9]

Of these, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride Anhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl -3-Cyclohexene-1,2-dicarboxylic 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-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, bicyclo [2,2,2] -oct-
7-ene-2,3,5,6-tetracarboxylic dianhydride,
Pyromellitic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-
Biphenyl sulfone tetracarboxylic acid dianhydride, 1,4,
5,8-naphthalenetetracarboxylic dianhydride, among compounds represented by the above formula (I), compounds represented by the following formulas (5) to (7) and compounds represented by the above formula (II) Among them, the compound represented by the following formula (8) is preferable from the viewpoint of exhibiting good liquid crystal alignment, and particularly preferable are 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 2 , 3,5-Tricarboxycyclopentyl acetic 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 Examples include -furanyl) -naphtho [1,2-c] furan-1,3-dione, pyromellitic dianhydride, and a compound represented by the following formula (5).

[0020]

[Chemical 10]

[Diamine] Examples of the diamine used in the synthesis of the above polyamic acid include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4 '. -Diaminodiphenyl sulfide, 4,4 '
-Diaminodiphenyl sulfone, 3,3'-dimethyl-
4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 4,4'-diaminodiphenyl ether,
1,5-diaminonaphthalene, 2,2'-dimethyl-4,
4'-diaminobiphenyl, 3,3'-dimethyl-4,
4'-diaminobiphenyl, 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 3,3'-ditrifluoromethyl-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, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane,
2,2-bis [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,
1,4,4 '-(p-phenylene isopropylidene) bisaniline, 4,4'-(m-phenylene isopropylidene) bisaniline, 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] -octafluoro Aromatic diamines such as biphenyl;

1,1-meta-xylylenediamine, 1,3-
Propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine,
1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine,
Aliphatic and cycloaliphatic diamines such as hexahydro-4,7-methanoindanylene dimethylene diamine, tricyclo [6.2.1.02,7] -undecylenedimethyl diamine, 4,4'-methylene bis (cyclohexyl amine);

2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyrazine, 5,6-diamino- 2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5
-Triazine, 1,4-bis (3-aminopropyl) piperazine, 2,4-diamino-6-isopropoxy-1,
3,5-triazine, 2,4-diamino-6-methoxy-
1,3,5-triazine, 2,4-diamino-6-phenyl-1,3,5-triazine, 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3, 5-
Triazine, 4,6-diamino-2-vinyl-s-triazine, 2,4-diamino-5-phenylthiazole,
2,6-diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5-diamino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridine lactate, 3,8- Diamino-6-phenylphenanthridine, 1,4-diaminopiperazine, 3,6-diaminoacridine, bis (4-aminophenyl) phenylamine and compounds represented by the following formulas (III) to (IV), A diamine having two primary amino groups in the molecule and a nitrogen atom other than the primary amino groups;

[0024]

[Chemical 11]

(In the formula, R ⁵ is pyridine, pyrimidine,
Represents a monovalent organic group having a ring structure containing a nitrogen atom selected from triazine, piperidine and piperazine, and X
Represents a divalent organic group. )

[0026]

[Chemical 12]

(In the formula, R ⁶ is pyridine, pyrimidine,
Represents a divalent organic group having a ring structure containing a nitrogen atom selected from triazine, piperidine and piperazine;
Represents a divalent organic group, and a plurality of X's may be the same or different. )

Monosubstituted phenylenediamines represented by the following formula (V); Diaminoorganosiloxanes represented by the following formula (VI);

[0029]

[Chemical 13]

(In the formula, R ⁷ is —O—, —COO—, —
OCO-, -NHCO-, -CONH- and -CO-
Represents a divalent organic group selected from, R ⁸ represents a steroid skeleton, a monovalent organic group or an alkyl group having 6 to 30 carbon atoms having a group selected from a trifluoromethyl group and a fluoro group. )

[0031]

[Chemical 14]

(In the formula, R ⁹ represents a hydrocarbon group having 1 to 12 carbon atoms, a plurality of R ⁹ may be the same or different, p is an integer of 1 to 3, and q is 1-2
It is an integer of 0. )

Examples thereof include compounds represented by the following formulas (9) to (13). These diamines can be used alone or in combination of two or more.

[0034]

[Chemical 15]

(In the formula, y is an integer of 2 to 12, and z is an integer of 1 to 5.)

Of these, p-phenylenediamine,
4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-ditrifluoromethyl-4, 4'-diaminobiphenyl, 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, 1,4
-Cyclohexanediamine, 4,4'-methylenebis (cyclohexylamine), 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, the above formulas (9) to (13) ), 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, a compound represented by the following formula (III): 14), compounds represented by the above formula (IV), compounds represented by the following formula (15) and compounds represented by the above formula (V): dodecanoxy-2,4- Diaminobenzene, pentadecanoxy-2,
4-diaminobenzene, hexadecanooxy-2,4-diaminobenzene, octadecanoxy-2,5-diaminobenzene, dodecanooxy-2,5-diaminobenzene,
Pentadecanoxy-2,5-diaminobenzene, hexadecanoxy-2,5-diaminobenzene, octadecanoxy-2,5-diaminobenzene, the following formula (16):
The compound represented by (21) is preferable.

[0037]

[Chemical 16]

[Synthesis of polyamic acid] The tetracarboxylic dianhydride and the diamine compound used in the synthesis reaction of the polyamic acid are used in such a manner that the tetracarboxylic dianhydride is used with respect to 1 equivalent of the amino group contained in the diamine compound. The ratio of the acid anhydride group of the product is 0.2 to 2 equivalents is preferable, and the ratio of 0.3 to 1.2 equivalents is more preferable. The synthesis reaction of polyamic acid is carried out in an organic solvent under temperature conditions of usually -20 to 150 ° C, preferably 0 to 100 ° C. Here, the organic solvent is not particularly limited as long as it can dissolve the polyamic acid to be synthesized, and examples thereof include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, and dimethyl sulfoxide. Aprotic polar solvents such as γ-butyrolactone, tetramethylurea and hexamethylphosphortriamide; and phenolic solvents such as m-cresol, xylenol, phenol and halogenated phenols. The amount (a) of the organic solvent used is usually the total amount (b) of the tetracarboxylic dianhydride and the diamine compound, and the total amount (a + b) of the reaction solution.
The amount is preferably 0.1 to 30% by weight with respect to the above.

The organic solvent includes alcohols, ketones, esters, which are poor solvents for polyamic acid,
Ethers, halogenated hydrocarbons, hydrocarbons and the like can be used in combination so long as the polyamic acid to be produced 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, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropione
G, 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 dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,
4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene and the like can be mentioned.

As described above, a reaction solution obtained by dissolving the polyamic acid 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 a polyamic acid. Further, the polyamic acid can be purified by performing the step of dissolving the polyamic acid again in the organic solvent and then precipitating it in the poor solvent once or several times.

Imidized Polymer The imidized polymer used in the present invention is obtained by dehydrating and ring-closing a polyamic acid obtained by reacting a tetracarboxylic dianhydride and a diamine.

[Tetracarboxylic acid dianhydride] Examples of the tetracarboxylic acid dianhydride used in the synthesis of the imidized polymer include the tetracarboxylic acid dianhydride used in the synthesis of the above polyamic acid. .

As the tetracarboxylic dianhydride used in the synthesis of the imidized polymer of the present invention, alicyclic tetracarboxylic dianhydride is preferable. As a particularly preferred specific example, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5-
(Tetrahydro-2,5-dioxo-3-furanyl)-
Naft [1,2-c] furan-1,3-dione, 1,3,3
and a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione.
Further, the alicyclic tetracarboxylic acid dianhydride and other tetracarboxylic acid dianhydride may be used in combination.

[Diamine] Examples of the diamine used for synthesizing the imidized polymer include the diamine used for synthesizing the polyamic acid described above.

As the diamine used in the synthesis of the imidized polymer of the present invention, the diamine represented by the above formula (V) is preferable. As preferred specific examples, and among the compounds represented by the above formula (V), dodecanoxy-2,4
-Diaminobenzene, pentadecanooxy-2,4-diaminobenzene, hexadecanoxy-2,4-diaminobenzene, octadecanoxy-2,5-diaminobenzene, dodecanoxy-2,5-diaminobenzene, pentadecanoxy-2,5-diaminobenzene, hexadecanoxy -2,5-diaminobenzene, octadecanoxy-
2,5-diaminobenzene, the above formulas (16) to (21)
The compound represented by

In the imidized polymer of the present invention, the diamine represented by the above formula (V) may be used in combination with another diamine. Preferred among the other diamines are p-phenylenediamine, 4,
4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 1,5-diaminonaphthalene,
2,2'-dimethyl-4,4'-diaminobiphenyl,
2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 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, 1,4-cyclohexanediamine, 4,4'-methylenebis (cyclohexylamine), 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) ) Biphenyl, compounds represented by the above formulas (9) to (13), 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, the above formula (III Of the compounds represented by the formula (14), and of the compounds represented by the formula (IV), represented by the formula (15). Such compounds, and the like. In the imidized polymer of the present invention, the diamine represented by the above formula (V) is preferably used in an amount of 0.5% by weight or more, and particularly preferably 1% by weight or more, based on all diamines.

[Synthesis of Imidized Polymer] The imidized polymer constituting the liquid crystal aligning agent of the present invention can be obtained by dehydration ring closure of the above polyamic acid. The dehydration ring closure of the polyamic acid is carried out by (i) heating the polyamic acid or (ii) dissolving the polyamic acid in an organic solvent,
A dehydrating agent and a dehydration ring-closing catalyst are added to this solution, and the mixture is heated if necessary. The reaction temperature in the method of heating the polyamic acid (i) is usually 5
The temperature is set to 0 to 200 ° C, preferably 60 to 170 ° C. If the reaction temperature is lower than 50 ° C, the dehydration ring closure reaction may not proceed sufficiently, and if the reaction temperature exceeds 200 ° C, the molecular weight of the imidized polymer obtained may decrease. On the other hand, in the method (ii) of adding a dehydrating agent and a dehydration ring-closing catalyst to the solution of polyamic acid, as the dehydrating agent, for example, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride should be used. You can The amount of the dehydrating agent used is 0.001 mol per 1 mol of repeating unit of polyamic acid.
It is preferably from 0.1 to 20 mol. Further, as the dehydration ring-closing catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, triethylamine and the like can be used. However, it is not limited to these. The amount of the dehydration ring-closing catalyst used is 0.
It is preferably from 0.1 to 10 mol. Examples of the organic solvent used for the dehydration ring-closing reaction include the organic solvents exemplified as those used for the synthesis of polyamic acid. The reaction temperature of the dehydration ring closure reaction is usually 0 to 180 ° C, preferably 10 to 150 ° C. Further, the imidized polymer can be purified by performing the same operation as in the method for purifying the polyamic acid on the reaction solution thus obtained.

The imidized polymer used in the present invention may be partially dehydrated and ring-closed and have a low imidization ratio. The imidization ratio of the imidized polymer used in the present invention is preferably 80% or more, more preferably 8%.
It is 5% or more. Here, the "imidization ratio" is a percentage of the number of repeating units forming an imide ring with respect to the total number of repeating units in the polymer. At this time, a part of the imide ring may be an isoimide ring.

End-Modified Polymer The above-mentioned polyamic acid and imidized polymer may be end-modified type with controlled molecular weight. 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 synthesizing the polyamic acid. Here, examples of the acid monoanhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, and n-tetradecylsuccinic anhydride. , N-
Hexadecyl succinic anhydride and the like can be mentioned. Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n
-Pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-
Decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n- Examples thereof include eicosylamine.
Examples of monoisocyanate compounds include phenyl isocyanate and naphthyl isocyanate.

Logarithmic Viscosity of Polymer The polyamic acid and imidized polymer obtained as described above have a logarithmic viscosity (η _ln ) of usually 0.05.
It is -10 dl / g, preferably 0.05-5 dl / g. The value of the logarithmic viscosity (η _ln ) in the present invention is 0.5 g when N-methyl-2-pyrrolidone is used as a solvent.
The viscosity is determined by the following formula (i) by measuring the viscosity of a solution of 100 ml / 100 ml at 30 ° C.

[0051]

[Equation 1]

(B) Silicon-Containing Compound The silicon-containing compound used in the present invention is a polyorganosiloxane having a polyether bond. The above polyorganosiloxane preferably has a polyether bond in the side chain. As the silicon-containing compound, a compound represented by the following formula (II) is particularly preferable.

[0053]

[Chemical 17]

(In the formula, A is a single bond, a methylene group or an alkylene group having 2 to 5 carbon atoms, B is a hydroxyl group or an alkyl group having 1 to 3 carbon atoms, and a and b are 1 independently of each other. Is a number from 1 to 100, c and d are independently from each other a number from 1 to 3, and m and n are independently from each other a number from 1 to 6.)

2 to 5 carbon atoms represented by A in the above formula (II)
Examples of the alkylene group include ethylene group, n-propylene group, n-butylene group, pentamethylene group and the like. Further, the alkyl group having 1 to 3 carbon atoms represented by B in the above formula (II) includes a methyl group, an ethyl group, n
A propyl group and the like. Formula (II) above
And a and b are independently of each other a number of 1 to 100,
The number is preferably 30 to 80. Further, c and d are numbers 1 to 3 independently of each other. Further, m and n are each independently a number of 1 to 6, and preferably a number of 1 to 3. Particularly, a combination in which m is 1 and n is 2, and a combination in which m is 2 and n is 3 are preferable. These compounds can be used alone or in combination of two or more.

The silicon-containing compound (B) used in the present invention usually has a molecular weight of 500 to 50,000,
It is preferably 1,000 to 10,000. The compounding ratio of the (B) silicon-containing compound in the liquid crystal aligning agent of the present invention is usually 0.01 with respect to 100 parts by weight of the (A) polymer.
To 2 parts by weight, preferably 0.05 to 1 part by weight, and more preferably 0.05 to 0.5 part by weight. 0.01
If it is less than 10 parts by weight, the effect of improving the printability may be insufficient, and if it exceeds 10 parts by weight, the viscosity may increase.

Liquid Crystal Aligning Agent The liquid crystal aligning agent of the present invention is usually constituted by dissolving and containing the above-mentioned polymer (A) and silicon-containing compound (B) in an organic solvent. The temperature when preparing the liquid crystal aligning agent of the present invention,
Usually, it is 0 ° C to 200 ° C, preferably 20 ° C to 60 ° C. As the organic solvent constituting the liquid crystal aligning agent of the present invention,
The solvents exemplified as those used in the synthesis reaction of polyamic acid can be mentioned. Further, the poor solvent exemplified as the one that can be used together during the synthesis reaction of the polyamic acid can also be appropriately selected and used together. The solid content concentration in the liquid crystal aligning agent of the present invention is selected in consideration of viscosity, volatility, etc., but is preferably 1 to 10% by weight.
The range is. That is, the liquid crystal aligning agent of the present invention is applied to the surface of a substrate to form a coating film which becomes a liquid crystal aligning film, but when the solid content concentration is less than 1% by weight, the film thickness of this coating film is If it is too small to obtain a good liquid crystal alignment film, and if the solid content concentration exceeds 10% by weight, the film thickness of the coating film becomes too large to obtain a good liquid crystal alignment film. In addition, the viscosity of the liquid crystal aligning agent increases, and the coating characteristics deteriorate.

The liquid crystal aligning agent of the present invention may contain an epoxy group-containing compound from the viewpoint of improving the adhesiveness to the substrate surface. Examples of such epoxy group-containing compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether,
Propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromo neopentyl glycol di Glycidyl ether, 1,3,5,6-tetraglycidyl-
2,4-hexanediol, N, N, N ', N',-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N ',-tetraglycidyl-4,
4'-diaminodiphenylmethane etc. can be mentioned as a preferable thing. The compounding ratio of these and the epoxy group-containing compound is usually 100 parts by weight of the polymer,
It is 40 parts by weight or less, preferably 0.1 to 30 parts by weight.

Liquid Crystal Display Element The liquid crystal display element 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 onto one surface of a substrate provided with a patterned transparent conductive film, preferably by a method such as a printing method, and then the applied surface is heated to form a coating film. Form. Here, as the substrate,
For example, a glass such as float glass or soda glass; a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone or polycarbonate can be used. As the transparent conductive film provided on one surface of the substrate, a NESA film made of tin oxide (SnO ₂ ) (registered trademark of PPG Co., USA), indium oxide-tin oxide (In ₂ O ₃ —Sn) is used.
An ITO film made of O 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. When applying the liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a functional silane-containing compound, a functional titanium-containing compound or the like is previously applied to the substrate surface. You can also do it. The heating temperature after applying the liquid crystal aligning agent is 80 to 300 ° C., preferably 120 to 300 ° C.
It is set to 250 ° C. The liquid crystal aligning agent of the present invention containing a polyamic acid forms a coating film to be an alignment film by removing the organic solvent after coating, but further heating promotes dehydration ring closure and is more imidized. It can also be a coated film. The thickness of the coating film formed is
Usually 0.001 to 1 μm, preferably 0.005
Is 0.5 μm.

(2) A rubbing treatment is performed in which the formed coating film surface is rubbed in a certain direction with a roll around which a cloth made of fibers such as nylon, rayon, and cotton is wound. As a result, the ability of aligning liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film. Further, a liquid crystal alignment film formed by the liquid crystal aligning agent of the present invention has a liquid crystal alignment film as disclosed in, for example, JP-A-6-222366 and JP-A-6-281937.
A process of changing the pretilt angle by partially irradiating ultraviolet rays, or Japanese Patent Laid-Open No. 5-10754.
As shown in Japanese Patent Publication No. 4, a resist film is partially formed on the surface of the liquid crystal alignment film subjected to the rubbing treatment, and the rubbing treatment is performed in a direction different from the previous rubbing treatment, and then the resist film is removed. By performing a treatment that changes the liquid crystal alignment ability of the liquid crystal alignment film, it is possible to improve the visibility characteristics of the liquid crystal display element.

(3) Two substrates on which the liquid crystal alignment film is formed as described above are prepared, and the two substrates are separated by a gap so that the rubbing directions of the liquid crystal alignment films are orthogonal or antiparallel. Facing each other through (cell gap),
The peripheral portions of the two substrates are bonded together using a sealant, and liquid crystal is injected and filled into the cell gap defined by the substrate surface and the sealant, and the injection holes are 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 that constitutes the liquid crystal cell, and the polarization direction thereof is the same as or orthogonal to the rubbing direction of the liquid crystal alignment film formed on the one surface of the substrate. A liquid crystal display device is obtained by laminating as described above.

Here, as the sealant, for example, a curing agent and an epoxy resin containing aluminum oxide spheres as spacers can be used. Examples of the liquid crystal include nematic type liquid crystal and smectic type liquid crystal, and among them, nematic type liquid crystal is preferable, for example, Schiff base type liquid crystal, azoxy type liquid crystal,
Biphenyl liquid crystals, phenylcyclohexane liquid crystals, ester liquid crystals, terphenyl liquid crystals, biphenylcyclohexane liquid crystals, pyrimidine liquid crystals, dioxane liquid crystals, bicyclooctane liquid crystals, cubane liquid crystals, and the like can be used. Further, to these liquid crystals, for example, 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). It is also possible to use by adding such as. Furthermore, p-decyloxybenzylidene-p
Ferroelectric liquid crystals such as -amino-2-methylbutyl cinnamate can also be used. Further, as a polarizing plate to be attached to the outer surface of a liquid crystal cell, a polarizing film or an H film in which a polarizing film called an H film that absorbs iodine while stretching and aligning polyvinyl alcohol is sandwiched between cellulose acetate protective films A polarizing plate composed of itself can be mentioned.

[0063]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

Synthesis Example 1 As tetracarboxylic dianhydride, pyromellitic dianhydride 109.06 g (0.5 mol) and 1,2,3,4-cyclobutanetetracarboxylic dianhydride 98.06 g (0.04 g). 5
Mol) and 200.2 g (1.0 mol) of 4,4-diaminodiphenyl ether as a diamine compound were dissolved in 4500 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours. Then, the reaction solution was poured into a large excess of methyl alcohol to precipitate the reaction product. Then, it was washed with methyl alcohol and dried under reduced pressure at 40 ° C. for 15 hours to give a polyamic acid having an inherent viscosity of 0.88 dl / g and an imidization rate of 0% (this was referred to as “polyamic acid (A
-1) ". ) 290 g were obtained.

Synthesis Example 2 109.06 g (0.5 mol) of pyromellitic dianhydride as tetracarboxylic dianhydride and 1,2,3,4-
Cyclobutane tetracarboxylic dianhydride 98.06g
(0.5 mol) and 198.27 g (1 mol) of 4,4′-diaminodiphenylmethane as a diamine compound were dissolved in 4500 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours. Then, the reaction solution was poured into a large excess of methyl alcohol to precipitate the reaction product. Then, it was washed with methyl alcohol and dried under reduced pressure at 40 ° C. for 15 hours to give a polyamic acid having an inherent viscosity of 0.92 dl / g and an imidization rate of 0% (this was referred to as “polyamic acid (A
-2) ". ) 310 g were obtained.

Synthesis Example 3 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride 196.12 g
(1.0 mol), 200.2 g (1.0 mol) of 4,4′-diaminodiphenyl ether as a diamine compound was dissolved in 4500 g of N-methyl-2-pyrrolidone, and 6
The reaction was carried out at 0 ° C for 6 hours. Then, the reaction solution was poured into a large excess of methyl alcohol to precipitate the reaction product. After that, it was washed with methyl alcohol and dried at 40 ° C under reduced pressure for 15 minutes.
By drying for an hour, the logarithmic viscosity is 0.90 dl /
As a result, 290 g of a polyamic acid having an imidization ratio of 0% (hereinafter referred to as "polyamic acid (A-3)") was obtained.

Synthesis Example 4 As tetracarboxylic acid dianhydride 1,196,12 g of 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride
(1.0 mol), 212 g (1.0 mol) of 2,2'-dimethyl-4,4'-aminobiphenyl as a diamine compound was dissolved in 4500 g of N-methyl-2-pyrrolidone and reacted at 60 ° C for 6 hours. Let Then, the reaction solution was poured into a large excess of methyl alcohol to precipitate the reaction product. After that, wash with methyl alcohol and depressurize at 40 ℃.
By drying for 15 hours, logarithmic viscosity of 0.99d
290 g of a polyamic acid having 1 / g and an imidization ratio of 0% (this is referred to as "polyamic acid (A-4)") was obtained.

Synthesis Example 5 224.17 g (1 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic acid dianhydride and 200.2 g of 4,4′-diaminodiphenyl ether as a diamine compound (1. 0 mol) was dissolved in 4500 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours. Then, the reaction solution was poured into a large excess of methyl alcohol to precipitate the reaction product. Then, it was washed with methyl alcohol and dried under reduced pressure at 40 ° C. for 15 hours to give a polyamic acid having an inherent viscosity of 0.87 dl / g and an imidization rate of 0% (this was referred to as “polyamic acid (A
-5) ". ) 280 g were obtained.

Synthesis Example 6 224.17 g (0.5 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5
-Methyl-5 (tetrahydro-2,5-dioxo-3-
Furanyl) -naphtho [1,2-c] -furan-1,3-
Dione 157.14 g (0.5 mol), p-phenylenediamine as a diamine compound 94.62 g (0.87)
5 mol), 2,2-ditrifluoromethyl-4,4-diaminobiphenyl 32.02 g (0.1 mol), 3,6
-Bis (4-aminobenzoyloxy) cholestane (compound represented by the above formula (9), the same applies hereinafter) 6.43 g
(0.01 mol) and 4.04 g (0.015 mol) of octadecanoxy-2,5-diaminobenzene were dissolved in 4500 g of N-methyl-2-pyrrolidone and reacted at 60 ° C for 6 hours. Then, the reaction solution was poured into a large excess of methyl alcohol to precipitate the reaction product. Then, it was washed with methyl alcohol and dried under reduced pressure at 40 ° C. for 15 hours to obtain 410 g of a polyamic acid having an inherent viscosity of 0.87 dl / g and an imidization ratio of 0%. 30 g of the obtained polyamic acid was added to N-methyl-2-pyrrolidone 570.
g, pyridine 23.4 g and acetic anhydride 18.
1 g was added and dehydration ring closure was performed at 110 ° C. for 4 hours, precipitation, washing and decompression were carried out in the same manner as above to obtain a logarithmic viscosity of 0.80 d.
17.5 g of an imidized polymer having an imidization ratio of 100% was obtained (hereinafter referred to as "imidized polymer (B-1)").

Synthesis Example 7 224.17 g (0.5 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5
-Methyl-5 (tetrahydro-2,5-dioxo-3-
Furanyl) -naphtho [1,2-c] -furan-1,3-
Dione 157.14 g (0.5 mol), p-phenylenediamine as a diamine compound 94.62 g (0.87)
5 mol), bisaminopropyltetramethyldisiloxane 24.85 g (0.1 mol), 3,6-bis (4-aminobenzoyloxy) cholestane 6.43 g (0.0
1 mol) and 4.04 g (0.015 mol) of octadecanoxy-2,5-diaminobenzene were dissolved in 4500 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours. Then, the reaction solution was poured into a large excess of methyl alcohol to precipitate the reaction product. Then, it was washed with methyl alcohol and dried under reduced pressure at 40 ° C. for 15 hours to obtain 370 g of a polyamic acid having a logarithmic viscosity of 0.82 dl / g and an imidization ratio of 0%. 30 g of the obtained polyamic acid was dissolved in 570 g of N-methyl-2-pyrrolidone, 23.4 g of pyridine and 18.1 g of acetic anhydride were added, and dehydration ring closure was performed at 110 ° C. for 4 hours, followed by precipitation, washing, and the like. Depressurize to obtain a logarithmic viscosity of 0.77 dl / g,
18.5 g of an imidized polymer having an imidization ratio of 100% (hereinafter, referred to as "imidized polymer (B-2)") was obtained.

Synthesis Example 8 224.17 g (1 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic acid dianhydride, and p-phenylenediamine 1 as a diamine compound
07.06 g (0.99 mol), 3,6-bis (4-aminobenzoyloxy) cholestane 6.43 g (0.0
1 mol) was dissolved in 4500 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours. Then, the reaction solution was poured into a large excess of methyl alcohol to precipitate the reaction product. Then, wash with methyl alcohol, and under reduced pressure 4
By drying at 0 ° C for 15 hours, the logarithmic viscosity of 0.9
410 g of polyamic acid with 0 dl / g and imidization ratio of 0%
Got 30 g of the obtained polyamic acid was N-methyl-
2-pyrrolidone dissolved in 570 g, pyridine 23.4
g and 18.1 g of acetic anhydride were dehydrated and ring-closed at 110 ° C. for 4 hours, followed by precipitation, washing and depressurization in the same manner as above to obtain an imidized polymer having an inherent viscosity of 0.85 dl / g and an imidization ratio of 100%. (This is "imidized polymer (B-3)"
And ) 17.5g was obtained.

Synthesis Example 9 224.17 g (0.5 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5
-Methyl-5 (tetrahydro-2,5-dioxo-3-
Furanyl) -naphtho [1,2-c] -furan-1,3-
157.14 g (0.5 mol) of dione and 89.21 g (0.82) of p-phenylenediamine as a diamine compound.
5 mol), 2,2'-ditrifluoromethyl-4,4 '
-Diaminobiphenyl 32.02 g (0.1 mol), 1
-(3,5-Diaminobenzoyloxy) -4- (4-
Trifluoromethylbenzoyloxy) -cyclohexane (compound represented by the above formula (20), the same applies hereinafter) 2
5.34 g (0.06 mol), octadecanoxy-2,
4.04 g (0.015 mol) of 5-diaminobenzene was dissolved in 4500 g of N-methyl-2-pyrrolidone, and 6
The reaction was carried out at 0 ° C for 6 hours. Then, the reaction solution was poured into a large excess of methyl alcohol to precipitate the reaction product. After that, it was washed with methyl alcohol and dried at 40 ° C under reduced pressure for 15 minutes.
By drying for an hour, the logarithmic viscosity is 0.90 dl /
g, 410 g of a polyamic acid having an imidization ratio of 0% was obtained.
30 g of the obtained polyamic acid was dissolved in 570 g of N-methyl-2-pyrrolidone, 23.4 g of pyridine and 18.1 g of acetic anhydride were added, and dehydration ring closure was performed at 110 ° C. for 4 hours, followed by precipitation, washing, and the like. The pressure was reduced to obtain 17.5 g of an imidized polymer having a logarithmic viscosity of 0.83 dl / g and an imidization ratio of 100% (this is referred to as “imidized polymer (B-4)”).

Example 1 100 parts by weight of the imidized polymer (B-1) obtained in Synthesis Example 6 and SH3771 (Toray Dow Corning Silicone ( Manufactured by K.K.) 0.075 parts by weight and γ-butyrolactone /
N-methyl-2-pyrrolidone / butyl cellosolve (71
/ 17/12 (weight ratio)) was dissolved in a mixed solvent to give a solution having a solid content concentration of 4% by weight, and this solution was filtered using a filter having a pore size of 1 μm to prepare the liquid crystal aligning agent of the present invention. The above liquid crystal aligning agent was applied to a transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film using a liquid crystal aligning film printer (manufactured by Nissha Printing Co., Ltd.), and dried on a hot plate at 80 ° C. for 1 minute. , 10 on a 200 ° C hot plate
After drying for a minute, a film having an average film thickness of 600 angstrom was formed. When this substrate was observed with a microscope at a magnification of 20 times, printing unevenness and pinholes were not seen, and the printability was good.

The number of rotations of the roll was set to 5 by a rubbing machine having a roll in which a nylon type cloth was wound around this coating.
A rubbing process was performed at 00 rpm, a stage moving speed of 3 cm / sec, and a length of pushing in the hairs of 0.4 mm to form a liquid crystal alignment film. Next, the liquid crystal alignment film-formed substrate was immersed in isopropyl alcohol for 1 minute and then dried on a hot plate at 100 ° C. for 5 minutes. Next, an epoxy resin adhesive containing 5.5 μm in diameter containing aluminum oxide spheres is applied to the outer edges of the pair of substrates each having a liquid crystal alignment film, and then the liquid crystal alignment films are superposed and pressure-bonded to each other, The adhesive was cured. Next, a nematic liquid crystal (MLC-622, manufactured by Merck & Co., Inc.) was inserted between the pair of substrates through the liquid crystal inlet.
After filling 1), the liquid crystal injection port is sealed with an acrylic photo-curing adhesive, and a polarizing plate is attached to both outer surfaces of the substrate,
A liquid crystal display device of the present invention was produced. An alternating current of 6.0 V (peak-peak) was superimposed on the obtained liquid crystal display device 30.
When a rectangular wave of 3.0 Hz and 3.0 V was applied for 500 hours at an ambient temperature of 70 ° C. and the element was visually observed, no display defect of the liquid crystal display element was found.

Examples 2 to 22, Comparative Examples 1 to 2 Using the polyamic acid and the imidized polymer obtained in Synthesis Examples 1 to 9 and Comparative Synthesis Examples 1 and 2, the kind and addition amount of the silicon-containing compound and the liquid crystal were used. A liquid crystal aligning agent was prepared in the same manner as in Example 1 except that the drying temperature of the alignment film was changed, a film was formed on the substrate, and the presence or absence of print unevenness and pinholes was observed. It was produced and observed for display defects. In Examples 5 to 22 and Comparative Examples 1 and 2, the polyamic acid and the imidized polymer were used in a ratio such that polyamic acid: imidized polymer = 4: 1 (weight ratio). The results are also shown in Table 1.

[0076]

[Table 1] C-1: SH3771 (manufactured by Toray Dow Corning Silicone Co., Ltd.) C-2: SH190 (manufactured by Toray Dow Corning Silicone Co., Ltd.)

[0077]

According to the liquid crystal aligning agent of the present invention, it is possible to prepare a liquid crystal aligning film having good printability without print unevenness and pinholes when printed and applied on a substrate. INDUSTRIAL APPLICABILITY The liquid crystal display device of the present invention can be suitably used not only for TN type and STN type liquid crystal display devices but also for selecting SH (Super Homeotropic) by selecting the liquid crystal to be used.
Type, IPS (In-Plane Switching)
It can also be suitably used for liquid crystal display devices of mold, ferroelectric and antiferroelectric properties. Furthermore, the liquid crystal display device of the present invention can be effectively used for various devices, and is used for display devices such as desk calculators, wrist watches, table clocks, coefficient display boards, word processors, personal computers, liquid crystal televisions, and the like.

Claims (4)

[Claims] 1. A polymer having (A) at least one repeating unit selected from a repeating unit represented by the following formula (I-1) and a repeating unit represented by the following formula (I-2), and ( B) A liquid crystal aligning agent comprising a silicon-containing compound having a polyether bond. [Chemical 1] (In the formula, P ¹ is a tetravalent organic group, and Q ¹ is a divalent organic group.) (In the formula, P ² is a tetravalent organic group, and Q ² is a divalent organic group.) 2. The polymer (A) is a polymer having a repeating unit represented by the following formula (I-1) and a repeating unit represented by the following formula (I-2). Liquid crystal aligning agent. [Chemical 3] (In the formula, P ¹ is a tetravalent organic group, and Q ¹ is a divalent organic group.) (In the formula, P ² is a tetravalent organic group, and Q ² is a divalent organic group.) 3. The silicon-containing compound (B) has the formula (I
The liquid crystal aligning agent according to claim 1, which is a compound represented by I). [Chemical 5] (In the formula, A is a single bond, a methylene group or an alkylene group having 2 to 5 carbon atoms, B is a hydroxyl group or an alkyl group having 1 to 3 carbon atoms, and a and b are 1 to 10 independently of each other.
0 is a number, c and d are numbers 1 to 3 independently of each other, and m and n are numbers 1 to 6 independently of each other. ) 4. A liquid crystal display device, comprising a liquid crystal alignment film obtained from the liquid crystal alignment agent according to claim 1.