KR101545354B1 - Liquid crystal aligning agent and liquid crystal display device - Google Patents

Abstract

SUMMARY OF THE INVENTION An object of the present invention is to provide a liquid crystal aligning agent which exhibits excellent heat resistance and provides a liquid crystal alignment film excellent in leakage of voltage.

The liquid crystal aligning agent is obtained by dehydrating and ring closure of a polyamic acid obtained by reaction of a tetracarboxylic dianhydride with a diamine containing a structure represented by the following formula (A) and a compound having two amino groups, 30% or more imidized polymer.

(A)

(In the formula (A), "*"

A liquid crystal aligning agent, a liquid crystal alignment film, a liquid crystal display element, a tetracarboxylic acid dianhydride, a polyamic acid, an imidized polymer, heat resistance,

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal aligning agent and a liquid crystal display element,

The present invention relates to a liquid crystal aligning agent and a liquid crystal display element. More particularly, the present invention relates to a liquid crystal aligning agent which exhibits excellent heat resistance and provides a liquid crystal alignment film excellent in high voltage leakage property, and a liquid crystal display element in which panel abnormal lighting caused by static electricity generated in a manufacturing process of a display element panel is suppressed.

As a liquid crystal display element, a liquid crystal alignment layer 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. Two liquid crystal alignment layers are disposed opposite to each other, and a nematic liquid crystal layer having positive dielectric anisotropy TN type liquid crystal display device having so-called TN type (Twisted Nematic) liquid crystal cell in which the long axis of the liquid crystal molecules is made to be a cell of a sandwich structure and is twisted by 90 degrees continuously from one substrate toward the other substrate is widely known. In addition, STN (Super Twisted Nematic) type liquid crystal display device or IPS (In-Plane Switching) type liquid crystal display device which can realize a higher contrast ratio than the TN type liquid crystal display device, An FBC (Fringe Field Switching) type liquid crystal display device which improves the luminance by increasing the aperture ratio of the display element portion, OCB (Optical Compensated Bend) type liquid crystal display device which has little visual dependency and is excellent in high- , A VA (Vertical Alignment) type liquid crystal display device using a nematic liquid crystal having negative dielectric anisotropy, and the like have been developed.

As a material of the liquid crystal alignment film in these liquid crystal display elements, a resin material such as a polyamic acid, an imidized polymer, a polyamide, and a polyester is known. Particularly, a liquid crystal alignment film containing a polyamic acid or an imidized polymer has heat resistance, And has been used in many liquid crystal display devices because of its excellent compatibility with liquid crystal (see, for example, Patent Documents 1 to 3 below).

A liquid crystal display element having a liquid crystal alignment film including these resin materials is designed on the premise that the lifetime of the liquid crystal display device exceeds 10 years as typified by liquid crystal televisions in recent years. With respect to this demand, by using an imidized polymer having an imide ring structure that is thermally and physically stable as a material for a liquid crystal alignment film, good characteristics for long-term driving, for example, voltage retention due to thermal stress and deterioration (Heat resistance) of suppressing the heat-resistant property of the resin. However, when an imidized polymer having a large number of imide structures, for example, an imidized polymer having an imidization rate of 50% or more (hereinafter referred to as "a degree of imidization rate imidized polymer") is used, The panel may cause abnormal lighting due to the influence of the static electricity generated from the electrostatic chuck used for fixing the panel. It takes a long time of about 24 hours for eliminating or alleviating the abnormal lighting, Is lowered. It is considered that the reason why a long time is required for eliminating or alleviating the abnormal lighting is that the leakage of the high voltage accumulated in the liquid crystal cell is low because the electrical insulation of the imidization polymer of the imidization ratio is very high.

As described above, it is considered that the heat resistance and the high-voltage leakage property in the liquid crystal panel are in the relationship of the yield rejection. Accordingly, there is a demand for a liquid crystal alignment film material excellent in the high voltage leakage property without deteriorating the heat resistance exhibited by the conventional imidization rate imide polymer. From such a viewpoint, there have been hardly known examples of the liquid crystal alignment film material being studied. Some examples of improvement in the afterimage characteristic of a liquid crystal display element are proposed from the viewpoints different from this point of view. However, some improvement methods or liquid crystal alignment film materials have been proposed (for example, see Patent Documents 4 and 5 below). However, improvements in the high-voltage leakage property in the liquid crystal panel are not achieved by these methods and materials.

[Patent Document 1] JP-A-9-197411

[Patent Document 2] Japanese Unexamined Patent Publication No. 2003-149648

[Patent Document 3] Japanese Unexamined Patent Publication No. 2003-107486

[Patent Document 4] JP-A-8-122793

[Patent Document 5] Japanese Patent Application Laid-Open No. 2005-120376

[Patent Document 6] JP-A-6-222366

[Patent Document 7] JP-A-6-281937

[Patent Document 8] JP-A-5-107544

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a liquid crystal aligning agent which exhibits excellent heat resistance and is excellent in high voltage leakage property and a liquid crystal aligning agent And to provide the suppressed liquid crystal display element.

Other objects and advantages of the present invention will be apparent from the following description.

According to the present invention, the above objects and advantages of the present invention are achieved by firstly,

Tetracarboxylic dianhydride, a compound having a structure represented by the following formula (A) and two amino groups, a compound represented by the following formula (D-III), and a compound represented by the following formula The reaction of the diamine containing at least one member selected from the group consisting of 4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether and bis [4- (4-aminophenoxy) phenyl] And a liquid crystal aligning agent containing an imidized polymer obtained by dehydrocondylating the polyamic acid obtained by the above process.

≪ Formula (A)

(화학식 D-III 중, R⁹는 -O-, -COO-, -OCO-, -NHCO-, -CONH- 또는 -CO-이고, R¹⁰은 스테로이드 골격, 트리플루오로메틸페닐기, 트리플루오로메톡시페닐기 및 플루오로페닐기로부터 선택되는 골격 또는 기를 갖는 1가의 유기기, 또는 탄소수 6 내지 30의 알킬기이고, R¹¹은 탄소수 1 내지 4의 알킬기이고, a3은 0 내지 3의 정수임)(In the formula (A), "*"
[Formula D-III]

(Wherein R ⁹ is -O-, -COO-, -OCO-, -NHCO-, -CONH- or -CO-, and R ¹⁰ is a steroid skeleton, a trifluoromethylphenyl group, a trifluoromethyl group, R ¹¹ is an alkyl group having 1 to 4 carbon atoms, and a 3 is an integer of 0 to 3. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group,

The above objects and advantages of the present invention are secondly,

And a liquid crystal alignment film formed of the above-mentioned liquid crystal aligning agent.

The liquid crystal aligning agent of the present invention does not deteriorate the voltage holding ratio and liquid crystal aligning ability even when heat resistance, that is, heat stress for a long time is applied, and even when abnormal lighting caused by static electricity occurs in the manufacturing process of the display element, A liquid crystal alignment film excellent in leakage of voltage is provided.

The liquid crystal alignment film formed of the liquid crystal aligning agent of the present invention can be suitably applied to various liquid crystal display devices.

The liquid crystal display element of the present invention including the liquid crystal alignment layer formed of the liquid crystal aligning agent of the present invention does not deteriorate the display performance even when the liquid crystal display element is driven for a long period of time. Therefore, the liquid crystal display of the present invention can be effectively applied to various devices, and can be applied to various devices such as a clock, a portable game machine, a word processor, a notebook computer, a car navigation system, a camcorder, a PDA, And can be preferably used for a display device such as a liquid crystal television.

Hereinafter, the present invention will be described in detail.

The liquid crystal aligning agent of the present invention comprises a tetracarboxylic dianhydride, a compound having a structure represented by the above formula (A) and a compound having two amino groups, a compound represented by the above formula (D-III) Diaminobenzoic acid, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether and bis [4- (4-aminophenoxy) phenyl] sulfone. Or more of a polyamic acid obtained by reacting a polyamic acid obtained by reacting a diamine containing an imidized polyimide.

≪ Tetracarboxylic acid dianhydride >

As the tetracarboxylic acid dianhydride used for synthesizing the imidized polymer contained in the liquid crystal aligning agent of the present invention, alicyclic tetracarboxylic dianhydride, aliphatic tetracarboxylic acid dianhydride and aromatic tetracarboxylic acid dianhydride .

Specific examples of the alicyclic tetracarboxylic acid dianhydride include 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracar 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,3-dichloro-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride , 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 1,2, 4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-dicyclohexyltetracarboxylic dianhydride, cis-3,7-dibutylcycloocta-1,5-diene- 1,2,5,6-tetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) 3-cyclohexene-1,2-dicarboxylic acid anhydride, 3,5,6-tricarbonyl-2-carboxynorbornane-2: Tetrahydrofuran tetracarboxylic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-fura 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5 (tetrahydro- Furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-ethyl-5- (tetrahydro- 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 (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [l, 2-c] , 9b-hexahydro-8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ , 3a, 4,5,9b-hexahydro-8-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ 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- dioxotetrahydrofuranyl) Hexene-1,2-dicarboxylic acid anhydride, bicyclo [2.2.2] -oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, 3-oxabicyclo [3.2.1 ] Octane-2,4-dione-6-spiro-3 '- (tetrahydrofuran-2', 5'-dione) and compounds represented by the following formulas TI and T-II.

[Chemical formula I-I]

[Chemical Formula T-II]

(In the formulas TI and T-II, R ¹ and R ³ are each a divalent organic group having an aromatic ring, R ² and R ⁴ are each a hydrogen atom or an alkyl group, and a plurality of R ² and R ^4, Or may be different)

Specific examples of the aliphatic tetracarboxylic acid dianhydride include butane tetracarboxylic dianhydride and the like.

Specific examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride, 3,3', 4,4'-bis Phenylsulfone tetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 3,3 ', 4,4' -Biphenyl ether tetracarboxylic acid dianhydride, 3,3 ', 4,4'-dimethyldiphenylsilane tetracarboxylic acid dianhydride, 3,3', 4,4'-tetraphenylsilanetetracarboxylic acid dianhydride Water, 1,2,3,4-furantetracarboxylic acid dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4'- 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoroisopropyl 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) dianhydride, (Triphenylphthalic acid) dianhydride, bisphenol-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis Dianhydrides, dianhydrides, bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride, ethylene glycol-bis (anhydrotrimellitate), propylene glycol-bis (anhydrotrimellitate) Bis (anhydrotrimellitate), 1,6-hexanediol-bis (anhydrotrimellitate), 1,8-octanediol-bis (anhydrotrimellitate), 2,2- Hydroxyphenyl) propane-bis (anhydrotrimellitate), compounds represented by each of the following formulas T-1 to T-4, and the like.

[Chemical formula (T-1)

[Chemical Formula T-2]

[Chemical Formula T-3]

[Chemical Formula T-4]

These tetracarboxylic acid dianhydrides may be used singly or in combination of two or more.

The tetracarboxylic acid dianhydride used for synthesizing the imidized polymer contained in the liquid crystal aligning agent of the present invention is preferably selected from the group consisting of alicyclic tetracarboxylic dianhydride and pyromellitic dianhydride in aromatic tetracarboxylic dianhydride and 2 , And 2 ', 3,3'-biphenyltetracarboxylic dianhydride (hereinafter referred to as "specific tetracarboxylic dianhydride"). Specific tetracarboxylic acid dianhydrides include 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1 , 2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 2,3,5- 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 5- 3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, cis-3,7-dibutylcycloocta-1,5-diene- 5,6-tetracarboxylic acid dianhydride, 3,5,6-tricarbonyl-2-carboxynorbornane-2: 3,5: 6-dianhydride, 1,3,3a, 4,5 , 9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ 5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) 2,3,4a, 4,5,9b-hexahydro-5,8-dimethyl-5- (tetrahydro-2,5-dioxo- 3-dione, bicyclo [2.2.2] -oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride Water, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '- (tetrahydrofuran-2', 5'-dione) The compound represented by each of formulas T-5 to T-7, the compound represented by formula (II), the compound represented by formula (T-8), pyromellitic dianhydride and 2,2 ', 3,3'- Phenyl tetracarboxylic acid dianhydride is more preferable in view of being able to exhibit good liquid crystal alignability, and more preferable is at least one selected from the group consisting of 1,2,3,4-cyclobutanetetracarboxylic acid Dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 2,3,5-tricaryl (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,5-diene-1,2,5,6-tetracarboxylic acid dianhydride, 3,5,6-tricarbonyl-2-carboxynorbornane-2: 3,5: Hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro- At least one compound selected from the group consisting of a compound represented by the formula T-5, pyromellitic dianhydride and 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, and particularly preferably 1, 2,3,4-tetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [l, 2-c] furan -1,3-dione, pyromellitic dianhydride and 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, and among them, at least one selected from the group consisting of 2,3,5- Tricarboxycyclopentylacetic acid dianhydride and 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) , 2-c] furan-1,3-dione.

[Chemical Formula T-5]

[Chemical Formula T-6]

[Chemical Formula T-7]

[Chemical Formula T-8]

The tetracarboxylic acid dianhydride used for synthesizing the imidized polymer contained in the liquid crystal aligning agent of the present invention may be obtained by reacting the specific tetracarboxylic dianhydride as described above with 60 mol% or more of the total tetracarboxylic acid dianhydride, Or more, and more preferably 80 mol% or more.

When the tetracarboxylic acid dianhydride contains a tetracarboxylic dianhydride other than the specific tetracarboxylic dianhydride, preferable examples of the tetracarboxylic dianhydride other than the specific tetracarboxylic dianhydride include, for example, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenylsulfone tetracarboxylic acid dianhydride, 1, 3 ' 4,5,8-naphthalenetetracarboxylic acid dianhydride, and the like.

<Diamine>

The diamine used for synthesizing the imidized polymer contained in the liquid crystal aligning agent of the present invention is preferably a compound containing a structure represented by the above formula (A) and a compound having two amino groups (hereinafter referred to as "compound (A) will be. As such a compound (A), for example, a compound represented by the following formula (A-1) can be mentioned.

[A-1]

(In formula (A-1), each of U ¹ and U ² independently represents an alkylene group having 2 to 5 carbon atoms or a divalent alicyclic group having 4 to 6 carbon atoms, or an aromatic ring having 6 to 10 Bivalent organic group)

Examples of the alkylene group having 2 to 5 carbon atoms represented by U ¹ and U ² in the above formula (A-1) include a 1,3-propylene group and a 1,5-pentylene group. Examples of the divalent alicyclic group having 4 to 6 carbon atoms represented by U ¹ and U ² include a 1,4-cyclohexylene group and the like. U ^1, and the "aromatic ring" refers to aromatic hydrocarbon rings in monocyclic from a divalent organic group containing an aromatic ring of U ² raw water 6 to 10, and aromatic hydrocarbons having an aromatic hydrocarbon ring and the condensed ring systems of the cyclic ring, and these And a heteroaromatic ring in which one or more carbon atoms constituting the ring of the ring is substituted with a hetero atom. As the divalent organic group containing an aromatic ring having 6 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms is preferable. Particularly preferred specific examples of U ¹ and U ² are, for example, 1,3-propylene, 1,4-cyclohexylene, 1,4-phenylene, naphthalene- , A 5-diyl group, and a triazine-2,4-diyl group.

Specific examples of the compound (A) include N, N'-bis (3-aminopropyl) piperazine, N, N'- ) Piperazine, and particularly N, N'-bis (4-aminophenyl) piperazine is preferable.

As the diamine used for synthesizing the imidized polymer contained in the liquid crystal aligning agent of the present invention, the compound (A) is used in combination with other diamines.

Examples of other diamines usable in the present invention include p-phenylenediamine, m-phenylenediamine, 3,5-diaminobenzoic acid, 4,4'-diaminodiphenylmethane, 4,4'- Diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminodiphenylsulfone, Diaminobiphenyl ether, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 5-amino-1- (4 ' Aminophenyl) -1,3,3-trimethyl indane, 3,4'-diaminodiphenyl ether, 3,3-trimethyl indane, Diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2'- Bis (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, ) Phenyl] sulfone, 1,4-bis (4-aminophenoxy) benz (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 2,7- (4-aminophenyl) fluorene, 4,4'-methylene-bis (2-chloroaniline), 2,2 ', 5,5'-tetrachloro-4,4 Diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'- (p-phenyleneisopropylidene) bisaniline, 4,4'- (m-phenyleneisopropylidene) bisaniline, 2,2'-bis [4- 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 4,4'-bis [(4-amino Aromatic diamines such as the compounds represented by the following formulas (D-1) to (D-5), such as the compounds represented by the following formulas (D-1) to (D-5);

[Formula D-1]

[Formula D-2]

[Formula D-3]

[Formula D-4]

[Formula D-5]

(Y in the formula (D-4) is an integer of 2 to 12, and z in the formula (D-5) is an integer of 1 to 5)

But are not limited to, 1,1-hexanediol, 1,1-meta-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, Isophoronediamine, isophoronediamine, tetrahydrodicyclopentadienylenediamine, tricyclo [6.2.1.0 ^2,7 ] undecylenediimethyldiamine, 4,4'-methylenebis (cyclohexylamine), 1,3-bis Aliphatic or alicyclic diamines such as cyclohexane;

Diaminopyridine, 5, 6-diamino-2,3-dicyanopyrimidine, 5, 6-diamino-2,3-dicyanopyrimidine, Dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis (3-aminopropyl) piperazine, Diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4- 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-triazine, 4,6- 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-ethoxy acridactate, 3,8-diamino-6-phenylphenanthridine, Aminophenyl) phenylamine, 1- (3,5-diaminophenyl) -3-decylsuccinimide, 1- (3,5-diaminophenyl) 3-jade A diamine having two primary amino groups and nitrogen atoms other than the primary amino group in the molecule such as tetradecylsuccinimide, a compound represented by the following formula (D-I) and a compound represented by the following formula (D-II);

[Formula D-I]

(In the formula DI, R ⁵ is a pyridine, pyrimidine, triazine, piperidine and a monovalent organic group having a ring structure containing a nitrogen atom is selected from piperazine, X ¹ is a divalent organic group, R ⁶ is an alkyl group having 1 to 4 carbon atoms, and a1 is an integer of 0 to 3)

[Formula D-II]

(In the formula (D-II), R ⁷ is a divalent organic group having a ring structure including a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine, X ² is a divalent organic group X ² may be the same or different, R ⁸ is an alkyl group having 1 to 4 carbon atoms, and a 2 is an integer of 0 to 3,

A mono-substituted phenylenediamine such as a compound represented by the following formula (D-III);

[Formula D-III]

(Wherein R ⁹ is -O-, -COO-, -OCO-, -NHCO-, -CONH- or -CO-, and R ¹⁰ is a steroid skeleton, a trifluoromethylphenyl group, a trifluoromethyl group, R ¹¹ is an alkyl group having 1 to 4 carbon atoms, and a 3 is an integer of 0 to 3. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group,

A diaminoorganosiloxane such as a compound represented by the following formula (D-IV)

And the like.

[Formula D-IV]

(In the formula (D-IV), R ¹² is a hydrocarbon group of 1 to 12 carbon atoms, plural R ^{12 s} may be the same or different, p is an integer of 1 to 3, and q is an integer of 1 to 20 Integer)

These other diamines may be used alone or in combination of two or more.

The benzene ring of the aromatic diamine may be substituted with one or more alkyl groups having 1 to 4 carbon atoms (preferably a methyl group). It is preferable that R ⁶ , R ⁸ and R ¹¹ in the above formulas DI, D-II and D-III are each a methyl group, and a1, a2 and a3 are each preferably 0 or 1, .

The steroid skeleton of R ¹⁰ in the above formula (D-III) means a skeleton having a cyclopentano-perhydrophenanthrene nucleus or a skeleton in which one or two or more carbon-carbon bonds thereof are double bonded. The monovalent organic group of R ⁵ having such a steroid skeleton preferably has 17 to 51 carbon atoms, more preferably 17 to 29 carbon atoms. Specific examples of R ¹⁰ include a cholestan-3-yl group, a cholesta-5-en-3-yl group, a cholesta-24- , And lanostan-3-yl group.

Examples of other diamines used for synthesizing the imidized polymer contained in the liquid crystal aligning agent of the present invention include p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl Diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,5-diaminonaphthalene, Bis (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoro 4,4'- (p-phenylenediisopropylidene) bisaniline, 4,4 '- (m-phenylenediisopropylidene) bisaniline, 1,4-cyclohexanediamine, (4-aminophenoxy) biphenyl, each of the above-mentioned formulas (D-1) to (D-5) Compounds to be displayed, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine , 3,6-diaminoacridine, a compound represented by the following formula (D-6) in the compound represented by the formula (DI), a compound represented by the formula (D-7) (3-diaminopropyl) tetramethyldisiloxane in the compound represented by the formula (D-IV) and the compound represented by the formula (D-IV), more preferably at least one compound selected from the group consisting of The compound represented by the general formula D-III and the compound represented by the general formula D-III and the compound represented by the general formula D-III, 4-aminophenoxy) phenyl] sulfone.

[Formula D-6]

[Formula D-7]

Specific examples of the compound represented by the above formula (D-III) include compounds represented by the following formulas (D-8) to (D-16).

[Formula D-8]

[Chemical formula D-9]

[Formula D-10]

[Formula D-11]

[Formula D-12]

[Formula D-13]

[Chemical Formula D-14]

[Formula D-15]

[Formula D-16]

Among the compounds represented by the above formula (D-III), compounds wherein R ⁷ is -O- or -COO- in the above formula (D-III) and R ⁸ is a monovalent organic group having a steroid skeleton are preferable, -8 to D-13 are preferred.

The diamine used for synthesizing the imidized polymer contained in the liquid crystal aligning agent of the present invention preferably contains 1 mol% or more, more preferably 10 mol% or more, of the compound (A) based on the total diamine .

The diamine to be used in the present invention may be prepared by reacting the compound (A), the compound represented by the above formula (D-III), p-phenylenediamine, 3,5-diaminobenzoic acid, 4,4'- , 4'-diaminodiphenyl ether, and bis [4- (4-aminophenoxy) phenyl] sulfone. In this case, the ratio of each compound to the total diamine is preferably 1 to 80 mol%, more preferably 5 to 70 mol%, relative to the compound (A) Preferably 1 to 50 mol%, and more preferably 5 to 30 mol%, and is preferably at least one member selected from the group consisting of p-phenylenediamine, 3,5-diaminobenzoic acid, 4,4'-diaminodiphenylmethane, Is preferably 30 to 90 mol%, more preferably 40 to 60 mol% based on at least one member selected from the group consisting of diaminodiphenyl ether and bis [4- (4-aminophenoxy) phenyl] sulfone .

&Lt; Synthesis of imidized polymer >

The imidized polymer contained in the liquid crystal aligning agent of the present invention can be obtained by reacting the tetracarboxylic dianhydride as described above with the compound (A), the compound represented by the above formula (D-III), and the p-phenylenediamine, Diaminobenzoic acid, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether and bis [4- (4-aminophenoxy) phenyl] sulfone. Or more of a polyamic acid obtained by reacting a polyamic acid obtained by the reaction of a diamine containing the above-mentioned diamine.

[Synthesis of polyamic acid]

The ratio of the tetracarboxylic dianhydride and the diamine used in the synthesis reaction of the polyamic acid is preferably such that the amount of the acid anhydride group of the tetracarboxylic dianhydride is from 0.2 to 2 equivalents based on 1 equivalent of the amino group of the diamine, Is 0.7 to 1.2 equivalents.

The synthesis reaction of the polyamic acid is preferably carried out in an organic solvent at a temperature of preferably -20 ° C to 150 ° C, more preferably 0 to 100 ° C, preferably for 1 to 72 hours, more preferably 3 to 48 Time. Here, the organic solvent is not particularly limited as long as it can dissolve the produced polyamic acid, and examples thereof include 1-methyl-2-pyrrolidone, N, N-dimethylacetamide, Amide compounds such as 3-butoxy-N, N-dimethylpropanamide, 3-methoxy-N, N-dimethylpropanamide and 3-hexyloxy- Nonpolar compounds such as butyrolactone, tetramethyl urea, and hexamethylphosphoric triamide; phenol compounds such as m-cresol, xylenol, phenol, halogenated phenol, and the like. The amount (?) Of the organic solvent is preferably such that the total amount (?) Of the tetracarboxylic dianhydride and the diamine compound is 0.1 to 30% by weight based on the total amount (? +?) Of the reaction solution. When the organic solvent is used in combination with a poor solvent to be described later, the amount (?) Of the above-mentioned organic solvent should be understood as the total amount of the organic solvent and the poor solvent.

Alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, etc., which are poor solvents of polyamic acid, may be added to the organic solvent within a range that the polyamic acid produced is not precipitated. Specific examples of such a poor solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol, propylene glycol, But are not limited to, 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, Propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether, ethylene glycol diisopropyl ether, diethylene glycol diethyl ether, diethylene glycol diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol- , Ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloro There may be mentioned ethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, diisobutylketone, isoamylpropionate, isoamylisobutyrate and diisopentylether.

When an organic solvent and a poor solvent are used in combination, the amount of the poor solvent to be used can be appropriately set within a range in which the produced polyamic acid is not precipitated, but is preferably 30% by weight or less based on the total amount of the solvent, desirable.

In this way, a reaction solution obtained by dissolving polyamic acid is obtained. The polyamic acid solution may be used for the dehydration ring-closure reaction of the subsequent step as it is or may be used for the dehydration ring-closure reaction after isolating the polyamic acid contained in the reaction solution. Alternatively, after the isolated polyamic acid is purified, . The polyamic acid may be isolated by pouring the polyamic acid solution into a large amount of a poor solvent to obtain a precipitate and drying the precipitate under reduced pressure, or by a method of distilling off the polyamic acid solution by an evaporator under reduced pressure. The polyamic acid can also be purified by once or repeatedly performing the step of dissolving the polyamic acid thus obtained in an organic solvent and then precipitating it with a poor solvent or by distillation under reduced pressure using an evaporator.

[Dehydration ring closure reaction]

The imidized polymer contained in the liquid crystal aligning agent of the present invention may be a completely imidized product in which all of the amic acid structure possessed by the raw material polyamic acid is dehydrated and cyclized and only a part of the amic acid structure is dehydrated and cyclized, And an imide ring structure in which an imidazole ring structure coexists.

The imidized polymer contained in the liquid crystal aligning agent of the present invention preferably has an imidization rate of 30 mol% or more. The imidization ratio is more preferably 40 mol% or more, still more preferably 50 mol% or more, particularly preferably 60 mol% or more. By using an imidized polymer having an imidization ratio of 30 mol% or more, it is possible to obtain a liquid crystal aligning agent which provides a liquid crystal alignment film excellent in heat resistance and excellent in voltage-voltage leakage exceeding the conventionally known high imidation rate imidized polymer. In addition, in the liquid crystal aligning agent of the present invention, since the high-voltage leakage property of the liquid crystal alignment film to be formed is not impaired even when the imidization ratio of the imidized polymer is increased, the imidization rate can be set high without such restrictions, For example, not less than 80 mol%, and more practically, not more than 100%, a liquid crystal aligning agent capable of providing a liquid crystal alignment film having both a high heat resistance and a good voltage-leaking property can be obtained.

The imidization ratio is expressed as a percentage of the ratio of the number of imide ring structures to the sum of the number of amic acid structures and the number of imide ring structures in the imidized polymer. At this time, a part of the imide ring may be an isoimide ring. The imidization ratio can be measured by dissolving the imidized polymer in a suitable deuterated solvent (for example, deuterated dimethyl sulfoxide) and measuring ¹ H-NMR at room temperature (for example, 25 캜) using tetramethylsilane as a reference material From the result, it can be obtained by the following expression (1).

Imidization rate (%) = (1-A ¹ / A ² × α) × 100

(Where A ¹ is the peak area derived from the proton of the NH group near 10 ppm of chemical shift, A ² is the peak area derived from other protons, and? Is the precursor of the imidized polymer (polyamic acid ) &Lt; / RTI &gt; is the ratio of the number of other protons to one proton of the NH group)

The dehydration ring closure of the polyamic acid is preferably carried out by (1) heating the polyamic acid, or (2) dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring-closing catalyst to the solution, . &Lt; / RTI &gt;

The reaction temperature in the method of heating the polyamic acid of (1) is preferably 50 to 200 ° C, more preferably 60 to 170 ° C. The reaction time is preferably 1 to 8 hours, more preferably 3 to 5 hours. If the reaction temperature is less than 50 ° C, the dehydration ring-closure reaction does not proceed sufficiently, and if the reaction temperature exceeds 200 ° C, the molecular weight of the resulting imidized polymer may be lowered.

On the other hand, in the method of adding the dehydrating agent and dehydrating ring-closing catalyst to the solution of the polyamic acid of the above (2), for example, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used as the dehydrating agent. The amount of the dehydrating agent used is preferably 0.01 to 20 mol based on 1 mol of the amic acid structure of the polyamic acid although it differs depending on the desired imidization ratio. As the dehydration cyclization catalyst, for example, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used. However, it is not limited thereto. The amount of the dehydration ring-closing catalyst to be used is preferably 0.01 to 10 mol based on 1 mol of the dehydrating agent to be used. The imidization rate can be increased as the amount of the dehydrating agent and the dehydrating ring closure agent used is larger. Examples of the organic solvent used in the dehydration ring-closure reaction include organic solvents exemplified for use in the synthesis of polyamic acid. The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C. The reaction time is preferably 1 to 8 hours, more preferably 3 to 5 hours.

In the method (2), a reaction solution containing an imidized polymer is obtained as described above. This reaction solution can be used as it is for the preparation of a liquid crystal aligning agent or after the dehydrating agent and the dehydration ring-closing catalyst are removed from the reaction solution, the reaction solution can be used for preparing a liquid crystal aligning agent or after the imidized polymer is isolated, Or may be used in the production of a liquid crystal aligning agent after purification of the isolated imidized polymer. In order to remove the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, for example, a method such as solvent substitution can be applied. Isolation and purification of the imidized polymer can be performed by carrying out the same operation as described above as a method for isolation and purification of polyamic acid.

[Polymer of terminal modified type]

The imidized polymer contained in the liquid crystal aligning agent of the present invention may be a terminal modified type having a controlled molecular weight. By using the polymer of the terminal modified type, the coating property and the like of the liquid crystal aligning agent can be further improved without impairing the effect of the present invention. Such a terminal modified polymer can be produced by adding a molecular weight regulator to a polymerization reaction system when synthesizing a polyamic acid. Examples of the molecular weight regulator include acid monoanhydrides, monoamine compounds, and monoisocyanate compounds.

Examples of the acid anhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride and n-hexadecylsuccinic anhydride. have. Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, hexadecylamine, n-heptadecylamine, n-octadecylamine, n-octadecylamine, n-octadecylamine, Eicosylamine and the like. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

The use ratio of the molecular weight modifier is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the total amount of the tetracarboxylic acid dianhydride and diamine used in synthesizing the polyamic acid.

[Solution viscosity]

The imidized polymer obtained as described above preferably has a solution viscosity of 20 to 800 mPa 으로 when it is a 10 wt% solution, more preferably a solution viscosity of 30 to 500 mPa..

The solution viscosity (mPa 占 퐏) of the polymer is a value measured at 25 占 폚 using an E-type rotational viscometer for a polymer solution having a concentration of 10% by weight prepared by using a good solvent for the polymer.

<Other ingredients>

The vertical alignment type liquid crystal alignment film of the present invention contains the above-mentioned imidized polymer as an essential component, but may contain other components as necessary. Examples of such other components include a polymer other than the imidized polymer (hereinafter referred to as "another polymer"), an adhesion improver, and the like.

The other polymer can be used for improving the solution characteristics and electrical properties. Such another polymer is a polymer other than the imidized polymer obtained by dehydration ring closure of a polyamic acid obtained by reacting a tetracarboxylic dianhydride and a diamine containing the compound (A), for example, a tetracarboxylic dianhydride and a compound (Hereinafter referred to as "other polyamic acid") obtained by reacting a diamine containing no polyamic acid (A) (hereinafter referred to as "another imidized polymer" Poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylate, and the like can be given as examples of the poly (amic acid) ester, polyester, polyamide, polysiloxane, cellulose derivative, polyacetal, polystyrene derivative. Of these, other polyamic acids or other imidized polymers are preferred.

The use ratio of the other polymer refers to the sum of the polymer (imidized polymer obtained by dehydration ring closure of the polyamic acid obtained by reacting the tetracarboxylic dianhydride and the diamine containing the compound (A)) and other polymers, Hereinafter the same), preferably 30% by weight or less, and more preferably 20% by weight or less.

The above adhesiveness improver can be used for the purpose of improving the adhesiveness of the obtained liquid crystal alignment film to the substrate surface. Examples of such an adhesion improver include a compound having at least one epoxy group in the molecule (hereinafter referred to as an "epoxy compound"), a functional silane compound, and the like.

Examples of the epoxy compound 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-dibromoneopentyl glycol diglycidyl ether, 1,3,5 Tetraglycidyloxy-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidyl N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 3- (N-allyl-N-glycidyl) aminopropyltrimethoxy Silane, 3- (N, N-diglycidyl) aminopropyltrimethoxysilane, and the like.

The use ratio of the epoxy compound as described above is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight based on 100 parts by weight of the total amount of the polymer.

Examples of the functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxy Silane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyl triethylenetriamine, N- 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-aminopropyl trimethoxysilane, N- Aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane and the like.

The use ratio of the functional silane compound as described above is preferably 2 parts by weight or less, more preferably 0.01 to 0.2 parts by weight based on 100 parts by weight of the total amount of the polymer.

<Liquid Crystal Aligner>

The liquid crystal aligning agent of the present invention is constituted by dissolving and containing the imidized polymer as described above and optionally other components optionally blended in an organic solvent.

Examples of the organic solvent usable in the liquid crystal aligning agent of the present invention include N-methyl-2-pyrrolidone,? -Butyrolactone,? -Butyrolactam, N, N-dimethylformamide, N, N -Methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxy propionate, ethyl ethoxypropionate, ethylene glycol methyl ether, N-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), 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, 3-butoxy-N, N-dimethylpropanamide, 3-methoxy-N, N-dimethylpropanamide and 3-hexyloxy-N, N-dimethylpropanamide.

The solid concentration in the liquid crystal aligning agent of the present invention (the ratio of the total weight of components other than the solvent of the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc., To 10% by weight. That is, the liquid crystal aligning agent of the present invention is applied to the surface of the substrate as described later, and preferably, when heated, forms a coating film which becomes a liquid crystal alignment film. However, when the solid concentration is less than 1% by weight, On the other hand, when the solid concentration exceeds 10% by weight, the film thickness of the coating film becomes too large to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal aligning agent is increased and the coating property is lowered There is a case.

Particularly preferable ranges of the solid concentration are different depending on the method used when the liquid crystal aligning agent is applied to the substrate. For example, in the case of the spinner method, the solid content concentration is particularly preferably in the range of 1.5 to 4.5 wt%. In the case of the printing method, it is particularly preferable that the solid concentration is in the range of 3 to 9% by weight and the solution viscosity is in the range of 12 to 50 mPa · s. In the case of the ink-jet method, it is particularly preferable that the solid concentration is in the range of 1 to 5 wt% and the solution viscosity is in the range of 3 to 15 mPa · s accordingly.

The temperature for producing the liquid crystal aligning agent of the present invention is preferably 0 to 200 캜, more preferably 20 to 60 캜.

<Liquid crystal display element>

The liquid crystal display element of the present invention comprises the liquid crystal alignment layer formed of the liquid crystal aligning agent of the present invention as described above.

A preferable operation mode in the liquid crystal display element of the present invention is TN type, STN type, VA type or IPS type.

The liquid crystal display element of the present invention can be produced, for example, by the following steps (1) to (3). The step (1) differs depending on the desired operation mode, the preferred application method of the substrate, the liquid crystal aligning agent, and the heating temperature after application of the liquid crystal aligning agent. Steps (2) and (3) are common to each operation mode.

(1) First, the liquid crystal aligning agent of the present invention is applied onto a substrate, and then a coated film is formed on the substrate by heating the coated surface.

(1-1) In the case of producing a TN type, STN type or VA type liquid crystal display device, two substrates on which a patterned transparent conductive film is provided are paired, and on the respective transparent conductive film forming surfaces, Is preferably applied by an offset printing method, a spin coating method or an ink jet printing method, and then each coated surface is heated to form a coated film. Examples of the substrate include glass such as float glass and soda glass; A transparent substrate containing plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and poly (alicyclic olefin) can be used. As the transparent conductive film to be provided on one side of the substrate, an ITO film including indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ), a NESA film containing tin oxide (SnO ₂ ) In order to obtain a patterned transparent conductive film, for example, a method of forming a pattern by photoetching after forming a transparent conductive film without a pattern, a method of using a mask having a desired pattern in forming a transparent conductive film Or the like. When applying the liquid crystal aligning agent, a functional silane compound, a functional titanium compound and the like are previously coated on the surface of the substrate surface on which the coating film is to be formed, in order to further improve adhesion between the substrate surface and the transparent conductive film and the coating film A pretreatment may be performed.

The heating temperature after application of the liquid crystal aligning agent is preferably 30 to 300 캜, more preferably 40 to 250 캜, and the heating time is preferably 1 to 60 minutes, more preferably 10 to 30 minutes. The film thickness of the formed coating film is preferably 0.001 to 1 mu m, more preferably 0.005 to 0.5 mu m.

(1-2) On the other hand, in the case of manufacturing an IPS type liquid crystal display element, the conductive film formation surface of the substrate on which the transparent conductive film patterned in the comb-like pattern is provided and the conductive film formation surface of the opposite substrate on which the conductive film is not provided The liquid crystal aligning agent of the present invention is preferably applied by a roll coater method, a spinner method, or an inkjet printing method, respectively, and then each coated surface is heated to form a coated film.

The substrate and the material of the transparent conductive film, the method of patterning the transparent conductive film, and the pretreatment of the substrate are the same as those in the above (1-1).

The heating temperature after application of the liquid crystal aligning agent is preferably 80 to 300 ° C, more preferably 120 to 250 ° C, and the heating time is preferably 1 to 60 minutes, more preferably 10 to 30 minutes.

The preferable film thickness of the formed coating film is the same as that of the above (1-1).

In any of the cases (1-1) and (1-2), the liquid crystal aligning agent of the present invention forms a coating film which becomes an alignment film by removing the organic solvent after coating, but the liquid crystal aligning agent of the present invention is a polyamic acid or imide ring When the imidized polymer containing the structure and the amic acid structure is contained, the dehydrated ring-closure reaction may be further advanced by heating after forming the coating film, so that a more imaged coating film can be obtained.

(2) When the liquid crystal display element manufactured by the method of the present invention is a VA type liquid crystal display element, the coating film formed as described above can be used as it is as a liquid crystal alignment film, It can also be used afterwards.

On the other hand, when a liquid crystal display device other than the VA type is manufactured, a coating film formed as described above is subjected to rubbing treatment to form a liquid crystal alignment film.

The rubbing treatment can be carried out by a method of rubbing the coating film surface formed as described above in a predetermined direction with a roll wound with a cloth containing fibers such as nylon, rayon or cotton. Accordingly, the alignment ability of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film.

Further, the liquid crystal alignment film formed by the liquid crystal aligning agent of the present invention can be produced, for example, in Patent Document 6 (Japanese Unexamined Patent Application Publication No. 6-222366) or Patent Document 7 (Japanese Patent Application Laid-Open No. 6-281937 (Japanese Patent Application Laid-Open No. 5-107544) or a process of changing the pretilt angle of a part of the liquid crystal alignment film by irradiating a part of the liquid crystal alignment film as described in Japanese Patent Application Laid- After the resist film is formed on a part of the surface of the liquid crystal alignment film as described in the above, the rubbing treatment is performed in a direction different from the above-mentioned rubbing treatment and then the resist film is removed so that the liquid crystal alignment film has a liquid crystal aligning ability It is possible to improve the clock characteristic of the liquid crystal display element obtained.

(3) A liquid crystal cell is prepared by preparing two substrates on which a liquid crystal alignment film is formed as described above, and arranging the liquid crystal between two substrates arranged opposite to each other. Here, when the coating film is subjected to the rubbing treatment, the two substrates are opposed to each other so that the rubbing directions in the respective coating films are made to have a predetermined angle, for example, orthogonal or inversely.

In order to produce a liquid crystal cell, for example, the following two methods can be mentioned.

The first method is a conventionally known method. First, two substrates are placed opposite each other with a gap (cell gap) so that the respective liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded together using a sealing agent. Then, After the liquid crystal is injected and filled in the interval, the injection hole is sealed to manufacture the liquid crystal cell.

The second method is a method called ODF (One Drop Fill) method. An ultraviolet light curable sealing material is applied to a predetermined place on one of the two substrates on which the liquid crystal alignment film is formed and the liquid crystal is dropped on the liquid crystal alignment film surface and then the other substrate is bonded so that the liquid crystal alignment film is opposed And then the ultraviolet light is irradiated to the entire surface of the substrate to cure the sealing agent, whereby the liquid crystal cell can be manufactured.

In any method, it is preferable to heat the liquid crystal cell manufactured as described above to a temperature at which the liquid crystal used becomes an isotropic phase, and then gradually cool to room temperature to remove the flow alignment at the time of liquid crystal injection.

Further, by bonding a polarizing plate to the outer surface of the liquid crystal cell, the liquid crystal display element of the present invention can be obtained.

As the sealing agent, for example, an epoxy resin containing an aluminum oxide sphere as a curing agent and a spacer can be used. Examples of the liquid crystal include nematic liquid crystals and smectic liquid crystals. Among them, nematic liquid crystals are preferable, and examples thereof include a shift base type liquid crystal, an agglutinative liquid crystal, a biphenyl type liquid crystal, a phenylcyclohexane type liquid crystal, Biphenylcyclohexane-based liquid crystal, pyrimidine-based liquid crystal, dioxane-based liquid crystal, bicyclooctane-based liquid crystal, quaternary-based liquid crystal and the like can be used. Examples of the liquid crystal include cholesteric liquid crystals such as cholestyl chloride, cholesteryl nonoate and cholesteryl carbonate; Chiral agents such as those sold under the trade names "C-15" and "CB-15" (manufactured by Merck); and a ferroelectric liquid crystal such as p-disiloxybenzylidene-p-amino-2-methylbutyl cinnamate.

As the polarizing plate to be bonded to the outer surface of the liquid crystal cell, a polarizing plate in which a polarizing film called "H film " in which iodine is absorbed while polyvinyl alcohol is oriented in a stretched polyvinyl alcohol is sandwiched between cellulose acetate protective films or a polarizing plate made of H film itself can be given.

The liquid crystal display element of the present invention can solve or alleviate the abnormal lighting in a short period of time even when the panel is abnormally turned on by the static electricity generated from the electrostatic chuck used in the manufacturing process of the liquid crystal display element of the present invention, It is available for improvement.

The liquid crystal display element of the present invention produced as described above has a lower display performance than that of a conventionally known liquid crystal display element even when the liquid crystal display element is continuously driven for a long time. Specifically, for example, The light leakage of the backlight, which is thought to be caused by the orientation defects, does not occur.

<Examples>

Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to these examples.

In the following Synthesis Examples, N, N'-bis (4-aminophenyl) piperazine was commercially available from Wakayama Seika Kogyo Co., Ltd.

The solution viscosities of the polymers in the synthesis examples were all values measured at 25 캜 using an E-type viscometer.

Synthesis Example 1 (Synthesis Example 1 of imidized polymer)

224 g (1.0 mole) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic acid anhydride, 96.1 g (0.89 mole) of p-phenylenediamine as diamine, 3,6-bis (0.10 mole) of N, N'-bis (4-aminophenyl) piperazine were dissolved in 3,100 g of N-methyl-2-pyrrolidone, The reaction was carried out for a period of time to obtain a solution containing 10 wt% of polyamic acid. The solution viscosity of this polyamic acid solution was 90 mPa s.

Subsequently, 600 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 136 g of pyridine and 105 g of acetic anhydride were added and the dehydration ring-closure reaction was carried out at 110 DEG C for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was replaced with a solvent with new? -Butyrolactone (by removing the pyridine and acetic anhydride used in the dehydration ring-closure reaction from the system by solvent substitution, the same applies hereinafter) 1,500 g of a solution containing 20% by weight of the imidization polymer (A-1) at a rate of about 88% was obtained. A small amount of this solution was collected, and the solution viscosity measured as a solution having a concentration of 6.0% by weight by adding? -Butyrolactone was 22 mPa 占 퐏.

Synthesis Example 2 (Synthesis Example 2 of imidized polymer)

112 g (0.50 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic acid anhydride, 38.0 g (0.35 mol) of p-phenylenediamine as diamine, 3 (3,5-diaminobenzoyloxy (0.10 mole) of cholestan and 13.4 g (0.050 mole) of N, N'-bis (4-aminophenyl) piperazine were dissolved in 1,900 g of N-methyl-2-pyrrolidone, To obtain a solution containing 10 wt% of polyamic acid. The solution viscosity of this polyamic acid solution was 58 mPa s.

Subsequently, 600 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 116 g of pyridine and 90 g of acetic anhydride were added, followed by dehydration ring closure reaction at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with fresh N-methyl-2-pyrrolidone and then concentrated to obtain a solution containing about 15% by weight of an imidization polymer (A-2) having an imidization rate of about 92% 1,430 g was obtained. A small amount of this solution was collected, and the solution viscosity measured as a solution having a concentration of 6.0% by weight by adding? -Butyrolactone was 23 mPa 占 퐏.

Synthesis Example 3 (Synthesis Example 3 of imidized polymer)

(0.50 mole) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 49 g (0.35 mole) of p-phenylenediamine as diamine, N, N'-bis (4- (0.050 mol) and 3 (3,5-diaminobenzoyloxy) cholestane (26 g, 0.050 mol) were dissolved in 1,800 g of N-methyl-2-pyrrolidone, The reaction was carried out for 6 hours to obtain a solution containing 10 wt% of polyamic acid. The solution viscosity of this polyamic acid solution was 60 mPa..

Then, 1,800 g of NMP was added to the obtained polyamic acid solution, and 40 g of pyridine and 51 g of acetic anhydride were added and the dehydration ring-closure reaction was carried out at 110 DEG C for 4 hours. After the dehydration ring closure reaction, about 1,200 g of a solution containing 15% by weight of the imidized polymer (A-3) having an imidization rate of about 55% was obtained by replacing the solvent in the system with fresh N-methyl- .

A small amount of this solution was collected and the solution viscosity was measured as a solution having a concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 85 mPa.s.

Synthesis Example 4 (Synthesis Example 4 of imidized polymer)

110 g (0.50 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride as tetracarboxylic dianhydride, 32 g (0.30 mol) of p-phenylenediamine as diamine, 4,4'-diaminodiphenyl 13 g (0.050 mol) of N, N'-bis (4-aminophenyl) piperazine and 26 g (0.05 mol) of 3 (3,5-diaminobenzoyloxy) cholestane were dissolved in N -Methyl-2-pyrrolidone, and the reaction was carried out at 60 DEG C for 6 hours to obtain a solution containing the polyamic acid. A small amount of the obtained polyamic acid solution was fractionated and N-methyl-2-pyrrolidone was added to measure a solution having a concentration of 10% by weight, whereby the solution viscosity was 60 mPa.s.

Then, 1,800 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 80 g of pyridine and 100 g of acetic anhydride were added and the dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, about 1,200 g of a solution containing 15% by weight of an imidization polymer (A-4) having an imidization rate of about 80% was obtained by replacing the solvent in the system with fresh N-methyl- . A small amount of this solution was collected, and the solution viscosity measured as a solution having a concentration of 10% by weight by adding? -Butyrolactone was 87 mPa 占 퐏.

Synthesis Example 5 (Synthesis Example 5 of imidized polymer)

(0.50 mole) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic acid anhydride, 27.0 g (0.25 mole) of p-phenylenediamine as diamine and N, N'-bis Phenyl) piperazine (67.0 g, 0.25 mol) was dissolved in 1,900 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours to obtain a solution containing 10 wt% of polyamic acid. The solution viscosity of this polyamic acid solution was 80 mPa..

Subsequently, 600 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 136 g of pyridine and 105 g of acetic anhydride were added and the dehydration ring-closure reaction was carried out at 110 DEG C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new gamma -butyrolactone solvent and then concentrated to obtain 1,100 g of a solution containing 15% by weight of imidized polymer (A-5) having an imidization rate of about 92%. A small amount of this solution was collected, and the solution viscosity measured as a solution having a concentration of 6.0% by weight by adding? -Butyrolactone was 24 mPa 占 퐏.

Synthesis Example 6 (Synthesis Example 6 of imidized polymer)

(0.50 mole) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic acid anhydride, 38 g (0.45 mole) of p-phenylenediamine as diamine, and N, N'-bis Phenyl) piperazine was dissolved in 1,900 g of N-methyl-2-pyrrolidone, and the reaction was carried out at room temperature for 6 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyamic acid solution was fractionated and concentrated under reduced pressure to give a solution viscosity of 82 mPa 으로서 as a solution having a concentration of 10% by weight.

Subsequently, 600 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 136 g of pyridine and 105 g of acetic anhydride were added and the dehydration ring-closure reaction was carried out at 110 DEG C for 4 hours. After the dehydration cyclization reaction, the solvent in the system was replaced with a new gamma -butyrolactone solvent and then concentrated to obtain 1,100 g of a solution containing 15% by weight of an imidized polymer (A-6) having an imidization ratio of about 90%. A small amount of this solution was collected, and the solution viscosity measured as a solution having a concentration of 6.0% by weight by adding? -Butyrolactone was 23 mPa 占 퐏.

Synthesis Example 7 (Synthesis Example 7 of the imidized polymer)

168 g (0.75 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic acid dianhydride, and 168 g (0.75 mol) of 1,3,3a, 4,5,9b-hexahydro- 157 g (0.25 mol) of p-phenylenediamine, 32 g (0.30 mol) of p-phenylenediamine as a diamine, , 80 g (0.40 mol) of 4,4'-diaminodiphenyl ether, 85 g (0.20 mol) of bis [4- (4-aminophenoxy) phenyl] sulfone and N, N'- (0.10 mol) of piperazine was dissolved in 4,200 g of N-methyl-2-pyrrolidone, and the mixture was reacted at room temperature for 6 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyamic acid solution was collected, and the solution viscosity was measured as a solution having a concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 85 mPa 占 퐏.

Next, 1,000 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 150 g of pyridine and 200 g of acetic anhydride were added, followed by dehydration ring closure reaction at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new gamma -butyrolactone solvent and then concentrated to obtain 2,600 g of a solution containing 15% by weight of the imidized polymer (A-7) having an imidization rate of about 88%.

Synthesis Example 8 (Synthesis Example 8 of imidized polymer)

112 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 38 g (0.25 mol) of 3,5-diaminobenzoic acid as diamine, N, N'-bis (0.25 mol) of 4-aminophenyl) piperazine was dissolved in 2,100 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyamic acid solution was fractionated and concentrated under reduced pressure to give a solution viscosity of 60 mPa 으로서 as a 10 wt% solution.

Next, 1,000 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 150 g of pyridine and 200 g of acetic anhydride were added, followed by dehydration ring closure reaction at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new gamma -butyrolactone solvent and then concentrated to obtain 1,400 g of a solution containing 15% by weight of an imidized polymer (A-8) having an imidization rate of about 88%.

Synthesis Example 9 (Synthesis Example 9 of imidized polymer)

112 g (0.50 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride as tetracarboxylic dianhydride and 134 g (0.50 mol) of N, N'-bis (4-aminophenyl) Dissolved in 2100 g of N-methyl-2-pyrrolidone, and reacted at room temperature for 6 hours to obtain a solution containing 10 wt% of polyamic acid. The solution viscosity of this polyamic acid solution was 100 mPa..

Next, 1,000 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 150 g of pyridine and 200 g of acetic anhydride were added, followed by dehydration ring closure reaction at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new gamma -butyrolactone solvent and then concentrated to obtain 1,600 g of a solution containing 15% by weight of an imidized polymer (A-9) having an imidization rate of about 90%.

Comparative Synthesis Example 1 (Synthesis Example 1 of other imidized polymer)

224 g (1.0 mole) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic acid anhydride, 107 g (0.99 mole) of p-phenylenediamine as diamine, 3,6-bis (4-aminobenzoyl (0.10 mole) of N, N'-bis (4-aminophenyl) piperazine was dissolved in 1,260 g of N-methyl-2-pyrrolidone, For a period of time to obtain a solution containing the polyamic acid. A small amount of the obtained polyamic acid solution was collected, and the solution viscosity was measured as a solution having a concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 90 mPa.s.

Subsequently, 600 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 136 g of pyridine and 105 g of acetic anhydride were added and the dehydration ring-closure reaction was carried out at 110 DEG C for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was replaced with a new? -Butyrolactone solvent and then concentrated to obtain 1,800 g of a solution containing 15% by weight of polyimide (B-1) having an imidization rate of about 88%.

A small amount of this solution was collected, and the solution viscosity measured as a solution having a concentration of 6.0% by weight by adding? -Butyrolactone was 22 mPa 占 퐏.

Comparative Synthesis Example 2 (Synthesis Example 2 of another imidized polymer)

112 g (0.50 mole) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic acid anhydride, 43.0 g (0.40 mole) of p-phenylenediamine as diamine, and 3 g of 3,5-diaminobenzoyloxy ) 53.0 g (0.10 mol) of cholestane were dissolved in 1,230 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyamic acid solution was collected, and the solution viscosity was measured as a solution having a concentration of 10% by weight by adding N-methyl-2-pyrrolidone to obtain 58 mPa.s.

Subsequently, 600 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 116 g of pyridine and 90 g of acetic anhydride were added, followed by dehydration ring closure reaction at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with fresh N-methyl-2-pyrrolidone and then concentrated to obtain a solution containing about 15% by weight of an imidization polymer (B-2) having an imidization rate of about 92% 1,000 g was obtained. A small amount of this solution was collected, and the solution viscosity measured as a solution having a concentration of 6.0% by weight by adding? -Butyrolactone was 23 mPa 占 퐏.

Comparative Synthesis Example 3 (Synthesis Example 3 of other imidized polymer)

110 g (0.50 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride as tetracarboxylic acid dianhydride, 56 g (0.40 mol) of p-phenylenediamine as diamine and 3 (3,5-diaminobenzoyl Oxy) cholestane were dissolved in 1,100 g of N-methyl-2-pyrrolidone and the reaction was carried out at 60 DEG C for 6 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyamic acid solution was fractionated and N-methyl-2-pyrrolidone was added to measure a solution having a concentration of 10% by weight, whereby the solution viscosity was 60 mPa.s.

Then, 1,800 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 40 g of pyridine and 51 g of acetic anhydride were added, followed by dehydration ring closure reaction at 110 ° C for 4 hours. After the dehydration ring closure reaction, about 1,150 g of a solution containing 15% by weight of the imidized polymer (B-3) having an imidization rate of about 50% was obtained by replacing the solvent in the system with fresh N-methyl- .

A small amount of this solution was collected and the solution viscosity was measured as a solution having a concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 85 mPa.s.

Comparative Synthesis Example 4 (Synthesis Example 4 of another imidized polymer)

110 g (0.50 mol) of 2,3,5-tricarboxycyclopentylacetic acid imumate as tetracarboxylic dianhydride, 44 g (0.35 mol) of p-phenylenediamine as a diamine, 4,4'-diaminodiphenyl 20 g (0.1 mol) of methane and 26 g (0.05 mol) of 3 (3,5-diaminobenzoyloxy) cholestane were dissolved in 800 g of N-methyl-2-pyrrolidone and reacted at 60 DEG C for 6 hours To obtain a solution containing polyamic acid. A small amount of the obtained polyamic acid solution was fractionated and N-methyl-2-pyrrolidone was added to measure a solution having a concentration of 10% by weight, whereby the solution viscosity was 60 mPa.s.

Then, 1,800 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 80 g of pyridine and 100 g of acetic anhydride were added and the dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, about 1,200 g of a solution containing 15% by weight of the imidized polymer (B-4) having an imidization rate of about 80% was obtained by replacing the solvent in the system with fresh N-methyl-2-pyrrolidone .

A small amount of this solution was collected, and the solution viscosity measured as a solution having a concentration of 10% by weight by adding? -Butyrolactone was 87 mPa 占 퐏.

Comparative Synthesis Example 5 (Synthesis Example 5 of another imidized polymer)

(0.50 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic acid anhydride and 54 g (0.50 mol) of p-phenylenediamine as diamine were dissolved in N-methyl-2-pyrrolidone 1,260 g and reacted at room temperature for 6 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyamic acid solution was fractionated and the solution viscosity was measured as a solution having a concentration of 10% by weight by adding N-methyl-2-pyrrolidone to 80 mPa.s.

Subsequently, 600 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 136 g of pyridine and 105 g of acetic anhydride were added and the dehydration ring-closure reaction was carried out at 110 DEG C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new gamma -butyrolactone solvent and then concentrated to obtain 1,000 g of a solution containing 15% by weight of imidation polymer (B-5) having an imidization rate of about 93%.

A small amount of this solution was collected, and the solution viscosity measured as a solution having a concentration of 6.0% by weight by adding? -Butyrolactone was 24 mPa 占 퐏.

Comparative Synthesis Example 6 (Synthesis Example 6 of another imidized polymer)

168 g (0.75 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic acid dianhydride, and 168 g (0.75 mol) of 1,3,3a, 4,5,9b-hexahydro- 157 g (0.25 mol) of p-phenylenediamine (43 g, 0.40 mol) as diamine, (0.40 mol) of 4,4'-diaminodiphenyl ether and 85 g (0.20 mol) of bis [4- (4-aminophenoxy) phenyl] sulfone were added to 2,700 g , And the reaction was carried out at room temperature for 6 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyamic acid solution was collected, and the solution viscosity was measured as a solution having a concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 85 mPa 占 퐏.

Next, 1,000 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 150 g of pyridine and 200 g of acetic anhydride were added, followed by dehydration ring closure reaction at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new gamma -butyrolactone solvent and then concentrated to obtain 2,600 g of a solution containing 15% by weight of an imidized polymer (B-6) having an imidization rate of about 88%.

Comparative Synthesis Example 7 (Synthesis Example 7 of another imidized polymer)

(0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride and 76 g (0.50 mol) of 3,5-diaminobenzoic acid as a diamine were dissolved in N-methyl-2- Dissolved in 2,100 g of ralidomide, and reacted at room temperature for 6 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyamic acid solution was fractionated and concentrated under reduced pressure to give a solution viscosity of 55 mPa 으로서 as a solution having a concentration of 10% by weight.

Next, 1,000 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 150 g of pyridine and 200 g of acetic anhydride were added, followed by dehydration ring closure reaction at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new gamma -butyrolactone solvent and then concentrated to obtain 1,200 g of a solution containing 15% by weight of imidized polymer (B-7) having an imidization rate of about 85%.

Example 1

? -Butyrolactone, N-methyl-2-pyrrolidone and butyl cellosolve were added to a solution containing the imidized polymer (A-1) obtained in Synthesis Example 1 in a mixed solvent of? -Butyrolactone: N, N ', N'-tetraglycidyl-4,4'-tetramethylphenol as an adhesive property improver was added in such a manner that the weight ratio of: -Diaminodiphenylmethane was added in an amount of 2 parts by weight based on 100 parts by weight of the imidized polymer contained in the polymer solution to prepare a solution having a solid concentration of 3.5% by weight. This solution was sufficiently stirred, and then filtered using a filter having an opening diameter of 1 탆 to prepare a liquid crystal aligning agent.

Using this liquid crystal aligning agent, evaluation was carried out as follows.

&Lt; Production and Evaluation of Liquid Crystal Display Device >

[Production of liquid crystal display device]

(1) Formation of coating film of liquid crystal aligning agent

The liquid crystal aligning agent prepared above was applied onto a transparent conductive film containing an ITO film provided on one side of a glass substrate having a thickness of 1 mm under the conditions of a rotation number of 2,000 rpm and a rotation time of 20 seconds by using a spinner, To remove the solvent, thereby forming a film having a film thickness of 0.08 mu m.

(2) Rubbing treatment

The rubbing treatment was carried out by a rubbing machine having a roll having a rayon cloth wound thereon under the conditions of a roll rotation speed of 400 rpm, a stage moving speed of 3 cm / sec, and a piercing length of 0.4 mm, Thereby giving a liquid crystal aligning ability and forming a liquid crystal alignment film.

(3) Cleaning and drying of substrate with liquid crystal alignment film

The substrate having the liquid crystal alignment film obtained above was ultrasonically cleaned in ultrapure water for 1 minute and then dried in a 100 ° C clean oven for 10 minutes.

By repeating the above operations (1) to (3), two substrates (one pair) having liquid crystal alignment films were produced.

(4) injection of liquid crystal and adhesion of polarizer

Subsequently, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 占 퐉 was applied to the outer edge portions of the substrate having the liquid crystal alignment film of the pair of liquid crystal alignment films, and then the liquid crystal alignment film surfaces were superimposed on each other so as to face each other, And cured. Subsequently, a nematic liquid crystal (MLC-6221, manufactured by Merck & Co., Inc.) having a positive value of anisotropy of dielectric constant was charged between the substrates from the liquid crystal injection port, the liquid crystal injection hole was sealed with an acrylic light curing adhesive, To thereby produce a liquid crystal display element.

[Evaluation of liquid crystal display element]

(1) Evaluation of liquid crystal alignment property

The above-prepared liquid crystal display element was observed using an optical microscope. At this time, when the light leakage was not observed, the liquid crystal alignment property was evaluated as "good ", and the light leakage was observed as the liquid crystal alignment property"

(2) Evaluation of high voltage leakage

After applying a DC voltage of 10 V for 1 second to the liquid crystal display device manufactured as described above, the circuit was left in an open state, and the change of the intensity of transmitted light transmitted through the liquid crystal cell with time was observed, And the time until returning to the state was measured. The time required for this liquid crystal display element to return to the initial transmittance state was evaluated as "Good" when the time was 20 minutes or less, and "Good" when the time exceeded 20 minutes was evaluated as " Min, and the high-voltage leakage property was "good".

(3) Evaluation of heat resistance (heat-resistant stress test)

First, a voltage of 5 V was applied to the liquid crystal display device manufactured in the above manner at an application time of 60 microseconds and a span of 167 milliseconds, and the voltage maintenance ratio after 167 milliseconds from the application of the release voltage was measured. The value at this time was defined as the initial voltage holding ratio (VHR _BF ). After the VHR _BF measurement, the liquid crystal display device was placed in an oven at 100 캜 and heat stress was applied for 1,000 hours. Subsequently, the liquid crystal display element was allowed to stand at room temperature, cooled to room temperature, and then the voltage holding ratio (VHR _AF ) after thermal stress was measured in the same manner as described above.

The rate of change of the voltage holding ratio before and after the application of the thermal stress was determined from the VHR _BF and the VHR _AF measured as described above. When the rate of change was less than 5.0%, the heat resistance was evaluated as " The heat resistance of the liquid crystal display element was "good &quot;.

Example 2

&Lt; Preparation of liquid crystal aligning agent &

An amount corresponding to 100 parts by weight of the imidized polymer (A-2) in the solution containing the imidized polymer (A-2) obtained in the above Synthesis Example 2 was converted to N- N, N ', N', N'-tetramethylcyclohexanecarboxylic acid as an adhesive property improving agent, and the ratio of N-methyl-2-pyrrolidone to butyl cellosolve was 50/50 by weight. 2 parts by weight of tetraglycidyl-4,4'-diaminodiphenylmethane was added to prepare a solution having a solid concentration of 3.5% by weight. This solution was sufficiently stirred, and then filtered using a filter having an opening diameter of 1 탆 to prepare a liquid crystal aligning agent.

&Lt; Production and Evaluation of Liquid Crystal Display Device >

(MLC-2038, manufactured by Merck & Co., Inc.) having negative anisotropy of dielectric constant as a liquid crystal in Example 1 was used, and in the liquid crystal display element manufacturing process, the "(2) rubbing" 3) Cleaning and drying of liquid crystal alignment film-attached substrate "was not carried out, liquid crystal display devices were produced in the same manner as in Example 1, and liquid crystal alignment properties and heat resistance were evaluated. The results are shown in Table 1 below.

Examples 3 and 4

A liquid crystal aligning agent was prepared in the same manner as in Example 2 except that each of the types shown in Table 1 was used as the imidized polymer in the amount shown in Table 1, and a liquid crystal display element was produced and evaluated. The results are shown in Table 1.

Example 5 (Reference Example)

&Lt; Preparation of liquid crystal aligning agent &

An amount corresponding to 100 parts by weight of the imidized polymer (A-5) in terms of the imidized polymer (A-5) obtained in Synthetic Example 5 was taken, and an amount of N, 10 parts by weight of N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane and 10 parts by weight of methyl 3- [2- (3-trimethoxysilylpropylamino) ethyl Amino] propionate, and further adding? -Butyrolactone and butyl cellosolve so that the? -Butyrolactone: butyl cellosolve ratio was 80:20 by weight to obtain a solid content concentration of 3.5% by weight, Lt; / RTI &gt; This solution was filtered using a filter having a pore size of 1 占 퐉 to prepare a liquid crystal aligning agent.

&Lt; Production and Evaluation of Liquid Crystal Display Device >

A liquid crystal display device was produced in the same manner as in Example 1 except that a nematic liquid crystal (MLC-2019, manufactured by Merck & Co., Inc.) having a positive dielectric constant anisotropy was used as the liquid crystal in Example 1, and liquid crystal alignability and heat resistance Were evaluated. The results are shown in Table 1.

Examples 6 to 9 (all reference examples)

A liquid crystal aligning agent was prepared in the same manner as in Example 5 except that each of the types shown in Table 1 was used as the imidized polymer in the amounts shown in Table 1, and a liquid crystal display device was produced and evaluated. The results are shown in Table 1.

Comparative Example 1

A liquid crystal aligning agent was prepared in the same manner as in Example 1, except that the kind of the imidized polymer shown in Table 1 was used in an amount as shown in Table 1, and a liquid crystal display device was produced and evaluated. The results are shown in Table 1.

Comparative Examples 2 to 4

A liquid crystal aligning agent was prepared in the same manner as in Example 2 except that each of the types shown in Table 1 was used as the imidized polymer in the amount shown in Table 1, and a liquid crystal display device was produced and evaluated. The results are shown in Table 1.

Comparative Examples 5 to 7

A liquid crystal aligning agent was prepared in the same manner as in Example 5 except that each of the types of imidized polymers described in Table 1 was used in amounts as shown in Table 1, and a liquid crystal display device was produced and evaluated. The results are shown in Table 1.

The abbreviations in the "type" column of the adhesion improver of Table 1 have the following meanings respectively.

[Epoxy Compound]

GAPM: N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane

[Functional silane compound]

MSPP: Methyl 3- [2- (3-trimethoxysilylpropylamino) ethylamino] propionate

Note that the description in the column of "liquid crystal name"

6221: MLC-6221 (trade name, manufactured by Merck Ltd.)

2038: MLC-2038 (trade name, manufactured by Merck Ltd.)

2019: MLC-2019 (trade name, manufactured by Merck Ltd.)

Claims (10)

Tetracarboxylic dianhydride, a compound having a structure represented by the following formula (A) and two amino groups, a compound represented by the following formula (D-III), and a compound represented by the following formula The reaction of the diamine containing at least one member selected from the group consisting of 4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether and bis [4- (4-aminophenoxy) phenyl] Wherein the liquid crystal aligning agent comprises an imidized polymer obtained by dehydrating and ring closure of a polyamic acid obtained by condensation polymerization. &Lt; Formula (A)

(In the formula (A), "*" [Formula D-III]

(Wherein R ⁹ is -O-, -COO-, -OCO-, -NHCO-, -CONH- or -CO-, and R ¹⁰ is a steroid skeleton, a trifluoromethylphenyl group, a trifluoromethyl group, R ¹¹ is an alkyl group having 1 to 4 carbon atoms, and a 3 is an integer of 0 to 3. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, The liquid crystal aligning agent according to claim 1, wherein the compound represented by the formula (A) and the compound having two amino groups is a compound represented by the following formula (A-1). [A-1]

(In the formula (A-1), each of U ¹ and U ² is independently an alkylene group having 2 to 5 carbon atoms or a divalent alicyclic group having 4 to 6 carbon atoms, or a divalent organic group containing an aromatic ring having 6 to 10 being) The liquid crystal aligning agent according to claim 1, wherein the ratio of the structure represented by the formula (A) and the compound having two amino groups is 1 mol% or more based on the total diamine. The liquid crystal aligning agent according to claim 1, wherein R ⁹ in the formula (D-III) is -O- or -COO-, and R ¹⁰ is a monovalent organic group having a steroid skeleton. 2. The process according to claim 1, wherein the tetracarboxylic dianhydride is 2,3,5-tricarboxycyclopentylacetic dianhydride and 1,3,3a, 4,5,9b-hexahydro-8-methyl- 2-c] furan-1, 3-dione. 2. The liquid crystal aligning agent according to claim 1, wherein the liquid crystal aligning agent is at least one selected from the group consisting of: The liquid crystal aligning agent according to claim 1, wherein the imidization ratio of the imidized polymer is 30% or more. The liquid crystal aligning agent according to claim 6, wherein the imidization ratio of the imidized polymer is 50% or more. A liquid crystal display element comprising a liquid crystal alignment film formed of the liquid crystal aligning agent according to any one of claims 1 to 7. delete delete