KR20090100274A - Liquid crystal aligning agent and liquid crystal display device - Google Patents

Abstract

PURPOSE: A liquid crystal alignment agent is provided to produce a liquid crystal alignment film in which ununiform alignment due to liquid crystal drop does not occur even if an ODF method is used in a liquid crystal recharge process. CONSTITUTION: A liquid crystal alignment agent comprises polyamic acid and at least one polymer. The polyamic acid is obtained by reacting tetracarboxylic acid dianhydride and diamine. The diamine includes a compound represented by chemical formula 1 or 2. The polymer is selected from the group consisting of imidized polymer of the polyamic acid. In chemical formula 1 and 2, n1 is independently an integer of 1 ~ 8.

Description

Liquid crystal aligning agent and liquid crystal display element {LIQUID CRYSTAL ALIGNING AGENT AND LIQUID CRYSTAL DISPLAY DEVICE}

This invention relates to a liquid crystal aligning agent and a liquid crystal display element.

At present, as a liquid crystal display element, the liquid crystal aligning film containing polyimide etc. is formed in the surface of the board | substrate with which the transparent conductive film is provided, and it is set as the board | substrate for liquid crystal display elements, and the pair (two sheets) is opposingly arranged in the clearance gap. A so-called twisted nematic liquid crystal in which a layer of a nematic liquid crystal having positive dielectric anisotropy is filled to form a sandwich cell, and the long axis of the liquid crystal molecule is continuously twisted 90 ° from one substrate to the other. TN type liquid crystal display elements having a cell are known. In addition, recently, a STN (Super Twisted Nematic) type liquid crystal display device having a higher duty ratio than a TN type liquid crystal display device has been developed. This STN type liquid crystal display element uses a mixture of a nematic liquid crystal and a chiral agent, which is an optically active substance, as a liquid crystal, and is produced by causing the long axis of the liquid crystal molecules to be continuously twisted over 180 ° between substrates. It is to use the birefringence effect. The orientation of the liquid crystal in these TN type liquid crystal display elements and STN type liquid crystal display elements is normally expressed by the liquid crystal aligning film in which the rubbing process was performed.

Moreover, as a kind of liquid crystal display element different from these, the VA (Vertical Alignment) type liquid crystal display element which orientates the liquid crystal molecule which has negative dielectric anisotropy perpendicular to a board | substrate is also known. In the VA liquid crystal display device, when a liquid crystal molecule is inclined toward a direction parallel to the substrate by applying a voltage between the substrates, the liquid crystal molecules need to be inclined toward one direction in the substrate plane from the substrate normal direction. As a means for this, for example, an MVA method (patent document 1 and a non-patent document 1) for forming projections on the ITO to control the alignment direction of the liquid crystal, and an EVA method for controlling the orientation direction by studying the electrode structure (the following ratio). Patent document 2), the photo-alignment system (following nonpatent literature 3) etc. which modify an orientation film by light irradiation and control an orientation direction, etc. are proposed.

However, polyimide obtained by polycondensation of tetracarboxylic dianhydride and diamine is known to be excellent in heat resistance and chemical resistance. Accordingly, polyimide is used for various applications, and in particular, it is widely used as a protective material and an insulating material in the electric and electronic materials field. In particular, in the orientation film use of a liquid crystal display element, polyimide was used entirely from the viewpoint of the durability of a coating film. However, as the performance of the liquid crystal display element is improved, the display density is increased, the surface characteristics of the polyimide are particularly important, and excellent performance is required for the conventional polyimide alignment film. For example, more advanced performance expression is calculated | required about liquid crystal orientation control force, pretilt angle characteristic, afterimage characteristic, etc.

The liquid crystal aligning film containing a polyimide is apply | coated on the board | substrate by apply | coating on the board | substrate the liquid crystal aligning agent which is an organic solvent solution of the polyamic acid which is a polyimide precursor normally, or the soluble imidation polymer formed by dehydrating and ring-closing this, and imidating by heating. Obtained. According to Patent Document 2, a liquid crystal aligning film providing a stable pretilt angle is formed by using a liquid crystal aligning agent containing a polyamic acid or an imidized polymer thereof synthesized from a diamine having a structure represented by the following formula (3) or (4). It is described. This technique aims at stabilizing the pretilt angle by introducing a liquid crystal like skeleton derived from the diamine represented by the formula (3) or (4) to the liquid crystal alignment film. It is described that the liquid crystal aligning film for VA type liquid crystal display elements (henceforth a "vertical alignment liquid crystal aligning film") can be formed by applying the polymer which has such a structure. However, in patent document 2, the voltage retention and the afterimage characteristic are not improved.

(In Formulas 3 and 4, n2 is 4 or 6, respectively.)

On the other hand, Patent Document 3 below contains a polymer synthesized using 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-anhydride as tetracarboxylic dianhydride. It is reported that high voltage retention in high temperature area | region is achieved by using the liquid crystal aligning agent mentioned above. However, the afterimage property is not improved even in this technique.

Here, if the manufacturing process of a liquid crystal display element is demonstrated, recent advances have made remarkable progress. For example, as a method of filling a liquid crystal material in the space | gap of a pair of board | substrates, the method of conventionally arrange | positioning a pair of board | substrates facing a gap, and then storing a liquid crystal in the space | gap was used. However, as a new method instead of this, a liquid crystal dropping method (One Drop Fill = ODF) has recently been proposed (Patent Document 4). The ODF method is a method of dropping droplets of liquid crystal material onto a liquid crystal alignment film of a substrate, and bonding the substrate in vacuum while spreading the liquid crystal droplets from the opposite substrate. According to this method, there is an advantage that the time required for the liquid crystal filling step can be greatly shortened, but a dropping trace occurs in the liquid crystal dropping portion, and the dropping trace becomes a liquid crystal alignment unevenness when the liquid crystal display element is used. There is this. It is thought that this liquid crystal aligning nonuniformity originates in the orientation of a liquid crystal aligning film being locally disturbed by the impact at the time of dropping a liquid crystal material on a liquid crystal aligning film. In order to solve this problem, a solution from a liquid crystal aligning film material has been attempted (Patent Document 5), but it is still insufficient, and in particular, the suppression of the liquid crystal alignment nonuniformity in manufacturing a VA type liquid crystal display element by an ODF method is required. It is becoming.

[Patent Document 1] Japanese Patent Application Laid-Open No. 11-258605

[Patent Document 2] Japanese Patent Application Laid-Open No. 09-278724

[Patent Document 3] Japanese Patent Laid-Open No. 11-84391

[Patent Document 4] Japanese Unexamined Patent Publication No. 6-3635

[Patent Document 5] Japanese Patent Application Laid-Open No. 2007-183564

[Patent Document 6] Japanese Unexamined Patent Publication No. 6-222366

[Patent Document 7] Japanese Unexamined Patent Publication No. 6-281937

[Patent Document 8] Japanese Patent Application Laid-Open No. 5-107544

[Patent Document 9] Japanese Patent Application Laid-Open No. 4-281427

[Non-Patent Document 1] "Liquid crystal" vol. 3, No. 2, 117 (1999)

[Nonpatent Document 2] "Liquid crystal" vol. 3, No. 4, 272 (1999)

[Non-Patent Document 3] "Jpn J. Appl. Phys." Vol. 36, L 428 (1997)

The 1st objective of this invention is providing the liquid crystal aligning agent which provides the liquid crystal aligning film excellent in the voltage retention and afterimage characteristic. The 2nd objective of this invention is providing the liquid crystal aligning agent which provides the liquid crystal aligning film which does not produce the liquid crystal orientation nonuniformity resulting from liquid crystal dropping even when the ODF system is used in a liquid crystal filling process. Especially the liquid crystal aligning agent of this invention can be preferably used for liquid crystal aligning film formation of a vertical alignment type liquid crystal display element.

Another object of the present invention is to provide a liquid crystal display device having excellent display quality.

Still other objects and advantages of the present invention are apparent from the following description.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in view of the said situation, the present inventors used the liquid crystal aligning agent containing the specific polymer synthesize | combined using the diamine which has a specific structure, and can form the liquid crystal aligning film excellent in voltage retention and an afterimage characteristic. It has been found that the present invention has been achieved.

That is, the above objects and advantages of the present invention are firstly

At least one polymer selected from the group consisting of a polyamic acid obtained by reacting a tetracarboxylic dianhydride with a diamine containing at least one selected from the compounds represented by the following formulas (1) and (2) and an imidized polymer thereof It is achieved by the liquid crystal aligning agent containing.

<Formula 1>

<Formula 2>

(In the formula, n1 is each independently an integer of 1 to 8)

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

It is achieved by the liquid crystal display element provided with the liquid crystal aligning film formed from the said liquid crystal aligning agent.

Thirdly, the object and advantages of the present invention are:

It is achieved by the compound represented by the formula (1) or (2).

The liquid crystal aligning agent of this invention provides the liquid crystal aligning film excellent in the voltage retention and afterimage characteristic. Moreover, even when the ODF system is used for a liquid crystal filling process, the liquid crystal aligning agent of this invention provides the liquid crystal aligning film which the liquid-crystal orientation nonuniformity resulting from liquid crystal dropping does not generate | occur | produce. The liquid crystal aligning agent of this invention can be used for TN type, STN type liquid crystal display element, etc., and can be used especially for VA type liquid crystal display element.

The liquid crystal display element of this invention can be effectively used for various apparatuses, For example, it is used suitably for display apparatuses, such as a table calculator, a wristwatch, a table clock, a counting plate, a word processor, a personal computer, and a liquid crystal television.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The liquid crystal aligning agent of this invention is a group which consists of a polyamic acid obtained by making tetracarboxylic dianhydride and the diamine containing 1 or more types chosen from the compound represented by each of said Formula (1) and (2), and its imidation polymer. It contains one or more polymers selected from.

Tetracarboxylic dianhydride

Examples of the tetracarboxylic dianhydride that can be used to synthesize the polyamic acid used in the present invention include butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3- Dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2 , 3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-dicyclohexyl tetracarboxylic dianhydride , 2,3,5-tricarboxycyclopentylacetic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5 (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] Furan-1,3-dione, 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-di Oxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-ethyl-5- (tetrahydro -2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl -5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b- Hexahydro-8-ethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3- Dione, 5- (2,5-dioxotetrahydrofuranyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, Cyclo [2.2.2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro- 3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicar Acid anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane Aliphatic or alicyclic tetracarboxylic dianhydrides such as -3,5,8,10-tetraone, a compound represented by each of the following formulas TI and T-II;

[Formula T-I]

[Formula T-II]

(Wherein, R ¹ and R ³ each represent a divalent organic group having an aromatic ring, R ² and R ⁴ each represent a hydrogen atom or an alkyl group, and a plurality of R ² and R ^{4 present} may be the same or different. has exist)

Pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenylsulfontetracarboxylic dianhydride, 1,4,5 , 8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylethertetracarboxylic dianhydride, 3,3 ', 4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3', 4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic Acid dianhydrides, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydrides, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydrides, 4 , 4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3', 4,4 '-Biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphineoxide dianhydride , p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (tri Phenylphthalic acid) -4,4'-diphenylmethane dianhydride, ethylene glycol-bis (anhydrotrimelitate), propylene glycol-bis (anhydrotrimelitate), 1,4-butanediol-bis (anhydrotri Mellitate), 1,6-hexanediol-bis (anhydrotrimellitate), 1,8-octanediol-bis (anhydrotrimelitate), 2,2-bis (4-hydroxyphenyl) propane- Aromatic tetracarboxylic dianhydride, such as a bis (anhydro trimellitate) and the compound represented by each of following General formula T-1-T-4, is mentioned. These are used individually by 1 type or in combination of 2 or more types.

[Formula T-1]

[Formula T-2]

[Formula T-3]

[Formula T-4]

The tetracarboxylic dianhydride used for synthesizing the polyamic acid used in the present invention is a butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl Acetic dianhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6- 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, 3-oxabi Cyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro-3-fura Yl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-anhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarb Acid dianhydride, 3,3 ', 4,4'-biphenylsulfontetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 1,4,5, 8-naphthalenetetracarboxylic dianhydride, a compound represented by each of the following formulas T-5 to T-7 among the compounds represented by the formula TI, and a compound represented by the following formula T-8 At least one selected from the group consisting of compounds represented (hereinafter referred to as "specific tetracarboxylic dianhydride") It is preferable from a viewpoint that it can express favorable liquid crystal alignability.

[Formula T-5]

[Formula T-6]

[Formula T-7]

[Formula T-8]

Specific tetracarboxylic dianhydrides include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic 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, 3-oxabi Cyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahidrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro-3- Furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-anhydride , 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, pyromellitic dianhydride and the compound represented by the formula (T-1) 1 or more types are preferable and especially 3,5,6-tricarboxy-2-carboxy is selected. Till norbornane-2: 3,5: 6 dianhydride is preferred.

The tetracarboxylic dianhydride used for synthesizing the polyamic acid used in the present invention preferably contains at least 80 mol% of the specific tetracarboxylic dianhydride as described above with respect to the total tetracarboxylic dianhydride. It is more preferable to contain 90 mol% or more, and it is preferable to contain 95 mol% or more especially.

<Diamine>

The diamine used for synthesizing the polyamic acid used in the present invention includes at least one selected from the compounds represented by the formulas (1) and (2).

In Formulas 1 and 2, n1 is preferably an integer of 3 to 6, respectively. It is preferable that two amino groups couple | bonded with the benzene ring are in 2, 4 position or 3, 5 position with respect to another substituent.

The compound represented by the formula (1) is a dinitro compound obtained after, for example, dehalogenated hydrogen condensation of a corresponding 4- (4- (4-n-alkylcyclohexyl) cyclohexyl) phenol and a halogenated dinitrobenzene. It can synthesize | combine by reducing. The compound represented by the formula (2) is a dinitro compound obtained after, for example, the esterification reaction of the corresponding 4- (4- (4-n-alkylcyclohexyl) cyclohexyl) phenol and dinitrobenzoic acid chloride It can synthesize | combine by reducing.

The compound represented by each of the formulas (1) and (2) may be substituted with one or two or more alkyl groups (preferably methyl groups) having 1 to 2 carbon atoms.

As the diamine used for synthesizing the polyamic acid used in the present invention, only one or more selected from the compounds represented by Formulas 1 and 2 may be used, or the compounds represented by Formulas 1 and 2, respectively. You may use together the 1 or more types chosen from another diamine.

As another diamine which can be used together here, For example, Diamine which has a steroid skeleton, such as a compound represented by following formula (D-I), a compound represented by following formula (D-II);

[Formula D-I]

(In formula DI, X <^1> represents the divalent organic group chosen from -O-, -COO-, -OCO-, -NHCO-, -CONH-, and -CO-, and R <^5> is monovalent which has a steroid skeleton. An organic group, R ⁶ represents an alkyl group having 1 to 4 carbon atoms, a1 represents an integer of 0 to 3)

[Formula D-II]

In Formula D-II, X ² represents a divalent organic group selected from -O-, -COO-, -OCO-, -NHCO-, -CONH-, and -CO-, respectively, and R ⁷ has a steroid skeleton Represents a divalent organic group, each R ⁸ represents an alkyl group having 1 to 4 carbon atoms, and a2 represents an integer of 0 to 3, respectively)

p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenylsulfide, 4,4 ' -Diaminodiphenylsulfone, 4,4'-diaminobenzanilide, 4,4'-diaminodiphenylether, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diamino Biphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 3,3'-ditrifluoro Methyl-4,4'-diaminobiphenyl, 5-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4'-aminophenyl) -1 , 3,3-trimethylindane, 3,4'-diaminodiphenylether, 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-amino Phenyl) hexafluoropropane, bis [4- (4-aminophenoxy) phenyl] sulfone, 1,4-bis (4-amino Oxy) 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-dimethyl-2,7-diaminofluorene, 9,9-bis (4-aminophenyl) fluorene, 4,4'-methylene-bis (2-chloroaniline ), 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4 '-(p-phenylenediisopropylidene) bisaniline, 4,4'-(m-phenylenediisopropylidene) bis Aniline, 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-diamino-2,2'-bis (trifluoro Methyl) biphenyl, 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl, 4,4'-bis (4-aminophenoxy) biphenyl Aromatic diamines;

1,1-methacrylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 1,4-diaminocyclohexane, Isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindanylenedimethylenediamine, tricyclo [6.2.1.0 ^2,7 ] -undecylenedimethylenediamine, 4,4'-methylene Aliphatic diamines and alicyclic diamines such as bis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane;

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-dia Mino-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-phenylphenanthtridine, 1,4-diaminopiperazine, 3,6-diaminoacridine, bis (4-aminophenyl) phenylamine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6- Aminocarbazole, N-phenyl-3,6-diaminocarbazole, N, N'-bis (4-aminophenyl) -benzidine, N, N'-bis (4-aminophenyl) -N, N'- Diamine which has two primary amino groups and nitrogen atoms other than the said primary amino group in a molecule | numerator, such as a dimethylbenzidine, the compound represented by following formula (D-III), and the compound represented by following formula (D-IV);

[Formula D-III]

In Formula D-III, R ⁹ represents a monovalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine, and piperazine, and X ³ represents a divalent organic group R ¹⁰ represents an alkyl group having 1 to 4 carbon atoms, and a3 represents an integer of 0 to 3).

[Formula D-IV]

In formula (D-IV), R ¹¹ represents a divalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine, and piperazine, and X ⁴ each represents a divalent organic group And a plurality of X ^{4 's} may be the same or different, and each R ¹² represents an alkyl group having 1 to 4 carbon atoms, and a4 each represents an integer of 0 to 3).

Mono substituted phenylenediamines such as compounds represented by the following general formula (D-V);

[Formula D-V]

In formula DV, X ⁵ represents a divalent organic group selected from -O-, -COO-, -OCO-, -NHCO-, -CONH-, and -CO-, and R ¹³ is a trifluoromethylphenyl group, a tri A monovalent organic group having a group selected from a fluoromethoxy phenyl group and a fluorophenyl group or an alkyl group having 6 to 30 carbon atoms, R ¹⁴ represents an alkyl group having 1 to 4 carbon atoms, and a5 represents an integer of 0 to 3)

Diamino organosiloxane, such as a compound represented by following formula (D-VI);

[Formula D-VI]

(In Formula D-VI, R <^15> represents a C1-C12 hydrocarbon group each, two or more R <^15> may be same or different, respectively, p is an integer of 1-3, q is 1-20 Integer)

The compound etc. which are represented by each of following formula D-1-D-2 are mentioned. The benzene ring of the aromatic diamine and the compound represented by each of the following formulas D-1 and D-2 may be substituted with one or two or more alkyl groups having 1 to 4 carbon atoms (preferably a methyl group).

[Formula D-1]

[Formula D-2]

(Y in Formula D-1 is an integer of 2-12, z in Formula D-2 is an integer of 1-5)

These diamine can be used individually or in combination of 2 or more types.

R ⁶ , R ⁸ , R ¹⁰ , R ¹² and R ¹⁴ in Formulas DI, D-II, D-III, D-IV and DV are each preferably a methyl group, and a1, a2, a3, a4 and a5. It is preferable that it is 0 or 1, respectively, and it is more preferable that it is 0.

The steroid backbone in R ⁵ and R ⁶ of the above formulas (DI) and (D-II) means a skeleton containing a cyclopentano-perhydrophenanthrene nucleus or one or two or more of its carbon-carbon bonds are double bonds. Say the skeleton. As the monovalent organic group of R ^{5 and} the divalent organic group of R ⁶ having such a steroid skeleton, each preferably has 17 to 40 carbon atoms, and more preferably 17 to 30 carbon atoms.

As a specific example of R <^5> , for example, a cholestan-3-yl group, a cholesta-5-en-3-yl group, a cholesta-24-en-3-yl group, a cholesta-5,24-diene-3-yl group , Ranostan-3-yl group, ranosta-5-en-3-yl group, ranosta-24-en-3-yl group, ranosta-5,24-diene-3-yl group and the like; As a specific example of R <^6> , a cholestan-3, ^6- diyl group, a cholesta-5-ene-3, ^6- diyl group, a cholesta-24-ene-3, ^6- diyl group, a cholestan- is mentioned, for example. 3,3-diyl group, lanostane-3,6-diyl group, lanostane-3,3-diyl group, etc. are mentioned, respectively.

As a specific example of the compound represented by the said general formula (DI), for example, the compound represented by each of the following general formula (D-3)-D-7 as a specific example of the compound represented by the said general formula (D-II), for example The compound represented by each of -9-D-11 can be mentioned, respectively.

[Formula D-3]

[Formula D-4]

[Formula D-5]

[Formula D-6]

[Formula D-7]

[Formula D-9]

[Formula D-10]

[Formula D-11]

Among the other diamines, at least one selected from the group consisting of a compound represented by the formula (DI) and a compound represented by the formula (D-II) (hereinafter referred to as "other specific diamine (1)") and p- Phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diamino ratio Phenyl, 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 2,7-diaminofluorene, 4,4'-diaminodiphenylether, 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-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 1,4-di Minocyclohexane, 4,4'-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-dia Minopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N- Phenyl-3,6-diaminocarbazole, N, N'-bis (4-aminophenyl) -benzidine, the compound represented by the following formula D-12 among the compounds represented by formula D-III, formula D- Among the compounds represented by IV, the compounds represented by the following general formula (D-13) and the compounds represented by the above general formula (DV) dodecaneoxy-2,4-diaminobenzene, pentadecaneoxy-2,4-diaminobenzene, and hexadecane Oxy-2,4-diaminobenzene, octadecaneoxy-2,4-diaminobenzene, dodecaneoxy-2,5-diaminobenzene, pentadecaneoxy-2,5-diaminobenzene, hexadecaneoxy- 2,5-diaminobenzene, octadecaneoxy-2,5-di Minobenzene, selected from the group consisting of 1,3-bis (3-aminopropyl) -tetramethyldisiloxane among the compounds represented by the formulas D-14 to D-16 and the compound represented by the formula D-VI 1 or more types (hereinafter, referred to as "other specific diamine (2)") are mentioned.

[Formula D-12]

[Formula D-13]

[Formula D-14]

[Formula D-15]

[Formula D-16]

The diamine used for synthesizing the polyamic acid used in the present invention preferably contains 5 mol% or more of one or more selected from the compounds represented by Formulas 1 and 2 with respect to the total diamines, It is more preferable to contain 90 mol%, It is further more preferable to contain 20-80 mol%, It is especially preferable to contain 30-50 mol%.

The diamine used for synthesizing the polyamic acid used in the present invention is, in addition to at least one selected from the compounds represented by the above formulas (1) and (2), other specific diamines (1) and specific diamines (2) as described above. It is preferable to contain 1 or more types chosen from the group which consists of the following), It is preferable to contain these 10-90 mol% with respect to all diamine, It is more preferable to contain 20-80 mol%, It is more preferable that it contains 50-70 mol% It is more preferable to include.

Diamine used for synthesizing the polyamic acid used in the present invention is particularly preferably any one of the following (1) or (2).

(1) containing at least one selected from the compounds represented by the formulas (1) and (2) in the above-mentioned ratios, and further comprising 10 to 90 mol% of other specific diamines (2) relative to the total diamines, More preferably, 20 to 80 mol%, More preferably, diamine containing 50 to 70 mol%.

(2) It contains 1 or more types chosen from the compound represented by said Formula (1) and (2) by said ratio, Furthermore, another specific diamine (1) is preferable with respect to total diamine, Preferably it is 1-20 mol%, More preferably, diamine containing 5-10 mol%.

In the case of (2), it is preferably a diamine including one or more selected from the compounds represented by the formulas (1) and (2), other specific diamines (1) and other specific diamines (2). As these content rates, it is said ratio with respect to 1 or more types and specific diamine (1) chosen from the compound represented by said Formula (1) and (2), respectively, and it is preferable with respect to all diamine with respect to the specific diamine (2). Preferably it is 10-80 mol%, More preferably, it is 20-70 mol%.

Synthesis of Polyamic Acid

The polyamic acid used by this invention can be synthesize | combined by making tetracarboxylic dianhydride and diamine as mentioned above react.

As for the usage ratio of the tetracarboxylic dianhydride and diamine used for the synthesis reaction of a polyamic acid, the ratio in which the acid anhydride group of tetracarboxylic dianhydride is 0.5-2 equivalent with respect to 1 equivalent of amino group contained in diamine, More preferably, it is the ratio used as 0.7 to 1.2 equivalent.

The synthesis reaction of the polyamic acid is preferably in an organic solvent, preferably at a temperature condition of -20 to 150 ° C, more preferably 0 to 100 ° C, preferably 0.5 to 120 hours, more preferably 2 to 10 It is carried out by reaction time of time.

The organic solvent is not particularly limited as long as it can dissolve the polyamic acid synthesized. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl Aprotic polar solvents such as sulfoxide, γ-butyrolactone, tetramethylurea and hexamethylphosphortriamide; and phenol solvents such as m-cresol, xylenol, phenol, and halogenated phenol. The amount of the organic solvent (a) is preferably such that the total amount (b) of the tetracarboxylic dianhydride and the diamine compound is 0.1 to 30% by weight based on the total amount (a + b) of the reaction solution. In addition, when using together an organic solvent and the poor solvent mentioned later, it should be understood that the usage-amount of this organic solvent means the total usage-amount of an organic solvent and a poor solvent.

In the organic solvent, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like, which are poor solvents of polyamic acids, can be used in combination without causing precipitation of the resulting polyamic acid. As a specific example of such a poor solvent, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, lactic acid Butyl, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, diethyl oxalate, diethyl malonate, di Ethyl 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 Recol 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, isoamyl propionate, isoamyl isobutyrate, diisopentyl ether and the like.

When using together an organic solvent and a poor solvent at the time of the synthesis | combination of a polyamic acid, as a use ratio of a poor solvent, Preferably it is 20 weight% or less with respect to the sum total of an organic solvent and a poor solvent, More preferably, it is 10 weight% or less.

As described above, a reaction solution obtained by dissolving the polyamic acid is obtained. This reaction solution may be used as it is for the production of a liquid crystal aligning agent, may be used for the production of a liquid crystal aligning agent after isolating the polyamic acid contained in the reaction solution, or after the isolated polyamic acid is purified to prepare a liquid crystal aligning agent. Can also be used for Isolation of a polyamic acid can be performed by pouring the said reaction solution in a large quantity of poor solvents, obtaining a precipitate, and drying this precipitate under reduced pressure, or the method of distilling a reaction solution under reduced pressure with an evaporator. Moreover, polyamic acid can be refine | purified by the method which melt | dissolves this polyamic acid again in an organic solvent, and then precipitates with a poor solvent, or performs the process of distilling off under reduced pressure with an evaporator once or several times.

<Imidated Polymer>

The imidation polymer used for this invention can be obtained by dehydrating and ring-closing the amic-acid structure of polyamic acid as mentioned above, and imidizing it. Here, the amic acid structure which a polyamic acid has may be the fully imidized body dehydrating and ring-closing, or the imidized polymer in which an amic acid structure and an imide ring coexist. The imidation ratio of the imidation polymer used for this invention becomes like this. Preferably it is 50% or more, More preferably, it is 55 to 95%, It is especially preferable that it is 60 to 90%. Here, "imidation ratio" shows the ratio of the number of the imide rings with respect to the sum of the number of the amic acid structures in the imidation polymer, and the number of imide rings as a percentage. At this time, a part of the imide ring may be an iso imide ring.

The dehydration ring closure of the polyamic acid may be carried out by (i) a method of heating the polyamic acid or (ii) dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst to the solution, and heating it as necessary. This can be done by.

Preferably the reaction temperature in the method of heating the polyamic acid of said (i) is 50-200 degreeC, More preferably, it is 60-170 degreeC. When reaction temperature is less than 50 degreeC, dehydration ring-closure reaction does not fully advance, and when reaction temperature exceeds 200 degreeC, the molecular weight of the imidation polymer obtained may fall. The reaction time is preferably 1 to 120 hours, more preferably 2 to 30 hours.

As a dehydrating agent, acid anhydrides, such as an acetic anhydride, a propionic anhydride, and a trifluoroacetic anhydride, can be used as a dehydrating agent in the method of adding a dehydrating agent and a dehydration ring-closure catalyst in the solution of said polyamic acid of said (ii). It is preferable that the usage-amount of a dehydrating agent shall be 0.01-20 mol with respect to 1 mol of repeating units of a polyamic acid. As the dehydration ring closure catalyst, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used, for example. However, it is not limited to this. It is preferable that the usage-amount of a dehydration ring-closure catalyst shall be 0.01-10 mol with respect to 1 mol of dehydrating agents used. Moreover, as an organic solvent used for dehydration ring-closure reaction, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid is mentioned. 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 0.5 to 30 hours, more preferably 2 to 10 hours.

The imidation polymer obtained by the said method (i) may be used for manufacture of a liquid crystal aligning agent as it is, or may be used for manufacture of a liquid crystal aligning agent after refine | purifying the imidation polymer obtained. On the other hand, in the said method (ii), the reaction solution containing an imidation polymer is obtained. This reaction solution may be used as it is for the production of a liquid crystal aligning agent, or may be used for the production of a liquid crystal aligning agent after removing the dehydrating agent and the dehydration ring-closure catalyst from the reaction solution. It may be used, or may be used for the production of a liquid crystal aligning agent after purifying the isolated imidized polymer. In order to remove a dehydrating agent and a dehydration ring-closure catalyst from a reaction solution, methods, such as solvent substitution, can be applied, for example. Isolation and purification of the imidized polymer can be performed by performing the same operation as described above as the isolation and purification method of the polyamic acid.

<Polymer of Terminal Modified Type>

The said polyamic acid and the imidation polymer may be terminal modified form in which the molecular weight was adjusted, respectively. Such a terminal-modified polymer can be synthesized by adding an appropriate molecular weight regulator such as an acid anhydride, a monoamine compound, a monoisocyanate compound and the like to synthesize a polyamic acid. Here, as acid anhydride, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n- tetradecyl succinic anhydride, n-hexadecyl succinic anhydride, etc. are mentioned, for example. Can be. 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-eico Silamine etc. are mentioned. As a monoisocyanate compound, phenyl isocyanate, naphthyl isocyanate, etc. are mentioned, for example.

As a usage ratio of a molecular weight modifier, it is 20 weight part or less with respect to a total of 100 weight part of tetracarboxylic dianhydride and diamine used when synthesize | combining a polyamic acid, More preferably, it is 10 weight part or less.

<Solution Viscosity of Polymer>

The polyamic acid and the imidized polymer obtained as described above preferably have a solution viscosity of 20 to 800 mPa · s, and have a solution viscosity of 30 to 500 mPa · s when each has a solution having a concentration of 10% by weight. It is more preferable.

The solution viscosity (mPa · s) of the polymer is a polymer solution having a concentration of 10% by weight using a good solvent of the polymer (for example, N-methyl-2-pyrrolidone, γ-butyrolactone, etc.). It is a value measured at 25 ° C. using an E-type rotational viscometer.

<Other Ingredients>

Although the liquid crystal aligning agent of this invention contains as an essential component 1 or more types of polymers chosen from the group which consists of polyamic acid and its imidation polymer as mentioned above, it adds so long as it does not impair the effect and advantage of this invention. It may also contain other components. Examples of such other components include other polymers, compounds having one or more epoxy groups in the molecule (hereinafter referred to as "epoxy compound"), and functional silane compounds.

As said other polymer, the polyamic acid obtained by making polyorganosiloxane, tetracarboxylic dianhydride, and the diamine which does not contain all the compounds represented by the said Formulas 1 and 2, for example, "other polyamic acid "And imidized polymers thereof (hereinafter referred to as" other imidized polymers "), polyamic acid esters, polyesters, polyamides, cellulose derivatives, polyacetals, polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives And poly (meth) acrylates. Among them, other polyamic acids or other imidized polymers are preferred in terms of excellent varnish properties and electrical properties.

Tetracarboxylic dianhydrides used for synthesizing other polyamic acids and other imidized polymers are the same as those exemplified as tetracarboxylic dianhydrides used for synthesizing the polyamic acid. Diamines used to synthesize other polyamic acids and other imidized polymers are the same as those exemplified as other diamines that can be used to synthesize the polyamic acid. In this case, the diamine containing 70 mol% or more of 1 or more types chosen from other specific diamine (1) and (2) with respect to all diamine is preferable, and the diamine containing 90 mol% or more is more preferable. The other polyamic acid and the other imidized polymer are the above-mentioned methods for synthesizing the polyamic acid and the imidized polymer except for using diamine which does not contain all of the compounds represented by the formulas (1) and (2) as the diamine, respectively. It can synthesize | combine in the same way. Among other polyamic acids and other imidized polymers, other polyamic acids are preferred.

The use ratio of the other polymer in the liquid crystal aligning agent of this invention is the sum total of a polymer (polyamic acid obtained by making the diamine containing the tetracarboxylic dianhydride and the compound represented by the said Formula (1 or 2), the imidation polymer thereof) And the total of other polymers optionally used, which are the same below), preferably 80% by weight or less, more preferably 60% by weight or less, and even more preferably 40% by weight or less.

The said epoxy compound can be used from a viewpoint of improving the adhesiveness with respect to the board | substrate surface of the liquid crystal aligning agent formed from the liquid crystal aligning agent of this invention further, for example, ethylene glycol diglycidyl ether, polyethyleneglycol diglycidyl Ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethyl Olpropanetriglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentylglycol diglycidyl ether, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N- Diglycidyl-benzylamine, N, N-diglycidyl-aminomethylcyclohexane and the like are preferred. Can be mentioned. The compounding ratio of these epoxy compounds becomes like this. Preferably it is 40 weight part or less with respect to a total of 100 weight part of polymers, More preferably, it is 0.1-30 weight part.

As said functional silane compound, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 2-aminopropyl trimethoxysilane, 2-aminopropyl triethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxy Silane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimeth Methoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecan, 10-triethoxysilyl-1,4,7-triazadecan, 9-trimethoxysilyl-3 , 6-Diazonayl acetate, 9-triethoxysilyl-3,6-diazanyl acetate, 9-trimethoxysilyl-3,6-methyl diazanoanoate, 9-trie Methyl cylyl-3,6-diazanonan acid, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane , N-phenyl-3-aminopropyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltri Ethoxysilane, 3-glycidoxy propyl trimethoxysilane, 3-glycidoxy propyl triethoxy silane, etc. are mentioned.

The compounding ratio of these functional silane compounds becomes like this. Preferably it is 2 weight part or less, More preferably, it is 0.2 weight part or less with respect to 100 weight part of polymers in total.

<Liquid crystal aligning agent>

The liquid crystal aligning agent of the present invention is preferably formed by dissolving and containing a polyamic acid as described above, at least one polymer selected from the group consisting of imidized polymers thereof, and other components optionally added in an organic solvent.

Only the polyamic acid may be used as the polymer, only the imidized polymer may be used, or both the polyamic acid and the imidized polymer may be used. The polymer contained in the liquid crystal aligning agent of this invention, Preferably it is an imidation polymer or the combination of a polyamic acid and an imidation polymer. Here, the ratio of the number of the imide rings which the imidation polymer has with respect to the sum total of the number of the amic acid structures which the polyamic acid contained in a liquid crystal aligning agent, the number of the amic acid structures which an imidation polymer has, and the number of imide rings (following) And "average imidization ratio", and when the liquid crystal aligning agent of this invention contains another polyamic acid and another imidation polymer, it should be understood that the average imidation ratio is also numerical value calculated by including these, and is 40% or more. It is preferable that it is 45 to 90%, and it is especially preferable that it is 50 to 80%.

As an organic solvent which can be used for the liquid crystal aligning agent of this invention, the solvent illustrated above as what is used for the synthesis reaction of a polyamic acid is mentioned. Moreover, the poor solvent illustrated as what can be used together at the time of the synthesis reaction of a polyamic acid can also be selected suitably, and can be used together.

As an especially preferable organic solvent which can be used for the liquid crystal aligning agent of this invention, N-methyl- 2-pyrrolidone, (gamma) -butyrolactone, (gamma) -butyrolactam, N, N- dimethylformamide, N , N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, ethylene glycol methyl Ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, di Ethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl Le acetate, and the like can be mentioned isoamyl propionate, isoamyl isobutyrate, diisobutyl ketone, di-isopentyl ether, ethylene carbonate, propylene carbonate. These may be used independently, or may mix and use 2 or more types. Especially preferable solvent composition is a composition obtained by combining the said solvent, and is a composition which does not precipitate a polymer in an alignment agent, and makes surface tension of an alignment agent into the range of 25-40 mN / m.

Solid content concentration (the ratio which the total weight of components other than the solvent contained in a liquid crystal aligning agent occupies for the total weight of a liquid crystal aligning agent) in the liquid crystal aligning agent of this invention is selected in consideration of viscosity, volatility, etc., Preferably it is 1 To 10% by weight. That is, although the liquid crystal aligning agent of this invention is apply | coated to the surface of a board | substrate, and the coating film used as a liquid crystal aligning film is formed by removing a solvent, when solid content concentration is less than 1 weight%, the film thickness of this coating film becomes too small and a favorable liquid crystal aligning film is formed. When it is hard to obtain and solid content concentration exceeds 10 weight%, the film thickness of a coating film becomes large too much and it is difficult to obtain a favorable liquid crystal aligning film similarly, the viscosity of a liquid crystal aligning agent increases, and coating property falls.

The range of especially preferable solid content concentration changes with the method used when apply | coating a liquid crystal aligning agent to a board | substrate. For example, in the case of a spinner method, the range of 1.5 to 4.5 weight% is especially preferable. In the case of the printing method, it is particularly preferable that the solid content 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. When using the inkjet method, it is especially preferable to make solid content concentration into the range of 1 to 5 weight%, and to make solution viscosity into the range of 3-15 mPa * s.

The temperature at the time of manufacturing the liquid crystal aligning agent of this invention becomes like this. Preferably it is 0 degreeC-200 degreeC, More preferably, it is 20 degreeC-60 degreeC.

<Liquid crystal display element>

The liquid crystal display element of this invention is equipped with the liquid crystal aligning film formed from the above-mentioned liquid crystal aligning agent of this invention. The liquid crystal aligning film formed from the liquid crystal aligning agent of this invention expresses high voltage retention and a good residual image characteristic as possible especially when using it as a liquid crystal aligning film of a vertical alignment type.

The liquid crystal display element of this invention can be manufactured by the following method, for example.

(1) The liquid crystal aligning agent of this invention is apply | coated to the one surface of the board | substrate with which the patterned transparent conductive film is provided by the appropriate coating methods, such as a roll coater method, a spin coating method, the printing method, and the inkjet method, for example. The coating film is formed by heating the coated surface. As a board | substrate, For example, glass, such as float glass and a soda glass; Transparent substrates containing plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and alicyclic polyolefin can be used. Examples of the transparent conductive film provided on one surface of the substrate include an NESA film (registered trademark of PPG Co., Ltd.) containing indium tin oxide (SnO ₂ ) and indium tin oxide (In ₂ O ₃ -SnO ₂ ). An ITO film or the like can be used. In patterning of these transparent conductive films, the method of using a mask beforehand when forming a photo-etching method or a transparent conductive film is used. At the time of application | coating of a liquid crystal aligning agent, in order to make adhesiveness of a board | substrate surface, a transparent conductive film, and a coating film more favorable, you may apply | coat a functional silane compound, a functional titanium compound, etc. previously on the said surface of a board | substrate. After application of the liquid crystal aligning agent, preliminary heating (pre-baking) is preferably performed first for the purpose of preventing liquid dripping of the applied alignment agent. Preliminary baking temperature becomes like this. Preferably it is 30-200 degreeC, More preferably, it is 40-150 degreeC, Especially preferably, it is 40-100 degreeC. The preliminary baking time is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes. Moreover, after removing a solvent completely, it is preferable to perform a heating (post-baking) process further. Thereafter, the baking temperature is preferably 80 to 300 ° C, more preferably 120 to 250 ° C. Post-baking time becomes like this. Preferably it is 5 to 200 minutes, More preferably, it is 10 to 100 minutes. Although the liquid crystal aligning agent of this invention forms a coating film used as an orientation film by removing an organic solvent after apply | coating as mentioned above, the polymer contained in the liquid crystal aligning agent of this invention is polyamic acid, or an imide ring structure and an amic acid structure. In the case of an imidized polymer having a compound, the dehydration ring-closing reaction can be advanced by further heating after the coating film is formed, thereby making the coating film more imidized.

The film thickness of the coating film formed becomes like this. Preferably it is 0.001-1 micrometer, More preferably, it is 0.005-0.5 micrometer.

(2) Although the coating film formed as mentioned above can be used as a vertically-aligned liquid crystal aligning film as it is, it is arbitrary direction by the roll which wound the cloth containing suitable fiber, such as nylon, rayon, cotton, etc. with respect to the coating film surface arbitrarily. After performing the rubbing process to rub with, it can also be used as a liquid crystal aligning film. In addition, about the coating film after a rubbing process, it is described in patent document 6 (Unexamined-Japanese-Patent No. 6-222366) and patent document 7 (Japanese Unexamined-Japanese-Patent No. 6-281937, for example). By irradiating a part of the same liquid crystal aligning film with an ultraviolet-ray, the process of changing the pretilt angle of a some area | region of a liquid crystal aligning film, and the liquid crystal aligning film as described in patent document 8 (Unexamined-Japanese-Patent No. 5-107544). Viewing characteristics of the liquid crystal display device obtained by forming a resist film on a part of the surface, then performing a rubbing treatment in a direction different from the rubbing treatment previously performed, and then removing the resist film so that the liquid crystal alignment film has a different liquid crystal alignment ability for each region. It is possible to improve it. When a rubbing process is performed with respect to a coating film surface, you may wash | clean after that as needed.

(3) The liquid crystal cell is manufactured by preparing two board | substrates with a liquid crystal aligning film as above-mentioned, and arrange | positioning a liquid crystal between these two board | substrates. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example.

The first method is a conventionally known method. First, two substrates are disposed to face each other with a gap (cell spacing) so that each liquid crystal alignment film faces each other, and the two substrate peripheries are bonded using a sealant, and the cell gap partitioned by the substrate surface and the sealant. After injecting and filling a liquid crystal in the inside, a liquid crystal cell can be manufactured by sealing an injection hole.

The second method is a method called an ODF (One Drop Fill) method. An ultraviolet-ray curable sealing material is apply | coated to the predetermined place on one board | substrate among two board | substrates with which the liquid crystal aligning film was formed, for example, after dropping a liquid crystal on the liquid crystal aligning film surface, the other board | substrate is bonded so that a liquid crystal aligning film may oppose. Then, the liquid crystal cell can be manufactured by irradiating ultraviolet light to the whole surface of a board | substrate, and hardening a sealing agent. The liquid crystal aligning agent of this invention has the advantage that the liquid crystal display element which does not generate | occur | produce the liquid-crystal orientation nonuniformity which originates in the trace of liquid crystal dropping even when a VA type liquid crystal display element was manufactured by ODF method. This advantage is particularly remarkable when the liquid crystal aligning agent of the present invention contains a polymer synthesized using a diamine containing a specific diamine (1) in addition to at least one selected from the compounds represented by the formulas (1) and (2). Do.

When using any of the said 1st and 2nd methods, it is preferable to remove the flow orientation at the time of liquid crystal filling by gradually cooling a liquid crystal cell to the temperature which the used liquid crystal takes an isotropic phase, and then gradually cooling to room temperature. .

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

Here, as a sealing agent, the epoxy resin etc. which contain the hardening agent and the aluminum oxide sphere as a spacer can be used, for example. Examples of the liquid crystals include nematic liquid crystals and smectic liquid crystals. Among them, nematic liquid crystals are preferred, and for example, Schiff base liquid crystals, subfamily clock liquid crystals, biphenyl liquid crystals, phenylcyclohexane liquid crystals, ester liquid crystals, A terphenyl type liquid crystal, a biphenyl cyclohexane type liquid crystal, a pyrimidine type liquid crystal, a dioxane type liquid crystal, a bicyclooctane type liquid crystal, a cuban type liquid crystal, etc. can be used. Furthermore, for these liquid crystals, for example, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonaate and cholesteryl carbonate; The chiral agent sold as brand names "C-15" and "CB-15" (made by Merck) can also be added and used.

As a polarizing plate bonded to the outer surface of a liquid crystal cell, the polarizing plate which sandwiched the polarizing film called "H film | membrane" which absorbed iodine while extending-stretching polyvinyl alcohol, and the polarizing plate which consists of H film itself is inserted.

<Example>

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to these Examples. The solution viscosity of the polymer in the following synthesis examples, and the imidation ratio of the imidation polymer were evaluated by the following methods, respectively.

[Solution Viscosity of Polymer]

The solution viscosity of a polymer is the value measured at 25 degreeC using the E-type viscosity meter with respect to the polymer solution indicated by each synthesis example.

[Imidation Rate of Imidized Polymer]

The imidized polymer was dried under reduced pressure at room temperature, dissolved in deuterated dimethyl sulfoxide, ¹ H-NMR was measured at room temperature using tetramethylsilane as a reference substance, and obtained by the following formula (1).

Imidation ratio (%) = (1-A1 / A2 × α) × 100

A1: peak area derived from the proton of the NH group which appears in the vicinity of 10 ppm

A2: peak area derived from other protons

α: ratio of the number of other protons to one of the protons in the NH group in the precursor (polyamic acid) of the polymer

<Synthesis of diamine represented by Formula 1 or 2>

Each synthesis example below was repeated on the following synthesis scale as needed, and the product of the required amount in the following synthesis example was ensured.

Synthesis Example 1 (Synthesis of 1 (2,4-diaminophenoxy) -4 (4 (4-n-pentylcyclohexyl) cyclohexyl) benzene)

1 (2,4-diaminophenoxy) -4 (4 (4-n-pentylcyclohexyl) cyclohexyl) benzene (hereinafter also referred to as "diamine A") was synthesized according to Scheme 1 below.

20.3 g (0.1 mol) of 1-chloro-2,4-dinitrobenzene, 32.9 g (0.1 mol) of 4 (4- (4-n-pentylcyclohexyl) cyclohexyl) phenol, and 41.4 g (0.3 mol) of potassium carbonate under a nitrogen atmosphere Mole) was dissolved in 500 mL of dimethylformamide, and the reaction was carried out at room temperature for 6 hours. 500 mL of distilled water was added to the reaction solution, the mixture was sufficiently stirred, extracted with 500 mL of chloroform, and the obtained organic layer was extracted and washed with distilled water. The organic layer after washing was dehydrated with magnesium sulfate, and then the solvent was removed using a rotary evaporator to obtain 47.0 g of 1 (2,4-dinitrophenoxy) -4 (4 (4-n-pentylcyclohexyl) cyclohexyl) benzene. .

Subsequently, palladium / carbon (Pd / C) to 24.8 g (0.05 mol) of 1 (2,4-dinitrophenoxy) -4 (4 (4-n-pentylcyclohexyl) cyclohexyl) benzene described above under a nitrogen atmosphere. 18.2 g and 300 mL of tetrahydrofuran were added and stirred at 70 ° C. for 1 hour. 30 mL of hydrazine monohydrate was added to this mixture, and the reaction was carried out by stirring at 80 DEG C for 3 hours under nitrogen. After completion of the reaction, the catalyst was separated by filtration, the filtrate was concentrated, and 300 mL of chloroform was added to dissolve the whole amount, and then the organic solvent layer was extracted and washed with distilled water. The organic solvent layer was dehydrated with magnesium sulfate, and then concentrated by rotary evaporation to obtain a diamine A preparation. This preparation was purified by column chromatography, and 18.1 g of diamine A was obtained by removing a solvent.

Synthesis Example 2 (Synthesis of 3,5-diaminobenzoic acid 4 (4 (4-n-pentylcyclohexyl) cyclohexyl) phenyl)

3,5-Diaminobenzoic acid 4 (4 (4-n-pentylcyclohexyl) cyclohexyl) phenyl (hereinafter also referred to as "diamine B") was synthesized according to Scheme 2 below.

Under a nitrogen atmosphere, 32.9 g (0.1 mol) of 4 (4 (4-n-pentylcyclohexyl) cyclohexyl) phenol, 10.6 g (0.105 mol) of triethylamine, and 300 mL of tetrahydrofuran were mixed and stirred at 0 ° C. Dissolved. A mixture of 21.8 g (0.105 mol) of 3,5-dinitrobenzoyl chloride and 100 mL of tetrahydrofuran was added dropwise to this solution over 30 minutes, followed by stirring at room temperature for 3 hours. The precipitated salt was separated by filtration, the filtrate was concentrated, 300 mL of chloroform was added, and the whole was dissolved, followed by extraction and washing with distilled water. The organic layer was dehydrated with magnesium sulfate and then concentrated on a rotary evaporator. The obtained crude product was purified by column chromatography and 51.2 g of 3,5-dinitrobenzoic acid 4 (4 (4-n-pentylcyclohexyl) cyclohexyl) phenyl was obtained by removing the solvent.

Subsequently, to 26.1 g (0.05 mol) of the above-mentioned 3,5-dinitrobenzoic acid 4 (4 (4-n-pentylcyclohexyl) cyclohexyl) phenyl under nitrogen atmosphere, 112.8 g (0.5 mol) of tin chloride dihydrate and acetic acid 400 mL of ethyl was added and the reaction was carried out by heating to reflux for 3 hours. After completion of the reaction, the reaction solution was mixed with 400 mL of saturated potassium fluoride aqueous solution, sufficiently stirred and separated, and the obtained organic layer was extracted and washed with distilled water. The organic layer was then dehydrated with magnesium sulfate, concentrated on a rotary evaporator, purified by column chromatography, and then the solvent was removed to obtain 17.4 g of diamine B.

Synthesis Example 3

Diamine C represented by the following chemical formula was synthesize | combined according to the method of patent document 2 (Unexamined-Japanese-Patent No. 09-278724).

Synthesis Example 4

According to the method of patent document 9 (Unexamined-Japanese-Patent No. 4-281427), the compound represented by the said general formula (D-5) (henceforth "a compound (D-5)") was synthesize | combined.

<Synthesis of imidized polymer>

Synthesis Example 5

3,5,6-tricarboxy-2-carboxynorbornane-2: 3,5: 6- dianhydride 12.5 g (0.05 mol) as tetracarboxylic dianhydride, 3.2 g of p-phenylenediamine as diamine ( 0.03 mol) and 8.7 g (0.02 mol) of diamine A synthesized in Synthesis Example 1 above were dissolved in 98 g of N-methyl-2-pyrrolidone (NMP), and the reaction was carried out at 60 ° C. for 6 hours. The solution viscosity measured as a small amount of the obtained polyamic-acid solution, the addition of NMP, and the solution of 10 weight% of polyamic-acid concentration was 51 mPa * s.

Subsequently, 120 g of NMP was added to the obtained polyamic acid solution, 20 g of pyridine and 20 g of acetic anhydride were added, and dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new γ-butyrolactone solvent (by this solvent substitution operation, the pyridine and acetic anhydride used for the dehydration ring closure reaction were removed to the outside of the system, which is the same below). About 170 g of a solution containing about 90% of the imidized polymer (A-1) was obtained. About this solution, the solution viscosity measured as (gamma) -butyrolactone solution of 10 weight% of polymer concentrations was 62 mPa * s.

Synthesis Example 6

3,5,6-tricarboxy-2-carboxynorbornane-2: 3,5: 6- dianhydride 12.5 g (0.05 mol) as tetracarboxylic dianhydride, 3.2 g of p-phenylenediamine as diamine ( 0.03 mol) and 9.2 g (0.02 mol) of diamine B were dissolved in 98 g of NMP, and the reaction was carried out at 60 ° C for 6 hours. The solution viscosity measured as a small amount of the obtained polyamic-acid solution, the addition of NMP, and the solution of 10 weight% of polyamic-acid concentration was 61 mPa * s.

Subsequently, 120 g of NMP was added to the obtained polyamic acid solution, 20 g of pyridine and 20 g of acetic anhydride were added, and dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. About 160 g of the solution containing the imidation polymer (A-2) of about 90% of imidation ratio was obtained by solvent substitution of the solvent in system with fresh (gamma) -butyrolactone after a dehydration ring-closure reaction. About this solution, the solution viscosity measured as (gamma) -butyrolactone solution of 10 weight% of polymer concentrations was 71 mPa * s.

Synthesis Example 7

11 g (0.05 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride as tetracarboxylic dianhydride, 3.2 g (0.03 mol) of p-phenylenediamine and 8.7 g (0.02 mol) of diamine A as diamine It dissolved in 93 g of NMP, and reacted at 60 degreeC for 6 hours. A small amount of the obtained polyamic acid solution was aliquoted, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight by adding NMP was 48 mPa · s.

Subsequently, 120 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 20 g of pyridine and 20 g of acetic anhydride were added, and dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. About 160 g of the solution containing the imidation polymer (A-3) of about 90% of imidation ratio was obtained by solvent substitution of the solvent in system with fresh (gamma) -butyrolactone after a dehydration ring-closure reaction. The solution viscosity measured as a (gamma) -butyrolactone solution of the polymer concentration of 10 weight% with respect to this solution was 58 mPa * s.

Synthesis Example 8

3,5,6-tricarboxy-2-carboxymethylnorbornane-2 as tetracarboxylic dianhydride: 12.5 g (0.05 mol) of 3,5: 6- dianhydride, 3.2 g of p-phenylenediamine as diamine (0.03 mol), 6.5 g (0.015 mol) of diamine A and 2.6 g (0.005 mol) of compound (D-5) were dissolved in 100 g of NMP, and the reaction was carried out at 60 ° C. for 6 hours. A small amount of the obtained polyamic acid solution was aliquoted, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight by adding NMP was 47 mPa · s.

Subsequently, 124 g of NMP were added to the obtained polyamic acid solution, 20 g of pyridine and 20 g of acetic anhydride were added, and dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring-closure reaction, about 180 g of the solution containing the imidation polymer (A-4) of about 90% of imidation ratio was obtained by solvent substitution of the solvent in system with fresh (gamma) -butyrolactone. About this solution, the solution viscosity measured as (gamma) -butyrolactone solution of 10 weight% of polymer concentrations was 57 mPa * s.

Synthesis Example 9

3,5,6-tricarboxy-2-carboxymethylnorbornane-2 as tetracarboxylic dianhydride: 12.5 g (0.05 mol) of 3,5: 6- dianhydride, 3.2 g of p-phenylenediamine as diamine (0.03 mol), 6.9 g (0.015 mol) of diamine B and 2.6 g (0.005 mol) of Compound (D-5) were dissolved in 101 g of NMP, and the reaction was carried out at 60 ° C. for 6 hours. A small amount of the obtained polyamic acid solution was aliquoted, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight by adding NMP was 46 mPa · s.

Subsequently, 126 g of NMP was added to the obtained polyamic acid solution, 20 g of pyridine and 20 g of acetic anhydride were added, and dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. After dehydration ring-closure reaction, about 185 g of solutions containing the imidation polymer (A-5) of about 90% of imidation ratio were obtained by solvent substitution of the solvent in system with fresh (gamma) -butyrolactone. The solution viscosity measured as a (gamma) -butyrolactone solution of 10 weight% of polymer concentrations with respect to this solution was 56 mPa * s.

Synthesis Example 10

11.2 g (0.05 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride as tetracarboxylic dianhydride, 3.2 g (0.03 mol) of p-phenylenediamine as diamine, 6.5 g (0.015 mol) of diamine A and 2.6 g (0.005 mol) of Compound (D-5) were dissolved in 94 g of NMP, and the reaction was carried out at 60 ° C for 6 hours. A small amount of the obtained polyamic acid solution was aliquoted, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight by adding NMP was 45 mPa · s.

Subsequently, 118 g of NMP was added to the obtained polyamic acid solution, 20 g of pyridine and 20 g of acetic anhydride were added, and dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. After dehydration ring-closure reaction, about 180 g of solutions containing the imidation polymer (A-6) of about 90% of imidation ratio were obtained by solvent substitution of the solvent in system with fresh (gamma) -butyrolactone. About this solution, the solution viscosity measured as (gamma) -butyrolactone solution of 10 weight% of polymer concentrations was 58 mPa * s.

Synthesis Example 11

3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6- dianhydride 12.5 g (0.05 mol) as tetracarboxylic dianhydride, 3.2 g of p-phenylenediamine as diamine (0.03 mol), 6.5 g (0.015 mol) of diamine A and 2.6 g (0.005 mol) of compound (D-5) were dissolved in 100 g of NMP, and the reaction was carried out at 60 ° C. for 6 hours. A small amount of the obtained polyamic acid solution was aliquoted, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight by adding NMP was 47 mPa · s.

Subsequently, 1243 g of NMP was added to the obtained polyamic acid solution, 4 g of pyridine and 5.1 g of acetic anhydride were added, and dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. After dehydration ring-closure reaction, about 170 g of solutions containing the imidation polymer (A-7) of about 45% of imidation ratio were obtained by solvent substitution of the solvent in system with fresh (gamma) -butyrolactone. About this solution, the solution viscosity measured as (gamma) -butyrolactone solution of 10 weight% of polymer concentrations was 63 mPa * s.

Synthesis of Other Polymers

(Synthesis of other imidized polymers)

Synthesis Example 12

125 g (0.5 mol) of 3,5,6-tricarboxy-2-carboxynorbornane-2: 3,5: 6- dianhydride as tetracarboxylic dianhydride, 32 g of p-phenylenediamine as diamine ( 0.3 mole) and 70 g (0.2 mole) of diamine C were dissolved in 910 g of NMP, and the reaction was carried out at 60 ° C for 6 hours. The solution viscosity measured as a small amount of the obtained polyamic-acid solution, the addition of NMP, and the solution of 10 weight% of polyamic-acid concentration was 55 mPa * s.

Subsequently, 1,100 g of NMP was added to the obtained polyamic acid solution, 200 g of pyridine and 200 g of acetic anhydride were added, and dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. After dehydration ring-closure reaction, about 1,600 g of solutions containing the imidation polymer (A-8) of about 90% of imidation ratio were obtained by solvent substitution of the solvent in system with fresh (gamma) -butyrolactone. About this solution, the solution viscosity measured as (gamma) -butyrolactone solution of 10 weight% of polymer concentrations was 65 mPa * s.

Synthesis Example 13

1,25 g (0.05 mol) of 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6- dianhydride as tetracarboxylic dianhydride, 4.3 g of p-phenylenediamine as diamine (0.04 mol) and 5.2 g (0.01 mol) of Compound (D-5) were dissolved in 88 g of NMP, and the reaction was carried out at 60 ° C. for 6 hours. A small amount of the obtained polyamic acid solution was aliquoted, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight by adding NMP was 45 mPa · s.

Subsequently, 110 g of NMP was added to the obtained polyamic acid solution, 20 g of pyridine and 20 g of acetic anhydride were added, and dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. After dehydration ring-closure reaction, about 170 g of solutions containing the imidation polymer (A-9) of about 90% of imidation ratio were obtained by solvent substitution of the solvent in system with fresh (gamma) -butyrolactone. About this solution, the solution viscosity measured as (gamma) -butyrolactone solution of 10 weight% of polymer concentrations was 55 mPa * s.

(Synthesis of Other Polyamic Acids)

Synthesis Example 14

55 g (0.25 mol) of pyromellitic dianhydrides as tetracarboxylic dianhydride and 49 g (0.25 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, p-phenylenediamine 54 as diamine g (0.5 mol) was dissolved in 630 g of NMP, and reacted at 60 ° C for 6 hours to obtain about 1,200 g of a solution containing 20% by weight of polyamic acid (B-1). The solution viscosity measured as a small amount of this polyamic-acid solution, the addition of NMP, and the solution of 10 weight% of polyamic-acid concentration was 70 mPa * s.

Example 1

<Production of Liquid Crystal Alignment Agent>

The weight ratio of the polymer which contains the solution containing the imidation polymer (A-1) obtained by the said synthesis example 5, and the solution containing the polyamic acid (B-1) obtained by the said synthesis example 14 in each solution is (A- 1): (B-1) = 80: 20, the mixture was mixed to add γ-butyrolactone, NMP and butyl cellosolve, the solvent composition of γ-butyrolactone: NMP: butyl cellosolve = 71:17:12 (weight ratio) and solid content concentration was made into the solution which is 2.5 weight%. The liquid crystal aligning agent (S-1) was manufactured by filtering this solution using the filter of 1 micrometer of pore diameters. The average imidation ratio of the polymer contained in this liquid crystal aligning agent is shown in following Table 1.

<Production of Vertically Oriented Liquid Crystal Cell>

After apply | coating the said liquid crystal aligning agent (S-1) to the transparent electrode surface of the glass substrate with a transparent electrode containing an ITO film by spin coating method, and prebaking for 1 minute on 80 degreeC hotplate, 200 degreeC hot It baked after 10 minutes on the plate, and formed the coating film (liquid crystal aligning film) of 60 nm of average film thickness. This operation was repeated and a pair (two pieces) of board | substrates which have a liquid crystal aligning film in the transparent electrode surface were manufactured.

After apply | coating the aluminum oxide sphere containing epoxy resin adhesive of diameter 5.5micrometer to each outer edge which has a pair of said liquid crystal aligning film board | substrate with a liquid crystal aligning film, it overlapped and crimp | bonded so that the liquid crystal aligning film surface might face, and hardened the adhesive agent. Subsequently, after filling a negative type liquid crystal (MLC-6608 by Merck Co., Ltd.) between a pair of board | substrates from a liquid crystal injection hole, the vertically-aligned liquid crystal cell was manufactured by sealing a liquid crystal injection hole with an acryl-type photocuring adhesive. About this liquid crystal cell, voltage retention and afterimage characteristic were evaluated as follows. The evaluation results are shown in Table 1.

<Evaluation of Voltage Retention Rate>

The voltage retention of 167 milliseconds after the release of the application was measured after applying a voltage of 1 V at 65 ° C. with an application time of 60 microseconds and a span of 167 milliseconds for the vertically aligned liquid crystal cell. The measurement apparatus used VHR-1 by Toyo Technica Corporation.

<Evaluation of Afterimage Characteristics>

As a substrate, a vertically oriented liquid crystal cell was produced in the same manner as in <Production of the vertically oriented liquid crystal cell> except that a glass substrate having two ITO transparent electrodes having a pattern as shown in FIG. 1 was used.

A DC voltage of 6.0 V was applied to electrode A and 0.5 V to electrode A simultaneously for 168 hours while irradiating the backlight with the liquid crystal cell under an environment of 40 to 50 ° C. After the stress was released, DC voltages of 0.1 to 5.0 V were applied to the electrodes A and B by 0.1 V, and residual image characteristics were determined by the luminance difference between the electrodes A and B at the respective voltages. The case where no luminance difference was observed was judged as the afterimage characteristic "good", the case where the luminance difference was small, the afterimage characteristic "good", and the case where the luminance difference was large as the afterimage characteristic "poor".

Examples 2-12 and Comparative Examples 1-3

Except having followed the polymer composition of Table 1, it carried out similarly to Example 1, and manufactures liquid crystal aligning agents (S-2)-(S-12) and (R-1)-(R-3), respectively, and a liquid crystal Cells were prepared and evaluated. The evaluation results are shown in Table 1.

In addition, the numerical value in parentheses after the polymer type name in Table 1 is the quantity (weight part) of the polymer contained in the used polymer solution, and the polyamic acid solution was not used in Examples 9-11 and Comparative Example 3.

Example 13

<Evaluation of Liquid Crystal Orientation Nonuniformity>

The liquid crystal aligning agent (S-6) manufactured in the said Example 6 was apply | coated by the spin coating method to the transparent electrode surface of the glass substrate with a transparent electrode containing an ITO film | membrane, and prebaked for 1 minute on 80 degreeC hotplate. Subsequently, after baking for 10 minutes on a 200 degreeC hotplate, the coating film (liquid crystal aligning film) of 60 nm of average film thickness was formed. This operation was repeated and a pair (two pieces) of board | substrates which have a liquid crystal aligning film in the transparent electrode surface were manufactured.

5 microliters of ultrapure water was dripped on the liquid crystal aligning film surface of one board | substrate with the liquid crystal aligning film manufactured above at the position of 5 mm in height using a micro pipette, and it naturally dried at room temperature as it is.

As described above, a vertically aligned liquid crystal cell was produced in the same manner as in Example 1 except that a pair of substrates including a substrate subjected to impact of dropping on the liquid crystal alignment film surface was used.

About this liquid crystal cell, when it observed under cross nicol, applying an AC 6.0V (peak-peak) and a 30-Hz rectangular wave at room temperature, the liquid crystal orientation nonuniformity characteristic was not observed when the drop of ultrapure water was not observed as liquid crystal orientation nonuniformity. It was set as "excellent", and the case where this was observed slightly was made into the liquid-crystal orientation nonuniformity characteristic "good", and the case where this was clearly observed was evaluated as liquid-crystal orientation nonuniformity characteristic "defect". The results are shown in Table 2 below.

In addition, the dropping of the ultrapure water mentioned above is an alternative evaluation for investigating the influence of the impact by the liquid crystal dropping in an ODF process.

Examples 14-19 and Comparative Examples 4 and 5

Except having used each of what was described in Table 2 as a liquid crystal aligning agent, it carried out similarly to Example 13, and used a pair of board | substrates containing the board | substrate which gave the impact by the drop of ultrapure water on the liquid crystal aligning film surface, and used the vertically-aligned liquid crystal The cell was produced and the liquid-crystal orientation nonuniformity characteristic was evaluated. The results are shown in Table 2.

BRIEF DESCRIPTION OF THE DRAWINGS The schematic explanatory drawing which shows the structure of the transparent electrode for image retention characteristics evaluation.

Claims (9)

A liquid crystal comprising at least one polymer selected from the group consisting of a polyamic acid obtained by reacting a tetracarboxylic dianhydride and a diamine containing a compound represented by the following formula (1) or (2) and an imidized polymer thereof Aligning agent. <Formula 1>

<Formula 2>

(In the formula, n1 is each independently an integer of 1 to 8) The liquid crystal aligning agent of Claim 1 in which the said diamine further contains 1 or more types chosen from the compound represented by each of following General formula D-I and D-II. [Formula D-I]

[Formula D-II]

In formula DI, X ¹ represents a divalent organic group selected from -O-, -COO-, -OCO-, -NHCO-, -CONH-, and -CO-, and R ⁵ is a monovalent organic having a steroid skeleton. Represents a group, R ⁶ represents an alkyl group having 1 to 4 carbon atoms, a1 represents an integer of 0 to 3, and in formula (D-II), X ² represents -O-, -COO-, -OCO-, and -NHCO-, respectively. Represents a divalent organic group selected from -CONH- and -CO-, R ⁷ represents a divalent organic group having a steroid skeleton, R ⁸ each represents an alkyl group having 1 to 4 carbon atoms, and a2 each represents 0 to 3 Represents an integer) The liquid crystal according to claim 1 or 2, wherein the tetracarboxylic dianhydride comprises 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6- dianhydride. Aligning agent. The polyamic acid and imidation polymer obtained in any one of Claims 1-3 by which the tetracarboxylic dianhydride and the diamine which does not contain all the compounds represented by said Formula (1) and (2) are made to react. The liquid crystal aligning agent which further contains 1 or more types of polymers chosen from the group which consists of. The sum of the number of the amic acid structures which the polyamic acid contained in the said liquid crystal aligning agent, the number of the amic acid structures which an imidation polymer has, and the number of imide rings as described in any one of Claims 1-4. The liquid crystal aligning agent whose ratio of the number of the imide rings which an imidation polymer has is 40% or more. The liquid crystal aligning agent of any one of Claims 1-5 used for formation of the liquid crystal aligning film of a vertical alignment type. The liquid crystal aligning film formed from the liquid crystal aligning agent in any one of Claims 1-6 is provided, The liquid crystal display element characterized by the above-mentioned. Compound represented by the formula (1). Compound represented by the formula (2).

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