KR20090063143A - Liquid crystal aligning agent and liquid crystal display device - Google Patents

Abstract

A liquid crystal aligning agent is provided to ensure excellent liquid crystal orientation when applied to TN and STN type or a vertically aligned liquid crystal display device and to produce a liquid crystal alignment film with voltage holding rate and afterimage characteristic. A liquid crystal aligning agent includes at least one kind of polymer selected from the group consisting of polyamic acid and an imidized polymer thereof. The polyamic acid is obtained by reacting tetracarboxylic acid dianhydride containing 1,2,3,4-cyclobutanetetracarboxylic dianhydride, and diamine containing compound represented by chemical formula 1 and a compound represented by chemical formula 2. In chemical formula 2, n is an integer of 16-18.

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.

In more detail, it is related with the liquid crystal aligning agent which provides the liquid crystal aligning film which is excellent in voltage retention and an afterimage characteristic, and the liquid crystal display element excellent in the afterimage characteristic.

Currently, as a liquid crystal display element, a liquid crystal aligning film is formed in the surface of the board | substrate with which the transparent conductive film containing an ITO (indium-tin oxide) film etc. is provided, and it is set as a board | substrate for liquid crystal display elements, and the two sheets are opposingly arranged in the clearance gap. A so-called TN type liquid crystal cell in which a layer of nematic liquid crystals having positive dielectric anisotropy is formed to form a sandwich cell, and the long axis of the liquid crystal molecules is continuously twisted by 90 ° from one substrate to the other. TN-type liquid crystal display elements having a compound are widely known. In addition, a STN (Super Twisted Nematic) type liquid crystal display element capable of realizing a high contrast ratio compared to a TN type liquid crystal display element has been developed. It is common for the orientation of the liquid crystal molecules in the said TN type and STN type liquid crystal display elements to be controlled by the liquid crystal aligning film in which the rubbing process was performed.

On the other hand, a multi-domain vertical alignment (MVA) type liquid crystal display device which is provided with a projection on the transparent conductive film and thereby adjusts the orientation of liquid crystal molecules to improve viewing angle characteristics (see Patent Document 1 and Non-Patent Document 1). EVA (Enhanced Vertical Allignment) type liquid crystal display element (refer nonpatent literature 2 below) which performs orientation control of liquid crystal molecules by a special electrode structure, and a vertical alignment type liquid crystal display element by the photo-alignment method (refer nonpatent literature 3 below) Vertically-aligned liquid crystal display elements, such as), are proposed. These vertically-aligned liquid crystal display elements are excellent in a viewing angle characteristic, contrast, etc., and also the aspect of a manufacturing process, such as not performing a rubbing process in formation of a liquid crystal aligning film. However, compared with the above-mentioned TN type and STN type liquid crystal display elements, performance is still inadequate, especially the performance improvement regarding the vertical alignment property and the afterimage characteristic of a liquid crystal display element is calculated | required.

In order to solve the above problems, paying attention to the relationship between the voltage retention and the afterimage characteristic, the voltage retention is improved by using a polyimide or an imidized polymer thereof synthesized using a diamine compound having an allyl group in the liquid crystal alignment film, thereby remaining. Attempts have been made to improve the characteristics (see Patent Document 2 below), but the improvement of the afterimage characteristics is still insufficient even with this technique.

Moreover, by using the polyamic acid synthesize | combined using tetracarboxylic dianhydride containing 1,2,3,4-cyclobutane tetracarboxylic dianhydride and pyromellitic dianhydride as a liquid crystal aligning agent, Attempts have been made to improve voltage retention, residual charge, and afterimage characteristics (see Patent Documents 3 to 6 below), but there is a problem that sufficient voltage retention cannot be obtained with these techniques.

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

[Patent Document 2] International Publication No. WO2005 / 052028

[Patent Document 3] Japanese Patent Application No. 2001-206168

[Patent Document 4] Japanese Patent Publication No. 2001-510497

[Patent Document 5] Japanese Patent Application Laid-Open No. 2001-296525

[Patent Document 6] Japanese Unexamined Patent Publication No. 10-197875

[Patent Document 7] Japanese Unexamined Patent Publication No. 6-222366

[Patent Document 8] Japanese Unexamined Patent Publication No. 6-281939

[Patent Document 9] Japanese Patent Application Laid-Open No. 5-107544

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

[Non-Patent Document 2] "Liquid Crystal" vol. 3 No. 4 272 (1999)

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

This invention is made | formed in view of the said situation, The objective is the liquid crystal aligning film which shows the favorable liquid-crystal orientation even if it is applied not only to TN type and STN type but also to a vertical alignment type liquid crystal display element, and was excellent in voltage retention and afterimage characteristic. It is characterized by providing the liquid crystal aligning agent which provides the liquid crystal display element which is excellent in a residual characteristic, and a residual characteristic.

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

According to the present invention, the above object of the present invention firstly,

Tetracarboxylic dianhydride containing 1,2,3,4-cyclobutanetetracarboxylic dianhydride,

It is achieved by the liquid crystal aligning agent containing the at least 1 sort (s) of polymer chosen from the group which consists of the polyamic acid obtained by reacting the compound represented by following formula (1), and the diamine containing the compound represented by following formula (2), and its imidation polymer. .

<Formula 1>

Wherein n is an integer of 16 to 18

The above object of the present invention is second,

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

According to the present invention, the liquid crystal aligning agent and the remaining characteristics which provide good liquid crystal alignment property and provide a liquid crystal alignment film excellent in voltage retention and afterimage characteristics even when applied to the TN type and the STN type, as well as to the vertical alignment type liquid crystal display device. An excellent liquid crystal display element can be provided.

<Polyamic acid>

The polyamic acid contained in the liquid crystal aligning agent of this invention is a tetracarboxylic dianhydride containing 1,2,3,4-cyclobutane tetracarboxylic dianhydride, the compound represented by the said General formula (1), and the said general formula It can synthesize | combine by making diamine containing the compound represented by 2 react.

Tetracarboxylic dianhydride

The tetracarboxylic dianhydride used for synthesizing the polyamic acid contains at least 1,2,3,4-cyclobutanetetracarboxylic dianhydride. In the synthesis of the polyamic acid, tetracarboxylic dianhydride other than 1,2,3,4-cyclobutanetetracarboxylic dianhydride may be used in combination.

As such other tetracarboxylic dianhydride, it is, for example.

Butanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic Acid dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarb Acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-dish Chlohexyl tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,5,6-tricarboxynorbornane-2-acetic dianhydride, 2,3,4,5-tetra Hydrofurante tetracarboxylic dianhydride,

1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3- Dione, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan -1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-ethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1, 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) Naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-ethyl-5- (tetrahydro-2,5-dioxo 3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro- 2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 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-hexa Hydro-5,8-dimethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 5- (2, 5-D Sotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [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-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2 : 3,5: 6-anhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, represented by the following general formula TI or T-II Aliphatic or alicyclic tetracarboxylic dianhydrides such as compounds

[Formula T-I]

[Formula T-II]

(In formula TI and T-II, R <^1> and R <^3> represents the divalent organic group which has an aromatic ring, R <^2> and R <^4> represents a hydrogen atom or an alkyl group, and ^two or more R <^2> and R <^4> are the same, or May be different);

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 dianhydrides, such as bis (anhydro trimellitate) and the compound represented by following formula T-1-T-4, are 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]

Among these, butanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic 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-fura Nil) -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-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-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane- 2: 3,5: 6-anhydrides, 4 , 9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic Acid dianhydrides, 3,3 ', 4,4'-biphenylsulfontetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 1,4,5,8 -Naphthalene tetracarboxylic dianhydride, a compound represented by the following formula T-5 to T-7 among the compound represented by the formula TI and a compound represented by the following formula T-8 among the compound represented by the formula T-II It is preferable from a viewpoint that this favorable liquid crystal alignability can be expressed. Other tetracarboxylic dianhydrides which are particularly preferable are pyromellitic dianhydride and 2,3,5-tricarboxycyclopentyl acetic dianhydride.

[Formula T-5]

[Formula T-6]

[Formula T-7]

[Formula T-8]

The tetracarboxylic dianhydride used for synthesizing the polyamic acid contained in the liquid crystal aligning agent of the present invention comprises 1,2,3,4-cyclobutanetetracarboxylic dianhydride to all tetracarboxylic dianhydrides. It is preferably 40 mol% or more, more preferably 60 mol% or more.

Moreover, the tetracarboxylic dianhydride used for synthesize | combining the polyamic acid contained in the liquid crystal aligning agent of this invention is pyromellitic dianhydride further in addition to a 1,2,3,4-cyclobutane tetracarboxylic dianhydride. It is preferable to contain water or 2,3,5-tricarboxycyclopentyl acetic dianhydride. In this case, the use ratio of pyromellitic dianhydride is preferably 10 mol% or less, more preferably 1 to 10 mol%, and even more preferably 3 to 8 mol% with respect to the total tetracarboxylic dianhydride. . As a usage ratio of 2,3,5-tricarboxycyclopentyl acetic dianhydride, Preferably it is 50 mol% or less with respect to all tetracarboxylic dianhydride, More preferably, it is 15-45 mol%, 20-40 mol It is more preferable that it is%. Pyromellitic dianhydride and 2,3,5-tricarboxycyclopentyl acetic dianhydride are preferably used together preferably within the above ranges.

By using the tetracarboxylic dianhydride which contains each tetracarboxylic dianhydride in the above ratio, the polymer which shows favorable solubility with respect to the solvent mentioned later can be obtained, and it is formed with the liquid crystal aligning agent containing this. A liquid crystal aligning film is preferable at the point which becomes excellent in orientation.

[Diamine]

The diamine used for synthesizing the polyamic acid contains a compound represented by the formula (1) and a compound represented by the formula (2).

In the synthesis of the polyamic acid, other diamines other than these may be used in combination.

As such other diamine, the diamine which has a steroid skeleton, and other diamine are mentioned, for example.

As a diamine which has the said steroid skeleton, the compound represented by the following general formula (D-I), and the compound represented by the following general formula (D-II) are mentioned, for example. As these specific examples, As a compound represented by the following general formula (D-I), For example, the compound etc. represented by the following general formula (D-1)-D-6;

[Formula D-I]

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. Group)

[Formula D-II]

In Formula D-II, X ² represents a divalent organic group selected from -O-, -COO-, -OCO-, -NHCO-, -CONH-, and -CO-, and R ⁶ is a 2 having a steroid skeleton. Represents an organic group)

[Formula D-1]

[Formula D-2]

[Formula D-3]

[Formula D-4]

[Formula D-5]

[Formula D-6]

As a compound represented by the said Formula (D-II), the compound etc. which are represented by following formula (D-7)-D-9 are mentioned, for example.

[Formula D-7]

[Formula D-8]

[Formula D-9]

As said other diamine, it is, for example

p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenylsulfide, 4,4 ' -Diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 4,4'-diaminodiphenylether, 1,5-dia Minonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-ditrifluoromethyl-4, 4'-diaminobiphenyl, 3,3'-ditrifluoromethyl-4,4'-diaminobiphenyl, 5-amino-1- (4'-aminophenyl) -1,3,3-trimethyl Indan, 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-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-amino Oxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9, 9-bis (4-aminophenyl) -10-hydroanthracene, 2,7-diaminofluorene, 9,9-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, 1,4,4 '-(p-phenyleneisopropylidene) Bisaniline, 4,4 '-(m-phenyleneisopropylidene) bisaniline, 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl Aromatic diamines such as;

1,1-methacrylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine , 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindenylenedimethylene diamine, tricyclo [6.2.1.0 ^2,7 ] -undecylene Aliphatic or alicyclic diamines such as dimethyldiamine, 4,4'-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane, and 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'-di (4-aminophenyl) -benzidine, a compound represented by the following formula D-III, represented by the following formula D-IV Diamine which has two primary amino groups and nitrogen atoms other than the said primary amino group in molecule | numerators, such as a compound;

[Formula D-III]

In Formula D-III, R ⁷ 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 )

[Formula D-IV]

In formula (D-IV), R ⁸ represents a divalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine, and X ⁴ represents a divalent organic group , A plurality of X ⁴ may be the same or different)

A compound represented by Formula D-V;

[Formula D-V]

(In formula DV, X <^5> represents the divalent organic group chosen from -O-, -COO-, -OCO-, -NHCO-, -CONH-, and -CO-, and R <^9> is monovalent which has a fluorine atom. An organic group or an alkyl group having 6 to 30 carbon atoms)

A compound represented by the following formula D-VI;

[Formula D-VI]

(In formula (D-VI), R <^10> represents a C1-C12 hydrocarbon group, two or more R <^10> may be same or different, p is an integer of 1-3, q is an integer of 1-20.

The compound etc. which are represented by following formula D-10 or D-11 are mentioned, respectively. These diamines can be used individually or in combination of 2 or more types.

[Formula D-10]

[Formula D-11]

(Y in Formula D-10 is an integer of 2 to 12, and z in Formula D-11 is an integer of 1 to 5)

Among them, diamine having a steroid skeleton, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 1,5-diaminonaphthalene, 2,2'- Dimethyl-4,4'-diaminobiphenyl, 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 2,7-diaminofluorene, 4,4'-diaminodi Phenylether, 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-phenyl Rendiisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 1,4-cyclohexanediamine, 4,4 ' Methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6- Dami Acridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole Bazol, N, N'-di (4-aminophenyl) -benzidine, the compound represented by the following formula D-12 among the compounds represented by the formula (D-III), the compound represented by the formula (D-IV) Compound represented by -13, dodecaneoxy-2,4-diaminobenzene, pentadecaneoxy-2,4-diaminobenzene, hexadecaneoxy-2,4-diaminobenzene among the compounds represented by the above formula DV , Octadecaneoxy-2,4-diaminobenzene, dodecaneoxy-2,5-diaminobenzene, pentadecaneoxy-2,5-diaminobenzene, hexadecaneoxy-2,5-diaminobenzene, octa 1,3-bis (3-aminopropyl) -tetramethyldi in decanoxyoxy 2,5-diaminobenzene, a compound represented by the following formula D-14 to D-16 or a compound represented by the above formula D-VI Siloxane is preferred The.

[Formula D-12]

[Formula D-13]

[Formula D-14]

[Formula D-15]

[Formula D-16]

Other particularly preferred diamines are diamines having a steroid backbone, of which compounds represented by the above formulas (D-I or D-II) are preferred.

The diamine used for synthesizing the polyamic acid contained in the liquid crystal aligning agent of the present invention is preferably 40 mol% or more, more preferably 50 to 80 mol%, More preferably, it contains 55-75 mol%. The diamine used for synthesizing the polyamic acid is preferably 20 mol% or more, more preferably 30 to 60 mol%, still more preferably 35 to 55 mol of the compound represented by the formula (2) relative to the total diamine. % Is contained.

It is preferable that the diamine used for synthesizing the polyamic acid further contains a diamine having a steroid skeleton as another diamine, and the use ratio of the diamine having a steroid skeleton in this case is preferably 50 mol based on the total diamine. % Or less, More preferably, it is 10-30 mol%.

It is preferable because the liquid crystal aligning agent which provides the liquid crystal aligning film excellent in voltage retention and afterimage characteristics can be obtained by using the diamine which contains each diamine in the ratio as above-mentioned.

[Synthesis of Polyamic Acid]

The polyamic acid which may be contained in the liquid crystal aligning agent of the present invention is a tetracarboxylic dianhydride containing 1,2,3,4-cyclobutanetetracarboxylic dianhydride, a compound represented by the formula (1) and It is obtained by making diamine containing the compound represented by the said Formula (2) react.

The use ratio of the tetracarboxylic dianhydride and the diamine used in the synthesis reaction of the polyamic acid is preferably a ratio in which the acid anhydride group of the tetracarboxylic dianhydride is 0.5 to 2 equivalents relative to 1 equivalent of the amino group of the diamine. Preferably a ratio of 0.7 to 1.2 equivalents.

The synthesis reaction of the polyamic acid is preferably in an organic solvent, preferably at -20 ° C to 150 ° C, more preferably under a temperature condition of 0 to 100 ° C, preferably 1 to 48 hours, more preferably 2 To 12 hours. The organic solvent is not particularly limited as long as it can dissolve the polyamic acid produced, for example, 1-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, 3 Amide compounds such as -butoxy-N, N-dimethylpropanamide, 3-methoxy-N, N-dimethylpropanamide, 3-hexyloxy-N, N-dimethylpropanamide, dimethyl sulfoxide, γ-buty Aprotic compounds such as rolactone, tetramethylurea and hexamethylphosphortriamide; Phenolic compounds, such as m-cresol, xylenol, a phenol, and a halogenated phenol, etc. can be illustrated. It is preferable that the usage-amount (a) of an organic solvent is the quantity which normally becomes 0.1-30 weight% with respect to the total amount (a + b) of the reaction solution, for the total amount (b) of tetracarboxylic dianhydride and a diamine compound.

You may use together with the said organic solvent in the range which polyamic acid which produces | generates the alcohol, ketone, ester, ether, halogenated hydrocarbon, hydrocarbon etc. which are poor solvents of a polyamic acid does not precipitate. As a specific example of such a poor solvent, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol, propylene glycol, 1,4-butanediol, Triethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxy propionate, ethyl ethoxy Propionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether , Ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloro Ethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisopentyl ether and the like.

When using together an organic solvent and a poor solvent, although the usage-amount of a poor solvent can be set suitably in the range which does not precipitate the polyamic acid produced | generated, it is preferable that it is 30 weight% or less with respect to whole quantity of a solvent, and it is more preferable that it is 20 weight% or less desirable.

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 of melt | dissolving this polyamic acid again in an organic solvent, and then depositing with a poor solvent or performing the process of distilling under reduced pressure with an evaporator once or several times.

<Imidated Polymer>

The imidation polymer which can be contained in the liquid crystal aligning agent of this invention can be obtained by dehydrating and ring-closing the polyamic acid as mentioned above and imidating it.

As tetracarboxylic dianhydride used for the synthesis | combination of the said imidation polymer, the compound similar to tetracarboxylic dianhydride used for the synthesis | combination of the polyamic acid mentioned above is mentioned. Moreover, the diamine same as the diamine compound used for the synthesis | combination of said polyamic acid is mentioned as a diamine used in the synthesis | combination of the imidation polymer contained in the liquid crystal aligning agent of this invention.

The imidized polymer contained in the liquid crystal aligning agent of this invention may be the complete imide which dehydrated and closed all the amic acid structures which the polyamic acid which is a raw material has, and only a part of amic acid structure is dehydrated and closed, and the amic acid structure The partial imide which the and imide ring structure coexists may be sufficient.

It is preferable that the imidation ratio of the imidation polymer contained in the liquid crystal aligning agent of this invention is 60% or more, It is more preferable that it is 70% or more, It is still more preferable that it is 80% or more. By using the imidation polymer whose imidation ratio is 60% or more, the liquid crystal aligning agent which can form the excellent liquid crystal aligning film by an afterimage characteristic can be obtained.

The said imidation ratio shows the ratio which the number of the imide ring structures to the sum total of the number of the amic acid structures and the number of imide ring structures of an imidation polymer occupies as a percentage. At this time, a part of the imide ring may be an isoimide ring. The imidation ratio is obtained by dissolving the imidized polymer in a suitable deuterated solvent (for example, deuterated dimethyl sulfoxide) and measuring ¹ H-NMR at room temperature using tetramethylsilane as a reference substance. Can be obtained by

Imidation ratio (%) = (1-A ¹ / A ² × α) × 100

(In Formula 1, A ¹ is the peak area derived from the proton of the NH group appearing near 10 ppm of chemical shift, A ² is the peak area derived from other protons, and α is a precursor of the imidized polymer (polyamic acid). Ratio of the number of other protons to one proton of the NH group in

The dehydration ring closure of the polyamic acid is preferably heated by (i) a method of heating the polyamic acid, or (ii) the polyamic acid is dissolved in an organic solvent, and a dehydrating agent and a dehydration ring closure catalyst are added to the solution, if necessary. It is done by the method.

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. The reaction time is preferably 1 to 120 hours, more preferably 2 to 48 hours. 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.

On the other hand, in the method of adding a dehydrating agent and a dehydrating ring-closure catalyst to the solution of the polyamic acid of said (ii), acid anhydrides, such as an acetic anhydride, a propionic anhydride, a trifluoroacetic anhydride, can be used, for example. Although the usage-amount of a dehydrating agent changes with a desired imidation ratio, it is preferable to set it as 0.01-20 mol with respect to 1 mol of amic-acid structures 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. The imidation ratio can be made higher, so that the usage-amount of said dehydrating agent and dehydrating ring closure agent is large. 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 1 to 24 hours, more preferably 2 to 8 hours.

In the said method (ii), the reaction solution containing an imidation polymer is obtained as mentioned above. 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.

Terminal Modified Polymer

The polyamic acid or imidation polymer contained in the liquid crystal aligning agent of this invention may be terminal modified form in which molecular weight was adjusted. By using the polymer of the terminal modification type, the coating characteristic of a liquid crystal aligning agent, etc. can be further improved, without impairing the effect of this invention. Such a terminal-modified polymer can be performed by adding a molecular weight modifier to the polymerization reaction system when synthesizing the polyamic acid. As a molecular weight modifier, an acid anhydride, a monoamine compound, a monoisocyanate compound, etc. are mentioned, for example.

Examples of the acid anhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride, n-hexadecylsuccinic anhydride, and the like. have. 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- Eicosylamine, etc. are mentioned. As said monoisocyanate compound, phenyl isocyanate, naphthyl isocyanate, etc. are mentioned, for example.

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 of tetracarboxylic dianhydride and diamine used when synthesizing the polyamic acid.

Solution viscosity

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

The solution viscosity (mPa * s) of the said polymer is 25 using the E-type rotational viscometer with respect to the polymer solution of 10 weight% of concentration manufactured using the good solvent of this polymer (for example, (gamma) -butyrolactone). It is the value measured at ° C.

<Other additives>

The liquid crystal aligning film of this invention contains 1 or more types of polymers chosen from the group which consists of the above-mentioned polyamic acid and its imidation polymer. As a polymer contained in the liquid crystal aligning agent of this invention, it is preferable that it is an imidation polymer.

Although the liquid crystal aligning film of this invention contains the above-mentioned polymer as an essential component, it may contain other components as needed. Examples of such other components include compounds having two or more epoxy groups in the molecule (hereinafter referred to as "epoxy compound"), functional silane compounds, and the like.

As said epoxy compound, for example

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, 1,3,5,6- tetraglycidyl-2 , 4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N- diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 3- (N-allyl-N-glycidyl) aminopropyltrimethoxysilane, 3- (N, N-di And glycidyl) aminopropyltrimethoxysilane.

As the use ratio of the epoxy compound as mentioned above, it is 40 weight part or less with respect to 100 weight part of total amounts of a polymer (referring to the total amount of the said polyamic acid and its imidation polymer contained in a liquid crystal aligning agent), More preferably, Preferably from 0.1 to 30 parts by weight.

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-urei dopropyltriethoxy 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-diazanyl acetate, 9-triethoxysilyl-3,6-diazanyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-acea Minopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyl triethoxysilane etc. are mentioned.

As a usage ratio of the above-mentioned functional silane compound, Preferably it is 2 weight part or less with respect to 100 weight part of total amounts of a polymer, More preferably, it is 0.2 weight part or less.

<Liquid crystal aligning agent>

The liquid crystal aligning agent of the present invention is preferably one or more selected from the group consisting of the polyamic acid and the imidized polymer thereof as described above, and other additives which are optionally blended as necessary, dissolved in an organic solvent. .

As said organic solvent, the solvent illustrated as what is used for the synthesis reaction of 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 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, 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 There may be mentioned the lactate, isoamyl propionate, isoamyl isobutyrate, di-isopentyl ether. These can be used independently, or can mix and use 2 or more types.

Although solid content concentration (the ratio which the total weight of components other than the solvent of 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 considered suitably in consideration of viscosity, volatility, etc., Preferably it is 1 To 10% by weight. That is, the liquid crystal aligning agent of this invention is apply | coated to the surface of a board | substrate as mentioned later, Preferably, the coating film used as a liquid crystal aligning film is formed by heating, However, when solid content concentration is less than 1 weight%, the film thickness of this coating film is too much. When it becomes small and a favorable liquid crystal aligning film is unable to be obtained, and solid content concentration exceeds 10 weight%, the film thickness of a coating film becomes large too much and a favorable liquid crystal aligning film cannot be obtained, the viscosity of a liquid crystal aligning agent increases and application | coating characteristic falls. Will be.

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, the range of 1.5 to 4.5 weight% of solid content concentration is especially preferable by the spinner method. 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 liquid crystal aligning agent of this invention as mentioned above.

The liquid crystal display element of this invention can be manufactured by the process of the following (1)-(3), for example.

(1) First, as a pair of two board | substrates with which the patterned transparent conductive film is provided, the liquid crystal aligning agent of this invention is used on each transparent conductive film formation surface, for example, the roll coater method, the spinner method, the offset printing method, Each coating surface is applied by appropriate coating such as an inkjet printing method, and then a coating film is formed by heating each coating surface. Here, 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, poly (alicyclic olefin) and the like can be used. Examples of the transparent conductive film provided on one side of the substrate include an NESA film containing tin oxide (SnO ₂ ) (registered trademark of PPG, USA) and an ITO film containing indium tin oxide (In ₂ O ₃ -SnO ₂ ). In order to obtain a patterned transparent conductive film, for example, a method of forming a pattern by photo-etching after forming a transparent conductive film without a pattern, and using a mask having a desired pattern when forming a transparent conductive film Method and the like can be used. At the time of coating of the liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a pretreatment for applying a functional silane compound, a functional titanium compound, or the like to the surface on which the coating film should be formed on the substrate surface in advance. May be performed.

The heating temperature after liquid crystal aligning agent application becomes like this. Preferably it is 30-300 degreeC, More preferably, it is 40-250 degreeC, Heating time becomes like this. Preferably it is 1-30 minutes, More preferably, it is 5-20 minutes. 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) Next, the rubbing process which rubs a predetermined surface with the roll which wound up the coating film surface formed as mentioned above with the cloth containing fibers, such as nylon, a rayon, a cotton, for example, is performed. Thereby, the orientation ability of a liquid crystal molecule is provided to a coating film, and it becomes a liquid crystal aligning film. In addition, a vertical alignment liquid crystal display element may not perform a rubbing process. In this case, the said coating film can be used as a liquid crystal aligning film as it is.

Moreover, about the liquid crystal aligning film formed with the liquid crystal aligning agent of this invention, for example, patent document 7 (Unexamined-Japanese-Patent No. 6-222366) and patent document 8 (Japanese Unexamined-Japanese-Patent No. 6-281939). 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 Publication No. 9 and Japanese Patent Laid-Open No. 5-107544. It is obtained by forming a resist film on a part of the surface of the liquid crystal alignment film as described and then performing a rubbing treatment in a direction different from the rubbing treatment previously performed, and then removing the resist film, and allowing the liquid crystal alignment film to have different liquid crystal alignment capabilities for each region. It is possible to improve the viewing characteristics of the liquid crystal display element.

(3) With respect to the pair of substrates on which the liquid crystal alignment film is formed as described above, the two substrates face each other through a gap (cell spacing) so that the rubbing direction of the liquid crystal alignment films of the two substrates is perpendicular or antiparallel to each other. The substrate periphery is bonded using a sealant, the liquid crystal is injected and filled into the cell surface partitioned by the substrate surface and the sealant, and the injection hole is sealed to form a liquid crystal cell. Moreover, a liquid crystal display element can be obtained by bonding a polarizing plate to the outer surface of a liquid crystal cell so that its polarization direction may coincide with or perpendicular to the rubbing direction of the liquid crystal aligning film formed in each board | substrate. 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 preferable, and for example, a siphon base liquid crystal, a subfamily clock liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal and an ester liquid crystal , Terphenyl-based liquid crystal, biphenylcyclohexane-based liquid crystal, pyrimidine-based liquid crystal, dioxane-based liquid crystal, bicyclooctane-based liquid crystal, kuban-based liquid crystal and the like can be used. Furthermore, for these liquid crystals, for example, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonaate and cholesteryl carbonate; Chiral agent sold as brand names "C-15" and "CB-15" (manufactured by Merck); Ferroelectric liquid crystals, such as p-disiloxybenzylidene-p-amino-2-methylbutyl cinnamate, can also be added and used.

As a polarizing plate joined 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 between the cellulose acetate protective film, or the polarizing plate which consists of H film itself is mentioned.

<Example>

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not restrict | limited to these Examples.

In addition, the imidation ratio of the imidation polymer in the following synthesis examples is ¹ H which melt | dissolved in the deuterated dimethyl sulfoxide after drying the imidation polymer sufficiently at room temperature, and measured tetramethylsilane at room temperature as a reference substance. It was calculated from -NMR and calculated according to Equation 1 above.

Synthesis Example 1

1,2,3,4-cyclobutanetetracarboxylic dianhydride 98 g (0.5 mol) as tetracarboxylic dianhydride, 61 g of 2,4-diamino-N, N- diallyl aniline as a diamine compound ( 0.3 mole) and 123 g (0.2 mole) of n-hexadecyl [3,5-bis (4-aminobenzoylamino)] benzoate are dissolved in 1,127 g of N-methyl-2-pyrrolidone and at 60 ° C. The reaction was carried out for 6 hours to obtain a polymer solution containing polyamic acid. The solution viscosity measured as a small amount of the obtained polyamic-acid solution, the addition of N-methyl- 2-pyrrolidone, and measured as a solution of 10 weight% of polyamic-acid concentration was 50 mPa * s.

Subsequently, 1,409 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 198 g of pyridine and 204 g of acetic anhydride were added, and a dehydration ring-closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring closure reaction, the solvent in the system was substituted with new γ-butyrolactone (pyridine and acetic anhydride used in the dehydration ring closure reaction were removed to the outside of the system), thereby imidating polymer having an imidation ratio of about 94% ( About 1,300 g of a polymer solution containing A-1) was obtained. The solution viscosity of this imidated polymer was fractionated, the solution viscosity measured as a solution of 10 weight% of polymer concentration by adding (gamma) -butyrolactone solution was 60 mPa * s.

Synthesis Example 2

1,2,3,4-cyclobutanetetracarboxylic dianhydride 98 g (0.5 mol) as tetracarboxylic dianhydride, 61 g of 2,4-diamino-N, N- diallyl aniline as a diamine compound ( 0.3 mol) and 128 g (0.2 mol) of n-octadecyl [3,5-bis (4-aminobenzoylamino)] benzoate are dissolved in 1,149 g of N-methyl-2-pyrrolidone and 6 at 60 ° C. The reaction was carried out for a time to obtain a polymer solution containing polyamic acid. A small amount of the obtained polyamic acid solution was fractionated, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 52 mPa · s.

Subsequently, 1,437 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 198 g of pyridine and 204 g of acetic anhydride were added, and a dehydration ring-closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring reaction, the solvent in the system was substituted with new γ-butyrolactone (pyridine and acetic anhydride used in the dehydration ring closure reaction were removed to the outside of the system), thereby imidating polymer having an imidation ratio of about 95% ( About 1,310 g of a polymer solution containing A-2) was obtained. The solution viscosity of this imidated polymer was fractionated, the solution viscosity measured as a solution of 10 weight% of polymer concentration by adding (gamma) -butyrolactone solution was 63 mPa * s.

Synthesis Example 3

1,2,3,4-cyclobutanetetracarboxylic dianhydride 93 g (0.48 mol) as tetracarboxylic dianhydride and 5 g (0.03 mol) pyromellitic dianhydride, 2,4-dia as diamine compound 61 g (0.3 mole) of mino-N, N-diallylaniline and 123 g (0.2 mole) of n-hexadecyl [3,5-bis (4-aminobenzoylamino)] benzoate are N-methyl-2-pi It melt | dissolved in 1,129 g of rolidones, and it reacted at 60 degreeC for 6 hours, and obtained the polymer solution containing polyamic acid. 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 N-methyl-2-pyrrolidone was 55 mPa · s.

Subsequently, 1,411 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 198 g of pyridine and 204 g of acetic anhydride were added, and a dehydration ring-closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring reaction, the solvent in the system was substituted with new γ-butyrolactone (pyridine and acetic anhydride used for the dehydration ring closure reaction were removed to the outside of the system), thereby imidating polymer having an imidation ratio of about 94% ( About 1,320 g of a polymer solution containing A-3) was obtained. The solution viscosity of this imidated polymer was fractionated, the solution viscosity measured as a solution of 10 weight% of polymer concentration by adding (gamma) -butyrolactone solution was 65 mPa * s.

Synthesis Example 4

1,2,3,4-cyclobutanetetracarboxylic dianhydride 93 g (0.48 mol) as tetracarboxylic dianhydride and 5 g (0.03 mol) pyromellitic dianhydride, 2,4-dia as diamine compound 61 g (0.3 mole) of mino-N, N-diallylaniline and 128 g (0.2 mole) of n-octadecyl [3,5-bis (4-aminobenzoylamino)] benzoate It dissolved in 1,152 g of ralidone and reacted at 60 degreeC for 6 hours, and obtained the polymer solution containing a polyamic acid. 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 N-methyl-2-pyrrolidone was 56 mPa · s.

Subsequently, 1,440 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 198 g of pyridine and 204 g of acetic anhydride were added, and a dehydration ring-closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring reaction, the solvent in the system was substituted with new γ-butyrolactone (pyridine and acetic anhydride used in the dehydration ring closure reaction were removed to the outside of the system), thereby imidating polymer having an imidization ratio of about 93% ( About 1,310 g of a polymer solution containing A-4) was obtained. The solution viscosity of this imidated polymer was fractionated, the solution viscosity measured as a solution of 10 weight% of polymer concentration by adding (gamma) -butyrolactone solution was 65 mPa * s.

Synthesis Example 5

1,2,3,4-cyclobutanetetracarboxylic dianhydride 93 g (0.48 mol) as tetracarboxylic dianhydride and 5 g (0.03 mol) pyromellitic dianhydride, 2,4-dia as diamine compound 71 g (0.35 mole) of mino-N, N-diallyl aniline, 61 g (0.1 mole) of n-hexadecyl [3,5-bis (4-aminobenzoylamino)] benzoate and represented by the above formula (D-3) 26 g (0.05 mol) of the compound was dissolved in 1,029 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours to obtain a polymer solution containing polyamic acid. The solution viscosity measured as a small amount of the obtained polyamic-acid solution, the addition of N-methyl- 2-pyrrolidone, and measured as a solution of 10 weight% of polyamic-acid concentration was 50 mPa * s.

Subsequently, 1,286 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 198 g of pyridine and 204 g of acetic anhydride were added, and a dehydration ring-closure reaction was performed at 110 ° C for 4 hours. After the dehydration ring reaction, the solvent in the system was substituted with new γ-butyrolactone (pyridine and acetic anhydride used in the dehydration ring closure reaction were removed to the outside of the system), thereby imidating polymer having an imidization ratio of about 93% ( About 1,300 g of a polymer solution containing A-5) was obtained. The solution viscosity of this imidated polymer was fractionated, the solution viscosity measured as a solution of 10 weight% of polymer concentration by adding (gamma) -butyrolactone solution was 60 mPa * s.

Synthesis Example 6

As tetracarboxylic dianhydride 64 g (0.33 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 34 g (0.15 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride and 5 g (0.03 mol) of pyromellitic dianhydride, 61 g (0.3 mol) of 2,4-diamino-N, N- diallyl aniline as a diamine compound and n-hexadecyl [3,5-bis (4-amino Benzoylamino)] benzoate 123 g (0.2 mol) was dissolved in 1,146 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours to obtain a polymer solution containing polyamic acid. 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 N-methyl-2-pyrrolidone was 55 mPa · s.

Subsequently, 1,433 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 198 g of pyridine and 204 g of acetic anhydride were added, and a dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring reaction, the solvent in the system was substituted with new γ-butyrolactone (pyridine and acetic anhydride used in the dehydration ring closure reaction were removed to the outside of the system), thereby imidating polymer having an imidization ratio of about 93% ( About 1,300 g of a polymer solution containing A-6) was obtained. The solution viscosity of this imidated polymer was fractionated, the solution viscosity measured as a solution of 10 weight% of polymer concentration by adding (gamma) -butyrolactone solution was 65 mPa * s.

Comparative Synthesis Example 1

1,2,3,4-cyclobutanetetracarboxylic dianhydride 98 g (0.5 mol) as tetracarboxylic dianhydride, 61 g of 2,4-diamino-N, N- diallyl aniline as a diamine compound ( 0.3 mole) and 76 g (0.2 mole) of 4- [4- (4-trans-n-heptylcyclohexyl) phenoxy] -1,3-diaminobenzene were added to 941 g of N-methyl-2-pyrrolidone. It melt | dissolved and reacted at 60 degreeC for 6 hours, and obtained the polymer solution containing a polyamic acid. A small amount of the obtained polyamic acid solution was aliquoted, and N-methyl-2-pyrrolidone was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight was 48 mPa · s.

Subsequently, 1,177 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 198 g of pyridine and 204 g of acetic anhydride were added, and a dehydration ring-closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring reaction, the solvent in the system was substituted with new γ-butyrolactone (pyridine and acetic anhydride used in the dehydration ring closure reaction were removed to the outside of the system), thereby imidating polymer having an imidation ratio of about 95% ( About 1,300 g of a polymer solution containing B-1) was obtained. The solution viscosity of this imidated polymer was fractionated, the solution viscosity measured as a solution of 10 weight% of polymer concentration by adding (gamma) -butyrolactone solution was 55 mPa * s.

Example 1

<Production of Liquid Crystal Alignment Agent>

(Gamma) -butyrolactone (BL), N-methyl-2-pyrrolidone (NMP), and butyl cellosolve (BC) are added to the solution containing the imidation polymer (A-1) obtained by the said synthesis example 1 To a solvent composition of BL: NMP: BC = 71:17:12 (weight ratio) and a solid content concentration of 4% by weight, and the solution was filtered using a filter having a pore diameter of 1 µm to prepare a liquid crystal aligning agent.

<Evaluation of Voltage Retention Rate>

The above-mentioned liquid crystal aligning agent was apply | coated to the transparent electrode surface of the glass substrate with a transparent electrode containing an ITO membrane using a liquid crystal aligning film printing machine (made by Nippon Shashin Insatsu Co., Ltd.), and it heated for 1 minute on 80 degreeC hotplates. Furthermore, the coating film of 600 kPa of average film thicknesses was formed by heating on a 200 degreeC hotplate for 10 minutes. This operation was repeated and two sheets (pair) of the board | substrate which has a coating film were manufactured. When the coating film on these board | substrates was observed with the microscope of 20 times the magnification, printing unevenness and pinhole were not observed and applicability | paintability was favorable.

After apply | coating the 5.5-micrometer-diameter aluminum oxide sphere containing epoxy resin adhesive agent on each outer edge which has a pair of liquid crystal aligning film with a coating film with a coating film, it bonded and crimped | 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-2038 by Merck Co., Ltd.) between a pair of board | substrates from a liquid crystal injection hole, the liquid crystal cell for evaluating voltage retention was produced by sealing a liquid crystal injection hole with an acryl-type photocuring adhesive.

About this liquid crystal cell, after applying the voltage of 5V by 60 microseconds application time and 167 milliseconds span at the environmental temperature of 60 degreeC, the voltage retention after 167 milliseconds after application | release cancellation was measured. The measurement apparatus used VHR-1 by Toyo Technica. The case where the voltage retention was 95% or more was evaluated as voltage retention "good".

<Evaluation of Afterimage Characteristics>

Except having used the board | substrate which has the ITO electrode like FIG. 1 as a board | substrate, the liquid crystal cell for evaluating an afterimage characteristic was produced according to the method described in the above-mentioned <evaluation of voltage retention>. A direct current voltage 6.0 V was applied to electrode A and a direct current voltage 0.5 V to electrode B for 24 hours at room temperature. After the voltage was removed, the luminance difference in the regions corresponding to the electrodes A and B when the DC voltages 0.1 to 5.0 V were applied in 0.1 V increments to the electrodes A and B was evaluated. It evaluated as the afterimage characteristic "good" when a luminance difference was small, and the afterimage characteristic "bad" when a luminance difference was large.

Examples 2 to 6 and Comparative Example 1

The liquid crystal aligning agent was produced and evaluated similarly to Example 1 except having used the solution containing the polymer of Table 1 instead of the solution containing an imidation polymer (A-1), respectively. The evaluation results are shown in Table 1 below.

BRIEF DESCRIPTION OF THE DRAWINGS The schematic diagram of the liquid crystal cell manufactured for evaluation of afterimage characteristic.

Claims (6)

Tetracarboxylic dianhydride containing 1,2,3,4-cyclobutanetetracarboxylic dianhydride, A liquid crystal aligning agent containing at least one polymer selected from the group consisting of a polyamic acid obtained by reacting a diamine containing a compound represented by the following formula (1) and a compound represented by the following formula (2) and an imidized polymer thereof . <Formula 1>

<Formula 2>

Wherein n is an integer of 16 to 18 The liquid crystal aligning agent of Claim 1 in which tetracarboxylic dianhydride contains 1-10 mol% pyromellitic dianhydride further with respect to all tetracarboxylic dianhydride. The liquid crystal aligning agent according to claim 1 or 2, wherein the diamine further contains a diamine having a steroid skeleton. The liquid crystal aligning agent according to any one of claims 1 to 3, wherein the tetracarboxylic dianhydride further contains 2,3,5-tricarboxycyclopentylacetic dianhydride. The liquid crystal aligning agent of any one of Claims 1-4 which further contains the compound which has two or more epoxy groups in a molecule | numerator. The liquid crystal aligning film formed from the liquid crystal aligning agent in any one of Claims 1-5 is provided. The liquid crystal display element characterized by the above-mentioned.

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