KR20010100887A - Materials for Aligning Liquid Crystals and Liquid Crystal Display Apparatus - Google Patents

Abstract

This invention relates to the liquid crystal aligning agent and liquid crystal display element which are used in order to form the liquid crystal aligning film of a liquid crystal display element. More specifically, in the liquid crystal aligning agent and the liquid crystal display element which provide a liquid crystal aligning film which has favorable liquid crystal alignability, and at the same time has a short afterimage erasing time of a liquid crystal display element, and also brings the outstanding long-term reliability to a liquid crystal display element. It is about.

Description

Liquid crystal aligning agent and liquid crystal display device {Materials for Aligning Liquid Crystals and Liquid Crystal Display Apparatus}

This invention relates to the liquid crystal aligning agent and liquid crystal display element which are used in order to form the liquid crystal aligning film of a liquid crystal display element. More specifically, in the liquid crystal aligning agent and the liquid crystal display element which provide a liquid crystal aligning film which has favorable liquid crystal alignability, and at the same time has a short afterimage erasing time of a liquid crystal display element, and also brings the outstanding long-term reliability to a liquid crystal display element. It is about.

Conventionally, a TN in which a nematic liquid crystal having positive dielectric anisotropy is sandwiched between substrates with a transparent electrode having a liquid crystal alignment film made of polyimide or the like is sandwiched so that the long axis of the liquid crystal molecules is continuously twisted 90 degrees between the substrates. BACKGROUND ART A liquid crystal display element (TN type liquid crystal display element) having a (Twisted Nematic) type liquid crystal cell is known. The liquid crystal orientation of this TN type liquid crystal display element is formed by the liquid crystal aligning film in which the rubbing process was performed.

Moreover, in recent years, STN (Super Twisted Nematic) type liquid crystal display element which is a liquid crystal display element excellent in contrast and visual dependence, and a vertical alignment type liquid crystal display element are developed. The STN type liquid crystal display element uses what mixed the nematic liquid crystal and the chiral agent which is an optically active substance as a liquid crystal, and uses the birefringence effect which arises when the long axis of a liquid crystal molecule twists continuously more than 180 degrees between board | substrates. . In addition, the vertically-aligned liquid crystal display element vertically aligns a liquid crystal having a negative dielectric anisotropy of the liquid crystal molecules, and operates by simple matrix driving by knocking down the molecules by voltage application.

However, when a liquid crystal display element is produced using a conventionally known polyamic acid or a liquid crystal aligning agent made of an imide polymer having a structure obtained by dehydrating and closing the ring, a residual image occurs because the residual voltage of the liquid crystal display element is large. However, there is a problem in that sufficient contrast cannot be obtained because the time for erasing this afterimage is long. In addition, when the liquid crystal display element is used for a long time, uneven display defects may occur, thereby impairing the reliability as the liquid crystal display element.

The object of the present invention is to exhibit good orientation characteristics, and to shorten the time required for the afterimage to be erased after releasing the voltage application of the liquid crystal display element (hereinafter referred to as "afterimage erase time"), and at the same time for a long time. It is providing the liquid crystal aligning agent which can form the liquid crystal aligning film which does not generate | occur | produce when voltage is applied.

Another object of this invention is to provide the liquid crystal display element provided with the liquid crystal aligning film of the liquid crystal aligning agent of this invention.

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

According to the present invention, the above objects and advantages of the present invention,

Obtained by reacting at least one compound selected from the group consisting of (A) (a) tetracarboxylic dianhydride, (b) diamine compound and (c) dicarboxylic anhydride, monoamine compound and monoisocyanate compound And, at the same time, an end-sealing polyamic acid having an alicyclic skeleton and (B) at least one end-sealing polymer selected from the group consisting of end-sealing imidized polymers obtained by dehydrating and closing the polyamic acid. Achieved by the alignment agent.

The liquid crystal aligning agent of this invention is the terminal unsealed polyamide obtained by making (A) tetracarboxylic dianhydride and (B) diamine compound react with the said terminal sealing polyamic acid and / or terminal sealing imidation polymer further. It is preferable to contain at least 1 type of terminal unsealed polymer selected from the group which consists of an acid and the terminal unsealed imidation polymer obtained by dehydrating and ring-closing this polyamic acid.

Moreover, it is more preferable that the liquid crystal aligning agent of this invention contains a terminal sealing imidation polymer and a terminal unsealed polyamic acid.

Moreover, according to this invention, the said objective and advantage of this invention are achieved by the liquid crystal display element characterized by providing the liquid crystal aligning film obtained from the liquid crystal aligning agent of this invention second.

Hereinafter, the present invention will be described in detail.

Tetracarboxylic dianhydride

The end-sealed polyamic acid and the end-sealed imidized polymer used in the present invention can introduce an alicyclic skeleton by using an alicyclic tetracarboxylic dianhydride and / or an alicyclic diamine. It is preferable to introduce an alicyclic skeleton by using acid dianhydride. Examples of the alicyclic tetracarboxylic dianhydride include 2,3,5-tricarboxycyclopentyl acetic dianhydride, 3,5,6-tricarboxynorbornane-2-acetic dianhydride, 2,4, 5-tricarboxycyclohexyl acetic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane tracarboxylic 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-cyclo Hexanetetracarboxylic dianhydride, 3,3 ', 4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurante tetracarboxylic dianhydride, 1,3, 3a, 4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl)- Proto [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-hexa Hydro-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-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid Anhydride, bicyclo [2,2,2] -octo-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-dione -6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), the tetracarboxylic dianhydride represented by following General formula (1), 2, 3, etc. are mentioned.

In formula, R <^1> , R <^3> and R <^5> represent a cycloaliphatic divalent organic group, R <^2> , R <^4> and R <^6> represent a hydrogen atom or an alkyl group, and ^two or more R <^2> , R <^4> and R <^6> represent Each may be the same or different.

These tetracarboxylic dianhydrides are used individually by 1 type or in combination of 2 or more types.

Of these, 2,3,5-tricarboxycyclopentyl acetic dianhydride, 3,5,6-tricarboxynorbornane-2-acetic dianhydride, 2,4,5-tricarboxycyclohexyl acetic dianhydride, 1 , 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetra Carboxylic dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic 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] -octo-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2, 4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione) is preferable from the viewpoint of being able to express good liquid crystal orientation. Especially preferred are 2,3,5-tricarboxycyclopentyl acetic dianhydride, 2,4,5-tricarboxycyclohexyl acetic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1 , 3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo- 3-furanyl) -naphtho [1,2-c] furan-1,3-dione, and 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-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro -3 '-(tetrahydrofuran-2', 5'-dione) is mentioned.

In addition, the terminal sealing polyamic acid and terminal sealing imidation polymer used by this invention can also be obtained using other tetracarboxylic dianhydride to the extent which does not reduce the effect of this invention. In addition, the terminal unsealed polyamic acid and the terminal unsealed imidized polymer may be obtained from an aromatic tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, and the like in addition to the alicyclic tetracarboxylic dianhydride.

As such other tetracarboxylic dianhydride, a pyromellitic dianhydride, 3,3 ', 4,4'- benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-biphenylsulfontetra Carboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyl Ethertetracarboxylic dianhydride, 3,3 ', 4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3', 4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1 , 2,3,4-furantetetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4'-bis (3,4-di Carboxyphenoxy) diphenylsulfonic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride , Bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride, Ethylene glycol-bis (anhydrotrimellitate), propylene glycol-bis (anhydrotrimellitate), 3,3 ', 4,4'-perfluoroisopropylidene diphthalic dianhydride, 1,4-butanediol -Bis (anhydrotrimellitate), 1,6-hexanediol-bis (anhydrotrimellitate), 1,8-octanediol-bis (anhydrotrimellitate), 2,2-bis (4- Aromatic tetracarboxylic dianhydrides such as hydroxyphenyl) propane-bis (anhydrotrimelitate) and a compound represented by the following formulas (4) to (7); Aliphatic tetracarboxylic dianhydrides, such as butanetetracarboxylic dianhydride, are mentioned. These are used individually by 1 type or in combination of 2 or more types.

[Diamine Compound]

As a diamine compound, paraphenylenediamine, metaphenylenediamine, 4,4'- diamino diphenylmethane, 4,4'- diamino diphenyl ethane, 4,4'- diamino diphenyl sulfide, for example. , 4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 4,4'-diaminodiphenylether, 1,5-diaminonaphthalene, 3,3-dimethyl-4,4'-diaminobiphenyl, 5-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 6-amino -1- (4'-aminophenyl) -1,3,3-trimethylindane, 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] hexafluoro Propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene , 1,3-bis (4-aminophenoxy) benzene, 1,3-bis ( 3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 2,7-diaminofluorene, 9,9-bis (4-aminophenyl) fluorene, 4, 4'-methylene-bis (2-chloroaniline), 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino -5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 1,4,4 '-(paraphenyleneisopropylidene) bisaniline, 4,4 '-(Metaphenyleneisopropylidene) bisaniline, 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-diamino Aromatic diamines such as -2,2'-bis (trifluoromethyl) biphenyl and 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl;

1,1-methaxylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine, etc. Aliphatic diamines; 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindenylenedimethylenediamine, tricyclo [6.2.1.0 ^2,7 ] -undecylenedimethyl Diamine, 4,4'-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 2,5-bis (aminomethyl) bicyclo Alicyclic diamines such as [2.2.1] heptane and 2,6-bis (aminomethyl) bicyclo [2.2.1] heptane;

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, Two in the molecule, such as 3,6-diaminoacridine, bis (4-aminophenyl) phenylamine, and the compounds represented by the following formulas (8) and (11) Diamines having a nitrogen atom other than the primary amino group and the primary amino group;

In the formula, 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 represents a divalent organic group.

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

Mono-substituted phenylenediamines represented by the following formula (10); Diaminoorganosiloxane represented by the following formula (11);

In the formula, R ⁹ represents a divalent organic group selected from -O-, -COO-, -OCO-, -NHCO-, -CONH-, and -CO-, and R ¹⁰ represents a steroid skeleton, a trifluoromethyl group and a fluorine group. Monovalent organic group or alkyl group having 6 to 30 carbon atoms having a group selected from a group.

In the formula, R ¹¹ represents a hydrocarbon group having 1 to 12 carbon atoms, and a plurality of R ^{11 's} may be the same or different, respectively, p is an integer of 1 to 3 and q is an integer of 1 to 20.

Moreover, the compound etc. which are represented by following formula (12)-(16) are mentioned. These diamine compounds can be used individually or in combination of 2 or more types.

In formula, y is an integer of 2-12 and z is an integer of 1-5.

Among them, paraphenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 1,5-diaminonaphthalene, 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'-diamino-2,2'-bis (trifluoromethyl) Biphenyl, 4,4 '-(paraphenylenediisopropylidene) bisaniline, 4,4'-(methphenylenediisopropylidene) bisaniline, 1,4-cyclohexanediamine, 4,4'-methylenebis (Cyclohexylamine), 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 1,3-bis (aminomethyl) cyclohexane, 1, 4-bis (aminomethyl) cyclohexane, 2,5-bis (aminomethyl) bicyclo [2.2.1] heptane, 2,6-bis (aminomethyl) bicyclo [2.2.1] heptane, Formula 12 16, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine and the compounds represented by the formula (8) As a specific example of the compound represented by the following formula (17), a compound represented by the above formula (9) Decanoxy-2,4-diaminobenzene as a specific example of the compound represented by the following formula (18), the compound represented by the formula (10) , Undecaneoxy-2,4-diaminobenzene, dodecaneoxy-2,4-diaminobenzene, pentadecaneoxy-2,4-diaminobenzene, hexadecaneoxy-2,4-diaminobenzene, octa Preferred are decanoxyoxy-2,4-diaminobenzenes and compounds represented by the following formulas (19) to (24). Moreover, the terminally sealed polyamic acid and terminally sealed imidation polymer used by this invention can introduce | transduce alicyclic skeleton by using the alicyclic diamine mentioned above.

[Dicarboxylic Anhydride]

Examples of the dicarboxylic acid anhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride, n-hexadecylsuccinic anhydride Can be. These may be used alone or in combination of two or more thereof.

Monoamine Compound

Examples of the monoamine compound include aniline derivatives such as aniline, p-trifluoromethylaniline, m-trifluoromethylaniline, and bistrifluoromethylaniline;

Cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine (cyclo) alkylamines such as n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-eicosylamine;

Aminomethyltrimethylsilane, aminomethyltriethylsilane, aminomethyltripropylsilane, aminoethyltrimethylsilane, aminoethyltriethylsilane, aminoethyltripropylsilane, aminopropyltrimethylsilane, aminopropyltriethylsilane, aminopropyltripropylsilane , Aminomethyltrimethoxysilane, aminomethyltriethoxysilane, aminomethyltripropoxysilane, aminomethyldimethoxymethylsilane, aminomethylmethoxydimethylsilane, aminomethyldiethoxymethylsilane, aminomethylethoxydimethylsilane, Aminomethyldimethoxyethylsilane, aminomethylmethoxydiethylsilane, aminomethyldiethoxyethylsilane, aminomethylethoxydiethylsilane, aminoethyldimethoxymethylsilane, aminoethylmethoxydimethylsilane, aminoethyldiethoxymethylsilane, Aminoethylethoxydimethylsilane, aminoethyldimethoxyethylsilane, aminoethyl Methoxydiethylsilane, aminoethyldiethoxyethylsilane, aminoethylethoxydiethylsilane, aminopropyldimethoxymethylsilane, aminopropylmethoxydimethylsilane, aminopropyldiethoxymethylsilane, aminopropylethoxydimethylsilane, aminopropyl And amino silanes such as dimethoxy ethyl silane, aminopropyl methoxy diethyl silane, amino propyl diethoxy ethyl silane, amino propyl ethoxy diethyl silane and amino methyl phenyl dimethyl silane. Among them, aniline derivatives such as aniline, p-trifluoromethylaniline, m-trifluoromethylaniline and bistrifluoromethylaniline; n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octa Alkylamines having 10 or more carbon atoms such as decylamine and n-eicosylamine; Aminomethyltrimethylsilane, aminomethyltriethylsilane, aminomethyltripropylsilane, aminoethyltrimethylsilane, aminoethyltriethylsilane, aminoethyltripropylsilane, aminopropyltrimethylsilane, aminopropyltriethylsilane, aminopropyltripropylsilane Preferred are aminoalkyltrialkylsilanes. These may be used alone or in combination of two or more thereof.

[Monoisocyanate Compound]

In addition, examples of the monoisocyanate compound include cyclohexyl isocyanate, n-decyl isocyanate, n-undecyl isocyanate, n-dodecyl isocyanate, n-tridecyl isocyanate, n-tetradecyl isocyanate, n-pentadedecyl isocyanate, n -Hexadecyl isocyanate, n-heptadecyl isocyanate, n-octadecyl isocyanate, n-eicosyl isocyanate, phenyl isocyanate, naphthyl isocyanate, etc. are mentioned. These may be used alone or in combination of two or more thereof.

[Polyamic acid]

The use ratio of the tetracarboxylic dianhydride and the diamine compound provided in the polyamic acid synthesis reaction is preferably such that the acid anhydride group of the tetracarboxylic dianhydride is 0.2 to 2 equivalents to 1 equivalent of the amino group contained in the diamine compound. More preferably, it is the ratio used as 0.3 to 1.2 equivalent. When producing terminal sealed polyamic acid, the terminal sealing agent which is a dicarboxylic acid anhydride, a monoamine compound, or a monoisocyanate compound can be used further. The use ratio of the dicarboxylic anhydride, the monoamine compound or the monoisocyanate compound is an acid anhydride group of the dicarboxylic acid anhydride, an amino group of the monoamine compound or an isocyanate group of the monoisocyanate compound with respect to 1 equivalent of the amino group contained in the diamine compound. The ratio which becomes 0.001-0.8 equivalent is preferable, and the ratio which becomes 0.01-0.2 equivalent is more preferable.

The synthesis reaction of the polyamic acid is preferably carried out in an organic solvent at a reaction temperature of preferably 0 to 150 캜, more preferably 0 to 100 캜 over 1 to 48 hours. The organic solvent is not particularly limited as long as it can dissolve the reactant produced in the reaction. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphotriamide and Same aprotic polar solvents; phenolic solvents such as m-cresol, xylenol, phenol and halogenated phenol. It is preferable that the usage-amount of an organic solvent shall be 0.1-40 weight% with respect to the total amount of tetracarboxylic dianhydride and a diamine compound with respect to the reaction solution total amount.

In the organic solvent, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like, which are poor solvents of polyamic acid, can be used in combination without causing polyamic acid to be precipitated. Specific examples of such poor solvents include methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, acetone, methyl ethyl ketone, cyclohexanone, Methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol monophenyl ether, ethylene glycol methylphenyl ether, ethylene glycol ethylphenyl ether, 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 ether acetate, ethylene glycol methyl ether acetate, ethylene glycol Ethyl ether acetate, 4-hydrate Hydroxy-4-methyl-2-pentanone, 2,4-pentanedione, 2,5-hexanedione, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2- Ethyl methyl propionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-E Methyl oxypropionate, methyl pyruvate, ethyl pyruvate, hydroxymethyl pyruvate, methyl acetacetic acid, ethyl acetate, methyl methoxybutanol, ethyl methoxybutanol, methylethoxybutanol, ethyl ethoxybutanol, tetrahydrofuran, tetrahydrofur Furyl alcohol, tetrahydro-3-furanmethanol, 1,3-dioxolane, 1,3-dioxane, 4-methyl-1,3-dioxolane, dichloromethane, 1,2-dichloroethane, 1,4- Dichlorobutane, trichloroethane, chlorbenzene, o-dichlorbenzene, hexane, heptane, octane, There may be mentioned Zen, toluene, xylene and the like. These are used individually or in combination of 2 or more types.

By the above synthesis reaction, a reaction solution obtained by dissolving polyamic acid can be obtained. The reaction solution is poured into a large amount of poor solvent to obtain a precipitate, and the polyamic acid can be obtained by drying the precipitate under reduced pressure. In addition, the polyamic acid can be purified by dissolving the polyamic acid again in an organic solvent and then performing the step of precipitating with a poor solvent once or several times.

[Imidated Polymer]

The terminal sealing and terminal unsealed imidation polymer which comprise the liquid crystal aligning agent of this invention can be manufactured by dehydrating and ring-closing the polyamic acid corresponding to the above. The dehydration ring closure of the polyamic acid may be carried out by (i) 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. It is done by the method. In addition, the imidization polymer used in the present invention has a partially dehydration-closed imidization ratio (in which the ratio of the imide repeat unit to the total number of the amic acid repeat units and the imide repeat units in the polymer is represented by%) is 100. Less than% imidized polymer may be included. The imidation ratio of the imidation polymer is preferably 40% or more, particularly preferably 80% or more.

The reaction temperature of the method of heating the polyamic acid of said (i) becomes like this. Preferably it is 50-200 degreeC, More preferably, it is 60-170 degreeC. If the reaction temperature is less than 50 ° C, the dehydration ring-closure reaction may not proceed sufficiently, and if the reaction temperature exceeds 200 ° C, the molecular weight of the imidized polymer obtained may decrease.

On the other hand, in the method of adding a dehydrating agent and a dehydrating ring-closure catalyst in the polyamic acid solution of the above (ii), acid anhydrides such as acetic anhydride, propionic anhydride and trifluoroacetic anhydride can be used as the dehydrating agent. It is preferable that the usage-amount of a dehydrating agent shall be 0.01-20 mol with respect to 1 mol of polyamic-acid repeating units. 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 these. 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, the organic solvent illustrated as what is used for polyamic-acid synthesis can be mentioned as an organic solvent used for dehydration ring-closure reaction. And the reaction temperature of dehydration ring-closure reaction becomes like this. Preferably it is 0-180 degreeC, More preferably, it is 10-150 degreeC. Moreover, the imidation polymer can be refine | purified by performing the same operation as the polyamic acid purification method with respect to the reaction solution obtained in this way.

[Logarithmic Viscosity of Polymer]

The polymer constituting the liquid crystal aligning agent used in the present invention preferably has a logarithmic viscosity (η 1 n) value of all polyamic acid and imidized polymer irrespective of the terminal encapsulation and terminal unsealing, preferably 0.05 to 10 dl / g, More preferably, it is 0.05-5 dl / g. Here, the value of the logarithmic viscosity (η1n) is obtained by measuring the viscosity at 30 ° C with respect to a solution having a polymer concentration of 0.5 g / 100 milliliter using N-methyl-2-pyrrolidone as a solvent, It is obtained by the expression shown.

η1n = {1n (solution throwing time / solvent throwing time)} / (weight concentration of polymer)

<Liquid crystal aligning agent>

The liquid crystal aligning agent of this invention is comprised by dissolving and containing terminal sealing polyamic acid and / or terminal sealing imidation polymer in an organic solvent. Each polyamic acid and / or imidation polymer used by this liquid crystal aligning agent can be used individually or in combination of 2 or more types.

The liquid crystal aligning agent of this invention may further contain terminal unsealed polyamic acid and / or terminal unsealed imidation polymer. Here, the ratio of the terminally sealed polyamic acid and / or the terminally sealed imidized polymer in the whole polyamic acid and the imidized polymer in the liquid crystal aligning agent is preferably 5 to 80% by weight, more preferably 10 to 60% by weight. desirable. Moreover, it is especially preferable to use terminally sealed imidation polymer and terminally unsealed polyamic acid together. In this case, as a terminal sealing imidation polymer, what used the monoamine compound as a terminal sealing agent is preferable. As an organic solvent which comprises this liquid crystal aligning agent, the thing similar to the solvent illustrated as what is used by the synthesis reaction of polyamic acid, and dehydration ring-closure reaction is mentioned. Moreover, the thing similar to the poor solvent illustrated as what can be used together at the time of the synthesis reaction of polyamic acid can be selected suitably, and can be used together.

In the liquid crystal aligning agent of the present invention, the total concentration of the terminal sealing polymer and the terminal unsealing polymer (if included) is selected in consideration of viscosity, volatility, and the like, but is preferably in the range of 1 to 10% by weight. Although the liquid crystal aligning agent of this invention forms on the surface of a board | substrate and forms the coating film used as a liquid crystal aligning film, when concentration is less than 1 weight%, the film thickness of this coating film becomes too small and it is difficult to obtain a favorable liquid crystal aligning film, and also the density | concentration When the content exceeds 10% by weight, the film thickness of the coating film is too large, making it difficult to obtain a good liquid crystal aligning film, and the viscosity of the liquid crystal aligning agent increases, resulting in poor coating properties.

The functional silane containing compound may be contained in the liquid crystal aligning agent of this invention from a viewpoint of improving the adhesiveness to the board | substrate surface of a polyamic acid and / or an imidation polymer. As such a functional silane containing compound, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 2-aminopropyl trimethoxysilane, 2-aminopropyl triethoxysilane, N- ( 2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidepropyltrimethoxysilane, 3-ureidepropyltrier Methoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-tri Methoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl- 3,6-diazanyl acetate, 9-triethoxysilyl-3,6-diazanyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N- Jyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltri Methoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, etc. are mentioned.

The liquid crystal aligning agent of this invention may contain an epoxy group containing compound in order to improve the adhesiveness to a board | substrate further. Examples of such epoxy group-containing compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and 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-diglycidylamino Methyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 3- (N-allyl-N-glycidyl) aminopropyltrimethoxysilane And 3- (N, N-diglycidyl) aminopropyltrimethoxysilane. Among these, compounds having a tertiary nitrogen atom in the molecule are preferable, and the compounding ratio of these epoxy group-containing compounds is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the polymer.

<Liquid crystal display element>

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

(1) Applying the liquid crystal aligning agent of this invention to one surface of the board | substrate with which the patterned transparent conductive film is provided by methods, such as a roll coater method, a spinner method, and a printing method, and then forming a film by heating a coating surface. do. Here, as a board | substrate, For example, glass, such as float glass and a soda glass; A transparent substrate made of a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate can be used. As the transparent conductive film provided on one surface of the substrate, for example, NESA film (registered trademark of PPG Co., Ltd.) made of tin oxide (SnO ₂ ), and ITO made of indium tin oxide (In ₂ O ₃ -SnO ₂ ) And the like can be used. The photoetching method and the method of using a mask beforehand are used for patterning these transparent conductive films. At the time of coating the liquid crystal aligning agent, a functional silane-containing compound, a functional titanium-containing compound, and the like are applied to the surface of the substrate in advance in order to further improve the adhesion between the substrate surface and the transparent conductive film and the film of the liquid crystal aligning agent. It may be. Moreover, heating temperature becomes like this. Preferably it is 80-250 degreeC, More preferably, it is 120-200 degreeC. The film thickness of the formed film becomes like this. Preferably it is 0.001-1 micrometer, More preferably, it is 0.005-0.5 micrometer. In addition, the liquid crystal aligning agent of this invention containing terminally sealed polyamic acid or terminal unsealed polyamic acid forms the film which becomes a liquid crystal aligning film by removing an organic solvent after application | coating, and further dehydration ring closure is carried out by further heating. It can also be set as the imidized or fully imidized film.

(2) The rubbing process which rubs the film surface formed with the liquid crystal aligning agent in the fixed direction with the roller which wound the cloth which consists of fibers, such as nylon, rayon, and cotton, for example is performed. Thereby, the orientation ability of liquid crystal molecules is provided to a film, and it becomes a liquid crystal aligning film. In addition to the method by the rubbing treatment, the liquid crystal alignment film may be formed by irradiating polarized ultraviolet rays, ion beams, electron beams, etc. on the surface of the resin film to impart orientation capability, or by obtaining a film by a uniaxial stretching method, a Langmuir project method, or the like. It may be formed. Moreover, in order to remove the fine powder (foreign substance) which arises at the time of a rubbing process, and to make a surface clean, it is preferable to wash the formed liquid crystal aligning film with isopropyl alcohol etc. Furthermore, a process of changing the pretilt angle by partially irradiating the surface of the formed liquid crystal alignment film with ultraviolet rays, ion beams, electron beams, and the like (Japanese Patent Laid-Open No. 6-222366, Japanese Patent Laid-Open No. 6-281937, Japanese Patent Laid-Open No. 7-) 168187 and Japanese Patent Application Laid-open No. Hei 8-234207), and a resist film is partially formed on the surface of the formed liquid crystal alignment film and subjected to a rubbing treatment in a direction different from the preceding rubbing treatment, and then the resist film is removed to obtain a liquid crystal alignment film. The viewing angle characteristic of the liquid crystal display element produced can also be improved by performing the process which changes an orientation ability (refer Unexamined-Japanese-Patent No. 5-107544).

(3) Two board | substrates with a liquid crystal aligning film were produced as mentioned above, and two board | substrates were opposingly arranged through a gap (cell gap) so that the orientation processing direction, ie, a rubbing direction, in each liquid crystal aligning film may become orthogonal or antiparallel. Then, the two peripheral portions of the substrate are bonded to each other using an encapsulant, and the liquid crystal is injected and filled into the cell gap partitioned by the substrate surface and the encapsulant, the injection hole is sealed to form a liquid crystal cell. And a liquid crystal display element is obtained by bonding a polarizing plate to the outer surface of a liquid crystal cell, ie, the other surface side of each board | substrate which comprises a liquid crystal cell so that the polarization direction may coincide or orthogonally cross with the rubbing direction of the liquid crystal aligning film formed in one surface of the said board | substrate. Can be.

Here, as a sealing agent, the epoxy resin etc. which contain a hardening agent and aluminum oxide sphere as a spacer can be used, for example.

Examples of the liquid crystal include nematic liquid crystals and smectic liquid crystals. Especially, a nematic type liquid crystal is preferable, for example, a Schiff base type liquid crystal, a subfamily clock liquid crystal, a biphenyl type liquid crystal, a phenyl cyclohexane type liquid crystal, an ester type liquid crystal, a terphenyl type liquid crystal, a biphenyl cyclohexane type liquid crystal, a pyrimi Din type liquid crystal, a dioxane type liquid crystal, a bicyclo octane type liquid crystal, a cuban type liquid crystal, etc. can be used. In addition, these liquid crystals are, for example, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonaate, cholesteryl carbonate, and trade names "C-15" and "CB-15" (manufactured by Melk Corporation). The chiral agent sold etc. can also be added and used. In addition, ferroelectric liquid crystals such as p-disiloxybenzylidene-p-amino-2-methylbutylcinnamate can also be used.

Moreover, as a polarizing plate joined to the outer surface of a liquid crystal cell, the polarizing plate called H film which absorbed iodine while extending | stretching polyvinyl alcohol was sandwiched between a cellulose acetate protective film, and the polarizing plate which consists of a polarizing plate or 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 pretilt angle measurement in an Example is described by T. J. Schffer, et al., J. Appl. Phys., 19, 2013 (1980)] by the crystal rotation method using a He-Ne laser light.

In addition, in the following Example and the comparative example, the evaluation method about the afterimage erasing time and liquid crystal orientation of a liquid crystal display element is as follows.

(Afterimage elimination time)

After applying a direct current voltage of 10 V to the liquid crystal cell for 1 hour, the application of the voltage was canceled, the display screen was visually observed to release the voltage, and the time taken until the afterimage on the screen was erased was measured.

(Alignment of liquid crystal)

The presence or absence of the abnormal domain at the time of turning on / off (applying / releasing) a voltage was observed with the polarization microscope, and the case where the abnormal domain was not confirmed was determined as "good".

(Reliability Test of Liquid Crystal Display Device)

The liquid crystal display device was driven by a square wave of 5 V and 60 Hz in a high temperature, high humidity environment (temperature 70 ° C., relative humidity 80%), and after 1500 hours, the presence of white uneven display defects was observed with a polarization microscope.

Synthesis Example 1

In a 500 ml separable flask, 32.84 g (146.48 mmol) of 2,3,5-tricarboxycyclopentylacetic dianhydride, 15.37 g (142.09 mmol) of paraphenylenediamine, cholesteryl-3,5-diaminobenzoate ( 1.53 g (2.93 mmol) and 0.27 g (2.93 mmol) of aniline were dissolved in 450 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours. The reaction solution was then poured into excess methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 DEG C for 15 hours under reduced pressure to obtain 45.42 g of polyamic acid having a logarithmic viscosity of 1.18 dl / g (called "polyamic acid (1)").

40 g of the obtained polyamic acid was dissolved in 360 g of N-methylpyrrolidone, 46.35 g of pyridine and 35.89 g of acetic anhydride were added, followed by dehydration ring-closure reaction by heating at 110 ° C for 4 hours. Subsequently, the reaction product was precipitated and dried in the same manner as in the polyamic acid synthesis, to obtain 36.4 g of a polyimide having a logarithmic viscosity of 1.05 dl / g (called "polyimide (1)").

Synthesis Example 2

32.92 g (146.85 mmol) of 2,3,5-tricarboxycyclopentylacetic dianhydride, 15.40 g (142.41 mmol) of paraphenylenediamine, 4- (4'-trifluoromethylbenzoyloxy) in a 500 ml separable flask 1.24 g (2.94 mmol) of cyclohexyl-3,5-diaminobenzoate (compound represented by Formula 23) and 0.44 g (2.94 mmol) of phthalic anhydride were dissolved in 450 g of N-methyl-2-pyrrolidone The reaction was carried out at room temperature for 6 hours. The reaction solution was then poured into excess methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 DEG C for 15 hours under reduced pressure to obtain 45.22 g of a polyamic acid having a logarithmic viscosity of 1.10 dl / g (called "polyamic acid (2)").

40 g of the obtained polyamic acid was dissolved in 360 g of N-methylpyrrolidone, 46.46 g of pyridine and 35.98 g of acetic anhydride were added, followed by dehydration ring-closure reaction by heating at 110 ° C for 4 hours. Subsequently, the reaction product was precipitated and dried in the same manner as in the synthesis of polyamic acid to obtain 36.1 g of a polyimide having a logarithmic viscosity of 1.01 dl / g (called "polyimide (2)").

Synthesis Example 3

31.14 g (138.3 mmol) of 2,3,5-tricarboxycyclopentylacetic dianhydride, 11.57 g (106.98 mmol) of paraphenylenediamine, 5.51 g (27.79 mmol) of diaminodiphenylmethane, in a 500 mL separable flask 1.45 g (2.78 mmol) of steryl-3,5-diaminobenzoate (compound represented by Formula 19) and 0.33 g (2.78 mmol) of phenylisocyanate were dissolved in 450 g of N-methyl-2-pyrrolidone The reaction was carried out at room temperature for 6 hours. The reaction solution was then poured into excess methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 DEG C for 15 hours under reduced pressure to give 44.28 g of polyamic acid having a logarithmic viscosity of 0.90 dl / g (called "polyamic acid (3)").

40 g of the obtained polyamic acid was dissolved in 360 g of N-methylpyrrolidone, 43.96 g of pyridine and 34.04 g of acetic anhydride were added, followed by dehydration ring-closure reaction by heating at 110 ° C for 4 hours. Subsequently, the reaction product was precipitated and dried in the same manner as in the polyamic acid synthesis, to obtain 36.06 g of a polyimide having a logarithmic viscosity of 0.88 dl / g (called "polyimide (3)").

Synthesis Example 4

1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2 in a 500 ml separable flask -c] furan-1,3-dione 36.05 g (114.70 mmol), paraphenylenediamine 11.78 g (108.96 mmol), 4- (4'-trifluoromethylbenzoyloxy) cyclohexyl-3,5-diamino 1.94 g (4.59 mmol) of benzoate (compound represented by Formula 23) and 0.23 g (2.29 mmol) of cyclohexylamine were dissolved in 450 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours. . The reaction solution was then poured into excess methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 DEG C for 15 hours under reduced pressure to obtain 45.78 g of a polyamic acid having a logarithmic viscosity of 0.92 dl / g (called "polyamic acid (4)").

40 g of the obtained polyamic acid was dissolved in 360 g of N-methylpyrrolidone, 29.03 g of pyridine and 65.58 g of acetic anhydride were added, followed by dehydration ring-closure reaction by heating at 80 ° C for 4 hours. Subsequently, the reaction product was precipitated and dried in the same manner as in the polyamic acid synthesis, to obtain 35.66 g of a polyimide having a logarithmic viscosity of 0.85 dl / g (called "polyimide (4)").

Synthesis Example 5

1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2 in a 500 ml separable flask 33.96 g (108.05 mmol) of furan-1,3-dione, 8.76 g (81.04 mmol) of paraphenylenediamine, 4.28 g (21.61 mmol) of diaminodiphenylmethane, 3,6-bis (4-aminobenzoyl 2.78 g (4.32 mmol) of oxy) cholestane (compound represented by Formula 12) and 0.21 g (2.16 mmol) of maleic anhydride are dissolved in 450 g of N-methyl-2-pyrrolidone and for 6 hours at room temperature. Reacted. The reaction solution was then poured into excess methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 DEG C for 15 hours under reduced pressure to obtain 43.71 g of polyamic acid having a logarithmic viscosity of 0.90 dl / g (called "polyamic acid (5)").

40 g of the obtained polyamic acid was dissolved in 360 g of N-methylpyrrolidone, and 27.35 g of pyridine and 61.77 g of acetic anhydride were added, followed by dehydration ring closure reaction by heating at 80 ° C for 4 hours. Subsequently, the reaction product was precipitated and dried in the same manner as in the polyamic acid synthesis, to obtain 34.39 g of a polyimide having a logarithmic viscosity of 0.83 dl / g (called "polyimide (5)").

Synthesis Example 6

1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2 in a 500 ml separable flask -c] 31.38 g (99.83 mmol) of furan-1,3-dione, 8.10 g (74.87 mmol) paraphenylenediamine, 8.20 g (19.97 mmol) 2,2-bis (4-aminophenoxyphenyl) propane, chole 2.08 g (3.99 mmol) of steryl-3,5-diaminobenzoate (compound represented by Formula 19) and 0.25 g (2.00 mmol) of cyclohexyl isocyanate are dissolved in 450 g of N-methyl-2-pyrrolidone. The mixture was allowed to react at room temperature for 6 hours. Then, the reaction solution was poured into excess methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 DEG C for 15 hours under reduced pressure to obtain 43.96 g of a polyamic acid having a logarithmic viscosity of 0.91 dl / g (called "polyamic acid (6)").

40 g of the obtained polyamic acid was dissolved in 360 g of N-methylpyrrolidone, and 25.27 g of pyridine and 57.07 g of acetic anhydride were added, followed by dehydration ring closure reaction by heating at 80 ° C for 4 hours. Subsequently, the reaction product was precipitated and dried in the same manner as in the synthesis of polyamic acid to obtain 34.67 g of a polyimide having a logarithmic viscosity of 0.84 dl / g (called "polyimide (6)").

Synthesis Example 7

1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2 in a 500 ml separable flask -c] furan-1,3-dione 18.07 g (57.50 mmol), 2,3,5-tricarboxycyclopentylacetic dianhydride 12.89 g (57.50 mmol), 9.58 g (88.55 mmol) paraphenylenediamine, 4, 7.37 g (23.00 mmol) of 4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 1.48 g (2.30 mmol) of 3,6-bis (4-aminobenzoyloxy) cholestane and stearyl 0.62 g (2.3 mmol) of amine was dissolved in 450 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours. The reaction solution was then poured into excess methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 DEG C for 15 hours under reduced pressure to give 44.42 g of polyamic acid having a logarithmic viscosity of 0.98 dl / g (called "polyamic acid (7)").

40 g of the obtained polyamic acid was dissolved in 360 g of N-methylpyrrolidone, 29.11 g of pyridine and 37.57 g of acetic anhydride were added, followed by dehydration ring-closure reaction by heating at 110 ° C for 4 hours. Subsequently, the reaction product was precipitated and dried in the same manner as in the synthesis of polyamic acid to obtain 36.82 g of a polyimide having a logarithmic viscosity of 0.96 dl / g (called "polyimide (7)").

Synthesis Example 8

1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2 in a 500 ml separable flask -c] 31.63 g (100.64 mmol) of furan-1,3-dione, 1.19 g (5.30 mmol) of 2,3,5-tricarboxycyclopentylacetic dianhydride, 8.82 g (81.56 mmol) of paraphenylenediamine, 4, 6.78 g (21.19 mmol) of 4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 3,6-bis (4-aminobenzoyloxy) cholestane (compound represented by Formula 12) 1.36 g (2.12 mmol) and 0.22 g (2.12 mmol) aminomethyltrimethylsilane were dissolved in 450 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours. The reaction solution was then poured into excess methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 DEG C for 15 hours under reduced pressure to obtain 43.63 g of polyamic acid having a logarithmic viscosity of 0.92 dl / g (called "polyamic acid (8)").

40 g of the obtained polyamic acid was dissolved in 360 g of N-methylpyrrolidone, and 26.81 g of pyridine and 34.60 g of acetic anhydride were added, followed by dehydration ring-closure reaction by heating at 80 ° C for 4 hours. Subsequently, the reaction product was precipitated and dried in the same manner as in the polyamic acid synthesis, to obtain 34.81 g of a polyimide having a logarithmic viscosity of 0.91 dl / g (called "polyimide (8)").

Synthesis Example 9

1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2 in a 500 ml separable flask 28.56 g (90.86 mmol) of furan-1,3-dione, 3.64 g (16.22 mmol) of 2,3,5-tricarboxycyclopentylacetic dianhydride, 9.12 g (84.37 mmol) of paraphenylenediamine, 2, 7.23 g (21.63 mmol) of 2-bis (4-aminophenyl) -1,1,1,3,3,3, -hexafluoropropane, cholestharyl-3,5-diaminobenzoate (Formula 20 above) 1.13 g (2.16 mmol) and phthalic anhydride 0.32 g (2.16 mmol) were dissolved in 450 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours. The reaction solution was then poured into excess methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 DEG C for 15 hours under reduced pressure to give 44.23 g of a polyamic acid having a logarithmic viscosity of 0.92 dl / g (called "polyamic acid (9)").

40 g of the obtained polyamic acid was dissolved in 360 g of N-methylpyrrolidone, and 27.65 g of pyridine and 35.69 g of acetic anhydride were added, followed by dehydration ring-closure reaction by heating at 80 ° C for 4 hours. Subsequently, the reaction product was precipitated and dried in the same manner as in the synthesis of polyamic acid to obtain 35.19 g of a polyimide having a logarithmic viscosity of 0.89 dl / g (called "polyimide (9)").

Synthesis Example 10

1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2 in a 500 ml separable flask 24.71 g (78.61 mmol) of furan-1,3-dione, 7.55 g (33.69 mmol) of 2,3,5-tricarboxycyclopentylacetic dianhydride, 10.32 g (95.43 mmol) of paraphenylenediamine, bis [ 4- (4-aminophenoxy) phenyl] sulfone 4.86 g (11.23 mmol), 4- (4'-trifluoromethylbenzoyloxy) cyclohexyl-3,5-diaminobenzoate (as represented by the formula (23) Compound) 1.90 g (4.49 mmol) and 0.66 g (2.25 mmol) octadecyl isocyanate were dissolved in 450 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours. The reaction solution was then poured into excess methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 DEG C for 15 hours under reduced pressure to give 44.68 g of polyamic acid having a logarithmic viscosity of 0.94 dl / g (called "polyamic acid (10)").

40 g of the obtained polyamic acid was dissolved in 360 g of N-methylpyrrolidone, and 28.43 g of pyridine and 36.69 g of acetic anhydride were added, followed by dehydration ring-closure reaction by heating at 80 ° C for 4 hours. Subsequently, the reaction product was precipitated and dried in the same manner as in the polyamic acid synthesis, to obtain 36.02 g of a polyimide having a logarithmic viscosity of 0.92 dl / g (called "polyimide (10)").

Synthesis Example 11

1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan in 500 ml separable flask 28.62 g (95.31 mmol) of 1,3-dione, 6.25 g (23.83 mmol) of 3,5,6-tricarboxynorbornane-2-acetic dianhydride, 11.98 g (110.79 mmol) of paraphenylenediamine, octadecane 2.24 g (5.96 mmol) of oxy-2,4-diaminobenzene and 0.91 g (4.77 mmol) of 3-aminopropylmethyldiethoxysilane were dissolved in 450 g of N-methyl-2-pyrrolidone and 6 hours at room temperature. Reacted for a while. The reaction solution was then poured into excess methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 DEG C for 15 hours under reduced pressure to give 44.25 g of polyamic acid having a logarithmic viscosity of 0.91 dl / g (called "polyamic acid (11)").

40 g of the obtained polyamic acid was dissolved in 360 g of N-methylpyrrolidone, 15.08 g of pyridine and 19.46 g of acetic anhydride were added, followed by dehydration ring-closing reaction by heating at 60 ° C for 3 hours. Subsequently, the reaction product was precipitated and dried in the same manner as in the synthesis of polyamic acid to obtain 35.81 g of a polyimide having a logarithmic viscosity of 0.88 dl / g (called "polyimide (11)").

Synthesis Example 12

1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan in 500 ml separable flask 34.06 g (113.45 mmol) of -1,3-dione, 10.80 g (99.80 mmol) of paraphenylenediamine, 4.27 g (11.34 mmol) of octadecaneoxy-2,4-diaminobenzene and 3-aminopropylmethyldiethoxysilane 0.87 g (4.54 mmol) was dissolved in 450 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours. The reaction solution was then poured into excess methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 DEG C for 15 hours under reduced pressure to give 44.25 g of polyamic acid having a logarithmic viscosity of 0.91 dl / g (called "polyamic acid (12)").

40 g of the obtained polyamic acid was dissolved in 360 g of N-methylpyrrolidone, 14.36 g of pyridine and 18.53 g of acetic anhydride were added, followed by dehydration ring-closing reaction by heating at 60 ° C for 3 hours. Subsequently, the reaction product was precipitated and dried in the same manner as in the polyamic acid synthesis, to obtain 35.81 g of a polyimide having a logarithmic viscosity of 0.88 dl / g (called "polyimide (12)").

Synthesis Example 13

34.06 g (126.79 mmol) of 3,5,6-tricarboxynorbornane-2-acetic dianhydride in a 500 mL separable flask, 12.34 g (114.11 mmol) of paraphenylenediamine, octadecaneoxy-2,4-dia 3.82 g (10.14 mmol) of minobenzene and 0.59 g (5.07 mmol) of 3-aminomethylethyldimethylsilane were dissolved in 450 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours. The reaction solution was then poured into excess methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 DEG C for 15 hours under reduced pressure to obtain 43.94 g of a polyamic acid having a logarithmic viscosity of 0.90 dl / g (called "polyamic acid (13)").

40 g of the obtained polyamic acid was dissolved in 360 g of N-methylpyrrolidone, and 32.11 g of pyridine and 41.41 g of acetic anhydride were added, followed by dehydration ring-closure reaction by heating at 110 ° C for 4 hours. Subsequently, the reaction product was precipitated and dried in the same manner as in the polyamic acid synthesis, to obtain 35.41 g of a polyimide having a logarithmic viscosity of 0.86 dl / g (called "polyimide (13)").

Synthesis Example 14

34.29 g (130.77 mmol) of 3,5,6-tricarboxynorbornane-2-acetic dianhydride, 13.71 g (126.84 mmol) of paraphenylenediamine, cholesteryl-3,5-dia, in a 500 ml separable flask 1.36 g (2.62 mmol) of minobenzoate (compound represented by Formula 19) and 0.63 g (2.62 mmol) of hexadecylamine were dissolved in 450 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours. I was. The reaction solution was then poured into excess methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 DEG C for 15 hours under reduced pressure to obtain 44.84 g of polyamic acid having a logarithmic viscosity of 0.95 dl / g (called "polyamic acid (14)").

40 g of the obtained polyamic acid was dissolved in 360 g of N-methylpyrrolidone, 33.10 g of pyridine and 42.72 g of acetic anhydride were added, followed by dehydration ring-closure reaction by heating at 110 ° C for 4 hours. Subsequently, the reaction product was precipitated and dried in the same manner as in the synthesis of polyamic acid to obtain 35.88 g of a polyimide having a logarithmic viscosity of 0.92 dl / g (called "polyimide (14)").

Synthesis Example 15

31.62 g (120.59 mmol) of 3,5,6-tricarboxynorbornane-2-acetic dianhydride, 9.05 g (83.67 mmol) of paraphenylenediamine, cholesteryl-3,5-dia, in a 500 mL separable flask 1.28 g (2.46 mmol) of minobenzoate (compound represented by Formula 19) and 0.73 g (4.92 mmol) of phthalic anhydride were dissolved in 450 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours. . The reaction solution was then poured into excess methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 DEG C for 15 hours under reduced pressure to give 43.73 g of a polyamic acid having a logarithmic viscosity of 0.78 dl / g (called "polyamic acid (15)").

40 g of the obtained polyamic acid was dissolved in 360 g of N-methylpyrrolidone, 15.88 g of pyridine and 20.50 g of acetic anhydride were added, followed by dehydration ring-closure reaction by heating at 110 ° C for 4 hours. Subsequently, the reaction product was precipitated and dried in the same manner as in the synthesis of polyamic acid to obtain 34.24 g of a polyimide having a logarithmic viscosity of 0.74 dl / g (called "polyimide (15)").

Synthesis Example 16

Dissolve 33.51 g (149.47 mmol) of 2,3,5-tricarboxycyclopentylacetic dianhydride and 16.49 g (149.47 mmol) of paraphenylenediamine in 450 g of N-methyl-2-pyrrolidone in a 500 ml separable flask. And reacted at room temperature for 6 hours. The reaction solution was then poured into excess methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 DEG C for 15 hours under reduced pressure to obtain 46.83 g of a polyamic acid having a logarithmic viscosity of 1.31 dl / g (called "polyamic acid (16)").

Synthesis Example 17

In a 500 ml separable flask, 16.84 g (75.12 mmol) of 2,3,5-tricarboxycyclopentylacetic dianhydride and 33.16 g (75.12 mmol) of bis [4- (4-aminophenoxy) phenyl] sulfone were N-methyl. It was dissolved in 450 g of 2-pyrrolidone and reacted for 6 hours at room temperature. The reaction solution was then poured into excess methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 DEG C for 15 hours under reduced pressure to give 46.23 g of a polyamic acid having a logarithmic viscosity of 1.24 dl / g (called "polyamic acid (17)").

Synthesis Example 18

17.43 g (77.75 mmol) of 2,3,5-tricarboxycyclopentylacetic dianhydride and 32.57 g (79.34 mmol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane in 500 ml separable flasks Was dissolved in 450 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours. The reaction solution was then poured into excess methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 DEG C for 15 hours under reduced pressure to obtain 46.33 g of polyamic acid having a logarithmic viscosity of 1.34 dl / g (called "polyamic acid (18)").

40 g of the obtained polyamic acid was dissolved in 360 g of N-methylpyrrolidone, and 24.60 g of pyridine and 25.40 g of acetic anhydride were added, followed by dehydration ring-closure reaction by heating at 110 ° C for 4 hours. Subsequently, the reaction product was precipitated and dried in the same manner as in the polyamic acid synthesis, to obtain 37.24 g of a polyimide having a logarithmic viscosity of 0.94 dl / g (called "polyimide (18)").

Synthesis Example 19

In a 500 ml separable flask, 33.20 g (152.21 mmol) of pyromellitic dianhydride and 16.80 g (152.21 mmol) of paraphenylenediamine were dissolved in 450 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours. I was. The reaction solution was then poured into excess methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried under reduced pressure at 40 ° C. for 15 hours to obtain 47.26 g of a polyamic acid having a logarithmic viscosity of 1.46 dl / g, referred to as “polyamic acid (19)”.

Synthesis Example 20

In a 500 ml separable flask, 13.25 g (60.76 mmol) pyromellitic dianhydride, 11.92 g (60.76 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 24.83 g (124.00 g) diaminodiphenylether Mmol) was dissolved in 450 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours. The reaction solution was then poured into excess methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 DEG C for 15 hours under reduced pressure to obtain 46.37 g of polyamic acid having a logarithmic viscosity of 1.36 dl / g (called "polyamic acid (20)").

Synthesis Example 21

13.32 g (61.06 mmol) pyromellitic dianhydride, 11.98 g (61.06 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 24.71 g (124.61) diaminodiphenylmethane in a 500 ml separable flask Mmol) was dissolved in 450 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours. The reaction solution was then poured into excess methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 DEG C for 15 hours under reduced pressure to obtain 46.37 g of a polyamic acid having a logarithmic viscosity of 1.35 dl / g (called "polyamic acid (21)").

Synthesis Example 22

1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan in 500 ml separable flask 37.01 g (117.74 mmol) of -1,3-dione and 12.99 g (120.15 mmol) of paraphenylenediamine were dissolved in 450 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours. The reaction solution was then poured into excess methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 DEG C for 15 hours under reduced pressure to obtain 45.77 g of polyamic acid having a logarithmic viscosity of 1.31 dl / g (called "polyamic acid (22)").

Synthesis Example 23

1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan in 500 ml separable flask 30.42 g (96.78 mmol) of -1,3-dione and 19.58 g (98.76 mmol) of diaminodiphenylmethane were dissolved in 450 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours. The reaction solution was then poured into excess methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 DEG C for 15 hours under reduced pressure to obtain 45.96 g of a polyamic acid having a logarithmic viscosity of 1.30 dl / g (called "polyamic acid (23)").

40 g of the obtained polyamic acid was dissolved in 360 g of N-methylpyrrolidone, and 24.40 g of pyridine and 55.12 g of acetic anhydride were added, followed by dehydration ring-closure reaction by heating at 80 ° C for 4 hours. Subsequently, the reaction product was precipitated and dried in the same manner as in the synthesis of polyamic acid to obtain 36.62 g of a polyimide having a logarithmic viscosity of 0.98 dl / g (called "polyimide (23)").

Synthesis Example 24

In a 500 ml separable flask, 36.36 g (123.59 mmol) of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and 13.64 g (126.11 mmol) of paraphenylenediamine were added to N-methyl-2-pyrroli. It was dissolved in 450 g of money and reacted at room temperature for 6 hours. The reaction solution was then poured into excess methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 DEG C for 15 hours under reduced pressure to obtain 45.16 g of polyamic acid having a logarithmic viscosity of 1.22 dl / g (called "polyamic acid (24)").

Synthesis Example 25

28.81 g (64.85 mmol) and 2,2'-bis (trifluoromethyl) -4,4'-diamino 4,4 '-(hexafluoroisopropylidene) diphthalic dianhydride in a 500 ml separable flask 21.19 g (66.17 mmol) of biphenyls were dissolved in 450 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours. The reaction solution was then poured into excess methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 DEG C for 15 hours under reduced pressure to obtain 44.27 g of polyamic acid having a logarithmic viscosity of 1.20 dl / g (called "polyamic acid (25)").

Synthesis Example 26

In a 500 ml separable flask, 26.16 g (116.69 mmol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride, and 23.84 g (119.07 mmol) of diaminodiphenylether were added N-methyl-2-pyrroli. It was dissolved in 450 g of money and reacted at room temperature for 6 hours. The reaction solution was then poured into excess methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 DEG C for 15 hours under reduced pressure to give 44.18 g of polyamic acid having a logarithmic viscosity of 1.25 dl / g (called "polyamic acid (26)").

Synthesis Example 27

13.52 g (60.32 mmol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride and 11.83 g (60.32 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride in a 500 ml separable flask ) And 24.65 g (123.10 mmol) of diaminodiphenyl ether were dissolved in 450 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours. The reaction solution was then poured into excess methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 DEG C for 15 hours under reduced pressure to give 44.49 g of a polyamic acid having a logarithmic viscosity of 1.26 dl / g (called "polyamic acid (27)").

Synthesis Example 28

In a 500 ml separable flask, 35.19 g (134.20 mmol) of 3,5,6-tricarboxynorbornane-2-acetic dianhydride and 14.81 g (136.94 mmol) of paraphenylenediamine were added N-methyl-2-pyrrolidone. It was dissolved in 450 g and reacted at room temperature for 6 hours. The reaction solution was then poured into excess methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 DEG C for 15 hours under reduced pressure to obtain 45.72 g of polyamic acid having a logarithmic viscosity of 1.26 dl / g (called "polyamic acid (28)").

Synthesis Example 29

1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2 in a 500 ml separable flask -c] furan-1,3-dione 18.07 g (57.50 mmol), 2,3,5-tricarboxycyclopentylacetic dianhydride 12.89 g (57.50 mmol), 9.58 g (88.55 mmol) paraphenylenediamine, 4, 7.37 g (23.00 mmol) of 4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 1.48 g (2.30 mmol) of 3,6-bis (4-aminobenzoyloxy) cholestane and p- 0.37 g (2.3 mmol) of trifluoromethylaniline was dissolved in 450 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours. The reaction solution was then poured into excess methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 DEG C for 15 hours under reduced pressure to obtain 44 g of polyamic acid having a logarithmic viscosity of 0.90 dl / g (called "polyamic acid (29)").

40 g of the obtained polyamic acid was dissolved in 360 g of N-methylpyrrolidone, 29.11 g of pyridine and 37.57 g of acetic anhydride were added, followed by dehydration ring-closure reaction by heating at 110 ° C for 4 hours. Subsequently, the reaction product was precipitated and dried in the same manner as in the synthesis of polyamic acid to obtain 37.0 g of a polyimide having a logarithmic viscosity of 0.91 dl / g (called "polyimide (29)").

Synthesis Example 30

20.81 g (92.83 mmol) of 3,5,6-tricarboxynorbornane-2-acetic dianhydride, 5.0 g (46.4 mmol) of paraphenylenediamine, cholesteryl-3,5-dia, in a 500 ml separable flask 24.17 g (46.4 mmol) of minobenzoate (compound represented by Formula 19) and 0.91 g (9.28 mmol) of maleic anhydride were dissolved in 205 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours. I was. The reaction solution was then poured into excess methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 DEG C for 15 hours under reduced pressure to obtain 43.73 g of a polyamic acid having a logarithmic viscosity of 0.48 dl / g (called "polyamic acid (30)").

Comparative Synthesis Example 1

In a 500 ml separable flask, 32.91 g (146.82 mmol) of 2,3,5-tricarboxycyclopentylacetic dianhydride, 15.56 g (143.88 mmol) of paraphenylenediamine and cholesteryl-3,5-diaminobenzoate ( 1.53 g (2.94 mmol) of the compound represented by Formula 19 were dissolved in 450 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours. The reaction solution was then poured into excess methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 DEG C for 15 hours under reduced pressure to obtain 45.52 g of polyamic acid having a logarithmic viscosity of 1.21 dl / g (called "polyamic acid (A)").

40 g of the obtained polyamic acid was dissolved in 360 g of N-methylpyrrolidone, 46.45 g of pyridine and 35.97 g of acetic anhydride were added, followed by dehydration ring-closure reaction by heating at 110 ° C for 4 hours. Subsequently, the reaction product was precipitated and dried in the same manner as in the synthesis of polyamic acid to obtain 36.5 g of a polyimide having a logarithmic viscosity of 1.08 dl / g (called "polyimide (A)").

Comparative Synthesis Example 2

1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan in 500 ml separable flask 35.87 g (114.12 mmol) of -1,3-dione, 11.72 g (108.41 mmol) of paraphenylenediamine and 4- (4'-trifluoromethylbenzoyloxy) cyclohexyl-3,5-diaminobenzoate (above) 2.41 g (5.71 mmol) of the compound represented by the formula (23) was dissolved in 450 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours. The reaction solution was then poured into excess methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 DEG C for 15 hours under reduced pressure to give 44.58 g of a polyamic acid having a logarithmic viscosity of 1.01 dl / g (called "polyamic acid (B)").

40 g of the obtained polyamic acid was dissolved in 360 g of N-methylpyrrolidone, and 28.88 g of pyridine and 65.24 g of acetic anhydride were added, followed by dehydration ring closure reaction by heating at 80 ° C for 4 hours. Subsequently, the reaction product was precipitated and dried in the same manner as in the synthesis of polyamic acid to obtain 36.19 g of a polyimide having a logarithmic viscosity of 0.98 dl / g (called "polyimide (B)").

Comparative Synthesis Example 3

1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan in 500 ml separable flask -1,3-dione 33.19 g (105.59 mmol), 2,3,5-tricarboxycyclopentylacetic dianhydride 1.25 g (5.56 mmol), 10.58 g (97.81 mmol) paraphenylenediamine, 2,2'-bis 3.56 g (11.12 mmol) of (trifluoromethyl) -4,4'-diaminobiphenyl and 1.43 g (2.22) of 3,6-bis (4-aminobenzoyloxy) cholestane (compound represented by Formula 12) Mmol) was dissolved in 450 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours. The reaction solution was then poured into excess methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 DEG C for 15 hours under reduced pressure to give 44.29 g of a polyamic acid having a logarithmic viscosity of 0.91 dl / g (called "polyamic acid (C)").

40 g of the obtained polyamic acid was dissolved in 360 g of N-methylpyrrolidone, and 28.13 g of pyridine and 36.31 g of acetic anhydride were added, followed by dehydration ring-closure reaction by heating at 80 ° C for 4 hours. Subsequently, the reaction product was precipitated and dried in the same manner as in the synthesis of polyamic acid to obtain 35.79 g of a polyimide having a logarithmic viscosity of 0.89 dl / g (called "polyimide (C)").

Comparative Synthesis Example 4

34.63 g (132.06 mmol) of 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 14.00 g (129.42 mmol) of paraphenylenediamine and cholestaryl-3,5-dia in 500 ml separable flasks 1.38 g (2.64 mmol) of minobenzoate (compound represented by Formula 19) were dissolved in 450 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours. The reaction solution was then poured into excess methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 DEG C for 15 hours under reduced pressure to obtain 45.23 g of a polyamic acid having a logarithmic viscosity of 0.95 dl / g (called "polyamic acid (D)").

40 g of the obtained polyamic acid was dissolved in 360 g of N-methylpyrrolidone, and 41.78 g of pyridine and 43.14 g of acetic anhydride were added, followed by dehydration ring-closure reaction by heating at 110 ° C for 4 hours. Subsequently, the reaction product was precipitated and dried in the same manner as in the polyamic acid synthesis, to obtain 35.86 g of a polyimide having a logarithmic viscosity of 0.92 dl / g (called "polyimide (D)").

Comparative Synthesis Example 5

1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan in 500 ml separable flask 29.00 g (96.57 mmol) of -1,3-dione, 6.33 g (24.14 mmol) of 3,5,6-tricarboxynorbornane-2-acetic dianhydride, 12.40 g (114.67 mmol) of paraphenylenediamine and octadecane 2.27 g (6.04 mmol) of oxy-2,4-diaminobenzene was dissolved in 450 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours. The reaction solution was then poured into excess methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 DEG C for 15 hours under reduced pressure to give 44.25 g of a polyamic acid having a logarithmic viscosity of 0.91 dl / g (called "polyamic acid (E)").

40 g of the obtained polyamic acid was dissolved in 360 g of N-methylpyrrolidone, 15.28 g of pyridine and 19.72 g of acetic anhydride were added, followed by dehydration ring-closing reaction by heating at 60 ° C for 3 hours. Subsequently, the reaction product was precipitated and dried in the same manner as in the polyamic acid synthesis, to obtain 35.81 g of a polyimide having a logarithmic viscosity of 0.88 dl / g (called "polyimide (E)").

<Example 1>

(1) Preparation of liquid crystal aligning agent:

The weight ratio of polyimide (1) and polyamic acid (16) to polyimide (1) (terminal encapsulation) obtained in Synthesis Example 1 and polyamic acid (16) (end unsealed) obtained in Synthesis Example 16 is 1: 3. It melt | dissolved in (gamma) -butyrolactone so that it might be set as the solution of 4 weight% of solid content concentration, and this solution was filtered through the filter of 1 micrometer of pore diameters, and the liquid crystal aligning agent of this invention was manufactured.

(2) Fabrication of liquid crystal display device:

(1) The liquid crystal aligning agent of the present invention prepared as described above was applied using a spinner on a transparent conductive film made of an ITO film provided on one surface of a glass substrate having a thickness of 1 mm, and dried by drying at 180 ° C. for 1 hour. A coating film having a thickness of 600 angstroms was formed.

(2) The liquid crystal aligning film was produced by rubbing process the formed coating film surface using the rubbing machine which has the roller which wound the cloth made from nylon. Here, rubbing process conditions were made into the rotation speed of the roll 500 rpm and the stage moving speed of 1 cm / sec.

(3) After producing two board | substrates with a liquid crystal aligning film as mentioned above, apply | coating the epoxy resin adhesive containing aluminum oxide sphere of diameter 17micrometer to each board | substrate outer edge part by the screen printing method, and then each liquid crystal aligning film Two board | substrates were opposingly arrange | positioned so that it might become a reverse direction to the rubbing direction in, and the outer edge parts contacted and crimped | bonded and hardened the adhesive agent.

(4) A nematic liquid crystal "MLC-5081" (manufactured by Melk Co., Ltd.) was filled in a cell gap partitioned by the adhesive on the substrate surface and the outer edge portion, and then the injection hole was sealed with an epoxy adhesive to constitute a liquid crystal cell. Then, the liquid crystal display element was produced by bonding a polarizing plate to the outer surface of a liquid crystal cell so that a polarization direction may correspond with the rubbing direction of the liquid crystal aligning film formed in one surface of this board | substrate.

(5) The abnormal domain was not confirmed when the voltage was applied to and released from the liquid crystal cell of the liquid crystal display device produced as described above, and the liquid crystal alignment property was good. The pretilt angle was measured and found to be 4.8 °. In addition, the afterimage erasing time of the liquid crystal display element was very short in 0.72 second. Moreover, although the pretilt angle was measured by changing rubbing conditions in the range of 200-800 rpm of roll rotations, and 0.5-5 cm / sec of moving speed of a stage, it was excellent in process conditions stability by the error of 4.8 +/- 0.3 degrees. Moreover, when the orientation and reliability test of the obtained liquid crystal display element were evaluated, the liquid-crystal orientation was favorable, and white unevenness was not recognized by the liquid crystal display element even after the reliability test. The results are shown in Table 1.

<Examples 2 to 91>

With the composition shown in Tables 1-3, the liquid crystal aligning agent was produced like Example 1 except having used the polyimide and polyamic acid obtained by the synthesis examples 2-29, and the liquid crystal display element was produced. The measurement and the reliability test of the liquid crystal orientation, the pretilt angle, the afterimage erasing time in the produced liquid crystal display element were performed. The results are shown in Tables 1-3.

Example Terminal encapsulation polymer Terminal unsealed polymer % Of end-sealing polymer Orientation Pretilt angle (°) Afterimage elimination time (s) responsibility Example 1 Polyimide 1 Polyamic Acid 19 25% Good 4.8 0.72 Good Example 2 Polyimide 1 Polyamic Acid 19 20% Good 4.7 0.75 Good Example 3 Polyimide 1 Polyamic Acid 22 30% Good 5.0 0.82 Good Example 4 Polyimide 1 Polyamic Acid 26 15% Good 4.6 0.70 Good Example 5 Polyimide 2 Polyamic Acid 17 20% Good 4.9 0.80 Good Example 6 Polyimide 2 Polyamic Acid 19 25% Good 5.1 0.84 Good Example 7 Polyimide 2 Polyamic Acid 23 20% Good 4.8 0.79 Good Example 8 Polyimide 2 Polyamic Acid 26 20% Good 4.7 0.81 Good Example 9 Polyimide 3 Polyamic Acid 18 20% Good 4.4 0.83 Good Example 10 Polyimide 3 Polyamic Acid 24 25% Good 4.6 0.79 Good Example 11 Polyimide 3 Polyamic Acid 22 30% Good 5.0 0.88 Good Example 12 Polyimide 3 Polyamic Acid 27 20% Good 4.8 0.83 Good Example 13 Polyimide 4 Polyamic Acid 16 25% Good 4.6 0.72 Good Example 14 Polyimide 4 Polyamic Acid 21 20% Good 4.5 0.65 Good Example 15 Polyimide 4 Polyamic Acid 22 15% Good 4.4 0.77 Good Example 16 Polyimide 4 Polyamic Acid 26 25% Good 4.6 0.78 Good Example 17 Polyimide 5 Polyamic Acid 17 20% Good 4.2 0.84 Good Example 18 Polyimide 5 Polyamic Acid 19 35% Good 4.8 0.78 Good Example 19 Polyimide 5 Polyamic Acid 23 18% Good 4.2 0.83 Good Example 20 Polyimide 5 Polyamic Acid 26 30% Good 4.6 0.80 Good Example 21 Polyimide 6 Polyamic Acid 18 20% Good 4.5 0.85 Good Example 22 Polyimide 6 Polyamic Acid 22 12% Good 4.3 0.86 Good Example 23 Polyimide 6 Polyamic Acid 24 25% Good 4.5 0.81 Good Example 24 Polyimide 6 Polyamic Acid 27 25% Good 4.5 0.82 Good Example 25 Polyimide 7 Polyamic Acid 18 30% Good 5.9 0.70 Good Example 26 Polyimide 7 Polyamic Acid 20 25% Good 5.8 0.61 Good Example 27 Polyimide 7 Polyamic Acid 21 20% Good 5.7 0.63 Good Example 28 Polyimide 7 Polyamic Acid 25 30% Good 6.1 0.65 Good Example 29 Polyimide 7 Polyamic Acid 27 20% Good 5.9 0.63 Good Example 30 Polyimide 8 Polyamic Acid 17 25% Good 4.5 0.74 Good

Example Terminal encapsulation polymer Terminal unsealed polymer % Of end-sealing polymer Orientation Pretilt angle (°) Afterimage elimination time (s) responsibility Example 31 Polyimide 8 Polyamic Acid 20 20% Good 4.4 0.59 Good Example 32 Polyimide 8 Polyamic Acid 21 20% Good 4.4 0.60 Good Example 33 Polyimide 8 Polyamic Acid 24 25% Good 4.6 0.69 Good Example 34 Polyimide 8 Polyamic Acid 25 30% Good 4.7 0.68 Good Example 35 Polyimide 8 Polyamic Acid 27 20% Good 4.5 0.62 Good Example 36 Polyimide 9 Polyamic Acid 18 17% Good 4.8 0.72 Good Example 37 Polyimide 9 Polyamic Acid 19 24% Good 4.9 0.66 Good Example 38 Polyimide 9 Polyamic Acid 23 16% Good 4.7 0.71 Good Example 39 Polyimide 9 Polyamic Acid 25 30% Good 5.1 0.68 Good Example 40 Polyimide 10 Polyamic Acid 17 30% Good 5.6 0.80 Good Example 41 Polyimide 10 Polyamic Acid 19 25% Good 5.5 0.72 Good Example 42 Polyimide 10 Polyamic Acid 24 18% Good 5.4 0.74 Good Example 43 Polyimide 10 Polyamic Acid 26 20% Good 5.6 0.71 Good Example 44 Polyimide 11 Polyamic Acid 21 20% Good 4.8 0.64 Good Example 45 Polyimide 11 Polyamic Acid 23 25% Good 4.9 0.70 Good Example 46 Polyimide 11 Polyamic Acid 27 22% Good 4.6 0.66 Good Example 47 Polyimide 11 Polyamic Acid 28 30% Good 4.9 0.72 Good Example 48 Polyimide 12 Polyamic Acid 20 20% Good 5.2 0.68 Good Example 49 Polyimide 12 Polyamic Acid 21 20% Good 5.2 0.69 Good Example 50 Polyimide 12 Polyamic Acid 27 22% Good 5.1 0.72 Good Example 51 Polyimide 12 Polyamic Acid 28 23% Good 5.3 0.75 Good Example 52 Polyimide 13 Polyamic Acid 20 25% Good 4.4 0.78 Good Example 53 Polyimide 13 Polyamic Acid 21 25% Good 4.4 0.80 Good Example 54 Polyimide 13 Polyamic Acid 27 28% Good 4.5 0.81 Good Example 55 Polyimide 14 Polyamic Acid 16 14% Good 5.9 0.89 Good Example 56 Polyimide 14 Polyamic Acid 21 26% Good 6.2 0.81 Good Example 57 Polyimide 14 Polyamic Acid 27 31% Good 6.3 0.82 Good Example 58 Polyimide 14 Polyamic Acid 28 21% Good 6.1 0.92 Good Example 59 Polyimide 15 Polyamic Acid 18 40% Good 4.6 0.89 Good Example 60 Polyimide 15 Polyamic Acid 21 25% Good 4.8 0.84 Good

Example Terminal encapsulation polymer Terminal unsealed polymer % Of end-sealing polymer Orientation Pretilt angle (°) Afterimage elimination time (s) responsibility Example 61 Polyimide 15 Polyamic Acid 27 20% Good 4.7 0.85 Good Example 62 Polyimide 15 Polyamic Acid 28 18% Good 4.4 0.91 Good Example 63 Polyamic acid 1 Polyamic Acid 16 25% Good 4.4 0.88 Good Example 64 Polyamic Acid 2 Polyamic Acid 22 30% Good 4.3 0.87 Good Example 65 Polyamic Acid 3 Polyamic Acid 19 20% Good 4.2 0.90 Good Example 66 Polyamic Acid 4 Polyamic Acid 22 16% Good 4.1 0.87 Good Example 67 Polyamic Acid 5 Polyamic Acid 19 24% Good 4.5 0.86 Good Example 68 Polyamic Acid 7 Polyamic Acid 20 30% Good 5.5 0.79 Good Example 69 Polyamic Acid 8 Polyamic Acid 21 21% Good 4.1 0.80 Good Example 70 Polyamic Acid 11 Polyamic Acid 20 20% Good 4.2 0.81 Good Example 71 Polyamic Acid 12 Polyamic Acid 21 20% Good 4.4 0.84 Good Example 72 Polyimide 1 Polyimide 18 30% Good 4.9 0.88 Good Example 73 Polyimide 2 Polyimide 18 25% Good 4.7 0.85 Good Example 74 Polyimide 4 Polyimide 23 20% Good 4.6 0.86 Good Example 75 Polyimide 5 Polyimide 23 24% Good 4.6 0.90 Good Example 76 Polyimide 7 Polyimide 23 35% Good 5.9 0.79 Good Example 77 Polyimide 8 Polyimide 18 18% Good 4.9 0.81 Good Example 78 Polyimide 12 Polyimide 23 20% Good 5.1 0.83 Good Example 79 Polyimide 13 Polyimide 23 20% Good 5.2 0.81 Good Example 80 Polyamic acid 1 Polyimide 18 18% Good 4.8 0.95 Good Example 81 Polyamic Acid 4 Polyimide 23 30% Good 4.8 0.94 Good Example 82 Polyamic Acid 7 Polyimide 23 20% Good 5.8 0.91 Good Example 83 Polyamic Acid 13 Polyimide 23 25% Good 4.8 0.62 Good Example 84 Polyimide 2 none 100% Good 4.3 0.96 Good Example 85 Polyimide 5 none 100% Good 4.1 0.94 Good Example 86 Polyimide 8 none 100% Good 4.2 0.90 Good Example 87 Polyimide 14 none 100% Good 4.4 0.92 Good Example 88 Polyamic Acid 3 none 100% Good 4.0 0.99 Good Example 89 Polyamic Acid 6 none 100% Good 4.1 0.96 Good Example 90 Polyamic Acid 9 none 100% Good 4.0 0.93 Good Example 91 Polyimide 29 Polyamic Acid 21 100% Good 5.2 0.58 Good

<Example>

(1) Preparation of liquid crystal aligning agent:

The polyamic acid (terminal encapsulation) (30) obtained in Synthesis Example 30 was dissolved in N-methylpyrrolidone to give a solution having a solid content of 4% by weight, and the solution was filtered through a filter having a pore size of 1 μm to give a liquid crystal of the present invention. An alignment agent was prepared.

(2) Fabrication of liquid crystal display device:

The liquid crystal display element was produced like Example 1 except having changed the nematic liquid crystal into "MLC-2012" (made by Melk, Inc.). When the voltage was applied and released to the liquid crystal cell with respect to the produced liquid crystal display element, the abnormal domain was not confirmed, and liquid crystal orientation was favorable. When the pretilt angle was measured, it was confirmed that it was vertically oriented at 89.5 degrees. In addition, the afterimage erasing time of the liquid crystal display element was as short as 0.95 second. Moreover, when the orientation and reliability test of the obtained liquid crystal display element were evaluated, the liquid-crystal orientation was favorable, and white unevenness was not recognized by the liquid crystal display element even after the reliability test.

Comparative Example 1

The liquid crystal aligning agent was produced like Example 1 except having used the polyimide (A) obtained by the comparative synthesis example 1 instead of the polyimide (1), and produced the liquid crystal display element. The measurement and the reliability test of the liquid crystal orientation, the pretilt angle, the afterimage erasing time in the produced liquid crystal display element were performed. The results are shown in Table 4.

<Comparative Examples 2 to 33>

With the composition shown in Table 4, a liquid crystal aligning agent was produced in the same manner as in Example 1 except that the polyimide obtained in Comparative Synthesis Examples 2 to 5 and the polyamic acid and polyimide obtained in Synthesis Examples 16 to 28 were used. The liquid crystal display element was produced. The measurement and the reliability test of the liquid-crystal orientation, the pretilt angle, the afterimage erase time in the produced liquid crystal display element were performed. The results are shown in Table 4.

Example Terminal encapsulation polymer Terminal unsealed polymer % Of end-sealing polymer Orientation Pretilt angle (°) Afterimage elimination time (s) responsibility Example 1 Polyimide A Polyamic Acid 16 25% Good 4.8 3.35 Good Example 2 Polyimide A Polyamic Acid 20 20% Good 4.3 2.55 Good Example 3 Polyimide A Polyamic Acid 22 30% Good 4.9 3.25 Good Example 4 Polyimide A Polyamic Acid 26 19% Good 4.6 3.08 Good Example 5 Polyimide B Polyamic Acid 18 22% Good 4.5 3.20 Bad Example 6 Polyimide B Polyamic Acid 19 25% Good 4.5 0.80 Bad Example 7 Polyimide B Polyamic Acid 24 16% Good 4.8 0.79 Bad Example 8 Polyimide B Polyamic Acid 27 20% Good 4.7 1.11 Bad Example 9 Polyimide C Polyamic Acid 20 20% Good 4.1 1.52 Good Example 10 Polyimide C Polyamic Acid 24 25% Good 4.2 1.49 Good Example 11 Polyimide C Polyamic Acid 27 30% Good 4.0 1.48 Good Example 12 Polyimide D Polyamic Acid 21 20% Good 4.4 3.13 Good Example 13 Polyimide D Polyamic Acid 24 18% Good 4.3 3.43 Good Example 14 Polyimide D Polyamic Acid 28 20% Good 4.2 3.65 Good Example 15 Polyimide E Polyamic Acid 21 25% Good 4.2 1.73 Good Example 16 Polyimide E Polyamic Acid 28 30% Good 4.4 1.78 Good Example 17 Polyamic acid A Polyamic Acid 16 25% Good 4.2 4.44 Bad Example 18 Polyamic acid B Polyamic Acid 21 20% Good 4.1 3.78 Bad Example 19 Polyamic acid C Polyamic Acid 20 21% Good 4.2 3.83 Bad Example 20 Polyamic acid D Polyamic Acid 21 20% Good 4.0 3.80 Bad Example 21 Polyamic acid E Polyamic Acid 21 20% Good 4.1 3.68 Bad Example 22 Polyimide A Polyimide 18 25% Good 4.1 5.80 Good Example 23 Polyimide B Polyimide 23 18% Good 4.6 4.31 Bad Example 24 Polyimide C Polyimide 23 20% Good 4.1 5.11 Bad Example 25 Polyimide D Polyimide 23 30% Good 4.2 4.29 Bad Example 26 Polyimide E Polyimide 18 25% Good 4.3 3.98 Good Example 27 Polyamic acid A Polyimide 18 20% Good 4.1 4.18 Bad Example 28 Polyamic acid B Polyimide 23 30% Good 4.3 4.83 Bad Example 29 Polyamic acid C Polyimide 23 10% Good 4.6 4.46 Bad Example 30 Polyamic acid D Polyimide 18 30% Good 4.6 4.75 Good Example 31 Polyamic acid E Polyimide 23 20% Good 4.6 4.14 Good Example 32 Polyimide A none 100% Good 4.1 4.64 Good Example 33 Polyimide B none 100% Good 4.5 4.89 Good

As described above, according to the present invention, when the liquid crystal aligning film is used, the liquid crystal alignment property is satisfactory, and while having a good alignment characteristic capable of expressing a high pretilt angle that does not depend on process conditions such as film thickness and rubbing conditions, The liquid crystal aligning agent which can form the liquid crystal aligning film which has short afterimage erasing time in a liquid crystal display element and at the same time has high reliability.

The liquid crystal aligning film formed by the liquid crystal aligning agent of this invention can be preferably used in order to comprise various liquid crystal display elements, such as a TN type liquid crystal display element, an STN type liquid crystal display element, and a SH (Super Homeotropic) type liquid crystal display element. Moreover, the liquid crystal display element provided with the said liquid crystal aligning film is excellent also in liquid crystal orientation and reliability, and can be effectively used for various apparatuses, for example, a desktop calculator, a wristwatch, a table clock, a coefficient display board, a word processor, a personal computer, a liquid crystal It can be used suitably as display apparatuses, such as a television.

Claims (6)

Obtained by reacting at least one compound selected from the group consisting of (A) (a) tetracarboxylic dianhydride, (b) diamine compound and (c) dicarboxylic anhydride, monoamine compound and monoisocyanate compound Terminally sealed polyamic acid having an alicyclic skeleton at the same time, (B) at least one terminal sealed polymer selected from the group consisting of terminal sealed imidized polymers obtained by dehydrating and closing the polyamic acid It contains, The liquid crystal aligning agent characterized by the above-mentioned. The liquid crystal aligning agent of Claim 1 which further contains the terminal sealing polyamic acid which used dicarboxylic acid anhydride as (c) component. (1) reacts at least one compound selected from the group consisting of (A) (a) tetracarboxylic dianhydride, (b) diamine compound and (c) dicarboxylic anhydride, monoamine compound and monoisocyanate compound At least one end-sealing polymer selected from the group consisting of a terminal-sealed polyamic acid obtained by the reaction step and at the same time having an alicyclic skeleton and (B) a terminal-sealed imidized polymer obtained by dehydrating and closing the polyamic acid; and (2) a terminal unsealed polyamic acid obtained by reacting (a) tetracarboxylic dianhydride and (b) a diamine compound, and a terminal unsealed imidized polymer obtained by dehydrating and closing the polyamic acid. A liquid crystal aligning agent containing at least one terminal unsealed polymer. 4. The liquid crystal aligning agent according to claim 3, wherein the terminal sealed polymer is a terminal sealed imidized polymer and the terminal unsealed polymer is a terminal unsealed polyamic acid. The liquid crystal aligning agent of Claim 4 in which a terminal sealing imidation polymer uses a monoamine compound as (c) component. The liquid crystal aligning film obtained from the liquid crystal aligning agent of any one of Claims 1-5 is provided, The liquid crystal display element characterized by the above-mentioned.