KR20060049699A - Vertical liquid crystal aligning agent and vertical liquid crystal display having a repeller - Google Patents

Abstract

This invention provides the liquid crystal aligning agent which provides the vertical liquid crystal aligning film excellent in the baking characteristic and reliability also when used with a reflective electrode.

According to the present invention, there is provided a vertical liquid crystal aligning agent comprising 100 parts by weight of a polymer having an amic acid repeating unit and / or an imide repeating unit, and 5 parts by weight or more of a compound having two or more epoxy groups in a molecule.

Vertical liquid crystal aligning agent, liquid crystal display element, reflective electrode, baking characteristics

Description

Vertical Liquid Crystal Aligning Agent and Vertical Liquid Crystal Display Having a Repeller

[Patent Document 1] Japanese Unexamined Patent Publication No. 2002-327058

The present invention relates to a vertical liquid crystal display element having a vertical liquid crystal aligning agent and a reflective electrode. More specifically, it relates to a liquid crystal display element having a vertical liquid crystal aligning agent for providing a vertical liquid crystal alignment film having good baking characteristics, regardless of the kind of electrode constituting the liquid crystal display element, and a reflective electrode including the vertical liquid crystal alignment film. will be.

Conventionally, a layer of a nematic liquid crystal having positive dielectric anisotropy is formed between two substrates on which a liquid crystal alignment film is formed on the surface via a transparent conductive film to form a sandwich cell, and the long axis of the liquid crystal molecules is one substrate. A TN type liquid crystal display element having a TN (Twisted Nematic) type liquid crystal cell which is twisted 90 degrees continuously from the side toward the other substrate is known.

In addition, the addition of a chiral agent causes the long axis of the liquid crystal molecules to be continuously twisted over 180 degrees between the substrates, and there is also a STN (Super Twisted Nematic) type liquid crystal display device using the birefringence effect. do. Further, recently, a nematic liquid crystal layer having a negative dielectric anisotropy or a cholesteric liquid crystal layer having a spiral axis parallel to a substrate normal is formed between opposing substrates, and pigments are formed in these liquid crystal layers. There has also been developed a guest-host type reflective liquid crystal display element. Orientation of the liquid crystal in these liquid crystal display elements is normally expressed by the liquid crystal aligning film in which the rubbing process was performed. Moreover, as a material of the liquid crystal aligning film which comprises a liquid crystal display element, polyimide, polyamide, polyester, etc. are known conventionally. In particular, polyimides are used in various liquid crystal display devices because of their excellent heat resistance, affinity with liquid crystals, mechanical strength, and the like.

In recent years, studies, such as display quality improvement, low power consumption, etc., including high definition of a liquid crystal display element, are progressing, and the range of utilization of a liquid crystal display element is also expanded. In particular, since reflective or semi-transmissive liquid crystal display elements capable of maintaining high display quality in outdoor use are used in portable terminals, various metal electrodes (hereinafter, referred to as reflective electrodes) have been used to express the function of reflecting external light. However, in the vertical liquid crystal display element having a reflective electrode, when an alignment film used as a conventional ITO electrode is used, there is a problem that reliability is deteriorated, such as burn-out or alignment defects during long-term lighting.

The objective of this invention is providing the liquid crystal aligning agent which provides the vertical liquid crystal aligning film excellent in the baking characteristic and reliability also when used with a reflective electrode.

Still another object of the present invention is to provide a vertical liquid crystal display device having a reflective electrode comprising a vertical liquid crystal alignment film obtained from the liquid crystal aligning agent of the present 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 are 100 parts by weight of a polymer having a repeating unit represented by the following formula (1) and / or a repeating unit represented by the following formula (2) and a compound having two or more epoxy groups in the molecule It is achieved by the liquid crystal aligning agent which consists of 5 weight part or more.

In the formula, P ¹ is a tetravalent organic group, and Q ¹ is a divalent organic group.

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

The vertical liquid crystal aligning film formed by the liquid crystal aligning agent of this invention is not limited to the case where it is used with an ITO electrode, and when it is used together with a reflection electrode, it is excellent in baking characteristics and reliability, and in order to comprise a liquid crystal display element. It can be used preferably.

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

Best Mode for Carrying Out the Invention

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

The liquid crystal aligning agent of the present invention contains a polymer having a repeating unit represented by the formula (1) and / or a repeating unit represented by the formula (2) (hereinafter referred to as "specific polymer"). The specific polymer may be a mixture of (1) a polyamic acid having a repeating unit represented by the formula (1) and a polyimide having a repeating unit represented by the formula (2), and (2) a repeating unit represented by the formula (1) And a repeating unit represented by the formula (2) may be a polymer (hereinafter, also referred to as a "partial imidation polymer") formed by combining randomly or block-like in the same molecule.

The said polyamic acid can be obtained by ring-opening polyaddition of tetracarboxylic dianhydride and a diamine compound. Moreover, polyimide can be obtained by dehydrating ring-closure of a polyamic acid normally. The partial imidation polymer can be obtained by the method of partially dehydrating and ring-closing polyamic acid, or the method of synthesizing a block copolymer by combining an amic acid prepolymer and an imide prepolymer.

<Polyamic acid>

Tetracarboxylic dianhydride

As tetracarboxylic dianhydride, a butane tetracarboxylic dianhydride, 1,2,3,4- cyclobutane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4- Cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarb Acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride , 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexa Hydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1, 3,3a, 4,5,9b-hexahydro-5-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1 , 3-dione, 1,3,3a, 4,5,9b-hexahydro-5-ethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naph Earth [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-ethyl-5- (tetrahydro-2,5-dioxo-3 -Furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2, 5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-ethyl-5- (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro- 5,8-dimethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 5- (2,5-di Oxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2.2.2] -jade To-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran -2 ', 5'-dione), aliphatic and alicyclic tetracarboxylic dianhydrides such as compounds represented by the following formulas (1a) and (1b);

In formula, R <^1> and R <^3> represents the divalent organic group which has an aromatic ring, R <^2> and R <^4> represents a hydrogen atom or an alkyl group, and ^two or more R <^2> and R <^4> may be same or different, respectively.

Pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenylsulfontetracarboxylic dianhydride, 1,4,5 , 8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylethertetracarboxylic dianhydride, 3,3 ', 4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3', 4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic Acid dianhydrides, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydrides, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydrides, 4 , 4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3', 4,4 '-Biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphineoxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenyl phthalic acid) -4,4'-diphenylmethane dianhydride, Ethylene glycol-bis (anhydrous trimellitate), propylene glycol-bis (anhydrous trimellitate), 1,4-butanediol-bis (anhydrous trimellitate), 1,6-hexanediol-bis (anhydrous trimellitate) , 1,8-octanediol-bis (anhydrous trimellitate), 2,2-bis (4-hydroxyphenyl) propane-bis (anhydrous trimellitate), represented by the following general formulas (1) to (4) Aromatic tetracarboxylic dianhydrides, such as a compound, are mentioned. These are used individually by 1 type or in combination of 2 or more types.

Among them, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride , 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic 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), pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4 '-Biphenylsulfontetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, the compound represented by the following formulas (5) to (7) among the compounds represented by the formula (1a) and The compound represented by following General formula (8) among the compound represented by the said Formula (1b) is preferable at the point which can express favorable liquid-crystal orientation. As particularly preferred, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5 -Cyclohexanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-di Oxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro- 2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane-2,4-dione-6- Spiro-3 '-(tetrahydrofuran-2', 5'-dione), a pyromellitic dianhydride, and the compound represented by following General formula (5) are mentioned.

In particular, when the repeating unit (amic acid unit) represented by the formula (1) and the repeating unit (imide unit) represented by the formula (2) are present together, a tetravalent organic group represented by P ¹ in the formula (1), The tetravalent organic groups represented by P ² in the repeating unit (imide unit) represented by ² may be the same or different, respectively, but as P ¹ , groups represented by the following formulas (i) and (i ′) are preferable. . As P ² , a group having an alicyclic skeleton is preferable, and a group represented by each of the following formulas (ii) and (ii ′) is particularly preferable.

In formula, R is a halogen atom, a methyl group, or an ethyl group, a is an integer of 0 or 1, b is an integer of 0-5, c and d are each independently an integer of 0-4.

As a specific example of the preferable tetracarboxylic dianhydride in each repeating unit, As tetracarboxylic dianhydride which comprises an amic acid unit, For example, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, pyromellitic dianhydride, and the like. . Moreover, as tetracarboxylic dianhydride which comprises an imide unit, alicyclic tetracarboxylic dianhydride is preferable, Especially 2,3,5- tricarboxy cyclopentyl acetic dianhydride, 1,3,3a, 4, 5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a , 4,5,9b-hexahydro-8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione) etc. are mentioned.

[Diamine Compound]

As a diamine compound used for the synthesis | combination of the said polyamic acid, p-phenylenediamine, m-phenylenediamine, 4,4'- diamino diphenylmethane, 4,4'- diamino diphenyl ethane, 4, for example , 4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 4 , 4'-diaminodiphenylether, 1,5-diaminonaphthalene, 2,2'-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'-diaminobenzo Phenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- ( 4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 1, 4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 2,7-diaminofluorene, 9 , 9-bis (4-aminophenyl) fluorene, 4,4'-methylene-bis (2-chloroaniline), 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl , 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 1,4,4 ' -(p-phenyleneisopropylidene) bisaniline, 4,4 '-(m-phenyleneisopropylidene) bisaniline, 2,2'-bis [4- (4-amino-2-trifluoromethyl Phenoxy) phenyl] hexafluoropropane, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 4,4'-bis [(4-amino-2-trifluoro Aromatic diamines such as methyl) phenoxy] -octafluorobiphenyl, 4- (4-n-heptylcyclohexyl) phenoxy-2,4-diaminobenzene and the like;

1,1-methacrylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine , 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindenylenedimethylenediamine, tricyclo [6.2.1.0 ^2,7 ] -undecylene Aliphatic and alicyclic diamines such as dimethyldiamine, 4,4'-methylenebis (cyclohexylamine), and the like;

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-phenylphenanthrizine, 1,4-diaminopiperazine, Molecules such as 3,6-diaminoacridine, bis (4-aminophenyl) phenylamine and compounds represented by the following formulas 1c to 1d A diamine having the nitrogen atoms other than two primary amino groups and the primary amino group;

In the formula, R ⁵ 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, X represents a divalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine, R ⁶ represents a divalent organic group, and a plurality of X May be the same or different.

 Mono substituted phenylenediamines represented by the following general formula (1e); Diaminoorganosiloxane represented by the following general formula (1f);

In the formula, R ⁷ represents a divalent organic group selected from -O-, -COO-, -OCO-, -NHCO-, -CONH- and -CO-, and R ⁸ represents a steroid skeleton, a trifluoromethyl group and a fluorine group. The monovalent organic group or the C6-C30 alkyl group which has group chosen from a furnace group is shown.

In formula, R <^9> represents a C1-C12 hydrocarbon group, two or more R <^9> may be same or different, p is an integer of 1-3, q is an integer of 1-20.

The compound etc. which are represented by following General formula (9)-(13) 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, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 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 '-(p-phenylenediisopropylidene) bisaniline, 4,4 '-(m-phenylenediisopropylidene) bisaniline, 1,4-cyclohexanediamine, 4,4'-methylenebis (cyclohexylamine), 1,4-bis (4-aminophenoxy) benzene, 4 , 4'-bis (4-aminophenoxy) biphenyl, 4- (4-n-heptylcyclohexyl) phenoxy-2,4-diaminobenzene, a compound represented by the above formulas (9) to (13) , 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, among the compounds represented by Formula 1c A compound represented by the following formulas (16) to (21) among the compound represented by the formula (14), the compound represented by the following formula (15) among the compound represented by the formula (1d) and the compound represented by the formula (1e) This is preferred.

[Synthesis reaction of polyamic acid]

The use ratio of the tetracarboxylic dianhydride and the diamine compound used for the polyamic acid synthesis reaction is preferably such that the acid anhydride group of the tetracarboxylic dianhydride is 0.2 to 2 equivalents relative to 1 equivalent of the amino group contained in the diamine compound. And the ratio which becomes 0.3-1.2 equivalent is more preferable.

Synthesis reaction of polyamic acid is performed in organic solvent, Preferably it is -20-150 degreeC, More preferably, it is performed on the temperature conditions of 0-100 degreeC. The organic solvent is not particularly limited as long as it can dissolve the polyamic acid synthesized. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl Aprotic polar solvents such as sulfoxide, γ-butyrolactone, tetramethyl urea, hexamethylphosphorotriamide and the like; phenolic solvents such as m-cresol, xylenol, phenol, halogenated phenol and the like can be exemplified. In addition, it is preferable that the usage-amount (a) of an organic solvent is an amount which will be 0.1-30 weight% with respect to the total amount (a + b) of the total reaction solution (b) of tetracarboxylic dianhydride and a diamine compound.

[Poor Solvent]

In the organic solvent, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like, which are poor solvents of the polyamic acid, can be used in combination without causing precipitation of the polyamic acid to be produced. Specific examples of such poor solvents include methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, acetone, Methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol Methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether , Diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoene Ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloro methane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dike Lorbenzene, hexane, heptane, octane, benzene, toluene, xylene and the like.

As described above, a reaction solution obtained by dissolving the polyamic acid is obtained. Furthermore, a polyamic acid can be obtained by putting this reaction solution in a large amount of poor solvents, obtaining a precipitate, and drying this precipitate under reduced pressure. In addition, the polyamic acid can be purified by dissolving the polyamic acid again in an organic solvent and then precipitating with a poor solvent once or several times.

[Imidated Polymer]

<Imidated Polymer>

The imidation polymer which comprises the liquid crystal aligning agent of this invention can be manufactured by dehydrating and ring-closing the said polyamic acid. The dehydration ring closure of the polyamic acid is, for example, 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 in this solution, and heating as necessary. It is advantageously done by the method.

50-200 degreeC is preferable and, as for the reaction temperature in the method of heating the polyamic acid of said (i), 60-170 degreeC is more preferable. When reaction temperature is less than 50 degreeC, dehydration ring-closure reaction does not fully advance, and when reaction temperature exceeds 200 degreeC, the molecular weight of the imidation polymer obtained may fall.

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

[Partial imide]

<Partially imidized polymer>

The partial imidation polymer used by this invention has a structure obtained by partially imidating the said polyamic acid. 10-90% is preferable and, as for the imidation ratio in the partial imidation polymer used by this invention, 30-70% is more preferable. Here, "imidation ratio" shall represent the ratio of the number of repeating units which form an imide ring with respect to the total number of repeating units in a polymer in%. At this time, part of the imide ring may be an isoimide ring.

As a method for synthesizing the partially imidized polymer, for example, (i) a method of partially dehydrating and closing the ring by heating the polyamic acid, and (ii) dissolving the polyamic acid in an organic solvent and dehydrating agent and dehydration in this solution. By adding a ring closure catalyst and heating as necessary, partially dehydrating and ring closing, or (iii) condensing and synthesizing by mixing tetracarboxylic dianhydride, diamine compound and diisocyanate compound and heating as necessary. Method is used.

300 degreeC or less is preferable and, as for the reaction temperature of the method of said (i), 100-250 degreeC is more preferable. When reaction temperature exceeds 300 degreeC, the molecular weight of the imide group containing polyamic acid obtained may fall.

On the other hand, as a dehydrating agent used by the method of said (ii), acid anhydrides, such as an acetic anhydride, a propionic anhydride, a trifluoroacetic anhydride, etc. are mentioned, for example. It is preferable that the usage-amount of a dehydrating agent shall be 0.2-20 mol with respect to 1 mol of repeating units of a polyamic acid. As the dehydration ring closure catalyst, tertiary amines such as pyridine, collidine, lutidine, triethylamine and the like can be used. It is not limited to these. In addition, it is preferable that the usage-amount of an imidation catalyst shall be 0.1-10 mol with respect to 1 mol of dehydrating agents to be used. Moreover, the organic solvent similar to the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid as an organic solvent used for reaction of dehydration ring closure is mentioned. Moreover, 0-180 degreeC is preferable and, as for the reaction temperature of dehydration ring closure, 60-150 degreeC is more preferable. In addition, the partial imidation polymer can be refine | purified by performing the same operation as the purification method of a polyamic acid with respect to the reaction solution obtained in this way.

Specific examples of the diisocyanate compound used in the reaction of (iii) include aliphatic diisocyanates such as hexamethylene diisocyanate; Cyclohexane-1,2-diisocyanate, 1-methylcyclohexane-2,4-diisocyanate, 1,2-dimethylcyclohexane-ω, ω'-diisocyanate, 1,4-dimethylcyclohexane-ω, ω Alicyclic diisocyanates such as' -diisocyanate, isophorone diisocyanate, 1,3,5-trimethyl-2-propylcyclohexane-1ω, 2ω-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate; Diphenylmethane-4,4'-diisocyanate, 1,3-phenylenediisocyanate, 1,4-phenylenediisocyanate, 1-methyl-2,4-phenylenediisocyanate, 1-methyl-2,6-phenylenedi Aromatic diisocyanate, such as an isocyanate and the diisocyanate represented by following formula (22)-(26), is mentioned.

Among them, dicyclohexyl methane-4,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, 1-methyl-2,4-phenylenedi isocyanate, 1-methyl-2,6-phenylene diisocyanate It is mentioned as a preferable thing. These can be used individually or in combination of 2 or more types. In addition, the reaction of said (iii) does not require a catalyst in particular, 50-200 degreeC is preferable and 100-160 degreeC of reaction temperature is more preferable.

[End modification]

<End-modified polymer>

The polyamic acid and partially imidized polymer may be of terminally modified type with controlled molecular weight. By using this terminal-modified polymer, the coating characteristic of a liquid crystal aligning agent, etc. can be improved, without the effect of this invention being impaired. Such terminal-modified type can be synthesize | combined by adding an acid anhydride, a monoamine compound, a monoisocyanate compound, etc. to a reaction system, when synthesize | combining a polyamic acid. Here, examples of the acid anhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride, n-hexadecylsuccinic anhydride, and the like. Can be. As the monoamine compound, for example, aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine , n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n -Eicosylamine, etc. are mentioned. Moreover, as a monoisocyanate compound, phenyl isocyanate, naphthyl isocyanate, etc. are mentioned, for example.

Logarithmic viscosity

Logarithmic viscosity of the polymer

As for the value of the logarithmic viscosity ((eta) _ln ) of the polyamic acid and partial imidation polymer obtained as mentioned above, 0.05-10 dl / g is preferable and 0.05-5 dl / g is more preferable.

The value of the logarithmic viscosity (η _ln ) of the present invention uses N-methyl-2-pyrrolidone as a solvent, and the viscosity is measured at 30 ° C for a solution having a concentration of 0.5 g / 100 ml. Obtained by

<Liquid crystal aligning agent>

It is advantageous that the liquid crystal aligning agent of this invention is comprised by dissolving and containing a specific polymer in an organic solvent.

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

Although solid content concentration of the liquid crystal aligning agent of this invention is selected in consideration of viscosity, volatility, etc., Preferably it is the range of 1 to 10 weight%. That is, although the liquid crystal aligning agent of this invention is apply | coated to the board | substrate surface, and the coating film used as a liquid crystal aligning film is formed, when solid content 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. When solid content concentration exceeds 10 weight%, the film thickness of a coating film becomes too large and it is difficult to obtain a favorable liquid crystal aligning film, and also the viscosity of a liquid crystal aligning agent increases, and coating property tends to be inferior. Moreover, 0-200 degreeC is preferable and, as for the temperature at the time of manufacturing the liquid crystal aligning agent of this invention, 20-60 degreeC is more preferable.

The liquid crystal aligning agent of this invention contains the compound which has two or more epoxy groups (henceforth "epoxy group containing compound") in a molecule | numerator 5 weight part or more with respect to 100 weight part of specific polymers. Such an epoxy group-containing compound may be selected from compounds represented by the following formulas (3) and (4).

In the formula, R ⁰¹ represents a divalent aliphatic group.

In the formula, R ⁰² represents a divalent organic group.

Examples of such epoxy group-containing compounds represented by the above formulas (3) and (4) include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and tripropylene glycol diglycidyl ether. , Polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol digly Cydyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis ( N, N- diglycidylaminomethyl) cyclohexane, N, N, N ', N'- tetraglycidyl-4,4'- diaminodiphenylmethane, etc. are mentioned as a preferable thing. As content of such an epoxy compound, Preferably it is 5-40 weight part, More preferably, it is 10-30 weight part with respect to 100 weight part of specific polymers contained in an aligning agent, and can contain it in the grade which does not impair the characteristic as an aligning agent. have.

In addition, the liquid crystal aligning agent of this invention may contain the functional silane containing compound (henceforth a "silane coupling agent"). As such a silane coupling agent, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 2-aminopropyl trimethoxysilane, 2-aminopropyl triethoxysilane, N- (2- Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane , N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxy Silylpropyltriethylenetriamine, 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-benzyl-3-ami Propyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N -Bis (oxyethylene) -3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, etc. are mentioned.

The blending ratio of these silane coupling agents 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 specific polymer.

<Liquid crystal display element>

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

(1) The liquid crystal aligning agent of this invention is apply | coated to one side of the board | substrate with which the patterned transparent conductive film was provided by methods, such as a roll coater method, a spinner method, the printing method, the inkjet method, etc., and then heating a coating surface. A coating film is formed. As a board | substrate here, For example, glass, such as float glass and a soda glass; Transparent substrates including plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate and the like can be used. Examples of the transparent conductive film provided on one side of the substrate include an NESA film containing tin oxide (SnO ₂ ) (registered trademark of PPG Co., Ltd.) and an ITO film containing indium tin oxide (In ₂ O ₃ -SnO ₂ ). Etc. can be used. The photoetching method and the method using a preliminary mask are used for patterning of these transparent conductive films. As the reflective electrode, a metal such as Al or Ag, an alloy containing these metals, or the like can be used. As long as it has sufficient reflectance, it is not limited to these. In the application of the liquid crystal aligning agent, a functional silane-containing compound, a functional titanium-containing compound, and the like are applied in advance to the surface of the substrate in order to further improve the adhesion between the substrate surface and the transparent conductive film, the reflective electrode and the coating film. It may be. 80-300 degreeC is preferable and, as for the heating temperature after apply | coating a liquid crystal aligning agent, 120-250 degreeC is more preferable. Although the liquid crystal aligning agent of this invention containing a polyamic acid forms the coating film used as an oriented film by removing an organic solvent after application | coating, it can also be made into a more imidized coating film by advancing dehydration ring closure by further heating. 0.001-1 micrometer is preferable and, as for the film thickness of the coating film formed, 0.005-0.5 micrometer is more preferable.

(2) As disclosed in Japanese Unexamined Patent Publication No. 2002-327058, the formed coating film surface is formed on the substrate using a photosensitive resin, and a vertical liquid crystal alignment film is formed thereon.

(3) As described above, two substrates on which a vertical liquid crystal alignment film was formed were prepared, two substrates were arranged to face each other through a gap (cell gap), and the peripheral portions of the two substrates were bonded together using a sealant, Liquid crystal is injected and filled into the cell gap partitioned by the substrate surface and the sealing agent to seal the injection hole to form a liquid crystal cell. Moreover, a liquid crystal display element is obtained by arrange | positioning a polarizing plate in the outer surface of a liquid crystal cell, ie, the transparent substrate side which comprises a liquid crystal cell.

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

Examples of the liquid crystal include nematic liquid crystals and smectic liquid crystals. Especially, a nematic type liquid crystal is preferable, For example, a siphonbase type liquid crystal, a subfamily clock liquid crystal, a biphenyl type liquid crystal, a phenyl cyclohexane type liquid crystal, 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, for these liquid crystals, for example, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonaate, cholesteryl carbonate and the like, and product names "C-15" and "CB-15" (manufactured by Merck) It is also possible to add and use a chiral agent sold as the above. Ferroelectric liquid crystals such as p-decyloxybenzylidene-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 which inserted the polarizing film called H film | membrane which absorbed iodine, and extended | stretched polyvinyl alcohol between the cellulose acetate protective films, or the polarizing plate containing H film itself is mentioned.

<Example>

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Transparency, voltage protection rate, voltage protection rate, and baking in Examples and Comparative Examples were evaluated by the following methods.

[Transparency]

A HITACHI U-2010 spectrophotometer (manufactured by Hitachi Seisakusho Co., Ltd.) was used as the measuring device. The liquid crystal aligning agent of this invention manufactured as mentioned above was applied to the quartz substrate of thickness 1.5mm using the spinner, and it dried at 180 degreeC for 1 hour, and formed the coating film of 800 mm of dry film thickness. The transmittance of the prepared coating film was measured. Transmittance measurements were taken at wavelengths of 700 nm, 600 nm, 500 nm, 450 nm, 400 nm, 350 nm and 300 nm. The case where the transmittance | permeability in a certain measurement wavelength is 90% or more was good, and the other case was judged as defect.

[Vertical orientation]

The liquid crystal display element at voltage OFF and AC 12V (peak-peak) was observed under cross nicol.

[Sobe]

A 30 Hz, 2.0 V square wave superimposed on a liquid crystal display device with a direct current of 1.0 V is applied at an environmental temperature of 50 ° C. for 1 hour, and the voltage remaining in the liquid crystal cell immediately after the DC voltage is cut off is retained by the flicker elimination method. It calculated | required as voltage. The case where the value of residual DC was 2 V or less irrespective of the electrode type which comprises a liquid crystal display element, and the difference of residual DC between each electrode type is 0.5 V or less was good, and the other case was called defect.

[Reliability Test (Presence or Absence of Display Defects) of Liquid Crystal Display Element]

The liquid crystal display element was driven by the square wave of 5 V and 60 Hz in a high temperature, high humidity environment (temperature 70 degreeC, 80% relative humidity), and the presence or absence of a display defect was observed with the polarization microscope 100 hours later.

Synthesis Example 1

2,3,5-tricarboxycyclopentylacetic dianhydride 224.17 g (1.0 mol) as a tetracarboxylic dianhydride, 54.07 g (0.5 mol) p-phenylenediamine as a diamine compound, represented by the said General formula (16) 261.41 g (0.5 mol) of diamine compounds were dissolved in 4,500 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours. Subsequently, the reaction solution was placed in a large excess of methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 ° C. for 15 hours under reduced pressure to obtain 520 g of polyamic acid having a logarithmic viscosity of 0.57 dl / g (this is referred to as "polyamic acid (A-1)").

Synthesis Example 2

In Synthesis Example 1, the same number as in Synthesis Example 1 was obtained except that 94.62 g (0.8 mol) of p-phenylenediamine and 104.56 g (0.2 mol) of the diamine compound represented by the formula (16) were used as the diamine compound. 390 g of polyamic acid having a viscosity of 0.46 dl / g were obtained. 30 g of the obtained polyamic acid was dissolved in 570 g of N-methyl-2-pyrrolidone, 5.7 g of pyridine and 7.4 g of acetic anhydride were added to dehydrate and ring-close at 110 DEG C for 4 hours, and precipitated, washed and decompressed as described above. 19.5 g of polyimides having a logarithmic viscosity of 0.53 dl / g were referred to as "polyimide (A-2)".

Synthesis Example 3

In Synthesis Example 2, the same number as in Synthesis Example 2 was obtained except that 64.88 g (0.6 mol) of p-phenylenediamine and 209.13 g (0.4 mol) of the diamine compound represented by the formula (16) were used as the diamine compound. 450 g of polyamic acid having a viscosity of 0.33 dl / g was obtained. Thereafter, except that 4.8 g of pyridine and 6.1 g of acetic anhydride were used, 20.1 g of a polyimide having a logarithmic viscosity of 0.41 dl / g (this was called "polyimide (A-3)") was obtained in the same manner as in Synthesis example 2. .

Synthesis Example 4

In Synthesis Example 2, 75.70 g (0.7 mol) of p-phenylenediamine, 39.65 g (0.2 mol) of 1,1-bis (4-aminophenyl) methane, and the diamine compound represented by the general formula (16) as the diamine compound Except having used 52.28 g (0.1 mol), it carried out similarly to the synthesis example 2, and obtained 363 g of polyamic acids with a logarithmic viscosity of 0.39 dl / g. Thereafter, except that 12.1 g of pyridine and 15.6 g of acetic anhydride were used, 24.3 g of a polyimide having a logarithmic viscosity of 0.50 dl / g (this is called "polyimide (A-4)") was used in the same manner as in Synthesis Example 2. Got it.

Synthesis Example 5

In Synthesis Example 4, the logarithmic viscosity was 0.42 dl / g in the same manner as in Synthesis Example 4, except that 37.66 g (0.1 mol) of 2,4-diamino-1-octadecyloxybenzene was used instead of the diamine compound (16). 24.3 g of a polyimide (which is referred to as "polyimide (A-5)) was obtained.

Synthesis Example 6

Synthesis Example 4 was the same as in Synthesis Example 4 except that 36.65 g (0.1 mol) of 4- (4-n-heptylcyclohexyl) phenoxy-2,4-diaminobenzene was used instead of the diamine compound (16). 24.0 g of polyimides having a logarithmic viscosity of 0.49 dl / g were referred to as "polyimide (A-6)".

Synthesis Example 7

In Synthesis Example 1, tetracarboxylic dianhydride was used as 109.06 g (0.5 mol) of pyromellitic dianhydride and 98.06 g (0.5 mol) of cyclobutanetetracarboxylic dianhydride, and the diamine compound was 4,4'-dia. Except having made 198.27 g (1.0 mol) of minodiphenylmethanes, it carried out similarly to the synthesis example 1, and obtained 401 g of polyamic acids (this is called "polyamic acid (B-1)") with a logarithmic viscosity of 0.95 dl / g.

Synthesis Example 8

In Synthesis Example 7, a polyamic acid having a logarithmic viscosity of 0.81 dl / g was obtained in the same manner as in Synthesis Example 7, except that the diamine compound was 200.5 g (1.01 mol) of 4,4'-diaminodiphenylmethane. 410 g of a polyamic acid (B-2) "was obtained.

Synthesis Example 9

In Synthesis Example 2, an imide prepolymer was synthesized in the same manner as in Synthesis Example 2, except that 85.43 g (0.79 mol) of p-phenylenediamine was used, and the solid content was dissolved in N-methyl-2-pyrrolidone. It was set as the solution of 10 weight% of concentration. In addition, the polyamic acid (B-2) obtained by the said synthesis example 8 was used as an amic acid prepolymer, it was melt | dissolved in N-methyl- 2-pyrrolidone similarly, and it was set as the solution of 10 weight% of solid content concentration. Subsequently, 500 g of the imide prepolymer solution and 500 g of the amic acid prepolymer were mixed and stirred for 2 hours, and then the reaction solution was placed in a large excess of methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 ° C. for 15 hours under reduced pressure to obtain 99 g of a partially imidized polymer having a logarithmic viscosity of 0.67 dl / g (this is referred to as "polymer (C-1)").

Synthesis Example 10

In Synthesis Example 3, an imide prepolymer was synthesized in the same manner as in Synthesis Example 3, except that 63.80 g (0.59 mol) of p-phenylenediamine was used. 98 g of dl / g partially imidized polymer (this is referred to as "polymer (C-2)") were obtained.

Synthesis Example 11

In Synthesis Example 4, except that 74.62 g (0.69 mol) of p-phenylenediamine was used, the imide prepolymer was synthesized in the same manner as in Synthesis Example 4, and then, in the same manner as in Synthesis Example 9, the logarithmic viscosity was 0.72 kPa 99 g of a / g partially imidized polymer (this is called "polymer (C-3)") was obtained.

Example 1

Polyamic acid (A-1) obtained in Synthesis Example 1 was dissolved in an N-methyl-2-pyrrolidone / γ-butyrolactone mixed solvent (weight ratio 30/70), and polyethylene glycol diglycidyl ether (molecular weight approx. 10 parts by weight of 400) was dissolved in 100 parts by weight of a polymer to prepare a solution having a solid content of 4% by weight, and after sufficiently stirring, the solution was filtered using a filter having a pore diameter of 1 µm to prepare a liquid crystal aligning agent of the present invention. It was. The liquid crystal aligning agent was applied using a spinner on a transparent conductive film including an ITO film provided on one side of a glass substrate having a thickness of 1 mm and a reflecting film containing Al, and dried at 200 ° C. for 1 hour to dry film thickness. A film of 0.08 mu m was formed. Subsequently, an epoxy resin adhesive containing an aluminum oxide sphere having a diameter of 5.5 µm was placed on each outer edge having a pair of transparent electrodes / transparent electrode substrates and a liquid crystal alignment film of the liquid crystal alignment film-coated substrate of the pair of transparent electrodes / reflective electrode substrates. After apply | coating, the liquid crystal aligning film surface was overlapped so that it might be crimped | bonded and hardened the adhesive agent. Subsequently, after filling a negative type liquid crystal (MLC-6608, Merck Co., Ltd.) between a liquid crystal injection hole and a board | substrate, the liquid crystal injection hole is sealed with acrylic photocuring adhesive agent, a polarizing plate is bonded to both surfaces of the outer side of a board | substrate, and a liquid crystal display element is Prepared. The baking and reliability of the obtained liquid crystal display element were evaluated. The liquid crystal aligning agent of this invention manufactured as mentioned above was apply | coated using the spinner on the quartz substrate of thickness 1.5mm, and the coating film was formed like the liquid crystal display element manufacture. Transparency was evaluated from the measurement of the transmittance of the prepared coating film. The results are shown in Table 2 below. It was confirmed that the liquid crystal aligning agent obtained in the present invention has good baking and reliability.

Examples 2-30

Polyimides (A-2) to (A-6), polyamic acids (B-1) to (B-2), and partially imidized polymers obtained in Synthesis Examples 2 to 7 according to the formulations shown in Tables 1 and 2 below. (C-1) to (C-3), an epoxy group-containing compound, and a silane coupling agent were dissolved in a mixed solvent containing γ-butyrolactone as a main component to obtain a solution having a solid content concentration of 4.0%, and the solution was 1 μm in diameter. The liquid crystal aligning agent of this invention was adjusted by filtering with the filter of. Thus, the coating film was formed on the board | substrate surface similarly to Example 1 using each of the adjusted liquid crystal aligning agent, and the liquid crystal display element was manufactured using the board | substrate with which the said liquid crystal aligning film was formed. In addition, transparency, baking characteristics and reliability were evaluated. The results are shown in Table 2 below.

Comparative Examples 1 to 5

According to the prescription shown in Tables 1 and 2, the liquid crystal display device was manufactured in the same manner as in the example. In addition, transparency, voltage retention and baking characteristics were evaluated. The results are shown in Table 2.

polymer Polymer mixing ratio Epoxy Group-Containing Compound Kinds Amount Example 1 A-1 Polyethylene Glycol Diglycidyl Ether 10 Example 2 A-1 Polyethylene Glycol Diglycidyl Ether 20 Example 3 A-1 Polyethylene Glycol Diglycidyl Ether 30 Example 4 A-2 Polyethylene Glycol Diglycidyl Ether 10 Example 5 A-3 Polyethylene Glycol Diglycidyl Ether 10 Example 6 A-4 Polyethylene Glycol Diglycidyl Ether 10 Example 7 A-5 Polyethylene Glycol Diglycidyl Ether 10 Example 8 A-6 Polyethylene Glycol Diglycidyl Ether 10 Example 9 A-4 B-1 50/50 Polyethylene Glycol Diglycidyl Ether 20 Example 10 A-4 B-1 40/60 Polyethylene Glycol Diglycidyl Ether 20 Example 11 A-4 B-1 60/40 Polyethylene Glycol Diglycidyl Ether 20 Example 12 A-4 B-1 50/50 Polyethylene Glycol Diglycidyl Ether 20 Example 13 A-4 B-1 50/50 Polyethylene Glycol Diglycidyl Ether 20 Example 14 A-4 B-1 50/50 Polyethylene Glycol Diglycidyl Ether 20 Example 15 A-4 B-1 50/50 Polyethylene Glycol Diglycidyl Ether 20 Example 16 A-4 B-1 50/50 Polyethylene Glycol Diglycidyl Ether 20 Example 17 A-4 B-1 50/50 Polyethylene Glycol Diglycidyl Ether 20 Example 18 A-4 B-1 50/50 Polyethylene Glycol Diglycidyl Ether 20 Example 19 A-4 B-1 50/50 1,3,5,6-tetraglycidyl-2,4-hexanediol 10 Example 20 A-4 B-1 50/50 1,3,5,6-tetraglycidyl-2,4-hexanediol 10 Example 21 A-4 B-1 50/50 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane 10 Example 22 A-4 B-1 50/50 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane 10 Example 23 A-4 B-1 50/50 N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane 20 Example 24 A-4 B-1 50/50 Polyethylene Glycol Diglycidyl Ether 5 Example 25 A-4 B-1 50/50 N, N, N ', N'-tetraglycidyl-m-xylylenediamine 5 Example 26 A-4 B-1 50/50 Polyethylene Glycol Diglycidyl Ether 20 Example 27 A-4 B-1 50/50 Ethylene Glycol Diglycidyl Ether 20 Example 28 C-1 Polyethylene Glycol Diglycidyl Ether 20 Example 29 C-2 Ethylene Glycol Diglycidyl Ether 20 Example 30 C-3 N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane 20 Comparative Example 1 A-1 - 10 Comparative Example 2 A-2 - 10 Comparative Example 3 A-2 B-1 50/50 - 10 Comparative Example 3 B-3 - 10 Comparative Example 4 C-1 - 10 Comparative Example 5 C-3 - 10

The addition amount of an epoxy group containing compound is a weight amount per 100 weight part of polymers.

Silane coupling agent Transparency Vertical orientation Sobu responsibility Kinds Amount Transmissive Reflective Transmissive Reflective Transmissive Reflective Example 1 - - Good Good Good Good Good Good Good Example 2 - - Good Good Good Good Good Good Good Example 3 - - Good Good Good Good Good Good Good Example 4 - - Good Good Good Good Good Good Good Example 5 - - Good Good Good Good Good Good Good Example 6 - - Good Good Good Good Good Good Good Example 7 - - Good Good Good Good Good Good Good Example 8 - - Good Good Good Good Good Good Good Example 9 - - Good Good Good Good Good Good Good Example 10 - - Good Good Good Good Good Good Good Example 11 - - Good Good Good Good Good Good Good Example 12 - - Good Good Good Good Good Good Good Example 13 - - Good Good Good Good Good Good Good Example 14 - - Good Good Good Good Good Good Good Example 15 3-glycidoxypropyltrimethoxysilane 2 Good Good Good Good Good Good Good Example 16 3-glycidoxypropyltrimethoxysilane 5 Good Good Good Good Good Good Good Example 17 3-glycidoxypropyltrimethoxysilane 15 Good Good Good Good Good Good Good Example 18 3-ureidopropyltrimethoxysilane 5 Good Good Good Good Good Good Good Example 19 - - Good Good Good Good Good Good Good Example 20 - - Good Good Good Good Good Good Good Example 21 - - Good Good Good Good Good Good Good Example 22 - - Good Good Good Good Good Good Good Example 23 - - Good Good Good Good Good Good Good Example 24 - - Good Good Good Good Good Good Good Example 25 - - Good Good Good Good Good Good Good Example 26 - - Good Good Good Good Good Good Good Example 27 - - Good Good Good Good Good Good Good Example 28 - - Good Good Good Good Good Good Good Example 29 - - Good Good Good Good Good Good Good Example 30 - - Good Good Good Good Good Good Good Comparative Example 1 - - Good Good Good Good Bad Good Bad Comparative Example 2 - - Good Good Good Good Bad Good Bad Comparative Example 3 - - Good Good Good Good Bad Good Bad Comparative Example 3 - - Good Good Good Good Bad Good Bad Comparative Example 4 - - Good Good Good Good Bad Good Bad Comparative Example 5 - - Good Good Good Good Bad Good Bad

The addition amount of a silane coupling agent is a weight amount per 100 weight part of polymers.

The vertical liquid crystal aligning film formed by the liquid crystal aligning agent of this invention is not limited to the case where it is used with an ITO electrode, and when used together with a reflection electrode, it is excellent in baking characteristic and reliability, and comprises a liquid crystal display element. Can be preferably used.

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

Claims (4)

A vertical component comprising 100 parts by weight of a polymer having a repeating unit represented by the following formula (1) and / or a repeating unit represented by the following formula (2), and 5 parts by weight or more of a compound having two or more epoxy groups in the molecule: Liquid crystal aligning agent. <Formula 1>

In the above formula, P ¹ is a tetravalent organic group, and Q ¹ is a divalent organic group. <Formula 2>

In the above formula, P ² is a tetravalent organic group, and Q ² is a divalent organic group. The vertical liquid crystal aligning agent according to claim 1, wherein the compound having two or more epoxy groups in the molecule is at least one epoxy-containing compound selected from the group consisting of a compound represented by the following formula (3) and a compound represented by the following formula (4). <Formula 3>

In the formula, R ⁰¹ represents a divalent aliphatic group. <Formula 4>

In the formula, R ⁰² represents a divalent organic group. The vertical liquid crystal aligning agent of Claim 1 or 2 whose transmittance | permeability in the wavelength range of 300 nm-700 nm of a polymer is 90% or more. It provided with the liquid crystal aligning film formed from the vertical liquid crystal aligning agent in any one of Claims 1-3, The vertical liquid crystal display element which has a reflection electrode characterized by the above-mentioned.