JP4793536B2 - Liquid crystal aligning agent and liquid crystal display element - Google Patents

Description

  The present invention relates to a liquid crystal aligning agent and a liquid crystal display element. More specifically, the present invention relates to a liquid crystal aligning agent excellent in printability and a liquid crystal display element obtained therefrom.

  Currently, as a liquid crystal display element, a liquid crystal alignment film is formed on the surface of a substrate provided with a transparent conductive film to form a substrate for a liquid crystal display element. A so-called TN type (a long axis of liquid crystal molecules is continuously twisted by 90 degrees from one substrate to the other substrate by forming a layer of a nematic liquid crystal having a directivity to form a sandwich cell. A TN type liquid crystal display element having a twisted liquid crystal cell is known. Further, by using a liquid crystal to which a chiral agent which is an optically active substance is added, a state in which the long axis of liquid crystal molecules is continuously twisted over 180 degrees between substrates is achieved, and STN utilizing the birefringence effect generated thereby. A (Super Twisted Nematic) type liquid crystal display element is also known. Furthermore, an IPS (In-Plane Switching) type liquid crystal display element and a vertical alignment type liquid crystal display element, which have less viewing angle dependency than a TN type liquid crystal display element, have been developed.

  Conventionally known materials for the liquid crystal alignment film in these liquid crystal display elements include polyimide, polyamide, and polyester. In particular, polyimide is excellent in heat resistance, affinity with liquid crystals, mechanical strength, and the like, and is used in many liquid crystal display elements. A liquid crystal alignment film made of polyimide is usually obtained by applying a polyamic acid as a polyimide precursor or a liquid crystal alignment agent as an organic solvent solution of a soluble polyimide onto a substrate and imidizing by heating. In the liquid crystal aligning agent, a surfactant may be added for the purpose of improving the leveling property with respect to the substrate.

However, although the liquid crystal aligning agent to which the surfactant is added improves the leveling property with respect to the substrate, there is a problem that the alignment property of the liquid crystal, the electrical characteristics and reliability of the obtained liquid crystal display element are lowered. Patent Document 1 discloses a liquid crystal aligning agent using a Si-based surfactant, but this liquid crystal aligning agent has no problem in the initial alignment and electrical characteristics, but a decrease in reliability remains as a problem. It had been.
JP 2003-49069 A

  An object of the present invention is to provide a liquid crystal aligning agent having good alignment properties, electrical characteristics, reliability and alignment film coating properties of a liquid crystal display element.

  Another object of the present invention is to provide a liquid crystal display device provided with a liquid crystal alignment film obtained from the liquid crystal alignment agent.

  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 as follows. First, (A) a repeating unit represented by the following formula (I-1) and a repeating unit represented by the following formula (I-2): A polymer having at least one repeating unit selected from the group, and (B) a fluorine-containing compound having a plurality of OR (R is an alkylene group) bond in the molecule , provided that the fluorine-containing compound has the following formula (II- 1), at least one compound selected from the group consisting of compounds having the structural formulas represented by each of (II-2) and (II-3), Achieved by the agent.

（式中、Ｐ¹ は４価の有機基でありそしてＱ¹ は２価の有機基である。）

(Wherein P ¹ is a tetravalent organic group and Q ¹ is a divalent organic group.)

（式中、Ｐ² は４価の有機基でありそしてＱ² は２価の有機基である。）

（上記式中、Ｒ ^１ はＣ _２ Ｈ _４ Ｏであり、Ｒ ^２ はＣ _３ Ｈ _６ Ｏであり、Ｒ ^３ はＳＯ _２ Ｎ（Ｅ）であり、Ｅは水素原子または炭素数１〜５のアルキル基であり、Ａは水素原子または炭素数１〜３のアルキル基であり、ｘおよびｙは相互に独立に１〜１０，０００の数であり、ｉ、ｊおよびｋは相互に独立に１〜１０の数であり、ｎは１〜１０の数である。）
本発明によれば、本発明の上記目的および利点は、第２に、本発明の上記液晶配向剤から得られた液晶配向膜を備えた液晶表示素子によって達成される。

(Wherein P ² is a tetravalent organic group and Q ² is a divalent organic group.)

(In the above formula, R ¹ is C ₂ H ₄ O, R ² is C ₃ H ₆ O, R ³ is SO ₂ N (E), and E is a hydrogen atom or having 1 to 5 carbon atoms. An alkyl group, A is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, x and y are independently 1 to 10,000, and i, j and k are 1 independently of each other. -10, and n is a number from 1 to 10.)
According to the present invention, the above objects and advantages of the present invention are secondly achieved by a liquid crystal display device comprising a liquid crystal alignment film obtained from the above liquid crystal aligning agent of the present invention.

According to the liquid crystal aligning agent of the present invention, it is possible to produce a liquid crystal aligning film having good printability without print unevenness and pinholes when printed on a substrate.
The liquid crystal display element of the present invention can be suitably used for TN type and STN type liquid crystal display elements, and by selecting the liquid crystal to be used, it is possible to select SH (Super Homeotropic) type, IPS (In-Plane Switching) type, strong It can also be suitably used for dielectric and antiferroelectric liquid crystal display elements.
Furthermore, the liquid crystal display element of the present invention can be used effectively in various devices, and is used in display devices such as a desk calculator, a wristwatch, a table clock, a counting display board, a word processor, a personal computer, and a liquid crystal television.

Hereinafter, the present invention will be described in detail.
(A) Polymer The polymer used in the present invention comprises at least one repeating unit selected from the repeating unit represented by the above formula (I-1) and the repeating unit represented by the above formula (I-2). Have. Examples of such a polymer include a polyamic acid composed of a repeating unit represented by the above formula (I-1) and a repeating unit represented by the above formula (I-2) obtained by dehydrating and ring-closing (imidizing) the polyamic acid. Or the imidation polymer which has both the repeating unit represented by each of said formula (I-1) and (I-2) is mentioned. The “imidized polymer” in the present invention includes those in which all of the repeating units are imidized and those that are partially imidized. Further, a part of the imide ring may be an isoimide ring.

A preferred polymer in the present invention is a polymer having both the repeating unit represented by the above formula (I-1) and the repeating unit represented by the above formula (I-2). Examples of the liquid crystal aligning agent having such a polymer include the following liquid crystal aligning agents (1) to (3).
(1) A liquid crystal aligning agent containing both a polyamic acid and an imidized polymer.
(2) A liquid crystal aligning agent containing a block copolymer of a prepolymer having an amic acid structure and a prepolymer having an imide structure.
(3) A liquid crystal aligning agent containing an imidized polymer obtained by partially dehydrating and ring-closing polyamic acid.
Of these, (1) and (2) are preferable, and (1) is particularly preferable.

Polyamic acid The polyamic acid used in the present invention is obtained by reacting a tetracarboxylic dianhydride and a diamine.

[Tetracarboxylic dianhydride]
Examples of the tetracarboxylic dianhydride used for the synthesis of the polyamic acid include butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, and 1,2-dimethyl-1. , 2,3,4-Cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4 -Cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid bis Anhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ′, 4,4′-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride 3,5,6-tricarbo Sinorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo- 3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5 (tetrahydro-2,5-dioxo- 3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-ethyl-5 (tetrahydro-2,5-dioxo- 3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-methyl-5 (tetrahydro-2,5-dioxo- 3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b- Xahydro-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-dioxotetrahydrofura ) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2.2. 2] -Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, aliphatic and alicyclic tetracarboxylic acids such as compounds represented by the following formulas (III) and (IV) Anhydride;

（式中、Ｒ^４ およびＲ^７ は、芳香環を有する２価の有機基を示し、Ｒ^５ およびＲ^６ は、水素原子またはアルキル基を示し、複数存在するＲ^５ およびＲ^６ は、それぞれ同一でも異なっていてもよい。）

(Wherein R ⁴ and R ⁷ represent a divalent organic group having an aromatic ring, R ⁵ and R ⁶ represent a hydrogen atom or an alkyl group, and a plurality of R ⁵ and R ⁶ are the same. But it may be different.)

Pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic dianhydride, 1,4,5, 8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ', 4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis ( 3,4-dicarboxyphenoxy) diph Nylpropane dianhydride, 3,3 ′, 4,4′-perfluoroisopropylidene diphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenyl Phosphine 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), 1,4- Butanediol-bis (anhydrotrimellitate), 1,6-hexanediol-bis (anhydrotrimellitate), 1,8-o Kutandiol-bis (anhydrotrimellitate), 2,2-bis (4-hydroxyphenyl) propane-bis (anhydrotrimellitate), compounds represented by the following formulas (1) to (4), etc. And aromatic tetracarboxylic dianhydrides. These may be used alone or in combination of two or more.

  Of these, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid 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-hex Hydro-5,8-dimethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, bicyclo [2.2.2] -oct -7-ene-2,3,5,6-tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, Among the compounds represented by the formula (III), 4,4′-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, the following formulas (5) to (7 Among the compounds represented by formula (IV) and the compound represented by formula (IV) above, the compound represented by formula (8) below is preferable and particularly preferable from the viewpoint of exhibiting good liquid crystal alignment. 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3, -Tricarboxycyclopentyl acetic acid 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, pyromellitic dianhydride, and a compound represented by the following formula (5).

[Diamine]
Examples of the diamine used for the synthesis of the polyamic acid include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 4,4′-diaminodiphenyl sulfide, 4 4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2 '-Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 3,3'-ditri Fluoromethyl-4,4′-diaminobiphenyl, 5-amino-1- (4′-aminophenyl) -1,3,3-trimethylindane, 6 Amino-1- (4′-aminophenyl) -1,3,3-trimethylindane, 3,4′-diaminodiphenyl ether, 3,3′-diaminobenzophenone, 3,4′-diaminobenzophenone, 4,4′- Diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-amino) Phenyl) hexafluoropropane, 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-diaminofluore 9,9-bis (4-aminophenyl) fluorene, 4,4′-methylene-bis (2-chloroaniline), 2,2 ′, 5,5′-tetrachloro-4,4′-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 1,4,4 '-(p-phenyleneisopropylidene ) Bisaniline, 4,4 ′-(m-phenyleneisopropylidene) bisaniline, 2,2′-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4′-diamino Aromatic diamines such as -2,2'-bis (trifluoromethyl) biphenyl, 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl;
p-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, diaminoheptamethylenediamine, 1,4-diaminocyclohexane, isophorone Diamine, Tetrahydrodicyclopentadienylenediamine, Hexahydro-4,7-methanoindanylene methylene diamine, Tricyclo [6.2.1.0 ^2,7 ] -Undecylenedimethyl diamine, 4,4'-methylene bis (cyclohexyl) Aliphatic and cycloaliphatic diamines such as amine);
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-diamino-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-phenylphenanthridine, 1,4-diaminopiperazine, 3, , 6-diaminoacridine, bis (4-aminophenyl) phenylamine, and two primary amino groups in the molecule, such as compounds represented by the following formulas (V) to (VI), and the primary amino group A diamine having a nitrogen atom other than

（式中、Ｒ^８ は、ピリジン、ピリミジン、トリアジン、ピペリジンおよびピペラジンから選ばれる窒素原子を含む環構造を有する１価の有機基を示し、Ｘは２価の有機基を示す。）

(Wherein R ⁸ 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.)

（式中、Ｘは、ピリジン、ピリミジン、トリアジン、ピペリジンおよびピペラジンから選ばれる窒素原子を含む環構造を有する２価の有機基を示し、Ｒ^９は２価の有機基を示し、複数存在するＸは、同一でも異なっていてもよい。）

(Wherein X represents a divalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine, R ⁹ represents a divalent organic group, and a plurality of X May be the same or different.)

Mono-substituted phenylenediamines represented by the following formula (VII); diaminoorganosiloxanes represented by the following formula (VIII);

（式中、Ｒ^１０ は、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−、−ＣＯＮＨ−および−ＣＯ−から選ばれる２価の有機基を示し、Ｒ^１１ は、ステロイド骨格、トリフルオロメチル基およびフルオロ基から選ばれる基を有する１価の有機基または炭素数６〜３０のアルキル基を示す。）

(Wherein R ¹⁰ represents a divalent organic group selected from —O—, —COO—, —OCO—, —NHCO—, —CONH— and —CO—, and R ¹¹ represents a steroid skeleton, A monovalent organic group having a group selected from a fluoromethyl group and a fluoro group or an alkyl group having 6 to 30 carbon atoms is shown.)

（式中、Ｒ^１２ は炭素数１〜１２の炭化水素基を示し、複数存在するＲ^１２ は、それぞれ同一でも異なっていてもよく、ｐは１〜３の整数であり、ｑは１〜２０の整数である。）

(Wherein R ¹² represents a hydrocarbon group having 1 to ¹² carbon atoms, and a plurality of R ¹² may be the same or different, p is an integer of 1 to 3, and q is 1 to 20) Is an integer.)

Examples include compounds represented by the following formulas (9) to (13). These diamines can be used alone or in combination of two or more.

（式中、ｙは２〜１２の整数であり、ｚは１〜５の整数である。）

(In the formula, y is an integer of 2 to 12, and z is an integer of 1 to 5.)

  Of these, p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2, 2′-ditrifluoromethyl-4,4′-diaminobiphenyl, 2,7-diaminofluorene, 4,4′-diaminodiphenyl ether, 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, the above formula (9) to (13) each of the compounds represented by 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, the compound represented by the above formula (V) Of these, among the compounds represented by the following formula (14), the compounds represented by the following formula (15) and the compounds represented by the above formula (VII), dodecanoxy- 2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecanoxy-2,4-diaminobenzene, octadecanoxy-2,5-diaminobenzene, Decanoxy-2,5-diaminobenzene, pentadecanoxy-2,5-diaminobenzene, hexadecanoxy-2,5-diaminobenzene, octadecanoxy-2,5-diaminobenzene, each represented by the following formulas (16) to (21) Are preferred.

[Synthesis of polyamic acid]
The ratio of the tetracarboxylic dianhydride and the diamine compound used for the polyamic acid synthesis reaction is such that the acid anhydride group of the tetracarboxylic dianhydride is 0.1 relative to 1 equivalent of the amino group contained in the diamine compound. A ratio of 2 to 2 equivalents is preferable, and a ratio of 0.3 to 1.2 equivalents is more preferable.

  The synthetic reaction of polyamic acid is preferably carried out in an organic solvent under a temperature condition of -20 to 150 ° C, more preferably 0 to 100 ° C. Here, the organic solvent is not particularly limited as long as it can dissolve the synthesized polyamic acid. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide And aprotic polar solvents such as γ-butyrolactone, tetramethylurea and hexamethylphosphortriamide; and phenolic solvents such as m-cresol, xylenol, phenol and halogenated phenol. The amount of organic solvent used (a) is, for example, such that the total amount (b) of tetracarboxylic dianhydride and diamine compound is 0.1 to 30% by weight with respect to the total amount (a + b) of the reaction solution. It is preferable that the amount is small.

  For the organic solvent, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, etc., which are poor solvents for polyamic acid, are used in combination as long as the polyamic acid to be produced does not precipitate. be able to. Specific examples of the poor solvent include, for example, 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 methoxypropionate, ethyl ethoxypropionate, 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- Chill ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1 , 4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene and the like.

  As described above, a reaction solution obtained by dissolving polyamic acid is obtained. The reaction solution is poured into a large amount of poor solvent to obtain a precipitate, and the precipitate is dried under reduced pressure to obtain a polyamic acid. 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.

Imidized Polymer The imidized polymer used in the present invention is obtained by dehydrating and ring-closing a polyamic acid obtained by reacting tetracarboxylic dianhydride and diamine.

[Tetracarboxylic dianhydride]
Examples of the tetracarboxylic dianhydride used for the synthesis of the imidized polymer include the same tetracarboxylic dianhydrides used for the synthesis of the polyamic acid described above.

  As the tetracarboxylic dianhydride used for the synthesis of the imidized polymer of the present invention, an alicyclic tetracarboxylic dianhydride is preferable. As a particularly preferred specific example, 2,3,5-tricarboxycyclopentylacetic acid 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. Moreover, you may use together alicyclic tetracarboxylic dianhydride and another tetracarboxylic dianhydride.

[Diamine]
Examples of the diamine used for the synthesis of the imidized polymer include the same diamines used for the synthesis of the polyamic acid described above.

  As the diamine used for the synthesis of the imidized polymer of the present invention, a diamine represented by the formula (VII) is preferable. Preferred examples include dodecanoxy-2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecanoxy-2,4-diaminobenzene, octadecanoxy-2, among the compounds represented by the formula (VII). 5-diaminobenzene, dodecanoxy-2,5-diaminobenzene, pentadecanoxy-2,5-diaminobenzene, hexadecanoxy-2,5-diaminobenzene, octadecanoxy-2,5-diaminobenzene, the above formulas (16) to (21) The compound represented by these is mentioned.

  In the imidized polymer of the present invention, the diamine represented by the above formula (VII) and other diamines may be used in combination. Among the other diamines, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4 ' -Diaminobiphenyl, 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 2,7-diaminofluorene, 4,4'-diaminodiphenyl ether, 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) hexafluoro Propane, 4,4 '-(p-phenylenediisopropylidene) bisaniline, 4,4'-(m-phenylenediiso Propylidene) bisaniline, 1,4-cyclohexanediamine, 4,4′-methylenebis (cyclohexylamine), 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, above Compounds represented by formulas (9) to (13), 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, represented by the above formula (V) Among the compounds represented by formula (14), and the compound represented by formula (15) among the compounds represented by formula (VI).

  In the imidized polymer of the present invention, the diamine represented by the above formula (VII) is preferably used in an amount of 0.5% by weight or more, particularly preferably 1% by weight or more of the total diamine.

[Synthesis of imidized polymer]
The imidized polymer constituting the liquid crystal aligning agent of the present invention can be obtained by dehydrating and ring-closing polyamic acid. The dehydration ring closure of the polyamic acid is preferably carried out by (i) a method of heating the polyamic acid, or (ii) dissolving the polyamic acid in an organic solvent, and adding a dehydrating agent and a dehydration ring closure catalyst to this solution as necessary. This is done by heating.

  The reaction temperature in the method of heating the polyamic acid (i) is preferably 50 to 200 ° C, more preferably 60 to 170 ° C. When the reaction temperature is less than 50 ° C., the dehydration ring-closing reaction does not proceed sufficiently, and when the reaction temperature exceeds 200 ° C., the molecular weight of the imidized polymer obtained may decrease.

  On the other hand, in the above method (ii) of adding a dehydrating agent and a dehydrating ring-closing catalyst to the polyamic acid solution, as the dehydrating agent, for example, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride is used. Can do. The amount of the dehydrating agent used is preferably 0.01 to 20 mol with respect to 1 mol of the polyamic acid repeating unit. Moreover, as a dehydration ring closure catalyst, tertiary amines, such as a pyridine, a collidine, a lutidine, a triethylamine, can be used, for example. However, it is not limited to these. The amount of the dehydration ring closure catalyst used is preferably 0.01 to 10 moles per mole of the dehydrating agent used. In addition, as an organic solvent used for dehydration ring closure reaction, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid can be mentioned. And reaction temperature of dehydration ring closure reaction becomes like this. Preferably it is 0-180 degreeC, More preferably, it is 10-150 degreeC. In addition, the imidized polymer can be purified by performing the same operation as the polyamic acid purification method on the reaction solution thus obtained.

  The imidized polymer used in the present invention may be partially dehydrated and closed and have a low imidization rate. The preferred imidization rate in the imidized polymer used in the present invention is 80% or more, more preferably 85% or more. Here, the “imidation ratio” is the percentage of the number of repeating units that form an imide ring with respect to the total number of repeating units in the polymer. At this time, an imide ring is used in the meaning including an isoimide ring.

Terminal-modified polymer The polyamic acid and imidized polymer may be of a terminal-modified type whose molecular weight is adjusted. Such a terminal-modified type can be synthesized, for example, by adding an acid monoanhydride, a monoamine compound, a monoisocyanate compound or the like to the reaction system when synthesizing the polyamic acid. Here, as the acid monoanhydride, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride , N-hexadecyl succinic anhydride and the like. Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, and n-undecyl. Amine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-eicosylamine, etc. be able to. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

The polyamic acid and imidized polymer obtained as described above have a logarithmic viscosity (η _ln ) of preferably 0.05 to 10 dl / g, more preferably 0.05 to 5 dl. / G.

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

(B) fluorine-containing compound a fluorine-containing compound used in the present invention, a plurality of OR (R is an alkylene group) in the molecule is a full-Oro carbon acrylate copolymers that have a binding.

The fluorine-containing compound, under Symbol formula (II-1), Ru compound der having a structure represented by each of (II-2) and (II-3).

（上記式中、Ｒ^１はＣ_２Ｈ_４Ｏであり、Ｒ^２はＣ_３Ｈ_６Ｏであり、Ｒ^３はＳＯ_２Ｎ（Ｅ）であり、Ｅは水素原子または炭素数１〜５のアルキル基であり、Ａは水素原子または炭素数１〜３のアルキル基であり、ｘおよびｙは相互に独立に１〜１０，０００の数であり、ｉ、ｊおよびｋは相互に独立に１〜１０の数であり、nは１〜１０の数である。）
上記式においてＡで表される炭素数１〜３のアルキル基としては、例えばメチル基、エチル基、ｎ−プロピル基などを挙げることができる。

(In the above formula, R ¹ is C ₂ H ₄ O, R ² is C ₃ H ₆ O, R ³ is SO ₂ N (E), and E is a hydrogen atom or having 1 to 5 carbon atoms. An alkyl group, A is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, x and y are independently 1 to 10,000, and i, j and k are 1 independently of each other. 10 is a number, and n is a number from 1 to 10.)
Examples of the alkyl group having 1 to 3 carbon atoms represented by A in the above formula include a methyl group, an ethyl group, and an n-propyl group.

Moreover, as a C1-C5 alkyl group represented by E in the said Formula, a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group etc. can be mentioned, for example.
In the above formula, x and y are each independently a number of 1 to 10,000, preferably a number of 1 to 1,000. i, j and k are each independently a number of 1 to 10, and n is a number of 1 to 10.
These compounds can be used alone or in combination of two or more.

  The blending ratio of the (B) fluorine-containing compound in the liquid crystal aligning agent of the present invention is preferably 0.01 to 2 parts by weight, more preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the polymer (A). More preferably, it is 0.01 to 0.5 part by weight. If it is less than 0.01 part by weight, the effect of improving the printability may be insufficient, and if it exceeds 10 parts by weight, foaming may occur.

Liquid crystal aligning agent The liquid crystal aligning agent of the present invention is constituted by dissolving the above-mentioned (A) polymer and (B) fluorine-containing compound, preferably in an organic solvent.
The temperature at which the liquid crystal aligning agent of the present invention is prepared is preferably 0 ° C to 200 ° C, more preferably 20 ° C to 60 ° C.
As an organic solvent which comprises the liquid crystal aligning agent of this invention, the solvent illustrated as what is used for the synthesis reaction of a polyamic acid can be mentioned. Moreover, the poor solvent illustrated as what can be used together in the case of the synthesis reaction of a polyamic acid can also be selected suitably, and can be used together.

  The solid content concentration in the liquid crystal aligning agent of the present invention is selected in consideration of viscosity, volatility, etc., but is preferably in the range of 1 to 10% by weight. That is, the liquid crystal aligning agent of the present invention is applied to the substrate surface to form a coating film that becomes a liquid crystal alignment film. When the solid content concentration is less than 1% by weight, the coating film thickness is When the solid content concentration exceeds 10% by weight, it is difficult to obtain a good liquid crystal alignment film because the film thickness is excessive. The viscosity of the liquid crystal aligning agent increases and the coating properties tend to be inferior.

  The liquid crystal aligning agent of the present invention may contain an epoxy group-containing compound from the viewpoint of improving the adhesion to the substrate surface. Examples of the epoxy group-containing compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6 -Hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ', N '-Tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N', N'-tetraglycidyl-4 , And the like as preferred 4'-diaminodiphenylmethane. The blending ratio of these and the epoxy group-containing compound 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 of this invention can be manufactured, for example with the following method.
(1) The liquid crystal aligning agent of the present invention is preferably applied to one surface of a substrate provided with a patterned transparent conductive film, preferably by a printing method or the like, and then the coated surface is heated by heating the coated surface. Form. Here, as the substrate, for example, a glass such as float glass or soda glass; a transparent substrate made of a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, or polycarbonate can be used. As the transparent conductive film provided on one surface of the substrate, for example, a NESA film (registered trademark of PPG, USA) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ —SnO ₂ ), etc. Can be used. For patterning these transparent conductive films, a photo-etching method or a method using a mask in advance is used. When applying the liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a functional silane-containing compound, a functional titanium-containing compound, or the like is previously applied to the surface of the substrate. You can also The heating temperature after application of the liquid crystal aligning agent is, for example, 80 to 300 ° C, and preferably 120 to 250 ° C. In addition, the liquid crystal aligning agent of the present invention containing a polyamic acid forms a coating film that becomes an alignment film by removing the organic solvent after coating, but further proceeds with dehydration ring closure by further heating, and is further imidized. It can also be set as a coating film. The film thickness of the formed coating film is preferably 0.001-1 μm, more preferably 0.005-0.5 μm.

(2) A rubbing process is performed in which the formed coating film surface is rubbed in a certain direction with a roll wound with a cloth made of a fiber such as nylon, rayon, or cotton. Thereby, the orientation ability of a liquid crystal molecule is provided to a coating film, and it becomes a liquid crystal aligning film.

  Further, by partially irradiating the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention with ultraviolet rays as disclosed in, for example, JP-A-6-222366 and JP-A-6-281937. A resist film is partially formed on the surface of the liquid crystal alignment film that has been subjected to a treatment for changing the pretilt angle or a rubbing treatment as disclosed in JP-A-5-107544, which is different from the previous rubbing treatment. The visibility characteristics of the liquid crystal display element can be improved by removing the resist film after performing the rubbing treatment in the direction and changing the liquid crystal alignment ability of the liquid crystal alignment film.

(3) Two substrates on which the liquid crystal alignment film is formed as described above are manufactured, and the two substrates are separated by a gap (cell gap) so that the rubbing directions in the respective liquid crystal alignment films are orthogonal or antiparallel. ), And the periphery of the two substrates are bonded together using a sealant, and liquid crystal is injected and filled in the cell gap defined by the substrate surface and the sealant, and the injection hole is sealed. A liquid crystal cell is constructed. A polarizing plate is disposed on the outer surface of the liquid crystal cell, that is, on the other surface side of each substrate constituting the liquid crystal cell, and the polarization direction thereof coincides with or is orthogonal to the rubbing direction of the liquid crystal alignment film formed on one surface of the substrate. A liquid crystal display element is obtained by pasting together.

  Here, as the sealing agent, for example, an epoxy resin containing a curing agent and aluminum oxide spheres as a spacer can be used.

  Examples of the liquid crystal include a nematic liquid crystal and a smectic liquid crystal. Among them, nematic liquid crystal is preferable, for example, Schiff base liquid crystal, azoxy liquid crystal, biphenyl liquid crystal, phenyl cyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane. Type liquid crystal, cubane type liquid crystal and the like can be used. Further, for these liquid crystals, for example, cholesteric liquid crystals such as cholestyl chloride, cholesteryl nonate, cholesteryl carbonate, and chiral agents such as those sold under the trade names “C-15” and “CB-15” (manufactured by Merck). Etc. can also be used. Furthermore, a ferroelectric liquid crystal such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate can also be used.

  In addition, as a polarizing plate bonded to the outer surface of the liquid crystal cell, for example, a polarizing plate in which a polarizing film called an H film that absorbs iodine while sandwiching and stretching polyvinyl alcohol is sandwiched between cellulose acetate protective films or H A polarizing plate made of the film itself can be used.

Reliability was determined using a liquid crystal cell prepared for reliability after confirming whether or not display defects or stains occurred after continuous driving in a constant temperature bath at 60 ° C. for 48 hours.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

Synthesis example 1
As tetracarboxylic dianhydride, pyromellitic dianhydride 109.06 g (0.5 mol) and 1,2,3,4-cyclobutanetetracarboxylic dianhydride 98.06 g (0.5 mol), diamine compound As a solution, 200.2 g (1.0 mol) of 4,4-diaminodiphenyl ether was dissolved in 4500 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, it was washed with methyl alcohol and dried at 40 ° C. under reduced pressure for 15 hours to obtain a polyamic acid having a logarithmic viscosity of 0.88 dl / g and an imidization ratio of 0% (this is referred to as “polyamic acid (A-1)”). ) 290 g was obtained.

Synthesis example 2
As tetracarboxylic dianhydride, pyromellitic dianhydride 109.06 g (0.5 mol) and 1,2,3,4-cyclobutanetetracarboxylic dianhydride 98.06 g (0.5 mol), diamine compound Was dissolved in 4500 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, it is washed with methyl alcohol and dried at 40 ° C. under reduced pressure for 15 hours to obtain a polyamic acid having a logarithmic viscosity of 0.92 dl / g and an imidization ratio of 0% (this is referred to as “polyamic acid (A-2)”). .) 310 g was obtained.

Synthesis example 3
196.12 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride, 200.2 g (1.0 mol) of 4,4′-diaminodiphenyl ether as diamine compound ) Was dissolved in 4500 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, it was washed with methyl alcohol and dried at 40 ° C. under reduced pressure for 15 hours to obtain a polyamic acid having a logarithmic viscosity of 0.90 dl / g and an imidization ratio of 0% (this is referred to as “polyamic acid (A-3)”). ) 290 g was obtained.

Synthesis example 4
196.12 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 212 g of 2,2′-dimethyl-4,4′-aminobiphenyl as diamine compound (1.0 mol) was dissolved in 4500 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, it is washed with methyl alcohol and dried at 40 ° C. under reduced pressure for 15 hours to give a polyamic acid having a logarithmic viscosity of 0.99 dl / g and an imidization ratio of 0% (this is referred to as “polyamic acid (A-4)”). ) 290 g was obtained.

Synthesis example 5
224.17 g (0.5 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 1,3,3a, 4,5,9b-hexahydro-5-methyl-5 ( Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione 157.14 g (0.5 mol), 94.62 g of p-phenylenediamine as a diamine compound ( 0.875 mol), 2,2-ditrifluoromethyl-4,4-diaminobiphenyl 32.02 g (0.1 mol), 3,6-bis (4-aminobenzoyloxy) cholestane (in the above formula (9)) 6.43 g (0.01 mol) and octadecanoxy-2,5-diaminobenzene 4.04 g (0.03 mol) were added to N-methyl-2-pyrrole. It was dissolved in 4500 g of Dong and reacted at 60 ° C. for 6 hours. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, it was washed with methyl alcohol and dried at 40 ° C. under reduced pressure for 15 hours to obtain 410 g of polyamic acid having a logarithmic viscosity of 0.87 dl / g and an imidization ratio of 0%. 30 g of the resulting polyamic acid was dissolved in 570 g of N-methyl-2-pyrrolidone, 23.4 g of pyridine and 18.1 g of acetic anhydride were added, and dehydration was carried out at 110 ° C. for 4 hours, followed by precipitation, washing, The pressure was reduced to obtain 17.5 g of an imidized polymer having a logarithmic viscosity of 0.80 dl / g and an imidization rate of 100% (hereinafter referred to as “imidized polymer (B-1)”).

Synthesis Example 6
224.17 g (0.5 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 1,3,3a, 4,5,9b-hexahydro-5-methyl-5 ( Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione 157.14 g (0.5 mol), 94.62 g of p-phenylenediamine as a diamine compound ( 0.875 mol), 24.85 g (0.1 mol) of bisaminopropyltetramethyldisiloxane, 6.43 g (0.01 mol) of 3,6-bis (4-aminobenzoyloxy) cholestane and octadecanoxy-2, 4.04 g (0.03 mol) of 5-diaminobenzene was dissolved in 4500 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, it was washed with methyl alcohol and dried at 40 ° C. under reduced pressure for 15 hours to obtain 370 g of polyamic acid having a logarithmic viscosity of 0.82 dl / g and an imidization ratio of 0%. 30 g of the resulting polyamic acid was dissolved in 570 g of N-methyl-2-pyrrolidone, 23.4 g of pyridine and 18.1 g of acetic anhydride were added, and dehydration was carried out at 110 ° C. for 4 hours, followed by precipitation, washing, Depressurization was performed to obtain 18.5 g of an imidized polymer having a logarithmic viscosity of 0.77 dl / g and an imidization ratio of 100% (hereinafter referred to as “imidized polymer (B-2)”).

Synthesis example 7
224.17 g (0.5 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 1,3,3a, 4,5,9b-hexahydro-5-methyl-5 ( Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione 157.14 g (0.5 mol), 89.21 g of p-phenylenediamine as a diamine compound ( 0.825 mol), 2,2′-ditrifluoromethyl-4,4′-diaminobiphenyl 32.02 g (0.1 mol), 1- (3,5-diaminobenzoyloxy) -4- (4-tri Fluoromethylbenzoyloxy) -cyclohexane (compound represented by the above formula (20), the same shall apply hereinafter) 25.34 g (0.06 mol) and octadecanoxy-2,5-diamino Benzene 4.04g (0.03 mol) was dissolved in N- methyl-2-pyrrolidone 4500 g, it was reacted for 6 hours at 60 ° C.. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, it was washed with methyl alcohol and dried at 40 ° C. under reduced pressure for 15 hours to obtain 410 g of polyamic acid having a logarithmic viscosity of 0.90 dl / g and an imidization ratio of 0%. 30 g of the resulting polyamic acid was dissolved in 570 g of N-methyl-2-pyrrolidone, 23.4 g of pyridine and 18.1 g of acetic anhydride were added, and dehydration was carried out at 110 ° C. for 4 hours, followed by precipitation, washing, Depressurization was performed to obtain 17.5 g of an imidized polymer having a logarithmic viscosity of 0.83 dl / g and an imidization ratio of 100% (hereinafter referred to as “imidized polymer (B-3)”).

Synthesis Example 8
224.17 g (0.5 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 1,3,3a, 4,5,9b-hexahydro-5-methyl-5 ( Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione 157.14 g (0.5 mol), p-phenylenediamine 94.08 g as a diamine compound ( 0.87 mol), 24.85 g (0.1 mol) of bisaminopropyltetramethyldisiloxane and 6.65 g (0.015 mol) of 3,6-bis (4-aminobenzoyloxy) cholestane, 2.79 g of aniline (0.03 mol) was dissolved in 4500 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, it was washed with methyl alcohol and dried at 40 ° C. under reduced pressure for 15 hours to obtain 350 g of polyamic acid having a logarithmic viscosity of 0.78 dl / g and an imidization ratio of 0%. 30 g of the resulting polyamic acid was dissolved in 570 g of N-methyl-2-pyrrolidone, 23.4 g of pyridine and 18.1 g of acetic anhydride were added, and dehydration was carried out at 110 ° C. for 4 hours, followed by precipitation, washing, The pressure was reduced to obtain 17.5 g of an imidized polymer having a logarithmic viscosity of 0.77 dl / g and an imidization rate of 100% (hereinafter referred to as “imidized polymer (B-4)”).

Example 1
100 parts by weight of the imidized polymer (B-1) obtained in Synthesis Example 6 and a fluorine-containing compound represented by the above formula (II) include a hydrocarbon acrylate-perfluorocarbon acrylate copolymer (EF801 (Gemco Co., Ltd.). 0.01 parts by weight, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane / 2 parts by weight and 3-glycidoxypropyltrimethoxysilane / 1 part by weight It is dissolved in a mixed solvent of γ-butyrolactone / N-methyl-2-pyrrolidone / butyl cellosolve (71/17/12 (weight ratio)) to obtain a solution having a solid content concentration of 4% by weight. The liquid crystal aligning agent of this invention was prepared by filtering. The liquid crystal aligning agent is applied to the transparent electrode surface of the glass substrate with a transparent electrode made of an ITO film using a liquid crystal alignment film printer (manufactured by Nissha Printing Co., Ltd.) and dried for 1 minute on an 80 ° C. hot plate. The film was dried on a hot plate at 200 ° C. for 10 minutes to form a film having an average film thickness of 600 Å. When this substrate was observed with a microscope having a magnification of 20 times, printing unevenness and pinholes were not observed, and the printability was good.

  A rubbing machine having a roll in which a nylon-type cloth is wound around this coating film was rubbed at a roll rotation speed of 500 rpm, a stage moving speed of 3 cm / sec, and a hair foot indentation length of 0.4 mm to form a liquid crystal alignment film. . Next, after the said liquid crystal aligning film formation board | substrate was immersed in isopropyl alcohol for 1 minute, it dried for 5 minutes on a 100 degreeC hotplate. Next, after applying an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm to the respective outer edges having the pair of liquid crystal alignment films on the substrate, the liquid crystal alignment film surfaces are overlapped and pressure bonded. The adhesive was cured. Next, a nematic liquid crystal (MLC-6221, manufactured by Merck & Co., Inc.) is filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port is sealed with an acrylic photo-curing adhesive. The liquid crystal display element of the present invention was produced by laminating the deflection plates.

  When the obtained liquid crystal display element was applied with a rectangular wave of 30 Hz and 3.0 V with an alternating current of 6.0 V (peak-peak) superimposed at an ambient temperature of 70 ° C. for 500 hours, the element was visually observed. There was no display defect of the element.

Examples 2 to 23 and Comparative Examples 1 to 4
Liquid crystal alignment in the same manner as in Example 1 except that the polyamic acid and imidized polymer obtained in Synthesis Examples 1 to 10 were used and the type and amount of fluorine-containing compound and the drying temperature of the liquid crystal alignment film were changed. An agent was prepared, a film was formed on the substrate, and the presence or absence of printing unevenness and pinholes was observed. Further, a liquid crystal display element was prepared and the presence or absence of display failure and the reliability were observed. In all Examples and Comparative Examples, polyamic acid and imidized polymer were used in such a ratio that polyamic acid: imidized polymer = 4: 1 (weight ratio). The results are also shown in Table 1.

Claims (3)

(A) a polymer having at least one repeating unit selected from the group consisting of repeating units represented by the following formulas (I-1) and (I-2), and (B) a plurality of polymers in the molecule. The fluorine-containing compound having an OR (R is an alkylene group) bond , provided that the fluorine-containing compound has a structural formula represented by each of the following formulas (II-1), (II-2) and (II-3): Is at least one compound selected from the group consisting of compounds having:
A liquid crystal aligning agent characterized by containing.

(Wherein P ¹ is a tetravalent organic group and Q ¹ is a divalent organic group.)

(Wherein P ² is a tetravalent organic group and Q ² is a divalent organic group.)

(In the above formula, R ¹ is C ₂ H ₄ O, R ² is C ₃ H ₆ O, R ³ is SO ₂ N (E), and E is a hydrogen atom or having 1 to 5 carbon atoms. An alkyl group, A is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, x and y are independently 1 to 10,000, and i, j and k are 1 independently of each other. -10, and n is a number from 1 to 10.) The liquid crystal aligning agent of Claim 1 whose (A) polymer is a polymer which has a repeating unit represented by the repeating unit represented by the said Formula (I-1), and the said Formula (I-2). The liquid crystal display element provided with the liquid crystal aligning film obtained from the liquid crystal aligning agent of Claim 1 or 2 .