KR20080076800A - Liquid crystal aligning agent and liquid crystal display device - Google Patents

Abstract

A liquid crystal aligning agent is provided to form liquid crystal aligning films having excellent liquid crystal aligning property and good electrical characteristics without being affected by solvent cleaning. A liquid crystal aligning agent contains (A) polymer obtained by a reaction of tetracarboxylic dianhydride with at least one diamine selected from diamines represented by the following formulae 1-4, and/or imidized polymer thereof, and (B) a compound having at least two epoxy groups in the molecule. In the formulae, each of R^1 to R^4 is a C1-40 linear, branched, or cyclic alkyl group or C4-40 linear, branched, or cyclic alkenyl group, 1-15 hydrogen atoms contained in the R^1 to R^4 are substitutable with fluorine atoms, and each of A^1 and A^2 is a hydrogen atom or methyl group.

Description

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

This invention relates to the liquid crystal display element which has a liquid crystal aligning agent and a liquid crystal aligning film. More specifically, it is related with the liquid crystal aligning agent which has a high vertical alignment property, and provides the liquid crystal aligning film excellent in heat resistance, and the liquid crystal aligning film formed from the said liquid crystal aligning agent.

Currently, as a liquid crystal display element, the liquid crystal aligning film containing polyamic acid, polyimide, etc. is formed in the surface of the board | substrate with which transparent conductive films, such as ITO (indium oxide-tin oxide), are provided, and it is set as the board | substrate for liquid crystal display elements, The two sheets were arranged to face each other to form a layer of nematic liquid crystal having positive dielectric anisotropy in the gap to form a sandwich cell, and the long axis of the liquid crystal molecules was continuously twisted by 90 ° from one substrate to the other substrate. TN type liquid crystal display elements having a so-called TN (Twisted Nematic) type liquid crystal cell are known. In addition, a STN (Super Twisted Nematic) type liquid crystal display device having a higher contrast and less visual dependence than a TN type liquid crystal display device has been developed. The STN type liquid crystal display element uses a blend of nematic liquid crystals with a chiral agent, an optically active substance, as a liquid crystal, and the birefringence effect caused by the long axis of the liquid crystal molecules continuously twisted over 180 ° between the substrates. It is to use.

In recent years, a transverse electric field type liquid crystal display device has been proposed in which two electrodes for driving a liquid crystal are arranged in a comb-tooth shape on one substrate, and an electric field parallel to the substrate surface is generated to control the liquid crystal molecules. This device is generally called an in-plane switching type (IPS type) and is known for its wide viewing angle characteristics. In particular, when the IPS device is used in combination with an optical compensation film, the viewing angle characteristic can be further improved, and a wide viewing angle comparable to the CRT can be obtained without grayscale inversion or color tone change.

In addition to these, a vertically aligned liquid crystal display device called a multi-domain vertical alignment (MVA) method or a patterned vertical alignment (PVA) method in which liquid crystal molecules having negative dielectric anisotropy are vertically aligned to a substrate has been proposed (the following patent) See Document 1 and Non-Patent Document 1). These vertically-aligned liquid crystal display elements are excellent in the viewing angle, contrast, etc., and also in the manufacturing process aspect, such as not having to perform a rubbing process in formation of a liquid crystal aligning film.

By the way, in the manufacturing process of a liquid crystal display element, the washing process with a solvent is generally performed in order to remove the foreign material etc. which generate | occur | produced in processes, such as a rubbing, and the removal of the adhering dust in a process. Ultrapure water and isopropanol are generally used as the cleaning solvent, and a method of further increasing the cleaning efficiency may be used by using brushing and ultrasonic waves at the time of cleaning. In the washing step, the solvent is removed (drying of the substrate) after washing by immersion in a solvent or the like. In a drying process, the solvent is evaporated by heating and the solvent is spread by an air knife in many cases. In this washing step, the liquid crystal alignment film (especially the surface state) is affected, and the non-uniformity of the pretilt angle and the non-uniformity of the electrical properties are generated, so that the display unevenness or display defect may occur when the liquid crystal display element is used. Known. Therefore, from the viewpoint of improving the yield of the product and improving the display quality, a high degree of durability to the cleaning process, in particular to the cleaning solvent, is required for the liquid crystal alignment film.

Moreover, the demand for the improvement of the display quality in recent years becomes more severe, and the liquid crystal aligning film which has the above characteristic with respect to liquid crystal aligning property and an electrical property especially is calculated | required.

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

[Non-Patent Document 1] "Liquid Crystal", Vol. 3 (No. 2), p117 (1999)

This invention is made | formed based on the said situation, The objective is the liquid crystal aligning agent which provides the liquid crystal aligning film which is excellent in liquid crystal alignability and has favorable electrical characteristics, without being influenced by solvent washing well, and the display characteristic of high quality. It is providing the liquid crystal display element which has.

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

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

(A) a polymer obtained by the reaction of tetracarboxylic dianhydride and at least one selected from diamines represented by the following formulas (1) to (4) and / or imidized polymers thereof, and

(B) It is achieved by the liquid crystal aligning agent containing the compound which has two or more epoxy groups in a molecule | numerator.

(Wherein R ¹ to R ⁴ are each independently a linear, branched or cyclic alkyl group having 1 to 40 carbon atoms or a linear, branched or cyclic alkenyl group having 4 to 40 carbon atoms, and among the hydrogen atoms which R ¹ to R ⁴ have 1 to 15 may be substituted with a fluorine atom, A ¹ and A ² are each independently a hydrogen atom or a methyl group)

The said object of this invention is 2nd achieved by the liquid crystal display element provided with the liquid crystal aligning film obtained from the said liquid crystal aligning agent.

Since the liquid crystal aligning film formed from the liquid crystal aligning agent of this invention has low surface free energy and high durability with respect to a washing | cleaning process, the liquid crystal aligning film excellent in process suitability is obtained. Moreover, since it has liquid crystal aligning property and high voltage retention characteristic at the same time, the liquid crystal aligning film which can be preferably applied to a liquid crystal display element is obtained.

The liquid crystal display element of this invention can be used suitably for various liquid crystal display devices, for example, a table calculator, a wristwatch, a table clock, a mobile telephone, a counting plate, a word processor, a personal computer, a liquid crystal television, etc.

<(A) Polymer>

The liquid crystal aligning agent of this invention is a polymer obtained by reaction with (A) tetracarboxylic dianhydride and 1 or more types chosen from the diamine represented by the said General formula (1)-(it calls "specific polyamic acid" hereafter.) ) And / or its imidized polymer (hereinafter referred to as "(A) polymer").

Hereinafter, the tetracarboxylic anhydride and diamine used in order to synthesize | combine the (A) polymer contained in the liquid crystal aligning agent of this invention are demonstrated.

Tetracarboxylic dianhydride

As tetracarboxylic dianhydride used for the synthesis | combination of specific polyamic acid and / or its imidation polymer, For example, aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride Etc. can be mentioned.

As said aliphatic tetracarboxylic dianhydride, butane tetracarboxylic dianhydride etc. are mentioned, for example.

As said alicyclic tetracarboxylic dianhydride, it is following General formula (5)

In formula (5), R ⁵ is independently a hydrogen atom, a halogen atom or a monovalent organic group. A compound represented by the following formula (6)

(6)

(6)

In formula (6), R <^6> is independently a C1-C10 alkyl group, n is an integer of 0-2, A compound represented by following formula (7) or (8)

(7)

(7)

(8)

(8)

In the formulas (7) and (8), R ⁷ and R ⁹ represent a divalent organic group having an aromatic ring, and R ⁸ and R ¹⁰ independently represent a hydrogen atom or an alkyl group, 1, 2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-dicyclohexyltetracarboxylic dianhydride Water, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,2,4-tricarboxycyclopentylacetic dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxyl Acid dianhydrides, 3,5,6-tricarboxynorbornane-2-acetic dianhydride, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecane-3,4,8,9-tetracar Acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene- 1,2-dicarboxylic anhydride, bicyclo [2.2.2] -oct-4-ene-2,3,5,6-tet Lacarboxylic dianhydride, bicyclo [2.2.2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3,5,6-tricarboxy-2-carboxynorbore Egg-2: 3,5: 6-anhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, etc. are mentioned.

As a halogen atom of R <^5> in the said General formula (5), a chlorine atom, a bromine atom, or an iodine atom is mentioned, for example, As a monovalent organic group of R <^5> , it is a C1-C10 alkyl group, an alkoxy, for example. A practical group etc. are mentioned, Specifically, a methyl group, an ethyl group, a methoxyl group, etc. are mentioned, for example.

As a specific example of the compound represented by the said General formula (5), a 1,2,3,4- cyclobutane tetracarboxylic dianhydride, a 1,2-dimethyl- 1,2,3,4- cyclobutane tetra, for example Carboxylic acid dianhydride, 1,2-diethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid Dianhydrides, 1,3-diethyl-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 etc. are mentioned.

As a specific example of a compound represented by the said General formula (6), it is 1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl) -naph, for example. Earth [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5 (tetrahydro-2,5-dioxo-3- Furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-ethyl-5 (tetrahydro-2,5- Dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-methyl-5 (tetrahydro -2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-ethyl -5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexa Hydro-8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4, 5,9b-hexahydro-8-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3 , 3a, 4,5,9b-hexahydro-5,8-dimethyl-5 (tetrahi -2,5-dioxo-3-furanyl) - and the like can be furan-1,3-dione-naphtho [1,2-c].

As said aromatic tetracarboxylic dianhydride, a pyromellitic dianhydride, 3,3 ', 4,4'- benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-biphenyl Sulfontetracarboxylic 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'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3', 4,4'- tetraphenylsilane tetracarboxylic dianhydride , 1,2,3,4-furtetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4'-bis (3,4 -Dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoroisopropyl Dendiphthalic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetraca Acid dianhydrides, bis (phthalic acid) phenylphosphineoxide dianhydrides, ethylene glycol-bis (anhydrotrimelitate), propylene glycol-bis (anhydrotrimelitate), 1,4-butanediol-bis (anhydro Trimellitate), 1,6-hexanediol-bis (anhydro trimellitate), 1,8-octanediol-bis (anhydro trimellitate), 2,2-bis (4-hydroxyphenyl) propane -Bis (anhydrotrimelitate), the compound represented by following General formula (9)-(12), etc. are mentioned.

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

As tetracarboxylic dianhydride used for the synthesis | combination of a specific polyamic acid, 1,2,3,4-cyclobutane tetracarboxylic dianhydride and a 1, 2- dimethyl- 1,2,3,4- cyclobutane tetra Carboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'- Dicyclohexyl tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,2,4-tricarboxycyclopentylacetic dianhydride, 5- (2,5-dioxotetrahydro- 3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, bicyclo [2.2.2] -oct-4-ene-2,3,5,6-tetracarr Acid dianhydrides, 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, pyromellit Acid dianhydrides, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 3,3 ', 4,4 It is preferable that it contains 1 or more types of compounds chosen from the group which consists of "-biphenyl tetracarboxylic dianhydride. Moreover, as especially preferable tetracarboxylic dianhydride, 2,3,5- tricarboxy cyclopentyl acetic dianhydride and 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3- Cyclohexene-1,2-dicarboxylic acid anhydride, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl)- Naphtho [1,2-c] -furan-1,3-dione. It is preferable that it is 20 mol% or more with respect to all tetracarboxylic dianhydride, and, as for the content rate of these preferable tetracarboxylic dianhydride, it is more preferable that it is 40 mol% or more.

<Diamine>

The diamine used for the synthesis of the specific polyamic acid and / or the imidized polymer thereof is at least one selected from the compounds represented by the formulas (1) to (4) (hereinafter also referred to as "specific diamine").

In the diamine represented by the above formulas (1) to (4), examples of the linear alkyl group having 1 to 40 carbon atoms represented by R ¹ to R ⁴ include, for example, n-hexyl group, n-octyl group, n-decyl group and n-dode Practical groups, n-pentadecyl groups, n-hexadecyl groups, n-octadecyl groups, n-eicosyl groups and the like;

As the branched alkyl group, for example, 1-methylhexyl group, 1-ethylhexyl group, 2-methylhexyl group, 2-ethylhexyl group, 1-ethyloctyl group, 2-ethyloctyl group, 3-ethyloctyl group, 1,2-dimethylhexyl group, 1,2-diethylhexyl group, 1,2-dimethyloctyl group, 1,2-diethyloctyl group, 1-methyldecyl group, 1-ethyldecyl group, 2-methyldecyl Practical groups, 2-ethyldecyl group and the like;

Examples of the cyclic alkyl group include groups obtained by removing one hydrogen atom from cyclic alkanes such as cyclobutane, cyclopentane, cyclohexane, cyclodecane, norbornene, bicyclooctane, bicycloundecane and adamantane, And groups each having a steroid skeleton. Examples of the group having the steroid skeleton include a group obtained by removing one hydrogen atom from a steroid compound such as cholesterol, cholestanol, lanosterol, or desosterol.

Examples of the linear, branched or cyclic alkenyl group having 4 to 40 carbon atoms include groups in which at least one of the carbon-carbon bonds of the alkyl group exemplified above is a double bond.

As specific diamine, R <^1> -R <^4> in the said Formula (1-4) is represented by the diamine which is a group which has a steroid skeleton, or said Formula (1), and R <^1> is a linear, branched or cyclic alkyl group or carbon number of C1-C20 Preference is given to diamines which are linear, branched or cyclic alkenyl groups of 4 to 20.

In the synthesis | combination of a specific polyamic acid and / or its imidation polymer, other diamine can be used together besides the said specific diamine. As another diamine, an aliphatic or alicyclic diamine, the diamine which has two primary amino groups in a molecule, and nitrogen atoms other than the said primary amino group, diamino organosiloxane, aromatic diamine, etc. are mentioned, for example.

Examples of the aliphatic or alicyclic diamines include 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, and 4,4-diaminoheptamethylene. Diamine, 1,4-diaminocyclohexane, 1,4-bis (aminomethyl) -bicyclo [2.2.1] heptane, 1,4-bis (aminopropyl) -bicyclo [2.2.1] heptane, 1 , 3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1,3-bis (aminopropyl) cyclohexane, methaxylylenediamine, paraxylylenediamine, isophoronediamine , Tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindanylenedimethylenediamine, tricyclo [6.2.1.0 ^2,7 ] -undecylenedimethyldiamine, 4,4'-methylenebis (cyclohexyl Amines);

Examples of the diamine having two primary amino groups and nitrogen atoms other than the primary amino group in the molecule include 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-dimethyl Amino-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-ethoxyacridinlac Tate, 3,8-diamino-6-phenylphenanthridine, 1,4-diaminopiperazine, 3,6- Amino quinoa acridine, bis (4-aminophenyl) phenylamine, and the like;

As said diamino organosiloxane, it is the following general formula (13), for example.

In formula (13), R ¹¹ represents a hydrogen atom or a monovalent organic group independently of each other, R ¹² independently of each other is a methylene group or an alkylene group having 2 to 20 carbon atoms, and p is an integer of 1 to 20. Compound;

Examples of the aromatic diamine include p-phenylenediamine, 2-methyl-1,4-phenylenediamine, 2-ethyl-1,4-phenylenediamine, and 2,5-dimethyl-1,4-phenylene. Diamine, 2,5-diethyl-1,4-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, m-phenylenediamine, 4,4'-diaminodi Phenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-dia Minobiphenyl, 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 ' -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- S (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 Methyl) phenoxy] -octafluorobiphenyl, 4- (4-n-heptylcyclohexyl) phenoxy-2,4-diaminobenzene, 3,6 -Diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, formula (14) To (16)

(In Formulas (14) to (16), X ¹ independently of each other is a single bond, -O-, -CO-, -COO-, -OCO-, -NHCO-, -CONH-, -S-, methylene group , An alkylene group having 2 to 6 carbon atoms or a phenylene group, R ¹³ is an alkyl group having 10 to 20 carbon atoms, a monovalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms, or a monovalent oil having a fluorine atom having 6 to 20 carbon atoms. And R ¹⁴ is a divalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms or a divalent organic group having a fluorine atom having 5 to 30 carbon atoms, and q is an integer of 1 to 20). Each can be mentioned.

As the diamine represented by the general formula (14), for example, the following general formulas (17) to (31)

As the compound represented by the above general formula (15), the compounds represented by the following general formulas (32) to (36)

The compound represented by these is mentioned, respectively.

When using together specific diamine and another diamine in the synthesis | combination of a specific polyamic acid, it is preferable that the use ratio of specific diamine is 1 mol% or more with respect to all diamine, Especially preferably, it is 5 mol% or more.

<Synthesis of specific polyamic acid>

Next, the synthesis | combining method of the specific polyamic acid which the liquid crystal aligning agent of this invention can contain is demonstrated.

The specific polyamic acid is the tetracarboxylic dianhydride and the specific diamine and optionally other diamine, preferably in an organic solvent, preferably -20 ° C to 150 ° C, more preferably 0 to 100 ° C. Under conditions, preferably, the reaction can be carried out by reacting for 0.5 to 72 hours.

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

The organic solvent is not particularly limited as long as it can dissolve the specific polyamic acid synthesized. For example, 1-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide Amide solvents such as 3-butoxy-N, N-dimethylpropanamide, 3-methoxy-N, N-dimethylpropanamide and 3-hexyloxy-N, N-dimethylpropanamide; Aprotic polar solvents such as dimethyl sulfoxide, γ-butyrolactone, tetramethylurea and hexamethylphosphortriamide; Phenol solvents, such as m-cresol, xylenol, a phenol, and a halogenated phenol, etc. can be illustrated. It is preferable that the usage-amount ((alpha)) of an organic solvent is an amount which the ratio (monomer concentration) with respect to whole quantity ((alpha) + (beta)) of the total amount ((beta)) of tetracarboxylic dianhydride and a diamine compound becomes 0.1-30 weight%.

In the organic solvent, alcohol, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like, which are poor solvents of specific polyamic acids, may be used in combination without causing specific polyamic acid to be precipitated. Specific examples of such a poor solvent include methanol, ethanol, isopropanol, cyclohexanol, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, Ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, Diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether , Ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, di Tylene 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, isoamyl propionate, isoamyl isobutylate, diisopentyl ether and the like.

As described above, a reaction solution obtained by dissolving a specific polyamic acid is obtained. Then, the reaction solution is poured into a large amount of poor solvent to obtain a precipitate, and the precipitate is dried under reduced pressure or the reaction solution is distilled off under reduced pressure with a evaporator to obtain a polyamic acid. Moreover, specific polyamic acid can be refine | purified by performing the process of dissolving this specific polyamic acid again in an organic solvent, and then depositing with a poor solvent or distilling off under reduced pressure with an evaporator once or several times.

<The synthesis method of the imidation polymer of specific polyamic acid>

Next, the synthesis | combining method of the imidation polymer of the specific polyamic acid which the liquid crystal aligning agent of this invention can contain is demonstrated.

The imidation polymer of a specific polyamic acid can be synthesize | combined by dehydrating and ring-closing part or all of the amic-acid structure which the said specific polyamic acid has.

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

The reaction temperature in the method of heating the specific polyamic acid of said (i) becomes like this. Preferably it is 50-200 degreeC, More preferably, it is 60-170 degreeC. When reaction temperature is less than 50 degreeC, dehydration ring-closure reaction does not fully advance, but when reaction temperature exceeds 200 degreeC, the molecular weight of the imidation polymer obtained may fall.

On the other hand, in the method of adding a dehydrating agent and a dehydrating ring-closure catalyst to the solution of the specific polyamic acid of said (ii), acid anhydrides, such as acetic anhydride, a propionic anhydride, trifluoroacetic anhydride, can be used as a dehydrating agent, for example. . Although the usage-amount of a dehydrating agent depends on a desired imidation ratio, it is preferable to set it as 0.01-20 mol with respect to 1 mol of repeating units of a specific polyamic acid. As the dehydration ring closure catalyst, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used, for example. However, it is not limited to 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. The imidation ratio can be made higher, so that the usage-amount of the said dehydrating agent and dehydration ring closure agent is large. As an organic solvent used for dehydration ring-closure reaction, the organic solvent illustrated above as what is used for the synthesis | combination of a specific polyamic acid is mentioned. The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C. Thus obtained imidized polymer can be refine | purified by performing the same operation as the purification method of a specific polyamic acid with respect to the obtained reaction solution.

<Average imidation ratio of the polymer>

The imidized polymer of a specific polyamic acid that can be used in the present invention may be partially dehydrated and closed, with a proportion of the repeating unit having an imide ring in all the repeating units (hereinafter also referred to as “imidization rate”) of less than 100%. have. The imidation ratio can be calculated | required by following formula (1) from <^1> H-NMR of a polymer.

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

(In Formula 1, A1 is the peak area around 10 ppm of the chemical shift derived from the protons of the NH group, A2 is the peak area near 7-8 ppm of the chemical shift derived from the aromatic protons, and α is before the imidization reaction. Ratio of the number of aromatic protons to one proton of NH group in the polyamic acid)

The average imidation ratio of the specific polyamic acid and / or its imidation polymer contained in the liquid crystal aligning agent of this invention becomes like this. Preferably it is 40 to 100%, More preferably, it is 50 to 100%. In addition, the "average imidation ratio" here means the imidation ratio measured by the said method with respect to the mixture containing the specific polyamic acid and all the imidation polymers contained in this invention. As will be described later, the specific polyamic acid and / or the imidized polymer contained in the liquid crystal aligning agent of the present invention may be replaced by at least one selected from the group consisting of other polyamic acid and the imidized polymer thereof. However, the average imidation rate in that case should be understood to refer to the imidization rate measured by the above method for a polymer mixture comprising a particular polyamic acid and its imidized polymer and all other polyamic acid and its imidized polymer. something to do.

<End modified polymer>

Certain polyamic acids or imidized polymers thereof used in the present invention may be of terminally modified type with controlled molecular weight. By using a terminal modified polymer, the effect of this invention is not impaired, and the application | coating characteristic of a liquid crystal aligning agent, etc. can be improved. These terminally modified polymers can be synthesized by adding an acid anhydride, a monoamine compound, a monoisocyanate compound and the like to the reaction system when synthesizing a specific polyamic acid. Here, as an acid anhydride, maleic anhydride, a phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n- tetradecyl succinic anhydride, n-hexadecyl succinic anhydride etc. are mentioned, for example. Can be. Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n Undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-eico Silamine etc. are mentioned. As a monoisocyanate compound, phenyl isocyanate, naphthyl isocyanate, etc. are mentioned, for example.

<Solution Viscosity of Polymer>

It is preferable that the specific polyamic acid obtained by the above and its imidation polymer have a viscosity of 20-800 mPa * s, and, as for 10% solution, it is more preferable to have a viscosity of 30-500 mPa * s.

In addition, the solution viscosity (mPa * s) of the polymer was measured at 25 degreeC using the E-type rotational viscometer with respect to the solution diluted to 10% of solid content concentration using the predetermined solvent.

<Other polymer>

In the liquid crystal aligning agent of this invention, unless the effect of this invention is impaired, 1 or more types chosen from the group which consists of a part of said specific polyamic acid or its imidation polymer from another polyamic acid and its imidation polymer ( Or "other polymer").

The said other polymer will not be specifically limited if it is polyamic acid other than specific polyamic acid, or its imidation polymer, It is preferable that it is a polymer obtained by reaction of the above-mentioned tetracarboxylic dianhydride and another diamine, or its imidation polymer. . As tetracarboxylic dianhydride used here, alicyclic tetracarboxylic dianhydride or aromatic tetracarboxylic dianhydride is preferable, and 1,2,3,4-cyclobutanetetracarboxylic dianhydride or fatigue is especially preferable. Mellitic dianhydride is preferred. As another diamine used here, aromatic diamine is preferable and 4, 4- diamino diphenylmethane is especially preferable.

The synthesis of such other polymers can be carried out in the same manner as the synthesis of specific polyamic acid and its imidized polymer, using other diamines instead of specific diamines.

When the liquid crystal aligning agent of this invention contains another polymer, the use ratio of another polymer becomes like this. Preferably it is 40 weight% or less with respect to the total amount of a specific polyamic acid and its imidation polymer, and another polymer, More preferably, It is weight% or less.

<(B) Compound Having Two or More Epoxy Groups in Molecule>

The liquid crystal aligning agent of this invention contains the compound (henceforth "epoxy compound") which has two or more epoxy groups in (B) molecule other than the said (A) polymer.

(B) As a epoxy compound, a glycidyl ether compound, a glycidyl amine compound, etc. are mentioned.

Examples of the glycidyl ether compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol di. Glycidyl 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, benzene-1,4-diol diglycidyl ether, 2-methylbenzene-1,4-diol diglycidyl ether, 2- Ethylbenzene-1,4-diol diglycidyl ether, 2-n-hexylbenzene-1,4-diol diglycidyl ether, 2-n-dodecylbenzene-1,4-diol diglycidyl ether , 2-trifluoromethylbenzene-1,4-diol diglycidyl ether, 2,5-diethylbenzene-1,4-diol diglycidyl ether, etc. are mentioned. Among these glycidyl ether compounds, polyethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, benzene- 1,4-diol diglycidyl ether or 2-methylbenzene-1,4-diol diglycidyl ether is mentioned as a preferable thing.

The glycidylamine compound is represented by the following formula (37)

It is a compound which has 1 or more, preferably 2, diglycidylamino group represented by these. As a specific example of a glycidyl amine compound, it is N, N, N ', N'- tetraglycidyl-p-phenylenediamine, N, N, N', N'- tetraglycidyl-2-, for example. Methyl-1,4-phenylenediamine, N, N, N ', N'-tetra glycidyl-2-n-propyl-1,4-phenylenediamine, N, N, N', N'-tetra Glycidyl-2-n-hexyl-1,4-phenylenediamine, N, N, N ', N'- tetraglycidyl-2-trifluoromethyl-1,4-phenylenediamine, N, N, N ', N'-tetraglycidyl-2,5-dimethyl-1,4-phenylenediamine, N, N, N', N'-tetraglycidyl-m-xylenediamine, N, N , N ', N'-tetraglycidyl-2,2'-dimethyl-4,4'-diaminobiphenyl, N, N, N', N'-tetraglycidyl-2,2'-di Ethyl-4,4'-diaminobiphenyl, N, N, N ', N'-tetraglycidyl-3,3'-dimethyl-4,4'-diaminobiphenyl, N, N, N' , N'-tetraglycidyl-3,3'-diethyl-4,4'-diaminobiphenyl, 2,2-bis [4- (N, N-diglycidyl-4-aminophenoxy ) Phenyl] propane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N, N', N'-tetraglycidyl -4,4'-diaminodiphenylether, 1,3-bis (N, N- diglycidylaminomethyl) cyclohexane, 1,4-bis (N, N- diglycidylaminomethyl) cyclo Hexane, 1,3-bis (N, N-diglycidylaminomethyl) benzene, 1,4-bis (N, N-diglycidylaminomethyl) benzene, 3- (N-allyl-N-gly Cydyl) aminopropyltrimethoxysilane, 3- (N, N-diglycidyl) aminopropyltrimethoxysilane, N, N-diglycidyl-benzylamine, N, N-diglycidyl- Aminomethyl cyclohexane etc. are mentioned. Among these glycidylamine compounds, N, N, N ', N'-tetraglycidyl-p-phenylenediamine, N, N, N', N'-tetraglycidyl-2-methyl-1, 4-phenylenediamine, N, N, N ', N'-tetraglycidyl-2,2'-dimethyl-4,4'-diaminobiphenyl, N, N, N', N'-tetragly Cydyl-4,4'-diaminodiphenylmethane, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, 1,4-bis (N, N-diglycidylaminomethyl ) Cyclohexane or N, N, N ', N'- tetraglycidyl-m-xylenediamine is mentioned as a preferable thing.

As the (B) epoxy compound contained in the liquid crystal aligning agent of this invention, a glycidyl amine compound is preferable.

The use ratio of the epoxy compound (B) in the liquid crystal aligning agent of the present invention is preferably with respect to 100 parts by weight of the whole polymer (the specific polyamic acid and its imidized polymer and other polyamic acid and all of the polymer thereof. Is 0.01 to 100 parts by weight, more preferably 0.1 to 50 parts by weight.

<Other ingredients>

Although the liquid crystal aligning agent of this invention contains the said (A) specific polyamic acid and / or its imidation polymer, and (B) epoxy compound as an essential component, it can contain other components arbitrarily. As such another additive, amine compounds (henceforth simply "amine compound") other than (C) glycidylamine compound, (D) functional silane containing compound, etc. are mentioned, for example.

(C) An amine compound can be added from the viewpoint of the improvement of the storage stability of a liquid crystal aligning agent, and the electrical characteristic of the obtained liquid crystal aligning film.

As such (C) amine compound, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecyl Amines, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-eicosylamine, 2-methoxyethylamine, 2-methoxybenzylamine, 4-methoxybenzylamine, diethylamine, diisopropylamine, methylethylamine, n-ethylcyclohexylamine, triethylamine, triethanolamine, aniline, o-toluidine, m-toluidine, p-toluidine, 2-ethylaniline, 3-ethylaniline, 4-ethylaniline, p-hexylaniline, 2-fluoroaniline, 4-fluoroaniline, 2,4,6- Trifluoroaniline, o-phenetidine, m-phenetidine, p-phenetidine, p-trifluoromethoxyaniline, p-trifluoroethoxyaniline, cyclohexylamine, cyclooctylamine, pyridine, Piperidine, pipepe Razine, 1-cyclohexylpiperazine 2-azabicyclo [2.2.2] octane, 9-azabicyclo [3.3.1] nonane, 9-methyl-9-azabicyclo [3.3.1] nonane, 1,4- Diazabicyclo [2.2.2] octane, 3,7-diazabicyclo [3.3.1] nonane, 1,8-diazabicyclo [5.4.0] undecene, and the like.

The said (D) functional silane containing compound can be added in order to improve the adhesiveness to the board | substrate surface of the liquid crystal aligning film obtained further. As a specific example of such (D) functional silane containing compound, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 2-aminopropyl trimethoxysilane, 2-aminopropyl triethoxy Silane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3- Ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetri Amine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecan, 10-triethoxysilyl-1,4,7-triazadecan, 9- Trimethoxysilyl-3,6-diazanyl acetate, 9-triethoxysilyl-3,6-diazanyl acetate, N-benzyl-3-aminopropyltrimeth Sisilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3 -Aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, 3- (N-allyl-N-glycidyl) aminopropyltrimethoxysilane, 3- (N, N- diglycidyl) aminopropyl trimethoxysilane etc. are mentioned.

<Liquid crystal aligning agent>

The liquid crystal aligning agent of this invention is manufactured as a solution state in which the specific polyamic acid and / or its imidation polymer, and the other component added arbitrarily are melt | dissolved in the organic solvent preferably.

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

As an especially preferable organic solvent used for the liquid crystal aligning agent of this invention, N-methyl- 2-pyrrolidone, (gamma) -butyrolactone, (gamma) -butyrolactam, N, N- dimethylformamide, N, N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, ethylene glycol methyl ether , Ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol Dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether The site can be like. These may be used independently, or may mix and use 2 or more types.

The solid content concentration (the value obtained by dividing the total weight of components other than the solvent in the liquid crystal aligning agent by the total weight of the liquid crystal aligning agent) in the liquid crystal aligning agent of the present invention is selected in the range of 1 to 10% by weight in consideration of viscosity, volatility, and the like. It is desirable to be. Although the liquid crystal aligning agent of this invention is apply | coated to the surface of a board | substrate, and the coating film used as a liquid crystal aligning film is formed, when solid content concentration is less than 1 weight%, the film thickness of this coating film becomes too small and a favorable liquid crystal aligning film cannot be obtained, while solid content concentration is When it exceeds 10 weight%, the film thickness of a coating film will become large too much and a favorable liquid crystal aligning film may not be obtained, the viscosity of a liquid crystal aligning agent may increase, and coating characteristics may fall, and neither is preferable.

The value of the more preferable solid content concentration of the liquid crystal aligning agent of this invention changes with the method employ | adopted when apply | coating the liquid crystal aligning agent of this invention to a board | substrate. For example, it is especially preferable to make solid content concentration into the range of 1.5 to 4.5 weight% by the spinner method. In the case of the printing method, the solid content concentration is in the range of 4 to 10% by weight, and the solution viscosity is particularly preferably in the range of 10 to 50 mPa · s. When using the inkjet method, it is especially preferable to make solid content concentration into the range of 2 to 5 weight%, and to make solution viscosity into the range of 3-15 mPa * s by this.

It is preferable that the surface tension of the liquid crystal aligning agent of this invention is 25-40 mN / m.

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

<Liquid crystal display element>

The liquid crystal display element of this invention is equipped with the liquid crystal aligning film obtained from the liquid crystal aligning agent of this invention obtained as mentioned above, It is characterized by the above-mentioned.

The liquid crystal display element of this invention can be manufactured by following process (1)-(4), for example.

(1) The liquid crystal aligning agent of this invention is apply | coated to the one surface of the board | substrate with which the patterned transparent conductive film is provided by appropriate coating methods, such as an offset printing method, a spin coating method, and an inkjet printing method, and then a coating film is heated by heating a coated surface. To form. Here, as a board | substrate, For example, glass, such as float glass and a soda glass; Transparent substrates containing plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone and polycarbonate can be used. Examples of the transparent conductive film provided on one surface of the substrate include an NESA film containing tin oxide (SnO ₂ ) (registered trademark of PPG Co., Ltd. USA), an ITO film containing indium tin oxide (In ₂ O ₃ -SnO ₂ ), and the like. The transparent conductive film can be used, and the photoetching method and the method of using a preliminary mask at the time of forming a transparent conductive film are used for patterning of these transparent conductive films. In application | coating of a liquid crystal aligning agent, in order to make adhesiveness of a board | substrate surface, a transparent conductive film, and a coating film more favorable, you may apply | coat a functional silane containing compound, a functional titanium containing compound, etc. previously on the said surface of a board | substrate. . The heating temperature after apply | coating a liquid crystal aligning agent becomes like this. Preferably it is 80-300 degreeC, More preferably, it is 120-250 degreeC. On the other hand, when the liquid crystal aligning agent of this invention contains the polymer which has an amic acid unit, after coating, an organic solvent is removed, but the coating film used as an alignment film is formed, but it heats further and the dehydration ring closure advances to a more imidized coating film. You may.

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

(2) Next, a rubbing treatment is performed to rub the coating film surface formed as described above in a predetermined direction with a roll wound with a cloth including fibers such as nylon, rayon, cotton, or the like, or irradiate polarized ultraviolet rays to the coating film surface. By the method or the method of irradiating an ion beam to the coating film surface, the orientation ability of a liquid crystal molecule can be provided to a coating film, and a liquid crystal aligning film can be obtained.

(3) The liquid crystal aligning film obtained by carrying out as said (1)-(2) can be wash | cleaned as needed. Examples of the washing solvent include water, acetone, methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, methyl ethyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, tetrahydrofuran, hexane, Heptane, octane and the like can be used. Surfactant may be added to a washing | cleaning solvent in order to improve washing | cleaning efficiency, or it may be based on the method of heating and washing a solvent, the method of using a brush together, and the method of using an ultrasonic wave together. After washing, after rinsing or the like with a suitable solvent or the like, heating and drying may be performed as necessary.

(4) Two board | substrates with a liquid crystal aligning film were manufactured as mentioned above, two board | substrates were opposingly arranged through a clearance gap (cell gap) so that the rubbing direction in each liquid crystal aligning film may be orthogonal or antiparallel, The peripheral part of the substrate is bonded using a sealant, the liquid crystal is injected and filled into the cell gap partitioned by the substrate surface and the sealant, and the injection hole is sealed to form a liquid crystal cell. And a liquid crystal display element by bonding a polarizing plate to the outer surface of the liquid crystal cell, ie, the other surface side of each board | substrate which comprises a liquid crystal cell, so that the polarization direction may coincide or orthogonally cross with the rubbing direction of the liquid crystal aligning film formed in one surface of the said board | substrate. Is obtained. Here, as the sealant, for example, an epoxy resin containing aluminum oxide spheres as a curing agent and a spacer can be used. Examples of the liquid crystals include nematic liquid crystals and smectic liquid crystals. Among them, nematic liquid crystals are preferred, and for example, Schiff base liquid crystals, subfamily clock liquid crystals, biphenyl liquid crystals, phenylcyclohexane liquid crystals, ester liquid crystals, A terphenyl type liquid crystal, a biphenyl cyclohexane type liquid crystal, a pyrimidine type liquid crystal, a dioxane type liquid crystal, a bicyclooctane type liquid crystal, a cuban type liquid crystal, etc. can be used. Moreover, it is sold to these liquid crystals as cholesteric liquid crystals, such as cholestyl chloride, cholesteryl nonaate, a cholesteryl carbonate, and brand names "C-15", "CB-15" (made by Merck), for example. It is also possible to add and use a chiral agent. Ferroelectric liquid crystals such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate can also be used.

As a polarizing plate bonded to the outer surface of a liquid crystal cell, the polarizing plate containing the polarizing plate called H film which absorbed iodine, and extending | stretching polyvinyl alcohol between the cellulose acetate protective films, or the polarizing plate containing H film itself is mentioned.

<Example>

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

Evaluation of the liquid crystal aligning agent manufactured by the following example and the comparative example followed the following method.

[Evaluation of Surface Free Energy of Liquid Crystal Alignment Film]

On the transparent conductive film of the glass substrate of thickness 1mm which has a transparent conductive film containing an ITO film in one surface, the liquid crystal aligning agent solution manufactured by each Example or the comparative example was apply | coated with a spinner, and it heated at 200 degreeC for 60 minutes. This obtained the board | substrate which has a film with a film thickness of 0.06 micrometer. About this film, the contact angle of water and diiomethane was measured, and the surface free energy of the film (liquid crystal aligning film) was calculated | required using the value of the extended hawks using the measured value.

[Measurement of Voltage Retention Rate]

Six glass substrates having a thickness of 1 mm having a transparent conductive film containing an ITO film on one surface were prepared, and a liquid crystal aligning agent solution prepared in each example or comparative example was applied by a spinner on the transparent conductive film of each substrate. Then, by heating at 200 ° C. for 60 minutes, six substrates having a film having a thickness of 0.06 μm were obtained.

Of these substrates, two sheets of ultrapure water were used as the cleaning solvent, and the other two sheets were cleaned using isopropanol as the cleaning solvent, and the ultrasonic cleaning was performed at 40 ° C for 1 minute, and then heated at 100 ° C for 10 minutes to remove the solvent. The remaining two sheets were subjected to subsequent processes without washing. Thus, three pairs of liquid crystal aligning film application board | substrates with different washing conditions were obtained.

Next, two board | substrates which make washing conditions the same are paired, and after apply | coating the aluminum oxide sphere containing epoxy resin adhesive of diameter 5.5micrometer except a liquid crystal injection hole to each outer edge which has each liquid crystal aligning film of each board | substrate, a liquid crystal The alignment film was inward, overlapped and crimped so that the rubbing direction became antiparallel, and the adhesive was cured. Subsequently, after filling a nematic liquid crystal (negative type | mold, Merck make, MLC-6608) between a board | substrate from a liquid crystal inlet, the liquid crystal inlet is sealed with an acryl-type photocuring adhesive agent, and a polarizing plate is bonded to both surfaces of the outer side of a board | substrate, Three pairs of liquid crystal display elements in which washing conditions are different were manufactured.

For each of these liquid crystal display elements, a voltage of 5 V was applied at 60 ° C. with an application time of 60 microseconds and a span of 16.7 microseconds, and then the voltage retention after 16.7 milliseconds from the release of the application was measured.

[Liquid Crystal Orientation Evaluation]

When the applied voltage is changed from AC 0V to 8V with respect to each liquid crystal display element manufactured by the said method, both the whole surface when it observes with the naked eye from a perpendicular direction with respect to a liquid crystal display element, and when it observes from an inclination direction. When the display was uniformly displayed without display defects at " good ", the " goodness " was defined as &quot; nonuniformity &quot; when the display unevenness occurred at one or both sides of the observation direction.

Monomer Synthesis Example 1 (Synthesis of 1- (3,5-diaminophenyl) -3-octadecylsuccinimide)

12.81 g (0.07 mol) of 3,5-dinitroaniline and 70 mL of acetic acid were added to a 300 mL three necked flask substituted with nitrogen gas, and the solid was dissolved by stirring while flowing nitrogen gas. To this was added 24.64 g (0.07 mol) of octadecyl succinic anhydride and reacted by refluxing for 20 hours under nitrogen. After cooling the reaction solution to room temperature, 70 mL of methanol was added and the mixture was allowed to stand overnight. The precipitated solid was filtered, fractionated, washed with methanol and dried to obtain 30 g of 1- (3,5-dinitrophenyl) -3-octadecylsuccinimide (yield 83%).

Next, 30 g (0.058 mol) of 1- (3,5-dinitrophenyl) -3-octadecylsuccinimide synthesized above in a 500 mL flask substituted with nitrogen gas, 100 mL of ethanol, tetrahydrofuran 100 mL of (THF) and 25 g of reduced catalyst palladium carbon (Pd / C) were added, and the mixture was stirred at 70 ° C for 1 hour. 42.5 mL (43.75 g) of hydrazine monohydrate was added thereto, and the mixture was heated and refluxed for 6 hours to react. Pd / C was filtered off, fractionated and the filtrate was concentrated on a rotary evaporator. The obtained crude product was dissolved in N-methyl-2-pyrrolidone by heating, cooled, and recrystallized to obtain 14.6 g (0.032 mol) of 1- (3,5-diaminophenyl) -3-octadecylsuccinimide as a target product. , Yield 55%) was obtained.

Monomer Synthesis Example 2 (Synthesis of 1- (3,5-diaminophenyl) -3-dodecylsuccinimide)

1- (3,5-diaminophenyl) -3-dode in the same manner as in Synthesis Example b1-1 except that 18.76 g (0.07 mol) of dodecyl succinic anhydride was used instead of 24.64 g (0.07 mol) of octadecyl succinic anhydride. 11 g (0.030 mol, yield 51%) of silsuccinimides were obtained.

Monomer Synthesis Example 3 (Synthesis of 1- (3,5-diaminophenyl) -3-heptadecyl-4-methylmaleimide)

31.5 g (0.25 mol) of dimethylmaleic anhydride, 89.0 g (0.5 mol) of N-bromosuccinimide, 1.0 g (4.15 mmol) of benzoyl peroxide and 1,500 mL of carbon tetrachloride were added to a 2,000 mL three-necked flask with nitrogen substitution. It was heated to reflux for 5 hours. The reaction solution was cooled to room temperature, left at room temperature overnight, and then filtered. After washing the filtrate with water, the organic layer was concentrated on a rotary evaporator. The crude oily product obtained was distilled under high vacuum (120 to 125 ° C / 2 mmHg) to obtain 20.0 g (0.1 mol, 39% yield) of 3-bromomethyl-4-methylmaleic anhydride as an intermediate.

Next, in a 2,000 mL three-necked flask substituted with argon gas, 16.4 g (80 mmol) of 3-bromomethyl-4-methylmaleic anhydride obtained above, 1.52 g (8.0 mmol) of copper iodide, and diethyl ether 400 were obtained. mL and 160 mL of HMPA (hexamethyl phosphate triamide) were added and then cooled to -5 to 0 ° C under argon gas flow. While stirring this mixed solution, the solution which melt | dissolved 400 mmol of hexadecyl magnesium bromide separately prepared in 400 mL of diethyl ether was dripped over about 20 minutes. The mixture was returned to room temperature and stirred for further 8 hours. Thereafter, 600 mL of 4N-sulfuric acid diluted with 600 mL of diethyl ether was added to make the solution acidic. The separated aqueous layer was further washed with diethyl ether 600 mL, and the organic layers were combined. The organic layer was washed with water, dehydrated with sodium sulfate, and the solution was concentrated with a rotary evaporator to obtain an oily crude product. The crude product was purified by silica gel column using a petroleum ether / ethyl acetate (19: 1) mixed solution as a developing solvent, to obtain 14.0 g (0.04 mol, 50% yield) of 3-heptadecyl-4-methyl maleic anhydride. Got.

Next, 6.4 g (0.035 mol) of 3,5-dinitroaniline and 35 mL of acetic acid were added to a nitrogen gas substituted 200 mL three neck flask. The solid was dissolved by stirring while flowing nitrogen gas. To this, 12.3 g (0.035 mol) of 3-heptadecyl-4-methylmaleic anhydride obtained above was added and reacted under reflux for 20 hours under nitrogen. After cooling the reaction solution to room temperature, 35 mL of methanol was added and the mixture was allowed to stand overnight. The solid was filtered, fractionated, washed with methanol and dried to give 14.6 g (0.029 mol, 81% yield) of 1- (3,5-dinitrophenyl) -3-heptadecyl-4-methylmaleimide.

Next, 13.4 g (0.026 mol) of 1- (3,5-dinitrophenyl) -3-heptadecyl-4-methylmaleimide, 50 mL of ethanol, 50 mL of THF and a reduction catalyst were placed in a nitrogen gas substituted 300 mL flask. 12.5 g of Pd / C were added and stirred at 70 ° C for 1 hour. Subsequently, 19 mL (19.6 g) of hydrazine monohydrate was added and reacted by heating under reflux for 6 hours. Pd / C was filtered off, fractionated and the filtrate was concentrated on a rotary evaporator. The obtained crude product was recrystallized by heating and dissolving with N-methyl-2-pyrrolidone and cooling to obtain 6.6 g of 1- (3,5-diaminophenyl) -3-heptadecyl-4-methylmaleimide as a target product. 0.015 mol, yield 56%) was obtained.

Monomer Synthesis Example 4 (Synthesis of 1- (3,5-diaminophenyl) -3-hexadecaneoxymethyl-4-methylmaleimide)

12.81 g (0.07 mol) of 3,5-dinitroaniline and 70 mL of acetic acid were added to a nitrogen-substituted 300 mL three-necked flask, followed by stirring while flowing nitrogen gas to dissolve the solid. 14.35 g (0.07 mol) of 3- (bromomethyl) -4-methylmaleic anhydride synthesized in the same manner as in the intermediate of Synthesis Example A-3 was added thereto, and the mixture was reacted under reflux for 20 hours under nitrogen. After cooling the reaction solution to room temperature, 70 mL of methanol was added and the mixture was allowed to stand overnight. The solid was filtered, fractionated, washed with methanol and dried to obtain 18.9 g (0.051 mol, 73% yield) of 1- (3,5-dinitrophenyl) -3-bromomethyl-4-methylmaleimide. .

Next, 18.1 g (0.049 mol) of 1- (3,5-dinitrophenyl) -3-bromomethyl-4-methylmaleimide, and 1-hexadecanol sodium salt 12.9 in the 500 mL three neck flask which carried out the nitrogen substitution. g (0.049 mol) and 100 mL of dimethyl sulfoxide were added, followed by stirring at 100 ° C. for 10 hours. After cooling the reaction solution to room temperature, 70 mL of methanol was added and the mixture was allowed to stand overnight. The solid was filtered, fractionated, washed with methanol and dried to give 20.8 g (0.039 mol, 80% yield) of 1- (3,5-dinitrophenyl) -3-hexadecaneoxymethyl-4-methylmaleimide. .

Next, 13.8 g (0.026 mol) of 1- (3,5-dinitrophenyl) -3-hexadecaneoxymethyl-4-methylmaleimide, 300 mL of ethanol, 50 mL of THF, 12.5 g of reduction catalyst Pd / C were added and stirred at 70 ° C for 1 hour. Thereafter, 19 mL (19.6 g) of hydrazine monohydrate was added thereto, and the mixture was heated and refluxed for 6 hours to react. Pd / C was filtered off, fractionated and the filtrate was concentrated on a rotary evaporator. The obtained crude product was recrystallized by heating and dissolving with N-methyl-2-pyrrolidone and cooling to obtain 1- (3,5-diaminophenyl) -3-hexadecaneoxymethyl-4-methylmaleimide 8.2 as a target product. g (0.018 mol, yield 67%) was obtained.

Polymer Synthesis Examples 1 to 19, Polymer Comparative Synthesis Examples 1 to 4

To N-methylpyrrolidone, diamine and tetracarboxylic dianhydride were added in this order in the composition shown in Table 1 below to obtain a solution having a monomer concentration of 20% by weight, and reacted at 60 ° C for 4 hours to give polyamic acid (A- Solutions containing 1) to (A-19) or (a-1) to (a-4) were obtained. To each of the obtained polyamic acid solutions, pyridine and acetic anhydride in double molar number (equivalent) shown in Table 1 were added to the total amount (moles) of the amic acid units in the solution, and then heated to 110 ° C to conduct a dehydration ring closing reaction for 4 hours. . The obtained solution was reprecipitated with diethyl ether, recovered and dried under reduced pressure to obtain (B-1) to (B-19) and (b-1) to (b-4) as imidized polymers. The imidation ratio of these imidation polymers is shown in Table 1.

Polymer Synthesis Examples 20-22

Diamine and tetracarboxylic dianhydride were added to N-methylpyrrolidone in the composition shown in Table 1 in this order to make a solution having a monomer concentration of 20% by weight, and reacted at 60 ° C for 4 hours. The obtained solution was reprecipitated with diethyl ether, recovered and dried under reduced pressure to obtain polyamic acid (A-20) to (A-22). On the other hand, in the polymer synthesis examples 20-22, the imidation reaction was not performed.

In Table 1, the number in parentheses shows the use ratio of the monomer (molar ratio) with respect to the diamine and the acid anhydride, and the meanings of the symbols in the table are as follows.

<Diamine Compound>

D-1: 1- (3,5-diaminophenyl) -3-octadecylsuccinimide

D-2: 1- (3,5-diaminophenyl) -3-dodecylsuccinimide

D-3: 1- (3,5-diaminophenyl) -3-heptadecyl-4-methylmaleimide

D-4: 1- (3,5-diaminophenyl) -3-hexadecaneoxymethyl-4-methylmaleimide

D-5: octadecaneoxy-2,4-diaminobenzene

D-6: p-phenylenediamine

D-7: 4,4-diaminodiphenylmethane

D-8: 4,4-diaminodiphenyl ether

D-9: 2,2'-dimethyl-4,4'-diaminobiphenyl

Tetracarboxylic dianhydride

T-1: 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride

T-2: 2,3,5-tricarboxycyclopentyl acetic dianhydride

T-3: 1,3,3a, 4,5,9b-hexahydro-8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] Furan-1,3-dione

T-4: 1,2,3,4-cyclobutanetetracarboxylic dianhydride

Example 1

(A) The imidized polymer B-1 obtained in the synthesis example 1 as a polymer is melt | dissolved in (gamma) -butyrolactone / N-methyl- 2-pyrrolidone / butyl cellosolve mixed solution (weight ratio 40:30:30). 20 parts by weight of polyethyleneglycol diglycidyl ether (molecular weight: about 400) was added to the resulting solution as a (B) epoxy compound based on 100 parts by weight of the entire polymer, to obtain a solution having a solid content concentration of 4.0% by weight. This solution was visually observed and found to be a clear solution without haze. Then, the liquid crystal aligning agent was obtained by filtering this solution with the filter of 0.2 micrometer of pore diameters.

Various evaluation was performed in accordance with the above-mentioned method using this liquid crystal aligning agent. The results are shown in Tables 2 and 3 below.

Examples 2 to 39, Comparative Examples 1 to 12

The liquid crystal aligning agent was produced like Example 1 except having carried out the kind and quantity of the (A) polymer and (B) epoxy compound which were mix | blended with the liquid crystal aligning agent as described in Table 2. Table 2 and Table 3 show the results of the evaluation performed according to the above-described methods using these alignment agents.

In Table 2, in the epoxy compound (B), the numbers in parentheses indicate the content ratio (parts by weight based on 100 parts by weight of the entire polymer), and the meanings of the symbols in the table are as follows.

Epoxy A: Polyethylene glycol diglycidyl ether (molecular weight about 400)

Epoxy B: 1,6-hexanediol diglycidyl ether

Epoxy C: N, N, N ', N'-tetraglycidyl-2,2'-dimethyl-4,4'-diaminobiphenyl

Epoxy D: N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane

Epoxy E: 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane

Epoxy F: N, N, N ', N'-tetraglycidyl-m-xylenediamine

Claims (7)

(A) a polymer obtained by the reaction of tetracarboxylic dianhydride and at least one selected from diamines represented by the following formulas (1) to (4) and / or imidized polymers thereof, and (B) The liquid crystal aligning agent containing the compound which has two or more epoxy groups in a molecule | numerator. <Formula 1>

<Formula 2>

<Formula 3>

<Formula 4>

(Wherein R ¹ to R ⁴ are each independently a linear, branched or cyclic alkyl group having 1 to 40 carbon atoms or a linear, branched or cyclic alkenyl group having 4 to 40 carbon atoms, and among the hydrogen atoms which R ¹ to R ⁴ have 1 to 15 may be substituted with a fluorine atom, A ¹ and A ² are each independently a hydrogen atom or a methyl group) The liquid crystal aligning agent of Claim 1 whose compound which has 2 or more epoxy groups in a molecule | numerator (B) is a glycidylamine compound. The liquid crystal aligning agent of Claim 1 or 2 which contains 0.01-100 weight part of compounds which have two or more epoxy groups in (B) molecule with respect to 100 weight part of (A) polymers. The liquid crystal aligning agent according to any one of claims 1 to 3, wherein the groups R ¹ to R ⁴ of the diamine represented by Formulas 1 to ⁴ have a steroid skeleton. The diamine according to any one of claims 1 to 3, wherein the diamine is represented by the formula (1), and R ¹ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms or a linear, branched or cyclic group having 4 to 20 carbon atoms. The liquid crystal aligning agent which is diamine which is an alkenyl group. The liquid crystal aligning agent of any one of Claims 1-5 whose average imidation ratio of (A) polymer is 40 to 100%. The liquid crystal aligning film obtained from the liquid crystal aligning agent in any one of Claims 1-6 is provided, The liquid crystal display element characterized by the above-mentioned.