KR100840859B1 - Liquid crystal aligning agent and liquid crystal display element - Google Patents

Abstract

This invention provides the liquid crystal aligning agent which provides the liquid crystal aligning film for liquid crystal display elements with high reliability, regardless of process conditions, such as a film thickness and a rubbing condition.

The liquid crystal aligning agent of this invention is a liquid crystal aligning agent containing the imidation polymer of polyamic acid, The said imidation polymer is characterized by satisfy | filling all of the following conditions (a) and (b).

(A) For example, the unit represented by following formula (1a) has in the main chain of an imidation polymer.

<Formula 1a>

(B) For example, the main chain has an alkyl group having 8 or more carbon atoms in the side chain of the imidized polymer or a 1,1-cycloalkylene group having 6 or more carbon atoms in the heavy chain of the imidized polymer.

Liquid crystal display element, liquid crystal aligning film, liquid crystal aligning agent, imidation polymer

Description

Liquid crystal aligning agent and a liquid crystal display device {Liquid Crystal Aligning Agent and Liquid Crystal Display Device}

This invention relates to the liquid crystal aligning agent used for forming the liquid crystal aligning film of a liquid crystal display element. More specifically, it is related with the liquid crystal aligning agent which provides the liquid crystal aligning film which is excellent in applicability | paintability, has favorable liquid-crystal orientation, and brings the long-term stability excellent to a liquid crystal display element.

Currently, as a liquid crystal display element, a liquid crystal aligning film containing polyamic acid, polyimide, or the like is formed on the surface of a substrate on which a transparent conductive film is provided to form a substrate for a liquid crystal display element, and the two sheets thereof are disposed opposite to each other in the gap thereof. A so-called twisted nematic liquid crystal cell was formed by forming a nematic liquid crystal layer having dielectric anisotropy of ie, forming a sandwich cell, and causing the long axis of the liquid crystal molecules to be twisted 90 degrees continuously from one substrate to the other. The TN type liquid crystal display element which has is known.

Moreover, the STN (Super Twisted Nematic) type liquid crystal display element which has high contrast with respect to a TN type liquid crystal display element, and its visual dependence is developed. This STN type liquid crystal display element uses a mixture of nematic liquid crystals and a chiral agent, which is an optically active substance, as a liquid crystal, and the birefringence generated when the major axis of the liquid crystal molecules is continuously twisted over 180 degrees between the substrates. To use the effect.

In addition, a transverse electric field type liquid crystal display device is known in which two electrodes for driving a liquid crystal are disposed in a base like comb teeth on one side, and an electric field parallel to the base surface is generated to control the liquid crystal molecules. Orientation of the liquid crystal in these liquid crystal display elements is normally expressed by the liquid crystal aligning film in which the rubbing process was performed.

As a liquid crystal display element different from the above, the liquid crystal display element which has the vertical alignment liquid crystal cell formed by orienting the liquid crystal molecule which has negative dielectric anisotropy perpendicular to a board | substrate is known. Also in such a liquid crystal display element, the orientation control of a liquid crystal is normally performed by the liquid crystal aligning film formed by the liquid crystal aligning agent containing polymers, such as a polyamic acid and polyimide.

In recent years, it has been tried to replace the glass substrate conventionally used for the purpose of weight reduction of a liquid crystal display element into a resin substrate. Since a resin substrate is low in heat-humidity, it is necessary to perform the baking process at the time of forming a liquid crystal aligning film at low temperature, and the liquid crystal aligning agent containing soluble polyimide which does not require the thermal imidation reaction by baking process is preferable.

However, since soluble polyimide has lower affinity with a solvent than polyamic acid, irregular film thickness at the time of printing often causes coating defects, such as a pinhole. Therefore, development of the low-temperature baking liquid crystal aligning agent excellent in applicability | paintability is calculated | required.

 This invention is made | formed in view of the above circumstances, The 1st objective of this invention is providing the liquid crystal display element provided with the liquid crystal aligning film which has the liquid crystal aligning property which has the liquid crystal aligning property which the crystallinity of the liquid crystal molecule is reliably provided by the rubbing process. It is to provide the liquid crystal aligning agent which can be provided.

A second object of the present invention is to provide a liquid crystal aligning agent capable of constituting a liquid crystal display device having a liquid crystal aligning film having excellent coating properties.

A third object of the present invention is to provide a liquid crystal aligning agent capable of constituting a liquid crystal display device having excellent reliability.

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

The above objects and advantages of the present invention are firstly a liquid crystal aligning agent comprising an imidized polymer of polyamic acid, and the imidized polymer satisfies both of the following conditions (a) and (b). It is achieved by the liquid crystal aligning agent characterized by the above-mentioned.

(A) At least one of the units represented by the following general formulas (1) and (2) is present in the main chain of the imidized polymer.

In the formula, R ₁ to R ₆ each independently represent hydrogen, a halogen atom or a monovalent organic group, and p, q, and r each independently represent an integer of 1 to 20.

(B) It has at least 1 group selected from the group shown to each of following A-D in the main chain of an imidation polymer, or as a side chain.

A: an alkyl group having a main chain of 8 or more carbon atoms, a perfluoroalkyl group having a main chain of 3 or more carbon atoms, or a substituted, 1,1-cycloalkylene group having 6 or more carbon atoms,

B: a group having a polycyclic structure of at least 3 rings,

C: a group represented by -RXA ¹ , wherein R represents a hydrocarbon group of 3 or more carbon atoms, X represents a single bond, -O-, -CO-, -COO-, -OCO-, -NH-, -NHCO-, Represents a bonding group represented by -CONH- or -S-, and A ¹ represents a halogen atom, a cyano group, a fluoroalkyl group or a substitutable chromamanyl group),

D: a group represented by -R ¹ -X ¹ -R ² -X ² -R ³ , wherein R ¹ to R ³ each independently represent a hydrocarbon group having 3 or more carbon atoms,-(Si-O-) _n (n is an integer of 5 or more), X ¹ and X ² are each independently a single bond, -O-, -CO-, -COO-, -OCO-, -NH-, -NHCO-, -CONH- Or a bond group represented by -S-.

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 liquid crystal aligning agent of the present invention.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail. The imidized polymer used by this invention can be obtained by dehydrating and ring-closing the polyamic acid synthesize | combined by making tetracarboxylic dianhydride and a diamine compound react in an organic solvent. These polymers can also be used in mixture of 2 or more types.

In order to introduce a unit represented by each of the general formulas (1) and (2) represented by the condition (a) into the main chain of the imidized polymer, a diamine compound having a unit represented by each of the general formulas (1) and (2) in at least one diamine compound can be used. have.

The condition (a) improves the applicability of the liquid crystal aligning agent, improves the reliability and orientation of the liquid crystal display element, and has the effect of improving the electrical stability and display quality of the liquid crystal display element.

In addition, in order to introduce | transduce the group shown in any one of A-D shown by condition (b) in the main chain or as a side chain of an imidation polymer, in any one of A-D to at least one of tetracarboxylic dianhydride and a diamine compound. The compound which has group represented by one can be used. The condition (b) has an effect of expressing the pretilt angle in the liquid crystal display element.

In the imidized polymer used in the present invention, the content ratio of the group represented by the condition (a) is preferably 1 to 95 mol%, more preferably 5 to 50 mol%, particularly preferably based on the total repeating units of the whole polymer. Is 10 to 50 mol%. Although the content rate of the group represented by conditions (B) in the imidation polymer used by this invention changes with kinds of target liquid crystal display element, For example, in TN type, STN type, transverse electric field type liquid crystal display element, It is preferably 0.1 to 50 mol%, more preferably 0.1 to 20 mol%, particularly preferably 0.5 to 10 mol% with respect to the total repeating units of the polymer. Moreover, in a vertically-aligned liquid crystal display element, Preferably it is 5 to 80 mol%, More preferably, it is 5-50 mol%, Especially preferably, it is 5-30 mol%.

Preferably, the tetracarboxylic dianhydride represented by following formula (3) is used for manufacture of an imidation polymer as at least 1 part of tetracarboxylic dianhydride.

In formula, R is a tetravalent organic group which has an alicyclic structure.

The structure derived from the tetracarboxylic dianhydride represented by the formula (3) can be stored in a stable state by providing solvent solubility to the imidized polymer obtained by dehydrating and closing the unstable polyamic acid which is liable to change during storage in the solution phase. It has an effect. The content ratio of the structure derived from the compound represented by the formula (3) in the imidized polymer is preferably 0.1 to 50 mol%, more preferably 10 to 50 mol%, particularly preferably based on the total repeating units of the entire polymer. 30 to 50 mol%.

Tetracarboxylic dianhydride

As tetracarboxylic dianhydride which has group represented by conditions (b), the compound represented by following General formula (82)-(90) is mentioned, for example. By using such tetracarboxylic dianhydride, the group (a), (c), (e) and (g) described in Claim 2 can be introduce | transduced in the imidation polymer of this invention.

Examples of the tetracarboxylic dianhydride represented by the general formula (3) include 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurante tetracarboxylic acid. Dianhydrides, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1 , 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl- 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride , 3,3 ', 4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid Dianhydrides, 2,3,4,5-tetrahydrofurantetracarboxylic acid Aquatic, 1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3 -Dione, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c]- Furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1, 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl)- Naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-ethyl-5 (tetrahydro-2,5-dioxo-3 -Furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5 (tetrahydro-2,5 -Dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-ethyl-5 (tetra Hydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5, 8-dimethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 5- (2,5-di Oxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2,2,2] -octo-7-ene-2,3,5,6- Tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), (4arH, 8arH ) -Decahydro-1t, 4t: 5c, 8c-dimethonanaphthalene-2t, 3t, 6c, 7c-tetracarboxylic dianhydride.

Moreover, you may use other tetracarboxylic dianhydride other than tetracarboxylic dianhydride represented by General formula (3). Examples of such other tetracarboxylic dianhydrides include compounds represented by the following formulas (4a) and (4b), for example compounds represented by the following formulas (4c to 4e), pyromellitic dianhydrides, 3,3 ', 4 , 4'-benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylsulfontetracarboxylic dianhydride, 3,3', 4,4'-biphenylethertetracarboxylic acid Dianhydrides, 3,3 ', 4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3', 4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3, 4-furantetetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) di Phenylsulfon dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoroisopropylidenediphthalic dianhydride, bis ( Phthalic acid) phenylphosphine oxide dianhydride, p-phenylene- S (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylether 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 (anhydro trimellitate), 1,8-octanediol-bis (anhydro trimellitate), 2,2-bis (4-hydroxyphenyl) propane-bis (anhydro trimellitate Aromatic tetracarboxylic dianhydrides such as tate). These are used individually by 1 type or in combination of 2 or more types.                     

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

[Diamine Compound]

As a diamine compound which has group represented by condition (a) among the diamine compounds used for the synthesis | combination of a polyamic acid, For example, bisaminopropyl tetramethyl disiloxane, 4,4'- oxydianiline, 3,4 ' -Oxydianiline, 1,4-bis (aminophenoxy) benzene, bis (4- (4-aminophenoxy) phenyl) ether and the like.

By using the said diamine compound, the group represented by the said Formula (1) or (2) can be introduce | transduced in the imidation polymer.

Moreover, the diamine compound represented by each of General formula (3)-(81) of Claim 3 can be mentioned as a diamine compound which has group represented by conditions (b). In the imidized polymer by using the diamine compounds represented by the formulas (3) to (81), respectively, in the formulas (b), (d), (f), (h), and (o) to (z) The group represented by either can be introduce | transduced.

In the present invention, other diamine compounds may be used in addition to the diamine compounds having the specific structure as described above. As another diamine compound, p-phenylenediamine, m-phenylenediamine, 4,4'- diamino diphenylmethane, 4,4'- diamino diphenylethane, 4,4'- diamino, for example Diphenylsulfide, 4,4'-diaminodiphenylsulfone, 4,4'-diaminobenzanilide, 5-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 6 -Amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzo Phenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) 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, 4,4'-methylene-bis (2-chloroaniline), 1,4,4 '-(p-phenyleneisopropylidene) bisaniline, 4,4' -(m-phenyleneisopropylidene) bisaniline, 2,2'-dimethyl-4,4'-diamino ratio Carbonyl, aromatic diamines such as 2,2'-tree-4,4'-diamino-biphenyl-fluoro;

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

2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyrazine, 5, 6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis (3-aminopropyl) piperazine, 2,4-diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino- 6-phenyl-1,3,5-triazine, 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-triazine, 4,6-dia Mino-2-vinyl-s-triazine, 2,4-diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5- Diamino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridine lactate, 3,8-diamino-6-phenylphenanthtridine, 1,4-diaminopiperazine, 2 in the molecule, such as 3,6-diaminoacridine, bis (4-aminophenyl) phenylamine, and the compound represented by the following formulas (5a to 5b): And diamines having nitrogen atoms other than the primary amino group and the primary amino group, and mono-substituted phenylenediamines represented by the following general formula (5c).

In the formula, R ⁵ represents a divalent organic group, and R ⁶ represents a monovalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine, and piperazine.

In the formula, R ⁷ represents a divalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and pepperazine, R ⁸ represents a divalent organic group, and a plurality of R ⁸ may be the same or different.

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

Synthesis of Polyamic Acid

The use ratio of tetracarboxylic dianhydride and diamine provided in the synthesis reaction of a polyamic acid has the preferable ratio that the acid anhydride group of tetracarboxylic dianhydride is 0.2-2 equivalent with respect to 1 equivalent of the amino group of a diamine, Furthermore, Preferably it is the ratio used as 0.3 to 1.2 equivalent.

Synthesis reaction of polyamic acid is performed in organic solvent, Preferably it is -20-150 degreeC, More preferably, it is carried out under the temperature conditions of 0-100 degreeC.

The organic solvent is not particularly limited as long as it can dissolve the polyamic acid synthesized, for example 1-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl Aprotic polar solvents such as sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide; and phenol solvents such as m-cresol, xylenol, phenol and halogenated phenol. Moreover, it is preferable that the usage-amount ((alpha)) of an organic solvent is an amount which normally makes the total amount (beta) of tetracarboxylic dianhydride and a diamine compound become 0.1-30 weight% with respect to the total amount ((alpha) + (beta)) of a reaction solution. .

In the organic solvent, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like, which are poor solvents of polyamic acid, can be used together in a range in which the resulting polyamic acid is not precipitated. As a specific example of such a poor solvent, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, 4-hydroxy-4-methyl-2-pentanol, 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 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- Butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Col monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane And 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 polyamic acid can be obtained by drying the precipitate under reduced pressure. In addition, the polyamic acid can be purified by dissolving the polyamic acid again in an organic solvent and then precipitating with a poor solvent once or plural times.

[Synthesis of imidized polymer]

The imidation polymer which comprises the liquid crystal aligning agent of this invention can be synthesize | combined by dehydrating and ring-closing the said polyamic acid. Dehydration ring closure of polyamic acid is carried out by the method of heating (I) polyamic acid, or (II) polyamic acid is dissolved in an organic solvent, and a dehydrating agent and a dehydration ring closure catalyst are added to this solution, and it heats as needed. It is done by the method.

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

On the other hand, in the method of adding a dehydrating agent and a dehydrating ring-closure catalyst to the solution of the polyamic acid of said (II), acid anhydrides, such as an acetic anhydride, a propionic anhydride, a trifluoroacetic anhydride, can be used as a dehydrating agent, for example. . Although the usage-amount of a dehydrating agent changes with a desired imidation ratio, it is preferable to set it as 0.01-20 mol with respect to 1 mol of repeating units of a polyamic acid. As the dehydration ring closure catalyst, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used, for example. However, it is not limited to 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 increased as the usage-amount of said dehydrating agent and dehydrating ring closure agent increases. The imidation ratio (the rate of change of the amic acid unit to the imide unit) is preferably 40% or more from the viewpoint of the residual image erasing rate of the liquid crystal display element. Moreover, as an organic solvent used for dehydration ring-closure reaction, the organic solvent illustrated to be used for the synthesis | combination of a polyamic acid is mentioned. And the reaction temperature of dehydration ring-closure reaction becomes like this. Preferably it is 0-180 degreeC, More preferably, it is 10-150 degreeC. Moreover, the imidation polymer can be refine | purified by performing the same operation as the purification method of polyamic acid with respect to the reaction solution obtained in this way.

[Terminal modified polymer]

The polyamic acid and the imidized polymer used in the present invention may be of terminally modified form with controlled molecular weight. By using this terminal modified polymer, the coating characteristic of a liquid crystal aligning agent, etc. can be improved, without degrading the effect of this invention. Such a terminally modified polymer can be synthesized by adding monofunctional compounds such as an acid anhydride, a monoamine compound, a monoisocyanate compound and the like to the reaction system when synthesizing the polyamic acid. Examples of the acid anhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride, n-hexadecylsuccinic anhydride, and the like. have. As the monoamine compound, for example, aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decyl Amines, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-eicosylamine etc. are mentioned. Moreover, as a monoisocyanate compound, phenyl isocyanate, naphthyl isocyanate, etc. are mentioned, for example.

[Logarithmic Viscosity of Polymer]

As for the polyamic acid and imidation polymer obtained as mentioned above, the value of the logarithmic viscosity ((eta) _ln ) becomes like this. Preferably it is 0.05-10 dl / g, More preferably, it is 0.05-5 dl / g.

The value of the logarithmic viscosity (η _ln ) is measured by using a N-methyl-2-pyrrolidone as a solvent and measuring the viscosity at 30 ° C with respect to a solution having a concentration of 0.5 g / 100 ml. Is obtained by

[Liquid crystal aligning agent]

The liquid crystal aligning agent of this invention is comprised by melt | dissolving and containing the said polyamic acid and / or the imidation polymer normally in an organic solvent.

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

As said organic solvent, for example, 1-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide, N, N-dimethylacetamide, 4-hydrate Roxy-4-methyl-2-pentanol, 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 And diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate and the like.

Although solid content concentration in the liquid crystal aligning agent of this invention is selected in consideration of viscosity, volatility, etc., Preferably it is the range of 1 to 10 weight%. That is, although the liquid crystal aligning agent of this invention is apply | coated to the 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%, since the film thickness of this coating film becomes too thin, a favorable liquid crystal aligning film cannot be obtained and solid content concentration is carried out. When the content exceeds 10% by weight, the film thickness of the coating film becomes too thick, so that a good liquid crystal aligning film cannot be obtained, and the viscosity of the liquid crystal aligning agent is increased, resulting in poor coating properties.

The liquid crystal aligning agent of this invention may contain the functional silane containing compound or an epoxy compound from a viewpoint of improving the adhesiveness to the surface of a board | substrate within the range which does not impair the target physical property. As such a functional silane containing compound, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 2-aminopropyl trimethoxysilane, 2-aminopropyl triethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltree Ethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, 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-aminopropyltrimethoxysilane, N-benzyl -3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimeth Oxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, etc. are mentioned. Examples of such epoxy compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether. , Neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5 , 6-tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylamino Methyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 3- (N-allyl-N-glycidyl) aminopropyltrimethoxysilane And 3- (N, N-diglycidyl) aminopropyltrimethoxysilane.

[Liquid Crystal Display Element]

The liquid crystal display element of this invention can be manufactured by the following method, 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 methods, such as a roll coater method, a spinner method, and a printing method, and then a coating film is formed by heating a coating surface. do. As a board | substrate, For example, glass, such as float glass and a soda glass; A transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone and polycarbonate can be used. As a transparent conductive film provided on one side of the substrate, an NESA film containing tin oxide (SnO ₂ ) (registered trademark of PPG Co., Ltd.) and an ITO film containing indium tin oxide (In ₂ O ₃ -SnO ₂ ) Etc. can be used. The photoetching method and the method of using a mask beforehand are used for patterning of these transparent conductive films. When apply | coating a liquid crystal aligning agent, in order to make the 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. In addition, although the liquid crystal aligning agent of this invention containing a polyamic acid forms the coating film which becomes an oriented film by removing an organic solvent after application | coating, further heating can advance dehydration ring closure, and can also form more imidized coating film. 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) A rubbing treatment is performed in which the formed coating film surface is rubbed in a predetermined direction with a roll wound around a cloth made of fibers 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.

In addition, as disclosed in Japanese Patent Application Laid-Open No. 6-222366 or Japanese Patent Application Laid-Open No. 6-281937 in the liquid crystal alignment film formed by the liquid crystal aligning agent of the present invention, infrared rays A treatment such as changing the pretilt angle by partially irradiating, or as shown in Japanese Patent Laid-Open No. Hei 5-107544, partially forms a resist film on the surface of the liquid crystal alignment film subjected to the rubbing treatment, and the rubbing treatment. It is possible to improve the field of view characteristics of the liquid crystal display element by performing a process such as changing the liquid crystal alignment ability of the liquid crystal aligning film by removing the resist film after performing the rubbing treatment in a different direction.

(3) As described above, each of the substrates on which the liquid crystal alignment film was formed and the non-patterned substrates of the transparent conductive film were prepared one by one, and the two substrates were spaced so that the rubbing directions were perpendicular or antiparallel to each liquid crystal alignment film. The cell gaps are disposed to face each other, and two substrate peripheral portions are bonded with a sealant to inject and fill the liquid crystal 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 is bonded to the outer surface of the liquid crystal cell, ie, the other surface side of each board | substrate which comprises a liquid crystal cell, by bonding a polarizing plate so that the polarization direction may coincide or orthogonally cross with the rubbing direction of the liquid crystal aligning film formed in one side of the said board | substrate. Can be obtained.

Here, as the sealant, for example, an epoxy resin or the like containing an aluminum oxide sphere as a curing agent and a spacer can be used.

Examples of the liquid crystal include nematic liquid crystals and smectic liquid crystals, and among them, nematic liquid crystals are preferable, and for example, a sieve base liquid crystal, a subfamily clock liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal and an ester type A liquid crystal, 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. As these liquid crystals, for example, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonaate, cholesteryl carbonate, and trade names "C-15" and "CB-15" (manufactured by Merck) The chiral agent etc. which are sold can also be added and used. Furthermore, ferroelectric liquid crystals such as p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate can also be used.

Moreover, as a polarizing plate bonded to the outer surface of a liquid crystal cell, the polarizing plate which consists of a polarizing plate called H film which absorbed iodine, and extended | stretched polyvinyl alcohol between the cellulose acetate protective film, or the polarizing plate which consists of H film itself is mentioned. .                     

<Example>

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not restrict | limited to these Examples. The evaluation method of each liquid crystal display element produced by the following example and the comparative example is shown below.

[Average imidation ratio of the imidation ratio and liquid crystal aligning agent of a polymer]

After drying a polymer or a liquid crystal aligning agent at room temperature under reduced pressure, it was dissolved in deuterated dimethyl sulfoxide, ¹ H-NMR was measured at room temperature using tetramethylsilane as a reference material, and it calculated | required by following formula (2).

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

A ¹ : peak area (10 ppm) derived from proton of NH group

A ² : peak area derived from other protons

α: ratio of the number of other protons to one proton of the NH group in the precursor (polyamic acid) of the polymer

[Solubility of imidized polymer and liquid crystal aligning agent]

The polymer or liquid crystal aligning agent was dried under reduced pressure at room temperature, and then shaken and dissolved in γ-butyrolactone at room temperature for 1 hour so as to have a solid concentration of 10% by weight solution. OK and the thing which remained without melt | dissolution were called NG.

[Printability Test of Imidized Polymer / Liquid Crystal Alignment Agent]

The polymer or liquid crystal aligning agent is dissolved in a γ-butyrolactone / N-methylpyrrolidone / butyl cellosolve (77/3/20 (weight ratio)) mixed solvent, made into a solution having a solid concentration of 4% by weight, and The solution was filtered using a filter having a pore size of 1 μm to prepare a liquid crystal aligning agent of the present invention. The said liquid crystal aligning agent was apply | coated to the transparent electrode surface of the glass substrate with which the transparent electrode containing an ITO film | membrane was mounted using the liquid crystal aligning film printer (made by Nippon Sashing Insatsuki Co., Ltd.), and after drying for 1 minute on 80 degreeC hotplate, 180 degreeC It dried on the photoplate for 20 minutes, and formed the film of average film thickness of 600 kPa. This board | substrate was observed under the microscope of 20 times the magnification, and the printability good and defective were determined by the printing irregularity and the presence or absence of the pinhole.

[Reliability Test of Liquid Crystal Display Device]

Under high temperature and high humidity environment (temperature 70 ° C, relative humidity 80%), the liquid crystal display device is driven by a square wave of 5 V and 60 Hz, and after 1,500 hours, the presence of a white speckle-shaped display defect is observed with a polarizing microscope. It was.

[Voltage retention rate of liquid crystal display element]

After applying a voltage of 5 V to the liquid crystal display element with an application time of 60 microseconds and a span of 167 milliseconds, the voltage retention after 167 milliseconds from the release of the application was measured. As a measuring apparatus, Toyo Technical Co., Ltd. VHR-1 was used.

<Synthesis Examples 1 to 9 and Comparative Synthesis Examples 1 to 2>                     

N-methyl-2-pyrrolidone was added to the composition shown in Table 1 in the order of diamine and tetracarboxylic dianhydride (denoted as "acid anhydride" in the table) to give a solution having a solid concentration of 15% by weight. The mixture was reacted at 60 ° C for 6 hours to obtain a polyamic acid having a logarithmic viscosity shown in Table 1. 5 mol% of pyridine and 3 mol% of acetic anhydride were added with respect to the total amount of the tetracarboxylic dianhydride and diamine used for the obtained polyamic acid, and it heated at 110 degreeC, and carried out dehydration ring-closure reaction for 4 hours. After the obtained solution was reprecipitated with diethyl ether, it was collect | recovered and dried, and the imidation polymer B1-B9, b1, b2 of the logarithmic viscosity and imidation ratio shown in Table 1 were obtained.                     

In Table 1, the diamine compound and tetracarboxylic dianhydride are as follows.

<Diamine Compound>

D-1: p-phenylenediamine

D-2: bisaminopropyltetramethyldisiloxane

D-3: 4,4'-oxydianiline                     

D-4: 1,4-bis (aminophenoxy) benzene

D-5: bis (4- (4-aminophenoxy) phenyl) ether

D-6: diamine represented by the above formula (13)

D-7: 4,4'-methylenedianiline

D-8: diamine represented by the formula (15)

D-9: diamine represented by the above formula (21)

D-10: 2,2'-dimethyl-4,4'-diaminobiphenyl

Tetracarboxylic dianhydride

T-1: 2,3,5-tricarboxycyclopentyl acetic dianhydride

T-2: pyromellitic dianhydride

<Example 1>

2 g of the imidized polymer (B1) obtained in Synthesis Example 1 was dissolved in γ-butyrolactone to give a solution having a solid content of 4% by weight, and the solution was filtered through a filter having a pore size of 1 μm to obtain a liquid crystal aligning agent of the present invention. Prepared.

The liquid crystal aligning agent was applied to a transparent electrode surface of a glass substrate equipped with a transparent electrode including an ITO film by using a printing machine for coating a liquid crystal alignment film, and dried on a hot plate at 180 ° C. for 20 minutes to form a coating film having a dry film thickness of 0.05 μm. It formed and evaluated the printability good and defect.

The rubbing process was performed by the rubbing machine which has the roll which wound the cloth made from rayon to this coating film by roll rotation speed 500rpm, the movement speed of a stage 1cm / sec, and the length of 0.4 mm which a hair tip enters.

Subsequently, after screen-printing apply | coating the epoxy resin adhesive in which the aluminum oxide sphere of diameter 17micrometer was inserted in each outer edge which has the liquid crystal aligning film of a pair of the liquid-crystal aligning substrate which was rubbed-processed, a pair of liquid crystal aligning substrate was carried out The adhesive was cured by overlapping and compressing so that the faces faced and the rubbing direction was antiparallel.

Subsequently, after filling a nematic liquid crystal (MLC-5081 by Merck Co., Ltd.) between a pair of board | substrates with a liquid crystal injection hole, the liquid crystal injection hole is sealed with an epoxy adhesive, and a polarizing plate is carried out on the outer both sides of a board | substrate of a polarizing plate. The polarization direction was opposed so that it might correspond with the rubbing direction of the liquid crystal aligning film of each board | substrate, and the liquid crystal display element of this invention was produced.

The reliability and voltage retention of the obtained liquid crystal display element were evaluated. The evaluation results along with the printability test results are shown in Table 2 below.

<Examples 2 to 9, Comparative Example 1>

Except having used the polymer shown in Table 1, the liquid crystal aligning agent was produced like Example 1, the liquid crystal display element was produced and evaluated using this. The evaluation results are shown in Table 2.                     

According to the liquid crystal aligning agent of this invention, when it is set as a liquid crystal aligning film, the liquid crystal aligning film suitable for highly reliable liquid crystal display elements is obtained, regardless of process conditions, such as a film thickness and rubbing conditions.

Moreover, the liquid crystal display element which has the alignment film formed using the liquid crystal aligning agent of this invention is excellent in the orientation and reliability of a liquid crystal, and can be effectively used for various apparatuses, for example, a desk calculator, a wristwatch, a table clock, a coefficient It is used for display devices, such as a display panel, a mobile telephone, a word processor, a personal computer, a liquid crystal data projector, and a liquid crystal television.

Claims (7)

It is a liquid crystal aligning agent containing the imidation polymer of polyamic acid, and the said imidation polymer satisfy | fills all of the following conditions (a) and (b), The liquid crystal aligning agent characterized by the above-mentioned. (A) At least one of the units represented by the following general formulas (1) and (2) is present in the main chain of the imidized polymer. <Formula 1>

<Formula 2>

(In formula, R <_1> -R <_6> respectively independently represents a hydrogen, a halogen atom, or monovalent organic group, and p, q, r each independently represents the integer of 1-20.) (B) It has at least 1 group selected from the group shown to each of following A-D in the main chain of an imidation polymer, or as a side chain. A: an alkyl group having a main chain of 8 or more carbon atoms, a perfluoroalkyl group having a main chain of 3 or more carbon atoms, or a substituted, 1,1-cycloalkylene group having 6 or more carbon atoms, B: a group having a polycyclic structure of at least 3 rings, C: a group represented by -RXA ¹ , wherein R represents a hydrocarbon group of 3 or more carbon atoms, X represents a single bond, -O-, -CO-, -COO-, -OCO-, -NH-, -NHCO-, Represents a bonding group represented by -CONH- or -S-, and A ¹ represents a halogen atom, a cyano group, a fluoroalkyl group or a substitutable chromamanyl group), D: a group represented by -R ¹ -X ¹ -R ² -X ² -R ³ , wherein R ¹ to R ³ each independently represent a hydrocarbon group having 3 or more carbon atoms,-(Si-O-) _n (n is an integer of 5 or more), X ¹ and X ² are each independently a single bond, -O-, -CO-, -COO-, -OCO-, -NH-, -NHCO-, -CONH- Or a bond group represented by -S-. The liquid crystal aligning agent of Claim 1 whose group represented by conditions (b) is 1 or more types chosen from group represented by following General formula (a)-(z).

Wherein A is a phenylene group or a single bond, and X, Y and P are each independently -O-, -CO-, -COO-, -OCO-, -NHCO-, -CONH-, -S-,- Ar-Ar-CH _2- (where Ar is a phenylene group), a methylene group, a divalent group selected from an alkylene group having 2 to 6 carbon atoms, and a phenylene group, Z is -CF ₃ , -CN, -COCH ₃ , -COOH, -NO ₂ , -SOCH ₃ , -SO ₂ CH ₃ , -F, -Cl, is a monovalent organic group selected from -OCF ₃ , R ¹ to R ⁹ , R ¹¹ to R ¹⁹ , R ²¹ , R ²³ , R ²⁴ , R ²⁵ , R ²⁷ to R ³³ each independently represent a halogen atom or a monovalent organic group, R ²⁰ , R ²² , and R ²⁶ are divalent organic groups, and R ¹⁰ is a trivalent oil. Q is an alkyl group having 6 to 16 carbon atoms, and m and n are each an integer of 1 or more. The liquid crystal aligning agent of Claim 1 in which group represented by conditions (b) originates in 1 or more types chosen from the diamine compound represented by following General formula (3)-(81).

In formula, y is an integer of 2-12 and z is an integer of 1-5. The liquid crystal aligning agent of Claim 1 in which group represented by condition (b) originates in 1 or more types chosen from tetracarboxylic dianhydride represented by following General formula (82)-(90).

The imidized polymer of the polyamic acid of any one of Claims 1-4 obtained using 0.1-50 mol% of tetracarboxylic dianhydride represented by following General formula (3) with respect to all the repeating units of all the polymers. Liquid crystal aligning agent containing. <Formula 3>

In formula, R is a tetravalent organic group which has an alicyclic structure. The liquid crystal aligning agent of Claim 5 whose tetracarboxylic dianhydride represented by the said General formula (3) is 2,3,5- tricarboxycyclopentyl acetic dianhydride. It comprises the liquid crystal aligning film obtained from the liquid crystal aligning agent in any one of Claims 1-4, The liquid crystal display element characterized by the above-mentioned.