CN109971494B - Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

The invention relates to a liquid crystal aligning agent, a liquid crystal alignment film and a liquid crystal display element. The present invention provides a liquid crystal display element which can suitably exhibit various properties in a well-balanced manner by including a polymer (P) having a partial structure represented by the following formula (1) in a liquid crystal aligning agent.

(in the formula (1), R ¹ Is a tetravalent organic radical, R ² Is a divalent organic radical; x ¹ And X ² Each independently represents a hydroxyl group or a monovalent organic group having 1 to 40 carbon atoms; wherein X ¹ And X ² At least any one of the following monovalent organic groups: the monovalent organic group has one selected from the group consisting of an aromatic amine structure in which two or more aromatic rings are directly bonded to a nitrogen atom, a heterocyclic group, a polymerizable group, and a photo-rearrangeable group).

Description

Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element

Divisional patent application

This patent application is a divisional application of an invention patent application entitled "liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element" having application number 201510530411.6, and the filing date of the original application is 26/08/2015.

Technical Field

The invention relates to a liquid crystal aligning agent, a liquid crystal alignment film and a liquid crystal display element.

Background

Conventionally, various driving methods such as a Twisted Nematic (TN) type, a Super Twisted Nematic (STN) type, a Vertical Alignment (VA) type, an In-Plane Switching (IPS) type, and a Fringe Field Switching (FFS) type have been developed for liquid crystal display elements, which have different electrode structures, physical properties of liquid crystal molecules used, and manufacturing steps. These liquid crystal display elements have a liquid crystal alignment film for aligning liquid crystal molecules. Polyamic acid or polyimide is generally used as a material of the liquid crystal alignment film in terms of good properties such as heat resistance, mechanical strength, and affinity for liquid crystal.

In recent years, liquid crystal aligning agents using a polyamic acid ester as at least a part of the polymer component have been proposed (for example, see patent document 1). Patent document 1 discloses: the polyamic acid ester and the polyamic acid are contained in the liquid crystal aligning agent as polymer components, and the weight average molecular weight of the polyamic acid ester is smaller than that of the polyamic acid. According to the liquid crystal aligning agent described in patent document 1, patent document 1 describes the following: the fine irregularities generated on the film surface of the liquid crystal alignment film are reduced, and the liquid crystal alignment properties and the electrical characteristics of the liquid crystal display element are improved.

[ Prior art documents ]

[ patent document ]

[ patent document 1] International publication No. 2011/115078

Disclosure of Invention

[ problems to be solved by the invention ]

In recent years, liquid crystal televisions with large screens and high definition have become the main units, and small display terminals such as smart phones and tablet PCs have been widely used, and the demand for high definition of liquid crystal panels has been further increased. In addition, with the recent trend toward more versatile liquid crystal display elements, the liquid crystal display elements are expected to be used under more severe conditions. Therefore, the liquid crystal display element preferably exhibits various desired characteristics in a well-balanced manner.

An object of the present invention is to provide a liquid crystal aligning agent which can obtain a liquid crystal display element capable of suitably exhibiting various characteristics in a well-balanced manner.

[ means for solving problems ]

The present inventors have conducted intensive studies to solve the above-mentioned problems of the prior art, and have found that the problems can be solved by introducing a functional group into the carboxyl group of the amic acid structure. Specifically, the following liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element are provided.

An aspect of the present disclosure is to provide a liquid crystal alignment agent containing a polymer (P) having a partial structure represented by formula (1) below.

[ solution 1]

(in the formula (1), R ¹ Is a tetravalent organic radical, R ² Is a divalent organic radical; x ¹ And X ² Each independently represents a hydroxyl group or a monovalent organic group having 1 to 40 carbon atoms; wherein, X ¹ And X ² At least any one of the following monovalent organic groups: the monovalent organic group has one selected from the group consisting of an aromatic amine structure in which two or more aromatic rings are directly bonded to a nitrogen atom, a heterocyclic group, a polymerizable group, and a light-rearranging group)

In addition, another aspect is to provide a liquid crystal alignment film formed using the liquid crystal aligning agent. In addition, a liquid crystal display element including the liquid crystal alignment film is provided.

[ Effect of the invention ]

By incorporating the polymer (P) having a specific partial structure in at least a part of the polymer component of the liquid crystal aligning agent, a liquid crystal display element which can exhibit various properties in a well-balanced manner can be obtained.

Drawings

Fig. 1 is a schematic configuration diagram of an FFS type liquid crystal cell.

Fig. 2 (a) and 2 (b) are schematic plan views of top electrodes used for manufacturing a liquid crystal display element by rubbing treatment. Fig. 2 (a) is a plan view of the top electrode, and fig. 2 (b) is a partially enlarged view of the top electrode.

Fig. 3 is a diagram showing a driving electrode of the system.

Fig. 4 (a) and 4 (b) are schematic plan views of top electrodes used in the production of liquid crystal display elements by photoalignment. Fig. 4 (a) is a plan view of the top electrode, and fig. 4 (b) is a partially enlarged view of the top electrode.

[ description of symbols ]

10: liquid crystal display element

11a, 11 b: glass substrate

12: liquid crystal alignment film

13: top electrode

14: insulating layer

15: bottom electrode

16: liquid crystal layer

d 1: line width of electrode

d 2: distance between electrodes

A. B, C, D, E: electrode for electrochemical cell

F: pixel edge portion

Detailed Description

Hereinafter, components to be blended in the liquid crystal aligning agent of the present disclosure and other components optionally blended as necessary will be described.

< Polymer (P) >

The liquid crystal aligning agent of the present disclosure contains a polymer (P) having a partial structure represented by the following formula (1).

[ solution 2]

(in the formula (1), R ¹ Is a tetravalent organic radical, R ² Is a divalent organic radical; x ¹ And X ² Each independently represents a hydroxyl group or a monovalent organic group having 1 to 40 carbon atoms; wherein X ¹ And X ² At least any one of the following monovalent organic groups: having an aromatic amine structure, hetero atom, selected from the group consisting of two or more aromatic rings directly bonded to a nitrogen atomOne of the group consisting of a ring group, a polymerizable group and a photo-rearranging group)

In the formula (1), X ¹ And X ² Examples of the monovalent organic group having 1 to 40 carbon atoms include: a C1-C40 monovalent hydrocarbon group; to methylene groups of hydrocarbon radicals by-O-, -S-, -CO-, -COO-, -COS-, -NR ³ -、-CO-NR ³ -、-Si(R ³ ) ₂ - (wherein, R) ³ Hydrogen atom or C1-12 monovalent hydrocarbon group), -N ═ N-, -SO) ₂ A monovalent group formed by substitution, etc.; a monovalent group obtained by substituting at least one of the hydrogen atoms bonded to carbon atoms of the monovalent group and the hydrocarbon group with a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), a hydroxyl group, an alkoxy group, a nitro group, an amino group, a mercapto group, a nitroso group, an alkylsilyl group, an alkoxysilyl group, a silanol group, a sulfinic acid group, a phosphino group, a carboxyl group, a cyano group, a sulfo group, an acyl group, or the like; monovalent group having a heterocyclic ring, and the like. Wherein, X ¹ And X ² At least any one of the following monovalent organic groups: the monovalent organic group has one functional group selected from the group consisting of an aromatic amine structure in which two or more aromatic rings are directly bonded to a nitrogen atom (hereinafter also referred to as a "specific aromatic amine structure"), a heterocyclic group, a polymerizable group, and a light-rearranging group.

Here, the term "hydrocarbon group" in the present specification means a chain hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group. The "chain hydrocarbon group" refers to a straight-chain hydrocarbon group and a branched hydrocarbon group that are composed of only a chain structure, without including a cyclic structure in the main chain. Among them, they may be saturated or unsaturated. The "alicyclic hydrocarbon group" refers to a hydrocarbon group containing only an alicyclic hydrocarbon structure as a ring structure and not an aromatic ring structure. Among them, the alicyclic hydrocarbon does not necessarily have to be constituted by only the structure of the alicyclic hydrocarbon, and a hydrocarbon group having a chain structure in a part thereof is also included. The "aromatic hydrocarbon group" refers to a hydrocarbon group containing an aromatic ring structure as a ring structure. Among them, it is not always necessary to constitute only an aromatic ring structure, and a chain structure or an alicyclic hydrocarbon structure may be included in a part thereof.

The polymer (P) can be synthesized by appropriately combining the conventional methods of organic chemistry. Examples of the synthesis method include the following methods: a tetracarboxylic acid dianhydride is reacted with a compound (E) having the functional group to synthesize a tetracarboxylic acid diester having the functional group, and then the resulting tetracarboxylic acid diester is reacted with a diamine.

In the present specification, the term "tetracarboxylic acid diester" refers to a compound in which two of the four carboxyl groups of a tetracarboxylic acid are esterified. By "tetracarboxylic acid diester dihalide" is meant a compound in which two of the four carboxyl groups possessed by a tetracarboxylic acid are esterified and the remaining two are halogenated.

[ tetracarboxylic dianhydride ]

Examples of the tetracarboxylic dianhydride used for synthesizing the polymer (P) include aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, and aromatic tetracarboxylic dianhydrides. Specific examples of the tetracarboxylic acid dianhydride include the following aliphatic tetracarboxylic acid dianhydrides: butane tetracarboxylic dianhydride, and the like;

examples of the alicyclic tetracarboxylic dianhydride include: 1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 2,3, 5-tricarboxylic cyclopentylacetic dianhydride, 5- (2, 5-dioxotetrahydrofuran-3-yl) -3a,4,5,9 b-tetrahydronaphtho [1,2-c ]]Furan-1, 3-dione, 5- (2, 5-dioxotetrahydrofuran-3-yl) -8-methyl-3 a,4,5,9 b-tetrahydronaphtho [1,2-c ]]Furan-1, 3-dione, 3-oxabicyclo [3.2.1]Octane-2, 4-dione-6-spiro-3 ' - (tetrahydrofuran-2 ',5' -dione), 5- (2, 5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, 3,5, 6-tricarboxyl-2-carboxymethylnorbornane-2: 3,5: 6-dianhydride, bicyclo [3.3.0]]Octane-2, 4,6, 8-tetracarboxylic acid 2:4,6: 8-dianhydride, bicyclo [2.2.1]Heptane-2, 3,5, 6-tetracarboxylic acid 2:3,5: 6-dianhydride, 4, 9-dioxatricyclo [5.3.1.0 ^2,6 ]Undecane-3, 5,8, 10-tetraone, 1,2,4, 5-cyclohexanetetracarboxylic dianhydride, bicyclo [2.2.2] benzene]Oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, ethylenediaminetetraacetic dianhydride, cyclopentanetetracarboxylic dianhydride, and the like;

examples of the aromatic tetracarboxylic dianhydride include: pyromellitic dianhydride, ethylene glycol bis (trimellitic anhydride ester), 1, 3-propanediol bis (trimellitic anhydride ester), and the like; in addition to this, Japanese patent can be usedA tetracarboxylic dianhydride described in JP-A2010-97188. The tetracarboxylic dianhydride used in the synthesis of the polymer (P) may be one of these compounds used alone or two or more of them used in combination. Further, R in the formula (1) ¹ Is a tetravalent group derived from a tetracarboxylic dianhydride, i.e., a residue obtained by removing two acid anhydride groups from a tetracarboxylic dianhydride.

Among these compounds, the tetracarboxylic dianhydride preferably comprises a dianhydride selected from the group consisting of bicyclo [2.2.1] heptane-2, 3,5, 6-tetracarboxylic acid 2:3,5: 6-dianhydride, 1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 2,3, 5-tricarboxycyclopentylacetic acid dianhydride, 5- (2, 5-dioxotetrahydrofuran-3-yl) -3a,4,5,9 b-tetrahydronaphtho [1,2-c ] furan-1, 3-dione, 5- (2, 5-dioxotetrahydrofuran-3-yl) -8-methyl-3 a,4,5,9 b-tetrahydronaphtho [1,2-c ] furan-1, 3-dione, bicyclo [3.3.0] octane-2, 4,6, at least one compound selected from the group consisting of 8-tetracarboxylic acid 2:4,6: 8-dianhydride, cyclohexanetetracarboxylic acid dianhydride, and pyromellitic acid dianhydride. The amount of these preferred compounds to be used (the total amount thereof in the case of using two or more kinds thereof) is preferably 5 mol% or more, more preferably 10 mol% or more, and still more preferably 20 mol% or more, based on the total amount of tetracarboxylic dianhydrides used for synthesizing the polymer (P).

[ Compound (E) ]

(Compound having a specific aromatic amine Structure)

When the compound (E) is a compound having a specific aromatic amine structure (hereinafter also referred to as "compound (E-1)"), examples of the aromatic ring directly bonded to the nitrogen atom in the specific aromatic amine structure include: benzene rings, naphthalene rings, anthracene rings, and the like. Preferably a benzene ring. Preferable specific examples of the specific aromatic amine structure include a group represented by the following formula (2-1) and a group represented by the following formula (2-2).

[ solution 3]

(formula (2-1) and formula (2-2) wherein R ⁵ Is a hydrogen atom or a monovalent hydrocarbon group; r ⁶ And R ⁷ Each independently is a monovalent substituent; d is an integer of 0 to 4, and e and f are each independently an integer of 0 to 5; "+" indicates a bond)

In the formula (2-1), R ⁵ Examples of the monovalent hydrocarbon group include: linear or branched alkyl groups such as methyl, ethyl, propyl, butyl, pentyl and hexyl, cyclohexyl, phenyl and methylphenyl, and the like. In the liquid crystal display element, R is a high-level property for improving the residual image characteristics (particularly, residual image characteristics called "DC residual image" due to residual charges accumulated by application of a DC voltage) ⁵ Preferably a hydrogen atom, a methyl group or a phenyl group, more preferably a hydrogen atom.

R ⁶ And R ⁷ Examples of the monovalent substituent(s) include: halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, aryl group having 5 to 20 carbon atoms (phenyl group, tolyl group, etc.), nitro group, hydroxyl group, amino group, mercapto group, nitroso group, alkylsilyl group, alkoxysilyl group, silanol group, sulfinic acid group, phosphino group, carboxyl group, cyano group, sulfo group, acyl group, etc.

d. e and f are preferably 0 or 1.

Examples of the compound (E-1) include compounds represented by the following formula (3-1).

[ solution 4]

A ¹ -R ¹¹ -OH (3-1)

(in the formula (3-1), A ¹ Is a group represented by the formula (2-1) or a group represented by the formula (2-2), R ¹¹ Is a single bond or a divalent hydrocarbon group)

In the formula (3-1), R ¹¹ Examples of the divalent hydrocarbon group of (2) include a chain hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group. Specific examples of the hydrocarbon group include a divalent chain hydrocarbon group such as: methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene and the like, and these hydrocarbon groups may be linear or branched. In addition, R ¹¹ The divalent alicyclic hydrocarbon group of (2) may be exemplified by: cyclohexylidene, -Rc- (CH) ₂ ) _n Examples of the divalent aromatic hydrocarbon group include (wherein Rc is cyclohexylene and n is an integer of 1 to 5): phenylene, biphenylene, -Ph- (CH) ₂ ) _n - (wherein Ph is phenylene and n is an integer of 1 to 5), and the like.

Specific examples of the compound represented by the above formula (3-1) include compounds represented by the following formulae (3-1-1) to (3-1-5). Further, the compound (E-1) may be used singly or in combination of two or more.

[ solution 5]

In the case of using the compound (E-1), X in said formula (1) can be obtained ¹ And X ² Has a specific aromatic amine structure. The liquid crystal aligning agent containing such a polymer (P) is preferable in terms of obtaining a liquid crystal display element having a small residual DC and excellent electrical characteristics and reliability.

(Compound having heterocyclic group)

In the case where the compound (E) is a compound having a heterocyclic group (hereinafter also referred to as "compound (E-2)"), the heterocyclic group is preferably a nitrogen-containing heterocyclic group in terms of high effect of improving reliability of the liquid crystal display element, and examples thereof include: and n-valent groups obtained by removing n hydrogen atoms from nitrogen-containing heterocycles such as pyrrole, imidazole, pyrazole, triazole, pyridine, pyrimidine, pyridazine, pyrazine, indole, benzimidazole, purine, quinoline, isoquinoline, naphthyridine, quinoxaline, phthalazine, triazine, thiazole, isothiazole, benzothiazole, 5,6,7, 8-tetrahydroquinoline, piperidine, piperazine, pyrrolidine, hexamethyleneimine, decahydroquinoline, and the like. Of these, the heterocyclic ring of the heterocyclic group is preferably pyrrole, imidazole, pyrazole, pyridine, pyrimidine, pyridazine, triazine, triazole, pyrazine or benzimidazole.

The heterocyclic group may be a group having a substituent introduced into the ring portion. Examples of such substituents include: halogen atoms such as fluorine atom, chlorine atom, and iodine atom; alkyl groups such as methyl, ethyl, and propyl; alkoxy groups such as methoxy, ethoxy, and propoxy; cycloalkyl groups such as cyclohexyl; and aryl groups such as phenyl and tolyl.

Examples of the compound (E-2) include compounds represented by the following formula (3-2).

[ solution 6]

A ² -R ¹² -OH (3-2)

(in the formula (3-2), A ² Is a nitrogen-containing heterocyclic group, R ¹² Is a single bond or a divalent hydrocarbon group)

In the formula (3-2), R ¹² (ii) description of the divalent hydrocarbon group of the formula (3-1) can be applied to R ¹¹ And (4) description.

Specific examples of the compound represented by the above formula (3-2) include compounds represented by the following formulae (3-2-1) to (3-2-22), respectively. Further, the compound (E-2) may be used singly or in combination of two or more.

[ solution 7]

[ solution 8]

In the case of using the compound (E-2), X in said formula (1) can be obtained ¹ And X ² At least one of the above polymers (P) having a heterocyclic group. The liquid crystal aligning agent containing such a polymer (P) is preferable in terms of obtaining a liquid crystal display device having excellent reliability and electric characteristics.

(Compound having polymerizable group)

In the case where the compound (E) is a compound having a polymerizable group (hereinafter, also referred to as "compound (E-3)"), examples of the polymerizable group include a group which starts polymerization by light or heat. Examples of the polymerizable group include groups having a polymerizable unsaturated bond, and specific examples of such groups include (A)Group) acryloyloxy group, styryl group, (meth) acrylamide group, vinyloxy group (CH) ₂ CH-O-), the following formula (p-1) and formula (p-2)

[ solution 9]

(in the formula (p-1), X ⁵ Is oxygen atom or-NH-; "+" indicates a bond)

The group represented, and the like. Further, (meth) acryloyloxy group means "acryloyloxy group" and "methacryloyloxy group". (meth) acrylamido is intended to include "acrylamido" and "methacrylamido". Among them, the polymerizable group is preferably a (meth) acryloyloxy group in terms of high reactivity to light or heat.

Examples of the compound (E-3) include compounds represented by the following formula (3-3).

[ solution 10]

A ³ -R ¹³ -OH (3-3)

(in formula (3-3), A ³ Is a polymerizable group, R ¹³ Is a single bond or a divalent hydrocarbon group)

In the formula (3-3), R ¹³ (ii) description of the divalent hydrocarbon group(s) applicable to the R of the formula (3-1) ¹¹ And (4) description.

Specific examples of the compound represented by the formula (3-3) include: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, hydroxyethyl (meth) acrylamide, 2-vinyloxyethanol, 2- (4-vinylbenzyloxy) ethanol, N- (hydroxymethyl) maleimide, N-hydroxymaleimide and the like. The compound (E-3) may be used singly or in combination of two or more.

In the case of using the compound (E-3), X in said formula (1) can be obtained ¹ And X ² At least one of the above polymers (P) having a polymerizable group. By using a liquid crystal aligning agent containing such a polymer (P), a liquid crystal display deviceWhen the alignment property is imparted by light irradiation, the pretilt angle characteristics are good, and a liquid crystal display element having good electrical characteristics and reliability is obtained.

(Compound having photo-rearranging group)

An example of the compound (E) is a compound having a photo-rearranging group (hereinafter also referred to as "compound (E-4)"). The photo-rearrangeable group of the compound (E-4) is a functional group having a structure that causes a rearrangement reaction by irradiation with light, and examples thereof include a group having a structure represented by the following formula (p-3) (hereinafter, also referred to as an "aromatic ester-containing structure").

[ solution 11]

(in the formula (p-3), X ³ Is sulfur atom, oxygen atom or-NH-; "" denotes a bond; wherein at least one of the two '+'s is bonded to the aromatic ring)

In the formula (p-3), examples of the aromatic ring bonded by "-" include: benzene rings, naphthalene rings, anthracene rings, and the like. Two "s" may be bonded to the aromatic ring, but from the viewpoint of photoresponsiveness, two "s" are preferably bonded to the aromatic ring, respectively.

The compound (E-4) having a photo-rearranging group is represented by, for example, the following formula (3-4).

[ solution 12]

A ⁴ -R ¹⁴ -OH (3-4)

(in the formula (3-4), A ⁴ Being a photo-rearranging group, R ¹⁴ Is a single bond or a divalent hydrocarbon group)

In the formula (3-4), R ¹⁴ (ii) description of the divalent hydrocarbon group(s) applicable to the R of the formula (3-1) ¹¹ And (4) description.

Specific examples of the compound represented by the above formula (3-4) include compounds represented by the following formulae (3-4-1) to (3-4-13), respectively. Further, the compound (E-4) may be used singly or in combination of two or more.

[ solution 13]

In the case of using the compound (E-4), X in said formula (1) can be obtained ¹ And X ² At least one of the above polymers (P) having a photo-rearranging group. The liquid crystal aligning agent containing such a polymer (P) is preferable in terms of obtaining a liquid crystal display element having less AC image sticking and excellent in electrical characteristics and reliability.

(reaction of Tetracarboxylic dianhydride with Compound (E))

The reaction of the tetracarboxylic dianhydride with the compound (E) may be carried out in an organic solvent as required. The organic solvent used is not particularly limited as long as it is inert to the tetracarboxylic dianhydride and the compound (E), and examples thereof include: ketones such as acetone and methyl ethyl ketone; hydrocarbons such as hexane, heptane, toluene and the like; halogen hydrocarbons such as chloroform and 1, 2-dichloroethane; ethers such as tetrahydrofuran, diethyl ether, and 1, 4-dioxane; nitrile compounds such as acetonitrile and propionitrile. These organic solvents may be used singly or in combination of two or more kinds.

The proportion of the compound (E) to be used is usually 2 to 100 moles, preferably 2 to 40 moles, based on 1 mole of the tetracarboxylic dianhydride. The reaction temperature in this case may be appropriately set according to the kind of the compound (E) to be used, and is preferably-20 to 150 ℃ and more preferably 0 to 100 ℃. The reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours. After the reaction, reprecipitation may be carried out as needed. Then, the obtained precipitate is washed and dried as necessary, whereby the desired tetracarboxylic acid diester can be obtained.

(diamine)

Examples of the diamine used in the reaction (polycondensation) with the tetracarboxylic acid diester include aliphatic diamines, alicyclic diamines, aromatic diamines, and diaminoorganosiloxanes. Specific examples of these diamines include aliphatic diamines such as: m-xylylenediamine, 1, 3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1, 3-bis (aminomethyl) cyclohexane, and the like; examples of the alicyclic diamine include: 1, 4-diaminocyclohexane, 4' -methylenebis (cyclohexylamine), and the like;

examples of the aromatic diamine include: dodecyloxydiaminobenzene, tetradecyloxydiaminobenzene, pentadecyloxydiaminobenzene, hexadecyloxydiaminobenzene, octadecyloxydiaminobenzene, cholestanoxydiaminobenzene, cholestenyloxydiaminobenzene, cholestanyl diaminobenzoate, cholestyryl diaminobenzoate, lanostanyl diaminobenzoate, 3, 6-bis (4-aminobenzoyloxy) cholestane, 3, 6-bis (4-aminophenoxy) cholestane, 1-bis (4- ((aminophenyl) methyl) phenyl) -4-butylcyclohexane, 1-bis (4- ((aminophenyl) methyl) phenyl) -4-heptylcyclohexane, 1-bis (4- ((aminophenoxy) methyl) phenyl) -4-heptylcyclohexane, dodecyloxydiaminobenzene, tetradecyloxydiaminobenzene, pentadecyloxydiaminobenzene, hexadecyloxydiaminobenzene, octadecyloxydiaminobenzene, cholestanoxydiaminobenzene, cholestanyl-1, 6-bis (4-aminophenoxy) cholestane, 1-bis (4- ((aminophenyl) methyl) phenyl) -4-butylcyclohexane, and mixtures thereof, 1, 1-bis (4- ((aminophenyl) methyl) phenyl) -4- (4-heptylcyclohexyl) cyclohexane, N- (2, 4-diaminophenyl) -4- (4-heptylcyclohexyl) benzamide, the following formula (D-1)

[ solution 14]

(in the formula (D-1), X ^I And X ^II Each independently is a single bond, -O-, -COO-or-OCO-, R ^I Is C1-3 alkanediyl, R ^II A is a single bond or an alkanediyl group having 1 to 3 carbon atoms, a is 0 or 1, b is an integer of 0 to 2, c is an integer of 1 to 20, and d is 0 or 1; wherein a and b do not become 0 simultaneously)

Diamines having an orientation group such as the compounds represented by the above;

4,4 '-diaminodiphenylamine, N-bis (4-aminophenyl) methylamine, N- (3, 5-diaminophenyl) aniline, N' -bis (4-aminophenyl) -benzidine, N '-bis (4-aminophenyl) -N, N' -dimethylbenzidine, the following formula (d-1)

[ chemical 15]

Diamines having a specific aromatic amine structure, such as the compounds represented by the above;

2, 6-diaminopyridine, 2, 4-diaminopyrimidine, 3, 6-diaminoacridine, 3, 6-diaminocarbazole, N-methyl-3, 6-diaminocarbazole, 1, 4-bis- (4-aminophenyl) -piperazine, the following formulae (d-2) to (d-5)

[ solution 16]

Heterocyclic group-containing diamines such as the compounds represented by the above formulae;

the following formula (d-6)

[ solution 17]

(in the formula (d-6), R ⁸ Is a hydrogen atom or a methyl group)

A diamine containing a polymerizable group such as the compound represented by the formula;

4-aminophenyl-4 '-aminobenzoate, 3' -dimethyl-4-aminophenyl-4 '-aminobenzoate, 3-methyl-4-aminophenyl-4' -aminobenzoate, the following formulae (d-7) to (d-14)

[ solution 18]

Diamines having a photo-rearranging group, such as the compounds represented by the above;

p-phenylenediamine, 4' -diaminodiphenylmethane, 4' -diaminodiphenylamine, 4' -diaminodiphenylsulfide, 4' -diaminoazobenzene, 1, 5-bis (4-aminophenoxy) pentane, 1, 7-bis (4-aminophenoxy) heptane, bis [2- (4-aminophenyl) ethyl ] adipic acid, 1, 5-diaminonaphthalene, 2' -dimethyl-4, 4' -diaminobiphenyl, 2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl, 4' -diaminodiphenyl ether, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 9-bis (4-aminophenyl) fluorene, 9-bis (4-aminophenoxy) fluorene, Other diamines such as 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 2-bis (4-aminophenyl) hexafluoropropane, 4'- (p-phenylenediisopropylidene) dianiline, 1, 4-bis (4-aminophenoxy) benzene, 4' -bis (4-aminophenoxy) biphenyl and 3, 5-diaminobenzoic acid;

examples of the diaminoorganosiloxanes include: 1, 3-bis (3-aminopropyl) -tetramethyldisiloxane, and other diamines described in JP-A No. 2010-97188 can be used.

-X in the formula (D-1) ^I -(R ^I -X ^II ) _d The divalent group represented by- "is preferably an alkanediyl group having 1 to 3 carbon atoms, -O-, -COO-or-O-C ₂ H ₄ -O- (wherein the bond with the "-" is bonded to the diaminophenyl). radical-C _c H _2c+1 Examples of "include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and the like, and these groups are preferably linear. The two amino groups in the diaminophenyl group are preferably in the 2, 4-or 3, 5-positions relative to the other groups.

Specific examples of the compound represented by the formula (D-1) include compounds represented by the following formulae (D-1-1) to (D-1-4).

[ formula 19]

In addition, one of these compounds may be used alone or two or more thereof may be appropriately selected and used as the diamine used in the reaction.

When the polymer (P) is used as a liquid crystal aligning agent for a TN type, STN type or vertical alignment type liquid crystal display device, it is preferable to use a diamine containing an aligning group as at least a part of the diamine used for synthesizing the polymer (P). Examples of the orientation group of the diamine having an orientation group include: an alkyl group having 4 to 20 carbon atoms, a fluoroalkyl group having 4 to 20 carbon atoms, an alkoxy group having 4 to 20 carbon atoms, a group having 17 to 51 carbon atoms and a steroid skeleton, a group having a polycyclic structure, and the like. In the case of using the diamine containing an alignment group, the proportion of the diamine containing an alignment group to be used is preferably 3 mol% or more, and more preferably 5 mol% to 70 mol% based on the total diamines used in the synthesis, from the viewpoint of improving the liquid crystal alignment properties.

R in the formula (1) ² Is a divalent radical derived from a diamine, i.e., a residue resulting from the removal of two primary amino groups from a diamine. Here, in the case where a diamine having the functional group is used for at least a part of the diamines used in the synthesis of the polymer (P), X in the formula (1) may be ¹ And X ² And R ² Into which the functional group is introduced. In this case, it is preferable that the number of the functional groups per molecule of the polymer is increased to sufficiently exhibit various properties of the functional groups.

In the case of using the diamine having the functional group, the use ratio of the diamine having the functional group is preferably 5 mol% or more, and more preferably 10 mol% or more, based on the total diamines used in the synthesis.

When a coating film formed of a liquid crystal aligning agent is provided with a liquid crystal aligning ability by a photo-alignment method, at least a part of tetracarboxylic dianhydride and diamine used in the reaction may be a compound having a photo-alignment structure. As the photo-alignment structure, a group which exhibits photo-alignment by photo-isomerization, photo-dimerization, photo-decomposition, or the like can be used. Specific examples thereof include: an azo group-containing group containing an azo compound or a derivative thereof as a basic skeleton, a cinnamic acid-containing group containing cinnamic acid or a derivative thereof as a basic skeleton, a chalcone-containing group containing chalcone or a derivative thereof as a basic skeleton, a benzophenone-containing group containing benzophenone or a derivative thereof as a basic skeleton, a coumarin-containing group containing coumarin or a derivative thereof as a basic skeleton, a cyclobutane-containing structure containing cyclobutane or a derivative thereof as a basic skeleton, a bicyclo [2.2.2] octene-containing structure containing bicyclo [2.2.2] octene or a derivative thereof as a basic skeleton, an aromatic ester-containing structure containing a partial structure represented by the formula (p-3) as a basic skeleton, and the like.

In the case of using a monomer having a photo-alignment structure, the proportion of the monomer used is preferably 20 mol% or more, and more preferably 30 to 80 mol% with respect to the total amount of the monomers used for synthesis of the polymer, from the viewpoint of photoreactivity.

(reaction of a tetracarboxylic acid diester with a diamine)

The reaction of the tetracarboxylic acid diester with the diamine is preferably carried out in an organic solvent in the presence of a dehydration catalyst and a base. The ratio of the tetracarboxylic diester and the diamine to be used in the reaction is preferably 0.2 to 2 equivalents, more preferably 0.3 to 1.2 equivalents, of the carboxyl group of the tetracarboxylic diester to 1 equivalent of the amino group of the diamine.

In the reaction of the tetracarboxylic acid diester with the diamine, at least one compound selected from the group consisting of tetracarboxylic acid dianhydrides and tetracarboxylic acid diesters having no functional groups may be used in combination. In this case, the ratio of the tetracarboxylic dianhydride to the tetracarboxylic diester having no functional group (the total amount of the tetracarboxylic dianhydride in the case of using two or more kinds thereof) used is preferably 50 mol% or less, more preferably 40 mol% or less, and particularly preferably 30 mol% or less, relative to the total amount of the tetracarboxylic diester and the tetracarboxylic dianhydride used for synthesizing the polymer (P).

Examples of the organic solvent used in the reaction include: aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and the like. Among these organic solvents, it is preferable to use one or more selected from the group consisting of aprotic polar solvents and phenolic solvents (organic solvents of the first group), or a mixture of one or more selected from the group consisting of one or more selected from the first group and one or more selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons (organic solvents of the second group). In the latter case, the ratio of the organic solvent of the second group to the total amount of the organic solvents of the first group and the second group is preferably 50% by weight or less, more preferably 40% by weight or less, and particularly preferably 30% by weight or less.

Particularly preferred as the organic solvent is one or more selected from the group consisting of N-methyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide, γ -butyrolactone, tetramethylurea, hexamethylphosphoric triamide, m-cresol, xylenol, and halogenated phenol, or a mixture of one or more of these organic solvents and another organic solvent in the above ratio. The amount (a) of the organic solvent used is preferably such that the total amount (b) of the monomers used in the reaction is 0.1 to 50% by weight based on the total amount (a + b) of the reaction solution.

Examples of the dehydration catalyst used in the reaction include: 4- (4, 6-dimethoxy-1, 3, 5-triazin-2-yl) -4-methylmorpholinium halide, carbonylimidazole, dicyclohexylcarbodiimide, phosphorus-based condensing agent, and the like. The proportion of the dehydration catalyst used is preferably 2 to 3 moles, more preferably 2 to 2.5 moles, based on 1 mole of the tetracarboxylic acid diester.

As the base, tertiary amines such as pyridine and triethylamine can be preferably used. The proportion of the base used is preferably 2 to 4 moles, more preferably 2 to 3 moles, based on 1 mole of the diamine. Further, the reaction may be carried out in the presence of a lewis acid for the purpose of promoting the reaction. Examples of the lewis acid include lithium halides such as lithium chloride.

The reaction temperature is preferably-20 ℃ to 150 ℃, more preferably 0 ℃ to 100 ℃. The reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours.

In the manner as described above, a reaction solution in which the polymer (P) is dissolved is obtained. The reaction solution may be directly supplied to the preparation of the liquid crystal aligning agent, or the polymer (P) contained in the reaction solution may be separated and then supplied to the preparation of the liquid crystal aligning agent, or the separated polymer (P) may be purified and then supplied to the preparation of the liquid crystal aligning agent. The isolation and purification of the polymer (P) can be carried out according to known methods.

In addition to the method of reacting the tetracarboxylic acid diester with the diamine, the polymer (P) can be obtained by, for example: [A] a method of reacting a polyamic acid with the compound (E); [B] a method of reacting a tetracarboxylic acid diester dihalide having the functional group with a diamine, and the like. The polymer (P) may have only the amic acid ester structure or may be a partially esterified product in which the amic acid structure and the amic acid ester structure coexist.

In the case of the method [ a ], the compound (E) used for the reaction with the polyamic acid is not particularly limited as long as it has the functional group, and examples thereof include: the compounds (E-1) to (E-4), epoxy compounds, thiol compounds and amine compounds having the functional group, and the like. When the polyamic acid is reacted with the compound (E), another esterifying agent having no functional group may be used together with the compound (E) if necessary. Examples of other esterification agents include: alcohols such as methanol and ethanol; phenols such as phenol and cresol; acetal compounds such as N, N-dimethylformamide diethylacetal and N, N-diethylformamide diethylacetal, and the like. When another esterification agent is used, the ratio of the other esterification agent to the total amount of the esterification agents used in the reaction is preferably 30 mol% or less, and more preferably 20 mol% or less.

The reaction of the polyamic acid with the compound (E) is preferably carried out in the presence of an organic solvent. In this case, the compound (E) is preferably used in a proportion of 0.002 to 10 mol, more preferably 0.02 to 6 mol, based on 1 mol of the repeating unit of the polyamic acid. As the organic solvent used, the organic solvent used in the reaction of the tetracarboxylic acid diester with the diamine can be used. The amount of the organic solvent used is preferably such that the polyamic acid is 0.1 to 50 wt% based on the total amount of the reaction solution. The reaction temperature is preferably-20 ℃ to 200 ℃, more preferably 0 ℃ to 120 ℃. The reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours.

The tetracarboxylic acid diester dihalide used in the method [ B ] can be obtained by reacting the tetracarboxylic acid diester obtained in the above manner with an appropriate chlorinating agent such as thionyl chloride. The acid derivative used in the reaction with the diamine may be only a tetracarboxylic acid diester dihalide, or a tetracarboxylic acid dianhydride may be used in combination. The diamine used in the reaction may be exemplified as the diamine used in the reaction with the tetracarboxylic acid diester. The ratio of the tetracarboxylic acid diester dihalide and the diamine to be used in the synthesis reaction of the polymer (P) is preferably such that the group "— COX (X is a halogen atom)" of the tetracarboxylic acid diester dihalide becomes 0.2 to 2 equivalents, more preferably 0.3 to 1.2 equivalents, based on 1 equivalent of the amino group of the diamine.

The reaction of the tetracarboxylic acid diester dihalide with the diamine is preferably carried out in an organic solvent in the presence of a base. The reaction temperature in this case is preferably-30 ℃ to 150 ℃, more preferably-10 ℃ to 100 ℃. The reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours. As the organic solvent used in the reaction, the organic solvent used in the reaction of the tetracarboxylic acid diester and the diamine can be used. The amount of the organic solvent used is preferably such that the total amount of the tetracarboxylic acid diester dihalide and the diamine is 0.1 to 50% by weight based on the total amount of the reaction solution. The base used in the reaction can be preferably used, for example: tertiary amines such as pyridine and triethylamine; alkali metals such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium and potassium, and the like. The amount of the base used is preferably 2 to 4 moles, more preferably 2 to 3 moles, based on 1 mole of the diamine.

The polymer (P) obtained as described above is preferably one having a solution viscosity of from 20 mPas to 1,800 mPas, more preferably from 50 mPas to 1,500 mPas, when prepared in a 15% by weight solution. The solution viscosity (mPa · s) of the polymer (P) is a value measured at 25 ℃ using an E-type rotational viscometer for a polymer solution having a concentration of 15% by weight prepared using a good solvent (e.g., γ -butyrolactone, N-methyl-2-pyrrolidone, etc.) for the polymer (P).

The weight average molecular weight (Mw) of the polymer (P) in terms of polystyrene, as measured by Gel Permeation Chromatography (GPC), is preferably 1,000 to 500,000, more preferably 2,000 to 300,000. The molecular weight distribution (Mw/Mn) represented by the ratio of Mw to the number average molecular weight (Mn) in terms of polystyrene measured by GPC is preferably 7 or less, and more preferably 5 or less. When the molecular weight is within the above range, good alignment properties and stability of the liquid crystal display element can be ensured.

< Polymer (Q) >

The liquid crystal aligning agent of the present disclosure may contain the polymer (P) alone as a polymer component, or may contain at least one polymer (Q) selected from the group consisting of polyamic acid and polyimide together with the polymer (P). In addition, when a coating film is formed on a substrate using a liquid crystal aligning agent containing the polymer (P) and the polymer (Q), the polymer (P) may be biased to an outer layer of the coating film depending on a difference in surface energy, and the above-described effects are presumed to be obtained.

(Polyamic acid)

The polyamic acid as the polymer (Q) can be obtained by, for example, reacting tetracarboxylic dianhydride with diamine. Examples of the tetracarboxylic dianhydride and diamine used in the reaction include those used in the synthesis of the polymer (P).

The ratio of the tetracarboxylic dianhydride to the diamine used in the synthesis reaction of the polyamic acid is preferably 0.2 to 2 equivalents, more preferably 0.3 to 1.2 equivalents, of the acid anhydride group of the tetracarboxylic dianhydride to 1 equivalent of the amino group of the diamine.

The synthesis reaction of the polyamic acid is preferably carried out in an organic solvent. The reaction temperature in this case is preferably-20 to 150 ℃ and more preferably 0 to 100 ℃. The reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours. Examples of the organic solvent used in the reaction include organic solvents used in the reaction of a tetracarboxylic acid diester and a diamine. The reaction temperature is preferably-20 ℃ to 150 ℃, more preferably 0 ℃ to 100 ℃. The reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours.

In the manner as described above, a reaction solution in which polyamide acid is dissolved is obtained. The reaction solution may be directly supplied to the preparation of the liquid crystal aligning agent, or the polyamic acid contained in the reaction solution may be separated and then supplied to the preparation of the liquid crystal aligning agent, or the separated polyamic acid may be purified and then supplied to the preparation of the liquid crystal aligning agent. In the case of forming a polyimide by subjecting a polyamic acid to dehydration ring closure, the reaction solution may be supplied directly to the dehydration ring closure reaction, the polyamic acid contained in the reaction solution may be separated and then supplied to the dehydration ring closure reaction, or the separated polyamic acid may be purified and then supplied to the dehydration ring closure reaction. The isolation and purification of the polyamic acid can be carried out according to a known method. When the polymer (Q) contains a polyamic acid, it is preferable in that the effect of the polymer (P) is obtained and the printability is further improved.

(polyimide)

The polyimide as the polymer (Q) can be obtained by, for example, imidizing a polyamic acid synthesized in the above-described manner by dehydrative ring closure.

The polyimide may be a complete imide product obtained by dehydration ring closure of the entire amic acid structure of the polyamic acid as a precursor thereof, or may be a partial imide product obtained by dehydration ring closure of only a part of the amic acid structure to allow the amic acid structure and the imide ring structure to coexist. The imidization ratio of the polyimide used in the reaction is preferably 20% or more, more preferably 30% to 99%, and particularly preferably 40% to 99%. The imidization ratio is a ratio of the number of imide ring structures to the total of the number of amic acid structures and the number of imide ring structures of the polyimide, and is expressed as a percentage. Here, a part of the imide ring may be an imide ring.

The dehydration ring-closing of the polyamic acid is preferably performed by the following method: a method of heating the polyamic acid; or a method in which the polyamic acid is dissolved in an organic solvent, and a dehydrating agent and a dehydration ring-closing catalyst are added to the solution, followed by heating as necessary. Among them, the latter method is preferably used.

In the method of adding the dehydrating agent and the dehydration ring-closing catalyst to the solution of polyamic acid, the dehydrating agent may be, for example, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride. The amount of the dehydrating agent to be used is preferably 0.01 to 20 moles based on 1 mole of the amic acid structure of the polyamic acid. As the dehydration ring-closure catalyst, for example, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used. The amount of the dehydration ring-closing catalyst to be used is preferably 0.01 to 10 mol based on 1 mol of the dehydrating agent to be used. Examples of the organic solvent used in the dehydration ring-closure reaction include organic solvents exemplified as compounds used in the reaction of a tetracarboxylic acid diester and a diamine. The reaction temperature of the dehydration ring-closure reaction is preferably 0 to 180 ℃, more preferably 10 to 150 ℃. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.

A reaction solution containing polyimide was obtained in the manner described. The reaction solution can be directly provided for the preparation of the liquid crystal aligning agent, or can be provided for the preparation of the liquid crystal aligning agent after the dehydrating agent and the dehydration ring-closing catalyst are removed from the reaction solution, or can be provided for the preparation of the liquid crystal aligning agent after the polyimide is separated, or can be provided for the preparation of the liquid crystal aligning agent after the separated polyimide is purified. These purification operations may be carried out according to known methods. When polyimide is contained as the polymer (Q), it is preferable in terms of not only obtaining the effect of blending the polymer (P) but also improving the electrical characteristics.

The polymer (Q) is preferably one having a solution viscosity of 20 to 1,800 mPas, more preferably 50 to 1,500 mPas, when it is prepared into a 15 wt.% solution. The solution viscosity (mPa · s) of the polymer (Q) is a value measured at 25 ℃ using an E-type rotational viscometer with respect to a polymer solution having a concentration of 15 wt% prepared using a good solvent (e.g., γ -butyrolactone, N-methyl-2-pyrrolidone, etc.) for the polymer (Q).

The weight average molecular weight (Mw) of the polymer (Q) in terms of polystyrene measured by GPC is preferably 1,000 to 500,000, more preferably 2,000 to 300,000. The molecular weight distribution (Mw/Mn) represented by the ratio of Mw to the number average molecular weight (Mn) in terms of polystyrene measured by GPC is preferably 7 or less, and more preferably 5 or less.

In the case where the liquid crystal aligning agent of the present disclosure contains the polymer (Q), the content ratio of the polymer (P) is preferably appropriately set according to the kind of the functional group which the polymer (P) has. Specifically, X in the formula (1) of the polymer (P) ¹ And X ² In the case where at least one of the polymer (a) and the polymer (Q) has a specific aromatic amine structure or heterocyclic group, the content of the polymer (P) is preferably 40 parts by weight or more based on 100 parts by weight of the total of the polymer (P) and the polymer (Q). If the content of the polymer (P) is less than 40 parts by weight, the reliability of the liquid crystal display device tends to be deteriorated. More preferably 45 to 99 parts by weight, particularly preferably 50 to 97 parts by weight, and particularly preferably 60 to 95 parts by weight.

X in the formula (1) of the polymer (P) ¹ And X ² In the case where at least any one of (a) and (b) has a polymerizable group, the content of the polymer (P) is preferably 3 parts by weight or more, more preferably 5 parts by weight to 95 parts by weight, particularly preferably 10 parts by weight to 90 parts by weight, and particularly preferably 15 parts by weight to 85 parts by weight, based on 100 parts by weight of the total of the polymer (P) and the polymer (Q), from the viewpoint of providing a coating film with a suitably high pretilt angle.

X in the formula (1) of the polymer (P) ¹ And X ² In the case where at least one of the above groups has a photo-rearranging group, the improvement effect of the afterimage characteristics of the liquid crystal display element (particularly, afterimage characteristics called "AC afterimage" caused by an AC voltage) can be sufficiently obtainedThe content of the polymer (P) is preferably 3 parts by weight or more, more preferably 5 to 95 parts by weight, particularly preferably 10 to 90 parts by weight, and particularly preferably 15 to 85 parts by weight, based on 100 parts by weight of the total of the polymer (P) and the polymer (Q).

< other ingredients >

The liquid crystal aligning agent of the present disclosure may contain components (other components) other than the polymer (P) and the polymer (Q) as needed. Examples of the other component include polymers other than the polymer (P) and the polymer (Q), a compound having at least one epoxy group in the molecule (hereinafter referred to as an "epoxy group-containing compound"), a functional silane compound, and the like.

[ other polymers ]

The other polymers may be used to improve solution characteristics or electrical characteristics. Examples of the other polymer include polymers having a main skeleton of polyamic acid ester, polyorganosiloxane, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenylmaleimide) derivative, poly (meth) acrylate, and the like, which do not have the functional group at the carboxyl group of the amic acid structure. When another polymer is blended in the liquid crystal aligning agent, the blending ratio of the other polymer is preferably 50 parts by weight or less, more preferably 0.1 to 40 parts by weight, and particularly preferably 0.1 to 30 parts by weight or less, based on 100 parts by weight of the total of the polymers contained in the liquid crystal aligning agent.

[ epoxy group-containing Compound ]

The epoxy group-containing compound is useful for improving the adhesion of the liquid crystal alignment film to the surface of the substrate or the electrical characteristics. Examples of such epoxy group-containing compounds include the following compounds: ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, N ' -tetraglycidyl-m-xylylenediamine, 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, N ' -tetraglycidyl-4, 4' -diaminodiphenylmethane, N-diglycidylaminomethylcyclohexane, ethyl glycidyl ether, and the like. In addition, as an example of the epoxy group-containing compound, an epoxy group-containing polyorganosiloxane described in international publication No. 2009/096598 can be used.

When the epoxy-containing compound is blended in the liquid crystal aligning agent, the blending ratio of the epoxy-containing compound is preferably 40 parts by weight or less, and more preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the total polymer contained in the liquid crystal aligning agent.

[ functional silane Compound ]

The functional silane compound may be used for the purpose of improving printability of the liquid crystal aligning agent. Examples of such functional silane compounds include: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, 10-trimethoxysilyl-1, 4, 7-triazadecane, N-benzyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane and the like.

When another functional silane compound is blended in the liquid crystal aligning agent, the blending ratio of the other functional silane compound is preferably 2 parts by weight or less, and more preferably 0.02 parts by weight to 0.2 parts by weight, based on 100 parts by weight of the total polymer contained in the liquid crystal aligning agent.

In addition, in addition to the compounds, other ingredients may be listed: a compound having at least one oxetanyl group in the molecule, an antioxidant, a metal chelate compound, a hardening accelerator, a surfactant, a filler, a dispersant, a sensitizer, and the like.

< solvent >

The liquid crystal aligning agent of the present disclosure is prepared as a liquid composition in which the polymer (P) and other components used as needed are preferably dispersed or dissolved in an appropriate solvent.

Examples of the organic solvent to be used include: n-methyl-2-pyrrolidone, gamma-butyrolactone, gamma-butyrolactam, N-dimethylformamide, N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-N-propyl ether, ethylene glycol-isopropyl 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 acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, gamma-butyrolactam, N-dimethylformamide, N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol dimethyl ether acetate, isobutyl ketone, isopentyl propionate, isopentyl isobutyrate, isopentyl acetate, methyl acetate, ethyl acetate, methyl acetate, ethyl acetate, diisoamyl ether, ethylene carbonate, propylene carbonate, and the like. These organic solvents may be used alone or in combination of two or more.

The solid content concentration in the liquid crystal aligning agent (the ratio of the total weight of the components other than the solvent of the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) may be appropriately selected in consideration of viscosity, volatility, and the like, and is preferably in the range of 1 to 10 wt%. That is, the liquid crystal aligning agent is applied to the surface of the substrate in the manner described below, and preferably heated to form a coating film as a liquid crystal alignment film or a coating film as a liquid crystal alignment film. In this case, when the solid content concentration is less than 1% by weight, the film thickness of the coating film becomes too small to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10 wt%, the film thickness of the coating film becomes too large to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent increases to decrease the coatability.

The particularly preferable range of the solid content concentration varies depending on the method used when the liquid crystal aligning agent is applied to the substrate. For example, when the liquid crystal alignment agent is applied to a substrate by a spinner method, the solid content concentration (the ratio of the total weight of all components other than the solvent in the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent) is particularly preferably in the range of 1.5 to 4.5 wt%. When the printing method is used, it is particularly preferable that the solution viscosity is set to a range of 12mPa · s to 50mPa · s by setting the solid content concentration to a range of 3 wt% to 9 wt%. In the case of using the ink jet method, it is particularly preferable to set the solution viscosity to a range of 3 to 15mPa · s by setting the solid content concentration to a range of 1 to 5 wt%. The temperature for preparing the liquid crystal aligning agent is preferably 10 to 50 ℃, more preferably 20 to 30 ℃.

< liquid crystal display element >

The liquid crystal display element of the present disclosure includes a liquid crystal alignment film formed using the liquid crystal alignment agent described above. The operation mode of the liquid crystal display element is not particularly limited, and the liquid crystal display element can be applied to various operation modes such as TN type, STN type, VA type (including Vertical Alignment-Multi-domain Vertical Alignment, VA-MVA type, Vertical Alignment-pattern Vertical Alignment (VA-PVA) type, and the like), IPS type, FFS type, and Optically Compensated Bend (OCB) type.

The liquid crystal display element can be manufactured by, for example, steps including the following steps (1) to (3). The step (1) uses different substrates according to the required operation mode. The step (2) and the step (3) are shared in each operation mode.

[ step (1): formation of coating film ]

First, a liquid crystal aligning agent is applied to a substrate, and then the coated surface is heated, thereby forming a coating film on the substrate.

(1-1) in the case of manufacturing, for example, a TN-type, STN-type, or VA-type liquid crystal display element, first, a pair of two substrates provided with a patterned transparent conductive film is coated with a liquid crystal aligning agent on each transparent conductive film-forming surface of the substrates, preferably by an offset printing method, a spin coating method, a roll coater method, or an inkjet printing method. The substrate may be, for example: float glass, soda glass, and the like; transparent substrates comprising plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, and poly (alicyclic olefin). The transparent conductive film disposed on one surface of the substrate may includeTin oxide (SnO) ₂ ) A film of (Nesa) (registered trademark of PPG Corp., USA) containing indium oxide-tin oxide (In) ₂ O ₃ -SnO ₂ ) Indium Tin Oxide (ITO) film, and the like. In order to obtain a patterned transparent conductive film, for example, the following method can be used: a method of forming a pattern by photolithography after forming a transparent conductive film without a pattern; a method of forming a transparent conductive film using a mask having a desired pattern. In the case of applying the liquid crystal aligning agent, the surface of the substrate on which the coating film is formed may be subjected to a pretreatment of previously applying a functional silane compound, a functional titanium compound or the like in order to improve the adhesion between the substrate surface and the transparent conductive film and the coating film.

After the liquid crystal aligning agent is applied, preheating (prebaking) is preferably performed for the purpose of preventing sagging of the applied liquid crystal aligning agent and the like. The prebaking temperature is preferably from 30 ℃ to 200 ℃, more preferably from 40 ℃ to 150 ℃, and particularly preferably from 40 ℃ to 100 ℃. The prebaking time is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes. Then, a calcination (post-baking) step is carried out for the purpose of completely removing the solvent, and if necessary, thermally imidizing the amic acid structure present in the polymer. The calcination temperature (post-baking temperature) in this case is preferably 80 to 300 ℃, more preferably 120 to 250 ℃. The post-baking time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. The film thickness of the film formed in this manner is preferably 0.001 to 1 μm, and more preferably 0.005 to 0.5. mu.m.

(1-2) in the case of producing an IPS type or FFS type liquid crystal display element, a liquid crystal aligning agent is applied to an electrode forming surface of a substrate provided with an electrode comprising a transparent conductive film or a metal film patterned into a comb-tooth shape and a surface of a counter substrate not provided with an electrode, and then the respective applied surfaces are heated to form a coating film. The preferable film thickness of the substrate and the transparent conductive film used in this case, the coating method, the heating condition after coating, the method for patterning the transparent conductive film or the metal film, the pretreatment of the substrate, and the formed coating film is the same as the above (1-1). As the metal film, a film containing a metal such as chromium can be used.

In both cases (1-1) and (1-2), a liquid crystal alignment film or a coating film to be a liquid crystal alignment film is formed by applying a liquid crystal alignment agent to a substrate and then removing the organic solvent. In this case, the polyamic acid, polyamic acid ester, and polyimide blended in the liquid crystal alignment agent may be subjected to a dehydration ring-closure reaction by further heating after the formation of the coating film, thereby forming a further imidized coating film.

[ step (2): orientation ability imparting treatment

In the case of manufacturing a TN-type, STN-type, IPS-type, or FFS-type liquid crystal display element, a treatment of imparting liquid crystal aligning ability to the coating film formed in the step (1) is performed. Thereby, the alignment ability of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film. Examples of the orientation ability imparting treatment include rubbing treatment in which a coating film is wiped in a certain direction by a roller around which a cloth containing fibers such as nylon, rayon, and cotton is wound, and photo-orientation treatment; the photo-alignment treatment irradiates the coating film with polarized or unpolarized radiation. On the other hand, in the case of producing a VA-type liquid crystal display element, the coating film formed in the step (1) may be used as it is as a liquid crystal alignment film, or the coating film may be subjected to an alignment ability imparting treatment.

In the photo-alignment treatment, ultraviolet rays and visible rays including light having a wavelength of 150nm to 800nm, for example, can be used as the radiation irradiated to the coating film. When the radiation is polarized light, the radiation may be linearly polarized light or partially polarized light. When the radiation used is linearly polarized light or partially polarized light, the substrate surface may be irradiated from the vertical direction, may be irradiated from the oblique direction, or may be irradiated in combination. When unpolarized radiation is irradiated, the irradiation direction is an oblique direction.

The light sources used may be, for example: low pressure mercury lamps, high pressure mercury lamps, deuterium lamps, metal halide lamps, argon resonance lamps, xenon lamps, excimer lasers, and the like. Ultraviolet light in a preferred wavelength region can be used by combining a light source with, for example, a filter, a diffraction grating, or the likeAnd the method used in the method is obtained. The irradiation dose of the radiation is preferably 100J/m ² ～50,000J/m ² More preferably 300J/m ² ～20,000J/m ² . In addition, in order to improve the reactivity, the coating film may be irradiated with light while being heated. The temperature at the time of heating is usually from 30 ℃ to 250 ℃, preferably from 40 ℃ to 200 ℃, and more preferably from 50 ℃ to 150 ℃.

Further, the liquid crystal alignment film after the rubbing treatment may be further subjected to the following treatment so that the liquid crystal alignment film has different liquid crystal alignment ability for each region: a process of changing the pretilt angle of a partial region of the liquid crystal alignment film by irradiating a part of the liquid crystal alignment film with ultraviolet rays; or a process of forming a resist film on a part of the surface of the liquid crystal alignment film, then performing a rubbing process in a direction different from the previous rubbing process, and then removing the resist film. In this case, the viewing characteristics of the resulting liquid crystal display element can be improved.

In the case of producing a Polymer Stabilized Alignment (PSA) type liquid crystal display element, the following step (3) can be carried out by directly using the coating film formed in the step (1), but alignment treatment such as weak rubbing treatment may be carried out for the purpose of controlling collapse of liquid crystal molecules and performing alignment division by a simple method. The liquid crystal alignment film suitable for the VA-type liquid crystal display element can also be suitably used for the PSA-type liquid crystal display element. When a coating film is formed using a liquid crystal aligning agent containing a polymerizable group-containing component, the following step (3) is performed using the coating film formed in the above step (1) as it is.

[ step (3): construction of liquid Crystal cell

(3-1) two substrates on which the liquid crystal alignment films are formed in this manner are prepared, and liquid crystal is disposed between the two substrates disposed in opposition to each other, thereby manufacturing a liquid crystal cell. In order to manufacture a liquid crystal cell, for example, the following two methods are listed. First, the first method is a conventionally known method. In this method, first, two substrates are arranged to face each other through a gap (cell gap) so that the liquid crystal alignment films face each other, peripheral portions of the two substrates are bonded to each other with a sealant, a liquid crystal is injected and filled into the cell gap defined by the substrate surfaces and the sealant, and then the injection hole is sealed, thereby manufacturing a liquid crystal cell. The second method is a method called a One Drop Fill (ODF) method. In this method, for example, an ultraviolet-curable sealant is applied to a predetermined portion of one of two substrates on which liquid crystal alignment films are formed, liquid crystal is dropped onto predetermined portions of the liquid crystal alignment film surface, and then the other substrate is bonded so that the liquid crystal alignment films face each other. Next, the liquid crystal is spread over the entire surface of the substrate, and then ultraviolet light is irradiated to the entire surface of the substrate to cure the sealant, thereby manufacturing a liquid crystal cell. In either method, it is preferable that the liquid crystal cell produced as described above is further heated to a temperature at which the liquid crystal used has an isotropic phase, and then gradually cooled to room temperature, thereby eliminating the flow alignment during filling of the liquid crystal.

As the sealant, for example, an epoxy resin containing a curing agent and alumina balls as spacers can be used. Examples of the liquid crystal include nematic liquid crystal and smectic liquid crystal, and among them, nematic liquid crystal is preferable, and for example: schiff base (Schiff base) liquid crystals, azoxy (azoxy) liquid crystals, biphenyl liquid crystals, phenylcyclohexane liquid crystals, ester liquid crystals, terphenyl liquid crystals, biphenylcyclohexane liquid crystals, pyrimidine liquid crystals, dioxane liquid crystals, bicyclooctane liquid crystals, cubane (cubane) liquid crystals, and the like. In addition, the following substances may be added to these liquid crystals: cholesteric liquid crystals (cholesteric crystals), such as cholesterol chloride (cholesteryl chloride), cholesterol nonanoate (cholesteryl nonaate), and cholesterol carbonate (cholesteryl carbonate); chiral agents sold under the trade names "C-15", "CB-15" (manufactured by Merck); ferroelectric liquid crystals such as p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate and the like.

(3-2) in the case of producing a PSA type liquid crystal display device, a liquid crystal cell was constructed in the same manner as in (3-1) above, except that the photopolymerizable compound was injected or dropped together with the liquid crystal. Then theThe liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates. The voltage applied here may be, for example, a direct current or an alternating current of 5V to 50V. The light to be irradiated may be ultraviolet light or visible light including light having a wavelength of 150nm to 800nm, for example, and preferably ultraviolet light including light having a wavelength of 300nm to 400 nm. Examples of the light source for irradiating light include a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, and an excimer laser. The ultraviolet light in the preferred wavelength range can be obtained by a method of using a light source in combination with, for example, a filter, a diffraction grating, or the like. The irradiation amount of light is preferably 1,000J/m ² More than and less than 200,000J/m ² More preferably 1,000J/m ² ～100,000J/m ² 。

(3-3) in the case of forming a coating film on a substrate using a liquid crystal aligning agent containing a polymer having a photopolymerizable group as the polymer (P), a liquid crystal display element can also be manufactured by passing through a step of irradiating a liquid crystal cell with light in a state where a voltage is applied between conductive films provided on a pair of substrates. The description of (3-2) can be applied to the applied voltage, or the condition of the irradiated light.

Next, a polarizing plate is attached to the outer surface of the liquid crystal cell to obtain a liquid crystal display element. Examples of the polarizing plate attached to the outer surface of the liquid crystal cell include: a polarizing plate formed by sandwiching a polarizing film called "H film" formed by absorbing iodine while extending and orienting polyvinyl alcohol, or a polarizing plate including the H film itself with a cellulose acetate protective film.

The liquid crystal display element of the present disclosure can be effectively applied to various devices, for example, can be used for: a clock, a portable game machine, a word processor, a notebook Personal computer, a car navigation system, a camcorder, a Personal Digital Assistant (PDA), a Digital camera, a mobile phone, a smart phone, various monitors, a liquid crystal television, and various display devices such as an information display.

[ examples ]

The present invention will be further specifically described below with reference to examples, but the present invention is not limited to these examples.

In the following examples, the weight average molecular weight Mw of the polymer and the solution viscosity of the polymer solution were measured by the following methods. Hereinafter, the compound represented by the formula X may be abbreviated as "compound X".

[ weight-average molecular weight Mw of Polymer ]

Mw is a polystyrene equivalent measured by GPC under the following conditions.

Pipe column: TSKgelGRCXLII manufactured by Tosoh (Strand, Tosoh)

Solvent: tetrahydrofuran (THF)

Temperature: 40 deg.C

Pressure: 68kgf/cm ²

[ solution viscosity of Polymer solution ]

The solution viscosity (mPas) of the polymer solution was measured at 25 ℃ using an E-type rotational viscometer.

< Synthesis of Polymer [1] >)

Synthesis examples 1-1: synthesis of Polymer (A-1-1)

1,2,3, 4-cyclobutanetetracarboxylic dianhydride as 100 parts by mole of tetracarboxylic dianhydride and 4-hydroxydiphenylamine (compound represented by the above formula (3-1-1)) as 200 parts by mole of compound (E) were added to tetrahydrofuran and stirred. The resulting precipitate was separated by filtration, washed with acetone, and dried under reduced pressure, whereby the compound (AE-1-1) was obtained as a tetracarboxylic acid diester in the form of a powder. Then, 100 parts by mole of the compound (AE-1-1) was dissolved in N-methyl-2-pyrrolidone (NMP), and then 100 parts by mole of 4,4' -diaminodiphenylamine as a diamine was added thereto and dissolved. To this solution was added 300 parts by mole of 4- (4, 6-dimethoxy-1, 3, 5-triazin-2-yl) -4-methylmorpholinium chloride (DMT-MM, 15. + -.2% by weight hydrate) and the reaction was carried out at room temperature for 4 hours to obtain a solution containing polymer (A-1-1) as a polyamic acid ester. The weight-average molecular weight Mw of the resulting polymer (A-1-1) was 91,000, and the polymer viscosity was 400 mPas. The polymer solution was allowed to stand at 20 ℃ for 3 days, and as a result, gelation did not occur and the storage stability was good.

Synthesis examples 1-2 to 1-4

A polyamic acid ester was synthesized in the same manner as in Synthesis example 1-1, except that the kinds and amounts of the tetracarboxylic acid diester and diamine used in the reaction were changed as shown in Table 1 below. Further, a ring-opening reaction of tetracarboxylic dianhydride with the compound (E) was carried out in the same manner as in synthesis example 1-1, except that the kinds of tetracarboxylic dianhydride and the compound (E) used were changed. Each of the polymer solutions obtained in Synthesis examples 1-2 to 1-4 was allowed to stand at 20 ℃ for 3 days, and as a result, neither gel was formed and the storage stability was good.

[ Table 1]

The values in table 1 indicate the use ratio (mol%) of the tetracarboxylic dianhydride to the total amount of the tetracarboxylic dianhydride used in the reaction, and the values in table 1 indicate the use ratio (mol%) of the diamine to the total amount of the diamine used in the reaction (the same applies to tables 4,7, and 10 below).

The acid derivatives and diamines in table 1 are abbreviated as follows.

(acid derivative)

AE-1-1: a reaction product of 1,2,3, 4-cyclobutanetetracarboxylic dianhydride and 4-hydroxydiphenylamine (the compound represented by the formula (3-1-1))

AE-1-2: a reaction product of pyromellitic dianhydride and 4-hydroxydiphenylamine (the compound represented by the formula (3-1-1)) (

AE-1-3: diethyl 1,2,3, 4-cyclobutanetetracarboxylic acid (reaction product of 1,2,3, 4-cyclobutanetetracarboxylic dianhydride with ethanol)

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

(diamine)

DA-1: 4,4' -diaminodiphenylamine

DA-2: 4,4' -diaminodiphenyl ether

Synthetic examples 1 to 5: synthesis of Polymer (B-1-1)

20g of 1,2,3, 4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride was added to 200mL of ethanol. The resulting precipitate was separated by filtration, washed with ethanol, and dried under reduced pressure, whereby the compound (AE-1-3) was obtained as a tetracarboxylic diester in the form of a powder. Then, 100 parts by mole of the compound (AE-1-3) was dissolved in NMP, and then 100 parts by mole of 4,4' -diaminodiphenylamine as a diamine was added thereto and dissolved. To this solution was added 300 parts by mole of 4- (4, 6-dimethoxy-1, 3, 5-triazin-2-yl) -4-methylmorpholinium chloride (DMT-MM, 15. + -.2% by weight hydrate) and the reaction was carried out at room temperature for 4 hours to obtain a solution containing polymer (B-1-1) as a polyamic acid ester. The weight-average molecular weight Mw of the resulting polymer (B-1-1) was 118,000, and the polymer viscosity was 520 mPas.

Synthetic examples 1 to 6: synthesis of Polymer (B-1-2)

1,2,3, 4-cyclobutane tetracarboxylic dianhydride as 100 parts by mole of tetracarboxylic dianhydride and 4,4' -diaminodiphenylamine as 100 parts by mole of diamine were dissolved in NMP and reacted at 30 ℃ for 6 hours to obtain a solution containing polymer (B-1-2) as polyamic acid. The polymer solution thus obtained was prepared to 15% by weight using NMP, and the polymer viscosity of the solution was measured to give 420 mPas.

Synthetic examples 1 to 7: synthesis of Polymer (B-1-3)

A solution containing polymer (B-1-3) as a polyamic acid was obtained by dissolving 100 parts by mole of pyromellitic dianhydride as tetracarboxylic dianhydride and 100 parts by mole of 1, 5-bis (aminophenoxy) pentane as diamine in NMP and reacting at 30 ℃ for 6 hours. The polymer solution thus obtained was prepared to 15% by weight using NMP, and the polymer viscosity of the solution was measured to be 380 mPas.

< preparation of liquid Crystal Aligning agent and evaluation [1] >)

[ example 1-1]

(1) Preparation of liquid crystal aligning agent

The polymer (a-1-1) obtained in synthesis example 1-1 as a polymer was dissolved in a mixed solvent containing N-methyl-2-pyrrolidone (NMP) and Butyl Cellosolve (BC) at a ratio of 50: 50 (weight ratio)) to prepare a solution having a solid content concentration of 3.5 wt%. The solution was filtered using a filter having a pore size of 0.2 μm, thereby preparing a liquid crystal aligning agent (R1-1).

(2) Evaluation of surface roughness of coating film

The prepared liquid crystal aligning agent (R1-1) was applied to a glass substrate using a spinner, prebaked on a hot plate at 80 ℃ for 1 minute, and then heated in an oven at 200 ℃ with a nitrogen gas inside the chamber (postbaking) for 1 hour, thereby forming a coating film having an average film thickness of 0.1. mu.m. The surface of the obtained coating film was observed with an Atomic Force Microscope (AFM), and the center average roughness (Ra) was measured. Evaluation was performed in the following manner: the surface roughness was evaluated as "good" when Ra was less than 5nm, as "acceptable" when Ra was 5nm or more and less than 10nm, and as "poor" when Ra was 10nm or more. In this example, Ra is 7nm, and the surface roughness is "ok".

(3) Manufacture of FFS type liquid crystal display element by rubbing treatment

An FFS type liquid crystal display device 10 shown in fig. 1 was produced. First, a glass substrate 11a having on one surface thereof a pair of electrodes, each having a bottom electrode 15 having no pattern, a silicon nitride film as an insulating layer 14, and a top electrode 13 patterned in a comb-like shape, and an opposing glass substrate 11b having no electrode formed in this order were used as a pair, and the liquid crystal alignment agent (R1-1) prepared in (1) above was applied to the surface of the glass substrate 11a having a transparent electrode and the one surface of the opposing glass substrate 11b using a spinner to form a coating film. Subsequently, the coating film was prebaked on a hot plate at 80 ℃ for 1 minute, and then heated at 230 ℃ for 15 minutes in an oven with nitrogen gas replacement in the storage (postbaking), to form a coating film having an average film thickness of 0.1. mu.m. Schematic plan views of the top electrode 13 used in this embodiment are shown in fig. 2 (a) and 2 (b). Fig. 2 (a) is a plan view of the top electrode 13, and fig. 2 (b) is an enlarged view of a portion C1 surrounded by a broken line in fig. 2 (a). In this example, the line width d1 of the electrode was set to 4 μm, and the distance d2 between the electrodes was set to 6 μm. The top electrode 13 is a four-system drive electrode using an electrode a, an electrode B, an electrode C, and an electrode D. Fig. 3 shows the structure of the driving electrodes used. In this case, the bottom electrode 15 functions as a common electrode that functions for all of the four systems of drive electrodes, and the regions of the four systems of drive electrodes are pixel regions, respectively.

Then, the surfaces of the coating films formed on the glass substrates 11a and 11b were rubbed with cotton to form the liquid crystal alignment film 12. In fig. 2 (b), the rubbing direction of the coating film formed on the glass substrate 11a is indicated by an arrow. Then, a sealant was applied to the outer edge of the surface of one of the pair of substrates having the liquid crystal alignment film, and then these substrates were bonded via a spacer having a diameter of 3.5 μm so that the rubbing directions of the substrates 11a and 11b were antiparallel to each other, and the sealant was cured. Then, liquid crystal MLC-6221 (manufactured by Merck) was injected between the pair of substrates from a liquid crystal injection port to form a liquid crystal layer 16. Further, polarizing plates (not shown) are bonded to both outer surfaces of the substrates 11a and 11b so that the polarization directions of the two polarizing plates are orthogonal to each other, thereby producing the liquid crystal display element 10.

(4) Evaluation of DC residual image characteristics (harsh conditions)

The FFS type liquid crystal display device thus manufactured was applied with a voltage of 20V DC for 500 hours at an ambient temperature of 100 ℃, and the voltage (residual DC voltage) remaining in the liquid crystal cell immediately after the DC voltage was cut was determined by a flicker elimination method. The evaluation was carried out in the following manner: the residual DC voltage was evaluated as "good" when the value was less than 300mV, as "ok" when the value was 300mV or more and less than 500mV, and as "bad" when the value was 500mV or more. As a result, in example 1-1, the residual DC voltage of the liquid crystal display element was 50mV, which is a "good" evaluation.

(5) Evaluation of DC residual image characteristics (Normal conditions)

The manufactured FFS type liquid crystal display device was applied with a voltage of 10V DC for 20 hours at an ambient temperature of 25 ℃, and the voltage (residual DC voltage) remaining in the liquid crystal cell immediately after the DC voltage was cut off was obtained by a flicker elimination method. The evaluation was carried out in the following manner: the residual DC voltage was evaluated as "good" when the value was less than 300mV, as "ok" when the value was 300mV or more and less than 500mV, and as "bad" when the value was 500mV or more. As a result, in example 1-1, the residual DC voltage of the liquid crystal display element was 10mV, which is a "good" evaluation.

(6) Measurement of Voltage holding ratio

The manufactured FFS type liquid crystal display device was measured for a Voltage Holding Ratio (VHR) after 2000 milliseconds from the release of the application after applying a voltage of 1V at 23 ℃ for an application time of 0.5 microseconds and a span of 2000 milliseconds. The measurement apparatus was VHR-1 manufactured by Toyang Technica (Toyo technical) (Inc.). The evaluation was carried out in the following manner: the voltage holding ratio was evaluated as "good" when it was 95% or more, as "ok" when it was 90% or more and less than 95%, and as "bad" when it was less than 90%. As a result, in example 1-1, the voltage holding ratio was 98%, which was a "good" result.

(7) Evaluation of reliability

The manufactured FFS type liquid crystal display device was measured for the voltage holding ratio in the same manner as in (6) and the value was defined as the initial VHR (VHR) _BF ). Then, the liquid crystal display element after the initial VHR measurement was left to stand in an oven at 60 ℃ for 1000 hours under irradiation of a Light Emitting Diode (LED) lamp. Then, the liquid crystal display element was left to stand at room temperature and naturally cooled to room temperature, and then the Voltage Holding Ratio (VHR) was measured in the same manner as in (6) above _AF ). Further, the rate of change of the voltage holding ratio (Δ VHR (%)) before and after the application of stress was determined by the following equation (EX-1).

ΔVHR＝((VHR _BF -VHR _AF )÷VHR _BF )×100…(EX-1)

The reliability was evaluated as follows: the case where the change rate Δ VHR was less than 10% was evaluated as "good", the case where the change rate Δ VHR was 10% or more and less than 20% was evaluated as "ok", and the case where the change rate Δ VHR was 20% or more was evaluated as "bad". As a result, in the liquid crystal display element of this example, Δ VHR was 4%, and the reliability was "good".

Example 1-2 to example 1-6 and comparative example 1-1 to comparative example 1-2

A liquid crystal aligning agent was prepared in the same manner as in example 1-1, except that the kind and amount of the polymer used were changed as described in the following table 2. Further, using the prepared liquid crystal aligning agent, a coating film and a liquid crystal display element were produced in the same manner as in example 1-1, and various evaluations were performed. The evaluation results are shown in table 3 below.

[ Table 2]

[ Table 3]

As shown in table 3, in examples 1-1 to 1-6, the surface roughness of the coating film, and the voltage holding ratio, DC residual image characteristics, and reliability of the liquid crystal display device were all "good" or "acceptable", and as a result, the various characteristics were balanced. In contrast, the DC afterimage characteristics in the comparative example are inferior to those in the examples.

< Synthesis of Polymer [2] >)

Synthesis examples 2-1 to 2-4

A polyamic acid ester was synthesized in the same manner as in Synthesis example 1-1, except that the kinds and amounts of the tetracarboxylic acid diester and diamine used in the reaction were changed as described in Table 4 below. Further, a ring-opening reaction of tetracarboxylic dianhydride with the compound (E) was carried out in the same manner as in synthesis example 1-1, except that the kinds of tetracarboxylic dianhydride and the compound (E) used were changed. The polymer solutions obtained in Synthesis examples 2-1 to 2-4 were allowed to stand at 20 ℃ for 3 days, and as a result, neither gel was formed, and the storage stability was good.

[ Table 4]

The acid derivatives and diamines in table 4 are abbreviated as follows.

(acid derivative)

AE-2-1: a reaction product of 1,2,3, 4-cyclobutanetetracarboxylic dianhydride and 4-hydroxypyridine (the compound represented by the formula (3-2-1))

AE-2-2: a reaction product of pyromellitic dianhydride and 4-hydroxypyridine (the compound represented by the formula (3-2-1))

AE-2-3: diethyl 1,2,3, 4-cyclobutanetetracarboxylic acid (reaction product of 1,2,3, 4-cyclobutanetetracarboxylic dianhydride with ethanol)

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

(diamine)

DA-2: 4,4' -diaminodiphenyl ether

DA-3: 2- (4-aminophenyl) -5-aminopyridine (the compound represented by the formula (d-5))

[ Synthesis examples 2 to 5: synthesis of Polymer (B-2-1)

Diethyl 1,2,3, 4-cyclobutanetetracarboxylic acid (compound (AE-2-3)) was synthesized by the same procedure as in Synthesis examples 1-5. Then, 100 parts by mole of the compound (AE-2-3) was dissolved in NMP, and then 100 parts by mole of 2- (4-aminophenyl) -5-aminopyridine as a diamine was added thereto and dissolved. To this solution was added 300 parts by mole of 4- (4, 6-dimethoxy-1, 3, 5-triazin-2-yl) -4-methylmorpholinium chloride (DMT-MM, 15. + -.2% by weight hydrate) and the reaction was carried out at room temperature for 4 hours to obtain a solution containing polymer (B-2-1) as a polyamic acid ester. The weight-average molecular weight Mw of the resulting polymer (B-2-1) was 80,000, and the viscosity of the polymer was 320 mPas.

Synthesis examples 2 to 6: synthesis of Polymer (B-2-2)

1,2,3, 4-cyclobutane tetracarboxylic dianhydride as 100 molar parts of tetracarboxylic dianhydride and 2- (4-aminophenyl) -5-aminopyridine as 100 molar parts of diamine were dissolved in NMP and reacted at 30 ℃ for 6 hours to obtain a solution containing polymer (B-2-2) as polyamic acid. The polymer solution thus obtained was prepared to 15% by weight using NMP, and the polymer viscosity of the solution was measured to be 300 mPas.

Synthesis examples 2 to 7: synthesis of Polymer (B-2-3)

By carrying out the same operation as in Synthesis examples 1 to 7, a solution containing polymer (B-2-3) as a polyamic acid using pyromellitic dianhydride and 1, 5-bis (aminophenoxy) pentane as starting materials was obtained.

< preparation of liquid Crystal alignment agent and evaluation [2] >)

[ example 2-1]

(1) Preparation of liquid crystal aligning agent

The polymer (a-2-1) obtained in synthesis example 2-1 as a polymer was dissolved in a mixed solvent containing NMP and Butyl Cellosolve (BC) at a ratio of 50: 50 (weight ratio)) to prepare a solution having a solid content of 3.5 wt%. The solution was filtered using a filter having a pore size of 0.2 μm, thereby preparing a liquid crystal aligning agent (R2-1).

(2) Evaluation of surface roughness of coating film

The same operation as in (2) of example 1-1 was carried out except that the liquid crystal aligning agent used was changed to the liquid crystal aligning agent (R2-1) obtained in (1), thereby evaluating the surface unevenness of the coating film. As a result, in this example, Ra was 9nm, and the surface unevenness was "fine".

(3) Manufacture of FFS type liquid crystal display element

An FFS type liquid crystal display device was produced by performing the same operation as in (3) of example 1-1, except that the liquid crystal aligning agent used was changed to the liquid crystal aligning agent (R2-1) obtained in (1).

(4) Measurement of Voltage holding ratio

For the FFS type liquid crystal display device manufactured in (3), the Voltage Holding Ratio (VHR) was measured in the same manner as in (6) of example 1-1. As a result, VHR was 99%, which is a "good" result.

(5) Evaluation of reliability

With respect to the FFS type liquid crystal display element produced in the above (3), the Voltage Holding Ratio (VHR) was measured in the same manner as in the above (7) of the example 1-1 _BF And VHR _AF ). The reliability of the liquid crystal display device was evaluated from the rate of change Δ VHR of the voltage holding ratio before and after application of the stress. As a result, Δ VHR was 6%, and it was judged that the reliability was "good".

Example 2-2 to example 2-6 and comparative example 2-1 to comparative example 2-2

Liquid crystal aligning agents were prepared in the same manner as in example 2-1 except that the kind and amount of the polymer were changed as shown in the following table 5. Further, using the prepared liquid crystal aligning agent, a coating film and a liquid crystal display element were produced in the same manner as in example 2-1, and various evaluations were performed. The evaluation results are shown in table 6 below.

[ Table 5]

[ Table 6]

As shown in table 6, in examples 2-1 to 2-6, the surface unevenness of the coating film and the voltage holding ratio and reliability of the liquid crystal display device were all "good" or "acceptable", and as a result, various characteristics were balanced. In contrast, in the comparative example, the evaluation of reliability was inferior to that in the examples.

< Synthesis of Polymer [3] >)

[ Synthesis examples 3-1 to 3-5]

A polyamic acid ester was synthesized in the same manner as in Synthesis example 1-1, except that the kinds and amounts of a tetracarboxylic acid diester and a diamine used in the reaction were changed as described in Table 7 below. Further, a ring-opening reaction of tetracarboxylic dianhydride with the compound (E) was carried out in the same manner as in synthesis example 1-1, except that the kinds of tetracarboxylic dianhydride and the compound (E) used were changed. Each of the polymer solutions obtained in Synthesis examples 3-1 to 3-5 was allowed to stand at 20 ℃ for 3 days, and as a result, neither gel was formed and the storage stability was good.

[ Table 7]

The acid derivatives and diamines in table 7 are abbreviated as follows.

(acid derivative)

AE-3-1: reaction product of 2,3, 5-tricarboxycyclopentylacetic dianhydride with 2-hydroxyethyl methacrylate

AE-3-2: reaction product of bicyclo [3.3.0] octane-2, 4,6, 8-tetracarboxylic dianhydride and 2-hydroxyethyl methacrylate

AE-3-3: reaction product of pyromellitic dianhydride and 2-hydroxyethyl methacrylate

AE-3-4: reaction product of 2,3, 5-tricarboxycyclopentylacetic dianhydride and ethanol

AN-2: 2,3, 5-tricarboxylic cyclopentyl acetic dianhydride

(diamine)

DA-4: r in the formula (d-6) ⁸ Compounds being methyl groups

DA-5: cholestanoxy-2, 4-diaminobenzene

DA-6: p-phenylenediamine

Synthesis examples 3 to 6: synthesis of Polymer (B-3-1)

20g of 2,3, 5-tricarboxycyclopentylacetic dianhydride as tetracarboxylic dianhydride was added to 200mL of ethanol. The obtained precipitate was separated by filtration, washed with ethanol, and dried under reduced pressure to obtain a compound (AE-3-4) as a tetracarboxylic acid diester in the form of a powder. Then, 100 parts by mole of compound (AE-3-4) was dissolved in NMP, and then 100 parts by mole of compound (DA-4) as diamine was added thereto and dissolved. To this solution was added 300 parts by mole of 4- (4, 6-dimethoxy-1, 3, 5-triazin-2-yl) -4-methylmorpholinium chloride (DMT-MM, 15. + -.2% by weight hydrate) and the reaction was carried out at room temperature for 4 hours to obtain a solution containing polymer (B-3-1) as a polyamic acid ester. The weight-average molecular weight Mw of the resulting polymer (B-3-1) was 103,000, and the viscosity of the polymer was 450 mPas.

Synthesis examples 3 to 7: synthesis of Polymer (B-3-2)

A solution containing a polymer (B-3-2) as a polyamic acid was obtained by dissolving 100 parts by mole of 2,3, 5-tricarboxycyclopentylacetic dianhydride as a tetracarboxylic dianhydride and 100 parts by mole of a compound (DA-4) as a diamine in NMP and reacting at 30 ℃ for 6 hours. The polymer solution thus obtained was prepared to 15% by weight using NMP, and the polymer viscosity of the solution was measured to be 280 mPas.

[ Synthesis examples 3 to 8: synthesis of Polymer (B-3-3)

The same operations as in Synthesis examples 1 to 7 were carried out except for using 1,2,3, 4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and p-phenylenediamine as diamine, thereby obtaining a solution containing polymer (B-3-3) as polyamic acid. The polymer solution thus obtained was prepared to 15% by weight using NMP, and the polymer viscosity of the solution was measured to be 320 mPas.

< preparation of liquid Crystal alignment agent and evaluation [3] >)

[ example 3-1]

(1) Preparation of liquid crystal aligning agent

The polymer (a-3-1) obtained in synthesis example 3-1 as a polymer was dissolved in a mixed solvent containing NMP and Butyl Cellosolve (BC) at a weight ratio of 50: 50 to prepare a solution having a solid content of 3.5 wt%. The solution was filtered using a filter having a pore size of 0.2 μm, thereby preparing a liquid crystal aligning agent (R3-1).

(2) Evaluation of surface roughness of coating film

The same operation as in (2) of example 1-1 was carried out except that the liquid crystal aligning agent used was changed to the liquid crystal aligning agent (R3-1) obtained in (1), thereby evaluating the surface unevenness of the coating film. As a result, in this example, Ra was 8nm, and the surface unevenness was "fine".

(3) Manufacture of VA type liquid crystal cell

The liquid crystal aligning agent (R3-1) prepared in (1) above was applied to each electrode surface of two glass substrates each having an ITO electrode patterned into a slit shape and divided into a plurality of regions using a liquid crystal alignment film printer (manufactured by japan portrait printing (jet)), and after removing the solvent by heating (pre-baking) for 1 minute on a hot plate at 80 ℃, heating (post-baking) for 10 minutes on a hot plate at 150 ℃ was performed to form a liquid crystal alignment film having an average film thickness of

Coating film of (3). The coating film was subjected to ultrasonic cleaning in ultrapure water for 1 minute and then dried in a clean oven at 100 ℃ for 10 minutes, thereby obtaining a substrate having a coating film to be a liquid crystal alignment film. This operation was repeated to obtain a pair (two) of substrates having a coating film. In addition, the pattern of the electrode used is the same pattern as that of the electrode in the PSA mode.

Then, an epoxy resin adhesive containing alumina balls having a diameter of 5.5 μm was applied to the outer edges of the pair of substrates having the coating films, and then the substrates were stacked and pressed so that the coating films were opposed to each other, thereby curing the adhesive. Then, a nematic liquid crystal (MLC-6608, manufactured by Merck) was filled between the pair of substrates from the liquid crystal inlet, and then the liquid crystal inlet was sealed with an acrylic photo-curing adhesive. Then, an alternating current of 10V was applied between the electrodes of the obtained liquid crystal cell at a frequency of 60Hz, and in a state where the liquid crystal was driven, an ultraviolet irradiation apparatus using a metal halide lamp as a light source was used at a rate of 100,000J/m ² The irradiation amount of (3) is such that ultraviolet rays are irradiated from the outside of the liquid crystal cell. The irradiation dose is a value measured using a light meter that measures with reference to a wavelength of 365 nm.

(4) Measurement of pretilt Angle

The pretilt angle was measured using the fabricated liquid crystal cell. Here, the value of the tilt angle of the liquid crystal molecules from the substrate surface measured by the crystal rotation method using He — Ne laser light is used as the pretilt angle according to the method described in non-patent literature (t.j. scheffer) et al, Journal of Applied Physics (j.appl.phys.) 19, 2013 (1980). The evaluation was carried out in the following manner: the measurement value of the pretilt angle was evaluated as "good" when it was less than 88.0 °, as "acceptable" when it was 88.0 ° or more and less than 89.0 °, and as "poor" when it was 89.0% or more. As a result, in this example, the pretilt angle was 87.0 °, which is an evaluation of "good" pretilt angle characteristics.

(5) Measurement of Voltage holding ratio

For the liquid crystal cell produced in (3), the Voltage Holding Ratio (VHR) was measured in the same manner as in (6) of the example 1-1. As a result, VHR was 97%, which was a "good" result.

(6) Evaluation of reliability

With respect to the liquid crystal cell produced in the above (3), the Voltage Holding Ratio (VHR) was measured in the same manner as in the above (7) of the example 1-1 _BF And VHR _AF ). The reliability of the liquid crystal display device was evaluated based on the rate of change Δ VHR of the voltage holding ratio before and after application of stress. As a result, Δ VHR was 5%, and it was judged that the reliability was "good".

Example 3-2 to example 3-7 and comparative example 3-1 to comparative example 3-2

Liquid crystal aligning agents were prepared in the same manner as in example 3-1 except that the kind and amount of the polymer were changed as described in the following Table 8. Further, using the prepared liquid crystal aligning agent, a coating film and a liquid crystal cell were prepared in the same manner as in example 3-1, and various evaluations were performed. The evaluation results are shown in table 9 below.

[ Table 8]

[ Table 9]

As shown in table 9, in examples 3-1 to 3-7, the surface unevenness of the coating film, and the pretilt angle characteristics, voltage holding ratio, and reliability of the liquid crystal display element were all "good" or "acceptable". In contrast, it is difficult to provide a pretilt angle in the comparative example.

< Synthesis of Polymer [4] >)

Synthesis examples 4-1 to 4-4

A polyamic acid ester was synthesized in the same manner as in Synthesis example 1-1, except that the kinds and amounts of a tetracarboxylic acid diester and a diamine used in the reaction were changed as shown in Table 10 below. Further, a ring-opening reaction of tetracarboxylic dianhydride with the compound (E) was carried out in the same manner as in synthesis example 1-1, except that the kinds of tetracarboxylic dianhydride and the compound (E) used were changed. Each of the polymer solutions obtained in Synthesis examples 4-1 to 4-4 was allowed to stand at 20 ℃ for 3 days, and as a result, neither of them was gelled, and the storage stability was good.

[ Table 10]

The acid derivatives and diamines in Table 10 are abbreviated as follows.

(acid derivative)

AE-4-1: a reaction product of pyromellitic dianhydride with 4-hydroxyphenyl benzoate (the compound represented by the formula (3-4-1)) (

AE-4-2: the reaction product of 2,3, 5-tricarboxycyclopentylacetic dianhydride and 4-hydroxyphenyl benzoate (the compound represented by said formula (3-4-1))

AE-4-3: reaction product of pyromellitic dianhydride and ethanol

AN-3: pyromellitic dianhydride

(diamine)

DA-6: p-phenylenediamine

DA-7: 4-aminophenyl-4' -aminobenzoic acid ester

[ Synthesis examples 4 to 5: synthesis of Polymer (B-4-1)

20g of pyromellitic dianhydride as tetracarboxylic dianhydride was added to 200mL of ethanol. The resulting precipitate was separated by filtration, washed with ethanol, and dried under reduced pressure to obtain a compound (AE-4-3) as a tetracarboxylic acid diester in the form of a powder. Then, 100 parts by mole of the compound (AE-4-3) was dissolved in NMP, and then 100 parts by mole of 4-aminophenyl-4' -aminobenzoate as diamine was added thereto and dissolved. To this solution was added 300 parts by mole of 4- (4, 6-dimethoxy-1, 3, 5-triazin-2-yl) -4-methylmorpholinium chloride (DMT-MM, 15. + -.2% by weight hydrate) and the reaction was carried out at room temperature for 4 hours to obtain a solution containing polymer (B-4-1) as a polyamic acid ester. The weight-average molecular weight Mw of the resulting polymer (B-4-1) was 97,000, and the polymer viscosity was 420 mPas.

Synthesis examples 4 to 6: synthesis of Polymer (B-4-2)

100 parts by mole of pyromellitic dianhydride as tetracarboxylic dianhydride and 100 parts by mole of 4-aminophenyl-4' -aminobenzoate as diamine were dissolved in NMP and reacted at 30 ℃ for 6 hours to obtain a solution containing polymer (B-4-2) as polyamic acid. The polymer solution thus obtained was prepared to 15% by weight using NMP, and the polymer viscosity of the solution was measured to be 350 mPas.

[ Synthesis examples 4 to 7: synthesis of Polymer (B-4-3)

The same operations as in synthesis examples 1 to 7 were carried out except for using 1,2,3, 4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and p-phenylenediamine as diamine, to thereby obtain a solution containing polymer (B-4-3) as polyamic acid.

< preparation of liquid Crystal Aligning agent and evaluation [4] >)

[ example 4-1]

(1) Preparation of liquid crystal aligning agent

The polymer (a-4-1) obtained in synthesis example 4-1 as a polymer was dissolved in a mixed solvent containing NMP and Butyl Cellosolve (BC) at a weight ratio of 50: 50 to prepare a solution having a solid content of 3.5 wt%. The solution was filtered using a filter having a pore size of 0.2 μm, thereby preparing a liquid crystal aligning agent (R4-1).

(2) Evaluation of surface roughness of coating film

The same operation as in (2) of example 1-1 was carried out except that the liquid crystal aligning agent used was changed to the liquid crystal aligning agent (R4-1) obtained in (1), thereby evaluating the surface unevenness of the coating film. As a result, Ra in this example was 9nm, and the surface roughness was "good".

(3) Manufacture of FFS type liquid crystal display element by optical alignment method

The liquid crystal aligning agent (R4-1) prepared in (1) was applied to each surface of the same pair of glass substrates 11a and 11b as in (3) of example 1-1 using a spinner to form a coating film. Then, the coating film was prebaked on a hot plate at 80 ℃ for 1 minute, and then heated at 230 ℃ for 15 minutes in an oven with nitrogen gas replacement in the storage (postbaking) to form an average film thickness

Coating film of (3). Schematic plan views of the top electrode 13 used in this embodiment are shown in fig. 4 (a) and 4 (b). Fig. 4 (a) is a plan view of the top electrode 13, and fig. 4 (b) is an enlarged view of a portion C1 surrounded by a broken line in fig. 4 (a). In this example, a substrate having a top electrode with a line width d1 of 4 μm and an inter-electrode distance d2 of 6 μm was used. Further, as the top electrode 13, four systems of driving electrodes of the electrode a, the electrode B, the electrode C, and the electrode D were used (see fig. 3) in the same manner as in (3) of the above-described example 1-1.

Then, each surface of these coating films was irradiated with 300J/m from the substrate normal direction using an Hg-Xe lamp and a Glan Taylor prism, respectively ² The pair of substrates having the liquid crystal alignment film was obtained by using polarized ultraviolet rays containing a bright line of 313 nm. At this time, the irradiation direction of the polarized ultraviolet rays is set from the substrate normal direction, the polarization plane direction is set so that the direction of a line segment projecting the polarization plane of the polarized ultraviolet rays onto the substrate becomes the direction of the double-headed arrow in fig. 4, and then the light irradiation treatment is performed.

Then, an epoxy resin adhesive containing alumina balls having a diameter of 5.5 μm was applied to the outer periphery of the surface having the liquid crystal alignment film of one of the substrates by screen printing, and then the liquid crystal alignment films of the pair of substrates were faced to each other, and were overlapped and pressed so that the directions of polarization planes of polarized ultraviolet rays projected onto the substrates were parallel to each other, and the adhesive was thermally cured at 150 ℃ for 1 hour. Subsequently, a liquid crystal "MLC-6221" manufactured by Merck (Merck) was filled into the gap between the substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy resin adhesive. Then, in order to remove the flow alignment at the time of liquid crystal injection, it was heated to 150 ℃ and then slowly cooled to room temperature. Further, polarizing plates are bonded to both outer sides of the substrates 11a and 11b, thereby producing a liquid crystal display element. In this case, one of the polarizing plates is attached so that the polarization direction thereof is parallel to the projection direction of the plane of polarization of the ultraviolet light of the liquid crystal alignment film on the substrate surface, and the other is attached so that the polarization direction thereof is orthogonal to the polarization direction of the polarizing plate immediately before.

(4) Evaluation of AC afterimage characteristics

The FFS type liquid crystal display device manufactured in (3) was placed in an environment of 25 ℃ and 1 atm. The bottom electrode was used as a common electrode for all of the four systems of drive electrodes, and the potential of the bottom electrode was set to 0V potential (ground potential). While the electrodes B and D and the common electrode were short-circuited and set in a 0V applied state, a combined voltage including an ac voltage of 5V was applied to the electrodes a and C for 100 hours. After 100 hours had elapsed, a voltage of 1.5V was applied to all of the electrodes A to D. Then, the time from the time when the application of the ac 1.5V voltage was started to all of the electrodes a to D until the difference in luminance between the driving stress applied region (the pixel region of the electrode a and the electrode C) and the driving stress non-applied region (the pixel region of the electrode B and the electrode D) could no longer be visually confirmed was measured and taken as the afterimage elimination time Ts. Further, the shorter the time, the more difficult afterimages are generated. The liquid crystal display device of the present embodiment was evaluated as "good" when the afterimage elimination time Ts was less than 30 seconds, as "good" when the afterimage elimination time Ts was 30 seconds or more and less than 120 seconds, and as "bad" when the afterimage elimination time Ts was 120 seconds or more.

(5) Measurement of Voltage holding ratio

For the FFS type liquid crystal display device manufactured in (3), the Voltage Holding Ratio (VHR) was measured in the same manner as in (6) of example 1-1. As a result, VHR was 96%, which is a "good" result.

(6) Evaluation of reliability

Using the liquid crystal display element produced in the above (3), the Voltage Holding Ratio (VHR) was measured in the same manner as in the above (7) of the example 1-1 _BF And VHR _AF ). The reliability of the liquid crystal display device was evaluated based on the rate of change Δ VHR of the voltage holding ratio before and after application of stress. As a result, Δ VHR was 12%, and evaluated as "ok" in reliability.

Example 4-2 to example 4-6 and comparative example 4-1 to comparative example 4-2

Liquid crystal aligning agents were prepared in the same manner as in example 4-1, except that the kind and amount of the polymer were changed as described in the following table 11. Further, using the prepared liquid crystal aligning agent, a coating film and a liquid crystal cell were produced in the same manner as in example 4-1, and various evaluations were performed. The evaluation results are shown in table 12 below.

[ Table 11]

[ Table 12]

As shown in table 12, in examples 4-1 to 4-6, the surface unevenness of the coating film and the AC image sticking characteristics, the voltage holding ratio, and the reliability of the liquid crystal display device were all "good" or "acceptable". In contrast, in the comparative example, the AC image sticking characteristic was evaluated as "poor", and was inferior to that in the examples.

Claims (3)

1. A liquid crystal aligning agent characterized by comprising:

a polymer (P) having a partial structure represented by the following formula (1); and

a polymer (Q) which is a polyamic acid,

in the formula (1), R ¹ Is a tetravalent organic radical, R ² Is a divalent organic radical; x ¹ And X ² Each independently represents a hydroxyl group or a monovalent organic group having 1 to 40 carbon atoms; wherein X ¹ And X ² Is a monovalent organic group having a nitrogen-containing heterocyclic group containing pyridine as a heterocyclic ring;

the content of the polymer (P) is 40 to 99 parts by weight, based on 100 parts by weight of the total of the polymer (P) and the polymer (Q).

2. A liquid crystal alignment film characterized in that: formed using the liquid crystal aligning agent according to claim 1.

3. A liquid crystal display element, characterized in that: comprising the liquid crystal alignment film according to claim 2.

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