WO2022220199A1

WO2022220199A1 - Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element

Info

Publication number: WO2022220199A1
Application number: PCT/JP2022/017388
Authority: WO
Inventors: 昂太郎溝口; 達也結城; 夏樹佐藤; 雄介山本
Original assignee: 日産化学株式会社
Priority date: 2021-04-13
Filing date: 2022-04-08
Publication date: 2022-10-20
Also published as: KR20230169081A; TW202307184A; JPWO2022220199A1; CN117222939A

Abstract

Provided are: a liquid crystal aligning agent which forms a liquid crystal alignment film that exhibits a high voltage retention ratio, suppresses the occurrence of after-images, and exhibits low liquid crystal pretilt angle characteristics; a liquid crystal alignment film obtained from said liquid crystal aligning agent; and a liquid crystal display element comprising said liquid crystal alignment film.　The liquid crystal aligning agent is characterized by containing a polymer having at least one repeating unit selected from the group consisting of a repeating unit (p1) represented by formula (1) and an imidized structure unit of said repeating unit (p1). (In formula (1), X₁ represents a tetravalent organic group. Y₁ is a divalent organic group represented by "-Ar₁-O-W-O-Ar₂-".　Ar₁ and Ar₂ each independently represent a divalent aromatic group of any one of a divalent benzene ring or a biphenyl structure, and any hydrogen atom of the aromatic group may be substituted with a monovalent group.　W is a divalent organic group having 4 to 20 carbon atoms, which is represented by *-(CH₂)_m-L-A-*(L represents -O-C(=O)- or -C(=O)-O-, and A represents -(CH₂)_n-. m is an integer of 1-6. n is an integer of 1-16. When n is 2 or greater, any -CH₂- constituting A may be substituted with -O-, -C(=O)-, -NH-, -O-C(=O)-, -C(=O)-O-, -C=C-, a phenylene group, or a cyclohexylene group. In addition, a portion of hydrogen atoms of W may be substituted with a halogen atom, a methyl group, a trifluoromethyl group, or a hydroxy group.)The symbol * represents a bond.) The symbol * represents a bond.　R and Z each independently represent a hydrogen atom or a monovalent organic group.)

Description

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

The present invention relates to a liquid crystal aligning agent, a liquid crystal aligning film obtained from the liquid crystal aligning agent, a liquid crystal display element comprising the liquid crystal aligning film, and a novel diamine and polymer suitable for them.

Liquid crystal display elements are used in a wide range of applications, from small applications such as mobile phones and smartphones to relatively large applications such as televisions and monitors. In addition, various driving methods with different electrode structures and physical properties of the liquid crystal molecules used have been developed. -Plane Switching), FFS (Fringe Field Switching), and other liquid crystal display devices using various modes are known. These liquid crystal display elements generally have a liquid crystal alignment film that is indispensable for controlling the alignment state of liquid crystal molecules. Polyamic acid and polyimide are generally used as materials for liquid crystal alignment films because of their excellent properties such as heat resistance, mechanical strength, and affinity with liquid crystals.

Liquid crystal display elements are required to have high display quality, and one of the required characteristics is, for example, to exhibit a high voltage holding ratio. For this purpose, Patent Document 1 discloses a composition for a liquid crystal alignment film containing an aromatic diamine such as 1,5-bis(4-aminophenoxy)pentane. Further, Patent Document 2 discloses that a polyamic acid or the like obtained by reacting a diamine having two aromatic rings linked by a specific alkylene group with a tetracarboxylic acid derivative is used as a polymer component of a liquid crystal aligning agent. It is

Japanese Patent Laid-Open No. 06-194670 Japanese Patent Application Laid-Open No. 2014-132326

In recent years, as the performance of liquid crystal display elements has improved, in addition to large-screen, high-definition liquid crystal televisions, it has been applied to in-vehicle applications such as car navigation systems, meter panels, surveillance cameras, and medical camera monitors. being considered. Therefore, the demand for higher performance, particularly higher definition, of liquid crystal display elements is increasing, and a liquid crystal alignment film capable of further improving various characteristics of liquid crystal display elements is desired.

The present invention provides long-term reliability of so-called display quality, in which display defects such as image burn-in (image burn-in of divisions and lines), unevenness, and staining that occur over time due to external stimuli such as light and temperature are suppressed. It is an object of the present invention to form a liquid crystal alignment film having a high voltage holding ratio which is a condition for bringing about. In addition, the present invention can form a liquid crystal alignment film exhibiting low liquid crystal pretilt angle characteristics that can suppress afterimages (hereinafter, also referred to as AC afterimages) generated by long-term AC driving and can meet the demand for viewing angle characteristics. Another object of the present invention is to provide a liquid crystal aligning agent, a liquid crystal display device having the liquid crystal aligning film, and a novel diamine and polymer suitable for them.

As a result of intensive research to achieve the above objects, the present inventors have found that a liquid crystal aligning agent containing a specific polymer is effective for achieving the above objects, and have completed the present invention. reached.

The gist of the present invention is as follows.
Characterized by containing a polymer having at least one repeating unit selected from the group consisting of a repeating unit (p1) represented by the following formula (1) and an imidized structural unit of the repeating unit (p1) Liquid crystal aligning agent.

(In Formula (1), X ₁ represents a tetravalent organic group. Y ₁ represents a divalent organic group represented by "-Ar ₁ -OWO-Ar ₂ -".
Ar ₁ and Ar ₂ each independently represent a divalent aromatic group of either a divalent benzene ring or a biphenyl structure, any hydrogen atom of the aromatic group being replaced with a monovalent group may
W represents *-(CH ₂ ) _m -L-A-* (L represents -O-C(=O)- or -C(=O)-O-, and A represents -(CH ₂ ) _n - represents.
m is an integer of 1-6. n is an integer from 1 to 16; When n is 2 or more, any —CH ₂ — constituting A is —O—, —C(=O)—, —NH—, —OC(=O)—, —C(=O ) —O—, —C═C—, a phenylene group, or a cyclohexylene group.
Also, some of the hydrogen atoms of W may be substituted with a halogen atom, a methyl group, a trifluoromethyl group, or a hydroxy group. ) is a divalent organic group having 4 to 20 carbon atoms. * represents a bond.
R and Z each independently represent a hydrogen atom or a monovalent organic group. )
In the present invention, the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and * represents a bond.

INDUSTRIAL APPLICABILITY According to the present invention, a liquid crystal aligning agent for forming a liquid crystal aligning film exhibiting a high voltage holding ratio, suppressing the generation of an afterimage, and exhibiting a low liquid crystal pretilt angle characteristic, and a liquid crystal aligning film obtained from the liquid crystal aligning agent. , a high-performance liquid crystal display device comprising the liquid crystal alignment film, and novel diamines and polymers used for their production are obtained.

Although the mechanism by which the above effects of the present invention are obtained is not necessarily clear, it is estimated as follows. First, the specific diamine, which will be described later, has a structure in which an oxygen atom is bonded to an aromatic group, so when it is used as a liquid crystal alignment film, it interacts with ionic impurities that cause display defects, and the diffusion of impurities is suppressed. It is considered that the voltage holding ratio is improved by the trapping phenomenon that is suppressed. In addition, it is considered that the above effect was obtained because the same trapping phenomenon for impurities also occurs in the ester bond of the specific diamine. Furthermore, since the specific diamine has an ester bond or an alkylene chain, the stretchability of the polymer during alignment treatment is increased, and high liquid crystal alignment is obtained, so the occurrence of AC afterimage is suppressed. Liquid crystal alignment film is obtained.

1 is a schematic partial cross-sectional view showing an example of a lateral electric field liquid crystal display device of the present invention; FIG. FIG. 4 is a schematic partial cross-sectional view showing another example of the horizontal electric field liquid crystal display device of the present invention;

<Polymer Contained in Liquid Crystal Aligning Agent>
As described above, the liquid crystal aligning agent of the present invention comprises at least one repeating unit selected from the group consisting of a repeating unit (p1) represented by the following formula (1) and an imidized structural unit of the repeating unit (p1) It is characterized by containing a polymer having a unit.

(In formula (1), X ₁ , Y ₁ , R and Z are each as defined above.)

Ar ₁ , W and Ar ₂ in Y ₁ (“—Ar ₁ —OW—O—Ar ₂ —”) in formula (1) above are Ar ₁ in formula (D _A ) described below, including preferred embodiments. , W and _Ar2 .
“—N(Z)—Ar ₁ —OW—O—Ar ₂ —N(Z)—” in the above formula (1) means that, for example, a diamine component containing the following specific diamine is used as a starting material for the polymer. However, it is not limited to this method.
The monovalent organic group for R and Z in the above formula (1) includes a monovalent hydrocarbon group having 1 to 6 carbon atoms, and the methylene group of the hydrocarbon group is -O-, -S-, -CO -, -COO-, -COS-, -NR ³ -, -CO-NR ³ -, -Si(R ³ ) ₂ - (where R ³ is a hydrogen atom or a monovalent carbon atom having 1 to 6 carbon atoms) is a hydrogen group), a monovalent group A substituted with —SO ₂ —, etc., the above monovalent hydrocarbon group, or at least one hydrogen atom bonded to a carbon atom of the above monovalent group A is a halogen Atoms, hydroxy groups, alkoxy groups, nitro groups, amino groups, mercapto groups, nitroso groups, alkylsilyl groups, alkoxysilyl groups, silanol groups, sulphino groups, phosphino groups, carboxy groups, cyano groups, sulfo groups, acyl groups, etc. Examples include a substituted monovalent group and a monovalent group having a heterocyclic ring.
The monovalent organic group for R and Z in the above formula (1) includes, among others, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, or a tert A -butoxycarbonyl group is preferred, an alkyl group having 1 to 3 carbon atoms is more preferred, and a methyl group is even more preferred.
From the viewpoint of suitably obtaining the effects of the present invention, R and Z are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group.
X ₁ in the above formula (1) includes, for example, a tetravalent organic group derived from a tetracarboxylic dianhydride or a derivative thereof, which will be described later. Preferred embodiments of the tetracarboxylic dianhydride or derivative thereof in X ₁ above include preferred embodiments of the tetracarboxylic dianhydride or derivative thereof that can be used for synthesizing the polymer (P) described later.

<Specific diamine>
The polymer contained in the liquid crystal aligning agent of the present invention is, for example, a polyimide precursor obtained using a diamine component containing a diamine (0) represented by the following formula (D _A ) (hereinafter also referred to as a specific diamine) and at least one polymer (P) selected from the group consisting of a polyimide which is an imidized product of the polyimide precursor.

In the above formula (D _A ), Ar ₁ , Ar ₂ and W are each as defined above.

In the above formula (D _A ), W is a divalent organic group having 4 to 20 carbon atoms represented by *-(CH ₂ ) _m -LA-*. From the viewpoint of obtaining, a divalent organic group having 4 to 18 carbon atoms is more preferable, and a divalent organic group having 4 to 16 carbon atoms is even more preferable.
Further, L in W above is preferably -OC(=O)-. A is preferably —(CH ₂ ) _n — (n is an integer of 1 to 16) or —(CH ₂ ) _n′ — (n′ is an integer of 2 to 16). of -CH ₂ - is -O-, -C(=O)-, -NH-, -O-C(=O)-, -C(=O)-O-, -C=C-, phenylene or a divalent organic group substituted with a cyclohexylene group.
From the viewpoint of obtaining high liquid crystal orientation, m is more preferably an integer of 2 to 6, more preferably an integer of 2 to 4, and even more preferably an integer of 2 or 4. n is preferably 1-13. A fluorine atom is preferable as the halogen atom that replaces the hydrogen atom of W.

More preferred specific examples of W are *-(CH ₂ ) _p -OC(=O)-(CH ₂ ) _q -*, *-(CH ₂ ) _p -OC(=O) -(CH ₂ ) _q -C(=O)-O-(CH ₂ ) _r -, *-(CH ₂ ) _p -C(=O)-O-(CH ₂ ) _q -O-C(=O )—(CH ₂ ) _r −*, *—(CH ₂ ) _p —O—C(=O)—QC(=O)—O—(CH ₂ ) _q —* (Q is a phenylene group or cyclohexane represents a silene group.), *-(CH ₂ ) _p -C(=O)-OQ-O-C(=O)-(CH ₂ ) _q -* (Q represents a phenylene group or a cyclohexylene group; represents.). Here, p is an integer of 1-6, preferably an integer of 2-6. q is an integer of 1 to 6, more preferably an integer of 2 to 6, even more preferably an integer of 2, 4 or 6. r is an integer of 1-6, preferably an integer of 2-6.

The monovalent group that substitutes the divalent aromatic hydrogen atoms of Ar ₁ and Ar ₂ in the above formula (D _A ) includes a halogen atom, an alkyl group having 1 to 10 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms. group, alkoxy group having 1 to 10 carbon atoms, fluoroalkyl group having 1 to 10 carbon atoms, fluoroalkenyl group having 2 to 10 carbon atoms, fluoroalkoxy group having 1 to 10 carbon atoms, carboxy group, hydroxy group, 1 carbon atom to 10 alkyloxycarbonyl groups, cyano groups, nitro groups, and the like. Among them, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a fluoroalkyl group having 1 to 5 carbon atoms, or a fluoroalkoxy group having 1 to 5 carbon atoms is preferable.

Preferred examples of divalent aromatic groups represented by Ar ₁ and Ar ₂ include 1,4-phenylene, 1,3-phenylene, 2-methyl-1,4-phenylene, 2-ethyl-1, 4-phenylene, 2-propyl-1,4-phenylene, 2-butyl-1,4-phenylene, 2-isopropyl-1,4-phenylene, 2-tert-butyl-1,4-phenylene, 2-methoxy- 1,4-phenylene, 2-ethoxy-1,4-phenylene, 2-propoxy-1,4-phenylene, 2-butoxy-1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3- dimethyl-1,4-phenylene, 4-methyl-1,3-phenylene, 5-methyl-1,3-phenylene, 4-fluoro-1,3-phenylene, 2,3,5,6-tetramethyl-1 ,4-phenylene, 4,4'-biphenylylene, 2-methyl-4,4'-biphenylylene, 2-ethyl-4,4'-biphenylylene, 2-propyl-4,4'-biphenylylene, 2-butyl-4 ,4'-biphenylylene, 2-tert-butyl-4,4'-biphenylylene, 2-methoxy-4,4'-biphenylylene, 2-ethoxy-4,4'-biphenylylene, 2-fluoro-4,4'- biphenylylene, 3-methyl-4,4'-biphenylylene, 3-ethyl-4,4'-biphenylylene, 3-propyl-4,4'-biphenylylene, 3-butyl-4,4'-biphenylylene, 3-tert- Butyl-4,4'-biphenylylene, 3-methoxy-4,4'-biphenylylene, 3-ethoxy-4,4'-biphenylylene, 3-fluoro-4,4'-biphenylylene, 2,2'-dimethyl-4 ,4'-biphenylylene, 3,3'-dimethyl-4,4'-biphenylylene, 3,3'-biphenylylene, 5-methyl-3,3'-biphenylylene, 5,5'-dimethyl-3,3'- biphenylylene and the like.

Preferred examples of the above formula (D _A ) include the following formulas (d _A -1) to (d _A -5). A hydrogen atom on the benzene ring in the following formulas (d _A -1) to (d _A -5) may be substituted with a monovalent substituent, and preferred specific examples of the substituent include the above formula ( Examples include the structures exemplified by the monovalent groups substituting the divalent aromatic hydrogen atoms of Ar ₁ and Ar ₂ in D _A ).

(Polymer (P))
The polymer (P) contained in the liquid crystal aligning agent of the present invention is, for example, a polyimide precursor obtained using a diamine component containing the diamine (0), or a polyimide that is an imidized product of the polyimide precursor. be. Here, the polyimide precursor is a polymer from which a polyimide can be obtained by imidating polyamic acid, polyamic acid ester, or the like.
A polyamic acid (P′), which is a polyimide precursor of the polymer (P), can be obtained by a polymerization reaction between a diamine component containing the diamine (0) and a tetracarboxylic acid component. The diamine (0) may be used alone or in combination of two or more.
The amount of diamine (0) used is preferably 5 mol % or more, more preferably 10 mol % or more, and even more preferably 20 mol % or more, relative to the total diamine component.

From the viewpoint of suitably obtaining the effects of the present invention, the polymer (P) has a total of repeating units (p1) and the imidized structure of the repeating units (p1) of 5 moles of all repeating units that the polymer (P) has. % or more, more preferably 10 mol % or more, and even more preferably 20 mol % or more. The total here includes the case where either the repeating unit (p1) or the imidized structure of the repeating unit (p1) is 0 mol %. In the following description, the term "total" also includes the case where one or more of the constituent elements are 0 mol %.

The diamine component used for producing the polyamic acid (P') may contain diamines other than diamine (0) (hereinafter also referred to as other diamines). When other diamines are used in addition to the diamine (0), the amount of the diamine (0) used is preferably 90 mol % or less, more preferably 80 mol % or less, relative to the diamine component.

Examples of other diamines are listed below, but are not limited to these. The other diamines may be used singly or in combination of two or more. p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2, 5-diaminotoluene, 2,6-diaminotoluene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4 ,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 2,2'-difluoro-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-diamino biphenyl, 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl, 3,3′-bis(trifluoromethyl)-4,4′-diaminobiphenyl, 3,4′-diaminobiphenyl, 4,4′-diaminobiphenyl, 3,3′-diaminobiphenyl, 2,2′-diaminobiphenyl, 2,3′-diaminobiphenyl represented by the following formulas (d _AL -1) to (d _AL -10) diamine, 1,7-bis(4-aminophenoxy)heptane, 1,7-bis(3-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3- aminophenoxy)octane, 1,9-bis(4-aminophenoxy)nonane, 1,9-bis(3-aminophenoxy)nonane, 1,10-bis(4-aminophenoxy)decane, 1,10-bis( 3-aminophenoxy)decane, 1,11-bis(4-aminophenoxy)undecane, 1,11-bis(3-aminophenoxy)undecane, 1,12-bis(4-aminophenoxy)dodecane, 1,12- bis(3-aminophenoxy)dodecane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 4-bis(4-aminophenoxy)biphenyl, 4,4' -bis(4-aminophenoxy)diphenyl ether, 1,4-bis[4-(4-aminophenoxy)phenoxy]benzene, 1,2-bis(6-amino-2-naphthyloxy)ethane, 1,2-bis (6-amino-2-naphthyl)ethane, 6-[2-(4-aminophenoxy)ethoxy]-2-naphthylamine, 1,4-phenylenebis(4-aminobenzoate), 1,4-phenylenebis(3 -aminobenzoate), 1,3-phenyl lenbis(4-aminobenzoate), 1,3-phenylenebis(3-aminobenzoate), bis(4-aminophenyl)terephthalate, bis(3-aminophenyl)terephthalate, bis(4-aminophenyl)isophthalate, bis (3-aminophenyl) isophthalate; diamines having photoalignable groups such as 4,4′-diaminoazobenzene or diaminotran; 2-(2,4-diaminophenoxy)ethyl methacrylate or 2,4-diamino-N , N-diallylaniline and other photopolymerizable group-terminated diamines; 1-(4-(2-(2,4-diaminophenoxy)ethoxy)phenyl)-2-hydroxy-2-methylpropanone, 2- Diamines with a radical polymerization initiator function such as (4-(2-hydroxy-2-methylpropanoyl)phenoxy)ethyl-3,5-diaminobenzoate; Diamines with an amide bond such as 4,4′-diaminobenzanilide , 1,3-bis(4-aminophenyl)urea, 1,3-bis(4-aminobenzyl)urea, 1,3-bis(4-aminophenethyl)urea, diamines having a urea bond; '-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 2,2 '-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis(4-aminophenyl)hexa Fluoropropane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2'-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2'-bis(4-aminophenyl ) propane, 2,2′-bis(3-aminophenyl)propane, 2,2′-bis(3-amino-4-methylphenyl)propane, 4,4′-diaminobenzophenone, 1,4-bis(4 -aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene; 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4- Diaminopyrimidine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, 1,4-bis-(4-aminophenyl)-pipe Radin, 3,6-diaminoacridine, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N-(3-(1H-imidazol-1-yl)propyl-3,5 -Diaminobenzamide, 4-[4-[(4-aminophenoxy)methyl]-4,5-dihydro-4-methyl-2-oxazolyl]-benzenamine, or the following formulas (z-1) to (z- 13), or heterocycle-containing diamines such as diamines represented by benzidine, N,N'-bis(4-aminophenyl)-N,N'-dimethylbenzidine, or N,N'-bis(4-aminophenyl)-N,N'-dimethyl-1,4-benzene At least one nitrogen atom-containing structure (hereinafter referred to as a specific nitrogen atom Also called inclusion structure. ) (provided that the molecule does not have an amino group bonded with a protective group that is eliminated by heating and replaced with a hydrogen atom.); 2,4-diaminophenol, 3,5-diaminophenol, 3,5- diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diamino-3,3'-dihydroxybiphenyl; 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,4'-diaminobiphenyl-3-carboxylic acid, 4,4'-diaminodiphenylmethane-3-carboxylic acid, 4,4'-diaminodiphenylethane-3-carboxylic acid, 4, 4'-diaminobiphenyl-3,3'-dicarboxylic acid, 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid, 3,3'-diaminobiphenyl-4,4'-dicarboxylic acid, 3,3'-diaminobiphenyl-2,4'-dicarboxylic acid, 4,4'-diaminodiphenylmethane-3,3'-dicarboxylic acid, 4,4'-diaminodiphenylethane-3,3'-dicarboxylic acid, 4,4'- Diamines having a carboxyl group such as diaminodiphenyl ether-3,3′-dicarboxylic acid; 4-(2-(methylamino)ethyl)aniline, 4-(2-aminoethyl)aniline, 1-(4-aminophenyl)- 1,3,3-trimethyl-1H-indan-5-amine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indene-6-amine; 5-1) to (5-6) groups such as "-N(D)-" (D represents a protecting group that is eliminated by heating and replaced by a hydrogen atom, preferably a carbamate-based protecting group, more preferably a tert -butoxycarbonyl group), cholestanyloxy-3,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, 3,5-diamino Diamines having a steroid skeleton such as cholestanyl benzoate, cholestenyl 3,5-diaminobenzoate, lanostanyl 3,5-diaminobenzoate and 3,6-bis(4-aminobenzoyloxy)cholestane, the following formula (V-1) Diamine represented by ~ (V-2); diamine having a siloxane bond such as 1,3-bis(3-aminopropyl)-tetramethyldisiloxane; meta-xylylenediamine, 1,3-propanediamine, Tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), described in WO 2018/117239 diamines in which two amino groups are bonded to a group represented by any one of the formulas (Y-1) to (Y-167);

(Boc represents a tert-butoxycarbonyl group.)

In the above formula (V-1), m and n are integers from 1 to 3 and satisfy 1≦m+n≦4. j is an integer of 0 or 1; X ¹ is -(CH ₂ ) _a - (a is an integer of 1 to 15), -CONH-, -NHCO-, -CO-N(CH ₃ )-, -NH-, -O-, represents -CH ₂ O-, -CH ₂ -OCO-, -COO- or -OCO-; R ¹ is a fluorine atom, a fluorine atom-containing alkyl group having 1 to 10 carbon atoms, a fluorine atom-containing alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and It represents a monovalent group such as an alkoxyalkyl group having 2 to 10 carbon atoms. In formula (V-2) above, X ² represents -O-, -CH ₂ O-, -CH ₂ -OCO-, -COO- or -OCO-. When two of m, n, X ¹ and R ¹ are present, each independently has the above definition.

When other diamines are used in addition to the diamine (0), the amount of the other diamines used is preferably 10 to 90 mol%, more preferably 20 to 90 mol%, based on the total diamine components used. 80 mol %.
The amount of the other diamine used is preferably 10 to 90 mol %, more preferably 20 to 80 mol %, based on the total diamine components used in the production of the polymer (P).

(Tetracarboxylic acid component)
When producing the polyamic acid (P'), the tetracarboxylic acid component to be reacted with the diamine component is not only tetracarboxylic dianhydride, but also tetracarboxylic acid, tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester, or tetracarboxylic acid. Derivatives of tetracarboxylic dianhydrides such as carboxylic acid dialkyl ester dihalides can also be used.

The tetracarboxylic dianhydride or derivative thereof includes an acyclic aliphatic tetracarboxylic dianhydride, an alicyclic tetracarboxylic dianhydride, an aromatic tetracarboxylic dianhydride, or derivatives thereof. . Among them, it is more preferable to contain a tetracarboxylic dianhydride having at least one partial structure selected from the group consisting of a benzene ring, a cyclobutane ring, a cyclopentane ring and a cyclohexane ring, or a derivative thereof. In particular, it is more preferable to contain a tetracarboxylic dianhydride having at least one structure selected from the group consisting of a cyclobutane ring, a cyclopentane ring and a cyclohexane ring, or a derivative thereof.
The aromatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups including at least one carboxy group bonded to an aromatic ring.
An acyclic aliphatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups bonded to a chain hydrocarbon structure. However, it does not need to be composed only of a chain hydrocarbon structure, and may partially have an alicyclic structure or an aromatic ring structure.
An alicyclic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups including at least one carboxy group bonded to an alicyclic structure. However, none of these four carboxy groups are bonded to the aromatic ring. Moreover, it is not necessary to consist only of an alicyclic structure, and a part thereof may have a chain hydrocarbon structure or an aromatic ring structure.

The tetracarboxylic acid component that can be used in the production of the polyamic acid (P′) preferably includes the following tetracarboxylic dianhydrides or derivatives thereof (in the present invention, these are collectively referred to as specific tetracarboxylic acids Also called derivatives.).
Acyclic aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride; 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl -1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3 ,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-difluoro-1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 1,3-bis(trifluoromethyl)-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3′,4,4′-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride product, 4-(2,5-dioxotetrahydrofuran-3-yl)tetrahydronaphthalene-1,2-dicarboxylic dianhydride, 5-(2,5-dioxotetrahydrofuran-3-yl)-3a, 4, 5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-dioxotetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydro naphtho[1,2-c]furan-1,3-dione, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2 .2]octane-2,3,5,6-tetracarboxylic dianhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride alicyclic tetracarboxylic dianhydrides such as products; pyromellitic dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 3,3′,4,4′-biphenylsulfone Tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-biphenyl ethertetracarboxylic dianhydride, 3,3′,4,4′-perfluoroisopropylidene diphthalic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 2,2 ',3,3'-biphenyltetracarboxylic dianhydride, 4,4'-bi Su(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, ethylene glycol bisanhydrotrimate, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 4,4'-carbonyldiphthalic anhydride 4,4′-oxydi(1,4-phenylene)bis(phthalic acid) dianhydride, or 4,4′-methylenedi(1,4-phenylene)bis(phthalic acid) dianhydride, etc. tetracarboxylic dianhydrides; other tetracarboxylic dianhydrides described in JP-A-2010-97188.

Preferred examples of the above specific tetracarboxylic acid derivatives include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl -1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl- 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-difluoro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-bis(trifluoromethyl)-1 , 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3, 3′,4,4′-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5-(2,5-dioxotetrahydrofuran-3-yl)-3a,4, 5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-dioxotetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydro naphtho[1,2-c]furan-1,3-dione, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, pyromellit acid dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 3,3′,4,4′-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8- naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3′,4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3′,4, 4′-biphenyltetracarboxylic dianhydride, 2,2′,3,3′-biphenyltetracarboxylic dianhydride, or derivatives thereof.

The proportion of the above-mentioned specific tetracarboxylic acid derivative used is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 50 mol% or more, relative to the total tetracarboxylic acid components used.

(Liquid crystal aligning agent)
The liquid crystal aligning agent of the present invention is, for example, a liquid composition in which the polymer (P) and optionally other components are preferably dispersed or dissolved in a suitable solvent.
The total content of the polymer contained in the liquid crystal aligning agent of the present invention can be appropriately changed depending on the setting of the thickness of the coating film to be formed. % or more is preferable, and 10% by mass or less is preferable from the viewpoint of storage stability of the solution. A particularly preferred total polymer content is 2 to 8% by weight.
The content of the polymer (P) used in the present invention is preferably 1 to 100% by mass, more preferably 10 to 100% by mass, and 20 to 100% by mass with respect to the total amount of the polymer contained in the liquid crystal aligning agent. % is particularly preferred.

The liquid crystal aligning agent of the present invention may contain polymers other than the polymer (P). Specific examples of other polymers include, in addition to the polymer (P), a polyimide precursor obtained using a diamine component that does not have the specific diamine and a polyimide that is an imidized product of the polyimide precursor. At least one polymer selected from the group (also referred to as polymer (B) in the present invention), polysiloxane, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivative, polyacetal, polystyrene derivative, poly(styrene-malein acid anhydride) copolymer, poly(isobutylene-maleic anhydride) copolymer, poly(vinyl ether-maleic anhydride) copolymer, poly(styrene-phenylmaleimide) derivative, poly(meth)acrylate and polymers selected from the group.

Specific examples of the poly(styrene-maleic anhydride) copolymer include SMA1000, SMA2000, SMA3000 (manufactured by Cray Valley), GSM301 (manufactured by Gifu Shellac Manufacturing Co., Ltd.) and the like. Anhydride) copolymers include Isoban-600 (manufactured by Kuraray Co., Ltd.). A specific example of the poly(vinyl ether-maleic anhydride) copolymer is Gantrez AN-139 (methyl vinyl ether maleic anhydride resin, manufactured by Ashland).
Among them, the polymer (B) is more preferable from the viewpoint of reducing afterimages derived from residual DC.
These other polymers may be used singly or in combination of two or more. The content of the other polymer is preferably 90 parts by mass or less, more preferably 10 to 90 parts by mass, and further 20 to 80 parts by mass with respect to the total 100 parts by mass of the polymer contained in the liquid crystal aligning agent. preferable.

(Polymer (B))
Specific examples of the tetracarboxylic acid component used in the production of the polymer (B) include the same compounds as those exemplified for the polymer (P), including preferred specific examples. The tetracarboxylic acid component used for producing the polymer (B) is more preferably a tetracarboxylic dianhydride having at least one partial structure selected from the group consisting of a benzene ring, a cyclobutane ring, a cyclopentane ring and a cyclohexane ring. or derivatives thereof, more preferably the above-mentioned specific tetracarboxylic acid derivative, and most preferably using more preferred specific examples of the above-mentioned specific tetracarboxylic acid derivative.
The amount of the specific tetracarboxylic acid derivative used is preferably 10 mol % or more, more preferably 20 mol % or more, more preferably 50 mol % or more, relative to the total tetracarboxylic acid component used in the production of the polymer (B). More preferably mol% or more.

Examples of the diamine component for obtaining the polymer (B) include the diamines exemplified for the polymer (P) above. Among them, diamines having at least one group selected from the group consisting of a urea bond, an amide bond, a carboxy group and a hydroxy group in the molecule, represented by the above formulas (d _AL -1) to (d _AL -10) It preferably contains at least one diamine selected from the group consisting of diamines and diamines having a specific nitrogen atom-containing structure (in the present invention, these are also referred to as specific diamines (b)). As the diamine component, one type of diamine may be used alone, or two or more types may be used in combination.
When the specific diamine (b) is used, the amount used is preferably 10 mol % or more, more preferably 20 mol % or more, of the total diamine component used in the production of the polymer (B). When using a diamine other than the specific diamine (b), the amount used is preferably 90 mol % or less, more preferably 80 mol % or less, of the total diamine component used in the production of the polymer (B).

(Production of polyamic acid)
A polyamic acid is produced by reacting a diamine component and a tetracarboxylic acid component in an organic solvent. The ratio of the tetracarboxylic acid component and the diamine component used in the polyamic acid production reaction is 0.5 to 2 equivalents of the acid anhydride group of the tetracarboxylic acid component per 1 equivalent of the amino group of the diamine component. is preferably 0.8 to 1.2 equivalents. As in ordinary polycondensation reactions, the closer the equivalent of the acid anhydride group of the tetracarboxylic acid component is to 1 equivalent, the greater the molecular weight of the resulting polyamic acid.
The reaction temperature in the production of polyamic acid is preferably -20 to 150°C, more preferably 0 to 100°C. Also, the reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours. Polyamic acid can be produced at any concentration, but the concentration of polyamic acid is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The initial stage of the reaction can be carried out at a high concentration, and then the solvent can be added.

Specific examples of the organic solvent include cyclohexanone, cyclopentanone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone. In addition, when the solvent solubility of the polymer is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Solvents such as glycol monopropyl ether, diethylene glycol monomethyl ether, or diethylene glycol monoethyl ether can be used.

(Production of Polyamic Acid Ester)
Polyamic acid esters are produced by, for example, [I] a method of reacting the polyamic acid obtained by the above method with an esterifying agent, [II] a method of reacting a tetracarboxylic acid diester with a diamine, [III] a tetracarboxylic acid It can be obtained by a known method such as a method of reacting a diester dihalide and a diamine.

(Manufacturing of polyimide)
A polyimide can be obtained by ring-closing (imidizing) a polyimide precursor such as the above polyamic acid or polyamic acid ester. The imidization ratio as used herein means the ratio of imide groups to the total amount of imide groups derived from tetracarboxylic dianhydride or derivatives thereof and carboxy groups (or derivatives thereof). The imidization rate does not necessarily have to be 100%, and can be arbitrarily adjusted according to the application and purpose.

Examples of the method for imidizing the polyimide precursor include thermal imidization in which the solution of the polyimide precursor is heated as it is, and catalytic imidization in which a catalyst is added to the solution of the polyimide precursor.
When the polyimide precursor is thermally imidized in the solution, the temperature is preferably 100 to 400° C., more preferably 120 to 250° C., and water generated by the imidization reaction is removed from the system. is preferred.

The catalytic imidization of the polyimide precursor can be carried out by adding a basic catalyst and an acid anhydride to the solution of the polyimide precursor and stirring at -20 to 250°C, preferably 0 to 180°C. The amount of the basic catalyst is 0.5 to 30 times the molar amount of the amic acid group, preferably 2 to 20 times the molar amount, and the amount of the acid anhydride is 1 to 50 times the molar amount of the amic acid group, preferably 3 to 30 times the molar amount. Double. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc. Among them, pyridine is preferable because it has appropriate basicity for advancing the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among them, acetic anhydride is preferably used because it facilitates purification after the reaction is completed. The imidization rate by catalytic imidization can be controlled by adjusting the catalyst amount, reaction temperature, and reaction time.

When recovering the generated polyimide precursor or polyimide from the polyimide precursor or polyimide reaction solution, the reaction solution may be put into a solvent to precipitate. Solvents used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water. The polymer precipitated by adding it to the solvent can be filtered and recovered, and then dried at room temperature or under heat under normal pressure or reduced pressure. In addition, the impurities in the polymer can be reduced by repeating the operation of redissolving the recovered polymer in an organic solvent and recovering it by reprecipitation 2 to 10 times. Solvents in this case include, for example, alcohols, ketones, hydrocarbons, and the like, and it is preferable to use three or more solvents selected from these, because the efficiency of purification is further increased.

When producing a polyimide precursor or polyimide in the present invention, a tetracarboxylic acid component containing a tetracarboxylic acid dianhydride or a derivative thereof, and a diamine component containing the diamine, together with an appropriate terminal blocker to end block A polymer of the type may be produced. The end-blocking polymer has the effect of improving the film hardness of the alignment film obtained by coating and improving the adhesion properties between the sealant and the alignment film.
Examples of the terminal of the polyimide precursor or polyimide in the present invention include an amino group, a carboxyl group, an acid anhydride group, or a group derived from a terminal blocking agent to be described later. An amino group, a carboxyl group, and an acid anhydride group can be obtained by a normal condensation reaction, or can be obtained by terminal blocking using the following terminal blocking agents.

Terminal blockers include, for example, acetic anhydride, maleic anhydride, nadic anhydride, phthalic anhydride, itaconic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, trimellitic anhydride, 3- (3-trimethoxysilyl)propyl)-3,4-dihydrofuran-2,5-dione, 4,5,6,7-tetrafluoroisobenzofuran-1,3-dione, 4-ethynylphthalic anhydride, etc. acid anhydrides; dicarbonic acid diester compounds such as di-tert-butyl dicarbonate and diallyl dicarbonate; acryloyl chloride, methacryloyl chloride, chlorocarbonyl compounds such as nicotinic acid chloride; aniline, 2-aminophenol, 3-aminophenol, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, Monoamine compounds such as n-heptylamine and n-octylamine; isocyanate having.
The proportion of the terminal blocker used is preferably 0.01 to 20 mol parts, more preferably 0.01 to 10 mol parts, per 100 mol parts of the total diamine component used.

The polystyrene equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the polyimide precursor and polyimide is preferably 1,000 to 500,000, more preferably 2,000 to 300,000. and more preferably 10,000 to 50,000. In addition, the molecular weight distribution (Mw/Mn) represented by the ratio of Mw to the polystyrene equivalent number average molecular weight (Mn) measured by GPC is preferably 15 or less, more preferably 10 or less. By being in this molecular weight range, it is possible to ensure good liquid crystal orientation of the liquid crystal display element.

The organic solvent contained in the liquid crystal aligning agent according to the present invention is not particularly limited as long as it uniformly dissolves the polymer (P) and other polymers added as necessary. For example, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethyllactamide, N,N-dimethylpropionamide, tetramethylurea, N,N-diethylformamide, N-methyl-2-pyrrolidone , N-ethyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone, γ-valerolactone, 1,3-dimethyl-2-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 3-methoxy-N,N-dimethyl Propanamide, 3-butoxy-N,N-dimethylpropanamide, N-(n-propyl)-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-(n-butyl)-2-pyrrolidone, N-( t-butyl)-2-pyrrolidone, N-(n-pentyl)-2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, N-ethoxyethyl-2-pyrrolidone, N-methoxybutyl-2-pyrrolidone, N- Cyclohexyl-2-pyrrolidone (collectively referred to as a good solvent) and the like. Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide and γ-butyrolactone are preferred. The content of the good solvent is preferably 20 to 99% by mass, more preferably 20 to 90% by mass, and particularly preferably 30 to 80% by mass of the total solvent contained in the liquid crystal aligning agent.

Further, the organic solvent contained in the liquid crystal aligning agent is a mixture of the above solvents and a solvent (also referred to as a poor solvent) that improves the coatability and the surface smoothness of the coating film when applying the liquid crystal aligning agent. The use of solvents is preferred. Specific examples of the poor solvent are given below, but are not limited thereto. The content of the poor solvent is preferably 1 to 80% by mass, more preferably 10 to 80% by mass, particularly preferably 20 to 70% by mass, of the total solvent contained in the liquid crystal aligning agent. The type and content of the poor solvent are appropriately selected according to the liquid crystal aligning agent coating device, coating conditions, coating environment, and the like.

Examples of poor solvents include diisopropyl ether, diisobutyl ether, diisobutyl carbinol (2,6-dimethyl-4-heptanol), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, and diethylene glycol. dimethyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2- ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, 1 -(2-butoxyethoxy)-2-propanol, 2-(2-butoxyethoxy)-1-propanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy)ethyl acetate, diethylene glycol acetate, propylene glycol diacetate, n-butyl acetate, Propylene glycol monoethyl ether acetate, cyclohexyl acetate, 4-methyl-2-pentyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxy Butyl propionate, n-butyl lactate, isoamyl lactate, diethylene glycol monoethyl ether, diisobutyl ketone (2,6-dimethyl-4-heptanone) and the like.

Among them, diisobutyl carbinol, propylene glycol monobutyl ether, propylene glycol diacetate, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monobutyl ether, ethylene Glycol monobutyl ether acetate or diisobutyl ketone are preferred.

Preferred solvent combinations of a good solvent and a poor solvent include N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone and ethylene glycol monobutyl ether, N-methyl-2- Pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone, N-ethyl-2- pyrrolidone and propylene glycol diacetate, N,N-dimethyllactamide and diisobutyl ketone, N-methyl-2-pyrrolidone and ethyl 3-ethoxypropionate, N-ethyl-2-pyrrolidone and ethyl 3-ethoxypropionate, N- Methyl-2-pyrrolidone and ethyl 3-ethoxypropionate and dipropylene glycol monomethyl ether, N-ethyl-2-pyrrolidone and 3-ethoxyethyl propionate and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone and 3-ethoxy Ethyl Propionate and Diethylene Glycol Monopropyl Ether, N-Ethyl-2-Pyrrolidone and 3-Ethoxy Ethyl Propionate and Diethylene Glycol Monopropyl Ether, N-Methyl-2-Pyrrolidone and Ethylene Glycol Monobutyl Ether Acetate, N-Ethyl-2- Pyrrolidone and dipropylene glycol dimethyl ether, N,N-dimethyl lactamide and ethylene glycol monobutyl ether, N,N-dimethyl lactamide and propylene glycol diacetate, N-ethyl-2-pyrrolidone and diethylene glycol diethyl ether, N-ethyl-2 - pyrrolidone and diethylene glycol monoethyl ether and butyl cellosolve acetate, N-methyl-2-pyrrolidone and diethylene glycol monomethyl ether and butyl cellosolve acetate, N,N-dimethyllactamide and diethylene glycol diethyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone 4-hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether, N-ethyl-2-pyrrolidone and N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone, N-ethyl-2- pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and propylene glycol mono Butyl ether, N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and diisobutyl ketone, N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and dipropylene glycol monomethyl ether , N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and propylene glycol diacetate , N-ethyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and dipropylene glycol dimethyl ether, γ-butyrolactone and 4-hydroxy-4-methyl-2-pentanone and diisobutyl ketone, γ-butyrolactone and 4 -hydroxy-4-methyl-2-pentanone and propylene glycol diacetate, N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether and diisobutyl ketone, N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol Monobutyl ether and diisopropyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether and diisobutylcarbinol, N-methyl-2-pyrrolidone, γ-butyrolactone and dipropylene glycol dimethyl ether, N-methyl-2- pyrrolidone and propylene glycol monobutyl ether and dipropylene glycol dimethyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether and dipropylene glycol monomethyl ether, N-ethyl-2-pyrrolidone and diethylene glycol diethyl ether and dipropylene glycol monomethyl ether, N -ethyl-2-pyrrolidone and propylene glycol monobutyl ether and propylene glycol diacetate, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether and diisobutyl ketone, N-ethyl-2-pyrrolidone and γ-butyrolactone and diisobutyl ketone, N- Ethyl-2-pyrrolidone and N,N-dimethyllactamide and diisobutyl ketone, N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether and ethylene glycol monobutyl ether acetate, γ-butyrolactone and ethylene glycol monobutyl ether acetate Dipropylene glycol dimethyl ether, N-ethyl-2-pyrrolidone and ethylene glycol monobutyl ether acetate and propylene glycol dimethyl ether, N-methyl-2-pyrrolidone and 4-methyl-2-pentyl acetate and ethylene glycol monobutyl ether, N-ethyl- 2-pyrrolidone and cyclohexyl acetate and 4-hydroxy-4-methyl-2-pentanone, cyclohexanone and propylene glycol monomethyl ether, cyclopentanone and propylene glycol monomethyl ether, N-methyl-2-pyrrolidone and cyclohexanone and propylene glycol monomethyl ether, etc. can be mentioned.

(Liquid crystal aligning agent)
The liquid crystal aligning agent of the present invention may contain other components (hereinafter also referred to as additive components) in addition to the polymer (P), the other polymer, and the organic solvent. Such additive components include, for example, a crosslinkable compound having at least one substituent selected from an oxiranyl group, an oxetanyl group, a blocked isocyanate group, an oxazoline group, a cyclocarbonate group, a hydroxy group and an alkoxy group; At least one crosslinkable compound selected from the group consisting of crosslinkable compounds having saturated groups, functional silane compounds, metal chelate compounds, curing accelerators, surfactants, antioxidants, sensitizers, preservatives, and compounds for adjusting the dielectric constant and electrical resistance of the liquid crystal alignment film.

Preferred specific examples of the crosslinkable compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, Epicoat 828 (Mitsubishi Chemical Co., Ltd.) ), bisphenol F type epoxy resins such as Epicoat 807 (manufactured by Mitsubishi Chemical Corporation), hydrogenated bisphenol A type epoxy resins such as YX-8000 (manufactured by Mitsubishi Chemical Corporation), YX6954BH30 (Mitsubishi Chemical Corporation (manufactured by Nippon Kayaku Co., Ltd.), phenol novolac type epoxy resins such as EPPN-201 (manufactured by Nippon Kayaku Co., Ltd.), and (o, m, p-) cresol novolacs such as EOCN-102S (manufactured by Nippon Kayaku Co., Ltd.). type epoxy resins, triglycidyl isocyanurates such as TEPIC (manufactured by Nissan Chemical Industries, Ltd.), alicyclic epoxy resins such as Celoxide 2021P (manufactured by Daicel Chemical Industries, Ltd.), N,N,N',N'-tetraglycidyl-m- Tertiary nitrogen atoms represented by xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, or N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane a compound having two or more oxiranyl groups such as tetrakis(glycidyloxymethyl)methane; Compounds having; Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (manufactured by Tosoh Corporation), Takenate B-830, B-815N, B-820NSU, B-842N, B -846N, B-870N, B-874N, compounds having a blocked isocyanate group such as B-882N (manufactured by Mitsui Chemicals, Inc.); 2,2'-bis(2-oxazoline), 2,2'-bis( 4-methyl-2-oxazoline), 2,2'-bis(5-methyl-2-oxazoline phosphorus), 1,2,4-tris-(2-oxazolinyl-2)-benzene, compounds having an oxazoline group such as Epocross (manufactured by Nippon Shokubai Co., Ltd.); paragraphs [0025] to [0030 of WO2011/155577 ], a compound having a cyclocarbonate group according to [0032]; phenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethoxymethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)-1,1,1,3 , 3,3-hexafluoropropane and other compounds having a hydroxy group or an alkoxy group; glycerin mono(meth)acrylate, glycerin di(meth)acrylate (1,2-, 1,3-body mixture), ) acrylate, glycerol 1,3-diglycerolate di (meth) acrylate, pentaerythrol tri (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate , pentaethylene glycol mono(meth)acrylate, and hexaethylene glycol mono(meth)acrylate.
The content of the crosslinkable compound is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the polymer component contained in the liquid crystal aligning agent.

Examples of compounds for adjusting the dielectric constant and electrical resistance include monoamines having a nitrogen atom-containing aromatic heterocycle such as 3-picolylamine. The content of the monoamine having a nitrogen atom-containing aromatic heterocyclic ring is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent. part by mass.

Preferred specific examples of the above functional silane compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltrimethoxysilane. Ethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltri ethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyl diethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, tris(3-trimethoxysilylpropyl) isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane and the like. The content of the functional silane compound is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass based on 100 parts by mass of the polymer component contained in the liquid crystal alignment agent.

The solid content concentration in the liquid crystal aligning agent (ratio of the total mass of components other than the solvent of the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc., but preferably It is 1 to 10% by mass.
A particularly preferable solid content concentration range varies depending on the method used when applying the liquid crystal aligning agent to the substrate. For example, when a spin coating method is used, the solid content concentration is particularly preferably 1.5 to 4.5% by mass. When the printing method is used, it is particularly preferable to set the solid content concentration to 3 to 9% by mass and thereby the solution viscosity to 12 to 50 mPa·s. In the case of the inkjet method, it is particularly preferable to set the solid content concentration to 1 to 5% by mass and thereby the solution viscosity to 3 to 15 mPa·s. The temperature in preparing the polymer composition is preferably 10-50°C, more preferably 20-30°C.

(Liquid crystal alignment film and liquid crystal display element)
A liquid crystal display element according to the present invention comprises a liquid crystal alignment film formed using the liquid crystal alignment agent. The operation mode of the liquid crystal display element is not particularly limited. , optically compensated bend type (OCB type), and various other operation modes.

The liquid crystal display element of the present invention can be produced, for example, by a method including the following steps (1) to (4), a method including steps (1) to (2) and (4), steps (1) to (3), ( 4-2) and (4-4), or by a method including steps (1) to (3), (4-3) and (4-4).

<Step (1): Step of applying a liquid crystal aligning agent onto a substrate>
A process (1) is a process of apply|coating a liquid crystal aligning agent on a board|substrate. A specific example of step (1) is as follows.
A liquid crystal aligning agent is applied to one surface of the substrate provided with the patterned transparent conductive film by an appropriate coating method such as a roll coater method, a spin coat method, a printing method, an inkjet method, or the like. Here, the material of the substrate is not particularly limited as long as it is highly transparent, and glass, silicon nitride, plastic such as acrylic, polycarbonate, etc. can also be used. In addition, in the reflective liquid crystal display element, if only one substrate is used, an opaque material such as a silicon wafer can be used, and in this case, a light-reflecting material such as aluminum can be used for the electrodes. In the case of manufacturing an IPS-type or FFS-type liquid crystal display element, a substrate provided with electrodes made of a transparent conductive film or a metal film patterned in a comb shape and a counter substrate provided with no electrodes are used. and

Screen printing, offset printing, flexographic printing, inkjet method, spray method, etc., can be used as methods for applying the liquid crystal aligning agent to the substrate and forming a film. Among them, the coating method and the film-forming method by the inkjet method can be preferably used.

<Step (2): Step of firing the applied liquid crystal aligning agent>
A process (2) is a process of baking the liquid crystal aligning agent apply|coated on the board|substrate, and forming a film|membrane. A specific example of step (2) is as follows.
After the liquid crystal aligning agent is applied onto the substrate in step (1), the solvent is evaporated or the polyamic acid is thermally imidized by heating means such as a hot plate, thermal circulation oven or IR (infrared) oven. you can go Drying after applying a liquid crystal aligning agent and a baking process can select arbitrary temperature and time, and may be performed in multiple times. The temperature for baking the liquid crystal aligning agent can be, for example, 40 to 180.degree. From the viewpoint of shortening the process, it may be carried out at 40 to 150°C. The firing time is not particularly limited, but may be 1 to 10 minutes or 1 to 5 minutes. When the polyamic acid is thermally imidized, a step of firing at, for example, 150 to 300° C. or 150 to 250° C. may be added after the above step. The firing time is not particularly limited, but may be 5 to 40 minutes or 5 to 30 minutes.
The thickness of the film-like material after baking is preferably 5 to 300 nm, more preferably 10 to 200 nm, because if it is too thin, the reliability of the liquid crystal display element may be lowered.

<Step (3): Step of performing alignment treatment on the film obtained in Step (2)>
Step (3) is a step of subjecting the film obtained in step (2) to orientation treatment. That is, in a horizontally aligned liquid crystal display element such as an IPS system or an FFS system, the coating film is subjected to an alignment ability imparting treatment. On the other hand, in a vertical alignment type liquid crystal display element such as VA mode or PSA mode, the formed coating film can be used as a liquid crystal alignment film as it is, but the coating film may be subjected to an alignment ability imparting treatment. Examples of the alignment treatment method for the liquid crystal alignment film include a rubbing treatment method and a photo-alignment treatment method. As a photo-alignment treatment method, the surface of the film is irradiated with radiation polarized in a certain direction, and optionally, preferably, heat treatment is performed at a temperature of 150 to 250 ° C. to improve liquid crystal orientation (liquid crystal orientation (also referred to as ability). As radiation, ultraviolet light or visible light having a wavelength of 100 to 800 nm can be used. Among them, ultraviolet rays having a wavelength of 100 to 400 nm, more preferably 200 to 400 nm are preferred.

The radiation dose is preferably 1 to 10,000 mJ/cm ² , more preferably 100 to 5,000 mJ/cm ² . In addition, when irradiating with radiation, the substrate having the film-like material may be irradiated with heating at 50 to 250° C. in order to improve liquid crystal orientation. The liquid crystal alignment film thus produced can stably orient liquid crystal molecules in a fixed direction.
Furthermore, the liquid crystal alignment film irradiated with polarized radiation can be subjected to contact treatment using water or a solvent, or the liquid crystal alignment film irradiated with radiation can be heat-treated.

The solvent used in the contact treatment is not particularly limited as long as it dissolves the decomposed product produced from the film-like material by irradiation with radiation. Specific examples include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, 3- methyl methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, cyclohexyl acetate and the like. Solvents may be used singly or in combination of two or more.

The temperature of the heat treatment for the above radiation-irradiated coating film is more preferably 50 to 300°C, more preferably 120 to 250°C. The heat treatment time is preferably 1 to 30 minutes.

<Step (4): Step of producing a liquid crystal cell>
Two substrates on which liquid crystal alignment films are formed as described above are prepared, and a liquid crystal composition is placed between the two substrates facing each other. Specifically, the following two methods are mentioned.
In the first method, first, two substrates are arranged to face each other with a gap (cell gap) interposed therebetween so that the respective liquid crystal alignment films face each other. Next, the peripheries of the two substrates are bonded together using a sealing agent, and a liquid crystal composition is injected and filled into the cell gap defined by the substrate surface and the sealing agent to contact the film surface, and then the injection hole is sealed. stop.

The second method is a method called ODF (One Drop Fill) method. A predetermined place on one of the two substrates on which the liquid crystal alignment film is formed is coated with, for example, an ultraviolet light-curing sealant, and a liquid crystal composition is applied to several predetermined places on the surface of the liquid crystal alignment film. drip. Thereafter, the other substrate is attached so that the liquid crystal alignment films face each other, and the liquid crystal composition is spread over the entire surface of the substrate and brought into contact with the film surface. Next, the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant. In any method, it is desirable to remove the flow orientation at the time of liquid crystal filling by heating the liquid crystal composition to a temperature at which the used liquid crystal composition assumes an isotropic phase and then slowly cooling to room temperature.
When the coating film is subjected to the rubbing treatment, the two substrates are arranged opposite to each other so that the rubbing directions of the respective coating films are at a predetermined angle, for example, orthogonal or antiparallel.
As the sealant, for example, an epoxy resin or the like containing a curing agent and aluminum oxide spheres as spacers can be used. The liquid crystal composition is not particularly limited, and may be a composition containing at least one liquid crystal compound (liquid crystal molecule) exhibiting a nematic phase (hereinafter also referred to as a nematic liquid crystal), or a liquid crystal exhibiting a smectic phase. , or liquid crystal compositions exhibiting a cholesteric phase, among which nematic liquid crystals are preferred. Also, various liquid crystal compositions having positive or negative dielectric anisotropy can be used. In the following description, a liquid crystal composition with a positive dielectric anisotropy is also referred to as a positive liquid crystal, and a liquid crystal composition with a negative dielectric anisotropy is also referred to as a negative liquid crystal.
The above liquid crystal composition contains a fluorine atom, a hydroxy group, an amino group, a fluorine atom-containing group (e.g., trifluoromethyl group), a cyano group, an alkyl group, an alkoxy group, an alkenyl group, an isothiocyanate group, a heterocyclic ring, a cycloalkane, A liquid crystal compound having a cycloalkene, a steroid skeleton, a benzene ring, or a naphthalene ring may be included, and a compound having two or more rigid sites (mesogenic skeleton) exhibiting liquid crystallinity in the molecule (for example, two rigid biphenyl structures or terphenyl structures linked by alkyl groups).
Moreover, the liquid crystal composition may further contain an additive from the viewpoint of improving liquid crystal orientation. Such additives include photopolymerizable monomers such as compounds having a polymerizable group; optically active compounds (eg, S-811 manufactured by Merck Co., Ltd.); antioxidants; UV absorbers; dyes; antifoaming agents; polymerization initiators; or polymerization inhibitors.
Positive liquid crystals include ZLI-2293, ZLI-4792, MLC-2003, MLC-2041, MLC-3019, and MLC-7081 manufactured by Merck.
Examples of negative liquid crystal include MLC-6608, MLC-6609, MLC-6610, MLC-7026 and MLC-7026-100 manufactured by Merck.
Further, as a liquid crystal containing a compound having a polymerizable group, MLC-3023 manufactured by Merck & Co., Ltd. can be mentioned.

The liquid crystal aligning agent of the present invention comprises a liquid crystal layer between a pair of substrates provided with electrodes, and a liquid crystal composition containing a polymerizable compound polymerized by at least one of active energy rays and heat between the pair of substrates. A liquid crystal display element (PSA type liquid crystal display element) manufactured through a process of polymerizing a polymerizable compound by at least one of irradiating an active energy ray and heating while placing an object and applying a voltage between electrodes. It is preferably used.
Further, the liquid crystal aligning agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and a polymerizable group polymerizable by at least one of active energy rays and heat is placed between the pair of substrates. It is also preferably used for a liquid crystal display element (SC-PVA mode type liquid crystal display element) manufactured through a process of arranging a liquid crystal alignment film containing a liquid crystal and applying a voltage between electrodes.

<Step (4-2): For PSA type liquid crystal display element>
It is carried out in the same manner as in (4) above, except that the liquid crystal composition containing a polymerizable compound is injected or dropped. Examples of the polymerizable compound include polymerizable compounds having one or more polymerizable unsaturated groups such as acrylate groups and methacrylate groups in the molecule.

<Step (4-3): For SC-PVA mode liquid crystal display element>
A method of manufacturing a liquid crystal display element may be employed in which a step of irradiating ultraviolet rays, which will be described later, is performed after performing the same as in the above (4). According to this method, a liquid crystal display device excellent in response speed can be obtained with a small amount of light irradiation, as in the case of manufacturing the PSA type liquid crystal display device. The compound having a polymerizable group may be a compound having one or more polymerizable unsaturated groups in the molecule, and its content is 0.1 to 30 per 100 parts by mass of all polymer components. It is preferably parts by mass, more preferably 1 to 20 parts by mass. Further, the polymerizable group may be present in the polymer used for the liquid crystal alignment agent, and such a polymer includes, for example, a diamine component containing a diamine having a photopolymerizable group at the end thereof, which is used in the reaction. The polymer obtained is mentioned.

<Step (4-4): Step of irradiating with ultraviolet rays>
The liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates obtained in (4-2) or (4-3) above. The voltage applied here can be, for example, 5 to 50 V direct current or alternating current. As the light to be irradiated, for example, ultraviolet rays and visible rays containing light having a wavelength of 150 to 800 nm can be used, but ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferable. As a light source for irradiation light, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used. The irradiation amount of light is preferably 1,000 to 200,000 J/m ² , more preferably 1,000 to 100,000 J/m ² .

Then, a liquid crystal display element can be obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell as necessary. As the polarizing plate to be attached to the outer surface of the liquid crystal cell, a polarizing film called "H film" in which polyvinyl alcohol is stretched and oriented while absorbing iodine is sandwiched between cellulose acetate protective films, or the H film itself. A polarizing plate consisting of

The IPS substrate, which is a comb-teeth electrode substrate used in the IPS mode, includes a base material, a plurality of linear electrodes formed on the base material and arranged in a comb-like shape, and the base material covering the linear electrodes. and a liquid crystal alignment film formed as follows.
The FFS substrate, which is a comb-teeth electrode substrate used in the FFS mode, includes a substrate, a plane electrode formed on the substrate, an insulating film formed on the plane electrode, and an insulating film formed on the insulating film. , a plurality of linear electrodes arranged in a comb shape, and a liquid crystal alignment film formed on an insulating film so as to cover the linear electrodes.

FIG. 1 is a schematic partial cross-sectional view showing an example of the lateral electric field liquid crystal display device of the present invention, which is an example of an IPS mode liquid crystal display device.
In the lateral electric field liquid crystal display element 1 illustrated in FIG. 1, the liquid crystal 3 is sandwiched between the comb-teeth electrode substrate 2 having the liquid crystal alignment film 2c and the opposing substrate 4 having the liquid crystal alignment film 4a. The comb-shaped electrode substrate 2 includes a substrate 2a, a plurality of linear electrodes 2b formed on the substrate 2a and arranged in a comb-like shape, and formed on the substrate 2a so as to cover the linear electrodes 2b. and a liquid crystal alignment film 2c. The counter substrate 4 has a base material 4b and a liquid crystal alignment film 4a formed on the base material 4b. The liquid crystal alignment film 2c is, for example, the liquid crystal alignment film of the present invention. The liquid crystal alignment film 4c is also the liquid crystal alignment film of the present invention.
In the lateral electric field liquid crystal display element 1, when a voltage is applied to the linear electrodes 2b, an electric field is generated between the linear electrodes 2b as indicated by the lines of electric force L. FIG.

FIG. 2 is a schematic partial sectional view showing another example of the horizontal electric field liquid crystal display device of the present invention, which is an example of the FFS mode liquid crystal display device.
In the lateral electric field liquid crystal display element 1 illustrated in FIG. 2, the liquid crystal 3 is sandwiched between the comb-teeth electrode substrate 2 having the liquid crystal alignment film 2h and the opposing substrate 4 having the liquid crystal alignment film 4a. The comb-teeth electrode substrate 2 includes a base material 2d, a plane electrode 2e formed on the base material 2d, an insulating film 2f formed on the plane electrode 2e, and formed on the insulating film 2f to form a comb-like shape. It has a plurality of arranged linear electrodes 2g and a liquid crystal alignment film 2h formed on the insulating film 2f so as to cover the linear electrodes 2g. The counter substrate 4 has a base material 4b and a liquid crystal alignment film 4a formed on the base material 4b. The liquid crystal alignment film 2h is, for example, the liquid crystal alignment film of the present invention. The liquid crystal alignment film 4a is also the liquid crystal alignment film of the present invention.
In the horizontal electric field liquid crystal display element 1, when a voltage is applied to the plane electrode 2e and the linear electrode 2g, an electric field is generated between the plane electrode 2e and the linear electrode 2g as indicated by electric lines of force L. FIG.

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not construed as being limited to these examples. The abbreviations of the compounds used and methods for measuring physical properties are as follows.
(organic solvent)
NMP: N-methyl-2-pyrrolidone, GBL: γ-butyrolactone,
BCS: butyl cellosolve, BCA: butyl cellosolve acetate THF: tetrahydrofuran, DMF: N,N-dimethylformamide

(Acid dianhydride)

(diamine)

(Additive)

<Measurement of viscosity>
Using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), a sample amount of 1.1 mL, and a cone rotor TE-1 (1°34', R24), measurement was performed at a temperature of 25°C.

<Measurement of molecular weight>
Mn and Mw were calculated as values in terms of polyethylene glycol and polyethylene oxide by measuring with the following normal temperature GPC (gel permeation chromatography) apparatus.
GPC apparatus: GPC-101 (manufactured by Showa Denko), column: GPC KD-803, GPC KD-805 (manufactured by Showa Denko) in series, column temperature: 50 ° C., eluent: N,N-dimethylformamide (added As agents, 30 mmol/L of lithium bromide monohydrate (LiBr.H2O), 30 mmol/L of phosphoric acid/anhydrous crystals (o-phosphoric acid), and 10 mL/L of tetrahydrofuran (THF)), flow rate: 1. 0 mL/min Standard sample for creating a calibration curve: TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000 and 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight: about 12,000, 4,000 and 1,000) (manufactured by Polymer Laboratories).

[Synthesis of Monomer]
DA-1 to DA-3 are novel compounds not disclosed in literature, etc., and the products in Synthesis Examples 1 to 3 below were identified by ¹ H-NMR analysis. Analysis conditions are as follows.
Equipment: BRUKER ADVANCE III-500MHz
Measurement solvent: deuterated dimethyl sulfoxide (DMSO-d ₆ )
Reference substance: tetramethylsilane (TMS) (δ0.0 ppm for ¹ H)

THF (120 g) and pyridine (14.0 g, 0.177 mol) were added to 2-(4-nitrophenoxy)ethanol (30.0 g, 0.164 mol), and the mixture was stirred while cooling in an ice bath (0°C). did. To the resulting solution, adipic acid dichloride (17.0 g, 0.0929 mol) dissolved in THF (60 g) was added dropwise. Stirred for 18 hours. After completion of the reaction, the mixture was cooled to room temperature (25° C.) and water (540 g) was added to precipitate crystals. The crystals obtained by filtration were dried to obtain crude crystals (39 g). THF (300 g) was added to the crude crystals, and the mixture was heated and stirred at 70° C., and was recrystallized by adding methanol (400 g) while cooling in an ice bath (0° C.). This was filtered and the obtained crystals were dried to obtain DA-1-1 (yield: 34.0 g, 0.0713 mol, yield 88%).
¹ H-NMR (500 MHz) in DMSO-d ₆ : δ (ppm) = 8.19 (d, J = 9.5 Hz, 4H), 7.16 (d, J = 9.5 Hz, 4H), 4. 37 (q, 4H), 4.34 (q, 4H), 2.33 (t, 4H), 1.54-1.51 (m, 4H).

To DA-1-1 (29.0 g, 0.0609 mol) obtained above, DMF (290 g) was added and nitrogen-substituted, and then carbon-supported palladium (5% Pd carbon powder (hydrous product) K type, N E Chemcat Co.) (2.32 g) was added, and the mixture was replaced with nitrogen again, attached with a hydrogen Tedlar bag, and heated and stirred at 50°C for 18 hours. After completion of the reaction, the solution was passed through a membrane filter to remove carbon-supported palladium, and water (1000 g) was added to the filtrate and stirred to precipitate crystals. This was filtered to obtain crude crystals (24 g). THF (92 g) was added to the crude crystals, and the slurry was washed with heating and stirring at 50° C., then cooled in an ice bath (0° C.), filtered, and the obtained crystals were dried to obtain crystals (22 g). DMF (66 g) was added to the obtained crystals, and the mixture was heated and stirred at 50°C, cooled in an ice bath (0°C), and recrystallized by adding acetonitrile (88 g). This was filtered and the obtained crystals were dried to obtain DA-1 (yield: 17.0 g, 0.0408 mol, yield 67%).
¹ H-NMR (500 MHz) in DMSO-d ₆ : δ (ppm) = 6.65 (d, J = 9.0 Hz, 4H), 6.49 (d, J = 9.0 Hz, 4H), 4. 60 (s, 4H), 4.26 (t, 4H), 4.01 (t, 4H), 2.33 (t, 4H), 1.56-1.53 (m, 4H).

DMF (210 g) and potassium carbonate (48.0 g, 0.347 mol) were added to 4′-hydroxy-4-nitrobiphenyl (30.0 g, 0.139 mol), and the mixture was heated and stirred at 80° C. for 30 minutes. 2-Bromoethanol (26 g, 0.208 mol) dissolved in DMF (30 g) was added dropwise to the obtained solution, and the mixture was heated and stirred at 80° C. for 18 hours. After completion of the reaction, the mixture was cooled to room temperature (25° C.) and water (480 g) was added to precipitate crystals. It was filtered and the crystals obtained were dried. Methanol was added to the filtrate, and the slurry was washed with heating and stirring at 50° C., cooled to room temperature (25° C.), and filtered. After concentrating the filtrate, the third crystal was collected by the same operation, and the obtained crystal was dried to obtain DA-2-1 (yield: 31.0 g, 0.120 mol, yield 86%).
¹ H-NMR (500 MHz) in DMSO-d ₆ : δ (ppm) = 8.27 (d, J = 8.5 Hz, 2H), 7.92 (d, J = 9.0 Hz, 2H), 7. 76 (d, J = 8.5Hz, 2H), 7.09 (d, J = 9.0Hz, 2H), 4.89 (t, 1H), 4.09-4.06 (m, 2H), 3.76-3.73 (m, 2H).

THF (230 g) and pyridine (8.20 g, 0.104 mol) were added to DA-2-1 (26.0 g, 0.100 mol) obtained above, and cooled in an ice bath (0°C). Stirred. Into this solution, adipic acid dichloride (9.9 g, 0.0541 mol) dissolved in THF (26 g) was added dropwise. After the addition was completed, the mixture was stirred at room temperature (25°C) for 5 hours, and then at 45°C for 1 hour. Stirred. After completion of the reaction, the mixture was cooled to room temperature (25° C.) and water (765 g) was added to precipitate crystals. This was filtered and the obtained crystals were dried to obtain crude crystals (29 g). THF (290 g) was added to the crude crystals and the mixture was heated and stirred at 60° C., and then recrystallized by adding methanol (290 g) while cooling in an ice bath (0° C.). This was filtered and the obtained crystals were dried to obtain DA-2-2 (yield: 24.0 g, 0.0382 mol, yield 76%).
¹ H-NMR (500 MHz) in DMSO-d ₆ : δ (ppm) = 8.25 (d, J = 9.0 Hz, 4H), 7.90 (d, J = 8.5 Hz, 4H), 7. 74 (d, J = 8.5 Hz, 4H), 7.09 (d, J = 8.5 Hz, 4H), 4.37 (t, 4H), 4.25 (t, 4H), 2.34 ( t, 4H), 1.57-1.54 (m, 4H).

To DA-2-2 (25.0 g, 0.0398 mol) obtained above, DMF (490 g) was added and nitrogen-substituted, and then carbon-supported palladium (5% Pd carbon powder (hydrous product) K type, N E Chemcat Co., Ltd.) (2.00 g) was added, and the mixture was replaced with nitrogen again, attached with a hydrogen Tedlar bag, and stirred at room temperature (25°C) for 48 hours. After completion of the reaction, the solution was passed through a membrane filter to remove carbon-supported palladium, and the filtrate was concentrated until crystals began to precipitate (remaining amount of DMF: about 140 g). This was heated and stirred at 55° C. to completely dissolve, cooled to room temperature (25° C.), and acetonitrile (80 g) was added to precipitate crystals. This was filtered and the obtained crystals were dried to obtain DA-2 (yield: 20.0 g, 0.0352 mol, yield 88%).
¹ H-NMR (500 MHz) in DMSO-d ₆ : δ (ppm) = 7.43 (d, J = 9.0 Hz, 4H), 7.27 (d, J = 8.5 Hz, 4H), 6. 93 (d, J = 8.5 Hz, 4H), 6.61 (d, J = 8.5 Hz, 4H), 5.10 (s, 4H), 4.33 (t, 4H), 4.17 ( t, 4H), 2.33 (t, 4H), 1.56-1.54 (m, 4H).
<Monomer Synthesis Example 3: Synthesis of DA-3>

THF (180 g) and pyridine (18.4 g, 0.232 mol) were added to 2-(4-nitrophenoxy)ethanol (35.7 g, 0.195 mol), and the mixture was stirred while cooling in an ice bath (0°C). did. To the resulting solution, suberic acid dichloride (19.6 g, 0.0929 mol) dissolved in THF (60 g) was added dropwise. Stirred for 18 hours. After completion of the reaction, the mixture was cooled to room temperature (25° C.) and water (400 g) was added to precipitate crystals. The crystals obtained by filtration were dried to obtain crude crystals (35 g). THF (180 g) was added to the crude crystals and the mixture was heated and stirred at 70° C., and was recrystallized by adding methanol (400 g) while cooling in an ice bath (0° C.). This was filtered and the obtained crystals were dried to obtain DA-3-1 (yield: 30.9 g, 0.0613 mol, yield 66%).
¹ H-NMR (500 MHz) in DMSO-d ₆ : δ (ppm) = 8.19 (d, J = 9.5 Hz, 4H), 7.17 (d, J = 9.5 Hz, 4H), 4. 38-4.34 (m, 8H), 2.28 (t, 4H), 1.48-1.45 (m, 4H), 1.25-1.23 (m, 4H).
To DA-3-1 (30.9 g, 0.0613 mol) obtained above, THF (770 g) was added and nitrogen-substituted, and then carbon-supported palladium (5% Pd carbon powder (hydrous product) K type, N E Chemcat Co.) (3.1 g) was added, and the mixture was replaced with nitrogen again, attached with a hydrogen Tedlar bag, and heated with stirring at 45° C. for 24 hours. After completion of the reaction, the filtrate was passed through a membrane filter to remove carbon-supported palladium, and after concentrating the filtrate, isopropyl alcohol (240 g) was added with stirring to precipitate crystals. This was filtered and the obtained crystals were dried to obtain DA-3 (yield: 24.9 g, 0.0560 mol, yield 91%).
¹ H-NMR (500 MHz) in DMSO-d ₆ : δ (ppm) = 6.66 (d, J = 9.0 Hz, 4H), 6.50 (d, J = 9.0 Hz, 4H), 4. 61 (s, 4H), 4.26 (t, 4H), 4.01 (t, 4H), 2.31-2.28 (m, 4H), 1.51-1.47 (m, 4H) , 1.28-1.24 (m, 4H).

[Synthesis of polymer]
<Synthesis Example 1>
DA-1 (2.29 g, 5.50 mmol) and NMP (16.8 g) are added to a 50 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while sending nitrogen. rice field. While stirring the resulting diamine solution under water cooling, CA-1 (1.15 g, 5.27 mmol) and NMP (8.10 g) were added and stirred at 50° C. for 18 hours to obtain a solid content concentration of 12. A mass % solution of polyamic acid (A-1) (viscosity: 239 mPa·s) was obtained. This polyamic acid had an Mn of 10,094 and an Mw of 33,198.

<Synthesis Example 2>
DA-1 (2.54 g, 6.10 mmol) and NMP (18.6 g) were added to a 50 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while sending nitrogen. rice field. While stirring the resulting diamine solution under water cooling, CA-2 (1.14 g, 5.81 mmol) and NMP (8.00 g) were added and stirred at room temperature for 18 hours to give a solid content concentration of 12 mass. % solution of polyamic acid (A-2) (viscosity: 241 mPa·s). This polyamic acid had an Mn of 12,332 and an Mw of 46,258.

<Synthesis Example 3>
DA-1 (3.12 g, 7.50 mmol) and NMP (22.9 g) were added to a 50 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while sending nitrogen. rice field. While stirring the resulting diamine solution under water cooling, CA-3 (1.60 g, 7.14 mmol) and NMP (10.8 g) were added and stirred at 40° C. for 18 hours to obtain a solid content concentration of 12. A mass % solution of polyamic acid (A-3) (viscosity: 282 mPa·s) was obtained. This polyamic acid had an Mn of 10,704 and an Mw of 39,144.

<Synthesis Example 4>
DA-3 (2.58 g, 5.80 mmol) and NMP (23.2 g) were added to a 50 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while sending nitrogen. rice field. While stirring the resulting diamine solution under water cooling, CA-3 (1.21 g, 5.40 mmol) and NMP (4.4 g) were added and stirred at 40° C. for 18 hours to give a solid content of 12. A solution (viscosity: 190 mPa·s) of polyamic acid (A-4) was obtained at 1% by mass. This polyamic acid had an Mn of 10,832 and an Mw of 43,395.

<Synthesis Example 5>
DA-1 (2.27 g, 5.44 mmol), DA-6 (0.390 g, 1.36 mmol) and NMP (19.5 g) were added to a 50 mL four-necked flask equipped with a stirrer and nitrogen inlet tube. was dissolved by stirring at room temperature while blowing nitrogen. While stirring the resulting diamine solution under water cooling, CA-3 (1.45 g, 6.46 mmol) and NMP (10.1 g) were added and stirred at 40° C. for 18 hours to give a solid content concentration of 12. A mass % solution of polyamic acid (A-5) (viscosity: 327 mPa·s) was obtained. This polyamic acid had an Mn of 10,534 and an Mw of 37,647.

<Synthesis Example 6>
DA-1 (1.46 g, 3.50 mmol), DA-6 (1.00 g, 3.50 mmol) and NMP (18.0 g) were added to a 50 mL four-necked flask equipped with a stirrer and nitrogen inlet tube. was dissolved by stirring at room temperature while blowing nitrogen. While stirring the resulting diamine solution under water cooling, CA-3 (1.48 g, 6.58 mmol) and NMP (10.8 g) were added and stirred at 40° C. for 18 hours to give a solid content of 12. A solution (viscosity: 225 mPa·s) of polyamic acid (A-6) with a mass % was obtained. This polyamic acid had an Mn of 10,400 and an Mw of 25,285.

<Synthesis Example 7>
DA-1 (0.73 g, 1.75 mmol), DA-6 (1.50 g, 5.24 mmol) and NMP (20.1 g) were added to a 50 mL four-necked flask equipped with a stirrer and nitrogen inlet tube. was dissolved by stirring at room temperature while blowing nitrogen. While stirring the resulting diamine solution under water cooling, CA-3 (1.47 g, 6.56 mmol) and NMP (6.9 g) were added and stirred at 40° C. for 18 hours to give a solid content of 12. A solution (viscosity: 236 mPa·s) of polyamic acid (A-7) was obtained at a mass %. This polyamic acid had an Mn of 10,634 and an Mw of 31,097.

<Synthesis Example 8>
DA-3 (0.80 g, 1.80 mmol), DA-6 (1.55 g, 5.41 mmol) and NMP (21.1 g) were added to a 50 mL four-necked flask equipped with a stirrer and nitrogen inlet tube. was dissolved by stirring at room temperature while blowing nitrogen. While stirring the resulting diamine solution under water cooling, CA-3 (1.52 g, 6.78 mmol) and NMP (7.0 g) were added and stirred at 40° C. for 18 hours to obtain a solid content of 12. A solution (viscosity: 209 mPa·s) of polyamic acid (A-8) with a mass % was obtained. This polyamic acid had an Mn of 9,900 and an Mw of 28,856.

<Synthesis Example 9>
DA-1 (1.67 g, 4.01 mmol), DA-4 (0.98 g, 4.01 mmol) and NMP (23.8 g) were added to a 50 mL four-necked flask equipped with a stirrer and nitrogen inlet tube. was dissolved by stirring at room temperature while blowing nitrogen. While stirring the resulting diamine solution under water cooling, CA-1 (1.63 g, 7.47 mmol) and NMP (7.6 g) were added and stirred at 50° C. for 18 hours to give a solid content concentration of 12. A solution (viscosity: 300 mPa·s) of polyamic acid (A-9) with a mass % was obtained. This polyamic acid had an Mn of 9,351 and an Mw of 31,020.

<Synthesis Example 10>
DA-2 (2.50 g, 4.40 mmol) and NMP (19.6 g) are added to a 50 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while sending nitrogen. rice field. While stirring the resulting diamine solution under water cooling, CA-1 (0.873 g, 4.00 mmol) and NMP (5.10 g) were added and stirred at 50° C. for 18 hours to give a solid content concentration of 12. A solution (viscosity: 231 mPa·s) of polyamic acid (A-10) of mass % was obtained. This polyamic acid had an Mn of 9,716 and an Mw of 25,390.

<Synthesis Example 11>
DA-2 (2.79 g, 4.90 mmol) and NMP (20.4 g) were added to a 50 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while sending nitrogen. rice field. While stirring the resulting diamine solution under water cooling, CA-2 (0.88 g, 4.49 mmol) and NMP (6.35 g) were added and stirred at room temperature for 18 hours to give a solid content concentration of 12 mass. % solution of polyamic acid (A-11) (viscosity: 230 mPa·s). This polyamic acid had an Mn of 11,774 and an Mw of 32,286.

<Synthesis Example 12>
DA-6 (3.72 g, 13.0 mmol) and NMP (31.3 g) were added to a 50 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while sending nitrogen. rice field. While stirring the resulting diamine solution under water cooling, CA-2 (2.37 g, 12.1 mmol) and NMP (13.4 g) were added and stirred at room temperature for 18 hours to give a solid content concentration of 12 mass. % solution of polyamic acid (A-12) (viscosity: 229 mPa·s). This polyamic acid had an Mn of 10,585 and an Mw of 27,581.

<Synthesis Example 13>
DA-7 (2.46 g, 6.40 mmol) and NMP (18.0 g) were added to a 50 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while sending nitrogen. rice field. While stirring the obtained diamine solution under water cooling, CA-2 (1.23 g, 6.26 mmol) and NMP (8.40 g) were added and stirred at room temperature for 18 hours to obtain a solid content concentration of 12 mass. % solution of polyamic acid (A-13) (viscosity: 292 mPa·s). This polyamic acid had an Mn of 16,511 and an Mw of 60,289.

<Synthesis Example 14>
DA-5 (2.07 g, 8.01 mmol) and NMP (18.6 g) were added to a 50 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while sending nitrogen. rice field. While stirring the obtained diamine solution under water cooling, CA-1 (1.65 g, 7.56 mmol) and NMP (14.8 g) were added and stirred at 50 ° C. for 18 hours to give a solid content concentration of 10. A solution (viscosity: 115 mPa·s) of polyamic acid (A-14) was obtained at 1% by mass. This polyamic acid had an Mn of 12,045 and an Mw of 27,326.

<Synthesis Example 15>
DA-6 (3.72 g, 13.0 mmol) and NMP (37.3 g) are added to a 50 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while sending nitrogen. rice field. While stirring the resulting diamine solution under water cooling, CA-1 (2.64 g, 12.1 mmol) and NMP (9.30 g) were added and stirred at 50° C. for 18 hours to give a solid content concentration of 12. A solution (viscosity: 278 mPa·s) of polyamic acid (A-15) with a mass % was obtained. This polyamic acid had an Mn of 10,832 and an Mw of 43,395.

<Synthesis Example 16>
DA-7 (3.08 g, 8.00 mmol) and NMP (22.6 g) are added to a 50 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while sending nitrogen. rice field. While stirring the resulting diamine solution under water cooling, CA-1 (1.61 g, 7.36 mmol) and NMP (11.8 g) were added and stirred at 50° C. for 18 hours to give a solid content concentration of 12. A mass % solution of polyamic acid (A-16) (viscosity: 256 mPa·s) was obtained. This polyamic acid had an Mn of 10,700 and an Mw of 37,763.

<Synthesis Example 17>
DA-6 (2.29 g, 8.00 mmol) and NMP (16.8 g) were added to a 50 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while sending nitrogen. rice field. While stirring the resulting diamine solution under water cooling, CA-3 (1.69 g, 7.52 mmol) and NMP (12.4 g) were added and stirred at 40° C. for 18 hours to give a solid content concentration of 12. A solution (viscosity: 240 mPa·s) of polyamic acid (A-17) with a mass % was obtained. This polyamic acid had an Mn of 11,482 and an Mw of 38,490.

<Synthesis Example 18>
DA-7 (2.69 g, 7.00 mmol) and NMP (19.7 g) were added to a 50 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while sending nitrogen. rice field. While stirring the resulting diamine solution under water cooling, CA-3 (1.54 g, 6.86 mmol) and NMP (10.1 g) were added and stirred at 40° C. for 18 hours to give a solid content concentration of 12. A solution (viscosity: 283 mPa·s) of polyamic acid (A-18) with a mass % was obtained. This polyamic acid had an Mn of 13,087 and an Mw of 45,255.

<Synthesis Example 19>
DA-8 (1.28 g, 6.42 mmol), DA-10 (0.32 g, 1.61 mmol) and NMP (14.3 g) were added to a 50 mL four-necked flask equipped with a stirrer and nitrogen inlet tube. was dissolved by stirring at room temperature while blowing nitrogen. While stirring the obtained diamine solution under water cooling, CA-2 (1.49 g, 7.60 mmol) and NMP (13.3 g) were added and stirred at room temperature for 18 hours to obtain a solid content concentration of 10 mass. % solution of polyamic acid (A-19) (viscosity: 125 mPa·s). This polyamic acid had an Mn of 11,120 and an Mw of 41,992.

<Synthesis Example 20>
DA-8 (2.99 g, 15.0 mmol), DA-9 (2.11 g, 5.01 mmol), DA-10 (0.99 g, 4.99 mmol) and NMP (44.6 g) were added and dissolved by stirring at room temperature with nitrogen sparging. While stirring the obtained diamine solution under water cooling, CA-2 (4.51 g, 23.0 mmol) and NMP (15.4 g) were added and stirred at room temperature for 18 hours to obtain a solid content concentration of 15 mass. % solution of polyamic acid (A-20) (viscosity: 592 mPa·s). This polyamic acid had an Mn of 12,080 and an Mw of 32,115.

<Synthesis Example 21>
DA-8 (5.42 g, 27.2 mmol), DA-10 (1.35 g, 6.80 mmol) and NMP (64.5 g) were added to a 100 mL four-necked flask equipped with a stirrer and nitrogen inlet tube. was dissolved by stirring at room temperature while blowing nitrogen. While stirring the resulting diamine solution under water cooling, CA-2 (1.53 g, 7.82 mmol) and NMP (10.2 g) were added and stirred at room temperature for 0.5 hours. Then, while stirring this solution under water cooling, CA-4 (6.38 g, 25.5 mmol) and NMP (8.50 g) were added and stirred at 50 ° C. for 18 hours to give a solid content concentration of 15 mass. % solution of polyamic acid (A-21) (viscosity: 1,250 mPa·s). This polyamic acid had an Mn of 15,100 and an Mw of 54,900.

<Synthesis Example 22>
DA-4 (0.98 g, 4.00 mmol), DA-8 (0.78 g, 4.00 mmol) and NMP (10.1 g) were added to a 50 mL four-necked flask equipped with a stirrer and nitrogen inlet tube. was dissolved by stirring at room temperature while blowing nitrogen. While stirring the resulting diamine solution under water cooling, CA-4 (1.50 g, 6.00 mmol) and NMP (8.50 g) were added and stirred at 50° C. for 2 hours. Then, while stirring this solution under water cooling, CA-5 (0.49 g, 1.68 mmol) and NMP (2.80 g) were added and stirred at 50 ° C. for 18 hours to give a solid content concentration of 15 mass. % solution of polyamic acid (A-22) (viscosity: 315 mPa·s). This polyamic acid had an Mn of 9,491 and an Mw of 26,134.

<Synthesis Example 23>
DA-4 (2.81 g, 11.5 mmol), DA-8 (2.29 g, 11.5 mmol) and NMP (45.9 g) were added to a 100 mL four-necked flask equipped with a stirrer and nitrogen inlet tube. was dissolved by stirring at room temperature while blowing nitrogen. While stirring the resulting diamine solution under water cooling, CA-4 (2.88 g, 11.5 mmol) and NMP (15.4 g) were added and stirred at 50° C. for 2 hours. Then, while stirring this solution under water cooling, CA-5 (2.86 g, 9.72 mmol) and NMP (2.8 g) were added and stirred at 50 ° C. for 18 hours to give a solid content concentration of 15 mass. % solution of polyamic acid (A-23) (viscosity: 298 mPa·s). This polyamic acid had an Mn of 8,290 and an Mw of 22,181.

<Synthesis Example 24>
DA-4 (2.81 g, 11.5 mmol), DA-8 (2.29 g, 11.5 mmol) and NMP (45.9 g) were added to a 100 mL four-necked flask equipped with a stirrer and nitrogen inlet tube. was dissolved by stirring at room temperature while blowing nitrogen. While stirring the resulting diamine solution under water cooling, CA-6 (2.58 g, 11.5 mmol) and NMP (10.4 g) were added and stirred at room temperature for 2 hours. Then, while stirring this solution under water cooling, CA-5 (2.87 g, 9.72 mmol) and NMP (3.3 g) were added and stirred at 50 ° C. for 18 hours to give a solid content concentration of 15 mass. % solution of polyamic acid (A-24) (viscosity: 300 mPa·s). This polyamic acid had an Mn of 9,018 and an Mw of 27,228.

<Synthesis Example 25>
DA-8 (4.14 g, 20.8 mmol), DA-10 (1.03 g, 5.19 mmol) and NMP (46.6 g) were added to a 100 mL four-necked flask equipped with a stirrer and nitrogen inlet tube. was dissolved by stirring at room temperature while blowing nitrogen. While stirring the resulting diamine solution under water cooling, CA-2 (2.20 g, 11.4 mmol) and NMP (7.50 g) were added and stirred at room temperature for 0.5 hours. Then, while stirring this solution under water cooling, CA-4 (3.25 g, 13.0 mmol) and NMP (6.20 g) were added and stirred at 50 ° C. for 18 hours to give a solid content concentration of 15 mass. % solution of polyamic acid (A-25) (viscosity: 535 mPa·s). This polyamic acid had an Mn of 10,218 and an Mw of 29,128.

<Synthesis Example 26>
DA-8 (5.42 g, 27.2 mmol), DA-10 (1.35 g, 6.80 mmol) and NMP (64.5 g) were added to a 100 mL four-necked flask equipped with a stirrer and nitrogen inlet tube. was dissolved by stirring at room temperature while blowing nitrogen. While stirring the resulting diamine solution under water cooling, CA-2 (1.48 g, 7.55 mmol) and NMP (10.2 g) were added and stirred at room temperature for 0.5 hours. Then, while stirring this solution under water cooling, CA-4 (6.38 g, 25.5 mmol) and NMP (8.50 g) were added and stirred at 50 ° C. for 18 hours to give a solid content concentration of 15 mass. % solution of polyamic acid (A-26) (viscosity: 530 mPa·s). This polyamic acid had an Mn of 9,982 and an Mw of 28,927.

Table 1 shows the types and amounts of the tetracarboxylic acid components and diamine components used in Synthesis Examples 1 to 26 above.

[Preparation of Liquid Crystal Aligning Agent]
<Example 1>
NMP (0.17 g), GBL (5.53 g), BCS (1.80 g), and BCA (0.60 g) were added to the solution (3.90 g) of polyamic acid (A-2) obtained in Synthesis Example 2. ) is added and stirred at room temperature for 2 hours, so that the mass ratio of the polymer solid content and each solvent (polymer solid content: NMP: GBL: BCS: BCA) is 4: 30: 46: 15: 5 liquid crystal An alignment agent (AL-1) was obtained.

<Examples 2 to 6, and Comparative Examples 1 to 6>
Liquid crystal aligning agents AL-2 to AL-6 of Examples 2 to 6 and Comparative Example 1 were prepared in the same manner as in Example 1 except that the polyamic acid solution used was changed as shown in Table 2. Liquid crystal aligning agents AL-C1 to AL-C6, which are ∼6, were obtained.

<Example 7>
To the solution (0.90 g) of polyamic acid (A-3) obtained in Synthesis Example 3, the solution (2.88 g) of polyamic acid (A-21) obtained in Synthesis Example 21, NMP (4.68 g ), BCS (3.00 g), and AD-1 (1% by mass NMP solution, 0.54 g) were added and stirred at room temperature for 2 hours to obtain a polymer mass ratio ((A-3): (A -15)) is 20: 80, the mass ratio of the polymer solid content and each solvent (polymer solid content: NMP: BCS) is 4.5: 70.5: 25, and 100 parts by mass of the polymer On the other hand, a liquid crystal aligning agent (AL-7) containing 1 part by mass of AD-1 was obtained.

<Examples 8 to 18, and Comparative Examples 7 to 10>
The polyamic acid solution to be used, the solvent, and the type and amount of the additive were changed as shown in Table 2. -8 to AL-18 and liquid crystal aligning agents AL-C7 to AL-C10 of Comparative Examples 7 to 10 were obtained.

In Table 2, the numbers in parentheses represent the ratio (parts by mass) of each polymer and additive to the total 100 parts by mass of the polymer components.

[Production of liquid crystal cell]
<Fabrication of FFS driven liquid crystal cell for negative liquid crystal>
A liquid crystal cell for negative liquid crystal having the structure of an FFS mode liquid crystal display element was produced.
First, a substrate with electrodes was prepared. A glass substrate having a size of 30 mm×35 mm and a thickness of 0.7 mm was used as the substrate. An ITO electrode having a solid pattern is formed as the first layer on the substrate to constitute the counter electrode, and a CVD (chemical vapor deposition) electrode is formed as the second layer on the first layer counter electrode. A SiN (silicon nitride) film was formed by the method. The SiN film of the second layer has a film thickness of 300 nm and functions as an interlayer insulating film. On the SiN film of the second layer, a comb-shaped pixel electrode formed by patterning an ITO film is arranged as a third layer, and two pixels of a first pixel and a second pixel are formed. was The size of each pixel was 10 mm long and about 5 mm wide. At this time, the counter electrode of the first layer and the pixel electrode of the third layer were electrically insulated by the action of the SiN film of the second layer.

The pixel electrode of the third layer has a comb shape in which a plurality of electrode elements each having a width of 3 μm and having a central portion bent at an internal angle of 160° are arranged in parallel with an interval of 6 μm. The pixel had a first region and a second region bounded by a line connecting bent portions of a plurality of electrode elements.
Comparing the first region and the second region of each pixel, the forming directions of the electrode elements of the pixel electrodes constituting them were different. That is, when the line connecting the bent portions of the plurality of pixel electrode elements is used as a reference, the electrode elements of the pixel electrode are formed so as to form an angle of 80° clockwise in the first region of the pixel, and the electrode elements of the pixel electrode in the second region of the pixel. The electrode elements of the pixel electrode are formed so as to form an angle of 80° counterclockwise. That is, in the first region and the second region of each pixel, the directions of the rotational movement (in-plane switching) of the liquid crystal induced by the voltage application between the pixel electrode and the counter electrode in the plane of the substrate are mutually different. It was configured in the opposite direction.

Next, the liquid crystal aligning agent obtained above was filtered through a filter with a pore size of 1.0 μm, and then applied to the surface of the prepared substrate with electrodes by a spin coating method. After drying on a hot plate at 80° C. for 2 minutes, baking was performed in an infrared heating furnace at 230° C. for 20 minutes to obtain a polyimide film with a film thickness of 60 nm. This polyimide film is rubbed and oriented with a rayon cloth (HY-5318 manufactured by Hyperflex) (roller diameter: 120 mm, roller rotation speed: 1000 rpm, moving speed: 20 mm / sec, indentation length: 0.4 mm, rubbing direction: 3rd layer 180° with respect to the line connecting the bent portions of the plurality of pixel electrode elements of the pixel electrode of the eye), ultrasonic irradiation is performed for 1 minute in pure water for cleaning, and water droplets are removed by air blow. Removed. Then, it dried at 80 degreeC for 10 minutes, and obtained the board|substrate with a liquid crystal aligning film. A glass substrate having columnar spacers with a height of 4 μm and having an ITO electrode formed on the back surface was also treated in the same manner as described above to obtain a substrate with a liquid crystal alignment film subjected to alignment treatment as a counter substrate. These two substrates with a liquid crystal alignment film are used as a set, and a sealant (Mitsui Chemicals XN-1500T) is printed on one of the substrates while leaving the liquid crystal injection port. They were laminated so that the alignment film surfaces faced each other and the rubbing directions were anti-parallel. After that, a heat treatment was performed at 150° C. for 60 minutes to cure the sealant, thereby producing an empty cell with a cell gap of 4 μm. A negative type liquid crystal MLC-7026-100 (manufactured by Merck Ltd.) was injected into this empty cell by a vacuum injection method, and the injection port was sealed to obtain an FFS liquid crystal cell for negative liquid crystals. After that, the obtained liquid crystal cell was heated at 120° C. for 1 hour, left at 23° C. overnight, and then used for evaluation.

<Fabrication of FFS driven liquid crystal cell for positive liquid crystal>
A liquid crystal cell for positive liquid crystal having the structure of an FFS mode liquid crystal display element was produced.
As the substrate with electrodes, the same one as in the FFS drive liquid crystal cell for negative liquid crystal was used.
The rubbing direction of the electrode-attached substrate is changed to a direction of 90° with respect to the line connecting the bent portions of the plurality of pixel electrode elements of the pixel electrode of the third layer, and the liquid crystal injected by the reduced-pressure injection method is positive. An FFS mode liquid crystal cell for positive liquid crystal was obtained in the same manner as the manufacturing method of the FFS drive liquid crystal cell for negative liquid crystal except that the liquid crystal was changed to type liquid crystal MLC-3019 (manufactured by Merck). After that, the obtained liquid crystal cell was heated at 120° C. for 1 hour and allowed to stand at 23° C. overnight before being used for evaluation.

<Preparation of liquid crystal cell for negative liquid crystal for evaluation of pretilt angle and voltage holding rate>
First, a substrate with electrodes was prepared. The substrate is a glass substrate with a size of 30 mm×40 mm and a thickness of 0.7 mm. An ITO electrode having a film thickness of 35 nm was formed on the substrate, and the electrode had a stripe pattern with an interval of 40 mm in length and 10 mm in width.
Next, the liquid crystal aligning agent obtained above was filtered through a filter having a pore size of 1.0 μm, and then applied to the prepared substrate with electrodes by a spin coating method. After drying on a hot plate at 80° C. for 2 minutes, baking was performed in an infrared heating furnace at 230° C. for 20 minutes to form a coating film having a thickness of 60 nm to obtain a substrate with a liquid crystal alignment film. Rubbing alignment treatment (roller diameter: 120 mm, roller rotation speed: 1000 rpm, moving speed: 20 mm / sec, indentation length: 0.4 mm) with a rayon cloth (HY-5318 manufactured by Hyperflex) is applied to the liquid crystal alignment film, and then pure water is applied. The substrate was cleaned by irradiating ultrasonic waves for 1 minute inside, water droplets were removed by an air blow, and dried at 80° C. for 10 minutes to obtain a substrate with a liquid crystal alignment film. Two substrates with the liquid crystal alignment film were prepared, and spherical spacers with a particle size of 4 μm were sprayed on the surface of one of the liquid crystal alignment films. 1500T) was printed thereon, and another substrate was pasted with the rubbing direction reversed and the film surfaces facing each other. After that, a heat treatment was performed at 150° C. for 60 minutes to cure the sealant to prepare an empty cell. A negative type liquid crystal MLC-7026-100 (manufactured by Merck & Co.) was injected into this empty cell by a vacuum injection method, and the injection port was sealed to obtain a liquid crystal cell. After that, the obtained liquid crystal cell was heated at 120° C. for 1 hour and allowed to stand at 23° C. overnight before being used for each evaluation.

<Preparation of liquid crystal cell for positive liquid crystal for evaluation of pretilt angle and voltage holding rate>
As the substrate with electrodes, the same one as the liquid crystal cell for negative liquid crystal for evaluating the pretilt angle and voltage holding rate was used. Except for changing the liquid crystal to be injected by the reduced pressure injection method to the positive type liquid crystal MLC-3019 (manufactured by Merck), by operating in the same manner as the manufacturing method of the negative liquid crystal cell for evaluating the pretilt angle and voltage holding rate, A liquid crystal cell for positive liquid crystal was obtained. After that, the obtained liquid crystal cell was heated at 120° C. for 1 hour and allowed to stand at 23° C. overnight before being used for evaluation.

[Characteristic evaluation of liquid crystal cell]
The characteristics of the FFS drive liquid crystal cell and the pretilt angle and voltage holding rate evaluation liquid crystal cell produced above were evaluated as follows.
<Evaluation of voltage holding ratio after backlight resistance test>
The voltage holding rate evaluation liquid crystal cell was left for 96 hours under irradiation with a high-brightness backlight (light source: LED, brightness: 30000 cd/m ² ) having a surface temperature of 50°C. Next, a voltage of 1 V was applied to the liquid crystal cell at a temperature of 60° C. for 60 μsec, the voltage was measured after 167 msec, and how much voltage was retained was calculated as a voltage holding ratio. The higher the voltage holding ratio, the better. Specifically, when a liquid crystal cell for negative liquid crystal was used, the voltage holding rate was evaluated as "O" when it was 54% or more, and as "X" when it was less than 54%. When the liquid crystal cell for positive liquid crystal was used, the voltage holding ratio was evaluated as "O" when it was 85% or more, and as "B" when it was less than 85%. It is known that when the voltage holding ratio, which is one of the electrical characteristics of the liquid crystal display element, is increased, line burn-in, which is one of the display defects of the liquid crystal display element, is less likely to occur.

<Afterimage evaluation by long-term AC drive>
Using the FFS-driven liquid crystal cell produced above, an AC voltage of ±5.5 V was applied at a frequency of 30 Hz for 96 hours under illumination from a high-brightness backlight (light source: LED, brightness: 30000 cd/m ² ). After that, the pixel electrode and the counter electrode of the FFS-driven liquid crystal cell were short-circuited and left at room temperature for one day.
After standing, the FFS-driven liquid crystal cell is placed between two polarizing plates arranged so that the polarizing axes are orthogonal to each other, and the backlight is turned on with no voltage applied to minimize the brightness of the transmitted light. The arrangement angle of the FFS-driven liquid crystal cell was adjusted as follows. Then, the rotation angle when the liquid crystal cell is rotated from the angle at which the second region of the first pixel is darkest to the angle at which the first region of the first pixel is darkest is calculated as the angle Δ. Similarly, for the second pixel, the angle Δ was similarly calculated by comparing the second region and the first region.
When this angle Δ was 0.1° or less, the afterimage property was excellent, that is, it was evaluated as “good”, and when the angle Δ was greater than 0.1°, it was defined as “poor” and evaluated.

<Evaluation of Viewing Angle Characteristics>
Using an AxoScan Muller matrix polarimeter manufactured by Optometrix, the pretilt angle in the liquid crystal cell for pretilt angle evaluation was measured. Viewing angle characteristics are better as the pretilt angle value is lower. Specifically, when the pretilt angle was 1.7° or less, it was evaluated as “◯”, and when it was greater than 1.7°, it was evaluated as “X”.

Table 3 shows the evaluation results of the voltage holding ratio, afterimage evaluation, and viewing angle characteristics of the liquid crystal cells for negative liquid crystals using the liquid crystal aligning agents of Examples 1 to 15 and Comparative Examples 1 to 9.

As shown in Table 3, the liquid crystal display elements using the liquid crystal alignment films of Examples 1 to 15 obtained from liquid crystal alignment agents using diamine components containing specific diamines DA-1 to DA-3 had a voltage holding rate of , afterimage characteristics and viewing angle characteristics were all good.

Table 4 shows the evaluation results of the voltage holding ratio, afterimage evaluation, and viewing angle characteristics of the liquid crystal cells for positive liquid crystals using the liquid crystal aligning agents of Examples 16 to 18 and Comparative Examples 9 and 10 above.

As shown in Table 4, the liquid crystal display elements using the liquid crystal alignment films of Examples 16 to 18 obtained from liquid crystal alignment agents using diamine components containing specific diamines DA-1 to DA-3 had a voltage holding rate of , afterimage characteristics and viewing angle characteristics were all good.

The liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention is widely used in liquid crystal display elements of various operation modes. It can also be used for a film or a liquid crystal alignment film for a transmission scattering type liquid crystal light control device.

The liquid crystal display device of the present invention can be effectively applied to devices having various functions, such as liquid crystal televisions, clocks, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, and digital cameras. , mobile phones, smart phones, various monitors, information displays, etc.

1: Horizontal electric field liquid crystal display element 2:

Comb electrode substrate

2a, 4b, 2d: Base material 2b, 2g:

Linear electrodes

2c, 2h, 4a: Liquid crystal alignment film 2e: Surface electrode 2f: Insulation Film, 3: liquid crystal, 4: counter substrate, L: electric lines of force

In addition, the entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2021-067838 filed on April 13, 2021 are cited here, and as a disclosure of the specification of the present invention, It is taken in.

Claims

Characterized by containing a polymer having at least one repeating unit selected from the group consisting of a repeating unit (p1) represented by the following formula (1) and an imidized structural unit of the repeating unit (p1) Liquid crystal aligning agent.

(In formula (1), X 1 represents a tetravalent organic group. Y 1 represents a divalent organic group represented by "-Ar 1 -OWO-Ar 2 -".
Ar 1 and Ar 2 each independently represent a divalent aromatic group of either a divalent benzene ring or a biphenyl structure, any hydrogen atom of the aromatic group being replaced with a monovalent group may
W is *-(CH 2 ) m -L-A-* (L represents -O-C(=O)- or -C(=O)-O-, A is -(CH 2 ) n - represents.
m is an integer of 1-6. n is an integer from 1 to 16; When n is 2 or more, any —CH 2 — constituting A is —O—, —C(=O)—, —NH—, —OC(=O)—, —C(=O ) —O—, —C═C—, a phenylene group, or a cyclohexylene group.
Also, some of the hydrogen atoms of W may be substituted with a halogen atom, a methyl group, a trifluoromethyl group, or a hydroxy group. ) is a divalent organic group having 4 to 20 carbon atoms. * represents a bond.
R and Z each independently represent a hydrogen atom or a monovalent organic group. )
At least one polymer selected from the group consisting of a polyimide precursor obtained using a diamine component containing a diamine (0) represented by the following formula (D A ) and a polyimide that is an imidized product of the polyimide precursor 2. The liquid crystal aligning agent according to claim 1, which is a seed polymer (P).

(Ar 1 , Ar 2 and W are as defined in claim 1.)
W in the formula (D A ) is *-(CH 2 ) p -O-C(=O)-(CH 2 ) q -*, *-(CH 2 ) p -O-C(=O)- (CH 2 ) q —C(=O)—O—(CH 2 ) r —*,*—(CH 2 ) p —C(=O)—O—(CH 2 ) q —O—C(=O )-(CH 2 ) r -*, *-(CH 2 ) p -O-C(=O)-QC(=O)-O-(CH 2 ) q -* or *-(CH 2 ) p —C(=O)—OQ—O—C(=O)—(CH 2 ) q −*, Q represents a phenylene group or a cyclohexylene group, and p, q, and r are each The liquid crystal aligning agent according to claim 2, which is independently an integer of 1 to 6.
4. The liquid crystal aligning agent according to claim 2, wherein the diamine (0) is any diamine selected from the group consisting of the following formulas (d A -1) to (d A -5).

(The hydrogen atom on the benzene ring in formulas (d A -1) to (d A -5) may be substituted with a monovalent substituent.)
The polymer (P) contains the diamine component, an acyclic aliphatic tetracarboxylic dianhydride, an alicyclic tetracarboxylic dianhydride, an aromatic tetracarboxylic dianhydride, or a derivative thereof. The liquid crystal aligning agent according to any one of claims 2 to 4, obtained by a polycondensation reaction with a tetracarboxylic acid component.
The liquid crystal aligning agent according to any one of claims 2 to 5, wherein the diamine (0) is used in an amount of 5 mol% or more with respect to the diamine component.
Furthermore, at least one polymer selected from the group consisting of a polyimide precursor obtained using a diamine component that does not contain the diamine (0) and a polyimide that is an imidized product of the polyimide precursor (B). The liquid crystal aligning agent according to any one of claims 2 to 6.
A crosslinkable compound having at least one substituent selected from an oxiranyl group, an oxetanyl group, a blocked isocyanate group, an oxazoline group, a cyclocarbonate group, a hydroxy group and an alkoxy group, and a crosslinkable compound having a polymerizable unsaturated group. At least one crosslinkable compound selected from the group, a functional silane compound, a metal chelate compound, a curing accelerator, a surfactant, an antioxidant, a sensitizer, an antiseptic, and the dielectric constant of the obtained liquid crystal alignment film, The liquid crystal aligning agent according to any one of claims 2 to 7, further comprising an additive component selected from compounds for adjusting electric resistance.
A liquid crystal alignment film obtained from the liquid crystal alignment agent according to any one of claims 1 to 8.
A liquid crystal display element comprising the liquid crystal alignment film according to claim 9.
The liquid crystal display element according to claim 10, which is a horizontal electric field liquid crystal display element.
A method for manufacturing a liquid crystal display element, comprising the following steps (1) to (3).
Step (1): A step of applying the liquid crystal aligning agent according to any one of claims 1 to 8 onto a substrate Step (2): A step of baking the applied liquid crystal aligning agent to obtain a film Step (3) ): the step of subjecting the film obtained in step (2) to orientation treatment
A diamine represented by the following formula (d A -1) or (d A -3).

(The hydrogen atom on the benzene ring in formulas (d A -1) and (d A -3) may be substituted with a monovalent substituent.)
A polymer obtained from a diamine component containing the diamine according to claim 13.
A polyimide that is a polyimide precursor or an imidized product thereof obtained by a polycondensation reaction of a diamine component containing the diamine according to claim 13 and a tetracarboxylic acid component.