JP2013241571A - Liquid crystal aligning agent, and liquid crystal display device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystal aligning agent excellent in alignability of the liquid crystal molecule, and having a high transmittance; and to provide an aligned film using the liquid crystal aligning agent, and a liquid crystal display device using the aligned film.SOLUTION: There are provided a polyamic acid or its derivative obtained by reacting a tetracarboxylic dianhydride containing at least a tetracarboxylic dianhydride represented by formula (1) with a diamine, a liquid crystal aligning agent and a liquid crystal aligned film containing the polyamic acid or its derivative, and a liquid crystal display device having the liquid crystal aligned film.

Description

  The present invention relates to a liquid crystal aligning agent containing a polyamic acid or a derivative thereof obtained by reacting a specific alicyclic tetracarboxylic dianhydride with a diamine, an alignment film using the liquid crystal aligning agent, and the liquid crystal alignment film The present invention relates to a liquid crystal display element having

  Various display devices such as personal computer monitors, LCD TVs, video camera viewfinders, and projection displays, as well as optoelectronic devices such as optical printer heads, optical Fourier transform elements, and light valves, have been commercialized today. Generally used liquid crystal display elements are display elements using nematic liquid crystals. As a display system of the nematic liquid crystal display element, a TN (Twisted Nematic) mode and an STN (Super Twisted Nematic) mode are well known. In recent years, in order to improve the narrow viewing angle, which is one of the problems of these modes, a TN liquid crystal display device using an optical compensation film, MVA (Multi -domain Vertical Alignment) mode or IPS (In-Plane Switching) mode of a horizontal electric field method has been proposed and put into practical use.

  In order to give these liquid crystal display elements uniform display characteristics, it is necessary to uniformly control the molecular arrangement of the liquid crystal. Specifically, the liquid crystal molecules on the substrate are uniformly aligned in one direction, the liquid crystal molecules have a certain tilt angle (pretilt angle) from the substrate surface, and the like. The liquid crystal alignment film plays such a role. The liquid crystal alignment film is one of the important elements related to the display quality of the liquid crystal display element, and the role of the liquid crystal alignment film is becoming important year by year as the quality of the display element is improved.

  The liquid crystal alignment film is formed using a liquid crystal alignment agent. The liquid crystal aligning agent mainly used at present is a solution (varnish) obtained by dissolving polyamic acid or soluble polyimide in an organic solvent. After this solution is applied to the substrate, it is formed by means such as heating to form a polyimide-based liquid crystal alignment film. The rubbing method is currently used industrially as a method for imparting the property of aligning liquid crystal molecules to this film (alignment treatment). The rubbing method is a process of rubbing the surface of the liquid crystal alignment film in one direction using a cloth in which fibers of nylon, rayon, polyester, or the like are planted, and this makes it possible to obtain uniform alignment of liquid crystal molecules. However, the rubbing method has problems such as display defects due to alignment film scraping and fiber dust adhesion that occur during the process, and display defects caused by destruction of TFT (Thin-Film-Transistor) elements due to static electricity. ing.

  In order to solve this problem, a photo-alignment method in which the formed film is irradiated with light and subjected to an alignment process has been proposed. To date, there are many photodecomposition methods, photoisomerization methods, photodimerization methods, photocrosslinking methods, etc. (See, for example, Non-Patent Document 1 and Patent Documents 1 to 5). The photo-alignment method has higher alignment uniformity than the rubbing method, and the non-contact alignment method does not damage the film, reducing the causes of display defects such as dust generation and static electricity. There are advantages such as being able to.

  Many studies have been made on materials used for a liquid crystal alignment film (hereinafter sometimes abbreviated as “photo-alignment film”) by a photo-alignment method, but tetracarboxylic dianhydride, particularly cyclobutane tetracarboxylic dianhydride. It has been reported that a photo-alignment film using polyimide using as a raw material can align liquid crystal molecules uniformly and stably (see, for example, Patent Document 1). This is a method of giving a function of aligning liquid crystals in a certain direction by irradiating a film formed on a substrate with ultraviolet rays or the like to cause a chemical change in polyimide. However, the photo-alignment film according to such a method has a problem that the electrical characteristics are inferior, as compared with the alignment film based on the rubbing method, such that the amount of impurity ions increases and the voltage holding ratio decreases. In order to solve this, various studies have been made on the molecular structure constituting polyimide (see, for example, Patent Documents 2 and 3).

  On the other hand, since the alignment of liquid crystal molecules is inferior to the rubbing method in the photo-alignment method, there is a problem that anchoring energy is small and the response speed of the liquid crystal display element is lowered and burn-in is caused.

JP-A-9-297313 JP 2004-206091 A International Publication No. 2005/83504 Pamphlet JP 2005-275364 A JP 2006-171304 A

Liquid Crystal, Vol. 3, No. 4, 262 pages, 1999

  The subject of this invention is providing the liquid crystal aligning agent which is excellent in the orientation of a liquid crystal molecule, and has a high transmittance | permeability. Another object of the present invention is to provide an alignment film using the liquid crystal aligning agent, and to provide a liquid crystal display element using the alignment film.

  The inventors of the present invention use a polyamic acid or a derivative thereof obtained from a tetracarboxylic dianhydride represented by formula (1) and a diamine as a liquid crystal aligning agent, thereby providing good alignment and transmission. The present inventors have found that a liquid crystal alignment film having a high rate can be obtained.

The present invention has the following configuration.
[1] A polyamic acid or a derivative thereof obtained by reacting a tetracarboxylic dianhydride containing at least a tetracarboxylic dianhydride represented by the following formula (1) with a diamine.

[2] The tetracarboxylic dianhydride represented by the formula (1) is at least one of the tetracarboxylic dianhydrides represented by the following formula (1-a) or (1-b): [1] Or a derivative thereof.

式（ＡＮ−Ｉ）、（ＡＮ−ＩＶ）および（ＡＮ−Ｖ）において、Ｘは独立して単結合または−ＣＨ₂−であり；
式（ＡＮ−ＩＩ）において、Ｇは単結合、炭素数１〜２０のアルキレン、−ＣＯ−、−Ｏ−、−Ｓ−、−ＳＯ₂−、−Ｃ（ＣＨ₃）₂−、または−Ｃ（ＣＦ₃）₂−であり；
式（ＡＮ−ＩＩ）〜（ＡＮ−ＩＶ）において、Ｙは独立して下記の３価の基の群から選ばれる１つであり；

これらの基の任意の水素はメチル、エチルまたはフェニルで置き換えられてもよく；
式（ＡＮ−ＩＩＩ）〜（ＡＮ−Ｖ）において、環Ａは炭素数３〜１０の単環式炭化水素の基または炭素数６〜３０の縮合多環式炭化水素の基であり、この基の任意の水素はメチル、エチルまたはフェニルで置き換えられていてもよく、環に掛かっている結合手は環を構成する任意の炭素に連結しており、２本の結合手が同一の炭素に連結してもよく；
式（ＡＮ−ＶＩ）において、Ｘ¹⁰は炭素数２〜６のアルキレンであり；
Ｍｅはメチルであり；
Ｐｈはフェニルであり；
式（ＡＮ−ＶＩＩ）において、Ｇ¹⁰は独立して−Ｏ−、−ＣＯＯ−または−ＯＣＯ−であり；そして、
ｒは独立して０または１である。 [3] The tetracarboxylic dianhydride contains at least one selected from the group of tetracarboxylic dianhydrides represented by the following formulas (AN-I) to (AN-VII), [1] or The polyamic acid or derivative thereof according to [2].

In formulas (AN-I), (AN-IV) and (AN-V), X is independently a single bond or —CH ₂ —;
In the formula (AN-II), G represents a single bond, alkylene having 1 to 20 carbon atoms, —CO—, —O—, —S—, —SO ₂ —, —C (CH ₃ ) ₂ —, or —C. (CF ₃ ) ₂ —;
In the formulas (AN-II) to (AN-IV), Y is independently one selected from the following group of trivalent groups;

Any hydrogen in these groups may be replaced by methyl, ethyl or phenyl;
In the formulas (AN-III) to (AN-V), the ring A is a monocyclic hydrocarbon group having 3 to 10 carbon atoms or a condensed polycyclic hydrocarbon group having 6 to 30 carbon atoms. Any hydrogen in may be replaced by methyl, ethyl or phenyl, and the bond on the ring is connected to any carbon constituting the ring, and the two bonds are connected to the same carbon May be;
In the formula (AN-VI), X ¹⁰ is alkylene having 2 to 6 carbons;
Me is methyl;
Ph is phenyl;
In formula (AN-VII), G ¹⁰ is independently —O—, —COO— or —OCO—; and
r is independently 0 or 1.

式（ＡＮ−４−１７）において、ｍは１〜１２の整数である。 [4] The tetracarboxylic dianhydride has the following formula (AN-1-1), (AN-1-13), (AN-2-1), (AN-3-1), (AN-3- 2) at least one selected from the group consisting of (AN-4-5), (AN-4-17), (AN-7-2), (AN-10), and (AN-11-3) The polyamic acid or derivative thereof according to any one of [1] to [3], which contains

In formula (AN-4-17), m is an integer of 1-12.

式（ＤＩ−１）において、ｍは１〜１２の整数であり；
（ＤＩ−３）および（ＤＩ−５）〜（ＤＩ−７）において、Ｇ²¹は独立して単結合、−ＮＨ−、−Ｏ−、−Ｓ−、−Ｓ−Ｓ−、−ＳＯ₂−、−ＣＯ−、−ＣＯＮＨ−、−ＣＯＮＣＨ₃−、−ＮＨＣＯ−、−Ｃ（ＣＨ₃）₂−、−Ｃ（ＣＦ₃）₂−、−（ＣＨ₂）_m'−、−Ｏ−（ＣＨ₂）_m'−Ｏ−、−Ｎ（ＣＨ₃）−（ＣＨ₂）_k−Ｎ（ＣＨ₃）−、または−Ｓ−（ＣＨ₂）_m'−Ｓ−であり、ｍ’は独立して１〜１２の整数であり、ｋは１〜５の整数であり；
（ＤＩ−６）および（ＤＩ−７）において、Ｇ²²は独立して単結合、−Ｏ−、−Ｓ−、−ＣＯ−、−Ｃ（ＣＨ₃）₂−、−Ｃ（ＣＦ₃）₂−、または炭素数１〜１０のアルキレンであり；
式（ＤＩ−２）〜（ＤＩ−７）中のシクロヘキサン環およびベンゼン環の任意の−Ｈは、−Ｆ、−ＣＨ₃、−ＯＨ、−ＣＦ₃、−ＣＯ₂Ｈ、−ＣＯＮＨ₂、またはベンジルで置き換えられていてもよく、加えて式（ＤＩ−４）においては、下記式（ＤＩ−４−ａ）〜（ＤＩ−４−ｃ）で置き換えられていてもよく、

式（ＤＩ−４−ａ）および（ＤＩ−４−ｂ）において、Ｒ²⁰は独立して−Ｈまたは−ＣＨ₃であり；
式（ＤＩ−２）〜（ＤＩ−７）において、環を構成するいずれかの炭素原子に結合位置が固定されていない基は、その環における結合位置が任意であることを示し；そして、
シクロヘキサン環またはベンゼン環への−ＮＨ₂の結合位置は、Ｇ²¹またはＧ²²の結合位置を除く任意の位置である。

式（ＤＩ−８）において、Ｒ²¹およびＲ²²は独立して炭素数１〜３のアルキルまたはフェニルであり；
Ｇ²³は独立して炭素数１〜６のアルキレン、フェニレンまたはアルキル置換されたフェニレンであり；
ｎは１〜１０の整数であり；
式（ＤＩ−９）において、Ｒ²³は独立して炭素数１〜５のアルキル、炭素数１〜５のアルコキシまたは−Ｃｌであり；
ｐは独立して０〜３の整数であり；
ｑは０〜４の整数であり；
式（ＤＩ−１０）において、Ｒ²⁴は−Ｈ、炭素数１〜４のアルキル、フェニル、またはベンジルであり；
式（ＤＩ−１１）において、Ｇ²⁴は−ＣＨ₂−または−ＮＨ−であり；
式（ＤＩ−１２）において、Ｇ²⁵は単結合、炭素数２〜６のアルキレンまたは１，４−フェニレンであり；
ｒは０または１であり；
式（ＤＩ−１２）において、環を構成するいずれかの炭素原子に結合位置が固定されていない基は、その環における結合位置が任意であることを示し；そして、
式（ＤＩ−９）、（ＤＩ−１１）および（ＤＩ−１２）において、ベンゼン環に結合する−ＮＨ₂の結合位置は任意の位置であり；

式（ＤＩ−１３）において、Ｇ²⁶は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−、−ＣＯＮＨ−、−ＣＨ₂Ｏ−、−ＯＣＨ₂−、−ＣＦ₂Ｏ−、−ＯＣＦ₂−、または−（ＣＨ₂）_m'−であり、ｍ’は１〜１２の整数であり；
Ｒ²⁵は炭素数３〜２０のアルキル、フェニル、ステロイド骨格を有する基、または下記の式（ＤＩ−１３−ａ）で表される基であり、このアルキルにおいて、任意の−Ｈは−Ｆで置き換えられてもよく、任意の−ＣＨ₂−は−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられていてもよく、このフェニルの−Ｈは、−Ｆ、−ＣＨ₃、−ＯＣＨ₃、−ＯＣＨ₂Ｆ、−ＯＣＨＦ₂、−ＯＣＦ₃、炭素数３〜２０のアルキル、または炭素数３〜２０のアルコキシで置き換えられていてもよく、このシクロヘキシルの−Ｈは炭素数３〜２０のアルキルまたは炭素数３〜２０のアルコキシで置き換えられていてもよく、ベンゼン環に結合する−ＮＨ₂の結合位置はその環において任意の位置であることを示し；

式（ＤＩ−１３−ａ）において、Ｇ²⁷、Ｇ²⁸およびＧ²⁹は結合基を表し、これらは独立して単結合、または炭素数１〜１２のアルキレンであり、このアルキレンの１以上の−ＣＨ₂−は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＣＨ＝ＣＨ−で置き換えられていてもよく；
環Ｂ²¹、環Ｂ²²、環Ｂ²³、および環Ｂ²⁴は独立して１，４−フェニレン、１，４−シクロへキシレン、１，３−ジオキサン−２，５−ジイル、ピリミジン−２，５−ジイル、ピリジン−２，５−ジイル、ナフタレン−１，４−ジイル、ナフタレン−１，５−ジイル、ナフタレン−２，６−ジイル、ナフタレン−２，７−ジイル、またはアントラセン−９，１０−ジイルであり；
環Ｂ²¹、環Ｂ²²、環Ｂ²³、および環Ｂ²⁴において、任意の−Ｈは−Ｆまたは−ＣＨ₃で置き換えられてもよく；
ｓ，ｔおよびｕは独立して０〜２の整数であり、これらの合計は１〜５であり；
ｓ，ｔまたはｕが２であるとき、各々の括弧内の２つの結合基は同じであっても異なってもよく、２つの環は同じであっても異なっていてもよく；
Ｒ²⁶は−Ｆ、−ＯＨ、炭素数１〜３０のアルキル、炭素数１〜３０のフッ素置換アルキル、炭素数１〜３０のアルコキシ、−ＣＮ、−ＯＣＨ₂Ｆ、−ＯＣＨＦ₂、または−ＯＣＦ₃であり、この炭素数１〜３０のアルキルの任意の−ＣＨ₂−は下記式（ＤＩ−１３−ｂ）で表される２価の基で置き換えられていてもよく；

式（ＤＩ−１３−ｂ）において、Ｒ²⁷およびＲ²⁸は独立して炭素数１〜３のアルキルであり；
ｖは１〜６の整数であり；

式（ＤＩ−１４）および式（ＤＩ−１５）において、Ｇ³⁰は独立して単結合、−ＣＯ−または−ＣＨ₂−であり；
Ｒ²⁹は独立して−Ｈまたは−ＣＨ₃であり；
Ｒ³⁰は−Ｈ、炭素数１〜２０のアルキル、または炭素数２〜２０のアルケニルであり；
式（ＤＩ−１５）におけるベンゼン環の１つの−Ｈは、炭素数１〜２０のアルキルまたはフェニルで置き換えられてもよく；
式（ＤＩ−１４）および式（ＤＩ−１５）において、環を構成するいずれかの炭素原子に結合位置が固定されていない基は、その環における結合位置が任意であることを示し；
ベンゼン環に結合する−ＮＨ₂はその環における結合位置が任意であることを示し；

式（ＤＩ−１６）および式（ＤＩ−１７）において、Ｇ³¹は独立して−Ｏ−または炭素数１〜６のアルキレンであり；
Ｇ³²は単結合または炭素数１〜３のアルキレンであり；
Ｒ³¹は−Ｈまたは炭素数１〜２０のアルキルであり、このアルキルの任意の−ＣＨ₂−は、−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく；
Ｒ³²は炭素数６〜２２のアルキルであり；
Ｒ³³は−Ｈまたは炭素数１〜２２のアルキルであり；
環Ｂ²⁵は１，４−フェニレンまたは１，４−シクロヘキシレンであり；
ｒは０または１であり；そして、
ベンゼン環に結合する−ＮＨ₂はその環における結合位置が任意であることを示す。 [5] The polyamic acid or derivative thereof according to any one of [1] to [4], wherein the diamine contains at least one selected from the group consisting of the following formulas (DI-1) to (DI-17): .

In the formula (DI-1), m is an integer of 1 to 12;
In (DI-3) and (DI-5) to (DI-7), G ²¹ is independently a single bond, —NH—, —O—, —S—, —S—S—, —SO ₂ —. , —CO—, —CONH—, —CONCH ₃ —, —NHCO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, — (CH ₂ ) _{m ′} —, —O— (CH _{2) m '-O -, -} N (CH 3) - (CH 2) k -N (CH 3) -, or -S- (CH _{2) m'} is -S-, m 'is independently An integer from 1 to 12, k is an integer from 1 to 5;
In (DI-6) and (DI-7), G ²² is independently a single bond, —O—, —S—, —CO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) _2. -Or alkylene having 1 to 10 carbon atoms;
In the formulas (DI-2) to (DI-7), any —H of the cyclohexane ring and the benzene ring is —F, —CH ₃ , —OH, —CF ₃ , —CO ₂ H, —CONH ₂ , or In the formula (DI-4), the following formulas (DI-4-a) to (DI-4-c) may be substituted,

In formulas (DI-4-a) and (DI-4-b), R ²⁰ is independently —H or —CH ₃ ;
In formulas (DI-2) to (DI-7), a group whose bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary; and
The bonding position of —NH ₂ to the cyclohexane ring or the benzene ring is an arbitrary position excluding the bonding position of G ²¹ or G ²² .

In formula (DI-8), R ²¹ and R ²² are independently alkyl having 1 to 3 carbons or phenyl;
G ²³ is independently alkylene having 1 to 6 carbons, phenylene or alkyl-substituted phenylene;
n is an integer from 1 to 10;
In formula (DI-9), R ²³ is independently alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons or —Cl;
p is independently an integer from 0 to 3;
q is an integer from 0 to 4;
In the formula (DI-10), R ²⁴ is —H, alkyl having 1 to 4 carbons, phenyl, or benzyl;
In the formula (DI-11), G ²⁴ is —CH ₂ — or —NH—;
In the formula (DI-12), G ²⁵ is a single bond, alkylene having 2 to 6 carbons or 1,4-phenylene;
r is 0 or 1;
In formula (DI-12), a group whose bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary; and
In formulas (DI-9), (DI-11) and (DI-12), the bonding position of —NH ₂ bonded to the benzene ring is an arbitrary position;

In the formula (DI-13), G ²⁶ represents a single bond, —O—, —COO—, —OCO—, —CO—, —CONH—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—. , -OCF ₂ -, or - (CH _{2) m '-} it is and, m' is an integer from 1 to 12;
R ²⁵ is alkyl having 3 to 20 carbons, phenyl, a group having a steroid skeleton, or a group represented by the following formula (DI-13-a). In this alkyl, any —H is —F Any —CH ₂ — may be replaced by —O—, —CH═CH— or —C≡C—, and —H of this phenyl is —F, —CH ₃ , _{-OCH 3, -OCH 2 F, -OCHF} 2, -OCF 3, alkyl having 3 to 20 carbon atoms, or may be replaced by alkoxy having 3 to 20 carbon atoms, -H of cyclohexyl 3 carbon atoms Which may be replaced by ˜20 alkyl or C 3-20 alkoxy, and indicates that the bonding position of —NH ₂ bonded to the benzene ring is an arbitrary position in the ring;

In the formula (DI-13-a), G ²⁷ , G ^28, and G ²⁹ each represent a bonding group, and these are each independently a single bond or alkylene having 1 to 12 carbons, and one or more — CH ₂ — may be replaced by —O—, —COO—, —OCO—, —CONH—, —CH═CH—;
Ring B ²¹ , Ring B ²² , Ring B ²³ , and Ring B ²⁴ are independently 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2, 5-diyl, pyridine-2,5-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, or anthracene-9,10 -Diyl;
In ring B ²¹ , ring B ²² , ring B ²³ , and ring B ²⁴ , any —H may be replaced by —F or —CH ₃ ;
s, t and u are independently integers from 0 to 2 and their sum is 1 to 5;
when s, t or u is 2, the two linking groups in each bracket may be the same or different and the two rings may be the same or different;
R ²⁶ represents —F, —OH, alkyl having 1 to 30 carbon atoms, fluorine-substituted alkyl having 1 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms, —CN, —OCH ₂ F, —OCHF ₂ , or —OCF. _And any —CH ₂ — in the alkyl having 1 to 30 carbon atoms may be replaced by a divalent group represented by the following formula (DI-13-b);

In the formula (DI-13-b), R ²⁷ and R ²⁸ are independently alkyl having 1 to 3 carbons;
v is an integer from 1 to 6;

In formula (DI-14) and formula (DI-15), G ³⁰ is independently a single bond, —CO— or —CH ₂ —;
R ²⁹ is independently —H or —CH ₃ ;
R ³⁰ is —H, alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons;
One -H of the benzene ring in formula (DI-15) may be replaced by alkyl having 1 to 20 carbons or phenyl;
In formula (DI-14) and formula (DI-15), a group whose bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary;
Bonded to the benzene ring -NH ₂ indicates that the binding position in the ring is optional;

In formula (DI-16) and formula (DI-17), G ³¹ is independently —O— or alkylene having 1 to 6 carbons;
G ³² is a single bond or alkylene having 1 to 3 carbon atoms;
R ³¹ is —H or alkyl having 1 to 20 carbons, and any —CH ₂ — in the alkyl may be replaced by —O—, —CH═CH— or —C≡C—;
R ³² is alkyl having 6 to 22 carbons;
R ³³ is —H or C 1-22 alkyl;
Ring B ²⁵ is 1,4-phenylene or 1,4-cyclohexylene;
r is 0 or 1; and
-NH ₂ bonded to the benzene ring indicates that the binding position in the ring is optional.

式（２−ａ）において、Ｇは単結合、炭素数１〜２０のアルキレン、−ＣＯ−、−Ｏ−、−Ｓ−、−ＳＯ₂−、−Ｃ（ＣＨ₃）₂−、または−Ｃ（ＣＦ₃）₂−であり；
式（２−ｂ）において、環Ｂはシクロヘキサン環、ベンゼン環またはナフタレン環であり、この基の任意の水素はメチル、エチル、またはフェニルで置き換えられてもよく；
式（２−ｃ）において、環Ｃはそれぞれ独立してシクロヘキサン環、またはベンゼン環であり、この基の任意の水素はメチル、エチル、またはフェニルで置き換えられてもよく；Ｙは単結合、炭素数１〜２０のアルキレン、−ＣＯ−、−Ｏ−、−Ｓ−、−ＳＯ₂−、−Ｃ（ＣＨ₃）₂−、または−Ｃ（ＣＦ₃）₂−である。 [6] The polyamic acid or derivative thereof according to any one of [1] to [5], wherein the diamine contains at least one dihydrazide selected from the following formulas (2-a) to (2-c).

In the formula (2-a), G represents a single bond, alkylene having 1 to 20 carbon atoms, —CO—, —O—, —S—, —SO ₂ —, —C (CH ₃ ) ₂ —, or —C. (CF ₃ ) ₂ —;
In formula (2-b), ring B is a cyclohexane ring, a benzene ring or a naphthalene ring, and any hydrogen of this group may be replaced with methyl, ethyl, or phenyl;
In formula (2-c), each ring C is independently a cyclohexane ring or a benzene ring, and any hydrogen of this group may be replaced by methyl, ethyl, or phenyl; Y is a single bond, carbon It is alkylene of formula 1 to 20, —CO—, —O—, —S—, —SO ₂ —, —C (CH ₃ ) ₂ —, or —C (CF ₃ ) ₂ —.

式（２−ａ−２）において、ｍは１〜１２の整数である。 [7] The dihydrazide is represented by the following formulas (2-a-1) to (2-a-2), (2-b-1) to (2-b-3) or (2-c-1) to ( The polyamic acid or derivative thereof according to [6], which is at least one dihydrazide selected from 2-c-6).

In formula (2-a-2), m is an integer of 1-12.

[8] The polyamic material according to any one of [1] to [7], wherein the diamine contains at least one photosensitive diamine selected from the following formulas (DI-19-1) to (DI-19-9): Acid or its derivative.

式（ＤＩ−５−１）、（ＤＩ−５−１２）、（ＤＩ−７−３）および（２−ａ−２）において、ｍは１〜１２の整数であり；
式（ＤＩ−５−３０）において、ｋは１〜５の整数であり；
式（ＤＩ−７−３）において、ｎは１または２あり；
式（ＤＩ−１３−４）および（ＤＩ−１３−５）において、Ｒ³⁵は炭素数１〜３０のアルキルまたは炭素数１〜３０のアルコキシであり；
式（ＤＩ−１６−１）および（ＤＩ−１６−２）において、Ｒ⁴⁰は−Ｈまたは炭素数１〜２０のアルキルであり；
式（ＤＩ−１６−４）において、Ｒ⁴¹は−Ｈまたは炭素数１〜１２のアルキルである。 [9] The diamine is represented by the following formulas (DI-1-3), (DI-1-4), (DI-4-1), (DI-5-1), (DI-5-5), (DI -5-9), (DI-5-12), (DI-5-21), (DI-5-28), (DI-5-30), (DI-5-31), (DI-7) -3), (DI-9-1), (DI-13-4), (DI-13-5), (DI-13-47), (DI-16-1), (DI-16-2) ), (DI-16-4), (DI-19-1), (2-a-1), (2-a-2), (2-b-1) or (2-b-2) The polyamic acid or derivative thereof according to any one of [1] to [8], which contains at least one selected from the group consisting of:

In the formulas (DI-5-1), (DI-5-12), (DI-7-3) and (2-a-2), m is an integer of 1 to 12;
In the formula (DI-5-30), k is an integer of 1 to 5;
In the formula (DI-7-3), n is 1 or 2;
In the formulas (DI-13-4) and (DI-13-5), R ³⁵ is alkyl having 1 to 30 carbons or alkoxy having 1 to 30 carbons;
In the formulas (DI-16-1) and (DI-16-2), R ⁴⁰ is —H or alkyl having 1 to 20 carbons;
In the formula (DI-16-4), R ⁴¹ represents —H or alkyl having 1 to 12 carbons.

[10] A liquid crystal aligning agent containing the polyamic acid or derivative thereof according to any one of [1] to [9].

[11] The method according to [10], further comprising at least one selected from the group consisting of an alkenyl-substituted nadiimide compound, a compound having a radical polymerizable unsaturated double bond, an oxazine compound, an oxazoline compound, and an epoxy compound. Liquid crystal aligning agent.

[12] The alkenyl-substituted nadiimide compound is bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) phenyl} methane, N, N′-m-xylylene- Bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) and N, N′-hexamethylene-bis (allylbicyclo [2.2.1] hept-5- The liquid crystal aligning agent according to [11], which is at least one selected from the group of compounds consisting of ene-2,3-dicarboximide).

[13] Compounds having a radical polymerizable unsaturated double bond are N, N′-ethylenebisacrylamide, N, N ′-(1,2-dihydroxyethylene) bisacrylamide, ethylenebisacrylate, and 4,4 ′. The liquid crystal aligning agent according to [11], which is at least one selected from the group of compounds consisting of methylene bis (N, N-dihydroxyethylene acrylate aniline).

[14] The epoxy compound is N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N '-Tetraglycidyl-4,4'-diaminodiphenylmethane, 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3-epoxy] Propoxy] phenyl)] ethyl] phenyl] propane, 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate, N-phenylmaleimide-glycidyl methacrylate copolymer, and 2- (3,4- The liquid crystal according to [11], which is at least one selected from the group of compounds consisting of (epoxycyclohexyl) ethyltrimethoxysilane. Mukozai.

[15] A liquid crystal alignment film formed by the liquid crystal aligning agent according to any one of [10] to [14].

[16] A liquid crystal alignment film for photoalignment obtained by irradiating polarized ultraviolet rays to a liquid crystal alignment film formed by the liquid crystal aligning agent according to any one of [10] to [14].

 [17] A step of applying the liquid crystal aligning agent according to any one of [10] to [14] to the substrate, a step of heating and drying the substrate coated with the aligning agent, and a step of irradiating the film with polarized ultraviolet rays. A liquid crystal alignment film for photo-alignment formed through the process.

[18] A step of applying the liquid crystal aligning agent according to any one of [10] to [14] to a substrate, a step of heating and drying the substrate coated with the aligning agent, and a step of irradiating the dried film with polarized ultraviolet rays. And a liquid crystal alignment film for photo-alignment formed through a step of heating and baking the film.

[19] A step of applying the liquid crystal aligning agent according to any one of [10] to [14] to the substrate, a step of heating and drying the substrate coated with the aligning agent, a step of heating and baking the dried film, Next, a liquid crystal alignment film for photoalignment formed through a step of irradiating the film with polarized ultraviolet rays.

[20] A liquid crystal display device having the liquid crystal alignment film according to any one of [15] to [19].

  If the aligning agent using the acid dianhydride of the present invention as a raw material is used, a rubbing alignment film or photo-alignment film excellent in alignment by rubbing or chemical change sensitivity by light irradiation and excellent in alignment of liquid crystal molecules Can be obtained. And the liquid crystal display element excellent in the display characteristic which has this alignment film can be obtained.

  Terms used in the present invention will be described. “Arbitrary” used in defining a chemical structural formula indicates that not only the position but also the number is arbitrary. In the chemical structural formula, a group in which a letter (for example, A) is surrounded by a hexagon means a group having a ring structure (ring A).

  The liquid crystal aligning agent of this invention contains the polyamic acid which is a reaction product of tetracarboxylic dianhydride and diamine, or its derivative (s). Examples of the diamine include non-side chain diamine, side chain diamine, photosensitive diamine, and hydrazide. The polyamic acid derivative is a component that dissolves in a solvent when the liquid crystal aligning agent described later contains a solvent. When the liquid crystal aligning agent is used as a liquid crystal aligning film described later, the main component is polyimide. It is a component that can form a liquid crystal alignment film. Examples of such polyamic acid derivatives include soluble polyimide, polyamic acid ester, polyhydrazide acid, polyamic acid amide, and polyhydrazide acid-amide acid, and more specifically, 1) all of polyamic acid Polyimide with amino and carboxyl dehydrating and ring-closing reaction, 2) Partial polyimide with partial dehydration and ring-closing reaction, 3) Polyamic acid ester in which carboxyl of polyamic acid is converted to ester, 4) Included in tetracarboxylic dianhydride compound A polyamic acid-polyamide copolymer obtained by replacing a part of the acid dianhydride with an organic dicarboxylic acid, and 5) a part or all of the polyamic acid-polyamide copolymer is subjected to a dehydration ring-closing reaction. And polyamide imide.

  If necessary, the alignment film formed from the liquid crystal aligning agent of the present invention may be provided with anisotropy by rubbing treatment or light irradiation.

  When anisotropy is imparted by light irradiation, the liquid crystal aligning agent of the present invention is applied to a substrate, dried by preheating, and then irradiated with ultraviolet linearly polarized light through a polarizing plate. Photopolymers derived from the photosensitive diamine in the polymer main chain that are substantially parallel cause photoisomerization. The polymer main chain that is substantially parallel to the polarization direction is selectively photoisomerized or photodimerized so that the polymer main chain forming the film is substantially perpendicular to the polarization direction of the irradiated ultraviolet light. The component in the direction becomes dominant. Therefore, after heating the substrate and dehydrating and cyclizing the polyamic acid to form a polyimide film, the liquid crystal molecules in the liquid crystal composition injected into the cell assembled using this substrate are in the polarization direction of the irradiated ultraviolet light. Orient with the major axis aligned in a perpendicular direction. The step of irradiating the film with ultraviolet linearly polarized light may be before the heating step for the formation of polyimide, or may be after the formation of polyimide by heating.

The tetracarboxylic dianhydride used for producing the polyamic acid or derivative thereof of the present invention will be described. In the following, the description of “tetracarboxylic dianhydride” represents not only the case where tetracarboxylic dianhydride is used alone, but also the case where a plurality of tetracarboxylic dianhydrides are used as a mixture. Yes. In the present invention, a tetracarboxylic dianhydride represented by the formula (1) is used. In the following description, the tetracarboxylic dianhydride represented by the formula (1) may be indicated by the acid dianhydride (1).

The following formulas (1-a) and (1-b) are examples that further embody the formula (1).

  As the acid dianhydride (1), one compound may be used alone, or two or more may be mixed and used. The acid dianhydride (1) may be used by mixing with other tetracarboxylic dianhydrides. In this case, the acid dianhydride (1) in the mixture of tetracarboxylic dianhydrides is used in a proportion of 10% by weight or more, preferably 30% by weight or more, and more preferably 50% by weight or more. .

  Other tetracarboxylic dianhydrides other than the acid dianhydride (1) can be selected from the known tetracarboxylic dianhydrides without limitation. Such tetracarboxylic dianhydrides are aromatic systems (including heteroaromatic ring systems) in which dicarboxylic dianhydrides are directly bonded to aromatic rings, and dicarboxylic dianhydrides are not directly bonded to aromatic rings. It may belong to any group of aliphatic (including heterocyclic).

式（ＡＮ−Ｉ）、（ＡＮ−ＩＶ）および（ＡＮ−Ｖ）において、Ｘは独立して単結合または−ＣＨ₂−であり、式（ＡＮ−ＩＩ）において、Ｇは単結合、炭素数１〜２０のアルキレン、−ＣＯ−、−Ｏ−、−Ｓ−、−ＳＯ₂−、−Ｃ（ＣＨ₃）₂−、または−Ｃ（ＣＦ₃）₂−であり、式（ＡＮ−ＩＩ）〜（ＡＮ−ＩＶ）において、Ｙは独立して下記の３価の基の群から選ばれる１つであり、結合手は任意の炭素に連結しており、この基の任意の水素はメチル、エチルまたはフェニルで置き換えられてもよく、

式（ＡＮ−ＩＩＩ）〜（ＡＮ−Ｖ）において、環Ａは炭素数３〜１０の単環式炭化水素の基または炭素数６〜３０の縮合多環式炭化水素の基であり、この基の任意の水素はメチル、エチルまたはフェニルで置き換えられていてもよく、環に掛かっている結合手は環を構成する任意の炭素に連結しており、２本の結合手が同一の炭素に連結してもよく、式（ＡＮ−ＶＩ）において、Ｘ¹⁰は炭素数２〜６のアルキレンであり、Ｍｅはメチルであり、そして、Ｐｈはフェニルであり、式（ＡＮ−ＶＩＩ）において、Ｇ¹⁰は独立して−Ｏ−、−ＣＯＯ−または−ＯＣＯ−であり、ｒは独立して０または１である。 Preferred examples of such tetracarboxylic dianhydrides include those represented by the formulas (AN-I) to (AN-VII) from the viewpoint of easy availability of raw materials, ease of polymer polymerization, and electrical characteristics of the film. The tetracarboxylic dianhydride represented is mentioned.

In the formulas (AN-I), (AN-IV), and (AN-V), X is independently a single bond or —CH ₂ —, and in the formula (AN-II), G is a single bond, carbon number 1 to 20 alkylene, —CO—, —O—, —S—, —SO ₂ —, —C (CH ₃ ) ₂ —, or —C (CF ₃ ) ₂ —, which has the formula (AN-II) In (AN-IV), Y is independently one selected from the group of the following trivalent groups, the bond is connected to any carbon, and any hydrogen in this group is methyl, May be replaced by ethyl or phenyl,

In the formulas (AN-III) to (AN-V), the ring A is a monocyclic hydrocarbon group having 3 to 10 carbon atoms or a condensed polycyclic hydrocarbon group having 6 to 30 carbon atoms. Any hydrogen in may be replaced by methyl, ethyl or phenyl, and the bond on the ring is connected to any carbon constituting the ring, and the two bonds are connected to the same carbon In formula (AN-VI), X ¹⁰ is alkylene having 2 to 6 carbon atoms, Me is methyl, and Ph is phenyl, and in formula (AN-VII), G ¹⁰ Is independently —O—, —COO— or —OCO—, and r is independently 0 or 1.

  More specifically, tetracarboxylic dianhydrides represented by the following formulas (AN-1) to (AN-16-14) may be mentioned.

式（ＡＮ−１）において、Ｇ¹¹は単結合、炭素数１〜１２のアルキレン、１，４−フェニレン、または１，４−シクロヘキシレンである。Ｘ¹¹は独立して単結合または−ＣＨ₂−である。Ｇ¹²は独立してＣＨまたはＮである。Ｇ¹²がＣＨであるとき、ＣＨの水素は−ＣＨ₃に置き換えられてもよい。Ｇ¹²がＮであるとき、Ｇ¹¹が単結合および−ＣＨ₂−であることはなく、Ｘ¹¹は単結合であることはない。そしてＲ¹¹は−Ｈまたは−ＣＨ₃である。式（ＡＮ−１）で表されるテトラカルボン酸二無水物の例としては、下記の式で表される化合物を挙げることができる。

式（ＡＮ−１−２）および（ＡＮ−１−１４）において、ｍは1〜１２の整数である。

In the formula (AN-1), G ¹¹ is a single bond, alkylene having 1 to 12 carbons, 1,4-phenylene, or 1,4-cyclohexylene. X ¹¹ is independently a single bond or —CH ₂ —. G ¹² is independently CH or N. When G ¹² is CH, the hydrogen of CH may be replaced with —CH ₃ . When G ¹² is N, G ¹¹ is not a single bond or —CH ₂ —, and X ¹¹ is not a single bond. R ¹¹ is —H or —CH ₃ . Examples of the tetracarboxylic dianhydride represented by the formula (AN-1) include compounds represented by the following formula.

In the formulas (AN-1-2) and (AN-1-14), m is an integer of 1 to 12.

式（ＡＮ−２）において、Ｒ¹²は独立して−Ｈ、−ＣＨ₃、−ＣＨ₂ＣＨ₃、またはフェニルである。式（ＡＮ−２）で表されるテトラカルボン酸二無水物の例としては、下記の式で表される化合物を挙げることができる。

In the formula (AN-2), R ¹² is independently —H, —CH ₃ , —CH ₂ CH ₃ , or phenyl. Examples of the tetracarboxylic dianhydride represented by the formula (AN-2) include compounds represented by the following formula.

式（ＡＮ−３）において、環Ａ¹¹はシクロヘキサン環もしくはベンゼン環である。式（ＡＮ−３）で表されるテトラカルボン酸二無水物の例としては、下記の式で表される化合物を挙げることができる。

In the formula (AN-3), the ring A ¹¹ is a cyclohexane ring or a benzene ring. Examples of the tetracarboxylic dianhydride represented by the formula (AN-3) include compounds represented by the following formula.

式（ＡＮ−４）において、Ｇ¹³は単結合、−ＣＨ₂−、−ＣＨ₂ＣＨ₂−、−Ｏ−、−Ｓ−、−Ｃ（ＣＨ₃）₂−、−ＳＯ₂−、−ＣＯ−または−Ｃ（ＣＦ₃）₂−である。環Ａ¹¹はそれぞれ独立してシクロヘキサン環またはベンゼン環である。Ｇ¹³は環Ａ¹¹の任意の位置に結合してよい。式（ＡＮ−４）で表されるテトラカルボン酸二無水物の例としては、下記の式で表される化合物を挙げることができる。

式（ＡＮ−４−１７）において、ｍは１〜１２の整数である。

In the formula (AN-4), G ¹³ represents a single _{bond, -CH 2 -, - CH 2} CH 2 -, - O -, - S -, - C (CH 3) 2 -, - SO 2 -, - CO - or -C (CF _{3) 2} - a. Each ring A ¹¹ is independently a cyclohexane ring or a benzene ring. G ¹³ may be bonded to any position of ring A ¹¹ . Examples of the tetracarboxylic dianhydride represented by the formula (AN-4) include compounds represented by the following formula.

In formula (AN-4-17), m is an integer of 1-12.

式（ＡＮ−５）において、Ｒ¹¹は−Ｈ、または−ＣＨ₃である。ベンゼン環を構成する炭素原子に結合位置が固定されていないＲ¹¹は、ベンゼン環における結合位置が任意であることを示す。式（ＡＮ−５）で表されるテトラカルボン酸二無水物の例としては、下記の式で表される化合物を挙げることができる。

In the formula (AN-5), R ¹¹ is —H or —CH ₃ . R ¹¹ whose bond position is not fixed to the carbon atom constituting the benzene ring indicates that the bond position in the benzene ring is arbitrary. Examples of the tetracarboxylic dianhydride represented by the formula (AN-5) include compounds represented by the following formula.

式（ＡＮ−６）において、Ｘ¹¹は独立して単結合または−ＣＨ₂−である。Ｘ¹²は−ＣＨ₂−、−ＣＨ₂ＣＨ₂−または−ＣＨ＝ＣＨ−である。ｎは１または２である。式（ＡＮ−６）で表されるテトラカルボン酸二無水物の例としては、下記の式で表される化合物を挙げることができる。

In the formula (AN-6), X ¹¹ is independently a single bond or —CH ₂ —. X ¹² is _{-CH 2 -, - CH 2 CH} 2 - or -CH = CH-. n is 1 or 2. Examples of the tetracarboxylic dianhydride represented by the formula (AN-6) include compounds represented by the following formula.

式（ＡＮ−７）において、Ｘ¹¹は単結合または−ＣＨ₂−である。式（ＡＮ−７）で表されるテトラカルボン酸二無水物の例としては、下記の式で表される化合物を挙げることができる。

In the formula (AN-7), X ¹¹ is a single bond or —CH ₂ —. Examples of the tetracarboxylic dianhydride represented by the formula (AN-7) include compounds represented by the following formula.

式（ＡＮ−８）において、Ｘ¹¹は単結合または−ＣＨ₂−である。Ｒ¹²は−Ｈ、−ＣＨ₃、−ＣＨ₂ＣＨ₃、またはフェニルであり、環Ａ¹²はシクロヘキサン環もしくはシクロヘキセン環である。式（ＡＮ−８）で表されるテトラカルボン酸二無水物の例としては、下記の式で表される化合物を挙げることができる。

In the formula (AN-8), X ¹¹ is a single bond or —CH ₂ —. R ¹² is —H, —CH ₃ , —CH ₂ CH ₃ , or phenyl, and ring A ¹² is a cyclohexane ring or a cyclohexene ring. Examples of the tetracarboxylic dianhydride represented by the formula (AN-8) include compounds represented by the following formula.

式（ＡＮ−９）において、ｒはそれぞれ独立して０または１である。式（ＡＮ−９）で表されるテトラカルボン酸二無水物の例としては、下記の式で表される化合物を挙げることができる。

In the formula (AN-9), each r is independently 0 or 1. Examples of the tetracarboxylic dianhydride represented by the formula (AN-9) include compounds represented by the following formula.

Formula (AN-10) is the following tetracarboxylic dianhydride.

式（ＡＮ−１１）において、環Ａ¹¹は独立してシクロヘキサン環またはベンゼン環である。式（ＡＮ−１１）で表されるテトラカルボン酸二無水物の例としては、下記の式で表される化合物を挙げることができる。

In formula (AN-11), ring A ¹¹ is independently a cyclohexane ring or a benzene ring. Examples of the tetracarboxylic dianhydride represented by the formula (AN-11) include compounds represented by the following formula.

式（ＡＮ−１２）において、環Ａ¹¹はそれぞれ独立してシクロヘキサン環またはベンゼン環である。式（ＡＮ−１２）で表されるテトラカルボン酸二無水物の例としては、下記の式で表される化合物を挙げることができる。

In formula (AN-12), each ring A ¹¹ is independently a cyclohexane ring or a benzene ring. As an example of the tetracarboxylic dianhydride represented by a formula (AN-12), the compound represented by a following formula can be mentioned.

式（ＡＮ−１３）において、Ｘ¹³は炭素数２〜６のアルキレンである。式（ＡＮ−１３）で表されるテトラカルボン酸二無水物の例としては、下記の式で表される化合物を挙げることができる。

In the formula (AN-13), X ¹³ is alkylene having 2 to 6 carbons. Examples of the tetracarboxylic dianhydride represented by the formula (AN-13) include compounds represented by the following formula.

式（ＡＮ−１４）において、Ｇ¹⁴は独立して−Ｏ−、−ＣＯＯ−または−ＯＣＯ−であり、ｒは独立して０または１である。式（ＡＮ−１４）で表されるテトラカルボン酸二無水物の例としては、下記の式で表される化合物を挙げることができる。

In the formula (AN-14), G ¹⁴ is independently —O—, —COO— or —OCO—, and r is independently 0 or 1. Examples of the tetracarboxylic dianhydride represented by the formula (AN-14) include compounds represented by the following formula.

式（ＡＮ−１５）において、ｗは１〜１０の整数である。式（ＡＮ−１５）で表されるテトラカルボン酸二無水物の例としては、下記の式で表される化合物を挙げることができる。

In formula (AN-15), w is an integer of 1-10. Examples of the tetracarboxylic dianhydride represented by the formula (AN-15) include compounds represented by the following formula.

Examples of tetracarboxylic dianhydrides other than the above include the following compounds.

  When importance is attached to improving the orientation of the liquid crystal display element, among the above acid dianhydrides, the formulas (AN-1-1), (AN-2-1), (AN-3-1) , (AN-3-2), (AN-4-5), (AN-4-17), (AN-4-21), (AN-7-2), (AN-10), and (AN The compound represented by -11-3) is particularly preferable.

  When importance is attached to improving the transmittance of the liquid crystal display element, among the above acid dianhydrides, the formulas (AN-1-1), (AN-1-13), (AN-2-1) , (AN-3-1), (AN-7-2) and (AN-10) are particularly preferred.

  The diamine used for producing the polyamic acid or derivative thereof of the present invention will be described. The diamine component of this invention can be selected without being restrict | limited from the well-known diamine used in order to manufacture polyamic acid or its derivative (s). The diamines may be used alone or in combination as a mixture.

  Diamine compounds can be divided into two types according to their structures. That is, when a skeleton connecting two amino groups is viewed as a main chain, a group branched from the main chain, that is, a diamine having a side chain group and a diamine having no side chain group. This side chain group is a group having an effect of increasing the pretilt angle. The side chain group having such an effect needs to be a group having 3 or more carbon atoms. Specific examples include alkyl having 3 or more carbon atoms, alkoxy having 3 or more carbon atoms, alkoxyalkyl having 3 or more carbon atoms, and A group having a steroid skeleton can be exemplified. A group having one or more rings, wherein the terminal ring has any one of alkyl having 1 or more carbon atoms, alkoxy having 1 or more carbon atoms and alkoxyalkyl having 2 or more carbon atoms as a substituent; It has an effect as a side chain group. In the following description, a diamine having such a side chain group may be referred to as a side chain diamine. Such a diamine having no side chain group may be referred to as a non-side chain diamine.

  By properly using the non-side chain diamine and the side chain diamine, it is possible to cope with the pretilt angle required for each. The side chain diamine is preferably used in combination so as not to impair the properties of the present invention. The side chain diamine and the non-side chain diamine are preferably selected and used for the purpose of improving the vertical alignment with respect to the liquid crystal, the voltage holding ratio, the image sticking property, and the alignment.

上記の式（ＤＩ−１）において、ｍは１〜１２の整数であり、アルキレンの任意の水素は−ＯＨに置き換えられてもよい。（ＤＩ−３）および（ＤＩ−５）〜（ＤＩ−７）において、Ｇ²¹は独立して単結合、−ＮＨ−、−Ｏ−、−Ｓ−、−Ｓ−Ｓ−、−ＳＯ₂−、−ＣＯ−、−ＣＯＮＨ−、−ＣＯＮＣＨ₃−、−ＮＨＣＯ−、−Ｃ（ＣＨ₃）₂−、−Ｃ（ＣＦ₃）₂−、−（ＣＨ₂）_m'−、−Ｏ−（ＣＨ₂）_m'−Ｏ−、−Ｎ（ＣＨ₃）−（ＣＨ₂）_k−Ｎ（ＣＨ₃）−、または−Ｓ−（ＣＨ₂）_m'−Ｓ−であり、ｍ’は独立して１〜１２の整数であり、ｋは１〜５の整数である。（ＤＩ−６）および（ＤＩ−７）において、Ｇ²²は独立して単結合、−Ｏ−、−Ｓ−、−ＣＯ−、−Ｃ（ＣＨ₃）₂−、−Ｃ（ＣＦ₃）₂−、または炭素数１〜１０のアルキレンである。式（ＤＩ−２）〜（ＤＩ−７）中のシクロヘキサン環およびベンゼン環の任意の−Ｈは、−Ｆ、−ＣＨ₃、−ＯＨ、−ＣＦ₃、−ＣＯ₂Ｈ、−ＣＯＮＨ₂、またはベンジルで置き換えられてもよく、加えて式（ＤＩ−４）においては、下記式（ＤＩ−４−ａ）〜（ＤＩ−４−ｃ）で置き換えられていてもよい。環を構成する炭素原子に結合位置が固定されていない基は、その環における結合位置が任意であることを示す。そして、シクロヘキサン環またはベンゼン環への−ＮＨ₂の結合位置は、Ｇ²¹またはＧ²²の結合位置を除く任意の位置である。

式（ＤＩ−４−ａ）および（ＤＩ−４−ｂ）において、Ｒ²⁰は独立して−Ｈまたは−ＣＨ₃である。
The non-side chain diamine will be described. Examples of diamines having no known side chain include diamines of the following formulas (DI-1) to (DI-12).

In the above formula (DI-1), m is an integer of 1 to 12, and any hydrogen of alkylene may be replaced with -OH. In (DI-3) and (DI-5) to (DI-7), G ²¹ is independently a single bond, —NH—, —O—, —S—, —S—S—, —SO ₂ —. , —CO—, —CONH—, —CONCH ₃ —, —NHCO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, — (CH ₂ ) _{m ′} —, —O— (CH _{2) m '-O -, -} N (CH 3) - (CH 2) k -N (CH 3) -, or -S- (CH _{2) m'} is -S-, m 'is independently It is an integer of 1-12, k is an integer of 1-5. In (DI-6) and (DI-7), G ²² is independently a single bond, —O—, —S—, —CO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) _2. -Or alkylene having 1 to 10 carbon atoms. In the formulas (DI-2) to (DI-7), any —H of the cyclohexane ring and the benzene ring is —F, —CH ₃ , —OH, —CF ₃ , —CO ₂ H, —CONH ₂ , or In the formula (DI-4), they may be replaced by the following formulas (DI-4-a) to (DI-4-c). A group in which the bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary. The bonding position of —NH ₂ to the cyclohexane ring or benzene ring is an arbitrary position excluding the bonding position of G ²¹ or G ²² .

In the formulas (DI-4-a) and (DI-4-b), R ²⁰ is independently —H or —CH ₃ .

式（ＤＩ−８）において、Ｒ²¹およびＲ²²は独立して炭素数１〜３のアルキルまたはフェニルであり、Ｇ²³は独立して炭素数１〜６のアルキレン、フェニレンまたはアルキル置換されたフェニレンであり、ｗは１〜１０の整数である。
式（ＤＩ−９）において、Ｒ²³は独立して炭素数１〜５のアルキル、炭素数１〜５のアルコキシまたは−Ｃｌであり、ｐは独立して０〜３の整数であり、ｑは０〜４の整数である。
式（ＤＩ−１０）において、Ｒ²⁴は−Ｈ、炭素数１〜４のアルキル、フェニル、またはベンジルである。
式（ＤＩ−１１）において、Ｇ²⁴は−ＣＨ₂−または−ＮＨ−である。
式（ＤＩ−１２）において、Ｇ²⁵は単結合、炭素数２〜６のアルキレンまたは１，４−フェニレンであり、ｒは０または１である。そして、環を構成する炭素原子に結合位置が固定されていない基は、その環における結合位置が任意であることを示す。
式（ＤＩ−９）、式（ＤＩ−１１）および式（ＤＩ−１２）において、ベンゼン環に結合する−ＮＨ₂の結合位置は、任意の位置である。

In formula (DI-8), R ²¹ and R ²² are independently alkyl or phenyl having 1 to 3 carbon atoms, and G ²³ is independently alkylene, phenylene or alkyl-substituted phenylene having 1 to 6 carbon atoms. And w is an integer of 1-10.
In the formula (DI-9), R ²³ is independently alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons or —Cl, p is independently an integer of 0 to 3, and q is It is an integer of 0-4.
In the formula (DI-10), R ²⁴ is —H, alkyl having 1 to 4 carbons, phenyl, or benzyl.
In the formula (DI-11), G ²⁴ is —CH ₂ — or —NH—.
In the formula (DI-12), G ²⁵ is a single bond, alkylene having 2 to 6 carbon atoms or 1,4-phenylene, and r is 0 or 1. A group whose bond position is not fixed to the carbon atoms constituting the ring indicates that the bond position in the ring is arbitrary.
Formula (DI-9), in formula (DI-11) and formula (DI-12), the bonding position of -NH ₂ bonded to the benzene ring is any position.

  Specific examples of the following formulas (DI-1-1) to (DI-12-1) can be given as diamines having no side chain of the above formulas (DI-1) to (DI-12).

Examples of diamines represented by formulas (DI-1) to (DI-3) are shown below.

Examples of the diamine represented by the formula (DI-4) are shown below.

式（ＤＩ−５−１）において、ｍは１〜１２の整数である。

式（ＤＩ−５−１２）および式（ＤＩ−５−１３）において、ｍは１〜１２の整数である。

式（ＤＩ−５−１６）において、ｖは１〜６の整数である。

式（ＤＩ−５−３０）において、ｋは１〜５の整数である。 Examples of the diamine represented by the formula (DI-5) are shown below.

In formula (DI-5-1), m is an integer of 1-12.

In Formula (DI-5-12) and Formula (DI-5-13), m is an integer of 1-12.

In the formula (DI-5-16), v is an integer of 1 to 6.

In the formula (DI-5-30), k is an integer of 1 to 5.

Examples of the diamine represented by the formula (DI-6) are shown below.

式（ＤＩ−７−３）および（ＤＩ−７−４）において、ｍは１〜１２の整数であり、ｎは独立して１または２である。

Examples of the diamine represented by the formula (DI-7) are shown below.

In formulas (DI-7-3) and (DI-7-4), m is an integer of 1 to 12, and n is independently 1 or 2.

Examples of the diamine represented by the formula (DI-8) are shown below.

Examples of the diamine represented by the formula (DI-9) are shown below.

Examples of the diamine represented by the formula (DI-10) are shown below.

Examples of the diamine represented by the formula (DI-11) are shown below.

Examples of the diamine represented by the formula (DI-12) are shown below.

  Such a non-side chain diamine has an effect of improving electrical characteristics, such as reducing the ion density of the liquid crystal display element. When a non-side chain diamine is used as the diamine used for producing the polyamic acid or polyimide used in the liquid crystal aligning agent of the present invention, the proportion of the total amount of the diamine is preferably 0 to 95 mol%. It is more preferable to set it to -90 mol%.

  The side chain type diamine will be described. Examples of the side chain group of the side chain type diamine include the following groups.

  As a side group, first, alkyl, alkyloxy, alkyloxyalkyl, alkylcarbonyl, alkylcarbonyloxy, alkyloxycarbonyl, alkylaminocarbonyl, alkenyl, alkenyloxy, alkenylcarbonyl, alkenylcarbonyloxy, alkenyloxycarbonyl, alkenylaminocarbonyl, Alkynyl, alkynyloxy, alkynylcarbonyl, alkynylcarbonyloxy, alkynyloxycarbonyl, alkynylaminocarbonyl and the like can be mentioned. Alkyl, alkenyl and alkynyl in these groups are all groups having 3 or more carbon atoms. However, in alkyloxyalkyl, it is sufficient if the entire group has 3 or more carbon atoms. These groups may be linear or branched.

  Next, phenyl, phenylalkyl, phenylalkyloxy, phenyloxy, provided that the terminal ring has alkyl having 1 or more carbon atoms, alkoxy having 1 or more carbon atoms or alkoxyalkyl having 2 or more carbon atoms as a substituent. Phenylcarbonyl, phenylcarbonyloxy, phenyloxycarbonyl, phenylaminocarbonyl, phenylcyclohexyloxy, cycloalkyl having 3 or more carbon atoms, cyclohexylalkyl, cyclohexyloxy, cyclohexyloxycarbonyl, cyclohexylphenyl, cyclohexylphenylalkyl, cyclohexylphenyloxy, bis ( Cyclohexyl) oxy, bis (cyclohexyl) alkyl, bis (cyclohexyl) phenyl, bis (cyclohexyl) phenylalkyl, bis ( Kurohekishiru) oxycarbonyl, and bis (cyclohexyl) phenyloxycarbonyl and cyclohexyl bis (phenyl) group of a ring structure, such as oxycarbonyl,.

  Further, a group having two or more benzene rings, a group having two or more cyclohexane rings, or two or more groups composed of a benzene ring and a cyclohexane ring, wherein the bonding groups are independently a single bond, -O-, -COO-, -OCO-, -CONH-, or alkylene having 1 to 3 carbon atoms, the terminal ring is alkyl having 1 or more carbon atoms as a substituent, fluorine-substituted alkyl having 1 or more carbon atoms, carbon A ring assembly group having an alkoxy of several or more or an alkoxyalkyl having two or more carbons can be given. A group having a steroid skeleton is also effective as a side chain group.

式（ＤＩ−１３）において、Ｇ²⁶は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−、−ＣＯＮＨ−、−ＣＨ₂Ｏ−、−ＯＣＨ₂−、−ＣＦ₂Ｏ−、−ＯＣＦ₂−、または−（ＣＨ₂）_m'−であり、ｍ’は１〜１２の整数である。Ｇ²⁶の好ましい例は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ₂Ｏ−、および炭素数１〜３のアルキレンであり、特に好ましい例は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ₂Ｏ−、−ＣＨ₂−および−ＣＨ₂ＣＨ₂−である。Ｒ²⁵は炭素数３〜３０のアルキル、フェニル、ステロイド骨格を有する基、または下記の式（ＤＩ−１３−ａ）で表される基である。このアルキルにおいて、任意の−Ｈは−Ｆで置き換えられてもよく、そして任意の−ＣＨ₂−は−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられていてもよい。このフェニルの−Ｈは、−Ｆ、−ＣＨ₃、−ＯＣＨ₃、−ＯＣＨ₂Ｆ、−ＯＣＨＦ₂、−ＯＣＦ₃、炭素数３〜３０のアルキルまたは炭素数３〜３０のアルコキシで置き換えられていてもよく、このシクロヘキシルの−Ｈは炭素数３〜３０のアルキルまたは炭素数３〜３０のアルコキシで置き換えられていてもよい。ベンゼン環に結合する−ＮＨ₂の結合位置はその環において任意の位置であることを示すが、その結合位置はメタまたはパラであることが好ましい。即ち、基「Ｒ²⁵−Ｇ²⁶−」の結合位置を１位としたとき、２つの結合位置は３位と５位、または２位と５位であることが好ましい。

式（ＤＩ−１３−ａ）において、Ｇ²⁷、Ｇ²⁸およびＧ²⁹は結合基であり、これらは独立して単結合、または炭素数１〜１２のアルキレンであり、このアルキレンの１以上の−ＣＨ₂−は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＣＨ＝ＣＨ−で置き換えられていてもよい。環Ｂ²¹、環Ｂ²²、環Ｂ²³および環Ｂ²⁴は独立して１，４−フェニレン、１，４−シクロへキシレン、１，３−ジオキサン−２，５−ジイル、ピリミジン−２，５−ジイル、ピリジン−２，５−ジイル、ナフタレン−１，５−ジイル、ナフタレン−２，７−ジイルまたはアントラセン−９，１０−ジイルであり、環Ｂ²¹、環Ｂ²²、環Ｂ²³および環Ｂ²⁴において、任意の−Ｈは−Ｆまたは−ＣＨ₃で置き換えられてもよく、ｓ、ｔおよびｕは独立して０〜２の整数であって、これらの合計は１〜５であり、ｓ、ｔまたはｕが２であるとき、各々の括弧内の２つの結合基は同じであっても異なってもよく、そして、２つの環は同じであっても異なっていてもよい。Ｒ²⁶は−Ｆ、−ＯＨ、炭素数１〜３０のアルキル、炭素数１〜３０のフッ素置換アルキル、炭素数１〜３０のアルコキシ、−ＣＮ、−ＯＣＨ₂Ｆ、−ＯＣＨＦ₂、または−ＯＣＦ₃であり、この炭素数１〜３０のアルキルの任意の−ＣＨ₂−は下記式（ＤＩ−１３−ｂ）で表される２価の基で置き換えられていてもよい。

式（ＤＩ−１３−ｂ）において、Ｒ²⁷およびＲ²⁸は独立して炭素数１〜３のアルキルであり、ｖは１〜６の整数である。Ｒ²⁶の好ましい例は炭素数１〜３０のアルキルおよび炭素数１〜３０のアルコキシである。 Examples of the diamine having a side chain include compounds represented by the following formulas (DI-13) to (DI-17).

In the formula (DI-13), G ²⁶ represents a single bond, —O—, —COO—, —OCO—, —CO—, —CONH—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—. , -OCF ₂ -, or - (CH _{2) m '-} it is and, m' is an integer from 1 to 12. Preferred examples of G ²⁶ are a single bond, —O—, —COO—, —OCO—, —CH ₂ O—, and alkylene having 1 to 3 carbon atoms, and particularly preferred examples are a single bond, —O—, — COO -, - OCO -, - CH 2 O -, - CH 2 - and -CH ₂ CH ₂ -. R ²⁵ is an alkyl group having 3 to 30 carbon atoms, phenyl, a group having a steroid skeleton, or a group represented by the following formula (DI-13-a). In this alkyl, any —H may be replaced with —F, and any —CH ₂ — may be replaced with —O—, —CH═CH— or —C≡C—. -H in which _{phenyl, -F, -CH 3, -OCH 3} , -OCH 2 F, -OCHF 2, -OCF 3, has been replaced by an alkoxy alkyl or 3 to 30 carbon atoms having 3 to 30 carbon atoms In this cyclohexyl group, —H may be substituted with alkyl having 3 to 30 carbon atoms or alkoxy having 3 to 30 carbon atoms. Although the bonding position of —NH ₂ bonded to the benzene ring indicates an arbitrary position in the ring, the bonding position is preferably meta or para. That is, when the bonding position of the group “R ²⁵ -G ²⁶ —” is the first position, the two bonding positions are preferably the third position and the fifth position, or the second position and the fifth position.

In the formula (DI-13-a), G ²⁷ , G ²⁸ and G ²⁹ are bonding groups, and these are each independently a single bond or alkylene having 1 to 12 carbons, and one or more — CH ₂ — may be replaced by —O—, —COO—, —OCO—, —CONH—, —CH═CH—. Ring B ²¹ , Ring B ²² , Ring B ²³ and Ring B ²⁴ are each independently 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5 - diyl, pyridine-2,5-diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl or anthracene-9,10-diyl, ring B ^21, ring B ^22, ring B ²³ and ring In B ²⁴ , any —H may be replaced by —F or —CH ₃ , s, t and u are each independently an integer of 0 to 2, and their sum is 1 to 5, When s, t or u is 2, the two linking groups in each parenthesis may be the same or different, and the two rings may be the same or different. R ²⁶ represents —F, —OH, alkyl having 1 to 30 carbon atoms, fluorine-substituted alkyl having 1 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms, —CN, —OCH ₂ F, —OCHF ₂ , or —OCF. _And any —CH ₂ — in the alkyl having 1 to 30 carbon atoms may be replaced by a divalent group represented by the following formula (DI-13-b).

In the formula (DI-13-b), R ²⁷ and R ²⁸ are independently alkyl having 1 to 3 carbon atoms, and v is an integer of 1 to 6. Preferred examples of R ²⁶ are alkyl having 1 to 30 carbons and alkoxy having 1 to 30 carbons.

式（ＤＩ−１４）および式（ＤＩ−１５）において、Ｇ³⁰は独立して単結合、−ＣＯ−または−ＣＨ₂−であり、Ｒ²⁹は独立して−Ｈまたは−ＣＨ₃であり、Ｒ³⁰は−Ｈ、炭素数１〜２０のアルキル、または炭素数２〜２０のアルケニルである。式（ＤＩ−１５）におけるベンゼン環の１つの−Ｈは、炭素数１〜２０のアルキルまたはフェニルで置き換えられてもよい。そして、環を構成するいずれかの炭素原子に結合位置が固定されていない基は、その環における結合位置が任意であることを示す。式（ＤＩ−１４）における２つの基「−フェニレン−Ｇ³⁰−Ｏ−」の一方はステロイド核の３位に結合し、もう一方はステロイド核の６位に結合していることが好ましい。式（ＤＩ−１５）における２つの基「−フェニレン−Ｇ³⁰−Ｏ−」のベンゼン環への結合位置は、ステロイド核の結合位置に対して、それぞれメタ位またはパラ位であることが好ましい。式（ＤＩ−１４）および式（ＤＩ−１５）において、ベンゼン環に結合する−ＮＨ₂はその環における結合位置が任意であることを示す。

In the formula (DI-14) and the formula (DI-15), G ³⁰ is independently a single bond, —CO— or —CH ₂ —, R ²⁹ is independently —H or —CH ₃ , R ³⁰ is —H, alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons. One -H of the benzene ring in formula (DI-15) may be replaced with alkyl having 1 to 20 carbons or phenyl. A group whose bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary. One of the two groups “-phenylene-G ³⁰ —O—” in formula (DI-14) is preferably bonded to the 3-position of the steroid nucleus and the other is bonded to the 6-position of the steroid nucleus. The bonding position of the two groups “-phenylene-G ³⁰ —O—” in the formula (DI-15) to the benzene ring is preferably a meta position or a para position, respectively, with respect to the bonding position of the steroid nucleus. In formula (DI-14) and formula (DI-15), —NH ₂ bonded to the benzene ring indicates that the bonding position in the ring is arbitrary.

式（ＤＩ−１６）および式（ＤＩ−１７）において、Ｇ³¹は独立して−Ｏ−または炭素数１〜６のアルキレンであり、Ｇ³²は単結合または炭素数１〜３のアルキレンである。Ｒ³¹は−Ｈまたは炭素数１〜２０のアルキルであり、このアルキルの任意の−ＣＨ₂−は、−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよい。Ｒ³²は炭素数６〜２２のアルキルであり、Ｒ³³は−Ｈまたは炭素数１〜２２のアルキルである。環Ｂ²⁵は１，４−フェニレンまたは１，４−シクロヘキシレンであり、ｒは０または１である。そしてベンゼン環に結合する−ＮＨ₂はその環における結合位置が任意であることを示すが、独立してＧ³¹の結合位置に対してメタ位またはパラ位であることが好ましい。

In the formula (DI-16) and the formula (DI-17), G ³¹ is independently —O— or alkylene having 1 to 6 carbons, and G ³² is a single bond or alkylene having 1 to 3 carbons. . R ³¹ is —H or alkyl having 1 to 20 carbons, and arbitrary —CH ₂ — of this alkyl may be replaced by —O—, —CH═CH— or —C≡C—. R ³² is alkyl having 6 to 22 carbon atoms, and R ³³ is —H or alkyl having 1 to 22 carbon atoms. Ring B ²⁵ is 1,4-phenylene or 1,4-cyclohexylene, and r is 0 or 1. In addition, —NH ₂ bonded to the benzene ring indicates that the bonding position in the ring is arbitrary, but it is preferably independently a meta position or a para position with respect to the bonding position of G ³¹ .

  Specific examples of the side chain diamine are illustrated below. Examples of the diamine compound having a side chain of the above formulas (DI-13) to (DI-17) include compounds represented by the following formulas (DI-13-1) to (DI-17-3). .

式（ＤＩ−１３−１）〜（ＤＩ−１３−１１）において、Ｒ³⁴は炭素数１〜３０のアルキルまたは炭素数１〜３０のアルコキシであり、好ましくは炭素数５〜２５のアルキルまたは炭素数５〜２５のアルコキシである。Ｒ³⁵は炭素数１〜３０のアルキルまたは炭素数１〜３０のアルコキシであり、好ましくは炭素数３〜２５のアルキルまたは炭素数３〜２５のアルコキシである。 Examples of the compound represented by the formula (DI-13) are shown below.

In the formulas (DI-13-1) to (DI-13-11), R ³⁴ is alkyl having 1 to 30 carbons or alkoxy having 1 to 30 carbons, preferably alkyl or carbon having 5 to 25 carbons. It is alkoxy of several 5-25. R ³⁵ is alkyl having 1 to 30 carbons or alkoxy having 1 to 30 carbons, preferably alkyl having 3 to 25 carbons or alkoxy having 3 to 25 carbons.

式（ＤＩ−１３−１２）〜（ＤＩ−１３−１７）において、Ｒ³⁶は炭素数４〜３０のアルキルであり、好ましくは炭素数６〜２５のアルキルである。Ｒ³⁷は炭素数６〜３０のアルキルであり、好ましくは炭素数８〜２５のアルキルである。

In formula (DI-13-12) ~ (DI -13-17), R 36 is alkyl of 4 to 30 carbon atoms, preferably an alkyl having 6 to 25 carbon atoms. R ³⁷ is alkyl having 6 to 30 carbons, preferably alkyl having 8 to 25 carbons.

式（ＤＩ−１３−１８）〜（ＤＩ−１３−４３）において、Ｒ³⁸は炭素数１〜２０のアルキルまたは炭素数１〜２０のアルコキシであり、好ましくは炭素数３〜２０のアルキルまたは炭素数３〜２０のアルコキシである。Ｒ³⁹は−Ｈ、−Ｆ、炭素数１〜３０のアルキル、炭素数１〜３０のアルコキシ、−ＣＮ、−ＯＣＨ₂Ｆ、−ＯＣＨＦ₂または−ＯＣＦ₃であり、好ましくは炭素数３〜２５のアルキル、または炭素数３〜２５のアルコキシである。そしてＧ³³は炭素数１〜２０のアルキレンである。

In the formulas (DI-13-18) to (DI-13-43), R ³⁸ is alkyl having 1 to 20 carbons or alkoxy having 1 to 20 carbons, preferably alkyl or carbon having 3 to 20 carbons. It is alkoxy of several 3-20. R ³⁹ is —H, —F, alkyl having 1 to 30 carbons, alkoxy having 1 to 30 carbons, —CN, —OCH ₂ F, —OCHF ₂ or —OCF ₃ , preferably ₃ to 25 carbons. Or alkyl having 3 to 25 carbon atoms. G ³³ is alkylene having 1 to 20 carbon atoms.

Examples of the compound represented by the formula (DI-14) are shown below.

Examples of the compound represented by the formula (DI-15) are shown below.

式（ＤＩ−１６−１）〜（ＤＩ−１６−１２）において、Ｒ⁴⁰は−Ｈまたは炭素数１〜２０のアルキル、好ましくは−Ｈまたは炭素数１〜１０のアルキルであり、そしてＲ⁴¹は−Ｈまたは炭素数１〜１２のアルキルである。 Examples of the compound represented by the formula (DI-16) are shown below.

In the formulas (DI-16-1) to (DI-16-12), R ⁴⁰ is —H or alkyl having 1 to 20 carbons, preferably —H or alkyl having 1 to 10 carbons, and R ⁴¹ Is —H or alkyl having 1 to 12 carbons.

式（ＤＩ−１７−１）〜（ＤＩ−１７−３）において、Ｒ³⁷は炭素数６〜３０のアルキルであり、Ｒ⁴¹は−Ｈまたは炭素数１〜１２のアルキルである。 Examples of the compound represented by the formula (DI-17) are shown below.

In formula (DI-17-1) ~ (DI -17-3), R 37 is alkyl of 6 to 30 carbon atoms, R ⁴¹ is -H or alkyl having 1 to 12 carbon atoms.

式（ＤＩ−１８−１）〜（ＤＩ−１８−８）中、Ｒ⁴²はそれぞれ独立して炭素数３〜３０のアルキル基を表す。

式（ＤＩ−１８−９）〜（ＤＩ−１８−１１）において、ｅは２〜１０の整数であり、式（ＤＩ−１８−１２）中、Ｒ⁴³はそれぞれ独立して−Ｈ、−ＮＨＢｏｃまたは−Ｎ（Ｂｏｃ）₂であり、Ｒ⁴³の少なくとも１つは−ＮＨＢｏｃまたは−Ｎ（Ｂｏｃ）₂であり、式（ＤＩ−１８−１３）において、Ｒ⁴⁴は−ＮＨＢｏｃまたは−Ｎ（Ｂｏｃ）₂であり、そして、ｍは１〜１２の整数である。ここでＢｏｃはｔ−ブトキシカルボニル基である。 As other diamines, for example, compounds represented by the following formulas (DI-18-1) to (DI-18-13) can be used.

In formulas (DI-18-1) to (DI-18-8), R ⁴² each independently represents an alkyl group having 3 to 30 carbon atoms.

In the formulas (DI-18-9) to (DI-18-11), e is an integer of 2 to 10, and in the formula (DI-18-12), each R ⁴³ independently represents —H, —NHBoc. Or —N (Boc) ₂ , at least one of R ⁴³ is —NHBoc or —N (Boc) ₂ , and in formula (DI-18-13), R ⁴⁴ is —NHBoc or —N (Boc) ₂ and m is an integer from 1 to 12. Here, Boc is a t-butoxycarbonyl group.

  When the liquid crystal display element using the liquid crystal aligning agent of the present invention requires a large pretilt angle, in particular, in order to develop a pretilt angle of 2 degrees or more, the production of polyamic acid and derivatives thereof used for the liquid crystal aligning agent of the present invention At this time, the proportion of the side chain type diamine in the total amount of diamine is preferably 5 to 70 mol%, more preferably 10 to 50 mol%.

  Dihydrazide can be used as a diamine for producing the polyamic acid or derivative thereof of the present invention. The dihydrazide used will be described. The dihydrazide used in the present invention can be selected from known dihydrazides without limitation.

式（２−ａ）において、Ｇは単結合、炭素数１〜２０のアルキレン、−ＣＯ−、−Ｏ−、−Ｓ−、−ＳＯ₂−、−Ｃ（ＣＨ₃）₂−、または−Ｃ（ＣＦ₃）₂−であり；
式（２−ｂ）において、環Ｂはシクロヘキサン環、ベンゼン環またはナフタレン環であり、この基の任意の水素はメチル、エチル、またはフェニルで置き換えられてもよく；
式（２−ｃ）において、環Ｃはそれぞれ独立してシクロヘキサン環、またはベンゼン環であり、この基の任意の水素はメチル、エチル、またはフェニルで置き換えられてもよく；Ｙは単結合、炭素数１〜２０のアルキレン、−ＣＯ−、−Ｏ−、−Ｓ−、−ＳＯ₂−、−Ｃ（ＣＨ₃）₂−、または−Ｃ（ＣＦ₃）₂−である。 Preferable examples of such dihydrazides include dihydrazides represented by formulas (2-a) to (2-c) from the viewpoint of easy availability of raw materials, ease of polymer polymerization, and electrical characteristics of the film. Can be mentioned.

In the formula (2-a), G represents a single bond, alkylene having 1 to 20 carbon atoms, —CO—, —O—, —S—, —SO ₂ —, —C (CH ₃ ) ₂ —, or —C. (CF ₃ ) ₂ —;
In formula (2-b), ring B is a cyclohexane ring, a benzene ring or a naphthalene ring, and any hydrogen of this group may be replaced with methyl, ethyl, or phenyl;
In formula (2-c), each ring C is independently a cyclohexane ring or a benzene ring, and any hydrogen of this group may be replaced by methyl, ethyl, or phenyl; Y is a single bond, carbon It is alkylene of formula 1 to 20, —CO—, —O—, —S—, —SO ₂ —, —C (CH ₃ ) ₂ —, or —C (CF ₃ ) ₂ —.

式（２−ａ−２）において、ｍは１〜１２の整数である。 More specifically, the following formulas (2-a-1) to (2-a-2), (2-b-1) to (2-b-3) or (2-c-1) to (2-c-) The dihydrazide represented by 6) is mentioned.

In formula (2-a-2), m is an integer of 1-12.

When using the liquid crystal aligning agent of this invention as a liquid crystal aligning agent for photo-alignment, in the diamine which comprises a polyamic acid or its derivative (s), the photosensitivity represented by following formula (DI-19-1)-(DI-19-9). It is essential to use a functional diamine.

  Among the specific examples of the diamine, when emphasizing further improving the orientation of the liquid crystal, the diamine is represented by the following formulas (DI-4-1), (DI-4-12) to (DI- 4-14), (DI-5-1), (DI-5-5), (DI-5-9), (DI-5-12), (DI-5-13), (DI-5-5) 22), (DI-5-28), (DI-5-30), (DI-7-3), (DI-9-1), (DI-13-4), (DI-13-5) , (DI-13-47), (DI-16-1), (DI-16-2) or (DI-16-4) is preferred. Or (DI-4-1), (DI-5-1), (DI-5-5), (DI-5-9), (DI-5-12), (DI-5-13), ( Diamines represented by (DI-5-22), (DI-7-3) and (DI-9-1) are more preferred.

  When importance is attached to improving the transmittance of the liquid crystal display element, among the above diamines, the formulas (DI-1-1) to (DI-1-4), (2-a-1) and (2) The compound represented by -a-2) is particularly preferable.

  When importance is attached to improving the photosensitivity of the liquid crystal display element, among the above photosensitive diamines, diamines represented by the formula (DI-19-1)-(DI-19-9) are preferable. Or the diamine represented by a formula (DI-19-1) is still more preferable.

  In each diamine, the ratio of the monoamine to the diamine may be 40 mol% or less, and a part of the diamine may be replaced with the monoamine. Such replacement can cause termination of the polymerization reaction when the polyamic acid is produced, and further progress of the polymerization reaction can be suppressed. For this reason, the molecular weight of the obtained polymer (polyamic acid or a derivative thereof) can be easily controlled by such replacement, and for example, the coating characteristics of the liquid crystal aligning agent are improved without impairing the effects of the present invention. be able to. As long as the effect of the present invention is not impaired, one or more diamines may be substituted for the monoamine. Examples of the monoamine include aniline, 4-hydroxyaniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n- Undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, and n-eicosylamine Is mentioned.

  The polyamic acid used for the liquid crystal aligning agent of this invention is obtained by making the acid dianhydride containing at least said acid dianhydride (1) and a diamine component react in a solvent. In this synthesis reaction, no special conditions other than the selection of the raw materials are required, and the conditions for normal polyamic acid synthesis can be applied as they are. The solvent to be used will be described later.

  The liquid crystal aligning agent of this invention may further contain other components other than polyamic acid or its derivative (s). The other component may be one type or two or more types.

  The polyamic acid or derivative thereof of the present invention may further contain a monoisocyanate compound in the monomer. By including the monoisocyanate compound in the monomer, the terminal of the resulting polyamic acid or derivative thereof is modified, and the molecular weight is adjusted. By using this terminal-modified polyamic acid or a derivative thereof, for example, the coating properties of the liquid crystal aligning agent can be improved without impairing the effects of the present invention. It is preferable from said viewpoint that content of the monoisocyanate compound in a monomer is 1-10 mol% with respect to the total amount of the diamine and tetracarboxylic dianhydride in a monomer. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

  The polyamic acid or derivative thereof of the present invention can be produced in the same manner as a known polyamic acid or derivative thereof used for forming a polyimide film. The total amount of tetracarboxylic dianhydride is preferably approximately equimolar to the total number of moles of diamine (molar ratio of about 0.9 to 1.1).

  The molecular weight of the polyamic acid or derivative thereof of the present invention is preferably from 10,000 to 500,000, more preferably from 20,000 to 200,000 in terms of polystyrene-equivalent weight average molecular weight (Mw). The molecular weight of the polyamic acid or derivative thereof can be determined from measurement by gel permeation chromatography (GPC).

  The presence of the polyamic acid or derivative thereof of the present invention can be confirmed by analyzing the solid content obtained by precipitation with a large amount of poor solvent by IR or NMR. It is also possible to confirm the monomer used by analyzing the extract of the decomposition product of the polyamic acid or its derivative with a strong alkaline aqueous solution such as KOH or NaOH by an organic solvent by GC, HPLC or GC-MS. it can.

<Alkenyl-substituted nadiimide compound>
For example, the liquid crystal aligning agent of the present invention may further contain an alkenyl-substituted nadiimide compound for the purpose of stabilizing the electrical characteristics of the liquid crystal display element over a long period of time. An alkenyl substituted nadiimide compound may be used by 1 type and may use 2 or more types together. For the above purpose, the content of the alkenyl-substituted nadiimide compound is preferably 1 to 100% by weight, more preferably 1 to 70% by weight, and more preferably 1 to 50% by weight with respect to the polyamic acid or derivative thereof. More preferably.

式（ＮＡ）において、Ｌ¹およびＬ²は独立して−Ｈ、炭素数１〜１２のアルキル、炭素数３〜６のアルケニル、炭素数５〜８のシクロアルキル、アリールまたはベンジルであり、ｎは１または２である。 The nadiimide compound will be specifically described below.
The alkenyl-substituted nadiimide compound is preferably a compound that can be dissolved in a solvent that dissolves the polyamic acid or derivative thereof used in the present invention. Examples of such alkenyl-substituted nadiimide compounds include compounds represented by the following formula (NA).

In the formula (NA), L ¹ and L ² are independently —H, alkyl having 1 to 12 carbons, alkenyl having 3 to 6 carbons, cycloalkyl having 5 to 8 carbons, aryl or benzyl, n Is 1 or 2.

In the formula (NA), when n = 1, W is alkyl having 1 to 12 carbons, alkenyl having 2 to 6 carbons, cycloalkyl having 5 to 8 carbons, aryl having 6 to 12 carbons, benzyl,- Z ¹ — (O) _r — (Z ² O) _k —Z ³ —H (wherein Z ¹ , Z ² and Z ³ are independently alkylene having 2 to 6 carbon atoms, and r is 0 or 1) And k is an integer of 1 to 30),-(Z ⁴ ) _r -BZ ⁵ -H (wherein Z ⁴ and Z ⁵ are each independently a carbon number) A group represented by the formula: -B-T-B-H (which is an alkylene having 1 to 4 carbon atoms or a cycloalkylene having 5 to 8 carbon atoms, B is phenylene, and r is 0 or 1) in, B is phenylene, and, T is _{-CH 2 -, - C (CH} 3) 2 -, - O -, - CO -, - S-, or -SO ₂ In a. Group represented by), or 1-3 -H is substituted with -OH groups of these groups.

  At this time, preferable W is alkyl having 1 to 8 carbons, alkenyl having 3 to 4 carbons, cyclohexyl, phenyl, benzyl, poly (ethyleneoxy) ethyl having 4 to 10 carbons, phenyloxyphenyl, phenylmethylphenyl, Phenyl isopropylidene phenyl, and one or two of these groups in which -H is replaced with -OH.

Wherein in (NA), when n = 2, W is alkylene of 2 to 20 carbon atoms, cycloalkylene of 5 to 8 carbon atoms, arylene having 6 to 12 carbon ^{atoms, -Z 1 -O- (Z 2 O} ) a group represented by _k— Z ³ — (wherein Z ^{1 to} Z ³ and k are as defined above), —Z ⁴ —BZ ⁵ — (where Z ⁴ , Z meaning of ⁵ and B are as defined above. groups represented by), -B- (O-B) r -T- (B-O) r -B- ( wherein, B is phenylene, T represents alkylene having 1 to 3 carbon atoms, —O— or —SO ₂ —, and r has the same meaning as described above.), Or 1 to 3 —H of these groups Is a group replaced by —OH.

In this case, preferable W is alkylene having 2 to 12 carbon atoms, cyclohexylene, phenylene, tolylene, xylylene, —C ₃ H ₆ —O— (Z ² —O) _n —O—C ₃ H ₆ — (where, Z ² is alkylene having 2 to 6 carbon atoms, and n is 1 or 2.) —B—T—B— (where B is phenylene, and T is — A group represented by CH ₂ —, —O— or —SO ₂ —), —B—O—B—C ₃ H ₆ —B—O—B— (where B is phenylene); And a group in which one or two -H of these groups are replaced by -OH.

  Such an alkenyl-substituted nadiimide compound, as described in, for example, Japanese Patent No. 2729565, holds an alkenyl-substituted nadic acid anhydride derivative and a diamine at a temperature of 80 to 220 ° C. for 0.5 to 20 hours. A compound obtained by synthesis by the method or a commercially available compound can be used. Specific examples of the alkenyl-substituted nadiimide compound include the following compounds.

  N-methyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-methyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3 -Dicarboximide, N-methyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-methyl-methallylmethylbicyclo [2.2.1] hept- 5-ene-2,3-dicarboximide, N- (2-ethylhexyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,

  N- (2-ethylhexyl) -allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-allyl-allylbicyclo [2.2.1] hept-5 -Ene-2,3-dicarboximide, N-allyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-allyl-methallylbicyclo [2.2 .1] Hept-5-ene-2,3-dicarboximide, N-isopropenyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-isopropenyl- Allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-isopropenyl-methallylbicyclo [2.2.1] hept-5-ene-2,3 -Dicarboxyl N-cyclohexyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-cyclohexyl-allyl (methyl) bicyclo [2.2.1] hept-5-ene -2,3-dicarboximide, N-cyclohexyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-phenyl-allylbicyclo [2.2.1] Hept-5-ene-2,3-dicarboximide,

  N-phenyl-allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-benzyl-allylbicyclo [2.2.1] hept-5-ene-2 , 3-dicarboximide, N-benzyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-benzyl-methallylbicyclo [2.2.1] hept -5-ene-2,3-dicarboximide, N- (2-hydroxyethyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2- Hydroxyethyl) -allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-hydroxyethyl) -methallylbicyclo [2.2.1] hept -5-ene- , 3-dicarboximide,

  N- (2,2-dimethyl-3-hydroxypropyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2,2-dimethyl-3-hydroxy Propyl) -allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2,3-dihydroxypropyl) -allylbicyclo [2.2.1] hept -5-ene-2,3-dicarboximide, N- (2,3-dihydroxypropyl) -allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (3-hydroxy-1-propenyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-hydroxycyclohexyl) -allyl (methyl) bicycle [2.2.1] hept-5-ene-2,3-dicarboximide,

  N- (4-hydroxyphenyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-hydroxyphenyl) -allyl (methyl) bicyclo [2.2 .1] hept-5-ene-2,3-dicarboximide, N- (4-hydroxyphenyl) -methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-hydroxyphenyl) -methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (3-hydroxyphenyl) -allylbicyclo [2.2. 1] Hept-5-ene-2,3-dicarboximide, N- (3-hydroxyphenyl) -allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide , -(P-hydroxybenzyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- {2- (2-hydroxyethoxy) ethyl} -allylbicyclo [2. 2.1] hept-5-ene-2,3-dicarboximide,

  N- {2- (2-hydroxyethoxy) ethyl} -allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- {2- (2-hydroxyethoxy) ) Ethyl} -methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- {2- (2-hydroxyethoxy) ethyl} -methallylmethylbicyclo [2.2 .1] Hept-5-ene-2,3-dicarboximide, N- [2- {2- (2-hydroxyethoxy) ethoxy} ethyl] -allylbicyclo [2.2.1] hept-5-ene -2,3-dicarboximide, N- [2- {2- (2-hydroxyethoxy) ethoxy} ethyl] -allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3- Dicarboximide, N- 2- {2- (2-hydroxyethoxy) ethoxy} ethyl] -methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- {4- (4-hydroxyphenyl) Isopropylidene) phenyl} -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- {4- (4-hydroxyphenylisopropylidene) phenyl} -allyl (methyl) bicyclo [2.2.1] Hept-5-ene-2,3-dicarboximide, N- {4- (4-hydroxyphenylisopropylidene) phenyl} -methallylbicyclo [2.2.1] hept-5 -Ene-2,3-dicarboximide, and oligomers thereof,

  N, N′-ethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-ethylene-bis (allylmethylbicyclo [2.2. 1] Hept-5-ene-2,3-dicarboximide), N, N′-ethylene-bis (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) N, N′-trimethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-hexamethylene-bis (allylbicyclo [2.2 .1] hept-5-ene-2,3-dicarboximide), N, N′-hexamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxy Imide), N, N′-dodecamethylene Bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N'-dodecamethylene-bis (allylmethylbicyclo [2.2.1] hept-5- Ene-2,3-dicarboximide), N, N′-cyclohexylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′— Cyclohexylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),

  1,2-bis {3 ′-(allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) propoxy} ethane, 1,2-bis {3 ′-(allylmethylbicyclo) [2.2.1] Hept-5-ene-2,3-dicarboximido) propoxy} ethane, 1,2-bis {3 ′-(methallylbicyclo [2.2.1] hept-5-ene -2,3-dicarboximido) propoxy} ethane, bis [2 '-{3'-(allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) propoxy} ethyl] Ether, bis [2 ′-{3 ′-(allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) propoxy} ethyl] ether, 1,4-bis {3 ′ -(Allylbicyclo [2.2.1] he To-5-ene-2,3-dicarboximido) propoxy} butane, 1,4-bis {3 ′-(allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxy Imido) propoxy} butane,

  N, N′-p-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-p-phenylene-bis (allylmethylbicyclo [ 2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3 -Dicarboximide), N, N′-m-phenylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N ′-{(1 -Methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N'-p-xylylene-bis (allylbicyclo) [2.2.1] Hept-5-ene-2,3-dica Boxoxyimide), N, N′-p-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-xylylene-bis ( Allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene -2,3-dicarboximide),

  2,2-bis [4- {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane, 2,2-bis [4- { 4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane, 2,2-bis [4- {4- (methallylbicyclo [2] 2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-di Carboximido) phenyl} methane, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane,

  Bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane, bis {4- (methallylmethylbicyclo [2.2.1] hept -5-ene-2,3-dicarboximido) phenyl} methane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} ether, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} ether, bis {4- (methallylbicyclo [2.2.1] hept-5 -Ene-2,3-dicarboximido) phenyl} ether, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} sulfone, bis {4 -(Ant Methylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) phenyl} sulfone,

  Bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} sulfone, 1,6-bis (allylbicyclo [2.2.1] hept- 5-ene-2,3-dicarboximide) -3-hydroxy-hexane, 1,12-bis (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide)- 3,6-dihydroxy-dodecane, 1,3-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -5-hydroxy-cyclohexane, 1,5-bis { 3 ′-(allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) propoxy} -3-hydroxy-pentane, 1,4-bis (allylbicyclo [2.2.1 ] Hept-5-ene 2,3-dicarboximide) -2-hydroxy - benzene,

  1,4-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -2,5-dihydroxy-benzene, N, N′-p- (2-hydroxy ) Xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-p- (2-hydroxy) xylylene-bis (allylmethylcyclo [2] 2.1] hept-5-ene-2,3-dicarboximide), N, N′-m- (2-hydroxy) xylylene-bis (allylbicyclo [2.2.1] hept-5-ene -2,3-dicarboximide), N, N'-m- (2-hydroxy) xylylene-bis (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) , N, N′-p- (2,3-dihi Proxy) xylylene - bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),

  2,2-bis [4- {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) -2-hydroxy-phenoxy} phenyl] propane, bis {4- (Allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -2-hydroxy-phenyl} methane, bis {3- (allylbicyclo [2.2.1] hept- 5-ene-2,3-dicarboximide) -4-hydroxy-phenyl} ether, bis {3- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -5-hydroxy-phenyl} sulfone, 1,1,1-tri {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide)} phenoxymethylpropane, N , N , N "- tri (ethylene methallyl ruby [2.2.1] hept-5-ene-2,3-dicarboximide) isocyanurate, and the like of these oligomers.

Furthermore, the alkenyl-substituted nadiimide compound used in the present invention may be a compound represented by the following formula containing an asymmetric alkylene / phenylene group.

Of the alkenyl-substituted nadiimide compounds, preferred compounds are shown below.
N, N′-ethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-ethylene-bis (allylmethylbicyclo [2.2. 1] Hept-5-ene-2,3-dicarboximide), N, N′-ethylene-bis (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) N, N′-trimethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-hexamethylene-bis (allylbicyclo [2.2 .1] hept-5-ene-2,3-dicarboximide), N, N′-hexamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxy Imide), N, N′-dodecamethylene-bis (a) Rilbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-dodecamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2 , 3-dicarboximide), N, N′-cyclohexylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-cyclohexylene- Bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),

  N, N′-p-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-p-phenylene-bis (allylmethylbicyclo [ 2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3 -Dicarboximide), N, N′-m-phenylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N ′-{(1 -Methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N'-p-xylylene-bis (allylbicyclo) [2.2.1] Hept-5-ene-2,3-dica Boxoxyimide), N, N′-p-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-xylylene-bis ( Allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene -2,3-dicarboximide), 2,2-bis [4- {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane 2,2-bis [4- {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane, 2,2-bis [4 -{4- (methallylbicyclo 2.2.1] Hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3- Dicarboximido) phenyl} methane, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane.

  Bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane, bis {4- (methallylmethylbicyclo [2.2.1] hept -5-ene-2,3-dicarboximido) phenyl} methane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} ether, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} ether, bis {4- (methallylbicyclo [2.2.1] hept-5 -Ene-2,3-dicarboximido) phenyl} ether, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} sulfone, bis {4 -(Ant Methylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} sulfone, bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2, 3-Dicarboximido) phenyl} sulfone.

Further preferred alkenyl-substituted nadiimide compounds are shown below.
N, N′-ethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-ethylene-bis (allylmethylbicyclo [2.2. 1] Hept-5-ene-2,3-dicarboximide), N, N′-ethylene-bis (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) N, N′-trimethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-hexamethylene-bis (allylbicyclo [2.2 .1] hept-5-ene-2,3-dicarboximide), N, N′-hexamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxy Imide), N, N′-dodecamethylene-bis (a) Rilbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-dodecamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2 , 3-dicarboximide), N, N′-cyclohexylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-cyclohexylene- Bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide).

  N, N′-p-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-p-phenylene-bis (allylmethylbicyclo [ 2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3 -Dicarboximide), N, N′-m-phenylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N ′-{(1 -Methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N'-p-xylylene-bis (allylbicyclo) [2.2.1] Hept-5-ene-2,3-dica Boxoxyimide), N, N′-p-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-xylylene-bis ( Allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene -2,3-dicarboximide).

  2,2-bis [4- {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane, 2,2-bis [4- { 4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane, 2,2-bis [4- {4- (methallylbicyclo [2] 2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-di Carboximido) phenyl} methane, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane, bis {4- (methallylbicyclo [2] 2.1] Hept 5-ene-2,3-dicarboximide) phenyl} methane, bis {4- (methallyl methyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) phenyl} methane.

And as a particularly preferable alkenyl substituted nadiimide compound, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) represented by the following formula (NA-1): Phenyl} methane, N, N′-m-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) represented by the formula (NA-2), and N, N′-hexamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) represented by the formula (NA-3) may be mentioned.

<Compound having radically polymerizable unsaturated double bond>
For example, the liquid crystal aligning agent of the present invention may further contain a compound having a radical polymerizable unsaturated double bond for the purpose of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time. The compound having a radically polymerizable unsaturated double bond may be one kind of compound or two or more kinds of compounds. The compound having a radical polymerizable unsaturated double bond does not include an alkenyl-substituted nadiimide compound. The content of the compound having a radically polymerizable unsaturated double bond is preferably 1 to 100% by weight, more preferably 1 to 70% by weight with respect to the polyamic acid or derivative thereof for the above purpose. Preferably, it is 1 to 50% by weight.

  The ratio of the compound having a radical polymerizable unsaturated double bond to the alkenyl-substituted nadiimide compound reduces the ion density of the liquid crystal display element, suppresses the increase in ion density over time, and further suppresses the occurrence of afterimages. Therefore, the compound / alkenyl-substituted nadiimide compound having a radically polymerizable unsaturated double bond is preferably 0.1 to 10 and more preferably 0.5 to 5 in weight ratio.

The compound having a radical polymerizable unsaturated double bond will be specifically described below.
Examples of the compound having a radical polymerizable unsaturated double bond include (meth) acrylic acid esters, (meth) acrylic acid derivatives such as (meth) acrylic acid amide, and bismaleimide. The compound having a radically polymerizable unsaturated double bond is more preferably a (meth) acrylic acid derivative having two or more radically polymerizable unsaturated double bonds.

  Specific examples of the (meth) acrylic acid ester include, for example, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentanyl (meth) acrylate. Examples include oxyethyl, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate.

  Specific examples of the bifunctional (meth) acrylic acid ester include, for example, ethylene bisacrylate, Aronix M-210, Aronix M-240 and Aronix M-6200, which are products of Toa Gosei Chemical Co., Ltd., Nippon Kayaku Co., Ltd. ) Products KAYARAD HDDA, KAYARAD HX-220, KAYARAD R-604 and KAYARAD R-684, Osaka Organic Chemicals Co., Ltd. products V260, V312 and V335HP, and products of Kyoeisha Oil Chemical Co., Ltd. Light acrylate BA-4EA, light acrylate BP-4PA and light acrylate BP-2PA.

  Specific examples of the trifunctional or higher polyfunctional (meth) acrylic acid ester include, for example, 4,4'-methylenebis (N, N-dihydroxyethylene acrylate aniline), Aronix M-, a product of Toa Gosei Chemical Co., Ltd. 400, Aronix M-405, Aronix M-450, Aronix M-7100, Aronix M-8030, Aronix M-8060, KAYARAD TMPTA, KAYARAD DPCA-20, KAYARAD DPCA-30, products of Nippon Kayaku Co., Ltd. Examples include KAYARAD DPCA-60, KAYARAD DPCA-120, and VGPT, which is a product of Osaka Organic Chemical Industry Co., Ltd.

  Specific examples of the (meth) acrylic acid amide derivative include, for example, N-isopropylacrylamide, N-isopropylmethacrylamide, Nn-propylacrylamide, Nn-propylmethacrylamide, N-cyclopropylacrylamide, N-cyclopropyl. Methacrylamide, N-ethoxyethylacrylamide, N-ethoxyethylmethacrylamide, N-tetrahydrofurfurylacrylamide, N-tetrahydrofurfurylmethacrylamide, N-ethylacrylamide, N-ethyl-N-methylacrylamide, N, N-diethyl Acrylamide, N-methyl-Nn-propylacrylamide, N-methyl-N-isopropylacrylamide, N-acryloylpiperidine, N-acryloylpyrrolidine, N, N′-me Renbisacrylamide, N, N′-ethylenebisacrylamide, N, N′-dihydroxyethylenebisacrylamide, N- (4-hydroxyphenyl) methacrylamide, N-phenylmethacrylamide, N-butylmethacrylamide, N- (iso -Butoxymethyl) methacrylamide, N- [2- (N, N-dimethylamino) ethyl] methacrylamide, N, N-dimethylmethacrylamide, N- [3- (dimethylamino) propyl] methacrylamide, N- ( Methoxymethyl) methacrylamide, N- (hydroxymethyl) -2-methacrylamide, N-benzyl-2-methacrylamide, and N, N′-methylenebismethacrylamide.

  Among the above (meth) acrylic acid derivatives, N, N′-methylenebisacrylamide, N, N′-dihydroxyethylene-bisacrylamide, ethylenebisacrylate, and 4,4′-methylenebis (N, N-dihydroxyethyleneacrylate) Aniline) is particularly preferred.

  Examples of the bismaleimide include BMI-70 and BMI-80 manufactured by Kay Kasei Co., Ltd., and BMI-1000, BMI-3000, BMI-4000, BMI-5000 and BMI- manufactured by Daiwa Kasei Kogyo Co., Ltd. 7000.

<Oxazine compound>
For example, the liquid crystal aligning agent of this invention may further contain the oxazine compound from the objective of stabilizing the electrical property in a liquid crystal display element for a long period of time. The oxazine compound may be a kind of compound or two or more kinds of compounds. The content of the oxazine compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, and more preferably 1 to 20% by weight with respect to the polyamic acid or derivative thereof for the above purpose. More preferably.

The oxazine compound will be specifically described below.
The oxazine compound is soluble in a solvent that dissolves the polyamic acid or a derivative thereof, and in addition, an oxazine compound having ring-opening polymerizability is preferable.

  Further, the number of oxazine structures in the oxazine compound is not particularly limited.

  Various structures are known for the structure of oxazine. In the present invention, the structure of oxazine is not particularly limited, but examples of the oxazine structure in the oxazine compound include an oxazine structure having an aromatic group containing a condensed polycyclic aromatic group such as benzoxazine and naphthoxazine.

式（ＯＸ−１）〜（ＯＸ−３）において、Ｌ³およびＬ⁴は炭素数１〜３０の有機基であり、式（ＯＸ−１）〜（ＯＸ−６）において、Ｌ⁵〜Ｌ⁸は−Ｈまたは炭素数１〜６の炭化水素基であり、式（ＯＸ−３）、式（ＯＸ−４）および式（ＯＸ−６）において、Ｑ¹は単結合、−Ｏ−、−Ｓ−、−Ｓ−Ｓ−、−ＳＯ₂−、−ＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−Ｃ（ＣＨ₃）₂−、−Ｃ（ＣＦ₃）₂−、−（ＣＨ₂）_v−、−Ｏ−（ＣＨ₂）_v−Ｏ−、−Ｓ−（ＣＨ₂）_v−Ｓ−であり、ここでｖは１〜６の整数であり、式（ＯＸ−５）および式（ＯＸ−６）において、Ｑ²は独立して単結合、−Ｏ−、−Ｓ−、−ＣＯ−、−Ｃ（ＣＨ₃）₂−、−Ｃ（ＣＦ₃）₂−または炭素数１〜３のアルキレンであり、Ｑ²におけるベンゼン環、ナフタレン環に結合している水素は独立して−Ｆ、−ＣＨ₃、−ＯＨ、−ＣＯＯＨ、−ＳＯ₃Ｈ、−ＰＯ₃Ｈ₂と置き換えられていてもよい。 Examples of the oxazine compound include compounds represented by the following formulas (OX-1) to (OX-6). In the following formula, the bond displayed toward the center of the ring indicates that it is bonded to any carbon that forms the ring and can be bonded to a substituent.

In formulas (OX-1) to (OX-3), L ³ and L ⁴ are organic groups having 1 to 30 carbon atoms, and in formulas (OX-1) to (OX-6), L ^{5 to} L ⁸ Is —H or a hydrocarbon group having 1 to 6 carbon atoms, and in formula (OX-3), formula (OX-4) and formula (OX-6), Q ¹ is a single bond, —O—, —S -, - S-S -, - SO 2 -, - CO -, - CONH -, - NHCO -, - C (CH 3) 2 -, - C (CF 3) 2 -, - (CH 2) v - , —O— (CH ₂ ) _v —O—, —S— (CH ₂ ) _v —S—, wherein v is an integer of 1 to 6, and the formula (OX-5) and the formula (OX— 6), Q ² is independently a single bond, —O—, —S—, —CO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ — or alkylene having 1 to 3 carbon atoms. , and the benzene ring in Q ^2, naphthoquinone Hydrogen bonded to Len ring is independently _{-F, -CH 3, -OH, -COOH} , -SO 3 H, may be replaced with -PO ₃ H _2.

  The oxazine compound includes an oligomer or polymer having an oxazine structure in the side chain, and an oligomer or polymer having an oxazine structure in the main chain.

Examples of the oxazine compound represented by the formula (OX-1) include the following oxazine compounds.

In Formula (OX-1-2), L ³ is preferably alkyl having 1 to 30 carbons, and more preferably alkyl having 1 to 20 carbons.

Examples of the oxazine compound represented by the formula (OX-2) include the following oxazine compounds.

In the formula, L ³ is preferably alkyl having 1 to 30 carbons, and more preferably alkyl having 1 to 20 carbons.

式（ＯＸ−３−Ｉ）において、Ｌ³およびＬ⁴は炭素数１〜３０の有機基であり、Ｌ⁵からＬ⁸は−Ｈまたは炭素数１〜６の炭化水素基であり、Ｑ¹は単結合、−ＣＨ₂−、−Ｃ（ＣＨ₃）₂−、−ＣＯ−、−Ｏ−、−ＳＯ₂−、−Ｃ（ＣＨ₃）₂−、または−Ｃ（ＣＦ₃）₂−である。式（ＯＸ−３−Ｉ）で表されるオキサジン化合物としては、例えば以下のオキサジン化合物が挙げられる。 As the oxazine compound represented by the formula (OX-3), an oxazine compound represented by the following formula (OX-3-I) can be given.

In the formula (OX-3-I), L ³ and L ⁴ are an organic group having 1 to 30 carbon atoms, L ⁵ to L ⁸ are —H or a hydrocarbon group having 1 to 6 carbon atoms, and Q ¹ Is a single bond, —CH ₂ —, —C (CH ₃ ) ₂ —, —CO—, —O—, —SO ₂ —, —C (CH ₃ ) ₂ —, or —C (CF ₃ ) ₂ —. is there. Examples of the oxazine compound represented by the formula (OX-3-I) include the following oxazine compounds.

式中、Ｌ³およびＬ⁴は炭素数１〜３０のアルキルが好ましく、炭素数１〜２０のアルキルがさらに好ましい。

In the formula, L ³ and L ⁴ are preferably alkyl having 1 to 30 carbon atoms, more preferably alkyl having 1 to 20 carbon atoms.

Examples of the oxazine compound represented by the formula (OX-4) include the following oxazine compounds.

Examples of the oxazine compound represented by the formula (OX-5) include the following oxazine compounds.

Examples of the oxazine compound represented by the formula (OX-6) include the following oxazine compounds.

  Of these, more preferably, the formulas (OX-2-1), (OX-3-1), (OX-3-3), (OX-3-5), (OX-3-7), ( OX-3-9), (OX-4-1) to (OX-4-6), (OX-5-3), (OX-5-4), and (OX-6-6-2) to (OX Oxazine compound represented by -6-4).

  The oxazine compound can be produced by the same method as described in International Publication No. 2004/009708, JP-A-11-12258, and JP-A-2004-352670.

  The oxazine compound represented by the formula (OX-1) is obtained by reacting a phenol compound, a primary amine, and an aldehyde (see International Publication No. 2004/009708 pamphlet).

  The oxazine compound represented by the formula (OX-2) is obtained by reacting by a method of gradually adding a primary amine to formaldehyde, and then adding and reacting a compound having a naphthol-based hydroxyl group (International Publication 2004 / (Refer to 009708 pamphlet.)

  The oxazine compound represented by the formula (OX-3) is a secondary aliphatic compound in which 1 mol of a phenol compound, at least 2 mol or more of an aldehyde, and 1 mol of a primary amine are added to one phenolic hydroxyl group in an organic solvent. It can be obtained by reacting in the presence of an amine, a tertiary aliphatic amine, or a basic nitrogen-containing heterocyclic compound (see International Publication No. 2004/009708 and JP-A-11-12258).

  Oxazine compounds represented by formulas (OX-4) to (OX-6) are aldehydes such as 4,4′-diaminodiphenylmethane, diamines having a plurality of benzene rings and organic groups that bind them, and aldehydes such as formalin. And phenol are subjected to a dehydration condensation reaction in n-butanol at a temperature of 90 ° C. or higher (see JP-A No. 2004-352670).

<Oxazoline compound>
For example, the liquid crystal aligning agent of this invention may further contain the oxazoline compound from the objective of stabilizing the electrical property in a liquid crystal display element for a long period of time. An oxazoline compound is a compound having an oxazoline structure. The oxazoline compound may be a single compound or two or more compounds. The content of the oxazoline compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, and more preferably 1 to 20% by weight with respect to the polyamic acid or a derivative thereof for the above purpose. It is preferable that Alternatively, the content of the oxazoline compound is preferably 0.1 to 40% by weight with respect to the polyamic acid or a derivative thereof when the oxazoline structure in the oxazoline compound is converted to oxazoline.

The oxazoline compound will be specifically described below.
The oxazoline compound may have only one type of oxazoline structure in one compound, or may have two or more types. Further, the oxazoline compound may have one oxazoline structure in one compound, but preferably has two or more. The oxazoline compound may be a polymer having an oxazoline ring structure in the side chain, or may be a copolymer. The polymer having an oxazoline structure in the side chain may be a homopolymer of a monomer having an oxazoline structure in the side chain, or a copolymer of a monomer having an oxazoline structure in the side chain and a monomer having no oxazoline structure It may be. The copolymer having an oxazoline structure in the side chain may be a copolymer of two or more monomers having an oxazoline structure in the side chain, or two or more monomers having an oxazoline structure in the side chain and an oxazoline structure. It may also be a copolymer with a monomer that does not have.

  The oxazoline structure is preferably a structure present in the oxazoline compound so that one or both of oxygen and nitrogen in the oxazoline structure can react with the carbonyl group of the polyamic acid.

  Examples of the oxazoline compound include 2,2′-bis (2-oxazoline), 1,2,4-tris- (2-oxazolinyl-2) -benzene, 4-furan-2-ylmethylene-2-phenyl-4H—. Oxazol-5-one, 1,4-bis (4,5-dihydro-2-oxazolyl) benzene, 1,3-bis (4,5-dihydro-2-oxazolyl) benzene, 2,3-bis (4- Isopropenyl-2-oxazolin-2-yl) butane, 2,2′-bis-4-benzyl-2-oxazoline, 2,6-bis (isopropyl-2-oxazolin-2-yl) pyridine, 2,2 ′ -Isopropylidenebis (4-tert-butyl-2-oxazoline), 2,2'-isopropylidenebis (4-phenyl-2-oxazoline), 2,2'-methylenebi (4-tert-butyl-2-oxazoline), and 2,2'-methylenebis (4-phenyl-2-oxazoline) and the like. In addition to these, polymers and oligomers having oxazolyl such as Epocross (trade name, manufactured by Nippon Shokubai Co., Ltd.) are also included. Of these, 1,3-bis (4,5-dihydro-2-oxazolyl) benzene is more preferable.

<Epoxy compound>
For example, the liquid crystal aligning agent of the present invention may further contain an epoxy compound for the purpose of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time. The epoxy compound may be a kind of compound or two or more kinds of compounds. The content of the epoxy compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, and more preferably 1 to 20% by weight with respect to the polyamic acid or derivative thereof for the above purpose. More preferably.

The epoxy compound will be specifically described below.
Examples of the epoxy compound include various compounds having one or more epoxy rings in the molecule. Examples of the compound having one epoxy ring in the molecule include phenyl glycidyl ether, butyl glycidyl ether, 3,3,3-trifluoromethyl propylene oxide, styrene oxide, hexafluoropropylene oxide, cyclohexene oxide, 3-glycidoxy Propyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-glycidylphthalimide, (nonafluoro-N-butyl) epoxide, perfluoroethylglycidyl ether, epichlorohydrin, epibromohydrin, N, N-diglycidylaniline, and 3- [2- (perfluorohexyl) ethoxy] -1,2-epoxypropane.

  Examples of the compound having two epoxy rings in the molecule include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl. Ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate and 3 -(N, N-diglycidyl) aminopropyltrimethoxysilane.

  Examples of the compound having three epoxy rings in the molecule include 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3- Epoxypropoxy] phenyl)] ethyl] phenyl] propane (trade name “Techmore VG3101L” (manufactured by Mitsui Chemicals, Inc.)).

  Examples of the compound having four epoxy rings in the molecule include 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane, and 3- (N-allyl-N-glycidyl) Aminopropyltrimethoxysilane is mentioned.

  In addition to the above, examples of the compound having an epoxy ring in the molecule include oligomers and polymers having an epoxy ring. Examples of the monomer having an epoxy ring include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and methyl glycidyl (meth) acrylate.

  Examples of other monomers copolymerized with a monomer having an epoxy ring include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and iso-butyl. (Meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, styrene, methylstyrene, chloromethyl Styrene, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, N-cyclohexylmaleimide and N-phenylmaleimide.

  Preferable specific examples of the monomer polymer having an epoxy ring include polyglycidyl methacrylate. Preferred examples of the copolymer of the monomer having an epoxy ring and another monomer include N-phenylmaleimide-glycidyl methacrylate copolymer, N-cyclohexylmaleimide-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate. Copolymer, butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer, (3-ethyl-3-oxetanyl) methyl methacrylate-glycidyl methacrylate copolymer and styrene-glycidyl methacrylate copolymer Is mentioned.

  Among these examples, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′— Tetraglycidyl-4,4′-diaminodiphenylmethane, trade name “Techmore VG3101L”, 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate, N-phenylmaleimide-glycidyl methacrylate copolymer, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane is particularly preferred.

  More systematically, examples of the epoxy compound include glycidyl ether, glycidyl ester, glycidyl amine, epoxy group-containing acrylic resin, glycidyl amide, glycidyl isocyanurate, chain aliphatic epoxy compound, and cyclic aliphatic epoxy compound. Is mentioned. In addition, an epoxy compound means the compound which has an epoxy group, and an epoxy resin means resin which has an epoxy group.

  Examples of the epoxy compound include glycidyl ether, glycidyl ester, glycidyl amine, epoxy group-containing acrylic resin, glycidyl amide, glycidyl isocyanurate, chain aliphatic epoxy compound, and cyclic aliphatic epoxy compound.

  Examples of the glycidyl ether include bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, bisphenol type epoxy compound, hydrogenated bisphenol-A type epoxy compound, hydrogenated bisphenol-F type epoxy compound, hydrogenated bisphenol. -S type epoxy compound, hydrogenated bisphenol type epoxy compound, brominated bisphenol-A type epoxy compound, brominated bisphenol-F type epoxy compound, phenol novolac type epoxy compound, cresol novolac type epoxy compound, brominated phenol novolak type epoxy compound Brominated cresol novolac type epoxy compound, bisphenol A novolac type epoxy compound, naphthalene skeleton-containing epoxy compound, aromatic polymer Glycidyl ether compounds, dicyclopentadiene phenol type epoxy compound, alicyclic diglycidyl ether compounds, aliphatic polyglycidyl ether compound, a polysulfide-type diglycidyl ether compound, and biphenol type epoxy compound.

  Examples of the glycidyl ester include a diglycidyl ester compound and a glycidyl ester epoxy compound.

  Examples of the glycidylamine include polyglycidylamine compounds and glycidylamine type epoxy resins.

  Examples of the epoxy group-containing acrylic compound include homopolymers and copolymers of monomers having oxiranyl.

  Examples of glycidyl amide include glycidyl amide type epoxy compounds.

  Examples of the chain aliphatic epoxy compound include compounds containing an epoxy group obtained by oxidizing a carbon-carbon double bond of an alkene compound.

  Examples of the cycloaliphatic epoxy compound include a compound containing an epoxy group obtained by oxidizing a carbon-carbon double bond of a cycloalkene compound.

  Examples of the bisphenol A type epoxy compound include jER828, jER1001, jER1002, jER1003, jER1004, jER1007, jER1010 (all manufactured by Mitsubishi Chemical Corporation), Epototo YD-128 (manufactured by Tohto Kasei Co., Ltd.), DER-331, DER-332, DER-324 (all manufactured by The Dow Chemical Company), Epicron 840, Epicron 850, Epicron 1050 (all manufactured by DIC Corporation), Epomic R-140, Epomic R-301, and Epomic R-304 (Both manufactured by Mitsui Chemicals, Inc.).

  Examples of the bisphenol F type epoxy compound include jER806, jER807, jER4004P (all manufactured by Mitsubishi Chemical Corporation), Epototo YDF-170, Epototo YDF-175S, Epototo YDF-2001 (all manufactured by Toto Kasei Co., Ltd.), DER-354 (manufactured by Dow Chemical Company), Epicron 830, and Epicron 835 (all manufactured by DIC Corporation) can be mentioned.

  Examples of the bisphenol type epoxy compound include epoxidized products of 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane.

  Examples of the hydrogenated bisphenol-A type epoxy compound include Santo Tote ST-3000 (manufactured by Tohto Kasei Co., Ltd.), Rica Resin HBE-100 (manufactured by Shin Nippon Rika Co., Ltd.), and Denacol EX-252 (Nagase ChemteX Corporation) ))).

  Examples of the hydrogenated bisphenol type epoxy compound include an epoxidized product of hydrogenated 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane.

  Examples of brominated bisphenol-A type epoxy compounds include jER5050, jER5051 (all manufactured by Mitsubishi Chemical Corporation), Epototo YDB-360, Epototo YDB-400 (all manufactured by Toto Kasei), DER-530, DER-538 (all manufactured by The Dow Chemical Company), Epicron 152, and Epicron 153 (all manufactured by DIC Corporation) may be mentioned.

  Examples of the phenol novolac type epoxy compound include jER152, jER154 (all manufactured by Mitsubishi Chemical Corporation), YDPN-638 (manufactured by Tohto Kasei Co., Ltd.), DEN431, DEN438 (all manufactured by The Dow Chemical Company), and Epicron N-770. (Made by DIC Corporation), EPPN-201, and EPPN-202 (all are made by Nippon Kayaku Co., Ltd.).

  Examples of the cresol novolac type epoxy compound include jER180S75 (manufactured by Mitsubishi Chemical Corporation), YDCN-701, YDCN-702 (all manufactured by Tohto Kasei Co., Ltd.), Epicron N-665, Epicron N-695 (all DIC Corporation) )), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, and EOCN-1027 (all manufactured by Nippon Kayaku Co., Ltd.).

  Examples of the bisphenol A novolac type epoxy compound include jER157S70 (manufactured by Mitsubishi Chemical Corporation) and Epicron N-880 (manufactured by DIC Corporation).

  Examples of the naphthalene skeleton-containing epoxy compound include Epicron HP-4032, Epicron HP-4700, Epicron HP-4770 (all manufactured by DIC Corporation), and NC-7000 (manufactured by Nippon Kayaku Co., Ltd.).

Examples of the aromatic polyglycidyl ether compound include hydroquinone diglycidyl ether (following formula EP-1), catechol diglycidyl ether (following formula EP-2) resorcinol diglycidyl ether (following formula EP-3), 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3-epoxypropoxy] phenyl)] ethyl] phenyl] propane (formula EP-4 below), Tris (4-glycidyloxyphenyl) methane (following formula EP-5), jER1031S, jER1032H60 (all manufactured by Mitsubishi Chemical Corporation), TACTIX-742 (manufactured by The Dow Chemical Company), Denacol EX-201 (Nagase ChemteX) Manufactured by Co., Ltd.), DPPN-503, DPPN-502H, DPPN-501H, C6000 (both manufactured by Nippon Kayaku Co., Ltd.), (manufactured by Mitsui Chemicals, Inc.) Techmore VG3101L, a compound represented by the following formula EP-6, and compounds represented by the following formula EP-7.

  Examples of the dicyclopentadiene phenol type epoxy compound include TACTIX-556 (manufactured by The Dow Chemical Company) and epiclone HP-7200 (manufactured by DIC Corporation).

  Examples of the alicyclic diglycidyl ether compound include a cyclohexane dimethanol diglycidyl ether compound and licarresin DME-100 (manufactured by Shin Nippon Rika Co., Ltd.).

Examples of the aliphatic polyglycidyl ether compound include ethylene glycol diglycidyl ether (following formula EP-8), diethylene glycol diglycidyl ether (following formula EP-9), polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether (following formula EP). -10), tripropylene glycol diglycidyl ether (following formula EP-11), polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether (following formula EP-12), 1,4-butanediol diglycidyl ether (following formula EP-13), 1,6-hexanediol diglycidyl ether (following formula EP-14), dibromoneopentyl glycol diglycidyl ether (following formula EP-15), Denacol EX 810, Denacol EX-851, Denacol EX-8301, Denacol EX-911, Denacol EX-920, Denacol EX-931, Denacol EX-211, Denacol EX-212, Denacol EX-313 (all Nagase ChemteX Corporation) ), DD-503 (manufactured by ADEKA Corporation), Rica Resin W-100 (manufactured by Shin Nippon Rika Co., Ltd.), 1,3,5,6-tetraglycidyl-2,4-hexanediol (following formula EP- 16), glycerin polyglycidyl ether, sorbitol polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, Denacol EX-313, Denacol EX-611, Denacol EX-321, and Denacol EX-411 Re also manufactured by Nagase Chemtex Co., Ltd.) and the like.

  Examples of the polysulfide type diglycidyl ether compound include FLDP-50 and FLDP-60 (both manufactured by Toray Rethiocol Co., Ltd.).

  Examples of the biphenol type epoxy compound include YX-4000, YL-6121H (all manufactured by Mitsubishi Chemical Corporation), NC-3000P, and NC-3000S (all manufactured by Nippon Kayaku Co., Ltd.).

Examples of the diglycidyl ester compound include diglycidyl terephthalate (following formula EP-17), diglycidyl phthalate (following formula EP-18), bis (2-methyloxiranylmethyl) phthalate (following formula EP-19), di Examples include glycidyl hexahydrophthalate (following formula EP-20), a compound represented by the following formula EP-21, a compound represented by the following formula EP-22, and a compound represented by the following formula EP-23.

  Examples of the glycidyl ester epoxy compound include jER871, jER872 (all manufactured by Mitsubishi Chemical Corporation), Epicron 200, Epicron 400 (all manufactured by DIC Corporation), Denacol EX-711, and Denacol EX-721 (all Nagase ChemteX Corporation).

Examples of the polyglycidylamine compound include N, N-diglycidylaniline (following formula EP-24), N, N-diglycidyl-o-toluidine (following formula EP-25), N, N-diglycidyl-m-toluidine ( The following formula EP-26), N, N-diglycidyl-2,4,6-tribromoaniline (the following formula EP-27), 3- (N, N-diglycidyl) aminopropyltrimethoxysilane (the following formula EP-28 ), N, N, O-triglycidyl-p-aminophenol (following formula EP-29), N, N, O-triglycidyl-m-aminophenol (following formula EP-30), N, N, N ′ , N′-tetraglycidyl-4,4′-diaminodiphenylmethane (following formula EP-31), N, N, N ′, N′-tetraglycidyl-m-xylylenediamine (TETRAD) X (Mitsubishi Gas Chemical Co., Ltd.), the following formula EP-32), 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane (TETRAD-C (Mitsubishi Gas Chemical Co., Ltd.)), the following formula EP-33), 1,4-bis (N, N-diglycidylaminomethyl) cyclohexane (following formula EP-34), 1,3-bis (N, N-diglycidylamino) cyclohexane (following formula EP-35) ), 1,4-bis (N, N-diglycidylamino) cyclohexane (following formula EP-36), 1,3-bis (N, N-diglycidylamino) benzene (following formula EP-37), 1, 4-bis (N, N-diglycidylamino) benzene (following formula EP-38), 2,6-bis (N, N-diglycidylaminomethyl) bicyclo [2.2.1] heptane (following formula EP- 39), N, N, N ′, N′-tetraglycidyl-4,4′-diaminodicyclohexylmethane (following formula EP-40), 2,2′-dimethyl- (N, N, N ′, N′-tetraglycidyl) -4,4 '-Diaminobiphenyl (following formula EP-41), N, N, N', N'-tetraglycidyl-4,4'-diaminodiphenyl ether (following formula EP-42), 1,3,5-tris (4- (N, N-diglycidyl) aminophenoxy) benzene (following formula EP-43), 2,4,4′-tris (N, N-diglycidylamino) diphenyl ether (following formula EP-44), tris (4- ( N, N-diglycidyl) aminophenyl) methane (following formula EP-45), 3,4,3 ′, 4′-tetrakis (N, N-diglycidylamino) biphenyl (following formula EP-46), 3,4 , 3 ', 4'-tetraki (N, N-diglycidyl amino) diphenyl ether (formula EP-47), a compound represented by the following formula EP-48, and compounds represented by the following formula EP-49.

  Examples of the homopolymer of the monomer having oxiranyl include polyglycidyl methacrylate. Examples of the copolymer of monomers having oxiranyl include N-phenylmaleimide-glycidyl methacrylate copolymer, N-cyclohexylmaleimide-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate-glycidyl methacrylate copolymer. Examples thereof include 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer, (3-ethyl-3-oxetanyl) methyl methacrylate-glycidyl methacrylate copolymer, and styrene-glycidyl methacrylate copolymer.

  Examples of the monomer having oxiranyl include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and methyl glycidyl (meth) acrylate.

  Examples of the monomer other than the monomer having oxiranyl in the copolymer of the monomer having oxiranyl include, for example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, and butyl (meth). Acrylate, iso-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, styrene, Examples include methylstyrene, chloromethylstyrene, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, N-cyclohexylmaleimide, and N-phenylmaleimide.

Examples of glycidyl isocyanurate include 1,3,5-triglycidyl-1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione (the following formula EP-50), 1,3. -Diglycidyl-5-allyl-1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione (following formula EP-51) and glycidyl isocyanurate type epoxy resin.

  Examples of the chain aliphatic epoxy compound include epoxidized polybutadiene and epolide PB3600 (manufactured by Daicel Corporation).

Examples of the cycloaliphatic epoxy compound include 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate (Celoxide 2021 (manufactured by Daicel Corporation), the following formula EP-52), 2-methyl -3,4-epoxycyclohexylmethyl-2'-methyl-3 ', 4'-epoxycyclohexylcarboxylate (following formula EP-53), 2,3-epoxycyclopentane-2', 3'-epoxycyclopentane ether (Formula EP-54), ε-caprolactone modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 1,2: 8,9-diepoxy limonene (Celoxide 3000 (Daicel Corporation) Manufactured), the following formula EP-55), a compound represented by the following formula EP-56, CY-1 5, CY-177, CY-179 (all are available from The Ciba-Geigy Chemical Corp. (available from Huntsman Japan)), EHPD-3150 (manufactured by Daicel Corporation), and cyclic aliphatic type An epoxy resin is mentioned.

  The epoxy compound is preferably one or more of a polyglycidylamine compound, a bisphenol A novolac type epoxy compound, a cresol novolac type epoxy compound, and a cyclic aliphatic type epoxy compound, and N, N, N ′, N′-tetraglycidyl -M-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane, trade name “Techmore VG3101L” 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate, N-phenylmaleimide-glycidyl methacrylate copolymer, N, N, O-triglycidyl-p-aminophenol, bisphenol A novolak type Epoxy compounds, It is preferred and is one or more cresol novolac type epoxy compound.

  For example, the liquid crystal aligning agent of this invention may further contain various additives. Examples of the various additives include high molecular compounds other than polyamic acid and its derivatives, and low molecular compounds, which can be selected and used according to their respective purposes.

  For example, the polymer compound includes a polymer compound that is soluble in an organic solvent. It is preferable to add such a polymer compound to the liquid crystal aligning agent of the present invention from the viewpoint of controlling the electrical characteristics and orientation of the liquid crystal alignment film to be formed. Examples of the polymer compound include polyamide, polyurethane, polyurea, polyester, polyepoxide, polyester polyol, silicone-modified polyurethane, and silicone-modified polyester.

  Examples of the low molecular weight compound include 1) a surfactant in accordance with the purpose when improvement in coatability is desired, 2) an antistatic agent when improvement in antistatic is required, and 3) adhesion to the substrate. In the case where it is desired to improve the properties, a silane coupling agent or a titanium-based coupling agent, and 4) an imidization catalyst in the case where imidization proceeds at a low temperature can be mentioned.

  Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyltri Methoxysilane, paraaminophenyltrimethoxysilane, paraaminophenyltriethoxysilane, metaaminophenyltrimethoxysilane, metaaminophenyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxy Propyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane , 3-mercaptopropyltrimethoxysilane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propylamine, and N, N′-bis [3- (trimethoxysilyl) Propyl] ethylenediamine. A preferred silane coupling agent is 3-aminopropyltriethoxysilane.

  Examples of imidation catalysts include aliphatic amines such as trimethylamine, triethylamine, tripropylamine, and tributylamine; aromatic amines such as N, N-dimethylaniline, N, N-diethylaniline, methyl-substituted aniline, and hydroxy-substituted aniline. And cyclic amines such as pyridine, methyl-substituted pyridine, hydroxy-substituted pyridine, quinoline, methyl-substituted quinoline, hydroxy-substituted quinoline, isoquinoline, methyl-substituted isoquinoline, hydroxy-substituted isoquinoline, imidazole, methyl-substituted imidazole, and hydroxy-substituted imidazole. . The imidation catalyst is preferably one or more selected from N, N-dimethylaniline, o-, m-, p-hydroxyaniline, o-, m-, p-hydroxypyridine, and isoquinoline. .

  The addition amount of the silane coupling agent is usually 0 to 20% by weight, preferably 0.1 to 10% by weight, based on the total weight of the polyamic acid or its derivative.

  The amount of the imidation catalyst added is usually 0.01 to 5 equivalents, preferably 0.05 to 3 equivalents, relative to the carbonyl group of the polyamic acid or derivative thereof.

  The addition amount of other additives varies depending on the application, but is usually 0 to 100% by weight, preferably 0.1 to 50% by weight, based on the total weight of the polyamic acid or derivative thereof.

  Further, for example, the liquid crystal aligning agent of the present invention is an acrylic acid polymer, an acrylate polymer, and a tetracarboxylic acid as long as the effects of the present invention are not impaired (preferably within 20% by weight of the polyamic acid or its derivative). It may further contain other polymer components such as polyamideimide which is a reaction product of acid dianhydride, dicarboxylic acid or its derivative and diamine.

  For example, the liquid crystal aligning agent of this invention may further contain the solvent from a viewpoint of the applicability | paintability of a liquid crystal aligning agent, and the adjustment of the density | concentration of the said polyamic acid or its derivative (s). The solvent can be applied without any particular limitation as long as it has a capability of dissolving the polymer component. The said solvent contains the solvent normally used in the manufacturing process and use surface of polymer components, such as a polyamic acid and a soluble polyimide, and can be suitably selected according to the intended purpose. The solvent may be one type or a mixed solvent of two or more types.

  Examples of the solvent include a parent solvent for the polyamic acid or a derivative thereof, and other solvents for the purpose of improving coatability.

  Examples of the aprotic polar organic solvent that is a parent solvent for polyamic acid or its derivatives include N-methyl-2-pyrrolidone, dimethylimidazolidinone, N-methylcaprolactam, N-methylpropionamide, N, N-dimethylacetamide. , Dimethyl sulfoxide, N, N-dimethylformamide, N, N-diethylformamide, diethylacetamide, γ-butyrolactone, and other lactones.

  Examples of other solvents for the purpose of improving coating properties include alkyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, ethylene glycol monoalkyl ethers such as ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, etc. Diethylene glycol monoalkyl ether, ethylene glycol monoalkyl or phenyl acetate, triethylene glycol monoalkyl ether, propylene glycol monoalkyl ether such as propylene glycol monomethyl ether, propylene glycol monobutyl ether, dialkyl malonate such as diethyl malonate, dipropylene glycol monomethyl Dipropylene glycol monoalkyl ethers such as ethers and esters such as these acetates Compounds, and the like.

  Among these, the solvent is N-methyl-2-pyrrolidone, dimethylimidazolidinone, γ-butyrolactone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether, and dipropylene glycol. Monomethyl ether is particularly preferred.

  The concentration of the polyamic acid in the alignment agent of the present invention is preferably 0.1 to 40% by weight. When this aligning agent is applied to the substrate, an operation of diluting the contained polyamic acid with a solvent in advance may be required to adjust the film thickness.

  The solid content concentration in the alignment agent of the present invention is not particularly limited, and an optimum value may be selected according to the following various coating methods. Usually, in order to suppress unevenness and pinholes at the time of application, the content is preferably 0.1 to 30% by weight, more preferably 1 to 10% by weight, based on the varnish weight.

  The liquid crystal alignment film of the present invention will be described in detail. The liquid crystal alignment film of this invention is a film | membrane formed by heating the coating film of the liquid crystal aligning agent of this invention mentioned above. The liquid crystal alignment film of the present invention can be obtained by an ordinary method for producing a liquid crystal alignment film from a liquid crystal aligning agent. For example, the liquid crystal alignment film of the present invention can be obtained through a step of forming a coating film of the liquid crystal alignment agent of the present invention, a step of drying by heating, and a step of baking by heating. About the liquid crystal aligning film of this invention, you may give anisotropy by rubbing the film | membrane obtained through a heat-drying process and a heat-firing process as needed later as needed. Or as needed, you may provide anisotropy by irradiating light after a coating-film process and a heat drying process, or irradiating light after a heat-firing process. Moreover, you may use as a liquid crystal aligning film for VA which does not perform a rubbing process.

A coating film can be formed by apply | coating the liquid crystal aligning agent of this invention to the board | substrate in a liquid crystal display element similarly to preparation of a normal liquid crystal aligning film. Examples of the substrate include a glass substrate in which electrodes such as ITO (Indium Tin Oxide), IZO (In ₂ O ₃ —ZnO), and IGZO (In—Ga—ZnO ₄ ) electrodes and a color filter may be provided. .

  As a method for applying a liquid crystal aligning agent to a substrate, a spinner method, a printing method, a dipping method, a dropping method, an ink jet method and the like are generally known. These methods are similarly applicable in the present invention.

  As the heat drying step, a method of heat treatment in an oven or an infrared furnace, a method of heat treatment on a hot plate, and the like are generally known. The heat drying step is preferably performed at a temperature within a range where the solvent can be evaporated, and more preferably at a temperature relatively lower than the temperature in the heat baking step. Specifically, the heat drying temperature is preferably in the range of 30 ° C to 150 ° C, and more preferably in the range of 50 ° C to 120 ° C.

  The heating and baking step can be performed under conditions necessary for the polyamic acid or its derivative to exhibit a dehydration / ring-closure reaction. As for the baking of the coating film, a method of heat treatment in an oven or an infrared furnace, a method of heat treatment on a hot plate, and the like are generally known. These methods are equally applicable in the present invention. In general, it is preferably performed at a temperature of about 100 to 300 ° C for 1 minute to 3 hours, more preferably 120 to 280 ° C, and further preferably 150 to 250 ° C.

  In the method for forming a liquid crystal alignment film of the present invention, as a means for imparting anisotropy to the alignment film in order to align the liquid crystal in one direction with respect to the horizontal and / or vertical direction, a rubbing method, a photo alignment method, or the like is known. The forming method can be suitably used. In particular, a photo-alignment method can be suitably used.

  The liquid crystal alignment film of the present invention using the rubbing method includes a step of applying the liquid crystal alignment agent of the present invention to a substrate, a step of heating and drying the substrate coated with the alignment agent, a step of heating and baking the film, Can be formed through a rubbing process.

  The rubbing treatment can be performed in the same manner as the rubbing treatment for the alignment treatment of a normal liquid crystal alignment film, and may be any conditions as long as sufficient retardation is obtained in the liquid crystal alignment film of the present invention. The preferable conditions are a push-in amount of 0.2 to 0.8 mm, a stage moving speed of 5 to 250 mm / sec, and a roller rotation speed of 500 to 2,000 rpm.

  The method for forming the liquid crystal alignment film of the present invention by the photo-alignment method will be described in detail. The liquid crystal alignment film of the present invention using the photo-alignment method gives the film anisotropy by irradiating with linearly polarized light or non-polarized light after the coating film is heated and dried, and the film is heated and fired. Can be formed. Or it can form by irradiating the linearly polarized light or non-polarized light of a radiation, after heat-drying a coating film and heat-baking. From the viewpoint of orientation, the radiation irradiation step is preferably performed before the heating and baking step.

  Furthermore, in order to raise the liquid crystal aligning ability of a liquid crystal aligning film, a linearly polarized light or non-polarized light can be irradiated while heating a coating film. Irradiation may be performed in a step of heating and drying the coating film or a step of heating and baking, or may be performed between the heating and drying step and the heating and baking step. The heating and drying temperature in this step is preferably in the range of 30 ° C to 150 ° C, and more preferably in the range of 50 ° C to 120 ° C. Moreover, it is preferable that the heat-firing temperature in this process is the range of 30 degreeC-300 degreeC, Furthermore, it is preferable that it is the range of 50 degreeC-250 degreeC.

  As the radiation, for example, ultraviolet light or visible light including light having a wavelength of 150 to 800 nm can be used, but ultraviolet light including light of 300 to 400 nm is preferable. Further, linearly polarized light or non-polarized light can be used. These lights are not particularly limited as long as they can impart a liquid crystal alignment ability to the coating film, but linearly polarized light is preferable when it is desired to develop a strong alignment regulating force for liquid crystals.

The liquid crystal alignment film of the present invention can exhibit high liquid crystal alignment ability even with low energy light irradiation. Dose of linearly polarized light in the irradiation step is preferably from 0.05~20J / cm ^2, more preferably 0.5~10J / cm ^2. The wavelength of linearly polarized light is preferably 200 to 400 nm, and more preferably 300 to 400 nm. Although the irradiation angle with respect to the film surface of linearly polarized light is not particularly limited, it is preferable from the viewpoint of shortening the alignment processing time that it is as perpendicular as possible to the film surface in order to develop a strong alignment regulating force for the liquid crystal. The liquid crystal alignment film of the present invention can align liquid crystal in a direction perpendicular to the polarization direction of linearly polarized light by irradiating linearly polarized light.

When the pretilt angle is to be expressed, the light applied to the film may be linearly polarized light or non-polarized light as described above. Dose of light applied to the film when it is desired to express a pre-tilt angle is preferably from 0.05~20J / cm ^2, particularly preferably 0.5~10J / cm ^2, its wavelength is 250 400 nm is preferable, and 300 to 380 nm is particularly preferable. When it is desired to develop a pretilt angle, the irradiation angle of the light applied to the film with respect to the film surface is not particularly limited, but is preferably 30 to 60 degrees from the viewpoint of shortening the alignment processing time.

  The light source used in the process of irradiating linearly polarized light or non-polarized light includes ultra-high pressure mercury lamp, high pressure mercury lamp, low pressure mercury lamp, deep UV lamp, halogen lamp, metal halide lamp, high power metal halide lamp, xenon lamp, mercury A xenon lamp, an excimer lamp, a KrF excimer laser, a fluorescent lamp, an LED lamp, a sodium lamp, a microwave excitation electrodeless lamp, and the like can be used without limitation.

  The liquid crystal alignment film of the present invention can be suitably obtained by a method that further includes steps other than the steps described above. For example, the liquid crystal alignment film of the present invention does not require a process of cleaning the film after baking or radiation irradiation with a cleaning liquid, but a cleaning process can be provided for convenience of other processes.

  Examples of the cleaning method using the cleaning liquid include brushing, jet spray, steam cleaning, and ultrasonic cleaning. These methods may be performed alone or in combination. The cleaning liquid is pure water, various alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, aromatic hydrocarbons such as benzene, toluene, xylene, halogen solvents such as methylene chloride, and ketones such as acetone and methyl ethyl ketone. Although it can be used, it is not limited to these. Of course, these cleaning liquids are sufficiently purified and have few impurities. Such a cleaning method can also be applied to the cleaning step in the formation of the liquid crystal alignment film of the present invention.

In order to enhance the liquid crystal alignment ability of the liquid crystal alignment film of the present invention, annealing treatment with heat or light can be used before or after the heating and baking step, before or after the rubbing step, or before or after irradiation with polarized or non-polarized radiation. . In the annealing treatment, the annealing temperature is 30 to 180 ° C., preferably 50 to 150 ° C., and the time is preferably 1 minute to 2 hours. Examples of the annealing light used for the annealing treatment include a UV lamp, a fluorescent lamp, and an LED lamp. The light irradiation amount is preferably 0.3 to 10 J / cm ² .

  Although the film thickness of the liquid crystal aligning film of this invention is not specifically limited, It is preferable that it is 10-300 nm, and it is more preferable that it is 30-150 nm. The film thickness of the liquid crystal alignment film of the present invention can be measured by a known film thickness measuring device such as a step meter or an ellipsometer.

  The liquid crystal alignment film of the present invention is particularly characterized by having a large alignment anisotropy. The magnitude of such anisotropy can be evaluated by a method using polarized IR described in JP-A-2005-275364. Further, as shown in the following examples, evaluation can also be made by a method using ellipsometry. When the alignment film of the present invention is used as an alignment film for a liquid crystal composition, a material having a larger film anisotropy is considered to have a large alignment regulating force for the liquid crystal composition.

  The liquid crystal alignment film of the present invention can be used for alignment control of an optical compensation material and all other liquid crystal materials in addition to the alignment use of a liquid crystal composition for a liquid crystal display. Further, since the alignment film of the present invention has large anisotropy, it can be used alone for an optical compensator application.

  The present invention is formed on a pair of substrates disposed opposite to each other, an electrode formed on one or both of the surfaces opposed to each of the pair of substrates, and a surface opposed to each of the pair of substrates. A liquid crystal display element having a liquid crystal alignment film formed and a liquid crystal layer formed between the pair of substrates, wherein the liquid crystal alignment film is the alignment film of the present invention.

  The electrode is not particularly limited as long as it is an electrode formed on one surface of the substrate. Examples of such electrodes include ITO and metal vapor deposition films. Further, the electrode may be formed on the entire surface of one surface of the substrate, or may be formed in a desired shape that is patterned, for example. Examples of the desired shape of the electrode include a comb shape or a zigzag structure. The electrode may be formed on one of the pair of substrates, or may be formed on both substrates. The form of electrode formation varies depending on the type of liquid crystal display element. For example, in the case of an IPS liquid crystal display element, an electrode is disposed on one of the pair of substrates, and in the case of other liquid crystal display elements, the electrodes of the pair of substrates are arranged. Electrodes are arranged on both sides. The liquid crystal alignment film is formed on the substrate or electrode.

  The liquid crystal layer is formed in such a manner that the liquid crystal composition is sandwiched between the pair of substrates facing each other on which the liquid crystal alignment film is formed. In the formation of the liquid crystal layer, a spacer such as fine particles or a resin sheet that is interposed between the pair of substrates to form an appropriate interval can be used as necessary.

  The liquid crystal composition is not particularly limited, and various liquid crystal compositions having a positive or negative dielectric anisotropy can be used. Preferred liquid crystal compositions having a positive dielectric anisotropy include Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Laid-Open No. 5-501735, Japanese Patent Laid-Open No. 8-157826, and Japanese Patent Laid-Open No. 8-231960. JP-A-9-241644 (EP88272A1 specification), JP-A-9-302346 (EP806466A1 specification), JP-A-8-199168 (EP722998A1 specification), JP-A-9-235552, JP Japanese Laid-Open Patent Publication Nos. 9-255958, 9-241463 (EP882711A1), 10-204016 (EP844229A1), 10-204436, 10-231482, and JP 2000-087040, JP 2001-48 It disclosed in 22 JP liquid crystal composition and the like are.

  Preferred liquid crystal compositions having a negative dielectric anisotropy include JP-A-57-114532, JP-A-2-4725, JP-A-4-222485, JP-A-8-40953, JP-A-8-104869, JP-A-10-168076, JP-A-10-168453, JP-A-10-236989, JP-A-10-236990, JP-A-10-236992, JP-A-10- No. 236993, JP-A-10-236994, JP-A-10-237000, JP-A-10-237004, JP-A-10-237024, JP-A-10-237035, JP-A-10-237075 Publication, Unexamined-Japanese-Patent No. 10-237076, Unexamined-Japanese-Patent No. 10-237448 (EP967261A1 specification), Japanese Unexamined Patent Publication Nos. 10-287874, 10-287875, 10-291945, 11-029581, 11-080049, 2000-256307, 2001 Examples thereof include liquid crystal compositions disclosed in Japanese Patent Application Publication No. -019655, Japanese Patent Application Laid-Open No. 2001-072626, Japanese Patent Application Laid-Open No. 2001-192657, and the like.

  One or more optically active compounds may be added to a liquid crystal composition having a positive or negative dielectric anisotropy.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these. The evaluation method of the liquid crystal display element in an Example is as follows.
<Weight average molecular weight (Mw)>
The weight average molecular weight of the polyamic acid was measured by GPC method using a 2695 separation module / 2414 differential refractometer (manufactured by Waters) and calculated by polystyrene conversion. The obtained polyamic acid was diluted with a phosphoric acid-DMF mixed solution (phosphoric acid / DMF = 0.6 / 100: weight ratio) so that the polyamic acid concentration was about 2% by weight. The column was HSPgel RT MB-M (manufactured by Waters), and measurement was performed under the conditions of a column temperature of 50 ° C. and a flow rate of 0.40 mL / min using the mixed solution as a developing agent. As the standard polystyrene, TSK standard polystyrene manufactured by Tosoh Corporation was used.
<Measurement of retardation and thickness of alignment film>
It was determined using a spectroscopic ellipsometer M-2000U (manufactured by JAWoollam Co. Inc.). In this example, the retardation value of the film increases in proportion to the degree of orientation of the polymer main chain. That is, those having a large retardation value have a large degree of orientation.
<Measurement of transmittance of alignment film>
Using a UV-Vis spectrum measurement device (JASCO V-660), the transmittance of the alignment film was measured. A glass substrate on which no alignment film was formed was used as a reference.

The solvents and additives used in the examples are as follows.
<Solvent>
N-methyl-2-pyrrolidone: NMP
Butyl cellosolve (ethylene glycol monobutyl ether): BC
<Additives>
Additive (Ad1): Bis [4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl] methane Additive (Ad2): N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane additive (Ad3): 3-aminopropyltriethoxysilane additive (Ad4): 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane additive (Ad5) ): 1,3-bis (4,5-dihydro-2-oxazolyl) benzene

<1. Synthesis of polyamic acid>
[Synthesis Example 1]
In a 50 mL brown four-necked flask equipped with a thermometer, stirrer, raw material charging inlet, and nitrogen gas inlet, 0.446 g of diamine in which m is 1 in formula (DI-5-1) and 13.5 g of dehydrated NMP are placed. The solution was stirred and dissolved under a dry nitrogen stream. Next, 1.054 g of acid dianhydride (1-a) (manufactured by Nippon Seika Co., Ltd.) and 5.0 g of dehydrated NMP were added, and stirring was continued at room temperature for 24 hours. BC5g was added to this reaction solution, and the polyamic acid solution whose polymer solid content concentration is 6 weight% was obtained. This polyamic acid solution is designated as PA1. The weight average molecular weight of the polyamic acid contained in PA1 was 74,000.

[Synthesis Examples 2-37]
A polyamic acid solution (PA2) having a polymer solid content concentration of 6% by weight according to Synthesis Example 1 except that tetracarboxylic dianhydride and diamine were changed as shown in Table 1-1 and Table 1-2. ~ (PA37) was prepared. The measurement results of the weight average molecular weight of the obtained polyamic acid including the results of Synthesis Example 1 are summarized in Table 1-1 and Table 1-2.

  The additive (Ad1) was added to the polyamic acid solution (PA1) having a polymer solid content concentration of 6% by weight prepared in Synthesis Example 1 at a ratio of 5% by weight per polymer weight. The obtained polyamic acid solution is designated as PA38.

  As shown in Table 2, additives (Ad2) to (Ad5) were added to the polyamic acid solution at a ratio shown in the table to prepare polyamic acid solutions (PA39) to (PA43).

<2. Measurement substrate fabrication method and transmittance / retardation measurement method>
[Example 1]
A mixed solvent of NMP / BC = 4/1 (weight ratio) was added to the polyamic acid solution (PA1) having a polymer solid concentration of 1% by weight prepared in Synthesis Example 1, and diluted to a polymer solids concentration of 4% by weight. A liquid crystal aligning agent was used. The liquid crystal aligning agent was applied to a glass substrate with a spinner (manufactured by Mikasa Co., Ltd., spin coater (1H-DX2)). In addition, including the following examples and comparative examples, the rotation speed of the spinner was adjusted according to the viscosity of the liquid crystal aligning agent so that the alignment film had the following film thickness. After coating, after heating and drying at 70 ° C. for 80 seconds on a hot plate (manufactured by AS ONE, EC hot plate (EC-1200N)), a clean oven (manufactured by ESPEC Corporation, clean oven (PVHC-231)) In this, a heat treatment was performed at 230 ° C. for 15 minutes to form an alignment film having a thickness of 100 ± 10 nm. When the transmittance of the obtained substrate was measured, the transmittance at a wavelength of 300 nm was 79.9%.
Next, using the rubbing treatment apparatus manufactured by Iinuma Gauge Corporation, the obtained liquid crystal alignment film was 0.20 mm in the amount of pushing the rubbing cloth (hair length 1.8 mm: rayon), and the stage moving speed was 60 mm / The rubbing process was performed on the condition that the roller rotation speed was 1,000 rpm for sec. It was 0.26 nm when the retardation of the obtained board | substrate was measured.

[Examples 2 to 29]
A mixed solvent of NMP / BC = 4/1 (weight ratio) is added to each of the polyamic acid solutions PA2 to PA25 and PA38 to PA41 having a polymer solid concentration of 6% by weight, and diluted to a polymer solids concentration of 4% by weight. A liquid crystal aligning agent was used. Using the obtained liquid crystal aligning agent, a measurement substrate was prepared by a method according to Example 1, and transmittance and retardation were measured. It was set as Examples 2-29 in order according to polyamic acid solution PA2-PA25 and PA38-PA41.

[Comparative Example 1]
A mixed solvent of NMP / BC = 4/1 (weight ratio) was added to the polyamic acid solution (PA36) having a polymer solid content concentration of 6% by weight prepared in Synthesis Example 36, and diluted to a polymer solid content concentration of 4% by weight. A liquid crystal aligning agent was used. Using the obtained liquid crystal aligning agent, a measurement substrate was prepared by a method according to Example 1, and transmittance and retardation were measured. The results are summarized in Table 3 together with the results of Examples 1 to 29.

  By comparison with Examples 1 to 29 and Comparative Example 1, the alignment film of the present invention is very useful for improving retardation, imparting high alignment to liquid crystal, and greatly improving the transmittance. I understand that

[Example 30]
A mixed solvent of NMP / BC = 4/1 (weight ratio) was added to the polyamic acid solution (PA26) having a polymer solid concentration of 1 wt% prepared in Synthesis Example 26, and diluted to a polymer solid concentration of 4 wt%. A liquid crystal aligning agent was used. The liquid crystal aligning agent was applied to a glass substrate with a spinner (manufactured by Mikasa Co., Ltd., spin coater (1H-DX2)). In addition, including the following examples and comparative examples, the rotation speed of the spinner was adjusted according to the viscosity of the liquid crystal aligning agent so that the alignment film had the following film thickness. After the coating, it was heated and dried at 70 ° C. for 80 seconds on a hot plate (manufactured by AS ONE, EC hot plate (EC-1200N)). Next, using a multi-light ML-501C / B manufactured by Ushio Electric Co., Ltd., the substrate was irradiated with linearly polarized ultraviolet light from the vertical direction through the polarizing plate. The exposure energy at this time is 5.0 ± 0.1 J / cm ² at a wavelength of 365 nm by measuring the amount of light using a UV integrated light meter UIT-150 (receiver UVD-S365) manufactured by USHIO INC. The exposure time was adjusted. The irradiation of ultraviolet rays was performed in air at room temperature by covering the entire apparatus with an ultraviolet ray preventing film. Subsequently, the film was heat-treated at 230 ° C. for 15 minutes in a clean oven (manufactured by ESPEC Corporation, clean oven (PVHC-231)) to form an alignment film having a thickness of 100 ± 10 nm. When the transmittance of the obtained substrate was measured, the transmittance at a wavelength of 300 nm was 63.0%. It was 3.26 nm when the retardation of the obtained board | substrate was measured.

[Examples 31 to 41]
A mixed solvent of NMP / BC = 4/1 (weight ratio) was added to each of the polyamic acid solutions PA27 to PA35 and PA42 to PA43 having a polymer solid concentration of 6% by weight, and diluted to a polymer solids concentration of 4% by weight. A liquid crystal aligning agent was used. Using the obtained liquid crystal aligning agent, a measurement substrate was prepared by a method according to Example 30, and transmittance and retardation were measured. It was set as Examples 31-41 in order according to polyamic acid solution PA27-PA35 and PA42-PA43.

[Comparative Example 2]
A mixed solvent of NMP / BC = 4/1 (weight ratio) was added to the polyamic acid solution (PA37) having a polymer solid concentration of 6% by weight prepared in Synthesis Example 37, and diluted to a polymer solids concentration of 4% by weight. A liquid crystal aligning agent was used. Using the obtained liquid crystal aligning agent, a measurement substrate was prepared by a method according to Example 30, and transmittance and retardation were measured. The results of Examples 30 to 41 are summarized in Table 4-1.

[Example 42]
A mixed solvent of NMP / BC = 4/1 (weight ratio) was added to the polyamic acid solution (PA26) having a polymer solid concentration of 1 wt% prepared in Synthesis Example 26, and diluted to a polymer solid concentration of 4 wt%. A liquid crystal aligning agent was used. The liquid crystal aligning agent was applied to a glass substrate with a spinner (manufactured by Mikasa Co., Ltd., spin coater (1H-DX2)). In addition, including the following examples and comparative examples, the rotation speed of the spinner was adjusted according to the viscosity of the liquid crystal aligning agent so that the alignment film had the following film thickness. After the coating, it was heated and dried at 70 ° C. for 80 seconds on a hot plate (manufactured by AS ONE, EC hot plate (EC-1200N)). Next, using a UV lamp (UVL-1500M2-N1) manufactured by Ushio Electric Co., Ltd., the substrate was irradiated with linearly polarized ultraviolet light from the vertical direction through the polarizing plate. The exposure energy at this time is 5.0 ± 0.1 J / cm ² at a wavelength of 365 nm by measuring the amount of light using a UV integrated light meter UIT-150 (receiver UVD-S365) manufactured by USHIO INC. The exposure time was adjusted. The irradiation of ultraviolet rays was performed in air at room temperature by covering the entire apparatus with an ultraviolet ray preventing film. Subsequently, the film was heat-treated at 230 ° C. for 15 minutes in a clean oven (manufactured by ESPEC Corporation, clean oven (PVHC-231)) to form an alignment film having a thickness of 100 ± 10 nm. Finally, the heated substrate was annealed at 120 ° C. for 30 minutes in a clean oven. When the transmittance of the obtained substrate was measured, the transmittance at a wavelength of 300 nm was 63.1%. It was 3.62 nm when the retardation of the obtained board | substrate was measured.

[Examples 43 to 45]
A mixed solvent of NMP / BC = 4/1 (weight ratio) is added to each of the polyamic acid solutions PA27, PA33, and PA34 having a polymer solid content concentration of 6% by weight, and the liquid crystal is diluted to a polymer solid content concentration of 4% by weight. An aligning agent was used. Using the obtained liquid crystal aligning agent, a measurement substrate was prepared by a method according to Example 42, and transmittance and retardation were measured. It was set as Examples 43-45 in order according to polyamic acid solution PA27, PA33, and PA34.

[Comparative Example 3]
A mixed solvent of NMP / BC = 4/1 (weight ratio) was added to the polyamic acid solution (PA37) having a polymer solid concentration of 6% by weight prepared in Synthesis Example 37, and diluted to a polymer solids concentration of 4% by weight. A liquid crystal aligning agent was used. Using the obtained liquid crystal aligning agent, a measurement substrate was prepared by a method according to Example 42, and transmittance and retardation were measured. The results of Examples 42 to 45 are summarized in Table 4-2.

[Example 46]
A mixed solvent of NMP / BC = 4/1 (weight ratio) was added to the polyamic acid solution (PA26) having a polymer solid concentration of 1 wt% prepared in Synthesis Example 26, and diluted to a polymer solid concentration of 4 wt%. A liquid crystal aligning agent was used. The liquid crystal aligning agent was applied to a glass substrate with a spinner (manufactured by Mikasa Co., Ltd., spin coater (1H-DX2)). In addition, including the following examples and comparative examples, the rotation speed of the spinner was adjusted according to the viscosity of the liquid crystal aligning agent so that the alignment film had the following film thickness. After the coating, it was heated and dried at 70 ° C. for 80 seconds on a hot plate (manufactured by AS ONE, EC hot plate (EC-1200N)). Next, using a multi-light ML-501C / B manufactured by Ushio Electric Co., Ltd., the substrate was irradiated with linearly polarized ultraviolet light from the vertical direction through the polarizing plate. The exposure energy at this time is 5.0 ± 0.1 J / cm ² at a wavelength of 365 nm by measuring the amount of light using a UV integrated light meter UIT-150 (receiver UVD-S365) manufactured by USHIO INC. The exposure time was adjusted. During the UV exposure, the temperature of the substrate was heated to 50 ° C. The irradiation of ultraviolet rays was performed in air at room temperature by covering the entire apparatus with an ultraviolet ray preventing film. Subsequently, the film was heat-treated at 230 ° C. for 15 minutes in a clean oven (manufactured by ESPEC Corporation, clean oven (PVHC-231)) to form an alignment film having a thickness of 100 ± 10 nm. When the transmittance of the obtained substrate was measured, the transmittance at a wavelength of 300 nm was 63.0%. When the retardation of the obtained substrate was measured, it was 3.69 nm.

[Examples 47 to 49]
A mixed solvent of NMP / BC = 4/1 (weight ratio) is added to each of the polyamic acid solutions PA27, PA33, and PA34 having a polymer solid content concentration of 6% by weight, and the liquid crystal is diluted to a polymer solid content concentration of 4% by weight. An aligning agent was used. Using the obtained liquid crystal aligning agent, a measurement substrate was produced by a method according to Example 46, and transmittance and retardation were measured. It was set as Examples 47-49 in order according to polyamic acid solution PA27, PA33, and PA34.

[Comparative Example 4]
A mixed solvent of NMP / BC = 4/1 (weight ratio) was added to the polyamic acid solution (PA37) having a polymer solid concentration of 6% by weight prepared in Synthesis Example 37, and diluted to a polymer solids concentration of 4% by weight. A liquid crystal aligning agent was used. Using the obtained liquid crystal aligning agent, a measurement substrate was produced by a method according to Example 46, and transmittance and retardation were measured. Together with the results of Examples 46 to 49, the results are summarized in Table 4-3.

  By comparison with Examples 30 to 49 and Comparative Examples 2 to 4, the photo-alignment film of the present invention is very useful for improving retardation, imparting high orientation to liquid crystals, and having a high transmittance. It turns out that it is greatly improved.

  If a polyamic acid using a specific alicyclic tetracarboxylic dianhydride of the present invention and a derivative thereof are used as a liquid crystal aligning agent, an alignment film having excellent liquid crystal molecule orientation and high transmittance can be provided. . And the liquid crystal display element excellent in the display characteristic which has this alignment film can be provided.

Claims (20)

A polyamic acid or a derivative thereof obtained by reacting a tetracarboxylic dianhydride containing at least a tetracarboxylic dianhydride represented by the following formula (1) with a diamine.

The tetracarboxylic dianhydride represented by Formula (1) is at least one of the tetracarboxylic dianhydrides represented by the following formula (1-a) or (1-b). A polyamic acid or a derivative thereof.

The tetracarboxylic dianhydride contains at least one selected from the group of tetracarboxylic dianhydrides represented by the following formulas (AN-I) to (AN-VII). A polyamic acid or a derivative thereof.

In formulas (AN-I), (AN-IV) and (AN-V), X is independently a single bond or —CH ₂ —;
In the formula (AN-II), G represents a single bond, alkylene having 1 to 20 carbon atoms, —CO—, —O—, —S—, —SO ₂ —, —C (CH ₃ ) ₂ —, or —C. (CF ₃ ) ₂ —;
In the formulas (AN-II) to (AN-IV), Y is independently one selected from the following group of trivalent groups;

Any hydrogen in these groups may be replaced by methyl, ethyl or phenyl;
In the formulas (AN-III) to (AN-V), the ring A is a monocyclic hydrocarbon group having 3 to 10 carbon atoms or a condensed polycyclic hydrocarbon group having 6 to 30 carbon atoms. Any hydrogen in may be replaced by methyl, ethyl or phenyl, and the bond on the ring is connected to any carbon constituting the ring, and the two bonds are connected to the same carbon May be;
In the formula (AN-VI), X ¹⁰ is alkylene having 2 to 6 carbons;
Me is methyl;
Ph is phenyl;
In formula (AN-VII), G ¹⁰ is independently —O—, —COO— or —OCO—; and
r is independently 0 or 1. Tetracarboxylic dianhydride is represented by the following formula (AN-1-1), (AN-1-13), (AN-2-1), (AN-3-1), (AN-3-2), Contains at least one selected from the group consisting of (AN-4-5), (AN-4-17), (AN-7-2), (AN-10), and (AN-11-3) The polyamic acid or derivative thereof according to any one of claims 1 to 3.

In formula (AN-4-17), m is an integer of 1-12. The polyamic acid or derivative thereof according to any one of claims 1 to 4, wherein the diamine contains at least one selected from the group consisting of the following formulas (DI-1) to (DI-17).

In the formula (DI-1), m is an integer of 1 to 12;
In (DI-3) and (DI-5) to (DI-7), G ²¹ is independently a single bond, —NH—, —O—, —S—, —S—S—, —SO ₂ —. , —CO—, —CONH—, —CONCH ₃ —, —NHCO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, — (CH ₂ ) _{m ′} —, —O— (CH _{2) m '-O -, -} N (CH 3) - (CH 2) k -N (CH 3) -, or -S- (CH _{2) m'} is -S-, m 'is independently An integer from 1 to 12, k is an integer from 1 to 5;
In (DI-6) and (DI-7), G ²² is independently a single bond, —O—, —S—, —CO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) _2. -Or alkylene having 1 to 10 carbon atoms;
In the formulas (DI-2) to (DI-7), any —H of the cyclohexane ring and the benzene ring is —F, —CH ₃ , —OH, —CF ₃ , —CO ₂ H, —CONH ₂ , or In the formula (DI-4), the following formulas (DI-4-a) to (DI-4-c) may be substituted,

In formulas (DI-4-a) and (DI-4-b), R ²⁰ is independently —H or —CH ₃ ;
In formulas (DI-2) to (DI-7), a group whose bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary; and
The bonding position of —NH ₂ to the cyclohexane ring or the benzene ring is an arbitrary position excluding the bonding position of G ²¹ or G ²² .

In formula (DI-8), R ²¹ and R ²² are independently alkyl having 1 to 3 carbons or phenyl;
G ²³ is independently alkylene having 1 to 6 carbons, phenylene or alkyl-substituted phenylene;
n is an integer from 1 to 10;
In formula (DI-9), R ²³ is independently alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons or —Cl;
p is independently an integer from 0 to 3;
q is an integer from 0 to 4;
In the formula (DI-10), R ²⁴ is —H, alkyl having 1 to 4 carbons, phenyl, or benzyl;
In the formula (DI-11), G ²⁴ is —CH ₂ — or —NH—;
In the formula (DI-12), G ²⁵ is a single bond, alkylene having 2 to 6 carbons or 1,4-phenylene;
r is 0 or 1;
In formula (DI-12), a group whose bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary; and
In formulas (DI-9), (DI-11) and (DI-12), the bonding position of —NH ₂ bonded to the benzene ring is an arbitrary position;

In the formula (DI-13), G ²⁶ represents a single bond, —O—, —COO—, —OCO—, —CO—, —CONH—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—. , -OCF ₂ -, or - (CH _{2) m '-} it is and, m' is an integer from 1 to 12;
R ²⁵ is alkyl having 3 to 20 carbons, phenyl, a group having a steroid skeleton, or a group represented by the following formula (DI-13-a). In this alkyl, any —H is —F Any —CH ₂ — may be replaced by —O—, —CH═CH— or —C≡C—, and —H of this phenyl is —F, —CH ₃ , _{-OCH 3, -OCH 2 F, -OCHF} 2, -OCF 3, alkyl having 3 to 20 carbon atoms, or may be replaced by alkoxy having 3 to 20 carbon atoms, -H of cyclohexyl 3 carbon atoms Which may be replaced by ˜20 alkyl or C 3-20 alkoxy, and indicates that the bonding position of —NH ₂ bonded to the benzene ring is an arbitrary position in the ring;

In the formula (DI-13-a), G ²⁷ , G ^28, and G ²⁹ each represent a bonding group, and these are each independently a single bond or alkylene having 1 to 12 carbons, and one or more — CH ₂ — may be replaced by —O—, —COO—, —OCO—, —CONH—, —CH═CH—;
Ring B ²¹ , Ring B ²² , Ring B ²³ , and Ring B ²⁴ are independently 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2, 5-diyl, pyridine-2,5-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, or anthracene-9,10 -Diyl;
In ring B ²¹ , ring B ²² , ring B ²³ , and ring B ²⁴ , any —H may be replaced by —F or —CH ₃ ;
s, t and u are independently integers from 0 to 2 and their sum is 1 to 5;
when s, t or u is 2, the two linking groups in each bracket may be the same or different and the two rings may be the same or different;
R ²⁶ represents —F, —OH, alkyl having 1 to 30 carbon atoms, fluorine-substituted alkyl having 1 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms, —CN, —OCH ₂ F, —OCHF ₂ , or —OCF. _And any —CH ₂ — in the alkyl having 1 to 30 carbon atoms may be replaced by a divalent group represented by the following formula (DI-13-b);

In the formula (DI-13-b), R ²⁷ and R ²⁸ are independently alkyl having 1 to 3 carbons;
v is an integer from 1 to 6;

In formula (DI-14) and formula (DI-15), G ³⁰ is independently a single bond, —CO— or —CH ₂ —;
R ²⁹ is independently —H or —CH ₃ ;
R ³⁰ is —H, alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons;
One -H of the benzene ring in formula (DI-15) may be replaced by alkyl having 1 to 20 carbons or phenyl;
In formula (DI-14) and formula (DI-15), a group whose bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary;
Bonded to the benzene ring -NH ₂ indicates that the binding position in the ring is optional;

In formula (DI-16) and formula (DI-17), G ³¹ is independently —O— or alkylene having 1 to 6 carbons;
G ³² is a single bond or alkylene having 1 to 3 carbon atoms;
R ³¹ is —H or alkyl having 1 to 20 carbons, and any —CH ₂ — in the alkyl may be replaced by —O—, —CH═CH— or —C≡C—;
R ³² is alkyl having 6 to 22 carbons;
R ³³ is —H or C 1-22 alkyl;
Ring B ²⁵ is 1,4-phenylene or 1,4-cyclohexylene;
r is 0 or 1; and
-NH ₂ bonded to the benzene ring indicates that the binding position in the ring is optional. The polyamic acid or derivative thereof according to any one of claims 1 to 5, wherein the diamine contains at least one dihydrazide selected from the following formulas (2-a) to (2-c).

In the formula (2-a), G represents a single bond, alkylene having 1 to 20 carbon atoms, —CO—, —O—, —S—, —SO ₂ —, —C (CH ₃ ) ₂ —, or —C. (CF ₃ ) ₂ —;
In formula (2-b), ring B is a cyclohexane ring, a benzene ring or a naphthalene ring, and any hydrogen of this group may be replaced with methyl, ethyl, or phenyl;
In formula (2-c), each ring C is independently a cyclohexane ring or a benzene ring, and any hydrogen of this group may be replaced by methyl, ethyl, or phenyl; Y is a single bond, carbon It is alkylene of formula 1 to 20, —CO—, —O—, —S—, —SO ₂ —, —C (CH ₃ ) ₂ —, or —C (CF ₃ ) ₂ —. The dihydrazide is represented by the following formulas (2-a-1) to (2-a-2), (2-b-1) to (2-b-3) or (2-c-1) to (2-c). The polyamic acid or derivative thereof according to claim 6, which is at least one dihydrazide selected from -6).

In formula (2-a-2), m is an integer of 1-12. The polyamic acid or derivative thereof according to any one of claims 1 to 7, wherein the diamine contains at least one photosensitive diamine selected from the following formulas (DI-19-1) to (DI-19-9). .

The diamine is represented by the following formulas (DI-1-3), (DI-1-4), (DI-4-1), (DI-5-1), (DI-5-5), (DI-5-5). 9), (DI-5-12), (DI-5-21), (DI-5-28), (DI-5-30), (DI-5-31), (DI-7-3) , (DI-9-1), (DI-13-4), (DI-13-5), (DI-13-47), (DI-16-1), (DI-16-2), ( DI-16-4), (DI-19-1), (2-a-1), (2-a-2), (2-b-1) or (2-b-2) The polyamic acid or derivative thereof according to any one of claims 1 to 8, comprising at least one selected from the group.

In the formulas (DI-5-1), (DI-5-12), (DI-7-3) and (2-a-2), m is an integer of 1 to 12;
In the formula (DI-5-30), k is an integer of 1 to 5;
In the formula (DI-7-3), n is 1 or 2;
In the formulas (DI-13-4) and (DI-13-5), R ³⁵ is alkyl having 1 to 30 carbons or alkoxy having 1 to 30 carbons;
In the formulas (DI-16-1) and (DI-16-2), R ⁴⁰ is —H or alkyl having 1 to 20 carbons;
In the formula (DI-16-4), R ⁴¹ represents —H or alkyl having 1 to 12 carbons.   The liquid crystal aligning agent containing the polyamic acid of any one of Claims 1-9, or its derivative (s).   The liquid crystal alignment according to claim 10, further comprising at least one selected from the group consisting of an alkenyl-substituted nadiimide compound, a compound having a radical polymerizable unsaturated double bond, an oxazine compound, an oxazoline compound, and an epoxy compound. Agent.   The alkenyl-substituted nadiimide compound is bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane, N, N′-m-xylylene-bis (allyl). Bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) and N, N′-hexamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2 The liquid crystal aligning agent according to claim 11, which is at least one selected from the group of compounds consisting of (, 3-dicarboximide).   Compounds having a radically polymerizable unsaturated double bond are N, N′-ethylenebisacrylamide, N, N ′-(1,2-dihydroxyethylene) bisacrylamide, ethylenebisacrylate, and 4,4′-methylenebis ( The liquid crystal aligning agent according to claim 11, which is at least one selected from the group of compounds consisting of (N, N-dihydroxyethylene acrylate aniline).   The epoxy compound is N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetra. Glycidyl-4,4′-diaminodiphenylmethane, 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3-epoxypropoxy] phenyl) )] Ethyl] phenyl] propane, 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate, N-phenylmaleimide-glycidyl methacrylate copolymer, and 2- (3,4-epoxycyclohexyl) The liquid crystal alignment according to claim 11, which is at least one selected from the group of compounds consisting of ethyltrimethoxysilane. .   The liquid crystal aligning film formed with the liquid crystal aligning agent of any one of Claims 10-14.   The liquid crystal aligning film for photo-alignment obtained by irradiating polarized ultraviolet rays to the liquid crystal aligning film formed of the liquid crystal aligning agent of any one of Claims 10-14.   It is formed through a step of applying the liquid crystal aligning agent according to any one of claims 10 to 14 to a substrate, a step of heating and drying the substrate coated with the aligning agent, and a step of irradiating the film with polarized ultraviolet rays. A liquid crystal alignment film for photo-alignment.   A step of applying the liquid crystal aligning agent according to any one of claims 10 to 14 to a substrate, a step of heating and drying the substrate coated with the aligning agent, a step of irradiating polarized ultraviolet rays to the dried film, and A liquid crystal alignment film for photo-alignment formed through a step of heating and baking the film.   The process of apply | coating the liquid crystal aligning agent of any one of Claims 10-14 to a board | substrate, the process of heat-drying the board | substrate which apply | coated the aligning agent, the process of heat-baking the dried film | membrane, and then the film | membrane A liquid crystal aligning film for photo-alignment formed through a step of irradiating with polarized ultraviolet rays.   The liquid crystal display element which has a liquid crystal aligning film of any one of Claims 15-19.