JP6520657B2 - Diamine, polyamic acid or derivative thereof, liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display device - Google Patents

Description

The present invention relates to a polyamic acid and a derivative thereof using a diamine represented by the formula (1) as a raw material, a liquid crystal aligning agent containing the polyamic acid and a derivative thereof, and a liquid crystal display device.

The liquid crystal display devices that have been commercialized today and are in general circulation are mainly display devices using nematic liquid crystal. As a display method of the nematic liquid crystal display element, a TN (Twisted Nematic) mode and a STN (Super Twisted Nematic) mode are well known. In recent years, in order to improve the narrowness of the viewing angle, which is one of the problems of these modes, TN type liquid crystal display devices using an optical compensation film, and MVA (Multi-technology using both the vertical alignment and the protrusion structure technology) -Domain Vertical Alignment mode, or IPS (In-Plane Switching) mode and FFS (Fringe Field Switching) mode of horizontal electric field type have been proposed and put to practical use (see Patent Documents 1 to 3).

The development of the liquid crystal display device technology is achieved not only by the improvement of the drive system and the device structure but also by the improvement of the component used for the device. Among the constituent members used for liquid crystal display elements, in particular, the liquid crystal alignment film is one of the important materials related to display quality, and it is possible to improve the performance of the alignment film as the liquid crystal display element is upgraded. It's getting important.

The liquid crystal alignment film mainly used at present is a polyimide-based liquid crystal alignment film formed by applying a solution (varnish) in which a polyamic acid or a soluble polyimide is dissolved in an organic solvent to a substrate and heating it. It is.

Industrially, a rubbing method capable of simple and large-area high-speed processing is widely used as an alignment processing method. The rubbing method is a process in which the surface of the liquid crystal alignment film is rubbed in one direction with a cloth on which fibers such as nylon, rayon, polyester and the like are flocked, whereby uniform alignment of liquid crystal molecules can be obtained.

Further, as an alignment processing method which replaces the rubbing method, a light alignment processing method in which alignment processing is performed by irradiating light is used. As the photoalignment treatment method, many alignment mechanisms such as a photolysis method, a photoisomerization method, a photodimerization method, a photocrosslinking method and the like have been proposed (see, for example, Non-Patent Document 1, Patent Documents 4 and 5). The photo alignment method is higher in uniformity of alignment than the rubbing method, and since it is a non-contact alignment treatment method, the film is not scratched, and causes the generation of display defects of liquid crystal display elements such as dust and static electricity. There is an advantage such as reduction.

Applications of the liquid crystal display element are variously from monitors for personal computers, liquid crystal televisions, mobile phones, display units of smartphones, liquid crystal projectors. In recent years, there are also applications where the brightness of the backlight serving as the light source is made higher than before in consideration of improvement in display quality and outdoor use, and liquid crystal that does not deteriorate display quality even when exposed to strong light for a long time There is a need for a display element.

In order to meet such requirements, various measures have been made to the liquid crystal alignment film, for example, a diamine having a structure of a hindered amine or a structure of a hindered phenol is contained in the raw material to have the same structure in the polyimide chain. (See Patent Document 6), a method of adding an antioxidant having a hindered amine structure or a hindered phenol structure to a liquid crystal aligning agent (see Patent Document 7), and a side chain type diamine Methods for introducing hindered amine structures at side chain sites are known (see Patent Document 8). However, no detailed study has been made on the influence of the above method on the viewing angle characteristics and the afterimage characteristics.

JP-A-6-194646 JP 2001-117083 JP 6-160878 JP-A-9-297313 JP 10-251646 A Unexamined-Japanese-Patent No. 2010-244015 JP 2013-127597 International Publication 2008/078629

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

An object of the present invention is to provide a liquid crystal display element in which the display quality does not deteriorate even when exposed to strong light for a long time, and by providing a liquid crystal display element excellent in viewing angle characteristics and afterimage characteristics. is there. And it is providing the liquid crystal aligning agent which can provide such a display element, and also a liquid crystal aligning film.

The present inventors use the diamine of the formula (1) described below after intensive studies, and are excellent in viewing angle characteristics and afterimage characteristics, and a liquid crystal display element in which the display quality does not deteriorate even when exposed to strong light for a long time It came to complete the liquid crystal aligning agent which can provide, and a liquid crystal aligning film. In particular, it can be suitably used in a liquid crystal display element of lateral electric field type such as IPS mode and FFS mode.

式（１）において、Ｒは水素、−ＯＨ、炭素数１〜６のアルキル、または炭素数１〜６のアルコキシであり；そして、
Ｘ^１およびＸ^２は、それぞれ独立して炭素数１〜８のアルキレンおよび／またはフェニレンを有する２価の有機基である。 The present invention consists of the following.
[1] A polyamic acid or a derivative thereof obtained by reacting a diamine containing at least one diamine represented by the formula (1) with a tetracarboxylic acid dianhydride.

In formula (1), R is hydrogen, -OH, alkyl having 1 to 6 carbons, or alkoxy having 1 to 6 carbons;
X ¹ and X ² are each independently a divalent organic group having an alkylene and / or phenylene having 1 to 8 carbon atoms.

式（１’）において、Ｒは水素、−ＯＨ、炭素数１〜６のアルキル、または炭素数１〜６のアルコキシであり；
Ａ^１およびＡ^２は、それぞれ独立して単結合または炭素数１〜６のアルキレンであり；そして、
環に結合する−ＮＨ_２の結合位置は、任意の位置である。 [2] The polyamic acid or derivative thereof according to item [1], wherein the diamine represented by the formula (1) is a diamine represented by the formula (1 ′).

In the formula (1 ′), R is hydrogen, —OH, alkyl having 1 to 6 carbons, or alkoxy having 1 to 6 carbons;
A ¹ and A ² are each independently a single bond or an alkylene having 1 to 6 carbon atoms;
The bonding position of —NH ₂ bonded to a ring is any position.

[3] The polyamic acid or derivative thereof according to item [1] or [2], wherein in the diamine represented by the formula (1), R is hydrogen or -OH.

[4] The polyamic acid according to [1] or [2], wherein the diamine represented by the formula (1) is a compound represented by the following formula (1-15) or formula (1-29) Or a derivative thereof.

式（ＡＮ−Ｉ）、式（ＡＮ−ＩＶ）および式（ＡＮ−Ｖ）において、Ｘは独立して単結合または−ＣＨ_２−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−、−ＳＯ_２−、−Ｃ（ＣＨ_３）_２−、または−Ｃ（ＣＦ_３）_２−であり；
式（ＡＮ−ＩＩ）〜式（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、

これらの基の少なくとも１つの水素はメチル、エチルまたはフェニルで置き換えられてもよく；
式（ＡＮ−ＩＩＩ）〜式（ＡＮ−Ｖ）において、環Ａ^１０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、この基の少なくとも１つの水素はメチル、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、Ｘ^１０は炭素数２〜６のアルキレンであり、Ｍｅはメチルを表し、Ｐｈはフェニルを表し、
式（ＡＮ−ＶＩＩ）において、Ｇ^１０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であり；

式（ＤＩ−１）において、Ｇ^２０は、−ＣＨ_２−であり、少なくとも１つの−ＣＨ_２−は−ＮＨ−、−Ｏ−に置き換えられてもよく、ｍは１〜１２の整数であり、アルキレンの少なくとも１つの水素は−ＯＨに置き換えられてもよく；
式（ＤＩ−３）および式（ＤＩ−５）〜式（ＤＩ−７）において、Ｇ^２１は独立して単結合、−ＮＨ−、−ＮＣＨ_３−、−Ｏ−、−Ｓ−、−Ｓ−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＣＯＯ−、−ＣＯＮＨ−、−ＣＯＮＣＨ_３−、−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）−、−（Ｏ−Ｃ_２Ｈ_４）_ｍ’−Ｏ−、−Ｏ−ＣＨ_２−Ｃ（ＣＦ_３）_２−ＣＨ_２−Ｏ−、−Ｏ−ＣＯ−（ＣＨ_２）_ｍ’−ＣＯ−Ｏ−、−ＣＯ−Ｏ−（ＣＨ_２）_ｍ’−Ｏ−ＣＯ−、−（ＣＨ_２）_ｍ’−ＮＨ−（ＣＨ_２）_ｍ’−、−ＣＯ−（ＣＨ_２）_ｋ−ＮＨ−（ＣＨ_２）_ｋ−、−（ＮＨ−（ＣＨ_２）_ｍ’) _ｋ−ＮＨ−、−ＣＯ−Ｃ_３Ｈ_６−（ＮＨ−Ｃ_３Ｈ_６）_ｎ−ＣＯ−、または−Ｓ−（ＣＨ_２）_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、ｎは１または２であり；
式（ＤＩ−４）において、ｓは独立して０〜２の整数であり；
式（ＤＩ−６）および式（ＤＩ−７）において、Ｇ^２２は独立して単結合、−Ｏ−、−Ｓ−、−ＣＯ−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−、−ＮＨ−、または炭素数１〜１０のアルキレンであり；
式（ＤＩ−２）〜式（ＤＩ−７）において、シクロヘキサン環およびベンゼン環の少なくとも１つの水素は、−Ｆ、−Ｃｌ、炭素数１〜３のアルキル、−ＯＣＨ_３、−ＯＨ、−ＣＦ_３、−ＣＯ_２Ｈ、−ＣＯＮＨ_２、−ＮＨＣ_６Ｈ_５、フェニル、またはベンジルで置き換えられてもよく、加えて式（ＤＩ−４）においてベンゼン環の少なくとも１つの水素は、下記式（ＤＩ−４−ａ）〜式（ＤＩ−４−ｅ）で表される基の群から選ばれる１つで置き換えられていてもよく；

式（ＤＩ−４−ａ）および式（ＤＩ−４−ｂ）において、Ｒ^２０は独立して水素または−ＣＨ_３であり；
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し、シクロヘキサン環またはベンゼン環への−ＮＨ_２の結合位置は、Ｇ^２１またはＧ^２２の結合位置を除く任意の位置であり；

式（ＤＩ−１１）において、ｒは０または１であり；
式（ＤＩ−８）〜式（ＤＩ−１１）において、環に結合する−ＮＨ_２の結合位置は、任意の位置であり；

式（ＤＩ−１２）において、Ｒ^２１およびＲ^２２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、Ｇ^２３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の整数であり；
式（ＤＩ−１３）において、Ｒ^２３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−１４）において、環Ｂは単環式複素芳香族であり、Ｒ^２４は水素、−Ｆ、−Ｃｌ、炭素数１〜６のアルキル、炭素数１〜６のアルコキシ、炭素数２〜６のアルケニル、炭素数２〜６のアルキニルであり、ｑは独立して０〜４の整数であり；
式（ＤＩ−１５）において、環Ｃはヘテロ原子を含む単環であり；
式（ＤＩ−１６）において、Ｇ^２４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−１３）〜式（ＤＩ−１６）において、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し；

式（ＤＩＨ−１）において、Ｇ^２５は単結合、炭素数１〜２０のアルキレン、−ＣＯ−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−Ｃ（ＣＨ_３）_２−、または−Ｃ（ＣＦ_３）_２−であり；
式（ＤＩＨ−２）において、環Ｄ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、この環の少なくとも１つの水素はメチル、エチル、またはフェニルで置き換えられてもよく；
式（ＤＩＨ−３）において、環Ｅ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、この環の少なくとも１つの水素はメチル、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−、−ＳＯ_２−、−Ｃ（ＣＨ_３）_２−、または−Ｃ（ＣＦ_３）_２−であり；
式（ＤＩＨ−２）および式（ＤＩＨ−３）において、環に結合する−ＣＯＮＨＮＨ_２の結合位置は、任意の位置であり；

式（ＤＩ−３１）において、Ｇ^２６は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−、−ＣＯＮＨ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、または−（ＣＨ_２）_ｍ’−であり、ｍ’は１〜１２の整数であり、Ｒ^２５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−３１−ａ）で表される基であり、このアルキルにおいて、少なくとも１つの水素は−Ｆで置き換えられてもよく、少なくとも１つの−ＣＨ_２−は−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられていてもよく、このフェニルの水素は、−Ｆ、−ＣＨ_３、−ＯＣＨ_３、−ＯＣＨ_２Ｆ、−ＯＣＨＦ_２、−ＯＣＦ_３、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、ベンゼン環に結合する−ＮＨ_２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−３１−ａ）において、Ｇ^２７、Ｇ^２８およびＧ^２９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−ＣＨ_２−は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、または−ＣＨ＝ＣＨ−で置き換えられていてもよく、環Ｂ^２１、環Ｂ^２２、環Ｂ^２３および環Ｂ^２４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、ピペリジン−１，４−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Ｂ^２１、環Ｂ^２２、環Ｂ^２３および環Ｂ^２４において、少なくとも１つの水素は−Ｆまたは−ＣＨ_３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、２つの環は同じであっても異なっていてもよく、
Ｒ^２６は水素、−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、−ＯＣＨ_２Ｆ、−ＯＣＨＦ_２、または−ＯＣＦ_３であり、この炭素数１〜３０のアルキルの少なくとも１つの−ＣＨ_２−は下記式（ＤＩ−３１−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−３１−ｂ）において、Ｒ^２７およびＲ^２８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−３２）および式（ＤＩ−３３）において、Ｇ^３０は独立して単結合、−ＣＯ−または−ＣＨ_２−であり、Ｒ^２９は独立して水素または−ＣＨ_３であり、Ｒ^３０は水素、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−３３）におけるベンゼン環の１つの水素は、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、そして、
式（ＤＩ−３２）および式（ＤＩ−３３）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；

式（ＤＩ−３４）および式（ＤＩ−３５）において、Ｇ^３１は独立して−Ｏ−、−ＮＨ−または炭素数１〜６のアルキレンであり、Ｇ^３２は単結合または炭素数１〜３のアルキレンであり、
Ｒ^３１は水素または炭素数１〜２０のアルキルであり、このアルキルの少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、Ｒ^３２は炭素数６〜２２のアルキルであり、Ｒ^３３は水素または炭素数１〜２２のアルキルであり、環Ｂ^２５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−ＮＨ_２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 tetracarboxylic acid dianhydride is at least one selected from the group of tetracarboxylic acid dianhydrides represented by the following formulas (AN-I) to (AN-VII);
Other diamines used together with the diamine represented by the formula (1) are represented by the following formulas (DI-1) to (DI-16), formulas (DIH-1) to (DIH-3), and formulas (DI) -31) The polyamic acid or a derivative thereof according to any one of [1] to [4], which is at least one selected from the group consisting of Formula (DI-35).

In formula (AN-I), formula (AN-IV) and formula (AN-V), X is independently a single bond or -CH _2- ;
In formula (AN-II), G is 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 formulas (AN-II) to (AN-IV), Y is independently one selected from the following group of trivalent groups,

At least one hydrogen of these groups may be replaced by methyl, ethyl or phenyl;
In formulas (AN-III) to (AN-V), ring A ¹⁰ is a monocyclic hydrocarbon group of 3 to ¹⁰ carbon atoms or a fused polycyclic hydrocarbon group of 6 to 30 carbon atoms, At least one hydrogen of this group may be replaced by methyl, ethyl or phenyl, and the bond attached to the ring is connected to any carbon constituting the ring, and two bonds are identical. May be linked to carbon;
In formula (AN-VI), X ¹⁰ is alkylene having 2 to 6 carbon atoms, Me represents methyl, and Ph represents phenyl.
In formula (AN-VII), G ¹⁰ is independently -O-, -COO- or -OCO-; and r is independently 0 or 1;

In formula (DI-1), G ²⁰ is —CH ₂ —, and at least one —CH ₂ — may be replaced by —NH— or —O—, and m is an integer of 1 to 12 , At least one hydrogen of alkylene may be replaced by -OH;
In formulas (DI-3) and (DI-5) to (DI-7), G ²¹ independently represents a single bond, -NH-, -NCH _3- , -O-, -S-, -S _{-S -, - SO 2 -,} - CO -, - COO -, - CONH -, - CONCH 3 -, - 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) -, - (O-C 2 H 4) m '-O- _{, -O-CH 2 -C (CF} 3) 2 -CH 2 -O -, - O-CO- (CH 2) m '-CO-O -, - CO-O- (CH 2) m' -O _{-CO -, - (CH 2)} m '-NH- (CH 2) m' -, - CO- (CH 2) k -NH- (CH 2) k -, - (NH- (CH 2) m ' _{) k -NH -, - CO-} C 3 _{6 - (NH-C 3 H} 6) n -CO-, or -S- _(CH 2) _{m 'is} -S-, m' is an integer from 1 to 12 independently, k is 1 to 5 N is an integer of 1 or 2;
In formula (DI-4), s is independently an integer of 0 to 2;
In Formula (DI-6) and Formula (DI-7), G ²² is independently a single bond, -O-, -S-, -CO-, -C (CH ₃ ) _2- , -C (CF _{3 2} )-, -NH-, or alkylene having 1 to 10 carbon atoms;
In formulas (DI-2) to (DI-7), at least one hydrogen of a cyclohexane ring and a benzene ring is —F, —Cl, an alkyl having 1 to 3 carbon atoms, —OCH ₃ , —OH, —CF ₃ , -CO ₂ H, -CONH ₂ , -NHC ₆ H ₅ , phenyl or benzyl may be substituted, and additionally, at least one hydrogen of the benzene ring in the formula (DI-4) is represented by the following formula (DI) And -4-a) may be substituted with one selected from the group of groups represented by formula (DI-4-e);

In formulas (DI-4-a) and (DI-4-b), R ²⁰ is independently hydrogen or -CH ₃ ;
A group whose bonding position is not fixed to the 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 benzene ring is G ²¹ or G ^22. Any position except for the bonding position of

In formula (DI-11), r is 0 or 1;
In formulas (DI-8) to (DI-11), the bonding position of -NH ₂ bonded to a ring is any position;

In formula (DI-12), R ²¹ and R ^{22 each} independently represent alkyl or phenyl having 1 to 3 carbon atoms, and G ²³ independently represents alkylene, phenylene or alkyl substituted phenylene having 1 to 6 carbon atoms And w is an integer of 1 to 10;
In formula (DI-13), R ²³ is independently alkyl of 1 to 5 carbons, alkoxy of 1 to 5 carbons, or -Cl, p is independently an integer of 0 to 3, and q is Is an integer from 0 to 4;
In Formula (DI-14), ring B is monocyclic heteroaromatic, R ²⁴ is hydrogen, -F, -Cl, alkyl having 1 to 6 carbons, alkoxy having 1 to 6 carbons, 2 carbons -6 alkenyl, alkynyl having 2 to 6 carbon atoms, and q is independently an integer of 0 to 4;
In formula (DI-15), ring C is a single ring containing a hetero atom;
In formula (DI-16), G ²⁴ is a single bond, alkylene having 2 to 6 carbon atoms, or 1,4-phenylene, and r is 0 or 1;
In formulas (DI-13) to (DI-16), a group whose bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position on the ring is arbitrary;

In formula (DIH-1), G ²⁵ is 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 (DIH-2), ring D is a cyclohexane ring, a benzene ring or a naphthalene ring, and at least one hydrogen of this ring may be replaced with methyl, ethyl or phenyl;
In Formula (DIH-3), each ring E is independently a cyclohexane ring or a benzene ring, at least one hydrogen of this ring may be replaced with methyl, ethyl or phenyl, and Y is a single bond, C 1-20 alkylene, -CO-, -O-, -S-, -SO _2- , -C (CH ₃ ) _2- , or -C (CF ₃ ) _2- ;
In the formulas (DIH-2) and (DIH-3), the bonding position of -CONHNH ₂ bonded to the ring is any position;

In formula (DI-31), G ²⁶ is a single bond, -O-, -COO-, -OCO-, -CO-, -CONH-, -CH ₂ O-, -OCH _2- , -CF ₂ O- , -OCF _2- , or-(CH ₂ ) _{m '} -, m' is an integer of 1 to 12, R ²⁵ is alkyl having 3 to 30 carbon atoms, phenyl, a group having a steroid skeleton, or In the alkyl, at least one hydrogen may be replaced by -F, and at least one -CH ₂ -is -O-, -CH = may be replaced by CH- or -C≡C-, hydrogen which _{phenyl, -F, -CH 3, -OCH 3} , -OCH 2 F, -OCHF 2, -OCF 3, 3~ carbon atoms 30 alkyl or alkoxy having 3 to 30 carbon atoms It may be substituted, and the bonding position of -NH ₂ bonded to the benzene ring is an arbitrary position in the ring,

In the formula (DI-31-a), G ²⁷ , G ²⁸ and G ^{29 each} represents a bonding group, which are independently a single bond or an alkylene having 1 to 12 carbon atoms, and one or more of this alkylene CH ₂ -may be replaced by -O-, -COO-, -OCO-, -CONH-, or -CH = CH-, and ring B ²¹ , ring B ²² , ring B ²³ and ring B ²⁴ are 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, piperidine-1,4 -Diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl or anthracene-9,10-diyl, at least one hydrogen in ring B ²¹ , ring B ²² , ring B ²³ and ring B ²⁴ Is It may be replaced by F or -CH _3, s, t and u is an integer of 0 to 2 independently, their sum is 1-5, 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 is hydrogen, -F, -OH, alkyl having 1 to 30 carbons, fluorine-substituted alkyl having 1 to 30 carbons, alkoxy having 1 to 30 carbons, -CN, -OCH ₂ F, -OCHF ₂ , or -OCF ₃ and at least one -CH _2- of the alkyl having 1 to 30 carbon atoms may be replaced by a divalent group represented by the following formula (DI- 31-b),

In formula (DI-31-b), R ²⁷ and R ²⁸ independently represent alkyl having 1 to 3 carbon atoms, and v is an integer of 1 to 6;

In formulas (DI-32) and (DI-33), G ³⁰ is independently a single bond, -CO- or -CH _2- , and R ²⁹ is independently hydrogen or -CH ₃ , R ³⁰ is hydrogen, alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons;
And one hydrogen of the benzene ring in formula (DI-33) may be replaced by alkyl having 1 to 20 carbon atoms or phenyl, and
In formulas (DI-32) and (DI-33), 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;

In formulas (DI-34) and (DI-35), G ³¹ is independently -O-, -NH- or alkylene having 1 to 6 carbon atoms, and G ³² is a single bond or 1 to 3 carbon atoms Is an alkylene of
R ³¹ is hydrogen or alkyl having 1 to 20 carbon atoms, and at least one —CH ₂ — of this alkyl may be replaced by —O—, —CH = CH— or —C≡C—, R ³² is alkyl having 6 to 22 carbons, R ³³ is hydrogen or alkyl having 1 to 22 carbons, ring B ²⁵ is 1,4-phenylene or 1,4-cyclohexylene, r is 0 or 1 and -NH ₂ attached to the benzene ring indicates that the attachment position on the ring is arbitrary.

式（ＡＮ−１−２）および式（ＡＮ−４−１７）において、ｍは１〜１２の整数であり；

式（ＤＩ−５−１）、式（ＤＩ−５−１２）、式（ＤＩ−５−１３）、および式（ＤＩ−７−３）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；そして、
式（ＤＩ−７−３）において、ｎは1または２である。 [6] The tetracarboxylic acid dianhydride is represented by the following formula (AN-1-1), formula (AN-1-2), formula (AN-1-13), formula (PA-1), formula (AN-) 3-1) Formula (AN-3-2) Formula (AN-4-5) Formula (AN-4-17) Formula (AN-4-21) Formula (AN-4-29) Formula (AN-4-30), Formula (AN-5-1), Formula (AN-7-2), Formula (AN-10-1), Formula (AN-11-3), Formula (AN-16) -1) at least one selected from Formula (AN-16-3), and Formula (AN-16-4);
The other diamine used together with the diamine represented by Formula (1) is a compound represented by the following Formula (DI-1-3), Formula (DI-2-1), Formula (DI-4-1), Formula (DI-4) -2), formula (DI-4-10), formula (DI-4-15), formula (DI-5-1), formula (DI-5-5), formula (DI-5-9), formula (DI-5-12), formula (DI-5-13), formula (DI-5-17), formula (DI-5-28), formula (DI-5-30), formula (DI-6-) 7), formula (DI-7-3), formula (DI-11-2), formula (DI-13-1), formula (DI-16-1), formula (DIH-2-1), and formula The polyamic acid or derivative thereof according to Item 5, which is at least one member selected from the group consisting of (DI-31-56).

In formula (AN-1-2) and formula (AN-4-17), m is an integer of 1 to 12;

In Formula (DI-5-1), Formula (DI-5-12), Formula (DI-5-13), and Formula (DI-7-3), m is an integer of 1 to 12;
In formula (DI-5-30), k is an integer of 1 to 5; and
In formula (DI-7-3), n is 1 or 2.

[ 7 ] Any one of [1] to [ 6 ] obtained by reacting a raw material monomer containing a compound having a photoreactive structure with at least one of tetracarboxylic acid dianhydride and diamine to be subjected to the reaction The polyamic acid or its derivative as described in a term.

式（Ｐ−１）中、Ｒ^６１は独立して、水素原子、炭素数１〜５のアルキル基、またはフェニル基である。 [ 8 ] The polyamic acid according to the item [ 7 ], or a polyamic acid thereof, wherein the photoreactive structure is at least one selected from the group consisting of the structures represented by the following formulas (P-1) to (P-7) Derivative.

In formula (P-1), R ⁶¹ is independently a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, or a phenyl group.

上記各式において、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、式（Ｖ−２）において、Ｒ^６は独立して−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、または−ＣＯＯＣＨ_３であり、ａはそれぞれ独立して０〜２の整数であり、式（Ｖ−３）において、環Ａおよび環Ｂはそれぞれ独立して、単環式炭化水素、縮合多環式炭化水素および複素環から選ばれる少なくとも１つであり、Ｒ^１１は、炭素数１〜２０の直鎖アルキレン、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−または−Ｎ（ＣＨ_３）ＣＯ−であり、Ｒ^１２は、炭素数１〜２０の直鎖アルキレン、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−または−Ｎ（ＣＨ_３）ＣＯ−であり、Ｒ^１１およびＲ^１２において、直鎖アルキレンの−ＣＨ_２−の１つまたは２つは−Ｏ−で置換されてもよく、Ｒ^７〜Ｒ^１０は、それぞれ独立して、−Ｆ、−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、または−ＯＨであり、そして、ｂ〜ｅは、それぞれ独立して、０〜４の整数である。 [ 9 ] Compounds having a photoreactive structure have the following formulas (II-1), (II-2), (III-1), (III-2), (IV-1), and (IV) -2), the formula (V-1) to the formula (V-3), and the formula (VI-1), at least one selected from the group consisting of the formula (VI-2), described in the item [ 7 ] Polyamic acid or its derivative.

In each of the above formulas, 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 the formula (V-2), R ⁶ is independent And in the formula (V-3), ring A and ring B are each independently -CH ₃ , -OCH ₃ , -CF ₃ , or -COOCH _3; Independently, it is at least one selected from monocyclic hydrocarbon, fused polycyclic hydrocarbon and heterocycle, and R ¹¹ is linear alkylene having 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO- or -N _(CH 3) a ^{CO-, R 12} is a straight-chain alkylene having 1 to 20 carbon atoms, -COO -, - OCO -, - NHCO- or -N _(CH 3) CO- in Yes, in R ¹¹ and R ¹² , linear One or two of -CH _2-of alkylene may be substituted by -O-, and R ^{7 to} R ¹⁰ each independently represent -F, -CH ₃ , -OCH ₃ , -CF ₃ , Or -OH, and b to e are each independently an integer of 0 to 4;

式（ＰＤＩ−７）において、Ｒ^５１はそれぞれ独立して−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、または−ＣＯＯＣＨ_３であり、ｓはそれぞれ独立して０〜２の整数である。 [ 10 ] The polyamic acid or derivative thereof according to item [ 7 ], wherein the compound having a photoreactive structure is a diamine represented by the following formula (PDI-7).

In formula (PDI-7), R ⁵¹ is each independently —CH ₃ , —OCH ₃ , —CF ₃ , or —COOCH ₃ , and s is each independently an integer of 0 to 2.

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

式（１）において、Ｒは水素、−ＯＨ、炭素数１〜６のアルキル、または炭素数１〜６のアルコキシであり；そして、
Ｘ^１およびＸ^２は、それぞれ独立して炭素数１〜８のアルキレンおよび／またはフェニレンを有する２価の有機基である。 [ 12 ] A liquid crystal aligning agent for photoalignment, comprising a polymer [A] which is a polyamic acid or a derivative thereof and a polymer [B];
A liquid crystal aligning agent for photoalignment, wherein at least one of the raw material monomers of the polymer has a photoreactive structure, and the raw material monomer of the polymer contains at least one of the compounds represented by the following formula (1) .

In formula (1), R is hydrogen, -OH, alkyl having 1 to 6 carbons, or alkoxy having 1 to 6 carbons;
X ¹ and X ² are each independently a divalent organic group having an alkylene and / or phenylene having 1 to 8 carbon atoms.

[ 13 ] At least one of polymers [A] obtained by reacting starting monomers containing a compound having at least one photoreactive structure selected from the group consisting of tetracarboxylic acid dianhydrides and diamines,
A polymer obtained by reacting a raw material monomer in which none of tetracarboxylic acid dianhydride and diamine has a photoreactive structure and the diamine contains at least one of the compounds represented by formula (1) The liquid crystal aligning agent for photoalignment as described in the item [ 12 ], which contains at least one of [B].

[ 14 ] A raw material comprising a compound having at least one photoreactive structure selected from the group consisting of tetracarboxylic acid dianhydrides and diamines, and wherein the diamine contains at least one of the compounds represented by formula (1) At least one of the polymers [A] obtained by reacting monomers,
The photoalignment as described in [ 12 ], wherein at least one of the polymers [B] obtained by reacting a raw material monomer having neither a tetracarboxylic acid dianhydride nor a diamine having a photoreactive structure is included. Liquid crystal aligning agent.

[ 15 ] A raw material comprising a compound having at least one photoreactive structure selected from the group consisting of tetracarboxylic acid dianhydrides and diamines, and wherein the diamine contains at least one of the compounds represented by formula (1) At least one of the polymers [A] obtained by reacting monomers,
A polymer obtained by reacting a raw material monomer including at least one of the compounds represented by the formula (1), wherein none of the tetracarboxylic acid dianhydride and the diamine have a photoreactive structure, and The liquid crystal aligning agent for optical alignment as described in [12] term containing B].

[ 16 ] A raw material comprising a compound having at least one photoreactive structure selected from the group consisting of tetracarboxylic acid dianhydride and diamine, and wherein the diamine comprises at least one of the compounds represented by formula (1) At least one of the polymers [A] obtained by reacting monomers,
A raw material monomer is reacted which contains a compound having at least one photoreactive structure selected from the group consisting of tetracarboxylic acid dianhydride and diamine, and the diamine contains at least one of the compounds represented by formula (1) The liquid crystal aligning agent for photoalignment as described in the item [ 12 ], containing at least one of the polymers [B] obtained by

式（１’）において、Ｒは水素、−ＯＨ、炭素数１〜６のアルキル、または炭素数１〜６のアルコキシであり；
Ａ^１およびＡ^２は、それぞれ独立して単結合または炭素数１〜６のアルキレンであり；そして、
環に結合する−ＮＨ_２の結合位置は、任意の位置である。 [ 17 ] The liquid crystal aligning agent for photoalignment according to any one of [ 12 ] to [ 16 ], wherein the diamine represented by the formula (1) is a diamine represented by the formula (1 ').

In the formula (1 ′), R is hydrogen, —OH, alkyl having 1 to 6 carbons, or alkoxy having 1 to 6 carbons;
A ¹ and A ² are each independently a single bond or an alkylene having 1 to 6 carbon atoms;
The bonding position of —NH ₂ bonded to a ring is any position.

[ 18 ] The liquid crystal aligning agent for photoalignment according to any one of [ 12 ] to [ 17 ], wherein R is hydrogen or -OH in the diamine represented by the formula (1).

[ 19 ] The diamine according to any one of [ 12 ] to [ 18 ], wherein the diamine represented by the formula (1) is a compound represented by the following formula (1-15) or the formula (1-29) Liquid crystal alignment agent for photo alignment.

式（Ｐ−１）中、Ｒ^６１は独立して、水素原子、炭素数１〜５のアルキル基、またはフェニル基である。 [ 20 ] In any one of [ 12 ] to [ 19 ], the compound having a photoreactive structure has at least one of the structures represented by the following formulas (P-1) to (P-7) The liquid crystal aligning agent for photo alignment as described.

In formula (P-1), R ⁶¹ is independently a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, or a phenyl group.

上記各式において、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、式（Ｖ−２）において、Ｒ^６は独立して−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、または−ＣＯＯＣＨ_３であり、ａはそれぞれ独立して０〜２の整数であり、式（Ｖ−３）において、環Ａおよび環Ｂはそれぞれ独立して、単環式炭化水素、縮合多環式炭化水素および複素環から選ばれる少なくとも１つであり、Ｒ^１１は、炭素数１〜２０の直鎖アルキレン、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−または−Ｎ（ＣＨ_３）ＣＯ−であり、Ｒ^１２は、炭素数１〜２０の直鎖アルキレン、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−または−Ｎ（ＣＨ_３）ＣＯ−であり、Ｒ^１１およびＲ^１２において、直鎖アルキレンの−ＣＨ_２−の１つまたは２つは−Ｏ−で置換されてもよく、Ｒ^７〜Ｒ^１０は、それぞれ独立して、−Ｆ、−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、または−ＯＨであり、そして、ｂ〜ｅは、それぞれ独立して、０〜４の整数である。 [ 21 ] The compound having a photoreactive structure is represented by the following formula (II-1), formula (II-2), formula (III-1), formula (III-2), formula (IV-1), formula (IV) −2), at least one selected from the group consisting of Formula (V-1) to Formula (V-3), and Formula (VI-1), Formula (VI-2), [ 12 ] to [ 19 ] The liquid crystal aligning agent for photo-alignment of any one of Claim 1.

In each of the above formulas, 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 the formula (V-2), R ⁶ is independent And in the formula (V-3), ring A and ring B are each independently -CH ₃ , -OCH ₃ , -CF ₃ , or -COOCH _3; Independently, it is at least one selected from monocyclic hydrocarbon, fused polycyclic hydrocarbon and heterocycle, and R ¹¹ is linear alkylene having 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO- or -N _(CH 3) a ^{CO-, R 12} is a straight-chain alkylene having 1 to 20 carbon atoms, -COO -, - OCO -, - NHCO- or -N _(CH 3) CO- in Yes, in R ¹¹ and R ¹² , linear One or two of -CH _2-of alkylene may be substituted by -O-, and R ^{7 to} R ¹⁰ each independently represent -F, -CH ₃ , -OCH ₃ , -CF ₃ , Or -OH, and b to e are each independently an integer of 0 to 4;

式（ＰＤＩ−７）において、Ｒ^５１はそれぞれ独立して−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、または−ＣＯＯＣＨ_３であり、ｓはそれぞれ独立して０〜２の整数である。 [ 22 ] The liquid crystal aligning agent for photoreaction according to any one of [ 12 ] to [ 19 ], wherein the compound having a photoreactive structure is a diamine represented by the following formula (PDI-7).

In formula (PDI-7), R ⁵¹ is each independently —CH ₃ , —OCH ₃ , —CF ₃ , or —COOCH ₃ , and s is each independently an integer of 0 to 2.

式（ＡＮ−Ｉ）、式（ＡＮ−ＩＶ）および式（ＡＮ−Ｖ）において、Ｘは独立して単結合または−ＣＨ_２−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−、−ＳＯ_２−、−Ｃ（ＣＨ_３）_２−、または−Ｃ（ＣＦ_３）_２−であり；
式（ＡＮ−ＩＩ）〜式（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、

これらの基の少なくとも１つの水素はメチル、エチルまたはフェニルで置き換えられてもよく；
式（ＡＮ−ＩＩＩ）〜式（ＡＮ−Ｖ）において、環Ａ^１０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、この基の少なくとも１つの水素はメチル、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、Ｘ^１０は炭素数２〜６のアルキレンであり、Ｍｅはメチルを表し、Ｐｈはフェニルを表し、
式（ＡＮ−ＶＩＩ）において、Ｇ^１０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であり；

式（ＤＩ−１）において、Ｇ^２０は、−ＣＨ_２−であり、少なくとも１つの−ＣＨ_２−は−ＮＨ−、−Ｏ−に置き換えられてもよく、ｍは１〜１２の整数であり、アルキレンの少なくとも１つの水素は−ＯＨに置き換えられてもよく；
式（ＤＩ−３）および式（ＤＩ−５）〜式（ＤＩ−７）において、Ｇ^２１は独立して単結合、−ＮＨ−、−ＮＣＨ_３−、−Ｏ−、−Ｓ−、−Ｓ−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＣＯＯ−、−ＣＯＮＨ−、−ＣＯＮＣＨ_３−、−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）−、−（Ｏ−Ｃ_２Ｈ_４）_ｍ’−Ｏ−、−Ｏ−ＣＨ_２−Ｃ（ＣＦ_３）_２−ＣＨ_２−Ｏ−、−Ｏ−ＣＯ−（ＣＨ_２）_ｍ’−ＣＯ−Ｏ−、−ＣＯ−Ｏ−（ＣＨ_２）_ｍ’−Ｏ−ＣＯ−、−（ＣＨ_２）_ｍ’−ＮＨ−（ＣＨ_２）_ｍ’−、−ＣＯ−（ＣＨ_２）_ｋ−ＮＨ−（ＣＨ_２）_ｋ−、−（ＮＨ−（ＣＨ_２）_ｍ’) _ｋ−ＮＨ−、−ＣＯ−Ｃ_３Ｈ_６−（ＮＨ−Ｃ_３Ｈ_６）_ｎ−ＣＯ−、または−Ｓ−（ＣＨ_２）_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、ｎは１または２であり；
式（ＤＩ−４）において、ｓは独立して０〜２の整数であり；
式（ＤＩ−６）および式（ＤＩ−７）において、Ｇ^２２は独立して単結合、−Ｏ−、−Ｓ−、−ＣＯ−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−、−ＮＨ−、または炭素数１〜１０のアルキレンであり；
式（ＤＩ−２）〜式（ＤＩ−７）において、シクロヘキサン環およびベンゼン環の少なくとも１つの水素は、−Ｆ、−Ｃｌ、炭素数１〜３のアルキル、−ＯＣＨ_３、−ＯＨ、−ＣＦ_３、−ＣＯ_２Ｈ、−ＣＯＮＨ_２、−ＮＨＣ_６Ｈ_５、フェニル、またはベンジルで置き換えられてもよく、加えて式（ＤＩ−４）においてベンゼン環の少なくとも１つの水素は、下記式（ＤＩ−４−ａ）〜式（ＤＩ−４−ｅ）で表される基の群から選ばれる１つで置き換えられていてもよく；

式（ＤＩ−４−ａ）および式（ＤＩ−４−ｂ）において、Ｒ^２０は独立して水素または−ＣＨ_３であり；
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し、シクロヘキサン環またはベンゼン環への−ＮＨ_２の結合位置は、Ｇ^２１またはＧ^２２の結合位置を除く任意の位置であり；

式（ＤＩ−１１）において、ｒは０または１であり；
式（ＤＩ−８）〜式（ＤＩ−１１）において、環に結合する−ＮＨ_２の結合位置は、任意の位置であり；

式（ＤＩ−１２）において、Ｒ^２１およびＲ^２２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、Ｇ^２３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の整数であり；
式（ＤＩ−１３）において、Ｒ^２３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−１４）において、環Ｂは単環式複素芳香族であり、Ｒ^２４は水素、−Ｆ、−Ｃｌ、炭素数１〜６のアルキル、炭素数１〜６のアルコキシ、炭素数２〜６のアルケニル、炭素数２〜６のアルキニルであり、ｑは独立して０〜４の整数であり；
式（ＤＩ−１５）において、環Ｃはヘテロ原子を含む単環であり；
式（ＤＩ−１６）において、Ｇ^２４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−１３）〜式（ＤＩ−１６）において、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し；

式（ＤＩＨ−１）において、Ｇ^２５は単結合、炭素数１〜２０のアルキレン、−ＣＯ−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−Ｃ（ＣＨ_３）_２−、または−Ｃ（ＣＦ_３）_２−であり；
式（ＤＩＨ−２）において、環Ｄ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、この環の少なくとも１つの水素はメチル、エチル、またはフェニルで置き換えられてもよく；
式（ＤＩＨ−３）において、環Ｅ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、この環の少なくとも１つの水素はメチル、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−、−ＳＯ_２−、−Ｃ（ＣＨ_３）_２−、または−Ｃ（ＣＦ_３）_２−であり；
式（ＤＩＨ−２）および式（ＤＩＨ−３）において、環に結合する−ＣＯＮＨＮＨ_２の結合位置は、任意の位置であり；

式（ＤＩ−３１）において、Ｇ^２６は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−、−ＣＯＮＨ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、または−（ＣＨ_２）_ｍ’−であり、ｍ’は１〜１２の整数であり、Ｒ^２５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−３１−ａ）で表される基であり、このアルキルにおいて、少なくとも１つの水素は−Ｆで置き換えられてもよく、少なくとも１つの−ＣＨ_２−は−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられていてもよく、このフェニルの水素は、−Ｆ、−ＣＨ_３、−ＯＣＨ_３、−ＯＣＨ_２Ｆ、−ＯＣＨＦ_２、−ＯＣＦ_３、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、ベンゼン環に結合する−ＮＨ_２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−３１−ａ）において、Ｇ^２７、Ｇ^２８およびＧ^２９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−ＣＨ_２−は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、または−ＣＨ＝ＣＨ−で置き換えられていてもよく、環Ｂ^２１、環Ｂ^２２、環Ｂ^２３および環Ｂ^２４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、ピペリジン−１，４−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Ｂ^２１、環Ｂ^２２、環Ｂ^２３および環Ｂ^２４において、少なくとも１つの水素は−Ｆまたは−ＣＨ_３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、２つの環は同じであっても異なっていてもよく、
Ｒ^２６は水素、−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、−ＯＣＨ_２Ｆ、−ＯＣＨＦ_２、または−ＯＣＦ_３であり、この炭素数１〜３０のアルキルの少なくとも１つの−ＣＨ_２−は下記式（ＤＩ−３１−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−３１−ｂ）において、Ｒ^２７およびＲ^２８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−３２）および式（ＤＩ−３３）において、Ｇ^３０は独立して単結合、−ＣＯ−または−ＣＨ_２−であり、Ｒ^２９は独立して水素または−ＣＨ_３であり、Ｒ^３０は水素、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−３３）におけるベンゼン環の１つの水素は、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、そして、
式（ＤＩ−３２）および式（ＤＩ−３３）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；

式（ＤＩ−３４）および式（ＤＩ−３５）において、Ｇ^３１は独立して−Ｏ−、−ＮＨ−または炭素数１〜６のアルキレンであり、Ｇ^３２は単結合または炭素数１〜３のアルキレンであり、
Ｒ^３１は水素または炭素数１〜２０のアルキルであり、このアルキルの少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、Ｒ^３２は炭素数６〜２２のアルキルであり、Ｒ^３３は水素または炭素数１〜２２のアルキルであり、環Ｂ^２５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−ＮＨ_２はその環における結合位置が任意であることを示す。 [23] At least one tetracarboxylic acid dianhydride having no photoreactive structure is selected from the group of tetracarboxylic acid dianhydrides represented by the following formulas (AN-I) to (AN-VII) One;
The diamine having no photoreactive structure is represented by the following formulas (DI-1) to (DI-16), formulas (DIH-1) to (DIH-3), and formulas (DI-31) to The liquid crystal aligning agent for photo alignments of any one of [12]-[22] which is at least one selected from the group which consists of DI-35).

In formula (AN-I), formula (AN-IV) and formula (AN-V), X is independently a single bond or -CH _2- ;
In formula (AN-II), G is 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 formulas (AN-II) to (AN-IV), Y is independently one selected from the following group of trivalent groups,

At least one hydrogen of these groups may be replaced by methyl, ethyl or phenyl;
In formulas (AN-III) to (AN-V), ring A ¹⁰ is a monocyclic hydrocarbon group of 3 to ¹⁰ carbon atoms or a fused polycyclic hydrocarbon group of 6 to 30 carbon atoms, At least one hydrogen of this group may be replaced by methyl, ethyl or phenyl, and the bond attached to the ring is connected to any carbon constituting the ring, and two bonds are identical. May be linked to carbon;
In formula (AN-VI), X ¹⁰ is alkylene having 2 to 6 carbon atoms, Me represents methyl, and Ph represents phenyl.
In formula (AN-VII), G ¹⁰ is independently -O-, -COO- or -OCO-, and r is independently 0 or 1;

In formula (DI-1), G ²⁰ is —CH ₂ —, and at least one —CH ₂ — may be replaced by —NH— or —O—, and m is an integer of 1 to 12 , At least one hydrogen of alkylene may be replaced by -OH;
In formulas (DI-3) and (DI-5) to (DI-7), G ²¹ independently represents a single bond, -NH-, -NCH _3- , -O-, -S-, -S _{-S -, - SO 2 -,} - CO -, - COO -, - CONH -, - CONCH 3 -, - 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) -, - (O-C 2 H 4) m '-O- _{, -O-CH 2 -C (CF} 3) 2 -CH 2 -O -, - O-CO- (CH 2) m '-CO-O -, - CO-O- (CH 2) m' -O _{-CO -, - (CH 2)} m '-NH- (CH 2) m' -, - CO- (CH 2) k -NH- (CH 2) k -, - (NH- (CH 2) m ' _{) k -NH -, - CO-} C 3 _{6 - (NH-C 3 H} 6) n -CO-, or -S- _(CH 2) _{m 'is} -S-, m' is an integer from 1 to 12 independently, k is 1 to 5 N is an integer of 1 or 2;
In formula (DI-4), s is independently an integer of 0 to 2;
In Formula (DI-6) and Formula (DI-7), G ²² is independently a single bond, -O-, -S-, -CO-, -C (CH ₃ ) _2- , -C (CF _{3 2} )-, -NH-, or alkylene having 1 to 10 carbon atoms;
In formulas (DI-2) to (DI-7), at least one hydrogen of a cyclohexane ring and a benzene ring is —F, —Cl, an alkyl having 1 to 3 carbon atoms, —OCH ₃ , —OH, —CF ₃ , -CO ₂ H, -CONH ₂ , -NHC ₆ H ₅ , phenyl or benzyl may be substituted, and additionally, at least one hydrogen of the benzene ring in the formula (DI-4) is represented by the following formula (DI) And -4-a) may be substituted with one selected from the group of groups represented by formula (DI-4-e);

In formulas (DI-4-a) and (DI-4-b), R ²⁰ is independently hydrogen or -CH ₃ ;
A group whose bonding position is not fixed to the 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 benzene ring is G ²¹ or G ^22. Any position except for the bonding position of

In formula (DI-11), r is 0 or 1;
In formulas (DI-8) to (DI-11), the bonding position of -NH ₂ bonded to a ring is any position;

In formula (DI-12), R ²¹ and R ^{22 each} independently represent alkyl or phenyl having 1 to 3 carbon atoms, and G ²³ independently represents alkylene, phenylene or alkyl substituted phenylene having 1 to 6 carbon atoms And w is an integer of 1 to 10;
In formula (DI-13), R ²³ is independently alkyl of 1 to 5 carbons, alkoxy of 1 to 5 carbons, or -Cl, p is independently an integer of 0 to 3, and q is Is an integer from 0 to 4;
In Formula (DI-14), ring B is monocyclic heteroaromatic, R ²⁴ is hydrogen, -F, -Cl, alkyl having 1 to 6 carbons, alkoxy having 1 to 6 carbons, 2 carbons -6 alkenyl, alkynyl having 2 to 6 carbon atoms, and q is independently an integer of 0 to 4;
In formula (DI-15), ring C is a single ring containing a hetero atom;
In formula (DI-16), G ²⁴ is a single bond, alkylene having 2 to 6 carbon atoms, or 1,4-phenylene, and r is 0 or 1;
In formulas (DI-13) to (DI-16), a group whose bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position on the ring is arbitrary;

In formula (DIH-1), G ²⁵ is 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 (DIH-2), ring D is a cyclohexane ring, a benzene ring or a naphthalene ring, and at least one hydrogen of this ring may be replaced with methyl, ethyl or phenyl;
In Formula (DIH-3), each ring E is independently a cyclohexane ring or a benzene ring, at least one hydrogen of this ring may be replaced with methyl, ethyl or phenyl, and Y is a single bond, C 1-20 alkylene, -CO-, -O-, -S-, -SO _2- , -C (CH ₃ ) _2- , or -C (CF ₃ ) _2- ;
In the formulas (DIH-2) and (DIH-3), the bonding position of -CONHNH ₂ bonded to the ring is any position;

In formula (DI-31), G ²⁶ is a single bond, -O-, -COO-, -OCO-, -CO-, -CONH-, -CH ₂ O-, -OCH _2- , -CF ₂ O- , -OCF _2- , or-(CH ₂ ) _{m '} -, m' is an integer of 1 to 12, R ²⁵ is alkyl having 3 to 30 carbon atoms, phenyl, a group having a steroid skeleton, or In the alkyl, at least one hydrogen may be replaced by -F, and at least one -CH ₂ -is -O-, -CH = may be replaced by CH- or -C≡C-, hydrogen which _{phenyl, -F, -CH 3, -OCH 3} , -OCH 2 F, -OCHF 2, -OCF 3, 3~ carbon atoms 30 alkyl or alkoxy having 3 to 30 carbon atoms It may be substituted, and the bonding position of -NH ₂ bonded to the benzene ring is an arbitrary position in the ring,

In the formula (DI-31-a), G ²⁷ , G ²⁸ and G ^{29 each} represents a bonding group, which are independently a single bond or an alkylene having 1 to 12 carbon atoms, and one or more of this alkylene CH ₂ -may be replaced by -O-, -COO-, -OCO-, -CONH-, or -CH = CH-, and ring B ²¹ , ring B ²² , ring B ²³ and ring B ²⁴ are 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, piperidine-1,4 -Diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl or anthracene-9,10-diyl, at least one hydrogen in ring B ²¹ , ring B ²² , ring B ²³ and ring B ²⁴ Is It may be replaced by F or -CH _3, s, t and u is an integer of 0 to 2 independently, their sum is 1-5, 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 is hydrogen, -F, -OH, alkyl having 1 to 30 carbons, fluorine-substituted alkyl having 1 to 30 carbons, alkoxy having 1 to 30 carbons, -CN, -OCH ₂ F, -OCHF ₂ , or -OCF ₃ and at least one -CH _2- of the alkyl having 1 to 30 carbon atoms may be replaced by a divalent group represented by the following formula (DI- 31-b),

In formula (DI-31-b), R ²⁷ and R ²⁸ independently represent alkyl having 1 to 3 carbon atoms, and v is an integer of 1 to 6;

In formulas (DI-32) and (DI-33), G ³⁰ is independently a single bond, -CO- or -CH _2- , and R ²⁹ is independently hydrogen or -CH ₃ , R ³⁰ is hydrogen, alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons;
And one hydrogen of the benzene ring in formula (DI-33) may be replaced by alkyl having 1 to 20 carbon atoms or phenyl, and
In formulas (DI-32) and (DI-33), 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;

In formulas (DI-34) and (DI-35), G ³¹ is independently -O-, -NH- or alkylene having 1 to 6 carbon atoms, and G ³² is a single bond or 1 to 3 carbon atoms Is an alkylene of
R ³¹ is hydrogen or alkyl having 1 to 20 carbon atoms, and at least one —CH ₂ — of this alkyl may be replaced by —O—, —CH = CH— or —C≡C—, R ³² is alkyl having 6 to 22 carbons, R ³³ is hydrogen or alkyl having 1 to 22 carbons, ring B ²⁵ is 1,4-phenylene or 1,4-cyclohexylene, r is 0 or 1 and -NH ₂ attached to the benzene ring indicates that the attachment position on the ring is arbitrary.

式（ＡＮ−１−２）および式（ＡＮ−４−１７）において、ｍは１〜１２の整数である。

式（ＤＩ−５−１）、式（ＤＩ−５−１２）、式（ＤＩ−５−１３）、および式（ＤＩ−７−３）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；そして、
式（ＤＩ−７−３）において、ｎはそれぞれ独立して１または２である。 [ 24 ] The tetracarboxylic acid dianhydride having no photoreactive structure is represented by the following formula (AN-1-1), formula (AN-1-2), formula (AN-1-13), formula (PA) -1), Formula (AN-3-1), Formula (AN-3-2), Formula (AN-4-5), Formula (AN-4-17), Formula (AN-4-21), Formula (AN-4-29), formula (AN-4-30), formula (AN-5-1), formula (AN-7-2), formula (AN-10-1), formula (AN-11-) 3) at least one selected from Formula (AN-16-1), Formula (AN-16-3), and Formula (AN-16-4);
The diamine having no photoreactive structure is represented by the following formula (DI-1-3), formula (DI-2-1), formula (DI-4-1), formula (DI-4-2), DI-4-10), Formula (DI-4-15), Formula (DI-5-1), Formula (DI-5-5), Formula (DI-5-9), Formula (DI-5-12) ), Formula (DI-5-13), formula (DI-5-17), formula (DI-5-28), formula (DI-5-30), formula (DI-6-7), formula (DI) -7-3), formula (DI-11-2), formula (DI-13-1), formula (DI-16-1), formula (DIH-2-1), and formula (DI-31-56) [ 23 ] The liquid crystal aligning agent for light alignment as described in [ 23 ], which is at least one selected from the group consisting of

In Formula (AN-1-2) and Formula (AN-4-17), m is an integer of 1-12.

In Formula (DI-5-1), Formula (DI-5-12), Formula (DI-5-13), and Formula (DI-7-3), m is an integer of 1 to 12;
In formula (DI-5-30), k is an integer of 1 to 5; and
In formula (DI-7-3), n is independently 1 or 2.

[ 25 ] The liquid crystal alignment according to any one of [ 11 ] to [ 24 ], further containing at least one selected from the group consisting of oxazine compounds, oxazoline compounds, epoxy compounds, and silane coupling agents. Agent.

[ 26 ] A liquid crystal alignment film formed of the liquid crystal alignment agent according to any one of [ 11 ] to [ 25 ].

[ 27 ] A liquid crystal alignment film for transverse electric field formed of the liquid crystal alignment agent according to any one of [ 11 ] to [ 25 ].

The liquid crystal display element which has a liquid crystal aligning film as described in a [ 28 ] [ 26 ] term or a [ 27 ] term.

式（１’）において、Ｒは水素、−ＯＨ、炭素数１〜６のアルキル、または炭素数１〜６のアルコキシであり；
Ａ^１およびＡ^２は、それぞれ独立して単結合または炭素数１〜６のアルキレンであり；そして、
環に結合する−ＮＨ_２の結合位置は、任意の位置である。 [ 29 ] A diamine represented by the formula (1 ').

In the formula (1 ′), R is hydrogen, —OH, alkyl having 1 to 6 carbons, or alkoxy having 1 to 6 carbons;
A ¹ and A ² are each independently a single bond or an alkylene having 1 to 6 carbon atoms;
The bonding position of —NH ₂ bonded to a ring is any position.

[ 30 ] The diamine according to item [ 29 ], which is represented by the following formula (1-15) or formula (1-29).

The liquid crystal aligning film formed from the liquid crystal aligning agent containing the polyamic acid which used the diamine represented by Formula (1) of this invention as a raw material or its derivative (s) is excellent in long-term reliability. In addition, in a liquid crystal display element of a lateral electric field type provided with a liquid crystal alignment film formed by a rubbing method, since the pretilt angle can be suppressed to a low level, the viewing angle characteristics are excellent. In a lateral electric field liquid crystal display device provided with a liquid crystal alignment film formed by a photoalignment method, the residual image characteristics are excellent. When it is desired to impart other properties, such as to improve the printability on a substrate, to provide a liquid crystal alignment film having desired properties by blending with other polymers and by using additives in combination. Can do.

In the diamine represented by formula (1), R is hydrogen, -OH, alkyl having 1 to 6 carbons, or alkoxy having 1 to 6 carbons; and X ¹ and X ² each independently have carbons It is a divalent organic group having 1 to 8 alkylene, a divalent organic group having phenylene, or a divalent organic group having alkylene having 1 to 8 carbon atoms and phenylene.

When a liquid crystal aligning agent having higher solubility in a solvent is desired, it is preferable to use a diamine in which R is alkoxy in the formula (1). Moreover, when a more reliable liquid crystal aligning film is desired, it is preferable to use the compound whose R is hydrogen or -OH in Formula (1).

Specific examples of the diamine represented by the formula (1) are compounds represented by the following formulas (1-1) to (1-84).

By using the diamine represented by the formula (1-1) to the formula (1-84) as one of the raw materials of the polymer constituting the liquid crystal aligning agent of the present invention, the display quality is deteriorated even when used for a long time Thus, a liquid crystal alignment film having high liquid crystal alignment can be obtained.

When a liquid crystal aligning agent having higher solubility in a solvent is desired, it is preferable to use diamines of formulas (1-23) and (1-37). Further, when a liquid crystal alignment film having higher reliability is desired, it is preferable to use the formula (1-1), the formula (1-15), the formula (1-29), and the formula (1-43). The diamines of formulas (1-15) and (1-29) are more preferred.

The polyamic acid and its derivative of the present invention will be described. The polyamic acid and the derivative thereof of the present invention are a reaction product of tetracarboxylic acid dianhydride and a diamine containing a diamine represented by the formula (1). Specifically, “a diamine containing a diamine represented by the formula (1)” is a diamine represented by one kind of the formula (1), a mixture of two or more kinds of diamines represented by the formula (1), And a mixture of at least one diamine represented by Formula (1) and at least one diamine other than the diamine represented by Formula (1). Moreover, the dihydrazide which plays a role similar to diamine in the polyamic acid of this invention and its derivative (s) is also contained in the "other diamine" mentioned later. In the present specification, descriptions exist which treat the dihydrazide as a diamine. That is, when it is described as "diamine" in this specification, it may be used in the meaning including dihydrazide.

The derivative of the polyamic acid is a component that dissolves in a solvent when it is a liquid crystal aligning agent described later containing a solvent, and when the liquid crystal aligning agent is a liquid crystal alignment film, a liquid crystal alignment containing polyimide as a main component It is an ingredient which can form a film. Examples of such polyamic acid derivatives include soluble polyimides, polyamic acid esters, and polyamic acid amides, and more specifically, 1) polyimides in which all the amino and carboxyl of polyamic acids undergo a ring closure reaction, 2) Partially depolymerized partial polyimide, 3) Polyamic acid ester in which carboxyl of polyamic acid is converted to ester, 4) Organic dicarboxylic acid as a part of acid dianhydride contained in tetracarboxylic acid dianhydride compound Examples thereof include polyamic acid-polyamide copolymers obtained by substituting acid for reaction, and 5) polyamide imides in which a partial or whole of the polyamic acid-polyamide copolymer is subjected to dehydration ring closure reaction. The said polyamic acid and its derivative (s) may be 1 type of compounds, and 2 or more types may be sufficient as them. Further, the polyamic acid and the derivative thereof may be any compound having a structure of a reaction product of tetracarboxylic acid dianhydride and diamine, and other raw materials may be used other than the reaction of tetracarboxylic acid dianhydride with diamine The reaction product of the other reaction may be contained.

The tetracarboxylic acid dianhydride used to produce the polyamic acid and its derivative of the present invention will be described. The tetracarboxylic acid dianhydride used in the present invention can be selected without limitation from known tetracarboxylic acid dianhydrides. Such tetracarboxylic acid dianhydrides are aromatic systems (including heteroaromatic ring systems) in which a dicarboxylic acid anhydride is directly bonded to the aromatic ring, and aliphatics in which the dicarboxylic acid anhydride is not directly bonded to the aromatic ring It may belong to any group of systems (including heterocyclic ring systems).

式（ＡＮ−Ｉ）、式（ＡＮ−ＩＶ）および式（ＡＮ−Ｖ）において、Ｘは独立して単結合または−ＣＨ_２−である。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−、−ＳＯ_２−、−Ｃ（ＣＨ_３）_２−、または−Ｃ（ＣＦ_３）_２−である。式（ＡＮ−ＩＩ）〜式（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、この基の少なくとも１つの水素はメチル、エチルまたはフェニルで置き換えられてもよい。

式（ＡＮ−ＩＩＩ）〜式（ＡＮ−Ｖ）において、環Ａ^１０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、この基の少なくとも１つの水素はメチル、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い。式（ＡＮ−ＶＩ）において、Ｘ^１０は炭素数２〜６のアルキレンであり、Ｍｅはメチルを表し、Ｐｈはフェニルを表す。式（ＡＮ−ＶＩＩ）において、Ｇ^１０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 acid dianhydrides include Formula (AN-I) to Formula (AN-VII) from the viewpoint of the availability of raw materials, the ease in polymer production, and the electrical properties of the film. Tetracarboxylic acid dianhydride represented by) is mentioned.

In formula (AN-I), formula (AN-IV) and formula (AN-V), X is independently a single bond or -CH _2- . In formula (AN-II), G is a single bond, alkylene having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO _2- , -C (CH ₃ ) _2- , or -C. _{(CF 3) 2} - a. In formulas (AN-II) to (AN-IV), Y is independently one selected from the following group of trivalent groups, and the bond is linked to any carbon, and this group At least one hydrogen of may be replaced by methyl, ethyl or phenyl.

In formulas (AN-III) to (AN-V), ring A ¹⁰ is a monocyclic hydrocarbon group of 3 to ¹⁰ carbon atoms or a fused polycyclic hydrocarbon group of 6 to 30 carbon atoms, At least one hydrogen of this group may be replaced by methyl, ethyl or phenyl, and the bond attached to the ring is connected to any carbon constituting the ring, and two bonds are identical. It may be linked to carbon. In the formula ^{(AN-VI), X 10} is alkylene of 2 to 6 carbon atoms, Me represents methyl, Ph represents phenyl. In formula (AN-VII), G ¹⁰ is independently -O-, -COO- or -OCO-, and r is independently 0 or 1.

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

式（ＡＮ−１）において、Ｇ^１１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。Ｘ^１１は独立して単結合または−ＣＨ_２−である。Ｇ^１２は独立して下記の３価の基のどちらかである。

Ｇ^１２が＞ＣＨ−であるとき、＞ＣＨ−の水素は−ＣＨ_３に置き換えられてもよい。Ｇ^１２が＞Ｎ−であるとき、Ｇ^１１が単結合および−ＣＨ_２−であることはなく、Ｘ^１１は単結合であることはない。そしてＲ^１１は水素または−ＣＨ_３である。 [Tetracarboxylic acid dianhydride represented by the formula (AN-1)]

In formula (AN-1), G ¹¹ is a single bond, alkylene having 1 to 12 carbon atoms, 1,4-phenylene or 1,4-cyclohexylene. X ¹¹ is independently a single bond or -CH _2- . G ¹² is independently one of the following trivalent groups:

When G ¹² is> CH—, hydrogen of> CH— may be replaced by —CH ₃ . When G ¹² is> ^{N-, G 11} is a single bond and -CH ₂ - that they are ^{not, X 11} is not a single bond. And R ¹¹ is hydrogen or —CH ₃ .

式（ＡＮ−１−２）および（ＡＮ−１−１４）において、ｍは1〜１２の整数である。 As an example of the tetracarboxylic dianhydride represented by Formula (AN-1), the compound represented by the following formula can be mentioned.

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

式（ＡＮ−３）において、環Ａ^１１はシクロヘキサン環またはベンゼン環である。 [Tetracarboxylic acid dianhydride represented by the formula (AN-3)]

In formula (AN-3), ring A ¹¹ is a cyclohexane ring or a benzene ring.

As an example of the tetracarboxylic dianhydride represented by Formula (AN-3), the compound represented by the following formula can be mentioned.

式（ＡＮ−４）において、Ｇ^１３は単結合、−（ＣＨ_２）_ｍ−、−Ｏ−、−Ｓ−、−Ｃ（ＣＨ_３）_２−、−ＳＯ_２−、−ＣＯ−、−Ｃ（ＣＦ_３）_２−、または下記の式（Ｇ１３−１）で表される２価の基であり、ｍは１〜１２の整数である。環Ａ^１１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。Ｇ^１３は環Ａ^１１の任意の位置に結合してよい。

式（Ｇ１３−１）において、Ｇ^１３ａおよびＧ^１３ｂはそれぞれ独立して、単結合、−Ｏ−または−ＮＨＣＯ−で表される２価の基である。フェニレンは、１，４−フェニレンおよび１，３−フェニレンが好ましい。 [Tetracarboxylic acid dianhydride represented by the formula (AN-4)]

In formula (AN-4), G ¹³ is a single bond,-(CH ₂ ) _m- , -O-, -S-, -C (CH ₃ ) _2- , -SO _2- , -CO-, -C (CF ₃ ) ₂ — or a divalent group represented by the following formula (G13-1), and m is an integer of 1 to 12. Rings A ¹¹ are each independently a cyclohexane ring or a benzene ring. G ¹³ may be bonded to any position of ring A ¹¹ .

In formula (G13-1), G ^13a and G ^13b are each independently a divalent group represented by a single bond, -O- or -NHCO-. The phenylene is preferably 1,4-phenylene and 1,3-phenylene.

式（ＡＮ−４−１７）において、ｍは１〜１２の整数である。

As an example of the tetracarboxylic dianhydride represented by Formula (AN-4), a compound represented by the following formula can be mentioned.

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

式（ＡＮ−５）において、Ｒ^１１は水素、または−ＣＨ_３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Ｒ^１１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。 [Tetracarboxylic acid dianhydride represented by formula (AN-5)]

In formula (AN-5), R ¹¹ is hydrogen or —CH ₃ . R ¹¹ whose bonding position is not fixed to the carbon atom constituting the benzene ring indicates that the bonding position on the benzene ring is arbitrary.

As an example of the tetracarboxylic dianhydride represented by Formula (AN-5), the compound represented by the following formula can be mentioned.

式（ＡＮ−６）において、Ｘ^１１は独立して単結合または−ＣＨ_２−である。Ｘ^１２は−ＣＨ_２−、−ＣＨ_２ＣＨ_２−または−ＣＨ＝ＣＨ−である。ｎは１または２である。 [Tetracarboxylic acid dianhydride represented by formula (AN-6)]

In 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;

As an example of the tetracarboxylic dianhydride represented by Formula (AN-6), the compound represented by a following formula can be mentioned.

式（ＡＮ−７）において、Ｘ^１１は単結合または−ＣＨ_２−である。 [Tetracarboxylic acid dianhydride represented by the formula (AN-7)]

In formula (AN-7), X ¹¹ is a single bond or -CH _2- .

As an example of the tetracarboxylic dianhydride represented by Formula (AN-7), the compound represented by a following formula can be mentioned.

式（ＡＮ−８）において、Ｘ^１１は単結合または−ＣＨ_２−である。Ｒ^１２は水素、−ＣＨ_３、−ＣＨ_２ＣＨ_３、またはフェニルであり、環Ａ^１２はシクロヘキサン環またはシクロヘキセン環である。 [Tetracarboxylic acid dianhydride represented by formula (AN-8)]

In formula (AN-8), X ¹¹ is a single bond or -CH _2- . R ¹² is hydrogen, —CH ₃ , —CH ₂ CH ₃ or phenyl, and ring A ¹² is a cyclohexane ring or a cyclohexene ring.

As an example of the tetracarboxylic dianhydride represented by Formula (AN-8), a compound represented by the following formula can be mentioned.

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。 [Tetracarboxylic acid dianhydride represented by the formula (AN-9)]

In formula (AN-9), each r is independently 0 or 1.

As an example of the tetracarboxylic acid dianhydride represented by the formula (AN-9), a compound represented by the following formula can be mentioned.

[Tetracarboxylic Acid Dianhydride Represented by Formula (AN-10-1) and Formula (AN-10-2)]

式（ＡＮ−１１）において、環Ａ^１１は独立してシクロヘキサン環またはベンゼン環である。 [Tetracarboxylic acid dianhydride represented by formula (AN-11)]

In formula (AN-11), ring A ¹¹ is independently a cyclohexane ring or a benzene ring.

Examples of the tetracarboxylic acid dianhydride represented by the formula (AN-11) include compounds represented by the following formula.

式（ＡＮ−１２）において、環Ａ^１１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。 [Tetracarboxylic acid dianhydride represented by the formula (AN-12)]

In formula (AN-12), the rings A ¹¹ are each independently a cyclohexane ring or a benzene ring.

As an example of the tetracarboxylic acid dianhydride represented by the formula (AN-12), a compound represented by the following formula can be mentioned.

式（ＡＮ−１３）において、Ｘ^１３は炭素数２〜６のアルキレンであり、Ｐｈはフェニルを表す。 [Tetracarboxylic acid dianhydride represented by the formula (AN-13)]

In the formula ^{(AN-13), X} 13 is alkylene of 2 to 6 carbon atoms, Ph represents phenyl.

式（ＡＮ−１３）において、Ｐｈはフェニルを表す。 Examples of the tetracarboxylic acid dianhydride represented by the formula (AN-13) include compounds represented by the following formula.

In formula (AN-13), Ph represents phenyl.

式（ＡＮ−１４）において、Ｇ^１４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。 [Tetracarboxylic acid dianhydride represented by the formula (AN-14)]

In formula (AN-14), G ¹⁴ is independently -O-, -COO- or -OCO-, and r is independently 0 or 1.

Examples of the tetracarboxylic acid 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。 [Tetracarboxylic acid dianhydride represented by the formula (AN-15)]

In formula (AN-15), w is an integer of 1 to 10.

Examples of the tetracarboxylic acid dianhydride represented by the formula (AN-15) include compounds represented by the following formula.

The following compounds may be mentioned as tetracarboxylic acid dianhydrides other than the above.

In the above-mentioned tetracarboxylic acid dianhydride, preferred materials for improving each property will be described. When importance is given to improving the orientation of the liquid crystal, compounds represented by Formula (AN-1), Formula (AN-3), and Formula (AN-4) are preferable, and 2) The compounds represented by the formula (AN-1-13), the formula (AN-3-2), the formula (AN-4-17), and the formula (AN-4-29) are particularly preferred, among which the formula In (AN-1-2), m = 4 or 8 is preferable, and in the formula (AN-4-17), m = 4 or 8 is preferable, and m = 8 is more preferable.

When importance is given to improving the transmittance of the liquid crystal display element, the formula (AN-1-1), the formula (AN-1-2), the formula (AN-3-1) and the formula (AN-4-4) can be used. 17) Formula (AN-4-30), Formula (AN-5-1), Formula (AN-7-2), Formula (AN-10-1), Formula (AN-16-3), and Formula Among the compounds represented by (AN-16-4), m = 4 or 8 is preferable in the formula (AN-1-2), and m = 4 in the formula (AN-4-17). Or 8 is preferable, and m = 8 is more preferable.

When importance is given to improving the VHR of the liquid crystal display element, the formula (AN-1-1), the formula (AN-1-2), the formula (AN-3-1), the formula (AN-4-17) And the formula (AN-4-30), the formula (AN-7-2), the formula (AN-10-1), the formula (AN-16-3), and the formula (AN-16-4) Among the compounds of formula (AN-1-2), m = 4 or 8 is preferable, and in the formula (AN-4-17), m = 4 or 8 is preferable, and m = 8 is particularly preferable. preferable.

It is effective to improve the relaxation rate of the residual charge (residual DC) in the alignment film by reducing the volume resistivity of the liquid crystal alignment film as one of the methods for preventing the image sticking. When the purpose is emphasized, the formula (AN-1-13), the formula (AN-3-2), the formula (AN-4-21), the formula (AN-4-29), and the formula (AN-) The compound represented by 11-3) is preferable.

The diamine and dihydrazide used to produce the polyamic acid and its derivative of the present invention will be described. In producing the polyamic acid of the present invention or its derivative, it can be selected without limitation from known diamines and dihydrazides.

Diamines 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, it is a group branched from the main chain, that is, a diamine having a side chain group and a diamine having no side chain group. The 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, and specific examples thereof include alkyl having 3 or more carbons, alkoxy having 3 or more carbons, alkoxyalkyl having 3 or more carbons, and A group having a steroid skeleton can be mentioned. A group having one or more rings, in which the terminal ring has 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, the diamine which has such a side chain group may be called side chain type diamine. And diamine which does not have such a side chain group may be called non side chain type diamine.

By properly using non-side chain type diamine and side chain type diamine, it is possible to cope with the pretilt angle required for each. The side chain type diamine is preferably used in combination to the extent that the properties of the present invention are not impaired. Further, it is preferable to select and use side chain type diamines and non-side chain type diamines for the purpose of improving the vertical alignment property to liquid crystal, voltage holding ratio, burn-in property and alignment property.

上記の式（ＤＩ−１）において、Ｇ^２０は、−ＣＨ_２−であり、少なくとも１つの−ＣＨ_２−は−ＮＨ−、−Ｏ−に置き換えられてもよく、ｍは１〜１２の整数であり、アルキレンの少なくとも１つの水素は−ＯＨに置き換えられてもよい。式（ＤＩ−３）および式（ＤＩ−５）〜式（ＤＩ−７）において、Ｇ^２１は独立して単結合、−ＮＨ−、−ＮＣＨ_３−、−Ｏ−、−Ｓ−、−Ｓ−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＣＯＯ−、−ＣＯＮＣＨ_３−、−ＣＯＮＨ−、−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）−、−（Ｏ−Ｃ_２Ｈ_４）_ｍ−Ｏ−、−Ｏ−ＣＨ_２−Ｃ（ＣＦ_３）_２−ＣＨ_２−Ｏ−、−Ｏ−ＣＯ−（ＣＨ_２）_ｍ−ＣＯ−Ｏ−、−ＣＯ−Ｏ−（ＣＨ_２）_ｍ−Ｏ−ＣＯ−、−（ＣＨ_２）_ｍ−ＮＨ−（ＣＨ_２）_ｍ−、−ＣＯ−（ＣＨ_２）_ｋ−ＮＨ−（ＣＨ_２）_ｋ−、−（ＮＨ−（ＣＨ_２）_ｍ) _ｋ−ＮＨ−、−ＣＯ−Ｃ_３Ｈ_６−（ＮＨ−Ｃ_３Ｈ_６）_ｎ−ＣＯ−、または−Ｓ−（ＣＨ_２）_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、ｎは１または２である。式（ＤＩ−４）において、ｓは独立して０〜２の整数である。式（ＤＩ−６）および式（ＤＩ−７）において、Ｇ^２２は独立して単結合、−Ｏ−、−Ｓ−、−ＣＯ−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−、−ＮＨ−、または炭素数１〜１０のアルキレンである。式（ＤＩ−２）〜式（ＤＩ−７）中のシクロヘキサン環およびベンゼン環の少なくとも１つの水素は、−Ｆ、−Ｃｌ、炭素数１〜３のアルキル、−ＯＣＨ_３、−ＯＨ、−ＣＦ_３、−ＣＯ_２Ｈ、−ＣＯＮＨ_２、−ＮＨＣ_６Ｈ_５、フェニル、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、シクロヘキサン環およびベンゼン環の少なくとも１つの水素は下記式（ＤＩ−４−ａ）〜式（ＤＩ−４−ｅ）で表される基の群から選ばれる１つ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−ＮＨ_２の結合位置は、Ｇ^２１またはＧ^２２の結合位置を除く任意の位置である。

式（ＤＩ−４−ａ）および式（ＤＩ−４−ｂ）において、Ｒ^２０は独立して水素または−ＣＨ_３である。 The non-side chain type diamine is described. As a diamine which does not have a known side chain, the diamine of the following formula (DI-1)-a formula (DI-16) can be mentioned.

In the above formula (DI-1), G ²⁰ is —CH ₂ —, and at least one —CH ₂ — may be replaced by —NH— or —O—, and m is an integer of 1 to 12 And at least one hydrogen of alkylene may be replaced by -OH. In formulas (DI-3) and (DI-5) to (DI-7), G ²¹ independently represents a single bond, -NH-, -NCH _3- , -O-, -S-, -S _{-S -, - SO 2 -,} - CO -, - COO -, - CONCH 3 -, - CONH -, - 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) -, - (O-C 2 H 4) m -O -, - O -CH ₂ -C (CF ₃ ) ₂ -CH ₂ -O-, -O-CO- (CH ₂ ) _m -CO-O-, -CO-O- (CH ₂ ) _m -O-CO-,- _{(CH 2) m -NH- (CH} 2) m -, - CO- (CH 2) k -NH- (CH 2) k -, - (NH- (CH 2) m) k -NH -, - CO -C ₃ H _{6 (NH-C 3 H 6)} n -CO-, or -S- _{(CH 2)} a m -S-, m is an integer from 1 to 12 independently, k is an integer from 1 to 5 , N is 1 or 2. In formula (DI-4), s is independently an integer of 0-2. In Formula (DI-6) and Formula (DI-7), G ²² is independently a single bond, -O-, -S-, -CO-, -C (CH ₃ ) _2- , -C (CF _{3 2} )-, -NH-, or alkylene having 1 to 10 carbon atoms. In the formulas (DI-2) to (DI-7), at least one hydrogen of a cyclohexane ring and a benzene ring is —F, —Cl, an alkyl having 1 to 3 carbon atoms, —OCH ₃ , —OH, —CF ₃ , -CO ₂ H, -CONH ₂ , -NHC ₆ H ₅ , phenyl or benzyl may be substituted, and additionally in formula (DI-4), at least one hydrogen of the cyclohexane ring and the benzene ring is It may be substituted by one selected from the group of groups represented by the following formulas (DI-4-a) to (DI-4-e). The group whose bonding position is not fixed to the carbon atom which comprises a ring shows that the bonding position in the ring is arbitrary. The bonding position of -NH ₂ to cyclohexane ring or benzene ring ^is any position except the bonding position of the ^{G 21} or ^{G 22.}

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

式（ＤＩ−１１）において、ｒは０または１である。式（ＤＩ−８）〜式（ＤＩ−１１）において、環に結合する−ＮＨ_２の結合位置は、任意の位置である。

In formula (DI-11), r is 0 or 1. In formulas (DI-8) to (DI-11), the bonding position of —NH ₂ bonded to a ring is an arbitrary position.

式（ＤＩ−１２）において、Ｒ^２１およびＲ^２２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、Ｇ^２３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−１３）において、Ｒ^２３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−１４）において、環Ｂは単環の複素環式芳香族基であり、Ｒ^２４は水素、−Ｆ、−Ｃｌ、炭素数１〜６のアルキル、炭素数１〜６のアルコキシ、ビニル、炭素数２〜６のアルキニルであり、ｑは独立して０〜４の整数である。式（ＤＩ−１５）において、環Ｃは複素環式芳香族基または複素環式脂肪族基である。式（ＤＩ−１６）において、Ｇ^２４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−１３）〜式（ＤＩ−１６）において、環に結合する−ＮＨ_２の結合位置は、任意の位置である。

In formula (DI-12), R ²¹ and R ^{22 each} independently represent alkyl or phenyl having 1 to 3 carbon atoms, and G ²³ independently represents alkylene, phenylene or alkyl substituted phenylene having 1 to 6 carbon atoms And w is an integer of 1 to 10. In formula (DI-13), R ²³ is independently alkyl of 1 to 5 carbons, alkoxy of 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 formula (DI-14), ring B is a monocyclic heteroaromatic group, R ²⁴ is hydrogen, -F, -Cl, alkyl having 1 to 6 carbons, alkoxy having 1 to 6 carbons , It is a vinyl and C2-C6 alkynyl, q is an integer of 0-4 independently. In formula (DI-15), ring C is a heteroaromatic group or heteroaliphatic group. In formula (DI-16), G ²⁴ is a single bond, alkylene having 2 to 6 carbon atoms, or 1,4-phenylene, and r is 0 or 1. And, a group whose bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary. In formulas (DI-13) to (DI-16), the bonding position of —NH ₂ bonded to a ring is any position.

Specific examples of the following formulas (DI-1-1) to (DI-16-1) can be given as diamines having no side chain of the above formulas (DI-1) to (DI-16) it can.

式（ＤＩ−１−７）および式（ＤＩ−１−８）において、ｋはそれぞれ独立して、１〜３の整数である。 Examples of diamines represented by formula (DI-1) are shown below.

In Formula (DI-1-7) and Formula (DI-1-8), k is each independently an integer of 1 to 3.

Examples of diamines represented by Formula (DI-2) to Formula (DI-3) are shown below.

The example of diamine represented by Formula (DI-4) is 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。

式（ＤＩ−５−３５）〜式（ＤＩ−５−３７）、および式（ＤＩ−５−３９）において、ｍは１〜１２の整数であり、式（ＤＩ−５−３８）および式（ＤＩ−５−３９）において、ｋは１〜５の整数であり、式（ＤＩ−５−４０）において、ｎは１または２の整数である。 The example of diamine represented by Formula (DI-5) is shown below.

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

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

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

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

In formulas (DI-5-35) to (DI-5-37) and formula (DI-5-39), m is an integer of 1 to 12, and formula (DI-5-38) and formula (DI-5-38) In DI-5-39), k is an integer of 1 to 5, and in the formula (DI-5-40), n is an integer of 1 or 2.

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

式（ＤＩ−７−３）および式（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。

式（ＤＩ−７−１２）において、ｍは１〜１２の整数である。 Examples of diamines represented by formula (DI-7) are shown below.

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

In formula (DI-7-12), m is an integer of 1-12.

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

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

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

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

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

Examples of diamines represented by formula (DI-13) are shown below.

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

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

Examples of diamines represented by formula (DI-16) are shown below.

The dihydrazide will be described. Examples of the known dihydrazide having no side chain include the following formulas (DIH-1) to (DIH-3).

式（ＤＩＨ−１）において、Ｇ^２５は単結合、炭素数１〜２０のアルキレン、−ＣＯ−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−Ｃ（ＣＨ_３）_２−、または−Ｃ（ＣＦ_３）_２−である。
式（ＤＩＨ−２）において、環Ｄ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、この基の少なくとも１つの水素はメチル、エチル、またはフェニルで置き換えられてもよい。式（ＤＩＨ−３）において、環Ｅ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、この基の少なくとも１つの水素はメチル、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−、−ＳＯ_２−、−Ｃ（ＣＨ_３）_２−、または−Ｃ（ＣＦ_３）_２−である。式（ＤＩＨ−２）および式（ＤＩＨ−３）において、環に結合する−ＣＯＮＨＮＨ_２の結合位置は、任意の位置である。

In formula (DIH-1), G ²⁵ is a single bond, alkylene having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO _2- , -C (CH ₃ ) _2- , or- C _{(CF 3) 2} - a.
In formula (DIH-2), ring D is a cyclohexane ring, a benzene ring or a naphthalene ring, and at least one hydrogen of this group may be replaced by methyl, ethyl or phenyl. In Formula (DIH-3), each ring E is independently a cyclohexane ring or a benzene ring, at least one hydrogen of this group may be replaced with methyl, ethyl or phenyl, and Y is a single bond, alkylene having 1 to 20 carbon atoms, -CO -, - O -, - S -, - SO 2 -, - C (CH 3) 2 -, or -C _{(CF 3) 2} - a. In formulas (DIH-2) and (DIH-3), the bonding position of -CONHNH ₂ bonded to a ring is any position.

式（ＤＩＨ−１−２）において、ｍは１〜１２の整数である。

Examples of formulas (DIH-1) to (DIH-3) are shown below.

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

Such non-side chain type diamines and hydrazides have the effect of improving the electrical characteristics, such as reducing the ion density of the liquid crystal display device. When non-side chain type diamine and / or hydrazide is used as a diamine used for producing a polyamic acid or a derivative thereof used in the liquid crystal aligning agent of the present invention, the proportion thereof in the total amount of diamine and dihydrazide is 0 to 90 mol % Is preferable, and 0 to 50 mol% is more preferable.

The side chain type diamine will be described. The following groups can be mentioned as a side chain group of side chain type diamine.

As a side chain 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. Each of alkyl, alkenyl and alkynyl in these groups is a group having 3 or more carbon atoms. However, in the alkyloxyalkyl, the total number of carbon atoms may be 3 or more. These groups may be linear or branched.

Next, phenyl, phenylalkyl, phenylalkyloxy, phenyloxy, and the like, provided that the terminal ring has alkyl having 1 or more carbons, alkoxy having 1 or more carbons, or alkoxyalkyl having 2 or more carbons 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,.

And a group having two or more benzene rings, a group having two or more cyclohexane rings, or a group having two or more rings composed of a benzene ring and a cyclohexane ring, wherein the bonding group is independently a single bond, -O-, -COO-, -OCO-, -CONH- or alkylene having 1 to 3 carbon atoms, the terminal ring being a substituent having alkyl of 1 or more carbons, fluorine-substituted alkyl having 1 or more carbons, carbon Examples include ring aggregation groups having one or more alkoxy or alkoxyalkyl having 2 or more carbon atoms. Groups having a steroid skeleton are also effective as side chain groups.

式（ＤＩ−３１）において、Ｇ^２６は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−、−ＣＯＮＨ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、または−（ＣＨ_２）_ｍ’−であり、ｍ’は１〜１２の整数である。Ｇ^２６の好ましい例は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ_２Ｏ−、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−、−ＣＨ_２Ｏ−、−ＣＨ_２−および−ＣＨ_２ＣＨ_２−である。Ｒ^２５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−３１−ａ）で表される基である。このアルキルにおいて、少なくとも１つの水素は−Ｆで置き換えられてもよく、そして少なくとも１つの−ＣＨ_２−は−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられていてもよい。このフェニルの水素は、−Ｆ、−ＣＨ_３、−ＯＣＨ_３、−ＯＣＨ_２Ｆ、−ＯＣＨＦ_２、−ＯＣＦ_３、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−ＮＨ_２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「Ｒ^２５−Ｇ^２６−」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−３１−ａ）において、Ｇ^２７、Ｇ^２８およびＧ^２９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−ＣＨ_２−は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＣＨ＝ＣＨ−で置き換えられていてもよい。環Ｂ^２１、環Ｂ^２２、環Ｂ^２３および環Ｂ^２４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、ピペリジン−１，４−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Ｂ^２１、環Ｂ^２２、環Ｂ^２３および環Ｂ^２４において、少なくとも１つの水素は−Ｆまたは−ＣＨ_３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。Ｒ^２６は水素、−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、−ＯＣＨ_２Ｆ、−ＯＣＨＦ_２、または−ＯＣＦ_３であり、この炭素数１〜３０のアルキルの少なくとも１つの−ＣＨ_２−は下記式（ＤＩ−３１−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−３１−ｂ）において、Ｒ^２７およびＲ^２８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。Ｒ^２６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。 As a diamine which has a side chain, the compound represented by the following formula (DI-31)-formula (DI-35) can be mentioned.

In formula (DI-31), G ²⁶ is 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 single bond, -O-, -COO-, -OCO-, -CH ₂ O-, and alkylene having 1 to 3 carbon atoms, and particularly preferred examples include single bond, -O-,- _{COO -, - OCO -, -} CH 2 O -, - CH 2 - and _-CH 2 CH ₂ -. R ²⁵ is alkyl having 3 to 30 carbons, phenyl, a group having a steroid skeleton, or a group represented by the following formula (DI-31-a). In this alkyl, at least one hydrogen may be replaced by -F, and at least one -CH ₂ -may be replaced by -O-, -CH = CH- or -C≡C-. Hydrogen which _{phenyl, -F, -CH 3, -OCH 3} , -OCH 2 F, -OCHF 2, -OCF 3, be replaced by an alkoxy alkyl or 3 to 30 carbon atoms having 3 to 30 carbon atoms It is also good. The bonding position of —NH ₂ bonded to a benzene ring is shown to be any position in the ring, but the bonding position is preferably meta or para. That is, the group "R ^{25 -G} 26 ^-" when the binding position of the 1-position, of the two coupling positions 3 and 5 positions, or preferably 2-position and 5-position.

In the formula (DI-31-a), G ²⁷ , G ²⁸ and G ^{29 each} represents a bonding group, which are independently a single bond or an alkylene having 1 to 12 carbon atoms, and one or more of this alkylene CH _2- may be replaced by -O-, -COO-, -OCO-, -CONH- or -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, piperidine-1,4-diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl or anthracene-9,10-diyl, ring B ²¹ , ring B ^22, the ring ^{B 23} and ring ^{B 24,} at least one hydrogen may be replaced by -F, or -CH _3, s, t and u is an integer of 0 to 2 independently of The sum is 1 to 5 and when s, t or u is 2, the two linking groups in each parenthesis may be the same or different, and even though the two rings are the same It may be different. R ²⁶ is hydrogen, -F, -OH, alkyl having 1 to 30 carbons, fluorine-substituted alkyl having 1 to 30 carbons, alkoxy having 1 to 30 carbons, -CN, -OCH ₂ F, -OCHF ₂ , or is -OCF _3, at least one -CH ₂ alkyl of 1 to 30 carbon atoms - may be replaced by a divalent group represented by the following formula (DI-31-b).

In formula (DI-31-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−３２）および式（ＤＩ−３３）において、Ｇ^３０は独立して単結合、−ＣＯ−または−ＣＨ_２−であり、Ｒ^２９は独立して水素または−ＣＨ_３であり、Ｒ^３０は水素、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−３３）におけるベンゼン環の少なくとも１つの水素は、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−３２）における２つの基「−フェニレン−Ｇ^３０−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−３３）における２つの基「−フェニレン−Ｇ^３０−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−３２）および式（ＤＩ−３３）において、ベンゼン環に結合する−ＮＨ_２はその環における結合位置が任意であることを示す。

In formulas (DI-32) and (DI-33), G ³⁰ is independently a single bond, -CO- or -CH _2- , and R ²⁹ is independently hydrogen or -CH ₃ , R ³⁰ is hydrogen, alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons. At least one hydrogen of the benzene ring in formula (DI-33) may be replaced by alkyl having 1 to 20 carbon atoms or phenyl. And, 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. It is preferable that one of the two groups "-phenylene-G ³⁰ -O-" in the formula (DI-32) be bonded to the 3-position of the steroid nucleus and the other be bonded to the 6-position of the steroid nucleus. The bonding position of the two groups “-phenylene-G ³⁰ -O-” in the formula (DI-33) to the benzene ring is preferably meta or para to the bonding position of the steroid nucleus, respectively. In formulas (DI-32) and (DI-33), -NH ₂ bonded to a benzene ring shows that the bonding position on the ring is arbitrary.

式（ＤＩ−３４）および式（ＤＩ−３５）において、Ｇ^３１は独立して−Ｏ−、−ＮＨ−または炭素数１〜６のアルキレンであり、Ｇ^３２は単結合または炭素数１〜３のアルキレンである。Ｒ^３１は水素または炭素数１〜２０のアルキルであり、このアルキルの少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよい。Ｒ^３２は炭素数６〜２２のアルキルであり、Ｒ^３３は水素または炭素数１〜２２のアルキルである。環Ｂ^２５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−ＮＨ_２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Ｇ^３１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 formulas (DI-34) and (DI-35), G ³¹ is independently -O-, -NH- or alkylene having 1 to 6 carbon atoms, and G ³² is a single bond or 1 to 3 carbon atoms Is alkylene. R ³¹ is hydrogen or alkyl having 1 to 20 carbon atoms, and at least one —CH ₂ — of this alkyl may be replaced by —O—, —CH = CH— or —C≡C—. R ³² is alkyl having 6 to 22 carbons, and R ³³ is hydrogen or alkyl having 1 to 22 carbons. Ring B ²⁵ is 1,4-phenylene or 1,4-cyclohexylene, and r is 0 or 1. And -NH ₂ bonded to the benzene ring shows that the bonding position in the ring is arbitrary, but is preferably independently at the meta position or para position with respect to the bonding position of G ³¹ .

The specific example of side chain type diamine is illustrated below. Examples of the diamine having a side chain of the above formulas (DI-31) to (DI-35) include compounds represented by the following formulas (DI-31-1) to (DI-35-3) it can.

式（ＤＩ−３１−１）〜式（ＤＩ−３１−１１）において、Ｒ^３４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。Ｒ^３５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 formula (DI-31) are shown below.

In formulas (DI-31-1) to (DI-31-11), R ³⁴ is alkyl having 1 to 30 carbons or alkoxy having 1 to 30 carbons, preferably alkyl having 5 to 25 carbons or It is a C5-C25 alkoxy. 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−３１−１２）〜式（ＤＩ−３１−１７）において、Ｒ^３６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。Ｒ^３７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 formulas (DI-31-12) to (DI-31-17), R ³⁶ is an alkyl having 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−３１−１８）〜式（ＤＩ−３１−４３）において、Ｒ^３８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。Ｒ^３９は水素、−Ｆ、炭素数１〜３０のアルキル、炭素数１〜３０のアルコキシ、−ＣＮ、−ＯＣＨ_２Ｆ、−ＯＣＨＦ_２または−ＯＣＦ_３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Ｇ^３３は炭素数１〜２０のアルキレンである。

In formulas (DI-31-18) to (DI-31-43), R ³⁸ is alkyl having 1 to 20 carbons or alkoxy having 1 to 20 carbons, preferably alkyl having 3 to 20 carbons or It is a C3-C20 alkoxy. R ³⁹ is hydrogen, -F, alkyl having 1 to 30 carbons, alkoxy having 1 to 30 carbons, -CN, -OCH ₂ F, -OCHF ₂ or -OCF ₃ , preferably having 3 to 25 carbons It is alkyl or alkoxy having 3 to 25 carbon atoms. The ^{G 33} is alkylene of 1 to 20 carbon atoms.

Examples of compounds represented by formula (DI-32) are shown below.

Examples of the compound represented by formula (DI-33) are shown below.

式（ＤＩ−３４−１）〜式（ＤＩ−３４−１４）において、Ｒ^４０は水素または炭素数１〜２０のアルキル、好ましくは水素または炭素数１〜１０のアルキルであり、そしてＲ^４１は水素または炭素数１〜１２のアルキルである。 Examples of compounds represented by formula (DI-34) are shown below.

In formulas (DI-34-1) to (DI-34-14), R ⁴⁰ is hydrogen or alkyl having 1 to 20 carbons, preferably hydrogen or alkyl having 1 to 10 carbons, and R ⁴¹ is It is hydrogen or alkyl having 1 to 12 carbons.

式（ＤＩ−３５−１）〜式（ＤＩ−３５−３）において、Ｒ^３７は炭素数６〜３０のアルキルであり、Ｒ^４１は水素または炭素数１〜１２のアルキルである。 The example of a compound represented by Formula (DI-35) is shown below.

In formulas (DI-35-1) to (DI-35-3), R ³⁷ is alkyl having 6 to 30 carbon atoms, and R ⁴¹ is hydrogen or alkyl having 1 to 12 carbon atoms.

式（ＤＩ−３６−１）〜式（ＤＩ−３６−８）において、Ｒ^４２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−３６−９）〜式（ＤＩ−３６−１１）において、ｅは２〜１０の整数であり、式（ＤＩ−３６−１２）中、Ｒ^４３はそれぞれ独立して水素、−ＮＨＢｏｃまたは−Ｎ（Ｂｏｃ）_２であり、Ｒ^４３の少なくとも１つは−ＮＨＢｏｃまたは−Ｎ（Ｂｏｃ）_２であり、式（ＤＩ−３６−１３）において、Ｒ^４４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。 Examples of the diamine in the present invention include formula (DI-1-1) to formula (DI-16-1), formula (DIH-1-1) to formula (DIH-3-6) and formula (DI-31-1) Diamines other than the diamines represented by the formulas (DI-35-3) can also be used. As such a diamine, the compound represented, for example by following formula (DI-36-1)-formula (DI-36-13) is mentioned.

In formulas (DI-36-1) to (DI-36-8), each R ⁴² independently represents an alkyl group having 3 to 30 carbon atoms.

In the formulas (DI-36-9) to (DI-36-11), e is an integer of 2 to 10, and in the formula (DI-36-12), each of R ⁴³ independently represents hydrogen, -NHBoc Or -N (Boc) ₂ and at least one of R ⁴³ is -NHBoc or -N (Boc) ₂ ; and in formula (DI-36-13), R ⁴⁴ is -NHBoc or -N (Boc) ₂ and m is an integer of 1-12. Here, Boc is a t-butoxycarbonyl group.

In the above diamines and dihydrazides, preferred materials for improving the respective properties are described. When importance is given to further improving the alignment of the liquid crystal, the formula (DI-1-3), the formula (DI-5-1), the formula (DI-5-5), the formula (DI-5-9) Formula (DI-5-12), Formula (DI-5-13), Formula (DI-5-29), Formula (DI-6-7), Formula (DI-7-3), and Formula It is preferable to use a compound represented by DI-11-2). In formula (DI-5-1), m = 2, 4 or 6 is preferable, and m = 4 is more preferable. In formula (DI-5-12), m = 2 to 6 is preferable, and m = 5 is more preferable. In formula (DI-5-13), m = 1 or 2 is preferable, and m = 1 is more preferable.

When importance is given to improving the transmittance, formula (DI-1-3), formula (DI-2-1), formula (DI-5-1), formula (DI-5-5), formula It is preferable to use the diamine represented by (DI-5-24) and Formula (DI-7-3), and the compound represented by Formula (DI-2-1) is more preferable. In formula (DI-5-1), m is preferably 2 to 4, or 6 and more preferably m = 4. In formula (DI-7-3), m = 2 or 3, n = 1 or 2 is preferable, and m = 3 and n = 1 are more preferable.

When importance is given to improving VHR of the liquid crystal display element, the formula (DI-2-1), the formula (DI-4-1), the formula (DI-4-2), the formula (DI-4-10) It is preferred to use the compounds represented by formula (DI-4-15), formula (DI-5-28), formula (DI-5-30), and formula (DI-13-1), The diamine represented by (DI-2-1), Formula (DI-5-1), and Formula (DI-13-1) is more preferable. In formula (DI-5-1), m = 1 is preferable. In formula (DI-5-30), k is preferably 2.

It is effective to improve the relaxation rate of the residual charge (residual DC) in the alignment film by reducing the volume resistivity of the liquid crystal alignment film as one of the methods for preventing the image sticking. When the purpose is emphasized, the formula (DI-4-1), the formula (DI-4-2), the formula (DI-4-10), the formula (DI-4-15) and the formula (DI-5) -1), formula (DI-5-12), formula (DI-5-13), formula (DI-5-28), formula (DI-7-12), and formula (DI-16-1) It is preferable to use the compound represented, and the compound represented by Formula (DI-4-1), Formula (DI-5-1), and Formula (DI-5-13) is more preferable. In formula (DI-5-1), m = 2, 4 or 6 is preferable, and m = 4 is more preferable. In formula (DI-5-12), m = 2 to 6 is preferable, and m = 5 is more preferable. In formula (DI-5-13), m = 1 or 2 is preferable, and m = 1 is more preferable. In formula (DI-7-12), m = 3 or 4 is preferable, and m = 4 is more preferable.

In each diamine, part of the diamine may be replaced by monoamine in the range of 40 mol% or less of the ratio of monoamine to diamine. Such substitution can cause termination of the polymerization reaction when producing the polyamic acid, and can suppress the progress of further polymerization reactions. Therefore, by such substitution, the molecular weight of the obtained polymer (polyamic acid or its derivative) can be easily controlled, and for example, the coating characteristics of the liquid crystal aligning agent can be improved without impairing the effects of the present invention. be able to. The diamine to be replaced by the monoamine may be one or more, as long as the effects of the present invention are not impaired. Examples of the monoamine include aniline, 4-hydroxyaniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, and n- Undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, and n-eicosylamine Can be mentioned.

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 its derivative is modified to control the molecular weight. By using this terminal-modified type polyamic acid or a derivative thereof, the coating properties of the liquid crystal aligning agent can be improved, for example, without the effects of the present invention being impaired. From the above viewpoint, the content of the monoisocyanate compound in the monomer is preferably 1 to 10 mol% with respect to the total amount of diamine and tetracarboxylic acid dianhydride in the monomer. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

式（Ｐ−１）中、Ｒ^６１は独立して、水素原子、炭素数１〜５のアルキル基、またはフェニル基である。 When the polyamic acid of the present invention or a derivative thereof is used as a photoalignment film to which liquid crystal alignment ability is imparted by light irradiation, for example, irradiation of ultraviolet light, a monomer having a photoreactive structure as a raw material of polyamic acid and its derivative It can be used suitably. By using a monomer having a photoreactive structure, polyamic acid having a photoreactive structure and a derivative thereof can be synthesized. The photoreactive structure is, for example, a photolysis structure represented by the following formula (P-1) that causes decomposition by ultraviolet irradiation, or a formula (P-2) to a formula (P-4) that causes isomerization. And photodimerization structures represented by formulas (P-5) to (P-7) which cause dimerization.

In formula (P-1), R ⁶¹ is independently a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, or a phenyl group.

As a compound which has a photolytic structure represented by Formula (P-1), the compound represented by following formula (PA-1)-formula (PA-3) is mentioned.

Among these compounds, the compounds represented by the above formula (PA-1) and the formula (PA-2) are suitably used.

The compounds represented by the formulas (PA-1) to (PA-3) are liquid crystal aligning agents utilizing liquid crystal alignment ability based on photoisomerization reaction, and liquid crystal alignment utilizing liquid crystal alignment ability based on photodimerization. When it is used as a raw material monomer of a polymer used for an agent or a liquid crystal aligning agent for rubbing, it is treated as a tetracarboxylic acid dianhydride having no photoreactive structure.

式（ＩＩ）〜式（Ｖ）において、Ｒ^２およびＲ^３は−ＮＨ_２を有する１価の有機基または−ＣＯ−Ｏ−ＣＯ−を有する１価の有機基であり、式（ＩＶ）においてＲ^４は２価の有機基であり、式（ＶＩ）においてＲ^５は−ＮＨ_２もしくは−ＣＯ−Ｏ−ＣＯ−を有する芳香環である。 As a compound which has a photoisomerization structure represented by Formula (P-2)-a formula (P-4), from the group of the compound represented by the following formula (II)-a formula (VI) with favorable photosensitivity Preferably, it is at least one selected, and more preferably a compound represented by formula (V).

In formulas (II) to (V), R ² and R ^{3 each} represents a monovalent organic group having —NH ₂ or a monovalent organic group having —CO—O—CO— in the formula (IV) R ⁴ is a divalent organic group, and in formula (VI), R ⁵ is an aromatic ring having —NH ₂ or —CO—O—CO—.

The photoisomerization structure may be incorporated into either the main chain or the side chain of the polyamic acid or the derivative thereof in the present invention, but by incorporating it into the main chain, it can be suitably used for a liquid crystal display device of transverse electric field type.

上記各式において、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、式（Ｖ−２）において、Ｒ^６は独立して−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、または−ＣＯＯＣＨ_３であり、ａは０〜２の整数であり、式（Ｖ−３）において、環Ａおよび環Ｂはそれぞれ独立して、単環式炭化水素、縮合多環式炭化水素および複素環から選ばれる少なくとも１つであり、Ｒ^１１は、炭素数１〜２０の直鎖アルキレン、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−または−Ｎ（ＣＨ_３）ＣＯ−であり、Ｒ^１２は、炭素数１〜２０の直鎖アルキレン、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−または−Ｎ（ＣＨ_３）ＣＯ−であり、Ｒ^１１およびＲ^１２において、直鎖アルキレンの−ＣＨ_２−の１つまたは２つは−Ｏ−で置換されてもよく、Ｒ^７〜Ｒ^１０は、それぞれ独立して、−Ｆ、−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、または−ＯＨであり、そして、ｂ〜ｅは、それぞれ独立して、０〜４の整数である。 As a material which has the said photoisomerization structure, following formula (II-1), Formula (II-2), Formula (III-1), Formula (III-2), Formula (IV-1), Formula (IV) -2) at least one selected from the group of compounds represented by Formula (V-1) to Formula (V-3), Formula (VI-1), and Formula (VI-2) Can.

In each of the above formulas, 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 the formula (V-2), R ⁶ is independent And in the formula (V-3), ring A and ring B are each independently -CH ₃ , -OCH ₃ , -CF ₃ or -COOCH ₃ ; R ¹¹ is at least one selected from a monocyclic hydrocarbon, a fused polycyclic hydrocarbon and a heterocycle, and R ¹¹ is a linear alkylene of 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO- or -N _(CH 3) a ^{CO-, R 12} is a straight-chain alkylene having 1 to 20 carbon atoms, -COO -, - OCO -, - NHCO- or -N _(CH 3) a ^{CO-, R 11} And R ^{12 represents} a linear alkylene of —C One or two of H _2- may be substituted with -O-, and R ^{7 to} R ¹⁰ are each independently -F, -CH ₃ , -OCH ₃ , -CF ₃ , or -OH And b to e each independently represent an integer of 0 to 4;

The compounds represented by the above formulas (V-1), (V-2) and (VI-2) can be particularly suitably used from the viewpoint of photosensitivity. In the formula (V-2) and the formula (VI-2), the compound at the para-position of the amino group is attached, and further, in the formula (V-2), the compound at a = 0 is the point of orientation Can be used more suitably.

An acid dianhydride or diamine having a structure capable of causing isomerization by ultraviolet irradiation as shown in formulas (II-1) to (VI-2) has the following formulas (II-1-1) to (VI-2-3) Can be specifically represented by

Among these, it is a compound having a structure capable of causing isomerization by irradiation with ultraviolet light of formulas (VI-1-1) to (V-3-8), and therefore, for photoalignment with higher sensitivity to ultraviolet irradiation. A liquid crystal aligning agent can be obtained. Formula (V-1-1), Formula (V-2-1), Formula (V-2-4) to Formula (V-2-11) and Formula (V-3-1) to Formula (V-3) By setting -8) to a compound including a structure capable of causing isomerization by ultraviolet irradiation, it is possible to obtain a liquid crystal aligning agent for photo alignment which can align liquid crystal molecules more uniformly. The liquid crystal for photo-alignment which can lessen coloring of the alignment film formed by setting it as a compound containing the structure which can raise | generate isomerization by ultraviolet irradiation by Formula (V-2-4)-Formula (V-3-8). An alignment agent can be obtained.

In synthesizing a polyamic acid having a photoreactive structure and a derivative thereof, a tetracarboxylic acid dianhydride having a photoreactive structure (hereinafter, may be referred to as photosensitive tetracarboxylic acid dianhydride) or the light described above. A diamine having a reactive structure (hereinafter, may be referred to as photosensitive diamine) can be used as a raw material. A diamine having a photoreactive structure and a tetracarboxylic acid dianhydride having a photoreactive structure may be used in combination.

When a photosensitive tetracarboxylic acid dianhydride is used as a raw material for synthesizing a polyamic acid having a photoreactive structure and a derivative thereof, a tetracarboxylic acid dianhydride having no photoreactive structure (hereinafter, non-photosensitive) ) May be used in combination. At this time, in order to prevent a decrease in sensitivity of the alignment film to light, the proportion of photosensitive tetracarboxylic acid dianhydride in the total amount of tetracarboxylic acid dianhydride used as a raw material is preferably 20 mol% or more, and 50 mol% The above is more preferable. Further, two or more photosensitive tetracarboxylic acid dianhydrides may be used in combination in order to improve various characteristics such as sensitivity to light, afterimage characteristics and the like.

In synthesizing a polyamic acid having a photoreactive structure and a derivative thereof, when a photosensitive diamine is used as a raw material, the diamine represented by the formula (1) of the present invention and the photosensitive diamine are used in combination. The diamine represented by Formula (1) does not have a photoreactive structure. A diamine having no photoreactive structure other than the diamine represented by formula (1) (hereinafter may be referred to as a non-photosensitive diamine) may be further used in combination. At this time, in order to prevent a decrease in the sensitivity of the alignment film to light, the proportion of the photosensitive diamine in the total amount of diamine used as the raw material is preferably 20 mol% or more, more preferably 50 mol% or more. Further, two or more photosensitive diamines may be used in combination to improve various characteristics such as sensitivity to light, afterimage characteristics and the like.

In the case of using a photosensitive tetracarboxylic acid dianhydride and a photosensitive diamine in combination as a raw material for synthesizing a polyamic acid having a photoreactive structure and a derivative thereof, a non-photosensitive tetracarboxylic acid dianhydride and a formula ( You may use together non-photosensitive diamine other than the diamine represented by 1). At this time, in order to prevent the decrease in sensitivity of the alignment film to light, the ratio of the total of photosensitive tetracarboxylic acid dianhydride and photosensitive diamine in the total amount of tetracarboxylic acid dianhydride and diamine used as a raw material is 20 moles. % Or more is preferable and 50 mol% or more is more preferable. Further, two or more photosensitive tetracarboxylic acid dianhydrides and / or photosensitive diamines may be used in combination in order to improve various characteristics described above such as sensitivity to light, afterimage characteristics and the like.

The liquid crystal aligning agent of the present invention will be described. The liquid crystal aligning agent of this invention may further contain other components other than the polyamic acid which used at least 1 of the diamine represented by Formula (1) as a raw material, or its derivative (s). One or more other components may be used. Examples of other components include other polymers and compounds described later.

The other polymers are polymers other than polyamic acid or its derivative obtained by reacting tetracarboxylic acid dianhydride and diamine containing diamine of formula (1). Specifically, a polyamic acid or derivative thereof obtained by reacting a diamine not containing diamine of formula (1) with tetracarboxylic dianhydride (hereinafter, may be referred to as other polyamic acid or derivative thereof). And polyesters, polyamides, polysiloxanes, cellulose derivatives, polyacetals, polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylates and the like. Among these, other polyamic acids or derivatives thereof and polysiloxanes are preferable, and other polyamic acids or derivatives thereof are more preferable.

The tetracarboxylic acid dianhydride and diamine used to synthesize other polyamic acids or derivatives thereof can be selected without limitation from the known tetracarboxylic acid dianhydrides and diamines exemplified above. .

In the present invention, a polyamic acid or a derivative thereof synthesized using a diamine containing a diamine of the formula (1) and another polyamic acid or a derivative thereof can be blended and used as an alignment agent. When such a two-component polymer is used, for example, a polymer having excellent performance in liquid crystal alignment ability is selected on one side, and the other has excellent performance on improving the electrical characteristics of the liquid crystal display element. There is an aspect of selecting a polymer having In this case, by controlling the structure and molecular weight of each polymer, a liquid crystal aligning agent in which these polymers are dissolved in a solvent is applied to a substrate as described later, and predrying is performed to form a thin film. In the process, it is possible to segregate the polymer having the performance excellent in liquid crystal alignment ability in the upper layer of the thin film and the polymer having the excellent performance in improving the electrical characteristics of the liquid crystal display element in the lower layer of the thin film. In this case, in the mixed polymer, a phenomenon in which the polymer with small surface energy is separated into the upper layer and the polymer with large surface energy is separated into the lower layer can be applied. The confirmation of such layer separation means that the surface energy of the formed alignment film is equal to or close to the surface energy of the film formed by the liquid crystal aligning agent containing only the polymer intended to be segregated in the upper layer. It can be confirmed by the value.

In the aspect in which the liquid crystal aligning agent of the present invention is a liquid crystal aligning agent for photoalignment, the polyamic acid having the photoreactive structure of the present invention or a derivative thereof can be used without intention of layer separation in a thin film. Moreover, the liquid crystal aligning agent which has a photoreactive structure can also be used as a polymer segregated to the upper layer of the said thin film. In this case, the polymer segregating in the lower layer of the thin film is a polyamic acid or a derivative thereof having no photoreactive structure, but the polymer segregating in the lower layer of the thin film is a polyamic acid having a photoreactive structure or a derivative thereof It may be.

The diamine represented by the formula (1) of the present invention may be used as a raw material monomer of the polymer which segregates in the upper layer of the thin film, or may be used as a raw material monomer of the polymer which segregates in the lower layer of the thin film. . The diamine represented by Formula (1) may be used as a raw material monomer of any one of both polymers, and may be used as a raw material monomer of both polymers.

The non-photosensitive tetracarboxylic acid dianhydride used to synthesize the polyamic acid or derivative thereof segregated in the upper layer of the thin film is selected without limitation from the known tetracarboxylic acid dianhydrides exemplified above. can do.

Among them, when importance is given to improving layer separation, compounds represented by Formula (AN-1-1), Formula (AN-4-17), and Formula (PA-1) are preferable. In formula (AN-4-17), m = 4 or 8 is preferable, and m = 8 is more preferable.

When importance is given to improving the transmittance of the liquid crystal display element, the formula (AN-1-1), the formula (AN-1-2), the formula (PA-1), the formula (AN-3-1) Formula (AN-4-17) Formula (AN-4-30) Formula (AN-5-1) Formula (AN-7-2) Formula (AN-10-1) Formula (AN-) 10-2) The compounds represented by the formula (AN-16-3) and the formula (AN-16-4) are preferable, and in the case of m = 4 or 8 in the formula (AN-1-2) among them Is preferred, and in the formula (AN-4-17), m = 4 or 8 is preferred, and m = 8 is more preferred.

When importance is given to improving the VHR of the liquid crystal display device, the formula (PA-1), the formula (AN-7-2), the formula (AN-10-1), the formula (AN-10-2), The compounds represented by the formula (AN-16-3) and the formula (AN-16-4) are preferable, and among them, in the formula (AN-1-2), m = 4 or 8 is preferable.

It is effective to improve the relaxation rate of the residual charge (residual DC) in the alignment film by reducing the volume resistivity of the liquid crystal alignment film as one of the methods for preventing the image sticking. When the purpose is emphasized, the formula (AN-1-13), the formula (AN-3-2), the formula (AN-4-21), the formula (AN-4-29), and the formula (AN-) The compound represented by 11-3) is preferable.

The tetracarboxylic acid dianhydride used to synthesize the polyamic acid or derivative thereof segregated in the upper layer of the thin film should contain 10 mol% or more of aromatic tetracarboxylic acid dianhydride in the total amount of tetracarboxylic acid dianhydride. Is preferable, and containing 30% or more is more preferable.

The non-photosensitive diamine and hydrazide used to synthesize the polyamic acid or derivative thereof segregated in the upper layer of the thin film can be selected without limitation from the known diamines exemplified above.

Among them, when it is important to further improve the layer separation, that is, the orientation of the liquid crystal, the formula (DI-4-1), the formula (DI-5-1), and the formula (DI-7-3) It is preferable to use a compound represented by). Among them, in the formula (DI-5-1), m = 1, 2 or 4 is preferable, and m = 4 is more preferable. In formula (DI-7-3), m = 3 and n = 1 are preferable.

When importance is given to improving the transmittance, it is preferable to use a diamine represented by Formula (PA-1), Formula (DI-5-1), and Formula (DI-7-3), The compound represented by (PA-1) is particularly preferable. In formula (DI-5-1), m = 1, 2 or 4 is preferable, and m = 1 or 2 is more preferable.

When importance is given to improving the VHR of the liquid crystal display element, the formula (DI-4-1), the formula (DI-4-2), the formula (DI-4-15), the formula (DI-5-1) It is preferable to use the compounds represented by formula (DI-5-17), formula (DI-5-28), formula (DI-5-30), and formula (DI-13-1), The compounds represented by (DI-5-1) and the formula (DI-13-1) are more preferable. Above all, compounds in which m = 1 or 2 in the formula (DI-5-1) and compounds in which k = 2 in the formula (DI-5-30) are more preferable.

It is effective to improve the relaxation rate of the residual charge (residual DC) in the alignment film by reducing the volume resistivity of the liquid crystal alignment film as one of the methods for preventing the image sticking. When the purpose is emphasized, the formula (DI-4-1), the formula (DI-4-2), the formula (DI-4-10), the formula (DI-4-15) and the formula (DI-5) -1), formula (DI-5-9), formula (DI-5-12), formula (DI-5-13), formula (DI-5-28), formula (DI-5-30), and It is preferable to use a compound represented by the formula (DI-16-1), and represented by the formula (DI-4-1), the formula (DI-5-1), and the formula (DI-5-12) Compounds are more preferred. In formula (DI-5-1), m is preferably 1 or 2. In formula (DI-5-12), m = 2 to 6 is preferable, and m = 5 is more preferable. In formula (DI-5-13), m = 1 or 2 is preferable, and m = 1 is more preferable. In formula (DI-5-30), k is preferably 2.

The non-photosensitive diamine used to synthesize the polyamic acid or derivative thereof segregated in the upper layer of the thin film preferably contains 30% by mole or more, more preferably 50% or more of the aromatic diamine in the total amount of diamine.

The tetracarboxylic acid dianhydride used to synthesize polyamic acid or a derivative thereof which segregates in the lower layer of the thin film can be selected without limitation from the known tetracarboxylic acid dianhydrides exemplified above. .

Among them, when importance is given to improving the layer separation, the formula (AN-3-2), the formula (AN-1-13), the formula (AN-1-1), and the formula (AN-4-4) The compound represented by 21) is preferable.

When importance is given to improving the transmittance of the liquid crystal display element, the formula (AN-1-1), the formula (AN-1-2), the formula (PA-1), the formula (AN-3-1) Formula (AN-4-17) Formula (AN-4-30) Formula (AN-5-1) Formula (AN-7-2) Formula (AN-10-1) Formula (AN-) Compounds represented by formula 10-2), formula (AN-16-3), and formula (AN-16-4) are preferred. In formula (AN-1-2), m = 4 or 8 is preferable, and in formula (AN-4-17), m = 4 or 8 is preferable, and m = 8 is more preferable.

When importance is given to improving the VHR of the liquid crystal display device, the formula (PA-1), the formula (AN-7-2), the formula (AN-10-1), the formula (AN-10-2), The compounds represented by the formula (AN-16-3) and the formula (AN-16-4) are preferable, and among them, in the formula (AN-1-2), m = 4 or 8 is preferable.

It is effective to improve the relaxation rate of the residual charge (residual DC) in the alignment film by reducing the volume resistivity of the liquid crystal alignment film as one of the methods for preventing the image sticking. When the purpose is emphasized, the formula (AN-1-13), the formula (AN-3-2), the formula (AN-4-21), the formula (AN-4-29), and the formula (AN-) The compound represented by 11-3) is preferable.

The tetracarboxylic acid dianhydride used to synthesize polyamic acid or a derivative thereof which is segregated in the lower layer of the thin film contains 10 mol% or more of aromatic tetracarboxylic acid dianhydride in the total amount of tetracarboxylic acid dianhydride. Is preferable, and containing 30% or more is more preferable.

The non-photosensitive diamines and hydrazides used to synthesize the polyamic acid or derivative thereof segregated in the lower layer of the thin film can be selected without limitation from the known diamines exemplified above.

Among them, when it is important to further improve the layer separation, that is, the alignment of the liquid crystal, the formula (DI-4-1), the formula (DI-4-2), the formula (DI-4-10), Compounds represented by formula (DI-5-9), formula (DI-5-28), formula (DI-5-30), and formula (DIH-2-1) are preferred. Among these, in the formula (DI-5-30), diamines in which k = 2 are preferable.

When importance is given to improving the transmittance, compounds represented by Formula (PA-1), Formula (DI-5-1), and Formula (DI-7-3) are preferable, and Formula (PA- The compound represented by 1) is more preferable. In formula (DI-5-1), m = 1, 2 or 4 is preferable, and m = 1 or 2 is more preferable.

When importance is given to improving the VHR of the liquid crystal display element, the formula (DI-4-1), the formula (DI-4-2), the formula (DI-4-15), the formula (DI-5-1) The compounds represented by formula (DI-5-17), formula (DI-5-28), formula (DI-5-30), and formula (DI-13-1) are preferable, and The compounds represented by 5-1) and formula (DI-13-1) are more preferable. Among them, in the formula (DI-5-1), m = 1 or 2 is particularly preferable, and in the formula (DI-5-30), k = 2 is particularly preferable.

It is effective to improve the relaxation rate of the residual charge (residual DC) in the alignment film by reducing the volume resistivity of the liquid crystal alignment film as one of the methods for preventing the image sticking. When the purpose is emphasized, the formula (DI-4-1), the formula (DI-4-2), the formula (DI-4-10), the formula (DI-4-15) and the formula (DI-5) -1), formula (DI-5-9), formula (DI-5-12), formula (DI-5-13), formula (DI-5-28), formula (DI-5-30), and Compounds represented by the formula (DI-16-1) are preferable, and compounds represented by the formulas (DI-4-1), (DI-5-1), and (DI-5-12) are more preferable. preferable. Among them, in the formula (DI-5-1), m = 1 or 2 is preferable. In formula (DI-5-12), m = 2 to 6 is preferable, and m = 5 is more preferable. In formula (DI-5-13), m = 1 or 2 is preferable, and m = 1 is more preferable. In formula (DI-5-30), k is preferably 2.

The non-photosensitive diamine used to synthesize polyamic acid or a derivative thereof which is segregated in the lower layer of the thin film preferably contains 30% by mole or more of the aromatic diamine with respect to all diamines, and contains 50% or more Is more preferred.

The polyamic acid or derivative thereof segregating in the upper layer of the thin film and the polyamic acid or derivative thereof segregating in the lower layer of the thin film are both described below as the synthesis method of the polyamic acid or derivative thereof which is an essential component of the liquid crystal aligning agent of the present invention. It can synthesize | combine according to the place described in these.

The proportion of polyamic acid or derivative thereof segregating in the upper layer of the thin film relative to the total amount of polyamic acid or derivative thereof segregating in the upper layer of the thin film and polyamic acid segregating in the lower layer of the film is 5 wt% to 50 wt% % Is preferable, and 10% by weight to 40% by weight is more preferable.

<Polysiloxane>
As polysiloxane, Unexamined-Japanese-Patent 2009-036966, Unexamined-Japanese-Patent 2010-185001, Unexamined-Japanese-Patent 2011-102963, Unexamined-Japanese-Patent 2011-253175, Unexamined-Japanese-Patent 2012-159825, International Publication 2008/044644, International Publication 2009/14948099, International Publication 2010 It is disclosed in / 074261, International Publication 2010/074264, International Publication 2010/126108, International Publication 2011/068123, International Publication 2011/068127, International Publication 2011/068128, International Publication 2012/115157, International Publication 2012/165354, etc. It can further contain a polysiloxane.

<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 electric characteristics of the liquid crystal display element over a long period of time. The alkenyl-substituted nadiimide compounds may be used alone or in combination of two or more. 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 based on the polyamic acid or its derivative from the above-mentioned purpose. It is further preferred that

式（ＮＡ）において、Ｌ^１およびＬ^２は独立して水素、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、炭素数６〜１２の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 is 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 independently represent hydrogen, alkyl having 1 to 12 carbons, alkenyl having 3 to 6 carbons, cycloalkyl having 5 to 8 carbons, aryl having 6 to 12 carbons or N is 1 or 2;

In the formula (NA), when n is 1, W is alkyl of 1 to 12 carbons, alkenyl of 2 to 6 carbons, cycloalkyl of 5 to 8 carbons, aryl of 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, r is 0 or 1 And k is an integer of 1 to 30),-(Z ⁴ ) _r -B-Z ⁵ -H (wherein Z ⁴ and Z ⁵ are independently carbon number A group represented by the alkylene of 1 to 4 or the cycloalkylene having 5 to 8 carbon atoms, B is phenylene, and r is 0 or 1. -B-T-B-H (wherein , B is phenylene, and T is -CH _2- , -C (CH ₃ ) _2- , -O-, -CO-,- Or a group represented by the formula S- or -SO _2- ) or a group in which 1 to 3 hydrogens of these groups are substituted by -OH.

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 groups in which one or two hydrogens of these groups have been replaced by -OH.

In the formula (NA), when n = 2, W is alkylene having 2 to 20 carbons, cycloalkylene having 5 to 8 carbons, arylene having 6 to 12 carbons, -Z ¹ -O- (Z ² O) a group represented by _k- Z ^3- (wherein the definitions of Z ^{1 to} Z ³ and k are as defined in the above n = 1), -Z ^4- B-Z ^5- (wherein , Z ⁴ , Z ⁵ and B are as defined in the above n = 1.), -B- (O-B) _r -T- (B-O) _r- B- (Wherein, B is phenylene, T is an alkylene having 1 to 3 carbon atoms, -O- or -SO _2- , and the definition of r is as defined in the above n = 1.) Groups, or groups in which 1 to 3 hydrogens of these groups are replaced by -OH.

At this time, preferable W is alkylene having 2 to 12 carbons, cyclohexylene, phenylene, tolylene, xylylene, -C ₃ H ₆ -O- (Z ² -O) _n -O-C ₃ H _6- (wherein Z ² is alkylene having 2 to 6 carbons, n is 1 or 2.), a group represented by -B-T-B- (wherein, B is phenylene, and T is- CH ₂ -, - O- or -SO ₂ -. a is a group represented _{by), -B-O-B-} C 3 H 6 -B-O-B- ( wherein, B is phenylene. And groups in which one or two hydrogens of these groups are replaced by -OH.

Such an alkenyl substituted nadiimide compound is synthesized, for example, by maintaining an alkenyl substituted nadic anhydride derivative and a diamine at a temperature of 80 to 220 ° C. for 0.5 to 20 hours as described in Patent 2729565. The compound obtained by this method or the compound marketed can be used. The following compounds may be mentioned as specific examples of the alkenyl substituted nadiimide compound.

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 -Dicarboxy De, 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- en- , 3-dicarboximide,

N- (2,2-dimethyl-3-hydroxypropyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2,2-dimethyl-3-hydroxyl) 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) bicyclic [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-dicarboximides and their oligomers,

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-dicarboximide) propoxy} ethane, 1,2-bis {3'-(allylmethylbicyclo) [2.2.1] Hept-5-ene-2,3-dicarboximide) 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] To-5-ene-2,3-dicarboximidopropoxy} butane, 1,4-bis {3 '-(allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxy] Imide) propoxy} butane,

N, N'-p-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N'-p-phenylene-bis (allylmethylbicyclo [2] 2.2.1] 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 Boxyimide), 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 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 -(Ari 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 (allylmethylbicyclo [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-di) Dorokishi) 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-dicarboximido) -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.

Among 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) Rylbicyclo [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] 2.2.1] 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 Boxyimide), 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 -(Ari 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) Rylbicyclo [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] 2.2.1] 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 Boxyimide), 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 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] Hepto 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 (allyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) represented by formula (NA-3) can 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 radically polymerizable unsaturated double bond for the purpose of stabilizing the electric characteristics of the liquid crystal display element for a long time. The compound having a radically polymerizable unsaturated double bond may be one type of compound or two or more types of compounds. In addition, the alkenyl substituted nadiimide compound is not contained in the compound which has a radically polymerizable unsaturated double bond. 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 its derivative, for the above purpose. Preferably, it is more preferably 1 to 50% by weight.

The ratio of the compound having a radically polymerizable unsaturated double bond to the alkenyl-substituted nadiimide compound reduces the ion density of the liquid crystal display element, suppresses the temporal increase of the ion density, and further suppresses the generation of a residual image. In order to achieve this, the weight ratio of the compound having a radically polymerizable unsaturated double bond / the alkenyl substituted nadiimide compound is preferably 0.1 to 10, and more preferably 0.5 to 5.

The compound having a radically polymerizable unsaturated double bond will be specifically described below.
Examples of the compound having a radically polymerizable unsaturated double bond include (meth) acrylic acid esters, (meth) acrylic acid derivatives such as (meth) acrylic acid amides, and bismaleimides. 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 (meth) acrylic acid esters include cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentanyl (meth) acrylate. Oxyethyl, isoboronyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate.

Specific examples of the difunctional (meth) acrylic acid ester include, for example, ethylene bis acrylate, Aronix M-210, Aronix M-240 and Aronix M-6200, which are products of Toa Synthetic Chemical Industry Co., Ltd., Nippon Kayaku Co., Ltd. The products of KAYARADHDDA, KAYARADHX-220, KAYARADR-604 and KAYARADR-684, products of Osaka Organic Chemical Industry Co., Ltd. V260, V312 and V335HP, and products of Kyoeisha Yuka Chemical Co., Ltd. BA-4EA, light acrylate BP-4PA and light acrylate BP-2PA can be mentioned.

Specific examples of the trifunctional or higher polyfunctional (meth) acrylic acid ester include, for example, 4,4′-methylene bis (N, N-dihydroxyethylene acrylate aniline), Alonix M, a product of Toagosei Chemical Industry Co., Ltd. 400, ALONIX M-405, ALONIX M-450, ALONIX M-7100, ALONIX M- 8030, ALONIX M-8060, products of Nippon Kayaku Co., Ltd. KAYARADTMPTA, KAYARADDPCA-20, KAYARADDPCA-30, KAYARADDPCA-60 And KAYARADDPCA-120, and VGPT which is a product of Osaka Organic Chemical Industry Co., Ltd.

Specific examples of (meth) acrylic acid amide derivatives include, for example, N-isopropyl acrylamide, N-isopropyl methacrylamide, N-n-propyl acrylamide, N-n-propyl methacrylamide, N-cyclopropyl acrylamide, N-cyclopropyl Methacrylamide, N-ethoxyethyl acrylamide, N-ethoxyethyl methacrylamide, N-tetrahydrofurfuryl acrylamide, N-tetrahydrofurfuryl methacrylamide, N-ethyl acrylamide, N-ethyl-N-methyl acrylamide, N, N-diethyl Acrylamide, N-methyl-N-n-propyl acrylamide, N-methyl-N-isopropyl acrylamide, N-acryloyl piperidine, N-acryloyl pyrrolidine, N, N'-methyl Bis acrylamide, N, N'-ethylene bis acrylamide, N, N'-dihydroxy ethylene bis acrylamide, N- (4-hydroxyphenyl) methacrylamide, N-phenyl methacrylamide, N-butyl methacrylamide, N- (iso -Butoxymethyl) methacrylamide, N- [2- (N, N-dimethylamino) ethyl] methacrylamide, N, N-dimethyl methacrylamide, 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.

As bismaleimides, for example, BMI-70 and BMI-80 manufactured by Kay I Kasei Co., Ltd., and BMI-1000, BMI-3000, BMI-4000, BMI-5000 and BMI-manufactured by Daiwa Kasei Kogyo Co., Ltd. There are 7000.

<Oxazine Compound>
For example, the liquid crystal aligning agent of the present invention may further contain an oxazine compound for the purpose of stabilizing the electric properties of the liquid crystal display element for a long time. The oxazine compound may be one type of compound or two or more types 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 the derivative thereof for the above-mentioned purpose. It is further preferred that

The oxazine compound is specifically described below.
The oxazine compound is soluble in a solvent in which the polyamic acid or its derivative is dissolved, and in addition, an oxazine compound having ring-opening polymerization is preferred.

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

Various structures are known as the structure of oxazine. In the present invention, the structure of oxazine is not particularly limited, but the oxazine structure in the oxazine compound includes the structure of an oxazine having an aromatic group containing a fused polycyclic aromatic group such as benzoxazine or naphthoxazine.

式（ＯＸ−１）〜式（ＯＸ−３）において、Ｌ^３およびＬ^４は炭素数１〜３０の有機基であり、式（ＯＸ−１）〜式（ＯＸ−６）において、Ｌ^５〜Ｌ^８は水素または炭素数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、Ｑ^１は単結合、−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−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、Ｑ^２は独立して単結合、−Ｏ−、−Ｓ−、−ＣＯ−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−または炭素数１〜３のアルキレンであり、Ｑ^２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、−ＣＨ_３、−ＯＨ、−ＣＯＯＨ、−ＳＯ_３Ｈ、−ＰＯ_３Ｈ_２と置き換えられていてもよい。 As an oxazine compound, the compound shown, for example to following formula (OX-1)-formula (OX-6) is mentioned. In the following formulas, a bond displayed toward the center of the ring indicates that it is bonded to any carbon which makes up the ring and which can be substituted.

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 hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, and in formulas (OX-3), (OX-4) and (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) in -6), ^{Q 2} is independently a single bond, -O -, - S -, - CO -, - C (CH 3) 2 -, - C (CF 3) 2 - or 1 to 3 carbon atoms It is an alkylene Or hydrogen attached to the benzene ring or naphthalene ring in Q ² may be independently replaced with -F, -CH ₃ , -OH, -COOH, -SO ₃ H, -PO ₃ H ₂ .

Further, the oxazine compounds include oligomers and polymers having an oxazine structure in a side chain, and oligomers and polymers 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 an alkyl having 1 to 30 carbon atoms, and more preferably an alkyl having 1 to 20 carbon atoms.

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、Ｌ^３およびＬ^４は炭素数１〜３０の有機基であり、Ｌ^５からＬ^８は水素または炭素数１〜６の炭化水素基であり、Ｑ^１は単結合、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−ＣＯ−、−Ｏ−、−ＳＯ_２−、−Ｃ（ＣＨ_３）_２−、または−Ｃ（ＣＦ_３）_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。 Examples of the oxazine compound represented by the formula (OX-3) include oxazine compounds represented by the following formula (OX-3-I).

In 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 hydrogen 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- . Examples of the oxazine compound represented by the formula (OX-3-I) include the following oxazine compounds.

式中、Ｌ^３およびＬ^４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, and 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.

Among these, more preferably, they are represented by the formula (OX-2-1), the formula (OX-3-1), the formula (OX-3-3), the formula (OX-3-5), the formula (OX-3-3) 7) Formula (OX-3-9), Formula (OX-4-1) to Formula (OX-4-6), Formula (OX-5-3), Formula (OX-5-4), and Formula The oxazine compounds represented by (OX-6-2) to the formula (OX-64) can be mentioned.

An oxazine compound can be manufactured by the method similar to the method as described in international publication 2004/009708, Unexamined-Japanese-Patent No. 11-12258, and Unexamined-Japanese-Patent No. 2004-352670.

The oxazine compound represented by Formula (OX-1) is obtained by making a phenol compound, a primary amine, and an aldehyde react (refer to international publication 2004/009708).

The oxazine compound represented by the formula (OX-2) is obtained by reacting a primary amine to formaldehyde by a method of gradually adding it, and then adding and reacting a compound having a naphtholic hydroxyl group (International Publication 2004/2006 See 009708).

In the organic solvent, the oxazine compound represented by the formula (OX-3) comprises one mole of a phenol compound, at least two moles or more of an aldehyde per one phenolic hydroxyl group, and one mole of a primary amine, a secondary aliphatic It can be obtained by reacting in the presence of an amine, a tertiary aliphatic amine or a basic nitrogen-containing heterocyclic compound (see WO 2004/009708 and JP-A-11-12258).

The oxazine compounds represented by the formulas (OX-4) to (OX-6) are, for example, diamines having a plurality of benzene rings such as 4,4'-diaminodiphenylmethane and an organic group which binds them, formalin and the like An aldehyde and phenol are obtained by dehydrating condensation reaction in n-butyl alcohol at a temperature of 90 ° C. or higher (see JP-A-2004-352670).

<Oxazoline compound>
For example, the liquid crystal aligning agent of the present invention may further contain an oxazoline compound for the purpose of stabilizing the electric characteristics of the liquid crystal display element for a long time. An oxazoline compound is a compound having an oxazoline structure. The oxazoline compound may be one type of compound or two or more types of 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 the derivative thereof from the above-mentioned purpose. Is preferred. 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 from the above-described purpose.

The oxazoline compound is specifically described below.
The oxazoline compound may have only one type of oxazoline structure in one compound, or may have two or more types. The oxazoline compound may have one oxazoline structure in one compound, but preferably has two or more oxazoline compounds. The oxazoline compound may be a polymer having an oxazoline structure in a side chain, or may be a copolymer. The polymer having an oxazoline structure in a side chain may be a homopolymer of a monomer having an oxazoline structure in a side chain, or a copolymer of a monomer having an oxazoline structure in a side chain and a monomer having no oxazoline structure. It may be The copolymer having an oxazoline structure in a side chain may be a copolymer of two or more types of monomers having an oxazoline structure in a side chain, or two or more types of monomers having an oxazoline structure in a side chain and the oxazoline structure It may be a copolymer with a monomer which 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.

As the oxazoline compound, for example, 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-oxazoline-2-yl) butane, 2,2′-bis-4-benzyl-2-oxazoline, 2,6-bis (isopropyl-2-oxazoline-2-yl) pyridine, 2,2 ′ -Isopropylidene bis (4-tert-butyl-2-oxazoline), 2,2'-isopropylidene bis (4-phenyl-2-oxazoline), 2,2'-methylenebi (4-tert-butyl-2-oxazoline), and 2,2'-methylenebis (4-phenyl-2-oxazoline) and the like. Besides these, polymers and oligomers having oxazolyl such as EPOCROS (trade name, manufactured by Nippon Shokubai Co., Ltd.) can also be mentioned. Among these, more preferably, 1,3-bis (4,5-dihydro-2-oxazolyl) benzene is mentioned.

<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 electric characteristics of the liquid crystal display element for a long time. The epoxy compound may be one type of compound or two or more types 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 based on the polyamic acid or the derivative thereof for the above purpose It is further preferred that

The epoxy compound is specifically described below.
The epoxy compounds include various compounds having one or more epoxy rings in the molecule. Examples of compounds having one epoxy ring in the molecule include phenyl glycidyl ether, butyl glycidyl ether, 3,3,3-trifluoromethylpropylene oxide, styrene oxide, hexafluoropropylene oxide, cyclohexene oxide, 3-glycidoxy Propyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-glycidyl phthalimide, (nonafluoro-n-butyl) epoxide, perfluoroethyl glycidyl ether, epichlorohydrin, epibromohydrin, Examples include N, N-diglycidyl aniline, and 3- [2- (perfluorohexyl) ethoxy] -1,2-epoxypropane.

Examples of compounds 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, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate and 3 -(N, N-diglycidyl) aminopropyl trimethoxysilane is mentioned.

The compound having three epoxy rings in the molecule is, for example, 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3- Epoxy propoxy] phenyl)] ethyl] phenyl] propane (trade name "Techmore VG3101L", manufactured by Mitsui Chemicals, Inc.) can be mentioned.

Examples of compounds having four epoxy rings in the molecule include 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylene diamine, 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 compounds having an epoxy ring in the molecule also include oligomers and polymers having an epoxy ring. Examples of monomers having an epoxy ring include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and methyl glycidyl (meth) acrylate.

Examples of other monomers to be copolymerized with the 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-cyclohexyl maleimide and N-phenyl maleimide may be mentioned.

Preferred specific examples of the polymer of the monomer having an epoxy ring include polyglycidyl methacrylate and the like. Moreover, as a preferable specific example of the copolymer of the monomer which has an epoxy ring, and another monomer, N-phenyl maleimide glycidyl methacrylate copolymer, N-cyclohexyl maleimide 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 Can be 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 Particularly preferred is 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

More systematically, as an epoxy compound, for example, glycidyl ether, glycidyl ester, glycidyl amine, epoxy group-containing acrylic resin, glycidyl amide, glycidyl isocyanurate, linear aliphatic epoxy compound, and cycloaliphatic epoxy compound Can be mentioned. The epoxy compound means a compound having an epoxy group, and the epoxy resin means a resin having an epoxy group.

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

As the glycidyl ether, for example, 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 compounds, hydrogenated bisphenol-type epoxy compounds, brominated bisphenol-A-type epoxy compounds, brominated bisphenol-F-type epoxy compounds, phenol novolac-type epoxy compounds, cresol novolac-type epoxy compounds, brominated phenol novolac-type epoxy compounds , Brominated cresol novolac epoxy compounds, bisphenol A novolac epoxy compounds, naphthalene skeleton-containing epoxy compounds, aromatic polymers 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 glycidyl esters include diglycidyl ester compounds and glycidyl ester epoxy compounds.

Examples of glycidyl amines include polyglycidyl amine compounds and glycidyl amine type epoxy resins.

Examples of epoxy group-containing acrylic compounds include homopolymers and copolymers of oxiranyl-containing monomers.

Examples of glycidyl amides include glycidyl amide type epoxy compounds.

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

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

Examples of bisphenol A epoxy compounds include jER 828, jER 1001, jER 1002, jER 1003, jER 1004, jER 1007, jER 1010 (all trade names, manufactured by Mitsubishi Chemical Corporation), Epototo YD-128 (manufactured by Toto Kasei Co., Ltd.), DER -331, DER-332, DER-324 (all from The Dow Chemical Company), Epiclon 840, Epiclon 850, Epiclon 1050 (all trade names from DIC Corporation), Epomic R-140, Epomic R-301 , And Epomic R-304 (all trade names, manufactured by Mitsui Chemicals, Inc.).

Examples of bisphenol F-type epoxy compounds include jER 806, jER 807, jER 4004 P (all trade names, manufactured by Mitsubishi Chemical Corporation), Epotote YDF-170, Epotote YDF-175 S, Epotote YDF- 2001 (all trade names, Toto Kasei Co., Ltd.) (Manufactured by Dow Chemical Co., Ltd.), DER-354 (trade name, manufactured by Dow Chemical Co., Ltd.), Epiclon 830, and Epiclon 835 (all trade names, manufactured by DIC Corporation).

As a bisphenol type epoxy compound, the epoxidized thing of 2, 2-bis (4-hydroxyphenyl) -1, 1, 1, 3, 3, 3- hexafluoro propane is mentioned, for example.

Examples of hydrogenated bisphenol-A type epoxy compounds include Suntote ST-3000 (trade name, manufactured by Toto Kasei Co., Ltd.), Rica Resin HBE-100 (trade name, manufactured by Shin Nippon Rika Co., Ltd.), and Denacol EX-252. (Trade name, manufactured by Nagase ChemteX Co., Ltd.).

As a hydrogenated bisphenol epoxy compound, for example, an epoxidized product of hydrogenated 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane can be mentioned.

Examples of brominated bisphenol-A type epoxy compounds include jER 5050, jER 5051 (all trade names, manufactured by Mitsubishi Chemical Corporation), Epototh YDB-360, Epototh YDB-400 (all trade names, manufactured by Toto Kasei Co., Ltd.) , DER-530, DER-538 (all trade names, manufactured by The Dow Chemical Company), Epiclon 152, and Epiclon 153 (all manufactured by DIC Corporation).

Examples of phenol novolac type epoxy compounds include jER152, jER154 (all trade names, manufactured by Mitsubishi Chemical Corporation), YDPN-638 (trade names, manufactured by Toto Kasei Co., Ltd.), DEN431, DEN438 (all trade names, The Dow) Chemical Company), Epiclon N-770 (trade name, manufactured by DIC Corporation), EPPN-201, and EPPN-202 (all trade names, manufactured by Nippon Kayaku Co., Ltd.).

Examples of cresol novolac type epoxy compounds include jER 180 S 75 (trade name, manufactured by Mitsubishi Chemical Corporation), YDCN-701, YDCN-702 (all manufactured by Toto Kasei Co., Ltd.), Epiclon N-665, Epiclon N-695 (All trade names, manufactured by DIC Corporation), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, and EOCN-1027 (all trade names, manufactured by Nippon Kayaku Co., Ltd.) Can be mentioned.

Examples of the bisphenol A novolac epoxy compound include jER157S70 (trade name, manufactured by Mitsubishi Chemical Corporation), and Epiclon N-880 (trade name, manufactured by DIC Corporation).

As the naphthalene skeleton-containing epoxy compound, for example, Epiclon HP-4032, Epiclon HP-4700, Epiclon HP-4770 (all are trade names, manufactured by DIC Corporation), and NC-7000 (trade names, manufactured by Nippon Kayaku Co., Ltd.) Can be mentioned.

Examples of the aromatic polyglycidyl ether compound include hydroquinone diglycidyl ether (the following formula EP-1), catechol diglycidyl ether (the following formula EP-2), resorcinol diglycidyl ether (the following formula EP-3), 2- [4 -(2,3-Epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3-epoxypropoxy] phenyl)] ethyl] phenyl] propane (the following formula EP-4) , Tris (4-glycidyloxyphenyl) methane (the following formula EP-5), jER1031S, jER1032H60 (all are trade names, manufactured by Mitsubishi Chemical Corporation), TACTIX-742 (trade names, manufactured by The Dow Chemical Company), Denacol EX-201 (trade name, manufactured by Nagase ChemteX Co., Ltd.), DPPN-503, DPPN-50 H, DPPN-501H, NC6000 (all trade names, manufactured by Nippon Kayaku Co., Ltd.), Techmore VG3101L (trade names, Mitsui Chemical Co., Ltd. made), a compound represented by the following formula EP-6, and the following formula The compound represented by EP-7 is mentioned.

Examples of dicyclopentadiene phenol type epoxy compounds include TACTIX-556 (trade name, manufactured by The Dow Chemical Company), and Epiclon HP-7200 (trade name, manufactured by DIC Corporation).

Examples of the alicyclic diglycidyl ether compound include cyclohexane dimethanol diglycidyl ether compound, and Rica Resin DME-100 (trade name, manufactured by Shin Nippon Chemical Co., Ltd.).

Examples of aliphatic polyglycidyl ether compounds 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), dibromo neopentyl glycol diglycidyl ether (following formula EP-15), Denacol EX 810, Denacole EX-851, Denacole EX-8301, Denacole EX-911, Denacole EX-920, Denacole EX-931, Denacole EX-211, Denacole EX-212, Denacole EX-313 (all are trade names, Nagase Chemex) Ltd., DD-503 (trade name, manufactured by ADEKA), Rica Resin W-100 (trade name, Shin Nippon Rika Co., Ltd.), 1,3,5,6-tetraglycidyl-2, 4-hexanediol (the 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 de Call EX-411 (trade names, manufactured by Nagase Chemtex Co., Ltd.) and the like.

Examples of polysulfide-type diglycidyl ether compounds include FLDP-50 and FLDP-60 (both of which are trade names, manufactured by Torethiol Co., Ltd.).

As biphenol type epoxy compounds, for example, YX-4000, YL-6121H (all trade names, manufactured by Mitsubishi Chemical Corporation), NC-3000P, and NC-3000S (all trade names, manufactured by Nippon Kayaku Co., Ltd.) Can be mentioned.

Examples of diglycidyl ester compounds include diglycidyl terephthalate (following formula EP-17), diglycidyl phthalate (following formula EP-18), bis (2-methyloxiranylmethyl) phthalate (following formula EP-19), A glycidyl hexahydro phthalate (following formula EP-20), the compound represented by the following formula EP-21, the compound represented by the following formula EP-22, and the compound represented by the following formula EP-23 are mentioned.

Examples of glycidyl ester epoxy compounds include jER 871 and jER 872 (all trade names, manufactured by Mitsubishi Chemical Corporation), Epiclon 200, Epiclon 400 (all trade names, DIC Corporation), Denacol EX-711, and Denacol. EX-721 (all trade names, manufactured by Nagase ChemteX Co., Ltd.) can be mentioned.

Examples of polyglycidyl amine compounds include N, N-diglycidyl aniline (the following formula EP-24), N, N-diglycidyl-o-toluidine (the following formula EP-25), and N, N-diglycidyl-m-toluidine (the following formula 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 (the following formula EP-29), N, N, O-triglycidyl-m-aminophenol (the following formula EP-30), N, N, N ′ , N'-tetraglycidyl-4,4'-diaminodiphenylmethane (the following formula EP-31), N, N, N ', N'-tetraglycidyl-m-xylylenediamine (TETRAD X (trade name, manufactured by Mitsubishi Gas Chemical Co., Ltd., the following formula EP-32), 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane (TETRAD-C (trade name, Mitsubishi Gas Chemical Co., Ltd.) ), The following formula EP-33), 1,4-bis (N, N-diglycidylaminomethyl) cyclohexane (the following formula EP-34), 1,3-bis (N, N-diglycidylamino) cyclohexane (The following formula EP-35), 1,4-bis (N, N-diglycidylamino) cyclohexane (the following formula EP-36), 1,3-bis (N, N-diglycidylamino) benzene (the following formula EP -37), 1,4-bis (N, N-diglycidylamino) benzene (the 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 (the following formula EP-40), 2,2'-dimethyl- (N, N, N', N'-) Tetraglycidyl) -4,4'-diaminobiphenyl (formula EP-41), N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenyl ether (formula EP-42), 1,3 5-tris (4- (N, N-diglycidyl) aminophenoxy) benzene (the following formula EP-43), 2,4,4'-tris (N, N-diglycidylamino) diphenyl ether (the following formula EP-44) ), Tris (4- (N, N-diglycidyl) aminophenyl) methane (the following formula EP-45), 3,4,3 ′, 4′-tetrakis (N, N-diglycidylamino) biphenyl (the following formula EP -46), 3, 4, 3 The compound represented by ', 4'- tetrakis (N, N- diglycidyl amino) diphenylether (following formula EP-47), the compound represented by following formula EP-48, and the compound represented by following formula EP-49 is mentioned.

Examples of homopolymers of oxiranyl-containing monomers include polyglycidyl methacrylate. As a copolymer of a monomer having oxiranyl, for example, N-phenylmaleimide-glycidyl methacrylate copolymer, N-cyclohexylmaleimide-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate-glycidyl methacrylate copolymer Examples include coalesced, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer, (3-ethyl-3-oxetanyl) methyl methacrylate-glycidyl methacrylate copolymer, and styrene-glycidyl methacrylate copolymer.

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

Examples of monomers other than oxiranyl-containing monomers in the copolymer of oxiranyl-containing monomers 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, Methyl styrene, chloromethyl styrene, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, N-cyclohexyl maleimide, and N-phenyl maleimide can be mentioned.

As glycidyl isocyanurate, for example, 1,3,5-triglycidyl-1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione (the following formula EP-50), 1, 3 And diglycidyl-5-allyl-1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione (the following formula EP-51), and glycidyl isocyanurate type epoxy resins.

As a chain aliphatic epoxy compound, for example, epoxidized polybutadiene, and Epolide PB3600 (trade name, manufactured by Daicel Co., Ltd.) can be mentioned.

Examples of cyclic aliphatic epoxy compounds include 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate (Celloxide 2021 (manufactured by Daicel Co., Ltd.), the following formula EP-52), 2-methyl -3,4-Epoxycyclohexylmethyl-2'-methyl-3 ', 4'-epoxycyclohexylcarboxylate (the following formula EP-53), 2,3-epoxycyclopentane-2', 3'-epoxycyclopentane ether (The following formula EP-54), ε-caprolactone modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 1,2: 8,9-diepoxylimonene (Celoxide 3000 (trade name, ( (Made by Daicel Co., Ltd.), the following formula EP-55), a compound represented by the following formula EP-56 CY-175, CY-177, CY-179 (all trade names, manufactured by The Ciba-Geigy Chemical Corp. (available from Huntsman Japan Ltd.)), EHPD-3150 (trade name, Daicel Co., Ltd.) And cycloaliphatic epoxy resins.

The epoxy compound is preferably one or more of a polyglycidyl amine compound, a bisphenol A novolac epoxy compound, a cresol novolac epoxy compound, and a cyclic aliphatic 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 "TECMOA VG3101L" 3,4-Epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate, N-phenylmaleimide-glycidyl methacrylate copolymer, N, N, O-triglycidyl-p-aminophenol, bisphenol A novolac type Epoxy compound, It is preferable and at least one cresol novolac type epoxy compound.

For example, the liquid crystal aligning agent of the present invention may further contain various additives. Examples of the various additives include polymer compounds other than polyamic acids and derivatives thereof, and low molecular compounds, and these can be selected and used according to the respective purposes.

For example, examples of the polymer compound include polymer compounds soluble in organic solvents. 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 properties and the alignment of the liquid crystal alignment film to be formed. Examples of the polymer compound include polyamides, polyurethanes, polyureas, polyesters, polyepoxides, polyester polyols, silicone-modified polyurethanes, and silicone-modified polyesters.

Further, as the low molecular weight compound, for example, 1) when it is desired to improve the coating property, 2) surfactant according to the purpose, 2) when it is necessary to improve antistatic, 3) adhesion to the substrate When it is desired to improve the properties, silane coupling agents and titanium-based coupling agents may be mentioned, and 4) an imidation catalyst may be mentioned if the imidation is allowed to proceed at a low temperature.

As a silane coupling agent, for example, vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyltritriol 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 is mentioned. The preferred silane coupling agent is 3-aminopropyltriethoxysilane.

Imidation catalysts include, for example, aliphatic amines such as trimethylamine, triethylamine, tripropylamine and tributylamine; and 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, hydroxy substituted imidazole and the like . The imidization catalyst may be one or more selected from N, N-dimethylaniline, o-, m-, p-hydroxyaniline, o-, m-, p-hydroxypyridine, and isoquinoline preferable.

The amount of the silane coupling agent to be added 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 addition amount of the imidization catalyst is usually 0.01 to 5 equivalents, preferably 0.05 to 3 equivalents with respect to the carbonyl group of the polyamic acid or its derivative.

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

The polyamic acid or derivative thereof of the present invention can be produced in the same manner as the known polyamic acid or derivative thereof used for forming a film of polyimide. It is preferable that the total preparation amount of tetracarboxylic acid dianhydride is approximately equal to the total number of moles of diamine (about a 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 7,000 to 500,000, and more preferably 10,000 to 200,000, in terms of weight average molecular weight (Mw) in terms of polystyrene. The molecular weight of the polyamic acid or its derivative can be determined from measurement by gel permeation chromatography (GPC).

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

For example, the liquid crystal aligning agent of the present invention may further contain a solvent from the viewpoint of the coating property of the liquid crystal aligning agent and the adjustment of the concentration of the polyamic acid or the derivative thereof. The solvent can be applied without particular limitation as long as the solvent has the ability to dissolve the polymer component. The solvent widely includes solvents generally used in the production process of polymeric components such as polyamic acid, soluble polyimide and the like, and can be appropriately selected according to the purpose of use. The solvent may be one or a mixture of two or more.

Examples of the solvent include a parent solvent for the polyamic acid or its derivative, and other solvents for the purpose of improving the coating property.

N-methyl-2-pyrrolidone, dimethylimidazolidinone, N-methylcaprolactam, N-methylpropionamide, N, N-dimethylacetamide as an aprotic polar organic solvent which is a parent solvent for polyamic acid or its derivative And lactones such as dimethylsulfoxide, N, N-dimethylformamide, N, N-diethylformamide, diethylacetamide, γ-butyrolactone and the like.

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, and diethylene glycol monoethyl ether. Diethylene glycol monoalkyl ether, ethylene glycol monoalkyl or phenyl acetate, triethylene glycol monoalkyl ether, propylene glycol monomethyl ether, propylene glycol monoalkyl ether such as propylene glycol monomethyl ether, dialkyl malonate such as diethyl malonate, dipropylene glycol monomethyl Dipropylene glycol monoalkyl ethers such as ether, 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 polyamic acid in the alignment agent of the present invention is preferably 0.1 to 40% by weight. When the alignment agent is applied to a 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 in accordance with various coating methods described below. In general, the amount is preferably 0.1 to 30% by weight, and more preferably 1 to 10% by weight, based on the weight of the varnish in order to suppress unevenness and pinholes during application.

The preferred range of the viscosity of the liquid crystal aligning agent of the present invention differs depending on the method of application, the concentration of the polyamic acid or its derivative, the type of polyamic acid or its derivative used, and the type and ratio of the solvent. For example, in the case of application by a printing machine, it is 5 to 100 mPa · s (more preferably 10 to 80 mPa · s). When it is less than 5 mPa · s, it becomes difficult to obtain a sufficient film thickness, and when it exceeds 100 mPa · s, printing unevenness may increase. In the case of spin coating, 5 to 200 mPa · s (more preferably 10 to 100 mPa · s) is suitable. In the case of coating using an inkjet coating apparatus, 5 to 50 mPa · s (more preferably 5 to 20 mPa · s) is suitable. The viscosity of the liquid crystal aligning agent is measured by rotational viscosity measurement, and is measured (measurement temperature: 25 ° C.) using, for example, a rotational viscometer (TVE-20L manufactured by Toki Sangyo Co., Ltd.).

The liquid crystal alignment film of the present invention will be described in detail. The liquid crystal aligning 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 aligning film of this invention can be obtained by the normal method of producing a liquid crystal aligning film from a liquid crystal aligning agent. For example, the liquid crystal aligning film of this invention can be obtained by passing through the process of forming the coating film of the liquid crystal aligning agent of this invention, the process of heat-drying, and the process of heat-baking. With respect to the liquid crystal alignment film of the present invention, the film obtained through the heating and drying process and the heating and baking process may be rubbed to impart anisotropy, as described later, as necessary. Alternatively, if necessary, light may be irradiated after the coating step and the heating and drying step, or light may be irradiated after the heating and baking step to impart anisotropy. Moreover, you may use as a liquid crystal aligning film for VA which does not carry out 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 glass-made substrates which may be provided with electrodes such as ITO (Indium Tin Oxide), IZO (In ₂ O ₃ -ZnO), IGZO (In-Ga-ZnO ₄ ) electrodes, color filters and the like. .

Generally as a method of apply | coating a liquid crystal aligning agent to a board | substrate, a spinner method, the printing method, the dipping method, the dripping method, the inkjet method etc. are known. These methods are equally applicable to the present invention.

As the heating and 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. It is preferable to carry out the heating and drying step at a temperature within the range where evaporation of the solvent is possible, and it is more preferable to carry out the heating and drying step at a temperature relatively lower than the temperature in the heating and baking step. Specifically, the heating and 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 calcining step can be performed under the conditions necessary for the polyamic acid or its derivative to exhibit a dehydration and ring closure reaction. As 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. Generally, it is preferable to carry out at a temperature of about 100 to 300 ° C. for 1 minute to 3 hours, more preferably 120 to 280 ° C., and still more preferably 150 to 250 ° C. In addition, heating and firing can be performed multiple times at different temperatures. A plurality of heating devices set to different temperatures may be used, or one heating device may be used while sequentially changing to different temperatures. When heat-baking is performed twice at different temperatures, it is preferable to carry out the heat treatment at a temperature of 90 to 140 ° C. for the first time and a temperature of 180 ° C. or more for the second time.

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

The liquid crystal alignment film of the present invention using the rubbing method comprises the steps of applying the liquid crystal alignment agent of the present invention to a substrate, heating and drying the substrate coated with the alignment agent, heating and baking the film, and film And a rubbing process.

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

The formation method of the liquid crystal aligning film of this invention by the photo-alignment method is demonstrated in detail. The liquid crystal alignment film of the present invention using the photoalignment method imparts anisotropy to the coating film by heating and drying the coating film and then irradiating it with linear polarization or non-polarization of radiation, and heating and baking the film It can be formed by Alternatively, it can be formed by irradiating the linearly polarized light or the non-polarized light of radiation after heating and drying the coating film and baking it. From the viewpoint of orientation, it is preferable to carry out the radiation irradiation step before the heating and firing step.

Furthermore, in order to increase the liquid crystal alignment ability of the liquid crystal alignment film, it is possible to irradiate linearly polarized light or non-polarized light while heating the coating. The irradiation of radiation may be carried out in the step of heat-drying or heat-baking the coated film, or may be carried out between the heat-drying step and the heat-baking step. The heating and drying temperature in the step is preferably in the range of 30 ° C. to 150 ° C., and more preferably in the range of 50 ° C. to 120 ° C. Further, the heating and firing temperature in the step is preferably in the range of 30 ° C. to 300 ° C., and more preferably in the range of 50 ° C. to 250 ° C.

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

The liquid crystal alignment film of the present invention can exhibit high liquid crystal alignment ability even when irradiated with low energy light. 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. The irradiation angle of the linearly polarized light with respect to the film surface is not particularly limited, but in order to express a strong alignment control force for liquid crystal, it is preferable from the viewpoint of shortening the alignment processing time that it be as perpendicular as possible to the film surface. Moreover, the liquid crystal aligning film of this invention can orientate a liquid crystal in the direction perpendicular | vertical with respect to the polarization direction of linearly polarized light by irradiating linearly polarized light.

Light sources used in the process of irradiating linearly polarized radiation or non-polarized radiation include ultra high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, deep UV lamps, halogen lamps, metal halide lamps, high power metal halide lamps, xenon lamps, 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, etc. can be used without limitation.

The liquid crystal alignment film of the present invention is suitably obtained by a method further including other steps other than the steps described above. For example, in the liquid crystal alignment film of the present invention, the step of washing the film after baking or irradiation with a washing solution is not essential, but a washing step can be provided for convenience of other steps.

Examples of the cleaning method using a cleaning solution include brushing, jet spray, steam cleaning, ultrasonic cleaning and the like. These methods may be performed alone or in combination. As the washing solution, pure water or various alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol, aromatic hydrocarbons such as benzene, toluene and xylene, halogen solvents such as methylene chloride, ketones such as acetone and methyl ethyl ketone Although it can be used, it is not limited to these. Of course, as these cleaning solutions, those which are sufficiently purified and low in impurities are used. Such a cleaning method can also be applied to the above-mentioned 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 and after the heating and firing step, before and after the rubbing step, or before and after polarized or non-polarized radiation irradiation. . 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. Further, as the annealing light used for the annealing process, a UV lamp, a fluorescent lamp, an LED lamp and the like can be mentioned. The irradiation dose of light 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 gauge or an ellipsometer.

The liquid crystal alignment film of the present invention is characterized by having particularly large anisotropy of alignment. The magnitude of such anisotropy can be evaluated by a method using polarized IR described in JP-A-2005-275364 and the like. It can also be evaluated by a method using ellipsometry as shown in the following examples. Specifically, the retardation value of the liquid crystal alignment film can be measured by a spectroscopic ellipsometer. 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 alignment, and when used as a liquid crystal alignment film, it is considered that an alignment film having larger anisotropy has a large alignment control power to the liquid crystal composition.

The liquid crystal alignment film of the present invention can be suitably used for a transverse electric field liquid crystal display element. When it is used for a liquid crystal display device of a transverse electric field system, the black display level in the dark state becomes higher and the contrast is improved as the Pt angle is smaller and the liquid crystal alignment ability is higher. The Pt angle is preferably 0.1 ° or less.

The liquid crystal alignment film of the present invention can be used for controlling the alignment of an optical compensatory material and all other liquid crystal materials, in addition to the alignment application of the liquid crystal composition for liquid crystal display. In addition, since the alignment film of the present invention has large anisotropy, it can be used alone as an optical compensatory material.

The liquid crystal display element of the present invention will be described in detail.
The present invention is formed on a pair of oppositely disposed substrates, an electrode formed on one or both of opposing surfaces of the pair of substrates, and an opposed surface of the pair of substrates. The liquid crystal display element which has the liquid crystal aligning film and the liquid crystal layer formed between a pair of board | substrates, Comprising: The said liquid crystal aligning film provides the liquid crystal display element which is an alignment film of this invention.

The said electrode will not be specifically limited if it is an electrode formed in one surface of a board | substrate. Examples of such an electrode include a deposited film of ITO or metal, and the like. The electrode may be formed on the entire surface of one side of the substrate, or may be formed, for example, in a desired shape which is patterned. The desired shape of the electrode includes, for example, a comb or zigzag structure. The electrode may be formed on one of the pair of substrates or may be formed on both of the substrates. The form of formation of the electrodes differs depending on the type of liquid crystal display element. For example, in the case of an IPS type liquid crystal display element, the electrode is disposed on one of the pair of substrates, and in the case of the other liquid crystal display elements Electrodes are disposed on both sides. The liquid crystal alignment film is formed on the substrate or the electrode.

The liquid crystal layer is formed in such a manner that a 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, it is possible to use a spacer, such as fine particles or a resin sheet, which is interposed between the pair of substrates to form an appropriate distance.

The liquid crystal composition is not particularly limited, and various liquid crystal compositions having positive or negative dielectric anisotropy can be used. Preferred examples of liquid crystal compositions having positive dielectric anisotropy include: Japanese Patent Nos. 3086228, 2635435, JP-A-5-01735, JP-A-8-157826, JP-A-8-231960 and JP-A-9-241644 (EP885272A1). JP-A-9-302346 (EP806466A1), JP-A-8-199168 (EP722998A1), JP-A-9-235552, JP-A-9-225956, JP-A-9-241643 (EP885272A1), JP-A-10-204016 (EP844229A1), JP-A-1020. Examples thereof include liquid crystal compositions disclosed in JP-A-204436, JP-A-10-231482, JP-A-2000-087040, JP-A-2001-48822, and the like.

It is also acceptable to use one or more optically active compounds added to a liquid crystal composition having positive or negative dielectric anisotropy.

ここで、Ｒ^１ａおよびＲ^２ａは独立して、炭素数１〜１２のアルキル、炭素数１〜１２のアルコキシ、炭素数２〜１２のアルケニル、または少なくとも１つの水素がフッ素で置き換えられた炭素数２〜１２のアルケニルであり、環Ａ^２および環Ｂ^２は独立して、１，４−シクロへキシレン、テトラヒドロピラン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、１，４−フェニレン、２−フルオロ−１，４−フェニレン、２，５−ジフルオロ−１，４−フェニレン、２，３−ジフルオロ−１，４−フェニレン、２−フルオロ−３−クロロ−１，４−フェニレン、２，３−ジフルオロ−６−メチル−１，４−フェニレン、２，６−ナフタレンジイル、または７，８−ジフルオロクロマン−２，６−ジイルであり、ここで、環Ａ^２および環Ｂ^２の少なくとも１つは２，３−ジフルオロ−１，４−フェニレン、２−フルオロ−３−クロロ−１，４−フェニレン、２，３−ジフルオロ−６−メチル−１，４−フェニレン、または７，８−ジフルオロクロマン−２，６−ジイルであり、Ｚ^１は独立して単結合、−（ＣＨ_２）_２−、−ＣＨ_２Ｏ−、−ＣＯＯ−、または−ＣＦ_２Ｏ−であり、ｊは１、２、または３であり、ｊが２または３である時、任意の２つの環Ａ^２は同じであっても異なってもよく、任意の２つのＺ^１は同じであっても異なってもよい。 The liquid crystal composition having a negative dielectric anisotropy will be described. Examples of the liquid crystal composition having negative dielectric anisotropy include, as a first component, a composition containing at least one liquid crystal compound selected from the group of liquid crystal compounds represented by the following formula (NL-1) .

Here, R ^1a and R ^2a are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or the number of carbons in which at least one hydrogen is replaced by fluorine And each of ring A ² and ring B ² is independently 1,4-cyclohexylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, 1 , 4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2-fluoro-3-chloro-1,4 - phenylene, a 2,3-difluoro-6-methyl-1,4-phenylene, 2,6-naphthalene-diyl or 7,8-difluoro-chroman-2,6-diyl, wherein the ring ^{a 2} Contact At least one 2,3-difluoro-1,4-phenylene fine ring ^{B 2,} 2-fluoro-3-chloro-1,4-phenylene, 2,3-difluoro-6-methyl-1,4-phenylene Or 7,8-difluorochroman-2,6-diyl, Z ¹ is independently a single bond,-(CH ₂ ) _2- , -CH ₂ O-, -COO-, or -CF ₂ O- And when j is 1, 2 or 3 and j is 2 or 3, any two rings A ² may be the same or different and any two Z ¹ are the same It may be different or different.

Preferred ring A ² and ring B ² are respectively 2,3-difluoro-1,4-phenylene or tetrahydropyran-2,5-diyl to increase dielectric anisotropy, and 1,2 to lower viscosity. 4-cyclohexylene.

Desirable Z ¹ is —CH ₂ O— for increasing the dielectric anisotropy, and a single bond for decreasing the viscosity.

Desirable j is 1 to lower the lower limit temperature and 2 to increase the upper limit temperature.

ここで、Ｒ^１aおよびＲ^２ａは独立して、炭素数１〜１２のアルキル、炭素数１〜１２のアルコキシ、炭素数２〜１２のアルケニル、または少なくとも１つの水素がフッ素で置き換えられた炭素数２〜１２のアルケニルであり、環Ａ^２１、環Ａ^２２、環Ａ^２３、環Ｂ^２１、および環Ｂ^２２は独立して、１，４−シクロへキシレンまたは１，４−フェニレンであり、Ｚ^１１およびＺ^１２は、独立して単結合、−（ＣＨ_２）_２−、−ＣＨ_２Ｏ−、または−ＣＯＯ−である。 As a specific example of the liquid crystal compound represented by the said Formula (NL-1), the compound represented by the following formula (NL-1-1)-a formula (NL-1-32) can be mentioned.

Here, R ^1a and R ^2a are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or the number of carbons in which at least one hydrogen is replaced by fluorine And each of ring A ²¹ , ring A ²² , ring A ²³ , ring B ²¹ and ring B ²² is independently 1,4-cyclohexylene or 1,4-phenylene; ¹¹ and ^{Z 12} are independently a single _{bond, - (CH 2) 2 -} , - CH 2 O-, or -COO-.

Desirable R ^1a and R ^2a are alkyl having 1 to 12 carbons to increase the stability to ultraviolet light or heat, or alkoxy having 1 to 12 carbons to increase the absolute value of dielectric anisotropy.

Preferred alkyl is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl. More preferred alkyl is ethyl, propyl, butyl, pentyl or heptyl to lower the viscosity.

Preferred alkoxy is methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy or heptyloxy. More desirable alkoxy is methoxy or ethoxy for decreasing the viscosity.

Preferred alkenyl is vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl or 5-hexenyl. More preferred alkenyl is vinyl, 1-propenyl, 3-butenyl or 3-pentenyl to reduce viscosity. The preferred configuration of -CH = CH- in these alkenyls depends on the position of the double bond. Trans is preferable in the alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl and 3-hexenyl for decreasing the viscosity and the like. Cis is preferable in the alkenyl such as 2-butenyl, 2-pentenyl and 2-hexenyl. In these alkenyls, linear alkenyls are preferable to branched ones.

Preferred examples of the alkenyl in which at least one hydrogen is replaced by fluorine are: 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3-butenyl, 5,5-difluoro-4 -Pentenyl and 6,6-difluoro-5-hexenyl. Further preferred examples are 2,2-difluorovinyl and 4,4-difluoro-3-butenyl for decreasing the viscosity.

Preferred rings A ²¹ , A ²² , A ²³ , B ²¹ and B ²² are each 1,4-cyclohexylene to reduce viscosity.

Desirable Z ¹¹ and Z ¹² are —CH ₂ O— for increasing the dielectric anisotropy, and a single bond for decreasing the viscosity.

The compound represented by the formula (NL-1) wherein the liquid crystal composition having the negative dielectric anisotropy is preferable as the first component is a compound represented by the formula (NL-1-1) or the formula (NL-1-4) A compound represented by Formula (NL-1-7) and Formula (NL-1-32).

As preferable examples of the liquid crystal composition having the negative dielectric constant anisotropy described in JP-A-57-114532, JP-A-2-4725, JP-A-4-224885, JP-A-8-40953, JP-A-8-104869, 10-168076, 10-168453, 10-236,989, 10-236990, 10-236,992, 10-236,993, 10-236,994, 10-23,7000, 10; JP-A-10-237024, JP-A-10-237035, JP-A-10-237 705, JP-A-10-237076, JP-A-10-237448 (EP967261 A1), JP-A-10-287874, JP-A-10-287875, JP-A-10-287875. 10-291945, JP-A-11-029581, JP-A-11-080049, JP-A-2000-256307, JP-A-2001-019656, JP-A-2001-072626, JP-A-2001-192657, JP-A-2010-037428, International Publication No. The liquid crystal composition currently disclosed by -537010, Unexamined-Japanese-Patent No. 2012-077201, Unexamined-Japanese-Patent No. 2009-084362 grade | etc., Is mentioned.

Further, for example, an additive may be further added to the liquid crystal composition used for the device of the present invention, for example, from the viewpoint of improving the orientation. Such additives include photopolymerizable monomers, optically active compounds, antioxidants, ultraviolet light absorbers, dyes, antifoaming agents, polymerization initiators, polymerization inhibitors and the like.

Examples of the most preferable structure of the photopolymerizable monomer or oligomer for the purpose of improving the orientation of the liquid crystal include structures represented by Formula (PM-1-1) to Formula (PM-1-6).

The content of the photopolymerizable monomer or oligomer is preferably 0.01% by weight or more in order to exert an effect of determining the tilt direction of the liquid crystal after they are polymerized. Also, in order to make the alignment effect of the polymer appropriate after polymerization, or to avoid the elution of unreacted monomers or oligomers into the liquid crystal after irradiation with ultraviolet light, it is 30% by weight or less desirable.

An optically active compound is mixed into the composition for the purpose of inducing a helical structure of liquid crystal to give a twist angle. Examples of such compounds are compounds represented by Formula (PAC-1-1) to Formula (PAC-1-4).
The preferred proportion of the optically active compound is 5% by weight or less. A further preferable ratio is in the range of 0.01% by weight to 2% by weight.

In order to prevent a decrease in specific resistance due to heating in the air, or to maintain a large voltage holding ratio not only at room temperature but also at high temperatures after the device has been used for a long time, an antioxidant is added to the liquid crystal composition. Be mixed.

Preferred examples of the antioxidant are compounds represented by the formula (AO-1) in which w is an integer of 1 to 10. In the formula (AO-1), preferable w is 1, 3, 5, 7 or 9. More preferable w is 1 or 7. The compound represented by the formula (AO-1) in which w is 1 is highly volatile, and thus is effective in preventing a decrease in specific resistance due to heating in the atmosphere. Since the compound represented by the formula (AO-1) in which w is 7 has low volatility, it is effective to maintain a large voltage holding ratio not only at room temperature but also at high temperatures after using the device for a long time is there. The preferable proportion of the antioxidant is 50 ppm or more to obtain the effect, and 600 ppm or less so as not to lower the upper limit temperature or to raise the lower limit temperature. A further preferred ratio is in the range of 100 ppm to 300 ppm.

Preferred examples of the UV absorbers are benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Also preferred are light stabilizers such as sterically hindered amines. The preferable ratio in these absorbents and stabilizers is 50 ppm or more to obtain the effect, and 10000 ppm or less so as not to lower the upper limit temperature or to raise the lower limit temperature. A further preferable ratio is in the range of 100 ppm to 10000 ppm.

In order to conform to a device of GH (Guest host) mode, a dichroic dye such as an azo dye or an anthraquinone dye is mixed into the composition. The preferred proportion of dye is in the range of 0.01% by weight to 10% by weight.

In order to prevent foaming, an antifoam agent such as dimethyl silicone oil, methylphenyl silicone oil, etc. is mixed into the composition. The preferable proportion of the antifoaming agent is 1 ppm or more in order to obtain the effect, and 1000 ppm or less in order to prevent display defects. A further preferred ratio is in the range of 1 ppm to 500 ppm.

A polymerizable compound can be mixed into the composition in order to conform to a device of PSA (polymer sustained alignment) mode. Preferred examples of the polymerizable compound are compounds having a polymerizable group such as acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxirane, oxetane), vinyl ketone and the like. Particularly preferred examples are derivatives of acrylates or methacrylates. Examples of such compounds are compounds represented by Formula (PM-2-1) to Formula (PM-2-9). The preferred proportion of the polymerizable compound is about 0.05% by weight or more to obtain the effect and about 10% by weight or less to prevent display defects. A further preferred ratio is in the range of about 0.1% by weight to about 2% by weight.

ここで、Ｒ^３ａ、Ｒ^４ａ、Ｒ^５ａ、およびＲ^６ａは独立して、アクリロイルまたはメタクリロイルであり、Ｒ^７ａおよびＲ^８ａは独立して、水素、ハロゲン、または炭素数１から１０のアルキルであり、Ｚ^１３、Ｚ^１４、Ｚ^１５、およびＺ^１６は独立して、単結合または炭素数１から１２のアルキレンであり、少なくとも１つの−ＣＨ_２−は−Ｏ−または−ＣＨ＝ＣＨ−により置き換えられていてもよく、ｓ、ｔ、およびｕはそれぞれ独立して、０、１、または２である。

Here, R ^3a , R ^4a , R ^5a and R ^6a are independently acryloyl or methacryloyl, and R ^7a and R ^8a are independently hydrogen, halogen or alkyl having 1 to 10 carbon atoms. , Z ¹³ , Z ¹⁴ , Z ¹⁵ and Z ¹⁶ are independently a single bond or alkylene having 1 to 12 carbon atoms, and at least one -CH ₂ -is replaced by -O- or -CH = CH- And s, t and u are each independently 0, 1 or 2.

A polymerization initiator can be mixed as a substance which easily generates radicals or ions and is necessary for initiating a chain polymerization reaction. For example, Irgacure 651 (registered trademark), Irgacure 184 (registered trademark), or Darocure 1173 (registered trademark) (Ciba Japan K. K.), which is a photopolymerization initiator, are suitable for radical polymerization. The polymerizable compound preferably comprises a photoinitiator in the range of 0.1% by weight to 5% by weight. Particularly preferably, the photopolymerization initiator is contained in the range of 1% by weight to 3% by weight.

In a radical polymerization system, it reacts rapidly with a polymerization initiator or a radical generated from a monomer to be converted into a stable radical or a neutral compound, and as a result, a polymerization inhibitor is mixed for the purpose of stopping a polymerization reaction. Can. The polymerization inhibitors are classified into several in structure. One of them is a radical which is itself stable such as tri-p-nitrophenylmethyl, di-p-fluorophenylamine and the like, and the other is a radical which is easily reacted with a radical present in the polymerization system. And nitro, nitroso, amino, polyhydroxy compounds and the like. As the latter, hydroquinone, dimethoxybenzene and the like can be mentioned. The preferred proportion of the polymerization inhibitor is 5 ppm or more in order to obtain the effect, and 1000 ppm or less in order to prevent display defects. A further preferred ratio is in the range of 5 ppm to 500 ppm.

By using a liquid crystal composition having negative dielectric constant anisotropy for the liquid crystal display element of the present invention, it is possible to provide a liquid crystal display element having excellent afterimage characteristics and having excellent alignment stability.

Hereinafter, the present invention will be described by way of examples. The evaluation methods and compounds used in the examples are as follows.

<Evaluation method>
1. 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 determined by polystyrene conversion. The obtained polyamic acid was diluted with a phosphoric acid-DMF mixed solution (phosphoric acid / DMF = 0.6 / 100: weight ratio) such that the polyamic acid concentration was about 2% by weight. The column used HSPgel RT MB-M (manufactured by Waters), and the 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 Corp. was used.
2. Measurement was made according to the pretilt angle measurement crystal rotation method. The pretilt angle is a physical property value that is an index for predicting the viewing angle characteristics, and if this value is 2.0 or less, the liquid crystal display element with excellent viewing angle characteristics in the IPS mode and the FFS mode is obtained.
3. Voltage retention was carried out according to the method described in Minamata et al., Proceedings of the 14th Liquid Crystal Display Symposium p78 (1988). The measurement was performed by applying a square wave of ± 5 V wave height to the cell. The measurement was performed at 60 ° C. This value is an index showing how much the applied voltage is held after the frame period, and if this value is 100%, it indicates that all charges are held. If the cell having the positive liquid crystal mounted thereon is 99.5% or more, and the cell having the negative liquid crystal mounted thereon is 97.5% or higher, the liquid crystal display element with good display quality is obtained.
4. Measurement of ion content in liquid crystal (ion density)
According to the method described in Applied Physics, Vol. 65, No. 10, 1065 (1996), it was measured using a liquid crystal physical property measuring system Model 6254 manufactured by Toyo Corporation. Using a triangular wave having a frequency of 0.01 Hz, measurement was performed at a temperature of 60 ° C. (voltage area of 1 cm ² ) at a voltage range of ± 10 V. If the ion density is large, problems such as burn-in due to ionic impurities are likely to occur. That is, the ion density is a physical property value that serves as an index for predicting the occurrence of burn-in. If this value is 40 pC or less, a liquid crystal display element with good display quality is obtained.
5. A phenomenon in which liquid crystals are aligned along the direction in which liquid crystals flow from the injection port when observed by visual observation by sandwiching a flow alignment liquid crystal cell between two polarizing plates arranged in cross nicol is called flow alignment. The flow alignment is an index of the alignment property of the alignment film, and the alignment film in which the flow alignment does not occur has a good alignment property.

<Diamine>

<Tetracarboxylic acid dianhydride>

<Monomer having photoisomerization structure>

<Solvent>
N, N-dimethylformamide: DMF
Tetrahydrofuran: THF
N-Methyl-2-pyrrolidone: NMP
γ-butyrolactone: GBL
Butyl cellosolve (ethylene glycol monobutyl ether): BC

Example 1
Synthesis of diamine represented by formula (1-15).
<Step 1> Synthesis of dinitro compound In a 500 mL three-necked flask equipped with a thermometer and a reflux condenser, 4-amino-2,2,6,6-tetramethylpiperidine (20.0 g, 128.0 mmol) and potassium carbonate (44.2 g, 320.0 mmol) was added, and 200 mL of DMF was added. To the solution was slowly added 4-fluoronitrobenzene (39.7 g, 281.6 mmol), keeping the solution below 5 ° C. Cooling of the reaction was stopped and stirred at room temperature for a further 24 hours. The reaction solution was poured into 500 mL of pure water and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate and filtered to remove the desiccant, and then the solvent was evaporated under reduced pressure to give a crude product. The obtained crude product was recrystallized from ethanol (50 mL) to obtain the following compound. Yield 26.3 g, 52% yield.

<Step 2> Reduction of Nitro Group The compound obtained in Step 1 (26.3 g, 66.0 mmol) and 5 wt% palladium carbon powder (2.6 g) were placed in a 1 L autoclave reactor, and 250 mL of THF was added. The mixture was stirred at 50 ° C. in a 0.5 mPa hydrogen atmosphere until hydrogen absorption ceased. After cooling, the palladium carbon powder was removed by filtration, and the solvent was evaporated under reduced pressure to obtain a crude product. The crude product was recrystallized from 40 mL of ethanol to give a compound represented by formula (1-15). Yield 19.3 g, 86%.

Example 2
Synthesis of Diamine Represented by Formula (1-29) <First Step> Synthesis of Dinitro Compound In a 500 mL three-necked flask equipped with a thermometer and a reflux condenser, 4-amino-2,2,6,6-tetramethyl Piperidine (20.0 g, 128.0 mmol) and potassium carbonate (44.2 g, 320.0 mmol) were added and 200 mL of DMF was added. A solution of 4-nitrobenzyl bromide (60.8 g, 281.6 mmol) in DMF (50 mL) was added slowly while keeping the solution below 5 ° C. Cooling of the reaction was stopped and stirred at room temperature for a further 5 hours. The reaction solution was poured into 500 mL of pure water and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate and filtered to remove the desiccant, and then the solvent was evaporated under reduced pressure to give a crude product. The obtained crude product was recrystallized from ethanol (50 mL) to obtain the following compound. Yield 46.2 g, yield 85%.

<Step 2> The compound (46.2 g, 108.3 mmol) obtained in Step 1 was placed in a 1000 mL three-necked flask equipped with a reduction thermometer of nitro group and a reflux condenser, and 300 mL of ethanol and 50 mL of water . Sodium sulfide nonahydrate (295.4 g, 649.9 mmol) was added slowly while keeping the solution below 25 ° C. The mixture was heated under reflux for 8 hours under nitrogen atmosphere, allowed to cool, poured into pure water (500 mL), extracted with ethyl acetate (500 mL), and the organic layer was washed 3 times with pure water (500 mL). The organic layer was dried over anhydrous sodium sulfate and filtered to remove the desiccant, and then the solvent was evaporated under reduced pressure to give a crude product. The obtained crude product was recrystallized from ethanol (50 mL) to give a compound represented by formula (1-29). Yield 27.3 g, yield 69%.

[Example 3]
Synthesis of Diamine Represented by Formula (1-1) <First Step> 2-Nitroethanol (30.0 g, 329.4 mmol) and triethylamine in a 2000 mL three-necked flask equipped with a methanesulfonylation thermometer and a reflux condenser (50.0 g, 494.2 mmol) was added and 600 mL of THF was added. Methanesulfonyl chloride (45.3 g, 395.3 mmol) was added slowly while keeping the solution below 5 ° C. Cooling of the reaction was stopped and stirred at room temperature for a further 24 hours. The reaction solution was poured into 500 mL of pure water and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate and filtered to remove the desiccant, and then the solvent was evaporated under reduced pressure to obtain the following compound. Yield 53.2 g, 95% yield.

<Step 2> Synthesis of dinitro compound In a 2000 mL three-necked flask equipped with a thermometer and a reflux condenser, 4-amino-2,2,6,6-tetramethylpiperidine (13.5 g, 86.5 mmol) and potassium carbonate (27.5 g, 199.0 mmol) was added and 200 mL of DMF was added. A solution of the compound obtained in the first step (30.0 g, 177.4 mmol) in DMF (50 mL) was slowly added while keeping the solution at 5 ° C. or less. Cooling of the reaction was stopped and stirred at room temperature for a further 5 hours. The reaction solution was poured into 500 mL of pure water and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate and filtered to remove the desiccant, and then the solvent was evaporated under reduced pressure to give a crude product. The obtained crude product was recrystallized from ethanol (50 mL) to obtain the following compound. Yield 19.2 g, 73%.

<Step 3> The compound (15.0 g, 49.6 mmol) obtained in Step 2 and 50 mL of methanol were added to a 1000 mL three-necked flask equipped with a reduction thermometer for a nitro group and a reflux condenser. While keeping the solution at -10 ° C, 10% Pd / C (1.5 g) and ammonium formate (30.8 g, 496.1 mmol) were slowly added and stirred at the same temperature for 8 hours. The catalyst was filtered off. After that, the solvent was distilled off under reduced pressure, and ethyl acetate and a saturated aqueous solution of sodium carbonate were added to adjust the pH to 7 or more. The organic layer was dried over anhydrous sodium sulfate and filtered to remove the desiccant, and then the solvent was evaporated under reduced pressure to give a crude product. The obtained crude product was recrystallized from ethanol (50 mL) to obtain a compound represented by the formula (1-1). Yield 9.6 g, yield 80%.

Example 4 Preparation of Varnish In a 200 mL pear-shaped flask equipped with a thermometer, a nitrogen purge port and a stirring rod, 2.5874 g of compound DI-7-3 (m = 3, n = 1), a compound of the formula (1--1-) 0.610 g of the compound represented by 1) was added, 59.0 g of NMP and 15.0 g of GBL were added. The solution is cooled to 5 ° C. or less, and 0.5553 g of the compound represented by the formula (AN-3-1), 0.9152 g of the compound represented by the formula (PA-1) and the formula (AN-1) are contained therein. 0.3261 g of a compound represented by 13) was added and stirred at room temperature for further 6 hours. Thereto, 20.0 g of butyl cellosolve (BC) was added, and the solution was heated and stirred at 70 ° C. until the viscosity of the solution became about 35.0 cP, to obtain Varnish 1 having a solid content of 6 wt%. The weight average molecular weight (Mw) of this varnish was 68,000.

[Examples 5 to 35 and Comparative Examples 1 to 3]
According to the method described in Example 4, a varnish with the following solid content of 6 wt% was obtained. The composition and weight average molecular weight (Mw) of the obtained varnish are shown in Tables 1-1 and 1-2. Example 4 is also listed again. The inside of [] represents the molar ratio of each of the tetracarboxylic acid compound group and the diamine compound group.

[Example 36]
<Preparation of liquid crystal aligning agent, preparation method of FFS cell, measurement of voltage holding ratio / ion density and pretilt angle>
10 g of varnish 1 was weighed in a 50 mL eggplant flask, 10 g of N-methyl-2-pyrrolidone and 10 g of butyl cellosolve were added thereto, and shaken for 2 hours to obtain liquid crystal aligning agent 1 having a solid content of 3 wt%. This alignment agent 1 was applied to a glass substrate with an FFS electrode and a glass substrate with a column spacer by a spinner method (2,000 rpm, 15 seconds). After pre-baking at 80 ° C. for about 5 minutes after coating, baking was carried out at 200 ° C. for 30 minutes to form a liquid crystal alignment film having a film thickness of about 100 nm. The obtained polyimide film was pressed on a rubbing cloth (hair foot length 1.9 mm: rayon) using a rubbing treatment apparatus manufactured by Iinuma Gauge Mfg. Co., Ltd., and the stage moving speed was 60 mm / sec, roller Rubbing was performed at a rotational speed of 1000 rpm. The obtained substrate was subjected to ultrasonic cleaning in ethanol for 5 minutes, then the surface was washed with ultrapure water and then dried in an oven at 120 ° C. for 30 minutes. A liquid crystal composition is formed between the alignment films which are opposed to each other, with the alignment film formed on the substrate facing each other on two substrates facing each other, with the rubbing direction parallel to each alignment film. A void for injection was formed and attached, and an empty FFS cell with a cell thickness of 4 μm was assembled. The following positive liquid crystal composition A was vacuum-injected into the empty FFS cell produced, and the inlet was sealed with a photo-curing agent. Next, heat treatment was performed at 110 ° C. for 30 minutes to prepare a liquid crystal cell for measurement.

物性値：ＮＩ １００．１℃； Δε ５．１； Δｎ ０．０９３； η ２５．６ｍＰａ・ｓ． <Positive Liquid Crystal Composition A>

Physical property values: NI 100.1 ° C .; Δε 5.1; Δn 0.093; η 25.6 mPa · s.

The voltage holding ratio of the obtained measurement cell was 99.8% at 5 V, 30 Hz, the ion density was 10 pC, and the pretilt angle was 1.3 °. The cell was placed on a backlight tester (FujiCOLOR LED Viewer Pro HR-2 manufactured by Fuji Film Co., Ltd .; luminance 2,700 cd / m ² ) for 1,000 hours to conduct a reliability test. The voltage holding ratio of the measuring cell after the reliability test was 99.7%, the ion density was 10 pC, and the pretilt angle was 1.3 °.

[Examples 37 to 67 and Comparative Examples 4 to 6]
Preparation of a liquid crystal aligning agent, preparation of a FFS cell, and measurement of voltage retention, ion density, and pretilt angle were also performed according to the method described in Example 36 for varnishes 2-32 and varnishes C1 to C3. The results are shown in Table 2. The results of Example 36 are also listed.

In all the results of the liquid crystal display device using the liquid crystal aligning agents 1 to 32, good results were obtained both in the initial stage and after the reliability test. In the liquid crystal display element using the liquid crystal aligning agents C1 to C2, although the voltage holding ratio and the ion density were good results, the pretilt angle was large, and the visual field characteristics were poor. In the liquid crystal display element using the liquid crystal aligning agent C3, the pretilt angle was a good result, but the ion density was large, and the result was poor in reliability.

[Examples 68 to 110 and Comparative Examples 7 to 9]
Varnishes 33 to 75 and varnishes C4 to 6 having a polymer solid concentration of 6% by weight were prepared according to Example 4 except that tetracarboxylic dianhydride and diamine were changed. The weight average molecular weight was adjusted from approximately 12,000 to 13,000 for polymers using a raw material having a photoisomerization structure, and 40,000 to 50,000 for polymers not using a raw material having a photoisomerization structure . The weight average molecular weights of the used tetracarboxylic acid dianhydride and diamine and the obtained polymer are shown in Tables 3-1 to 3-4.

[Example 111] Preparation of single layer type alignment agent, preparation of cell for measurement of electrical characteristics and measurement of electrical characteristics 10.0 g of the varnish 33 synthesized in Example 68 was added to a 50 mL recovery flask equipped with a stirring blade and a nitrogen introducing pipe. Then, 5.0 g of N-methyl-2-pyrrolidone and 5.0 g of butyl cellosolve were added thereto, and the mixture was stirred at room temperature for 1 hour to obtain an alignment agent 33 having a resin concentration of 3% by weight. The alignment agent was applied to a glass substrate with an FFS electrode and a glass substrate with a column spacer by a spinner method (2,000 rpm, 15 seconds). After coating, the substrate is heated at 80 ° C. for 3 minutes to evaporate the solvent, and then using UV light manufactured by Ushio Inc., Multilight ML-501C / B, UV rays from the vertical direction through the polarizing plate with respect to the substrate It was irradiated with linearly polarized light. The exposure energy at this time is measured to be 1.3 ± 0.1 J / cm ² at a wavelength of 365 nm by measuring the amount of light using an integrated UV light meter UIT-150 (photodetector: UVD-S365) manufactured by Ushio Inc. The exposure time was adjusted to be Subsequently, heat treatment was performed at 230 ° C. for 15 minutes in a clean oven (Espec Corp., PVHC-231) to form an alignment film with a film thickness of 100 ± 10 nm. The two substrates on which these alignment films were formed were bonded together with the surfaces on which the alignment films were formed facing each other, and gaps for injecting a liquid crystal composition provided between the facing alignment films. At this time, the polarization directions of the linearly polarized light irradiated to the respective alignment films were made parallel. The positive liquid crystal composition A was injected into these cells to prepare a liquid crystal cell (liquid crystal display element) having a cell thickness of 7 μm.

The liquid crystal cell produced as mentioned above was pinched | interposed into two polarizing plates arrange | positioned to cross nicol, and it observed visually. As a result, no so-called flow alignment was observed along the direction in which the liquid crystal flowed from the inlet. The voltage holding ratio of this liquid crystal cell was 99.8% at 5 V-30 Hz, and the ion density was 10 pC. The cell was placed on a backlight tester (FujiCOLOR LED Viewer Pro HR-2 manufactured by Fuji Film Co., Ltd .; luminance 2,700 cd / m ² ) for 1,000 hours to conduct a reliability test. The voltage holding ratio of the measuring cell after the reliability test was 99.7%, and the ion density was 10 pC.

[Examples 112 to 123 and Comparative Examples 10 to 12]
A liquid crystal cell was produced according to Example 111 except that the varnish used was changed, and observation of flow alignment and measurement of voltage holding ratio and ion density before and after reliability test were performed. The measurement results are shown in Table 4 together with Example 111.

Good results were obtained with the initial value and the value after the reliability test in all the cells of Examples 111 to 123. Here, the initial value is the result of measurement without placing the cell on the above-mentioned backlight tester after cell preparation. In the cells of Comparative Examples 10 to 11, good results were obtained for the voltage holding ratio and the ion density at the initial value and the value after the reliability test, but the flow alignment was observed and the result that the alignment of the liquid crystal was poor It became. In Comparative Example 12, no flow alignment was observed and good liquid crystal alignment was obtained, but the value of ion density was large, resulting in poor reliability.

[Example 124] Preparation of blend-type alignment agent, preparation of cell for measurement of electrical properties and measurement of electrical properties 2.0 g of varnish 38 synthesized in Example 73 in a 50 mL recovery flask equipped with a stirring blade and a nitrogen introduction tube 8.0 g of the varnish 67 synthesized in Example 102 is weighed, 5.0 g of N-methyl-2-pyrrolidone and 5.0 g of butyl cellosolve are added thereto, and the mixture is stirred at room temperature for 1 hour to obtain an alignment agent 46 having a resin concentration of 3% by weight. Obtained. A liquid crystal cell was produced according to the method described in Example 111. As a result of visually observing the liquid crystal cell by sandwiching it between two polarizing plates arranged in cross nicol, so-called flow alignment was not observed at all, in which the liquid crystal was aligned along the direction in which the liquid flowed from the injection port. The voltage holding ratio of this liquid crystal cell was 99.8% at 5 V-30 Hz, and the ion density was 10 pC. The voltage holding ratio of the measuring cell after the reliability test was 99.7%, and the ion density was 10 pC.

[Examples 125 to 172 and Comparative Examples 13-15]
A liquid crystal cell was produced according to Example 124 except that the varnish used was changed, and observation of flow alignment and measurement of voltage holding ratio and ion density before and after reliability test were performed. The varnishes used and the measurement results are shown in Tables 5-1 and 5-2 together with Example 124. In the Table, varnish A indicates a varnish containing a polymer using a raw material having a photoisomerization structure, and varnish B indicates a varnish containing a polymer not using a raw material having a photoisomerization structure.

Good results were obtained with the initial value and the value after the reliability test in all the cells of Examples 124-172. Here, the initial value is the result of measurement without placing the cell on the above-mentioned backlight tester after cell preparation. In the cells of Comparative Examples 13 to 14, good results were obtained for the voltage holding ratio and the ion density at the initial value and the value after the reliability test, but the flow alignment was observed and the result that the liquid crystal alignment was bad became. In Comparative Example 15, no flow alignment was observed and good liquid crystal alignment was obtained, but the value of ion density was large, resulting in poor reliability.

The liquid crystal display element which comprised the liquid crystal aligning film formed from the liquid crystal aligning agent of this invention from the above Example becomes a liquid crystal display element which is excellent in a viewing angle characteristic and maintains a favorable display quality also after long time progress. I understand.

By using a liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention, it is possible to obtain an excellent liquid crystal display element which is excellent in viewing angle characteristics and afterimage characteristics and which does not deteriorate in display quality even when used for a long time. In particular, it can be suitably used in the IPS mode and the FFS mode which are liquid crystal display elements of a lateral electric field system.

Claims (30)

A polyamic acid or a derivative thereof obtained by reacting a diamine containing at least one of the diamines represented by the formula (1) with a tetracarboxylic acid dianhydride ;
The derivative of polyamic acid is at least one selected from polyimide, partial polyimide, polyamic acid ester, polyamic acid-polyamide copolymer, and polyamide imide .

In formula (1), R is hydrogen, -OH, alkyl having 1 to 6 carbons, or alkoxy having 1 to 6 carbons;
X ¹ and X ² are each independently a divalent organic group having an alkylene and / or phenylene having 1 to 8 carbon atoms. The polyamic acid or its derivative (s) of Claim 1 whose diamine represented by Formula (1) is diamine represented by Formula (1 ').

In the formula (1 ′), R is hydrogen, —OH, alkyl having 1 to 6 carbons, or alkoxy having 1 to 6 carbons;
A ¹ and A ² are each independently a single bond or an alkylene having 1 to 6 carbon atoms;
The bonding position of —NH ₂ bonded to a ring is any position. The polyamic acid or its derivative (s) of Claim 1 or 2 whose R is hydrogen or -OH in the diamine represented by Formula (1). The polyamic acid or its derivative (s) of Claim 1 or 2 whose diamine represented by Formula (1) is a compound represented by a following formula (1-15) or Formula (1-29).

The tetracarboxylic acid dianhydride is at least one selected from the group of tetracarboxylic acid dianhydrides represented by the following formulas (AN-I) to (AN-VII);
Other diamines used together with the diamine represented by the formula (1) are represented by the following formulas (DI-1) to (DI-16), formulas (DIH-1) to (DIH-3), and formulas (DI) The polyamic acid or derivative thereof according to any one of claims 1 to 4, which is at least one selected from the group consisting of -31) to formula (DI-35).

In formula (AN-I), formula (AN-IV) and formula (AN-V), X is independently a single bond or -CH _2- ;
In formula (AN-II), G is 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 formulas (AN-II) to (AN-IV), Y is independently one selected from the following group of trivalent groups,

At least one hydrogen of these groups may be replaced by methyl, ethyl or phenyl;
In formulas (AN-III) to (AN-V), ring A ¹⁰ is a monocyclic hydrocarbon group of 3 to ¹⁰ carbon atoms or a fused polycyclic hydrocarbon group of 6 to 30 carbon atoms, At least one hydrogen of this group may be replaced by methyl, ethyl or phenyl, and the bond attached to the ring is connected to any carbon constituting the ring, and two bonds are identical. May be linked to carbon;
In formula (AN-VI), X ¹⁰ is alkylene having 2 to 6 carbon atoms, Me represents methyl, and Ph represents phenyl.
In formula (AN-VII), G ¹⁰ is independently -O-, -COO- or -OCO-; and r is independently 0 or 1;

In formula (DI-1), G ²⁰ is —CH ₂ —, and at least one —CH ₂ — may be replaced by —NH— or —O—, and m is an integer of 1 to 12 , At least one hydrogen of alkylene may be replaced by -OH;
In formulas (DI-3) and (DI-5) to (DI-7), G ²¹ independently represents a single bond, -NH-, -NCH _3- , -O-, -S-, -S _{-S -, - SO 2 -,} - CO -, - COO -, - CONH -, - CONCH 3 -, - 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) -, - (O-C 2 H 4) m '-O- _{, -O-CH 2 -C (CF} 3) 2 -CH 2 -O -, - O-CO- (CH 2) m '-CO-O -, - CO-O- (CH 2) m' -O _{-CO -, - (CH 2)} m '-NH- (CH 2) m' -, - CO- (CH 2) k -NH- (CH 2) k -, - (NH- (CH 2) m ' _{) k -NH -, - CO-} C 3 _{6 - (NH-C 3 H} 6) n -CO-, or -S- _(CH 2) _{m 'is} -S-, m' is an integer from 1 to 12 independently, k is 1 to 5 N is an integer of 1 or 2;
In formula (DI-4), s is independently an integer of 0 to 2;
In Formula (DI-6) and Formula (DI-7), G ²² is independently a single bond, -O-, -S-, -CO-, -C (CH ₃ ) _2- , -C (CF _{3 2} )-, -NH-, or alkylene having 1 to 10 carbon atoms;
In formulas (DI-2) to (DI-7), at least one hydrogen of a cyclohexane ring and a benzene ring is —F, —Cl, an alkyl having 1 to 3 carbon atoms, —OCH ₃ , —OH, —CF ₃ , -CO ₂ H, -CONH ₂ , -NHC ₆ H ₅ , phenyl or benzyl may be substituted, and additionally, at least one hydrogen of the benzene ring in the formula (DI-4) is represented by the following formula (DI) And -4-a) may be substituted with one selected from the group of groups represented by formula (DI-4-e);

In formulas (DI-4-a) and (DI-4-b), R ²⁰ is independently hydrogen or -CH ₃ ;
A group whose bonding position is not fixed to the 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 benzene ring is G ²¹ or G ^22. Any position except for the bonding position of

In formula (DI-11), r is 0 or 1;
In formulas (DI-8) to (DI-11), the bonding position of -NH ₂ bonded to a ring is any position;

In formula (DI-12), R ²¹ and R ^{22 each} independently represent alkyl or phenyl having 1 to 3 carbon atoms, and G ²³ independently represents alkylene, phenylene or alkyl substituted phenylene having 1 to 6 carbon atoms And w is an integer of 1 to 10;
In formula (DI-13), R ²³ is independently alkyl of 1 to 5 carbons, alkoxy of 1 to 5 carbons, or -Cl, p is independently an integer of 0 to 3, and q is Is an integer from 0 to 4;
In Formula (DI-14), ring B is monocyclic heteroaromatic, R ²⁴ is hydrogen, -F, -Cl, alkyl having 1 to 6 carbons, alkoxy having 1 to 6 carbons, 2 carbons -6 alkenyl, alkynyl having 2 to 6 carbon atoms, and q is independently an integer of 0 to 4;
In formula (DI-15), ring C is a single ring containing a hetero atom;
In formula (DI-16), G ²⁴ is a single bond, alkylene having 2 to 6 carbon atoms, or 1,4-phenylene, and r is 0 or 1;
In formulas (DI-13) to (DI-16), a group whose bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position on the ring is arbitrary;

In formula (DIH-1), G ²⁵ is 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 (DIH-2), ring D is a cyclohexane ring, a benzene ring or a naphthalene ring, and at least one hydrogen of this ring may be replaced with methyl, ethyl or phenyl;
In Formula (DIH-3), each ring E is independently a cyclohexane ring or a benzene ring, at least one hydrogen of this ring may be replaced with methyl, ethyl or phenyl, and Y is a single bond, C 1-20 alkylene, -CO-, -O-, -S-, -SO _2- , -C (CH ₃ ) _2- , or -C (CF ₃ ) _2- ;
In the formulas (DIH-2) and (DIH-3), the bonding position of -CONHNH ₂ bonded to the ring is any position;

In formula (DI-31), G ²⁶ is a single bond, -O-, -COO-, -OCO-, -CO-, -CONH-, -CH ₂ O-, -OCH _2- , -CF ₂ O- , -OCF _2- , or-(CH ₂ ) _{m '} -, m' is an integer of 1 to 12, R ²⁵ is alkyl having 3 to 30 carbon atoms, phenyl, a group having a steroid skeleton, or In the alkyl, at least one hydrogen may be replaced by -F, and at least one -CH ₂ -is -O-, -CH = may be replaced by CH- or -C≡C-, hydrogen which _{phenyl, -F, -CH 3, -OCH 3} , -OCH 2 F, -OCHF 2, -OCF 3, 3~ carbon atoms 30 alkyl or alkoxy having 3 to 30 carbon atoms It may be substituted, and the bonding position of -NH ₂ bonded to the benzene ring is an arbitrary position in the ring,

In the formula (DI-31-a), G ²⁷ , G ²⁸ and G ^{29 each} represents a bonding group, which are independently a single bond or an alkylene having 1 to 12 carbon atoms, and one or more of this alkylene CH ₂ -may be replaced by -O-, -COO-, -OCO-, -CONH-, or -CH = CH-, and ring B ²¹ , ring B ²² , ring B ²³ and ring B ²⁴ are 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, piperidine-1,4 -Diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl or anthracene-9,10-diyl, at least one hydrogen in ring B ²¹ , ring B ²² , ring B ²³ and ring B ²⁴ Is It may be replaced by F or -CH _3, s, t and u is an integer of 0 to 2 independently, their sum is 1-5, 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 is hydrogen, -F, -OH, alkyl having 1 to 30 carbons, fluorine-substituted alkyl having 1 to 30 carbons, alkoxy having 1 to 30 carbons, -CN, -OCH ₂ F, -OCHF ₂ , or -OCF ₃ and at least one -CH _2- of the alkyl having 1 to 30 carbon atoms may be replaced by a divalent group represented by the following formula (DI- 31-b),

In formula (DI-31-b), R ²⁷ and R ²⁸ independently represent alkyl having 1 to 3 carbon atoms, and v is an integer of 1 to 6;

In formulas (DI-32) and (DI-33), G ³⁰ is independently a single bond, -CO- or -CH _2- , and R ²⁹ is independently hydrogen or -CH ₃ , R ³⁰ is hydrogen, alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons;
And one hydrogen of the benzene ring in formula (DI-33) may be replaced by alkyl having 1 to 20 carbon atoms or phenyl, and
In formulas (DI-32) and (DI-33), 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;

In formulas (DI-34) and (DI-35), G ³¹ is independently -O-, -NH- or alkylene having 1 to 6 carbon atoms, and G ³² is a single bond or 1 to 3 carbon atoms Is an alkylene of
R ³¹ is hydrogen or alkyl having 1 to 20 carbon atoms, and at least one —CH ₂ — of this alkyl may be replaced by —O—, —CH = CH— or —C≡C—, R ³² is alkyl having 6 to 22 carbons, R ³³ is hydrogen or alkyl having 1 to 22 carbons, ring B ²⁵ is 1,4-phenylene or 1,4-cyclohexylene, r is 0 or 1 and -NH ₂ attached to the benzene ring indicates that the attachment position on the ring is arbitrary. The tetracarboxylic acid dianhydride is represented by the following formula (AN-1-1), formula (AN-1-2), formula (AN-1-13), formula (PA-1), formula (AN-3-1) ), Formula (AN-3-2), formula (AN-4-5), formula (AN-4-17), formula (AN-4-21), formula (AN-4-29), formula (AN) -4-30), formula (AN-5-1), formula (AN-7-2), formula (AN-10-1), formula (AN-11-3), formula (AN-16-1) At least one selected from Formula (AN-16-3), and Formula (AN-16-4);
The other diamine used together with the diamine represented by Formula (1) is a compound represented by the following Formula (DI-1-3), Formula (DI-2-1), Formula (DI-4-1), Formula (DI-4) -2), formula (DI-4-10), formula (DI-4-15), formula (DI-5-1), formula (DI-5-5), formula (DI-5-9), formula (DI-5-12), formula (DI-5-13), formula (DI-5-17), formula (DI-5-28), formula (DI-5-30), formula (DI-6-) 7), formula (DI-7-3), formula (DI-11-2), formula (DI-13-1), formula (DI-16-1), formula (DIH-2-1), and formula The polyamic acid or derivative thereof according to claim 5, which is at least one selected from the group consisting of (DI-31-56).

In formula (AN-1-2) and formula (AN-4-17), m is an integer of 1 to 12;

In Formula (DI-5-1), Formula (DI-5-12), Formula (DI-5-13), and Formula (DI-7-3), m is an integer of 1 to 12;
In formula (DI-5-30), k is an integer of 1 to 5; and
In formula (DI-7-3), n is 1 or 2. The polyamic according to any one of claims 1 to 6 , which is obtained by reacting a raw material monomer containing a compound having a photoreactive structure with at least one of tetracarboxylic acid dianhydride and diamine to be subjected to the reaction. Acid or its derivative. The polyamic acid or derivative thereof according to claim 7 , wherein the photoreactive structure is at least one selected from the group consisting of structures represented by the following formulas (P-1) to (P-7).

In formula (P-1), R ⁶¹ is independently a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, or a phenyl group. The compound having a photoreactive structure is represented by the following formula (II-1), formula (II-2), formula (III-1), formula (III-2), formula (IV-1), formula (IV-2) The polyamic acid or the polyamic acid according to claim 7 , which is at least one selected from the group consisting of: (V-1) to (V-3), and (VI-1), (VI-2) Its derivatives.

In each of the above formulas, 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 the formula (V-2), R ⁶ is independent And in the formula (V-3), ring A and ring B are each independently -CH ₃ , -OCH ₃ , -CF ₃ , or -COOCH _3; Independently, it is at least one selected from monocyclic hydrocarbon, fused polycyclic hydrocarbon and heterocycle, and R ¹¹ is linear alkylene having 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO- or -N _(CH 3) a ^{CO-, R 12} is a straight-chain alkylene having 1 to 20 carbon atoms, -COO -, - OCO -, - NHCO- or -N _(CH 3) CO- in Yes, in R ¹¹ and R ¹² , linear One or two of -CH _2-of alkylene may be substituted by -O-, and R ^{7 to} R ¹⁰ each independently represent -F, -CH ₃ , -OCH ₃ , -CF ₃ , Or -OH, and b to e are each independently an integer of 0 to 4; The polyamic acid or derivative thereof according to claim 7 , wherein the compound having a photoreactive structure is a diamine represented by the following formula (PDI-7).

In formula (PDI-7), R ⁵¹ is each independently —CH ₃ , —OCH ₃ , —CF ₃ , or —COOCH ₃ , and s is each independently an integer of 0 to 2. Liquid crystal aligning agent containing the polyamic acid or a derivative thereof according to any one of claims 1-10. It is a liquid crystal aligning agent for photo alignment which comprises polymer [A] and polymer [B] which are polyamic acid or its derivative;
A liquid crystal aligning agent for photoalignment, wherein at least one of the raw material monomers of the polymer has a photoreactive structure, and the raw material monomer of the polymer contains at least one of the compounds represented by the following formula (1) .

In formula (1), R is hydrogen, -OH, alkyl having 1 to 6 carbons, or alkoxy having 1 to 6 carbons;
X ¹ and X ² are each independently a divalent organic group having an alkylene and / or phenylene having 1 to 8 carbon atoms. At least one of polymers [A] obtained by reacting starting monomers including a compound having at least one photoreactive structure selected from the group consisting of tetracarboxylic acid dianhydride and diamine;
A polymer obtained by reacting a raw material monomer in which none of tetracarboxylic acid dianhydride and diamine has a photoreactive structure and the diamine contains at least one of the compounds represented by formula (1) The liquid crystal aligning agent for light alignment of Claim 12 containing at least 1 of [B]. A raw material monomer is reacted which contains a compound having at least one photoreactive structure selected from the group consisting of tetracarboxylic acid dianhydride and diamine, and the diamine contains at least one of the compounds represented by formula (1) With at least one of the polymers [A] obtained by
The liquid crystal for photoalignment according to claim 12 , wherein at least one of the polymer [B] obtained by reacting a raw material monomer having no photoreactive structure with any of tetracarboxylic acid dianhydride and diamine contains the polymer [B]. Alignment agent. A raw material monomer is reacted which contains a compound having at least one photoreactive structure selected from the group consisting of tetracarboxylic acid dianhydride and diamine, and the diamine contains at least one of the compounds represented by formula (1) With at least one of the polymers [A] obtained by
A polymer obtained by reacting a raw material monomer including at least one of the compounds represented by the formula (1), wherein none of the tetracarboxylic acid dianhydride and the diamine have a photoreactive structure, and The liquid crystal aligning agent for light alignment of Claim 12 containing B]. A raw material monomer is reacted which contains a compound having at least one photoreactive structure selected from the group consisting of tetracarboxylic acid dianhydride and diamine, and the diamine contains at least one of the compounds represented by formula (1) With at least one of the polymers [A] obtained by
A raw material monomer is reacted which contains a compound having at least one photoreactive structure selected from the group consisting of tetracarboxylic acid dianhydride and diamine, and the diamine contains at least one of the compounds represented by formula (1) The liquid crystal aligning agent for photo alignments of Claim 12 containing at least 1 of polymer [B] obtained by making it. Diamine represented by the formula (1) is a diamine of the formula (1 '), a liquid crystal aligning agent for optical alignment as claimed in any one of claims 12 to 16.

In the formula (1 ′), R is hydrogen, —OH, alkyl having 1 to 6 carbons, or alkoxy having 1 to 6 carbons;
A ¹ and A ² are each independently a single bond or an alkylene having 1 to 6 carbon atoms;
The bonding position of —NH ₂ bonded to a ring is any position. In diamine represented by the formula (1), R is hydrogen or -OH, a liquid crystal aligning agent for optical alignment as claimed in any one of claims 12 to 17. The liquid crystal for photoalignment according to any one of claims 12 to 18 , wherein the diamine represented by the formula (1) is a compound represented by the following formula (1-15) or the formula (1-29) Alignment agent.

The photoalignment device according to any one of claims 12 to 19 , wherein the compound having a photoreactive structure has at least one of the structures represented by the following formulas (P-1) to (P-7) Liquid crystal aligning agent.

In formula (P-1), R ⁶¹ is independently a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, or a phenyl group. The compound having a photoreactive structure is represented by the following formula (II-1), formula (II-2), formula (III-1), formula (III-2), formula (IV-1), formula (IV-2) The compound according to any one of claims 12 to 19 , which is at least one selected from the group consisting of: (V-1) to (V-3), and (VI-1), and (VI-2). The liquid crystal aligning agent for photo alignment as described in a term.

In each of the above formulas, 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 the formula (V-2), R ⁶ is independent And in the formula (V-3), ring A and ring B are each independently -CH ₃ , -OCH ₃ , -CF ₃ , or -COOCH _3; Independently, it is at least one selected from monocyclic hydrocarbon, fused polycyclic hydrocarbon and heterocycle, and R ¹¹ is linear alkylene having 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO- or -N _(CH 3) a ^{CO-, R 12} is a straight-chain alkylene having 1 to 20 carbon atoms, -COO -, - OCO -, - NHCO- or -N _(CH 3) CO- in Yes, in R ¹¹ and R ¹² , linear One or two of -CH _2-of alkylene may be substituted by -O-, and R ^{7 to} R ¹⁰ each independently represent -F, -CH ₃ , -OCH ₃ , -CF ₃ , Or -OH, and b to e are each independently an integer of 0 to 4; Compounds having a photoreactive structure is a diamine represented by the following formula (PDI-7), the liquid crystal aligning agent for photoreaction according to any one of claims 12-19.

In formula (PDI-7), R ⁵¹ is each independently —CH ₃ , —OCH ₃ , —CF ₃ , or —COOCH ₃ , and s is each independently an integer of 0 to 2. The tetracarboxylic acid dianhydride having no photoreactive structure is at least one selected from the group of tetracarboxylic acid dianhydrides represented by the following formulas (AN-I) to (AN-VII) ;
The diamine having no photoreactive structure is represented by the following formulas (DI-1) to (DI-16), formulas (DIH-1) to (DIH-3), and formulas (DI-31) to The liquid crystal aligning agent for photo alignment of any one of Claims 12-22 which are at least one chosen from the group which consists of DI-35).

In formula (AN-I), formula (AN-IV) and formula (AN-V), X is independently a single bond or -CH _2- ;
In formula (AN-II), G is 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 formulas (AN-II) to (AN-IV), Y is independently one selected from the following group of trivalent groups,

At least one hydrogen of these groups may be replaced by methyl, ethyl or phenyl;
In formulas (AN-III) to (AN-V), ring A ¹⁰ is a monocyclic hydrocarbon group of 3 to ¹⁰ carbon atoms or a fused polycyclic hydrocarbon group of 6 to 30 carbon atoms, At least one hydrogen of this group may be replaced by methyl, ethyl or phenyl, and the bond attached to the ring is connected to any carbon constituting the ring, and two bonds are identical. May be linked to carbon;
In formula (AN-VI), X ¹⁰ is alkylene having 2 to 6 carbon atoms, Me represents methyl, and Ph represents phenyl.
In formula (AN-VII), G ¹⁰ is independently -O-, -COO- or -OCO-, and r is independently 0 or 1;

In formula (DI-1), G ²⁰ is —CH ₂ —, and at least one —CH ₂ — may be replaced by —NH— or —O—, and m is an integer of 1 to 12 , At least one hydrogen of alkylene may be replaced by -OH;
In formulas (DI-3) and (DI-5) to (DI-7), G ²¹ independently represents a single bond, -NH-, -NCH _3- , -O-, -S-, -S _{-S -, - SO 2 -,} - CO -, - COO -, - CONH -, - CONCH 3 -, - 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) -, - (O-C 2 H 4) m '-O- _{, -O-CH 2 -C (CF} 3) 2 -CH 2 -O -, - O-CO- (CH 2) m '-CO-O -, - CO-O- (CH 2) m' -O _{-CO -, - (CH 2)} m '-NH- (CH 2) m' -, - CO- (CH 2) k -NH- (CH 2) k -, - (NH- (CH 2) m ' _{) k -NH -, - CO-} C 3 _{6 - (NH-C 3 H} 6) n -CO-, or -S- _(CH 2) _{m 'is} -S-, m' is an integer from 1 to 12 independently, k is 1 to 5 N is an integer of 1 or 2;
In formula (DI-4), s is independently an integer of 0 to 2;
In Formula (DI-6) and Formula (DI-7), G ²² is independently a single bond, -O-, -S-, -CO-, -C (CH ₃ ) _2- , -C (CF _{3 2} )-, -NH-, or alkylene having 1 to 10 carbon atoms;
In formulas (DI-2) to (DI-7), at least one hydrogen of a cyclohexane ring and a benzene ring is —F, —Cl, an alkyl having 1 to 3 carbon atoms, —OCH ₃ , —OH, —CF ₃ , -CO ₂ H, -CONH ₂ , -NHC ₆ H ₅ , phenyl or benzyl may be substituted, and additionally, at least one hydrogen of the benzene ring in the formula (DI-4) is represented by the following formula (DI) And -4-a) may be substituted with one selected from the group of groups represented by formula (DI-4-e);

In formulas (DI-4-a) and (DI-4-b), R ²⁰ is independently hydrogen or -CH ₃ ;
A group whose bonding position is not fixed to the 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 benzene ring is G ²¹ or G ^22. Any position except for the bonding position of

In formula (DI-11), r is 0 or 1;
In formulas (DI-8) to (DI-11), the bonding position of -NH ₂ bonded to a ring is any position;

In formula (DI-12), R ²¹ and R ^{22 each} independently represent alkyl or phenyl having 1 to 3 carbon atoms, and G ²³ independently represents alkylene, phenylene or alkyl substituted phenylene having 1 to 6 carbon atoms And w is an integer of 1 to 10;
In formula (DI-13), R ²³ is independently alkyl of 1 to 5 carbons, alkoxy of 1 to 5 carbons, or -Cl, p is independently an integer of 0 to 3, and q is Is an integer from 0 to 4;
In Formula (DI-14), ring B is monocyclic heteroaromatic, R ²⁴ is hydrogen, -F, -Cl, alkyl having 1 to 6 carbons, alkoxy having 1 to 6 carbons, 2 carbons -6 alkenyl, alkynyl having 2 to 6 carbon atoms, and q is independently an integer of 0 to 4;
In formula (DI-15), ring C is a single ring containing a hetero atom;
In formula (DI-16), G ²⁴ is a single bond, alkylene having 2 to 6 carbon atoms, or 1,4-phenylene, and r is 0 or 1;
In formulas (DI-13) to (DI-16), a group whose bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position on the ring is arbitrary;

In formula (DIH-1), G ²⁵ is 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 (DIH-2), ring D is a cyclohexane ring, a benzene ring or a naphthalene ring, and at least one hydrogen of this ring may be replaced with methyl, ethyl or phenyl;
In Formula (DIH-3), each ring E is independently a cyclohexane ring or a benzene ring, at least one hydrogen of this ring may be replaced with methyl, ethyl or phenyl, and Y is a single bond, C 1-20 alkylene, -CO-, -O-, -S-, -SO _2- , -C (CH ₃ ) _2- , or -C (CF ₃ ) _2- ;
In the formulas (DIH-2) and (DIH-3), the bonding position of -CONHNH ₂ bonded to the ring is any position;

In formula (DI-31), G ²⁶ is a single bond, -O-, -COO-, -OCO-, -CO-, -CONH-, -CH ₂ O-, -OCH _2- , -CF ₂ O- , -OCF _2- , or-(CH ₂ ) _{m '} -, m' is an integer of 1 to 12, R ²⁵ is alkyl having 3 to 30 carbon atoms, phenyl, a group having a steroid skeleton, or In the alkyl, at least one hydrogen may be replaced by -F, and at least one -CH ₂ -is -O-, -CH = may be replaced by CH- or -C≡C-, hydrogen which _{phenyl, -F, -CH 3, -OCH 3} , -OCH 2 F, -OCHF 2, -OCF 3, 3~ carbon atoms 30 alkyl or alkoxy having 3 to 30 carbon atoms It may be substituted, and the bonding position of -NH ₂ bonded to the benzene ring is an arbitrary position in the ring,

In the formula (DI-31-a), G ²⁷ , G ²⁸ and G ^{29 each} represents a bonding group, which are independently a single bond or an alkylene having 1 to 12 carbon atoms, and one or more of this alkylene CH ₂ -may be replaced by -O-, -COO-, -OCO-, -CONH-, or -CH = CH-, and ring B ²¹ , ring B ²² , ring B ²³ and ring B ²⁴ are 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, piperidine-1,4 -Diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl or anthracene-9,10-diyl, at least one hydrogen in ring B ²¹ , ring B ²² , ring B ²³ and ring B ²⁴ Is It may be replaced by F or -CH _3, s, t and u is an integer of 0 to 2 independently, their sum is 1-5, 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 is hydrogen, -F, -OH, alkyl having 1 to 30 carbons, fluorine-substituted alkyl having 1 to 30 carbons, alkoxy having 1 to 30 carbons, -CN, -OCH ₂ F, -OCHF ₂ , or -OCF ₃ and at least one -CH _2- of the alkyl having 1 to 30 carbon atoms may be replaced by a divalent group represented by the following formula (DI- 31-b),

In formula (DI-31-b), R ²⁷ and R ²⁸ independently represent alkyl having 1 to 3 carbon atoms, and v is an integer of 1 to 6;

In formulas (DI-32) and (DI-33), G ³⁰ is independently a single bond, -CO- or -CH _2- , and R ²⁹ is independently hydrogen or -CH ₃ , R ³⁰ is hydrogen, alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons;
And one hydrogen of the benzene ring in formula (DI-33) may be replaced by alkyl having 1 to 20 carbon atoms or phenyl, and
In formulas (DI-32) and (DI-33), 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;

In formulas (DI-34) and (DI-35), G ³¹ is independently -O-, -NH- or alkylene having 1 to 6 carbon atoms, and G ³² is a single bond or 1 to 3 carbon atoms Is an alkylene of
R ³¹ is hydrogen or alkyl having 1 to 20 carbon atoms, and at least one —CH ₂ — of this alkyl may be replaced by —O—, —CH = CH— or —C≡C—, R ³² is alkyl having 6 to 22 carbons, R ³³ is hydrogen or alkyl having 1 to 22 carbons, ring B ²⁵ is 1,4-phenylene or 1,4-cyclohexylene, r is 0 or 1 and -NH ₂ attached to the benzene ring indicates that the attachment position on the ring is arbitrary. The tetracarboxylic acid dianhydride which does not have a photoreactive structure is represented by the following formula (AN-1-1), formula (AN-1-2), formula (AN-1-13), formula (PA-1) Formula (AN-3-1), Formula (AN-3-2), Formula (AN-4-5), Formula (AN-4-17), Formula (AN-4-21), Formula (AN- 4-29), Formula (AN-4-30), Formula (AN-5-1), Formula (AN-7-2), Formula (AN-10-1), Formula (AN-11-3), At least one selected from Formula (AN-16-1), Formula (AN-16-3), and Formula (AN-16-4);
The diamine having no photoreactive structure is represented by the following formula (DI-1-3), formula (DI-2-1), formula (DI-4-1), formula (DI-4-2), DI-4-10), Formula (DI-4-15), Formula (DI-5-1), Formula (DI-5-5), Formula (DI-5-9), Formula (DI-5-12) ), Formula (DI-5-13), formula (DI-5-17), formula (DI-5-28), formula (DI-5-30), formula (DI-6-7), formula (DI) -7-3), formula (DI-11-2), formula (DI-13-1), formula (DI-16-1), formula (DIH-2-1), and formula (DI-31-56) The liquid crystal aligning agent for light alignment of Claim 23 which is at least one selected from the group which consists of.

In Formula (AN-1-2) and Formula (AN-4-17), m is an integer of 1-12.

In Formula (DI-5-1), Formula (DI-5-12), Formula (DI-5-13), and Formula (DI-7-3), m is an integer of 1 to 12;
In formula (DI-5-30), k is an integer of 1 to 5; and
In formula (DI-7-3), n is independently 1 or 2. Oxazine compounds, oxazoline compounds, epoxy compounds, and further containing at least one selected from the group consisting of silane coupling consists compound, a liquid crystal alignment agent according to any one of claims 12 to 24. Liquid crystal alignment film formed by the liquid crystal alignment agent according to any one of claims 12-25. Lateral electric field liquid crystal alignment film formed by the liquid crystal alignment agent according to any one of claims 12-25. The liquid crystal display element which has a liquid crystal aligning film of Claim 26 or 27 . The diamine represented by Formula (1 ').

In the formula (1 ′), R is hydrogen, —OH, alkyl having 1 to 6 carbons, or alkoxy having 1 to 6 carbons;
A ¹ and A ² are each independently a single bond or an alkylene having 1 to 6 carbon atoms;
The bonding position of —NH ₂ bonded to a ring is any position. The diamine of Claim 29 represented by following formula (1-15) or Formula (1-29).