JP2016029447A - Diamine, polyamic acid or derivative thereof, liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystal display device that prevents a reduction in display quality even after being exposed to strong light for a long period, a liquid crystal alignment film that can realize such a function of the liquid crystal display device even after being burnt at a high temperature, and a liquid crystal alignment agent for forming the liquid crystal alignment film.SOLUTION: There is provided a liquid crystal alignment film formed by using a liquid crystal alignment agent including a polyamic acid or a derivative thereof, which is obtained by causing at least one of diamines represented by the formula (1) to react with tetracarboxylic acid dianhydride. In the formula (1), Ris hydrogen or methyl; Ris hydrogen, -OH, alkyl having 1 to 6 carbon atoms, or alkoxy having 1 to 6 carbon atoms.SELECTED DRAWING: None

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 element.

The liquid crystal display elements that have been commercialized and are generally distributed today are display elements using nematic liquid crystals. As a display system of the nematic liquid crystal display element, a TN (Twisted Nematic) mode and an STN (Super Twisted Nematic) mode are well known. In recent years, in order to improve the narrow viewing angle, which is one of the problems of these modes, a TN liquid crystal display device using an optical compensation film, MVA (Multi A -domain vertical alignment (IPS) mode, a horizontal electric field type IPS (In-Plane Switching) mode, and an FFS (Fringe Field Switching) mode have been proposed and put into practical use (see Patent Documents 1 to 3).

The development of the technology of the liquid crystal display element is achieved not only by simply improving these driving methods and element structures but also by improving the components used in the elements. Among the components used in liquid crystal display elements, the liquid crystal alignment film is one of important materials related to display quality, and the performance of the alignment film can be improved with the improvement in quality of the liquid crystal display element. It is becoming important.

Currently, the liquid crystal alignment film mainly used is a polyimide-based liquid crystal alignment film formed by applying a solution (varnish) in which polyamic acid or soluble polyimide is dissolved in an organic solvent to a substrate and then heating the film. It is. In general, a liquid crystal display element in which the formed polyimide-based liquid crystal alignment film is subjected to alignment treatment is used. Several alignment treatments are known, and industrially, a rubbing method that is simple and capable of high-speed processing over a large area is widely used as the alignment treatment method. The rubbing method is a process of rubbing the surface of the liquid crystal alignment film in one direction using a cloth in which fibers of nylon, rayon, polyester, or the like are planted, and this makes it possible to obtain uniform alignment of liquid crystal molecules.

Applications of liquid crystal display devices are diverse, including monitors for personal computers, liquid crystal televisions, mobile phones, smartphone displays, and liquid crystal projectors. In recent years, considering the improvement of display quality and outdoor use, there are also applications where the brightness of the backlight as the light source is higher than the previous one, and the liquid crystal that does not deteriorate the display quality even when exposed to strong light for a long time There is a need for display elements.

In order to meet such a demand, various devices have been made for the liquid crystal alignment film. For example, a diamine having a hindered amine structure or a hindered phenol structure is contained in the raw material, and the same structure is formed in the polyimide chain. (See Patent Document 4) or a method of adding an antioxidant having a hindered amine structure or a hindered phenol structure into a liquid crystal aligning agent (see Patent Document 5). ing. However, even if these techniques are used, there is a problem that the desired performance is not exhibited depending on the difference in the manufacturing process of the liquid crystal display element, especially the firing temperature in the process of forming the liquid crystal alignment film on the substrate.

In addition, for the purpose of suppressing the occurrence of “burn-in” in the vertical alignment type liquid crystal display element, an attempt has been made to introduce a hindered amine structure into the side chain portion of the side chain diamine (see Patent Document 6). The pretilt angle of the liquid crystal molecules appears and is not suitable for the IPS and FFS modes which are transverse electric field modes.

JP-A-6-194646 JP2001-117083A JP-A-6-160878 JP2010-244015 JP2012-194537 International Publication 2008/0778629

An object of the present invention is to provide a liquid crystal display element whose display quality does not deteriorate even when exposed to strong light for a long time. In addition, a process for manufacturing a liquid crystal display element, particularly a process for forming a liquid crystal alignment film on a substrate It is to provide a liquid crystal display device that exhibits desired performance even when a high baking temperature is selected. And it is providing the liquid crystal aligning agent which can provide such a display element, and also a liquid crystal aligning film.

After intensive studies and by using the compound of formula (1), it is stable and strong for a long time without being influenced by the manufacturing process of the liquid crystal display element described above, particularly the difference in the baking temperature of the liquid crystal alignment film. A liquid crystal aligning agent and an alignment film that can provide a liquid crystal display element whose display quality does not deteriorate even when exposed to light have been completed. In particular, the effects of the present invention are more exhibited in the IPS mode and the FFS mode.

式（１）において、Ｒ^１は水素またはメチルであり；そして、
Ｒ^２は水素、−ＯＨ、炭素数１〜６のアルキル、または炭素数１〜６のアルコキシである。 The present invention comprises the following.
[1] A polyamic acid or a derivative thereof obtained by reacting at least one diamine represented by the formula (1) with at least one tetracarboxylic dianhydride.

In formula (1), R ¹ is hydrogen or methyl; and
R ² is hydrogen, —OH, alkyl having 1 to 6 carbons, or alkoxy having 1 to 6 carbons.

式（１−１）において、Ｒ^２は水素、−ＯＨ、炭素数１〜６のアルキル、または炭素数１〜６のアルコキシである。 [2] The polyamic acid or derivative thereof according to item [1], wherein the diamine represented by formula (1) is at least one diamine represented by formula (1-1).

In Formula (1-1), R ² is hydrogen, —OH, alkyl having 1 to 6 carbons, or alkoxy having 1 to 6 carbons.

式（１−２）において、Ｒ^２は水素、−ＯＨ、炭素数１〜６のアルキル、または炭素数１〜６のアルコキシである。 [3] The polyamic acid or derivative thereof according to item [1], wherein the diamine represented by formula (1) is at least one of the diamines represented by formula (1-2).

In Formula (1-2), R ² is hydrogen, —OH, alkyl having 1 to 6 carbons, or alkoxy having 1 to 6 carbons.

[4] Item [2], wherein the diamine represented by formula (1) is at least one selected from the group of compounds represented by formula (1-1-1) to formula (1-1-28). Or a derivative thereof.

[5] The item [3], wherein the diamine represented by the formula (1) is at least one selected from the group of compounds represented by the formulas (1-2-1) to (1-228). Or a derivative thereof.

[6] [1] to [5] obtained by reacting a mixture of at least one diamine represented by the formula (1) and at least one other diamine with at least one tetracarboxylic dianhydride. The polyamic acid or derivative thereof according to any one of the above.

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である。 [7] The tetracarboxylic dianhydride is at least one selected from the group of tetracarboxylic dianhydrides represented by the following formulas (AN-I) to (AN-VII): [6] The polyamic acid or derivative thereof according to any one of [6].

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 carbons, —CO—, —O—, —S—, —SO ₂ —, —C (CH ₃ ) ₂ —, or —C. (CF ₃ ) ₂ —;
In formula (AN-II) to formula (AN-IV), Y is independently one selected from the group of trivalent groups below,

At least one hydrogen of these groups may be replaced by methyl, ethyl or phenyl;
In Formula (AN-III) to Formula (AN-V), Ring A ¹⁰ is a monocyclic hydrocarbon group having 3 to ¹⁰ carbon atoms or a condensed polycyclic hydrocarbon group having 6 to 30 carbon atoms, At least one hydrogen of this group may be replaced by methyl, ethyl or phenyl, and the bond on the ring is connected to any carbon constituting the ring, and the two bonds are the same. May be linked to carbon;
In the formula (AN-VI), X ¹⁰ is alkylene having 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.

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。 [8] The tetracarboxylic dianhydride has the following formula (AN-1-1), formula (AN-1-2), formula (AN-1-13), formula (AN-2-1), 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), formula (AN-11-3), formula (AN-16) -3) and the polyamic acid or derivative thereof according to item [7], which is at least one selected from the formula (AN-16-4).

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

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−、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のアルキレン、−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１〜６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−、−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、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−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。 [9] Other diamines include the following formula (DI-1) to formula (DI-16), formula (DIH-1) to formula (DIH-3), and formula (DI-31) to formula (DI-35). ) The polyamic acid or derivative thereof according to item [6], which is at least one selected from the group consisting of:

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

In formula (DI-4-a) and formula (DI-4-b), R ²⁰ is independently hydrogen or —CH ₃ ;
A group in which the bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary, and the bonding position of —NH ₂ to the cyclohexane ring or the benzene ring is G ²¹ or G ^22. Any position except the binding position of

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

In formula (DI-12), R ²¹ and R ²² are independently alkyl or phenyl having 1 to 3 carbon atoms, and G ²³ is independently alkylene, phenylene or alkyl-substituted phenylene having 1 to 6 carbon atoms. And w is an integer from 1 to 10;
In the formula (DI-13), R ²³ is independently alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons or —Cl, p is independently an integer of 0 to 3, and q is An integer from 0 to 4;
In the formula (DI-14), ring B is a monocyclic heteroaromatic, R ²⁴ is hydrogen, —F, —Cl, alkyl having 1 to 6 carbons, alkoxy having 1 to 6 carbons, or carbon 2 -6 alkenyl, C1-C6 alkynyl, q is independently an integer of 0-4;
In formula (DI-15), ring C is a monocycle containing a heteroatom;
In the formula (DI-16), G ²⁴ is a single bond, alkylene having 2 to 6 carbons or 1,4-phenylene, and r is 0 or 1;
In formula (DI-13) to formula (DI-16), a group in which the bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary;

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

In the formula (DI-31), G ²⁶ represents a single bond, —O—, —COO—, —OCO—, —CO—, —CONH—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—. , —OCF ₂ —, or — (CH ₂ ) _{m ′} —, 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 of a group represented by the formula (DI-31-a), and in the alkyl, at least one hydrogen may be replaced by -F, at least one of -CH ₂ - -O -, - CH = CH— or —C≡C— may be substituted, and the hydrogen of this phenyl is —F, —CH ₃ , —OCH ₃ , —OCH ₂ F, —OCHF ₂ , —OCF ₃ , With 30 alkyls or C 3-30 alkoxys It may be replaced, 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 are bonding groups, and these are each independently a single bond or alkylene having 1 to 12 carbons, and one or more — CH ₂ — may be replaced by —O—, —COO—, —OCO—, —CONH—, —CH═CH—, and ring B ²¹ , ring B ²² , ring B ²³ and ring B ²⁴ are independently 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, naphthalene-1,5- Diyl, naphthalene-2,7-diyl or anthracene-9,10-diyl, wherein in ring B ²¹ , ring B ²² , ring B ²³ and ring B ²⁴ at least one hydrogen is replaced by —F or —CH ₃ Being S, t, and u are each independently an integer of 0-2, and their sum is 1-5, and when s, t, or u is 2, two bonds in each parenthesis The groups 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 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 the formula (DI-31-b), R ²⁷ and R ²⁸ are independently alkyl having 1 to 3 carbons, and v is an integer of 1 to 6;

In the formula (DI-32) and the formula (DI-33), G ³⁰ is independently a single bond, —CO— or —CH ₂ —, R ²⁹ is independently hydrogen or —CH ₃ , R 30 ³⁰ is hydrogen, alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons;
One hydrogen of the benzene ring in formula (DI-33) may be replaced by alkyl or phenyl having 1 to 20 carbon atoms, and
In formula (DI-32) and formula (DI-33), a group in which the bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary;

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

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。 [10] Other diamines are 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-5-9), formula (DI-5-12), formula (DI-5-13), formula (DI-5-28), Formula (DI-5-30), Formula (DI-7-3), Formula (DI-13-1), Formula (DI-16-1), and Formula (DIH-2) The polyamic acid or derivative thereof according to item [6], which is at least one selected from the group consisting of -1).

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 from 1 to 5;
In the formula (DI-7-3), n is 1 or 2.

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

[12] A liquid crystal aligning agent comprising the polyamic acid or derivative thereof according to any one of [1] to [10] and a polymer other than that.

[13] Item [11] or further containing at least one selected from the group consisting of an alkenyl-substituted nadiimide compound, a compound having a radical polymerizable unsaturated double bond, an oxazine compound, an oxazoline compound, and an epoxy compound The liquid crystal aligning agent as described in the item [12].

[14] The liquid crystal aligning agent for a horizontal electric field type liquid crystal display element according to any one of [11] to [13].

[15] A liquid crystal alignment film formed by the liquid crystal aligning agent according to any one of [11] to [14].

[16] A liquid crystal display device comprising the liquid crystal alignment film according to the item [15].

式（１−２）において、Ｒ^２は水素、−ＯＨ、炭素数１〜６のアルキル、または炭素数１〜６のアルコキシである。 [17] A diamine represented by the formula (1-2).

In Formula (1-2), R ² is hydrogen, —OH, alkyl having 1 to 6 carbons, or alkoxy having 1 to 6 carbons.

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 reliability. Moreover, a certain performance can be exhibited without depending on the difference in the manufacturing process. The liquid crystal display element provided with the liquid crystal alignment film does not deteriorate the display quality even when used for a long time. In addition, if you want to give other properties such as further reducing afterimages and improving printability on the substrate, liquid crystals with the desired properties can also be blended with other polymers or combined with additives. A display element can be provided.

In the diamine represented by the formula (1), R ¹ is hydrogen or methyl, and R ² is hydrogen, —OH, alkyl having 1 to 6 carbons, or alkoxy having 1 to 6 carbons. The substitution position of the two amino groups in the benzene ring is not particularly limited. However, in order to obtain a liquid crystal aligning agent that aligns liquid crystal molecules better, the substitution position of the amide group is 3, 5 or 2, 5th place is desirable.

式（１−１）および式（１−２）において、Ｒ^２は水素、−ＯＨ、炭素数１〜６のアルキル、または炭素数１〜６のアルコキシである。 Diamines represented by formula (1) are classified into diamines represented by formula (1-1) in which R ¹ is hydrogen and diamines represented by formula (1-2) in which R ¹ is methyl. Is done.

In Formula (1-1) and Formula (1-2), R ² is hydrogen, —OH, alkyl having 1 to 6 carbons, or alkoxy having 1 to 6 carbons.

When a liquid crystal aligning agent having higher solubility in a solvent is desired, it is preferable to use a diamine of the formula (1-1). When a more reliable liquid crystal alignment film is desired, it is preferable to use a compound in which R ² is hydrogen or —OH in formulas (1-1) and (1-2).

Specific examples of the diamine represented by the formula (1-1) are compounds represented by the following formulas (1-1-1) to (1-1-28).

Specific examples of the diamine represented by the formula (1-2) are compounds represented by the following formulas (1-2-1) to (1-228).

Diamines represented by formula (1-1-1) to formula (1-1-4), formula (1-2-1) and formula (1-2-2) constitute the liquid crystal aligning agent of the present invention. By using it as one of the raw materials for the polymer, a liquid crystal alignment film having high liquid crystal alignment properties can be obtained without deteriorating display quality even when used for a long time.

By using the diamine represented by the formula (1-2-1) to the formula (1-2-6) as one of the raw materials of the polymer constituting the liquid crystal aligning agent of the present invention, it is represented by the formula (1). Even when other diamines other than diamines are used in combination, gelation can be suppressed during polymer synthesis. This is thought to be because the intermolecular interaction due to hydrogen bonding disappears because the hydrogen of the amide group is replaced with a methyl group.

３，５−ジニトロベンゾイルクロライドと市販の４−アミノ−２，２，６，６−テトラメチルピペリジン誘導体をトリエチルアミンなどの塩基存在下で反応させ、続いてパラジウム炭素触媒存在下、水素雰囲気下でニトロ基の還元を行うことで、アミノ基の置換位置が３，５−位であり、Ｒ^１が水素の式（１）のジアミンが得られる。 <Synthesis Method of Diamine Represented by Formula (1)>
The diamine represented by the formula (1) can be synthesized by the following route.
<Compound in which the amino group is substituted at the 3,5-position and R ¹ is hydrogen>

3,5-dinitrobenzoyl chloride and a commercially available 4-amino-2,2,6,6-tetramethylpiperidine derivative are reacted in the presence of a base such as triethylamine, followed by nitrocarburization in the presence of a palladium carbon catalyst in a hydrogen atmosphere. By performing group reduction, a diamine of formula (1) in which the amino group is substituted at the 3,5-position and R ¹ is hydrogen is obtained.

<Compound in which the substitution position of the amino group is 3,5-position and R ¹ is methyl>

A commercially available 4-amino-2,2,6,6-tetramethylpiperidine derivative is reacted with methyl iodide to obtain a 4-methylamino-2,2,6,6-tetramethylpiperidine derivative. The subsequent reaction is carried out according to the synthesis of the compound in which the amino group is substituted at the 3,5-position, and R1 is substituted at the 3,5-position, and R1 is methyl. The diamine represented by (1) is obtained.

市販の２−ブロモ−５−ニトロ安息香酸を塩化チオニルと反応させ２−ブロモ−５−ニトロベンゾイルクロライドを得る。得られた２−ブロモ−５−ニトロベンゾイルクロライドと市販の４−アミノ−２，２，６，６−テトラメチルピペリジン誘導体をトリエチルアミンなどの塩基存在下で反応させアミド体を得る。そのアミド体の臭素を、Ｂｕｃｈｗａｌｄ反応を利用してベンゾフェノンイミンで置換された化合物を得る。塩酸などの酸でベンゾフェノンイミン部位をアミノ基に変換し、続いてパラジウム炭素触媒存在下、水素雰囲気下でニトロ基の還元を行うことで、アミノ基の置換位置が２，５−位であり、Ｒ^１が水素の式（１）で表されるジアミンが得られる。 <Compound whose amino group is substituted at the 2,5-position and R ¹ is hydrogen>

Commercially available 2-bromo-5-nitrobenzoic acid is reacted with thionyl chloride to give 2-bromo-5-nitrobenzoyl chloride. The obtained 2-bromo-5-nitrobenzoyl chloride and a commercially available 4-amino-2,2,6,6-tetramethylpiperidine derivative are reacted in the presence of a base such as triethylamine to obtain an amide. A compound in which the amide bromine is substituted with benzophenone imine using the Buchwald reaction is obtained. By converting the benzophenone imine moiety to an amino group with an acid such as hydrochloric acid, and subsequently reducing the nitro group in the presence of a palladium carbon catalyst in a hydrogen atmosphere, the amino group substitution position is 2,5-position, A diamine represented by the formula (1) in which R ¹ is hydrogen is obtained.

市販の４−アミノ−２，２，６，６−テトラメチルピペリジン誘導体をヨウ化メチルと反応させ、４−メチルアミノ−２，２，６，６−テトラメチルピペリジン誘導体を得る。その後の反応はアミノ基の置換位置が２，５−位であり、Ｒ^１が水素の化合物の合成に準じて行うことでアミノ基の置換位置が２，５−位であり、Ｒ^１がメチルの式（１）で表されるジアミンが得られる。 <Compound in which the amino group is substituted at the 2,5-position and R ¹ is methyl>

A commercially available 4-amino-2,2,6,6-tetramethylpiperidine derivative is reacted with methyl iodide to obtain a 4-methylamino-2,2,6,6-tetramethylpiperidine derivative. Subsequent reaction is performed according to the synthesis of the compound in which the amino group is substituted at the 2,5-position, and R ¹ is hydrogen, whereby the amino group is substituted at the 2,5-position, and R ¹ is methyl. A diamine represented by the formula (1) is obtained.

The polyamic acid and derivatives thereof of the present invention will be described.
The polyamic acid and derivatives thereof of the present invention are reaction products of tetracarboxylic dianhydride and a diamine containing a diamine represented by the formula (1). The derivative of the polyamic acid is a component that dissolves in a solvent when a liquid crystal aligning agent containing a solvent, which will be described later, is used. It is a component that can form a film. Examples of such a derivative of polyamic acid include soluble polyimide, polyamic acid ester, polyamic acid amide, and the like. More specifically, 1) polyimide in which all amino acids and carboxyl of polyamic acid are subjected to a dehydration ring-closing reaction, 2) Partially dehydrated ring-closing partial polyimide, 3) Polyamic acid ester in which carboxyl of polyamic acid is converted to ester, 4) Part of acid dianhydride contained in tetracarboxylic dianhydride compound is organic dicarboxylic Examples thereof include polyamic acid-polyamide copolymers obtained by reacting with an acid, and 5) polyamideimide obtained by subjecting a part or all of the polyamic acid-polyamide copolymer to a dehydration ring-closing reaction. One kind of compound may be sufficient as the said polyamic acid and its derivative (s), and 2 or more types may be sufficient as it. The polyamic acid and its derivative may be a compound having a structure of a reaction product of tetracarboxylic dianhydride and diamine, and other raw materials may be used except for the reaction of tetracarboxylic dianhydride and diamine. It may contain reaction products from other reactions.

The tetracarboxylic dianhydride used for producing the polyamic acid and derivatives thereof of the present invention will be described.
The tetracarboxylic dianhydride used in the present invention can be selected without limitation from known tetracarboxylic dianhydrides. Such tetracarboxylic dianhydrides include aromatic systems (including heteroaromatic ring systems) in which dicarboxylic acid anhydrides are directly bonded to aromatic rings, and aliphatic groups in which dicarboxylic acid anhydrides are not directly bonded to aromatic rings. It may belong to any group of systems (including heterocyclic ring systems).

式（ＡＮ−Ｉ）、（ＡＮ−ＩＶ）および（ＡＮ−Ｖ）において、Ｘは独立して単結合または−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）〜（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）〜（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 dianhydrides include those represented by the formulas (AN-I) to (AN-VII) from the viewpoint of easy availability of raw materials, ease of polymer polymerization, and electrical characteristics of the film. The tetracarboxylic dianhydride represented is mentioned.

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

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

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

式（ＡＮ−１）において、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 dianhydride represented by the formula (AN-1)]

In the formula (AN-1), G ¹¹ is a single bond, alkylene having 1 to 12 carbons, 1,4-phenylene, or 1,4-cyclohexylene. X ¹¹ is independently a single bond or —CH ₂ —. G ¹² is independently one of the following trivalent groups.

When G ¹² is> CH—, the hydrogen of> CH— may be replaced with —CH ₃ . When G ¹² is> N—, G ¹¹ is not a single bond and —CH ₂ —, and X ¹¹ is not a single bond. 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。 Examples of the tetracarboxylic dianhydride represented by the formula (AN-1) include compounds represented by the following formula.

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

式（ＡＮ−２）において、Ｒ^１２は独立して水素、−ＣＨ_３、−ＣＨ_２ＣＨ_３、またはフェニルである。 [Tetracarboxylic dianhydride represented by the formula (AN-2)]

In formula (AN-2), R ¹² is independently hydrogen, —CH ₃ , —CH ₂ CH ₃ , or phenyl.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-2) include compounds represented by the following formula.

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

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

Examples of the tetracarboxylic dianhydride represented by the formula (AN-3) include compounds represented by the following formula.

式（ＡＮ−４）において、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 dianhydride represented by the formula (AN-4)]

In the 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. Each ring A ¹¹ is independently a cyclohexane ring or a benzene ring. G ¹³ may be bonded to any position of ring A ¹¹ .

In formula (G13-1), G ^13a and G ^13b each independently represent a single bond, a divalent group represented by —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。

Examples of the tetracarboxylic dianhydride represented by the formula (AN-4) include compounds represented by the following formula.

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

式（ＡＮ−５）において、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 dianhydride represented by the formula (AN-5)]

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

Examples of the tetracarboxylic dianhydride represented by the formula (AN-5) include compounds represented by the following formula.

式（ＡＮ−６）において、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 dianhydride represented by the formula (AN-6)]

In the formula (AN-6), X ¹¹ is independently a single bond or —CH ₂ —. X ¹² is _{-CH 2 -, - CH 2 CH} 2 - or -CH = CH-. n is 1 or 2.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-6) include compounds represented by the following formula.

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

In the formula (AN-7), X ¹¹ is a single bond or —CH ₂ —.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-7) include compounds represented by the following formula.

式（ＡＮ−８）において、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 dianhydride represented by the formula (AN-8)]

In the 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.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-8) include compounds represented by the following formula.

式（ＡＮ−９）において、ｒはそれぞれ独立して０または１である。 [Tetracarboxylic dianhydride represented by the formula (AN-9)]

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

Examples of the tetracarboxylic dianhydride represented by the formula (AN-9) include compounds represented by the following formula.

[Tetracarboxylic dianhydrides 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 dianhydride represented by the formula (AN-11)]

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

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

式（ＡＮ−１２）において、環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 dianhydride represented by the formula (AN-12)]

In formula (AN-12), each of ring A ¹¹ is independently a cyclohexane ring or a benzene ring.

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

式（ＡＮ−１３）において、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 dianhydride represented by the formula (AN-13)]

In the formula (AN-13), X ¹³ is alkylene having 2 to 6 carbon atoms, and Ph represents phenyl.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-13) include compounds represented by the following formula.

式（ＡＮ−１４）において、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 dianhydride represented by the formula (AN-14)]

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

Examples of the tetracarboxylic dianhydride represented by the formula (AN-14) include compounds represented by the following formula.

式（ＡＮ−１５）において、ｗは１〜１０の整数である。 [Tetracarboxylic dianhydride represented by the formula (AN-15)]

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

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

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

In the acid dianhydride, suitable materials for improving each property will be described. When importance is attached to improving the orientation of the liquid crystal, compounds represented by the formulas (AN-1), (AN-3), and (AN-4) are preferred, and the formula (AN-1-2) , (AN-1-13), (AN-3-2), (AN-4-17) and (AN-4-29) are particularly preferred, and among them, the formula (AN-1-2) In the formula, 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.

When importance is attached to improving the transmittance of the liquid crystal display element, among the above acid dianhydrides, the formulas (AN-1-1), (AN-1-2), (AN-2-1) , (AN-3-1), (AN-4-17), (AN-4-30), (AN-5-1), (AN-7-2), (AN-10), (AN- 16-3) and compounds represented by (AN-16-4) are preferable, and in Formula (AN-1-2), m = 4 or 8 is preferable, and Formula (AN-4-17) is preferable. ), M = 4 or 8 is preferable, and m = 8 is particularly preferable.

In the case where importance is attached to improving the VHR of the liquid crystal display element, among the above acid dianhydrides, the formulas (AN-1-1), (AN-1-2), (AN-2-1), (AN-3-1), (AN-4-17), (AN-4-30), (AN-7-2), (AN-10), (AN-16-3), and (AN- 16-4) is preferred, and in formula (AN-1-2), m = 4 or 8 is preferred, and in formula (AN-4-17), m = 4, or 8 is preferred, and m = 8 is particularly preferred.

Increasing the relaxation rate of residual charges (residual DC) in the alignment film by reducing the volume resistance value of the liquid crystal alignment film is an effective method for preventing burn-in. When the purpose is emphasized, among the above acid dianhydrides, the formulas (AN-1-13), (AN-3-2), (AN-4-21), (AN-4-29) And a compound represented by (AN-11-3) is preferable.

The diamine and dihydrazide used for producing the polyamic acid and derivatives thereof of the present invention will be described. In producing the polyamic acid or derivative thereof of the present invention, 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, a group branched from the main chain, that is, a diamine having a side chain group and a diamine having no side chain group. This side chain group is a group having an effect of increasing the pretilt angle. The side chain group having such an effect needs to be a group having 3 or more carbon atoms. Specific examples include alkyl having 3 or more carbon atoms, alkoxy having 3 or more carbon atoms, alkoxyalkyl having 3 or more carbon atoms, and A group having a steroid skeleton can be exemplified. A group having one or more rings, wherein the terminal ring has any one of alkyl having 1 or more carbon atoms, alkoxy having 1 or more carbon atoms and alkoxyalkyl having 2 or more carbon atoms as a substituent; It has an effect as a side chain group. In the following description, a diamine having such a side chain group may be referred to as a side chain diamine. Such a diamine having no side chain group may be referred to as a non-side chain diamine.

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

上記の式（ＤＩ−１）において、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−、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のアルキレン、−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 diamine will be described. Examples of diamines having no known side chain include diamines of the following formulas (DI-1) to (DI-16).

In the above formula (DI-1), G ²⁰ is —CH ₂ —, at least one —CH ₂ — may be replaced by —NH—, —O—, and m is an integer of 1-12. And at least one hydrogen of the alkylene may be replaced by -OH. In Formula (DI-3) and Formula (DI-5) to Formula (DI-7), G ²¹ is independently 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 an integer of 0-2 independently. In the formula (DI-6) and the formula (DI-7), G ²² is independently a single bond, —O—, —S—, —CO—, —C (CH ₃ ) ₂ —, —C (CF _{3 2} ) or alkylene having 1 to 10 carbon atoms. At least one hydrogen of the cyclohexane ring and the benzene ring in the formula (DI-2) to the formula (DI-7) is —F, —Cl, alkylene having 1 to 3 carbon atoms, —OCH ₃ , —OH, —CF. ₃ , —CO ₂ H, —CONH ₂ , —NHC ₆ H ₅ , phenyl, or benzyl, and in Formula (DI-4), at least one hydrogen of the cyclohexane ring and the benzene ring is It may be replaced with one selected from the group of groups represented by the following formula (DI-4-a) to formula (DI-4-e). A group in which the bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary. The bonding position of —NH ₂ to the cyclohexane ring or the benzene ring is an arbitrary position excluding the bonding position of G ²¹ or G ²² .

In Formula (DI-4-a) and Formula (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 the formula (DI-11), r is 0 or 1. In Formula (DI-8) to Formula (DI-11), the bonding position of —NH ₂ bonded to the 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、アルコキシ、ビニル、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 are independently alkyl or phenyl having 1 to 3 carbon atoms, and G ²³ is independently alkylene, phenylene or alkyl-substituted phenylene having 1 to 6 carbon atoms. And w is an integer of 1-10. In the formula (DI-13), R ²³ is independently alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons or —Cl, p is independently an integer of 0 to 3, and q is It is an integer of 0-4. In the formula (DI-14), ring B is a monocyclic heterocyclic aromatic group, R ²⁴ is hydrogen, —F, —Cl, C 1-6 alkyl, alkoxy, vinyl, alkynyl, q is an integer of 0 to 4 independently. In formula (DI-15), ring C is a heterocyclic aromatic group or a heterocyclic aliphatic group. In the 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. A group whose bond position is not fixed to the carbon atoms constituting the ring indicates that the bond position in the ring is arbitrary. In Formula (DI-13) to Formula (DI-16), the bonding position of —NH ₂ bonded to the ring is an arbitrary position.

Specific examples of the following formulas (DI-1-1) to (DI-16-1) include diamines having no side chain of the above formula (DI-1) to formula (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 the diamine represented by the 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.

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

式（ＤＩ−５−１）において、ｍは１〜１２の整数である。

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

式（ＤＩ−５−１６）において、ｖは１〜６の整数である。

式（ＤＩ−５−３０）において、ｋは１〜５の整数である。

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。 Examples of the diamine represented by the formula (DI-5) are shown below.

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

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

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

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

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

Examples of the diamine represented by the 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。

Examples of the diamine represented by the 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.

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

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

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

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

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

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

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

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

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

Dihydrazide will be described. Examples of the dihydrazide having no known 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 the formula (DIH-1), G ²⁵ represents a single bond, alkylene having 1 to 20 carbon atoms, —CO—, —O—, —S—, —SO ₂ —, —C (CH ₃ ) ₂ —, or — C (CF ₃ ) ₂ —.
In formula (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 with methyl, ethyl or phenyl. In the formula (DIH-3), each ring E is independently a cyclohexane ring or a benzene ring, and at least one hydrogen of this group may be replaced with methyl, ethyl, or phenyl, 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 Formula (DIH-2) and Formula (DIH-3), the bonding position of -CONHNH ₂ bonded to the ring is an arbitrary 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 1-12.

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

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

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

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

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

式（ＤＩ−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、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。 Examples of the diamine having a side chain include compounds represented by the following formula (DI-31) to formula (DI-35).

In the formula (DI-31), G ²⁶ represents a single bond, —O—, —COO—, —OCO—, —CO—, —CONH—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—. , —OCF ₂ —, or — (CH ₂ ) _{m ′} —, and m ′ is an integer of 1 to 12. Preferred examples of G ²⁶ include a single bond, —O—, —COO—, —OCO—, —CH ₂ O—, and alkylene having 1 to 3 carbon atoms, and particularly preferred examples include a single bond, —O—, — _{COO -, - OCO -, -} CH 2 O -, - CH 2 - and _-CH 2 CH ₂ -. R ²⁵ is a group having 3 to 30 carbon atoms, phenyl, a group having a steroid skeleton, or a group represented by the following formula (DI-31-a). In the alkyl, at least one hydrogen may be replaced by -F, and at least one -CH ₂ - is -O -, - CH = CH- or may be replaced by -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 Also good. The bonding position of —NH ₂ bonded to the benzene ring indicates an arbitrary position in the ring, but the bonding position is preferably meta or para. That is, when the bonding position of the group “R ²⁵ -G ²⁶ —” is the first position, the two bonding positions are preferably the third position and the fifth position, or the second position and the fifth position.

In the formula (DI-31-a), G ²⁷ , G ²⁸ and G ²⁹ are bonding groups, and these are each independently a single bond or alkylene having 1 to 12 carbons, and one or more — CH ₂ — may be replaced by —O—, —COO—, —OCO—, —CONH—, —CH═CH—. Ring B ²¹ , Ring B ²² , Ring B ²³ and Ring B ²⁴ are independently 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5. - diyl, pyridine-2,5-diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl or anthracene-9,10-diyl, ring ^{B 21,} ring ^{B 22,} ring ^{B 23} and ring in B ^24, at least one hydrogen 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 the formula (DI-31-b), R ²⁷ and R ²⁸ are each 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 the formula (DI-32) and the formula (DI-33), G ³⁰ is independently a single bond, —CO— or —CH ₂ —, R ²⁹ is independently hydrogen or —CH ₃ , R 30 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 with alkyl having 1 to 20 carbons or phenyl. A group whose bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary. One of the two groups “-phenylene-G ³⁰ —O—” in formula (DI-32) is preferably bonded to the 3-position of the steroid nucleus and the other is bonded to the 6-position of the steroid nucleus. The bonding position of the two groups “-phenylene-G ³⁰ —O—” in formula (DI-33) to the benzene ring is preferably a meta position or a para position, respectively, with respect to the bonding position of the steroid nucleus. In formula (DI-32) and formula (DI-33), -NH ₂ bonded to the benzene ring indicates that the binding position in the ring is optional.

式（ＤＩ−３４）および式（ＤＩ−３５）において、Ｇ^３１は独立して−Ｏ−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 Formula (DI-34) and Formula (DI-35), G ³¹ is independently —O— or alkylene having 1 to 6 carbons, and G ³² is a single bond or alkylene having 1 to 3 carbons. . R ³¹ is hydrogen or alkyl having 1 to 20 carbons, and at least one —CH ₂ — of the alkyl may be replaced by —O—, —CH═CH— or —C≡C—. R ³² is alkyl having 6 to 22 carbon atoms, and R ³³ is hydrogen or alkyl having 1 to 22 carbon atoms. Ring B ²⁵ is 1,4-phenylene or 1,4-cyclohexylene, and r is 0 or 1. And although -NH ₂ bonded to the benzene ring indicates that the binding position in the ring is optional, it is preferable independently a meta or para position with respect to the binding position of the G ^31.

Specific examples of the side chain diamine are illustrated below. Examples of the diamine having a side chain of the above formula (DI-31) to formula (DI-35) include compounds represented by the following formula (DI-31-1) to formula (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 the formula (DI-31) are shown below.

In the formula (DI-31-1) to the formula (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 Alkoxy having 5 to 25 carbon atoms. 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 Formula (DI-31-12) to Formula (DI-31-17), R ³⁶ is alkyl having 4 to 30 carbons, and preferably alkyl having 6 to 25 carbons. R ³⁷ is alkyl having 6 to 30 carbon atoms, preferably alkyl having 8 to 25 carbon atoms.

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 formula (DI-31-18) to formula (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 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 ₃ to 25 carbons. Alkyl or alkoxy having 3 to 25 carbon atoms. G ³³ is alkylene having 1 to 20 carbon atoms.

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

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

式（ＤＩ−３４−１）〜式（ＤＩ−３４−１２）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 the compound represented by the formula (DI-34) are shown below.

In Formula (DI-34-1) to Formula (DI-34-12), R ⁴⁰ is hydrogen or alkyl having 1 to 20 carbons, preferably hydrogen or alkyl having 1 to 10 carbons, and R ⁴¹ 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。 Examples of the compound represented by the formula (DI-35) are shown below.

In formula (DI-35-1) ~ formula ^{(DI-35-3), R 37} is alkyl of 6 to 30 carbon ^{atoms, 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。 As the diamine in the present invention, the formula (DI-1-1) to the formula (DI-16-1), the formula (DIH-1-1) to the formula (DIH-3-6), and the formula (DI-31-1). ) To diamines other than the diamines represented by formula (DI-35-3) can also be used. Examples of such diamines include compounds represented by the following formulas (DI-36-1) to (DI-36-13).

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

In the formula (DI-36-9) to the formula (DI-36-11), e is an integer of 2 to 10, and in the formula (DI-36-12), each R ⁴³ is independently hydrogen, —NHBoc. Or —N (Boc) ₂ , 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 from 1 to 12. Here, Boc is a t-butoxycarbonyl group.

When importance is attached to further improving the orientation of the liquid crystal, among the above diamines and dihydrazides, the formula (DI-1-3), formula (DI-5-1), formula (DI-5-5) , 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 a diamine represented by the formula (DI-11-2) are preferably used, and in the formula (DI-5-1), m = 2, 4 or 6 is preferable, and m = 4 is preferable. Particularly preferably, in formula (DI-5-12), m = 2 to 6 is preferable, m = 5 is particularly preferable, and in formula (DI-5-13), m = 1 or 2 is preferable, and m = 1. Is particularly preferred.

When importance is attached to improving the transmittance, among the above diamines and dihydrazides, the formula (DI-1-3), the formula (DI-2-1), the formula (DI-5-1), the formula ( It is preferable to use diamines represented by DI-5-5), formula (DI-5-24), and formula (DI-7-3), and diamines represented by (DI-2-1) are particularly preferred. preferable. In Formula (DI-5-1), m = 2, 4 or 6 is preferable, and m = 4 is particularly preferable. In Formula (DI-7-3), m = 2, 3, or n = 1. Or 2 is preferable, and m = 1 is particularly preferable.

When importance is attached to improving the VHR of the liquid crystal display element, among the above diamines and dihydrazides, the formula (DI-2-1), formula (DI-4-1), formula (DI-4-2) , Formula (DI-4-10), formula (DI-4-15), formula (DI-5-28), formula (DI-5-30), and formula (DI-13-1) A diamine is preferably used, and diamines represented by the formula (DI-2-1), the formula (DI-5-1), and the formula (DI-13-1) are particularly preferable. Among them, in the formula (DI-5-1), m = 1 is particularly preferable, and in the formula (DI-5-30), k = 2 is particularly preferable.

Increasing the relaxation rate of residual charges (residual DC) in the alignment film by reducing the volume resistance value of the liquid crystal alignment film is an effective method for preventing burn-in. When emphasizing this purpose, among the above diamines and dihydrazides, formula (DI-4-1), formula (DI-4-2), formula (DI-4-10), formula (DI-4- 15), Formula (DI-5-1), Formula (DI-5-12), Formula (DI-5-13), Formula (DI-5-28), and Formula (DI-16-1) It is preferable to use diamines represented by formula (DI-4-1), formula (DI-5-1), and diamines represented by formula (DI-5-13). Among them, in the formula (DI-5-1), m = 2, 4 or 6 is preferable, m = 4 is particularly preferable, and in the formula (DI-5-12), m = 2 to 6 is preferable and m = 5 is Particularly preferably, in formula (DI-5-13), m = 1 or 2 is preferable, and m = 1 is particularly preferable.

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

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

The polyamic acid and derivatives thereof of the present invention can be obtained by reacting the above-mentioned acid anhydride mixture with a diamine in a solvent. In this synthesis reaction, no special conditions other than the selection of the raw materials are required, and the conditions for normal polyamic acid synthesis can be applied as they are. The solvent to be used will be described later.

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

The liquid crystal aligning agent of this invention may further contain other polymers other than the polyamic acid of this invention, or its derivative (s). The other polymer is a polymer other than polyamic acid obtained by reacting tetracarboxylic dianhydride and a diamine containing the diamine of the present invention or a derivative thereof, and reacts with a diamine not containing the diamine of formula (1). Polyamic acid or its derivative (hereinafter referred to as “other polyamic acid or its derivative”), polyester, polyamide, polysiloxane, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenylmaleimide) derivative, poly A (meth) acrylate etc. can be mentioned. 1 type or 2 types or more may be sufficient. Of these, other polyamic acids or derivatives thereof and polysiloxanes are preferred, and other polyamic acids or derivatives thereof are more preferred.

In the aligning agent blended with the polyamic acid or derivative thereof of the present invention and other polyamic acid or derivative thereof, the structure and molecular weight of each polymer are controlled, and applied to a substrate and pre-dried as described later. The polyamic acid or derivative component [A] of the present invention can be separated into an upper layer, and the other polyamic acid or derivative component [B] can be separated into a lower layer. This can be controlled by using a phenomenon in which a polymer having a small surface energy is separated into an upper layer and a polymer having a large surface energy is separated into a lower layer in a mixed polymer. Confirmation of layer separation can be confirmed by confirming that the surface energy of the formed alignment film is the same as or close to the surface energy of the film formed by the liquid crystal aligning agent containing only the component [A].

Examples of the tetracarboxylic dianhydride used for synthesizing other polyamic acid or derivatives thereof include tetracarboxylic acid dianhydrides used for synthesizing polyamic acid or derivatives thereof which are essential components of the liquid crystal aligning agent of the present invention. The anhydride can be selected without limitation from known tetracarboxylic dianhydrides, and the same ones as exemplified above can be exemplified.

Among them, in the acid dianhydride, when importance is attached to improving the layer separation property, the formula (AN-3-2), the formula (AN-1-13), and the formula (AN-4-30) Is preferred.

When importance is attached to improving the transmittance of the liquid crystal display element, among the above acid dianhydrides, the formula (AN-1-1), the formula (AN-1-2), the formula (AN-2-) 1), Formula (AN-3-1), Formula (AN-4-17), Formula (AN-4-30), Formula (AN-5-1), Formula (AN-7-2), Formula ( AN-10-1), the formula (AN-10-2), the formula (AN-16-3), and the compound represented by the formula (AN-16-4) are preferable, among which the formula (AN-1-2) In the formula (AN-4-17), m = 4 or 8 is preferable, and m = 8 is particularly preferable.

When importance is attached to improving the VHR of the liquid crystal display element, among the above acid dianhydrides, the formula (AN-2-1), the formula (AN-7-2), the formula (AN-10-1) ), The formula (AN-10-2), the formula (AN-16-3), and the compound represented by the formula (AN-16-4) are preferable, and in the formula (AN-1-2), m = 4 or 8 is preferred.

Increasing the relaxation rate of residual charges (residual DC) in the alignment film by reducing the volume resistance value of the liquid crystal alignment film is an effective method for preventing burn-in. In the case where the purpose is emphasized, among the above acid dianhydrides, the formula (AN-1-13), the formula (AN-3-2), the formula (AN-4-21), the formula (AN-4) -29) and a compound represented by the formula (AN-11-3) are preferable.

The tetracarboxylic dianhydride used for synthesizing other polyamic acid or its derivative should contain 10 mol% or more of aromatic tetracarboxylic dianhydride with respect to the total tetracarboxylic dianhydride. It is more preferable that it contains 30% or more.

As the diamine and hydrazide used for synthesizing other polyamic acid or its derivative, the above as other diamine that can be used for synthesizing the polyamic acid or its derivative which is an essential component of the liquid crystal aligning agent of the present invention. The same thing as illustrated in (1) can be mentioned.

Among them, when emphasizing further improving the layer separation, that is, the orientation of the liquid crystal, among the above diamine and dihydrazide, the formula (DI-4-1), the formula (DI-4-2), the formula Diamines represented by (DI-4-10), formula (DI-5-1), formula (DI-5-9), formula (DI-5-28), and formula (DIH-2-1); It is preferable to use hydrazide, and in the formula (DI-5-1), m = 1, 2, or 4 is preferable, and m = 1 or 2 is particularly preferable.

When importance is attached to improving the transmittance, among the above diamines and dihydrazides, the formula (DI-1-2), the formula (DI-2-1), the formula (DI-5-1), and the formula It is preferable to use a diamine represented by (DI-7-3), and a diamine represented by the formula (DI-2-1) is particularly preferable. In formula (DI-5-1), m = m = 1, 2, or 4 is preferable, m = 1 or 2 is particularly preferable, and in formula (AN-7-3), m = 2 or 3 , N = 1, or 2 is preferable, and m = 1 is particularly preferable.

When importance is attached to improving the VHR of the liquid crystal display element, among the above diamines and dihydrazides, the formula (DI-2-1), formula (DI-4-1), formula (DI-4-2) , Formula (DI-4-15), formula (DI-5-1), formula (DI-5-28), formula (DI-5-30), and formula (DI-13-1) A diamine is preferably used, and diamines represented by the formula (DI-2-1), the formula (DI-5-1), and the formula (DI-13-1) are particularly 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.

Increasing the relaxation rate of residual charges (residual DC) in the alignment film by reducing the volume resistance value of the liquid crystal alignment film is an effective method for preventing burn-in. When emphasizing this purpose, among the above diamines and dihydrazides, formula (DI-4-1), formula (DI-4-2), formula (DI-4-10), formula (DI-4- 15), 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 diamines represented by formula (DI-16-1) are preferably used, and formula (DI-4-1), formula (DI-5-1), and formula (DI- The diamine represented by 5-12) is particularly preferred. Among them, in the formula (DI-5-1), m = 1 or 2 is preferable. In the formula (DI-5-12), m = 2 to 6 is preferable, m = 5 is particularly preferable, and the formula (DI-5 −13), m = 1 or 2 is preferable, m = 1 is particularly preferable, and in the formula (DI-5-30), k = 2 is particularly preferable.

The diamine used for synthesizing other polyamic acid or a derivative thereof preferably contains 30% by mole or more, and more preferably 50% or more of the aromatic diamine with respect to the total diamine.

Other polyamic acids or derivatives thereof can be synthesized according to the method described below as a method for synthesizing polyamic acid or derivatives thereof, which are essential components of the liquid crystal aligning agent of the present invention.

The ratio of the [A] component to the total amount of the polyamic acid or derivative thereof (the above [A] component) and other polyamic acid or derivative thereof (the above [B] component) of the present invention is 10% by weight to 100% by weight. Is preferable, and 20% by weight to 100% by weight is more preferable.

Examples of the polysiloxane include JP2009-036966, JP2010-185001, JP2011-109633, JP2011-253175, JP2012-159825, International Publication 2008/044644, International Publication 2009/148099, International Publication. 2010/074261, 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. The polysiloxane may be further contained.

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

式（ＮＡ）において、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 will be specifically described below.
The alkenyl-substituted nadiimide compound is preferably a compound that can be dissolved in a solvent that dissolves the polyamic acid or derivative thereof used in the present invention. Examples of such alkenyl-substituted nadiimide compounds include compounds represented by the following formula (NA).

In the formula (NA), L ¹ and L ² are independently 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 Benzyl and n is 1 or 2.

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

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

In this case, preferable W is alkylene having 2 to 12 carbon atoms, cyclohexylene, phenylene, tolylene, xylylene, —C ₃ H ₆ —O— (Z ² —O) _n —O—C ₃ H ₆ — (where, Z ² is alkylene having 2 to 6 carbon atoms, and n is 1 or 2.) —B—T—B— (where B is phenylene, and T is — A group represented by CH ₂ —, —O— or —SO ₂ —), —B—O—B—C ₃ H ₆ —B—O—B—, wherein B is phenylene. And a group 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 acid anhydride derivative and a diamine at a temperature of 80 to 220 ° C. for 0.5 to 20 hours as described in Japanese Patent No. 2729565. Or a commercially available compound can be used. Specific examples of the alkenyl-substituted nadiimide compound include the following compounds.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

<Oxazine compound>
For example, the liquid crystal aligning agent of this invention may further contain the oxazine compound from the objective of stabilizing the electrical property in a liquid crystal display element for a long period of time. The oxazine compound may be 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 derivative thereof for the above purpose. More preferably.

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

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

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

式（ＯＸ−１）〜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。 Examples of the oxazine compound include compounds represented by the following formulas (OX-1) to (OX-6). In the following formula, the bond displayed toward the center of the ring indicates that it is bonded to any carbon that forms the ring and can be bonded to a substituent.

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

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

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

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

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

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

式（ＯＸ−３−Ｉ）において、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。 As the oxazine compound represented by the formula (OX-3), an oxazine compound represented by the following formula (OX-3-I) can be given.

In Formula (OX-3-I), L ³ and L ⁴ are each 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, more preferably alkyl having 1 to 20 carbon atoms.

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

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

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

Of these, more preferably, the formula (OX-2-1), the formula (OX-3-1), the formula (OX-3-3), the formula (OX-3-5), and the formula (OX-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 Oxazine compounds represented by (OX-6-6-2) to formula (OX-6-4) can be given.

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

The oxazine compound represented by the formula (OX-1) is obtained by reacting a phenol compound, a primary amine, and an aldehyde (see International Publication 2004/009708).

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

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

The oxazine compound represented by the formula (OX-4) to the formula (OX-6) is a diamine having a plurality of benzene rings and an organic group that binds them, such as 4,4′-diaminodiphenylmethane, and formalin. It can be obtained by subjecting an aldehyde and phenol to a dehydration condensation reaction in n-butyl alcohol at a temperature of 90 ° C. or higher (see JP 2004-352670 A).

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

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

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

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

<Epoxy compound>
For example, the liquid crystal aligning agent of the present invention may further contain an epoxy compound for the purpose of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time. The epoxy compound may be 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 with respect to the polyamic acid or derivative thereof for the above purpose. More preferably.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Examples of glycidyl amide include glycidyl amide type epoxy compounds.

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

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

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

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

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

Examples of the hydrogenated bisphenol-A type epoxy compound include Santo Tote ST-3000 (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 Corporation).

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

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

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

Examples of the cresol novolac type epoxy compound include jER180S75 (trade name, manufactured by Mitsubishi Chemical Corporation), YDCN-701, YDCN-702 (all trade names, manufactured by Tohto Kasei Co., Ltd.), Epicron N-665, Epicron 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.) ).

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

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

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

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

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

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

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

Examples of the biphenol type epoxy compound include 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.). ).

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

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

Examples of the polyglycidylamine compound include N, N-diglycidylaniline (following formula EP-24), N, N-diglycidyl-o-toluidine (following formula EP-25), N, N-diglycidyl-m-toluidine ( The following formula EP-26), N, N-diglycidyl-2,4,6-tribromoaniline (the following formula EP-27), 3- (N, N-diglycidyl) aminopropyltrimethoxysilane (the following formula EP-28 ), N, N, O-triglycidyl-p-aminophenol (following formula EP-29), N, N, O-triglycidyl-m-aminophenol (following formula EP-30), N, N, N ′ , N′-tetraglycidyl-4,4′-diaminodiphenylmethane (following formula EP-31), N, N, N ′, N′-tetraglycidyl-m-xylylenediamine (TETRAD) X (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.) )), Following formula EP-33), 1,4-bis (N, N-diglycidylaminomethyl) cyclohexane (following formula EP-34), 1,3-bis (N, N-diglycidylamino) cyclohexane (Formula EP-35), 1,4-bis (N, N-diglycidylamino) cyclohexane (Formula EP-36), 1,3-bis (N, N-diglycidylamino) benzene (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 (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 (following formula EP-41), N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenyl ether (following formula EP-42), 1,3 , 5-Tris (4- (N, N-diglycidyl) aminophenoxy) benzene (following formula EP-43), 2,4,4′-tris (N, N-diglycidylamino) diphenyl ether (following formula EP-44) ), Tris (4- (N, N-diglycidyl) aminophenyl) methane (following formula EP-45), 3,4,3 ′, 4′-tetrakis (N, N-diglycidylamino) biphenyl (following formula EP) -46), 3, 4, 3 Examples include ', 4'-tetrakis (N, N-diglycidylamino) diphenyl ether (the following formula EP-47), a compound represented by the following formula EP-48, and a compound represented by the following formula EP-49.

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

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

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

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

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

Examples of the cycloaliphatic epoxy compound include 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate (Celoxide 2021 (manufactured by Daicel Corporation), the following formula EP-52), 2-methyl -3,4-epoxycyclohexylmethyl-2'-methyl-3 ', 4'-epoxycyclohexylcarboxylate (following formula EP-53), 2,3-epoxycyclopentane-2', 3'-epoxycyclopentane ether (Formula EP-54), ε-caprolactone-modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 1,2: 8,9-diepoxy limonene (Celoxide 3000 (trade name, ( Manufactured by Daicel Corporation), the following formula EP-55), a compound represented by the following formula EP-56, Y-175, CY-177, CY-179 (all are trade names, manufactured by The Ciba-Geigy Chemical Corp. (available from Huntsman Japan)), EHPD-3150 (trade names, Daicel Corporation) And cycloaliphatic epoxy resins.

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

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

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

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

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

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

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

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

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

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

The molecular weight of the polyamic acid or derivative thereof according to the present invention is preferably 7,000 to 500,000, more preferably 10,000 to 200,000 in terms of polystyrene-equivalent weight average molecular weight (Mw). The molecular weight of the polyamic acid or derivative thereof can be determined from measurement by gel permeation chromatography (GPC).

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The liquid crystal composition is not particularly limited, and various liquid crystal compositions having a positive or negative dielectric anisotropy can be used. Preferred liquid crystal compositions having a positive dielectric anisotropy include Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Application Laid-Open No. 5-501735, Japanese Patent Application Laid-Open No. 8-157826, Japanese Patent Application Laid-Open No. 8-231960, Japanese Patent Application Laid-Open No. 9-241644 (EP 8852272A1), Kaihei 9-302346 (EP806466A1), JP-A-8-199168 (EP722998A1), JP-A-9-235552, JP-A-9-255556, JP-A-9-241643 (EP885271A1), JP-A-10-204016 (EP844229A1), JP-A-10 -204436, JP-A-10-231482, JP-A-2000-087040, JP-A-2001-48822, and the like.

One or more optically active compounds may be added to a liquid crystal composition having a 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 negative dielectric anisotropy liquid crystal composition include a composition containing at least one liquid crystal compound selected from the group of liquid crystal compounds represented by the following formula (NL-1) as the first component. .

Here, R ^1a and R ^2a are independently an alkyl having 1 to 12 carbons, an alkoxy having 1 to 12 carbons, an alkenyl having 2 to 12 carbons, or a carbon number in which at least one hydrogen is replaced by fluorine. 2-12 alkenyl, ring A ² and ring B ² are 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, and Z ¹ is independently a single bond, — (CH ₂ ) ₂ —, —CH ₂ O—, —COO—, or —CF ₂ O—. And j is 1, 2 or 3, and when 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 or may not be.

Preferred ring A ² and ring B ² are each 2,3-difluoro-1,4-phenylene or tetrahydropyran-2,5-diyl for increasing the dielectric anisotropy, and 1, for decreasing the viscosity, 4-cyclohexylene.

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

Preferred j is 1 for decreasing the minimum temperature, and 2 for increasing the maximum 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。 Specific examples of the liquid crystal compound of the above formula (NL-1) include compounds represented by the following formulas (NL-1-1) to (NL-1-32).

Here, R ^1a and R ^2a are independently an alkyl having 1 to 12 carbons, an alkoxy having 1 to 12 carbons, an alkenyl having 2 to 12 carbons, or a carbon number in which at least one hydrogen is replaced by fluorine. 2-12 alkenyl, ring A ²¹ , ring A ²² , ring A ²³ , ring B ²¹ , and ring B ²² are independently 1,4-cyclohexylene or 1,4-phenylene; ¹¹ and Z ¹² are each 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 for increasing the stability to ultraviolet light or heat, or alkoxy having 1 to 12 carbons for increasing the absolute value of dielectric anisotropy.

Preferred alkyl is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl. More desirable alkyl is ethyl, propyl, butyl, pentyl, or heptyl for decreasing 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 desirable alkenyl is vinyl, 1-propenyl, 3-butenyl or 3-pentenyl for decreasing the viscosity. The preferred configuration of —CH═CH— in these alkenyls depends on the position of the double bond. Trans is preferable in alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl and 3-hexenyl for decreasing the viscosity. Cis is preferable in alkenyl such as 2-butenyl, 2-pentenyl and 2-hexenyl. In these alkenyl, linear alkenyl is preferable to branching.

Preferred examples of 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.

Desirable ring A ²¹ , ring A ²² , ring A ²³ , ring B ²¹ , and ring B ²² are each 1,4-cyclohexylene for decreasing the 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 (NL-1) in which the liquid crystal composition having negative dielectric anisotropy is preferably used as the first component is the compounds (NL-1-1), (NL-1-4), (NL-1- 7) or (NL-1-32).

Preferred examples of the liquid crystal composition having negative dielectric anisotropy are disclosed in JP-A-57-114532, JP-A-2-4725, JP-A-4-224855, JP-A-8-40953, JP-A-8-104869, Kaihei 10-168076, JP-A-10-168453, JP-A-10-236989, JP-A-10-236990, JP-A-10-236992, JP-A-10-236993, JP-A-10-236994, JP-A-10-237000, JP-A-10-237000 -237004, JP-A-10-237024, JP-A-10-237035, JP-A-10-237075, JP-A-10-237076, JP-A-10-237448 (EP967261A1), JP-A-10-287874, JP-A-10-287875, JP-A-10-287875. 10-291945, JP-A-11-029581, Kaihei 11-080049, JP 2000-256307, JP 2001-019965, JP 2001-072626, JP 2001-192657, JP 2010-037428, International Publication 2011/024666, International Publication 2010/072370, Special Table 2010. Examples thereof include liquid crystal compositions disclosed in Japanese Patent No. 5370010, Japanese Patent Application Laid-Open No. 2012-0702201, Japanese Patent Application Laid-Open No. 2009-084362, and the like.

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

As the most preferable structure of the photopolymerizable monomer or oligomer for the purpose of improving the orientation of the liquid crystal, the structures (PM-1-1) to (PM-1-6) are exemplified.

The photopolymerizable monomer or oligomer is desirably 0.01% by weight or more in order to exhibit the effect of determining the tilt direction of the liquid crystal after polymerization. Further, in order to make the orientation effect of the polymer after polymerization appropriate, or in order to avoid the unreacted monomer or oligomer from eluting into the liquid crystal after ultraviolet irradiation, the content is preferably 30% by weight or less.

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

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

A preferred example of the antioxidant is a compound (AO-1) wherein w is an integer of 1 to 10. In the compound (AO-1), preferred w is 1, 3, 5, 7, or 9. Further preferred w is 1 or 7. Since the compound (AO-1) in which w is 1 has high volatility, it is effective in preventing a decrease in specific resistance due to heating in the atmosphere. Since the compound (AO-1) in which w is 7 has low volatility, it is effective for maintaining a large voltage holding ratio not only at room temperature but also at a high temperature after the device has been used for a long time. A desirable ratio of the antioxidant is 50 ppm or more for achieving its effect, and is 600 ppm or less for avoiding a decrease in the maximum temperature or avoiding an increase in the minimum temperature. A more desirable ratio is in the range of 100 ppm to 300 ppm.

Preferred examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Also preferred are light stabilizers such as sterically hindered amines. A desirable ratio in these absorbents and stabilizers is 50 ppm or more for obtaining the effect thereof, and 10,000 ppm or less for avoiding a decrease in the maximum temperature or avoiding an increase in the minimum temperature. A more desirable ratio is in the range of 100 ppm to 10,000 ppm.

A dichroic dye such as an azo dye or an anthraquinone dye is mixed with the composition in order to adapt to a GH (Guest host) mode element. A preferred ratio of the dye is in the range of 0.01% by weight to 10% by weight.

In order to prevent foaming, an antifoaming agent such as dimethyl silicone oil or methylphenyl silicone oil is mixed with the composition. A desirable ratio of the antifoaming agent is 1 ppm or more for obtaining the effect thereof, and 1000 ppm or less for preventing a poor display. A more desirable ratio is in the range of 1 ppm to 500 ppm.

A polymerizable compound can be mixed with the composition in order to adapt to a device having a polymer sustained alignment (PSA) 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 acrylate or methacrylate derivatives. Examples of such a compound are from the compound (PM-2-1) to the compound (PM-2-9). A desirable ratio of the polymerizable compound is approximately 0.05% by weight or more for obtaining the effect thereof, and approximately 10% by weight or less for preventing a display defect. A more desirable ratio is in the range of approximately 0.1% by weight to approximately 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。

Wherein 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 carbons. , Z ¹³ , Z ¹⁴ , Z ¹⁵ , and Z ¹⁶ are each independently a single bond or alkylene having 1 to 12 carbons, and at least one —CH ₂ — is replaced by —O— or —CH═CH—. S, t, and u are each independently 0, 1, or 2.

A polymerization initiator can be mixed as a substance necessary for easily generating radicals or ions and initiating a chain polymerization reaction. For example, Irgacure 651 (registered trademark), Irgacure 184 (registered trademark), or Darocure 1173 (registered trademark) (Ciba Japan KK), which is a photopolymerization initiator, is suitable for radical polymerization. The polymerizable compound preferably contains a photopolymerization initiator in the range of 0.1% 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, a polymerization inhibitor is mixed for the purpose of rapidly reacting with a radical generated from a polymerization initiator or monomer to change to a stable radical or neutral compound, and as a result, stop the polymerization reaction. Can do. Polymerization inhibitors are classified into several structures. One is a radical that is itself stable, such as tri-p-nitrophenylmethyl, di-p-fluorophenylamine, and the other is a stable radical that reacts readily with radicals present in the polymerization system. Typical examples include nitro, nitriso, amino, and polyhydroxy compounds. Representative examples of the latter include hydroquinone and dimethoxybenzene. A desirable ratio of the polymerization inhibitor is 5 ppm or more for obtaining the effect thereof, and 1000 ppm or less for preventing a poor display. A more desirable ratio is in the range of 5 ppm to 500 ppm.

By using a liquid crystal composition having negative dielectric anisotropy for the liquid crystal display element of the present invention, a liquid crystal display element having excellent afterimage characteristics and good alignment stability can be provided.

Hereinafter, the present invention will be described with reference to 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 calculated by polystyrene conversion. The obtained polyamic acid was diluted with a phosphoric acid-DMF mixed solution (phosphoric acid / DMF = 0.6 / 100: weight ratio) so that the polyamic acid concentration was about 2% by weight. The column was HSPgel RT MB-M (manufactured by Waters), and measurement was performed under the conditions of a column temperature of 50 ° C. and a flow rate of 0.40 mL / min using the mixed solution as a developing agent. As the standard polystyrene, TSK standard polystyrene manufactured by Tosoh Corporation was used.
2. Pretilt angle measurement Measured according to the crystal rotation method.
3. The voltage holding ratio was measured by the method described in “Mizushima et al., 14th Liquid Crystal Discussion Group Proceedings p78 (1988)”. The measurement was performed by applying a rectangular wave having a wave height of ± 5 V to the cell. The measurement was performed at 60 ° C. This value is an index indicating how much the applied voltage is retained after the frame period. If this value is 100%, it indicates that all charges are retained. A liquid crystal display element having a good display quality is obtained when the cell having the positive type liquid crystal is 99.5% or more and the cell having the negative type liquid crystal is 97.5% or more.
4). Measurement of ion content in liquid crystal (ion density)
According to the method described in Applied Physics, Vol. 65, No. 10, 1065 (1996), measurement was performed using a liquid crystal property measuring system 6254 type manufactured by Toyo Technica. Using a triangular wave with a frequency of 0.01 Hz, measurement was performed at a voltage range of ± 10 V and a temperature of 60 ° C. (electrode area is 1 cm ² ). If the ion density is high, defects such as seizure 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 image sticking. If this value is 40 pC or less, a liquid crystal display element with good display quality is obtained.

<Tetracarboxylic dianhydride>
(AN-1-1): 1,2,3,4-butanetetracarboxylic dianhydride (AN-1-13): ethylenediaminetetraacetic acid dianhydride (AN-2-1): 1,2,3 , 4-cyclobutanetetracarboxylic dianhydride (AN-3-2): pyromellitic dianhydride (AN-4-30): N, N ′-(1,4-phenylene) bis (1,3- Dioxooctahydroisobenzofuran-5-carboxamide)
(AN-7-2): 2,3,5-Tricarboxycyclopentylacetic acid dianhydride (AN-10-1): Octahydropentalene-1,3,4,6-tetracarboxylic acid-1,3 4,6-dianhydride

<Diamine>
(DI-5-1, m = 1): 4,4′-diaminodiphenylmethane (DI-5-1, m = 4): 4,4′-diaminodiphenylbutane (DI-5-9): 4,4 '-Diaminodiphenyl ether (DI-5-12, m = 3): 1,3-bis (4-aminophenoxy) propane (DI-5-30, k = 2): N, N'-bis (4-amino) Phenyl) -N, N′-dimethylethylenediamine (DI-7-3, m = 3, n = 1): 1,3-bis (4-((4-aminophenyl) methyl) phenyl) propane (DI-13 -1): 4,4′-N, N′-bis (4-aminophenyl) piperazine (DI-34-6, R ⁴¹ = n—C ₅ H ₁₁ ): 4 ′, 4 ′-(4- ( 2- (4-aminoenyl) ethyl) phenyl) -4-pentylbicyclohexane (DI 31-44): cholesteryl 3,5-aminobenzoate

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

[Synthesis Example 1]
Synthesis of compound represented by formula (1-1-1).
<First stage> Synthesis of amide compound Thermometer and 300 mL three-necked flask equipped with a reflux tube were charged with 4-amino-2,2,6,6-tetramethylpiperidine (15.0 g, 96.0 mmol) and potassium carbonate. (19.9 g, 144.0 mmol) was added, and 100 mL of tetrahydrofuran (THF) was added. While keeping the solution at 5 ° C. or lower, a solution prepared by dissolving 3,5-dinitrobenzoyl chloride (24.3 g, 105.6 mmol) in 100 mL of THF was slowly added thereto. Cooling of the reaction solution was stopped, and the mixture was further stirred at room temperature for 3 hours. The reaction solution was poured into 500 mL of pure water, and the precipitated crystals were collected by filtration and dried at 80 ° C. for 6 hours to obtain the following compound. Yield 32.0 g, yield 95%.

<Second Stage> Reduction of Nitro Group The compound obtained in the first stage (32.0 g, 91.3 mmol) and 5 wt% palladium carbon powder (3.2 g) were placed in a 1 L autoclave reactor, and 300 mL of tetrahydrofuran was added. The mixture was stirred at 50 ° C. in a 0.5 mPa hydrogen atmosphere until hydrogen absorption stopped. After allowing to cool, palladium carbon powder was removed by filtration, and the solvent was distilled off under reduced pressure to obtain crude crystals. The crude crystal was recrystallized from 50 mL of ethanol to obtain a compound represented by the formula (1-1-1). Yield 25.0 g, yield 70%.

[Synthesis Example 2]
Synthesis of compound represented by formula (1-1-2).
<First Stage> Synthesis of Acid Chloride 2-Bromo-5-nitrobenzoic acid (25.0 g, 101.6 mmol) was added to a 300 mL eggplant flask, and 100 mL of thionyl chloride was added. The mixture was heated to reflux for 6 hours, allowed to cool, and thionyl chloride was distilled off under reduced pressure to obtain 2-bromo-5-nitrobenzoyl chloride. Yield 23.5 g, 87% yield.

<Second stage> Synthesis of amide compound Thermometer and 300 mL three-necked flask equipped with a reflux tube were charged with 4-amino-2,2,6,6-tetramethylpiperidine (13.6 g, 87.0 mmol) and potassium carbonate. (14.4 g, 104.4 mmol) was added, and 100 mL of THF was added. While keeping the solution at 5 ° C. or lower, a solution obtained by dissolving the compound obtained in the first step (23.0 g, 87.0 mmol) in 100 mL of THF was slowly added. Cooling of the reaction solution was stopped, and the mixture was further stirred at room temperature for 3 hours. The reaction solution was poured into 500 mL of pure water, and the precipitated crystals were collected by filtration and dried at 80 ° C. for 6 hours to obtain the following compound. Yield 29.0 g, yield 87%.

<Third stage>
To a 500 mL three-necked flask equipped with a thermometer and a reflux tube, the compound obtained in the second stage (29.0 g, 75.5 mmol), benzophenone imine (15.0 g, 83.0 mmol), [1,3-bis ( 2,6-diisopropylphenyl) imidazol-2-ylidene] (3-chloro-pyridyl) palladium (II) dichloride (2.1 g, 3.0 mmol) and potassium t-butoxy (12.7 g, 113.2 mmol) Toluene 200 mL was added. The mixture was heated to reflux for 8 hours under a nitrogen atmosphere, allowed to cool, and after removing insolubles by filtration, the filtrate was poured into pure water (500 mL) and extracted with ethyl acetate (500 mL). The organic layer was washed 3 times with pure water (500 mL). After drying the organic layer with anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain crude crystals. The crude crystals were separated and purified by silica gel column chromatography (eluent; toluene: ethyl acetate = 6: 4) to obtain the following compounds. Yield 22.4 g, 62% yield.

<Fourth Stage> Conversion to Amino Group A 500 mL eggplant flask was charged with the compound obtained in the third stage (22.0 g, 45.3 mmol), and thereto were added 6N hydrochloric acid 50 mL and THF 200 mL. After stirring at room temperature for 12 hours, the solvent was distilled off under reduced pressure. 100 mL of pure water was added to the residue, and a 20% aqueous sodium hydroxide solution was added while stirring until the liquid reached pH> 7, and the mixture was further stirred at room temperature for 2 hours. The precipitated crystals were collected by filtration and washed with pure water to obtain the following compound. Yield 12.3 g, 85% yield.

<Fifth Stage> Reduction of Nitro Group The compound obtained in the fourth stage (12.0 g, 37.5 mmol) and 5 wt% palladium carbon powder (1.2 g) were placed in a 1 L autoclave reactor, and 100 mL of THF was added. The mixture was stirred at 50 ° C. in a 0.5 mPa hydrogen atmosphere until hydrogen absorption stopped. After allowing to cool, palladium carbon powder was removed by filtration, and the solvent was distilled off under reduced pressure to obtain crude crystals. The crude crystal was recrystallized from 20 mL of ethanol to obtain a compound represented by the formula (1-1-2). Yield 9.4 g, 86% yield.

＜第１段階＞エステル体の合成
温度計および還流管を装着した３００ｍＬ３つ口フラスコに、４−アミノ−２，２，６，６−テトラメチルピペリジン（１５．０ｇ、９５．４ｍｍｏｌ）および炭酸カリウム（１９．８ｇ、１４３．１ｍｍｏｌ）をいれＴＨＦを１００ｍＬ加えた。溶液を５℃以下に保ちながら、そこに３，５−ジニトロベンゾイルクロライド（２４．２ｇ、１０５．０ｍｍｏｌ）をＴＨＦ１００ｍＬに溶解させた溶液をゆっくり加えた。反応液の冷却を止め、室温でさらに３時間攪拌した。反応溶液を純水５００ｍＬにあけ、析出した結晶を濾取し、８０℃で６時間乾燥させて下記の化合物を得た。収量３０．３ｇ、収率９０％。

[Synthesis Example 3]
Synthesis of compound represented by formula (C1).

<First stage> Synthesis of ester body Thermometer and 300 mL three-necked flask equipped with a reflux tube were charged with 4-amino-2,2,6,6-tetramethylpiperidine (15.0 g, 95.4 mmol) and potassium carbonate. (19.8 g, 143.1 mmol) was added, and 100 mL of THF was added. While keeping the solution at 5 ° C. or lower, a solution prepared by dissolving 3,5-dinitrobenzoyl chloride (24.2 g, 105.0 mmol) in 100 mL of THF was slowly added thereto. Cooling of the reaction solution was stopped, and the mixture was further stirred at room temperature for 3 hours. The reaction solution was poured into 500 mL of pure water, and the precipitated crystals were collected by filtration and dried at 80 ° C. for 6 hours to obtain the following compound. Yield 30.3 g, yield 90%.

<Second Stage> Reduction of Nitro Group The compound obtained in the first stage (30.0 g, 85.4 mmol) and 5 wt% palladium carbon powder (3.0 g) were placed in a 1 L autoclave reactor, and 300 mL of THF was added. The mixture was stirred at 50 ° C. in a 0.5 mPa hydrogen atmosphere until hydrogen absorption stopped. After allowing to cool, palladium carbon powder was removed by filtration, and the solvent was distilled off under reduced pressure to obtain crude crystals. The crude crystal was recrystallized from 40 mL of ethanol to obtain a compound represented by the formula (C1). Yield 17.6 g, 71% yield.

＜第１段階＞エーテル化
温度計および還流管を装着した３００ｍＬ３つ口フラスコに、３，５−ジニトロブロモベンゼン（２０．０ｇ、８１．０ｍｍｏｌ）、４−ヒドロキシ−２，２，６，６−テトラメチルピペリジン（１４．０ｇ、８９．１ｍｍｏｌ）、炭酸カリウム（１３．４ｇ、９７．２ｍｍｏｌ）およびヨウ化カリウム（１．３ｇ、８．１ｍｍｏｌ）をいれＮ，Ｎ−ジメチルホルムアミドを２００ｍＬ加えた。窒素雰囲気下８０℃で８時間攪拌し、放冷後、反応溶液を純水５００ｍＬにあけ、析出した結晶を濾取し、８０℃で６時間乾燥させて下記の化合物を得た。収量１８．９ｇ、収率７２％。

[Synthesis Example 4]
Synthesis of a compound represented by formula (C2).

<First stage> To a 300 mL three-necked flask equipped with an etherification thermometer and a reflux tube, 3,5-dinitrobromobenzene (20.0 g, 81.0 mmol), 4-hydroxy-2,2,6,6- Tetramethylpiperidine (14.0 g, 89.1 mmol), potassium carbonate (13.4 g, 97.2 mmol) and potassium iodide (1.3 g, 8.1 mmol) were added, and 200 mL of N, N-dimethylformamide was added. The mixture was stirred at 80 ° C. for 8 hours under a nitrogen atmosphere and allowed to cool, then the reaction solution was poured into 500 mL of pure water, and the precipitated crystals were collected by filtration and dried at 80 ° C. for 6 hours to obtain the following compound. Yield 18.9 g, yield 72%.

<Second Stage> Reduction of Nitro Group The compound obtained in the first stage (18.0 g, 55.7 mmol) and 5 wt% palladium carbon powder (1.8 g) were placed in a 1 L autoclave reactor, and 200 mL of THF was added. The mixture was stirred at 50 ° C. in a 0.5 mPa hydrogen atmosphere until hydrogen absorption stopped. After allowing to cool, palladium carbon powder was removed by filtration, and the solvent was distilled off under reduced pressure to obtain crude crystals. The crude crystal was recrystallized from 30 mL of a mixed solvent of toluene / ethanol = 5/1 to obtain a compound represented by the formula (C2). Yield 11.9 g, 81% yield.

[Example 1] Preparation of varnish 2.587g of compound DI-7-3 (m = 3, n = 1), compound (1-1) in a 200 mL eggplant flask equipped with a thermometer, nitrogen purge port and stirring rod -1) was added in an amount of 0.610 g, 59.0 g of N-methyl-2-pyrrolidone (NMP) and 15.0 g of γ-butyrolactone (GBL) were added. The solution was cooled to 5 ° C. or less, and 0.5553 g of compound (AN-3-1), 0.9152 g of (AN-2-1) and 0.3261 g of (AN-1-13) were added thereto, The mixture was further stirred at room temperature for 6 hours. Thereto, 20.0 g of butyl cellosolve (BC) was added, and the mixture was heated and stirred at 70 ° C. until the viscosity of the solution reached about 35.0 cP to obtain varnish 1 having a solid content of 6 wt%. The varnish had a weight average molecular weight (Mw) of 68,000.

Based on the method described in Example 1, the following varnish with a solid content of 6 wt% was obtained. Table 1 shows the composition and weight average molecular weight (Mw) of the obtained varnish. Example 1 is also shown again. [] Represents each molar ratio in the tetracarboxylic acid compound group and the diamine compound group.

[Example 35]
<Preparation of liquid crystal aligning agent, FFS cell manufacturing method, voltage holding ratio and measurement of ion density>
In a 50 mL eggplant flask, 10 g of varnish 1 was weighed, 10 g of N-methyl-2-pyrrolidone and 10 g of butyl cellosolve were added, and the mixture was shaken for 2 hours to obtain liquid crystal aligning agent 1 having a solid content of 3 wt%.
The obtained coating varnish was coated on an FFS cell glass substrate with a spinner. The coating conditions were 2300 rpm and 15 seconds. After the coating, it was pre-baked at 80 ° C. for about 5 minutes, and then baked at 200 ° C. for 30 minutes to form a liquid crystal alignment film having a thickness of about 100 nm. Using a rubbing treatment apparatus manufactured by Iinuma Gauge Co., Ltd., the resulting polyimide film was pushed into a rubbing cloth (hair leg length 1.9 mm: rayon) by 0.40 mm, and the stage moving speed was 60 mm / sec. The rubbing process was performed at a rotation speed of 1000 rpm. The obtained substrate was subjected to ultrasonic cleaning in ethanol for 5 minutes, the surface was cleaned with ultrapure water, and then dried in an oven at 120 ° C. for 30 minutes. A liquid crystal composition between two alignment films facing each other so that the surfaces on which two alignment films are formed are opposed to each other and the rubbing direction is parallel to each alignment film. A void for injecting was formed and bonded together to assemble an empty FFS cell having a cell thickness of 4 μm. The following positive liquid crystal composition A was vacuum injected into the produced empty FFS cell, and the injection port was sealed with a photocuring agent. Next, a heat treatment was performed at 110 ° C. for 30 minutes to produce an FFS liquid crystal display element (FFS cell) 1-1 for evaluating electrical characteristics.

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 5V30 Hz, and the ion density was 10 pC. A reliability test was conducted by placing the cell on a backlight tester (Fuji Film Co., Ltd., FujiCOLOR LED Viewer Pro HR-2; luminance 2,700 cd / m ² ) for 1,000 hours. The voltage holding ratio of the measurement cell after the reliability test was 99.7%, and the ion density was 10 pC.

[Examples 36 to 68 and Comparative Examples 5 to 7]
For varnishes 2-34 and varnishes C1-C3, the liquid crystal aligning agent was prepared, the FFS cell was prepared, the voltage holding ratio, and the ion density were measured in accordance with the method described in Example 35. The results are shown in Table 2. The results of Example 35 are also shown again.

ジアミンＣ３を原料の１つとして使用した配向剤からなる配向膜を具備した表示素子以外のすべてのセルにおいて、初期、信頼性試験後ともに良好な結果であった。

In all cells other than the display element including the alignment film made of the alignment agent using diamine C3 as one of the raw materials, both the initial results and the reliability test were good results.

[Examples 69 to 102 and Comparative Examples 8 to 10]
An FFS cell for electrical property evaluation was prepared according to the method described in Example 35 except that the firing temperature for forming the liquid crystal alignment film was set to 230 ° C. at the time of creating the electrical property evaluation FFS cell. Density was measured. The results are shown in Table 3.

In the cells 1-2 to 34-2, good results were obtained both in the initial stage and after the reliability. However, in the cells C1-2 to C3-2, the voltage holding ratio and the ion density were reduced in the initial stage, and the reliability test was performed. Later, further deterioration was confirmed.

[Examples 103 to 136 and Comparative Examples 11 to 13]
According to the method described in Example 35 except that the liquid crystal composition to be injected was changed from the positive liquid crystal composition A to the negative liquid crystal composition B, FFS cells for electrical property evaluation were produced, and the voltages of these cells were Retention and ion density were measured. The results are shown in Table 4.

物性値：ＮＩ ７５．７℃； Δε −４．１； Δｎ ０．１０１； η １４．５ｍＰａ・ｓ． <Negative liquid crystal composition B>

Physical property values: NI 75.7 ° C .; Δε-4.1; Δn 0.101; η 14.5 mPa · s.

実施例に係るすべてのセルにおいて良好な結果が得られた。

Good results were obtained in all the cells according to the examples.

[Examples 137 to 170 and Comparative Examples 14 to 16]
The liquid crystal composition to be injected was changed from the positive liquid crystal composition A to the negative liquid crystal composition B, and the firing temperature at the time of forming the liquid crystal alignment film was changed to 230 ° C. FFS cells for evaluation were produced, and the voltage holding ratio and ion density of those cells were measured. The results are shown in Table 5.

セル１−４〜３４−４においては初期、信頼性後ともに良好な結果を示したが、セルＣ１−４〜Ｃ３−４では初期で電圧保持率およびイオン密度の低下がみられ、信頼性試験後では更なる悪化が確認された。

In the cells 1-4 to 34-4, good results were shown both in the initial stage and after the reliability. In the cells C1-4 to C3-4, the voltage holding ratio and the ion density were initially reduced, and the reliability test was performed. Later, further deterioration was confirmed.

From the above examples, the liquid crystal display device provided with the liquid crystal alignment film formed from the liquid crystal alignment agent of the present invention always exhibits a certain performance regardless of the difference in the manufacturing process, and is good even after a long period of time. It can be seen that the liquid crystal display element maintains a good display quality.

[Examples 171 to 177] Confirmation of effect with polymer blend type alignment agent Based on the method described in Example 1, the following varnish with a solid content of 6 wt% was obtained. Table 6 shows the composition and weight average molecular weight (Mw) of the obtained varnish. [] Represents each molar ratio in the tetracarboxylic acid compound group and the diamine compound group.

[Example 178] Preparation of polymer blend alignment agent 0.2 g of varnish 1 and 0.8 g of varnish 39 were weighed into a sample bottle, and NMP / BC = 1/1 (weight ratio) was added to obtain 1.67 g of the alignment agent. B1 was obtained.

[Examples 179 to 207]
Table 7 shows polymer blend type alignment agents similarly prepared. Example 178 is also repeated. The numbers in [] in Table 7 represent% by weight.

[Example 208] Evaluation of electrical properties of alignment film made of polymer blend type aligning agent The method described in Example 35, except that the prepared polymer blend aligning agent B1 was used and the temperature of the baking treatment was changed from 200 ° C to 230 ° C. According to the above, an FFS liquid crystal display element (FFS cell) B1C for electrical property evaluation was produced.

The voltage holding ratio of the obtained measurement cell B1C was 99.7% at 5 V 30 Hz, and the ion density was 10 pC. A reliability test was performed by placing the cell on a backlight tester (Fuji Film Co., Ltd., FujiCOLOR LED Viewer Pro HR-2; luminance 2,700 cd / m ² ) for 1,000 hours. The voltage holding ratio of the measurement cell after the reliability test was 99.7%, and the ion density was 10 pC.

[Examples 209 to 237, Comparative Examples 23 to 28]
According to the method described in Example 208, the polymer blend alignment agents B2 to B30 and C1-B to C6-B were also subjected to FFS cell preparation, voltage holding ratio, ion density measurement, and reliability test. The results are shown in Table 8. The results of Example 208 are also shown again.

[Example 238]
According to the method described in Example 35, except that the prepared polymer blend alignment agent B1 was used, the temperature of the baking treatment was changed from 200 ° C. to 230 ° C., and the liquid crystal composition to be injected was replaced with the negative liquid crystal composition B. The FFS liquid crystal display element (FFS cell) B1C-N for characteristic evaluation was produced.

The voltage holding ratio of the obtained measurement cell B1C-N was 98.0% at 5V30 Hz, and the ion density was 15 pC. A reliability test was performed by placing the cell on a backlight tester (Fuji Film Co., Ltd., FujiCOLOR LED Viewer Pro HR-2; luminance 2,700 cd / m ² ) for 1,000 hours. The voltage holding ratio of the measurement cell after the reliability test was 97.9%, and the ion density was 15 pC.

[Examples 239 to 267, Comparative Examples 29 to 34]
The polymer blend alignment agents B2 to B30 and C1-B to C6-B were also subjected to FFS cell production, voltage holding ratio, ion density measurement, and reliability test according to the method described in Example 238. The results are shown in Table 9. The results of Example 238 are also shown again.

From the above results, it was found that the alignment film made of the liquid crystal aligning agent of the present invention has the effects of the invention even in the polymer blend system. In addition, the liquid crystal to be sandwiched exhibits the effects of the invention regardless of whether it is a positive type or a negative type.

[Comparative Example 35]
1.0 g of varnish 41 synthesized in Example 177 was weighed, and 0.18 mg of an amine-based antioxidant (manufactured by ADEKA, trade name: Adegas Tab LA-72) was added thereto, and NMP / BC = 1/1. (Weight ratio) was added to 1.67 g, and the mixture was shaken at room temperature for 1 hour to obtain an aligning agent R3HA.

An FFS liquid crystal display element (FFS cell) R3HACC for electrical property evaluation was prepared according to the method described in Example 35 except that the prepared alignment agent R3HA was used and the liquid crystal composition to be injected was replaced with the negative liquid crystal composition B. did.

The voltage holding ratio of the obtained measurement cell R3HAC was 97.5% at 5V30 Hz, and the ion density was 20 pC. A reliability test was performed by placing the cell on a backlight tester (Fuji Film Co., Ltd., FujiCOLOR LED Viewer Pro HR-2; luminance 2,700 cd / m ² ) for 1,000 hours. The voltage holding ratio of the measurement cell after the reliability test was 83.2%, and the ion density was 195 pC.

[Comparative Example 36]
Alignment agent R3HB was prepared by the method described in Comparative Example 35 except that the amount of adegastab LA-72 added was changed to 1.8 mg, to produce an FFS liquid crystal display element R3HBC for electrical characteristics.

The voltage holding ratio of the obtained measurement cell R3HBC was 97.8% at 5V30 Hz, and the ion density was 25 pC. A reliability test was performed by placing the cell on a backlight tester (Fuji Film Co., Ltd., FujiCOLOR LED Viewer Pro HR-2; luminance 2,700 cd / m ² ) for 1,000 hours. The voltage holding ratio of the measurement cell after the reliability test was 91.1%, and the ion density was 105 pC. However, in the cell R3HBC, a display defect due to a bright spot was confirmed from the beginning. It is considered that this display defect was caused by the added JF-90 being segregated on the outermost surface during the alignment film formation, and the bright spot defect was generated therefrom.

[Comparative Example 37]
An alignment agent R3HC was prepared by the method described in Comparative Example 35, except that the amount of adegastab LA-72 added was changed to 18.0 mg, to produce an FFS liquid crystal display element R3HCC for electrical characteristics.

The voltage holding rate of the obtained measurement cell R3HCC was 97.6% at 5V30 Hz, and the ion density was 25 pC. A reliability test was performed by placing the cell on a backlight tester (Fuji Film Co., Ltd., FujiCOLOR LED Viewer Pro HR-2; luminance 2,700 cd / m ² ) for 1,000 hours. The voltage holding ratio of the measurement cell after the reliability test was 91.9%, and the ion density was 95 pC. However, in the cell R3HCC, display defects due to bright spots were confirmed from the beginning.

By using the liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention, an excellent liquid crystal display element in which the display quality does not deteriorate for a long time can be obtained. This effect is characteristically exhibited in IPS mode and FFS mode liquid crystal display elements.

Claims (17)

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

In formula (1), R ¹ is hydrogen or methyl; and
R ² is hydrogen, —OH, alkyl having 1 to 6 carbons, or alkoxy having 1 to 6 carbons. The polyamic acid or derivative thereof according to claim 1, wherein the diamine represented by the formula (1) is at least one of the diamines represented by the formula (1-1).

In Formula (1-1), R ² is hydrogen, —OH, alkyl having 1 to 6 carbons, or alkoxy having 1 to 6 carbons. The polyamic acid or derivative thereof according to claim 1, wherein the diamine represented by the formula (1) is at least one of the diamines represented by the formula (1-2).

In Formula (1-2), R ² is hydrogen, —OH, alkyl having 1 to 6 carbons, or alkoxy having 1 to 6 carbons. The polyamic acid according to claim 2, wherein the diamine represented by the formula (1) is at least one selected from the group of compounds represented by the formulas (1-1-1) to (1-1-28). Acid or its derivative.

The polyamic acid according to claim 3, wherein the diamine represented by formula (1) is at least one selected from the group of compounds represented by formula (1-2-1) to formula (1-228). Acid or its derivative.

6. The method according to claim 1, which is obtained by reacting a mixture of at least one diamine represented by the formula (1) and at least one other diamine with at least one tetracarboxylic dianhydride. Or a derivative thereof. The tetracarboxylic dianhydride is at least one selected from the group of tetracarboxylic dianhydrides represented by the following formulas (AN-I) to (AN-VII): 2. The polyamic acid or derivative thereof according to claim 1.

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 carbons, —CO—, —O—, —S—, —SO ₂ —, —C (CH ₃ ) ₂ —, or —C. (CF ₃ ) ₂ —;
In formula (AN-II) to formula (AN-IV), Y is independently one selected from the group of trivalent groups below,

At least one hydrogen of these groups may be replaced by methyl, ethyl or phenyl;
In Formula (AN-III) to Formula (AN-V), Ring A ¹⁰ is a monocyclic hydrocarbon group having 3 to ¹⁰ carbon atoms or a condensed polycyclic hydrocarbon group having 6 to 30 carbon atoms, At least one hydrogen of this group may be replaced by methyl, ethyl or phenyl, and the bond on the ring is connected to any carbon constituting the ring, and the two bonds are the same. May be linked to carbon;
In the formula (AN-VI), X ¹⁰ is alkylene having 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. Tetracarboxylic dianhydride has the following formula (AN-1-1), formula (AN-1-2), formula (AN-1-13), formula (AN-2-1), 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), Formula (AN-11-3), Formula (AN-16-3) And at least one selected from the formula (AN-16-4), or a polyamic acid or a derivative thereof according to claim 7.

In Formula (AN-1-2) and Formula (AN-4-17), m is an integer of 1-12. Other diamines are composed of the following formula (DI-1) to formula (DI-16), formula (DIH-1) to formula (DIH-3), and formula (DI-31) to formula (DI-35). The polyamic acid or derivative thereof according to claim 6, which is at least one selected from the group.

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

In formula (DI-4-a) and formula (DI-4-b), R ²⁰ is independently hydrogen or —CH ₃ ;
A group in which the bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary, and the bonding position of —NH ₂ to the cyclohexane ring or the benzene ring is G ²¹ or G ^22. Any position except the binding position of

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

In formula (DI-12), R ²¹ and R ²² are independently alkyl or phenyl having 1 to 3 carbon atoms, and G ²³ is independently alkylene, phenylene or alkyl-substituted phenylene having 1 to 6 carbon atoms. And w is an integer from 1 to 10;
In the formula (DI-13), R ²³ is independently alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons or —Cl, p is independently an integer of 0 to 3, and q is An integer from 0 to 4;
In the formula (DI-14), ring B is a monocyclic heteroaromatic, R ²⁴ is hydrogen, —F, —Cl, alkyl having 1 to 6 carbons, alkoxy having 1 to 6 carbons, or carbon 2 -6 alkenyl, C1-C6 alkynyl, q is independently an integer of 0-4;
In formula (DI-15), ring C is a monocycle containing a heteroatom;
In the formula (DI-16), G ²⁴ is a single bond, alkylene having 2 to 6 carbons or 1,4-phenylene, and r is 0 or 1;
In formula (DI-13) to formula (DI-16), a group in which the bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary;

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

In the formula (DI-31), G ²⁶ represents a single bond, —O—, —COO—, —OCO—, —CO—, —CONH—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—. , —OCF ₂ —, or — (CH ₂ ) _{m ′} —, 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 of a group represented by the formula (DI-31-a), and in the alkyl, at least one hydrogen may be replaced by -F, at least one of -CH ₂ - -O -, - CH = CH— or —C≡C— may be substituted, and the hydrogen of this phenyl is —F, —CH ₃ , —OCH ₃ , —OCH ₂ F, —OCHF ₂ , —OCF ₃ , With 30 alkyls or C 3-30 alkoxys It may be replaced, 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 are bonding groups, and these are each independently a single bond or alkylene having 1 to 12 carbons, and one or more — CH ₂ — may be replaced by —O—, —COO—, —OCO—, —CONH—, —CH═CH—, and ring B ²¹ , ring B ²² , ring B ²³ and ring B ²⁴ are independently 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, naphthalene-1,5- Diyl, naphthalene-2,7-diyl or anthracene-9,10-diyl, wherein in ring B ²¹ , ring B ²² , ring B ²³ and ring B ²⁴ at least one hydrogen is replaced by —F or —CH ₃ Being S, t, and u are each independently an integer of 0-2, and their sum is 1-5, and when s, t, or u is 2, two bonds in each parenthesis The groups 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 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 the formula (DI-31-b), R ²⁷ and R ²⁸ are independently alkyl having 1 to 3 carbons, and v is an integer of 1 to 6;

In the formula (DI-32) and the formula (DI-33), G ³⁰ is independently a single bond, —CO— or —CH ₂ —, R ²⁹ is independently hydrogen or —CH ₃ , R 30 ³⁰ is hydrogen, alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons;
One hydrogen of the benzene ring in formula (DI-33) may be replaced by alkyl or phenyl having 1 to 20 carbon atoms, and
In formula (DI-32) and formula (DI-33), a group in which the bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary;

In the formula (DI-34) and the formula (DI-35), G ³¹ is independently —O— or alkylene having 1 to 6 carbons, and G ³² is a single bond or alkylene having 1 to 3 carbons. ,
R ³¹ is hydrogen or alkyl having 1 to 20 carbon atoms, and at least one —CH ₂ — of the alkyl may be replaced by —O—, —CH═CH—, or —C≡C—. ³² is alkyl having 6 to 22 carbon atoms, R ³³ is hydrogen or alkyl having 1 to 22 carbon atoms, ring B ²⁵ is 1,4-phenylene or 1,4-cyclohexylene, and r is 0 or 1 and —NH ₂ bonded to the benzene ring indicates that the bonding position in the ring is arbitrary. Other diamines include 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-5-9), formula (DI-5-12), formula (DI-5-13), formula (DI- 5-28), Formula (DI-5-30), Formula (DI-7-3), Formula (DI-13-1), Formula (DI-16-1), and Formula (DIH-2-1) The polyamic acid or derivative thereof according to claim 6, which is at least one selected from the group consisting of:

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 from 1 to 5;
In the formula (DI-7-3), n is 1 or 2. The liquid crystal aligning agent containing the polyamic acid of any one of Claims 1-10, or its derivative (s). The liquid crystal aligning agent containing the polyamic acid of any one of Claims 1-10, its derivative (s), and a polymer other than that. The alkenyl-substituted nadiimide compound, a compound having a radical polymerizable unsaturated double bond, an oxazine compound, an oxazoline compound, and at least one selected from the group consisting of epoxy compounds, further comprising: The liquid crystal aligning agent of description. The liquid crystal aligning agent for horizontal electric field type liquid crystal display elements of any one of Claims 11-13. The liquid crystal aligning film formed with the liquid crystal aligning agent of any one of Claims 11-14. A liquid crystal display device comprising the liquid crystal alignment film according to claim 15. Diamine represented by Formula (1-2).

In Formula (1-2), R ² is hydrogen, —OH, alkyl having 1 to 6 carbons, or alkoxy having 1 to 6 carbons.