JP2014205659A - Photosensitive diamine, liquid crystal alignment agent, and liquid crystal display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystal alignment agent that has high transmittance and high alignment properties, to provide an alignment film using the liquid crystal alignment agent, and to provide a liquid crystal display element using the alignment film.SOLUTION: The liquid crystal alignment film is formed by using a liquid crystal alignment agent containing a polyamic acid or a derivative thereof produced by reacting a diamine component including a photosensitive diamine represented by formula (1) with a tetracarboxylic acid dianhydride. In formula (1), a ring A and a ring B each independently represent a monocyclic hydrocarbon, a condensed polycyclic hydrocarbon or a heterocycle; Rrepresents a 2-20C linear alkylene, -COO-. -OCO-, -NHCO-, or -N(CH)CO-; Rrepresents a 2-20C linear alkylene, -COO-, -OCO-, -CONH-, or -CON(CH)-; Rto Reach independently represent -F, -CH-, -OCH-, -CF, or, -OH; and a to d each independently represent an integer of 0 to 4.

Description

The present invention relates to a novel photosensitive diamine, a polyamic acid obtained using the same, or a derivative thereof, and further uses thereof. The term “liquid crystal aligning agent” in the present invention means a polymer-containing composition used for forming a liquid crystal aligning film.

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

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.

The liquid crystal alignment film is formed from a liquid crystal aligning agent. The liquid crystal aligning agent mainly used at present is a solution (varnish) obtained by dissolving polyamic acid or soluble polyimide in an organic solvent. After this solution is applied to the substrate, it is formed by means such as heating to form a polyimide-based liquid crystal alignment film.

Industrially, a rubbing method that is simple and capable of high-speed processing of a large area is widely used as an alignment processing 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. However, problems such as dust generation due to the rubbing method and generation of static electricity have been pointed out, and the development of an orientation treatment method that replaces the rubbing method has become active.

A photo alignment treatment method in which alignment treatment is performed by irradiating light is attracting attention as an alignment treatment method replacing the rubbing method. Many alignment mechanisms such as a photodecomposition method, a photoisomerization method, a photodimerization method, and a photocrosslinking method have been proposed for the photoalignment treatment method (see, for example, Non-Patent Document 1, Patent Documents 1 and 2). The photo-alignment method has higher uniformity of alignment than the rubbing method, and it is a non-contact alignment method, so the film is not damaged and causes the display defects of liquid crystal display elements such as dust generation and static electricity. There are advantages such as reduction. However, the anchoring energy is low and the orientation is low compared to the rubbing method, which causes a decrease in the response speed of the liquid crystal molecules and causes burn-in, and therefore improvement has been demanded.

In order to overcome such disadvantages of the photo-alignment treatment method, we have studied photo-alignment films having photoreactive groups that cause photoisomerization or photo-dimerization in the polyamic acid structure (for example, patent documents). See 3-7.) After applying a liquid crystal aligning agent comprising a liquid crystalline polyamic acid or its derivative to a substrate, it is irradiated with light and then baked, resulting in large anchoring energy, good orientation, and electrical characteristics such as voltage holding ratio However, an excellent photo-alignment film could be obtained. However, since the photoreactive group absorbs light, there is a problem that the transmittance is lowered, and there is still room for improvement because higher orientation is required.

JP-A-9-297313 JP-A-10-251646 JP-A-2005-275364 JP2007-248637 JP2009-069493 JP2010-049230 JP 2010-197999 A

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

An object of the present invention is to provide a liquid crystal aligning agent having high transmittance and high alignment. Another object of the present invention is to provide an alignment film using the liquid crystal aligning agent, and to provide a liquid crystal display element using the alignment film.

The present inventors have developed a photosensitive diamine represented by the formula (1). It has been found that a liquid crystal alignment film having a high transmittance and orientation can be obtained by using a liquid crystal aligning agent containing polyamic acid or a derivative thereof using diamine as a raw material, and the present invention has been completed.

式（１）において、環Ａおよび環Ｂはそれぞれ独立して、単環式炭化水素、縮合多環式炭化水素および複素環から選ばれる少なくとも１つであり；
Ｒ^１は、炭素数２〜２０の直鎖アルキレン、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−、または−Ｎ（ＣＨ_３）ＣＯ−であり；
Ｒ^２は、炭素数２〜２０の直鎖アルキレン、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、または−ＣＯＮ（ＣＨ_３）−であり；
Ｒ^１およびＲ^２において、直鎖アルキレンの−ＣＨ_２−の１つまたは２つは−Ｏ−で置換されてもよく；
Ｒ^ａ〜Ｒ^ｄは、それぞれ独立して、−Ｆ、−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、または−ＯＨであり；
ａ〜ｄは、それぞれ独立して、０〜４の整数であり；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。 The present invention has the following configuration.
[1] A photosensitive diamine represented by the formula (1).

In formula (1), ring A and ring B are each independently at least one selected from monocyclic hydrocarbons, condensed polycyclic hydrocarbons and heterocyclic rings;
R ¹ is a linear alkylene having 2 to 20 carbon atoms, —COO—, —OCO—, —NHCO—, or —N (CH ₃ ) CO—;
R ² is a linear alkylene having 2 to 20 carbon atoms, —COO—, —OCO—, —CONH—, or —CON (CH ₃ ) —;
In R ¹ and R ² , ^one or ^two of the linear alkylene —CH ₂ — may be substituted with —O—;
R ^{a to} R ^d are each independently —F, —CH ₃ , —OCH ₃ , —CF ₃ , or —OH;
a to d are each independently an integer of 0 to 4; and
A group whose bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary.

式（２）において、Ｒ^１は、炭素数２〜２０の直鎖アルキレン、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−、または−Ｎ（ＣＨ_３）ＣＯ−であり；
Ｒ^２は、炭素数２〜２０の直鎖アルキレン、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、または−ＣＯＮ（ＣＨ_３）−であり；
Ｒ^１およびＲ^２において、直鎖アルキレンの−ＣＨ_２−の１つまたは２つは−Ｏ−で置換されてもよく；
Ｒ^ａ〜Ｒ^ｄは、それぞれ独立して、−Ｆ、−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、または−ＯＨであり；
ａ〜ｄは、それぞれ独立して、０〜４の整数であり；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。 [2] The photosensitive diamine according to item [1], represented by formula (2).

In Formula (2), R ¹ is a linear alkylene having 2 to 20 carbon atoms, —COO—, —OCO—, —NHCO—, or —N (CH ₃ ) CO—;
R ² is a linear alkylene having 2 to 20 carbon atoms, —COO—, —OCO—, —CONH—, or —CON (CH ₃ ) —;
In R ¹ and R ² , ^one or ^two of the linear alkylene —CH ₂ — may be substituted with —O—;
R ^{a to} R ^d are each independently —F, —CH ₃ , —OCH ₃ , —CF ₃ , or —OH;
a to d are each independently an integer of 0 to 4; and
A group whose bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary.

式（３）において、Ｒ^１は、炭素数２〜２０の直鎖アルキレン、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−、または−Ｎ（ＣＨ_３）ＣＯ−であり；
Ｒ^２は、炭素数２〜２０の直鎖アルキレン、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、または−ＣＯＮ（ＣＨ_３）−であり；
Ｒ^ａ〜Ｒ^ｄは、それぞれ独立して、−Ｆ、−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、または−ＯＨであり；そして、
ａ〜ｄは、それぞれ独立して、０〜４の整数であり；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。 [3] The photosensitive diamine according to the item [1] or [2], which is represented by the formula (3).

In Formula (3), R ¹ is a linear alkylene having 2 to 20 carbon atoms, —COO—, —OCO—, —NHCO—, or —N (CH ₃ ) CO—;
R ² is a linear alkylene having 2 to 20 carbon atoms, —COO—, —OCO—, —CONH—, or —CON (CH ₃ ) —;
R ^{a to} R ^d are each independently —F, —CH ₃ , —OCH ₃ , —CF ₃ , or —OH; and
a to d are each independently an integer of 0 to 4; and
A group whose bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary.

[4] The photosensitive diamine according to any one of [1] to [3], which is represented by any one of formulas (1-1) to (1-5).

[5] A polyamic acid or a derivative thereof obtained by reacting a diamine containing at least one photosensitive diamine according to any one of [1] to [4] with a tetracarboxylic dianhydride.

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（ＤＩ−５）〜（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（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）〜（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）においては、下記式（ＤＩ−４−ａ）〜（ＤＩ−４−ｅ）で置き換えられていてもよく；
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−４−ａ）および（ＤＩ−４−ｂ）において、Ｒ^２０は独立して水素または−ＣＨ_３であり；

式（ＤＩ−１１）において、ｒは０または１であり；
式（ＤＩ−８）〜（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はへ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）〜（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（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−ＣＨ₂−は−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられていてもよく、このフェニルの水素は、−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、このシクロヘキシルの水素は炭素数３〜３０のアルキルまたは炭素数３〜３０のアルコキシで置き換えられていてもよく、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−ＣＨ₂−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−ＣＨ₂−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。 [6] In addition to the photosensitive diamine represented by the formula (1), the following formulas (DI-1) to (DI-16), (DIH-1) to (DIH-3), and (DI-31) to The polyamic acid or derivative thereof according to item [5], obtained by reacting a diamine containing at least one selected from the group consisting of (DI-35) and tetracarboxylic dianhydride.

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 the formulas (DI-3) and (DI-5) to (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 _{- (NH-C 3 H 6} ) n -CO-, or -S- _(CH 2) _{m 'is} -S-, m' is an integer from 1 to 12 independently, k is from 1 to 5 An integer, n is 1 or 2;
In formula (DI-4), s is independently an integer of 0 to 2;
In the formulas (DI-6) and (DI-7), G ²² is independently a single bond, —O—, —S—, —CO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ). ₂ or alkylene having 1 to 10 carbon atoms;
In formula (DI-2) ~ (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, and in Formula (DI-4), the following formulas (DI-4-a) to (DI May be replaced by -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, 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 formulas (DI-4-a) and (DI-4-b), R ²⁰ is independently hydrogen or —CH ₃ ;

In the formula (DI-11), r is 0 or 1;
In formulas (DI-8) to (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 formulas (DI-13) to (DI-16), a group whose bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position 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 formulas (DIH-2) and (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, Place with 30 alkyls or alkoxys with 3-30 carbons The hydrogen of this cyclohexyl may be replaced by alkyl having 3 to 30 carbons or alkoxy having 3 to 30 carbons, and the bonding position of —NH ₂ bonded to the benzene ring is Indicates an arbitrary 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—, 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,
The sum of these is 1-5, and 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. May be different,
R ²⁶ is hydrogen, —F, —OH, alkyl having 1 to 30 carbons, fluorine-substituted alkyl having 1 to 30 carbons, alkoxy having 1 to 30 carbons, —CN, —OCH ₂ F, —OCHF ₂ , or is -OCF _3, at least one -CH ₂ in the alkyl of a carbon number of 1-30 - 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）、（ＤＩ−５−１２）、（ＤＩ−５−１３）、および（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。 [7] In addition to the photosensitive diamine of the formula (1), the following formulas (DI-1-3), (DI-2-1), (DI-4-1), (DI-4-2), (DI -4-10), (DI-4-15), (DI-5-1), (DI-5-5), (DI-5-9), (DI-5-12), (DI-5 -13), (DI-5-24), (DI-5-28) to (DI-5-30), (DI-6-7), (DI-7-3), (DI-11-2) ) And a mixture of diamines containing at least one selected from (DI-13-1) and tetracarboxylic dianhydride, and the polyamic acid or derivative thereof according to item [6].

In the formulas (DI-5-1), (DI-5-12), (DI-5-13), and (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.

[8] Further described in any one of [5] to [7], which is obtained by reacting a mixture of diamine containing at least one photosensitive diamine other than formula (1) with tetracarboxylic dianhydride. A polyamic acid or a derivative thereof.

[9] In item [8], the photosensitive diamine other than formula (1) is at least one selected from the group consisting of azobenzene derivatives, stilbene derivatives, acetylene derivatives, coumarin derivatives, cinnamic acid derivatives, and benzophenone derivatives. The polyamic acid or its derivative as described.

式（ＰＤＩ−７）において、Ｒ^５１は独立して−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、または−ＣＯＯＣＨ_３であり、ｓは０〜２の整数であり、そして式（ＰＤＩ−１２）において、Ｒ^５２は炭素数１〜１０のアルキルまたはアルコキシであり、少なくとも１つの水素はフッ素に置き換えられてもよい。 [10] In the item [8] or [9], the photosensitive diamine other than the formula (1) is at least one compound selected from the group consisting of the following formulas (PDI-1) to (PDI-12). The polyamic acid or its derivative as described.

In formula (PDI-7), R ⁵¹ is independently —CH ₃ , —OCH ₃ , —CF ₃ , or —COOCH ₃ , s is an integer from 0 to 2, and formula (PDI-12) In the formula, R ⁵² is alkyl or alkoxy having 1 to 10 carbon atoms, and at least one hydrogen may be replaced by fluorine.

式（ＰＤＩ−７）において、Ｒ^５１は独立して−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、または−ＣＯＯＣＨ_３であり、ｓは独立して０〜２の整数である。 [11] The polyamic acid or derivative thereof according to any one of [8] to [10], wherein the photosensitive diamine other than the formula (1) is a compound represented by the following formula (PDI-7).

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

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）〜（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）〜（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。 [12] The tetracarboxylic dianhydride is at least one selected from the group of tetracarboxylic dianhydrides represented by the following formulas (AN-I) to (AN-VII): [5] to [5] [11] The polyamic acid or derivative thereof according to any one of [11].

In 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 formulas (AN-II) to (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 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 May be linked to;
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（ＡＮ−４−１７）において、ｍは１〜１２の整数である。 [13] The tetracarboxylic dianhydride has the following formulas (AN-1-1), (AN-1-2), (AN-1-13), (AN-2-1), (AN-3) -1), (AN-3-2), (AN-4-5), (AN-4-17), (AN-4-21), (AN-4-29), (AN-4-30) ), (AN-5-1), (AN-7-2), (AN-10), (AN-11-3), (AN-16-3), and (AN-16-4) The polyamic acid or the derivative thereof according to the item [12], which is a tetracarboxylic dianhydride containing at least one selected from the group consisting of

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

[14] A liquid crystal aligning agent containing the polyamic acid or derivative thereof according to any one of [5] to [13].

[15] A liquid crystal aligning agent containing the polyamic acid or derivative thereof according to any one of [7] to [13] and another polyamic acid or derivative thereof.

[16] The other polyamic acids or derivatives thereof are represented by the formulas (DI-1) to (DI-16), (DIH-1) to (DIH-3), and (DI-31) according to the item [6]. The liquid crystal aligning agent as described in the item [15], which is a polyamic acid obtained by reacting at least one diamine selected from the group consisting of (DI-35) and tetracarboxylic dianhydride or a derivative thereof.

式（ＤＩ−５−１）、（ＤＩ−５−１２）、（ＤＩ−５−１３）、および（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。 [17] Other polyamic acids or derivatives thereof are represented by the following formulas (DI-1-3), (DI-2-1), (DI-4-1), (DI-4-2), (DI-4). -10), (DI-4-15), (DI-5-1), (DI-5-9), (DI-5-12), (DI-5-13), (DI-5-28) ), (DI-5-30), (DI-7-3), (DI-13-1), (DI-16-1), and (DIH-2-1) The liquid crystal aligning agent as described in the item [16], which is a polyamic acid obtained by reacting tetracarboxylic dianhydride or a derivative thereof.

In the formulas (DI-5-1), (DI-5-12), (DI-5-13), and (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.

[18] The other polyamic acid or derivative thereof is at least one tetracarboxylic acid selected from the group of tetracarboxylic dianhydrides represented by the formulas (AN-I) to (AN-VII) according to claim 12. The liquid crystal aligning agent of any one of [15]-[17] which is a polyamic acid obtained by making an acid dianhydride and diamine react, or its derivative (s).

式（ＡＮ−１−２）および（ＡＮ−４−１７）において、ｍは１〜１２の整数である。 [19] Other polyamic acids or derivatives thereof are represented by the following formulas (AN-1-1), (AN-1-2), (AN-1-13), (AN-2-1), (AN-3). -1), (AN-3-2), (AN-4-5), (AN-4-17), (AN-4-21), (AN-4-29), (AN-4-30) ), (AN-5-1), (AN-7-2), (AN-10), (AN-11-3), (AN-16-3), and (AN-16-4) The liquid crystal aligning agent as described in the item [18], which is a polyamic acid obtained by reacting at least one tetracarboxylic dianhydride and a diamine.

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

[20] It further contains 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, [14] to [14] [19] The liquid crystal aligning agent according to any one of [19].

[21] The liquid crystal aligning agent for photo-alignment according to any one of [14] to [20].

[22] The liquid crystal aligning agent for a horizontal electric field type liquid crystal display element according to any one of [14] to [21].

[23] A liquid crystal alignment film formed by the liquid crystal aligning agent according to any one of [14] to [22].

[24] A liquid crystal display device having the liquid crystal alignment film according to the item [23].

The photo-alignment film containing a polymer obtained using the photosensitive diamine compound of the present invention as a raw material is excellent in orientation and has very little coloring. A liquid crystal display device provided with these alignment films has good display performance and good electrical characteristics. In addition, an alignment film obtained from an aligning agent prepared by blending the above polymer with a base polymer is excellent in orientation, further reduced in color, and has no decrease in sensitivity to light. By using this alignment film, a liquid crystal display element having good display characteristics and good electrical characteristics can be provided.

Terms used in the present invention will be described. The compound represented by the formula (I-1) may be described as the compound (I-1). Similarly, compounds represented by other formulas may be abbreviated. “Arbitrary” used in defining a chemical structural formula indicates that not only the position but also the number is arbitrary. In the chemical structural formula, a group in which a letter (for example, A) is surrounded by a circle or a hexagon means that the group has a ring structure (ring A).

The photosensitive diamine of the present invention will be described. Hereinafter, the “photosensitive diamine” may be simply referred to as “diamine” in the specification.

式（１）において、環Ａおよび環Ｂはそれぞれ独立して、単環式炭化水素、縮合多環式炭化水素および複素環式芳香族基から選ばれる少なくとも１つであり、Ｒ^１は、炭素数２〜２０の直鎖のアルキレン、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−、または−Ｎ（ＣＨ_３）ＣＯ−であり、Ｒ^２は、炭素数２〜２０の直鎖のアルキレン、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、または−ＣＯＮ（ＣＨ_３）−である。Ｒ^１およびＲ^２において、直鎖アルキレンの少なくとも１つの−ＣＨ_２−は、−Ｏ−で置換されてもよい。Ｒ^ａ〜Ｒ^ｄは、それぞれ独立して、−Ｆ、−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３または−ＯＨであり、ａ〜ｄは、それぞれ独立して、０〜４のいずれかである。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。 The photosensitive diamine of the present invention is represented by the following formula (1).

In formula (1), ring A and ring B are each independently at least one selected from monocyclic hydrocarbons, condensed polycyclic hydrocarbons and heterocyclic aromatic groups, and R ¹ is carbon A linear alkylene having 2 to 20 carbon atoms, —COO—, —OCO—, —NHCO—, or —N (CH ₃ ) CO—, wherein R ² is a linear alkylene having 2 to 20 carbon atoms, — COO -, - OCO -, - CONH-, or -CON (CH ₃₎ - is. In R ¹ and R ² , at least one —CH ₂ — of the linear alkylene may be substituted with —O—. R ^{a to} R ^d are each independently —F, —CH ₃ , —OCH ₃ , —CF ₃ or —OH, and ^{a to d} are each independently any one of 0 to 4 . 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.

As described above, the diamine of the present invention has four ring structures, and an azo having a spacer group of a linear alkylene having 2 to 20 carbon atoms, an ester group, an amide group or an N-methylamide group between the rings. It is a group-containing diamine. A polyamic acid obtained by reacting an azobenzene-containing diamine having two rings such as 4,4′-diaminoazobenzene with tetracarboxylic dianhydride or a derivative thereof has a long conjugated system through an azo group. Absorbs long wavelength light. When used as a liquid crystal alignment film, the transmittance is lowered and the display quality of the liquid crystal display element is lowered. On the other hand, the polyamic acid or derivative thereof obtained by reacting the diamine of the present invention with tetracarboxylic dianhydride has a spacer group represented by R ¹ and R ^{2 as} compared with the above-described polyamic acid or derivative thereof. Therefore, the conjugated system is shortened and the absorption wavelength is shifted to the short wavelength side, so that a decrease in transmittance can be suppressed. Moreover, since it becomes a more flexible structure, it becomes easy to show liquid crystallinity and can improve orientation.

式（２）において、Ｒ^１は、炭素数２〜２０の直鎖のアルキレン、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−、または−Ｎ（ＣＨ_３）ＣＯ−であり、Ｒ^２は、炭素数２〜２０の直鎖のアルキレン、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、または−ＣＯＮ（ＣＨ_３）−である。Ｒ^１およびＲ^２において、直鎖アルキレンの−ＣＨ_２−の１つまたは２つは、−Ｏ−で置き換えられてもよい。Ｒ^ａ〜Ｒ^ｄは、それぞれ独立して、−Ｆ、−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３または−ＯＨであり、ａ〜ｄは、それぞれ独立して、０〜４のいずれかである。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アミノ基は、その環における結合位置が任意であることを示す。 In the diamine compound represented by the formula (1), the diamine compound represented by the formula (2) is preferable because of easy availability of raw materials.

In Formula (2), R ¹ is a linear alkylene having 2 to 20 carbon atoms, —COO—, —OCO—, —NHCO—, or —N (CH ₃ ) CO—, and R ² is carbon It is a linear alkylene having a number of 2 to 20, —COO—, —OCO—, —CONH—, or —CON (CH ₃ ) —. In R ¹ and R ² , one or two of —CH ₂ — in the linear alkylene may be replaced with —O—. R ^{a to} R ^d are each independently —F, —CH ₃ , —OCH ₃ , —CF ₃ or —OH, and ^{a to d} are each independently any one of 0 to 4 . An amino group whose bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary.

式（３）において、Ｒ^１は、炭素数２〜２０の直鎖のアルキレン、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−、または−Ｎ（ＣＨ_３）ＣＯ−であり、Ｒ^２は、炭素数２〜２０の直鎖のアルキレン、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、または−ＣＯＮ（ＣＨ_３）−である。Ｒ^ａ〜Ｒ^ｄは、それぞれ独立して、−Ｆ、−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３または−ＯＨであり、そして、ａ〜ｄは、それぞれ独立して、０〜４のいずれかである。 Among the formulas (2), when importance is attached to improving the orientation of the liquid crystal, a diamine compound represented by the formula (3) in which the amino group is bonded to the para position is preferable.

In Formula (3), R ¹ is a linear alkylene having 2 to 20 carbon atoms, —COO—, —OCO—, —NHCO—, or —N (CH ₃ ) CO—, and R ² is carbon It is a linear alkylene having a number of 2 to 20, —COO—, —OCO—, —CONH—, or —CON (CH ₃ ) —. R ^{a to} R ^d are each independently —F, —CH ₃ , —OCH ₃ , —CF ₃ or —OH, and ^{a to d} are each independently any one of 0 to 4 It is.

ジアミン（ａ）および（ｂ）を、たとえばトリフルオロアセチル基で一方のアミノ基を保護し、ペルオキソホウ酸ナトリウム四水和物およびホウ酸を作用させることにより、（ｃ）で表される化合物が得られる。次に炭酸カリウムを作用させ、トリフルオロアセチル基を脱保護し、本発明の式（３）で表されるジアミンが得られる。保護基としては、トリフルオロアセチル基の他、アセチル基、ｔ−ブトキシカルボニル基も有用であり、これらの保護および脱保護に関する合成法は多くの有機合成に関する成書に記載されている。 The diamine of formula (3) can be synthesized, for example, by the following route.

By protecting one of the diamines (a) and (b) with, for example, a trifluoroacetyl group and allowing sodium peroxoborate tetrahydrate and boric acid to act, the compound represented by (c) is obtained. can get. Next, potassium carbonate is allowed to act to deprotect the trifluoroacetyl group, whereby the diamine represented by the formula (3) of the present invention is obtained. In addition to the trifluoroacetyl group, an acetyl group and a t-butoxycarbonyl group are also useful as the protecting group, and synthetic methods relating to the protection and deprotection thereof are described in many books on organic synthesis.

Regarding the diamines of the formulas (1) and (2), by making one of the phenylenes of the diamines (a) and (b) into the ring A, and by making the bonding position of the amine any position, It can be synthesized similarly.

As the diamine of the present invention, those purified by various purification methods such as recrystallization and column chromatography can be used as necessary. In addition, the diamine of the present invention can be used for various polyimide coating agents, polyimide resin molded products, films, fibers and the like in addition to liquid crystal alignment agent applications.

Examples of the diamine represented by the formula (1) include compounds represented by the following formula.

In the diamine, when anchoring energy is high, that is, when importance is attached to further improving the orientation of the liquid crystal, diamines represented by the formulas (1-1) to (1-9) are preferable, and the transmittance is When emphasizing the improvement, in order to obtain an alignment film with less coloring, the diamine of the present invention of formulas (1-10) to (1-12) is used and an aligner having higher solubility in a solvent. In order to obtain it, the alignment film which can achieve a desired characteristic is obtained by using the diamine of this invention of Formula (1-13) and (1-14). In addition, as in formulas (1-1) to (1-4) and (1-7) to (1-18), R ¹ and R ² in formula (1) are main chains composed of an even number of atoms. By using the diamine of the present invention, the polyamic acid of the present invention and its derivative exhibiting liquid crystallinity in a wider temperature range can be prepared.

From the viewpoint of ease of synthesis and suppression of coloring, formulas (1-1) to (1-5), (1-8), (1-12), (1-13), (1-15), and (1-19) to (1-22) are preferable, and formula (1-1) is particularly preferable.

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 polyamic acid derivative is a component that dissolves in a solvent when the liquid crystal aligning agent described later containing a solvent is used. When the liquid crystal aligning agent is used as a liquid crystal aligning film, the liquid crystal alignment is mainly composed of polyimide. It is a component that can form a film. Examples of such polyamic acid derivatives include soluble polyimides, polyamic acid esters, and polyamic acid amides. More specifically, 1) polyimide in which all amino acids and carboxyls 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 the formula (AN-II), G represents 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 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。式（ＡＮ−１）で表されるテトラカルボン酸二無水物の例としては、下記の式で表される化合物を挙げることができる。

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

In the formula (AN-1), G ¹¹ is a single bond, alkylene having 1 to 12 carbons, 1,4-phenylene, or 1,4-cyclohexylene. X ¹¹ is independently a single bond or —CH ₂ —. G ¹² is independently 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 . 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。式（ＡＮ−２）で表されるテトラカルボン酸二無水物の例としては、下記の式で表される化合物を挙げることができる。

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

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

式（ＡＮ−４）において、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。

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。

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.

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。

Each ring A ¹¹ is independently a cyclohexane ring or a benzene ring. G ¹³ may be bonded to any position of ring A ¹¹ . Examples of the tetracarboxylic dianhydride represented by the formula (AN-4) include compounds represented by the following formula.

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

式（ＡＮ−５）において、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。式（ＡＮ−５）で表されるテトラカルボン酸二無水物の例としては、下記の式で表される化合物を挙げることができる。

In the formula (AN-5), R ¹¹ is 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。式（ＡＮ−６）で表されるテトラカルボン酸二無水物の例としては、下記の式で表される化合物を挙げることができる。

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

式（ＡＮ−７）において、Ｘ^１１は単結合または−ＣＨ_２−である。式（ＡＮ−７）で表されるテトラカルボン酸二無水物の例としては、下記の式で表される化合物を挙げることができる。

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

式（ＡＮ−８）において、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もしくはシクロヘキセン環である。式（ＡＮ−８）で表されるテトラカルボン酸二無水物の例としては、下記の式で表される化合物を挙げることができる。

In the formula (AN-8), X ¹¹ is a single bond or —CH ₂ —. R ¹² is 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。式（ＡＮ−９）で表されるテトラカルボン酸二無水物の例としては、下記の式で表される化合物を挙げることができる。

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

式（ＡＮ−１０）は下記のテトラカルボン酸二無水物である。

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

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。式（ＡＮ−１１）で表されるテトラカルボン酸二無水物の例としては、下記の式で表される化合物を挙げることができる。

In 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。式（ＡＮ−１２）で表されるテトラカルボン酸二無水物の例としては、下記の式で表される化合物を挙げることができる。

In formula (AN-12), each 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。式（ＡＮ−１３）で表されるテトラカルボン酸二無水物の例としては、下記の式で表される化合物を挙げることができる。

In the formula (AN-13), X ¹³ is alkylene having 2 to 6 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。式（ＡＮ−１４）で表されるテトラカルボン酸二無水物の例としては、下記の式で表される化合物を挙げることができる。

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

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

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

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

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. 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.

In this invention, the photosensitive diamine of Formula (1) and another photosensitive material can be used together, and it can select without restrict | limiting from well-known photosensitive tetracarboxylic dianhydride. Examples of such photosensitive tetracarboxylic dianhydrides include the following formulas (PAN-1) and (PAN-8).

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（ＤＩ−５）〜（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（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）〜（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、下記式（ＤＩ−４−ａ）〜（ＤＩ−４−ｅ）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（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 the formulas (DI-3) and (DI-5) to (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) _{m 'is} -S-, m' is an integer from 1 to 12 independently, k is from 1 to 5 It is an integer and n is 1 or 2. In formula (DI-4), s is an integer of 0-2 independently. In the formulas (DI-6) and (DI-7), G ²² is independently a single bond, —O—, —S—, —CO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ). _2- or alkylene having 1 to 10 carbon atoms. At least one hydrogen of the cyclohexane ring and the benzene ring in the formulas (DI-2) to (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), the following formulas (DI-4-a) to (DI It may be replaced with -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 formulas (DI-4-a) and (DI-4-b), R ²⁰ is independently hydrogen or —CH ₃ .

式（ＤＩ−１１）において、ｒは０または１である。式（ＤＩ−８）〜（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) ~ (DI -11), the bonding position of -NH ₂ of bonding 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）〜（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 heteroaromatic 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) ~ (DI -16), the bonding position of -NH ₂ of bonding to the ring is an arbitrary position.

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

式（ＤＩ−１−７）および（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 formulas (DI-1-7) and (DI-1-8), k is each independently an integer of 1 to 3.

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

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

式（ＤＩ−５−１）において、ｍは１〜１２の整数である。

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

式（ＤＩ−５−１６）において、ｖは１〜６の整数である。

式（ＤＩ−５−３０）において、ｋは１〜５の整数である。

式（ＤＩ−５−３５）〜（ＤＩ−５−３７）、および（ＤＩ−５−３９）において、ｍは１〜１２の整数であり、式（ＤＩ−５−３８）および（ＤＩ−５−３９）において、ｋは１〜５の整数であり、（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 the formulas (DI-5-35) to (DI-5-37) and (DI-5-39), m is an integer of 1 to 12, and the formulas (DI-5-38) and (DI-5 -39), k is an integer of 1 to 5, and in (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（ＤＩ−７−４）において、ｍは１〜１２の整数であり、ｎは独立して１または２である。

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

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

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

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

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

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

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

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（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 the formulas (DIH-2) and (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, 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−ＣＨ₂−は−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられていてもよい。このフェニルの水素は、−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、このシクロヘキシルの水素は炭素数３〜３０のアルキルまたは炭素数３〜３０のアルコキシで置き換えられていてもよい。ベンゼン環に結合する−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 formulas (DI-31) to (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 Alternatively, the hydrogen of the cyclohexyl may be replaced by alkyl having 3 to 30 carbons or alkoxy having 3 to 30 carbons. 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−ＣＨ₂−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−ＣＨ₂−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 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 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 are 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 diamines having side chains of the above formulas (DI-31) to (DI-35) include compounds represented by the following formulas (DI-31-1) to (DI-35-3).

式（ＤＩ−３１−１）〜（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 formulas (DI-31-1) to (DI-31-11), R ³⁴ is alkyl having 1 to 30 carbons or alkoxy having 1 to 30 carbons, preferably alkyl or carbon having 5 to 25 carbons. It is alkoxy of several 5-25. R ³⁵ is alkyl having 1 to 30 carbons or alkoxy having 1 to 30 carbons, preferably alkyl having 3 to 25 carbons or alkoxy having 3 to 25 carbons.

式（ＤＩ−３１−１２）〜（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 the formulas (DI-31-12) to (DI-31-17), R ³⁶ is alkyl having 4 to 30 carbons, 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）〜（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 the formulas (DI-31-18) to (DI-31-43), R ³⁸ is alkyl having 1 to 20 carbons or alkoxy having 1 to 20 carbons, preferably alkyl or carbon having 3 to 20 carbons. It is alkoxy of several 3-20. 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）〜（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 the formulas (DI-34-1) to (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 it is a C1-C12 alkyl.

式（ＤＩ−３５−１）〜（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) ~ (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）〜（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）〜（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 formulas (DI-1-1) to (DI-16-1), (DIH-1-1) to (DIH-3-6) and (DI-31-1) to (DI A diamine other than the diamine represented by -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 formulas (DI-36-1) to (DI-36-8), R ⁴² each independently represents an alkyl group having 3 to 30 carbon atoms.

In formulas (DI-36-9) to (DI-36-11), e is an integer of 2 to 10, and in formula (DI-36-12), each R ⁴³ independently represents 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 emphasizing further improving the orientation of the liquid crystal, among the diamines and dihydrazides, the formulas (DI-1-3), (DI-5-1), (DI-5-5), ( (DI-5-9), (DI-5-12), (DI-5-13), (DI-5-29), (DI-6-7), (DI-7-3), and (DI -11-2) is preferably used, and in formula (DI-5-1), m = 2, 4 or 6 is preferable, m = 4 is particularly preferable, and (DI-5-12) ), M = 2 to 6 is preferable, m = 5 is particularly preferable. In (DI-5-13), m = 1 or 2 is preferable, and m = 1 is particularly preferable.

When emphasizing improving the transmittance, among the above diamines and dihydrazides, the formulas (DI-1-3), (DI-2-1), (DI-5-1), (DI-5) -5), (DI-5-24), and diamines represented by (DI-7-3) are preferably used, and diamines represented by (DI-2-1) are particularly preferred. 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 diamines and dihydrazides, the formulas (DI-2-1), (DI-4-1), (DI-4-2), ( It is preferable to use a diamine represented by (DI-4-10), (DI-4-15), (DI-5-28), (DI-5-30), and (DI-13-1). Diamines represented by formulas (DI-2-1), (DI-5-1), and (DI-13-1) are particularly preferable. Among them, in (DI-5-1), m = 1 is particularly preferable, and in (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 the purpose is emphasized, among the above diamines and dihydrazides, the formulas (DI-4-1), (DI-4-2), (DI-4-10), (DI-4-15), It is preferable to use a diamine represented by (DI-5-1), (DI-5-12), (DI-5-13), (DI-5-28), and (DI-16-1). Diamines represented by formulas (DI-4-1), (DI-5-1), and (DI-5-13) are particularly preferable. Among them, in the formula (DI-5-1), m = 2, 4 or 6 is preferable, m = 4 is particularly preferable, and in (DI-5-12), m = 2 to 6 is preferable, and m = 5 is particularly preferable. Preferably, in (DI-5-13), m = 1 or 2 is preferable, and m = 1 is particularly preferable.

式（ＰＤＩ−７）において、Ｒ^５１は独立して−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、または−ＣＯＯＣＨ_３であり、ｓは０〜２の整数であり、そして式（ＰＤＩ−１２）において、Ｒ^５２は炭素数１〜１０のアルキルまたはアルコキシであり、少なくとも１つの水素はフッ素に置き換えられても良い。 In the present invention, the photosensitive diamine of formula (1) and other photosensitive materials can be used in combination, and can be selected without limitation from known photosensitive diamines. For example, it can be selected from azobenzene derivatives, stilbene derivatives, acetylene derivatives, coumarin derivatives, cinnamic acid derivatives, and benzophenone derivatives. Examples of such photosensitive diamine compounds include the following formulas (PDI-1) to (PDI-12).

In formula (PDI-7), R ⁵¹ is independently —CH ₃ , —OCH ₃ , —CF ₃ , or —COOCH ₃ , s is an integer from 0 to 2, and formula (PDI-12) In the formula, R ⁵² is alkyl or alkoxy having 1 to 10 carbon atoms, and at least one hydrogen may be replaced by fluorine.

Among the other photosensitive diamines, (PDI-7) is preferred when importance is attached to further improving the orientation of the liquid crystal. In the embodiment in which the photosensitive diamine of the formula (1) of the present invention and the above other photosensitive diamine compounds are used in combination, in consideration of the improvement of the orientation and the transmittance, the photosensitive diamine (1) / other photosensitive diamine The ratio is preferably 100/0 (mol%) to 50/50 (mol%), more preferably 100/0 (mol%) to 80/20 (mol%). In addition, two or more other photosensitive diamines may be used in combination in order to improve the above-described various characteristics such as electrical characteristics and afterimage characteristics.

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 above acid dianhydride, when importance is attached to improving the layer separation property, the formulas (AN-3-2), (AN-1-13), and (AN-4-30) are 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.

When importance is attached to improving the VHR of the liquid crystal display element, among the above acid dianhydrides, the formulas (AN-2-1), (AN-7-2), (AN-10), (AN -16-3) and compounds represented by (AN-16-4) are preferred, and in 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. 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 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 these diamines and dihydrazides, when the importance of further improving the layer separation, that is, the orientation of the liquid crystal, is represented by the formulas (DI-4-1), (DI-4-2), (DI -4-10), (DI-5-1), (DI-5-9), (DI-5-28), and (DIH-2-1) represented by diamines and hydrazides are preferably used. Among them, 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 formulas (DI-1-2), (DI-2-1), (DI-5-1), and (DI- The diamine represented by 7-3) is preferably used, and the diamine represented by (DI-2-1) is particularly preferred. 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 diamines and dihydrazides, the formulas (DI-2-1), (DI-4-1), (DI-4-2), ( It is preferable to use a diamine represented by (DI-4-15), (DI-5-1), (DI-5-28), (DI-5-30), and (DI-13-1). Diamines represented by formulas (DI-2-1), (DI-5-1), and (DI-13-1) are particularly preferable. Among them, in (DI-5-1), m = 1 or 2 is particularly preferable, and in (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 the purpose is emphasized, among the above diamines and dihydrazides, the formulas (DI-4-1), (DI-4-2), (DI-4-10), (DI-4-15), (DI-5-1), (DI-5-9), (DI-5-12), (DI-5-13), (DI-5-28), (DI-5-30), and ( It is preferable to use a diamine represented by DI-16-1), and diamines represented by formulas (DI-4-1), (DI-5-1), and (DI-5-12) are particularly preferable. . Among them, in the formula (DI-5-1), m = 1 or 2 is preferable, and in (DI-5-12), m = 2 to 6 is preferable, m = 5 is particularly preferable, and (DI-5-13) ), M = 1 or 2 is preferable, m = 1 is particularly preferable, and in (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 carbon number) A group represented by the formula: -B-T-B-H (which is an alkylene having 1 to 4 carbon atoms or a cycloalkylene having 5 to 8 carbon atoms, B is phenylene, and r is 0 or 1) 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 have the same meanings as described above), —Z ⁴ —BZ ⁵ — (where Z ⁴ , Z meaning of ⁵ and B are as defined above. groups represented _{by), -B- (O-B)} r -T- (B-O) r -B- ( wherein, B is phenylene, T is alkylene having 1 to 3 carbon atoms, —O— or —SO ₂ —, and r has the same meaning 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′-me Renbisacrylamide, N, N′-ethylenebisacrylamide, N, N′-dihydroxyethylenebisacrylamide, N- (4-hydroxyphenyl) methacrylamide, N-phenylmethacrylamide, N-butylmethacrylamide, N- (iso -Butoxymethyl) methacrylamide, N- [2- (N, N-dimethylamino) ethyl] methacrylamide, N, N-dimethylmethacrylamide, N- [3- (dimethylamino) propyl] methacrylamide, N- ( Methoxymethyl) methacrylamide, N- (hydroxymethyl) -2-methacrylamide, N-benzyl-2-methacrylamide, and N, N′-methylenebismethacrylamide.

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

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

<Oxazine compound>
For example, the liquid crystal aligning agent of this invention may further contain the oxazine compound from the objective of stabilizing the electrical property in a liquid crystal display element for a long period of time. The oxazine compound may be 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）〜（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）〜（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−、−ＳＯ₂−、−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（ＣＨ₃）₂−、−Ｃ（ＣＦ₃）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 formulas (OX-1) to (OX-3), L ³ and L ⁴ are organic groups having 1 to 30 carbon atoms, and in formulas (OX-1) to (OX-6), L ^{5 to} L ⁸ Is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, and in formula (OX-3), formula (OX-4) and formula (OX-6), Q ¹ is a single bond, —O—, —S—. , -S-S -, - SO 2 -, - CO -, - CONH -, - NHCO -, - C (CH 3) 2 -, - C (CF 3) 2 -, - (CH 2) v -, _{-O- (CH 2) v -O -} , - S- (CH 2) v 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 alkylene having 1 to 3 carbon atoms. Yes, in Q ² Definitive benzene ring, _-F hydrogen is independently attached to the naphthalene _{ring, -CH 3, -OH, -COOH,} -SO 3 H, may be replaced with _-PO 3 _{H 2.}

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

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

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

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

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

式（ＯＸ−３−Ｉ）において、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、−ＣＨ₂−、−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 formulas (OX-2-1), (OX-3-1), (OX-3-3), (OX-3-5), (OX-3-7), ( OX-3-9), (OX-4-1) to (OX-4-6), (OX-5-3), (OX-5-4), and (OX-6-6-2) to (OX Oxazine compound represented by -6-4).

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

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

Oxazine compounds represented by formulas (OX-4) to (OX-6) are aldehydes such as 4,4′-diaminodiphenylmethane, diamines having a plurality of benzene rings and organic groups that bind them, and aldehydes such as formalin. And phenol are subjected to a dehydration condensation reaction in n-butyl alcohol at a temperature of 90 ° C. or higher (see JP-A-2004-352670).

<Oxazoline compound>
For example, the liquid crystal aligning agent of 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 ring structure in the side chain, or may be a copolymer. The polymer having an oxazoline structure in the side chain may be a homopolymer of a monomer having an oxazoline structure in the side chain, or a copolymer of a monomer having an oxazoline structure in the side chain and a monomer having no oxazoline structure It may be. The copolymer having an oxazoline structure in the side chain may be a copolymer of two or more monomers having an oxazoline structure in the side chain, or two or more monomers having an oxazoline structure in the side chain and an oxazoline structure. It may also be a copolymer with a monomer that does not have.

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

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

<Epoxy compound>
For example, the liquid crystal aligning agent of the present invention may further contain an epoxy compound for the purpose of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time. The epoxy compound may be 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 manufactured by Mitsubishi Chemical Corporation), Epototo YD-128 (manufactured by Tohto Kasei Co., Ltd.), DER-331, DER-332, DER-324 (all manufactured by The Dow Chemical Company), Epicron 840, Epicron 850, Epicron 1050 (all manufactured by DIC Corporation), Epomic R-140, Epomic R-301, and Epomic R-304 (Both manufactured by Mitsui Chemicals, Inc.).

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Examples of imidation catalysts include aliphatic amines such as trimethylamine, triethylamine, tripropylamine, and tributylamine; aromatic amines such as N, N-dimethylaniline, N, N-diethylaniline, methyl-substituted aniline, and hydroxy-substituted aniline. And cyclic amines such as pyridine, methyl-substituted pyridine, hydroxy-substituted pyridine, quinoline, methyl-substituted quinoline, hydroxy-substituted quinoline, isoquinoline, methyl-substituted isoquinoline, hydroxy-substituted isoquinoline, imidazole, methyl-substituted imidazole, and hydroxy-substituted imidazole. . The imidation catalyst 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 a strong alkaline aqueous solution 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. In particular, a photo-alignment method can be suitably used.

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

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

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

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

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

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

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

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

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

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

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

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

The liquid crystal alignment film of the present invention is particularly characterized by having a large alignment anisotropy. The magnitude of such anisotropy can be evaluated by a method using polarized IR described in JP-A-2005-275364. Further, as shown in the following examples, evaluation can also be made by a method using ellipsometry. 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 is characterized by little coloring and high transmittance. The transmittance can be evaluated using an ultraviolet-visible spectrophotometer. In order to show good display characteristics, the transmittance calculated from the average value of absorbance at 380 nm to 780 nm is preferably 85% or more, and more preferably 87% or more.

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 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 Laid-Open No. 5-501735, Japanese Patent Laid-Open No. 8-157826, Japanese Patent Laid-Open No. 8-231960, Japanese Patent Laid-Open No. 9-241644 (EP8827272A1), 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である。 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. Ring A ² and ring B ² are independently 1,4-cyclohexylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, 1-2 alkenyl; , 4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2-fluoro-3-chloro-1,4 - phenylene, a 2,3-difluoro-6-methyl-1,4-phenylene, 2,6-naphthalene-diyl or 7,8-difluoro-chroman-2,6-diyl, wherein the ring ^{a 2} Contact At least one 2,3-difluoro-1,4-phenylene fine ring ^{B 2,} 2-fluoro-3-chloro-1,4-phenylene, 2,3-difluoro-6-methyl-1,4-phenylene , Or 7,8-difluorochroman-2,6-diyl; Z ¹ is independently a single bond, — (CH ₂ ) ₂ —, —CH ₂ O—, —COO—, or —CF ₂ O—. And j is 1, 2, or 3.

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のアルケニルである。好ましいＲ^１aおよびＲ^２ａは、紫外線または熱に対する安定性などを上げるために炭素数１〜１２のアルキル、または誘電率異方性の絶対値を上げるために炭素数１〜１２のアルコキシである。 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 to 12 alkenyl. 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.

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, 2,3-difluoro -6-methyl-1,4-phenylene, 2,6-naphthalenediyl, 7,8-difluorochroman-2,6-diyl, wherein at least one of ring A ² and ring B ² is 2, 3-difluoro-1,4-phenylene, 2-fluoro-3-chloro-1,4-phenylene, 2,3-difluoro-6-methyl-1,4-phenylene, 7,8-difluorochroman-2,6 -In diyl And when j is 2 or 3, any two rings A ² may be the same or different. 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.

Ring A ²¹ , Ring A ²² , Ring A ²³ , Ring B ²¹ , and Ring B ²² are each independently 1,4-cyclohexylene or 1,4-phenylene. 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.

Z ¹ and Z ² are each independently a single bond, — (CH ₂ ) ₂ —, —CH ₂ O—, —COO—, —CF ₂ O—, and when j is 2 or 3, any Two Z ¹ may be the same or different, and when k is 2 or 3, any two Z ² may be the same or different, and preferred Z ¹ and Z ² are dielectric constants It is —CH ₂ O— for increasing anisotropy and a single bond for decreasing the viscosity.

Z ¹¹ and Z ¹² are each independently a single bond, — (CH ₂ ) ₂ —, —CH ₂ O—, or —COO—. Desirable Z ¹¹ and Z ¹² are —CH ₂ O— for increasing the dielectric anisotropy, and a single bond for decreasing the viscosity.

j is 1, 2, or 3. Preferred j is 1 for decreasing the minimum temperature, and 2 for increasing the maximum temperature.

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 of (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. It measured at 25 degreeC using the viscometer (the Toki Sangyo company make, TV-22).
2. 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.
3. Retardation of alignment film and film thickness measurement Spectroscopic ellipsometer M-2000U (manufactured by JAWoollam Co. Inc.) was used. In this example, the retardation value of the film increases in proportion to the degree of orientation of the polymer main chain. That is, those having a large retardation value have a large degree of orientation.
4). Transmittance The transmittance of a substrate on which a liquid crystal alignment film described later was formed was measured, and the average value of absorbance at 380 nm to 780 nm was calculated. An ultraviolet-visible spectrophotometer V-660 (manufactured by JASCO Corporation) was used as the ultraviolet-visible spectrophotometer.
5. Pretilt angle measurement Measured according to the crystal rotation method.
6). 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.
8). 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.

<Tetracarboxylic dianhydride>
Acid dianhydride (AN-1-1): 1,2,3,4-butanetetracarboxylic dianhydride acid dianhydride (AN-1-2, m = 8): 3,3 ′-(octane -1,8-diyl) bis (dihydrofuran-2,5-dione)
Acid dianhydride (AN-1-13): ethylenediaminetetraacetic acid dianhydride acid dianhydride (AN-2-1): 1,2,3,4, -cyclobutanetetracarboxylic dianhydride acid dianhydride (AN-3-1): 1,2,4,5-cyclohexanetetracarboxylic dianhydride dianhydride (AN-3-2): pyromellitic dianhydride dianhydride (AN-4-) 5): 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride dianhydride (AN-4-17, m = 4): 1,4-bis (phenyl 3,4-dicarboxylate) Butane dianhydride dianhydride (AN-4-17, m = 8): 1,8-bis (phenyl 3,4-dicarboxylate) octane dianhydride dianhydride (AN-4-21): 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride dianhydride (AN-4-29): 5,5′-p-phenylenebis (isobenzofuran-1,3-dione)
Acid dianhydride (AN-4-30): N, N ′-(1,4-phenylene) bis (1,3-dioxooctahydroisobenzofuran-5-carboxamide)
Acid dianhydride (AN-7-2): 2,3,5-tricarboxycyclopentyl acetic acid dianhydride acid dianhydride (AN-10): Bicyclo [3.3.0] octane-2,4,6 , 8-Tetracarboxylic dianhydride

<Diamine and dihydrazide>
Diamine (1-1): Diamine compound obtained by the synthesis route of Example 1 Diamine (1-2): Diamine compound obtained by the synthesis route of Example 2 (1-4): Synthesis of Example 3 Diamine compound diamine (1-5) obtained by the route: Diamine compound diamine (1-8) obtained by the synthesis route of Example 373: Diamine compound diamine obtained according to the synthesis route of Example 1 ( 1-12): Diamine compound diamine obtained according to the synthesis route of Example 1 (1-13): Diamine compound diamine obtained according to the synthesis route of Example 1 (1-19): Implementation Diamine compound obtained by the synthesis route of Example 374

Diamine (DI-1-3): 1,6-diaminohexanediamine (DI-2-1): 1,4-cyclohexanediaminediamine (DI-4-1): 1,4-phenylenediaminediamine (DI-5) -1, m = 1): 4,4'-diaminodiphenylmethanediamine (DI-5-1, m = 2): 4,4'-diaminodiphenylethanediamine (DI-5-1, m = 4): 4 , 4′-diaminodiphenylbutanediamine (DI-5-9): 4,4′-diaminodiphenyl ether diamine (DI-5-12, m = 5): 1,5-bis (4-aminophenoxy) pentanediamine ( DI-5-28): 4,4′-diaminodiphenylaminediamine (DI-5-30, k = 2): N, N′-bis (4-aminophenyl) -N, N′-dimethylethylenediaminedi Amine (DI-6-7): 4,4′-p-phenylenedianilinediamine (DI-7-3, m = 3, n = 1): 1,3-bis (4-((4-aminophenyl) ) Methyl) phenyl) propanediamine (DI-13-1): 4,4'-N, N'-bis (4-aminophenyl) piperazinediamine (DI-16-1): 1- (4-aminophenyl) -1H-indole-5-amine dihydrazide (DHI-2-1): terephthalic acid dihydrazide diamine (PDI-7-a): 4,4'-diaminoazobenzenediamine (PDI-8-a): 4,4'- Bis [(4-aminophenyl) methyl] azobenzene

<Solvent>
N-methyl-2-pyrrolidone: NMP
Butyl cellosolve (ethylene glycol monobutyl ether): BC
<Additives>
Additive (Ad1): 1,3-bis (4,5-dihydro-oxazolyl) benzene additive (Ad2): N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane additive ( Ad3): 3-aminopropyltriethoxysilane

Example 1 Synthesis of Compound (1-1) <First Step; Protection of Amino Group>
To a 500 mL three-necked flask equipped with a thermometer, a nitrogen inlet tube and a dropping funnel, 1,2-bis (4-aminophenyl) ethane (25.0 g, 117.8 mmol), 4-dimethylaminopyridine (2.9 g, 23.5 mmol) and triethylamine (17.9 g, 176.6 mmol) were added, and 250 mL of dichloromethane was added. The solution was cooled to 0 ° C. Thereto was added dropwise trifluoroacetic anhydride (37.1 g, 176.6 mmol) while keeping the solution at 0 ° C. Thereafter, the solution was stirred under a nitrogen atmosphere for 6 hours while maintaining the temperature at 0 ° C. The reaction solution was poured into 250 mL of water, and the organic layer was washed 3 times with pure water. After drying the organic layer with magnesium sulfate, the solvent was distilled off under reduced pressure to obtain crude crystals. The crude crystals were recrystallized with a mixed solvent of toluene / ethanol = 10/1 to obtain 1- (4-N-trifluoroacetylphenyl) -2- (4-aminophenyl) ethane (yield 33.4 g, yield). 92%).

<Second stage; synthesis of azo compound>
1- (4-N-trifluoroacetylphenyl) -2- (4-aminophenyl) ethane (30 g, 97.3 mmol) obtained in the first stage in a 500 mL three-necked flask equipped with a reflux tube and a thermometer, Sodium peroxoborate tetrahydrate (20.0 g, 131.3 mmol) and boric acid (5.1 g, 84.7 mmol) were added, and 300 mL of acetic acid was added. To the mixture was heated and stirred at 60 ° C. for 1 hour, sodium peroxoborate tetrahydrate (7.7 g, 48.7 mmol) was added, and the mixture was further heated and stirred for 6 hours. The reaction solution was poured into 600 mL of pure water, and the precipitate was collected by filtration. The obtained precipitate was washed three times with pure water, and the obtained crystal was vacuum-dried at 60 ° C. for 8 hours to obtain 4,4′-bis (2- (4-N-trifluoroacetylphenyl) ethyl) azobenzene. (Yield 25.3 g, Yield 85%).

<Stage 3; Deprotection>
To a three-necked flask equipped with a thermometer and a reflux tube, 4,4′-bis (2- (4-N-trifluoroacetylphenyl) ethyl) azobenzene (25.0 g, 40.8 mmol) obtained in the second stage was added. ) And potassium carbonate (13.5 g, 98.0 mmol), methanol (200 mL), tetrahydrofuran (25 mL) and pure water (10 mL) were added, and the mixture was stirred with heating at 60 ° C. for 12 hours. After the organic layer was dried over magnesium sulfate, the solvent was distilled off under reduced pressure to obtain crude crystals, which were recrystallized with a mixed solvent of toluene / ethanol = 1/1 (volume ratio). 4,4′-bis (2- (4-aminophenyl) ethyl) azobenzene was obtained (yield; 15.5 g, yield 90%).

Example 2 Synthesis of Compound (1-2) <First Stage; Esterification>
A three-necked flask equipped with a thermometer and a dropping funnel was charged with azobenzene-4,4′-dicarbonyl dichloride (25.0 g, 81.4 mmol) and triethylamine (19.8 g, 195.4 mmol), and 150 mL of dichloromethane was added. added. While keeping this solution at 5 ° C. or lower, a solution of 4- (Nt-butoxycarbonylamino) phenol (34.5 g, 179.1 mmol) dissolved in dichloromethane (100 mL) was added dropwise thereto, and the temperature was raised to room temperature. Allow to warm and stir for 6 hours. The reaction solution was poured into water (250 mL), and the organic layer was washed 3 times with pure water (300 mL). The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain azobenzene-4,4′-bis (4- (Nt-butoxycarbonylamino) phenyl) dibenzoate (yield 44. 6 g, 84% yield).

<Second stage: Deprotection>
A three-necked flask equipped with a thermometer and a dropping funnel was charged with azobenzene-4,4′-bis (4- (Nt-butoxycarbonylamino) phenyl) dibenzoate (44.0 g, 67) obtained in the first step. .4 mmol) and dichloromethane (300 mL) was added. While maintaining this solution at 5 ° C. or lower, a mixed solution of 47% hydrobromic acid (25.5 g, 148.3 mmol) and acetic acid (75 mL) was added dropwise thereto. The reaction was warmed to room temperature and allowed to stir for 6 hours. To this reaction solution, a saturated aqueous sodium hydrogen carbonate solution was added until the pH of the solution reached 7 or higher. This solution was poured into water (500 mL), 200 mL of dichloromethane was added, extraction operation was performed, and 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 obtained crude crystals were recrystallized with ethanol to obtain azobenzene-4,4′-bis (4-aminophenyl) dibenzoate (yield 23.8 g, yield 78%).

Example 3 Synthesis of Compound (1-4) <First Step; Amidation>
A three-necked flask equipped with a thermometer and a dropping funnel was charged with azobenzene-4,4′-dicarbonyl dichloride (25.0 g, 81.4 mmol) and triethylamine (19.8 g, 195.4 mmol), and 150 mL of dichloromethane was added. added. While keeping this solution at 5 ° C. or lower, a solution of 4- (Nt-butoxycarbonylamino) aniline (37.3 g, 179.1 mmol) dissolved in dichloromethane (100 mL) was added dropwise thereto, and the temperature was raised to room temperature. Allow to warm and stir for 6 hours. The reaction solution was poured into water (250 mL), and the organic layer was washed 3 times with pure water (300 mL). The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain the following compound (yield 42.9 g, yield 81%).

<Second stage: Deprotection>
The compound obtained in the first step (40.0 g, 61.5 mmol) was placed in a three-necked flask equipped with a thermometer and a dropping funnel, and dichloromethane (300 mL) was added. While maintaining this solution at 5 ° C. or lower, a mixed solution of 47% hydrobromic acid (23.3 g, 135.2 mmol) and acetic acid (75 mL) was added dropwise thereto. The reaction was warmed to room temperature and allowed to stir for 6 hours. To this reaction solution, a saturated aqueous sodium hydrogen carbonate solution was added until the pH of the solution reached 7 or higher. This solution was poured into water (500 mL), 200 mL of dichloromethane was added, extraction operation was performed, and 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 obtained crude crystals were recrystallized from ethanol to give compound (1-4) (yield 20.2 g, yield 73%).

[Example 4]
<Synthesis of polyamic acid>
In a three-necked flask equipped with a stirring blade and a thermometer, 2.5427 g of the compound (1-1) synthesized in Example 1 and 2.4573 g of the compound (AN-4-17) (m = 8) were weighed. To this was added 65 g of N-methyl-2-pyrrolidone (NMP). The mixture was stirred at room temperature for 12 hours, 30 g of ethylene glycol monobutyl ether (BC) was added thereto, and the mixture was further stirred for 2 hours. The solution was heated to 60 ° C. until the viscosity of the solution reached 35 m · Pa, and the viscosity was reduced to obtain a solution having a polyamic acid concentration of 5% by weight. This solution is designated as varnish A. The weight average molecular weight of the polyamic acid in this varnish was 72,000.

[Examples 5 to 20]
As shown in Table 1 below, a varnish having a polyamic acid concentration of 5% by weight, which becomes a polymer for forming a photoalignment film, was obtained according to the method described in Example 4. The value in () represents mol% when the total amount of raw materials is 100 mol%. In Examples 15 to 17, after adjusting the varnish as described above, the additives (Ad1) to (Ad3) were added at a rate of 10 parts by weight per 100 parts by weight of the polymer, respectively. Example 4 is also shown in the table.

[Comparative Examples 1-3]
As shown in Table 2 below, a varnish having a polyamic acid concentration of 5% by weight, which becomes a polymer for forming a photoalignment film, was obtained according to the method described in Example 4. The value in () represents mol% when the total amount of raw materials is 100 mol%.

[Example 21]
1.0 g of varnish A was weighed into a sample bottle and NMP / BC = 1/1 (weight ratio) was added to make 1.67 g. The polyamic acid solution of about 3% by weight was dropped on a transparent glass substrate and applied by a spinner method (2,000 rpm, 15 seconds). After coating, the substrate was heated at 80 ° C. for 3 minutes to evaporate the solvent, and then UV light was passed through the polarizing plate from the vertical direction with respect to the substrate using Multilight ML-501C / B manufactured by USHIO INC. The linearly polarized light was irradiated. The exposure energy at this time is 1.3 ± 0.1 J / cm ² at a wavelength of 365 nm by measuring the amount of light using a UV integrated light meter UIT-150 (receiver: UVD-S365) manufactured by USHIO INC. The exposure time was adjusted. The substrate after light irradiation was heat-treated in an oven at 210 ° C. for 15 minutes to obtain an alignment film A having a thickness of about 100 nm. The retardation of the alignment film A was determined using a spectroscopic ellipsometer M-2000U manufactured by JAWoollam Co. Inc. In this example, the retardation value of the film increases in proportion to the degree of orientation of the polymer main chain. That is, those having a large retardation value have a large degree of orientation. When the retardation of this alignment film A was measured, it was 19.2 nm. Moreover, when the UV-Vis spectrum of the obtained alignment film A was measured using V-660 manufactured by JASCO Corporation, the average value of the transmittances of 380 to 780 nm was calculated as the transmittance of the alignment film A. %Met. A glass substrate on which no alignment film was formed was used as a reference for the UV-Vis spectrum of the alignment film.

[Examples 22 to 34] and [Comparative Examples 4 to 6]
For varnishes B to N and X to Z, alignment films B to I and X to Z were formed by the operation according to Example 21, and the retardation and transmittance were measured according to the method of Example 21. The results are shown in Tables 3 and 4. The results of Example 21 are also shown in Table 3.

In the alignment films A to N obtained from the varnishes A to N, it was found that all the alignment films have large retardation and high transmittance. The alignment film X obtained from the varnish X had a large retardation, but it was visually observed that the transmittance was low and the film was colored. It was found that the alignment film obtained from varnishes Y and Z had a small retardation and a low transmittance.

物性値：ＮＩ １００．１℃； Δε ５．１； Δｎ ０．０９３； η ２５．６ｍＰａ・ｓ． [Example 35]
An alignment film A having a thickness of about 100 nm was obtained by the method according to Example 21 except that the glass substrate was replaced with a transparent glass substrate provided with an ITO electrode on one side. Two substrates on which the alignment films are formed on the ITO electrode are opposed to each other on the surface on which the alignment films are formed, and a gap for injecting the liquid crystal composition is provided between the facing alignment films. Pasted together. At this time, the polarization directions of the linearly polarized light irradiated to the respective alignment films were made parallel. A positive type liquid crystal composition A shown below was injected into this cell to prepare a liquid crystal cell A (liquid crystal display element) having a cell thickness of 7 μm.
<Positive liquid crystal composition A>

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

When this liquid crystal cell A was visually observed, no so-called flow alignment was observed in which liquid crystals were arranged radially from the inlet. When the polarizing microscope was set in a crossed Nicol state and the liquid crystal cell A was rotated, clear bright and dark states were observed. The pretilt angle of the liquid crystal cell A (hereinafter sometimes abbreviated as Pt angle) was 0.0 °. VHR (voltage holding ratio) and ion density were 99.0% (30 Hz), 87.0% (0.3 Hz) and 80 pC.

[Examples 36 to 48] and [Comparative Examples 7 to 9]
In accordance with the method described in Example 35, liquid crystal cells B to N and XY were also prepared for varnishes B to N and X to Y, and the alignment state, pretilt angle, VHR, and ion density were measured. The measurement results are shown in Tables 5 and 6. Example 35 is also shown in Table 5.

In the liquid crystal cells A to N and X, a good alignment state was exhibited, and a Pt angle was 0.1 ° or less, and a good black display was shown. Moreover, the electrical characteristics represented by VHR and ion density were also good results. In the liquid crystal cells Y and Z, the electrical characteristics were good, but the liquid crystal flow alignment was confirmed, resulting in a liquid crystal cell with poor display.

<Polymer blend>
[Examples 49 to 58]
As shown in Table 5 below, according to the method described in Example 4, a varnish having a polyamic acid concentration of 5% by weight as a base polymer was obtained. The value in () represents mol% when the total amount of raw materials is 100 mol%.

[Example 59]
In a sample bottle, 0.2 g of varnish A and 0.8 g of varnish a were weighed, NMP / BC = 1/1 (weight ratio) was added to obtain 1.67 g, and a photo-alignment film-forming polymer varnish: base polymer varnish = 2: 8 (weight ratio) of polymer blended varnish Aa was obtained. The polyamic acid solution of about 3% by weight was dropped on a transparent glass substrate and applied by a spinner method (2,000 rpm, 15 seconds). After coating, the substrate was heated at 80 ° C. for 3 minutes to evaporate the solvent, and then UV light was passed through the polarizing plate from the vertical direction with respect to the substrate using Multilight ML-501C / B manufactured by USHIO INC. The linearly polarized light was irradiated. The exposure energy at this time is 1.3 ± 0.1 J / cm ² at a wavelength of 365 nm by measuring the amount of light using a UV integrated light meter UIT-150 (receiver: UVD-S365) manufactured by USHIO INC. The exposure time was adjusted so that The substrate after light irradiation was heat-treated in an oven at 210 ° C. for 15 minutes to obtain an alignment film Aa having a thickness of about 100 nm. The retardation of the alignment film Aa was determined using a spectroscopic ellipsometer M-2000U manufactured by JAWoollam Co. Inc. In this example, the retardation value of the film increases in proportion to the degree of orientation of the polymer main chain. That is, those having a large retardation value have a large degree of orientation. When the retardation of this alignment film Aa was measured, it was 19.3 nm. Moreover, when the UV-Vis spectrum of obtained alignment film Aa was measured using JASCO V-660, the average value of the transmittance | permeability of 380-780 nm was computed as the transmittance | permeability of alignment film Aa, and it was 95.5. %Met. A glass substrate on which no alignment film was formed was used as a reference for the UV-Vis spectrum of the alignment film.

[Examples 60 to 158] and [Comparative Examples 10 to 19]
For varnishes B to N and X, polymer blended varnishes Ab to Nj and Xa to Xj were obtained by an operation according to Example 59. Subsequently, alignment films Ab to Nj and Xa to Xj were formed according to Example 59, and retardation and transmittance were measured. The results are shown in Tables 8-12. The results of Example 59 are also shown in Table 8. As described above, when the varnish or the alignment film is represented by a combination of uppercase and lowercase letters, the uppercase letter represents the type of the photo-alignment film forming polymer, and the lowercase letter represents the type of the base polymer. The weight ratio of the two blended varnishes is all photoalignment film-forming polymer varnish: base polymer varnish = 2: 8.

In Examples 129 to 158 shown in Table 11 and Table 12, the additive (Ad1), (Ad2) or (Ad3) was added to the blended varnish. The addition amount of the additive is 10 parts by weight with respect to 100 parts by weight of the total polymer weight after the polymer blend. In the table, the symbols of the additives are shown in the frame together with the uppercase letters and lowercase letters.

It was found that the varnishes A to N did not decrease the sensitivity to light from the fact that an alignment film having a large retardation was obtained even when polymer blending was performed. It was also found that an alignment film having higher transmittance can be obtained by polymer blending. In the varnish X, the sensitivity to light did not decrease, but the transmittance was low even when polymer blending was performed.

[Example 159]
An alignment film Aa having a film thickness of about 100 nm was obtained by the method according to Example 56 except that the glass substrate was replaced with a transparent glass substrate provided with an ITO electrode on one side. Two substrates on which the alignment films are formed on the ITO electrode are opposed to each other on the surface on which the alignment films are formed, and a gap for injecting the liquid crystal composition is provided between the facing alignment films. Pasted together. At this time, the polarization directions of the linearly polarized light irradiated to the respective alignment films were made parallel. The liquid crystal composition A described above was injected into these cells to prepare a liquid crystal cell Aa (liquid crystal display element) having a cell thickness of 7 μm.

When the liquid crystal cell Aa was visually observed, no so-called flow alignment in which liquid crystals were arranged radially from the inlet was not observed at all. When the polarizing microscope was set in a crossed Nicol state and the liquid crystal cell Aa was rotated, clear bright and dark states were observed. The pretilt angle of the liquid crystal cell A was 0.0 °. VHR (voltage holding ratio) and ion density were 99.2% (30 Hz), 87.3% (0.3 Hz) and 60 pC.

[Examples 160 to 258] and [Comparative Examples 20 to 29]
In accordance with the method described in Example 159, liquid crystal cells Ab to Kj, Oa to Qj, and Xa to Xj were prepared for varnishes Ab to Kj, Oa to Qj, and Xa to Xj, and the alignment state, pretilt angle, VHR and ion density were measured. The measurement results are shown in Tables 14-19. Example 159 is also shown in Table 14.

All the produced liquid crystal cells showed a good alignment state, and a good black display was obtained with a Pt angle of 0.1 ° or less. Moreover, the electrical characteristics represented by VHR and ion density were also good results.

[Example 259]
A liquid crystal cell A ′ was produced according to the method described in Example 32 except that the liquid crystal composition was changed from the positive liquid crystal composition A to the following negative liquid crystal composition B. When this liquid crystal cell A ′ was visually observed, so-called flow alignment in which liquid crystals were arranged radially from the inlet was not observed at all. When the polarizing microscope was set in a crossed Nicol state and the liquid crystal cell A ′ was rotated, clear bright and dark states were observed. The pretilt angle of the liquid crystal cell A ′ was 0.0 °. VHR (voltage holding ratio) and ion density were 99.0% (30 Hz), 87.0% (0.3 Hz) and 80 pC.

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.

[Examples 260 to 272]
In accordance with the method described in Example 259, liquid crystal cells B ′ to N ′ were also prepared for varnishes B to N, and the alignment state, pretilt angle, VHR, and ion density were measured. The measurement results are shown in Table 20. Example 259 is also shown in Table 20.

[Examples 273 to 372]
In accordance with the method described in Example 259, liquid crystal cells Aa ′ to Kj ′ and Oa ′ to Qj ′ were prepared for varnishes Aa to Kj and Oa to Qj, and the alignment state, pretilt angle, VHR, and ion density were measured. did. The measurement results are shown in Tables 21-25.

It has been found that even when the liquid crystal composition is changed from the positive liquid crystal composition A to the negative liquid crystal composition B, the liquid crystal display device provided with the alignment film of the present invention is excellent in viewing characteristics and electrical characteristics.

Example 373 Synthesis of Compound (1-5) <First Step; Amidation>
Azobenzene-4,4′-dicarbonyl dichloride (25.0 g, 81.4 mmol) was placed in a three-necked flask equipped with a thermometer and a dropping funnel, and 150 mL of dichloromethane was added. A solution in which 4-nitro-N-methylaniline (27.3 g, 179.1 mmol) and triethylamine (19.8 g, 195.4 mmol) were dissolved in dichloromethane (100 mL) while keeping this solution at 5 ° C. or lower. Was added dropwise, the temperature was raised to room temperature, and the mixture was stirred for 6 hours. The reaction solution was poured into water (250 mL), and the organic layer was washed 3 times with pure water (300 mL). The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain the following compound (yield 33.3 g, yield 76%).

<Second stage; reduction of nitro group>
Into a 2 L eggplant flask, the compound obtained in the first stage (30.0 g, 55.7 mmol) and sodium sulfate nonahydrate (80.3 g, 334.2 mmol) were added, 750 mL of ethanol and 750 mL of pure water were added, and 8 Heated to reflux for hours. The reaction solution was poured into 1000 mL of ethyl acetate, and the organic layer was washed 3 times with pure water (1000 mL). After drying the organic layer with anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain crude crystals. The obtained crude crystals were recrystallized from ethanol to obtain compound (1-5) (yield 19.2 g, yield 72%).

Example 374 Synthesis of Compound (1-19) <First Step>
To a 1 L three-necked flask equipped with a thermometer and dropping funnel was added 1,4-dibromocyclohexane (25.0 g, 103.3 mmol), dichlorobistriphenylphosphine palladium (II) (1.5 g, 2.1 mmol) and iodide. Copper (I) (0.8 g, 4.1 mmol) was added, and triethylamine (200 mL) and tetrahydrofuran (100 mL) were added. While this solution was heated to reflux, a solution of 4-ethynylaniline (11.5 g, 98.1 mmol) dissolved in 60 mL of tetrahydrofuran was added dropwise thereto, and after completion of the addition, the solution was further heated to reflux in a nitrogen atmosphere for 3 hours. . After allowing to cool, the insoluble material was removed by filtration, and 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 column chromatography (silica gel, eluent; toluene: methanol = 10: 1 (volume ratio)) to obtain the following compound (yield; 16.2 g, yield; 63%).

<Second stage>
In a 1 L eggplant flask, the compound obtained in the first step (16.0 g, 57.5 mmol) and N.I. E Chemcat hydrogenation catalyst BNA-5D (1.6 g) was added. The mixture was stirred at room temperature for 18 hours under a hydrogen atmosphere, the catalyst was removed by filtration, and the solvent was distilled off under reduced pressure to obtain crude crystals. The crude crystals were recrystallized from a mixed solvent of ethanol: toluene = 1: 3 to obtain the following compound (yield: 14.8 g, yield: 91%).

<Third stage>
In a 1 L eggplant flask, the compound obtained in the second stage (14.5 g, 51.4 mmol), benzophenone imine (10.2 g, 56.5 mmpl), [1,3-bis (2,6-diisopropylphenyl) imidazole-2 -Ilidene] (3-chloro-pyridyl) palladium (II) dichloride (1.4 g, 2.1 mmol) and potassium t-butoxy (8.7 g, 77.1 mmol) were added, and 1,4-dioxane (100 mL) was added. In addition, the mixture was stirred at 80 ° C. for 8 hours under a nitrogen atmosphere. After allowing to cool, the insoluble material was removed by filtration, and 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 column chromatography (silica gel, eluent; toluene: methanol = 10: 1 (volume ratio)) to obtain the following compound (yield; 16.1 g, yield; 82%).

<Fourth stage>
In a third stage, a 500 mL three-necked flask equipped with a reflux tube and thermometer was equipped with compound (16.0 g, 41.8 mmol), sodium peroxoborate tetrahydrate (8.6 g, 56.4 mmol) and boric acid (2 0.2 g, 36.4 mmol) and 150 mL of acetic acid was added. To the mixture was heated and stirred at 60 ° C. for 1 hour, sodium peroxoborate tetrahydrate (3.2 g, 20.9 mmol) was added, and the mixture was further heated and stirred for 6 hours. The reaction solution was poured into 400 mL of pure water, and the precipitate was collected by filtration. The obtained precipitate was washed 3 times with pure water, and the obtained crystal was vacuum-dried at 60 ° C. for 8 hours to obtain the following compound (yield 12.6 g, yield 79%).

<Fifth stage>
The compound obtained in the fourth step (12.0 g, 15.8 mmol) was placed in a 500 mL eggplant flask, and 40 mL of 3N hydrochloric acid and 120 mL of tetrahydrofuran were added. The mixture was stirred at room temperature for 12 hours, and the solvent was distilled off under reduced pressure. Pure water (100 mL) was added thereto, and 20% aqueous sodium hydroxide solution was added until the pH of the solution reached 8.
The precipitated crystals were collected by filtration, and the crude crystals were recrystallized from a mixed solvent of ethanol: toluene = 1: 1 (volume ratio) to obtain the following compound (1-19) (yield: 5.5 g, yield) 80%).

[Examples 375 and 376]
As shown in Table 26 below, a varnish having a polyamic acid concentration of 5% by weight, which becomes a polymer for forming a photoalignment film, was obtained according to the method described in Example 4. The value in () represents mol% when the total amount of raw materials is 100 mol%.

[Examples 377 and 378]
The alignment film R was formed using the varnish R and the alignment film S was formed using the varnish S by the operation according to Example 21, and the retardation and transmittance were measured according to the method of Example 21. The results are shown in Table 27.

It was found that both the alignment film R obtained from the varnish R and the alignment film S obtained from the varnish S have large retardation and high transmittance in all the alignment films.

Examples 379 and 380
In accordance with the method described in Example 35, a liquid crystal cell R was produced using varnish R, and a liquid crystal cell S was produced using varnish S, and the alignment state, pretilt angle, VHR and ion density were measured. The measurement results are shown in Table 28.

Both the liquid crystal cell R and the liquid crystal cell S showed a good alignment state, and a good black display was shown with a Pt angle of 0.1 ° or less. Moreover, the electrical characteristics represented by VHR and ion density were also good results.

[Examples 381 and 382]
Varnish Rd polymer-blended was obtained in the same manner as in Example 59 except that varnish R was used instead of varnish A in Example 59 and varnish d was used instead of varnish a. Similarly, polymer blended varnish Sh was obtained by the operation according to Example 59 except that varnish S was used instead of varnish A in Example 59 and varnish h was used instead of varnish a. Next, alignment films Rd and Sh were formed according to Example 59, and retardation and transmittance were measured. The results are shown in Table 29. As described above, when the varnish or alignment film is represented by a combination of uppercase and lowercase letters, the uppercase letter represents the type of polymer for forming a photoalignment film, and the lowercase letter represents the type of base polymer. The weight ratio of the two blended varnishes is all photoalignment film-forming polymer varnish: base polymer varnish = 2: 8.

It was found that varnishes R and S were not reduced in sensitivity to light because an alignment film having a large retardation was obtained even after polymer blending.

[Examples 383 and 384]
In accordance with the method described in Example 159, a liquid crystal cell Rd was produced using varnish Rd and a liquid crystal cell Sh was produced using varnish Sh, and the alignment state, pretilt angle, VHR and ion density were measured. The measurement results are shown in Table 30.

Both the liquid crystal cell Rd in which the liquid crystal alignment film is formed using the varnish Rd and the liquid crystal cell Sh in which the liquid crystal alignment film is formed using the varnish Sh exhibit a good alignment state, and the Pt angle is also 0.1 ° or less. Black display was shown. Moreover, the electrical characteristics represented by VHR and ion density were also good results.

[Examples 385 and 386]
In accordance with the method described in Example 259, a liquid crystal cell R ′ was produced using varnish R, and a liquid crystal cell S ′ was produced using varnish S, and the alignment state, pretilt angle, VHR and ion density were measured. The measurement results are shown in Table 31.

[Examples 387 and 388]
In accordance with the method described in Example 259, a liquid crystal cell Rd ′ was produced using varnish Rd and a liquid crystal cell Sh ′ was produced using varnish Sh, and the alignment state, pretilt angle, VHR and ion density were measured. The measurement results are shown in Table 32.

Even if the liquid crystal composition is changed from the positive type liquid crystal composition A to the negative type liquid crystal composition B, the liquid crystal display device produced using the varnish R, varnish S, varnish Rd, and varnish Sh has excellent viewing characteristics and electrical characteristics. I found out that

By using a photo-alignment agent using a polyamic acid or a derivative thereof using the diamine of the present invention as a raw material, it is possible to obtain an alignment film having good sensitivity of chemical change due to light irradiation and high transmittance and orientation. By using this alignment film, a liquid crystal display element excellent in display characteristics and electrical characteristics can be obtained.

Claims (24)

Photosensitive diamine represented by Formula (1).

In formula (1), ring A and ring B are each independently at least one selected from monocyclic hydrocarbons, condensed polycyclic hydrocarbons and heterocyclic rings;
R ¹ is a linear alkylene having 2 to 20 carbon atoms, —COO—, —OCO—, —NHCO—, or —N (CH ₃ ) CO—;
R ² is a linear alkylene having 2 to 20 carbon atoms, —COO—, —OCO—, —CONH—, or —CON (CH ₃ ) —;
In R ¹ and R ² , ^one or ^two of the linear alkylene —CH ₂ — may be substituted with —O—;
R ^{a to} R ^d are each independently —F, —CH ₃ , —OCH ₃ , —CF ₃ , or —OH;
a to d are each independently an integer of 0 to 4; and
A group whose bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary. The photosensitive diamine of Claim 1 represented by Formula (2).

In Formula (2), R ¹ is a linear alkylene having 2 to 20 carbon atoms, —COO—, —OCO—, —NHCO—, or —N (CH ₃ ) CO—;
R ² is a linear alkylene having 2 to 20 carbon atoms, —COO—, —OCO—, —CONH—, or —CON (CH ₃ ) —;
In R ¹ and R ² , ^one or ^two of the linear alkylene —CH ₂ — may be substituted with —O—;
R ^{a to} R ^d are each independently —F, —CH ₃ , —OCH ₃ , —CF ₃ , or —OH;
a to d are each independently an integer of 0 to 4; and
A group whose bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary. The photosensitive diamine of Claim 1 or 2 represented by Formula (3).

In Formula (3), R ¹ is a linear alkylene having 2 to 20 carbon atoms, —COO—, —OCO—, —NHCO—, or —N (CH ₃ ) CO—;
R ² is a linear alkylene having 2 to 20 carbon atoms, —COO—, —OCO—, —CONH—, or —CON (CH ₃ ) —;
R ^{a to} R ^d are each independently —F, —CH ₃ , —OCH ₃ , —CF ₃ , or —OH; and
a to d are each independently an integer of 0 to 4; and
A group whose bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary. The photosensitive diamine of any one of Claims 1-3 represented by any one of Formula (1-1)-(1-5).

A polyamic acid or a derivative thereof obtained by reacting a diamine containing at least one photosensitive diamine according to any one of claims 1 to 4 with tetracarboxylic dianhydride. In addition to the photosensitive diamine represented by the formula (1), the following formulas (DI-1) to (DI-16), (DIH-1) to (DIH-3), and (DI-31) to (DI-) The polyamic acid or derivative thereof according to claim 5, obtained by reacting a diamine containing at least one selected from the group consisting of 35) and tetracarboxylic dianhydride.

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 the formulas (DI-3) and (DI-5) to (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 'is} -S-, m' is an integer from 1 to 12 independently, k is from 1 to 5 An integer, n is 1 or 2;
In formula (DI-4), s is independently an integer of 0 to 2;
In the formulas (DI-6) and (DI-7), G ²² is independently a single bond, —O—, —S—, —CO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ). ₂ or alkylene having 1 to 10 carbon atoms;
In formula (DI-2) ~ (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, and in Formula (DI-4), the following formulas (DI-4-a) to (DI May be replaced by -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, 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 formulas (DI-4-a) and (DI-4-b), R ²⁰ is independently hydrogen or —CH ₃ ;

In the formula (DI-11), r is 0 or 1;
In formulas (DI-8) to (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 formulas (DI-13) to (DI-16), a group whose bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position 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 formulas (DIH-2) and (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, Place with 30 alkyls or alkoxys with 3-30 carbons The hydrogen of this cyclohexyl may be replaced by alkyl having 3 to 30 carbons or alkoxy having 3 to 30 carbons, and the bonding position of —NH ₂ bonded to the benzene ring is Indicates an arbitrary 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—, 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,
The sum of these is 1-5, and 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. May be different,
R ²⁶ is hydrogen, —F, —OH, alkyl having 1 to 30 carbons, fluorine-substituted alkyl having 1 to 30 carbons, alkoxy having 1 to 30 carbons, —CN, —OCH ₂ F, —OCHF ₂ , or is -OCF _3, at least one -CH ₂ in the alkyl of a carbon number of 1-30 - 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. In addition to the photosensitive diamine of formula (1), the following formulas (DI-1-3), (DI-2-1), (DI-4-1), (DI-4-2), (DI-4-) 10), (DI-4-15), (DI-5-1), (DI-5-5), (DI-5-9), (DI-5-12), (DI-5-13) , (DI-5-24), (DI-5-28) to (DI-5-30), (DI-6-7), (DI-7-3), (DI-11-2), and The polyamic acid or derivative thereof according to claim 6, obtained by reacting a mixture of diamines containing at least one selected from (DI-13-1) and tetracarboxylic dianhydride.

In the formulas (DI-5-1), (DI-5-12), (DI-5-13), and (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. Furthermore, the polyamic acid of any one of Claims 5-7 obtained by making the mixture of the diamine containing at least 1 of photosensitive diamines other than Formula (1), and tetracarboxylic dianhydride react, or its Derivative. The polyamic acid according to claim 8, wherein the photosensitive diamine other than formula (1) is at least one selected from the group consisting of azobenzene derivatives, stilbene derivatives, acetylene derivatives, coumarin derivatives, cinnamic acid derivatives, and benzophenone derivatives. Or its derivatives. The polyamic acid or derivative thereof according to claim 8 or 9, wherein the photosensitive diamine other than the formula (1) is at least one compound selected from the group consisting of the following formulas (PDI-1) to (PDI-12). .

In formula (PDI-7), R ⁵¹ is independently —CH ₃ , —OCH ₃ , —CF ₃ , or —COOCH ₃ , s is an integer from 0 to 2, and formula (PDI-12) In the formula, R ⁵² is alkyl or alkoxy having 1 to 10 carbon atoms, and at least one hydrogen may be replaced by fluorine. The polyamic acid or derivative thereof according to any one of claims 8 to 10, wherein the photosensitive diamine other than the formula (1) is a compound represented by the following formula (PDI-7).

In the formula (PDI-7), R ⁵¹ is independently —CH ₃ , —OCH ₃ , —CF ₃ , or —COOCH ₃ , and s is independently an integer of 0 to 2. 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 item 1.

In 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 formulas (AN-II) to (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 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 May be linked to;
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. The tetracarboxylic dianhydride is represented by the following formulas (AN-1-1), (AN-1-2), (AN-1-13), (AN-2-1), (AN-3-1). , (AN-3-2), (AN-4-5), (AN-4-17), (AN-4-21), (AN-4-29), (AN-4-30), ( At least one selected from (AN-5-1), (AN-7-2), (AN-10), (AN-11-3), (AN-16-3), and (AN-16-4) The polyamic acid or derivative thereof according to claim 12, which is a tetracarboxylic dianhydride containing one.

In formulas (AN-1-2) and (AN-4-17), m is an integer of 1-12. The liquid crystal aligning agent containing the polyamic acid of any one of Claims 5-13, or its derivative (s). A liquid crystal aligning agent containing the polyamic acid or derivative thereof according to any one of claims 7 to 13 and another polyamic acid or derivative thereof. Other polyamic acids or derivatives thereof are represented by formulas (DI-1) to (DI-16), (DIH-1) to (DIH-3), and (DI-31) to (DI-) according to claim 6. The liquid crystal aligning agent according to claim 15, which is a polyamic acid or a derivative thereof obtained by reacting at least one diamine selected from the group consisting of 35) and tetracarboxylic dianhydride. Other polyamic acids or derivatives thereof are represented by the following formulas (DI-1-3), (DI-2-1), (DI-4-1), (DI-4-2), (DI-4-10). , (DI-4-15), (DI-5-1), (DI-5-9), (DI-5-12), (DI-5-13), (DI-5-28), ( At least one diamine selected from (DI-5-30), (DI-7-3), (DI-13-1), (DI-16-1), and (DIH-2-1) and a tetracarboxylic acid The liquid crystal aligning agent of Claim 16 which is the polyamic acid obtained by making a dianhydride react, or its derivative (s).

In the formulas (DI-5-1), (DI-5-12), (DI-5-13), and (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 other polyamic acid or derivative thereof is at least one tetracarboxylic dianhydride selected from the group of tetracarboxylic dianhydrides represented by the formulas (AN-I) to (AN-VII) according to claim 12. The liquid crystal aligning agent of any one of Claims 15-17 which is the polyamic acid obtained by making a product and diamine react, or its derivative (s). Other polyamic acids or their derivatives may be represented by the following formulas (AN-1-1), (AN-1-2), (AN-1-13), (AN-2-1), (AN-3-1). , (AN-3-2), (AN-4-5), (AN-4-17), (AN-4-21), (AN-4-29), (AN-4-30), ( At least one selected from (AN-5-1), (AN-7-2), (AN-10), (AN-11-3), (AN-16-3), and (AN-16-4) The liquid crystal aligning agent of Claim 18 which is a polyamic acid obtained by making one tetracarboxylic dianhydride and diamine react, or its derivative (s).

In formulas (AN-1-2) and (AN-4-17), m is an integer of 1-12. The alkenyl-substituted nadiimide compound, a compound having a radically polymerizable unsaturated double bond, an oxazine compound, an oxazoline compound, and at least one selected from the group consisting of epoxy compounds, further containing any one of claims 14 to 19 Item 1. A liquid crystal aligning agent according to item 1. The liquid crystal aligning agent for photo-alignment of any one of Claims 14-20. The liquid crystal aligning agent for liquid crystal display elements of a horizontal electric field type according to any one of claims 14 to 21. The liquid crystal aligning film formed with the liquid crystal aligning agent of any one of Claims 14-22. 24. A liquid crystal display device comprising the liquid crystal alignment film according to claim 23.