JP6699417B2 - Liquid crystal aligning agent for forming liquid crystal aligning film for optical alignment, liquid crystal aligning film and liquid crystal display device using the same - Google Patents

Description

The present invention relates to a liquid crystal aligning agent for photoalignment used in a photoalignment method, a photoalignment film using the same, and a liquid crystal display device.

Various display devices such as personal computer monitors, LCD TVs, video camera viewfinders, projection displays, and optical printer heads, optical Fourier transform elements, light valves, and other optoelectronic-related elements have been commercialized today. The liquid crystal display elements in general use are mainly display elements using nematic liquid crystal. As a display system of a 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 narrowing of the viewing angle, which is one of the problems of these modes, a TN type liquid crystal display device using an optical compensation film and an MVA (Multi -domain Vertical Alignment) mode, IPS (In-Plane Switching) mode of lateral electric field system, FFS (Fringe Field Switching) mode, etc. have been proposed and put into practical use.

The technological development of liquid crystal display devices has been achieved not only by improving these driving methods and device structures, but also by improving the constituent members used for the devices. Among the components used for the liquid crystal display element, the liquid crystal alignment film is one of the important materials related to the display quality, and it is possible to improve the performance of the alignment film as the quality of the liquid crystal display element increases. It's getting important.

The liquid crystal alignment film is formed of a liquid crystal aligning agent. Currently, the liquid crystal aligning agent that is mainly used is a solution (varnish) in which polyamic acid or soluble polyimide is dissolved in an organic solvent. After applying this solution to the substrate, a film is formed by a means such as heating to form a polyimide-based liquid crystal alignment film. After film formation, if necessary, an alignment treatment suitable for the above-mentioned display mode is performed.

Industrially, a rubbing method, which is simple and capable of high-speed processing over a large area, is widely used as an alignment treatment method. The rubbing method is a treatment in which the surface of the liquid crystal alignment film is rubbed in one direction with a cloth in which fibers such as nylon, rayon, and polyester are flocked, and this makes it possible to obtain uniform alignment of liquid crystal molecules. However, problems such as dust generation and static electricity generation due to the rubbing method have been pointed out, and in recent years, an alignment treatment method that replaces the rubbing method has been actively developed.

As an alternative alignment treatment method to the rubbing method, an optical alignment treatment method in which light is irradiated to perform the alignment treatment is attracting attention. Many alignment mechanisms such as a photolysis method, a photoisomerization method, a photodimerization method, and a photocrosslinking method have been proposed for the photoalignment treatment method (for example, see Non-Patent Document 1, Patent Documents 1 and 2). The photo-alignment method has higher uniformity of alignment than the rubbing method, and since it is a non-contact alignment treatment method, it does not scratch the film, causing dust and static electricity to cause display defects in liquid crystal display elements. There are advantages such as reduction.

So far, studies have been conducted on photoalignment films having a photoreactive group that causes photoisomerization or photodimerization in the polyamic acid structure (for example, see Patent Documents 1 to 7). Among them, by applying the photoisomerization technique described in Patent Documents 3 to 5, the photoalignment film has a large anchoring energy, a good alignment property, and good electrical characteristics such as voltage holding ratio. It was found to give a liquid crystal display device. Furthermore, it has been found that the combined use of a specific tetracarboxylic dianhydride and a diamine makes it possible to prevent a residual voltage (residual DC) from accumulating and to provide a liquid crystal display element having a good afterimage characteristic (for example, see Patent Document 7). reference.). However, with the progress of panel technology, a liquid crystal aligning agent in which residual DC is less likely to be accumulated and whose relaxation is fast is required. Here, the residual voltage (residual DC) is a voltage that remains when the voltage is returned to 0V after the voltage is applied to drive the liquid crystal. It is known that when an arbitrary image is displayed on a liquid crystal display element for a long time and then changed to another image, a phenomenon in which the previous image remains as an afterimage occurs and the display quality is deteriorated. It is known that this afterimage can be suppressed by suppressing the above and shortening the relaxation time.

In recent years, with the spread of tablet-type liquid crystal display devices and smartphones, liquid crystal display devices having a narrow frame and a large display screen have been developed. Since it is necessary to apply a sealant on the liquid crystal alignment film in order to form a narrow frame, a liquid crystal aligning agent having high adhesiveness with the sealant is required.

JP-A-9-297313 JP-A-10-251646 JP-A-2005-275364 JP-A-2007-248637 JP-A-2009-069493 JP 2008-233713 A International publication 2013/1574643

Liquid Crystal, Volume 3, Issue 4, Page 262, 1999

An object of the present invention is to provide a liquid crystal aligning agent for photo-alignment, which has a high liquid crystal aligning property and can form a photo-aligning film having high adhesiveness with a sealant, and which can provide a liquid crystal display device having good afterimage characteristics. Is to provide. Another object of the present invention is to provide a photo-alignment film formed of the liquid crystal alignment agent and a liquid crystal display device having the liquid crystal alignment film.

As a result of intensive studies, the present inventors have used a tetracarboxylic acid dianhydride represented by the formula (I) of the present invention as a raw material for a liquid crystal aligning agent for photo-alignment, and thereby have a high liquid crystal aligning property and a sealing agent. The present invention has been completed by finding that a photo-alignment film having high adhesion with can be formed and a liquid crystal display device having good afterimage characteristics can be provided.

式（Ｉ）において、ａは１〜１２の整数である。 The present invention consists of the following.
[1] A liquid crystal aligning agent for photo-alignment, comprising at least one polymer selected from polyamic acid and its derivatives, which is a reaction product of tetracarboxylic dianhydride and diamine;
A liquid crystal aligning agent for photoalignment, wherein at least one of the raw material monomers of the polymer has a photoisomerization structure, and the raw material monomer of the polymer contains at least one compound represented by the following formula (I).

In the formula (I), a is an integer of 1-12.

[2] A compound having at least one photoisomerization structure selected from the group consisting of tetracarboxylic dianhydride and diamine, wherein the tetracarboxylic dianhydride is at least a compound represented by formula (I). Contains at least one polymer that is a reaction product of one of the starting monomers; or
At least one polymer which is a reaction product of a raw material monomer containing a compound having at least one photoisomerization structure selected from the group consisting of tetracarboxylic dianhydride and diamine;
Neither tetracarboxylic dianhydride nor diamine has a photoisomerization structure, and a reactant of a raw material monomer in which the tetracarboxylic dianhydride contains at least one compound represented by formula (I) The liquid crystal aligning agent for photo-alignment according to the item [1], which simultaneously contains at least one of the polymers

[3] A compound having at least one photoisomerization structure selected from the group consisting of tetracarboxylic dianhydride and diamine, wherein the tetracarboxylic dianhydride is at least a compound represented by the formula (I). At least one polymer that is a reaction product of a raw material monomer containing one, and other polymers used by mixing with the polymer,
The liquid crystal aligning agent for photo-alignment according to the item [2], wherein the other polymer is a polymer in which neither tetracarboxylic dianhydride nor diamine is a reaction product of a raw material monomer having a photoisomerization structure.

[4] A compound having at least one photoisomerization structure selected from the group consisting of tetracarboxylic dianhydride and diamine, wherein the tetracarboxylic dianhydride is at least a compound represented by formula (I). At least one polymer that is a reaction product of a raw material monomer containing one, and other polymers used by mixing with the polymer,
At least one of the compounds represented by formula (I) in which the other polymer has no photoisomerization structure of tetracarboxylic dianhydride and its derivative, and diamine The liquid crystal aligning agent for optical alignment according to the item [2], which is a polymer that is a reaction product of a raw material monomer containing one of

[5] At least one polymer which is a reaction product of a raw material monomer containing a compound having at least one photoisomerization structure selected from the group consisting of tetracarboxylic dianhydride and diamine,
Neither tetracarboxylic dianhydride nor diamine has a photoisomerization structure, and a reactant of a raw material monomer in which the tetracarboxylic dianhydride contains at least one compound represented by formula (I) The liquid crystal aligning agent for photo-alignment according to the item [1], which simultaneously contains at least one of the polymers

[6] Any one of [1] to [5], wherein the tetracarboxylic dianhydride represented by the formula (I) is a tetracarboxylic dianhydride represented by the formula (I-1). A liquid crystal aligning agent for photo-alignment according to item 1;

式（ＩＩ）〜（Ｖ）において、Ｒ^２およびＲ^３は独立して−ＮＨ_２を有する１価の有機基または−ＣＯ−Ｏ−ＣＯ−を有する１価の有機基であり、式（ＩＶ）においてＲ^４は２価の有機基であり、式（ＶＩ）においてＲ^５は独立して−ＮＨ_２を有する芳香環または−ＣＯ−Ｏ−ＣＯ−を有する芳香環である。 [7] Any one of [1] to [6], wherein the tetracarboxylic dianhydride or diamine having a photoisomerization structure is at least one of the compounds represented by formulas (II) to (VI). A liquid crystal aligning agent for photo-alignment according to item 1;

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

上記各式において、環を構成するいずれかの炭素原子に結合位置が固定されていない基は、その環における結合位置が任意であることを示し；
式（Ｖ−２）において、Ｒ^６は独立して−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、または−ＣＯＯＣＨ_３であり、ａは独立して０〜２の整数であり；
式（Ｖ−３）において、環Ａおよび環Ｂは独立して、単環式炭化水素、縮合多環式炭化水素および複素環から選ばれる少なくとも１つであり、
Ｒ^１１は、炭素数１〜２０の直鎖アルキレン、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−、−ＣＯＮＨ−、−Ｎ（ＣＨ_３）ＣＯ−、または−ＣＯＮ（ＣＨ_３）−であり、
Ｒ^１２は、炭素数１〜２０の直鎖アルキレン、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−、−ＣＯＮＨ−、−Ｎ（ＣＨ_３）ＣＯ−、または−ＣＯＮ（ＣＨ_３）−であり、
Ｒ^１１およびＲ^１２において、直鎖アルキレンの−ＣＨ_２−の１つまたは２つは−Ｏ−で置換されてもよく、
Ｒ^７〜Ｒ^１０は、独立して、−Ｆ、−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、または−ＯＨであり、そして、
ｂ〜ｅは、独立して、０〜４の整数である。 [8] The tetracarboxylic dianhydride or diamine having a photoisomerization structure is represented by the formula (II-1), (II-2), (III-1), (III-2), (IV-1), ( IV-2), (V-1) to (V-3), (VI-1), and at least one selected from the group of compounds represented by (VI-2), in the item [7] The liquid crystal aligning agent for optical alignment described above;

In each of the above formulas, 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 formula (V-2), R ⁶ is independently —CH ₃ , —OCH ₃ , —CF ₃ , or —COOCH ₃ , and a is independently an integer of 0 to 2;
In formula (V-3), ring A and ring B are independently at least one selected from monocyclic hydrocarbons, condensed polycyclic hydrocarbons and heterocycles,
R ¹¹ is linear alkylene having 1 to 20 carbon atoms, —COO—, —OCO—, —NHCO—, —CONH—, —N(CH ₃ )CO—, or —CON(CH ₃ )—,
R ¹² is linear alkylene having 1 to 20 carbon atoms, —COO—, —OCO—, —NHCO—, —CONH—, —N(CH ₃ )CO—, or —CON(CH ₃ )—,
In R ¹¹ and R ¹² , one or two of —CH ₂ — of the linear alkylene may be substituted with —O—,
R ⁷ to R ¹⁰ are _{independently,} -F, -CH _3, -OCH 3, a -CF ₃ or -OH,, and,
b to e are each independently an integer of 0 to 4.

式（ＡＮ−Ｉ）、式（ＡＮ−ＩＶ）および式（ＡＮ−Ｖ）において、Ｘは独立して単結合または−ＣＨ_２−であり；
式（ＡＮ−ＩＩ）において、Ｇは単結合、炭素数１〜２０のアルキレン、−ＣＯ−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−Ｃ（ＣＨ_３）_２−、または−Ｃ（ＣＦ_３）_２−であり；
式（ＡＮ−ＩＩ）〜式（ＡＮ−ＩＶ）において、Ｙは独立して下記の３価の基の群から選ばれる１つであり、

これらの基の少なくとも１つの水素はメチル、エチルまたはフェニルで置き換えられてもよく；
式（ＡＮ−ＩＩＩ）〜式（ＡＮ−Ｖ）において、環Ａ^１０は炭素数３〜１０の単環式炭化水素の基または炭素数６〜３０の縮合多環式炭化水素の基であり、この基の少なくとも１つの水素はメチル、エチルまたはフェニルで置き換えられていてもよく、環に掛かっている結合手は環を構成する任意の炭素に連結しており、２本の結合手が同一の炭素に連結してもよく；
式（ＡＮ−ＶＩ）において、Ｘ^１０は独立して炭素数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。 [9] The tetracarboxylic dianhydride having no photoisomerization structure is at least 1 selected from the group of tetracarboxylic dianhydrides represented by the following formulas (AN-I) to (AN-VII). The liquid crystal aligning agent for photo-alignment according to any one of [1] to [8];

Formula (AN-I), in formula (AN-IV) and formula (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 formulas (AN-II) to (AN-IV), Y is independently one selected from the group of the following trivalent groups,

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

式（ＡＮ−１−２）および式（ＡＮ−４−１７）において、ｍは１〜１２の整数である。 [10] The tetracarboxylic acid dianhydride having no photoisomerization structure is represented by the following formula (AN-1-1), formula (AN-1-2), formula (AN-1-13), and formula (AN). 2-1), Formula (AN-3-1), Formula (AN-3-2), Formula (AN-4-5), Formula (AN-4-17), Formula (AN-4-21). , Formula (AN-4-29), formula (AN-4-30), formula (AN-5-1), formula (AN-7-2), formula (AN-10-1), formula (AN- 11-3), the formula (AN-16-1), the formula (AN-16-3), and the formula (AN-16-4), which is at least one selected from the optical alignment according to the item [9]. Liquid crystal aligning agent;

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

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

式（ＤＩ−４−ａ）および式（ＤＩ−４−ｂ）において、Ｒ^２０は独立して水素または−ＣＨ_３であり；
環を構成する炭素原子に結合位置が固定されていない基は、その環における結合位置が任意であることを示し、シクロヘキサン環またはベンゼン環への−ＮＨ_２の結合位置は、Ｇ^２１またはＧ^２２の結合位置を除く任意の位置であり；

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

式（ＤＩ−１２）において、Ｒ^２１およびＲ^２２は独立して炭素数１〜３のアルキルまたはフェニルであり、Ｇ^２３は独立して炭素数１〜６のアルキレン、フェニレンまたはアルキル置換されたフェニレンであり、ｗは１〜１０の整数であり；
式（ＤＩ−１３）において、Ｒ^２３は独立して炭素数１〜５のアルキル、炭素数１〜５のアルコキシまたは−Ｃｌであり、ｐは独立して０〜３の整数であり、ｑは０〜４の整数であり；
式（ＤＩ−１４）において、環Ｂは単環式複素芳香族であり、Ｒ^２４は水素、−Ｆ、−Ｃｌ、炭素数１〜６のアルキル、炭素数１〜６のアルコキシ、炭素数２〜６のアルケニル、炭素数１〜６のアルキニルであり、ｑは独立して０〜４の整数であり；
式（ＤＩ−１５）において、環Ｃはヘテロ原子を含む単環であり；
式（ＤＩ−１６）において、Ｇ^２４は単結合、炭素数２〜６のアルキレンまたは１，４−フェニレンであり、ｒは０または１であり；
式（ＤＩ−１３）〜式（ＤＩ−１６）において、環を構成する炭素原子に結合位置が固定されていない基は、その環における結合位置が任意であることを示し；

式（ＤＩＨ−１）において、Ｇ^２５は単結合、炭素数１〜２０のアルキレン、−ＣＯ−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−Ｃ（ＣＨ_３）_２−、または−Ｃ（ＣＦ_３）_２−であり；
式（ＤＩＨ−２）において、環Ｄはシクロヘキサン環、ベンゼン環またはナフタレン環であり、この環の少なくとも１つの水素はメチル、エチル、またはフェニルで置き換えられてもよく；
式（ＤＩＨ−３）において、環Ｅは独立してシクロヘキサン環、またはベンゼン環であり、この環の少なくとも１つの水素はメチル、エチル、またはフェニルで置き換えられてもよく、Ｙは単結合、炭素数１〜２０のアルキレン、−ＣＯ−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−Ｃ（ＣＨ_３）_２−、または−Ｃ（ＣＦ_３）_２−であり；
式（ＤＩＨ−２）および式（ＤＩＨ−３）において、環に結合する−ＣＯＮＨＮＨ_２の結合位置は、任意の位置であり；

式（ＤＩ−３１）において、Ｇ^２６は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−、−ＣＯＮＨ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、または−（ＣＨ_２）_ｍ’−であり、ｍ’は１〜１２の整数であり、Ｒ^２５は炭素数３〜３０のアルキル、フェニル、ステロイド骨格を有する基、または下記の式（ＤＩ−３１−ａ）で表される基であり、このアルキルにおいて、少なくとも１つの水素は−Ｆで置き換えられてもよく、少なくとも１つの−ＣＨ_２−は−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられていてもよく、このフェニルの水素は、−Ｆ、−ＣＨ_３、−ＯＣＨ_３、−ＯＣＨ_２Ｆ、−ＯＣＨＦ_２、−ＯＣＦ_３、炭素数３〜３０のアルキルまたは炭素数３〜３０のアルコキシで置き換えられていてもよく、ベンゼン環に結合する−ＮＨ_２の結合位置はその環において任意の位置であることを示し、

式（ＤＩ−３１−ａ）において、Ｇ^２７、Ｇ^２８およびＧ^２９は結合基であり、これらは独立して単結合、または炭素数１〜１２のアルキレンであり、このアルキレンの１以上の−ＣＨ_２−は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＣＨ＝ＣＨ−で置き換えられていてもよく、環Ｂ^２１、環Ｂ^２２、環Ｂ^２３および環Ｂ^２４は独立して１，４−フェニレン、１，４−シクロへキシレン、１，３−ジオキサン−２，５−ジイル、ピリミジン−２，５−ジイル、ピリジン−２，５−ジイル、ピペリジン−１，４−ジイル、ナフタレン−１，５−ジイル、ナフタレン−２，７−ジイルまたはアントラセン−９，１０−ジイルであり、環Ｂ^２１、環Ｂ^２２、環Ｂ^２３および環Ｂ^２４において、少なくとも１つの水素は−Ｆまたは−ＣＨ_３で置き換えられてもよく、ｓ、ｔおよびｕは独立して０〜２の整数であって、これらの合計は０〜５であり、ｓ、ｔまたはｕが２であるとき、各々の括弧内の２つの結合基は同じであっても異なってもよく、２つの環は同じであっても異なっていてもよく、
Ｒ^２６は水素、−Ｆ、−ＯＨ、炭素数１〜３０のアルキル、炭素数１〜３０のフッ素置換アルキル、炭素数１〜３０のアルコキシ、−ＣＮ、−ＯＣＨ_２Ｆ、−ＯＣＨＦ_２、または−ＯＣＦ_３であり、この炭素数１〜３０のアルキルの少なくとも１つの−ＣＨ_２−は下記式（ＤＩ−３１−ｂ）で表される２価の基で置き換えられていてもよく、

式（ＤＩ−３１−ｂ）において、Ｒ^２７およびＲ^２８は独立して炭素数１〜３のアルキルであり、ｖは１〜６の整数であり；

式（ＤＩ−３２）および式（ＤＩ−３３）において、Ｇ^３０は独立して単結合、−ＣＯ−または−ＣＨ_２−であり、Ｒ^２９は独立して水素または−ＣＨ_３であり、Ｒ^３０は独立して水素、炭素数１〜２０のアルキル、または炭素数２〜２０のアルケニルであり；
式（ＤＩ−３３）におけるベンゼン環の１つの水素は、炭素数１〜２０のアルキルまたはフェニルで置き換えられてもよく、そして、
式（ＤＩ−３２）および式（ＤＩ−３３）において、環を構成するいずれかの炭素原子に結合位置が固定されていない基は、その環における結合位置が任意であることを示し；

式（ＤＩ−３４）および式（ＤＩ−３５）において、Ｇ^３１は独立して−Ｏ−または炭素数１〜６のアルキレンであり、Ｇ^３２は単結合または炭素数１〜３のアルキレンであり、
Ｒ^３１は水素または炭素数１〜２０のアルキルであり、このアルキルの少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、Ｒ^３２は炭素数６〜２２のアルキルであり、Ｒ^３３は水素または炭素数１〜２２のアルキルであり、環Ｂ^２５は１，４−フェニレンまたは１，４−シクロヘキシレンであり、ｒは０または１であり、そして、ベンゼン環に結合する−ＮＨ_２はその環における結合位置が任意であることを示す。 [11] A diamine having no photoisomerization structure is represented by the following formula (DI-1) to formula (DI-16), formula (DIH-1) to formula (DIH-3), and formula (DI-31). To the liquid crystal aligning agent for optical alignment according to any one of [1] to [10], which is at least one selected from the group consisting of formula (DI-35):

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

In formula (DI-4-a) and formula (DI-4-b), R ²⁰ is independently hydrogen or —CH ₃ .
A group in which the bonding position is not fixed to a 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 bonding position of

In formula (DI-11), r is 0 or 1;
In formulas (DI-8) to (DI-11), the bonding position of —NH ₂ bonded to the ring is any 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 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 Is an integer from 0 to 4;
In 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, and 2 carbons. To alkenyl, alkynyl having 1 to 6 carbon atoms, q is independently an integer of 0 to 4;
In formula (DI-15), ring C is a monocycle containing a heteroatom;
In formula (DI-16), G ²⁴ is a single bond, C 2-6 alkylene or 1,4-phenylene, and r is 0 or 1;
In the formulas (DI-13) to (DI-16), a group in which the bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary.

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

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

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

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

In formula (DI-32) and formula (DI-33), G ³⁰ is independently a single bond, —CO— or —CH ₂ —, R ²⁹ is independently hydrogen or —CH ₃ , and R 30 is ³⁰ is independently 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 with alkyl having 1 to 20 carbons or phenyl, 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 formula (DI-34) and formula (DI-35), G ³¹ is independently —O— or alkylene having 1 to 6 carbons, and G ³² is a single bond or alkylene having 1 to 3 carbons. ,
R ³¹ is hydrogen or alkyl having 1 to 20 carbons, and at least one —CH ₂ — of this alkyl may be replaced with —O—, —CH═CH— or —C≡C—, R ^{31 32} is alkyl having 6 to 22 carbons, R ³³ is hydrogen or alkyl having 1 to 22 carbons, ring B ²⁵ is 1,4-phenylene or 1,4-cyclohexylene, r is 0 or 1 and —NH ₂ bonded to the benzene ring indicates that the bonding position in the ring is arbitrary.

式（ＤＩ−５−１）、式（ＤＩ−５−１２）、式（ＤＩ−５−１３）、および式（ＤＩ−７−３）において、ｍは独立して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は独立して１または２である。 [12] A diamine having no photoisomerization structure is represented by the following formula (DI-1-3), formula (DI-2-1), formula (DI-4-1), formula (DI-4-2). , Formula (DI-4-10), formula (DI-4-15), formula (DI-5-1), formula (DI-5-5), formula (DI-5-9), formula (DI- 5-12), Formula (DI-5-13), Formula (DI-5-17), Formula (DI-5-28), Formula (DI-5-30), Formula (DI-6-7), Formula (DI-7-3), Formula (DI-11-2), Formula (DI-13-1), Formula (DI-16-1), Formula (DI-31-56), and Formula (DIH-. 2-1) A liquid crystal aligning agent for optical alignment according to the item [11], which is at least one selected from the group consisting of:

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

[13] At least one selected from the group of compounds consisting of an alkenyl-substituted nadimide compound, a compound having a radical-polymerizable unsaturated double bond, an oxazine compound, an oxazoline compound, and an epoxy compound, [1] to [1]. [12] The liquid crystal aligning agent for optical alignment according to any one of [12].

[14] The liquid crystal aligning agent for optical alignment according to any one of [1] to [13], which is used for manufacturing a horizontal electric field drive type liquid crystal display device.

[15] The liquid crystal aligning agent for optical alignment according to any one of [1] to [14], which can be applied by an inkjet method.

[16] A liquid crystal alignment film formed by the liquid crystal alignment agent for optical alignment according to any one of [1] to [15].

[17] A liquid crystal display device having the liquid crystal alignment film according to the item [16].

[18] A horizontal electric field drive type liquid crystal display device having the liquid crystal alignment film according to the item [16].

The photo-alignment liquid crystal alignment film formed by the photo-alignment liquid crystal alignment agent of the present invention has good adhesion to the sealant and high liquid crystal alignment. The liquid crystal display element having the liquid crystal alignment film for optical alignment has good afterimage characteristics, good contrast, and high display quality can be maintained.

式（Ｉ）において、ａは１〜１２の整数である。 <Liquid crystal aligning agent for photo-alignment>
The liquid crystal aligning agent for photo-alignment of the present invention contains at least one polymer of a polyamic acid and its derivative obtained by reacting a tetracarboxylic dianhydride and a diamine, and at least one of the raw material monomers of the polymer is photoisomerized. A liquid crystal aligning agent for photo-alignment, which has a chemical structure and in which the raw material monomer of the polymer contains at least one compound represented by the following formula (I).

In the formula (I), a is an integer of 1-12.

The polyamic acid derivative is a component that dissolves in a solvent when it is used as a liquid crystal aligning agent described later containing a solvent, and when the liquid crystal aligning agent is used as a liquid crystal aligning film described later, it contains polyimide as a main component. It is a component that can form a liquid crystal alignment film. Examples of such a polyamic acid derivative include soluble polyimide, polyamic acid ester, and polyamic acid amide, and more specifically, 1) polyimide in which all amino and carboxyl of polyamic acid are subjected to dehydration ring closure reaction, 2) Partial polyimide partially dehydrated and ring-closed, 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 partially converted into organic dicarboxylic acid. Examples thereof include a polyamic acid-polyamide copolymer obtained by substituting an acid for reaction, and 5) a polyamideimide obtained by subjecting a part or all of the polyamic acid-polyamide copolymer to a dehydration ring-closing reaction. The polyamic acid or its derivative may be one type of compound or two or more types.

<Photoreactive structure>
In the present invention, the photoreactive structure means a photoisomerization structure that causes isomerization upon irradiation with ultraviolet rays. A raw material monomer having a structure that causes isomerization upon irradiation with ultraviolet rays can be appropriately used.

式（ＩＩ）〜（Ｖ）において、Ｒ^２およびＲ^３は独立して−ＮＨ_２を有する１価の有機基または−ＣＯ−Ｏ−ＣＯ−を有する１価の有機基であり、式（ＩＶ）においてＲ^４は２価の有機基であり、式（ＶＩ）においてＲ^５は独立して−ＮＨ_２を有する芳香環または−ＣＯ−Ｏ−ＣＯ−を有する芳香環である。 Examples of the monomer having a photoisomerization structure include tetracarboxylic dianhydride having a photoisomerization structure and diamine having a photoisomerization structure, and the following formulas (II) to (VI) having good photosensitivity are given. It is preferably at least one selected from the group of compounds represented by: and more preferably a compound represented by formula (V).

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

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

上記各式において、環を構成するいずれかの炭素原子に結合位置が固定されていない基は、その環における結合位置が任意であることを示し、式（Ｖ−２）において、Ｒ^６は独立して−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、または−ＣＯＯＣＨ_３であり、ａは独立して０〜２の整数であり、式（Ｖ−３）において、環Ａおよび環Ｂは独立して、単環式炭化水素、縮合多環式炭化水素および複素環から選ばれる少なくとも１つであり、Ｒ^１１は、炭素数１〜２０の直鎖アルキレン、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−、−ＣＯＮＨ−、−Ｎ（ＣＨ_３）ＣＯ−、または−ＣＯＮ（ＣＨ_３）−であり、Ｒ^１２は、炭素数１〜２０の直鎖アルキレン、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−、−ＣＯＮＨ−、−Ｎ（ＣＨ_３）ＣＯ−、または−ＣＯＮ（ＣＨ_３）−であり、Ｒ^１１およびＲ^１２において、直鎖アルキレンの−ＣＨ_２−の１つまたは２つは−Ｏ−で置換されてもよく、Ｒ^７〜Ｒ^１０は、独立して、−Ｆ、−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、または−ＯＨであり、そして、ｂ〜ｅは、独立して、０〜４の整数である。 Examples of the material having the photoisomerization structure include the following formulas (II-1), (II-2), (III-1), (III-2), (IV-1), (IV-2) and (II At least one selected from the group of compounds represented by V-1) to (V-3), (VI-1), and (VI-2) can be preferably used.

In each of the above formulas, a group in which the bond position is not fixed to any carbon atom constituting the ring indicates that the bond position in the ring is arbitrary, and in formula (V-2), R ⁶ is independent. _-CH 3 _and, -OCH 3, a -CF ₃ or -COOCH _3,, a is an integer of 0 to 2 independently, in formula (V-3), ring a and ring B are independently And at least one selected from monocyclic hydrocarbons, condensed polycyclic hydrocarbons, and heterocycles, and R ¹¹ is linear alkylene having 1 to 20 carbon atoms, —COO—, —OCO—, —NHCO. _{-, - CONH -, - N} (CH 3) CO-, or -CON (CH ₃₎ - and ^{is, R 12} is a straight-chain alkylene having 1 to 20 carbon atoms, -COO -, - OCO -, - NHCO _{-, - CONH -, - N} (CH 3) CO-, or -CON (CH ₃₎ - and ^{is, R 11} and the ^{R 12,} a straight-chain alkylene -CH ₂ - 1 or 2 of -O - may be substituted ^with, R 7 ^{to R 10} are _{independently,} -F, -CH _3, -OCH 3, a -CF ₃ or -OH,, and, b to e are independently , An integer of 0 to 4.

The compounds represented by the above formulas (V-1), (V-2) and (VI-2) can be particularly preferably used from the viewpoint of their photosensitivity. In the formulas (V-2) and (VI-2), the compound in which the amino group is bound to the para position is further defined, and in the formula (V-2), the compound in which a=0 is selected from the viewpoint of its orientation. It can be used more preferably.

An acid dianhydride or a diamine having a structure capable of causing isomerization by ultraviolet irradiation represented by the formulas (II-1) to (VI-2) is represented by the following formulas (II-1-1) to (VI-2-3). It can be specifically expressed.

Among these, by using (VI-1-1) to (V-3-8) as a compound containing a structure capable of causing isomerization by UV irradiation, liquid crystal alignment for photo-alignment with higher sensitivity to UV irradiation The agent can be obtained. UV irradiation of (V-1-1), (V-2-1), (V-2-4) to (V-2-11) and (V-3-1) to (V-3-8). By using a compound having a structure capable of causing isomerization at 1, it is possible to obtain a liquid crystal aligning agent for photo-alignment that can align liquid crystal molecules more uniformly. By using (V-2-4) to (V-3-8) as a compound containing a structure capable of causing isomerization by irradiation with ultraviolet rays, a liquid crystal aligning agent for photo-alignment in which an alignment film to be formed can be less colored Can be obtained.

In an embodiment in which a (non-photosensitive) tetracarboxylic acid dianhydride having no photoreactive structure and a (photosensitive) tetracarboxylic acid dianhydride having a photoreactive structure are used in combination, the sensitivity of the alignment film to light is reduced. In order to prevent the decrease, the photosensitive tetracarboxylic dianhydride is preferably 0 to 70 mol% with respect to the total amount of the tetracarboxylic dianhydride used as a raw material when producing the polyamic acid or its derivative of the present invention. , 0 to 50 mol% is particularly preferable. Further, two or more photosensitive tetracarboxylic acid dianhydrides may be used in combination in order to improve the above-mentioned various characteristics such as sensitivity to light, electric characteristics, and afterimage characteristics.

In an embodiment in which a (non-photosensitive) diamine having no photoreactive structure and a (photosensitive) diamine having a photoreactive structure are used in combination, the polyamic acid of the present invention is used in order to prevent deterioration of the sensitivity of the alignment film to light. The photosensitive diamine is preferably 20 to 100 mol %, particularly preferably 50 to 100 mol %, based on the total amount of diamine used as a raw material when producing an acid or a derivative thereof. Further, two or more photosensitive diamines may be used in combination in order to improve the above-mentioned various characteristics such as sensitivity to light and afterimage characteristics. As described above, the embodiment of the present invention includes the case where the total amount of the tetracarboxylic acid dianhydride is occupied by the non-photosensitive tetracarboxylic acid dianhydride, and even in that case, at least 20 mol% of the total amount of the diamine is exposed to light. It is required to be a diamine.

In order to improve the above-mentioned various characteristics such as sensitivity to light and afterimage characteristics, a photosensitive tetracarboxylic dianhydride and a photosensitive diamine may be used in combination, or two or more of each may be used in combination.

式（Ｉ）において、ａは１〜１２の整数である。 The tetracarboxylic dianhydride represented by the formula (I) of the present invention will be described. The tetracarboxylic dianhydride represented by the formula (I) can be synthesized by the synthetic method described in JP-A-2002-097186. Since the tetracarboxylic dianhydride represented by the formula (I) has a flexible site of —O-alkylene-O—, it has an anisotropic property when used as a material of the polyamic acid or its derivative of the present invention. It is possible to form a photo-alignment film having a high liquid crystal alignment property. Further, since it has two —O—, it is possible to provide a liquid crystal display element having a fast relaxation of residual DC and excellent afterimage characteristics. Further, the adhesiveness can be improved by interacting with the polar group of the sealant.

In the formula (I), a is an integer of 1-12.

Specific examples of the tetracarboxylic dianhydride represented by the formula (I) are shown below.

Among the tetracarboxylic dianhydrides represented by the formula (I), the formulas (I-4) to (I-12) are preferable in order to give higher liquid crystal alignment. If the flexibility is too high, the formed photo-alignment film becomes brittle and tends to be easily scratched. When used in a liquid crystal display element such as a touch panel to which impact is applied, the formulas (I-4) to (I-10) are preferable, and the formula (I-6) is more preferable.

A non-photosensitive tetracarboxylic acid other than the tetracarboxylic dianhydride of the formula (I), which is used for producing a liquid crystal aligning agent for photo-alignment containing at least one selected from the polyamic acid and its derivative of the present invention. The acid dianhydride will be described.
The non-photosensitive tetracarboxylic dianhydride used in the present invention can be selected from known non-photosensitive tetracarboxylic dianhydrides without any limitation. Such a non-photosensitive tetracarboxylic dianhydride has an aromatic ring (including a heteroaromatic ring system) in which a dicarboxylic acid anhydride is directly bonded, and an aromatic ring in which a dicarboxylic acid anhydride is directly bonded. It may belong to any group of non-aliphatic system (including heterocyclic system).

Preferable examples of such a non-photosensitive tetracarboxylic dianhydride are represented by formulas (AN-I) to (AN-) from the viewpoint of easy availability of raw materials, ease of polymer polymerization, and electric properties of the film. And tetracarboxylic dianhydride represented by VII).

Formula (AN-I), (AN -IV) and in (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} - a. In formulas (AN-II) to (AN-IV), Y is independently one selected from the group of the following trivalent groups, the bond is linked to any carbon, and At least one hydrogen may be replaced with methyl, ethyl or phenyl.

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

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

式（ＡＮ−１）において、Ｇ^１１は単結合、炭素数１〜１２のアルキレン、１，４−フェニレン、または１，４−シクロヘキシレンである。Ｘ^１１は独立して単結合または−ＣＨ_２−である。Ｇ^１２は独立して下記の３価の基のどちらかである。

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

In 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- is,> CH- hydrogen may be replaced by -CH _3. When G ¹² is> ^{N-, G 11} is a single bond and -CH ₂ - that they are ^{not, X 11} is not a single bond. And R ¹¹ is hydrogen or —CH ₃ .

式（ＡＮ−１−２）および（ＡＮ−１−１４）において、ｍは１〜１２の整数である。 Examples of the tetracarboxylic dianhydride represented by the formula (AN-1) include compounds represented by the following formulas.

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

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

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

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

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

In formula (AN-3), 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 formulas.

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

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

In the formula ^{(AN-4), G 13} represents 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 formula (G13-1) below, m is an integer from 1 to 12. Ring A ¹¹ is independently a cyclohexane ring or a benzene ring. G ¹³ may be attached at any position on ring A ¹¹ .

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

式（ＡＮ−４−１７）において、ｍは１〜１２の整数である。

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

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

式（ＡＮ−５）において、Ｒ^１１は水素、または−ＣＨ_３である。ベンゼン環を構成する炭素原子に結合位置が固定されていないＲ^１１は、ベンゼン環における結合位置が任意であることを示す。 [Tetracarboxylic acid dianhydride represented by formula (AN-5)]

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

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

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は独立して−ＣＨ_２−、−ＣＨ_２ＣＨ_２−または−ＣＨ＝ＣＨ−である。ｎは１または２である。 [Tetracarboxylic acid dianhydride represented by formula (AN-6)]

In formula (AN-6), X ¹¹ is independently a single bond or —CH ₂ —. X ¹² is _-CH independently _{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 formulas.

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

In 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 formulas.

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

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

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

式（ＡＮ−９）において、ｒは独立して０または１である。 [Tetracarboxylic acid dianhydride represented by formula (AN-9)]

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

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

[Tetracarboxylic acid dianhydride represented by formula (AN-10-1) and formula (AN-10-2)]

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

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

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

式（ＡＮ−１２）において、環Ａ^１１は独立してシクロヘキサン環またはベンゼン環である。 [Tetracarboxylic acid dianhydride represented by formula (AN-12)]

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

Examples of the tetracarboxylic dianhydride represented by the formula (AN-12) include compounds represented by the following formulas.

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

In formula (AN-13), X ¹³ is independently 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 formulas.

式（ＡＮ−１４）において、Ｇ^１４は独立して−Ｏ−、−ＣＯＯ−または−ＯＣＯ−であり、ｒは独立して０または１である。 [Tetracarboxylic acid dianhydride represented by formula (AN-14)]

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

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

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

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

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

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

In the above acid dianhydride, suitable materials for improving each property will be described.

In the acid dianhydride used for the polymer using the monomer having a photoisomerization structure, when importance is placed on improving the orientation of the liquid crystal, the compounds of formulas (AN-1), (AN-3), and The compound represented by (AN-4) is preferable, and the compounds of formulas (AN-1-2), (AN-1-13), (AN-3-2), (AN-4-5) and (AN-4) are preferred. Compounds represented by -17) and (AN-4-29) are more preferred. In the formula (AN-1-2), m=4 or 8 is preferable. In Formula (AN-4-17), m=4 or 8 is preferable, and m=8 is more preferable.

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

When it is important to improve the VHR of the liquid crystal display element, among the above-mentioned acid dianhydrides, the compounds represented by 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-16-1), (AN-16). -3), and compounds represented by (AN-16-4) are preferable. In the formula (AN-1-2), m=4 or 8 is preferable. In Formula (AN-4-17), m=4 or 8 is preferable, and m=8 is more preferable.

Improving the relaxation rate of the residual charge (residual DC) in the alignment film by reducing the volume resistance value of the liquid crystal alignment film is effective as one of the methods for preventing image sticking. When this purpose is emphasized, among the above-mentioned acid dianhydrides, formulas (AN-1-13), (AN-3-2), (AN-4-21), (AN-4-29) are used. , And compounds represented by (AN-11-3) are preferable.

In the acid dianhydride used for the polymer that does not use the monomer having a photoisomerization structure, when importance is attached to improving the orientation of the liquid crystal, formulas (AN-1), (AN-3), and The compound represented by (AN-4) is preferable, and the compounds of formulas (AN-1-1), (AN-1-2), (AN-1-13), (AN-2-1) and (AN-3) are preferred. -2), the compounds represented by (AN-4-17) and (AN-4-29) are more preferable. In the formula (AN-1-2), m=4 or 8 is preferable. In the formula (AN-4-17), m=4 or 8 is preferable.

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

When it is important to improve the VHR of the liquid crystal display element, among the above-mentioned acid dianhydrides, the compounds represented by 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-16-1), (AN-16). -3), and compounds represented by (AN-16-4) are preferable. In the formula (AN-1-2), m=4 or 8 is preferable. In Formula (AN-4-17), m=4 or 8 is preferable, and m=8 is more preferable.

Improving the relaxation rate of the residual charge (residual DC) in the alignment film by reducing the volume resistance value of the liquid crystal alignment film is effective as one of the methods for preventing image sticking. When this purpose is emphasized, among the above-mentioned acid dianhydrides, formulas (AN-1-13), (AN-3-2), (AN-4-21), (AN-4-29) are used. , And compounds represented by (AN-11-3) are preferable.

The non-photosensitive diamine and the non-photosensitive dihydrazide used for producing the liquid crystal aligning agent for photo-alignment containing at least one selected from the polyamic acid and its derivative of the present invention will be described. In producing the liquid crystal aligning agent for photo-alignment of the present invention, known non-photosensitive diamines and non-photosensitive dihydrazides can be selected without limitation.

Diamines can be divided into two types depending on their structure. That is, when the skeleton connecting two amino groups is viewed as a main chain, it is a diamine having 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, and specific examples thereof include alkyl having 3 or more carbon atoms, alkoxy having 3 or more carbon atoms, alkoxyalkyl having 3 or more carbon atoms, and The group which has a steroid skeleton can be mentioned. A group having one or more rings, the terminal ring of which has as a substituent 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 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 type diamine. A diamine having no such side chain group may be referred to as a non-side chain type diamine.

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

The non-side chain type diamine will be described. Examples of the known diamine having no side chain include the 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 to 12. And at least one hydrogen of the alkylene may be replaced with -OH. In formula (DI-3) and formula (DI-5) to formula (DI-7), G ²¹ is independently a single bond, —NH—, —NCH ₃ —, —O—, —S—, —S. _{-S -, - SO 2 -,} - CO -, - COO -, - CONCH 3 -, - CONH -, - C (CH 3) 2 -, - C (CF 3) 2 -, - (CH 2) m _{-, - O- (CH 2)} m -O -, - N (CH 3) - (CH 2) k -N (CH 3) -, - (O-C 2 H 4) m -O -, - O _{-CH 2 -C (CF 3) 2} -CH 2 -O -, - O-CO- (CH 2) m -CO-O -, - CO-O- (CH 2) m -O-CO -, - _{(CH 2) m -NH- (CH} 2) m -, - CO- (CH 2) k -NH- (CH 2) k -, - (NH- (CH 2) m) k -NH -, - CO _{-C 3 H 6 - (NH-} C 3 H 6) n -CO-, or -S- _{(CH 2)} a m -S-, m is an integer from 1 to 12 independently, k is independently And is an integer of 1 to 5, and n is 1 or 2. In formula (DI-4), s is independently an integer of 0-2. In formula (DI-6) and formula ^{(DI-7), G 22} are independently a single bond, -O -, - S -, - CO -, - C (CH 3) 2 -, - C (CF 3 ) _2- , -NH-, or alkylene having 1 to 10 carbon atoms. Formula (DI-2) at least one hydrogen of cyclohexane ring and benzene ring in ~ formula (DI-7) is, -F, -Cl, alkyl of 1 to 3 carbon _atoms, -OCH _{3, -OH,} -CF _{3, -CO 2 H, -CONH 2} , -NHC 6 H 5, may be replaced by phenyl or benzyl, in the addition formula (DI-4), at least one hydrogen of cyclohexane ring and benzene ring It may be replaced with one selected from the group of groups represented by the following formulas (DI-4-a) to (DI-4-e). A group in which the bonding position is not fixed to the carbon atoms forming 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 any position except the bonding position of G ²¹ or G ²² .

式（ＤＩ−４−ａ）および式（ＤＩ−４−ｂ）において、Ｒ^２０は独立して水素または−ＣＨ_３である。

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

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

In the formula (DI-11), r is 0 or 1. In 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 of 1-10. In 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 formula (DI-14), ring B is a monocyclic heterocyclic aromatic group, R ²⁴ is hydrogen, —F, —Cl, alkyl having 1 to 6 carbons, alkoxy, vinyl, alkynyl, q is independently an integer of 0-4. 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. Then, a group in which the bonding position is not fixed to the carbon atom forming the ring indicates that the bonding position in the ring is arbitrary. In formulas (DI-13) to (DI-16), the bonding position of —NH ₂ bonded to the ring is an arbitrary position.

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

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

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

Examples of the 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は独立して１〜１２の整数である。

式（ＤＩ−５−１６）において、ｖは１〜６の整数である。

式（ＤＩ−５−３０）において、ｋは１〜５の整数である。

式（ＤＩ−５−３５）〜式（ＤＩ−５−３７）、および式（ＤＩ−５−３９）において、ｍは独立して１〜１２の整数であり、式（ＤＩ−５−３８）および式（ＤＩ−５−３９）において、ｋは独立して１〜５の整数であり、式（ＤＩ−５−４０）において、ｎは１または２の整数である。 Examples of the diamine represented by the formula (DI-5) are shown below.

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

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

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

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

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

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

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

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

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

式（ＤＩ−７−１２）において、ｍは１〜１２の整数である。

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

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.

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

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

式（ＤＩＨ−１−２）において、ｍは１〜１２の整数である。

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

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

Such non-side chain type diamines and dihydrazides have the effect of improving the electrical characteristics such as lowering the ion density of the liquid crystal display element. When a non-side chain type diamine and/or dihydrazide is used as the diamine used for producing the liquid crystal aligning agent for photo-alignment, which is used for the liquid crystal aligning agent of the present invention, polyamic acid, polyamic acid ester or polyimide, diamine and dihydrazide are used. The proportion of the total amount of the above is preferably 0 to 90 mol %, and more 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.

First as a side chain group, alkyl, alkyloxy, alkyloxyalkyl, alkylcarbonyl, alkylcarbonyloxy, alkyloxycarbonyl, alkylaminocarbonyl, alkenyl, alkenyloxy, alkenylcarbonyl, alkenylcarbonyloxy, alkenyloxycarbonyl, alkenylaminocarbonyl, Examples thereof include alkynyl, alkynyloxy, alkynylcarbonyl, alkynylcarbonyloxy, alkynyloxycarbonyl and alkynylaminocarbonyl. Alkyl, alkenyl and alkynyl in these groups are all groups having 3 or more carbon atoms. However, in the alkyloxyalkyl, the number of carbon atoms in the entire group may be 3 or more. These groups may be linear or branched.

Next, phenyl, phenylalkyl, phenylalkyloxy, phenyloxy, and 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( Ring structures such as cyclohexyl)oxy, bis(cyclohexyl)alkyl, bis(cyclohexyl)phenyl, bis(cyclohexyl)phenylalkyl, bis(cyclohexyl)oxycarbonyl, bis(cyclohexyl)phenyloxycarbonyl, and cyclohexylbis(phenyl)oxycarbonyl Groups may be mentioned.

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

式（ＤＩ−３１）において、Ｇ^２６は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−、−ＣＯＮＨ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、または−（ＣＨ_２）_ｍ’−であり、ｍ’は１〜１２の整数である。Ｇ^２６の好ましい例は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ_２Ｏ−、および炭素数１〜３のアルキレンであり、特に好ましい例は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ_２Ｏ−、−ＣＨ_２−および−ＣＨ_２ＣＨ_２−である。Ｒ^２５は炭素数３〜３０のアルキル、フェニル、ステロイド骨格を有する基、または下記の式（ＤＩ−３１−ａ）で表される基である。このアルキルにおいて、少なくとも１つの水素は−Ｆで置き換えられてもよく、そして少なくとも１つの−ＣＨ_２−は−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられていてもよい。このフェニルの水素は、−Ｆ、−ＣＨ_３、−ＯＣＨ_３、−ＯＣＨ_２Ｆ、−ＯＣＨＦ_２、−ＯＣＦ_３、炭素数３〜３０のアルキルまたは炭素数３〜３０のアルコキシで置き換えられていてもよい。ベンゼン環に結合する−ＮＨ_２の結合位置はその環において任意の位置であることを示すが、その結合位置はメタまたはパラであることが好ましい。即ち、基「Ｒ^２５−Ｇ^２６−」の結合位置を１位としたとき、２つの結合位置は３位と５位、または２位と５位であることが好ましい。 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 is a single bond, —O—, —COO—, —OCO—, —CO—, —CONH—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—. , -OCF ₂ -, or - _(CH 2) _{m '-} it is and, m' is an integer from 1 to 12. Preferred examples of G ²⁶ represents a single bond, -O -, - COO -, - OCO -, - CH 2 O-, and alkylene having 1 to 3 carbon atoms, particularly preferred examples are 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 Good. The bonding position of —NH ₂ bonded to the benzene ring is shown to be 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 1-position, the two bonding positions are preferably the 3-position and the 5-position, or the 2-position and the 5-position.

式（ＤＩ−３１−ａ）において、Ｇ^２７、Ｇ^２８およびＧ^２９は結合基であり、これらは独立して単結合、または炭素数１〜１２のアルキレンであり、このアルキレンの１以上の−ＣＨ_２−は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＣＨ＝ＣＨ−で置き換えられていてもよい。環Ｂ^２１、環Ｂ^２２、環Ｂ^２３および環Ｂ^２４は独立して１，４−フェニレン、１，４−シクロへキシレン、１，３−ジオキサン−２，５−ジイル、ピリミジン−２，５−ジイル、ピリジン−２，５−ジイル、ピペリジン−１，４−ジイル、ナフタレン−１，５−ジイル、ナフタレン−２，７−ジイルまたはアントラセン−９，１０−ジイルであり、環Ｂ^２１、環Ｂ^２２、環Ｂ^２３および環Ｂ^２４において、少なくとも１つの水素は−Ｆまたは−ＣＨ_３で置き換えられてもよく、ｓ、ｔおよびｕは独立して０〜２の整数であって、これらの合計は０〜５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。

In formula (DI-31-a), G ²⁷ , G ^28, and G ²⁹ are linking groups, which are independently a single bond or an alkylene having 1 to 12 carbons, and one or more of these alkylenes are -. CH ₂ - is -O -, - COO -, - OCO -, - CONH -, - it may be replaced by 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 and pyridine-2,5-diyl, piperidine-1,4-diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl or anthracene-9,10-diyl, ring ^{B 21,} ring B ^22, the ring ^{B 23} and ring ^{B 24,} at least one hydrogen may be replaced by -F, or -CH _3, s, t and u is an integer of 0 to 2 independently of The sum is 0-5, when s, t or u is 2, the two linking groups within each bracket 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 alkyl of 1 to 30 carbon atoms - may be replaced by a divalent group represented by the following formula (DI-31-b).

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。

In 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. Preferred examples of R ²⁶ are alkyl having 1 to 30 carbons and alkoxy having 1 to 30 carbons.

In formula (DI-32) and formula (DI-33), G ³⁰ is independently a single bond, —CO— or —CH ₂ —, R ²⁹ is independently hydrogen or —CH ₃ , and R 30 is 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 in which the bonding position is not fixed to any carbon atom forming the ring indicates that the bonding position in the ring is arbitrary. Formula (DI-32) in two groups - one of the "phenylene -G 30 ^-O-" is attached to the 3 position of the steroid nucleus, it is preferable that the other is bound to 6-position of the steroid nucleus. The bonding positions of the two groups “-phenylene-G ³⁰ —O—” in the formula (DI-33) to the benzene ring are preferably meta or para 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 bonding position in the ring is arbitrary.

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

Specific examples of the side chain type diamine are shown below. Examples of the diamine having a side chain of the above formula (DI-31) to formula (DI-35) include compounds represented by the following formula (DI-31-1) to formula (DI-35-3). it can.

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 independently alkyl having 1 to 30 carbons or alkoxy having 1 to 30 carbons, preferably 5 to 25 carbons. Or alkyl having 5 to 25 carbon atoms. R ³⁵ is independently alkyl having 1 to 30 carbons or alkoxy having 1 to 30 carbons, preferably alkyl having 3 to 25 carbons or alkoxy having 3 to 25 carbons.

式（ＤＩ−３１−１２）〜式（ＤＩ−３１−１７）において、Ｒ^３６は独立して炭素数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は独立して炭素数６〜３０のアルキルであり、好ましくは炭素数８〜２５のアルキルである。

In formulas (DI-31-12) to (DI-31-17), R ³⁶ is independently alkyl having 4 to 30 carbons, preferably alkyl having 6 to 25 carbons. R ³⁷ is independently alkyl having 6 to 30 carbons, preferably alkyl having 8 to 25 carbons.

式（ＤＩ−３１−１８）〜式（ＤＩ−３１−４３）において、Ｒ^３８は独立して炭素数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は独立して水素、−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は独立して炭素数１〜２０のアルキレンである。

In formulas (DI-31-18) to (DI-31-43), R ³⁸ is independently alkyl having 1 to 20 carbons or alkoxy having 1 to 20 carbons, preferably 3 to 20 carbons. Or an alkoxy having 3 to 20 carbon atoms. R ³⁹ is independently hydrogen, —F, alkyl having 1 to 30 carbons, alkoxy having 1 to 30 carbons, —CN, —OCH ₂ F, —OCHF ₂ or —OCF ₃ , and preferably 3 carbons. Is alkyl having 25 to 25, or alkoxy having 3 to 25 carbons. G ³³ is independently alkylene having 1 to 20 carbon atoms.

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

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

式（ＤＩ−３４−１）〜式（ＤＩ−３４−１４）において、Ｒ^４０は独立して水素または炭素数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は独立して水素または炭素数１〜１２のアルキルである。 Examples of the compound represented by the formula (DI-34) are shown below.

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

式（ＤＩ−３５−１）〜式（ＤＩ−３５−３）において、Ｒ^３７は独立して炭素数６〜３０のアルキルであり、Ｒ^４１は独立して水素または炭素数１〜１２のアルキルである。 Examples of the compound represented by the formula (DI-35) are shown below.

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

式（ＤＩ−３６−１）〜式（ＤＩ−３６−８）において、Ｒ^４２は独立して炭素数３〜３０のアルキル基を表す。 Examples of the diamine in the present invention include formula (DI-1-1) to formula (DI-16-1), formula (DIH-1-1) to formula (DIH-3-6) and formula (DI-31-1). )-Diamine other than the diamine represented by the formula (DI-35-3) can 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 independently represents an alkyl group having 3 to 30 carbon atoms.

式（ＤＩ−３６−９）〜式（ＤＩ−３６−１１）において、ｅは独立して２〜１０の整数であり、式（ＤＩ−３６−１２）中、Ｒ^４３は独立して水素、−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。

In formula (DI-36-9) to formula (DI-36-11), e is independently an integer of 2 to 10, and in formula (DI-36-12), R ⁴³ is independently hydrogen, a -NHBoc or -N _{(Boc) ^2,} at least one of ^{R 43} is -NHBoc or -N _{(Boc) 2,} 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.

In the above diamine and dihydrazide, suitable materials for improving each property will be described.

In the diamine and dihydrazide used for the polymer using the monomer having a photoisomerization structure, when it is important to further improve the alignment property of the liquid crystal, among the above diamine and dihydrazide, a compound represented by the formula (DI-1- 3), formula (DI-5-1), formula (DI-5-5), formula (DI-5-9), formula (DI-5-12), formula (DI-5-13), formula ( It is preferable to use diamines represented by DI-5-29), formula (DI-6-7), formula (DI-7-3), and formula (DI-11-2). In the formula (DI-5-1), m=2, 4 or 6 is preferable, and m=4 is more preferable. In formula (DI-5-12), m=2 to 6 is preferable, and m=5 is more preferable. In Formula (DI-5-13), m=1 or 2 is preferable, and m=1 is more preferable. In the formula (DI-5-30), k=2 is preferable. In formula (DI-7-3), m=2, 3 or 4, and n=1 or 2 are preferable, and m=3 and n=1 are more preferable.

When importance is attached to improving the transmittance, among the above diamines and dihydrazides, the formula (DI-1-3), the formula (DI-2-1), the formula (DI-5-1), the formula ( DI-5-5), the formula (DI-5-17), and the diamine represented by the formula (DI-7-3) are preferably used, and the diamine represented by (DI-2-1) is more preferable. preferable. In the formula (DI-5-1), m=2, 4 or 6 is preferable, and m=4 is more preferable. In the formula (DI-7-3), m=2 or 3, n=1 or 2 is preferable, and m=3 and n=1 are more preferable.

When importance is placed on improving the VHR of the liquid crystal display element, among the above diamines and dihydrazides, the formula (DI-2-1), the formula (DI-4-1), the formula (DI-4-2) , Formula (DI-4-10), Formula (DI-4-15), Formula (DI-5-1), Formula (DI-5-28), Formula (DI-5-30), Formula (DI- 13-1), the formula (DI-31-56), and the diamine represented by the formula (DI-36-14) are preferably used, and the formula (DI-2-1) and the formula (DI-5-1) are used. ), and the diamine represented by the formula (DI-13-1) are more preferable. In the formula (DI-5-1), m=1 is preferable. In the formula (DI-5-30), k=2 is preferable.

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

In the diamine and dihydrazide used in the polymer that does not use the monomer having a photoisomerization structure, layer separation, that is, in the case where it is important to further improve the orientation of the liquid crystal, among the above diamine and dihydrazide, the formula: (DI-4-1), Formula (DI-4-2), Formula (DI-4-10), Formula (DI-5-1), Formula (DI-5-9), Formula (DI-5- 28) and diamines and dihydrazides of formula (DIH-2-1) are preferably used. In the formula (DI-5-1), m=1, 2 or 4 is preferable, and m=1 or 2 is more preferable.

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

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

Improving the relaxation rate of the residual charge (residual DC) in the alignment film by reducing the volume resistance value of the liquid crystal alignment film is effective as one of the methods for preventing image sticking. When this purpose is emphasized, among the above diamines and dihydrazides, the formula (DI-4-1), the formula (DI-4-2), the formula (DI-4-10), the formula (DI-4-). 15), formula (DI-5-1), formula (DI-5-9), formula (DI-5-12), formula (DI-5-13), formula (DI-5-28), formula ( DI-5-30), the formula (DI-7-12), and the diamine represented by the formula (DI-16-1) are preferably used, and the formula (DI-4-1) and the formula (DI-5) are used. -1) and the diamine represented by the formula (DI-5-12) are particularly preferable. Among them, in the formula (DI-5-1), m=1 or 2 is preferable, in the formula (DI-5-12), m=2 to 6 is preferable, m=5 is particularly preferable, and the formula (DI-5 In -13), m=1 or 2 is preferable, m=1 is particularly preferable, and in the formula (DI-5-30), k=2 is particularly preferable. In the formula (DI-7-12), m=3 or 4 is preferable, and m=4 is more preferable.

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

The polyamic acid and its derivative of the present invention may further contain a monoisocyanate compound in its monomer. By including the monoisocyanate compound in the monomer, the end of the obtained polyamic acid or its derivative is modified and the molecular weight is adjusted. By using this end-modified polyamic acid or its derivative, the coating properties of the liquid crystal aligning agent can be improved without impairing the effects of the present invention. From the above viewpoint, the content of the monoisocyanate compound in the monomer is preferably 1 to 10 mol% with respect to the total amount of the diamine and the tetracarboxylic dianhydride in the monomer. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

The polyamic acid and its derivative 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 are required other than the selection of the raw materials, and the conditions for ordinary polyamic acid synthesis can be applied as they are. The solvent used will be described later.

The liquid crystal aligning agent for photo-alignment of the present invention may further contain components other than the polyamic acid and its derivative of the present invention. The other component may be one type or two or more types. Other components include, for example, other polymers and compounds described later.

Examples of the other polymer include a polyamic acid or a derivative thereof obtained by reacting a raw material monomer having no photoisomerization structure and not containing the tetracarboxylic dianhydride of the formula (I) (hereinafter, referred to as “other polyamic acid”). Or a derivative thereof”), polyester, polyamide, polysiloxane, cellulose derivative, polyacetal, polystyrene derivative, poly(styrene-phenylmaleimide) derivative, poly(meth)acrylate and the like. It may be one kind or two or more kinds. Of these, other polyamic acids or their derivatives and polysiloxanes are preferable, and other polyamic acids or their derivatives are more preferable.

Examples of the tetracarboxylic acid dianhydride used for synthesizing other polyamic acid or its derivative include tetracarboxylic acid dianhydride used for synthesizing polyamic acid or its derivative which is an essential component of the liquid crystal aligning agent of the present invention. The anhydride can be selected from known tetracarboxylic dianhydrides without any limitation, and the same as those exemplified above can be mentioned.

Preferred tetracarboxylic acid dianhydrides include the tetracarboxylic acid dianhydrides used in polymers that do not use the above-mentioned monomer having a photoisomerization structure.

The tetracarboxylic acid dianhydride used for synthesizing the other polyamic acid or its derivative is one containing aromatic tetracarboxylic acid dianhydride in an amount of 10 mol% or more based on the total tetracarboxylic acid dianhydride. Are preferred, and those containing 30 mol% or more are more preferred.

As the diamine and dihydrazide used for synthesizing the other polyamic acid or its derivative, as the 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 can be mentioned.

Preferred diamines and dihydrazides include diamines and dihydrazides used in polymers that do not use the above-mentioned monomer having a photoisomerization structure.

The diamine used for synthesizing the other polyamic acid or its derivative preferably contains aromatic diamine in an amount of 30 mol% or more, and more preferably 50 mol% or more, based on all diamines.

The other polyamic acid or its derivative can be synthesized according to the method described below as a method for synthesizing the polyamic acid or its derivative, which is an essential component of the liquid crystal aligning agent of the present invention.

As described above, in the liquid crystal aligning agent for photo-alignment of the present invention, at least one selected from the group consisting of tetracarboxylic dianhydride and its derivative and diamine has a photoisomerization structure, and The anhydride contains at least one polymer obtained by reacting a raw material monomer containing at least one compound represented by formula (I), or from the group consisting of tetracarboxylic acid and its derivative, and diamine. At least one of the polymers obtained by reacting at least one selected raw material monomer having a photoisomerization structure, tetracarboxylic dianhydride and its derivative, and none of the diamines have a photoisomerization structure, In addition, the liquid crystal aligning agent for photo-alignment, wherein the tetracarboxylic dianhydride simultaneously contains at least one polymer obtained by reacting a raw material monomer containing at least one compound represented by the formula (I).

The liquid crystal aligning agent for photo-alignment of the present invention may contain at least two polymers. Of the two polymers, the polymer having a photoisomerization structure is [A], and the polymer having no photoisomerization structure is [B], the weight average molecular weight of [A] is higher than the weight average molecular weight of [B]. By controlling to a small value, a liquid crystal aligning agent containing a mixture of both polymers is applied to a substrate and preliminarily dried. In the process of forming the polymer film, [A] having a photoisomerized structure is formed in the lower layer in the upper layer. It is considered that [B] having no photoisomerization structure can be segregated. For this reason, the presence of the polymer [A] having a photoisomerization structure is dominant on the surface of the alignment film, and the content of the polymer [A] having a photoisomerization structure is small based on the total amount of the polymers forming the alignment film. However, the alignment film formed by the liquid crystal aligning agent for photo-alignment of the present invention exhibits high liquid crystal aligning property.

It is known that, in the process of forming a thin film using a liquid crystal aligning agent containing two polymers as described above, 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. Whether or not the alignment film is separated into layers can be confirmed by, for example, measuring the surface energy of the formed film, and confirming that it is the same as the value of the surface energy of the film formed by the liquid crystal aligning agent containing only the polymer [A]. , Can be confirmed by the value close to it.

In order to exhibit good photo-alignment properties as described above, the content of [A] in the liquid crystal aligning agent for photo-alignment of the present invention is 20% by weight or more when the total amount of the polymer contained is 100. It is necessary, preferably 30% by weight or more, and more preferably 50% by weight or more. Further, in order to keep the transmittance of the liquid crystal alignment film favorable, the content of [A] needs to be 90% by weight or less, preferably 70% by weight or less, and 50% by weight or less. Is more preferable. However, the preferable content of [A] described here is one guide, and may vary depending on the combination of the tetracarboxylic dianhydride or diamine used as the raw material. In particular, when a raw material compound having the structure of azobenzene is used, the content of [A] is set to be approximately 10 to 20% by weight less than the above-mentioned ratio in order to maintain good permeability.

The weight average molecular weight of the polymer is preferably adjusted by adjusting [A] to 8,000 to 40,000 and [B] to 50,000 to 200,000 so that the molecular weight (MW) of [A] is 10, By adjusting the molecular weight (MW) of [B] to 000 to 30,000 and 80,000 to 160,000, the above-mentioned layer separation can be caused. The weight average molecular weight of the polymer can be adjusted by, for example, the time for reacting the tetracarboxylic dianhydride and the diamine. A small amount of the reaction liquid during the polymerization reaction is sampled, the weight average molecular weight of the polymer contained therein is determined by gel permeation chromatography (GPC) method, and the end point of the reaction can be determined by the measured value. Further, a method of controlling the weight average molecular weight by terminating the polymerization reaction by substituting a considerable amount of tetracarboxylic dianhydride and diamine at the start of the reaction with monocarboxylic acid or monoamine is also well known. ..

The ratio of the component [A] to the total amount of the component [A] and the component [B] is preferably 10% by weight to 100% by weight, and more preferably 20% by weight to 100% by weight.

Examples of the polysiloxane include JP2009-036966, JP2010-185001, JP2011-102963, JP2011-253175, JP2012-159825, International Publication 2008/044644, International Publication 2009/148099, International Publication. Disclosed in 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. It may further contain polysiloxane.

<Alkenyl-substituted nadiimide compound>
For example, the liquid crystal aligning agent of the present invention may further contain an alkenyl-substituted nadimide compound for the purpose of stabilizing the electrical characteristics of the liquid crystal display device for a long period of time. The alkenyl-substituted nadiimide compounds may be used alone or in combination of two or more. From the above-mentioned purpose, the content of the alkenyl-substituted nadiimide compound is preferably 1 to 100% by weight, more preferably 1 to 70% by weight, and further preferably 1 to 50% by weight based on the polyamic acid or its derivative. Is more preferable.

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 its derivative used in the present invention. Examples of such an alkenyl-substituted nadiimide compound include compounds represented by the following formula (NA).

In 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 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 - with ^{_{(Z 2 O) k -Z 3}} -H ( ^wherein, Z 1, ^{Z 2} and ^{Z 3} are independently alkylene of 2 to 6 carbon atoms, r is 0 or 1 and a, and, k is an integer from 1 to 30 groups represented _{^{by), -. (Z 4)}} r -B-Z 5 -H ( wherein, ^{Z 4} and ^{Z 5} carbon atoms independently A group represented by 1 to 4 alkylene or cycloalkylene having 5 to 8 carbon atoms, B is phenylene, and r is 0 or 1, and -B-T-B-H (here). in, B is phenylene, and, T is _{-CH 2 -, - C (CH} 3) 2 -, - O -, - CO -, - S-, or -SO ₂ - is represented by a is). Or a group in which 1 to 3 hydrogens of these groups are replaced 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, Phenyl isopropylidene phenyl, and groups in which one or two hydrogens of these groups have been replaced by -OH.

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

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

Such an alkenyl-substituted nadiimide compound is synthesized by holding 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, for example, Japanese Patent No. 2729565. The compound obtained by this and the compound marketed can be used. Specific examples of the alkenyl-substituted nadiimide compound include the compounds shown below.

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 -Dicarboximide, 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-2,3-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)bicyclo[ 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 , N-(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-hydroxyphenylisopropylidene)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-dicarboxyl) Imido), N,N′-dodecamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide), N,N′-dodecamethylene-bis(allylmethylbicyclo) [2.2.1]Hept-5-ene-2,3-dicarboximide), N,N'-cyclohexylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3 -Dicarboximide), N,N'-cyclohexylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide),

1,2-bis{3'-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide)propoxy}ethane, 1,2-bis{3'-(allylmethylbicyclo [2.2.1]hept-5-ene-2,3-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-dicarboximide)propoxy}ethyl] ether, 1,4-bis{3' -(Allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide)propoxy}butane, 1,4-bis{3'-(allylmethylbicyclo[2.2.1]hept -5-ene-2,3-dicarboximido)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-dicarboximide), 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-dicarboximide)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] 1.2.1]Hept-5-ene-2,3-dicarboximide)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 -(Allylmethylbicyclo[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, 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-dicarboximido)propoxy}-3-hydroxy-pentane, 1,4-bis(allylbicyclo[2.2.1] ] Hept-5-ene-2,3-dicarboximido)-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] 1.2.1]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-dihydroxy)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-dicarboximide)-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(ethylenemethallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide) isocyanurate, and oligomers thereof.

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

Among the alkenyl-substituted nadiimide compounds, preferable 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-dicarboxyl) Imido), 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),

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-dicarboximide), 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-dicarboximide)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 -(Allylmethylbicyclo[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.

More preferable 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-dicarboxyl) Imido), 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),

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-dicarboximide), 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-dicarboximide)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] 1.2.1]Hept-5-ene-2,3-dicarboximide)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] 1.2.1]Hept-5-ene-2,3-dicarboximido)phenyl}methane, bis{4-(methallylmethylbicyclo[2.2.1]hept-5-ene-2,3-di Carboximido)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 Examples include N,N′-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide) represented by the formula (NA-3).

<Compound Having Radical 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 device for a long period of time. The compound having a radical-polymerizable unsaturated double bond may be one kind of compound or two or more kinds of compounds. The compound having a radically polymerizable unsaturated double bond does not include an alkenyl-substituted nadimide compound. From the above-mentioned purpose, 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 based on the polyamic acid or its derivative. It is preferably from 1 to 50% by weight, and further preferably.

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

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

Specific examples of the (meth)acrylic acid ester include cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and dicyclopentanyl (meth)acrylate. And 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 Toagosei Kagaku Kogyo Co., Ltd., Nippon Kayaku Co., Ltd. ) Products KAYARAD HDDA, KAYARADHX-220, KAYARADR-604 and KAYARADR-684, products of Osaka Organic Chemical Co., Ltd. V260, V312 and V335HP, and products of Kyoeisha Oil and Fat Chemical Co., Ltd. light acrylate. BA-4EA, light acrylate BP-4PA and light acrylate BP-2PA are mentioned.

Specific examples of the trifunctional or higher polyfunctional (meth)acrylic acid ester include, for example, 4,4′-methylenebis(N,N-dihydroxyethylene acrylateaniline), Aronix M- which is a product of Toagosei Chemical Industry Co., Ltd. 400, Aronix M-405, Aronix M-450, Aronix M-7100, Aronix M-8030, Aronix M-8060, products of KAYARADTMPTA, KAYARADDPCA-20, KAYARADPDPCA-30, and KAYARADPDPCA-60 manufactured by Nippon Kayaku Co., Ltd. , KAYARADDPCA-120, and VGPT, 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'-methylenebisacrylamide, 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 KI Kasei Co., Ltd., and BMI-1000, BMI-3000, BMI-4000, BMI-5000 and BMI- manufactured by Daiwa Kasei Kogyo Co., Ltd. 7,000 is included.

<Oxazine compound>
For example, the liquid crystal aligning agent of the present invention may further contain an oxazine compound for the purpose of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time. The oxazine compound may be one kind of compound or two or more kinds of compounds. From the above-mentioned purpose, the content of the oxazine compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, and 1 to 20% by weight based on the polyamic acid or its derivative. Is more preferable.

The oxazine compound will be specifically described below.
The oxazine compound is soluble in a solvent that dissolves the polyamic acid or its derivative, 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 of oxazine are known. In the present invention, the structure of oxazine is not particularly limited, but examples of the oxazine structure in the oxazine compound include structures of oxazine having an aromatic group including a condensed polycyclic aromatic group such as benzoxazine and naphthoxazine.

式（ＯＸ−１）〜式（ＯＸ−３）において、Ｌ^３およびＬ^４は炭素数１〜３０の有機基であり、式（ＯＸ−１）〜式（ＯＸ−６）において、Ｌ^５〜Ｌ^８は水素または炭素数１〜６の炭化水素基であり、式（ＯＸ−３）、式（ＯＸ−４）および式（ＯＸ−６）において、Ｑ^１は単結合、−Ｏ−、−Ｓ−、−Ｓ−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−、−（ＣＨ_２）_ｖ−、−Ｏ−（ＣＨ_２）_ｖ−Ｏ−、−Ｓ−（ＣＨ_２）_ｖ−Ｓ−であり、ここでｖは１〜６の整数であり、式（ＯＸ−５）および式（ＯＸ−６）において、Ｑ^２は独立して単結合、−Ｏ−、−Ｓ−、−ＣＯ−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−または炭素数１〜３のアルキレンであり、Ｑ^２におけるベンゼン環、ナフタレン環に結合している水素は独立して−Ｆ、−ＣＨ_３、−ＯＨ、−ＣＯＯＨ、−ＳＯ_３Ｈ、−ＰＯ_３Ｈ_２と置き換えられていてもよい。 Examples of the oxazine compound include compounds represented by the following formulas (OX-1) to (OX-6). In the following formula, the bond shown toward the center of the ring indicates that it is bonded to any carbon that constitutes the ring and is capable of forming a substituent bond.

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 in -6), ^{Q 2} is independently a single bond, -O -, - S -, - CO -, - C (CH 3) 2 -, - C (CF 3) 2 - or 1 to 3 carbon atoms It is alkylene, and the hydrogen bonded to the benzene ring and the naphthalene ring in Q ² is independently replaced with —F, —CH ₃ , —OH, —COOH, —SO ₃ H, and —PO ₃ H _2. Good.

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

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

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

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

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

式（ＯＸ−３−Ｉ）において、Ｌ^３およびＬ^４は炭素数１〜３０の有機基であり、Ｌ^５からＬ^８は水素または炭素数１〜６の炭化水素基であり、Ｑ^１は単結合、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−ＣＯ−、−Ｏ−、−ＳＯ_２−、−Ｃ（ＣＨ_３）_２−、または−Ｃ（ＣＦ_３）_２−である。式（ＯＸ−３−Ｉ）で表されるオキサジン化合物としては、例えば以下のオキサジン化合物が挙げられる。 Examples of the oxazine compound represented by the formula (OX-3) include oxazine compounds represented by the following formula (OX-3-I).

In formula (OX-3-I), L ³ and L ⁴ are organic groups 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 single _{bond, -CH 2 -, - C (} CH 3) 2 -, - CO -, - O -, - SO 2 -, - C (CH 3) 2 -, or -C _{(CF 3) 2} - is .. 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 carbons, and more preferably alkyl having 1 to 20 carbons.

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, formula (OX-2-1), formula (OX-3-1), formula (OX-3-3), formula (OX-3-5), formula (OX-3-). 7), formula (OX-3-9), formula (OX-4-1) to formula (OX-4-6), formula (OX-5-3), formula (OX-5-4), and formula Examples thereof include oxazine compounds represented by (OX-6-2) to formula (OX-6-4).

The oxazine compound can be produced by a method similar to the method described in International Publication 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 with a primary amine and an aldehyde (see International Publication 2004/097008).

The oxazine compound represented by the formula (OX-2) is obtained by reacting a primary amine with formaldehyde gradually and then reacting it with a compound having a naphthol-based hydroxyl group (International Publication 2004/ See 090708.).

The oxazine compound represented by the formula (OX-3) is obtained by adding 1 mol of a phenol compound, at least 2 mol or more of an aldehyde to 1 phenolic hydroxyl group thereof, and 1 mol of a primary amine to a secondary aliphatic compound in an organic solvent. It is obtained by reacting in the presence of an amine, a tertiary aliphatic amine or a basic nitrogen-containing heterocyclic compound (see International Publication 2004/09708 and JP-A No. 11-12258).

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

<Oxazoline compound>
For example, the liquid crystal aligning agent of the present invention may further contain an oxazoline compound for the purpose of stabilizing the electrical characteristics of the liquid crystal display device for a long period of time. The oxazoline compound is a compound having an oxazoline structure. The oxazoline compound may be one kind of compound or two or more kinds of compounds. From the above-mentioned purpose, the content of the oxazoline compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, and 1 to 20% by weight based on the polyamic acid or its derivative. Is more preferable. Alternatively, the content of the oxazoline compound is preferably 0.1 to 40% by weight based on the polyamic acid or its derivative when the oxazoline structure in the oxazoline compound is converted to oxazoline, from the above-mentioned object.

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. The oxazoline compound may have one oxazoline structure in one compound, but preferably has two or more oxazoline structures. The oxazoline compound may be a polymer having an oxazoline structure in its side chain or a copolymer. The polymer having an oxazoline structure in its side chain may be a homopolymer of a monomer having an oxazoline structure in its side chain, or may be a copolymer of a monomer having an oxazoline structure in its side chain and a monomer not having an oxazoline structure. Good. The copolymer having an oxazoline structure in a side chain may be a copolymer of two or more kinds of monomers having an oxazoline structure in a side chain, or two or more kinds of monomers having an oxazoline structure in a side chain and a monomer not having an oxazoline structure. It may be a copolymer with.

The oxazoline structure is preferably a structure present in the oxazoline compound such 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′ -Isopropylidene bis(4-tert-butyl-2-oxazoline), 2,2'-isopropylidene bis(4-phenyl-2-oxazoline), 2,2'-methylenebis(4-tert-butyl-2-oxazoline) ), and 2,2′-methylenebis(4-phenyl-2-oxazoline). In addition to these, polymers and oligomers having oxazolyl such as Epocros (trade name, manufactured by Nippon Shokubai Co., Ltd.) are also included. Of these, more preferable is 1,3-bis(4,5-dihydro-2-oxazolyl)benzene.

<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 device for a long period of time. The epoxy compound may be one kind of compound or two or more kinds of compounds. From the above-mentioned purpose, 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 its derivative. Is more preferable.

The epoxy compound will be specifically described below.
Examples of the epoxy compound include various compounds having one or two or more epoxy rings in the molecule. Examples of compounds having one epoxy ring in the molecule include phenyl glycidyl ether, butyl glycidyl ether, 3,3,3-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'-epoxycyclohexenecarboxylate 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 may be mentioned.

In addition to the above, examples of compounds 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 methylglycidyl (meth)acrylate.

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

Specific preferred examples of the polymer of a monomer having an epoxy ring include polyglycidyl methacrylate. Further, preferred specific examples of the copolymer of a monomer having an epoxy ring and another monomer include N-phenylmaleimide-glycidylmethacrylate copolymer, N-cyclohexylmaleimide-glycidylmethacrylate copolymer, benzylmethacrylate-glycidylmethacrylate copolymer, butylmethacrylate-glycidyl. Mention may be made of methacrylate copolymers, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymers, (3-ethyl-3-oxetanyl)methyl methacrylate-glycidyl methacrylate copolymers and styrene-glycidyl methacrylate copolymers.

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′-epoxycyclohexenecarboxylate, 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 cycloaliphatic epoxy compound. Is mentioned. The epoxy compound means a compound having an epoxy group, and the epoxy resin means a resin having an epoxy group.

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

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

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

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

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

Examples of glycidyl amides include glycidyl amide type epoxy compounds.

Examples of the chain aliphatic epoxy compound include a compound having an epoxy group, which is obtained by oxidizing a carbon-carbon double bond of an alkene compound.

Examples of the cycloaliphatic epoxy compound include a compound having an epoxy group, which is 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 are trade names, manufactured by Mitsubishi Chemical Corporation), Epotote YD-128 (manufactured by Tohto Kasei Co., Ltd.), DER. -331, DER-332, DER-324 (all manufactured by The Dow Chemical Company), Epiclon 840, Epiclon 850, Epiclon 1050 (all trade names, manufactured by DIC Corporation), Epomic R-140, Epomic R-301. , And Epomic R-304 (both are trade names, manufactured by Mitsui Chemicals, Inc.).

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

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

Examples of the hydrogenated bisphenol-A type epoxy compound include Santoto ST-3000 (trade name, manufactured by Tohto Kasei Co., Ltd.), Licaredin HBE-100 (trade name, manufactured by Shin Nippon Rika Co., Ltd.), and Denacol EX-252. (Trade name, manufactured by Nagase Chemtex Co., Ltd.).

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

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

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

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

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

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

Examples of the aromatic polyglycidyl ether compound include hydroquinone diglycidyl ether (the following formula EP-1), catechol diglycidyl ether (the following formula EP-2), resorcinol diglycidyl ether (the following formula EP-3), and 2-[4 -(2,3-Epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-([2,3-epoxypropoxy]phenyl)]ethyl]phenyl]propane (the following formula EP-4) , Tris(4-glycidyloxyphenyl)methane (the following formula EP-5), jER1031S, jER1032H60 (all are trade names, manufactured by Mitsubishi Chemical Corporation), TACTIX-742 (trade name, manufactured by The Dow Chemical Company), Denacol EX-201 (trade name, manufactured by Nagase Chemtex Co., Ltd.), DPPN-503, DPPN-502H, DPPN-501H, NC6000 (all are trade names, manufactured by Nippon Kayaku Co., Ltd.), Techmore VG3101L (trade name, Mitsui Chemicals, Inc.), a compound represented by the following formula EP-6, and a compound represented by the following formula EP-7.

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

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

Examples of the aliphatic polyglycidyl ether compound include ethylene glycol diglycidyl ether (the following formula EP-8), diethylene glycol diglycidyl ether (the following formula EP-9), polyethylene glycol diglycidyl ether, and propylene glycol diglycidyl ether (the 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 (the following formula EP-14), dibromoneopentyl glycol diglycidyl ether (the 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 are trade names, manufactured by Nagase ChemteX Corporation), DD-503 ( Trade name, manufactured by ADEKA Co., Ltd., Lycarezin W-100 (trade name, manufactured by Shin Nippon Rika Co., Ltd.), 1,3,5,6-tetraglycidyl-2,4-hexanediol (following formula EP-16) ), glycerin polyglycidyl ether, sorbitol polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, Denacol EX-313, Denacol EX-611, Denacol EX-321, and Denacol EX-411 (all are trade names. , Nagase Chemtex Co., Ltd.).

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

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

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

Examples of the glycidyl ester epoxy compound include jER871 and jER872 (both are trade names, manufactured by Mitsubishi Chemical Corporation), Epicron 200, epicron 400 (both are trade names, manufactured by DIC Corporation), Denacol EX-711, and Denacol. EX-721 (trade name, manufactured by Nagase Chemtex Co., Ltd.) can be used.

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

Examples of homopolymers of oxiranyl-containing monomers include polyglycidyl methacrylate. Examples of the copolymer of monomers having oxiranyl include N-phenylmaleimide-glycidylmethacrylate copolymer, N-cyclohexylmaleimide-glycidylmethacrylate copolymer, benzylmethacrylate-glycidylmethacrylate copolymer, butylmethacrylate-glycidylmethacrylate copolymer, 2-hydroxyethylmethacrylate-glycidylmethacrylate. Copolymers, (3-ethyl-3-oxetanyl)methylmethacrylate-glycidylmethacrylate copolymers, and styrene-glycidylmethacrylate copolymers.

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

Examples of the monomer other than the oxiranyl-containing monomer in the copolymer of oxiranyl-containing monomers include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, and the like. iso-butyl (meth)acrylate, t-butyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, styrene, 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 (the following formula EP-51), and glycidyl isocyanurate type epoxy resin.

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

Examples of the cycloaliphatic epoxy compound include 3,4-epoxycyclohexenylmethyl-3′,4′-epoxycyclohexenecarboxylate (Celoxide 2021 (manufactured by Daicel Corp.), the following formula EP-52), and 2-methyl. -3,4-Epoxycyclohexylmethyl-2'-methyl-3',4'-epoxycyclohexylcarboxylate (the following formula EP-53), 2,3-epoxycyclopentane-2',3'-epoxycyclopentane ether (The following formula EP-54), ε-caprolactone-modified 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarbochelate, 1,2:8,9-diepoxylimonene (celoxide 3000 (trade name, ( (Manufactured by Daicel Co., Ltd.), the following formula EP-55), compounds represented by the following formula EP-56, CY-175, CY-177, and CY-179 (all are trade names, manufactured by The Ciba-Geigy Chemical Corp. ( Huntsman Japan KK)), EHPD-3150 (trade name, manufactured by Daicel Corporation), and a cycloaliphatic epoxy resin.

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 cycloaliphatic epoxy compound, and N,N,N′,N′-tetraglycidyl. -M-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, trade name "Techmore VG3101L" , 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate, N-phenylmaleimide-glycidyl methacrylate copolymer, N,N,O-triglycidyl-p-aminophenol, bisphenol A novolac type epoxy compound , And one or more of cresol novolac type epoxy compounds are more preferable.

Further, for example, the liquid crystal aligning agent of the present invention may further contain various additives. Examples of 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 may be a polymer compound 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 the orientation of the liquid crystal aligning 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 for the purpose of improving the coating property, 2) an antistatic agent for improving the antistatic property, and 3) adhesion to the substrate. A silane coupling agent or a titanium-based coupling agent may be used to improve the properties, and 4) an imidization catalyst may be used to promote imidization at low temperature.

Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyltrisilane. 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. The preferred silane coupling agent is 3-aminopropyltriethoxysilane.

Examples of the imidization catalyst 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. Cyclic amines such as pyridine, methyl-substituted pyridine, hydroxy-substituted pyridine, quinoline, methyl-substituted quinoline, hydroxy-substituted quinoline, isoquinoline, methyl-substituted isoquinoline, hydroxy-substituted isoquinoline, imidazole, methyl-substituted imidazole, hydroxy-substituted imidazole, etc. .. The imidization catalyst may be one or more selected from N,N-dimethylaniline, o-,m-,p-hydroxyaniline, o-,m-,p-hydroxypyridine, and isoquinoline. preferable.

The 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 addition amount of the imidization catalyst is usually 0.01 to 5 equivalents, and preferably 0.05 to 3 equivalents, relative to the carbonyl group of the polyamic acid or its derivative.

The amount of the other additives added 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 its derivative.

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

The molecular weight of the polyamic acid or its derivative of the present invention is preferably 7,000 to 500,000, and 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 its derivative can be determined by measurement by gel permeation chromatography (GPC) method.

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

Further, for example, the liquid crystal aligning agent of the present invention may further contain a solvent from the viewpoint of adjusting the coating property of the liquid crystal aligning agent and the concentration of the polyamic acid or its derivative. The solvent can be applied without particular limitation as long as it is a solvent capable of dissolving a polymer component. The solvent includes a wide range of solvents that are usually used in the manufacturing process and application of polymer components such as polyamic acid and soluble polyimide, and can be appropriately selected according to the purpose of use. The solvent may be one kind or a mixed solvent of two or more kinds.

Examples of the solvent include a hydrophilic solvent for the polyamic acid or its derivative, and another solvent for improving the coating property.

Examples of the aprotic polar organic solvent which is a hydrophilic solvent for polyamic acid or its derivative include N-methyl-2-pyrrolidone, dimethylimidazolidinone, N-methylcaprolactam, N-methylpropionamide, and N,N-dimethylacetamide. And lactones such as dimethyl sulfoxide, N,N-dimethylformamide, N,N-diethylformamide, diethylacetamide, and γ-butyrolactone.

Examples of other solvents for the purpose of improving coatability include alkyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, ethylene glycol monoalkyl ethers such as ethylene glycol monobutyl ether, and diethylene glycol monoethyl ether. Propylene glycol monoalkyl ether such as diethylene glycol monoalkyl ether, ethylene glycol monoalkyl ether or phenyl acetate, triethylene glycol monoalkyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dialkyl malonate such as diethyl malonate, dipropylene glycol monomethyl ether Examples include dipropylene glycol monoalkyl ethers such as ethers and ester compounds such as acetates.

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.

Further, when the coating film is printed by the inkjet method, the above-mentioned solvent and another solvent for the purpose of improving the coating property can be appropriately selected. By using the following first solvent to fourth solvent in combination, a liquid crystal aligning agent having more excellent coatability can be obtained.

As the first solvent, at least one selected from the group consisting of N-methyl-2-pyrrolidone, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone and N-ethyl-2-pyrrolidone, and the second solvent , Butyl cellosolve, 1-butoxy-2-propanol, diethylene glycol ethyl methyl ether, diethylene glycol propyl methyl ether, at least one selected from the group consisting of diisobutyl ketone, dipentyl ether, diethylene glycol diethyl ether as the third solvent It is preferable that at least one selected from the group consisting of diethylene glycol ethyl propyl ether, diethylene glycol butyl methyl ether, and diethylene glycol butyl ethyl ether be contained as the fourth solvent. The ratio is 20 to 89% by weight based on the total solvent weight, the ratio of the second solvent is 10 to 60% by weight based on the total solvent weight, and the ratio of the third solvent is 0. More preferably, it is 1 to 15% by weight, and the proportion of the fourth solvent is 0.1 to 20% by weight, based on the total weight of the solvent.

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

The solid content concentration in the liquid crystal aligning agent for photo-alignment of the present invention is not particularly limited, and an optimum value may be selected according to various coating methods described below. Usually, it is preferably 0.1 to 30% by weight, more preferably 1 to 10% by weight based on the weight of the varnish in order to suppress unevenness and pinholes during coating.

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 its derivative, the type of the polyamic acid or its derivative used, the type and ratio of the solvent. For example, in the case of coating with a printing machine, it is 5 to 100 mPa·s (more preferably 10 to 80 mPa·s). If it is less than 5 mPa·s, it may be difficult to obtain a sufficient film thickness, and if it exceeds 100 mPa·s, printing unevenness may increase. In the case of coating by spin coating, 5 to 200 mPa·s (more preferably 10 to 100 mPa·s) is suitable. When coating using an inkjet coating device, 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, for example, using a rotational viscometer (TVE-20L type manufactured by Toki Sangyo) (measurement temperature: 25° C.).

The liquid crystal alignment film of the present invention will be described in detail. The liquid crystal alignment film of the present invention is a film formed by heating the coating film of the liquid crystal alignment agent of the present invention described above. The liquid crystal alignment film of the present invention can be obtained by a usual method for producing a liquid crystal alignment film from a liquid crystal alignment agent. For example, the liquid crystal alignment film of the present invention can be obtained by the steps of forming a coating film of the liquid crystal aligning agent of the present invention, heating and drying, and heating and baking. As for the liquid crystal alignment film of the present invention, anisotropy may be imparted by rubbing the film obtained through the heating and drying process and the heating and baking process, as described later, if necessary. Alternatively, if necessary, anisotropy may be imparted by irradiating light after the coating step and heat drying step, or by irradiating light after the heat baking step. It may also be used as a VA liquid crystal alignment film that is not subjected to rubbing treatment.

The coating film can be formed by applying the liquid crystal aligning agent of the present invention to a substrate in a liquid crystal display device, as in the case of producing a normal liquid crystal aligning film. Examples of the substrate include a glass substrate that may be provided with electrodes such as ITO (Indium Tin Oxide), IZO (In ₂ O ₃ —ZnO), and IGZO (In—Ga—ZnO ₄ ) electrodes and a color filter. ..

The spinner method, the printing method, the dipping method, the dropping method, the inkjet method and the like are generally known as methods for applying the liquid crystal aligning agent to the substrate. These methods are similarly applicable to the present invention.

In 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, etc. are generally known. The heating and drying step is preferably carried out at a temperature within the range where the solvent can be evaporated, and more preferably at a temperature relatively lower than the temperature in the heating and baking step. Specifically, the heating and drying temperature is preferably in the range of 30°C to 150°C, and more preferably in the range of 50°C to 120°C.

The heating and firing step can be performed under the conditions necessary for the polyamic acid or its derivative to undergo a dehydration/ring-closing reaction. 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, etc. are generally known. These methods are similarly applicable to the present invention. Generally, it is preferably carried out at a temperature of about 100 to 300° C. for 1 minute to 3 hours, more preferably 120 to 280° C., further preferably 150 to 250° C. In addition, heating and baking can be performed a plurality of times at different temperatures. A plurality of heating devices set to different temperatures may be used, or one heating device may be used while sequentially changing to different temperatures. When the heating and firing are performed twice at different temperatures, it is preferable that the first heating is performed at 90 to 180° C. and the second heating is performed at a temperature of 185° C. or higher.

In the method for forming a liquid crystal alignment film of the present invention, a rubbing method or a photo-alignment method is known 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. The forming method of can be preferably used.

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

The rubbing treatment can be performed in the same manner as the usual rubbing treatment for the alignment treatment of the liquid crystal alignment film, and may be carried out under the condition that sufficient retardation can be obtained in the liquid crystal alignment film of the present invention. 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 rotating 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, after heating and drying the coating film, imparts anisotropy to the coating film by irradiating it with linearly polarized light or unpolarized light, and heat-bakes the film. Can be formed. Alternatively, the coating film can be formed by heating and drying the coating film, baking it by heating, and then irradiating it with linearly polarized light or unpolarized light. From the viewpoint of orientation, it is preferable to perform the radiation irradiation step before the heating and firing step.

Further, in order to improve the liquid crystal aligning ability of the liquid crystal aligning film, it is possible to irradiate linearly polarized light or non-polarized light while heating the coating film. The irradiation of radiation may be performed in the step of heating and drying the coating film, or in the step of heating and firing, or may be performed between the heating and drying step and the heating and firing step. The heat 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. The heating and firing temperature in this step is preferably in the range of 30°C to 300°C, and more preferably in the range of 50°C to 250°C.

As the radiation, for example, ultraviolet rays containing light with a wavelength of 150 to 800 nm or visible light can be used, but ultraviolet rays containing light with a wavelength of 300 to 400 nm is preferable. Further, linearly polarized light or non-polarized light can be used. The light is not particularly limited as long as it can impart liquid crystal aligning ability to the coating film, but linear polarization is preferable when it is desired to exert a strong alignment regulating force on the liquid crystal.

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

The light with which the film is irradiated when a pretilt angle is desired to be expressed 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 It is preferably 400 nm, particularly preferably 300 to 380 nm. The irradiation angle of the light with which the film is irradiated onto the surface of the film when a pretilt angle is desired to be expressed is not particularly limited, but is preferably 30 to 60 degrees from the viewpoint of shortening the alignment treatment time.

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

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

Examples of the cleaning method using the cleaning liquid include brushing, jet spraying, steam cleaning, ultrasonic cleaning and the like. These methods may be used alone or in combination. As the cleaning liquid, pure water or various alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol, aromatic hydrocarbons such as benzene, toluene and xylene, halogen solvents such as methylene chloride, ketones such as acetone and methyl ethyl ketone are used. It can be used, but is not limited thereto. Of course, as these cleaning liquids, those which are sufficiently purified and contain few impurities are used. Such a cleaning method can be applied to the cleaning step in forming 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, heat or light annealing treatment can be used before and after the heating and baking step, before and after the rubbing step, or before and after irradiation with polarized or unpolarized 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. The annealing light used for the annealing treatment may be a UV lamp, a fluorescent lamp, an LED lamp or the like. The light irradiation amount is preferably 0.3 to 10 J/cm ² .

The thickness of the liquid crystal alignment film of the present invention is not particularly limited, but is preferably 10 to 300 nm, more preferably 30 to 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 characterized by having a particularly large anisotropy of alignment. The magnitude of such anisotropy can be evaluated by the method using polarized IR described in JP-A-2005-275364. It can also be evaluated by a method using ellipsometry as shown in the following examples. Specifically, the retardation value of the liquid crystal alignment film can be measured with 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 larger anisotropy is considered to have a large alignment regulating force with respect to the liquid crystal composition.

The liquid crystal alignment film of the present invention can be suitably used for a horizontal electric field type liquid crystal display device. 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 higher the contrast. The Pt angle is preferably 0.1° or less.

The liquid crystal alignment film of the present invention can be used to control the alignment of liquid crystal compositions for liquid crystal displays such as smartphones, tablets, in-vehicle monitors, and televisions. Further, the liquid crystal alignment film of the present invention can be used not only for the purpose of aligning a liquid crystal composition for a liquid crystal display but also for controlling the alignment of an optical compensating material and all other liquid crystal materials. Further, since the alignment film of the present invention has a large anisotropy, it can be used alone as an optical compensator.

The liquid crystal display element of the present invention will be described in detail.
According to the present invention, a pair of substrates arranged to face each other, an electrode formed on one or both of the facing surfaces of each of the pair of substrates, and an electrode formed on the facing surface of each of the pair of substrates. A liquid crystal display element having the above-mentioned liquid crystal alignment film 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 an electrode include an ITO film and a metal vapor deposition film. 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 the electrodes differs depending on the type of liquid crystal display element. For example, in the case of an IPS type liquid crystal display element, the electrodes are arranged on one of the pair of substrates, and in the case of other liquid crystal display elements, the pair of substrates is formed. Electrodes are arranged on both sides. The liquid crystal alignment film is formed on the substrate or the electrode.

The liquid crystal layer is formed such that the liquid crystal composition is sandwiched between the pair of substrates whose surfaces on which the liquid crystal alignment film is formed face each other. In the formation of the liquid crystal layer, spacers such as fine particles and a resin sheet that intervene between the pair of substrates and form an appropriate space 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 JP3086228, JP2635435, JP-A-5-501735, JP-A-8-157526, JP-A-8-231960, JP-A-9-241644 (EP885272A1), and JP Kaihei 9-302346 (EP806466A1), JP-A-8-199168 (EP722998A1), JP-A-9-235552, JP-A-9-255556, JP-A-9-241643 (EP885271A1), JP-A-10-201416 (EP844229A1), JP-A-10-19984. The liquid crystal compositions disclosed in, for example, -204436, JP-A-10-231482, JP-A-2000-087040, and JP-A-2001-48822 are mentioned.

There is no problem in using one or more optically active compounds added to a liquid crystal composition having a positive or negative dielectric anisotropy.

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

Here, R ^1a and R ^2a are each independently an alkyl having 1 to 12 carbons, an alkoxy having 1 to 12 carbons, an alkenyl having 2 to 12 carbons, or a carbon number in which at least one hydrogen is replaced by fluorine. 2-12 alkenyl, wherein 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, or 7,8-difluorochroman-2,6-diyl, where ring A ² and ring At least one of B ² is 2,3-difluoro-1,4-phenylene, 2-fluoro-3-chloro-1,4-phenylene, 2,3-difluoro-6-methyl-1,4-phenylene, or 7,8 difluoromethoxy chroman-2,6-diyl, ^{Z 1} is independently a single _{bond, - (CH 2) 2 -} , - CH 2 O -, - COO-, or _-CF 2 O-a and , J is 1, 2, or 3, and when j is 2 or 3, any two rings A ² may be the same or different, and any two Z ¹ are the same. May also be different.

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

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

Preferable j is 1 for decreasing the minimum temperature and 2 for increasing the maximum temperature.

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

Here, R ^1a and R ^2a are each 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, and ring A ²¹ , ring A ²² , ring A ²³ , ring B ²¹ , and ring B ²² are independently 1,4-cyclohexylene or 1,4-phenylene, and Z ¹¹ and Z ¹² are independently a single bond, —(CH ₂ ) ₂ —, —CH ₂ O—, or —COO—.

Preferable R ^1a and R ^2a are alkyl having 1 to 12 carbons for increasing stability against ultraviolet rays or heat, or alkoxy having 1 to 12 carbons for increasing 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, It is 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 the alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl and 3-hexenyl for decreasing the viscosity. Cis is preferable in the alkenyl such as 2-butenyl, 2-pentenyl and 2-hexenyl. Among these alkenyls, linear alkenyl is preferable to branched one.

Preferred examples of alkenyl in which at least one hydrogen has been 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. More preferable examples are 2,2-difluorovinyl and 4,4-difluoro-3-butenyl for decreasing the viscosity.

Preferred 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.

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

The compound (NL-1) preferable as the first component in the liquid crystal composition having the negative dielectric anisotropy is compound (NL-1-1), (NL-1-4), (NL-1-). 7) or (NL-1-32).

Preferable examples of the liquid crystal composition having the negative dielectric anisotropy include JP-A-57-114532, JP-A-2-4725, JP-A-4-224885, JP-A-8-40953, and 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 (EP9672661A1), JP-A-10-287874, JP-A-10-287875, and JP-A-10-287875. 10-291945, JP-A-11-029581, JP-A-11-080049, JP-A-2000-256307, JP-A-2001-019965, JP-A-2001-072626, JP-A-2001-192657, JP-A-2010-037428, International Publication 2011/ The liquid crystal compositions disclosed in 024666, International Publication 2010/072370, Japanese Patent Laid-Open No. 2010-537010, JP 2012-077201, JP 2009-084362 and the like can be mentioned.

Further, for example, the liquid crystal composition used for 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, defoamers, polymerization initiators, polymerization inhibitors and the like.

The most preferable structure of the photopolymerizable monomer or oligomer for the purpose of improving the orientation of the liquid crystal includes the structures of formulas (PM-1-1) to (PM-1-6).

The photopolymerizable monomer or oligomer is preferably 0.01% by weight or more in order to exert 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 to prevent the unreacted monomer or oligomer from eluting into the liquid crystal after irradiation with ultraviolet rays, it 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% by weight to 2% by weight.

In order to prevent a decrease in the 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 preferable example of the antioxidant is a compound (AO-1) in which w is an integer of 1 to 10. In compound (AO-1), preferable w is 1, 3, 5, 7, or 9. More desirable w is 1 or 7. Since the compound (AO-1) in which w is 1 is highly volatile, it is effective in preventing a decrease in specific resistance due to heating in the atmosphere. The compound (AO-1) in which w is 7 is small in volatility, and therefore is effective in maintaining a large voltage holding ratio not only at room temperature but also at high temperature after using the device for a long time. The preferable ratio of the antioxidant is 50 ppm or more for obtaining the effect, and 600 ppm or less so as not to lower the upper limit temperature or to raise the lower limit temperature. A more desirable ratio is in the range of 100 ppm to 300 ppm.

Preferred examples of the ultraviolet absorber are benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Light stabilizers such as sterically hindered amines are also preferred. The preferable ratio of these absorbents and stabilizers is 50 ppm or more for obtaining the effect, and 10,000 ppm or less so as not to lower the upper limit temperature or to raise the lower limit 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 suit a GH (Guest host) mode device. A desirable ratio of the dye is in the range of 0.01% by weight to 10% by weight.

An antifoaming agent such as dimethyl silicone oil or methylphenyl silicone oil is mixed with the composition to prevent foaming. The preferable ratio of the defoaming agent is 1 ppm or more for obtaining the effect, and 1000 ppm or less for preventing display defects. 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 adjust to a device of PSA (polymer sustained alignment) mode. Preferred examples of the polymerizable compound are compounds having a polymerizable group such as acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxirane, oxetane) and vinyl ketone. Particularly preferred examples are acrylate or methacrylate derivatives. Examples of such compounds are the compound (PM-2-1) to the compound (PM-2-9). The preferable ratio of the polymerizable compound is about 0.05% by weight or more for obtaining the effect, and about 10% by weight or less for preventing display failure. 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 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 independently 0, 1, or 2.

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

In a radical polymerization system, mixing a polymerization inhibitor for the purpose of rapidly reacting with a radical generated from a polymerization initiator or a monomer to change to a stable radical or a neutral compound, and as a result, to terminate the polymerization reaction. You can Polymerization inhibitors are classified into some structures. One is a stable radical such as tri-p-nitrophenylmethyl, di-p-fluorophenylamine, etc., and the other is a stable radical that easily reacts with a radical existing in the polymerization system. The representative ones are nitro, nitriso, amino, and polyhydroxy compounds. Typical examples of the latter include hydroquinone and dimethoxybenzene. The preferred ratio of the polymerization inhibitor is 5 ppm or more to obtain the effect, and 1000 ppm or less to prevent display defects. A more desirable ratio is in the range of 5 ppm to 500 ppm.

By using a liquid crystal composition having a 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.

1. Weight average molecular weight (Mw)
The weight average molecular weight of the polyamic acid was measured by the GPC method using a 2695 Separation Module/2414 Differential Refractometer (manufactured by Waters) and determined by converting to polystyrene. 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. As the column, HSPgel RT MB-M (manufactured by Waters) was used, and the mixed solution was used as a developing agent, and the measurement was performed at a column temperature of 50° C. and a flow rate of 0.40 mL/min. As the standard polystyrene, TSK standard polystyrene manufactured by Tosoh Corporation was used.
2. Alignment Film Retardation and Film Thickness Measurement It was measured using a spectroscopic ellipsometer M-2000U (manufactured by JA Woollam 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, a material having a large retardation value has a large degree of orientation. It can be said that the single-layer photo-alignment film has a liquid crystal alignment property of 20 nm or more and the blend-type photo-alignment film of 5.0 nm or more has a high liquid crystal alignment property.
3. Residual DC
A DC voltage of 5 V was applied to a liquid crystal display element described later for 15 minutes, short-circuited for 1 second, and residual DC after release for 15 minutes was measured. The values are taken at the initial stage and after relaxation for 15 minutes. The initial value is the voltage remaining in the cell, which is the maximum value. The measurement temperature was 60°C. A liquid crystal physical property measurement system 6254 type manufactured by Toyo Technica was used as a measuring device. The smaller the initial value of the residual DC is, and the larger the value after relaxation for 15 minutes is from the initial value, the smaller the residual DC is accumulated, and the relaxation time can be shortened. It can be said that the occurrence of an afterimage can be prevented when the initial value is 500 mV or less and the value after relaxation for 15 minutes is 70 mV or less.
4. Seal Adhesion The sample for seal adhesion measurement described later is fixed to the table-top precision universal testing machine AGS-X 500N manufactured by Shimadzu Corporation with the ends of the upper and lower substrates pressed in from the upper center of the substrate, and the pressure for peeling ( N) was measured. Then, the seal adhesion was evaluated using a value obtained by normalizing the pressure (N) with the area (cm ² ) estimated from the measured diameter of the sealing agent. It can be said that the seal adhesion is good when it is 50 N/cm 2 or more.

<Tetracarboxylic acid dianhydride>

<Diamine>

<Solvent>
NMP: N-methyl-2-pyrrolidone BC: Butyl cellosolve (ethylene glycol monobutyl ether)
GBL: γ-butyrolactone EDE: diethylene glycol diethyl ether DIBK: diisobutyl ketone BP: 2-butoxypropanol BDM: diethylene glycol butyl methyl ether

<Additive>
Additive (Ad1): N,N,N',N'-Tetraglycidyl-4,4'-diaminodiphenylmethane Additive (Ad2): Addition of 1,3-bis(4,5-dihydro-2-oxazolyl)benzene Agent (Ad3): 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane

[Synthesis Example 1] 1.578 g of the compound represented by the formula (V-2-1) and the formula (DI-5-1) (m =4) 1.787 g of the compound represented by the formula (4) was added, and 34.0 g of N-methyl-2-pyrrolidone was added. The solution was cooled to 5°C in an ice bath, 2.634 g of the compound represented by the formula (I-2) was added, and the mixture was stirred at room temperature for 12 hours. 30.0 g of γ-butyrolactone and 30.0 g of butyl cellosolve were added thereto, and the solution was heated and stirred at 60° C. until the weight average molecular weight of the polymer of the solute reached a desired weight average molecular weight, and the weight average molecular weight of the solute was A varnish 1 having a resin content of about 25,000 and a resin content of 6% by weight was obtained.

[Synthesis examples 2 to 19]
Varnishes 2 to 19 having a polymer solid concentration of 6% by weight were prepared according to Synthesis Example 1 except that the tetracarboxylic dianhydride and the diamine were changed. The weight average molecular weight was adjusted to about 22,000 to 26,000 for the polymer using the raw material having the photoisomerization structure and 45,000 to 50,000 for the polymer not using the raw material having the photoisomerization structure. The weight average molecular weights of the used tetracarboxylic dianhydride and diamine and the obtained polymer are shown in Table 1-1 to Table 1-3. Synthesis Example 1 is also listed in Table 1-1.

<Preparation of Single Layer Liquid Crystal Alignment Agent, Preparation and Measurement of Retardation Measurement Substrate>
[Example 1]
Liquid crystal aligning agent 1 was prepared by adding a mixed solvent of NMP/BC=1/1 (weight ratio) to Varnish 1 having a polymer solid content concentration of 6% by weight and diluting it to a polymer solid content concentration of 4% by weight. The liquid crystal aligning agent was applied to a glass substrate with a spinner (Mikasa Co., Ltd., spin coater (1H-DX2)). In addition, including the following examples and comparative examples, the rotation speed of the spinner was adjusted according to the viscosity of the liquid crystal aligning agent so that the liquid crystal aligning film had the following thickness. After applying the liquid crystal aligning agent 1, it was heated and dried at 70° C. for 80 seconds on a hot plate (EC hot plate (EC-1200N, manufactured by As One Co., Ltd.)), and Multilight ML-501C/B manufactured by USHIO INC. was used. The substrate was irradiated with linearly polarized ultraviolet rays from the vertical direction through a polarizing plate. The exposure energy at this time is 5.0±0.1 J/cm ² at a wavelength of 365 nm by measuring the light amount using a UVT photometer UIT-150 (light receiver UVD-S365) manufactured by USHIO INC. So that the exposure time was adjusted. The irradiation of ultraviolet rays was carried out in the air at room temperature by covering the entire apparatus with an ultraviolet ray prevention film. Then, in a clean oven (Clean oven (PVHC-231) manufactured by Espec Corporation), heat treatment was performed at 230° C. for 15 minutes to form an alignment film having a film thickness of 100±10 nm. When the retardation of the obtained substrate was measured, it was 23.2 nm.

[Examples 2 to 11] [Comparative examples 1 and 2]
Also in the varnish 2 to the varnish 13 having a polymer solid content concentration of 6% by weight, a mixed solvent of NMP/BC=1/1 (weight ratio) was added, respectively, and diluted to a polymer solid content concentration of 4% by weight to obtain a liquid crystal aligning agent 2 to 2. The liquid crystal aligning agent 13 was used. Using the obtained liquid crystal aligning agent, a measurement substrate was prepared by the method according to Example 1, and the retardation was measured. The results of Example 1 are shown together in Tables 2-1 and 2-2.

<Preparation of residual DC measurement cell using single-layer liquid crystal aligning agent and residual DC measurement>
[Example 12]
The liquid crystal aligning agent 1 prepared in Example 1 was applied to a glass substrate with an ITO electrode by a spinner (Mikasa Co., Ltd., spin coater (1H-DX2)) (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. Was irradiated with linearly polarized light. The exposure energy at this time is 1.3±0.1 J/cm ² at a wavelength of 365 nm by measuring the light amount using a UVT photometer UIT-150 (light receiver: UVD-S365) manufactured by USHIO INC. The exposure time was adjusted so that Then, a baking treatment was performed at 230° C. for 20 minutes to form a liquid crystal alignment film having a film thickness of about 100 nm. Two substrates on which these liquid crystal alignment films are formed are attached so that the surfaces on which the liquid crystal alignment films are formed face each other and a space for injecting a liquid crystal composition is provided between the opposing liquid crystal alignment films. I matched it. At this time, the polarization directions of the linearly polarized light irradiated on the respective liquid crystal alignment films were made parallel. The positive type liquid crystal composition A was injected into these cells to prepare a liquid crystal cell (liquid crystal display element) having a cell thickness of 7 μm.

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

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

When the residual DC was measured by the method described above using the liquid crystal display device produced above, the initial value of the residual DC was 452 mV and the value after relaxation for 15 minutes was 34 mV.

[Examples 13 to 22] [Comparative examples 3 and 4]
A liquid crystal cell was prepared and residual DC was measured according to Example 12 except that the varnish used was changed. The measurement results are shown in Table 3-1 and Table 3-2 together with Example 12.

In all the cells of Examples 12 to 22, the initial value was small, and the value after relaxation for 15 minutes was also greatly attenuated, and it was confirmed that the occurrence of an afterimage could be suppressed. In the cells of Comparative Examples 3 and 4, the initial value was 500 mV or more, and the value after relaxation for 15 minutes was 100 mV or more, and the target afterimage characteristics could not be achieved.

<Production and Evaluation of Seal Adhesion Evaluation Cell Using Single-Layer Liquid Crystal Alignment Agent>
[Example 23]
Two substrates prepared by using the liquid crystal aligning agent 1 in Example 1 were prepared, 4 μm bead spacers were sprayed on the liquid crystal aligning film surface of one substrate, and then a sealing agent (XN-1500T manufactured by Kyoritsu Kagaku) was used. Dropped. Next, the liquid crystal alignment film surface of the other substrate was placed inside, and bonding was performed so that the overlapping width of the substrates was 1 cm. At that time, the amount of the sealing agent dropped was adjusted so that the diameter of the sealing agent after bonding was about 3 mm. After fixing the two bonded substrates with a clip, they were heat-cured at 120° C. for 1 hour to prepare a sample for evaluation of seal adhesion. The seal adhesion was evaluated using the above measuring method.

[Examples 24 to 33] [Comparative Examples 5 and 6]
A seal adhesion evaluation sample was prepared and the seal adhesion was evaluated in accordance with Example 23, except that the substrates prepared in Examples 2 to 12 and Comparative Examples 1 and 2 were used. The measurement results are shown in Table 4-1 and Table 4-2 together with that of Example 23.

In Examples 23 to 33, the seal adhesiveness was 70 N/cm ² or more, and it was found that the liquid crystal aligning agents 1 to 11 have high adhesiveness. On the other hand, in Comparative Examples 5 and 6, the seal adhesiveness could not reach 50 N/cm ² , and it was found that the liquid crystal aligning agent 12 and the liquid crystal aligning agent 13 had weak seal adhesiveness.

<Preparation of blend type liquid crystal aligning agent, preparation and measurement of retardation measurement substrate>
Example 34
3.0 g of varnish 1 synthesized in Synthesis Example 1 and 7.0 g of varnish 14 synthesized in Synthesis Example 14 were weighed in a 50 mL eggplant flask equipped with a stirring blade and a nitrogen introducing tube, and NMP/BC=1/ The liquid crystal aligning agent 14 was prepared by adding 1 (weight ratio) of the mixed solvent and diluting it to a polymer solid concentration of 4% by weight. A substrate was prepared according to the method described in Example 1 and its retardation was measured and found to be 8.2 nm.

[Examples 35 to 45] [Comparative examples 7 and 8]
A substrate for measurement was prepared and the retardation was measured according to Example 34 except that the varnish used was changed. The results of Example 34 are shown together in Tables 5-1 and 5-2.

It was found that the retardation values of Examples 34 to 45 were greater than 5.0 nm and the orientation was high. Comparative Example 7 showed a high orientation of 8.6 nm, while Comparative Example 8 showed a low orientation of 2.2 nm.

<Preparation of cell for residual DC measurement using blend type liquid crystal aligning agent and residual DC measurement>
[Example 46]
A liquid crystal cell was produced and residual DC was measured in accordance with Example 12 except that the liquid crystal aligning agent 14 prepared in Example 34 was used.

<Preparation of cell for residual DC measurement using blend type liquid crystal aligning agent and residual DC measurement>
[Examples 47 to 57] [Comparative Examples 9 and 10]
A liquid crystal cell was prepared according to Example 46 except that the liquid crystal aligning agents 15 to 27 prepared in Examples 35 to 45, Comparative Examples 7 and 8 were used, and the residual DC was measured. The measurement results are shown in Tables 6-1 and 6-2 together with that of Example 46.

In all the cells of Examples 46 to 57, the initial value was small, and the value after relaxation for 15 minutes was also greatly attenuated, and it was confirmed that the occurrence of an afterimage could be suppressed. In Comparative Examples 9 and 10, the initial value was 500 mV or more, and the value after relaxation for 15 minutes was 100 mV or more, and the target afterimage characteristics could not be achieved.

<Production and Evaluation of Seal Adhesion Evaluation Cell Using Blend Type Liquid Crystal Alignment Agent>
Example 58
Using the two substrates prepared in Example 34, a seal adhesion evaluation cell was prepared in accordance with Example 23, and the seal adhesion was evaluated.

[Examples 59 to 69] [Comparative examples 11 and 12]
A seal adhesion evaluation cell was prepared and seal adhesion was evaluated in accordance with Example 58 except that the substrates prepared in Examples 35 to 45, Comparative Examples 5 and 6 were used. The measurement results are shown in Table 7-1 and Table 7-2 together with that of Example 58.

In Examples 58 to 69, the seal adhesiveness was 70 N/cm ² or more, and it was found that the blend liquid crystal aligning agent also has high adhesiveness. On the other hand, in Comparative Example 11 and Comparative Example 12, it was found that the seal adhesion could not reach 50 N/cm ² , and the seal adhesion was weak.

Example 70
<Preparation of Additive-Containing Liquid Crystal Alignment Agent, Preparation and Evaluation of Seal Adhesion Evaluation Cell>
In a 50 mL round-bottomed flask, 10 g of the liquid crystal aligning agent 14 was weighed, 15 parts by weight of the additive (Ad-1) was added to 100 parts by weight of the polymer, and the mixture was shaken for 2 hours, and the solid content was 4 wt%. The agent 28 was obtained. In accordance with Example 1, two substrates were prepared using the liquid crystal aligning agent 28. According to Example 23, a seal adhesion evaluation cell was prepared using the two prepared substrates, and the seal adhesion was evaluated.

[Example 71 and Example 72]
Additive-containing liquid crystal aligning agents 29 and 30 were prepared in accordance with Example 70 except that the varnish and the additives used were changed as shown in Table 8, and the seal adhesion was evaluated. The measurement results are shown in Table 8 together with that of Example 70.

[Liquid crystal aligning agent for inkjet coating]
The liquid crystal aligning agent of the present invention becomes a liquid crystal aligning agent suitable for coating by an inkjet method by appropriately selecting a solvent to be used.

Example 73
The varnish synthesized in Synthesis Example 1 was poured into a large excess of methanol to precipitate a reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40° C. for 15 hours to obtain 3 g of polyamic acid (PAA-1). To this polyamic acid (PAA-1), 48.0 g of NMP, 12.0 g of γ-butyrolactone (GBL), 16.0 g of 1-butoxy-2-propanol (BP), and diethylene glycol ethyl methyl ether (EDM). 15.0 g, 3.0 g of diethylene glycol butyl methyl ether (BDM) and 3.0 g of diisobutyl ketone (DIBK) were added, the solid content concentration was 3.0% by weight, and the solvent composition was NMP/GBL/BP/EDM/BDM/DIBK. A varnish (1-a) having a ratio of 48/12/16/15/3/3 was prepared.

Example 74
Similarly, for the varnish synthesized in Synthesis Example 14, according to Example 73, the solid content concentration was 3.0% by weight, and the solvent composition was NMP/GBL/BP/EDM/BDM/DIBK=48/12/16/15. A varnish (14-a) having a ratio of /3/3 was prepared.

Example 75
3.0 g of the varnish (1-a) prepared in Example 73 and 7.0 g of the varnish (14-a) prepared in Example 74 were weighed to obtain a solid concentration of 3.0% by weight and a solvent composition of NMP. A liquid crystal aligning agent (IJ-1) for coating by an inkjet method, which has a ratio of /GBL/BP/EDM/BDM/DIBK=48/12/16/15/3/3, was prepared.

Example 76
2.0 g of varnish 3 synthesized in Synthesis Example 3 and 8.0 g of varnish 15 synthesized in Synthesis Example 15 were weighed, and 6.2 g of NMP, 1.0 g of BDM and 2.8 g of EDE were added thereto. Then, a liquid crystal aligning agent (IJ-2) for inkjet coating having a solid content concentration of 3.0% by weight and a solvent composition of NMP:GBL:BC:BDM:EDE=48:15:15:5:14 was prepared.

Example 77
The liquid crystal alignment agent for inkjet coating (IJ-1) was coated on a glass substrate with an inkjet coating device (DMP-2831, manufactured by Fuji Film Co., Ltd.), and a substrate was prepared according to Example 1. Using the produced substrate, the seal adhesion was evaluated according to Example 23.

Example 78
The seal adhesion was evaluated according to Example 77 except that the liquid crystal aligning agent used was changed. The measurement results are shown in Table 9 together with that of Example 77.

It was confirmed that the liquid crystal aligning agent for photo-alignment of the present invention has good seal adhesion even when applied by the inkjet method.

When the liquid crystal aligning agent for photo-alignment of the present invention is used, it is possible to form a coating film having high adhesiveness with a seal and high liquid crystal alignment, and to provide a liquid crystal display device having good afterimage characteristics. A liquid crystal aligning agent for alignment can be provided. The liquid crystal aligning agent for optical alignment of the present invention can be suitably applied to a horizontal electric field type liquid crystal display device.

Claims (18)

A liquid crystal aligning agent for photo-alignment, comprising at least one polymer selected from polyamic acid and its derivatives, which is a reaction product of tetracarboxylic dianhydride and diamine;
A liquid crystal aligning agent for photoalignment, wherein at least one of the raw material monomers of the polymer has a photoisomerization structure, and the raw material monomer of the polymer contains at least one compound represented by the following formula (I).

In the formula (I), a is an integer of 1-12. A compound having at least one photoisomerization structure selected from the group consisting of tetracarboxylic dianhydride and diamine, wherein tetracarboxylic dianhydride is at least one of the compounds represented by formula (I) Or at least one of the polymers that is a reaction product of the raw material monomer;
At least one polymer which is a reaction product of a raw material monomer containing a compound having at least one photoisomerization structure selected from the group consisting of tetracarboxylic dianhydride and diamine;
Neither tetracarboxylic dianhydride nor diamine has a photoisomerization structure, and a reactant of a raw material monomer in which the tetracarboxylic dianhydride contains at least one compound represented by formula (I) The liquid crystal aligning agent for photo-alignment according to claim 1, which simultaneously contains at least one of the polymers A compound having at least one photoisomerization structure selected from the group consisting of tetracarboxylic dianhydride and diamine, wherein tetracarboxylic dianhydride is at least one of the compounds represented by formula (I) At least one of the polymers which is a reaction product of the raw material monomer containing, and other polymers used by mixing with the polymer,
The liquid crystal aligning agent for photoalignment according to claim 2, wherein the other polymer is a polymer which is a reaction product of a raw material monomer in which neither tetracarboxylic dianhydride nor diamine has a photoisomerization structure. A compound having at least one photoisomerization structure selected from the group consisting of tetracarboxylic dianhydride and diamine, wherein tetracarboxylic dianhydride is at least one of the compounds represented by formula (I) At least one of the polymers which is a reaction product of the raw material monomer containing, and other polymers used by mixing with the polymer,
At least one of the compounds represented by formula (I) in which the other polymer has no photoisomerization structure of tetracarboxylic dianhydride and its derivative, and diamine The liquid crystal aligning agent for photo-alignment according to claim 2, which is a polymer which is a reaction product of a raw material monomer containing one. At least one polymer which is a reaction product of a raw material monomer containing a compound having at least one photoisomerization structure selected from the group consisting of tetracarboxylic dianhydride and diamine;
Neither tetracarboxylic dianhydride nor diamine has a photoisomerization structure, and a reactant of a raw material monomer in which the tetracarboxylic dianhydride contains at least one compound represented by formula (I) The liquid crystal aligning agent for photo-alignment according to claim 1, which simultaneously contains at least one of the polymers The photo-alignment according to any one of claims 1 to 5, wherein the tetracarboxylic dianhydride represented by the formula (I) is a tetracarboxylic dianhydride represented by the formula (I-1). Liquid crystal aligning agent;

The photo-alignment according to any one of claims 1 to 6, wherein the tetracarboxylic dianhydride or diamine having a photoisomerization structure is at least one of the compounds represented by formulas (II) to (VI). Liquid crystal aligning agent;

In formulas (II) to (V), R ² and R ³ are independently a monovalent organic group having —NH ₂ or a monovalent organic group having —CO—O—CO—, and have the formula (IV ), R ⁴ is a divalent organic group, and in formula (VI), R ⁵ is independently an aromatic ring having —NH ₂ or an aromatic ring having —CO—O—CO—. The tetracarboxylic dianhydride or diamine having a photoisomerization structure is represented by the formula (II-1), (II-2), (III-1), (III-2), (IV-1), (IV-2 ), (V-1) to (V-3), (VI-1), and at least one selected from the group of compounds represented by (VI-2), the optical alignment according to claim 7. Liquid crystal aligning agent;

In each of the above formulas, 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 formula (V-2), R ⁶ is independently —CH ₃ , —OCH ₃ , —CF ₃ , or —COOCH ₃ , and a is independently an integer of 0 to 2;
In formula (V-3), ring A and ring B are independently at least one selected from monocyclic hydrocarbons, condensed polycyclic hydrocarbons and heterocycles,
R ¹¹ is linear alkylene having 1 to 20 carbon atoms, —COO—, —OCO—, —NHCO—, —CONH—, —N(CH ₃ )CO—, or —CON(CH ₃ )—,
R ¹² is linear alkylene having 1 to 20 carbon atoms, —COO—, —OCO—, —NHCO—, —CONH—, —N(CH ₃ )CO—, or —CON(CH ₃ )—,
In R ¹¹ and R ¹² , one or two of —CH ₂ — of the linear alkylene may be substituted with —O—,
R ⁷ to R ¹⁰ are _{independently,} -F, -CH _3, -OCH 3, a -CF ₃ or -OH,, and,
b to e are each independently an integer of 0 to 4. The tetracarboxylic dianhydride having no photoisomerization structure is at least one selected from the group of tetracarboxylic dianhydrides represented by the following formulas (AN-I) to (AN-VII). A liquid crystal aligning agent for photo-alignment according to any one of claims 1 to 8;

Formula (AN-I), in formula (AN-IV) and formula (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 formulas (AN-II) to (AN-IV), Y is independently one selected from the group of the following trivalent groups,

At least one hydrogen of these groups may be replaced by methyl, ethyl or phenyl;
In formulas (AN-III) to (AN-V), ring A ¹⁰ is a monocyclic hydrocarbon group having 3 to ¹⁰ carbon atoms or a condensed polycyclic hydrocarbon group having 6 to 30 carbon atoms, At least one hydrogen of this group may be replaced by methyl, ethyl or phenyl, the bond attached to the ring is linked to any carbon constituting the ring, and the two bonds are the same. May be linked to carbon;
In formula (AN-VI), X ¹⁰ is independently alkylene having 2 to 6 carbon atoms, Me represents methyl, Ph represents phenyl,
In the formula ^{(AN-VII), G 10} is independently -O -, - COO- or a -OCO-; and, r is 0 or 1 independently. The tetracarboxylic acid dianhydride having no photoisomerization structure is represented by the following formula (AN-1-1), formula (AN-1-2), formula (AN-1-13), formula (AN-2-). 1), formula (AN-3-1), formula (AN-3-2), formula (AN-4-5), formula (AN-4-17), formula (AN-4-21), formula ( AN-4-29), Formula (AN-4-30), Formula (AN-5-1), Formula (AN-7-2), Formula (AN-10-1), Formula (AN-11-3). ), the formula (AN-16-1), the formula (AN-16-3), and the formula (AN-16-4), at least one selected from the group consisting of: ;

In formula (AN-1-2) and formula (AN-4-17), m is an integer of 1-12. The diamine having no photoisomerization structure is represented by the following formula (DI-1) to formula (DI-16), formula (DIH-1) to formula (DIH-3), and formula (DI-31) to formula (DI-31). DI-35), which is at least one selected from the group consisting of DI-35), and the liquid crystal aligning agent for optical alignment according to any one of claims 1 to 10;

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

In formula (DI-4-a) and formula (DI-4-b), R ²⁰ is independently hydrogen or —CH ₃ .
A group in which the bonding position is not fixed to a 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 bonding position of

In formula (DI-11), r is 0 or 1.
In formulas (DI-8) to (DI-11), the bonding position of —NH ₂ bonded to the ring is any 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 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 Is an integer from 0 to 4;
In 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, and 2 carbons. To alkenyl, alkynyl having 1 to 6 carbon atoms, q is independently an integer of 0 to 4;
In formula (DI-15), ring C is a monocycle containing a heteroatom;
In formula (DI-16), G ²⁴ is a single bond, alkylene having 2 to 6 carbon atoms or 1,4-phenylene, and r is 0 or 1.
In the formulas (DI-13) to (DI-16), a group in which the bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary.

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

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

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

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

In formula (DI-32) and formula (DI-33), G ³⁰ is independently a single bond, —CO— or —CH ₂ —, R ²⁹ is independently hydrogen or —CH ₃ , and R ²⁹ is ³⁰ is independently 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 having 1 to 20 carbons or phenyl, 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 formula (DI-34) and formula (DI-35), G ³¹ is independently —O— or alkylene having 1 to 6 carbons, and G ³² is a single bond or alkylene having 1 to 3 carbons. ,
R ³¹ is hydrogen or alkyl having 1 to 20 carbons, and at least one —CH ₂ — of this alkyl may be replaced by —O—, —CH═CH— or —C≡C—, R ^{31 32} is alkyl having 6 to 22 carbons, R ³³ is hydrogen or alkyl having 1 to 22 carbons, ring B ²⁵ is 1,4-phenylene or 1,4-cyclohexylene, r is 0 or 1 and —NH ₂ bonded to the benzene ring indicates that the bonding position in the ring is arbitrary. The diamine having no photoisomerization structure is represented by the following formula (DI-1-3), formula (DI-2-1), formula (DI-4-1), formula (DI-4-2), formula ( DI-4-10), Formula (DI-4-15), Formula (DI-5-1), Formula (DI-5-5), Formula (DI-5-9), Formula (DI-5-12). ), Formula (DI-5-13), Formula (DI-5-17), Formula (DI-5-28), Formula (DI-5-30), Formula (DI-6-7), Formula (DI. -7-3), Formula (DI-11-2), Formula (DI-13-1), Formula (DI-16-1), Formula (DI-31-56), and Formula (DIH-2-1). The liquid crystal aligning agent for photo-alignment according to claim 11, which is at least one selected from the group consisting of:

In formula (DI-5-1), formula (DI-5-12), formula (DI-5-13), and formula (DI-7-3), m is independently an integer of 1 to 12. ;
In formula (DI-5-30), k is an integer from 1 to 5; and
In formula (DI-7-3), n is independently 1 or 2. The alkenyl-substituted nadimide compound, a compound having a radically polymerizable unsaturated double bond, an oxazine compound, an oxazoline compound, and at least one compound selected from the group consisting of epoxy compounds, further containing at least one of claims 1 to 12. The liquid crystal aligning agent for optical alignment according to item 1. The liquid crystal aligning agent for optical alignment according to any one of claims 1 to 13, which is used for manufacturing a horizontal electric field driving type liquid crystal display device. The liquid crystal aligning agent for photo-alignment according to any one of claims 1 to 14, which can be applied by an inkjet method. A liquid crystal alignment film formed by the liquid crystal alignment agent for optical alignment according to claim 1. A liquid crystal display device comprising the liquid crystal alignment film according to claim 16. A lateral electric field drive type liquid crystal display device comprising the liquid crystal alignment film according to claim 16.