JP2012155311A - Liquid crystal aligning agent for forming photo-aligning liquid crystal alignment layer, liquid crystal alignment layer and liquid crystal display element using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystal aligning agent for forming a photo-alignment layer having good sensitivity in chemical changes by irradiation with light, excellent aligning property for liquid crystal molecules and high light transmittance while maintaining electric characteristics commonly required for a liquid crystal alignment layer such as a high voltage retention rate, a small amount of ions and a little residual charge, and to provide a photo-alignment layer using the liquid crystal aligning agent, and a liquid crystal display element using the photo-alignment layer.SOLUTION: A photo-alignment layer is formed of the following liquid crystal aligning agent, and is used for a liquid crystal display element. The liquid crystal aligning agent contains a polyamic acid or its derivative obtained by reacting a cyclobutane tetracarboxylic acid dianhydride or a mixture of tetracarboxylic acid dianhydrides including a cyclobutane tetracarboxylic acid dianhydride with a specified diamine having at least two nitrogen atoms except for a nitrogen atom in an amino group in the molecule.

Description

The present invention relates to a liquid crystal aligning agent for photo-alignment using a photo-alignment method, a photo-alignment film using the same, and a liquid crystal display element.

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

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

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

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

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

On the other hand, the photo-alignment method has a smaller anchoring energy than the rubbing method, and the alignment property of liquid crystal molecules is inferior. In order to overcome such drawbacks, we have found a method of applying a liquid crystal aligning agent made of polyamic acid to a substrate, irradiating with light, and then baking it by the method described in Patent Document 4, for example. A photo-alignment film having a large anchoring energy was obtained by this method. However, a photo-alignment film using a polyamic acid produced using a diamine having an azo group as a raw material has a problem that the light transmittance is low and the luminance of the liquid crystal display element is lowered.

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

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

The object of the present invention is that the sensitivity of chemical change due to light irradiation is good while maintaining the electrical characteristics commonly required for liquid crystal alignment films, such as high voltage holding ratio, small amount of ions, and low residual charge. Another object of the present invention is to provide a liquid crystal aligning agent for forming a photo-alignment film having excellent alignment properties of liquid crystal molecules and high light transmittance. Another object of the present invention is to provide a photo-alignment film using this liquid crystal aligning agent, and to provide a liquid crystal display element using this photo-alignment film.

We have cyclobutanetetracarboxylic dianhydride or a mixture of tetracarboxylic dianhydrides including cyclobutanetetracarboxylic dianhydride and at least two nitrogen atoms in the molecule other than the amino nitrogen atoms. A photo-alignment film formed by a liquid crystal aligning agent containing a polyamic acid obtained by reacting with a specific diamine or a derivative thereof has good sensitivity to chemical changes due to light irradiation, excellent alignment of liquid crystal molecules, and The present inventors have found that the light transmittance is high and completed the present invention.

式（Ｉ）において、Ｒ^Ａ〜Ｒ^Ｄは独立して水素または炭素数１〜４のアルキルである。

式（Ｎ−１）において、Ｒ^Ｅは独立して１価の有機基であり；
Ｒ^Ｆは独立して水素、１価の有機基またはハロゲンであり；そして、
Ｚは炭素数１〜５のアルキレンを含む２価の基である。

式（Ｎ−２）において、Ｒ^Ｇは独立して１価の有機基またはハロゲンであり；
Ｒ^Ｈは独立して１価の有機基であり；
ｍは独立して０〜３の整数であり；そして、
ｎは０〜４の整数である。 The present invention has the following configuration.
[1] In a liquid crystal aligning agent for forming a liquid crystal aligning film for photo-alignment, comprising polyamic acid obtained by reacting tetracarboxylic dianhydride and diamine or a derivative thereof,
The tetracarboxylic dianhydride includes a tetracarboxylic dianhydride represented by the following formula (I);
The diamine is a liquid crystal aligning agent containing at least one selected from the group of diamines represented by the following formula (N-1) and formula (N-2).

In the formula (I), R ^{A to} R ^D are independently hydrogen or alkyl having 1 to 4 carbons.

In formula (N-1), R ^E is independently a monovalent organic group;
R ^F is independently hydrogen, a monovalent organic group or halogen; and
Z is a divalent group containing an alkylene having 1 to 5 carbon atoms.

In formula (N-2), R ^G is independently a monovalent organic group or halogen;
R ^H is independently a monovalent organic group;
m is independently an integer from 0 to 3; and
n is an integer of 0-4.

[2] In formula (N-1), R ^E is independently alkyl having 1 to 3 carbons, and R ^F is independently hydrogen, alkyl having 1 to 3 carbons, fluorine, chlorine, or bromine. The liquid crystal aligning agent as described in the said [1] item containing the polyamic acid obtained by making the diamine represented or the diamine mixture containing this diamine react with tetracarboxylic dianhydride, or its derivative (s).

[3] Polyamics obtained by reacting a diamine represented by the formula (N-1) having an amino group at each para position in phenyl at both ends of the molecule or a diamine mixture containing this diamine with tetracarboxylic dianhydride The liquid crystal aligning agent according to the item [1] or [2], which contains an acid or a derivative thereof.

[4] At least one selected from the group of diamines represented by the following formulas (N-1-1) to (N-1-20) or a diamine mixture containing the diamine is reacted with tetracarboxylic dianhydride. The liquid crystal aligning agent of any one of said [1]-[3] containing the polyamic acid obtained by these, or its derivative (s).

[5] R ^G is independently alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, carbamoyl, fluorine, chlorine, or bromine, and R ^H is independently alkyl having 1 to 3 carbons. The polyamic acid obtained by reacting a diamine represented by the formula (N-2) or a diamine mixture containing the diamine with tetracarboxylic dianhydride or a derivative thereof, according to the above [1] to [4] The liquid crystal aligning agent of any one of Claims.

[6] Polyamics obtained by reacting a diamine represented by formula (N-2) having an amino group at each para position in phenyl at both ends of the molecule or a diamine mixture containing this diamine with tetracarboxylic dianhydride The liquid crystal aligning agent of any one of said [1]-[5] containing an acid or its derivative (s).

[7] At least one selected from the group of diamines represented by the following formulas (N-2-1) to (N-2-15) or a diamine mixture containing the diamine is reacted with tetracarboxylic dianhydride. The liquid crystal aligning agent of any one of said [1]-[6] containing the polyamic acid obtained by these, or its derivative (s).

[8] At least one of the diamines represented by the formulas (N-2-1) and (N-2-2) according to the item [7] or a diamine mixture containing the diamine is used as a tetracarboxylic dianhydride. The liquid crystal aligning agent of any one of said [1]-[6] containing the polyamic acid obtained by making it react with, or its derivative (s).

式（ＩＩＩ）において、Ａ^１は−（ＣＨ_２）_ｍ−であり、ｍは１〜６の整数であり；
式（Ｖ）、（ＶＩＩ）および（ＩＸ）において、Ｘは単結合、−Ｏ−、−Ｓ−、−Ｓ−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−、−（ＣＨ_２）_ｍ−、−Ｏ−（ＣＨ_２）_ｍ−Ｏ−、または−Ｓ−（ＣＨ_２）_ｍ−Ｓ−であり、ｍは１〜６の整数であり；
式（ＶＩＩ）において、Ｌ^１およびＬ^２は−Ｈであるが、Ｘが−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、または−Ｃ（ＣＦ_３）_２−であるときには互いに結合して単結合を形成してもよく；
式（ＶＩＩＩ）および（ＩＸ）において、Ｙは単結合、−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；
式（ＸＶ）において、Ｒ^３３およびＲ^３４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；ｍは１〜１０の整数であり；そして、
上記の各式において、シクロヘキサン環またはベンゼン環の−Ｈは、−Ｆ、−ＣＨ_３、−ＯＨ、−ＣＯＯＨ、−ＳＯ_３Ｈ、−ＰＯ_３Ｈ_２、ベンジル、またはヒドロキシベンジルで置き換えられていてもよい。 [9] A polyamic acid obtained by reacting a diamine mixture further containing at least one selected from the group of diamines represented by the following formulas (III) to (IX) and (XV) with tetracarboxylic dianhydride or The liquid crystal aligning agent of any one of said [1]-[8] containing the derivative | guide_body.

In Formula (III), A ¹ is — (CH ₂ ) _m —, and m is an integer of 1 to 6;
In the formulas (V), (VII) and (IX), X represents a single bond, —O—, —S—, —S—S—, —SO ₂ —, —CO—, —NH—, —N (CH _{3) -, - C (CH} 3) 2 -, - C (CF 3) 2 -, - (CH 2) m -, - O- (CH 2) m -O-, or -S- _(CH 2) _m -S-, m is an integer from 1 to 6;
In Formula (VII), L ¹ and L ² are —H, but X is —NH—, —N (CH ₃ ) —, —CH ₂ —, —C (CH ₃ ) ₂ —, or —C ( When CF ₃ ) ₂ —, they may combine with each other to form a single bond;
In Formulas (VIII) and (IX), Y represents a single bond, —O—, —S—, —CO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, or a carbon number of 1 to 3 alkylene;
In formula (XV), R ³³ and R ³⁴ are independently alkyl having 1 to 3 carbons or phenyl; G is independently alkylene having 1 to 6 carbons, phenylene or alkyl-substituted phenylene; m is an integer from 1 to 10;
In each formula above, _-H cyclohexane ring or benzene ring, -F, -CH 3, -OH, -COOH, -SO 3 H, -PO 3 H 2, be replaced by benzyl or hydroxybenzyl, Also good.

[10] In any one of [1] to [9] above, containing a polyamic acid obtained by reacting a diamine mixture further containing a diamine having a side chain structure with tetracarboxylic dianhydride or a derivative thereof. The liquid crystal aligning agent of description.

式（Ｘ）において、
Ｚ^１は、単結合、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、または−（ＣＨ_２）_ｍ−であり、ｍは１〜６の整数であり、このアルキレンにおける任意の−ＣＨ_２−は−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられていてもよく；
Ｒ^３は、ステロイド骨格を有する基、炭素数３〜３０のアルキル、炭素数１〜３０のアルキルもしくは炭素数１〜３０のアルコキシを置換基として有するフェニル、または下記式（Ｘ−ａ）で表される基であり、この炭素数１〜３０のアルキルにおける任意の−ＣＨ_２−は−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられていてもよく；

式（Ｘ−ａ）において、
Ａ^２およびＡ^３は独立して、単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＣＨ＝ＣＨ−、または炭素数１〜１２のアルキレンであり、ａおよびｂは独立して０〜４の整数であり；
環Ｂおよび環Ｃは独立して１，４−フェニレン、１，４−シクロヘキシレン、１，３−ジオキサン−２，５−ジイル、ピリミジン−２，５−ジイル、ピリジン−２，５−ジイル、ナフタレン−１，５−ジイル、ナフタレン−２，７−ジイル、またはアントラセン−９，１０−ジイルであり；
Ｒ^４およびＲ^５は独立して、−ＦまたはＣＨ_３であり、ｆおよびｇは独立して０〜２の整数であり；
Ｒ^６は−Ｆ、−ＯＨ、−ＣＮ、炭素数１〜３０のアルキル、炭素数１〜３０のアルコキシ、または炭素数２〜３０のアルコキシアルキルであり、これらのアルキル、アルコキシ、アルコキシアルキルにおいて、任意の−Ｈは−Ｆで置き換えられていてもよく、任意の−ＣＨ_２−は−ＣＦ_２−または下記式（ｓ）で表される２価の基で置き換えられていてもよく；

式（ｓ）において、Ｒ^３５およびＲ^３６は独立して炭素数１〜３のアルキルであり、ｍは１〜６の整数であり；
ｃ、ｄおよびｅは独立して０〜３の整数であり、そして、ｃ＋ｄ＋ｅ≧１である。

式（ＸＩ）および（ＸＩＩ）において、
Ｒ^７は独立して−Ｈまたは−ＣＨ_３であり；
Ｒ^８は−Ｈ、炭素数１〜２０のアルキルまたは炭素数２〜２０のアルケニルであり；
Ａ^４は独立して単結合、−ＣＯ−または−ＣＨ_２−であり；
式（ＸＩＩ）において、
Ｒ^９およびＲ^１０は独立して炭素数１〜２０のアルキルまたはフェニルである。

式（ＸＩＩＩ）および（ＸＩＶ）において、Ａ^５は独立して−Ｏ−または炭素数１〜６のアルキレンであり；
式（ＸＩＩＩ）において、Ｒ^１１は−Ｈまたは炭素数１〜３０のアルキルであり、このアルキルの任意の−ＣＨ_２−は、−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく；
Ａ^６は単結合または炭素数１〜３のアルキレンであり；
環Ｔは１，４−フェニレンまたは１，４−シクロヘキシレンであり；
ｈは０または１であり；
式（ＸＩＶ）において、Ｒ^１２は炭素数６〜２２のアルキルであり；そして、
Ｒ^１３は炭素数１〜２２のアルキルである。 [11] The liquid crystal aligning agent for photoalignment according to the above [10], wherein the diamine having a side chain structure is at least one selected from the group of diamines represented by the following formulas (X) to (XIV).

In formula (X),
Z ¹ is a single bond, —O—, —CO—, —COO—, —OCO—, —CONH—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, or - _{(CH 2) m} - and is, m is an integer from 1 to 6, any -CH ₂ - in this alkylene -O -, - be replaced by CH = CH- or -C≡C- Well;
R ³ is a group having a steroid skeleton, alkyl having 3 to 30 carbon atoms, phenyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms as a substituent, or a group represented by the following formula (X-a): Any —CH ₂ — in the alkyl having 1 to 30 carbon atoms may be replaced by —O—, —CH═CH— or —C≡C—;

In the formula (Xa),
A ² and A ³ are independently a single bond, —O—, —COO—, —OCO—, —CONH—, —CH═CH—, or alkylene having 1 to 12 carbons, and a and b are Independently an integer from 0 to 4;
Ring B and Ring C are independently 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, Naphthalene-1,5-diyl, naphthalene-2,7-diyl, or anthracene-9,10-diyl;
R ⁴ and R ⁵ are independently —F or CH ₃ and f and g are independently integers from 0 to 2;
R ⁶ is —F, —OH, —CN, alkyl having 1 to 30 carbons, alkoxy having 1 to 30 carbons, or alkoxyalkyl having 2 to 30 carbons. In these alkyls, alkoxys, alkoxyalkyls, Any —H may be replaced by —F, and any —CH ₂ — may be replaced by —CF ₂ — or a divalent group represented by the following formula (s);

In the formula (s), R ³⁵ and R ³⁶ are independently alkyl having 1 to 3 carbon atoms, and m is an integer of 1 to 6;
c, d and e are each independently an integer of 0 to 3, and c + d + e ≧ 1.

In formulas (XI) and (XII)
R ⁷ is independently —H or —CH ₃ ;
R ⁸ is —H, alkyl having 1 to 20 carbons or alkenyl having 2 to 20 carbons;
A ⁴ is independently a single bond, —CO— or —CH ₂ —;
In formula (XII):
R ⁹ and R ¹⁰ are independently alkyl having 1 to 20 carbons or phenyl.

In formulas (XIII) and (XIV), A ⁵ is independently —O— or alkylene having 1 to 6 carbons;
In the formula (XIII), R ¹¹ is —H or alkyl having 1 to 30 carbons, and arbitrary —CH ₂ — of this alkyl is replaced by —O—, —CH═CH— or —C≡C—. May be
A ⁶ is a single bond or alkylene having 1 to 3 carbon atoms;
Ring T is 1,4-phenylene or 1,4-cyclohexylene;
h is 0 or 1;
In formula (XIV), R ¹² is alkyl having 6 to 22 carbons; and
R ¹³ is alkyl having 1 to 22 carbons.

式（Ａｎ−１）、（Ａｎ−４）および（Ａｎ−５）において、Ｘ^１は独立して単結合または−ＣＨ_２−であり；
式（Ａｎ−２）において、Ｇ^１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−２）〜（Ａｎ−４）において、Ｙ^１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；

式（Ａｎ−３）〜（Ａｎ−５）において、環Ｅは炭素数３〜１０の単環式炭化水素の基または炭素数６〜２０の縮合多環式炭化水素の基を表し、この基の任意の水素はメチル、エチルまたはフェニルで置き換えられていてもよく；
環に掛かっている結合手は環を構成する任意の炭素に連結しており、２本の結合手が同一の炭素に連結してもよく；
式（Ａｎ−６）において、Ｘ^１１は炭素数２〜６のアルキレンであり；
Ｍｅはメチルを表し、そして、Ｐｈはフェニルを表す。 [12] As the tetracarboxylic dianhydride to be reacted with diamine, at least one selected from the group of compounds represented by the following formulas (An-1) to (An-6) is further used. [11] The liquid crystal aligning agent according to any one of [11].

In formulas (An-1), (An-4) and (An-5), X ¹ is independently a single bond or —CH ₂ —;
In Formula (An-2), G ¹ represents a single bond, alkylene having 1 to 20 carbons, —CO—, —O—, —S—, —SO ₂ —, —C (CH ₃ ) ₂ —, or — C (CF ₃ ) ₂ —;
In formulas (An-2) to (An-4), Y ¹ is independently one selected from the group of trivalent groups described below;

In the formulas (An-3) to (An-5), the ring E represents a monocyclic hydrocarbon group having 3 to 10 carbon atoms or a condensed polycyclic hydrocarbon group having 6 to 20 carbon atoms. Any hydrogen in may be replaced by methyl, ethyl or phenyl;
The bond on the ring is linked to any carbon that makes up the ring, and two bonds may be linked to the same carbon;
In the formula (An-6), X ¹¹ is alkylene having 2 to 6 carbons;
Me represents methyl and Ph represents phenyl.

[13] As tetracarboxylic dianhydride to be reacted with diamine, aromatic tetracarboxylic dianhydride represented by the following formulas (1), (2), (5) to (7) and (17) The liquid crystal aligning agent according to any one of [1] to [11], further using at least one selected from the group.

[14] Fats represented by the following formulas (23), (25), (36) to (39), (44), (49) and (68) as tetracarboxylic dianhydrides to be reacted with diamine The liquid crystal aligning agent according to any one of [1] to [11], further using at least one selected from the group of cyclic tetracarboxylic dianhydrides and aliphatic tetracarboxylic dianhydrides.

[15] As tetracarboxylic dianhydride to be reacted with diamine, at least one selected from the group of aromatic tetracarboxylic dianhydrides according to claim 13, and alicyclic tetracarboxylic dianhydrides according to claim 14. The liquid crystal aligning agent according to any one of the above [1] to [11], further using at least one selected from the group consisting of a product and an aliphatic tetracarboxylic dianhydride.

[16] A liquid crystal aligning agent obtained by mixing at least two liquid crystal aligning agents according to any one of [1] to [15].

[17] The liquid crystal aligning agent according to any one of [1] to [16], further including at least one selected from an alkenyl-substituted nadiimide compound, an epoxy compound, and a silane coupling agent.

[18] The alkenyl-substituted nadiimide compound is bis [4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl] methane, N, N′-m-xylylene- Bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) and N, N′-hexamethylene-bis (allylbicyclo [2.2.1] hept-5- The liquid crystal aligning agent according to [17], which is at least one selected from the group consisting of ene-2,3-dicarboximide).

[19] The item [17], wherein the alkenyl-substituted nadiimide compound is bis [4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl] methane. Liquid crystal aligning agent.

[20] The liquid crystal alignment according to any one of [17] to [19], wherein the alkenyl-substituted nadiimide compound is contained in an amount of 0.01 to 50% by weight based on the total amount of the polyamic acid or a derivative thereof. Agent.

[21] The epoxy compound is N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N '-Tetraglycidyl-4,4'-diaminodiphenylmethane, 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3-epoxy] Propoxy] phenyl)] ethyl] phenyl] propane, 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate, N-phenylmaleimide-glycidyl methacrylate copolymer, and 2- (3,4- The liquid according to [17], which is at least one selected from the group consisting of (epoxycyclohexyl) ethyltrimethoxysilane. Alignment agent.

[22] The item [17], wherein the epoxy compound is N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane or 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Liquid crystal aligning agent as described in.

[23] The liquid crystal aligning agent according to the above [17], [21] or [22], wherein the epoxy compound is contained in an amount of 1 to 40% by weight based on the total amount of the polyamic acid or a derivative thereof.

[24] The silane coupling agent is vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyl. Trimethoxysilane, paraaminophenyltrimethoxysilane, paraaminophenyltriethoxysilane, metaaminophenyltrimethoxysilane, metaaminophenyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycid Xylpropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysila , 3-mercaptopropyltrimethoxysilane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propylamine, and N, N′-bis [3- (trimethoxysilyl) propyl The liquid crystal aligning agent according to the above [17], which is at least one selected from the group consisting of ethylenediamine.

[25] The liquid crystal aligning agent according to the above [17], wherein the silane coupling agent is 3-aminopropyltriethoxysilane.

[26] The liquid crystal aligning agent according to the above [17], [24] or [25], wherein the silane coupling agent is contained in an amount of 0.1 to 10% by weight based on the total amount of the polyamic acid or derivative thereof .

[27] A step of applying the liquid crystal aligning agent according to any one of [1] to [26] to a substrate, a step of heating and drying the substrate coated with the aligning agent, and irradiating the film with polarized ultraviolet rays Liquid crystal alignment film for photo-alignment formed through the process of performing.

[28] A step of applying the liquid crystal aligning agent according to any one of [1] to [26] to the substrate, a step of heating and drying the substrate to which the aligning agent has been applied, and a polarized ultraviolet ray on the dried film. A liquid crystal alignment film for photo-alignment formed through a step of irradiating and then a step of heating and baking the film.

[29] A step of applying the liquid crystal aligning agent according to any one of [1] to [26] to the substrate, a step of heating and drying the substrate coated with the aligning agent, and heating and baking the dried film. A liquid crystal alignment film for photo-alignment formed through a step of performing and a step of irradiating the film with polarized ultraviolet rays.

[30] A liquid crystal display device having the liquid crystal alignment film for photo-alignment according to any one of [27] to [29].

According to the present invention, it has electrical characteristics such as a high voltage holding ratio, a small amount of ions, and a small residual charge, and has good sensitivity to chemical change by light irradiation, excellent alignment of liquid crystal molecules, and light transmittance. Can be obtained. And the liquid crystal display element excellent in the display characteristic which has this photo-alignment film can be obtained.

The liquid crystal aligning agent of this invention contains the polyamic acid which is a reaction product of tetracarboxylic dianhydride and diamine, or its derivative (s). The polyamic acid derivative is a component that dissolves in a solvent when the liquid crystal aligning agent described later contains a solvent. When the liquid crystal aligning agent is used as a liquid crystal aligning film described later, the main component is polyimide. It is a component that can form a liquid crystal alignment film. Examples of such polyamic acid derivatives include soluble polyimides, polyamic acid esters, and polyamic acid amides. More specifically, 1) polyimide in which all amino acids and carboxyls of polyamic acid are subjected to a dehydration ring-closing reaction, 2) Partially dehydrated ring-closing partial polyimide, 3) Polyamic acid ester in which carboxyl of polyamic acid is converted to ester, 4) Part of acid dianhydride contained in tetracarboxylic dianhydride compound is organic dicarboxylic Examples thereof include polyamic acid-polyamide copolymers obtained by reacting with an acid, and 5) polyamideimide obtained by subjecting a part or all of the polyamic acid-polyamide copolymer to a dehydration ring-closing reaction. One kind of compound may be sufficient as the said polyamic acid or its derivative (s), and 2 or more types may be sufficient as it.

The tetracarboxylic dianhydride includes a tetracarboxylic dianhydride represented by the following formula (I).

When the liquid crystal aligning agent of the present invention is applied to a substrate, dried by preheating, and then irradiated with linearly polarized light of ultraviolet rays through a polarizing plate, the above-described formula ( The cyclobutane ring of the structural unit derived from the tetracarboxylic dianhydride represented by I) causes a photolysis reaction. The main chain of the polymer that forms the film is selectively decomposed by the main chain of the polymer that is substantially parallel to the polarization direction, so that the component of the polymer main chain is oriented in a direction substantially perpendicular to the polarization direction of the irradiated ultraviolet light. Becomes dominant. Therefore, after heating the substrate and dehydrating and cyclizing the polyamic acid to form a polyimide film, the liquid crystal molecules in the liquid crystal composition injected into the cell assembled using this substrate are in the polarization direction of the irradiated ultraviolet light. Orient with the major axis aligned in a perpendicular direction. The step of irradiating the film with ultraviolet linearly polarized light may be before the heating step for the formation of polyimide, or may be after the formation of polyimide by heating.

R ^{A to} R ^D in the formula (I) are independently hydrogen or alkyl having 1 to 4 carbon atoms. C1-C4 alkyl is specifically methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl. R ^{A to} R ^D are preferably hydrogen or methyl, more preferably hydrogen.

As the tetracarboxylic dianhydride represented by the formula (I), one compound may be used alone, or two or more may be mixed and used. The tetracarboxylic dianhydride represented by the formula (I) may be used by mixing with other tetracarboxylic dianhydrides. In this case, the tetracarboxylic dianhydride represented by the formula (I) in the mixture of tetracarboxylic dianhydrides is used in a proportion of 10% by weight or more, preferably 50% by weight or more, and 80% by weight. % Or more is more preferable.

The diamine includes at least one selected from the group of diamines represented by the following formula (N-1) and formula (N-2).

In the formula (N-1), R ^E is independently a monovalent organic group. Of the monovalent organic groups, alkyl is preferable, and alkyl having 1 to 3 carbon atoms is preferable. Specifically, the alkyl having 1 to 3 carbon atoms is methyl, ethyl, n-propyl, and isopropyl, and methyl is more preferable. R ^F is independently hydrogen, a monovalent organic group or halogen. Of the monovalent organic groups, alkyl is preferable, and alkyl having 1 to 3 carbon atoms is preferable. Specifically, the alkyl having 1 to 3 carbon atoms is methyl, ethyl, n-propyl, and isopropyl, and methyl is more preferable. Halogen is preferably fluorine, chlorine and bromine. Of these, hydrogen is more preferred. Z is a divalent group containing an alkylene having 1 to 5 carbon atoms, and is preferably an alkylene having 1 to 5 carbon atoms. The bonding position of the amino group in phenyl at both ends of the molecule may be arbitrary, but the para position and the meta position are preferred, and the para position is more preferred.

In the formula (N-2), R ^G is independently a monovalent organic group or halogen. Of the monovalent organic groups, alkyl, alkoxy and carbamoyl are preferred. Among alkyl having 1 to 10 carbon atoms, alkyl having 1 to 4 carbon atoms is more preferable. Specifically, the alkyl having 1 to 4 carbon atoms is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl, and methyl is more preferable. Among alkoxy having 1 to 10 carbon atoms, alkoxy having 1 to 4 carbon atoms is more preferable. C1-C4 alkoxy is specifically methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, and t-butyloxy, with methoxy being more preferred. Halogen is preferably fluorine, chlorine and bromine. R ^H is independently a monovalent organic group. Of the monovalent organic groups, alkyl is preferable, and alkyl having 1 to 3 carbon atoms is preferable. Specifically, the alkyl having 1 to 3 carbon atoms is methyl, ethyl, n-propyl, and isopropyl, and methyl is more preferable. m is an integer of 0-3 independently. When m is selected from an integer of 1 to 3, it is preferably 1 or 2, and more preferably 1. m is preferably 0 or 1. When m is 2 or 3, R ^G may be the same or different. n is an integer of 0-4. When n is selected from an integer of 1 to 4, it is preferably 1 or 2, and more preferably 1. n is preferably 0 or 1, and more preferably 0. The bonding position of the amino group in phenyl at both ends of the molecule may be arbitrary, but the para position and the meta position are preferred, and the para position is more preferred.

Specific examples of the diamine represented by the formula (N-1) are compounds represented by the following formulas (N-1-1) to (N-1-20).

Specific examples of the diamine represented by the formula (N-2) are compounds represented by the following formulas (N-2-1) to (N-2-15).

Among the above specific examples, diamines represented by the formulas (N-1-2), (N-2-1) and (N-2-2) are preferable.

As the diamine represented by the formula (N-1) and the diamine represented by the formula (N-2), one compound may be used alone, or two or more may be mixed and used. The diamine represented by the formula (N-1) and the diamine represented by the formula (N-2) may be mixed with other diamines. In this case, the diamine represented by the formula (N-1) and the diamine represented by the formula (N-2) in the mixture of diamines are used in a proportion of 10% by weight or more and should be 50% by weight or more. Preferably, it is more preferably 80% by weight or more.

Other diamines that can be used in combination with the diamine represented by the formula (N-1) and the diamine represented by the formula (N-2) include, for example, a diamine having no side chain structure and a side chain structure. The diamine which has. Such other diamines may be one compound or two or more compounds.

The liquid crystal aligning agent of the present invention is preferably used for a liquid crystal display element in which liquid crystal molecules are aligned in parallel with a substrate and operated by an electric field, such as IPS mode. In such a case, since it is not necessary for the liquid crystal molecules to have a pretilt angle with respect to the substrate surface, other diamines having no side chain structure are preferably used.

The diamine having no side chain structure is at least one selected from the group of diamines represented by the following formulas (III) to (IX) and (XV).

In the formula (III), A ¹ is — (CH ₂ ) _m —, and m is an integer of 1 to 6. In the formulas (V), (VII) and (IX), X represents a single bond, —O—, —S—, —S—S—, —SO ₂ —, —CO—, —NH—, —N (CH _{3) -, - C (CH} 3) 2 -, - C (CF 3) 2 -, - (CH 2) m -, - O- (CH 2) m -O-, or -S- _(CH 2) _m -S-, m is an integer of 1-6. In Formula (VII), L ¹ and L ² are —H, but X is —NH—, —N (CH ₃ ) —, —CH ₂ —, —C (CH ₃ ) ₂ —, or —C ( When CF ₃ ) ₂ —, they may be bonded to each other to form a single bond. In Formulas (VIII) and (IX), Y represents a single bond, —O—, —S—, —CO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, or a carbon number of 1 to 3 alkylene. In formula (XV), R ³³ and R ³⁴ are independently alkyl or phenyl having 1 to 3 carbon atoms, G is independently alkylene, phenylene or alkyl-substituted phenylene having 1 to 6 carbon atoms, m is an integer of 1-10. In each of the above formulas, —H of the cyclohexane ring or the benzene ring is replaced with —F, —CH ₃ , —OH, —COOH, —SO ₃ H, —PO ₃ H ₂ , benzyl, or hydroxybenzyl. It may be.

Examples of the diamine represented by the formula (III) include diamines represented by the following formulas (III-1) to (III-3).

Examples of the diamine represented by the formula (IV) include diamines represented by the following formulas (IV-1) and (IV-2).

Examples of the diamine represented by the formula (V) include diamines represented by the following formulas (V-1) to (V-3).

Examples of the diamine represented by the formula (VI) include diamines represented by the following formulas (VI-1) to (VI-17).

Examples of the diamine represented by the formula (VII) include diamines represented by the following formulas (VII-1) to (VII-36).

Examples of the diamine represented by the formula (VIII) include diamines represented by the following formulas (VIII-1) to (VIII-6).

Examples of the diamine represented by the formula (IX) include diamines represented by the following formulas (IX-1) to (IX-16).

Examples of the diamine represented by the formula (XV) include a compound represented by the following formula (XV-1).

The liquid crystal aligning agent of the present invention can also be used in a liquid crystal display element such as a TN mode in which liquid crystal molecules need to have a pretilt angle with respect to the substrate surface. In that case, a diamine having a side chain structure may be mixed with the diamine represented by the formula (N-1) and the diamine represented by the formula (N-2). When it is desired to adjust the pretilt angle appropriately, the diamine represented by the formula (N-1) and the diamine represented by the formula (N-2) have a side chain structure and a diamine that does not have the above side chain structure. A mixture of both diamines can also be used.

式（Ｘ）において、
Ｚ^１は、単結合、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、または−（ＣＨ_２）_ｍ−であり、ｍは１〜６の整数であり、このアルキレンにおける任意の−ＣＨ_２−は−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられていてもよく；
Ｒ^３は、ステロイド骨格を有する基、炭素数３〜３０のアルキル、炭素数１〜３０のアルキルもしくは炭素数１〜３０のアルコキシを置換基として有するフェニル、または下記式（Ｘ−ａ）で表される基であり、この炭素数１〜３０のアルキルにおける任意の−ＣＨ_２−は−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられていてもよく；

式（Ｘ−ａ）において、
Ａ^２およびＡ^３は独立して、単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＣＨ＝ＣＨ−、または炭素数１〜１２のアルキレンであり、ａおよびｂは独立して０〜４の整数であり；
環Ｂおよび環Ｃは独立して１，４−フェニレン、１，４−シクロヘキシレン、１，３−ジオキサン−２，５−ジイル、ピリミジン−２，５−ジイル、ピリジン−２，５−ジイル、ナフタレン−１，５−ジイル、ナフタレン−２，７−ジイル、またはアントラセン−９，１０−ジイルであり；
Ｒ^４およびＲ^５は独立して、−ＦまたはＣＨ_３であり、ｆおよびｇは独立して０〜２の整数であり；
Ｒ^６は−Ｆ、−ＯＨ、−ＣＮ、炭素数１〜３０のアルキル、炭素数１〜３０のアルコキシ、または炭素数２〜３０のアルコキシアルキルであり、これらのアルキル、アルコキシ、アルコキシアルキルにおいて、任意の−Ｈは−Ｆで置き換えられていてもよく、任意の−ＣＨ_２−は−ＣＦ_２−または下記式（ｓ）で表される２価の基で置き換えられていてもよく；

式（ｓ）において、Ｒ^３５およびＲ^３６は独立して炭素数１〜３のアルキルであり、ｍは１〜６の整数であり；
ｃ、ｄおよびｅは独立して０〜３の整数であり、そして、ｃ＋ｄ＋ｅ≧１である。

式（ＸＩ）および（ＸＩＩ）において、
Ｒ^７は独立して−Ｈまたは−ＣＨ_３であり；
Ｒ^８は−Ｈ、炭素数１〜２０のアルキルまたは炭素数２〜２０のアルケニルであり；
Ａ^４は独立して単結合、−ＣＯ−または−ＣＨ_２−であり；
式（ＸＩＩ）において、
Ｒ^９およびＲ^１０は独立して炭素数１〜２０のアルキルまたはフェニルである。

式（ＸＩＩＩ）および（ＸＩＶ）において、Ａ^５は独立して−Ｏ−または炭素数１〜６のアルキレンであり；
式（ＸＩＩＩ）において、Ｒ^１１は−Ｈまたは炭素数１〜３０のアルキルであり、このアルキルの任意の−ＣＨ_２−は、−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく；
Ａ^６は単結合または炭素数１〜３のアルキレンであり；
環Ｔは１，４−フェニレンまたは１，４−シクロヘキシレンであり；
ｈは０または１であり；
式（ＸＩＶ）において、Ｒ^１２は炭素数６〜２２のアルキルであり；そして、
Ｒ^１３は炭素数１〜２２のアルキルである。 The diamine having a side chain structure is at least one selected from the group of diamines represented by the following formulas (X) to (XIV).

In formula (X),
Z ¹ is a single bond, —O—, —CO—, —COO—, —OCO—, —CONH—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, or - _{(CH 2) m} - and is, m is an integer from 1 to 6, any -CH ₂ - in this alkylene -O -, - be replaced by CH = CH- or -C≡C- Well;
R ³ is a group having a steroid skeleton, alkyl having 3 to 30 carbon atoms, phenyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms as a substituent, or a group represented by the following formula (X-a): Any —CH ₂ — in the alkyl having 1 to 30 carbon atoms may be replaced by —O—, —CH═CH— or —C≡C—;

In the formula (Xa),
A ² and A ³ are independently a single bond, —O—, —COO—, —OCO—, —CONH—, —CH═CH—, or alkylene having 1 to 12 carbons, and a and b are Independently an integer from 0 to 4;
Ring B and Ring C are independently 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, Naphthalene-1,5-diyl, naphthalene-2,7-diyl, or anthracene-9,10-diyl;
R ⁴ and R ⁵ are independently —F or CH ₃ and f and g are independently integers from 0 to 2;
R ⁶ is —F, —OH, —CN, alkyl having 1 to 30 carbons, alkoxy having 1 to 30 carbons, or alkoxyalkyl having 2 to 30 carbons. In these alkyls, alkoxys, alkoxyalkyls, Any —H may be replaced by —F, and any —CH ₂ — may be replaced by —CF ₂ — or a divalent group represented by the following formula (s);

In the formula (s), R ³⁵ and R ³⁶ are independently alkyl having 1 to 3 carbon atoms, and m is an integer of 1 to 6;
c, d and e are each independently an integer of 0 to 3, and c + d + e ≧ 1.

In formulas (XI) and (XII)
R ⁷ is independently —H or —CH ₃ ;
R ⁸ is —H, alkyl having 1 to 20 carbons or alkenyl having 2 to 20 carbons;
A ⁴ is independently a single bond, —CO— or —CH ₂ —;
In formula (XII):
R ⁹ and R ¹⁰ are independently alkyl having 1 to 20 carbons or phenyl.

In formulas (XIII) and (XIV), A ⁵ is independently —O— or alkylene having 1 to 6 carbons;
In the formula (XIII), R ¹¹ is —H or alkyl having 1 to 30 carbons, and arbitrary —CH ₂ — of this alkyl is replaced by —O—, —CH═CH— or —C≡C—. May be
A ⁶ is a single bond or alkylene having 1 to 3 carbon atoms;
Ring T is 1,4-phenylene or 1,4-cyclohexylene;
h is 0 or 1;
In formula (XIV), R ¹² is alkyl having 6 to 22 carbons; and
R ¹³ is alkyl having 1 to 22 carbons.

Examples of the diamine represented by the formula (X) include diamines represented by the following formulas (X-1) to (X-37) and formulas (X-38) to (X-43).

In the formulas (X-1) to (X-11), R ²³ is preferably alkyl having 1 to 30 carbons or alkoxy having 1 to 30 carbons, and alkyl having 5 to 25 carbons or 5 to 5 carbons. More preferably, it is 25 alkoxy. R ²⁴ is preferably alkyl having 1 to 30 carbons or alkoxy having 1 to 30 carbons, and more preferably alkyl having 3 to 25 carbons or alkoxy having 3 to 25 carbons.

In the formulas (X-12) to (X-17), R ²⁵ is preferably alkyl having 4 to 30 carbons, and more preferably alkyl having 6 to 25 carbons. In the formulas (X-16) and (X-17), R ²⁶ is preferably an alkyl having 6 to 30 carbon atoms, and more preferably an alkyl having 8 to 25 carbon atoms.

In the formulas (X-18) to (X-37), R ²⁷ is preferably alkyl having 1 to 30 carbons or alkoxy having 1 to 30 carbons, and alkyl having 3 to 25 carbons or 3 to 3 carbons. More preferably, it is 25 alkoxy. R ²⁸ is preferably —H, —F, alkyl having 1 to 30 carbons, alkoxy having 1 to 30 carbons, —CN, —OCH ₂ F, —OCHF ₂ or —OCF _3. More preferably, it is 3-25 alkyl or C3-C25 alkoxy.

The diamine represented by the formula (X) is preferably a diamine represented by the formulas (X-1) to (X-11), represented by the formulas (X-2) and (X-4) to (X-6). More preferred are diamines.

In the diamine represented by the formula (XI), in the formula (XI), one of the two “NH ₂ -Ph-A ⁴ —O—” is bonded to the 3-position of the steroid skeleton, and the other is bonded to the 6-position. It is preferable. The two amino groups are each bonded to phenyl, and preferably bonded to the meta position or the para position with respect to the bonding position of A ⁴ .

Examples of the diamine represented by the formula (XI) include diamines represented by the following formulas (XI-1) to (XI-4).

In the diamine represented by the formula (XII), in the formula (XII), two “NH ₂ — (R ¹⁰ —) Ph—A ⁴ —O—” are each bonded to phenyl. It is bonded to carbon in the meta or para position relative to the carbon to which the skeleton is bonded. The two amino groups are each bonded to phenyl, but are preferably bonded to the meta position or the para position with respect to A ⁴ .

Examples of the diamine represented by the formula (XII) include diamines represented by the following formulas (XII-1) to (XII-8).

The diamine represented by the formula (XIII), in the formula (XIII), the two amino groups are respectively bonded to the phenyl, it is preferably in meta or para position relative to A ^5.

Examples of the diamine represented by the formula (XIII) include diamines represented by the following formulas (XIII-1) to (XIII-8).

In Formulas (XIII-1) to (XIII-3), R ²⁹ is preferably —H, alkyl having 1 to 30 carbons or alkoxy having 1 to 30 carbons, and alkyl or carbon having 3 to 30 carbons. It is more preferable that it is several 3-30 alkoxy. In the formulas (XII-4) to (XII-8), R ³⁰ is preferably —H, alkyl having 1 to 30 carbons or alkoxy having 1 to 30 carbons, and alkyl having 3 to 30 carbons or More preferably, it is C3-C30 alkoxy.

The diamine represented by the formula (XIV), in the formula (XIV), the two amino groups are respectively bonded to the phenyl, it is preferably in meta or para position relative to A ^5.

Examples of the diamine represented by the formula (XIV) include diamines represented by the following formulas (XIV-1) to (XIV-3).

In the formulas (XIV-1) to (XIV-3), R ³¹ is preferably alkyl having 6 to 22 carbons, and more preferably alkyl having 6 to 20 carbons. R ³² is preferably —H or alkyl having 1 to 22 carbons, and more preferably alkyl having 1 to 10 carbons.

The diamine having a side chain structure is derived from the compounds represented by formulas (X-2), (X-4) to (X-6), (XIII-2), (XIII-4) and (XIII-6). It is preferable that at least one selected.

As other diamines in the present invention, diamines other than the diamines represented by the aforementioned formulas (III) to (IX), (XV) and (X) to (XIV) can also be used. Examples of such other diamines include naphthalene-based diamines having a naphthalene structure, fluorene-based diamines having a fluorene structure, and diamines having a side chain structure other than formulas (VIII) to (XII).

Examples of other diamines include compounds represented by the following formulas (1 ′) to (8 ′).

式（１'）〜（８'）中、Ｒ^３５およびＲ^３６はそれぞれ独立して炭素数３〜３０のアルキル基を表す。

In formulas (1 ′) to (8 ′), R ³⁵ and R ³⁶ each independently represents an alkyl group having 3 to 30 carbon atoms.

Said other diamine can be used in the range which does not impair the effect of this invention in the diamine which comprises the polyamic acid in the liquid crystal aligning agent of this invention.

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

式（Ａｎ−１）、（Ａｎ−４）および（Ａｎ−５）において、Ｘ^１は独立して単結合または−ＣＨ_２−であり；
式（Ａｎ−２）において、Ｇ^１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−２）〜（Ａｎ−４）において、Ｙ^１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；

式（Ａｎ−３）〜（Ａｎ−５）において、環Ｅは炭素数３〜１０の単環式炭化水素の基または炭素数６〜２０の縮合多環式炭化水素の基を表し、この基の任意の水素はメチル、エチルまたはフェニルで置き換えられていてもよく；
環に掛かっている結合手は環を構成する任意の炭素に連結しており、２本の結合手が同一の炭素に連結してもよく；
式（Ａｎ−６）において、Ｘ^１１は炭素数２〜６のアルキレンであり；
Ｍｅはメチルを表し、そして、Ｐｈはフェニルを表す。 Other tetracarboxylic dianhydrides used by mixing with the tetracarboxylic dianhydride represented by the formula (I) in the present invention are represented by the following formulas (An-1) to (An-6). At least one selected from the group of compounds.

In formulas (An-1), (An-4) and (An-5), X ¹ is independently a single bond or —CH ₂ —;
In Formula (An-2), G ¹ represents a single bond, alkylene having 1 to 20 carbons, —CO—, —O—, —S—, —SO ₂ —, —C (CH ₃ ) ₂ —, or — C (CF ₃ ) ₂ —;
In formulas (An-2) to (An-4), Y ¹ is independently one selected from the group of trivalent groups described below;

In the formulas (An-3) to (An-5), the ring E represents a monocyclic hydrocarbon group having 3 to 10 carbon atoms or a condensed polycyclic hydrocarbon group having 6 to 20 carbon atoms. Any hydrogen in may be replaced by methyl, ethyl or phenyl;
The bond on the ring is linked to any carbon that makes up the ring, and two bonds may be linked to the same carbon;
In the formula (An-6), X ¹¹ is alkylene having 2 to 6 carbons;
Me represents methyl and Ph represents phenyl.

The other tetracarboxylic dianhydride may be one compound or two or more compounds. The tetracarboxylic acids are roughly classified into aromatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, aliphatic tetracarboxylic dianhydrides, and silsesquioxane-based tetracarboxylic dianhydrides. Is done.

An aromatic tetracarboxylic dianhydride is a compound in which at least one of the two acid anhydrides is an acid anhydride with two carboxyls attached to the aromatic compound. Examples of the aromatic tetracarboxylic dianhydride include compounds represented by the following formulas (1) to (18).

The aromatic tetracarboxylic dianhydride is preferably a compound represented by the formulas (1), (2), (5) to (7) and (17), and is represented by the formula (1). More preferably, it is a compound.

An alicyclic tetracarboxylic dianhydride is a compound in which at least one of the two acid anhydrides is an acid anhydride with two carboxyls attached to the alicyclic compound. Examples of the alicyclic tetracarboxylic dianhydride include the following formulas (24) to (34), (36) to (40), (42) to (44) and (49) to (58), and ( 62) to (64).

The alicyclic tetracarboxylic dianhydride is preferably a compound represented by the formulas (25), (36) to (39), (44), (49), and (68). More preferred are compounds represented by 37) and (49).

An aliphatic tetracarboxylic dianhydride is a compound having two acid anhydrides with two carboxy groups bonded to an aliphatic compound. Examples of the aliphatic tetracarboxylic dianhydride include compounds represented by the following formulas (23), (45) to (48), (66), (67), and (68).

The aliphatic tetracarboxylic dianhydride is preferably a compound represented by the formulas (23) and (68).

A part of tetracarboxylic dianhydride may be replaced with dicarboxylic dianhydride. Such replacement can cause termination of the polymerization reaction when the polyamic acid is produced, and further progress of the polymerization reaction can be suppressed. For this reason, the molecular weight of the obtained polymer (polyamic acid or a derivative thereof) can be easily controlled by such replacement, and for example, the coating characteristics of the liquid crystal aligning agent are improved without impairing the effects of the present invention. be able to. The ratio of the dicarboxylic acid monoanhydride to the tetracarboxylic acid dianhydride may be in a range that does not impair the effects of the present invention, but as a guideline, it is preferably 10 mol% or less of the total tetracarboxylic acid dianhydride amount. The tetracarboxylic dianhydride replaced with the dicarboxylic acid monoanhydride may be one type or two or more types as long as the effects of the present invention are not impaired. Examples of the dicarboxylic acid monoanhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, Examples include n-hexadecyl succinic anhydride and cyclohexane anhydride.

In the tetracarboxylic dianhydride, the ratio of the dicarboxylic acid to the tetracarboxylic dianhydride is in the range of 10 mol% or less, and a part of the tetracarboxylic dianhydride may be replaced with the dicarboxylic acid. The tetracarboxylic dianhydride replaced with the dicarboxylic acid may be one type or two or more types as long as the effects of the present invention are not impaired.

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

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

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

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

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

For example, the liquid crystal aligning agent of the present invention may further contain an alkenyl-substituted nadiimide compound from the viewpoint of stabilizing the electrical characteristics of the liquid crystal display element over a long period of time. The alkenyl-substituted nadiimide compound may be a single compound or two or more compounds. From the above viewpoint, the content of the alkenyl-substituted nadiimide compound is preferably 0.01 to 1.00, preferably 0.01 to 0.70, in a weight ratio with respect to the polyamic acid or its derivative in the liquid crystal aligning agent. Is more preferable, and it is still more preferable that it is 0.01-0.50.

The alkenyl-substituted nadiimide compound is preferably a compound that can be dissolved in a solvent that dissolves the polyamic acid or derivative thereof used in the present invention. Examples of such alkenyl-substituted nadiimide compounds include compounds represented by the following formula (Ina).

In the formula (Ina), L ¹ and L ² are each independently hydrogen, alkyl having 1 to 12 carbons, alkenyl having 3 to 6 carbons, cycloalkyl having 5 to 8 carbons, aryl or benzyl, n is 1 or 2.

When n = 1, W is alkyl of 1 to 12 carbon atoms, alkenyl having 2 to 6 carbon atoms, cycloalkyl of 5 to 8 carbon atoms, having 6 to 12 carbon atoms aryl, benzyl, ^-Z 1 - (O) _{^{q - (Z 2 O) r}} -Z 3 -H (Z 1, Z 2 and ^{Z 3} are independently alkylene of 2 to 6 carbon atoms, q is 0 or 1, and r is 1 to 30 -(Z ⁴ ) _s -BZ ⁵ -H (Z ⁴ and Z ⁵ are each independently an alkylene having 1 to 4 carbon atoms or a cyclo having 5 to 8 carbon atoms). Alkylene, B is phenylene, and s is 0 or 1.) -B-T-B-H (B is phenylene, and T is -CH ₂ -,- _{C (CH 3) 2 -,} - O -, - CO -, - S- or SO ₂ -. a a) a group represented by child 1-3 hydrogens et groups represent substituted groups with hydroxyl groups.

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

When n = 2 in formula (Ina), W is an alkylene of 2 to 20 carbon atoms, cycloalkylene of 5 to 8 carbon atoms, arylene having 6 to 12 carbon ^{atoms, -Z 1 -O- (Z 2 O} ) r ^{-Z 3 - (Z 1 ~Z 3} , and r means the are as defined above.) groups represented ^{by, -Z 4 -B-Z 5 -} ( mean of Z 4, ^{Z 5} and B are the is as. a group represented _{by), -B- (O-B)} s -T- (B-O) s -B- (B represents a phenylene, T is alkylene of 1 to 3 carbon atoms, -O- or SO 2 _- and is, s is 0 or 1 group represented by) or 1-3 hydrogen of these groups, is replaced with a hydroxyl group..

At this time, preferable W is alkylene having 2 to 12 carbon atoms, cyclohexylene, phenylene, tolylene, xylylene, —C ₃ H ₆ —O— (Z ² —O) _r —O—C ₃ H ₆ — (Z ² is . an alkylene of 2 to 6 carbon atoms, r is 1 or 2 groups represented by), -B-T-B- ( B represents a phenylene, and T is _-CH 2 -, - O- or SO ₂ -.. represents a group represented _{by), -B-O-B-} C 3 H 6 -B-O-B- (B is phenylene), a group represented by and these groups In which one or two hydrogens are replaced by a hydroxyl group.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Among the alkenyl-substituted nadiimide compounds, preferred compounds are shown below.

N, N′-ethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-ethylene-bis (allylmethylbicyclo [2.2. 1] Hept-5-ene-2,3-dicarboximide), N, N′-ethylene-bis (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) N, N′-trimethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-hexamethylene-bis (allylbicyclo [2.2 .1] hept-5-ene-2,3-dicarboximide), N, N′-hexamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxy Imide), N, N′-dodecamethylene Bis (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-dica Boxoxyimide), N, N′-p-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-xylylene-bis ( Allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene -2,3-dicarboximide), 2,2-bis [4- {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane 2,2-bis [4- {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane, 2,2-bis [4 -{4- (methallylbicyclo 2.2.1] Hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3- Dicarboximido) phenyl} methane, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane,

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

Further preferred alkenyl-substituted nadiimide compounds are shown below.

N, N′-ethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-ethylene-bis (allylmethylbicyclo [2.2. 1] Hept-5-ene-2,3-dicarboximide), N, N′-ethylene-bis (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) N, N′-trimethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-hexamethylene-bis (allylbicyclo [2.2 .1] hept-5-ene-2,3-dicarboximide), N, N′-hexamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxy Imide), N, N′-dodecamethylene Bis (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-dica Boxoxyimide), N, N′-p-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-xylylene-bis ( Allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene -2,3-dicarboximide),

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

As a particularly preferred alkenyl-substituted nadiimide compound, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) represented by the following formula (Ina-1) Phenyl} methane, N, N′-m-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) of the formula (Ina-2), and the formula N, N′-hexamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) represented by (Ina-3).

For example, the liquid crystal aligning agent of this invention may further contain the compound which has a radically polymerizable unsaturated double bond from a viewpoint of stabilizing the electrical property of a liquid crystal display element for a long term. The compound having a radically polymerizable unsaturated double bond may be one type of compound or two or more types of compounds. The compound having a radically polymerizable unsaturated double bond does not include the alkenyl-substituted nadiimide compound. From the above viewpoint, the content of the compound having a radical polymerizable unsaturated double bond is preferably 0.01 to 1.00 in terms of weight ratio to the polyamic acid or its derivative, and is preferably 0.01 to 0.00. 70 is more preferable, and 0.01 to 0.50 is even more preferable.

The ratio of the compound having a radical polymerizable unsaturated double bond to the alkenyl-substituted nadiimide compound is from the viewpoint of reducing the ion density of the liquid crystal display element, suppressing the increase in ion density over time, and further suppressing the afterimage. The weight ratio is preferably 0.1 to 10, and more preferably 0.5 to 5.

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

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

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

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

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

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

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

For example, the liquid crystal aligning agent of this invention may further contain the oxazine compound from a viewpoint of the long-term stability of the electrical property in a liquid crystal display element. The oxazine compound may be one kind of compound or two or more kinds of compounds. From the above viewpoint, the content of the oxazine compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, and more preferably 1 to 20% with respect to the polyamic acid or a derivative thereof. More preferably, it is% by weight.

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

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

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

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

In the formulas (a) to (c), R ¹ and R ² are organic groups having 1 to 30 carbon atoms. In formulas (a) to (f), R ³ to R ⁶ represent hydrogen or a hydrocarbon group having 1 to 6 carbon atoms. In the formulas (c), (d) and (f), X represents a single bond, —O—, —S—, —S—S—, —SO ₂ —, —CO—, —CONH—, —NHCO. _{-, - C (CH 3)} 2 -, - C (CF 3) 2 -, - (CH 2) m -, - O- (CH 2) m -O -, - S- (CH 2) m -S -. Here, m is an integer of 1-6. In the formulas (e) and (f), Y is independently a single bond, —O—, —S—, —CO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —. Or it is C1-C3 alkylene. Then, the benzene ring of formula (a) ~ (f), is hydrogen bonded to the naphthalene ring, _{-F independently, -CH 3, -OH, -COOH,} -SO 3 H, -PO 3 H 2 May be replaced.

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

式中、Ｒ^１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。 Examples of the oxazine compound represented by the formula (a) include the following oxazine compounds.

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

式中、Ｒ^１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。 Examples of the oxazine compound represented by the formula (b) include the following oxazine compounds.

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

式（ｃ’）中、Ｒ^１およびＲ^２は炭素数１〜３０の有機基、Ｒ^３からＲ^６は水素または炭素数１〜６の炭化水素基、Ｘは単結合、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−ＣＯ−、−Ｏ−、−ＳＯ_２−またはＣ（ＣＦ_３）_２−を表す。 Examples of the oxazine compound represented by the formula (c) include an oxazine compound represented by the following formula (c ′).

In the formula (c ′), R ¹ and R ² are organic groups having 1 to 30 carbon atoms, R ³ to R ⁶ are hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, X is a single bond, —CH ₂ —, _{-C (CH 3) 2 -,} - CO -, - O -, - SO 2 - or C _{(CF 3) 2} - represents a.

Examples of the oxazine compound represented by the formula (c ′) include the following oxazine compounds.

上記式中、Ｒ^１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 above formula, R ¹ 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 (d) include the following oxazine compounds.

Examples of the oxazine compound represented by the formula (e) include the following oxazine compounds.

Examples of the oxazine compound represented by the formula (f) include the following oxazine compounds.

Of these, more preferably, the formula (b-1), the formula (c-1), the formula (c-3), the formula (c-5), the formula (c-7), the formula (c-9), Oxazine compounds represented by formula (d-1) to formula (d-6), formula (e-3), formula (e-4), and formula (f-2) to formula (f-4) can be given. .

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

For example, the oxazine compound represented by the formula (a) can be obtained by reacting a phenol compound, a primary amine and an aldehyde (see International Publication No. 2004/009708 pamphlet).

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

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

In addition, the oxazine compounds represented by the formulas (d) to (f) include diamines such as 4,4′-diaminodiphenylmethane, diamines having a plurality of benzene rings and an organic group that binds them, and aldehydes such as formalin, and It can be obtained by dehydrating and condensing phenol in n-butanol at a temperature of 90 ° C. or higher (see JP 2004-352670 A).

For example, the liquid crystal aligning agent of this invention may further contain the oxazoline compound from a viewpoint of the long-term stability of the electrical property in a liquid crystal display element. The oxazoline compound is a compound having an oxazoline structure. The oxazoline compound may be a kind of compound or two or more kinds of compounds. From the above viewpoint, the content of the oxazoline compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, and more preferably 1 to 20% with respect to the polyamic acid or a derivative thereof. It is preferable that it is weight%. Or it is preferable from said viewpoint that content of the said oxazoline compound is 0.1 to 40 weight% with respect to the said polyamic acid or its derivative (s), when the oxazoline structure in an oxazoline compound is converted into oxazoline. .

The oxazoline compound may have only one type of oxazoline structure in one compound, or may have two or more types. Moreover, the said oxazoline compound should just have one said oxazoline structure in one compound, but it is preferable to have 2 or more. The oxazoline compound may be a polymer having an oxazoline ring structure in the side chain, or may be a copolymer. The polymer having an oxazoline structure in the side chain may be a homopolymer of a monomer having an oxazoline structure in the side chain, or a copolymer of a monomer having an oxazoline structure in the side chain and a monomer having no oxazoline structure It may be. The copolymer having an oxazoline structure in the side chain may be a copolymer of two or more monomers having an oxazoline structure in the side chain, or two or more monomers having an oxazoline structure in the side chain and an oxazoline structure. It may also be a copolymer with a monomer that does not have.

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

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

More preferred oxazoline compounds include, for example, 2,2'-bis (2-oxazoline) and 1,3-bis (4,5-dihydro-2-oxazolyl) benzene.

For example, the liquid crystal aligning agent of this invention may further contain the epoxy compound from a viewpoint of the long-term stability of the electrical property in a liquid crystal display element. The epoxy compound may be one type of compound or two or more types of compounds. From the above viewpoint, 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% with respect to the polyamic acid or a derivative thereof. More preferably, it is% by weight.

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

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

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

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

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

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

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

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

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

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

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

Examples of glycidylamine include polyglycidylamine compounds.

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

Examples of glycidyl amide include glycidyl amide type epoxy compounds.

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

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

As the bisphenol A type epoxy compound, for example, 828, 1001, 1002, 1003, 1004, 1007, 1010 (all are made by Japan Epoxy Resin (currently available as a product of jER series of Mitsubishi Chemical Corporation)) Epototo YD-128 (manufactured by Toto Kasei Co., Ltd.), DER-331, DER-332, DER-324 (all manufactured by The Dow Chemical Company), Epicron 840, Epicron 850, Epicron 1050 (all DIC Corporation) Manufactured), Epomic R-140, Epomic R-301, and Epomic R-304 (all manufactured by Mitsui Chemicals, Inc.).

Examples of the bisphenol F type epoxy compound include 806, 807, and 4004P (all manufactured by Japan Epoxy Resin Co., Ltd.), Epototo YDF-170, Epototo YDF-175S, and Epototo YDF-2001 (all manufactured by Toto Kasei Co., Ltd.). DER-354 (manufactured by The Dow Chemical Company), Epicron 830, and Epicron 835 (all manufactured by DIC Corporation).

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

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

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

Examples of brominated bisphenol-A type epoxy compounds include 5050 and 5051 (both manufactured by Japan Epoxy Resin Co., Ltd.), Epototo YDB-360, Epototo YDB-400 (both manufactured by Toto Kasei Co., Ltd.), and DER-530. DER-538 (all manufactured by The Dow Chemical Company), Epicron 152, and Epicron 153 (all manufactured by DIC Corporation).

Examples of the phenol novolac type epoxy compound include 152, 154 (all manufactured by Japan Epoxy Resin), YDPN-638 (manufactured by Toto Kasei Co., Ltd.), DEN431, DEN438 (all manufactured by The Dow Chemical Company), and Epicron N-770. (Made by DIC Corporation), EPPN-201, and EPPN-202 (all are made by Nippon Kayaku Co., Ltd.).

Examples of the cresol novolac type epoxy compound include 180S75 (manufactured by Japan Epoxy Resin Co., Ltd.), YDCN-701, YDCN-702 (both manufactured by Toto Kasei Co., Ltd.), Epicron N-665, and Epicron N-695 (all of them). DIC Corporation), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, and EOCN-1027 (all manufactured by Nippon Kayaku Co., Ltd.).

Examples of the bisphenol A novolac type epoxy compound include 157S70 (manufactured by Japan Epoxy Resin Co., Ltd.) and Epicron N-880 (manufactured by DIC Corporation).

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

Examples of the aromatic polyglycidyl ether compound include hydroquinone diglycidyl ether (following formula E101), catechol diglycidyl ether (following formula E102) resorcinol diglycidyl ether (following formula E103), tris (4-glycidyloxyphenyl) methane (described below). Formula E105), 1031S, 1032H60 (all manufactured by Japan Epoxy Resins Co., Ltd.), TACTIX-742 (manufactured by The Dow Chemical Company), Denacol EX-201 (manufactured by Nagase ChemteX Corporation), DPPN-503, DPPN- 502H, DPPN-501H, NC6000 (all manufactured by Nippon Kayaku Co., Ltd.), Techmore VG3101L (manufactured by Mitsui Chemicals, Inc.), a compound represented by the following formula E106, and a compound represented by the following formula E107 It is done.

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

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

Examples of the aliphatic polyglycidyl ether compound include ethylene glycol diglycidyl ether (following formula E108), diethylene glycol diglycidyl ether (following formula E109), polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether (following formula E110), and tripropylene. Glycol diglycidyl ether (following formula E111), polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether (following formula E112), 1,4-butanediol diglycidyl ether (following formula E113), 1,6-hexanediol di Glycidyl ether (following formula E114), dibromoneopentyl glycol diglycidyl ether (following formula E115), Denacol EX-810, Cole EX-851, Denacol EX-8301, Denacol EX-911, Denacol EX-920, Denacol EX-931, Denacol EX-211, Denacol EX-212, Denacol EX-313 (all manufactured by Nagase ChemteX Corporation) DD-503 (manufactured by ADEKA Corporation), Rica Resin W-100 (manufactured by Shin Nippon Rika Co., Ltd.), 1,3,5,6-tetraglycidyl-2,4-hexanediol (formula E116 below), 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 Nagaseke Made Tex Co., Ltd.) and the like.

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

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

Examples of the diglycidyl ester compound include diglycidyl terephthalate (the following formula 117), diglycidyl phthalate (the following formula E118), bis (2-methyloxiranylmethyl) phthalate (the following formula E119), and the following formula E121. Examples thereof include a compound, a compound represented by the following formula E122, and a compound represented by the following formula E123.

Examples of the glycidyl ester epoxy compound include 871, 872 (all manufactured by Japan Epoxy Resin Co., Ltd.), Epicron 200, Epicron 400 (all manufactured by DIC Corporation), Denacol EX-711, and Denacol EX-721 (any Also manufactured by Nagase ChemteX Corporation).

Examples of the polyglycidylamine compound include N, N-diglycidylaniline (following formula E124), N, N-diglycidyl-o-toluidine (following formula E125), N, N-diglycidyl-m-toluidine (following formula E126). N, N-diglycidyl-2,4,6-tribromoaniline (following formula E127), 3- (N, N-diglycidyl) aminopropyltrimethoxysilane (following formula E128), N, N, O-triglycidyl -P-aminophenol (formula E129 below), N, N, O-triglycidyl-m-aminophenol (formula E130 below), N, N, N ', N'-tetraglycidyl-m-xylylenediamine (TETRAD) -X (Mitsubishi Gas Chemical Co., Ltd.), the following formula E132), 1,3-bis (N, N-diglycidylaminomethyl) cyclo Xan (TETRAD-C (Mitsubishi Gas Chemical Co., Ltd.), the following formula E133), 1,4-bis (N, N-diglycidylaminomethyl) cyclohexane (the following formula E134), 1,3-bis (N, N-diglycidylamino) cyclohexane (formula E135), 1,4-bis (N, N-diglycidylamino) cyclohexane (formula E136), 1,3-bis (N, N-diglycidylamino) benzene ( Formula E137), 1,4-bis (N, N-diglycidylamino) benzene (Formula E138), 2,6-bis (N, N-diglycidylaminomethyl) bicyclo [2.2.1] heptane (Formula E139 below), N, N, N ′, N′-tetraglycidyl-4,4′-diaminodicyclohexylmethane (formula E140 below), 2,2′-dimethyl- (N, , N ′, N′-tetraglycidyl) -4,4′-diaminobiphenyl (the following formula E141), N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenyl ether (the following formula E142), 1,3,5-tris (4- (N, N-diglycidyl) aminophenoxy) benzene (following formula E143), 2,4,4′-tris (N, N-diglycidylamino) diphenyl ether (following formula E144) , Tris (4- (N, N-diglycidyl) aminophenyl) methane (following formula E145), 3,4,3 ′, 4′-tetrakis (N, N-diglycidylamino) biphenyl (following formula E146), 3 , 4,3 ′, 4′-tetrakis (N, N-diglycidylamino) diphenyl ether (formula E147 below), a compound represented by formula E148 below, and And a compound represented by the formula E149.

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

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

Examples of monomers other than the monomer having oxiranyl in the copolymer of monomers having oxiranyl include, for example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth ) Acrylate, iso-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, styrene , 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 E150), 1,3-diglycidyl. Examples include -5-allyl-1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione (formula E151 below) and glycidyl isocyanurate type epoxy resin.

Examples of the chain aliphatic epoxy compound include epoxidized polybutadiene and epolide PB3600 (manufactured by Daicel Chemical Industries, Ltd.).

Examples of the cycloaliphatic epoxy compound include 2-methyl-3,4-epoxycyclohexylmethyl-2′-methyl-3 ′, 4′-epoxycyclohexylcarboxylate (formula E153 below), 2,3-epoxycyclopentane. -2 ', 3'-epoxycyclopentane ether (formula E154 below), ε-caprolactone modified 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarbochelate, 1,2: 8,9-diepoxy Limonene (Celoxide 3000 (manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexenylmethyl-3, '4'-epoxycyclohexene carboxylate (Celoxide 2021P (manufactured by Daicel Chemical Industries, Ltd.), the following formula E155) , A compound represented by the following formula E156, CY-175, CY-177, Y-179 (all manufactured by The Ciba-Geigy Chemical Corp. (available from Huntsman Japan)), EHPD-3150 (manufactured by Daicel Chemical Industries, Ltd.), and cyclic aliphatic epoxy resins. It is done.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

In the present invention, the concentration of the polymer component containing the polyamic acid or derivative thereof in the liquid crystal aligning agent is not particularly limited, but is preferably 0.1 to 40% by weight. When the liquid crystal aligning agent is applied to the substrate, it may be necessary to dilute the polymer component contained in advance with a solvent in order to adjust the film thickness. At this time, from the viewpoint of adjusting the viscosity of the liquid crystal aligning agent to a viscosity suitable for easily mixing the solvent with the liquid crystal aligning agent, the concentration of the polymer component is preferably 40% by weight or less.

The concentration of the polymer component in the liquid crystal aligning agent may be adjusted depending on the method of applying the liquid crystal aligning agent. When the application method of the liquid crystal aligning agent is a spinner method or a printing method, the concentration of the polymer component is usually 10% by weight or less in order to maintain a good film thickness. Other coating methods such as dipping and ink jet methods may further reduce the concentration. On the other hand, when the concentration of the polymer component is 0.1% by weight or more, the thickness of the obtained liquid crystal alignment film tends to be optimal. Therefore, the concentration of the polymer component is 0.1% by weight or more, preferably 0.5 to 10% by weight in the usual spinner method or printing method. However, depending on the application method of the liquid crystal aligning agent, it may be used at a lower concentration.

In addition, when using for preparation of a liquid crystal aligning film, the viscosity of the liquid crystal aligning agent of this invention can be determined according to the means and method of forming this liquid crystal aligning agent film. For example, when forming a film of a liquid crystal aligning agent using a printing machine, it is preferably 5 mPa · s or more from the viewpoint of obtaining a sufficient film thickness, and 100 mPa · s or less from the viewpoint of suppressing printing unevenness. It is preferably 10 to 80 mPa · s. When a liquid crystal aligning agent is applied by spin coating to form a liquid crystal aligning agent film, it is preferably 5 to 200 mPa · s, more preferably 10 to 100 mPa · s from the same viewpoint. The viscosity of the liquid crystal aligning agent can be reduced by curing with dilution or stirring with a solvent.

The liquid crystal aligning agent of the present invention may be in a form containing one kind of polyamic acid or a derivative thereof, or may be in the form of a so-called polymer blend in which two or more kinds of polyamic acid or a derivative thereof are mixed. Good.

The liquid crystal alignment film of the present invention is a film formed by heating the coating film of the liquid crystal aligning agent of the present invention, but as described above, ultraviolet linearly polarized light is irradiated before or after heating the coating film. The

The said coating film can be formed by apply | coating the liquid crystal aligning agent of this invention to the board | substrate in a liquid crystal display element similarly to preparation of a normal liquid crystal aligning film. Examples of the substrate include a glass substrate on which an electrode such as an ITO (Indium Tin Oxide) electrode, a color filter, or the like may be provided.

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

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

The liquid crystal alignment film of the present invention can be suitably obtained by a method that further includes steps other than the steps described above. Examples of such other steps include a step of drying the coating film. Note that the liquid crystal alignment film of the present invention does not require a step of cleaning the film after baking or ultraviolet irradiation with a cleaning liquid, but does not hinder the provision of a cleaning step for the convenience of other steps.

As the drying step, a method of heat-treating in an oven or an infrared furnace, a method of heat-treating on a hot plate, and the like are generally known as in the baking step. These methods are also applicable to the drying step. The drying step is preferably performed at a temperature within a range where the solvent can be evaporated, and more preferably at a temperature relatively lower than the temperature in the baking step.

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

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

The liquid crystal display element of the present invention includes a pair of substrates, a liquid crystal layer containing liquid crystal molecules, formed between the pair of substrates, an electrode for applying a voltage to the liquid crystal layer, and the liquid crystal molecules in a predetermined direction. And a liquid crystal alignment film to be aligned. The liquid crystal alignment film of the present invention is used for the liquid crystal alignment film.

As the substrate, the glass substrate described above in the liquid crystal alignment film of the present invention can be used. As the electrode, an ITO electrode formed on the glass substrate as described above in the liquid crystal alignment film of the present invention is used. Can be used.

The liquid crystal layer is formed of a liquid crystal composition that is sealed in a gap between a pair of substrates facing each other so that a surface on which a liquid crystal alignment film is formed on one substrate of the pair of substrates faces the other substrate.

The liquid crystal composition is not particularly limited, and various liquid crystal compositions having a positive or negative dielectric anisotropy can be used. Preferred liquid crystal compositions having a positive dielectric anisotropy include Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Laid-Open No. 5-501735, Japanese Patent Laid-Open No. 8-157826, and Japanese Patent Laid-Open No. 8-231960. JP-A-9-241644 (EP88272A1 specification), JP-A-9-302346 (EP806466A1 specification), JP-A-8-199168 (EP722998A1 specification), JP-A-9-235552, JP Japanese Laid-Open Patent Publication Nos. 9-255958, 9-241463 (EP882711A1), 10-204016 (EP844229A1), 10-204436, 10-231482, and JP 2000-087040, JP 2001-488 The liquid crystal composition disclosed in 2 publications, and the like.

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

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

In the liquid crystal display element of the present invention, the liquid crystal alignment film of the present invention is formed on at least one of a pair of substrates, and the obtained pair of substrates are opposed to each other with a liquid crystal alignment film facing inward through a spacer. It is obtained by enclosing a liquid crystal composition in the formed gap to form a liquid crystal layer. The production of the liquid crystal display element of the present invention may include additional steps such as attaching a polarizing film to the substrate as necessary.

The liquid crystal display element of the present invention can form liquid crystal display elements for various electric field systems. In such a liquid crystal display element for electric field mode, a liquid crystal display element for horizontal electric field mode in which the electrode applies a voltage to the liquid crystal layer in a horizontal direction with respect to the surface of the substrate, or a surface of the substrate. In addition, there is a vertical electric field type liquid crystal display element in which the electrode applies a voltage to the liquid crystal layer in the vertical direction.

The liquid crystal alignment film produced using the liquid crystal aligning agent of the present invention as a raw material can be applied to liquid crystal display elements of various display drive systems by appropriately selecting the polymer as the raw material.

The liquid crystal display element of the present invention may further include elements other than the above-described components. As such other components, the liquid crystal display element of the present invention is mounted with components usually used for liquid crystal display elements such as a polarizing plate (polarizing film), a wave plate, a light scattering film, and a drive circuit. May be.

Hereinafter, the present invention will be described with reference to examples. The compounds used in the examples are as follows.

<Tetracarboxylic dianhydride>
Acid dianhydride (A1): 1,2,3,4-cyclobutanetetracarboxylic dianhydride acid dianhydride (A2): pyromellitic dianhydride acid dianhydride (A3): 1,2,3 , 4-Tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride

<Diamine>
Diamine (D1): N, N′-bis (4-aminophenyl) -N, N′-dimethylethylenediaminediamine (D2): N, N′-bis (4-aminophenyl) piperazinediamine (D3): 4, 4'-diaminodiphenylmethanediamine (D4): 3,3'-diaminodiphenylmethanediamine (D5): 1,4-phenylenediaminediamine (D6): 4,4'-diaminoazobenzenediamine (D7): 4,4'- Diaminodiphenylamine

<Solvent>
N-methyl-2-pyrrolidone: NMP
Butyl cellosolve (ethylene glycol monobutyl ether): BC

<Additives>
Additive (Ad1): Bis [4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl] methane additive (Ad2): N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane additive (Ad3): 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane additive (Ad4): 3-aminopropyltriethoxysilane

<1. Synthesis of polyamic acid>
[Synthesis Example 1]
Into a 100 mL four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen gas inlet, 3.397 g of diamine (D1) and 40.0 g of dehydrated NMP were placed and dissolved under stirring in a dry nitrogen stream. Next, 1.232 g of acid dianhydride (A1), 1.370 g of acid dianhydride (A2) and 40.0 g of dehydrated NMP were added, and stirring was continued at room temperature for 24 hours. BC 14.0g was added to this reaction solution, and the polyamic acid solution whose polymer solid content concentration is 6 weight% was obtained. This polyamic acid solution is designated as PA1. The weight average molecular weight of the polyamic acid contained in PA1 was 104,500.

The weight average molecular weight of the polyamic acid was measured by GPC method using a 2695 separation module / 2414 differential refractometer (manufactured by Waters) and calculated by polystyrene conversion. The obtained polyamic acid was diluted with a phosphoric acid-DMF mixed solution (phosphoric acid / DMF = 0.6 / 100: weight ratio) so that the polyamic acid concentration was about 2% by weight. The column was HSPgel RT MB-M (manufactured by Waters), and measurement was performed under the conditions of a column temperature of 50 ° C. and a flow rate of 0.40 mL / min using the mixed solution as a developing agent. As the standard polystyrene, TSK standard polystyrene manufactured by Tosoh Corporation was used.

[Synthesis Examples 2 to 19]
Except for changing the tetracarboxylic dianhydride and diamine as shown in Table 1, polyamic acid solutions (PA2) to (PA19) having a polymer solid concentration of 6% by weight were prepared according to Synthesis Example 1. . Table 1 summarizes the measurement results of the weight average molecular weight of the obtained polyamic acid including the results of Synthesis Example 1.

<2. Fabrication of transmittance evaluation substrate>
[Example 1]
A mixed solvent of NMP / BC = 4/1 (weight ratio) was added to the polyamic acid solution (PA1) having a polymer solid content concentration of 6% by weight prepared in Synthesis Example 1, and diluted to a polymer solid content concentration of 4% by weight. A liquid crystal aligning agent was used. Using the obtained liquid crystal aligning agent, a transmittance evaluation substrate was prepared as follows.

<Method 1 for Producing Transmissivity Evaluation Substrate>
The liquid crystal aligning agent was apply | coated to the glass substrate with the spinner. In addition, including the following examples and comparative examples, the rotation speed of the spinner was adjusted according to the viscosity of the liquid crystal aligning agent so that the alignment film had the following film thickness. After coating and drying at 70 ° C. for 1 minute, the substrate was irradiated with linearly polarized ultraviolet light from the vertical direction through the polarizing plate using Multilight ML-501C / B manufactured by USHIO INC. . The exposure energy at this time is 3.0 ± 0.1 J / cm ² at a wavelength of 365 nm by measuring the amount of light using a UV integrated light meter UIT-150 (receiver UVD-S365) manufactured by USHIO INC. The exposure time was adjusted. The irradiation of ultraviolet rays was performed in air at room temperature by covering the entire apparatus with an ultraviolet ray preventing film. Next, heat treatment was performed at 230 ° C. for 15 minutes to form an alignment film having a thickness of 100 ± 10 nm.

[Examples 2 to 17]
A mixed solvent of NMP / BC = 4/1 (weight ratio) was added to each of the polyamic acid solutions (PA2 to PA17) having a polymer solid content concentration of 6% by weight prepared in Synthesis Examples 2 to 17, and the polymer solid content concentration was 4% by weight. % To obtain a liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, a transmittance evaluation substrate was produced by the method according to Example 1.

[Example 18]
To the polyamic acid solution (PA10) having a polymer solid content concentration of 6% by weight prepared in Synthesis Example 10, the additive (Ad1) was added at a rate of 20% by weight per polymer weight. Thereafter, a mixed solvent of NMP / BC = 4/1 (weight ratio) was added and diluted to a polymer solid content concentration of 4% by weight to obtain a liquid crystal aligning agent. In addition, the weight of an additive is not included in calculation of the polymer solid content concentration at the time of using an additive including the following Example. Using the obtained liquid crystal aligning agent, a transmittance evaluation substrate was produced by the method according to Example 1.

[Example 19]
The additive (Ad2) was added to the polyamic acid solution (PA10) having a polymer solid content concentration of 6% by weight prepared in Synthesis Example 10 at a rate of 20% by weight per polymer weight. Thereafter, a mixed solvent of NMP / BC = 4/1 (weight ratio) was added and diluted to a polymer solid content concentration of 4% by weight to obtain a liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, a transmittance evaluation substrate was produced by the method according to Example 1.

[Example 20]
To the polyamic acid solution (PA10) having a polymer solid concentration of 6% by weight prepared in Synthesis Example 10, the additive (Ad3) was added at a rate of 10% by weight per polymer weight. Thereafter, a mixed solvent of NMP / BC = 4/1 (weight ratio) was added and diluted to a polymer solid content concentration of 4% by weight to obtain a liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, a transmittance evaluation substrate was produced by the method according to Example 1.

[Example 21]
The additive (Ad4) was added to the polyamic acid solution (PA10) having a polymer solid content concentration of 6 wt% prepared in Synthesis Example 10 at a ratio of 0.5 wt% per polymer weight. Thereafter, a mixed solvent of NMP / BC = 4/1 (weight ratio) was added and diluted to a polymer solid content concentration of 4% by weight to obtain a liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, a transmittance evaluation substrate was produced by the method according to Example 1.

[Example 22]
A mixed solvent of NMP / BC = 4/1 (weight ratio) was added to the polyamic acid solution (PA10) having a polymer solid concentration of 6% by weight prepared in Synthesis Example 10, and diluted to a polymer solids concentration of 4% by weight. A liquid crystal aligning agent was used. Using the obtained liquid crystal aligning agent, a transmittance evaluation substrate was prepared as follows.

<Method 2 for Producing Transmissivity Evaluation Substrate>
The liquid crystal aligning agent was apply | coated to the glass substrate with the spinner. After the coating, it was dried by heating at 70 ° C. for 1 minute, and then heat-treated at 230 ° C. for 15 minutes. This glass substrate was irradiated with linearly polarized ultraviolet light through a polarizing plate from the vertical direction with respect to the substrate using Multilight ML-501C / B manufactured by Ushio Electric Co., Ltd. (exposure energy: 3. at 365 nm). 0 ± 0.1 J / cm ² ) and an alignment film having a thickness of 100 ± 10 nm were formed. The conditions of ultraviolet irradiation and adjustment of exposure energy were in accordance with the method of Example 1.

[Comparative Examples 1 and 2]
A mixed solvent of NMP / BC = 4/1 (weight ratio) was added to each of the polyamic acid solutions (PA 18 and 19) having a polymer solid concentration of 6% by weight prepared in Synthesis Examples 18 and 19, and the polymer solid content concentration was 4%. % To obtain a liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, a transmittance evaluation substrate was produced by the method according to Example 1.

[Comparative Example 3]
A mixed solvent of NMP / BC = 4/1 (weight ratio) was added to the polyamic acid solution (PA19) having a polymer solid concentration of 6% by weight prepared in Synthesis Example 19, and diluted to a polymer solids concentration of 4% by weight. A liquid crystal aligning agent was used. Using the obtained liquid crystal aligning agent, a transmittance evaluation substrate was produced by a method according to Example 22.

<3. Evaluation of transmittance>
The transmittance of the alignment film was measured using a UV-Vis spectrum measuring device (V-660 manufactured by JASCO Corporation). A glass substrate on which no alignment film was formed was used as a reference. The measurement was performed in the wavelength range of 380 to 780 nm every 1 nm at a scanning speed of 400 nm / min. The average value of the transmittance in the wavelength region was defined as the transmittance of the alignment film. It can be said that the larger the value, the better the transmittance. The measurement results are shown in Table 2.

表中の「−」は添加剤を加えていないことを表す。

"-" In the table indicates that no additive is added.

Since Comparative Example 1 uses a polyamic acid synthesized from a diamine having an azobenzene structure as a raw material, the transmittance is remarkably inferior. It turns out that the transmittance | permeability of the alignment film of Examples 1-22 of this invention is favorable, and there is little coloring.

<4. Production of liquid crystal display element>
[Example 23]
A mixed solvent of NMP / BC = 4/1 (weight ratio) was added to the polyamic acid solution (PA1) having a polymer solid content concentration of 6% by weight prepared in Synthesis Example 1, and diluted to a polymer solid content concentration of 4% by weight. A liquid crystal aligning agent was used. A liquid crystal cell was prepared as follows using the obtained liquid crystal aligning agent.

<Method 1 for manufacturing liquid crystal display element>
The liquid crystal aligning agent was apply | coated to the glass substrate with two ITO electrodes with the spinner. After coating and drying for about 1 minute at 70 ° C, UV light is irradiated from the vertical direction to the substrate through a polarizing plate using Multilight ML-501C / B manufactured by Ushio Electric Co., Ltd. (Exposure energy: 3.0 ± 0.1 J / cm ^{2 at} 365 nm). The conditions for ultraviolet irradiation and the method for adjusting the exposure energy were the same as in Example 1. Next, heat treatment was performed at 230 ° C. for 15 minutes to form an alignment film having a thickness of 100 ± 10 nm.

Two substrates on which an alignment film is formed on an ITO electrode are opposed to each other, and the alignment films are further opposed so that the polarization directions of ultraviolet rays irradiated to the respective alignment films are parallel to each other. A gap for injecting the liquid crystal composition was formed between and bonded together to assemble an empty cell having a cell thickness of 4 μm. The injection port for injecting the liquid crystal into the empty cell was provided at a position where the liquid crystal flow direction at the time of injection was substantially parallel to the polarization direction of the ultraviolet rays irradiated to the alignment film.

The liquid crystal composition A shown below was vacuum-injected into the empty cell produced as described above to prepare a liquid crystal cell.
<Liquid crystal composition A>

[Examples 24-39]
A mixed solvent of NMP / BC = 4/1 (weight ratio) was added to each of the polyamic acid solutions (PA2 to PA17) having a polymer solid content concentration of 6% by weight prepared in Synthesis Examples 2 to 17, and the polymer solid content concentration was 4% by weight. % To obtain a liquid crystal aligning agent. An empty cell was assembled by the method according to Example 23 using the obtained liquid crystal aligning agent. And liquid crystal composition A was vacuum-injected into these empty cells, and the liquid crystal cell was created.

[Example 40]
To the polyamic acid solution (PA10) having a polymer solid content concentration of 6% by weight prepared in Synthesis Example 10, the additive (Ad1) was added at a rate of 20% by weight per polymer weight. Thereafter, a mixed solvent of NMP / BC = 4/1 (weight ratio) was added and diluted to a polymer solid content concentration of 4% by weight to obtain a liquid crystal aligning agent. An empty cell was assembled by the method according to Example 23 using the obtained liquid crystal aligning agent. And liquid crystal composition A was vacuum-injected into this empty cell, and the liquid crystal cell was created.

[Example 41]
The additive (Ad2) was added to the polyamic acid solution (PA10) having a polymer solid content concentration of 6% by weight prepared in Synthesis Example 10 at a rate of 20% by weight per polymer weight. Thereafter, a mixed solvent of NMP / BC = 4/1 (weight ratio) was added and diluted to a polymer solid content concentration of 4% by weight to obtain a liquid crystal aligning agent. An empty cell was assembled by the method according to Example 23 using the obtained liquid crystal aligning agent. And liquid crystal composition A was vacuum-injected into this empty cell, and the liquid crystal cell was created.

[Example 42]
To the polyamic acid solution (PA10) having a polymer solid concentration of 6% by weight prepared in Synthesis Example 10, the additive (Ad3) was added at a rate of 10% by weight per polymer weight. Thereafter, a mixed solvent of NMP / BC = 4/1 (weight ratio) was added and diluted to a polymer solid content concentration of 4% by weight to obtain a liquid crystal aligning agent. An empty cell was assembled by the method according to Example 23 using the obtained liquid crystal aligning agent. And liquid crystal composition A was vacuum-injected into this empty cell, and the liquid crystal cell was created.

[Example 43]
The additive (Ad4) was added to the polyamic acid solution (PA10) having a polymer solid content concentration of 6 wt% prepared in Synthesis Example 10 at a ratio of 0.5 wt% per polymer weight. Thereafter, a mixed solvent of NMP / BC = 4/1 (weight ratio) was added and diluted to a polymer solid content concentration of 4% by weight to obtain a liquid crystal aligning agent. An empty cell was assembled by the method according to Example 23 using the obtained liquid crystal aligning agent. And liquid crystal composition A was vacuum-injected into this empty cell, and the liquid crystal cell was created.

[Example 44]
A mixed solvent of NMP / BC = 4/1 (weight ratio) was added to the polyamic acid solution (PA10) having a polymer solid concentration of 6% by weight prepared in Synthesis Example 10, and diluted to a polymer solids concentration of 4% by weight. A liquid crystal aligning agent was used. A liquid crystal cell was prepared as follows using the obtained liquid crystal aligning agent.

<Method 2 for manufacturing liquid crystal display element>
The liquid crystal aligning agent was apply | coated to the glass substrate with two ITO electrodes with the spinner. After the coating, it was dried by heating at 70 ° C. for 1 minute, and then heat-treated at 230 ° C. for 15 minutes. The glass substrate on which the alignment film is formed is irradiated with linearly polarized ultraviolet light through a polarizing plate from the vertical direction with respect to the substrate using Multilight ML-501C / B manufactured by Ushio Electric Co., Ltd. (exposure energy: An alignment film having an energy of 3.0 ± 0.1 J / cm ² at 365 nm and a thickness of 100 ± 10 nm was formed. The conditions for ultraviolet irradiation and the method for adjusting the exposure energy were the same as in Example 1.

Two substrates on which an alignment film is formed on an ITO electrode are opposed to each other, and the alignment films are further opposed so that the polarization directions of ultraviolet rays irradiated to the respective alignment films are parallel to each other. A gap for injecting the liquid crystal composition was formed between and bonded together to assemble an empty cell having a cell thickness of 4 μm. The injection port for injecting the liquid crystal into the empty cell was provided at a position where the liquid crystal flow direction at the time of injection was substantially parallel to the polarization direction of the ultraviolet rays irradiated to the alignment film. The liquid crystal composition A was vacuum-injected into the empty cell to prepare a liquid crystal cell.

[Comparative Example 4]
A mixed solvent of NMP / BC = 4/1 (weight ratio) was added to the polyamic acid solution (PA12) having a polymer solid content concentration of 6% by weight prepared in Synthesis Example 19, and diluted to a polymer solid content concentration of 4% by weight. A liquid crystal aligning agent was used. An empty cell was assembled by the method according to Example 23 using the obtained liquid crystal aligning agent. And liquid crystal composition A was vacuum-injected into this empty cell, and the liquid crystal cell was created.

[Comparative Example 5]
A mixed solvent of NMP / BC = 4/1 (weight ratio) was added to the polyamic acid solution (PA12) having a polymer solid content concentration of 6% by weight prepared in Synthesis Example 19, and diluted to a polymer solid content concentration of 4% by weight. A liquid crystal aligning agent was used. An empty cell was assembled by the method according to Example 44 using the obtained liquid crystal aligning agent. And liquid crystal composition A was vacuum-injected into this empty cell, and the liquid crystal cell was created.

<5. Observation of flow orientation>
The liquid crystal cell produced as described above was observed visually by sandwiching it between two polarizing plates arranged in crossed Nicols. In these liquid crystal cells, since the cyclobutane skeleton of the polymer main chain substantially along the polarization direction of the ultraviolet rays is cut due to the ultraviolet rays irradiated to the liquid crystal alignment film, the liquid crystal composition is almost the same as the polarization direction of the ultraviolet rays. Oriented at right angles. In a liquid crystal cell using an alignment film with good alignment, no so-called flow alignment was observed in which the liquid crystal was aligned along the direction in which the liquid crystal flowed from the injection port. On the other hand, fluid alignment was observed in a liquid crystal cell using an alignment film with poor alignment. The observation results of the flow orientation are shown in Table 3.

表中の「−」は添加剤を加えていないことを表す。 <6. Observation of orientation defects>
The liquid crystal cell in which the flow alignment was observed was subjected to isotropic treatment at 110 ° C. for 30 minutes and cooled to room temperature. When this liquid crystal cell was observed again with the polarizing microscope in a crossed Nicol state, no alignment defect of the liquid crystal was observed in the liquid crystal cell using an alignment film with good alignment. On the other hand, in the liquid crystal cell using the alignment film having poor alignment properties, alignment defects of the liquid crystal were observed. Table 3 shows the observation results of the alignment defects.

"-" In the table indicates that no additive is added.

When the exposure energy of ultraviolet rays is 3.0 ± 0.1 J / cm ² , some of Examples 23 to 44 have defects observed, and Comparative Examples 4 and 5 both have both flow defects and alignment defects. It was.

[Examples 45 to 61]
A mixed solvent of NMP / BC = 4/1 (weight ratio) was added to each of the polyamic acid solutions (PA1 to PA17) having a polymer solid content concentration of 6% by weight prepared in Synthesis Examples 1 to 17, and the polymer solid content concentration was 4%. % To obtain a liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, an empty cell having a cell thickness of 4 μm was assembled in the same manner as in Example 23 except that the irradiation energy of ultraviolet rays was changed to 5.0 ± 0.1 J / cm ² at 365 nm. And liquid crystal composition A was vacuum-injected into these empty cells, and the liquid crystal cell was created.

[Example 62]
To the polyamic acid solution (PA10) having a polymer solid content concentration of 6% by weight prepared in Synthesis Example 10, the additive (Ad1) was added at a rate of 20% by weight per polymer weight. Thereafter, a mixed solvent of NMP / BC = 4/1 (weight ratio) was added and diluted to a polymer solid content concentration of 4% by weight to obtain a liquid crystal aligning agent. An empty cell was assembled by the method according to Example 45 using the obtained liquid crystal aligning agent. And liquid crystal composition A was vacuum-injected into this empty cell, and the liquid crystal cell was created.

[Example 63]
The additive (Ad2) was added to the polyamic acid solution (PA10) having a polymer solid content concentration of 6% by weight prepared in Synthesis Example 10 at a rate of 20% by weight per polymer weight. Thereafter, a mixed solvent of NMP / BC = 4/1 (weight ratio) was added and diluted to a polymer solid content concentration of 4% by weight to obtain a liquid crystal aligning agent. An empty cell was assembled by the method according to Example 45 using the obtained liquid crystal aligning agent. And liquid crystal composition A was vacuum-injected into this empty cell, and the liquid crystal cell was created.

[Example 64]
To the polyamic acid solution (PA10) having a polymer solid concentration of 6% by weight prepared in Synthesis Example 10, the additive (Ad3) was added at a rate of 10% by weight per polymer weight. Thereafter, a mixed solvent of NMP / BC = 4/1 (weight ratio) was added and diluted to a polymer solid content concentration of 4% by weight to obtain a liquid crystal aligning agent. An empty cell was assembled by the method according to Example 45 using the obtained liquid crystal aligning agent. And liquid crystal composition A was vacuum-injected into this empty cell, and the liquid crystal cell was created.

[Example 65]
The additive (Ad4) was added to the polyamic acid solution (PA10) having a polymer solid content concentration of 6 wt% prepared in Synthesis Example 10 at a ratio of 0.5 wt% per polymer weight. Thereafter, a mixed solvent of NMP / BC = 4/1 (weight ratio) was added and diluted to a polymer solid content concentration of 4% by weight to obtain a liquid crystal aligning agent. An empty cell was assembled by the method according to Example 45 using the obtained liquid crystal aligning agent. And liquid crystal composition A was vacuum-injected into this empty cell, and the liquid crystal cell was created.

[Example 66]
A mixed solvent of NMP / BC = 4/1 (weight ratio) was added to the polyamic acid solution (PA10) having a polymer solid concentration of 6% by weight prepared in Synthesis Example 10, and diluted to a polymer solids concentration of 4% by weight. A liquid crystal aligning agent was used. Using the obtained liquid crystal aligning agent, an empty cell was assembled in the same manner as in Example 44 except that the irradiation energy of ultraviolet rays was changed to 5.0 ± 0.1 J / cm ² at 365 nm. And liquid crystal composition A was vacuum-injected into these empty cells, and the liquid crystal cell was created.

[Comparative Example 6]
A mixed solvent of NMP / BC = 4/1 (weight ratio) was added to the polyamic acid solution (PA19) having a polymer solid concentration of 6% by weight prepared in Synthesis Example 19, and diluted to a polymer solids concentration of 4% by weight. A liquid crystal aligning agent was used. An empty cell was assembled by the method according to Example 45 using the obtained liquid crystal aligning agent. And liquid crystal composition A was vacuum-injected into this empty cell, and the liquid crystal cell was created.

[Comparative Example 7]
A mixed solvent of NMP / BC = 4/1 (weight ratio) was added to the polyamic acid solution (PA19) having a polymer solid concentration of 6% by weight prepared in Synthesis Example 19, and diluted to a polymer solids concentration of 4% by weight. A liquid crystal aligning agent was used. An empty cell was assembled by the method according to Example 66 using the obtained liquid crystal aligning agent. And liquid crystal composition A was vacuum-injected into this empty cell, and the liquid crystal cell was created.

<Observation of flow orientation>
In the same manner as described above, the liquid crystal cell was sandwiched between two polarizing plates arranged in crossed Nicols, and the flow alignment was visually observed. The observation results of the flow orientation are shown in Table 4.

表中の「−」は添加剤を加えていないことを表す。 <Observation of orientation defects>
The liquid crystal cell in which the flow alignment was observed was subjected to isotropic treatment at 110 ° C. for 30 minutes and cooled to room temperature. The liquid crystal cell was observed again with the polarizing microscope in a crossed Nicols state. The observation results of the alignment defects are shown in Table 4.

"-" In the table indicates that no additive is added.

When the ultraviolet exposure energy was 5.0 ± 0.1 J / cm ² , both Comparative Example 6 and 7 were recognized as both flow defects and alignment defects, but the defects were observed in Examples 45 to 66. Only Example 63.

[Examples 67 to 83]
A mixed solvent of NMP / BC = 4/1 (weight ratio) was added to each of the polyamic acid solutions (PA1 to PA17) having a polymer solid content concentration of 6% by weight prepared in Synthesis Examples 1 to 17, and the polymer solid content concentration was 4%. % To obtain a liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, an empty cell was assembled by the method according to Example 23 except that the irradiation energy of ultraviolet rays was changed to 10.0 ± 0.1 J / cm ² at 365 nm. And liquid crystal composition A was vacuum-injected into these empty cells, and the liquid crystal cell was created.

[Example 84]
To the polyamic acid solution (PA10) having a polymer solid content concentration of 6% by weight prepared in Synthesis Example 10, the additive (Ad1) was added at a rate of 20% by weight per polymer weight. Thereafter, a mixed solvent of NMP / BC = 4/1 (weight ratio) was added and diluted to a polymer solid content concentration of 4% by weight to obtain a liquid crystal aligning agent. An empty cell was assembled by a method according to Example 67 using the obtained liquid crystal aligning agent. And liquid crystal composition A was vacuum-injected into this empty cell, and the liquid crystal cell was created.

[Example 85]
The additive (Ad2) was added to the polyamic acid solution (PA10) having a polymer solid content concentration of 6% by weight prepared in Synthesis Example 10 at a rate of 20% by weight per polymer weight. Thereafter, a mixed solvent of NMP / BC = 4/1 (weight ratio) was added and diluted to a polymer solid content concentration of 4% by weight to obtain a liquid crystal aligning agent. An empty cell was assembled by a method according to Example 67 using the obtained liquid crystal aligning agent. And liquid crystal composition A was vacuum-injected into this empty cell, and the liquid crystal cell was created.

[Example 86]
To the polyamic acid solution (PA10) having a polymer solid concentration of 6% by weight prepared in Synthesis Example 10, the additive (Ad3) was added at a rate of 10% by weight per polymer weight. Thereafter, a mixed solvent of NMP / BC = 4/1 (weight ratio) was added and diluted to a polymer solid content concentration of 4% by weight to obtain a liquid crystal aligning agent. An empty cell was assembled by a method according to Example 67 using the obtained liquid crystal aligning agent. And liquid crystal composition A was vacuum-injected into this empty cell, and the liquid crystal cell was created.

[Example 87]
The additive (Ad4) was added to the polyamic acid solution (PA10) having a polymer solid content concentration of 6 wt% prepared in Synthesis Example 10 at a ratio of 0.5 wt% per polymer weight. Thereafter, a mixed solvent of NMP / BC = 4/1 (weight ratio) was added and diluted to a polymer solid content concentration of 4% by weight to obtain a liquid crystal aligning agent. An empty cell was assembled by a method according to Example 67 using the obtained liquid crystal aligning agent. And liquid crystal composition A was vacuum-injected into this empty cell, and the liquid crystal cell was created.

[Example 88]
A mixed solvent of NMP / BC = 4/1 (weight ratio) was added to the polyamic acid solution (PA10) having a polymer solid concentration of 6% by weight prepared in Synthesis Example 10, and diluted to a polymer solids concentration of 4% by weight. A liquid crystal aligning agent was used. Using the obtained liquid crystal aligning agent, an empty cell having a cell thickness of 4 μm was assembled in the same manner as in Example 44 except that the irradiation energy of ultraviolet rays was changed to 10.0 ± 0.1 J / cm ² at 365 nm. And liquid crystal composition A was vacuum-injected into this empty cell to prepare a liquid crystal cell.

[Comparative Example 8]
A mixed solvent of NMP / BC = 4/1 (weight ratio) was added to the polyamic acid solution (PA19) having a polymer solid concentration of 6% by weight prepared in Synthesis Example 19, and diluted to a polymer solids concentration of 4% by weight. A liquid crystal aligning agent was used. An empty cell was assembled by a method according to Example 67 using the obtained liquid crystal aligning agent. And liquid crystal composition A was vacuum-injected into this empty cell to prepare a liquid crystal cell.

[Comparative Example 9]
A mixed solvent of NMP / BC = 4/1 (weight ratio) was added to the polyamic acid solution (PA19) having a polymer solid concentration of 6% by weight prepared in Synthesis Example 19, and diluted to a polymer solids concentration of 4% by weight. A liquid crystal aligning agent was used. An empty cell was assembled by a method according to Example 88 using the obtained liquid crystal aligning agent. And liquid crystal composition A was vacuum-injected into this empty cell, and the liquid crystal cell was created.

<Observation of flow orientation>
In the same manner as described above, the liquid crystal cell was sandwiched between two polarizing plates arranged in crossed Nicols, and the flow alignment was visually observed. Table 5 shows the observation results of the flow orientation.

表中の「−」は添加剤を加えていないことを表す。 <Observation of orientation defects>
The liquid crystal cell in which the flow alignment was observed was subjected to isotropic treatment at 110 ° C. for 30 minutes and cooled to room temperature. The liquid crystal cell was observed again with the polarizing microscope in a crossed Nicols state. The observation results of the orientation defects are shown in Table 5.

"-" In the table indicates that no additive is added.

When the exposure energy of ultraviolet rays was further increased to 10.0 ± 0.1 J / cm ² , no defects were observed in Examples 67 to 88, whereas alignment defects were still observed in Comparative Example 8. It was. From the results of Examples 23 to 88 and Comparative Examples 4 to 9, it can be seen that the alignment film of the present invention has good orientation even when irradiated with low energy ultraviolet rays, and has good sensitivity to chemical change due to light irradiation.

Thus, when the alignment film of the present invention is applied to an alignment film for a liquid crystal display element, it can be seen that both the transmittance and the alignment have sufficient characteristics to withstand practical use. In addition, the alignment film of the present invention can be sufficiently photo-aligned with ultraviolet rays having a commonly used wavelength, and can be subjected to photo-alignment treatment even by irradiation with ultraviolet rays having a lower energy than conventionally known photo-alignment films.

Claims (30)

In the liquid crystal aligning agent for forming the liquid crystal aligning film for photo-alignment containing the polyamic acid obtained by making tetracarboxylic dianhydride and diamine react, or its derivative (s),
The tetracarboxylic dianhydride includes a tetracarboxylic dianhydride represented by the following formula (I);
The diamine is a liquid crystal aligning agent containing at least one selected from the group of diamines represented by the following formula (N-1) and formula (N-2).

In the formula (I), R ^{A to} R ^D are independently hydrogen or alkyl having 1 to 4 carbons.

In formula (N-1), R ^E is independently a monovalent organic group;
R ^F is independently hydrogen, a monovalent organic group or halogen; and
Z is a divalent group containing an alkylene having 1 to 5 carbon atoms.

In formula (N-2), R ^G is independently a monovalent organic group or halogen;
R ^H is independently a monovalent organic group;
m is independently an integer from 0 to 3; and
n is an integer of 0-4. R ^E is independently alkyl having 1 to 3 carbon atoms, and R ^F is independently hydrogen, alkyl having 1 to 3 carbon atoms, fluorine, chlorine, or bromine. The liquid crystal aligning agent of Claim 1 containing the polyamic acid obtained by making diamine or the diamine mixture containing this diamine react with tetracarboxylic dianhydride, or its derivative (s). A polyamic acid obtained by reacting a diamine represented by the formula (N-1) having an amino group at each para position in phenyl at both ends of the molecule or a diamine mixture containing this diamine with tetracarboxylic dianhydride or the The liquid crystal aligning agent of Claim 1 or 2 containing a derivative | guide_body. It is obtained by reacting at least one selected from the group of diamines represented by the following formulas (N-1-1) to (N-1-20) or a diamine mixture containing this diamine with tetracarboxylic dianhydride. The liquid crystal aligning agent of any one of Claims 1-3 containing a polyamic acid or its derivative (s).

Formula where R ^G is independently alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, alkoxy, carbamoyl, fluorine, chlorine, or bromine, and R ^H is independently alkyl having 1 to 3 carbons ( The polyamic acid obtained by making the diamine represented by N-2) or the diamine mixture containing this diamine react with a tetracarboxylic dianhydride or its derivative (s) is described in any one of Claims 1-4. Liquid crystal aligning agent. A polyamic acid obtained by reacting a diamine represented by the formula (N-2) having an amino group at each para position in phenyl at both ends of the molecule or a diamine mixture containing this diamine with tetracarboxylic dianhydride, or a compound thereof The liquid crystal aligning agent of any one of Claims 1-5 containing a derivative | guide_body. Obtained by reacting at least one selected from the group of diamines represented by the following formulas (N-2-1) to (N-2-15) or a diamine mixture containing the diamine with tetracarboxylic dianhydride. The liquid crystal aligning agent of any one of Claims 1-6 containing a polyamic acid or its derivative (s).

It is obtained by reacting at least one of the diamines represented by the formulas (N-2-1) and (N-2-2) according to claim 7 or a diamine mixture containing the diamine with tetracarboxylic dianhydride. The liquid crystal aligning agent of any one of Claims 1-6 containing the polyamic acid obtained or its derivative (s). A polyamic acid or a derivative thereof obtained by reacting a diamine mixture further containing at least one selected from the group of diamines represented by the following formulas (III) to (IX) and (XV) with tetracarboxylic dianhydride: The liquid crystal aligning agent of any one of Claims 1-8 to contain.

In Formula (III), A ¹ is — (CH ₂ ) _m —, and m is an integer of 1 to 6;
In the formulas (V), (VII) and (IX), X represents a single bond, —O—, —S—, —S—S—, —SO ₂ —, —CO—, —NH—, —N (CH _{3) -, - C (CH} 3) 2 -, - C (CF 3) 2 -, - (CH 2) m -, - O- (CH 2) m -O-, or -S- _(CH 2) _m -S-, m is an integer from 1 to 6;
In Formula (VII), L ¹ and L ² are —H, but X is —NH—, —N (CH ₃ ) —, —CH ₂ —, —C (CH ₃ ) ₂ —, or —C ( When CF ₃ ) ₂ —, they may combine with each other to form a single bond;
In Formulas (VIII) and (IX), Y represents a single bond, —O—, —S—, —CO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, or a carbon number of 1 to 3 alkylene;
In formula (XV), R ³³ and R ³⁴ are independently alkyl having 1 to 3 carbons or phenyl; G is independently alkylene having 1 to 6 carbons, phenylene or alkyl-substituted phenylene; m is an integer from 1 to 10;
In each formula above, _-H cyclohexane ring or benzene ring, -F, -CH 3, -OH, -COOH, -SO 3 H, -PO 3 H 2, be replaced by benzyl or hydroxybenzyl, Also good. The liquid crystal aligning agent of any one of Claims 1-9 containing the polyamic acid obtained by making the diamine mixture which further contains the diamine which has a side chain structure react with tetracarboxylic dianhydride, or its derivative (s). The liquid crystal aligning agent of Claim 10 whose diamine which has a side chain structure is at least 1 chosen from the group of the diamine represented by following formula (X)-(XIV).

In formula (X),
Z ¹ is a single bond, —O—, —CO—, —COO—, —OCO—, —CONH—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, or - _{(CH 2) m} - and is, m is an integer from 1 to 6, any -CH ₂ - in this alkylene -O -, - be replaced by CH = CH- or -C≡C- Well;
R ³ is a group having a steroid skeleton, alkyl having 3 to 30 carbon atoms, phenyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms as a substituent, or a group represented by the following formula (X-a): Any —CH ₂ — in the alkyl having 1 to 30 carbon atoms may be replaced by —O—, —CH═CH— or —C≡C—;

In the formula (Xa),
A ² and A ³ are independently a single bond, —O—, —COO—, —OCO—, —CONH—, —CH═CH—, or alkylene having 1 to 12 carbons, and a and b are Independently an integer from 0 to 4;
Ring B and Ring C are independently 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, Naphthalene-1,5-diyl, naphthalene-2,7-diyl, or anthracene-9,10-diyl;
R ⁴ and R ⁵ are independently —F or CH ₃ and f and g are independently integers from 0 to 2;
R ⁶ is —F, —OH, —CN, alkyl having 1 to 30 carbons, alkoxy having 1 to 30 carbons, or alkoxyalkyl having 2 to 30 carbons. In these alkyls, alkoxys, alkoxyalkyls, Any —H may be replaced by —F, and any —CH ₂ — may be replaced by —CF ₂ — or a divalent group represented by the following formula (s);

In the formula (s), R ³⁵ and R ³⁶ are independently alkyl having 1 to 3 carbon atoms, and m is an integer of 1 to 6;
c, d and e are each independently an integer of 0 to 3, and c + d + e ≧ 1.

In formulas (XI) and (XII)
R ⁷ is independently —H or —CH ₃ ;
R ⁸ is —H, alkyl having 1 to 20 carbons or alkenyl having 2 to 20 carbons;
A ⁴ is independently a single bond, —CO— or —CH ₂ —;
In formula (XII):
R ⁹ and R ¹⁰ are independently alkyl having 1 to 20 carbons or phenyl.

In formulas (XIII) and (XIV), A ⁵ is independently —O— or alkylene having 1 to 6 carbons;
In the formula (XIII), R ¹¹ is —H or alkyl having 1 to 30 carbons, and arbitrary —CH ₂ — of this alkyl is replaced by —O—, —CH═CH— or —C≡C—. May be
A ⁶ is a single bond or alkylene having 1 to 3 carbon atoms;
Ring T is 1,4-phenylene or 1,4-cyclohexylene;
h is 0 or 1;
In formula (XIV), R ¹² is alkyl having 6 to 22 carbons; and
R ¹³ is alkyl having 1 to 22 carbons. The tetracarboxylic dianhydride to be reacted with the diamine further uses at least one selected from the group of compounds represented by the following formulas (An-1) to (An-6). Item 1. A liquid crystal aligning agent according to item 1.

In formulas (An-1), (An-4) and (An-5), X ¹ is independently a single bond or —CH ₂ —;
In Formula (An-2), G ¹ represents a single bond, alkylene having 1 to 20 carbons, —CO—, —O—, —S—, —SO ₂ —, —C (CH ₃ ) ₂ —, or — C (CF ₃ ) ₂ —;
In formulas (An-2) to (An-4), Y ¹ is independently one selected from the group of trivalent groups described below;

In the formulas (An-3) to (An-5), the ring E represents a monocyclic hydrocarbon group having 3 to 10 carbon atoms or a condensed polycyclic hydrocarbon group having 6 to 20 carbon atoms. Any hydrogen in may be replaced by methyl, ethyl or phenyl;
The bond on the ring is linked to any carbon that makes up the ring, and two bonds may be linked to the same carbon;
In the formula (An-6), X ¹¹ is alkylene having 2 to 6 carbons;
Me represents methyl and Ph represents phenyl. The tetracarboxylic dianhydride to be reacted with diamine is selected from the group of aromatic tetracarboxylic dianhydrides represented by the following formulas (1), (2), (5) to (7) and (17) The liquid crystal aligning agent of any one of Claims 1-11 which further uses at least 1 to be used.

As tetracarboxylic dianhydride to be reacted with diamine, alicyclic tetra represented by the following formulas (23), (25), (36) to (39), (44), (49) and (68) The liquid crystal aligning agent of any one of Claims 1-11 which further uses at least 1 chosen from the group of carboxylic dianhydride and aliphatic tetracarboxylic dianhydride.

The tetracarboxylic dianhydride to be reacted with diamine is at least one selected from the group of aromatic tetracarboxylic dianhydrides according to claim 13, and the alicyclic tetracarboxylic dianhydrides and fats according to claim 14. The liquid crystal aligning agent of any one of Claims 1-11 which further uses at least 1 chosen from the group of group tetracarboxylic dianhydride. The liquid crystal aligning agent which mixed at least 2 of the liquid crystal aligning agent in any one of Claims 1-15. The liquid crystal aligning agent of any one of Claims 1-16 which further contains at least 1 chosen from an alkenyl substituted nadiimide compound, an epoxy compound, and a silane coupling agent. The alkenyl-substituted nadiimide compound is bis [4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl] methane, N, N′-m-xylylene-bis (allyl). Bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) and N, N′-hexamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2 The liquid crystal aligning agent of Claim 17 which is at least 1 chosen from the group which consists of (3-dicarboximide). The liquid crystal aligning agent of Claim 17 whose alkenyl substituted nadiimide compound is bis [4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl] methane. The liquid crystal aligning agent of any one of Claims 17-19 in which the alkenyl substituted nadiimide compound is contained 0.01 to 50weight% with respect to the total amount of the said polyamic acid or its derivative (s). The epoxy compound is N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetra. Glycidyl-4,4′-diaminodiphenylmethane, 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3-epoxypropoxy] phenyl) )] Ethyl] phenyl] propane, 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate, N-phenylmaleimide-glycidyl methacrylate copolymer, and 2- (3,4-epoxycyclohexyl) The liquid crystal aligning agent of Claim 17 which is at least 1 chosen from the group which consists of ethyltrimethoxysilane. The liquid crystal alignment according to claim 17, wherein the epoxy compound is N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane or 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Agent. The liquid crystal aligning agent of Claim 17, 21 or 22 in which 1 to 40 weight% of epoxy compounds are contained with respect to the total amount of the said polyamic acid or its derivative (s). Silane coupling agent is vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyltrimethoxysilane , Paraaminophenyltrimethoxysilane, paraaminophenyltriethoxysilane, metaaminophenyltrimethoxysilane, metaaminophenyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltri Methoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methyl From captopropyltrimethoxysilane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propylamine, and N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine The liquid crystal aligning agent of Claim 17 which is at least 1 chosen from the group which consists of. The liquid crystal aligning agent of Claim 17 whose silane coupling agent is 3-aminopropyl triethoxysilane. The liquid crystal aligning agent of Claim 17, 24 or 25 in which 0.1-10 weight% of silane coupling agents are contained with respect to the total amount of the said polyamic acid or its derivative (s). It forms through the process of apply | coating the liquid crystal aligning agent of any one of Claims 1-26 to a board | substrate, the process of heat-drying the board | substrate which applied the aligning agent, and the process of irradiating a film | membrane with polarized ultraviolet rays. Liquid crystal alignment film for photo-alignment. A step of applying the liquid crystal aligning agent according to any one of claims 1 to 26 to a substrate, a step of heating and drying the substrate coated with the aligning agent, a step of irradiating polarized ultraviolet rays to the dried film, Next, a liquid crystal alignment film for photo-alignment formed through a step of heating and baking the film. The process of apply | coating the liquid crystal aligning agent of any one of Claims 1-26 to a board | substrate, the process of heat-drying the board | substrate which applied the aligning agent, the process of heat-baking the dried film | membrane, A liquid crystal alignment film for photo-alignment formed through a step of irradiating the film with polarized ultraviolet rays. A liquid crystal display element comprising the liquid crystal alignment film for photo-alignment according to any one of claims 27 to 29.