JP2011065149A - Liquid crystal aligning agent, liquid crystal alignment layer, and liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid crystal aligning agent with which a liquid crystal alignment layer excellent in long term thermal reliability of a liquid crystal display element, that is, holding a high voltage holding ratio for a long period of time in a heating test of the element is formed, and further to provide the liquid crystal alignment layer formed by using the liquid crystal aligning agent, and the liquid crystal display element using the liquid crystal alignment layer. <P>SOLUTION: The liquid crystal alignment layer is formed from the liquid crystal aligning agent, which includes a polyamic acid obtained by making a tetracarboxylic acid dianhydride expressed by formula (G) and a diamine react with each other, or a derivative thereof, and is used for the liquid crystal display element. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a liquid crystal alignment agent containing a polyamic acid obtained by reacting diamine with tetracarboxylic dianhydride or a derivative thereof, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display having the liquid crystal alignment film In particular, the present invention relates to a liquid crystal aligning agent suitably used for a liquid crystal display element that is not subjected to physical rubbing treatment, a liquid crystal aligning film obtained from the liquid crystal aligning agent, and a liquid crystal display element having the liquid crystal aligning film.

Liquid crystal display elements are used in various liquid crystal display devices such as monitors for notebook personal computers and desktop personal computers, viewfinders for video cameras, and projection displays. Recently, they are also used for televisions. Furthermore, liquid crystal display elements are also used in optoelectronic-related elements such as optical printer heads, optical Fourier transform elements, and light valves.

Various elements are known as liquid crystal display elements, but the development of the technology of liquid crystal display elements is not only the improvement of the driving method of the liquid crystal display elements and the structure of the liquid crystal display elements, but also the configuration used for the liquid crystal display elements This is achieved by improving the members. The liquid crystal display element usually has a liquid crystal alignment film for aligning the liquid crystal composition in the liquid crystal layer in a specific direction. 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 has become important year by year as the quality of the liquid crystal display element is improved.

The liquid crystal alignment film is prepared from a liquid crystal aligning agent. The liquid crystal aligning agent mainly used at present is a solution in which polyamic acid or soluble polyimide is dissolved in an organic solvent. After applying such a solution to the substrate, a polyimide-based alignment film is formed by film formation by means such as heating. Various liquid crystal aligning agents other than polyamic acid or soluble polyimide are also being studied, but the points such as heat resistance, chemical resistance (liquid crystal resistance), coating properties, liquid crystal alignment properties, electrical properties, optical properties, display properties, etc. Therefore, it is hardly put into practical use.

With the widespread use of liquid crystal televisions, liquid crystal alignment films are also required to have a long life (high reliability), and one of the means for solving them is the use of aliphatic tetracarboxylic dianhydrides (for example, patents). References 1 and 2).

A typical example of the aliphatic tetracarboxylic dianhydride is cyclohexanetetracarboxylic dianhydride, and many examples have been used for liquid crystal alignment agents (see, for example, Patent Documents 2 to 6).

These cyclohexanetetracarboxylic dianhydrides have not been able to obtain an arbitrary three-dimensional structure so far, but in recent years, a structure-controlled product has become available (see Non-Patent Document 1).

Japanese Patent Laid-Open No. 8-036183 International Publication No. 2003/005114 Pamphlet JP 2007-332357 A JP 2007-241249 A International Publication No. 2008/117760 Pamphlet International Publication No. 2008/117759 Pamphlet

Polymer Preprints, Japan Vol. 57, No. 2 (2008)

The present invention is intended to provide a liquid crystal aligning agent that is excellent in long-term thermal reliability of a liquid crystal display element, that is, can form a liquid crystal alignment film that maintains a high voltage holding ratio for a long time in a heating test of the element. Furthermore, the present invention intends to provide a liquid crystal alignment film formed using the liquid crystal alignment agent and a liquid crystal display element using the liquid crystal alignment film.

The present inventors use a composition containing a specific acid dianhydride and a polyamic acid derived from diamine or a derivative thereof as a liquid crystal aligning agent, and a liquid crystal display device having a liquid crystal alignment film formed thereby is long-term. It was found that the thermal reliability was excellent, and the present invention was completed.

In the present specification, the right and left groups in the left and right sides may be oriented in either direction. For example, when expressed as “—COCH═CH—”, either “—COCH═CH—” or “—CH═CHCO—” may be used. When —CH ₂ — in alkyl or alkylene is replaced by —O—, —O— is not consecutive. Alkyl or alkylene may be linear or branched.

The present invention has the following configuration.
[1] A liquid crystal aligning agent using a polyamic acid or a derivative thereof obtained by reacting a tetracarboxylic dianhydride represented by the formula (G) with a diamine.

式（Ｖ−２）において、
Ｘ^１０は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−、−ＣＯＮＨ−、または−（ＣＨ_２）_ｍ−であり、ｍは１〜６の整数であり；
Ｙ^１１はステロイド骨格、スクシンイミド骨格、フタルイミド骨格、またはシンナメート骨格を有する基、あるいは下記式（XXIII）で表される基を有する。

式（XXIII）において、
Ａ^４は独立して、単結合、または炭素数１〜１２のアルキレンであり、
アルキレン中の−ＣＨ_２−は−Ｏ−、−ＮＨ−、または−ＣＯ−で置き換えられてもよく、
−ＣＨ_２ＣＨ_２−は−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、または−Ｎ＝Ｎ−で置き換えられてもよく、
アルキレンの−Ｈは−Ｆ、−Ｃｌ、−Ｃ≡Ｎ、−ＯＨ、−ＣＯＯＨ、−ＳＯ_３Ｈ、または−ＰＯ_３Ｈ_２で置き換えられてもよく；
Ｙ^１２は独立して、−Ｆまたは−ＣＨ_３であり；
環Ｓ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、ピペリジン−１，４−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；
Ｙ^１３は−Ｈ、−Ｆ、−Ｃｌ、−Ｃ≡Ｎ、−ＯＨ、−ＣＯＯＨ、−ＳＯ_３Ｈ、−ＰＯ_３Ｈ_２、または炭素数１〜３０のアルキルであり、
アルキル中の−ＣＨ_２−は−Ｏ−、−ＮＨ−または−ＣＯ−で置き換えられてもよく、
−ＣＨ_２ＣＨ_２−は−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−または−Ｎ＝Ｎ−で置き換えられてもよく、
アルキルの−Ｈは−Ｆ、−Ｃｌ、−Ｃ≡Ｎ、−ＯＨ、−ＣＯＯＨ、−ＳＯ_３Ｈ、または−ＰＯ_３Ｈ_２で置き換えられてもよく；
ｂは独立して０〜４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、ｆは独立して０〜２の整数であり、かつｃ＋ｄ＋ｅ≧１である。 [2] The liquid crystal aligning agent according to the above [1], wherein a part or all of the diamine is a diamine having a side chain structure represented by the following formula (V-2).

In the formula (V-2),
X ¹⁰ is a single bond, —O—, —COO—, —OCO—, —CO—, —CONH—, or — (CH ₂ ) _m —, and m is an integer of 1 to 6;
Y ¹¹ has a group having a steroid skeleton, a succinimide skeleton, a phthalimide skeleton, or a cinnamate skeleton, or a group represented by the following formula (XXIII).

In formula (XXIII):
A ⁴ is independently a single bond or alkylene having 1 to 12 carbons,
It is -O - - -CH ₂ in the alkylene, - NH-, or -CO- may be replaced by,
—CH ₂ CH ₂ — may be replaced by —CH═CH—, —C≡C—, or —N═N—
-H alkylene is -F, -Cl, -C≡N, -OH, -COOH, it may be replaced by _-SO 3 H or _-PO 3 _{H 2,;}
Y ¹² is independently —F or —CH ₃ ;
Ring S is independently 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, piperidine-1,4-diyl, pyrimidine-2,5-diyl, pyridine-2. , 5-diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl, or anthracene-9,10-diyl;
Y ¹³ is —H, —F, —Cl, —C≡N, —OH, —COOH, —SO ₃ H, —PO ₃ H ₂ , or alkyl having 1 to 30 carbons;
Is -O - - -CH ₂ in the alkyl, - NH- or -CO- may be replaced by,
—CH ₂ CH ₂ — may be replaced by —CH═CH—, —C≡C— or —N═N—
-H alkyl is -F, -Cl, -C≡N, -OH, -COOH, it may be replaced by _-SO 3 H or _-PO 3 _{H 2,;}
b is independently an integer of 0 to 4, c, d and e are independently integers of 0 to 3, f is independently an integer of 0 to 2 and c + d + e ≧ 1.

式（Ｙ^１１−１）〜（Ｙ^１１−７）において、
Ｙ^２は−Ｈ、−Ｆ、炭素数１〜３０のアルキル、炭素数１〜３０のフッ素置換アルキル、炭素数１〜３０のアルコキシ、炭素数２〜３０のアルケニル、−Ｃ≡Ｎ、−ＯＣＨ_２Ｆ、−ＯＣＨＦ_２、または−ＯＣＦ_３であり；
Ａ^１は−Ｏ−または炭素数１〜６のアルキレンである。 [3] In the above item [2], Y ¹¹ in the formula (V-2) is one selected from the group of groups represented by the following formulas (Y ¹¹ -1) to (Y ¹¹ -7). The liquid crystal aligning agent of description.

In the formulas (Y ¹¹ -1) to (Y ¹¹ -7),
Y ² is —H, —F, alkyl having 1 to 30 carbon atoms, fluorine-substituted alkyl having 1 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms, alkenyl having 2 to 30 carbon atoms, —C≡N, —OCH. ₂ F, —OCHF ₂ , or —OCF ₃ ;
A ¹ is —O— or alkylene having 1 to 6 carbon atoms.

式（Ｖ−２−２）〜（Ｖ−２−８）および（Ｖ−２−５３）において、
Ｙ^２は独立して−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；
Ｙ^１８は−Ｆ、−ＣＦ_３または−ＯＣＦ_３である。 [4] Part or all of the diamine is at least one selected from the group of compounds represented by the following formulas (V-2-2) to (V-2-8) and (V-2-53) The liquid crystal aligning agent as described in the above item [2].

In the formulas (V-2-2) to (V-2-8) and (V-2-53),
Y ² is independently —H, alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons;
Y ¹⁸ is —F, —CF ₃ or —OCF ₃ .

[5] A part or all of the diamine is represented by the following formulas (V-1-1) to (V-1-5), (V-1-14), (V-1-15), (VI-1). -1) to (VI-1-12), (VI-1-28) to (VI-1-30), (VI-1-33), (VI-1-35) to (VI-1-39) ), (VII-2-1), and (VII-2-2), which is at least one selected from the group of diamines having no side chain structure, [1] Agent.

[6] In addition to the tetracarboxylic dianhydride represented by the formula (G), the aromatics represented by the following formulas (1), (2), (5) to (7), and (12) The liquid crystal aligning agent as described in the said [1] item using the polyamic acid obtained by making at least 1 chosen from the group of tetracarboxylic dianhydride react with diamine, or its derivative (s).

[7] In addition to the tetracarboxylic dianhydride represented by the formula (G), the following structural formulas (19), (23), (26), (35) to (39) (44), (49) And the polyamic acid obtained by reacting at least one selected from the group of aliphatic tetracarboxylic dianhydrides represented by (69) with a diamine or a derivative thereof, as described in the above item [1]. Liquid crystal aligning agent.

[8] The liquid crystal aligning agent according to the above [1], wherein a part or all of the diamine is at least one selected from the group of diamines having the following photosensitive structure.

[9] A polyamic acid obtained by reacting an aromatic tetracarboxylic dianhydride represented by the following formula (68) with a diamine in addition to the tetracarboxylic dianhydride represented by the formula (G) Or the liquid crystal aligning agent as described in the said [1] item using the derivative (s).

[10] Any of [1] to [9], further containing at least one selected from an alkenyl-substituted nadiimide compound, a compound having a radical polymerizable unsaturated double bond, an oxazine compound, an oxazoline compound, and an epoxy compound 2. A liquid crystal aligning agent according to item 1.

[11] A liquid crystal alignment film formed by heating a coating film of the liquid crystal aligning agent according to any one of [1] to [10].

[12] A liquid crystal display element having a pair of substrates, a liquid crystal layer formed between the substrates, an electrode for applying a voltage to the liquid crystal layer, and a liquid crystal alignment film for aligning the liquid crystal molecules in a predetermined direction Wherein the liquid crystal alignment film is the liquid crystal alignment film according to the item [11].

According to the present invention, it is possible to provide a liquid crystal display element excellent in long-term thermal reliability of voltage holding ratio.

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. The polyamic acid or derivative thereof may be used alone in the liquid crystal aligning agent, or a plurality of compounds may be used in combination.

また、式（Ｇ）で表されるテトラカルボン酸二無水物は、これとジアミンと反応させて得たポリアミック酸またはその誘導体を液晶配向膜に用いると、液晶表示素子の電圧保持率を高くし、そしてその長期熱信頼性を実現させるという観点から、本発明の液晶配向剤におけるポリアミック酸を構成する酸二無水物中モル比で１０〜１００％含まれることが好ましく、２０〜１００％含まれることがより好ましい。 The tetracarboxylic dianhydride used for this invention contains the tetracarboxylic dianhydride represented by the said Formula (G).

Further, the tetracarboxylic dianhydride represented by the formula (G) increases the voltage holding ratio of the liquid crystal display element when a polyamic acid obtained by reacting it with a diamine or a derivative thereof is used for a liquid crystal alignment film. From the viewpoint of realizing long-term thermal reliability, the molar ratio in the acid dianhydride constituting the polyamic acid in the liquid crystal aligning agent of the present invention is preferably 10 to 100%, and preferably 20 to 100%. It is more preferable.

In addition to the tetracarboxylic dianhydride represented by the formula (G), an aromatic tetracarboxylic dianhydride may be included. An aromatic tetracarboxylic dianhydride is a compound in which at least one of two —CO—O—CO— is bonded to an aromatic compound. Examples of the aromatic tetracarboxylic dianhydride include compounds represented by the following formulas (1) to (13).

The aromatic tetracarboxylic dianhydride used together with the tetracarboxylic dianhydride represented by the formula (G) is represented by the formulas (1), (2), (5) to (7), and (12). The compound represented by Formula (1) and (12) is more preferable. When an aromatic tetracarboxylic dianhydride is used in combination, the light resistance of the liquid crystal display device is increased and the residual DC is reduced. In the total tetracarboxylic dianhydride constituting the polyamic acid in the liquid crystal aligning agent of the present invention, the aromatic tetracarboxylic dianhydride is preferably contained in a molar ratio of 1 to 90%, more preferably 2 to 60%. preferable.

The liquid crystal aligning agent of the present invention is a fat which is a compound in which at least one of two —CO—O—CO— is bonded to an alicyclic compound in addition to the tetracarboxylic dianhydride represented by the formula (G). Either or both of a cyclic tetracarboxylic dianhydride and an aliphatic tetracarboxylic dianhydride, which is a compound in which at least one of two —CO—O—CO— is bonded to an aliphatic compound, are combined with a diamine. It is preferable to use a polyamic acid obtained by reaction or a derivative thereof. Examples of the alicyclic tetracarboxylic dianhydride include compounds represented by the following formulas (19) to (44), (49) to (58), and (62) to (64).

Examples of the aliphatic tetracarboxylic dianhydride include compounds represented by the following formulas (23), (45) to (48), (66), (67), and (69).

The alicyclic tetracarboxylic dianhydride and the aliphatic tetracarboxylic dianhydride have the formulas (19), (23), (26), (35)-(39), (44), (49), and The compound represented by (69) is preferred, and the compounds represented by formulas (19) and (23) are more preferred. When an alicyclic tetracarboxylic dianhydride and / or an aliphatic tetracarboxylic dianhydride are used in combination, there is an effect of increasing the heat resistance of the liquid crystal display element and an effect of improving the transparency. The tetracarboxylic dianhydride constituting the polyamic acid in the liquid crystal aligning agent of the present invention contains alicyclic tetracarboxylic dianhydride and / or aliphatic tetracarboxylic dianhydride in a molar ratio of 1 to 90%. Is preferable, and it is more preferable to contain 10 to 80%.

The tetracarboxylic dianhydride used in the present invention preferably contains silsesquioxane dianhydride. Since silsesquioxane is a highly crosslinked product and is not hydrolyzed, the storage stability as a liquid crystal aligning agent is excellent by containing. In addition, since it is not hydrolyzed after film formation, a liquid crystal alignment film with high thermal reliability can be formed.

As the silsesquioxane dianhydride used in the present invention, for example, a compound represented by the following formula (S) described in International Publication No. 03/024870 pamphlet can be used.

式（ａ）および式（ｂ）中のＸは、それぞれ独立して、水素、ハロゲン、水酸基または酸無水物の構造（−ＣＯ−Ｏ−ＣＯ−）を有する１価の有機基であり、Ｘの少なくとも２つは酸無水物の構造（−ＣＯ−Ｏ−ＣＯ−）を有する１価の有機基であり、Ｚは−Ｏ−、−ＣＨ_２−または単結合である。但し、炭素数１〜４５のアルキルにおいて、任意の水素はフッ素で置き換えられてもよく、任意のＣＨ_２−は−Ｏ−、−ＣＨ＝ＣＨ−、シクロアルキレンまたはシクロアルケニレンで置き換えられてもよい。置換または非置換のアリールアルキル中のアルキレンにおいて、任意の水素はフッ素に置き換えられてもよく、任意の−ＣＨ_２−は−Ｏ−、−ＣＨ＝ＣＨ−、またはシクロアルキレンで置き換えられてもよい。 In the formula (S), each R is independently selected from hydrogen, alkyl having 1 to 45 carbon atoms, substituted or unsubstituted aryl and substituted or unsubstituted arylalkyl, and Y is represented by the following (a) or (b ).

X in the formula (a) and the formula (b) is each independently a monovalent organic group having a structure of hydrogen, halogen, hydroxyl group or acid anhydride (—CO—O—CO—), At least two of them are monovalent organic groups having an acid anhydride structure (—CO—O—CO—), and Z is —O—, —CH ₂ — or a single bond. However, in alkyl having 1 to 45 carbon atoms, arbitrary hydrogen may be replaced with fluorine, and arbitrary CH ₂ — may be replaced with —O—, —CH═CH—, cycloalkylene, or cycloalkenylene. . In the alkylene in the substituted or unsubstituted arylalkyl, any hydrogen may be replaced with fluorine, and any —CH ₂ — may be replaced with —O—, —CH═CH—, or cycloalkylene. .

Of the silsesquioxane dianhydrides represented by the formula (S), a compound represented by the following formula (S-1) is particularly preferable.

When the silsesquioxane dianhydride derivative is used in combination, the voltage holding ratio of the liquid crystal display element is increased, the light resistance and the heat resistance are increased, and the ion density is reduced. In the acid dianhydride constituting the polyamic acid in the liquid crystal aligning agent of the present invention, the silsesquioxane dianhydride is preferably contained in a molar ratio of 1 to 60%, more preferably 10 to 40%.

The tetracarboxylic dianhydride used in combination with the tetracarboxylic dianhydride represented by the formula (G) can be used as appropriate for the type and blending amount as long as the effects of the present invention are achieved. In the present invention, it is possible to use a copolymer obtained by reacting a diamine with at least one other tetracarboxylic dianhydride together with the tetracarboxylic dianhydride represented by the formula (G). It is preferable because storage stability is improved.

A part of the tetracarboxylic dianhydride used in combination with the tetracarboxylic dianhydride represented by the formula (G) may be replaced with a carboxylic anhydride. By such replacement, the termination of the polymerization reaction when producing the polyamic acid can be caused, and the progress of the polymerization reaction can be suppressed. For this reason, the molecular weight of the polymer (polyamic acid or its derivative) obtained can be easily controlled, and for example, the coating properties of the liquid crystal aligning agent can be improved without impairing the effects of the present invention. The ratio of the carboxylic acid anhydride to the tetracarboxylic dianhydride may be in a range that does not impair the effects of the present invention, but it is preferably set to 10 mol% or less of the total tetracarboxylic dianhydride amount. As long as the effects of the present invention are not impaired, one carboxylic acid anhydride may be used, or two or more carboxylic acid anhydrides may be used. Carboxylic anhydride is maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n-hexadecyl succinic anhydride, and cyclohexanedicarboxylic anhydride Things are illustrated.

The tetracarboxylic dianhydride used in combination with the tetracarboxylic dianhydride represented by the above formula (G) has a ratio of dicarboxylic acid to tetracarboxylic dianhydride in the range of 10 mol% or less, and partly It may be replaced by a dicarboxylic acid. As long as the effect of the present invention is not impaired, one dicarboxylic acid may be used, or two or more dicarboxylic acids may be used.

The diamine that can be reacted with tetracarboxylic dianhydride in the present invention is represented by the following formula (I).

_{^{H 2 N-X 1 -X 1}} -X 1 -X 1 -X 1 -X 1 -X 1 -NH 2 (I)

In formula (I):
X ¹ independently represents a single bond, alkylene having 1 to 30 carbon atoms, or a divalent group having a ring in which the sum of the numbers of carbon, nitrogen and oxygen atoms constituting the skeleton is 3 to 30;
_-CH 2 in the alkylene - is ^{-O -, - NH -, -} CO -, - CHY 1 -, - C (Y 1) 2 -, - NY 1 -, - S -, - SO -, - SO 2 -, Or -Si (Y ¹ ) _2- may be substituted,
_-CH 2 CH ₂ in the alkylene - is -CH = CH -, - C≡C-, or -N = may be replaced by N-,
-H alkylene is -F, -Cl, -Br, -C≡N, -OH, -COOH, -SO 3 H, or may be replaced by _-PO 3 _{H 2,}
-H of a ring in which the sum of the numbers of carbon, nitrogen and oxygen atoms constituting the skeleton is 3 to 30 is -F, -Cl, -Br, -C≡N, -OH, -COOH, -SO May be replaced with ₃ H, or —PO ₃ H ₂ , or —Y ¹ ;

Y ¹ independently represents —H, —F, —Cl, —Br, —C≡N, —OH, —COOH, —SO ₃ H, —PO ₃ H ₂ , or the following formula (XXI):

^{~A 1 -A 1 -A 1 -A 1} -A 1 -A 1 -A 2 (XXI)
In formula (XXI):
A ¹ is independently a single bond, alkylene having 1 to 12 carbons, or a ring in which the sum of the numbers of carbon, nitrogen and oxygen atoms constituting the skeleton is 3 to 30;
It is -O - - -CH ₂ in the ^{alkylene, - NH -, - CO -} , - CHY 2 -, - C (Y 2) 2 -, or -NY ² - may be replaced by,
_-CH 2 CH ₂ in the alkylene - is -CH = CH -, - C≡C-, or -N = may be replaced by N-,
-H alkylene is -F, -Cl, -Br, -C≡N, -OH, -COOH, -SO 3 H, or may be replaced by _-PO 3 _{H 2,}
Ring of -H is _{-F, -Cl, -Br, -C≡N,} -OH, -COOH, -SO 3 H, -PO 3 H 2, -N (Y 2) 2 or the following formula, (XXII) May be replaced with

^{~A 3 -A 3 -A 3 -A 2} (XXII)
In formula (XXII):
A ³ is independently a single bond, alkylene having 1 to 12 carbons, or a ring in which the sum of the numbers of carbon, nitrogen and oxygen atoms constituting the skeleton is 3 to 30;
It is -O - - -CH ₂ in the ^{alkylene, - NH -, - CO -} , - CHY 2 -, - C (Y 2) 2 -, or -NY ² - may be replaced by,
_-CH 2 CH ₂ in the alkylene - is -CH = CH -, - C≡C-, or -N = may be replaced by N-,
-H alkylene is -F, -Cl, -Br, -C≡N, -OH, -COOH, -SO 3 H, or may be replaced by _-PO 3 _{H 2,}
Ring of -H is _{-F, -Cl, -Br, -C≡N,} -CH 3, -OCH 3, -OCH 2 F, -OCHF 2, -OCF 3, -OH, -COOH, -SO 3 H , it may be replaced by _-PO 3 _{H 2} or -N ^(Y ₂₎ 2,,

In formula (XXI) or formula (XXII),
A ² is independently —H, —F, —Cl, —Br, —C≡N, —OH, —COOH, —SO ₃ H, —PO ₃ H ₂ , or alkyl having 1 to 40 carbon atoms. ,
It is -O - - -CH ₂ in the alkyl, - NH-, or -CO- may be replaced by,
—CH ₂ CH ₂ — in alkyl may be replaced by —CH═CH—, —C≡C—, or —N═N—,
-H alkyl is -F, -Cl, -Br, -C≡N, -OH, -COOH, -SO 3 H, or may be replaced by _-PO 3 _{H 2,}
Y ² is independently —H, alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons;
In formula (I):
When a plurality of Y ¹ are present, they may be bonded to each other to form a ring;
However, at least one of X ¹ is an alkylene having 1 to 30 carbon atoms, or a ring having 3 to 30 sum of the numbers of carbon, nitrogen and oxygen atoms constituting the skeleton.

The diamine represented by the formula (I) is specifically represented by the following formula (II), (III), (IV), (V), (VI), (VII), (VIII), or (IX). It is a compound represented.

In the formulas (II), (III), (IV), (V), (VI), (VII), (VIII), and (IX),
X ² is independently alkylene having 1 to 12 carbons,
It is -O - - -CH ₂ in the alkylene, - NH-, or -CO- may be replaced by,
_-CH 2 CH ₂ in the alkylene - is -CH = CH -, - C≡C-, or -N = may be replaced by N-,
-H alkylene is -F, -Cl, -Br, -C≡N, -OH, -COOH, -SO 3 H, may be replaced by alkyl of _-PO 3 _{H 2} or 1 to 10 carbon atoms, ,
X ³ is independently a single bond, —O—, —S—, —S—S—, —SO ₂ —, —CO—, —CONH—, —COO—, —NH—, —N (CH ₃ ). _{- (CH 2) m -N (} CH 3) -, - C (CH 3) 2 -, - C (CF 3) 2 -, - (CH 2) m -, - O- (CH 2) m -O _{-, - S- (CH 2)} m -S- (m is an integer from 1 to 6), - COCH = CH -, - N = N-, or -C≡C- a group including,

X ⁴ independently represents alkylene having 1 to 6 carbon atoms or phenylene, and -H of phenylene may be replaced with alkyl having 1 to 30 carbon atoms,
l is an integer of 1 to 10,

Y ¹ is independently —H, —F, —Cl, —Br, —C≡N, —OH, —COOH, —SO ₃ H, —PO ₃ H ₂ , or the following formula (XXI):

^{~A 1 -A 1 -A 1 -A 1} -A 1 -A 1 -A 2 (XXI)
In formula (XXI):
A ¹ is independently a single bond, alkylene having 1 to 12 carbons, or a ring in which the sum of the numbers of carbon, nitrogen and oxygen atoms constituting the skeleton is 3 to 30;
It is -O - - -CH ₂ in the ^{alkylene, - NH -, - CO -} , - CHY 2 -, - C (Y 2) 2 -, or -NY ² - may be replaced by,
_-CH 2 CH ₂ in the alkylene - is -CH = CH -, - C≡C-, or -N = may be replaced by N-,
-H alkylene is -F, -Cl, -Br, -C≡N, -OH, -COOH, -SO 3 H, or may be replaced by _-PO 3 _{H 2,}
Ring of -H is _{-F, -Cl, -Br, -C≡N,} -OH, -COOH, -SO 3 H, -PO 3 H 2, -N (Y 2) 2 or the following formula, (XXII) May be replaced with

^{~A 3 -A 3 -A 3 -A 2} (XXII)
In formula (XXII):
A ³ is independently a single bond, alkylene having 1 to 12 carbons, or a ring in which the sum of the numbers of carbon, nitrogen and oxygen atoms constituting the skeleton is 3 to 30;
It is -O - - -CH ₂ in the ^{alkylene, - NH -, - CO -} , - CHY 2 -, - C (Y 2) 2 -, or -NY ² - may be replaced by,
_-CH 2 CH ₂ in the alkylene - is -CH = CH -, - C≡C-, or -N = may be replaced by N-,
-H alkylene is -F, -Cl, -Br, -C≡N, -OH, -COOH, -SO 3 H, or may be replaced by _-PO 3 _{H 2,}
Ring of -H is _{-F, -Cl, -Br, -C≡N,} -CH 3, -OCH 3, -OCH 2 F, -OCHF 2, -OCF 3, -OH, -COOH, -SO 3 H , it may be replaced by _-PO 3 _{H 2} or -N ^(Y ₂₎ 2,,

In formula (XXI) or formula (XXII),
A ² is independently —H, —F, —Cl, —Br, —C≡N, —OH, —COOH, —SO ₃ H, —PO ₃ H ₂ , or alkyl having 1 to 40 carbon atoms. ,
It is -O - - -CH ₂ in the alkyl, - NH-, or -CO- may be replaced by,
—CH ₂ CH ₂ — in alkyl may be replaced by —CH═CH—, —C≡C—, or —N═N—,
-H alkyl is -F, -Cl, -Br, -C≡N, -OH, -COOH, -SO 3 H, or may be replaced by _-PO 3 _{H 2,}
Y ² is independently —H, alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons;
In formula (I):
When a plurality of Y ¹ are present, they may be bonded to each other to form a ring;

In the formulas (II), (III), (IV), (V), (VI), (VII), and (VIII),
a is an integer of 0 to 4 depending on the structure of the atom or ring to which Y ¹ is bonded;
In formulas (V), (VI), (VII) and (VIII)
Benzene ring is piperidine ring, piperazine ring, pyrrolidine ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, triazole ring, naphthalene ring , Anthracene ring, indole ring, steroid ring, or hexahydro-furo [3.2-b] furan ring.

The diamine that can be used in the present invention can be appropriately used depending on the required properties.
For example, it is preferable to use a diamine having an oriented side chain structure for a VA or TN liquid crystal display element. A diamine having an oriented side chain structure, for example, has a substituent (side chain) branched from the main chain when the substituent connecting two amino groups is the main chain, and is perpendicular to the liquid crystal Or a diamine having a property of developing a pretilt angle. The side chain may be appropriately selected according to the required orientation.
On the other hand, it is preferable to use a diamine having no oriented side chain structure for an IPS liquid crystal display element or the like.

In these diamines, when two amino groups are bonded to the same six-membered carbon, they are preferably bonded to each other meta or para.
The diamine that can be used in the present invention may be appropriately selected according to the required properties, but the formulas (II-1), (III-1), (IV-1), (V-1), ( V-2), (V-11), (VI-1), (VI-2), (VI-3), (VI-11), (VI-12), (VII-1), (VII- 2), (VII-3), (VII-11), (VII-12), (VIII-1), (VIII-2), (VIII-3), (VIII-4), (VIII-11) Or a compound represented by (IX-1).

Formulas (II-1), (III-1), (IV-1), (V-1), (V-2), (V-11), (VI-1), (VI-2), ( VI-3), (VI-11), (VI-12), (VII-1), (VII-2), (VII-3), (VII-11), (VII-12), (VIII- 1), (VIII-2), (VIII-3), (VIII-4), (VIII-11), and (IX-1)

X ¹¹ is independently alkylene having 1 to 12 carbons, and —H of alkylene may be replaced with alkyl having 1 to 10 carbons;
X ⁵ is independently —COCH═CH—, —N═N—, or —C≡C—,
X ⁶ is independently a single bond, —O—, —S—, —S—S—, —SO ₂ —, —CO—, —CONH—, —COO—, —NH—, —N (CH ₃ ). _{- (CH 2) m -N (} CH 3) -, - C (CH 3) 2 -, - C (CF 3) 2 -, - (CH 2) m -, - O- (CH 2) m -O _{-, - S- (CH 2)} m -S- ( where m is an integer of 1 to 6), - COCH = CH -, - N = N-, or a -C≡C-,

X ⁷ independently represents methylene or phenylene, and —H of phenylene may be substituted with alkyl having 1 to 30 carbons;
X ⁸ is independently a single bond or alkylene having 1 to 3 carbon atoms,
X ⁹ is independently a single bond, 1,4-phenylene or 1,4-cyclohexylene,
X ¹⁰ is a single bond, —O—, —COO—, —CO—, —CONH—, — (CH ₂ ) _m — (m is an integer of 1 to 6), —CHY ² —, —C (Y ²⁾ ₂ -, or -NY ² - a it is,

a is an integer of 0 to 4 depending on the structure of the bond destination,
l represents an integer of 1 to 10,

Y ² is independently —H, alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons;
Y ³ is independently —H, —F, —Cl, —Br, —C≡N, —OH, —COOH, —SO ₃ H, or —PO ₃ H ₂ , or alkyl having 1 to 2 carbon atoms. Yes,
When a plurality of Y ³ are present, they may be bonded to each other to form a ring,
Y ⁴ is independently benzyl, —H, —F, —Cl, —OH, —COOH, —SO ₃ H, —PO ₃ H ₂ , —NHY ⁵ , or —N (Y ⁵ ) ₂ ;
Y ⁵ is independently alkyl having 1 to 20 carbons or alkenyl having 2 to 20 carbons;
Y ⁶ is independently alkyl or phenyl having 1 to 3 carbon atoms,
Y ⁷ is independently alkyl having 1 to 30 carbons, cyclohexyl, or bicyclohexyl, and —H of cyclohexyl or bicyclohexyl may be replaced with alkyl having 1 to 30 carbons;

Y ⁸ is —H or alkyl having 1 to 30 carbons,
It is -O - - -CH ₂ in the alkyl, - NH-, or -CO- may be replaced by,
—CH ₂ CH ₂ — in alkyl may be replaced by —CH═CH—, —C≡C—, or —N═N—,
-H alkyl is -F, -Cl, -Br, -C≡N, -OH, -COOH, -SO 3 H, or may be replaced by _-PO 3 _{H 2,}
Y ⁹ is alkyl having 6 to 30 carbon atoms,
Y ¹⁰ is alkyl having 1 to 30 carbon atoms,

Y ¹⁷ is —H, —F, —Cl, —Br, —C≡N, —OH, —COOH, —SO ₃ H, —PO ₃ H ₂ , or alkyl having 1 to 20 carbons;
It is -O - - -CH ₂ in the alkyl, - NH-, or -CO- may be replaced by,
—CH ₂ CH ₂ — in alkyl may be replaced by —CH═CH—, —C≡C—, or —N═N—,
-H alkyl is -F, -Cl, -Br, -C≡N, -OH, -COOH, -SO 3 H, or may be replaced by _-PO 3 _{H 2,}

Y ¹¹ has a group having a steroid skeleton, a succinimide skeleton, or a phthalimide skeleton, or a group represented by the following formula (XXIII),

In formula (XXIII),
-H rings _{-F, -Cl, -OH, -COOH,} -SO 3 H, -PO 3 H 2, may be replaced by alkyl having 1 to 30 carbon atoms or phenyl,
It is -O - - -CH ₂ in the alkyl, - NH-, or -CO- may be replaced by,
—CH ₂ CH ₂ — in alkyl may be replaced by —CH═CH—, —C≡C—, or —N═N—,
-H alkyl is -F, -Cl, -Br, -C≡N, -OH, -COOH, -SO 3 H, or may be replaced by _-PO 3 _{H 2,}
-H phenyl independently, -F, -Cl, -Br, -C≡N , -CH 3, -OCH 3, -OCH 2 F, -OCHF 2, -OCF 3, -OH, -COOH, -SO ₃ H, or may be replaced by _-PO 3 _{H 2,}

A ⁴ is independently a single bond or alkylene having 1 to 12 carbons,
It is -O - - -CH ₂ in the alkylene, - NH-, or -CO- may be replaced by,
_-CH 2 CH ₂ in the alkylene - is -CH = CH -, - C≡C-, or -N = may be replaced by N-,
-H alkylene is -F, -Cl, -Br, -C≡N, -OH, -COOH, -SO 3 H, or may be replaced by _-PO 3 _{H 2,}
Y ¹² is independently —F or CH ₃ ;
Ring S is independently cyclohexane, 1,3-dioxane, piperidine, piperazine, pyrrolidine, phenylene, pyridine, pyrazine, pyridazine, pyrimidine, triazine, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, triazole, naphthalene, anthracene, Indole, steroid, or hexahydro-furo [3.2-b] furan;
b is independently an integer of 0 to 1, c, d and e are independently integers of 0 to 3, f is independently an integer of 0 to 4, and c + d + e ≧ 1 and 6 ≧ b + c + d + e,

Y ¹³ is —H, —F, —Cl, —Br, —C≡N, —OH, —COOH, —SO ₃ H, —PO ₃ H ₂ , or alkyl having 1 to 30 carbons;
It is -O - - -CH ₂ in the alkyl, - NH-, or -CO- may be replaced by,
—CH ₂ CH ₂ — in alkyl may be replaced by —CH═CH—, —C≡C—, or —N═N—,
Alkyl —H may be replaced by —F, —Cl, —Br, —C≡N, —OH, —COOH, —SO ₃ H, or —PO ₃ H ₂ .

More specifically, the diamine represented by the formula (I) is a compound represented by the following formula.
Examples of the diamine represented by the formula (II-1) include compounds represented by the following formulas (II-1-1) to (II-1-4).

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

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

Examples of the diamine represented by the formula (V-1) include diamines represented by the following formulas (V-1-1) to (V-1-19).

Examples of the diamine represented by the formula (V-2) include compounds represented by the following formulas (V-2-1) to (V-2-54).

In the formulas (V-2-1) to (V-2-54),
Y ² is independently —H, —F, alkyl having 1 to 30 carbon atoms, fluorine-substituted alkyl having 1 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms, alkenyl having 2 to 30 carbon atoms, —C≡N , -OCH ₂ F, a -OCHF ₂ or -OCF _3,,
Preferably, independently -H, alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons,
Y ⁵ is independently alkyl having 1 to 30 carbons or alkenyl having 2 to 30 carbons,
Y ¹⁶ is independently —H, alkyl having 1 to 30 carbons, alkoxy having 1 to 29 carbons, or alkenyl having 2 to 30 carbons,
Y ¹⁸ is independently —F, —CF ₃ , or —OCF ₃ .

Examples of the diamine represented by the general formula (V-11) include compounds represented by the following formulas (V-11-1) to (V-11-19).

Examples of the diamine represented by the formula (VI-1) include compounds represented by the following formulas (VI-1-1) to (VI-1-39).

Examples of the diamine represented by the formula (VI-2) include compounds represented by the following formulas (VI-2-1) to (VI-2-8).

In formulas (VI-2-1) to (VI-2-8),
Y ¹⁵ is independently alkyl having 3 to 30 carbons, alkoxy having 3 to 29 carbons, or alkenyl having 3 to 30 carbons.
Y ¹⁶ is independently —H, alkyl having 1 to 30 carbons, alkoxy having 1 to 29 carbons, or alkenyl having 2 to 30 carbons.

Examples of the diamine represented by the formula (VI-3) include compounds represented by the following formulas (VI-3-1) and (VI-3-2).

In formulas (VI-3-1) to (VI-3-2),
Y ¹⁵ is independently alkyl having 3 to 30 carbons, alkoxy having 3 to 29 carbons, or alkenyl having 3 to 30 carbons.
Y ¹⁶ is independently —H, alkyl having 1 to 30 carbons, alkoxy having 1 to 29 carbons, or alkenyl having 2 to 30 carbons.

Examples of the diamine represented by the formula (VI-11) include compounds represented by the following formulas (VI-11-1) to (VI-11-16).

Examples of the diamine represented by the general formula (VI-12) include compounds represented by the following formula (VI-12-1).

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

Examples of the diamine represented by the formula (VII-2) include compounds represented by the following formulas (VII-2-1) to (VII-2-15).

Examples of the diamine represented by the formula (VII-3) include compounds represented by the following formulas (VII-3-1) to (VII-3-4).

Examples of the diamine represented by the formula (VII-11) include diamines represented by the following formulas (VII-11-1) to (VII-11-6).

Examples of the diamine represented by the general formula (VII-12) include compounds represented by the following formula (VII-12-1).

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

Examples of the diamine represented by the formula (VIII-2) include compounds represented by the following formulas (VIII-2-1) to (VIII-2-8).

In formulas (VIII-2-1) to (VIII-2-8),
Y ¹⁶ is independently —H, alkyl having 1 to 30 carbons, alkoxy having 1 to 29 carbons, or alkenyl having 2 to 30 carbons.

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

In formulas (VIII-3-1) to (VIII-3-3),
Y ¹⁶ is independently —H, alkyl having 1 to 30 carbons, alkoxy having 1 to 29 carbons, or alkenyl having 2 to 30 carbons,
Y ⁹ is alkyl having 6 to 30 carbon atoms.

Examples of the diamine represented by the formula (VIII-4) include compounds represented by the following formulas (VIII-4-1) to (VIII-4-8).

Examples of the diamine represented by the formula (VIII-11) include compounds represented by the following formula (VIII-11-1).

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

Examples of diamines other than the compounds exemplified so far include naphthalene-based diamines having a naphthalene structure, and fluorene-based diamines having a fluorene structure.

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. The content of the monoisocyanate compound in the monomer is preferably 1 to 10 mol% with respect to the total amount of diamine and tetracarboxylic dianhydride in the monomer. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

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. In addition, the polyamic acid of the present invention or a derivative thereof is decomposed with a strong alkaline aqueous solution such as KOH or NaOH, and then the components extracted from the decomposition product with an organic solvent are analyzed by GC, HPLC or GC-MS. Monomer can be confirmed.

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

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. As the alkenyl-substituted nadiimide compound, one compound may be used alone, or two or more compounds may be used in combination. The content of the alkenyl-substituted nadiimide compound is preferably 0.01 to 1.00, more preferably 0.01 to 0.70 in terms of a weight ratio with respect to the total amount of polyamic acid or derivative thereof in the liquid crystal aligning agent. Preferably, 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 having 1 to 12 carbons, alkenyl having 2 to 6 carbons, cycloalkyl having 5 to 8 carbons, aryl having 6 to 12 carbons, benzyl, -Z ^1- (O) _q- (Z ² O ) A group represented by _r -Z ³ -H, a group represented by-(Z ⁴ ) _s -BZ ⁵ -H, a group represented by -BTBH, or a group thereof In which 1 to 3 hydrogen atoms are substituted with a hydroxyl group.
Wherein Z ¹ , Z ² and Z ³ are independently alkylene having 2 to 6 carbons, q is 0 or 1, and r is an integer of 1 to 30,
Z ⁴ and Z ⁵ are independently alkylene having 1 to 4 carbons or cycloalkylene having 5 to 8 carbons, B is phenylene, and s is 0 or 1,
B is phenylene and T is —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, —CO—, —S— or —SO ₂ —.

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
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 - , a group represented by - ^{Z 4} -B-Z ⁵ -, a group represented _{by, -B- (O-B) s} -T- (B-O) s group represented by -B- or 1-3 of these groups, In which hydrogen is replaced by a hydroxyl group.
Here, the meanings of Z ^{1 to} Z ³ , r, Z ⁴ , Z ⁵ , and B are as described above,
B is phenylene, T is alkylene having 1 to 3 carbon atoms, —O— or SO ₂ —, and s is 0 or 1.

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 is phenylene, and T is _-CH 2 -, - O- Or —SO ₂ —), a group represented by —B—O—B—C ₃ H ₆ —B—O—B— (B is phenylene), and A group in which one or two hydrogens of a group 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 are the compounds shown below.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

A particularly preferred alkenyl-substituted nadiimide compound is bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) represented by the following formula (Ina-1). Phenyl} methane, N, N′-m-xylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) represented by the formula (Ina-2), and N, N′-hexamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) represented by the formula (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. As the compound having a radical polymerizable unsaturated double bond, one compound may be used alone, or two or more compounds may be used in combination. The compound having a radical polymerizable unsaturated double bond does not include the alkenyl-substituted nadiimide compound. The content of the compound having a radically polymerizable unsaturated double bond is preferably 0.01 to 1.00, preferably 0.01 to 0.70, in a weight ratio with respect to the total amount of the polyamic acid or its derivative. Is more preferable and 0.01 to 0.50 is still 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 (meth) acrylic acid esters include cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, Isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate. They are 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.

Specific examples of the bifunctional (meth) acrylic acid ester include ethylene bisacrylate, Aronix M-210, Aronix M-240 and Aronix M-6200, which are products of Toa Synthetic Chemical Industry Co., Ltd., Nippon Kayaku Co., Ltd. KAYARAD HDDA, KAYARAD HX-220, KAYARAD R-604 and KAYARAD R-684, products of Osaka Organic Chemical Industry Co., Ltd., V260, V312 and V335HP, and Kyoeisha Yushi Chemical Co., Ltd. Light acrylate BA-4EA, light acrylate BP-4PA, and light acrylate BP-2PA.

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

Specific examples of the (meth) acrylic acid amide derivative are N-isopropylacrylamide, N-isopropylmethacrylamide, Nn-propylacrylamide, Nn-propylmethacrylamide, N-cyclopropylacrylamide, N-cyclopropylmethacrylamide. N-ethoxyethylacrylamide, N-ethoxyethylmethacrylamide, N-tetrahydrofurfurylacrylamide, N-tetrahydrofurfurylmethacrylamide, N-ethylacrylamide, N-ethyl-N-methylacrylamide, N, N-diethylacrylamide, N-methyl-Nn-propylacrylamide, N-methyl-N-isopropylacrylamide, N-acryloylpiperidine, N-acryloylpyrrolidine, N, N′-methylenebisa Rilamide, N, N′-ethylenebisacrylamide, N, N′-dihydroxyethylenebisacrylamide, N- (4-hydroxyphenyl) methacrylamide, N-phenylmethacrylamide, N-butylmethacrylamide, N- (iso-butoxy Methyl) 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.

Specific examples of bismaleimide include, for example, BMI-70 and BMI-80 manufactured by Kay Kasei Co., Ltd., and BMI-1000, BMI-3000, BMI-4000, BMI-5000 manufactured by Daiwa Kasei Kogyo Co., Ltd. BMI-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. As the oxazine compound, one compound may be used alone, or two or more compounds may be used in combination. 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 with respect to the total amount of the polyamic acid or its derivative, More preferably, it is 20% 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. Although the structure of the oxazine compound used by this invention is not specifically limited, The structure of the oxazine which has aromatic groups containing condensed polycyclic aromatic groups, such as a benzoxazine and a naphthoxazine, is illustrated.

Specific 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 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 are 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- It is. Here, m is an integer of 1-6.
In formulas (e) and (f), Y is independently a single bond, —O—, —S—, —CO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —. Or alkylene having 1 to 3 carbon atoms.

The oxazine compound also 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 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 compounds.

In the 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 (c) include a compound represented by the following formula (c ′).

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 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 —. Specific examples of the oxazine compound represented by the formula (c ′) are the following compounds.

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

Specific examples of the oxazine compound represented by the formula (d) are the following compounds.

Specific examples of the oxazine compound represented by the formula (e) are the following compounds.

Specific examples of the oxazine compound represented by the formula (f) are the following compounds.

Among these, the formula (b-1), the formula (c-1), the formula (c-3), the formula (c-5), the formula (c-7), the formula (c-9), and the formula are preferable. It is an oxazine compound represented by (d-1) to formula (d-6), formula (e-3), formula (e-4), and formula (f-2) to formula (f-4).

The oxazine compound can be produced by a method similar to the method described in International Publication No. 2004/009708, JP-A-11-12258, and JP-A-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 No. 2004/009708). Issue pamphlet).

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

The oxazine compounds represented by the formulas (d) to (f) include diamines such as 4,4′-diaminodiphenylmethane and diamines having a plurality of benzene rings and organic groups that bind them, formalins and other aldehydes, and phenols. Can be obtained by dehydrating condensation reaction at a temperature of 90 ° C. or higher in n-butyl alcohol (see JP-A No. 2004-352670).

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. An oxazoline compound is a compound having an oxazoline structure. As the oxazoline compound, one compound may be used alone, or two or more compounds may be used in combination. The content of the oxazoline compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, and more preferably 1 to 20% by weight with respect to the total amount of the polyamic acid or derivative thereof. It is preferable. Alternatively, the content of the oxazoline compound is preferably 0.1 to 40% by weight with respect to the polyamic acid or a derivative thereof when the oxazoline structure in the oxazoline compound is converted to oxazoline.

The oxazoline compound may have one oxazoline structure in one compound, but preferably has two or more. The oxazoline compound may be a homopolymer having a oxazoline ring structure in the side chain or 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. There 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, and may comprise two or more monomers having an oxazoline structure in the side chain and an oxazoline structure. It may be a copolymer with a monomer that it 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.

Specific 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'-methylenebis ( -tert- butyl-2-oxazoline), and 2,2'-methylenebis (4-phenyl-2-oxazoline). In addition to these, polymers and oligomers having oxazolyl such as Epocross (trade name, manufactured by Nippon Shokubai Co., Ltd.) can also be exemplified.

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. As the epoxy compound, one compound may be used alone, or two or more compounds may be used in combination. The content of the epoxy compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, and 1 to 20% by weight based on the total amount of the polyamic acid or derivative thereof. Is more preferable.

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

Specific examples of 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, hydrogenation 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 Compounds, brominated cresol novolac type epoxy compounds, bisphenol A novolac type epoxy compounds, epoxy compounds containing naphthalene skeleton, aromatic polyg 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 diglycidyl ester compounds and glycidyl ester epoxy compounds.

The glycidylamine is exemplified by a polyglycidylamine compound.

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

The glycidyl amide is exemplified by a glycidyl amide type epoxy compound.

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.

The cycloaliphatic epoxy compound is exemplified by a compound containing an epoxy group obtained by oxidizing a carbon-carbon double bond of a cycloalkene compound.

Specific examples of the bisphenol A type epoxy compound are 828, 1001, 1002, 1003, 1004, 1007, 1010 (all are made by Japan Epoxy Resin Co., Ltd. (currently available as a product of jER series of Mitsubishi Chemical Corporation) / The same applies hereinafter)), 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), Epomic R-140, Epomic R-301, and Epomic R-304 (all manufactured by Mitsui Chemicals, Inc.).

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

A specific example of the bisphenol type epoxy compound is an epoxidized product of 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane.

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

A specific example of the hydrogenated bisphenol type epoxy compound is an epoxidized product of hydrogenated 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane.

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

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

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

Specific examples of the bisphenol A novolak type epoxy compound are 157S70 (manufactured by Japan Epoxy Resin Co., Ltd.) and Epicron N-880 (manufactured by DIC Corporation).

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

Specific 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 ( Formula E105), 1031S, 1032H60 (all Japan Epoxy Resin 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), a compound represented by the following formula E106, and a compound represented by the following structural formula E107 is there.

Specific examples of the dicyclopentadienephenol type epoxy compound are TACTIX-556 (manufactured by The Dow Chemical Company), and Epicron HP-7200 (manufactured by DIC Corporation).

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

Specific examples of the aliphatic polyglycidyl ether compound include ethylene glycol diglycidyl ether (formula E108), diethylene glycol diglycidyl ether (formula E109), polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether (formula E110), tri Propylene 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 Diglycidyl ether (following formula E114), dibromoneopentyl glycol diglycidyl ether (following formula E115), Denacol EX-810, Denaco 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 Nagase Chemte A box Co., Ltd.).

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

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

Specific examples of the diglycidyl ester compound are represented by, for example, diglycidyl terephthalate (the following formula 117), diglycidyl phthalate (the following formula E118), bis (2-methyloxiranylmethyl) phthalate (the following formula E119), A compound represented by the following formula E122, and a compound represented by the following formula E123.

Specific 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 ( Both are manufactured by Nagase ChemteX Corporation.

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

A specific example of a homopolymer of a monomer having oxiranyl is polyglycidyl methacrylate. Specific examples of the copolymer of monomers having oxiranyl include N-phenylmaleimide-glycidyl methacrylate copolymer, N-cyclohexylmaleimide-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate-glycidyl methacrylate copolymer. Polymers, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer, (3-ethyl-3-oxetanyl) methyl methacrylate-glycidyl methacrylate copolymer, and styrene-glycidyl methacrylate copolymer.

Specific examples of monomers having oxiranyl are glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and methyl glycidyl (meth) acrylate.

Other than the oxiranyl-containing monomer in the oxiranyl-containing monomer copolymer, (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, methyl Examples include styrene, chloromethylstyrene, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, N-cyclohexylmaleimide, and N-phenylmaleimide.

Specific 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-5-allyl-1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione (formula E151 below) and glycidyl isocyanurate type epoxy resin.

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

Specific examples of the cycloaliphatic epoxy compound include 2-methyl-3,4-epoxycyclohexylmethyl-2′-methyl-3 ′, 4′-epoxycyclohexylcarboxylate (formula E153 below), 2,3-epoxycyclohexane. Pentane-2 ′, 3′-epoxycyclopentane ether (formula E154 below), ε-caprolactone-modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 1,2: 8,9-di Epoxy limonene (Celoxide 3000 (manufactured by Daicel Chemical Industries, Ltd.), the following formula E155), a compound represented by the following formula E156, CY-175, CY-177, CY-179 (all are The Ciba-Geigy Chemical Corp. (Available from Huntsman Japan Co., Ltd.), EHPD-3150 (Daicel Chemical Industries, Ltd.) ), And a cyclic aliphatic epoxy resin.

For example, the liquid crystal aligning agent of this invention may further contain various additives. Examples of various additives are 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.

The polymer compound is exemplified by a polymer compound that is soluble in an organic solvent. By adding such a polymer compound to the liquid crystal aligning agent of the present invention, the voltage holding ratio of the liquid crystal display element is increased, the ion density is decreased, and the light resistance and heat resistance are increased, thereby improving reliability. A high liquid crystal display element can be manufactured. Specific examples of the polymer compound are polyamide, polyurethane, polyurea, polyester, polyepoxide, polyester polyol, silicone-modified polyurethane, and silicone-modified polyester.

Low molecular weight compounds are: 1) surfactants that meet the purpose when improvement in coating properties is desired; 2) antistatic agents when improvement in antistatic properties is required; 3) adhesion to substrates and rubbing resistance. A silane coupling agent or a titanium-based coupling agent can be exemplified when improvement of the above is desired, or 4) an imidization catalyst can be exemplified when imidization proceeds at a low temperature.

Specific examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N- (2-aminoethyl) -3-aminopropylmethyl. Trimethoxysilane, paraaminophenyltrimethoxysilane, paraaminophenyltriethoxysilane, metaaminophenyltrimethoxysilane, metaaminophenyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycid Xylpropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyl Limethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propylamine, and N, N '-Bis [3- (trimethoxysilyl) propyl] ethylenediamine.

Specific examples of imidation catalysts include aliphatic amines such as trimethylamine, triethylamine, tripropylamine, and tributylamine; aromatics such as N, N-dimethylaniline, N, N-diethylaniline, methyl-substituted aniline, and hydroxy-substituted aniline Amines: cyclic amines such as pyridine, methyl substituted pyridine, hydroxy substituted pyridine, quinoline, methyl substituted quinoline, hydroxy substituted quinoline, isoquinoline, methyl substituted isoquinoline, hydroxy substituted isoquinoline, imidazole, methyl substituted imidazole, hydroxy substituted imidazole . 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 0.1 to 50% by weight, preferably 0.1 to 20% by weight, based on the total amount 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 30% by weight, preferably 0.1 to 10% by weight, based on the total amount of polyamic acid or a 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 total amount 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 the ability to dissolve the polymer component. The solvent includes a wide variety of solvents usually used in the production process and applications of polymer components such as polyamic acid and soluble polyimide, and can be appropriately selected according to the purpose of use. One type of solvent may be used, and two or more types may be used as a mixed solvent.

The solvent is roughly classified into a polyamic acid or a parent solvent of a derivative thereof and another solvent for the purpose of improving coatability.

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

Other solvents for improving coating properties include alkyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, ethylene glycol monoalkyl ethers such as ethylene glycol monobutyl ether, and diethylene glycol monoalkyls such as diethylene glycol monoethyl ether. Ether, ethylene glycol monoalkyl or phenyl acetate, triethylene glycol monoalkyl ether, propylene glycol monomethyl ether, propylene glycol monoalkyl ether such as propylene glycol monobutyl ether, dialkyl malonate such as diethyl malonate, dipropylene glycol monomethyl ether, etc. Examples include dipropylene glycol monoalkyl ether and ester compounds such as acetates. It is.

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

The liquid crystal aligning agent in the present invention is practically used in the form of a solution obtained by diluting a polymer component containing the polyamic acid or a derivative thereof with a normal solvent. The concentration of the polymer component at that time 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 density | concentration of the high molecular component in a liquid crystal aligning agent may be adjusted according to the coating method of a 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 film 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 a film of a liquid crystal aligning agent is formed 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 lowered 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 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. When the liquid crystal aligning agent in the form of a polymer blend is a composition containing polyamic acid or its derivative A and polyamic acid or its derivative B, tetracarboxylic dianhydride represented by (G) in either or both An embodiment including a structural unit derived from diamine and a structural unit derived from a diamine having a side chain structure in either one of A and B is represented by the above formula (V-2). The structural unit derived from the diamine may be contained in either one of the polyamic acid or its derivatives A and B mixed in the polymer blend, but may be contained in both A and B. When blending three or more kinds of polyamic acids or their derivatives, they may be contained in all the polyamic acids or their derivatives to be mixed.

The liquid crystal alignment film of the present invention is a film formed by heating the above-described coating film of the liquid crystal aligning agent of the present invention. The liquid crystal alignment film of the present invention can be obtained by an ordinary method for producing a liquid crystal alignment film from a liquid crystal aligning agent. For example, the liquid crystal alignment film of this invention can be obtained by the process of forming the coating film of the liquid crystal aligning agent of this invention, and the process of heating and baking this. About the liquid crystal aligning film of this invention, you may rub the film | membrane obtained at the said baking process as needed.

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

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

The coating film can be baked under conditions necessary for the polyamic acid or its derivative to undergo 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 rubbing treatment can be performed in the same manner as the rubbing treatment for the alignment treatment of a normal liquid crystal alignment film, and may be any conditions as long as sufficient retardation is obtained in the liquid crystal alignment film of the present invention. Particularly preferable conditions are a push-in amount of 0.2 to 0.8 mm, a stage moving speed of 5 to 250 mm / sec, and a roller rotation speed of 500 to 2,000 rpm. As an alignment treatment method for the liquid crystal alignment film, in addition to the rubbing method, an optical alignment method, a transfer method, and the like are generally known. As long as the effects of the present invention can be obtained, these other alignment treatment methods may be used in combination in the rubbing treatment.

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 processes include a process of drying the coating film and a process of cleaning the film before and after the rubbing treatment with a cleaning liquid.

As the drying step, a method of heat treatment in an oven or an infrared furnace, a method of heat treatment on a hot plate, and the like are generally known as in the baking step. These methods are also applicable to the drying process. 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 for the liquid crystal alignment film before and after the alignment treatment include brushing, jet spray, vapor 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 a cleaning step in forming 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.

The glass substrate described above with the liquid crystal alignment film of the present invention can be used as the substrate, and the ITO electrode formed on the glass substrate as described above with the liquid crystal alignment film of the present invention is used as the electrode. be able to.

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 such that a surface of one of the pair of substrates on which the liquid crystal alignment film is formed 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, 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 Patent Application Publication No. 019965, Japanese Patent Application Laid-Open No. 2001-072626, Japanese Patent Application Laid-Open No. 2001-192657, and the like.

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.

Since the liquid crystal display element for the transverse electric field method does not have to exhibit a relatively large pretilt angle, a side chain structure such as a polyamic acid obtained from a diamine not containing a diamine having a side chain structure or a derivative thereof is used. A liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention containing a polyamic acid not containing benzene or a derivative thereof is suitably used for a liquid crystal display element for a horizontal electric field mode.

Since the liquid crystal display element for a vertical electric field system requires a relatively large pretilt angle, a polyamic acid having a side chain structure such as a polyamic acid obtained from a diamine containing a diamine having a side chain structure or a derivative thereof is used. Or the liquid crystal aligning film formed from the liquid crystal aligning agent of this invention containing the derivative | guide_body is used suitably for the liquid crystal display element for vertical electric field systems.

As described above, 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 a 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.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples. The compounds used in the examples are as follows.

<Tetracarboxylic dianhydride>
PMDA-HH: cyclohexanetetracarboxylic dianhydride (three-dimensional structure controlled: Iwatani Gas Co., Ltd.): Structural formula (G)
H-PMDA: cyclohexanetetracarboxylic dianhydride (without structure control)
CBDA: cyclobutane tetracarboxylic dianhydride: structural formula (19)
PMDA: pyromellitic dianhydride: structural formula (1)
BTDA: butanetetracarboxylic dianhydride: structural formula (23)
EDDA: 4,4 ′-(ethane-1,2-diyl) bis (morpholine-2,6-dione): Structural formula (69)
PSQ1: 18,21-bis (3- (2,5-dioxotetrahydrofuran-3-yl) propyl) -18,21-dimethyl-1,3,5,7,9,11,13,15-octaphenyl -Pentacyclo [10.5.1.25, 13.17, 11.19,15] decasiloxane: Structural formula (S-1)

<Diamine>
MBMA: 4,4′-methylenebis (3-methylaniline): Structural formula (VI-1-5)
5HHP1PDA: 5- (4- (4′-pentylbicyclohexane-4-yl) phenylmethyl) benzene-1,3-diamine: a diamine in which Y ^{2 has} an alkyl chain length of 5 in the structural formula (V-2-7) DATA: 3,5-diamino-1,2,4-triazole DDM: 4,4′-diaminodiphenylmethane: Structural formula (VI-1-1)
PRDA: 4,4 ′-(piperazine-1,4-diyl) dianiline: Structural formula (VII-2-1)
BAPDEA: N, N′-bis (4-aminophenyl) -N, N′-dimethylethylenediamine: Structural formula (VI-1-36)

<Additives>
BANI-M: bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane HEA: N, N′-dihydroxyethylenebisacrylamide EHS: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane GPS: 3-glycidoxypropyltrimethoxysilane

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

<Synthesis of polyamic acid>
[Synthesis Example 1]
0.3250 g of 5HHP1PDA, 1.5301 g of MBMA and 30.0 g of dehydrated NMP were placed in a 100 ml four-necked flask equipped with a thermometer, a stirrer, a raw material charging inlet and a nitrogen gas inlet, and dissolved under stirring in a dry nitrogen stream. . Next, 1.3472 g of PMDA-HH and 0.2977 g of BTDA were added and stirred for 30 hours. If the temperature increased during the reaction, the flask was cooled to keep the temperature below about 70 ° C. After the completion of stirring, 16.5 g of BC was added to the reaction solution to prepare a polyamic acid solution PA1 having a polymer solid concentration of 7% by weight.

The weight average molecular weight of the 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 1% by weight. Using a 2695 separation module / 2414 differential refractometer (manufactured by Waters), the above mixed solution was measured by a GPC method using a developing agent, and was calculated by polystyrene conversion. In addition, the column used HSPgel RT MB-M (product made from Waters), and measured on conditions with column temperature of 40 degreeC and the flow rate of 0.35 mL / min.

[Comparative Synthesis Examples 1 and 2]
Polyamic acid solutions CP1 and CP2 were prepared according to Synthesis Example 1 except that tetracarboxylic dianhydride was changed as shown in Table 1 instead of PMDA-HH.

[Synthesis Examples 2 and 3]
Polyamic acid solutions PA2 and PA3 used by blending with PA1 were prepared according to Synthesis Example 1 except that tetracarboxylic dianhydride and diamine were changed as shown in Table 1.

[Synthesis Examples 4 to 10]
Polyamic acid solutions PA4 to PA10 were prepared according to Synthesis Example 1 except that tetracarboxylic dianhydride, or tetracarboxylic dianhydride and diamine were changed as shown in Table 1.

<Production of liquid crystal display element>
[Example 1]
The 7 wt% polyamic acid solution (PA1) synthesized in Synthesis Example 1 was diluted to 4 wt% by adding a mixed solvent of NMP / BC = 1/1 (weight ratio) to obtain a liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, a liquid crystal display element was produced as follows.

<Method for Manufacturing VA Type Liquid Crystal Display Element>
The obtained liquid crystal aligning agent was apply | coated to a pair of board | substrate with an ITO transparent electrode by the spin coat method, and it dried on the hotplate at 80 degreeC for 90 second. Subsequently, it heat-baked for 60 minutes in the oven set to 200 degreeC, and the board | substrate with which the liquid crystal aligning film was formed was obtained. With the surface on which the alignment film is formed facing inside, one substrate is sealed with an epoxy adhesive leaving the periphery of the liquid crystal injection hole, and 4.25 μm gap material is spread and pasted on the other substrate. Combined. A liquid crystal composition shown below was vacuum injected into the obtained cell, the injection hole was sealed with a light sealant, and UV was irradiated to cure the injection hole. Finally, a heat treatment (isotropic treatment) was performed at 110 ° C. for 30 minutes to obtain a VA liquid crystal display element.

[Examples 2 and 3]
The polyamic acid solution PA1 having a polymer solid content concentration of 7% by weight synthesized in Synthesis Example 1 and the polyamic acid solution PA2 having a polymer solid content concentration of 7% by weight synthesized in Synthesis Example 2 were mixed at a weight ratio of 80/20 (the former / the latter). Next, a mixed solvent of NMP / BC = 1/1 (weight ratio) was added and diluted to a polymer solid content concentration of 4% by weight to prepare a liquid crystal aligning agent AL2. Similarly, PA1 and polyamic acid solution PA3 having a polymer solid content concentration of 7% by weight synthesized in Synthesis Example 3 were mixed at a weight ratio of 80/20 (the former / the latter), and then NMP / BC = 1/1 (weight ratio). Was added to dilute the polymer solid content concentration to 4% by weight to prepare a liquid crystal aligning agent AL3. Using these liquid crystal aligning agents, a liquid crystal display element was produced according to Example 1.

[Examples 4 to 10 and Comparative Examples 1 to 3]
The polyamic acid solution having a concentration of 7% by weight synthesized in Synthesis Examples 4 to 10 and Comparative Synthesis Examples 1 to 3 was similarly added with a mixed solvent of NMP / BC = 1/1 (weight ratio) to a concentration of 4% by weight. Diluted to obtain liquid crystal aligning agents AL4 to AL10 and CA1 to CA3. Using these liquid crystal aligning agents, a liquid crystal display element was produced according to Example 1.

The compositions of the liquid crystal aligning agents used in the above examples are summarized in Table 2.

[Examples 11 to 14]
To the polyamic acid solutions PA5 and PA6 having a concentration of 7% by weight, an additive of 20% by weight per polymer weight as shown in Table 3 was added, and then a mixed solvent of NMP / BC = 1/1 (weight ratio) Was added to dilute to a polymer solids concentration of 4% by weight. A liquid crystal display element was produced according to Example 1 using diluted liquid crystal aligning agents AL11 to AL14.

[Examples 15 to 18]
To the polyamic acid solutions PA1 and PA4 having a concentration of 7% by weight, an additive of 20% by weight per polymer weight as shown in Table 3 was added, and then a mixed solvent of NMP / BC = 1/1 (weight ratio) Was added to dilute to a polymer solids concentration of 4% by weight. A liquid crystal display element was produced according to Example 1 using diluted liquid crystal aligning agents AL15 to AL18.

<Evaluation of long-term thermal reliability of VHR>
About the liquid crystal display element produced in Examples 1-18 and Comparative Examples 1-3, the long-term thermal reliability evaluation of VHR was performed as follows.

<Measurement of VHR>
The voltage holding ratio of the VA liquid crystal display element was measured using a liquid crystal property evaluation apparatus 6254 type manufactured by Toyo Technica. The measurement conditions are a gate width of 60 μsec, a frequency of 30 Hz, a wave height of ± 1 V, and a measurement temperature of 60 ° C.

<Calculation of long-term thermal reliability of VHR>
It measured about the liquid crystal display element produced in Example 1, Examples 4-7, 11-14, and the comparative examples 1 and 2. FIG. The value of VHR measured within 24 hours after device fabrication was defined as VHR (initial). The liquid crystal display element after VHR measurement was stored in an oven maintained at 100 ° C. for 300 hours, and the value of VHR measured under the above-mentioned conditions was defined as VHR (300 hours). From the two obtained VHRs, the VHR reduction rate was calculated according to the following formula. It can be said that the smaller the value, the better the long-term thermal reliability of the VHR. The results are shown in Table 4.
VHR reduction rate = [{VHR (initial) −VHR (300 hours)} × 100] / VHR (initial)

表４における実施例１、４に（１）が付記され、下記の表５における実施例１、４に（２）が付記されているのは、それぞれの試験に別の液晶表示素子が供されたことを表している。

Examples (1) and (1) are added to Examples 1 and 4 in Table 4, and (2) is added to Examples 1 and 4 in Table 5 below, and another liquid crystal display element is provided for each test. It represents that.

  As shown in Table 4, in the liquid crystal display element using the liquid crystal alignment film obtained from the liquid crystal aligning agent containing the polyamic acid containing the acid anhydride having the three-dimensional structure of the present invention, no other three-dimensional structure is formed. Compared with H-PMDA and widely used CBDA, the initial characteristics of VHR and the long-term thermal reliability of VHR are extremely high.

<Evaluation of long-term optical reliability of VHR>
About the liquid crystal display element produced in Examples 1-4, 8-10, 15-18, and the comparative example 3, the long-term optical reliability evaluation of VHR was performed as follows.

<Calculation of long-term optical reliability of VHR>
For each liquid crystal display element, the value of VHR measured within 24 hours after the element fabrication was defined as VHR (initial). Further, the liquid crystal display element after the VHR measurement was stored on a 6000 cd / m ² backlight for 200 hours, and the VHR value measured under the above-mentioned conditions was defined as VHR (200 hours). From the two obtained VHRs, the VHR reduction rate was calculated according to the following formula. It can be said that the smaller the value, the better the long-term optical reliability of the VHR. The results are shown in Table 5.
VHR reduction rate = [{VHR (initial) −VHR (200 hours)} × 100] / VHR (initial)

As shown in Table 5, the liquid crystal aligning agent containing a polyamic acid including an acid anhydride having a three-dimensional structure according to the present invention has good VHR long-term light reliability, and moreover an aromatic acid anhydride, PRDA, BAPDEA, DATA By using a smaller amount of polyamic acid or monomer containing a structure that easily absorbs ultraviolet rays, VHR long-term light reliability can be further enhanced.

Claims (12)

Liquid crystal aligning agent using the polyamic acid obtained by making the tetracarboxylic dianhydride represented by Formula (G), and diamine react, or its derivative (s).

The liquid crystal aligning agent of Claim 1 which is a diamine in which a part or all of diamine has a side chain structure represented by a following formula (V-2).

In the formula (V-2),
X ¹⁰ is a single bond, —O—, —COO—, —OCO—, —CO—, —CONH—, or — (CH ₂ ) _m —, and m is an integer of 1 to 6;
Y ¹¹ has a group having a steroid skeleton, a succinimide skeleton, a phthalimide skeleton, or a cinnamate skeleton, or a group represented by the following formula (XXIII).

In formula (XXIII):
A ⁴ is independently a single bond or alkylene having 1 to 12 carbons,
It is -O - - -CH ₂ in the alkylene, - NH-, or -CO- may be replaced by,
—CH ₂ CH ₂ — may be replaced by —CH═CH—, —C≡C—, or —N═N—
-H alkylene is -F, -Cl, -C≡N, -OH, -COOH, it may be replaced by _-SO 3 H or _-PO 3 _{H 2,;}
Y ¹² is independently —F or —CH ₃ ;
Ring S is independently 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, piperidine-1,4-diyl, pyrimidine-2,5-diyl, pyridine-2. , 5-diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl, or anthracene-9,10-diyl;
Y ¹³ is —H, —F, —Cl, —C≡N, —OH, —COOH, —SO ₃ H, —PO ₃ H ₂ , or alkyl having 1 to 30 carbons;
Is -O - - -CH ₂ in the alkyl, - NH- or -CO- may be replaced by,
—CH ₂ CH ₂ — may be replaced by —CH═CH—, —C≡C— or —N═N—
-H alkyl is -F, -Cl, -C≡N, -OH, -COOH, it may be replaced by _-SO 3 H or _-PO 3 _{H 2,;}
b is independently an integer of 0 to 4, c, d and e are independently integers of 0 to 3, f is independently an integer of 0 to 2 and c + d + e ≧ 1. The liquid crystal aligning agent according to claim 2, wherein Y ¹¹ in the formula (V-2) is one selected from the group of groups represented by the following formulas (Y ¹¹ -1) to (Y ¹¹ -7). .

In the formulas (Y ¹¹ -1) to (Y ¹¹ -7),
Y ² is —H, —F, alkyl having 1 to 30 carbon atoms, fluorine-substituted alkyl having 1 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms, alkenyl having 2 to 30 carbon atoms, —C≡N, —OCH. ₂ F, —OCHF ₂ , or —OCF ₃ ;
A ¹ is —O— or alkylene having 1 to 6 carbon atoms. A part or all of the diamine is at least one selected from the group of compounds represented by the following formulas (V-2-2) to (V-2-8) and (V-2-53): Item 3. A liquid crystal aligning agent according to Item 2.

In the formulas (V-2-2) to (V-2-8) and (V-2-53),
Y ² is independently —H, alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons;
Y ¹⁸ is —F, —CF ₃ or —OCF ₃ . A part or all of the diamine is represented by the following formulas (V-1-1) to (V-1-5), (V-1-14), (V-1-15), (VI-1-1). To (VI-1-12), (VI-1-28) to (VI-1-30), (VI-1-33), (VI-1-35) to (VI-1-39), ( The liquid crystal aligning agent of Claim 1 which is at least 1 chosen from the group of the diamine which does not have the side chain structure represented by (VII-2-1) and (VII-2-2).

In addition to the tetracarboxylic dianhydride represented by the formula (G), the aromatic tetracarboxylic acid represented by the following formulas (1), (2), (5) to (7), and (12) The liquid crystal aligning agent of Claim 1 using the polyamic acid obtained by making at least 1 chosen from the group of a dianhydride react with diamine, or its derivative (s).

In addition to the tetracarboxylic dianhydride represented by the formula (G), the following formulas (19), (23), (26), (35) to (39) (44), (49), and ( 69. The liquid crystal aligning agent according to claim 1, wherein a polyamic acid obtained by reacting at least one selected from the group consisting of aliphatic tetracarboxylic dianhydrides represented by 69) or a derivative thereof is used.

2. The liquid crystal aligning agent according to claim 1, wherein a part or all of the diamine is at least one selected from the group of diamines having the following photosensitive structure.

A polyamic acid obtained by reacting an aromatic tetracarboxylic dianhydride represented by the following formula (68) with a diamine in addition to the tetracarboxylic dianhydride represented by the formula (G) or a derivative thereof The liquid crystal aligning agent of Claim 1 using.

The alkenyl-substituted nadiimide compound, a compound having a radically polymerizable unsaturated double bond, an oxazine compound, an oxazoline compound, and at least one selected from an epoxy compound, further comprising at least one of claims 1 to 9 Liquid crystal aligning agent. The liquid crystal aligning film formed by the coating film of the liquid crystal aligning agent of any one of Claims 1-10 being heated. In the liquid crystal display element having a pair of substrates, a liquid crystal layer formed between the substrates, an electrode for applying a voltage to the liquid crystal layer, and a liquid crystal alignment film for aligning the liquid crystal molecules in a predetermined direction, The liquid crystal display element whose liquid crystal aligning film is a liquid crystal aligning film of Claim 11.