JP2011085901A - Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display device - Google Patents

Abstract

【選択図】なし【Task】
The liquid crystal display element is excellent in long-term thermal reliability, that is, a voltage holding ratio can be kept high for a long time in a heating test of the element, and a liquid crystal alignment film for vertical alignment that reduces residual DC of the liquid crystal display element is formed A liquid crystal aligning agent that can be used is provided. Furthermore, the liquid crystal aligning film formed using the liquid crystal aligning agent, and the liquid crystal display element using the liquid crystal aligning film are provided.
[Solution]
A liquid crystal alignment film is formed using a liquid crystal aligning agent containing a polyamic acid obtained by reacting a tetracarboxylic dianhydride represented by the formula (Q) and a specific side chain diamine, or a derivative thereof, and a liquid crystal display Used for elements.

[Selection figure] None

Description

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

Liquid crystal display elements are used in various liquid crystal display devices such as monitors for notebook computers and desktop computers, video camera viewfinders, and projection displays. Recently, they have also been used as televisions. . Furthermore, it is also used as an optoelectronic-related element such as an optical printer head, an optical Fourier transform element, or a light valve. Conventional liquid crystal display elements are mainly nematic liquid crystal display elements. 1) TN (twisted nematic) type liquid crystal display element twisted 90 degrees, 2) STN (super twisted nematic) type liquid crystal twisted more than 180 degrees normally. 3) A so-called TFT (Thin Film Transistor) type liquid crystal display element using a thin film transistor has been put into practical use.

These liquid crystal display elements have a drawback that a viewing angle at which an image can be properly viewed is narrow, and when viewed from an oblique direction, luminance and contrast are lowered and luminance is inverted in a halftone. In recent years, the problem of viewing angle is as follows: 1) TN-TFT type liquid crystal display element using optical compensation film, 2) VA (vertical alignment) type liquid crystal display element using vertical alignment and optical compensation film, 3) vertical MVA (Multi Domain Vertical Alignment) type liquid crystal display element using alignment and projection structure technology together, or 4) IPS (In-Plane Switching) type liquid crystal display element of horizontal electric field type, 5) ECB (Electrically Controlled Birefringence type) Liquid crystal display element, 6) Optically compensated bend (Optically self-compensated birefringence: OCB) type Been improved by techniques such as crystal display device, these display devices are commercialized or practically has been studied.

The development of the technology of the liquid crystal display element has been achieved not only by improving the drive system and the element structure, but also by improving the components used for the display element. Among the components used for display elements, the liquid crystal alignment film is one of the important elements related to the display quality of the liquid crystal display element, and the role of the liquid crystal alignment film is increasing year by year as the quality of the display element is improved. It is becoming important.

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 obtained by dissolving polyamic acid or soluble polyimide in an organic solvent. After applying such a solution to a 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.

Important characteristics required for the liquid crystal alignment film in order to improve the display quality of the liquid crystal display element include voltage holding ratio and residual DC. If the voltage holding ratio is low, the voltage applied to the liquid crystal during the frame period decreases, resulting in a decrease in luminance and hinders normal gradation display. On the other hand, if the residual DC is large, a so-called “afterimage” is generated in which an erased image remains even though the voltage is turned off after the voltage is applied.

As an attempt to solve the above problems, several methods have been proposed recently.
(1) A polyamic acid composition using a combination of two or more polyamic acids having different physical properties for forming a liquid crystal alignment film is known (Patent Document 1; JP-A-11-193345, Patent Document 2). ; See JP-A-11-193347).
(2) A varnish composition using a polymer component using polyamic acid and polyamide and a solvent is known (see Patent Document 3; International Publication No. 00/061684 pamphlet).
(3) Varnish compositions using two or more polyamic acids and polyamides having different physical properties and a solvent are known. (See Patent Document 4; International Publication No. 01/000733 pamphlet).
(4) A varnish composition using a polymer material using a polyamic acid or the like synthesized using an amine component having a specific structure is known (see Patent Document 5; JP 2002-162630 A). .
However, the reduction of residual DC by tetracarboxylic dianhydride to be reacted with diamine has not been studied much, and there is room for further improvement.

As an example of the invention of tetracarboxylic dianhydride, for example, a liquid crystal alignment film using bicyclohexanetetracarboxylic dianhydride is known. This alignment film is used as a horizontal alignment and sealant and encapsulant in a low voltage driving panel. It is disclosed that the contamination of the liquid crystal is improved (Patent Document 6; see JP 2000-214467 A).

JP 11-193345 A JP-A-11-193347 International Publication No. 00/061684 Pamphlet International Publication No. 01/000733 Pamphlet JP 2002-162630 A JP 2000-214467 A

The present invention is excellent in the long-term thermal reliability of the liquid crystal display element, that is, the voltage holding ratio can be kept high for a long time in the heating test of the element, and the liquid crystal alignment for vertical alignment that reduces the residual DC of the liquid crystal display element. An object of the present invention is to provide a liquid crystal aligning agent capable of forming a film, and further to provide a liquid crystal aligning film formed using the liquid crystal aligning agent, and a liquid crystal display element using the liquid crystal aligning film It is.

The present inventors use a composition containing a polyamic acid or a derivative thereof made of a specific tetracarboxylic dianhydride and a diamine having a vertical alignment side chain as a raw material as a liquid crystal alignment agent for vertical alignment, and is formed thereby. The liquid crystal display device having the liquid crystal alignment film was found to have excellent long-term thermal reliability and low residual DC, and the present invention was completed.

In the detailed description of the invention, a group in which left and right are asymmetrical is defined as that the right and left may face in either direction (for example, -COCH = CH- is "-COCH = CH-" or "-CH = CHCO-" means any one).
When —CH ₂ — in alkyl or alkylene is replaced by —O—, —O— is not consecutive.
Alkyl or alkylene shall be either linear or branched.
The present invention has the following configuration.

式（Ｖ−２）中、
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、もしくはシンナメート骨格を有する基、または下記式（ＸＸＩＩＩ）で表される基であり、

式（ＸＸＩＩＩ）中、
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、アルキレンの−ＣＨ_２−は−Ｏ−、−ＮＨ−、または−ＣＯ−で置き換えられてよく、−ＣＨ_２ＣＨ_２−は−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−または−Ｎ＝Ｎ−で置き換えられてよく、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、アルキルの−ＣＨ_２−は−Ｏ−、−ＮＨ−または−ＣＯ−で置き換えられてよく、−ＣＨ_２ＣＨ_２−は−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−または−Ｎ＝Ｎ−で置き換えられてよく、アルキルの−Ｈは−Ｆ、−Ｃｌ、−Ｃ≡Ｎ、−ＯＨ、−ＣＯＯＨ、−ＳＯ_３Ｈ、または−ＰＯ_３Ｈ_２で置き換えられてよく；そして、
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。 [1] A tetracarboxylic dianhydride represented by the formula (Q) and a diamine having a side chain structure represented by the formula (V-2) or a side chain structure represented by the formula (V-2). A liquid crystal aligning agent for vertical alignment containing a polyamic acid or a derivative thereof obtained by reacting a mixture of a diamine having a diamine with another diamine.

In 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 is 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, and —CH ₂ — in alkylene may be replaced by —O—, —NH—, or —CO—, and —CH ₂ CH _2- may be replaced by —CH═CH—, —C≡C— or —N═N—, and —H of alkylene is —F, —Cl, —C≡N, —OH, —COOH, —SO May be replaced by 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, alkyl of -SO 3 _{H, -PO} 3 H ₂ or 1 to 30 carbon atoms, alkyl of -CH ₂ - it is -O -, - may be replaced by NH- or -CO-, _{-CH 2} CH 2 - is -CH = CH -, - C≡C- or -N = may be replaced by N-, alkyl of -H is -F, -Cl, -C≡N, -OH, -COOH, may be replaced by _-SO 3 H or _-PO 3 _{H 2,;} and,
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^１１−８）中、
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のアルキレンであり；そして、
Ａ^２は−ＯＣＯ−、−ＣＯＯ−、−Ｏ−または炭素数１〜６のアルキレンである。 [2] The item [1], 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 -8). Liquid crystal aligning agent for vertical alignment.

In formulas (Y ¹¹ -1) to (Y ¹¹ -8),
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 carbons; and
A ² is —OCO—, —COO—, —O—, or alkylene having 1 to 6 carbon atoms.

式（Ｖ−２−２）において、Ｙ^２は炭素数６〜３０のアルキルであり；
式（Ｖ−２−３）〜（Ｖ−２−６）において、Ｙ^２は炭素数３〜３０のアルキルであり；
式（Ｖ−２−７）において、Ｙ^２は炭素数２〜３０のアルキルであり；
式（Ｖ−２−８）において、Ｙ^２は炭素数２〜３０のアルキルであり；そして
式（Ｖ−２−５３）において、Ｙ^１８は−Ｆ、−ＣＦ_３または−ＯＣＦ_３である。 [3] The diamine having a side chain group is at least one selected from the group of compounds represented by the following formulas (V-2-1) to (V-2-8) and (V-2-53). The liquid crystal aligning agent for vertical alignment as described in said [1] term.

In Formula (V-2-2), Y ² is alkyl having 6 to 30 carbons;
In formulas (V-2-3) to (V-2-6), Y ² is alkyl having 3 to 30 carbons;
In formula (V-2-7), Y ² is alkyl having 2 to 30 carbons;
In Formula (V-2-8), Y ² is alkyl having 2 to 30 carbons; and in Formula (V-2-53), Y ¹⁸ is —F, —CF ₃ or —OCF ₃ .

[4] At least one diamine represented by formula (V-2) and 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-1-35) to (VI-1- 39), a liquid crystal aligning agent for vertical alignment according to item [1], which is at least one mixture selected from the group of diamines represented by (VII-2-1) and (VII-2-2) .

[5] In addition to the tetracarboxylic dianhydride represented by the formula (Q), an aromatic tetra represented by the following formulas (1), (2), (5) to (7), and (12) The liquid crystal aligning agent for vertical alignment according to [1], wherein a polyamic acid obtained by reacting at least one selected from the group of carboxylic acids with a diamine or a derivative thereof is used.

[6] In addition to the tetracarboxylic dianhydride represented by the formula (Q), the following formulas (19), (23), (25), (35) to (39), (44), and (49) The polyamic acid obtained by reacting at least one selected from the group of alicyclic tetracarboxylic dianhydride and aliphatic tetracarboxylic dianhydride represented by diamine with a diamine, or the derivative thereof, The liquid crystal aligning agent for vertical alignment as described in item [1].

[7] The diamine is at least one of diamines represented by the formula (V-2), and the following formulas (VI-11-4) to (VI-11-16), (V-11-2), and (V -11-17) to (V-11-19), which is at least one mixture selected from the group of diamines having a photosensitive structure, and has a photo-alignment property, as described in [1] above. Liquid crystal aligning agent for alignment.

[8] The diamine is at least one diamine represented by the formula (V-2), and the following formulas (VI-11-7), (VI-11-11), (V-11-2), and (V -11-17) to (V-11-19), which is at least one mixture selected from the group of diamines having a photosensitive structure, and has a photo-alignment property, as described in [1] above. Liquid crystal aligning agent for alignment.

[9] Any of the above [1] to [8], further comprising 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 Item 2. A liquid crystal aligning agent for vertical alignment according to item 1.

[10] A liquid crystal alignment film for vertical alignment formed by heating a coating film of the liquid crystal aligning agent for vertical alignment according to any one of [1] to [9].

[11] 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 The liquid crystal display element, wherein the liquid crystal alignment film is the vertical alignment liquid crystal alignment film of item [10].

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

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). A polyamic acid derivative is a component that dissolves in a solvent when a liquid crystal aligning agent containing a solvent is formed. When the liquid crystal aligning agent is used as a liquid crystal aligning film, a liquid crystal aligning film mainly composed of polyimide is formed. Is a component that can be. Examples of such polyamic acid derivatives include soluble polyimides, polyamic acid esters, and polyamic acid amides. More specifically, 1) a polyimide in which all amino acids and carboxyls of polyamic acid are subjected to dehydration ring-closing reaction, 2) a partial polyimide in which partial dehydration ring-closing reaction is performed, and 3) polyamic acid in which carboxyl of polyamic acid is converted to an ester. 4) A polyamic acid-polyamide copolymer obtained by reacting a part of the acid dianhydride contained in the tetracarboxylic dianhydride compound with an organic dicarboxylic acid, and 5) the polyamic acid-polyamide. Examples thereof include polyamideimide obtained by subjecting a part or all of the 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.

式（Ｑ）で表されるテトラカルボン酸二無水物は、液晶表示素子において所望の電圧保持率を発現させ、またその長期熱信頼性を実現させる観点から、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１０〜１００モル％含まれることが好ましく、２０〜１００モル％含まれることがより好ましい。 The tetracarboxylic dianhydride used in the present invention includes a tetracarboxylic dianhydride represented by the formula (Q).

The tetracarboxylic dianhydride represented by the formula (Q) is a polyamic acid in the liquid crystal aligning agent of the present invention from the viewpoint of expressing a desired voltage holding ratio in a liquid crystal display device and realizing its long-term thermal reliability. It is preferable that 10-100 mol% is contained in the acid dianhydride which comprises, and it is more preferable that 20-100 mol% is contained.

The tetracarboxylic dianhydride constituting the polyamic acid in the liquid crystal aligning agent of the present invention may include an aromatic tetracarboxylic dianhydride in addition to the tetracarboxylic dianhydride represented by the formula (Q). . 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 tetracarboxylic dianhydride represented by the formula (Q) is an aromatic tetracarboxylic dianhydride used together with the formula (1), (2), (5) to (7), and (12). Compounds represented by formulas (1) and (12) are more preferred. 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. The total acid dianhydride constituting the polyamic acid in the liquid crystal aligning agent of the present invention preferably contains 1 to 90 mol% of aromatic tetracarboxylic dianhydride, more preferably 2 to 60 mol%.

In addition to the tetracarboxylic dianhydride represented by the formula (Q), the tetracarboxylic dianhydride constituting the polyamic acid in the liquid crystal aligning agent of the present invention is an alicyclic tetracarboxylic dianhydride and / or Aliphatic tetracarboxylic dianhydrides may be included. An alicyclic tetracarboxylic dianhydride is a compound in which at least one of two —CO—O—CO— is bonded to an alicyclic compound. An aliphatic tetracarboxylic dianhydride is a compound in which at least one of two —CO—O—CO— is bonded to an aliphatic compound. The alicyclic tetracarboxylic dianhydrides are represented by the following formulas (19) to (22), (24), (25), (27) to (44) (49) to (58), and (62) to (64). ) Is exemplified.

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

The alicyclic tetracarboxylic dianhydride and the aliphatic tetracarboxylic dianhydride have the formulas (19), (23), (25), (35) to (39), (44), and (49). A compound represented by formula (19) and (23) is 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. 1 to 90 mol% of alicyclic tetracarboxylic dianhydride and / or aliphatic tetracarboxylic dianhydride is included in all tetracarboxylic dianhydrides constituting the polyamic acid in the liquid crystal aligning agent of the present invention. Preferably, 10 to 80 mol% is more preferable.

The tetracarboxylic dianhydride used in the present invention preferably contains a silsesquioxane dianhydride derivative. 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.

The silsesquioxane dianhydride used for this invention can use the compound described, for example in the international publication 03/024870 pamphlet, and is represented by the following formula | equation.

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よい。 In 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 formula (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.

式（Ｓ−１）中、Ｒは上記式（Ｓ）におけるＲと同じである。 Of the silsesquioxane dianhydrides represented by the formula (S), a compound represented by the following formula (S-1) is particularly preferable.

In the formula (S-1), R is the same as R in the above formula (S).

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

The tetracarboxylic dianhydride used in combination with the tetracarboxylic dianhydride represented by the formula (Q) can be arbitrarily used with respect to its 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 (Q). 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 (Q) 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, the carboxylic acid anhydride may be used alone, 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.

In the tetracarboxylic dianhydride used in combination with the tetracarboxylic dianhydride represented by the formula (Q), the ratio of the dicarboxylic acid to the tetracarboxylic dianhydride is 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.

式（Ｖ−２）中、
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、もしくはシンナメート骨格を有する基、または下記式（ＸＸＩＩＩ）で表される基であり、 The diamine to be reacted with the tetracarboxylic dianhydride represented by the formula (Q) constituting the polyamic acid or the derivative thereof in the liquid crystal aligning agent of the present invention is a side chain structure represented by the following formula (V-2). It is a compound which has this.

In 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 is 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);

式（ＸＸＩＩＩ）中、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、アルキレンの−ＣＨ_２−は−Ｏ−、−ＮＨ−、または−ＣＯ−で置き換えられてよく、−ＣＨ_２ＣＨ_２−は−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−または−Ｎ＝Ｎ−で置き換えられてよく、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、アルキルの−ＣＨ_２−は−Ｏ−、−ＮＨ−または−ＣＯ−で置き換えられてよく、−ＣＨ_２ＣＨ_２−は−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、または−Ｎ＝Ｎ−で置き換えられてよく、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。

In formula (XXIII), A ⁴ is independently a single bond or alkylene having 1 to 12 carbons, and —CH ₂ — in alkylene is replaced by —O—, —NH—, or —CO—. Well, —CH ₂ CH ₂ — may be replaced by —CH═CH—, —C≡C— or —N═N—, and —H of 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, alkyl of -SO 3 _{H, -PO} 3 H ₂ or 1 to 30 carbon atoms, alkyl of -CH ₂ - is -O -, - may be replaced by NH- or -CO-, _{-CH 2} CH 2 - is -CH = CH -, - C≡C-, or -N = may be replaced by N-, -H alkyl is -F, -Cl, -C≡N, -OH, -COOH, 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^１１−８）中、
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のアルキレンであり、そして、
Ａ^２は−ＯＣＯ−、−ＣＯＯ−、−Ｏ−または炭素数１〜６のアルキレンである。 Diamines of the formula (V-2) ^{is, Y 11} is one selected from the group consisting of groups represented by the following formula ^{(Y 11 -1) ~ (Y} 11 -8) compounds are preferred.

In formulas (Y ¹¹ -1) to (Y ¹¹ -8),
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 carbons, and
A ² is —OCO—, —COO—, —O—, or alkylene having 1 to 6 carbon atoms.

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

In 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, it is 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, and
Y ¹⁸ is —F, —CF ₃ or —OCF ₃ .

式（Ｖ−２−２）において、Ｙ^２は炭素数６〜３０のアルキルが好ましく、炭素数９〜２０のアルキルがより好ましい。
式（Ｖ−２−３）〜（Ｖ−２−６）において、Ｙ^２は炭素数３〜３０のアルキルが好ましく、炭素数５〜２０のアルキルがより好ましい。
式（Ｖ−２−７）において、Ｙ^２は炭素数２〜３０のアルキルが好ましく、炭素数４〜２５のアルキルがより好ましい。
式（Ｖ−２−８）において、Ｙ^２は炭素数２〜３０のアルキルが好ましく、炭素数２〜１２のアルキルがより好ましい。そして、
式（Ｖ−２−５３）におけるＹ^１８は−Ｆ、−ＣＦ_３または−ＯＣＦ_３である。 The diamine represented by the formula (V-2) is at least selected from the group of compounds represented by the above formulas (V-2-2) to (V-2-8) and (V-2-53). One is preferred.

In Formula (V-2-2), Y ² is preferably alkyl having 6 to 30 carbons, and more preferably alkyl having 9 to 20 carbons.
In formulas (V-2-3) to (V-2-6), Y ² is preferably an alkyl having 3 to 30 carbon atoms, and more preferably an alkyl having 5 to 20 carbon atoms.
In Formula (V-2-7), Y ² is preferably alkyl having 2 to 30 carbons, and more preferably alkyl having 4 to 25 carbons.
In formula (V-2-8), Y ² is preferably alkyl having 2 to 30 carbons, and more preferably alkyl having 2 to 12 carbons. And
Y ¹⁸ in the formula (V-2-53) is —F, —CF ₃ or —OCF ₃ .

Other diamines to be reacted with the tetracarboxylic dianhydride represented by the formula (Q) in combination with the diamine represented by the formula (V-2) can be appropriately used depending on the required properties. When using for the liquid crystal aligning agent for vertical alignment of this invention, use of the diamine which has an orientation side chain structure similarly to the diamine represented by Formula (V-2) is preferable. A diamine having an oriented side chain structure has a substituent branched from the main chain (side chain) when the substituent connecting two amino groups is the main chain, and is perpendicular to the liquid crystal. Or it is diamine which has the property to express a pretilt angle. The side chain may be appropriately selected according to the required orientation. As the diamine to be used in combination, a compound having no oriented side chain structure can be selected as long as the effects of the present invention are not impaired. The liquid crystal aligning agent of the present invention can be applied to a TN or IPS liquid crystal display element depending on the structure of the diamine used in combination.

Other diamines that can be used in the present invention may be appropriately selected according to the required properties, but those represented by formulas (II-1), (III-1), (IV-1), and (V-1) , (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 (IX- The compound represented by 1) is mentioned.
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.

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

X ¹¹ is independently alkylene having 1 to 12 carbons, and —H on the 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 -, - COCH = CH -, - N = N-, or a -C≡C-, and,
m is an integer of 1-6,

X ⁷ is independently methylene or phenylene, and —H of phenylene may be replaced by 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 —, —CHY ² —, —C (Y ² ) ₂ —, or —NY ² —. Yes, and
m is an integer of 1-6,

a is an integer of 0 to 4 depending on the structure of the atom or ring to which Y ² , Y ³ , Y ⁴ , Y ⁷ , and Y ¹⁴ are bonded;
l is 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 substituted with alkyl having 1 to 30 carbons;

Y ⁸ is —H or alkyl having 1 to 30 carbons,
Alkyl —CH ₂ — may be replaced by —O—, —NH— or —CO—,
The alkyl —CH ₂ CH ₂ — may be replaced by —CH═CH—, —C≡C— or —N═N—
-H alkyl is -F, -Cl, -Br, -C≡N, -OH, -COOH, may be replaced by _-SO 3 H or _-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;
Alkyl —CH ₂ — may be replaced by —O—, —NH— or —CO—,
The alkyl —CH ₂ CH ₂ — may be replaced by —CH═CH—, —C≡C— or —N═N—
-H alkyl is -F, -Cl, -Br, -C≡N, -OH, -COOH, may be replaced by _-SO 3 H or _-PO 3 _{H 2,,}

式（ＸＸＩＩＩ）中、
環上の−Ｈは−Ｆ、−Ｃｌ、−ＯＨ、−ＣＯＯＨ、−ＳＯ_３Ｈ、−ＰＯ_３Ｈ_２、炭素数１〜３０のアルキル、またはフェニルで置き換えられてよく、
アルキルの−ＣＨ_２−は−Ｏ−、−ＮＨ−または−ＣＯ−で置き換えられてよく、
アルキルの−ＣＨ_２ＣＨ_２−は−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−または−Ｎ＝Ｎ−で置き換えられてよく、
アルキルの−Ｈは−Ｆ、−Ｃｌ、−Ｂｒ、−Ｃ≡Ｎ、−ＯＨ、−ＣＯＯＨ、−ＳＯ_３Ｈ、または−ＰＯ_３Ｈ_２で置き換えられてよく、
フェニルの−Ｈは独立して、−Ｆ、−Ｃｌ、−Ｂｒ、−Ｃ≡Ｎ、−ＣＨ_３、−ＯＣＨ_３、−ＯＣＨ_２Ｆ、−ＯＣＨＦ_２、−ＯＣＦ_３、−ＯＨ、−ＣＯＯＨ、−ＳＯ_３Ｈ、または−ＰＯ_３Ｈ_２で置き換えられてよく、 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 on the ring is _{-F, -Cl, -OH, -COOH,} -SO 3 H, -PO 3 H 2, may be replaced by alkyl having 1 to 30 carbon atoms or phenyl,
Alkyl —CH ₂ — may be replaced by —O—, —NH— or —CO—,
The alkyl —CH ₂ CH ₂ — may be replaced by —CH═CH—, —C≡C— or —N═N—
-H alkyl is -F, -Cl, -Br, -C≡N, -OH, -COOH, may be replaced by _-SO 3 H or _-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,
The alkylene —CH ₂ — may be replaced by —O—, —NH— or —CO—,
The alkylene —CH ₂ CH ₂ — may be replaced by —CH═CH—, —C≡C— or —N═N—,
-H alkylene is -F, -Cl, -Br, -C≡N, -OH, -COOH, may be replaced by _-SO 3 H or _-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;
Alkyl —CH ₂ — may be replaced by —O—, —NH— or —CO—,
The alkyl —CH ₂ CH ₂ — 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 .

Y ¹⁴ independently represents the following general formula (XXI),

^{~A 1 -A 1 -A 1 -A 1} -A 1 -A 1 -A 2 (XXI)
A ¹ independently represents 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,
Y ² independently represents —H, alkyl having 1 to 30 carbons, alkoxy having 1 to 29 carbons, or alkenyl having 2 to 30 carbons,
—CH ₂ CH ₂ — may be replaced by —CH═CH—, —C≡C—, or N═N—
-H alkylene is -F, -Cl, -C≡N, -OH, -COOH, may be replaced by _-SO 3 H or _PO 3 _{H 2,,}
-H rings -F, -Cl, -C≡N, -OH, -COOH, -SO 3 H, may be replaced by _-PO 3 _{H 2} or the following general formula, (XXII),

^{~A 3 -A 3 -A 3 -A 2} (XXI)
A ³ independently represents a single bond, a linear or branched alkylene having 1 to 12 carbon atoms, or a ring in which the sum of the numbers of carbon, nitrogen and oxygen atoms constituting the skeleton is 3 to 30;
The —CH ₂ — of alkylene may be replaced with —O—, —NH—, —CO—, —CHY ² —, —C (Y ² ) ₂ —, or NY ² —.
Y ² independently represents —H, alkyl having 1 to 20 carbons, alkoxy having 1 to 19 carbons, or alkenyl having 2 to 20 carbons;
—CH ₂ CH ₂ — may be replaced by —CH═CH—, —C≡C—, or N═N—
-H alkylene is -F, -Cl, -C≡N, -OH, -COOH, may be replaced by _-SO 3 H or _PO 3 _{H 2,,}
-H rings -F, -Cl, -C≡N, -OH, -COOH, may be replaced by _-SO 3 H or _PO 3 _{H 2,,}

A ² is independently —H, —F, —Cl, —C≡N, —OH, —COOH, —SO ₃ H, —PO ₃ H ₂ , or linear or branched alkyl having 1 to 40 carbon atoms. Represents
Is -O - - -CH ₂ in the alkyl, - NH-, or may be replaced by CO-,
—CH ₂ CH ₂ — may be replaced by —CH═CH—, —C≡C—, or N═N—
-H alkyl is -F, -Cl, -OH, -COOH, may be replaced by _-SO 3 H or _PO 3 _{H 2,,}
Provided that at least one of Y ¹⁴ is a group comprising —COCH═CH—, —N═N—, or C≡C—, and

Formula (II-1), (III-1), (IV-1), (V-1), (V-11), (VI-1), (VI-2), (VI-3), ( VI-11), (VI-12), (VII-1), (VII-2), (VII-12), (VII-3), (VII-11), (VIII-1), (VIII- 2), (VIII-3), (VIII-4), (VIII-11), and (IX-1), the benzene ring is a piperazine ring, piperidine ring, pyrrolidine ring, pyrrole ring, furan ring, thiophene ring, Imidazole ring, oxazole ring, thiazole ring, triazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, indole ring, steroid ring, bicyclo [2.2.1] heptane ring, bicyclo [2.2. 2] Octane ring The hexahydro - may be replaced by furo [3.2-b] furan ring.

More specifically, other diamines include compounds 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 formulas (IV-1-1) to (IV-1-3).

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

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

Examples of the diamine represented by the formula (VII-12) include a compound 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 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.

Other diamines that can be used in the present invention can be used in a range that does not impair the effects of the present invention in the diamine constituting the polyamic acid in the liquid crystal aligning agent of the present invention.

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

The 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 each independently alkylene having 1 to 4 carbons or cycloalkylene having 5 to 8 carbons, B is phenylene, s is 0 or 1, 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.
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 A group having 2 to 6 carbon atoms, r is represented by 1 or 2, and -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 these In this group, one or two hydrogen atoms are replaced with 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-xylylene-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. From the above viewpoint, the content of the compound having a radically polymerizable unsaturated double bond is preferably 0.01 to 1.00 as a weight ratio with respect to the total amount of the polyamic acid or its derivative, and is preferably 0.01 to 0. .70 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, for example, ethylene bisacrylate, Aronix M-210, Aronix M-240 and Aronix M-6200, which are products of Toa Gosei Chemical Co., Ltd., Nippon Kayaku Co., Ltd. Products of 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 products of Kyoeisha Oil Chemical Co., Ltd. Certain light acrylates BA-4EA, light acrylate BP-4PA and light acrylate BP-2PA.

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

Specific examples of the (meth) acrylic acid amide derivative are, for example, N-isopropylacrylamide, N-isopropylmethacrylamide, Nn-propylacrylamide, Nn-propylmethacrylamide, N-cyclopropylacrylamide, N-cyclopropylmethacrylic. Amide, 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′-methylene Sacrylamide, N, N'-ethylenebisacrylamide, N, N'-dihydroxyethylenebisacrylamide, N- (4-hydroxyphenyl) methacrylamide, N-phenylmethacrylamide, N-butylmethacrylamide, N- (iso- Butoxymethyl) methacrylamide, N- [2- (N, N-dimethylamino) ethyl] methacrylamide, N, N-dimethylmethacrylamide, N- [3- (dimethylamino) propyl] methacrylamide, N- (methoxy Methyl) methacrylamide, N- (hydroxymethyl) -2-methacrylamide, N-benzyl-2-methacrylamide, and N, N′-methylenebismethacrylamide.

Among the above (meth) acrylic acid derivatives, particularly preferred compounds are N, N′-methylenebisacrylamide, N, N′-dihydroxyethylene-bisacrylamide, ethylenebisacrylate, and 4,4′-methylenebis (N, N -Dihydroxyethylene acrylate aniline).

Specific examples of bismaleimide include BMI-70 and BMI-80 manufactured by KAI Kasei Co., Ltd., and BMI-1000, BMI-3000, BMI-4000, BMI-5000 and BMI manufactured by Daiwa Kasei Kogyo Co., Ltd. -7000.

For example, the liquid crystal aligning agent of this invention may further contain the oxazine compound from a viewpoint of the long-term stability of the electrical property in a liquid crystal display element. As the oxazine compound, one compound may be used alone, or two or more compounds may be used in combination. The content of the oxazine compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, and 1 to 20% by weight based on the total amount of the polyamic acid or derivative thereof. Is more preferable.

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 of oxazine compounds are known. Although the structure of the oxazine compound used by this invention is not specifically limited, The oxazine compound which has aromatic groups containing condensed polycyclic aromatic groups, such as a benzoxazine and a naphthoxazine, is illustrated.

Examples of the oxazine compound are 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 it is C1-C3 alkylene.

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

式中、Ｒ^１は炭素数１〜３０のアルキルが好ましく、炭素数１〜２０のアルキルがさらに好ましい。 Examples of the oxazine compound represented by the formula (a) include the following 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 an oxazine 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 an organic group 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} - a. 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 formulas (b-1), (c-1), (c-3), (c-5), (c-7), (c-9), (d-1) to It is an oxazine compound represented by (d-6), (e-3), (e-4), and (f-2) to (f-4).

The oxazine compound can be produced by referring to the methods described in WO 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).

The oxazine compound represented by the formula (b) is obtained by reacting by adding a primary amine to formaldehyde gradually, and then adding and reacting a compound having a naphthol-based hydroxyl group (International Publication No. 2004). / 009708 pamphlet).

Further, the oxazine compound represented by the formula (c) contains 1 mol of a phenol compound in an organic solvent, at least 2 mol of an aldehyde and 1 mol of an equimolar monocytic amine with respect to one phenolic hydroxyl group thereof as a secondary fat. It can be obtained by reacting in the presence of an aromatic amine, tertiary aliphatic amine or 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. Is obtained by dehydration condensation reaction in n-butanol at a temperature of 90 ° C. or higher (see JP-A-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. Is more preferable. Or it is preferable that content of the said oxazoline compound is 0.1 to 40 weight% with respect to the said polyamic acid or its derivative (s), when the oxazoline structure in an oxazoline compound is converted into oxazoline.

The oxazoline compound only needs to 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, and 1010 (all are available as products of Japan Epoxy Resin Co., Ltd. (currently, jER series products 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 806, 807, 4004P (all manufactured by Japan Epoxy Resin), Epototo YDF-170, Epototo YDF-175S, Epototo YDF-2001 (all manufactured by Toto Kasei Co., Ltd.), DER -354 (manufactured by The Dow Chemical Company), Epicron 830, and Epicron 835 (all manufactured by DIC Corporation).

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 ( Co., Ltd.).

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), Epototo YDB-360, Epototo YDB-400 (all manufactured by Toto Kasei Co., Ltd.), DER-530, DER. -538 (all from The Dow Chemical Company), Epicron 152, and Epicron 153 (all from 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 novolac 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 manufactured by Japan Epoxy Resin), 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 formula E107.

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 ChemteX It is a 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 diglycidyl terephthalate (the following formula 117), diglycidyl phthalate (the following formula E118), bis (2-methyloxiranylmethyl) phthalate (the following formula E119), and the following formula E121. 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 include 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 It is done. 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 30% by weight, based on the total weight of the polyamic acid or its derivative.

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

The addition amount of other additives varies depending on the use, but is usually 0.1 to 50% by weight, preferably 0.1 to 30% by weight, based on the total weight of the polyamic acid or derivative thereof. .

Further, for example, the liquid crystal aligning agent of the present invention is an acrylic acid polymer, an acrylate polymer, and a tetracarboxylic acid as long as the effects of the present invention are not impaired (preferably within 20% by weight of the total amount of the polyamic acid or its derivative). You may further contain other polymer components, such as polyamide imide which is a reaction product of acid dianhydride, dicarboxylic acid or its derivative (s), 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). Any solvent can be used without 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 usually put into practical use in the form of a solution by diluting a polymer component containing the polyamic acid or a derivative thereof with a 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 concentration of the polymer component in the liquid crystal aligning agent may be adjusted depending on the application method of the liquid crystal aligning agent. When the application method of the liquid crystal aligning agent is a spinner method or a printing method, the concentration of the polymer component is usually 10% by weight or less in order to maintain a good film thickness. Other coating methods such as dipping and ink jet methods may further reduce the concentration. On the other hand, when the concentration of the polymer component is 0.1% by weight or more, the 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 may be in the form of a so-called polymer blend in which two or more kinds of polyamic acid or a derivative thereof are mixed. Good. 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 acid represented by formula (Q) in either A or B or both The aspect containing the structural unit derived from the diamine which has the structural unit derived from an acid dianhydride and the side chain structure represented by Formula (V-2) can be illustrated. However, when it is assumed that the polyamic acid or derivative thereof having such a side chain structure is segregated in the upper layer of the alignment film by the polymer blend method, the polyamic acid or derivative thereof segregated in the lower layer needs to have a side chain structure. There is no. Therefore, the structural unit derived from the tetracarboxylic dianhydride represented by the formula (Q) on the polyamic acid or its derivative to be segregated in the upper layer, usually A or B, and the formula (V-2) The polyamic acid or its derivative comprised from the diamine which contains the structural unit derived from the diamine which has the side chain structure represented by these, and does not contain a side chain structure is used. It is not impeded that the other polyamic acid or derivative thereof contains a structural unit derived from the tetracarboxylic dianhydride represented by the formula (Q).

When blending 3 or more types of polyamic acid or its derivatives, the structural unit derived from tetracarboxylic dianhydride represented by formula (Q) and the diamine having a side chain structure represented by formula (V-2) The derived structural unit may be contained in only one of the mixed polyamic acids or derivatives thereof, may be contained in two, or may be contained in all the polyamic acids or derivatives thereof. However, as described above, the structural unit derived from the tetracarboxylic dianhydride represented by the formula (Q) and the formula (V-2) are usually expressed only in the polyamic acid or its derivative segregated at the top. It becomes the aspect containing the structural unit derived from the diamine which has a side chain structure. Also in this case, it is not prevented that the remaining two polyamic acids or derivatives thereof contain a structural unit derived from the tetracarboxylic dianhydride represented by the formula (Q).

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, a color filter, or the like may be provided.

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

The coating film can be fired under conditions necessary for the polyamic acid or its derivative to exhibit a dehydration / ring-closure reaction. As for the baking of the coating film, a method of heat treatment in an oven or an infrared furnace, a method of heat treatment on a hot plate, and the like are generally known. These methods are equally applicable in the present invention. In general, it is preferably performed at a temperature of about 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 can be replaced with the rubbing treatment, and may be used in combination with the rubbing treatment.

With respect to the photo-alignment method in which alignment treatment is performed by irradiating light, many alignment mechanisms such as photodecomposition method, photoisomerization method, photodimerization method, photocrosslinking method have been proposed (for example, liquid crystal, Vol. 3, No. 4, page 262, 1999, see JP-A-2005-275364 and JP-A-11-15001.) Among these, development of a photodimerization method and a photoisomerization method in which there is no fear of contaminating the liquid crystal composition with decomposition products and additives is progressing.

As for the photodimerization method, for example, M.M. Schadt et al., Jpn. J. et al. Appl. Phys. , 31, 155 (1992) and Japanese Patent No. 2806661, there are documents introducing photo-alignment films using photodimerization that occurs by irradiating polyvinyl cinnamate or its derivatives with linearly polarized ultraviolet light. . Japanese Patent Application Laid-Open No. 10-251513 introduces a liquid crystal alignment film formed by a photoalignment composition containing polyimide having a cinnamate group in the side chain, and Japanese Patent Application Laid-Open No. 2002-069180 discloses a substituted cinnamoyl group in the side chain. There has been proposed a liquid crystal alignment film formed of a polyamic acid having s.

On the other hand, a photo-alignment method using a photoisomerization reaction such as an azo group is also disclosed. JP-A-2005-275364 discloses that a liquid crystal alignment film having a large alignment index is obtained when a polyamic acid film containing an azo group or the like in a main chain is irradiated with linearly polarized ultraviolet light and then heated imidized. It is written.

As described above, the liquid crystal aligning agent of the present invention includes a tetracarboxylic dianhydride represented by the formula (Q) and a diamine having a side chain structure represented by the formula (V-2) or the formula (V-2). Containing a polyamic acid or derivative thereof obtained by reacting a mixture of a diamine having a side chain structure represented by formula (II) with another diamine with tetracarboxylic dianhydride, and applying and heating on a substrate. A ring-closure reaction occurs to become polyimide. As a diamine represented by the formula (V-2), a diamine containing a photosensitive group in the side chain, for example, compounds represented by the formulas (V-11-1) to (V-11-19) are appropriately used. The polyimide film formed on the substrate is irradiated with linearly polarized ultraviolet light by the liquid crystal aligning agent containing the prepared polyamic acid or derivative thereof, and then the liquid crystal composition is applied to the cell produced by bonding the two substrates together. When encapsulated, a liquid crystal display element in which liquid crystal molecules are given a desired alignment state by photo-aligned side chains can be obtained. In this case, a diamine containing a photosensitive group represented by formulas (V-11-1) to (V-11-19) and a diamine represented by formula (V-2) having other side chain structures. May be used in combination. Furthermore, a diamine containing a photosensitive group represented by formulas (V-11-1) to (V-11-19), a diamine represented by formula (V-2) having a side chain structure other than this, You may use together the other diamine which does not contain a side chain structure.

Moreover, the diamine represented by Formula (V-2), and the diamine which has a photosensitive group as another diamine, for example, the compound represented by Formula (VI-11-1)-(VI-11-16), and The film of polyamic acid or its derivative formed on the substrate is irradiated with ultraviolet light by a liquid crystal aligning agent containing a polyamic acid or its derivative obtained by reacting a mixture of tetracarboxylic dianhydride with If a liquid crystal composition is sealed in a cell produced by heating imidization and then bonding two substrates together, a liquid crystal display element in which liquid crystal molecules are given a desired alignment state due to the effect of a photoaligned main chain is obtained. Can do.

Thus, in a liquid crystal display element having an alignment film manufactured using a liquid crystal aligning agent including a polymer containing a photosensitive group in the main chain, when a predetermined pretilt angle is desired to be expressed, the substrate is irradiated with ultraviolet light. On the other hand, a method of irradiating linearly polarized light from an arbitrary angle or a method of combining linearly polarized light irradiation from a direction perpendicular to the substrate and non-polarized light irradiation from an arbitrary angle can be appropriately selected. In a liquid crystal display device in which a liquid crystal alignment film is formed using the liquid crystal alignment agent of the present invention, when the pretilt angle is to be expressed in the liquid crystal molecules, the polyamic acid or its derivative film is irradiated with polarized ultraviolet light. Alternatively, non-polarized ultraviolet light may be irradiated.

The liquid crystal alignment film of the present invention can be suitably obtained by a method that further includes steps other than the steps described above. Examples of such other steps include a step of drying the coating film and a step of washing the film before and after the rubbing treatment with a washing 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, similar to the above-described baking step. These methods are similarly applicable. 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 the cleaning step in the formation of the liquid crystal alignment film of the present invention.

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

The liquid crystal display element of the present invention includes a pair of substrates, a liquid crystal layer formed between the pair of substrates, an electrode that applies a voltage to the liquid crystal layer, and a liquid crystal alignment film that aligns liquid crystal molecules in a predetermined direction. Have The liquid crystal alignment film of the present invention described above is used for the liquid crystal alignment film.

The glass substrate described above in the liquid crystal alignment film of the present invention can be used as the substrate, and the ITO electrode formed on the glass substrate exemplified in the description of the liquid crystal alignment film can be used as the electrode.

The liquid crystal layer is formed of a liquid crystal composition that is sealed between the pair of substrates that are bonded so that the surfaces on which the liquid crystal alignment film is formed face each other. A liquid crystal composition having a negative dielectric anisotropy is preferably used for a liquid crystal display element having a liquid crystal alignment film produced by the liquid crystal aligning agent for vertical alignment of the present invention.

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.

When a liquid crystal display element having a liquid crystal alignment film manufactured by the liquid crystal aligning agent of the present invention is driven by a TN mode or an IPS mode, a liquid crystal composition having a positive dielectric anisotropy is also used for the liquid crystal display element. Can do. 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.

One or more optically active compounds may be added to the 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 further steps such as attaching a polarizing film to the substrate as necessary.

The liquid crystal display element of the present invention is a liquid crystal display element for a vertical electric field method in which a voltage is applied to a liquid crystal layer in a direction perpendicular to the substrate surface. Since the liquid crystal display element for a vertical electric field mode requires a relatively large pretilt angle, it includes tetracarboxylic dianhydride and a diamine having a side chain structure represented by the formula (V-2) or the same. The liquid crystal aligning film formed from the liquid crystal aligning agent of this invention containing the polyamic acid obtained by making the mixture of diamine react or its derivative (s) is used suitably.

The liquid crystal alignment film produced by the liquid crystal aligning agent of the present invention can also be used for a liquid crystal display element driven by a TN method or an IPS method which is a lateral electric field method. In such a case, since a relatively large pretilt angle is not required in the TN method or the IPS method, a mixture of a diamine represented by the formula (V-2) and a diamine having no side chain structure is converted to a tetracarboxylic acid dicarboxylic acid. In making it react with an anhydride, it becomes possible to set the aspect suitable for a TN system or an IPS system by reducing suitably content of diamine represented by a formula (V-2).

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>
BPDA-H: Bicyclohexanetetracarboxylic dianhydride: Formula (Q): H-PMDA manufactured by Iwatani Gas Co., Ltd .: Cyclohexanetetracarboxylic dianhydride: Formula (25)
CBDA: cyclobutane tetracarboxylic dianhydride: Formula (19)
BTDA: Butanetetracarboxylic dianhydride: Formula (23)
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: Formula (S-1)

<Diamine>
MBMA: 4,4′-methylenebis (3-methylaniline): Formula (VI-1-5)
DDM: 4,4′-diaminodiphenylmethane: Formula (VI-1-1)
5ChCh: 5- {4- [4- (4-npentylcyclohexyl)] cyclohexyl} phenylmethyl-1,3-diaminobenzene: a diamine in which Y ² is alkyl having a chain length of 5 in formula (V-2-7) 16Ch :: diamine diamine in which Y ² is alkyl having a chain length of 16 in formula (V-2-2) DABC: 3,5-diaminobenzylcinnamate: formula (V-11-2)
PDAB: 4,4′-diaminoazobenzene: Formula (VI-11-11)
OPDA: 6- (2,5-Dioxo-3-phenyl-2,5-dihydro-1H-pyrrol-1-yl) hexyl 3,5-diaminobenzoate: Formula (V-11-19)

<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]
In a 100 ml four-necked flask equipped with a thermometer, stirrer, raw material charging inlet and nitrogen gas inlet, 0.285 g of 5ChCh, 1.341 g of MBMA and 30.0 g of dehydrated NMP were added and stirred under a dry nitrogen stream. did. Next, 1.613 g of BPDA-H and 0.2610 g of BTDA were added and reacted for 30 hours, and then 16.5 g of BC was added to synthesize a polyamic acid solution PA1 having a polymer solid concentration of 7% by weight. When the temperature rose due to the reaction temperature during the reaction of the raw materials, the reaction was carried out while suppressing the reaction temperature to about 70 ° C or lower.

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]
As shown in Table 1, polyamic acid solutions CP1 and CP2 having a polymer solid content concentration of 7% by weight and using BPDA-H as a monomer were prepared according to Synthesis Example 1 except that tetracarboxylic dianhydride was changed. .

[Synthesis Example 2]
As shown in Table 1, except that the tetracarboxylic dianhydride and the diamine were changed, a polymer solid content concentration of 7% by weight using an anhydride having a silsesquioxane skeleton as a monomer was used in accordance with Synthesis Example 1. A polyamic acid solution PA2 was prepared. Table 1 summarizes the monomer compositions of the polyamic acid solutions of Synthesis Examples 1 and 2 and Comparative Examples 1 and 2 and the weight average molecular weights of the obtained polymers.

[Example 1]
The polyamic acid solution with a polymer solid content concentration of 7% by weight synthesized in Synthesis Example 1 is diluted with a mixed solvent of NMP / BC = 1/1 (weight ratio) to a polymer solid content concentration of 4% by weight to obtain a liquid crystal aligning agent. AL1. Using the obtained liquid crystal aligning agent, a liquid crystal display element was produced as follows.

<Production of VA liquid crystal display element>
The obtained liquid crystal aligning agent AL1 was apply | coated to a pair of board | substrate with 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 inside, one substrate is coated with an epoxy adhesive in the form of a band leaving a liquid crystal injection hole at the periphery, and a 4.25 μm gap material is sprayed on the other substrate. And pasted together. The liquid crystal composition shown below was vacuum injected into the obtained cell, and the injection hole was sealed with a UV curable sealant. Finally, a heat treatment (isotropic treatment) was performed at 110 ° C. for 30 minutes to obtain a VA liquid crystal display element.

[Example 2, Comparative Examples 1 and 2]
A polymer solid solution having a solid content concentration of 7% by weight synthesized in Synthesis Example 2 and Comparative Synthesis Examples 1 and 2, PA2, CP1 and CP2 was added to a mixed solvent of NMP / BC = 1/1 (weight ratio) to form a polymer solid. The liquid crystal alignment agents AL2, CA1, and CA2 were diluted to a partial concentration of 4% by weight. A liquid crystal display element was produced according to Example 1 using the obtained liquid crystal aligning agent.

[Examples 3 to 6]
The additives shown in Table 2 were added to the polyamic acid solutions PA1 and PA2 by 30% by weight per polymer weight, respectively, and then a mixed solvent of NMP / BC = 1/1 (weight ratio) was added to obtain a polymer solid content concentration of 4 Dilute to weight percent. A liquid crystal display device was produced according to Example 1 using the diluted liquid crystal aligning agent.

<Measurement of VHR>
The VHR 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 0.3 Hz, a wave height of ± 5 V, and a measurement temperature of 60 ° C.

<Measurement of ion density>
The ion density of the VA liquid crystal display element was measured using a Toyo Technica liquid crystal property evaluation apparatus 6254 type. The measurement conditions are: frequency: 0.01 Hz, voltage: ± 10 V, and measurement temperature is 60 ° C.

As shown in Table 2, obtained from a liquid crystal aligning agent containing a polyamic acid obtained by reacting a tetracarboxylic dianhydride represented by the formula (Q) with a diamine represented by the formula (V-2) In the VA liquid crystal display element using the liquid crystal alignment film, an extremely high VHR value was exhibited as compared with the case where other tetracarboxylic dianhydrides were used. Furthermore, it has been shown that by further using an anhydride having a silsesquioxane skeleton such as PSQ1, further improvement in voltage holding ratio and reduction in ion density can be realized.

<Evaluation of residual DC>
A rectangular wave of 30 Hz and 3 V is applied to a VA type liquid crystal display element mounted on a polarizing microscope made by Nikon Corporation with a polarizing plate by using a jig with a FG110 type function generator made by Yokogawa Electric Corporation. Was applied. After superimposing the DC voltage of 3V for 30 minutes, the superimposition of the DC voltage was terminated, and the amount of light transmitted through the liquid crystal display element was detected by a photomultiplier tube made by Hamamatsu Photonics connected to a DSO3062 oscilloscope made by Agilent Technologies. did. The offset voltage of the function generator was adjusted so that the change in the waveform representing the change in the amount of light projected on the oscilloscope was minimized, and the offset voltage was recorded as the flicker elimination voltage. The absolute value of this value was defined as residual DC. It can be said that the smaller the residual DC is, the better the less seizure.

The liquid crystal display elements manufactured in Examples 1 to 6 and Comparative Examples 1 and 2 were measured for residual DC, and the flicker erasing voltage after 1 minute and 30 minutes after the completion of the superposition of the DC voltage was measured between the elements. Compared. The results are shown in Table 3.

As shown in Table 3, obtained from a liquid crystal aligning agent containing a polyamic acid obtained by reacting a tetracarboxylic dianhydride represented by the formula (Q) with a diamine represented by the formula (V-2) It can be seen that in the VA liquid crystal display element using the liquid crystal alignment film, the reduction of residual DC is significant.

<Synthesis of polyamic acid forming photo-alignment liquid crystal aligning agent>
[Synthesis Examples 3-6, Comparative Synthesis Examples 3-5]
Polyamic acid solutions PA3-6 and CP3-5 for photo-alignment with a concentration of 7% by weight were prepared in the same manner as in Synthesis Example 1 except that the synthesis was performed in a yellow room using a fluorescent lamp with ultraviolet rays cut. In addition, although the diamine which has the side chain structure represented by Formula (V-2) is not contained in the raw material of the polyamic acid PA6 of the synthesis example 6, this is polyamic acid PA3-5 and CP3 as mentioned later. 5 is a polyamic acid solution for blending with No. 5. Table 4 summarizes the measurement results of the compositions and weight average molecular weights of Synthesis Examples 3 to 6 and Comparative Synthesis Examples 3 to 5.

[Examples 7 to 9 and Comparative Examples 3 to 5]
The polyamic acid solution PA3 having a polymer solid content concentration of 7% by weight synthesized in Synthesis Example 3 and the polyamic acid solution PA6 having a polymer solid content concentration of 7% by weight synthesized in Synthesis Example 6 were mixed at a weight ratio of 20/80 (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 obtain a liquid crystal aligning agent AL7. According to this method, AL8, AL9 and CA3 to CA5 were prepared at the composition ratio shown in Table 5.

[Examples 10 to 13]
The polyamic acid solution was mixed at the composition ratio shown in Table 5, and 30% by weight of the additive was added to the total polymer weight. 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 liquid crystal alignment agents AL10 to AL13.

[Example 14]
<Production of photo-alignment VA type liquid crystal display element>
The liquid crystal aligning agent AL7 was applied to a pair of substrates with ITO transparent electrodes by a spin coating method, and dried on a hot plate at 80 ° C. for 90 seconds. Subsequently, it heat-processed for 15 minutes in oven set to 210 degreeC, and formed the polyimide film with a film thickness of about 100 nm. Next, an ultraviolet irradiation device (ML-501C / B) using an ultra high pressure mercury lamp (USH-500BY1) manufactured by Ushio Electric Co., Ltd. is used through a polarizing plate from a direction inclined about 40 ° from the normal line of the substrate. Were irradiated with linearly polarized light (energy of about 200 mJ / cm ^{2 at} 365 nm) to obtain a substrate on which a liquid crystal alignment film was formed. With the surface on which the alignment film is formed inside, one substrate is coated with an epoxy adhesive in the form of a band leaving a liquid crystal injection hole at the periphery, and a 4.25 μm gap material is sprayed on the other substrate. And pasted together. The liquid crystal composition was vacuum injected into the obtained cell, and the injection hole was sealed with a UV curable sealant. Finally, heat treatment (isotropy treatment) was performed at 110 ° C. for 30 minutes to obtain a photo-alignment VA liquid crystal display element.

[Examples 15 to 20 and Comparative Examples 6 to 8]
Using the liquid crystal alignment agents AL8 to AL13 and CA3 to CA5, photoalignment VA type liquid crystal display elements were produced according to Example 14.

<Evaluation of long-term thermal reliability of VHR>
About the photo-alignment VA type | mold liquid crystal display element produced in Examples 14-20 and Comparative Examples 6-8, long-term thermal reliability evaluation of VHR was performed as follows.

<Measurement of VHR>
The VHR of the VA liquid crystal display device was measured using the same device as that used in Example 1. 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>
About the liquid crystal display element produced in Examples 14-20 and Comparative Examples 6-8, the value of VHR measured within 24 hours after element preparation was set to VHR (initial stage). The liquid crystal display element after VHR measurement was stored in an oven maintained at 100 ° C. for 100 hours, and then the VHR value measured under the above conditions was defined as VHR (100 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 6.

VHR reduction rate = [{VHR (initial) −VHR (100 hours)} × 100] / VHR (initial)

As shown in Table 6, in the liquid crystal display element using the liquid crystal alignment film obtained from the liquid crystal aligning agent containing polyamic acid containing BPDA-H, the liquid crystal containing polyamic acid containing monocyclic H-PMDA Compared with a liquid crystal display element using a liquid crystal alignment film obtained from an aligning agent, there is an effect that initial characteristics of VHR and long-term thermal reliability of VHR are high.

<Evaluation of residual DC>
Residual DC measurement was evaluated in accordance with Example 1 for the liquid crystal display devices produced in Examples 14 to 20 and Comparative Examples 6 to 8. The results are shown in Table 7.

As shown in Table 7, obtained from a liquid crystal aligning agent containing a polyamic acid obtained by reacting a tetracarboxylic dianhydride represented by the formula (Q) with a diamine represented by the formula (V-2) It can be seen that also in the photo-alignment VA type liquid crystal display element using the photo-alignment type liquid crystal alignment film, the reduction of residual DC is remarkable.

Claims (11)

A tetracarboxylic dianhydride represented by the formula (Q) and a diamine having a side chain structure represented by the formula (V-2) or a diamine having a side chain structure represented by the formula (V-2); A liquid crystal aligning agent for vertical alignment containing a polyamic acid obtained by reacting a mixture of other diamines or a derivative thereof.

In 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 is 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, and —CH ₂ — in alkylene may be replaced by —O—, —NH—, or —CO—, and —CH ₂ CH _2- may be replaced by —CH═CH—, —C≡C— or —N═N—, and —H of alkylene is —F, —Cl, —C≡N, —OH, —COOH, —SO May be replaced by 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, alkyl of -SO 3 _{H, -PO} 3 H ₂ or 1 to 30 carbon atoms, alkyl of -CH ₂ - it is -O -, - may be replaced by NH- or -CO-, _{-CH 2} CH 2 - is -CH = CH -, - C≡C- or -N = may be replaced by N-, alkyl of -H is -F, -Cl, -C≡N, -OH, -COOH, may be replaced by _-SO 3 H or _-PO 3 _{H 2,;} and,
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. Is one ^{of Y 11} in the formula (V-2) is selected from the group consisting of groups represented by the following formula ^{(Y 11 -1) ~ (Y} 11 -8), liquid crystal vertical alignment according to claim 1 Alignment agent.

In formulas (Y ¹¹ -1) to (Y ¹¹ -8),
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 carbons; and
A ² is —OCO—, —COO—, —O—, or alkylene having 1 to 6 carbon atoms. The diamine having a side chain group 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). 2. A liquid crystal aligning agent for vertical alignment according to 1.

In Formula (V-2-2), Y ² is alkyl having 6 to 30 carbons;
In formulas (V-2-3) to (V-2-6), Y ² is alkyl having 3 to 30 carbons;
In formula (V-2-7), Y ² is alkyl having 2 to 30 carbons;
In Formula (V-2-8), Y ² is alkyl having 2 to 30 carbons; and in Formula (V-2-53), Y ¹⁸ is —F, —CF ₃ or —OCF ₃ . The diamine is at least one diamine represented by the formula (V-2) and 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-1-35) to (VI-1-39), The liquid crystal aligning agent for vertical alignment according to claim 1, which is at least one mixture selected from the group of diamines represented by (VII-2-1) and (VII-2-2).

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

In addition to the tetracarboxylic dianhydride represented by the formula (Q), it is represented by the following formulas (19), (23), (25), (35) to (39), (44), and (49). The polyamic acid obtained by reacting at least one selected from the group of alicyclic tetracarboxylic dianhydride and aliphatic tetracarboxylic dianhydride to be reacted with a diamine, or a derivative thereof, according to claim 1. The liquid crystal aligning agent for vertical alignment of description.

The diamine is at least one diamine represented by the formula (V-2), and the following formulas (VI-11-4) to (VI-11-16), (V-11-2) and (V-11- The liquid crystal aligning agent for vertical alignment of Claim 1 which has a photo-alignment which is at least 1 mixture chosen from the group of the diamine which has the photosensitive structure represented by 17)-(V-11-19). .

The diamine is at least one diamine represented by the formula (V-2), and the following formulas (VI-11-7), (VI-11-11), (V-11-2) and (V-11- The liquid crystal aligning agent for vertical alignment of Claim 1 which has a photo-alignment which is at least 1 mixture chosen from the group of the diamine which has the photosensitive structure represented by 17)-(V-11-19). .

The alkenyl-substituted nadiimide compound, a compound having a radically polymerizable unsaturated double bond, an oxazine compound, an oxazoline compound, and an epoxy compound, and further containing at least one of claim 1-8. Liquid crystal aligning agent for vertical alignment. A liquid crystal alignment film for vertical alignment formed by heating a coating film of the liquid crystal aligning agent for vertical alignment according to claim 1. In 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, A liquid crystal display element, wherein the alignment film is the vertical alignment liquid crystal alignment film according to claim 10.