JP2011257731A - Diamine, liquid crystal aligning agent and liquid crystal display element - Google Patents

Abstract

A liquid crystal display element having a low ion density and excellent long-term reliability, a liquid crystal alignment film that provides the characteristics, a liquid crystal alignment agent for forming the liquid crystal alignment film, and the liquid crystal Provided are a polymer used as an alignment agent, and a diamine as a raw material for the polymer.
A liquid crystal alignment agent formed from a liquid crystal alignment agent containing a polymer obtained by reacting a specific diamine having a triazine structure in the molecule with tetracarboxylic dianhydride. A liquid crystal display element including a film has a low ion density and excellent long-term reliability.
[Selection] Figure 1

Description

The present invention relates to a novel diamine having a triazine ring and a side chain structure, a polymer obtained by reacting the diamine with tetracarboxylic dianhydride, a liquid crystal aligning agent containing the polymer, and a liquid crystal formed from the liquid crystal aligning agent. The present invention relates to an alignment film and a liquid crystal display element including the liquid crystal alignment film.

Liquid crystal display elements are used in various liquid crystal display devices, such as monitors for laptop computers and desktop computers, video camera viewfinders, and projection displays. Recently, they have also been used as televisions. . Furthermore, they are also used as optoelectronic-related elements such as optical printer heads, optical Fourier transform elements, and light valves. As a conventional liquid crystal display element, a display element using a nematic liquid crystal is a mainstream, and 1) a TN (twisted nematic) type liquid crystal display element twisted by 90 degrees, and 2) a STN (super twisted nematic) twisted usually by 180 degrees or more. 3) A so-called TFT (Thin Film Transistor) type liquid crystal display element using a thin film transistor as a switching element for a voltage applied to a liquid crystal layer has been put into practical use.

These liquid crystal display elements have the disadvantage that the viewing angle at which an image can be properly viewed is narrow, and when viewed from an oblique direction, the luminance and contrast are lowered and the luminance is inverted in 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 It is improved by techniques such as crystal display device, some of which are in practical use.

The development of the technology of the liquid crystal display element is achieved not only by the improvement of the driving system and the element structure, but also by the improvement of components used for the display element. Among the constituent members 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 elements, and the role of the liquid crystal alignment film is increasing year by year as the quality of the display elements is improved. It is becoming important.

The liquid crystal alignment film is formed by 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 the substrate, a polyimide-based alignment film is formed by film formation by means such as heating. Various liquid crystal aligning agents other than polyamic acid or soluble polyimide are also being studied, but in terms of heat resistance, chemical resistance (liquid crystal resistance), coatability, liquid crystal alignment, electrical characteristics, optical characteristics, display characteristics, etc. Almost no practical use.

An important characteristic required for the liquid crystal alignment film in order to improve the display quality of the liquid crystal display element is ion density. When the ion density is high, the voltage applied to the liquid crystal during the frame period is lowered, and as a result, the luminance is lowered, which may hinder normal gradation display. Moreover, even if the initial ion density is low, it is not preferable when the ion density (long-term reliability) after the high-temperature acceleration test increases.

As an attempt to solve the above-described problem, for example, a polyamic acid composition containing a combination of two or more polyamic acids having different physical properties for forming a liquid crystal alignment film is known (see, for example, Patent Documents 1 and 2). .

On the other hand, as a liquid crystal aligning agent for forming a film with a high imidation rate even at low temperature baking, a diamine having a divalent organic group having a basic nitrogen atom such as piperazine and a tetracarboxylic dianhydride are reacted. There is known a liquid crystal aligning agent containing a polyamic acid obtained by the method (for example, see Patent Document 3).

Furthermore, a polyamic acid obtained by reacting an aromatic diamine having a nitrogen atom with tetracarboxylic dianhydride and its thermal characteristics are known (for example, see Non-Patent Document 1).

However, the liquid crystal aligning agent obtained by these prior arts still has room for further study on the problem of reducing the ion density.

On the other hand, although an example in which a polyimide synthesized using a side chain diamine having a triazine ring in the molecule is used for a liquid crystal alignment film has been reported, no mention is made regarding ion density (see Non-Patent Documents 2 and 3). ).

JP 11-193345 A JP-A-11-193347 JP-A-9-194725

Journal of Polymer Science: Part A: Polymer Chemistry, vol. 30, p1099-1102 (1992) Proceedings of the 17th Japan Polyimide / Aromatic Polymers Conference, P-34 Abstracts of 2009 Tohoku Branch Research Presentation, A-15

An object of the present invention is to provide a liquid crystal display element having a low ion density and excellent long-term reliability, a liquid crystal alignment film that provides the characteristics, and a liquid crystal alignment agent for forming the liquid crystal alignment film The present invention provides a polymer used for the liquid crystal aligning agent and a diamine which is a raw material for the polymer.

The present inventors have found a novel diamine having a triazine ring and a side chain structure in the molecule. As a result of using a composition containing a polymer obtained by reacting this diamine with tetracarboxylic dianhydride as a liquid crystal aligning agent, a liquid crystal display device having a liquid crystal alignment film formed by this liquid crystal aligning agent has a low ion density. As a result, the inventors have found that the long-term reliability is also excellent, and have completed the present invention.

式（Ｉ）において、
Ｒ¹は−Ｈ、−Ｆ、−ＣＮ、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、または炭素数１〜３０のフッ素置換アルコキシであり；
Ａは１，４−フェニレンまたは１，４−シクロヘキシレンであり；
Ｚは単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−または−（ＣＨ₂）_m−であり、ｍは１〜６の整数であり；
ｎは０または１であり；そして、
Ｒ²は−Ｈまたは炭素数１〜５のアルキルである。
〔２〕Ｒ¹が炭素数４〜２０のアルキル、炭素数４〜２０のフッ素置換アルキル、炭素数４〜２０のアルコキシ、または炭素数４〜２０のフッ素置換アルコキシであり；
ｎが０であり；そして、
Ｒ²が−Ｈまたは−ＣＨ₃である、上記〔１〕に記載のジアミン。
〔３〕Ｒ¹が炭素数４〜２０のアルキル、炭素数４〜２０のフッ素置換アルキル、炭素数４〜２０のアルコキシ、または炭素数４〜２０のフッ素置換アルコキシであり；
ｎが１であり；
Ａが１，４−フェニレンであり；
Ｚが単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、または−（ＣＨ₂）₂−であり；そして、
Ｒ²が−Ｈまたは−ＣＨ₃である、上記〔１〕に記載のジアミン。
〔４〕酸成分としてテトラカルボン酸二無水物を、ジアミン成分として上記〔１〕記載の側鎖構造を有するジアミンの少なくとも１つを用い、これらを反応させて得られるポリマー。
〔５〕ジアミン成分として、下記式（ＩＩＩ）〜（ＩＸ）および（ＸＶ）で表されるジアミンの群から選択される少なくとも１つをさらに用いる、上記〔４〕に記載のポリマー。

式（ＩＩＩ）において、Ａ¹は−（ＣＨ₂）_m−であり、ｍは１〜６の整数であり；
式（Ｖ）、（ＶＩＩ）および（ＩＸ）において、Ｘは単結合、−Ｏ−、−Ｓ−、−Ｓ−Ｓ−、−ＳＯ₂−、−ＣＯ−、−ＮＨ−、−Ｎ（ＣＨ₃）−、−ＣＯＮＨ−、−ＮＨＣＯ−、−Ｃ（ＣＨ₃）₂−、−Ｃ（ＣＦ₃）₂−、−（ＣＨ₂）_m−、−Ｏ−（ＣＨ₂）_m−Ｏ−、−Ｎ（ＣＨ₃）−（ＣＨ₂）_m−Ｎ（ＣＨ₃）−、または−Ｓ−（ＣＨ₂）_m−Ｓ−であり、ｍは１〜６の整数であり；
式（ＶＩＩ）において、Ｌ¹およびＬ²は−Ｈであるが、Ｘが−ＮＨ−、−Ｎ（ＣＨ₃）−、−ＣＨ₂−、−Ｃ（ＣＨ₃）₂−、または−Ｃ（ＣＦ₃）₂−であるときには互いに結合して単結合を形成してもよく；
式（ＶＩＩＩ）および（ＩＸ）において、Ｙは単結合、−Ｏ−、−Ｓ−、−ＣＯ−、−Ｃ（ＣＨ₃）₂−、−Ｃ（ＣＦ₃）₂−、または炭素数１〜３のアルキレンであり；
式（ＶＩＩＩ）において、環Ｄはフェニレンまたはピラジン−１，４−ジイルであり；
式（ＶＩ）において、ベンゼン環の−Ｈはベンジルで置き換えられていてもよく；
式（ＸＶ）において、Ｒ³³およびＲ³⁴は独立して炭素数１〜３のアルキルまたはフェニルであり；Ｇは独立して炭素数１〜６のアルキレン、フェニレンまたはアルキル置換されたフェニレンであり；ｍは１〜１０の整数であり；そして、
上記の各式において、シクロヘキサン環またはベンゼン環の−Ｈは、−Ｆ、−ＣＨ₃、−ＯＨ、−ＣＯＯＨ、−ＳＯ₃Ｈ、−ＰＯ₃Ｈ₂、ベンジル、またはヒドロキシベンジルで置き換えられていてもよい。
〔６〕ジアミン成分として、式（Ｉ）で表されるジアミン以外の側鎖構造を有するジアミンをさらに用いる、上記〔５〕に記載のポリマー。
〔７〕ジアミン成分として、下記式（Ｘ）〜（ＸＩＶ）で表されるジアミンの群から選択される少なくとも１つをさらに用いる、上記〔４〕に記載のポリマー。

式（Ｘ）において、
Ｚ¹は、単結合、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＣＨ₂Ｏ−、−ＯＣＨ₂−、−ＣＦ₂Ｏ−、−ＯＣＦ₂−、または−（ＣＨ₂）_m−であり、ｍは１〜６の整数であり、このアルキレンにおける任意の−ＣＨ₂−は−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられていてもよく；
Ｒ³は、ステロイド骨格を有する基、炭素数３〜３０のアルキル、炭素数１〜３０のアルキルもしくは炭素数１〜３０のアルコキシを置換基として有するフェニル、または下記式（Ｘ−ａ）で表される基であり、この炭素数１〜３０のアルキルにおける任意の−ＣＨ₂−は−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられていてもよく；

式（Ｘ−ａ）において、
Ａ²およびＡ³は独立して、単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＣＨ＝ＣＨ−、または炭素数１〜１２のアルキレンであり、ａおよびｂは独立して０〜４の整数であり；
環Ｂおよび環Ｃは独立して１，４−フェニレン、１，４−シクロヘキシレン、１，３−ジオキサン−２，５−ジイル、ピリミジン−２，５−ジイル、ピリジン−２，５−ジイル、ナフタレン−１，５−ジイル、ナフタレン−２，７−ジイル、またはアントラセン−９，１０−ジイルであり；
Ｒ⁴およびＲ⁵は独立して、−ＦまたはＣＨ₃であり、ｆおよびｇは独立して０〜２の整数であり；
Ｒ⁶は−Ｆ、−ＯＨ、−ＣＮ、炭素数１〜３０のアルキル、炭素数１〜３０のアルコキシ、または炭素数２〜３０のアルコキシアルキルであり、これらのアルキル、アルコキシ、アルコキシアルキルにおいて、任意の−Ｈは−Ｆで置き換えられていてもよく、任意の−ＣＨ₂−は−ＣＦ₂−または下記式（ｓ）で表される２価の基で置き換えられていてもよく；

式（ｓ）において、Ｒ³³およびＲ³⁴は独立して炭素数１〜３のアルキルであり、ｍは１〜６の整数であり；
ｃ、ｄおよびｅは独立して０〜３の整数であり、そして、ｃ＋ｄ＋ｅ≧１である。

式（ＸＩ）および（ＸＩＩ）において、
Ｒ⁷は独立して−Ｈまたは−ＣＨ₃であり；
Ｒ⁸は−Ｈ、炭素数１〜２０のアルキルまたは炭素数２〜２０のアルケニルであり；
Ａ⁴は独立して単結合、−ＣＯ−または−ＣＨ₂−であり；
式（ＸＩＩ）において、
Ｒ⁹およびＲ¹⁰は独立して炭素数１〜２０のアルキルまたはフェニルである。

式（ＸＩＩＩ）および（ＸＩＶ）において、Ａ⁵は独立して−Ｏ−または炭素数１〜６のアルキレンであり；
式（ＸＩＩＩ）において、Ｒ¹¹は−Ｈまたは炭素数１〜３０のアルキルであり、このアルキルの任意の−ＣＨ₂−は、−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく；
Ａ⁶は単結合または炭素数１〜３のアルキレンであり；
環Ｔは１，４−フェニレンまたは１，４−シクロヘキシレンであり；
ｈは０または１であり；
式（ＸＩＶ）において、Ｒ¹²は炭素数６〜２２のアルキルであり；そして、
Ｒ¹³は炭素数１〜２２のアルキルである。
〔８〕式（Ｉ）で表されるジアミン以外の側鎖構造を有するジアミンが、上記〔７〕に記載の式（Ｘ）〜（ＸＩＶ）で表されるジアミンの群から選択される少なくとも１つである、上記〔６〕に記載のポリマー。
〔９〕ジアミンと反応させるテトラカルボン酸二無水物が、下記式（Ａｎ−１）〜（Ａｎ−６）で表される化合物から選択される少なくとも１つである、上記〔４〕〜〔８〕のいずれか１項に記載のポリマー。

式（Ａｎ−１）、（Ａｎ−４）および（Ａｎ−５）において、Ｘ¹は独立して単結合または−ＣＨ₂−であり；
式（Ａｎ−２）において、Ｇ¹は単結合、炭素数１〜２０のアルキレン、−ＣＯ−、−Ｏ−、−Ｓ−、−ＳＯ₂−、−Ｃ（ＣＨ₃）₂−、または−Ｃ（ＣＦ₃）₂−であり；
式（Ａｎ−２）〜（Ａｎ−４）において、Ｙ¹は独立して下記の３価の基の群から選ばれる１つであり；

式（Ａｎ−３）〜（Ａｎ−５）において、環Ｅは炭素数３〜１０の単環式炭化水素の基または炭素数６〜２０の縮合多環式炭化水素の基を表し、この基の任意の水素はメチル、エチルまたはフェニルで置き換えられていてもよく；
環に掛かっている結合手は環を構成する任意の炭素に連結しており、２本の結合手が同一の炭素に連結してもよく；
式（Ａｎ−６）において、Ｘ¹¹は炭素数２〜６のアルキレンであり；
Ｍｅはメチルを表し、そして、Ｐｈはフェニルを表す。
〔１０〕ジアミンと反応させるテトラカルボン酸二無水物が、芳香族テトラカルボン酸二無水物の少なくとも１つと、脂環式テトラカルボン酸二無水物および脂肪族テトラカルボン酸二無水物の群から選択される少なくとも１つの混合物である、上記〔４〕〜〔８〕のいずれか１項に記載のポリマー。
〔１１〕ジアミンと反応させるテトラカルボン酸二無水物が、脂環式テトラカルボン酸二無水物および脂肪族テトラカルボン酸二無水物の群から選択される少なくとも１つまたは２つ以上の混合物である、上記〔４〕〜〔８〕のいずれか１項に記載のポリマー。
〔１２〕芳香族テトラカルボン酸二無水物が下記の式（１）、（２）、（５）〜（７）および（１７）で表される化合物から選ばれる少なくとも１つである、上記〔１０〕に記載のポリマー。

〔１３〕脂環式テトラカルボン酸二無水物および／または脂肪族テトラカルボン酸二無水物が下記の式（１９）、（２３）、（２５）、（３５）〜（３９）、（４４）、（４９）および（６８）で表される化合物から選ばれる少なくとも１つである、上記〔１０〕または〔１１〕に記載のポリマー。

〔１４〕上記〔４〕〜〔１３〕に記載のポリマーを含有する液晶配向剤。
〔１５〕上記〔４〕〜〔１３〕に記載のポリマーの少なくとも１つと、
上記〔５〕に記載の式（ＩＩＩ）〜（ＩＸ）および（ＸＶ）で表されるジアミンの群から選択される少なくとも１つおよび／または上記〔７〕に記載の式（Ｘ）〜（ＸＩＶ）で表されるジアミンの群から選択される少なくとも１つをテトラカルボン酸二無水物と反応させて得られるポリマーの少なくとも１つを混合した液晶配向剤。
〔１６〕上記〔１４〕または〔１５〕に記載の液晶配向剤を塗布し、加熱することによって形成される液晶配向膜。
〔１７〕上記〔１６〕に記載の液晶配向膜を有する液晶表示素子。 The present invention has the following configuration.
[1] A diamine having a side chain structure represented by the formula (1).

In formula (I):
R ¹ is —H, —F, —CN, alkyl having 1 to 30 carbons, fluorine-substituted alkyl having 1 to 30 carbons, alkoxy having 1 to 30 carbons, or fluorine-substituted alkoxy having 1 to 30 carbons. ;
A is 1,4-phenylene or 1,4-cyclohexylene;
Z is a single bond, —O—, —COO—, —OCO—, —CO—, —CONH—, —NHCO— or — (CH ₂ ) _m —, and m is an integer of 1 to 6;
n is 0 or 1; and
R ² is —H or alkyl having 1 to 5 carbons.
[2] R ¹ is alkyl having 4 to 20 carbon atoms, fluorine-substituted alkyl having 4 to 20 carbon atoms, alkoxy having 4 to 20 carbon atoms, or fluorine-substituted alkoxy having 4 to 20 carbon atoms;
n is 0; and
The diamine according to the above [1], wherein R ² is —H or —CH ₃ .
[3] R ¹ is alkyl having 4 to 20 carbon atoms, fluorine-substituted alkyl having 4 to 20 carbon atoms, alkoxy having 4 to 20 carbon atoms, or fluorine-substituted alkoxy having 4 to 20 carbon atoms;
n is 1;
A is 1,4-phenylene;
Z is a single bond, —O—, —COO—, —OCO—, or — (CH ₂ ) ₂ —; and
The diamine according to the above [1], wherein R ² is —H or —CH ₃ .
[4] A polymer obtained by reacting tetracarboxylic dianhydride as an acid component and at least one diamine having a side chain structure described in [1] above as a diamine component.
[5] The polymer according to the above [4], wherein at least one selected from the group of diamines represented by the following formulas (III) to (IX) and (XV) is further used as a diamine component.

In formula (III), A ¹ is - (CH _{2) m} - and is, m is an integer from 1 to 6;
In the formulas (V), (VII) and (IX), X is a single bond, —O—, —S—, —S—S—, —SO ₂ —, —CO—, —NH—, —N (CH _{3) -, - CONH -,} - NHCO -, - C (CH 3) 2 -, - C (CF 3) 2 -, - (CH 2) m -, - O- (CH 2) m -O-, _{-N (CH 3) - (CH} 2) m -N (CH 3) -, or -S- (CH ₂₎ a _m -S-, m is an integer from 1 to 6;
In Formula (VII), L ¹ and L ² are —H, but X is —NH—, —N (CH ₃ ) —, —CH ₂ —, —C (CH ₃ ) ₂ —, or —C ( CF ₃ ) ₂ — may combine with each other to form a single bond;
In formulas (VIII) and (IX), Y represents a single bond, —O—, —S—, —CO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, or 3 alkylene;
In formula (VIII), ring D is phenylene or pyrazine-1,4-diyl;
In formula (VI), -H on the benzene ring may be replaced by benzyl;
In formula (XV), R ³³ and R ³⁴ are independently alkyl or phenyl having 1 to 3 carbon atoms; G is independently alkylene, phenylene or alkyl-substituted phenylene having 1 to 6 carbon atoms; m is an integer from 1 to 10;
In each formula above, -H cyclohexane ring or benzene _{ring, -F, -CH 3, -OH,} -COOH, -SO 3 H, -PO 3 H 2, be replaced by benzyl or hydroxybenzyl, Also good.
[6] The polymer according to [5], wherein a diamine having a side chain structure other than the diamine represented by the formula (I) is further used as a diamine component.
[7] The polymer according to [4], wherein at least one selected from the group of diamines represented by the following formulas (X) to (XIV) is further used as a diamine component.

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

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

In the formula (s), R ³³ and R ³⁴ are independently alkyl having 1 to 3 carbon atoms, and m is an integer of 1 to 6;
c, d and e are each independently an integer of 0 to 3, and c + d + e ≧ 1.

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

In formulas (XIII) and (XIV), A ⁵ is independently —O— or alkylene having 1 to 6 carbons;
In the formula (XIII), R ¹¹ is —H or alkyl having 1 to 30 carbons, and arbitrary —CH ₂ — of this alkyl is replaced by —O—, —CH═CH— or —C≡C—. May be
A ⁶ is a single bond or alkylene having 1 to 3 carbon atoms;
Ring T is 1,4-phenylene or 1,4-cyclohexylene;
h is 0 or 1;
In formula (XIV), R ¹² is alkyl having 6 to 22 carbon atoms; and
R ¹³ is alkyl having 1 to 22 carbons.
[8] The diamine having a side chain structure other than the diamine represented by the formula (I) is at least one selected from the group of diamines represented by the formulas (X) to (XIV) according to the above [7]. The polymer as described in [6] above.
[9] The tetracarboxylic dianhydride to be reacted with the diamine is at least one selected from compounds represented by the following formulas (An-1) to (An-6), [4] to [8] ] The polymer of any one of these.

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

In the formulas (An-3) to (An-5), the ring E represents a monocyclic hydrocarbon group having 3 to 10 carbon atoms or a condensed polycyclic hydrocarbon group having 6 to 20 carbon atoms. Any hydrogen in may be replaced by methyl, ethyl or phenyl;
The bond on the ring is linked to any carbon that makes up the ring, and two bonds may be linked to the same carbon;
In the formula (An-6), X ¹¹ is alkylene having 2 to 6 carbons;
Me represents methyl and Ph represents phenyl.
[10] The tetracarboxylic dianhydride to be reacted with the diamine is selected from the group of at least one of an aromatic tetracarboxylic dianhydride, an alicyclic tetracarboxylic dianhydride and an aliphatic tetracarboxylic dianhydride The polymer according to any one of the above [4] to [8], which is at least one mixture.
[11] The tetracarboxylic dianhydride to be reacted with the diamine is at least one or a mixture of two or more selected from the group of alicyclic tetracarboxylic dianhydride and aliphatic tetracarboxylic dianhydride The polymer according to any one of [4] to [8] above.
[12] The above, wherein the aromatic tetracarboxylic dianhydride is at least one selected from compounds represented by the following formulas (1), (2), (5) to (7) and (17): 10].

[13] An alicyclic tetracarboxylic dianhydride and / or an aliphatic tetracarboxylic dianhydride is represented by the following formulas (19), (23), (25), (35) to (39), (44): The polymer according to [10] or [11], which is at least one selected from the compounds represented by (49) and (68).

[14] A liquid crystal aligning agent containing the polymer described in [4] to [13].
[15] At least one of the polymers described in [4] to [13] above,
At least one selected from the group of diamines represented by formulas (III) to (IX) and (XV) described in [5] above and / or formulas (X) to (XIV described in [7] above) The liquid crystal aligning agent which mixed at least 1 of the polymer obtained by making at least 1 selected from the group of diamine represented by tetracarboxylic dianhydride react.
[16] A liquid crystal alignment film formed by applying the liquid crystal aligning agent according to the above [14] or [15] and heating.
[17] A liquid crystal display device having the liquid crystal alignment film according to [16].

The composition containing the polymer obtained by making the diamine concerning the preferable aspect of this invention react with tetracarboxylic dianhydride can be used for a liquid crystal aligning agent. A liquid crystal display element having a liquid crystal alignment film formed of the liquid crystal alignment agent exhibits a low ion density and is excellent in long-term reliability.

1 is a ¹ H-NMR chart of diamine (I-1). ^{1 is} a ¹ H-NMR chart of diamine (I-2). It is a chart of ¹ H-NMR of diamine (I-3). It is a chart of ¹ H-NMR of diamine (I-33). ^{1 is} a ¹ H-NMR chart of diamine (I-34).

Terms used in this specification will be described. The diamine represented by formula (I-1) may be abbreviated as diamine (I-1). Similarly, diamines represented by other formulas may be abbreviated. The tetracarboxylic dianhydride represented by Formula (1) may be abbreviated as an acid anhydride (1). Similarly, tetracarboxylic dianhydrides represented by other formulas may be abbreviated in the same manner. “(Meth) acryloyloxy” is a generic term for acryloyloxy and methacryloyloxy, “(meth) acrylate” is a generic term for acrylates and methacrylates, and “(meth) acrylic acid” is a term for acrylic acid and methacrylic acid. It is a generic name.

The term “arbitrary” used in describing a chemical structural formula means that not only the position but also the number is arbitrary. And, for example, the expression “any A may be replaced by B, C or D” means that at least one A may be replaced by B and at least one A is replaced by C. It means that at least one A may be replaced by D, and a plurality of A may be further replaced by at least two of B to D. However, it does not include that a plurality of consecutive —CH ₂ — are replaced with the same group.

A substituent in which the bonding position with the carbon constituting the ring is not clear means that the bonding position may be bonded to any carbon in the ring as long as the bonding position is not chemically problematic. In the chemical structural formula, a group in which a letter (for example, B or C) is surrounded by a hexagon means a group having a ring structure (ring B or ring C). When the same symbol is used in more than one formula, it means that the groups have the same scope of definition but does not mean that all formulas must be the same group at the same time. The same group may be used in a plurality of formulas, or different groups may be used for each formula.

<Diamine having a side chain structure of the present invention>
The diamine of the present invention is a diamine having a triazine ring and a side chain structure represented by the following formula (I). A liquid crystal display element having a liquid crystal alignment film formed by a liquid crystal alignment agent containing a polymer obtained by reacting the diamine of the present invention with tetracarboxylic dianhydride exhibits a low ion density and has long-term reliability. Also excellent. Furthermore, a liquid crystal display element having a high pretilt angle can be obtained due to the side chain effect of diamine (I).

式（Ｉ）において、Ｒ¹は−Ｈ、−Ｆ、−ＣＮ、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、または炭素数１〜３０のフッ素置換アルコキシである。ここで挙げるアルキル、フッ素置換アルキル、アルコキシ、およびフッ素置換アルコキシとしては、直鎖および分枝鎖のいずれでもよいが、分岐鎖の場合側鎖の直線性を保つために主鎖から分岐するアルキルはメチル、エチル、プロピル等の短鎖のアルキルが好ましい。

In Formula (I), R ¹ is —H, —F, —CN, alkyl having 1 to 30 carbons, fluorine-substituted alkyl having 1 to 30 carbons, alkoxy having 1 to 30 carbons, or 1 to 30 carbons. Is a fluorine-substituted alkoxy. The alkyl, fluorine-substituted alkyl, alkoxy, and fluorine-substituted alkoxy listed here may be either linear or branched, but in the case of a branched chain, the alkyl branched from the main chain in order to maintain the linearity of the side chain is Short chain alkyls such as methyl, ethyl and propyl are preferred.

Examples of the alkyl having 1 to 30 carbons include linear alkyl having 1 to 30 carbons and branched alkyl having 3 to 30 carbons. Preferred alkyl is alkyl having 4 to 20 carbon atoms.

Specific examples of alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, and 1-methyl. Pentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propyl Pentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n-dodecyl, n- Tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl Le, n- octadecyl, such as n- eicosyl, and the like.

Examples of the alkoxy having 1 to 30 carbons include linear alkoxy having 1 to 30 carbons and branched alkoxy having 3 to 30 carbons. Preferred alkoxy is alkoxy having 4 to 20 carbon atoms.

Specific alkoxy includes methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, s-butyloxy, t-butyloxy, n-pentyloxy, isopentyloxy, neopentyloxy, t-pentyl. Oxy, n-hexyloxy, 1-methylpentyloxy, 4-methyl-2-pentyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-heptyloxy, 1-methylhexyloxy, n-octyl Oxy, t-octyloxy, 1-methylheptyloxy, 2-ethylhexyloxy, 2-propylpentyloxy, n-nonyloxy, 2,2-dimethylheptyloxy, 2,6-dimethyl-4-heptyloxy, 3,5 , 5-Trimethylhexyloxy, n Decyloxy, n-undecyloxy, 1-methyldecyloxy, n-dodecyloxy, n-tridecyloxy, 1-hexylheptyloxy, n-tetradecyloxy, n-pentadecyloxy, n-hexadecyloxy, n -Heptadecyloxy, n-octadecyloxy, n-eicosyloxy and the like.

Examples of the fluorine-substituted alkyl having 1 to 30 carbon atoms include straight-chain fluorine-substituted alkyl having 1 to 30 carbon atoms and branched-chain fluorine-substituted alkyl having 3 to 30 carbon atoms. Preferred fluorine-substituted alkyl is a fluorine-substituted alkyl having 4 to 20 carbon atoms. In the fluorine-substituted alkyl, all hydrogens of the corresponding alkyl may be replaced with fluorine, or hydrogen bonded to about 1 to 3 carbons at the terminal may be replaced with fluorine.

Specific examples of the fluorine-substituted alkyl include trifluoromethyl, difluoromethyl, monofluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, heptafluoropropyl, 2,2,3,3,3-pentafluoro. Propyl, 3,3,3-trifluoropropyl, n-nonafluorobutyl, 4,4,4-trifluorobutyl, undecafluoropentyl, 5,5,5-trifluoropentyl, perfluorohexyl, 3,3, 4,4,5,5,6,6,6-nonafluorohexyl, 6,6,6-trifluorohexyl, perfluoroheptyl, 7,7,7-trifluoroheptyl, perfluorooctyl, tridecafluoro-1, 1,2,2-tetrahydrooctyl, 8,8,8-trifluorooctyl, perfluorononyl 9,9,9-trifluorononyl, perfluorodecyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl, 10,10,10-trifluorodecyl, perfluoroundecyl, perfluorododecyl, perfluorotridecyl, perfluoro Examples include tetradecyl, perfluoro-1H, 1H, 2H, 2H-tetradecyl, perfluoropentadecyl, perfluorohexadecyl, perfluoroheptadecyl, perfluorooctadecyl, perfluoroeicosyl and the like.

Examples of the fluorine-substituted alkoxy having 1 to 30 carbon atoms include straight-chain fluorine-substituted alkoxy having 1 to 30 carbon atoms and branched-chain fluorine-substituted alkoxy having 3 to 30 carbon atoms. Preferred alkoxy is fluorine-substituted alkoxy having 4 to 20 carbon atoms.

Specific fluorine-substituted alkoxy includes trifluoromethoxy, difluoromethoxy, monofluoromethoxy, pentafluoroethoxy, 2,2,2-trifluoroethoxy, heptafluoropropyloxy, 2,2,3,3,3-penta Fluoropropyloxy, 3,3,3-trifluoropropyloxy, n-nonafluorobutyloxy, 4,4,4-trifluorobutyloxy, undecafluoropentyloxy, 5,5,5-trifluoropentyloxy, Perfluorohexyloxy, 3,3,4,4,5,5,6,6,6-nonafluorohexyloxy, 6,6,6-trifluorohexyloxy, perfluoroheptyloxy, 7,7,7-trifluoro Heptyloxy, perfluorooctyloxy, tridecafluoro- , 1,2,2-tetrahydrooctyloxy, 8,8,8-trifluorooctyloxy, perfluorononyloxy, 9,9,9-trifluorononyloxy, perfluorodecyloxy, heptadecafluoro-1,1,2 , 2-tetrahydrodecyloxy, 10,10,10-trifluorodecyloxy, perfluoroundecyloxy, perfluorododecyloxy, perfluorotridecyloxy, perfluorotetradecyloxy, perfluoro-1H, 1H, 2H, 2H-tetradecyloxy Perfluoropentadecyloxy, perfluorohexadecyloxy, perfluoroheptadecyloxy, perfluorooctadecyloxy, perfluoroeicosyloxy and the like.

n is 0 or 1, and when n = 1, A is 1,4-phenylene or 1,4-cyclohexylene, and A is preferably 1,4-phenylene. n may be 0, but n is preferably 1 when it is desired to increase the pretilt angle of the liquid crystal display element.

Z is a single bond, alkylene represented by —O—, —COO—, —OCO—, —CO—, —CONH—, —NHCO—, or — (CH ₂ ) _m —. M in alkylene is an integer of 1-6. Z may have any structure as long as it is a divalent group for linking two rings, but considering the decrease in ion density, which is an effect of the present invention, a single bond, —O—, —COO—, —OCO— , or - (CH _{2) m} - are preferred. In the case of alkylene, —CH ₂ CH ₂ — is preferable.

R ² is —H or alkyl having 1 to 5 carbons. Specifically, the alkyl having 1 to 5 carbon atoms is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, and t-pentyl. Is mentioned. R ² is preferably —H, methyl, ethyl, n-propyl, isopropyl and n-butyl, more preferably —H and methyl.

Specific examples of diamine (I) are listed below.

上記反応の第１段では、ジアミン（Ｉ）の側鎖となるアミンと塩化シアヌルを等モル反応させて中間体を得る。続いて、この中間体に２倍モル以上のｐ−フェニレンジアミンを反応させて目的物を得ることができる。例示したジアミン（Ｉ−１）以外の化合物も、原料であるアミンを適宜代えることにより、上記に準じた方法で製造することができる。 <Method for producing diamine (I)>
Diamine (I) can be produced by the method exemplified below. Here, the production of diamine (I-1) will be described as an example.

In the first stage of the above reaction, an intermediate is obtained by causing equimolar reaction between the amine that is the side chain of diamine (I) and cyanuric chloride. Subsequently, the intermediate can be reacted with two or more moles of p-phenylenediamine to obtain the desired product. Compounds other than the exemplified diamine (I-1) can also be produced by a method similar to the above by appropriately replacing the amine as the raw material.

The diamine that is a raw material when producing the polymer used for the liquid crystal aligning agent of the present invention may be at least one of diamine (I), and further includes at least one of other diamines other than these. May be. The proportion of diamine (I) used is 1 to 100 mol%, preferably 10 to 100 mol%, and more preferably 20 to 100 mol%, as a proportion of the diamine raw material used for polymer production. By making diamine (I) into such a use ratio, the ion density of a liquid crystal display element can be reduced and a low ion density can be maintained over a long period of time.

<Other diamines>
Other diamines can be divided into two types depending on the structure. That is, when a skeleton connecting two amino groups is viewed as a main chain, a group branched from the main chain, that is, a diamine having a side chain group and a diamine having no side chain group. By reacting a diamine having a side chain group with tetracarboxylic dianhydride, a polyamic acid having a large number of side chain groups with respect to the main chain of the polymer is obtained. When a polyamic acid having a side chain group with respect to such a polymer main chain is used, the liquid crystal alignment film formed from the liquid crystal aligning agent containing the polymer can increase the pretilt angle in the liquid crystal display element. . That is, this side chain group is a group having an effect of increasing the pretilt angle. The side chain group having such an effect needs to be a group having 3 or more carbon atoms. Specific examples include alkyl having 3 or more carbon atoms, alkoxy having 3 or more carbon atoms, alkoxyalkyl having 3 or more carbon atoms, and A group having a steroid skeleton can be exemplified. A group having one or more rings, wherein the terminal ring has any one of alkyl having 1 or more carbon atoms, alkoxy having 1 or more carbon atoms and alkoxyalkyl having 2 or more carbon atoms as a substituent; It has an effect as a side chain group. The side chain group in the present invention is selected from these groups. In the following description, a diamine having such a side chain group may be referred to as a side chain diamine. Such a diamine having no side chain group may be referred to as a non-side chain diamine.

Then, by properly using the side chain diamine and the non-side chain diamine, it is possible to cope with the pretilt angle required for each of the various display elements. That is, in the vertical electric field method represented by the TN method and the VA method, a relatively large pretilt angle is required, and therefore a side chain type diamine is mainly used. At this time, in order to further control the pretilt angle, a non-side chain diamine may be used in combination. What is necessary is just to determine the compounding ratio of non-side chain type diamine and side chain type diamine according to the magnitude | size of the target pretilt angle. Of course, it is possible to use only a side chain type diamine by appropriately selecting a side chain group. As described above, the liquid crystal aligning agent of the present invention can be applied to any kind of liquid crystal display element.

Specific examples of the side chain group are as follows. First, alkyl, alkoxy, alkoxyalkyl, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkylaminocarbonyl, alkenyl, alkenyloxy, alkenylcarbonyl, alkenylcarbonyloxy, alkenyloxycarbonyl, alkenylaminocarbonyl, alkynyl, alkynyloxy, Alkynylcarbonyl, alkynylcarbonyloxy, alkynyloxycarbonyl, alkynylaminocarbonyl and the like can be mentioned. Alkyl, alkenyl and alkynyl in these groups are all groups having 3 or more carbon atoms. However, in alkoxyalkyl, it is sufficient if it has 3 or more carbon atoms as a whole. These groups may be linear or branched.

Next, phenyl, phenylalkyl, phenylalkyloxy, phenyloxy, provided that the terminal ring has alkyl having 1 or more carbon atoms, alkoxy having 1 or more carbon atoms or alkoxyalkyl having 2 or more carbon atoms as a substituent. Phenylcarbonyl, phenylcarbonyloxy, phenyloxycarbonyl, phenylaminocarbonyl, phenylcyclohexyloxy, cycloalkyl having 3 or more carbon atoms, cyclohexylalkyl, cyclohexyloxy, cyclohexyloxycarbonyl, cyclohexylphenyl, cyclohexylphenylalkyl, cyclohexylphenyloxy, bis ( Cyclohexyl) oxy, bis (cyclohexyl) alkyl, bis (cyclohexyl) phenyl, bis (cyclohexyl) phenylalkyl, bis ( Kurohekishiru) oxycarbonyl, and bis (cyclohexyl) phenyloxycarbonyl and cyclohexyl bis (phenyl) group of a ring structure, such as oxycarbonyl,. In addition to phenyl and cyclohexyl, rings such as 1,3-dioxane, pyrimidine, pyridine, naphthalene, and anthracene can be used as appropriate.

Further, a group having two or more benzene rings, a group having two or more cyclohexane rings, or two or more groups composed of a benzene ring and a cyclohexane ring, wherein the bonding groups are independently a single bond, -O-, -COO-, -OCO-, -CONH-, -CH = CH-, or alkylene having 1 to 12 carbon atoms, the terminal ring is alkyl having 1 or more carbon atoms as a substituent, carbon number 1 Examples thereof include a ring assembly group having the above fluorine-substituted alkyl, alkoxy having 1 or more carbon atoms, fluorine-substituted alkoxy having 1 or more carbon atoms, or alkoxyalkyl having 2 or more carbon atoms. Here, in addition to benzene and cyclohexane, rings such as 1,3-dioxane, pyrimidine, pyridine, naphthalene, and anthracene can be appropriately used. A group having a steroid skeleton is also effective as a side chain group.

<Non-side chain diamine>
Examples of the diamine having no side chain group, that is, non-side chain diamines include compounds represented by formulas (III) to (IX) and (XV).

In formula (III), A ¹ is - (CH _{2) m} - and is, m is an integer from 1 to 6;
In the formulas (V), (VII) and (IX), X is a single bond, —O—, —S—, —S—S—, —SO ₂ —, —CO—, —NH—, —N (CH _{3) -, - CONH -,} - NHCO -, - C (CH 3) 2 -, - C (CF 3) 2 -, - (CH 2) m -, - O- (CH 2) m -O-, _{-N (CH 3) - (CH} 2) m -N (CH 3) -, or -S- (CH ₂₎ a _m -S-, m is an integer from 1 to 6;
In Formula (VII), L ¹ and L ² are —H, but X is —NH—, —N (CH ₃ ) —, —CH ₂ —, —C (CH ₃ ) ₂ —, or —C ( CF ₃ ) ₂ — may combine with each other to form a single bond;
In formulas (VIII) and (IX), Y represents a single bond, —O—, —S—, —CO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, or 3 alkylene;
In formula (VIII), ring D is phenylene or pyrazine-1,4-diyl;
In formula (VI), -H on the benzene ring may be replaced by benzyl;
In formula (XV), R ³³ and R ³⁴ are independently alkyl or phenyl having 1 to 3 carbon atoms; G is independently alkylene, phenylene or alkyl-substituted phenylene having 1 to 6 carbon atoms; m is an integer from 1 to 10;
In each formula above, -H cyclohexane ring or benzene _{ring, -F, -CH 3, -OH,} -COOH, -SO 3 H, -PO 3 H 2, be replaced by benzyl or hydroxybenzyl, Also good.

Specific examples of diamine (III) are shown below.

Specific examples of diamine (IV) are shown below.

Specific examples of diamine (V) are shown below.

Specific examples of diamine (VI) are shown below.

Specific examples of diamine (VII) are shown below.

Specific examples of diamine (VIII) are shown below.

Specific examples of diamine (IX) are shown below.

Specific examples of diamine (XV) are shown below.

Among the above-mentioned non-side chain diamines, diamines (VI-1) to (VI-5), diamines (VI-15) to (VI-17), diamines (VII-1) to (VII-12), diamines (VII-26), diamine (VII-27), diamine (VII-31), diamine (VII-33), diamine (VII-35) to (VII-37), diamine (VIII-1), diamine (VIII -2), diamine (VIII-6), diamine (VIII-1) to (IX-5) and diamine (XV-1) are preferred, and diamine (VI-1), diamine (VI-2), diamine (VI -15) to (VI-17), diamine (VII-1) to (VII-12), diamine (VII-33), diamine (VII-35) to (VII-37), diamine (VIII-) ), Diamine (IX-2) and the diamine (XV-1) is more preferable.

Such a non-side chain diamine is preferably contained in a molar ratio of 1 to 98% in the total amount of diamine as a raw material of polyamic acid in the liquid crystal aligning agent of the present invention in order to bring about a low ion density in the liquid crystal display device. 10 to 95% is more preferable.

式（Ｘ）において、Ｚ¹は、単結合、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＣＨ₂Ｏ−、−ＯＣＨ₂−、−ＣＦ₂Ｏ−、−ＯＣＦ₂−、または−（ＣＨ₂）_m−であり、ｍは１〜６の整数である。このアルキレンにおける任意の−ＣＨ₂−は−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられていてもよい。Ｒ³は、ステロイド骨格を有する基、炭素数３〜３０のアルキル、炭素数１〜３０のアルキルもしくは炭素数１〜３０のアルコキシを置換基として有するフェニル、または下記式（Ｘ−１）で表される基であり、この炭素数１〜３０のアルキルにおける任意の−ＣＨ₂−は−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられていてもよい。Ｒ³の好ましい例は炭素数３〜３０のアルキル、炭素数１〜３０のアルキルもしくは炭素数１〜３０のアルコキシを置換基として有するフェニル、および式（Ｘ−１）で表される基である。２つのアミノ基のベンゼン環との結合位置は、Ｚ¹の結合位置を１位とするとき、３位と５位または２位と５位であることが好ましい。 <Side-chain diamine>
Examples of the diamine having a side chain structure, that is, a side chain diamine, include compounds represented by formulas (X) to (XIV).

In the formula (X), Z ¹ is a single bond, —O—, —CO—, —COO—, —OCO—, —CONH—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ — or — (CH ₂ ) _m —, where m is an integer of 1-6. Any —CH ₂ — in the alkylene may be replaced by —O—, —CH═CH— or —C≡C—. R ³ is a group having a steroid skeleton, an alkyl having 3 to 30 carbon atoms, an alkyl having 1 to 30 carbon atoms or an alkoxy having 1 to 30 carbon atoms as a substituent, or a group represented by the following formula (X-1). In this alkyl group having 1 to 30 carbon atoms, any —CH ₂ — may be replaced by —O—, —CH═CH— or —C≡C—. Preferred examples of R ³ is a group represented by phenyl having alkyl having 3 to 30 carbon atoms, an alkoxy alkyl or C1-30 C1-30 as a substituent, and Formula (X-1) . The bonding positions of the two amino groups with the benzene ring are preferably the 3-position and 5-position or the 2-position and 5-position when the bonding position of Z ¹ is the ^1- position.

式（Ｘ−ａ）において、Ａ²およびＡ³は独立して、単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＣＨ＝ＣＨ−、または炭素数１〜１２のアルキレンであり、ａおよびｂは独立して０〜４の整数である。環Ｂおよび環Ｃは独立して１，４−フェニレン、１，４−シクロヘキシレン、１，３−ジオキサン−２，５−ジイル、ピリミジン−２，５−ジイル、ピリジン−２，５−ジイル、ナフタレン−１，５−ジイル、ナフタレン−２，７−ジイル、またはアントラセン−９，１０−ジイルである。Ｒ⁴およびＲ⁵は独立して−ＦまたはＣＨ₃であり、ｆおよびｇは独立して０〜２の整数である。Ｒ⁶は−Ｆ、−ＯＨ、−ＣＮ、炭素数１〜３０のアルキル、炭素数１〜３０のアルコキシ、または炭素数２〜３０のアルコキシアルキルであり、これらのアルキル、アルコキシ、アルコキシアルキルにおいて、任意の−Ｈは−Ｆで置き換えられていてもよく、任意の−ＣＨ₂−は−ＣＦ₂−または下記式（ｓ）で表される２価の基で置き換えられていてもよい。

式（ｓ）において、Ｒ³³およびＲ³⁴は独立して炭素数１〜３のアルキルであり、ｍは１〜６の整数であり、ｃ、ｄおよびｅは独立して０〜３の整数であり、そして、ｃ＋ｄ＋ｅ≧１である。Ｒ⁶の好ましい例は炭素数１〜３０のアルキルおよび炭素数１〜３０のアルコキシである。

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

In the formula (s), R ³³ and R ³⁴ are independently alkyl having 1 to 3 carbon atoms, m is an integer of 1 to 6, and c, d and e are independently an integer of 0 to 3. Yes, and c + d + e ≧ 1. Preferred examples of R ⁶ are alkyl having 1 to 30 carbons and alkoxy having 1 to 30 carbons.

式（ＸＩ）および（ＸＩＩ）において、Ｒ⁷は独立して−Ｈまたは−ＣＨ₃である。Ｒ⁸は−Ｈ、炭素数１〜２０のアルキルまたは炭素数２〜２０のアルケニルである。Ａ⁴は独立して単結合、−ＣＯ−または−ＣＨ₂−である。式（ＸＩＩ）において、Ｒ⁹およびＲ¹⁰は独立して炭素数１〜２０のアルキルまたはフェニルである。式（ＸＩ）において、２つの「ＮＨ₂−Ｐｈ−Ａ⁴−Ｏ−」の一方はステロイド骨格の３位に結合し、もう一方は６位に結合していることが好ましい。また、２つのアミノ基のベンゼン環との結合位置は、いずれもＡ⁴の結合位置に対して、メタ位またはパラ位であることが好ましい。式（ＸＩＩ）において、２つの「ＮＨ₂−（Ｒ¹⁰−）Ｐｈ−Ａ⁴−Ｏ−」のベンゼン環との結合位置は、いずれもステロイド骨格が結合している炭素に対してメタ位またはパラ位であることが好ましい。また、２つのアミノ基のベンゼン環との結合位置は、いずれもＡ⁴の結合位置に対して、メタ位またはパラ位であることが好ましい。

In formulas (XI) and (XII), R ⁷ is independently —H or —CH ₃ . R ⁸ is —H, alkyl having 1 to 20 carbons or alkenyl having 2 to 20 carbons. A ⁴ is independently a single bond, —CO— or —CH ₂ —. In formula (XII), R ⁹ and R ¹⁰ are independently alkyl having 1 to 20 carbons or phenyl. In the formula (XI), it is preferable that one of the two “NH ₂ —Ph—A ⁴ —O—” is bonded to the 3-position of the steroid skeleton and the other is bonded to the 6-position. The coupling position of the benzene ring of the two amino groups is preferably both with respect to the binding position of A ^4, a meta or para position. In formula (XII), the bonding positions of the two “NH ₂ — (R ¹⁰ —) Ph—A ⁴ —O—” with the benzene ring are all meta-positions relative to the carbon to which the steroid skeleton is bonded. The para position is preferred. The coupling position of the benzene ring of the two amino groups is preferably both with respect to the binding position of A ^4, a meta or para position.

式（ＸＩＩＩ）および（ＸＩＶ）において、Ａ⁵は独立して−Ｏ−または炭素数１〜６のアルキレンである。式（ＸＩＩＩ）において、Ｒ¹¹は−Ｈまたは炭素数１〜３０のアルキルであり、このアルキルの任意の−ＣＨ₂−は、−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよい。Ａ⁶は単結合または炭素数１〜３のアルキレンであり、環Ｔは１，４−フェニレンまたは１，４−シクロヘキシレンであり、ｈは０または１である。式（ＸＩＶ）において、Ｒ¹²は炭素数６〜２２のアルキルであり、Ｒ¹³は炭素数１〜２２のアルキルである。式（ＸＩＩＩ）において、２つのアミノ基のベンゼン環との結合位置は、いずれもＡ⁵の結合位置に対してメタ位またはパラ位であることが好ましい。式（ＸＩＶ）において、２つのアミノ基のベンゼン環との結合位置は、いずれもＡ⁵の結合位置に対してメタ位またはパラ位であることが好ましい。

In formulas (XIII) and (XIV), A ⁵ is independently —O— or alkylene having 1 to 6 carbons. In the formula (XIII), R ¹¹ is —H or alkyl having 1 to 30 carbons, and arbitrary —CH ₂ — of this alkyl is replaced by —O—, —CH═CH— or —C≡C—. May be. A ⁶ is a single bond or alkylene having 1 to 3 carbon atoms, ring T is 1,4-phenylene or 1,4-cyclohexylene, and h is 0 or 1. In the formula (XIV), R ¹² is alkyl having 6 to 22 carbon atoms, and R ¹³ is alkyl having 1 to 22 carbon atoms. In the formula (XIII), it is preferable that the bonding positions of the two amino groups with the benzene ring are both meta or para with respect to the bonding position of A ⁵ . In the formula (XIV), it is preferable that the bonding positions of the two amino groups with the benzene ring are both meta or para with respect to the bonding position of A ⁵ .

Specific examples of diamine (X) are shown below.

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

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

In the formulas (X-18) to (X-37), R ²⁷ is alkyl having 1 to 30 carbons or alkoxy having 1 to 30 carbons, preferably alkyl having 3 to 25 carbons or 3 to 25 carbons. Of alkoxy. R ²⁸ is hydrogen, fluorine, alkyl having 1 to 30 carbons, alkoxy having 1 to 30 carbons, —C≡N, —OCH ₂ F, —OCHF ₂ or —OCF ₃ , preferably ₃ to 25 carbons. Or alkyl having 3 to 25 carbon atoms.

Among the diamines (X-1) to (X-43), diamines (X-1) to (X-11) are preferable, and the diamine (X-2) and the diamines (X-4) to (X-6). ) Is more preferable.

Specific examples of diamine (XI) are shown below.

Specific examples of diamine (XII) are shown below.

Specific examples of diamine (XIII) are shown below.

In the formulas (XIII-1) to (XIII-3), R ²⁹ is alkyl having 1 to 30 carbons or alkoxy having 1 to 30 carbons, preferably alkyl having 3 to 30 carbons or 3 to 30 carbons. Of alkoxy. In the formulas (XIII-4) to (XIII-8), R ³⁰ is alkyl having 1 to ³⁰ carbons or alkoxy having 1 to 30 carbons, preferably alkyl having 3 to 30 carbons or 3 to 30 carbons. Of alkoxy.

Specific examples of diamine (XIV) are shown below.

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

Among the specific examples of the above-mentioned side chain diamine, diamine (X-2), diamine (X-4) to (X-6), diamine (XII-2), diamine (XIII-4), and (XIII- 6) is preferred.

When the above-mentioned side chain type diamine including diamine (I) is used for a liquid crystal display element that requires a large pretilt angle, when the polymer used in the liquid crystal aligning agent of the present invention is produced, the ratio in the total amount of diamine is 1 to It is preferable to set it as 90 mol%, and it is more preferable to set it as 5-70 mol%.

In the present invention, diamines other than the above diamines (III) to (VIII), diamines (X) to (XIV) and diamine (XV) can also be used. Examples of such diamines include fluorene-based diamines having a fluorene ring and side chain diamines other than diamines (X) to (XIV). Specific examples of such side chain diamines are shown below.

In these formulas, R ³⁵ and R ³⁶ are each independently alkyl having 3 to 30 carbon atoms. These diamines can be used as long as the effects of the present invention are not impaired when the polymer in the liquid crystal aligning agent of the present invention is produced.

The diamine contained in the amine component as the raw material of the polymer of the present invention is not limited to the above diamine, and other diamines having various structures may be used within the scope of achieving the object of the present invention. Needless to say, you can. In this case, one diamine may be used alone, or two or more diamines may be used in combination.

The amine component used as the raw material of the polymer of the present invention can impart a suitable pretilt angle to the liquid crystal alignment film formed using the liquid crystal aligning agent of the present invention by appropriately selecting the type of diamine and the combination thereof. it can. In the case of a VA liquid crystal display element, a large pretilt angle of about 80 to 90 ° is often required. The liquid crystal aligning agent of this invention which can adjust a high pretilt angle suitably is used suitably for such a liquid crystal display element.

<Polymer of the present invention>
The liquid crystal aligning agent of the present invention is obtained by reacting at least one of diamine (I) or a mixture of these (these) diamines and other diamines not represented by formula (I) with tetracarboxylic dianhydride. Contains the resulting polymer. The polymer is a polyamic acid or a polyamic acid derivative, and each may be used alone or may be a mixture of a polyamic acid and a derivative thereof.

Derivatives of polyamic acid are 1) polyimide obtained by completely dehydrating and ring-closing reaction of polyamic acid, 2) partially imidized polyamic acid obtained by partially dehydrating and ring-closing reaction of polyamic acid, 3) polyamic acid ester, 4) Polyamic acid-polyamide copolymer obtained by substituting a part of tetracarboxylic dianhydride with dicarboxylic acid, 5) Obtained by subjecting a part or all of this polyamic acid-polyamide copolymer to a dehydration ring-closing reaction. And polyamideimide. Of these, polyimide and partially imidized polyamic acid are preferable, and polyimide is more preferable. In the present specification, “polyamic acid” is used as a general term for polyamic acid and its derivatives except in Examples.

When producing a polyamic acid, a monoamine may be added to the diamine. By adding a monoamine, termination of the polymerization reaction when producing the polyamic acid can be caused, and further progress of the polymerization reaction can be suppressed. That is, the molecular weight of the obtained polymer (polyamic acid or derivative thereof) 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 addition ratio of monoamine may be appropriately adjusted in consideration of the molecular weight of the target polyamic acid, but the ratio of monoamine to all amine components is preferably 10 mol% or less.

If the effects of the present invention are not impaired, two or more monoamines may be added. Examples of monoamines are aniline, 4-hydroxyaniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecyl. Amine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, and n-eicosylamine .

In the present invention, when a diamine is reacted with tetracarboxylic dianhydride to obtain a polyamic acid, a diamine selected from the group of diamine (I) can be used alone or a mixture of a plurality of diamines (I) can be used. . Mixtures of diamines selected from the group of diamine (I) and other diamines can also be used. At this time, one of the preferable examples of the other diamine is at least one of non-side chain diamines selected from the group consisting of diamines (III) to (IX) and diamine (XV). When used for a liquid crystal display device that requires a particularly high pretilt angle, it is preferable to use at least one side chain diamine selected from the group of diamines (X) to (XIV) as the other diamine. The other diamine may be a mixture of at least one non-side chain diamine selected from the group of diamines (III) to (IX) and diamine (XV) and at least one side chain diamine. The side chain diamine is preferably at least one side chain diamine selected from the group of diamines (X) to (XIV). The above items [5] to [8] are preferable examples of a combination of a diamine selected from the group of diamine (I) and a non-side chain diamine and / or a side chain diamine.

In the liquid crystal aligning agent of this invention, the polyamic acid obtained by making diamine (I) or the mixture of diamine (I) and another diamine react with tetracarboxylic dianhydride as mentioned above contains as a polymer component. One polyamic acid may be used alone, or two or more may be used in combination.

In the liquid crystal aligning agent of this invention, it is good also considering the mixture of the polyamic acid derived from diamine (I) and the polyamic acid derived from the raw material which does not contain diamine (I) as a polymer component. One preferred example of such a mixture of polyamic acids is selected from the group of diamine (III) to diamine (IX) and diamine (XV), and at least one diamine selected from the group of diamine (I). A polyamic acid obtained by reacting a mixture of at least one non-side chain diamine with tetracarboxylic dianhydride, and at least one of the non-side chain diamines reacted with tetracarboxylic dianhydride; It is a mixture with the polyamic acid obtained by making the polyamic acid obtained react.

Another preferred example is at least one diamine selected from the group of diamines (I), at least one of non-side chain diamines selected from the group of diamines (III) to (IX) and diamine (XV). And a polyamic acid obtained by reacting a mixture of at least one side chain diamine selected from the group of diamines (X) to (XIV) with tetracarboxylic dianhydride, and the non-side chain diamine described above It is a mixture with the polyamic acid obtained by making the polyamic acid obtained by making at least 1 of these react with tetracarboxylic dianhydride.

<Tetracarboxylic dianhydride>
The acid component of the present invention consists of one or more tetracarboxylic dianhydrides. Tetracarboxylic dianhydrides are roughly classified into aromatic tetracarboxylic dianhydrides and non-aromatic tetracarboxylic dianhydrides. Examples of non-aromatic tetracarboxylic dianhydrides are alicyclic tetracarboxylic dianhydrides and aliphatic tetracarboxylic dianhydrides. The aromatic tetracarboxylic dianhydride in the present invention refers to a tetracarboxylic dianhydride in which four carboxyl groups are directly bonded to one or more aromatic rings.

Examples of aromatic tetracarboxylic dianhydrides are shown below.

Among the above aromatic tetracarboxylic dianhydrides, acid anhydride (1), acid anhydride (2), acid anhydride (5) to acid anhydride (7), acid anhydride (11) and acid anhydride The product (17) is preferred, and the acid anhydride (1) is particularly preferred.

Examples of alicyclic tetracarboxylic dianhydrides are shown below.

Of the above alicyclic tetracarboxylic dianhydrides, acid anhydride (19), acid anhydride (25), acid anhydride (35) to acid anhydride (37), acid anhydride (39), acid Anhydride (44) and acid anhydride (49) are preferred, and acid anhydride (19) is more preferred.

Examples of aliphatic tetracarboxylic dianhydrides are shown below. Of the following examples, acid anhydride (23) and acid anhydride (68) are preferred.

  In this invention, tetracarboxylic dianhydrides other than said acid anhydride (1)-acid anhydride (68) can also be used. Examples thereof include tetracarboxylic dianhydride having a side chain group. By using tetracarboxylic dianhydride having a side chain group, the pretilt angle in the liquid crystal display element can be increased. Examples of the tetracarboxylic dianhydride having a side chain group include an acid anhydride (69) having a steroid skeleton and an acid anhydride (70).

When manufacturing a polyamic acid, you may use it, adding a dicarboxylic acid anhydride to tetracarboxylic dianhydride. By doing so, termination of the polymerization reaction at the time of producing the polyamic acid can be caused, and further progress of the polymerization reaction can be suppressed. That is, the molecular weight of the resulting polymer (polyamic acid) 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 addition ratio of the dicarboxylic acid anhydride may be appropriately adjusted in consideration of the molecular weight of the target polyamic acid, but the ratio of the dicarboxylic acid to the total acid component is preferably 10 mol% or less. Two or more kinds of dicarboxylic acid anhydrides may be added as long as the effects of the present invention are not impaired. Examples of dicarboxylic acid anhydrides are 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.

In the present invention, a monoisocyanate compound may be further added when producing a polyamic acid. By adding a monoisocyanate compound, the terminal of the resulting polyamic acid is modified, and the molecular weight is adjusted. By using this terminal-modified polyamic acid, for example, the coating properties of the liquid crystal aligning agent can be improved without impairing the effects of the present invention. The addition amount of the monoisocyanate compound is preferably 1 to 10 mol% with respect to the total amount of diamine and tetracarboxylic dianhydride from the above viewpoint. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

<Synthesis of polyamic acid>
The polyamic acid of this invention can be manufactured similarly to the well-known polyamic acid used for formation of a polyimide film. That is, under a nitrogen stream, a tetracarboxylic dianhydride dissolved in the same solvent was added to a place where the diamine was stirred and dissolved in an appropriate solvent such as N-methyl-2-pyrrolidone dehydrated, and the temperature was 0 to 70 ° C. The solution of polyamic acid can be obtained by stirring for 1 to 48 hours. The amount of diamine and tetracarboxylic dianhydride charged is preferably approximately equimolar.

The molecular weight of the polyamic acid is preferably a weight average molecular weight (Mw) in terms of polystyrene of 10,000 to 500,000, and more preferably 20,000 to 200,000. The molecular weight of the polyamic acid can be determined from a measured value by a gel permeation chromatography (GPC) method.

The presence of polyamic acid can be confirmed by analyzing the solid content obtained by precipitation with a large amount of poor solvent by IR or NMR. The raw material used can be confirmed by decomposing polyamic acid with an aqueous solution of strong alkali such as KOH and NaOH and analyzing the extract of the decomposed product with an organic solvent by GC, HPLC or GC-MS. .

<Additives>
The liquid crystal aligning agent of this invention may further contain other components other than the said polyamic acid. 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. Preferred examples of this alkenyl-substituted nadiimide compound are shown below.

The liquid crystal aligning agent of this invention may further contain the compound which has a radically polymerizable unsaturated double bond from a viewpoint which stabilizes the electrical property of a liquid crystal display element for a long term, for example. 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. A (meth) acrylic acid derivative having two or more bonds is more preferred.

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

In the formulas (a) to (f), R ⁴¹ and R ⁴² are an organic group having 1 to 30 carbon atoms; R ^{43 to} R ⁴⁶ are hydrogen or a hydrocarbon group having 1 to 6 carbon atoms; X ²⁰ Is 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—, wherein m is an integer of 1 to 6; Y ²⁰ Is independently a single bond, —O—, —S—, —CO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, or alkylene having 1 to 3 carbon atoms.

The liquid crystal aligning agent of this invention may further contain the epoxy compound which has a 1 or 2 or more epoxy ring in a molecule | numerator from a viewpoint of the long-term stability of the electrical property in a liquid crystal display element, for example. This epoxy compound may be a monomer, oligomer or polymer having an epoxy ring.

The liquid crystal aligning agent of the present invention may further contain various additives. Examples of the various additives include polymers other than polyamic acid and its derivatives, and low molecular weight compounds, which can be selected and used according to their respective purposes. Examples of the polymer include polymers that are soluble in organic solvents. It is preferable to add such a polymer to the liquid crystal aligning agent of the present invention from the viewpoint of controlling the electrical characteristics and orientation of the liquid crystal alignment film to be formed. Examples of the polymer include polyamide, polyurethane, polyurea, polyester, polyepoxide, polyester polyol, silicone-modified polyurethane, and silicone-modified polyester.

Examples of the low molecular weight compound include 1) a surfactant in accordance with this purpose when improvement in coating properties is desired, 2) an antistatic agent when improvement in antistatic properties is required, and 3) adhesion to the substrate. When improvement in rubbing resistance is desired, a silane coupling agent or a titanium-based coupling agent, and 4) an imidization catalyst when imidization proceeds at a low temperature.

Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyltri Methoxysilane, paraaminophenyltrimethoxysilane, paraaminophenyltriethoxysilane, metaaminophenyltrimethoxysilane, metaaminophenyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-chloropropylmethyl Dimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N- (1,3-dimethylbutylidene) -3- (to Triethoxysilyl) -1-propylamine, and N, N'-bis [3- (trimethoxysilyl) propyl] ethylenediamine.

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

<Solvent>
The liquid crystal aligning agent of the present invention may further contain a solvent from the viewpoint of the application property of the liquid crystal aligning agent and the adjustment of the concentration of the polyamic acid. This solvent can be applied without any particular limitation as long as it has the ability to dissolve the polymer component. The said solvent contains the solvent normally used in the manufacturing process and application surface of polymer components, such as a polyamic acid and a soluble polyimide, and can be suitably selected according to the intended purpose. The solvent may be one kind or a mixed solvent of two or more kinds. Examples of such a solvent include a parent solvent for the polyamic acid and other solvents for improving coating properties.

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

Examples of other solvents for improving coating properties include alkyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, ethylene glycol monoalkyl ether (for example, ethylene glycol monobutyl ether), diethylene glycol monoalkyl ether (Eg, diethylene glycol monoethyl ether), ethylene glycol monoalkyl ether acetate, ethylene glycol monophenyl ether acetate, triethylene glycol monoalkyl ether, propylene glycol monoalkyl ether (eg, propylene glycol monomethyl ether, propylene glycol monobutyl ether), malon Dialkyl acid (eg, diethyl malonate), dipropylene glycol monoalkyl ether For example, dipropylene glycol monomethyl ether), and esterified acetates terminal OH groups of these compounds.

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

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

The concentration of the polymer component in the liquid crystal aligning agent may be adjusted depending on the method of applying the liquid crystal aligning agent. When the application method of the liquid crystal aligning agent is a spinner method or a printing method, the concentration of the polymer component is usually 10% by weight or less in order to maintain a good film thickness. Other coating methods such as dipping and ink jet methods may further reduce the concentration. On the other hand, when the concentration of the polymer component is 0.1% by weight or more, the 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 reduced by curing with dilution or stirring with a solvent.

<Liquid crystal alignment film>
The liquid crystal alignment film of the present invention is a film formed by heating the coating film of the liquid crystal aligning agent of the present invention described above. The liquid crystal alignment film of the present invention can be obtained by an ordinary method for producing a liquid crystal alignment film from a liquid crystal aligning agent. For example, the liquid crystal alignment film of the present invention includes a step of forming a coating film of the liquid crystal aligning agent of the present invention. The step of heating and baking this can be obtained. Since the liquid crystal alignment film of the present invention is used for a liquid crystal display element that requires a high pretilt angle, it usually does not require a rubbing treatment, but if necessary in the manufacturing process of the liquid crystal display element to be applied, the firing step The film obtained in step 1 may be rubbed.

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

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

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

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

The liquid crystal alignment film of the present invention can be suitably obtained by a method that further includes steps other than the steps described above. Examples of such other 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-treating in an oven or an infrared furnace, a method of heat-treating on a hot plate, and the like are generally known as in the baking step. These methods are also applicable to the drying step. The drying step is preferably performed at a temperature within a range where the solvent can be evaporated, and more preferably at a temperature relatively lower than the temperature in the baking step.

Examples of the cleaning method using the cleaning liquid 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 30-200 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 contains a pair of substrates and liquid crystal molecules, a liquid crystal layer formed between the pair of substrates, an electrode for applying a voltage to the liquid crystal layer, and the liquid crystal molecules aligned in a predetermined direction. And the liquid crystal alignment film of the present invention.

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 as described above in the liquid crystal alignment film of the present invention can be used as the electrode. it can. The liquid crystal layer is formed of a liquid crystal composition that is sealed between substrates having a liquid crystal alignment film surface inside.

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

Preferred liquid crystal compositions having a negative dielectric anisotropy include JP-A-57-114532, JP-A-2-4725, JP-A-4-222485, JP-A-8-40953, JP-A-8-104869, JP-A-10-168076, JP-A-10-168453, JP-A-10-236989, JP-A-10-236990, JP-A-10-236992, JP-A-10- No. 236993, JP-A-10-236994, JP-A-10-237000, JP-A-10-237004, JP-A-10-237024, JP-A-10-237035, JP-A-10-237075 Publication, Unexamined-Japanese-Patent No. 10-237076, Unexamined-Japanese-Patent No. 10-237448 (EP967261A1 specification), Japanese Laid-Open Patent Publication Nos. 10-287874, 10-287875, 10-291945, 11-029581, 11-080049, 2000-256307, 2001-2001. Examples thereof include liquid crystal compositions disclosed in Japanese Patent Laid-Open No. 019965, Japanese Patent Laid-Open No. 2001-072626, Japanese Patent Laid-Open No. 2001-192657, and the like.

It is possible to add at least one optically active compound to the liquid crystal composition having a positive or negative dielectric anisotropy.

If the liquid crystal alignment film of the present invention is used, liquid crystal display elements for various electric field systems can be formed. A liquid crystal display element for a vertical electric field system requires a relatively large pretilt angle. Therefore, a liquid crystal alignment film formed from a liquid crystal alignment agent containing a side chain type polyamic acid obtained by using a side chain type diamine or a diamine mixture containing the same is suitably used for a liquid crystal display element for a vertical electric field mode. It is done. The liquid crystal alignment film of the present invention is suitably used for a vertical electric field type liquid crystal display element. The liquid crystal alignment film produced using the liquid crystal aligning agent of the present invention as a raw material can be applied to liquid crystal display elements of various display drive systems by appropriately selecting the polymer as the raw material.

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

Hereinafter, the present invention will be described with reference to examples. The compounds used in the examples are as follows.
<Tetracarboxylic dianhydride>
Acid anhydride (1): pyromellitic dianhydride (19): 1,2,3,4-cyclobutanetetracarboxylic dianhydride (23): 1,2,3,4 Butanetetracarboxylic dianhydride (25): 1,2,4,5-cyclohexanetetracarboxylic dianhydride (37): 3,4-dicarboxy-1,2,3,4 -Tetrahydro-1-naphthalene succinic dianhydride (39): 3,5,6-tricarboxy-2-carboxymethylnorbornane 2: 3,5: 6-acid dianhydride (49) : 2,3,5-tricarboxycyclopentylacetic acid dianhydride acid anhydride (68): ethylenediaminetetraacetic acid dianhydride

<Diamine>
Diamine (I-1): 4- (4,6-bis (4-aminophenylamino) -1,3,5-triazin-2-ylamino) phenyl 4-dodecyloxybenzoate diamine (I-2): N2 , N4-bis (4-aminophenyl) -N6- (4-dodecylphenyl) -1,3,5-triazine-2,4,6-triaminediamine (I-3): 4-((4,6- Bis (4-aminophenylamino) -1,3,5-triazin-2-yl) (methyl) amino) phenyl 4-dodecyloxybenzoatediamine (I-33): 4- (4,6-bis (4 -Aminophenylamino) -1,3,5-triazin-2-ylamino) phenyl 4-octyloxybenzoatediamine (I-34): 4- (4,6-bis (4-aminophenylamino) -1 3,5-triazin-2-ylamino) phenyl 4-hexadecyloxybenzoatediamine (BATT): a compound in which X = n-dodecyloxy described in Non-Patent Documents 2 and 3: 4- (4,6-bis (4-aminophenylamino) -1,3,5-triazin-2-ylamino) phenyl 3,4,5-tri (dodecyloxy) benzoatediamine (VII-1): 4,4′-diaminodiphenylmethanediamine ( VII-5): 4,4′-methylenebis (3-methylaniline)
Diamine (VII-7): 4,4′-diamino-1,2-diphenylethanediamine (IX-2): 1,3-bis (4- (4-aminophenylmethyl) phenyl) propanediamine (XIII-4) -1): Compound in which R ³⁰ of (XIII-4) is n-pentyl: 1,1-bis (4- (4-aminophenoxy) phenyl) -4- (trans-4-n-pentylcyclohexyl) cyclohexane

<Solvent>
NMP: N-methyl-2-pyrrolidone BC: Butyl cellosolve (ethylene glycol monobutyl ether)
<Additives>
Compound: 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate (Product name: Celoxide 2021P): EHE
Compound: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane: EHS
Compound: 4,4′-methylenebis (N, N-diglycidylaniline): MGA
Compound: N, N ′-(1,2-dihydroxyethylene) bisacrylamide: HBA

<Synthesis of diamine>
Synthesis Example 1 Synthesis of Diamine (I-1) [1-1] 4- (4,6-Dichloro-1,3,5-triazin-2-ylamino) phenyl 4-dodecyloxybenzoate Cyanuric chloride (8.82 g) and THF (200 ml) were added, and the mixture was completely dissolved by stirring with cooling to 0 to 5 ° C. in an ice bath. A solution prepared by dissolving 17.28 g of 4-aminophenyl 4-dodecyloxybenzoate in 150 ml of THF was added dropwise thereto with stirring. After completion of dropping, stirring was continued for 2 hours while maintaining the temperature at 0 to 5 ° C. To this, 2.53 g of solid sodium carbonate was added little by little so that the temperature of the solution did not exceed 5 ° C. After completion of dropping, the mixture was further stirred for 4 hours while maintaining the temperature at 0 to 5 ° C. After completion of the stirring, the reaction mixture was transferred to a separatory funnel and washed three times with saturated brine, and the collected organic layer was dehydrated with magnesium sulfate overnight. After removing magnesium sulfate by filtration, the solvent was distilled off under reduced pressure, and the residue was dried under reduced pressure at 60 ° C. for 6 hours. This was recrystallized from toluene to give 19.02 g of 4- (4,6-dichloro-1,3,5-triazin-2-ylamino) phenyl 4-dodecyloxybenzoate (colorless needles, yield 81. 1%) was obtained.

[1-2] 4- (4,6-bis (4-aminophenylamino) -1,3,5-triazin-2-ylamino) phenyl 4-dodecyloxybenzoate: Synthesis of (I-1) Three-necked flask To the mixture, 60.33 g of p-phenylenediamine, 100 ml of 1,4-dioxane, and 3.70 g of sodium carbonate were added and stirred at reflux temperature. Then, 19.2-g of 4- (4,6-dichloro-1,3,5-triazin-2-ylamino) phenyl 4- (dodecyloxy) benzoate synthesized in [1-1] was added to 1,4-dioxane. A solution dissolved in 100 ml was added dropwise over 5 hours. After stirring at reflux temperature for 24 hours, the reaction mixture was poured into a large amount of hot water, and the precipitated solid was separated by suction filtration. The obtained solid was transferred to an eggplant flask, dissolved in 1000 ml of acetone, and stirred at reflux temperature for 1 hour. The solution was cooled to room temperature and suction filtered to remove insolubles. The solvent was distilled off under reduced pressure, and the residue was dried under reduced pressure at 60 ° C. for 6 hours. This was recrystallized from toluene to give 17.53 g of 4- (4,6-bis (4-aminophenylamino) -1,3,5-triazin-2-ylamino) phenyl 4-dodecyloxybenzoate (milky white needle) A crystal, yield 72.9%) was obtained. FIG. 1 shows a ¹ H-NMR chart of the present compound.

[Synthesis Example 2] Synthesis of Diamine (I-2) According to the method described in Synthesis Example 1, except that 4-dodecylaniline was used instead of 4-aminophenyl 4-dodecyloxybenzoate, N2, N4- Bis (4-aminophenyl) -N6- (4-dodecylphenyl) -1,3,5-triazine-2,4,6-triamine: (I-2) was synthesized. FIG. 2 shows a ¹ H-NMR chart of the present compound.

Synthesis Example 3 Synthesis of Diamine (I-3) Synthesis Example 1 except that 4- (N-methylamino) phenyl 4-dodecyloxybenzoate was used instead of 4-aminophenyl 4-dodecyloxybenzoate. According to the method described, 4-((4,6-bis (4-aminophenylamino) -1,3,5-triazin-2-yl) (methyl) amino) phenyl 4-dodecyloxybenzoate: ( I-3) was synthesized. FIG. 3 shows a ¹ H-NMR chart of the present compound.

[Synthesis Example 4] Synthesis of diamine (I-33) According to the method described in Synthesis Example 1 except that 4-aminophenyl 4-octyloxybenzoate was used instead of 4-aminophenyl 4-dodecyloxybenzoate. 4- (4,6-bis (4-aminophenylamino) -1,3,5-triazin-2-ylamino) phenyl 4-octyloxybenzoate: (I-33) was synthesized. FIG. 4 shows a ¹ H-NMR chart of the present compound.

[Synthesis Example 5] Synthesis of diamine (I-34) The method described in Synthesis Example 1 except that 4-aminophenyl 4-hexadecyloxybenzoate was used instead of 4-aminophenyl 4-dodecyloxybenzoate. Accordingly, 4- (4,6-bis (4-aminophenylamino) -1,3,5-triazin-2-ylamino) phenyl 4-hexadodecyloxybenzoate: (I-34) was synthesized. FIG. 5 shows a ¹ H-NMR chart of the present compound.

<Synthesis of polyamic acid>
[Polyamic acid synthesis example 1]
In a 100 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet and a nitrogen gas inlet, 4.613 g of diamine (I-1) and 27.0 g of dehydrated NMP were placed and dissolved under stirring in a dry nitrogen stream. Next, 0.730 g of acid anhydride (1), 0.657 g of acid anhydride (19) and 27.0 g of dehydrated NMP were added, and the mixture was stirred at room temperature for 30 hours. When the temperature increased during stirring, the reaction was carried out by suppressing the temperature to about 70 ° C. or lower using a water bath. BC40.0g was added to the obtained reaction liquid, and the polyamic acid solution whose concentration of the polymer solid content (henceforth abbreviated as polymer solid content) containing an unreacted monomer and a by-product was 6 weight% was obtained. . This polyamic acid is designated as PA1. The weight average molecular weight of PA1 was 75,400.

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 2% 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 (made by Waters), and measured on condition of column temperature 50 degreeC and flow rate 0.40 ml / min.

[Polyamic acid synthesis examples 2 to 17 and 19 to 28]
Polyamic acid solutions PA2 to 17 and PA19 to PA28 were produced according to Synthesis Example 1 except that tetracarboxylic dianhydride and diamine were changed as shown in Table 1. The results are summarized in Table 1 including Synthesis Example 1.

[Soluble Polyimide Synthesis Example 18]
In a 100 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet and a nitrogen gas inlet, 4.5269 g of diamine (I-1) and 24.0 g of dehydrated NMP were placed and dissolved under stirring in a dry nitrogen stream. Next, 1.4731 g of acid anhydride (49) and 20.0 g of dehydrated NMP were added, and the mixture was stirred at room temperature for 30 hours. When the temperature increased during stirring, the reaction was carried out by suppressing the temperature to about 70 ° C. or lower using a water bath. To 50 g of the obtained polyamic acid intermediate solution, 2 g of acetic anhydride and 0.5 g of pyridine were added as an imidization catalyst and reacted at 50 ° C. for 3 hours to obtain a polyimide solution. This solution was put into 200 ml of methanol, and the resulting white precipitate was filtered off to obtain a polyimide powder. When the imidation ratio of the obtained polyimide was determined from ¹ H-NMR, it was 53%. Here, the imidization ratio was determined as follows.
<Imidization rate>
After drying the polyimide polymer under reduced pressure at room temperature, it was dissolved in deuterated dimethyl sulfoxide, and ¹ H-NMR was measured at room temperature using tetramethylsilane as a reference substance, and determined by the formula shown in the following formula (i).
Formula (i) Imidization rate (%) = (1−A1 / A2 × B) × 100
A1: Peak area derived from proton of NH group (10 ppm)
A2: Peak area derived from proton of aromatic group (7 to 8 ppm)
B: In a polymer precursor (polyamic acid), 3 g of polyimide obtained from the number ratio of aromatic protons to one NH group proton was dissolved in 37.0 g of dehydrated NMP and 10.0 g of BC, and 6% by weight of polyimide. A solution was prepared. This polyimide is designated as PI18. The results are listed in Table 1.

[Polyamic acid synthesis examples 29 to 31]
Polyamic acid solutions PAX to PAZ were prepared according to Synthesis Example 1 except that the diamine (BATT) described in Non-Patent Documents 2 and 3 was used. The results are summarized in Table 2.

<Evaluation of coatability>
The polyamic acid solutions PA1, PA2, PA16, PAX, PAY, and PAZ were applied to a glass substrate with ITO with a spinner, and the presence or absence of repelling or unevenness was visually observed. The results are summarized in Table 3. In the table, those having no repellency or unevenness were designated as applicability ◯, and some were designated as applicability x.

[Example 1]
A mixed solvent of NMP / BC = 1/1 (weight ratio) was added to the polyamic acid solution PA1 having a concentration of 6% by weight produced in the polyamic acid synthesis example 1 to dilute the polymer solids concentration to 4% by weight. To obtain a liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, a liquid crystal display element was produced as follows.

<Production of liquid crystal display element>
The liquid crystal aligning agent was applied to two glass substrates with an ITO electrode by a spinner to form a film having a thickness of 80 nm. After coating, the film was heated and dried at 80 ° C. for about 1 minute, and then heat-treated at 210 ° C. for 15 minutes to form a liquid crystal alignment film. Next, the glass substrate on which the liquid crystal alignment film was formed was ultrasonically cleaned in ultrapure water for 5 minutes, and then dried in an oven at 120 ° C. for 30 minutes.

A 4 μm gap material was sprayed on one glass substrate, and two glass substrates were placed with the surface on which the liquid crystal alignment film was formed facing inside, and then sealed with an epoxy curing agent to produce a cell with a gap of 4 μm. The following liquid crystal composition was injected into this cell, and the injection port was sealed with a photocurable sealant. Next, a heat treatment was performed at 110 ° C. for 30 minutes to manufacture a liquid crystal display element.

[Example 2]
A mixed solvent of NMP / BC = 1/1 (weight ratio) is added to the polyamic acid solution PA2 having a concentration of 6% by weight produced in the polyamic acid synthesis example 2 to dilute the polymer solids concentration to 4% by weight. To obtain a liquid crystal aligning agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

[Example 3]
A mixed solvent of NMP / BC = 1/1 (weight ratio) was added to the polyamic acid solution PA3 having a concentration of 6% by weight produced in Polyamic Acid Synthesis Example 3 to dilute the polymer solids concentration to 4% by weight. To obtain a liquid crystal aligning agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

[Example 4]
A mixed solvent of NMP / BC = 1/1 (weight ratio) was added to the polyamic acid solution PA4 having a concentration of 6% by weight produced in Polyamic Acid Synthesis Example 4 to dilute the polymer solids concentration to 4% by weight. To obtain a liquid crystal aligning agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

[Example 5]
A mixed solvent of NMP / BC = 1/1 (weight ratio) was added to the polyamic acid solution PA5 having a concentration of 6% by weight produced in Polyamic Acid Synthesis Example 5 to dilute the polymer to a solid content of 4% by weight. To obtain a liquid crystal aligning agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

[Example 6]
A mixed solvent of NMP / BC = 1/1 (weight ratio) is added to the polyamic acid solution PA6 having a concentration of 6% by weight produced in the polyamic acid synthesis example 6 to dilute the polymer solids concentration to 4% by weight. To obtain a liquid crystal aligning agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

[Example 7]
A mixed solvent of NMP / BC = 1/1 (weight ratio) was added to the polyamic acid solution PA7 having a concentration of 6% by weight produced in the polyamic acid synthesis example 7 to dilute the polymer solids concentration to 4% by weight. To obtain a liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, a liquid crystal display element was produced in the same manner as in Example 1.

[Example 8]
A mixed solvent of NMP / BC = 1/1 (weight ratio) was added to the polyamic acid solution PA8 having a concentration of 6% by weight produced in the polyamic acid synthesis example 8 to dilute the polymer solids concentration to 4% by weight. To obtain a liquid crystal aligning agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

[Example 9]
A mixed solvent of NMP / BC = 1/1 (weight ratio) was added to the polyamic acid solution PA9 having a concentration of 6% by weight produced in the polyamic acid synthesis example 9 to dilute the polymer solids concentration to 4% by weight. To obtain a liquid crystal aligning agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

[Example 10]
A mixed solvent of NMP / BC = 1/1 (weight ratio) was added to the polyamic acid solution PA10 having a concentration of 6% by weight produced in the polyamic acid synthesis example 10 to dilute the polymer solids concentration to 4% by weight. To obtain a liquid crystal aligning agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

[Example 11]
A mixed solvent of NMP / BC = 1/1 (weight ratio) was added to the polyamic acid solution PA11 having a concentration of 6% by weight produced in the polyamic acid synthesis example 11 to dilute the polymer solids concentration to 4% by weight. To obtain a liquid crystal aligning agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

[Example 12]
A mixed solvent of NMP / BC = 1/1 (weight ratio) was added to the polyamic acid solution PA12 having a concentration of 6% by weight produced in the polyamic acid synthesis example 12 to dilute the polymer solids concentration to 4% by weight. To obtain a liquid crystal aligning agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

[Example 13]
A mixed solvent of NMP / BC = 1/1 (weight ratio) was added to the polyamic acid solution PA13 having a concentration of 6% by weight produced in the polyamic acid synthesis example 13 to dilute the polymer solids concentration to 4% by weight. To obtain a liquid crystal aligning agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

[Example 14]
The polyamic acid solution PA3 having a concentration of 6% by weight produced in the polyamic acid synthesis example 3 and the polyamic acid solution PA15 having a concentration of 6% by weight produced in the polyamic acid synthesis example 15 were mixed at a weight ratio of 2/8. Next, a mixed solvent of NMP / BC = 1/1 (weight ratio) was added to dilute the polymer solid content concentration to 4% by weight to obtain a liquid crystal aligning agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

[Example 15]
The polyamic acid solution PA6 having a concentration of 6% by weight produced in the polyamic acid synthesis example 6 and the polyamic acid solution PA15 having a concentration of 6% by weight produced in the polyamic acid synthesis example 15 were mixed at a weight ratio of 2/8. Next, a mixed solvent of NMP / BC = 1/1 (weight ratio) was added to dilute the polymer solid content concentration to 4% by weight to obtain a liquid crystal aligning agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

[Example 16]
A mixed solvent of NMP / BC = 1/1 (weight ratio) is added to the polyamic acid solution PA16 having a concentration of 6% by weight prepared in the polyamic acid synthesis example 16 to dilute the polymer solids concentration to 4% by weight. To obtain a liquid crystal aligning agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

[Example 17]
A mixed solvent of NMP / BC = 1/1 (weight ratio) was added to the polyamic acid solution PA17 having a concentration of 6% by weight prepared in Polyamic Acid Synthesis Example 17 to dilute the polymer solids concentration to 4% by weight. To obtain a liquid crystal aligning agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

[Example 18]
Liquid crystal alignment by adding a mixed solvent of NMP / BC = 1/1 (weight ratio) to the polyimide solution PI18 having a concentration of 6% by weight prepared in Synthesis Example 18 to make the polymer solid content concentration 4% by weight. An agent was used. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

[Example 19]
A mixed solvent of NMP / BC = 1/1 (weight ratio) was added to the polyamic acid solution PA19 having a concentration of 6% by weight prepared in the polyamic acid synthesis example 19 to dilute the polymer solids concentration to 4% by weight. To obtain a liquid crystal aligning agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

[Example 20]
A mixed solvent of NMP / BC = 1/1 (weight ratio) is added to the polyamic acid solution PA20 having a concentration of 6% by weight prepared in Polyamic Acid Synthesis Example 20, and diluted so that the polymer solids concentration becomes 4% by weight. To obtain a liquid crystal aligning agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

[Example 21]
To the polyamic acid solution (PA13) having a concentration of 6% by weight prepared in Polyamic Acid Synthesis Example 13, 20% by weight of MGA was added per polymer weight. The obtained mixture was diluted to 4% by weight with a mixed solvent of NMP / BC = 1/1 (weight ratio) to obtain a liquid crystal aligning agent. A liquid crystal display element was produced in the same manner as in Example 1 using a liquid crystal aligning agent.

[Example 22]
To the polyamic acid solution (PA17) having a concentration of 6% by weight prepared in Polyamic Acid Synthesis Example 17, 20% by weight of EHS was added per polymer weight. The obtained mixture was diluted to 4% by weight with a mixed solvent of NMP / BC = 1/1 (weight ratio) to obtain a liquid crystal aligning agent. A liquid crystal display element was produced in the same manner as in Example 1 using a liquid crystal aligning agent.

[Example 23]
The polyamic acid solution PA6 having a concentration of 6% by weight produced in the polyamic acid synthesis example 6 and the polyamic acid solution PA15 having a concentration of 6% by weight produced in the polyamic acid synthesis example 15 were mixed at a weight ratio of 2/8, and EHE was polymerized. 20% by weight was added per weight. Next, a mixed solvent of NMP / BC = 1/1 (weight ratio) was added to dilute the polymer solid content concentration to 4% by weight to obtain a liquid crystal aligning agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

[Comparative Example 1]
A mixed solvent of NMP / BC = 1/1 (weight ratio) was added to the polyamic acid solution PA14 having a concentration of 6% by weight produced in the polyamic acid synthesis example 14 to dilute the polymer solids concentration to 4% by weight. To obtain a liquid crystal aligning agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

<Evaluation of electrical characteristics>
About the liquid crystal display element produced in Examples 1-23 and the comparative example 1, the measurement of ion density and the measurement of long-term reliability were performed as follows.

1) Measurement of ion density Ion density was measured using a liquid crystal property evaluation apparatus 6254 type manufactured by Toyo Technica. The measurement conditions were waveform: triangular wave, frequency: 0.01 Hz, voltage: ± 10 V, and measurement temperature was 60 ° C. It can be said that the smaller this value, the better the electrical characteristics. The results are shown in Table 2.

2) Measurement of holding property of ion density With respect to the produced liquid crystal display element, ion density [pC] was obtained over time, and the holding property was evaluated. As a test method for the holding characteristics, a method was adopted in which the liquid crystal display element was left in an atmosphere at a temperature of 100 ° C., and the ion density [pC] was taken out over time. The ion density data after 300 hours and after 500 hours are shown in Table 4. The amount of increase in Table 4 is a value obtained by subtracting the initial (0 hour) ion density from the ion density after 500 hours. It can be said that the smaller the increase in ion density (for example, when the increase amount is less than 200), the better the ion density retention property and the better the long-term reliability of the electrical property.

[Example 24]
<Production of liquid crystal display element>
The polyamic acid solution (PA21) having a concentration of 6% by weight synthesized in Synthesis Example 21 was added to a mixed solvent of NMP / BC = 1/1 (weight ratio) to dilute the whole to 4% by weight to obtain a liquid crystal aligning agent. . Using the obtained liquid crystal aligning agent, a liquid crystal display element was produced as follows.

<Method for manufacturing liquid crystal display element>
The liquid crystal aligning agent was applied to two glass substrates with an ITO electrode with a spinner to form a film with a thickness of 100 nm. After coating, the film was heated and dried at 80 ° C. for about 1 minute, and then heat-treated at 210 ° C. for 15 minutes to form a liquid crystal alignment film. Using a rubbing treatment device manufactured by Iinuma Gauge Co., Ltd., with a rubbing cloth (hair length 1.8 mm: rayon) push-in amount of 0.40 mm, stage moving speed 60 mm / sec, roller rotation speed 1,000 rpm The obtained liquid crystal alignment film was rubbed. Thereafter, the liquid crystal alignment film was ultrasonically cleaned in ultrapure water for 5 minutes and then dried in an oven at 120 ° C. for 30 minutes.

  One glass substrate was sprayed with a gap material of 4 μm, and the surface on which the liquid crystal alignment film was formed was placed inside so that the rubbing direction was antiparallel, then sealed with an epoxy curing agent, and an anti-gap with a gap of 4 μm. A parallel cell was produced. The liquid crystal composition shown below was injected into the cell, and the injection port was sealed with a photocuring agent. Next, a heat treatment was performed at 110 ° C. for 30 minutes to manufacture a liquid crystal display element.

[Examples 25 to 31]
A polyamic acid solution (PA22 to PA28) having a concentration of 6% by weight shown in Table 1 was diluted to 4% by weight by adding a mixed solvent of NMP / BC = 1/1 (weight ratio) to obtain a liquid crystal aligning agent and did. A liquid crystal display element was produced in the same manner as in Example 24 using the obtained liquid crystal aligning agent.

[Example 32]
The polyamic acid solution (PA15) having a concentration of 6% by weight synthesized in Synthesis Example 15 and the polyamic acid solution (PA24) having a concentration of 6% by weight synthesized in Synthesis Example 24 were mixed at a weight ratio of 8/2, and HBA was polymer weight. 20% by weight was added per unit. Next, a mixed solvent of NMP / BC = 1/1 (weight ratio) was added to the obtained mixture to dilute the whole to 4% by weight to obtain a liquid crystal aligning agent. A liquid crystal display element was produced in the same manner as in Example 24 using the obtained liquid crystal aligning agent.

[Example 33]
The 6% polyamic acid solution (PA15) synthesized in Synthesis Example 15 and the 6% polyamic acid solution (PA27) synthesized in Synthetic Example 27 were mixed at a weight ratio of 8/2. A mixed solvent of NMP / BC = 1/1 (weight ratio) was added to the obtained mixture to dilute the whole to 4% by weight to obtain a liquid crystal aligning agent. A liquid crystal display element was produced in the same manner as in Example 24 using the obtained liquid crystal aligning agent.

[Comparative Example 2]
A polyamic acid solution (PA15) having a concentration of 6% by weight shown in Table 1 was diluted to 4% by weight by adding a mixed solvent of NMP / BC = 1/1 (weight ratio) to obtain a liquid crystal aligning agent. A liquid crystal display element was produced in the same manner as in Example 24 using the obtained liquid crystal aligning agent.

<Evaluation of electrical characteristics>
Table 5 shows the results of ion density and long-term reliability of the liquid crystal display elements produced in Examples 24-33 and Comparative Example 2.

Claims (17)

Diamine which has a side chain structure represented by Formula (1).

In formula (I):
R ¹ is —H, —F, —CN, alkyl having 1 to 30 carbons, fluorine-substituted alkyl having 1 to 30 carbons, alkoxy having 1 to 30 carbons, or fluorine-substituted alkoxy having 1 to 30 carbons. ;
A is 1,4-phenylene or 1,4-cyclohexylene;
Z is a single bond, —O—, —COO—, —OCO—, —CO—, —CONH—, —NHCO— or — (CH ₂ ) _m —, and m is an integer of 1 to 6;
n is 0 or 1; and
R ² is —H or alkyl having 1 to 5 carbons. R ¹ is alkyl having 4 to 20 carbon atoms, fluorine-substituted alkyl having 4 to 20 carbon atoms, alkoxy having 4 to 20 carbon atoms, or fluorine-substituted alkoxy having 4 to 20 carbon atoms;
n is 0; and
The diamine according to claim 1, wherein R ² is —H or —CH ₃ . R ¹ is alkyl having 4 to 20 carbon atoms, fluorine-substituted alkyl having 4 to 20 carbon atoms, alkoxy having 4 to 20 carbon atoms, or fluorine-substituted alkoxy having 4 to 20 carbon atoms;
n is 1;
A is 1,4-phenylene;
Z is a single bond, —O—, —COO—, —OCO—, or — (CH ₂ ) ₂ —; and
The diamine according to claim 1, wherein R ² is —H or —CH ₃ . A polymer obtained by reacting tetracarboxylic dianhydride as an acid component and at least one diamine having a side chain structure according to claim 1 as a diamine component. The polymer according to claim 4, wherein at least one selected from the group of diamines represented by the following formulas (III) to (IX) and (XV) is further used as the diamine component.

In formula (III), A ¹ is - (CH _{2) m} - and is, m is an integer from 1 to 6;
In the formulas (V), (VII) and (IX), X is a single bond, —O—, —S—, —S—S—, —SO ₂ —, —CO—, —NH—, —N (CH _{3) -, - CONH -,} - NHCO -, - C (CH 3) 2 -, - C (CF 3) 2 -, - (CH 2) m -, - O- (CH 2) m -O-, _{-N (CH 3) - (CH} 2) m -N (CH 3) -, or -S- (CH ₂₎ a _m -S-, m is an integer from 1 to 6;
In Formula (VII), L ¹ and L ² are —H, but X is —NH—, —N (CH ₃ ) —, —CH ₂ —, —C (CH ₃ ) ₂ —, or —C ( CF ₃ ) ₂ — may combine with each other to form a single bond;
In formulas (VIII) and (IX), Y represents a single bond, —O—, —S—, —CO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, or 3 alkylene;
In formula (VIII), ring D is phenylene or pyrazine-1,4-diyl;
In formula (VI), -H on the benzene ring may be replaced by benzyl;
In formula (XV), R ³³ and R ³⁴ are independently alkyl or phenyl having 1 to 3 carbon atoms; G is independently alkylene, phenylene or alkyl-substituted phenylene having 1 to 6 carbon atoms; m is an integer from 1 to 10;
In each formula above, -H cyclohexane ring or benzene _{ring, -F, -CH 3, -OH,} -COOH, -SO 3 H, -PO 3 H 2, be replaced by benzyl or hydroxybenzyl, Also good. The polymer according to claim 5, wherein a diamine having a side chain structure other than the diamine represented by formula (I) is further used as the diamine component. The polymer according to claim 4, wherein at least one selected from the group of diamines represented by the following formulas (X) to (XIV) is further used as the diamine component.

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

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

In the formula (s), R ³³ and R ³⁴ are independently alkyl having 1 to 3 carbon atoms, and m is an integer of 1 to 6;
c, d and e are each independently an integer of 0 to 3, and c + d + e ≧ 1.

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

In formulas (XIII) and (XIV), A ⁵ is independently —O— or alkylene having 1 to 6 carbons;
In the formula (XIII), R ¹¹ is —H or alkyl having 1 to 30 carbons, and arbitrary —CH ₂ — of this alkyl is replaced by —O—, —CH═CH— or —C≡C—. May be
A ⁶ is a single bond or alkylene having 1 to 3 carbon atoms;
Ring T is 1,4-phenylene or 1,4-cyclohexylene;
h is 0 or 1;
In formula (XIV), R ¹² is alkyl having 6 to 22 carbon atoms; and
R ¹³ is alkyl having 1 to 22 carbons. The diamine having a side chain structure other than the diamine represented by the formula (I) is at least one selected from the group of diamines represented by the formulas (X) to (XIV) according to claim 7. The polymer according to claim 6. The tetracarboxylic dianhydride to be reacted with a diamine is at least one selected from the compounds represented by the following formulas (An-1) to (An-6), 9. The polymer described in 1.

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

In the formulas (An-3) to (An-5), the ring E represents a monocyclic hydrocarbon group having 3 to 10 carbon atoms or a condensed polycyclic hydrocarbon group having 6 to 20 carbon atoms. Any hydrogen in may be replaced by methyl, ethyl or phenyl;
The bond on the ring is linked to any carbon that makes up the ring, and two bonds may be linked to the same carbon;
In the formula (An-6), X ¹¹ is alkylene having 2 to 6 carbons;
Me represents methyl and Ph represents phenyl. The tetracarboxylic dianhydride to be reacted with the diamine is at least one selected from the group consisting of at least one aromatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride and aliphatic tetracarboxylic dianhydride. 9. A polymer according to any one of claims 4 to 8 which is a mixture. The tetracarboxylic dianhydride to be reacted with the diamine is at least one or a mixture of two or more selected from the group of alicyclic tetracarboxylic dianhydrides and aliphatic tetracarboxylic dianhydrides. The polymer according to any one of 4 to 8. The aromatic tetracarboxylic dianhydride is at least one selected from the compounds represented by the following formulas (1), (2), (5) to (7) and (17). Polymer.

The alicyclic tetracarboxylic dianhydride and / or the aliphatic tetracarboxylic dianhydride is represented by the following formulas (19), (23), (25), (35) to (39), (44), (49 The polymer according to claim 10 or 11, which is at least one selected from the compounds represented by (68) and (68).

The liquid crystal aligning agent containing the polymer of any one of Claims 4-13. At least one of the polymers of claims 4-13;
At least one selected from the group of diamines represented by formulas (III) to (IX) and (XV) according to claim 5 and / or formulas (X) to (XIV) according to claim 7 Liquid crystal aligning agent which mixed at least 1 of the polymer obtained by making at least 1 selected from the group of the represented diamine react with tetracarboxylic dianhydride. The liquid crystal aligning film formed by apply | coating the liquid crystal aligning agent of Claim 14 or 15, and heating. The liquid crystal display element which has a liquid crystal aligning film of Claim 16.

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