JP2012193167A - Diamine, liquid crystal alignment agent using the same, liquid crystal display element, and method of forming liquid crystal alignment film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a diamine compound capable of obtaining a liquid crystal alignment agent for forming a liquid crystal alignment film with high liquid crystal alignment properties, low volume resistivity, and good electric characteristics such as VHR when used as a part of materials for polyamic acid and its derivative used for the liquid crystal alignment agent.SOLUTION: A diamine, which includes a primary or secondary amino group protected with a group detachable by heat in the molecule, is used as a material for polyamic acid and its derivative.

Description

The present invention relates to a diamine having in the molecule thereof at least one primary or secondary amino group protected by a group capable of leaving by heat, a polyamic acid and a derivative thereof using the diamine as a raw material, these polyamic acids and their The present invention relates to a liquid crystal aligning agent containing a derivative, uses of these liquid crystal aligning agents, and methods for forming these liquid crystal aligning films.

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

The development of the technology of the liquid crystal display element is achieved not only by simply improving these driving methods and element structures but also by improving the components used in the elements. Among the components used in liquid crystal display elements, the liquid crystal alignment film is one of important materials related to display quality, and the performance of the alignment film can be improved with the improvement in quality of the liquid crystal display element. It is becoming important.

The liquid crystal alignment film is prepared from a liquid crystal aligning agent. The liquid crystal aligning agent mainly used at present is a solution (varnish) obtained by dissolving polyamic acid or soluble polyimide in an organic solvent. After this solution is applied to the substrate, it is formed by means such as heating to form a polyimide-based liquid crystal alignment film.

The liquid crystal alignment film is required to bring the following characteristics to the liquid crystal display element.
(1) Giving an appropriate pretilt angle to liquid crystal molecules. In addition, the pretilt angle is not easily affected by indentation strength during rubbing or temperature conditions during heating.
(2) High liquid crystal orientation. In addition, alignment defects of liquid crystal molecules due to alignment rubbing unevenness, scratches, or alignment film scraping do not occur.
(3) Give an appropriate voltage holding ratio (VHR) to the liquid crystal display element.
(4) A phenomenon called “burn-in” in which an image is displayed as an afterimage when an arbitrary image is displayed on the liquid crystal display element for a long time and then changed to another image, is less likely to occur.

As one of the methods for reducing the afterimage (4), it is well known that it is important to reduce the residual voltage (RDC) (see, for example, Patent Document 1). RDC is a voltage that remains when the voltage is returned to 0 V after the liquid crystal is driven by applying a voltage. In particular, in an alignment film used for an IPS liquid crystal display element, an alignment film material having a small volume resistance value is required in order to reduce the RDC (see, for example, Patent Documents 2 to 4).

The following diamine compound (DI-A) is known as a diamine for alignment film materials having a small volume resistance and excellent liquid crystal alignment (see, for example, Patent Document 5). If it is possible to develop a diamine having a high volume resistivity and a small volume resistance value, it is expected that an alignment film having further excellent afterimage characteristics can be obtained. Therefore, the authors apply a diamine compound (DI-B) in which the central —NCH ₃ group of the diamine compound (DI-A) is changed to an —NH group as a diamine having such properties as a diamine for alignment film materials. I tried to synthesize it. Although this diamine compound and tetracarboxylic dianhydride were reacted in an organic solvent, all four amino groups were involved in the reaction, causing gelation, and as a result, the target product (polyamic acid) could be obtained. There wasn't.

JP 2008-233713 A JP-A-7-159786 JP 2006-284887 A International Publication No. 2004/053583 Pamphlet JP 2009-058928 A

As described above, the volume resistance that can satisfy the above-mentioned characteristics (1) to (4) required for the liquid crystal display element in a well-balanced manner, and in particular, can form an alignment film suitable for satisfying the characteristics (4). An alignment film material having a small value is demanded.

The present inventors have used the above-mentioned polyamic acid and its derivatives, which are made from a diamine having a primary or secondary amino group protected by a group capable of leaving by heat, in the molecule, as a liquid crystal aligning agent. The inventors have found that a liquid crystal display element satisfying the required characteristics can be obtained, and have completed the present invention.

式（１）において、Ｒ^１は熱により脱離する基であり；
Ｒ^２は独立して−Ｈ、熱により脱離する基または熱により脱離する基を有する基であり；
Ｇ^１およびＧ^４は独立して芳香環を有する２価の有機基であり；
Ｇ^２は単結合または炭素数１〜１０のアルキレンであり；
Ｇ^３は単結合、−Ｏ−、−ＣＯＮＨ−、−ＮＭｅ−、または−ＮＲ^１−であり；
ａ、ｂ、およびｃは独立して０または１であるが、Ｒ^２が−Ｈであるときｂは１であり；そして、
ａ、ｃそれぞれが１であるとき、−ＮＨ_２は２価の有機基の芳香環に直接結合している。 The present invention has the following configuration.
[1] Diamine represented by formula (1):

In the formula (1), R ¹ is a group capable of leaving by heat;
R ² is independently -H, a group capable of leaving by heat or a group having a group leaving by heat;
G ¹ and G ⁴ are independently a divalent organic group having an aromatic ring;
G ² is a single bond or alkylene having 1 to 10 carbons;
G ³ is a single bond, —O—, —CONH—, —NMe—, or —NR ¹ —;
a, b, and c are independently 0 or 1, but b is 1 when R ² is —H; and
When each of a and c is 1, —NH ₂ is directly bonded to the aromatic ring of the divalent organic group.

[2] The diamine according to item [1], wherein in the diamine represented by the formula (1), the group capable of leaving by heat in R ¹ and R ² is a carbamate protecting group.

[3] The diamine according to item [1], wherein R ¹ is Boc and R ² is —H, —NHBoc or —N (Boc) ₂ in the diamine represented by formula (1):
Here, Boc is a t-butoxycarbonyl group.

式（１−ａ）〜式（１−ｄ）において、Ｂｏｃはｔ−ブトキシカルボニル基であり;
Ｇ^５は炭素数２〜１０のアルキレンであり；
Ｒ^３は独立して−Ｈ、−ＮＨＢｏｃまたは−Ｎ（Ｂｏｃ）_２であり、そして、Ｒ^３の少なくとも１つは−ＮＨＢｏｃまたは−Ｎ（Ｂｏｃ）_２である。 [4] The diamine according to item [1], represented by any one of formulas (1-a) to (1-d):

In the formula (1-a) to the formula (1-d), Boc is a t-butoxycarbonyl group;
G ⁵ is alkylene having 2 to 10 carbons;
R ³ is independently —H, —NHBoc or —N (Boc) ₂ , and at least one of R ³ is —NHBoc or —N (Boc) ₂ .

[5] A diamine mixture containing at least one of the diamines according to any one of [1] to [4] or at least one of the diamines according to any one of [1] to [4]. And a polyamic acid obtained by reacting tetracarboxylic dianhydride or a derivative thereof.

[6] The method according to item [5], which is obtained by reacting a mixture of at least one of the diamine according to any one of [1] to [4] with another diamine with tetracarboxylic dianhydride. Polyamic acid or its derivative.

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

これらの基の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もよく；
式（ＡＮ−ＩＩＩ）〜（ＡＮ−Ｖ）において、環Ａは炭素数３〜１０の単環式炭化水素の基または炭素数６〜３０の縮合多環式炭化水素の基であり、この基の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−ＶＩ）において、Ｘ^１０は炭素数２〜６のアルキレンであり；
Ｍｅはメチルであり；
Ｐｈはフェニルであり；
式（ＡＮ−ＶＩＩ）において、Ｇ^１０は独立して−Ｏ−、−ＣＯＯ−または−ＯＣＯ−であり；そして、
ｒは独立して０または１である。 [7] The polyamic acid according to the item [5] or [6], wherein the tetracarboxylic dianhydride is at least one selected from the group consisting of the following formulas (AN-I) to (AN-VII): Or its derivatives:

In formulas (AN-I), (AN-IV) and (AN-V), X is independently a single bond or —CH ₂ —;
In Formula (AN-II), G 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-II) to (AN-IV), Y is independently one selected from the group of trivalent groups below,

Any hydrogen in these groups may be replaced by methyl, ethyl or phenyl;
In the formulas (AN-III) to (AN-V), the ring A is a monocyclic hydrocarbon group having 3 to 10 carbon atoms or a condensed polycyclic hydrocarbon group having 6 to 30 carbon atoms. Any hydrogen in may be replaced by methyl, ethyl or phenyl, and the bond on the ring is connected to any carbon constituting the ring, and the two bonds are connected to the same carbon May be;
In the formula (AN-VI), X ¹⁰ is alkylene having 2 to 6 carbons;
Me is methyl;
Ph is phenyl;
In formula (AN-VII), G ¹⁰ is independently —O—, —COO— or —OCO—; and
r is independently 0 or 1.

式（ＡＮ−４−１７）において、ｍは１〜１２の整数である。 [8] The tetracarboxylic dianhydride has the following formulas (AN-1-1), (AN-1-13), (AN-2-1), (AN-3-1), (AN-3- 2) at least one selected from the group consisting of (AN-4-5), (AN-4-17), (AN-7-2), (AN-10), and (AN-11-3) The polyamic acid or derivative thereof according to item [7]:

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

式（ＤＩ−１）〜（ＤＩ−７）において、ｍは１〜１２の整数であり；
Ｇ^２１は独立して単結合、−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−、または−Ｓ−（ＣＨ_２）_ｍ’−Ｓ−であり、ｍ’は独立して１〜１２の整数であり；
Ｇ^２２は独立して単結合、−Ｏ−、−Ｓ−、−ＣＯ−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−、または炭素数１〜１０のアルキレンであり；
各式中のシクロヘキサン環およびベンゼン環の任意の−Ｈは、−Ｆ、−ＣＨ_３、−ＯＨ、−ＣＦ_３またはベンジルで置き換えられていてもよく、加えて式（ＤＩ−４）においては、下記式（ＤＩ−４−ａ）〜（ＤＩ−４−ｃ）で置き換えられていてもよく、

式（ＤＩ−４−ａ）〜（ＤＩ−４−ｃ）において、Ｒ^２０は独立して−Ｈまたは−ＣＨ_３であり；
式（ＤＩ−２）〜（ＤＩ−７）において、環を構成するいずれかの炭素原子に結合位置が固定されていない基は、その環における結合位置が任意であることを示し；そして、
シクロヘキサン環またはベンゼン環への−ＮＨ_２の結合位置は、Ｇ^２１またはＧ^２２の結合位置を除く任意の位置である。

式（ＤＩ−８）において、Ｒ^２１およびＲ^２２は独立して炭素数１〜３のアルキルまたはフェニルであり；
Ｇ^２３は独立して炭素数１〜６のアルキレン、フェニレンまたはアルキル置換されたフェニレンであり；
ｎは１〜１０の整数であり；
式（ＤＩ−９）において、Ｒ^２３は独立して炭素数１〜３のアルキルであり；
ｐは独立して０〜３の整数であり；
ｑは０〜４の整数であり；
式（ＤＩ−１０）において、Ｒ^２４は−Ｈ、炭素数１〜４のアルキル、フェニル、またはベンジルであり；
式（ＤＩ−１１）において、Ｇ^２４は−ＣＨ_２−または−ＮＨ−であり；
式（ＤＩ−１２）において、Ｇ^２５は単結合、炭素数２〜６のアルキレンまたは１，４−フェニレンであり；
ｒは０または１であり；
式（ＤＩ−１２）において、環を構成するいずれかの炭素原子に結合位置が固定されていない基は、その環における結合位置が任意であることを示し；そして、
式（ＤＩ−９）、（ＤＩ−１１）および（ＤＩ−１２）において、ベンゼン環に結合する−ＮＨ_２の結合位置は任意の位置であり；

式（ＤＩ−１３）において、Ｇ^２６は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−、−ＣＯＮＨ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、または−（ＣＨ_２）_ｍ’−であり、ｍ’は１〜１２の整数であり；
Ｒ^２５は炭素数３〜２０のアルキル、フェニル、ステロイド骨格を有する基、または下記の式（ＤＩ−１３−ａ）で表される基であり、このアルキルにおいて、任意の−Ｈは−Ｆで置き換えられてもよく、任意の−ＣＨ_２−は−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられていてもよく、このフェニルの−Ｈは、−Ｆ、−ＣＨ_３、−ＯＣＨ_３、−ＯＣＨ_２Ｆ、−ＯＣＨＦ_２、−ＯＣＦ_３、炭素数３〜２０のアルキル、または炭素数３〜２０のアルコキシで置き換えられていてもよく、このシクロヘキシルの−Ｈは炭素数３〜２０のアルキルまたは炭素数３〜２０のアルコキシで置き換えられていてもよく、ベンゼン環に結合する−ＮＨ_２の結合位置はその環において任意の位置であることを示し；

式（ＤＩ−１３−ａ）において、Ｇ^２７、Ｇ^２８およびＧ^２９は結合基を表し、これらは独立して単結合、または炭素数１〜１２のアルキレンであり、このアルキレン中の１以上の−ＣＨ_２−は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＣＨ＝ＣＨ−で置き換えられていてもよく；
環Ｂ^２１、環Ｂ^２２、環Ｂ^２３、および環Ｂ^２４は独立して１，４−フェニレン、１，４−シクロへキシレン、１，３−ジオキサン−２，５−ジイル、ピリミジン−２，５−ジイル、ピリジン−２，５−ジイル、ナフタレン−１，４−ジイル、ナフタレン−１，５−ジイル、ナフタレン−２，６−ジイル、ナフタレン−２，７−ジイル、またはアントラセン−９，１０−ジイルであり；
環Ｂ^２１、環Ｂ^２２、環Ｂ^２３、および環Ｂ^２４において、任意の−Ｈは−Ｆまたは−ＣＨ_３で置き換えられてもよく；
ｓ，ｔおよびｕは独立して０〜２の整数であり、これらの合計は１〜５であり；
ｓ，ｔまたはｕが２であるとき、各々の括弧内の２つの結合基は同じであっても異なってもよく、２つの環は同じであっても異なっていてもよく；
Ｒ^２６は−Ｆ、−ＯＨ、炭素数１〜３０のアルキル、炭素数１〜３０のフッ素置換アルキル、炭素数１〜３０のアルコキシ、−ＣＮ、−ＯＣＨ_２Ｆ、−ＯＣＨＦ_２、または−ＯＣＦ_３であり、この炭素数１〜３０のアルキルの任意の−ＣＨ_２−は下記式（ＤＩ−１３−ｂ）で表される２価の基で置き換えられていてもよく；

式（ＤＩ−１３−ｂ）において、Ｒ^２７およびＲ^２８は独立して炭素数１〜３のアルキルであり；
ｖは１〜６の整数であり；

式（ＤＩ−１４）および式（ＤＩ−１５）において、Ｇ^３０は独立して単結合、−ＣＯ−または−ＣＨ₂−であり；
Ｒ^２９は独立して−Ｈまたは−ＣＨ_３であり；
Ｒ^３０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；
式（ＤＩ−１５）におけるベンゼン環の１つの−Ｈは、炭素数１〜２０のアルキルまたはフェニルで置き換えられてもよく；
式（ＤＩ−１４）および式（ＤＩ−１５）において、環を構成するいずれかの炭素原子に結合位置が固定されていない基は、その環における結合位置が任意であることを示し；
ベンゼン環に結合する−ＮＨ_２はその環における結合位置が任意であることを示し；

式（ＤＩ−１６）および式（ＤＩ−１７）において、Ｇ^３１は独立して−Ｏ−または炭素数１〜６のアルキレンであり；
Ｇ^３２は単結合または炭素数１〜３のアルキレンであり；
Ｒ^３１は−Ｈまたは炭素数１〜２０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；
Ｒ^３２は炭素数６〜２２のアルキルであり；
Ｒ^３３は−Ｈまたは炭素数１〜２２のアルキルであり；
環Ｂ^２５は１，４−フェニレンまたは１，４−シクロヘキシレンであり；
ｒは０または１であり；そして、
ベンゼン環に結合する−ＮＨ_２はその環における結合位置が任意であることを示す。 [9] The polyamic acid or derivative thereof according to item [6], wherein the other diamine is at least one selected from the group consisting of the following formulas (DI-1) to (DI-17):

In formulas (DI-1) to (DI-7), m is an integer of 1 to 12;
G ²¹ is independently 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—, or —S— (CH ₂ ) _{m ′} —S—, and m ′ is independent. An integer from 1 to 12;
G ²² is independently a single bond, —O—, —S—, —CO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, or alkylene having 1 to 10 carbons;
Arbitrary —H of the cyclohexane ring and the benzene ring in each formula may be replaced by —F, —CH ₃ , —OH, —CF ₃ or benzyl. In addition, in the formula (DI-4), The following formulas (DI-4-a) to (DI-4-c) may be substituted,

In formulas (DI-4-a) to (DI-4-c), R ²⁰ is independently —H or —CH ₃ ;
In formulas (DI-2) to (DI-7), a group whose bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary; and
The bonding position of —NH ₂ to the cyclohexane ring or the benzene ring is an arbitrary position excluding the bonding position of G ²¹ or G ²² .

In formula (DI-8), R ²¹ and R ²² are each independently alkyl or phenyl having 1 to 3 carbon atoms;
G ²³ is independently alkylene having 1 to 6 carbons, phenylene or alkyl-substituted phenylene;
n is an integer from 1 to 10;
In formula (DI-9), R ²³ is independently alkyl having 1 to 3 carbons;
p is independently an integer from 0 to 3;
q is an integer from 0 to 4;
In the formula (DI-10), R ²⁴ is —H, alkyl having 1 to 4 carbons, phenyl, or benzyl;
In the formula (DI-11), G ²⁴ is —CH ₂ — or —NH—;
In the formula (DI-12), G ²⁵ is a single bond, alkylene having 2 to 6 carbons or 1,4-phenylene;
r is 0 or 1;
In formula (DI-12), a group whose bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary; and
In formulas (DI-9), (DI-11) and (DI-12), the bonding position of —NH ₂ bonded to the benzene ring is an arbitrary position;

In the formula (DI-13), G ²⁶ represents a single bond, —O—, —COO—, —OCO—, —CO—, —CONH—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—. , -OCF ₂ -, or - _(CH 2) _{m '-} it is and, m' is an integer from 1 to 12;
R ²⁵ is alkyl having 3 to 20 carbon atoms, phenyl, a group having a steroid skeleton, or a group represented by the following formula (DI-13-a). In this alkyl, any —H is —F. Any —CH ₂ — may be replaced by —O—, —CH═CH— or —C≡C—, and —H of this phenyl is —F, —CH ₃ , _{-OCH 3, -OCH 2 F, -OCHF} 2, -OCF 3, alkyl having 3 to 20 carbon atoms, or may be replaced by alkoxy having 3 to 20 carbon atoms, -H of cyclohexyl 3 carbon atoms Which may be substituted with ˜20 alkyl or C 3-20 alkoxy, and indicates that the bonding position of —NH ₂ bonded to the benzene ring is an arbitrary position in the ring;

In the formula (DI-13-a), G ²⁷ , G ²⁸ and G ²⁹ each represent a bonding group, and these are each independently a single bond or alkylene having 1 to 12 carbons, and one or more of the alkylene —CH ₂ — may be replaced by —O—, —COO—, —OCO—, —CONH—, —CH═CH—;
Ring B ²¹ , Ring B ²² , Ring B ²³ , and Ring B ²⁴ are independently 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2, 5-diyl, pyridine-2,5-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, or anthracene-9,10 -Diyl;
In ring B ²¹ , ring B ²² , ring B ²³ , and ring B ²⁴ , any —H may be replaced by —F or —CH ₃ ;
s, t and u are independently integers from 0 to 2 and their sum is 1 to 5;
when s, t or u is 2, the two linking groups in each bracket may be the same or different and the two rings may be the same or different;
R ²⁶ represents —F, —OH, alkyl having 1 to 30 carbon atoms, fluorine-substituted alkyl having 1 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms, —CN, —OCH ₂ F, —OCHF ₂ , or —OCF. _And any —CH ₂ — in the alkyl having 1 to 30 carbon atoms may be replaced by a divalent group represented by the following formula (DI-13-b);

In the formula (DI-13-b), R ²⁷ and R ²⁸ are independently alkyl having 1 to 3 carbons;
v is an integer from 1 to 6;

In formula (DI-14) and formula (DI-15), G ³⁰ is independently a single bond, —CO— or —CH ₂ —;
R ²⁹ is independently —H or —CH ₃ ;
R ³⁰ is —H, alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons;
One -H of the benzene ring in formula (DI-15) may be replaced by alkyl having 1 to 20 carbons or phenyl;
In formula (DI-14) and formula (DI-15), a group whose bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary;
Bonded to the benzene ring -NH ₂ indicates that the binding position in the ring is optional;

In formula (DI-16) and formula (DI-17), G ³¹ is independently —O— or alkylene having 1 to 6 carbons;
G ³² is a single bond or alkylene having 1 to 3 carbon atoms;
R ³¹ is —H or alkyl having 1 to 20 carbons, and any —CH ₂ — in the alkyl may be replaced by —O—, —CH═CH— or —C≡C—;
R ³² is alkyl having 6 to 22 carbons;
R ³³ is —H or C 1-22 alkyl;
Ring B ²⁵ is 1,4-phenylene or 1,4-cyclohexylene;
r is 0 or 1; and
-NH ₂ bonded to the benzene ring indicates that the binding position in the ring is optional.

式（ＤＩ−５−１）、（ＤＩ−５−１２）および（ＤＩ−７−３）において、ｍは１〜１２の整数であり；
式（ＤＩ−５−２９）において、ｋは１〜５の整数であり；
式（ＤＩ−７−３）において、ｎは１または２あり；
式（ＤＩ−１３−４）および（ＤＩ−１３−５）において、Ｒ^３５は炭素数１〜３０のアルキルまたは炭素数１〜３０のアルコキシであり；
式（ＤＩ−１６−１）および（ＤＩ−１６−２）において、Ｒ^４０は−Ｈまたは炭素数１〜２０のアルキルであり；
式（ＤＩ−１６−４）において、Ｒ^４１は−Ｈまたは炭素数１〜１２のアルキルである。 [10] Other diamines are represented by the following formulas (DI-4-1), (DI-5-1), (DI-5-5), (DI-5-9), (DI-5-12). , (DI-5-21), (DI-5-27), (DI-5-29), (DI-7-3), (DI-9-1), (DI-13-4), ( DI-13-5), (DI-13-47), (DI-16-1), (DI-16-2), and (DI-16-4) are at least one selected from the group consisting of The polyamic acid or derivative thereof according to item [9]:

In the formulas (DI-5-1), (DI-5-12) and (DI-7-3), m is an integer of 1 to 12;
In the formula (DI-5-29), k is an integer of 1 to 5;
In the formula (DI-7-3), n is 1 or 2;
In formulas (DI-13-4) and (DI-13-5), R ³⁵ is alkyl having 1 to 30 carbons or alkoxy having 1 to 30 carbons;
In the formulas (DI-16-1) and (DI-16-2), R ⁴⁰ is —H or alkyl having 1 to 20 carbons;
In the formula (DI-16-4), R ⁴¹ represents —H or alkyl having 1 to 12 carbons.

[11] A varnish containing at least one polymer selected from the polyamic acid according to any one of [5] to [10] or a derivative thereof.

[12] A liquid crystal aligning agent containing the varnish according to the item [11].

[13] The item [12] further contains at least one selected from the group consisting of alkenyl-substituted nadiimide compounds, compounds having a radical polymerizable unsaturated double bond, oxazine compounds, oxazoline compounds, and epoxy compounds. The liquid crystal aligning agent of description.

[14] The alkenyl-substituted nadiimide compound is bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) phenyl} methane, N, N′-m-xylylene- Bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) and N, N′-hexamethylene-bis (allylbicyclo [2.2.1] hept-5- The liquid crystal aligning agent according to item [13], which is at least one selected from the group of compounds consisting of ene-2,3-dicarboximide).

[15] Compounds having radically polymerizable unsaturated double bonds are N, N′-ethylenebisacrylamide, N, N ′-(1,2-dihydroxyethylene) bisacrylamide, ethylenebisacrylate, and 4,4 ′. The liquid crystal aligning agent as described in the item [13], which is at least one selected from the group of compounds consisting of methylene bis (N, N-dihydroxyethylene acrylate aniline).

[16] The epoxy compound is N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N '-Tetraglycidyl-4,4'-diaminodiphenylmethane, 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3-epoxy] Propoxy] phenyl)] ethyl] phenyl] propane, 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate, N-phenylmaleimide-glycidyl methacrylate copolymer, and 2- (3,4- Item [13], which is at least one selected from the group of compounds consisting of (epoxycyclohexyl) ethyltrimethoxysilane. The liquid crystal alignment agent.

[17] A liquid crystal alignment film formed by the liquid crystal aligning agent according to any one of [12] to [16].

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

[19] A polyamic acid or a derivative thereof having a group that generates an —NH— group by heating to 100 to 300 ° C. is baked to a temperature that generates an —NH— group by the group elimination, and then liquid crystal alignment A method for forming a liquid crystal alignment film, characterized by being used as a film.

[20] The method for forming a liquid crystal alignment film according to the item [19], wherein the liquid crystal aligning agent according to any one of the items [12] to [16] is used.

[21] A method for producing a liquid crystal display element, comprising forming a liquid crystal alignment film by the method according to the item [19] or [20].

By using the diamine compound of the present invention as a part of the raw materials of polyamic acid and its derivatives used for the liquid crystal aligning agent, liquid crystal alignment with high liquid crystal alignment, low volume resistance, and good electrical characteristics such as VHR A liquid crystal aligning agent that forms a film can be obtained. The liquid crystal aligning agent can be easily synthesized without causing gelation.

It is a conceptual diagram of the volume resistance value measurement of alignment film.

式（１）において、Ｒ^１は熱により脱離する基であり、Ｒ^２は独立して−Ｈ、熱により脱離する基または熱により脱離する基を有する基である。Ｇ^１およびＧ^４は独立して芳香環を有する２価の有機基である。Ｇ^２は単結合または炭素数１〜１０のアルキレンである。Ｇ^３は単結合、−Ｏ−、−ＣＯＮＨ−、−ＮＭｅ−、または−ＮＲ^１−である。ａ、ｂおよびｃは独立して０または１であるが、Ｒ^２が−Ｈであるときｂは１であり、そして、ａ、ｃそれぞれが１であるとき、−ＮＨ_２は２価の有機基の芳香環に直接結合している。 The diamine of the present invention will be described.
The diamine of the present invention is a diamine having a primary or secondary amino group represented by formula (1) and protected with a group capable of leaving by heat in the molecule.

In the formula (1), R ¹ is a group capable of leaving by heat, and R ² is independently a group having —H, a group leaving by heat or a group leaving by heat. G ¹ and G ⁴ are independently a divalent organic group having an aromatic ring. G ² is a single bond or alkylene having 1 to 10 carbon atoms. G ³ is a single bond, —O—, —CONH—, —NMe—, or —NR ¹ —. a, b and c are independently 0 or 1, but b is 1 when R ² is —H, and —NH ₂ is a divalent organic when each of a, c is 1. It is directly bonded to the aromatic ring of the group.

In general, amines have high nucleophilic ability and are highly reactive. Therefore, for example, when the amino group of a compound having a secondary amine structure in the molecule other than the amino group at the end of the molecule is chemically reacted (in the present invention, amidation) as in the above formula (DI-B). In some cases, the secondary amine described above is protected in advance using an electron-withdrawing functional group. Such a functional group is referred to as a protecting group, and carbamate-based protecting groups, amide-based protecting groups, imide-based protecting groups and the like are known as amino-protecting groups. Of these, carbamate-based protecting groups can be preferably used as the group capable of leaving by heat used in the present invention. The calcination temperature at the time of forming the liquid crystal alignment film is 150 ° C. to 300 ° C. The protective groups that undergo elimination under these conditions include t-butoxycarbonyl group (Boc), 1,1-dimethyl-2-haloethyloxy Examples include carbonyl group, 1,1-dimethyl-2-cyanoethyloxycarbonyl group, 9-fluorenylmethyloxycarbonyl group and the like. Among them, the t-butoxycarbonyl group (Boc) can be particularly preferably used because it is easily eliminated.

By using a liquid crystal aligning agent containing a polyamic acid and a derivative thereof using the diamine compound of the present invention as one of raw materials, a liquid crystal display element satisfying the above required characteristics can be obtained. At this time, the compounds represented by the formulas (1-a) to (1-d) can be suitably used as diamine raw materials that have particularly high liquid crystal orientation and can be easily and inexpensively synthesized.

Among the compounds represented by the formulas (1-a) to (1-d), particularly preferred examples include the compounds of the following formulas (1-a-1) to (1-d-5). It is done.

The polyamic acid and derivatives thereof of the present invention will be described.
The polyamic acid and its derivative of the present invention are a reaction product of tetracarboxylic dianhydride and a diamine containing a diamine represented by the formula (1). The polyamic acid derivative is a component that dissolves in a solvent when the liquid crystal aligning agent described later containing a solvent is used. When the liquid crystal aligning agent is used as a liquid crystal aligning film, the liquid crystal alignment is mainly composed of polyimide. It is a component that can form a film. Examples of such a derivative of polyamic acid include soluble polyimide, polyamic acid ester, polyamic acid amide, and the like. More specifically, 1) polyimide in which all amino acids and carboxyl of polyamic acid are subjected to a dehydration ring-closing reaction, 2) Partially dehydrated ring-closing partial polyimide, 3) Polyamic acid ester in which carboxyl of polyamic acid is converted to ester, 4) Part of acid dianhydride contained in tetracarboxylic dianhydride compound is organic dicarboxylic Examples thereof include polyamic acid-polyamide copolymers obtained by reacting with an acid, and 5) polyamideimide obtained by subjecting a part or all of the polyamic acid-polyamide copolymer to a dehydration ring-closing reaction. The polyamic acid and the derivative thereof may be one kind of compound or two or more kinds. The polyamic acid and its derivative may be a compound having a structure of a reaction product of tetracarboxylic dianhydride and diamine, and other raw materials may be used except for the reaction of tetracarboxylic dianhydride and diamine. It may contain reaction products from other reactions.

The tetracarboxylic dianhydride used for producing the polyamic acid and derivatives thereof of the present invention will be described.
The tetracarboxylic dianhydride used in the present invention can be selected without limitation from known tetracarboxylic dianhydrides. Such tetracarboxylic dianhydrides include aromatic systems (including heteroaromatic ring systems) in which dicarboxylic acid anhydrides are directly bonded to aromatic rings, and aliphatic groups in which dicarboxylic acid anhydrides are not directly bonded to aromatic rings. It may belong to any group of systems (including heterocyclic ring systems).

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

式（ＡＮ−ＩＩＩ）〜（ＡＮ−Ｖ）において、環Ａは炭素数３〜１０の単環式炭化水素の基または炭素数６〜３０の縮合多環式炭化水素の基であり、この基の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−ＶＩ）において、Ｘ^１０は炭素数２〜６のアルキレンであり、Ｍｅはメチルであり、そして、Ｐｈはフェニルであり、式（ＡＮ−ＶＩＩ）において、Ｇ^１０は独立して−Ｏ−、−ＣＯＯ−または−ＯＣＯ−であり、ｒは独立して０または１である。 Preferred examples of such tetracarboxylic dianhydrides include those represented by the formulas (AN-I) to (AN-VII) from the viewpoint of easy availability of raw materials, ease of polymer polymerization, and electrical characteristics of the film. The tetracarboxylic dianhydride represented is mentioned.

In the formulas (AN-I), (AN-IV) and (AN-V), X is independently a single bond or —CH ₂ —, and in the formula (AN-II), G is a single bond, the number of carbon atoms 1-20 alkylene, —CO—, —O—, —S—, —SO ₂ —, —C (CH ₃ ) ₂ —, or —C (CF ₃ ) ₂ —, and having the formula (AN-II) In (AN-IV), Y is independently one selected from the group of the following trivalent groups, the bond is connected to any carbon, and any hydrogen in this group is methyl, May be replaced by ethyl or phenyl,

In the formulas (AN-III) to (AN-V), the ring A is a monocyclic hydrocarbon group having 3 to 10 carbon atoms or a condensed polycyclic hydrocarbon group having 6 to 30 carbon atoms. Any hydrogen in may be replaced by methyl, ethyl or phenyl, and the bond on the ring is connected to any carbon constituting the ring, and the two bonds are connected to the same carbon In formula (AN-VI), X ¹⁰ is alkylene having 2 to 6 carbon atoms, Me is methyl, and Ph is phenyl, and in formula (AN-VII), G ¹⁰ Is independently —O—, —COO— or —OCO—, and r is independently 0 or 1.

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

式（ＡＮ−１）において、Ｇ^１１は単結合、炭素数１〜１２のアルキレン、１，４−フェニレン、または１，４−シクロヘキシレンである。Ｘ^１１は独立して単結合または−ＣＨ_２−である。Ｇ^１２は独立してＣＨまたはＮである。Ｇ^１２がＣＨであるとき、ＣＨの水素は−ＣＨ_３に置き換えられてもよい。Ｇ^１２がＮであるとき、Ｇ^１１が単結合および−ＣＨ_２−であることはなく、Ｘ^１１は単結合であることはない。そしてＲ^１１は−Ｈまたは−ＣＨ_３である。式（ＡＮ−１）で表されるテトラカルボン酸二無水物の例としては、下記の式で表される化合物を挙げることができる。

式（ＡＮ−１−２）および（ＡＮ−１−１４）において、ｍは1〜１２の整数である。

In the formula (AN-1), G ¹¹ is a single bond, alkylene having 1 to 12 carbons, 1,4-phenylene, or 1,4-cyclohexylene. X ¹¹ is independently a single bond or —CH ₂ —. G ¹² is independently CH or N. When G ¹² is CH, the hydrogen of CH may be replaced with —CH ₃ . When G ¹² is N, G ¹¹ is not a single bond and —CH ₂ —, and X ¹¹ is not a single bond. R ¹¹ is —H or —CH ₃ . Examples of the tetracarboxylic dianhydride represented by the formula (AN-1) include compounds represented by the following formula.

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

式（ＡＮ−２）において、Ｒ^１２は独立して−Ｈ、−ＣＨ_３、−ＣＨ_２ＣＨ_３、またはフェニルである。式（ＡＮ−２）で表されるテトラカルボン酸二無水物の例としては、下記の式で表される化合物を挙げることができる。

In formula (AN-2), R ¹² is independently —H, —CH ₃ , —CH ₂ CH ₃ , or phenyl. Examples of the tetracarboxylic dianhydride represented by the formula (AN-2) include compounds represented by the following formula.

式（ＡＮ−３）において、環Ａ^１１はシクロヘキサン環もしくはベンゼン環である。式（ＡＮ−３）で表されるテトラカルボン酸二無水物の例としては、下記の式で表される化合物を挙げることができる。

In the formula (AN-3), the ring A ¹¹ is a cyclohexane ring or a benzene ring. Examples of the tetracarboxylic dianhydride represented by the formula (AN-3) include compounds represented by the following formula.

式（ＡＮ−４）において、Ｇ^１３は単結合、−ＣＨ_２−、−ＣＨ_２ＣＨ_２−、−Ｏ−、−Ｓ−、−Ｃ（ＣＨ_３）_２−、−ＳＯ_２−、−ＣＯ−または−Ｃ（ＣＦ_３）_２−である。環Ａ^１１はそれぞれ独立してシクロヘキサン環またはベンゼン環である。Ｇ^１３は環Ａ^１１の任意の位置に結合してよい。式（ＡＮ−４）で表されるテトラカルボン酸二無水物の例としては、下記の式で表される化合物を挙げることができる。

式（ＡＮ−４−１７）において、ｍは１〜１２の整数である。

In the formula ^{(AN-4), G 13} represents a single _{bond, -CH 2 -, - CH 2} CH 2 -, - O -, - S -, - C (CH 3) 2 -, - SO 2 -, - CO - or -C _{(CF 3) 2} - a. Each ring A ¹¹ is independently a cyclohexane ring or a benzene ring. G ¹³ may be bonded to any position of ring A ¹¹ . Examples of the tetracarboxylic dianhydride represented by the formula (AN-4) include compounds represented by the following formula.

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

式（ＡＮ−５）において、Ｒ^１１は−Ｈ、または−ＣＨ_３である。ベンゼン環を構成する炭素原子に結合位置が固定されていないＲ^１１は、ベンゼン環における結合位置が任意であることを示す。式（ＡＮ−５）で表されるテトラカルボン酸二無水物の例としては、下記の式で表される化合物を挙げることができる。

In the formula (AN-5), R ¹¹ is —H or —CH ₃ . R ¹¹ whose bond position is not fixed to the carbon atom constituting the benzene ring indicates that the bond position in the benzene ring is arbitrary. Examples of the tetracarboxylic dianhydride represented by the formula (AN-5) include compounds represented by the following formula.

式（ＡＮ−６）において、Ｘ^１１は独立して単結合または−ＣＨ_２−である。Ｘ^１２は−ＣＨ_２−、−ＣＨ_２ＣＨ_２−または−ＣＨ＝ＣＨ−である。ｎは１または２である。式（ＡＮ−６）で表されるテトラカルボン酸二無水物の例としては、下記の式で表される化合物を挙げることができる。

In the formula (AN-6), X ¹¹ is independently a single bond or —CH ₂ —. X ¹² is _{-CH 2 -, - CH 2 CH} 2 - or -CH = CH-. n is 1 or 2. Examples of the tetracarboxylic dianhydride represented by the formula (AN-6) include compounds represented by the following formula.

式（ＡＮ−７）において、Ｘ^１１は単結合または−ＣＨ_２−である。式（ＡＮ−７）で表されるテトラカルボン酸二無水物の例としては、下記の式で表される化合物を挙げることができる。

In the formula (AN-7), X ¹¹ is a single bond or —CH ₂ —. Examples of the tetracarboxylic dianhydride represented by the formula (AN-7) include compounds represented by the following formula.

式（ＡＮ−８）において、Ｘ^１１はそれぞれ独立して単結合または−ＣＨ_２−である。Ｒ^１２は−Ｈ、−ＣＨ_３、−ＣＨ_２ＣＨ_３、またはフェニルであり、環Ａ^１２はシクロヘキサン環もしくはシクロヘキセン環である。式（ＡＮ−８）で表されるテトラカルボン酸二無水物の例としては、下記の式で表される化合物を挙げることができる。

In formula (AN-8), X ¹¹ each independently represents a single bond or —CH ₂ —. R ¹² is —H, —CH ₃ , —CH ₂ CH ₃ , or phenyl, and ring A ¹² is a cyclohexane ring or a cyclohexene ring. Examples of the tetracarboxylic dianhydride represented by the formula (AN-8) include compounds represented by the following formula.

式（ＡＮ−９）において、ｒはそれぞれ独立して０または１である。式（ＡＮ−９）で表されるテトラカルボン酸二無水物の例としては、下記の式で表される化合物を挙げることができる。

In the formula (AN-9), each r is independently 0 or 1. Examples of the tetracarboxylic dianhydride represented by the formula (AN-9) include compounds represented by the following formula.

式（ＡＮ−１０）は下記のテトラカルボン酸二無水物である。

Formula (AN-10) is the following tetracarboxylic dianhydride.

式（ＡＮ−１１）において、環Ａ^１１は独立してシクロヘキサン環またはベンゼン環である。式（ＡＮ−１１）で表されるテトラカルボン酸二無水物の例としては、下記の式で表される化合物を挙げることができる。

In the formula (AN-11), ring A ¹¹ is independently a cyclohexane ring or a benzene ring. Examples of the tetracarboxylic dianhydride represented by the formula (AN-11) include compounds represented by the following formula.

式（ＡＮ−１２）において、環Ａ^１１はそれぞれ独立してシクロヘキサン環またはベンゼン環である。式（ＡＮ−１２）で表されるテトラカルボン酸二無水物の例としては、下記の式で表される化合物を挙げることができる。

In formula (AN-12), each of ring A ¹¹ is independently a cyclohexane ring or a benzene ring. As an example of the tetracarboxylic dianhydride represented by a formula (AN-12), the compound represented by a following formula can be mentioned.

式（ＡＮ−１３）において、Ｘ^１３は炭素数２〜６のアルキレンである。式（ＡＮ−１３）で表されるテトラカルボン酸二無水物の例としては、下記の式で表される化合物を挙げることができる。

In the formula (AN-13), X ¹³ is alkylene having 2 to 6 carbons. Examples of the tetracarboxylic dianhydride represented by the formula (AN-13) include compounds represented by the following formula.

式（ＡＮ−１４）において、Ｇ^１４は独立して−Ｏ−、−ＣＯＯ−または−ＯＣＯ−であり、ｒは独立して０または１である。式（ＡＮ−１４）で表されるテトラカルボン酸二無水物の例としては、下記の式で表される化合物を挙げることができる。

In the formula (AN-14), G ¹⁴ is independently —O—, —COO— or —OCO—, and r is independently 0 or 1. Examples of the tetracarboxylic dianhydride represented by the formula (AN-14) include compounds represented by the following formula.

式（ＡＮ−１５）において、ｗは１〜１０の整数である。式（ＡＮ−１５）で表されるテトラカルボン酸二無水物の例としては、下記の式で表される化合物を挙げることができる。

In formula (AN-15), w is an integer of 1-10. Examples of the tetracarboxylic dianhydride represented by the formula (AN-15) include compounds represented by the following formula.

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

When importance is attached to further improving the orientation of the liquid crystal, among the above acid anhydrides, the formulas (AN-1-1), (AN-1-3), (AN-1-13), ( AN-2-1), (AN-3-1), (AN-3-2), (AN-4-5), (AN-4-17), (AN-5-1), (AN- 7-2), (AN-8-1), (AN-11-3), (AN-16-3), and compounds represented by (AN-16-14) are more preferable. The compound represented by 1-1), (AN-1-13), (AN-3-2), (AN-11-3), and (AN-16-14) is particularly preferable.

In the case where emphasis is placed on improving the VHR of the liquid crystal display element, among the above acid anhydrides, the formulas (AN-1-1), (AN-1-4), (AN-2-1), ( AN-3-1), (AN-5-1), (AN-6-3), (AN-7-1), (AN-7-2), (AN-8-1), (AN- 8-2), (AN-9-3), (AN-10), (AN-13-1), (AN-16-3), and (AN-16-4) alicyclic More preferred are compounds of formulas (AN-1-4), (AN-2-1), (AN-3-1), (AN-7-2), (AN-10), and (AN-13). The compound represented by 1) is particularly preferred.

The diamine used for producing the polyamic acid and derivatives thereof of the present invention will be described.
The polyamic acid and derivatives thereof of the present invention are characterized by using a diamine represented by the formula (1) as one of the raw materials. The diamine represented by formula (1) may be used alone or as a mixture of two or more diamines represented by formula (1). Furthermore, a mixture of at least one diamine represented by the formula (1) and at least one other diamine may be used.

In the polyamic acid and the derivative thereof of the present invention, in order to develop high liquid crystal alignment characteristics and reduce RDC, the copolymerization ratio of the diamine raw material represented by the formula (1) is 5 to 100 mol% with respect to the total amine component. Is preferable, and 10 to 100 mol% is more preferable.

Other diamine compounds used for producing the polyamic acid and derivatives thereof of the present invention can be selected without limitation from known diamine compounds.

Here, the structure of the diamine compound will be described. Diamine compounds can be divided into two types according to their structures. 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. 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. 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.

By properly using the non-side chain diamine and the side chain diamine, it is possible to cope with the pretilt angle required for each. The side chain diamine is preferably used in combination so as not to impair the properties of the present invention. The side chain diamine and the non-side chain diamine are preferably selected and used for the purpose of improving the vertical alignment with respect to the liquid crystal, the voltage holding ratio, the image sticking property, and the photo alignment.

上記の式（ＤＩ−１）〜（ＤＩ−７）において、ｍは１〜１２の整数である。Ｇ^２１は独立して単結合、−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−、または−Ｓ−（ＣＨ_２）_ｍ’−Ｓ−であり、ｍ’は独立して１〜１２の整数である。Ｇ^２２は独立して単結合、−Ｏ−、−Ｓ−、−ＣＯ−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−、または炭素数１〜１０のアルキレンである。各式中のシクロヘキサン環およびベンゼン環の任意の−Ｈは、−Ｆ、−ＣＨ_３、−ＯＨ、−ＣＦ_３またはベンジルで置き換えられてもよく、加えて式（ＤＩ−４）においては、下記式（ＤＩ−４−ａ）〜（ＤＩ−４−ｃ）で置き換えられていてもよい。環を構成する炭素原子に結合位置が固定されていない基は、その環における結合位置が任意であることを示す。そして、シクロヘキサン環またはベンゼン環への−ＮＨ_２の結合位置は、Ｇ^２１またはＧ^２２の結合位置を除く任意の位置である。

式（ＤＩ−４−ａ）〜（ＤＩ−４−ｃ）において、Ｒ^２０は独立して−Ｈまたは−ＣＨ_３である。 The non-side chain diamine will be described.
Examples of diamines having no known side chain include diamines of the following formulas (DI-1) to (DI-12).

In said formula (DI-1)-(DI-7), m is an integer of 1-12. G ²¹ is independently 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—, or —S— (CH ₂ ) _{m ′} —S—, and m ′ is independent. And an integer of 1 to 12. G ²² is independently a single bond, —O—, —S—, —CO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, or alkylene having 1 to 10 carbon atoms. Arbitrary —H of the cyclohexane ring and the benzene ring in each formula may be replaced with —F, —CH ₃ , —OH, —CF ₃ or benzyl. In addition, in formula (DI-4), The formulas (DI-4-a) to (DI-4-c) may be substituted. A group in which the bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary. The bonding position of —NH ₂ to the cyclohexane ring or the benzene ring is an arbitrary position excluding the bonding position of G ²¹ or G ²² .

In formulas (DI-4-a) to (DI-4-c), R ²⁰ is independently —H or —CH ₃ .

式（ＤＩ−８）において、Ｒ^２１およびＲ^２２は独立して炭素数１〜３のアルキルまたはフェニルであり、Ｇ^２３は独立して炭素数１〜６のアルキレン、フェニレンまたはアルキル置換されたフェニレンであり、ｗは１〜１０の整数である。
式（ＤＩ−９）において、Ｒ^２３は独立して炭素数１〜３のアルキルであり、ｐは独立して０〜３の整数であり、ｑは０〜４の整数である。
式（ＤＩ−１０）において、Ｒ^２４は−Ｈ、炭素数１〜４のアルキル、フェニル、またはベンジルである。
式（ＤＩ−１１）において、Ｇ^２４は−ＣＨ_２−または−ＮＨ−である。
式（ＤＩ−１２）において、Ｇ^２５は単結合、炭素数２〜６のアルキレンまたは１，４−フェニレンであり、ｒは０または１である。そして、環を構成する炭素原子に結合位置が固定されていない基は、その環における結合位置が任意であることを示す。
式（ＤＩ−９）、式（ＤＩ−１１）および式（ＤＩ−１２）において、ベンゼン環に結合する−ＮＨ_２の結合位置は、任意の位置である。

In formula (DI-8), R ²¹ and R ²² are independently alkyl or phenyl having 1 to 3 carbon atoms, and G ²³ is independently alkylene, phenylene or alkyl-substituted phenylene having 1 to 6 carbon atoms. And w is an integer of 1-10.
In the formula (DI-9), R ²³ is independently alkyl having 1 to 3 carbon atoms, p is independently an integer of 0 to 3, and q is an integer of 0 to 4.
In the formula (DI-10), R ²⁴ is —H, alkyl having 1 to 4 carbons, phenyl, or benzyl.
In the formula (DI-11), G ²⁴ represents —CH ₂ — or —NH—.
In the formula (DI-12), G ²⁵ is a single bond, alkylene having 2 to 6 carbon atoms or 1,4-phenylene, and r is 0 or 1. A group whose bond position is not fixed to the carbon atoms constituting the ring indicates that the bond position in the ring is arbitrary.
In Formula (DI-9), Formula (DI-11), and Formula (DI-12), the bonding position of —NH ₂ bonded to the benzene ring is an arbitrary position.

Specific examples of the following formulas (DI-1-1) to (DI-12-1) can be given as diamines having no side chain of the above formulas (DI-1) to (DI-12).

Examples of diamines represented by formulas (DI-1) to (DI-3) are shown below.

Examples of the diamine represented by the formula (DI-4) are shown below.

式（ＤＩ−５−１）において、ｍは１〜１２の整数である。

式（ＤＩ−５−１２）において、ｍは１〜１２の整数である。

式（ＤＩ−５−１５）において、ｖは１〜６の整数である。

式（ＤＩ−５−２９）において、ｋは１〜５の整数である。 Examples of the diamine represented by the formula (DI-5) are shown below.

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

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

In the formula (DI-5-15), v is an integer of 1 to 6.

In the formula (DI-5-29), k is an integer of 1 to 5.

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

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

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

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

Examples of the diamine represented by the formula (DI-8) are shown below.

Examples of the diamine represented by the formula (DI-9) are shown below.

Examples of the diamine represented by the formula (DI-10) are shown below.

Examples of the diamine represented by the formula (DI-11) are shown below.

Examples of the diamine represented by the formula (DI-12) are shown below.

Such a non-side chain diamine has an effect of improving electrical characteristics, such as reducing the ion density of the liquid crystal display element. When a non-side chain diamine is used as the diamine used for producing the polyamic acid or polyimide used in the liquid crystal aligning agent of the present invention, the proportion of the total amount of the diamine is preferably 0 to 95 mol%. It is more preferable to set it to -90 mol%.

The side chain type diamine will be described.
Examples of the side chain group of the side chain diamine include the following groups.

As a side group, first, alkyl, alkyloxy, alkyloxyalkyl, alkylcarbonyl, alkylcarbonyloxy, alkyloxycarbonyl, 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 alkyloxyalkyl, it is sufficient if the entire group has 3 or more carbon atoms. 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,.

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-, or alkylene having 1 to 3 carbon atoms, the terminal ring is alkyl having 1 or more carbon atoms as a substituent, fluorine-substituted alkyl having 1 or more carbon atoms, carbon A ring assembly group having an alkoxy of several or more or an alkoxyalkyl having two or more carbons can be given. A group having a steroid skeleton is also effective as a side chain group.

式（ＤＩ−１３）において、Ｇ^２６は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−、−ＣＯＮＨ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、または−（ＣＨ_２）_ｍ’−であり、ｍ’は１〜１２の整数である。Ｇ^２６の好ましい例は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ_２Ｏ−、および炭素数１〜３のアルキレンであり、特に好ましい例は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ_２Ｏ−、−ＣＨ_２−および−ＣＨ_２ＣＨ_２−である。Ｒ^２５は炭素数３〜３０のアルキル、フェニル、ステロイド骨格を有する基、または下記の式（ＤＩ−１３−ａ）で表される基である。このアルキルにおいて、任意の−Ｈは−Ｆで置き換えられてもよく、そして任意の−ＣＨ₂−は−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられていてもよい。このフェニルの−Ｈは、−Ｆ、−ＣＨ_３、−ＯＣＨ_３、−ＯＣＨ_２Ｆ、−ＯＣＨＦ_２、−ＯＣＦ_３、炭素数３〜３０のアルキルまたは炭素数３〜３０のアルコキシで置き換えられていてもよく、このシクロヘキシルの−Ｈは炭素数３〜３０のアルキルまたは炭素数３〜３０のアルコキシで置き換えられていてもよい。ベンゼン環に結合する−ＮＨ_２の結合位置はその環において任意の位置であることを示すが、その結合位置はメタまたはパラであることが好ましい。即ち、基「Ｒ^２５−Ｇ^２４−」の結合位置を１位としたとき、２つの結合位置は３位と５位、または２位と５位であることが好ましい。

式（ＤＩ−１３−ａ）において、Ｇ^２７、Ｇ^２８およびＧ^２９は結合基であり、これらは独立して単結合、または炭素数１〜１２のアルキレンであり、このアルキレン中の１以上の−ＣＨ_２−は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＣＨ＝ＣＨ−で置き換えられていてもよい。環Ｂ^２１、環Ｂ^２２、環Ｂ^２３および環Ｂ^２４は独立して１，４−フェニレン、１，４−シクロへキシレン、１，３−ジオキサン−２，５−ジイル、ピリミジン−２，５−ジイル、ピリジン−２，５−ジイル、ナフタレン−１，５−ジイル、ナフタレン−２，７−ジイルまたはアントラセン−９，１０−ジイルであり、環Ｂ^２１、環Ｂ^２２、環Ｂ^２３および環Ｂ^２４において、任意の−Ｈは−Ｆまたは−ＣＨ_３で置き換えられてもよく、ｓ、ｔおよびｕは独立して０〜２の整数であって、これらの合計は１〜５であり、ｓ、ｔまたはｕが２であるとき、各々の括弧内の２つの結合基は同じであっても異なってもよく、そして、２つの環は同じであっても異なっていてもよい。Ｒ^２６は−Ｆ、−ＯＨ、炭素数１〜３０のアルキル、炭素数１〜３０のフッ素置換アルキル、炭素数１〜３０のアルコキシ、−ＣＮ、−ＯＣＨ_２Ｆ、−ＯＣＨＦ_２、または−ＯＣＦ_３であり、この炭素数１〜３０のアルキルの任意の−ＣＨ_２−は下記式（ＤＩ−１３−ｂ）で表される２価の基で置き換えられていてもよい。

式（ＤＩ−１３−ｂ）において、Ｒ^２７およびＲ^２８は独立して炭素数１〜３のアルキルであり、ｖは１〜６の整数である。Ｒ^２６の好ましい例は炭素数１〜３０のアルキルおよび炭素数１〜３０のアルコキシである。 Examples of the diamine having a side chain include compounds represented by the following formulas (DI-13) to (DI-17).

In the formula (DI-13), G ²⁶ represents a single bond, —O—, —COO—, —OCO—, —CO—, —CONH—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—. , —OCF ₂ —, or — (CH ₂ ) _{m ′} —, and m ′ is an integer of 1 to 12. Preferred examples of G ²⁶ include a single bond, —O—, —COO—, —OCO—, —CH ₂ O—, and alkylene having 1 to 3 carbon atoms, and particularly preferred examples include a single bond, —O—, — _{COO -, - OCO -, -} CH 2 O -, - CH 2 - and _-CH 2 CH ₂ -. R ²⁵ is a group having 3 to 30 carbon atoms, phenyl, a group having a steroid skeleton, or a group represented by the following formula (DI-13-a). In this alkyl, any —H may be replaced with —F, and any —CH ₂ — may be replaced with —O—, —CH═CH— or —C≡C—. _-H in which _{phenyl, -F, -CH 3, -OCH 3} , -OCH 2 F, -OCHF 2, -OCF 3, has been replaced by an alkoxy alkyl or 3 to 30 carbon atoms having 3 to 30 carbon atoms In this cyclohexyl group, —H may be substituted with alkyl having 3 to 30 carbon atoms or alkoxy having 3 to 30 carbon atoms. The bonding position of —NH ₂ bonded to the benzene ring indicates an arbitrary position in the ring, but the bonding position is preferably meta or para. That is, when the bonding position of the group “R ²⁵ -G ²⁴ —” is the first position, the two bonding positions are preferably the third position and the fifth position, or the second position and the fifth position.

In the formula (DI-13-a), G ²⁷ , G ²⁸ and G ²⁹ are bonding groups, and these are each independently a single bond or alkylene having 1 to 12 carbons, and one or more of these alkylenes —CH ₂ — may be replaced by —O—, —COO—, —OCO—, —CONH— or —CH═CH—. Ring B ²¹ , Ring B ²² , Ring B ²³ and Ring B ²⁴ are independently 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5. - diyl, pyridine-2,5-diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl or anthracene-9,10-diyl, ring ^{B 21,} ring ^{B 22,} ring ^{B 23} and ring in B ^24, any -H may be replaced by -F, or -CH _3, s, t and u is an integer of independently 0-2, these sum is 1-5, When s, t or u is 2, the two linking groups in each parenthesis may be the same or different, and the two rings may be the same or different. R ²⁶ represents —F, —OH, alkyl having 1 to 30 carbon atoms, fluorine-substituted alkyl having 1 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms, —CN, —OCH ₂ F, —OCHF ₂ , or —OCF. _And any —CH ₂ — in the alkyl having 1 to 30 carbon atoms may be replaced by a divalent group represented by the following formula (DI-13-b).

In the formula (DI-13-b), R ²⁷ and R ²⁸ are each independently alkyl having 1 to 3 carbon atoms, and v is an integer of 1 to 6. Preferred examples of R ²⁶ are alkyl having 1 to 30 carbons and alkoxy having 1 to 30 carbons.

式（ＤＩ−１４）および式（ＤＩ−１５）において、Ｇ^３０は独立して単結合、−ＣＯ−または−ＣＨ₂−であり、Ｒ^２９は独立して−Ｈまたは−ＣＨ_３であり、Ｒ^３０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。式（ＤＩ−１５）におけるベンゼン環の１つの−Ｈは、炭素数１〜２０のアルキルまたはフェニルで置き換えられてもよい。そして、環を構成するいずれかの炭素原子に結合位置が固定されていない基は、その環における結合位置が任意であることを示す。式（ＤＩ−１４）における２つの基「−フェニレン−Ｇ^３０−Ｏ−」の一方はステロイド核の３位に結合し、もう一方はステロイド核の６位に結合していることが好ましい。式（ＤＩ−１５）における２つの基「−フェニレン−Ｇ^３０−Ｏ−」のベンゼン環への結合位置は、ステロイド核の結合位置に対して、それぞれメタ位またはパラ位であることが好ましい。式（ＤＩ−１４）および式（ＤＩ−１５）において、ベンゼン環に結合する−ＮＨ_２はその環における結合位置が任意であることを示す。

In Formula (DI-14) and Formula (DI-15), G ³⁰ is independently a single bond, —CO— or —CH ₂ —, R ²⁹ is independently —H or —CH ₃ , R ³⁰ is —H, alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons. One -H of the benzene ring in formula (DI-15) may be replaced with alkyl having 1 to 20 carbons or phenyl. A group whose bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary. One of the two groups “-phenylene-G ³⁰ —O—” in formula (DI-14) is preferably bonded to the 3-position of the steroid nucleus and the other is bonded to the 6-position of the steroid nucleus. The bonding position of the two groups “-phenylene-G ³⁰ —O—” in formula (DI-15) to the benzene ring is preferably the meta position or the para position, respectively, with respect to the bonding position of the steroid nucleus. In Formula (DI-14) and Formula (DI-15), —NH ₂ bonded to a benzene ring indicates that the bonding position in the ring is arbitrary.

式（ＤＩ−１６）および式（ＤＩ−１７）において、Ｇ^３１は独立して−Ｏ−または炭素数１〜６のアルキレンであり、Ｇ^３２は単結合または炭素数１〜３のアルキレンである。Ｒ^３１は−Ｈまたは炭素数１〜２０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。Ｒ^３２は炭素数６〜２２のアルキルであり、Ｒ^３３は−Ｈまたは炭素数１〜２２のアルキルである。環Ｂ^２５は１，４−フェニレンまたは１，４−シクロヘキシレンであり、ｒは０または１である。そしてベンゼン環に結合する−ＮＨ_２はその環における結合位置が任意であることを示すが、独立してＧ^２９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 Formula (DI-16) and Formula (DI-17), G ³¹ is independently —O— or alkylene having 1 to 6 carbons, and G ³² is a single bond or alkylene having 1 to 3 carbons. . R ³¹ is —H or alkyl having 1 to 20 carbons, and any —CH ₂ — in the alkyl may be replaced by —O—, —CH═CH— or —C≡C—. R ³² is alkyl having 6 to 22 carbon atoms, and R ³³ is —H or alkyl having 1 to 22 carbon atoms. Ring B ²⁵ is 1,4-phenylene or 1,4-cyclohexylene, and r is 0 or 1. And -NH ₂ bonded to the benzene ring shows that the binding position in the ring is optional, it is preferable independently a meta or para position with respect to the binding position of the G ^29.

Specific examples of the side chain diamine are illustrated below.
Examples of the diamine compound having a side chain of the above formulas (DI-13) to (DI-17) include compounds represented by the following formulas (DI-13-1) to (DI-17-3). .

式（ＤＩ−１３−１）〜（ＤＩ−１３−１１）において、Ｒ^３４は炭素数１〜３０のアルキルまたは炭素数１〜３０のアルコキシであり、好ましくは炭素数５〜２５のアルキルまたは炭素数５〜２５のアルコキシである。Ｒ^３５は炭素数１〜３０のアルキルまたは炭素数１〜３０のアルコキシであり、好ましくは炭素数３〜２５のアルキルまたは炭素数３〜２５のアルコキシである。 Examples of the compound represented by the formula (DI-13) are shown below.

In the formulas (DI-13-1) to (DI-13-11), R ³⁴ is alkyl having 1 to 30 carbons or alkoxy having 1 to 30 carbons, preferably alkyl or carbon having 5 to 25 carbons. It is alkoxy of several 5-25. R ³⁵ 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.

式（ＤＩ−１３−１２）〜（ＤＩ−１３−１７）において、Ｒ^３６は炭素数４〜３０のアルキルであり、好ましくは炭素数６〜２５のアルキルである。Ｒ^３７は炭素数６〜３０のアルキルであり、好ましくは炭素数８〜２５のアルキルである。

In the formulas (DI-13-12) to (DI-13-17), R ³⁶ is alkyl having 4 to 30 carbons, and preferably alkyl having 6 to 25 carbons. R ³⁷ is alkyl having 6 to 30 carbon atoms, preferably alkyl having 8 to 25 carbon atoms.

式（ＤＩ−１３−１８）〜（ＤＩ−１３−４３）において、Ｒ^３８は炭素数１〜２０のアルキルまたは炭素数１〜２０のアルコキシであり、好ましくは炭素数３〜２０のアルキルまたは炭素数３〜２０のアルコキシである。Ｒ^３９は−Ｈ、−Ｆ、炭素数１〜３０のアルキル、炭素数１〜３０のアルコキシ、−ＣＮ、−ＯＣＨ_２Ｆ、−ＯＣＨＦ_２または−ＯＣＦ_３であり、好ましくは炭素数３〜２５のアルキル、または炭素数３〜２５のアルコキシである。そしてＧ^３３は炭素数１〜２０のアルキレンである。

In the formulas (DI-13-18) to (DI-13-43), R ³⁸ is alkyl having 1 to 20 carbons or alkoxy having 1 to 20 carbons, preferably alkyl or carbon having 3 to 20 carbons. It is alkoxy of several 3-20. R ³⁹ is —H, —F, alkyl having 1 to 30 carbons, alkoxy having 1 to 30 carbons, —CN, —OCH ₂ F, —OCHF ₂ or —OCF ₃ , preferably ₃ to 25 carbons. Or alkyl having 3 to 25 carbon atoms. G ³³ is alkylene having 1 to 20 carbon atoms.

Examples of the compound represented by the formula (DI-14) are shown below.

Examples of the compound represented by the formula (DI-15) are shown below.

式（ＤＩ−１６−１）〜（ＤＩ−１６−１２）において、Ｒ^４０は−Ｈまたは炭素数１〜２０のアルキル、好ましくは−Ｈまたは炭素数１〜１０のアルキルであり、そしてＲ^４１は−Ｈまたは炭素数１〜１２のアルキルである。 Examples of the compound represented by the formula (DI-16) are shown below.

In the formulas (DI-16-1) to (DI-16-12), R ⁴⁰ is —H or alkyl having 1 to 20 carbons, preferably —H or alkyl having 1 to 10 carbons, and R ⁴¹ Is —H or alkyl having 1 to 12 carbons.

式（ＤＩ−１７−１）〜（ＤＩ−１７−３）において、Ｒ^３７は炭素数６〜３０のアルキルであり、Ｒ^４１は−Ｈまたは炭素数１〜１２のアルキルである。 Examples of the compound represented by the formula (DI-17) are shown below.

In formula (DI-17-1) ~ (DI -17-3), R 37 is alkyl of 6 to 30 carbon ^{atoms, R 41} is -H or alkyl having 1 to 12 carbon atoms.

As other diamines in the present invention, diamines other than the diamines represented by the formulas (DI-1-1) to (DI-17-3) described above can also be used. Examples of such other diamines include diamines having a side chain structure other than formulas (DI-13-1) to (DI-17-3) and photosensitive diamines.

式（ＤＩ−１８−１）〜（ＤＩ−１８−８）中、Ｒ^４２はそれぞれ独立して炭素数３〜３０のアルキル基を表す。 Examples of other diamines other than the photosensitive diamine described below include compounds represented by the following formulas (DI-18-1) to (DI-18-8).

In formulas (DI-18-1) to (DI-18-8), R ⁴² each independently represents an alkyl group having 3 to 30 carbon atoms.

When the liquid crystal display element using the liquid crystal aligning agent of the present invention requires a large pretilt angle, in particular, in order to develop a pretilt angle of 2 degrees or more, the production of polyamic acid and derivatives thereof used for the liquid crystal aligning agent of the present invention At this time, the proportion of the side chain type diamine in the total amount of diamine is preferably 5 to 70 mol%, more preferably 10 to 50 mol%.

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

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

Among the specific examples of the diamine, when emphasizing further improving the orientation of the liquid crystal, the formulas (DI-5-1), (DI-5-12), (DI-5-14), (DI-5-29), (DI-6-1) to (DI-6-5), (DI-6-7), (DI-7-1), (DI-7-3), (DI -7-5), (DI-7-9), (DI-11-1), (DI-12-1), (DI-13-1) to (DI-13-11), (DI-16) -1), (DI-16-2), (DI-16-4), (DI-16-5), (DI-16-7), (DI-16-8), (DI-16-10) ) And a diamine represented by (DI-16-11) are preferable, and are represented by the formulas (DI-5-1), (DI-5-29), (DI-7-3), (DI-11). -1), (DI- 2-1) and (DI-13-1) diamines represented by ~ (DI-13-11) is more preferred. In the formula (DI-5-1), a compound where m = 2, 3, 4, or 6 is particularly preferable. In the formula (DI-5-29), a compound where k = 2 is particularly preferable. In the formula (DI-7-3), a compound in which m = 3 or 6 and n = 1 is particularly preferable.

Among the specific examples of the diamine, when emphasizing the application of high VHR to the liquid crystal alignment film, the formulas (DI-5-1), (DI-5-2), (DI-5-21) , (DI-5-29), (DI-6-1), (DI-7-1), (DI-7-3), (DI-7-5), (DI-9-1), ( DI-11-1), (DI-12-1), (DI-13-1) to (DI-13-11), (DI-16-1), (DI-16-2), (DI- 16-4), (DI-16-5), (DI-16-7), and diamines represented by the formula (DI-16-11) are preferably used, and the formula (DI-5-1), (DI-5-2), (DI-5-21), (DI-5-29), (DI-7-3), (DI-9-1), and formulas (DI-13-1) to (DI-13-6) More preferably the diamine is. In the formula (DI-5-1), a compound where m = 1 is particularly preferable. In the formula (DI-5-29), a compound where k = 2 is particularly preferable. In the formula (DI-7-3), a compound in which m = 3 and n = 1 is particularly preferable.

Among the specific examples of the diamine, when importance is attached to further reducing the volume resistance value of the liquid crystal alignment film, the formulas (DI-5-1), (DI-5-2), (DI-5- 9) to (DI-5-11), (DI-5-13) to (DI-5-15), (DI-5-21), (DI-5-29), (DI-6-3) It is preferable to use a diamine represented by (DI-6-5), (DI-9-1), (DI-11-1), and (DI-12-1). 1), (DI-5-2), (DI-5-9) to (DI-5-11), (DI-5-21), (DI-5-29), and (DI-9-1) The diamine represented by this is more preferable. In the formula (DI-5-1), a compound where m = 1 is particularly preferable, and in the formula (DI-5-29), a compound where k = 2 is particularly preferable.

On the other hand, in order to give a pretilt angle to an alignment film for the purpose of reducing defects such as alignment failure and light leakage due to rubbing, or for improving the response speed of liquid crystal in the VA mode, a photo alignment film has recently been used. It has come into practical use. The diamine represented by the formula (1) of the present invention can be suitably used in order to improve the afterimage characteristics even in such a photo-alignment film application. Since the diamine represented by the formula (1) of the present invention usually does not have a photosensitive functional group, the polyamic acid obtained by reacting a mixture with the photosensitive diamine with tetracarboxylic dianhydride or a derivative thereof. Is used. This photosensitive diamine can be selected without limitation from known compounds.

式（ＤＩ−１９−８）において、Ｒ^４３は炭素数１〜６のアルキレンまたはアルコキシであり、アルキレンまたはアルコキシの任意の−Ｈは−ＣＦ_３で置き換えられていてもよい。 The photosensitive diamine will be described.
Examples of the photosensitive diamine include diamine compounds represented by the following formulas (DI-19-1) to (DI-19-8).

In formula (DI-19-8), R ⁴³ represents alkylene or alkoxy having 1 to 6 carbons, and any —H of alkylene or alkoxy may be replaced by —CF ₃ .

In the embodiment in which the diamine represented by the formula (1) of the present invention and the photosensitive diamine are used in combination as described above, the diamine / photosensitivity represented by the formula (1) is used in order to prevent the sensitivity of the alignment film to light. The ratio of the functional diamine is preferably 5/95 (mol%) to 70/30 (mol%), more preferably 5/95 (mol%) to 50/50 (mol%). Further, in order to improve the above-mentioned various characteristics such as electrical characteristics and afterimage characteristics, the above-mentioned non-photosensitive diamine other than the diamine and photosensitive diamine of the present invention represented by the formula (1) may be used in combination. Good. In this case, the ratio of diamine / non-photosensitive diamine represented by formula (1) is preferably 50/50 (mol%) to 90/10 (mol%), and the sensitivity to light is lowered. In order to prevent this, the ratio of the diamine represented by formula (1) and the non-photosensitive diamine / photosensitive diamine is preferably in the range of 10/90 (mol%) to 50/50 (mol%). .

In addition, by introducing a functional group having photosensitivity to any part of G ¹ and G ⁴ of the diamine of the present invention represented by the formula (1) to impart photosensitivity, the photo-alignment film is used as a photo-sensitive diamine. It can also be suitably used for.

The polyamic acid used for the liquid crystal aligning agent of this invention is obtained by making the mixture of said acid anhydride and diamine react in a solvent. In this synthesis reaction, no special conditions other than the selection of the raw materials are required, and the conditions for normal polyamic acid synthesis can be applied as they are. The solvent to be used will be described later.

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

For example, the liquid crystal aligning agent of the present invention may further contain an alkenyl-substituted nadiimide compound for the purpose of stabilizing the electrical characteristics of the liquid crystal display element over a long period of time. An alkenyl substituted nadiimide compound may be used by 1 type, and may use 2 or more types together. For the above purpose, the content of the alkenyl-substituted nadiimide compound is preferably 1 to 100% by weight, more preferably 1 to 70% by weight, and more preferably 1 to 50% by weight with respect to the polyamic acid or derivative thereof. More preferably.

式（ＮＡ）において、Ｌ^１およびＬ^２は独立して−Ｈ、炭素数１〜１２のアルキル、炭素数３〜６のアルケニル、炭素数５〜８のシクロアルキル、アリールまたはベンジルであり、ｎは１または２である。 The nadiimide compound will be specifically described below.
The alkenyl-substituted nadiimide compound is preferably a compound that can be dissolved in a solvent that dissolves the polyamic acid or derivative thereof used in the present invention. Examples of such alkenyl-substituted nadiimide compounds include compounds represented by the following formula (NA).

In the formula (NA), L ¹ and L ² are independently —H, alkyl having 1 to 12 carbons, alkenyl having 3 to 6 carbons, cycloalkyl having 5 to 8 carbons, aryl or benzyl, n Is 1 or 2.

In the formula (NA), when n = 1, W is alkyl having 1 to 12 carbons, alkenyl having 2 to 6 carbons, cycloalkyl having 5 to 8 carbons, aryl having 6 to 12 carbons, benzyl,- Z ^1- (O) _r- (Z ² O) _k -Z ³ -H (wherein Z ¹ , Z ² and Z ³ are independently alkylene having 2 to 6 carbon atoms, and r is 0 or 1 And k is an integer of 1 to 30.), a group represented by — (Z ⁴ ) _r —BZ ⁵ —H (wherein Z ⁴ and Z ⁵ are independently a carbon number) A group represented by the formula: -B-T-B-H (which is an alkylene having 1 to 4 carbon atoms or a cycloalkylene having 5 to 8 carbon atoms, B is phenylene, and r is 0 or 1) B is phenylene, and T is —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, —CO—, — S— or —SO ₂ —), or a group in which 1 to 3 —H of these groups are substituted with —OH.

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

Wherein in (NA), when n = 2, W is alkylene of 2 to 20 carbon atoms, cycloalkylene of 5 to 8 carbon atoms, arylene having 6 to 12 carbon ^{atoms, -Z 1 -O- (Z 2 O} ) a group represented by _k— Z ³ — (wherein Z ^{1 to} Z ³ and k have the same meanings as described above), —Z ⁴ —BZ ⁵ — (where Z ⁴ , Z meaning of ⁵ and B are as defined above. groups represented _{by), -B- (O-B)} r -T- (B-O) r -B- ( wherein, B is phenylene, T is alkylene having 1 to 3 carbon atoms, —O— or —SO ₂ —, and r has the same meaning as described above.), Or 1 to 3 —H of these groups Is a group replaced by —OH.

In this case, preferable W is alkylene having 2 to 12 carbon atoms, cyclohexylene, phenylene, tolylene, xylylene, —C ₃ H ₆ —O— (Z ² —O) _n —O—C ₃ H ₆ — (where, Z ² is alkylene having 2 to 6 carbon atoms, and n is 1 or 2.) —B—T—B— (where B is phenylene, and T is — A group represented by CH ₂ —, —O— or —SO ₂ —), —B—O—B—C ₃ H ₆ —B—O—B—, wherein B is phenylene. ), And one or two of these groups in which —H is replaced by —OH.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

And as a particularly preferable alkenyl substituted nadiimide compound, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) represented by the following formula (NA-1): Phenyl} methane, N, N′-m-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) represented by the formula (NA-2), and N, N′-hexamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) represented by the formula (NA-3) may be mentioned.

For example, the liquid crystal aligning agent of the present invention may further contain a compound having a radical polymerizable unsaturated double bond for the purpose of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time. The compound having a radically polymerizable unsaturated double bond may be one kind of compound or two or more kinds of compounds. The compound having a radical polymerizable unsaturated double bond does not include an alkenyl-substituted nadiimide compound. The content of the compound having a radically polymerizable unsaturated double bond is preferably 0.01 to 1.00, preferably 0.01 to 0.70 in terms of the above-mentioned purpose, as a polyamic acid or a derivative thereof. Is more preferable, and it is still more preferable that it is 0.01-0.50.

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

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

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

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

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

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

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

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

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

The oxazine compound will be specifically described below.
The oxazine compound is soluble in a solvent for dissolving the polyamic acid or its derivative, and in addition, an oxazine compound having ring-opening polymerizability is preferable.

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

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

式（ＯＸ−１）〜（ＯＸ−３）において、Ｌ^３およびＬ^４は炭素数１〜３０の有機基であり、式（ＯＸ−１）〜（ＯＸ−６）において、Ｌ^５〜Ｌ^８は−Ｈまたは炭素数１〜６の炭化水素基であり、式（ＯＸ−３）、式（ＯＸ−４）および式（ＯＸ−６）において、Ｑ^１は単結合、−Ｏ−、−Ｓ−、−Ｓ−Ｓ−、−ＳＯ₂−、−ＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−、−（ＣＨ_２）_ｖ−、−Ｏ−（ＣＨ_２）_ｖ−Ｏ−、−Ｓ−（ＣＨ_２）_ｖ−Ｓ−であり、ここでｖは１〜６の整数であり、式（ＯＸ−５）および式（ＯＸ−６）において、Ｑ^２は独立して単結合、−Ｏ−、−Ｓ−、−ＣＯ−、−Ｃ（ＣＨ₃）₂−、−Ｃ（ＣＦ₃）₂−または炭素数１〜３のアルキレンであり、Ｑ^２におけるベンゼン環、ナフタレン環に結合している水素は独立して−Ｆ、−ＣＨ_３、−ＯＨ、−ＣＯＯＨ、−ＳＯ_３Ｈ、−ＰＯ_３Ｈ_２と置き換えられていてもよい。 Examples of the oxazine compound include compounds represented by the following formulas (OX-1) to (OX-6). In the following formula, the bond displayed toward the center of the ring indicates that it is bonded to any carbon that forms the ring and can be bonded to a substituent.

In formulas (OX-1) to (OX-3), L ³ and L ⁴ are organic groups having 1 to 30 carbon atoms, and in formulas (OX-1) to (OX-6), L ^{5 to} L ⁸ Is —H or a hydrocarbon group having 1 to 6 carbon atoms, and in Formula (OX-3), Formula (OX-4), and Formula (OX-6), Q ¹ is a single bond, —O—, —S -, - S-S -, - SO 2 -, - CO -, - CONH -, - NHCO -, - C (CH 3) 2 -, - C (CF 3) 2 -, - (CH 2) v - _{, -O- (CH 2) v -O} -, - S- (CH 2) v is -S-, where v is an integer from 1 to 6, formula (OX-5) and formula (OX 6), Q ² is independently a single bond, —O—, —S—, —CO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ — or alkylene having 1 to 3 carbon atoms. And in Q ² Definitive benzene ring, _-F hydrogen is independently attached to the naphthalene _{ring, -CH 3, -OH, -COOH,} -SO 3 H, may be replaced with _-PO 3 _{H 2.}

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

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

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

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

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

式（ＯＸ−３−Ｉ）において、Ｌ^３およびＬ^４は炭素数１〜３０の有機基であり、Ｌ^５からＬ^８は−Ｈまたは炭素数１〜６の炭化水素基であり、Ｑ^１は単結合、−ＣＨ₂−、−Ｃ（ＣＨ_３）_２−、−ＣＯ−、−Ｏ−、−ＳＯ_２−またはＣ（ＣＦ_３）_２−である。式（ＯＸ−３−Ｉ）で表されるオキサジン化合物としては、例えば以下のオキサジン化合物が挙げられる。 As the oxazine compound represented by the formula (OX-3), an oxazine compound represented by the following formula (OX-3-I) can be given.

In Formula (OX-3-I), L ³ and L ⁴ are each an organic group having 1 to 30 carbon atoms, L ⁵ to L ⁸ are —H or a hydrocarbon group having 1 to 6 carbon atoms, and Q ¹ Is a single bond, —CH ₂ —, —C (CH ₃ ) ₂ —, —CO—, —O—, —SO ₂ — or C (CF ₃ ) ₂ —. Examples of the oxazine compound represented by the formula (OX-3-I) include the following oxazine compounds.

式中、Ｌ^３は炭素数１〜３０のアルキルが好ましく、炭素数１〜２０のアルキルがさらに好ましい。

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

Examples of the oxazine compound represented by the formula (OX-4) include the following oxazine compounds.

Examples of the oxazine compound represented by the formula (OX-5) include the following oxazine compounds.

Examples of the oxazine compound represented by the formula (OX-6) include the following oxazine compounds.

Of these, more preferably, the formulas (OX-2-1), (OX-3-1), (OX-3-3), (OX-3-5), (OX-3-7), ( OX-3-9), (OX-4-1) to (OX-4-6), (OX-5-3), (OX-5-4), and (OX-6-6-2) to (OX Oxazine compound represented by -6-4).

The oxazine compound can be produced by the same method as described in International Publication No. 2004/009708, JP-A-11-12258, and JP-A-2004-352670.

The oxazine compound represented by the formula (OX-1) is obtained by reacting a phenol compound, a primary amine, and an aldehyde (see International Publication No. 2004/009708 pamphlet).

The oxazine compound represented by the formula (OX-2) is obtained by reacting by a method of gradually adding a primary amine to formaldehyde, and then adding and reacting a compound having a naphthol-based hydroxyl group (International Publication 2004 / (Refer to 009708 pamphlet.)

The oxazine compound represented by the formula (OX-3) is a secondary aliphatic compound in which 1 mol of a phenol compound, at least 2 mol or more of an aldehyde, and 1 mol of a primary amine are added to one phenolic hydroxyl group in an organic solvent. It can be obtained by reacting in the presence of an amine, a tertiary aliphatic amine, or a basic nitrogen-containing heterocyclic compound (see International Publication No. 2004/009708 and JP-A-11-12258).

Oxazine compounds represented by formulas (OX-4) to (OX-6) are aldehydes such as 4,4′-diaminodiphenylmethane, diamines having a plurality of benzene rings and organic groups that bind them, and aldehydes such as formalin. And phenol are subjected to a dehydration condensation reaction in n-butanol at a temperature of 90 ° C. or higher (see JP-A No. 2004-352670).

For example, the liquid crystal aligning agent of this invention may further contain the oxazoline compound from the objective of stabilizing the electrical property in a liquid crystal display element for a long period of time. An oxazoline compound is a compound having an oxazoline structure. The oxazoline compound may be a single compound or two or more compounds. The content of the oxazoline compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, and more preferably 1 to 20% by weight with respect to the polyamic acid or a derivative thereof for the above purpose. It is preferable that Alternatively, the content of the oxazoline compound is preferably 0.1 to 40% by weight with respect to the polyamic acid or a derivative thereof when the oxazoline structure in the oxazoline compound is converted to oxazoline.

The oxazoline compound will be specifically described below.
The oxazoline compound may have only one type of oxazoline structure in one compound, or may have two or more types. Further, the oxazoline compound may have one oxazoline structure in one compound, but preferably has two or more. The oxazoline compound may be a polymer having an oxazoline ring structure in the side chain, or may be a copolymer. The polymer having an oxazoline structure in the side chain may be a homopolymer of a monomer having an oxazoline structure in the side chain, or a copolymer of a monomer having an oxazoline structure in the side chain and a monomer having no oxazoline structure It may be. The copolymer having an oxazoline structure in the side chain may be a copolymer of two or more monomers having an oxazoline structure in the side chain, or two or more monomers having an oxazoline structure in the side chain and an oxazoline structure. It may also be a copolymer with a monomer that does not have.

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

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

For example, the liquid crystal aligning agent of the present invention may further contain an epoxy compound for the purpose of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time. The epoxy compound may be a kind of compound or two or more kinds of compounds. The content of the epoxy compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, and more preferably 1 to 20% by weight with respect to the polyamic acid or derivative thereof for the above purpose. More preferably.

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

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

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

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

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

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

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

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

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

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

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

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

Examples of the glycidylamine include polyglycidylamine compounds and glycidylamine type epoxy resins.

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

Examples of glycidyl amide include glycidyl amide type epoxy compounds.

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

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

Examples of the bisphenol A type epoxy compound include 828, 1001, 1002, 1003, 1004, 1007 and 1010 (all manufactured by Mitsubishi Chemical Corporation), Epototo YD-128 (manufactured by Toto Kasei Co., Ltd.), DER-331, DER-332, DER-324 (all manufactured by The Dow Chemical Company), Epicron 840, Epicron 850, Epicron 1050 (all manufactured by DIC Corporation), Epomic R-140, Epomic R-301, and Epomic R-304 (Both manufactured by Mitsui Chemicals, Inc.).

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

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

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

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

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

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

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

Examples of the bisphenol A novolak type epoxy compound include 157S70 (manufactured by Mitsubishi Chemical Corporation) and Epicron N-880 (manufactured by DIC Corporation).

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

Examples of the aromatic polyglycidyl ether compound include hydroquinone diglycidyl ether (following formula EP-1), catechol diglycidyl ether (following formula EP-2) resorcinol diglycidyl ether (following formula EP-3), 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3-epoxypropoxy] phenyl)] ethyl] phenyl] propane (formula EP-4 below), Tris (4-glycidyloxyphenyl) methane (formula EP-5 below), 1031S, 1032H60 (all manufactured by Mitsubishi Chemical Corporation), TACTIX-742 (manufactured by The Dow Chemical Company), Denacol EX-201 (Nagase ChemteX) Manufactured by Co., Ltd.), DPPN-503, DPPN-502H, DPPN-501H, NC6000 Both Nippon Kayaku Co., Ltd.), made by Techmore VG3101L (Mitsui Chemicals, Inc.), compounds represented by the following formula EP-6, and compounds represented by the following formula EP-7.

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

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

Examples of the aliphatic polyglycidyl ether compound include ethylene glycol diglycidyl ether (following formula EP-8), diethylene glycol diglycidyl ether (following formula EP-9), polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether (following formula EP). -10), tripropylene glycol diglycidyl ether (following formula EP-11), polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether (following formula EP-12), 1,4-butanediol diglycidyl ether (following formula EP-13), 1,6-hexanediol diglycidyl ether (following formula EP-14), dibromoneopentyl glycol diglycidyl ether (following formula EP-15), Denacol EX 810, Denacol EX-851, Denacol EX-8301, Denacol EX-911, Denacol EX-920, Denacol EX-931, Denacol EX-211, Denacol EX-212, Denacol EX-313 (all Nagase ChemteX Corporation) ), DD-503 (manufactured by ADEKA Corporation), Rica Resin W-100 (manufactured by Shin Nippon Rika Co., Ltd.), 1,3,5,6-tetraglycidyl-2,4-hexanediol (following formula EP- 16), glycerin polyglycidyl ether, sorbitol polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, Denacol EX-313, Denacol EX-611, Denacol EX-321, and Denacol EX-411 Re also manufactured by Nagase Chemtex Co., Ltd.) and the like.

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

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

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

Examples of the glycidyl ester epoxy compounds include 871, 872 (all manufactured by Mitsubishi Chemical Corporation), Epicron 200, Epicron 400 (all manufactured by DIC Corporation), Denacol EX-711, and Denacol EX-721 (all Nagase ChemteX Corporation).

Examples of the polyglycidylamine compound include N, N-diglycidylaniline (following formula EP-24), N, N-diglycidyl-o-toluidine (following formula EP-25), N, N-diglycidyl-m-toluidine ( The following formula EP-26), N, N-diglycidyl-2,4,6-tribromoaniline (the following formula EP-27), 3- (N, N-diglycidyl) aminopropyltrimethoxysilane (the following formula EP-28 ), N, N, O-triglycidyl-p-aminophenol (following formula EP-29), N, N, O-triglycidyl-m-aminophenol (following formula EP-30), N, N, N ′ , N′-tetraglycidyl-4,4′-diaminodiphenylmethane (following formula EP-31), N, N, N ′, N′-tetraglycidyl-m-xylylenediamine (TETRAD) X (Mitsubishi Gas Chemical Co., Ltd.), the following formula EP-32), 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane (TETRAD-C (Mitsubishi Gas Chemical Co., Ltd.)), the following formula EP-33), 1,4-bis (N, N-diglycidylaminomethyl) cyclohexane (following formula EP-34), 1,3-bis (N, N-diglycidylamino) cyclohexane (following formula EP-35) ), 1,4-bis (N, N-diglycidylamino) cyclohexane (following formula EP-36), 1,3-bis (N, N-diglycidylamino) benzene (following formula EP-37), 1, 4-bis (N, N-diglycidylamino) benzene (following formula EP-38), 2,6-bis (N, N-diglycidylaminomethyl) bicyclo [2.2.1] heptane (following formula EP- 39), N, N, N ′, N′-tetraglycidyl-4,4′-diaminodicyclohexylmethane (following formula EP-40), 2,2′-dimethyl- (N, N, N ′, N′-tetraglycidyl) -4,4 '-Diaminobiphenyl (following formula EP-41), N, N, N', N'-tetraglycidyl-4,4'-diaminodiphenyl ether (following formula EP-42), 1,3,5-tris (4- (N, N-diglycidyl) aminophenoxy) benzene (following formula EP-43), 2,4,4′-tris (N, N-diglycidylamino) diphenyl ether (following formula EP-44), tris (4- ( N, N-diglycidyl) aminophenyl) methane (following formula EP-45), 3,4,3 ′, 4′-tetrakis (N, N-diglycidylamino) biphenyl (following formula EP-46), 3,4 , 3 ', 4'-tetraki (N, N-diglycidyl amino) diphenyl ether (formula EP-47), a compound represented by the following formula EP-48, and compounds represented by the following formula EP-49.

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

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

Examples of the monomer other than the monomer having oxiranyl in the copolymer of the monomer having oxiranyl include, for example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, and butyl (meth). Acrylate, iso-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, styrene, Examples include methylstyrene, chloromethylstyrene, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, N-cyclohexylmaleimide, and N-phenylmaleimide.

Examples of glycidyl isocyanurate include 1,3,5-triglycidyl-1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione (the following formula EP-50), 1,3. -Diglycidyl-5-allyl-1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione (following formula EP-51) and glycidyl isocyanurate type epoxy resin.

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

Examples of the cycloaliphatic epoxy compound include 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate (Celoxide 2021 (manufactured by Daicel Chemical Industries, Ltd.), the following formula EP-52), 2 -Methyl-3,4-epoxycyclohexylmethyl-2'-methyl-3 ', 4'-epoxycyclohexylcarboxylate (formula EP-53 below), 2,3-epoxycyclopentane-2', 3'-epoxycyclo Pentane ether (following formula EP-54), ε-caprolactone-modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 1,2: 8,9-diepoxy limonene (Celoxide 3000 (Daicel Chemical) (Industry Co., Ltd.), the following formula EP-55), represented by the following formula EP-56 Compound, CY-175, CY-177, CY-179 (all manufactured by The Ciba-Geigy Chemical Corp. (available from Huntsman Japan KK)), EHPD-3150 (manufactured by Daicel Chemical Industries, Ltd.) ), And cycloaliphatic epoxy resins.

The epoxy compound is preferably one or more of a polyglycidylamine compound, a bisphenol A novolac type epoxy compound, a cresol novolac type epoxy compound, and a cyclic aliphatic type epoxy compound, and N, N, N ′, N′-tetraglycidyl -M-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane, trade name “Techmore VG3101L” 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate, N-phenylmaleimide-glycidyl methacrylate copolymer, N, N, O-triglycidyl-p-aminophenol, bisphenol A novolak type Epoxy compounds, It is preferred and is one or more cresol novolac type epoxy compound.

For example, the liquid crystal aligning agent of the present invention may further contain a polymer other than polyamic acid and derivatives thereof for the purpose of controlling the electrical characteristics and orientation of the liquid crystal display element. Examples of the polymer include polymers that are soluble in organic solvents. The polymer may be used alone or in combination of two or more. The content of the polymer is preferably from 0.01 to 100% by weight, more preferably from 0.1 to 70% by weight, more preferably from 0.1 to 70% by weight, based on the above-mentioned purpose. More preferably, it is ˜50% by weight. Examples of the polymer include polyamide, polyurethane, polyurea, polyester, polyepoxide, polyester polyol, silicone-modified polyurethane, silicone-modified polyester, polyacrylic acid alkyl ester, polymethacrylic acid alkyl ester, acrylic acid alkyl ester, and methacrylic acid alkyl ester. Examples include polymers, polyoxyethylene glycol diacrylate, polyoxyethylene glycol dimethacrylate, polyoxypropylene glycol diacrylate, and polyoxypropylene glycol dimethacrylate.

For example, the liquid crystal aligning agent of the present invention may further contain a low molecular compound. 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 and resistance to substrates. A silane coupling agent or a titanium-based coupling agent is desired when improving rubbing properties, and 4) an imidization catalyst when imidization proceeds at a low temperature. From the above viewpoint, the content of the low molecular compound is preferably 0.1 to 50% by weight, more preferably 0.1 to 40% by weight with respect to the polyamic acid or a derivative thereof. More preferably, it is 1 to 20% by weight.

The silane coupling agent includes silane compounds containing an epoxy group exemplified as the epoxy compound. In addition to improving adhesion to the substrate and rubbing resistance, a silane coupling agent containing an epoxy group may be added to the liquid crystal aligning agent of the present invention for the purpose of stabilizing electrical characteristics over a long period of time.

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 Ethoxysilyl) -1-propylamine, and N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine, and the silane coupling agent containing an epoxy group includes 3-glycidoxypropyltri Examples include methoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

Preferable silane coupling agents include 3-glycidoxypropyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

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 imidization catalyst is one or two selected from N, N-dimethylaniline, o-hydroxyaniline, m-hydroxyaniline, p-hydroxyaniline, o-hydroxypyridine, m-hydroxypyridine, p-hydroxypyridine, and isoquinoline. It is preferable to be a seed or more.

As the liquid crystal aligning agent of the present invention, it is preferable to use at least one of polyamic acid and its derivatives derived from the diamine represented by the formula (1), and the diamine of the present invention represented by the formula (1). Other polyamic acids or their derivatives that are not used as a raw material may be mixed and used. The mixing ratio when combining other polyamic acids or derivatives thereof is 10 to 95% by weight of the polyamic acid or derivative thereof of the present invention, and 5 to 90% by weight of other polyamic acid or derivative thereof based on the total amount of the polymer. Even if the ratio of the polyamic acid of the present invention or its derivative is small, a sufficient effect can be obtained. In the liquid crystal aligning agent of this invention, polymers other than the polyamic acid obtained by reaction with an acid anhydride and diamine, or its derivative (s), for example, polyester, an epoxy resin, etc. can be used together. However, the ratio when such other polymer is used in combination is preferably 30% by weight or less based on the total weight of the polymer.

The aligning agent of the present invention is a solution in which polyamic acid is dissolved in a solvent. This solvent can be appropriately selected from known solvents used in the production and use of polyamic acid according to the purpose of use. Examples of these solvents are as follows.

Examples of aprotic polar organic solvents include N-methyl-2-pyrrolidone (NMP), dimethylimidazolidinone, N-methylcaprolactam, N-methylpropionamide, N, N-dimethylacetamide, dimethyl sulfoxide, N, Examples include lactones such as N-dimethylformamide (DMF), N, N-diethylformamide, N, N-diethylacetamide (DMAc), and γ-butyrolactone (GBL).

Preferred examples of solvents other than those described above for the purpose of improving coatability include alkyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, ethylene glycol monoalkyl ether (eg, ethylene glycol monoalkyl). Butyl ether (BCS)), diethylene glycol monoalkyl ether (eg, diethylene glycol monoethyl ether), ethylene glycol monophenyl ether, triethylene glycol monoalkyl ether, propylene glycol monoalkyl ether (eg, propylene glycol monobutyl ether), dialkyl malonate ( Example: diethyl malonate), dipropylene glycol monoalkyl ether (eg, dipropylene glycol monomethyl ether), and these glycol monoethers Ester compound of ethers may be mentioned. Of these, NMP, dimethylimidazolidinone, GBL, BCS, diethylene glycol monoethyl ether, propylene glycol monobutyl ether and dipropylene glycol monomethyl ether are particularly preferred.

The concentration of the polymer in the alignment agent of the present invention is preferably 0.1 to 40% by weight, and more preferably 1 to 10% by weight. When it is necessary to adjust the film thickness when applying this aligning agent to the substrate, the concentration of the contained polymer can be adjusted by diluting with a solvent in advance.

The preferred range of the viscosity of the liquid crystal aligning agent of the present invention varies depending on the coating method, the concentration of the polyamic acid or derivative thereof, the type of polyamic acid or derivative used, and the type and ratio of the solvent. For example, in the case of application by a printing press, it is 5 to 100 mPa · s (more preferably 10 to 80 mPa · s). If it is less than 5 mPa · s, it is difficult to obtain a sufficient film thickness, and if it exceeds 100 mPa · s, printing unevenness may increase. In the case of spin coating, 5 to 200 mPa · s (more preferably 10 to 100 mPa · s) is suitable. In the case of coating using an inkjet coating apparatus, 5 to 50 mPa · s (more preferably 5 to 20 mPa · s) is suitable. The viscosity of the liquid crystal aligning agent is measured by a rotational viscosity measuring method, and is measured using a rotational viscometer (TVE-20L type manufactured by Toki Sangyo Co., Ltd.) (measurement temperature: 25 ° C.).

The method for forming the liquid crystal alignment film of the present invention will be described.
Usually, the liquid crystal alignment film is prepared by applying a liquid crystal aligning agent to the substrate, heating and baking the film, and, if necessary, subjecting the film obtained in the baking process to a rubbing process or a photo-alignment process. Can do. Among these processes, the method for forming a liquid crystal alignment film of the present invention is characterized by a process of heating and baking.

Examples of the substrate include a glass substrate on which an electrode such as an ITO (Indium Tin Oxide) electrode or a color filter may be provided. As a method for applying the liquid crystal aligning agent, a spinner method, a printing method, a dipping method, a dropping method, an ink jet method and the like are generally known.

The step of heating and baking will be described in detail.
The coating film can be baked under conditions necessary for the polyamic acid or its derivative to exhibit a dehydration / ring-closing reaction. As for the baking of the coating film, a method of heating in an oven or an infrared furnace, a method of heat treatment on a hot plate, and the like are known. When the polyimide film is heated to 300 ° C. or higher, the polymer itself often decomposes. In general, it is preferably performed at a temperature of about 150 to 300 ° C for 1 minute to 3 hours, particularly preferably 180 to 280 ° C, and more preferably 200 to 250 ° C.

The liquid crystal alignment film of the present invention is formed by applying the liquid crystal aligning agent of the present invention using the method as described above, followed by heating and baking, whereby the functional group that can be removed by heat is released, A liquid crystal alignment film that exhibits desired characteristics such as a low volume resistance value and high liquid crystal alignment properties can be formed.

Therefore, as described above, in the diamine represented by the formula (1) of the present invention, the functional group detachable at the calcination temperature is preferably a thermally decomposable carbamate group, and is a Boc group from the viewpoint of cost and safety. This is particularly preferred.

In the method for forming a liquid crystal alignment film of the present invention, a rubbing method or a photo-alignment method is suitable as a means for imparting anisotropy to the alignment film in order to align the liquid crystal in one direction with respect to the horizontal and / or vertical direction. Can be used. Particularly in the photo-alignment method which has recently attracted attention, linearly polarized light or non-polarized light is used for the alignment of the polyamic acid or its derivative. These lights are not particularly limited as long as they can orient the polyamic acid or its derivative in the liquid crystal alignment film. The polyamic acid or derivative thereof of the present invention can orient the film by low energy light irradiation. Therefore, the irradiation amount of linearly polarized light in the photo-alignment treatment of the polyamic acid or its derivative is preferably 0.5 to 10 J / cm2. The wavelength of linearly polarized light is preferably 250 to 400 nm. Although the irradiation angle with respect to the film surface of linearly polarized light is not particularly limited, it is preferable from the viewpoint of shortening the alignment processing time that it is as perpendicular as possible to the film surface in order to develop a strong alignment regulating force for the liquid crystal.

In the method for forming a liquid crystal alignment film of the present invention, the light irradiated to the film when it is desired to express a pretilt angle may be polarized light or non-polarized light. When it is desired to develop a pretilt angle, the amount of light applied to the film is preferably 0.5 to 10 J / cm 2, and the wavelength is preferably 250 to 400 nm. When it is desired to express the pretilt angle, the irradiation angle of the light irradiated to the film with respect to the film surface is not particularly limited, but is preferably 30 to 60 degrees from the viewpoint of shortening the alignment processing time.

The liquid crystal display element of the present invention will be described.
The liquid crystal display element according to the present invention includes a pair of substrates disposed opposite to each other, electrodes formed on one or both of the opposed surfaces of each of the pair of substrates, A liquid crystal display element having a liquid crystal alignment film of the present invention formed on a surface on which the liquid crystal is formed and a liquid crystal layer formed between the pair of substrates.

The electrode is not particularly limited as long as it is an electrode formed on one surface of the substrate. Examples of such electrodes include ITO and metal vapor deposition films. Further, the electrode may be formed on the entire surface of one surface of the substrate, or may be formed in a desired shape that is patterned, for example. Examples of the desired shape of the electrode include a comb shape or a zigzag structure. The electrode may be formed on one of the pair of substrates, or may be formed on both substrates. The form of electrode formation varies depending on the type of liquid crystal display element. For example, in the case of an IPS liquid crystal display element, an electrode is disposed on one of the pair of substrates, and in the case of other liquid crystal display elements, the electrodes of the pair of substrates are arranged. Electrodes are arranged on both sides. The liquid crystal alignment film is formed on the substrate or electrode.

The liquid crystal layer is formed in such a manner that the liquid crystal composition is sandwiched between the pair of substrates facing each other on which the liquid crystal alignment film is formed. In the formation of the liquid crystal layer, a spacer such as fine particles or a resin sheet that is interposed between the pair of substrates to form an appropriate interval can be used as necessary. The liquid crystal composition is not particularly limited, and a known liquid crystal composition can be used.

The alignment film of the present invention can improve the characteristics of all known liquid crystal compositions when a liquid crystal display element is formed as the liquid crystal alignment film. The alignment film of the present invention produced by the above method is particularly effective for a large screen display that requires an afterimage characteristic. Such a large screen display is driven and controlled by TFTs. Liquid crystal compositions used for such TFT type liquid crystal display elements are described in Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Laid-Open No. 5-501735, and Japanese Patent Laid-Open No. 9-255556. Yes. Therefore, the alignment film of the present invention is preferably used in combination with the liquid crystal composition described therein.

The liquid crystal display element of the present invention is also excellent in electrical characteristics relating to the reliability of the liquid crystal display element. Such electrical characteristics include voltage holding ratio and ion density. The voltage holding ratio (VHR) is a ratio at which the voltage applied to the liquid crystal display element during the frame period is held in the liquid crystal display element, and indicates display characteristics of the liquid crystal display element. The liquid crystal display element of the present invention uses a rectangular wave of 5 V and a frequency of 30 Hz, uses a rectangular wave having a voltage holding ratio of 97.0% or more measured at a temperature of 60 ° C., and a rectangular wave of 5 V and a frequency of 0.3 Hz. From the viewpoint of preventing display defects, it is preferable that the voltage holding ratio measured at a temperature of 60 ° C. is 85.0% or more.

The ion density is a transient current other than that caused by driving of the liquid crystal generated when a voltage is applied to the liquid crystal display element, and indicates the magnitude of the concentration of ionic impurities contained in the liquid crystal in the liquid crystal display element. The liquid crystal display element of the present invention preferably has an ion density of 300 pC or less from the viewpoint of preventing image sticking of the liquid crystal display element.

The present invention will be described with reference to examples and comparative examples.
The evaluation method of the liquid crystal display element in an Example is as follows.
<Pretilt angle measurement>
Measured according to the crystal rotation method.
<Voltage holding ratio>
It carried out by the method as described in "Mizushima et al., The 14th Liquid Crystal Discussion Meeting Proceedings p78 (1988)". The measurement was performed by applying a rectangular wave having a wave height of ± 5 V to the cell. The measurement was performed at 60 ° C. This value is an index indicating how much the applied voltage is retained after the frame period. If this value is 100%, it indicates that all charges are retained.
<Measurement of ion content in liquid crystal (ion density)>
According to the method described in Applied Physics, Vol. 65, No. 10, 1065 (1996), measurement was performed using a liquid crystal property measuring system 6254 type manufactured by Toyo Technica. Using a triangular wave with a frequency of 0.01 Hz, measurement was performed at a voltage range of ± 10 V and a temperature of 60 ° C. (electrode area is 1 cm ² ). If the ion density is high, defects such as seizure due to ionic impurities are likely to occur. That is, the ion density is a physical property value that serves as an index for predicting the occurrence of image sticking.
<Weight average molecular weight (Mw)>
The weight average molecular weight (Mw) of the polyamic acid in the liquid crystal aligning agent was determined by using gel permeation chromatography (GPC, manufactured by Shodex, GF7MHQ), and using 0.6% by weight phosphoric acid-containing DMF as an eluent. The column temperature was 50 ° C., and TSK standard polystyrene manufactured by Tosoh Corporation was used as a standard solution.
<Viscosity>
It measured at 25 degreeC using the viscometer (the Toki Sangyo company make, TV-22).
<Exposure of photo-alignment film>
Light irradiation was performed using a Ushio-made 500 W high-pressure mercury lamp (lamp; USH-500BY1) and using a bandpass filter to irradiate ultraviolet rays having a wavelength of about 300 to 380 nm. Irradiation was performed in air at room temperature.
<Measurement of retardation and thickness of alignment film>
It was determined using a spectroscopic ellipsometer M-2000U (manufactured by JAWoollam Co. Inc.). In this example, the retardation value of the film increases in proportion to the degree of orientation of the polymer main chain. That is, those having a large retardation value have a large degree of orientation.

The names of tetracarboxylic dianhydrides, diamines and solvents used in the examples and comparative examples are indicated by abbreviations. This abbreviation may be used in the following description.

<Tetracarboxylic dianhydride>
PMDA: pyromellitic dianhydride EDTA: ethylenediaminetetraacetic acid dianhydride CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride NTDA: 2,3,6,7-naphthalene tetracarboxylic dianhydride BDA: Butanetetracarboxylic dianhydride H-PMDA: 1,2,4,5-cyclohexanetetracarboxylic dianhydride TCDA: 2,3,5-tricarboxycyclopentylacetic acid dianhydride OHPDA: bicyclo [2 2.1] Heptanetetracarboxylic dianhydride BS8: 1,8-bis (3,4-phthaloyl anhydride) octane

<Diamine>
DD2: 4,4′-diaminodiphenylethane DDM: 4,4′-diaminodiphenylmethane DD4: 4,4′-diaminodiphenylbutane DDE: 4,4′-diaminodiphenyl ether NDAMe: N, N′-bis (4-amino Phenyl) -N, N′-dimethylethylenediamine DADPA: 4,4′-diaminodiphenylamine APDA: N, N-bis (4-aminophenyl) piperazine BZ3: 1,3-bis (4-((4-aminophenyl) Methyl) phenyl) propane 5HHA: 1,1-bis [4- (4-aminophenoxy) phenyl-4- (trans-4-n-pentylcyclohexyl) cyclohexane 5HHPDA: 1,1-bis [4- (4-amino Phenyl) methylphenyl] -4-n-heptylcyclohexane DABP: 4, '- diamino biphenyl DAAB: 4,4'-di-aminoazobenzene Anth: The following compounds described in International Publication 2010/050523 pamphlet

<Additives>
BANI-M: Bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane EP31: N, N, N ′, N′-tetraglycidyl -4,4'-diaminodiphenylmethane S510: 3-glycidoxypropyltrimethoxysilane

<Solvent>
THF: Tetrahydrofuran NMP: N-methyl-2-pyrrolidone BC: Butyl cellosolve (ethylene glycol monobutyl ether)
GBL: γ-butyrolactone

Synthesis Example 1 Synthesis of Compound (1-a-1) 20 g (66 mmol) of N, N′-bis (4-nitrophenyl) ethylenediamine and 1.6 g (1.3 mmol) of 4- (N, N-dimethyl) pyridine ) Was dissolved in tetrahydrofuran (THF, 100 ml) and refluxed. Di-tert-butyl dicarbonate (40 g, 0.20 mol) was slowly added thereto, followed by 30 minutes at room temperature, and then refluxed for 2 hours. After cooling, the reaction solution was added to pure water (1 L), and the resulting precipitate was filtered. The obtained crystals were vacuum-dried to obtain 32 g (yield: 96%) of the target N, N′-bis (4-nitrophenyl) -N, N′-bis (t-butoxycarbonyl) ethylenediamine. It was.

Hydrogenation reaction of 5.0 g (9.9 mmol) of the above compound was performed at room temperature in THF (40 ml) using 5% Pd / C1 g. After filtering the catalyst, the solvent was distilled off under reduced pressure to obtain 4.3 g of the desired product (yield: 99%).

Synthesis Example 2 Synthesis of Compound (1-a-4) Instead of N, N′-bis (4-nitrophenyl) ethylenediamine, N, N′-bis (4-nitrophenyl) -1,6- The target product was obtained by a method according to Synthesis Example 1 using xylenediamine (total yield: 72%).

¹ H-NMR (CDCl ₃ ): 6.8-7.0 (m, 4H), 6.62 (m, 4H, J = 8.40 Hz), 3.63 (s, 4H), 3.49 ( t, 4H, J = 7.35 Hz), 1.2-1.6 (m, 26H).
Melting point: 193.0-195.4 ° C.

Synthesis Example 3 Synthesis of Compound (1-b-1) 40 g (0.28 mol) of 4-fluoronitrobenzene and 43 g (0.31 mmol) of K ₂ CO ₃ were added to DMF (50 ml), and N-methyl was added thereto. Ethylenediamine 10 g (0.13 mmol) was added at room temperature. The reaction was allowed to proceed at room temperature (the reaction temperature rose to about 50 ° C.), and then reacted at 90 ° C. for 4 hours. After cooling, the reaction solution was added into pure water (1 L), and the resulting precipitate was filtered. The precipitate was washed with 50 ml of methanol to obtain 36 g of the desired N, N′-bis (4-nitrophenyl) -N-methylethylenediamine (yield 84%).

Using 20 g (63 mmol) of the above compound, 0.78 g (6.4 mmol) of 4- (N, N-dimethyl) pyridine and 19.2 g (95 mmol) of di-ter-butyldicarbonate, the reaction was carried out in the same manner as in Synthesis Example 1. Went. The obtained crude crystals were purified by recrystallization (ethyl acetate-ethanol) to obtain 20 g of N, N′-bis (4-nitrophenyl) -Nt-butoxycarbonyl-N′-methylethylenediamine ( Yield 76%).

By a method according to Synthesis Example 1, 20 g of the compound was subjected to a hydrogenation reaction to obtain 17 g of the desired product (yield: 99%).
¹ H-NMR (CDCl ₃ ): 6.5-7.1 (m, 8H), 3.6-3.7 (m, 4H), 3.39 (t, 2H, d = 7.06), 3.31 (br s, 4H), 1.2-1.6 (m, 9H).

[Synthesis Example 4] Synthesis of Compound (1-c-1) To a solution of 1.5 g (38 mmol) of 60% NaH dispersed in THF (20 ml), 8.0 g (34 mmol) of 4-Nt-butoxycarbonylaminonitrobenzene was prepared. ) In THF (20 ml) was added and stirred for about 30 minutes until hydrogen evolution ceased. A solution of 7.4 g (34 mmol) of 4-nitrobenzyl bromide in THF (10 ml) was added thereto and refluxed for 3 hours. After cooling, the reaction solution was added to pure water (50 ml) and extracted with ethyl acetate (70 ml). The organic layer was washed with pure water (50 ml), separated, and dried over anhydrous MgSO ₄ . After filtration and evaporation of the solvent under reduced pressure, the residue was purified by column chromatography (silica gel / toluene: ethyl acetate = 20: 1 (volume ratio)) to obtain the desired 4-N- (4-nitrobenzyl) -N. 8.5 g (yield 67%) of -t-butoxycarbonylaminonitrobenzene was obtained.

J. et al. Am. Chem. Soc. 81,136 (1959), a solution prepared by dissolving 5.0 g (13 mmol) of the above compound in EtOH (40 ml) and dissolving 2.6 g of ammonium chloride in 10 ml of pure water, zinc The powder 5.2g was added and it was made to recirculate | reflux for 30 minutes. 2.6 g of zinc powder was added to the reaction solution, and the mixture was further refluxed for 30 minutes. The mixture was filtered while hot, and after cooling, the filtrate was extracted with ethyl acetate (50 ml). The organic layer was washed twice with pure water (30 ml) and then dried over anhydrous MgSO ₄ . After filtration and evaporation of the solvent under reduced pressure, the residue was purified by column chromatography (silica gel / methylene chloride: methanol = 20: 1 (volume ratio)) to obtain the desired compound (1-c-1). 2.3 g (54% yield).

Synthesis Example 5 Synthesis of Compound (1-d-2) 2-amino-4,4′-dinitrobiphenyl 5.0 g (19 mmol), di-ter-butyl dicarbonate 8.4 g (38 mmol), pyridine 3. 0 g (38 mmol) was dissolved in tetrahydrofuran (50 ml) and refluxed for 2 hours. After cooling, the reaction solution was distilled off under reduced pressure, and the residue was dissolved in toluene (100 ml) and washed twice with pure water (70 ml). The organic layer was dried over anhydrous magnesium sulfate, filtered and the solvent was removed under reduced pressure. The residue was purified by column chromatography (silica gel / toluene ethyl acetate = 20: 1 (volume ratio)) and recrystallization (ethanol) to give the desired 2-N, N-bis-t-butoxycarbonyl-4, 7.4 g (yield 85%) of 4′-dinitrobiphenyl was obtained.

A hydrogenation reaction was performed at room temperature in toluene / ethanol (40 ml / 40 ml) using 7.0 g (15 mmol) of the above compound and 0.7 g of 5% Pd / C. After filtering the catalyst, the solvent was distilled off under reduced pressure to obtain the desired product. 6.0 g (99% yield)
¹ H-NMR (CDCl ₃ ): 7.1-7.2 (m, 3H), 6.6-6.7 (m, 3H), 6.47 (d, 1H, d = 2 Hz), 3. 65 (br s, 4H), 1.31 (s, 18H).

[Polymer Synthesis Example 1] Production of polyamic acid Into a three-necked flask equipped with a stirring blade and a thermometer, 2.0701 g (4.678 mmol) of compound (1-a-1) and 20.99927 g (4.676 mmol) of DD were placed. Then, 30 g of NMP was added and dissolved therein. The solution was allowed to cool to 5 ° C., and PMDA 1.0202 g (4.677 mmol) and CBDA 0.9170 g (4.676 mmol) were added thereto. The reaction was warmed to room temperature and stirred at room temperature for 12 hours. NMP30g and BC35g were added there, and also it stirred for 2 hours, and obtained the polyamic acid solution (varnish 1) with a density | concentration of 5 weight%. The viscosity of this varnish 1 was 19 mPa · s, and the weight average molecular weight of the polyamic acid in the varnish 1 was 38,000.

[Polymer Synthesis Examples 2-35]
Except that the combination of diamine and tetracarboxylic dianhydride was changed to the combinations listed in Table 1, an operation according to Polymer Synthesis Example 1 was performed to obtain a varnish having a polyamic acid concentration of 5% by weight. The prepared varnish is shown in Table 1 together with Polymer Synthesis Example 1. The numbers in parentheses on the right side of the abbreviations for diamine and tetracarboxylic dianhydride indicate mol%.

[Polymer synthesis example 36] Preparation of polyimide solution (varnish) To the varnish prepared in polymer synthesis example 11, 4.0 g (39 mmol) of acetic anhydride and 1.6 g (20 mmol) of pyridine were added and heated at 100 ° C for 30 minutes. After cooling, the reaction solution was added into pure water (200 ml), and the resulting precipitate was filtered to obtain polyimide. 3.5 g of this polyimide was dissolved in a mixed solvent of 10 g of NMP and 26.5 g of GBL, and further 10 g of BC was added to obtain a solution having a polyimide concentration of 8% by weight (varnish 36). The viscosity of the varnish 36 was 36.5 mPa · s, and the weight average molecular weight of the polyimide in the varnish was 32,000.

[Polymer Synthesis Example 37] Preparation of Varnish for Photoalignment Film 1.3881 g (5.156 mmol) of Compound (1-b-1), 1.0942 g (5.155 mmol) of DAAB, 0.4500 (2.063 mmol) of PMDA, and CBDA1 Using 6180 g (8.250 mmol), a polyamic acid solution (varnish 37) having a concentration of 5% by weight was obtained by the method according to Polymer Synthesis Example 1. The viscosity of the varnish 37 was 24 mPa · s, and the weight average molecular weight of the polyamic acid in the varnish 37 was 51,000.

[Polymer synthesis examples 38 to 41]
Except that the combination of diamine and tetracarboxylic dianhydride was changed to the combinations listed in Table 2, an operation according to Polymer Synthesis Example 37 was performed to obtain a polyamic acid solution (varnish 38 to 41) having a concentration of 5% by weight. The viscosity and weight average molecular weight of these varnishes are summarized in Table 2 together with Polymer Synthesis Example 37.

[Example 1] Preparation of cell for measuring pretilt angle and electrical characteristics 1.0 g of varnish 1 was weighed into a sample bottle and NMP / BC = 1/1 (% by weight) was added to obtain 1.67 g. A solution having a polyamic acid concentration of about 3% by weight was dropped on a glass substrate with ITO and applied by a spinner method (2,000 rpm, 15 seconds). After coating, the substrate was heated at 80 ° C. for 3 minutes to evaporate the solvent and then heat-treated in an oven at 230 ° C. for 20 minutes. The polyimide film having a film thickness of about 70 nm formed by this heat treatment was rubbed (pushing: 0.3 mm, stage feed speed: 60 m / s, rotation speed: 1000 rpm, rubbing cloth: YA-18-R (rayon)) . The alignment film was ultrasonically cleaned in ultrapure water for 5 minutes and then dried in an oven at 120 ° C. for 30 minutes. Two glass substrates are placed opposite to each other so that the rubbing direction is antiparallel with the surface on which the alignment film is formed, sealed with an epoxy hardener containing a gap agent of 4 μm, and anti-parallel with a gap of 4 μm. A cell was produced. The following liquid crystal composition A was injected into this 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. The pretilt angle of this cell was 1.6 degrees, the voltage holding ratio was 99.5% (30 Hz) and 96.3% (0.3 Hz), and the ion density was 14 pC.

<Liquid crystal composition A>

[Examples 2 to 28]
A cell was prepared by the method described in Example 1 except that varnish 1 was replaced with varnishes 2 to 28. Table 3 shows the measurement results of the pretilt angle and electrical characteristics together with the results of Example 1.

The liquid crystal alignment of the liquid crystal cells prepared in Examples 1 to 28 was confirmed by observation with a polarizing microscope. As a result, the generation of domains and the like due to rubbing scraping or deterioration of liquid crystal alignment was not observed at all.

偏光顕微鏡観察によって、これら実施例２９〜３１で作成した液晶セルの液晶配向性を確認した。その結果、ラビング削れによるまたは液晶配向性が悪化した事によるドメイン等の発生は全く観察されなかった。 [Examples 29 to 31]
A cell was prepared by the method described in Example 1 except that 3 wt% of the following compounds were added to the varnish 7 based on the solid content of the varnish. Table 4 shows the measurement results of the pretilt angle and electrical characteristics.

The liquid crystal orientation of the liquid crystal cells prepared in Examples 29 to 31 was confirmed by observation with a polarizing microscope. As a result, the occurrence of domains and the like due to rubbing scraping or deterioration of liquid crystal alignment was not observed at all.

[Example 32] Preparation of cell using photo-alignment film 1.0 g of varnish 37 was weighed out into a sample bottle, and NMP / BC = 1/1 (% by weight) was added to obtain 1.67 g. A solution having a polyamic acid concentration of about 3% by weight was dropped on a glass substrate with ITO and applied by a spinner method (1900 rpm, 15 seconds). After coating, the substrate was heated at 80 ° C. for 3 minutes to evaporate the solvent. This substrate was irradiated with linearly polarized light (illuminance of 30 mW / cm ² at 360 nm) for 30 seconds. Then, it heat-processed for 230 minutes at 230 degreeC in oven. Two glass substrates are placed opposite to each other so that the polarization direction at the time of exposure is parallel with the surface on which the alignment film is formed facing, and then sealed with an epoxy curing agent containing a gap agent of 4 μm, and a gap of 4 μm An anti-parallel cell was produced. The liquid crystal composition A was injected into this 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. The pretilt angle of this cell was 0.0 degree, the voltage holding ratio was 99.0% (30 Hz) and 93.8% (0.3 Hz), and the ion density was 48 pC.
[Examples 33 to 35]
A cell was produced by the method described in Example 32 except that the varnish 37 was replaced with the varnish 38-40. The measurement results of the pretilt angle and electrical characteristics are shown in Table 5 together with the results of Example 32.

[Comparative Examples 1-5]
A cell was prepared by the method described in Example 1 except that the varnish 1 was replaced with the following varnishes 30 to 33 and 35, and the pretilt angle and electrical characteristics were measured. Table 6 shows the measurement results.

The liquid crystal alignment of the liquid crystal cells prepared in Comparative Examples 1 to 5 was confirmed by observation with a polarizing microscope. As a result, in the liquid crystal cells prepared in Comparative Examples 1 to 4, the generation of domains and the like due to rubbing scraping or deterioration of liquid crystal alignment was not observed at all. However, rubbing scraping was observed in the liquid crystal cell prepared in Comparative Example 5, and some domains due to it were generated.

[Comparative Example 6]
A cell was produced by the method described in Example 32 except that the varnish 37 was replaced with the varnish 41. The pretilt angle of this cell was 0.1 degree, the voltage holding ratio was 95.8% (30 Hz) and 79.8% (0.3 Hz), and the ion density was 123 pC.

As is apparent from the comparison between Examples 7 and 8 and Comparative Examples 1 and 2, comparison between Example 26 and Comparative Example 3, and comparison between Examples 32 and 33 and Comparative Examples 5 and 6, the diamine of the present invention was used. The liquid crystal aligning agent has a high VHR value and a low ion density. Therefore, it can be seen that the battery has practically sufficient electrical characteristics and liquid crystal orientation.

[Example 36] Preparation and evaluation of VA cell Example 1 except that instead of varnish 1, a mixed varnish of varnish 29 and varnish 30 (mixing ratio; varnish 29: varnish 30 = 2: 8 v / v) was used. By the method according to this, the board | substrate which formed the polyimide film with a film thickness of about 70 nm on the upper surface of the glass substrate with ITO was obtained. Without rubbing the substrate, washing with pure water, and drying, the two glass substrates were placed facing each other with the surface on which the alignment film was formed, and then sealed with an epoxy curing agent containing a 4 μm gap agent. A non-rubbing cell with a gap of 4 μm was produced. The following liquid crystal composition B was injected into this 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. The pretilt angle of this cell was 90 °, and when observed with a polarizing microscope, no light leakage was observed in the crossed Nicol state, and it was confirmed that the alignment film had good vertical alignment.

The voltage holding ratio of this liquid crystal cell was 99.2% (30 Hz) and 92.1% (0.3 Hz), and the ion density was 76 pC.

<Liquid crystal composition B>

[Comparative Example 7]
A VA liquid crystal cell was prepared according to the method described in Example 36 except that varnish 34 was used instead of varnish 29.

The pretilt angle of this cell was 90 °, and when observed with a polarizing microscope, no light leakage was observed in the crossed Nicol state, and it was confirmed that the alignment film had good vertical alignment. The voltage holding ratio of this liquid crystal cell was 98.3% (30 Hz) and 85.9% (0.3 Hz), and the ion density was 245 pC.

As is clear from a comparison between Example 36 and Comparative Example 7, the liquid crystal aligning agent using the diamine of the present invention has a high VHR value and a low ion density. Therefore, it can be seen that the battery has practically sufficient electrical characteristics and liquid crystal orientation.

[Example 37] Measurement of volume resistivity of alignment film According to the method described in Example 1, a polyimide film prepared using varnish 1 was formed on a glass substrate with ITO on the entire surface (film thickness 300 nm, rubbing treatment). Does not go). Al was vapor-deposited on the alignment film surface of this substrate to form an upper electrode (electrode area 0.23 cm ² , FIG. 1). A voltage of 3 V was applied between the ITO electrode and the upper electrode, and the volume resistance value was measured from the current value after 300 seconds. As a result, it was 3.0 × 10 ¹² Ωcm.

[Examples 38 to 42]
In accordance with the method described in Example 37, the volume resistance value of an alignment film produced from the following varnish was measured. Table 7 shows the results of Example 37.

[Comparative Examples 8 to 11]
In accordance with the method described in Example 37, the volume resistance value of an alignment film produced from the following varnish was measured. The results are shown in Table 8.

As is apparent from the comparison of Examples 37 to 42 and Comparative Examples 8 to 11, it can be seen that the diamine of the present invention is very useful for reducing the volume resistance value of the alignment film.

[Examples 43 to 45]
In accordance with the method described in Example 1 except that a glass substrate without ITO was used instead of the glass substrate with ITO, an alignment film was formed using varnish 15, 25, or 3 and rubbed. As a result of measuring retardation of this substrate, it was as shown in Table 9.

[Comparative Examples 12 and 13]
An alignment film was formed using varnish 33 or 35 in accordance with the method described in Example 1 except that a glass substrate without ITO was used instead of a glass substrate with ITO, and a rubbing treatment was performed. As a result of measuring retardation of this substrate, it was as shown in Table 9.

Comparison with Examples 43 to 45 and Comparative Examples 12 and 13 shows that the diamine of the present invention is very useful for improving the retardation of the alignment film and imparting high alignment to the liquid crystal.

Claims (21)

Diamine represented by formula (1):

In the formula (1), R ¹ is a group capable of leaving by heat;
R ² is independently -H, a group capable of leaving by heat or a group having a group leaving by heat;
G ¹ and G ⁴ are independently a divalent organic group having an aromatic ring;
G ² is a single bond or alkylene having 1 to 10 carbons;
G ³ is a single bond, —O—, —CONH—, —NMe—, or —NR ¹ —;
a, b, and c are independently 0 or 1, but b is 1 when R ² is —H; and
When each of a and c is 1, —NH ₂ is directly bonded to the aromatic ring of the divalent organic group. The diamine according to claim 1, wherein in the diamine represented by the formula (1), the group capable of leaving by heat in R ¹ and R ² is a carbamate-based protecting group. The diamine according to claim ¹ , wherein R ¹ is Boc and R ² is —H, —NHBoc or —N (Boc) ₂ in the diamine represented by formula (1):
Here, Boc is a t-butoxycarbonyl group. The diamine according to claim 1, which is represented by any one of formulas (1-a) to (1-d):

In the formula (1-a) to the formula (1-d), Boc is a t-butoxycarbonyl group;
G ⁵ is alkylene having 2 to 10 carbons;
R ³ is independently —H, —NHBoc or —N (Boc) ₂ , and at least one of R ³ is —NHBoc or —N (Boc) ₂ . A diamine mixture containing at least one of the diamines according to any one of claims 1 to 4 or at least one of the diamines according to any one of claims 1 to 4, and a tetracarboxylic dianhydride A polyamic acid obtained by reacting a product or a derivative thereof. The polyamic acid or derivative thereof according to claim 5, which is obtained by reacting a mixture of at least one of the diamine according to any one of claims 1 to 4 with another diamine with tetracarboxylic dianhydride. The polyamic acid or derivative thereof according to claim 5 or 6, wherein the tetracarboxylic dianhydride is at least one selected from the group consisting of the following formulas (AN-I) to (AN-VII):

In formulas (AN-I), (AN-IV) and (AN-V), X is independently a single bond or —CH ₂ —;
In Formula (AN-II), G 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-II) to (AN-IV), Y is independently one selected from the group of trivalent groups below,

Any hydrogen in these groups may be replaced by methyl, ethyl or phenyl;
In the formulas (AN-III) to (AN-V), the ring A is a monocyclic hydrocarbon group having 3 to 10 carbon atoms or a condensed polycyclic hydrocarbon group having 6 to 30 carbon atoms. Any hydrogen in may be replaced by methyl, ethyl or phenyl, and the bond on the ring is connected to any carbon constituting the ring, and the two bonds are connected to the same carbon May be;
In the formula (AN-VI), X ¹⁰ is alkylene having 2 to 6 carbons;
Me is methyl;
Ph is phenyl;
In formula (AN-VII), G ¹⁰ is independently —O—, —COO— or —OCO—; and
r is independently 0 or 1. Tetracarboxylic dianhydride has the following formulas (AN-1-1), (AN-1-13), (AN-2-1), (AN-3-1), (AN-3-2), It is at least one selected from the group consisting of (AN-4-5), (AN-4-17), (AN-7-2), (AN-10), and (AN-11-3). The polyamic acid or derivative thereof according to claim 7:

In formula (AN-4-17), m is an integer of 1-12. The polyamic acid or derivative thereof according to claim 6, wherein the other diamine is at least one selected from the group consisting of the following formulas (DI-1) to (DI-17):

In formulas (DI-1) to (DI-7), m is an integer of 1 to 12;
G ²¹ is independently 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—, or —S— (CH ₂ ) _{m ′} —S—, and m ′ is independent. An integer from 1 to 12;
G ²² is independently a single bond, —O—, —S—, —CO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, or alkylene having 1 to 10 carbons;
Arbitrary —H of the cyclohexane ring and the benzene ring in each formula may be replaced by —F, —CH ₃ , —OH, —CF ₃ or benzyl. In addition, in the formula (DI-4), The following formulas (DI-4-a) to (DI-4-c) may be substituted,

In formulas (DI-4-a) to (DI-4-c), R ²⁰ is independently —H or —CH ₃ ;
In formulas (DI-2) to (DI-7), a group whose bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary; and
The bonding position of —NH ₂ to the cyclohexane ring or the benzene ring is an arbitrary position excluding the bonding position of G ²¹ or G ²² .

In formula (DI-8), R ²¹ and R ²² are each independently alkyl or phenyl having 1 to 3 carbon atoms;
G ²³ is independently alkylene having 1 to 6 carbons, phenylene or alkyl-substituted phenylene;
n is an integer from 1 to 10;
In formula (DI-9), R ²³ is independently alkyl having 1 to 3 carbons;
p is independently an integer from 0 to 3;
q is an integer from 0 to 4;
In the formula (DI-10), R ²⁴ is —H, alkyl having 1 to 4 carbons, phenyl, or benzyl;
In the formula (DI-11), G ²⁴ is —CH ₂ — or —NH—;
In the formula (DI-12), G ²⁵ is a single bond, alkylene having 2 to 6 carbons or 1,4-phenylene;
r is 0 or 1;
In formula (DI-12), a group whose bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary; and
In formulas (DI-9), (DI-11) and (DI-12), the bonding position of —NH ₂ bonded to the benzene ring is an arbitrary position;

In the formula (DI-13), G ²⁶ represents a single bond, —O—, —COO—, —OCO—, —CO—, —CONH—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—. , -OCF ₂ -, or - _(CH 2) _{m '-} it is and, m' is an integer from 1 to 12;
R ²⁵ is alkyl having 3 to 20 carbon atoms, phenyl, a group having a steroid skeleton, or a group represented by the following formula (DI-13-a). In this alkyl, any —H is —F. Any —CH ₂ — may be replaced by —O—, —CH═CH— or —C≡C—, and —H of this phenyl is —F, —CH ₃ , _{-OCH 3, -OCH 2 F, -OCHF} 2, -OCF 3, alkyl having 3 to 20 carbon atoms, or may be replaced by alkoxy having 3 to 20 carbon atoms, -H of cyclohexyl 3 carbon atoms Which may be substituted with ˜20 alkyl or C 3-20 alkoxy, and indicates that the bonding position of —NH ₂ bonded to the benzene ring is an arbitrary position in the ring;

In the formula (DI-13-a), G ²⁷ , G ²⁸ and G ²⁹ each represent a bonding group, and these are each independently a single bond or alkylene having 1 to 12 carbons, and one or more of the alkylene —CH ₂ — may be replaced by —O—, —COO—, —OCO—, —CONH—, —CH═CH—;
Ring B ²¹ , Ring B ²² , Ring B ²³ , and Ring B ²⁴ are independently 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2, 5-diyl, pyridine-2,5-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, or anthracene-9,10 -Diyl;
In ring B ²¹ , ring B ²² , ring B ²³ , and ring B ²⁴ , any —H may be replaced by —F or —CH ₃ ;
s, t and u are independently integers from 0 to 2 and their sum is 1 to 5;
when s, t or u is 2, the two linking groups in each bracket may be the same or different and the two rings may be the same or different;
R ²⁶ represents —F, —OH, alkyl having 1 to 30 carbon atoms, fluorine-substituted alkyl having 1 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms, —CN, —OCH ₂ F, —OCHF ₂ , or —OCF. _And any —CH ₂ — in the alkyl having 1 to 30 carbon atoms may be replaced by a divalent group represented by the following formula (DI-13-b);

In the formula (DI-13-b), R ²⁷ and R ²⁸ are independently alkyl having 1 to 3 carbons;
v is an integer from 1 to 6;

In formula (DI-14) and formula (DI-15), G ³⁰ is independently a single bond, —CO— or —CH ₂ —;
R ²⁹ is independently —H or —CH ₃ ;
R ³⁰ is —H, alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons;
One -H of the benzene ring in formula (DI-15) may be replaced by alkyl having 1 to 20 carbons or phenyl;
In formula (DI-14) and formula (DI-15), a group whose bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary;
Bonded to the benzene ring -NH ₂ indicates that the binding position in the ring is optional;

In formula (DI-16) and formula (DI-17), G ³¹ is independently —O— or alkylene having 1 to 6 carbons;
G ³² is a single bond or alkylene having 1 to 3 carbon atoms;
R ³¹ is —H or alkyl having 1 to 20 carbons, and any —CH ₂ — in the alkyl may be replaced by —O—, —CH═CH— or —C≡C—;
R ³² is alkyl having 6 to 22 carbons;
R ³³ is —H or C 1-22 alkyl;
Ring B ²⁵ is 1,4-phenylene or 1,4-cyclohexylene;
r is 0 or 1; and
-NH ₂ bonded to the benzene ring indicates that the binding position in the ring is optional. Other diamines may be represented by the following formulas (DI-4-1), (DI-5-1), (DI-5-5), (DI-5-9), (DI-5-12), (DI -5-21), (DI-5-27), (DI-5-29), (DI-7-3), (DI-9-1), (DI-13-4), (DI-13 -5), (DI-13-47), (DI-16-1), (DI-16-2), and (DI-16-4), which is at least one selected from the group consisting of 9. The polyamic acid or derivative thereof according to 9,

In the formulas (DI-5-1), (DI-5-12) and (DI-7-3), m is an integer of 1 to 12;
In the formula (DI-5-29), k is an integer of 1 to 5;
In the formula (DI-7-3), n is 1 or 2;
In formulas (DI-13-4) and (DI-13-5), R ³⁵ is alkyl having 1 to 30 carbons or alkoxy having 1 to 30 carbons;
In the formulas (DI-16-1) and (DI-16-2), R ⁴⁰ is —H or alkyl having 1 to 20 carbons;
In the formula (DI-16-4), R ⁴¹ represents —H or alkyl having 1 to 12 carbons. A varnish containing at least one polymer selected from the polyamic acid according to any one of claims 5 to 10 or a derivative thereof. The liquid crystal aligning agent containing the varnish of Claim 11. The liquid crystal alignment according to claim 12, further comprising at least one selected from the group consisting of an alkenyl-substituted nadiimide compound, a compound having a radical polymerizable unsaturated double bond, an oxazine compound, an oxazoline compound, and an epoxy compound. Agent. The alkenyl-substituted nadiimide compound is bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane, N, N′-m-xylylene-bis (allyl). Bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) and N, N′-hexamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2 The liquid crystal aligning agent of Claim 13 which is at least 1 chosen from the group of the compound which consists of a (, 3- dicarboximide). Compounds having a radically polymerizable unsaturated double bond are N, N′-ethylenebisacrylamide, N, N ′-(1,2-dihydroxyethylene) bisacrylamide, ethylenebisacrylate, and 4,4′-methylenebis ( The liquid crystal aligning agent of Claim 13 which is at least 1 chosen from the group of the compound which consists of N, N- dihydroxyethylene acrylate aniline). The epoxy compound is N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetra. Glycidyl-4,4′-diaminodiphenylmethane, 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3-epoxypropoxy] phenyl) )] Ethyl] phenyl] propane, 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate, N-phenylmaleimide-glycidyl methacrylate copolymer, and 2- (3,4-epoxycyclohexyl) The liquid crystal alignment according to claim 13, which is at least one selected from the group of compounds consisting of ethyltrimethoxysilane. . The liquid crystal aligning film formed with the liquid crystal aligning agent of any one of Claims 12-16. The liquid crystal display element which has a liquid crystal aligning film of Claim 17. A polyamic acid or a derivative thereof having a group that generates an —NH— group by being heated to 100 to 300 ° C. is baked to a temperature at which an —NH— group is generated by the elimination of the group, and then used as a liquid crystal alignment film. A method for forming a liquid crystal alignment film, characterized by the above. The method for forming a liquid crystal alignment film according to claim 19, wherein the liquid crystal aligning agent according to any one of claims 12 to 16 is used. A method for producing a liquid crystal display element, comprising forming a liquid crystal alignment film by the method according to claim 19 or 20.

Images