JP5245329B2 - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Description

  The present invention relates to a liquid crystal aligning agent containing an alkenyl-substituted nadiimide compound and at least one polymer selected from a polyamic acid and a derivative of this polyamic acid, a liquid crystal aligning film formed from this liquid crystal aligning agent, and this liquid crystal aligning film. The present invention relates to a liquid crystal display element.

  Liquid crystal display elements are used in various liquid crystal display devices such as monitors for notebook computers and desktop computers, video camera viewfinders, and projection displays. Recently, they have also been used as televisions. . Furthermore, it is also used as an optoelectronic-related element such as an optical printer head, an optical Fourier transform element, or a light valve.

Liquid crystal display elements are usually
1) a pair of substrates arranged opposite to each other;
2) Electrodes formed on one or both of the opposing surfaces of the pair of substrates,
3) a liquid crystal alignment film formed on the opposing surfaces of each of the pair of substrates; and 4) a liquid crystal layer formed between the pair of substrates.

  As a conventional liquid crystal display element, a display element using a nematic liquid crystal is mainly used, and a TN (Twisted Nematic) type liquid crystal display element twisted by 90 degrees, an STN (Super Twisted Nematic) type liquid crystal display element usually twisted by 180 degrees or more, A so-called TFT (Thin Film Transistor) type liquid crystal display element using a thin film transistor has been put into practical use. These liquid crystal display elements have a drawback that the viewing angle at which an image can be properly viewed is narrow, and when viewed from an oblique direction, luminance and contrast decrease and luminance inversion occurs in a halftone.

  In recent years, with regard to this viewing angle problem, TN-TFT type liquid crystal display elements using optical compensation films, VA (Vertical Alignment) type liquid crystal display elements using vertical alignment and optical compensation films, vertical alignment and protrusion structures MVA (Multi Domain Vertical Alignment) type liquid crystal display device combined with technology, lateral electric field type IPS (In-Plane Switching) type liquid crystal display device, ECB (Electrically Controlled Birefringence) type liquid crystal display device, Optically Compensated Bend (Optically Compensated Bend) Alternatively, it has been improved by a technique such as an optically self-compensated birefringence (OCB) type liquid crystal display element, and the improved technique has been put into practical use or being studied.

  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 liquid crystal display element. Among the structural members used in the liquid crystal display element, the liquid crystal alignment film is one of the important elements related to the display quality of the liquid crystal display element. Roles are becoming important year after year.

  The liquid crystal alignment film is prepared from a liquid crystal aligning agent. Currently, the liquid crystal aligning agent mainly used is a solution in which polyamic acid or soluble polyimide is dissolved in an organic solvent. After applying such a solution to a substrate, a polyimide-based alignment film is formed by film formation by means such as heating. Liquid crystal aligning agents that use various polymers other than polyamic acid are also being studied, but in terms of heat resistance, chemical resistance (liquid crystal resistance), coating properties, liquid crystal alignment properties, electrical properties, optical properties, display properties, etc. Almost no practical use.

  An important characteristic required for the liquid crystal alignment film in order to improve the display quality of the liquid crystal display element is a voltage holding ratio. When the voltage holding ratio is low, the voltage applied to the liquid crystal during the frame period is lowered, and as a result, the luminance is lowered, and normal gradation display may be hindered. Moreover, even if the initial voltage holding ratio is high, there is a problem when the voltage holding ratio (long-term reliability) after the high temperature acceleration test is lowered.

As an attempt to solve the above problems, the following several methods have been proposed recently.
1) A polyamic acid composition containing a combination of two or more polyamic acids having different physical properties for forming a liquid crystal alignment film is known (see, for example, Patent Documents 1 and 2).
2) A varnish composition containing a polymer component containing polyamic acid and polyamide and a solvent is known (see, for example, Patent Document 3).
3) A varnish composition containing two or more polyamic acids and polyamides having different physical properties and a solvent is known (see, for example, Patent Document 4).
4) A varnish composition containing a polymer material containing a polyamic acid or the like synthesized using a diamine compound having a specific structure is known (see, for example, Patent Document 5).
5) A technique of adding a low-molecular epoxy resin to polyimide and polyamic acid varnish is known (see, for example, Patent Document 6).
6) It should be noted that inventions similar to the present invention are disclosed in Patent Documents 7 and 8.
However, these prior arts have not sufficiently solved the problems of voltage holding ratio and long-term reliability.

JP 11-193345 A JP-A-11-193347 International Publication No. 00/61684 Pamphlet WO 01/000733 pamphlet JP 2002-162630 A JP 2005-189270 A JP-A-9-269491 JP 2004-341030 A

  In consideration of the above situation, a liquid crystal aligning agent for a liquid crystal display element in which the problems of voltage holding ratio and long-term reliability are improved, a liquid crystal alignment film formed using the same, and a liquid crystal display having the liquid crystal alignment film Development of devices is desired.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have formed a liquid crystal alignment film using a liquid crystal aligning agent containing an alkenyl-substituted nadiimide compound and a polyamic acid or a derivative thereof. It has been found that a good voltage holding ratio and long-term reliability can be imparted to a liquid crystal display element having the above, and the present invention has been completed.

  Furthermore, it has been found that by appropriately selecting the polyamic acid, a liquid crystal alignment film that can be appropriately applied to liquid crystal display elements of various display driving methods can be obtained.

ここに、Ｐｈはフェニルを、Ｍｅはメチルを意味する。 The liquid crystal aligning agent of this invention is shown by the following [1] term.
[1] A composition comprising an alkenyl-substituted nadiimide compound and a polymer component selected from a polyamic acid and a polyamic acid derivative, wherein the polymer component is at least one of the compounds represented by formulas (1) to (17). A liquid crystal aligning agent that is at least one of polymers obtained by reacting a tetracarboxylic dianhydride with a diamine:

Here, Ph means phenyl and Me means methyl.

  According to the present invention, it is possible to provide liquid crystal display elements of various driving methods that have a high voltage holding ratio and good long-term reliability.

本明細書中の化学構造式において、環に対する置換基または結合基の結合位置が明示されていない場合には、その結合位置を自由に選択できることを意味する。但し、上記のナジイミド基における置換基は、５、６または７位に結合していることが好ましい。式（１）で示される化合物を化合物（１）と略称することがある。他の式で示される化合物についても同様である。 First, terms will be explained. “Nadiimide compound” means a compound having the following nadiimide group.

In the chemical structural formulas in the present specification, when the bonding position of the substituent or bonding group to the ring is not clearly shown, it means that the bonding position can be freely selected. However, the substituent in the nadiimide group is preferably bonded to the 5, 6 or 7 position. A compound represented by the formula (1) may be abbreviated as a compound (1). The same applies to compounds represented by other formulas.

“Arbitrary” means that not only the position but also the number can be freely selected. And the expression “any A may be replaced by B, C or D” means that if any A is replaced by B, any A is replaced by C and any A is replaced by D In addition to the case, it is meant to include the case where a plurality of A is replaced by at least two of B to D. For example, alkyl in which any —CH ₂ — may be replaced by —O— or —CH═CH— includes alkyl, alkenyl, alkoxy, alkoxyalkyl, alkoxyalkenyl, alkenyloxyalkyl, and the like. In the present invention, it is not preferable that two consecutive —CH ₂ — are replaced by —O—.

  Regarding the side chain type diamine and the non-side chain type diamine, definitions of these terms will be described at the beginning of the explanation regarding the diamine used in the present invention.

The present invention is composed of the above item [1] and the following items [2] to [15].
[2] A composition comprising an alkenyl-substituted nadiimide compound and a polymer component selected from a polyamic acid and a derivative of this polyamic acid, wherein the polymer component is represented by the compound represented by the formula (16) and the formula (17). Tetra, which is a mixture of at least one of the compounds represented by formula (16) and at least one of the compounds represented by formula (17) and at least one of the compounds represented by formula (1) to formula (15) The liquid crystal aligning agent as described in the item [1], which is a polymer obtained by a reaction of a carboxylic dianhydride and a diamine.

ここに、Ｒ^１およびＲ^２は独立して水素、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であり；
ｎが１であるとき、Ｒ^３は炭素数１〜１２のアルキル、炭素数５〜８のシクロアルキル、炭素数６〜１２のアリール、ベンジル、−Ｌ^１−（Ｏ）_ｑ−（Ｌ^２Ｏ）_ｒ−Ｒ^４（Ｌ^１およびＬ^２は独立して炭素数２〜６のアルキレンであり、Ｒ^４は炭素数２〜６のアルキルであり、ｑは０または１であり、そしてｒは１〜３０の整数である。）、−（Ｌ^３）_ｓ−Ｂ^２−Ｒ^５（Ｌ^３は炭素数１〜４のアルキレンであり、ｓは０または１であり、Ｂ^２は任意の水素が−ＯＨで置き換えられてもよいフェニレンであり、そしてＲ^５は炭素数１〜４のアルキルである。）、または−Ｂ^２−Ｔ−Ｂ^１（Ｂ^２は任意の水素が−ＯＨで置き換えられてもよいフェニレンであり、Ｔは−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−ＣＯ−、−Ｏ−、−Ｓ−または−ＳＯ_２−であり、そしてＢ^１は任意の水素が−ＯＨで置き換えられてもよいフェニルである。）であり；
ｎが２であるとき、Ｒ^３は炭素数２〜２０のアルキレン、炭素数５〜８のシクロアルキレン、炭素数６〜１２のアリーレン、−Ｌ^１−（Ｏ）_ｑ−（Ｌ^２Ｏ）_ｒ−Ｌ^４−（Ｌ^１、Ｌ^２およびＬ^４は独立して炭素数２〜６のアルキレンであり、ｑは０または１であり、そしてｒは１〜３０の整数である。）、−（Ｌ^３）_ｓ−Ｂ^２−Ｌ^５−（Ｌ^３およびＬ^５は独立して炭素数１〜４のアルキレンであり、ｓは０または１であり、Ｂ^２は任意の水素が−ＯＨで置き換えられてもよいフェニレンである。）、−Ｂ^２−Ｔ−Ｂ^２−（Ｂ^２は独立して任意の水素が−ＯＨで置き換えられてもよいフェニレンであり、そしてＴは−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−ＣＯ−、−Ｏ−、−Ｓ−または−ＳＯ_２−である。）、または−Ｂ^２−Ｏ−Ｂ^２−Ｃ（ＣＨ_３）_２−Ｂ^２−Ｏ−Ｂ^２−（Ｂ^２は独立して任意の水素が−ＯＨで置き換えられてもよいフェニレンである。）である。 [3] The liquid crystal aligning agent according to the item [1] or [2], wherein the alkenyl-substituted nadiimide compound is a compound represented by the formula (a):

Wherein R ¹ and R ² are independently hydrogen, alkyl having 1 to 12 carbons, alkenyl having 3 to 6 carbons, cycloalkyl having 5 to 8 carbons, aryl or benzyl, and n is 1 or 2 Is;
When n is 1, R ³ is alkyl having 1 to 12 carbons, cycloalkyl having 5 to 8 carbons, aryl having 6 to 12 carbons, benzyl, -L ^1- (O) _q- (L ² O ) _R— R ⁴ (L ¹ and L ² are independently alkylene having 2 to 6 carbons, R ⁴ is alkyl having 2 to 6 carbons, q is 0 or 1, and r is 1 ),-(L ³ ) _s -B ² -R ⁵ (L ³ is alkylene having 1 to 4 carbon atoms, s is 0 or 1, and B ² is any hydrogen. Phenylene, which may be replaced with —OH, and R ⁵ is alkyl having 1 to 4 carbon atoms), or —B ² -T-B ¹ (B ² is any hydrogen replaced with —OH; and is also phenylene, T is _{-CH 2 -, - C (CH} 3) 2 -, - CO -, - O-, S- or -SO ₂ -, and ^{B 1} represents be a) phenyl which may be replaced arbitrary hydrogen in -OH;.
When n is 2, R ³ is alkylene having 2 to 20 carbon atoms, cycloalkylene having 5 to 8 carbon atoms, arylene having 6 to 12 carbon atoms, -L ^1- (O) _q- (L ² O) _r -L ⁴ - ^(L 1, ^{L 2} and ^{L 4} are independently alkylene of 2 to 6 carbon atoms, q is 0 or 1, and r is an integer from 1 to 30.), - ( L ³ ) _s -B ² -L ^5- (L ³ and L ⁵ are each independently an alkylene having 1 to 4 carbon atoms, s is 0 or 1, and B ² is any hydrogen replaced with -OH. -B ² -T-B ^2- (B ² is independently phenylene in which any hydrogen may be replaced by -OH, and T is -CH _2- , _{-C (CH 3) 2 -,} - CO -, - O -, - S- or -SO ₂ -. a a), or - _{^{2 -O-B 2 -C (CH}} 3) 2 -B 2 -O-B 2 - a ^{(B 2} is any independently hydrogen is phenylene which may be replaced by -OH.).

[4] The liquid crystal aligning agent according to the item [1], wherein the alkenyl-substituted nadiimide compound is at least one of compounds represented by formulas (a-1) to (a-3):

[5] The liquid crystal aligning agent according to any one of [1] to [4], wherein the ratio of the alkenyl-substituted nadiimide compound is 0.01 to 2 by weight ratio to the polymer component in the liquid crystal aligning agent.

ここに、Ａ^１は炭素数２〜１２の直鎖アルキレンであり；Ａ^２は炭素数１〜１２の直鎖アルキレンであり；Ａ^３は独立して単結合、−Ｏ−、−ＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−、−Ｏ−Ａ^２−Ｏ−、−Ｓ−、−Ｓ−Ｓ−、−ＳＯ_２−、−Ｓ−Ａ^２−Ｓ−、またはＡ^２であり；シクロヘキサン環およびベンゼン環の任意の水素はフッ素、−ＣＨ_３、−ＯＨ、−ＣＯＯＨ、−ＳＯ_３Ｈ、ＰＯ_３Ｈ_２、ベンジルまたはヒドロキシベンジルで置き換えられてもよい。 [6] The liquid crystal aligning agent according to any one of claims 1 to 5, wherein the diamine is at least one selected from the group of non-side chain diamines represented by formulas (I) to (VII):

Wherein A ¹ is a linear alkylene having 2 to 12 carbon atoms; A ² is a linear alkylene having 1 to 12 carbon atoms; A ³ is independently a single bond, —O—, —CO—, —CONH—, —NHCO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —O—A ² —O—, —S—, —S—S—, —SO ₂ —, ^-S-a 2 -S-, or be ^{a 2;} any hydrogen in cyclohexane ring and benzene ring are _{fluorine, -CH 3, -OH, -COOH,} -SO 3 H, PO 3 H 2, benzyl or hydroxy It may be replaced with benzyl.

[7] The diamine is represented by formula (IV-1), formula (IV-2), formula (IV-15), formula (IV-16), formula (V-1) to formula (V-13), and formula (IV). The liquid crystal aligning agent according to any one of [1] to [5], which is at least one selected from the group of non-side chain diamines represented by VII-2):

ここに、Ａ^１は炭素数２〜１２の直鎖アルキレンであり；Ａ^２は炭素数１〜１２の直鎖アルキレンであり；Ａ^３は独立して単結合、−Ｏ−、−ＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−、−Ｏ−Ａ^２−Ｏ−、−Ｓ−、−Ｓ−Ｓ−、−ＳＯ_２−、−Ｓ−Ａ^２−Ｓ−、またはＡ^２であり；シクロヘキサン環およびベンゼン環の任意の水素はフッ素、−ＣＨ_３、−ＯＨ、−ＣＯＯＨ、−ＳＯ_３Ｈ、ＰＯ_３Ｈ_２、ベンジルまたはヒドロキシベンジルで置き換えられてもよい。 [8] The diamine is a mixture of at least one selected from the group of non-side chain diamines represented by formulas (I) to (VII) and at least one side chain diamine having a side chain group, Alkyl having 3 or more carbon atoms, alkoxy having 3 or more carbon atoms, alkoxyalkyl having 3 or more carbon atoms, a group having a steroid skeleton, alkyl having 3 or more carbon atoms at the terminal, alkoxy having 3 or more carbon atoms or carbon The liquid crystal aligning agent according to any one of [1] to [5], which is a group selected from groups having several or more alkoxyalkyl groups:

Wherein A ¹ is a linear alkylene having 2 to 12 carbon atoms; A ² is a linear alkylene having 1 to 12 carbon atoms; A ³ is independently a single bond, —O—, —CO—, —CONH—, —NHCO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —O—A ² —O—, —S—, —S—S—, —SO ₂ —, ^-S-a 2 -S-, or be ^{a 2;} any hydrogen in cyclohexane ring and benzene ring are _{fluorine, -CH 3, -OH, -COOH,} -SO 3 H, PO 3 H 2, benzyl or hydroxy It may be replaced with benzyl.

（ここに、Ｒ^６は単結合、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＣＨ_２Ｏ−、−ＣＦ_２Ｏ−、または炭素数１〜６のアルキレンであって、このアルキレンにおける任意の−ＣＨ_２−は−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく；Ｒ^７はステロイド骨格を有する基、炭素数３〜３０のアルキル、置換基として炭素数３〜３０のアルキルもしくは炭素数３〜３０のアルコキシを有するフェニル、または式（Ｄ−１）で表される基であって、このアルキルにおける任意の−ＣＨ_２−は−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく；

ここに、Ｒ^１８、Ｒ^１９およびＲ^２０は独立して単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、炭素数１〜４のアルキレン、炭素数１〜３のオキシアルキレン、または炭素数１〜３のアルキレンオキシであり；環Ｂおよび環Ｃは独立して１，４−フェニレンまたは１，４−シクロヘキシレンであり；Ｒ^２１およびＲ^２２は独立してフッ素またはメチルであって、ｍ１およびｍ２は独立して０、１または２であり；ｅ、ｆおよびｇは独立して０〜３の整数であって、これらの合計は１以上であり；Ｒ^２３は炭素数３〜３０のアルキル、炭素数３〜３０のアルコキシ、または炭素数３〜３０のアルコキシアルキルであり、これらのアルキル、アルコキシおよびアルコキシアルキルにおいて、任意の水素はフッ素で置き換えられてもよく、そして任意の−ＣＨ_２−はジフルオロメチレンまたは式（Ｄ−２）で表される基で置き換えられてもよく；

ここに、Ｒ^２４、Ｒ^２５、Ｒ^２６およびＲ^２７は、独立して炭素数１〜１０のアルキルまたはフェニルであり、そしてｎは１〜１００の整数である。）

（ここに、Ｒ^８は独立して水素またはメチルであり；Ｒ^９は水素、炭素数１〜３０のアルキル、または炭素数２〜３０のアルケニルであり；そして、Ｒ^１０は独立して単結合、−ＣＯ−または−ＣＨ_２−である。）

（ここに、Ｒ^８は独立して水素またはメチルであり；Ｒ^９は水素、炭素数１〜３０のアルキル、または炭素数２〜３０のアルケニルであり；Ｒ^１０は独立して単結合、−ＣＯ−または−ＣＨ_２−であり；そして、Ｒ^１１およびＲ^１２は独立して水素、炭素数１〜３０のアルキル、またはフェニルである。）

（ここに、Ｒ^１３は炭素数３〜３０のアルキルであって、このアルキルの任意の−ＣＨ_２−は−Ｏ−、−ＣＨ＝ＣＨ−またはＣ≡Ｃ−で置き換えられてもよく；Ｒ^１４は独立して−Ｏ−または炭素数１〜６のアルキレンであり；環Ａは１，４−フェニレンまたは１，４−シクロヘキシレンであり；ａは０または１であり；ｂは０、１または２であり；そして、ｃは独立して０または１である。）

（ここに、Ｒ^１５は炭素数３〜３０のアルキルまたは炭素数３〜３０のフッ素化アルキルであり；Ｒ^１６は水素、炭素数１〜３０のアルキルまたは炭素数１〜３０のフッ素化アルキルであり；Ｒ^１７は独立して−Ｏ−または炭素数１〜６のアルキレンであり；そして、ｄは独立して０または１である。） [9] The liquid crystal aligning agent according to item [8], wherein the side chain diamine is a diamine selected from the group of compounds represented by formulas (VIII) to (XII):

(Here, ^{R 6} represents a single bond, -O -, - CO -, - COO -, - OCO -, - CONH -, - CH 2 O -, - CF 2 O-, or an alkylene having 1 to 6 carbon atoms And any —CH ₂ — in the alkylene may be replaced by —O—, —CH═CH— or —C≡C—; R ⁷ is a group having a steroid skeleton, having 3 to 30 carbon atoms Alkyl having 3 to 30 carbon atoms or phenyl having 3 to 30 carbon atoms as a substituent, or a group represented by formula (D-1), and any —CH ₂ — in the alkyl May be replaced by —O—, —CH═CH— or —C≡C—;

Here, R ¹⁸ , R ¹⁹ and R ²⁰ are independently a single bond, —O—, —COO—, —OCO—, —CONH—, alkylene having 1 to 4 carbons, or oxyalkylene having 1 to 3 carbons. Or Ring C and C are independently 1,4-phenylene or 1,4-cyclohexylene; R ²¹ and R ²² are independently fluorine or methyl; There are, m1 and m2 is independently 0, 1 or 2; e, f and g is an integer of 0 to 3 independently, their sum is 1 or ^{more; R 23} is the number of carbon atoms An alkyl having 3 to 30 carbons, an alkoxy having 3 to 30 carbons, or an alkoxyalkyl having 3 to 30 carbons, and in these alkyls, alkoxys and alkoxyalkyls, any hydrogen is replaced by fluorine. And any —CH ₂ — may be replaced by difluoromethylene or a group represented by formula (D-2);

Here, R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ are each independently alkyl or phenyl having 1 to 10 carbon atoms, and n is an integer of 1 to 100. )

(Wherein R ⁸ is independently hydrogen or methyl; R ⁹ is hydrogen, alkyl having 1 to 30 carbons, or alkenyl having 2 to 30 carbons; and R ¹⁰ is independently a single bond) , -CO- or -CH ₂ - is).

(Wherein R ⁸ is independently hydrogen or methyl; R ⁹ is hydrogen, alkyl having 1 to 30 carbons, or alkenyl having 2 to 30 carbons; R ¹⁰ is independently a single bond, — CO— or —CH ₂ —; and R ¹¹ and R ¹² are independently hydrogen, alkyl having 1 to 30 carbons, or phenyl.)

(Wherein R ¹³ is alkyl having 3 to 30 carbon atoms, and any —CH ₂ — in the alkyl may be replaced by —O—, —CH═CH— or C≡C—; R ¹⁴ is independently -O- or alkylene having 1 to 6 carbon atoms; ring A is 1,4-phenylene or 1,4-cyclohexylene; a is 0 or 1; b is 0, 1 Or 2; and c is independently 0 or 1.)

(Wherein R ¹⁵ is alkyl having 3 to 30 carbon atoms or fluorinated alkyl having 3 to 30 carbon atoms; R ¹⁶ is hydrogen, alkyl having 1 to 30 carbon atoms or fluorinated alkyl having 1 to 30 carbon atoms. Yes; R ¹⁷ is independently —O— or alkylene having 1 to 6 carbons; and d is independently 0 or 1.

ここに、Ｒ^２８およびＲ^２９は独立して炭素数３〜３０のアルキル、または炭素数３〜３０のアルコキシである。 [10] The side chain diamine is a diamine selected from the group of compounds represented by formula (VIII-2), formula (VIII-4), formula (VIII-5) and formula (VIII-6). ] Liquid crystal aligning agent as described in the term:

Here, R ²⁸ and R ²⁹ are independently alkyl having 3 to 30 carbons or alkoxy having 3 to 30 carbons.

ここに、Ｒ^２８およびＲ^２９は独立して炭素数３〜３０のアルキル、または炭素数３〜３０のアルコキシである。 [11] The non-side chain diamine is represented by formula (IV-1), formula (IV-2), formula (IV-15), formula (IV-16), formula (V-1) to formula (V-13). And a diamine selected from the group of compounds represented by formula (VII-2), wherein the side chain diamine is formula (VIII-2), formula (VIII-4), formula (VIII-5) and formula (VIII- The liquid crystal aligning agent according to item [8], which is a diamine selected from the group of compounds represented by 6):

Here, R ²⁸ and R ²⁹ are independently alkyl having 3 to 30 carbons or alkoxy having 3 to 30 carbons.

（ここに、Ｐｈはフェニルを、Ｍｅはメチルを意味する。 ポリマー成分が少なくとも２つのポリマーの混合物である。）

（ここに、Ａ^１は炭素数２〜１２の直鎖アルキレンであり；Ａ^２は炭素数１〜１２の直鎖アルキレンであり；Ａ^３は独立して単結合、−Ｏ−、−ＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−、−Ｏ−Ａ^２−Ｏ−、−Ｓ−、−Ｓ−Ｓ−、−ＳＯ_２−、−Ｓ−Ａ^２−Ｓ−、またはＡ^２であり；シクロヘキサン環およびベンゼン環の任意の水素は、フッ素、−ＣＨ_３、−ＯＨ、−ＣＯＯＨ、−ＳＯ_３Ｈ、ＰＯ_３Ｈ_２、ベンジルまたはヒドロキシベンジルで置き換えられてもよい。）

（ここに、Ｒ^６は単結合、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＣＨ_２Ｏ−、−ＣＦ_２Ｏ−、または炭素数１〜６のアルキレンであって、このアルキレンにおける任意の−ＣＨ_２−は−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく；Ｒ^７はステロイド骨格を有する基、炭素数３〜３０のアルキル、置換基として炭素数３〜３０のアルキルもしくは炭素数３〜３０のアルコキシを有するフェニル、または式（Ｄ−１）で表される基であって、このアルキルにおける任意の−ＣＨ_２−は−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく；

ここに、Ｒ^１８、Ｒ^１９およびＲ^２０は独立して単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、炭素数１〜４のアルキレン、炭素数１〜３のオキシアルキレン、または炭素数１〜３のアルキレンオキシであり；環Ｂおよび環Ｃは独立して１，４−フェニレンまたは１，４−シクロヘキシレンであり；Ｒ^２１およびＲ^２２は独立してフッ素またはメチルであって、ｍ１およびｍ２は独立して０、１または２であり；ｅ、ｆおよびｇは独立して０〜３の整数であって、これらの合計は１以上であり；Ｒ^２３は炭素数３〜３０のアルキル、炭素数３〜３０のアルコキシ、または炭素数３〜３０のアルコキシアルキルであり、これらのアルキル、アルコキシおよびアルコキシアルキルにおいて、任意の水素はフッ素で置き換えられてもよく、そして任意の−ＣＨ_２−はジフルオロメチレンまたは式（Ｄ−２）で表される基で置き換えられてもよく；

ここに、Ｒ^２４、Ｒ^２５、Ｒ^２６およびＲ^２７は、独立して炭素数１〜１０のアルキルまたはフェニルであり、そしてｎは１〜１００の整数である。）

（ここに、Ｒ^８は独立して水素またはメチルであり；Ｒ^９は水素、炭素数１〜３０のアルキル、または炭素数２〜３０のアルケニルであり；そして、Ｒ^１０は独立して単結合、−ＣＯ−または−ＣＨ_２−である。）

（ここに、Ｒ^８は独立して水素またはメチルであり；Ｒ^９は水素、炭素数１〜３０のアルキル、または炭素数２〜３０のアルケニルであり；Ｒ^１０は独立して単結合、−ＣＯ−または−ＣＨ_２−であり；そして、Ｒ^１１およびＲ^１２は独立して水素、炭素数１〜３０のアルキル、またはフェニルである。）

（ここに、Ｒ^１３は炭素数３〜３０のアルキルであって、このアルキルの任意の−ＣＨ_２−は−Ｏ−、−ＣＨ＝ＣＨ−またはＣ≡Ｃ−で置き換えられてもよく；Ｒ^１４は独立して−Ｏ−または炭素数１〜６のアルキレンであり；環Ａは１，４−フェニレンまたは１，４−シクロヘキシレンであり；ａは０または１であり；ｂは０、１または２であり；そして、ｃは独立して０または１である。）

（ここに、Ｒ^１５は炭素数３〜３０のアルキルまたは炭素数３〜３０のフッ素化アルキルであり；Ｒ^１６は水素、炭素数１〜３０のアルキルまたは炭素数１〜３０のフッ素化アルキルであり；Ｒ^１７は独立して−Ｏ−または炭素数１〜６のアルキレンであり；そして、ｄは独立して０または１である。） [12] A tetracarboxylic dianhydride whose polymer component is at least one of the compounds represented by formulas (1) to (17) and a non-side chain diamine represented by formulas (I) to (VII) A polyamic acid obtained by reaction with at least one selected from the group of: or a derivative thereof, at least selected from the group of the above-mentioned tetracarboxylic dianhydrides and side chain diamines represented by formulas (VIII) to (XII) A polyamic acid or derivative thereof obtained by reaction with one, and a polyamic acid or derivative thereof obtained by reaction of the tetracarboxylic dianhydride with a mixture of the non-side chain diamine and side chain diamine. The liquid crystal aligning agent according to item [1], which is at least two polymers selected:

(Here, Ph means phenyl and Me means methyl. The polymer component is a mixture of at least two polymers.)

(Wherein A ¹ is a linear alkylene having 2 to 12 carbon atoms; A ² is a linear alkylene having 1 to 12 carbon atoms; A ³ is independently a single bond, —O—, —CO—. , —CONH—, —NHCO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —O—A ² —O—, —S—, —S—S—, —SO ₂ —. , —S—A ² —S—, or A ² ; any hydrogen in the cyclohexane ring and the benzene ring is fluorine, —CH ₃ , —OH, —COOH, —SO ₃ H, PO ₃ H ₂ , benzyl Or may be replaced by hydroxybenzyl.)

(Here, ^{R 6} represents a single bond, -O -, - CO -, - COO -, - OCO -, - CONH -, - CH 2 O -, - CF 2 O-, or an alkylene having 1 to 6 carbon atoms And any —CH ₂ — in the alkylene may be replaced by —O—, —CH═CH— or —C≡C—; R ⁷ is a group having a steroid skeleton, having 3 to 30 carbon atoms Alkyl having 3 to 30 carbon atoms or phenyl having 3 to 30 carbon atoms as a substituent, or a group represented by formula (D-1), and any —CH ₂ — in the alkyl May be replaced by —O—, —CH═CH— or —C≡C—;

Here, R ¹⁸ , R ¹⁹ and R ²⁰ are independently a single bond, —O—, —COO—, —OCO—, —CONH—, alkylene having 1 to 4 carbons, or oxyalkylene having 1 to 3 carbons. Or Ring C and C are independently 1,4-phenylene or 1,4-cyclohexylene; R ²¹ and R ²² are independently fluorine or methyl; There are, m1 and m2 is independently 0, 1 or 2; e, f and g is an integer of 0 to 3 independently, their sum is 1 or ^{more; R 23} is the number of carbon atoms An alkyl having 3 to 30 carbons, an alkoxy having 3 to 30 carbons, or an alkoxyalkyl having 3 to 30 carbons, and in these alkyls, alkoxys and alkoxyalkyls, any hydrogen is replaced by fluorine. And any —CH ₂ — may be replaced by difluoromethylene or a group represented by formula (D-2);

Here, R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ are each independently alkyl or phenyl having 1 to 10 carbon atoms, and n is an integer of 1 to 100. )

(Wherein R ⁸ is independently hydrogen or methyl; R ⁹ is hydrogen, alkyl having 1 to 30 carbons, or alkenyl having 2 to 30 carbons; and R ¹⁰ is independently a single bond) , -CO- or -CH ₂ - is).

(Wherein R ⁸ is independently hydrogen or methyl; R ⁹ is hydrogen, alkyl having 1 to 30 carbons, or alkenyl having 2 to 30 carbons; R ¹⁰ is independently a single bond, — CO— or —CH ₂ —; and R ¹¹ and R ¹² are independently hydrogen, alkyl having 1 to 30 carbons, or phenyl.)

(Wherein R ¹³ is alkyl having 3 to 30 carbon atoms, and any —CH ₂ — in the alkyl may be replaced by —O—, —CH═CH— or C≡C—; R ¹⁴ is independently -O- or alkylene having 1 to 6 carbon atoms; ring A is 1,4-phenylene or 1,4-cyclohexylene; a is 0 or 1; b is 0, 1 Or 2; and c is independently 0 or 1.)

(Wherein R ¹⁵ is alkyl having 3 to 30 carbon atoms or fluorinated alkyl having 3 to 30 carbon atoms; R ¹⁶ is hydrogen, alkyl having 1 to 30 carbon atoms or fluorinated alkyl having 1 to 30 carbon atoms. Yes; R ¹⁷ is independently —O— or alkylene having 1 to 6 carbons; and d is independently 0 or 1.

ここに、Ｒ^２８およびＲ^２９は独立して炭素数３〜３０のアルキル、または炭素数３〜３０のアルコキシである。 [13] The polymer component is at least one of the compound represented by the formula (16) and the compound represented by the formula (17) or at least one of the compound represented by the formula (16) and the compound represented by the formula (17). Tetracarboxylic dianhydride that is a mixture with at least one of the compounds represented by formula (1) to formula (15), formula (IV-1), formula (IV-2), formula (IV-15), formula (IV-16), polyamic acid obtained by reaction with at least one selected from the group of non-side chain diamines represented by formula (V-1) to formula (V-13) and formula (VII-2) or A derivative thereof, selected from the group consisting of the tetracarboxylic dianhydrides and side chain diamines represented by formula (VIII-2), formula (VIII-4), formula (VIII-5) and formula (VIII-6) Polya obtained by reaction with at least one At least two polymers selected from a mimic acid or derivative thereof, and a polyamic acid or derivative thereof obtained by reacting the tetracarboxylic dianhydride with a mixture of the non-side chain diamine and the side chain diamine. The liquid crystal aligning agent as described in the item [12]:

Here, R ²⁸ and R ²⁹ are independently alkyl having 3 to 30 carbons or alkoxy having 3 to 30 carbons.

[14] A liquid crystal alignment film formed by firing the liquid crystal aligning agent according to any one of [1] to [13] in a film state.

[15] A pair of substrates disposed opposite to each other, electrodes formed on one or both of the surfaces facing each other of the pair of substrates, and surfaces facing each of the pair of substrates. A liquid crystal display device comprising the liquid crystal alignment film according to item [14] and a liquid crystal layer formed between the pair of substrates.

  The liquid crystal aligning agent of the present invention is a composition containing an alkenyl-substituted nadiimide compound and a polymer component selected from a polyamic acid and a derivative of this polyamic acid. A polyamic acid is a polymer obtained by reacting a tetracarboxylic dianhydride and a diamine, dissolved in a solvent, applied to a substrate, and heated to form a liquid crystal hard coating comprising a polyimide thin film on the substrate surface. Can be formed. Examples of such polyamic acid derivatives are soluble polyimides, polyamic acid esters, and polyamic acid amides. More specifically, a polyimide obtained by completely dehydrating and cyclizing an amide bond and a carboxyl group of a polyamic acid, a partial polyimide obtained by partially dehydrating and cyclizing a polyamic acid, a polyamic acid ester obtained by converting a carboxyl group of a polyamic acid into an ester, tetra A polyamic acid-polyamide copolymer obtained by reacting a part of a carboxylic dianhydride with a dicarboxylic acid (or its halide or anhydride), and the polyamic acid-polyamide copolymer partially or completely. And polyamideimide obtained by dehydration ring closure. In addition, when tetracarboxylic dianhydride and dicarboxylic acid are mixed and used as an acid component, not only a polyamic acid-polyamide copolymer but also a mixture containing polyamide and / or polyamic acid may be obtained. However, in the present invention, it is referred to as a polyamic acid-polyamide copolymer based on such a possibility. In the present invention, at least one polymer selected from such polyamic acids and derivatives thereof is used. And it is preferable to mix and use at least two of such polymers.

ここに、Ｒ^１およびＲ^２は独立して水素、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。 A preferred example of the alkenyl-substituted nadiimide compound used in the present invention is a compound represented by the formula (a).

Wherein R ¹ and R ² are independently hydrogen, alkyl having 1 to 12 carbons, alkenyl having 3 to 6 carbons, cycloalkyl having 5 to 8 carbons, aryl or benzyl, and n is 1 or 2 It is.

When n is 1, R ³ is alkyl having 1 to 12 carbons, cycloalkyl having 5 to 8 carbons, aryl having 6 to 12 carbons, benzyl, -L ^1- (O) _q- (L ² O ) _R -R ⁴ ,-(L ³ ) _s -B ² -R ⁵ , or -B ² -T-B ¹ . At this time, L ¹ and L ² are independently alkylene having 2 to 6 carbon atoms, L ³ is alkylene having 1 to ⁴ carbon atoms, R ⁴ is alkyl having 2 to 6 carbon atoms, and R ⁵ Is alkyl having 1 to 4 carbon atoms, B ¹ is phenyl in which any hydrogen may be replaced with —OH, B ² is phenylene in which any hydrogen is replaced with —OH, and T Is —CH ₂ —, —C (CH ₃ ) ₂ —, —CO—, —O—, —S— or —SO ₂ —, q is 0 or 1, and r is an integer of 1-30. Yes, and s is 0 or 1.

When n is 2, R ³ is alkylene having 2 to 20 carbon atoms, cycloalkylene having 5 to 8 carbon atoms, arylene having 6 to 12 carbon atoms, -L ^1- (O) _q- (L ² O) _{r ^{-L 4 -, - (L 3}} ) s -B 2 -L 5 -, - B 2 -T-B 2 -, or _{^{-B 2 -O-B 2 -C (}} CH 3) 2 -B 2 -O -B ² - is. At this time, L ¹ , L ² and L ⁴ are independently alkylene having 2 to 6 carbons, L ³ and L ⁵ are independently alkylene having 1 to 4 carbons, and B ² is independently Any hydrogen is phenylene which may be replaced by —OH, and T is —CH ₂ —, —C (CH ₃ ) ₂ —, —CO—, —O—, —S— or —SO ₂ —. , Q is 0 or 1, r is an integer from 1 to 30, and s is 0 or 1.

Specific examples of the alkenyl-substituted nadiimide compound include the following compounds and oligomers thereof.
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) -allylmethylbicyclo [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-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-isopropenyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-cyclohexyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-cyclohexyl-allylmethylbicyclo [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-allylmethylbicyclo [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) -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (2′-hydroxyethyl) -methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide

N- (2 ′, 2′-dimethyl-3′-hydroxypropyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (2 ′, 2′-dimethyl-3′-hydroxypropyl) -allylmethylbicyclo [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) -allylmethylbicyclo [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′-hydroxy-cyclohexyl) -allylmethylbicyclo [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) -allylmethylbicyclo [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) -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (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} -allylmethylbicyclo [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] -allylmethylbicyclo [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′-hydroxyphenylisopropylidene) phenyl} -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- {4 ′-(4′-hydroxyphenylisopropylidene) phenyl} -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- {4 ′-(4′-hydroxyphenylisopropylidene) phenyl} -methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide

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-dicarboximide),
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-dicarboximide) propoxy} ethane,
1,2-bis {3 ′-(allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) propoxy} ethane,
1,2-bis {3 ′-(methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) 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] hept-5-ene-2,3-dicarboximide) propoxy} butane,
1,4-bis {3 ′-(allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) 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-dicarboximide),
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- (allylmethylbicyclo [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,
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-dihydroxy) 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-dicarboximide) -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 (ethylenemethallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) isocyanurate

Further, the following one containing an asymmetric alkylene-phenylene group may be used.

  Said alkenyl substituted nadiimide compound may be used independently and may mix and use two or more compounds. Examples of preferred alkenyl-substituted nadiimide compounds are listed 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-dicarboximide),
N, N′-dodecamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-dodecamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-cyclohexylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-cyclohexylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide)

N, N′-p-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-p-phenylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-m-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-m-phenylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N ′-{(1-methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-p-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
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- (allylmethylbicyclo [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

Examples of further preferred alkenyl-substituted nadiimide compounds are given 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-dicarboximide),
N, N′-dodecamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-dodecamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-cyclohexylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-cyclohexylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide)

N, N′-p-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-p-phenylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-m-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-m-phenylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N ′-{(1-methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-p-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
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

Particularly preferred examples of the alkenyl-substituted nadiimide compound are the compound (a-1), the compound (a-2) and the compound (a-3).

  The use ratio of such an alkenyl-substituted nadiimide compound is 0.001-5 by weight ratio with respect to the polymer component, preferably 0.01-2, more preferably 0.05-1.2. When the addition amount of the alkenyl-substituted nadiimide compound of the present invention is within these ranges, a liquid crystal aligning agent varnish that maintains a balance among long-term reliability, liquid crystal alignment, and display quality can be obtained.

式（１６）および式（１７）において、Ｐｈはフェニルを、Ｍｅはメチルを意味する。 The polymer component used in the present invention is at least one polymer selected from polyamic acid and derivatives thereof. And the polyamic acid of this invention is obtained by making diamine react with at least one of the carboxylic dianhydrides of the following formulas (1) to (17).

In the formulas (16) and (17), Ph means phenyl, and Me means methyl.

  A preferred tetracarboxylic dianhydride used in the present invention is at least one of the compound represented by the formula (16) and the compound represented by the formula (17), or the compound represented by the formula (16) and the formula (17). It is a mixture of at least one of the compounds shown and at least one of the compounds of formula (1) to formula (15).

  A part of the tetracarboxylic dianhydride used in the present invention may be replaced with a carboxylic anhydride. By replacing a part of tetracarboxylic dianhydride with carboxylic anhydride, the termination of polymerization reaction can be caused, and further progress of the reaction can be suppressed, so the resulting polymer (polyamic acid) The molecular weight of can be easily controlled. The ratio of the carboxylic acid anhydride to the tetracarboxylic dianhydride may be in a range that does not impair the effects of the present invention, but it is preferably set to 10 mol% or less of the total tetracarboxylic dianhydride amount.

  In the present invention, any diamine can be used. However, in the case of a VA liquid crystal display element, a large pretilt angle of about 80 to 90 °, and in the case of an OCB type liquid crystal display element, a pretilt angle of about 7 to 20 ° has a TN liquid crystal display element or an STN liquid crystal display. In the case of a display element, a pretilt angle of about 3 to 10 ° is often required, and in the case of an IPS liquid crystal display element, a small pretilt angle of about 0 to 3 ° is often required. Therefore, it is necessary to consider the adjustment of the pretilt angle.

  By the way, diamine can be divided into two types depending on the difference in structure. That is, when a skeleton connecting two amino groups is viewed as a main chain, a group branched from the main chain, that is, a diamine having a side chain group and a diamine having no side chain group. By reacting a diamine having a side chain group with tetracarboxylic dianhydride, a polyamic acid or polyimide having a large number of side chain groups with respect to the main chain of the polymer is obtained. When a polyamic acid or polyimide having a side chain group with respect to such a polymer main chain is used, the liquid crystal alignment film formed from the liquid crystal aligning agent containing this polymer increases the pretilt angle in the liquid crystal display element. Can do. That is, this side chain group is a group having an effect of increasing the pretilt angle, and is an alkyl having 3 or more carbon atoms, an alkoxy having 3 or more carbon atoms, an alkoxyalkyl having 3 or more carbon atoms, a group having a steroid skeleton, and a terminal group. It is selected from a group having alkyl having 3 or more carbon atoms, alkoxy having 3 or more carbon atoms or alkoxyalkyl having 3 or more carbon atoms. In the present invention, a diamine having such a side chain group is referred to as a side chain diamine. Such a diamine having no side chain group is referred to as a non-side chain diamine.

  Then, by appropriately combining the side chain type diamine and the non-side chain type diamine, it is possible to cope with the pretilt angle required for each of the various display elements. That is, when a large pretilt angle is not required, at least one non-side chain diamine may be used. In the case of applications such as the VA type liquid crystal display element, OCB type liquid crystal display element, STN type liquid crystal display element, etc., at least one non-side chain diamine and at least one side chain diamine may be used in combination. . At this time, the blending ratio of the non-side chain diamine and the side chain diamine may be determined according to the target pretilt angle. Of course, it is possible to use only a side chain type diamine by appropriately selecting a side chain group. As described above, the liquid crystal aligning agent of the present invention can be applied to any kind of liquid crystal display element.

Specific examples of the side chain group are as follows.
First of all, 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 it has 3 or more carbon atoms as a whole. These groups may be linear or branched.

  Next, phenyl, phenylalkyl, phenylalkyloxy, phenyloxy, on condition that the terminal ring has alkyl having 3 or more carbon atoms, alkoxy having 3 or more carbon atoms or alkoxyalkyl having 3 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,. Note that bis (cyclohexyl) and bis (phenyl) may be bonded not by a single bond but by alkylene.

  Further, two or more benzene rings or cyclohexane rings are bonded via a single bond, —O—, —COO—, —OCO—, —CONH— or alkylene having 1 to 3 carbon atoms, and the terminal ring is a substituent. Examples thereof include a ring assembly group having alkyl having 3 or more carbon atoms, fluorine-substituted alkyl having 3 or more carbon atoms, alkoxy having 3 or more carbon atoms, or alkoxyalkyl having 3 or more carbon atoms. Of course, a group having a steroid skeleton is also effective as a side chain group.

Preferred examples of non-side chain diamines are listed below.

In formulas (I) to (VII), A ¹ is a linear alkylene having 2 to 12 carbon atoms; A ² is a linear alkylene having 1 to 12 carbon atoms; A ³ is independently a single bond; -O -, - CO -, - CONH -, - NHCO -, - C (CH 3) 2 -, - C (CF 3) 2 -, - O-A 2 -O -, - S -, - S- S—, —SO ₂ —, —SA ² —S—, or A ² ; any hydrogen of the cyclohexane ring and the benzene ring is fluorine, —CH ₃ , —OH, —COOH, —SO ₃ H, It may be replaced with PO ₃ H ₂ , benzyl or hydroxybenzyl.

Examples of the diamine represented by the formula (I) are the compound (I-1) to the compound (I-4).

Examples of the diamine represented by the formula (II) are the compound (II-1) and the compound (II-2).

Examples of the diamine represented by the formula (III) are the compound (III-1) to the compound (III-3).

Examples of the diamine represented by the formula (IV) are the compound (IV-1) to the compound (IV-16).

Examples of the diamine represented by the formula (V) are the compound (V-1) to the compound (V-34).

Examples of the diamine represented by the formula (VI) are the compound (VI-1) to the compound (VI-6).

Examples of the diamine represented by the formula (VII) are the compound (VII-1) to the compound (VII-16).

  Of the above diamines, more preferred examples are Compound (IV-1) to Compound (IV-5), Compound (IV-15), Compound (IV-16), Compound (V-1) to Compound (V-20). ), Compound (V-26), Compound (V-27), Compound (V-31), Compound (VI-1), Compound (VI-2), Compound (VI-6), Compound (VII-1) To Compound (VII-5), and particularly preferred examples are Compound (IV-1), Compound (IV-2), Compound (IV-15), Compound (IV-16), Compound (V-1) to Compound (V-13) and compound (VII-2).

  One of these compounds (I) to (VII) may be used alone, or two or more may be used in combination. The ratio of compound (I) to compound (VII) in the total amount of diamine may be adjusted according to the structure of the selected diamine and the desired voltage holding ratio, and is preferably 1 to 100 mol%. More preferably, it is -80 mol%.

  As described above, in the present invention, at least one diamine is used. However, in applications where a large pretilt angle is required, such as a VA liquid crystal display element, an OCB liquid crystal display element, and an STN liquid crystal display element, the side chain is used. It is preferable to use a type diamine.

ここに、Ｒ^６は単結合、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＣＨ_２Ｏ−、−ＣＦ_２Ｏ−、または炭素数１〜６のアルキレンであって、このアルキレンにおける任意の−ＣＨ_２−は−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく；Ｒ^７はステロイド骨格を有する基、炭素数３〜３０のアルキル、置換基として炭素数３〜３０のアルキルもしくは炭素数３〜３０のアルコキシを有するフェニル、または式（Ｄ−１）で表される基であって、このアルキルにおける任意の−ＣＨ_２−は−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよい。 Preferable examples of the side chain type diamine are diamines represented by the formulas (VIII) to (XII).

Here, ^{R 6} is a single bond, -O -, - CO -, - COO -, - OCO -, - CONH -, - CH 2 O -, - CF 2 O-, or an alkylene having 1 to 6 carbon atoms And any —CH ₂ — in the alkylene may be replaced by —O—, —CH═CH— or —C≡C—; R ⁷ is a group having a steroid skeleton, having 3 to 30 carbon atoms Alkyl, phenyl having 3 to 30 carbons or alkoxy having 3 to 30 carbons as a substituent, or a group represented by formula (D-1), wherein any —CH ₂ — in the alkyl is -O-, -CH = CH-, or -C≡C- may be substituted.

ここに、Ｒ^１８、Ｒ^１９およびＲ^２０は独立して単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、炭素数１〜４のアルキレン、炭素数１〜３のオキシアルキレン、または炭素数１〜３のアルキレンオキシであり；環Ｂおよび環Ｃは独立して１，４−フェニレンまたは１，４−シクロヘキシレンであり；Ｒ^２１およびＲ^２２は独立してフッ素またはメチルであって、ｍ１およびｍ２は独立して０、１または２であり；ｅ、ｆおよびｇは独立して０〜３の整数であって、これらの合計は１以上であり；Ｒ^２３は炭素数３〜３０のアルキル、炭素数３〜３０のアルコキシ、または炭素数３〜３０のアルコキシアルキルであり、これらのアルキル、アルコキシおよびアルコキシアルキルにおいて、任意の水素はフッ素で置き換えられてもよく、そして任意の−ＣＨ_２−はジフルオロメチレンまたは式（Ｄ−２）で表される基で置き換えられてもよい。

Here, R ¹⁸ , R ¹⁹ and R ²⁰ are independently a single bond, —O—, —COO—, —OCO—, —CONH—, alkylene having 1 to 4 carbons, or oxyalkylene having 1 to 3 carbons. Or Ring C and C are independently 1,4-phenylene or 1,4-cyclohexylene; R ²¹ and R ²² are independently fluorine or methyl; There are, m1 and m2 is independently 0, 1 or 2; e, f and g is an integer of 0 to 3 independently, their sum is 1 or ^{more; R 23} is the number of carbon atoms An alkyl having 3 to 30 carbons, an alkoxy having 3 to 30 carbons, or an alkoxyalkyl having 3 to 30 carbons, and in these alkyls, alkoxys and alkoxyalkyls, any hydrogen is replaced by fluorine. And any —CH ₂ — may be replaced by difluoromethylene or a group represented by the formula (D-2).

ここに、Ｒ^２４、Ｒ^２５、Ｒ^２６およびＲ^２７は、独立して炭素数１〜１０のアルキルまたはフェニルであり、そしてｎは１〜１００の整数である。

Here, R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ are each independently alkyl or phenyl having 1 to 10 carbon atoms, and n is an integer of 1 to 100.

ここに、Ｒ^８は独立して水素またはメチルであり；Ｒ^９は水素、炭素数１〜３０のアルキル、または炭素数２〜３０のアルケニルであり；そして、Ｒ^１０は独立して単結合、−ＣＯ−または−ＣＨ_２−である。

Wherein R ⁸ is independently hydrogen or methyl; R ⁹ is hydrogen, alkyl having 1 to 30 carbons, or alkenyl having 2 to 30 carbons; and R ¹⁰ is independently a single bond, —CO— or —CH ₂ —.

ここに、Ｒ^８は独立して水素またはメチルであり；Ｒ^９は水素、炭素数１〜３０のアルキル、または炭素数２〜３０のアルケニルであり；Ｒ^１０は独立して単結合、−ＣＯ−または−ＣＨ_２−であり；そして、Ｒ^１１およびＲ^１２は独立して水素、炭素数１〜３０のアルキル、またはフェニルである。

Wherein R ⁸ is independently hydrogen or methyl; R ⁹ is hydrogen, alkyl having 1 to 30 carbons, or alkenyl having 2 to 30 carbons; R ¹⁰ is independently a single bond, —CO — Or —CH ₂ —; and R ¹¹ and R ¹² are independently hydrogen, alkyl having 1 to 30 carbons, or phenyl.

ここに、Ｒ^１３は炭素数３〜３０のアルキルであって、このアルキルの任意の−ＣＨ_２−は−Ｏ−、−ＣＨ＝ＣＨ−またはＣ≡Ｃ−で置き換えられてもよく；Ｒ^１４は独立して−Ｏ−または炭素数１〜６のアルキレンであり；環Ａは１，４−フェニレンまたは１，４−シクロヘキシレンであり；ａは０または１であり；ｂは０、１または２であり；そして、ｃは独立して０または１である。

Wherein R ¹³ is an alkyl having 3 to 30 carbon atoms, and any —CH ₂ — in the alkyl may be replaced by —O—, —CH═CH— or C≡C—; R ¹⁴ Is independently —O— or alkylene having 1 to 6 carbon atoms; ring A is 1,4-phenylene or 1,4-cyclohexylene; a is 0 or 1; b is 0, 1 or And c is independently 0 or 1.

ここに、Ｒ^１５は炭素数３〜３０のアルキルまたは炭素数３〜３０のフッ素化アルキルであり；Ｒ^１６は水素、炭素数１〜３０のアルキルまたは炭素数１〜３０のフッ素化アルキルであり；Ｒ^１７は独立して−Ｏ−または炭素数１〜６のアルキレンであり；そして、ｄは独立して０または１である。

Wherein R ¹⁵ is alkyl having 3 to 30 carbon atoms or fluorinated alkyl having 3 to 30 carbon atoms; R ¹⁶ is hydrogen, alkyl having 1 to 30 carbon atoms or fluorinated alkyl having 1 to 30 carbon atoms. R ¹⁷ is independently —O— or alkylene having 1 to 6 carbons; and d is independently 0 or 1.

Examples of compound (VIII) are shown below.

In the formula (VIII-1) to the formula (VIII-11), R ²⁸ is alkyl having 3 to 30 carbons or alkoxy having 3 to 30 carbons, preferably alkyl having 5 to 25 carbons or 5 to 5 carbons. 25 alkoxy. R ²⁹ is alkyl having 3 to 30 carbons or alkoxy having 3 to 30 carbons, preferably alkyl having 3 to 25 carbons or alkoxy having 3 to 25 carbons.

In formula (VIII-12) to formula (VIII-17), R ³⁰ is alkyl having 4 to ³⁰ carbons, preferably alkyl having 6 to 25 carbons. R ³¹ is alkyl having 6 to 30 carbon atoms, preferably alkyl having 8 to 25 carbon atoms.

In formula (VIII-18) to formula (VIII-37), R ³² and R ³³ are independently alkyl having 3 to 30 carbons or alkoxy having 3 to 30 carbons, preferably 3 to 25 carbons. Or alkyl having 3 to 25 carbon atoms.

  Of these, compound (VIII-1) to compound (VIII-11) are preferable, and compound (VIII-2), compound (VIII-4), compound (VIII-5) and compound (VIII-6) are more preferable. .

In the formula (IX), it is preferable that one of the two “NH ₂ — (Ph) —R ¹⁰ —O—” is bonded to the 3-position of the steroid nucleus and the other is bonded to the 6-position. The two amino groups are preferably bonded to the meta position or the para position with respect to the bonding position of R ¹⁰ .

Examples of diamines represented by formula (IX) include compounds (IX-1) to (IX-4).

In the formula (X), the bonding positions of the two “NH ₂ — (R ¹² —) (Ph) —R ¹⁰ —O—” with respect to the benzene ring are in the meta position or the para position relative to the carbon to which the steroid nucleus is bonded. Is preferred. The bonding positions of the two amino groups with respect to the benzene ring are each preferably meta or para with respect to R ¹⁰ .

Examples of the diamine represented by the formula (X) are the compound (X-1) to the compound (X-8).

In formula (XI), the preferred bonding position of the two amino groups to the benzene ring is the meta position or the para position with respect to R ¹⁴ . Examples of the diamine represented by the formula (XI) are the compound (XI-1) to the compound (XI-8).

In Formula (XI-1) to Formula (XI-8), R ³⁴ is alkyl having 3 to 30 carbons, and R ³⁵ is alkyl having 3 to 20 carbons.

これらの式において、Ｒ^３６は炭素数６〜２０のアルキルであり、Ｒ^３７は水素、または炭素数１〜１０のアルキルである。 In the formula (XII), a preferred bonding position of the two amino groups to the benzene ring is the meta position or the para position with respect to R ¹⁷ . Preferred examples of the diamine represented by the formula (XII) are the compound (XII-1) to the compound (XII-3).

In these formulas, R ³⁶ is alkyl having 6 to 20 carbon atoms, and R ³⁷ is hydrogen or alkyl having 1 to 10 carbon atoms.

  One of these compounds (VIII) to (XII) may be used alone, or two or more may be used in combination. The ratio of compound (VIII) to compound (XII) in the total amount of diamine may be adjusted according to the structure of the selected diamine and the desired pretilt angle, and is preferably 1 to 100 mol%. More preferably, it is 100 mol%.

ここに、Ｒ^２８およびＲ^２９は独立して、炭素数３〜３０のアルキルまたは炭素数３〜３０のアルコキシである。 Of the compounds (VIII) to (XII), the following compound (VIII-2), compound (VIII-4), compound (VIII-5) and compound (VIII-6) are preferred.

Here, R ²⁸ and R ²⁹ are independently alkyl having 3 to 30 carbons or alkoxy having 3 to 30 carbons.

  In the present invention, it is preferable to use a mixture of a diamine selected from Compound (I) to Compound (VII) and a diamine selected from Compound (VIII) to Compound (XII). Compound (IV-1), Compound (IV-2), Compound (IV-15), Compound (IV-16), Compound (V-1) to Compound (V-13) and Compound (VII-2) It is particularly preferable to use a mixture of at least one selected from the group consisting of compound (VIII-2), compound (VIII-4), compound (VIII-5) and compound (VIII-6). The proportion of the diamine selected from the compound (VIII-2), the compound (VIII-4), the compound (VIII-5) and the compound (VIII-6) in the total amount of diamine is 10 to 100 mol%. Is preferable, and it is more preferable that it is 30-100 mol%.

  Furthermore, other diamines other than compound (I) to compound (VII) and compound (VIII) to compound (XII) can be used as the diamine in the present invention. Such other diamines are optional, for example, naphthalene-based diamine having a naphthalene structure, fluorene-based diamine having a fluorene structure, or a siloxane-based diamine having a siloxane bond, or other than compounds (VIII) to (XII) A diamine having a side chain structure of

ここに、Ｒ^３８およびＲ^３９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、Ａ^４は独立してメチレン、フェニレンまたはアルキル置換されたフェニレンである。ｌは１〜６の整数であり、ｍは１〜１０の整数である。 The siloxane-based diamine is not particularly limited, but those represented by the following formula (XV) are preferably used in the present invention.

Here, R ³⁸ and R ³⁹ are independently alkyl or phenyl having 1 to 3 carbon atoms, and A ⁴ is independently methylene, phenylene or alkyl-substituted phenylene. l is an integer of 1 to 6, and m is an integer of 1 to 10.

ここに、Ｒ^４０およびＲ^４１は独立して炭素数３〜３０のアルキルである。 Further, other diamines are not particularly limited, but for example, those represented by the following formulas (1 ′) to (8 ′) are preferably used in the present invention.

Here, R ⁴⁰ and R ⁴¹ are independently alkyl having 3 to 30 carbon atoms.

  The diamine in the present invention can give a suitable pretilt angle to the liquid crystal alignment film formed using the liquid crystal aligning agent of the present invention by appropriately selecting the type of diamine and the combination thereof.

  A part of the diamine in the present invention may be replaced with a monoamine. By substituting a part of the diamine with a monoamine, the termination of the polymerization reaction can be caused, and further progress of the reaction can be suppressed, so the molecular weight of the resulting polymer (polyamic acid) can be easily controlled. Can do. The ratio of the monoamine to the diamine may be in a range that does not impair the effects of the present invention, but as a guideline, it is preferably 10 mol% or less of the total amine amount.

  The polyamic acid and its derivative in the present invention can have any weight average molecular weight. The weight average molecular weight of the polyamic acid and its derivative is not particularly limited, but when used as a component of a liquid crystal aligning agent, it is preferably 5 × 10 3 or more, and more preferably 1 × 10 4 or more. The polyamic acid having a weight average molecular weight of 5 × 103 or more and its derivative do not evaporate in the step of firing the liquid crystal alignment film, and have preferable physical properties as a component of the liquid crystal aligning agent.

  The weight average molecular weight of the polyamic acid and its derivative is measured by a gel permeation chromatography (GPC) method. For example, the obtained polyamic acid and its derivative are diluted with dimethylformamide (DMF) so that the polyamic acid concentration is about 1% by weight, and DMF is used as a developing solvent using Chromatopack C-R7A (manufactured by Shimadzu Corporation). As measured by gel permeation chromatographic analysis (GPC) and converted to polystyrene. Furthermore, in order to perform GPC measurement of polyamic acid, polyacrylic acid, etc. with high accuracy, a developing solvent in which inorganic acid such as phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid, etc. and inorganic salt such as lithium bromide, lithium chloride, etc. are dissolved in DMF solvent. May be prepared.

  The polyamic acid and its derivative in the present invention can be produced using a known method. For example, a reaction vessel equipped with a raw material inlet, a nitrogen inlet, a thermometer, a stirrer and a condenser is selected from at least one of the diamines represented by the formulas (I) to (XII) and optionally other diamines. The desired amount of diamine and, if necessary, monoamine is charged.

  Next, at least one of a solvent (for example, N-methyl-2-pyrrolidone or dimethylformamide which is an amide polar solvent) and tetracarboxylic dianhydride, and further a carboxylic anhydride as required are added. At this time, it is preferable that the total charge amount of tetracarboxylic dianhydride is approximately equal to the total number of moles of diamine (molar ratio of about 0.9 to 1.1).

  A polyamic acid solution can be obtained by reacting at a temperature of 0 to 70 ° C. for 1 to 48 hours under stirring. Moreover, the polyamic acid with a small molecular weight can also be obtained by heating and raising reaction temperature (for example, 50-80 degreeC).

  The polyamic acid in the present invention can be identified by precipitating with a large amount of a poor solvent, separating the solid and the solvent completely by filtration or the like, and analyzing by IR or NMR. Furthermore, after decomposing solid polyamic acid with an aqueous solution of strong alkali such as KOH or NaOH, the monomer used can be identified by extracting with an organic solvent and analyzing by GC, HPLC or GC-MS. it can.

  The obtained polyamic acid solution can be used after being diluted with a solvent in order to adjust to a desired viscosity.

  In the case where the polyamic acid in the present invention is a soluble polyimide that is a polyamic acid derivative, the polyamic acid solution is composed of a dehydrating agent such as acetic anhydride, propionic anhydride, and anhydrous trifluoroacetic acid, and a dehydrating ring-closing catalyst. It can be obtained by imidization reaction at a temperature of 20 to 150 ° C. with a tertiary amine such as triethylamine, pyridine and collidine.

  A polyamic acid is precipitated from a polyamic acid solution using a large amount of poor solvent (alcohol solvent or glycol solvent such as methanol, ethanol, isopropanol), and the precipitated polyamic acid is added in a solvent such as toluene or xylene. It can also be obtained by carrying out an imidization reaction at a temperature of 20 to 150 ° C. together with the same dehydrating agent and dehydrating ring-closing catalyst.

  In the imidization reaction, the ratio of the dehydrating agent to the dehydrating ring-closing catalyst is preferably 0.1 to 10 (molar ratio). The total amount used of both is preferably 1.5 to 10 times the total molar amount of acid dianhydride contained in the tetracarboxylic dianhydride used. By adjusting the dehydrating agent, catalyst amount, reaction temperature and reaction time of this chemical imidization, the degree of imidization can be controlled and a partial polyimide can be obtained.

  As described above, a part of the acid dianhydride used for the tetracarboxylic dianhydride in the present invention may be replaced with an organic dicarboxylic acid. If the polyamic acid in this invention is manufactured using organic dicarboxylic acid and tetracarboxylic dianhydride, a polyamic acid-polyamide copolymer can be obtained. Here, the ratio of the organic dicarboxylic acid to the tetracarboxylic dianhydride may be within a range that does not impair the effects of the present invention, but as a guideline, the ratio is preferably 10 mol% or less.

  Furthermore, a polyamideimide can be produced by chemically imidizing this polyamic acid-polyamide copolymer.

  The liquid crystal aligning agent of the present invention preferably contains a solvent from the viewpoints of adjustment of physical properties such as viscosity, ease of handling, and simplification of the process. Moreover, various additives contained in a normal liquid crystal aligning agent may be further included.

  The content rate of the polyamic acid in the liquid crystal aligning agent of this invention can be suitably selected with the coating method to the board | substrate of a liquid crystal aligning agent. For example, when used in a printing machine (including an offset printing machine and an ink jet printing machine, which may be abbreviated as “printing machine” hereinafter) used in a manufacturing process of a normal liquid crystal display element, the polyamic in the liquid crystal aligning agent is used. The acid content is preferably 0.5 to 30% by weight, more preferably 1 to 15% by weight, based on the total amount of the liquid crystal aligning agent. However, it may be appropriately adjusted in relation to the viscosity (described later) of the liquid crystal aligning agent.

  The solvent used in the present invention widely includes solvents usually used in the production process and applications of polymer components such as polyamic acid, soluble polyimide, and polyamideimide, and is appropriately selected depending on the purpose of use. This solvent is a mixed solvent containing 1) an aprotic polar organic solvent that is easily soluble in polyamic acid and soluble polyimide, and 2) a solvent for changing the surface tension to improve coatability. Is preferred. Examples of these solvents are as follows.

  1) Aprotic polar organic solvent which is a good solvent for polyamic acid and soluble polyimide (hereinafter, aprotic polar organic solvent): for example, N-methyl-2-pyrrolidone, dimethylimidazolidinone, N-methylcaprolactam, N-methylpropionamide, N, N-dimethylacetamide, dimethyl sulfoxide, N, N-dimethylformamide, N, N-diethylformamide, diethylacetamide, γ-butyrolactone, and γ-valerolactone. Of these, N-methyl-2-pyrrolidone, dimethylimidazolidinone, γ-butyrolactone, γ-valerolactone, and the like are more preferred.

  2) Solvents for improving coating properties by changing surface tension (hereinafter referred to as other solvents): for example, ethylene glycol such as alkyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, ethylene glycol monobutyl ether Monoalkyl ether, diethylene glycol monoalkyl ether such as diethylene glycol monoethyl ether, ethylene glycol monoalkyl or phenyl acetate, propylene glycol monoalkyl ether such as triethylene glycol monoalkyl ether, propylene glycol monobutyl ether, dialkyl malonate such as diethyl malonate , Dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, and ester compounds such as these acetates A. Of these, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, and the like are more preferred.

  The types and ratios of the aprotic polar solvent and the other solvent can be appropriately set in consideration of the printability, coatability, solubility, storage stability, and the like of the liquid crystal aligning agent. Aprotic polar solvents are relatively superior in solubility and storage stability to other solvents, and other solvents tend to be excellent in printability and coatability.

  As described above, the liquid crystal aligning agent of the present invention may contain various additives. As various additives, high molecular compounds other than polymic acid and its derivatives, or low molecular compounds can be selected and used according to each purpose.

  For example, a polymer compound soluble in an organic solvent may be used as an additive, and by adding them, the electrical characteristics and orientation of the liquid crystal alignment film to be formed can be controlled. Examples of the polymer compound include polyamide, polyurethane, polyurea, polyester, polyepoxide, polyester polyol, silicone-modified polyurethane, and silicone-modified polyester.

  Examples of additives for low molecular weight compounds include 1) a surfactant in accordance with the purpose when improvement in coating properties is desired, 2) an antistatic agent when improvement in antistatic properties is required, and 3). A silane coupling agent and a titanium-based coupling agent can be used when it is desired to improve adhesion to the substrate and rubbing resistance, and 4) an imidization catalyst can be used when imidization proceeds at a low temperature.

  Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N- (2-aminoethyl) -3-aminopropyl. Methyltrimethoxysilane, paraaminophenyltrimethoxysilane, paraaminophenyltriethoxysilane, metaaminophenyltrimethoxysilane, metaaminophenyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycyl Sidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyl Pyrtrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propylamine, N, N Examples include '-bis [3- (trimethoxysilyl) propyl] ethylenediamine.

  Examples of the imidization catalyst include aliphatic amines such as trimethylamine, triethylamine, tripropylamine, and tributylamine; aromatics such as N, N-dimethylaniline, N, N-diethylaniline, methyl-substituted aniline, and hydroxy-substituted aniline. Aromatic amines: cyclic amines such as pyridine, methyl substituted pyridine, hydroxy substituted pyridine, quinoline, methyl substituted quinoline, hydroxy substituted quinoline, isoquinoline, methyl substituted isoquinoline, hydroxy substituted isoquinoline, imidazole, methyl substituted imidazole, hydroxy substituted imidazole, etc. It is preferable to add the catalyst. In particular, N, N-dimethylaniline, o-hydroxyaniline, m-hydroxyaniline, p-hydroxyaniline, o-hydroxypyridine, m-hydroxypyridine, p-hydroxypyridine, isoquinoline and the like can be mentioned.

  The addition amount of the silane coupling agent is usually 0 to 0.1 by weight ratio with respect to the polymer component, and preferably 0.001 to 0.03.

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

  The addition amount of other additives varies depending on the application, but is usually 0 to 0.3 by weight ratio with respect to the polymer component, and preferably 0.001 to 0.1.

  The viscosity of the liquid crystal aligning agent of the present invention varies widely depending on the coating method, the concentration of polyamic acid and its derivative, the type of polyamic acid and its derivative used, and the type and ratio of the solvent. For example, in the case of application by a printing press, it is preferably 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 application by spin coating, 5 to 200 mPa · s (more preferably 10 to 100 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.).

  Another preferable form of the liquid crystal aligning agent of the present invention is a composition containing two or more kinds of polymers selected from polyamic acid and derivatives thereof. At this time, one group of polymers is a polyamic acid obtained by reacting tetracarboxylic dianhydride and a non-side chain diamine selected from compounds (I) to (VII) or a derivative thereof (polymer component A). ). In addition to compounds (I) to (VII), diamines other than compounds (I) to (XII) may be used in combination. The liquid crystal alignment film formed using the liquid crystal aligning agent containing the polymer component A can give a favorable voltage holding ratio to the liquid crystal display element containing it.

  Another group of polymers is a polyamic acid obtained by reacting a tetracarboxylic dianhydride and a side chain diamine selected from compound (VIII) to compound (XII) or a derivative thereof (polymer component B). . In addition to compounds (VIII) to (XII), diamines other than compounds (I) to (XII) may be used in combination. The liquid crystal alignment film formed using the liquid crystal aligning agent containing the polymer component B can increase the pretilt angle of the liquid crystal display element including the liquid crystal alignment film.

  Yet another group of polymers is a polyamic acid or a derivative thereof (polymer component C) obtained by reacting a tetracarboxylic dianhydride with a mixture of the aforementioned non-side chain diamine and side chain diamine. In addition to compounds (I) to (XII), diamines other than these compounds may be used in combination.

  In the present invention, it is preferable to use a mixture of at least two polymers selected from polymer component A, polymer component B and polymer component C. For example, when the polymer component A and the polymer component B are mixed, the mixing ratio of these polymers is A / B = 99/1 to 50/50, and a more preferable ratio is A / B = 95/5 to 80 / 20. This weight ratio may be appropriately adjusted according to the required pretilt angle, and the pretilt angle can be increased by increasing the ratio of the polymer component B. If anything, the polymer component C is preferably combined with the polymer component A instead of the polymer component B, and the mixing ratio is the same as above. In addition, all of the polymer component A, the polymer component B, and the polymer component C may be composed of a plurality of polymers. The liquid crystal aligning agent of the present invention may contain a polyamic acid other than the polymer component A, the polymer component B, and the polymer component C.

  The liquid crystal aligning film of this invention is a liquid crystal aligning film formed by baking the said polyamic acid in the liquid crystal aligning agent of this invention in the state of the film of the liquid crystal aligning agent of this invention.

  The liquid crystal alignment film is, for example, a liquid crystal display element substrate, or a liquid crystal alignment agent of the present invention applied to a measurement substrate such as calcium fluoride or silicon. Preferably it can form by heating at 180-280 degreeC. The film thickness of the liquid crystal alignment film is preferably 10 to 300 nm, and more preferably 30 to 100 nm. The liquid crystal alignment film is preferably rubbed.

  The film thickness of a liquid crystal aligning film can be adjusted with the viscosity of a liquid crystal aligning agent, and the coating method of a liquid crystal aligning agent. This film thickness can be measured by a known film thickness measuring device such as a step meter or an ellipsometer. Furthermore, the components in the liquid crystal alignment film can be analyzed using a normal analysis means such as IR or MS after performing a treatment such as hydrolysis as necessary.

  The liquid crystal display element of the present invention includes 1) a pair of substrates arranged opposite to each other, 2) the liquid crystal alignment film of the present invention formed on the opposed surfaces of each of the pair of substrates, and 3) between the pair of substrates. A liquid crystal layer sandwiched between the two. It is preferable that a pair of board | substrate with an electrode arrange | positioned facing is a transparent substrate (for example, glass substrate).

  An electrode is provided on the surface of at least one or both of the pair of substrates according to the form of the liquid crystal display element. 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. The electrode may be formed on the entire surface of the substrate, or may be formed in a predetermined shape that is patterned, for example. The liquid crystal alignment film of the present invention is formed on the surface of the substrate on which the electrode is not provided, and the liquid crystal alignment film of the present invention is formed on the electrode on the substrate on which the electrode is provided. The formation of the liquid crystal alignment film of the present invention is as described above.

  The liquid crystal layer sandwiched between the pair of substrates includes a liquid crystal composition. Here, the liquid crystal composition is not particularly limited, and either a liquid crystal composition having a positive dielectric anisotropy or a liquid crystal composition having a negative dielectric anisotropy may be used depending on the driving mode. it can.

  Examples of preferable liquid crystal compositions having a positive dielectric anisotropy include Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Laid-Open No. 5-501735, Japanese Patent Laid-Open No. 8-157826, Japanese Patent Laid-Open No. 8- No. 231960, JP-A-9-241644 (EP882722A1), JP-A-9-302346 (EP806466A1), JP-A-8-199168 (EP722998A1), JP-A-9-235552, JP-A-9-255556. JP, 9-241643 (EP882711A1), JP 10-204016 (EP844229A1), JP 10-204436, JP 10-231482, JP 2000-087040, JP It is disclosed in 2001-48822 gazette etc. .

  The liquid crystal composition used in the VA liquid crystal display element can be various liquid crystal compositions having negative dielectric anisotropy. Examples of preferred liquid crystal compositions include JP-A-57-141432, JP-A-2-4725, JP-A-4-224858, JP-A-8-40953, JP-A-8-104869, Japanese Laid-Open Patent Publication No. 10-168076, Japanese Laid-Open Patent Publication No. 10-168453, Japanese Laid-Open Patent Publication No. 10-236989, Japanese Laid-Open Patent Publication No. 10-236990, Japanese Laid-Open Patent Publication No. 10-236992, Japanese Laid-Open Patent Publication No. 10-236993, Japanese Laid-open Patent Publication No. -236994, JP-A-10-237000, JP-A-10-237004, JP-A-10-237024, JP-A-10-237035, JP-A-10-237075, JP-A-10-237076 JP, 10-237448, (EP967261A1), JP 10-28787. JP-A-10-287875, JP-A-10-291945, JP-A-11-029581, JP-A-11-080049, JP-A-2000-256307, JP-A-2001-019965, JP 2001-072626 A, JP 2001-192657 A, and the like.

  One or more optically active compounds may be used by adding to the liquid crystal composition having a positive or negative dielectric anisotropy.

  The liquid crystal display element of the present invention may have other members. For example, in a color display TFT type liquid crystal element using a thin film transistor, a thin film transistor, an insulating film, a protective film, a signal electrode, a pixel electrode, and the like are formed on a first transparent substrate, and the second transparent substrate is formed. A black matrix, a color filter, a planarization film, a pixel electrode, and the like that block light outside the pixel region may be included.

  Further, in a VA liquid crystal display element, in particular, an MVA liquid crystal display element, a minute protrusion called a domain is formed on a first transparent substrate. A spacer may be formed for adjusting the cell gap between the substrates.

  The liquid crystal display element of the present invention can be produced by any method. For example, 1) a step of applying a liquid crystal alignment agent on the two transparent substrates, 2) a step of drying the applied liquid crystal alignment agent, 3 ) A step of performing a heat treatment necessary for dehydration and ring-closing reaction of the dried liquid crystal alignment agent, 4) a step of aligning the obtained alignment film, and 5) after bonding the two substrates together, The liquid crystal is manufactured by a method including a step of encapsulating a liquid crystal in the substrate, or a step of dropping a liquid crystal on one substrate and then bonding it to the other substrate.

  As a coating method in the step of 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. These methods are also applicable in the present invention.

  Further, as a method of the drying step and the step of performing the heat treatment necessary for the dehydration reaction, a method of heat treatment in an oven or an infrared furnace, a method of heat treatment on a hot plate, and the like are generally known. These methods are also applicable in the present invention. The drying step is preferably performed at a relatively low temperature (50 to 140 ° C.) within a range where the solvent can be evaporated. In general, the heat treatment step is preferably performed at a temperature of about 150 to 300 ° C.

  The alignment treatment for the liquid crystal alignment film is usually a rubbing treatment for IPS liquid crystal display elements, OCB liquid crystal display elements, TN liquid crystal display elements, and STN liquid crystal display elements. In many cases, the VA liquid crystal display element is not subjected to the rubbing treatment.

  Next, an adhesive is applied onto one substrate, and the liquid crystal is injected in a vacuum. In the case of the dropping injection method, the liquid crystal is dropped on the substrate before bonding, and then bonded on the other substrate. The liquid crystal display element of the present invention is produced by curing the adhesive used for bonding with heat or ultraviolet rays.

  A polarizing plate (polarizing film), a wave plate, a light scattering film, a driving circuit, and the like may be mounted on the liquid crystal display element of the present invention.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples. In addition, the material used in the Example is shown next. Moreover, milliliter which is a unit of capacity is indicated by the symbol mL.

３，３’，４，４’−ジフェニルエーテルテトラカルボン酸二無水物：ＯＤＰＡ [Tetracarboxylic dianhydride]
Compound (1): pyromellitic dianhydride Compound (7): 1,2,3,4-cyclobutanetetracarboxylic dianhydride Compound (8): 1,2,3,4-butanetetracarboxylic dianhydride Compound (16):

3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride: ODPA

[Diamine]
Compound (V-1): 4,4′-diaminodiphenylmethane Compound (V-13): 4,4′-diaminodiphenyl ether Compound (VII-2): 1,3-bis (4-aminobenzylphenyl) propane compound ( VIII-2-1): 1,3-diamino-5- (4-hexadecylbenzyl) benzene Compound (VIII-5-1): 1,3-diamino-5- (4- (4- (4-pentyl) Cyclohexyl) cyclohexyl) phenyl) methyl-benzene

この化合物は丸善石油化学（株）から入手できるＢＡＮＩ−Ｍである。
化合物（ａ−２）：

この化合物は丸善石油化学（株）から入手できるＢＡＮＩ−Ｘである。
化合物（ａ−３）：

この化合物は丸善石油化学（株）から入手できるＢＡＮＩ−Ｈである。 [Alkenyl-substituted nadiimide compound]
Compound (a-1):

This compound is BANI-M available from Maruzen Petrochemical Co., Ltd.
Compound (a-2):

This compound is BANI-X available from Maruzen Petrochemical Co., Ltd.
Compound (a-3):

This compound is BANI-H available from Maruzen Petrochemical Co., Ltd.

[solvent]
N-methyl-2-pyrrolidone: NMP
Butyl cellosolve (ethylene glycol monobutyl ether): BC
γ-butyrolactone: BL

<1. Synthesis of polyamic acid>
[Synthesis Example 1]
3.958 g of compound (VIII-2-1) and 60.0 g of dehydrated NMP were placed in a 100 mL four-necked flask equipped with a thermometer, stirrer, raw material charging inlet and nitrogen gas inlet, and stirred under a dry nitrogen stream. Dissolved. Next, 2.042 g of compound (1) was added and reacted for 30 hours in a room temperature environment. When the reaction temperature rose during the reaction, the reaction temperature was kept at about 70 ° C. or lower for the reaction. BC34.0g was added to the obtained solution, and the polyamic acid solution with a density | concentration of 6 weight% was obtained. This polyamic acid is designated as PA1. The weight average molecular weight of PA1 was 27,000.

  The weight average molecular weight of the polyamic acid was determined by diluting the obtained polyamic acid with a diluted solution (phosphoric acid / DMF = 0.6 / 100: weight ratio) so that the polyamic acid concentration was about 1% by weight. Using -R7A (manufactured by Shimadzu Corporation), the above diluent was measured by the GPC method using a developing agent, and determined by polystyrene conversion. In addition, the column used GF-7HQ (made by Showa Denko KK), and measured it on conditions with a column temperature of 50 degreeC and the flow rate of 0.6 mL / min.

[Synthesis Examples 2 and 3]
A solution of polyamic acid PA2 and a solution of polyamic acid PA3 were obtained in accordance with Synthesis Example 1 except that tetracarboxylic dianhydride and diamine were changed as shown in Table 1.

[Synthesis Example 4]
In a 100 mL four-necked flask equipped with a thermometer, a stirrer, a raw material charging inlet and a nitrogen gas inlet, 0.438 g of compound (V-1), 1.796 g of compound (VII-2), and compound (V- 13) 0.884 g and dehydrated NMP 54.0 g were added and dissolved under stirring in a dry nitrogen stream. Next, 0.633 g of the compound (16), 0.563 g of the compound (7), 1.686 g of the compound (1) and 15.0 g of dehydrated BL were added and reacted for 30 hours in a room temperature environment. When the reaction temperature rose during the reaction, the reaction temperature was kept at about 70 ° C. or lower for the reaction. 25.0 g of BC was added to the obtained solution to obtain a polyamic acid solution having a concentration of 6% by weight. This polyamic acid is referred to as PA4. The weight average molecular weight of PA4 was 44,000.

[Synthesis Examples 5 and 6]
A solution of polyamic acid PA5 and a solution of polyamic acid PA6 were obtained in accordance with Synthesis Example 4 except that tetracarboxylic dianhydride and diamine were changed as shown in Table 1.
<Table 1>

<2. Production of liquid crystal display element>
[Example 1]
The 6 wt% polyamic acid solution (PA1) synthesized in Synthesis Example 1 and the 6 wt% polyamic acid solution (PA3) synthesized in Synthesis Example 3 were mixed at a weight ratio of 1/9. To the obtained mixture, 10% by weight of BANI-M, which is an alkenyl-substituted nadiimide compound, was added per polymer weight. Thereafter, a mixed solvent of NMP / BC = 1/1 (weight ratio) was added to dilute the whole to 4% by weight to obtain a liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, a liquid crystal display element was produced as follows.

[Example 2]
The 6 wt% polyamic acid solution (PA2) synthesized in Synthesis Example 2 and the 6 wt% polyamic acid solution (PA3) synthesized in Synthesis Example 3 were mixed at a weight ratio of 1/9. To the obtained mixture, 10% by weight of BANI-M, which is an alkenyl-substituted nadiimide compound, was added per polymer weight. Thereafter, a mixed solvent of NMP / BC = 1/1 (weight ratio) was added to dilute the whole to 4% by weight to obtain a liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, a liquid crystal display element was produced as follows.

[Example 3]
The 6 wt% polyamic acid solution (PA1) synthesized in Synthesis Example 1 and the 6 wt% polyamic acid solution (PA3) synthesized in Synthesis Example 3 were mixed at a weight ratio of 1/9. To the resulting mixture, 10% by weight of the compound (a-3), which is an alkenyl-substituted nadiimide compound, was added per polymer weight. Thereafter, a mixed solvent of NMP / BC = 1/1 (weight ratio) was added to dilute the whole to 4% by weight to obtain a liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, a liquid crystal display element was produced as follows.

[Example 4]
The 6 wt% polyamic acid solution (PA1) synthesized in Synthesis Example 1 and the 6 wt% polyamic acid solution (PA3) synthesized in Synthesis Example 3 were mixed at a weight ratio of 1/9. The compound (a-2) which is an alkenyl substituted nadiimide compound was added to the obtained mixture by 10% by weight per polymer weight. Thereafter, a mixed solvent of NMP / BC = 1/1 (weight ratio) was added to dilute the whole to 4% by weight to obtain a liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, a liquid crystal display element was produced as follows.

[Comparative Example 1]
The 6 wt% polyamic acid solution (PA1) synthesized in Synthesis Example 1 and the 6 wt% polyamic acid solution (PA3) synthesized in Synthesis Example 3 were mixed at a weight ratio of 1/9. A mixed solvent of NMP / BC = 1/1 (weight ratio) was added to the obtained mixture to dilute the whole to 4% by weight to obtain a liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, a liquid crystal display element was produced as follows.

[Example 5]
To the polyamic acid solution (PA4) having a concentration of 6% by weight synthesized in Synthesis Example 4, 10% by weight of the compound (a-1) which is an alkenyl-substituted nadiimide compound was added per polymer weight. Thereafter, a mixed solvent of NMP / BC = 1/1 (weight ratio) was added to dilute the whole to 4% by weight to obtain a liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, a liquid crystal display element was produced as follows.

[Example 6]
To the polyamic acid solution (PA4) having a concentration of 6% by weight synthesized in Synthesis Example 4, 20% by weight of the compound (a-1) was added per polymer weight. Thereafter, a mixed solvent of NMP / BC = 1/1 (weight ratio) was added to dilute the whole to 4% by weight to obtain a liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, a liquid crystal display element was produced as follows.

[Example 7]
To the polyamic acid solution (PA5) having a concentration of 6% by weight synthesized in Synthesis Example 5, 10% by weight of the compound (a-1) was added per polymer weight. Thereafter, a mixed solvent of NMP / BC = 1/1 (weight ratio) was added to dilute the whole to 4% by weight to obtain a liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, a liquid crystal display element was produced as follows.

[Example 8]
To the polyamic acid solution (PA5) having a concentration of 6% by weight synthesized in Synthesis Example 5, 20% by weight of the compound (a-1) was added per polymer weight. Thereafter, a mixed solvent of NMP / BC = 1/1 (weight ratio) was added to dilute the whole to 4% by weight to obtain a liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, a liquid crystal display element was produced as follows.

[Comparative Example 2]
A mixed solvent of NMP / BC = 1/1 (weight ratio) was added to the polyamic acid solution (PA4) having a concentration of 6 wt% synthesized in Synthesis Example 4 to dilute the whole to 4 wt% to obtain a liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, a liquid crystal display element was produced as follows.

[Comparative Example 3]
A mixed solvent of NMP / BC = 1/1 (weight ratio) was added to the polyamic acid solution (PA5) having a concentration of 6% by weight synthesized in Synthesis Example 5 to dilute the whole to 4% by weight to obtain a liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, a liquid crystal display element was produced as follows.

[Comparative Example 4]
To the polyamic acid solution (PA6) having a concentration of 6% by weight synthesized in Synthesis Example 6, 20% by weight of the compound (a-3) was added per polymer weight. Thereafter, a mixed solvent of NMP / BC = 1/1 (weight ratio) was added to dilute the whole to 4% by weight to obtain a liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, a liquid crystal display element was produced as follows.

<Method for Manufacturing Liquid Crystal Display Element (Examples 1 to 4, Comparative Example 1)>
The liquid crystal aligning agent was applied to two glass substrates with an ITO electrode with a spinner to form a film with a thickness of 70 nm. After coating, the film was heated and dried at 80 ° C. for about 5 minutes, and then heat-treated at 220 ° C. for 40 minutes to form a liquid crystal alignment film. Next, the liquid crystal alignment film formed on the glass substrate was ultrasonically cleaned in ultrapure water for 5 minutes and then dried in an oven at 120 ° C. for 30 minutes.

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

<Method for Producing Liquid Crystal Display Elements (Examples 5 to 8, Comparative Examples 2 to 4)>
The liquid crystal aligning agent was applied to two glass substrates with an ITO electrode with a spinner to form a film with a thickness of 70 nm. After coating, the film was heated and dried at 80 ° C. for about 5 minutes, and then heat-treated at 230 ° C. for 20 minutes to form a liquid crystal alignment film. Next, the surface of the substrate on which the alignment film was formed was subjected to an alignment process by rubbing with a rubbing apparatus. Thereafter, the alignment film was ultrasonically cleaned in ultrapure water for 5 minutes and then dried in an oven at 120 ° C. for 30 minutes.

One glass substrate was sprayed with a 7 μm gap material, and the surface on which the liquid crystal alignment film was formed was placed inside so as to face each other so that the rubbing direction was antiparallel. A parallel cell was produced. The liquid crystal composition shown below was injected into the cell, and the injection port was sealed with a photocuring agent. Next, a heat treatment was performed at 110 ° C. for 30 minutes to manufacture a liquid crystal display element.

<3. Evaluation of electrical characteristics>
About the liquid crystal display element produced in Examples 1-8 and Comparative Examples 1-4, the measurement of the voltage holding rate and the long-term reliability were performed as follows.

1) Measurement of voltage holding ratio <Test Examples 1 to 12>
The voltage holding ratio was measured using a liquid crystal property evaluation apparatus 6254 type manufactured by Toyo Technica. The measurement conditions were a gate width of 60 μs, a frequency of 0.3 Hz, a wave height of ± 5 V, and a measurement temperature of 60 ° C. It can be said that the larger this value, the better the electrical characteristics. The results are shown in Tables 2 and 3.

2) Measurement of long-term reliability <Test Examples 1 to 5 (Examples 1 to 4 and Comparative Example 1)>
About the produced liquid crystal display element, the voltage holding rate was calculated | required with time and the holding | maintenance characteristic was evaluated. As a test method for holding characteristics, a liquid crystal display element was left in an atmosphere at a temperature of 100 ° C. for 100 hours, taken out during the course of time, and measured for voltage holding ratio. It can be said that the smaller the decrease in the voltage holding ratio (for example, if the standing time is 100 hours or more under the above conditions and the amount of decrease in the voltage holding ratio is less than 1%), the better the long-term reliability. The results are shown in Table 2.

<Table 2>

<Test Examples 6 to 12 (Examples 5 to 8 and Comparative Examples 2 to 4)>
About the produced liquid crystal display element, the voltage holding rate was calculated | required with time and the holding | maintenance characteristic was evaluated. As a test method for holding characteristics, a liquid crystal display element was left for 540 hours in an atmosphere at a temperature of 60 ° C., and the voltage holding ratio measurement was taken out over time during the course. It can be said that the smaller the decrease in the voltage holding ratio (for example, if the standing time is 540 hours under the above conditions and the amount of decrease in the voltage holding ratio is less than 1%), the better the long-term reliability. The results are shown in Table 3.

<Table 3>

  As is apparent from Tables 2 and 3, in the case of a liquid crystal display element having a liquid crystal alignment film formed using the liquid crystal aligning agent of the present invention, the voltage holding ratio is high and the deterioration of storage characteristics is remarkably suppressed. .

Claims (14)

A composition comprising an alkenyl-substituted nadiimide compound and a polymer component selected from polyamic acid and a derivative of polyamic acid, wherein the polymer component is at least a compound represented by formula (16) and a compound represented by formula (17) Tetracarboxylic acid dianhydride which is a mixture of one or at least one of the compounds represented by the formula (16) and the formula (17) and at least one of the compounds represented by the formulas (1) to (15) A liquid crystal aligning agent which is at least one of polymers obtained by reacting a product with a diamine:

Here, Ph means phenyl and Me means methyl. Alkenyl substituted nadimide compound is a compound represented by formula (a), the liquid crystal alignment agent according to claim 1:

Wherein R ¹ and R ² are independently hydrogen, alkyl having 1 to 12 carbons, alkenyl having 3 to 6 carbons, cycloalkyl having 5 to 8 carbons, aryl or benzyl, and n is 1 or 2 Is;
When n is 1, R ³ is alkyl having 1 to 12 carbons, cycloalkyl having 5 to 8 carbons, aryl having 6 to 12 carbons, benzyl, -L ^1- (O) _q- (L ² O ) _R— R ⁴ (L ¹ and L ² are independently alkylene having 2 to 6 carbons, R ⁴ is alkyl having 2 to 6 carbons, q is 0 or 1, and r is 1 ),-(L ³ ) _s -B ² -R ⁵ (L ³ is alkylene having 1 to 4 carbon atoms, s is 0 or 1, and B ² is any hydrogen. Phenylene, which may be replaced with —OH, and R ⁵ is alkyl having 1 to 4 carbon atoms), or —B ² -T-B ¹ (B ² is any hydrogen replaced with —OH; and is also phenylene, T is _{-CH 2 -, - C (CH} 3) 2 -, - CO -, - O-, S- or -SO ₂ -, and ^{B 1} represents be a) phenyl which may be replaced arbitrary hydrogen in -OH;.
When n is 2, R ³ is alkylene having 2 to 20 carbon atoms, cycloalkylene having 5 to 8 carbon atoms, arylene having 6 to 12 carbon atoms, -L ^1- (O) _q- (L ² O) _r -L ⁴ - ^(L 1, ^{L 2} and ^{L 4} are independently alkylene of 2 to 6 carbon atoms, q is 0 or 1, and r is an integer from 1 to 30.), - ( L ³ ) _s -B ² -L ^5- (L ³ and L ⁵ are each independently an alkylene having 1 to 4 carbon atoms, s is 0 or 1, and B ² is any hydrogen replaced with -OH. -B ² -T-B ^2- (B ² is independently phenylene in which any hydrogen may be replaced by -OH, and T is -CH _2- , _{-C (CH 3) 2 -,} - CO -, - O -, - S- or -SO ₂ -. a a), or - _{^{2 -O-B 2 -C (CH}} 3) 2 -B 2 -O-B 2 - a ^{(B 2} is any independently hydrogen is phenylene which may be replaced by -OH.). Alkenyl substituted nadimide compound is at least one compound of formula (a-1) ~ formula (a-3), a liquid crystal aligning agent of claim 1:

The liquid crystal aligning agent of any one of Claims 1-3 whose ratio of the alkenyl substituted nadiimide compound is 0.01-2 by weight ratio with respect to the polymer component in a liquid crystal aligning agent. The liquid crystal aligning agent of any one of Claims 1-4 whose diamine is at least 1 chosen from the group of the non-side chain type diamine shown by Formula (I)-Formula (VII):

Wherein A ¹ is a linear alkylene having 2 to 12 carbon atoms; A ² is a linear alkylene having 1 to 12 carbon atoms; A ³ is independently a single bond, —O—, —CO—, —CONH—, —NHCO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —O—A ² —O—, —S—, —S—S—, —SO ₂ —, ^-S-a 2 -S-, or be ^{a 2;} any hydrogen in cyclohexane ring and benzene ring are _{fluorine, -CH 3, -OH, -COOH,} -SO 3 H, PO 3 H 2, benzyl or hydroxy It may be replaced with benzyl. The diamine is represented by formula (IV-1), formula (IV-2), formula (IV-15), formula (IV-16), formula (V-1) to formula (V-13), and formula (VII-2). The liquid crystal aligning agent of any one of Claims 1-4 which is at least 1 chosen from the group of the non-side chain type diamine shown by these:

A diamine is a mixture of at least one selected from the group of non-side chain diamines represented by formulas (I) to (VII) and at least one side chain diamine having a side chain group, wherein the side chain group Is an alkyl having 3 or more carbon atoms, an alkoxy having 3 or more carbon atoms, an alkoxyalkyl having 3 or more carbon atoms, a group having a steroid skeleton, an alkyl having 3 or more carbon atoms at the terminal, an alkoxy having 3 or more carbon atoms, or 3 or more carbon atoms The liquid crystal aligning agent of any one of Claims 1-4 which is group chosen from group which has the alkoxyalkyl of:

Wherein A ¹ is a linear alkylene having 2 to 12 carbon atoms; A ² is a linear alkylene having 1 to 12 carbon atoms; A ³ is independently a single bond, —O—, —CO—, —CONH—, —NHCO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —O—A ² —O—, —S—, —S—S—, —SO ₂ —, ^-S-a 2 -S-, or be ^{a 2;} any hydrogen in cyclohexane ring and benzene ring are _{fluorine, -CH 3, -OH, -COOH,} -SO 3 H, PO 3 H 2, benzyl or hydroxy It may be replaced with benzyl. The liquid crystal aligning agent according to claim 7 , wherein the side chain diamine is a diamine selected from the group of compounds represented by formulas (VIII) to (XII):

(Here, ^{R 6} represents a single bond, -O -, - CO -, - COO -, - OCO -, - CONH -, - CH 2 O -, - CF 2 O-, or an alkylene having 1 to 6 carbon atoms And any —CH ₂ — in the alkylene may be replaced by —O—, —CH═CH— or —C≡C—; R ⁷ is a group having a steroid skeleton, having 3 to 30 carbon atoms Alkyl having 3 to 30 carbon atoms or phenyl having 3 to 30 carbon atoms as a substituent, or a group represented by formula (D-1), and any —CH ₂ — in the alkyl May be replaced by —O—, —CH═CH— or —C≡C—;

Here, R ¹⁸ , R ¹⁹ and R ²⁰ are independently a single bond, —O—, —COO—, —OCO—, —CONH—, alkylene having 1 to 4 carbons, or oxyalkylene having 1 to 3 carbons. Or Ring C and C are independently 1,4-phenylene or 1,4-cyclohexylene; R ²¹ and R ²² are independently fluorine or methyl; There are, m1 and m2 is independently 0, 1 or 2; e, f and g is an integer of 0 to 3 independently, their sum is 1 or ^{more; R 23} is the number of carbon atoms An alkyl having 3 to 30 carbons, an alkoxy having 3 to 30 carbons, or an alkoxyalkyl having 3 to 30 carbons, and in these alkyls, alkoxys and alkoxyalkyls, any hydrogen is replaced by fluorine. And any —CH ₂ — may be replaced by difluoromethylene or a group represented by formula (D-2);

Here, R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ are each independently alkyl or phenyl having 1 to 10 carbon atoms, and n is an integer of 1 to 100. )

(Wherein R ⁸ is independently hydrogen or methyl; R ⁹ is hydrogen, alkyl having 1 to 30 carbons, or alkenyl having 2 to 30 carbons; and R ¹⁰ is independently a single bond) , -CO- or -CH ₂ - is).

(Wherein R ⁸ is independently hydrogen or methyl; R ⁹ is hydrogen, alkyl having 1 to 30 carbons, or alkenyl having 2 to 30 carbons; R ¹⁰ is independently a single bond, — CO— or —CH ₂ —; and R ¹¹ and R ¹² are independently hydrogen, alkyl having 1 to 30 carbons, or phenyl.)

(Wherein R ¹³ is alkyl having 3 to 30 carbon atoms, and any —CH ₂ — in the alkyl may be replaced by —O—, —CH═CH— or C≡C—; R ¹⁴ is independently -O- or alkylene having 1 to 6 carbon atoms; ring A is 1,4-phenylene or 1,4-cyclohexylene; a is 0 or 1; b is 0, 1 Or 2; and c is independently 0 or 1.)

(Wherein R ¹⁵ is alkyl having 3 to 30 carbon atoms or fluorinated alkyl having 3 to 30 carbon atoms; R ¹⁶ is hydrogen, alkyl having 1 to 30 carbon atoms or fluorinated alkyl having 1 to 30 carbon atoms. Yes; R ¹⁷ is independently —O— or alkylene having 1 to 6 carbons; and d is independently 0 or 1. Side chain type diamine has the formula (VIII-2), formula (VIII-4), a diamine selected from the group of compounds of formula (VIII-5) and formula (VIII-6), according to claim 7 Liquid crystal aligning agent:

Here, R ²⁸ and R ²⁹ are independently alkyl having 3 to 30 carbons or alkoxy having 3 to 30 carbons. The non-side chain diamine is represented by formula (IV-1), formula (IV-2), formula (IV-15), formula (IV-16), formula (V-1) to formula (V-13), and formula (IV). VII-2) is a diamine selected from the group of compounds represented by formula (VIII-2), formula (VIII-4), formula (VIII-5) and formula (VIII-6). The liquid crystal aligning agent of Claim 7 which is diamine chosen from the group of the compound shown:

Here, R ²⁸ and R ²⁹ are independently alkyl having 3 to 30 carbons or alkoxy having 3 to 30 carbons. The polymer component comprises at least one of the compound represented by formula (16) and the compound represented by formula (17) or at least one of the compound represented by formula (16) and the compound represented by formula (17) and the formula (1 ) To at least one selected from the group consisting of a tetracarboxylic dianhydride which is a mixture with at least one of the compounds represented by formula (15) and a non-side chain diamine represented by formulas (I) to (VII) Or a derivative thereof, a polyamic acid obtained by reaction of the above tetracarboxylic dianhydride with at least one selected from the group of side chain diamines represented by formulas (VIII) to (XII) It is obtained by reacting an acid or a derivative thereof, and the tetracarboxylic dianhydride with a mixture of the non-side chain diamine and the side chain diamine. The liquid crystal aligning agent according to claim 1, which is at least two polymers selected from the group consisting of polyamic acids and derivatives thereof:

(Here, Ph means phenyl and Me means methyl. The polymer component is a mixture of at least two polymers.)

(Wherein A ¹ is a linear alkylene having 2 to 12 carbon atoms; A ² is a linear alkylene having 1 to 12 carbon atoms; A ³ is independently a single bond, —O—, —CO—. , —CONH—, —NHCO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —O—A ² —O—, —S—, —S—S—, —SO ₂ —. , —S—A ² —S—, or A ² ; any hydrogen in the cyclohexane ring and the benzene ring is fluorine, —CH ₃ , —OH, —COOH, —SO ₃ H, PO ₃ H ₂ , benzyl Or may be replaced by hydroxybenzyl.)

(Here, ^{R 6} represents a single bond, -O -, - CO -, - COO -, - OCO -, - CONH -, - CH 2 O -, - CF 2 O-, or an alkylene having 1 to 6 carbon atoms And any —CH ₂ — in the alkylene may be replaced by —O—, —CH═CH— or —C≡C—; R ⁷ is a group having a steroid skeleton, having 3 to 30 carbon atoms Alkyl having 3 to 30 carbon atoms or phenyl having 3 to 30 carbon atoms as a substituent, or a group represented by formula (D-1), and any —CH ₂ — in the alkyl May be replaced by —O—, —CH═CH— or —C≡C—;

Here, R ¹⁸ , R ¹⁹ and R ²⁰ are independently a single bond, —O—, —COO—, —OCO—, —CONH—, alkylene having 1 to 4 carbons, or oxyalkylene having 1 to 3 carbons. Or Ring C and C are independently 1,4-phenylene or 1,4-cyclohexylene; R ²¹ and R ²² are independently fluorine or methyl; There are, m1 and m2 is independently 0, 1 or 2; e, f and g is an integer of 0 to 3 independently, their sum is 1 or ^{more; R 23} is the number of carbon atoms An alkyl having 3 to 30 carbons, an alkoxy having 3 to 30 carbons, or an alkoxyalkyl having 3 to 30 carbons, and in these alkyls, alkoxys and alkoxyalkyls, any hydrogen is replaced by fluorine. And any —CH ₂ — may be replaced by difluoromethylene or a group represented by formula (D-2);

Here, R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ are each independently alkyl or phenyl having 1 to 10 carbon atoms, and n is an integer of 1 to 100. )

(Wherein R ⁸ is independently hydrogen or methyl; R ⁹ is hydrogen, alkyl having 1 to 30 carbons, or alkenyl having 2 to 30 carbons; and R ¹⁰ is independently a single bond) , -CO- or -CH ₂ - is).

(Wherein R ⁸ is independently hydrogen or methyl; R ⁹ is hydrogen, alkyl having 1 to 30 carbons, or alkenyl having 2 to 30 carbons; R ¹⁰ is independently a single bond, — CO— or —CH ₂ —; and R ¹¹ and R ¹² are independently hydrogen, alkyl having 1 to 30 carbons, or phenyl.)

(Wherein R ¹³ is alkyl having 3 to 30 carbon atoms, and any —CH ₂ — in the alkyl may be replaced by —O—, —CH═CH— or C≡C—; R ¹⁴ is independently -O- or alkylene having 1 to 6 carbon atoms; ring A is 1,4-phenylene or 1,4-cyclohexylene; a is 0 or 1; b is 0, 1 Or 2; and c is independently 0 or 1.)

(Wherein R ¹⁵ is alkyl having 3 to 30 carbon atoms or fluorinated alkyl having 3 to 30 carbon atoms; R ¹⁶ is hydrogen, alkyl having 1 to 30 carbon atoms or fluorinated alkyl having 1 to 30 carbon atoms. Yes; R ¹⁷ is independently —O— or alkylene having 1 to 6 carbons; and d is independently 0 or 1. The polymer component comprises at least one of the compound represented by formula (16) and the compound represented by formula (17) or at least one of the compound represented by formula (16) and the compound represented by formula (17) and the formula (1 ) To tetracarboxylic dianhydride which is a mixture with at least one of the compounds represented by formula (15), formula (IV-1), formula (IV-2), formula (IV-15), formula (IV- 16) a polyamic acid or a derivative thereof obtained by reaction with at least one selected from the group of non-side chain diamines represented by formula (V-1) to formula (V-13) and formula (VII-2), At least one selected from the group consisting of the above tetracarboxylic dianhydrides and side chain diamines represented by formula (VIII-2), formula (VIII-4), formula (VIII-5) and formula (VIII-6) Polyamic acid obtained by reaction with one Or a derivative thereof, and a polyamic acid or a derivative thereof obtained by reacting the tetracarboxylic dianhydride with the mixture of the non-side chain diamine and the side chain diamine. The liquid crystal aligning agent according to claim 11 :

Here, R ²⁸ and R ²⁹ are independently alkyl having 3 to 30 carbons or alkoxy having 3 to 30 carbons. A liquid crystal alignment film formed by firing the liquid crystal aligning agent according to any one of claims 1 to 12 in a film state. A pair of substrates disposed opposite to each other, an electrode formed on one or both of the surfaces facing each other of the pair of substrates, and a surface facing each of the pair of substrates. 14. A liquid crystal display device comprising the liquid crystal alignment film according to 13 , and a liquid crystal layer formed between the pair of substrates.