JP5062109B2 - 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 obtained by combining a polyamic acid with an alkenyl-substituted nadiimide compound and a compound having a radical polymerizable unsaturated double bond.

  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.

  The liquid crystal display element usually has 1) a pair of substrates arranged opposite to each other, 2) electrodes formed on one or both of the opposed surfaces of each of the pair of substrates, and 3) each of the pair of substrates. And 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. 1) TN (Twisted Nematic) type liquid crystal display element twisted by 90 degrees, 2) STN (Super Twisted Nematic) twisted by 180 degrees or more. 3) A so-called TFT (Thin Film Transistor) type liquid crystal display element using a thin film transistor has been put into practical use. These liquid crystal display elements have a drawback that the viewing angle at which an image can be properly viewed is narrow, and when viewed from an oblique direction, luminance and contrast are lowered and luminance is inverted in a halftone.

  In recent years, the problems of viewing angle are as follows: 1) TN-TFT type liquid crystal display element using optical compensation film, 2) VA (vertical alignment) type liquid crystal display element using vertical alignment and optical compensation film, 3) vertical MVA (Multi Domain Vertical Alignment) type liquid crystal display element using both alignment and protrusion structure technology, or 4) In-plane switching (IPS) type liquid crystal display element of horizontal electric field type, 5) ECB (Electrically Controlled Birefringence) type Liquid crystal display element 6) It is improved by a technique such as an optically compensated bend (Optically Compensated Bend or Optically Self-Compensated Birefringence: OCB) type liquid crystal display element. And the improved technique is put to practical use or practical use is 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 components 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. Various liquid crystal aligning agents other than polyamic acid are also being studied, but they are almost practical in terms of heat resistance, chemical resistance (liquid crystal resistance), coating properties, liquid crystal alignment properties, electrical properties, optical properties, display properties, etc. It has not been converted.

  An important characteristic required for the liquid crystal alignment film in order to improve the display quality of the liquid crystal display element is ion density. When the ion density is high, the voltage applied to the liquid crystal during the frame period is lowered, and as a result, the luminance is lowered, which may hinder normal gradation display. Moreover, even if the initial ion density is low, there is a problem when the ion density (long-term reliability) after the high-temperature acceleration test becomes high. On the other hand, when the residual charge is large, a so-called “afterimage” is generated in which an erased image remains even though the voltage is turned off after the voltage is applied. Long-term reliability and afterimages are problematic because they degrade the display quality of liquid crystals.

Recently, several methods have been proposed as an attempt to solve the above-described long-term reliability problem.
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 (for example, see 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).

  In addition, several techniques have been proposed for solving problems including improvement of performance of a liquid crystal display element by adding an additive to polyamic acid. As such a technique, for example, a liquid crystal alignment agent containing a polyamic acid and a curing accelerator having a pyridine structure or a quinoline structure (see, for example, Patent Document 7), a liquid crystal alignment containing a polyamic acid and an alkenyl-substituted nadiimide compound. And a liquid crystal aligning agent (for example, see Patent Documents 10 and 11) containing a polyamic acid and an epoxy group-containing compound.

  However, these prior arts have not fully solved the problem of ion density and long-term reliability. For example, in Patent Document 7, the curing accelerator is assumed to evaporate, sublimate, and decompose in imidization when a liquid crystal alignment film is manufactured. In a liquid crystal alignment film manufactured using such a liquid crystal alignment film, The effect of the curing accelerator on the electrical properties of the liquid crystal alignment film has not been studied.

  For example, in patent document 11, adsorption | suction of an ionic impurity is included in the subject, and the voltage holding rate of the produced liquid crystal display element is described in the Example. However, although the voltage holding ratio and the ion density may be correlated, the initial voltage holding ratio and the ion density over time may not be correlated. This is presumably because the ionic impurities are not only contained in the liquid crystal display element when it is manufactured, but also are caused by, for example, decomposition of the liquid crystal accompanying the operation of the liquid crystal display element and change with time. Therefore, although the technique of Patent Document 11 that adsorbs ionic impurities seems to be effective in reducing the ionic impurities contained in the liquid crystal display device, the generation of ionic impurities over time is suppressed. There is still room for consideration.

In recent years, several methods have been proposed as an attempt to solve the above-mentioned “afterimage” problem.
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 Patent Documents 12 to 13).
2) A varnish composition containing a polyamic acid and a polymer component containing polyamide and a solvent is known (Patent Document 14).
3) Varnish compositions containing two or more polyamic acids and polyamides having different physical properties and a solvent are known. (Patent Document 15).
4) A varnish composition containing a polymer material containing a polyamic acid synthesized using a diamine compound having a specific structure is known (see Patent Document 16).
However, these prior arts do not sufficiently solve the problem of “afterimage” due to a large residual charge.

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-9-302225 JP 2004-341030 A JP-A-9-269491 JP 7-234410 A JP 2002-323701 A JP 11-193345 A JP-A-11-193347 International Publication No. 00/61684 Pamphlet WO 01/000733 pamphlet JP 2002-162630 A

  In consideration of the above situation, a liquid crystal aligning agent for a liquid crystal display device in which the problem of long-term reliability with respect to the electric density due to the ion density and the fluctuation of the ion density over time and the problem of the afterimage characteristic are improved, and using the same Development of a liquid crystal alignment film formed in this manner, and a liquid crystal display device including the same is desired.

  The inventors of the present invention have intensively studied to solve the above problems. As a result, when using a liquid crystal aligning agent that combines an alkenyl-substituted nadiimide compound and a compound having a radical polymerizable unsaturated double bond with a polyamic acid as an improver, a liquid crystal display element having a prepared liquid crystal alignment film, It has been found that good ion density and long-term reliability and improved afterimage characteristics can be imparted, and the present invention has been completed.

The liquid crystal aligning agent of this invention is shown by the following [1] term.
[1] A liquid crystal aligning agent containing an alkenyl-substituted nadiimide compound, a compound having a radical polymerizable unsaturated double bond, and a polyamic acid or a derivative thereof.

  According to the present invention, it is possible to provide a liquid crystal display element having a low ion density, good long-term reliability with respect to a change with time, and an improved afterimage characteristic problem.

そして、「アルケニル置換ナジイミド化合物」は、このナジイミド基の水素がアルケニルで置換されている化合物を意味する。アルケニルの置換位置は、５位、６位または７位である。ラジカル重合性不飽和二重結合を有する化合物はアルケニル置換ナジイミド化合物を含まない化合物として定義される。（メタ）アクリル酸は、アクリル酸およびメタクリル酸の総称として用いられる。式（１）で表される化合物を化合物（１）と称することがある。他の式で表される化合物についても同様である。 First, terms used in the present invention will be described.
“Nadiimide compound” means a compound having the following nadiimide group.

The “alkenyl-substituted nadiimide compound” means a compound in which the hydrogen of the nadiimide group is substituted with alkenyl. The substitution position of alkenyl is the 5-position, 6-position or 7-position. A compound having a radically polymerizable unsaturated double bond is defined as a compound not containing an alkenyl-substituted nadiimide compound. (Meth) acrylic acid is used as a general term for acrylic acid and methacrylic acid. The compound represented by formula (1) may be referred to as compound (1). The same applies to compounds represented by other formulas.

  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.

ここに、Ｌ^１およびＬ^２は、それぞれ独立して水素、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、炭素数６〜１２の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＝１のとき、Ｗは炭素数１〜１２のアルキル、炭素数２〜６のアルケニル、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、−Ｚ^１−（Ｏ）_ｑ−（Ｚ^２Ｏ）_ｒ−Ｚ^３−Ｈで表される基（この基において、Ｚ^１、Ｚ^２およびＺ^３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。）、−（Ｚ^４）_ｓ−Ｂ−Ｚ^５−Ｈで表される基（この基において、Ｚ^４およびＺ^５は独立して炭素数１〜４のアルキレンまたは炭素数５〜８のシクロアルキレンであり、Ｂはフェニレンであり、そしてｓは０または１である。）、または−Ｂ−Ｔ−Ｂ−Ｈで表される基（この基において、Ｂはフェニレンであり、そしてＴは−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、−ＣＯ−、−Ｓ−または−ＳＯ_２−である。）であり、このようなＷにおける１〜３個の水素は水酸基で置き換えられてもよく；ｎ＝２のとき、Ｗ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、−Ｚ^１−（Ｏ）_ｑ−（Ｚ^２Ｏ）_ｒ−Ｚ^３−で表される基（この基におけるＺ^１〜Ｚ^３、ｑおよびｒの意味は前記の通りである。）、−（Ｚ^４）_ｓ−Ｂ−Ｚ^５−で表される基（この基におけるＺ^４、Ｚ^５、Ｂおよびｓの意味は前記の通りである。）、または−Ｂ−Ｔ−Ｂ−で表される基（この基におけるＢおよびＴの意味は前記の通りである。）であり、このようなＷにおける１〜３個の水素は水酸基で置き換えられてもよい。 The present invention comprises the above item [1] and the following item [26].
[2] A composition containing an alkenyl-substituted nadiimide compound, a compound having a radical polymerizable unsaturated double bond, and a polyamic acid or a derivative thereof, wherein the alkenyl-substituted nadiimide compound is a compound represented by the formula (Ina) The liquid crystal aligning agent as described in the item [1].

Here, L ¹ and L ² are each independently hydrogen, alkyl having 1 to 12 carbons, alkenyl having 3 to 6 carbons, cycloalkyl having 5 to 8 carbons, aryl having 6 to 12 carbons, or benzyl N is 1 or 2, and when n = 1, W is alkyl having 1 to 12 carbons, alkenyl having 2 to 6 carbons, cycloalkyl having 5 to 8 carbons, or 6 to 12 carbons. A group represented by aryl, benzyl, -Z ^1- (O) _q- (Z ² O) _r -Z ³ -H (in this group, Z ¹ , Z ² and Z ³ are each independently a group having 2 to 2 carbon atoms; 6 is alkylene, q is 0 or 1, and r is an integer of 1 to 30.), a group represented by — (Z ⁴ ) _s —BZ ⁵ —H (in this group, sheet of Z ⁴ and ^{Z 5} number alkylene or C 1 to 4 carbon atoms are independently 5-8 Alkylene, B is phenylene, and s is 0 or 1.), or a group represented by -B-T-B-H, in which B is phenylene and T is —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, —CO—, —S— or —SO ₂ —. And when n = 2, W is alkylene having 2 to 20 carbon atoms, cycloalkylene having 5 to 8 carbon atoms, arylene having 6 to 12 carbon atoms, -Z ^1- (O) _q- ( Z ² O) a group represented by _r —Z ³ — (the meanings of Z ^{1 to} Z ³ , q and r in this group are as described above), — (Z ⁴ ) _s —BZ ⁵ — (The meanings of Z ⁴ , Z ⁵ , B and s in this group are as described above), Or a group represented by -B-T-B- (the meanings of B and T in this group are as described above), and 1 to 3 hydrogens in such W are replaced by hydroxyl groups. May be.

[3] A composition containing an alkenyl-substituted nadiimide compound, a polyamic acid or a derivative thereof, and a compound having a radical polymerizable unsaturated double bond, wherein the alkenyl-substituted nadiimide compound is represented by formulas (Ina-1) to (Ina- The liquid crystal aligning agent according to item [2], which is at least one of the compounds represented by 3).

[4] A composition containing an alkenyl-substituted nadiimide compound, a compound having a radical polymerizable unsaturated double bond, and a polyamic acid or a derivative thereof, wherein the ratio of the alkenyl-substituted nadiimide compound to the polyamic acid or the derivative thereof is a weight ratio. The liquid crystal aligning agent of any one of [1]-[3] which is 0.01-1.00.

[5] A composition containing an alkenyl-substituted nadiimide compound, a compound having a radical polymerizable unsaturated double bond, and a polyamic acid or a derivative thereof, wherein the compound having a radical polymerizable unsaturated double bond is (meth) The liquid crystal aligning agent of any one of [1]-[4] which is an acrylic acid derivative.

[6] A composition containing an alkenyl-substituted nadiimide compound, a compound having a radically polymerizable unsaturated double bond, and a polyamic acid or a derivative thereof, wherein the compound having a radically polymerizable unsaturated double bond is radically polymerizable A compound having two or more unsaturated double bonds or a mixture containing the compound, and the ratio of the compound having a radical polymerizable unsaturated double bond is 0.01 to 1.% by weight relative to the polyamic acid or derivative thereof. The liquid crystal aligning agent of any one of [1]-[4] which is 00.

[7] A composition containing an alkenyl-substituted nadiimide compound, a compound having a radical polymerizable unsaturated double bond, and a polyamic acid or a derivative thereof, wherein the compound having a radical polymerizable unsaturated double bond is N, N In item [6], which is at least one of '-methylenebisacrylamide, N, N'-dihydroxyethylene-bisacrylamide, ethylenebisacrylate, and 4,4'-methylenebis (N, N-dihydroxyethyleneacrylate aniline) The liquid crystal aligning agent of description.

[8] The polyamic acid reacts dialysis with at least one of the aromatic tetracarboxylic dianhydrides represented by formula (1), formula (2), formula (5) to formula (7) and formula (14). The liquid crystal aligning agent of any one of [1]-[7] which is a polymer obtained by this.

[9] The polymer according to any one of [1] to [7], wherein the polyamic acid is a polymer obtained by reacting an aromatic tetracarboxylic dianhydride represented by the formula (1) with a diamine. Liquid crystal aligning agent.

[10] The polyamic acid is a compound other than an aromatic tetracarboxylic dianhydride represented by the formula (1), the formula (2), the formula (5) to the formula (7), and the formula (14). The liquid crystal aligning agent according to any one of [1] to [7], which is a polymer obtained by reacting a mixture of tetracarboxylic dianhydride with diamine.

[11] The polyamic acid is a polymer obtained by reacting a mixture of an aromatic tetracarboxylic dianhydride represented by the formula (1) and a non-aromatic tetracarboxylic dianhydride with a diamine, [ The liquid crystal aligning agent of any one of [1]-[7].

[12] The polyamic acid is a compound other than an aromatic tetracarboxylic dianhydride represented by the formula (1), the formula (2), the formula (5) to the formula (7), and the formula (14). A polymer obtained by reacting a mixture of a tetracarboxylic dianhydride with a diamine, wherein the tetracarboxylic dianhydride other than aromatic is represented by formula (19), formula (23), formula (25), formula The liquid crystal aligning agent as described in the item [10], which is at least one of the compounds represented by (35) to (37), (39), (44) and (49).

[13] A polymer obtained by reacting a diamine with a mixture of an aromatic tetracarboxylic dianhydride represented by formula (1) and a tetracarboxylic dianhydride other than aromatic polyamine, Non-aromatic tetracarboxylic dianhydrides are represented by formula (19), formula (23), formula (25), formula (35) to formula (37), formula (39), formula (44) and formula (49). The liquid crystal aligning agent as described in the item [11], which is at least one of the compounds represented by:

[14] A polymer obtained by reacting a diamine with a mixture of an aromatic tetracarboxylic dianhydride represented by formula (1) and a tetracarboxylic dianhydride other than aromatic polyamine, The liquid crystal aligning agent as described in the item [11], wherein the tetracarboxylic dianhydride other than aromatic is a compound represented by the formula (19).

ここに、Ｘ^１は炭素数２〜１２の直鎖アルキレンであり；Ｘ^２は炭素数１〜１２の直鎖アルキレンであり；Ｘ^３は独立して単結合、−Ｏ−、−ＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−、−Ｏ−（ＣＨ_２）_ｔ−Ｏ−、−Ｓ−、−Ｓ−Ｓ−、−ＳＯ_２−、−Ｓ−（ＣＨ_２）_ｔ−Ｓ−または炭素数１〜１２の直鎖アルキレンであって、ｔは１〜１２の整数であり；シクロヘキサン環またはベンゼン環の任意の水素は、−Ｆ、−ＣＨ_３または−ＯＨ、−ＣＯＯＨ、−ＳＯ_３Ｈ、または−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。 [15] The liquid crystal according to any one of [8] to [14], wherein the diamine is at least one selected from the group of non-side chain diamines represented by formulas (I) to (VII). Alignment agent:

Wherein X ¹ is a linear alkylene having 2 to 12 carbon atoms; X ² is a linear alkylene having 1 to 12 carbon atoms; X ³ is independently a single bond, —O—, —CO—, —CONH—, —NHCO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —O— (CH ₂ ) _t —O—, —S—, —S—S—, —SO _{2 -, - S- (CH 2} ) a t -S- or straight chain alkylene of 1 to 12 carbon atoms, t is an integer from 1 to 12; any hydrogen cyclohexane ring or benzene ring, - F, —CH ₃ or —OH, —COOH, —SO ₃ H, or —PO ₃ H ₂ , benzyl or hydroxybenzyl may be substituted.

[16] The diamine is represented by formula (IV-1), formula (IV-2), formula (IV-15), formula (IV-16), formula (V-1) to formula (V-12), formula (V -33) and the liquid crystal aligning agent of any one of [8]-[14] which is at least 1 chosen from the non-side chain type diamine represented by Formula (VII-2).

ここに、Ｘ^１は炭素数２〜１２の直鎖アルキレンであり；Ｘ^２は炭素数１〜１２の直鎖アルキレンであり；Ｘ^３は独立して単結合、−Ｏ−、−ＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−、−Ｏ−（ＣＨ_２）_ｔ−Ｏ−、−Ｓ−、−Ｓ−Ｓ−、−ＳＯ_２−、−Ｓ−（ＣＨ_２）_ｔ−Ｓ−または炭素数１〜１２の直鎖アルキレンであって、ｔは１〜１２の整数であり；シクロヘキサン環またはベンゼン環の任意の水素は、−Ｆ、−ＣＨ_３または−ＯＨ、−ＣＯＯＨ、−ＳＯ_３Ｈ、または−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。 [17] At least one diamine selected from non-side chain diamines represented by formulas (I) to (VII), alkyl having 3 or more carbon atoms, alkoxy having 3 or more carbon atoms, alkoxy having 3 or more carbon atoms At least one side chain diamine having a side chain group selected from alkyl, a group having a steroid skeleton, and an alkyl having 1 or more carbon atoms, an alkoxy having 1 or more carbon atoms, or an alkoxyalkyl having 2 or more carbon atoms at the terminal. The liquid crystal aligning agent of any one of [8]-[14] which is a mixture with one:

Wherein X ¹ is a linear alkylene having 2 to 12 carbon atoms; X ² is a linear alkylene having 1 to 12 carbon atoms; X ³ is independently a single bond, —O—, —CO—, —CONH—, —NHCO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —O— (CH ₂ ) _t —O—, —S—, —S—S—, —SO _{2 -, - S- (CH 2} ) a t -S- or straight chain alkylene of 1 to 12 carbon atoms, t is an integer from 1 to 12; any hydrogen cyclohexane ring or benzene ring, - F, —CH ₃ or —OH, —COOH, —SO ₃ H, or —PO ₃ H ₂ , benzyl or hydroxybenzyl may be substituted.

（ここに、Ｒ^１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^２はステロイド骨格を有する基、炭素数３〜３０のアルキル、炭素数３〜３０のアルキルもしくは炭素数３〜３０のアルコキシを置換基として有するフェニル、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^１３、Ｒ^１４およびＲ^１５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^１６およびＲ^１７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^１８は炭素数１〜３０のアルキル、炭素数１〜３０のアルコキシ、または炭素数２〜３０のアルコキシアルキルであり、これらのアルキル、アルコキシ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^１９、Ｒ^２０、Ｒ^２１およびＲ^２２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^３は独立して水素またはメチルであり；Ｒ^４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^５は独立して単結合、−ＣＯ−または−ＣＨ_２−である。）

（ここに、Ｒ^３は独立して水素またはメチルであり；Ｒ^４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^５は独立して単結合、−ＣＯ−または−ＣＨ_２−であり；そして、Ｒ^６およびＲ^７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^８は炭素数１〜３０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^９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^１０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^１１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^１２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。） [18] The liquid crystal aligning agent according to the item [17], wherein the side chain diamine is a diamine selected from the group of compounds represented by formulas (VIII) to (XII).

(Here, ^{R 1} 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 ² is a group having a steroid skeleton, having 3 to 30 carbon atoms Or an alkyl group having 3 to 30 carbon atoms or phenyl having 3 to 30 carbon atoms as a substituent, or a group represented by the formula (D-1), and any —CH ₂ — group in the alkyl group May be replaced by —O—, —CH═CH— or —C≡C—;

Here, R ¹³ , R ¹⁴ and R ¹⁵ are each 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 ¹⁶ and R ¹⁷ are independently fluorine or methyl; M1 and m2 are independently 0, 1 or 2; e, f and g are each independently an integer of 0 to 3, and their sum is 1 or more; R ¹⁸ is carbon number 1-30 alkyl, C1-C30 alkoxy, or C2-C30 alkoxyalkyl, and in these alkyl, alkoxy and alkoxyalkyl, any hydrogen is replaced with fluorine. And any —CH ₂ — may be replaced by difluoromethylene or a group represented by formula (D-2);

Here, R ¹⁹ , R ²⁰ , R ²¹ and R ²² are independently alkyl having 1 to 10 carbons or phenyl, and n is an integer of 1 to 100. )

(Wherein R ³ is independently hydrogen or methyl; R ⁴ is hydrogen, alkyl having 1 to 30 carbons, or alkenyl having 2 to 30 carbons; and R ⁵ is independently a single bond. , -CO- or -CH ₂ - is).

(Wherein R ³ is independently hydrogen or methyl; R ⁴ is hydrogen, alkyl having 1 to 30 carbons, or alkenyl having 2 to 30 carbons; R ⁵ is independently a single bond, — CO— or —CH ₂ —; and R ⁶ and R ⁷ are independently hydrogen, alkyl having 1 to 30 carbons, or phenyl.)

(Where R ⁸ is alkyl having 1 to 30 carbon atoms, and any —CH ₂ — in the alkyl may be replaced by —O—, —CH═CH— or C≡C—; R ⁹ 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.)

(Where R ¹⁰ is alkyl having 3 to 30 carbon atoms or fluorinated alkyl having 3 to 30 carbon atoms; R ¹¹ is hydrogen, alkyl having 1 to 30 carbon atoms or fluorinated alkyl having 1 to 30 carbon atoms. Yes; R ¹² is independently —O— or alkylene having 1 to 6 carbons; and d is independently 0 or 1.

（ここに、Ｒ^２３およびＲ^２４は独立して炭素数３〜３０のアルキル、または炭素数３〜３０のアルコキシであり、Ｒ^２９およびＲ^３０は独立して炭素数１〜３０のアルキル、または炭素数１〜３０のアルコキシである。） [19] The side chain diamine is represented by formula (VIII-2), formula (VIII-4), formula (VIII-5), formula (VIII-6), formula (XI-2) and formula (XI-4). The liquid crystal aligning agent as described in the item [ 17 ], which is a diamine selected from the represented compounds.

(Wherein R ²³ and R ²⁴ are independently alkyl having 3 to 30 carbons, or alkoxy having 3 to 30 carbons, and R ²⁹ and R ³⁰ are independently alkyl having 1 to 30 carbons, or (It is an alkoxy having 1 to 30 carbon atoms.)

（ここに、Ｒ^２３およびＲ^２４は独立して炭素数３〜３０のアルキル、または炭素数３〜３０のアルコキシであり、Ｒ^２９およびＲ^３０は独立して炭素数１〜３０のアルキル、または炭素数１〜３０のアルコキシである。） [20] 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-12). , A diamine selected from the compounds represented by formula (V-33) and formula (VII-2), and the side chain diamine is formula (VIII-2), formula (VIII-4), formula (VIII-5) ), A liquid crystal aligning agent according to item [17], which is a diamine selected from compounds represented by formula (VIII-6), formula (XI-2) and formula (XI-4).

(Wherein R ²³ and R ²⁴ are independently alkyl having 3 to 30 carbons, or alkoxy having 3 to 30 carbons, and R ²⁹ and R ³⁰ are independently alkyl having 1 to 30 carbons, or (It is an alkoxy having 1 to 30 carbon atoms.)

（ここに、Ｒ^２３およびＲ^２４は独立して炭素数３〜３０のアルキル、または炭素数３〜３０のアルコキシであり、Ｒ^２９およびＲ^３０は独立して炭素数１〜３０のアルキル、または炭素数１〜３０のアルコキシである。） [21] The polymer comprises at least one aromatic tetracarboxylic dianhydride represented by the formula (1), the formula (2), the formula (5) to the formula (7), and the formula (14), and the formula (19). Formula (23), Formula (25), Formula (35) to Formula (37), Formula (39), Formula (44), and Non-aromatic tetracarboxylic dianhydride represented by Formula (49) Mixtures of at least one, formula (IV-1), formula (IV-2), formula (IV-15), formula (IV-16), formula (V-1) to formula (V-12), formula (V-33) and a polyamic acid obtained by reacting at least one of the non-side chain diamines represented by formula (VII-2) and a derivative thereof, and a mixture of the tetracarboxylic dianhydride and the formula (VIII-2), formula (VIII-4), formula (VIII-5), formula (VIII-6), formula (XI-2) and formula (XI-4) [1] to at least one selected from a polyamic acid obtained by reacting a mixture of at least one selected from side-chain diamines and at least one non-side-chain diamine and a derivative thereof. [7] The liquid crystal aligning agent according to any one of [7].

(Wherein R ²³ and R ²⁴ are independently alkyl having 3 to 30 carbons, or alkoxy having 3 to 30 carbons, and R ²⁹ and R ³⁰ are independently alkyl having 1 to 30 carbons, or (It is an alkoxy having 1 to 30 carbon atoms.)

[22] The polymer is obtained by reacting a mixture of at least one of an aromatic tetracarboxylic dianhydride and at least one of a non-aromatic tetracarboxylic dianhydride and at least one of a non-side chain diamine. The liquid crystal aligning agent according to item [21], which is a polyamic acid.

[23] A polymer is obtained by reacting a mixture of at least one aromatic tetracarboxylic dianhydride and at least one non-aromatic tetracarboxylic dianhydride with at least one non-side chain diamine. And a mixture of the above-mentioned tetracarboxylic dianhydrides with a mixture of at least one non-side chain diamine and at least one side chain diamine, [21] ] The liquid crystal aligning agent of a term.

[24] The polymer is a mixture of at least one of aromatic tetracarboxylic dianhydrides and at least one of non-aromatic tetracarboxylic dianhydrides, at least one of non-side chain diamines, and at least of side chain diamines. The liquid crystal aligning agent according to item [21], which is at least one selected from a polyamic acid obtained by reacting a mixture with one and a derivative thereof.

[25] A liquid crystal alignment film formed by applying the liquid crystal aligning agent according to any one of [1] to [24] on a substrate and baking it in a film state.

[26] 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. A liquid crystal display element having a liquid crystal alignment film and a liquid crystal layer formed between the pair of substrates, wherein the liquid crystal alignment film is the liquid crystal alignment film according to item [25]. .

  Below, the liquid crystal aligning agent of this invention is demonstrated in detail. The liquid crystal aligning agent of the present invention is a composition containing an alkenyl-substituted nadiimide compound, a compound having a radical polymerizable unsaturated double bond, and a polyamic acid.

First, the alkenyl-substituted nadiimide compound will be described. The alkenyl-substituted nadiimide compound is preferably a compound that can be dissolved in a solvent that dissolves the polyamic acid or derivative thereof used in the present invention. An example of such an alkenyl-substituted nadiimide compound is a compound represented by the formula (Ina).

L ¹ and L ^{2 in} formula (Ina) are each independently hydrogen, alkyl having 1 to 12 carbons, alkenyl having 3 to 6 carbons, cycloalkyl having 5 to 8 carbons, aryl or benzyl, n is 1 or 2.

When n = 1, W is alkyl of 1 to 12 carbon atoms, alkenyl having 2 to 6 carbon atoms, cycloalkyl of 5 to 8 carbon atoms, having 6 to 12 carbon atoms aryl, benzyl, ^-Z 1 - (O) _{^{q - (Z 2 O) r}} -Z 3 -H (Z 1, Z 2 and ^{Z 3} are independently alkylene of 2 to 6 carbon atoms, q is 0, or 1, and r is 1 to 30 -(Z ⁴ ) _s -BZ ⁵ -H (Z ⁴ and Z ⁵ are each independently an alkylene having 1 to 4 carbon atoms or a cyclo having 5 to 8 carbon atoms). Alkylene, B is phenylene, and s is 0 or 1.) -B-T-B-H (B is phenylene, and T is -CH ₂ -,- _{C (CH 3) 2 -,} - O -, - CO -, - S- or -SO ₂ -. and is) a group represented by also, 1-3 hydrogens these groups are substituted groups with hydroxyl groups.

In this case, preferable R ³ is alkyl having 1 to 8 carbons, alkenyl having 3 to 4 carbons, cyclohexyl, phenyl, benzyl, poly (ethyleneoxy) ethyl having 4 to 10 carbons, phenyloxyphenyl, phenylmethylphenyl. , Phenylisopropylidenephenyl, and groups in which one or two hydrogens of these groups are replaced by hydroxyl groups.

In the formula (Ina), when n = 2, W is alkylene having 2 to 20 carbon atoms, cycloalkylene having 5 to 8 carbon atoms, arylene having 6 to 12 carbon atoms, -Z ¹ -O- (Z ² O) _r A group represented by —Z ³ — (the meanings of Z ^{1 to} Z ³ and r are as defined above), —Z ⁴ —B—Z ⁵ — (the meanings of Z ⁴ , Z ⁵ and B are the same as those described above; is as. a group represented _{by), -B- (O-B)} s -T- (B-O) s -B- (B is phenylene, T is alkylene of 1 to 3 carbon atoms, -O- or -SO 2 _- and is, s is 0 or 1 group represented by) or 1-3 hydrogen of these groups, is replaced with a hydroxyl group..

At this time, preferable W is alkylene having 2 to 12 carbon atoms, cyclohexylene, phenylene, tolylene, xylylene, —C ₃ H ₆ —O— (Z ² —O) _r —O—C ₃ H ₆ — (Z ² is an alkylene of 2 to 6 carbon atoms, r is 1 or 2 groups represented by), -B-T-B- ( B is phenylene, and T is _-CH 2 -., - O A group represented by-or -SO _2- ), a group represented by -B-O-B-C ₃ H ₆ -B-O-B- (B is phenylene), and these In this group, one or two hydrogen atoms are replaced with a hydroxyl group.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

In the present invention, these alkenyl-substituted nadiimide compounds may be used alone, or a mixture of two or more of these may be used. Among the alkenyl-substituted nadiimide compounds, preferred compounds are shown below.
N, N′-ethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-ethylene-bis (allylmethylbicyclo [2.2. 1] Hept-5-ene-2,3-dicarboximide), N, N′-ethylene-bis (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) N, N′-trimethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-hexamethylene-bis (allylbicyclo [2.2 .1] hept-5-ene-2,3-dicarboximide), N, N′-hexamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxy Imide), N, N′-dodecamethylene-bis (a) Rilbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-dodecamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2 , 3-dicarboximide), N, N′-cyclohexylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-cyclohexylene- Bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),

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

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

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

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

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

  As a particularly preferred alkenyl-substituted nadiimide compound, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) represented by the following formula (Ina-1) Phenyl} methane, N, N′-m-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) of the formula (Ina-2), and the formula N, N′-hexamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) represented by (Ina-3).

  Next, the compound having a radical polymerizable unsaturated double bond used in the present invention will be described. The alkenyl-substituted nadiimide compound also has a radical polymerizable unsaturated double bond, but the compound having a radical polymerizable unsaturated double bond used in the present invention does not include an alkenyl-substituted nadiimide compound as described above. As the compound having such a radical polymerizable unsaturated double bond, (meth) acrylic acid esters, (meth) acrylic acid derivatives such as (meth) acrylic acid amide, and bismaleimide are preferable. A (meth) acrylic acid derivative having two or more radically polymerizable unsaturated double bonds is more preferable.

  Specific examples of the (meth) acrylic acid ester include cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, Isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate. Mention may be made of 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.

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

  Specific examples of polyfunctional (meth) acrylic esters having three or more functional groups include 4,4'-methylenebis (N, N-dihydroxyethylene acrylate aniline), Aronix M-400, Aronix M-405, Aronix M-450, Aronix M-7100, Aronix M-8030, Aronix M-8060, KAYARAD TMPTA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, and VGPT, a product of Osaka Organic Chemical Industry Co., Ltd. Can be mentioned.

  Specific examples of (meth) acrylic acid amide derivatives include N-isopropylacrylamide, N-isopropylmethacrylamide, Nn-propylacrylamide, Nn-propylmethacrylamide, N-cyclopropylacrylamide, N-cyclopropylmethacrylamide. N-ethoxyethylacrylamide, N-ethoxyethylmethacrylamide, N-tetrahydrofurfurylacrylamide, N-tetrahydrofurfurylmethacrylamide, N-ethylacrylamide, N-ethyl-N-methylacrylamide, N, N-diethylacrylamide, N-methyl-Nn-propylacrylamide, N-methyl-N-isopropylacrylamide, N-acryloylpiperidine, N-acryloylpyrrolidine, N, N′-methylenebi Acrylamide, N, N′-ethylenebisacrylamide, N, N′-dihydroxyethylenebisacrylamide, N- (4-hydroxyphenyl) methacrylamide, N-phenylmethacrylamide, N-butylmethacrylamide, N- (iso-butoxy Methyl) methacrylamide, N- [2- (N, N-dimethylamino) ethyl] methacrylamide, N, N-dimethylmethacrylamide, N- [3- (dimethylamino) propyl] methacrylamide, N- (methoxymethyl) ) Methacrylamide, N- (hydroxymethyl) -2-methacrylamide, N-benzyl-2-methacrylamide, and N, N′-methylenebismethacrylamide.

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

  Specific examples of bismaleimides include BMI-70 and BMI-80 manufactured by Kay Kasei Co., Ltd., and BMI-1000, BMI-3000, BMI-4000, BMI-5000 and BMI manufactured by Daiwa Kasei Kogyo Co., Ltd. -7000 can be mentioned.

Next, the polyamic acid and its derivative used in the present invention will be described.
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.

  The tetracarboxylic dianhydride can be selected on the condition that the polyamic acid obtained using the tetracarboxylic dianhydride is soluble in the solvent used for the liquid crystal aligning agent. And among such tetracarboxylic dianhydrides, it is preferable to use at least one of aromatic tetracarboxylic dianhydrides. Preferred examples of the aromatic tetracarboxylic dianhydride are shown below.

  Of the above aromatic tetracarboxylic dianhydrides, compound (1), compound (2), compound (5), compound (6), compound (7) and compound (14) are more preferred, and compound (1) (Pyromellitic dianhydride) is particularly preferred.

In the present invention, at least one of the above-mentioned aromatic tetracarboxylic dianhydrides and at least one of the non-aromatic tetracarboxylic dianhydrides can be used in combination. Preferred examples of non-aromatic tetracarboxylic dianhydrides are shown below.

  Of the above tetracarboxylic dianhydrides other than aromatic compounds, compound (19) to compound (39) and compound (49) are more preferred, and compound (19), compound (23), compound (25), compound ( 35) to Compound (37), Compound (39), Compound (44) and Compound (49) are more preferable. Compound (19) (1,2,3,4-cyclobutanetetracarboxylic dianhydride) is particularly preferable.

  On the other hand, in order to make the polyamic acid or its derivative in the present invention into a solvent-soluble polyimide, the formula (24), formula (35) to formula (44), formula (49), formula (50), formula ( 53) and tetracarboxylic dianhydrides represented by the formula (60) are preferably used.

  In the present invention, it is preferable to use a combination of at least one of the above-mentioned aromatic tetracarboxylic dianhydrides and at least one of the non-aromatic tetracarboxylic dianhydrides, compound (1) (pyromellitic acid) The dianhydride) and the compound (19) (1,2,3,4-cyclobutanetetracarboxylic dianhydride) are particularly preferably used in combination. When a liquid crystal alignment film is formed using a liquid crystal aligning agent containing the polyamic acid thus obtained and the compound (A), the liquid crystal display element including the liquid crystal display element is given good long-term reliability with respect to voltage holding ratio. can do.

  Furthermore, other tetracarboxylic dianhydrides other than the compounds (1) to (67) can be used for the tetracarboxylic dianhydride in the present invention. The selection of other tetracarboxylic dianhydrides is arbitrary as long as the object of the present invention is achieved, and various forms of tetracarboxylic dianhydrides can be used. Mention may also be made of a tetracarboxylic dianhydride having a structure. When a polyamic acid obtained using a tetracarboxylic dianhydride having a side chain structure is used as a liquid crystal aligning agent, the liquid crystal aligning film formed from this liquid crystal aligning agent has a large pretilt angle in a liquid crystal display device including the polyamic acid. can do.

The tetracarboxylic dianhydride having a side chain structure is not particularly limited, but preferred examples include compound (68) and compound (69) having a steroid skeleton.

  In the present invention, a part of the tetracarboxylic dianhydride may be replaced with a carboxylic anhydride. Replacing a part of tetracarboxylic dianhydride with carboxylic acid anhydride can cause polymerization reaction termination, and further progress of the reaction can be suppressed, so the molecular weight of the resulting polyamic acid is easy Can be 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 carbon number. It is selected from ring-containing groups having one or more alkyls, alkoxy having 1 or more carbon atoms, or alkoxyalkyl having 2 or more carbon atoms at the terminal. 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. In addition, the effect of such a side chain group is the same also in the said tetracarboxylic dianhydride.

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, provided that the terminal ring has alkyl having 1 or more carbon atoms, alkoxy having 1 or more carbon atoms or alkoxyalkyl having 2 or more carbon atoms as a substituent. Phenylcarbonyl, phenylcarbonyloxy, phenyloxycarbonyl, phenylaminocarbonyl, phenylcyclohexyloxy, cycloalkyl having 3 or more carbon atoms, cyclohexylalkyl, cyclohexyloxy, cyclohexyloxycarbonyl, cyclohexylphenyl, cyclohexylphenylalkyl, cyclohexylphenyloxy, bis ( Cyclohexyl) oxy, bis (cyclohexyl) alkyl, bis (cyclohexyl) phenyl, bis (cyclohexyl) phenylalkyl, bis ( Kurohekishiru) oxycarbonyl, and bis (cyclohexyl) phenyloxycarbonyl and cyclohexyl bis (phenyl) group of a ring structure, such as oxycarbonyl,. 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.

ここに、Ｘ^１は炭素数２〜１２の直鎖アルキレンであり；Ｘ^２は炭素数１〜１２の直鎖アルキレンであり；Ｘ^３は独立して単結合、−Ｏ−、−ＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−、−Ｏ−（ＣＨ_２）_ｔ−Ｏ−、−Ｓ−、−Ｓ−Ｓ−、−ＳＯ_２−、−Ｓ−（ＣＨ_２）_ｔ−Ｓ−または炭素数１〜１２の直鎖アルキレンであって、ｔは１〜１２の整数であり；シクロヘキサン環またはベンゼン環の任意の水素は、−Ｆ、−ＣＨ_３または−ＯＨ、−ＣＯＯＨ、−ＳＯ_３Ｈ、または−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。 Preferred examples of non-side chain diamines are listed below.

Wherein X ¹ is a linear alkylene having 2 to 12 carbon atoms; X ² is a linear alkylene having 1 to 12 carbon atoms; X ³ is independently a single bond, —O—, —CO—, —CONH—, —NHCO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —O— (CH ₂ ) _t —O—, —S—, —S—S—, —SO _{2 -, - S- (CH 2} ) a t -S- or straight chain alkylene of 1 to 12 carbon atoms, t is an integer from 1 to 12; any hydrogen cyclohexane ring or benzene ring, - F, —CH ₃ or —OH, —COOH, —SO ₃ H, or —PO ₃ H ₂ , benzyl or hydroxybenzyl may be substituted.

Preferred examples of the diamine represented by the formula (I) are shown below.

Preferred examples of the diamine represented by the formula (II) are shown below.

Preferred examples of the diamine represented by the formula (III) are shown below.

Preferred examples of the diamine represented by the formula (IV) are shown below.

Preferred examples of the diamine represented by the formula (V) are shown below.

Preferred examples of the diamine represented by the formula (VI) are shown below.

Preferred examples of the diamine represented by the formula (VII) are shown below.

  Among these diamines, more preferred examples include compound (IV-1) to compound (IV-5), compound (IV-15), compound (IV-16), compound (V-1) to compound (V- 12), Compound (V-26), Compound (V-27), Compound (V-31), Compound (V-33), Compound (VI-1), Compound (VI-2), Compound (VI-6) ), And compound (VII-1) to compound (VII-5), and particularly preferred examples are compound (IV-1), compound (IV-2), compound (IV-15), and compound (IV-16). Compound (V-1) to Compound (V-12), Compound (V-33), and Compound (VII-2).

Specific examples of the side chain diamine used in the present invention include diamines represented by the following formulas (VIII) to (XII).

Wherein (VIII), ^{R 1} is a single bond, -O -, - CO -, - COO -, - OCO -, - CONH -, - CH 2 O -, - CF 2 O-, or 6 carbon atoms Wherein any —CH ₂ — in the alkylene may be replaced by —O—, —CH═CH—, or —C≡C—; R ² is a group having a steroid skeleton, 3 carbon atoms A group represented by formula (D-1), or an arbitrary —CH in the alkyl, having a substituent of ˜30 alkyl, C 3-30 alkyl or C 3-30 alkoxy as a substituent, ₂ — may be replaced by —O—, —CH═CH— or —C≡C—.

ここに、Ｒ^１３、Ｒ^１４およびＲ^１５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^１６およびＲ^１７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^１８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 ¹³ , R ¹⁴ and R ¹⁵ are each 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 ¹⁶ and R ¹⁷ are independently fluorine or methyl; M1 and m2 are independently 0, 1 or 2; e, f and g are each independently an integer of 0 to 3, and their sum is 1 or more; R ¹⁸ is carbon number 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^１９、Ｒ^２０、Ｒ^２１およびＲ^２２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 ¹⁹ , R ²⁰ , R ²¹ and R ²² are independently alkyl having 1 to 10 carbons or phenyl, and n is an integer of 1 to 100.

ここに、Ｒ^３は独立して水素またはメチルであり；Ｒ^４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^５は独立して単結合、−ＣＯ−または−ＣＨ_２−である。２つのアミノフェニル−Ｒ^５−Ｏ−基の一方はステロイド骨格の３位に結合し、もう一方は６位に結合していることが好ましい。また、２つのアミノ基のベンゼン環への結合位置はそれぞれ、Ｒ^５の結合位置に対してメタ位またはパラ位であることが好ましい。なお、ステロイド骨格を形成する炭素に結合している任意の水素はメチルで置き換えられてもよい。

Wherein R ³ is independently hydrogen or methyl; R ⁴ is hydrogen, alkyl having 1 to 30 carbons, or alkenyl having 2 to 30 carbons; and R ⁵ is independently a single bond, —CO— or —CH ₂ —. One of the two aminophenyl-R ⁵ —O— groups is preferably bonded to the 3-position of the steroid skeleton and the other is bonded to the 6-position. Moreover, it is preferable that the bonding position of the two amino groups to the benzene ring is meta or para with respect to the bonding position of R ⁵ . Note that any hydrogen bonded to carbon forming the steroid skeleton may be replaced with methyl.

ここに、Ｒ^３は独立して水素またはメチルであり；Ｒ^４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^５は独立して単結合、−ＣＯ−または−ＣＨ_２−であり；そして、Ｒ^６およびＲ^７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。２つのＲ^７置換アミノフェニル−Ｒ^５−Ｏ−基のベンゼン環への結合位置はそれぞれ、ステロイド骨格が結合している炭素に対してメタ位またはパラ位であることが好ましい。また、２つのアミノ基のベンゼン環への結合位置はそれぞれ、Ｒ^５に対してメタ位またはパラ位であることが好ましい。

Wherein R ³ is independently hydrogen or methyl; R ⁴ is hydrogen, alkyl having 1 to 30 carbons, or alkenyl having 2 to 30 carbons; R ⁵ is independently a single bond, —CO — Or —CH ₂ —; and R ⁶ and R ⁷ are independently hydrogen, alkyl having 1 to 30 carbons, or phenyl. The bonding positions of the two R ⁷ -substituted aminophenyl-R ⁵ —O— groups to the benzene ring are each preferably in the meta position or the para position with respect to the carbon to which the steroid skeleton is bonded. Moreover, it is preferable that the bonding position of the two amino groups to the benzene ring is meta or para with respect to R ⁵ .

ここに、Ｒ^８は炭素数１〜３０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^９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。２つのアミノ基のベンゼン環への結合位置は、それぞれＲ⁹に対してメタ位またはパラ位であることが好ましい。

Wherein R ⁸ is alkyl having 1 to 30 carbons, and any —CH ₂ — in the alkyl may be replaced by —O—, —CH═CH— or C≡C—; R ⁹ 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. The bonding position of the two amino groups to the benzene ring is preferably meta or para to R ⁹ , respectively.

ここに、Ｒ^１０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^１１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^１２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。２つのアミノ基のベンゼン環への結合位置は、それぞれＲ^１２に対してメタ位またはパラ位であることが好ましい。

Wherein R ¹⁰ is alkyl having 3 to 30 carbon atoms or fluorinated alkyl having 3 to 30 carbon atoms; R ¹¹ is hydrogen, alkyl having 1 to 30 carbon atoms or fluorinated alkyl having 1 to 30 carbon atoms. R ¹² is independently —O— or alkylene having 1 to 6 carbons; and d is independently 0 or 1. The bonding position of the two amino groups to the benzene ring is preferably meta or para to R ¹² , respectively.

  Examples of the diamine represented by the formula (VIII) include diamines represented by the formula (VIII-1) to the formula (VIII-43).

In the formulas (VIII-1) to (VIII-11), R ²³ and R ²⁴ are each preferably alkyl having 3 to 30 carbons or alkoxy having 3 to 30 carbons, and having 5 to 25 carbons. More preferably, it is alkyl or alkoxy having 5 to 25 carbon atoms.

In Formula (VIII-12) to Formula (VIII-15), R ²⁵ is preferably alkyl having 4 to 30 carbons, and more preferably alkyl having 6 to 25 carbons. In the formulas (VIII-16) and (VIII-17), R ²⁶ is preferably alkyl having 6 to 30 carbons, and more preferably alkyl having 8 to 25 carbons.

In formulas (VIII-18) to (VIII-37), R ²⁷ and R ²⁸ are each preferably alkyl having 3 to 30 carbons or alkoxy having 3 to 30 carbons, and having 5 to 25 carbons. It is more preferable that they are alkyl or alkoxy having 5 to 25 carbon atoms.

  Of these, diamines represented by the formulas (VIII-1) to (VIII-11) are preferable, and the formulas (VIII-2), (VIII-4), (VIII-5) and (VIII-) are preferred. The diamine represented by any one of 6) is more preferable.

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

Examples of the diamine represented by the formula (X) include diamines represented by the formula (X-1) to the formula (X-8).

Examples of the diamine represented by the formula (XI) include diamines represented by the formula (XI-1) to the formula (XI-8).

In Formula (XI-1) to Formula (XI-3), R ²⁹ is preferably alkyl having 1 to 30 carbons. In Formula (XI-4) to Formula (XI-8), R ³⁰ is carbon. It is preferable that it is a C1-C20 alkyl.

これらの式において、Ｒ^３１は炭素数６〜２０のアルキルであることが好ましく、Ｒ^３２は水素、または炭素数１〜１０のアルキルであることが好ましい。 Examples of the diamine represented by the formula (XII) include diamines represented by the formula (XII-1) to the formula (XII-3).

In these formulas, R ³¹ is preferably alkyl having 6 to 20 carbon atoms, and R ³² is preferably hydrogen or alkyl having 1 to 10 carbon atoms.

  In the present invention, other diamines other than the diamines represented by the formulas (I) to (XII) may be used in combination. Examples of such other diamines include naphthalene diamines having a naphthalene structure, fluorene diamines having a fluorene structure, and siloxane diamines having a siloxane bond, and these diamines have side chain groups. It may be.

式（XV）において、Ｒ^３３およびＲ^３４はそれぞれ独立して炭素数１〜３のアルキルまたはフェニルであり、Ｘ^４は独立して炭素数１〜６のアルキレン、またはフェニレンであり、ｍは１〜１０の整数である。なお、このフェニレンの任意の水素は炭素数１〜４のアルキルで置き換えられてもよい。 A preferred example of the siloxane-based diamine is a compound represented by the following formula (XV).

In the formula (XV), R ³³ and R ³⁴ are each independently alkyl or phenyl having 1 to 3 carbon atoms, X ⁴ is independently alkylene having 1 to 6 carbon atoms or phenylene, and m is 1 It is an integer of -10. In addition, arbitrary hydrogen of this phenylene may be replaced by C1-C4 alkyl.

これらの式において、Ｒ^３５およびＲ^３６はそれぞれ独立して炭素数３〜３０のアルキルである。 Preferable examples of other diamines include compounds represented by the following formulas (1 ′) to (8 ′) in addition to the siloxane-based diamines.

In these formulas, R ³⁵ and R ³⁶ are each independently alkyl having 3 to 30 carbon atoms.

  In the present invention, a monoamine may be used in addition to the diamine. By doing so, the termination of the polymerization reaction can be caused, and further progress of the reaction can be suppressed, so that the molecular weight of the resulting polymer (polyamic acid) can be easily controlled. 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 or derivative thereof in the present invention can have any weight average molecular weight. The weight average molecular weight of the polyamic acid or derivative thereof 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 or derivative thereof having a weight average molecular weight of 5 × 10 ³ or more does not evaporate in the step of baking the liquid crystal alignment film, and has preferable physical properties as a component of the liquid crystal alignment agent.

The polyamic acid or derivative thereof in the present invention can have any weight average molecular weight. The weight average molecular weight of the polyamic acid or derivative thereof 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 or derivative thereof having a weight average molecular weight of 5 × 10 ³ or more does not evaporate in the step of firing the liquid crystal alignment film, and has preferable physical properties as a component of the liquid crystal alignment agent.

  This weight average molecular weight is measured by a gel permeation chromatography (GPC) method. For example, the obtained polyamic acid or its derivative is diluted with dimethylformamide (DMF) so that the polymer concentration is about 1% by weight, and DMF is developed using a 2695 separation module / 2414 differential refractometer (manufactured by Waters). It is determined by gel permeation chromatographic analysis (GPC) as a solvent 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 or derivative thereof 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. At least one diamine, and optionally the desired amount of monoamine.

  Next, one or more of a solvent (for example, N-methyl-2-pyrrolidone or dimethylformamide, which is an amide polar solvent) and tetracarboxylic dianhydride, and a carboxylic acid anhydride if necessary To do. 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 obtained polyamic acid solution can be used after being diluted with a solvent in order to adjust to a desired viscosity.

  The polyamic acid in the present invention is 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.

  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.

  The obtained polyimide is separated from the solvent and re-dissolved in a solvent described later together with an improving agent that combines at least one selected from the alkenyl-substituted nadiimide compound and the heterocyclic compound, and used as a liquid crystal aligning agent. Alternatively, the improver can be added without separation from the solvent and used as a liquid crystal aligning agent.

  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.

  Next, the liquid crystal aligning agent of this invention is demonstrated. The liquid crystal aligning agent of this invention is a composition containing the alkenyl substituted nadiimide compound, the compound which has a radically polymerizable unsaturated double bond, and a polyamic acid or its derivative (s). The liquid crystal aligning agent of the present invention may further contain a solvent from the viewpoints of adjusting physical properties such as viscosity, ease of handling, simplification of the process, and the like, and further includes various additives contained in a normal liquid crystal aligning agent. May be included.

  The ratio of the alkenyl-substituted nadiimide compound in the liquid crystal aligning agent of the present invention is 0.01 to 1.00 in terms of a weight ratio with respect to the polyamic acid or its derivative in the liquid crystal aligning agent from the viewpoint of stabilizing the electrical characteristics of the liquid crystal display element for a long period. Is preferable, 0.01 to 0.70 is more preferable, and 0.01 to 0.50 is further preferable.

  The ratio of the compound having a radical polymerizable unsaturated double bond in the liquid crystal aligning agent of the present invention is 0.01 to 1 by weight ratio to the polyamic acid or its derivative from the viewpoint of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time. 0.00 is preferable, 0.01 to 0.70 is more preferable, and 0.01 to 0.50 is more preferable.

  The ratio of the compound having a radical polymerizable unsaturated double bond to the alkenyl-substituted nadiimide compound is reduced in weight from the viewpoint of reducing the ion density of the liquid crystal display element, suppressing the increase in ion density over time, and further suppressing the afterimage. The ratio is preferably 0.1 to 10, and more preferably 0.5 to 5.

  The content rate of the polyamic acid or its derivative 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, a polyamic acid or a polyamic acid in a liquid crystal aligning agent 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 content of the derivative is preferably 0.5 to 30% by weight in total, and more preferably 1 to 15% by weight in total, but is appropriately adjusted in relation to the viscosity of the liquid crystal aligning agent. Is done.

  The solvent used in the present invention includes a wide variety of solvents usually used in production processes and applications of polymer components such as polyamic acid, soluble polyimide, and polyamideimide, and is appropriately selected according to the purpose of use. The solvent should be 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. preferable. 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, and γ-valerolactone are particularly 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, and dipropylene glycol monomethyl ether are 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, etc. 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, a high molecular compound other than polyamic acid or a derivative thereof, or a low molecular compound can be selected and used according to each purpose.

  For example, a polymer 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 such polymers include polyamides, polyurethanes, polyureas, polyesters, polyepoxides, polyester polyols, silicone modified polyurethanes, and silicone modified polyesters.

  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 or a titanium-based coupling agent can be used when it is desired to improve adhesion to the substrate or 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 0.10 by weight ratio with respect to the polyamic acid or derivative thereof, 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 or derivative thereof.

  Although the addition amount of another additive changes according to the use, it is 0-0.30 by weight ratio with respect to polyamic acid or its derivative normally, and it is preferable that it is 0.001-0.10.

  Another preferable form of the liquid crystal aligning agent of the present invention is a composition containing two or more kinds of polyamic acids. For example, the first polyamic acid in which neither a tetracarboxylic dianhydride nor a diamine has a compound having a side chain group, and one or both of the tetracarboxylic dianhydride and the diamine have a side chain group A liquid crystal aligning agent containing the 2nd polyamic acid in which the compound is used is mentioned. More specifically, one kind of the polyamic acid is an aromatic tetracarboxylic dianhydride (preferably at least one of the above-mentioned compounds (1) to (18)) and a non-aromatic tetracarboxylic diacid. At least one or both of an anhydride (preferably compound (19) to compound (67)) and at least one non-side chain diamine (preferably compound (I) to compound (VII)) are reacted. Or a derivative thereof (hereinafter sometimes referred to as “polyamic acid I”), and another one is the above-mentioned aromatic tetracarboxylic dianhydride and a non-aromatic tetracarboxylic acid. One or both of the dianhydrides, at least one of the side chain diamines (preferably compound (VIII) to compound (XII)), or at least one of the side chain diamines; It is a polyamic acid obtained by reacting with at least one mixture of non-side chain diamines or a derivative thereof (hereinafter sometimes referred to as “polyamic acid II”).

  The composition containing polyamic acid I and polyamic acid II in the present invention is prepared by mixing polyamic acid I and polyamic acid II described above. The weight ratio of the polyamic acid I and the polyamic acid II to be mixed is preferably I / II = 99/1 to 50/50, and more preferably I / II = 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 polyamic acid II.

  In addition, the liquid crystal aligning agent of this invention may contain only polyamic acid I and polyamic acid II, and may further contain polyamic acids other than polyamic acid I and polyamic acid II, or its derivative (s).

  On the other hand, the polyamic acid II is effective for imparting a suitable pretilt angle to a liquid crystal display element including a liquid crystal alignment film formed using a liquid crystal aligning agent containing the polyamic acid II. When synthesizing polyamic acid II, a diamine other than a diamine having a side chain may be used in combination. Examples of the diamine that may be used in combination include the compounds (I) to (VII), fluorene-based diamine, and siloxane-based diamine.

  By combining (blending) the polyamic acid I and the polyamic acid II, preferable characteristics can be imparted as the liquid crystal aligning agent of the present invention. Specifically, for the diamine that is the raw material of the polyamic acid, the liquid crystal alignment film formed by using the composition of the present invention can be further improved by selecting the kind of diamine to be used and the combination thereof appropriately. And a suitable pretilt angle can be provided.

  The liquid crystal aligning film of the present invention is obtained by, for example, applying the liquid crystal aligning agent of the present invention to a substrate for a liquid crystal display element or a measuring substrate such as calcium fluoride or silicon, and the film of the liquid crystal aligning agent is, for example, 150 to 400 It can be formed by heating to ℃, preferably 180 to 280 ℃. Here, the film thickness of the liquid crystal alignment film is preferably 10 to 300 nm, and more preferably 30 to 150 nm. The liquid crystal alignment film is preferably rubbed.

  The film thickness of the liquid crystal alignment film can be adjusted by the viscosity of the liquid crystal aligning agent and the application method of the liquid crystal aligning agent. The film thickness of the liquid crystal alignment film 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.

  The pair of substrates with electrodes arranged opposite to each other is preferably a transparent substrate (for example, a 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 any liquid crystal composition having a positive dielectric anisotropy and a liquid crystal composition having a negative dielectric anisotropy can 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 added to the liquid crystal composition having a positive or negative dielectric anisotropy.

  Of course, 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 can be provided.

  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 is manufactured by an arbitrary method. For example, 1) a step of applying a liquid crystal aligning agent on the two transparent substrates, 2) a step of drying the applied liquid crystal aligning agent, 3 ) A step of performing 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) two substrates having a predetermined gap. After bonding, the liquid crystal is manufactured in a method including a step of sealing liquid crystal in a gap between the substrates, or a step of dropping liquid crystal on one substrate and then bonding 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. The compounds used in the examples are as follows.
<Tetracarboxylic dianhydride>
Compound (1): Pyromellitic dianhydride compound (19): 1,2,3,4-cyclobutanetetracarboxylic dianhydride compound (23): 1,2,3,4-butanetetracarboxylic dianhydride <Diamine>
Compound (V-1): 4,4′-diaminodiphenylmethane compound (V-7): 1,2-bis (4-aminophenyl) ethane compound (VII-2): 1,3-bis (4- (4 -Aminobenzyl) phenyl) propane compound (XI-6-1): 1,1-bis [4- (4-aminophenoxy) phenyl] -4-[(4-heptylcyclohexyl) ethyl] cyclohexane compound (XI-4 -1): 1,1-bis [4- (4-aminophenoxy) phenyl-4- (trans-4-n-pentylcyclohexyl) cyclohexane compound (XI-6-2): 1,1-bis [4- (4-Aminophenoxy) phenyl] -4-[(4-ethylcyclohexyl) ethyl] cyclohexane compound (XI-2-1): 1,1-bis [4- (4-aminophenyl) methylphenyl] -4- n-Hepti Cyclohexane

<Alkenyl-substituted nadiimide compound>
Compound (Ina-1): bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane

<Compound having radically polymerizable unsaturated double bond>
EBA: ethylene bisacrylate NEBA: N, N′-ethylenebisacrylamide HEA: N, N′-dihydroxyethylenebisacrylamide MHA: 4,4′-methylenebis (N, N-dihydroxyethylene acrylate aniline)

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

[Synthesis Example 1] (Synthesis of polyamic acid)
Compound (V-1) (2.91 g), dehydrated NMP (54 g) and GBL (15 g) were placed in a 100 mL four-necked flask equipped with a thermometer, stirrer, raw material charging inlet and nitrogen gas inlet. The solution was stirred and dissolved under a dry nitrogen stream. Next, compound (19) (1.01 g) and compound (1) (2.08 g) were added, and the mixture was 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. BC (25 g) was added to the resulting solution to prepare a polyamic acid solution (PA1) having a concentration of 6% by weight. The obtained polyamic acid had a weight average molecular weight of 57,000.

  The weight average molecular weight of the polyamic acid was diluted with a phosphoric acid-DMF mixed solution (phosphoric acid / DMF = 0.6 / 100: weight ratio) so that the polyamic acid concentration was about 1% by weight. Using a 2695 separation module / 2414 differential refractometer (manufactured by Waters), the above mixed solution was measured by a GPC method using a developing agent, and was calculated by polystyrene conversion. In addition, the column used HSPgel RT MB-M (made by Waters), and measured it on conditions with a column temperature of 40 degreeC, and the flow rate of 0.35 mL / min.

[Synthesis Examples 2 to 8]
Polyamic acid solutions (PA2) to (PA8) were prepared according to Synthesis Example 1 except that tetracarboxylic dianhydride and diamine were changed as shown in Table 1. Including synthesis example 1, the blending ratio of the raw materials and the weight average molecular weight of the obtained polyamic acid are summarized in Table 1.

（注）ＰＡ酸はポリアミック酸を意味し、４ＣＡはテトラカルボン酸を意味する。 <Table 1>

(Note) PA acid means polyamic acid, and 4CA means tetracarboxylic acid.

[Example 1] (Production of liquid crystal display element)
The polyamic acid solution (PA1) having a concentration of 6% by weight prepared in Synthesis Example 1 and the polyamic acid solution (PA2) having a concentration of 6% by weight prepared in Synthesis Example 2 were mixed at a weight ratio of 8/2. To the obtained mixture, 10 parts by weight per 100 parts by weight of polyamic acid were added to each of the compounds (Ina-1) which is an alkenyl-substituted nadiimide compound and MHA which is a compound having a radical polymerizable unsaturated double bond. did. Thereafter, a mixed solvent of NMP / BC = 1/1 (weight ratio) was added and diluted to obtain a liquid crystal aligning agent having a polyamic acid concentration of 4% by weight. Using the obtained liquid crystal aligning agent, a liquid crystal display element was produced as follows.

  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, then heat-treated at 210 ° C. for 20 minutes, and then rubbed to form a liquid crystal alignment film. The substrate was ultrasonically cleaned in ultrapure water for 5 minutes and then dried in an oven at 120 ° C. for 30 minutes.

  A gap material of 7 μm was sprayed on one of these glass substrates, and the other glass substrate was disposed so as to face the rubbing direction in antiparallel with the surface on which the liquid crystal alignment film was formed facing inward. Thereafter, the periphery of the liquid crystal alignment film was sealed with an epoxy curing agent to produce an anti-parallel cell with a gap of 7 μm. The liquid crystal composition shown below was injected into this cell, and the injection port for the liquid crystal composition 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.

<Liquid crystal composition>

[Example 2]
The polyamic acid solution (PA1) having a concentration of 6% by weight prepared in Synthesis Example 1 and the polyamic acid solution (PA3) having a concentration of 6% by weight prepared in Synthesis Example 3 were mixed at a weight ratio of 8/2. To the obtained mixture, 10 parts by weight per 100 parts by weight of polyamic acid were added to each compound (Ina-1) which is an alkenyl-substituted nadiimide compound and HEA which is a compound having a radical polymerizable unsaturated double bond. did. Thereafter, a mixed solvent of NMP / BC = 1/1 (weight ratio) was added and diluted to obtain a liquid crystal aligning agent having a polyamic acid concentration of 4% by weight. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

[Example 3]
The polyamic acid solution (PA1) having a concentration of 6% by weight prepared in Synthesis Example 1 and the polyamic acid solution (PA2) having a concentration of 6% by weight prepared in Synthesis Example 2 were mixed at a weight ratio of 8/2. To the obtained mixture, 10 parts by weight per 100 parts by weight of polyamic acid were added to each compound (Ina-1) which is an alkenyl-substituted nadiimide compound and NEBA which is a compound having a radical polymerizable unsaturated double bond. did. Thereafter, a mixed solvent of NMP / BC = 1/1 (weight ratio) was added and diluted to obtain a liquid crystal aligning agent having a polyamic acid concentration of 4% by weight. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

[Example 4]
The polyamic acid solution (PA1) having a concentration of 6% by weight prepared in Synthesis Example 1 and the polyamic acid solution (PA2) having a concentration of 6% by weight prepared in Synthesis Example 2 were mixed at a weight ratio of 8/2. To the obtained mixture, 10 parts by weight per 100 parts by weight of polyamic acid were added to each of the compounds (Ina-1) which is an alkenyl-substituted nadiimide compound and MHA which is a compound having a radical polymerizable unsaturated double bond. The total amount of the improver comprising these compounds was 20 parts by weight. Thereafter, a mixed solvent of NMP / BC = 1/1 (weight ratio) was added, and the polyamic acid was diluted to 4% by weight with respect to the whole to obtain a liquid crystal aligning agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

[Example 5]
To the polyamic acid solution (PA4) having a concentration of 6% by weight prepared in Synthesis Example 4, a compound (Ina-1) that is an alkenyl-substituted nadiimide compound and MHA that is a compound having a radically polymerizable unsaturated double bond, Each 10 parts by weight per 100 parts by weight of polyamic acid was added. Thereafter, a mixed solvent of NMP / BC = 1/1 (weight ratio) was added and diluted to obtain a liquid crystal aligning agent having a polyamic acid concentration of 4% by weight. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

[Example 6]
In a polyamic acid solution (PA4) having a concentration of 6% by weight prepared in Synthesis Example 4, a compound (Ina-1) that is an alkenyl-substituted nadiimide compound and EBA that is a compound having a radically polymerizable unsaturated double bond, Each 10 parts by weight per 100 parts by weight of polyamic acid was added. Thereafter, a mixed solvent of NMP / BC = 1/1 (weight ratio) was added and diluted to obtain a liquid crystal aligning agent having a polyamic acid concentration of 4% by weight. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

[Example 7]
The polyamic acid solution (PA1) having a concentration of 6% by weight prepared in Synthesis Example 1 and the polyamic acid solution (PA6) having a concentration of 6% by weight prepared in Synthesis Example 6 were mixed at a weight ratio of 8/2. To the obtained mixture, a compound (Ina-1) which is an alkenyl-substituted nadiimide compound and HEA which is a compound having a radical polymerizable unsaturated double bond are respectively added to each compound (Ina-1) per 100 parts by weight of polyamic acid. 20 parts by weight and 5 parts by weight of HEA were added. Thereafter, a mixed solvent of NMP / BC = 1/1 (weight ratio) was added, and the polyamic acid was diluted to 4% by weight with respect to the whole to obtain a liquid crystal aligning agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

[Example 8]
The polyamic acid solution (PA5) having a concentration of 6% by weight prepared in Synthesis Example 5 and the polyamic acid solution (PA6) having a concentration of 6% by weight prepared in Synthesis Example 6 were mixed at a weight ratio of 8/2. To the obtained mixture, a compound (Ina-1) which is an alkenyl-substituted nadiimide compound and HEA which is a compound having a radical polymerizable unsaturated double bond are respectively added to each compound (Ina-1) per 100 parts by weight of polyamic acid. 20 parts by weight and 5 parts by weight of HEA were added. Thereafter, a mixed solvent of NMP / BC = 1/1 (weight ratio) was added, and the polyamic acid was diluted to 4% by weight with respect to the whole to obtain a liquid crystal aligning agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

[Example 9]
The polyamic acid solution (PA5) having a concentration of 6% by weight prepared in Synthesis Example 5 and the polyamic acid solution (PA7) having a concentration of 6% by weight prepared in Synthesis Example 7 were mixed at a weight ratio of 8/2. To the obtained mixture, a compound (Ina-1) which is an alkenyl-substituted nadiimide compound and HEA which is a compound having a radical polymerizable unsaturated double bond are respectively added to each compound (Ina-1) per 100 parts by weight of polyamic acid. 30 parts by weight and HEA 20 parts by weight. Thereafter, a mixed solvent of NMP / BC = 1/1 (weight ratio) was added, and the polyamic acid was diluted to 4% by weight with respect to the whole to obtain a liquid crystal aligning agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

[Example 10]
The polyamic acid solution (PA5) having a concentration of 6% by weight prepared in Synthesis Example 5 and the polyamic acid solution (PA7) having a concentration of 6% by weight prepared in Synthesis Example 7 were mixed at a weight ratio of 8/2. To the obtained mixture, a compound (Ina-1) which is an alkenyl-substituted nadiimide compound and HEA which is a compound having a radical polymerizable unsaturated double bond are respectively added to each compound (Ina-1) per 100 parts by weight of polyamic acid. 20 parts by weight and 10 parts by weight of HEA were added. Thereafter, a mixed solvent of NMP / BC = 1/1 (weight ratio) was added, and the polyamic acid was diluted to 4% by weight with respect to the whole to obtain a liquid crystal aligning agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

[Example 11]
In a polyamic acid solution (PA8) having a concentration of 6% by weight prepared in Synthesis Example 8, a compound (Ina-1) that is an alkenyl-substituted nadiimide compound and HEA that is a compound having a radically polymerizable unsaturated double bond, In each case, 20 parts by weight of the compound (Ina-1) and 10 parts by weight of HEA were added per 100 parts by weight of the polyamic acid. Thereafter, a mixed solvent of NMP / BC = 1/1 (weight ratio) was added, and the polyamic acid was diluted to 4% by weight with respect to the whole to obtain a liquid crystal aligning agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

[Comparative Example 1]
The polyamic acid solution (PA1) having a concentration of 6% by weight prepared in Synthesis Example 1 and the polyamic acid solution (PA2) having a concentration of 6% by weight prepared in Synthesis Example 2 were mixed at a weight ratio of 8/2. The obtained mixture was diluted by adding a mixed solvent of NMP / BC = 1/1 (weight ratio) to obtain a liquid crystal aligning agent having a polyamic acid concentration of 4% by weight. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

[Comparative Example 2]
The polyamic acid solution (PA1) having a concentration of 6% by weight prepared in Synthesis Example 1 and the polyamic acid solution (PA2) having a concentration of 6% by weight prepared in Synthesis Example 2 were mixed at a weight ratio of 8/2. To the obtained mixture, 10 parts by weight of MHA, which is a compound having a radical polymerizable unsaturated double bond, was added per 100 parts by weight of polyamic acid. The obtained mixture was diluted by adding a mixed solvent of NMP / BC = 1/1 (weight ratio) to obtain a liquid crystal aligning agent having a polyamic acid concentration of 4% by weight. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

[Comparative Example 3]
A polyamic acid solution (PA4) having a concentration of 6% by weight prepared in Synthesis Example 4 was diluted by adding a mixed solvent of NMP / BC = 1/1 (weight ratio), and a liquid crystal aligning agent having a polyamic acid concentration of 4% by weight. did. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

[Comparative Example 4]
To the polyamic acid solution (PA4) having a concentration of 6% by weight prepared in Synthesis Example 4, 10 parts by weight of the compound (Ina-1), which is an alkenyl-substituted nadiimide compound, was added per 100 parts by weight of the polyamic acid. The obtained mixture was diluted by adding a mixed solvent of NMP / BC = 1/1 (weight ratio) to obtain a liquid crystal aligning agent having a polyamic acid concentration of 4% by weight. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

[Test Examples 1 to 15] (Evaluation of electrical characteristics)
With respect to the liquid crystal display elements produced in Examples 1 to 11 and Comparative Examples 1 to 4, measurement of ion density (long-term reliability of electrical characteristics) and measurement of residual DC by a flicker-free method were performed as follows.

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

2) Measurement of holding property of ion density With respect to the produced liquid crystal display element, the ion density was obtained over time, and the holding property was evaluated. As a test method for holding characteristics, a method was adopted in which the liquid crystal display element was left in an atmosphere at a temperature of 60 ° C., and the ion density was taken out over time during the course. It can be said that the smaller the increase amount of the ion density (for example, if the increase amount of the ion density after the standing time of 500 hours is 100 pC or less under the above-mentioned conditions), the better the retention characteristics, and the long-term reliability of the electrical characteristics Can be said to be good. The data after 245 hours and after 500 hours are shown in Table 2.

3) Measurement of residual DC by flicker free method Using FG-110 manufactured by Yokogawa Electric Corporation, a DC voltage of 3 V was superimposed on a 30 Hz, 1.64 V rectangular wave and applied for 30 minutes. The flicker erasing voltage was measured for 30 minutes immediately after the application was completed. The table shows the flicker erasing voltage after 5 minutes from the end of application. The measurement temperature was 25 ° C. The closer this value is to 0, the better the electrical characteristics. The results are shown in Table 2.

<Table 2>

  As shown in Table 2, when preparing a liquid crystal aligning agent by mixing a polyamic acid with an improver that combines an alkenyl-substituted nadiimide compound and a compound having a radical polymerizable unsaturated double bond, this liquid crystal aligning agent is used. In the liquid crystal display element using the liquid crystal alignment film obtained from the above, the effect of suppressing the increase in the ion density with time was recognized, and the afterimage characteristics were remarkably improved.

Claims (26)

  A liquid crystal aligning agent comprising an alkenyl-substituted nadiimide compound, a compound having a radical polymerizable unsaturated double bond, and a polyamic acid or a derivative thereof. A composition containing an alkenyl-substituted nadiimide compound, a compound having a radical polymerizable unsaturated double bond, and a polyamic acid or a derivative thereof, wherein the alkenyl-substituted nadiimide compound is a compound represented by the formula (Ina) Item 2. A liquid crystal aligning agent according to Item 1.

Here, L ¹ and L ² are each independently hydrogen, alkyl having 1 to 12 carbons, alkenyl having 3 to 6 carbons, cycloalkyl having 5 to 8 carbons, aryl having 6 to 12 carbons, or benzyl N is 1 or 2, and when n = 1, W is alkyl having 1 to 12 carbons, alkenyl having 2 to 6 carbons, cycloalkyl having 5 to 8 carbons, or 6 to 12 carbons. A group represented by aryl, benzyl, -Z ^1- (O) _q- (Z ² O) _r -Z ³ -H (in this group, Z ¹ , Z ² and Z ³ are each independently a group having 2 to 2 carbon atoms; 6 is alkylene, q is 0 or 1, and r is an integer of 1 to 30.), a group represented by — (Z ⁴ ) _s —BZ ⁵ —H (in this group, sheet of Z ⁴ and ^{Z 5} number alkylene or C 1 to 4 carbon atoms are independently 5-8 Alkylene, B is phenylene, and s is 0 or 1.), or a group represented by -B-T-B-H, in which B is phenylene and T is —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, —CO—, —S— or —SO ₂ —. And when n = 2, W is alkylene having 2 to 20 carbon atoms, cycloalkylene having 5 to 8 carbon atoms, arylene having 6 to 12 carbon atoms, -Z ^1- (O) _q- ( Z ² O) a group represented by _r —Z ³ — (the meanings of Z ^{1 to} Z ³ , q and r in this group are as described above), — (Z ⁴ ) _s —BZ ⁵ — (The meanings of Z ⁴ , Z ⁵ , B and s in this group are as described above), Or a group represented by -B-T-B- (the meanings of B and T in this group are as described above), and 1 to 3 hydrogens in such W are replaced by hydroxyl groups. May be. A composition containing an alkenyl-substituted nadiimide compound, a polyamic acid or a derivative thereof and a compound having a radical polymerizable unsaturated double bond, wherein the alkenyl-substituted nadiimide compound is represented by formulas (Ina-1) to (Ina-3) The liquid crystal aligning agent of Claim 2 which is at least 1 of the compound represented.

  A composition containing an alkenyl-substituted nadiimide compound, a compound having a radically polymerizable unsaturated double bond, and a polyamic acid or a derivative thereof, wherein the ratio of the alkenyl-substituted nadiimide compound is 0. The liquid crystal aligning agent of any one of Claims 1-3 which is 01-1.00.   A composition containing an alkenyl-substituted nadiimide compound, a compound having a radical polymerizable unsaturated double bond, and a polyamic acid or a derivative thereof, wherein the compound having a radical polymerizable unsaturated double bond is a (meth) acrylic acid derivative The liquid crystal aligning agent of any one of Claims 1-4 which is.   A composition containing an alkenyl-substituted nadiimide compound, a compound having a radically polymerizable unsaturated double bond, and a polyamic acid or a derivative thereof, wherein the compound having a radically polymerizable unsaturated double bond is a radically polymerizable unsaturated divalent bond. A compound having two or more double bonds or a mixture containing the compound, and the ratio of the compound having a radical polymerizable unsaturated double bond is 0.01 to 1.00 in terms of weight ratio to the polyamic acid or derivative thereof. The liquid crystal aligning agent of any one of Claims 1-4.   A composition containing an alkenyl-substituted nadiimide compound, a compound having a radically polymerizable unsaturated double bond, and a polyamic acid or a derivative thereof, wherein the compound having a radically polymerizable unsaturated double bond is N, N′-methylene The liquid crystal alignment according to claim 6, which is at least one of bisacrylamide, N, N′-dihydroxyethylene-bisacrylamide, ethylene bisacrylate, and 4,4′-methylenebis (N, N-dihydroxyethyleneacrylate aniline). Agent. A polyamic acid is obtained by reacting diamine with at least one of aromatic tetracarboxylic dianhydrides represented by formula (1), formula (2), formula (5) to formula (7) and formula (14). The liquid crystal aligning agent of any one of Claims 1-7 which is a polymer obtained.

The liquid crystal aligning agent of any one of Claims 1-7 whose polyamic acid is a polymer obtained by making the aromatic tetracarboxylic dianhydride represented by Formula (1) and diamine react.

The polyamic acid is an aromatic tetracarboxylic dianhydride represented by the formula (1), the formula (2), the formula (5) to the formula (7), and the formula (14), and a tetracarboxylic acid other than aromatic. The liquid crystal aligning agent of any one of Claims 1-7 which is a polymer obtained by making the mixture with a dianhydride and diamine react.

The polyamic acid is a polymer obtained by reacting a diamine with a mixture of an aromatic tetracarboxylic dianhydride represented by the formula (1) and a tetracarboxylic dianhydride other than aromatic. 8. The liquid crystal aligning agent according to any one of 7 above.

The polyamic acid is an aromatic tetracarboxylic dianhydride represented by the formula (1), the formula (2), the formula (5) to the formula (7), and the formula (14), and a tetracarboxylic acid other than aromatic. A polymer obtained by reacting a mixture of a dianhydride and a diamine, wherein the tetracarboxylic dianhydride other than aromatic is represented by the formula (19), formula (23), formula (25), formula (35): The liquid crystal aligning agent of Claim 10 which is at least 1 of the compound represented by-Formula (37), Formula (39), Formula (44), and Formula (49).

A polyamic acid is a polymer obtained by reacting a mixture of an aromatic tetracarboxylic dianhydride represented by the formula (1) and a non-aromatic tetracarboxylic dianhydride with a diamine, other than aromatic Are represented by formula (19), formula (23), formula (25), formula (35) to formula (37), formula (39), formula (44) and formula (49). The liquid crystal aligning agent according to claim 11, which is at least one of the following compounds.

A polyamic acid is a polymer obtained by reacting a mixture of an aromatic tetracarboxylic dianhydride represented by the formula (1) and a non-aromatic tetracarboxylic dianhydride with a diamine, other than aromatic The liquid crystal aligning agent of Claim 11 whose tetracarboxylic dianhydride of is a compound represented by Formula (19).

The liquid crystal aligning agent of any one of Claims 8-14 whose diamine is at least 1 chosen from the group of the non-side chain type diamine represented by Formula (I)-Formula (VII):

Wherein X ¹ is a linear alkylene having 2 to 12 carbon atoms; X ² is a linear alkylene having 1 to 12 carbon atoms; X ³ is independently a single bond, —O—, —CO—, —CONH—, —NHCO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —O— (CH ₂ ) _t —O—, —S—, —S—S—, —SO _{2 -, - S- (CH 2} ) a t -S- or straight chain alkylene of 1 to 12 carbon atoms, t is an integer from 1 to 12; any hydrogen cyclohexane ring or benzene ring, - F, —CH ₃ or —OH, —COOH, —SO ₃ H, or —PO ₃ H ₂ , benzyl or hydroxybenzyl may be substituted. The diamine is represented by formula (IV-1), formula (IV-2), formula (IV-15), formula (IV-16), formula (V-1) to formula (V-12), or formula (V-33). The liquid crystal aligning agent of any one of Claims 8-14 which is at least 1 chosen from non-side chain type diamine represented by Formula (VII-2).

At least one selected from non-side chain diamines represented by formulas (I) to (VII), an alkyl having 3 or more carbon atoms, an alkoxy having 3 or more carbon atoms, an alkoxyalkyl having 3 or more carbon atoms, and a steroid A group having a skeleton and at least one side chain diamine having a side chain group selected from a ring-containing group having an alkyl having 1 or more carbon atoms, an alkoxy having 1 or more carbon atoms or an alkoxyalkyl having 2 or more carbon atoms at the terminal The liquid crystal aligning agent of any one of Claims 8-14 which is a mixture of these:

Wherein X ¹ is a linear alkylene having 2 to 12 carbon atoms; X ² is a linear alkylene having 1 to 12 carbon atoms; X ³ is independently a single bond, —O—, —CO—, —CONH—, —NHCO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —O— (CH ₂ ) _t —O—, —S—, —S—S—, —SO _{2 -, - S- (CH 2} ) a t -S- or straight chain alkylene of 1 to 12 carbon atoms, t is an integer from 1 to 12; any hydrogen cyclohexane ring or benzene ring, - F, —CH ₃ or —OH, —COOH, —SO ₃ H, or —PO ₃ H ₂ , benzyl or hydroxybenzyl may be substituted. The liquid crystal aligning agent of Claim 17 whose side chain type diamine is diamine chosen from the group of the compound represented by Formula (VIII)-Formula (XII).

(Here, ^{R 1} 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 ² is a group having a steroid skeleton, having 3 to 30 carbon atoms Or an alkyl group having 3 to 30 carbon atoms or phenyl having 3 to 30 carbon atoms as a substituent, or a group represented by the formula (D-1), and any —CH ₂ — group in the alkyl group May be replaced by —O—, —CH═CH— or —C≡C—;

Here, R ¹³ , R ¹⁴ and R ¹⁵ are each 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 ¹⁶ and R ¹⁷ are independently fluorine or methyl; M1 and m2 are independently 0, 1 or 2; e, f and g are each independently an integer of 0 to 3, and their sum is 1 or more; R ¹⁸ is carbon number 1-30 alkyl, C1-C30 alkoxy, or C2-C30 alkoxyalkyl, and in these alkyl, alkoxy and alkoxyalkyl, any hydrogen is replaced with fluorine. And any —CH ₂ — may be replaced by difluoromethylene or a group represented by formula (D-2);

Here, R ¹⁹ , R ²⁰ , R ²¹ and R ²² are independently alkyl having 1 to 10 carbons or phenyl, and n is an integer of 1 to 100. )

(Wherein R ³ is independently hydrogen or methyl; R ⁴ is hydrogen, alkyl having 1 to 30 carbons, or alkenyl having 2 to 30 carbons; and R ⁵ is independently a single bond. , -CO- or -CH ₂ - is).

(Wherein R ³ is independently hydrogen or methyl; R ⁴ is hydrogen, alkyl having 1 to 30 carbons, or alkenyl having 2 to 30 carbons; R ⁵ is independently a single bond, — CO— or —CH ₂ —; and R ⁶ and R ⁷ are independently hydrogen, alkyl having 1 to 30 carbons, or phenyl.)

(Where R ⁸ is alkyl having 1 to 30 carbon atoms, and any —CH ₂ — in the alkyl may be replaced by —O—, —CH═CH— or C≡C—; R ⁹ 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.)

(Where R ¹⁰ is alkyl having 3 to 30 carbon atoms or fluorinated alkyl having 3 to 30 carbon atoms; R ¹¹ is hydrogen, alkyl having 1 to 30 carbon atoms or fluorinated alkyl having 1 to 30 carbon atoms. Yes; R ¹² is independently —O— or alkylene having 1 to 6 carbons; and d is independently 0 or 1. The side chain diamine is represented by formula (VIII-2), formula (VIII-4), formula (VIII-5), formula (VIII-6), formula (XI-2) and formula (XI-4). The liquid crystal aligning agent of Claim 17 which is a diamine chosen from a compound.

(Wherein R ²³ and R ²⁴ are independently alkyl having 3 to 30 carbons, or alkoxy having 3 to 30 carbons, and R ²⁹ and R ³⁰ are independently alkyl having 1 to 30 carbons, or (It is an alkoxy having 1 to 30 carbon atoms.) 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-12), formula (IV) V-33) and a diamine selected from the compounds represented by formula (VII-2), and the side chain diamine is represented by formula (VIII-2), formula (VIII-4), formula (VIII-5), formula The liquid crystal aligning agent of Claim 17 which is a diamine chosen from the compound represented by (VIII-6), Formula (XI-2), and Formula (XI-4).

(Wherein R ²³ and R ²⁴ are independently alkyl having 3 to 30 carbons, or alkoxy having 3 to 30 carbons, and R ²⁹ and R ³⁰ are independently alkyl having 1 to 30 carbons, or (It is an alkoxy having 1 to 30 carbon atoms.) The polymer is composed of at least one aromatic tetracarboxylic dianhydride represented by formula (1), formula (2), formula (5) to formula (7) and formula (14), and formula (19), formula ( 23), formula (25), formula (35) to formula (37), formula (39), formula (44), and at least one tetracarboxylic dianhydride other than aromatic represented by formula (49) And the formula (IV-1), formula (IV-2), formula (IV-15), formula (IV-16), formula (V-1) to formula (V-12), formula (V- 33) and at least one non-side chain diamine represented by the formula (VII-2) and a mixture of the polyamic acid and derivatives thereof and the tetracarboxylic dianhydride described above and the formula (VIII- 2) side represented by formula (VIII-4), formula (VIII-5), formula (VIII-6), formula (XI-2) and formula (XI-4) Any one of Claim 1-7 which is at least 1 chosen from the polyamic acid obtained by making the mixture of at least 1 chosen from chain type diamine and at least 1 of said non-side chain type diamine react. 2. A liquid crystal aligning agent according to item 1.

(Wherein R ²³ and R ²⁴ are independently alkyl having 3 to 30 carbons, or alkoxy having 3 to 30 carbons, and R ²⁹ and R ³⁰ are independently alkyl having 1 to 30 carbons, or (It is an alkoxy having 1 to 30 carbon atoms.)   A polyamic acid obtained by reacting a mixture of at least one non-aromatic tetracarboxylic dianhydride and at least one non-aromatic tetracarboxylic dianhydride with at least one non-side chain diamine. The liquid crystal aligning agent of Claim 21 which exists.   A polyamic acid obtained by reacting a mixture of at least one aromatic tetracarboxylic dianhydride and at least one non-aromatic tetracarboxylic dianhydride with at least one non-side chain diamine And a mixture of polyamic acids obtained by reacting said mixture of tetracarboxylic dianhydrides with a mixture of at least one non-side chain diamine and at least one side chain diamine. Liquid crystal aligning agent.   The polymer comprises a mixture of at least one aromatic tetracarboxylic dianhydride and at least one non-aromatic tetracarboxylic dianhydride, at least one non-side chain diamine and at least one side chain diamine. The liquid crystal aligning agent of Claim 21 which is at least 1 chosen from the polyamic acid obtained by making a mixture react, and its derivative (s). The liquid crystal aligning film formed by apply | coating the liquid crystal aligning agent of any one of Claims 1-24 on a board | substrate, and baking in the state of a film | membrane.
  A pair of substrates arranged opposite to each other, electrodes formed on one or both of the opposed surfaces of each of the pair of substrates, and liquid crystal alignment formed on the opposed surfaces of each of the pair of substrates A liquid crystal display element having a film and a liquid crystal layer formed between the pair of substrates, wherein the liquid crystal alignment film is the liquid crystal alignment film according to claim 25.