JP5293943B2 - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

A liquid crystal aligning agent for a liquid crystal display device is provided to improve the long period reliability of electrical characteristic due to the change of voltage holding rate according to the time. A liquid crystal aligning agent contains one or more polymers selected from a polyamic acid and its derivative and a compound having a plurality of allyl groups. The compound having a plurality of allyl groups is at lease one selected from a group of the compounds indicated as the following chemical formula (A-1) ~ (A-7). In the chemical formulae, Z^1 is independently, a single bond, -O-, -CO-, -CONH-, -NHCO-, -C(CH3)2-, -C(CF3)2-, -(CH2)t-, or -O-(CH2)t-O-; t is an integer of 1~8; Z is -CH2CH2- or 1,4- phenylene; Q^1 is a group indicated as the following chemical formula (B-1); Q^2 is a group indicated as the following chemical formula (B-2); and Q^3 is hydrogen or is a group indicated as the following chemical formula (B-3).

Description

  The present invention relates to a liquid crystal aligning agent containing a polyamic acid and a compound having a plurality of allyl groups, and uses thereof.

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

  The liquid crystal alignment film is prepared from a liquid crystal aligning agent. Currently, the liquid crystal aligning agent mainly used is a solution in which polyamic acid or soluble polyimide is dissolved in an organic solvent. After applying such a solution to a substrate, a polyimide-based alignment film is formed by film formation by means such as heating. 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 a voltage holding ratio. When the voltage holding ratio is low, the voltage applied to the liquid crystal during the frame period is lowered, and as a result, the luminance is lowered, and normal gradation display may be hindered. Moreover, even if the initial voltage holding ratio is high, there is a problem when the voltage holding ratio (long-term reliability) after the high temperature acceleration test is lowered.

As an attempt to solve the above problem, several methods have been proposed recently.
1) A polyamic acid composition containing a combination of two or more polyamic acids having different physical properties for forming a liquid crystal alignment film is known (see, for example, Patent Documents 1 and 2).
2) A varnish composition containing a polymer component containing polyamic acid and polyamide and a solvent is known (see, for example, Patent Document 3).
3) A varnish composition containing two or more polyamic acids and polyamides having different physical properties and a solvent is known (see, for example, Patent Document 4).
4) A varnish composition containing a polyamic acid or the like synthesized using a diamine 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).

  Several techniques have been proposed for solving problems including improvement of the performance of liquid crystal display elements by adding an additive to polyamic acid. Examples of such a technique include a liquid crystal alignment agent containing a polyamic acid and a curing accelerator having an oxazine structure or an oxazoline structure (see, for example, Patent Document 7), and 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.

  In addition, several techniques have been proposed in which problems including improvement of the performance of the liquid crystal display element are solved by adding an additive to the photoalignment compound. Examples of such a technique include a photoalignment composition containing a dichroic molecule and a compound having a nadiimide group as a radical polymerizable group (see, for example, Patent Document 12).

  However, these prior arts have not sufficiently solved the problems of voltage holding ratio 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.

JP 11-193345 A JP-A-11-193347 International Publication No. 2000/61684 Pamphlet International Publication No. 2001/00733 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 2003-270638 A

  In consideration of the above situation, a liquid crystal aligning agent for a liquid crystal display element in which the problem of long-term reliability with respect to electrical characteristics due to a change in voltage holding ratio with time is improved, a liquid crystal alignment film formed using the same, and Development of a liquid crystal display device including the same is desired.

  The present inventors have intensively studied to solve the above problems. As a result, when preparing a liquid crystal alignment film using a liquid crystal aligning agent containing a polymer selected from a polyamic acid and a derivative of this polyamic acid and a compound having a plurality of allyl groups in the molecule, It has been found that the liquid crystal display element can have good long-term reliability, and the present invention has been completed.

（ここに、Ｚ^１は独立して単結合、−Ｏ−、−ＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−、−（ＣＨ_２）_ｔ−、または−Ｏ−（ＣＨ_２）_ｔ−Ｏ−であって、ｔは１〜８の整数であり；Ｚ^２は−ＣＨ_２ＣＨ_２−または１，４−フェニレンであり；Ｑ^１は式（Ｂ−１）で表される基であり；Ｑ^２は式（Ｂ−２）で表される基であり；Ｑ^３は水素または式（Ｂ−３）で表される基であり；そして、ベンゼン環の任意の水素はフッ素、メチルまたは−ＯＨで置き換えられてもよい。） The liquid crystal aligning agent of this invention is shown by the following [1] term.
[1] A composition containing at least one polymer selected from polyamic acid and derivatives thereof and a compound having a plurality of allyl groups, wherein the compounds having a plurality of allyl groups are represented by formulas (A-1) to ( A-7) A liquid crystal aligning agent which is at least one selected from the group of compounds represented by:

(Wherein Z ¹ is independently a single bond, —O—, —CO—, —CONH—, —NHCO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, — (CH _{2) t} -, or -O- _{(CH 2)} a t -O-, t is an integer from 1 to 8; ^{Z 2} is _-CH 2 CH ₂ - be or 1,4-phenylene; Q ¹ is a group represented by the formula (B-1); ^{Q 2} is a group represented by the formula (B-2); ^{Q 3} is a group represented by hydrogen or the formula (B-3) Yes; and any hydrogen on the benzene ring may be replaced with fluorine, methyl or —OH.)

  By using the liquid crystal aligning agent of this invention as a liquid crystal aligning film, the fall of the voltage holding rate of a liquid crystal display element can be suppressed notably.

First, terms used in this specification will be described. The compound represented by formula (A-1) may be abbreviated as compound (A-1). Similar abbreviations may be applied to compounds represented by other formulas. The term “arbitrary” used in defining a chemical formula means that not only the position but also the number is arbitrary. And for example, the expression “any A may be replaced by B, C or D” means that any A is replaced by B, any A is replaced by C, and any A is D In addition to the case where it is replaced with, it is meant to include the case where a plurality of A are replaced with at least two of B to D. However, in the case where any —CH ₂ — may be replaced by —O—, the replacement of a plurality of consecutive —CH ₂ — with —O— is not included.

Symbols such as B and C surrounded by hexagons mean ring B and ring C, respectively. A substituent or a free radical in which a bond is not fixed at a carbon atom position of a ring structure group means that the bonding position with the ring structure group is arbitrary. The bonding position of the substituent in the following nadiimide group is the 1, 5 or 7 position.

  The allyl-substituted nadiimide compound represented by the above formula (A-6) or formula (A-7) is obtained by reacting a compound having three or four maleimide groups with allylcyclopentadiene or three amino groups. Alternatively, it can be obtained by reacting a compound having four with allylbicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic anhydride. Allylbicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic anhydride is obtained by reacting allylcyclopentadiene with maleic anhydride. That is, allylcyclopentadiene is an essential intermediate for producing an allyl-substituted nadiimide compound. The allylcyclopentadiene obtained by reacting allyl chloride with cyclopentadiene is more likely to be a mixture of a plurality of compounds having different allyl group bonding positions than a single compound. And it is very difficult from an economic viewpoint to fractionate this mixture into a single compound. In addition, the use of this single compound is not essential for achieving the object of the present invention. That is, in the present invention, even if the allyl-substituted nadiimide compound is a mixture of compounds having different allyl group substitution positions, the same effect can be obtained, so that this allylcyclopentadiene is used with the possibility of being a mixture. Therefore, there is a strong possibility that the allyl-substituted nadiimide compound is also a mixture of compounds having different allyl group bonding positions. This is the reason why the substitution position of the allyl group is not fixed to any carbon constituting the ring in the formula showing the allyl-substituted nadiimide compound.

  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、Ｚ^１は独立して単結合、−Ｏ−、−（ＣＨ_２）_ｔ−、または−Ｏ−（ＣＨ_２）_ｔ−Ｏ−であって、ｔは１〜８の整数であり；そして、ベンゼン環の任意の水素は−ＯＨで置き換えられてもよい。） The present invention comprises the above item [1] and the following items [2] to [23].
[2] A composition containing at least one polymer selected from polyamic acid and derivatives thereof and a compound having a plurality of allyl groups, wherein the compound having a plurality of allyl groups is represented by formulas (A-1) and ( The liquid crystal aligning agent as described in the item [1], which is at least one compound selected from the group of compounds represented by A-2), formula (A-6) and formula (A-7).

(Where Z ¹ is independently a single bond, —O—, — (CH ₂ ) _t —, or —O— (CH ₂ ) _t —O—, and t is an integer of 1-8. And any hydrogen on the benzene ring may be replaced with -OH.)

[3] A composition containing at least one polymer selected from polyamic acid and derivatives thereof and a compound having a plurality of allyl groups, wherein the compound having a plurality of allyl groups is represented by formula (A-1-1), A compound represented by formula (A-2-1), formula (A-6-1), formula (A-6-2), formula (A-7-1) or formula (A-7-2); The liquid crystal aligning agent of 1 with a certain item.

[4] A composition containing at least one polymer selected from polyamic acid and derivatives thereof and a compound having a plurality of allyl groups, wherein the ratio of the compound having a plurality of allyl groups is 0 by weight to the polymer The liquid crystal aligning agent of any one of [1]-[3] which is 0.01-1.0.

[5] The polyamic acid reacts with at least one of the aromatic tetracarboxylic dianhydrides represented by formula (1), formula (2), formula (5) to formula (7) and formula (14) and diamine. The liquid crystal aligning agent of any one of [1]-[4] which is a polymer obtained by making it.

[6] The method according to any one of [1] to [4], 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.

[7] The polyamic acid is at least one of the aromatic tetracarboxylic dianhydrides represented by the formula (1), the formula (2), the formula (5) to the formula (7), and the formula (14) and other than the aromatic The liquid crystal aligning agent according to any one of [1] to [4], which is a polymer obtained by reacting a mixture of tetracarboxylic dianhydride with diamine.

[8] 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, [ The liquid crystal aligning agent of any one of [1]-[4].

[9] 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 [7], which is at least one of the compounds represented by (35) to (37), (39), (44) and (49).

[10] 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 polyamic acid, 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 [8], which is at least one of the compounds represented by:

[11] 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 an aromatic polyamic acid, The liquid crystal aligning agent as described in the item [8], 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、−ＯＨ、−ＣＯＯＨ、−ＳＯ_３Ｈ、−ＰＯ_３Ｈ_２、ベンジルまたはヒドロキシベンジルで置き換えられてもよい。 [12] The liquid crystal according to any one of [5] to [11], 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, -OH, -COOH} , -SO 3 H, -PO 3 H 2, may be replaced by benzyl or hydroxybenzyl.

[13] The diamine is represented by the 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 [5]-[11] which is at least 1 chosen from the non-side chain type diamine represented by a formula (VII-2).

[14] At least one diamine selected from non-side chain diamines represented by formula (I) to formula (VII) according to claim 12, alkyl having 3 or more carbon atoms, alkoxy having 3 or more carbon atoms, A side having a side chain group selected from an alkoxyalkyl having 3 or more carbon atoms, a group having a steroid skeleton, and an alkyl having 3 or more carbon atoms, an alkoxy having 3 or more carbon atoms or an alkoxyalkyl having 3 or more carbon atoms at the terminal The liquid crystal aligning agent of any one of [5]-[11] which is a mixture with at least 1 of chain type diamine.

（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３〜３０のアルキル、炭素数３〜３０のアルコキシ、または炭素数３〜３０のアルコキシアルキルであり、これらのアルキル、アルコキシおよびアルコキシアルキルにおいて、任意の水素はフッ素で置き換えられてもよく、そして任意の−ＣＨ_２−はジフルオロメチレンまたは式（Ｄ−２）で表される基で置き換えられてもよく；

ここに、Ｒ^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３〜３０のアルキルであって、このアルキルの任意の−ＣＨ_２−は−Ｏ−、−ＣＨ＝ＣＨ−またはＣ≡Ｃ−で置き換えられてもよく；Ｒ^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。） [15] The liquid crystal aligning agent according to item [14], 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 An alkyl having 3 to 30 carbons, an alkoxy having 3 to 30 carbons, or an alkoxyalkyl having 3 to 30 carbons, and in these alkyls, alkoxys and alkoxyalkyls, any hydrogen is replaced by fluorine. And any —CH ₂ — may be replaced by difluoromethylene or a group represented by formula (D-2);

Here, R 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.)

(Wherein R ⁸ is alkyl having 3 to 30 carbon atoms, and any —CH ₂ — in this 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、Ｒ^２４、Ｒ^２９およびＲ^３０は、独立して炭素数３〜３０のアルキル、または炭素数３〜３０のアルコキシである。） [16] 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 [14], which is a diamine selected from the represented compounds.

(Here, R ²³ , R ²⁴ , R ²⁹ and R ³⁰ are each independently alkyl having 3 to 30 carbon atoms or alkoxy having 3 to 30 carbon atoms.)

（ここに、Ｒ^２３、Ｒ^２４、Ｒ^２９およびＲ^３０は、独立して炭素数３〜３０のアルキル、または炭素数３〜３０のアルコキシである。） [17] 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 [14], which is a diamine selected from compounds represented by formula (VIII-6), formula (XI-2) and formula (XI-4).

(Here, R ²³ , R ²⁴ , R ²⁹ and R ³⁰ are each independently alkyl having 3 to 30 carbon atoms or alkoxy having 3 to 30 carbon atoms.)

（ここに、Ｒ^２３、Ｒ^２４、Ｒ^２９およびＲ^３０は、独立して炭素数３〜３０のアルキル、または炭素数３〜３０のアルコキシである。） [18] The polymer comprises 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 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. The liquid crystal aligning agent of any one of [4].

(Here, R ²³ , R ²⁴ , R ²⁹ and R ³⁰ are each independently alkyl having 3 to 30 carbon atoms or alkoxy having 3 to 30 carbon atoms.)

[19] The 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. The liquid crystal aligning agent according to item [18], which is a polyamic acid.

[20] 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 and a mixture of at least one non-side chain diamine and at least one side chain diamine, [18] ] The liquid crystal aligning agent of a term.

[21] The polymer is a mixture of at least one of an aromatic tetracarboxylic dianhydride and at least one of a non-aromatic tetracarboxylic dianhydride, at least one of a non-side chain diamine and at least one of a side chain diamine. The liquid crystal aligning agent according to item [18], which is at least one selected from a polyamic acid obtained by reacting a mixture with one and a derivative thereof.

[22] A liquid crystal alignment film formed by applying the liquid crystal aligning agent according to any one of [1] to [21] on a substrate and baking it in a film state.

[23] A pair of opposed substrates, electrodes formed on one or both of the opposed surfaces of the pair of substrates, and formed on the opposed surfaces 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 described in the item [22]. .

The liquid crystal aligning agent of the present invention is a composition containing at least one polymer selected from polyamic acid and derivatives thereof and a compound having a plurality of allyl groups. The compound having a plurality of allyl groups is at least one compound selected from the group of compounds represented by formula (A-1) to formula (A-7).

In Formula (A-1) to Formula (A-7), Z ¹ is independently a single bond, —O—, —CO—, —CONH—, —NHCO—, —C (CH ₃ ) ₂ —, — C (CF ₃ ) ₂ —, — (CH ₂ ) _t —, or —O— (CH ₂ ) _t —O—, wherein t is an integer of 1 to 8; Z ² is —CH ₂ CH ₂ -Or 1,4-phenylene; Q ¹ is a group represented by formula (B-1); Q ² is a group represented by formula (B-2); Q ³ is hydrogen or a formula A group represented by (B-3); and any hydrogen in the benzene ring may be replaced by fluorine, methyl or —OH. Of these, -OH is preferred.

（ここに、Ｚ^１は独立して単結合、−Ｏ−、−（ＣＨ_２）_ｔ−、または−Ｏ−（ＣＨ_２）_ｔ−Ｏ−であって、ｔは１〜８の整数であり；Ｑ^１およびＱ^２の意味は前記の通りであり；そして、ベンゼン環の任意の水素は−ＯＨで置き換えられてもよい。） Preferred examples of the compound having a plurality of allyl groups are at least selected from the group of compounds represented by formula (A-1), formula (A-2), formula (A-6) and formula (A-7). One compound.

(Where Z ¹ is independently a single bond, —O—, — (CH ₂ ) _t —, or —O— (CH ₂ ) _t —O—, and t is an integer of 1-8. Q ¹ and Q ² are as defined above; and any hydrogen on the benzene ring may be replaced by —OH.

Specific examples of compound (A-1) are shown below.

Specific examples of compound (A-2) are shown below.

Specific examples of compound (A-3) are shown below.

（Ｑ^２の意味は前記の通りである。） Compound (A-6) and Compound (A-7) are allyl-substituted nadiimide compounds. Specific examples of these are shown below.

(Q ^{2 has} the same meaning as described above.)

  More preferable examples of the compound having a plurality of allyl groups are the formula (A-1-1), the formula (A-2-1), the formula (A-6-1), and the formula (A-6-2). , At least one compound selected from the group of compounds represented by formula (A-7-1) and formula (A-7-2).

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. If 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. By replacing a part of the tetracarboxylic dianhydride with a carboxylic acid anhydride, the polymerization reaction can be terminated. And since this termination can suppress the further progress of the reaction, the molecular weight of the resulting polyamic acid can be easily controlled. The ratio of the carboxylic acid anhydride to the tetracarboxylic dianhydride may be in a range that does not impair the effects of the present invention, but it is preferably set to 10 mol% or less of the total tetracarboxylic dianhydride amount.

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

  By the way, diamine can be divided into two types depending on the difference in structure. That is, when a skeleton connecting two amino groups is viewed as a main chain, a group branched from the main chain, that is, a diamine having a side chain group and a diamine having no side chain group. By reacting a diamine having a side chain group with tetracarboxylic dianhydride, a polyamic acid or polyimide having a large number of side chain groups with respect to the main chain of the polymer is obtained. When a polyamic acid or polyimide having a side chain group with respect to such a polymer main chain is used, the liquid crystal alignment film formed from the liquid crystal aligning agent containing this polymer increases the pretilt angle in the liquid crystal display element. Can do. That is, this side chain group is a group having an effect of increasing the pretilt angle, and is an alkyl having 3 or more carbon atoms, an alkoxy having 3 or more carbon atoms, an alkoxyalkyl having 3 or more carbon atoms, a group having a steroid skeleton, and a carbon number. It is selected from a group having 3 or more alkyl, alkoxy having 3 or more carbon atoms or alkoxyalkyl having 3 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, on condition that the terminal ring has alkyl having 3 or more carbon atoms, alkoxy having 3 or more carbon atoms or alkoxyalkyl having 3 or more carbon atoms as a substituent, Phenylcarbonyl, phenylcarbonyloxy, phenyloxycarbonyl, phenylaminocarbonyl, phenylcyclohexyloxy, cycloalkyl having 3 or more carbon atoms, cyclohexylalkyl, cyclohexyloxy, cyclohexyloxycarbonyl, cyclohexylphenyl, cyclohexylphenylalkyl, cyclohexylphenyloxy, bis ( Cyclohexyl) oxy, bis (cyclohexyl) alkyl, bis (cyclohexyl) phenyl, bis (cyclohexyl) phenylalkyl, bis ( Kurohekishiru) oxycarbonyl, and bis (cyclohexyl) phenyloxycarbonyl and cyclohexyl bis (phenyl) group of a ring structure, such as oxycarbonyl,. Note that bis (cyclohexyl) and bis (phenyl) may be bonded not by a single bond but by alkylene.

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

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

In the formulas (I) to (VII), 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- a _{(CH 2)} t -S- or straight chain alkylene of 1 to 12 carbon atoms, t is an integer from 1 to 12; cyclohexane ring or benzene arbitrary hydrogen _rings, -F, -CH 3, -OH, -COOH, -SO 3 H, -PO 3 H 2, may be replaced by benzyl or hydroxybenzyl.

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３〜３０のアルキルであって、このアルキルの任意の−ＣＨ_２−は−Ｏ−、−ＣＨ＝ＣＨ−またはＣ≡Ｃ−で置き換えられてもよく；Ｒ^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。

Here, R ⁸ is alkyl having 3 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 3 to 30 carbon atoms. In Formula (XI-4) to Formula (XI-8), R ³⁰ is carbon. It is preferable that it is a C3-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 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 derivative thereof is diluted with dimethylformamide (DMF) so that the polymer concentration is about 1% by weight, and a gel is prepared using Chromatopack C-R7A (manufactured by Shimadzu Corporation) with DMF as a developing solvent. It is determined by measuring by a permeation chromatographic analysis (GPC) method and converting 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 prepared by using an acid anhydride such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride as dehydrating agents, and dehydrating ring closure. It can be obtained by imidization reaction at a temperature of 20 to 150 ° C. with a tertiary amine such as triethylamine, pyridine, collidine and the like as a catalyst.

  Alternatively, 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 or isopropanol), and the precipitated polyamic acid is dissolved in a solvent such as toluene or xylene. It can also be obtained by imidization reaction at a temperature of 20 to 150 ° C. together with the same dehydrating agent and dehydration ring closure catalyst as described above.

  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, polyamideimide can be produced by chemically imidizing the polyamic acid-polyamide copolymer.

  The liquid crystal aligning agent of the present invention may contain a solvent from the viewpoints of adjustment of physical properties such as viscosity, ease of handling, simplification of processes, and the like, and various additives contained in ordinary liquid crystal aligning agents. Further, it may be included.

  The content ratio of the compound (A) in the liquid crystal aligning agent of the present invention is 0.00 by weight ratio with respect to the polyamic acid or the derivative thereof in the liquid crystal aligning agent from the viewpoint of stabilizing the electrical characteristics for a long time when used in the liquid crystal display element. It is preferably 01 to 1.0, more preferably 0.01 to 0.7, and still more preferably 0.01 to 0.5. A particularly preferred range of this weight ratio is 0.1 to 0.5.

  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 the production process and applications of polymer components such as polyamic acid, soluble polyimide, and polyamideimide, and can be appropriately selected depending on the purpose of use. The solvent is a mixed solvent containing 1) an aprotic polar organic solvent which is easily soluble in polyamic acid and soluble polyimide, and 2) a solvent for improving coating properties by changing the surface tension. Is preferred.
Examples of these solvents are as follows.

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

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

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

  The liquid crystal aligning agent of this invention may contain various additives. 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 polyamide, polyurethane, polyurea, polyester, polyepoxide, polyester polyol, silicone-modified polyurethane, silicone-modified polyester, and the like.

  Other additives include, for example, 1) a surfactant in accordance with the purpose when improvement in coatability is desired, 2) an antistatic agent when improvement in antistatic is required, and 3) adhesion to the substrate. Silane coupling agents and titanium-based coupling agents can be used when it is desired to improve the properties and rubbing resistance, and 4) an imidization catalyst can be used when imidization proceeds at a low temperature.

  Examples of silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyl. Trimethoxysilane, paraaminophenyltrimethoxysilane, paraaminophenyltriethoxysilane, metaaminophenyltrimethoxysilane, metaaminophenyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycid Xylpropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropiyl Trimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propylamine, and N, N Mention may be made of '-bis [3- (trimethoxysilyl) propyl] ethylenediamine.

  Preferred examples of the imidation 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. Amines; and cyclic amines such as pyridine, methyl substituted pyridine, hydroxy substituted pyridine, quinoline, methyl substituted quinoline, hydroxy substituted quinoline, isoquinoline, methyl substituted isoquinoline, hydroxy substituted isoquinoline, imidazole, methyl substituted imidazole, hydroxy substituted imidazole, etc. Can be mentioned. In particular, N, N-dimethylaniline, o-, m-, p-hydroxyaniline, o-, m-, p-hydroxypyridine, and isoquinoline are preferred.

  The addition amount of the silane coupling agent is usually 0 to 10% by weight, preferably 0.1 to 3% by weight, based on the total weight of the polyamic acid or derivative thereof.

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

  The addition amount of other additives varies depending on the application, but is usually 0 to 30% by weight, preferably 0.1 to 10% by weight, based on the total weight of the polyamic acid or derivative thereof. .

  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 acid 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 applying the liquid crystal aligning agent film to, 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 100 nm. The liquid crystal alignment film is preferably rubbed.

  The film thickness of a liquid crystal aligning film can be adjusted with the viscosity of a liquid crystal aligning agent, and the coating method of a liquid crystal aligning agent. 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.

  Next, the liquid crystal display element of the present invention will be described. The liquid crystal display element of the present invention includes 1) a pair of substrates arranged opposite to each other, 2) a liquid crystal alignment film of the present invention formed on the opposed surfaces of each of the pair of substrates, and 3) between the pair of substrates. A liquid crystal layer sandwiched between the two. It is preferable that the pair of substrates with electrodes disposed to face each other is a transparent substrate (for example, a glass substrate).

  Electrodes are provided on at least one or both surfaces 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 is usually composed of 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-A-9-241643 (EP882711A1), JP-A-10-204016 (EP844229A1), JP-A-10-204436, JP-A-10-231482, JP-A-2000-087040, Special Disclosed in Japanese Laid-Open Patent Publication No. 2001-48822 There.

  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. No. 1, 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-A-2001-072626, JP-A-2001-192657, and the like.

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

  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 may be included.

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

  The liquid crystal display element of the present invention can be produced by any method. One example is 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, and 3) dehydrating and ring-closing the dried liquid crystal aligning agent. A step of performing heat treatment necessary for the above, 4) a step of aligning the obtained alignment film, and 5) bonding two substrates together with a predetermined gap, and then enclosing a liquid crystal in the gap between the substrates Or a step of attaching a liquid crystal to one substrate and then bonding it to the other substrate.

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

  In the drying process and 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-2-1): 1,1-bis (4- (4-aminobenzyl) phenyl) -4-heptylcyclohexane compound (XI-4-1): 1,1- Bis [4- (4-aminophenoxy) phenyl-4- (trans-4-n-pentylcyclohexyl) cyclohexane

化合物（Ａ−２−１）：

<Compound having a plurality of allyl groups>
Compound (A-1-1):

Compound (A-2-1):

化合物（Ａ−６−２）：

Compound (A-6-1):

Compound (A-6-2):

Compound (A-7-1):

＜溶剤＞
ＮＭＰ：Ｎ−メチル−２−ピロリドン
ＢＣ：ブチルセロソルブ（エチレングリコールモノブチルエーテル）
ＧＢＬ：γ―ブチロラクトン Compound (A-7-2):

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

[Synthesis Example 1]
<Synthesis of polyamic acid>
In a 100 mL four-necked flask equipped with a thermometer, stirrer, raw material charging inlet and nitrogen gas inlet, compound (V-1) (2.919 g), dehydrated NMP (54 g), and dehydrated GBL (15 g) were added. And dissolved by stirring under a dry nitrogen stream. Subsequently, the compound (19) (1.155 g) and the compound (1) (1.927 g) were added and reacted for 30 hours in a room temperature environment. When the reaction temperature rose during the reaction, the reaction temperature was kept at about 70 ° C. or lower for the reaction. BC (25 g) was added to the obtained solution to obtain a polyamic acid solution (PA1) having a polymer concentration of 6% by weight. The weight average molecular weight of the polymer in PA1 was 58,000.

  The weight average molecular weight of the polyamic acid was determined as follows. First, a solution having a polyamic acid concentration of 6% by weight obtained by the synthesis reaction was diluted to obtain a solution having a polyamic acid concentration of about 1% by weight. Next, the GPC method was applied to this diluted solution, and the measurement data was converted to polystyrene to determine the weight average molecular weight. For diluting the polyamic acid solution, a phosphoric acid-DMF mixed solution (phosphoric acid / DMF weight ratio = 0.6 / 100) was used, and this mixed solution was also used as a developing agent for the GPC method. In addition, Chromatopack C-R7A (manufactured by Shimadzu Corporation) is used as a measuring apparatus of the GPC method, GF-7HQ (manufactured by Showa Denko KK) is used for the column, the column temperature is 50 ° C., and the flow rate is 0.6 mL / min. It was.

[Synthesis Examples 2 to 5]
A polyamic acid solution (PA2 to PA5) was obtained according to Synthesis Example 1 except that tetracarboxylic dianhydride and diamine were changed as shown in Table 1. The results are summarized in Table 1 including Synthesis Example 1.
<Table 1>

[Example 1]
PA1 obtained in Synthesis Example 1 and PA2 obtained in Synthesis Example 2 were mixed at a weight ratio of 8/2. The compound (A-2-1) corresponding to 0.2 by weight ratio with respect to the polyamic acid contained therein was added to the resulting mixture. Thereafter, a mixed solvent of NMP / BC = 1/1 (weight ratio) was added and diluted so that the polyamic acid concentration was 4% by weight to obtain a liquid crystal aligning agent.

  The obtained liquid crystal aligning agent was apply | coated to the glass substrate with two ITO electrodes with a spinner, and the film | membrane with a film thickness of 70 nm was formed. 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 liquid crystal alignment film formed on this glass substrate was ultrasonically cleaned in ultrapure water for 5 minutes and then dried in an oven at 120 ° C. for 30 minutes. Next, after spraying a 7 μm gap material on one glass substrate and placing the other glass substrate oppositely so that the surface on which the liquid crystal alignment film is formed is on the inside and the rubbing direction is antiparallel 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 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]
PA1 obtained in Synthesis Example 1 and PA3 obtained in Synthesis Example 3 were mixed at a weight ratio of 8/2. The compound (A-2-1) corresponding to 0.2 by weight ratio with respect to the polyamic acid contained therein was added to the resulting mixture. Thereafter, a mixed solvent of NMP / BC = 1/1 (weight ratio) was added and diluted so that the polyamic acid concentration was 4% by weight to obtain a liquid crystal aligning agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

[Example 3]
To PA4 obtained in Synthesis Example 4, a compound (A-1-1) corresponding to 0.2 in weight ratio to the polyamic acid contained therein was added. Thereafter, a mixed solvent of NMP / BC = 1/1 (weight ratio) was added and diluted so that the polyamic acid concentration was 4% by weight to obtain a liquid crystal aligning agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

[Example 4]
A compound (A-2-1) corresponding to 0.2 in terms of the weight ratio to the polyamic acid contained therein was added to the PA4. Thereafter, a mixed solvent of NMP / BC = 1/1 (weight ratio) was added and diluted so that the polyamic acid concentration was 4% by weight to obtain a liquid crystal aligning agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

[Example 5]
The PA1 and PA2 were mixed at a weight ratio of 8/2. The compound (A-6-2) corresponding to 0.2 by weight ratio to the polyamic acid contained therein was added to the obtained mixture. Thereafter, a mixed solvent of NMP / BC = 1/1 (weight ratio) was added and diluted so that the polyamic acid concentration was 4% by weight to obtain a liquid crystal aligning agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

[Example 6]
PA5 obtained in Synthesis Example 5 and the above PA2 were mixed at a weight ratio of 8/2. The compound (A-7-1) corresponding to 0.2 by weight ratio with respect to the polyamic acid contained therein was added to the obtained mixture. Thereafter, a mixed solvent of NMP / BC = 1/1 (weight ratio) was added and diluted so that the polyamic acid concentration was 4% by weight to obtain a liquid crystal aligning agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

[Example 7]
The PA1 and PA2 were mixed at a weight ratio of 8/2. The compound (A-6-1) corresponding to 0.2 by weight ratio with respect to the polyamic acid contained therein was added to the obtained mixture. Thereafter, a mixed solvent of NMP / BC = 1/1 (weight ratio) was added and diluted so that the polyamic acid concentration was 4% by weight to obtain a liquid crystal aligning agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

[Example 8]
The PA1 and PA2 were mixed at a weight ratio of 8/2. The compound (A-6-1) corresponding to 0.4 by weight ratio with respect to the polyamic acid contained therein was added to the resulting mixture. Thereafter, a mixed solvent of NMP / BC = 1/1 (weight ratio) was added and diluted so that the polyamic acid concentration was 4% by weight to obtain a liquid crystal aligning agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

[Example 9]
The PA5 and PA2 were mixed at a weight ratio of 8/2. The compound (A-6-1) corresponding to 0.2 by weight ratio with respect to the polyamic acid contained therein was added to the obtained mixture. Thereafter, a mixed solvent of NMP / BC = 1/1 (weight ratio) was added and diluted so that the polyamic acid concentration was 4% by weight to obtain a liquid crystal aligning agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

[Example 10]
The PA1 and PA2 were mixed at a weight ratio of 8/2. The compound (A-7-2) corresponding to 0.2 by weight ratio with respect to the polyamic acid contained therein was added to the obtained mixture. Thereafter, a mixed solvent of NMP / BC = 1/1 (weight ratio) was added and diluted so that the polyamic acid concentration was 4% by weight to obtain a liquid crystal aligning agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

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

[Comparative Example 2]
The PA1 and PA3 were mixed at a weight ratio of 8/2. A mixed solvent of NMP / BC = 1/1 (weight ratio) was added to the obtained mixture, and the mixture was diluted so that the polyamic acid concentration was 4% by weight to obtain a liquid crystal aligning agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent.

[Comparative Example 3]
A liquid crystal aligning agent was prepared by adding a mixed solvent of NMP / BC = 1/1 (weight ratio) to the PA4 and diluting the polyamic acid concentration to 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 13]
<Evaluation of electrical characteristics>
About the liquid crystal display element produced in Examples 1-10 and Comparative Examples 1-3, the measurement of the voltage holding rate and the long-term reliability were performed as follows.
1) Measurement of voltage holding ratio (%) The voltage holding ratio was measured using a liquid crystal property evaluation apparatus 6254 type manufactured by Toyo Technica. The measurement conditions were a gate width of 60 μs, a frequency of 0.3 Hz, a wave height of ± 5 V, and a measurement temperature of 60 ° C. It can be said that the larger this value, the better the electrical characteristics. The results are shown in Table 2.
2) Measurement of long-term reliability About the produced liquid crystal display element, the voltage holding rate was calculated | required with time and the holding | maintenance characteristic was evaluated. As a test method for holding characteristics, a liquid crystal display element was left in an atmosphere at a temperature of 60 ° C. for 500 hours, and the voltage holding ratio was measured by taking it out over time. It can be said that the smaller the decrease in the voltage holding ratio (for example, if the standing time is 500 hours or more under the above conditions and the decrease in the voltage holding ratio is less than 2%), the better the long-term reliability. The results are shown in Table 2. The measurement temperature was 60 ° C.

<Table 2>

  As shown in Table 2, in the case of the liquid crystal display element obtained using the liquid crystal aligning agent of the present invention, the decrease in the voltage holding ratio was remarkably suppressed.

Claims (23)

A composition comprising at least one polymer selected from polyamic acid and derivatives thereof and a compound having a plurality of allyl groups, wherein the compounds having a plurality of allyl groups are represented by formulas (A-1) to (A-7): ) A liquid crystal aligning agent that is at least one selected from the group of compounds represented by:

(Wherein Z ¹ is independently a single bond, —O—, —CO—, —CONH—, —NHCO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, — (CH _{2) t} -, or -O- _{(CH 2)} a t -O-, t is an integer from 1 to 8; ^{Z 2} is _-CH 2 CH ₂ - be or 1,4-phenylene; Q ¹ is a group represented by the formula (B-1); ^{Q 2} is a group represented by the formula (B-2); ^{Q 3} is a group represented by hydrogen or the formula (B-3) Yes; and any hydrogen on the benzene ring may be replaced with fluorine, methyl or —OH.) A composition containing at least one polymer selected from polyamic acid and derivatives thereof and a compound having a plurality of allyl groups, wherein the compound having a plurality of allyl groups is represented by formula (A-1) or formula (A-2). ), A liquid crystal aligning agent according to claim 1, which is at least one compound selected from the group of compounds represented by formula (A-6) and formula (A-7).

(Where Z ¹ is independently a single bond, —O—, — (CH ₂ ) _t —, or —O— (CH ₂ ) _t —O—, and t is an integer of 1-8. And any hydrogen on the benzene ring may be replaced with -OH.) A composition containing at least one polymer selected from polyamic acid and derivatives thereof and a compound having a plurality of allyl groups, wherein the compound having a plurality of allyl groups is represented by formula (A-1-1) or formula (A 2-1), a compound represented by formula (A-6-1), formula (A-6-2), formula (A-7-1) or formula (A-7-2), Item 2. A liquid crystal aligning agent according to Item 1.

  A composition comprising at least one polymer selected from polyamic acid and derivatives thereof and a compound having a plurality of allyl groups, wherein the ratio of the compound having a plurality of allyl groups is 0.01 to The liquid crystal aligning agent of any one of Claims 1-3 which is 1.0. By reacting at least one of the aromatic tetracarboxylic dianhydrides represented by the formula (1), formula (2), formula (5) to formula (7) and formula (14) with the diamine and the polyamic acid The liquid crystal aligning agent of any one of Claims 1-4 which is a polymer obtained.

The liquid crystal aligning agent of any one of Claims 1-4 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 1-4 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. 5. The liquid crystal aligning agent according to any one of 4 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 7 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 of Claim 8 which is at least 1 of the compound which becomes.

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 8 whose tetracarboxylic dianhydride of is a compound represented by Formula (19).

The liquid crystal aligning agent according to any one of claims 5 to 11, wherein the diamine is at least one selected from the group of non-side chain diamines represented by formulas (I) to (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, -OH, -COOH} , -SO 3 H, -PO 3 H 2, may be replaced by benzyl or hydroxybenzyl. 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 5-11 which is at least 1 chosen from non-side chain type diamine represented by Formula (VII-2).

  The diamine is at least one selected from the non-side chain diamines represented by the formulas (I) to (VII) according to claim 12, an alkyl having 3 or more carbon atoms, an alkoxy having 3 or more carbon atoms, and 3 carbon atoms. Side chain type diamine having a side chain group selected from the above alkoxyalkyl, a group having a steroid skeleton, and an alkyl having 3 or more carbon atoms, an alkoxy having 3 or more carbon atoms or an alkoxyalkyl having 3 or more carbon atoms. The liquid crystal aligning agent of any one of Claims 5-11 which is a mixture with at least 1 of these. The liquid crystal aligning agent of Claim 14 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 An alkyl having 3 to 30 carbons, an alkoxy having 3 to 30 carbons, or an alkoxyalkyl having 3 to 30 carbons, and in these alkyls, alkoxys and alkoxyalkyls, any hydrogen is replaced by fluorine. And any —CH ₂ — may be replaced by difluoromethylene or a group represented by formula (D-2);

Here, R 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.)

(Wherein R ⁸ is alkyl having 3 to 30 carbon atoms, and any —CH ₂ — in this 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 14 which is a diamine chosen from a compound.

(Here, R ²³ , R ²⁴ , R ²⁹ and R ³⁰ are each independently alkyl having 3 to 30 carbon atoms or alkoxy having 3 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 14 which is a diamine chosen from the compound represented by (VIII-6), Formula (XI-2), and Formula (XI-4).

(Here, R ²³ , R ²⁴ , R ²⁹ and R ³⁰ are each independently alkyl having 3 to 30 carbon atoms or alkoxy having 3 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 Claims 1-4 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.

(Here, R ²³ , R ²⁴ , R ²⁹ and R ³⁰ are each independently alkyl having 3 to 30 carbon atoms or alkoxy having 3 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 18 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 the mixture of the 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 18 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 1-21 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 23. 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 22.