JP6720661B2 - Liquid crystal alignment agent for forming liquid crystal alignment film for optical alignment, liquid crystal alignment film and liquid crystal display device using the same - Google Patents

Description

The present invention relates to a photo-alignment liquid crystal alignment agent used in a photo-alignment method, a photo-alignment film using the same, and a liquid crystal display device.

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

The technological development of liquid crystal display devices has been achieved not only by improving these driving methods and device structures, but also by improving the constituent members used for the devices. Among the components used in the liquid crystal display element, the liquid crystal alignment film is one of the important materials related to the display quality, and it is necessary to improve the performance of the liquid crystal alignment film as the quality of the liquid crystal display element increases. Is becoming important.

The liquid crystal alignment film is formed of a liquid crystal aligning agent. Currently, the liquid crystal aligning agent that is mainly used is a solution (varnish) obtained by dissolving polyamic acid or soluble polyimide in an organic solvent. After applying this solution to the substrate, a film is formed by means of heating or the like to form a polyimide-based liquid crystal alignment film. After film formation, if necessary, an alignment treatment suitable for the above-mentioned display mode is performed.

Industrially, a rubbing method, which is simple and capable of high-speed processing over a large area, is widely used as an alignment treatment method. The rubbing method is a treatment in which the surface of the liquid crystal alignment film is unidirectionally rubbed with a cloth in which fibers such as nylon, rayon, and polyester are flocked, and thereby uniform alignment of liquid crystal molecules can be obtained. However, problems such as dust generation and static electricity generation due to the rubbing method have been pointed out, and in recent years, development of an alignment treatment method replacing the rubbing method has been actively carried out.

As an alternative alignment treatment method to the rubbing method, an optical alignment treatment method in which light is irradiated to perform the alignment treatment is attracting attention. Many alignment mechanisms such as a photolysis method, a photoisomerization method, a photodimerization method, and a photocrosslinking method have been proposed for the photoalignment treatment method (see, for example, Non-Patent Document 1, Patent Documents 1 and 2). The photo-alignment method has higher uniformity of alignment than the rubbing method, and since it is a non-contact alignment treatment method, the film is not scratched, which may cause display defects such as dust generation and static electricity in the liquid crystal display element. There are advantages such as reduction.

Heretofore, studies have been conducted on a photo-alignment film in which a structure in which a bond is cleaved by ultraviolet rays is introduced into polyamic acid (see, for example, Patent Document 3). Patent Document 3 states that a polymer whose molecular chain length has been shortened by the cleavage of bonds due to ultraviolet rays is rearranged and the rearranged polymer is re-crosslinked with a certain probability, thereby imparting an orientation regulating force. ..

In recent years, in the liquid crystal display element, in consideration of improvement of display quality and outdoor use, there is also an application in which the brightness of a backlight as a light source is made higher than that of the previous one, and even when exposed to strong light for a long time. There is a demand for a liquid crystal display device that does not deteriorate the display quality. One of the causes of the deterioration of display quality due to long-term use is a decrease in the voltage holding ratio of liquid crystal display elements. Providing agents was difficult and needed further improvement.

JP-A-9-297313 JP, 10-251646, A JP, 2011-107266, A

Liquid Crystal, Volume 3, Issue 4, Page 262, 1999

An object of the present invention is to provide a liquid crystal display device that does not deteriorate in display quality even when exposed to strong light for a long time, and a liquid crystal aligning agent and a liquid crystal alignment film that can provide such a display device. Is to provide.

The present inventors have developed a liquid crystal aligning agent for photo-alignment having a structure in which a bond is cleaved by ultraviolet rays, which uses a diamine represented by the following formula (1) as one of the raw materials. It has been found that a liquid crystal display device having a liquid crystal alignment film formed by applying this liquid crystal alignment agent for photo-alignment does not deteriorate in display quality even when exposed to strong light for a long time. The present invention consists of the following.

式（１）において、Ｒ^１は水素またはメチルであり；そして、
Ｒ^２は水素、−ＯＨ、炭素数１〜６のアルキル、または炭素数１〜６のアルコキシであり；
前記テトラカルボン酸二無水物の誘導体とは、テトラカルボン酸ジエステルまたはテトラカルボン酸ジエステルジクロリドである。 [1] At least one selected from the group consisting of tetracarboxylic dianhydride and derivatives thereof is selected from the group consisting of polyamic acid, polyamic acid ester obtained by reacting diamine, and polyimide obtained by imidizing these. A liquid crystal aligning agent for photo-alignment, comprising at least one polymer
A liquid crystal aligning agent for photoalignment, wherein at least one of the raw material monomers of the polymer has a structure in which a bond is cleaved by ultraviolet rays, and the diamine contains at least one compound represented by the following formula (1).

In formula (1), R ¹ is hydrogen or methyl; and
R ² is hydrogen, —OH, alkyl having 1 to 6 carbons, or alkoxy having 1 to 6 carbons;
The derivative of tetracarboxylic dianhydride is tetracarboxylic acid diester or tetracarboxylic acid diester dichloride.

式（１）において、Ｒ^１は水素またはメチルであり；そして、
Ｒ^２は水素、−ＯＨ、炭素数１〜６のアルキル、または炭素数１〜６のアルコキシである。 [2] At least one selected from tetracarboxylic dianhydride and its derivative has a structure in which the bond is cleaved by ultraviolet light, and the diamine contains at least one compound represented by the following formula (1). Contains at least one polymer obtained by reacting raw material monomers; or
At least one selected from tetracarboxylic dianhydride and its derivative, at least one of the polymers obtained by reacting a raw material monomer having a structure in which the bond is cleaved by ultraviolet rays,
Neither tetracarboxylic dianhydride nor its derivative has a structure in which the bond is cleaved by ultraviolet light, and the diamine reacts with a raw material monomer containing at least one compound represented by the following formula (1). The liquid crystal aligning agent for photo-alignment according to the item [1], which simultaneously contains at least one of the polymers obtained in this way.

In formula (1), R ¹ is hydrogen or methyl; and
R ² is hydrogen, —OH, alkyl having 1 to 6 carbons, or alkoxy having 1 to 6 carbons.

式（１）において、Ｒ^１は水素またはメチルであり；そして、
Ｒ^２は水素、−ＯＨ、炭素数１〜６のアルキル、または炭素数１〜６のアルコキシである。 [3] At least one selected from tetracarboxylic dianhydride and its derivative has a structure in which the bond is cleaved by ultraviolet rays, and the diamine is a raw material containing at least one compound represented by the following formula (1): The other polymer used by mixing with at least one of the polymers obtained by reacting the monomers is
Both tetracarboxylic dianhydride and its derivatives are polymers obtained by reacting raw material monomers having no structure in which the bond is cleaved by ultraviolet rays,
The liquid crystal aligning agent for photo-alignment according to the item [2].

In formula (1), R ¹ is hydrogen or methyl; and
R ² is hydrogen, —OH, alkyl having 1 to 6 carbons, or alkoxy having 1 to 6 carbons.

式（１）において、Ｒ^１は水素またはメチルであり；そして、
Ｒ^２は水素、−ＯＨ、炭素数１〜６のアルキル、または炭素数１〜６のアルコキシである。 [4] At least one selected from tetracarboxylic dianhydride and its derivative has a structure in which the bond is cleaved by ultraviolet rays, and the diamine is a raw material monomer containing at least one compound represented by the following formula (1): Other polymer used by mixing with at least one of the polymers obtained by reacting
Neither tetracarboxylic dianhydride nor its derivative has a structure in which the bond is cleaved by ultraviolet rays, and the diamine is reacted with a raw material monomer containing at least one compound represented by the following formula (1). The resulting polymer,
The liquid crystal aligning agent for photo-alignment according to the item [2].

In formula (1), R ¹ is hydrogen or methyl; and
R ² is hydrogen, —OH, alkyl having 1 to 6 carbons, or alkoxy having 1 to 6 carbons.

式（１−１）および式（１−２）において、Ｒ^２は水素、−ＯＨ、炭素数１〜６のアルキル、または炭素数１〜６のアルコキシである。 [5] The diamine represented by the formula (1) is at least one selected from the group consisting of the diamine represented by the formula (1-1) and the diamine represented by the formula (1-2), 1] to [4], the liquid crystal aligning agent for photo-alignment according to any one of items 1 to 4;

In formulas (1-1) and (1-2), R ² is hydrogen, —OH, alkyl having 1 to 6 carbons, or alkoxy having 1 to 6 carbons.

[6] The diamine represented by the formula (1) is represented by the following formula (1-1-1) to formula (1-1-6), formula (1-1-17), formula (1-1-18). At least 1 selected from the group consisting of diamines represented by formulas (1-2-1) to (1-2-6), formulas (1-2-17), and formulas (1-2-18). The liquid crystal aligning agent for optical alignment according to any one of [1] to [4].

式（２）〜式（６）において、Ｒ^３は式（７）〜式（９）で表される構造であり；そして、
Ｒ^８は独立して炭素数１〜５のアルキル基である。

式（７）〜式（９）において、Ｒ^４〜Ｒ^７は独立して水素、炭素数１〜５のアルキル基またはフェニル基である。 [7] A tetracarboxylic acid dianhydride having a structure in which a bond is cleaved by ultraviolet rays and a derivative thereof are composed of a tetracarboxylic acid dianhydride having a structure represented by the following formulas (2) to (6) and a derivative thereof. The liquid crystal aligning agent for optical alignment according to any one of [1] to [4], which is at least one selected from the group.

In formulas (2) to (6), R ³ is a structure represented by formulas (7) to (9); and
R ⁸ is independently an alkyl group having 1 to 5 carbon atoms.

In formulas (7) to (9), R ^{4 to} R ⁷ are independently hydrogen, an alkyl group having 1 to 5 carbon atoms or a phenyl group.

式（１０）〜式（１４）において、Ｒ^９〜Ｒ^１２は独立して水素、メチル基、フェニル基であり；そして
Ｒ^１３は独立して炭素数１〜５のアルキル基である。 [8] A tetracarboxylic acid dianhydride having a structure in which a bond is cleaved by ultraviolet rays and a derivative thereof are selected from the group consisting of tetracarboxylic acid dianhydrides and their derivatives represented by the following formulas (10) to (14). The liquid crystal aligning agent for optical alignment according to the item [7], which is at least one selected.

In formulas (10) to (14), R ^{9 to} R ¹² are independently hydrogen, a methyl group, and a phenyl group; and R ¹³ is independently an alkyl group having 1 to 5 carbon atoms.

式（１５）から式（２４）において、Ｒ^１４は独立して炭素数１〜５のアルキル基である。 [9] A tetracarboxylic acid dianhydride having a structure in which a bond is cleaved by ultraviolet light and a derivative thereof are selected from the group consisting of tetracarboxylic acid dianhydrides and their derivatives represented by the following formulas (15) to (25). The liquid crystal aligning agent for optical alignment according to the item [8], which is at least one selected.

In formulas (15) to (24), R ¹⁴ is independently an alkyl group having 1 to 5 carbon atoms.

式（ＡＮ−１−２）および式（ＡＮ−４−１７）において、ｍは１〜１２の整数である。 [10] A tetracarboxylic acid dianhydride having no structure in which a bond is cleaved by ultraviolet rays is represented by the following formula (AN-1-1), formula (AN-1-2), formula (AN-1-13), Formula (AN-3-2), Formula (AN-4-5), Formula (AN-4-17), Formula (AN-4-21), Formula (AN-4-29), Formula (AN-4). -30), formula (AN-5-1), formula (AN-7-2), formula (AN-10-1), formula (AN-11-3), formula (AN-16-1), formula The liquid crystal aligning agent for optical alignment according to any one of [1] to [9], which is at least one selected from (AN-16-3) and formula (AN-16-4).

In Formula (AN-1-2) and Formula (AN-4-17), m is an integer of 1-12.

式（ＤＩ−１）において、Ｇ^２０は、−ＣＨ_２−であり、少なくとも１つの−ＣＨ_２−は−ＮＨ−、−Ｏ−に置き換えられてもよく、ｍは１〜１２の整数であり、アルキレンの少なくとも１つの水素は−ＯＨに置き換えられてもよく；
式（ＤＩ−３）および式（ＤＩ−５）〜式（ＤＩ−７）において、Ｇ^２１は独立して単結合、−ＮＨ−、−ＮＣＨ_３−、−Ｏ−、−Ｓ−、−Ｓ−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＣＯＯ−、−ＣＯＮＨ−、−ＣＯＮＣＨ_３−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−、−（ＣＨ_２）_ｍ’−、−Ｏ−（ＣＨ_２）_ｍ’−Ｏ−、−Ｎ（ＣＨ_３）−（ＣＨ_２）_ｋ−Ｎ（ＣＨ_３）−、−（Ｏ−Ｃ_２Ｈ_４）_ｍ’−Ｏ−、−Ｏ−ＣＨ_２−Ｃ（ＣＦ_３）_２−ＣＨ_２−Ｏ−、−Ｏ−ＣＯ−（ＣＨ_２）_ｍ’−ＣＯ−Ｏ−、−ＣＯ−Ｏ−（ＣＨ_２）_ｍ’−Ｏ−ＣＯ−、−（ＣＨ_２）_ｍ’−ＮＨ−（ＣＨ_２）_ｍ’−、−ＣＯ−（ＣＨ_２）_ｋ−ＮＨ−（ＣＨ_２）_ｋ−、−（ＮＨ−（ＣＨ_２）_ｍ’）_ｋ−ＮＨ−、−ＣＯ−Ｃ_３Ｈ_６−（ＮＨ−Ｃ_３Ｈ_６）_ｎ−ＣＯ−、−（ＣＨ_２）_ｋ−ＮＨ−ＣＯ−ＮＨ−（ＣＨ_２）_ｋ−、または−Ｓ−（ＣＨ_２）_ｍ’−Ｓ−であり、ｍ’は独立して１〜１２の整数であり、ｋは１〜５の整数であり、ｎは１または２であり；
式（ＤＩ−４）において、ｓは独立して０〜２の整数であり；
式（ＤＩ−６）および式（ＤＩ−７）において、Ｇ^２２は独立して単結合、−Ｏ−、−Ｓ−、−ＣＯ−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−、または炭素数１〜１０のアルキレンであり；
式（ＤＩ−２）〜式（ＤＩ−７）において、シクロヘキサン環およびベンゼン環の少なくとも１つの水素は、−Ｆ、−Ｃｌ、炭素数１〜３のアルキレン、−ＯＣＨ_３、−ＯＨ、−ＣＦ_３、−ＣＯ_２Ｈ、−ＣＯＮＨ_２、−ＮＨＣ_６Ｈ_５、フェニル、またはベンジルで置き換えられてもよく、加えて式（ＤＩ−４）においてベンゼン環の少なくとも１つの水素は、下記式（ＤＩ−４−ａ）〜式（ＤＩ−４−ｅ）で表される基の群から選ばれる１つで置き換えられていてもよく；

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

式（ＤＩ−１１）において、ｒは０または１であり；
式（ＤＩ−８）〜式（ＤＩ−１１）において、環に結合する−ＮＨ_２の結合位置は、任意の位置であり；

式（ＤＩ−１２）において、Ｒ^２１およびＲ^２２は独立して炭素数１〜３のアルキルまたはフェニルであり、Ｇ^２３は独立して炭素数１〜６のアルキレン、フェニレンまたはアルキル置換されたフェニレンであり、ｗは１〜１０の整数であり；
式（ＤＩ−１３）において、Ｒ^２３は独立して炭素数１〜５のアルキル、炭素数１〜５のアルコキシまたは−Ｃｌであり、ｐは独立して０〜３の整数であり、ｑは０〜４の整数であり；
式（ＤＩ−１４）において、環Ｂは単環式複素芳香族であり、Ｒ^２４は水素、−Ｆ、−Ｃｌ、炭素数１〜６のアルキル、炭素数１〜６のアルコキシ、炭素数２〜６のアルケニル、炭素数１〜６のアルキニルであり、ｑは独立して０〜４の整数であり；
式（ＤＩ−１５）において、環Ｃはヘテロ原子を含む単環であり；
式（ＤＩ−１６）において、Ｇ^２４は単結合、炭素数２〜６のアルキレンまたは１，４−フェニレンであり、ｒは０または１であり；
式（ＤＩ−１３）〜式（ＤＩ−１６）において、環を構成する炭素原子に結合位置が固定されていない基は、その環における結合位置が任意であることを示し；

式（ＤＩＨ−１）において、Ｇ^２５は単結合、炭素数１〜２０のアルキレン、−ＣＯ−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−Ｃ（ＣＨ_３）_２−、または−Ｃ（ＣＦ_３）_２−であり；
式（ＤＩＨ−２）において、環Ｄはシクロヘキサン環、ベンゼン環またはナフタレン環であり、この環の少なくとも１つの水素はメチル、エチル、またはフェニルで置き換えられてもよく；
式（ＤＩＨ−３）において、環Ｅはそれぞれ独立してシクロヘキサン環、またはベンゼン環であり、この環の少なくとも１つの水素はメチル、エチル、またはフェニルで置き換えられてもよく、Ｙは単結合、炭素数１〜２０のアルキレン、−ＣＯ−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−Ｃ（ＣＨ_３）_２−、または−Ｃ（ＣＦ_３）_２−であり；
式（ＤＩＨ−２）および式（ＤＩＨ−３）において、環に結合する−ＣＯＮＨＮＨ_２の結合位置は、任意の位置であり；

式（ＤＩ−３１）において、Ｇ^２６は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−、−ＣＯＮＨ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、または−（ＣＨ_２）_ｍ’−であり、ｍ’は１〜１２の整数であり、Ｒ^２５は炭素数３〜３０のアルキル、フェニル、ステロイド骨格を有する基、または下記の式（ＤＩ−３１−ａ）で表される基であり、このアルキルにおいて、少なくとも１つの水素は−Ｆで置き換えられてもよく、少なくとも１つの−ＣＨ_２−は−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられていてもよく、このフェニルの水素は、−Ｆ、−ＣＨ_３、−ＯＣＨ_３、−ＯＣＨ_２Ｆ、−ＯＣＨＦ_２、−ＯＣＦ_３、炭素数３〜３０のアルキルまたは炭素数３〜３０のアルコキシで置き換えられていてもよく、ベンゼン環に結合する−ＮＨ_２の結合位置はその環において任意の位置であることを示し、

式（ＤＩ−３１−ａ）において、Ｇ^２７、Ｇ^２８およびＧ^２９は結合基であり、これらは独立して単結合、または炭素数１〜１２のアルキレンであり、このアルキレンの１以上の−ＣＨ_２−は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＣＨ＝ＣＨ−で置き換えられていてもよく、環Ｂ^２１、環Ｂ^２２、環Ｂ^２３および環Ｂ^２４は独立して１，４−フェニレン、１，４−シクロへキシレン、１，３−ジオキサン−２，５−ジイル、ピリミジン−２，５−ジイル、ピリジン−２，５−ジイル、ナフタレン−１，５−ジイル、ナフタレン−２，７−ジイルまたはアントラセン−９，１０−ジイルであり、環Ｂ^２１、環Ｂ^２２、環Ｂ^２３および環Ｂ^２４において、少なくとも１つの水素は−Ｆまたは−ＣＨ_３で置き換えられてもよく、ｓ、ｔおよびｕは独立して０〜２の整数であって、これらの合計は１〜５であり、ｓ、ｔまたはｕが２であるとき、各々の括弧内の２つの結合基は同じであっても異なってもよく、２つの環は同じであっても異なっていてもよく、
Ｒ^２６は水素、−Ｆ、−ＯＨ、炭素数１〜３０のアルキル、炭素数１〜３０のフッ素置換アルキル、炭素数１〜３０のアルコキシ、−ＣＮ、−ＯＣＨ_２Ｆ、−ＯＣＨＦ_２、または−ＯＣＦ_３であり、この炭素数１〜３０のアルキルの少なくとも１つの−ＣＨ_２−は下記式（ＤＩ−３１−ｂ）で表される２価の基で置き換えられていてもよく、

式（ＤＩ−３１−ｂ）において、Ｒ^２７およびＲ^２８は独立して炭素数１〜３のアルキルであり、ｖは１〜６の整数であり；

式（ＤＩ−３２）および式（ＤＩ−３３）において、Ｇ^３０は独立して単結合、−ＣＯ−または−ＣＨ_２−であり、Ｒ^２９は独立して水素または−ＣＨ_３であり、Ｒ^３０は水素、炭素数１〜２０のアルキル、または炭素数２〜２０のアルケニルであり；
式（ＤＩ−３３）におけるベンゼン環の１つの水素は、炭素数１〜２０のアルキルまたはフェニルで置き換えられてもよく、そして、
式（ＤＩ−３２）および式（ＤＩ−３３）において、環を構成するいずれかの炭素原子に結合位置が固定されていない基は、その環における結合位置が任意であることを示し；

式（ＤＩ−３４）および式（ＤＩ−３５）において、Ｇ^３１は独立して−Ｏ−または炭素数１〜６のアルキレンであり、Ｇ^３２は単結合または炭素数１〜３のアルキレンであり、
Ｒ^３１は水素または炭素数１〜２０のアルキルであり、このアルキルの少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、Ｒ^３２は炭素数６〜２２のアルキルであり、Ｒ^３３は水素または炭素数１〜２２のアルキルであり、環Ｂ^２５は１，４−フェニレンまたは１，４−シクロヘキシレンであり、ｒは０または１であり、そして、ベンゼン環に結合する−ＮＨ_２はその環における結合位置が任意であることを示す。 [11] A diamine having no structure in which a bond is cleaved by ultraviolet rays is represented by the following formula (DI-1) to formula (DI-16), formula (DIH-1) to formula (DIH-3), and formula (DI). -31) to the liquid crystal aligning agent for optical alignment according to any one of [1] to [10], which is at least one selected from the group consisting of formula (DI-35).

In formula (DI-1), G ²⁰ is —CH ₂ —, at least one —CH ₂ — may be replaced by —NH—, —O—, and m is an integer of 1 to 12. , At least one hydrogen of the alkylene may be replaced with —OH;
In formula (DI-3) and formula (DI-5) to formula (DI-7), G ²¹ is independently a single bond, —NH—, —NCH ₃ —, —O—, —S—, —S. _{-S -, - SO 2 -,} - CO -, - COO -, - CONH -, - CONCH 3 -, - C (CH 3) 2 -, - C (CF 3) 2 -, - (CH 2) m _{'-, - O- (CH 2} ) m' -O -, - N (CH 3) - (CH 2) k -N (CH 3) -, - (O-C 2 H 4) m '-O- _{, -O-CH 2 -C (CF} 3) 2 -CH 2 -O -, - O-CO- (CH 2) m '-CO-O -, - CO-O- (CH 2) m' -O _{-CO -, - (CH 2)} m '-NH- (CH 2) m' -, - CO- (CH 2) k -NH- (CH 2) k -, - (NH- (CH 2) m ' _{) k -NH -, - CO-} C 3 H 6 - (NH-C 3 H 6) n -CO -, - (CH 2) k -NH-CO-NH- (CH 2) k -, or -S - _(CH 2) _{m 'is} -S-, m' is an integer from 1 to 12 independently, k is an integer of 1 to 5, n represents 1 or 2;
In formula (DI-4), s is independently an integer of 0 to 2;
In formula (DI-6) and formula ^{(DI-7), G 22} are independently a single bond, -O -, - S -, - CO -, - C (CH 3) 2 -, - C (CF 3 ) _2- or alkylene having 1 to 10 carbon atoms;
In formulas (DI-2) to (DI-7), at least one hydrogen of the cyclohexane ring and the benzene ring is —F, —Cl, alkylene having 1 to 3 carbon atoms, —OCH ₃ , —OH, —CF. _{3, -CO 2 H, -CONH 2} , -NHC 6 H 5, may be replaced by phenyl or benzyl, in addition at least one hydrogen of the benzene ring in formula (DI-4) represented by the following formula (DI -4-a) to may be substituted with one selected from the group of groups represented by formula (DI-4-e);

In formula (DI-4-a) and formula (DI-4-b), R ²⁰ is independently hydrogen or —CH ₃ .
A group in which the bonding position is not fixed to the carbon atoms constituting the ring indicates that the bonding position in the ring is arbitrary, and the bonding position of —NH ₂ to the cyclohexane ring or the benzene ring is G ²¹ or G ^22. Any position except the bonding position of

In formula (DI-11), r is 0 or 1;
In formulas (DI-8) to (DI-11), the bonding position of —NH ₂ bonded to the ring is any position;

In formula (DI-12), R ²¹ and R ²² are independently alkyl or phenyl having 1 to 3 carbon atoms, and G ²³ is independently alkylene, phenylene, or alkyl-substituted phenylene having 1 to 6 carbon atoms. And w is an integer from 1 to 10;
In formula (DI-13), R ²³ is independently alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons or —Cl, p is independently an integer of 0 to 3, and q is Is an integer from 0 to 4;
In formula (DI-14), ring B is a monocyclic heteroaromatic, R ²⁴ is hydrogen, —F, —Cl, alkyl having 1 to 6 carbons, alkoxy having 1 to 6 carbons, and 2 carbons. To alkenyl, alkynyl having 1 to 6 carbon atoms, q is independently an integer of 0 to 4;
In formula (DI-15), ring C is a monocycle containing a heteroatom;
In formula (DI-16), G ²⁴ is a single bond, alkylene having 2 to 6 carbon atoms or 1,4-phenylene, and r is 0 or 1.
In the formulas (DI-13) to (DI-16), a group in which the bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary;

In formula (DIH-1), G ²⁵ is a single bond, alkylene having 1 to 20 carbon atoms, —CO—, —O—, —S—, —SO ₂ —, —C(CH ₃ ) ₂ —, or —. C _{(CF 3) 2} - a and;
In formula (DIH-2), ring D is a cyclohexane ring, a benzene ring or a naphthalene ring, at least one hydrogen of which may be replaced by methyl, ethyl or phenyl;
In formula (DIH-3), each ring E is independently a cyclohexane ring or a benzene ring, at least one hydrogen of this ring may be replaced with methyl, ethyl, or phenyl, and Y is a single bond, alkylene having 1 to 20 carbon atoms, -CO -, - O -, - S -, - SO 2 -, - C (CH 3) 2 -, or -C _{(CF 3) 2} - a and;
In formula (DIH-2) and formula (DIH-3), the bonding position of —CONHNH ₂ bonded to the ring is any position;

In the formula (DI-31), G ²⁶ is a single bond, —O—, —COO—, —OCO—, —CO—, —CONH—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—. , -OCF ₂ -, or - _(CH 2) _{m '-} is and, m' is an integer from 1 to ^{12, R 25} is a group having alkyl of 3 to 30 carbon atoms, phenyl, a steroid skeleton or below, of a group represented by the formula (DI-31-a), and in the alkyl, at least one hydrogen may be replaced by -F, at least one of -CH ₂ - -O -, - CH = may be replaced by CH- or -C≡C-, hydrogen which _{phenyl, -F, -CH 3, -OCH 3} , -OCH 2 F, -OCHF 2, -OCF 3, 3~ carbon atoms It may be substituted with alkyl of 30 or alkoxy of 3 to 30 carbon atoms, and the bonding position of —NH ₂ bonded to the benzene ring is any position in the ring,

In formula (DI-31-a), G ²⁷ , G ^28, and G ²⁹ are bonding groups, which are independently a single bond or an alkylene having 1 to 12 carbons, and one or more of these alkylenes are -. CH ₂ - is -O -, - COO -, - OCO -, - CONH -, - CH = CH- may be replaced by ring ^{B 21,} ring ^{B 22,} ring ^{B 23} and ring ^{B 24} is independently 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, naphthalene-1,5- diyl, naphthalene-2,7-diyl or anthracene-9,10-diyl, ring ^{B 21,} ring ^{B 22,} the ring ^{B 23} and ring ^{B 24,} at least one hydrogen replaced by -F or -CH ₃ S, t and u are each independently an integer from 0 to 2, the sum of which is 1 to 5, and when s, t or u is 2, 2 in each parenthesis is used. The two linking groups may be the same or different, the two rings may be the same or different,
R ²⁶ is hydrogen, —F, —OH, alkyl having 1 to 30 carbons, fluorine-substituted alkyl having 1 to 30 carbons, alkoxy having 1 to 30 carbons, —CN, —OCH ₂ F, —OCHF ₂ , or is -OCF _3, at least one -CH ₂ alkyl of 1 to 30 carbon atoms - may be replaced by a divalent group represented by the following formula (DI-31-b),

In formula (DI-31-b), R ²⁷ and R ²⁸ are independently alkyl having 1 to 3 carbons, and v is an integer from 1 to 6;

In formula (DI-32) and formula (DI-33), G ³⁰ is independently a single bond, —CO— or —CH ₂ —, R ²⁹ is independently hydrogen or —CH ₃ , and R ²⁹ is ³⁰ is hydrogen, alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons;
One hydrogen of the benzene ring in formula (DI-33) may be replaced with alkyl having 1 to 20 carbons or phenyl, and
In formula (DI-32) and formula (DI-33), a group in which the bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary;

In formula (DI-34) and formula (DI-35), G ³¹ is independently —O— or alkylene having 1 to 6 carbons, and G ³² is a single bond or alkylene having 1 to 3 carbons. ,
R ³¹ is hydrogen or alkyl having 1 to 20 carbons, and at least one —CH ₂ — of this alkyl may be replaced by —O—, —CH═CH— or —C≡C—, R ^{31 32} is alkyl having 6 to 22 carbons, R ³³ is hydrogen or alkyl having 1 to 22 carbons, ring B ²⁵ is 1,4-phenylene or 1,4-cyclohexylene, r is 0 or 1 and —NH ₂ bonded to the benzene ring indicates that the bonding position in the ring is arbitrary.

式（ＤＩ−５−１）、式（ＤＩ−５−１２）、式（ＤＩ−５−１３）、式（ＤＩ−７−３）、および式（ＤＩ−３６−１３）において、ｍは１〜１２の整数であり；
式（ＤＩ−５−３０）および式（ＤＩ−５−４２）において、ｋは独立して１〜５の整数であり；
式（ＤＩ−７−３）において、ｎは独立して１または２であり；
式（ＤＩ−３６−９）において、ｅは２〜１０の整数であり；そして
式（ＤＩ−３６−１３）において、Ｒ^４４は−ＮＨＢｏｃまたは−Ｎ（Ｂｏｃ）_２である。
ここでＢｏｃは、ｔ−ブトキシカルボニル基のことである。 [12] The diamine having no structure in which the bond is cleaved by ultraviolet rays is represented by the following formula (DI-1-3), formula (DI-2-1), formula (DI-4-1), formula (DI-4). -2), Formula (DI-4-10), Formula (DI-4-15), Formula (DI-5-1), Formula (DI-5-9), Formula (DI-5-12), Formula (DI-5-13), Formula (DI-5-28), Formula (DI-5-30), Formula (DI-7-3), Formula (DI-13-1), Formula (DI-16-). 1), formula (DIH-2-1), formula (DI-5-42), formula (DI-36-9) and formula (DI-36-13), at least one selected from the group consisting of: The liquid crystal aligning agent for optical alignment as described in [11].

In formula (DI-5-1), formula (DI-5-12), formula (DI-5-13), formula (DI-7-3), and formula (DI-36-13), m is 1 Is an integer from 12 to 12;
In formula (DI-5-30) and formula (DI-5-42), k is independently an integer of 1 to 5;
In formula (DI-7-3), n is independently 1 or 2.
In formula (DI-36-9), e is an integer from 2 to 10; and in formula ^{(DI-36-13), R 44} is -NHBoc or -N _{(Boc) 2.}
Boc is a t-butoxycarbonyl group here.

[13] At least one selected from the group of compounds consisting of an alkenyl-substituted nadimide compound, a compound having a radical-polymerizable unsaturated double bond, an oxazine compound, an oxazoline compound, and an epoxy compound, [1] to [1]. [12] The liquid crystal aligning agent for optical alignment according to any one of [12].

[14] The liquid crystal aligning agent for optical alignment according to any one of [1] to [13], which is used for manufacturing a horizontal electric field type liquid crystal display device.

[15] A liquid crystal alignment film formed by the liquid crystal alignment agent for optical alignment according to any one of [1] to [14].

[16] A liquid crystal display device having the liquid crystal alignment film according to the item [15].

[17] A horizontal electric field type liquid crystal display device having the liquid crystal alignment film according to the item [15].

The liquid crystal display device having the liquid crystal alignment film for photo-alignment formed by the liquid crystal aligning agent for photo-alignment of the present invention does not decrease the voltage holding ratio even after long-term use, and has a high display quality even when exposed to strong light. Can be maintained.

<Liquid crystal aligning agent for photo-alignment>
The liquid crystal aligning agent for photoalignment of the present invention is a reaction product of at least one selected from tetracarboxylic dianhydride and its derivative with a diamine, polyamic acid, polyamic acid ester, and polyimide obtained by imidizing these. A compound containing at least one polymer selected from the group consisting of, at least one of the raw material monomers of the polymer has a structure in which the bond is cleaved by ultraviolet rays, and the diamine is represented by the following formula (1): At least one of the above is included. The polyamic acid, a polyamic acid ester and a polyimide obtained by imidizing these are components that dissolve in a solvent when the liquid crystal aligning agent containing a solvent described below is used, and the liquid crystal aligning film is a liquid crystal aligning film described below. Is a component that can form a liquid crystal alignment film containing polyimide as a main component. The polyamic acid ester is a method of synthesizing by reacting the above-mentioned polyamic acid with a hydroxyl group-containing compound, a halide, an epoxy group-containing compound, or a tetracarboxylic acid diester or tetracarboxylic acid derived from tetracarboxylic dianhydride. It can be synthesized by a method of reacting an acid diester dichloride with a diamine. The tetracarboxylic acid diester derived from tetracarboxylic acid dianhydride can be obtained, for example, by reacting tetracarboxylic acid dianhydride with 2 equivalents of an alcohol to open the ring, and tetracarboxylic acid diester dichloride is tetracarboxylic acid. It can be obtained by reacting a diester with 2 equivalents of a chlorinating agent such as thionyl chloride. The polyamic acid ester may have only an amic acid ester structure, or may be a partial esterified product in which an amic acid structure and an amic acid ester structure coexist. The liquid crystal aligning agent for photo-alignment of the present invention may contain one of these polyamic acids, polyamic acid esters and polyimides obtained by imidizing these, or may contain two or more thereof.

The liquid crystal aligning agent for photoalignment of the present invention has a structure in which at least one selected from the group consisting of tetracarboxylic dianhydride and its derivative, and diamine has a structure in which the bond is cleaved by ultraviolet light, and the diamine has the above formula ( 1) containing at least one of the polymers obtained by reacting a raw material monomer containing at least one of the compounds, or selected from the group consisting of tetracarboxylic dianhydrides and their derivatives, and diamines. At least one of the polymers obtained by reacting at least one raw material monomer having a structure in which a bond is cleaved by ultraviolet rays, tetracarboxylic dianhydride and its derivative, and diamine are cleaved by ultraviolet rays. A liquid crystal aligning agent for photo-alignment, which does not have a structure, and in which the diamine simultaneously contains at least one polymer obtained by reacting a raw material monomer containing at least one compound represented by the formula (1) is there.

<Photolytic structure>
In the present invention, the photolytic structure means a structure in which the bond is cleaved by ultraviolet rays. A raw material monomer having a structure in which the bond is cleaved by ultraviolet rays can be appropriately used.

式（２）〜式（６）において、Ｒ^３は式（７）〜（９）で表される構造であり、Ｒ^８は独立して炭素数１〜５のアルキル基である。 Examples of the monomer having a photodegradable structure include tetracarboxylic dianhydride and a derivative thereof having a photodegradable structure, and compounds represented by the following formulas (2) to (6) having good photosensitivity. It is preferably at least one selected from the group

In formulas (2) to (6), R ³ is a structure represented by formulas (7) to (9), and R ⁸ is independently an alkyl group having 1 to 5 carbon atoms.

式（７）〜式（９）において、Ｒ^４〜Ｒ^７は独立して水素、炭素数１〜５のアルキル基またはフェニル基である。特にＲ^３が（７）で表されるテトラカルボン酸二無水物およびその誘導体であることが好ましく、下記式（１０）〜式（１４）で表されるテトラカルボン酸二無水物およびその誘導体がより好ましい。

In formulas (7) to (9), R ^{4 to} R ⁷ are independently hydrogen, an alkyl group having 1 to 5 carbon atoms or a phenyl group. In particular, R ³ is preferably a tetracarboxylic acid dianhydride represented by (7) and a derivative thereof, and a tetracarboxylic acid dianhydride represented by the following formulas (10) to (14) and a derivative thereof are More preferable.

式（１０）〜式（１４）において、Ｒ^９〜Ｒ^１２は独立して水素、メチル基、フェニル基であり、Ｒ^１３は独立して炭素数１〜５のアルキル基である。

In formulas (10) to (14), R ^{9 to} R ¹² are independently hydrogen, a methyl group, and a phenyl group, and R ¹³ is independently an alkyl group having 1 to 5 carbon atoms.

式（１５）〜式（２４）において、Ｒ^１４は独立して炭素数１〜５のアルキル基である。 Specific examples of the tetracarboxylic dianhydride having a photolytic structure and its derivative are shown below.

In formulas (15) to (24), R ¹⁴ is independently an alkyl group having 1 to 5 carbon atoms.

The photolytic structure may be incorporated into either the main chain or the side chain of the polyamic acid, polyamic acid ester and polyimide obtained by imidizing these in the present invention. It can be suitably used for display devices.

In an embodiment in which a tetracarboxylic dianhydride having no photolytic structure and a tetracarboxylic dianhydride having a photolytic structure or a derivative thereof are used in combination, in order to prevent a decrease in sensitivity to light of the liquid crystal alignment film, Polyamic acid of the present invention, polyamic acid ester and tetracarboxylic dianhydride used as a raw material when producing a polyimide obtained by imidizing these and the total amount of the derivative thereof, tetracarboxylic having a photolytic structure The acid dianhydride is preferably 30 to 100 mol %, particularly preferably 70 to 100 mol %. Further, two or more tetracarboxylic dianhydrides having a photolytic structure and derivatives thereof may be used in combination in order to improve the above-mentioned various characteristics such as sensitivity to light, electric characteristics, and afterimage characteristics.

The diamine represented by the formula (1) of the present invention will be described. In the diamine represented by the formula (1), R ¹ is hydrogen or methyl, and R ² is hydrogen, —OH, alkyl having 1 to 6 carbons, or alkoxy having 1 to 6 carbons. The substitution positions of the two amino groups on the benzene ring are not particularly limited, but in order to make the liquid crystal aligning agent capable of better aligning the liquid crystal molecules, the substitution position of the amide group is 3, 5, or 2, 2. 5th place is desirable.

式（１−１）および式（１−２）において、Ｒ^２は水素、−ＯＨ、炭素数１〜６のアルキル、または炭素数１〜６のアルコキシである。 The diamine represented by the formula (1) is classified into a diamine represented by the formula (1-1) in which R ¹ is hydrogen and a diamine represented by the formula (1-2) in which R ¹ is methyl. To be done.

In formulas (1-1) and (1-2), R ² is hydrogen, —OH, alkyl having 1 to 6 carbons, or alkoxy having 1 to 6 carbons.

When a liquid crystal aligning agent having higher solubility in a solvent is desired, it is preferable to use the diamine of the formula (1-1). Further, when a more reliable liquid crystal alignment film is desired, it is preferable to use a compound in which R ² is hydrogen or —OH in the formulas (1-1) and (1-2).

Specific examples of the diamine represented by the formula (1-1) are compounds represented by the following formulas (1-1-1) to (1-1-28).

Specific examples of the diamine represented by the formula (1-2) are compounds represented by the following formulas (1-2-1) to (1-2-28).

The diamines represented by formulas (1-1-1) to (1-1-4), formulas (1-2-1) and (1-2-2) constitute the liquid crystal aligning agent of the present invention. By using it as one of the polymer raw materials, a liquid crystal alignment film having a high liquid crystal alignment property can be obtained without lowering the display quality even when used for a long time.

By using the diamine represented by the formula (1-2-1) to the formula (1-2-6) as one of the raw materials of the polymer constituting the liquid crystal aligning agent of the present invention, the diamine represented by the formula (1) is represented. When other diamines other than the above diamines are used together, gelation can be suppressed during polymer synthesis. It is considered that this is because the hydrogen of the amide group is replaced with the methyl group, and the interaction between the molecules due to the hydrogen bond disappears.

The tetracarboxylic dianhydride can be roughly classified into a tetracarboxylic dianhydride having a photolytic structure and a tetracarboxylic dianhydride having no photolytic structure.

Regarding a tetracarboxylic dianhydride having no photodegradable structure, which is used for producing a liquid crystal aligning agent for photo-alignment containing at least one selected from the polyamic acid, polyamic acid ester and polyimide of the present invention explain.
The tetracarboxylic acid dianhydride having no photolytic structure used in the present invention can be selected from known tetracarboxylic acid dianhydrides having no photolytic structure without limitation. Tetracarboxylic acid dianhydrides that do not have such a photodegradable structure are aromatic systems (including heteroaromatic ring systems) in which a dicarboxylic acid anhydride is directly bonded to an aromatic ring, and direct dicarboxylic acid anhydrides to an aromatic ring. It may belong to any group of an aliphatic system (including a heterocyclic system) to which a substance is not bound.

Preferable examples of the tetracarboxylic dianhydride having no photodegradable structure are represented by the formula (AN-I) from the viewpoint of easy availability of raw materials, ease of polymer polymerization, and electric properties of the film. The tetracarboxylic acid dianhydride represented by (AN-VII) is mentioned.

Formula (AN-I), (AN -IV) and in (AN-V), X is independently a single bond or -CH ₂ -. In the formula (AN-II), G represents a single bond, an alkylene having 1 to 20 carbon atoms, -CO -, - O -, - S -, - SO 2 -, - C (CH 3) 2 -, or -C _{(CF 3) 2} - a. In formulas (AN-II) to (AN-IV), Y is independently one selected from the group of the following trivalent groups, the bond is linked to any carbon, and At least one hydrogen may be replaced with methyl, ethyl or phenyl.

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

More specifically, tetracarboxylic dianhydrides represented by the following formulas (AN-1) and (AN-3) to (AN-16-15) can be mentioned.

式（ＡＮ−１）において、Ｇ^１１は単結合、炭素数１〜１２のアルキレン、１，４−フェニレン、または１，４−シクロヘキシレンである。Ｘ^１１は独立して単結合または−ＣＨ_２−である。Ｇ^１２は独立して下記の３価の基のどちらかである。

Ｇ^１２が＞ＣＨ−であるとき、＞ＣＨ−の水素は−ＣＨ_３に置き換えられてもよい。Ｇ^１２が＞Ｎ−であるとき、Ｇ^１１が単結合および−ＣＨ_２−であることはなく、Ｘ^１１は単結合であることはない。そしてＲ^１１は水素または−ＣＨ_３である。 [Tetracarboxylic acid dianhydride represented by formula (AN-1)]

In formula (AN-1), G ¹¹ is a single bond, alkylene having 1 to 12 carbon atoms, 1,4-phenylene, or 1,4-cyclohexylene. X ¹¹ is independently a single bond or —CH ₂ —. G ¹² is independently one of the following trivalent groups.

When G ¹² is> CH- is,> CH- hydrogen may be replaced by -CH _3. When G ¹² is> ^{N-, G 11} is a single bond and -CH ₂ - that they are ^{not, X 11} is not a single bond. And R ¹¹ is hydrogen or —CH ₃ .

式（ＡＮ−１−２）および（ＡＮ−１−１４）において、ｍは１〜１２の整数である。 Examples of the tetracarboxylic dianhydride represented by the formula (AN-1) include compounds represented by the following formula.

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

式（ＡＮ−３）において、環Ａ^１１はベンゼン環である。 [Tetracarboxylic acid dianhydride represented by formula (AN-3)]

In formula (AN-3), ring A ¹¹ is a benzene ring.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-3) include compounds represented by the following formulas.

式（ＡＮ−４）において、Ｇ^１３は単結合、−（ＣＨ_２）_ｍ−、−Ｏ−、−Ｓ−、−Ｃ（ＣＨ_３）_２−、−ＳＯ_２−、−ＣＯ−、−Ｃ（ＣＦ_３）_２−、または下記の式（Ｇ１３−１）で表される２価の基であり、ｍは１〜１２の整数である。環Ａ^１１はそれぞれ独立してシクロヘキサン環またはベンゼン環である。Ｇ^１３は環Ａ^１１の任意の位置に結合してよい。

式（Ｇ１３−１）において、Ｇ^１３ａおよびＧ^１３ｂはそれぞれ独立して、単結合、−Ｏ−または−ＮＨＣＯ−で表される２価の基である。フェニレンは、１，４−フェニレンおよび１，３−フェニレンが好ましい。 [Tetracarboxylic acid dianhydride represented by formula (AN-4)]

In the formula ^{(AN-4), G 13} represents a single _{bond, - (CH 2) m -} , - O -, - S -, - C (CH 3) 2 -, - SO 2 -, - CO -, - C _{(CF 3) 2} -, or a divalent group represented by the formula (G13-1) below, m is an integer from 1 to 12. Rings A ¹¹ are each independently a cyclohexane ring or a benzene ring. G ¹³ may be attached at any position on ring A ¹¹ .

In formula (G13-1), G ^13a and G ^13b are each independently a single bond, or a divalent group represented by —O— or —NHCO—. Phenylene is preferably 1,4-phenylene and 1,3-phenylene.

式（ＡＮ−４−１７）において、ｍは１〜１２の整数である。

Examples of the tetracarboxylic dianhydride represented by the formula (AN-4) include compounds represented by the following formulas.

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

式（ＡＮ−５）において、Ｒ^１１は水素、または−ＣＨ_３である。ベンゼン環を構成する炭素原子に結合位置が固定されていないＲ^１１は、ベンゼン環における結合位置が任意であることを示す。 [Tetracarboxylic acid dianhydride represented by formula (AN-5)]

In formula (AN-5), R ¹¹ is hydrogen or —CH ₃ . R ¹¹ in which the bonding position is not fixed to the carbon atom forming the benzene ring indicates that the bonding position in the benzene ring is arbitrary.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-5) include compounds represented by the following formulas.

式（ＡＮ−６）において、Ｘ^１１は独立して単結合または−ＣＨ_２−である。Ｘ^１２は−ＣＨ_２−、−ＣＨ_２ＣＨ_２−または−ＣＨ＝ＣＨ−である。ｎは１または２である。 [Tetracarboxylic acid dianhydride represented by formula (AN-6)]

In formula (AN-6), X ¹¹ is independently a single bond or —CH ₂ —. X ¹² is _{-CH 2 -, - CH 2 CH} 2 - or -CH = CH-. n is 1 or 2.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-6) include compounds represented by the following formulas.

式（ＡＮ−７）において、Ｘ^１１は−ＣＨ_２−である。 [Tetracarboxylic acid dianhydride represented by formula (AN-7)]

In the formula (AN-7), X ¹¹ is —CH ₂ —.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-7) include compounds represented by the following formulas.

式（ＡＮ−８）において、Ｘ^１１は単結合または−ＣＨ_２−である。Ｒ^１２は水素、−ＣＨ_３、−ＣＨ_２ＣＨ_３、またはフェニルであり、環Ａ^１２はシクロヘキサン環またはシクロヘキセン環である。 [Tetracarboxylic acid dianhydride represented by formula (AN-8)]

In the formula (AN-8), X ¹¹ is a single bond or —CH ₂ —. R ¹² is hydrogen, —CH ₃ , —CH ₂ CH ₃ , or phenyl, and ring A ¹² is a cyclohexane ring or a cyclohexene ring.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-8) include compounds represented by the following formulas.

式（ＡＮ−９）において、ｒはそれぞれ独立して０または１である。 [Tetracarboxylic acid dianhydride represented by formula (AN-9)]

In formula (AN-9), r is 0 or 1 each independently.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-9) include compounds represented by the following formulas.

[Tetracarboxylic acid dianhydride represented by formula (AN-10-1) and formula (AN-10-2)]

式（ＡＮ−１１）において、環Ａ^１１は独立してシクロヘキサン環またはベンゼン環である。 [Tetracarboxylic acid dianhydride represented by formula (AN-11)]

In formula (AN-11), ring A ¹¹ is independently a cyclohexane ring or a benzene ring.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-11) include compounds represented by the following formulas.

式（ＡＮ−１２）において、環Ａ^１１はそれぞれ独立してシクロヘキサン環またはベンゼン環である。 [Tetracarboxylic acid dianhydride represented by formula (AN-12)]

In formula (AN-12), each ring A ¹¹ is independently a cyclohexane ring or a benzene ring.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-12) include compounds represented by the following formulas.

式（ＡＮ−１３）において、Ｘ^１３は炭素数２〜６のアルキレンであり、Ｐｈはフェニルを表す。 [Tetracarboxylic acid dianhydride represented by formula (AN-13)]

In the formula (AN-13), X ¹³ is alkylene having 2 to 6 carbon atoms, and Ph represents phenyl.

式（ＡＮ−１３−１）において、Ｐｈはフェニルを表す。 Examples of the tetracarboxylic dianhydride represented by the formula (AN-13) include compounds represented by the following formulas.

In Formula (AN-13-1), Ph represents phenyl.

式（ＡＮ−１４）において、Ｇ^１４は独立して−Ｏ−、−ＣＯＯ−または−ＯＣＯ−であり、ｒは独立して０または１である。 [Tetracarboxylic acid dianhydride represented by formula (AN-14)]

In formula (AN-14), G ¹⁴ is independently —O—, —COO— or —OCO—, and r is independently 0 or 1.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-14) include compounds represented by the following formulas.

式（ＡＮ−１５）において、ｗは１〜１０の整数である。 [Tetracarboxylic acid dianhydride represented by the formula (AN-15)]

In formula (AN-15), w is an integer of 1 to 10.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-15) include compounds represented by the following formula.

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

In the above tetracarboxylic dianhydride having no photodegradable structure, suitable materials for improving each property will be described.

When importance is attached to improving the orientation of the liquid crystal, compounds represented by formulas (AN-1), (AN-3), and (AN-4) are preferable, and compounds represented by formula (AN-1-2) are preferable. , (AN-1-13), (AN-3-2), (AN-4-5), (AN-4-17) and (AN-4-29) are particularly preferable, and among them, In formula (AN-1-2), m=4 or 8 is preferable, and in formula (AN-4-17), m=4 or 8 is preferable, and m=8 is particularly preferable.

When it is important to improve the transmittance of the liquid crystal display element, among the above tetracarboxylic dianhydrides, the compounds represented by the formulas (AN-1-1), (AN-1-2) and (AN-4-) are used. 17), (AN-4-30), (AN-5-1), (AN-7-2), (AN-10-1), (AN-16-3), and (AN-16-4). ) Is preferable, and in formula (AN-1-2), m=4 or 8 is preferable, and in formula (AN-4-17), m=4 or 8 is preferable. , M=8 is particularly preferable.

When it is important to improve the VHR of the liquid crystal display element, among the above tetracarboxylic dianhydrides, the compounds represented by the formulas (AN-1-1), (AN-1-2), and (AN-4-17) are used. ), (AN-4-30), (AN-7-2), (AN-10-1), (AN-16-1), (AN-16-3), and (AN-16-4). In the formula (AN-1-2), m=4 or 8 is preferable, and in the formula (AN-4-17), m=4 or 8 is preferable. m=8 is particularly preferred.

Improving the relaxation rate of the residual charge (residual DC) in the alignment film by lowering the volume resistance value of the liquid crystal alignment film is effective as one of the methods for preventing image sticking. When this purpose is emphasized, among the above tetracarboxylic acid dianhydrides, formulas (AN-1-13), (AN-3-2), (AN-4-21), (AN-4-) are used. 29), and the compounds represented by (AN-11-3) are preferable.

In the acid dianhydride used for the polymer using the monomer having no photodegradable structure, when importance is placed on improving the orientation of the liquid crystal, formulas (AN-1-1) and (AN -1-2), (AN-1-13), (AN-4-17) and compounds represented by (AN-4-29) are particularly preferable, and in formula (AN-1-2), It is preferable that m=4 or 8, and in the formula (AN-4-17), m=4 or 8 is preferable.

When importance is attached to improving the transmittance of the liquid crystal display element, among the above-mentioned acid dianhydrides, one of formulas (AN-1-1), (AN-1-2) and (AN-4-17) is used. , (AN-4-30), (AN-5-1), (AN-7-2), (AN-10), (AN-16-3), and (AN-16-4). In the formula (AN-1-2), m=4 or 8 is preferable, and in the formula (AN-4-17), m=4 or 8 is preferable, and m=8. Is particularly preferable.

When importance is attached to improving the VHR of the liquid crystal display element, among the above-mentioned acid dianhydrides, one of formulas (AN-1-1), (AN-1-2), (AN-4-17), Represented by (AN-4-30), (AN-7-2), (AN-10), (AN-16-1), (AN-16-3), and (AN-16-4). Compounds are preferable, and in formula (AN-1-2), m=4 or 8 is preferable, and in formula (AN-4-17), m=4 or 8 is preferable, and m=8 is Particularly preferred.

Improving the relaxation rate of the residual charge (residual DC) in the alignment film by lowering the volume resistance value of the liquid crystal alignment film is effective as one of the methods for preventing image sticking. When this purpose is emphasized, among the above-mentioned acid dianhydrides, formulas (AN-1-13), (AN-3-2), (AN-4-21), and (AN-4-29) are used. , And compounds represented by (AN-11-3) are preferable.

Diamine and dihydrazide other than the diamine represented by the formula (1), which is used for producing a liquid crystal aligning agent for photo-alignment containing at least one selected from the polyamic acid, polyamic acid ester and polyimide of the present invention explain. In producing the liquid crystal aligning agent for photoalignment of the present invention, known diamines and dihydrazides can be selected without limitation.

Diamines can be divided into two types depending on their structure. That is, when the skeleton connecting two amino groups is viewed as a main chain, it is a diamine having a group branched from the main chain, that is, a diamine having a side chain group and a diamine having no side chain group. This side chain group is a group having an effect of increasing the pretilt angle. The side chain group having such an effect needs to be a group having 3 or more carbon atoms, and specific examples thereof include alkyl having 3 or more carbon atoms, alkoxy having 3 or more carbon atoms, alkoxyalkyl having 3 or more carbon atoms, and The group which has a steroid skeleton can be mentioned. A group having one or more rings, the terminal ring of which has as a substituent any one of alkyl having 1 or more carbon atoms, alkoxy having 1 or more carbon atoms and alkoxyalkyl having 2 or more carbon atoms. It has an effect as a side chain group. In the following description, a diamine having such a side chain group may be referred to as a side chain type diamine. A diamine having no such side chain group may be referred to as a non-side chain type diamine.

By properly using the non-side chain type diamine and the side chain type diamine, it is possible to correspond to the respective pretilt angles required. The side chain type diamine is preferably used in combination to the extent that the characteristics of the present invention are not impaired. Further, it is preferable to select and use the side chain type diamine and the non-side chain type diamine for the purpose of improving vertical alignment property with respect to liquid crystal, voltage holding ratio, burn-in property and alignment property.

The non-side chain type diamine will be described. Examples of the known diamine having no side chain include the diamines of the following formulas (DI-1) to (DI-16).

In the above formula (DI-1), G ²⁰ is —CH ₂ —, at least one —CH ₂ — may be replaced by —NH—, —O—, and m is an integer of 1 to 12. And at least one hydrogen of the alkylene may be replaced with -OH. In formula (DI-3) and formula (DI-5) to formula (DI-7), G ²¹ is independently a single bond, —NH—, —NCH ₃ —, —O—, —S—, —S. _{-S -, - SO 2 -,} - CO -, - COO -, - CONCH 3 -, - CONH -, - C (CH 3) 2 -, - C (CF 3) 2 -, - (CH 2) m _{-, - O- (CH 2)} m -O -, - N (CH 3) - (CH 2) k -N (CH 3) -, - (O-C 2 H 4) m -O -, - O _{-CH 2 -C (CF 3) 2} -CH 2 -O -, - O-CO- (CH 2) m -CO-O -, - CO-O- (CH 2) m -O-CO -, - _{(CH 2) m -NH- (CH} 2) m -, - CO- (CH 2) k -NH- (CH 2) k -, - (NH- (CH 2) m) k -NH -, - CO _{-C 3 H 6 - (NH-} C 3 H 6) n -CO -, - (CH 2) k -NH-CO-NH- (CH 2) k -, or -S- _{(CH 2)} m -S -, m is independently an integer of 1 to 12, k is an integer of 1 to 5, and n is 1 or 2. In formula (DI-4), s is independently an integer of 0-2. In formula (DI-6) and formula ^{(DI-7), G 22} are independently a single bond, -O -, - S -, - CO -, - C (CH 3) 2 -, - C (CF 3 ) _2- or alkylene having 1 to 10 carbon atoms. Formula (DI-2) at least one hydrogen of cyclohexane ring and benzene ring in ~ formula (DI-7) is, -F, -Cl, alkylene of 1 to 3 carbon _atoms, -OCH _{3, -OH,} -CF _{3, -CO 2 H, -CONH 2} , -NHC 6 H 5, may be replaced by phenyl or benzyl, in the addition formula (DI-4), at least one hydrogen of cyclohexane ring and benzene ring It may be replaced with one selected from the group of groups represented by the following formulas (DI-4-a) to (DI-4-e). A group in which the bonding position is not fixed to the carbon atoms forming the ring indicates that the bonding position in the ring is arbitrary. The bonding position of —NH ₂ to the cyclohexane ring or the benzene ring is any position except the bonding position of G ²¹ or G ²² .

式（ＤＩ−４−ａ）および式（ＤＩ−４−ｂ）において、Ｒ^２０は独立して水素または−ＣＨ_３である。

In formula (DI-4-a) and formula (DI-4-b), R ²⁰ is independently hydrogen or —CH ₃ .

式（ＤＩ−１１）において、ｒは０または１である。式（ＤＩ−８）〜式（ＤＩ−１１）において、環に結合する−ＮＨ_２の結合位置は、任意の位置である。

In the formula (DI-11), r is 0 or 1. In formulas (DI-8) to (DI-11), the bonding position of —NH ₂ bonded to the ring is an arbitrary position.

In formula (DI-12), R ²¹ and R ²² are independently alkyl or phenyl having 1 to 3 carbon atoms, and G ²³ is independently alkylene, phenylene, or alkyl-substituted phenylene having 1 to 6 carbon atoms. And w is an integer of 1-10. In formula (DI-13), R ²³ is independently alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons or —Cl, p is independently an integer of 0 to 3, and q is It is an integer of 0-4. In formula (DI-14), ring B is a monocyclic heterocyclic aromatic group, R ²⁴ is hydrogen, —F, —Cl, alkyl having 1 to 6 carbons, alkoxy, vinyl, alkynyl, q is independently an integer of 0-4. In the formula (DI-15), ring C is a heterocyclic aromatic group or a heterocyclic aliphatic group. In formula (DI-16), G ²⁴ is a single bond, C 2-6 alkylene or 1,4-phenylene, and r is 0 or 1. Then, a group in which the bonding position is not fixed to the carbon atom forming the ring indicates that the bonding position in the ring is arbitrary. In formulas (DI-13) to (DI-16), the bonding position of —NH ₂ bonded to the ring is an arbitrary position.

Specific examples of the following formulas (DI-1-1) to (DI-16-1) are listed as diamines having no side chains of the above formulas (DI-1) to (DI-16). it can.

式（ＤＩ−１−７）および式（ＤＩ−１−８）において、ｋはそれぞれ独立して、１〜３の整数である。 Examples of the diamine represented by the formula (DI-1) are shown below.

In Formula (DI-1-7) and Formula (DI-1-8), k is an integer of 1-3 each independently.

Examples of the diamines represented by the formulas (DI-2) to (DI-3) are shown below.

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

式（ＤＩ−５−１）において、ｍは１〜１２の整数である。

式（ＤＩ−５−１２）および式（ＤＩ−５−１３）において、ｍは１〜１２の整数である。

式（ＤＩ−５−１６）において、ｖは１〜６の整数である。

式（ＤＩ−５−３０）において、ｋは１〜５の整数である。

式（ＤＩ−５−３５）〜式（ＤＩ−５−３７）、および式（ＤＩ−５−３９）において、ｍは独立して１〜１２の整数であり、式（ＤＩ−５−３８）、式（ＤＩ−５−３９）および式（ＤＩ−５−４２）において、ｋは独立して１〜５の整数であり、式（ＤＩ−５−４０）において、ｎは１または２の整数である。 Examples of the diamine represented by the formula (DI-5) are shown below.

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

In Formula (DI-5-12) and Formula (DI-5-13), m is an integer of 1-12.

In the formula (DI-5-16), v is an integer of 1 to 6.

In the formula (DI-5-30), k is an integer of 1 to 5.

In formula (DI-5-35) to formula (DI-5-37) and formula (DI-5-39), m is independently an integer of 1 to 12, formula (DI-5-38) In formula (DI-5-39) and formula (DI-5-42), k is independently an integer of 1 to 5, and in formula (DI-5-40), n is an integer of 1 or 2. Is.

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

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

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

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

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

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

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

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

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

Examples of the diamine represented by the formula (DI-13) are shown below.

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

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

Examples of the diamine represented by the formula (DI-16) are shown below.

The dihydrazide will be described. Examples of the known dihydrazide having no side chain include the following formulas (DIH-1) to (DIH-3).

In formula (DIH-1), G ²⁵ is a single bond, alkylene having 1 to 20 carbon atoms, —CO—, —O—, —S—, —SO ₂ —, —C(CH ₃ ) ₂ —, or —. C _{(CF 3) 2} - a. In formula (DIH-2), ring D is a cyclohexane ring, a benzene ring or a naphthalene ring, and at least one hydrogen of this group may be replaced by methyl, ethyl, or phenyl. In formula (DIH-3), each ring E is independently a cyclohexane ring or a benzene ring, at least one hydrogen of this group may be replaced by methyl, ethyl, or phenyl, and Y is a single bond, alkylene having 1 to 20 carbon atoms, -CO -, - O -, - S -, - SO 2 -, - C (CH 3) 2 -, or -C _{(CF 3) 2} - a. In formula (DIH-2) and formula (DIH-3), the bonding position of —CONHNH ₂ bonded to the ring is an arbitrary position.

式（ＤＩＨ−１−２）において、ｍは１〜１２の整数である。

Examples of formulas (DIH-1) to (DIH-3) are shown below.

In the formula (DIH-1-2), m is an integer of 1-12.

Such non-side chain type diamines and hydrazides have the effect of improving the electrical characteristics such as lowering the ion density of the liquid crystal display element. When a non-side chain type diamine and/or dihydrazide is used as the diamine used for producing the liquid crystal aligning agent for photo-alignment, which is used for the liquid crystal aligning agent of the present invention, polyamic acid, polyamic acid ester or polyimide, diamine and dihydrazide are used. The proportion of the total amount of the above is preferably 0 to 90 mol %, and more preferably 0 to 50 mol %.

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

First as a side chain group, alkyl, alkyloxy, alkyloxyalkyl, alkylcarbonyl, alkylcarbonyloxy, alkyloxycarbonyl, alkylaminocarbonyl, alkenyl, alkenyloxy, alkenylcarbonyl, alkenylcarbonyloxy, alkenyloxycarbonyl, alkenylaminocarbonyl, Examples thereof include alkynyl, alkynyloxy, alkynylcarbonyl, alkynylcarbonyloxy, alkynyloxycarbonyl and alkynylaminocarbonyl. Alkyl, alkenyl and alkynyl in these groups are all groups having 3 or more carbon atoms. However, in the case of alkyloxyalkyl, the number of carbon atoms in the entire group is 3 or more. These groups may be linear or branched.

Next, phenyl, phenylalkyl, phenylalkyloxy, phenyloxy, provided that the terminal ring has alkyl having 1 or more carbon atoms, alkoxy having 1 or more carbon atoms or alkoxyalkyl having 2 or more carbon atoms as a substituent, Phenylcarbonyl, phenylcarbonyloxy, phenyloxycarbonyl, phenylaminocarbonyl, phenylcyclohexyloxy, cycloalkyl having 3 or more carbon atoms, cyclohexylalkyl, cyclohexyloxy, cyclohexyloxycarbonyl, cyclohexylphenyl, cyclohexylphenylalkyl, cyclohexylphenyloxy, bis( Ring structures such as cyclohexyl)oxy, bis(cyclohexyl)alkyl, bis(cyclohexyl)phenyl, bis(cyclohexyl)phenylalkyl, bis(cyclohexyl)oxycarbonyl, bis(cyclohexyl)phenyloxycarbonyl, and cyclohexylbis(phenyl)oxycarbonyl The following groups can be mentioned.

Furthermore, a group having two or more benzene rings, a group having two or more cyclohexane rings, or two or more rings composed of a benzene ring and a cyclohexane ring, wherein the bonding groups are independently a single bond, -O-, -COO-, -OCO-, -CONH- or alkylene having 1 to 3 carbon atoms, and the terminal ring is a substituent having 1 or more carbon atoms, fluorine having 1 or more carbon atoms, carbon Examples thereof include ring assembly groups having an alkoxy having a number of 1 or more, or an alkoxyalkyl having a carbon number of 2 or more. A group having a steroid skeleton is also effective as a side chain group.

式（ＤＩ−３１）において、Ｇ^２６は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−、−ＣＯＮＨ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、または−（ＣＨ_２）_ｍ’−であり、ｍ’は１〜１２の整数である。Ｇ^２６の好ましい例は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ_２Ｏ−、および炭素数１〜３のアルキレンであり、特に好ましい例は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ_２Ｏ−、−ＣＨ_２−および−ＣＨ_２ＣＨ_２−である。Ｒ^２５は炭素数３〜３０のアルキル、フェニル、ステロイド骨格を有する基、または下記の式（ＤＩ−３１−ａ）で表される基である。このアルキルにおいて、少なくとも１つの水素は−Ｆで置き換えられてもよく、そして少なくとも１つの−ＣＨ_２−は−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられていてもよい。このフェニルの水素は、−Ｆ、−ＣＨ_３、−ＯＣＨ_３、−ＯＣＨ_２Ｆ、−ＯＣＨＦ_２、−ＯＣＦ_３、炭素数３〜３０のアルキルまたは炭素数３〜３０のアルコキシで置き換えられていてもよい。ベンゼン環に結合する−ＮＨ_２の結合位置はその環において任意の位置であることを示すが、その結合位置はメタまたはパラであることが好ましい。即ち、基「Ｒ^２５−Ｇ^２６−」の結合位置を１位としたとき、２つの結合位置は３位と５位、または２位と５位であることが好ましい。 Examples of the diamine having a side chain include compounds represented by the following formulas (DI-31) to (DI-35).

In the formula (DI-31), G ²⁶ is a single bond, —O—, —COO—, —OCO—, —CO—, —CONH—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—. , -OCF ₂ -, or - _(CH 2) _{m '-} it is and, m' is an integer from 1 to 12. Preferred examples of G ²⁶ represents a single bond, -O -, - COO -, - OCO -, - CH 2 O-, and alkylene having 1 to 3 carbon atoms, particularly preferred examples are a single bond, -O -, - _{COO -, - OCO -, -} CH 2 O -, - CH 2 - and _-CH 2 CH ₂ -. R ²⁵ is an alkyl group having 3 to 30 carbon atoms, phenyl, a group having a steroid skeleton, or a group represented by the following formula (DI-31-a). In the alkyl, at least one hydrogen may be replaced by -F, and at least one -CH ₂ - is -O -, - CH = CH- or may be replaced by -C≡C-. Hydrogen which _{phenyl, -F, -CH 3, -OCH 3} , -OCH 2 F, -OCHF 2, -OCF 3, be replaced by an alkoxy alkyl or 3 to 30 carbon atoms having 3 to 30 carbon atoms Good. The bonding position of —NH ₂ bonded to the benzene ring is shown to be an arbitrary position in the ring, but the bonding position is preferably meta or para. That is, when the bonding position of the group "R ²⁵ -G ²⁶ -" is the 1-position, the two bonding positions are preferably the 3-position and the 5-position, or the 2-position and the 5-position.

式（ＤＩ−３１−ａ）において、Ｇ^２７、Ｇ^２８およびＧ^２９は結合基であり、これらは独立して単結合、または炭素数１〜１２のアルキレンであり、このアルキレンの１以上の−ＣＨ_２−は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＣＨ＝ＣＨ−で置き換えられていてもよい。環Ｂ^２１、環Ｂ^２２、環Ｂ^２３および環Ｂ^２４は独立して１，４−フェニレン、１，４−シクロへキシレン、１，３−ジオキサン−２，５−ジイル、ピリミジン−２，５−ジイル、ピリジン−２，５−ジイル、ナフタレン−１，５−ジイル、ナフタレン−２，７−ジイルまたはアントラセン−９，１０−ジイルであり、環Ｂ^２１、環Ｂ^２２、環Ｂ^２３および環Ｂ^２４において、少なくとも１つの水素は−Ｆまたは−ＣＨ_３で置き換えられてもよく、ｓ、ｔおよびｕは独立して０〜２の整数であって、これらの合計は１〜５であり、ｓ、ｔまたはｕが２であるとき、各々の括弧内の２つの結合基は同じであっても異なってもよく、そして、２つの環は同じであっても異なっていてもよい。Ｒ^２６は水素、−Ｆ、−ＯＨ、炭素数１〜３０のアルキル、炭素数１〜３０のフッ素置換アルキル、炭素数１〜３０のアルコキシ、−ＣＮ、−ＯＣＨ_２Ｆ、−ＯＣＨＦ_２、または−ＯＣＦ_３であり、この炭素数１〜３０のアルキルの少なくとも１つの−ＣＨ_２−は下記式（ＤＩ−３１−ｂ）で表される２価の基で置き換えられていてもよい。

In formula (DI-31-a), G ²⁷ , G ^28, and G ²⁹ are bonding groups, which are independently a single bond or an alkylene having 1 to 12 carbons, and one or more of these alkylenes are -. CH ₂ - is -O -, - COO -, - OCO -, - CONH -, - it may be replaced by CH = CH-. Ring B ²¹ , ring B ²² , ring B ²³ and ring B ²⁴ are independently 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5. - diyl, pyridine-2,5-diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl or anthracene-9,10-diyl, ring ^{B 21,} ring ^{B 22,} ring ^{B 23} and ring in B ^24, at least one hydrogen may be replaced by -F, or -CH _3, s, t and u is an integer of 0 to 2 independently, their sum is 1-5, When s, t or u is 2, the two linking groups within each bracket may be the same or different, and the two rings may be the same or different. R ²⁶ is hydrogen, —F, —OH, alkyl having 1 to 30 carbons, fluorine-substituted alkyl having 1 to 30 carbons, alkoxy having 1 to 30 carbons, —CN, —OCH ₂ F, —OCHF ₂ , or is -OCF _3, at least one -CH ₂ alkyl of 1 to 30 carbon atoms - may be replaced by a divalent group represented by the following formula (DI-31-b).

式（ＤＩ−３１−ｂ）において、Ｒ^２７およびＲ^２８は独立して炭素数１〜３のアルキルであり、ｖは１〜６の整数である。Ｒ^２６の好ましい例は炭素数１〜３０のアルキルおよび炭素数１〜３０のアルコキシである。

In formula (DI-31-b), R ²⁷ and R ²⁸ are independently alkyl having 1 to 3 carbons, and v is an integer of 1 to 6. Preferred examples of R ²⁶ are alkyl having 1 to 30 carbons and alkoxy having 1 to 30 carbons.

In formula (DI-32) and formula (DI-33), G ³⁰ is independently a single bond, —CO— or —CH ₂ —, R ²⁹ is independently hydrogen or —CH ₃ , and R 30 is ³⁰ is hydrogen, alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons. At least one hydrogen of the benzene ring in formula (DI-33) may be replaced with alkyl having 1 to 20 carbons or phenyl. A group in which the bonding position is not fixed to any carbon atom forming the ring indicates that the bonding position in the ring is arbitrary. Formula (DI-32) in two groups - one of the "phenylene -G 30 ^-O-" is attached to the 3 position of the steroid nucleus, it is preferable that the other is bound to 6-position of the steroid nucleus. The bonding positions of the two groups “-phenylene-G ³⁰ —O—” in the formula (DI-33) to the benzene ring are preferably meta or para to the bonding position of the steroid nucleus. In formula (DI-32) and formula (DI-33), —NH ₂ bonded to the benzene ring indicates that the bonding position in the ring is arbitrary.

In formula (DI-34) and formula (DI-35), G ³¹ is independently —O— or alkylene having 1 to 6 carbons, and G ³² is a single bond or alkylene having 1 to 3 carbons. .. R ³¹ is hydrogen or alkyl having 1 to 20 carbons, and at least one —CH ₂ — of this alkyl may be replaced by —O—, —CH═CH— or —C≡C—. R ³² is alkyl having 6 to 22 carbons, and R ³³ is hydrogen or alkyl having 1 to 22 carbons. Ring B ²⁵ is 1,4-phenylene or 1,4-cyclohexylene, and r is 0 or 1. And -NH ₂ bonded to the benzene ring indicates that the bonding position in the ring is arbitrary, but it is preferably independently in the meta position or the para position with respect to the bonding position of G ³¹ .

Specific examples of the side chain type diamine are illustrated below. Examples of the diamine having a side chain of the formula (DI-31) to the formula (DI-35) include compounds represented by the following formula (DI-31-1) to the formula (DI-35-3). it can.

Examples of the compound represented by the formula (DI-31) are shown below.

In formulas (DI-31-1) to (DI-31-11), R ³⁴ is alkyl having 1 to 30 carbons or alkoxy having 1 to 30 carbons, preferably alkyl having 5 to 25 carbons or It is an alkoxy having 5 to 25 carbon atoms. R ³⁵ is alkyl having 1 to 30 carbons or alkoxy having 1 to 30 carbons, preferably alkyl having 3 to 25 carbons or alkoxy having 3 to 25 carbons.

式（ＤＩ−３１−１２）〜式（ＤＩ−３１−１７）において、Ｒ^３６は炭素数４〜３０のアルキルであり、好ましくは炭素数６〜２５のアルキルである。Ｒ^３７は炭素数６〜３０のアルキルであり、好ましくは炭素数８〜２５のアルキルである。

In formulas (DI-31-12) to (DI-31-17), R ³⁶ is alkyl having 4 to 30 carbons, preferably alkyl having 6 to 25 carbons. R ³⁷ is alkyl having 6 to 30 carbon atoms, preferably alkyl having 8 to 25 carbon atoms.

式（ＤＩ−３１−１８）〜式（ＤＩ−３１−４３）において、Ｒ^３８は炭素数１〜２０のアルキルまたは炭素数１〜２０のアルコキシであり、好ましくは炭素数３〜２０のアルキルまたは炭素数３〜２０のアルコキシである。Ｒ^３９は水素、−Ｆ、炭素数１〜３０のアルキル、炭素数１〜３０のアルコキシ、−ＣＮ、−ＯＣＨ_２Ｆ、−ＯＣＨＦ_２または−ＯＣＦ_３であり、好ましくは炭素数３〜２５のアルキル、または炭素数３〜２５のアルコキシである。そしてＧ^３３は炭素数１〜２０のアルキレンである。

In formulas (DI-31-18) to (DI-31-43), R ³⁸ is alkyl having 1 to 20 carbons or alkoxy having 1 to 20 carbons, preferably alkyl having 3 to 20 carbons or It is an alkoxy having 3 to 20 carbon atoms. R ³⁹ is hydrogen, —F, alkyl having 1 to 30 carbons, alkoxy having 1 to 30 carbons, —CN, —OCH ₂ F, —OCHF ₂ or —OCF ₃ , and preferably ₃ to 25 carbons. Alkyl or alkoxy having 3 to 25 carbon atoms. G ³³ is alkylene having 1 to 20 carbon atoms.

Examples of the compound represented by the formula (DI-32) are shown below.

Examples of the compound represented by the formula (DI-33) are shown below.

式（ＤＩ−３４−１）〜式（ＤＩ−３４−１２）において、Ｒ^４０は水素または炭素数１〜２０のアルキル、好ましくは水素または炭素数１〜１０のアルキルであり、そしてＲ^４１は水素または炭素数１〜１２のアルキルである。 Examples of the compound represented by the formula (DI-34) are shown below.

In formulas (DI-34-1) to (DI-34-12), R ⁴⁰ is hydrogen or alkyl having 1 to 20 carbons, preferably hydrogen or alkyl having 1 to 10 carbons, and R ⁴¹ is It is hydrogen or alkyl having 1 to 12 carbons.

式（ＤＩ−３５−１）〜式（ＤＩ−３５−３）において、Ｒ^３７は炭素数６〜３０のアルキルであり、Ｒ^４１は水素または炭素数１〜１２のアルキルである。 Examples of the compound represented by the formula (DI-35) are shown below.

In formulas (DI-35-1) to (DI-35-3), R ³⁷ is alkyl having 6 to 30 carbons, and R ⁴¹ is hydrogen or alkyl having 1 to 12 carbons.

式（ＤＩ−３６−１）〜式（ＤＩ−３６−８）において、Ｒ^４２はそれぞれ独立して炭素数３〜３０のアルキル基を表す。 Examples of the diamine in the present invention include formula (DI-1-1) to formula (DI-16-1), formula (DIH-1-1) to formula (DIH-3-6) and formula (DI-31-1). )-Diamine other than the diamine represented by the formula (DI-35-3) can be used. Examples of such diamines include compounds represented by the following formulas (DI-36-1) to (DI-36-13).

In formulas (DI-36-1) to (DI-36-8), each R ⁴² independently represents an alkyl group having 3 to 30 carbon atoms.

式（ＤＩ−３６−９）〜式（ＤＩ−３６−１１）において、ｅは２〜１０の整数であり、式（ＤＩ−３６−１２）中、Ｒ^４３はそれぞれ独立して水素、−ＮＨＢｏｃまたは−Ｎ（Ｂｏｃ）_２であり、Ｒ^４３の少なくとも１つは−ＮＨＢｏｃまたは−Ｎ（Ｂｏｃ）_２であり、式（ＤＩ−３６−１３）において、Ｒ^４４は−ＮＨＢｏｃまたは−Ｎ（Ｂｏｃ）_２であり、そして、ｍは１〜１２の整数である。ここでＢｏｃはｔ−ブトキシカルボニル基である。

In Formula (DI-36-9) to Formula (DI-36-11), e is an integer of 2 to 10, and in Formula (DI-36-12), R ⁴³ is independently hydrogen or -NHBoc. Or -N(Boc) ₂ and at least one of R ⁴³ is -NHBoc or -N(Boc) ₂ , and in the formula (DI-36-13), R ⁴⁴ is -NHBoc or -N(Boc). ₂ and m is an integer from 1 to 12. Here, Boc is a t-butoxycarbonyl group.

In the above diamine and dihydrazide, suitable materials for improving each property will be described.

In the diamine and dihydrazide used in the polymer using the monomer having a photodegradable structure, when it is important to further improve the orientation of the liquid crystal, among the above diamine and dihydrazide, a compound represented by the formula (DI-1 -3), formula (DI-5-1), formula (DI-5-5), formula (DI-5-9), formula (DI-5-12), formula (DI-5-13), formula (DI-5-29), Formula (DI-6-7), Formula (DI-7-3), Formula (DI-11-2), and the diamine represented by Formula (DI-36-9). It is preferable to use, and in the formula (DI-5-1), m=2, 4 or 6 is preferable, m=4 is particularly preferable, and in the formula (DI-5-12), m=2-6 is preferable. , M=5 is particularly preferable, m=1 or 2 is preferable in formula (DI-5-13), m=1 is particularly preferable, and k=2 is particularly preferable in formula (DI-5-30). In the formula (DI-7-3), m=1, 2 or 3, and n=1 or 2 are preferable, m=1 is particularly preferable, and in the formula (DI-36-9), e=5 is preferable.

When importance is attached to improving the transmittance, among the above diamines and dihydrazides, the formula (DI-1-3), the formula (DI-2-1), the formula (DI-5-1), the formula ( DI-5-5), the formula (DI-5-17), and the diamine represented by the formula (DI-7-3) are preferably used, and the diamine represented by the (DI-2-1) is particularly preferable. preferable. In formula (DI-5-1), m=2, 4 or 6 is preferable, m=4 is particularly preferable, and in formula (DI-7-3), m=1, 2 or 3, n= 1 or 2 is preferable, and m=1 is particularly preferable.

When importance is placed on improving the VHR of the liquid crystal display element, among the above diamines and dihydrazides, the formula (DI-2-1), the formula (DI-4-1), the formula (DI-4-2) , Formula (DI-4-10), formula (DI-4-15), formula (DI-5-1), formula (DI-5-28), formula (DI-5-30), and formula (DI It is preferable to use the diamine represented by formula (13-1), especially the diamine represented by formula (DI-2-1), formula (DI-5-1), and formula (DI-13-1). preferable. Among them, in the formula (DI-5-1), m=1 is particularly preferable, and in the formula (DI-5-30), k=2 is particularly preferable.

Improving the relaxation rate of the residual charge (residual DC) in the alignment film by lowering the volume resistance value of the liquid crystal alignment film is effective as one of the methods for preventing image sticking. When this purpose is emphasized, among the above diamines and dihydrazides, the formula (DI-4-1), the formula (DI-4-2), the formula (DI-4-10), and the formula (DI-4-4). 15), formula (DI-5-1), formula (DI-5-12), formula (DI-5-13), formula (DI-5-28), and formula (DI-16-1). The diamine represented by the formula (DI-4-1), the formula (DI-5-1) or the formula (DI-5-13) is particularly preferable. Among them, in the formula (DI-5-1), m=2, 4 or 6 is preferable, m=4 is particularly preferable, and in the formula (DI-5-12), m=2 to 6 is preferable and m=5 is Particularly preferably, in the formula (DI-5-13), m=1 or 2 is preferable, and m=1 is particularly preferable.

In the diamine and dihydrazide used in the polymer that does not use a monomer having a photodegradable structure, the layer separation property, that is, in the case where it is important to further improve the orientation of the liquid crystal, among the above diamine and dihydrazide, Formula (DI-4-1), Formula (DI-4-2), Formula (DI-4-10), Formula (DI-5-1), Formula (DI-5-9), Formula (DI-5) -28), the formula (DI-5-42), and the diamine and dihydrazide represented by the formula (DIH-2-1) are preferably used, and in formula (DI-5-1), m=1, 2 or 4 is preferable, and m=1 or 2 is particularly preferable.

When importance is attached to improving the transmittance, among the above diamines and dihydrazides, the formula (DI-1-2), the formula (DI-2-1), the formula (DI-5-1), and the formula (DI-5-1) The diamine represented by (DI-7-3) is preferably used, and the diamine represented by the formula (DI-2-1) is particularly preferable. In the formula (DI-5-1), m=1, 2, or 4 is preferable, m=1 or 2 is particularly preferable, and in the formula (DI-5-42), k=2 is preferable.

When importance is placed on improving the VHR of the liquid crystal display element, among the above diamines and dihydrazides, the formula (DI-2-1), the formula (DI-4-1), the formula (DI-4-2) , Formula (DI-4-15), formula (DI-5-1), formula (DI-5-28), formula (DI-5-30), and formula (DI-13-1). A diamine is preferably used, and diamines represented by formula (DI-2-1), formula (DI-5-1), and formula (DI-13-1) are particularly preferable. Among them, in the formula (DI-5-1), m=1 or 2 is particularly preferable, and in the formula (DI-5-30), k=2 is particularly preferable.

Improving the relaxation rate of the residual charge (residual DC) in the alignment film by lowering the volume resistance value of the liquid crystal alignment film is effective as one of the methods for preventing image sticking. When this purpose is emphasized, among the above diamines and dihydrazides, the formula (DI-4-1), the formula (DI-4-2), the formula (DI-4-10), and the formula (DI-4-4). 15), formula (DI-5-1), formula (DI-5-9), formula (DI-5-12), formula (DI-5-13), formula (DI-5-28), formula ( DI-5-30) and a diamine represented by the formula (DI-16-1) are preferably used, and the formula (DI-4-1), the formula (DI-5-1), and the formula (DI-). The diamine represented by 5-12) is particularly preferable. Among them, in the formula (DI-5-1), m=1 or 2 is preferable, in the formula (DI-5-12), m=2 to 6 is preferable, m=5 is particularly preferable, and the formula (DI-5 In -13), m=1 or 2 is preferable, m=1 is particularly preferable, and in the formula (DI-5-30), k=2 is particularly preferable.

In each diamine, part of the diamine may be replaced with the monoamine in the range of the monoamine to diamine ratio of 40 mol% or less. Such replacement can cause termination of the polymerization reaction when producing the polyamic acid, and can suppress the further progress of the polymerization reaction. Therefore, by such replacement, the molecular weight of the resulting polymer (polyamic acid, polyamic acid ester or polyimide) can be easily controlled, and, for example, the coating properties of the liquid crystal aligning agent without impairing the effects of the present invention. Can be improved. The diamine to be replaced with the monoamine may be one kind or two or more kinds as long as the effect of the present invention is not impaired. Examples of the monoamine include aniline, 4-hydroxyaniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n- Undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, and n-eicosylamine Are listed.

The polyamic acid, polyamic acid ester and polyimide of the present invention may further contain a monoisocyanate compound in the monomer thereof. By including the monoisocyanate compound in the monomer, the end of the obtained polyamic acid or its derivative is modified and the molecular weight is adjusted. By using this end-modified polyamic acid or its derivative, the coating properties of the liquid crystal aligning agent can be improved without impairing the effects of the present invention. From the above viewpoint, the content of the monoisocyanate compound in the monomer is preferably 1 to 10 mol% with respect to the total amount of the diamine and the tetracarboxylic dianhydride in the monomer. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

The polyamic acid, polyamic acid ester and polyimide of the present invention can be obtained by reacting the above-mentioned acid anhydride mixture with a diamine in a solvent. In this synthetic reaction, no special conditions are required other than the selection of the raw materials, and the conditions for ordinary polyamic acid synthesis can be applied as they are. The solvent used will be described later.

The liquid crystal aligning agent for photo-alignment of the present invention may further contain components other than the polyamic acid, polyamic acid ester and polyimide of the present invention. The other component may be one type or two or more types. Other components include, for example, other polymers and compounds described later.

As the other polymer, a polyamic acid, a polyamic acid ester, or a polyimide (hereinafter, referred to as “other polyamic acid or "Derivative thereof"), polyester, polyamide, polysiloxane, cellulose derivative, polyacetal, polystyrene derivative, poly(styrene-phenylmaleimide) derivative, poly(meth)acrylate, and the like. It may be one kind or two or more kinds. Among these, other polyamic acids or their derivatives and polysiloxanes are preferable, and other polyamic acids or their derivatives are more preferable.

Examples of the tetracarboxylic dianhydride used for synthesizing other polyamic acid or its derivative include tetracarboxylic dianhydride used for synthesizing polyamic acid or its derivative which is an essential component of the liquid crystal aligning agent of the present invention. The anhydride can be selected from known tetracarboxylic acid dianhydrides without any limitation, and examples thereof include the same ones exemplified above.

Preferred tetracarboxylic acid dianhydrides include the tetracarboxylic acid dianhydrides used in the polymers that do not use the above-mentioned monomer having a photolytic structure.

The tetracarboxylic acid dianhydride used for synthesizing the other polyamic acid or its derivative is one containing aromatic tetracarboxylic acid dianhydride in an amount of 10 mol% or more based on the total tetracarboxylic acid dianhydride. Are preferred, and those containing 30 mol% or more are more preferred.

As the diamine and dihydrazide used for synthesizing the other polyamic acid or its derivative, other diamine and dihydrazide which can be used for synthesizing the polyamic acid or its derivative which is an essential component of the liquid crystal aligning agent of the present invention are used. Can be the same as those exemplified above.

Preferred diamines and dihydrazides include the diamines and dihydrazides used in polymers that do not use the above-mentioned monomer having a photodegradable structure.

The diamine used for synthesizing the other polyamic acid or the derivative thereof preferably contains the aromatic diamine in an amount of 30 mol% or more, and more preferably 50 mol% or more, based on all diamines.

The other polyamic acid or its derivative can be synthesized according to the method described below as a method for synthesizing the polyamic acid or its derivative which is an essential component of the liquid crystal aligning agent of the present invention.

As described above, in the liquid crystal aligning agent for photo-alignment of the present invention, at least one selected from the group consisting of tetracarboxylic dianhydride and its derivative and diamine has a photolytic structure, and the diamine has the formula ( 1) containing at least one of the polymers obtained by reacting a raw material monomer containing at least one of the compounds, or selected from the group consisting of tetracarboxylic dianhydrides and their derivatives, and diamines. At least one of the polymers obtained by reacting at least one raw material monomer having a photodegradable structure, tetracarboxylic dianhydride and its derivative, and diamine have no photodegradable structure, Further, it is a liquid crystal aligning agent for photo-alignment, in which the diamine simultaneously contains at least one of the polymers obtained by reacting the raw material monomer containing at least one of the compounds represented by the formula (1).

The liquid crystal aligning agent for photo-alignment of the present invention may contain at least two polymers. Of the two polymers, the polymer having a photodegradable structure is [A], and the polymer having no photodegradable structure is [B], the weight average molecular weight of the polymer [A] is the weight average molecular weight of the polymer [B]. By controlling the amount to be smaller than that, a liquid crystal aligning agent containing a mixture of both polymers is applied to the substrate and preliminarily dried. It is considered that the polymer [B] having no photolytic structure can be segregated in the lower layer. For this reason, the presence of the polymer [A] having a photodegradable structure is dominant on the surface of the alignment film, and the content of the polymer [A] having a photodegradable structure is small based on the total amount of the polymers forming the alignment film. However, the alignment film formed by the liquid crystal aligning agent for photo-alignment of the present invention exhibits high liquid crystal aligning property.

It is known that, in the process of forming a thin film using a liquid crystal aligning agent containing two polymers as described above, a polymer having a small surface energy is separated into an upper layer and a polymer having a large surface energy is separated into a lower layer. Whether or not the above-mentioned alignment film is layer-separated can be confirmed by, for example, measuring the surface energy of the formed film and confirming that it is the same as the value of the surface energy of the film formed by the liquid crystal aligning agent containing only the polymer [A]. , It can be confirmed by the value close to it.

The weight average molecular weight of the polymer is preferably adjusted by adjusting the polymer [A] to 8,000 to 40,000 and the polymer [B] to 50,000 to 200,000, preferably the molecular weight (Mw) of the polymer [A]. Is adjusted to 10,000 to 30,000, and the molecular weight (Mw) of the polymer [B] is adjusted to 80,000 to 160,000, whereby the layer separation as described above can be caused. The weight average molecular weight of the polymer can be adjusted by, for example, the time for reacting the tetracarboxylic dianhydride and the diamine. A small amount of the reaction liquid during the polymerization reaction is sampled, the weight average molecular weight of the polymer contained therein is determined by gel permeation chromatography (GPC) method, and the end point of the reaction can be determined by the measured value. Further, a method of controlling the weight average molecular weight by terminating the polymerization reaction by replacing the equivalent amount of tetracarboxylic dianhydride and diamine at the start of the reaction with monocarboxylic acid or monoamine is also well known. ..

In order to exhibit good photo-alignment property as described above, the content of the polymer [A] in the liquid crystal aligning agent for photo-alignment of the present invention is 20% by weight or more when the total amount of the polymer is 100% by weight. It is necessary to be present, preferably 30% by weight or more, and more preferably 50% by weight or more.

Examples of the polysiloxane include JP2009-036966A, JP2010-185001, JP2011-102963, JP2011-253175, JP2012-159825, International Publication 2008/044644, International Publication 2009/148099, International Publication. Disclosed in 2010/074261, International Publication 2010/074264, International Publication 2010/126108, International Publication 2011/068123, International Publication 2011/068127, International Publication 2011/068128, International Publication 2012/115157, International Publication 2012/165354, etc. The polysiloxane may further be contained.

<Alkenyl-substituted nadiimide compound>
For example, the liquid crystal aligning agent of the present invention may further contain an alkenyl-substituted nadimide compound for the purpose of stabilizing the electrical characteristics of the liquid crystal display device for a long period of time. The alkenyl-substituted nadiimide compounds may be used alone or in combination of two or more. From the above-mentioned purpose, the content of the alkenyl-substituted nadiimide compound is preferably 1 to 100% by weight, more preferably 1 to 70% by weight, and further preferably 1 to 50% by weight based on the polyamic acid or its derivative. Is more preferable.

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

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

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

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

In formula (NA), when n=2, W is alkylene having 2 to 20 carbon atoms, cycloalkylene having 5 to 8 carbon atoms, arylene having 6 to 12 carbon atoms, and -Z ¹ -O-(Z ² O). _k -Z ³ - ^(where the definition of Z 1 to Z ^3, and k are as defined above.) groups represented ^{by, -Z 4 -B-Z 5 -} ( ^{where Z} 4, Z defining ⁵ and B are as defined above. groups represented _{by), -B- (O-B)} r -T- (B-O) r -B- ( wherein, B is phenylene, T is an alkylene having 1 to 3 carbon atoms, —O— or —SO ₂ —, and r is as defined above.), or 1 to 3 hydrogens of these groups are It is a group replaced with —OH.

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

Such an alkenyl-substituted nadiimide compound is synthesized by holding an alkenyl-substituted nadic acid anhydride derivative and a diamine at a temperature of 80 to 220° C. for 0.5 to 20 hours, as described in, for example, Japanese Patent No. 2729565. The compound obtained by this and the compound marketed can be used. The following compounds may be mentioned as specific examples of the alkenyl-substituted nadiimide compound.

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

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

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

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

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

N-{2-(2-hydroxyethoxy)ethyl}-allyl(methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-{2-(2-hydroxyethoxy) ) Ethyl}-methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-{2-(2-hydroxyethoxy)ethyl}-methallylmethylbicyclo[2.2] .1] Hept-5-ene-2,3-dicarboximide, N-[2-{2-(2-(2-hydroxyethoxy)ethoxy}ethyl]-allylbicyclo[2.2.1]hept-5-ene -2,3-Dicarboximide, N-[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]-allyl(methyl)bicyclo[2.2.1]hept-5-ene-2,3- Dicarboximide, N-[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]-methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-{ 4-(4-hydroxyphenylisopropylidene)phenyl}-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-{4-(4-hydroxyphenylisopropylidene)phenyl }-Allyl(methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-{4-(4-hydroxyphenylisopropylidene)phenyl}-methallylbicyclo[2. 2.1] hept-5-ene-2,3-dicarboximide, and oligomers thereof,

N,N'-ethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide), N,N'-ethylene-bis(allylmethylbicyclo[2.2. 1] hept-5-ene-2,3-dicarboximide), N,N'-ethylene-bis(methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide) , N,N'-trimethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide), N,N'-hexamethylene-bis(allylbicyclo[2.2] .1]Hept-5-ene-2,3-dicarboximide), N,N'-hexamethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl) Imido), N,N′-dodecamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide), N,N′-dodecamethylene-bis(allylmethylbicyclo) [2.2.1]Hept-5-ene-2,3-dicarboximide), N,N'-cyclohexylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3 -Dicarboximide), N,N'-cyclohexylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide),

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

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

2,2-bis[4-{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide)phenoxy}phenyl]propane, 2,2-bis[4-{ 4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximido)phenoxy}phenyl]propane, 2,2-bis[4-{4-(methallylbicyclo[2] 1.2.1]hept-5-ene-2,3-dicarboximide)phenoxy}phenyl]propane, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-di] Carboximido)phenyl}methane, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximido)phenyl}methane,

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

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

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

2,2-bis[4-{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximido)-2-hydroxy-phenoxy}phenyl]propane, bis{4- (Allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide)-2-hydroxy-phenyl}methane, bis{3-(allylbicyclo[2.2.1]hept- 5-ene-2,3-dicarboximide)-4-hydroxy-phenyl} ether, bis{3-(methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide) -5-hydroxy-phenyl} sulfone, 1,1,1-tri{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide)}phenoxymethylpropane, N , N′,N″-tri(ethylenemethallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide) isocyanurate, and oligomers thereof.

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

Among the alkenyl-substituted nadiimide compounds, preferable compounds are shown below.
N,N'-ethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide), N,N'-ethylene-bis(allylmethylbicyclo[2.2. 1] hept-5-ene-2,3-dicarboximide), N,N'-ethylene-bis(methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide) , N,N'-trimethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide), N,N'-hexamethylene-bis(allylbicyclo[2.2] .1]Hept-5-ene-2,3-dicarboximide), N,N'-hexamethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl) Imido), N,N′-dodecamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide), N,N′-dodecamethylene-bis(allylmethylbicyclo) [2.2.1]Hept-5-ene-2,3-dicarboximide), N,N'-cyclohexylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3 -Dicarboximide), N,N'-cyclohexylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide),

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

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

More preferable alkenyl-substituted nadiimide compounds are shown below.
N,N'-ethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide), N,N'-ethylene-bis(allylmethylbicyclo[2.2. 1] hept-5-ene-2,3-dicarboximide), N,N'-ethylene-bis(methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide) , N,N'-trimethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide), N,N'-hexamethylene-bis(allylbicyclo[2.2] .1]Hept-5-ene-2,3-dicarboximide), N,N'-hexamethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl) Imido), N,N′-dodecamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide), N,N′-dodecamethylene-bis(allylmethylbicyclo) [2.2.1]Hept-5-ene-2,3-dicarboximide), N,N'-cyclohexylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3 -Dicarboximide), N,N'-cyclohexylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide).

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

2,2-bis[4-{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide)phenoxy}phenyl]propane, 2,2-bis[4-{ 4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximido)phenoxy}phenyl]propane, 2,2-bis[4-{4-(methallylbicyclo[2] 1.2.1]hept-5-ene-2,3-dicarboximide)phenoxy}phenyl]propane, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-di] Carboximido)phenyl}methane, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximido)phenyl}methane, bis{4-(methallylbicyclo[2] 1.2.1]hept-5-ene-2,3-dicarboximido)phenyl}methane, bis{4-(methallylmethylbicyclo[2.2.1]hept-5-ene-2,3-di Carboximido)phenyl}methane.

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

<Compound Having Radical Polymerizable Unsaturated Double Bond>
For example, the liquid crystal aligning agent of the present invention may further contain a compound having a radical-polymerizable unsaturated double bond for the purpose of stabilizing the electrical characteristics of the liquid crystal display device for a long period of time. The compound having a radical-polymerizable unsaturated double bond may be one kind of compound or two or more kinds of compounds. The compound having a radically polymerizable unsaturated double bond does not include an alkenyl-substituted nadimide compound. The content of the compound having a radical-polymerizable unsaturated double bond is preferably 1 to 100% by weight, more preferably 1 to 70% by weight based on the polyamic acid or its derivative, for the above purpose. It is preferably from 1 to 50% by weight, and further preferably.

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

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

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

Specific examples of the bifunctional (meth)acrylic acid ester include, for example, ethylene bisacrylate, Aronix M-210, Aronix M-240 and Aronix M-6200, which are products of Toagosei Kagaku Kogyo Co., Ltd., Nippon Kayaku Co., Ltd. ) Products, KAYARAD HDDA, KAYARADHX-220, KAYARADR-604 and KAYARADR-684, products of Osaka Organic Chemical Industry Co., Ltd. V260, V312 and V335HP, and products of Kyoeisha Oil and Fat Chemical Industry Co., Ltd. light acrylate. BA-4EA, light acrylate BP-4PA and light acrylate BP-2PA are mentioned.

Specific examples of trifunctional or higher polyfunctional (meth)acrylic acid esters include, for example, 4,4′-methylenebis(N,N-dihydroxyethylene acrylate aniline), Aronix M- which is a product of Toagosei Kagaku Kogyo Co., Ltd. 400, Aronix M-405, Aronix M-450, Aronix M-7100, Aronix M-8030, Aronix M-8060, products of Nippon Kayaku Co., Ltd. KAYARADDTMPTA, KAYARADDPCA-20, KAYARADDPCA-30, KAYAARDDPCA-60. , KAYARADDPCA-120, and VGPT, a product of Osaka Organic Chemical Industry Co., Ltd.

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

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

Examples of the bismaleimide include BMI-70 and BMI-80 manufactured by KI Kasei Co., Ltd., and BMI-1000, BMI-3000, BMI-4000, BMI-5000 and BMI- manufactured by Daiwa Kasei Kogyo Co., Ltd. 7,000 is included.

<Oxazine compound>
For example, the liquid crystal aligning agent of the present invention may further contain an oxazine compound for the purpose of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time. The oxazine compound may be one kind of compound or two or more kinds of compounds. From the above-mentioned purpose, the content of the oxazine compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, and 1 to 20% by weight based on the polyamic acid or its derivative. Is more preferable.

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

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

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

式（ＯＸ−１）〜式（ＯＸ−３）において、Ｌ^３およびＬ^４は炭素数１〜３０の有機基であり、式（ＯＸ−１）〜式（ＯＸ−６）において、Ｌ^５〜Ｌ^８は水素または炭素数１〜６の炭化水素基であり、式（ＯＸ−３）、式（ＯＸ−４）および式（ＯＸ−６）において、Ｑ^１は単結合、−Ｏ−、−Ｓ−、−Ｓ−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−、−（ＣＨ_２）_ｖ−、−Ｏ−（ＣＨ_２）_ｖ−Ｏ−、−Ｓ−（ＣＨ_２）_ｖ−Ｓ−であり、ここでｖは１〜６の整数であり、式（ＯＸ−５）および式（ＯＸ−６）において、Ｑ^２は独立して単結合、−Ｏ−、−Ｓ−、−ＣＯ−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−または炭素数１〜３のアルキレンであり、Ｑ^２におけるベンゼン環、ナフタレン環に結合している水素は独立して−Ｆ、−ＣＨ_３、−ＯＨ、−ＣＯＯＨ、−ＳＯ_３Ｈ、−ＰＯ_３Ｈ_２と置き換えられていてもよい。 Examples of the oxazine compound include compounds represented by the following formulas (OX-1) to (OX-6). In addition, in the following formula, the bond shown toward the center of the ring indicates that it is bonded to any carbon that constitutes the ring and is capable of bonding with a substituent.

In formulas (OX-1) to (OX-3), L ³ and L ⁴ are organic groups having 1 to 30 carbon atoms, and in formulas (OX-1) to (OX-6), L ⁵ to L ⁸ is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, and in formula (OX-3), formula (OX-4) and formula (OX-6), Q ¹ is a single bond, —O—, — _{S -, - S-S -} , - SO 2 -, - CO -, - CONH -, - NHCO -, - C (CH 3) 2 -, - C (CF 3) 2 -, - (CH 2) v _{-, - O- (CH 2)} v -O -, - S- (CH 2) v is -S-, where v is an integer from 1 to 6, formula (OX-5) and formula (OX In -6), Q ² is independently a single bond, —O—, —S—, —CO—, —C(CH ₃ ) ₂ —, —C(CF ₃ ) ₂ —, or a group having 1 to 3 carbon atoms. It is alkylene, and the hydrogen bonded to the benzene ring and the naphthalene ring in Q ² is independently replaced with -F, -CH ₃ , -OH, -COOH, -SO ₃ H, -PO ₃ H _2. Good.

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

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

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

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

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

式（ＯＸ−３−Ｉ）において、Ｌ^３およびＬ^４は炭素数１〜３０の有機基であり、Ｌ^５からＬ^８は水素または炭素数１〜６の炭化水素基であり、Ｑ^１は単結合、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−ＣＯ−、−Ｏ−、−ＳＯ_２−、−Ｃ（ＣＨ_３）_２−、または−Ｃ（ＣＦ_３）_２−である。式（ＯＸ−３−Ｉ）で表されるオキサジン化合物としては、例えば以下のオキサジン化合物が挙げられる。 Examples of the oxazine compound represented by the formula (OX-3) include oxazine compounds represented by the following formula (OX-3-I).

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

式中、Ｌ^３およびＬ^４は炭素数１〜３０のアルキルが好ましく、炭素数１〜２０のアルキルがさらに好ましい。

In the formula, L ³ and L ⁴ are preferably alkyl having 1 to 30 carbons, and more preferably alkyl having 1 to 20 carbons.

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

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

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

Of these, more preferably, formula (OX-2-1), formula (OX-3-1), formula (OX-3-3), formula (OX-3-5), formula (OX-3-). 7), formula (OX-3-9), formula (OX-4-1) to formula (OX-4-6), formula (OX-5-3), formula (OX-5-4), and formula Examples thereof include oxazine compounds represented by (OX-6-2) to formula (OX-6-4).

The oxazine compound can be produced by a method similar to the method described in International Publication 2004/009708, JP-A-11-12258, and JP-A-2004-352670.

The oxazine compound represented by the formula (OX-1) is obtained by reacting a phenol compound with a primary amine and an aldehyde (see International Publication 2004/097008).

The oxazine compound represented by the formula (OX-2) is obtained by gradually reacting a primary amine with formaldehyde and then adding and reacting a compound having a naphthol-based hydroxyl group (International Publication 2004/ 099070.).

The oxazine compound represented by the formula (OX-3) is obtained by adding 1 mol of a phenol compound, at least 2 mol or more of an aldehyde to 1 phenolic hydroxyl group thereof, and 1 mol of a primary amine to a secondary aliphatic compound in an organic solvent. It can be obtained by reacting in the presence of an amine, a tertiary aliphatic amine or a basic nitrogen-containing heterocyclic compound (see International Publication 2004/09708 and JP-A-11-12258).

The oxazine compounds represented by the formulas (OX-4) to (OX-6) include diamines having a plurality of benzene rings and an organic group bonding them, such as 4,4′-diaminodiphenylmethane, and formalin. It is obtained by subjecting an aldehyde and a phenol to a dehydration condensation reaction in n-butyl alcohol at a temperature of 90° C. or higher (see JP 2004-352670 A).

<Oxazoline compound>
For example, the liquid crystal aligning agent of the present invention may further contain an oxazoline compound for the purpose of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time. The oxazoline compound is a compound having an oxazoline structure. The oxazoline compound may be one kind of compound or two or more kinds of compounds. From the above-mentioned purpose, the content of the oxazoline compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, and 1 to 20% by weight based on the polyamic acid or its derivative. Is more preferable. Alternatively, the content of the oxazoline compound is preferably 0.1 to 40% by weight based on the polyamic acid or its derivative when the oxazoline structure in the oxazoline compound is converted into oxazoline, from the above-mentioned object.

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

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

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

<Epoxy compound>
For example, the liquid crystal aligning agent of the present invention may further contain an epoxy compound for the purpose of stabilizing the electrical characteristics of the liquid crystal display device for a long period of time. The epoxy compound may be one kind of compound or two or more kinds of compounds. From the above-mentioned purpose, the content of the epoxy compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, and 1 to 20% by weight based on the polyamic acid or its derivative. Is more preferable.

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

Examples of the compound having two epoxy rings in the molecule include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl. Ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate, celoxide 8000 (trade name, manufactured by Daicel Corporation), and 3-(N,N-diglycidyl)aminopropyltrimethoxysilane.

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

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

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

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

Specific preferred examples of the polymer of a monomer having an epoxy ring include polyglycidyl methacrylate. Further, as preferable specific examples of the copolymer of a monomer having an epoxy ring and another monomer, N-phenylmaleimide-glycidylmethacrylate copolymer, N-cyclohexylmaleimide-glycidylmethacrylate copolymer, benzylmethacrylate-glycidylmethacrylate. Copolymer, butylmethacrylate-glycidylmethacrylate copolymer, 2-hydroxyethylmethacrylate-glycidylmethacrylate copolymer, (3-ethyl-3-oxetanyl)methylmethacrylate-glycidylmethacrylate copolymer and styrene-glycidylmethacrylate copolymer Are listed.

Among these examples, N,N,N',N'-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'- Tetraglycidyl-4,4′-diaminodiphenylmethane, trade name “Techmore VG3101L”, 3,4-epoxycyclohexenylmethyl-3′,4′-epoxycyclohexenecarboxylate, N-phenylmaleimide-glycidylmethacrylate copolymer, celoxide 8000 (trade name, manufactured by Daicel Corporation) and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane are particularly preferable.

More systematically, examples of the epoxy compound include glycidyl ether, glycidyl ester, glycidyl amine, epoxy group-containing acrylic resin, glycidyl amide, glycidyl isocyanurate, chain aliphatic epoxy compound, and cycloaliphatic epoxy compound. Are listed. The epoxy compound means a compound having an epoxy group, and the epoxy resin means a resin having an epoxy group.

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

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

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

Examples of glycidyl amines include polyglycidyl amine compounds and glycidyl amine type epoxy resins.

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

Examples of glycidyl amides include glycidyl amide type epoxy compounds.

Examples of the chain aliphatic epoxy compound include a compound having an epoxy group, which is obtained by oxidizing a carbon-carbon double bond of an alkene compound.

Examples of the cycloaliphatic epoxy compound include a compound having an epoxy group, which is obtained by oxidizing a carbon-carbon double bond of a cycloalkene compound.

Examples of the bisphenol A type epoxy compound include jER828, jER1001, jER1002, jER1003, jER1004, jER1007, jER1010 (all are trade names, manufactured by Mitsubishi Chemical Corporation), Epotote YD-128 (manufactured by Tohto Kasei Co., Ltd.), DER. -331, DER-332, DER-324 (all manufactured by The Dow Chemical Company), Epiclon 840, Epiclon 850, Epiclon 1050 (all trade names, manufactured by DIC Corporation), Epomic R-140, Epomic R-301. , And Epomic R-304 (both are trade names, manufactured by Mitsui Chemicals, Inc.).

Examples of the bisphenol F type epoxy compound include jER806, jER807, jER4004P (all are trade names, manufactured by Mitsubishi Chemical Corporation), Epotote YDF-170, Epotote YDF-175S, Epotote YDF-2001 (all trade names, Toto Kasei). Co., Ltd.), DER-354 (trade name, manufactured by Dow Chemical Co.), Epicron 830, and Epicron 835 (all are trade names, manufactured by DIC Corporation).

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

Examples of the hydrogenated bisphenol-A type epoxy compound include Santoto ST-3000 (trade name, manufactured by Tohto Kasei Co., Ltd.), Licaredin HBE-100 (trade name, manufactured by Shin Nippon Rika Co., Ltd.), and Denacol EX-252. (Trade name, manufactured by Nagase Chemtex Co., Ltd.).

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

Examples of the brominated bisphenol-A type epoxy compound include jER5050, jER5051 (both are trade names, manufactured by Mitsubishi Chemical Corporation), Epotote YDB-360, and Epotote YDB-400 (both are trade names, manufactured by Toto Kasei Co., Ltd.). ), DER-530, DER-538 (all are trade names, manufactured by The Dow Chemical Company), Epiclon 152, and epiclon 153 (all are trade names, manufactured by DIC Corporation).

Examples of the phenol novolac type epoxy compound include jER152, jER154 (trade names, manufactured by Mitsubishi Chemical Corporation), YDPN-638 (trade name, manufactured by Toto Kasei Co., Ltd.), DEN431, DEN438 (trade names, The Dow). Chemical Company), Epiclon N-770 (trade name, manufactured by DIC Corporation), EPPN-201, and EPPN-202 (all are trade names, manufactured by Nippon Kayaku Co., Ltd.).

Examples of the cresol novolac type epoxy compound include jER180S75 (trade name, manufactured by Mitsubishi Chemical Corporation), YDCN-701, YDCN-702 (all are trade names, manufactured by Toto Kasei Co., Ltd.), Epicron N-665, Epicron N-695. (All are trade names, manufactured by DIC Corporation), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, and EOCN-1027 (all are trade names, manufactured by Nippon Kayaku Co., Ltd.). ) Is mentioned.

Examples of the bisphenol A novolac type epoxy compound include jER157S70 (trade name, manufactured by Mitsubishi Chemical Corporation) and Epicron N-880 (trade name, manufactured by DIC Corporation).

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

Examples of the aromatic polyglycidyl ether compound include hydroquinone diglycidyl ether (the following formula EP-1), catechol diglycidyl ether (the following formula EP-2), resorcinol diglycidyl ether (the following formula EP-3), and 2-[4 -(2,3-Epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-([2,3-epoxypropoxy]phenyl)]ethyl]phenyl]propane (the following formula EP-4) , Tris(4-glycidyloxyphenyl)methane (the following formula EP-5), jER1031S, jER1032H60 (all are trade names, manufactured by Mitsubishi Chemical Corporation), TACTIX-742 (trade name, manufactured by The Dow Chemical Company), Denacol EX-201 (trade name, manufactured by Nagase Chemtex Co., Ltd.), DPPN-503, DPPN-502H, DPPN-501H, NC6000 (all are trade names, manufactured by Nippon Kayaku Co., Ltd.), Techmore VG3101L (trade name, Mitsui Chemicals, Inc.), a compound represented by the following formula EP-6, and a compound represented by the following formula EP-7.

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

Examples of the alicyclic diglycidyl ether compound include cyclohexanedimethanol diglycidyl ether compound, and lycaredin DME-100 (trade name, manufactured by Shin Nippon Rika Co., Ltd.).

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

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

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

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

Examples of the glycidyl ester epoxy compound include jER871 and jER872 (both are trade names, manufactured by Mitsubishi Chemical Co., Ltd.), Epicron 200, epicron 400 (both are trade names, manufactured by DIC Corporation), Denacol EX-711, and Denacol. EX-721 (trade name, manufactured by Nagase Chemtex Co., Ltd.) can be mentioned.

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

Examples of homopolymers of oxiranyl-containing monomers include polyglycidyl methacrylate. Examples of the copolymer of monomers having oxiranyl include N-phenylmaleimide-glycidylmethacrylate copolymer, N-cyclohexylmaleimide-glycidylmethacrylate copolymer, benzylmethacrylate-glycidylmethacrylate copolymer, butylmethacrylate-glycidylmethacrylate copolymer. Examples thereof include a combination, a 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer, a (3-ethyl-3-oxetanyl)methyl methacrylate-glycidyl methacrylate copolymer, and a styrene-glycidyl methacrylate copolymer.

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

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

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

Examples of the chain aliphatic epoxy compound include epoxidized polybutadiene and Epolide PB3600 (trade name, manufactured by Daicel Corporation).

Examples of the cycloaliphatic epoxy compound include 3,4-epoxycyclohexenylmethyl-3′,4′-epoxycyclohexenecarboxylate (Celoxide 2021 (manufactured by Daicel Corporation), the following formula EP-52), and 2-methyl. -3,4-Epoxycyclohexylmethyl-2'-methyl-3',4'-epoxycyclohexylcarboxylate (the following formula EP-53), 2,3-epoxycyclopentane-2',3'-epoxycyclopentane ether (The following formula EP-54), ε-caprolactone-modified 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarbochelate, 1,2:8,9-diepoxylimonene (celoxide 3000 (trade name, ( Compound) represented by the following formula EP-55), the following formula EP-56, Celoxide 8000 (trade name, manufactured by Daicel Corporation, the following formula EP-57), CY-175, CY-177. , CY-179 (trade name, manufactured by The Ciba-Geigy Chemical Corp. (available from Huntsman Japan KK)), EHPD-3150 (trade name, manufactured by Daicel Corporation), and cycloaliphatic. Type epoxy resin.

The epoxy compound is preferably one or more of a polyglycidylamine compound, a bisphenol A novolac type epoxy compound, a cresol novolac type epoxy compound, and a cycloaliphatic epoxy compound, and N,N,N′,N′-tetraglycidyl. -M-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, trade name "Techmore VG3101L" ,3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate, N-phenylmaleimide-glycidyl methacrylate copolymer, N,N,O-triglycidyl-p-aminophenol, bisphenol A novolac type More preferably, it is one or more of an epoxy compound and a cresol novolac type epoxy compound.

Further, for example, the liquid crystal aligning agent of the present invention may further contain various additives. Examples of various additives include high molecular compounds other than polyamic acid and its derivatives, and low molecular compounds, which can be selected and used according to their respective purposes.

For example, the polymer compound may be a polymer compound soluble in an organic solvent. It is preferable to add such a polymer compound to the liquid crystal aligning agent of the present invention from the viewpoint of controlling the electrical characteristics and the orientation of the liquid crystal aligning film to be formed. Examples of the polymer compound include polyamide, polyurethane, polyurea, polyester, polyepoxide, polyester polyol, silicone-modified polyurethane, and silicone-modified polyester.

Examples of the low molecular weight compound include 1) a surfactant that meets such a purpose when it is desired to improve coatability, 2) an antistatic agent when it is necessary to improve antistatic property, and 3) adhesion to a substrate. A silane coupling agent or a titanium-based coupling agent may be used to improve the properties, and 4) an imidization catalyst may be used to promote imidization at low temperature.

Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, and N-(2-aminoethyl)-3-aminopropylmethyltrisilane. Methoxysilane, paraaminophenyltrimethoxysilane, paraaminophenyltriethoxysilane, metaaminophenyltrimethoxysilane, metaaminophenyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxy Propyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N- (1,3-Dimethylbutylidene)-3-(triethoxysilyl)-1-propylamine, and N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine. The preferred silane coupling agent is 3-aminopropyltriethoxysilane.

Examples of the imidization catalyst include aliphatic amines such as trimethylamine, triethylamine, tripropylamine and tributylamine; aromatic amines such as N,N-dimethylaniline, N,N-diethylaniline, methyl-substituted aniline and hydroxy-substituted aniline. 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. .. The imidization catalyst may be one or more selected from N,N-dimethylaniline, o-, m-, p-hydroxyaniline, o-, m-, p-hydroxypyridine, and isoquinoline. preferable.

The addition amount of the silane coupling agent is usually 0 to 20% by weight, and preferably 0.1 to 10% by weight, based on the total weight of the polyamic acid or its derivative.

The addition amount of the imidization catalyst is usually 0.01 to 5 equivalents, preferably 0.05 to 3 equivalents, relative to the carbonyl group of the polyamic acid or its derivative.

The amount of other additives added varies depending on the application, but is usually 0 to 100% by weight, and preferably 0.1 to 50% by weight, based on the total weight of the polyamic acid or its derivative.

The polyamic acid or its derivative of the present invention can be produced in the same manner as the known polyamic acid or its derivative used for forming a polyimide film. The total charged amount of tetracarboxylic dianhydride is preferably approximately equimolar to the total number of moles of diamine (molar ratio of about 0.9 to 1.1).

The molecular weight of the polyamic acid or its derivative of the present invention is preferably 7,000 to 500,000, and more preferably 10,000 to 200,000 in terms of polystyrene equivalent weight average molecular weight (Mw). The molecular weight of the polyamic acid or its derivative can be determined by measurement by gel permeation chromatography (GPC) method.

The presence of the polyamic acid or its derivative of the present invention can be confirmed by analyzing the solid content obtained by precipitation with a large amount of a poor solvent by IR or NMR. Further, the monomer used can be confirmed by analyzing the extract of the decomposition product of the above polyamic acid or its derivative with an organic solvent with an aqueous solution of a strong alkali such as KOH or NaOH by GC, HPLC or GC-MS. it can.

Further, for example, the liquid crystal aligning agent of the present invention may further contain a solvent from the viewpoint of coating properties of the liquid crystal aligning agent and adjusting the concentration of the polyamic acid or its derivative. The solvent can be applied without particular limitation as long as it is a solvent capable of dissolving a polymer component. The solvent includes a wide range of solvents that are usually used in the manufacturing process and application of polymer components such as polyamic acid and soluble polyimide, and can be appropriately selected according to the purpose of use. The solvent may be one kind or a mixed solvent of two or more kinds.

Examples of the solvent include a hydrophilic solvent for the polyamic acid or its derivative, and other solvents for improving coating properties.

Examples of the aprotic polar organic solvent which is a hydrophilic solvent for polyamic acid or its derivative include N-methyl-2-pyrrolidone, dimethylimidazolidinone, N-methylcaprolactam, N-methylpropionamide, and N,N-dimethylacetamide. And lactones such as dimethyl sulfoxide, N,N-dimethylformamide, N,N-diethylformamide, diethylacetamide, and γ-butyrolactone.

Examples of other solvents for the purpose of improving coatability include alkyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, ethylene glycol monoalkyl ethers such as ethylene glycol monobutyl ether, and diethylene glycol monoethyl ether. Diethylene glycol monoalkyl ether, ethylene glycol monoalkyl ether or phenyl acetate, triethylene glycol monoalkyl ether, propylene glycol monomethyl ether, propylene glycol monoalkyl ether such as propylene glycol monobutyl ether, dialkyl malonate such as diethyl malonate, dipropylene glycol monomethyl ether Examples include dipropylene glycol monoalkyl ethers such as ethers and ester compounds such as acetates.

Among these, the solvent is N-methyl-2-pyrrolidone, dimethylimidazolidinone, γ-butyrolactone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether, and dipropylene glycol. Monomethyl ether is particularly preferred.

The concentration of polyamic acid in the aligning agent of the present invention is preferably 0.1 to 40% by weight. When applying this aligning agent to the substrate, an operation of previously diluting the contained polyamic acid with a solvent may be required in order to adjust the film thickness.

The solid content concentration in the aligning agent of the present invention is not particularly limited, and an optimum value may be selected according to various coating methods described below. Usually, it is preferably 0.1 to 30% by weight, more preferably 1 to 10% by weight based on the weight of the varnish in order to suppress unevenness and pinholes during coating.

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

The liquid crystal alignment film of the present invention will be described in detail. The liquid crystal alignment film of the present invention is a film formed by heating the coating film of the liquid crystal alignment agent of the present invention described above. The liquid crystal alignment film of the present invention can be obtained by a usual method for producing a liquid crystal alignment film from a liquid crystal alignment agent. For example, the liquid crystal alignment film of the present invention can be obtained by the steps of forming a coating film of the liquid crystal aligning agent of the present invention, heating and drying, and heating and baking. The liquid crystal alignment film of the present invention may be subjected to a rubbing treatment to give anisotropy to the film obtained through the heating and drying process and the heating and baking process, as described later, if necessary. Alternatively, if necessary, anisotropy may be imparted by irradiating light after the coating step and heat drying step, or by irradiating light after the heating and firing step. It may also be used as a VA liquid crystal alignment film that is not subjected to rubbing treatment.

The coating film can be formed by applying the liquid crystal aligning agent of the present invention to a substrate in a liquid crystal display element, as in the case of producing a normal liquid crystal aligning film. Examples of the substrate include a glass substrate that may be provided with electrodes such as ITO (Indium Tin Oxide), IZO (In ₂ O ₃ —ZnO), and IGZO (In—Ga—ZnO ₄ ) electrodes and a color filter. ..

The spinner method, the printing method, the dipping method, the dropping method, the inkjet method and the like are generally known as methods for applying the liquid crystal aligning agent to the substrate. These methods are similarly applicable to the present invention.

In the heat drying step, a method of heat treatment in an oven or an infrared furnace, a method of heat treatment on a hot plate, etc. are generally known. The heating/drying step is preferably carried out at a temperature within a range where the solvent can be evaporated, and more preferably at a temperature relatively lower than the temperature in the heating/baking step. Specifically, the heating and drying temperature is preferably in the range of 30°C to 150°C, and more preferably in the range of 50°C to 120°C.

The heating and firing step can be performed under the conditions necessary for the polyamic acid or its derivative to undergo dehydration/ring-closing reaction. For the baking of the coating film, a method of heat treatment in an oven or an infrared furnace, a method of heat treatment on a hot plate, etc. are generally known. These methods are similarly applicable in the present invention. Generally, it is preferably carried out at a temperature of about 100 to 300° C. for 1 minute to 3 hours, more preferably 120 to 280° C., further preferably 150 to 250° C.

In the method for forming a liquid crystal alignment film of the present invention, a rubbing method or a photo-alignment method is known as a means for imparting anisotropy to the alignment film in order to align the liquid crystal in one direction with respect to the horizontal and/or vertical direction. The forming method of can be preferably used.

The liquid crystal alignment film of the present invention using the rubbing method, the step of applying the liquid crystal alignment agent of the present invention to the substrate, the step of heating and drying the substrate coated with the alignment agent, the step of heating and baking the film, Can be formed by a rubbing treatment.

The rubbing treatment can be performed in the same manner as the usual rubbing treatment for the alignment treatment of the liquid crystal alignment film, and may be performed under the condition that sufficient retardation can be obtained in the liquid crystal alignment film of the present invention. Preferable conditions are a push-in amount of 0.2 to 0.8 mm, a stage moving speed of 5 to 250 mm/sec, and a roller rotating speed of 500 to 2,000 rpm.

The method for forming the liquid crystal alignment film of the present invention by the photo-alignment method will be described in detail. The liquid crystal alignment film of the present invention using the photo-alignment method, after heating and drying the coating film, imparts anisotropy to the coating film by irradiating it with linearly polarized light or non-polarized light, and heat-bakes the film. Can be formed. Alternatively, the coating film can be formed by heating and drying the coating film, baking it by heating, and then irradiating it with linearly polarized light or unpolarized light. From the viewpoint of orientation, the radiation irradiation step is preferably performed after the heating and firing step.

Further, in order to improve the liquid crystal aligning ability of the liquid crystal aligning film, it is possible to irradiate linearly polarized light or non-polarized radiation while heating the coating film. The irradiation of radiation may be performed in the step of heating and drying the coating film, or in the step of heating and baking, or may be performed between the heating and drying step and the heating and baking step. The heating and drying temperature in this step is preferably in the range of 30°C to 150°C, and more preferably in the range of 50°C to 120°C. The heating and firing temperature in this step is preferably in the range of 30°C to 300°C, and more preferably in the range of 50°C to 250°C.

As the radiation, for example, ultraviolet rays or visible light containing light with a wavelength of 150 to 800 nm can be used, but ultraviolet rays containing light with 200 to 400 nm is preferable. Further, linearly polarized light or non-polarized light can be used. The light is not particularly limited as long as it can impart liquid crystal aligning ability to the coating film, but linear polarization is preferable when it is desired to exert a strong alignment regulating force on the liquid crystal.

The liquid crystal alignment film of the present invention can exhibit a high liquid crystal alignment ability even with low energy light irradiation. Dose of linearly polarized light in the irradiation step is preferably from 0.05~20J / cm ^2, more preferably 0.5~10J / cm ^2. The wavelength of linearly polarized light is preferably 150 to 800 nm, more preferably 200 to 400 nm. The irradiation angle of the linearly polarized light with respect to the film surface is not particularly limited, but when it is desired to exert a strong alignment regulating force on the liquid crystal, it is preferable to be as perpendicular as possible to the film surface from the viewpoint of shortening the alignment treatment time. Further, the liquid crystal alignment film of the present invention can align the liquid crystal in a direction perpendicular to the polarization direction of the linearly polarized light by irradiating the liquid crystal with the linearly polarized light.

The light with which the film is irradiated when a pretilt angle is desired to be expressed may be linearly polarized light or non-polarized light as described above. Dose of light applied to the film when it is desired to express a pre-tilt angle is preferably from 0.05~20J / cm ^2, particularly preferably 0.5~10J / cm ^2, its wavelength is 250 It is preferably 400 nm, particularly preferably 200 to 300 nm. When the pretilt angle is desired to be expressed, the irradiation angle of the light for irradiating the film with respect to the film surface is not particularly limited, but it is preferably 30 to 60 degrees from the viewpoint of shortening the alignment treatment time.

Light sources used in the process of irradiating linearly polarized or unpolarized radiation include ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, deep UV lamps, halogen lamps, metal halide lamps, high power metal halide lamps, xenon lamps, and mercury. A xenon lamp, an excimer lamp, a KrF excimer laser, a fluorescent lamp, an LED lamp, a sodium lamp, a microwave excitation electrodeless lamp, or the like can be used without limitation.

The liquid crystal alignment film of the present invention can be suitably obtained by a method further including steps other than the steps described above. For example, the liquid crystal alignment film of the present invention does not require a step of washing the film after baking or irradiation with radiation with a washing liquid, but a washing step can be provided for the convenience of other steps.

Examples of the cleaning method using the cleaning liquid include brushing, jet spraying, steam cleaning, ultrasonic cleaning and the like. These methods may be used alone or in combination. As the cleaning liquid, pure water or various alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol, aromatic hydrocarbons such as benzene, toluene and xylene, halogen solvents such as methylene chloride, ketones such as acetone and methyl ethyl ketone are used. It can be used, but is not limited thereto. Of course, as these cleaning liquids, those which are sufficiently purified and contain few impurities are used. Such a cleaning method can also be applied to the cleaning step in the formation of the liquid crystal alignment film of the present invention.

In order to enhance the liquid crystal alignment ability of the liquid crystal alignment film of the present invention, heat or light annealing treatment can be used before and after the heating and baking step, before and after the rubbing step, or before and after irradiation with polarized or unpolarized radiation. .. In the annealing treatment, the annealing temperature is 30 to 180° C., preferably 50 to 150° C., and the time is preferably 1 minute to 2 hours. The annealing light used for the annealing treatment may be a UV lamp, a fluorescent lamp, an LED lamp or the like. The irradiation amount of light is preferably 0.3 to 10 J/cm ² .

The thickness of the liquid crystal alignment film of the present invention is not particularly limited, but is preferably 10 to 300 nm, more preferably 30 to 150 nm. The film thickness of the liquid crystal alignment film of the present invention can be measured by a known film thickness measuring device such as a step meter or an ellipsometer.

The degree of anisotropy of the liquid crystal alignment film of the present invention can be evaluated by the method using polarized IR described in JP-A-2005-275364. It can also be evaluated by a method using ellipsometry as shown in the following examples. Specifically, the retardation value of the liquid crystal alignment film can be measured with a spectroscopic ellipsometer. The retardation value of the film increases in proportion to the degree of orientation of the polymer main chain. That is, those having a large retardation value have a large degree of alignment, and when used as a liquid crystal alignment film, an alignment film having a larger anisotropy is considered to have a large alignment regulating force with respect to the liquid crystal composition.

The liquid crystal alignment film of the present invention can be suitably used for a horizontal electric field type liquid crystal display device. When used in a horizontal electric field type liquid crystal display element, the smaller the pretilt angle and the higher the liquid crystal alignment ability, the higher the black display level in the dark state and the higher the contrast. The pretilt angle is preferably 0.1° or less.

The liquid crystal alignment film of the present invention can be used for alignment control of optical compensators and all other liquid crystal materials, in addition to the alignment use of liquid crystal compositions for liquid crystal displays. Further, since the alignment film of the present invention has a large anisotropy, it can be used alone as an optical compensator.

The liquid crystal display element of the present invention will be described in detail.
According to the present invention, a pair of substrates arranged to face each other, an electrode formed on one or both of the facing surfaces of each of the pair of substrates, and an electrode formed on the facing surface of each of the pair of substrates. In a liquid crystal display element having the liquid crystal alignment film formed as described above and a liquid crystal layer formed between the pair of substrates, there is provided a liquid crystal display element in which the liquid crystal alignment film is the alignment film of the present invention.

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

The liquid crystal layer is formed such that the liquid crystal composition is sandwiched between the pair of substrates whose surfaces on which the liquid crystal alignment film is formed face each other. In the formation of the liquid crystal layer, spacers such as fine particles and a resin sheet that intervene between the pair of substrates and form an appropriate interval can be used as necessary.

The liquid crystal composition is not particularly limited, and various liquid crystal compositions having a positive or negative dielectric anisotropy can be used. Preferred liquid crystal compositions having a positive dielectric anisotropy include JP3086228, JP2635435, JP-A-5-501735, JP-A-8-157526, JP-A-8-231960, JP-A-9-241644 (EP885272A1), and JP Kaihei 9-302346 (EP806466A1), JP-A-8-199168 (EP722998A1), JP-A-9-235552, JP-A-9-2559596, JP-A-9-241643 (EP885271A1), JP-A-10-201416 (EP844229A1), JP-A-10-19984. Liquid crystal compositions disclosed in, for example, -204436, JP-A-10-231482, JP-A-2000-0887040, and JP-A-2001-48822.

There is no problem in using one or more optically active compounds added to a liquid crystal composition having a positive or negative dielectric anisotropy.

ここで、Ｒ^１ａおよびＲ^２ａは独立して、炭素数１〜１２のアルキル、炭素数１〜１２のアルコキシ、炭素数２〜１２のアルケニル、または少なくとも１つの水素がフッ素で置き換えられた炭素数２〜１２のアルケニルであり、環Ａ^２および環Ｂ^２は独立して、１，４−シクロへキシレン、テトラヒドロピラン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、１，４−フェニレン、２−フルオロ−１，４−フェニレン、２，５−ジフルオロ−１，４−フェニレン、２，３−ジフルオロ−１，４−フェニレン、２−フルオロ−３−クロロ−１，４−フェニレン、２，３−ジフルオロ−６−メチル−１，４−フェニレン、２，６−ナフタレンジイル、または７，８−ジフルオロクロマン−２，６−ジイルであり、ここで、環Ａ^２および環Ｂ^２の少なくとも１つは２，３−ジフルオロ−１，４−フェニレン、２−フルオロ−３−クロロ−１，４−フェニレン、２，３−ジフルオロ−６−メチル−１，４−フェニレン、または７，８−ジフルオロクロマン−２，６−ジイルであり、Ｚ^１は独立して単結合、−（ＣＨ_２）_２−、−ＣＨ_２Ｏ−、−ＣＯＯ−、または−ＣＦ_２Ｏ−であり、ｊは１、２、または３であり、ｊが２または３である時、任意の２つの環Ａ^２は同じであっても異なってもよく、任意の２つのＺ^１は同じであっても異なってもよい。 The liquid crystal composition having a negative dielectric anisotropy will be described. Examples of the liquid crystal composition having a negative dielectric anisotropy include a composition containing, as the first component, at least one liquid crystal compound selected from the group of liquid crystal compounds represented by the following formula (NL-1). ..

Here, R ^1a and R ^2a are each independently an alkyl having 1 to 12 carbons, an alkoxy having 1 to 12 carbons, an alkenyl having 2 to 12 carbons, or a carbon number in which at least one hydrogen is replaced by fluorine. 2-12 alkenyl, wherein ring A ² and ring B ² are independently 1,4-cyclohexylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, 1 , 4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2-fluoro-3-chloro-1,4 -Phenylene, 2,3-difluoro-6-methyl-1,4-phenylene, 2,6-naphthalenediyl, or 7,8-difluorochroman-2,6-diyl, where ring A ² and ring At least one of B ² is 2,3-difluoro-1,4-phenylene, 2-fluoro-3-chloro-1,4-phenylene, 2,3-difluoro-6-methyl-1,4-phenylene, or 7,8 difluoromethoxy chroman-2,6-diyl, ^{Z 1} is independently a single _{bond, - (CH 2) 2 -} , - CH 2 O -, - COO-, or _-CF 2 O-a and , J is 1, 2, or 3, and when j is 2 or 3, any two rings A ² may be the same or different and any two Z ¹ are the same. May also be different.

Preferred ring A ² and ring B ² are 2,3-difluoro-1,4-phenylene or tetrahydropyran-2,5-diyl for increasing the dielectric anisotropy, and 1,2 for decreasing the viscosity. It is 4-cyclohexylene.

Preferred Z ¹ is —CH ₂ O— for increasing the dielectric anisotropy, and a single bond for decreasing the viscosity.

Preferable j is 1 for decreasing the minimum temperature and 2 for increasing the maximum temperature.

ここで、Ｒ^１aおよびＲ^２ａは独立して、炭素数１〜１２のアルキル、炭素数１〜１２のアルコキシ、炭素数２〜１２のアルケニル、または少なくとも１つの水素がフッ素で置き換えられた炭素数２〜１２のアルケニルであり、環Ａ^２１、環Ａ^２２、環Ａ^２３、環Ｂ^２１、および環Ｂ^２２は独立して、１，４−シクロへキシレンまたは１，４−フェニレンであり、Ｚ^１１およびＺ^１２は、独立して単結合、−（ＣＨ_２）_２−、−ＣＨ_２Ｏ−、または−ＣＯＯ−である。 Specific examples of the liquid crystal compound of the above formula (NL-1) include compounds represented by the following formulas (NL-1-1) to (NL-1-32).

Here, R ^1a and R ^2a are each independently an alkyl having 1 to 12 carbons, an alkoxy having 1 to 12 carbons, an alkenyl having 2 to 12 carbons, or a carbon number in which at least one hydrogen is replaced by fluorine. 2 to 12 alkenyl, and ring A ²¹ , ring A ²² , ring A ²³ , ring B ²¹ , and ring B ²² are independently 1,4-cyclohexylene or 1,4-phenylene, and Z ¹¹ and ^{Z 12} are independently a single _{bond, - (CH 2) 2 -} , - CH 2 O-, or -COO-.

Preferred R ^1a and R ^2a are alkyl having 1 to 12 carbons for increasing the stability against ultraviolet rays or heat, or alkoxy having 1 to 12 carbons for increasing the absolute value of the dielectric anisotropy.

Preferred alkyl is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl. More desirable alkyl is ethyl, propyl, butyl, pentyl, or heptyl for decreasing the viscosity.

Preferred alkoxy is methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy or heptyloxy. More desirable alkoxy is methoxy or ethoxy for decreasing the viscosity.

Preferred alkenyl is vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, It is 3-hexenyl, 4-hexenyl, or 5-hexenyl. More desirable alkenyl is vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl for decreasing the viscosity. The preferred configuration of -CH=CH- in these alkenyls depends on the position of the double bond. Trans is preferable in the alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl and 3-hexenyl for decreasing the viscosity. Cis is preferable in the alkenyl such as 2-butenyl, 2-pentenyl and 2-hexenyl. Of these alkenyls, linear alkenyls are preferred to branched ones.

Preferred examples of alkenyl in which at least one hydrogen has been replaced by fluorine are 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3-butenyl, 5,5-difluoro-4. -Pentenyl, and 6,6-difluoro-5-hexenyl. More preferable examples are 2,2-difluorovinyl and 4,4-difluoro-3-butenyl for decreasing the viscosity.

Preferred ring A ²¹ , ring A ²² , ring A ²³ , ring B ²¹ , and ring B ²² are each 1,4-cyclohexylene for decreasing the viscosity.

Preferred Z ¹¹ and Z ¹² are —CH ₂ O— for increasing the dielectric anisotropy, and a single bond for decreasing the viscosity.

The compound (NL-1) preferred as the first component in the liquid crystal composition having the negative dielectric anisotropy is compound (NL-1-1), (NL-1-4), (NL-1-). 7) or (NL-1-32).

Preferred examples of the liquid crystal composition having the negative dielectric anisotropy include JP-A-57-114532, JP-A-2-4725, JP-A-4-224885, JP-A-8-40953, and JP-A-8-104869. Kaihei 10-168076, JP-A-10-168453, JP-A-10-236989, JP-A-10-236990, JP-A-10-236992, JP-A-10-236933, JP-A-10-236994, JP-A-10-237000, JP-A-10-237000. -237004, JP-A-10-237024, JP-A-10-237035, JP-A-10-237075, JP-A-10-237076, JP-A-10-237448 (EP9672661A1), JP-A-10-287874, JP-A-10-287875, and JP-A-10-287875. 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, JP-A-2010-037428, International Publication 2011/ Liquid crystal compositions disclosed in 024666, International Publication 2010/072370, Japanese Patent Laid-Open No. 2010-5370010, JP 2012-077201, JP 2009-084362 and the like can be mentioned.

Further, for example, the liquid crystal composition used for the device of the present invention may further contain an additive from the viewpoint of improving the alignment property, for example. Such additives are photopolymerizable monomers, optically active compounds, antioxidants, ultraviolet absorbers, dyes, defoamers, polymerization initiators, polymerization inhibitors and the like.

The most preferable structure of the photopolymerizable monomer or oligomer for the purpose of improving the orientation of the liquid crystal includes the structures of formulas (PM-1-1) to (PM-1-6).

The amount of the photopolymerizable monomer or oligomer added is 0.01 parts by weight or more based on 100 parts by weight of the liquid crystal composition containing no additives in order to exert the effect of determining the tilt direction of the liquid crystal after polymerization. Is desirable. Further, in order to make the orientation effect of the polymer after polymerization appropriate, or to avoid elution of unreacted monomer or oligomer into the liquid crystal after irradiation with ultraviolet rays, it is preferably 30 parts by weight or less.

An optically active compound is mixed with the composition for the purpose of inducing a helical structure of liquid crystal to give a twist angle. Examples of such compounds are compound (PAC-1-1) to compound (PAC-1-4).

The preferred addition amount of the optically active compound is 5 parts by weight or less based on 100 parts by weight of the liquid crystal composition containing no additive. A more preferable addition amount is in the range of 0.01 to 2 parts by weight.

An antioxidant is added to the liquid crystal composition in order to prevent a decrease in the specific resistance due to heating in the atmosphere or to maintain a large voltage holding ratio not only at room temperature but also at a high temperature after the device has been used for a long time. Mixed.

A preferable example of the antioxidant is a compound (AO-1) in which w is an integer of 1 to 10. In compound (AO-1), preferable w is 1, 3, 5, 7, or 9. More desirable w is 1 or 7. The compound (AO-1) in which w is 1 is highly volatile and is effective in preventing a decrease in specific resistance due to heating in the atmosphere. The compound (AO-1) in which w is 7 has low volatility, and is therefore effective in maintaining a large voltage holding ratio not only at room temperature but also at high temperature after the device has been used for a long time. The preferred addition amount of the antioxidant is 50 ppm or more with respect to 100 parts by weight of the liquid crystal composition to which the additive is not added in order to obtain the effect, so that the upper limit temperature is not lowered or the lower limit temperature is not raised. It is 600 ppm or less. A further preferable amount of addition is in the range of 100 ppm to 300 ppm.

Preferred examples of the ultraviolet absorber are benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Light stabilizers such as sterically hindered amines are also preferred. The preferable addition amount of these absorbers and stabilizers is 50 ppm or more relative to 100 parts by weight of the liquid crystal composition to which the additive is not added in order to obtain the effect, so as not to lower the upper limit temperature or the lower limit temperature. Is 10000 ppm or less so as not to raise the value. A more preferable addition amount is in the range of 100 ppm to 10,000 ppm.

A dichroic dye such as an azo dye, anthraquinone dye, or the like is mixed with the composition in order to suit a GH (Guest host) mode device. A desirable ratio of the dye is in the range of 0.01% by weight to 10% by weight.

An antifoaming agent such as dimethyl silicone oil or methylphenyl silicone oil is mixed with the composition to prevent foaming. The preferable addition amount of the defoaming agent is 1 ppm or more with respect to 100 parts by weight of the liquid crystal composition to which the additive is not added in order to obtain the effect, and 1000 ppm or less in order to prevent defective display. A more preferable addition amount is in the range of 1 ppm to 500 ppm.

A polymerizable compound may be mixed with the composition in order to adjust to a device of PSA (polymer sustained alignment) mode. Preferred examples of the polymerizable compound are compounds having a polymerizable group such as acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxirane, oxetane) and vinyl ketone. Particularly preferred examples are acrylate or methacrylate derivatives. Examples of such a compound are the compound (PM-2-1) to the compound (PM-2-9). The preferable addition amount of the polymerizable compound is about 0.05 parts by weight or more based on 100 parts by weight of the liquid crystal composition to which the additive is not added in order to obtain the effect, and about 10 parts by weight to prevent display defects. Below the section. A further preferred amount of addition is in the range of about 0.1 part by weight to about 2 parts by weight.

ここで、Ｒ^３ａ、Ｒ^４ａ、Ｒ^５ａ、およびＲ^６ａは独立して、アクリロイルまたはメタクリロイルであり、Ｒ^７ａおよびＲ^８ａは独立して、水素、ハロゲン、または炭素数１から１０のアルキルであり、Ｚ^１３、Ｚ^１４、Ｚ^１５、およびＺ^１６は独立して、単結合または炭素数１から１２のアルキレンであり、少なくとも１つの−ＣＨ_２−は−Ｏ−または−ＣＨ＝ＣＨ−により置き換えられていてもよく、ｓ、ｔ、およびｕはそれぞれ独立して、０、１、または２である。

Wherein R ^3a , R ^4a , R ^5a , and R ^6a are independently acryloyl or methacryloyl, and R ^7a and R ^8a are independently hydrogen, halogen, or alkyl having 1 to 10 carbons. , Z ¹³ , Z ¹⁴ , Z ¹⁵ and Z ¹⁶ are independently a single bond or alkylene having 1 to 12 carbons, and at least one —CH ₂ — is replaced by —O— or —CH═CH—. S, t, and u are each independently 0, 1, or 2.

As a substance necessary for easily generating radicals or ions and initiating a chain polymerization reaction, a polymerization initiator can be mixed with the polymerizable compound in the liquid crystal composition. For example, the photopolymerization initiators Irgacure 651 (registered trademark), Irgacure 184 (registered trademark), or Darocure 1173 (registered trademark) (Ciba Japan KK) are suitable for radical polymerization. The photopolymerization initiator is preferably added in the range of 0.1% by weight to 5% by weight, particularly preferably in the range of 1% by weight to 3% by weight, based on 100 parts by weight of the polymerizable compound.

In a radical polymerization system, a polymerization initiator can be polymerized for the purpose of rapidly reacting with a polymerization initiator or a radical generated from a monomer to be converted into a stable radical or a neutral compound, and as a result, stopping the polymerization reaction. It can be mixed with the compound in the liquid crystal composition. Polymerization inhibitors are classified into some structures. One is a stable radical such as tri-p-nitrophenylmethyl, di-p-fluorophenylamine, etc., and the other is a stable radical that easily reacts with a radical existing in the polymerization system. Nitro, nitroso, amino, polyhydroxy compounds, etc. are typical. Typical examples of the latter include hydroquinone and dimethoxybenzene. The preferable addition amount of the polymerization inhibitor is 5 ppm or more with respect to 100 parts by weight of the polymerizable compound in order to obtain the effect, and 1000 ppm or less in order to prevent defective display. A more preferable addition amount is in the range of 5 ppm to 500 ppm.

By using a liquid crystal composition having a negative dielectric anisotropy for the liquid crystal display device of the present invention, it is possible to provide a liquid crystal display device having excellent afterimage characteristics and good alignment stability.

Hereinafter, the present invention will be described with reference to examples. The evaluation methods and compounds used in the examples are as follows.

1. Weight average molecular weight (Mw)
The weight average molecular weight of the polyamic acid was measured by the GPC method using a 2695 Separation Module/2414 Differential Refractometer (manufactured by Waters) and determined by converting to polystyrene. The obtained polyamic acid was diluted with a phosphoric acid-DMF mixed solution (phosphoric acid/DMF=0.6/100:weight ratio) so that the polyamic acid concentration was about 2% by weight. HSPgel RT MB-M (manufactured by Waters) was used as a column, and the mixed solution was used as a developing agent, and the measurement was performed at a column temperature of 50° C. and a flow rate of 0.40 mL/min. As the standard polystyrene, TSK standard polystyrene manufactured by Tosoh Corporation was used.
2. The voltage holding ratio was performed by the method described in "Mizushima et al., Proceedings of the 14th Liquid Crystal Conference" p78 (1988). The measurement was performed by applying a rectangular wave with a wave height of ±5 V to the cell. The measurement was performed at 60°C. This value is an index showing how much the applied voltage is retained after the frame period, and if this value is 100%, it indicates that all the charges are retained. A liquid crystal display device having good display quality can be obtained if the positive type liquid crystal mounted cell has 99.0% or more and the negative type liquid crystal mounted cell has 97.5% or more.
3. Measurement of ion content in liquid crystal (ion density)
According to the method described in Applied Physics, Vol. 65, No. 10, 1065 (1996), it was measured using a liquid crystal physical property measurement system 6254 manufactured by Toyo Technica. Using a triangular wave having a frequency of 0.01 Hz, the measurement was performed in a voltage range of ±10 V and a temperature of 60° C. (the area of the electrode was 1 cm ² ). If the ion density is high, problems such as seizure due to ionic impurities are likely to occur. That is, the ion density is a physical property value that is an index for predicting the occurrence of image sticking. When this value is 40 pC or less, the liquid crystal display device has a good display quality.

<Photolytic acid dianhydride and its derivative>

<Non-photolytic acid dianhydride>

式（ＤＩ−３６−１３）において、Ｒ^４４はＮＨＢｏｃ基である。ここでＢｏｃはｔ−ブトキシカルボニル基である。 <Diamine>

In formula (DI-36-13), R ⁴⁴ is an NHBoc group. Here, Boc is a t-butoxycarbonyl group.

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

<Additive>
Additive (Ad1): N,N,N',N'-Tetraglycidyl-4,4'-diaminodiphenylmethane Additive (Ad2): Add 1,3-bis(4,5-dihydro-2-oxazolyl)benzene Agent (Ad3): 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane Additive (Ad4): Celoxide 8000 (manufactured by Daicel Corporation)

Example 1 In a 100 mL three-necked flask equipped with a varnish synthetic stirring blade and a nitrogen introducing tube, 0.4308 g of the compound represented by the formula (1-1-1) and the formula (DI-5-28) were represented. Then, 2.6602 g of the compound described above was placed, and 34.0 g of N-methyl-2-pyrrolidone was added. The solution was ice-cooled and the liquid temperature was adjusted to 5° C., 2.9090 g of the compound represented by the formula (15) was added, and the mixture was stirred for 12 hours at room temperature. 30.0 g of γ-butyrolactone and 30.0 g of butyl cellosolve were added thereto, and the solution was heated and stirred at 60° C. until the weight average molecular weight of the polymer of the solute reached a desired weight average molecular weight, and the weight average molecular weight of the solute was approximately A varnish 1 having a content of 22,000 and a resin content of 6% by weight was obtained.

[Examples 2 to 73]
Varnishes 2 to 73 having a polymer solid content concentration of 6% by weight were prepared according to Example 1 except that the tetracarboxylic dianhydride and the diamine were changed. The weight average molecular weight was adjusted to about 20,000 to 25,000 for the polymer using the raw material having the photolytic structure and 60,000 to 70,000 for the polymer not using the raw material having the photolytic structure. Table 1 shows the tetracarboxylic dianhydride and the diamine used and the weight average molecular weight of the obtained polymer. Example 1 is also listed in Table 1.

[Example 74] Preparation of single-layer type aligning agent, preparation of cell for measuring electric characteristics and measurement of electric characteristics 10.0 g of varnish 1 synthesized in Example 1 was weighed in a 50 mL eggplant flask equipped with a stirring blade and a nitrogen introducing tube. Then, 5.0 g of N-methyl-2-pyrrolidone and 5.0 g of butyl cellosolve were added thereto, and the mixture was stirred at room temperature for 1 hour to obtain an aligning agent 1 having a resin content concentration of 3% by weight. This aligning agent was applied to a glass substrate with an IPS electrode and a glass substrate with a column spacer by a spinner method (2,000 rpm, 15 seconds). After coating, the substrate was heated at 80° C. for 3 minutes to evaporate the solvent, and then baked at 230° C. for 60 minutes to form a film having a thickness of about 100 nm. Then, using Ushio Denki Co., Ltd. Multi Light ML-501C/B, the substrate was irradiated with linearly polarized ultraviolet rays from the vertical direction through a polarizing plate. The exposure energy at this time was 1.0±0.1 J/cm ² at a wavelength of 254 nm by measuring the light amount with a UVT photometer UIT-150 (light receiver: UVD-S254) manufactured by Ushio Inc. The exposure time was adjusted so that Two substrates on which these alignment films were formed were bonded to each other with the surfaces on which the alignment films were formed facing each other and a space for injecting the liquid crystal composition provided between the facing alignment films. At this time, the polarization directions of the linearly polarized light irradiated on the respective alignment films were made parallel. The positive type liquid crystal composition A was injected into these cells to prepare a liquid crystal cell (liquid crystal display element) having a cell thickness of 7 μm.

物性値：ＮＩ １００．１℃； Δε ５．１； Δｎ ０．０９３； η ２５．６ｍＰａ・ｓ． <Positive Liquid Crystal Composition A>

Physical property values: NI 100.1°C; Δε 5.1; Δn 0.093; η 25.6 mPa·s.

The voltage holding ratio of this liquid crystal cell was 99.7% at 5 V-30 Hz, and the ion density was 8 pC. A reliability test was conducted by placing the cell on a backlight tester (Fuji Film Co., Ltd., FujiCOLOR LED Viewer Pro HR-2; brightness 2,700 cd/m ² ) for 1,000 hours with the cell turned on. The voltage holding ratio of the measuring cell after the reliability test was 99.5%, and the ion density was 10 pC.

[Examples 75 to 134]
A liquid crystal cell was prepared in accordance with Example 74 except that the varnish used was changed, and the voltage holding ratio, the ion density, and the reliability test were performed. The measurement results are shown in Table 2 together with Example 74.

Good results were obtained in the initial values and the values after the reliability test in all the cells of Examples 74 to 134. Here, the initial value is a result of measurement after the cell was manufactured and not mounted on the backlight tester.

[Example 135] Preparation of blend type orienting agent, preparation of cell for measuring electrical characteristics and measurement of electrical characteristics In a 50 mL eggplant flask equipped with a stirring blade and a nitrogen introducing tube, 2.0 g of the varnish 1 synthesized in Example 1 was used. 8.0 g of the varnish 65 synthesized in Example 71 was weighed, 5.0 g of N-methyl-2-pyrrolidone and 5.0 g of butyl cellosolve were added thereto, and the mixture was stirred at room temperature for 1 hour to obtain an aligning agent 62 having a resin content of 3% by weight. Obtained. A liquid crystal cell was produced according to the method described in Example 74. The voltage holding ratio of this liquid crystal cell was 99.8% at 5 V-30 Hz, and the ion density was 3 pC. The voltage holding ratio of the measurement cell after the reliability test was 99.6%, and the ion density was 10 pC.

[Examples 136 to 215]
A liquid crystal cell was prepared according to Example 135, except that the varnish used was changed, and the voltage holding ratio, the ion density, and the reliability test were performed. The varnish used and the measurement results are shown in Table 3 together with Example 135. In Table 3, varnish A is a varnish containing a polymer using a raw material having a photodegradable structure, and varnish B is a varnish containing a polymer not using a raw material having a photodegradable structure.

Good results were obtained in the initial values and the values after the reliability test in all the cells of Examples 135 to 215. Here, the initial value is a result of measurement after the cell was manufactured and not mounted on the backlight tester.

Example 216
An aligning agent was prepared according to the method described in Example 74 except that the negative liquid crystal composition B was used instead of the positive liquid crystal composition A to be injected into the cell, a liquid crystal cell was prepared, and the electrical characteristics were measured.

物性値：ＮＩ ７５．７℃； Δε −４．１； Δｎ ０．１０１； η １４．５ｍＰａ・ｓ． <Negative liquid crystal composition B>

Physical property value: NI 75.7° C.; Δε-4.1; Δn 0.101; η 14.5 mPa·s.

The voltage holding ratio of this liquid crystal cell was 99.4% at 5 V-30 Hz, and the ion density was 18 pC. The voltage holding ratio of the measurement cell after the reliability test was 99.2%, and the ion density was 26 pC.

[Examples 217 to 276]
A liquid crystal cell was produced according to Example 216 except that the varnish used was changed, and the voltage holding ratio, the ion density, and the reliability test were performed. The measurement results are shown in Table 4 together with Example 216.

Good results were obtained in the initial value and the value after the reliability test in all the cells of Examples 216 to 276. Here, the initial value is a result of measurement after the cell was manufactured and not mounted on the backlight tester.

Example 277
According to the method described in Example 135 except that the negative liquid crystal composition B was used instead of the positive liquid crystal composition A to be injected into the cell, an aligning agent was prepared, a liquid crystal cell was prepared, and a voltage holding ratio and an ion density were prepared. Was measured and a reliability test was performed. The voltage holding ratio of this liquid crystal cell was 99.5% at 5 V-30 Hz, and the ion density was 16 pC. The voltage holding ratio of the measurement cell after the reliability test was 99.4%, and the ion density was 23 pC.

[Examples 278 to 357]
A liquid crystal cell was prepared in accordance with Example 277 except that the varnish used was changed, and the voltage holding ratio, the ion density, and the reliability test were performed. The measurement results are shown in Table 5 together with that of Example 277.

Good results were obtained in the initial value and the value after the reliability test in all the cells of Examples 277 to 357. Here, the initial value is a result of measurement after the cell was manufactured and not mounted on the backlight tester.

Example 358
5 parts by weight of the additive (Ad1) was added to 100 parts by weight of the polymer, which was prepared in Example 10 and had a solid polymer concentration of 3% by weight. Using the obtained aligning agent 143, a liquid crystal cell was produced by a method according to Example 74, and voltage holding ratio, ion density measurement and reliability test were performed.

Example 359
5 parts by weight of the additive (Ad2) was added to 100 parts by weight of the polymer in the aligning agent 10 having a polymer solid content concentration of 3% by weight prepared in Example 10. Using the obtained aligning agent 144, a liquid crystal cell was produced by a method according to Example 74, and voltage holding ratio, ion density measurement and reliability test were performed.

Example 360
5 parts by weight of the additive (Ad3) was added to 100 parts by weight of the polymer in the aligning agent 10 having a polymer solid content concentration of 3% by weight prepared in Example 10. Using the obtained aligning agent 145, a liquid crystal cell was produced by the method according to Example 74, and the voltage holding ratio, the ion density were measured and the reliability test was performed.

[Example 361]
5 parts by weight of the additive (Ad4) was added to 100 parts by weight of the polymer, which was prepared in Example 10 and had a polymer solid content of 3% by weight. Using the obtained aligning agent 146, a liquid crystal cell was produced by a method according to Example 74, and voltage holding ratio, ion density measurement and reliability test were performed.

[Example 362]
5 parts by weight of the additive (Ad1) was added to 100 parts by weight of the polymer with respect to the aligning agent 107 having a polymer solid content concentration of 3% by weight prepared in Example 180. Using the obtained aligning agent 147, a liquid crystal cell was produced by the method according to Example 74, and the voltage holding ratio, the ion density were measured and the reliability test was performed.

[Example 363]
5 parts by weight of the additive (Ad2) was added to 100 parts by weight of the polymer with respect to the orienting agent 107 having a polymer solid content concentration of 3% by weight prepared in Example 180. Using the obtained aligning agent 148, a liquid crystal cell was produced by a method according to Example 74, and voltage holding ratio, ion density measurement and reliability test were performed.

Table 6 shows the measurement results of Examples 358 to 363.

In all the cells of Examples 358 to 363, good results were obtained in the initial value and the value after the reliability test even when the additive was added. Here, the initial value is a result of measurement after the cell was manufactured and not mounted on the backlight tester.

[Comparative Examples 1 to 3]
A liquid crystal cell was produced according to the method described in Example 74 except that the varnish 1 was replaced with the varnish 62, 63 or 64, and the voltage holding ratio, the ion density was measured and the reliability test was performed. The measurement results are shown in Table 7.

In all the cells of Comparative Examples 1 to 3, the result was obtained in which the value after the reliability test was significantly reduced.

[Comparative Examples 4 to 6]
Liquid crystal cells were prepared according to the methods described in Comparative Examples 1 to 3 except that the positive type liquid crystal composition A to be injected into the cell was replaced with the negative type liquid crystal composition B, and the voltage holding ratio and the ion density were measured. And a reliability test was conducted. The measurement results are shown in Table 8.

In all the cells of Comparative Examples 4 to 6, the result was obtained in which the value after the reliability test was significantly reduced.

[Comparative Examples 7 to 15]
A liquid crystal cell was prepared according to Example 135 except that the varnish used was changed, and the voltage holding ratio, the ion density, and the reliability test were performed. Table 9 shows the varnish used and the measurement results.

In all the cells of Comparative Examples 7 to 15, the result was obtained in which the value particularly after the reliability test was significantly reduced.

[Comparative Examples 16 to 24]
A liquid crystal cell was prepared according to the method described in Comparative Examples 7 to 15 except that the positive type liquid crystal composition A to be injected into the cell was replaced with the negative type liquid crystal composition B, and the voltage holding ratio and the ion density were measured. And a reliability test was conducted. The measurement results are shown in Table 10.

In all the cells of Comparative Examples 16 to 24, the result was obtained in which the value particularly after the reliability test was significantly reduced.

Example 364
In a 300 mL three-necked flask equipped with a stirring blade and a nitrogen introduction tube, 0.914 g of the diamine represented by the formula (1-1-1) and diamine 6 represented by the formula (DI-5-1) (m=2). 0.018 g, 7.80 g of the tetracarboxylic acid diester represented by the formula (26), 1.60 g of triethylamine as a base, and 4-(4,6-dimethoxy-1,3,5-triazine-as a condensing agent). 2-yl)-4-methylmorpholin-4-nium (24.90 g) and N-methyl-2-pyrrolidone (230.8 g) were added, and the mixture was reacted at room temperature for 3 hours to obtain a polyamic acid ester solution 74.

The obtained polyamic acid ester solution 74 was put into 1500 g of methanol, and the precipitated solid content was recovered. The solid content was dried under reduced pressure at 100° C. to obtain polyamic acid ester powder 74. The weight average molecular weight of the polyamic acid ester powder 74 was about 30,000.

6.0 g of polyamic acid ester powder 74 was weighed, 34.0 g of N-methyl-2-pyrrolidone, 30.0 g of γ-butyrolactone and 30.0 g of butyl cellosolve were added, and the mixture was stirred at room temperature for 4 hours. The ester powder 74 was completely dissolved. The thus obtained 6% by weight polyamic acid ester solution was varnish No. It was set to 74.

[Example 365]
In a 300 mL three-necked flask equipped with a stirring blade and a nitrogen introducing tube, 0.8616 g of the diamine represented by the formula (1-1-1), 2.5608 g of the diamine represented by the formula (DI-4-1), and the formula ( DI-36-9) (e=5), diamine 1.435 g, tetracarboxylic acid diester dichloride dichloride represented by formula (27) 9.689 g, and pyridine as a base 4.74 g were added, and N was added. 215.1 g of -methyl-2-pyrrolidone was added and reacted at room temperature for 3 hours to obtain a polyamic acid ester solution 75.

The obtained polyamic acid ester solution 75 was put into 1500 g of methanol, and the precipitated solid content was recovered. The solid content was dried under reduced pressure at 100° C. to obtain polyamic acid ester powder 75. The weight average molecular weight of the polyamic acid ester powder 75 was about 32,000.

6.0 g of polyamic acid ester powder 75 was weighed, 34.0 g of N-methyl-2-pyrrolidone, 30.0 g of γ-butyrolactone and 30.0 g of butyl cellosolve were added, and the mixture was stirred at room temperature for 4 hours. The ester powder 75 was completely dissolved. The thus obtained 6% by weight polyamic acid ester solution was varnish No. It was set to 75.

[Examples 366 to 385]
Varnish No. in which the solid content concentration of the polyamic acid ester was 6% by weight based on Example 364 or 365 except that the diamine was changed. 76-varnish No. 95 was prepared. Table 11 shows the weight average molecular weights of the used tetracarboxylic acid diester dichloride, dicarboxylic acid diester and diamine, and the obtained polyamic acid ester. Examples 364 and 365 are also listed in Table 11.

[Examples 386 to 403]
According to Example 74, varnish No. Nos. 74 to 91 were used for the alignment agent No. 158-175 were prepared. A liquid crystal cell was prepared using these aligning agents, and voltage holding ratio, ion density measurement and reliability test were performed. The measurement results are shown in Table 12.

Good results were obtained in the initial values and the values after the reliability test in all the cells of Examples 386 to 403. Here, the initial value is a result of measurement after the cell was manufactured and not mounted on the backlight tester.

[Examples 404 to 421]
Based on Example 135, the aligning agents 176 to 193 were obtained. Using this aligning agent, a liquid crystal cell was prepared according to the method described in Example 74. Table 13 shows the varnish used and the measurement results. In Table 13, varnish A is a varnish containing a polyamic acid ester using a raw material having a photolytic structure, and varnish B is a varnish containing a polymer not using a raw material having a photolytic structure.

In all the cells of Examples 404 to 421, good results were obtained in the initial value and the value after the reliability test. Here, the initial value is a result of measurement after the cell was manufactured and not mounted on the backlight tester.

[Examples 422 to 439]
Using the varnishes used in Examples 386 to 403 and replacing the positive liquid crystal composition A injected into the cell with the negative liquid crystal composition B, an aligning agent was prepared according to the method described in Example 74, A liquid crystal cell was prepared and its electrical characteristics were measured. The measurement results are shown in Table 14.

Good results were obtained in the initial value and the value after the reliability test in all the cells of Examples 422 to 439. Here, the initial value is a result of measurement after the cell was manufactured and not mounted on the backlight tester.

[Examples 440 to 457]
Using the varnishes used in Examples 404 to 421 and replacing the positive liquid crystal composition A to be injected into the cell with the negative liquid crystal composition B, an aligning agent was prepared according to the method described in Example 74, A liquid crystal cell was prepared and its electrical characteristics were measured. The measurement results are shown in Table 15.

Good results were obtained in the initial values and the values after the reliability test in all the cells of Examples 440 to 457. Here, the initial value is the result of measurement after the cell was manufactured without placing it on the backlight tester.

[Example 458]
5 parts by weight of the additive (Ad1) was added to 100 parts by weight of the polymer with respect to the aligning agent 176 prepared in Example 440 and having a polymer solid content of 3% by weight. Using the obtained aligning agent 194, a liquid crystal cell was produced by a method according to Example 440, and voltage holding ratio, ion density measurement and reliability test were performed.

[Example 459]
5 parts by weight of the additive (Ad2) was added to 100 parts by weight of the polymer with respect to the aligning agent 177 prepared in Example 441 and having a polymer solid content of 3% by weight. Using the obtained aligning agent 195, a liquid crystal cell was produced by a method according to Example 440, and voltage holding ratio, ion density measurement and reliability test were performed.

[Example 460]
5 parts by weight of the additive (Ad3) was added to 100 parts by weight of the polymer with respect to the aligning agent 178 prepared in Example 442 and having a polymer solid content of 3% by weight. Using the obtained aligning agent 196, a liquid crystal cell was produced by a method according to Example 440, and the voltage holding ratio, the ion density were measured and the reliability test was performed.

[Example 461]
5 parts by weight of the additive (Ad4) was added to 100 parts by weight of the polymer with respect to the aligning agent 179 prepared in Example 443 and having a polymer solid content concentration of 3% by weight. Using the obtained aligning agent 197, a liquid crystal cell was produced by a method according to Example 440, and voltage holding ratio, ion density measurement and reliability test were performed.

Table 16 shows the measurement results of Examples 458 to 461.

[Comparative Examples 25 to 28]
Varnish No. 92 to 95 according to the method described in Example 74. 198-201 was prepared. A liquid crystal cell was prepared using the obtained aligning agent, and voltage holding ratio, ion density measurement and reliability test were performed. The measurement results are shown in Table 17.

[Comparative Examples 29 to 32]
A liquid crystal cell was prepared according to the method described in Comparative Examples 25 to 28 except that the positive liquid crystal composition A to be injected into the cell was replaced with the negative liquid crystal composition B, and the voltage holding ratio and the ion density were measured. And a reliability test was conducted. The measurement results are shown in Table 18.

[Comparative Examples 33 to 36]
A liquid crystal cell was prepared according to Example 135 except that the varnish used was changed, and the voltage holding ratio, the ion density, and the reliability test were performed. Table 19 shows the varnish used and the measurement results.

[Comparative Examples 37 to 40]
A liquid crystal cell was prepared according to the method described in Comparative Examples 33 to 36 except that the positive liquid crystal composition A to be injected into the cell was replaced with the negative liquid crystal composition B, and the voltage holding ratio and the ion density were measured. And a reliability test was conducted. Table 20 shows the measurement results.

In all the cells of Comparative Examples 25 to 40, the value after the reliability test was significantly decreased.

By using the liquid crystal aligning agent for photoalignment of the present invention, it is possible to provide a liquid crystal display device having high display quality while maintaining a high voltage holding ratio and light resistance even after long-term use. The liquid crystal aligning agent for optical alignment of the present invention can be suitably applied to a horizontal electric field type liquid crystal display device.

Claims (17)

At least one selected from the group consisting of polyamic acid, polyamic acid ester obtained by reacting at least one selected from the group consisting of tetracarboxylic acid dianhydride and its derivative with diamine, and polyimide obtained by imidizing these. A liquid crystal aligning agent for photo-alignment, comprising one polymer;
A liquid crystal aligning agent for photo-alignment, wherein at least one of the raw material monomers of the polymer has a structure in which a bond is cleaved by ultraviolet rays, and the diamine contains at least one compound represented by the following formula (1) :

In formula (1), R ¹ is hydrogen or methyl; and
R ² is hydrogen, —OH, alkyl having 1 to 6 carbons, or alkoxy having 1 to 6 carbons;
The derivative of tetracarboxylic dianhydride is tetracarboxylic acid diester or tetracarboxylic acid diester dichloride. At least one selected from tetracarboxylic dianhydride and its derivative has a structure in which the bond is cleaved by ultraviolet light, and diamine reacts with a raw material monomer containing at least one compound represented by the following formula (1). other polymers used in admixture with the polymer obtained by the,
At least one selected from the group consisting of tetracarboxylic dianhydride and its derivative, and a polymer selected from the group consisting of polyamic acid, polyamic acid ester obtained by reacting diamine, and polyimide obtained by imidizing these. In addition, none of the tetracarboxylic dianhydride and its derivative has a structure in which the bond is cleaved by ultraviolet light , and the diamine is a raw material monomer containing no compound represented by the formula (1). It is a polymer obtained by reacting,
The liquid crystal aligning agent for optical alignment according to claim 1 .

In formula (1), R ¹ is hydrogen or methyl; and
R ² is hydrogen, —OH, alkyl having 1 to 6 carbons, or alkoxy having 1 to 6 carbons. At least one selected from tetracarboxylic dianhydride and its derivative has a structure in which the bond is cleaved by ultraviolet rays, and diamine is reacted with a raw material monomer containing at least one of the compounds represented by the following formula (1). used as a mixture with polymers obtained Te other polymer,
At least one selected from the group consisting of tetracarboxylic dianhydride and its derivative, and a polymer selected from the group consisting of polyamic acid, polyamic acid ester obtained by reacting diamine, and polyimide obtained by imidizing these. a is includes at least one of the any of the tetracarboxylic acid dianhydride and its derivatives has no structure which cleaves the bond with ultraviolet, and the diamine represented by the following formula (1) compound A polymer obtained by reacting raw material monomers,
The liquid crystal aligning agent for optical alignment according to claim 1 .

In formula (1), R ¹ is hydrogen or methyl; and
R ² is hydrogen, —OH, alkyl having 1 to 6 carbons, or alkoxy having 1 to 6 carbons. At least one selected from the group consisting of polyamic acid, polyamic acid ester obtained by reacting at least one selected from the group consisting of tetracarboxylic acid dianhydride and its derivative with diamine, and polyimide obtained by imidizing these. A liquid crystal aligning agent for photo-alignment, comprising two one polymer;
One of the polymers has a structure in which at least one of the raw material monomers has a bond cleaved by ultraviolet rays, and the diamine is a polymer obtained by reacting a raw material monomer containing no compound represented by the following formula (1). And
Another of the polymers is a raw material monomer in which none of the raw material monomers has a structure in which the bond is cleaved by ultraviolet rays, and the diamine contains at least one compound represented by the following formula (1). A liquid crystal aligning agent for photo-alignment, which is a polymer obtained by

In the formula (1), R ¹ Is hydrogen or methyl; and
R ^Two Is hydrogen, -OH, alkyl having 1 to 6 carbons, or alkoxy having 1 to 6 carbons;
The derivative of tetracarboxylic dianhydride is tetracarboxylic acid diester or tetracarboxylic acid diester dichloride. The diamine represented by the formula (1) is at least one selected from the group consisting of the diamine represented by the formula (1-1) and the diamine represented by the formula (1-2). 4. The liquid crystal aligning agent for optical alignment according to any one of 4 above;

In formulas (1-1) and (1-2), R ² is hydrogen, —OH, alkyl having 1 to 6 carbons, or alkoxy having 1 to 6 carbons. The diamine represented by the formula (1) is represented by the following formula (1-1-1) to formula (1-1-6), formula (1-1-17), formula (1-1-18), formula ( 1-2-1) to formula (1-2-6), formula (1-2-17), and at least one selected from the group consisting of diamines represented by formula (1-2-18). the liquid crystal aligning agent for optical alignment as claimed in any one of claims 1-5.

The tetracarboxylic acid dianhydride having a structure in which the bond is cleaved by ultraviolet rays and its derivative are selected from the group consisting of tetracarboxylic acid dianhydride having the structure represented by the following formulas (2) to (6) and its derivative. at least one is a liquid crystal aligning agent for optical alignment as claimed in any one of claims 1 to 6, which;

In formulas (2) to (6), R ³ is a structure represented by formulas (7) to (9),
R ⁸ is Ri alkyl der of 1 to 5 carbon atoms independently;

And in formula (7)-formula (9), R< ⁴ >-R< ⁷ > is independently hydrogen, a C1-C5 alkyl group, or a phenyl group. The tetracarboxylic dianhydride and its derivative having a structure in which the bond is cleaved by ultraviolet rays are at least selected from the group consisting of tetracarboxylic dianhydride and its derivative represented by the following formulas (10) to (14). The liquid crystal aligning agent for photo-alignment according to claim 7, which is one ;

In formulas (10) to (14), R ^{9 to} R ¹² are independently hydrogen, a methyl group, and a phenyl group; and R ¹³ is independently an alkyl group having 1 to 5 carbon atoms. The tetracarboxylic dianhydride and its derivative having a structure in which the bond is cleaved by ultraviolet rays is at least selected from the group consisting of tetracarboxylic dianhydride and its derivative represented by the following formulas (15) to (25). 9. The liquid crystal aligning agent for photo-alignment according to claim 8, which is one ;

In formulas (15) to (24), R ¹⁴ is independently an alkyl group having 1 to 5 carbon atoms. The tetracarboxylic acid dianhydride having no structure in which the bond is cleaved by ultraviolet rays is represented by the following formula (AN-1-1), formula (AN-1-2), formula (AN-1-13) and formula (AN). -3-2), Formula (AN-4-5), Formula (AN-4-17), Formula (AN-4-21), Formula (AN-4-29), Formula (AN-4-30). , Formula (AN-5-1), formula (AN-7-2), formula (AN-10-1), formula (AN-11-3), formula (AN-16-1), formula (AN- 16-3) and at least one selected from the formula (AN-16-4) : the liquid crystal aligning agent for photo-alignment according to any one of claims 1 to 9 ;

In Formula (AN-1-2) and Formula (AN-4-17), m is an integer of 1-12. The diamine having no structure in which the bond is cleaved by ultraviolet rays is represented by the following formula (DI-1) to formula (DI-16), formula (DIH-1) to formula (DIH-3), and formula (DI-31). ~ Liquid crystal aligning agent for photo-alignment according to any one of claims 1 to 10, which is at least one selected from the group consisting of formula (DI-35) ;

In formula (DI-1), G ²⁰ is —CH ₂ —, at least one —CH ₂ — may be replaced by —NH—, —O—, and m is an integer of 1 to 12. , At least one hydrogen of the alkylene may be replaced with —OH;
In formula (DI-3) and formula (DI-5) to formula (DI-7), G ²¹ is independently a single bond, —NH—, —NCH ₃ —, —O—, —S—, —S. _{-S -, - SO 2 -,} - CO -, - COO -, - CONH -, - CONCH 3 -, - C (CH 3) 2 -, - C (CF 3) 2 -, - (CH 2) m _{'-, - O- (CH 2} ) m' -O -, - N (CH 3) - (CH 2) k -N (CH 3) -, - (O-C 2 H 4) m '-O- _{, -O-CH 2 -C (CF} 3) 2 -CH 2 -O -, - O-CO- (CH 2) m '-CO-O -, - CO-O- (CH 2) m' -O _{-CO -, - (CH 2)} m '-NH- (CH 2) m' -, - CO- (CH 2) k -NH- (CH 2) k -, - (NH- (CH 2) m ' _{) k -NH -, - CO-} C 3 H 6 - (NH-C 3 H 6) n -CO -, - (CH 2) k -NH-CO-NH- (CH 2) k -, or -S - _(CH 2) _{m 'is} -S-, m' is an integer from 1 to 12 independently, k is an integer of 1 to 5, n represents 1 or 2;
In formula (DI-4), s is independently an integer of 0 to 2;
In formula (DI-6) and formula ^{(DI-7), G 22} are independently a single bond, -O -, - S -, - CO -, - C (CH 3) 2 -, - C (CF 3 ) _2- or alkylene having 1 to 10 carbon atoms;
In formulas (DI-2) to (DI-7), at least one hydrogen of the cyclohexane ring and the benzene ring is —F, —Cl, alkylene having 1 to 3 carbon atoms, —OCH ₃ , —OH, —CF. _{3, -CO 2 H, -CONH 2} , -NHC 6 H 5, may be replaced by phenyl or benzyl, in addition at least one hydrogen of the benzene ring in formula (DI-4) represented by the following formula (DI -4-a) to may be substituted with one selected from the group of groups represented by formula (DI-4-e);

In formula (DI-4-a) and formula (DI-4-b), R ²⁰ is independently hydrogen or —CH ₃ .
A group in which the bonding position is not fixed to the carbon atoms constituting the ring indicates that the bonding position in the ring is arbitrary, and the bonding position of —NH ₂ to the cyclohexane ring or the benzene ring is G ²¹ or G ^22. Any position except the bonding position of

In formula (DI-11), r is 0 or 1;
In formulas (DI-8) to (DI-11), the bonding position of —NH ₂ bonded to the ring is any position;

In formula (DI-12), R ²¹ and R ²² are independently alkyl or phenyl having 1 to 3 carbon atoms, and G ²³ is independently alkylene, phenylene, or alkyl-substituted phenylene having 1 to 6 carbon atoms. And w is an integer from 1 to 10;
In formula (DI-13), R ²³ is independently alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons or —Cl, p is independently an integer of 0 to 3, and q is Is an integer from 0 to 4;
In formula (DI-14), ring B is a monocyclic heteroaromatic, R ²⁴ is hydrogen, —F, —Cl, alkyl having 1 to 6 carbons, alkoxy having 1 to 6 carbons, and 2 carbons. To alkenyl, alkynyl having 1 to 6 carbon atoms, q is independently an integer of 0 to 4;
In formula (DI-15), ring C is a monocycle containing a heteroatom;
In formula (DI-16), G ²⁴ is a single bond, alkylene having 2 to 6 carbon atoms or 1,4-phenylene, and r is 0 or 1.
In the formulas (DI-13) to (DI-16), a group in which the bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary;

In formula (DIH-1), G ²⁵ is a single bond, alkylene having 1 to 20 carbon atoms, —CO—, —O—, —S—, —SO ₂ —, —C(CH ₃ ) ₂ —, or —. C _{(CF 3) 2} - a and;
In formula (DIH-2), ring D is a cyclohexane ring, a benzene ring or a naphthalene ring, at least one hydrogen of which may be replaced by methyl, ethyl or phenyl;
In formula (DIH-3), each ring E is independently a cyclohexane ring or a benzene ring, at least one hydrogen of this ring may be replaced with methyl, ethyl, or phenyl, and Y is a single bond, alkylene having 1 to 20 carbon atoms, -CO -, - O -, - S -, - SO 2 -, - C (CH 3) 2 -, or -C _{(CF 3) 2} - a and;
In formula (DIH-2) and formula (DIH-3), the bonding position of —CONHNH ₂ bonded to the ring is any position;

In the formula (DI-31), G ²⁶ is a single bond, —O—, —COO—, —OCO—, —CO—, —CONH—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—. , -OCF ₂ -, or - _(CH 2) _{m '-} is and, m' is an integer from 1 to ^{12, R 25} is a group having alkyl of 3 to 30 carbon atoms, phenyl, a steroid skeleton or below, of a group represented by the formula (DI-31-a), and in the alkyl, at least one hydrogen may be replaced by -F, at least one of -CH ₂ - -O -, - CH = may be replaced by CH- or -C≡C-, hydrogen which _{phenyl, -F, -CH 3, -OCH 3} , -OCH 2 F, -OCHF 2, -OCF 3, 3~ carbon atoms It may be substituted with alkyl of 30 or alkoxy of 3 to 30 carbon atoms, and the bonding position of —NH ₂ bonded to the benzene ring is any position in the ring,

In formula (DI-31-a), G ²⁷ , G ^28, and G ²⁹ are bonding groups, which are independently a single bond or an alkylene having 1 to 12 carbons, and one or more of these alkylenes are -. CH ₂ - is -O -, - COO -, - OCO -, - CONH -, - CH = CH- may be replaced by ring ^{B 21,} ring ^{B 22,} ring ^{B 23} and ring ^{B 24} is independently 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, naphthalene-1,5- diyl, naphthalene-2,7-diyl or anthracene-9,10-diyl, ring ^{B 21,} ring ^{B 22,} the ring ^{B 23} and ring ^{B 24,} at least one hydrogen replaced by -F or -CH ₃ S, t and u are each independently an integer from 0 to 2, the sum of which is 1 to 5, and when s, t or u is 2, 2 in each parenthesis is used. The two linking groups may be the same or different, the two rings may be the same or different,
R ²⁶ is hydrogen, —F, —OH, alkyl having 1 to 30 carbons, fluorine-substituted alkyl having 1 to 30 carbons, alkoxy having 1 to 30 carbons, —CN, —OCH ₂ F, —OCHF ₂ , or is -OCF _3, at least one -CH ₂ alkyl of 1 to 30 carbon atoms - may be replaced by a divalent group represented by the following formula (DI-31-b),

In formula (DI-31-b), R ²⁷ and R ²⁸ are independently alkyl having 1 to 3 carbons, and v is an integer from 1 to 6;

In formula (DI-32) and formula (DI-33), G ³⁰ is independently a single bond, —CO— or —CH ₂ —, R ²⁹ is independently hydrogen or —CH ₃ , and R ²⁹ is ³⁰ is hydrogen, alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons;
One hydrogen of the benzene ring in formula (DI-33) may be replaced with alkyl having 1 to 20 carbons or phenyl, and
In formula (DI-32) and formula (DI-33), a group in which the bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary;

In formula (DI-34) and formula (DI-35), G ³¹ is independently —O— or alkylene having 1 to 6 carbons, and G ³² is a single bond or alkylene having 1 to 3 carbons. ,
R ³¹ is hydrogen or alkyl having 1 to 20 carbons, and at least one —CH ₂ — of this alkyl may be replaced by —O—, —CH═CH— or —C≡C—, R ^{31 32} is alkyl having 6 to 22 carbons, R ³³ is hydrogen or alkyl having 1 to 22 carbons, ring B ²⁵ is 1,4-phenylene or 1,4-cyclohexylene, r is 0 or 1 and —NH ₂ bonded to the benzene ring indicates that the bonding position in the ring is arbitrary. A diamine having no structure in which a bond is cleaved by ultraviolet rays is represented by the following formula (DI-1-3), formula (DI-2-1), formula (DI-4-1), formula (DI-4-2). , Formula (DI-4-10), formula (DI-4-15), formula (DI-5-1), formula (DI-5-9), formula (DI-5-12), formula (DI- 5-13), Formula (DI-5-28), Formula (DI-5-30), Formula (DI-7-3), Formula (DI-13-1), Formula (DI-16-1), It is at least one selected from the group consisting of formula (DIH-2-1), formula (DI-5-42), formula (DI-36-9) and formula (DI-36-13). The liquid crystal aligning agent for photo-alignment according to.

In formula (DI-5-1), formula (DI-5-12), formula (DI-5-13), formula (DI-7-3), and formula (DI-36-13), m is 1 Is an integer from 12 to 12;
In formula (DI-5-30) and formula (DI-5-42), k is independently an integer of 1 to 5;
In formula (DI-7-3), n is independently 1 or 2.
In formula (DI-36-9), e is an integer from 2 to 10; and in formula ^{(DI-36-13), R 44} is -NHBoc or -N _{(Boc) 2.}
Boc is a t-butoxycarbonyl group here. The alkenyl-substituted nadimide compound, a compound having a radical-polymerizable unsaturated double bond, an oxazine compound, an oxazoline compound, and at least one compound selected from the group consisting of epoxy compounds, further containing any one of claims 1 to 12. Item 1. The liquid crystal aligning agent for optical alignment according to item 1. The liquid crystal aligning agent for optical alignment according to claim 1, which is used for manufacturing a horizontal electric field type liquid crystal display element. A liquid crystal alignment film for photo-alignment, which is formed by the liquid crystal alignment agent according to claim 1. A liquid crystal display device comprising the liquid crystal alignment film according to claim 15. A horizontal electric field type liquid crystal display device having the liquid crystal alignment film according to claim 15.