JP5967144B2 - Manufacturing method of liquid crystal display element - Google Patents

Description

The present invention provides a photopolymerizable monomer and / or a photopolymerizable oligomer comprising at least one selected from a polyimide obtained by reacting a diamine and tetracarboxylic dianhydride or a precursor thereof, polyamic acid or polyamic acid derivative. It is related with the liquid crystal aligning agent comprised as a component, the liquid crystal aligning film obtained from this liquid crystal aligning agent, its manufacturing method, and the liquid crystal display element which has this liquid crystal aligning film.

Liquid crystal display elements are used in various liquid crystal display devices such as monitors for televisions, notebook computers and desktop personal computers, viewfinders for video cameras, and projection displays. Various liquid crystal display elements such as TN (twisted nematic), STN (super twisted nematic), VA (vertical alignment), IPS (in-plane switching), and OCB (optical compensation vent) have been known so far. Among them, the VA display element is normally black and has high contrast, so that it is useful as a display for TV use, and demand is increasing.

The development of the technology of the liquid crystal display element is achieved not only by improving the driving method of the liquid crystal display element and the structure of the liquid crystal display element, but also by improving the components used in the liquid crystal display element. The liquid crystal display element usually has a liquid crystal alignment film for aligning the liquid crystal composition in the liquid crystal layer in a specific direction. The liquid crystal alignment film is one of the important elements related to the display quality of the liquid crystal display element, and the role of the liquid crystal alignment film has become important year by year as the quality of the liquid crystal display element is improved.

The liquid crystal alignment film is formed using a liquid crystal aligning agent. Currently, the liquid crystal aligning agent mainly used is a solution in which polyamic acid or soluble polyimide is dissolved in an organic solvent. The liquid crystal alignment film is formed by applying such a solution to a substrate and then forming the film by means such as heating.

The formed liquid crystal alignment film is rendered anisotropic by rubbing in a specific direction with a cloth such as rayon or cotton, and the liquid crystal is aligned in a predetermined direction.

On the other hand, there are some problems with the method of orientation control by rubbing. Some of them are listed.
1) Since the rubbing method is a mechanical method, it is difficult to precisely adjust the initial alignment state of the liquid crystal, and it is difficult to express different alignment directions in a fine region.
2) Scratches and scratches generated during rubbing cause a decrease in yield.
3) When the driving voltage is applied to the liquid crystal display device to complete the alignment of the liquid crystal molecules and then the driving voltage is turned off and the driving voltage is applied again, the final alignment state of the liquid crystal molecules is different from the previous driving voltage application. For this reason, every time a driving voltage is applied, the final alignment state of the liquid crystal molecules changes irregularly, and thus it takes a long time for the liquid crystal molecules to reach the final alignment state. Therefore, the response time of the liquid crystal becomes long.
4) In the case of the VA system, the viewing angle is deteriorated by using the orientation in a single direction.

In order to solve the above-mentioned problems, a method for improving response speed and contrast by using a PSA (Polymer Sustained Alignment) technique is particularly known for a VA display element (Patent Document 1: JP-A-10-186330). See the publication). However, in the PSA method, it is necessary to add a highly reactive monomer to a liquid crystal material that requires a high retention rate. The addition of a reactive compound to a liquid crystal material can cause a liquid crystal display failure, and therefore development of a display quality improving means replacing PSA has been desired.

Japanese Patent Laid-Open No. 10-186330

The present invention relates to a liquid crystal display device that achieves a desired response time and / or improved display quality, and a liquid crystal alignment that achieves a desired response time and / or improved display quality in the liquid crystal display device. Provided are a film, a manufacturing method thereof, and a liquid crystal aligning agent capable of forming the film.

The inventors of the present invention are composed of at least one selected from the following diamine and tetracarboxylic dianhydride polyimide or a precursor thereof, polyamic acid or polyamic acid derivative, and a photopolymerizable monomer and / or oligomer as components. The present inventors have found that a liquid crystal display element having a liquid crystal alignment film formed of a liquid crystal aligning agent that contributes to shortening of response time and display quality can be improved.

The present invention has the following configuration.

[1] A pair of opposed substrates, electrodes formed on one or both of the opposed surfaces of the pair of substrates, and formed on the opposed surfaces of the pair of substrates. A liquid crystal alignment film, and a liquid crystal layer formed between the pair of substrates,
By applying a voltage higher than the threshold voltage (Vth) of the liquid crystal composition to the liquid crystal composition, the liquid crystal aligns part or all of the photopolymerizable monomer or photopolymerizable oligomer present on the surface of the liquid crystal alignment film. Oriented along the direction to
Used in a liquid crystal display element that is created through a step of fixing the alignment state by irradiating light while applying a voltage,
Liquid crystal containing polyimide obtained by reacting diamine and tetracarboxylic dianhydride, at least one selected from the precursor polyamic acid and polyamic acid derivative, and a photopolymerizable monomer and / or photopolymerizable oligomer Alignment agent.

式（Ｉ）および（ＩＩ）において、
Ｒ’は独立して水素または炭素数１〜４のアルキルであり；
Ｒ^１は独立して２価の有機基であり；
Ｒ^２は独立して４価の有機基であり；そして、
Ｒ^１およびＲ^２は構成単位ごとに異なっていてもよい。 [2] A polyimide obtained by reacting diamine and tetracarboxylic dianhydride or a precursor thereof, polyamic acid or polyamic acid derivative, has a structural unit represented by the following formula (I) or (II) The liquid crystal aligning agent according to item [1], which is a compound.

In formulas (I) and (II):
R ′ is independently hydrogen or alkyl having 1 to 4 carbons;
R ¹ is independently a divalent organic group;
R ² is independently a tetravalent organic group; and
R ¹ and R ² may be different for each structural unit.

上記式中、ｍは独立して１〜１２の整数であり、ｎは独立して０〜２の整数であり；Ｇ^１は独立して単結合、−Ｏ−、−Ｓ−、−Ｓ−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−、−（ＣＨ_２）_ｐ−、−Ｏ−（ＣＨ_２）_ｐ−Ｏ−、または−Ｓ−（ＣＨ_２）_ｐ−Ｓ−であり、前記ｐは独立して１〜１２の整数であり；Ｇ^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１〜１０のアルキレンであり；
式中のシクロヘキサン環およびベンゼン環の任意の−Ｈは、−Ｆ、−ＯＨ、−ＣＦ_３、−ＣＨ_３またはベンジルで置き換えられていてもよく；そして、
シクロヘキサン環またはベンゼン環への−ＮＨ_２の結合位置は、Ｇ^１またはＧ^２の結合位置を除く任意の位置である。 [3] At least one selected from the group of compounds represented by the following formulas (III-1) to (III-7), or represented by formulas (III-1) to (III-7): The liquid crystal aligning agent as described in the above item [2], which is a mixture of at least one selected from the group of compounds to be prepared and other diamines.

In the above formula, m is independently an integer of 1 to 12, n is independently an integer of 0 to 2; G ¹ is independently a single bond, —O—, —S—, —S—. _{S -, - SO 2 -,} - CO -, - CONH -, - NHCO -, - C (CH 3) 2 -, - C (CF 3) 2 -, - (CH 2) p -, - O- ( CH ₂ ) _p —O—, or —S— (CH ₂ ) _p —S—, wherein p is independently an integer of 1 to 12; G ² is independently a single bond, —O—, _{-S -, - CO -, -} C (CH 3) 2 -, - C (CF 3) 2 - be or alkylene having 1 to 10 carbon atoms;
Any —H in the cyclohexane and benzene rings in the formula may be replaced by —F, —OH, —CF ₃ , —CH ₃ or benzyl; and
The bonding position of —NH ₂ to the cyclohexane ring or the benzene ring is an arbitrary position excluding the bonding position of G ¹ or G ² .

[4] The diamine is represented by the formula (III-2-3), (III-4-1) to (III-4-5), (III-4-9), (III-5-1) to (III-5). -12), (III-5-31) to (III-5-35) and (III-7-3), which is at least one selected from the group of compounds described in the above item [3]. The liquid crystal aligning agent of description.

[5] The liquid crystal aligning agent according to the above [2], wherein the diamine is a mixture of at least one diamine having a side chain structure or at least one diamine having a side chain structure and another diamine.

式（ＩＩＩ−８）において、Ｇ^３は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−、−ＣＯＮＨ−、または−（ＣＨ_２）_ｍ−であり、ｍは１〜１２の整数であり；
Ｒ^４は炭素数３〜２０のアルキル、フェニル、ステロイド骨格を有する基、シクロヘキシルまたは式（ＩＩＩ−８−ａ）で表される基であり；
このアルキルにおいて、任意の−Ｈは−Ｆで置き換えられていてもよく、任意の−ＣＨ₂−は−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられていてもよく；
このフェニルの−Ｈは、−Ｆ、−ＣＨ_３、−ＯＣＨ_３、−ＯＣＨ_２Ｆ、−ＯＣＨＦ_２、−ＯＣＦ_３、炭素数３〜２０のアルキルまたは炭素数３〜２０のアルコキシで置き換えられていてもよく；このシクロヘキシルの−Ｈは炭素数３〜２０のアルキルまたは炭素数３〜２０のアルコキシで置き換えられていてもよく；そして、
ベンゼン環への−ＮＨ_２の結合位置は任意である。
ただし、Ｇ^３が−（ＣＨ_２）_ｍ−であり、ｍが１であり、Ｒ^４がフェニルであるとき、このフェニルの少なくとも１つの−Ｈは、−Ｆ、−ＣＨ_３、−ＯＣＨ_３、−ＯＣＨ_２Ｆ、−ＯＣＨＦ_２、−ＯＣＦ_３、炭素数３〜２０のアルキルまたは炭素数３〜２０のアルコキシで置き換えられている。

式（ＩＩＩ−８−ａ）において、Ｒ^５は−Ｈ、−Ｆ、炭素数１〜２０のアルキル、炭素数１〜２０のフッ素置換アルキル、炭素数１〜２０のアルコキシ、−ＣＮ、−ＯＣＨ_２Ｆ、−ＯＣＨＦ_２、または−ＯＣＦ_３であり；
Ｇ^４、Ｇ^５およびＧ^６は結合基であり、これらは独立して単結合、または炭素数１〜１２のアルキレンであり；このアルキレン中の１以上の−ＣＨ_２−は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＣＨ＝ＣＨ−で置き換えられていても良く；
Ａ、Ａ^１、Ａ^２およびＡ^３は環であり、これらは独立して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；
Ａ、Ａ^１、Ａ^２およびＡ^３において、任意の−Ｈは−Ｆまたは−ＣＨ_３で置き換えられていてもよく；
ａ、ｂおよびｃは独立して０〜２の整数であり、これらの合計は１〜５であり；そして、
ａ、ｂまたはｃ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いてもよく、２つの環は同じであっても異なっていてもよい。

式（ＩＩＩ−９）および（ＩＩＩ−１０）において、
Ｒ^６は独立して−Ｈまたは−ＣＨ_３であり；
Ｒ^７は独立して−Ｈ、炭素数１〜２０のアルキル、または炭素数２〜２０のアルケニルであり；
Ｇ^７は独立して単結合、−ＣＯ−または−ＣＨ₂−であり；
式（ＩＩＩ−１０）におけるベンゼン環の１つの−Ｈは、炭素数１〜２０のアルキルまたはフェニルで置き換えられていてもよく；そして、
環を構成するいずれかの炭素原子に結合位置が固定されていない基は、その結合位置が任意であることを示す。

式（ＩＩＩ−１１）および（ＩＩＩ−１２）において、
Ｒ^８は−Ｈまたは炭素数１〜２０のアルキルであり、このアルキルにおける任意の−ＣＨ_２−は、−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられていてもよく；
Ｒ^９は炭素数６〜２２のアルキルであり；
Ｒ^１０は−Ｈまたは炭素数１〜２２のアルキルであり；
Ｇ^８は−Ｏ−または炭素数１〜６のアルキレンであり；
Ａ^４は１，４−フェニレンまたは１，４−シクロヘキシレンであり；
Ｇ^９は単結合または炭素数１〜３のアルキレンであり；
ｄは０または１であり；そして、
ベンゼン環への−ＮＨ_２の結合位置は任意である。 [6] The liquid crystal alignment according to item [5], wherein the diamine having a side chain structure is at least one selected from the group of compounds represented by formulas (III-8) to (III-12). Agent.

In Formula (III-8), G ³ is a single bond, —O—, —COO—, —OCO—, —CO—, —CONH—, or — (CH ₂ ) _m —, and m is 1 to 12. An integer of;
R ⁴ is alkyl having 3 to 20 carbon atoms, phenyl, a group having a steroid skeleton, cyclohexyl, or a group represented by the formula (III-8-a);
In this alkyl, any —H may be replaced by —F, and any —CH ₂ — may be replaced by —O—, —CH═CH— or —C≡C—;
_-H in which _{phenyl, -F, -CH 3, -OCH 3} , -OCH 2 F, -OCHF 2, -OCF 3, has been replaced by an alkoxy alkyl or C3-20 having 3 to 20 carbon atoms The —H of the cyclohexyl may be replaced by alkyl having 3 to 20 carbons or alkoxy having 3 to 20 carbons; and
The bonding position of —NH ₂ to the benzene ring is arbitrary.
Provided that when G ³ is — (CH ₂ ) _m —, m is 1, and R ⁴ is phenyl, at least one —H of the phenyl is —F, —CH ₃ , —OCH ₃ , _{-OCH 2 F, -OCHF 2, -OCF} 3, is replaced by an alkoxy alkyl or C3-20 having 3 to 20 carbon atoms.

In the formula (III-8-a), R ⁵ is —H, —F, alkyl having 1 to 20 carbons, fluorine-substituted alkyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons, —CN, —OCH ₂ F, —OCHF ₂ , or —OCF ₃ ;
G ⁴ , G ⁵ and G ⁶ are a linking group, and these are independently a single bond or alkylene having 1 to 12 carbons; one or more —CH ₂ — in the alkylene is —O—, — May be replaced by COO-, -OCO-, -CONH-, -CH = CH-;
A, A ¹ , A ² and A ³ are rings, which 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;
In A, A ¹ , A ² and A ³ , any —H may be replaced by —F or —CH ₃ ;
a, b and c are independently integers from 0 to 2 and their sum is from 1 to 5;
When a, b or c is 2, the two linking groups in each parenthesis may be the same or different, and the two rings may be the same or different.

In formulas (III-9) and (III-10),
R ⁶ is independently —H or —CH ₃ ;
R ⁷ is independently —H, alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons;
G ⁷ is independently a single bond, —CO— or —CH ₂ —;
One -H of the benzene ring in formula (III-10) may be replaced by alkyl or phenyl having 1 to 20 carbon atoms; and
A group whose bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position is arbitrary.

In formulas (III-11) and (III-12),
R ⁸ is —H or alkyl having 1 to 20 carbons, and any —CH ₂ — in the alkyl may be replaced by —O—, —CH═CH— or —C≡C—;
R ⁹ is alkyl having 6 to 22 carbons;
R ¹⁰ is —H or alkyl having 1 to 22 carbons;
G ⁸ is —O— or alkylene having 1 to 6 carbons;
A ⁴ is 1,4-phenylene or 1,4-cyclohexylene;
G ⁹ is a single bond or alkylene having 1 to 3 carbon atoms;
d is 0 or 1; and
The bonding position of —NH ₂ to the benzene ring is arbitrary.

[7] The liquid crystal aligning agent according to the above [6], wherein the diamine having a side chain structure is at least one selected from the group of compounds represented by formula (III-8).

[8] The liquid crystal aligning agent according to the above [6], wherein the diamine having a side chain structure is at least one selected from the group of compounds represented by formulas (III-9) and (III-10) .

[9] The liquid crystal aligning agent according to the above [6], wherein the diamine having a side chain structure is at least one selected from the group of compounds represented by formulas (III-11) and (III-12) .

式（ＩＩＩ−８−１）および（ＩＩＩ−８−２）において、Ｒ^４ａは炭素数３〜２０のアルキルまたは炭素数３〜２０のアルコキシであり；
式（ＩＩＩ−８−４）〜（ＩＩＩ−８−６）において、Ｒ^５aは炭素数１〜１８のアルキルまたは炭素数１〜１８のアルコキシであり；
式（ＩＩＩ−８−２１）、（ＩＩＩ−８−２７）および（ＩＩＩ−８−３９）において、Ｒ^５ｂは−Ｈ、−Ｆ、炭素数１〜２０のアルキル、炭素数１〜２０のアルコキシ、−ＣＮ、−ＯＣＨ_２Ｆ、−ＯＣＨＦ_２または−ＯＣＦ_３であり；そして、
式（ＩＩＩ−８−２２）、（ＩＩＩ−８−２８）および（ＩＩＩ−８−３０）において、Ｒ^４ｄは炭素数１〜２０のアルキル、または炭素数１〜２０のアルコキシである。 [10] The diamine having a side chain structure is represented by the following formulas (III-8-1), (III-8-2), (III-8-4) to (III-8-6), (III-8-21). ), (III-8-22), (III-8-27), (III-8-28), (III-8-30), (III-8-39), (III-8-41) to The liquid crystal according to item [6], which is at least one selected from the group of compounds represented by (III-8-45) and (III-9-1) to (III-9-4): Display element.

In formulas (III-8-1) and (III-8-2), R ^4a is alkyl having 3 to 20 carbons or alkoxy having 3 to 20 carbons;
In formulas (III-8-4) to (III-8-6), R ^5a is alkyl having 1 to 18 carbons or alkoxy having 1 to 18 carbons;
In the formulas (III-8-21), (III-8-27) and (III-8-39), R ^5b is —H, —F, alkyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons. , _-CN, be -OCH 2 F, -OCHF ₂ or -OCF _3; and,
In formulas (III-8-22), (III-8-28) and (III-8-30), R ^4d is alkyl having 1 to 20 carbons or alkoxy having 1 to 20 carbons.

式（ＩＩＩ−１３）において、
Ｒ^１１およびＲ^１２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^１０はメチレン、フェニレンまたはアルキル置換されたフェニレンであり；
ｊは１〜６の整数であり；そして
ｋは１〜１０の整数である。 [11] The liquid crystal aligning agent according to the above [2], wherein the diamine is at least one selected from the group of compounds represented by formula (III-13).

In formula (III-13):
R ¹¹ and R ¹² are independently alkyl or phenyl having 1 to 3 carbon atoms;
G ¹⁰ is methylene, phenylene or alkyl-substituted phenylene;
j is an integer from 1 to 6; and k is an integer from 1 to 10.

[12] The liquid crystal aligning agent according to the above [11], wherein the diamine is a compound represented by the formula (III-13-1).

式（ＩＶ−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り；そして、
Ｘ^１は独立して単結合または−ＣＨ_２−である。

式（ＩＶ−２）において、
Ｒ^１３、Ｒ^１４、Ｒ^１５、およびＲ^１６は−Ｈ、−ＣＨ_３、−ＣＨ_２ＣＨ_３、またはフェニルである。

式（ＩＶ−３）において、環Ａ^５はシクロヘキサン環またはベンゼン環である。

式（ＩＶ−４）において、
Ｇ^１２は単結合、炭素数１〜１２のアルキレン、−Ｏ−、−ＣＯ−、−Ｓ−、−Ｃ（ＣＨ_３）_２−、−ＳＯ−、または−Ｃ（ＣＦ_３）_２−であり；そして、
環Ａ^５は独立してシクロヘキサン環またはベンゼン環である。

式（ＩＶ−５）において、Ｒ^１７は独立して−Ｈ、または−ＣＨ_３である。

式（ＩＶ−６）において、
Ｘ^１は独立して単結合または−ＣＨ_２−であり；そして、
ｖは１または２である。

式（ＩＶ−７）において、Ｘ^１は単結合または−ＣＨ_２−である。

式（ＩＶ−８）において、
Ｒ^１８は−Ｈ、−ＣＨ_３、−ＣＨ_２ＣＨ_３、またはフェニルであり；そして、
Ａ^６はシクロヘキサン環またはシクロヘキセン環である。

式（ＩＶ−９）において、ｗ１およびｗ２は０または１である。

式（ＩＶ−１１）において、Ａ^５は独立してシクロヘキサン環またはベンゼン環である。

式（ＩＶ−１２）において、Ｘ^２は炭素数２〜６のアルキレンであり、そして、
Ｐｈはフェニルの略号である。

[13] The tetracarboxylic dianhydride is at least one selected from the group of compounds represented by the following formulas (IV-1) to (IV-13), or the formulas (IV-1) to (IV): The liquid crystal aligning agent according to item [2], which is a mixture of at least one selected from the group of compounds represented by -13) and other tetracarboxylic dianhydrides.

In formula (IV-1),
G ¹¹ is a single bond, alkylene having 1 to 12 carbons, 1,4-phenylene, or 1,4-cyclohexylene; and
X ¹ is independently a single bond or —CH ₂ —.

In formula (IV-2),
R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ are —H, —CH ₃ , —CH ₂ CH ₃ , or phenyl.

In the formula (IV-3), ring ^{A 5} are a cyclohexane ring or a benzene ring.

In formula (IV-4),
G ¹² is a single bond, alkylene having 1 to 12 carbons, —O—, —CO—, —S—, —C (CH ₃ ) ₂ —, —SO—, or —C (CF ₃ ) ₂ —. And
Ring A ⁵ are a cyclohexane ring or benzene ring independently.

In the formula (IV-5), R ¹⁷ is independently —H or —CH ₃ .

In formula (IV-6):
X ¹ is independently a single bond or —CH ₂ —; and
v is 1 or 2.

In the formula (IV-7), X ¹ is a single bond or —CH ₂ —.

In formula (IV-8):
R ¹⁸ is —H, —CH ₃ , —CH ₂ CH ₃ , or phenyl; and
A ⁶ is a cyclohexane ring or a cyclohexene ring.

In formula (IV-9), w1 and w2 are 0 or 1.

In formula (IV-11), A ⁵ is independently a cyclohexane ring or a benzene ring.

In formula (IV-12), X ² is alkylene having 2 to 6 carbons, and
Ph is an abbreviation for phenyl.

式（ＩＶ−１２−１）において、Ｐｈはフェニルの略号である。 [14] The tetracarboxylic dianhydride has the formula (IV-1-1), (IV-2-1), (IV-3-1), (IV-3-2), (IV-4-23). ), (IV-5-3), (IV-7-2), (IV-10), (IV-12-1), and (IV-13). The liquid crystal aligning agent according to item [13], which is one.

In formula (IV-12-1), Ph is an abbreviation for phenyl.

[15] The tetracarboxylic dianhydride is at least one selected from the group of compounds represented by formulas (IV-1), (IV-2) and (IV-3), or formula (IV-1) ), (IV-2), and a liquid crystal according to item [14], which is a mixture of at least one selected from the group of compounds represented by (IV-3) and other tetracarboxylic dianhydrides Alignment agent.

式（Ｖ−１−１）〜（Ｖ−１−５）において、Ｒ^ｂは−Ｈ、ハロゲン、−ＣＦ_３または炭素数１〜５のアルキルである。 [16] The liquid crystal aligning agent according to the above [1], wherein the photopolymerizable monomer is at least one compound represented by the following formula (V).

R ^a1 -Z- (BZ) _m1 -R ^a1 (V)

In formula (V):
R ^a1 is independently a polymerizable group represented by the following formulas (V-1-1) to (V-1-5), —H, halogen, —CN, —CF ₃ , —CF ₂ H, -CFH _2, -OCF _3, alkyl having _{-OCF 2 H, -N = C =} O, -N = C = S or C 1-20;
In this alkyl, any —CH ₂ — represents —O—, —S—, —SO ₂ —, —CO—, —COO—, —OCO—, —CH═CH—, —CF═CF— or — May be replaced by C≡C-;
Optional -H may be replaced by halogen or -CN;
At least one of R ^a1 is a polymerizable group represented by formulas (V-1-1) to (V-1-5);
B is a ring and is independently a saturated or unsaturated independent ring having 3 to 20 carbon atoms, a condensed ring, or a spirocyclic divalent group;
In these rings, any —CH ₂ — may be replaced by —O—;
Any —CH═ may be replaced by —N═;
Any -H is _{halogen, -CN, -NO 2, -NC,} -N = C = O, -N = C = S, silyl which is substituted with 1 to 3 alkyl of 1 to 4 carbon atoms, May be substituted with linear or branched alkyl having 1 to 10 carbon atoms or halogenated alkyl having 1 to 10 carbon atoms;
In this alkyl, any —CH ₂ — may be replaced by —O—, —CO—, —COO—, —OCO—, —OCOO—, —CH═CH— or —C≡C—. ;
Z is independently a single bond or alkylene having 1 to 20 carbon atoms;
In this alkylene, arbitrary —CH ₂ — represents —O—, —S—, —SO ₂ —, —CO—, —COO—, —OCO—, —OCOO—, —CH═CH—, —CF═. May be replaced by CF-, -CH = N-, -N = CH-, -N = N-, -N (O) = N-, or -C≡C-;
Optional -H may be replaced by halogen, alkyl having 1 to 10 carbons, or alkyl halide having 1 to 10 carbons; and
m1 is an integer from 1 to 6,
When m1 is an integer of 2 to 6, a plurality of -BZ- in parentheses may be the same or different.

In the formulas (V-1-1) to (V-1-5), R ^b is —H, halogen, —CF _3, or alkyl having 1 to 5 carbons.

[17] At least one of R ^a1 in the formula (V) is a polymerizable group represented by any one of the formulas (V-1-1), (V-1-2), or (V-1-3). The liquid crystal aligning agent as described in the above item [16].

[18] Ring B in formula (V) is independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6. -Diyl, fluorene-2,7-diyl, bicyclo [2.2.2] octane-1,4-diyl, bicyclo [3.1.0] hexane-3,6-diyl or triptycene-1,4-diyl A divalent group represented by:
In these rings, any —CH ₂ — may be replaced by —O—;
Any —CH═ may be replaced by —N═;
Arbitrary —H is substituted with halogen, —CN, —NO ₂ , —NC, —N═C═O, —N═C═S, 1 to 3 C 1-4 alkyl or phenyl Optionally substituted by silyl, linear or branched alkyl having 1 to 10 carbon atoms or alkyl halide having 1 to 10 carbon atoms;
In this alkyl, any —CH ₂ — may be replaced by —O—, —CO—, —COO—, —OCO—, —OCOO—, —CH═CH—, or —C≡C—. The liquid crystal aligning agent as described in the above item [16].

式（Ｖ−２−１）〜（Ｖ−２−２５）において、Ｌはハロゲン、炭素数１〜３のアルキル、炭素数１〜３のアルコキシ、または炭素数１〜３のハロゲン化アルキルを表す。 [19] The ring B in the formula (V) is independently one selected from the group of groups represented by the following formulas (V-2-1) to (V-2-25), The liquid crystal aligning agent as described in the item [18].

In formulas (V-2-1) to (V-2-25), L represents a halogen, an alkyl having 1 to 3 carbon atoms, an alkoxy having 1 to 3 carbon atoms, or an alkyl halide having 1 to 3 carbon atoms. .

（式（Ｖ−３−１）〜（Ｖ−３−１２）において、Ｒ^ｃは−Ｈまたは−ＣＨ_３を示し、ベンゼン環上の−Ｈはハロゲン、−ＣＨ_３、−ＣＦ_３または−ＯＣＨ_３で置き換えられていてもよく；
Ｒ^ｄは独立して−Ｈ、ハロゲン、−ＣＨ_３、−ＣＦ_３、−ＯＣＨ_３、フェニルまたは同一炭素上にある２つのＲ^ｄが炭素数６〜１５の飽和または不飽和の炭化水素環を形成していても良く；
そして、ｍ２およびｍ３は独立して１〜２０の整数である。 [20] The item [16], wherein the photopolymerizable monomer is at least one selected from the group of compounds represented by the following formulas (V-3-1) to (V-3-12): The liquid crystal aligning agent of description.

(In the formulas (V-3-1) to (V-3-12), R ^c represents —H or —CH _3, and —H on the benzene ring represents halogen, —CH ₃ , —CF ₃ or —OCH. _May be replaced by ₃ ;
R ^d independently represents —H, halogen, —CH ₃ , —CF ₃ , —OCH ₃ , phenyl, or two R ^d on the same carbon each represents a saturated or unsaturated hydrocarbon ring having 6 to 15 carbon atoms. May be formed;
And m2 and m3 are integers of 1-20 independently.

[21] The liquid crystal alignment according to the above [1], containing a photopolymerizable monomer or photopolymerizable oligomer in an amount of 0.01 to 50% by weight of the total solid content including polyimide, polyamic acid, or polyamic acid derivative. Agent.

[22] The liquid crystal aligning agent according to the above [1], further comprising a polymerization initiator and / or a polymerization inhibitor.

[23] At least one additive selected from the group consisting of an alkenyl-substituted nadiimide compound, a compound having a radical polymerizable unsaturated double bond, an oxazine compound, an oxazoline compound, a liquid crystal alignment polyorganosiloxane, and an epoxy compound. The liquid crystal aligning agent according to item [1], further contained.

[24] The additive is N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, 1,3 A group of compounds consisting of -bis (N, N-diglycidylaminomethyl) cyclohexane, liquid crystal alignment polyorganosiloxane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 3-glycidyloxypropyltrimethoxysilane The liquid crystal aligning agent according to the above [23], which is at least one selected from the group consisting of:

[25] When the liquid crystal aligning agent layer applied on the substrate is baked at a temperature of 100 to 230 ° C., 50% by weight or more of the photopolymerizable monomer and / or photopolymerizable oligomer remains without being thermally polymerized. A liquid crystal alignment film formed from the liquid crystal aligning agent according to item [1].

[26] When the liquid crystal aligning agent layer applied on the substrate is baked at a temperature of 180 to 230 ° C., 50% by weight or more of the photopolymerizable monomer and / or photopolymerizable oligomer remains without being thermally polymerized. The liquid crystal alignment film according to the above [25].

[27] The liquid crystal aligning agent according to the above [1], which is obtained by reacting a photopolymerizable monomer and / or a photopolymerizable oligomer by irradiating ultraviolet light of 1,000 to 300,000 mJ / cm ^2. A liquid crystal alignment film formed from

[28] The polyimide, polyamic acid, or polyamic acid derivative represented by the formula (I) or (II) is a group in which R ¹ and R ² in the molecule are 4 to 50% of the total number of each radical by light. The liquid crystal aligning agent according to the item [2], which is a compound having a radical generating group.

[29] The liquid crystal aligning agent according to the above [26], wherein the radical generating group is at least one selected from the group of groups having a benzophenone skeleton and a cinnamate skeleton.

上記式中、Ｒ^１９は−Ｈまたは炭素数１〜２５の炭化水素基であり；
この炭化水素基の任意の−Ｈは−Ｆで置き換えられていてもよく；
Ｘ^３およびＸ^４は独立して単結合、−ＣＯＯ−または−Ｏ−であり；そして、
Ｇ^１３は炭素数２〜６のアルキレンである。

[30] The above [28], wherein the radical generating group is at least one selected from the group of groups represented by the following formulas (VI-1) to (VI-4) and (VII-1): A liquid crystal aligning agent according to item.

In the above formula, R ¹⁹ is —H or a hydrocarbon group having 1 to 25 carbon atoms;
Any —H of the hydrocarbon group may be replaced by —F;
X ³ and X ⁴ are independently a single bond, —COO— or —O—; and
G ¹³ is alkylene having 2 to 6 carbon atoms.

[31] A liquid crystal alignment film formed using the liquid crystal aligning agent according to any one of [1] to [24] and [28] to [30].

[32] A liquid crystal display device having the liquid crystal alignment film according to the item [31].

According to the present invention, it is possible to provide a liquid crystal display element in which response time is shortened and / or display quality is improved.

In the present specification, hereinafter, for example, the “compound represented by the formula (III-1)” may be referred to as “compound (III-1)”. Other formula numbers are handled in the same manner.

The term “arbitrary” used in describing a chemical structural formula means that not only the position but also the number is arbitrary. And, for example, the expression “any A may be replaced by B, C or D” means that at least one A may be replaced by B and at least one A may be replaced by C , Meaning that at least one A may be replaced by D, and more than one A may be replaced by at least two of BD. However, when arbitrary —CH ₂ — may be replaced with another group, it does not include the replacement of a plurality of consecutive —CH ₂ — with the same group. Ph means phenyl and Me means methyl.

A substituent that is not clearly bonded to any one of the carbons constituting the ring means that the bonding position is free as long as there is no chemical problem. In the chemical structural formula, a group in which a letter (for example, A) is surrounded by a hexagon means a group having a ring structure (ring A). When the same symbol is used in more than one formula, it means that the ring, linking group or terminal group represented by the symbol has the same defined range, but the same group within the defined range at the same time in all formulas Doesn't mean it must be. The same group may be used in a plurality of formulas, or different groups may be used for each formula.

The present invention relates to a polyimide obtained by reacting a diamine with tetracarboxylic dianhydride, at least one polymer selected from polyamic acid and polyamic acid derivatives as precursors thereof, a photopolymerizable monomer and / or photopolymerization. Liquid crystal aligning agent containing a functional oligomer. The liquid crystal aligning agent of the present invention includes a pair of opposed substrates, electrodes formed on one or both of the opposed surfaces of the pair of substrates, and the pair of substrates facing each other. And a liquid crystal layer formed between the pair of substrates, and a voltage higher than a threshold voltage (Vth) of the liquid crystal composition is applied to the liquid crystal composition. By aligning part or all of the photopolymerizable monomer or photopolymerizable oligomer present on the liquid crystal alignment film surface along the direction in which the liquid crystal is aligned, light is applied while voltage is applied to fix the alignment state. It is used for the liquid crystal display element produced through the process of making it.

The voltage higher than the threshold voltage (Vth) of the liquid crystal composition is defined as follows. A voltage is applied to the liquid crystal display element in which various conditions such as the arrangement of polarizing plates corresponding to the display mode (TN mode, IPS mode, VA mode, etc.) are set, and the transmitted light intensity that changes according to the change in voltage is observed. The transmitted light intensity when no voltage is applied is 0% (in the case of normally black), and the transmitted light intensity when the maximum is within the observable range is 100% (in the case of normally white, no voltage is applied). Sometimes the transmitted light intensity is 100%.) Here, the voltage at which the transmitted light intensity becomes 10% is V _10, that is, the threshold voltage (Vth). The voltage applied in the step of fixing the alignment state by irradiating light needs to be higher than the threshold voltage (Vth). The upper limit of the voltage to be applied is not particularly defined, but a voltage having a height at which the displacement of liquid crystal molecules is saturated (cannot be displaced any more) by the applied voltage may be considered as the upper limit. The voltage to be applied can be arbitrarily selected between the threshold voltage (Vth) and the voltage at which the displacement of the liquid crystal molecules is saturated.

The voltage V ₉₀ when the transmitted light intensity is 90% is defined as a saturation voltage (Vsat). The upper limit of the voltage to be applied may be based on this saturation voltage (Vsat). The applied voltage may exceed the saturation voltage (Vsat).

式（Ｉ）および（ＩＩ）において、Ｒ’は独立して水素または炭素数１〜４のアルキルであり、Ｒ^１は独立して２価の有機基であり、Ｒ^２は独立して４価の有機基であり、そして、Ｒ^１およびＲ^２は構成単位ごとに異なっていてもよい。 The polymer contained in the liquid crystal aligning agent of the present invention is a compound having a structural unit represented by the following formula (I) or (II).

In the formulas (I) and (II), R ′ is independently hydrogen or alkyl having 1 to 4 carbon atoms, R ¹ is independently a divalent organic group, and R ² is independently tetravalent. And R ¹ and R ² may be different for each structural unit.

The above polymers include not only polyimide obtained by completely dehydrating and ring-closing reaction of polyamic acid, but also partially imidized polyamic acid and tetracarboxylic dianhydride obtained by partially dehydrating and ring-closing reaction of polyamic acid. A polyamic acid-polyamide copolymer obtained by substituting a part with a dicarboxylic acid, and a polyamideimide obtained by subjecting a part or all of this polyamic acid-polyamide copolymer to a dehydration ring-closing reaction are also included.

The diamine and tetracarboxylic dianhydride, the photopolymerizable monomer and the photopolymerizable oligomer, which are raw materials for the polymer contained in the liquid crystal aligning agent of the present invention, will be described in this order.

上記式中、ｍは独立して１〜１２の整数であり、ｎは独立して０〜２の整数であり；
Ｇ^１は独立して単結合、−Ｏ−、−Ｓ−、−Ｓ−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−、−（ＣＨ_２）_ｐ−、−Ｏ−（ＣＨ_２）_ｐ−Ｏ−、または−Ｓ−（ＣＨ_２）_ｐ−Ｓ−であり、前記ｐは独立して１〜１２の整数であり；Ｇ^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１〜１０のアルキレンであり；
式中のシクロヘキサン環およびベンゼン環の任意の−Ｈは、−Ｆ、−ＯＨ、−ＣＦ_３、−ＣＨ_３またはベンジルで置き換えられていてもよく；そして、
シクロヘキサン環またはベンゼン環への−ＮＨ_２の結合位置は、Ｇ^１またはＧ^２の結合位置を除く任意の位置である。 Examples of the diamine used in the present invention are compounds represented by formulas (III-1) to (III-7). One of these diamines may be selected and used alone, two or more of these diamines may be selected and mixed, or at least one selected from these diamines and other A diamine (a diamine other than the compounds (III-1) to (III-7)) may be mixed and used.

In the above formula, m is independently an integer of 1 to 12, and n is independently an integer of 0 to 2;
G ¹ is independently a single bond, —O—, —S—, —S—S—, —SO ₂ —, —CO—, —CONH—, —NHCO—, —C (CH ₃ ) ₂ —, — C (CF ₃ ) ₂ —, — (CH ₂ ) _p —, —O— (CH ₂ ) _p —O—, or —S— (CH ₂ ) _p —S—, wherein p is independently 1 G ² is independently a single bond, —O—, —S—, —CO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, or C 1 10 alkylene;
Any —H in the cyclohexane and benzene rings in the formula may be replaced by —F, —OH, —CF ₃ , —CH ₃ or benzyl; and
The bonding position of —NH ₂ to the cyclohexane ring or the benzene ring is an arbitrary position excluding the bonding position of G ¹ or G ² .

Examples of compound (III-1) to compound (III-3) are shown below.

Examples of compound (III-4) are shown below.

Examples of compound (III-5) are shown below.

Examples of compound (III-6) are shown below.

Examples of compound (III-7) are shown below.

Among the specific examples of the compounds (III-1) to (III-7), more preferable examples are the formulas (III-2-3), (III-4-1) to (III-4-5), ( III-4-9), (III-5-1) to (III-5-12), (III-5-26), (III-5-27), (III-5-31) to (III- 5-35) (III-6-1), (III-6-2), (III-6-6), (III-7-1) to (III-7-5) and (III-7-15) ) To (III-7-16), and particularly preferred examples are the formulas ((III-2-3), (III-4-1) to (III-4-5), (III- 4-9), (III-5-1) to (III-5-12), (III-5-31) to (III-5-35) and (III-7-3) A compound represented.

When compounds (III-1) to (III-7) are used in the present invention, the ratio of compounds (III-1) to (III-7) to the total amount of diamine used depends on the structure of the selected diamine and the desired It is adjusted according to the voltage holding ratio and the residual DC reduction effect. The preferable ratio is 20 to 100 mol%, the more preferable ratio is 50 to 100 mol%, and the still more preferable ratio is 70 to 100 mol%.

Another example of a preferred diamine is a diamine having a side chain structure. These diamines are used in applications that require a large pretilt angle, such as VA liquid crystal display elements, OCB liquid crystal display elements, and STN liquid crystal display elements. In the present specification, a diamine having a side chain structure means a diamine having a substituent located on the side of the main chain when a chain connecting two amino groups is the main chain. That is, a diamine having a side chain structure reacts with a tetracarboxylic dianhydride, so that a polyamic acid, a polyamic acid derivative or a polyimide having a substituent in a side orientation with respect to the polymer main chain (branched polyamic acid, branched) A polyamic acid derivative or a branched polyimide) can be provided. The liquid crystal alignment film formed from such a liquid crystal alignment agent containing polyamic acid or polyimide can increase the pretilt angle in the liquid crystal display element.

Therefore, the side substituents in the diamine having a side chain structure may be appropriately selected according to the required pretilt angle. For example, this lateral substituent is preferably a group having 3 or more carbon atoms. In particular,
1) phenyl which may have a substituent, cyclohexyl which may have a substituent, cyclohexylphenyl which may have a substituent, bi (cyclohexyl) phenyl which may have a substituent Or an alkyl, alkenyl or alkynyl having 3 or more carbon atoms,
2) phenyloxy which may have a substituent, cyclohexyloxy which may have a substituent, bi (cyclohexyl) oxy which may have a substituent, which may have a substituent Phenylcyclohexyloxy, cyclohexylphenyloxy which may have a substituent, or alkyloxy, alkenyloxy or alkynyloxy having 3 or more carbon atoms,
3) phenylcarbonyl, or alkylcarbonyl, alkenylcarbonyl or alkynylcarbonyl having 3 or more carbon atoms,
4) Phenylcarbonyloxy, or alkylcarbonyloxy, alkenylcarbonyloxy or alkynylcarbonyloxy having 3 or more carbon atoms,
5) phenyloxycarbonyl which may have a substituent, cyclohexyloxycarbonyl which may have a substituent, bicyclohexyloxycarbonyl which may have a substituent, may have a substituent A good bicyclohexylphenyloxycarbonyl, an optionally substituted cyclohexylbiphenyloxycarbonyl, or an alkyloxycarbonyl, alkenyloxycarbonyl or alkynyloxycarbonyl having 3 or more carbon atoms,
6) phenylaminocarbonyl, or alkylaminocarbonyl having 3 or more carbon atoms, alkenylaminocarbonyl or alkynylaminocarbonyl,
7) cyclic alkyl having 3 or more carbon atoms,
8) Cycloalkylalkyl which may have a substituent, phenylalkyl which may have a substituent, bicyclohexylalkyl which may have a substituent, cyclohexylphenyl which may have a substituent Alkyl, optionally substituted bicyclohexylphenylalkyl, optionally substituted phenylalkyloxy, alkylphenyloxycarbonyl, or alkylbiphenylyloxycarbonyl,
9) A benzene ring which may have a substituent and / or a cyclohexane ring which may have a substituent is a single bond, —O—, —COO—, —OCO—, —CONH— or a carbon number of 1 to A group having two or more rings or a group having a steroid skeleton bonded via 3 alkylenes,
However, it is not limited to these.

Examples of the above substituent groups include alkyl, fluorine-substituted alkyl, alkoxy, and alkoxyalkyl. In the present specification, “alkyl” used without particular explanation indicates that either a straight-chain alkyl or a branched-chain alkyl may be used. The same applies to “alkenyl” and “alkynyl”.

Preferred examples of the diamine having a side chain structure are compounds selected from the group of compounds represented by each of formula (III-8) to formula (III-12).

式（ＩＩＩ−８）における記号の意味は次の通りである。Ｇ^３は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−、−ＣＯＮＨ−または−（ＣＨ_２）_ｍ−であって、ｍは１〜１２の整数である。Ｒ^４は炭素数３〜２０のアルキル、フェニル、ステロイド骨格を有する基、または下記の式（ＩＩＩ−８−ａ）で表される基である。このアルキルにおいて、任意の−Ｈは−Ｆで置き換えられてもよく、そして任意の−ＣＨ₂−は−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられていてもよい。このフェニルの−Ｈは、−Ｆ、−ＣＨ_３、−ＯＣＨ_３、−ＯＣＨ_２Ｆ、−ＯＣＨＦ_２、−ＯＣＦ_３、炭素数３〜２０のアルキルまたは炭素数３〜２０のアルコキシで置き換えられていてもよく；このシクロヘキシルの−Ｈは炭素数３〜２０のアルキルまたは炭素数３〜２０のアルコキシで置き換えられていてもよい。ベンゼン環へのＮＨ_２の結合位置は任意であるが、２つのＮＨ_２の結合位置関係はメタまたはパラであることが好ましい。即ち、基「Ｒ^４−Ｇ^３−」の結合位置を１位としたとき、２つのＮＨ_２はそれぞれ、３位と５位、または２位と５位に結合していることが好ましい。

式（ＩＩＩ−８−ａ）において、Ｒ^５は−Ｈ、−Ｆ、炭素数１〜２０のアルキル、炭素数１〜２０のフッ素置換アルキル、炭素数１〜２０のアルコキシ、−ＣＮ、−ＯＣＨ_２Ｆ、−ＯＣＨＦ_２、または−ＯＣＦ_３であり；Ｇ^４、Ｇ^５およびＧ^６は結合基であり、これらは独立して単結合、または炭素数１〜１２のアルキレンであり；このアルキレン中の１以上の−ＣＨ_２−は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＣＨ＝ＣＨ−で置き換えられていても良く；
Ａ、Ａ^１、Ａ^２およびＡ^３は環であり、これらは独立して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；Ａ、Ａ^１、Ａ^２およびＡ^３において、任意の−Ｈは−Ｆまたは−ＣＨ_３で置き換えられてもよく；ａ、ｂおよびｃ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；ａ、ｂまたはｃ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。

The meanings of symbols in formula (III-8) are as follows. G ³ is a single bond, —O—, —COO—, —OCO—, —CO—, —CONH— or — (CH ₂ ) _m —, and m is an integer of 1 to 12. R ⁴ is an alkyl having 3 to 20 carbon atoms, phenyl, a group having a steroid skeleton, or a group represented by the following formula (III-8-a). In this alkyl, any —H may be replaced with —F, and any —CH ₂ — may be replaced with —O—, —CH═CH— or —C≡C—. _-H in which _{phenyl, -F, -CH 3, -OCH 3} , -OCH 2 F, -OCHF 2, -OCF 3, has been replaced by an alkoxy alkyl or C3-20 having 3 to 20 carbon atoms The —H of the cyclohexyl may be replaced by alkyl having 3 to 20 carbons or alkoxy having 3 to 20 carbons. The bonding position of NH ₂ to the benzene ring is arbitrary, but the bonding position relationship between the _two NH ₂ is preferably meta or para. That is, when the bonding position of the group “R ⁴ —G ³ —” is the 1-position, the two NH ₂ are preferably bonded to the 3-position and the 5-position, or the 2-position and the 5-position, respectively.

In the formula (III-8-a), R ⁵ is —H, —F, alkyl having 1 to 20 carbons, fluorine-substituted alkyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons, —CN, —OCH ₂ F, —OCHF ₂ , or —OCF ₃ ; G ⁴ , G ⁵ and G ⁶ are linking groups, and these are independently a single bond or alkylene having 1 to 12 carbon atoms; One or more of —CH ₂ — may be replaced by —O—, —COO—, —OCO—, —CONH—, —CH═CH—;
A, A ¹ , A ² and A ³ are rings, which 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; in A, A ¹ , A ² and A ³ Any —H may be replaced by —F or —CH ₃ ; a, b and c are independently integers from 0 to 2 and their sum is from 1 to 5; a, b or When c is 2, the two linking groups in each parenthesis may be the same or different, and the two rings may be the same or different.

The meanings of symbols in formula (III-9) and formula (III-10) are as follows. R ⁶ is independently —H or —CH ₃ . R ⁷ is independently —H, alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons. G ⁷ is independently a single bond, —CO— or —CH ₂ —. One -H of the benzene ring in formula (III-10) may be substituted with alkyl having 1 to 20 carbons or phenyl. A group whose bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary.

Formula (III-9) in two groups - one of the "NH ₂ phenylene ^-G 7 -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 . Formula (III-10) in two groups - bonded to the benzene rings "NH ₂ phenylene ^-G 7 -O-" is that with respect to the binding position of the steroid nucleus, are each meta or para position preferable. In Formula (III-9) and Formula (III-10), the NH ₂ bonding position to the benzene ring is preferably the meta position or the para position with respect to the G ⁷ bonding position.

式（ＩＩＩ−１１）および式（ＩＩＩ−１２）における記号の意味は次の通りである。Ｒ^８は−Ｈまたは炭素数１〜２０のアルキルであって、このアルキルの任意の−ＣＨ₂−は、−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよい。Ｒ^９は炭素数６〜２２のアルキルであり、そしてＲ^１０は−Ｈまたは炭素数１〜２２のアルキルである。Ｇ^８は−Ｏ−または炭素数１〜６のアルキレンである。Ａ^４は１，４−フェニレンまたは１，４−シクロヘキシレンであり、Ｇ^９は単結合または炭素数１〜３のアルキレンであり、そしてｄは０または１である。ベンゼン環へのＮＨ_２の結合位置は任意であるが、Ｇ^８の結合位置に対してメタ位またはパラ位であることが好ましい。

The meanings of symbols in formula (III-11) and formula (III-12) are as follows. R ⁸ is —H or alkyl having 1 to 20 carbons, and any —CH ₂ — in the alkyl may be replaced by —O—, —CH═CH— or —C≡C—. R ⁹ is alkyl having 6 to 22 carbon atoms, and R ¹⁰ is —H or alkyl having 1 to 22 carbon atoms. G ⁸ is —O— or alkylene having 1 to 6 carbons. A ⁴ is 1,4-phenylene or 1,4-cyclohexylene, G ⁹ is a single bond or alkylene having 1 to 3 carbon atoms, and d is 0 or 1. Although the bonding position of NH ₂ to the benzene ring is arbitrary, it is preferably a meta position or a para position with respect to the bonding position of G ⁸ .

In the present invention, when compound (III-8) to compound (III-12) are used as a diamine raw material, at least one of these diamines may be selected and used, or these (these) diamines and Other diamines (diamines other than compound (III-8) to compound (III-12)) may be mixed and used. At this time, the selection range of other diamines includes the above-mentioned compounds (III-1) to (III-7).

これらの式において、Ｒ^４ａは炭素数３〜２０のアルキルまたは炭素数３〜２０のアルコキシであり、好ましくは炭素数５〜２０のアルキルまたは炭素数５〜２０のアルコキシである。Ｒ^５ａは炭素数１〜１８のアルキルまたは炭素数１〜１８のアルコキシであり、好ましくは炭素数３〜１８のアルキルまたは炭素数３〜１８のアルコキシである。 Examples of compound (III-8) are shown below.

In these formulas, R ^4a is alkyl having 3 to 20 carbons or alkoxy having 3 to 20 carbons, preferably alkyl having 5 to 20 carbons or alkoxy having 5 to 20 carbons. R ^5a is alkyl having 1 to 18 carbons or alkoxy having 1 to 18 carbons, preferably alkyl having 3 to 18 carbons or alkoxy having 3 to 18 carbons.

これらの式において、Ｒ^４ｂは炭素数４〜１６のアルキルであり、好ましくは炭素数６〜１６のアルキルである。Ｒ^４ｃは炭素数６〜２０のアルキルであり、好ましくは炭素数８〜２０のアルキルである。

In these formulas, R ^4b is alkyl having 4 to 16 carbon atoms, preferably alkyl having 6 to 16 carbon atoms. R ^4c is alkyl having 6 to 20 carbons, preferably alkyl having 8 to 20 carbons.

これらの式において、Ｒ^４ｄ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^５ｂは−Ｈ、−Ｆ、炭素数１〜２０のアルキル、炭素数１〜２０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３〜２０のアルキルまたは炭素数３〜２０のアルコキシである。そして、Ｇ^１４は炭素数１〜２０のアルキレンである。

In these formulas, R ^4d is alkyl having 1 to 20 carbons or alkoxy having 1 to 20 carbons, preferably alkyl having 3 to 20 carbons or alkoxy having 3 to 20 carbons. R ^5b is —H, —F, alkyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons, —CN, —OCH ₂ F, —OCHF ₂ or —OCF ₃ , preferably ₃ to 20 carbons. Or alkyl having 3 to 20 carbon atoms. G ¹⁴ is alkylene having 1 to 20 carbon atoms.

化合物（ＩＩＩ−８）に関する上記の具体例のうち、化合物（ＩＩＩ−８−１）〜化合物（ＩＩＩ−８−１１）、化合物（ＩＩＩ−８−３９）および化合物（ＩＩＩ−８−４１）が好ましく、化合物（ＩＩＩ−８−２）、化合物（ＩＩＩ−８−４）、化合物（ＩＩＩ−８−５）、化合物（ＩＩＩ−８−６）、化合物（ＩＩＩ−８−３９）および化合物（ＩＩＩ−８−４１）がより好ましい。

Among the specific examples of Compound (III-8), Compound (III-8-1) to Compound (III-8-11), Compound (III-8-39) and Compound (III-8-41) Preferably, compound (III-8-2), compound (III-8-4), compound (III-8-5), compound (III-8-6), compound (III-8-39) and compound (III -8-41) is more preferable.

Examples of compound (III-9) are shown below.

Examples of compound (III-10) are shown below.

これらの式において、Ｒ^５ｃは−Ｈまたは炭素数１〜２０のアルキル、好ましくは−Ｈまたは炭素数１〜１０のアルキルであり、そしてＲ^５ｄは−Ｈまたは炭素数１〜１０のアルキルである。 Examples of compound (III-11) are shown below.

In these formulas, R ^5c is —H or alkyl having 1 to 20 carbons, preferably —H or alkyl having 1 to 10 carbons, and R ^5d is —H or alkyl having 1 to 10 carbons. .

これらの式において、Ｒ^９は炭素数６〜２０のアルキルであり、Ｒ^１０は−Ｈまたは炭素数１〜１０のアルキルである。 Examples of compound (III-12) are shown below.

In these formulas, R ⁹ is alkyl having 6 to 20 carbon atoms, and R ¹⁰ is —H or alkyl having 1 to 10 carbon atoms.

More specifically, the following diamines are used.

Particularly preferred diamines represented by the general formula (III-12) include the formulas (III-12-1-1), (III-12-1-2), and (III-12-1-3). .

When using the compound (III-8) to the compound (III-12) in the present invention, the ratio of the compound (III-8) to the compound (III-12) with respect to the total amount of the diamine used depends on the selected side chain structure. It is adjusted according to the structure of the diamine it has and the desired pretilt angle. The ratio is 1-100 mol%, and a preferable ratio is 5-80 mol%.

In the present invention, a diamine that is not compound (III-1) to compound (III-7) or compound (III-8) to compound (III-12) can be used. Examples of such diamines include naphthalene-based diamines, diamines having a fluorene ring, diamines having a siloxane bond, and the like, and include diamines having a side chain structure other than compound (III-8) to compound (III-12). You can also

式（ＩＩＩ−１３）において、Ｒ^１１およびＲ^１２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^１０はメチレン、フェニレンまたはアルキル置換されたフェニレンである。ｊは１〜６の整数を表し、ｋは１〜１０の整数を表す。） An example of a diamine having a siloxane bond is a diamine represented by the following formula (III-13).

In formula (III-13), R ¹¹ and R ¹² are each independently alkyl or phenyl having 1 to 3 carbon atoms, and G ¹⁰ is methylene, phenylene or alkyl-substituted phenylene. j represents an integer of 1 to 6, and k represents an integer of 1 to 10. )

Examples of compound (III-13) are shown below.

上記式中、Ｒ^３２およびＲ^３３は独立して炭素数３〜２０のアルキルである。 Examples of diamines having a side chain structure other than compound (III-1) to compound (III-13) are shown below.

In the above formula, R ³² and R ³³ are each independently alkyl having 3 to 20 carbon atoms.

Examples of the tetracarboxylic dianhydride used in the present invention include tetracarboxylic dianhydrides represented by formulas (IV-1) to (IV-13).

式（ＩＶ−１）において、Ｇ^１１は単結合、炭素数１〜１２のアルキレン、１，４−フェニレン環、もしくは１，４−シクロヘキシレン環を表し、Ｘ^１はそれぞれ独立して単結合もしくはＣＨ_２を表し、例えば下記構造式で表されるテトラカルボン酸二無水物が挙げられる。

In Formula (IV-1), G ¹¹ represents a single bond, an alkylene having 1 to 12 carbon atoms, a 1,4-phenylene ring, or a 1,4-cyclohexylene ring, and each X ¹ independently represents a single bond or It represents CH _2, tetracarboxylic acid dianhydride represented e.g. by the following structural formulas.

式（ＩＶ−２）において、Ｒ^１３、Ｒ^１４、Ｒ^１５、およびＲ^１６は−Ｈ、−ＣＨ_３、−ＣＨ_２ＣＨ_３、もしくはフェニルを表し、例えば下記構造式で表されるテトラカルボン酸二無水物が挙げられる。

In the formula (IV-2), R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ represent —H, —CH ₃ , —CH ₂ CH ₃ , or phenyl. For example, a tetracarboxylic acid represented by the following structural formula And dianhydrides.

式（ＩＶ−３）において、環Ａ^５はシクロヘキサン環もしくはベンゼン環を表し、例えば下記構造式で表されるテトラカルボン酸二無水物が挙げられる。

In the formula (IV-3), ring A ⁵ are represent cyclohexane ring or benzene ring, tetracarboxylic acid dianhydride represented e.g. by the following structural formulas.

式（ＩＶ−４）において、Ｇ^１２は単結合、−ＣＨ_２−、−ＣＨ_２ＣＨ_２−、−Ｏ−、−Ｓ−、−Ｃ（ＣＨ_３）_２−、−ＳＯ−、または−Ｃ（ＣＦ_３）_２−を表し、環Ａ^５はそれぞれ独立してシクロヘキサン環もしくはベンゼン環を表し、例えば下記構造式で表されるテトラカルボン酸二無水物が挙げられる。

In the formula ^{(IV-4), G 12} represents a single _{bond, -CH 2 -, - CH 2} CH 2 -, - O -, - S -, - C (CH 3) 2 -, - SO-, or -C (CF ₃ ) ₂ — and ring A ⁵ each independently represents a cyclohexane ring or a benzene ring, and examples thereof include tetracarboxylic dianhydrides represented by the following structural formula.

式（ＩＶ−５）において、Ｒ^１７は独立に−Ｈ、または−ＣＨ_３を表し、例えば下記構造式で表されるテトラカルボン酸二無水物が挙げられる。

In the formula (IV-5), R ¹⁷ independently represents —H or —CH ₃ , and examples thereof include a tetracarboxylic dianhydride represented by the following structural formula.

式（ＩＶ−６）において、Ｘ^１はそれぞれ独立して単結合もしくは−ＣＨ_２−を表し、ｖは１または２を表し、例えば下記構造式で表されるテトラカルボン酸二無水物が挙げられる。

In the formula (IV-6), X ¹ each independently represents a single bond or —CH ₂ —, v represents 1 or 2, and examples thereof include tetracarboxylic dianhydride represented by the following structural formula. .

式（ＩＶ−７）において、Ｘ^１は単結合もしくは−ＣＨ_２−を表し、例えば下記構造式で表されるテトラカルボン酸二無水物が挙げられる。

In formula (IV-7), X ¹ represents a single bond or —CH ₂ —, and examples thereof include tetracarboxylic dianhydrides represented by the following structural formula.

式（ＩＶ−８）において、Ｒ^１８は−Ｈ、−ＣＨ_３、−ＣＨ_２ＣＨ_３、もしくはフェニルを表し、環Ａ^６はシクロヘキサン環もしくはシクロヘキセン環を表し、例えば下記構造式で表されるテトラカルボン酸二無水物が挙げられる。

In the formula (IV-8), R ¹⁸ represents —H, —CH ₃ , —CH ₂ CH ₃ , or phenyl, and ring A ⁶ represents a cyclohexane ring or a cyclohexene ring. Carboxylic dianhydrides are mentioned.

式（ＩＶ−９）において、ｗ１およびｗ２は０または１を表す。例えば下記構造式で表されるテトラカルボン酸二無水物が挙げられる。

In formula (IV-9), w1 and w2 represent 0 or 1. For example, the tetracarboxylic dianhydride represented by the following structural formula is mentioned.

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

式（ＩＶ−１１）において、環Ａ^５は独立してシクロヘキサン環またはベンゼン環を表す。例えば下記構造式で表されるテトラカルボン酸二無水物が挙げられる。

In the formula (IV-11), the ring ^{A 5} are representative of a cyclohexane ring or benzene ring independently. For example, the tetracarboxylic dianhydride represented by the following structural formula is mentioned.

式（ＩＶ−１２）において、Ｘ^２は炭素数２〜６のアルキレンを表し、例えば下記構造式で表されるテトラカルボン酸二無水物が挙げられる。

In the formula (IV-12), X ² represents an alkylene having 2 to 6 carbon atoms, and examples thereof include tetracarboxylic dianhydrides represented by the following structural formula.

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

Preferred tetracarboxylic dianhydrides include the following structures.

式（Ｖ−１−１）〜（Ｖ−１−５）において、Ｒ^ｂは−Ｈ、ハロゲン、−ＣＦ_３または炭素数１〜５のアルキルである。 The photopolymerizable monomer or photopolymerizable oligomer used in the present invention is at least one compound represented by the formula (V).

R ^a1 -Z- (BZ) _m1 -R ^a1 (V)

In formula (V):
R ^a1 is independently a polymerizable group represented by the following formulas (V-1-1) to (V-1-5), —H, halogen, —CN, —CF ₃ , —CF ₂ H, -CFH _2, -OCF _3, alkyl having _{-OCF 2 H, -N = C =} O, -N = C = S or C 1-20;
In this alkyl, any —CH ₂ — represents —O—, —S—, —SO ₂ —, —CO—, —COO—, —OCO—, —CH═CH—, —CF═CF— or — May be replaced by C≡C-;
Optional -H may be replaced by halogen or -CN;
At least one of R ^a1 is a polymerizable group represented by formulas (V-1-1) to (V-1-5);
B is a ring and is independently a saturated or unsaturated independent ring having 3 to 20 carbon atoms, a condensed ring, or a spirocyclic divalent group;
In these rings, any —CH ₂ — may be replaced by —O—;
Any —CH═ may be replaced by —N═;
Any -H is _{halogen, -CN, -NO 2, -NC,} -N = C = O, -N = C = S, silyl which is substituted with 1 to 3 alkyl of 1 to 4 carbon atoms, May be substituted with linear or branched alkyl having 1 to 10 carbon atoms or halogenated alkyl having 1 to 10 carbon atoms;
In this alkyl, any —CH ₂ — may be replaced by —O—, —CO—, —COO—, —OCO—, —OCOO—, —CH═CH— or —C≡C—. ;
Z is independently a single bond or alkylene having 1 to 20 carbon atoms;
In this alkylene, arbitrary —CH ₂ — represents —O—, —S—, —SO ₂ —, —CO—, —COO—, —OCO—, —OCOO—, —CH═CH—, —CF═. May be replaced by CF-, -CH = N-, -N = CH-, -N = N-, -N (O) = N-, or -C≡C-;
Optional -H may be replaced by halogen, alkyl having 1 to 10 carbons, or alkyl halide having 1 to 10 carbons; and
m1 is an integer from 1 to 6,
When m1 is an integer of 2 to 6, a plurality of -BZ- in parentheses may be the same or different.

In the formulas (V-1-1) to (V-1-5), R ^b is —H, halogen, —CF _3, or alkyl having 1 to 5 carbons.

As a preferable structure of the photopolymerizable monomer or photopolymerizable oligomer, in the formula (V), at least one of R ^a1 is the formula (V-1-1), (V-1-2) or (V- The structure represented by any one of 1-3) is mentioned.

In the formula (V), examples of the ring B include 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, A divalent group represented by fluorene-2,7-diyl, bicyclo [2.2.2] octane-1,4-diyl, bicyclo [3.1.0] hexane-3,6-diyl, In these rings, any —CH ₂ — may be replaced by —O—, any —CH═ may be replaced by —N═, and any —H may be halogen, cyano, nitro, May be replaced by isocyano, isothiocyanato, alkyl having 1 to 4 carbon atoms or silyl substituted with 1 to 3 carbon atoms, linear or branched alkyl having 1 to 10 carbon atoms or alkyl halide having 1 to 10 carbon atoms In the alkyl, arbitrary _-CH 2 -, -O -, - CO -, - COO -, - OCO -, - OCOO -, - may be replaced by CH = CH- or -C≡C-.

式（Ｖ−２−１）〜式（Ｖ−２−２５）において、Ｌはハロゲン、炭素数１〜３のアルキル、炭素数１〜３のアルコキシ、または炭素数１〜３のハロゲン化アルキルを表す。 In the formula (V), the ring B is preferably the following formulas (V-2-1) to (V-2-25).

In the formula (V-2-1) to the formula (V-2-25), L represents a halogen, an alkyl having 1 to 3 carbon atoms, an alkoxy having 1 to 3 carbon atoms, or an alkyl halide having 1 to 3 carbon atoms. Represent.

上記式中、Ｒ^ｃは−Ｈまたは−ＣＨ_３を示し、ベンゼン環上の−Ｈはハロゲン、−ＣＨ_３、−ＣＦ_３または−ＯＣＨ_３で置き換えられていてもよく；
Ｒ^ｄは独立して−Ｈ、ハロゲン、−ＣＨ_３、−ＣＦ_３、−ＯＣＨ_３、フェニルまたは同一炭素上にある２つのＲ^ｄが炭素数６〜１５の飽和または不飽和の炭化水素環を形成していても良く；そして、ｍ２およびｍ３は独立して１〜２０の整数である。 More preferable structures of the photopolymerizable monomer or photopolymerizable oligomer include the following structures.

In the above formula, R ^c represents —H or —CH _3, and —H on the benzene ring may be replaced by halogen, —CH ₃ , —CF ₃ or —OCH ₃ ;
R ^d independently represents —H, halogen, —CH ₃ , —CF ₃ , —OCH ₃ , phenyl, or two R ^d on the same carbon each represents a saturated or unsaturated hydrocarbon ring having 6 to 15 carbon atoms. And m2 and m3 are each independently an integer of 1-20.

More preferable structures of the photopolymerizable monomer or photopolymerizable oligomer include the following structures.

As a particularly preferred structure of the photopolymerizable monomer or photopolymerizable oligomer, (V-3-1-1), (V-3-2-2-3), (V-3-2-6), (V-3) -2-6-1), (V3-3-6), (V-3-4-6), (V-3-5-6), (V-3-6-6), (V-3) -6-6-1), (V-3-10-1), (V-3-10-1-1), (V-3-10-2), (V-3-10-2-1) ), (V-3-10-3), (V-3-10-3-1), (V-3-10-4), (V-3-10-4-1), (V-3) -11-1), (V-3-11-1-1), (V-3-11-2), (V-3-11-2-1), (V-3-13-1) and (V-3-13-2).

The photopolymerizable monomer or photopolymerizable oligomer can be contained in an amount of 0.01 to 50% by weight of the total solid content including polyimide, polyamic acid or polyamic acid derivative.

The photopolymerizable monomer or photopolymerizable oligomer is preferably mixed in an amount of 0.01% by weight or more in order to develop the effect of determining the tilt direction of the liquid crystal after polymerizing it. On the other hand, the orientation effect of the polymer formed after polymerizing the polymerizable monomer or photopolymerizable oligomer becomes too strong, and the orientation effect due to the polyimide or polyamic acid is diminished, and / or the unreacted monomer and after UV irradiation In order to prevent oligomers from remaining and / or eluting into the liquid crystal, the amount of the photopolymerizable monomer or photopolymerizable oligomer mixed is preferably 50% by weight or less.

In the polyimide, polyamic acid or polyamic acid derivative represented by the above formula (I) or (II), in R ¹ and R ² in the molecule, groups of 4 to 50 mol% of the total number of the respective radicals are radicals by light. You may have the group which generate | occur | produces.

An example of a group that generates a radical by light is a group having a benzophenone skeleton or a group having a cinnamate skeleton.

上記式中、Ｒ^１９は−Ｈまたは炭素数１〜２５の炭化水素基であり；
この炭化水素基の任意の−Ｈは−Ｆで置き換えられていてもよく；
Ｘ^３およびＸ^４は独立して単結合、−ＣＯＯ−または−Ｏ−であり；そして、
Ｇ^１３は炭素数２〜６のアルキレンである。 The further specific example of the group which generates a radical by light is at least one selected from the group of groups represented by the following formulas (VI-1) to (VI-4) and (VII-1) .

In the above formula, R ¹⁹ is —H or a hydrocarbon group having 1 to 25 carbon atoms;
Any —H of the hydrocarbon group may be replaced by —F;
X ³ and X ⁴ are independently a single bond, —COO— or —O—; and
G ¹³ is alkylene having 2 to 6 carbon atoms.

上記式中、Ｒ^３４は−Ｈまたは炭素数１から２５のアルキルである。 As the compound having a group represented by formulas (VI-1) to (VI-4) and (VII-1), the following compounds are preferable.

In the above formula, R ³⁴ is —H or alkyl having 1 to 25 carbons.

In addition, for the convenience of classifying the properties expected of the compound, the compound having a radical generating group listed above is given a formula number (VI-O-O) or (VII-O-O). Yes. However, the above compound is the diamine or tetra-amine exemplified hereinbefore, so that the compound (X-1-1) is the same as the diamine (V-5-29) exemplified earlier. It may also fall under the category of carboxylic dianhydrides. In such a case, unless otherwise specified in the present specification, the classification formula number exemplified above is used in preference to the formula number (X-o-o) or (VII-o-o).

The molecular weight of the polyimide, polyamic acid or polyamic acid derivative is, for example, a polystyrene-reduced weight average molecular weight (Mw) by gel permeation chromatography (GPC), preferably 10,000 to 500,000, more preferably 20, 000-200,000.

The polyimide, polyamic acid, or polyamic acid derivative can be produced in the same manner as a known polyimide or polyamic acid used for forming a polyimide film, except that the above-described tetracarboxylic dianhydride and diamine are used. For example, in a reaction vessel equipped with a raw material inlet, a nitrogen inlet, a thermometer, a stirrer and a condenser, one or more diamines represented by general formulas (III-1) to (III-13), Optionally, one or more diamines selected from other diamines, and optionally a desired amount of monoamine are charged.

Next, one or more of a solvent (for example, N-methyl-2-pyrrolidone or dimethylformamide, which is an amide polar solvent) and tetracarboxylic dianhydride, and a carboxylic acid anhydride if necessary To do. At this time, it is preferable that the total charge amount of tetracarboxylic dianhydride is approximately equal to the total number of moles of diamine (molar ratio of about 0.9 to 1.1).

The structure represented by the general formula (I) or (II) in the polyimide, polyamic acid, or polyamic acid derivative can be specified by an ordinary technique in specifying the structure of the polymer, and more specifically, IR or It can be identified by NMR.

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

The liquid crystal aligning agent of this invention may further contain other components other than the said polyimide, polyamic acid, or a polyamic acid derivative, and a photopolymerizable monomer or an oligomer. The other component may be one type or two or more types.

For example, a polymerization initiator or a polymerization inhibitor can be added to the polyimide, polyamic acid or polyamic acid derivative, and photopolymerizable monomer or oligomer.

Examples of the polymerization initiator include radical polymerization initiators.

Specific examples of the structure of the radical polymerization initiator include benzoin derivatives and compounds composed of peroxides.

Preferred examples of the benzoin derivative include (±) -camphorquinone, 2,2-diethoxyacetophenone, 2,4-diethylthioxanthen-9-one, 2-benzoylbenzoic acid, 2-chlorobenzophenone, 2-chlorothioxanthone, 2-ethylanthraquinone, 2-isonitrosopropiophenone, 2-isopropylthioxanthone, 2-phenyl-2- (p-toluenesulfonyloxy) acetophenone, 4,4′-dichlorobenzophenone, 4-benzoyl-4′-methyldiphenyl Sulfide, 4-benzoylbenzoic acid, 4-chlorobenzophenone, acetophenone, diphenylethanedione, benzoin, benzoin ethyl ether, benzoin isobutyl ether, benzoin isopropyl ether, benzoin methyl ether Benzophenone, dibenzosuberone, 9-fluorenone, methyl 2-benzoylbenzoate, 4,4-dimethoxybenzoyl, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, Michler's ketone, Examples include “Darocur Series 1173, 4265” and “Irgacure Series 184, 500, 651, 819, 2959” manufactured by Ciba Specialty Co., Ltd.

Preferable examples of the compound composed of peroxide include “Pertetra A, Perhexa HC, Perhexa C, Perhexa V, Perhexa 22, Perbutyl D, Perhexyl D, Parroyl 355, Parroyl L, Nyper BW, and Nyper manufactured by NOF Corporation. BMT, Parroyl TCP, Park Mill ND, Perocta ND, Perhexyl ND, Perbutyl NHP, Perhexyl PV, Perbutyl PV, Perhexa 25O, Perocta O, Perhexyl O, Perbutyl O, Perbutyl L, Perbutyl 355, Perhexyl I, Perbutyl E, Perhexa 25Z, Perbutyl A, perhexyl Z, perbutyl Z, perbutyl ZT "and the like.

A particularly preferred example of the benzoin derivative is Irgacure 651 manufactured by Ciba Specialty Co., Ltd.

Particularly preferred examples of the peroxide compound include “Parroyl L, Nyper BW, Nyper BMT, Perocta O, Perhexyl O, Perbutyl O” manufactured by NOF Corporation.

Two or more of these polymerization initiators may be combined, and an example of a preferable combination is a benzophenone / Michler's ketone mixture.

The addition amount of the polymerization initiator is desirably 10% by weight or less with respect to the photopolymerizable monomer or oligomer in order to prevent the polymerization initiator from acting as an impurity and degrading the display quality of the display element.

Since the photopolymerizable monomer or oligomer has high polymerizability, a polymerization inhibitor may be added for easy handling.

Further, the addition amount of the polymerization inhibitor is preferably 10% by weight or less with respect to the photopolymerizable monomer or oligomer in order to prevent the polymerization inhibitor from acting as an impurity.

For example, the polyimide, polyamic acid or polyamic acid derivative, and photopolymerizable monomer or oligomer may further contain an alkenyl-substituted nadiimide compound from the viewpoint of stabilizing the electrical characteristics of the liquid crystal display element over a long period of time. An alkenyl substituted nadiimide compound may be used by 1 type, and may use 2 or more types together. The content of the alkenyl-substituted nadiimide compound is preferably 0.01 to 1.00, more preferably 0.01 to 0.70 in terms of a weight ratio to the polyamic acid in the liquid crystal aligning agent, More preferably, it is -0.50.

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

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

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

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

In the general formula (Ina), when n = 2, W is alkylene of 2 to 20 carbon atoms, cycloalkylene of 5 to 8 carbon atoms, arylene having 6 to 12 carbon ^atoms, -Z 1 -O- ^(Z 2 O ) _R -Z ^3- (wherein Z ^{1 to} Z ³ and r have the same meanings as described above), a group represented by -Z ⁴ -BZ ^5- (where Z ⁴ , meaning of Z ⁵ and B are as defined above groups represented _{by.), -B- (O-B} ) s -T- (B-O) s -B- ( wherein, B is phenylene , T is alkylene having 1 to 3 carbon atoms, —O— or —SO ₂ —, and s is 0 or 1.), or 1 to 3 —H of these groups are It is a group replaced by —OH.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

For example, the polyimide, polyamic acid or polyamic acid derivative, and photopolymerizable monomer or oligomer further contain a compound having a radical polymerizable unsaturated double bond from the viewpoint of stabilizing the electrical properties of the liquid crystal display element over a long period of time. You may do it. Examples of the compound having a radical polymerizable unsaturated double bond include (meth) acrylic acid esters, (meth) acrylic acid derivatives such as (meth) acrylic acid amide, and bismaleimide. A (meth) acrylic acid derivative having two or more bonds is preferred.

Specific examples of (meth) acrylic acid esters include cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentanyloxyethyl (meth) acrylate. , 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 ethylenebisacrylate, Aronix M-210, Aronix M-240 and Aronix M-6200, which are products of Toa Gosei Co., Ltd., products of Nippon Kayaku Co., Ltd. KAYARAD HDDA, KAYARAD HX-220, KAYARAD R-604 and KAYARAD R-684, V260, V312 and V335HP which are products of Osaka Organic Chemical Co., Ltd., and light acrylate BA which is a product of Kyoeisha Chemical Co., Ltd. -4EA, light acrylate BP-4PA, and light acrylate BP-2PA.

Specific examples of the trifunctional or higher polyfunctional (meth) acrylic acid ester include 4,4′-methylenebis (N, N-dihydroxyethylene acrylate aniline), Aronix M-400, Aronix M-405, Aronix M-450, Aronix M-7100, Aronix M-8030, Aronix M-8060, KAYARAD TMPTA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, and Osaka Organic Chemical Co., Ltd. VGPT is mentioned.

Specific examples of (meth) acrylic acid amide derivatives include N-isopropylacrylamide, N-isopropylmethacrylamide, Nn-propylacrylamide, Nn-propylmethacrylamide, N-cyclopropylacrylamide, N-cyclopropylmethacrylic. Amide, N-ethoxyethylacrylamide, N-ethoxyethylmethacrylamide, N-tetrahydrofurfurylacrylamide, N-tetrahydrofurfurylmethacrylamide, N-ethylacrylamide, N-ethyl-N-methylacrylamide, N, N-diethylacrylamide N-methyl-Nn-propylacrylamide, N-methyl-N-isopropylacrylamide, N-acryloylpiperidine, N-acryloylpyrrolidine, N, N′-methylene Sacrylamide, 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- (methoxy Methyl) methacrylamide, N- (hydroxymethyl) -2-methacrylamide, N-benzyl-2-methacrylamide, and N, N′-methylenebismethacrylamide.

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

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

For example, the polyimide, polyamic acid or polyamic acid derivative, and photopolymerizable monomer or oligomer may further contain an oxazine compound from the viewpoint of long-term stability of electrical characteristics in a liquid crystal display device. Examples of the oxazine compound include compounds represented by the following formulas (a) to (f).

In the formulas (a) to (f), R ¹ and R ² are organic groups having 1 to 30 carbon atoms. R ^{3 to} R ⁶ are —H or a hydrocarbon group having 1 to 6 carbon atoms. X is a single bond, —O—, —S—, —S—S—, —SO ₂ —, —CO—, —CONH—, —NHCO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ −, — (CH ₂ ) _m —, —O— (CH ₂ ) _m —O—, —S— (CH ₂ ) _m —S—, and m is an integer of 1 to 6. Y is independently a single bond, —O—, —S—, —CO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, or alkylene having 1 to 3 carbon atoms.

The liquid crystal aligning agent of this invention may further contain the oxazoline compound from a viewpoint of the long-term stability of the electrical property in a liquid crystal display element. An oxazoline compound is a compound having an oxazoline structure. An oxazoline compound may be used by 1 type and may use 2 or more types together. The content of the oxazoline compound is preferably 0.001 to 0.50 by weight ratio to the polyamic acid, more preferably 0.01 to 0.40, and 0.01 to 0.20. Is more preferable. Alternatively, the content of the oxazoline compound is preferably 0.001 to 0.40 with respect to the polyamic acid when the oxazoline structure in the oxazoline compound is converted to oxazoline.

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

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

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

More preferable examples of the oxazoline compound include 2,2′-bis (2-oxazoline) and 1,3-bis (4,5-dihydro-2-oxazolyl) benzene.

For example, the polyimide, polyamic acid or polyamic acid derivative, and photopolymerizable monomer or oligomer may further contain an epoxy compound from the viewpoint of long-term stability of electrical characteristics in the liquid crystal display device. This epoxy compound may be a monomer, oligomer or polymer having an epoxy ring. An epoxy compound may be used by 1 type and may use 2 or more types together. The content of the epoxy compound is preferably 0.001 to 0.50, more preferably 0.01 to 0.40, and more preferably 0.01 to 0.20 in terms of a weight ratio to the polyamic acid. Is more preferable.

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

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

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

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

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

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

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

Among these examples, 3-glycidyloxypropyltrimethoxysilane, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N , N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane, trade name “Techmore VG3101L”, 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate, N-phenyl Maleimide-glycidyl methacrylate copolymer and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane are preferred, 3-glycidyloxypropyltrimethoxysilane, N, N, N ′, N′-tetraglycidyl-m- Xylenediamine, 1,3-bis (N, N-diglycy Ruaminomechiru) cyclohexane, N, N, N ', N'- tetraglycidyl-4,4'-diaminodiphenylmethane 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 cyclic aliphatic epoxy. Compounds. In addition, an epoxy compound means the compound which has an epoxy group, and an epoxy resin means resin which has an epoxy group.

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

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

Examples of glycidylamine include polyglycidylamine compounds.

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

Examples of glycidyl amide include glycidyl amide type epoxy compounds.

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

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

As the bisphenol A type epoxy compound, for example, 828, 1001, 1002, 1003, 1004, 1007, 1010 (all manufactured by Japan Epoxy Resin Co., Ltd.) (currently available as a product of jER series of Mitsubishi Chemical Corporation) / The same shall apply hereinafter)), Epototo YD-128 (manufactured by Toto Kasei Co., Ltd.), DER-331, DER-332, DER-324 (all available from Dow Chemical Japan Co., Ltd.), Epicron 840, Epicron 850, Epicron 1050 (all manufactured by DIC Corporation), Epomic R-140, Epomic R-301, and Epomic R-304 (all manufactured by Mitsui Chemicals, Inc.) may be mentioned.

Examples of the bisphenol F type epoxy compound include 806, 807, and 4004P (all manufactured by Japan Epoxy Resin Co., Ltd.), Epototo YDF-170, Epototo YDF-175S, and Epototo YDF-2001 (all manufactured by Toto Kasei Co., Ltd.). DER-354 (available from Dow Chemical Japan Co., Ltd.), Epicron 830, and Epicron 835 (all 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 Santo Tote ST-3000 (manufactured by Tohto Kasei Co., Ltd.), Rica Resin HBE-100 (manufactured by Shin Nippon Rika Co., Ltd.), and Denacol EX-252 (Nagase ChemteX Corporation) ))).

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

Examples of brominated bisphenol-A type epoxy compounds include 5050 and 5051 (both manufactured by Japan Epoxy Resin Co., Ltd.), Epototo YDB-360, Epototo YDB-400 (both manufactured by Toto Kasei Co., Ltd.), and DER-530. DER-538 (both can be purchased from Dow Chemical Japan Co., Ltd.), Epicron 152, and Epicron 153 (both manufactured by DIC Corporation).

Examples of the phenol novolac type epoxy compound are 152, 154 (all manufactured by Japan Epoxy Resin Co., Ltd.), YDPN-638 (manufactured by Toto Kasei Co., Ltd.), DEN431, DEN438 (all from Dow Chemical Japan Co., Ltd.). And Epiclon N-770 (manufactured by DIC Corporation), EPPN-201, and EPPN-202 (all manufactured by Nippon Kayaku Co., Ltd.).

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

Examples of the bisphenol A novolac type epoxy compound include 157S70 (manufactured by Japan Epoxy Resin Co., Ltd.) and Epicron N-880 (manufactured by DIC Corporation).

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

Examples of the aromatic polyglycidyl ether compound include hydroquinone diglycidyl ether (following formula E101), catechol diglycidyl ether (following formula E102) resorcinol diglycidyl ether (following formula E103), tris (4-glycidyloxyphenyl) methane (described below). Formula E105), 1031S, 1032H60 (all manufactured by Japan Epoxy Resin Co., Ltd.), TACTIX-742 (available for purchase from Dow Chemical Japan Co., Ltd.), Denacol EX-201 (manufactured by Nagase ChemteX Corporation), DPPN -503, DPPN-502H, DPPN-501H, NC6000 (all manufactured by Nippon Kayaku Co., Ltd.), Techmore VG3101L (manufactured by Mitsui Chemicals), a compound represented by the following formula E106, and a table represented by the following formula E107 Compound And the like.

Examples of the dicyclopentadiene phenol type epoxy compound include TACTIX-556 (available from Dow Chemical Japan Co., Ltd.) and Epicron HP-7200 (manufactured by DIC Corporation).

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

Examples of the aliphatic polyglycidyl ether compound include ethylene glycol diglycidyl ether (following formula E108), diethylene glycol diglycidyl ether (following formula E109), polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether (following formula E110), and tripropylene. Glycol diglycidyl ether (following formula E111), polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether (following formula E112), 1,4-butanediol diglycidyl ether (following formula E113), 1,6-hexanediol di Glycidyl ether (following formula E114), dibromoneopentyl glycol diglycidyl ether (following formula E115), Denacol EX-810, Cole EX-851, Denacol EX-8301, Denacol EX-911, Denacol EX-920, Denacol EX-931, Denacol EX-211, Denacol EX-212, Denacol EX-313 (all manufactured by Nagase ChemteX Corporation) DD-503 (manufactured by ADEKA Corporation), Rica Resin W-100 (manufactured by Shin Nippon Rika Co., Ltd.), 1,3,5,6-tetraglycidyl-2,4-hexanediol (formula E116 below), 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 Nagaseke Made Tex Co., Ltd.) and the like.

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

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

Examples of the diglycidyl ester compound include diglycidyl terephthalate (the following formula 117), diglycidyl phthalate (the following formula E118), bis (2-methyloxiranylmethyl) phthalate (the following formula E119), and the following formula E121. Examples thereof include a compound, a compound represented by the following formula E122, and a compound represented by the following formula E123.

Examples of the glycidyl ester epoxy compound include 871, 872 (all manufactured by Japan Epoxy Resin Co., Ltd.), Epicron 200, Epicron 400 (all manufactured by DIC Corporation), Denacol EX-711, and Denacol EX-721 (any Also manufactured by Nagase ChemteX Corporation).

Examples of the polyglycidylamine compound include N, N-diglycidylaniline (following formula E124), N, N-diglycidyl-o-toluidine (following formula E125), N, N-diglycidyl-m-toluidine (following formula E126). N, N-diglycidyl-2,4,6-tribromoaniline (following formula E127), 3- (N, N-diglycidyl) aminopropyltrimethoxysilane (following formula E128), N, N, O-triglycidyl -P-aminophenol (formula E129 below), N, N, O-triglycidyl-m-aminophenol (formula E130 below), N, N, N ', N'-tetraglycidyl-m-xylylenediamine (TETRAD) -X (Mitsubishi Gas Chemical Co., Ltd.), the following formula E132), 1,3-bis (N, N-diglycidylaminomethyl) cyclo Xan (TETRAD-C (Mitsubishi Gas Chemical Co., Ltd.), the following formula E133), 1,4-bis (N, N-diglycidylaminomethyl) cyclohexane (the following formula E134), 1,3-bis (N, N-diglycidylamino) cyclohexane (formula E135), 1,4-bis (N, N-diglycidylamino) cyclohexane (formula E136), 1,3-bis (N, N-diglycidylamino) benzene ( Formula E137), 1,4-bis (N, N-diglycidylamino) benzene (Formula E138), 2,6-bis (N, N-diglycidylaminomethyl) bicyclo [2.2.1] heptane (Formula E139 below), N, N, N ′, N′-tetraglycidyl-4,4′-diaminodicyclohexylmethane (formula E140 below), 2,2′-dimethyl- (N, , N ′, N′-tetraglycidyl) -4,4′-diaminobiphenyl (the following formula E141), N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenyl ether (the following formula E142), 1,3,5-tris (4- (N, N-diglycidyl) aminophenoxy) benzene (following formula E143), 2,4,4′-tris (N, N-diglycidylamino) diphenyl ether (following formula E144) , Tris (4- (N, N-diglycidyl) aminophenyl) methane (following formula E145), 3,4,3 ′, 4′-tetrakis (N, N-diglycidylamino) biphenyl (following formula E146), 3 , 4,3 ′, 4′-tetrakis (N, N-diglycidylamino) diphenyl ether (formula E147 below), a compound represented by formula E148 below, and And a compound represented by the formula E149.

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

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

Examples of monomers other than the monomer having oxiranyl in the copolymer of monomers having oxiranyl include, for example, (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, 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 E150), 1,3-diglycidyl. Examples include -5-allyl-1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione (formula E151 below) and glycidyl isocyanurate type epoxy resin.

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

Examples of the cycloaliphatic epoxy compound include 2-methyl-3,4-epoxycyclohexylmethyl-2′-methyl-3 ′, 4′-epoxycyclohexylcarboxylate (formula E153 below), 2,3-epoxycyclopentane. -2 ', 3'-epoxycyclopentane ether (formula E154 below), ε-caprolactone modified 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarbochelate, 1,2: 8,9-diepoxy Limonene (Celoxide 3000 (manufactured by Daicel Chemical Industries), 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate (Celoxide 2021P (manufactured by Daicel Chemical Industries), formula E155) , A compound represented by the following formula E156, CY- 75, CY-177, CY-179 (all manufactured by CIBA-GEIGY Ltd. (available from Huntsman Japan)), EHPD-3150 (manufactured by Daicel Chemical Industries, Ltd.), and cyclic aliphatic type An epoxy resin is mentioned.

Among these epoxy compounds, a compound having a plurality of epoxy rings is expected to react so as to be crosslinked with the polymer main chain, and is also used for the purpose of improving the durability of the liquid crystal alignment film.

For example, the polyimide, polyamic acid or polyamic acid derivative, and photopolymerizable monomer or oligomer may further contain various additives from the viewpoint of long-term stability of electrical characteristics in the liquid crystal display device. Examples of the various additives include polymers other than polyamic acid and its derivatives, and low molecular weight compounds, which can be selected and used according to their respective purposes. Examples of the polymer include polymers that are soluble in organic solvents. It is preferable to add such a polymer to the liquid crystal aligning agent of the present invention from the viewpoint of controlling the electrical characteristics and orientation of the liquid crystal alignment film to be formed. Examples of the polymer include liquid crystal alignment polyorganosiloxane, polyamide, polyurethane, polyurea, polyester, polyepoxide, polyester polyol, silicone-modified polyurethane, and silicone-modified polyester. Among these examples, liquid crystal aligning polyorganosiloxane is preferable.

The liquid crystal alignment polyorganosiloxane can be synthesized by reacting a reactive polyorganosiloxane with a reactive compound, preferably in the presence of a catalyst. Examples of the liquid crystal aligning polyorganosiloxane include liquid crystal aligning polyorganosiloxanes disclosed in WO2009 / 096598, JP2009-282440A, JP2010-097007A, and the like.

Examples of the low molecular weight compound include 1) a surfactant in accordance with this purpose when improvement in coating properties is desired, 2) an antistatic agent when improvement in antistatic properties is required, and 3) adhesion and resistance to substrates. A silane coupling agent or a titanium-based coupling agent is desired when improving rubbing properties, and 4) an imidization catalyst when imidization proceeds at a low temperature. The low molecular weight compound may be one type of compound or two or more types of compounds.

Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyltri Methoxysilane, paraaminophenyltrimethoxysilane, paraaminophenyltriethoxysilane, metaaminophenyltrimethoxysilane, metaaminophenyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-chloropropylmethyl Dimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N- (1,3-dimethylbutylidene) -3- (to Triethoxysilyl) -1-propylamine, and N, N'-bis [3- (trimethoxysilyl) propyl] ethylenediamine.

The content of the coupling agent is preferably 0.01 to 6% by weight based on the polymer solid content in the liquid crystal aligning agent.

Examples of imidation catalysts include aliphatic amines such as trimethylamine, triethylamine, tripropylamine, and tributylamine; aromatic amines such as N, N-dimethylaniline, N, N-diethylaniline, methyl-substituted aniline, and hydroxy-substituted aniline. And cyclic amines such as pyridine, methyl-substituted pyridine, hydroxy-substituted pyridine, quinoline, methyl-substituted quinoline, hydroxy-substituted quinoline, isoquinoline, methyl-substituted isoquinoline, hydroxy-substituted isoquinoline, imidazole, methyl-substituted imidazole, and hydroxy-substituted imidazole. . The imidation catalyst is one selected from N, N-dimethylaniline, o-hydroxyaniline, m-hydroxyaniline, p-hydroxyaniline, o-hydroxypyridine, m-hydroxypyridine, p-hydroxypyridine, and isoquinoline. Or it is preferable that they are 2 or more types.

For example, the polyimide, polyamic acid or polyamic acid derivative, and photopolymerizable monomer or oligomer may further contain a solvent from the viewpoint of adjusting the coating property of the liquid crystal aligning agent and the concentration of the polyamic acid. Any solvent can be used without particular limitation as long as it has the ability to dissolve the polymer component. The solvent includes a wide variety of solvents usually used in the production process and applications 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 type or a mixed solvent of two or more types. Examples of such a solvent include a parent solvent for the polyamic acid and other solvents for improving coating properties.

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

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

Among these, the solvent includes N-methyl-2-pyrrolidone, dimethylimidazolidinone, γ-butyrolactone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, and the like. It can be preferably used.

In the present invention, the concentration of the polymer component containing the polyimide, polyamic acid or polyamic acid derivative in the liquid crystal aligning agent is not particularly limited, but is preferably 0.1 to 40% by weight. When the liquid crystal aligning agent is applied to the substrate, it may be necessary to dilute the polymer component contained in advance with a solvent in order to adjust the film thickness. A concentration of the polymer component of 40% by weight or less is suitable for easily mixing a solvent with the liquid crystal aligning agent when the liquid crystal aligning agent needs to be diluted for film thickness adjustment. The viscosity is preferable from the viewpoint of adjusting the viscosity of the liquid crystal aligning agent.

Further, the concentration of the polymer component in the liquid crystal aligning agent may be adjusted by a coating method of the liquid crystal aligning agent. When the application method of the liquid crystal aligning agent is a spinner method or a printing method, the concentration of the polymer component is usually 10% by weight or less in order to maintain a good film thickness. Other coating methods such as a dipping method or an ink jet method may further reduce the concentration. On the other hand, when the concentration of the polymer component is 0.1% by weight or more, the thickness of the obtained liquid crystal alignment film tends to be optimal. Therefore, the concentration of the polymer component is 0.1% by weight or more, preferably 0.5 to 10% by weight in the usual spinner method or printing method. However, depending on the application method of the liquid crystal aligning agent, it may be used at a dilute concentration.

In addition, when using for preparation of a liquid crystal aligning film, the viscosity of the liquid crystal aligning agent of this invention can be determined according to the means and method of forming this liquid crystal aligning agent film. For example, when a film of a liquid crystal aligning agent is formed using a printing machine, it is preferably 5 mPa · s or more from the viewpoint of obtaining a sufficient film thickness, and 100 mPa · s or less from the viewpoint of suppressing printing unevenness. It is preferably 10 to 80 mPa · s. When a liquid crystal aligning agent is applied by spin coating to form a liquid crystal aligning agent film, it is preferably 5 to 200 mPa · s, more preferably 10 to 100 mPa · s from the same viewpoint. The viscosity of the liquid crystal aligning agent can be reduced by curing with dilution or stirring with a solvent.

The liquid crystal aligning agent of the present invention may be in the form of a so-called polymer blend. The liquid crystal aligning agent of such a form includes a reaction product of polyamic acid or its derivative A, which is a reaction product of tetracarboxylic dianhydride A and diamine A, and a reaction product of tetracarboxylic dianhydride B and diamine B. In the liquid crystal aligning agent containing the polyamic acid or its derivative B which is a product, the diamine A contains a diamine represented by the formulas (III-1) to (III-13), and the diamine B is represented by the formula (III-1) The liquid crystal aligning agent which does not contain the diamine represented by-(III-13) is mentioned.

The polyamic acid or derivative A thereof is the same as the polyamic acid or derivative thereof in the present invention described above. The polyamic acid or its derivative B is the present invention described above except that the diamine does not contain the diamines represented by formulas (III-1) to (III-13), that is, the diamine is used as the diamine. The same as the polyamic acid or its derivative in

As the tetracarboxylic dianhydrides A and B, the above-described tetracarboxylic acids can be used. The diamine A only needs to contain diamines represented by formulas (III-1) to (III-13), and may further contain other diamines described above. As the diamine B, other diamines other than the diamines represented by the formulas (III-1) to (III-13) can be used.

The content of the polyamic acid or its derivative B in the liquid crystal aligning agent of the present invention is not particularly limited as long as the effect of the present invention is manifested, but is 1 to the total amount of the polymer in the liquid crystal aligning agent. The amount is preferably 50% by weight from the viewpoint of achieving both the expression of the effect of the present invention and the adjustment of the orientation, and more preferably 2 to 30% by weight.

The liquid crystal aligning film of this invention is obtained from the liquid crystal aligning agent of this invention mentioned above. The liquid crystal alignment film of the present invention comprises a step of forming a coating film of the liquid crystal aligning agent of the present invention, a step of heating and baking the liquid crystal aligning agent by injecting liquid crystal, and then adjusting the liquid crystal display element by an electric field. Anisotropy can be developed at the liquid crystal interface, and it can be obtained by fixing it by light irradiation.

The said coating film can be formed by apply | coating the liquid crystal aligning agent of this invention to the board | substrate in a liquid crystal display element similarly to preparation of a normal liquid crystal aligning film. Examples of the substrate include a glass substrate on which an electrode such as an ITO (Indium Tin Oxide) electrode, a color filter, or the like may be provided.

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

The coating film can be fired under conditions necessary for the polyamic acid or its derivative to exhibit a dehydration / ring-closure reaction. As 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, and the like are generally known. These methods are equally applicable in the present invention. In general, it is preferably performed at a temperature of about 100 to 300 ° C. for 1 minute to 3 hours, and by baking at 100 ° C. to 230 ° C., 50% by weight or more of the photopolymerizable monomer and / or photopolymerizable oligomer does not undergo thermal polymerization. More preferably, it remains as it is, and it is more preferable that 50% by weight or more of the photopolymerizable monomer and / or photopolymerizable oligomer remain as it is without thermal polymerization by baking at 180 to 230 ° C.

The liquid crystal alignment film of the present invention can be suitably obtained by a method that further includes steps other than the steps described above. Examples of such other processes include a process of drying the coating film and a process of cleaning the film with a cleaning liquid.

As the drying step, a method of heat treatment in an oven or an infrared furnace, a method of heat treatment on a hot plate, and the like are generally known as in the baking step. These methods are also applicable to the drying step. The drying step is preferably performed 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 baking step.

Examples of the cleaning method using the cleaning liquid for the liquid crystal alignment film include brushing, jet spray, steam cleaning, and ultrasonic cleaning. These methods may be performed alone or in combination. The cleaning liquid is pure water, various alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, aromatic hydrocarbons such as benzene, toluene, xylene, halogen solvents such as methylene chloride, and ketones such as acetone and methyl ethyl ketone. Although it can be used, it is not limited to these. Of course, these cleaning liquids are sufficiently purified and have few impurities. 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.

Although the film thickness of the liquid crystal aligning film of this invention is not specifically limited, It is preferable that it is 10-300 nm, and it is more preferable that it is 30-150 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 liquid crystal display element of the present invention includes a pair of substrates, a liquid crystal layer containing liquid crystal molecules, formed between the pair of substrates, an electrode for applying a voltage to the liquid crystal layer, and the liquid crystal molecules in a predetermined direction. And a liquid crystal alignment film to be aligned. The liquid crystal alignment film of the present invention is used for the liquid crystal alignment film.

The glass substrate described above with the liquid crystal alignment film of the present invention can be used as the substrate, and the ITO electrode formed on the glass substrate as described above with the liquid crystal alignment film of the present invention can be used as the electrode. Can be used.

The liquid crystal layer is formed of a liquid crystal composition that is sealed in a gap between a pair of substrates facing each other so that a surface of one of the pair of substrates on which a liquid crystal alignment film is formed faces the other substrate. .

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 positive dielectric anisotropy include Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Laid-Open No. 5-501735, Japanese Patent Laid-Open No. 8-157826, and Japanese Patent Laid-Open No. 8-231960. JP-A-9-241644 (EP88272A1 specification), JP-A-9-302346 (EP806466A1 specification), JP-A-8-199168 (EP722998A1 specification), JP-A-9-235552, JP Japanese Laid-Open Patent Publication Nos. 9-255958, 9-241463 (EP882711A1), 10-204016 (EP844229A1), 10-204436, 10-231482, and JP 2000-087040, JP 2001-488 The liquid crystal composition disclosed in 2 publications, and the like.

Preferred liquid crystal compositions having a negative dielectric anisotropy include JP-A-57-114532, JP-A-2-4725, JP-A-4-222485, JP-A-8-40953, JP-A-8-104869, JP-A-10-168076, JP-A-10-168453, JP-A-10-236989, JP-A-10-236990, JP-A-10-236992, JP-A-10- No. 236993, JP-A-10-236994, JP-A-10-237000, JP-A-10-237004, JP-A-10-237024, JP-A-10-237035, JP-A-10-237075 Publication, Unexamined-Japanese-Patent No. 10-237076, Unexamined-Japanese-Patent No. 10-237448 (EP967261A1 specification), Japanese Laid-Open Patent Publication Nos. 10-287874, 10-287875, 10-291945, 11-029581, 11-080049, 2000-256307, 2001-2001. Examples thereof include liquid crystal compositions disclosed in Japanese Patent Application Publication No. 019965, Japanese Patent Application Laid-Open No. 2001-072626, Japanese Patent Application Laid-Open No. 2001-192657, and the like.

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

In the liquid crystal display element of the present invention, the liquid crystal alignment film of the present invention is formed on at least one of a pair of substrates, and the obtained pair of substrates are opposed to each other with a liquid crystal alignment film facing inward through a spacer. It is obtained by enclosing a liquid crystal composition in the formed gap to form a liquid crystal layer. The production of the liquid crystal display element of the present invention may include additional steps such as attaching a polarizing film to the substrate as necessary.

When polymerizing the photopolymerizable monomer and / or photopolymerizable oligomer, a voltage is applied. In that case, a voltage that is five times the threshold voltage of the liquid crystal to the transmittance of 100% is applied, preferably the voltage of the transmittance of 50% to the transmittance of 100%. A voltage that is three times the voltage is applied.

When polymerizing the photopolymerizable monomer and / or photopolymerizable oligomer, ultraviolet rays or visible light is usually used. The wavelength of light used for light irradiation is in the range of 150 to 500 nm, preferably 250 to 450 nm, more preferably 300 to 400 nm. As a light source for light irradiation, for example, a low-pressure mercury lamp (sterilization lamp, fluorescent chemical lamp, black light), a high-pressure discharge lamp (high-pressure mercury lamp, metal halide lamp) and a short arc discharge lamp (ultra-high pressure mercury lamp, xenon lamp, mercury) Xenon lamp). Among these, a metal halide lamp, a xenon lamp, and a high-pressure mercury lamp are preferable.

For the light from the light source, the wavelength region of the irradiation light source may be selected by passing only a specific wavelength region by installing a filter or the like. Energy radiated from a light source, 1,000~300,000mJ / cm ^2, preferably in the range 2,000~100,000mJ / cm ^2, more preferably of 5,000~50,000mJ / cm ^2.

The liquid crystal display element of the present invention can form liquid crystal display elements for various electric field systems. In such a liquid crystal display element for electric field mode, a liquid crystal display element for horizontal electric field mode in which the electrode applies a voltage to the liquid crystal layer in a horizontal direction with respect to the surface of the substrate, or a surface of the substrate. In addition, there is a vertical electric field type liquid crystal display element in which the electrode applies a voltage to the liquid crystal layer in the vertical direction.

Since the liquid crystal display element for the horizontal electric field mode does not have to exhibit a relatively large pretilt angle, a liquid crystal alignment film using the liquid crystal alignment agent of the present invention obtained from a diamine not containing a diamine having a side chain is suitable. Used.

Since the liquid crystal display element for the vertical electric field system requires a relatively large pretilt angle, the liquid crystal display element is obtained from a diamine containing a diamine having a side chain, or the diamine B contains a diamine having a side chain. A liquid crystal alignment film made of a liquid crystal aligning agent is preferably used.

As described above, the liquid crystal alignment film produced using the liquid crystal aligning agent of the present invention as a raw material can be applied to liquid crystal display elements of various display drive systems by appropriately selecting a polymer as the raw material.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples. The compounds used in the examples are as follows.

<Tetracarboxylic dianhydride>
Compound (IV-1-1): 1,2,3,4-butanetetracarboxylic dianhydride compound (IV-2-1): 1,2,3,4-cyclobutanetetracarboxylic dianhydride compound ( IV-3-1): 1,2,4,5-cyclohexanetetracarboxylic dianhydride compound (IV-3-2): pyromellitic anhydride compound (IV-4-23): 4,4′- (Octane-1,8-diyl) diphthalic dianhydride compound (IV-5-3): 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5- Dioxo-3-furanyl) -naphtho [1,2-C] -furan-1,3-dione compound (IV-7-2): 2,3,5-tricarboxycyclopentylacetic acid dianhydride compound (IV-10) ): Bicyclo [3.3.0] octane-2,4,6, 8-tetracarboxylic dianhydride compound (IV-12-1): 18,21-bis (3- (2,5-dioxotetrahydrofuran-3-yl) propyl) -18,21-dimethyl-1,3 , 5,7,9,11,13,15-octaphenyl-pentacyclo [10.5.1.25, 13.17, 11.19,15] decasiloxane compound (VII-1-1): benzophenone-3 , 3 ', 4,4'-tetracarboxylic dianhydride

<Diamine>
Compound (III-2-3): 1,3-bis (aminomethyl) cyclohexane compound (III-4-1): p-phenylenediamine compound (III-4-9): m-xylenediamine compound (III-5) -1): 4,4'-methylenedianiline compound (III-5-5): 4,4'-methylenebis (3-methylaniline)
Compound (III-5-7): 4,4′-ethylenedianiline compound (III-5-33): 2,2′-dimethyl-4,4′-diaminobiphenyl compound (III-5-34): 2 , 2′-di (trifluoromethyl) -4,4′-diaminobiphenyl compound (III-5-35): 2,2′-bis (4-aminophenyl) hexafluoropropane compound (III-8-2- 12): Compound in which R ^4a is dodecyl in formula (III-8-2): 5- (4-dodecylbenzyl) benzene-1,3-diamine compound (III-8-2-20): Formula (III- Compound in which R ^4a is icosyl in 8-2): 5- (4-hexadecylbenzyl) benzene-1,3-diamine compound (III-8-5-5): R in formula (III-8-5) ^5a pliers Compound: 5- (4- (4′-pentylbicyclohexane-4-yl) benzyl) benzene-1,3-diamine compound (III-8-39-5): In the formula (III-8-39) Compound in which R ^5b is pentyl: 4- (4- (4′-pentylbi (cyclohexane) -4-yl) phenoxy) -1,3-diaminobenzene compound (III-8-41): cholesteryl-3,5- Diaminobenzoate compound (III-8-42): Cholestalyl-3,5-diaminobenzoate compound (III-11-2-7): Compound in which R ^5c is heptyl in formula (III-11-2): 1 , 1-bis (4- (4-aminophenyl) methylphenyl) -4-heptylcyclohexane compound (III-11-7-7): In formula (III-11-7) Compound ^{R 5d} is heptyl Te: 1,1-bis (4- (4-aminophenoxy) phenyl) -4- (2- (4-heptylcyclohexyl) ethyl) cyclohexane

Compound (VI-1-1): 4,4′-diaminobenzophenone compound (VI-2-1-14): Compound in which R ³⁴ is tetradecyl in formula (VI-2-1): (3,5-diamino) Phenyl) (4-tetradecylphenyl) methanone compound (VI-3-5): (E) -6- (3- (4-pentylphenyl) acryloyloxy) hexyl 3,5-diaminobenzoate compound (VI-4) -1): (E) -7- (4-hexyloxyphenyl) -5-oxohept-6-enyl 3,5-diaminobenzoate

<Photopolymerizable monomer> Compound (V-3-1-1): 4,4′-bis (methacryloyloxy) biphenyl compound (V-3-2-2): 2-methyl-1,4-phenylene bis ( 4- (3- (acryloyloxy) propoxy) benzoate)
Compound (V-3-2-6): 2-methyl-1,4-phenylene bis (4- (6- (acryloyloxy) hexyloxy) benzoate)
Compound (V-3-2-6-1): 2-methyl-1,4-phenylene bis (4- (6- (methacryloyloxy) hexyloxy) benzoate)
Compound (V-3-3-6): 4,4′-bis (6- (acryloyloxy) hexyloxy) biphenyl compound (V-3-4-6): 4-cyanophenyl 4- (6- (acryloyl) Oxy) hexyloxy) benzoate compound (V-3-5-6): 4-methoxyphenyl 4- (6- (acryloyloxy) hexyloxy) benzoate compound (V-3-6-6): 2-methyl -1,4-phenylene bis (4-((6- (acryloyloxy) hexyloxy) carbonyloxy) benzoate)

Compound (V-3-10-1): 4,4 ′-(perfluoropropane-2,2-diyl) bis (4,1-phenylene) bis (4- (6- (acryloyloxy) hexyloxy) benzoate )
Compound (V-3-10-1-1): 4,4 ′-(perfluoropropane-2,2-diyl) bis (4,1-phenylene) bis (4- (6- (methacryloyloxy) hexyloxy) Benzoart)
Compound (V-3-10-2): 4,4 ′-(perfluoropropane-2,2-diyl) bis (4,1-phenylene) bis (4- (6- (acryloyloxy) hexyloxy) -2 -Fluorobenzoate)
Compound (V-3-10-2-1): 4,4 ′-(perfluoropropane-2,2-diyl) bis (4,1-phenylene) bis (4- (6- (methacryloyloxy) hexyloxy) -2-Fluorobenzoate)
Compound (V-3-10-3): 6,6 ′-(4,4 ′-(3,3 ′-(4,4 ′-(perfluoropropane-2,2-diyl) bis (4,1- Phenylene)) bis (oxy) bis (3-oxopropane-3,1-diyl)) bis (4,1-phenylene)) bis (oxy) bis (hexane-6,1-diyl) diacrylate compound (V- 3-10-3-1): 6,6 ′-(4,4 ′-(3,3 ′-(4,4 ′-(perfluoropropane-2,2-diyl) bis (4,1-phenylene)) ) Bis (oxy) bis (3-oxopropane-3,1-diyl)) bis (4,1-phenylene)) bis (oxy) bis (hexane-6,1-diyl) dimethacrylate compound (V-3- 10-4): 4,4 ′-(perfluoropropane-2,2-diyl) bis (2,6-di) Ruoro-4,1-phenylene) bis (4- (6- (acryloyloxy) hexyloxy) benzoate)
Compound (V-3-10-4-1): 4,4 ′-(perfluoropropane-2,2-diyl) bis (2,6-difluoro-4,1-phenylene) bis (4- (6- ( Methacryloyloxy) hexyloxy) benzoate)
Compound (V-3-10-5): 4,4 ′-(propane-2,2-diyl) bis (4,1-phenylene) bis (4- (6- (acryloyloxy) hexyloxy) benzoate)
Compound (V-3-10-6): 4,4 ′-(ethane-1,1-diyl) bis (4,1-phenylene) bis (4- (6- (acryloyloxy) hexyloxy) benzoate)
Compound (V-3-10-7): 4,4′-methylenebis (4,1-phenylene) bis (4- (6- (acryloyloxy) hexyloxy) benzoate)

Compound (V-3-11-1): 9,9-dimethyl-9H-fluorene-2,7-diyl bis (4- (6- (acryloyloxy) hexyloxy) benzoate)
Compound (V-3-11-1-1): 9,9-dimethyl-9H-fluorene-2,7-diyl bis (4- (6- (methacryloyloxy) hexyloxy) benzoate)
Compound (V-3-11-2): 9,9-dimethyl-9H-fluorene-2,7-diyl bis (4- (6- (acryloyloxy) hexyloxy) -2-fluorobenzoate)
Compound (V-3-11-2-1): 9,9-dimethyl-9H-fluorene-2,7-diyl bis (4- (6- (methacryloyloxy) hexyloxy) -2-fluorobenzoate)
Compound (V-3-11-3): Bis (4- (acryloyloxy) butyl) ′-9,9-dimethyl-9H-fluorene-2,7-diyl diterephthalate compound (V-3-11-4) : 9,9-dimethyl-9H-fluorene-2,7-diyl bis (4-((4- (acryloyloxy) butyloxy) carbonyloxy) benzoate)
Compound (V-3-11-5): 4,4 ′-(4,4 ′-(3,3 ′-(9,9-dimethyl-9H-fluorene-2,7-diyl) bis (oxy) bis (3-Oxopropane-3,1-diyl)) bis (4,1-phenylene)) bis (oxy) bis (oxomethylene) bis (oxy) bis (butane-4,1-diyl) diacrylate compound (V -3-11-6): 6,6 ′-(4,4 ′-(3,3 ′-(9,9-dimethyl-9H-fluorene-2,7-diyl) bis (oxy) bis (3- Oxopropane-3,1-diyl)) bis (4,1-phenylene)) bis (oxy) bis (hexane-6,1-diyl) diacetate compound (V-3-11-7): 6,6 ′ -(4,4 '-(2,2'-(9,9-dimethyl-9H-fluorene-2,7-diyl) bis Ethane-2,1-diyl)) bis (4,1-phenylene)) bis (oxy) bis (hexane-6,1-diyl) diacrylate compound (V-3-11-8): 9,9'- Spirobi [fluorene] -2,7-diyl bis (4- (6- (acryloyloxy) hexyloxy) benzoate)
Compound (V-3-13-1): 4,4 ′-(cyclohexane-1,1-diyl) bis (4,1-phenylene) bis (4- (6- (acryloyloxy) hexyloxy) acrylate)
Compound (V-3-13-2): 4,4 ′-(9H-fluorene-9,9-diyl) bis (4,1-phenylene) bis (4- (6- (acryloyloxy) hexyloxy) acrylate )

<Polymerization initiator>
Ciba Specialty Co., Ltd. Irgacure 651

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

<Additives>
<Epoxy compound>
Additive A: N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane additive B: N, N, N ′, N′-tetraglycidyl-m-xylenediamine additive C: 1 , 3-Bis (N, N-diglycidylaminomethyl) cyclohexane <additive polymer>
Additive D: Liquid crystal aligning polyorganosiloxane (see Synthesis Example 1 and Example 1 of WO2009 / 096598)
<Silane coupling agent>
Additive E: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Additive F: 3-glycidyloxypropyltrimethoxysilane

<1. Synthesis of polyamic acid>
[Synthesis Example 1]
2.100 g of compound (III-5-5), 1.069 g of compound (III-8-5-5) in a 100 mL four-necked flask equipped with a thermometer, a stirrer, a raw material charging charge port and a nitrogen gas inlet port, Then, 80.0 g of dehydrated NMP was added and dissolved by stirring under a dry nitrogen stream. Next, 2.694 g of compound (IV-3-2) was added, and the reaction was allowed to stir for 30 hours in a room temperature environment. When the temperature rose during stirring, it was cooled so as to keep about 70 ° C. or lower. BC14.0g was added to the obtained reaction liquid, and the polyamic acid solution (PA1) whose solid content concentration is 6 weight% was obtained. The weight average molecular weight of the polyamic acid contained in PA1 was 89,000.

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

[Synthesis Examples 2 to 129]
Polyamic acid solutions (PA2) to (PA129) were prepared according to Synthesis Example 1 except that tetracarboxylic dianhydride and diamine were changed as shown in Tables 1-1 to 1-5. The results including Synthesis Example 1 are summarized in Tables 1-1 to 1-5.

<2. Synthesis of polyimide>
[Synthesis Example 130]
The polyamic acid solution (PA124) obtained in Synthesis Example 124 is poured into a large excess of methyl alcohol to precipitate the reaction product. Then, it wash | cleans with methyl alcohol, A polyamic acid is obtained by making it dry at 40 degreeC under pressure reduction for 15 hours. The obtained polyamic acid is dissolved in dehydrated NMP, pyridine and acetic anhydride are added, dehydration ring closure is performed at 110 ° C. for 4 hours, precipitation, washing and decompression are performed, and the obtained polyimide powder is dehydrated NMP / BC / GBL = It is dissolved in 45/15/40 (weight ratio) to obtain a polyimide solution (PI124) having a solid content concentration of 4% by weight. (See JP 2007-047662 A.)

表中ＰＡ酸溶液とは以降も含めてポリアミック酸溶液を指す。 [Synthesis Examples 131 to 135]
Except for changing the tetracarboxylic dianhydride and diamine as shown in Table 1-6, polyimides (PI125) to (PI129) are prepared according to Synthesis Example 130. (See JP2007-047662, JP2007-256822, JP2007-332357, and WO2009 / 096598.)

In the table, the PA acid solution means a polyamic acid solution including the following.

表中ＰＩ溶液とは以降も含めて可溶性ポリイミド溶液を指す。

In the table, the PI solution refers to a soluble polyimide solution including the following.

<2. Production of liquid crystal display element>
[Example 1]
To the polyamic acid solution (PA1) synthesized in Synthesis Example 1, a compound (V-3-2-6) corresponding to 30% by weight of the solid content of PA1 was added, and NMP / BC = 1/1 (weight ratio) ) Was added so that the solid content of PA1 was 4% by weight to obtain a liquid crystal aligning agent.

The liquid crystal aligning agent was applied to two glass substrates with an ITO electrode with a spinner to form a film with a thickness of 100 nm. After coating, the film was heated and dried at 80 ° C. for about 10 minutes, and then heat-treated at 180 ° C. for 60 minutes to form a liquid crystal alignment film.

One glass substrate is sprayed with a 4.25 μm gap material, and the other substrate is sealed with an epoxy adhesive leaving the liquid crystal inlet, and the surface on which the liquid crystal alignment film is formed is attached inside. Combined. ZLI-6610 (Δε = −3.1, Δn = 0.0996) was vacuum-injected into the cell, the inlet was sealed with a photocuring agent, and UV was irradiated to cure the photocuring agent. Next, a heat treatment was performed at 110 ° C. for 30 minutes to manufacture a liquid crystal display element.

A ± 9 V rectangular wave (frequency 30 Hz) was applied to the manufactured liquid crystal display element for 1 minute, and then UV of 30,000 mJ / cm ² was applied while applying a ± 9 V rectangular wave. Here, the voltage value of ± 9 V substantially corresponds to the saturation voltage (Vsat) obtained from the voltage-transmittance curve of the cell.

[Examples 2-32 and Comparative Examples 1-3]
A liquid crystal display device was produced according to Example 1 except that the varnish and the photopolymerizable monomer were changed. In Example 2, Irgacure 651 corresponding to 10% by weight of the weight of the compound (V-3-2-6) was added. The production conditions of the liquid crystal display element are summarized in Tables 2-1 and 2-2 including Example 1. The addition of Irgacure 651 is indicated by a circle in the table.

[Examples 33 to 162]
A liquid crystal display device was produced according to Example 1 except that the compound (V-3-2-6) was used as the photopolymerizable monomer and the polyamic acid solution was changed to another polyamic acid solution or a soluble polyimide solution. did. For Examples 152 to 162, a solution obtained by adding an additive to a polyamic acid solution or a polyimide solution was used. Table 2-3 summarizes the polyamic acid solution, soluble polyimide solution, additives, and amounts added in each Example. In addition, the addition amount of an additive shows the weight amount per 100 weight of solid content of a polyamic acid solution or a polyimide solution.

<3. Evaluation of response time>
About the liquid crystal display element produced in Examples 1-162 and Comparative Examples 1-3, the response time was measured in the following procedures.

For measuring the response time (τ; measured at 25 ° C .; ms), an LCD 5200 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used. The light source is a halogen lamp. The low pass filter was set to 5 kHz. A rectangular wave (60 Hz, 10 V, 0.5 seconds) was applied to the manufactured liquid crystal display element. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. The transmittance is 100% when the light amount is maximum, and the transmittance is 0% when the light amount is minimum. The rise time (τr: rise time) is the time required for the transmittance to change from 10% to 90%. Fall time (τf: fall time) is the time required to change the transmittance from 90% to 10%. The response time is the sum of the rise time and fall time obtained in this way. The results are shown in Table 3.

A liquid crystal aligning film was formed on a glass substrate using a liquid crystal aligning agent containing a polyamic acid containing a photopolymerizable monomer, and a liquid crystal display element was constituted with the glass substrate. When UV light is applied to the liquid crystal display element while irradiating UV to react the photopolymerizable monomer, as shown in Table 3, the effect of shortening the response time when driving the liquid crystal display element is remarkable. there were.

In addition, a liquid crystal display device was produced in accordance with the method described in Example 1, using a varnish in which the weight ratio of the photopolymerizable monomer added to the polyamic acid solution was changed. As shown in Tables 4-1 to 4-3, there was a tendency that the response time further shortened as the weight ratio of the photopolymerizable monomer increased.

It was also confirmed that the contrast of the liquid crystal cell produced using this technology was improved over the contrast of the PSA liquid crystal cell.

Claims (20)

A pair of substrates disposed opposite to each other, electrodes formed on one or both of the opposed surfaces of each of the pair of substrates, and liquid crystal alignment formed on the opposed surfaces of the pair of substrates A film, and a liquid crystal layer formed between the pair of substrates,
By applying a voltage higher than the threshold voltage (Vth) of the liquid crystal composition to the liquid crystal composition, the liquid crystal aligns part or all of the photopolymerizable monomer or photopolymerizable oligomer present on the surface of the liquid crystal alignment film. Oriented along the direction to
Method of manufacturing a liquid crystal display device through the step of immobilizing the alignment state by irradiating light while applying a voltage.
Here, the liquid crystal alignment film is a polyimide obtained by reacting a diamine and tetracarboxylic dianhydride, at least one selected from a polyamic acid and a polyamic acid derivative as a precursor thereof, a photopolymerizable monomer and / or The photopolymerizable oligomer is formed by using a liquid crystal aligning agent containing 0.01 to 50% by weight of the total solid content including polyimide, polyamic acid or polyamic acid derivative, and further containing a polymerization initiator and / or a polymerization inhibitor. ;
A polyimide obtained by reacting the diamine with tetracarboxylic dianhydride or a precursor thereof, a polyamic acid or a polyamic acid derivative, is a compound having a structural unit represented by the following formula (I) or (II). Yes;

In formulas (I) and (II):
R ′ is independently hydrogen or alkyl having 1 to 4 carbons;
R ¹ is independently 2 from at least one diamine selected from the group of compounds represented by the following formulas (III-1) to (III-7) and formulas (III-8) to (III-12): A residue without two amino groups;
R ² is independently a tetravalent organic group; and
R ¹ and R ² may be different for each structural unit:

In the above formula, m is independently an integer of 1 to 12. In the formulas (III-2), (III-3), and (III-5) to (III-7), n is independently 0 to 2. In formula (III-4), n is independently 1 or 2;
G ¹ is independently a single bond, —O—, —S—, —S—S—, —SO ₂ —, —CO—, —CONH—, —NHCO—, —C (CH ₃ ) ₂ —, — C (CF ₃ ) ₂ —, — (CH ₂ ) _p —, —O— (CH ₂ ) _p —O—, or —S— (CH ₂ ) _p —S—, wherein p is independently 1 G ² is independently a single bond, —O—, —S—, —CO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, or C 1 10 alkylene;
Any —H in the cyclohexane and benzene rings in the formula may be replaced by —F, —OH, —CF ₃ , —CH ₃ or benzyl; and
The bonding position of —NH ₂ to the cyclohexane ring or the benzene ring is any position except the bonding position of G ¹ or G ² ;

In Formula (III-8), G ³ is a single bond, —O—, —COO—, —OCO—, —CO—, —CONH—, or — (CH ₂ ) _m —, and m is 1 to 12. An integer of;
R ⁴ is alkyl having 3 to 20 carbon atoms, phenyl, a group having a steroid skeleton, cyclohexyl, or a group represented by the formula (III-8-a);
In this alkyl, any —H may be replaced by —F, and any —CH ₂ — may be replaced by —O—;
_-H in which _{phenyl, -F, -CH 3, -OCH 3} , -OCH 2 F, -OCHF 2, -OCF 3, has been replaced by an alkoxy alkyl or C3-20 having 3 to 20 carbon atoms The —H of the cyclohexyl may be replaced by alkyl having 3 to 20 carbons or alkoxy having 3 to 20 carbons;
The group having the steroid skeleton does not include an alkenyl linked group at the C-17 position of the steroid nucleus; and
The bonding position of —NH ₂ to the benzene ring is arbitrary.
Provided that when G ³ is — (CH ₂ ) _m —, m is 1, and R ⁴ is phenyl, at least one —H of the phenyl is —F, —CH ₃ , —OCH ₃ , _{-OCH 2 F, -OCHF 2, -OCF} 3, has been replaced by an alkoxy alkyl or C3-20 having 3 to 20 carbon atoms;

In the formula (III-8-a), R ⁵ is —H, —F, alkyl having 1 to 20 carbons, fluorine-substituted alkyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons, —CN, —OCH ₂ F, —OCHF ₂ , or —OCF ₃ ;
G ⁴ , G ⁵ and G ⁶ are a linking group, and these are independently a single bond or alkylene having 1 to 12 carbons; one or more —CH ₂ — in the alkylene is —O—, — May be replaced by COO-, -OCO-, -CONH-;
A, A ¹ , A ² and A ³ are rings, which 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;
In A, A ¹ , A ² and A ³ , any —H may be replaced by —F or —CH ₃ ;
a, b and c are independently integers from 0 to 2 and their sum is from 1 to 5;
when a, b or c is 2, the two linking groups in each bracket may be the same or different and the two rings may be the same or different;

In formulas (III-9) and (III-10),
R ⁶ is independently —H or —CH ₃ ;
R ⁷ is independently —H or alkyl having 1 to 20 carbons;
G ⁷ is independently a single bond, —CO— or —CH ₂ —;
One -H of the benzene ring in formula (III-10) may be replaced by alkyl or phenyl having 1 to 20 carbon atoms; and
A group whose bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position is arbitrary;

In formulas (III-11) and (III-12),
R ⁸ is —H or alkyl having 1 to 20 carbons, and any —CH ₂ — in the alkyl may be replaced by —O—;
R ⁹ is alkyl having 6 to 22 carbons;
R ¹⁰ is —H or alkyl having 1 to 22 carbons;
G ⁸ is —O— or alkylene having 1 to 6 carbons;
A ⁴ is 1,4-phenylene or 1,4-cyclohexylene;
G ⁹ is a single bond or alkylene having 1 to 3 carbon atoms;
d is 0 or 1; and
The bonding position of —NH ₂ to the benzene ring is arbitrary. A pair of substrates disposed opposite to each other, electrodes formed on one or both of the opposed surfaces of each of the pair of substrates, and liquid crystal alignment formed on the opposed surfaces of the pair of substrates A film, and a liquid crystal layer formed between the pair of substrates,
By applying a voltage higher than the threshold voltage (Vth) of the liquid crystal composition to the liquid crystal composition, the liquid crystal aligns part or all of the photopolymerizable monomer or photopolymerizable oligomer present on the surface of the liquid crystal alignment film. Oriented along the direction to
Method of manufacturing a liquid crystal display device through the step of immobilizing the alignment state by irradiating light while applying a voltage.
Here, the liquid crystal alignment film is a polyimide obtained by reacting a diamine and tetracarboxylic dianhydride, at least one selected from a polyamic acid and a polyamic acid derivative as a precursor thereof, a photopolymerizable monomer and / or A photopolymerizable oligomer containing 0.01 to 50% by weight of the total solid content including polyimide, polyamic acid or polyamic acid derivative, alkenyl-substituted nadiimide compound, compound having radical polymerizable unsaturated double bond, oxazine compound, oxazoline Formed using a liquid crystal aligning agent further containing at least one additive selected from the group of compounds consisting of a compound, a liquid crystal aligning polyorganosiloxane and an epoxy compound;
A polyimide obtained by reacting the diamine with tetracarboxylic dianhydride or a precursor thereof, a polyamic acid or a polyamic acid derivative, is a compound having a structural unit represented by the following formula (I) or (II). Yes;

In formulas (I) and (II):
R ′ is independently hydrogen or alkyl having 1 to 4 carbons;
R ¹ is independently 2 from at least one diamine selected from the group of compounds represented by the following formulas (III-1) to (III-7) and formulas (III-8) to (III-12): A residue without two amino groups;
R ² is independently a tetravalent organic group; and
R ¹ and R ² may be different for each structural unit:

In the above formula, m is independently an integer of 1 to 12. In the formulas (III-2), (III-3), and (III-5) to (III-7), n is independently 0 to 2. In formula (III-4), n is independently 1 or 2;
G ¹ is independently a single bond, —O—, —S—, —S—S—, —SO ₂ —, —CO—, —CONH—, —NHCO—, —C (CH ₃ ) ₂ —, — C (CF ₃ ) ₂ —, — (CH ₂ ) _p —, —O— (CH ₂ ) _p —O—, or —S— (CH ₂ ) _p —S—, wherein p is independently 1 G ² is independently a single bond, —O—, —S—, —CO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, or C 1 10 alkylene;
Any —H in the cyclohexane and benzene rings in the formula may be replaced by —F, —OH, —CF ₃ , —CH ₃ or benzyl; and
The bonding position of —NH ₂ to the cyclohexane ring or the benzene ring is any position except the bonding position of G ¹ or G ² ;

In Formula (III-8), G ³ is a single bond, —O—, —COO—, —OCO—, —CO—, —CONH—, or — (CH ₂ ) _m —, and m is 1 to 12. An integer of;
R ⁴ is alkyl having 3 to 20 carbon atoms, phenyl, a group having a steroid skeleton, cyclohexyl, or a group represented by the formula (III-8-a);
In this alkyl, any —H may be replaced by —F, and any —CH ₂ — may be replaced by —O—;
_-H in which _{phenyl, -F, -CH 3, -OCH 3} , -OCH 2 F, -OCHF 2, -OCF 3, has been replaced by an alkoxy alkyl or C3-20 having 3 to 20 carbon atoms The —H of the cyclohexyl may be replaced by alkyl having 3 to 20 carbons or alkoxy having 3 to 20 carbons;
The group having the steroid skeleton does not include an alkenyl linked group at the C-17 position of the steroid nucleus; and
The bonding position of —NH ₂ to the benzene ring is arbitrary.
Provided that when G ³ is — (CH ₂ ) _m —, m is 1, and R ⁴ is phenyl, at least one —H of the phenyl is —F, —CH ₃ , —OCH ₃ , _{-OCH 2 F, -OCHF 2, -OCF} 3, has been replaced by an alkoxy alkyl or C3-20 having 3 to 20 carbon atoms;

In the formula (III-8-a), R ⁵ is —H, —F, alkyl having 1 to 20 carbons, fluorine-substituted alkyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons, —CN, —OCH ₂ F, —OCHF ₂ , or —OCF ₃ ;
G ⁴ , G ⁵ and G ⁶ are a linking group, and these are independently a single bond or alkylene having 1 to 12 carbons; one or more —CH ₂ — in the alkylene is —O—, — May be replaced by COO-, -OCO-, -CONH-;
A, A ¹ , A ² and A ³ are rings, which 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;
In A, A ¹ , A ² and A ³ , any —H may be replaced by —F or —CH ₃ ;
a, b and c are independently integers from 0 to 2 and their sum is from 1 to 5;
when a, b or c is 2, the two linking groups in each bracket may be the same or different and the two rings may be the same or different;

In formulas (III-9) and (III-10),
R ⁶ is independently —H or —CH ₃ ;
R ⁷ is independently —H or alkyl having 1 to 20 carbons;
G ⁷ is independently a single bond, —CO— or —CH ₂ —;
One -H of the benzene ring in formula (III-10) may be replaced by alkyl or phenyl having 1 to 20 carbon atoms; and
A group whose bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position is arbitrary;

In formulas (III-11) and (III-12),
R ⁸ is —H or alkyl having 1 to 20 carbons, and any —CH ₂ — in the alkyl may be replaced by —O—;
R ⁹ is alkyl having 6 to 22 carbons;
R ¹⁰ is —H or alkyl having 1 to 22 carbons;
G ⁸ is —O— or alkylene having 1 to 6 carbons;
A ⁴ is 1,4-phenylene or 1,4-cyclohexylene;
G ⁹ is a single bond or alkylene having 1 to 3 carbon atoms;
d is 0 or 1; and
The bonding position of —NH ₂ to the benzene ring is arbitrary. The additive is N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, 1,3-bis ( N, N-diglycidylaminomethyl) cyclohexane, liquid crystal alignment polyorganosiloxane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 3-glycidyloxypropyltrimethoxysilane. The manufacturing method of the liquid crystal display element of Claim 2 which is at least one. At least one diamine having a side chain structure represented by formulas (III-8) to (III-12), or a side chain structure represented by formulas (III-8) to (III-12) The manufacturing method of the liquid crystal display element of any one of Claims 1-3 which is a mixture of at least 1 of the diamine which has diamine, and the diamine represented by Formula (III-1)-(III-7). The method for producing a liquid crystal display element according to claim 4, wherein the diamine having a side chain structure is at least one selected from the group of compounds represented by formula (III-8). The method for producing a liquid crystal display element according to claim 4, wherein the diamine having a side chain structure is at least one selected from the group of compounds represented by formulas (III-9) and (III-10). The method for producing a liquid crystal display element according to claim 4, wherein the diamine having a side chain structure is at least one selected from the group of compounds represented by formulas (III-11) and (III-12). Diamines having a side chain structure are represented by the following formulas (III-8-1), (III-8-2), (III-8-4) to (III-8-6), (III-8-21), ( III-8-22), (III-8-27), (III-8-28), (III-8-30), (III-8-39), (III-8-41), (III- The manufacturing method of the liquid crystal display element of Claim 4 which is at least 1 selected from the group of the compound represented by 8-42), (III-9-1), and (III-9-3). .

In formulas (III-8-1) and (III-8-2), R ^4a is alkyl having 3 to 20 carbons or alkoxy having 3 to 20 carbons;
In formulas (III-8-4) to (III-8-6), R ^5a is alkyl having 1 to 18 carbons or alkoxy having 1 to 18 carbons;
In the formulas (III-8-21), (III-8-27) and (III-8-39), R ^5b is —H, —F, alkyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons. , _-CN, be -OCH 2 F, -OCHF ₂ or -OCF _3; and,
In formulas (III-8-22), (III-8-28) and (III-8-30), R ^4d is alkyl having 1 to 20 carbons or alkoxy having 1 to 20 carbons. The diamine is represented by the formula (III-2-3), (III-4-9), (III-5-1) to (III-5-12), (III-5-31) to (III-5-35). The method for producing a liquid crystal display element according to claim 4, which is at least one selected from the group of compounds represented by (III-7-3):

The tetracarboxylic dianhydride is at least one selected from the group of compounds represented by the following formulas (IV-1) to (IV-13), or formulas (IV-1) to (IV-13): The manufacturing method of the liquid crystal display element of any one of Claims 1-3 which is a mixture of at least 1 selected from the group of the compound represented by other tetracarboxylic dianhydrides.

In formula (IV-1),
G ¹¹ is a single bond, alkylene having 1 to 12 carbons, 1,4-phenylene, or 1,4-cyclohexylene; and
X ¹ is independently a single bond or —CH ₂ —.

In formula (IV-2),
R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ are —H, —CH ₃ , —CH ₂ CH ₃ , or phenyl.

In the formula (IV-3), ring ^{A 5} are a cyclohexane ring or a benzene ring.

In formula (IV-4),
G ¹² is a single bond, alkylene having 1 to 12 carbons, —O—, —CO—, —S—, —C (CH ₃ ) ₂ —, —SO—, or —C (CF ₃ ) ₂ —. And
Ring A ⁵ are a cyclohexane ring or benzene ring independently.

In the formula (IV-5), R ¹⁷ is independently —H or —CH ₃ .

In formula (IV-6):
X ¹ is independently a single bond or —CH ₂ —; and
v is 1 or 2.

In the formula (IV-7), X ¹ is a single bond or —CH ₂ —.

In formula (IV-8):
R ¹⁸ is —H, —CH ₃ , —CH ₂ CH ₃ , or phenyl; and
A ⁶ is a cyclohexane ring or a cyclohexene ring.

In formula (IV-9), w1 and w2 are 0 or 1.

In formula (IV-11), A ⁵ is independently a cyclohexane ring or a benzene ring.

In formula (IV-12), X ² is alkylene having 2 to 6 carbons, and
Ph is an abbreviation for phenyl.

Tetracarboxylic dianhydride has the formula (IV-1-1), (IV-2-1), (IV-3-1), (IV-3-2), (IV-4-23), ( IV-5-3), (IV-7-2), (IV-10), (IV-12-1), and at least one selected from the group of compounds represented by (IV-13) The manufacturing method of the liquid crystal display element of Claim 10 which exists.

In formula (IV-12-1), Ph is an abbreviation for phenyl. The tetracarboxylic dianhydride is at least one selected from the group of compounds represented by formulas (IV-1), (IV-2) and (IV-3), or formula (IV-1), ( The method for producing a liquid crystal display element according to claim 10, which is a mixture of at least one selected from the group of compounds represented by IV-2) and (IV-3) and other tetracarboxylic dianhydrides. . The manufacturing method of the liquid crystal display element of any one of Claims 1-3 whose photopolymerizable monomer is at least 1 sort (s) of compound represented by following formula (V).

R ^a1 -Z- (BZ) _m1 -R ^a1 (V)

In formula (V):
R ^a1 is independently a polymerizable group represented by the following formulas (V-1-1) to (V-1-5), —H, halogen, —CN, —CF ₃ , —CF ₂ H, -CFH _2, -OCF _3, alkyl having _{-OCF 2 H, -N = C =} O, -N = C = S or C 1-20;
In this alkyl, any —CH ₂ — represents —O—, —S—, —SO ₂ —, —CO—, —COO—, —OCO—, —CH═CH—, —CF═CF— or — May be replaced by C≡C-;
Optional -H may be replaced by halogen or -CN;
At least one of R ^a1 is a polymerizable group represented by formulas (V-1-1) to (V-1-5);
B is a ring and is independently a saturated or unsaturated independent ring having 3 to 20 carbon atoms, a condensed ring, or a spirocyclic divalent group;
In these rings, any —CH ₂ — may be replaced by —O—;
Any —CH═ may be replaced by —N═;
Any -H is _{halogen, -CN, -NO 2, -NC,} -N = C = O, -N = C = S, silyl which is substituted with 1 to 3 alkyl of 1 to 4 carbon atoms, May be substituted with linear or branched alkyl having 1 to 10 carbon atoms or halogenated alkyl having 1 to 10 carbon atoms;
In this alkyl, any —CH ₂ — may be replaced by —O—, —CO—, —COO—, —OCO—, —OCOO—, —CH═CH— or —C≡C—. ;
Z is independently a single bond or alkylene having 1 to 20 carbon atoms;
In this alkylene, arbitrary —CH ₂ — represents —O—, —S—, —SO ₂ —, —CO—, —COO—, —OCO—, —OCOO—, —CH═CH—, —CF═. May be replaced by CF-, -CH = N-, -N = CH-, -N = N-, -N (O) = N-, or -C≡C-;
Optional -H may be replaced by halogen, alkyl having 1 to 10 carbons, or alkyl halide having 1 to 10 carbons; and
m1 is an integer from 1 to 6,
When m1 is an integer of 2 to 6, a plurality of -BZ- in parentheses may be the same or different.

In the formulas (V-1-1) to (V-1-5), R ^b is —H, halogen, —CF _3, or alkyl having 1 to 5 carbons. At least one of R ^a1 in the formula (V) is a polymerizable group represented by any one of the formulas (V-1-1), (V-1-2), or (V-1-3). Item 14. A method for producing a liquid crystal display element according to Item 13. Ring B in formula (V) is independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, Represented by fluorene-2,7-diyl, bicyclo [2.2.2] octane-1,4-diyl, or bicyclo [3.1.0] hexane-3,6-diyl, triptycene-1,4-diyl A divalent group that is
In these rings, any —CH ₂ — may be replaced by —O—;
Any —CH═ may be replaced by —N═;
Arbitrary —H is substituted with halogen, —CN, —NO ₂ , —NC, —N═C═O, —N═C═S, 1 to 3 C 1-4 alkyl or phenyl Optionally substituted by silyl, linear or branched alkyl having 1 to 10 carbon atoms or alkyl halide having 1 to 10 carbon atoms;
In this alkyl, any —CH ₂ — may be replaced by —O—, —CO—, —COO—, —OCO—, —OCOO—, —CH═CH—, or —C≡C—. The manufacturing method of the liquid crystal display element of Claim 13 which is good. The ring B in the formula (V) is one independently selected from the group of groups represented by the following formulas (V-2-1) to (V-2-25): The manufacturing method of the liquid crystal display element of description.

In formulas (V-2-1) to (V-2-25), L represents a halogen, an alkyl having 1 to 3 carbon atoms, an alkoxy having 1 to 3 carbon atoms, or an alkyl halide having 1 to 3 carbon atoms. . The liquid crystal display element according to claim 13, wherein the photopolymerizable monomer is at least one selected from the group of compounds represented by the following formulas (V-3-1) to (V-3-12). Manufacturing method .

(In the formulas (V-3-1) to (V-3-12), R ^c represents —H or —CH _3, and —H on the benzene ring represents halogen, —CH ₃ , —CF ₃ or —OCH. _May be replaced by ₃ ;
R ^d independently represents —H, halogen, —CH ₃ , —CF ₃ , —OCH ₃ , phenyl, or two R ^d on the same carbon each represents a saturated or unsaturated hydrocarbon ring having 6 to 15 carbon atoms. May be formed; and
m2 and m3 are each independently an integer of 1-20. When the liquid crystal aligning agent layer applied on the substrate is baked at a temperature of 100 to 230 ° C., 50% by weight or more of the photopolymerizable monomer and / or photopolymerizable oligomer remains without thermal polymerization. Item 4. The method for producing a liquid crystal display element according to any one of Items 1 to 3. When the liquid crystal aligning agent layer applied on the substrate is baked at a temperature of 180 to 230 ° C., 50% by weight or more of the photopolymerizable monomer and / or photopolymerizable oligomer remains without thermal polymerization. Item 19. A method for producing a liquid crystal display element according to Item 18. 1,000~300,000mJ / cm ² of ultraviolet light was irradiated Ru reacting a photopolymerizable monomer and / or photopolymerizable oligomer, the liquid crystal display device according to claim 1 Manufacturing method .