JP6572912B2 - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Description

  The present invention relates to a liquid crystal alignment treatment agent, a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent, and a liquid crystal display element using the liquid crystal alignment film.

Liquid crystal display elements are now widely used as display devices that are thin and light. Usually, in this liquid crystal display element, a liquid crystal alignment film is used to determine the alignment state of the liquid crystal.
One of the characteristics required for the liquid crystal alignment film is the control of the so-called pretilt angle of the liquid crystal, which maintains the alignment tilt angle of the liquid crystal molecules with respect to the substrate surface at an arbitrary value. It is known that the magnitude of the pretilt angle can be changed by selecting the structure of the polyimide constituting the liquid crystal alignment film. Among the techniques for controlling the pretilt angle depending on the structure of the polyimide, the method using a diamine compound having a side chain as a part of the polyimide raw material can control the pretilt angle according to the proportion of the diamine compound used. Is relatively easy and is useful as means for increasing the pretilt angle (see Patent Document 1). In addition, the diamine compound for increasing the pretilt angle of the liquid crystal has been studied for improving the stability and process dependency of the pretilt angle, and the side chain structure used here is phenyl. Those containing a ring structure such as a group or a cyclohexyl group have been proposed (see Patent Document 2).

  In order to manufacture a liquid crystal display element, a step of filling liquid crystal between two substrates (cell gaps) on which a liquid crystal alignment film is formed is necessary. Until now, liquid crystal filling has been generally performed by a vacuum injection method in which a liquid crystal is filled between two substrates using a pressure difference between atmospheric pressure and vacuum. However, in this method, since the liquid crystal injection port is provided only on one side of the substrate, it takes a long time to fill the liquid crystal, and it is difficult to simplify the manufacturing process of the liquid crystal display element. This has been a big problem particularly in the production of liquid crystal TVs and large monitors that have been put into practical use in recent years.

  Therefore, in order to solve the problems in the above-described vacuum injection method, a liquid crystal dropping method (ODF (One Drop Filling) method) has been developed. In this method, a liquid crystal is dropped on a substrate on which a liquid crystal alignment film is formed, bonded to the other substrate in a vacuum, and then the sealing material is UV cured to fill the liquid crystal. On the other hand, as the definition of liquid crystal display elements becomes higher, it is necessary to suppress display unevenness. The liquid crystal dropping method has been solved by optimizing the manufacturing process so as to reduce the influence of adsorbed water and impurities, such as reducing the dropping amount of liquid crystal and improving the degree of vacuum at the time of bonding. However, as the liquid crystal display element production line becomes larger, it is no longer possible to suppress display unevenness by optimizing the manufacturing process so far, and a liquid crystal alignment film that can reduce alignment unevenness more than before has been demanded.

In addition, as liquid crystal display elements have become higher in definition, the liquid crystal alignment film used there also has a high voltage holding ratio and a direct current voltage, from the viewpoint of suppressing the reduction in contrast of the liquid crystal display elements and reducing the afterimage phenomenon. The characteristic that the accumulated charge at the time of applying a small amount of charge or that the charge accumulated by the DC voltage is quickly relaxed has become increasingly important.
In a polyimide-based liquid crystal alignment film, a liquid crystal alignment treatment agent containing a tertiary amine having a specific structure in addition to polyamic acid or an imide group-containing polyamic acid is assumed to have a short time until an afterimage generated by a DC voltage disappears. Those used (for example, see Patent Document 3), those using a liquid crystal alignment treatment agent containing a soluble polyimide using a specific diamine compound having a pyridine skeleton or the like as a raw material (see Patent Document 4), and the like are known. .

  In addition to polyamic acid and its imidized polymer, a compound containing one carboxylic acid group in the molecule, assuming that the voltage holding ratio is high and the time until the afterimage generated by direct current voltage disappears is short , Using a liquid crystal alignment treatment agent containing a very small amount of a compound selected from a compound containing one carboxylic anhydride group in the molecule and a compound containing one tertiary amino group in the molecule (patent Document 5) is known.

JP-A-2-282726 JP-A-9-278724 JP 9-316200 A JP-A-10-104633 JP-A-8-76128

  The liquid crystal alignment film is also used for controlling the angle of the liquid crystal with respect to the substrate, that is, the pretilt angle of the liquid crystal. In particular, in the VA mode, the PSA mode, and the like, since the liquid crystal needs to be aligned vertically, the liquid crystal alignment film is required to have an ability to align the liquid crystal vertically (also referred to as a vertical alignment property or a high pretilt angle). Furthermore, the liquid crystal alignment film has become important not only for high vertical alignment but also for its stability. In particular, a liquid crystal display element using a backlight that generates a large amount of heat and has a large amount of light to obtain high brightness, such as a car navigation system or a large television, is exposed to high temperature and light irradiation for a long time. There are cases where it is used or left in a dark environment. Under such severe conditions, when the vertical alignment property is lowered, problems such as failure to obtain initial display characteristics or occurrence of unevenness in display occur.

  In addition, in the ODF method, since the liquid crystal is dropped directly on the alignment film, physical stress is applied to the alignment film when the liquid crystal is dropped, and it is necessary to fill the entire panel with liquid crystal, and it is necessary to increase the dropping point of the liquid crystal. is there. Therefore, so-called alignment unevenness such as dripping traces and lattice unevenness occurs in the liquid crystal dropping portion or the portion where the liquid crystal droplets are in contact with the adjacent liquid droplets. When this is used as a liquid crystal display element, display unevenness due to alignment unevenness occurs. There was a problem that occurred. This alignment unevenness is caused by the adsorbed water and impurities adhering to the surface of the liquid crystal alignment film formed on the substrate being swept away by the liquid crystal dropped in the ODF process, so that the liquid crystal dropping part and the liquid crystal droplets are in contact with each other. It is thought to be generated due to the difference in the amount of adsorbed water and impurities.

  Furthermore, regarding the voltage holding ratio which is one of the electrical characteristics of the liquid crystal display element, high stability under the above severe conditions is also required. That is, if the voltage holding ratio is reduced by light irradiation from the backlight, a burn-in defect (also referred to as line burn-in), which is one of display defects of the liquid crystal display element, is likely to occur. A high liquid crystal display element cannot be obtained. Therefore, in the liquid crystal alignment film, in addition to good initial characteristics, for example, it is required that the voltage holding ratio does not easily decrease even after being exposed to light irradiation for a long time. Furthermore, there is a need for a liquid crystal alignment film that can quickly relieve residual charges accumulated by a direct current voltage by light irradiation from a backlight, even for another surface burn-in, which is another burn-in defect.

  Therefore, the present invention exhibits stable vertical stability even after being exposed to high temperature and light irradiation for a long time, suppresses a decrease in voltage holding ratio, and reduces the residual charge accumulated by a DC voltage. An object of the present invention is to provide a liquid crystal alignment film that can reduce liquid crystal alignment unevenness generated by the ODF method quickly. In addition, it is providing the liquid crystal aligning agent for obtaining said liquid crystal aligning film, and a liquid crystal display element provided with said liquid crystal aligning film.

（Ｘ^１は単結合、−（ＣＨ_２）_ａ−（ａは１〜１５の整数である）、−Ｏ−、−ＣＨ_２Ｏ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＮ（ＣＨ_３）−、−Ｎ（ＣＨ_３）ＣＯ−、−ＣＯＯ−及び−ＯＣＯ−からなる群から選ばれる少なくとも１種の結合基を示す。Ｘ^２は単結合又は−（ＣＨ_２）_ｂ−（ｂは１〜１５の整数である）を示す。Ｘ³は単結合、−（ＣＨ₂）_ｃ−（ｃは1〜1５の整数である）、−Ｏ−、−ＣＨ_２Ｏ−、−ＣＯＯ−及び−ＯＣＯ−からなる群から選ばれる少なくとも１種を示す。Ｘ^４はベンゼン環、シクロヘキサン環及び複素環からなる群から選ばれる少なくとも１種の２価の環状基、又はステロイド骨格を有する炭素数１７〜５１の２価の有機基を示し、前記環状基上の任意の水素原子は、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシ基、炭素数１〜３のフッ素含有アルキル基、炭素数１〜３のフッ素含有アルコキシ基又はフッ素原子で置換されていてもよい。Ｘ^５はベンゼン環、シクロヘキサン環及び複素環からなる群から選ばれる少なくとも１種の環状基を示し、これらの環状基上の任意の水素原子が、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシ基、炭素数１〜３のフッ素含有アルキル基、炭素数１〜３のフッ素含有アルコキシ基又はフッ素原子で置換されていてもよい。ｎは０〜４の整数を示す。Ｘ^６は炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、炭素数１〜１８のフッ素含有アルキル基、炭素数１〜１８のアルコキシ基及び炭素数１〜１８のフッ素含有アルコキシ基からなる群から選ばれる少なくとも１種を示す。）

（Ｗ^１は−Ｏ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＯ−、−ＣＯＮ（ＣＨ_３）−及び−Ｎ（ＣＨ_３）ＣＯ−からなる群から選ばれる少なくとも１種の結合基を示す。Ｗ^２は単結合、炭素数１〜２０のアルキレン基、非芳香族環及び芳香族環からなる群から選ばれる少なくとも１種を示す。Ｗ^３は単結合、−Ｏ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮ（ＣＨ_３）−、−Ｎ（ＣＨ_３）ＣＯ−及び−Ｏ（ＣＨ_２）_ｍ−（ｍは１〜５の整数を示す）からなる群から選ばれる少なくとも１種を示す。Ｗ^４は窒素有芳香族複素環を示す。As a result of intensive studies, the present inventor has found that a liquid crystal aligning agent containing three polymers having a specific structure is extremely effective for achieving the above object, and completes the present invention. It came. That is, the present invention has the following gist.
(1) Liquid crystal aligning agent containing the following (A) component, (B) component, and (C) component.
Component (A): a polyimide precursor obtained by reaction of a diamine having a structure of the following formula [1] and a diamine component having a structure of the following formula [2] with a tetracarboxylic acid component or the polyimide Polyimide with imidized precursor.
(B) Component: A polyimide precursor obtained by reaction of a diamine component containing a diamine having the structure of the following formula [2] and a tetracarboxylic acid component or a polyimide obtained by imidizing the polyimide precursor.
(C): a polyimide obtained by reaction of a diamine component containing a diamine having at least one substituent selected from the group consisting of a carboxy group (COOH group) and a hydroxy group (OH group) with a tetracarboxylic acid component The polyimide which imidized the precursor or this polyimide precursor.

(X ¹ is a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, —CONH—, —NHCO—, —CON (CH ₃ ). —, —N (CH ₃ ) CO—, —COO—, and —OCO— represent at least one linking group selected from the group consisting of X ² is a single bond or — (CH ₂ ) _b — (b is 1 X ³ is a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— and —. X ⁴ represents at least one selected from the group consisting of OCO-, and X ⁴ has at least one divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, or a carbon number of 17 to 17 having a steroid skeleton. 51 represents a divalent organic group, and an arbitrary hydrogen atom on the cyclic group has 1 to 3 carbon atoms. An alkyl group, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom, X ⁵ may be a benzene ring, And at least one cyclic group selected from the group consisting of a cyclohexane ring and a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, It may be substituted with a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom, n is an integer of 0 to 4. X ⁶ is 1 to 18 carbon atoms. Selected from the group consisting of an alkyl group having 2 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and a fluorine-containing alkoxy group having 1 to 18 carbon atoms. Even without showing one.)

(W ¹ is —O—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —OCO—, —CON (CH ₃ ) — and —N (CH ₃ ) at least one linking group selected from the group consisting of CO-, wherein W ² is at least one selected from the group consisting of a single bond, an alkylene group having 1 to 20 carbon atoms, a non-aromatic ring and an aromatic ring. W ³ represents a single bond, —O—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —COO—, —OCO—, —CON (CH ₃ ) —, At least one selected from the group consisting of —N (CH ₃ ) CO— and —O (CH ₂ ) _m — (m represents an integer of 1 to 5), W ⁴ represents a nitrogen-containing aromatic heterocyclic ring; Show.

（Ｘは前記式［１］の構造を示す。ｎ１は１〜４の整数を示す。）
（７）前記式［２］の構造を有するジアミンが、下記式［２ａ］で示される上記（１）〜上記（６）のいずれかに記載の液晶配向処理剤。

（Ｗは前記式［２］の構造を示す。ｐ１は１〜４の整数を示す。）
（８）前記カルボキシ基及びヒドロキシ基からなる群から選ばれる少なくとも１種の置換基を有するジアミンが、下記式［３ａ］で示される上記（１）〜（７）のいずれかに記載の液晶配向処理剤。

（Ｙは下記式［３−１］又は式［３−２］の構造を示す。ｍ１は１〜４の整数を示す。）

（ａ及びｂはそれぞれ、０〜４の整数を示す。）
（９）前記（Ａ）成分、（Ｂ）成分及び（Ｃ）成分におけるテトラカルボン酸成分が、下記の式［４］のテトラカルボン酸二無水物を含む上記（１）〜（８）のいずれかに記載の液晶配向処理剤。

（Ｚは下記式［４ａ］〜式［４ｋ］の構造からなる群から選ばれる少なくとも１種の構造を示す。）

（Ｚ^１〜Ｚ^４はそれぞれ独立して、水素原子、メチル基、塩素原子及びベンゼン環からなる群から選ばれる少なくとも１種を示す。Ｚ^５及びＺ^６はそれぞれ独立して、水素原子又はメチル基を示す。）
（１０）Ｎ−メチル−２−ピロリドン、Ｎ−エチル−２−ピロリドン及びγ−ブチロラクトンからなる群から選ばれる少なくとも１種の溶媒を含有する上記（１）〜（９）のいずれかに記載の液晶配向処理剤。
（１１）１−ヘキサノール、シクロヘキサノール、１，２−エタンジオール、１，２−プロパンジオール、プロピレングリコールモノブチルエーテル、エチレングリコールモノブチルエーテル、ジプロピレングリコールジメチルエーテル及び下記式［Ｄ１］〜式［Ｄ３］の溶媒からなる群から選ばれる少なくとも１種の溶媒を含有する上記（１）〜（１０）のいずれかに記載の液晶配向処理剤。

（Ｄ^１は炭素数１〜３のアルキル基を示す。Ｄ^２は炭素数１〜３のアルキル基を示す。Ｄ^３は炭素数１〜４のアルキル基を示す。）
（１２）前記液晶配向処理剤が、エポキシ基、イソシアネート基、オキセタン基及びシクロカーボネート基からなる群から選ばれる架橋性化合物、ヒドロキシ基、ヒドロキシアルキル基及び低級アルコキシアルキル基からなる群から選ばれる架橋性化合物、又は重合性不飽和結合基を有する架橋性化合物を含有する上記（１）〜上記（１１）のいずれかに記載の液晶配向処理剤。
（１３）上記（１）〜（１２）のいずれかに記載の液晶配向処理剤から得られる液晶配向膜。
（１４）上記（１）〜（１２）のいずれかに記載の液晶配向処理剤をインクジェット法により塗布して得られる液晶配向膜。
（１５）上記（１３）又は（１４）に記載の液晶配向膜を有する液晶表示素子。
（１６）電極を備えた一対の基板の間に液晶層を有してなり、前記一対の基板の間に活性エネルギー線及び熱の少なくとも一方により重合する重合性化合物を含む液晶組成物を配置し、前記電極間に電圧を印加しつつ前記重合性化合物を重合させる工程を経て製造される液晶表示素子に用いられる上記（１３）又は（１４）に記載の液晶配向膜。
（１７）上記（１６）に記載の液晶配向膜を有する液晶表示素子。
（１８）電極を備えた一対の基板の間に液晶層を有してなり、前記一対の基板の間に活性エネルギー線及び熱の少なくとも一方により重合する重合性基を含む液晶配向膜を配置し、前記電極間に電圧を印加しつつ前記重合性基を重合させる工程を経て製造される液晶表示素子に用いられる上記（１３）又は（１４）に記載の液晶配向膜。
（１９）上記（１８）に記載の液晶配向膜を有する液晶表示素子。(2) The liquid-crystal aligning agent as described in said (1) in which the diamine which has the structure of said Formula [1] is used only for the diamine component in the said (A) component.
(3) When the use ratio (mol%) of the diamine having the structure represented by the formula [1] in the component (A) to the entire diamine component is 1.0, the formula [1 in the component (B) ] The liquid-crystal aligning agent as described in said (1) whose usage-ratio (mol%) with respect to the whole diamine component of the diamine which has a structure shown by is a ratio of 0.01-0.8.
(4) When the usage ratio (mol%) of the diamine having the structure represented by the formula [1] in the component (A) to the entire diamine component is 1.0, the formula [1 in the component (C) ] The liquid-crystal aligning agent as described in said (1) or (3) whose usage rate (mol%) with respect to the whole diamine component of the diamine which has a structure shown by is a ratio of 0.01-0.3.
(5) The above (1), wherein a diamine having at least one substituent selected from the group consisting of the carboxy group (COOH group) and the hydroxy group (OH group) is used only as a diamine component in the component (C). Liquid crystal aligning agent in any one of-(4).
(6) The liquid-crystal aligning agent in any one of said (1)-(5) by which the diamine which has the structure of said Formula [1] is shown by following formula [1a].

(X shows the structure of said Formula [1]. N1 shows the integer of 1-4.)
(7) The liquid crystal aligning agent according to any one of (1) to (6), wherein the diamine having the structure of the formula [2] is represented by the following formula [2a].

(W represents the structure of the formula [2]. P1 represents an integer of 1 to 4.)
(8) The liquid crystal alignment according to any one of the above (1) to (7), wherein the diamine having at least one substituent selected from the group consisting of the carboxy group and the hydroxy group is represented by the following formula [3a]. Processing agent.

(Y represents the structure of the following formula [3-1] or [3-2]. M1 represents an integer of 1 to 4.)

(A and b each represent an integer of 0 to 4)
(9) Any of the above (1) to (8), wherein the tetracarboxylic acid component in the (A) component, the (B) component, and the (C) component contains a tetracarboxylic dianhydride of the following formula [4] A liquid crystal alignment treatment agent according to claim 1.

(Z represents at least one structure selected from the group consisting of the structures of the following formulas [4a] to [4k].)

(Z ^{1 to} Z ⁴ each independently represents at least one selected from the group consisting of a hydrogen atom, a methyl group, a chlorine atom and a benzene ring. Z ⁵ and Z ⁶ each independently represent a hydrogen atom or a methyl group. Group.)
(10) The system according to any one of (1) to (9) above, which contains at least one solvent selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and γ-butyrolactone. Liquid crystal aligning agent.
(11) 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether and the following formulas [D1] to [D3] The liquid-crystal aligning agent in any one of said (1)-(10) containing the at least 1 sort (s) of solvent chosen from the group which consists of a solvent.

(D ¹ represents an alkyl group having 1 to 3 carbon atoms, D ² represents an alkyl group having 1 to ³ carbon atoms, and D ³ represents an alkyl group having 1 to 4 carbon atoms.)
(12) The liquid crystal aligning agent is a crosslinkable compound selected from the group consisting of an epoxy group, an isocyanate group, an oxetane group and a cyclocarbonate group, a crosslink selected from the group consisting of a hydroxy group, a hydroxyalkyl group and a lower alkoxyalkyl group. Liquid crystal aligning agent in any one of said (1)-(11) containing the crosslinkable compound which has a crystalline compound or a polymerizable unsaturated bond group.
(13) A liquid crystal alignment film obtained from the liquid crystal alignment treatment agent according to any one of (1) to (12).
(14) A liquid crystal alignment film obtained by applying the liquid crystal aligning agent according to any one of (1) to (12) by an ink jet method.
(15) A liquid crystal display device having the liquid crystal alignment film according to (13) or (14).
(16) A liquid crystal composition having a liquid crystal layer between a pair of substrates provided with electrodes and including a polymerizable compound that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates. The liquid crystal alignment film according to (13) or (14), which is used for a liquid crystal display device produced through a step of polymerizing the polymerizable compound while applying a voltage between the electrodes.
(17) A liquid crystal display device having the liquid crystal alignment film according to (16).
(18) A liquid crystal alignment film having a liquid crystal layer between a pair of substrates provided with electrodes and including a polymerizable group that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates. The liquid crystal alignment film according to the above (13) or (14), which is used for a liquid crystal display device produced through a step of polymerizing the polymerizable group while applying a voltage between the electrodes.
(19) A liquid crystal display device having the liquid crystal alignment film according to (18).

  The liquid crystal aligning agent of this invention can obtain the liquid crystal aligning film which shows the stable vertical alignment property, even after being exposed to high temperature and light irradiation for a long time. In addition, it is possible to obtain a liquid crystal alignment film that can reduce liquid crystal alignment unevenness generated by the ODF method. Furthermore, even after being exposed to light irradiation for a long time, it is possible to obtain a liquid crystal alignment film that suppresses the decrease in the voltage holding ratio and quickly relaxes the residual charges accumulated by the DC voltage.

The reason why the liquid crystal display device having the above excellent characteristics can be obtained by the present invention is not necessarily clear, but is estimated as follows.
The specific structure (1) in the specific polymer (A) has a C 17-51 divalent organic group having a benzene ring, a cyclohexane ring, a heterocyclic ring, or a steroid skeleton. The side chain structure of these rings and organic groups is a structure that is more rigid than a long-chain alkyl group that is a conventional technique for vertically aligning liquid crystals and is stable to light such as ultraviolet rays. Therefore, the liquid crystal alignment film obtained from the liquid crystal aligning agent having the specific structure (1) exhibits higher vertical alignment than the prior art, and further, even when exposed to light irradiation for a long time, the vertical alignment Can be suppressed. In addition, even when exposed to light irradiation, it is possible to reduce the voltage holding ratio and to suppress the decomposition products of side chain components that accumulate residual charges due to a direct current voltage.

Moreover, since the specific structure (1) is a highly hydrophobic structure, it is possible to suppress adsorbed water and impurities generated in the liquid crystal display element manufacturing process from adhering to the surface of the liquid crystal alignment film. Therefore, liquid crystal alignment unevenness generated by the ODF method can be reduced.
In addition, the nitrogen-containing heterocycle of the specific structure (2) in the specific polymers (A) and (B) is an electrostatic such as salt formation or hydrogen bonding with the carboxy group or hydroxy group in the specific polymer (C). By being linked by the interaction, charge transfer easily occurs between the nitrogen-containing aromatic heterocycle and the carboxy group or the hydroxy group. Thereby, the transferred electric charge can efficiently move in and between the molecules of the polyimide polymer, and the residual charge accumulated by the DC voltage can be relaxed quickly. Thus, the liquid crystal display element having the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention has excellent reliability.

Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４、Ｘ^５、Ｘ^６及びｎは、上記に定義した通りであるが、Ｘ^１は、原料の入手性や合成の容易さの点から、単結合、−（ＣＨ_２）_ａ−（ａは１〜１５の整数である）、−Ｏ−、−ＣＨ_２Ｏ−又は−ＣＯＯ−が好ましい。より好ましいのは、単結合、−（ＣＨ_２）_ａ−（ａは１〜１０の整数である）、−Ｏ−、−ＣＨ_２Ｏ−又は−ＣＯＯ−である。
Ｘ^２は、単結合又は−（ＣＨ_２）_ｂ−（ｂは１〜１０の整数である）が好ましい。
Ｘ^３は、合成の容易さの点から、単結合、−（ＣＨ_２）_ｃ−（ｃは１〜１５の整数である）、−Ｏ−、−ＣＨ_２Ｏ−又は−ＣＯＯ−が好ましい。より好ましいのは、単結合、−（ＣＨ_２）_ｃ−（ｃは１〜１０の整数である）、−Ｏ−、−ＣＨ_２Ｏ−又は−ＣＯＯ−である。
Ｘ^４は、合成の容易さの点から、ベンゼン環、シクロへキサン環又はステロイド骨格を有する炭素数１７〜５１の有機基が好ましい。
Ｘ^５は、ベンゼン環又はシクロへキサン環が好ましい。
Ｘ^６は、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、炭素数１〜１０のフッ素含有アルキル基、炭素数１〜１８のアルコキシ基又は炭素数１〜１０のフッ素含有アルコキシ基が好ましい。より好ましくは、炭素数１〜１２のアルキル基、炭素数２〜１８のアルケニル基又は炭素数１〜１２のアルコキシ基である。特に好ましくは、炭素数１〜９のアルキル基、炭素数２〜１２のアルケニル基又は炭素数１〜９のアルコキシ基である。
ｎは、原料の入手性や合成の容易さの点から、０〜３が好ましい。より好ましいのは、０〜２である。In the present invention, “part” and “%” mean “part by mass” and “% by mass”, respectively, unless otherwise specified.
<Specific structure (1) / Specific diamine (1)>
The specific diamine (1) in this invention has the specific structure (1) of following formula [1].

X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and n are as defined above, but X ¹ is a single bond, from the viewpoint of availability of raw materials and ease of synthesis, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O— or —COO— is preferable. More preferred is a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 10), —O—, —CH ₂ O— or —COO—.
X ² is preferably a single bond or — (CH ₂ ) _b — (b is an integer of 1 to 10).
X ³ is preferably a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ O— or —COO— from the viewpoint of ease of synthesis. More preferred is a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 10), —O—, —CH ₂ O— or —COO—.
X ⁴ is preferably an organic group having 17 to 51 carbon atoms having a benzene ring, a cyclohexane ring or a steroid skeleton from the viewpoint of ease of synthesis.
X ⁵ is preferably a benzene ring or a cyclohexane ring.
X ⁶ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a fluorine containing group having 1 to 10 carbon atoms. Alkoxy groups are preferred. More preferably, they are a C1-C12 alkyl group, a C2-C18 alkenyl group, or a C1-C12 alkoxy group. Particularly preferred are an alkyl group having 1 to 9 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkoxy group having 1 to 9 carbon atoms.
n is preferably 0 to 3 in view of availability of raw materials and ease of synthesis. More preferably, it is 0-2.

Preferred combinations of X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and n are listed in Tables 6 to 47 on pages 13 to 34 of International Publication No. WO2011 / 132751 (published 2011.10.20). (2-1) to (2-629) listed in (1). In each table of International Publication, ^X 1 to X ⁶ in the present invention is shown as Y1 to Y6, Y1 to ^Y6, shall read X 1 to X ^6. Moreover, in (2-605)-(2-629) published in each table | surface of international publication gazette, the C17-C51 organic group which has a steroid skeleton in this invention has 12-12 carbon atoms which have a steroid skeleton. An organic group having 25 to 25 carbon atoms having a steroid skeleton is to be read as an organic group having 17 to 51 carbon atoms having a steroid skeleton.

  Among them, (2-25) to (2-96), (2-145) to (2-168), (2-217) to (2-240), (2-268) to (2-315) , (2-364) to (2-387), (2-436) to (2-483), or (2-603) to (2-615) are preferred. Particularly preferred combinations are (2-49) to (2-96), (2-145) to (2-168), (2-217) to (2-240), (2-603) to (2- 606), (2-607) to (2-609), (2-611), (2-612) or (2-624).

Ｘは、前記式［１］の構造を示す。また、式［１ａ］中のＸ^１、Ｘ^２、Ｘ^３、Ｘ^４、Ｘ^５、Ｘ^６、及びｎの詳細、及び好ましい組み合せは、前記式［１］に記載される通りである。
ｎ１は、１〜４の整数を示す。なかでも、１の整数が好ましい。As the specific diamine (1), it is particularly preferable to use a diamine of the following formula [1a].

X represents the structure of the formula [1]. The details and preferred combinations of X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , and n in the formula [1a] are as described in the formula [1].
n1 shows the integer of 1-4. Among these, an integer of 1 is preferable.

Specifically, the formula [2-1] to the formula [2-6] and the formula [2-9] to be described on pages 15 to 19 of International Publication No. WO2013 / 125595 (published 2013.8.29) Examples include diamines of the formula [2-31]. In the description of International Publication WO2013 / 125595, _{R 4} in the formula [2-1] _{R 2} and wherein in ~ formula [2-3] [2-4] to the formula [2-6], the carbon It shows at least one selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and a fluorine-containing alkoxy group having 1 to 18 carbon atoms. Moreover, _{A 4} in the formula [2-13] is a straight or branched alkyl group having 3 to 18 carbon atoms. In addition, R ₃ in the formulas [2-4] to [2-6] represents at least one selected from the group consisting of —O—, —CH ₂ O—, —COO—, and —OCO—. .
Among these, preferred diamines can exhibit a stable pretilt angle, can reduce liquid crystal alignment unevenness generated by the ODF method, and have a high effect of suppressing a decrease in voltage holding ratio after being exposed to light irradiation for a long time. From the point, the formula [2-1] to the formula [2-6], the formula [2-9] to the formula [2-13], or the formula [2-22] to the formula [2] described in the international publication WO2013 / 125595 2-31].

From the above point, the specific diamine (1) is preferably used in an amount of 10 to 70 mol% based on the entire diamine component in the specific polymer (A). More preferred is 15 to 70 mol%, and particularly preferred is 20 to 60 mol%. In a specific polymer (B), 0-40 mol% is preferable with respect to the whole diamine component. More preferred is 0 to 30 mol%, and particularly preferred is 0 to 25 mol%. In the specific polymer (C), 0 to 20 mol% is preferable. More preferably, it is 0-10 mol%.
Moreover, specific diamine (1) is 1 type or depending on characteristics, such as the solubility to the solvent of a polyimide-type polymer, the liquid crystal aligning property at the time of setting it as a liquid crystal aligning film, and the optical characteristic of a liquid crystal display element. Two or more kinds can be mixed and used.

<Specific structure (2) / Specific diamine (2)>
The specific diamine (2) of the present invention has a specific structure represented by the following formula [2].

W ¹ , W ² , W ³ and W ⁴ are as defined above. Among these, the following are preferable.
W ¹ is preferably —O—, —NH—, —CONH—, —NHCO—, —CH ₂ O—, —OCO—, —CON (CH ₃ ) — or —N (CH ₃ ) CO—. More preferable is —O—, —NH—, —CONH—, —NHCO—, —CH ₂ O—, —OCO— or —CON (CH ₃ ) — from the viewpoint of ease of synthesis. Particularly preferred is —O—, —CONH— or —CH ₂ O—.
W ² represents at least one selected from the group consisting of a single bond, an alkylene group having 1 to 20 carbon atoms, a non-aromatic ring and an aromatic ring. The alkylene group having 1 to 20 carbon atoms may be linear or branched. Moreover, you may have an unsaturated bond. Among these, an alkylene group having 1 to 10 carbon atoms is preferable from the viewpoint of ease of synthesis.

  Specific examples of the non-aromatic ring include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cycloundecane ring, a cyclododecane ring, and a cyclotridecane ring. , Cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicosane ring, tricycloeicosan ring, tricyclodecosan ring, bicycloheptane ring, decahydronaphthalene ring, norbornene A ring, an adamantane ring, etc. are mentioned. Among these, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a norbornene ring, or an adamantane ring is preferable.

Specific examples of the aromatic ring include benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring and phenalene ring. Of these, a benzene ring, naphthalene ring, tetrahydronaphthalene ring, fluorene ring or anthracene ring is preferred.
W ² includes a single bond, an alkylene group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a norbornene ring, an adamantane ring, a benzene ring, a naphthalene ring, and a tetrahydronaphthalene ring. , A fluorene ring or an anthracene ring is preferred. Among them, a single bond, an alkylene group having 1 to 5 carbon atoms, cyclohexane, because of the ease of synthesis and the quickening of the residual charge accumulated by direct current voltage after exposure to light irradiation for a long time. A ring or a benzene ring is preferred.

（Ｚは炭素数１〜５のアルキル基を示す。）W ³ is preferably a single bond, —O—, —COO—, —OCO—, or —O (CH ₂ ) _m — (m represents an integer of 1 to 5). More preferable is a single bond, —O—, —OCO— or —O (CH ₂ ) _m — (m is 1 to 5) from the viewpoint of ease of synthesis.
W ⁴ represents a nitrogen-containing aromatic heterocycle and contains at least one structure selected from the group consisting of the following formula [a], formula [b] and formula [c].

(Z represents an alkyl group having 1 to 5 carbon atoms.)

More specifically, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring, pyridazine ring, pyrazoline ring , Triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, cinnoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring and acridine ring be able to. Among these, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, or a benzimidazole ring is preferable. More preferable is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring or a pyrimidine ring from the viewpoint that relaxation of residual charges accumulated by direct current voltage after being exposed to light irradiation for a long time is accelerated. Particularly preferred is an imidazole ring or a pyridine ring. Further, W ³ in Formula [2] is preferably bonded to a substituent that is not adjacent to Formula [a], Formula [b], and Formula [c] included in W ⁴ .
Tables 1 to 31 show preferable combinations of W ¹ , W ² , W ³ , and W ⁴ .

  Among them, (a-43) to (a-49), (a-57) to (a-63), (a-218) to (a-224), (a-232) to (a-238) , (A-323) to (a-329), (a-337) to (a-343), (a-428) to (a-434) or (a-442) to (a-448) Is preferred. More preferably, (a-44), (a-45), (a-58) or (A-59) combination.

Ｗは、前記式［２］の構造を示す。Ｗ^１、Ｗ^２、Ｗ^３、及びＷ^４の詳細、及び好ましい組み合せは、前記式［２］に記載される通りである。ｐ１は、１〜４の整数を示す。なかでも、合成の容易さの点から１が好ましい。As the specific diamine (2), it is particularly preferable to use a diamine of the following formula [2a].

W represents the structure of the formula [2]. Details and preferred combinations of W ¹ , W ² , W ³ , and W ⁴ are as described in the above formula [2]. p1 represents an integer of 1 to 4. Among these, 1 is preferable from the viewpoint of ease of synthesis.

From the above points, the use ratio of the specific diamine (2) is preferably the following use ratio. In a specific polymer (A), 1-60 mol% is preferable with respect to the whole diamine component. More preferred is 5 to 50 mol%, and particularly preferred is 10 to 50 mol%. In a specific polymer (B), 5-100 mol% is preferable with respect to the whole diamine component. More preferred is 10 to 95 mol%, and particularly preferred is 15 to 95 mol%. In the specific polymer (C), 0 to 20 mol% is preferable. More preferred is 0 to 10 mol%, and particularly preferred is 0 mol%.
Moreover, specific diamine (2) is 1 type or according to characteristics, such as the solubility to the solvent of a polyimide-type polymer, the liquid crystal aligning property at the time of setting it as a liquid crystal aligning film, and the optical characteristic of a liquid crystal display element. Two or more kinds can be mixed and used.

<Specific diamine (3)>
The specific diamine (3) in the present invention has at least one substituent selected from the group consisting of a carboxy group (COOH group) and a hydroxy group (OH group).

Ｙは、下記式［３−１］又は式［３−２］の構造を示す。
ｍ１は、１〜４の整数を示す。

ａは、０〜４の整数を示す。なかでも、原料の入手性や合成の容易さの点から、０又は１の整数が好ましい。Specifically, it is preferable to use a diamine of the following formula [3a].

Y represents the structure of the following formula [3-1] or [3-2].
m1 shows the integer of 1-4.

a represents an integer of 0 to 4. Especially, the integer of 0 or 1 is preferable from the point of the availability of a raw material or the ease of a synthesis | combination.

In formula [3-2], b represents an integer of 0 to 4. Especially, the integer of 0 or 1 is preferable from the point of the availability of a raw material or the ease of a synthesis | combination.
More specifically, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 2,4-diaminobenzoic acid 2,5-diaminobenzoic acid or 3,5-diaminobenzoic acid.
Among these, 2,4-diaminophenol, 3,5 is preferable because it suppresses a decrease in the voltage holding ratio after being exposed to light irradiation for a long time and accelerates the relaxation of residual charges accumulated by a DC voltage. -Diaminophenol, 3,5-diaminobenzyl alcohol or 3,5-diaminobenzoic acid are preferred.

From the above point, the use ratio of the specific diamine (3) is preferably the following use ratio. In a specific polymer (A), 0-20 mol% is preferable with respect to the whole diamine component. More preferred is 0 to 10 mol%, and particularly preferred is 0 mol%. In a specific polymer (B), 0-20 mol% is preferable with respect to the whole diamine component. More preferred is 0 to 10 mol%, and particularly preferred is 0 mol%. In a specific polymer (C), 40-100 mol% is preferable. More preferred is 50 to 100 mol%, and particularly preferred is 60 to 100 mol%.
Moreover, specific diamine (3) is 1 type or depending on characteristics, such as the solubility to the solvent of a polyimide-type polymer, the liquid crystal aligning property at the time of setting it as a liquid crystal aligning film, and the optical characteristic of a liquid crystal display element. Two or more kinds can be mixed and used.

（Ｒ^１は４価の有機基を示す。Ｒ^２は２価の有機基を示す。Ａ^１及びＡ^２はそれぞれ独立して、水素原子又は炭素数１〜８のアルキル基を示す。Ａ^３及びＡ^４はそれぞれ独立して、水素原子、炭素数１〜５のアルキル基又はアセチル基を示す。ｎＡは正の整数を示す。）<Specific polymer (A) to specific polymer (C)>
The specific polymers (A), (B) and (C) in the present invention mean the components (A), (B) and (C), respectively, and are polyimide precursors or polyimides (collectively polyimides). Also referred to as a polymer). They are preferably a polyimide precursor or polyimide obtained by reacting a diamine component and a tetracarboxylic acid component.
The polyimide precursor has a structure of the following formula [A].

(R ¹ represents a tetravalent organic group. R ² represents a divalent organic group. A ¹ and A ² each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. A ³ And A ⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an acetyl group, and nA represents a positive integer.)

  Examples of the diamine component include diamines having two primary or secondary amino groups in the molecule. Examples of the tetracarboxylic acid component include tetracarboxylic acid compounds, tetracarboxylic dianhydrides, tetracarboxylic acid dihalide compounds, tetracarboxylic acid dialkyl ester compounds, and tetracarboxylic acid dialkyl ester dihalide compounds.

（Ｒ^１及びＲ^２は、式［Ａ］で定義したものと同義である。）The polyimide-based polymer is obtained by using the tetracarboxylic dianhydride represented by the following formula [B] and the diamine represented by the following formula [C] as raw materials. Polyamic acid composed of a structural formula of repeating units or polyimide obtained by imidizing the polyamic acid is preferable. Especially, it is preferable that it is a polyimide from the point of the physical and chemical stability of a liquid crystal aligning film.

(R ¹ and R ² have the same meaning as defined in formula [A].)

（Ｒ^１、Ｒ^２及びｎＡは、前記式［Ａ］で定義したものと同義である。）
また、通常の合成手法で、上記で得られた式［Ｄ］の重合体に、式［Ａ］中のＡ^１及びＡ^２の炭素数１〜８のアルキル基、及び式［Ａ］中のＡ^３及びＡ^４の炭素数１〜５のアルキル基又はアセチル基を導入することもできる。

(R ¹ , R ² and nA are as defined in the formula [A].)
Further, in the polymer of the formula [D] obtained above by a general synthesis method, the alkyl group having 1 to 8 carbon atoms of A ¹ and A ^{2 in} the formula [A], and the polymer in the formula [A] It is also possible to introduce an alkyl group having 1 to 5 carbon atoms or an acetyl group of A ³ and A ⁴ .

For the specific polymers (A), (B) and (C) in the present invention, other diamines (also referred to as other diamines) may be used in addition to the specific diamines as long as the effects of the present invention are not impaired. it can.
Specifically, the diamine shown by the following formula [D1]-a formula [D6] is mentioned.

更に、国際公開公報ＷＯ２０１３／１２５５９５（２０１３．８．２９公開）の１９頁〜２３頁に記載されるその他のジアミン、同公報の２３頁〜２４頁に記載される式［ＤＡ１］〜式［ＤＡ１２］及び式［ＤＡ１５］〜式［ＤＡ２０］で示されるジアミン、及び同公報の２６頁に記載される式［ＤＡ２７］及び式［ＤＡ２８］で示されるジアミンが挙げられる。

Furthermore, other diamines described on pages 19 to 23 of International Publication No. WO2013 / 125595 (published on 2013.8.29), formulas [DA1] to [DA12] described on pages 23 to 24 of the publication. And diamines represented by formula [DA15] to [DA20], and diamines represented by formula [DA27] and [DA28] described on page 26 of the publication.

Other diamines may be used for the diamine component of any one of the specific polymers (A), (B) and (C). It can be used for the diamine component of the coalescence.
In addition, other diamines may be used alone or in combination of two or more depending on the solubility of the polyimide polymer in the solvent, the liquid crystal alignment when the liquid crystal alignment film is formed, and the optical characteristics of the liquid crystal display element. Can be used in combination.

Ｚは、前記式［４ａ］〜式［４ｋ］の構造からなる群から選ばれる少なくとも１種の構造を示す。Ｚは、合成の容易さやポリマーを製造する際の重合反応性のし易さの点から、式［４ａ］、式［４ｃ］、式［４ｄ］、式［４ｅ］、式［４ｆ］、式［４ｇ］又は式［４ｋ］が好ましい。より好ましいのは、式［４ａ］、式［４ｅ］、式［４ｆ］、式［４ｇ］又は式［４ｋ］である。特に好ましいのは、式［４ｅ］、式［４ｆ］、式［４ｇ］又は式［４ｋ］である。The tetracarboxylic acid component in at least one of the specific polymers (A), (B), and (C) includes a tetracarboxylic dianhydride represented by the following formula [4] (also referred to as a specific tetracarboxylic acid component). Is preferably used. More preferably, a specific tetracarboxylic acid component is used for all the specific polymers.

Z represents at least one structure selected from the group consisting of the structures of the formulas [4a] to [4k]. Z represents the formula [4a], the formula [4c], the formula [4d], the formula [4e], the formula [4f], the formula from the viewpoint of the ease of synthesis and the ease of polymerization reactivity when producing the polymer. [4g] or formula [4k] is preferred. More preferable is the formula [4a], the formula [4e], the formula [4f], the formula [4g], or the formula [4k]. Particularly preferable is the formula [4e], the formula [4f], the formula [4g], or the formula [4k].

The use ratio of the specific tetracarboxylic acid component is preferably 1 mol% or more with respect to the total tetracarboxylic acid component. More preferably, it is 5 mol% or less. Particularly preferred is 10 mol% or more, and most preferred is 10 to 90 mol% from the viewpoint of suppressing a decrease in voltage holding ratio after being exposed to light irradiation for a long time.
Moreover, when using the tetracarboxylic-acid component of the structure of said Formula [4e], Formula [4f], Formula [4g], or Formula [4k], the usage-amount shall be 20 mol% or more of the whole tetracarboxylic-acid component. Thus, a desired effect can be obtained. Preferably, it is 30 mol% or more. Further, all of the tetracarboxylic acid component may be a tetracarboxylic acid component having a structure of the formula [4e], the formula [4f], the formula [4g], or the formula [4k].

In all the specific polymers, other tetracarboxylic acid components other than the specific tetracarboxylic acid component can be used as long as the effects of the present invention are not impaired.
Specific examples include other tetracarboxylic acid components described on pages 27 to 28 of International Publication No. WO2013 / 125595 (2013.8.29 publication). Moreover, the specific tetracarboxylic acid component and other tetracarboxylic acid components can be used alone or in combination of two or more according to the respective characteristics.

The specific polymer (A) is a polyimide precursor obtained by a reaction between a diamine component containing the specific diamine (1) and the specific diamine (2) and a tetracarboxylic acid component or a polyimide obtained by imidizing the polyimide precursor. is there.
In that case, the use ratio of specific diamine (1) and specific diamine is as follows. That is, 10-70 mol% of specific diamine (1) is preferable with respect to the whole diamine component. More preferred is 15 to 70 mol%, and particularly preferred is 20 to 60 mol%. Moreover, 1-60 mol% of specific diamine (2) is preferable with respect to the whole diamine component. More preferred is 5 to 50 mol%, and particularly preferred is 10 to 50 mol%. In addition, in the specific diamine (3), the specific diamine (3) is preferably 0 to 20 mol% with respect to the entire diamine component, because liquid crystal alignment unevenness generated by the ODF method can be reduced. More preferably, it is 0-10 mol%, and especially preferable is 0 mol%, ie, not using specific diamine (3).

The specific polymer (B) is a polyimide precursor obtained by a reaction between a diamine component containing the specific diamine (2) and a tetracarboxylic acid component or a polyimide obtained by imidizing the polyimide precursor. In that case, the usage-amount of specific diamine (2) is as follows. That is, 5-100 mol% of specific diamine (2) is preferable with respect to the whole diamine component. More preferred is 10 to 95 mol%, and particularly preferred is 15 to 95 mol%. Moreover, in specific diamine (1), 0-40 mol% is preferable with respect to the whole diamine component. More preferred is 0 to 30 mol%, and particularly preferred is 0 to 25 mol%.
However, the usage ratio (mol%) of the specific diamine (1) in the specific polymer (B) to the entire diamine component is 1.0% of the usage ratio (mol%) of the specific diamine (1) in the specific polymer (A). When used, the use ratio (mol%) is such that the ratio is less than 1.0. At that time, when the ratio is 0, that is, when the specific diamine (1) is not used for the diamine component of the specific polymer (B), the voltage holding ratio after being exposed to light irradiation for a long time. This is preferable in that the decrease of the residual charge is suppressed and the relaxation of the residual charge accumulated by the DC voltage is accelerated. Moreover, when using specific diamine (1) for a specific polymer (B), the said ratio has preferable 0.01-0.9. More preferred is 0.01 to 0.8, and particularly preferred is 0.05 to 0.7.
In addition, in specific diamine (3), 0-20 mol% is preferable with respect to the whole diamine component. More preferably, it is 0 to 10 mol%, and particularly preferable is 0 mol%, that is, the specific diamine is added to the diamine component of the specific polymer (B) from the viewpoint that liquid crystal alignment unevenness generated by the ODF method can be reduced. (3) is not used.

The specific polymer (C) is a polyimide precursor obtained by a reaction of a diamine component containing the specific diamine (3) and a tetracarboxylic acid component or a polyimide obtained by imidizing the polyimide precursor. In that case, the usage-amount of specific diamine (3) is as follows. That is, 40-100 mol% of specific diamine (3) is preferable with respect to the whole diamine component. More preferred is 50 to 100 mol%, and particularly preferred is 60 to 100 mol%. Moreover, in specific diamine (1), it is preferable that it is 0-20 mol% with respect to the whole diamine component. More preferably, it is 0-10 mol%. However, the usage ratio (mol%) of the specific diamine (1) in the specific polymer (C) to the entire diamine component is 1.0% of the usage ratio (mol%) of the specific diamine (1) in the specific polymer (A). When used, the use ratio (mol%) is such that the ratio is less than 1.0. At that time, when the ratio is 0, that is, when the specific diamine (1) is not used for the diamine component of the specific polymer (C), the voltage holding ratio after being exposed to light irradiation for a long time. This is preferable in that the decrease of the residual charge is suppressed and the relaxation of the residual charge accumulated by the DC voltage is accelerated. Moreover, when using specific diamine (1) for specific polymer (C), the said ratio has preferable 0.01-0.4. More preferred is 0.01 to 0.3, and particularly preferred is 0.01 to 0.2.
Furthermore, 0-20 mol% of specific diamine (3) is preferable with respect to the whole diamine component. More preferably, it is 0 to 10 mol%, and particularly preferable is that the decrease in the voltage holding ratio after being exposed to light irradiation for a long time is suppressed, and the residual charge accumulated by the DC voltage is alleviated. From the point of speed, it is 0 mol%, that is, the specific diamine (3) is not used for the diamine component of the specific polymer (C).

  In the present invention, the method for producing all the specific polymers, that is, these polyimide polymers is not particularly limited. Usually, it is obtained by reacting a diamine component and a tetracarboxylic acid component. Generally, by reacting at least one tetracarboxylic acid component selected from the group consisting of tetracarboxylic dianhydride and its derivative, a diamine component consisting of one or more diamines, The method of obtaining a polyamic acid is mentioned. Specifically, tetracarboxylic dianhydride and primary or secondary diamine are polycondensed to obtain polyamic acid, tetracarboxylic acid and primary or secondary diamine are subjected to dehydration polycondensation reaction. A method of obtaining a polyamic acid or a method of obtaining a polyamic acid by reacting a tetracarboxylic acid dihalide with a primary or secondary diamine is used.

To obtain the polyamic acid alkyl ester, a method of polycondensing a tetracarboxylic acid obtained by dialkyl esterifying a carboxylic acid group and a primary or secondary diamine, a tetracarboxylic acid dihalide obtained by dialkyl esterifying a carboxylic acid group, and a primary Alternatively, a method of reacting with a secondary diamine or a method of converting a carboxy group of a polyamic acid into an ester is used.
In order to obtain polyimide, a method is used in which the polyamic acid or polyamic acid alkyl ester is cyclized to form polyimide.
The reaction between the diamine component and the tetracarboxylic acid component is usually performed in an organic solvent with the diamine component and the tetracarboxylic acid component. The organic solvent used at that time is not particularly limited as long as the produced polyimide precursor is dissolved. Although the specific example of the organic solvent used for reaction below is given, it is not limited to these examples.

  For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide or 1,3-dimethyl-imidazolidinone Can be mentioned. When the solvent solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or a solvent represented by the following formula [D-1] to formula [D-3] Can be used.

（Ｄ^１は炭素数１〜３のアルキル基を示す。Ｄ^２は炭素数１〜３のアルキル基を示す。Ｄ^３は炭素数１〜４のアルキル基を示す。）
これらは単独で使用しても、混合して使用してもよい。更に、ポリイミド前駆体を溶解させない溶媒であっても、生成したポリイミド前駆体が析出しない範囲で、上記溶媒に混合して使用してもよい。また、有機溶媒中の水分は重合反応を阻害し、更には生成したポリイミド前駆体を加水分解させる原因となるので、有機溶媒は脱水乾燥させたものを用いることが好ましい。

(D ¹ represents an alkyl group having 1 to 3 carbon atoms, D ² represents an alkyl group having 1 to ³ carbon atoms, and D ³ represents an alkyl group having 1 to 4 carbon atoms.)
These may be used alone or in combination. Further, even a solvent that does not dissolve the polyimide precursor may be used by mixing with the above solvent as long as the generated polyimide precursor does not precipitate. Moreover, since the water | moisture content in an organic solvent inhibits a polymerization reaction and also causes the produced polyimide precursor to hydrolyze, it is preferable to use what dehydrated and dried the organic solvent.

When the diamine component and the tetracarboxylic acid component are reacted in an organic solvent, the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic acid component is added as it is, or dispersed in the organic solvent or Examples include a method of adding by dissolving, a method of adding a diamine component to a solution obtained by dispersing or dissolving a tetracarboxylic acid component in an organic solvent, and a method of adding a diamine component and a tetracarboxylic acid component alternately. Any of these methods may be used. Moreover, when making it react using multiple types of diamine component and tetracarboxylic acid component, respectively, you may make it react in the state mixed beforehand, you may make it react separately one by one, and it is further made to react individually. May be mixed and reacted to form a polymer. Although the polymerization temperature in that case can select the arbitrary temperature of -20 degreeC-150 degreeC, Preferably it is the range of -5 degreeC-100 degreeC. The reaction can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. It becomes. Therefore, it is preferably 1 to 50%, more preferably 5 to 30%. The initial stage of the polymerization reaction can be carried out at a high concentration, and then an organic solvent can be added.
In the polymerization reaction of the polyimide precursor, the ratio of the total number of moles of the diamine component and the total number of moles of the tetracarboxylic acid component is preferably 0.8 to 1.2. Similar to the normal polymerization reaction, the closer the molar ratio is to 1.0, the higher the molecular weight of the polyimide precursor produced.

  Polyimide is a polyimide obtained by ring closure of the polyimide precursor, and the ring closure rate (also referred to as imidation rate) of the amic acid group does not necessarily need to be 100%, and can be arbitrarily adjusted according to the application and purpose. can do. Especially, in this invention, it is preferable that all the specific polymers are the polyimides which imidated the polyimide precursor. It is preferable that the imidation ratio in that case is as follows. That is, the specific polymer (A) is preferably 50 to 90%. More preferred is 55 to 90%, and particularly preferred is 60 to 90%. The specific polymer (B) is preferably 50 to 95%. More preferred is 55 to 95%, and particularly preferred is 60 to 95%. The specific polymer (C) is preferably 50 to 90%. 60 to 90% is more preferable, and 60 to 80% is particularly preferable.

Examples of the method for imidizing the polyimide precursor include thermal imidization in which the polyimide precursor solution is heated as it is, or catalytic imidization in which a catalyst is added to the polyimide precursor solution. The temperature at which the polyimide precursor is thermally imidized in the solution is 100 ° C. to 400 ° C., preferably 120 ° C. to 250 ° C., and is preferably performed while removing water generated by the imidization reaction from the system.
The catalyst imidation of the polyimide precursor can be performed by adding a basic catalyst and an acid anhydride to the polyimide precursor solution and stirring at -20 to 250 ° C, preferably 0 to 180 ° C. The amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times of the amidic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol of the amido acid group. Is double. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Of these, pyridine is preferable because it has a basicity suitable for advancing the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Of these, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated. The imidation ratio by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature and reaction time.

  When recovering the produced polyimide precursor or polyimide from the polyimide precursor or polyimide reaction solution, the reaction solution may be poured into a solvent and precipitated. Examples of the solvent used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water. The polymer precipitated in the solvent can be recovered by filtration, and then dried at normal temperature or under reduced pressure at room temperature or by heating. Moreover, when the operation of re-dissolving the precipitated and recovered polymer in an organic solvent and re-precipitation and recovery is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of solvents selected from these because purification efficiency is further improved.

The molecular weight of the polyimide-based polymer is the weight average molecular weight measured by GPC (Gel Permeation Chromatography) when considering the strength of the liquid crystal alignment film obtained therefrom, the workability at the time of forming the liquid crystal alignment film, and the coating properties. It is preferably 5,000 to 1,000,000. Especially, 10,000-150,000 are preferable.
As described above, all the specific polymers in the present invention exhibit stable vertical stability even after being exposed to high temperature and light irradiation for a long time, and maintain voltage even after being exposed to light irradiation for a long time. It is preferable that it is the polyimide which carried out the catalyst imidation of the polyimide precursor mentioned above from the point which can suppress the fall of a rate. The imidation ratio at that time is preferably in the above-described range.

<Liquid crystal alignment agent>
The use ratio of the specific polymers (A), (B) and (C) in the liquid crystal aligning agent is 30 to 300 parts of the specific polymer (B) relative to 100 parts of the specific polymer (A). The polymer (C) is preferably 60 to 500 parts. More preferably, the specific polymer (B) is 50 to 250 parts, the specific polymer (C) is 100 to 350 parts, and particularly preferably, the specific polymer (B) is 50 to 200 parts. The specific polymer (C) is 100 to 300 parts.

All of the polymer components in the liquid crystal aligning agent may be specific polymers, or other polymers may be mixed. At that time, the content of the other polymer is preferably 0.5 to 15 parts with respect to 100 parts of all the specific polymers. More preferred is 1 to 10 parts. Examples of other polymers include cellulosic polymers, acrylic polymers, methacrylic polymers, polystyrenes, polyamides, and polysiloxanes.
As for the solvent in a liquid-crystal aligning agent, 70-99.9% of content of the solvent in a liquid-crystal aligning agent is preferable from the point that a uniform liquid crystal aligning film is formed by application | coating. This content can be appropriately changed depending on the film thickness of the target liquid crystal alignment film.

The solvent used for the liquid-crystal aligning agent of this invention will not be specifically limited if it is a solvent (it is also called a good solvent) which dissolves all the specific polymers. Although the specific example of a good solvent is given to the following, it is not limited to these.
For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone , Cyclohexanone, cyclopentanone or 4-hydroxy-4-methyl-2-pentanone.
Of these, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone is preferably used.

Furthermore, when the solubility of the specific polymer in the solvent is high, it is preferable to use the solvent of the formula [D-1] to the formula [D-3].
The good solvent in the liquid crystal aligning agent is preferably 10 to 100% of the total solvent contained in the liquid crystal aligning agent. More preferably, it is 20 to 90%. Particularly preferred is 30 to 80%.
As long as the effects of the present invention are not impaired, a solvent (also referred to as a poor solvent) that improves the coating properties and surface smoothness of the liquid crystal alignment film when the liquid crystal alignment treatment agent is applied is used as the liquid crystal alignment treatment agent. it can. Although the specific example of a poor solvent is given to the following, it is not limited to these.

  Specifically, the poor solvent described in pages 35 to 37 of International Publication No. WO2013 / 125595 (published 2013.8.29) can be mentioned.

Among them, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, or the above formula [D-1] to formula [D -3] is preferably used.
These poor solvents are preferably 1 to 70% of the total solvent contained in the liquid crystal aligning agent. More preferably, it is 1 to 60%. Particularly preferred is 5 to 60%.

  As long as the effects of the present invention are not impaired, the liquid crystal aligning agent includes a crosslinkable compound selected from the group consisting of an epoxy group, an isocyanate group, an oxetane group and a cyclocarbonate group, a hydroxy group, a hydroxyalkyl group and a lower alkoxyalkyl group. It is preferable to introduce a crosslinkable compound selected from the group consisting of the above or a crosslinkable compound having a polymerizable unsaturated bond group (also collectively referred to as a specific crosslinkable compound). In that case, it is necessary to have two or more of these groups in the compound.

  As an example of the crosslinkable compound having an epoxy group or an isocyanate group, specifically, an epoxy group or an isocyanate group described on pages 37 to 38 of International Publication No. WO2013 / 125595 (published 2013.8.29) is used. The crosslinkable compound which has.

  Specific examples of the crosslinkable compound having an oxetane group include crosslinkable compounds represented by the formulas [4a] to [4k] described on pages 58 to 59 of International Publication WO2011 / 132751.

  Specific examples of the crosslinkable compound having a cyclocarbonate group include the crosslinkability represented by the formulas [5-1] to [5-42] described on pages 76 to 82 of International Publication WO2012 / 014898. Compounds.

  As the crosslinkable compound having at least one group selected from the group consisting of a hydroxy group, a hydroxyalkyl group and a lower alkoxyalkyl group, specifically, International Publication No. 2013/125595 (published 2013.8.29) Melamine derivatives or benzoguanamine derivatives described on pages 39 to 40, and formulas [6-1] to formulas published on pages 62 to 66 of International Publication WO2011 / 132751 (published 2011.10.20) And a crosslinkable compound represented by [6-48].

  Specific examples of the crosslinkable compound having a polymerizable unsaturated bond include crosslinks having a polymerizable unsaturated bond described on pages 40 to 41 of International Publication WO2013 / 125595 (published 2013.8.29). Compound.

The content of the specific crosslinkable compound in the liquid crystal aligning agent is preferably 0.1 to 100 parts with respect to 100 parts of all polymer components. More preferably, the amount is 0.1 to 50 parts because the crosslinking reaction proceeds and the desired effect is exhibited. Particularly preferred is 1 to 30 parts.
In the liquid crystal alignment treatment agent of the present invention, in order to promote charge transfer in the liquid crystal alignment film and promote charge release of the element, pages 69 to 73 of International Publication No. WO2011 / 132751 (2011.10.27 published). The nitrogen-containing heterocyclic amine of the formula [M1] to the formula [M156] described in the above can be added. The amine may be added directly to the liquid crystal aligning agent, but it is preferable to add the amine after forming a solution with a suitable solvent in a concentration of 0.1 to 10%, preferably 1 to 7%. The solvent is not particularly limited as long as it is an organic solvent that dissolves the specific polymer.

As long as the effects of the present invention are not impaired, a compound that improves the uniformity of the thickness of the liquid crystal alignment film and the surface smoothness when the liquid crystal alignment treatment agent is applied can be used as the liquid crystal alignment treatment agent. Furthermore, a compound that improves the adhesion between the liquid crystal alignment film and the substrate can be used.
Examples of the compound that improves the film thickness uniformity and surface smoothness of the liquid crystal alignment film include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. Specific examples include surfactants described on pages 42 to 43 of International Publication No. WO2013 / 125595 (published 2013.8.29).
The amount of these surfactants used is preferably 0.01 to 2 parts by weight, more preferably 0.01 to 1 part by weight with respect to 100 parts by weight of all polymer components contained in the liquid crystal alignment treatment agent. Part.

  Specific examples of the compound that improves the adhesion between the liquid crystal alignment film and the substrate include a functional silane-containing compound and an epoxy group-containing compound. Specific examples include compounds described on pages 43 to 44 of International Publication No. WO2013 / 125595 (published 2013.8.29).

The use ratio of the compound to be in close contact with these substrates is preferably 0.1 to 30 parts, more preferably 1 to 20 with respect to 100 parts of all polymer components contained in the liquid crystal aligning agent. Part. If it is less than 0.1 part, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts, the storage stability of the liquid crystal aligning agent may be deteriorated.
In addition to the compounds other than the above, the liquid crystal aligning agent includes a dielectric or conductive material for changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal alignment film as long as the effects of the present invention are not impaired. Substances may be added.

<Liquid crystal alignment film and liquid crystal display element>
The liquid crystal alignment treatment agent of the present invention can be used as a liquid crystal alignment film by applying and baking on a substrate and then performing alignment treatment by rubbing treatment, light irradiation or the like. Further, in the case of vertical alignment use etc., it can be used as a liquid crystal alignment film without alignment treatment. The substrate used at this time is not particularly limited as long as it is a highly transparent substrate. In addition to a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate can also be used. From the viewpoint of simplifying the process, it is preferable to use a substrate on which an ITO electrode or the like for driving the liquid crystal is formed. In the reflective liquid crystal display element, an opaque substrate such as a silicon wafer can be used as long as only one substrate is used, and a material that reflects light such as aluminum can be used as an electrode in this case.

A method for applying the liquid crystal alignment treatment agent is not particularly limited, but industrially, a method of screen printing, offset printing, flexographic printing, an inkjet method, or the like is generally used. Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method, or a spray method, and these may be used depending on the purpose.
After applying the liquid crystal alignment treatment agent on the substrate, it is preferably 30 to 300 ° C., depending on the solvent used for the liquid crystal alignment treatment agent, by a heating means such as a hot plate, a thermal circulation oven or an IR (infrared) oven. Can evaporate the solvent at a temperature of 30 to 250 ° C. to obtain a liquid crystal alignment film. If the thickness of the liquid crystal alignment film after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. Is 10 to 100 nm. When the liquid crystal is horizontally aligned or tilted, the fired liquid crystal alignment film is treated by rubbing or irradiation with polarized ultraviolet rays.

The liquid crystal display element of the present invention is a liquid crystal display element obtained by obtaining a substrate with a liquid crystal alignment film from the liquid crystal alignment treatment agent of the present invention by the method described above, and then preparing a liquid crystal cell by a known method.
As a method for producing a liquid crystal cell, for example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, spacers are dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is on the inside, There is a method of pasting the other substrate and injecting liquid crystal under reduced pressure, or a method in which the substrate is pasted after the liquid crystal is dropped on the liquid crystal alignment film surface on which spacers are dispersed (ODF method), etc. It can be illustrated.

The liquid-crystal aligning agent of this invention has a liquid-crystal layer between a pair of board | substrates provided with the electrode, The liquid crystal containing the polymeric compound superposed | polymerized by at least one of an active energy ray and a heat | fever between a pair of board | substrates. The composition is also preferably used for a liquid crystal display device produced through a step of polymerizing a polymerizable compound by at least one of irradiation with active energy rays and heating while applying a voltage between electrodes. Here, ultraviolet rays are suitable as the active energy ray. The ultraviolet light has a wavelength of 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C. Moreover, you may perform an ultraviolet-ray and a heating simultaneously.
The liquid crystal display element controls the pretilt of liquid crystal molecules by the PSA method. In the PSA method, a small amount of a photopolymerizable compound, for example, a photopolymerizable monomer is mixed in a liquid crystal material, and after assembling a liquid crystal cell, a predetermined voltage is applied to the liquid crystal layer and an ultraviolet ray is applied to the photopolymerizable compound. The pretilt of the liquid crystal molecules is controlled by the produced polymer. Since the alignment state of the liquid crystal molecules when the polymer is formed is stored even after the voltage is removed, the pretilt of the liquid crystal molecules can be adjusted by controlling the electric field formed in the liquid crystal layer. The PSA method does not require a rubbing process and is suitable for forming a vertical alignment type liquid crystal layer in which it is difficult to control the pretilt by the rubbing process. That is, in the liquid crystal display element of the present invention, after obtaining a substrate with a liquid crystal alignment film from the liquid crystal alignment treatment agent by the above-described method, a liquid crystal cell is prepared, and a polymerizable compound is polymerized by at least one of ultraviolet irradiation and heating. Thus, the alignment of liquid crystal molecules can be controlled.

  An example of production of a PSA type liquid crystal cell is as follows. That is, a liquid crystal cell is manufactured by the manufacturing method described above. In the liquid crystal at that time, a polymerizable compound that is polymerized by heat or ultraviolet irradiation is mixed. Examples of the polymerizable compound include compounds having at least one polymerizable unsaturated group such as an acrylate group or a methacrylate group in the molecule. In that case, it is preferable that a polymeric compound is 0.01-10 parts with respect to 100 parts of a liquid-crystal component, More preferably, it is 0.1-5 parts. When the polymerizable compound is less than 0.01 part, the polymerizable compound is not polymerized and the alignment of the liquid crystal cannot be controlled. When the polymerizable compound is more than 10 parts, the amount of unreacted polymerizable compound increases and the liquid crystal display element is burned. Characteristics are degraded. After the liquid crystal cell is produced, the polymerizable compound is polymerized by irradiating heat or ultraviolet rays while applying an AC or DC voltage to the liquid crystal cell. Thereby, the alignment of the liquid crystal molecules can be controlled.

  Furthermore, the liquid crystal aligning agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and a polymerizable group that is polymerized by at least one of active energy rays and heat between the pair of substrates. It can also be used for a liquid crystal display element manufactured through a process of disposing a liquid crystal alignment film containing and applying a voltage between the electrodes, that is, the SC-PVA mode. Here, ultraviolet rays are suitable as the active energy ray. As an ultraviolet-ray, a wavelength is 300-400 nm, More preferably, it is 310-360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120 ° C, more preferably 60 to 80 ° C. Moreover, you may perform an ultraviolet-ray and a heating simultaneously.

In order to obtain a liquid crystal alignment film containing a polymerizable group that polymerizes from at least one of active energy rays and heat, a method of adding a compound containing this polymerizable group to a liquid crystal aligning agent, A method using a coalescing component may be mentioned.
An example of the production of the SC-PVA mode liquid crystal cell is as follows. That is, a liquid crystal cell is manufactured by the manufacturing method described above. Thereafter, the orientation of the liquid crystal molecules can be controlled by irradiating heat or ultraviolet rays while applying an AC or DC voltage to the liquid crystal cell.

The present invention will be described in more detail with reference to the following examples, but the present invention should not be construed as being limited thereto. Abbreviations used below are as follows.
(Specific diamine (1))
A1: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene A2: 1,3-diamino-5- [4- (trans-4-n-heptylcyclo) Hexyl) phenoxymethyl] benzene A3: 1,3-diamino-4- {4- [trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxy} benzene A4: the following formula [A4 ] Of diamine

（特定ジアミン（３））

(Specific diamine (2))

(Specific diamine (3))

(Other diamines)
D1: p-phenylenediamine, D2: m-phenylenediamine D3: 1,3-diamino-4-octadecyloxybenzene

(Specific tetracarboxylic dianhydride)
E1: 1,2,3,4-cyclobutanetetracarboxylic dianhydride E2: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride E3: the following formula [E3] E4: tetracarboxylic dianhydride of the following formula [E4] E5: tetracarboxylic dianhydride of the following formula [E5]

(Crosslinkable compound)

(solvent)
NMP: N-methyl-2-pyrrolidone, NEP: N-ethyl-2-pyrrolidone γ-BL: γ-butyrolactone, BCS: ethylene glycol monobutyl ether, PB: propylene glycol monobutyl ether, DME: dipropylene glycol dimethyl ether, DPM: Dipropylene glycol monomethyl ether "Molecular weight measurement of polyimide polymer"
It measured as follows using the normal temperature gel permeation chromatography (GPC) apparatus (GPC-101, the Showa Denko company make) and column (KD-803, KD-805, the Shodex company make).
Column temperature: 50 ° C
Eluent: N, N′-dimethylformamide (as additives, lithium bromide-hydrate (LiBr · H ₂ O) is 30 mmol / L (liter), phosphoric acid / anhydrous crystal (o-phosphoric acid) is 30 mmol / L, 10 ml / L of tetrahydrofuran (THF))
Flow rate: 1.0 ml / min Standard sample for preparing calibration curve: TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000 and 30,000, manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight: about 12 , 4,000, 4,000 and 1,000, manufactured by Polymer Laboratories).

"Measurement of imidization rate of polyimide polymer"
Add 20 mg of polyimide powder to an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, φ5 (manufactured by Kusano Kagaku)) and mix with deuterated dimethyl sulfoxide (DMSO-d6, 0.05% TMS (tetramethylsilane)) Product) (0.53 ml) was added and completely dissolved by sonication. This solution was measured for proton NMR at 500 MHz with an NMR measuring machine (JNW-ECA500, manufactured by JEOL Datum). The imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of amic acid appearing in the vicinity of 9.5 ppm to 10.0 ppm. It calculated | required by the following formula | equation using the integrated value.
Imidation ratio (%) = (1−α · x / y) × 100
(X is the accumulated proton peak value derived from NH group of amic acid, y is the accumulated peak value of reference proton, α is the reference proton for one NH group proton of amic acid in the case of polyamic acid (imidation rate is 0%) The number ratio.
"Synthesis of polyimide polymers"

<Synthesis Example 1>
E2 (2.17 g, 8.67 mmol), A1 (2.67 g, 7.02 mmol), B1 (1.28 g, 5.28 mmol) and D1 (0.57 g, 5.27 mmol) were added to NMP (16.8 g). After mixing at 80 ° C. for 5 hours, E1 (1.70 g, 8.67 mmol) and NMP (8.39 g) were added and reacted at 40 ° C. for 6 hours to adjust the concentration (resin solid content concentration). A 25% polyamic acid solution was obtained in the following examples.
After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6%, acetic anhydride (4.50 g) and pyridine (3.30 g) were added as imidization catalysts, and the reaction was carried out at 80 ° C. for 4 hours. I let you. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (1). The imidation ratio of this polyimide was 80%, the number average molecular weight (Mn) was 17,400, and the weight average molecular weight (Mw) was 47,500.

<Synthesis Example 2>
E2 (0.89 g, 3.56 mmol), A3 (2.35 g, 5.43 mmol), B1 (1.75 g, 7.22 mmol) and D1 (0.59 g, 5.46 mmol) NMP (16.8 g) After mixing at 80 ° C. for 5 hours, E1 (2.80 g, 14.3 mmol) and NMP (8.38 g) were added and reacted at 40 ° C. for 6 hours. A solution was obtained.
After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6%, acetic anhydride (4.50 g) and pyridine (3.30 g) were added as an imidization catalyst, and 3.5% at 80 ° C. Reacted for hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (2). The imidation ratio of this polyimide was 75%, Mn was 16,100, and Mw was 44,400.

<Synthesis Example 3>
E2 (3.06 g, 12.2 mmol), A2 (2.61 g, 6.61 mmol), B1 (1.20 g, 4.95 mmol) and D1 (0.54 g, 4.99 mmol) NEP (16.4 g) After mixing at 80 ° C. for 5 hours, E1 (0.80 g, 4.08 mmol) and NEP (8.21 g) were added and reacted at 40 ° C. for 6 hours. A solution was obtained.
After adding NEP to the obtained polyamic acid solution (30.0 g) and diluting to 6%, acetic anhydride (4.50 g) and pyridine (3.30 g) were added as imidization catalysts, and the reaction was carried out at 80 ° C. for 3 hours. I let you. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (3). The imidation ratio of this polyimide was 70%, Mn was 17,800, and Mw was 47,600.

<Synthesis Example 4>
E2 (2.17 g, 8.67 mmol), A4 (2.16 g, 4.38 mmol), B1 (1.91 g, 7.88 mmol) and D1 (0.57 g, 5.27 mmol) to NMP (17.0 g) After mixing at 80 ° C. for 5 hours, E1 (1.70 g, 8.67 mmol) and NMP (8.52 g) were added and reacted at 40 ° C. for 6 hours. A solution was obtained.
After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6%, acetic anhydride (4.50 g) and pyridine (3.30 g) were added as an imidization catalyst, and 2.5% at 80 ° C. Reacted for hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (4). The imidation ratio of this polyimide was 65%, Mn was 15,300, and Mw was 42,100.

<Synthesis Example 5>
E3 (3.80 g, 17.0 mmol), A2 (2.03 g, 5.14 mmol), B1 (1.66 g, 6.85 mmol) and D2 (0.56 g, 5.18 mmol) NEP (24.2 g) And mixed at 40 ° C. for 8 hours to obtain a polyamic acid solution having a concentration of 25%.
After adding NEP to the obtained polyamic acid solution (30.0 g) and diluting to 6%, acetic anhydride (4.50 g) and pyridine (3.30 g) were added as imidization catalysts, and the reaction was carried out at 80 ° C. for 3 hours. I let you. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (5). The imidation ratio of this polyimide was 70%, Mn was 18,600, and Mw was 48,800.

<Synthesis Example 6>
E4 (2.60 g, 8.66 mmol), A2 (2.08 g, 5.27 mmol), B1 (1.70 g, 7.02 mmol) and D1 (0.57 g, 5.27 mmol) were added to NMP (17.3 g). After mixing at 80 ° C. for 5 hours, E1 (1.70 g, 8.67 mmol) and NMP (8.65 g) were added and reacted at 40 ° C. for 6 hours. A solution was obtained.
After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6%, acetic anhydride (4.50 g) and pyridine (3.30 g) were added as imidization catalysts, and the reaction was carried out at 80 ° C. for 4 hours. I let you. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (6). The imidation ratio of this polyimide was 80%, Mn was 16,300, and Mw was 45,400.

<Synthesis Example 7>
E2 (0.89 g, 3.56 mmol), A1 (2.75 g, 7.23 mmol), B1 (1.31 g, 5.41 mmol) and D2 (0.59 g, 5.46 mmol) NMP (16.7 g) After mixing at 80 ° C. for 5 hours, E1 (2.80 g, 14.3 mmol) and NMP (8.35 g) were added and reacted at 40 ° C. for 6 hours. A solution was obtained.
After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6%, acetic anhydride (4.50 g) and pyridine (3.30 g) were added as imidization catalysts, and the reaction was performed at 80 ° C. for 3 hours. I let you. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (7). The imidation ratio of this polyimide was 70%, Mn was 17,100, and Mw was 45,900.

<Synthesis Example 8>
E2 (3.06 g, 12.2 mmol), A1 (3.15 g, 8.28 mmol), B2 (0.64 g, 2.47 mmol) and D2 (0.63 g, 5.83 mmol) NEP (16.6 g) After mixing at 80 ° C. for 5 hours, E1 (0.80 g, 4.08 mmol) and NEP (8.28 g) were added and reacted at 40 ° C. for 6 hours. A solution was obtained.
After adding NEP to the obtained polyamic acid solution (30.0 g) and diluting to 6%, acetic anhydride (4.50 g) and pyridine (3.30 g) were added as imidization catalysts, and the reaction was carried out at 80 ° C. for 3 hours. I let you. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (8). The imidation ratio of this polyimide was 70%, Mn was 15,800, and Mw was 42,100.

<Synthesis Example 9>
E2 (0.89 g, 3.56 mmol), B1 (1.75 g, 7.22 mmol), D1 (0.59 g, 5.46 mmol) and D3 (2.04 g, 5.42 mmol) were added to NMP (16.2 g). After mixing at 80 ° C. for 5 hours, E1 (2.80 g, 14.3 mmol) and NMP (8.28 g) were added and reacted at 40 ° C. for 6 hours. A solution was obtained.
After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6%, acetic anhydride (4.50 g) and pyridine (3.30 g) were added as an imidization catalyst, and 3.5% at 80 ° C. Reacted for hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (9). The imidation ratio of this polyimide was 75%, Mn was 16,500, and Mw was 43,300.

<Synthesis Example 10>
E2 (0.89 g, 3.56 mmol), A1 (1.38 g, 3.63 mmol) and B1 (3.50 g, 14.4 mmol) were mixed in NMP (17.2 g) and reacted at 80 ° C. for 5 hours. After that, E1 (2.80 g, 14.3 mmol) and NMP (8.57 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution having a concentration of 25%.
After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6%, acetic anhydride (4.50 g) and pyridine (3.30 g) were added as imidization catalysts, and the reaction was carried out at 80 ° C. for 5 hours. I let you. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (10). The imidation ratio of this polyimide was 90%, Mn was 17,800, and Mw was 46,900.

<Synthesis Example 11>
E2 (0.96 g, 3.84 mmol), A1 (1.47 g, 3.86 mmol), B1 (1.88 g, 7.76 mmol) and D1 (0.84 g, 7.77 mmol) were added to NMP (16.3 g). After mixing at 80 ° C. for 5 hours, E1 (3.00 g, 15.3 mmol) and NMP (8.15 g) were added, and the mixture was reacted at 40 ° C. for 6 hours. A solution was obtained.
After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6%, acetic anhydride (4.50 g) and pyridine (3.30 g) were added as an imidization catalyst, and 3.5% at 80 ° C. Reacted for hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (11). The imidation ratio of this polyimide was 75%, Mn was 18,600, and Mw was 48,300.

<Synthesis Example 12>
E2 (2.30 g, 9.19 mmol), B1 (4.05 g, 16.7 mmol) and D2 (0.20 g, 1.85 mmol) were mixed in NMP (16.7 g) and reacted at 80 ° C. for 5 hours. After that, E1 (1.80 g, 9.18 mmol) and NMP (8.35 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution having a concentration of 25%.
After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6%, acetic anhydride (4.50 g) and pyridine (3.30 g) were added as an imidization catalyst, and 2.5% at 80 ° C. Reacted for hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (12). The imidation ratio of this polyimide was 65%, Mn was 22,100, and Mw was 53,400.

<Synthesis Example 13>
E2 (2.55 g, 10.2 mmol), A1 (1.57 g, 4.13 mmol), B1 (1.07 g, 4.13 mmol) and D2 (1.34 g, 12.4 mmol) NMP (17.1 g) After mixing at 80 ° C. for 5 hours, E1 (2.00 g, 10.2 mmol) and NMP (8.54 g) were added, and the mixture was reacted at 40 ° C. for 6 hours. A solution was obtained.
After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6%, acetic anhydride (4.50 g) and pyridine (3.30 g) were added as an imidization catalyst, and 3.5% at 80 ° C. Reacted for hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (13). The imidation ratio of this polyimide was 75%, Mn was 17,900, and Mw was 46,500.

<Synthesis Example 14>
E2 (2.81 g, 11.2 mmol) and C1 (3.46 g, 22.7 mmol) were mixed in NMP (16.9 g), reacted at 80 ° C. for 5 hours, and then E1 (2.20 g, 11 0.2 mmol) and NMP (8.46 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution having a concentration of 25%.
After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6%, acetic anhydride (4.50 g) and pyridine (3.30 g) were added as an imidization catalyst, and 3.5% at 80 ° C. Reacted for hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (14). The imidation ratio of this polyimide was 75%, Mn was 21,800, and Mw was 52,100.

<Synthesis Example 15>
E2 (2.81 g, 11.2 mmol), C1 (2.94 g, 19.3 mmol) and D2 (0.37 g, 3.42 mmol) were mixed in NMP (16.6 g) and reacted at 80 ° C. for 5 hours. After that, E1 (2.20 g, 11.2 mmol) and NMP (8.31 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution having a concentration of 25%.
After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6%, acetic anhydride (4.50 g) and pyridine (3.30 g) were added as imidization catalysts, and the reaction was performed at 80 ° C. for 3 hours. I let you. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (15). The imidation ratio of this polyimide was 70%, Mn was 23,200, and Mw was 54,200.

<Synthesis Example 16>
E5 (2.30 g, 10.8 mmol), C1 (2.84 g, 18.7 mmol) and D2 (0.36 g, 3.33 mmol) were mixed in NEP (16.4 g) and reacted at 80 ° C. for 5 hours. After that, E1 (2.30 g, 10.8 mmol) and NEP (8.21 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution having a concentration of 25%.
After adding NEP to the obtained polyamic acid solution (30.0 g) and diluting to 6%, acetic anhydride (4.50 g) and pyridine (3.30 g) were added as imidization catalysts, and the reaction was carried out at 80 ° C. for 3 hours. I let you. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (16). The imidation ratio of this polyimide was 70%, Mn was 20,500, and Mw was 51,800.

<Synthesis Example 17>
E2 (2.17 g, 8.67 mmol), A1 (2.67 g, 7.02 mmol), B1 (1.28 g, 5.28 mmol) and C1 (0.80 g, 5.26 mmol) NMP (17.2 g) After mixing at 80 ° C. for 5 hours, E1 (1.70 g, 8.67 mmol) and NMP (8.62 g) were added and reacted at 40 ° C. for 6 hours. A solution was obtained.
After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6%, acetic anhydride (4.50 g) and pyridine (3.30 g) were added as imidization catalysts, and the reaction was carried out at 80 ° C. for 4 hours. I let you. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (17). The imidation ratio of this polyimide was 80%, Mn was 16,300, and Mw was 46,300.
Tables 32 and 33 summarize the details of the polyimide-based polymer obtained in each synthesis example.

"Evaluation of inkjet coating properties of liquid crystal alignment treatment agents"
Using the liquid crystal aligning agent obtained in Example 3 and Example 8 which will be described later, the inkjet coating property was evaluated. Specifically, a substrate with an ITO (indium tin oxide) electrode (length: 100 mm) obtained by pressure-filtering these liquid crystal alignment treatment agents with a membrane filter having a pore diameter of 1 μm and washing with pure water and IPA (isopropyl alcohol). The coating was performed on an ITO surface having a width of 100 mm and a thickness of 0.7 mm under the conditions of a coating area of 70 × 70 mm, a nozzle pitch of 0.423 mm, a scan pitch of 0.5 mm, and a coating speed of 40 mm / second. At that time, HIS-200 (manufactured by Hitachi Plant Technology) was used as an inkjet coating machine. The time from application to temporary drying was 60 seconds, and the temporary drying was performed on a hot plate at 70 ° C. for 5 minutes.
The applicability was evaluated by visually observing the coating surface of the substrate with a liquid crystal alignment film obtained above. Specifically, the coating film surface was visually observed under a sodium lamp to confirm the presence or absence of pinholes. As a result, in any of the liquid crystal alignment films obtained in any of the examples, no pinhole was observed on the coating film surface, and a liquid crystal alignment film having excellent coating properties was obtained.

"Production of liquid crystal cell and evaluation of pretilt angle (normal cell)"
A liquid crystal cell was prepared and the pretilt angle was evaluated using the liquid crystal aligning agents obtained in Examples and Comparative Examples described later. Specifically, these liquid crystal aligning agents were pressure filtered through a membrane filter having a pore diameter of 1 μm, and washed with pure water and IPA (40 mm long × 30 mm wide, 0.7 mm thick). The ITO substrate is spin-coated on the ITO surface and heated at 100 ° C. for 5 minutes on a hot plate, and at 230 ° C. for 30 minutes in a heat-circulating clean oven. Got. In addition, the liquid crystal aligning agent of Example 3 and Example 8 produced a board | substrate on the conditions similar to said "evaluation of the inkjet applicability | paintability of a liquid crystal aligning agent", and then 230 in a heat circulation type clean oven A heat treatment was carried out at 30 ° C. for 30 minutes to obtain an ITO substrate with a liquid crystal alignment film having a film thickness of 100 nm.

Next, the coating surface of the substrate is rubbed with a rubbing apparatus having a roll diameter of 120 mm using a rayon cloth under the conditions of a roll rotation speed of 1000 rpm, a roll traveling speed of 50 mm / sec, and an indentation amount of 0.1 mm. did.
Thereafter, two substrates after the rubbing treatment were prepared, combined with a 6 μm spacer sandwiched with the coating surface on the inside, and the periphery was adhered with a sealing agent to produce an empty cell. MLC-6608 (manufactured by Merck Japan) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell.

Using the obtained liquid crystal cell, the pretilt angle was measured. Specifically, the measurement was performed with a liquid crystal cell after performing an isotropic treatment of liquid crystal (heat treatment at 95 ° C. for 5 minutes) and a liquid crystal cell after heat treatment (heat treatment at 120 ° C. for 5 hours).
Further, a liquid crystal cell produced under the same conditions as described above was subjected to isotropic treatment, and then the liquid crystal cell after irradiation with 10 J / cm ² of ultraviolet rays in terms of 365 nm was also measured. The pretilt angle was measured at room temperature using PAS-301 (manufactured by ELSICON). Furthermore, ultraviolet irradiation was performed using a desktop UV curing device (HCT3B28HEX-1) (manufactured by Senlite).
Evaluation is performed after heat treatment (also referred to after high temperature treatment) and after irradiation with ultraviolet rays (also referred to after ultraviolet irradiation) with respect to the pretilt angle after liquid crystal isotropic treatment (also referred to as initial). The smaller the change in the pretilt angle, the better the evaluation. Tables 37 to 39 show the values of the respective pretilt angles.

"Evaluation of liquid crystal alignment unevenness generated by ODF method"
The liquid crystal alignment unevenness generated by the ODF method was evaluated using the liquid crystal aligning agents obtained in Examples and Comparative Examples described later. Specifically, these liquid crystal aligning agents were pressure filtered through a membrane filter having a pore diameter of 1 μm and washed with pure water and IPA (100 mm long × 100 mm wide, 0.7 mm thick). The ITO substrate is spin-coated on the ITO surface and heated at 100 ° C. for 5 minutes on a hot plate, and at 230 ° C. for 30 minutes in a heat-circulating clean oven. Got. In addition, the liquid crystal aligning agent of Example 3 and Example 8 produced a board | substrate on the conditions similar to said "evaluation of the inkjet applicability | paintability of a liquid crystal aligning agent", and then 230 in a heat circulation type clean oven A heat treatment was carried out at 30 ° C. for 30 minutes to obtain an ITO substrate with a liquid crystal alignment film having a film thickness of 100 nm.

Next, the coating surface of the substrate is rubbed with a rubbing apparatus having a roll diameter of 120 mm using a rayon cloth under the conditions of a roll rotation speed of 1000 rpm, a roll traveling speed of 50 mm / sec, and an indentation amount of 0.1 mm. did.
Thereafter, two substrates, the substrate subjected to the rubbing treatment and the substrate not treated, were prepared, and a 6 μm spacer was sprayed on the coating surface of the substrate not treated. Thereafter, an ultraviolet curable sealant is drawn around the substrate, and nematic liquid crystal (MLC-6608, manufactured by Merck Japan Ltd.) is applied to the surface of the coating on the inner side of the sealant by the ODF method. (2 vertical points × 3 horizontal points, and the interval between each point was 10 mm in the vertical and horizontal directions), and the rubbed substrate was bonded to obtain a liquid crystal cell. Then, in order to cure the sealant, the liquid crystal cell was cut using a metal halide lamp with an illuminance of 60 mW, the wavelength of 310 nm or less was cut, and ultraviolet rays of 5 J / cm ² were converted in terms of 365 nm. A liquid crystal cell was obtained by heating at 120 ° C. for 60 minutes.
Using the obtained liquid crystal cell, liquid crystal dropping mark unevenness, that is, liquid crystal alignment unevenness was confirmed. Specifically, a voltage of AC (AC drive) 5 V is applied to the liquid crystal cell, and the presence or absence of liquid crystal alignment unevenness in the region where the liquid crystal is dropped is confirmed by visual observation using a polarizing plate and a backlight. did.
In this evaluation, in the above, the liquid crystal alignment unevenness was not observed, and this evaluation was excellent (good display in Tables 37 to 39).

"Evaluation of voltage holding ratio (normal cell)"
The voltage holding ratio was evaluated using a liquid crystal cell manufactured under the same conditions as those described above for “Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”. Specifically, a voltage of 1 V is applied to the liquid crystal cell obtained by the above method at a temperature of 80 ° C. for 60 μs, the voltage after 50 ms is measured, and the voltage holding ratio ( (Also referred to as VHR). The measurement was performed using a voltage holding ratio measuring device (VHR-1, manufactured by Toyo Technica Co., Ltd.) with settings of Voltage: ± 1 V, Pulse Width: 60 μs, and Flame Period: 50 ms.

Further, the liquid crystal cell whose voltage holding ratio was measured immediately after the liquid crystal cell was manufactured was irradiated with ultraviolet rays of 50 J / cm ^{2 in} terms of 365 nm using a desktop UV curing device (HCT3B28HEX-1, manufactured by Senlite). The voltage holding ratio was measured under the same conditions as described above.
In this evaluation, the value of the voltage holding ratio immediately after the production of the liquid crystal cell is high, and further, the value after the ultraviolet irradiation (also called after the ultraviolet irradiation) with respect to the value of the voltage holding ratio immediately after the production of the liquid crystal cell (also referred to as the initial). ), The smaller the decrease, the better the evaluation. In Table 40 to Table 42, the value of each VHR is shown.

"Evaluation of residual charge relaxation (normal cell)"
Evaluation of relaxation of residual charges was performed using a liquid crystal cell manufactured under the same conditions as those described above for “preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”. Specifically, a DC voltage of 10 V was applied to the liquid crystal cell for 30 minutes and short-circuited for 1 second, and then the potential generated in the liquid crystal cell was measured for 1800 seconds. Among them, the value of the residual charge after 50 seconds was used to evaluate the relaxation of the residual charge. In addition, the measurement used the 6254 type liquid crystal physical-property evaluation apparatus (Toyo Technica company make).
Furthermore, 30 J / cm ² of ultraviolet rays in terms of 365 nm were irradiated to the liquid crystal cell for which the residual charge measurement was completed immediately after the liquid crystal cell was manufactured, using a tabletop UV curing device (HCT3B28HEX-1, manufactured by Senlite). The residual charge was measured under the same conditions as described above.
In this evaluation, the smaller the value immediately after the production of the liquid crystal cell (also referred to as initial) and the value of the residual charge after ultraviolet irradiation (also referred to after ultraviolet irradiation), the better the evaluation. Tables 40 to 42 show the values of the residual charges.

"Production of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell)"
Using the liquid crystal aligning agent obtained in Example 3 and Example 9 to be described later, production of a liquid crystal cell and evaluation of liquid crystal alignment (PSA cell) were performed. Specifically, these liquid crystal aligning agents are pressure filtered through a membrane filter having a pore size of 1 μm, and washed with pure water and IPA, and an electrode with ITO with an ITO of 10 × 10 mm and a pattern spacing of 20 μm is attached to the center. Spin on each of the ITO surfaces of the substrate (40 mm long x 30 mm wide, 0.7 mm thick) and the electrode-attached substrate (40 mm long x 30 mm wide, 0.7 mm thick) with 10 x 40 mm ITO in the center. Coating was carried out on a hot plate at 100 ° C. for 5 minutes and in a heat circulation clean oven at 230 ° C. for 30 minutes to obtain an ITO substrate with a liquid crystal alignment film having a film thickness of 100 nm. In addition, the liquid crystal aligning agent of Example 3 produced a board | substrate on the conditions similar to said "evaluation of the inkjet applicability | paintability of a liquid crystal aligning agent", and then 30 minutes at 230 degreeC in a heat circulation type clean oven. Heat treatment was performed to obtain an ITO substrate with a liquid crystal alignment film having a thickness of 100 nm.

Next, the two substrates were combined with a 6 μm spacer sandwiched with the coating surface facing inward, and the periphery was adhered with a sealant to produce an empty cell. A polymerizable compound (1) of the following formula is added to a nematic liquid crystal (MLC-6608, manufactured by Merck Japan Ltd.) by vacuum injection into this empty cell, and the polymerizable compound (1) is added to 100% of the nematic liquid crystal. A liquid crystal cell was obtained by injecting 0.3% mixed liquid crystal and then sealing the injection port.

While applying a voltage of AC 5 V to the obtained liquid crystal cell, using a metal halide lamp with an illuminance of 60 mW, the wavelength of 350 nm or less was cut, and ultraviolet irradiation of 20 J / cm ^{2 in} terms of 365 nm was performed. A controlled liquid crystal cell was obtained. The temperature in the irradiation apparatus when the liquid crystal cell was irradiated with ultraviolet rays was 50 ° C.
Thereafter, the response speed of the liquid crystal cell before and after ultraviolet irradiation was measured. The response speed was measured as T90 → T10 from 90% transmittance to 10% transmittance.
The liquid crystal cell obtained in any of the examples confirmed that the alignment direction of the liquid crystal was controlled because the response speed of the liquid crystal cell after ultraviolet irradiation was higher than that of the liquid crystal cell before ultraviolet irradiation. . Further, in any liquid crystal cell, it was confirmed by observation with a polarizing microscope (ECLIPSE E600WPOL, manufactured by Nikon Corp.) that the liquid crystal was uniformly aligned.

<Example 1>
NEP (3.92 g) was added to the polyimide powder (1) (0.50 g) obtained in Synthesis Example 1, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (3.92 g) was added and stirred at 40 ° C. for 4 hours to obtain a solution.
On the other hand, NEP (5.88 g) was added to the polyimide powder (10) (0.75 g) obtained in Synthesis Example 10, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (5.88 g) was added and stirred at 40 ° C. for 4 hours to obtain a solution.
Further, NEP (9.79 g) was added to the polyimide powder (14) (1.25 g) obtained in Synthesis Example 14, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (9.79 g) was added and stirred at 40 ° C. for 4 hours to obtain a solution.
The three solutions obtained above were mixed and stirred at 40 ° C. for 4 hours to obtain a liquid crystal alignment treatment agent (1). This liquid crystal alignment treatment agent was confirmed to be a uniform solution without any abnormalities such as turbidity and precipitation.

<Example 2>
NEP (3.92 g) was added to the polyimide powder (2) (0.50 g) obtained in Synthesis Example 2, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (2.35 g) and PB (1.57 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
On the other hand, NEP (5.88 g) was added to the polyimide powder (10) (0.75 g) obtained in Synthesis Example 10, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (3.53 g) and PB (2.35 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
Further, NEP (9.79 g) was added to the polyimide powder (14) (1.25 g) obtained in Synthesis Example 14, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (5.88 g) and PB (3.92 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
The three solutions obtained above were mixed and stirred at 40 ° C. for 4 hours to obtain a liquid crystal alignment treatment agent (2). This liquid crystal alignment treatment agent was confirmed to be a uniform solution without any abnormalities such as turbidity and precipitation.

<Example 3>
Polyimide powder (3) (0.30 g) obtained in Synthesis Example 3, polyimide powder (10) (0.45 g) obtained in Synthesis Example 10, and polyimide powder (14) obtained in Synthesis Example 14 (0) NEP (16.5 g) and γ-BL (4.18 g) were added to .75 g) and dissolved by stirring at 70 ° C. for 24 hours. BCS (8.27g), PB (8.27g) and DME (4.14g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (3). This liquid crystal alignment treatment agent was confirmed to be a uniform solution without any abnormalities such as turbidity and precipitation.

<Example 4>
NMP (6.27 g) was added to the polyimide powder (4) (0.80 g) obtained in Synthesis Example 4, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (5.02 g) and DME (1.25 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
On the other hand, NMP (6.27 g) was added to the polyimide powder (12) (0.80 g) obtained in Synthesis Example 12, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (5.02 g) and DME (1.25 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
Further, NMP (8.36 g) was added to the polyimide powder (14) (1.07 g) obtained in Synthesis Example 14, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (6.68 g) and DME (1.67 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
The three solutions obtained above were mixed and stirred at 40 ° C. for 4 hours to obtain a liquid crystal alignment treatment agent (4). This liquid crystal alignment treatment agent was confirmed to be a uniform solution without any abnormalities such as turbidity and precipitation.

<Example 5>
NEP (7.52 g) was added to the polyimide powder (5) (0.80 g) obtained in Synthesis Example 5, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (2.51 g) and PB (2.51 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
On the other hand, NEP (7.52 g) was added to the polyimide powder (10) (0.80 g) obtained in Synthesis Example 10 and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (2.51 g) and PB (2.51 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
Further, NEP (10.0 g) was added to the polyimide powder (14) (1.07 g) obtained in Synthesis Example 14, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (3.34 g) and PB (3.34 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
The three solutions obtained above were mixed and stirred at 40 ° C. for 4 hours to obtain a liquid crystal alignment treatment agent (5). This liquid crystal alignment treatment agent was confirmed to be a uniform solution without any abnormalities such as turbidity and precipitation.

<Example 6>
Polyimide powder (6) (0.50 g) obtained in Synthesis Example 6, polyimide powder (10) (0.75 g) obtained in Synthesis Example 10, and polyimide powder (14) (1) obtained in Synthesis Example 14 (1 NEP (21.5 g) was added to 25 g) and dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (17.6 g) was added and stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (6). This liquid crystal alignment treatment agent was confirmed to be a uniform solution without any abnormalities such as turbidity and precipitation.

<Example 7>
NMP (3.76 g) and NEP (3.76 g) were added to the polyimide powder (7) (0.80 g) obtained in Synthesis Example 7, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (2.51 g) and PB (2.51 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
On the other hand, NMP (3.76 g) and NEP (3.76 g) were added to the polyimide powder (10) (0.80 g) obtained in Synthesis Example 10, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (2.51 g) and PB (2.51 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
Further, NMP (5.02 g) and NEP (5.02 g) were added to the polyimide powder (14) (1.07 g) obtained in Synthesis Example 14, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (3.34 g) and PB (3.34 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
The three solutions obtained above were mixed and stirred at 40 ° C. for 4 hours to obtain a liquid crystal alignment treatment agent (7). This liquid crystal alignment treatment agent was confirmed to be a uniform solution without any abnormalities such as turbidity and precipitation.

<Example 8>
Polyimide powder (8) (0.30 g) obtained in Synthesis Example 8, polyimide powder (10) (0.45 g) obtained in Synthesis Example 10, and polyimide powder (14) obtained in Synthesis Example 14 (0) NEP (12.4 g) and γ-BL (6.21 g) were added to .75 g) and dissolved by stirring at 70 ° C. for 24 hours. BCS (8.27g) and PB (14.5g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (8). This liquid crystal alignment treatment agent was confirmed to be a uniform solution without any abnormalities such as turbidity and precipitation.

<Example 9>
NEP (5.09 g) was added to the polyimide powder (1) (0.50 g) obtained in Synthesis Example 1, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (1.18 g) and PB (1.57 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
On the other hand, NEP (7.64 g) was added to the polyimide powder (11) (0.75 g) obtained in Synthesis Example 11, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (1.76 g) and PB (2.35 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
Further, NEP (12.7 g) was added to the polyimide powder (14) (1.25 g) obtained in Synthesis Example 14, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (2.94 g) and PB (3.92 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
The three solutions obtained above were mixed and stirred at 40 ° C. for 4 hours to obtain a liquid crystal alignment treatment agent (9). This liquid crystal alignment treatment agent was confirmed to be a uniform solution without any abnormalities such as turbidity and precipitation.

<Example 10>
NEP (4.70 g) was added to the polyimide powder (5) (0.50 g) obtained in Synthesis Example 5, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (3.13 g) was added and stirred at 40 ° C. for 4 hours to obtain a solution.
On the other hand, NEP (7.05 g) was added to the polyimide powder (12) (0.75 g) obtained in Synthesis Example 12, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (4.70 g) was added and stirred at 40 ° C. for 4 hours to obtain a solution.
Furthermore, NEP (11.8 g) was added to the polyimide powder (14) (1.25 g) obtained in Synthesis Example 14, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (7.83 g) was added and stirred at 40 ° C. for 4 hours to obtain a solution.
The three solutions obtained above were mixed and stirred at 40 ° C. for 4 hours to obtain a liquid crystal alignment treatment agent (10). This liquid crystal alignment treatment agent was confirmed to be a uniform solution without any abnormalities such as turbidity and precipitation.

<Example 11>
NEP (4.70 g) was added to the polyimide powder (1) (0.50 g) obtained in Synthesis Example 1, and dissolved by stirring at 70 ° C. for 24 hours. BCS (0.78g) and PB (2.35g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.
On the other hand, NEP (7.05 g) was added to the polyimide powder (13) (0.75 g) obtained in Synthesis Example 13 and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (1.18 g) and PB (3.53 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
Furthermore, NEP (11.8 g) was added to the polyimide powder (14) (1.25 g) obtained in Synthesis Example 14, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (1.96 g) and PB (5.88 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
The three solutions obtained above were mixed and stirred at 40 ° C. for 4 hours to obtain a liquid crystal alignment treatment agent (11). This liquid crystal alignment treatment agent was confirmed to be a uniform solution without any abnormalities such as turbidity and precipitation.

<Example 12>
NMP (6.27 g) was added to the polyimide powder (1) (0.80 g) obtained in Synthesis Example 1, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (2.51 g) and PB (3.76 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
On the other hand, NMP (4.18 g) was added to the polyimide powder (10) obtained in Synthesis Example 10 (0.53 g) and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (1.67 g) and PB (2.51 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
Furthermore, NMP (10.4 g) was added to the polyimide powder (15) obtained in Synthesis Example 15 (1.33 g), and the mixture was dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (4.18 g) and PB (6.27 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
The three solutions obtained above were mixed, M1 (0.19 g) was further added, and the mixture was stirred at 40 ° C. for 6 hours to obtain a liquid crystal alignment treatment agent (12). This liquid crystal alignment treatment agent was confirmed to be a uniform solution without any abnormalities such as turbidity and precipitation.

<Example 13>
Polyimide powder (1) (0.80 g) obtained in Synthesis Example 1, polyimide powder (10) (0.80 g) obtained in Synthesis Example 10, and polyimide powder (16) obtained in Synthesis Example 16 (1) 0.07 g) was added NEP (20.9 g) and dissolved by stirring at 70 ° C. for 24 hours. BCS (8.36g) and PB (12.5g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (13). This liquid crystal alignment treatment agent was confirmed to be a uniform solution without any abnormalities such as turbidity and precipitation.

<Example 14>
Polyimide powder (1) (0.80 g) obtained in Synthesis Example 1, polyimide powder (10) (0.80 g) obtained in Synthesis Example 10, and polyimide powder (16) obtained in Synthesis Example 16 (1) 0.07 g) was added NEP (20.9 g) and dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (12.5 g) and DPM (8.36 g) were added and stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (22). This liquid crystal alignment treatment agent was confirmed to be a uniform solution without any abnormalities such as turbidity and precipitation.

<Comparative Example 1>
NEP (19.6 g) was added to the polyimide powder (1) (2.50 g) obtained in Synthesis Example 1, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (19.6 g) was added and stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (14). This liquid crystal alignment treatment agent was confirmed to be a uniform solution without any abnormalities such as turbidity and precipitation.

<Comparative example 2>
NEP (19.6 g) was added to the polyimide powder (10) (2.50 g) obtained in Synthesis Example 10, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (19.6 g) was added and stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (15). This liquid crystal alignment treatment agent was confirmed to be a uniform solution without any abnormalities such as turbidity and precipitation.

<Comparative Example 3>
NEP (19.6 g) was added to the polyimide powder (14) (2.50 g) obtained in Synthesis Example 14, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (19.6 g) was added and stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (16). This liquid crystal alignment treatment agent was confirmed to be a uniform solution without any abnormalities such as turbidity and precipitation.

<Comparative example 4>
NEP (10.2 g) was added to the polyimide powder (1) (1.30 g) obtained in Synthesis Example 1, and dissolved by stirring at 70 ° C. for 24 hours. BCS (10.2g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.
On the other hand, NEP (10.2 g) was added to the polyimide powder (10) (1.30 g) obtained in Synthesis Example 10, and dissolved by stirring at 70 ° C. for 24 hours. BCS (10.2g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.
The two solutions obtained above were mixed and stirred at 40 ° C. for 4 hours to obtain a liquid crystal alignment treatment agent (17). This liquid crystal alignment treatment agent was confirmed to be a uniform solution without any abnormalities such as turbidity and precipitation.

<Comparative Example 5>
NEP (10.2 g) was added to the polyimide powder (1) (1.30 g) obtained in Synthesis Example 1, and dissolved by stirring at 70 ° C. for 24 hours. BCS (10.2g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.
On the other hand, NEP (10.2 g) was added to the polyimide powder (14) (1.30 g) obtained in Synthesis Example 14, and dissolved by stirring at 70 ° C. for 24 hours. BCS (10.2g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.
The two solutions obtained above were mixed and stirred at 40 ° C. for 4 hours to obtain a liquid crystal alignment treatment agent (18). This liquid crystal alignment treatment agent was confirmed to be a uniform solution without any abnormalities such as turbidity and precipitation.

<Comparative Example 6>
NEP (10.2 g) was added to the polyimide powder (10) (1.30 g) obtained in Synthesis Example 10, and dissolved by stirring at 70 ° C. for 24 hours. BCS (10.2g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.
On the other hand, NEP (10.2 g) was added to the polyimide powder (14) (1.30 g) obtained in Synthesis Example 14, and dissolved by stirring at 70 ° C. for 24 hours. BCS (10.2g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.
The two solutions obtained above were mixed and stirred at 40 ° C. for 4 hours to obtain a liquid crystal alignment treatment agent (19). This liquid crystal alignment treatment agent was confirmed to be a uniform solution without any abnormalities such as turbidity and precipitation.

<Comparative Example 7>
NEP (3.92 g) was added to the polyimide powder (9) (0.50 g) obtained in Synthesis Example 9 and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (2.35 g) and PB (1.57 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
On the other hand, NEP (5.88 g) was added to the polyimide powder (10) (0.75 g) obtained in Synthesis Example 10, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (3.53 g) and PB (2.35 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
Further, NEP (9.79 g) was added to the polyimide powder (14) (1.25 g) obtained in Synthesis Example 14, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (5.88 g) and PB (3.92 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.
The three solutions obtained above were mixed and stirred at 40 ° C. for 4 hours to obtain a liquid crystal alignment treatment agent (20). This liquid crystal alignment treatment agent was confirmed to be a uniform solution without any abnormalities such as turbidity and precipitation.

<Comparative Example 8>
NEP (19.6) was added to the polyimide powder (17) (2.50 g) obtained in Synthesis Example 17 and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (19.6 g) was added and stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (21). This liquid crystal alignment treatment agent was confirmed to be a uniform solution without any abnormalities such as turbidity and precipitation.

The summary of each liquid-crystal aligning agent obtained by said Example and comparative example is shown in Table 34-Table 36. In addition, Tables 37 to 42 show the results of liquid crystal display element evaluation using these liquid crystal alignment treatment agents.
In the table, * 1: An introduction amount (parts) of the specific polymer (A) with respect to 100 parts of all polymers is shown.
* 2 is the introduction amount (parts) of the specific polymer (B) to 100 parts of all polymers, * 3 is the introduction amount (parts) of the specific polymer (C) to 100 parts of all polymers, and * 4 is all The amount (parts) of the other polymer introduced relative to 100 parts of the polymer, * 5 indicates the content ratio (solid content concentration) of all the polymers in the liquid crystal aligning agent.

＊１：液晶を滴下した領域に、丸状の配向ムラが見られた。

* 1: Round alignment unevenness was observed in the region where the liquid crystal was dropped.

  As can be seen from the above results, the liquid crystal aligning agent of the example showed a stable pretilt angle even when the liquid crystal cell was subjected to high temperature treatment and ultraviolet irradiation, as compared with the liquid crystal aligning agent of the comparative example. Further, liquid crystal alignment unevenness generated by the ODF method could be reduced. Furthermore, even when the liquid crystal cell was irradiated with ultraviolet light, the decrease in the voltage holding ratio was suppressed, and the residual charge accumulated by the DC voltage was quickly relaxed.

  That is, in the comparison example of the liquid crystal alignment treatment agent using three kinds of specific polymers (A), (B) and (C) and a comparative example using only one of them, in the comparative example, All the effects of the present invention could not be satisfied. Specifically, it is shown in the comparison between Example 1 and Comparative Examples 1, 2, or 3, and the comparison between Example 1 and Comparative Examples 4, 5, or 6.

Furthermore, in the comparison between Example 2 using the specific diamine (1) and the comparative example using the conventional diamine having an alkyl group-type side chain structure, the liquid crystal aligning agent of Comparative Example 7 is All the effects could not be satisfied.
Further, in comparison between Example 1 and Comparative Example 8 using all of the specific diamines (1), (2) and (3), Comparative Example 8 shows all the effects of the present invention, in particular, the ODF method. Inferior results were obtained with respect to the occurrence of uneven liquid crystal alignment and a decrease in voltage holding ratio after exposure to light irradiation for a long time.

  The liquid crystal aligning agent of the present invention is useful for liquid crystal display elements using VA mode, PSA mode and SC-PVA mode, particularly TN elements, STN elements, TFT liquid crystal elements, particularly vertical alignment type liquid crystal display elements. . A liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention can be suitably used for a large-screen, high-definition liquid crystal television, a small-sized car navigation system, a smartphone, and the like.

  The entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2014-262605 filed on December 25, 2014 are cited herein as disclosure of the specification of the present invention. Incorporate.

Claims (19)

Liquid crystal aligning agent containing the following (A) component, (B) component, and (C) component.
Component (A): a polyimide precursor obtained by reaction of a diamine having a structure of the following formula [1] and a diamine component having a structure of the following formula [2] with a tetracarboxylic acid component or the polyimide Polyimide with imidized precursor.
(B) Component: A polyimide precursor obtained by reaction of a diamine component containing a diamine having the structure of the following formula [2] and a tetracarboxylic acid component or a polyimide obtained by imidizing the polyimide precursor.
(C): a polyimide obtained by reaction of a diamine component containing a diamine having at least one substituent selected from the group consisting of a carboxy group (COOH group) and a hydroxy group (OH group) with a tetracarboxylic acid component The polyimide which imidized the precursor or this polyimide precursor.

(X ¹ is a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, —CONH—, —NHCO—, —CON (CH ₃ ). —, —N (CH ₃ ) CO—, —COO—, and —OCO— represent at least one linking group selected from the group consisting of X ² is a single bond or — (CH ₂ ) _b — (b is 1 X ³ is a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— and —. X ⁴ represents at least one selected from the group consisting of OCO-, and X ⁴ has at least one divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, or a carbon number of 17 to 17 having a steroid skeleton. 51 represents a divalent organic group, and an arbitrary hydrogen atom on the cyclic group has 1 to 3 carbon atoms. An alkyl group, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom, X ⁵ may be a benzene ring, And at least one cyclic group selected from the group consisting of a cyclohexane ring and a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, It may be substituted with a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom, n is an integer of 0 to 4. X ⁶ is 1 to 18 carbon atoms. Selected from the group consisting of an alkyl group having 2 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and a fluorine-containing alkoxy group having 1 to 18 carbon atoms. Even without showing one.)

(W ¹ is —O—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —OCO—, —CON (CH ₃ ) — and —N (CH ₃ ) at least one linking group selected from the group consisting of CO-, wherein W ² is at least one selected from the group consisting of a single bond, an alkylene group having 1 to 20 carbon atoms, a non-aromatic ring and an aromatic ring. W ³ represents a single bond, —O—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —COO—, —OCO—, —CON (CH ₃ ) —, At least one selected from the group consisting of —N (CH ₃ ) CO— and —O (CH ₂ ) _m — (m represents an integer of 1 to 5), W ⁴ represents a nitrogen-containing aromatic heterocyclic ring; Show.)   The liquid crystal aligning agent of Claim 1 in which the diamine which has the structure of said Formula [1] is used only for the diamine component in the said (A) component.   When the use ratio (mol%) of the diamine having the structure represented by the formula [1] in the component (A) to the diamine component is 1.0, the formula [1] in the component (B) is used. The liquid-crystal aligning agent of Claim 1 whose usage-amount (mol%) with respect to the whole diamine component of the diamine which has a structure is 0.01-0.8.   When the usage ratio (mol%) of the diamine having the structure represented by the formula [1] in the component (A) to the diamine component is 1.0, the formula [1] in the component (C) The liquid-crystal aligning agent of Claim 1 or 3 whose usage-amount (mol%) with respect to the whole diamine component of the diamine which has a structure shown is a ratio of 0.01-0.3.   The diamine having at least one substituent selected from the group consisting of the carboxy group (COOH group) and the hydroxy group (OH group) is used only for the diamine component in the component (C). The liquid crystal aligning agent according to claim 1. The liquid-crystal aligning agent as described in any one of Claims 1-5 by which the diamine which has the structure of said Formula [1] is shown by following formula [1a].

(X shows the structure of said Formula [1]. N1 shows the integer of 1-4.) The liquid-crystal aligning agent as described in any one of Claims 1-6 by which the diamine which has the structure of the said Formula [2] is shown by following formula [2a].

(W represents the structure of the formula [2]. P1 represents an integer of 1 to 4.) The liquid crystal aligning agent according to any one of claims 1 to 7, wherein the diamine having at least one substituent selected from the group consisting of the carboxy group and the hydroxy group is represented by the following formula [3a].

(Y represents the structure of the following formula [3-1] or [3-2]. M1 represents an integer of 1 to 4.)

(A and b each represent an integer of 0 to 4) The liquid crystal as described in any one of Claims 1-8 in which the tetracarboxylic acid component in the said (A) component, (B) component, and (C) component contains the tetracarboxylic dianhydride of following formula [4]. Alignment treatment agent.

(Z represents at least one structure selected from the group consisting of the following formulas [4a] to [4k].)

(Z ^{1 to} Z ⁴ each independently represents at least one selected from the group consisting of a hydrogen atom, a methyl group, a chlorine atom and a benzene ring. Z ⁵ and Z ⁶ each independently represent a hydrogen atom or a methyl group. Group.)   The liquid-crystal aligning agent as described in any one of Claims 1-9 containing the at least 1 sort (s) of solvent chosen from the group which consists of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and (gamma) -butyrolactone. . 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, and the group consisting of the following formulas [D1] to [D3] The liquid-crystal aligning agent as described in any one of Claims 1-10 containing the at least 1 sort (s) of solvent chosen.

(D ¹ represents an alkyl group having 1 to 3 carbon atoms, D ² represents an alkyl group having 1 to ³ carbon atoms, and D ³ represents an alkyl group having 1 to 4 carbon atoms.)   A crosslinkable compound having at least one group selected from the group consisting of an epoxy group, an isocyanate group, an oxetane group and a cyclocarbonate group, at least one selected from the group consisting of a hydroxy group, a hydroxyalkyl group and a lower alkoxyalkyl group The liquid crystal aligning agent as described in any one of Claims 1-11 containing the crosslinkable compound which has a group, or the crosslinkable compound which has a polymerizable unsaturated bond group.   The liquid crystal aligning film obtained from the liquid-crystal aligning agent as described in any one of Claims 1-12.   The liquid crystal aligning film obtained by apply | coating the liquid-crystal aligning agent as described in any one of Claims 1-12 by the inkjet method.   The liquid crystal display element which has a liquid crystal aligning film of Claim 13 or 14.   A liquid crystal composition comprising a liquid crystal layer between a pair of substrates provided with electrodes and comprising a polymerizable compound that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates, and the electrodes The liquid crystal aligning film of Claim 13 or 14 used for the liquid crystal display element manufactured through the process of superposing | polymerizing the said polymeric compound, applying a voltage in between.   The liquid crystal display element which has a liquid crystal aligning film of Claim 16.   A liquid crystal layer between a pair of substrates provided with electrodes, and a liquid crystal alignment film containing a polymerizable group that is polymerized by at least one of active energy rays and heat between the pair of substrates; The liquid crystal aligning film of Claim 13 or 14 used for the liquid crystal display element manufactured through the process of superposing | polymerizing the said polymeric group, applying a voltage in between.   The liquid crystal display element which has a liquid crystal aligning film of Claim 18.