JP2017226647A - Novel diamine compound, polyimide precursor and polyimide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide novel diamine compounds, polyimide precursors and polyimides used for liquid crystal orientation treatment agents and the like.SOLUTION: A diamine compound is represented by formula [2A] (Xis -O-, -COO-, -OCO-, -CONH-, -NHCO-, -NH-, -N(R)- or -S-; Ris a C1-5 linear/branched alkyl group; Xand Xindependently represent a divalent C1-3 alkyl group, alkoxyl group, F-containing alkyl group, F-containing alkoxyl group or F-substituted/unsubstituted cyclic group, selected from a benzene ring, a cyclohexyl ring or a heterocycle; Xis a C1-18 alkyl group, F-containing alkyl group, alkoxyl group or F-containing alkoxyl group; m is an integer of 2-15; n is an integer of 1-3; p is an integer of 0-3; 1≤n+p≤6).SELECTED DRAWING: None

Description

  The present invention relates to a novel diamine compound, a polyimide precursor obtained by reacting the compound as a part of the raw material, a polyimide obtained by imidizing the polyimide precursor, and a liquid crystal alignment comprising these polymers. The present invention relates to a treatment agent, a liquid crystal alignment film, and a liquid crystal display element having 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.
In many cases, a polyimide film is used as the liquid crystal alignment film. In the formation of this polyimide film, a method of applying a polyamic acid solution or a solvent-soluble polyimide solution, which is a polyimide precursor, to a substrate and baking it is employed. This polyamic acid or solvent-soluble polyimide is generally formed by a reaction between a tetracarboxylic acid derivative such as tetracarboxylic dianhydride and a diamine component.

  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 by the polyimide structure, the method using a diamine having a side chain as a part of the polyimide raw material can control the pretilt angle according to the proportion of the diamine used. It is relatively easy to obtain and is useful as means for increasing the pretilt angle (see, for example, Patent Document 1).

In addition, with regard to the diamine component for increasing the pretilt angle of the liquid crystal as described above, a structural study for improving the stability and process dependency of the pretilt angle has been conducted. Here, as a side chain structure to be used, a structure containing a ring structure such as a phenyl group or a cyclohexyl group has been proposed (see, for example, 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 between the substrates having a cell gap of 3 to 5 μm. It was difficult to simplify the manufacturing process. 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 (also referred to as an ODF 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, it has become necessary to suppress display unevenness as the liquid crystal display element has been improved in definition. The ODF method has been solved by optimizing the manufacturing process so as to reduce the influence of adsorbed water and impurities, such as reducing the dripping 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 has become impossible 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.

Japanese Unexamined Patent Publication No. 2-282726 Japanese Unexamined Patent Publication No. 9-278724

  The liquid crystal alignment film is also used to control the angle of the liquid crystal with respect to the substrate, that is, the pretilt angle of the liquid crystal. However, as the liquid crystal display element becomes more sophisticated and its use range is expanding year by year, Not only can a predetermined pretilt angle be obtained, but also the stability of the pretilt angle has become increasingly important.

  In the manufacturing process of the liquid crystal display element, in order to improve the alignment uniformity of the liquid crystal, the liquid crystal is sometimes isotropically treated by heat treatment after sealing the liquid crystal. However, when the stability of the pretilt angle is low, there arises a problem that a pretilt angle having a target size cannot be obtained after this isotropic processing or the pretilt angle varies. 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 pretilt angle is gradually changed, problems such as inability to obtain initial display characteristics or occurrence of unevenness in display occur.

  In the ODF method, which is a liquid crystal filling process when manufacturing a liquid crystal display element, liquid crystal is dropped directly on the alignment film, so that physical stress is applied to the liquid crystal and the liquid crystal alignment film when the liquid crystal is dropped or the substrate is bonded. In addition, since it is necessary to fill the entire panel with liquid crystal, it is necessary to increase the dropping point of the liquid crystal. For this reason, liquid crystal drops and liquid crystal droplets are in contact with adjacent liquid droplets, so that so-called alignment unevenness such as drop marks and lattice unevenness is likely to occur. There was a problem of unevenness. This alignment unevenness is caused by adsorbed water and impurities adhering to the interface of the liquid crystal alignment film formed on the substrate being swept away by the liquid crystal dropped by the ODF method, so that the liquid crystal dropping part and the liquid crystal droplets are in contact with each other. It is thought to be generated by the amount of adsorbed water and impurities.

  The present invention has been made in view of the above circumstances. That is, an object of the present invention is to provide a liquid crystal alignment film whose pretilt angle does not change even when exposed to high temperature and light irradiation for a long time, and a liquid crystal alignment film that can reduce liquid crystal alignment unevenness generated by the ODF method. It is to provide. Furthermore, an object of the present invention is to provide a liquid crystal display device having the above liquid crystal alignment film, a liquid crystal alignment treatment agent capable of providing the above liquid crystal alignment film, a polymer for obtaining the liquid crystal alignment treatment agent, and a weight thereof. The object is to provide a diamine compound for obtaining a coalescence.

（式［１Ａ］中、Ｘ_１は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＮＨ−、−Ｎ（Ｒ_１）−（Ｒ_１は炭素数１〜５の直鎖状アルキル基又は炭素数１〜５の分岐状アルキル基である）又は−Ｓ−である。Ｘ_２はベンゼン環、シクロヘキシル環又は複素環から選ばれる２価の環状基を示し、これらの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のアルコキシル基、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ル基又はフッ素原子で置換されていてもよい。Ｘ_３はベンゼン環、シクロヘキシル環又は複素環から選ばれる２価の環状基を示し、これらの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のアルコキシル基、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ル基又はフッ素原子で置換されていてもよい。Ｘ_４は炭素数１〜１８のアルキル基、炭素数１〜１８のフッ素含有アルキル基、炭素数１〜１８のアルコキシル基又は炭素数１〜１８のフッ素含有アルコキシル基である。ｍは２〜１５の整数であり、ｎは１〜３の整数であり、ｐは０〜３の整数であり、ｎ＋ｐは１〜６の整数である。）

（式［１Ｂ］中、Ｘ_５は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＮＨ−、−Ｎ（Ｒ_２）−（Ｒ_２は炭素数１〜５の直鎖状アルキル基又は炭素数１〜５の分岐状アルキル基である）又は−Ｓ−である。Ｘ_６はステロイド骨格を有する炭素数１２〜２５の有機基である。ｑは２〜１５の整数である。） As a result of intensive studies, the present inventor has found that a liquid crystal aligning agent containing a polymer having a side chain having a specific structure is extremely effective for achieving the above object, and completes the present invention. It came to.
That is, the present invention has the following gist.
(1) Containing at least one polymer selected from the group consisting of a polyimide precursor having a side chain represented by the following formula [1A] or formula [1B] and a polyimide obtained by imidizing the polyimide precursor. Liquid crystal aligning agent characterized by the above.

(In the formula [1A], X ₁ is a single bond, —O—, —COO—, —OCO—, —CONH—, —NHCO—, —NH—, —N (R ₁ ) — (R ₁ is the number of carbon atoms. A linear alkyl group of 1 to 5 or a branched alkyl group of 1 to 5 carbon atoms) or -S-, wherein X ₂ represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring or a heterocyclic ring. And any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a fluorine atom having 1 to 3 carbon atoms. X ₃ represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring, and a heterocyclic ring, and any hydrogen atom on these cyclic groups may have a carbon number. 1-3 alkyl groups, 1-3 alkoxy groups, charcoal Number 1-3 fluorine-containing alkyl group, fluorine-containing alkoxyl group or .X ₄ be substituted by fluorine atoms having 1 to 3 carbon atoms is an alkyl group having 1 to 18 carbon atoms, fluorine having 1 to 18 carbon atoms A containing alkyl group, an alkoxyl group having 1 to 18 carbon atoms or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms, m is an integer of 2 to 15, n is an integer of 1 to 3, and p is 0 to 0. 3 is an integer, and n + p is an integer of 1 to 6.)

(In the formula [1B], X ₅ represents a single bond, —O—, —COO—, —OCO—, —CONH—, —NHCO—, —NH—, —N (R ₂ ) — (R ₂ represents the number of carbon atoms. A linear alkyl group having 1 to 5 or a branched alkyl group having 1 to 5 carbon atoms) or -S-, X ₆ is an organic group having 12 to 25 carbon atoms having a steroid skeleton, and q is It is an integer from 2 to 15.)

（式［２Ａ］中、Ｘ_１は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＮＨ−、−Ｎ（Ｒ_１）−（Ｒ_１は炭素数１〜５の直鎖状アルキル基又は炭素数１〜５の分岐状アルキル基である）又は−Ｓ−である。Ｘ_２はベンゼン環、シクロヘキシル環又は複素環から選ばれる２価の環状基を示し、これらの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のアルコキシル基、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ル基又はフッ素原子で置換されていてもよい。Ｘ_３はベンゼン環、シクロヘキシル環又は複素環から選ばれる２価の環状基を示し、これらの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のアルコキシル基、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ル基又はフッ素原子で置換されていてもよい。Ｘ_４は炭素数１〜１８のアルキル基、炭素数１〜１８のフッ素含有アルキル基、炭素数１〜１８のアルコキシル基又は炭素数１〜１８のフッ素含有アルコキシル基である。ｍは２〜１５の整数であり、ｎは１〜３の整数であり、ｐは０〜３の整数であり、ｎ＋ｐは１〜６の整数である。） (2) The polyimide precursor according to (1) above, which is obtained by reacting a diamine component containing a diamine compound having a side chain represented by the formula [1A] or the formula [1B] with a tetracarboxylic acid component. Liquid crystal aligning agent.
(3) The liquid crystal aligning agent according to (2), wherein the diamine compound having a side chain represented by the formula [1A] is represented by the following formula [2A].

(In Formula [2A], X ₁ is a single bond, —O—, —COO—, —OCO—, —CONH—, —NHCO—, —NH—, —N (R ₁ ) — (R ₁ is the number of carbon atoms. A linear alkyl group of 1 to 5 or a branched alkyl group of 1 to 5 carbon atoms) or -S-, wherein X ₂ represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring or a heterocyclic ring. And any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a fluorine atom having 1 to 3 carbon atoms. X ₃ represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring, and a heterocyclic ring, and any hydrogen atom on these cyclic groups may have a carbon number. 1-3 alkyl groups, 1-3 alkoxy groups, charcoal Number 1-3 fluorine-containing alkyl group, fluorine-containing alkoxyl group or .X ₄ be substituted by fluorine atoms having 1 to 3 carbon atoms is an alkyl group having 1 to 18 carbon atoms, fluorine having 1 to 18 carbon atoms A containing alkyl group, an alkoxyl group having 1 to 18 carbon atoms or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms, m is an integer of 2 to 15, n is an integer of 1 to 3, and p is 0 to 0. 3 is an integer, and n + p is an integer of 1 to 6.)

（式［２ａ］中、Ｒ_１は炭素数１〜１８のアルキル基、炭素数１〜１８のフッ素含有アルキル基、炭素数１〜１８のアルコキシル基又は炭素数１〜１８のフッ素含有アルコキシル基であり、ｍ１は２〜１５の整数であり、ｐ１は０〜３の整数である。
式［２ｂ］中、Ｒ_２は炭素数１〜１８のアルキル基、炭素数１〜１８のフッ素含有アルキル基、炭素数１〜１８のアルコキシル基又は炭素数１〜１８のフッ素含有アルコキシル基であり、ｍ２は２〜１５の整数であり、ｐ２は０〜３の整数である。
式［２ｃ］中、Ｒ_３は炭素数１〜１８のアルキル基、炭素数１〜１８のフッ素含有アルキル基、炭素数１〜１８のアルコキシル基又は炭素数１〜１８のフッ素含有アルコキシル基であり、ｍ３は２〜１５の整数であり、ｎ１は１〜３の整数であり、ｐ３は０〜３の整数であり、ｎ１＋ｐ３は１〜６の整数である。
式［２ｄ］中、Ｒ_４は炭素数１〜１８のアルキル基、炭素数１〜１８のフッ素含有アルキル基、炭素数１〜１８のアルコキシル基又は炭素数１〜１８のフッ素含有アルコキシル基であり、ｍ４は２〜１５の整数であり、ｎ２は１〜３の整数であり、ｐ４は０〜３の整数であり、ｎ２＋ｐ４は１〜６の整数である。） (4) The liquid crystal aligning agent according to (3), wherein the diamine compound represented by the formula [2A] is represented by the following formulas [2a] to [2d].

(In the formula [2a], R ₁ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. Yes, m1 is an integer from 2 to 15, and p1 is an integer from 0 to 3.
In the formula [2b], R ₂ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. , M2 is an integer from 2 to 15, and p2 is an integer from 0 to 3.
In Formula [2c], R ₃ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. , M3 is an integer of 2 to 15, n1 is an integer of 1 to 3, p3 is an integer of 0 to 3, and n1 + p3 is an integer of 1 to 6.
In the formula [2d], R ₄ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. , M4 is an integer of 2 to 15, n2 is an integer of 1 to 3, p4 is an integer of 0 to 3, and n2 + p4 is an integer of 1 to 6. )

（式［２Ｂ］中、Ｘ_５は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＮＨ−、−Ｎ（Ｒ_２）−（Ｒ_２は炭素数１〜５の直鎖状アルキル基又は炭素数１〜５の分岐状アルキル基である）又は−Ｓ−である。Ｘ_６はステロイド骨格を有する炭素数１２〜２５の有機基である。ｑは２〜１５の整数である。）
（６）前記式［２Ａ］又は式［２Ｂ］で示されるジアミン化合物が、ジアミン成分中の５〜８０モル％である上記（３）〜（５）のいずれかに記載の液晶配向処理剤。
（７）前記式［２ａ］〜式［２ｄ］で示されるジアミン化合物が、ジアミン成分中の５〜８０モル％である上記（４）に記載の液晶配向処理剤。 (5) The liquid crystal aligning agent according to (2), wherein the diamine compound having a side chain represented by the formula [1B] is represented by the following formula [2B].

(In the formula [2B], X ₅ represents a single bond, —O—, —COO—, —OCO—, —CONH—, —NHCO—, —NH—, —N (R ₂ ) — (R ₂ represents the number of carbon atoms. A linear alkyl group having 1 to 5 or a branched alkyl group having 1 to 5 carbon atoms) or -S-, X ₆ is an organic group having 12 to 25 carbon atoms having a steroid skeleton, and q is It is an integer from 2 to 15.)
(6) The liquid-crystal aligning agent in any one of said (3)-(5) whose diamine compound shown by said Formula [2A] or Formula [2B] is 5-80 mol% in a diamine component.
(7) The liquid-crystal aligning agent as described in said (4) whose diamine compound shown by said Formula [2a]-Formula [2d] is 5-80 mol% in a diamine component.

（式［３］中、Ｚ_１は炭素数４〜１３の４価の有機基であり、かつ炭素数４〜１０の非芳香族環状炭化水素基を含有する。）
（９）前記Ｚ_１が、下記の式［３ａ］〜式［３ｊ］で示される構造である上記（８）に記載の液晶配向処理剤。

（式［３ａ］中、Ｚ_２〜Ｚ_５は水素原子、メチル基、塩素原子又はベンゼン環であり、それぞれ、同じであっても異なってもよい。式［３ｇ］中、Ｚ_６、Ｚ_７は水素原子又はメチル基であり、それぞれ、同じであっても異なってもよい）。
（１０）液晶配向処理剤中に８０〜９９質量％の有機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）有機溶媒が、５〜６０質量％の貧溶媒を含有する上記（１０）に記載の液晶配向処理剤。 (8) The liquid-crystal aligning agent in any one of said (2)-(7) whose said tetracarboxylic-acid component is the tetracarboxylic dianhydride shown by following formula [3].

(In the formula [3], Z ₁ is a tetravalent organic group having 4 to 13 carbon atoms and contains a non-aromatic cyclic hydrocarbon group having 4 to 10 carbon atoms.)
(9) wherein _{Z 1} is a liquid crystal alignment treating agent according to (8) is a structure represented by the following formula [3a] ~ formula [3j].

(In the formula [3a], Z _{2 to} Z ₅ are a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different. In the formula [3g], Z ₆ and Z ₇ Are hydrogen atoms or methyl groups, which may be the same or different.
(10) The liquid-crystal aligning agent in any one of said (1)-(9) containing 80-99 mass% organic solvent in a liquid-crystal aligning agent.
(11) The liquid-crystal aligning agent as described in said (10) in which an organic solvent contains 5-60 mass% poor solvent.

(12) A liquid crystal alignment film obtained from the liquid crystal aligning agent according to any one of (1) to (11).
(13) A liquid crystal alignment film obtained by an inkjet coating method using the liquid crystal alignment treatment agent according to any one of (1) to (11).
(14) A liquid crystal display device having the liquid crystal alignment film according to (12) or (13).
(15) A liquid crystal composition comprising 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 the above (12) or (13), 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.
(16) A liquid crystal display device having the liquid crystal alignment film according to (15).
(17) A polymerizable compound that includes a liquid crystal layer between a pair of substrates including an electrode and the liquid crystal alignment film and that is polymerized by at least one of active energy rays and heat between the pair of substrates. The liquid crystal display element according to the above (16), which is produced through a step of polymerizing the polymerizable compound while disposing a liquid crystal composition and applying a voltage between the electrodes.

(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 (12) or (13), which is used in 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 element comprising the liquid crystal alignment film according to (18).
(20) A liquid crystal alignment film comprising 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 display device according to (19), which is produced through a step of polymerizing the polymerizable group while applying a voltage between the electrodes.
(21) A diamine compound represented by the formula [2A].
(22) A diamine compound represented by the formula [2a] to the formula [2d].
(23) Polyamic acid obtained by reacting a diamine component containing the diamine compound represented by the above formula [2A] or formula [2B] with a tetracarboxylic acid component or a polyimide obtained by dehydrating and ring-closing the polyamic acid.
(24) Polyamic acid obtained by reacting a diamine component containing the diamine compound represented by the above formulas [2a] to [2d] with a tetracarboxylic acid component or a polyimide obtained by dehydrating and ring-closing the polyamic acid.

  By using the liquid crystal aligning agent containing a polymer having a side chain of a specific structure according to the present invention, the pretilt angle does not change even when exposed to high temperature and light irradiation for a long time, and in addition, it is generated by the ODF method. A liquid crystal alignment film capable of reducing liquid crystal alignment unevenness can be provided. Accordingly, by using this liquid crystal alignment film, a highly reliable liquid crystal display element having excellent display characteristics can be provided.

（式［１Ａ］中、Ｘ_１は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＮＨ−、−Ｎ（Ｒ_１）−（Ｒ_１は炭素数１〜５の直鎖状アルキル基又は炭素数１〜５の分岐状アルキル基である）又は−Ｓ−である。Ｘ_２はベンゼン環、シクロヘキシル環又は複素環から選ばれる２価の環状基を示し、これらの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のアルコキシル基、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ル基又はフッ素原子で置換されていてもよい。Ｘ_３はベンゼン環、シクロヘキシル環又は複素環から選ばれる２価の環状基を示し、これらの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のアルコキシル基、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ル基又はフッ素原子で置換されていてもよい。Ｘ_４は炭素数１〜１８のアルキル基、炭素数１〜１８のフッ素含有アルキル基、炭素数１〜１８のアルコキシル基又は炭素数１〜１８のフッ素含有アルコキシル基である。ｍは２〜１５の整数であり、ｎは１〜３の整数であり、ｐは０〜３の整数であり、ｎ＋ｐは１〜６の整数である。）

（式［１Ｂ］中、Ｘ_５は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＮＨ−、−Ｎ（Ｒ_２）−（Ｒ_２は炭素数１〜５の直鎖状アルキル基又は炭素数１〜５の分岐状アルキル基である）又は−Ｓ−である。Ｘ_６はステロイド骨格を有する炭素数１２〜２５の有機基である。ｑは２〜１５の整数である。） The present invention is described in detail below.
The present invention is at least selected from the group consisting of a polyimide precursor having a side chain represented by the following formula [1A] or [1B] (also referred to as a specific side chain structure) and a polyimide obtained by imidizing the polyimide precursor. It is a liquid crystal aligning agent having one type of polymer (also referred to as a specific polymer).

(In the formula [1A], X ₁ is a single bond, —O—, —COO—, —OCO—, —CONH—, —NHCO—, —NH—, —N (R ₁ ) — (R ₁ is the number of carbon atoms. A linear alkyl group of 1 to 5 or a branched alkyl group of 1 to 5 carbon atoms) or -S-, wherein X ₂ represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring or a heterocyclic ring. And any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a fluorine atom having 1 to 3 carbon atoms. X ₃ represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring, and a heterocyclic ring, and any hydrogen atom on these cyclic groups may have a carbon number. 1-3 alkyl groups, 1-3 alkoxy groups, charcoal Number 1-3 fluorine-containing alkyl group, fluorine-containing alkoxyl group or .X ₄ be substituted by fluorine atoms having 1 to 3 carbon atoms is an alkyl group having 1 to 18 carbon atoms, fluorine having 1 to 18 carbon atoms A containing alkyl group, an alkoxyl group having 1 to 18 carbon atoms or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms, m is an integer of 2 to 15, n is an integer of 1 to 3, and p is 0 to 0. 3 is an integer, and n + p is an integer of 1 to 6.)

(In the formula [1B], X ₅ represents a single bond, —O—, —COO—, —OCO—, —CONH—, —NHCO—, —NH—, —N (R ₂ ) — (R ₂ represents the number of carbon atoms. A linear alkyl group having 1 to 5 or a branched alkyl group having 1 to 5 carbon atoms) or -S-, X ₆ is an organic group having 12 to 25 carbon atoms having a steroid skeleton, and q is It is an integer from 2 to 15.)

The specific side chain structure of the present invention is a structure represented by the formula [1A] or the formula [1B].
The structure represented by the formula [1A] has a benzene ring, a cyclohexyl ring, or a heterocyclic ring. Thereby, the stability with respect to the heat | fever and ultraviolet-ray of a side chain site | part improves. Therefore, a liquid crystal alignment film having a stable pretilt angle against heat and light can be obtained.
The structure represented by the formula [1B] has a cyclic group composed of a steroid skeleton. Therefore, the same effect as that of the formula [1A], that is, the stability of the side chain site to heat and ultraviolet light is improved, and a liquid crystal alignment film having a stable pretilt angle against heat and light can be obtained.
The structure represented by the formula [1A] has a benzene ring, a cyclohexyl ring, or a heterocyclic ring. The structure represented by the formula [1B] has a cyclic group composed of a steroid skeleton. Since the benzene ring, cyclohexyl ring or heterocyclic ring in the formula [1A] and the cyclic group consisting of the steroid skeleton in the formula [1B] have a structure similar to the liquid crystal, the liquid crystal of the liquid crystal dropped by the ODF method is used. The wet spreading property on the alignment film is increased. Thereby, physical stress on the liquid crystal and the liquid crystal alignment film generated when the substrates are bonded can be reduced. From these points, the liquid crystal alignment film having the structure of the formula [1A] or the formula [1B] which is the specific side chain structure of the present invention can reduce liquid crystal alignment unevenness generated in the ODF method.

The structure represented by the formula [1A] is between the polymer main chain and the moiety of — (CH ₂ ) _m —X ₁ — (X ₂ ) _n — (X ₃ ) _p —X _{4 in} the formula [1A]. Have an alkyl group. That is, a portion of — (CH ₂ ) _m —X ₁ — (X ₂ ) _n — (X ₃ ) _p —X ₄ having high hydrophobicity exists at a position away from the polymer main chain. Therefore, when the liquid crystal alignment film is used, the portion of-(CH ₂ ) _m -X _1- (X ₂ ) _n- (X ₃ ) _p -X ₄ efficiently appears at the alignment film interface. The hydrophobicity of the liquid crystal alignment film can be increased. Thereby, adsorption | suction of the water and impurity of a liquid crystal aligning film interface can be suppressed. In addition, since the moiety of — (CH ₂ ) _m —X ₁ — (X ₂ ) _n — (X ₃ ) _p —X ₄ exists at a position away from the polymer main chain, a benzene ring similar to liquid crystal, A cyclohexyl ring or a heterocyclic ring can be efficiently formed at the alignment film interface. Therefore, the wet spread property on the liquid crystal alignment film of the liquid crystal dropped by the ODF method is increased.

Similarly, the specific side chain structure in the formula [1B] has the same function as the specific side chain structure in the formula [1A].
From the above points, by using the liquid crystal aligning agent containing a polymer having a side chain of a specific structure of the present invention, the pretilt angle does not change even when exposed to high temperature and light irradiation for a long time, and the ODF method The liquid crystal alignment film which can reduce the liquid crystal alignment nonuniformity which generate | occur | produces in can be provided. Further, by using this liquid crystal alignment film, a highly reliable liquid crystal display element having excellent display characteristics can be provided.

式［１Ａ］中、Ｘ_１は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＮＨ−、−Ｎ（Ｒ_１）−（Ｒ_１は炭素数１〜５の直鎖状アルキル基又は炭素数１〜５の分岐状アルキル基である）又は−Ｓ−である。なかでも、単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＮＨ−又は−Ｎ（Ｒ_１）−（Ｒ_１は炭素数１〜５の直鎖状アルキル基又は炭素数１〜５の分岐状アルキル基である）が好ましい。より好ましくは、−Ｏ−、−ＣＯＮＨ−、−ＮＨＣＯ−又は−ＮＨ−である。さらに好ましくは、−Ｏ−、−ＣＯＮＨ−又は−ＮＨＣＯ−である。
式［１Ａ］中、Ｘ_２はベンゼン環、シクロヘキシル環又は複素環から選ばれる２価の環状基を示し、これらの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のアルコキシル基、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ル基又はフッ素原子で置換されていてもよい。その際、Ｘ_２は、同一であっても異なっていてもよい。なかでも、Ｘ_２はベンゼン環又はシクロヘキシル環が好ましい。 <Specific side chain structure>
At least one selected from the group consisting of a polyimide precursor which is a specific polymer of the present invention and a polyimide obtained by imidizing the polyimide precursor has a specific side chain structure represented by the following formula [1A].

In the formula [1A], X ₁ is a single bond, —O—, —COO—, —OCO—, —CONH—, —NHCO—, —NH—, —N (R ₁ ) — (R ₁ has ₁ carbon atom) A linear alkyl group of -5 or a branched alkyl group of 1 to 5 carbon atoms) or -S-. Among them, a single bond, —O—, —COO—, —OCO—, —CONH—, —NHCO—, —NH— or —N (R ₁ ) — (R ₁ is a straight chain having 1 to 5 carbon atoms) An alkyl group or a branched alkyl group having 1 to 5 carbon atoms) is preferred. More preferred is —O—, —CONH—, —NHCO— or —NH—. More preferred is —O—, —CONH— or —NHCO—.
In the formula [1A], X ₂ represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring or a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, carbon It may be substituted with an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. At that time, X ₂ may be the same or different. Of these, X ₂ is preferably a benzene ring or a cyclohexyl ring.

In the formula [1A], X ₃ represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring or a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, carbon It may be substituted with an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. At that time, X ₃ may be the same or different. Among these, X ₃ is preferably a benzene ring or a cyclohexyl ring.
In the formula [1A], X ₄ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. . Especially, a C1-C18 alkyl group, a C1-C10 fluorine-containing alkyl group, a C1-C18 alkoxyl group, or a C1-C10 fluorine-containing alkoxyl group is preferable. More preferably, they are a C1-C12 alkyl group or a C1-C12 alkoxyl group. More preferably, they are a C1-C10 alkyl group or a C1-C10 alkoxyl group.
In formula [1A], m is an integer of 2-15. Especially, the integer of 2-10 is preferable. More preferred is an integer of 2 to 7.
In the formula [1A], n is an integer of 1 to 3. Among these, an integer of 1 or 2 is preferable.
In formula [1A], p is an integer of 0-3. Especially, the integer of 0-2 is preferable.
N + p is an integer of 1-6 in a formula [1A]. Especially, the integer of 1-4 is preferable.
Preferred combinations of X ₁ , X ₂ , X ₃ , X ₄ , m, n and p in the formula [1A] are as shown in Tables 1 to 36.

式［１Ｂ］中、Ｘ_５は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＮＨ−、−Ｎ（Ｒ_２）−（Ｒ_２は炭素数１〜５の直鎖状アルキル基又は炭素数１〜５の分岐状アルキル基である）又は−Ｓ−である。なかでも、単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＮＨ−、又は−Ｎ（Ｒ_２）−（Ｒ_２は炭素数１〜５の直鎖状アルキル基又は炭素数１〜５の分岐状アルキル基である）が好ましい。より好ましくは、−Ｏ−、−ＣＯＮＨ−、−ＮＨＣＯ−又は−ＮＨ−である。さらに好ましくは、−Ｏ−、−ＣＯＮＨ−又は−ＮＨＣＯ−である。
式［１Ｂ］中、Ｘ_６はステロイド骨格を有する炭素数１２〜２５の有機基であり、より好ましくはステロイド骨格を有する炭素数１５〜２５の有機基である。
式［１Ｂ］中、ｑは２〜１５の整数である。なかでも、２〜１０の整数が好ましい。より好ましいのは、２〜７の整数である。 In addition, the specific polymer of the present invention is a polyimide precursor and at least one selected from the group consisting of polyimides obtained by imidizing the polyimide precursor has a specific side chain structure represented by the following formula [1B]. .

In the formula [1B], X ₅ is a single bond, —O—, —COO—, —OCO—, —CONH—, —NHCO—, —NH—, —N (R ₂ ) — (R ₂ has 1 carbon atom) A linear alkyl group of -5 or a branched alkyl group of 1 to 5 carbon atoms) or -S-. Among them, a single bond, —O—, —COO—, —OCO—, —CONH—, —NHCO—, —NH—, or —N (R ₂ ) — (R ₂ is a straight chain having 1 to 5 carbon atoms) And a branched alkyl group having 1 to 5 carbon atoms is preferred. More preferred is —O—, —CONH—, —NHCO— or —NH—. More preferred is —O—, —CONH— or —NHCO—.
In the formula [1B], X ₆ is an organic group having 12 to 25 carbon atoms having a steroid skeleton, and more preferably an organic group having 15 to 25 carbon atoms having a steroid skeleton.
In formula [1B], q is an integer of 2-15. Especially, the integer of 2-10 is preferable. More preferred is an integer of 2 to 7.

式［２Ａ］中、Ｘ_１は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＮＨ−、−Ｎ（Ｒ_１）−（Ｒ_１は炭素数１〜５の直鎖状アルキル基又は炭素数１〜５の分岐状アルキル基である）又は−Ｓ−である。なかでも、単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＮＨ−又は−Ｎ（Ｒ_１）−（Ｒ_１は炭素数１〜５の直鎖状アルキル基又は炭素数１〜５の分岐状アルキル基である）が好ましい。より好ましくは、−Ｏ−、−ＣＯＮＨ−、−ＮＨＣＯ−又は−ＮＨ−である。さらに好ましくは、−Ｏ−、−ＣＯＮＨ−又は−ＮＨＣＯ−である。
式［２Ａ］中、Ｘ_２はベンゼン環、シクロヘキシル環又は複素環から選ばれる２価の環状基を示し、これらの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のアルコキシル基、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ル基又はフッ素原子で置換されていてもよい。その際、Ｘ_２は、同一であっても異なっていてもよい。なかでも、Ｘ_２はベンゼン環又はシクロヘキシル環が好ましい。 <Specific side chain diamine compound>
Specific polymer of the present invention, that is, at least one selected from the group consisting of a polyimide precursor obtained by reaction of a diamine component and a tetracarboxylic acid component and a polyimide obtained by dehydrating and ring-closing the polyimide precursor As a method for introducing the side chain structure, a diamine compound represented by the following formula [2A] (also referred to as a specific side chain diamine compound) is preferably used as a part of the raw material.

In Formula [2A], X ₁ represents a single bond, —O—, —COO—, —OCO—, —CONH—, —NHCO—, —NH—, —N (R ₁ ) — (R ₁ represents ₁ carbon atom) A linear alkyl group of -5 or a branched alkyl group of 1 to 5 carbon atoms) or -S-. Among them, a single bond, —O—, —COO—, —OCO—, —CONH—, —NHCO—, —NH— or —N (R ₁ ) — (R ₁ is a straight chain having 1 to 5 carbon atoms) An alkyl group or a branched alkyl group having 1 to 5 carbon atoms) is preferred. More preferred is —O—, —CONH—, —NHCO— or —NH—. More preferred is —O—, —CONH— or —NHCO—.
In the formula [2A], X ₂ represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring or a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, carbon It may be substituted with an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. At that time, X ₂ may be the same or different. Of these, X ₂ is preferably a benzene ring or a cyclohexyl ring.

In the formula [2A], X ₃ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. . Especially, a C1-C18 alkyl group, a C1-C10 fluorine-containing alkyl group, a C1-C18 alkoxyl group, or a C1-C10 fluorine-containing alkoxyl group is preferable. More preferably, they are a C1-C12 alkyl group or a C1-C12 alkoxyl group. More preferably, they are a C1-C10 alkyl group or a C1-C10 alkoxyl group.
In formula [2A], m is an integer of 2-15. Especially, the integer of 2-10 is preferable. More preferred is an integer of 2 to 7.
In the formula [2A], n is an integer of 1 to 3. Among these, an integer of 1 or 2 is preferable.
In formula [2A], p is an integer of 0-3. Especially, the integer of 0-2 is preferable.
In formula [2A], n + p is an integer of 1-6. Especially, the integer of 1-4 is preferable.
The bonding position of the _two amino groups (—NH ₂ ) in Formula [2A] is not limited. Specifically, with respect to the side chain linking group (— (CH ₂ ) _m —), 2, 3 position, 2, 4 position, 2, 5 position, 2, 6 position on the benzene ring , 3, 4 or 3, 5 positions. Among these, from the viewpoint of reactivity when synthesizing the polyimide precursor, positions 2, 4, 2, 5, or 3, 5 are preferable. More preferably, the position is 2, 4 or 3, 5 taking into account the ease of synthesis of the diamine compound.
The preferable combinations of X ₁ , X ₂ , X ₃ , m, n, and p in the formula [2A] are as shown in Table 1 to Table 30, as in the formula [1A].

式［２ａ］中、Ｒ_１は炭素数１〜１８のアルキル基、炭素数１〜１８のフッ素含有アルキル基、炭素数１〜１８のアルコキシル基又は炭素数１〜１８のフッ素含有アルコキシル基である。なかでも、炭素数１〜１８のアルキル基、炭素数１〜１０のフッ素含有アルキル基、炭素数１〜１８のアルコキシル基又は炭素数１〜１０のフッ素含有アルコキシル基が好ましい。より好ましくは、炭素数１〜１２のアルキル基又は炭素数１〜１２のアルコキシル基である。さらに好ましくは、炭素数１〜９のアルキル基又は炭素数１〜９のアルコキシル基である。
式［２ａ］中、ｍ１は２〜１５の整数である。なかでも、２〜１０の整数が好ましい。より好ましいのは、２〜７の整数である。
式［２ａ］中、ｐ１は０〜３の整数である。なかでも、０〜２の整数が好ましい。 A more preferable structure of the specific side chain type diamine compound of the present invention is a structure represented by the following formulas [2a] to [2d].

In Formula [2a], R ₁ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. . Especially, a C1-C18 alkyl group, a C1-C10 fluorine-containing alkyl group, a C1-C18 alkoxyl group, or a C1-C10 fluorine-containing alkoxyl group is preferable. More preferably, they are a C1-C12 alkyl group or a C1-C12 alkoxyl group. More preferably, they are a C1-C9 alkyl group or a C1-C9 alkoxyl group.
In formula [2a], m1 is an integer of 2-15. Especially, the integer of 2-10 is preferable. More preferred is an integer of 2 to 7.
In formula [2a], p1 is an integer of 0-3. Especially, the integer of 0-2 is preferable.

In the formula [2b], R ₂ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. . Especially, a C1-C18 alkyl group, a C1-C10 fluorine-containing alkyl group, a C1-C18 alkoxyl group, or a C1-C10 fluorine-containing alkoxyl group is preferable. More preferably, they are a C1-C12 alkyl group or a C1-C12 alkoxyl group. More preferably, they are a C1-C10 alkyl group or a C1-C10 alkoxyl group.
In formula [2b], m2 is an integer of 2-15. Especially, the integer of 2-10 is preferable. More preferred is an integer of 2 to 7.
In formula [2b], p2 is an integer of 0-3. Especially, the integer of 0-2 is preferable.
In Formula [2c], R ₃ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. . Especially, a C1-C18 alkyl group, a C1-C10 fluorine-containing alkyl group, a C1-C18 alkoxyl group, or a C1-C10 fluorine-containing alkoxyl group is preferable. More preferably, they are a C1-C12 alkyl group or a C1-C12 alkoxyl group. More preferably, they are a C1-C10 alkyl group or a C1-C10 alkoxyl group.
In formula [2c], m3 is an integer of 2-15. Especially, the integer of 2-10 is preferable. More preferred is an integer of 2 to 7.
In the formula [2c], n1 is an integer of 1 to 3. Among these, an integer of 1 or 2 is preferable.
In formula [2c], p3 is an integer of 0-3. Especially, the integer of 0-2 is preferable.
In formula [2c], n1 + p3 is an integer of 1-6. Especially, the integer of 1-4 is preferable.

In the formula [2d], R ₄ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. . Especially, a C1-C18 alkyl group, a C1-C10 fluorine-containing alkyl group, a C1-C18 alkoxyl group, or a C1-C10 fluorine-containing alkoxyl group is preferable. More preferably, they are a C1-C12 alkyl group or a C1-C12 alkoxyl group. More preferably, they are a C1-C10 alkyl group or a C1-C10 alkoxyl group.
In formula [2d], m4 is an integer of 2-15. Especially, the integer of 2-10 is preferable. More preferred is an integer of 2 to 7.
In formula [2d], n2 is an integer of 1 to 3. Among these, an integer of 1 or 2 is preferable.
In formula [2d], p4 is an integer of 0-3. Especially, the integer of 0-2 is preferable.
In formula [2d], n2 + p4 is an integer of 1-6. Especially, the integer of 1-4 is preferable.

The bonding position of the _two amino groups (—NH ₂ ) in Formula [2a] to Formula [2d] is not limited. Specifically, with respect to the side chain linking group (— (CH ₂ ) _{m1 to m4} —), 2, 3 positions, 2, 4 positions, 2, 5 positions on the benzene ring, 2, 6 Position, 3, 4 position, or 3, 5 position. Among these, from the viewpoint of reactivity when synthesizing the polyimide precursor, positions 2, 4, 2, 5, or 3, 5 are preferable. More preferably, the position is 2, 4 or 3, 5 taking into account the ease of synthesis of the diamine compound.
More specifically, for example, the structures are represented by the following formulas [2-1] to [2-40].

(In Formula [2-1] to Formula [2-40], R ₅ is each independently an alkyl group having 1 to 10 carbon atoms or an alkoxyl group having 1 to 10 carbon atoms, and m ₅ is each Independently, it is an integer of 2-7).
Among the above specific examples, [2-1] to [2-5], [2-8], [2-11], [2-12], formulas [2-14], [2-15], [2-15], 2-17] to [2-20], [2-25], [2-26], [2-29], and [2-30] are more preferable,
[2-1] to [2-5], [2-8], [2-11], [2-12], [2-14], [2-15], [2-17] to [2 −20] is more preferable.

式［２Ｂ］中、Ｘ_５は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＮＨ−、−Ｎ（Ｒ_２）−（Ｒ_２は炭素数１〜５の直鎖状アルキル基又は炭素数１〜５の分岐状アルキル基である）又は−Ｓ−である。なかでも、単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、ＮＨ−又は−Ｎ（Ｒ_２）−（Ｒ_２は炭素数１〜５の直鎖状アルキル基又は炭素数１〜５の分岐状アルキル基である）が好ましい。より好ましくは、−Ｏ−、−ＣＯＮＨ−、−ＮＨＣＯ−又は−ＮＨ−である。さらに好ましくは、−Ｏ−、−ＣＯＮＨ−又は−ＮＨＣＯ−である。
式［２Ｂ］中、Ｘ_６はステロイド骨格を有する炭素数１２〜２５の有機基であり、より好ましくはステロイド骨格を有する炭素数１５〜２５の有機基である。
式［２Ｂ］中、ｑは２〜１５の整数である。なかでも、２〜１０の整数が好ましい。より好ましいのは、２〜７の整数である。 In the specific polymer of the present invention, a diamine compound represented by the following formula [2B] (also referred to as a specific side chain diamine compound in the same manner as the diamine compound represented by the formula [2A]) is used as a part of the raw material. You can also.

In the formula [2B], X ₅ is a single bond, —O—, —COO—, —OCO—, —CONH—, —NHCO—, —NH—, —N (R ₂ ) — (R ₂ has 1 carbon atom) A linear alkyl group of -5 or a branched alkyl group of 1 to 5 carbon atoms) or -S-. Among them, a single bond, —O—, —COO—, —OCO—, —CONH—, —NHCO—, NH— or —N (R ₂ ) — (R ₂ is a linear alkyl having 1 to 5 carbon atoms. Group or a branched alkyl group having 1 to 5 carbon atoms) is preferable. More preferred is —O—, —CONH—, —NHCO— or —NH—. More preferred is —O—, —CONH— or —NHCO—.
In the formula [2B], X ₆ is an organic group having 12 to 25 carbon atoms having a steroid skeleton, and more preferably an organic group having 15 to 25 carbon atoms having a steroid skeleton.
In formula [2B], q is an integer of 2-15. Especially, the integer of 2-10 is preferable. More preferred is an integer of 2 to 7.

式［２−Ｉ］のジニトロ体は、ジニトロ体の−（ＣＨ_２）_ｍ−部を、連結部Ｘ_１を介して、−（Ｘ_２）_ｎ−（Ｘ_３）_ｐ−Ｘ_４を結合させる方法などで得ることができる。
Ｘ_１は単結合、−Ｏ−（エーテル結合）、−ＣＯＯ−（エステル結合）、−ＯＣＯ−（逆エステル結合）、−ＣＯＮＨ−（アミド結合）、−ＮＨＣＯ−（逆アミド結合）、−ＮＨ−（アミノ結合）、−Ｎ（Ｒ_１）−（Ｒ_１は炭素数１〜５の直鎖状アルキル基又は炭素数１〜５の分岐状アルキル基であるアルキル化アミノ結合）又は−Ｓ−（Ｓ結合）より選ばれる結合基であり、これらの結合基は、有機合成における公知の手法を適宜選択して用い、形成することができる。

<Synthesis Method of Specific Side Chain Type Diamine Compound>
Although the method for producing the specific side chain diamine compound represented by the formula [2A] or the formula [2B] of the present invention is not particularly limited, for example, it can be produced by the following method.
For example, the specific diamine compound represented by the formula [2A] of the present invention can be obtained by synthesizing a dinitro compound represented by the formula [2-I] and further reducing the nitro group to convert it to an amino group. The method for reducing the dinitro compound is not particularly limited. Usually, palladium-carbon, platinum oxide, Raney nickel, platinum black, rhodium-alumina, platinum sulfide carbon, etc. are used as a catalyst, ethyl acetate, toluene, tetrahydrofuran, dioxane, There is a method in which hydrogen gas, hydrazine, hydrogen chloride, or the like is used in an alcohol-based solvent. X ₁ , X ₂ , X ₃ , X ₄ , m, n, and p in the formula [2-I] are the same as defined in the formula [2A].

Dinitro of formula [2-I] is of the dinitro product - _{(CH 2) m} - the part, through the connecting portion _{X 1, - (X 2)} n - to _{(X 3)} binding the p -X ₄ It can be obtained by a method.
X ₁ is a single bond, —O— (ether bond), —COO— (ester bond), —OCO— (reverse ester bond), —CONH— (amide bond), —NHCO— (reverse amide bond), —NH -(Amino bond), -N (R ₁ )-(R ₁ is an alkylated amino bond which is a linear alkyl group having 1 to 5 carbon atoms or a branched alkyl group having 1 to 5 carbon atoms) or -S- These linking groups are selected from (S bonds), and these linking groups can be formed by appropriately selecting and using known methods in organic synthesis.

For example, when X ₁ is —O— (ether bond), a dinitro group-containing halogen derivative in which Xa in the formula [2-II] is a halogen, and Xb in the formula [2-III] are a hydroxyl group (OH group). And a method of reacting with a hydroxyl group derivative in the presence of an alkali. The halogen of the dinitro group-containing halogen derivative is preferably Cl (chlorine) or Br (bromine). A dinitro group-containing halogen derivative can be obtained by halogenation of a corresponding dinitrobenzyl alcohol. Examples of the halogenating agent used at that time include BBr ₃ , BCl ₃ , PBr ₃ , PCl ₃ , PPh ₃ / CBr ₄ , PPh ₃ / CCl ₄ , SOBr ₂ , and SOCl ₂ .
When X ₁ is —COO— (ester bond), a dinitro group-containing acid chloride derivative in which Xa in the formula [2-II] is an acid chloride, and Xb in the formula [2-III] are a hydroxyl group (OH group). And a method of reacting with a hydroxyl group derivative in the presence of an alkali.
When X ₁ is —OCO— (reverse ester bond), a dinitro group-containing hydroxyl derivative in which Xa in formula [2-II] is a hydroxyl group (OH group), and Xb in formula [2-III] is an acid chloride. And a method in which an acid chloride derivative is reacted in the presence of an alkali.
When X ₁ is —CONH— (amide bond), a dinitro group-containing acid chloride derivative in which Xa in the formula [2-II] is an acid chloride, and Xb in the formula [2-III] are an amino group (NH ₂ And an amino group derivative which is a group) in the presence of an alkali.

When X ₁ is —NHCO— (reverse amide bond), a dinitro group-containing amino group derivative in which Xa in formula [2-II] is an amino group (NH ₂ group), and Xb in formula [2-III] And an acid chloride derivative in which is an acid chloride is reacted in the presence of an alkali.
When X ₁ is —NH— (amino bond) or N (R ₁ ) — (alkylated amino bond), a dinitro group-containing halogen derivative in which Xa in the formula [2-II] is a halogen, III] in which Xb is an amino group (NH ₂ group) or an alkylated amino group (NH (R ₁ ) group) is reacted in the presence of an alkali.
In the specific side chain diamine compound represented by the above formula [2A], a novel compound is also included.

<Other diamine compounds>
In the present invention, as long as the effects of the present invention are not impaired, other diamine compounds (also referred to as other diamine compounds) other than the specific side chain diamine compound can be used as the diamine component. Specific examples are given below.
p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2, 5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4 , 6-diaminoresorcinol, 4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 3,3′-dihydroxy -4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-diph Fluoro-4,4′-biphenyl, 3,3′-trifluoromethyl-4,4′-diaminobiphenyl, 3,4′-diaminobiphenyl, 3,3′-diaminobiphenyl, 2,2′-diaminobiphenyl, 2,3′-diaminobiphenyl, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 2,2′-diaminodiphenylmethane, 2,3′-diaminodiphenylmethane, 4, 4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldianiline, 3,3 '-Sulfonyldianiline, bis (4-aminophenyl) silane, bis (3-amino Nophenyl) silane, dimethyl-bis (4-aminophenyl) silane, dimethyl-bis (3-aminophenyl) silane, 4,4′-thiodianiline, 3,3′-thiodianiline, 4,4′-diaminodiphenylamine, 3, 3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl (4,4'-diaminodiphenyl) amine, N-methyl (3 3'-diaminodiphenyl) amine, N-methyl (3,4'-diaminodiphenyl) amine, N-methyl (2,2'-diaminodiphenyl) amine, N-methyl (2,3'-diaminodiphenyl) amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone 1,4-diaminonaphthalene, 2,2′-diaminobenzophenone, 2,3′-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8- Diaminonaphthalene, 2,5-diaminonaphthalene, 2,6 diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis (4-aminophenyl) ethane, 1,2-bis (3 -Aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,3-bis (3-aminophenyl) propane, 1,4-bis (4aminophenyl) butane, 1,4-bis ( 3-aminophenyl) butane, bis (3,5-diethyl-4-aminophenyl) methane, 1,4-bis (4-aminophenoxy) ben 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (4-amino) Benzyl) benzene, 1,3-bis (4-aminophenoxy) benzene, 4,4 ′-[1,4-phenylenebis (methylene)] dianiline, 4,4 ′-[1,3-phenylenebis (methylene) ] Dianiline, 3,4 ′-[1,4-phenylenebis (methylene)] dianiline, 3,4 ′-[1,3-phenylenebis (methylene)] dianiline, 3,3 ′-[1,4-phenylene Bis (methylene)] dianiline, 3,3 ′-[1,3-phenylenebis (methylene)] dianiline, 1,4-phenylenebis [(4-aminophenyl) methanone], 1,4-phenylenebis [(3 -Ami Phenyl) methanone], 1,3-phenylenebis [(4-aminophenyl) methanone], 1,3-phenylenebis [(3-aminophenyl) methanone], 1,4-phenylenebis (4-aminobenzoate), 1,4-phenylenebis (3-aminobenzoate), 1,3-phenylenebis (4-aminobenzoate), 1,3-phenylenebis (3-aminobenzoate), bis (4-aminophenyl) terephthalate, bis ( 3-aminophenyl) terephthalate, bis (4-aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, N, N ′-(1,4-phenylene) bis (4-aminobenzamide), N, N '-(1,3-phenylene) bis (4-aminobenzamide), N, N'-(1,4-phenylene) bi (3-aminobenzamide), N, N ′-(1,3-phenylene) bis (3-aminobenzamide), N, N′-bis (4-aminophenyl) terephthalamide, N, N′-bis (3 -Aminophenyl) terephthalamide, N, N'-bis (4-aminophenyl) isophthalamide, N, N'-bis (3-aminophenyl) isophthalamide, 9,10-bis (4-aminophenyl) anthracene, 4,4′-bis (4-aminophenoxy) diphenylsulfone, 2,2′-bis [4- (4-aminophenoxy) phenyl] propane, 2,2′-bis [4- (4-aminophenoxy) phenyl ] Hexafluoropropane, 2,2'-bis (4-aminophenyl) hexafluoropropane, 2,2'-bis (3-aminophenyl) hexafluoropropane, , 2′-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2′-bis (4-aminophenyl) propane, 2,2′-bis (3-aminophenyl) propane, 2,2 '-Bis (3-amino-4-methylphenyl) propane, 1,3-bis (4-aminophenoxy) propane, 1,3-bis (3-aminophenoxy) propane, 1,4-bis (4-amino) Phenoxy) butane, 1,4-bis (3-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 1,5-bis (3-aminophenoxy) pentane, 1,6-bis (4 -Aminophenoxy) hexane, 1,6-bis (3-aminophenoxy) hexane, 1,7-bis (4-aminophenoxy) heptane, 1,7- (3-aminophenoxy) heptane 1,8-bis (4-aminophenoxy) octane, 1,8-bis (3-aminophenoxy) octane, 1,9-bis (4-aminophenoxy) nonane, 1,9-bis (3-aminophenoxy) Nonane, 1,10- (4-aminophenoxy) decane, 1,10- (3-aminophenoxy) decane, 1,11- (4-aminophenoxy) undecane, 1,11- (3-aminophenoxy) undecane, 1,12- (4-aminophenoxy) dodecane, 1,12- (3-aminophenoxy) dodecane, 4- (aminomethyl) aniline, 3- (aminomethyl) aniline, 4- (2-aminoethyl) aniline or Aromatic diamines such as 3- (2-aminoethylaniline); bis (4-aminocyclohexyl) methane, bis (4-amino-3-methyl Cyclohexyl) alicyclic diamines such as methane; 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8- Aliphatic diamines such as diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane.

（式［ＤＡ−１］〜式［ＤＡ−３］中、Ｒ_１は、−Ｏ−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−ＣＯＯＣＨ_２−又は−ＣＨ_２ＯＣＯ−であり、Ｒ_２は、炭素数１〜２２の直鎖状又は分岐状アルキル基、炭素数１〜２２の直鎖状又は分岐状アルコキシル基、炭素数１〜２２の直鎖状又は分岐状フッ素含有アルキル基、又は炭素数１〜２２の直鎖状又は分岐状フッ素含有アルコキシル基である。）

（式［ＤＡ−４］〜式［ＤＡ−６］中、Ｒ_３は、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＯＣＨ_２−、−ＣＨ_２ＯＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−又は−ＣＨ_２−であり、Ｒ_４は、炭素数１〜２２の直鎖状又は分岐状アルキル基、炭素数１〜２２の直鎖状又は分岐状アルコキシル基、炭素数１〜２２の直鎖状又は分岐状フッ素含有アルキル基、又は炭素数１〜２２の直鎖状又は分岐状フッ素含有アルコキシル基である。）

（式［ＤＡ−７］及び式［ＤＡ−８］中、Ｒ_５は、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＯＣＨ_２−、−ＣＨ_２ＯＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＨ_２−又は−Ｏ−であり、Ｒ_６は、フッ素基、シアノ基、トリフルオロメタン基、ニトロ基、アゾ基、ホルミル基、アセチル基、アセトキシ基又は水酸基である。）

（式［ＤＡ−９］及び式［ＤＡ−１０］中、Ｒ_７は、炭素数３〜１２の直鎖状又は分岐状アルキル基であり、１,４-シクロヘキシレンのシス−トランス異性は、それぞれトランス異性体である。）

（式［ＤＡ−１１］及び式［ＤＡ−１２］中、Ｒ_８は、炭素数３〜１２の直鎖状又は分岐状アルキル基であり、１,４-シクロヘキシレンのシス−トランス異性は、それぞれトランス異性体である。） Moreover, as long as the effect of this invention is not impaired, the diamine compound shown by the following formula [DA-1]-a formula [DA-31] can be used.

(In Formula [DA-1] to Formula [DA-3], R ₁ is —O—, —OCH ₂ —, —CH ₂ O—, —COOCH ₂ — or —CH ₂ OCO—, and R ₂ Is a linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched alkoxyl group having 1 to 22 carbon atoms, a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms, or (It is a linear or branched fluorine-containing alkoxyl group having 1 to 22 carbon atoms.)

(In Formula [DA-4] to Formula [DA-6], R ₃ represents —COO—, —OCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH ₂ O—, —OCH ₂ — or —CH ₂ — and R ₄ is a linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched alkoxyl group having 1 to 22 carbon atoms, or a linear chain having 1 to 22 carbon atoms. Or a branched fluorine-containing alkyl group or a linear or branched fluorine-containing alkoxyl group having 1 to 22 carbon atoms.)

(In Formula [DA-7] and Formula [DA-8], R ₅ represents —COO—, —OCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH ₂ O—, —OCH ₂ —, —CH ₂ — or —O—, and R ₆ is a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group, or a hydroxyl group.

(In Formula [DA-9] and Formula [DA-10], R ₇ is a linear or branched alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is Each is a trans isomer.)

(In Formula [DA-11] and Formula [DA-12], R ₈ is a linear or branched alkyl group having 3 to 12 carbon atoms, and cis-trans isomerism of 1,4-cyclohexylene is Each is a trans isomer.)

（式［ＤＡ−１３］中、Ａ_４は、フッ素原子で置換されていてもよい炭素数３〜２０の直鎖状又は分岐状アルキル基であり、Ａ_３は、１，４−シクロへキシレン基又は１，４−フェニレン基であり、Ａ_２は、−Ｏ−又は−ＣＯＯ−＊（ただし、「＊」を付した結合手がＡ_３と結合する）であり、Ａ_１は、−Ｏ−又は−ＣＯＯ−＊（ただし、「＊」を付した結合手が（ＣＨ_２）ａ_２）と結合する）である。また、ａ_１は０又は１の整数であり、ａ_２は２〜１０の整数であり、ａ_３は０又は１の整数である。）

(In the formula [DA-13], A ₄ is a linear or branched alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, and A ₃ is 1,4-cyclohexylene. Or a 1,4-phenylene group, A ₂ is —O— or —COO— * (where a bond marked with “*” is bonded to A ₃ ), and A ₁ is —O— - or -COO - * (wherein "*" a bond marked is _(CH 2) _{a 2)} is a bond to). A ₁ is an integer of 0 or 1, a ₂ is an integer of ₂ to 10, and a ₃ is an integer of 0 or 1. )

（式［ＤＡ−３２］中、Ａ_１は、−Ｏ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＯ−、−ＣＯＮ（ＣＨ_３）−又は−Ｎ（ＣＨ_３）ＣＯ−より選ばれる２価の有機基であり、Ａ_２は、単結合、炭素数１〜２０の脂肪族炭化水素基、非芳香族環式炭化水素基又は芳香族炭化水素基である。Ａ_３は、単結合、−Ｏ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮ（ＣＨ_３）−、−Ｎ（ＣＨ_３）ＣＯ−又は−Ｏ（ＣＨ_２）_ｍ−（ｍは１〜５の整数である）であり、Ａ_４は、窒素含有芳香族複素環である。ｎは１〜４の整数である。）
また、本発明の効果を損なわない限りにおいて、ジアミン側鎖にアルキル基又はフッ素含有アルキル基を有するジアミン化合物を用いることができる。
具体的には、下記の式［ＤＡ−３３］〜式［ＤＡ−４４］で示されるジアミンを例示することができる。

（式［ＤＡ−３３］〜式［ＤＡ−３７］中、Ａ_１は、炭素数１〜２２の直鎖状又は分岐状アルキル基、又は炭素数１〜２２の直鎖状又は分岐状フッ素含有アルキル基である。） Furthermore, a diamine compound represented by the following formula [DA-32] can be used as long as the effects of the present invention are not impaired.

(In the formula [DA-32], A ₁ represents —O—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —OCO—, —CON ( A divalent organic group selected from CH ₃ ) — or —N (CH ₃ ) CO—, and A ₂ is a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a non-aromatic cyclic hydrocarbon. A ₃ is a single bond, —O—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —COO—, —OCO—, — CON (CH ₃ ) —, —N (CH ₃ ) CO—, or —O (CH ₂ ) _m — (m is an integer of 1 to 5), and A ₄ is a nitrogen-containing aromatic heterocycle. N is an integer of 1 to 4.)
Moreover, as long as the effect of this invention is not impaired, the diamine compound which has an alkyl group or a fluorine-containing alkyl group in a diamine side chain can be used.
Specifically, diamines represented by the following formulas [DA-33] to [DA-44] can be exemplified.

(In Formula [DA-33] to Formula [DA-37], A ₁ is a linear or branched alkyl group having 1 to 22 carbon atoms, or a linear or branched fluorine group having 1 to 22 carbon atoms. An alkyl group.)

（式［ＤＡ−３８］〜式［ＤＡ−４３］中、Ａ_２は、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２−、−Ｏ−、−ＣＯ−又は−ＮＨ−であり、Ａ_３は、炭素数１〜２２の直鎖状又は分岐状アルキル基、又は炭素数１〜２２の直鎖状又は分岐状フッ素含有アルキル基である。）

（式［ＤＡ−４４］中、ｐは１〜１０の整数である。）
さらに、本発明の効果を損なわない限りにおいて、下記の式［ＤＡ−４５］〜式［ＤＡ−５２］で示されるジアミン化合物を用いることもできる。

（式［ＤＡ−４９］中、ｍは０〜３の整数である。式［ＤＡ−５２］中、ｎは１〜５の整数である。）

(In Formula [DA-38] to Formula [DA-43], A ₂ represents —COO—, —OCO—, —CONH—, —NHCO—, —CH ₂ —, —O—, —CO— or — NH— and A ₃ is a linear or branched alkyl group having 1 to 22 carbon atoms, or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms.

(In Formula [DA-44], p is an integer of 1 to 10.)
Furthermore, as long as the effects of the present invention are not impaired, diamine compounds represented by the following formulas [DA-45] to [DA-52] can also be used.

(In Formula [DA-49], m is an integer of 0-3. In Formula [DA-52], n is an integer of 1-5.)

（式［ＤＡ−５３］中、ｍ_１は１〜４の整数である。式［ＤＡ−５４］中、Ａ_４は、単結合、−ＣＨ_２−、−Ｃ_２Ｈ_４−、−Ｃ（ＣＨ_３）_２−、−ＣＦ_２−、−Ｃ（ＣＦ_３）_２−、−Ｏ−、−ＣＯ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮ（ＣＨ_３）−又は−Ｎ（ＣＨ_３）ＣＯ−であり、ｍ_２及びｍ_３は、それぞれ独立して、０〜４の整数であり、かつｍ_２＋ｍ_３は、１〜４の整数である。式［ＤＡ−５５］中、ｍ_４及びｍ_５は、それぞれ独立して、１〜５の整数である。式［ＤＡ−５６］中、Ａ_５は、炭素数１〜５の直鎖状又は分岐状アルキル基であり、ｍ_６は、１〜５の整数である。式［ＤＡ−５７］中、Ａ_６は、単結合、−ＣＨ_２−、−Ｃ_２Ｈ_４−、−Ｃ（ＣＨ_３）_２−、−ＣＦ_２−、−Ｃ（ＣＦ_３）_２−、−Ｏ−、−ＣＯ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮ（ＣＨ_３）−又は−Ｎ（ＣＨ_３）ＣＯ−であり、ｍ_７は、１〜４の整数である。） Furthermore, as long as the effects of the present invention are not impaired, a diamine compound having a carboxyl group in the molecule represented by the following formula [DA-53] to formula [DA-57] can also be used.

(In Formula [DA-53], m ₁ is an integer of ₁ to 4. In Formula [DA-54], A ₄ represents a single bond, —CH ₂ —, —C ₂ H ₄ —, —C ( _{CH 3) 2 -, - CF} 2 -, - C (CF 3) 2 -, - O -, - CO -, - NH -, - N (CH 3) -, - CONH -, - NHCO -, - CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —CON (CH ₃ ) — or —N (CH ₃ ) CO—, each of m ₂ and m ₃ independently represents 0 to And m ₂ + m ₃ is an integer of 1 to 4. In the formula [DA-55], m ₄ and m ₅ are each independently an integer of 1 to 5. In [DA-56], A ₅ is a linear or branched alkyl group having 1 to 5 carbon atoms, and m ₆ is an integer of 1 to 5. In Formula [DA-57], A ₆ Is simply _{If, -CH 2 -, - C 2} H 4 -, - C (CH 3) 2 -, - CF 2 -, - C (CF 3) 2 -, - O -, - CO -, - NH -, - N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —CON (CH ₃ ) — or —N (CH ₃ ) CO— And m ₇ is an integer of 1 to 4.)

上記のその他ジアミン化合物は、液晶配向膜とした際の液晶配向性、電圧保持率、蓄積電荷などの特性に応じて、１種類又は２種類以上を混合して使用することもできる。 Furthermore, as long as the effects of the present invention are not impaired, diamine compounds represented by the following formulas [DA-58] and [DA-59] can also be used.

Said other diamine compound can also be used 1 type or in mixture of 2 or more types according to characteristics, such as liquid crystal orientation at the time of setting it as a liquid crystal aligning film, a voltage holding rate, and an accumulation charge.

式［３］中、Ｚ_１は、炭素数４〜１３の４価の有機基であり、かつ炭素数４〜１０の非芳香族環状炭化水素基を含有する。
Ｚ_１は、具体的には、例えば下記の式［３ａ］〜式［３ｊ］で示される４価の基である。

<Specific tetracarboxylic dianhydride>
In order to obtain the specific polymer of the present invention, it is preferable to use a tetracarboxylic dianhydride (also referred to as a specific tetracarboxylic dianhydride) represented by the following formula [3] as a part of the raw material.

In the formula [3], Z ₁ is a tetravalent organic group having 4 to 13 carbon atoms and contains a non-aromatic cyclic hydrocarbon group having 4 to 10 carbon atoms.
Specifically, Z ₁ is a tetravalent group represented by, for example, the following formula [3a] to formula [3j].

In the formula [3a], Z _{2 to} Z ₅ are groups selected from a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different.
In the formula [3g], Z ₆ and Z ₇ are a hydrogen atom or a methyl group, and may be the same or different.
In the formula [3], particularly preferred structure of Z ₁ is the formula [3a], the formula [3c], the formula [3d], the formula [3e], the formula [3f] or the formula from the viewpoint of polymerization reactivity and ease of synthesis. [3 g]. Among these, the formula [3a], the formula [3e], the formula [3f], or the formula [3g] is preferable.

<Other tetracarboxylic dianhydrides>
In the present invention, other tetracarboxylic dianhydrides other than the specific tetracarboxylic dianhydride (also referred to as other tetracarboxylic dianhydrides) can be used as long as the effects of the present invention are not impaired. Other tetracarboxylic dianhydrides include tetracarboxylic dianhydrides of the following tetracarboxylic acids.
Pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7 Anthracene tetracarboxylic acid, 1,2,5,6-anthracene tetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4-biphenyltetracarboxylic acid, bis ( 3,4-dicarboxyphenyl) ether, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) methane, 2 , 2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3,4-dicarboxyphenyl) propane, bi (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis (3,4-dicarboxy) Phenyl) pyridine, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid acid.
The above-mentioned specific tetracarboxylic dianhydride and other tetracarboxylic dianhydrides may be used alone or in combination of two or more depending on the properties such as liquid crystal alignment, voltage holding ratio and accumulated charge when the liquid crystal alignment film is used. It can also be used by mixing.

（式［Ａ］中、Ｒ_１は４価の有機基であり、Ｒ_２は２価の有機基であり、Ａ_１及びＡ_２は、水素原子又は炭素数１〜８のアルキル基であり、それぞれ同じであっても異なってもよい。ｎは正の整数を示す。）
本発明の特定重合体は、下記の式［Ｂ］で示されるジアミン成分と、下記の式［Ｃ］で示されるテトラカルボン酸二無水物とを原料とすることで比較的簡便に得られるという理由から、下記の式［Ｄ］で示される繰り返し単位の構造式からなるポリアミド酸又は該ポリアミド酸をイミド化させたポリイミドが好ましい。

（式［Ｂ］、式［Ｃ］及び式［Ｄ］中、Ｒ_１及びＲ_２は、式［Ａ］で定義したものと同意義である。）
式［Ａ］及び式［Ｄ］において、Ｒ_１及びＲ_２は、それぞれ１種類でもあっても、それぞれ異なったＲ_１及びＲ_２を有して、繰り返し単位として異なった複数種を組み合わせたものでもよい。 <Specific polymer>
The specific polymer of the present invention is at least one polymer selected from the group consisting of a polyamic acid obtained by reacting a diamine component and a tetracarboxylic acid component and a polyimide obtained by dehydrating and ring-closing the polyamic acid. .
The polyimide precursor has a structure represented by the following formula [A].

(In the formula [A], R ₁ is a tetravalent organic group, R ₂ is a divalent organic group, A ₁ and A ₂ are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, Each may be the same or different, and n represents a positive integer.)
The specific polymer of the present invention is relatively easily obtained by using a diamine component represented by the following formula [B] and a tetracarboxylic dianhydride represented by the following formula [C] as raw materials. For the reason, a polyamic acid having a structural formula of a repeating unit represented by the following formula [D] or a polyimide obtained by imidizing the polyamic acid is preferable.

(In formula [B], formula [C] and formula [D], R ₁ and R ₂ have the same meaning as defined in formula [A].)
In the formulas [A] and [D], R ₁ and R ₂ may be one kind each, but each may have different R ₁ and R ₂ and may be a combination of different kinds as repeating units. But you can.

In the present invention, the method for synthesizing the specific polymer is not particularly limited. Usually, it is obtained by reacting a diamine component and a tetracarboxylic acid component. Generally, at least one tetracarboxylic acid component selected from the group consisting of tetracarboxylic acids and derivatives thereof is reacted with a diamine component consisting of one or more diamine compounds to obtain a polyamic acid. Specifically, a method of obtaining polyamic acid by polycondensation of tetracarboxylic dianhydride and a diamine component, a method of obtaining polyamic acid by dehydration polycondensation reaction of tetracarboxylic acid and a diamine component, or tetracarboxylic acid A method of polycondensation of a dihalide and a diamine component to obtain a polyamic acid is used.
To obtain the polyamic acid alkyl ester, a method of polycondensing a tetracarboxylic acid obtained by dialkyl esterification of a carboxylic acid group and a diamine component, and a polycondensation of a tetracarboxylic acid dihalide obtained by dialkyl esterifying a carboxylic acid group and a diamine component. The method or the method of converting the carboxyl group of a polyamic acid into 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.

When the liquid crystal alignment film obtained by using the specific polymer of the present invention is a liquid crystal alignment film as the content ratio of the specific side chain structure represented by the formula [1A] or the formula [1B] in the diamine component increases. The hydrophobicity of the liquid crystal and the pretilt angle of the liquid crystal can be increased. In that case, it is preferable to use the specific side chain type diamine compound shown by the said Formula [2A] or Formula [2B] for a diamine component. Particularly preferably, a specific side chain diamine compound represented by the formula [2A] is used. In order to enhance this property, it is preferable that 5 mol% or more and 80 mol% or less of the diamine component is the specific side chain type diamine compound. Especially, it is preferable that 5 mol% or more and 60 mol% or less of a diamine component are a specific side chain type diamine compound from the viewpoint of the applicability | paintability of a liquid crystal aligning agent, and the electrical property as a liquid crystal aligning film.
In order to obtain the specific polymer of this invention, it is preferable to use the specific tetracarboxylic dianhydride shown by said Formula [3] as a tetracarboxylic-acid component. In particular, it is preferable to use a tetracarboxylic dianhydride in which Z ₁ in Formula [3] is a structure represented by Formula [3a] to Formula [3j]. In that case, it is preferable that 1 mol% or more of a tetracarboxylic acid component is a specific tetracarboxylic dianhydride, More preferably, it is 5 mol% or more, More preferably, it is 10 mol% or more. Further, 100 mol% of the tetracarboxylic acid component may be a specific tetracarboxylic dianhydride.
The reaction of the diamine component and the tetracarboxylic acid component is usually performed in an organic solvent. The organic solvent used at that time is not particularly limited as long as the produced polyimide precursor is dissolved. Specific examples are given below.

For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone or 4 -Hydroxy-4-methyl-2-pentanone and the like.
These may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve a polyimide precursor, you may mix and use the said solvent in the range which the produced | 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 dispersed or dissolved in the organic solvent as it is. And a method of adding a diamine component to a solution obtained by dispersing or dissolving a tetracarboxylic acid component in an organic solvent, a method of alternately adding a tetracarboxylic acid component and a diamine component, etc. Any of these methods may be used. In addition, when reacting using a plurality of diamine components or tetracarboxylic acid components, they may be reacted in a premixed state, individually or sequentially, or further individually reacted low molecular weight substances. May be mixed and reacted to form a specific polymer. Although the polymerization temperature in that case can select arbitrary temperature of -20-150 degreeC, Preferably it is the range of -5-100 degreeC. The reaction can be carried out at any concentration, but if the concentration is too low, it will be difficult to obtain a specific polymer having a high molecular weight, and if the concentration is too high, the viscosity of the reaction solution will become too high and uniform stirring will occur. It becomes difficult. Therefore, Preferably it is 1-50 mass%, More preferably, it is 5-30 mass%. It is also possible to carry out at a high concentration in the initial stage of the reaction and then add an organic solvent.

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 a normal polycondensation reaction, the molecular weight of the polyimide precursor formed increases as the molar ratio approaches 1.0.
The polyimide of the present invention is a polyimide obtained by ring-closing the above polyimide precursor, and is useful as a polymer for obtaining a liquid crystal alignment film.
In the polyimide of the present invention, the cyclization rate (imidization rate) of the amic acid group is not necessarily 100%, and can be arbitrarily adjusted according to the application and purpose.
Examples of the method for imidizing the polyimide precursor include thermal imidization in which the polyimide precursor solution is heated as it is or catalyst imidization in which a catalyst is added to the polyimide precursor solution.
The temperature when the polyimide precursor is thermally imidized in the solution is 100 to 400 ° C., preferably 120 to 250 ° C., and it is preferable to carry out while removing water generated by the imidation 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 amic acid group, and the amount of the acid anhydride is 1 to 50 mol times of the amido group, preferably 3 to 3 times. 30 mole times. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Among them, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated. The imidization rate 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 collected by filtration, and then dried by normal temperature or reduced pressure at room temperature or by heating. Moreover, when the polymer which carried out precipitation collection | recovery is re-dissolved in an organic solvent and the operation which carries out reprecipitation collection | recovery is repeated 2 to 10 times, the impurity in a polymer can be decreased. 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 specific polymer of the present invention was measured by GPC (Gel Permeation Chromatography) method in consideration of the strength of the polymer film obtained therefrom, workability at the time of forming the polymer film, and uniformity of the polymer film. The weight average molecular weight is preferably 5,000 to 1,000,000, and more preferably 10,000 to 150,000.

<Liquid crystal alignment agent>
The liquid-crystal aligning agent of this invention is a coating liquid for forming a liquid crystal aligning film, and is a coating liquid for forming the resin film containing a specific polymer and an organic solvent.
In the liquid crystal alignment treatment agent of the present invention, all the polymer components may be all specific polymers used in the present invention, and other polymers are mixed with the specific polymer of the present invention. May be. In that case, content of the other polymer other than that is 0.5 to 15% by mass, preferably 1 to 10% by mass. Other polymers include polyimide precursors or polyimides that do not contain a specific side chain structure. Furthermore, polyimide precursors and polymers other than polyimide, specifically, acrylic polymers, methacrylic polymers, polystyrene, polyamides, etc. are mentioned. The organic solvent in the liquid crystal alignment treatment agent of the present invention forms a uniform film by coating. From the viewpoint of forming, the content of the organic solvent is preferably 70 to 99% by mass, and more preferably 80 to 99% by mass. This content can be appropriately changed depending on the film thickness of the target liquid crystal alignment film. The organic solvent at that time is not particularly limited as long as it is an organic solvent capable of dissolving the specific polymer. Specific examples are given below.
For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4 -Hydroxy-4-methyl-2-pentanone and the like.
These may be used alone or in combination.

As long as the effects of the present invention are not impaired, the liquid crystal aligning agent of the present invention includes a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group, a cyclocarbonate group, etc., a hydroxyl group, a hydroxyalkyl group, and a lower alkoxyalkyl group. A crosslinkable compound having at least one substituent selected from the group, a crosslinkable compound having a polymerizable unsaturated bond, and the like can also be introduced. It is necessary to have two or more of these substituents and polymerizable unsaturated bonds in the crosslinkable compound.
Examples of the crosslinkable compound having an epoxy group or an isocyanate group include bisphenolacetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidylaminodiphenylene, tetraglycidyl-m-xylenediamine, Tetraglycidyl-1,3-bis (aminoethyl) cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetodiglycidyl ether, 1,3-bis (1- (2,3-epoxypropoxy) -1-trifluoromethyl-2,2,2-trifluoromethyl) benzene, 4,4-bis (2,3-epoxypropoxy) octafluorobiphenyl Triglycidyl-p-aminophenol, tetraglycidylmetaxylenediamine, 2- (4- (2,3-epoxypropoxy) phenyl) -2- (4- (1,1-bis (4- (2,3-epoxy) Propoxy) phenyl) ethyl) phenyl) propane, 1,3-bis (4- (1- (4- (2,3-epoxypropoxy) phenyl) -1- (4- (1- (4- (2,3 -Epoxypropoxy) phenyl) -1-methylethyl) phenyl) ethyl) phenoxy) -2-propanol and the like.

具体的には、下記の式［４−１］〜式［４−１１］で示される架橋性化合物である。

The crosslinkable compound having an oxetane group is a crosslinkable compound having at least two oxetane groups represented by the following formula [4].

Specifically, it is a crosslinkable compound represented by the following formula [4-1] to formula [4-11].

具体的には、下記の式［５−１］〜式［５−３７］で示される架橋性化合物である。

The crosslinkable compound having a cyclocarbonate group is a crosslinkable compound having at least two cyclocarbonate groups represented by the following formula [5].

Specifically, it is a crosslinkable compound represented by the following formula [5-1] to formula [5-37].

（式［５−２４］中、ｎは１〜５の整数である。式［５−２５］中、ｎは１〜５の整数である。式［５−３６］中、ｎは１〜１００の整数である。式［５−３７］中、ｎは１〜１０の整数である。）

(In Formula [5-24], n is an integer of 1-5. In Formula [5-25], n is an integer of 1-5. In Formula [5-36], n is 1-100. (In the formula [5-37], n is an integer of 1 to 10.)

（式［５−３８］〜式［５−４０］中、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４及びＲ_５は、それぞれ独立して、式［５］で示される構造、水素原子、水酸基、炭素数１〜１０のアルキル基、アルコキシル基、脂肪族環又は芳香族環であり、少なくとも１つは式［５］で示される構造である。）
より具体的には、下記の式［５−４１］及び式［５−４２］の化合物が挙げられる。

（式［５−４２］中、ｎは１〜１０の整数である。） Furthermore, the polysiloxane which has at least 1 type of structure shown by the following formula [5-38]-a formula [5-40] can also be mentioned.

(In Formula [5-38] to Formula [5-40], R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently a structure represented by Formula [5], a hydrogen atom, a hydroxyl group. And an alkyl group having 1 to 10 carbon atoms, an alkoxyl group, an aliphatic ring or an aromatic ring, at least one of which is a structure represented by the formula [5].
More specifically, compounds of the following formula [5-41] and formula [5-42] are mentioned.

(In Formula [5-42], n is an integer of 1 to 10.)

Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxyl group include, for example, amino resins having a hydroxyl group or an alkoxyl group, such as melamine resin, urea resin, guanamine resin, glycol Examples include uril-formaldehyde resin, succinylamide-formaldehyde resin, and ethylene urea-formaldehyde resin. Specifically, a melamine derivative, a benzoguanamine derivative, glycoluril, or the like in which a hydrogen atom of an amino group is substituted with a methylol group and / or an alkoxymethyl group can be used. The melamine derivative or benzoguanamine derivative can exist as a dimer or a trimer. These preferably have an average of 3 to 6 methylol groups or alkoxymethyl groups per triazine ring.
As an example of such a melamine derivative or a benzoguanamine derivative, MX-750 in which an average of 3.7 methoxymethyl groups is substituted per one triazine ring in a commercially available product, and an average of 5. methoxymethyl groups per one triazine ring. Eight-substituted MW-30 (manufactured by Sanwa Chemical Co., Ltd.), Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712 and other methoxymethylated melamine, Cymel 235, Of methoxymethylated butoxymethylated melamine such as 236, 238, 212, 253, 254, butoxymethylated melamine such as Cymel 506, 508, carboxyl group-containing methoxymethylated isobutoxymethylated melamine such as Cymel 1141, Cymel 1123 Methoxymethylated etoxy Methylated benzoguanamine, methoxymethylated butoxymethylated benzoguanamine such as Cymel 1123-10, butoxymethylated benzoguanamine such as Cymel 1128, carboxyl group-containing methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1125-80 Cyanamide). Examples of glycoluril include butoxymethylated glycoluril such as Cymel 1170, methylolated glycoluril such as Cymel 1172, and methoxymethylolated glycoluril such as Powderlink 1174.

Examples of the benzene or phenolic compound having a hydroxyl group or an alkoxyl group include 1,3,5-tris (methoxymethyl) benzene, 1,2,4-tris (isopropoxymethyl) benzene, 1,4-bis ( sec-butoxymethyl) benzene, 2,6-dihydroxymethyl-p-tert-butylphenol and the like.
More specifically, it is a crosslinkable compound represented by the following formula [6-1] to formula [6-48].

  Examples of the crosslinkable compound having a polymerizable unsaturated bond include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and tri (meth) acryloyloxyethoxytrimethylol. Crosslinkable compounds having three polymerizable unsaturated groups in the molecule such as propane and glycerin polyglycidyl ether poly (meth) acrylate; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meta ) Acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) Acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide bisphenol A type di (meth) acrylate, propylene oxide bisphenol type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) Acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, neopentyl glycol dihydroxypivalate ( Crosslinkable compound having two polymerizable unsaturated groups in the molecule such as (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (Meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meta) ) Crosslinkable compounds having one polymerizable unsaturated group in the molecule such as acrylate, glycerin mono (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate ester, N-methylol (meth) acrylamide; It is done.

（式［７］中、Ｅ_１は、シクロヘキシル環、ビシクロヘキサン環、ベンゼン環、ビフェニル環、ターフェニル環、ナフタレン環、フルオレン環、アントラセン環及びフェナントレン環からなる群から選ばれる基であり、Ｅ_２は、下記の式［７ａ］及び式［７ｂ］から選ばれる基であり、ｎは１〜４の整数である。）

上記化合物は架橋性化合物の一例であり、これらに限定されるものではない。また、本発明の液晶配向処理剤に含有される架橋性化合物は、１種類であってもよく、２種類以上組み合わせてもよい。
本発明の液晶配向処理剤における、架橋性化合物の含有量は、すべての重合体成分１００質量部に対して、０．１〜１５０質量部であることが好ましい。架橋反応が進行し目的の効果を発現し、かつ液晶の配向性を低下させないためには、すべての重合体成分１００質量部に対して０．１〜１００質量部がより好ましく、特に、１〜５０質量部が好ましい。 Furthermore, a compound represented by the following formula [7] can also be used.

(In the formula [7], E ₁ is a group selected from the group consisting of a cyclohexyl ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring and a phenanthrene ring, ₂ is a group selected from the following formula [7a] and formula [7b], and n is an integer of 1 to 4.

The said compound is an example of a crosslinkable compound, It is not limited to these. Moreover, the crosslinkable compound contained in the liquid crystal aligning agent of this invention may be one type, and may be combined two or more types.
It is preferable that content of the crosslinkable compound in the liquid-crystal aligning agent of this invention is 0.1-150 mass parts with respect to 100 mass parts of all the polymer components. In order for the crosslinking reaction to proceed and to exhibit the desired effect and not to reduce the orientation of the liquid crystal, 0.1 to 100 parts by mass is more preferable with respect to 100 parts by mass of all the polymer components. 50 parts by mass is preferred.

As long as the liquid crystal aligning agent of the present invention does not impair the effects of the present invention, the compound for promoting charge transfer in the liquid crystal aligning film and promoting charge release of the liquid crystal cell using the liquid crystal aligning film is represented by the following formula: It is preferable to add a nitrogen-containing heterocyclic amine compound represented by [M1] to [M156]. The amine compound may be added directly to the solution of the specific polymer. However, the amine compound may be added after making a solution having a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass with an appropriate solvent. preferable. The solvent is not particularly limited as long as it is an organic solvent that dissolves the specific polymer described above.

Unless the effect of this invention is impaired, the liquid-crystal aligning agent of this invention is the organic solvent (poor solvent) which improves the film thickness uniformity and surface smoothness at the time of apply | coating a liquid-crystal aligning agent. Or compounds may be used. Furthermore, a compound that improves the adhesion between the liquid crystal alignment film and the substrate can also be used.
Specific examples of the poor solvent that improves the uniformity of the film thickness and the surface smoothness include the following.
For example, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1,2- Etanji 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentane Diol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2 Heptanone, 4-heptanone, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate , Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2- (methoxymethoxy) ethanol, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol hexyl ether, 2- (hexyloxy) ethanol, Furfuryl alcohol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, 1- (butoxyethoxy) propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl Ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene group Cole monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2- (2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, lactic acid Ethyl, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl lactate, ethyl lactate Ester, lactic n- propyl ester, lactate n- butyl ester, the surface tension of the solvent, such as lactic isoamyl ester is low organic solvent.
These poor solvents may be used alone or in combination. When using the above poor solvent, it is preferable that it is 5-80 mass% of the whole organic solvent contained in a liquid-crystal aligning agent, More preferably, it is 20-60 mass%.

Examples of compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.
More specifically, for example, F-top EF301, EF303, EF352 (manufactured by Tochem Products), MegaFuck F171, F173, R-30 (manufactured by Dainippon Ink), Florard FC430, FC431 (manufactured by Sumitomo 3M) Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.) and the like. The use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of all the polymer components contained in the liquid crystal aligning agent. It is.

Specific examples of the compound that improves the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds and epoxy group-containing compounds.
For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxy Carbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-tri Toxisilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxy Silane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyl Trimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, poly Lopylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl -2,4-hexanediol, N, N, N ′, N ′,-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′ , N ′,-tetraglycidyl-4,4′-diaminodiphenylmethane and the like.
When using a compound that improves the adhesion to the substrate, it is preferably 0.1 to 30 parts by weight, more preferably 100 parts by weight of all polymer components contained in the liquid crystal aligning agent. 1 to 20 parts by mass. If the amount is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the orientation of the liquid crystal may deteriorate.
The liquid crystal alignment treatment agent of the present invention includes the above-mentioned crosslinkable compound, poor solvent, compound for improving film thickness uniformity and surface smoothness, and compound for improving adhesion to the substrate, and the effects of the present invention. As long as the thickness of the liquid crystal alignment film is not impaired, a dielectric material or conductive material for changing the electrical properties such as the dielectric constant or conductivity of the liquid crystal alignment film 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 after being applied and baked on a substrate and then subjected to alignment treatment by rubbing treatment or light irradiation.
Moreover, 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 simplification of the process, it is preferable to use a substrate on which an ITO electrode for driving a liquid crystal is formed. In the reflective liquid crystal display element, an opaque substrate such as a silicon wafer can be used if only one substrate is used, and a material that reflects light such as aluminum can be used as an electrode in this case.
The method for applying the liquid crystal aligning agent is not particularly limited, but industrially, screen printing, offset printing, flexographic printing, inkjet method, and the like are common. Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method, and a spray method, and these may be used depending on the purpose.
After applying the liquid crystal alignment treatment agent on the substrate, the solvent is evaporated at 50 to 300 ° C., preferably 80 to 250 ° C. by a heating means such as a hot plate, a heat circulation type oven, an IR (infrared) type oven, It can be a polymer coating. If the thickness of the polymer 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 aligned horizontally or tilted, the fired polymer film is treated by rubbing, irradiation with polarized ultraviolet rays, or the like.
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 liquid crystal cell manufacturing method, a pair of substrates on which a liquid crystal alignment film is formed are prepared, spacers are dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is on the inside, so that the other Examples include a method of bonding substrates and injecting liquid crystal under reduced pressure, and a method of sealing by bonding substrates after dropping liquid crystal on the liquid crystal alignment film surface on which spacers are dispersed.
Furthermore, the liquid-crystal aligning agent of this invention has a liquid-crystal layer between a pair of board | substrates provided with the electrode, 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 liquid crystal composition is also preferably used for a liquid crystal display element 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 a pretilt of liquid crystal molecules by a PSA (Polymer Sustained Alignment) method. In the PSA method, a small amount of a photopolymerizable compound such as 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, The pretilt of liquid crystal molecules is controlled by the polymer produced by irradiation with ultraviolet rays. 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, the liquid crystal display element of the present invention is prepared by obtaining a substrate with a liquid crystal alignment film from the liquid crystal alignment treatment agent of the present invention by the above-described method, and then preparing a liquid crystal cell and polymerizing by at least one of ultraviolet irradiation and heating. By polymerizing the compound, the alignment of the liquid crystal molecules can be controlled.
To give an example of manufacturing a PSA type liquid crystal cell, 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. Then, the other substrate is bonded, the liquid crystal is injected under reduced pressure and sealed, the liquid crystal is dropped on the liquid crystal alignment film surface on which the spacers are dispersed, and then the substrate is bonded and sealed. .
In the liquid crystal, 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 mass parts with respect to 100 mass parts of a liquid-crystal component, More preferably, it is 0.1-5 mass parts. When the polymerizable compound is less than 0.01 part by mass, the polymerizable compound is not polymerized and the alignment of the liquid crystal cannot be controlled. When the polymerizable compound exceeds 10 parts by mass, the amount of the unreacted polymerizable compound increases, and the liquid crystal display The burn-in characteristic of the element is deteriorated.
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. The liquid crystal display element manufactured through the process of arrange | positioning the liquid crystal aligning film containing this, and applying a voltage between electrodes is used preferably. 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.
In order to obtain a liquid crystal alignment film containing a polymerizable group that is polymerized by 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. Since the liquid crystal aligning agent of the present invention contains a specific compound having a double bond site that reacts by irradiation with heat or ultraviolet rays, the alignment of liquid crystal molecules can be controlled by at least one of ultraviolet irradiation and heating. .
If an example of liquid crystal cell production is given, prepare a pair of substrates on which a liquid crystal alignment film is formed, spread spacers on the liquid crystal alignment film of one substrate, and make the liquid crystal alignment film surface inside, Examples include a method in which the other substrate is bonded and liquid crystal is injected under reduced pressure to seal, and a method in which the liquid crystal is dropped on the liquid crystal alignment film surface on which spacers are dispersed and then the substrate is bonded and sealed.
After the liquid crystal cell is manufactured, 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.
As described above, the liquid crystal display device manufactured using the liquid crystal aligning agent of the present invention has excellent reliability and can be suitably used for a large-screen, high-definition liquid crystal television.

  The present invention will be described in more detail with reference to the following examples, but is not limited thereto.

[Synthesis of Specific Side Chain Type Diamine Compound]
The analyzer and analysis conditions employed in the identification of the specific side chain diamine compound of the present invention are as follows.
(Measurement of ¹ H-NMR)
Apparatus: Varian NMR System 400NB (400 MHz) (manufactured by Varian)
Measurement solvent: CDCl ₃ (deuterated chloroform) and DMSO-d ₆ (deuterated dimethyl sulfoxide)
Reference materials: TMS (tetramethylsilane) (δ: 0.0 ppm, ¹ H) and CDCl ₃ (δ: 77.0 ppm, ¹³ C)

フェノール誘導体（ａ）（３０．０ｇ，１０９ｍｍｏｌ）のＤＭＦ（ジメチルホルムアミド）溶液（１９０ｍｌ）に、Ｋ_２ＣＯ_３（炭酸カリウム）（１８．１ｇ，１３１ｍｍｏｌ）とＫＩ（ヨウ化カリウム）（１．８１ｇ，１０．９ｍｍｏｌ）を加え、６０℃に加温した。そこに、プロパルギルブロミド（１９．５ｇ，１６４ｍｍｏｌ）を滴下し、２４時間反応させた。その後、反応溶液を水（３６０ｍｌ）に注いだ。析出した固体を濾別し、得られた固体をメタノール中で攪拌洗浄して、プロパギルエーテル体（ｂ）の粗物を得た（収量：３２．５ｇ，収率：９５％）。得られた粗物は、そのまま次の反応に用いた。
プロパギルエーテル体（ｂ）：
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，δｐｐｍ）：７．１４（ｄ，２Ｈ），６．９１（ｄ，２Ｈ），４．６７（ｄ，２Ｈ），２．５１（ｔ，１Ｈ），２．４６−２．３７）（ｍ，１Ｈ），１．９０−１．８１（ｍ，４Ｈ），１．４６−１．１８（ｍ，１５Ｈ），１．１１−０．９５（ｍ，２Ｈ），０．８９（ｔ，３Ｈ）． <Example 1>
Synthesis of specific side chain diamine compound (1)

To a DMF (dimethylformamide) solution (190 ml) of the phenol derivative (a) (30.0 g, 109 mmol), K ₂ CO ₃ (potassium carbonate) (18.1 g, 131 mmol) and KI (potassium iodide) (1.81 g , 10.9 mmol) was added and heated to 60 ° C. To this, propargyl bromide (19.5 g, 164 mmol) was added dropwise and reacted for 24 hours. Thereafter, the reaction solution was poured into water (360 ml). The precipitated solid was separated by filtration, and the obtained solid was stirred and washed in methanol to obtain a crude product of propargyl ether (b) (yield: 32.5 g, yield: 95%). The obtained crude product was directly used in the next reaction.
Propagyl ether (b):
¹ H-NMR (CDCl ₃ , δ ppm): 7.14 (d, 2H), 6.91 (d, 2H), 4.67 (d, 2H), 2.51 (t, 1H), 2.46 -2.37) (m, 1H), 1.90-1.81 (m, 4H), 1.46-1.18 (m, 15H), 1.11-0.95 (m, 2H), 0.89 (t, 3H).

３，５−ジニトロヨードベンゼン（ｃ）（２３．５ｇ，８０．１ｍｍｏｌ）のＴＨＦ（テトラヒドロフラン）溶液（１０６ｍｌ）に、ＰｄＣｌ_２（ＰＰｈ_３）_２（０．５６２ｇ，０．８０１ｍｍｏｌ）、ＣｕＩ（ヨウ化銅（Ｉ））（０．３０５ｇ，１．６０ｍｍｏｌ）、及びＥｔ_２ＮＨ（ジエチルアミン）（７．６１ｇ，１０４ｍｍｏｌ）を加えた後、水浴で冷却した。この溶液に、プロパギルエーテル体（ｂ）（３２．５ｇ，１０４ｍｍｏｌ）のＴＨＦ溶液（２２．０ｍｌ）を滴下した。１時間攪拌し、反応溶液を水（５６０ｍｌ）に注いだ。析出した固体を濾別し、得られた固体を、酢酸エチルとヘキサンの混合溶媒で再結晶を行い、ジニトロ体（ｄ）を得た（収量：２３．６ｇ，収率：６２％）。
ジニトロ体（ｄ）：
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，δｐｐｍ）：８．９８（ｔ，１Ｈ），８．５６（ｄ，２Ｈ），７．１８（ｄ，２Ｈ），６．９４（ｄ，２Ｈ），４．９３（ｓ，２Ｈ），２．４８−２．３８（ｍ，１Ｈ），１．９２−１．８１（ｍ，４Ｈ），１．４７−１．１８（ｍ，１５Ｈ），１．１０−０．９４（ｍ，２Ｈ），０．８９（ｔ，３Ｈ）．
^１３Ｃ−ＮＭＲ（ＣＤＣｌ_３，δｐｐｍ）：１５５．４３，１４８．３４，１４１．５２，１３１．４８，１２７．８１，１２６．０２，１１８．３８，１１４．５７，９０．３１，８２．４６，５６．１４，４３．７１，３７．３８，３７．２６，３４．４９，３３．５６，３１．８９，２９．９３，２９．３６，２６．９７，２２．６８，１４．１１．

To a THF (tetrahydrofuran) solution (106 ml) of 3,5-dinitroiodobenzene (c) (23.5 g, 80.1 mmol), PdCl ₂ (PPh ₃ ) ₂ (0.562 g, 0.801 mmol), CuI (iodine) Copper (I) chloride) (0.305 g, 1.60 mmol) and Et ₂ NH (diethylamine) (7.61 g, 104 mmol) were added, followed by cooling in a water bath. To this solution was added dropwise a THF solution (22.0 ml) of propargyl ether form (b) (32.5 g, 104 mmol). After stirring for 1 hour, the reaction solution was poured into water (560 ml). The precipitated solid was separated by filtration, and the obtained solid was recrystallized with a mixed solvent of ethyl acetate and hexane to obtain a dinitro compound (d) (yield: 23.6 g, yield: 62%).
Dinitro form (d):
¹ H-NMR (CDCl ₃ , δ ppm): 8.98 (t, 1H), 8.56 (d, 2H), 7.18 (d, 2H), 6.94 (d, 2H), 4.93 (S, 2H), 2.48-2.38 (m, 1H), 1.92-1.81 (m, 4H), 1.47-1.18 (m, 15H), 1.10-0 .94 (m, 2H), 0.89 (t, 3H).
¹³ C-NMR (CDCl ₃ , δ ppm): 155.43, 148.34, 141.52, 131.48, 127.81, 126.02, 118.38, 114.57, 90.31, 82.46 56.14, 43.71, 37.38, 37.26, 34.49, 33.56, 31.89, 29.93, 29.36, 26.97, 22.68, 14.11.

ジニトロ体（ｄ）（２３．３ｇ，４８．７ｍｍｏｌ）のＴＨＦ（１３１ｍｌ）及びトルエン（１３４ｍｌ）の混合溶液中に、Ｐｄ／Ｃ（パラジウムカーボン）（２．３３ｇ）を加え、水素雰囲気下、室温で攪拌した。９６時間反応させた後、濾過によりＰｄ／Ｃを取り除いた。濾液を濃縮し、得られた固体を１，４−ジオキサンとヘキサンの混合溶媒で再結晶を行い、特定側鎖型ジアミン化合物（１）を得た（収量：１１．９ｇ，収率：５８％）。
特定側鎖型ジアミン化合物（１）：
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，δｐｐｍ）：７．１１（ｄ，２Ｈ），６．８２（ｄ，２Ｈ），５．９９（ｄ，２Ｈ），５．８９（ｔ，１Ｈ），３．９３（ｔ，２Ｈ），３．５１（Ｂｒｏａｄ，４Ｈ），２．６０（ｔ，２Ｈ），２．４５−２．３５（ｍ，１Ｈ），２．０７−１．９８（ｍ，２Ｈ），１．９０−１．８１（ｍ，４Ｈ），１．４４−１．１７（ｍ，１５Ｈ），１．０８−０．９３（ｍ，２Ｈ），０．８９（ｔ，３Ｈ）．
^１３Ｃ−ＮＭＲ（ＣＤＣｌ_３，δｐｐｍ）：１５７．０９，１４７．４３，１４３．９７，１３９．９３，１２７．５３，１１４．２７，１０６．３０，９９．７１，６６．９８，４３．６７，３７．４０，３７．２６，３４．５４，３３．６１，３２．０９，３１．８８，３０．５４，２９．９３，２９．３５，２６．９６，２２．６６，１４．１０．

Pd / C (palladium carbon) (2.33 g) was added to a mixed solution of dinitro compound (d) (23.3 g, 48.7 mmol) in THF (131 ml) and toluene (134 ml). And stirred. After reacting for 96 hours, Pd / C was removed by filtration. The filtrate was concentrated, and the obtained solid was recrystallized with a mixed solvent of 1,4-dioxane and hexane to obtain a specific side chain diamine compound (1) (yield: 11.9 g, yield: 58%). ).
Specific side chain diamine compound (1):
¹ H-NMR (CDCl ₃ , δ ppm): 7.11 (d, 2H), 6.82 (d, 2H), 5.99 (d, 2H), 5.89 (t, 1H), 3.93 (T, 2H), 3.51 (Broad, 4H), 2.60 (t, 2H), 2.45-2.35 (m, 1H), 2.07-1.98 (m, 2H), 1.90-1.81 (m, 4H), 1.44-1.17 (m, 15H), 1.08-0.93 (m, 2H), 0.89 (t, 3H).
¹³ C-NMR (CDCl ₃ , δ ppm): 157.09, 147.43, 143.97, 139.93, 127.53, 114.27, 106.30, 99.71, 66.98, 43.67 37.40, 37.26, 34.54, 33.61, 32.09, 31.88, 30.54, 29.93, 29.35, 26.96, 22.66, 14.10.

フェノール誘導体（ａ）（３０．０ｇ，１０９ｍｍｏｌ）のＤＭＦ溶液（６４．０ｍｌ）に、Ｋ_２ＣＯ_３（２７．２ｇ，１９７ｍｍｏｌ）、ＫＩ（０．９０７ｇ，５．４７ｍｍｏｌ）、及び５−クロロ−１−ペンチン（１５．７ｇ，１５３ｍｍｏｌ）を加え、１００℃に加温して４８時間反応させた。その後、２５℃まで冷却してからＤＭＦ（９５．０ｍｌ）を加え、この反応溶液に水（３０ｍｌ）を滴下し、反応を停止させた。この反応混合物を水（１５０ｍｌ）に注ぎ、析出した固体を濾別した。得られた固体を酢酸エチルとメタノールの混合溶媒で再結晶を行い、エーテル体（ｅ）を得た（収量：３３．７ｇ，収率：９１％）。
エーテル体（ｅ）：
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，δｐｐｍ）：７．１１（ｄ，２Ｈ），６．８３（ｄ，２Ｈ），４．０４（ｔ，２Ｈ），２．４５−２．３６（ｍ，１Ｈ），２．４０（ｄｔ，２Ｈ），２．０３−１．９５（ｍ，２Ｈ），１．９６（ｔ，１Ｈ），１．８９−１．７９（ｍ，４Ｈ），１．４４−１．１７（ｍ，１５Ｈ），１．０８−０．９４（ｍ，２Ｈ），０．８９（ｔ，３Ｈ）．
^１３Ｃ−ＮＭＲ（ＣＤＣｌ_３，δｐｐｍ）：１５６．９３，１４０．２１，１２７．６２，１１４．２４，８３．５９，６８．７４，６６．０５，４３．７２，３７．４４，３７．３１，３４．５７，３３．６５，３１．９２，２９．９６，２９．３９，２８．２６，２７．００，２２．７０，１５．１９，１４．１３． <Example 2>
Synthesis of specific side chain diamine compound (2)

To a DMF solution (64.0 ml) of the phenol derivative (a) (30.0 g, 109 mmol), K ₂ CO ₃ (27.2 g, 197 mmol), KI (0.907 g, 5.47 mmol), and 5-chloro- 1-Pentine (15.7 g, 153 mmol) was added, and the mixture was heated to 100 ° C. and reacted for 48 hours. Then, after cooling to 25 degreeC, DMF (95.0 ml) was added, water (30 ml) was dripped at this reaction solution, and reaction was stopped. The reaction mixture was poured into water (150 ml), and the precipitated solid was filtered off. The obtained solid was recrystallized with a mixed solvent of ethyl acetate and methanol to obtain an ether form (e) (yield: 33.7 g, yield: 91%).
Ether form (e):
¹ H-NMR (CDCl ₃ , δ ppm): 7.11 (d, 2H), 6.83 (d, 2H), 4.04 (t, 2H), 2.45-2.36 (m, 1H) , 2.40 (dt, 2H), 2.03-1.95 (m, 2H), 1.96 (t, 1H), 1.89-1.79 (m, 4H), 1.44-1 .17 (m, 15H), 1.08-0.94 (m, 2H), 0.89 (t, 3H).
¹³ C-NMR (CDCl ₃ , δ ppm): 156.93, 140.21, 127.62, 114.24, 83.59, 68.74, 66.05, 43.72, 37.44, 37.31 34.57, 33.65, 31.92, 29.96, 29.39, 28.26, 27.00, 22.70, 15.19, 14.13.

３，５−ジニトロヨードベンゼン（ｃ）（２０．０ｇ，６８．０ｍｍｏｌ）のＴＨＦ溶液（９０ｍｌ）に、ＰｄＣｌ_２（ＰＰｈ_３）_２（０．４７７ｇ，０．６８０ｍｍｏｌ）、ＣｕＩ（０．２５９ｇ，１．３６ｍｍｏｌ）、及びＥｔ_２ＮＨ（６．４７ｇ，８８．４ｍｍｏｌ）を加えた後、水浴で冷却した。この溶液に、末端アセチレン体（ｅ）（３０．１ｇ，８８．４ｍｍｏｌ）のＴＨＦ溶液（４５．０ｍｌ）を滴下した。２０時間攪拌し、反応溶液を水（６００ｍｌ）に注いだ。析出した固体を濾別し、得られた固体をＴＨＦとメタノールの混合溶媒で再結晶を行い、ジニトロ体（ｆ）を得た（収量：３０．０ｇ，収率：８７％）。
ジニトロ体（ｆ）：
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，δｐｐｍ）：８．９２（ｔ，１Ｈ），８．５０（ｄ，２Ｈ），７．１４（ｄ，２Ｈ），６．８５（ｄ，２Ｈ），４．１０（ｔ，２Ｈ），２．７１（ｔ，２Ｈ），２．４５−２．３６（ｍ，１Ｈ），２．１５−２．０５（ｍ，２Ｈ），１．８９−１．７８（ｍ，４Ｈ），１．４４−１．１６（ｍ，１５Ｈ），１．０９−０．９４（ｍ，２Ｈ），０．８９（ｔ，３Ｈ）．
^１３Ｃ−ＮＭＲ（ＣＤＣｌ_３，δｐｐｍ）：１５６．７６，１４８．３３，１４０．４５，１３１．３４，１２７．６９，１２７．５６，１１７．４３，１１４．１９，９６．２３，７７．３５，６５．９３，４３．７１，３７．４１，３７．２９，３４．５５，３３．６１，３１．９１，２９．９４，２９．３８，２８．０３，２２．６９，１６．２８，１４．１１．

To a THF solution (90 ml) of 3,5-dinitroiodobenzene (c) (20.0 g, 68.0 mmol), PdCl ₂ (PPh ₃ ) ₂ (0.477 g, 0.680 mmol), CuI (0.259 g, 1.36 mmol) and Et ₂ NH (6.47 g, 88.4 mmol) were added and then cooled in a water bath. To this solution, a THF solution (45.0 ml) of the terminal acetylene body (e) (30.1 g, 88.4 mmol) was added dropwise. After stirring for 20 hours, the reaction solution was poured into water (600 ml). The precipitated solid was separated by filtration, and the obtained solid was recrystallized with a mixed solvent of THF and methanol to obtain a dinitro compound (f) (yield: 30.0 g, yield: 87%).
Dinitro form (f):
¹ H-NMR (CDCl ₃ , δ ppm): 8.92 (t, 1H), 8.50 (d, 2H), 7.14 (d, 2H), 6.85 (d, 2H), 4.10 (T, 2H), 2.71 (t, 2H), 2.45-2.36 (m, 1H), 2.15-2.05 (m, 2H), 1.89-1.78 (m , 4H), 1.4-1.16 (m, 15H), 1.09-0.94 (m, 2H), 0.89 (t, 3H).
¹³ C-NMR (CDCl ₃ , δ ppm): 156.76, 148.33, 140.45, 131.34, 127.69, 127.69, 117.43, 114.19, 96.23, 77.35 , 65.93, 43.71, 37.41, 37.29, 34.55, 33.61, 31.91, 29.94, 29.38, 28.03, 22.69, 16.28, 14 .11.

ジニトロ体（ｆ）（２９．７ｇ，５８．６ｍｍｏｌ）のＴＨＦ（１６７ｍｌ）及びトルエン（１７２ｍｌ）の混合溶液中に、Ｐｄ／Ｃ（２．９７ｇ）を加え、水素雰囲気下、室温で攪拌した。７２時間反応させた後、濾過によりＰｄ／Ｃを取り除いた。濾液を濃縮し、得られた固体をＴＨＦとヘキサンの混合溶媒で再結晶を行い、特定側鎖型ジアミン化合物（２）を得た（２２．１ｇ，８４％）。
特定側鎖型ジアミン化合物（２）：
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，δｐｐｍ）：７．１１（ｄ，２Ｈ），６．８２（ｄ，２Ｈ），５．９７（ｄ，２Ｈ），５．８９（ｔ，１Ｈ），３．９２（ｔ，２Ｈ），３．５１（Ｂｒｏａｄ，４Ｈ），２．４４（ｔ，２Ｈ），２．４８−２．３４（ｍ，１Ｈ），１．８９−１．７４（ｍ，６Ｈ），１．６６−１．５７（ｍ，２Ｈ），１．５２−１．１８（ｍ，１７Ｈ），１．０７−０．９５（ｍ，２Ｈ），０．８９（ｔ，３Ｈ）．
^１３Ｃ−ＮＭＲ（ＣＤＣｌ_３，δｐｐｍ）：１５７．１２，１４７．３４，１４４．９８，１３９．８９，１２７．５４，１１４．１７，１０６．２７，９９．６０，６７．７７，４３．６８，３７．４１，３７．２７，３５．８３，３４．５５，３３．６２，３１．８９，３０．８９，２９．９３，２９．３６，２９．２０，２６．９７，２５．７６，２２．６７，１４．１１．

Pd / C (2.97 g) was added to a mixed solution of dinitro compound (f) (29.7 g, 58.6 mmol) in THF (167 ml) and toluene (172 ml), and the mixture was stirred at room temperature in a hydrogen atmosphere. After reacting for 72 hours, Pd / C was removed by filtration. The filtrate was concentrated, and the resulting solid was recrystallized with a mixed solvent of THF and hexane to obtain a specific side chain diamine compound (2) (22.1 g, 84%).
Specific side chain type diamine compound (2):
¹ H-NMR (CDCl ₃ , δ ppm): 7.11 (d, 2H), 6.82 (d, 2H), 5.97 (d, 2H), 5.89 (t, 1H), 3.92 (T, 2H), 3.51 (Broad, 4H), 2.44 (t, 2H), 2.48-2.34 (m, 1H), 1.89-1.74 (m, 6H), 1.66-1.57 (m, 2H), 1.52-1.18 (m, 17H), 1.07-0.95 (m, 2H), 0.89 (t, 3H).
¹³ C-NMR (CDCl ₃ , δ ppm): 157.12, 147.34, 144.98, 139.89, 127.54, 114.17, 106.27, 99.60, 67.77, 43.68 37.41, 37.27, 35.83, 34.55, 33.62, 31.89, 30.89, 29.93, 29.36, 29.20, 26.97, 25.76, 22 .67, 14.11.

末端アセチレン体（ｅ）（１７．０ｇ，４９．９ｍｍｏｌ）のＴＨＦ溶液（９６．０ｍｌ）に、カテコールボランの１規定（８０．０ｍｍｏｌ）のＴＨＦ溶液（８０．０ｍｌ）を１時間かけて滴下し、８０℃で２４時間、還流攪拌した。その後、２５℃まで放冷後、反応溶液に、２規定の塩酸水溶液（１５０）ｍｌを加え、２時間攪拌し、水（２０００ｍｌ）に注いだ。析出した固体を濾別し、ヘキサンで洗浄してボロン酸誘導体（ｈ）を得た。得られたボロン酸誘導体は、そのまま次の工程に使用した。 <Example 3>
Synthesis of specific side chain diamine compound (3)

To a THF solution (96.0 ml) of the terminal acetylene body (e) (17.0 g, 49.9 mmol), a 1N (80.0 mmol) THF solution (80.0 ml) of catecholborane was added dropwise over 1 hour. The mixture was stirred at 80 ° C. for 24 hours under reflux. Then, after cooling to 25 ° C., 2N aqueous hydrochloric acid (150) ml was added to the reaction solution, stirred for 2 hours, and poured into water (2000 ml). The precipitated solid was separated by filtration and washed with hexane to obtain a boronic acid derivative (h). The obtained boronic acid derivative was directly used in the next step.

ボロン酸誘導体（ｈ）（１７．７ｇ，４５．８ｍｍｏｌ）、２，４−ジニトロクロロベンゼン（ｋ）（８．８４ｇ，４３．６ｍｍｏｌ）、及びＰｄ（ＰＰｈ_３）_４（０．５３０ｇ，０．４５９ｍｍｏｌ）の１，４−ジオキサン溶液（５５．７ｍｌ）に、２．０ｍｏｌ／Ｌの炭酸カリウム水溶液（５５．７ｍｌ）を加え、８０℃で２時間攪拌した。その後、酢酸エチルと水で分液を行い、有機層を硫酸マグネシウムで乾燥させた。有機層を濃縮して得られた固体を酢酸エチルとヘキサンを用いてカラムクロマトグラフィーを行い、ジニトロ体（ｍ）を得た（１３．１ｇ，５９％）。
ジニトロ体（ｍ）：
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，δｐｐｍ）：８．７６（ｄ，１Ｈ），８．３７（ｄｄ，１Ｈ），７．７９（ｄ，２Ｈ），７．１２（ｄ，２Ｈ），６．９５（ｄ，１Ｈ），６．８３（ｄ，２Ｈ），６．５３（ｄｔ，１Ｈ），４．０２（ｔ，２Ｈ），２．５８−２．５０（ｍ，２Ｈ），２．４６−２．３７（ｍ，１Ｈ），２．０５−１．９７（ｍ，２Ｈ），１．９２−１．８１（ｍ，４Ｈ），１．４６−１．１７（ｍ，１５Ｈ），１，０９−０．９８（ｍ，２Ｈ），０．８９（ｔ，３Ｈ）．

Boronic acid derivative (h) (17.7 g, 45.8 mmol), 2,4-dinitrochlorobenzene (k) (8.84 g, 43.6 mmol), and Pd (PPh ₃ ) ₄ (0.530 g, 0.459 mmol) ) Was added to a 1,4-dioxane solution (55.7 ml), and a 2.0 mol / L aqueous potassium carbonate solution (55.7 ml) was added thereto, followed by stirring at 80 ° C. for 2 hours. Then, liquid separation was performed with ethyl acetate and water, and the organic layer was dried with magnesium sulfate. The solid obtained by concentrating the organic layer was subjected to column chromatography using ethyl acetate and hexane to obtain a dinitro compound (m) (13.1 g, 59%).
Dinitro body (m):
¹ H-NMR (CDCl ₃ , δ ppm): 8.76 (d, 1H), 8.37 (dd, 1H), 7.79 (d, 2H), 7.12 (d, 2H), 6.95 (D, 1H), 6.83 (d, 2H), 6.53 (dt, 1H), 4.02 (t, 2H), 2.58-2.50 (m, 2H), 2.46- 2.37 (m, 1H), 2.05-1.97 (m, 2H), 1.92-1.81 (m, 4H), 1.46-1.17 (m, 15H), 1, 09-0.98 (m, 2H), 0.89 (t, 3H).

ジニトロ体（ｍ）（１３．０ｇ，２５．６ｍｍｏｌ）のＴＨＦ溶液（１３０ｍｌ）に、Ｐｄ／Ｃ（１．３０ｇ）を加え、水素雰囲気下、室温で攪拌した。２４時間反応させた後、濾過によりＰｄ／Ｃを取り除いた。濾液に活性炭を加えて２時間攪拌し、濾過により活性炭を取り除いた。その後、濾液を濃縮し、特定側鎖型ジアミン化合物（３）を得た（１１．０ｇ，９５％）。
特定側鎖型ジアミン化合物（３）：
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，δｐｐｍ）：７．１０（ｄ，２Ｈ），６．８１１（ｄ，２Ｈ），６．８０５（ｄ，１Ｈ），６．１０（ｄｄ，１Ｈ），６．０４（ｄ，１Ｈ），３．９２（ｔ，２Ｈ），３．４９（Ｂｒｏａｄ，４Ｈ），２．４１（ｔ，２Ｈ），２．４４−２．３４（ｍ，１Ｈ），１．９０−１．７５（ｍ，６Ｈ），１．６８−１．５７（ｍ，２Ｈ），１．５７−１．４７（ｍ，２Ｈ），１．４６−１．３６（ｍ，２Ｈ）１．３５−１．１６（ｍ，１３Ｈ），１．０８−０．９６（ｍ，２Ｈ），０．８８（ｔ，３Ｈ）．
^１３Ｃ−ＮＭＲ（ＣＤＣｌ_３，δｐｐｍ）：１５３．８９，１４２．１８，１４１．５７，１３６．７２，１２７．１０，１２４．３４，１１４．１２，１１０．９７，１０２．８９，９９．３２，６４．５９，４０．４７，３４．２１，３４．０６，３１．３４，３０．４１，２８．６９，２７．２９，２６．７３，２６．１６，２６．０３，２５．７８，２３．７７，２２．８５，１９．４７，１０．９１．

Pd / C (1.30 g) was added to a THF solution (130 ml) of the dinitro compound (m) (13.0 g, 25.6 mmol), and the mixture was stirred at room temperature in a hydrogen atmosphere. After reacting for 24 hours, Pd / C was removed by filtration. Activated carbon was added to the filtrate and stirred for 2 hours, and the activated carbon was removed by filtration. Thereafter, the filtrate was concentrated to obtain a specific side chain diamine compound (3) (11.0 g, 95%).
Specific side chain type diamine compound (3):
¹ H-NMR (CDCl ₃ , δ ppm): 7.10 (d, 2H), 6.811 (d, 2H), 6.805 (d, 1H), 6.10 (dd, 1H), 6.04 (D, 1H), 3.92 (t, 2H), 3.49 (Broad, 4H), 2.41 (t, 2H), 2.44-2.34 (m, 1H), 1.90- 1.75 (m, 6H), 1.68-1.57 (m, 2H), 1.57-1.47 (m, 2H), 1.46-1.36 (m, 2H) 1.35 -1.16 (m, 13H), 1.08-0.96 (m, 2H), 0.88 (t, 3H).
¹³ C-NMR (CDCl ₃ , δ ppm): 153.89, 142.18, 141.57, 136.72, 127.10, 124.34, 114.12, 110.97, 102.89, 99.32 , 64.59, 40.47, 34.21, 34.06, 31.34, 30.41, 28.69, 27.29, 26.73, 26.16, 26.03, 25.78, 23 .77, 22.85, 19.47, 10.91.

（特定側鎖型ジアミン化合物）
Ａ−１：実施例１の合成経路で得られた特定側鎖型ジアミン化合物（１）
Ａ−２：実施例２の合成経路で得られた特定側鎖型ジアミン化合物（２）
Ａ−３：実施例３の合成経路で得られた特定側鎖型ジアミン化合物（３）

（その他ジアミン化合物）
ｐ−ＰＤＡ：ｐ−フェニレンジアミン
ｍ−ＰＤＡ：ｍ−フェニレンジアミン
ＤＢＡ：３，５−ジアミノ安息香酸
ＡＰ１８：１，３−ジアミノ−４−オクタデシルオキシベンゼン

（有機溶媒）
ＮＭＰ：Ｎ−メチル−２−ピロリドン
ＢＣＳ：ブチルセロソルブ [Synthesis of polyimide precursor and polyimide]
The abbreviations of the compounds used in Examples and Comparative Examples are as follows.
(Tetracarboxylic dianhydride)
CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride BODA: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride TCA: shown by the following formula Tetracarboxylic dianhydride TDA: tetracarboxylic dianhydride represented by the following formula

(Specific side chain diamine compounds)
A-1: Specific side chain diamine compound (1) obtained by the synthesis route of Example 1
A-2: Specific side chain type diamine compound (2) obtained by the synthesis route of Example 2
A-3: Specific side chain diamine compound (3) obtained by the synthesis route of Example 3

(Other diamine compounds)
p-PDA: p-phenylenediamine m-PDA: m-phenylenediamine DBA: 3,5-diaminobenzoic acid AP18: 1,3-diamino-4-octadecyloxybenzene

(Organic solvent)
NMP: N-methyl-2-pyrrolidone
BCS: Butyl cellosolve

The molecular weight and imidation rate were measured as follows.
(Molecular weight measurement)
The molecular weight of the polyimide in the synthesis example is as follows using a normal temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko KK) and columns (KD-803, KD-805) (manufactured by Shodex). The measurement was performed as described above.
Column temperature: 50 ° C
Eluent: N, N′-dimethylformamide (as additives, lithium bromide-hydrate (LiBr · H ₂ O) is 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphoric acid) is 30 mmol / L, Tetrahydrofuran (THF) 10ml / L)
Flow rate: 1.0 ml / min Standard sample for preparing a 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 12,000, 4,000, and 1,000) (manufactured by Polymer Laboratory).

(Measurement of imidization rate)
20 mg of polyimide powder is put into an NMR sample tube (NMR sampling tube standard φ5 (manufactured by Kusano Kagaku)), deuterated dimethyl sulfoxide (DMSO-d6, 0.05 mass% TMS (tetramethylsilane) mixed 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 instrument (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 to 10.0 ppm. It calculated | required by the following formula | equation using the integrated value.
Imidation ratio (%) = (1−α · x / y) × 100
In the above formula, x is a proton peak integrated value derived from NH group of amic acid, y is a peak integrated value of reference proton, α is one NH group proton of amic acid in the case of polyamic acid (imidation rate is 0%) Is the number ratio of the reference proton to.

<Example 4>
CBDA (4.50 g, 22.9 mmol), A-1 (1.94 g, 4.6 mmol), and p-PDA (1.99 g, 18.4 mmol) were mixed in NMP (25.3 g). The reaction was carried out at ° C for 5.5 hours to obtain a polyamic acid solution (1) having a resin solid content concentration of 25.0% by mass. The number average molecular weight of this polyamic acid was 25,900, and the weight average molecular weight was 78,100.

<Example 5>
BODA (3.83 g, 15.3 mmol), A-1 (2.59 g, 6.1 mmol), and DBA (2.17 g, 14.3 mmol) were mixed in NMP (15.8 g) at 80 ° C. After reacting for 4 hours, CBDA (1.00 g, 5.1 mmol) and NMP (12.9 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%. Obtained.
After adding NMP to the obtained polyamic acid solution (20.1 g) and diluting to 6% by mass, acetic anhydride (2.45 g) and pyridine (1.85 g) were added as an imidization catalyst, The reaction was allowed for 5 hours. This reaction solution was put into methanol (350 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 55%, the number average molecular weight was 22,100, and the weight average molecular weight was 60,100.

<Example 6>
BODA (2.37 g, 9.5 mmol), A-2 (2.56 g, 5.7 mmol), and DBA (2.02 g, 13.3 mmol) were mixed in NMP (14.6 g) at 80 ° C. After reacting for 4 hours, CBDA (1.86 g, 9.5 mmol) and NMP (11.9 g) were added, and the mixture was reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0% by mass ( 3) was obtained. The number average molecular weight of this polyamic acid was 23,500, and the weight average molecular weight was 72,600.

<Example 7>
After adding NMP to the polyamic acid solution (3) (20.0 g) obtained in Example 6 and diluting to 6% by mass, acetic anhydride (4.50 g) and pyridine (3.25 g) were used as imidization catalysts. And reacted at 90 ° C. for 3.5 hours. This reaction solution was poured into methanol (450 ml), and the resulting precipitate was filtered off. 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 80%, the number average molecular weight was 19,500, and the weight average molecular weight was 50,100.

<Example 8>
BODA (3.04 g, 12.2 mmol), A-3 (2.34 g, 5.2 mmol), m-PDA (0.56 g, 5.2 mmol), and DBA (1.06 g, 7.0 mmol) were added to NMP. (13.2 g), and reacted at 80 ° C. for 5 hours. Then, CBDA (1.02 g, 5.2 mmol) and NMP (10.8 g) were added, and reacted at 40 ° C. for 6.5 hours. A polyamic acid solution having a resin solid content concentration of 25.0% by mass was obtained.
After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting to 6% by mass, acetic anhydride (4.51 g) and pyridine (3.25 g) were added as imidization catalysts, and The reaction was allowed for 5 hours. This reaction solution was poured into methanol (450 ml), and the resulting precipitate was filtered off. 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 81%, the number average molecular weight was 18,300, and the weight average molecular weight was 47,400.

<Example 9>
BODA (2.11 g, 8.4 mmol), A-3 (2.28 g, 5.1 mmol), p-PDA (0.36 g, 3.3 mmol), and DBA (1.28 g, 8.4 mmol) were added to NMP. (12.7 g), and after reacting at 80 ° C. for 5 hours, CBDA (1.65 g, 8.4 mmol) and NMP (10.5 g) were added and reacted at 40 ° C. for 6.5 hours. A polyamic acid solution having a resin solid content concentration of 25.0% by mass was obtained.
After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting to 6% by mass, acetic anhydride (4.50 g) and pyridine (3.31 g) were added as imidization catalysts, and The reaction was allowed for 5 hours. This reaction solution was poured into methanol (450 ml), and the resulting precipitate was filtered off. 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 68%, the number average molecular weight was 19,300, and the weight average molecular weight was 50,900.

<Example 10>
TCA (4.48 g, 20.0 mmol), A-1 (1.70 g, 4.0 mmol), and DBA (2.44 g, 16.0 mmol) were mixed in NMP (25.8 g) at 40 ° C. The reaction was performed for 6 hours to obtain a polyamic acid solution (7) having a resin solid content concentration of 25.0% by mass. The number average molecular weight of this polyamic acid was 24,200, and the weight average molecular weight was 75,800.

<Example 11>
After adding NMP to the polyamic acid solution (7) (20.5 g) obtained in Example 11 and diluting to 6% by mass, acetic anhydride (1.91 g) and pyridine (1.50 g) were used as imidization catalysts. And reacted at 80 ° C. for 4 hours. This reaction solution was put into methanol (350 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 58%, the number average molecular weight was 20,700, and the weight average molecular weight was 55,100.

<Example 12>
TCA (4.48 g, 20.0 mmol), A-3 (2.72 g, 6.0 mmol), p-PDA (0.65 g, 6.0 mmol), and DBA (1.22 g, 8.0 mmol) were added to NMP. (27.2 g) and the mixture was reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%.
After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting to 6% by mass, acetic anhydride (1.90 g) and pyridine (1.45 g) were added as an imidization catalyst, Reacted for hours. This reaction solution was put into methanol (350 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 55%, the number average molecular weight was 21,400, and the weight average molecular weight was 56,900.

<Example 13>
TDA (1.77 g, 5.9 mmol), A-2 (2.66 g, 5.9 mmol), and DBA (2.09 g, 13.7 mmol) were mixed in NMP (15.2 g) at 80 ° C. After reacting for 5.5 hours, CBDA (2.68 g, 13.7 mmol) and NMP (12.5 g) were added and reacted at 40 ° C. for 6 hours, and the polyamic acid having a resin solid content concentration of 25.0 mass% A solution was obtained.
After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting to 6% by mass, acetic anhydride (4.50 g) and pyridine (3.30 g) were added as imidization catalysts, and The reaction was allowed for 5 hours. This reaction solution was poured into methanol (500 ml), and the resulting precipitate was filtered off. 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 82%, the number average molecular weight was 19,400, and the weight average molecular weight was 48,300.

<Example 14>
TDA (4.06 g, 13.5 mmol), A-3 (3.65 g, 8.1 mmol), and p-PDA (2.05 g, 19.0 mmol) were mixed in NMP (20.5 g) and 80 After reacting at 5.5 ° C. for 5.5 hours, CBDA (2.65 g, 13.5 mmol) and NMP (16.8 g) were added, and reacted at 40 ° C. for 6 hours. The resin solid content concentration was 25.0% by mass. A polyamic acid solution was obtained.
After adding NMP to the obtained polyamic acid solution (20.5 g) and diluting to 6% by mass, acetic anhydride (1.95 g) and pyridine (1.50 g) were added as imidization catalysts, Reacted for hours. This reaction solution was put into methanol (350 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 56%, the number average molecular weight was 21,100, and the weight average molecular weight was 52,500.

<Comparative Example 1>
BODA (2.36 g, 9.4 mmol), AP18 (2.13 g, 5.7 mmol), and DBA (2.01 g, 13.2 mmol) were mixed in NMP (14.0 g) and at 80 ° C. for 4 hours. After the reaction, CBDA (1.85 g, 9.4 mmol) and NMP (11.0 g) were added, the mixture was reacted at 40 ° C. for 6 hours, and the polyamic acid solution (12) having a resin solid content concentration of 25.0 mass% Got. The number average molecular weight of this polyamic acid was 24,200, and the weight average molecular weight was 74,100.

<Comparative example 2>
After adding NMP to the polyamic acid solution (12) (20.0 g) obtained in Synthesis Example 1 and diluting to 6% by mass, acetic anhydride (4.50 g) and pyridine (3.20 g) were used as imidization catalysts. And reacted at 90 ° C. for 3.5 hours. This reaction solution was poured into methanol (450 ml), and the resulting precipitate was filtered off. 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 80%, the number average molecular weight was 19,900, and the weight average molecular weight was 51,600.
Table 37 summarizes the polyamic acid and polyimide obtained in Examples 4 to 14 and Comparative Examples 1 and 2.

＊１：ポリアミド酸

* 1: Polyamic acid

[Preparation of liquid crystal alignment treatment agent]
In Examples 15 to 25 and Comparative Examples 3 and 4, preparation examples of liquid crystal aligning agents were described. The obtained liquid crystal aligning agent is summarized in Table 38.

[Preparation of liquid crystal alignment film], [Liquidity evaluation of liquid crystal alignment film], [Evaluation of wettability of liquid crystal on liquid crystal alignment film], [Preparation of liquid crystal cell (ordinary cell)], [Preparation of liquid crystal cell (PSA) Cell)] and [Evaluation of Pretilt Angle] were performed as follows.
The characteristics of the liquid crystal alignment films obtained in Examples 15 to 25 and Comparative Examples 3 and 4 are collectively shown in Tables 39 to 42.
Table 39 shows the evaluation result of the hydrophobicity of the liquid crystal alignment film, Table 40 shows the evaluation result of the wettability of the liquid crystal on the liquid crystal alignment film, Table 41 shows the evaluation result of the pretilt angle using a normal cell, and Table 42 shows the evaluation result of the pretilt angle using the PSA cell.

[Preparation of liquid crystal alignment film]
A liquid crystal alignment treatment agent is spin-coated on the ITO surface of a 30 mm × 40 mm ITO electrode substrate, and heat-treated at 80 ° C. for 5 minutes on a hot plate and at 230 ° C. for 30 minutes in a heat-circulating clean oven. Thus, a substrate with a 100 nm-thick polyimide liquid crystal alignment film was obtained.

[Hydrophobic evaluation of liquid crystal alignment film]
The contact angle of water was measured using the substrate with the liquid crystal alignment film obtained in [Preparation of liquid crystal alignment film]. At that time, the higher the water contact angle, the higher the hydrophobicity, and the lower the water contact angle, the lower the hydrophobicity. In addition, the automatic contact angle meter CA-Z type (made by Kyowa Interface Science Co., Ltd.) was used for the measurement of the contact angle of water.

[Evaluation of wettability of liquid crystal on liquid crystal alignment film]
The contact angle of the liquid crystal was measured using the substrate with the liquid crystal alignment film obtained in [Preparation of liquid crystal alignment film]. At that time, the contact angle of the liquid crystal 10 seconds after dropping the liquid crystal was measured, and the liquid crystal alignment film having a lower liquid crystal contact angle was considered to have better wet spreadability on the liquid crystal alignment film. The higher the liquid crystal alignment film, the worse the wetting and spreading property of the liquid crystal on the liquid crystal alignment film. In addition, MLC-6608 (made by Merck Japan) was used for the liquid crystal, and the automatic contact angle meter CA-Z type (made by Kyowa Interface Science Co., Ltd.) was used for the measurement of a contact angle.

[Production of liquid crystal cell (normal cell)]
A liquid crystal alignment treatment agent is spin-coated on the ITO surface of a substrate with an ITO electrode of 30 mm × 40 mm, and heat-treated on a hot plate at 80 ° C. for 5 minutes and in a heat-circulating clean oven at 230 ° C. for 45 minutes. Thus, an ITO substrate with a polyimide liquid crystal alignment film having a thickness of 100 nm was obtained. The coated surface of the ITO substrate was rubbed using a rayon cloth with a rubbing apparatus having a roll diameter of 120 mm 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.
Two obtained ITO substrates with a liquid crystal alignment film were prepared, combined with a liquid crystal alignment film surface on the inside with a 6 μm spacer in between, and the periphery was adhered with a sealant to produce an empty cell. MLC-6608 (manufactured by Merck Japan Co., Ltd.) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell (normal cell).
About the liquid crystal cell obtained by the Example and the comparative example, the orientation uniformity of the liquid crystal was confirmed by polarizing microscope observation. In any of the liquid crystal cells, there was no shaving or poor alignment due to the rubbing treatment, and the liquid crystal was uniformly aligned.

[Preparation of liquid crystal cell (PSA cell)]
A liquid crystal alignment treatment agent is spin-coated on the ITO surface of a 10 mm × 10 mm ITO electrode substrate with a pattern spacing of 20 μm and a 10 mm × 40 mm ITO electrode substrate, and heat-circulating on a hot plate at 80 ° C. for 5 minutes. Heat treatment was performed at 230 ° C. for 30 minutes in a clean oven to obtain a polyimide coating film having a thickness of 100 nm. The coating surface was washed with pure water, and then heat-treated at 100 ° C. for 15 minutes in a heat-circulating clean oven to obtain a substrate with a liquid crystal alignment film.
This substrate with a liquid crystal alignment film was combined with the liquid crystal alignment film surface inside, with a 6 μm spacer in between, and the periphery was adhered with a sealant to produce an empty cell. The polymerizable compound (1) represented by the following formula was added to MLC-6608 (manufactured by Merck Japan Ltd.) by a reduced pressure injection method into this empty cell, and 0% of the polymerizable compound was 100% by mass of MLC-6608. .3 mass% mixed and injected, and then the injection port was sealed to obtain a liquid crystal cell.

While applying an AC voltage of 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, and the alignment direction of the liquid crystal A liquid crystal cell (PSA cell) was controlled. The temperature in the irradiation apparatus when the liquid crystal cell was irradiated with ultraviolet rays was 50 ° C.
The response speed of the liquid crystal before and after the ultraviolet irradiation of the liquid crystal cell was measured. As the response speed, T90 → T10 from 90% transmittance to 10% transmittance was measured. The PSA cells obtained in Examples and Comparative Examples have confirmed that the alignment direction of the liquid crystal was controlled because the response speed of the liquid crystal cell after ultraviolet irradiation was faster than that of the liquid crystal cell before ultraviolet irradiation. did.
In any liquid crystal cell, it was confirmed that the liquid crystal was uniformly aligned by observation with a polarizing microscope.

[Evaluation of pretilt angle]
The pretilt angle of the liquid crystal cell obtained in [Preparation of liquid crystal cell (normal cell)] and [Preparation of liquid crystal cell (PSA cell)] was measured. The pretilt angle was measured after the liquid crystal injection and after heat treatment at 95 ° C. for 5 minutes and after heat treatment at 120 ° C. for 5 hours. Furthermore, after the liquid crystal injection, the measurement was performed after the liquid crystal cell after the heat treatment at 95 ° C. for 5 minutes was irradiated with ultraviolet rays of 10 J / cm ^{2 in} terms of 365 nm. The pretilt angle was measured at room temperature using PAS-301 (ELSICON). Furthermore, ultraviolet irradiation was performed using a desktop UV curing device (HCT3B28HEX-1) (manufactured by Senlite).

<Example 15>
NMP (12.9 g) and BCS (18.8 g) were added to the polyamic acid solution (1) (10.0 g) having a resin solid content concentration of 25.0 mass% obtained in Example 4, and the mixture was added at 25 ° C. It stirred for 3 hours and obtained the liquid-crystal aligning agent (1). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the obtained liquid crystal aligning agent (1), production of cells and various evaluations were performed under the above-described conditions.

<Example 16>
NMP (18.8 g) and BCS (23.0 g) were added to the polyimide powder (2) (2.51 g) obtained in Example 5, and the mixture was stirred at 25 ° C. for 8 hours. 2) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the obtained liquid crystal aligning agent (2), cell preparation and various evaluations were performed under the above-described conditions.

<Example 17>
NMP (11.4 g) and BCS (21.9 g) were added to the polyamic acid solution (3) (10.5 g) having a resin solid content concentration of 25.0% by mass obtained in Example 6, and at 25 ° C. By stirring for 3 hours, a liquid crystal aligning agent (3) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the obtained liquid crystal aligning agent (3), cell preparation and various evaluations were performed under the above-described conditions.

<Example 18>
NMP (22.9 g) and BCS (18.8 g) were added to the polyimide powder (4) (2.50 g) obtained in Example 7, and the mixture was stirred at 25 ° C. for 8 hours. 4) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the obtained liquid crystal aligning agent (4), cell preparation and various evaluations were performed under the above-described conditions.

<Example 19>
NMP (21.0 g) and BCS (21.0 g) were added to the polyimide powder (5) (2.52 g) obtained in Example 8, and the mixture was stirred at 25 ° C. for 8 hours. 5) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the obtained liquid crystal aligning agent (5), cell preparation and various evaluations were performed under the above-described conditions.

<Example 20>
NMP (25.0 g) and BCS (16.7 g) were added to the polyimide powder (6) (2.50 g) obtained in Example 9, and the mixture was stirred at 25 ° C. for 8 hours. 6) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the obtained liquid crystal aligning agent (6), a cell was prepared and various evaluations were performed under the above-described conditions.

<Example 21>
NMP (15.0 g) and BCS (16.7 g) were added to the polyamic acid solution (7) (10.0 g) having a resin solid content concentration of 25.0% by mass obtained in Example 10, and at 25 ° C. The liquid crystal aligning agent (7) was obtained by stirring for 3 hours. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the obtained liquid crystal aligning agent (7), cell preparation and various evaluations were performed under the above-described conditions.

<Example 22>
NMP (27.1 g) and BCS (14.6 g) were added to the polyimide powder (8) (2.50 g) obtained in Example 11, and the mixture was stirred at 25 ° C. for 8 hours to obtain a liquid crystal alignment treatment agent ( 8) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the obtained liquid crystal aligning agent (8), a cell was prepared and various evaluations were performed under the above-described conditions.

<Example 23>
NMP (22.9 g) and BCS (18.8 g) were added to the polyimide powder (9) obtained in Example 12 (2.50 g), and the mixture was stirred at 25 ° C. for 8 hours. 9) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the obtained liquid crystal aligning agent (9), cell preparation and various evaluations were performed under the above-described conditions.

<Example 24>
NMP (25.0 g) and BCS (16.7 g) were added to the polyimide powder (10) (2.50 g) obtained in Example 13, and the mixture was stirred at 25 ° C. for 8 hours. 10) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the obtained liquid crystal aligning agent (10), cell preparation and various evaluations were performed under the above-described conditions.

<Example 25>
NMP (23.1 g) and BCS (18.9 g) were added to the polyimide powder (11) (2.52 g) obtained in Example 14, and the mixture was stirred at 25 ° C. for 8 hours. 11) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the obtained liquid crystal aligning agent (11), production of cells and various evaluations were performed under the above-described conditions.

<Comparative Example 3>
NMP (10.9 g) and BCS (21.0 g) were added to the polyamic acid solution (12) (10.1 g) having a resin solid content concentration of 25.0% by mass obtained in Comparative Example 1, and at 25 ° C. The liquid crystal aligning agent (12) was obtained by stirring for 3 hours. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the obtained liquid crystal aligning agent (12), cell preparation and various evaluations were performed under the above-described conditions.

<Comparative Example 4>
NMP (23.1 g) and BCS (18.9 g) were added to the polyimide powder (13) (2.52 g) obtained in Comparative Example 2, and the mixture was stirred at 25 ° C. for 8 hours. 13) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the obtained liquid crystal aligning agent (13), cell preparation and various evaluations were performed under the above-described conditions.

As can be seen from the above results, the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the example of the present invention has a longer temperature and light than the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the comparative example. Even when exposed to ultraviolet (UV) radiation, the change in the pretilt angle is small. The same result was obtained for both the normal cell and the PSA cell. In particular, Comparative Example 3 and Comparative Example 4 which do not contain a specific side chain type diamine compound have a large change in pretilt angle after being exposed to high temperature for a long time, and in particular, after being exposed to light (ultraviolet rays) irradiation. The change in the pretilt angle was large.
In addition, when polyimide precursors and polyimides having the same structure are used, in examples including specific side chain type diamine compounds, the change in pretilt angle even after being exposed to high temperature and light (ultraviolet rays) for a long time. Was small. Specifically, the comparison is made in the normal cells of Example 17 and Comparative Example 3 and Example 18 and Comparative Example 4 shown in Table 41. Moreover, it is the comparison in the PSA cell of Example 17 and Comparative Example 3 and Example 18 and Comparative Example 4 which are shown in Table 42.

Furthermore, the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the example of the present invention has a larger water contact angle of the liquid crystal alignment film than the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the comparative example. That is, the hydrophobicity of the liquid crystal alignment film is high. In particular, Comparative Example 3 and Comparative Example 4 that do not contain a specific side chain diamine compound have a small water contact angle of the liquid crystal alignment film and poor liquid crystal wettability on the liquid crystal alignment film (the liquid crystal contact angle is low). large).
Moreover, when the polyimide precursor and polyimide which are the same structure are used, in the Example containing a specific side chain type diamine compound, the contact angle of water of a liquid crystal aligning film is large, and the hydrophobicity of a liquid crystal aligning film is high. Moreover, in the Example containing a specific side chain type diamine compound, it is excellent in the wet spreading property on the liquid crystal aligning film of a liquid crystal. Specifically, it is a comparison of the evaluation of the water contact angle of the liquid crystal alignment films of Example 17 and Comparative Example 3 and Example 18 and Comparative Example 4 shown in Table 39. Moreover, it is a comparison of the evaluation of wet spreadability on the liquid crystal alignment film of the liquid crystal of Example 17 and Comparative Example 3 and Example 18 and Comparative Example 4 shown in Table 42.

By using the liquid crystal aligning agent containing a polymer having a side chain of a specific structure according to the present invention, the pretilt angle does not change even when exposed to high temperature and light irradiation for a long time, and liquid crystal generated by the ODF method A liquid crystal alignment film that can reduce alignment unevenness can be provided. By using the liquid crystal alignment film, it is possible to provide a highly reliable liquid crystal display element with excellent display characteristics, and a large-screen high-definition liquid crystal television. , TN element, STN element, TFT liquid crystal element and the like.
Furthermore, the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention is also useful in the production of a liquid crystal display element that needs to be irradiated with ultraviolet rays when producing a liquid crystal display element.
The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2011-240340 filed on November 1, 2011 are incorporated herein as the disclosure of the specification of the present invention. Is.

Claims (7)

A diamine compound represented by the following formula [2A].

(In the formula [2A], X ₁ represents —O—, —COO—, —OCO—, —CONH—, —NHCO—, —NH—, —N (R ₁ ) — (R ₁ represents 1 to ₁ carbon atoms) X ₂ represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring, or a heterocyclic ring, which is a linear alkyl group having 5 or a branched alkyl group having 1 to 5 carbon atoms), or S-. Arbitrary hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 3 carbon atoms. X ₃ represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring or a heterocyclic ring, and any hydrogen atom on these cyclic groups has 1 to 3 carbon atoms. Alkyl group, alkoxy group having 1 to 3 carbon atoms, 1 to carbon atoms Fluorine-containing alkyl group, fluorine-containing alkoxyl group or fluorine substituents .X ₄ be substituted with atoms of the alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms having 1 to 3 carbon atoms, An alkoxyl group having 1 to 18 carbon atoms or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms, m is an integer of 2 to 15, n is an integer of 1 to 3, and p is an integer of 0 to 3. And n + p is an integer of 1 to 6.) In the formula [1A], X ₁ is —O—, —CONH— or —NHCO—, X ₂ is a benzene ring or a cyclohexyl ring, and X ₃ is a benzene ring or a cyclohexyl ring. The diamine compound described. The diamine compound according to claim 1 or 2, wherein the diamine compound represented by the formula [2A] is represented by the following formula [2a] to formula [2d].

(In the formula [2a], R ₁ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. Yes, m1 is an integer from 2 to 15, and p1 is an integer from 0 to 3.
In the formula [2b], R ₂ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. , M2 is an integer from 2 to 15, and p2 is an integer from 0 to 3.
In Formula [2c], R ₃ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. , M3 is an integer of 2 to 15, n1 is an integer of 1 to 3, p3 is an integer of 0 to 3, and n1 + p3 is an integer of 1 to 6.
In the formula [2d], R ₄ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. , M4 is an integer of 2 to 15, n2 is an integer of 1 to 3, p4 is an integer of 0 to 3, and n2 + p4 is an integer of 1 to 6. )   The polyimide obtained by making the polyamic acid obtained by making the diamine component and tetracarboxylic acid component containing the diamine compound as described in any one of Claims 1-3 react, or dehydrating and ring-closing this polyamic acid.   The polyimide obtained by carrying out dehydration ring closure of the polyamic acid of Claim 4 which contains 5-80 mol% of diamine compounds as described in any one of Claims 1-3 in a diamine component. 6. The polyamic acid according to claim 4 or 5, wherein the tetracarboxylic acid component is a tetracarboxylic dianhydride represented by the following formula [3], or a polyimide obtained by dehydrating and ring-closing the polyamic acid.

(In the formula [3], Z ₁ is a tetravalent organic group having 4 to 13 carbon atoms and contains a non-aromatic cyclic hydrocarbon group having 4 to 10 carbon atoms.) The polyamic acid according to claim 6, wherein Z ₁ in the formula [3] is _{one of the structures} represented by the following formulas [3a] to [3j], or a polyimide obtained by dehydrating and ring-closing the polyamic acid. .

(In the formula [3a], Z _{2 to} Z ₅ are a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different. In the formula [3g], Z ₆ and Z ₇ Are hydrogen atoms or methyl groups, which may be the same or different.