JP5142450B2 - Diamino compound, vinyl compound, polymer compound, alignment film, organic semiconductor device using alignment film, conductive polymer, electroluminescence element using the conductive polymer, liquid crystal alignment film, and liquid crystal alignment film Optical element used - Google Patents

Description

  The present invention relates to a novel polymer compound and a liquid crystal alignment film for aligning a liquid crystalline compound containing these polymer compounds (however, including an alignment film for an organic semiconductor device, that is, a liquid crystalline semiconductor material) Alignment films), and optical elements having these liquid crystal alignment films and made from liquid crystalline compounds, for example, optical compensation sheets represented by retardation plates, polarizing plates, etc. used in liquid crystal display devices, Various optical filters typified by light polarizing prisms, polarizers, liquid crystal polarization control elements, etc., and liquid crystal display elements, backlights for liquid crystal display devices, electronic paper (flexible display elements), semiconductor lasers, and recording media (Optical elements such as hologram recording media), alignment films (alignment films for aligning low molecular compounds for organic semiconductor devices), conductive polymers, etc. To.

First, the liquid crystal display device includes a liquid crystal display element, a polarizing element, and an optical compensation sheet (retardation plate). In the transmissive liquid crystal display device, two polarizing elements are attached to both sides of the liquid crystal display element, and one or two optical compensation sheets are disposed between the liquid crystal display element and the polarizing element. In a reflective liquid crystal display device, a reflector, a liquid crystal display element, a single optical compensation sheet, and a single polarizing element are arranged in this order. The liquid crystal display element includes a liquid crystal molecular layer , two substrates for enclosing it, an electrode layer for applying a voltage to the liquid crystal molecules, and a liquid crystal alignment film for controlling the alignment of the liquid crystal molecules. The liquid crystal display element is different in the alignment state of liquid crystal molecules. As for the transmission type, TN (Twisted Nematic), IPS (In-Plane Switching), FLC (Ferroelectric Liquid Crystal), OCB (Optically Compensatory Bend), STN (STN) Various display modes such as TN, HAN (Hybrid Aligned Nematic), and GH (Guest-Host) have been proposed for Supper Twisted Nematic (VA), VA (Vertically Aligned), ECB (Electrically Controlled Birefringence), and reflective types. .

  Optical compensation sheets are used in various liquid crystal display devices in order to eliminate image coloring and expand the viewing angle. As the optical compensation sheet, a stretched birefringent polymer film has been conventionally used. It has been proposed to use an optical compensation sheet having an optically anisotropic layer formed of liquid crystalline molecules on a transparent support, instead of the optical compensation sheet made of a stretched birefringent film. Since liquid crystal molecules have various alignment forms, the use of liquid crystal molecules makes it possible to realize optical properties that cannot be obtained with conventional stretched birefringent polymer films.

  The optical property of the optical compensation sheet is determined according to the optical property of the liquid crystal display element, specifically, the difference in the display mode as described above. When liquid crystalline molecules are used, optical compensation sheets having various optical properties corresponding to various display modes of the liquid crystal display element can be produced. In general, liquid crystal molecules or discotic liquid crystal molecules are used as the liquid crystal molecules. Optical compensation sheets using liquid crystal molecules have already been proposed for various display modes. For example, an optical compensation sheet for a TN mode liquid crystal display element is described in the specification of Patent Document 1. An optical compensation sheet for liquid crystal display elements in IPS mode or FLC mode is described in Patent Document 2. Further, an optical compensation sheet for liquid crystal display elements in OCB mode or HAN mode is described in the specification of Patent Document 3. Furthermore, an optical compensation sheet for a liquid crystal display element in STN mode is described in Patent Document 4. An optical compensation sheet for a VA mode liquid crystal display element is described in Patent Document 5.

  Secondly, a liquid crystal display element used in a watch or a calculator is obtained by filling a liquid crystal between a pair of upper and lower electrode substrates. In these liquid crystal display elements, in order to function as a display element, it is necessary to align the liquid crystal inside the element in a predetermined direction. However, since the liquid crystal used here is a rod-like molecule, the refractive index varies depending on the direction in which the liquid crystal display element is viewed, and the phenomenon of gradation inversion and a reduction in viewing angle occurs. In order to solve this problem, a method has been proposed in which each pixel or a pixel is divided into two and rubbed in different directions. However, in this method, it is necessary to form a photoresist film after the first rubbing, remove a part of the photoresist film, and then perform the second rubbing to remove the remaining photoresist film, which complicates the process. There's a problem.

  Therefore, the alignment division is performed by providing the polymer for aligning the liquid crystal parallel to the rubbing direction and the polymer for aligning the liquid crystal perpendicular to the rubbing direction in a fixed pattern and performing rubbing once. A method was proposed. Although this method can perform alignment division more easily, polystyrene disclosed in Patent Document 6 and known as a polymer that orients liquid crystal perpendicular to the rubbing direction is aligned when heated after rubbing. The direction changes from the perpendicular direction to the parallel direction with respect to the rubbing direction. In particular, after the liquid crystal display element is created, when the liquid crystal is heated to an isotropic liquid state and annealed to correct the alignment defects of the liquid crystal display element, the alignment direction changes from a direction perpendicular to the rubbing direction to a parallel direction. There was a problem of doing. On the other hand, it has also been desired that the liquid crystal alignment film can be fired at a low temperature of 120 ° C. to 140 ° C. from the viewpoint of low heat resistance of the color filter and energy saving.

  In Patent Document 7, as an example of a polymer compound that aligns liquid crystal molecules in a direction perpendicular to the rubbing direction, a polymer having a ring structure in the side chain is considered, and a cyclopentane ring, a cyclohexane ring in the side chain, Listed are polymers containing benzene ring, naphthalene ring, furan ring, oxolane ring, dioxolane ring, thiophene ring, pyrrole ring, pyran ring, oxane ring, dioxane ring, pyridine ring, piperidine ring, pyrimidine ring, pyrazine ring, etc. . However, only the polymer compound having a benzene ring in the side chain is specifically disclosed in this publication, and other polymer compounds are only suggested to be usable. Not too much. Patent Document 8 discloses that a polymer having a polyamic acid and / or an imide group obtained from 9,9-bis (4-aminophenyl) fluorene and tetracarboxylic dianhydride is perpendicular to the rubbing direction. Discloses the alignment of liquid crystal molecules.

Further, the photocrosslinking type liquid crystal alignment film is disclosed in Japanese Patent Application Laid-Open Publication No. 9-133826. Further, the liquid crystal alignment film is disclosed in Japanese Patent Application Laid-Open No. 10-133826. Moreover, although the optical compensation sheet and the polarizer are disclosed in Japanese Patent Application Laid-Open No. 11-260, they have not been put into practical use. Moreover, although it disclosed by patent document 12 and patent document 13 as a conductive polymer and an electroluminescent element, it has not reached the practical use. An organic semiconductor device is disclosed in Patent Publication 14, but has not yet been put into practical use.

JP-A-6-214116 Japanese Patent Laid-Open No. 10-54982 International patent application WO 96/37804 JP-A-9-26572 Japanese Patent No. 2866372 Japanese Patent Laid-Open No. 2-77015 JP-A-1-304424 Japanese Patent Laid-Open No. 11-212097 JP 2000-98394 A JP 2002-350859 A JP 2002-98836 A JP 2003-155476 A Japanese Patent Application No. 2002-322413 Japanese Patent Application No. 2004-006754

  First, in an optical compensation sheet having an optically anisotropic layer formed from liquid crystalline molecules, the average direction of lines obtained by projecting the major axis direction of liquid crystalline molecules onto a transparent support surface is the optical compensation sheet. Corresponds to the slow axis. The average direction of the lines obtained by projecting the major axis direction of the liquid crystal molecules onto the transparent support surface generally corresponds to the rubbing direction of the liquid crystal alignment film. The optical compensation sheet is roll-shaped in actual production, and the rubbing process is most easily performed in the longitudinal direction of the roll-shaped optical compensation sheet. Therefore, in an optical compensation sheet having an optically anisotropic layer formed from liquid crystalline molecules, an embodiment having a slow axis in the longitudinal direction can be most easily produced. The transmission axis of the polarizing film corresponds to a direction perpendicular to the stretching direction of the polymer film constituting the polarizing film. The polarizing element is also roll-shaped in actual production, and the stretching process is most easily performed in the longitudinal direction of the roll-shaped polarizing film. Therefore, a polarizing element having a transmission axis in a direction perpendicular to the longitudinal direction (width direction) can be most easily produced.

  From the above relationship, when laminating a roll-shaped optical compensation sheet and a roll-shaped polarizing element, it is most produced to arrange the slow axis of the optical compensation sheet and the transmission axis of the polarizing film to be substantially perpendicular to each other. Is easy. On the other hand, depending on the display mode of the liquid crystal display element, it may be preferable to arrange the slow axis of the optical compensation sheet and the transmission axis of the polarizing film so as to be substantially parallel. In order for the slow axis of the roll-shaped optical compensation sheet to be the width direction of the optical compensation sheet, it is necessary to align the liquid crystal molecules so that the major axis direction is perpendicular to the rubbing direction of the liquid crystal alignment film. is there. In this specification, “the long axis direction of the liquid crystal molecules is perpendicular to the rubbing direction of the liquid crystal alignment film” means that the average direction of the lines obtained by projecting the long axis direction of the liquid crystal molecules on the transparent support surface is Means orthogonal to the rubbing direction. In order to align liquid crystal molecules so as to be perpendicular to the rubbing direction, a liquid crystal alignment film having such an alignment function is required. A conventional liquid crystal alignment film has a function of aligning liquid crystal molecules in parallel to the rubbing direction.

One of the objects of the present invention is to provide a liquid crystal alignment film having a function of aligning liquid crystal molecules substantially perpendicular to the rubbing and / or stretching direction.
Secondly, another object of the present invention is to solve the above-mentioned problems relating to the liquid crystal alignment film, by aligning the liquid crystal in a direction different from the rubbing direction by rubbing and performing a heat treatment such as annealing. Another object of the present invention is to provide a liquid crystal alignment film that can be fired at a low temperature without changing the alignment direction, and a liquid crystal display element using the liquid crystal alignment film.
Yet another object of the present invention is to provide a roll-shaped optical compensation sheet having a slow axis in the width direction. Still another object of the present invention is to provide a polarizing plate that can be easily arranged so that the slow axis of the optical compensation sheet and the transmission axis of the polarizing film are substantially parallel.
Thirdly, another object of the present invention is to solve the problem of alignment failure due to scratches or rubbing scraps that are frequently generated by rubbing, and to provide a liquid crystal alignment film using a photocrosslinking polymer compound. An object of the present invention is to provide a liquid crystal alignment film capable of avoiding problems due to rubbing.

The present inventor does not use even experimental equipment alone, and when a polymer compound having a specific structure is rubbed or irradiated with polarized ultraviolet rays, the liquid crystal is aligned in a direction different from the rubbing direction or in the polarization direction, and annealed. The present inventors invented the present invention under a thought experiment, convinced that a liquid crystal alignment film that can be baked at a low temperature can be obtained without changing the alignment direction even when heat treatment as described above is performed.

In the case of a liquid crystal alignment film used for a liquid crystal display device, since the support is often a glass substrate, a high-temperature baking process is often applicable. That is, it is desirable to apply a polymer such as polyamic acid or soluble polyimide that stabilizes the orientation of the liquid crystal when baked at high temperature. That is, in the case of polyamic acid, it is desirable to form a polyimide by reacting a carboxyl group (—COOH) and an imino group (—NH—) of an amide bond by firing, and even a soluble polyimide such as NMP ( N-methyl-2-pyrrolidone) and the like are preferably completely dried.
That is, the raw material of these polymer compounds is preferably a polymer compound containing indole in which at least one aromatic compound is bonded to one of a diamino compound and tetracarboxylic dianhydride in the side chain.
In the case of a liquid crystal alignment film used for an optical compensation sheet, since the support is a polymer film such as triacetyl cellulose (TAC) or polyethylene terephthalate (PET), the liquid crystal alignment film is inferior in heat resistance. Is an acrylic acid and / or vinyl polymer compound, that is, formed of a compound having an indole to which at least one aromatic compound is bonded as a side chain of the acrylic acid and / or vinyl polymer compound It is desirable to be a polymer compound.
That is, the configuration of the present invention is as follows.

(1) (refers to an organic group having an aromatic heterocyclic ring, hereinafter the same) aromatic heterocyclic compound group containing a nitrogen atom of the skeleton structure other than a carbazole derivative and an imide derivative at least one aromatic ring compound Monomoto to A polymer compound, wherein a compound to which a compound to which an organic group having an aromatic ring (hereinafter the same applies) is bonded contains a group bonded through a nitrogen atom is included in a side chain of the polymer.

(2) A diamino compound represented by the following general formula [1].

（但し、一般式［１］においてＧ_１は炭素数２〜２０の３価の有機基、Ｇ_２は独立に単結合、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−、−ＣＯＮＨ−、−Ｏ−、−Ｓ−、−ＣＯ−、アルキレン基、アリーレン基、アリーレンビニレン基、２価の芳香族複素環化合物基または２価の芳香族環化合物基を示し、Ｇ_３は単結合、アリーレン基、アリーレンビニレン基、２価の芳香族複素環化合物基、２価の芳香族環化合物基または炭素数１〜２０のアルキレン基を示し、Ｘは水素原子、フッ素原子、塩素原子、シアノ基、ニトロ基または炭素数１〜１２のアルキル基、ハロアルキル基、アルコキシ基若しくはハロアルコキシ基、または炭素数３〜８のシクロアルキル基、または炭素数９〜１４のトランス−４−アルキルシクロヘキシル基を示し、ｍは０〜３の整数を表し、ベンゼン環ＡおよびＢは、それぞれ、他のベンゼン環が縮合していてもよく、ベンゼン環Ａ、Ｂおよびそれらの縮合環は、置換基を有していてもよい。）

(In the general formula [1], G ₁ is a trivalent organic group having 2 to 20 carbon atoms, G ₂ is independently a single bond, —COO—, —OCO—, —NHCO—, —CONH—, —O -, -S-, -CO-, an alkylene group, an arylene group, an arylene vinylene group, a divalent aromatic heterocyclic compound group or a divalent aromatic ring compound group, G ₃ is a single bond, an arylene group, An arylene vinylene group, a divalent aromatic heterocyclic compound group, a divalent aromatic ring compound group or an alkylene group having 1 to 20 carbon atoms, wherein X is a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or a nitro group. Or an alkyl group having 1 to 12 carbon atoms, a haloalkyl group, an alkoxy group or a haloalkoxy group, a cycloalkyl group having 3 to 8 carbon atoms, or a trans-4-alkylcyclohexyl group having 9 to 14 carbon atoms, Represents an integer of 0 to 3, and each of the benzene rings A and B may be condensed with another benzene ring, and the benzene rings A and B and their condensed rings may have a substituent. Good.)

(3) A vinyl compound represented by the following general formula [2].

（但し、一般式［２］においてＧ_２は独立に単結合、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−、−ＣＯＮＨ−、−Ｏ−、−Ｓ−、−ＣＯ−、アルキレン基、アリーレン基、アリーレンビニレン基、２価の芳香族複素環化合物基または２価の芳香族環化合物基を示し、Ｇ_３は単結合、アリーレン基、アリーレンビニレン基、２価の芳香族複素環化合物基、２価の芳香族環化合物基または炭素数１〜２０のアルキレン基を示し、Ｇ_４は水素、フッ素、塩素原子、もしくは炭素数１〜１２の１価の有機基を示し、Ｘは水素原子、フッ素原子、塩素原子、シアノ基、ニトロ基または炭素数１〜１２のアルキル基、ハロアルキル基、アルコキシ基若しくはハロアルコキシ基、または炭素数３〜８のシクロアルキル基、または炭素数９〜１４のトランス−４−アルキルシクロヘキシル基を示し、ｍは０〜３の整数を表し、ベンゼン環ＡおよびＢは、それぞれ、他のベンゼン環が縮合していてもよく、ベンゼン環Ａ、Ｂおよびそれらの縮合環は、置換基を有していてもよい。）

(In the general formula [2], G ₂ is independently a single bond, —COO—, —OCO—, —NHCO—, —CONH—, —O—, —S—, —CO—, an alkylene group, an arylene group. , An arylene vinylene group, a divalent aromatic heterocyclic compound group or a divalent aromatic ring compound group, and G ₃ represents a single bond, an arylene group, an arylene vinylene group, a divalent aromatic heterocyclic compound group, 2 A valent aromatic ring compound group or an alkylene group having 1 to 20 carbon atoms, G ₄ represents hydrogen, fluorine, a chlorine atom, or a monovalent organic group having 1 to 12 carbon atoms, X is a hydrogen atom, fluorine An atom, a chlorine atom, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms, a haloalkyl group, an alkoxy group or a haloalkoxy group, or a cycloalkyl group having 3 to 8 carbon atoms, or trans having 9 to 14 carbon atoms A 4-alkylcyclohexyl group, m represents an integer of 0 to 3, benzene rings A and B may each be condensed with another benzene ring, and benzene rings A and B and their condensed rings are And may have a substituent.)

(4) A polymer compound having at least one group of the following general formula [3] in the side chain.

（但し、一般式［３］において基中の任意の水素原子は、ハロゲン、アリル基、アルキル基、アルコキシ基、アルキルチオ基、アルキルシリル基、アリール基、アリールオキシ基、アリールシリル基、アルキルアミノ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルシリル基、アリールアルケニル基、アリールアルキニル基、アリールアミノ基、1価の複素環基またはシアノ基で置換されていてもよく、Ｌは任意の二価基を示し、ベンゼン環ＡおよびＢは、それぞれ、他のベンゼン環が縮合していてもよく、ベンゼン環Ａ、Ｂおよびそれらの縮合環は、置換基を有していてもよい。）

(However, in the general formula [3], any hydrogen atom in the group is halogen, allyl group, alkyl group, alkoxy group, alkylthio group, alkylsilyl group, aryl group, aryloxy group, arylsilyl group, alkylamino group. , Arylalkyl group, arylalkoxy group, arylalkylsilyl group, arylalkenyl group, arylalkynyl group, arylamino group, monovalent heterocyclic group or cyano group, L may be any divalent group And the benzene rings A and B may be condensed with other benzene rings, respectively, and the benzene rings A and B and the condensed rings thereof may have a substituent.)

(5) A polymer compound comprising the following general formula [4] as at least a part of a structural unit.

（但し、一般式［４］においてＧ₁は水素、フッ素、塩素原子、もしくは炭素数１〜１２の１価の有機基を表す。Ｇ₂は独立に単結合、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−、−ＣＯＮＨ−、−Ｏ−、−Ｓ−、−ＣＯ−、アルキレン基、アリーレン基、アリーレンビニレン基、２価の芳香族複素環化合物基または２価の芳香族環化合物基を示し、Ｇ₃は単結合、アリーレン基、アリーレンビニレン基、２価の芳香族複素環化合物基、２価の芳香族環化合物基または炭素数１〜２０のアルキレン基を示す。Ｘは水素原子、フッ素原子、塩素原子、シアノ基、ニトロ基または炭素数１〜１２のそれぞれ、アルキル基、ハロアルキル基、アルコキシ基若しくはハロアルコキシ基または炭素数３〜８のシクロアルキル基または炭素数９〜１４のトランス−４−アルキルシクロヘキシル基を示し、ｍは０〜３の整数を表し、ベンゼン環ＡおよびＢは、それぞれ、他のベンゼン環が縮合していてもよく、ベンゼン環Ａ、Ｂおよびそれらの縮合環は、置換基を有していてもよい。）

(In the general formula [4], G ₁ represents hydrogen, fluorine, chlorine atom, or a monovalent organic group having 1 to 12 carbon atoms. G ₂ independently represents a single bond, —COO—, —OCO—, —NHCO—, —CONH—, —O—, —S—, —CO—, alkylene group, arylene group, arylene vinylene group, divalent aromatic heterocyclic compound group or divalent aromatic ring compound group. , G ₃ represents a single bond, an arylene group, an arylene vinylene group, a divalent aromatic heterocyclic compound group, a divalent aromatic ring compound group or an alkylene group having 1 to 20 carbon atoms, X is a hydrogen atom, fluorine An atom, a chlorine atom, a cyano group, a nitro group or a C 1-12 alkyl group, a haloalkyl group, an alkoxy group, a haloalkoxy group, a C 3-8 cycloalkyl group, or a C 9-14 transaction -4-alkylcyclohexyl group, m represents an integer of 0 to 3, benzene rings A and B may be condensed with other benzene rings, respectively, benzene rings A and B and their condensed rings May have a substituent.)

(6) At least one type of structural unit represented by the following general formula [5] by addition polymerization of a compound containing a double bond other than the general formula [2] and the general formula [2]. A polymer compound characterized by comprising

（但し、一般式［５］においてＧ_６およびＧ_７はそれぞれ独立に水素、フッ素、塩素原子、もしくは炭素数１〜１２の一価の有機基を表す。）

(However, in General Formula [5], G ₆ and G ₇ each independently represent hydrogen, fluorine, a chlorine atom, or a monovalent organic group having 1 to 12 carbon atoms.)

(7) An optical element including a liquid crystal alignment film provided on a support, wherein the liquid crystal alignment film includes a polymer compound of (4) to (6).

(8) A liquid crystal alignment film comprising an optical functional layer comprising a support, a liquid crystal alignment film, and a liquid crystal compound and used for the production of an optical element, wherein the liquid crystal alignment film according to claim 7 An optical element manufactured using

(9) A conductive polymer comprising the polymer compound of (4) to (6).

(10) An organic electroluminescence device comprising the conductive polymer of (9)

(11) An organic semiconductor device comprising the liquid crystal alignment film of (7)

The diamino compound of the present invention is represented by the general formula [1]. The structure of the G ₁ moiety in the general formula [1] is not particularly limited as long as it is a trivalent organic group having 2 to 20 carbon atoms.

等が挙げられる（ただし、ｐは０〜１０の整数、ｑは１〜１０の整数を示す）が上記の基には限定されない。この中で、好ましくは、

(However, p represents an integer of 0 to 10, q represents an integer of 1 to 10), but is not limited to the above groups. Of these, preferably

であり、最も好ましくは

And most preferably

It is. In addition, any hydrogen atom in these groups is halogen, allyl group, alkyl group, alkoxy group, alkylthio group, alkylsilyl group, aryl group, aryloxy group, arylsilyl group, alkylamino group, arylalkyl group, The arylalkoxy group, arylalkylsilyl group, arylalkenyl group, arylalkynyl group, arylamino group, monovalent heterocyclic group or cyano group may be substituted.

The structure of the L moiety in the general formula [3] of the present invention may be any divalent group, but preferably is independently a single bond, —COO—, —OCO—, —NHCO—, —CONH—, A group selected from -O-, -S-, -CO-, an alkylene group, an arylene group, an arylene vinylene group, a divalent aromatic heterocyclic compound group, a divalent aromatic ring compound group, and combinations thereof , Preferably -COO-, -OCO-, -O-, -CO-, an alkylene group having 1 to 20 carbon atoms, an arylene group, an arylene vinylene group, a divalent aromatic heterocyclic compound group or a divalent aromatic Any group selected from a ring compound group and a combination thereof may be used.

The present inventors have for the first, the result of the discussion, the side of at least one aromatic ring compound group is bonded groups to the aromatic heterocyclic compound group containing a nitrogen atom of the skeleton structure other than mosquitoes carbazole derivatives and imide derivatives Polymer compounds containing a chain, specifically 2-phenylindole derivatives, 2- (2-naphthyl) indole derivatives or addition polymerization compounds containing 2- (1-naphthyl) indole derivatives in the side chain (for example, vinyl polymers) , Acrylic acid polymers, etc.) or condensation polymerization compounds (eg, polyimide or polyamic acid) are used for the liquid crystal alignment film, and it has been found that liquid crystal molecules can be uniformly aligned so as to be substantially perpendicular to the rubbing direction. did.

  Thereby, it is possible to produce an optical compensation sheet in which liquid crystalline molecules are aligned in a direction different from the rubbing direction, for example, substantially perpendicular to the rubbing direction. Accordingly, it has become possible to easily produce a roll-shaped optical compensation sheet having a slow axis in a direction (width direction) perpendicular to the longitudinal direction. On the other hand, as described above, a roll-shaped polarizing element having a transmission axis in a direction (width direction) perpendicular to the longitudinal direction can be most easily produced. Therefore, the polarizing plate in which the slow axis of the optical compensation sheet and the transmission axis of the polarizing film are substantially parallel by bonding the roll-shaped optical compensation sheet and the roll-shaped polarizing element according to the present invention in a roll state. Can be produced. As described above, by using the optical compensation sheet according to the present invention, the slow axis of the optical compensation sheet and the transmission axis of the polarizing film can be easily arranged so as to be substantially parallel.

  Secondly, according to the present invention, the liquid crystal alignment film is provided with a liquid crystal alignment ability in a direction different from the rubbing direction by rubbing, and the alignment direction does not change even when heat treatment such as annealing is performed, and is fired at a low temperature. And a liquid crystal display element using the liquid crystal alignment film. Since the liquid crystal alignment film of the present invention aligns the liquid crystal in a direction different from the rubbing direction, a coating film is formed on the substrate in a certain pattern together with a polymer that aligns the liquid crystal parallel to the rubbing direction. By performing this once, orientation division can be easily performed. Further, since the alignment direction does not change even when heat treatment such as annealing is performed, it can be suitably used as a liquid crystal alignment film. In addition, since it can be fired at a low temperature of 120 ° C. to 140 ° C., it can be used even if the heat resistance of the color filter is low, and it is advantageous from the viewpoint of energy saving. In addition, it can be suitably used for a recording material, a polarizing element, an optical compensation plate, a light control element, and the like.

In the present invention the side chain end groups {e.g., 2-phenyl-indolinium group, 2- (2-naphthyl) indolinium group, 2- (2-naphthyl) and India Li Le group} between the main chain A connection group such as COO may be inserted. Thus, in the liquid crystal alignment film aligned with the radiation (UV, electron beam, etc.) is improved reaction rate by spread variable dynamic range of the side chains, resulting in orientation of the liquid crystal molecules was improved. Moreover, the effect that the solubility improved and the adhesive strength with a support body also improved was produced. Furthermore, in the case of nematic liquid crystals, the liquid crystalline molecules can expand and contract perpendicularly with respect to the support instead of the layer structure, so that the alignment position of the nematic liquid crystals can be accommodated, and as a result, the alignment is improved.
In addition, when the connecting group is COO, it is electron withdrawing, so that intramolecular donors and intramolecular acceptors are generated in the liquid crystal alignment film, and the interaction between intramolecular donors and intramolecular acceptors in the liquid crystal molecules is increased. As a result, the orientation characteristics were improved.

The using 2-phenylindole in the side chain in the present invention is poor in solubility in solvents polyvinylcarbazole, is because has the disadvantage that not raise the molecular weight. Polyvinylcarbazole and the like have low solvent solubility, and it has become difficult to produce a high molecular weight liquid crystal alignment film by coating. Therefore, in the present invention, an aromatic heterocyclic compound group in the side chain of the polymer, for example, groups obtained by binding an aromatic ring compound group such as a naphthyl group in India Lil groups {e.g. 2- (2-naphthyl) indolyl group, with improved solubility in a solvent by increasing the freedom of the three-dimensional rotation in the coupling axis by which to have a 2-like (1-naphthyl) indolyl group}.
In addition, the film thickness is less likely to vary in the plane of the support when applied in order to improve solubility, and as a result, uneven application is less likely to occur.

  When orientation is imparted by rubbing, scratches or the like are likely to occur due to scraping of the liquid crystal alignment film by rubbing on the rubbing roller and the film surface. This is considered that when the liquid crystal alignment film is charged, shavings are easily adsorbed on the film surface and scratches are likely to occur. Therefore, a liquid crystal alignment film is formed of a polymer compound containing, in a side chain, an aromatic heterocyclic compound group containing a nitrogen atom having a skeleton structure other than a carbazole derivative and an imide derivative and a group in which at least one aromatic ring compound group is bonded. By forming the film, scratches on the film surface caused by rubbing could be reduced.

Since the side chain has a group in which at least one aromatic ring compound group is bonded to an aromatic heterocyclic compound group containing a nitrogen atom having a skeleton structure other than a carbazole derivative and an imide derivative, a simple carbazole (one aromatic complex) ring group) only increased amorphous than polyvinylcarbazole on the side chain, bulky group is improved transparency under up Rukoto the density of the polymer film. In addition, there was no light birefringence seen in crystalline polymers, and transparency was improved.

  The use of 2-phenylindole, which is highly amorphous in the side chain and has a high degree of freedom of steric rotation around the bond axis, causes a bias in the electrons in the side chain molecule, so intermolecular interactions between the side chain molecules As a result, in the case of an optical compensation sheet in which a liquid crystal-containing solution must be applied to the upper layer of the liquid crystal alignment film or a liquid crystal display element in direct contact with the liquid crystal, the swelling of the liquid crystal alignment film with respect to the solvent or liquid crystal is suppressed. be able to.

In the polymer compound of the present invention, the steric structure of the side chain is not a structure close to a plane like carbazole, but the side chain is aromatic in the aromatic heterocyclic compound group containing a nitrogen atom of a skeleton structure other than the carbazole derivative and the imide derivative. A structure in which a ring compound group is bonded, and as a result, the entanglement between side chains or between the side chain and the polymer main chain increases, thereby improving the glass transition point of the liquid crystal alignment film composed of the polymer compound of the present invention. As a result, since the heat resistance was improved, the product life was extended.

Furthermore, at least one aromatic ring compound group in the aromatic heterocyclic compound group containing a nitrogen atom of a skeleton structure other than the carbazole derivative and imide derivative in the side chain of the polymer compound constituting the liquid crystal alignment film with biphenyl It becomes easy to align a liquid crystal containing an electron donating group such as biphenyl by intermolecular interaction with a group to which is bonded.
In addition, when the aromatic ring compound group bonded to the aromatic heterocyclic compound group containing a nitrogen atom of a skeleton structure other than the side chain carbazole derivative and imide derivative is a compound such as naphthalene, naphthalene itself forms a crystal. As a result, it becomes easy to uniformly align the liquid crystal containing naphthalene.

Further, in the optical compensation sheet, the adhesion between the optically anisotropic layer and the liquid crystal alignment film becomes a problem. In this case, there is a method of improving the adhesion by adding a slight amount of a polyfunctional monomer. When the solution containing it is applied, the polyfunctional monomer oozes into the upper liquid crystal layer and adversely affects the orientation. Therefore the Kaoru incense ring freely rotates in the side chain of the polymer compound contained in the liquid crystal alignment film by introducing the polymer compound, it is possible to improve the adhesion to the support.
Further, by mixing these polymer compounds with conventional polyvinyl carbazole at a certain ratio, it is possible to form a liquid crystal alignment film having a concentration gradient in which the ratio of both components is different with respect to the depth direction. As a result, the surface of the liquid crystal alignment film has good adhesion to an optically anisotropic layer made of liquid crystalline molecules, for example, a polymer compound (carbazole derivative and carbazole derivative) containing a group containing a 2- (2-naphthyl) indole derivative in the side chain. Polymer containing in side chain a group in which at least one aromatic ring compound group is bonded to a nitrogen atom-containing aromatic heterocyclic compound group having a skeleton structure other than an imide derivative via a nitrogen atom Compound) is easily deposited, and the inside of the liquid crystal alignment film is a polymer compound mainly composed of, for example, polyvinyl carbazole. Therefore, a polymer compound having high alignment function and / or high adhesion to the optically anisotropic layer is formed on the surface layer. It was possible to introduce a polymer compound having good film-forming properties and / or good adhesion to a support such as TAC. As a result, it is possible to form an alignment film having a functionally separated component concentration gradient, and a liquid crystal alignment film having good adhesion to both the support and the optically anisotropic layer can be formed. .

The aromatic heterocyclic compound group containing a nitrogen atom having a skeleton structure other than the carbazole derivative and the imide derivative and the terminal group containing the aromatic ring compound group bonded thereto all interact with the biphenyl group of the liquid crystal. Therefore, a group in which at least one aromatic ring compound group is bonded to an aromatic heterocyclic compound group containing a nitrogen atom having a skeleton structure other than the carbazole derivative and imide derivative of the present invention is bonded via the nitrogen atom. By synthesizing a polymer compound containing a group in a side chain and using it as a liquid crystal alignment film, the alignment property of liquid crystal molecules in the liquid crystal alignment film is improved.
In particular, in a liquid crystal display device, an alignment film that does not require rubbing can be formed by using the polymer compound of the present invention as the photo-alignment film. In addition, an alignment film having a gradient distribution of concentration in the depth direction is prepared by mixing the polymer compound of the present invention and another polymer compound. As a result, molecules capable of crosslinking on the surface of the liquid crystal alignment film are obtained. Precipitation improved the alignment of the liquid crystal molecules on the surface of the liquid crystal alignment film.

In the present invention, when an acrylic acid-based and / or vinyl-based polymer compound, an imide-based polymer compound (polyimide) or an amic acid-based polymer compound (polyamic acid) having a carbazole skeleton in the side chain is used for the liquid crystal alignment film, It was found that liquid crystal molecules can be uniformly aligned so as to be substantially perpendicular to the rubbing direction. Thereby, an optical compensation sheet in which liquid crystalline molecules are aligned substantially perpendicular to the rubbing direction can be produced. Accordingly, it has become possible to easily produce a roll-shaped optical compensation sheet having a slow axis in a direction (width direction) perpendicular to the longitudinal direction. On the other hand, as described above, a roll-shaped polarizing element having a transmission axis in a direction (width direction) perpendicular to the longitudinal direction can be most easily produced. Therefore, the polarizing plate in which the slow axis of the optical compensation sheet and the transmission axis of the polarizing film are substantially parallel by bonding the roll-shaped optical compensation sheet and the roll-shaped polarizing element according to the present invention in a roll state. Can be produced. As described above, by using the optical compensation sheet according to the present invention, the slow axis of the optical compensation sheet and the transmission axis of the polarizing film can be easily arranged so as to be substantially parallel.
In addition, an alignment film for a liquid crystal display element characterized by using a photosensitive polymer compound having an indole residue in the side chain obtained by the present invention is highly sensitive to polarized ultraviolet light, and Upon irradiation, the side chain rapidly photoreacts to form a cyclobutane ring. In addition, the film after the photoreaction is excellent in thermal stability and shape retention, exhibits good liquid crystal molecule alignment performance substantially equivalent to the rubbing treatment, and is useful as a non-rubbed alignment film.

  The liquid crystal alignment film for aligning liquid crystal in a direction different from the rubbing direction or in a polarization direction by rubbing and / or radiation (indicating ultraviolet rays, electron beams, etc., and polarization etc. may be added for ultraviolet rays) of the present invention. . Alternatively, an alignment film that aligns liquid crystal in the rubbing direction may be used. At this time, heat treatment may be used before and after the alignment treatment. At this time, the heat treatment can be performed at a low temperature. Furthermore, the liquid crystal alignment film of the present invention is a liquid crystal alignment film whose alignment direction does not change even when heat treatment such as annealing is performed.

In the polymer compound of the present invention, at least one or more kinds of side chain groups in which at least one aromatic ring compound group is bonded to an aromatic heterocyclic compound group containing a nitrogen atom having a skeleton structure other than a carbazole derivative and an imide derivative a polymer compound having, for example, as the imidazole and / or groups to at least one or more Kaoru incense ring is bonded groups such indole, for example, groups represented by the general formula [3]. In addition, examples of the polymer compound of the present invention include a polymer compound obtained by condensation polymerization of a diamino compound represented by the general formula [1] and, for example, tetracarboxylic dianhydride, and a general formula [2] such as other acrylics. Examples thereof include a polymer compound obtained by addition polymerization with an acid or the like.

（但し、一般式［３］において基中の任意の水素原子は、ハロゲン、アリル基、アルキル基、アルコキシ基、アルキルチオ基、アルキルシリル基、アリール基、アリールオキシ基、アリールシリル基、アルキルアミノ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルシリル基、アリールアルケニル基、アリールアルキニル基、アリールアミノ基、1価の複素環基またはシアノ基で置換されていてもよく、Ｌは任意の二価基を示し、ベンゼン環ＡおよびＢは、それぞれ、他のベンゼン環が縮合していてもよく、ベンゼン環Ａ、Ｂおよびそれらの縮合環は、置換基を有していてもよい。）

(However, in the general formula [3], any hydrogen atom in the group is halogen, allyl group, alkyl group, alkoxy group, alkylthio group, alkylsilyl group, aryl group, aryloxy group, arylsilyl group, alkylamino group. , Arylalkyl group, arylalkoxy group, arylalkylsilyl group, arylalkenyl group, arylalkynyl group, arylamino group, monovalent heterocyclic group or cyano group, L may be any divalent group And the benzene rings A and B may be condensed with other benzene rings, respectively, and the benzene rings A and B and the condensed rings thereof may have a substituent.)

Examples of the group in which at least one aromatic ring compound group is bonded to an aromatic heterocyclic compound group containing a nitrogen atom having a skeleton structure other than a carbazole derivative and an imide derivative include, for example, 2-phenylimidazole derivatives, 2- (2-naphthyl) ) Imidazole derivatives, 2- (1-naphthyl) imidazole derivatives, 2- (2-naphthyl) indole derivatives, 2- (1-naphthyl) indole derivatives, groups composed of 2-phenylindole derivatives, and the like. The side chain of the polymer compound is not limited to the above compounds.

  Specific chemical structures contained in the terminal group of the side chain in the polymer compound of the present invention include 2-phenyl-6-nitrobenzimidazole, 2-phenylimidazole, 2- (2-naphthyl) imidazole, 2- ( 1-naphthyl) imidazole, 2- (2-naphthyl) indole, 2- (1-naphthyl) indole, 2-phenylindole, 2-phenylindole-3-acetonitrile, 2-phenylindolecarboxyartehydride and the like. The terminal group in the side chain of the polymer compound of the present invention is not limited to the above compound.

The terminal groups of a specific side chain in the polymer compound of the present invention, 2- (2-naphthyl) indole-1-b group, 2- (1-naphthyl) indole-1-b group, 2- (5-naphthyl) pyrrolo [2,3-b] pyridin-1-b group, 2- (5-naphthyl) but derivatives such as pyrrolo [3,2-b] pyridin-1-y le group However, the present invention is not limited to these.

（但し、一般式［１］においてＧ_１は炭素数２〜２０の３価の有機基、Ｇ_２は独立に単結合、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−、−ＣＯＮＨ−、−Ｏ−、−Ｓ−、−ＣＯ−を示し、Ｇ_３は単結合または炭素数１〜２０のアルキレン基を示し、Ｘは水素原子、フッ素原子、塩素原子、シアノ基、ニトロ基または炭素数１〜１２のアルキル基、ハロアルキル基、アルコキシ基若しくはハロアルコキシ基、または炭素数３〜８のシクロアルキル基、または炭素数９〜１４のトランス−４−アルキルシクロヘキシル基を示し、ｍは０〜３の整数を表し、ベンゼン環ＡおよびＢは、それぞれ、他のベンゼン環が縮合していてもよく、ベンゼン環Ａ、Ｂおよびそれらの縮合環は、置換基を有していてもよい。）

(In the general formula [1], G ₁ is a trivalent organic group having 2 to 20 carbon atoms, G ₂ is independently a single bond, —COO—, —OCO—, —NHCO—, —CONH—, —O —, —S—, —CO—, G ₃ represents a single bond or an alkylene group having 1 to 20 carbon atoms, X represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group or a carbon number of 1 to 12 represents an alkyl group, a haloalkyl group, an alkoxy group or a haloalkoxy group, a cycloalkyl group having 3 to 8 carbon atoms, or a trans-4-alkylcyclohexyl group having 9 to 14 carbon atoms, and m is an integer of 0 to 3 The benzene rings A and B may each be condensed with another benzene ring, and the benzene rings A and B and their condensed rings may have a substituent.

(However, G in the general formula [2] ₂ Are independently a single bond, —COO—, —OCO—, —NHCO—, —CONH—, —O—, —S—, —CO—, an alkylene group, an arylene group, an arylene vinylene group, a divalent aromatic complex. A ring compound group or a divalent aromatic ring compound group, ₃ Represents a single bond, an arylene group, an arylene vinylene group, a divalent aromatic heterocyclic compound group, a divalent aromatic ring compound group or an alkylene group having 1 to 20 carbon atoms; ₄ Represents hydrogen, fluorine, chlorine atom, or a monovalent organic group having 1 to 12 carbon atoms, X represents a hydrogen atom, fluorine atom, chlorine atom, cyano group, nitro group, or alkyl group having 1 to 12 carbon atoms, haloalkyl Group, an alkoxy group or a haloalkoxy group, a cycloalkyl group having 3 to 8 carbon atoms, or a trans-4-alkylcyclohexyl group having 9 to 14 carbon atoms, m represents an integer of 0 to 3, and benzene ring A And B may each be condensed with another benzene ring, and the benzene rings A and B and those condensed rings may have a substituent. )

  The polymer compound of the present invention has at least one or more kinds of side chains each having a group in which at least one aromatic ring compound group is bonded to an aromatic heterocyclic compound group containing a nitrogen atom having a skeleton structure other than a carbazole derivative and an imide derivative. A polymer compound having a side chain having at least one group of the following general formula [6].

（但し、一般式［６］において基中の任意の水素原子は、ハロゲン、アリル基、アルキル基、アルコキシ基、アルキルチオ基、アルキルシリル基、アリール基、アリールオキシ基、アリールシリル基、アルキルアミノ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルシリル基、アリールアルケニル基、アリールアルキニル基、アリールアミノ基、1価の複素環基またはシアノ基で置換されていてもよく、Ｌは任意の二価基を示し、ＥＧはカルバゾール誘導体およびイミド誘導体以外の骨格構造の窒素原子を含む芳香族複素環化合物基に少なくとも一つ以上の芳香族環化合物基が結合した基を示す。）
本発明の一般式［６］に示される末端基のＥＧとして具体的には

(However, in the general formula [6], any hydrogen atom in the group is halogen, allyl group, alkyl group, alkoxy group, alkylthio group, alkylsilyl group, aryl group, aryloxy group, arylsilyl group, alkylamino group. , Arylalkyl group, arylalkoxy group, arylalkylsilyl group, arylalkenyl group, arylalkynyl group, arylamino group, monovalent heterocyclic group or cyano group, L may be any divalent group EG represents a group in which at least one aromatic ring compound group is bonded to an aromatic heterocyclic compound group containing a nitrogen atom having a skeleton structure other than the carbazole derivative and imide derivative.)
Specifically, the EG of the terminal group represented by the general formula [6] of the present invention is

The EG represented by the general formula [6] of the present invention is not limited to the above chemical structure. (Any hydrogen atom in these groups is halogen, allyl group, alkyl group, alkoxy group, alkylthio group, alkylsilyl group, aryl group, aryloxy group, arylsilyl group, alkylamino group, arylalkyl group, aryl (It may be substituted with an alkoxy group, an arylalkylsilyl group, an arylalkenyl group, an arylalkynyl group, an arylamino group, a monovalent heterocyclic group or a cyano group.)

Further, it is needless to say that the end group EG of the side chain in the polymer compound of the present invention may be the end group in [Chemical Formula 53] to [Chemical Formula 125] (General Formula 42 to General Formula 114) of Japanese Patent Application No. 2004-209725. . However, the optical compensation film has a problem because it is expensive, but it seems to be applicable only to a relatively expensive product group.

Further, as an example of the polymer compound of the present invention, the EG represented by the general formula [6] is a fragrance in which a part of the structure of the liquid crystal and / or the chiral agent contains a nitrogen atom having a skeleton structure other than the carbazole derivative and the imide derivative. It may be contained in an aromatic ring compound group bonded to an aromatic heterocyclic compound group and / or an aromatic heterocyclic compound group containing a nitrogen atom having a skeleton structure other than a carbazole derivative and an imide derivative. Specifically, a polymer compound having a chemical structure represented by the general formula [7] to the general formula [12] can be given.

具体的には、

In particular,

さらに具体的には、

More specifically,

などの構造が挙げられるが、本発明の高分子化合物が有する側鎖の末端基に含む化学構造は上記に限られない。（これらの基中の任意の水素原子は、ハロゲン、アリル基、アルキル基、アルコキシ基、アルキルチオ基、アルキルシリル基、アリール基、アリールオキシ基、アリールシリル基、アルキルアミノ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルシリル基、アリールアルケニル基、アリールアルキニル基、アリールアミノ基、1価の複素環基またはシアノ基で置換されていてもよい。）
また、一般式［７］〜一般式［１２］中のＺは下記の構造が挙げられるが、任意の芳香族環化合物および／もしくは芳香族複素環化合物および／もしくはアルキルおよび／もしくはアリールおよび／もしくはハロゲンおよび／もしくはアリルの骨格構造を有する二価基が挙げられる。具体的には、

However, the chemical structure contained in the terminal group of the side chain of the polymer compound of the present invention is not limited to the above. (Any hydrogen atom in these groups is halogen, allyl group, alkyl group, alkoxy group, alkylthio group, alkylsilyl group, aryl group, aryloxy group, arylsilyl group, alkylamino group, arylalkyl group, aryl (It may be substituted with an alkoxy group, an arylalkylsilyl group, an arylalkenyl group, an arylalkynyl group, an arylamino group, a monovalent heterocyclic group or a cyano group.)
Z in the general formula [7] to the general formula [12] has the following structure, and any aromatic ring compound and / or aromatic heterocyclic compound and / or alkyl and / or aryl and / or Examples thereof include a divalent group having a halogen and / or allyl skeleton structure. In particular,

(However, p represents an integer of 0 to 10 and q represents an integer of 1 to 10), but the chemical structure contained in Z is not limited to the above. (Any hydrogen atom in these groups is halogen, allyl group, alkyl group, alkoxy group, alkylthio group, alkylsilyl group, aryl group, aryloxy group, arylsilyl group, alkylamino group, arylalkyl group, aryl (It may be substituted with an alkoxy group, an arylalkylsilyl group, an arylalkenyl group, an arylalkynyl group, an arylamino group, a monovalent heterocyclic group or a cyano group.)

Further, the polymer compound of the present invention may be a polymer compound having the following structure in the end group of the side chain in addition to the above structure to such an extent that the alignment performance of the liquid crystal is not deteriorated.

(Any hydrogen atom in these groups is halogen, allyl group, alkyl group, alkoxy group, alkylthio group, alkylsilyl group, aryl group, aryloxy group, arylsilyl group, alkylamino group, arylalkyl group, aryl (It may be substituted with an alkoxy group, an arylalkylsilyl group, an arylalkenyl group, an arylalkynyl group, an arylamino group, a monovalent heterocyclic group or a cyano group.)

Further, as an example of the polymer compound of the present invention, a group in which at least one aromatic ring compound group is bonded to an aromatic heterocyclic compound group containing a nitrogen atom having a skeleton structure other than a carbazole derivative and an imide derivative is provided on the side. A structure having a side chain containing a cyclic group and a polymer compound contained in the chain (hereinafter sometimes referred to as a raw material polymer D), and sharing one atom in the cyclic group with the main chain It may be a polymer compound containing as a main component at least one polymer compound selected from the group consisting of a polymer compound (hereinafter sometimes referred to as raw material polymer J).
Specific examples of the raw material polymer D include polymer compounds having at least one of the groups represented by the above [Chemical Formula 34] to [Chemical Formula 60] as side chains. May be a polymer compound containing two or more of these.
Specific examples of the raw material polymer J include polymer compounds containing at least one of the divalent groups represented by the following [Chemical Formula 93] to [Chemical Formula 126] as a part of the structural unit. May be a polymer compound containing two or more of these.

(Any hydrogen atom in these groups is halogen, allyl group, alkyl group, alkoxy group, alkylthio group, alkylsilyl group, aryl group, aryloxy group, arylsilyl group, alkylamino group, arylalkyl group, aryl (It may be substituted with an alkoxy group, an arylalkylsilyl group, an arylalkenyl group, an arylalkynyl group, an arylamino group, a monovalent heterocyclic group or a cyano group.)

  Furthermore, specific examples of the structural unit of the polymer compound of the present invention include the structural units of the following [Chemical 127] to [Chemical 165].

(Any hydrogen atom in these groups is halogen, allyl group, alkyl group, alkoxy group, alkylthio group, alkylsilyl group, aryl group, aryloxy group, arylsilyl group, alkylamino group, arylalkyl group, aryl (It may be substituted with an alkoxy group, an arylalkylsilyl group, an arylalkenyl group, an arylalkynyl group, an arylamino group, a monovalent heterocyclic group or a cyano group.)

  Specifically, the raw material polymer D of the polymer compound of the present invention is, for example, addition-polymerized with a vinyl derivative having one of the groups represented by the above [Chemical Formula 34] to [Chemical Formula 60] as a substituent, or In the raw material polymer D, for example, an amine derivative having one of the groups represented by the above [Chemical Formula 34] to [Chemical Formula 60] as a substituent is subjected to condensation polymerization with tetracarboxylic dianhydride, trimellitic acid, or the like. Thus, the polymer compound (polyamic acid derivative, polyimide derivative or polyvinyl derivative) of the present invention can be obtained. In addition to the vinyl derivative, a propylene derivative or butylene derivative having one of the groups represented by [Chemical Formula 34] to [Chemical Formula 60] as a substituent can be used as the addition-polymerizable monomer. Furthermore, the addition-polymerizable monomer may be addition-polymerized alone, or two or more of these may be copolymerized. The monomers capable of condensation polymerization may be subjected to condensation polymerization alone, or two or more of them may be copolymerized.

  Furthermore, as long as the liquid crystal alignment ability in a direction different from the desired alignment direction is not inhibited, even a copolymer of one or more of these monomers and a monomer not having these groups is used. be able to.

  The polymer compound (raw polymer J) having at least one of the groups represented by the above [Chemical Formula 93] to [Chemical Formula 126] as a structural unit is polymerized after one of the carbon atoms constituting the ring is polymerized. The compound having a cyclic group having a structure that becomes a part of the main chain can be obtained by polymerizing the compound. The polymerization method may be a condensation polymerization reaction with another compound or an addition polymerization reaction. That is, as the raw material polymer J, polymer compounds such as polyester, polycarbonate, polyamide, polyimide, polyurethane, polysulfone, and polyethersulfone can be used. The raw material polymer J may be a polymer compound containing two or more of the groups represented by [Chemical Formula 93] to [Chemical Formula 126], and may be added by rubbing and / or radiation irradiation and / or stretching treatment. In addition to one or more of these groups, as long as the liquid crystal alignment ability (the performance of the film that aligns liquid crystal molecules substantially substantially uniformly in a certain direction) is not inhibited, [ A group other than the groups shown in Chemical Formula 93] to [Chemical Formula 126] may be included as a structural unit.

  Preferred polymer compounds from the viewpoint of orientation stability and the like are one or more selected from the following [Chemical Formula 166] to [Chemical Formula 190] among the groups represented by the above [Chemical Formula 93] to [Chemical Formula 126]. It is a polymer compound having a group as a structural unit. (In the following, any hydrogen atom in the formula includes halogen, allyl group, alkyl group, alkoxy group, alkylthio group, alkylsilyl group, aryl group, aryloxy group, arylsilyl group, alkylamino group, arylalkyl group, aryl (It may be substituted with an alkoxy group, an arylalkylsilyl group, an arylalkenyl group, an arylalkynyl group, an arylamino group, a monovalent heterocyclic group or a cyano group.)

  A more preferable polymer compound from the viewpoint of easy availability of raw materials is a polymer compound having a group represented by the following [Chemical 191] as a constituent unit, and represented by the following [Chemical 192]. More preferred is a polymer compound having a repeating unit. (In the following, any hydrogen atom in the formula includes halogen, allyl group, alkyl group, alkoxy group, alkylthio group, alkylsilyl group, aryl group, aryloxy group, arylsilyl group, alkylamino group, arylalkyl group, aryl (It may be substituted with an alkoxy group, an arylalkylsilyl group, an arylalkenyl group, an arylalkynyl group, an arylamino group, a monovalent heterocyclic group or a cyano group.)

  In the present invention, the raw material polymer D and the raw material polymer J can be mixed and used. In addition, in order to improve various properties related to the liquid crystal alignment film, such as solvent resistance, liquid crystal resistance, alignment stability, heat resistance, water resistance, adhesion to the substrate, etc. The molecule J may be blended with other polymers. Examples of the polymer to be blended include polyester, polycarbonate, polyamide, polyimide, polyvinyl alcohol, polyacrylamide, polyacrylonitrile, polysulfone, and polyethersulfone. However, when blending these polymers, care must be taken not to lose the property of aligning the liquid crystal in a direction different from the rubbing direction. At this time, by utilizing the fact that a polymer having a smaller surface energy moves to the surface of the coating film, the object of the present invention can be achieved even if the amount of the raw material polymer D or the raw material polymer J is small. Can do.

In the diamino compound represented by the general formula [1] of the present invention, the G ₁ group of the diamine moiety is bonded to the photosensitive moiety through the linking group G ₂ . Therefore, in the production method of this compound, if both of the diamine part and the photosensitive group part have functional groups capable of reacting with each other, the reaction can be performed using them to connect the two. If not, the necessary functional group can be introduced and then both can be reacted and linked. Inspired by the type of G ₂ , these linking reactions are simply exemplified. In the case of an ester bond, a dehydration reaction of a carboxyl group and a hydroxyl group, an amide bond is a dehydration reaction of an amino group and a carboxyl group, and in the case of an ether bond, In the case of a sulfide bond, a sodium salt of sodium alcoholate and halide is converted to an alkyl halide, and then both are dehalogenated with potassium sulfide. In the case of a carbonyl bond, a cyano group and a Grignard reagent are reacted. Then, it can be synthesized by a known method such as hydrolysis, and in the case of a single bond, a dehydration reaction between an alcohol and an α-arylindole. As a specific example of the method for producing a diamino compound, when G ₂ is a single bond, a nitro group of dinitroalkylene-α-arylindole obtained by a dehydration reaction such as a Mitsunobu reaction with dinitroalcohols and arylindole, for example. Can be produced by reducing it with a metal such as tin or iron and concentrated hydrochloric acid to form a diamino compound. This is represented by the following reaction formula [Chemical 193].

  A diamino compound having an α, β-substituted indole residue in the side chain synthesized in this way is subjected to a polymerization reaction with a tetracarboxylic dianhydride represented by the general formula [13] while retaining the indole residue. Thus, a polyamic acid solution having an indole residue at the end of the side chain, which is composed of the structural unit represented by the general formula [4], can be obtained.

ここでＧ_５は独立に、単結合、−ＣＨ_２−、−Ｏ−、−ＣＯ−、−ＳＯ_２−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−結合である。環Ａ及び環Ｂはそれぞれ独立にベンゼン環またはシクロヘキサン環を示す。このポリアミド酸を加熱または化学的に脱水する等の公知の方法でイミド化した後、偏光させた紫外線を照射することにより本発明のポリイミドを得ることができる。偏光させた紫外線および／もしくは電子線を照射することによって電子線および／もしくは紫外線の照射された部分のインドール残基が重合し、ラビング処理をすることなく液晶配向膜として使用することができるのである。本発明の液晶配向膜は、側鎖の末端にインドール残基を有する本発明のポリアミド酸の溶液を基板に塗布し、加熱等によりイミド化した後、偏光させた紫外線を照射して膜表面に異方性を付与することで製造される。
また本発明の別の態様として、一般式［４］と一般式［１４］

Here, G ₅ is independently a single bond, —CH ₂ —, —O—, —CO—, —SO ₂ —, —C (CH ₃ ) ₂ —, or —C (CF ₃ ) ₂ —. Ring A and ring B each independently represent a benzene ring or a cyclohexane ring. The polyimide of the present invention can be obtained by imidizing the polyamic acid by a known method such as heating or chemical dehydration and then irradiating with polarized ultraviolet rays. By irradiating polarized ultraviolet rays and / or electron beams, the indole residues in the portions irradiated with the electron beams and / or ultraviolet rays are polymerized and can be used as liquid crystal alignment films without rubbing treatment. . The liquid crystal alignment film of the present invention is obtained by applying a solution of the polyamic acid of the present invention having an indole residue at the end of the side chain to a substrate, imidizing by heating or the like, and then irradiating polarized ultraviolet rays on the film surface. Manufactured by imparting anisotropy.
As another embodiment of the present invention, the general formula [4] and the general formula [14]

からなるポリアミド酸を挙げることができる。これらの化合物は一般式［１］で示されるジアミノ化合物に、更に、後述するような他のジアミンを加えてジアミン成分とし、これらのジアミン成分と一般式［１５］で示されるテトラカルボン酸二無水物を、上述したように反応させることにより、ポリアミド酸、更にポリイミドを得ることができる。

The polyamic acid which consists of can be mentioned. These compounds are added to the diamino compound represented by the general formula [1] to further add other diamines as described later to form diamine components, and these diamine components and the tetracarboxylic dianhydride represented by the general formula [15]. By reacting the product as described above, polyamic acid and further polyimide can be obtained.

ここでＧ_９は独立に、単結合、−ＣＨ_２−、−Ｏ−、−ＣＯ−、−ＳＯ_２−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−結合であり、環Ａ及び環Ｂはそれぞれ独立にベンゼン環またはシクロヘキサン環を示す。 Ｇ_８を与える炭素数２〜３６の２価の有機基となるジアミンとしては以下の化合物を挙げることができるがこれらのジアミンには特に限定されない。 即ち、トリメチレンジアミン、テトラメチレンジアミン、ヘキサメチレンジアミン、４，４−ジメチルヘプタメチレンジアミン、２，１１−ドデカンジアミン等の脂肪族ジアミン、ビス（４−アミノフェニル）エーテル、ビス（４−アミノフェニル）メタン、ビス（４−アミノ−３−メチルフェニル）メタン、ビス（４−アミノ−３，５−ジメチルフェニル）メタン、ビス（４−アミノフェニル）スルフォン、ビス（４−アミノフェニル）サルフィド、ビス（４−（３−アミノフェノキシ）フェニル）スルフォン、２，２−ビス（４−（４−アミノフェノキシ）フェニル）プロパン、ビス（４−（４−アミノフェノキシ）フェニル）スルフォン、１，２−ジアミノベンゼン、１，３−ジアミノベンゼン、１，４−ジアミノベンゼン、１，４−ジアミノ−２−ブチルベンゼン、１，４−ジアミノ−２−ドデシロキシベンゼン、ベンジジン、２，２−ジアミノベンゾフェノン、４，４−ジアミノベンゾフェノン、２，２−ビス（４−アミノフェニル）プロパン、１，５−ジアミノナフタリン、１，５−ジアミノナフタリン、４，４−ジアミノ−３−オクチルジフェニルメタン、２，２−ビス（４−（４−アミノフェノキシ）フェニル）−１，１，１，３，３，３−ヘキサフルオロプロパン、４，４−ビス（４−アミノフェノキシ）ビフェニル、１，２−ビス（４−アミノフェニル）エタン、１，２−ビス（４−アミノ−２−メチルフェニル）エタン、１，１−ビス（４−（４−アミノフェノキシ）フェニル）シクロヘキサン、１，１−ビス（４−（４−アミノフェノキシ）フェニル）−４−プロピルシクロヘキサン、１，１−ビス（４−（４−アミノベンジル）フェニル）シクロヘキサン、１，３−ビス（４−（４−アミノベンジル）フェニル）プロパン、１，４−ビス（４−アミノフェノキシ）ベンゼン、ビス−ｐ−アミノフェニルアニリン等の芳香族ジアミン、１，４−ジアミノシクロヘキサン、４，４−ジアミノジシクロヘキシルメタン、４，４−ジアミノ−３，３−ジメチルジシクロヘキシルメタン、４，４−ジアミノ−３，３−ジメチルジシクロヘキシル、等の脂環式ジアミン、等を挙げることができる。これらの化合物には異性体を含むものもあるが、これらの異性体混合物であってもかまわない。また、２種以上の化合物を併用しても良い。
また、ポリシロキサンを骨格とするジアミノ化合物であっても良い。

Here, G ₉ is independently a single bond, —CH ₂ —, —O—, —CO—, —SO ₂ —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, Ring A and ring B each independently represent a benzene ring or a cyclohexane ring. Examples of the diamine that is a divalent organic group having 2 to 36 carbon atoms that gives G ₈ include the following compounds, but are not particularly limited to these diamines. That is, aliphatic diamine such as trimethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4-dimethylheptamethylenediamine, 2,11-dodecanediamine, bis (4-aminophenyl) ether, bis (4-aminophenyl) ) Methane, bis (4-amino-3-methylphenyl) methane, bis (4-amino-3,5-dimethylphenyl) methane, bis (4-aminophenyl) sulfone, bis (4-aminophenyl) sulfide, bis (4- (3-aminophenoxy) phenyl) sulfone, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, bis (4- (4-aminophenoxy) phenyl) sulfone, 1,2-diamino Benzene, 1,3-diaminobenzene, 1,4-diaminobenzene, 1,4- Amino-2-butylbenzene, 1,4-diamino-2-dodecyloxybenzene, benzidine, 2,2-diaminobenzophenone, 4,4-diaminobenzophenone, 2,2-bis (4-aminophenyl) propane, 1 , 5-diaminonaphthalene, 1,5-diaminonaphthalene, 4,4-diamino-3-octyldiphenylmethane, 2,2-bis (4- (4-aminophenoxy) phenyl) -1,1,1,3,3 , 3-hexafluoropropane, 4,4-bis (4-aminophenoxy) biphenyl, 1,2-bis (4-aminophenyl) ethane, 1,2-bis (4-amino-2-methylphenyl) ethane, 1,1-bis (4- (4-aminophenoxy) phenyl) cyclohexane, 1,1-bis (4- (4-aminophenoxy) phenyl)- -Propylcyclohexane, 1,1-bis (4- (4-aminobenzyl) phenyl) cyclohexane, 1,3-bis (4- (4-aminobenzyl) phenyl) propane, 1,4-bis (4-aminophenoxy) ) Aromatic diamines such as benzene and bis-p-aminophenylaniline, 1,4-diaminocyclohexane, 4,4-diaminodicyclohexylmethane, 4,4-diamino-3,3-dimethyldicyclohexylmethane, 4,4-diamino Alicyclic diamines such as −3,3-dimethyldicyclohexyl, and the like. Some of these compounds include isomers, but a mixture of these isomers may be used. Two or more compounds may be used in combination.
Further, it may be a diamino compound having a polysiloxane skeleton.

  Examples of the tetracarboxylic dianhydride used in the present invention include chemical structures represented by [Chemical Formula 200] to [Chemical Formula 215].

 Further, for example, specific examples of tetracarboxylic dianhydride compounds that can be used in the present invention include 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3, 3'-biphenyltetracarboxylic dianhydride, 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, 2,3 , 3 ′, 4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis ( 3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 3,3 ′, 4,4′-hexafluoroisopropylidenediphthalic dianhydride 3,3 ′, 4,4′-bicyclohexanetetracarboxylic dianhydride, bis (3,4-dicarboxycyclohexyl) ether dianhydride, bis (3,4-dicarboxycyclohexyl) sulfone dianhydride, bis (3,3-dicarboxycyclohexyl) methane dianhydride and the like can be mentioned. Some of these compounds include isomers, but a mixture of these isomers may be used. Two or more compounds may be used in combination. Moreover, the tetracarboxylic dianhydride used for this invention is not limited to said exemplary compound. In addition, it is preferable to use tetracarboxylic dianhydrides represented by [Chemical Formula 200] to [Chemical Formula 215], but are not limited to the compounds exemplified above.

  The above-mentioned diamino compound, diamine, and / or tetracarboxylic acid is reacted with an acid anhydride group and an amino group by a known method in the presence of a known solvent such as N-methyl-2-pyrrolidone (NMP). Thus, the polyamic acid which is the polyimide precursor of the present invention can be obtained.

  The above-mentioned diamino compound and / or diamine and tetracarboxylic dianhydride are reacted with an acid anhydride group and an amino group by a known method in the presence of a known solvent such as N-methyl-2-pyrrolidone (NMP). By making it, the polyamic acid which is the polyimide precursor of this invention can be obtained.

 In this reaction, the diamino compound represented by the general formula [1] is preferably 10 mol% or more, more preferably 50 mol% or more of all amines. When this amount is reduced, the photosensitivity is lowered, and anisotropy due to polarized light tends to hardly occur. In addition, the aminosilicon compound is preferably 30 mol% or less, more preferably 10 mol% or less, based on all raw materials. These raw materials may be subjected to random copolymerization, block copolymerization, or (co) polymerized polymers having different compositions. When a tetracarboxylic dianhydride having an asymmetric structure is used, the bonding form between the diamine and the diamine in the polyimide molecule does not necessarily have to be in a certain direction, even if a head-tail structure and a head-head structure are mixed. Good. Further, it may be a polyimide composed of a plurality of tetracarboxylic dianhydrides or a plurality of diamines.

  In order to produce the polyimide used for the liquid crystal alignment film of the present invention, for example, a solution of a polyamic acid having a structural unit represented by the general formula [4] or general formula [14] is applied on a substrate, and the temperature is 150 to 300 ° C. A method of forming a polyimide thin film on a substrate by heat treatment at a temperature to cause a dehydration reaction, or a polyamic acid is chemically dehydrated using acetic anhydride or the like to form a polyimide, and then the solution is applied on the substrate A method of forming a thin film by drying is preferred.

  FIG. 1 shows a typical structure of an element having a liquid crystal alignment film of the present invention. The liquid crystal alignment film of the present invention can be formed by applying a solution containing the polymer of the present invention on a substrate and then performing a heat treatment. Solvents used in the liquid crystal alignment film of the present invention include toluene, xylene, methyl isobutyl ketone, cyclohexanone, γ-butyrolactone, γ-butyllactone, N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc), dimethyl Formamide (DMF), dimethyl sulfoxide (DMSO), ethylene glycol monoalkyl ethers (such as ethylene glycol monobutyl ether), propylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoalkyl ether (such as diethylene glycol monoethyl ether), Ethylene glycol dimethyl ether, ethyl acetate, butyl acetate, butyrocellosolve (BC), or diethylene glycol dimethyl ether ← Pyridine, acetonitrile, ethyl lactate, n-butyl acetate, ethyl cellosolve acetate, propylene glycol monoethyl ether acetate (PGMEA), 3-methylmethoxypropionate, ethoxyethylpropionate, n-hexane, cyclohexane, γ-butyrolactone , O-dioxane, m-dioxane, p-dioxane (1,4-dioxane), N, N′-dimethylacetamide, dimethylformamide, N, N-dimethylformamide, dimethyl sulfoxide, diglyme, chloroform, carbon tetrachloride, γ-butyrolactone, γ-valerolactone, phenol, o-cresol, m-cresol, p-cresol, ethanol, methanol, xylene, toluene, tetrahydrofuran, water, trichloroethylene, Trachlorethylene, 1,1,1-tochloroloethane, 1,1,2-tochloroloethane, 1,2-dichloroethylene, 1,1-dichloroethylene, 1,3-dichloropropene, pentachlorophenol, dichloromethane, methyl ethyl ketone , Cyclohexanone, 1-methoxy-2-propanol, 2-propanol, 2-butoxyethanol, ethyl 2-ethoxypropionate, acrylonitrile, propylene glycol, 1-monomethyl ether-2-acetate, ethyl 3-ethoxypropionate, oleic acid , Diphenyl ether, diethyl ether, petroleum ether, 2-butoxyethanol, perchloric acid, 1-bromooctane, 1-bromododecane, 3-methoxybutyl acetate, 1,4-dimethylbenzene, benzene, monochrome Rhobenzene, pyridine, hydrochloride, tetralin, o-dichlorobenzene, acetic acid, diphenyl ether, biphenyl ether, 1,2-dimethoxyethane, monochlorobenzene, benzonitrile, quinoline, 1,3-dimethylbenzene, nitrobenzene, aqueous ammonia, 1- Butanol, diethylene glycol dimethyl ether, propylene glycol, 2-propanol, 2-butanone, 4-methyl-2-pentanone, dimethyl diglycol, 1,1,2,2-tetrachloroethane, ethylbenzene, 1,2-dimethylbenzene, anisole, 1-cyclohexyl-2-pyrrolidone, n-dodecyl mercaptan, carbon disulfide, 1-propanol, 1-dodecanol, n-pentyl alcohol, 2-dimethylaminoethanol, 2-a Minoethanol, trifluoroacetic acid, ethyl 3-oxobutanoate, ethyl acetoacetate, n-pentyl alcohol, 3-methoxybutyl acetate, acetone, 2,2 ′, 2 ″ -nitriloethanol, tri-n-propylamine n -Hexylamine, dodecylamine, dibutylamine, dimethylamine aqueous solution, diethyltriamine, aniline, triethylamine, heptane, cholic acid, o-tolidine, N-methylcaprolactam, N-methylpropionamide, 1,2,4-trimethylbenzene 1,3,5-trimethylbenzene, methylene chloride, N, N-dimethylacetamide, N, N-diethylformamide, diethylacetamide, dichloroethane, dimethyladipate, dimethylimidozolidinone, alkyl lactate, 3-methoxybutanol And solvents such as tetralin, isophorone, ethylene glycol monoalkyl or phenyl acetate, triethylene glycol monoalkyl ether, propylene glycol monoalkyl ether (propylene glycol monobutyl ether, etc.), dialkyl malonate (diethyl malonate, etc.) However, the solvent used in the present invention is not limited to these solvents. Using the above solvent, the polymer of the present invention is dissolved to prepare a 0.1 to 30% by weight solution, preferably a 1 to 10% by weight solution.

[Support]
And as a support body, a transparent thing is preferable, and when a liquid crystal layer is piled up with a pair of support body like a liquid crystal display element etc., it is preferable that at least one is transparent. As a support of an optical element, a support mainly composed of an organic substance such as a polymer film such as polyethylene terephthalate (PET), triacetyl cellulose (TAC), polyether sulphone, polyether imide, polycarbonate, or a composite thereof. And / or a support mainly composed of an inorganic substance such as a glass substrate or a silicon wafer. Moreover, you may equip the surface and the inside of a support body with electrodes and wiring, such as Al, Cr, and ITO.
A substrate provided with a so-called TFT (Thin-Film Transistor), or a color filter substrate may be used.

Further, the support of the optical compensation sheet is preferably transparent. The support of the optical compensation sheet is a glass plate or a polymer film, preferably a polymer film. That the support is transparent means that the light transmittance is 80% or more. In general, an optically isotropic polymer film is used as the transparent support. Specifically, the optical isotropy preferably has an in-plane retardation (Re) of less than 10 nm, more preferably less than 5 nm. In addition, in the optically isotropic transparent support, the thickness direction retardation (Rth) is preferably less than 10 nm, and more preferably less than 5 nm. In-plane retardation (Re) and thickness direction retardation (Rth) of the transparent support are respectively defined by the following formulae.
Re = (nx−ny) xd
Rth = [{(nx + ny) / 2} -nz] xd
Where nx and ny are the in-plane refractive indices of the support, nz is the refractive index in the thickness direction of the support, and d is the thickness of the support.

And this solution is brush coating method, dipping method, spin coating method, spray method, spin coating method, cast coating method, dip coating method, die coating method, bead coating method, bar coating method, roll coating method, spray coating method, It is applied onto a support by a gravure coating method, a flexographic printing method, a screen printing method, or an offset printing method to form a coating film.

The heating temperature after the coating film is formed varies depending on the heat resistance temperature of the support. In order to prevent unevenness of the film, the drying process and the main baking process may be separated and the temperature of each process may be set in multiple stages. For example, in a liquid crystal alignment film formed by coating on PET, the solvent is evaporated at 50 to 140 ° C., preferably 80 to 120 ° C. in consideration of the heat resistant temperature of PET, and then dried at 120 to 150 ° C. A liquid crystal alignment film is formed.
Since the glass substrate mainly used in the liquid crystal display device has a high heat-resistant temperature of the substrate, the orientation is stabilized by promoting the imidization by performing the main baking at a baking temperature of 180 ° C. to 250 ° C., preferably 210 to 235 ° C. Can be improved.
The surface of the formed polymer film is rubbed in one direction with a cloth and / or irradiated with radiation (electron beam and / or ultraviolet light) to obtain a liquid crystal alignment film capable of aligning liquid crystalline molecules.

  As a method for aligning the liquid crystal alignment film containing the polymer compound of the present invention in a desired alignment direction, irradiation with polarized light and / or obliquely incident radiation (ultraviolet ray, electron beam, etc.) and / or rubbing and / or Or it is added by extending | stretching.

  The desired alignment direction in the liquid crystal alignment film of the present invention may be a liquid crystal alignment film having a direction different from the stretching direction. As a specific example of the desired alignment direction, a liquid crystal compound in a substantially constant direction. This is the direction in which the molecules are oriented. Typical orientation directions include a rubbing direction and / or a stretching direction and / or a polarization direction that is substantially perpendicular, a substantially 45 ° direction, or a substantially parallel direction.

  In particular, the present invention aims to increase the production efficiency of optical elements and improve the mass production yield by aligning liquid crystals in different directions of rubbing, and the alignment direction is different from rubbing direction and / or stretching direction and / or polarization direction. It may be substantially parallel.

  Furthermore, the orientation direction does not change even when heat treatment such as annealing is performed.

  FIG. 3 shows a liquid crystal display element of the present invention. The liquid crystal display element of the present invention is a polymer film formed using the above raw material polymer, and by rubbing this, a liquid crystal alignment imparted with a liquid crystal alignment ability in a direction different from the rubbing direction A liquid crystal display element using a film. The liquid crystal display element of the present invention is usually produced by the following method. That is, an electrode (specifically, an ITO (indium oxide-tin oxide) or tin oxide transparent electrode) is formed on a substrate such as glass, and the liquid crystal alignment film is provided on the electrode. The two substrates formed in this manner are held with a certain distance between them with the liquid crystal alignment film inside, and the periphery is sealed with an epoxy resin or the like to form a cell. Thereafter, liquid crystal is injected into the cell, and the injection port is sealed and gradually cooled to produce a liquid crystal display element. Alternatively, a liquid crystal display element may be manufactured by spraying and overlapping liquid crystals on two substrates on which electrodes and a liquid crystal alignment film are formed, and sealing the liquid crystals so as not to leak. Furthermore, characters, figures, color filters, etc. may be printed on the outside of the cell, or polarizing plates, reflectors, lighting, etc. may be arranged as necessary.

The optical functional layer described in the present invention is formed of an optically anisotropic layer, a liquid crystal composition, or the like. The range of the liquid crystal display element of the present invention includes two liquid crystal compositions used in the display element such as merocyanine, styryl, azo, azomethine, azoxy, quinophthalone, anthraquinone and tetrazine. Guest-host (GH) mode liquid crystal display element containing chromatic dye; NCAP produced by microencapsulating nematic liquid crystal; polymer dispersed liquid crystal display element (PDLCD, typical example: in liquid crystal) Polymer network liquid crystal display device (PNLCD) produced by forming a three-dimensional network polymer; including birefringence control (ECB) mode and dynamic scattering (DS) mode liquid crystal display device It is.

  The substrate thus formed is made into a cell, liquid crystal is injected, and the injection port is sealed to make a liquid crystal display element. As the liquid crystal to be sealed, various liquid crystals such as a liquid crystal to which a dichroic dye is added can be used in addition to a normal nematic liquid crystal.

The compounds represented by the general formula [1], and in the structural unit represented by the general formula [2], the length G ₃ of the spacer is preferably 0-12 carbons, more preferably 0-6. When the number of carbon atoms is 12 or more, the structure is inferior in heat resistance, which may adversely affect the thermal stability of the film after photocrosslinking.

In the general formulas [1] and [2], the number m of the benzene ring or naphthalene ring substituted at the 2-position of the side chain indole ring is preferably 1 to 2. When the number of rings is more than this, the substituents are too rigid, so that the solubility and coating properties of the resulting polyamic acid are extremely lowered, and there is a risk of inhibiting the photoreaction due to steric hindrance.
Specific examples of the substituent X in the general formulas [1] and [2] include the following atoms and functional groups, but are not necessarily limited thereto. That is, hydrogen, fluorine, chlorine, cyano group, nitro group, cyclopropyl group, cyclobutyl group, cyclopentyl group, methylcyclopropyl group, ethylcyclopropyl group, propylcyclopropyl group, n-butylcyclopropyl group, methylcyclobutyl group, Examples include atoms or cyclic substituents such as ethylcyclobutyl group, propylcyclobutyl group, n-butylcyclobutyl group, methylcyclopentyl group, ethylcyclopentyl group, propylcyclopentyl group, n-butylcyclopentyl group. As the alkyl group, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, t-butyl group, n-pentyl group, iso-pentyl group, Examples include neo-pentyl group, t-pentyl group, n-hexyl group, iso-hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group and the like.

Examples of the haloalkyl group include trifluoromethyl group, trichloromethyl group, tribromomethyl group, triiodomethyl group, pentafluoroethyl group, pentachloroethyl group, pentabromoethyl group, pentaiodoethyl group, 1,1,1-trichloro Ethyl group, 1,1,1-trifluoroethyl group, 1,1,1-tribromoethyl group, 1,1,1-triiodoethyl group, heptafluoropropyl group, heptachloropropyl group, heptabromopropyl group , Heptaiodopropyl group, 1,1,1-trifluoropropyl group, 1,1,1-trichloropropyl group, 1,1,1-tribromopropyl group, 1,1,1-triiodopropyl group, nona Fluorobutyl group, nonachlorobutyl group, nonabromobutyl group, nonaiodobutyl group, perfluoropentyl group, Perchloropentyl group, perbromopentyl group, perfluorohexyl group, perchlorohexyl group, perbromohexyl group, periodohexyl group, perfluoroheptyl group, perchloroheptyl group, perbromoheptyl group, perfluorooctyl group, perchlorooctyl group Group, perbromooctyl group, perfluorononyl group, perchlorononyl group, perbromononyl group, perfluorodecyl group, perchlorodecyl group, perbromodecyl group and the like.

As alkoxy groups and haloalkoxy groups, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group, t-butoxy group, n-pentyloxy group, iso-pentyloxy group, neo-pentyloxy group, t-pentyloxy group, n-hexyloxy group, iso-hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyl Oxy group, trifluoromethoxy group, trichloromethoxy group, tribromomethoxy group, triiodomethoxy group, pentafluoroethoxy group, pentachloroethoxy group, pentabromoethoxy group, pentaiodoethoxy group, 1,1,1-trichloroethoxy Group, 1,1,1-triflu Loethoxy group, 1,1,1-tribromoethoxy group, 1,1,1-triiodoethoxy group, heptafluoropropoxy group, heptachloropropoxy group, heptabromopropoxy group, heptaiodopropoxy group, 1,1,1 -Trifluoropropoxy group, 1,1,1-trichloropropoxy group, 1,1,1-tribromopropoxy group, 1,1,1-triiodopropoxy group, nonafluorobutoxy group, nonachlorobutoxy group, nona Bromobutoxy group, Nonaiodobutoxy group, Perfluoropentyloxy group, Perchloropentyloxy group, Perbromopentyloxy group, Perfluorohexyloxy group, Perchlorohexyloxy group, Perbromohexyloxy group, Periodohexyloxy group, Perfluoro Heptyloxy group, perchloro Ptyloxy group, perbromoheptyloxy group, perfluorooctyloxy group, perchlorooctyloxy group, perbromooctyloxy group, perfluorononyloxy group, perchlorononyloxy group, perbromononyloxy group, perfluorodecyloxy group, perchloro A decyloxy group, a perbromodecyloxy group, etc. are mentioned.

  Among the above substituents, hydrogen, fluorine, cyano group, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, heptyl group, octyl group, nonyl group, Decyl, undecyl, dodecyl, heptafluoropropyl, nonafluorobutyl, perfluoropentyl, perfluorohexyl, perfluoroheptyl, perfluorooctyl, perfluorononyl, perfluorodecyl, methoxy, ethoxy, n -Propoxy group, n-butoxy group, n-pentyloxy group, n-hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group, heptafluoropropoxy group, nona Fluorobutoxy group, perfluoropen Aryloxy group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluorononyl group include perfluoro decyl group. More preferably, hydrogen, fluorine, cyano group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, perfluorohexyl Group, perfluoroheptyl group, perfluorooctyl group, perfluorononyl group, perfluorodecyl group, n-hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group, perfluorohexyloxy Group, perfluoroheptyloxy group, perfluorooctyloxy group, perfluorononyloxy group, and perfluorodecyloxy group.

Furthermore, specific examples of the structural unit of the polymer compound of the present invention include the following structural units of [Chemical Formula 216] to [Chemical Formula 230].

The liquid crystal display element that can use the liquid crystal alignment film and the optical compensation sheet containing the polymer compound of the present invention includes TN (Twisted Nematic), IPS (In-Plane Switching), FLC (Ferroelectric Liquid Crystal), OCB (Optically Compensatory). Bend), STN (Supper Twisted Nematic), VA (Vertically Aligned), ECB (Electrically Controlled Birefringence), and reflective types, such as TN, HAN (Hybrid Aligned Nematic), and GH (Guest-Host). The liquid crystal display element is mentioned.

[Optically anisotropic layer]
The optical functional layer described in the present invention is formed of an optically anisotropic layer, a liquid crystal composition, or the like. FIG. 2 shows the optical compensation sheet of the present invention. Here, the optically anisotropic layer used in the optical compensation sheet of the present invention is formed from liquid crystalline molecules. The liquid crystalline molecules are preferably aligned in a state where the average tilt angle between the major axis direction of the liquid crystalline molecules and the support surface is less than 5 °. It is preferable to adjust the retardation of the entire optical compensation sheet by providing an optically anisotropic layer. The in-plane retardation (Re) of the entire optical compensation sheet is preferably 20 to 200 nm, more preferably 20 to 100 nm, and most preferably 20 to 70 nm. The retardation (Rth) in the thickness direction of the entire optical compensation sheet is preferably 70 to 500 nm, more preferably 70 to 400 m, and still more preferably 70 to 300 nm. The in-plane retardation (Re) and the thickness direction retardation (Rth) of the optical compensation sheet are defined by the following equations, respectively.
Re = (nx−ny) xd
Rth = [{(nx + ny) / 2} -nz] xd
In the formula, nx and ny are the in-plane refractive indexes of the optical compensation sheet, nz is the refractive index in the thickness direction of the optical compensation sheet, and d is the thickness of the optical compensation sheet. The retardation of the entire optical compensation sheet can be adjusted by combining the optically anisotropic layer and a transparent support having optical uniaxiality or optical biaxiality. A transparent support having optical uniaxiality or optical biaxiality will be described later.

It is preferable that the molecules of the liquid crystal compound (hereinafter also referred to as “liquid crystal molecules”) for forming the optically anisotropic layer in the optical compensation sheet of the present invention can be fixed in an aligned state. The alignment state can be fixed using a polymer binder, but is preferably fixed by a polymerization reaction. Depending on the display mode of the liquid crystal display element, the liquid crystalline molecules may be cholesterically aligned. When the liquid crystal molecules are cholesterically aligned, the selective reflection region is preferably outside the visible region. Examples of liquid crystalline molecules include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines, Phenyldioxanes, tolanes and alkenylcyclohexylbenzonitriles are preferably used. Note that the liquid crystal molecules include metal complexes. In addition, a liquid crystal polymer containing a liquid crystal molecule in a repeating unit can also be used as the liquid crystal molecule. In other words, the liquid crystalline molecule may be bonded to a (liquid crystal) polymer. For liquid crystal molecules, see Chapter 4, Chapter 7 and Chapter 11 of the Chemistry of the Quarterly Chemical Review Vol. 22 Liquid Crystal Chemistry (1994) edited by the Chemical Society of Japan, and the 142th Committee of the Japan Society for the Promotion of Science. Described in Chapter 3. The birefringence of the liquid crystalline molecules is preferably 0.001 to 0.7.

The liquid crystalline molecules for forming the optically anisotropic layer in the optical compensation sheet of the present invention preferably have a polymerizable group. Examples of the polymerizable group are shown in [Chemical Formula 231] to [Chemical Formula 247].

  The polymerizable group in the liquid crystalline molecule for forming the optically anisotropic layer in the optical compensation sheet of the present invention is an unsaturated polymerizable group ([Chemical Formula 231] to [Chemical Formula 237]), an epoxy group ([ It is preferably an aziridinyl group ([Chemical Formula 239]), more preferably an unsaturated polymerizable group, and an ethylenically unsaturated polymerizable group (Chemical Formula 231) to [Chemical Formula 236]). Most preferably it is. The liquid crystalline molecules preferably have a molecular structure that is substantially symmetrical with respect to the minor axis direction. For that purpose, it is preferable to have a polymerizable group at both ends of the rod-like molecular structure. Examples of liquid crystal molecules are shown below. Two or more kinds of liquid crystal molecules may be mixed and used.

  The optically anisotropic layer in the optical compensation sheet of the present invention is composed of a liquid crystalline molecule, the following polymerizable initiator or any additive (eg, plasticizer, monomer, surfactant, cellulose ester, 1, 3, 5). A liquid crystal composition (coating liquid) containing a triazine compound and a chiral agent is applied on the liquid crystal alignment film. As the solvent used for preparing the liquid crystal composition, an organic solvent is preferably used. Examples of organic solvents include amides (eg, N, N-dimethylformamide), sulfoxides (eg, dimethyl sulfoxide), heterocyclic compounds (eg, pyridine), hydrocarbons (eg, benzene, hexane), alkyl halides (eg, , Chloroform, dichloromethane), esters (eg, methyl acetate, butyl acetate), ketones (eg, acetone, methyl ethyl ketone), ethers (eg, tetrahydrofuran, 1,2-dimethoxyethane). Alkyl halides and ketones are preferred. Two or more organic solvents may be used in combination. The liquid crystal composition can be applied by a known method (eg, wire bar coating method, extrusion coating method, direct gravure coating method, reverse gravure coating method, die coating method).

The polymerization reaction of the liquid crystalline molecules in the optical compensation sheet of the present invention includes a thermal polymerization reaction using a thermal polymerization initiator and a photopolymerization reaction using a photopolymerization initiator. A photopolymerization reaction is preferred. Examples of the photopolymerization initiator include α-carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ether (described in US Pat. No. 2,448,828), α-hydrocarbon substituted aromatic acyloin. Compound (described in US Pat. No. 2,722,512), polynuclear quinone compound (described in US Pat. Nos. 3,046,127 and 2,951,758), a combination of triarylimidazole dimer and p-aminophenyl ketone (US Pat. No. 3,549,367) Acridine and phenazine compounds (JP-A-60-105667, U.S. Pat. No. 4,239,850) and oxadiazole compounds (U.S. Pat. No. 4,212,970). The amount of the photopolymerization initiator used is preferably 0.01 to 20% by mass, more preferably 0.5 to 5% by mass, based on the solid content of the coating solution. It is preferable to use ultraviolet rays for light irradiation for polymerization of liquid crystalline molecules. The irradiation energy is preferably 20 mJ / cm 2 to 50 J / cm 2, and more preferably 100 to 800 mJ / cm 2. In order to accelerate the photopolymerization reaction, light irradiation may be performed under heating conditions. The thickness of the optically anisotropic layer is preferably 0.1 to 20 μm, more preferably 0.2 to 15 μm, and most preferably 0.3 to 10 μm.

In the optical compensation sheet of the present invention, an optically anisotropic polymer film may be used as a support depending on the type of liquid crystal display mode. That is, in addition to the optical anisotropy of the optically anisotropic layer, the optical anisotropy of the support may be added to correspond to the optical anisotropy of the liquid crystal display element (optically compensated). In such a case, the transparent support preferably has optical uniaxiality or optical biaxiality. In the case of an optically uniaxial support, even if it is optically positive (the refractive index in the optical axis direction is larger than the refractive index in the direction perpendicular to the optical axis), it is negative (the refractive index in the optical axis direction is It may be smaller than the refractive index in the vertical direction. In the case of an optical biaxial support, the refractive indices nx, ny and nz in the above formula are all different values (nx ≠ ny ≠ nz). The in-plane retardation (Re) of the optically anisotropic transparent support is preferably 0 to 300 nm, more preferably 0 to 200 nm, and most preferably 0 to 100 nm. The retardation (Rth) in the thickness direction of the optically anisotropic transparent support is preferably 10 to 1000 nm, more preferably 50 to 400 nm, and still more preferably 100 to 300 nm.

The material forming the transparent support in the optical compensation sheet of the present invention is determined depending on whether it is an optical isotropic support or an optical anisotropic support. In the case of an optically isotropic support, glass or cellulose ester is generally used. In the case of an optically anisotropic support, a synthetic polymer (eg, polycarbonate, polysulfone, polyethersulfone, polyacrylate, polymethacrylate, norbornene resin) is generally used. However, (1) Use of a retardation increasing agent (birefringence increasing agent) described in the specification of European Patent 0911656A2, (2) Decreasing degree of acetylation of cellulose acetate, or (3) by cooling dissolution method By producing the film, a cellulose ester film having optical anisotropy (high retardation) can also be produced. The transparent support made of a polymer film is preferably formed by a solvent cast method.

In order to obtain an optically anisotropic transparent support in the optical compensation sheet of the present invention, it is preferable to subject the polymer film to stretching. When an optical uniaxial support is produced, a normal uniaxial stretching process or biaxial stretching process may be performed. When producing an optical biaxial support, it is preferable to perform an unbalanced biaxial stretching process. In unbalanced biaxial stretching, the polymer film is stretched in a certain direction (for example, 3 to 100%, preferably 5 to 30%) in a certain direction, and further in the direction perpendicular thereto (for example, 6 to 200%, preferably 10 to 90%). The bi-directional stretching process may be performed simultaneously. The stretching direction (the direction in which the stretching ratio is high in unbalanced biaxial stretching) and the in-plane slow axis of the film after stretching are preferably substantially the same direction. The angle between the stretching direction and the slow axis is preferably less than 10 °, more preferably less than 5 °, and most preferably less than 3 °. When a transparent support having optical uniaxiality or optical biaxiality is used, the average of the lines obtained by projecting the major axis direction of the liquid crystalline molecules of the optically anisotropic layer onto the transparent support surface It is preferable to arrange the direction so that it is substantially parallel or orthogonal to the slow axis in the plane of the transparent support.

In the optical compensation sheet of the present invention, the thickness of the support is preferably 10 to 500 μm, and more preferably 50 to 200 μm. In order to improve adhesion between the support and the layer provided thereon (adhesion layer, liquid crystal alignment film or optically anisotropic layer), the support is subjected to surface treatment (eg, glow discharge treatment, corona discharge treatment, ultraviolet ray ( UV) treatment, flame treatment). An ultraviolet absorber may be added to the support. An adhesion layer (undercoat layer) may be provided on the support. The adhesive layer is described in JP-A-7-333433. The thickness of the adhesion layer is preferably 0.1 to 2 μm, and more preferably 0.2 to 1 μm.

[Conductive polymer]
A group in which at least one aromatic ring compound group is bonded to an aromatic heterocyclic compound group containing a nitrogen atom having a skeletal structure other than a carbazole derivative and an imide derivative is bonded to the polymer via the nitrogen atom. In the conductive polymer of the present invention, which is a polymer compound contained in a side chain, at least one aromatic heterocyclic compound group containing a nitrogen atom having a skeleton structure other than a carbazole derivative and an imide derivative Although the following chemical structures are mentioned as a compound which the aromatic ring compound group couple | bonded, This invention is not limited to the following. In addition, a conductive polymer in which these compound structures are included as one of repeating units of the alternating polymer may be used.

A group in which at least one aromatic ring compound group is bonded to an aromatic heterocyclic compound group containing a nitrogen atom having a skeletal structure other than a carbazole derivative and an imide derivative is bonded to the polymer via the nitrogen atom. The conductive polymer of the present invention, which is a polymer compound contained in a side chain, may contain the following chemical structure as one of repeating units of an alternating polymer in the conductive polymer, The repeating unit capable of alternating polymerization with the conductive polymer of the present invention is not limited to the following.

As disclosed in JP-A No. 2002-356684, the introduction of an alkyloxy group or the like that does not have a conjugated bond to the side chain originally prevents oxygen atoms and carbon groups from transferring charges in the main chain, so that a conductive polymer material Although it is not preferable in terms of design, it seems that fluorene has been so poorly introduced that it is unavoidably introduced. Although the repeating unit which has an alkyl group in a side chain below is shown below, the repeating unit which can be alternately polymerized to the conductive polymer of this invention is not restricted to the following.

Oxygen hinders the movement of charge, so oxygen is removed to make only the side chain of the alkyl group, and there are some that seem to have increased the steric hindrance of the alkyl group (introducing dimethyloctyl instead of just octyl into the side chain) { That is, since 2-methyl-5- (3,7-dimethyloctyl) -p-xylylene dibromide is alternately polymerized as a raw material}, the number described in JP-A No. 2002-356664 is small. There seems to be no effect to improve the conductivity. However, it is needless to say that repeating units capable of alternating polymerization described in JP-A No. 2002-356664 may be used.

Unless substantial electron-withdrawing repeating units are directly bonded to fluorene and the solubility is not improved by that, it does not reach a conductive polymer recording the highest current conductivity and brightness. In that respect, unless there is a significant breakthrough, it is unlikely to be replaced for the time being. Although the specific example of the conductive polymer of this invention is illustrated below, the conductive polymer of this invention is not limited to the following.
Further, as a polymer terminal group described in JP-A-2003-226744 and JP-A-2003-155476, a diphenylamino group is substituted with a 2-phenylindoyl group, 2- (2-naphthyl) indoyl group as a terminal group of the present invention, Needless to say, it may be a polymer compound (conductive polymer) that has been changed to a derivative of 2- (1-naphthyl) indoyl group. Furthermore, it goes without saying that a substituent such as a soluble alkyl group may be introduced into the above polymer compound to solubilize it.
In addition, a polymer that branches the tertiary amine compound of Japanese Patent Application No. 2004-209745 to the side chain of a vinyl polymer (acrylic polymer, etc.) cannot expect main chain conduction, and further, the side chain conformation. However, since it is random and packing does not occur, it cannot be a polymer showing good conductivity and orientation. Such polymers are simply rubber. However, of course, such materials are within the conceivable range. In the conductive polymer of the present invention, only chemical structures with high functionality are illustrated.

Although there is a chemical structure in which a triphenylamine skeleton is introduced into the main chain as in the above [Chemical Formula 265], the conductivity is very low because the conductivity of the main chain falls. Do not confuse the conduction mechanism of low and high molecules. Rather, the following polymer compounds having an aromatic heterocyclic compound group introduced into the main chain are considered to have higher conductivity. Considering the conductive mechanism of the polaron or bipolaron of the conductive polymer, the chemical structure of the conductive polymer that easily exhibits the effect of the invention of the present invention is exemplified below. The conductive polymer of the present invention is the following: It is not limited to things. n represents a polymer.

 In the electroluminescent device of the present invention, the conductive polymer of the present invention may contain a metal complex. Any metal complex having a heavy metal ion at the center and exhibiting phosphorescence can be used.

Hereinafter, the diamino compound, vinyl compound, polymer compound, alignment film, organic semiconductor device using the alignment film, conductive polymer, light-emitting element using the conductive polymer, and liquid crystal alignment film according to the present invention will be described. The optical element using the liquid crystal alignment film will be described in more detail, but the present invention is not limited to these examples. In the examples shown below, the alignment direction of the liquid crystal display device was confirmed as follows. First, one polarizing plate with a known polarization axis direction is placed on the light source. A liquid crystal composition that does not contain a chiral agent is injected over this, and a cell in which liquid crystal is sealed is placed and rotated after being overlapped so that the rubbing directions are parallel to each other with a pair of substrates. At this time, when the polarization axis coincides with the major axis direction of the liquid crystal molecules, light is transmitted so that the light of the light source can be seen. I can know. The orientation direction can be known not only in the orientation direction but also in the retardation by using OMS-1 (manufactured by Chuo Seiki Co., Ltd.).
Further, in the optical compensation sheet, the orientation direction and retardation can be confirmed in the same manner by arranging the optical compensation sheet in place of the liquid crystal display device or the cell in the above-described method for confirming the orientation direction. Moreover, you may measure an orientation direction, a phase difference, and the transmittance | permeability using KOBRA-21ADH (made by Oji Scientific Instruments).

Next, the physical properties of the polymer compounds obtained in the examples were measured by the following methods.

Melting point: A polarizing microscope was equipped with a hot stage (FP-82 manufactured by METTLER) and measured at a rate of temperature increase of 5 ° C. per minute.

Nuclear magnetic resonance spectrum (MNR): EX-90A manufactured by JEOL Ltd., measured using tetramethylsilane as an internal standard substance.

Rotational viscosity: measured at 25 ° C. using an E-type viscometer.

Example 1
(1) Synthesis of polyimide represented by the unit structure represented by [Chemical 276] below:

滴下ロート、攪拌装置を付けた１Ｌの三つ口フラスコに、Ｎ−（２−ヒドロキシエチル）−２−（２−ナフチル）インドール１１．１ｇとジオキサン５００ｍｌを取り、０℃攪拌下トリエチルアミン７．７１ｍｌを加えた。ここに３，５−ジニトロベンゾイルクロリド１１．５ｇのジオキサン溶液を０℃で滴下し、室温で一晩攪拌した。反応終了後、反応液を１Ｌの水に加えて得られた結晶をろ集した。これを酢酸エチルで２回再結晶して、Ｎ−（２−（３，５−ジニトロベンゾイル）オキシエチル）−２−ナフチルインドールを６．１０ｇ得た。この化合物はこれ以上精製せずニトロ基の還元を行った。この化合物の融点は１７８．１〜１７９．７℃であった。

In a 1 L three-necked flask equipped with a dropping funnel and a stirrer, 11.1 g of N- (2-hydroxyethyl) -2- (2-naphthyl) indole and 500 ml of dioxane were taken, and 7.71 ml of triethylamine was stirred at 0 ° C. Was added. The dioxane solution of 3,5-dinitrobenzoyl chloride 11.5g was dripped here at 0 degreeC, and it stirred at room temperature overnight. After completion of the reaction, the reaction solution was added to 1 L of water, and the resulting crystals were collected by filtration. This was recrystallized twice with ethyl acetate to obtain 6.10 g of N- (2- (3,5-dinitrobenzoyl) oxyethyl) -2-naphthylindole. This compound was subjected to nitro group reduction without further purification. The melting point of this compound was 178.1 to 179.7 ° C.

In a 300 ml three-necked flask equipped with a dropping funnel and a stirrer, N- (2- (3,5-dinitrobenzoyl) oxyethyl) -2-naphthylindole (8.22 g) and dioxane (150 ml) were taken and stirred at room temperature. 30.2 g of stannous (dihydrate) was added. Concentrated hydrochloric acid 30.2g was dripped at 10 degreeC here, and it stirred at room temperature after dripping for 3 hours. After completion of the reaction, 2N aqueous sodium hydroxide solution was added dropwise until neutrality, and the reaction solution was filtered through celite. The filtrate was extracted twice with ethyl acetate, and the organic phase was washed three times with water and then dried over anhydrous magnesium sulfate. The desiccant was filtered off and concentrated under reduced pressure to give a yellow solid. This was recrystallized twice with ethyl acetate to obtain 6.42 g of N- (2- (3,5-diaminobenzoyl) oxyethyl) -2-naphthylindole.

2) Polymerization reaction A 100 ml three-necked flask was charged with 3.514 g of N- (2- (3,5-diaminobenzoyl) oxyethyl) -2-naphthylindole and 31.0 g of NMP, and stirred and dissolved at room temperature in a nitrogen stream. Next, the reaction solution was kept at 10 ° C., 1.961 g of 1,2,3,4-cyclobutanetetracarboxylic dianhydride was added, and the reaction was performed at room temperature for 6 hours to obtain a 15.0 wt% polymer solution. The viscosity at this time was 118 mP · s, and the weight average molecular weight (Mw) was 93100.

3) Formation of a liquid crystal alignment film for liquid crystal display elements by irradiation with polarized light;
The polyamic acid solution obtained in 2) was diluted to 5.0 wt% with NMP / butyl cellosolve = 1/1 solvent, and this was filtered through a 0.1 μm filter to obtain a liquid crystal aligning agent solution. Subsequently, coating was performed on a pair of ITO glass substrates by a spin coating method (spinner method). After coating, the film was baked at 230 ° C. for 60 minutes to form a thin film having a thickness of about 740 Å. Orientation treatment was performed by irradiating the surface of the thin film with 2.0 J / cm 2 of linearly polarized ultraviolet light having a wavelength of about 365 nm from an ultrahigh pressure mercury lamp.

4) Preparation of liquid crystal display element, evaluation of orientation 3) The substrates obtained in 3) are bonded together using a sealing agent so that the polarization direction of ultraviolet rays is parallel, and columnar spacers are used so that the thickness of the liquid crystal layer is 5 μm. Alternatively, a liquid crystal display element in which beads were sandwiched together was manufactured, a liquid crystal composition (LA) was injected, and sealing was performed with a sealant. The prepared liquid crystal display element was annealed at 110 ° C. for 30 minutes, and then the alignment of the liquid crystal was confirmed.

Example 2
Example except that a polymer compound having a mixing ratio of 3: 7 with the polyimide shown in [Chemical 278] having the carbazole side chain and the polyimide of Example 1 is used as the liquid crystal alignment film instead of the polyimide of Example 1 In the same manner as in Example 1, a thin film was prepared and evaluated. When the orientation of the obtained thin film and the orientation of the liquid crystalline molecules were observed with a polarizing microscope, it was good. The alignment film of Example 2 is called a tilted alignment film in which the composition ratio of the alignment film changes between the surface and the inside of the alignment film. The concentration of the alignment film having an alignment function on the film surface and / or the alignment film component having good adhesion to the liquid crystal can be improved, and the concentration of the component having good adhesion to the substrate can be given inside.

Example 3
A thin film was prepared and evaluated in the same manner as in Example 1 except that a polymer compound composed of a polyimide copolymer represented by [Chemical Formula 279] instead of the polyimide of Example 1 was used as the liquid crystal alignment film. . When the orientation of the obtained thin film and the orientation of the liquid crystalline molecules were observed with a polarizing microscope, it was good.

Comparative Example 1
Instead of the liquid crystal alignment film shown in Chemical Formula 210, the liquid crystal alignment film was changed to a polymer compound composed of the structural unit shown in the following [Chemical 280] in which no aromatic compound was connected to the indole. A cell was prepared in the same manner as in Example 1, and the liquid crystal composition (LA) was injected. When the alignment direction of the liquid crystal in the cell thus prepared was observed, the liquid crystal alignment was almost good. However, after the cell was annealed at 120 ° C. for 60 minutes and the orientation direction of the liquid crystal was observed, the orientation of the liquid crystal was lowered unlike before the annealing treatment.

Hereinafter, examples of the optical compensation sheet will be described in detail. The optical compensation sheet of the present invention is a roll-shaped optical compensation sheet having a transparent support, a liquid crystal alignment film, and an optically anisotropic layer formed from liquid crystal molecules in this order. A group containing a compound in which at least one aromatic ring compound group is bonded to an aromatic heterocyclic compound group containing a nitrogen atom having a skeleton structure other than carbazole and imide, specifically 2- (2-naphthyl) indole A composition comprising a high molecular compound of a derivative, a 2-phenylindole derivative, a polyimide derivative having a skeleton having a group containing a 2- (1-naphthyl) indole derivative in the side chain, a polyamic acid derivative and / or a vinyl derivative, The average direction of the lines obtained by projecting the long axis direction of the liquid crystal molecules onto the transparent support surface is substantially perpendicular to the rubbing direction of the liquid crystal alignment film. An optical compensation sheet, wherein the liquid crystal molecules are oriented to.

Furthermore, the polarizing plate of the present invention is a roll-shaped polarizing plate having a liquid crystal alignment film, an optically anisotropic layer formed from liquid crystalline molecules, a transparent support, a polarizing film and a transparent protective film, and the liquid crystal alignment A group containing a compound in which at least one aromatic ring compound group is bonded to an aromatic heterocyclic compound group containing a nitrogen atom having a skeleton structure other than a carbazole derivative and an imide derivative in the side chain, specifically 2 -(2-naphthyl) indole derivatives, 2- (1-naphthyl) indole derivatives, 2-phenylindole derivatives, polyimide derivatives having a skeleton having a side chain containing a group containing 2-phenylbenzimidazole derivatives, polyamic acid derivatives, and the like And / or a composition containing a vinyl derivative polymer compound, and the average tilt angle between the major axis direction of the liquid crystal molecules and the transparent support surface is 5 °. The liquid crystal molecules are aligned in the full state, and the average direction of the line obtained by projecting the long axis direction of the liquid crystal molecules onto the surface of the transparent support is substantially perpendicular to the longitudinal direction of the polarizing plate. A polarizing plate characterized in that the transmission axis of the polarizing film and the average direction of the lines obtained by projecting the major axis direction of the liquid crystalline molecules onto the surface of the transparent support are substantially parallel to each other. is there.

Example 4
(Formation of liquid crystal alignment film)
The following acrylic acid copolymer (PA1) and triethylamine (neutralizing agent) are dissolved in a methanol / water mixed solvent (mass ratio = 30/70) on a saponified TAC film to prepare a 4% by mass solution. did. This solution was applied to a thickness of 1 μm on a glass support using a bar coater. The coating layer was heated at 120 ° C. for 5 minutes and dried. The surface of the coating layer was rubbed to form a liquid crystal alignment film.

Both block structures of PA1

After applying the liquid crystal alignment film solution with a wire bar coater, it was dried with warm air at 80 ° C. for 10 minutes to obtain a coating film having a thickness of 0.8 μm. After rubbing the surface of the coating film, a liquid crystal alignment film was formed by polymerizing liquid crystalline molecules by irradiation with 50 mJ / cm 2 UV using a high pressure mercury lamp.
(Formation of optically anisotropic layer)

  On the liquid crystal alignment film, a coating layer having a thickness of 0.7 μm was formed using a coating solution having the following composition using a bar coater.

────────────────────────────────────
Optically anisotropic coating solution ────────────────────────────────────
Liquid crystalline compound (Chemical Formula 250) 100 parts by weight Photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy Japan Ltd.) 3 parts by weight
Sensitizer (Kayacure DEXT, Nippon Kayaku Co., Ltd.) 1 part by weight Methyl ethyl ketone 400 parts by weight ──────────────────────────── ────────

  This coating layer was heated at 100 ° C. for 1 minute to align the liquid crystalline molecules. At that temperature, ultraviolet rays were irradiated for 4 seconds to polymerize the liquid crystalline molecules, and the alignment state was fixed to form an optically anisotropic layer.

  Thus, an optically anisotropic layer was formed, and an optical compensation sheet was produced. When the orientation of the thin film thus obtained and the director of the liquid crystal molecules were observed using a polarizing microscope, the long axis direction of the liquid crystal molecules was in the rubbing direction of the optical compensation sheet (in the plane of the film). It was substantially oriented in the vertical direction. Further, when the retardation of the entire optical compensation sheet at a wavelength of 550 nm was measured using an ellipsometer (M-150, manufactured by JASCO Corporation), the in-plane retardation (Re) was 30 nm, and the thickness direction of the film The retardation (Rth) of was 115 nm.

(Function of polarizing plate)
[Polarizing film] Examples of the polarizing film include an iodine polarizing film, a dye polarizing film using a dichroic dye, and a polyene polarizing film. The iodine polarizing film and the dye polarizing film are generally manufactured using a polyvinyl alcohol film. The transmission axis of the polarizing film corresponds to a direction perpendicular to the stretching direction of the film. The transmission axis of the polarizing film is arranged so as to be substantially parallel to the average direction (slow axis) of the lines obtained by projecting the major axis direction of the liquid crystalline molecules onto the transparent support surface.

(Preparation of polarizing plate)
A roll-shaped polyvinyl alcohol film having a thickness of 80 μm was continuously stretched 5 times in an aqueous iodine solution and dried to obtain a polarizing film. The slow axis (long axis direction of liquid crystalline molecules) of the roll-shaped optical compensation sheet saponified on one side of the polarizing film and the saponified roll on the other side and the transmission axis of the polarizing film And parallel.

(Attaching a polarizing plate to a liquid crystal display)
From the commercially available MVA liquid crystal display device (VL-1530S, manufactured by Fujitsu Limited), the polarizing plate and the optical compensation sheet on the observer side and the backlight side were deleted, and two produced polarizing plates were pasted instead. About the produced MVA liquid crystal display device, the viewing angle was measured with a viewing angle measuring device (EZ Contrast 160D, manufactured by ELDIM). As a result, the viewing angle in the transmission axis direction of the polarizing film and the viewing angle in the direction of 45 ° from the transmission axis direction were values exceeding 80 °.

Example 5
A thin film was prepared and evaluated in the same manner as in Example 4 except that the acrylic acid copolymer (PA2) was used instead of the acrylic acid copolymer (PA1). When the orientation of the obtained thin film and the orientation direction of the liquid crystalline molecules were observed using a polarizing microscope, the major axis of the liquid crystalline molecules was oriented substantially perpendicular to the rubbing direction. Further, the retardation (Rh) was measured with an ellipsometer and found to be 115 nm.

PA2 block structure

Example 6
A thin film was prepared and evaluated in the same manner as in Example 4 except that the acrylic acid copolymer (PA3) was used instead of the acrylic acid copolymer (PA1). When the orientation of the obtained thin film and the orientation direction of the liquid crystalline molecules were observed using a polarizing microscope, the major axis of the liquid crystalline molecules was oriented substantially perpendicular to the rubbing direction. Further, the retardation (Rh) was measured with an ellipsometer and found to be 115 nm.

Both block structures of PA3

Example 7
A thin film was prepared and evaluated in the same manner as in Example 4 except that the acrylic acid copolymer (PA4) was used instead of the acrylic acid copolymer (PA1). When the orientation of the obtained thin film and the orientation direction of the liquid crystalline molecules were observed using a polarizing microscope, the major axis of the liquid crystalline molecules was oriented substantially perpendicular to the rubbing direction. Further, the retardation (Rh) was measured with an ellipsometer and found to be 115 nm.

Both block structures of PA4

Example 8
Instead of the acrylic acid copolymer (PA1), an acrylic acid polymer (PA5, Mw. 800,000, Tg 150 ° C.) and poly (9-vinylcarbazole) (manufactured by Aldrich, Mw. 1100000, Tg 200 ° C.) in a ratio of 3: 7 A thin film was prepared and evaluated in the same manner as in Example 4 except that the mixed polymer was used. When the orientation of the obtained thin film and the orientation direction of the liquid crystalline molecules were observed using a polarizing microscope, the major axis of the liquid crystalline molecules was oriented substantially perpendicular to the rubbing direction. Further, the retardation (Rh) was measured with an ellipsometer and found to be 115 nm.

Both block structures of PA5

Comparative Example 2
A thin film was prepared in the same manner as in Example 4 except that poly (9-vinylcarbazole) (manufactured by Aldrich, Mw. 1100000, Tg 200 ° C.) was used alone instead of the acrylic acid copolymer (PA1) of Example 4. And evaluated. When the orientation of the obtained thin film and the orientation direction of the liquid crystalline molecules were observed using a polarizing microscope, the major axis of the liquid crystalline molecules was oriented substantially perpendicular to the rubbing direction. When the alignment direction of the liquid crystal was observed after the annealing treatment for 60 minutes, the liquid crystal was substantially aligned in the direction parallel to the rubbing direction, unlike before the annealing treatment. Further, the retardation (Rh) was measured with an ellipsometer and found to be 115 nm.

Example 9 (Hologram)
A composition having the composition described in [Chemical Formula 286] was dissolved in 10 g of 1,4-dioxane, and filtered through a filter having a pore size of 0.25 μm to obtain a photosensitive solution.

This photosensitive solution is applied onto a 100 μm thick inner surface primer-treated PET film (Teijin Limited: HP-7) as a support using a roller coater so that the film thickness after drying is 5 μm. After drying at 70 ° C. for 45 minutes, a 10% aqueous solution of polyvinyl alcohol (PVA205, polymerization degree 500, saponification degree 88%, manufactured by Kuraray Co., Ltd.) was applied with a roller coater. This was dried at 60 ° C. for 10 minutes to obtain a recording film as an element having a liquid crystal alignment film.

Next, in the state as shown in FIG. 4, the recording film has a polyvinyl alcohol coated surface on the lower side and a PET film base surface on the upper side, and the index matching liquid is bromobenzene to bring the refractive index close to the recording film. (Refractive index 1.56) is used, and light having a wavelength of 488 nm oscillated from an Ar laser is used as a transparent incident body 23 made of polyester resin (refractive index 1.57), θ = 27.7 ° The recording film was continuously supplied at a speed of 0.9 cm / second, and the interference fringes were recorded on the recording film.

After exposure with an Ar laser, exposure was performed using an ultraviolet emission lamp (trade name: Chemical Lamp FL-20BL, manufactured by Toshiba Corporation) so as to be 0.1 J / cm @ 2. At this time, only a visible light of 400 nm or more was irradiated using a sharp cut filter L39.

After exposure, the recording medium was washed with water in a flowing water bath for 1 minute to remove the polyvinyl alcohol layer and dried.

Subsequently, after being immersed in an acetone bath for 2 minutes, the recording film was taken out by being immersed in a heptane bath for 1 minute.

The diffraction efficiency of the hologram thus obtained was measured and found to be 78% at a wavelength near 950 nm. That is, a diffraction grating having a diffraction efficiency of 78% in which interference fringes with a pitch of 302 nm were recorded in a direction substantially parallel to the recording layer of the recording film was obtained. This value was uniform within a range of ± 3% at any part of the recording film.

In the above, the value of the refractive index is that of the sodium D line measured with an Abbe refractometer. Further, in the measurement of the diffraction efficiency in the above, the recording film after forming the interference fringes is cut into a size of about 5 cm square, and a spectrophotometer manufactured by Shimadzu Corporation (Shimadzu double monochromator self-recording spectrophotometer UV-365). The transmittance for perpendicular incident light in the range of 1400 nm to 400 nm was measured, and the value obtained by subtracting this transmittance from 100% was regarded as the reflectance, that is, the diffraction efficiency.

Example 10
Dioctylfluorene-2,7-bis (ethylene boronate) 0.305 g (0.576 mmol), 2,5-bis {2 ′-{4 ″-{2 ′ ″-(2 ′ ″-naphthyl)] Indolyl}} phenyl} ethenyl} -1,4-dibromobenzene 0.540 g (0.548 mmol) and aliquat 336 (230 mg, 0.57 mmol) were dissolved in toluene (10 ml), and potassium carbonate (240 mg, 1.7 mmol) was dissolved therein. 10 ml of an aqueous solution of Further, tetrakis (triphenylphosphine) palladium (1.3 mg, 0.0011 mmol) was added and heated to reflux for 10 hours. The organic layer was added dropwise to methanol, and the deposited precipitate was separated by filtration. The obtained precipitate was dissolved in toluene, this was dropped into methanol, and the deposited precipitate was separated by filtration to obtain 0.14 g of a polymer. This polymer is referred to as conductive polymer 1. The number average molecular weight in terms of polystyrene of the conductive polymer 1 was 8.8 × 10 ⁴ . From the monomer charge ratio, the ratio of the repeating units of [Chemical 287] and [Chemical 288] in the polymeric fluorescent substance 7 is 50:50. The polymeric fluorescent substance 7 is an alternating copolymer.

2,5-bis {2 ′-{4 ″-{2 ′ ″-(2 ′ ″-naphthyl) indolyl}} phenyl} ethenyl} -1,4-dibromobenzene instead of 2,5-bis The polymer may be synthesized using {2 ′-{4 ″-{2 ′ ″-(1 ′ ″-naphthyl) indolyl}} phenyl} ethenyl} -1,4-dibromobenzene.

Example 11
Bayron {PEDOT {poly (3,4-ethylenedioxythiophene) and PSS (polystyrene sulfonic acid) solution} manufactured by Bayer Co., Ltd. was spin-coated on an alkali-free glass substrate on which an ITO electrode pattern was formed as an anode electrode. The film was formed with a thickness of 70 nm. The ratio of the repeating units of [Chemical 287] and [Chemical 288] is 50:50. The polymer is dissolved in xylene as a solvent to give 1.5 wt% of the conductive polymer 1 shown in Example 10. After forming the solution, the solubilized iridium complex represented by [Chemical Formula 225] {Tris (2-phenylpyridinate) iridium (III) complex having an octyl group as a substituent on the ligand, that is, tris (2- (4 A solution in which -octylphenyl) pyridinate) iridium (III) complex} was dissolved to 7 wt% with respect to the polymer weight was spin-coated to form a film having a thickness of 100 nm. Then, 5 nm of Ca was vapor-deposited by a vacuum vapor deposition method, and 200 nm of aluminum was vapor-deposited on the upper layer to form a cathode electrode. The electroluminescent device thus formed had a light emission luminance of 4000 cd / m ² , a light emission efficiency of 1.72 cd / A, and a device lifetime (time until the initial luminance was reduced by half) of 1000 hours.

Example 12
In some cases, a low molecular weight compound or a liquid crystal compound is used as the semiconductor layer of the organic semiconductor device. Therefore, the alignment film of the present invention was used as an alignment film for aligning the semiconductor layer of the organic semiconductor device. First, a gate electrode is formed on a glass substrate by sputtering with chromium (Cr film thickness 400 mm), and an alignment film shown in [Chemical 290] of the present invention is formed thereon as a gate insulating layer (alignment film). In the same manner as above, it was diluted to 5.0 wt% with NMP / butyl cellosolve = 1/1 solvent, and this was filtered through a 0.1 μm filter to obtain a liquid crystal aligning agent solution. It apply | coated with the spin coating method (spinner method) on the glass substrate in which the gate electrode was formed. After coating, the film was baked at 230 ° C. for 60 minutes to form a thin film having a thickness of about 740 Å. Orientation treatment was performed by irradiating the surface of the thin film with 2.0 J / cm 2 of linearly polarized ultraviolet light having a wavelength of about 365 nm from an ultrahigh pressure mercury lamp. A pair of chromium electrodes was formed as a source electrode and a drain electrode on the upper layer by a sputtering method, and gold was coated on the upper layer (electrode shape 2 mm × 4 mm rectangle, Au film thickness 300 mm, Cr film thickness 400 mm). The width between the source electrode and the drain electrode was 6 μm. Further, a tertiary amine compound represented by [Chemical 291] is deposited through a mask in a vacuum bell jar of 10 ⁻⁴ Pa by a vapor deposition method to form a semiconductor layer composed of a tertiary amine compound having a thickness of 1 μm. Formed. The organic semiconductor device shown in FIG. 6 manufactured in this manner has a resistance value of less than 10 ⁸ Ω · cm, which is lower than that of an organic semiconductor device without an alignment film (10 ¹⁰ Ω · cm or more) and has a long lifetime. The reliability was high at 50000 hours (10000 hours without alignment film). Needless to say, a liquid crystal compound (such as a smectic conductive liquid crystal or a discotic conductive liquid crystal) may be used for the semiconductor layer of this embodiment.

It is sectional drawing which shows the typical structure of the element which has the liquid crystal aligning film of this invention. It is sectional drawing which shows the outline of the optical compensation sheet | seat of this invention. It is sectional drawing which shows the outline of the optical switching part in the liquid crystal display element of this invention. It is a figure which shows one form of the arrangement | positioning for implementing the hologram recording method of this invention. It is sectional drawing which shows the typical structure of the electroluminescent element which has the conductive polymer of this invention. It is sectional drawing which shows the typical structure of the organic-semiconductor device which has the oriented film of this invention.

Explanation of symbols

1, support
2, liquid crystal alignment film
3. Optically anisotropic layer (composition containing polymerizable liquid crystal compound)

11. Liquid crystal composition 12, TFT substrate 13, color filter substrate 14, sealing material 15, spacer

21, roll row 22, recording film 23, transparent incident body 24, index matching liquid 25, contact surface 26 of transparent incident body, incident surface 27 of transparent incident body, supply nozzle 28, incident area

Claims (10)

A polymer compound comprising the following general formula [1a] as at least a part of a structural unit.

(In the general formula [1a], G ₁ represents a trivalent organic group having 6 to 20 carbon atoms having an aromatic ring , and G ₂ independently represents a single bond, —COO—, —OCO—, —NHCO—, —CONH—, —O—, —S—, —CO— or an alkylene group having 1 to 20 carbon atoms, G ₃ represents a single bond or an alkylene group having 1 to 20 carbon atoms, X is a hydrogen atom, fluorine An atom, a chlorine atom, a cyano group, a nitro group, or an alkyl group having 1 to 12 carbon atoms, a haloalkyl group, an alkoxy group or a haloalkoxy group, or a cycloalkyl group having 3 to 8 carbon atoms, and m is 0 to 3 Represents an integer, wherein m is 0 means a structure in which a hydrogen atom or an alkyl group having 1 to 12 carbon atoms is bonded to the 2-position of the indole ring instead of ring B, and m is 2 is 2 in the indole ring. Bi consisting of two rings B This means a structure in which a phenyl group is bonded, and m = 3 means a structure in which a triphenyl group consisting of three rings B is bonded to the 2-position of the indole ring. Ring B is condensed with another benzene ring. And the condensed rings to rings A and B and ring B may have a substituent.) G ₁ is a benzene ring, G ₂ is —COO— or —OCO—, X is a hydrogen atom, m is 1, and ring B is condensed with another benzene ring to form a naphthalene ring. The polymer compound according to claim 1, wherein the condensed ring to ring A, B and ring B does not have a substituent. The polymer compound according to claim 1, comprising the following general formula [4] as at least a part of the structural unit.

(In the general formula [4], G ₁ represents a trivalent organic group having 6 to 20 carbon atoms having an aromatic ring , and G ₂ independently represents a single bond, —COO—, —OCO—, —NHCO—, -CONH -, - O -, - S -, - CO- or an alkylene group having a carbon number of 1 to 20, _{G 3} represents a single bond or an alkylene group having a carbon number of 1 to 20, _{G 5} represents a single bond, —CH ₂ —, —O—, —CO—, —SO ₂ —, —C (CH ₃ ) ₂ — or —C (CF ₃ ) ₂ — is represented, and X is a hydrogen atom, a fluorine atom, a chlorine atom, cyano. A nitro group or an alkyl group having 1 to 12 carbon atoms, a haloalkyl group, an alkoxy group or a haloalkoxy group, or a cycloalkyl group having 3 to 8 carbon atoms, and m represents an integer of 0 to 3, provided that m Is a hydrogen at the 2-position of the indole ring instead of ring B A structure in which a child or an alkyl group having 1 to 12 carbon atoms is bonded, m being 2 means a structure in which a biphenyl group consisting of two rings B is bonded to the 2-position of the indole ring, and m is 3 Means a structure in which a triphenyl group consisting of three rings B is bonded to the 2-position of the indole ring. Ring B may be condensed with another benzene ring, and rings C and D are benzene rings. Other benzene rings may be condensed, and rings A, B, C and D and condensed rings to rings B, C and D may have a substituent.) G ₁ is a benzene ring, G ₂ is —COO— or —OCO—, G ₅ is a single bond, X is a hydrogen atom, m is 1, ring B is another benzene ring and The polymer according to claim 3, wherein the polymer is condensed to form a naphthalene ring, and the condensed ring to ring A, B, C and D and ring B, C and D has no substituent. Compound. A diamino compound represented by the following general formula [1].

(In the general formula [1], G ₁ represents a trivalent organic group having 6 to 20 carbon atoms having an aromatic ring , and G ₂ independently represents a single bond, —COO—, —OCO—, —NHCO—, —CONH—, —O—, —S—, —CO— or an alkylene group having 1 to 20 carbon atoms, G ₃ represents a single bond or an alkylene group having 1 to 20 carbon atoms, X is a hydrogen atom, fluorine An atom, a chlorine atom, a cyano group, a nitro group, or an alkyl group having 1 to 12 carbon atoms, a haloalkyl group, an alkoxy group or a haloalkoxy group, or a cycloalkyl group having 3 to 8 carbon atoms, and m is 0 to 3 Represents an integer, wherein m is 0 means a structure in which a hydrogen atom or an alkyl group having 1 to 12 carbon atoms is bonded to the 2-position of the indole ring instead of ring B, and m is 2 is 2 in the indole ring. Biff consisting of two rings B This means a structure in which a phenyl group is bonded, and m = 3 means a structure in which a triphenyl group consisting of three rings B is bonded to the 2-position of the indole ring. Ring B is condensed with another benzene ring. And the condensed rings to rings A and B and ring B may have a substituent.) G ₁ is a benzene ring, G ₂ is —COO— or —OCO—, X is a hydrogen atom, m is 1, and ring B is condensed with another benzene ring to form a naphthalene ring. The diamino compound according to claim 5, wherein the condensed ring to ring A, B and ring B does not have a substituent.   A liquid crystal alignment film comprising the polymer compound according to claim 1. A liquid crystal alignment film comprising a polymer compound containing the following general formula [2a] as at least a part of a structural unit.

(However, in General Formula [2a], G ₂ is independently a single bond, —COO—, —OCO—, —NHCO—, —CONH—, —O—, —S—, —CO—, C 1-20. divalent represents an organic group, G ₃ represents a single bond or an alkylene group having a carbon number of 1 to 20, G ₄ represents a hydrogen atom, a fluorine atom, a chlorine atom having 6 to 20 carbon atoms and having an alkylene group or an aromatic ring Or an alkyl or haloalkyl group having 1 to 12 carbon atoms, wherein X is a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, or an alkyl group having 1 to 12 carbon atoms, a haloalkyl group, an alkoxy group or a halo group, respectively. An alkoxy group or a cycloalkyl group having 3 to 8 carbon atoms, wherein m represents an integer of 0 to 3, provided that m is 0 instead of ring B, a hydrogen atom or a carbon number of 1 to 2 at the 2-position of the indole ring; 12 This means a structure in which an alkyl group is bonded, m being 2 means a structure in which a biphenyl group consisting of two rings B is bonded to the 2-position of the indole ring, and m is 3 means being a 2-position in the indole ring. This means a structure in which a triphenyl group consisting of three rings B is bonded. Ring B may be condensed with another benzene ring, and the condensed ring to rings A, B and B has a substituent. You may do it.)   9. An optical element comprising an optical functional layer comprising a support, a liquid crystal alignment film, and a liquid crystal compound, wherein the liquid crystal alignment film is the liquid crystal alignment film according to claim 7 or 8.   An organic semiconductor device comprising the liquid crystal alignment film according to claim 7.

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