JPWO2018097155A1 - Liquid crystal display element manufacturing method, liquid crystal display element substrate, and liquid crystal display element assembly - Google Patents

Abstract

A liquid crystal alignment film forming step of forming a liquid crystal alignment film with a liquid crystal aligning agent having the same composition containing a polymer having a radical generating structure that generates radicals by light irradiation on each of the surfaces of the pair of substrates; and the pair of substrates A liquid crystal alignment film light irradiating step in which at least one of the liquid crystal is irradiated with light to change the amount of light applied to the liquid crystal alignment films in different states, and then a liquid crystal layer containing a liquid crystal compound is formed between the pair of substrates And a liquid crystal layer forming step.

Description

  The present invention relates to a method for manufacturing a liquid crystal display element, a substrate for a liquid crystal display element, and a liquid crystal display element assembly, and in particular, a vertical alignment type liquid crystal display produced by irradiating ultraviolet rays with voltage applied to liquid crystal molecules. The present invention relates to an element manufacturing method, a liquid crystal display element substrate, and a liquid crystal display element assembly.

  A liquid crystal display element of a method in which liquid crystal molecules aligned perpendicular to the substrate respond by an electric field (also referred to as a vertical alignment (VA) method) is irradiated with ultraviolet rays while applying a voltage to the liquid crystal molecules in the manufacturing process. There is a thing including the process to do.

  In such a vertical alignment type liquid crystal display element, a photopolymerizable compound is previously added to the liquid crystal composition, and a polyimide-based vertical alignment film is used, and ultraviolet rays are applied while applying a voltage to the liquid crystal cell. Therefore, a technique for increasing the response speed of liquid crystal (PSA (Polymer Sustained Alignment) type element, see, for example, Patent Document 1 and Non-Patent Document 1) is known.

  In such a PSA device, the direction in which the liquid crystal molecules incline in response to an electric field is usually controlled by protrusions provided on the substrate or slits provided on the display electrode, but photopolymerization is performed in the liquid crystal composition. By applying UV light while applying a voltage to the liquid crystal cell and applying a voltage to the liquid crystal cell, a polymer structure in which the tilted direction of the liquid crystal molecules is memorized is formed on the liquid crystal alignment film. It is said that the response speed of the liquid crystal display element is faster than the method of controlling the tilt direction of the liquid crystal molecules.

  In recent years, with the improvement of the quality of liquid crystal display elements, it is desired to further increase the response speed of the liquid crystal to voltage application and further improve the reliability. For that purpose, it is necessary that the polymerizable compound reacts efficiently and exhibits the ability to fix alignment by irradiation with ultraviolet rays having a long wavelength without decomposition of components in the liquid crystal. Furthermore, it is necessary that unreacted polymerizable compound does not remain after ultraviolet irradiation and does not adversely affect the reliability of the liquid crystal display element.

  Therefore, a specific structure that generates radicals by ultraviolet irradiation is introduced into the polymer constituting the liquid crystal aligning agent, and through use of this liquid crystal aligning agent, the polymerizable compound in the liquid crystal and / or liquid crystal alignment film is reacted. There has been proposed a liquid crystal aligning agent capable of improving the response speed of the liquid crystal display element by increasing the reactivity of the polymerizable compound in the liquid crystal display element obtained by using the step of forming (see Patent Document 2).

  Meanwhile, the first alignment film is formed on the first substrate using the first alignment liquid containing the first alignment agent, and the second alignment film is formed on the second substrate using the second alignment liquid containing the second alignment agent. Then, light irradiation is performed while applying an electric field with a liquid crystal layer sandwiched between these substrates, and the first pretilt angle is expressed in the liquid crystal molecules adjacent to the first alignment film, while adjacent to the second alignment film. A method of manufacturing a liquid crystal display element that causes a liquid crystal molecule to exhibit a second pretilt angle has been proposed (see Patent Document 3).

JP 2003-307720 A WO2015 / 033921 Republic of Korea Publication No. 10-2016-0002599

K. Hanaoka, SID 04 DIGEST, P.1200-1202

  However, in the method of Patent Document 3, it is necessary to use two kinds of liquid crystal aligning agents, and there is a problem that a great equipment investment is required due to an increase in the number of processes and an increase in production lines.

  An object of the present invention is to provide a method for producing a liquid crystal display element capable of producing a liquid crystal display element having liquid crystal layers having different alignment states on both sides more easily without involving the above-mentioned problems, and this production method. It is an object to provide a substrate for a liquid crystal display element and a liquid crystal display element assembly using the above.

  As a result of intensive studies, the present inventors have used a liquid crystal aligning agent containing a polymer having a radical generating structure that generates radicals by light irradiation, and before providing a liquid crystal layer, liquid crystal on at least one side in advance. Irradiate light to the alignment film and invalidate at least part of the radical generation structure of the radical generation structure of the liquid crystal alignment film on one side, or perform light irradiation so that the amount of light irradiation differs for both radicals. The inventors have found that a liquid crystal layer having different alignment states can be formed on both sides of the liquid crystal layer by making the generation ability different, and the present invention has been completed.

That is, the present invention has the following gist.
A liquid crystal alignment film forming step of forming a liquid crystal alignment film with a liquid crystal aligning agent having the same composition containing a polymer having a radical generating structure that generates radicals by light irradiation on each of the surfaces of the pair of substrates; and the pair of substrates A liquid crystal alignment film light irradiating step in which at least one of the liquid crystal is irradiated with light to change the amount of light applied to the liquid crystal alignment films in different states, and then a liquid crystal layer containing a liquid crystal compound is formed between the pair of substrates And a liquid crystal layer forming step.

  Also, a substrate for forming a liquid crystal display element comprising a liquid crystal alignment film, wherein the liquid crystal alignment film is formed of a liquid crystal alignment agent containing a polymer having a radical generating structure that generates radicals upon light irradiation. A substrate for forming a liquid crystal display element, wherein a radical is generated from at least a part of the radical generating structure by light irradiation.

  A liquid crystal display element assembly comprising a liquid crystal display element forming substrate having a pair of liquid crystal alignment films and a liquid crystal layer provided between the pair of liquid crystal display element substrates, The liquid crystal alignment film of the formation substrate for a liquid crystal display element is formed of a liquid crystal aligning agent having the same composition containing a polymer having a radical generating structure that generates radicals upon light irradiation, and at least one is irradiated with light. The liquid crystal display element assembly is characterized in that the light irradiation amounts of the two differ from each other.

  According to the present invention, a liquid crystal aligning agent containing a polymer having a radical generating structure that generates radicals by light irradiation is used, and at least one liquid crystal alignment film is irradiated in advance before providing a liquid crystal layer. , Invalidate at least part of the radical generation capability of the radical generation structure of the liquid crystal alignment film on one side, or perform light irradiation so that the amount of light irradiation is different between the two to make the radical generation capability on both sides different Thus, a liquid crystal layer having different alignment states on both sides of the liquid crystal layer can be formed, and a liquid crystal display element having a liquid crystal layer having different alignment states on both sides can be more easily manufactured. A method, a liquid crystal display element substrate and a liquid crystal display element assembly used in the manufacturing method can be provided.

  Further, according to the present invention, it is possible to provide a liquid crystal aligning agent suitable for a vertical alignment type liquid crystal display element having a high response speed, particularly a PSA type liquid crystal display element.

The present invention will be described in detail below.
<Method for manufacturing liquid crystal display element>
The method for producing a liquid crystal display element according to the present invention includes forming a liquid crystal alignment film on each of the surfaces of a pair of substrates with a liquid crystal alignment agent containing a polymer having a radical generating structure that generates radicals upon light irradiation. Between the forming step, the liquid crystal alignment film light irradiating step in which at least one of the pair of substrates is irradiated with light and the amount of light irradiation to the liquid crystal alignment film is different, and then between the pair of substrates, And a liquid crystal layer forming step of forming a liquid crystal layer containing a liquid crystal compound.

  In the liquid crystal alignment film forming step of the present invention, a substrate on which a liquid crystal alignment film formed with a liquid crystal aligning agent having the same composition is prepared. The liquid crystal aligning agent used here is a liquid crystal aligning agent containing a polymer having a radical generating structure that generates radicals by light irradiation. Details of the liquid crystal aligning agent will be described later.

  In the present invention, next, there is provided a liquid crystal alignment film light irradiating step in which at least one of the pair of substrates is irradiated with light so that the light irradiation amounts to the liquid crystal alignment films of the both are different. In this liquid crystal alignment film light irradiation step, the liquid crystal alignment film of the substrate used on one side is irradiated with light to invalidate at least part of the radical generating ability of the radical generating structure of the liquid crystal alignment film on one side, or both Irradiation is performed so that the amount of light irradiation is different so that the radical generating ability on both sides is different.

  Here, the light irradiation is to invalidate at least a part of the radical generation structure of the provided liquid crystal alignment film, that is, to generate radicals at this point and not to generate radicals thereafter. Specifically, the light irradiation may be performed with light having a wavelength necessary to deactivate the radical generating structure.

  Specifically, in the liquid crystal alignment film light irradiation step, for example, the liquid crystal alignment film of the substrate used on one side is irradiated with light to invalidate at least a part of the radical generating structure, thereby invalidating the radical generating ability. Thus, one is a liquid crystal alignment film having no radical generation ability, the other is a liquid crystal alignment film having radical generation ability, or one is a liquid crystal alignment film having low radical generation ability, and the other is a liquid crystal alignment film having high radical generation ability. , Make the radical generation ability on both sides different.

  Further, for example, the liquid crystal alignment films on the substrates on both sides are irradiated with light, but the amount of light irradiation is different on both sides, and the amount of radical generating structure to be invalidated is different on both sides. Thus, one is a liquid crystal alignment film having a low radical generation capability and the other is a liquid crystal alignment film having a high radical generation capability so that the radical generation capability on both sides is different.

  In this invention, after that, the liquid crystal layer formation process of forming the liquid crystal layer containing a polymeric compound between said pair of board | substrates is included. Accordingly, since the liquid crystal layer is formed by being sandwiched between a pair of liquid crystal alignment films having different radical generation capabilities, it is possible to form an asymmetric liquid crystal layer having different pretilt angles on both sides.

<Polymer having radical generating structure>
Although the polymer which has the radical generating structure contained in the liquid crystal aligning agent used by this invention is demonstrated with a specific example, it is not limited to the following specific examples.
The polymer having a radical generating structure used in the present invention (hereinafter also referred to as a specific polymer) has a site where a radical is generated by light irradiation, for example, ultraviolet irradiation, as a side chain. Examples of the specific polymer include a polymer having a side chain structure represented by the following formula (I) as a radical generating structure in which radicals are generated by ultraviolet irradiation.

Ar represents an aromatic hydrocarbon group selected from phenylene, naphthylene, and biphenylene, in which an organic group may be substituted, and a hydrogen atom may be substituted with a halogen atom. R ₁ and R ₂ are each independently an alkyl group or alkoxy group having 1 to 10 carbon atoms, and T 1 and T 2 are each independently a single bond or —O—, —COO—, —OCO—, — NHCO—, —CONH—, —NH—, —CH ₂ O—, —N (CH ₃ ) —, —CON (CH ₃ ) —, —N (CH ₃ ) CO— An alkylene group having 1 to 20 carbon atoms which is bonded or unsubstituted or substituted by a fluorine atom; However, the alkylene group —CH ₂ — or —CF ₂ — may be optionally replaced with —CH═CH—, and when any of the following groups is not adjacent to each other, these groups are replaced with these groups: -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, a divalent carbocycle, a divalent heterocycle, and Q is a structure selected from the following: Represents.

（Ｒは水素原子又は炭素原子数１〜４のアルキル基を表し、Ｒ_３は-ＣＨ_２-、−ＮＲ−、−Ｏ−、又は−Ｓ−を表す。）

(R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₃ represents —CH ₂ —, —NR—, —O—, or —S—).

  In the above formula (I), Ar to which carbonyl is bonded is involved in the absorption wavelength of ultraviolet rays. Therefore, when the wavelength is increased, a structure having a long conjugate length such as naphthylene or biphenylene is preferable. Ar may be substituted with a substituent, and the substituent is preferably an electron-donating organic group such as an alkyl group, a hydroxyl group, an alkoxy group, and an amino group.

  In the formula (I), when Ar has a structure such as naphthylene or biphenylene, the solubility becomes poor and the difficulty of synthesis increases. A phenyl group is most preferred because sufficient characteristics can be obtained even with a phenyl group if the wavelength of ultraviolet rays is in the range of 250 nm to 380 nm.

R ₁ and R ₂ are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group, a benzyl group, or a phenethyl group. In the case of an alkyl group or an alkoxy group, R ₁ and R ₂ are cyclic rings. May be formed.

In the formula (I), Q is preferably an electron donating organic group, and the above group is preferable.
In the case where Q is an amino derivative, there is a possibility that in the polymerization of polyamic acid which is a precursor of polyimide, there is a possibility that a carboxylic acid group generated and an amino group form a salt. Or it is an alkoxyl group.

  When a polyimide precursor and / or polyimide is used as the specific polymer and the structure of the above formula (I) is to be introduced into the side chain, the side chain structure of the formula (I) can be handled as a raw material. It is preferable from the viewpoint of easy synthesis of the polymer.

  Specifically, the site where radicals are generated by ultraviolet irradiation in the above formula (I) is preferably as follows. In particular, (b) or (c) is preferable from the viewpoint of the reliability of the obtained liquid crystal display element.

In formula (I), -T ₁ -ST ₂ -functions as a linking group that connects diaminobenzene and a site that generates a radical upon irradiation with ultraviolet rays. T ₁ and T ₂ are each independently a single bond, —O—, —S—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —CH ₂ O—, —N. _{(CH 3) -, - CON} (CH 3) -, or -N _(CH 3) a CO-. S is a single bond or an alkylene group having 1 to 20 carbon atoms which may be substituted with a fluorine atom (provided that —CH ₂ — or —CF ₂ — of the alkylene group is optionally substituted with —CH═CH—). And when any of the following groups are not adjacent to each other, these groups may be substituted: -O-, -COO-, -OCO-, -NHCO-, -CONH-,- NH-, a divalent carbocycle or a heterocycle.). In particular, T ₂ is most preferably —O— in terms of synthesis difficulty. S is preferably an alkylene group having 2 to 10 carbon atoms, more preferably 4 to 8 carbon atoms, from the viewpoint of synthesis difficulty or solubility.

  Moreover, as a specific polymer used by this invention, the polymer containing the side chain structure represented by following formula (II) can be mentioned, for example.

In the formula (II), a point means a bond to the main chain of the polymer, n is an integer selected from 1 to 12, and X is a single bond, —O—, —COO—, —OCO—, — _{NHCO -, - CONH -, -} NH -, - CH 2 O -, - N (CH 3) -, - CON (CH 3) -, or an -N _(CH 3) CO-. Cy represents a cyclic hydrocarbon group having 5 to 14 carbon atoms having at least one unsaturated bond that is necessarily bonded to the carbonyl carbon of the imide group, and a part of the carbon atoms constituting the cyclic hydrocarbon is heterogeneous. It may be replaced by an atom.

  Such a specific polymer has an organic group represented by the above formula (II) in the side chain. It is considered that this organic group is excited by ultraviolet irradiation to generate a radical, or has a function of chain-transferring a radical generated by another organic group, and functions as a radical generating structure. The structure having the function of chain-transferring this radical is also included in the radical generating structure of the present invention.

  In the formula (I), it is important that Cy, that is, a cyclic hydrocarbon group having at least one unsaturated bond, is bonded to two carbonyl carbons in the imide ring, and in particular, unsaturated to two carbonyl carbons. A structure in which the bonds are directly connected is preferable. In particular, the greater the number of unsaturated bonds, the higher the absorbance in the ultraviolet region and the longer the absorption wavelength, which is preferable when performing long wavelength exposure. Furthermore, a C6-C14 aromatic hydrocarbon group, a heterocyclic compound, etc. are more preferable. In view of the availability of reagents and the difficulty of synthesis, a cyclic hydrocarbon group containing no hetero atom is preferable. Although the example of preferable Cy is shown below, it is not limited to this. The two points of Cy each represent a bond to imidocarbonyl carbon.

  On the other hand, as the number of carbon atoms forming the ring structure increases, the structure becomes more rigid and the solubility in the solvent becomes poor. Therefore, from the viewpoint of monomer synthesis and the ease of handling of the monomer, the number of carbon atoms is relatively high. Fewer cyclic hydrocarbon groups are preferred, and particularly preferred are cyclohexene, benzene, naphthalene, biphenylene and the like. More preferred is the following structure.

  The hydrogen atom of the cyclic hydrocarbon group directly connected to the imide ring may be replaced with a fluorine atom or the like, or an organic group may be substituted. The organic group to be substituted is not particularly limited, but introduction of an organic group having a strong electron donating property or electron accepting property is preferable because an effect of increasing the absorption wavelength is expected. On the other hand, since a nitro group or an amino group may trap a generated radical, a monovalent organic group having a molecular weight of 14 to 100 is preferable, for example, an organic group such as a hydroxy group or a hydroxyl group, An alkoxyl group or an alkyl group having a relatively small molecular weight can be mentioned, but since the introduced substituent may trap the generated radical, it is necessary to pay attention to the selection of the substituent. For the above reasons, it is most preferably unsubstituted.

In the above formula (II), —X—C _n (H ₂ ) _n — represents a connecting site with a polymer chain. In the present invention, since the structure bonded to the imide carbonyl group of the side chain represented by the formula (II) is important, the linking site is not particularly limited. A bond, —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —CH ₂ O—, —N (CH ₃ ) —, —CON (CH ₃ ) —, or — N _(CH 3) CO-, and the like. The alkylene linked to X is preferably an alkylene having 1 to 12 carbon atoms, and the alkylene may have an unsaturated bond, a branched chain, or a cyclic structure, and the hydrogen atom in the alkylene is replaced with fluorine. It may be done. From the viewpoint of reagent availability and synthesis, X is —O— as the most easily synthesized structure, and alkylene is a linear alkylene having 1 to 6 carbon atoms.

  In the present invention, in the polymer having the organic group represented by the above formula (II) as a side chain, the means for introducing the side chain into the polymer is not particularly limited. Examples thereof include a method of obtaining a polymer by polymerization using a monomer having a side chain structure represented by the above formula (II), a method of introducing by polymer modification, and the like. Preferably, it is a method of introducing into a polymer using a monomer having an organic group represented by the above formula (I).

  The radical generating structure of the present invention is not limited to those described above, and any other side chain structure having a radical generating structure other than the described side chain structure can be suitably used. For example, a polymer containing a radical generating structure containing a reactive mesogen structure (see Patent Document 3, claim 1, etc.) in the side chain can be used.

<Side chains that align liquid crystal vertically>
The specific polymer contained in the liquid crystal aligning agent used in the present invention contains a liquid crystal in addition to the side chain having a radical generating structure represented by the above formula (I) or (II) (hereinafter also referred to as a specific side chain). It is preferred to have side chains that are oriented vertically. The side chain that vertically aligns the liquid crystal is represented by the following formula [III-1] or [III-2]. In addition, you may mix | blend the polymer which has a side chain which aligns a liquid crystal perpendicularly with a liquid crystal aligning agent separately from the specific polymer mentioned above.

（Ｘ^１は、単結合、−（ＣＨ_２）_ａ−（ａは１〜１５の整数である）、−Ｏ−、−ＣＨ_２Ｏ−、−ＣＯＯ−又は−ＯＣＯ−を表す。Ｘ^２は、単結合又は（ＣＨ_２）_ｂ−（ｂは１〜１５の整数である）を表す。Ｘ^３は、単結合、−（ＣＨ_２）_ｃ−（ｃは１〜１５の整数である）、−Ｏ−、−ＣＨ_２Ｏ−、−ＣＯＯ−又は−ＯＣＯ−を表す。Ｘ^４はベンゼン環、シクロヘキサン環、及び複素環から選ばれる２価の環状基で表し、これらの環状基の任意の水素原子は、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシル基、炭素数１〜３のフッ素含有アルキル基、炭素数１〜３のフッ素含有アルコキシル基又はフッ素原子で置換されていてもよく、さらに、Ｘ^４は、ステロイド骨格を有する炭素数１７〜５１の有機基から選ばれる２価の有機基であってもよい。Ｘ^５はベンゼン環、シクロヘキサン環及び複素環から選ばれる２価の環状基を表し、これらの環状基上の任意の水素原子は、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシル基、炭素数１〜３のフッ素含有アルキル基、炭素数１〜３のフッ素含有アルコキシル基又はフッ素原子で置換されていてもよい。ｎは０〜４の整数を表す。Ｘ^６は炭素数１〜１８のアルキル基、炭素数１〜１８のフッ素含有アルキル基、炭素数１〜１８のアルコキシル基、又は炭素数１〜１８のフッ素含有アルコキシル基を表す。）

^{(X 1} is a single _{bond, - (CH 2) a -} (a is an integer of _{1~15), - O -, -} CH 2 O -, - COO- or -OCO- .X ² representing a is , A single bond or (CH ₂ ) _b — (b is an integer of 1 to 15), X ³ is a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), Represents —O—, —CH ₂ O—, —COO— or —OCO—, wherein X ⁴ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring; The hydrogen atom is substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. at best, further, ^{X 4} is selected from an organic group having 17 to 51 carbon atoms having a steroid skeleton That divalent good .X ⁵ be an organic radical is a divalent cyclic group selected from benzene ring, cyclohexane ring and heterocyclic, any of hydrogen atoms on these cyclic groups, 1 to carbon atoms 3 may be substituted with an alkyl group having 1 to 3, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. Represents an integer of 4. X ⁶ represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. To express.)

Among these, X ¹ is a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O from the viewpoint of availability of raw materials and ease of synthesis. - or -COO-, and more preferred are a single _{bond, - (CH 2) a -} (a is an integer of 1 to 10), - O -, - _CH 2 O-or -COO- in which . Among these, X ² is preferably a single bond or (CH ₂ ) _b — (b is an integer of 1 to 10). X ³ is a single bond, — (CH ₂ ) _c — (where c is an integer of 1 to 15), —O—, —CH ₂ O—, or —COO— from the viewpoint of ease of synthesis. And more preferably a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 10), —O—, —CH ₂ O— or —COO—.

Among these, X ⁴ is preferably an organic group having 17 to 51 carbon atoms having a benzene ring, a cyclohexane ring or a steroid skeleton from the viewpoint of ease of synthesis. X ⁵ is preferably a benzene ring or a cyclohexane ring. In particular, n is preferably 0 to 3 and more preferably 0 to 2 in view of availability of raw materials and ease of synthesis.

X ⁶ is preferably an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 10 carbon atoms. More preferably, they are a C1-C12 alkyl group or a C1-C12 alkoxyl group. Particularly preferred is an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.

As preferred combinations of X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and n in the formula [III-1], International Publication No. WO2011 / 132751 (published 2011.10.27), page 13 to The same combinations as (2-1) to (2-629) listed in Table 6 to Table 47 on page 34 are mentioned. In each table of International Publication, ^X 1 to X ⁶ in the present invention is shown as Y1 to Y6, Y1 to ^Y6, shall read X 1 to X ^6.

  Moreover, in (2-605)-(2-629) published in each table | surface of international publication gazette, the C17-C51 organic group which has a steroid skeleton in this invention has 12-12 carbon atoms which have a steroid skeleton. An organic group having 25 to 25 carbon atoms having a steroid skeleton is to be read as an organic group having 17 to 51 carbon atoms having a steroid skeleton. Among them, (2-25) to (2-96), (2-145) to (2-168), (2-217) to (2-240), (2-268) to (2-315) , (2-364) to (2-387), (2-436) to (2-483), or (2-603) to (2-615) are preferred. Particularly preferred combinations are (2-49) to (2-96), (2-145) to (2-168), (2-217) to (2-240), (2-603) to (2- 606), (2-607) to (2-609), (2-611), (2-612) or (2-624).

X ⁷ represents a single bond, —O—, —CH ₂ O—, —CONH—, —NHCO—, —CON (CH ₃ ) —, —N (CH ₃ ) CO—, —COO— or —OCO—. To express. X ⁸ represents an alkyl group having 8 to 22 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms. Among these, X ⁷ is preferably a single bond, —O—, —CH ₂ O—, —CONH—, —CON (CH ₃ ) — or —COO—, and more preferably a single bond, —O—, — CONH- or -COO-. X ⁸ is preferably an alkyl group having 8 to 18 carbon atoms.

  As the side chain for vertically aligning the liquid crystal, it is preferable to use a structure represented by the formula [III-1] from the viewpoint that a high and stable vertical alignment of the liquid crystal can be obtained.

  The ability of a polymer having side chains for vertically aligning liquid crystals to align liquid crystals vertically varies depending on the structure of the side chains for vertically aligning liquid crystals, but in general, the side chains for vertically aligning liquid crystals. As the amount increases, the ability to align the liquid crystal vertically increases, and as the amount decreases, it decreases. Moreover, when it has a cyclic structure, compared with what does not have a cyclic structure, there exists a tendency for the capability to orientate a liquid crystal vertically.

<Photoreactive side chain>
The specific polymer contained in the liquid crystal aligning agent of the present invention has, for example, a photoreactive side chain in addition to the side chain having a radical generating structure represented by the above formula (I) or (II). May be. The photoreactive side chain has a functional group (hereinafter also referred to as a photoreactive group) that can react by irradiation with light such as ultraviolet rays (UV) to form a covalent bond. In addition, you may mix | blend the polymer which has a photoreactive side chain with a liquid crystal aligning agent separately from the specific polymer mentioned above.

  The photoreactive side chain may be directly bonded to the main chain of the polymer, or may be bonded via a linking group. The photoreactive side chain is represented, for example, by the following formula [IV].

R ⁸ is a single bond, —CH ₂ —, —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —CH ₂ O—, —N (CH ₃ ) —, —CON (CH ₃ ) — or —N (CH ₃ ) CO— is represented. R ⁹ represents a single bond or an alkylene group having 1 to 20 carbon atoms which may be substituted with a fluorine atom, and —CH ₂ — in the alkylene group is optionally substituted with —CF ₂ — or —CH═CH—. And when any of the following groups are not adjacent to each other, these groups may be substituted: -O-, -COO-, -OCO-, -NHCO-, -CONH-,- NH-, divalent carbocyclic or heterocyclic ring. R ¹⁰ represents a photoreactive group selected from the following formulae. Among these, R ⁸ is preferably a single bond, —O—, —COO—, —NHCO—, or —CONH—. R ⁹ can be formed by a general organic synthetic method, but a single bond or an alkylene group having 1 to 12 carbon atoms is preferable from the viewpoint of ease of synthesis.

Y ₁ represents —CH ₂ —, —O—, —CONH—, —NHCO—, —COO—, —OCO—, —NH—, or —CO—. Y ₂ is an alkylene group having 1 to 30 carbon atoms, a divalent carbocycle or a heterocycle, and one or more hydrogen atoms of the alkylene group, divalent carbocycle or heterocycle are fluorine atoms or organic It may be substituted with a group. Y ₂ represents that when the following groups are not adjacent to each other, —CH ₂ — may be substituted with these groups; —O—, —NHCO—, —CONH—, —COO—, —OCO—, -NH-, -NHCONH-, -CO-. Y ₃ represents —CH ₂ —, —O—, —CONH—, —NHCO—, —COO—, —OCO—, —NH—, —CO—, or a single bond. Y ₄ represents a cinnamoyl group. Y ₅ is a single bond, an alkylene group having 1 to 30 carbon atoms, a divalent carbocycle or a heterocycle, and one or more hydrogen atoms of the alkylene group, divalent carbocycle or heterocycle are fluorine atoms Alternatively, it may be substituted with an organic group. Y ₅ represents that when the following groups are not adjacent to each other, —CH ₂ — may be substituted with these groups; —O—, —NHCO—, —CONH—, —COO—, —OCO—, -NH-, -NHCONH-, -CO-. Y ₆ represents a photopolymerizable group which is an acrylic group or a methacryl group.

Further, in the formula [IV], specific examples of the divalent carbocycle or heterocycle for replacing any —CH ₂ — in R ⁹ include the following.

R ¹⁰ is preferably a methacryl group, an acryl group or a vinyl group from the viewpoint of photoreactivity.

  The abundance of the photoreactive side chain is preferably within a range in which the response speed of the liquid crystal can be increased by reacting with ultraviolet irradiation to form a covalent bond.

<Polymer forming liquid crystal aligning agent>
The polymer having a radical generating structure used in the present invention is not particularly limited, but a polyimide-based, poly (meth) acrylate-based, polysiloxane-based polymer, or the like can be preferably used. Hereinafter, although only the polyimide structure will be described in detail in the present specification, other polymers can be synthesized using known techniques (radical polymerization, sol-gel method, etc.).

  A method for producing a polyimide precursor having a specific side chain and a polyimide obtained by imidizing the polyimide precursor is not particularly limited. For example, a method of polymerizing a diamine having a specific side chain and a tetracarboxylic dianhydride, a method of polymerizing a diamine having a specific side chain and a tetracarboxylic acid diester, a tetracarboxylic dianhydride and a diamine containing a specific side chain Examples include a method of polymerizing a compound, a method of polymerizing a tetracarboxylic dianhydride and a diamine, and then modifying a compound containing a specific side chain into a polymer by some kind of reaction. Among these, from the viewpoint of ease of production, a method of polymerizing a diamine compound containing a specific side chain and tetracarboxylic dianhydride or tetracarboxylic diester is preferable.

The method similar to the above-mentioned is mentioned also about the method of manufacturing the polyimide precursor which has the side chain which orientates a liquid crystal vertically in addition to a specific side chain, and the polyimide which imidated this polyimide precursor. The preferable method is also preferably a method of polymerizing a diamine compound containing a side chain for vertically aligning a liquid crystal and a tetracarboxylic dianhydride or a tetracarboxylic acid diester.
The polyimide having a radical generating structure in the side chain can be prepared by using one or more of diamines such as the following specific diamines 1 to 3, for example.

<Specific diamine 1>
The diamine (hereinafter also referred to as a specific diamine) used in the production of the above-mentioned polymer forming the liquid crystal aligning agent of the present invention has, as a side chain, a site having a radical generating structure that is decomposed by ultraviolet irradiation to generate radicals. And represented by the following formula (1).

Ar, R ₁ , R ₂ , T ₁ , T ₂ , and S in the above formula (1) are as defined above.

  The diaminobenzene in the formula (1) may have any structure of o-phenylenediamine, m-phenylenediamine, or p-phenylenediamine, but in terms of reactivity with acid dianhydride, m-phenylenediamine, or p-Phenylenediamine is preferred.

  The specific diamine 1 is most preferably a structure represented by the following formula from the viewpoint of ease of synthesis, high versatility, characteristics, and the like. In the formula, n is an integer of 2 to 8.

<Synthesis of specific diamine 1>
In the present invention, the specific diamine 1 is a dinitro compound through each step, a mononitro compound having an amino group with a protective group that can be removed in the reduction process, or a diamine, and is synthesized by a reduction reaction that is usually used. It can be obtained by converting a group into an amino group or deprotecting a protecting group.

  There are various methods for synthesizing the diamine precursor. For example, a method of synthesizing a site where radicals are generated by ultraviolet irradiation, introducing a spacer site, and then binding to dinitrobenzene is shown below. In the formula, n is an integer of 2 to 8.

  In the case of the above reaction, one having two hydroxyl groups is used, but it can be selectively synthesized by optimizing the kind of base (catalyst) and the charging ratio.

  The base to be used is not particularly limited, but inorganic bases such as potassium carbonate, sodium carbonate and cesium carbonate, and organic bases such as pyridine, dimethylaminopyridine, trimethylamine, triethylamine and tributylamine are preferable.

  The method for reducing the dinitro compound, which is a diamine precursor, is not particularly limited. Usually, palladium carbon, platinum oxide, Raney nickel, platinum carbon, rhodium-alumina, platinum sulfide carbon, etc. are used as a catalyst, ethyl acetate, toluene, tetrahydrofuran. There is a method in which reduction is carried out with hydrogen gas, hydrazine, hydrogen chloride or the like in a solvent such as dioxane or alcohol. You may use an autoclave etc. as needed.

  On the other hand, when an unsaturated bond site is included in the structure, if palladium carbon or platinum carbon is used, the unsaturated bond site may be reduced and become a saturated bond. Reduction conditions using a transition metal such as tin chloride, poisoned palladium carbon or platinum carbon, platinum carbon doped with iron or the like as a catalyst are preferable.

  Similarly, the diamine of the present invention can be obtained by deprotecting a diaminobenzene derivative protected with a benzyl group or the like in the reduction step.

  The specific diamine 1 is preferably 10 to 80 mol%, more preferably 20 to 60 mol%, and particularly preferably 30 to 50 mol% of the diamine component used for the synthesis of the polyamic acid.

<Specific diamine 2>
The specific diamine 2 of the present invention can be represented by a diamine having an organic group represented by the formula (II) as a side chain, that is, the following formula (VI).

  In formula (VI), Sp is an alkylene group having 1 to 12 carbon atoms, and the alkylene group may have an unsaturated bond, a branched chain, or a cyclic structure. X represents a single bond or a linking group. Cy represents a cyclic hydrocarbon group having 5 to 14 carbon atoms having at least one unsaturated bond that is necessarily bonded to the carbonyl carbon of the imide group, and a part of the carbon atoms constituting the cyclic hydrocarbon is heterogeneous. It may be replaced by an atom.

  The diaminobenzene in the formula (VI) may have a structure of any of o-phenylenediamine, m-phenylenediamine, or p-phenylenediamine, but in terms of reactivity with acid dianhydride, m-phenylenediamine, Or p-phenylenediamine is preferable. A preferred structure of the formula (VI) is a diamine represented by the following formula (X),

（式中のｎは１〜６の整数）

(Where n is an integer from 1 to 6)

  More preferably, the structure represented by the following formula (XI) is most preferable from the viewpoint of easiness of synthesis, high versatility, characteristics and the like.

（式中ｍは１〜３の整数）

(Where m is an integer from 1 to 3)

<Synthesis of specific diamine 2>
In the present invention, the specific diamine 2 is a dinitro compound through each step, a mononitro compound having an amino group with a protective group that can be removed in the reduction process, or a diamine, and is synthesized by a reduction reaction usually used. It can be obtained by converting a group into an amino group or deprotecting a protecting group.

  Various methods for synthesizing the diamine precursor are conceivable. For example, a method of obtaining a diamine precursor by reacting an alcohol, alkylamine, alkyl halide or the like having a target imide structure with dinitrobenzene, or by reacting an alkylamine having dinitrobenzene already introduced with an acid anhydride. Examples thereof include a Mitsunobu reaction between an alcohol already introduced with dinitrobenzene and an N unsubstituted imide, and a method of condensing an alkyl halide already introduced with dinitrobenzene and an N unsubstituted imide in the presence of a base or a metal catalyst.

  The above is an example of synthesis in which the bond to the dinitro compound is an ether bond, but other bonds having an ester bond or an amide bond can be synthesized according to the above method.

  The method for reducing the dinitro compound, which is a diamine precursor, is not particularly limited. Usually, palladium carbon, platinum oxide, Raney nickel, platinum carbon, rhodium-alumina, platinum sulfide carbon, etc. are used as a catalyst, ethyl acetate, toluene, tetrahydrofuran. There is a method in which reduction is carried out with hydrogen gas, hydrazine, hydrogen chloride or the like in a solvent such as dioxane or alcohol. You may use an autoclave etc. as needed.

  On the other hand, when an unsaturated bond site is included in the structure, if palladium carbon or platinum carbon is used, the unsaturated bond site may be reduced and become a saturated bond. Reduction conditions using a transition metal such as tin chloride, poisoned palladium carbon or platinum carbon, platinum carbon doped with iron or the like as a catalyst are preferable.

  Similarly, the diamine of the present invention can be obtained by deprotecting a diaminobenzene derivative protected with a benzyl group or the like in the reduction step.

<Specific diamine 3>
The specific diamine 3 of the present invention is represented by the following formula (11).

The specific diamine 3 has a photoreactive structure in which radicals are generated by ultraviolet irradiation in a single molecular structure and a structure in which liquid crystals are aligned vertically. That is, the light reactive structure is a 4-chromanone structure bonded via X ¹¹ phenylenediamine skeleton, also, the structure of aligning the liquid crystal vertically, are attached to the 4-chromanone -X ₂ -X ₃ -X ₄ structure.
In the above formula (11), each definition of X ¹¹ , X ¹² , X ¹³ and X ¹⁴ is as described above. Among these, X ¹¹ is preferably —O— or —CH ₂ O— from the viewpoint of ease of synthesis. X ¹² _and X ¹³ are preferably cyclohexane rings from the viewpoint of high vertical alignment. ^{Furthermore, X 14,} from the viewpoint of the availability of raw materials, preferably an alkyl group having 3 to 7 carbon atoms.

  Preferable specific examples of the specific diamine 3 include the following.

<Production of specific diamine 3>
Although the synthesis | combining method of the specific diamine 3 in this invention is not specifically limited, For example, it is compoundable by the method shown below.
That is, a dinitro compound represented by the following general formula (12) corresponding to the specific diamine 3 (wherein X ^{11 to} X ¹⁴ are the same as those in the formula (11)) is synthesized, and the nitro group is further reduced to form an amino group. Obtained by converting to.

There is no restriction | limiting in particular in the method of reducing the said dinitro compound, Usually, palladium-carbon, platinum-carbon, platinum oxide, Raney nickel, iron, tin chloride, platinum black, rhodium-alumina, platinum carbon sulfide etc. are used as a catalyst. , Ethyl acetate, toluene, tetrahydrofuran, dioxane, alcohol-based solvents, hydrogen gas, hydrazine, hydrogen chloride, ammonium chloride, and the like.
The method for synthesizing the dinitro compound represented by the general formula (12) is not particularly limited and can be synthesized by any method. Specific examples thereof include those shown in the following scheme (13). It can be synthesized by the method.

In scheme (13), the dinitro compound A and the compound B having a hydroxyl group are reacted in an organic solvent (for example, ethyl acetate, toluene, tetrahydrofuran, dioxane, chloroform, dichloromethane, DMF, DMSO, etc.) in the presence of an alkali. Can be synthesized. As the alkali, for example, an organic amine such as triethylamine, or an inorganic salt such as potassium carbonate or sodium hydroxide can be used.
In the dinitrobenzene compound A, X ¹⁵ is any one of chlorine, bromine, iodine, fluorine, —OH, —COOH, —COOCl, — (CH ₂ ) _a OH (a is an integer of 1 to 15). Thus, X ^{12 to} X ¹⁴ in the phenol compound B are the same as those in Formula 1. In addition, the compound shown here is an example and is not specifically limited.

  The specific diamine is preferably 10 mol% to 80 mol%, more preferably 20 mol% to 60 mol%, particularly preferably 30 mol% to 50 mol% of the diamine component used for the synthesis of the polyamic acid. is there.

<Diamines with side chains that align liquid crystals vertically>
In the method of introducing a side chain for vertically aligning liquid crystal into the polyimide polymer, it is preferable to use a diamine having a specific side chain structure as a part of the diamine component.

  X represents the structure of the above formula [III-1] or [III-2], and n represents an integer of 1 to 4.

R ⁸ , R ⁹ and R ¹⁰ are as defined above.

Y _{1 to} Y ₆ are as described above.

  Specific examples of the specific side chain diamine include structures represented by the following formulas [2a-1] to [2a-31].

（Ｒ^１は−Ｏ−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−ＣＯＯＣＨ_２−又は−ＣＨ_２ＯＣＯ−を示し、Ｒ^２は炭素数１〜２２の直鎖状若しくは分岐状アルキル基、炭素数１〜２２の直鎖状若しくは分岐状アルコキシル基、炭素数１〜２２の直鎖状若しくは分岐状の、フッ素含有アルキル基又はフッ素含有アルコキシル基である。）

(R ¹ represents —O—, —OCH ₂ —, —CH ₂ O—, —COOCH ₂ — or —CH ₂ OCO—, and R ² represents a linear or branched alkyl group having 1 to 22 carbon atoms, C1-C22 linear or branched alkoxyl group, C1-C22 linear or branched fluorine-containing alkyl group or fluorine-containing alkoxyl group.)

（Ｒ^３は、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＯＣＨ_２−、−ＣＨ_２ＯＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−又は−ＣＨ_２−を示し、Ｒ^４は炭素数１〜２２の直鎖状若しくは分岐状アルキル基、炭素数１〜２２の直鎖状若しくは分岐状アルコキシル基、炭素数１〜２２の直鎖状若しくは分岐状の、フッ素含有アルキル基又はフッ素含有アルコキシル基である。）

(R ³ represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH ₂ O—, —OCH ₂ — or —CH ₂ —, R ⁴ is a linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched alkoxyl group having 1 to 22 carbon atoms, a linear or branched alkyl group having 1 to 22 carbon atoms, fluorine-containing alkyl Group or fluorine-containing alkoxyl group.)

（Ｒ^５は、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＯＣＨ_２−、−ＣＨ_２ＯＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＨ_２−、−Ｏ−又は−ＮＨ−を示し、Ｒ^６はフッ素基、シアノ基、トリフルオロメタン基、ニトロ基、アゾ基、ホルミル基、アセチル基、アセトキシ基又は水酸基である。）

(R ⁵ is —COO—, —OCO—, —CONH—, —NHCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH ₂ O—, —OCH ₂ —, —CH ₂ —, —O -Represents-or -NH-, and R ⁶ represents a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group or a hydroxyl group.

（Ｒ^７は炭素数３〜１２の直鎖状又は分岐状アルキル基であり、１，４−シクロヘキシレンのシス−トランス異性は、それぞれトランス異性体である。）

(R ⁷ is a linear or branched alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.)

（Ｒ^８は炭素数３〜１２の直鎖状又は分岐状アルキル基であり、１，４−シクロヘキシレンのシス−トランス異性は、それぞれトランス異性体である。）

(R ⁸ is a linear or branched alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.)

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

(A ₄ is a linear or branched alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, and A ₃ is a 1,4-cyclohexylene group or a 1,4-phenylene group. , A ₂ is an oxygen atom or COO- * (where a bond with “*” is bonded to A ₃ ), and A ₁ is an oxygen atom or COO— * (where “*” is a bond) The hand binds to (CH ₂ ) a ₂ ). A ₁ is an integer of 0 or 1, a ₂ is an integer of ₂ to 10, and a ₃ is an integer of 0 or 1. )

  Among the above formulas [2a-1] to [2a-31], particularly preferred are formula [2a-1] to formula [2a-6], formula [2a-9] to formula [2a-13] or formula [ 2a-22] to [2a-31].

  Examples of the diamine having a specific side chain structure represented by the formula [III-2] include diamines represented by the following formulas [2b-1] to [2b-10].

（Ａ^１は、炭素数１〜２２のアルキル基又はフッ素含有アルキル基を示す。）

^{(A 1} is an alkyl group or a fluorine-containing alkyl group having 1 to 22 carbon atoms.)

In the above formula [2b-5] to formula [2b-10], A ¹ represents —COO—, —OCO—, —CONH—, —NHCO—, —CH ₂ —, —O—, —CO— or —NH. -And A ² represents a linear or branched alkyl group having 1 to 22 carbon atoms or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms.

  Said diamine can also be used 1 type or in mixture of 2 or more types according to characteristics, such as a liquid crystal aligning property at the time of setting it as a liquid crystal aligning film, a pretilt angle, a voltage holding characteristic, and a stored charge.

  The diamine having a side chain for vertically aligning the liquid crystal is preferably used in an amount of 5 to 70 mol% of the diamine component used for the synthesis of the polyamic acid, more preferably 20 mol% to 60 mol% of the diamine component, Most preferably, it is 20 mol%-50 mol%.

<Diamine containing photoreactive side chain>
As a method for introducing a side chain having photoreactivity into a polyimide polymer, it is preferable to use a diamine having a specific side chain structure as a part of the diamine component. The diamine having a photoreactive side chain is a diamine having a side chain represented by Formula [VIII] or Formula [IX].

（［ＶＩＩＩ］中のＲ^８、Ｒ^９及びＲ^１０の定義は、上記式［ＩＶ］と同じである。）

(The definitions of R ⁸ , R ⁹ and R ¹⁰ in [VIII] are the same as those in the above formula [IV].)

（式［ＩＸ］中のＹ₁、Ｙ_２，Ｙ_３，Ｙ_４，Ｙ_５，及びＹ_６の定義は、上記式［Ｖ］と同じである。）

(The definitions of Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , and Y ₆ in Formula [IX] are the same as in Formula [V] above.)

The bonding positions of the two amino groups (—NH ₂ ) in Formula [VIII] and Formula [IX] are not limited. Specifically, with respect to the linking group of the side chain, 2, 3 position, 2, 4 position, 2, 5 position, 2, 6 position, 3, 4 position on the benzene ring, 3, 4 position, 5 positions. Among these, from the viewpoint of reactivity when synthesizing a polyamic acid, positions 2, 4, 2, 5, or 3, 5 are preferable. Considering the ease in synthesizing the diamine, the positions 2, 4 or 3, 5 are more preferable.

  Specific examples of the diamine having a photoreactive side chain include, but are not limited to, the following.

（Ｘ^９、Ｘ^１０は、それぞれ独立に、単結合、−Ｏ−、−ＣＯＯ−、−ＮＨＣＯ−、又は−ＮＨ−である結合基、Ｙはフッ素原子で置換されていてもよい炭素数１〜２０のアルキレン基を表す。）

(X ⁹ and X ¹⁰ each independently represents a single bond, —O—, —COO—, —NHCO—, or —NH—, a bonding group that is —NH—, and Y is a carbon atom that may be substituted with a fluorine atom. Represents an alkylene group of ˜20.)

  Examples of the diamine having a photoreactive side chain include a diamine having a group causing a photodimerization reaction and a group causing a photopolymerization reaction represented by the following formula in the side chain.

In the above formula, Y ₁ represents —CH ₂ —, —O—, —CONH—, —NHCO—, —COO—, —OCO—, —NH—, or —CO—. Y ₂ is an alkylene group having 1 to 30 carbon atoms, a divalent carbocycle or a heterocycle, and one or more hydrogen atoms of the alkylene group, divalent carbocycle or heterocycle are fluorine atoms or organic It may be substituted with a group. Y ₂ represents that when the following groups are not adjacent to each other, —CH ₂ — may be substituted with these groups; —O—, —NHCO—, —CONH—, —COO—, —OCO—, -NH-, -NHCONH-, -CO-. Y ₃ represents —CH ₂ —, —O—, —CONH—, —NHCO—, —COO—, —OCO—, —NH—, —CO—, or a single bond. Y ₄ represents a cinnamoyl group. Y ₅ is a single bond, an alkylene group having 1 to 30 carbon atoms, a divalent carbocycle or a heterocycle, and one or more hydrogen atoms of the alkylene group, divalent carbocycle or heterocycle are fluorine atoms Alternatively, it may be substituted with an organic group. Y ₅ represents that when the following groups are not adjacent to each other, —CH ₂ — may be substituted with these groups; —O—, —NHCO—, —CONH—, —COO—, —OCO—, -NH-, -NHCONH-, -CO-. Y ₆ represents a photopolymerizable group which is an acrylic group or a methacryl group.

  The diamine having a photoreactive side chain depends on the liquid crystal alignment property when it is used as a liquid crystal alignment film, the pretilt angle, the voltage holding property, the characteristics such as accumulated charge, the response speed of the liquid crystal when it is used as a liquid crystal display device, etc. 1 type or 2 types or more can be mixed and used.

  Moreover, it is preferable to use 10-70 mol% of the diamine component used for the synthesis | combination of a polyamic acid as a diamine which has a photoreactive side chain, More preferably, it is 20-60 mol%, Most preferably, it is 30-50 mol%. It is.

<(B) component>
The liquid crystal aligning agent of the present invention comprises, as component (A), a polyimide precursor having a side chain for vertically aligning liquid crystals and a side chain having a radical generating structure represented by the above formula (I), and this Contains at least one polymer selected from polyimides obtained by imidizing a polyimide precursor, and at least one diamine selected from the following formulas (B-1) to (B-5) as component (B) A polyimide precursor obtained using a diamine component as a raw material, a polymer selected from a polyimide obtained by imidizing this polyimide precursor, or at least one selected from the following formulas (3) and (4) A polyimide precursor obtained by reaction of a tetracarboxylic dianhydride component containing tetracarboxylic dianhydride and a diamine, and the polyimide precursor The can contain polymer selected from the resulting polyimide by imidization.

（式中Ｙ₁は二級アミン、三級アミン、または、複素環構造を有する一価の有機基を表し、Ｙ₂は二級アミン、三級アミン、または、複素環構造を有する二価の有機基を表す。）

Wherein Y ₁ represents a secondary amine, tertiary amine, or a monovalent organic group having a heterocyclic structure, and Y ₂ represents a secondary amine, tertiary amine, or a divalent organic group having a heterocyclic structure. Represents an organic group.)

  When at least one tetracarboxylic dianhydride selected from the above formulas (3) and (4) is used as a raw material, the accumulated charge characteristics are improved because of interaction between [liquid crystal-alignment film] by light irradiation. be able to. Examples of the tetracarboxylic dianhydride represented by the formula selected from the formulas (3) and (4) include, but are not limited to, the following compounds.

  At least one tetracarboxylic dianhydride selected from the above formulas (1-1) to (1-4) is a tetracarboxylic dianhydride component used for the synthesis of the component (B) which is a polyamic acid. It is preferable to use an amount of 10 to 100% of the above. More preferably, 10 to 60% is used.

  Moreover, as long as the effect of this invention is not impaired, you may use tetracarboxylic dianhydrides other than said Formula (1-1)-(1-4) as a raw material of (B) component. Specific examples include, but are not limited to, the tetracarboxylic dianhydrides described in the component (A).

  For example, when a tetracarboxylic dianhydride having an aliphatic group or an alicyclic group is also used as a raw material, 0 to 90% of the tetracarboxylic dianhydride component used for the synthesis of the component (B) that is a polyamic acid; Is preferably used.

  When at least one tetracarboxylic dianhydride selected from the above formulas (1-1) to (1-4) is used as the component (B), the diamine component to be reacted is not particularly limited, and specific examples thereof Examples of the diamine include the diamines mentioned in the component (A), and at least one diamine selected from the above formulas (B-1) to (B-5) is preferably used from the viewpoint of accumulated charge characteristics.

  In addition, the polymer which is (B) component is a polyimide precursor obtained by using as a raw material a diamine component containing at least one kind of diamine selected from the following formulas (B-1) to (B-5), and this The polymer selected from the polyimide obtained by imidating a polyimide precursor may be sufficient.

（式中Ｙ₁は二級アミン、三級アミン、または、複素環構造を有する一価の有機基を表し、Ｙ₂は二級アミン、三級アミン、または、複素環構造を有する二価の有機基を表す。）

Wherein Y ₁ represents a secondary amine, tertiary amine, or a monovalent organic group having a heterocyclic structure, and Y ₂ represents a secondary amine, tertiary amine, or a divalent organic group having a heterocyclic structure. Represents an organic group.)

  A diamine having a specific structure with high polarity, selected from the above formulas (B-1) to (B-5), or a diamine having a carboxyl group and a diamine having a nitrogen-containing aromatic heterocyclic ring. By using at least one or more of each in combination, charge transfer is promoted by electrostatic interactions such as salt formation and hydrogen bonding, so that accumulated charge characteristics can be improved. Examples of the at least one diamine selected from the above formulas (B-1) to (B-5) include, but are not limited to, the following diamines.

<Other diamines>
In addition, when manufacturing a polyimide precursor and / or a polyimide, unless the effect of this invention is impaired, other diamines other than the above-mentioned diamine can be used together. Specifically, for example, p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl- m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2, 4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl 3,3′-dihydroxy-4,4′-diaminobiphenyl, 3,3′-dicarboxy-4,4′-diaminobiph Nyl, 3,3′-difluoro-4,4′-biphenyl, 3,3′-trifluoromethyl-4,4′-diaminobiphenyl, 3,4′-diaminobiphenyl, 3,3′-diaminobiphenyl, 2 , 2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3 '-Diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'- Sulfonyl dianiline, 3,3′-sulfonyl dianiline, bis (4-aminophenyl) si Lan, bis (3-aminophenyl) silane, dimethyl-bis (4-aminophenyl) silane, dimethyl-bis (3-aminophenyl) silane, 4,4'-thiodianiline, 3,3'-thiodianiline, 4,4 '-Diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl (4,4'-diaminodiphenyl) amine N-methyl (3,3′-diaminodiphenyl) amine, N-methyl (3,4′-diaminodiphenyl) amine, N-methyl (2,2′-diaminodiphenyl) amine, N-methyl (2,3 '-Diaminodiphenyl) amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4' Diaminobenzophenone, 1,4-diaminonaphthalene, 2,2′-diaminobenzophenone, 2,3′-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8 -Diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis (4-aminophenyl) ethane, 1,2-bis (3-aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,3-bis (3-aminophenyl) propane, 1,4-bis (4-aminophenyl) butane, 1,4 -Bis (3-aminophenyl) butane, bis (3,5-diethyl-4-aminophenyl) methane, 1,4-bis (4 -Aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (4-aminobenzyl) benzene, 1,3-bis (4-aminophenoxy) benzene, 4,4 ′-[1,4-phenylenebis (methylene)] dianiline, 4,4 ′-[1,3-phenylene Bis (methylene)] dianiline, 3,4 ′-[1,4-phenylenebis (methylene)] dianiline, 3,4 ′-[1,3-phenylenebis (methylene)] dianiline, 3,3 ′-[1 , 4-phenylenebis (methylene)] dianiline, 3,3 ′-[1,3-phenylenebis (methylene)] dianiline, 1,4-phenylenebis [(4-aminophenyl) methanone], 1 4-phenylenebis [(3-aminophenyl) methanone], 1,3-phenylenebis [(4-aminophenyl) methanone], 1,3-phenylenebis [(3-aminophenyl) methanone], 1,4- Phenylenebis (4-aminobenzoate), 1,4-phenylenebis (3-aminobenzoate), 1,3-phenylenebis (4-aminobenzoate), 1,3-phenylenebis (3-aminobenzoate), bis ( 4-aminophenyl) terephthalate, bis (3-aminophenyl) terephthalate, bis (4-aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, N, N ′-(1,4-phenylene) bis ( 4-aminobenzamide), N, N ′-(1,3-phenylene) bis (4-aminobenzamide), N , N ′-(1,4-phenylene) bis (3-aminobenzamide), N, N ′-(1,3-phenylene) bis (3-aminobenzamide), N, N′-bis (4-aminophenyl) ) Terephthalamide, N, N′-bis (3-aminophenyl) terephthalamide, N, N′-bis (4-aminophenyl) isophthalamide, N, N′-bis (3-aminophenyl) isophthalamide, 9 , 10-bis (4-aminophenyl) anthracene, 4,4′-bis (4-aminophenoxy) diphenyl sulfone, 2,2′-bis [4- (4-aminophenoxy) phenyl] propane, 2,2 ′ -Bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2'-bis (4-aminophenyl) hexafluoropropane, 2,2'-bis (3-aminophenyl) Nyl) hexafluoropropane, 2,2′-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2′-bis (4-aminophenyl) propane, 2,2′-bis (3-amino) Phenyl) propane, 2,2′-bis (3-amino-4-methylphenyl) propane, 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid, 1,3-bis (4-aminophenoxy) propane 1,3-bis (3-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, 1,4-bis (3-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) ) Pentane, 1,5-bis (3-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) hexane, 1,6-bis (3-aminophenoxy) hexane, 7-bis (4-aminophenoxy) heptane, 1,7- (3-aminophenoxy) heptane, 1,8-bis (4-aminophenoxy) octane, 1,8-bis (3-aminophenoxy) octane, 1 , 9-bis (4-aminophenoxy) nonane, 1,9-bis (3-aminophenoxy) nonane, 1,10- (4-aminophenoxy) decane, 1,10- (3-aminophenoxy) decane, , 11- (4-aminophenoxy) undecane, 1,11- (3-aminophenoxy) undecane, 1,12- (4-aminophenoxy) dodecane, 1,12- (3-aminophenoxy) dodecane, etc. Alicyclic diamines such as diamine, bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, 1,3 -Diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10- Examples include aliphatic diamines such as diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane.

  The above-mentioned other diamines can be used alone or in combination of two or more according to properties such as liquid crystal orientation, pretilt angle, voltage holding property, and accumulated charge when the liquid crystal alignment film is used.

<Tetracarboxylic dianhydride>
The tetracarboxylic dianhydride component to be reacted with the diamine component is not particularly limited. Specifically, pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2, 3,6,7-anthracenetetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4-biphenyltetra Carboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxy) Phenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3,4-dicarboxyphenyl) Lopan, bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis (3,4) -Dicarboxyphenyl) pyridine, 3,3 ', 4,4'-diphenylsulfonetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 1,3-diphenyl-1,2,3,4- Cyclobutanetetracarboxylic acid, oxydiphthaltetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic Acid, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2-dimethyl-1,2,3,4-cyclobut Tetracarboxylic acid, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cycloheptanetetracarboxylic acid, 2,3,4,5-tetrahydrofurantetracarboxylic acid 3,4-dicarboxy-1-cyclohexylsuccinic acid, 2,3,5-tricarboxycyclopentylacetic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid, bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid, bicyclo [4,3,0] nonane-2,4,7,9-tetracarboxylic acid, bicyclo [4,4,0 ] Decane-2,4,7,9-tetracarboxylic acid, bicyclo [4,4,0] decane-2,4,8,10-tetracarboxylic acid, tricyclo [6.3.0.0 <2,6 >] Undecane 3,5,9,11-tetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetra Hydrinaphthalene-1,2-dicarboxylic acid, bicyclo [2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic acid, 5- (2,5-dioxotetrahydrofuryl) -3 -Methyl-3-cyclohexane-1,2-dicarboxylic acid, tetracyclo [6,2,1,1,0,2,7] dodeca-4,5,9,10-tetracarboxylic acid, 3,5, Examples include 6-tricarboxynorbornane-2: 3,5: 6 dicarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, and the like. Of course, tetracarboxylic dianhydride may be used alone or in combination of two or more depending on the liquid crystal alignment properties, voltage holding characteristics, accumulated charge, and the like when the liquid crystal alignment film is formed.

<Polymerizable compound>
The liquid crystal aligning agent of the present invention may contain a polymerizable compound having a photopolymerizable or photocrosslinkable group at two or more terminals as required. Such a polymerizable compound is a compound having two or more terminals having a group that undergoes photopolymerization or photocrosslinking. Here, the polymerizable compound having a photopolymerizable group is a compound having a functional group that causes polymerization upon irradiation with light. The compound having a photocrosslinking group is at least one selected from a polymer of a polymerizable compound, a polyimide precursor, and a polyimide obtained by imidizing the polyimide precursor by irradiating light. It is a compound having a functional group capable of reacting with the polymer and crosslinking with these polymers. A compound having a photocrosslinkable group also reacts with a compound having a photocrosslinkable group.

  By using the liquid crystal aligning agent of the present invention containing the polymerizable compound in a vertical alignment type liquid crystal display element such as an SC-PVA type liquid crystal display, the side chain and the photoreactive property of aligning the liquid crystal vertically are used. Compared to the case of using a polymer having a side chain and this polymerizable compound alone, the response speed can be remarkably improved, and the response speed can be sufficiently improved even with a small amount of the polymerizable compound added. Can do.

  Examples of the group that undergoes photopolymerization or photocrosslinking include monovalent groups represented by the following formula (X).

（Ｒ^１２は、水素原子、又は炭素数１〜４のアルキル基を表す。Ｚ^１は、炭素数１〜１２のアルキル基又は炭素数１〜１２のアルコキシル基によって置換されていてもよい二価の芳香環若しくは複素環を表す。Ｚ^２は炭素数１〜１２のアルキル基又は炭素数１〜１２のアルコキシル基によって置換されていてもよい一価の芳香環若しくは複素環を表す。）

(R ¹² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Z ¹ is a divalent group that may be substituted by an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. Z ² represents a monovalent aromatic ring or heterocyclic ring optionally substituted by an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms.

  Specific examples of the polymerizable compound include a compound having a photopolymerizable group at each of two terminals represented by the following formula (XI), a terminal having a photopolymerizable group represented by the following formula (XII), and light. Examples thereof include a compound having a terminal having a cross-linking group and a compound having a photo-crosslinking group at each of two terminals represented by the following formula (XIII).

In Formula ^{(XI) ~ (XIII),} R 12, Z 1 and ^{Z 2} are the same as ^R 12, ^{Z 1} and ^{Z 2} in the formula (X), ^{Q 1} is a divalent organic group is there. Q ¹ has a ring structure such as a phenylene group (—C ₆ H ₄ —), a biphenylene group (—C ₆ H ₄ —C ₆ H ₄ —), a cyclohexylene group (—C ₆ H ₁₀ —), and the like. Preferably it is. This is because the interaction with the liquid crystal tends to increase.

Specific examples of the polymerizable compound represented by the formula [XI] include a polymerizable compound represented by the following formula (4). In the following formula (4), V and W are represented by a single bond or —R ¹ O—, and R ¹ is a linear or branched alkylene group having 1 to 10 carbon atoms, preferably — R ¹ O— is represented, and R ¹ is a linear or branched alkylene group having 2 to 6 carbon atoms. V and W may be the same or different, but synthesis is easy when they are the same.

  In addition, even if it is a polymerizable compound having an acrylate group or a methacrylate group instead of an α-methylene-γ-butyrolactone group as a group for photopolymerization or photocrosslinking, the acrylate group or methacrylate group is a spacer such as an oxyalkylene group. The polymerizable compound having a structure bonded to the phenylene group via the silane can particularly greatly improve the response speed, similarly to the polymerizable compound having α-methylene-γ-butyrolactone groups at both ends. . In addition, a polymerizable compound having a structure in which an acrylate group or a methacrylate group is bonded to a phenylene group through a spacer such as an oxyalkylene group has improved heat stability, and a high temperature, for example, a firing temperature of 200 ° C. or higher. Can withstand enough.

<Synthesis of polyamic acid>
In obtaining a polyamic acid by a reaction between a diamine component and tetracarboxylic dianhydride, a known synthesis method can be used. In general, a diamine component and a tetracarboxylic dianhydride component are reacted in an organic solvent. The reaction of the diamine component and tetracarbonic dianhydride is advantageous in that it proceeds relatively easily in an organic solvent and no by-products are generated.

  The organic solvent used in the above reaction is not particularly limited as long as the generated polyamic acid dissolves. Furthermore, even if it is an organic solvent in which a polyamic acid does not melt | dissolve, you may mix and use the said solvent in the range which the produced | generated polyamic acid does not precipitate. In addition, since the water | moisture content in an organic solvent inhibits a polymerization reaction and also causes the produced polyamic acid to hydrolyze, it is preferable to use what dehydrated and dried the organic solvent.

  Examples of the organic solvent used in the above reaction include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N-methylformamide, N-methyl-2-pyrrolidone, and N-ethyl-2. -Pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide, N-methylcaprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl Sulfoxide, γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, Lucerosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether , Propylene glycol monobutyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether , Dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl -3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether , Dihexyl ether, dioxane, n-hexane, n-pentane, n-octa , Diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate , Methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4- Examples thereof include methyl-2-pentanone and 2-ethyl-1-hexanol. These organic solvents may be used alone or in combination.

  The method of reacting a diamine component and a tetracarboxylic dianhydride component in an organic solvent is to stir a solution in which the diamine component is dispersed or dissolved in the organic solvent, and the tetracarboxylic dianhydride component as it is or an organic solvent. Dispersing or dissolving in a solution, adding a diamine component to a solution obtained by dispersing or dissolving a tetracarboxylic dianhydride component in an organic solvent, alternating tetracarboxylic dianhydride component and diamine component Any of the methods of adding to In addition, when the diamine component or tetracarboxylic dianhydride component is composed of a plurality of types of compounds, they may be reacted in a premixed state, may be individually reacted sequentially, or may be further reacted individually. The body may be mixed and reacted to form a high molecular weight body.

  The temperature at the time of making a diamine component and a tetracarboxylic dianhydride component react is -20 degreeC-150 degreeC, for example, Preferably it is the range of -5 degreeC-100 degreeC. Moreover, 1-50 mass% of the sum total density | concentration of a diamine component and a tetracarboxylic dianhydride component is preferable with respect to reaction liquid, for example, and 5-30 mass% is more preferable for reaction.

  The ratio of the total number of moles of the tetracarboxylic dianhydride component to the total number of moles of the diamine component in the polymerization reaction can be selected according to the molecular weight of the polyamic acid to be obtained. Similar to the usual polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the polyamic acid produced, and 0.8 to 1.2 if a preferred range is shown.

  The method for synthesizing the polyamic acid used in the present invention is not limited to the above-described method, and in the same manner as the general polyamic acid synthesis method, instead of the tetracarboxylic dianhydride, a tetracarboxylic acid having a corresponding structure is used. The corresponding polyamic acid can also be obtained by reacting by a known method using a tetracarboxylic acid derivative such as acid or tetracarboxylic acid dihalide.

  Examples of the method for imidizing the polyamic acid to form a polyimide include thermal imidization in which a polyamic acid solution is heated as it is, and catalytic imidization in which a catalyst is added to the polyamic acid solution. The imidation ratio from polyamic acid to polyimide is not necessarily 100%.

  The temperature at which the polyamic acid is thermally imidized in the solution is 100 ° C. to 400 ° C., preferably 120 ° C. to 250 ° C., and is preferably performed while removing water generated by the imidation reaction from the system.

  The catalytic imidation of the polyamic acid can be performed by adding a basic catalyst and an acid anhydride to the polyamic acid solution and stirring at -20 to 250 ° C, preferably 0 to 180 ° C. The amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times of the amidic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol of the amido acid group. Is double. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Among them, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated. The imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.

  The polyamic acid ester is a reaction of a tetracarboxylic acid diester dichloride with a diamine similar to the synthesis of the polyamic acid, a suitable condensing agent with a diamine similar to the synthesis of the tetracarboxylic acid diester and the polyamic acid, It can be produced by reacting in the presence of a base or the like. It can also be obtained by previously synthesizing a polyamic acid by the above method and esterifying the carboxylic acid in the amic acid using a polymer reaction. Specifically, for example, tetracarboxylic acid diester dichloride and diamine are -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C in the presence of a base and an organic solvent, for 30 minutes to 24 hours, preferably 1 hour. A polyamic acid ester can be synthesized by reacting for ˜4 hours. The polyimide can also be obtained by heating the polyamic acid ester at a high temperature to promote dealcoholization and ring closure.

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

<Liquid crystal aligning agent>
Although the agent of this invention contains the at least 1 specific polymer which has a radical generating structure in a side chain, 0.5-20 mass% is preferable, and, as for content of this specific polymer, More preferably, it is 0.5-15. It is 1 mass%, Most preferably, it is 1-10 mass%.

  Moreover, the liquid crystal aligning agent of this invention may contain other polymers other than the said polymer. In that case, 0.5-80 mass% is preferable, and, as for content of this other polymer in a polymer whole component, More preferably, it is 20-50 mass%.

  The molecular weight of the polymer of the liquid crystal aligning agent is determined by GPC (Gel Permeation Chromatography) in consideration of the strength of the liquid crystal aligning film obtained by applying the liquid crystal aligning agent, the workability at the time of forming the coating film, and the uniformity of the coating film. ) The weight average molecular weight measured by the method is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000.

  The solvent contained in the liquid crystal aligning agent is not particularly limited. The polymer having a structure represented by the above formula (I) in the side chain, and photopolymerization at two or more terminals contained as necessary. Or what is necessary is just to be able to melt | dissolve or disperse | distribute components, such as a polymeric compound which respectively has the group which carries out photocrosslinking. For example, the organic solvent which was illustrated by the synthesis | combination of said polyamic acid can be mentioned. Among them, N-methyl-2-pyrrolidone, γ-butyrolactone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and 3-methoxy-N, N-dimethylpropanamide are soluble. To preferred. Of course, two or more kinds of mixed solvents may be used.

  Moreover, it is preferable to mix and use the solvent which improves the uniformity and smoothness of a coating film in the solvent with the high solubility of the component of a liquid crystal aligning agent. Examples of such solvents include isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, Ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol Diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, Dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene , Amyl acetate , Butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n acetate -Butyl, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropion Acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propano Propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol , Lactate methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n-butyl ester, lactate isoamyl ester, 2-ethyl-1-hexanol and the like. A plurality of these solvents may be mixed. 5-80 mass% of the whole solvent contained in a liquid crystal aligning agent is preferable, and, as for these solvents, 20-60 mass% is more preferable.

  The liquid crystal aligning agent may contain components other than those described above. Examples thereof include compounds that improve the film thickness uniformity and surface smoothness when a liquid crystal aligning agent is applied, and compounds that improve the adhesion between the liquid crystal aligning film and the substrate.

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

  Specific examples of compounds that improve the adhesion between the liquid crystal alignment film and the substrate include functional silane-containing compounds and epoxy group-containing compounds. For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxy Carbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-to Ethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltri Methoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-amino Propyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether , Polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetra Glycidyl-2,4-hexanediol, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′ , N′-tetraglycidyl-4,4′-diaminodiphenylmethane, 3- (N-allyl-N-glycidyl) aminopropyltrimethoxysilane, 3- (N, N-diglycidyl) aminopropyltrimethoxysilane, and the like. .

  In order to further increase the film strength of the liquid crystal alignment film, a phenol compound such as 2,2'-bis (4-hydroxy-3,5-dihydroxymethylphenyl) propane or tetra (methoxymethyl) bisphenol may be added. 0.1-30 mass parts is preferable with respect to 100 mass parts of total amounts of the polymer contained in a liquid crystal aligning agent, and, as for these compounds, 1-20 mass parts is more preferable.

  In addition to the above, the liquid crystal aligning agent is added with a dielectric or conductive material for changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal aligning film, as long as the effects of the present invention are not impaired. May be.

  By applying and baking this liquid crystal aligning agent on a substrate, a liquid crystal alignment film for vertically aligning liquid crystals can be formed. By using the liquid crystal aligning agent of this invention, the response speed of the liquid crystal display element using the liquid crystal aligning film obtained can be made quick. In addition, the polymerizable compound that has two or more terminal groups that are photopolymerized or photocrosslinked, which may be contained in the liquid crystal aligning agent of the present invention, is not contained in the liquid crystal aligning agent, or the liquid crystal aligning agent. In addition, by incorporating it in the liquid crystal, the photoreaction becomes highly sensitive even in the so-called PSA mode, and a tilt angle can be imparted even with a small amount of ultraviolet irradiation.

  For example, after apply | coating the liquid crystal aligning agent of this invention to a board | substrate, after drying as needed, the cured film obtained by baking can also be used as a liquid crystal aligning film as it is. In addition, the cured film is rubbed, irradiated with polarized light or light of a specific wavelength, or treated with an ion beam, or a voltage is applied to the liquid crystal display element after filling the liquid crystal as a PSA alignment film It is also possible to irradiate with UV. In particular, it is useful to use as an alignment film for PSA.

  In this case, the substrate to be used is not particularly limited as long as it is a highly transparent substrate. Glass plate, polycarbonate, poly (meth) acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, polyetherketone , Plastic substrates such as trimethylpentene, polyolefin, polyethylene terephthalate, (meth) acrylonitrile, triacetyl cellulose, diacetyl cellulose, and acetate butyrate cellulose can be used. In addition, it is preferable to use a substrate on which an ITO electrode or the like for driving liquid crystal is formed from the viewpoint of simplifying the process. Further, in the reflection type liquid crystal display element, an opaque material such as a silicon wafer can be used as long as the substrate is only on one side, and in this case, a material that reflects light such as aluminum can be used.

  The application method of the liquid crystal aligning agent is not particularly limited, and examples thereof include screen printing, offset printing, flexographic printing, and other printing methods, ink jet methods, spray methods, roll coating methods, dip, roll coater, slit coater, spinner and the like. From the standpoint of productivity, the transfer printing method is widely used industrially, and is preferably used in the present invention.

  The coating film formed by applying the liquid crystal aligning agent by the above method can be baked to obtain a cured film. The drying process after applying the liquid crystal aligning agent is not necessarily required, but if the time from application to baking is not constant for each substrate, or if baking is not performed immediately after application, the drying process is performed. It is preferable. The drying is not particularly limited as long as the solvent is removed to such an extent that the shape of the coating film is not deformed by transporting the substrate or the like. For example, a method of drying on a hot plate at a temperature of 40 ° C. to 150 ° C., preferably 60 ° C. to 100 ° C., for 0.5 minutes to 30 minutes, preferably 1 minute to 5 minutes.

  The baking temperature of the coating film formed by applying a liquid crystal aligning agent is not limited, for example, 100-350 degreeC, Preferably it is 120-300 degreeC, More preferably, it is 150 degreeC-250 degreeC. The firing time is 5 minutes to 240 minutes, preferably 10 minutes to 90 minutes, and more preferably 20 minutes to 90 minutes. Heating can be performed by a generally known method such as a hot plate, a hot air circulating furnace, an infrared furnace, or the like.

  Moreover, the thickness of the liquid crystal alignment film obtained by baking is not particularly limited, but is preferably 5 to 300 nm, more preferably 20 to 200 nm.

<Method for manufacturing liquid crystal display element>
In the method for producing a liquid crystal display element of the present invention, first, a liquid crystal alignment film forming step for forming a liquid crystal alignment film as described above is performed on each of the surfaces of a pair of substrates.

  Next, a liquid crystal alignment film light irradiation step is performed in which at least one of the pair of substrates is irradiated with light so that the light irradiation amounts to the liquid crystal alignment films are different.

  In this liquid crystal alignment film light irradiation step, the liquid crystal alignment film of the substrate used on one side is irradiated with light to invalidate at least part of the radical generating ability of the radical generating structure of the liquid crystal alignment film on one side, or both Irradiation is performed so that the amount of light irradiation is different so that the radical generating ability on both sides is different.

  Specifically, in the liquid crystal alignment film light irradiation step, for example, the liquid crystal alignment film of the substrate used on one side is irradiated with light to invalidate at least a part of the radical generating structure, thereby invalidating the radical generating ability. Accordingly, one is a liquid crystal alignment film having no radical generation capability, the other is a liquid crystal alignment film having radical generation capability, or one is a liquid crystal alignment film having low radical generation capability and the other is a liquid crystal alignment film having high radical generation capability. , Make the radical generation ability on both sides different.

  Further, for example, the liquid crystal alignment films on the substrates on both sides are irradiated with light, but the amount of light irradiation is different on both sides, and the amount of radical generating structure to be invalidated is different on both sides. Thus, one is a liquid crystal alignment film having a low radical generation capability and the other is a liquid crystal alignment film having a high radical generation capability so that the radical generation capability on both sides is different.

Thus, the liquid crystal alignment film using the liquid crystal aligning agent of the same composition of the present invention has a predetermined liquid crystal alignment ability based on the functions of various side chains of the polymer described above. By performing a process with different generation capacities, the amount of radicals generated by the ultraviolet rays during the PSA process differs for each substrate.
Therefore, the reaction rate of the polymerizable compound is different at each substrate interface, and the liquid crystal alignment ability is also different.

  As the light irradiation for the treatment for deactivating the radical generating structure, a wavelength of about 250 nm to 600 nm can be used, and the wavelength is preferably adjusted appropriately for the radical generating structure.

For example, since the structure shown in the formula (I) often has absorption up to about 250 nm to 420 nm, it is preferable to irradiate ultraviolet rays of 250 nm to 420 nm in accordance with the absorption wavelength. Although it is necessary to match the desired light irradiation amount with a desired panel characteristic, it is preferable to change the light irradiation suitably because long-time light irradiation leads to an increase in tact time in the element manufacturing process. Generally, it is considered that the radical generating structure can be deactivated more efficiently by performing light irradiation in accordance with the maximum absorption wavelength of the radical generating structure. Influence of the tact time of the manufacturing line, when considering the damage to the other members, it is preferred that a suitable amount of light irradiation is ^{500mJ / cm 2 ~100J / cm 2} , more preferably ^1J / cm 2 ^~70J / cm ^2, more preferably is at ^1J / cm ^{2 ~40J} / cm 2

  Therefore, when a liquid crystal layer is formed between a pair of substrates having a liquid crystal alignment film having the same composition but having different liquid crystal alignment capabilities, the portion close to the surface of the liquid crystal layer is adjacent. Since the alignment state is formed based on the liquid crystal alignment ability of the liquid crystal alignment film, the alignment states on both surfaces are different. Specifically, when the side chain is vertically aligned, an asymmetric liquid crystal layer having different pretilt angles on both sides can be realized.

  In the manufacturing method of the liquid crystal display element of this invention, the liquid crystal layer formation process of forming the liquid crystal layer containing a liquid crystal compound between the pair of said board | substrate is included after that. Accordingly, since the liquid crystal layer is formed by being sandwiched between a pair of liquid crystal alignment films having different radical generation capabilities, it is possible to form an asymmetric liquid crystal layer having different pretilt angles on both sides.

<Liquid crystal display device substrate>
When a liquid crystal alignment film is formed using a liquid crystal aligning agent containing a specific polymer having a radical generating structure, the radical generating structure is used to generate radicals by light irradiation when forming the liquid crystal layer. Is normal.

  However, in the present invention, the liquid crystal alignment film of the substrate used on at least one side is irradiated with light to invalidate at least a part of the radical generating structure and invalidate the radical generating ability before being provided with the liquid crystal layer.

  A liquid crystal display element substrate before providing a liquid crystal layer as described above, in which a liquid crystal alignment film is formed using a liquid crystal alignment agent containing a specific polymer having a radical generating structure, and is irradiated with light. A substrate in which at least a part of the radical generating structure is invalidated is the substrate for a liquid crystal display element of the present invention.

<Liquid crystal display element assembly>
The liquid crystal display element assembly of the present invention uses the liquid crystal display element substrate of the present invention described above and a substrate in which a liquid crystal alignment film is formed using a liquid crystal aligning agent having the same composition, and a liquid crystal material that forms a liquid crystal layer therebetween. Is sandwiched between them. Moreover, it is a liquid crystal display element substrate according to the present invention, wherein a pair of substrates with different light irradiation amounts irradiated in advance is used, and a liquid crystal material to be a liquid crystal layer is sandwiched therebetween.

<Liquid crystal display element>
The liquid crystal display element manufactured by the method for manufacturing a liquid crystal display element of the present invention can produce a liquid crystal cell by a known method using the above-described substrate for a liquid crystal display element of the present invention, and thereby a pair of radical generating ability is different. Since the liquid crystal layer is formed between the liquid crystal alignment films, an asymmetric liquid crystal layer having different pretilt angles on both sides can be obtained.

  Specific examples of the liquid crystal display element include two substrates disposed so as to face each other, a liquid crystal layer provided between the substrates, and a liquid crystal aligning agent provided between the substrate and the liquid crystal layer. A vertical alignment type liquid crystal display device comprising a liquid crystal cell having the above-described liquid crystal alignment film. Specifically, the liquid crystal alignment agent of the present invention is applied to two substrates and baked to form a liquid crystal alignment film, and at least one of the radical generating structures is invalidated by irradiating light to at least one of them. Two substrates are arranged so that liquid crystal alignment films having different radical generating capabilities of the radical generating structure face each other, and a liquid crystal layer composed of liquid crystals is sandwiched between the two substrates, that is, the liquid crystal alignment film A liquid crystal layer is provided in contact with each other, and is produced by irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer. Thus, a vertical alignment type liquid crystal display device having asymmetric liquid crystal cells having different pretilt angles on both sides is obtained.

  The liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention is used to irradiate ultraviolet rays while applying voltage to the liquid crystal alignment film and the liquid crystal layer to polymerize the polymerizable compound, and the photoreactive property of the polymer. By reacting the side-chains or the photoreactive side chain of the polymer with the polymerizable compound, the alignment of the liquid crystal is more efficiently fixed, and the liquid crystal display device is remarkably excellent in response speed.

  The substrate used in the liquid crystal display element of the present invention is not particularly limited as long as it is a highly transparent substrate, but is usually a substrate on which a transparent electrode for driving liquid crystal is formed. As a specific example, the thing similar to the board | substrate described with the said liquid crystal aligning film can be mentioned. A substrate provided with a conventional electrode pattern or protrusion pattern may be used. However, in the liquid crystal display element of the present invention, since the liquid crystal aligning agent of the present invention is used, a line of 1 to 10 μm, for example, is formed on one side substrate. / Slit electrode pattern is formed, and it is possible to operate even in the structure where slit pattern or projection pattern is not formed on the counter substrate. The liquid crystal display element of this structure can simplify the process at the time of manufacture and has high transmittance. Can be obtained.

  As a high-performance element such as a TFT type element, an element in which an element such as a transistor is formed between an electrode for driving a liquid crystal and a substrate is used.

  In the case of a transmissive liquid crystal display element, it is common to use a substrate as described above. However, in a reflective liquid crystal display element, if only one substrate is used, an opaque substrate such as a silicon wafer may be used. Is possible. At that time, a material such as aluminum that reflects light may be used for the electrode formed on the substrate.

  The liquid crystal material constituting the liquid crystal layer of the liquid crystal display element of the present invention is not particularly limited, and a liquid crystal material used in a conventional vertical alignment method, for example, a negative type such as MLC-6608 or MLC-6609 manufactured by Merck Liquid crystal can be used. In the PSA mode, for example, a liquid crystal containing a polymerizable compound represented by the following formula can be used.

  In the present invention, a known method can be used as a method of sandwiching the liquid crystal layer between two substrates. For example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, and spacers such as beads are dispersed on the liquid crystal alignment film on one substrate so that the surface on which the liquid crystal alignment film is formed is on the inside. Then, the other substrate is bonded, and liquid crystal is injected under reduced pressure to seal. Also, a pair of substrates on which a liquid crystal alignment film is formed are prepared, and spacers such as beads are dispersed on the liquid crystal alignment film on one substrate, and then liquid crystal is dropped, and then the surface on which the liquid crystal alignment film is formed A liquid crystal cell can also be produced by a method in which the other substrate is bonded to each other so as to be inside, and sealing is performed. The thickness of the spacer is preferably 1 to 30 μm, more preferably 2 to 10 μm.

The step of producing a liquid crystal cell by irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer includes, for example, applying an electric field between the electrodes installed on the substrate to apply an electric field to the liquid crystal alignment film and the liquid crystal layer. And applying ultraviolet rays while maintaining this electric field. Here, the voltage applied between the electrodes is, for example, 5 to 30 Vp-p, preferably 5 to 20 Vp-p. The irradiation amount of ultraviolet rays is, for example, 1 to 60 J / cm ² , preferably 40 J / cm ² or less, and the smaller the ultraviolet irradiation amount, the lowering of reliability caused by the destruction of the members constituting the liquid crystal display element can be suppressed, In addition, the production efficiency is improved by reducing the ultraviolet irradiation time, which is preferable.

  As described above, when ultraviolet rays are irradiated while applying a voltage to the liquid crystal alignment film and the liquid crystal layer, the polymerizable compound reacts to form a polymer, and the direction in which the liquid crystal molecules are tilted is stored by this polymer. Thus, the response speed of the obtained liquid crystal display element can be increased. In addition, a polyimide precursor having a side chain for vertically aligning liquid crystal and a photoreactive side chain when irradiated with ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer, and the polyimide precursor as an imide Since the photoreactive side chains of at least one polymer selected from the polyimide obtained by the reaction or the photoreactive side chains of the polymer react with the polymerizable compound, the liquid crystal display element obtained The response speed can be increased.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to the examples.

<Synthesis of liquid crystal alignment agent>
The abbreviations used in the preparation of the following liquid crystal aligning agents are as follows.
(Acid dianhydride)
BODA: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride PMDA: pyromellitic dianhydride object

(Diamine)
DBA: 3,5-diaminobenzoic acid 3AMPDA: 3,5-diamino-N- (pyridin-3-ylmethyl) benzamide TCA: 2,3,5-tricarboxycyclopentylacetic acid dianhydride DSDA: 3,3 ′, 4 , 4'-Diphenylsulfonetetracarboxylic dianhydride

Diamine having a radical generating structure represented by the following formula DA-1 obtained in Synthesis Example

Vertically oriented diamines represented by the following formulas DA-2 to DA-3

Diamine compounds represented by the following formulas DA-4 to DA-7.

Vertically oriented diamine represented by the following formula DA-8.

<Solvent>
NMP: N-methyl-2-pyrrolidone BCS: Butyl cellosolve

<Additives>
3AMP: 3-picolylamine

Moreover, the molecular weight measurement conditions of polyimide are as follows.
Apparatus: Room temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Scientific Co., Ltd. Column: Columns manufactured by Shodex (KD-803, KD-805) Column temperature: 50 ° C. Eluent: N, N′-dimethyl Formamide (as additives, lithium bromide-hydrate (LiBr · H ₂ O) 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphoric acid) 30 mmol / L, tetrahydrofuran (THF) 10 ml / L) Flow rate: 1.0 ml / standard curve preparation standard sample: Tosoh TSK standard polyethylene oxide (molecular weight about 9,000,150,000, 100,000, 30,000) and polymer laboratory polyethylene glycol ( Molecular weight about 12,000, 4,000, 1,000).

Moreover, the imidation ratio of polyimide was measured as follows. Add 20 mg of polyimide powder to an NMR sample tube (NMR sampling tube standard φ5 manufactured by Kusano Kagaku Co., Ltd.), add 1.0 ml of deuterated dimethyl sulfoxide (DMSO-d ₆ , 0.05% TMS mixture), and apply ultrasonic waves. To dissolve completely. 500 MHz proton NMR was measured for this solution with the NMR measuring device by the JEOL datum company (JNW-ECA500). The imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of amic acid appearing near 9.5 to 10.0 ppm. It calculated | required by the following formula | equation using the integrated value. In the following formula, x is the proton peak integrated value derived from the NH group of the amic acid, y is the peak integrated value of the reference proton, and α is the proton of the NH group of the amic acid in the case of polyamic acid (imidation rate is 0%). This is the ratio of the number of reference protons to one.
Imidation ratio (%) = (1−α · x / y) × 100

(Synthesis Example 1)
BODA (3.75 g, 15.0 mmol), DA-1 (4.96 g, 15.0 mmol), DA-2 (5.71 g, 15.0 mmol) were dissolved in NMP (51.9 g), and 60 ° C. Then, CBDA (2.88 g, 14.7 mmol) and NMP (17.3 g) were added and reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution.

  After adding NMP to this polyamic acid solution (50 g) and diluting to 6.5% by mass, acetic anhydride (8.8 g) and pyridine (2.7 g) were added as imidation catalysts, and the mixture was added at 75 ° C. for 2.5 hours. Reacted. This reaction solution was poured into methanol (700 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (A). The imidation ratio of this polyimide was 71%, the number average molecular weight was 12000, and the weight average molecular weight was 49000.

  NMP (44.0 g) was added to the obtained polyimide powder (A) (6.0 g), and the mixture was dissolved by stirring at 70 ° C. for 20 hours. 3AMP (1 wt% NMP solution) 6.0g, NMP (4.0g), and BCS (40.0g) were added to this solution, and the liquid crystal aligning agent (A1) was obtained by stirring at room temperature for 5 hours.

(Synthesis Example 2)
BODA (3.75, 15.0 mmol), DA-3 (3.91 g, 9.0 mmol), DBA (0.91 g, 6.0 mmol), DA-1 (4.96 g, 15.0 mmol) were mixed with NMP ( 49.3 g), and after reacting at 60 ° C. for 5 hours, CBDA (2.88 g, 14.7 mmol) and NMP (16.4 g) were added and reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution. Obtained.

  After adding NMP to this polyamic acid solution (50 g) and diluting to 6.5% by mass, acetic anhydride (9.3 g) and pyridine (2.9 g) were added as an imidization catalyst and reacted at 70 ° C. for 3 hours. It was. This reaction solution was poured into methanol (700 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (B). The imidation ratio of this polyimide was 71%, the number average molecular weight was 13000 and the weight average molecular weight was 51000.

  NMP (44.0 g) was added to the obtained polyimide powder (B) (6.0 g), and the mixture was dissolved by stirring at 70 ° C. for 20 hours. 3AMP (1 wt% NMP solution) 6.0g, NMP (4.0g), and BCS (40.0g) were added to this solution, and the liquid crystal aligning agent (B1) was obtained by stirring at room temperature for 5 hours.

(Synthesis Example 3)
BODA (1.50 g, 6.0 mmol), DBA (1.83 g, 12.0 mmol), 3AMPDA (2.18 g, 9.0 mmol), DA-2 (3.43 g, 9.0 mmol) and NMP (41. 1 g), and after reacting at 60 ° C. for 3 hours, PMDA (1.31 g, 6.0 mmol) was added, followed by CBDA (3.47 g, 17.7 mmol) and NMP (13.71 g). The mixture was reacted at 25 ° C. for 10 hours to obtain a polyamic acid solution.

  After adding NMP to this polyamic acid solution (50 g) and diluting to 6.5% by mass, acetic anhydride (11.1 g) and pyridine (3.4 g) were added as an imidization catalyst and reacted at 60 ° C. for 3 hours. It was. This reaction solution was poured into methanol (700 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (C). The imidation ratio of this polyimide was 79%, the number average molecular weight was 11000, and the weight average molecular weight was 24000.

  NMP (44.0 g) was added to the obtained polyimide powder (C) (6.0 g) and dissolved by stirring at 70 ° C. for 20 hours. 3AMP (1 mass% NMP solution) 6.0g, NMP (4.0g), and BCS (40.0g) were added to this solution, and the liquid crystal aligning agent (C1) was obtained by stirring at room temperature for 5 hours.

(Synthesis Example 4)
3.0 g of the liquid crystal aligning agent (A1) obtained in Synthesis Example 1 was mixed as the first component, and 7.0 g of the liquid crystal aligning agent (C1) obtained in Synthesis Example 3 was mixed as the second component and stirred for 1 hour. By doing so, a liquid crystal aligning agent (A2) was prepared.

(Synthesis Example 5)
3.0 g of the liquid crystal aligning agent (B1) obtained in Example 1 was mixed as the first component, and 7.0 g of the liquid crystal aligning agent (C1) obtained in Synthesis Example 3 was mixed as the second component, and stirred for 1 hour. By doing so, a liquid crystal aligning agent (B2) was prepared.

(Synthesis Example 6) TCA
TCA (11.1 g, 50.0 mmol), DA-1 (6.61 g, 20.0 mmol), DA-4 (3.97 g, 20.0 mmol), DA-8 (4.95 g, 10.0 mmol). It melt | dissolved in NMP (106.5g), it was made to react at 60 degreeC for 6 hours, and the polyamic acid solution was obtained.

  After adding NMP to this polyamic acid solution (50 g) and diluting to 6.5% by mass, acetic anhydride (9.5 g) and pyridine (3.0 g) were added as an imidation catalyst and reacted at 100 ° C. for 3 hours. It was. This reaction solution was poured into methanol (700 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (D). The imidation ratio of this polyimide was 67%, the number average molecular weight was 13000 and the weight average molecular weight was 31000.

  NMP (44.0 g) was added to the obtained polyimide powder (D) (6.0 g), and the mixture was dissolved by stirring at 70 ° C. for 20 hours. NMP (10.0g) and BCS (40.0g) were added to this solution, and the liquid crystal aligning agent (D1) was obtained by stirring at room temperature for 5 hours.

(Synthesis Example 7) BEMS
BODA (5.00 g, 20.0 mmol), DA-1 (3.96 g, 12.0 mmol), DA-5 (2.11 g, 8.0 mmol), DA-2 (7.61 g, 20.0 mmol). After dissolving in NMP (67.6.g) and reacting at 60 ° C for 5 hours, CBDA (3.84g, 20.0mmol) and NMP (22.5g) were added and reacted at 40 ° C for 10 hours. A polyamic acid solution was obtained.

  After adding NMP to this polyamic acid solution (50 g) and diluting to 6.5% by mass, acetic anhydride (3.6 g) and pyridine (14.0 g) were added as imidization catalysts, and the mixture was reacted at 50 ° C. for 3 hours. It was. This reaction solution was poured into methanol (700 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (E). The imidation ratio of this polyimide was 51%, the number average molecular weight was 18000, and the weight average molecular weight was 53000.

  NMP (44.0 g) was added to the obtained polyimide powder (E) (6.0 g), and the mixture was dissolved by stirring at 50 ° C. for 10 hours. 3AMP (1 wt% NMP solution) 6.0g, NMP (4.0g), and BCS (40.0g) were added to this solution, and the liquid crystal aligning agent (E1) was obtained by stirring at room temperature for 5 hours.

(Synthesis Example 8) DSDA
BODA (5.00 g, 20.0 mmol), DBA (3.04 g, 20.0 mmol), DA-7 (4.93 g, 12.0 mmol), DA-2 (3.04 g, 8.0 mmol) were mixed with NMP ( 65.2 g), the mixture was reacted at 60 ° C. for 3 hours, CBDA (1.41 g, 7.0 mmol) was added, and the mixture was reacted at 40 ° C. for 1 hour. Then, DSDA (4.30 g, 12.0 mmol) and NMP (21.7 g) were added and reacted at 25 ° C. for 10 hours to obtain a polyamic acid solution.

  After adding NMP to this polyamic acid solution (50 g) and diluting to 6.5% by mass, acetic anhydride (9.3 g) and pyridine (2.9 g) were added as an imidization catalyst and reacted at 80 ° C. for 2 hours. It was. This reaction solution was poured into methanol (700 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (F). The imidation ratio of this polyimide was 76%, the number average molecular weight was 13000 and the weight average molecular weight was 34000.

  NMP (44.0 g) was added to the obtained polyimide powder (F) (6.0 g), and the mixture was dissolved by stirring at 70 ° C. for 20 hours. 3AMP (1 wt% NMP solution) 6.0g, NMP (4.0g), and BCS (40.0g) were added to this solution, and the liquid crystal aligning agent (F1) was obtained by stirring at room temperature for 5 hours.

(Synthesis Example 9) A199
BODA (2.50 g, 10.0 mmol), DA-6 (3.49 g, 14.0 mmol), DA-2 (2.28 g, 6.00 mmol) were mixed in NMP (40.2 g) at 50 ° C. Then, CBDA (1.76 g, 9.00 mmol) was added and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution.

(Synthesis Example 10)
The liquid crystal aligning agent (D1) obtained in Synthesis Example 6 is mixed with 5.0 g as the first component, and the liquid crystal aligning agent (F1) obtained in Synthesis Example 8 is mixed with 5.0 g as the second component and stirred for 1 hour. By doing so, a liquid crystal aligning agent (D2) was prepared.

(Synthesis Example 11)
The liquid crystal aligning agent (E1) obtained in Synthesis Example 7 is mixed with 5.0 g as the first component, and the liquid crystal aligning agent (G1) obtained in Synthesis Example 9 is mixed with 5.0 g as the second component and stirred for 1 hour. By doing so, a liquid crystal aligning agent (E2) was prepared.

  Table 1 shows the compositions of the liquid crystal alignment agents A1, B1, and C1. Table 2 shows the compositions of the liquid crystal alignment agents D1, E1, F1, and G1.

<Production of liquid crystal cell>
Example 1
Using the liquid crystal aligning agent (A2) obtained in Synthesis Example 4, a liquid crystal cell was prepared according to the procedure shown below. The liquid crystal aligning agent (A2) obtained in Synthesis Example 4 was spin-coated on the ITO surface of the ITO electrode substrate on which an ITO electrode pattern having a pixel size of 100 μm × 300 μm and a line / space of 5 μm was formed, After drying for 90 seconds on the hot plate, baking was performed for 30 minutes in a hot air circulation oven at 230 ° C. to form a liquid crystal alignment film (A2-1) having a film thickness of 100 nm.

  Moreover, after spin-coating the liquid crystal aligning agent (A2) on the ITO surface where the electrode pattern is not formed and drying for 90 seconds on a hot plate at 80 ° C., baking is performed for 30 minutes in a hot air circulation oven at 230 ° C., A liquid crystal alignment film (A2-2) having a thickness of 100 nm was formed.

Subsequently, each of the liquid crystal alignment films (A2-1, A2-2) was irradiated with 10 J / cm ² of UV of a high-pressure mercury lamp with a wavelength of 325 nm or less cut to deactivate the radical generating structure present in the alignment film. (Pre-UV). For the measurement of the irradiation amount, a UV-35 light receiver was connected to UV-M03A manufactured by ORC.

  After spraying a 4 μm bead spacer on the liquid crystal alignment film of one of the two substrates, a sealant (a thermosetting sealant XN-1500T manufactured by Mitsui Chemicals) was printed thereon. Next, the surface of the other substrate on which the liquid crystal alignment film was formed was faced inward and bonded to the previous substrate, and then the sealing agent was cured to produce an empty cell. A negative liquid crystal MLC-3023 (trade name, manufactured by Merck & Co., Inc.) containing a polymerizable compound for PSA was injected into this empty cell by a reduced pressure injection method to produce a liquid crystal cell.

With a DC voltage of 15 V applied to the liquid crystal cell, UV of a high pressure mercury lamp passed through a 365 nm band pass filter was irradiated from the outside of the liquid crystal cell at 10 J / cm ² (1st-UV). Thereafter, irradiation with a fluorescent UV lamp (FLR40SUV32 / A-1) for 30 minutes without applying a voltage to the liquid crystal cell (2nd-UV) to deactivate unreacted polymerizable compounds present in the liquid crystal cell. It was.

  Thereafter, the pretilt angle and response speed of the pixel portion of the liquid crystal cell were measured (a liquid crystal cell symmetric with the pretilt angle). The results are shown in Table 2.

"Measurement of pretilt angle"
An LCD analyzer LCA-LUV42A manufactured by Meiryo Technica was used.

"Response speed measurement method"
First, a liquid crystal cell was arranged between a pair of polarizing plates in a measuring device configured in the order of a backlight, a set of polarizing plates in a crossed Nicol state, and a light amount detector. At this time, the ITO electrode pattern in which the line / space was formed was at an angle of 45 ° with respect to the crossed Nicols. Then, a rectangular wave having a voltage of ± 7 V and a frequency of 1 kHz is applied to the liquid crystal cell, and the change until the luminance observed by the light amount detector is saturated is captured by an oscilloscope, and the luminance when no voltage is applied is obtained. A voltage of 0% and ± 7 V was applied, the value of saturated luminance was taken as 100%, and the time taken for the luminance to change from 10% to 90% was taken as the response speed.

  Further, a liquid crystal cell having an asymmetric pretilt angle was prepared in the same procedure as described above except that the liquid crystal alignment film (A2-1) was not irradiated with Pre-UV, and the response speed was measured. The results are shown in Table 3.

(Examples 2-3)
Except that irradiation with 20~40J / cm ² instead of Example 1 10J / cm ² was irradiated as Pre-UV at working in the same manner as in Example 1, to prepare a liquid crystal cell, the pretilt angle of the liquid crystal cell Was measured.

Example 4
The same operation as in Example 1 was performed except that 1 J / cm ² of UV of a high-pressure mercury lamp passed through a band-pass filter with a wavelength of 313 nm was irradiated instead of 10 J / cm ² irradiated as Pre-UV in Example 1. A liquid crystal cell was prepared, and the pretilt angle of the liquid crystal cell was measured.

(Examples 5 to 8)
A liquid crystal cell was prepared in the same manner as in Examples 1 to 4 except that the alignment agent used was changed from the liquid crystal alignment agent (A2) to the liquid crystal alignment agent (B2), and the pretilt angle of the liquid crystal cell was measured. Went.
An alignment film (B2-1) applied on the ITO surface of the ITO electrode substrate on which an ITO electrode pattern having a pixel size of 100 μm × 300 μm and a line / space of 5 μm is formed is formed on the ITO film on which the electrode pattern is not formed. The alignment film applied to the surface was designated as (B2-2).

(Comparative Example 1)
A liquid crystal cell was prepared in the same manner as in Example 1 except that Pre-UV was not irradiated in Example 1, and the pretilt angle of the liquid crystal cell was measured.

(Comparative Example 2)
A liquid crystal cell was produced in the same manner as in Example 5 except that Pre-UV was not irradiated in Example 5, and the pretilt angle of the liquid crystal cell was measured.

(Examples 9 to 12)
Except having changed into the liquid crystal aligning agent (D2) from the liquid crystal aligning agent (A2), operation similar to Examples 1-4 was performed, the liquid crystal cell was produced, and the pretilt angle of the liquid crystal cell was measured.
An alignment film applied on the ITO surface of an ITO electrode substrate on which an ITO electrode pattern having a pixel size of 100 μm × 300 μm and a line / space of 5 μm is formed (D2-1), ITO without an electrode pattern The alignment film applied to the surface was designated as (D2-2).

(Examples 13 to 16)
Except having changed into the liquid crystal aligning agent (E2) from the liquid crystal aligning agent (A2), operation similar to Example 1-4 was performed, the liquid crystal cell was produced, and the pretilt angle of the liquid crystal cell was measured.
An alignment film (E2-1) applied on the ITO surface of an ITO electrode substrate on which an ITO electrode pattern having a pixel size of 100 μm × 300 μm and a line / space of 5 μm is formed is formed on the ITO without an electrode pattern. The alignment film applied to the surface was designated as (E2-2).

(Comparative Example 3)
A liquid crystal cell was produced in the same manner as in Example 9 except that Pre-UV was not irradiated in Example 9, and the pretilt angle of the liquid crystal cell was measured.

(Comparative Example 4)
A liquid crystal cell was prepared in the same manner as in Example 13 except that Pre-UV was not irradiated in Example 13, and the pretilt angle of the liquid crystal cell was measured.

  First, from the results shown in Tables 3 and 5, the substrate is irradiated with Pre-UV to deactivate the radical generating structure in the alignment film, and the pretilt angle is less likely to be exhibited during PSA treatment (1st-UV), and the response speed. It was confirmed that it would be too late. On the other hand, in the comparative example, since Pre-UV irradiation is not performed, a radical generating structure remains in the alignment film, and a sufficient pretilt can be obtained even when a wavelength of 365 nm with relatively weak energy is used during PSA treatment (1st-UV). It can be seen that the angle and response speed can be obtained.

  Next, from the results of Tables 4 and 6, it was found that a sufficient response speed can be obtained when only one substrate is irradiated with Pre-UV. The pretilt angle on the side irradiated with Pre-UV (the side on which the ITO electrode pattern is not formed in this embodiment) should be the pretilt angle described in the examples of Table 3 and Table 5, but Pre-UV It is considered that the pretilt angle described in the comparative examples in Table 3 and Table 5 is the non-irradiated side (ITO electrode pattern side in this example).

  In this way, by irradiating only one substrate with Pre-UV, a liquid crystal display element having an asymmetric pretilt angle can be obtained using one type of liquid crystal aligning agent without impairing the response speed required for the liquid crystal display element. It becomes possible to create.

Claims (16)

A liquid crystal alignment film forming step of forming a liquid crystal alignment film with a liquid crystal aligning agent of the same composition containing a specific polymer having a radical generating structure that generates radicals by light irradiation on each of the surfaces of the pair of substrates; A liquid crystal alignment film light irradiation step in which at least one of the substrates is irradiated with light to change the amount of light irradiation to the liquid crystal alignment films in different states, and then a liquid crystal layer containing a liquid crystal compound is interposed between the pair of substrates. And a liquid crystal layer forming step of forming a liquid crystal display element. 2. The liquid crystal display element according to claim 1, wherein the liquid crystal layer is a PSA type liquid crystal layer, and in the liquid crystal layer forming step, radicals are generated from the radical generating structure by light irradiation while applying a voltage. Production method. 3. The liquid crystal alignment film light irradiating step performs light irradiation only on the liquid crystal alignment film on one substrate and does not perform light irradiation on the liquid crystal alignment film on the other substrate. A method for manufacturing a liquid crystal display element. The said specific polymer contains the polymer which has a side chain structure represented by following formula (I), The manufacturing method of the liquid crystal display element of any one of Claims 1-3 characterized by the above-mentioned.

(Ar represents an aromatic hydrocarbon group selected from phenylene, naphthylene, and biphenylene, in which an organic group may be substituted, and a hydrogen atom may be substituted with a halogen atom. R ₁ , R ₂ is each independently an alkyl group or alkoxy group having 1 to 10 carbon atoms, and T ₁ and T ₂ are each independently a single bond or —O—, —COO—, —OCO—, —NHCO—. , —CONH—, —NH—, —CH ₂ O—, —N (CH ₃ ) —, —CON (CH ₃ ) —, —N (CH ₃ ) CO—, and S is a single bond or An alkylene group having 1 to 20 carbon atoms which is unsubstituted or substituted by a fluorine atom, where —CH ₂ — or —CF ₂ — in the alkylene group may be optionally replaced by —CH═CH— Any of In the case where groups are not adjacent to each other, these groups may be substituted; —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, a divalent carbocycle, (It is a divalent heterocyclic ring, and Q represents a structure selected from the following.)

R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The specific polymer having a side chain structure represented by the formula (I) is selected from the group consisting of a polyimide precursor having a side chain structure represented by the formula (I) and a polyimide obtained by imidizing it. The method for producing a liquid crystal display element according to claim 4, wherein the liquid crystal display element is at least one polymer. The said specific polymer contains the polymer which has a side chain structure represented by following formula (II), The manufacturing method of the liquid crystal display element of any one of Claims 1-3 characterized by the above-mentioned.

(In the formula (II), the point means a bond to the main chain of the polymer, n is an integer selected from 1 to 12, X is a single bond, -O-, -COO-, -OCO-, _{-NHCO -, - CONH -, -} NH -, - CH 2 O -, - N (CH 3) -, - CON (CH 3) -, or -N _(CH 3) .Cy imido group represented by CO- Represents a cyclic hydrocarbon group having 5 to 14 carbon atoms and having at least one unsaturated bond which is necessarily bonded to the carbonyl carbon of the carbon atom, and a part of the carbon atoms constituting the cyclic hydrocarbon is replaced by a hetero atom. May be.) 7. The liquid crystal according to claim 6, wherein n in the formula (II) is an integer of 1 to 6, Cy is a cyclic hydrocarbon group shown below, and two points each represent a bond to imide carbonyl carbon. A method for manufacturing a display element.

The liquid crystal display element according to claim 6 or 7, wherein n in the formula (II) is an integer of 1 to 6, X represents -O-, and Cy is cyclohexene, benzene, naphthalene, or biphenylene. Production method. The manufacturing method of the liquid crystal display element of any one of Claims 4-8 in which the said specific polymer further has a side chain which orientates a liquid crystal vertically. The method for producing a liquid crystal display element according to claim 9, wherein the side chain for vertically aligning the liquid crystal is at least one selected from the following formulas (III-1) and (III-2).

^{(X 1} is a single _{bond, - (CH 2) a -} (a is an integer of _{1~15), - O -, -} CH 2 O -, - COO- or -OCO- .X ² representing a is , A single bond or (CH ₂ ) _b — (b is an integer of 1 to 15), X ³ is a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), Represents —O—, —CH ₂ O—, —COO— or —OCO—, wherein X ⁴ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring; The hydrogen atom is substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. at best, further, ^{X 4} is selected from an organic group having 17 to 51 carbon atoms having a steroid skeleton That divalent good .X ⁵ be an organic radical is a divalent cyclic group selected from benzene ring, cyclohexane ring and heterocyclic, any of hydrogen atoms on these cyclic groups, 1 to carbon atoms 3 may be substituted with an alkyl group having 1 to 3, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. Represents an integer of 4. X ⁶ represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. To express.)

(X ⁷ is a single bond, —O—, —CH ₂ O—, —CONH—, —NHCO—, —CON (CH ₃ ) —, —N (CH ₃ ) CO—, —COO— or —OCO—. X ⁸ represents an alkyl group having 8 to 22 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms.) The said specific polymer contains at least 1 polymer of the polyimide precursor which has the diamine component represented by following formula (1) as a structural unit, and the polyimide obtained by imidating it. The manufacturing method of the liquid crystal display element of any one.

(The definitions of symbols in the formula are the same as those in the formula (I).) The specific polymer further contains at least one polymer of a polyimide precursor having a diamine component containing a diamine represented by the following formula (VII) as a constituent unit and a polyimide obtained by imidizing the polyimide precursor. Item 12. A method for producing a liquid crystal display element according to Item 11.

(X shows the structure of the said Formula [III-1] or Formula [III-2], and n shows the integer of 1-4.) The specific polymer is a polyimide precursor having a diamine component containing a diamine represented by the following formula (VIII) or (IX) as a constituent unit, and at least one polymer obtained by imidizing it. The liquid crystal aligning agent of Claim 11 or 12 containing.

(R ⁸ is a single bond, —CH ₂ —, —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —CH ₂ O—, —N (CH ₃ ) —. , -CON (CH ₃ )-, or -N (CH ₃ ) CO-, wherein R ⁹ represents a single bond, an alkylene group having 1 to 20 carbon atoms which may be substituted with a fluorine atom, and an alkylene group —CH ₂ — may be optionally substituted with —CF ₂ — or —CH═CH—, and may be substituted with these groups when any of the following groups are not adjacent to each other; -O -, - COO -, - OCO -, - NHCO -, - CONH -, - NH-, a divalent carbocyclic or heterocyclic ^{.R 10} of represents a photoreactive group selected from the following formulas. )

(Y ₁ represents —CH ₂ —, —O—, —CONH—, —NHCO—, —COO—, —OCO—, —NH—, or —CO—. Y ₂ has 1 to 30 carbon atoms. An alkylene group, a divalent carbocycle or a heterocycle, and one or more hydrogen atoms of the alkylene group, divalent carbocycle or heterocycle may be substituted with a fluorine atom or an organic group. ₂ represents that, when the following groups are not adjacent to each other, —CH ₂ — may be substituted with these groups; —O—, —NHCO—, —CONH—, —COO—, —OCO—, — NH—, —NHCONH—, —CO—, Y ₃ represents —CH ₂ —, —O—, —CONH—, —NHCO—, —COO—, —OCO—, —NH—, —CO—, or .Y ₄ representing the bond represents a cinnamoyl group .Y ₅ is a single bond, 1 to 3 carbon atoms An alkylene group, a divalent carbocycle or a heterocycle, and one or more hydrogen atoms of the alkylene group, divalent carbocycle or heterocycle may be substituted with a fluorine atom or an organic group. Y ₅ represents that when the following groups are not adjacent to each other, —CH ₂ — may be substituted with these groups; —O—, —NHCO—, —CONH—, —COO—, —OCO—, -NH -, - NHCONH -, - CO-.Y 6 shows the photopolymerizable group is an acrylic group or methacrylic group). The said polymer contains the following (A) component and the following (B) component, The manufacturing method of the liquid crystal display element of any one of Claims 1-3 characterized by the above-mentioned.
Component (A): a polyimide precursor having a side chain for vertically aligning liquid crystals and a side chain having a site that generates radicals by ultraviolet irradiation represented by the following formula (1), and this polyimide precursor: At least one polymer selected from polyimides obtained by imidization; and

(Ar represents an aromatic hydrocarbon group selected from phenylene, naphthylene, and biphenylene, in which an organic group may be substituted, and a hydrogen atom may be substituted with a halogen atom. R ₁ , R ₂ is each independently an alkyl group or alkoxy group having 1 to 10 carbon atoms, and T ₁ and T ₂ are each independently a single bond or —O—, —COO—, —OCO—, —NHCO—. , —CONH—, —NH—, —CH ₂ O—, —N (CH ₃ ) —, —CON (CH ₃ ) —, —N (CH ₃ ) CO—, and S is a single bond or An alkylene group having 1 to 20 carbon atoms which is unsubstituted or substituted by a fluorine atom, where —CH ₂ — or —CF ₂ — in the alkylene group may be optionally replaced by —CH═CH— Any of In the case where groups are not adjacent to each other, these groups may be substituted; —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, a divalent carbocycle, (It is a divalent heterocyclic ring, and Q represents a structure selected from the following.)

(R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)
(B) component: a polyimide precursor obtained by using a diamine component containing at least one diamine selected from the following formulas (B-1) to (B-5) as a raw material, and imidating the polyimide precursor A polyimide selected from a polymer selected from polyimides obtained or a tetracarboxylic dianhydride component containing at least one tetracarboxylic dianhydride selected from the following formulas (3) and (4) A polymer selected from a precursor and a polyimide obtained by imidizing the polyimide precursor.

(Y ₁ is a monovalent organic group having a secondary amine, tertiary amine or heterocyclic structure, and Y ₂ is a divalent organic group having a secondary amine, tertiary amine or heterocyclic structure.)

(N and m are 0 or 1, and X and y are a single bond, carbonyl, ester, phenylene or sulfonyl group.)   A substrate for forming a liquid crystal display element comprising a liquid crystal alignment film, wherein the liquid crystal alignment film is formed of a liquid crystal alignment agent containing a polymer having a radical generating structure that generates radicals upon light irradiation, A substrate for forming a liquid crystal display element, wherein radicals are generated from at least a part of the radical generating structure by light irradiation.   A liquid crystal display element assembly comprising a liquid crystal display element forming substrate having a pair of liquid crystal alignment films and a liquid crystal layer provided between the pair of liquid crystal display element substrates, wherein the pair of liquid crystal displays The liquid crystal alignment film of the device formation substrate is formed of a liquid crystal aligning agent having the same composition containing a polymer having a radical generating structure that generates radicals by light irradiation, and at least one is irradiated with light. Thus, the liquid crystal display element assembly is characterized in that the light irradiation amounts of the two are different.