WO2015115588A1

WO2015115588A1 - Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element

Info

Publication number: WO2015115588A1
Application number: PCT/JP2015/052638
Authority: WO
Inventors: 章吾檜森; ダニエルアントニオ櫻葉汀; 司藤枝; 耕平後藤; 亮一芦澤; 真文高橋
Original assignee: 日産化学工業株式会社
Priority date: 2014-01-30
Filing date: 2015-01-30
Publication date: 2015-08-06
Also published as: JPWO2015115588A1; TW201541163A; TWI657297B; CN106164760A; KR102357093B1; CN106164760B; KR20160114645A

Abstract

Provided is a liquid crystal aligning agent which contains a polymerizable compound having improved solubility in a liquid crystal aligning agent as well as improved solubility in a liquid crystal, and which has improved storage stability. The present invention discloses a liquid crystal aligning agent which contains: [I] at least one polymerizable compound that is selected from the group consisting of compounds represented by general formulae (I-1)-(I-3) (wherein each of Ar₁-Ar₃ independently represents a divalent organic group containing an aromatic ring having at least one halogen-substituted group; each of n₁, n₂ and n₆ independently represents an integer of 0-6; each of n₃, n₄ and n₅ independently represents an integer of 1-6; and each of R₁-R₃ independently represents a hydrogen atom or a linear or branched alkyl group having 1-4 carbon atoms); and [II] at least one polymer that is selected from among polyimide precursors and polyimides.

Description

Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element

The present invention relates to a liquid crystal aligning agent that can be used for the production of a liquid crystal display device produced by irradiating ultraviolet rays with voltage applied to liquid crystal molecules, a liquid crystal aligning film formed with the liquid crystal aligning agent, The present invention relates to a liquid crystal display element having a liquid crystal alignment film.

In a liquid crystal display element of a method in which liquid crystal molecules aligned perpendicular to a substrate are responded by an electric field (also referred to as a vertical alignment (VA) method), an ultraviolet ray is applied while applying a voltage to the liquid crystal molecules in the manufacturing process. There is a thing including the process of irradiating.
In such a vertical alignment type liquid crystal display element, a photopolymerizable compound is added to a liquid crystal composition in advance and used together with a vertical alignment film such as polyimide to irradiate ultraviolet rays while applying a voltage to a liquid crystal cell. A technique for increasing the response speed of liquid crystal (for example, see Patent Document 1 and Non-Patent Document 1) is known (PSA (Polymer sustained Alignment) type liquid crystal display).

Usually, the direction in which the liquid crystal molecules tilt in response to an electric field is controlled by protrusions provided on the substrate or slits provided on the display electrode, but a liquid crystal composition is added with a photopolymerizable compound. By irradiating ultraviolet rays while applying voltage to the 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 control method.
It has also been reported that the response speed of the liquid crystal display element is increased by adding a photopolymerizable compound to the liquid crystal alignment film instead of the liquid crystal composition (SC-PVA liquid crystal display) (for example, Non-patent document 2).

Japanese Patent Laid-Open No. 2003-307720.

However, it is desired to further increase the response speed of the liquid crystal display element. Here, it is conceivable to increase the response speed of the liquid crystal display element by increasing the amount of the photopolymerizable compound added, but the conventional photopolymerizable compound is dissolved in the solvent or liquid crystal used in the liquid crystal aligning agent. It has the property of being difficult. Therefore, when storing the liquid crystal aligning agent, there arises a storage stability problem that the photopolymerizable compound is precipitated. In addition, when the liquid crystal display element is exposed to a temperature change during the manufacturing process, a part of the polymerizable compound may be eluted from the liquid crystal alignment film into the liquid crystal or further crystallized in the liquid crystal. . In particular, when the solubility of the polymerizable compound in the liquid crystal is low, crystallization in the liquid crystal is likely to occur. Such crystallization of the polymerizable compound in the liquid crystal serves as a bright spot source in the display element, leading to deterioration in display quality of the element. Furthermore, if an undissolved photopolymerizable compound remains, it becomes an impurity, which may cause a decrease in the reliability of the liquid crystal display element. For example, image sticking or an afterimage may occur in the liquid crystal display element, which may reduce display quality.

An object of the present invention is to solve the problems of the prior art described above.
Specifically, an object of the present invention is a liquid crystal alignment agent containing a polymerizable compound having improved solubility in a liquid crystal alignment agent and solubility in a liquid crystal, and having improved storage stability. It is to provide an agent.
Another object of the present invention is to provide a liquid crystal alignment film formed with the liquid crystal alignment agent and a liquid crystal display element having the liquid crystal alignment film.

The inventors have found the following invention.
<1> [I] The following general formulas I-1 to I-3
(Wherein Ar ₁ to Ar ₃ are each independently a divalent organic group containing an aromatic ring having at least one halogen substituent, and n ₁ , n ₂ and n ₆ are each independently N represents an integer of 0 to 6, n ₃ , n ₄ and n ₅ each independently represents an integer of 1 to 6, and R ₁ to R ₃ each independently represent hydrogen or a straight chain of 1 to 4 carbon atoms or Indicates a branched alkyl group)
At least one polymerizable compound selected from the group consisting of compounds represented by: and [II] at least one polymer selected from polyimide precursors and polyimides;
Liquid crystal aligning agent containing.

<2> In the above <1>, Ar ₁ to Ar ₃ are each independently represented by the following formulas IB-1 to IB-3 (wherein X represents a halogen group, and m ₁ to m ₈ are each independently an integer) M ₁ + m ₂ is 1 or more and 8 or less, m ₃ + m ₄ + m ₅ is 1 or more and 10 or less, and m ₆ + m ₇ + m ₈ is 1 or more and 12 or less. It is good that it is an organic group.

<3> In the above <2>, the group represented by the formula IB-1 is preferably represented by the following formula IB-1a, and the group represented by the formula IB-2 is represented by the following formula IB-2a The group represented by the formula IB-3 is preferably represented by the following formula IB-3a.

<4> In any one of the above items <1> to <3>, the [II] polymer may have (I) a side chain that vertically aligns the liquid crystal.
<5> In the above <4>, the [II] polymer may further include (II) a photoreactive side chain.
<6> A liquid crystal alignment film formed by including the liquid crystal aligning agent according to any one of the above items <1> to <5>.
<7> A liquid crystal display device having the liquid crystal alignment film of <6> above.

According to the present invention, it is possible to provide a liquid crystal aligning agent containing a polymerizable compound having improved solubility in a liquid crystal aligning agent and solubility in a liquid crystal, and having improved storage stability. .
In addition, according to the present invention, it is possible to provide a liquid crystal alignment film formed with the liquid crystal alignment agent and a liquid crystal display element having the liquid crystal alignment film.

Hereinafter, the invention described in the present application will be described in detail.
This application provides the liquid crystal aligning agent containing the polymeric compound which improved the solubility to a liquid crystal aligning agent, and the solubility to a liquid crystal.
The present application also provides a liquid crystal alignment film formed with the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film.
Hereinafter, a liquid crystal alignment agent, a liquid crystal alignment film formed using the liquid crystal alignment agent, and a liquid crystal display element including the liquid crystal alignment film will be described in this order.

<Liquid crystal aligning agent>
This application provides the liquid crystal aligning agent containing the polymeric compound which improved the solubility to a liquid crystal aligning agent, and the solubility to a liquid crystal.
The liquid crystal aligning agent of the present application is selected from [I] at least one polymerizable compound selected from the group consisting of compounds represented by the following general formulas I-1 to I-3; and [II] a polyimide precursor and a polyimide. At least one polymer.
In the general formulas I-1 to I-3, Ar ₁ to Ar ₃ are each independently a divalent organic group containing an aromatic ring having at least one halogen substituent, and n ₁ , n ₂ and n ₆ each independently represents an integer of 0 to 6, n ₃ , n ₄ and n ₅ each independently represents an integer of 1 to 6; R ₁ to R ₃ each independently represents hydrogen or carbon number 1 to 4 linear or branched alkyl groups are shown.

<< [I] polymerizable compound >>
The liquid crystal aligning agent of the present application contains [I] at least one polymerizable compound selected from the group consisting of the compounds represented by the general formulas I-1 to I-3.
Ar ₁ to Ar _{3 in the} general formulas I-1 to I-3 are each independently represented by the following formulas IB-1 to IB-3 (wherein X represents a halogen group, and m ₁ to m ₈ are each independently an integer) M ₁ + m ₂ is 1 or more and 8 or less, preferably 1 or more and 4 or less, m ₃ + m ₄ + m ₅ is 1 or more and 10 or less, preferably 1 or more and 6 or less, and m ₄ + m ₅ is 2 or less, and m ₆ + m ₇ + m ₈ is 1 or more and 12 or less, preferably 1 or more and 4 or less.
In the liquid crystal aligning agent of this application, 1 type of polymeric compounds may be sufficient even if it is multiple types as needed.
The amount of the polymerizable compound is preferably 1 to 30% by mass, preferably 3 to 20% by mass, and more preferably 5 to 15% by mass with respect to the solid content in the liquid crystal aligning agent.

Specific examples of the divalent group represented by the formulas IB-1 to IB-3 include, but are not limited to, groups represented by the following formulae.

The divalent groups represented by the formulas IB-1 to IB-3 are preferably the following groups. That is, the group represented by the formula IB-1 is preferably a group represented by the following formula IB-1a, and the group represented by the formula IB-2 is a group represented by the following formula IB-2a. And the group represented by the formula IB-3 is preferably a group represented by the following formula IB-3a.

<[II] At least one polymer selected from polyimide precursor and polyimide>
[II] As the at least one polymer selected from the polyimide precursor and the polyimide, a conventionally known or future known polyimide precursor or polyimide used for a liquid crystal aligning agent can be used. Note that the polyimide precursor specifically includes polyamic acid and polyamic acid ester.

[II] The polyimide precursor or polyimide may have (I) a side chain for vertically aligning liquid crystal for use in a PSA type liquid crystal display.
<< (I) Side chain for vertically aligning liquid crystal >>
(I) A side chain that aligns liquid crystal vertically (hereinafter also referred to as side chain A) is a side chain that has the ability to align liquid crystal molecules vertically with respect to the substrate. Its structure is not limited. As such a side chain, for example, a long-chain alkyl group or a fluoroalkyl group, a cyclic group having an alkyl group or a fluoroalkyl group at the terminal, a steroid group, or the like is known, and is preferably used in the present invention. . As long as these groups have the above-mentioned ability, they may be directly bonded to the polyimide precursor or the main chain of the polyimide, or may be bonded via an appropriate bonding group.

Examples of the side chain A include those represented by the following formula (a).
In the formula (a), l, m and n each independently represents an integer of 0 or 1, and R ¹ represents an alkylene group having 2 to 6 carbon atoms, —O—, —COO—, —OCO—, —NHCO—, —CONH—, or an alkylene-ether group having 1 to 3 carbon atoms, R ² , R ³ and R ⁴ each independently represents a phenylene group or a cycloalkylene group, R ⁵ represents a hydrogen atom, It represents an alkyl group having 2 to 24 carbon atoms or a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, or a macrocyclic substituent composed thereof.

R ¹ in the formula (a) is an alkylene group having 2 to 6 carbon atoms, —O—, —COO—, —OCO—, —NHCO—, —CONH—, or an alkylene ether having 1 to 3 carbon atoms. Represents a group. Among these, from the viewpoint of ease of synthesis, —O—, —COO—, —CONH—, and an alkylene-ether group having 1 to 3 carbon atoms are preferable.

R ² , R ³ and R ⁴ in the formula (a) each independently represent a phenylene group or a cycloalkylene group. From the viewpoint of ease of synthesis and ability to align liquid crystals vertically, combinations of l, m, n, R ² , R ³ and R ⁴ shown in the following table are preferred.

R ⁵ in the formula (a) represents a hydrogen atom, an alkyl group having 2 to 24 carbon atoms or a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, or a macrocyclic substituent composed thereof. When at least one of l, m and n is 1, the structure of R ⁵ is preferably a hydrogen atom, an alkyl group having 2 to 14 carbon atoms or a fluorine-containing alkyl group, more preferably a hydrogen atom or carbon atom number. 2 to 12 alkyl groups or fluorine-containing alkyl groups.
When l, m, and n are all 0, the structure of R ⁵ is preferably an alkyl group having 12 to 22 carbon atoms, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, or the like. A macrocyclic substituent, more preferably an alkyl group having 12 to 20 carbon atoms or a fluorine-containing alkyl group.

The ability to align the liquid crystal vertically depends on the structure of the side chain A described above, but generally, as the amount of the side chain A contained in the polymer increases, the ability to align the liquid crystal vertically increases and decreases. Go down. Further, the side chain A containing a cyclic structure tends to align the liquid crystal vertically even with a small content as compared with the side chain A of the long-chain alkyl group.

The abundance of the side chain A in the polyimide precursor or polyimide used in the present invention is not particularly limited as long as the liquid crystal alignment film can vertically align the liquid crystal. However, in the liquid crystal display device having the liquid crystal alignment film, when it is desired to increase the response speed of the liquid crystal, the amount of the side chain A is preferably as small as possible within the range in which the vertical alignment can be maintained. .

[II] The polyimide precursor or polyimide has (II) a photoreactive side chain in addition to (I) the side chain for vertically aligning the liquid crystal for SC-PVA type liquid crystal display. Is good.

<(II) Photoreactive side chain>
A photoreactive side chain (hereinafter also referred to as side chain B) is a crosslinkable side chain having a functional group (hereinafter also referred to as photocrosslinking group) that can react by irradiation with ultraviolet rays to form a covalent bond, or A photoradical generating side chain having a functional group capable of generating radicals upon irradiation with ultraviolet rays, and its structure is not limited as long as it has this ability.
Among such side chains, for example, a side chain containing a vinyl group, an acrylic group, a methacryl group, an anthracenyl group, a cinnamoyl group, a chalcone group, a coumarin group, a maleimide group, a stilbene group or the like as a photocrosslinking group is known. And is also preferably used in the present invention. In addition, a specific structure that generates radicals by ultraviolet irradiation is also preferably used. As long as these groups have the above-mentioned ability, they may be directly bonded to the polyimide precursor or the main chain of the polyimide, or may be bonded via an appropriate bonding group.

Examples of the side chain B include those represented by the following formulas (b-1) to (b-3). The compound represented by the formula (b-2) has a structure having a cinnamoyl group and a methacryl group, and the compound represented by the formula (b-3) has a structure that generates a radical by ultraviolet irradiation. . In the formula, Ar ₄ , Q, R ⁶ to R ¹⁷ , S, T ₁ and T ₂ will be described later.

In the formula (b-1), R ⁶ represents —CH ₂ —, —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —CH ₂ O—, —N (CH ₃ ) —, —CON (CH ₃ ) —, —N (CH ₃ ) CO—, wherein R ⁷ is cyclic, unsubstituted or substituted with a fluorine atom having 1 to 20 carbon atoms Represents alkylene, wherein any —CH ₂ — in the alkylene may be replaced by —CF ₂ — or —CH═CH—, and when any of the following groups are not adjacent to each other: May be replaced by a group; —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, carbocycle, heterocycle. R ⁸ represents —CH ₂ —, —O—, —COO—, —OCO—, —NHCO—, —NH—, —N (CH ₃ ) —, —CON (CH ₃ ) —, —N (CH ₃ ). Represents CO—, a carbocycle, or a heterocycle, and R ⁹ represents a vinylphenyl group, —CR ¹⁰ ═CH ₂ group, a carbocycle, a heterocycle, or the following formulas R9-1 to R9-34 R ¹⁰ represents a structure, and R ¹⁰ represents a hydrogen atom or a methyl group which may be substituted with a fluorine atom.

In the formula (b-1), R ⁶ represents —CH ₂ —, —O—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —COO—, A linking group selected from —OCO—, —CON (CH ₃ ) —, and —N (CH ₃ ) CO—. These linking groups can be formed by ordinary organic synthetic techniques, but from the viewpoint of ease of synthesis, —CH ₂ —, —O—, —COO—, —NHCO—, —NH—, —CH ₂ O- is preferred.

In the formula (b-1), R ⁷ represents cyclic, unsubstituted or alkylene having 1 to 20 carbon atoms which is unsubstituted or substituted by a fluorine atom, wherein any —CH ₂ — in the alkylene is —CF ₂ —. Or —CH═CH— may be substituted for any of the following groups when they are not adjacent to each other: —O—, —COO—, —NHCO -, -NH-, carbocycle, heterocycle.
Specific examples of the carbocycle and heterocycle include the following structures, but are not limited thereto.

In the formula (b-1), R ⁸ represents —CH ₂ —, —O—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —COO—, It is a linking group selected from —OCO—, —CON (CH ₃ ) —, —N (CH ₃ ) CO—, carbocycle and heterocycle. Among these, —CH ₂ —, —O—, —COO—, —OCO—, NHCO—, —NH—, a carbocycle, or a heterocyclic ring is preferable from the viewpoint of ease of synthesis. Specific examples of the carbocycle and the heterocycle are as described above.

In the formula (b-1), R ⁹ represents a styryl group, —CR ¹⁰ ═CH ₂ , a carbocycle, a heterocyclic ring, or a structure represented by the above formulas R9-1 to R9-31, and R ¹⁰ represents a hydrogen atom or It represents a methyl group which may be substituted with a fluorine atom.

Among these, from the viewpoint of photoreactivity, R ⁹ is more preferably a styryl group, —CH═CH ₂ , —C (CH ₃ ) ═CH _2, or the above formulas R9-2, R9-12, or R9-15. .

In the formula (b-2), R ¹⁰ represents a group selected from —CH ₂ —, —O—, —CONH—, —NHCO—, —COO—, —OCO—, —NH—, and —CO—.
R ¹¹ 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 , May be replaced by a fluorine atom or an organic group. In addition, R ¹¹ may be substituted with —CH ₂ — when any of the following groups are not adjacent to each other; —O—, —NHCO—, —CONH—, — COO—, —OCO—, —NH—, —NHCONH—, —CO—.
R ¹² represents —CH ₂ —, —O—, —CONH—, —NHCO—, —COO—, —OCO—, —NH—, —CO—, or a single bond.
R ¹³ represents a photocrosslinkable group such as a cinnamoyl group, a chalcone group, or a coumarin group.
R ¹⁴ is a single bond, or an alkylene group having 1 to 30 carbon atoms, a divalent carbocycle or a heterocycle, and one or more of the alkylene group, divalent carbocycle or heterocycle The hydrogen atom may be replaced with a fluorine atom or an organic group. In addition, R ¹⁴ may be substituted with —CH ₂ — when any of the following groups are not adjacent to each other: —O—, —NHCO—, —CONH—, — COO—, —OCO—, —NH—, —NHCONH—, —CO—.
R ¹⁵ represents a photopolymerizable group selected from either an acryl group or a methacryl group.
Among the side chains represented by the formula (b-2), specific examples of the group represented by —R ¹³ —R ¹⁴ —R ¹⁵ can include the following structures, but are not limited thereto. In the following structures, R represents a hydrogen atom or a methyl group.

In the formula (b-3), Ar ₄ represents an aromatic hydrocarbon group selected from phenylene, naphthylene, and biphenylene, which may be substituted with an organic group, and a hydrogen atom may be replaced with a halogen atom. good.
R ₁₆ and R ₁₇ 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 ₁₆ and R ₁₇ form a ring. You may do it.
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} ) - or -N _(CH 3) shows a binding group CO-.
S is a single bond or an alkylene group having 1 to 20 carbon atoms that is unsubstituted or substituted by a fluorine atom (wherein the alkylene group —CH ₂ — or —CF ₂ — is optionally replaced by —CH═CH—) In the case where any of the following groups are not adjacent to each other, these groups may be substituted: —O—, —COO—, —OCO—, —NHCO—, —CONH -, -NH-, divalent carbocycle, divalent heterocycle.).
Q is represented by the following formula (wherein R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₃ represents —CH ₂ —, —NR—, —O—, —S—). Represents the structure.

Among the side chains represented by the formula (b-3), specific examples of the group represented by —Ar ₄ —CO—CQR ¹⁶ R ¹⁷ can include the following structures, but are not limited thereto. .

The amount of the side chain B is not particularly limited as long as the response speed of the liquid crystal in the liquid crystal display element can be increased. When it is desired to increase the response speed of the liquid crystal in the liquid crystal display element, it is preferable to increase the response speed as much as possible without affecting other characteristics.

<Polyimide precursor>
As described above, the polyimide precursor includes a polyamic acid and a polyamic acid ester. In the following, the polyamic acid will be described in detail. The polyamic acid ester can also be prepared by a conventionally known method or by a method similar to or similar to the polyamic acid described later.
<Polyamic acid>
A polyamic acid having a side chain A is obtained by reacting the raw material by either having the side chain A or both of the raw material diamine and tetracarboxylic acid anhydride having the side chain A. be able to. Among these, the method using a diamine compound having a side chain A is preferable from the viewpoint of ease of raw material synthesis.
The polyamic acid having a side chain A and a side chain B is either a side chain A or a side chain B, or only one side chain A is a raw material of diamine and tetracarboxylic anhydride. And the other has only the side chain B, either one has the side chain A and the side chain B and the other has the side chain A, either one has the side chain A and the side chain B And the other has side chain B, or both have side chain A and side chain B, and can be obtained by reacting the raw materials. Among these, the method using a diamine compound having a side chain A, a diamine compound having a side chain B, and a tetracarboxylic acid having no side chain A or side chain B is preferable from the viewpoint of ease of raw material synthesis.
Hereinafter, the diamine compound having the side chain A will be described, and then the diamine compound having the side chain B will be described.

<Diamine compound having side chain A>
As a diamine compound having a side chain A (hereinafter also referred to as diamine A), the diamine side chain has an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, or a macrocyclic substituent composed thereof. A diamine can be mentioned as an example. Specific examples include diamines having a side chain represented by the formula (a). More specifically, examples include diamines represented by the following formulas (1), (3), (4), and (5), but are not limited thereto. The definitions of l, m, n and R ¹ to R ^{5 in} the formula (1) are the same as those in the formula (a).

In formula (3) or formula (4), each of A ₁₀ independently represents —COO—, —OCO—, —CONH—, —NHCO—, —CH ₂ —, —O—, —CO—, or —NH. - represents, a ₁₁ represents a single bond or a phenylene radical, a represents the side chain a, a 'is an alkyl group, a fluorine-containing alkyl group, aromatic ring, aliphatic ring, any structure selected from heterocycle It represents a macrocyclic substituent composed of a combination.

In the formula (5), A ₁₄ is an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, and A ₁₅ is a 1,4-cyclohexylene group or 1,4-phenylene. A ₁₆ is an oxygen atom or —COO— * (where a bond marked with “*” is bonded to A ₃ ), and A ₁₇ is an oxygen atom or —COO— * (wherein , “*” Is a bond with (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. )

The bonding position of the two amino groups (—NH ₂ ) in the formula (1) is 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 compound, the positions 2, 4 or 3, 5 are more preferable.

Specific examples of the structure of the formula (1) include diamines represented by the following formulas [A-1] to [A-24], but are not limited thereto.

In the formulas [A-1] to [A-5], A ₁ each independently represents an alkyl group having 2 to 24 carbon atoms or a fluorine-containing alkyl group.
In formula [A-6] and [A-7], A ₂ each independently represents —O—, —OCH ₂ —, —CH ₂ O—, —COOCH ₂ —, or —CH ₂ OCO—. , A ₃ are each independently an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group, or a fluorine-containing alkoxy group.
In formulas [A-8] to [A-10], A ₄ each independently represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH ₂ —, —CH ₂ OCO—, — _{_{CH 2 O -, - OCH 2}} -, or -CH ₂ - indicates, _{a 5} are each independently 1 to 22 alkyl group carbon atoms, an alkoxy group, a fluorine-containing alkyl group or fluorine-containing alkoxy group.

In Formula [A-11] and Formula [A-12], A ₆ each independently represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH ₂ —, —CH ₂ OCO—, — CH ₂ O—, —OCH ₂ —, —CH ₂ —, —O—, or —NH—, and A ₇ 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.
In formulas [A-13] and [A-14], A ₈ each independently represents an alkyl group having 3 to 12 carbon atoms, and cis-trans isomerism of 1,4-cyclohexylene is trans isomerism, respectively. Is the body.
In formula [A-15] and formula [A-16], A ₉ is each independently an alkyl group having 3 to 12 carbon atoms, and cis-trans isomerism of 1,4-cyclohexylene is trans isomerism, respectively. Is the body.

Specific examples of diamines represented by the formula (3), the following formula [A-25] ~ formula _[A-30] (A 12 are, -COO -, - OCO -, - CONH -, - NHCO- , —CH ₂ —, —O—, —CO—, or —NH—, and A ₁₃ represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group. Yes, but not limited to this.

Specific examples of the diamine represented by the formula (4) include diamines represented by the following formulas [A-31] to [A-32], but are not limited thereto.

Of these, [A-1], [A-2], [A-3], [A-7], [A-14], [A-14], [A-14], [A-14], [A-14], [A-14], [A-14], [A-14] The diamines of A-16], [A-21] and [A-22] are preferred.
The diamine compounds can be used alone or in combination of two or more depending on the liquid crystal alignment properties, pretilt angle, voltage holding characteristics, accumulated charge, and the like when the liquid crystal alignment film is formed.

Of 100 mol% of the diamine component used for the synthesis of the polyamic acid having the side chain A, the diamine A should be 5-70 mol%, preferably 10-50 mol%, more preferably 20-50 mol%. .

<Diamine compound having side chain B>
Examples of diamine compounds having side chain B (hereinafter also referred to as diamine B) include vinyl group, acrylic group, methacryl group, anthracenyl group, cinnamoyl group, chalconyl group, coumarin group, maleimide group, stilbene group, etc. And a diamine having a specific structure capable of generating radicals upon irradiation with ultraviolet rays. Specific examples include diamines having side chains represented by the formulas (b-1) to (b-3). As a specific example, it is represented by the following general formula (2) (the definitions of R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ in formula (2) are the same as those in formula (b-1)). Although a diamine can be mentioned, it is not limited to this.

The bonding position of the two amino groups (—NH ₂ ) in the formula (2) is 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 compound, the positions 2, 4 or 3, 5 are more preferable.
Specific examples include the following compounds, but are not limited thereto. In the following compounds, X independently represents a single bond, a bond group selected from the group consisting of ether, benzyl ether, ester, amide and amino, R represents a hydrogen atom or a methyl group, and S ₁ represents a single bond. An alkylene group having 1 to 20 carbon atoms which is bonded, unsubstituted or substituted with a fluorine atom. L, m, and n each independently represent an integer of 0 to 20.

The diamine compound may be one kind or two depending on the liquid crystal orientation, the pretilt angle, the voltage holding characteristics, the accumulated charge characteristics, and the liquid crystal response speed when the liquid crystal display element is used. A mixture of more than one can also be used.

Among 100 mol% of the diamine component used for the synthesis of the polyamic acid, the diamine B is 0% to 95 mol%, preferably 20-80 mol%, more preferably 40-70 mol%.

<Other diamine compounds>
The polyamic acid used in the present invention can be used in combination with other diamine compounds other than diamine A and diamine B as the diamine component as long as the effects of the present invention are not impaired. Specific examples are given below.

p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2, 5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4 , 6-diaminoresorcinol, 4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 3,3′-dihydroxy -4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl 3,3′-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'-sulfonyldi Aniline, 3,3′-sulfonyldianiline, bis ( -Aminophenyl) silane, 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-diamino Naphthalene, 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- Minophenyl) 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-phenylenebis (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-phenylenebi [(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-phen Nylene) 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) diphenylsulfone, 2,2′-bis [4- (4- Aminophenoxy) phenyl] propane, 2,2′-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2′-bis (4-aminopheny) ) Hexafluoropropane, 2,2′-bis (3-aminophenyl) hexafluoropropane, 2,2′-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2′-bis (4- Aminophenyl) propane, 2,2′-bis (3-aminophenyl) propane, 2,2′-bis (3-amino-4-methylphenyl) propane, 3,5-diaminobenzoic acid, 2,5-diamino Benzoic acid, bis (4-aminophenoxy) methane, 1,2-bis (4-aminophenoxy) ethane, 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, 1,7-bis (4-amino) Phenoxy) heptane, 1,7- (3-aminophenoxy) heptane, 1,8-bis (4-aminophenoxy) octane, 1,8-bis (3-aminophenoxy) octane, 1,9-bis (4- Aminophenoxy) nonane, 1,9-bis (3-aminophenoxy) nonane, 1,10- (4-aminophenoxy) decane, 1,10- (3-aminophenoxy) decane, 1,11- (4-amino Phenoxy) undecane, 1,11- (3-aminophenoxy) undecane, 1,12- (4-aminophenoxy) dodecane, 1,12- (3-aminophenoxy) dodecane Aromatic diamines such as ethylene, alicyclic diamines such as bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, 1,3-diaminopropane, 1,4-diaminobutane, , 5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1, Aliphatic diamines such as 12-diaminododecane.

The above-mentioned other diamine compounds may be used alone or in combination of two or more depending on the properties such as the liquid crystal orientation, the pretilt angle, the voltage holding property, and the accumulated charge when the liquid crystal alignment film is used.

<Tetracarboxylic dianhydride>
In the synthesis of the polyamic acid used in the present invention, the tetracarboxylic dianhydride to be reacted with the diamine component is not particularly limited. Specific examples are given below.

Pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7 -Anthracene tetracarboxylic acid, 1,2,5,6-anthracene tetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4'-biphenyltetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3,4-dicarboxyphenyl) propyl Bread, 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-cyclo Tantetracarboxylic 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- Tetrahydraphthalene-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 , 6-tricarboxynorbornane-2: 3,5: 6 dicarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid and the like, and the like.

The tetracarboxylic dianhydride can be used singly or in combination of two or more according to properties such as liquid crystal alignment properties, voltage holding properties, and accumulated charges when formed into a liquid crystal alignment film.

<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, the diamine component and tetracarboxylic dianhydride are reacted in an organic solvent. The reaction between the diamine component and tetracarboxylic 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 produced polyamic acid dissolves. Furthermore, even if it is an organic solvent which does not dissolve a polyamic acid, it may be mixed with the said solvent and used as long as the produced 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.
Specific examples of the organic solvent are given below.
N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N-methylformamide, N-methyl-2-pyrrolidone, 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, methoxymethyl Pentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, butyl cellosolve Cetate, 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 mono Methyl 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-octane, diethyl ether, cyclohexanone, e Len 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, 3-ethoxypropionic acid Methyl ethyl, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 2-Ethyl-1-hexanol. These organic solvents may be used alone or in combination.

When the diamine component and the tetracarboxylic dianhydride component are reacted in an organic solvent, the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic dianhydride component is used as it is or in an organic solvent. A method of adding by dispersing or dissolving in a solvent, a method of adding a diamine component to a solution in which a tetracarboxylic dianhydride component is dispersed or dissolved in an organic solvent, and a tetracarboxylic dianhydride component and a diamine component. The method of adding alternately etc. is mentioned, You may use any of these methods. 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 reacting the diamine component and the tetracarboxylic dianhydride component can be selected arbitrarily, and is, for example, in the range of −20 ° C. to 150 ° C., preferably −5 ° C. to 100 ° C. The reaction can be carried out at any concentration, for example 1 to 50% by mass, preferably 5 to 30% by mass.

In the above polymerization reaction, the ratio of the total number of moles of the tetracarboxylic dianhydride component to the total number of moles of the diamine component can be selected according to the molecular weight of the polyamic acid to be obtained. Similar to the normal polycondensation reaction, the molecular weight of the polyamic acid produced increases as the molar ratio approaches 1.0. If it shows a preferable range, it is 0.8 to 1.2.

The method for synthesizing the polyamic acid used in the present invention is not limited to the above-described method, and, like 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.

<Polyimide>
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.
In the polyimide used in the present invention, the imidization 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 it is preferable to carry out while removing water generated by the imidation reaction from the outside of the system.

The catalyst imidation of the polyimide precursor can be performed by adding a basic catalyst and an acid anhydride to the polyimide precursor solution and stirring at -20 to 250 ° C, preferably 0 to 180 ° C. The amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, 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.

When recovering the produced polyimide precursor or polyimide from the polyimide precursor or polyimide 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. In addition, when the polymer collected by precipitation is redissolved in an organic solvent and reprecipitation and collection is 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>
The liquid crystal aligning agent of the present invention comprises the above [I] polymerizable compound; and the above [II] polyimide precursor or polyimide; in addition to the [I] and [II] components, for forming a resin film You may have a resin component. The content of all the resin components is 1% by mass to 20% by mass, preferably 3% by mass to 15% by mass, and more preferably 3% by mass to 10% by mass in 100% by mass of the liquid crystal aligning agent.

In the liquid crystal aligning agent used in the present invention, all of the above resin components may be a polyimide precursor or polyimide having side chain A, or a polyimide precursor or polyimide having side chain A and side chain B. A mixture of these may be used, and other polymers may be further mixed. In that case, the content of the other polymer in the resin component is preferably 0.5% by mass to 15% by mass, and more preferably 1% by mass to 10% by mass.
Examples of such other polymers include polyimide precursors or polyimides that do not have side chain B, polyimide precursors or polyimides that do not have side chain A and side chain B at the same time. It is not limited.

The molecular weight of the polymer of the above resin component is the weight measured by GPC (Gel Permeation Chromatography) method in consideration of the strength of the coating film obtained therefrom, workability at the time of coating film formation, and uniformity of the coating film The average molecular weight is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000.

<Solvent>
The organic solvent used for the liquid crystal aligning agent of this invention will not be specifically limited if it is an organic solvent in which the resin component mentioned above is dissolved. This organic solvent may be one type of solvent or a mixed solvent of two or more types. If the specific example of an organic solvent is given dare, the organic solvent illustrated by the said polyamic acid synthesis 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 dissolve resin components. From the viewpoint of sex.
Moreover, since the solvent as shown below improves the uniformity and smoothness of the coating film, it is preferable to use the solvent by mixing it with a solvent having high solubility of the resin component.
For example, 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 Cole 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-butyl acetate, propylene acetate Glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxy Propyl propionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, 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, methyl lactate Examples thereof include esters, lactate ethyl esters, lactate n-propyl esters, lactate n-butyl esters, lactyl isoamyl esters, and 2-ethyl-1-hexanol. A plurality of these solvents may be mixed. When these solvents are used, the content is preferably 5 to 80% by mass, more preferably 20 to 60% by mass based on the total amount of the solvent contained in the liquid crystal aligning agent.

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, F-top EF301, EF303, EF352 (manufactured by Tochem Products), MegaFuck F171, F173, R-30 (manufactured by Dainippon Ink), Florard FC430, FC431 (manufactured by Sumitomo 3M) Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.). When these surfactants are used, the proportions used are preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part per 100 parts by mass of the resin component contained in the liquid crystal aligning agent. Part by mass.

Specific examples of the compound that improves the adhesion between the liquid crystal alignment film and the substrate include a functional silane-containing compound and an epoxy group-containing compound. For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxy Carbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-tri Toxisilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxy Silane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyl Trimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, poly Lopylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl -2,4-hexanediol, N, N, N ′, N ′,-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′ , N ′,-tetraglycidyl-4, 4′-diaminodiphenylmethane, 3- (N-allyl-N-glycidyl) aminopropyltrimethoxysilane, 3- (N, N-diglycidyl) aminopropyltrimethoxysilane, etc. It is done. In order to further increase the rubbing resistance of the resin using the present invention, a phenol compound such as 2,2′-bis (4-hydroxy-3,5-dihydroxymethylphenyl) propane or tetra (methoxymethyl) bisphenol is added. Also good. When these compounds are used, the amount is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the resin component contained in the liquid crystal aligning agent.
In addition to the above, the liquid crystal aligning agent used in the present invention is a dielectric or conductive material for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal alignment film as long as the effects of the present invention are not impaired. Substances may be added.

<Liquid crystal alignment film>
A cured film obtained by applying the liquid crystal aligning agent of the present invention to a substrate and then drying and baking as necessary can be used as a liquid crystal aligning film as it is. In addition, this cured film is rubbed, irradiated with polarized light or light of a specific wavelength, treated with an ion beam, etc., and a voltage is applied to the liquid crystal display element after filling the liquid crystal as an alignment film for SC-PVA. It is also possible to irradiate UV in such a state.

At this time, 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, Trimethylpentene, polyolefin, polyethylene terephthalate, (meth) acrylonitrile, triacetyl cellulose, diacetyl cellulose, acetate butyrate cellulose, and the like can be used. In addition, it is preferable to use a substrate on which an ITO (Indium Tin Oxide) electrode or the like for driving a 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 method for applying 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 coaters, slit coaters, and spinners. 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 firing temperature of the coating film formed by applying the liquid crystal aligning agent is not limited, and can be performed at any temperature of, for example, 100 to 350 ° C., preferably 120 ° C. to 300 ° C., more preferably 150 to 250 ° C. Firing can be performed at an arbitrary time of 5 minutes to 240 minutes. The time is preferably 10 minutes to 90 minutes, 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.

The thickness of the liquid crystal alignment film obtained by firing is not particularly limited, but is preferably 5 to 300 nm, more preferably 10 to 120 nm.

<Liquid crystal display element having liquid crystal alignment film>
The liquid crystal display element of the present invention can be obtained by forming a liquid crystal alignment film on a substrate by the above method and then preparing a liquid crystal cell by a known method. 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 aligning agent of the present invention is applied onto two substrates and baked to form a liquid crystal aligning film, and the two substrates are arranged so that the liquid crystal aligning films face each other. A liquid crystal layer composed of liquid crystal is sandwiched between two substrates, that is, a liquid crystal layer is provided in contact with the liquid crystal alignment film, and ultraviolet rays are applied while applying a voltage to the liquid crystal alignment film and the liquid crystal layer. This is a vertical alignment type liquid crystal display device including a liquid crystal cell to be manufactured. As described above, 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 light possessed by the polymer. A liquid crystal display device in which the alignment of the liquid crystal is more efficiently fixed and the response speed is remarkably improved by reacting the reactive side chains or the photoreactive side chain of the polymer with the polymerizable compound. It becomes.

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, but in the liquid crystal display element of the present invention, the liquid crystal aligning agent of the present invention is used as the liquid crystal aligning agent for forming the liquid crystal aligning film. It is possible to operate even in a structure in which a line / slit electrode pattern of 1 to 10 μm, for example, is formed on one side substrate and a slit pattern or projection pattern is not formed on the opposite substrate. This process can be simplified and high transmittance can be obtained.

As a high-performance element such as a TFT 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 alignment film is formed by applying the liquid crystal aligning agent of the present invention on this substrate and baking it, and the details are as described above.

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 liquid crystal such as MLC-6608 or MLC-6609 manufactured by Merck Can be used.

As a method for sandwiching the liquid crystal layer between two substrates, a known method can be exemplified. 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 the inside so as to be inside and sealed. The thickness of the spacer at this time 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 to the liquid crystal alignment film and the liquid crystal layer by applying a voltage between electrodes installed on the substrate. 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 amount of ultraviolet irradiation is, for example, 1 to 60 J / cm ² , preferably 40 J / cm ² or less, and more preferably 20 J / cm ² or less. It is preferable that the amount of ultraviolet irradiation be small because it is possible to suppress a decrease in reliability caused by the destruction of the liquid crystal and members constituting the liquid crystal display element, and the manufacturing efficiency is increased by reducing the ultraviolet irradiation time.

Thus, when ultraviolet rays are applied 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 memorized by this polymer. The response speed of the obtained liquid crystal display element can be increased. Moreover, when ultraviolet rays are irradiated while applying a voltage to the liquid crystal alignment film and the liquid crystal layer, at least one selected from a polyimide precursor having a reactive side chain and a polyimide obtained by imidizing the polyimide precursor Since the photoreactive side chains of the polymer or the photoreactive side chains of the polymer react with the polymerizable compound, the response speed of the obtained liquid crystal display element can be increased.

The liquid crystal aligning agent is not only useful as a liquid crystal aligning agent for producing a vertical alignment type liquid crystal display element such as a PSA type liquid crystal display or an SC-PVA type liquid crystal display, but also by a rubbing process or a photo-alignment process. It can also be suitably used for applications of the liquid crystal alignment film to be produced.
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples.

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.
TCA: 2,3,5-tricarboxycyclopentylacetic acid-1,4,2,3-dianhydride.

The diamine represented by the following formula DA-1 was synthesized by the method described in Japanese Patent No. 4085206.
The diamine represented by the following formula DA-2 was synthesized by the method described in Japanese Patent No. 4466373.
The diamine represented by the following formula DA-3 was synthesized by the method described in Japanese Patent No. 5273035.
The diamine represented by the following formula DA-4 was purchased from Tokyo Chemical Industry Co., Ltd.
The diamine represented by the following formula DA-5 was synthesized by the method described in WO2009 / 093704.
A diamine represented by the following formula DA-6 was prepared by the method described in Japanese Patent Application No. 2013-132874.
The diamine represented by the following formula DA-7 was purchased from Wako Pure Chemical Industries.
A diamine represented by the following formula DA-8 was prepared by the method described in Japanese Patent Application No. 2013-182351.
The diamine represented by the following formula DA-9 was prepared by the method described later (raw material synthesis example: synthesis of DA-9).

<Solvent>
NMP: N-methyl-2-pyrrolidone.
BCS: Butyl cellosolve.
<Additives>
3AMP: 3-picolylamine.
<Polymerizable compound>
Polymerizable compounds represented by the following formulas RM1 to RM10 and RM11.

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: Column manufactured by Shodex (KD-803, KD-805),
Column temperature: 50 ° C.
Eluent: N, N′-dimethylformamide (as additives, lithium bromide-hydrate (LiBr · H ₂ O) is 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphoric acid) is 30 mmol / L, Tetrahydrofuran (THF) at 10 ml / L),
Flow rate: 1.0 ml / min,
Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight: about 9,000,150,000, 100,000, 30,000) manufactured by Tosoh Corporation, and polyethylene glycol (molecular weight: about 12,000, 4) manufactured by Polymer Laboratory , 1,000, 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 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. This solution was measured for proton NMR at 500 MHz with an NMR measuring instrument (JNW-ECA500) manufactured by JEOL Datum. The imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of amic acid appearing in the vicinity of 9.5 to 10.0 ppm. It calculated | required by the following formula | equation using the integrated value. 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.
Imidization rate (%) = (1−α · x / y) × 100

The products described in the synthesis examples below were identified by ¹ H-NMR analysis (analysis conditions are as follows).
Apparatus: Varian NMR System 400 NB (400 MHz)
Measurement solvent: CDCl _3, DMSO-d ₆
Reference substance: Tetramethylsilane (TMS) (δ0.0 ppm for ¹ H)
(Example of raw material synthesis: synthesis of DA-9)

<Synthesis of DA-9-1>
A 1000 mL four-necked flask was charged with 120 g (310 mmol, 1.0 eq) of cholesterol and 33.3 g (329 mmol, 1.1 eq) of triethylamine in 600 g of THF, and 69.2 g (300 mmol) of 3,5-dinitrobenzoyl chloride was added over 1 hour. Added. After the addition, the mixture was stirred overnight at room temperature and then reprecipitated with water. The obtained solid was recrystallized with IPA and ethyl acetate, respectively, to obtain 179 g of a crude product of DA-9-1 (crude yield: 100%).
¹ H-NMR (CDCl ₃ , δ ppm): 9.22 (s, 1H), 9.16 (s, 2H), 5.46-5.44 (m, 1H), 5.00-4.95 ( m, 1H), 2.56-2.48 (m, 2H), 2.06-1.95 (m, 4H), 1.87-1.81 (m, 2H), 1.63-0. 86 (m, 32H), 0.70 (s, 3H).

<Synthesis of DA-9>
In a 2000 mL four-necked flask, 146 g (251 mmol) of DA-9-1 and 284 g of tin chloride (1497 mmol, 6.0 eq) in 750 g of THF and 750 g of pure water were charged and stirred at 70 ° C. overnight. After completion of the reaction, neutralization was performed, and precipitated tin was removed by filtration. Thereafter, recrystallization was performed with liquid separation and IPA to obtain 76.3 g of DA-9 (yield: 58%).
¹ H-NMR (CDCl ₃ , δ ppm): 6.78 (s, 2H), 6.18 (s, 1H), 5.42-5.40 (m, 1H), 4.84-4.77 ( m, 1H), 3.67 (s, 4H), 2.43 (d, 2H), 1.63-0.86 (m, 38H), 0.69 (s, 3H).

<Synthesis of RM1-A>
A 1 L four-necked flask equipped with a magnetic stirrer was charged with 58.3 g (305 mmol) of 4-bromo-2-fluorophenol and 4- (4,4,5,5-tetramethyl-1,3 in 350 g of THF and 117 g of water. , 2-Dioxaborolan-2-yl) phenol 67.2 g (1.0 eq), potassium carbonate 84.8 g (2.0 eq), tri (o-tolyl) phosphine 7.42 g (8 mol%), and after nitrogen substitution Bis (triphenylphosphine) palladium (II) chloride (10.9 g, 5 mol%) was added and reacted at 65 ° C. for 15 hours.
After completion of the reaction, THF was distilled off by concentration under reduced pressure. After dilution with 466 g of ethyl acetate, 268 g of 3.0 M HCl aqueous solution was added, and insoluble matters such as Pd were removed by filtration. Further, 233 g of ethyl acetate was used to remove the flask and filtrate. Washing was performed. Subsequently, the aqueous phase is separated and the organic phase is recovered, and the recovered organic phase is washed three times with 350 g of pure water, dehydrated with magnesium sulfate, and then activated carbon (brand: special white birch dry product manufactured by Nippon Enviro Chemical) 2. 92 g was added and stirred at room temperature for about 30 minutes, followed by filtration and drying to obtain a crude product. The crude product was repulped twice with 292 g of toluene at room temperature and then filtered and dried to obtain 42.0 g of RM1-A (yield: 67%, property: light pink crystals).
¹ H-NMR (400 MHz) in DMSO-d ₆ : 6.80 ppm (dd, J = 2.0 Hz, J = 6.8 Hz, 2H), 6.97 ppm (t, J = 8.8 Hz, 1H), 7.21 ppm (dd, J = 2.0 Hz, J = 8.4 Hz, 1H), 7.35 ppm (dd, J = 2,4 Hz, J = 13.2 Hz, 1H), 7.42 ppm (dd, J = 2.0 Hz, J = 6.4 Hz, 2H), 9.49 ppm (s, 1H), 9.82 ppm (s, 1H).

<Synthesis of RM1-B>
A 200 ml four-necked flask equipped with a magnetic stirrer was charged with 6.00 g (24.5 mmol) of the compound (RM1-A) obtained above and 2- (4-bromobutyl) -1,3-dioxolane in 80 ml of acetone. 0.0 g (2.2 eq) and potassium carbonate 13.8 g (4.0 eq) were charged and reacted at 60 ° C. for 24 hours. Thereafter, the reaction solution was poured into pure water to precipitate crystals, followed by filtration and drying to obtain 10.4 g of RM1-B (yield: 92%).
¹ H-NMR (400 MHz) in CDCl ₃ : 1.60-1.67 ppm (m, 4H), 1.71-1.78 ppm (m, 4H), 1.82-1.93 ppm (m, 4H), 3.82-4.10 ppm (m, 12H) , 4.89 ppm (t, J = 4.6 Hz, 2H), 6.92-7.00 ppm (m, 3H), 7.20-7.30 ppm (m, 2H), 7.43 ppm (d, J = 8.8Hz, 2H).

<Synthesis of RM1>
In a 100 ml four-necked flask equipped with a magnetic stirrer, 2.90 g (6.30 mmol) of the compound (RM1-B) obtained above and 2.5 g (2.4 eq) of 2- (bromomethyl) acrylic acid in 40 ml of THF. Then, 2.8 g (2.4 eq) of tin chloride (anhydride) was added, and 12 ml of 10% HCl aqueous solution was added and reacted at 70 ° C. for 20 hours. Thereafter, the reaction solution was poured into pure water to precipitate crystals, and filtered and dried to obtain a crude product. The obtained crude product was recrystallized in THF / EtOH to obtain 2.2 g of RM1 (yield: 69%).
¹ H-NMR (400 MHz) in CDCl ₃ : 1.55-1.93 ppm (m, 12H), 2.61 ppm (dd, J = 7.6 Hz, J = 18.4 Hz, 2H), 3.09 ppm (dd, J = 6.8 Hz, J = 16.6 Hz, 2H), 4.00 ppm (t, J = 6.2 Hz, 2H), 4.08 ppm (t, J = 6.4 Hz, 2H), 4.35-4.60 ppm (m, 2H), 5.64 ppm (s, 2H) , 6.24 ppm (s, 2H), 6.93-7.01 ppm (m, 3H), 7.22-7.289 ppm (m, 2H), 7.45 ppm (d, J = 8.8Hz, 2H).

<Synthesis of RM2-A>
A 1 L four-necked flask equipped with a magnetic stirrer was charged with 70.2 g (539 mmol) of 2-hydroxyethyl methacrylate and 76.4 g (1.4 eq) of triethylamine in 281 g of THF, and diluted with 35.1 g of THF under stirring with ice cooling. After dropwise addition of 74.6 g (1.2 eq) of methanesulfonyl chloride, the mixture was stirred at room temperature for 2 hours. Thereafter, the salt precipitated from the reaction solution was filtered, and 0.35 g of dibutylhydroxytoluene was added to the filtrate, followed by concentration and drying. Next, 281 g of ethyl acetate was added to the concentrate residue and 210 g of pure water was added. As a result, insoluble matter was generated. Stir for 30 minutes. Subsequently, this was filtered, and after confirming that insoluble matter was removed, the aqueous phase was removed. Further, the organic phase was washed twice with 210 g of pure water, dehydrated with magnesium sulfate, and concentrated and dried to obtain 99.0 g of RM2-A (yield: 86%, property: yellow liquid).
¹ H-NMR (400 MHz) in CDCl ₃ : 1.93-1.94 ppm (m, 3H), 3.03 ppm (s, 3H), 4.39-4.41 ppm (m, 2H), 4.46-4.44 ppm (m, 2H), 5.61 -5.62 ppm (m, 1H), 6.15 (m, 1H).

<Synthesis of RM2-B>
In a 300 ml four-necked flask equipped with a magnetic stirrer, 10.4 g (54.4 mmol) of 4-bromo-2-fluorophenol and 6-hydroxy-2-naphthaleneboronic acid 9 in 72.8 g of THF and 31.2 g of pure water .68 g (1.0 eq), potassium carbonate 15.1 g (2.0 eq), tri (o-tolyl) phosphine 1.32 g (8 mol%) were charged, and after nitrogen substitution, bis (triphenylphosphine) palladium (II) chloride 1.91 g (5 mol%) was added and reacted at 65 ° C. for 2 hours. Then, THF was removed by concentration under reduced pressure, diluted with 104 g of ethyl acetate, and 47.8 g of 3.0 M HCl aqueous solution was added and stirred. Subsequently, Pd was removed by filtration, and the residue was washed with 52.0 g of ethyl acetate, and then the aqueous phase was separated. The recovered organic phase was washed with 72.8 g of pure water three times and dehydrated with magnesium sulfate, and then added with 0.52 g of activated carbon (brand: special white birch dry product manufactured by Nippon Enviro Chemical) and stirred at room temperature for about 1 hour. And filtered and dried. The crude product was repulped with 72.8 g of toluene and purified by silica gel column chromatography (ethyl acetate / toluene / hexane (= 1/1/2 vol)) to obtain 6.47 g of RM2-B (yield: 49%, property: white solid).
¹ H-NMR (400 MHz) in DMSO-d ₆ : 7.03-7.13 ppm (m, 3H), 7.42-7.40 ppm (m, 1H), 7.57 ppm (dd, J = 13 Hz, J = 2.2 Hz, 1H) , 7.67 ppm (dd, J = 8.6 Hz, J = 1.8 Hz, 1H), 7.72 ppm (d, J = 8.4 Hz, 1H), 7.80 ppm (d, J = 8.4 Hz, 1H), 8.01 ppm (s, 1H), 9.78 ppm (s, 1H), 9.96 ppm (s, 1H).

<Synthesis of RM2>
In a 200 mL four-necked flask equipped with a magnetic stirrer, 6.07 g (23.9 mmol) of the compound (RM2-B) obtained above and 11.1 g of a polymerizable side chain (RM2-A) in 48.6 g of DMF ( 2.2 eq) and 9.93 g (3.0 eq) of potassium carbonate were charged and reacted at 65 ° C. for 22 hours under a nitrogen atmosphere.
Thereafter, the reaction solution was diluted with 48.6 g of ethyl acetate, inorganic salts were removed by filtration, and the residue was washed with 42.5 g of ethyl acetate. The recovered organic phase was washed 3 times with 48.6 g of pure water, and the organic phase was dehydrated with magnesium sulfate and concentrated and dried. After drying, 12.1 mg of 2,6-di-tert-butyl-p-cresol is added to the recovered crude product, and 5.77 g of THF is added and heated at 45 ° C. to completely dissolve, 35.8 g of methanol. And was recrystallized at 5.0 ° C. However, since impurities were confirmed, 4.89 g of THF was added to the collected solid and completely dissolved by heating at 45 ° C., and 24.9 g of methanol was added and recrystallized at room temperature to obtain 6.37 g of RM2. (Yield: 56%, property: white crystals).
¹ H-NMR (400 MHz) in DMSO-d ₆ : 1.89 ppm (s, 6H), 4.38-4.42 ppm (m, 4H), 4.46-2.47 ppm (m, 2H), 4.49-4.51 ppm (m, 2H) , 5.70-5.71 ppm (m, 2H), 6.05 ppm (d, J = 6.8 Hz, 2H), 7.22 ppm (dd, J = 9.0 Hz, J = 2.8 Hz, 1H), 7.33 ppm (t, J = 9.0 Hz, 1H), 7.40 ppm (d, J = 2.4 Hz, 1H), 7.59 ppm (d, J = 9.6 Hz, 1H), 7.70 ppm (dd, J = 12.8 Hz, J = 2.0 Hz, 1H), 7.80 ppm (dd, J = 8.6 Hz, J = 1.8 Hz, 1H), 7.88 ppm (t, J = 9.2 Hz, 2H), 8.15 ppm (s, 1H).

<Synthesis of RM3-A>
In a 2 L four-necked flask equipped with a mechanical stirrer, 25.5 g (101 mmol) of 1,4-dibromo-2-fluorobenzene, 4- (4,4,5,5-tetramethyl) in 179 g of THF and 76.6 g of pure water. -1,3,2-Dioxaborolan-2-yl) phenol 45.5 g (2.0 eq), potassium carbonate 41.7 g (3.0 eq), bis (triphenylphosphine) palladium (II) chloride 2.12 g The mixture was stirred at 65 ° C. for 24 hours under a nitrogen atmosphere. Then, THF was distilled off by concentration under reduced pressure, the reaction solution was diluted with 255 g of ethyl acetate, 3.0M HCl aqueous solution 99.5 g was added, and insoluble matters such as Pd were removed by filtration. After removing the aqueous phase from the filtrate, the obtained organic phase was washed with 179 g of pure water three times. The recovered organic phase is dehydrated with magnesium sulfate, 1.30 g of activated carbon (brand: special white birch dry product, Nippon Enviro Chemical) is added and stirred for about 30 minutes at room temperature, and then filtered and dried to obtain a crude product. Obtained. The recovered crude product was suspended in 153 g of toluene, washed with repulp at 60 ° C. for 1 hour twice, and filtered and dried to obtain 22.4 g of RM3-A (yield: 79%, property: light pink) crystal).
¹ H-NMR (400 MHz) in DMSO-d6: 6.85-6.88 ppm (m, 4H), 7.41 ppm (dd, J = 1.2 Hz J = 8.4 Hz, 2H), 7.46-7.49 ppm (m, 3H), 7.57 ppm (d, J = 8.8 Hz, 2H), 9.65 ppm (s, 2H).

<Synthesis of RM3>
In a 500 mL four-necked flask equipped with a mechanical stirrer, 23.0 g (2.2 eq) of a polymerizable side chain (RM2-A) and 14.1 g (50.2 mmol) of the compound (RM3-A) obtained above in DMF 113 g ), 20.9 g (3.0 eq) of potassium carbonate, and stirred at 65 ° C. for 18 hours under a nitrogen atmosphere. After 18 hours, since the raw material remained, a polymerizable side chain (RM2-A) (0.2 eq / 2) was added, and the reaction was further continued for 4 hours. Thereafter, the reaction solution was diluted with 113 g of ethyl acetate, inorganic salts were removed by filtration, and the residue was washed with 70.5 g of ethyl acetate. As a result of washing the recovered organic phase with 141 g of pure water, a small amount of white crystals was formed. Therefore, 70.5 g of ethyl acetate was added, and further washed with 141 g of pure water twice, and the organic phase was dehydrated with magnesium sulfate. , Filtered and dried. Add 0.71 g of activated carbon (brand: special white birch dry product manufactured by Nippon Enviro Chemical) to the recovered crude material, stir for about 30 minutes at room temperature, filter dry, add 222 g of ethyl acetate and heat at 50 ° C. This was completely dissolved, 98.2 g of hexane was added, and 15.0 g of RM3 was obtained by recrystallization at 2 ° C. (yield: 59%, property: white crystals).
¹ H-NMR (400 MHz) in DMSO-d6: 1.89 ppm (s, 6H), 4.30-4.33 ppm (m, 4H), 4.45-4.46 ppm (m, 4H), 5.71 ppm (s, 2H), 6.05 ppm (s, 2H), 7.07-7.10 ppm (m, 4H), 7.52-7.56 ppm (m, 5H), 7.70 ppm (d, J = 8.4 Hz, 2H).

<Synthesis of RM4>
In a 300 mL four-necked flask equipped with a magnetic stirrer, 9.18 g (45.0 mmol) of F-containing biphenol compound (RM1-A) and 18.6 g (3.0 eq) of potassium carbonate in 73.4 g of DMF, polymerizable side chain 20.7 g (2.2 eq) of (RM2-A) was charged and reacted at 62 ° C. for 15 hours under a nitrogen atmosphere. Thereafter, the reaction solution was diluted with 138 g of ethyl acetate, and inorganic salts were removed by filtration. Further, 45.9 g of ethyl acetate was added to the collected filtrate, washed with 91.8 g of pure water three times, and dehydrated with sodium sulfate. Subsequently, 0.46 g of activated carbon (brand: special white birch dry product manufactured by Nippon Enviro Chemical) was added and stirred at room temperature for about 30 minutes, followed by filtration, and the filtrate was concentrated and dried. 9.2 mg of 2,6-di-tert-butyl-p-cresol was added to the concentrate, 184 g of IPA was added, and the mixture was completely dissolved by heating to 57 ° C., recrystallized at room temperature, and RM4 13. 4 g was obtained (yield: 70%, property: pale yellow crystals).
¹ H-NMR (400 MHz) in DMSO-d6: 1.87-1.88 ppm (m, 6H), 4.27-4.29 ppm (m, 2H), 4.34-4.37 ppm (m, 2H), 4.43-4.46 ppm (m, 4H ), 5.69-5.70 ppm (m, 2H), 6.03 ppm (d, J = 4.8 Hz, 2H), 7.03 ppm (d, J = 8.8 Hz, 2H), 7.25 ppm (t, J = 8.8 Hz, 1H) , 7.39 ppm (dd, J = 1.6 Hz, J = 8.4 Hz, 1H), 7.50 ppm (dd, J = 2.0 Hz, J = 13 Hz, 1H), 7.58 ppm (d, J = 8.8 Hz, 2H).

<Synthesis Example 5 -Synthesis of RM5->
RM5 described above was synthesized by the method described in WO2012 / 002513.

<Synthesis Example 6 -Synthesis of RM6->
RM6 described above was synthesized by the method described in WO2012 / 133820 (see in particular paragraph [0163]).

<Synthesis of RM7-A>
In a 200 mL four-necked flask equipped with a magnetic stirrer, 9.00 g (44.1 mmol) of an F-containing biphenol compound (RM1-A), 22.4 g (3.0 eq) of bromoacetaldehyde dimethylacetal, 18 kg of NMP in 18 g of NMP 0.4 g (4.0 eq) and potassium iodide 2.2 g (0.30 eq) were charged and stirred at 120 ° C. for 18 hours. After 18 hours, 7.45 g (1.0 eq) of bromoacetaldehyde dimethyl acetal and 1.4 g (0.2 eq) of potassium iodide were added, and the mixture was further stirred for 8 hours. After completion of the reaction, the reaction solution was diluted with 99.0 g of THF, the inorganic salt was filtered, and the filtrate was concentrated under reduced pressure. Next, this residue was diluted with 198 g of ethyl acetate, washed twice with 99.0 g of pure water, and dehydrated with magnesium sulfate. Thereafter, 0.45 g of activated carbon (brand: special white birch dry product manufactured by Nippon Enviro Chemical) was added and stirred at room temperature for 1 hour, this was filtered, and the filtrate was concentrated under reduced pressure. Subsequently, 19.8 g of THF was added to the obtained crude product and dissolved at 50 ° C., then 60.3 g of IPA was added, and the mixture was stirred under ice cooling. The crystals thus precipitated were filtered and dried to obtain 11.5 g of RM7-A (yield: 62%, property: light brown crystals).
¹ H-NMR (400 MHz) in DMSO-d ₆ : 3.36 ppm (m, 12H), 4.01 ppm (d, J = 5.2 Hz, 2H), 4.08 ppm (d, J = 5.2 Hz, 2H), 4.74-4.69 ppm (m, 2H), 7.03 ppm (d, J = 11.6 Hz 2H), 7.25 ppm (t, J = 8.8 Hz 1H), 7.40-7.37 ppm (m, 1H), 7.51 ppm (dd, J = 13Hz, J = 2.2 Hz 1H), 7.58 ppm (d, J = 8.4 Hz 2H).

<Synthesis of RM7>
In a 500 mL four-necked flask equipped with a magnetic stirrer, 10.4 g (27.2 mmol) of the compound (RM7-A) obtained above in 103 g of THF, 11.6 g of ethyl 2- (bromomethyl) acrylate (2. 2eq), tin chloride 12.4 g (2.4 eq), 10 wt% HCl aqueous solution 36.2 g were charged and stirred at 70 ° C. for 39 hours. After completion of the reaction, 30 mg of 2,6-di-tert-butyl-p-cresol was added, THF was distilled off under reduced pressure, and diluted with 104 g of ethyl acetate. After removing the aqueous phase thus separated, the organic phase was washed 3 times with 62.4 g of pure water at 40 ° C. Next, after dehydrating the organic phase with magnesium sulfate, 0.52 g of activated carbon (brand: special white birch dry product manufactured by Nippon Enviro Chemical) was added and stirred at room temperature for 1 hour, this was filtered, and the filtrate was concentrated under reduced pressure. Left. Subsequently, 52 g of THF was added to the obtained crude product and dissolved at 60 ° C., 156 g of EtOH was added, and the mixture was stirred under ice cooling. Thereby, the precipitated crystals were filtered and dried to obtain 3.42 g of RM7 (yield: 30%, property: white crystals).
¹ H-NMR (400 MHz) in DMSO-d ₆ : 2.88-2.50 ppm (m, 2H), 3.17-2.11 ppm (m, 2H), 4.14 ppm (dd, J = 5.6 Hz, 11.2 Hz, 1H), 4.28 -4.20ppm (m, 2H), 4.33ppm (dd, J = 2.8 Hz, 11.0 Hz, 1H), 5.00-4.95ppm (m, 2H), 6.99ppm (d, J = 6.8 Hz, 2H), 7.22ppm (t, J = 8.8Hz, 1H), 7.41ppm (d, J = 8.4Hz, 1H), 7.52ppm (dd, J = 2Hz, 12.8Hz, 1H), 7.61ppm (d, J = 2.0Hz, 2H ).

<Synthesis of RM8-A>
In a 200 mL four-necked flask equipped with a magnetic stirrer, 10.0 g (53.7 mmol) of an F-containing biphenol compound (RM1-A) in 15.3 g of NMP, 20.4 g (3.0 eq) of potassium carbonate, 1 potassium iodide .61 g (0.20 eq) was charged, and 16.6 g (2.2 eq) of 4-chlorobutyraldehyde dimethyl acetal diluted with 5.30 g of NMP was added dropwise at 80 ° C. in a nitrogen atmosphere over 3 hours. 19 hours after the dropwise addition, 2.25 g (0.3 eq) of 4-chlorobutyraldehyde dimethyl acetal and 1.61 g (0.2 eq) of potassium iodide were added, and the mixture was further reacted for 25 hours. After completion of the reaction, the reaction solution was diluted with 80.0 g of ethyl acetate, and potassium carbonate was removed by filtration. Further, 20.0 g of ethyl acetate was added, washed 3 times with 60.0 g of pure water, and dehydrated with magnesium sulfate. Thereafter, the solvent was removed by concentration under reduced pressure to obtain a crude product. To the obtained crude product, 10 g of THF and 70 g of MeOH were added and heated at 50 ° C., and the crystals were precipitated by cooling with ice, and 11.7 g of RM8-A was obtained by filtration and drying (yield: 55%, properties). : White solid). The filtrate was concentrated under reduced pressure to remove the solvent, and the crude product was added with 5 g of THF and 70 g of IPA, heated at 40 ° C., and cooled with ice to precipitate crystals to obtain 3.0 g of RM8-A (yield) 14%, property: pale yellow solid).
¹ H-NMR (400 MHz) in DMSO-d ₆ : 1.77-1.67 ppm (m, 8H), 3.23 ppm (s, 12H), 4.01 ppm (t, J = 6 Hz, 2H), 4.08 ppm (t, J = 6 Hz, 2H), 4.44-4.41 ppm (m, 2H), 6.97 ppm (d, J = 6.8 Hz, 2H), 7.19 ppm (t, J = 8.8 Hz, 1H), 7.38 ppm (d, J = 7.6 Hz, 1H), 7.48 ppm (dd, J = 13.2 Hz, 2.4 Hz, 1H), 7.56 ppm (d, J = 8.8 Hz, 2H).

<Synthesis of RM8>
In a 300 mL four-necked flask equipped with a magnetic stirrer, 13.2 g (30.3 mmol) of the compound (RM8-A) obtained above in 133 g of THF, 12.9 g (2.2 eq) of ethyl 2- (bromomethyl) acrylate ), 13.8 g (2.4 eq) of tin chloride, and 46.3 g of 10 wt% aqueous HCl solution were charged and reacted at 50 ° C. for 5 hours. After 5 hours, 13.2 g of a 20 wt% aqueous HCl solution was added and allowed to react for 19 hours. After completion of the reaction, THF was distilled off under reduced pressure, diluted with 106 g of ethyl acetate, and washed with water 52.8 g three times. Subsequently, 26.4 g of ethyl acetate and 79.2 g of pure water were further added, and sodium hydrogen carbonate was added for neutralization. After neutralization, the salt was removed by filtration, 0.70 g of activated carbon (brand: special white birch dry product, Nippon Enviro Chemical) was added to the filtrate, and the mixture was stirred at room temperature and filtered. After washing the obtained solution twice with 66 g of pure water, the solvent was removed by concentration under reduced pressure, and 79.2 g of THF and 158 g of IPA were added and heated at 50 ° C., and the crystals were precipitated by cooling with ice and filtered. Crystals were collected. To the obtained crystals, 46.2 g of THF and 92.4 g of MeOH were added and heated at 50 ° C., and the crystals were precipitated by cooling with ice, and filtered and dried to obtain 8.92 g of RM8 (yield: 61% , Properties: white crystals).
¹ H-NMR (400 MHz) in CDCl3: 2.02-1.87 ppm (m, 8H), 2.67-2.60 ppm (m, 2H), 3.15-3.08 ppm (m, 2H), 4.13-4.02 ppm (m, 4H), 4.65-4.60 ppm (m, 2H), 5.66 ppm (s, 2H), 6.25 ppm (d, J = 2.4 Hz, 2H), 6.94 ppm (d, J = 8.8 Hz, 2H), 6.99 ppm (t, J = 8.6 Hz, 1H) 7.28-7.22 ppm (m, 2H), 7.44 ppm (d, J = 8.8 Hz, 2H).

<Synthesis of RM9-A>
In a 300 mL four-necked flask equipped with a magnetic stirrer, 20.0 g (4,7 ') of 4,4′-biphenol, 44.6 g (3.0 eq) of potassium carbonate, and 1.82 g (0. 1 eq) was charged, heated to 100 ° C., and 39.8 g (2.2 eq) of 2-bromomethyl-1,3-dioxolane diluted with 10.0 g of DMF was added dropwise, followed by stirring at the same temperature for 6 hours. After 6 hours, an additional 5.38 g (0.3 eq) of 2-bromomethyl-1,3-dioxolane was added and stirred for 18 hours. After completion of the reaction, the reaction solution was added to 400 g of pure water to precipitate crystals, filtered, and the filtrate was slurry washed with 60.0 g of MeOH and filtered again to obtain a white solid. The obtained white solid was suspended in 500 g of THF, and 1.00 g of activated carbon (brand: special white rice dry product, Nippon Enviro Chemical) was added, stirred at 60 ° C. for 30 minutes, and then filtered while hot (45 ° C.). As a result of the cooling of the filtrate, white crystals were precipitated, and 13.0 g of RM9-A was obtained by filtration and drying (yield: 34%, property: white solid).
¹ H-NMR (400 MHz) in DMSO-d6: 3.85-3.93 ppm (m, 4H), 3.95-3.99 ppm (m, 4H), 4.03 ppm (d, J = 4.0 Hz, 4H), 5.21 ppm (t, J = 4.0 Hz, 2H), 7.01 ppm (d, J = 8.8 Hz, 4H), 7.53 ppm (d, J = 8.4 Hz, 4H).

<Synthesis of RM9>
To a 300 mL four-necked flask equipped with a magnetic stirrer, in 99.5 g of THF, 9.95 g (27.8 mmol) of the compound (RM9-A) obtained above, 11.8 g of ethyl 2- (bromomethyl) acrylate (2 .2 eq), 12.6 g (2.4 eq) of tin chloride, and 34.8 g of a 10 wt% aqueous hydrochloric acid solution were added and stirred at 60 ° C. for 1.5 hours. After 1.5 hours, 9.95 g of a 20 wt% hydrochloric acid aqueous solution was added, and the mixture was further stirred for 21 hours to complete the reaction. Thereafter, THF was distilled off under reduced pressure, 199 g of ethyl acetate was added, and the aqueous phase was removed. Next, the organic layer was washed twice with 59.7 g of pure water. The organic phase was recovered, and ethyl acetate was distilled off under reduced pressure, and then 149 g of THF was added and stirred under reflux. Subsequently, 0.48 g of activated carbon (brand: special white birch dry product manufactured by Nippon Enviro Chemical) was added and stirred for 1 hour, dehydrated with magnesium sulfate, and then filtered to obtain a uniform filtrate. Subsequently, this was concentrated under reduced pressure to make the amount of THF 79.6 g, 159 g of MeOH was added at 55 ° C., and the mixture was stirred for a while on ice. The crystals thus precipitated were filtered and dried to obtain 8.4 g of RM9 (yield: 74%, property: white crystals).
¹ H-NMR (400 MHz) in DMSO-d6: 2.82-2.89 ppm (m, 2H), 3.10-3.18 ppm (m, 2H), 4.14 ppm (dd, J = 5.4 Hz, J = 11.0 Hz, 2H), 4.25 ppm (dd, J = 2.6Hz, J = 11.0 Hz, 2H), 5.78-5.79 ppm (m, 2H), 6.10-6.08 ppm (m, 2H), 7.00 ppm (d, J = 8.4 Hz, 4H) , 7.55 ppm (d, J = 8.4 Hz).

<Synthesis of RM10-A>
In a 200 mL four-necked flask equipped with a magnetic stirrer, 10.0 g (53.7 mmol) of 4,4′-biphenol, 18.4 g (2.2 eq) of 4-chlorobutyraldehyde dimethylacetal in 20.0 g of NMP, carbonic acid, Potassium 22.3 g (3.0 eq) and potassium iodide 1.78 g (0.2 eq) were charged and stirred at 80 ° C. for 3 hours. Thereafter, 2.45 g (0.3 eq) of 4-chlorobutyraldehyde dimethyl acetal was added, and the mixture was further stirred for 16 hours. After the reaction, the reaction solution was diluted with 50.0 g of ethyl acetate, the inorganic salt was filtered off, and the filtrate was diluted with 50.0 g of ethyl acetate, which was washed 3 times with 50.0 g of pure water at 50 ° C. . Thereafter, this organic phase was dehydrated with sodium sulfate, concentrated under reduced pressure to a total weight of 68.0 g, and the precipitated crystals were filtered. To the crude product, 5.0 g of THF and 20.0 g of MeOH were added and dissolved at 50 ° C., then cooled and stirred for a while. The precipitated crystals were filtered and dried to obtain 15.8 g of RM10-A (yield: 70%, property: white solid).
¹ H-NMR (400 MHz) in DMSO-d6: 1.66-1.75 ppm (m, 8H), 3.24 ppm (s, 12H), 4.00 ppm (t, J = 6.2 Hz, 4H), 4.42 ppm (t, J = 5.2 Hz, 2H), 6.97 ppm (d, J = 8.8 Hz, 4H), 7.52 ppm (d, J = 8.4 Hz, 4H).

<Synthesis of RM10>
In a 500 mL four-necked flask equipped with a magnetic stirrer, 14.8 g (35.4 mmol) of the compound (RM10-A) obtained above in 56.4 g of THF, 15.0 g of ethyl 2- (bromomethyl) acrylate (2 .2 eq), 16.1 g (2.4 eq) of tin chloride, 0.39 g (5 mol%) of 2,6-di-tert-butyl-p-cresol, 51.8 g of 20 wt% aqueous HCl solution, and 3 at 60 ° C. Stir for hours. After the reaction, the reaction solution was concentrated under reduced pressure, 148 g of pure water was added, and the precipitated crystals were filtered and washed twice with 148 g of pure water. Subsequently, 118 g of THF and 118 g of MeOH were added to the crystals and dissolved at 50 ° C., then allowed to cool to room temperature and stirred for a while. A crude product was obtained by filtering the crystals thus obtained. Further, 237 g of THF and 237 g of IPA were added to this crude product and dissolved at 60 ° C., and then cooled to room temperature and stirred for a while. The crystals thus precipitated were filtered, washed 3 times with 74.0 g of THF, and then dried under reduced pressure to obtain 7.20 g of RM10 (yield: 44%, properties: white crystals).
¹ H-NMR (400 MHz) in DMSO-d6: 1.75-1.85 ppm (m, 8H), 2.60-2.68 ppm (m, 2H), 3.08-3.15 ppm (m, 2H), 4.03 ppm (t, J = 5.2 Hz, 4H), 4.61-4.67 ppm (m, 2H) 5.72-5.73 ppm (m, 2H), 6.04-6.05 ppm (m, 2H), 6.98 ppm (d, J = 8.8 Hz, 4H), 7.52 ppm ( d, J = 8.8 Hz, 4H).

<Synthesis Example 11 -Synthesis of Liquid Crystal Alignment Agent D1->
BODA (2.00 g, 8.0 mmol), DA-2 (2.40 g, 6.0 mmol), DA-4 (0.94 g, 6.2 mmol), DA-6 (1.77 g, 3.8 mmol), DA-8 (1.32 g, 4.0 mmol) was dissolved in NMP (32.2 g), reacted at 60 ° C. for 3 hours, and then CBDA (2.27 g, 11.6 mmol) and NMP (10. 7 g) was added and reacted at room temperature for 10 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (50 g) and diluting to 6% by mass, acetic anhydride (5.7 g) and pyridine (2.9 g) were added as imidization catalysts, and the mixture was reacted at 50 ° C. for 3 hours. This reaction solution was poured into methanol (700 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (A) -1. The imidation ratio of this polyimide was 60%, the number average molecular weight was 12000, and the weight average molecular weight was 33000.
NMP (44.0 g) was added to the obtained polyimide powder (A) -1 (6.0 g), and dissolved by stirring at 50 ° C. for 5 hours. 3AMP (1 wt% NMP solution) 6.0g, NMP (14.0g), and BCS (30.0g) were added to this solution, and the liquid crystal aligning agent D1 was obtained by stirring at room temperature for 5 hours.

<Synthesis Example 12 -Synthesis of Liquid Crystal Alignment Agent D2->
BODA (2.00 g, 8.0 mmol), DA-8 (3.30 g, 10.0 mmol), DA-2 (4.00 g, 10.0 mmol) were dissolved in NMP (34.8 g) at 60 ° C. Then, CBDA (2.27 g, 11.6 mmol) and NMP (11.6 g) were added and reacted at room temperature for 10 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (50 g) and diluting to 6% by mass, acetic anhydride (5.3 g) and pyridine (2.7 g) were added as imidization catalysts, and the mixture was reacted at 50 ° C. for 3 hours. This reaction solution was poured into methanol (700 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (A) -2. The imidation ratio of this polyimide was 60%, the number average molecular weight was 15000, and the weight average molecular weight was 41000.
NMP (44.0 g) was added to the obtained polyimide powder (A) -2 (6.0 g), and the mixture was dissolved by stirring at 50 ° C. for 5 hours. To this solution, 6.0 g of 3AMP (1 wt% NMP solution), NMP (14.0 g), and BCS (30.0 g) were added and stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent D2.

<Synthesis Example 13 -Synthesis of Liquid Crystal Alignment Agent D3->
BODA (2.00 g, 8.0 mmol), DA-6 (4.67 g, 10.0 mmol), DA-2 (4.00 g, 10.0 mmol) were dissolved in NMP (38.9 g) at 60 ° C. Then, CBDA (2.27 g, 11.6 mmol) and NMP (13.0 g) were added and reacted at room temperature for 10 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (50 g) and diluting to 6% by mass, acetic anhydride (3.1 g) and pyridine (12.1 g) were added as an imidization catalyst, and the mixture was reacted at 50 ° C. for 3 hours. This reaction solution was poured into methanol (700 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (A) -3. The imidation ratio of this polyimide was 60%, the number average molecular weight was 15000, and the weight average molecular weight was 36000.
NMP (44.0 g) was added to the obtained polyimide powder (A) -3 (6.0 g) and dissolved by stirring at 50 ° C. for 5 hours. 3AMP (1 wt% NMP solution) 6.0g, NMP (14.0g), and BCS (30.0g) were added to this solution, and the liquid crystal aligning agent D3 was obtained by stirring at room temperature for 5 hours.

<Synthesis Example 14 -Synthesis of Liquid Crystal Alignment Agent D4->
BODA (2.00 g, 8.0 mmol), DA-7 (2.64 g, 10.0 mmol), DA-2 (4.00 g, 10.0 mmol) were dissolved in NMP (32.8 g) at 60 ° C. Then, CBDA (2.27 g, 11.6 mmol) and NMP (10.9 g) were added and reacted at room temperature for 10 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (50 g) and diluting to 6% by mass, acetic anhydride (3.7 g) and pyridine (14.4 g) were added as imidization catalysts, and the mixture was reacted at 50 ° C. for 3 hours. This reaction solution was poured into methanol (700 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (A) -4. The imidation ratio of this polyimide was 60%, the number average molecular weight was 25000, and the weight average molecular weight was 45000.
NMP (44.0 g) was added to the obtained polyimide powder (A) -4 (6.0 g) and dissolved by stirring at 50 ° C. for 5 hours. 3AMP (1 wt% NMP solution) 6.0g, NMP (14.0g), and BCS (30.0g) were added to this solution, and the liquid crystal aligning agent D4 was obtained by stirring at room temperature for 5 hours.

<Synthesis Example 15 -Synthesis of Liquid Crystal Alignment Agent D5->
TCA (1.35 g, 6.0 mmol), DA-1 (2.28 g, 6.0 mmol), DA-8 (2.97 g, 9.0 mmol) were dissolved in NMP (24.9 g) at 80 ° C. Then, CBDA (1.74 g, 8.9 mmol) and NMP (8.3 g) were added and reacted at room temperature for 10 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (36 g) and diluting to 6% by mass, acetic anhydride (4.0 g) and pyridine (2.1 g) were added as an imidization catalyst, and the mixture was reacted at 50 ° C. for 3 hours. This reaction solution was poured into methanol (700 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (A) -5. The imidation ratio of this polyimide was 60%, the number average molecular weight was 20000, and the weight average molecular weight was 43,000.
NMP (44.0 g) was added to the obtained polyimide powder (A) -5 (6.0 g) and dissolved by stirring at 50 ° C. for 5 hours. 3AMP (1 wt% NMP solution) 6.0g, NMP (14.0g), and BCS (30.0g) were added to this solution, and the liquid crystal aligning agent D5 was obtained by stirring at room temperature for 5 hours.

<Synthesis Example 16 -Synthesis of Liquid Crystal Alignment Agent D6->
BODA (2.00 g, 8.0 mmol), DA-8 (4.63 g, 14.0 mmol), DA-3 (2.61 g, 6.0 mmol) were dissolved in NMP (34.5 g) at 60 ° C. Then, CBDA (2.27 g, 11.6 mmol) and NMP (11.5 g) were added and reacted at room temperature for 10 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (50 g) and diluting to 6% by mass, acetic anhydride (5.3 g) and pyridine (2.7 g) were added as imidization catalysts, and the mixture was reacted at 50 ° C. for 3 hours. This reaction solution was poured into methanol (700 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (A) -6. The imidation ratio of this polyimide was 60%, the number average molecular weight was 17000, and the weight average molecular weight was 35000.
NMP (44.0 g) was added to the obtained polyimide powder (A) -6 (6.0 g), and dissolved by stirring at 50 ° C. for 5 hours. 3AMP (1 wt% NMP solution) 6.0g, NMP (14.0g), and BCS (30.0g) were added to this solution, and the liquid crystal aligning agent D6 was obtained by stirring at room temperature for 5 hours.

<Synthesis Example 17 -Synthesis of Liquid Crystal Alignment Agent D7->
BODA (1.30 g, 5.2 mmol), DA-9 (2.09 g, 3.9 mmol), DA-8 (3.00 g, 9.1 mmol) were dissolved in NMP (23.5 g) at 60 ° C. Then, CBDA (1.43 g, 7.3 mmol) and NMP (7.8 g) were added and reacted at room temperature for 10 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (36 g) and diluting to 6% by mass, acetic anhydride (3.6 g) and pyridine (1.9 g) were added as imidization catalysts, and the mixture was reacted at 50 ° C. for 3 hours. This reaction solution was poured into methanol (700 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (A) -7. The imidation ratio of this polyimide was 60%, the number average molecular weight was 16000, and the weight average molecular weight was 36000.
NMP (44.0 g) was added to the obtained polyimide powder (A) -7 (6.0 g), and the mixture was dissolved by stirring at 50 ° C. for 5 hours. 3AMP (1 wt% NMP solution) 6.0g, NMP (14.0g), and BCS (30.0g) were added to this solution, and the liquid crystal aligning agent D7 was obtained by stirring at room temperature for 5 hours.

<Synthesis Example 18 -Synthesis of Liquid Crystal Alignment Agent D8->
BODA (2.00 g, 8.0 mmol), DA-8 (3.96 g, 12.0 mmol), DA-1 (3.04 g, 8.0 mmol) were dissolved in NMP (33.9 g) at 60 ° C. Then, CBDA (2.27 g, 11.6 mmol) and NMP (11.3 g) were added and reacted at room temperature for 10 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (50 g) and diluting to 6% by mass, acetic anhydride (5.4 g) and pyridine (2.8 g) were added as imidation catalysts, and the mixture was reacted at 50 ° C. for 3 hours. This reaction solution was poured into methanol (700 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (A) -8. The imidation ratio of this polyimide was 60%, the number average molecular weight was 18000, and the weight average molecular weight was 40000.
NMP (44.0 g) was added to the obtained polyimide powder (A) -8 (6.0 g), and dissolved by stirring at 50 ° C. for 5 hours. 3AMP (1 wt% NMP solution) 6.0g, NMP (14.0g), and BCS (30.0g) were added to this solution, and the liquid crystal aligning agent D8 was obtained by stirring at room temperature for 5 hours.

<Synthesis Example 19 -Synthesis of Liquid Crystal Alignment Agent D9->
BODA (2.00 g, 8.0 mmol), DA-1 (2.28 g, 6.0 mmol), DA-4 (1.22 g, 8.0 mmol), DA-5 (1.45 g, 6.0 mmol). After dissolving in NMP (29.5 g) and reacting at 60 ° C. for 3 hours, PMDA (2.53 g, 11.6 mmol) and NMP (9.5 g) were added, and the mixture was reacted at room temperature for 10 hours to obtain a polyamic acid solution Got.
After adding NMP to this polyamic acid solution (50 g) and diluting to 6% by mass, acetic anhydride (6.4 g) and pyridine (3.3 g) were added as imidization catalysts, and the mixture was reacted at 50 ° C. for 3 hours. This reaction solution was poured into methanol (700 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (A) -9. The imidation ratio of this polyimide was 60%, the number average molecular weight was 10,000, and the weight average molecular weight was 31000.
NMP (44.0 g) was added to the obtained polyimide powder (A) -9 (6.0 g), and the mixture was dissolved by stirring at 50 ° C. for 5 hours. 3AMP (1 wt% NMP solution) 6.0g, NMP (14.0g), and BCS (30.0g) were added to this solution, and the liquid crystal aligning agent D9 was obtained by stirring at room temperature for 5 hours.

<Synthesis Example 20 -Synthesis of Liquid Crystal Alignment Agent D10->
By adding 3.0 g of the liquid crystal aligning agent D9 obtained in Synthesis Example 19 to 7.0 g of the liquid crystal aligning agent D8 obtained in Synthesis Example 18, the liquid crystal aligning agent D10 is obtained by stirring at room temperature for 5 hours. It was.

<Synthesis Example 21 -Synthesis of Liquid Crystal Alignment Agent D11->
BODA (2.00 g, 8.0 mmol), DA-1 (1.52 g, 4.0 mmol), DA-4 (1.22 g, 8.0 mmol), DA-8 (2.64 g, 8.0 mmol). After dissolving in NMP (20.7 g) and reacting at 60 ° C. for 3 hours, PMDA (2.53 g, 11.6 mmol) and NMP (9.9 g) were added, and the mixture was reacted at room temperature for 10 hours to obtain a polyamic acid solution Got.
After adding NMP to this polyamic acid solution (50 g) and diluting to 6% by mass, acetic anhydride (6.1 g) and pyridine (3.2 g) were added as an imidization catalyst, and the mixture was reacted at 50 ° C. for 3 hours. This reaction solution was poured into methanol (700 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (A) -10. The imidation ratio of this polyimide was 60%, the number average molecular weight was 9000, and the weight average molecular weight was 25000.
NMP (44.0 g) was added to the resulting polyimide powder (A) -10 (6.0 g), and dissolved by stirring at 50 ° C. for 5 hours. 3AMP (1 wt% NMP solution) 6.0g, NMP (14.0g), and BCS (30.0g) were added to this solution, and the liquid crystal aligning agent D11 was obtained by stirring at room temperature for 5 hours.

<Synthesis Example 22 -Synthesis of Liquid Crystal Alignment Agent D12->
By adding 3.0 g of the liquid crystal aligning agent D11 obtained in Synthesis Example 21 to 7.0 g of the liquid crystal aligning agent D8 obtained in Synthesis Example 18, the liquid crystal aligning agent D12 is obtained by stirring at room temperature for 5 hours. It was.

<Synthesis Example 23 -Synthesis of Liquid Crystal Alignment Agent D13->
BODA (3.75 g, 15.0 mmol), DA-1 (3.81 g, 10.0 mmol), DA-4 (1.52 g, 10.0 mmol) were dissolved in NMP (30.0 g) and dissolved at 80 ° C. Then, CBDA (0.94 g, 4.8 mmol) and NMP (10.0 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% by mass, acetic anhydride (4.7 g) and pyridine (3.7 g) were added as imidation catalysts, and the mixture was reacted at 80 ° C. for 3 hours. This reaction solution was poured into methanol (700 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (A) -11. The imidation ratio of this polyimide was 55%, the number average molecular weight was 20000, and the weight average molecular weight was 40000.
NMP (44.0 g) was added to the obtained polyimide powder (A) -11 (6.0 g), and dissolved by stirring at 50 ° C. for 5 hours. 3AMP (1 wt% NMP solution) 6.0g, NMP (14.0g), and BCS (30.0g) were added to this solution, and the liquid crystal aligning agent D13 was obtained by stirring at room temperature for 5 hours.

<Synthesis Example 24 -Synthesis of Liquid Crystal Alignment Agent D14->
BODA (2.00 g, 8.0 mmol), DA-6 (6.53 g, 14.0 mmol), DA-2 (2.40 g, 6.0 mmol) were dissolved in NMP (26.4 g) at 60 ° C. Then, CBDA (2.27 g, 11.6 mmol) and NMP (13.2 g) were added and reacted at room temperature for 10 hours to obtain a polyamic acid solution. The number average molecular weight of this polyamic acid solution was 20000, and the weight average molecular weight was 40000.
NMP (40.0g) and BCS (30.0g) were added to this polyamic acid solution (30g), and the liquid crystal aligning agent D14 was obtained by stirring at room temperature for 5 hours.

<Synthesis of RM11-A>
A 300 ml four-necked flask equipped with a magnetic stirrer was charged with 9.0 g (44.1 mmol) of RM1-A in 18.1 g of NMP, washed with 17.9 g of NMP, and then 18.3 g of potassium carbonate (3. 0 eq) was added and co-washed with 18.0 g NMP. While this was stirred at 80 ° C., 17.6 g (2.2 eq) of 2- (2-bromoethyl) -1,3-dioxolane was added dropwise over 30 minutes, and then stirred for 18 hours. After 18 hours, an additional 2.4 g (0.3 eq) of 2- (2-bromoethyl) -1,3-dioxolane was added, and the reaction was further continued for 3.5 hours, confirming the disappearance of the intermediate. After completion of the reaction, a large amount of water was added to the reaction solution at room temperature, and crystals of the target product were precipitated while dissolving potassium carbonate, followed by filtration. The recovered crystals were washed twice with pure water and filtered and dried to obtain 17.8 g of a crude product of RM11-A (yield: 100%, properties: light brown crystals).
¹ H-NMR (400 MHz) in DMSO-d ₆ : 7.57 ppm (d, J = 8.8 Hz, 2H), 7.49 ppm (dd, J = 2.2 Hz, J = 13.0 Hz, 1H), 7.38 ppm (d, J = 10.0Hz, 1H), 7.21ppm (t, J = 8.8Hz, 1H), 6.99ppm (d, J = 8.4Hz, 2H), 5.02-4.99ppm (m, 2H), 4.18ppm (t, J = 6.6Hz, 2H), 4.10ppm (t, J = 6.6Hz, 2H), 3.94-3.91ppm (m, 4H), 3.82-3.78ppm (m, 4H), 2.09-2.02ppm (m, 4H).

<Synthesis of RM11>
In a 500 ml four-necked flask equipped with a magnetic stirrer, 15.0 g (37.1 mmol) of RM11-A, 16.9 g (2.4 eq) of tin (II) chloride anhydride, 2- (bromomethyl) acrylic acid in 135 g of THF After adding 15.9 g (2.2 eq) of ethyl, 52.5 g of 10 wt% aqueous HCl solution was added dropwise at 20-30 ° C. over 45 minutes. Then, it stirred at room temperature for 7 days and the raw material and the intermediate body were lose | disappeared. Next, 300 g of toluene was added to the reaction solution to separate it into two phases, and the hydrochloric acid phase was removed by hot separation (50 ° C.). The organic phase was once recovered in a flask and dropped into a jacketed separable flask with 300 g of 6 wt% KOH aqueous solution and stirred at 50 ° C. Since insoluble matter was generated at the interface, 150 g of 6 wt% KOH aqueous solution was added. Next, after removing the alkali phase, the organic phase was washed three times with 300 g of pure water, and then the organic phase was recovered. To this was added 0.75 g of activated carbon (brand: special white birch dry product manufactured by Nippon Enviro Chemical), 30.0 g of sodium sulfate, and 105 g of THF, and the mixture was stirred at room temperature for 30 minutes, followed by solid-liquid separation, and the filtrate was collected. This was concentrated to dryness, 45.0 g of MeOH was added, and the slurry was washed at room temperature for 1 hour. After filtration, the obtained residue was washed with 7.5 g of MeOH and then dried under reduced pressure to obtain 7.6 g of RM11 (yield: 45%, property: white crystals).
¹ H-NMR (400 MHz) in DMSO-d ₆ : 7.59 ppm (d, J = 8.8 Hz, 2H), 7.51 ppm (dd, J = 2.0 Hz, J = 12.8 Hz, 1H), 7.40 ppm (dd, J = 1.6 Hz, J = 8.0 Hz, 1H), 7.34 ppm (t, J = 9.0 Hz, 1H), 7.01 ppm (d, J = 8.8 Hz, 2H), 6.05 ppm (dd, J = 2.6 Hz, J = 5.0Hz, 2H), 5.74ppm (d, J = 2.0Hz, 2H), 4.81-4.75ppm (m, 2H), 4.20ppm (t, J = 6.2Hz, 2H), 4.13ppm (t, J = 6.2 Hz, 2H), 3.21-3.12ppm (m, 2H), 2.79-2.71ppm (m, 2H), 2.17-2.08ppm (m, 4H).

0.06 g (10% by mass based on solid content) of the polymerizable compound RM1 obtained in Synthesis Example 1 is added to 10.0 g of the liquid crystal aligning agent D1 obtained in Synthesis Example 11, and the mixture is stirred at room temperature for 3 hours. And dissolved to prepare liquid crystal aligning agent D15.
When the obtained liquid crystal aligning agent D15 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.

In Example 1, liquid crystal aligning agent D16 was prepared by the method similar to Example 1 except the quantity of polymeric compound RM1 having been 0.09g (15 mass% with respect to solid content).
When the obtained liquid crystal aligning agent D16 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.

In Example 1, a liquid crystal aligning agent D17 was prepared in the same manner as in Example 1 except that the polymerizable compound RM2 obtained in Synthesis Example 2 was used instead of the polymerizable compound RM1.
When the obtained liquid crystal aligning agent D17 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.

In Example 2, a liquid crystal aligning agent D18 was prepared in the same manner as in Example 2, except that the polymerizable compound RM2 obtained in Synthesis Example 2 was used instead of the polymerizable compound RM1.
When the obtained liquid crystal aligning agent D18 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.

In Example 1, a liquid crystal aligning agent D19 was prepared in the same manner as in Example 1 except that the polymerizable compound RM3 obtained in Synthesis Example 3 was used instead of the polymerizable compound RM1.
When the obtained liquid crystal aligning agent D19 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.

In Example 2, a liquid crystal aligning agent D20 was prepared in the same manner as in Example 2, except that the polymerizable compound RM3 obtained in Synthesis Example 3 was used instead of the polymerizable compound RM1.
When the obtained liquid crystal aligning agent D20 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.

In Example 1, a liquid crystal aligning agent D21 was prepared in the same manner as in Example 1 except that the polymerizable compound RM4 obtained in Synthesis Example 4 was used instead of the polymerizable compound RM1.
When the obtained liquid crystal aligning agent D21 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.

In Example 2, a liquid crystal aligning agent D22 was prepared in the same manner as in Example 2, except that the polymerizable compound RM4 obtained in Synthesis Example 4 was used instead of the polymerizable compound RM1.
When the obtained liquid crystal aligning agent D22 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.

In Example 1, a liquid crystal aligning agent D23 was prepared in the same manner as in Example 2 except that the liquid crystal aligning agent D2 obtained in Synthesis Example 12 was used instead of the liquid crystal aligning agent D1.
When the obtained liquid crystal aligning agent D23 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.

In Example 1, a liquid crystal aligning agent D24 was prepared in the same manner as in Example 2, except that the liquid crystal aligning agent D3 obtained in Synthesis Example 13 was used instead of the liquid crystal aligning agent D1.
When the obtained liquid crystal aligning agent D24 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.

In Example 1, a liquid crystal aligning agent D25 was prepared in the same manner as in Example 2 except that the liquid crystal aligning agent D4 obtained in Synthesis Example 14 was used instead of the liquid crystal aligning agent D1.
When the obtained liquid crystal aligning agent D25 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.

In Example 1, a liquid crystal aligning agent D26 was prepared in the same manner as in Example 2 except that the liquid crystal aligning agent D5 obtained in Synthesis Example 15 was used instead of the liquid crystal aligning agent D1.
When the obtained liquid crystal aligning agent D26 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.

In Example 1, a liquid crystal aligning agent D27 was prepared in the same manner as in Example 2, except that the liquid crystal aligning agent D6 obtained in Synthesis Example 16 was used instead of the liquid crystal aligning agent D1.
When the obtained liquid crystal aligning agent D27 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.

In Example 1, a liquid crystal aligning agent D28 was prepared in the same manner as in Example 2 except that the liquid crystal aligning agent D7 obtained in Synthesis Example 17 was used instead of the liquid crystal aligning agent D1.
When the obtained liquid crystal aligning agent D28 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.

In Example 1, the liquid crystal aligning agent D29 was prepared by the same method as Example 2 except having used the liquid crystal aligning agent D10 obtained by the synthesis example 20 instead of the liquid crystal aligning agent D1.
When the obtained liquid crystal aligning agent D29 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.

In Example 1, a liquid crystal aligning agent D30 was prepared in the same manner as in Example 2, except that the liquid crystal aligning agent D12 obtained in Synthesis Example 22 was used instead of the liquid crystal aligning agent D1.
When the obtained liquid crystal aligning agent D30 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.

In Example 1, a liquid crystal aligning agent D31 was prepared in the same manner as in Example 2, except that the liquid crystal aligning agent D13 obtained in Synthesis Example 23 was used instead of the liquid crystal aligning agent D1.
When the obtained liquid crystal aligning agent D31 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.

In Example 1, a liquid crystal aligning agent D32 was prepared in the same manner as in Example 2, except that the liquid crystal aligning agent D14 obtained in Synthesis Example 24 was used instead of the liquid crystal aligning agent D1.
When the obtained liquid crystal aligning agent D32 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.

In Example 1, a liquid crystal aligning agent D33 was prepared in the same manner as in Example 1 except that the polymerizable compound RM7 obtained in Synthesis Example 7 was used instead of the polymerizable compound RM1.
When the obtained liquid crystal aligning agent D33 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.

In Example 1, a liquid crystal aligning agent D34 was prepared in the same manner as in Example 1 except that the polymerizable compound RM8 obtained in Synthesis Example 8 was used instead of the polymerizable compound RM1.
When the obtained liquid crystal aligning agent D34 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.

(Comparative Example 1)
In Example 1, a liquid crystal aligning agent D35 was prepared in the same manner as in Example 1 except that the polymerizable compound RM5 obtained in Synthesis Example 5 was used instead of the polymerizable compound RM1.
When the obtained liquid crystal aligning agent D35 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.

(Comparative Example 2)
In Example 2, a liquid crystal aligning agent D36 was prepared in the same manner as in Example 2 except that the polymerizable compound RM5 obtained in Synthesis Example 5 was used instead of the polymerizable compound RM1.
The obtained liquid crystal aligning agent D36 was stored in a freezer at −20 ° C. for 1 day, and left to stand at room temperature for 3 hours to thaw, and precipitates were confirmed.

(Comparative Example 3)
In Example 1, a liquid crystal aligning agent D37 was prepared in the same manner as in Example 1 except that the polymerizable compound RM6 obtained in Synthesis Example 6 was used instead of the polymerizable compound RM1.
The obtained liquid crystal aligning agent D37 was stored in a freezer at −20 ° C. for 1 day, and allowed to stand at room temperature for 3 hours to thaw, and precipitates were confirmed.

(Comparative Example 4)
In Example 2, a liquid crystal aligning agent D38 was prepared in the same manner as in Example 2, except that the polymerizable compound RM6 obtained in Synthesis Example 6 was used instead of the polymerizable compound RM1.
The obtained liquid crystal aligning agent D38 was stored in a freezer at −20 ° C. for 1 day, and allowed to stand at room temperature for 3 hours to thaw, and precipitates were confirmed.

(Comparative Example 5)
In Example 1, a liquid crystal aligning agent D39 was prepared in the same manner as in Example 1 except that the polymerizable compound RM9 obtained in Synthesis Example 9 was used instead of the polymerizable compound RM1.
When the obtained liquid crystal aligning agent D39 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.

(Comparative Example 6)
In Example 1, a liquid crystal aligning agent D40 was prepared in the same manner as in Example 1 except that the polymerizable compound RM10 obtained in Synthesis Example 10 was used instead of the polymerizable compound RM1.
When the obtained liquid crystal aligning agent D40 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.

<Production of liquid crystal cell>
Using the liquid crystal aligning agent D15 obtained in Example 1, an SC-PVA liquid crystal cell was prepared according to the following procedure.
The liquid crystal aligning agent D15 obtained in Example 1 was spin-coated 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 was formed, and then heated at 80 ° C. After drying on a plate for 90 seconds, baking was performed in a hot air circulation oven at 200 ° C. for 30 minutes to form a liquid crystal alignment film having a thickness of 100 nm.
Further, after spin-coating the liquid crystal aligning agent D1 on the ITO surface on which 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 200 ° C. A 100 nm liquid crystal alignment film was formed.
After spraying 4 μm bead spacers on the liquid crystal alignment film of one of the two substrates, a sealant (solvent type thermosetting epoxy resin) 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. Liquid crystal MLC-6608 (trade name, manufactured by Merck & Co., Inc.) was injected into this empty cell by a reduced pressure injection method to produce a liquid crystal cell. The produced liquid crystal cell was then placed in a 120 ° C. hot-air circulating oven for 1 hour to realign the liquid crystal.

The response speed of the obtained liquid crystal cell was measured by the following method. Thereafter, with a DC voltage of 15 V applied to the liquid crystal cell, UV was applied from the outside of the liquid crystal cell through a 365 nm bandpass filter at 10 J / cm ² . Thereafter, the response speed was measured again, and the response speed before and after UV irradiation was compared.
Further, the pretilt angle of the pixel portion of the cell after UV irradiation was measured.
Further, the cell not irradiated with UV was left for one day, and then the liquid crystal cell was observed with a polarizing microscope. When the solubility of the polymerizable compound in the liquid crystal is low, it is likely to precipitate in the liquid crystal cell and a bright spot is generated. The results are shown in Table 2.

<Measurement method of response speed>
First, a liquid crystal cell was arranged between a pair of polarizing plates in a measuring apparatus configured in the order of a backlight, a pair 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 with a voltage of ± 6 V and a frequency of 1 kHz is applied to the liquid crystal cell, and the change until the luminance observed by the light quantity detector is saturated is captured by an oscilloscope. The luminance when no voltage is applied is obtained. A voltage of 0% and ± 4 V was applied, the saturated luminance value was set to 100%, and the time taken for the luminance to change from 10% to 90% was defined as the response speed.
<Measurement of pretilt angle>
An LCD analyzer LCA-LUV42A manufactured by Meiryo Technica was used.

(Examples 22 to 40)
Instead of the liquid crystal aligning agent D15, the same operation as in Example 21 was performed except that the liquid crystal aligning agent described in Table 1 was used, and the response speed before and after UV irradiation was compared. In addition, the pretilt angle was measured and the bright spots in the liquid crystal cell were observed.
In Examples 23, 24, 27 and 28, a hot air circulation oven at 140 ° C. was used instead of the hot air circulation oven at 200 ° C.

(Example 41)
The liquid crystal aligning agent D9 (3.0 g) obtained in Synthesis Example 19 is added to the liquid crystal aligning agent D8 (7.0 g) obtained in Synthesis Example 18, and the liquid crystal aligning agent is stirred at room temperature for 5 hours. 10.0 g of D10 was prepared. To this liquid crystal aligning agent D10 (10.0 g), 0.06 g of RM11 synthesized in Synthesis Example 25 (10% by mass with respect to the solid content of the liquid crystal aligning agent D10) is added and stirred for 3 hours to dissolve. A liquid crystal aligning agent D41 was prepared.
When the obtained liquid crystal aligning agent D41 was stored in a freezer at −20 ° C. for 1 day and allowed to thaw for 3 hours at room temperature, no precipitate was confirmed.

(Example 42)
The liquid crystal aligning agent D41 prepared in Example 41 was subjected to the same operation as in Example 21, and the response speed before and after UV irradiation was compared. In addition, the pretilt angle was measured and the bright spots in the liquid crystal cell were observed.

(Comparative Examples 7 to 12)
The response speed before and after UV irradiation was compared by performing the same operation as in Example 21 except that the liquid crystal aligning agents D35 to D40 were used instead of the liquid crystal aligning agent D15. In addition, the pretilt angle was measured and the bright spots in the liquid crystal cell were observed.

When Examples 21 and 22 are compared with Comparative Examples 7 and 8, particularly when Example 22 and Comparative Example 8 are compared, when the same skeleton is present (RM1 and RM5 have F substitution (RM1) / none (Difference in (RM5)), it can be seen that the introduction of a halogen group improves the solubility in varnish. In addition, the observation of the bright spot in the liquid crystal cell shows that the solubility of the polymerizable compound in the liquid crystal is also improved.
From the same viewpoint, Example 39 and Comparative Example 11 (RM7 and RM9 are different in F substitution (RM7) / No (RM9)), Example 40 and Comparative Example 12 (RM8 and RM10 are F Comparison of the presence of substitution (RM8) and absence (RM10)) shows that the solubility of the polymerizable compound in the liquid crystal is improved by observation of the bright spot in the liquid crystal cell.

Further, from Example 25 and Example 26, even when the terphenyl skeleton is rigid and less soluble than the biphenyl skeleton, the introduction of the halogen group improves the solubility of the polymerizable compound in the liquid crystal aligning agent. It can be confirmed that the storage stability of the liquid crystal aligning agent is also improved.
Similarly, from Examples 23, 24, 27, and 28, high solubility of the polymerizable compound in the liquid crystal aligning agent was confirmed.
Therefore, it is understood that the halogen-substituted polymerizable compound improves the solubility of the polymerizable compound in the liquid crystal aligning agent, the liquid crystal aligning agent exhibits high storage stability, and further improves the solubility in the liquid crystal. .

Furthermore, a liquid crystal aligning agent to which a halogen-substituted polysynthetic compound is added can exhibit a tilt angle in a SC-PVA liquid crystal cell in the same manner as a liquid crystal aligning agent to which a non-halogen-substituted polymerizable compound is added. confirmed.

Claims

[I] The following general formulas I-1 to I-3
(Wherein Ar 1 to Ar 3 are each independently a divalent organic group containing an aromatic ring having at least one halogen substituent, and n 1 , n 2 and n 6 are each independently N represents an integer of 0 to 6, n 3 , n 4 and n 5 each independently represents an integer of 1 to 6, and R 1 to R 3 each independently represent hydrogen or a straight chain of 1 to 4 carbon atoms or At least one polymerizable compound selected from the group consisting of compounds represented by the following formula: and [II] at least one polymer selected from polyimide precursors and polyimides;
Liquid crystal aligning agent containing.
Ar 1 to Ar 3 are each independently represented by the following formulas IB-1 to IB-3 (wherein X represents a halogen group, m 1 to m 8 are each independently an integer, and m 1 + m 2 is 1) 2. The divalent group selected from the group consisting of 8 or less, m 3 + m 4 + m 5 is 1 or more and 10 or less, and m 6 + m 7 + m 8 is 1 or more and 12 or less. Liquid crystal aligning agent.
The group represented by the formula IB-1 is a group represented by the following formula IB-1a, and the group represented by the formula IB-2 is a group represented by the following formula IB-2a. The liquid crystal aligning agent according to claim 2, wherein the group represented by the formula IB-3 is a group represented by the following formula IB-3a.
4. The liquid crystal aligning agent according to claim 1, wherein the [II] polymer has (I) a side chain for vertically aligning liquid crystals.
The liquid crystal aligning agent according to claim 4, wherein the [II] polymer further has (II) a photoreactive side chain.
A liquid crystal alignment film formed with the liquid crystal aligning agent according to any one of claims 1 to 5.
A liquid crystal display element having the liquid crystal alignment film according to claim 6.