JP6249197B2 - Diamine compound - Google Patents

Description

  The present invention relates to a liquid crystal aligning agent, a liquid crystal aligning agent, a liquid crystal aligning film, a liquid crystal display element, and a diamine compound.

  In a liquid crystal display element that responds by an electric field to liquid crystal molecules that are aligned perpendicular to the substrate (also referred to as a vertical alignment method), ultraviolet light is applied while applying a voltage to the liquid crystal molecules during the manufacturing process. Some include processes.

  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 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.

  In this PSA type liquid crystal display element, there is a problem that the polymerizable compound added to the liquid crystal is low in solubility, and precipitates at a low temperature when the addition amount is increased. On the other hand, when the addition amount of the polymerizable compound is reduced, a good alignment state cannot be obtained. Moreover, since the unreacted polymerizable compound remaining in the liquid crystal becomes an impurity (contamination) in the liquid crystal, there is a problem that the reliability of the liquid crystal display element is lowered. In addition, when the UV irradiation treatment necessary in the PSA mode is large, the components in the liquid crystal are decomposed and the reliability is lowered.

  Here, it has been reported that the response speed of the liquid crystal display element is increased by adding the 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).

JP 2003-307720 A

K. Hanaoka, SID 04 DIGEST, P.1200-1202 K.H Y.-J.Lee, SID 09 DIGEST, P.666-668

  In such an SC-PVA mode, a liquid crystal aligning agent to which a photopolymerizable compound is added is used. However, since the photopolymerizable compound is not so soluble in the liquid crystal aligning agent, the photopolymerization added to the liquid crystal aligning agent. When the addition amount of the functional compound is increased, the storage stability of the liquid crystal aligning agent is adversely affected. Further, when the unreacted photopolymerizable compound dissolves into the liquid crystal from the liquid crystal alignment film, it becomes an impurity and causes a decrease in the reliability of the liquid crystal display element.

  An object of the present invention is to solve the above-mentioned problems of the prior art, and a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal that can improve the response speed of a liquid crystal display element without adding a photopolymerizable compound. It is providing a display element and a diamine compound.

  As a result of intensive studies to solve the above problems, the inventors have found that a novel diamine compound having a group causing a photodimerization reaction and a group causing a photopolymerization reaction in the side chain (hereinafter also referred to as a specific diamine compound). .) By using a liquid crystal aligning agent containing at least one selected from a polyimide precursor obtained by reaction of a diamine component containing tetracarboxylic dianhydride component and an imidized polyimide. The inventors have found that the above problems can be solved, and have completed the present invention. That is, the present invention has the following gist.

  1. At least one selected from a polyimide precursor obtained by a reaction of a diamine component containing a diamine compound represented by the following formula [1] and a tetracarboxylic dianhydride component, and a polyimide obtained by imidizing it. Liquid crystal aligning agent containing a polymer.

（式中、Ｒ^３は−ＣＨ_２−、−Ｏ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＨ−、−ＣＯ−より選ばれる基を表す。Ｒ^４は、炭素数１から炭素数３０で形成されるアルキレン基、二価の炭素環もしくは複素環であり、このアルキレン基、二価の炭素環もしくは複素環の１つまたは複数の水素原子は、フッ素原子もしくは有機基で置き換えられていてもよい。また、Ｒ^４は、次に挙げるいずれかの基が互いに隣り合わない場合において、−ＣＨ_２−がこれらの基に置き換えられていてもよい；−Ｏ−、−ＮＨＣＯ−、−ＣＯＮＨ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＨ−、−ＮＨＣＯＮＨ−、−ＣＯ−。Ｒ^５は、−ＣＨ_２−、−Ｏ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＨ−、−ＣＯ−、単結合のいずれかを表す。Ｒ^６は光二量化を起こす基を表す。Ｒ^７は単結合、または、炭素数１から炭素数３０で形成されるアルキレン基、二価の炭素環もしくは複素環であり、このアルキレン基、二価の炭素環もしくは複素環の１つまたは複数の水素原子は、フッ素原子もしくは有機基で置き換えられていてもよい。また、Ｒ^７は、次に挙げるいずれかの基が互いに隣り合わない場合において、−ＣＨ_２−がこれらの基に置き換えられていてもよい；−Ｏ−、−ＮＨＣＯ−、−ＣＯＮＨ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＨ−、−ＮＨＣＯＮＨ−、−ＣＯ−。Ｒ^８は光重合性基を示す。）

(In the formula, R ³ represents a group selected from —CH ₂ —, —O—, —CONH—, —NHCO—, —COO—, —OCO—, —NH—, —CO—. R ⁴ represents 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 a fluorine atom or R ⁴ may be substituted with an organic group, and R ⁴ 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 ⁵ represents —CH ₂ —, —O—, —CONH—, —NHCO—, -COO-, -OCO-, -NH-, -CO-, R ⁶ represents a single bond, R ⁶ represents a group that causes photodimerization, R ⁷ represents a single bond, an alkylene group having 1 to 30 carbon atoms, a divalent carbocyclic ring or a heterocyclic ring. And one or more hydrogen atoms of the alkylene group, divalent carbocycle or heterocycle may be replaced by a fluorine atom or an organic group, and R ⁷ may be any of the following groups: in the case but which are not next to each other, -CH ₂ - may be replaced by these groups; -O -, - NHCO -, - CONH -, - COO -, - OCO -, - NH -, - NHCONH -, - CO-.R ⁸ shows a photopolymerizable group).

2. R ⁶ is a divalent group represented by the following formula: Liquid crystal aligning agent as described in.

（式中、＊はＲ^５もしくはＲ^７との結合位置を表す。）

(In the formula, * represents a bonding position with R ⁵ or R ^7. )

3. 3. The liquid crystal aligning agent according to 1 or 2, wherein R ⁸ is a monovalent group represented by the following formula.

（式中、＊はＲ^７との結合位置を表す。）

(In the formula, * represents a bonding position with R ^7. )

  4). The diamine component further includes a diamine compound having a side chain that vertically aligns the liquid crystal. ~ 3. The liquid crystal aligning agent in any one of.

  5. 1. The diamine compound represented by the formula [1] is 10 mol% to 80 mol% in the diamine component. ~ 4. The liquid crystal aligning agent in any one of.

  6). 1. The diamine compound having a side chain for vertically aligning the liquid crystal is 5 mol% to 70 mol% in the diamine component. ~ 5. The liquid crystal aligning agent in any one of.

  7.1. ~ 6. Liquid crystal aligning film obtained from the liquid crystal aligning agent in any one of.

  8.7. A liquid crystal display device comprising the liquid crystal alignment film.

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

（式中、Ｒ^１１は炭素数２〜６のアルキレン基を表し、Ｒ^１２は炭素数２〜４のアルキレン基を表す。）

(In the formula, R ¹¹ represents an alkylene group having 2 to 6 carbon atoms, and R ¹² represents an alkylene group having 2 to 4 carbon atoms.)

  10. A diamine compound represented by the following formula [3].

（式［３］中、Ａは以下のものより選ばれる。Ｒ^１３は炭素数２〜６のアルキレン基を表す。）

(In formula [3], A is selected from the following: R ¹³ represents an alkylene group having 2 to 6 carbon atoms.)

（式中、＊はＯとの結合位置を表し、＊＊はＲ^１３との結合位置を表す。）

(In the formula, * represents a bonding position with O, and ** represents a bonding position with R ^13. )

  11. A diamine compound represented by the following formula [4].

（式［４］中、Ｂは以下のものより選ばれる。ｋは０〜１、ｌは１〜６の整数、ｍは１（ただし、ｎが０の場合はｍも０）、ｎは０〜６の整数である。）

(In formula [4], B is selected from the following: k is 0 to 1, l is an integer of 1 to 6, m is 1 (provided that n is 0, m is also 0), and n is 0. It is an integer of ~ 6.)

（式中、＊は−（ＣＨ_２）_ｌ−との結合位置を表し、＊＊はＯとの結合位置を表す。）

(In the formula, * represents a bonding position with — (CH ₂ ) ₁ —, and ** represents a bonding position with O.)

  ADVANTAGE OF THE INVENTION According to this invention, even if it does not contain a photopolymerizable compound, the liquid crystal aligning agent which can improve the response speed of a liquid crystal display element, especially the liquid crystal display element of a vertical alignment system can be provided. The liquid crystal aligning agent is not limited to a vertical alignment type liquid crystal display element, but can be used for a liquid crystal display element that performs alignment processing by irradiating polarized ultraviolet rays, for example, and has a good liquid crystal alignment and an alternating current (AC). A liquid crystal alignment film effective for improving the afterimage can be obtained.

Hereinafter, the present invention will be described in detail.
The liquid crystal aligning agent of this invention is a polyimide obtained by imidating the polyimide precursor obtained by reaction with the diamine component containing the diamine compound represented by the said Formula [1], and a tetracarboxylic dianhydride component. Containing at least one polymer selected from the group consisting of: The liquid crystal alignment agent is a solution for forming a liquid crystal alignment film, and the liquid crystal alignment film is a film for aligning liquid crystals in a predetermined direction. Each component contained in the liquid crystal aligning agent of this invention is explained in full detail below.

<Specific diamine compound>
The diamine component which is a raw material of at least one polymer selected from a polyimide precursor contained in the liquid crystal aligning agent of the present invention and a polyimide obtained by imidizing the same is a diamine compound represented by the above formula [1] including.

In the formula [1], R ³ -R ⁴ -R ⁵ is a spacer site connecting the diaminobenzene skeleton in the side chain and R ⁶ which is a group causing photodimerization, and R ³ is a diaminobenzene skeleton in the spacer site. Represents a bonding group. The linking group R ³ is —CH ₂ — (ie methylene), —O— (ie ether), —CONH— (ie amide), —NHCO— (ie reverse amide), —COO— (ie ester), — It is selected from OCO- (ie reverse ester), -NH- (ie amino), -CO- (ie carbonyl). These linking groups R ³ can be formed by a general organic synthetic method. From the viewpoint of ease of synthesis, —CH ₂ —, —O—, —COO—, —NHCO—, —NH— preferable.

R ⁴ in the formula [1] is a central part of the spacer moiety, and is an alkylene group having 1 to 30 carbon atoms, a divalent carbocycle or a heterocycle. However, any hydrogen atom of this alkylene group, divalent carbocycle or heterocyclic ring may be replaced with a fluorine atom or an organic group. Further, the hydrogen atom to be replaced may be one place or a plurality of places. In addition, one or more of —CH ₂ — of the alkylene group, divalent carbocyclic ring or heterocyclic ring is replaced with these linking groups when any of the following linking groups is not adjacent to each other. -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, -NH, -CO-. This means that R ⁴ may include a configuration of an alkylene group, a divalent carbocycle or a heterocycle-the linking group-alkylene group, a divalent carbocycle or a heterocycle. In addition, when R ³ is —CH ₂ —, it means that the terminal on the R ³ side in R ⁴ may be the linking group. Similarly, when R ⁵ is —CH ₂ —, it means that the terminal on the R ⁵ side in R ⁴ may be the linking group. Therefore, when R ³ is —CH ₂ — and R ⁵ is —CH ₂ —, R ⁴ is a structure of the linking group-alkylene group, divalent carbocycle or heterocyclic-the linking group, ⁴ means that the structure may be any of the bonding groups. Note that —CH ₂ — replaced by the linking group may be at one location, and may be at a plurality of locations as long as the linking groups are not adjacent to each other. Specific examples of the divalent carbocycle or heterocycle include the following structures, but are not limited thereto.

R ⁵ in the formula [1] represents a bonding group to R ⁶ in the spacer site. This linking group R ⁵ is selected from —CH ₂ —, —O—, —CONH—, —NHCO—, —COO—, —OCO—, —NH—, —CO—, and a single bond. These linking groups R ⁵ can be formed by a general organic synthetic method, but from the viewpoint of ease of synthesis, —CH ₂ —, —O—, —COO—, —NHCO—, —NH— Is preferred.

R ⁶ in the formula [1] represents a divalent organic group composed of a group that causes photodimerization. The group that causes photodimerization is a functional group that becomes a dimer when reacted by light irradiation. Examples of R ⁶ include a divalent group including a cinnamoyl group, a coumarin group, and a chalcone group. Specific examples include a divalent group represented by the following formula, but are not limited thereto. is not. In addition, one or more hydrogen atoms of the group represented by the following formula may be substituted with an organic group.

（式中、＊はＲ^５もしくはＲ^７との結合位置を表す。）

(In the formula, * represents a bonding position with R ⁵ or R ^7. )

R ⁷ in the formula [1] is a site connecting R ⁶ which is a group causing photodimerization in a side chain and R ⁸ which is a photopolymerizable group, and R ⁷ is a single bond or a carbon number of 1 An alkylene group having 30 carbon atoms, a divalent carbocyclic ring or a heterocyclic ring. However, any hydrogen atom of this alkylene group, divalent carbocycle or heterocyclic ring may be replaced with a fluorine atom or an organic group. Further, the hydrogen atom to be replaced may be one place or a plurality of places. In addition, one or more of —CH ₂ — of the alkylene group, divalent carbocyclic ring or heterocyclic ring is replaced with these linking groups when any of the following linking groups is not adjacent to each other. -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, -NH-, -CO-. This is because, for example, R ⁷ is an alkylene group, a divalent carbocyclic ring or a heterocyclic ring-the linking group-alkylene group, a divalent carbocyclic ring or a heterocyclic ring, or the linking group-alkylene group, It means that it may contain a structure of carbocycle or heterocycle. Note that —CH ₂ — replaced by the linking group may be at one location, and may be at a plurality of locations as long as the linking groups are not adjacent to each other. Specific examples of the divalent carbocycle or heterocycle include the following structures, but are not limited thereto.

R ⁸ in the formula [1] represents a photopolymerizable group. The photopolymerizable group is a functional group that causes polymerization when irradiated with light. Examples of R ⁸ include a monovalent group including an acryl group, a methacryl group, a lactone group, a maleimide group, a vinyl group, an allyl group, and a styryl group, and specifically, a monovalent group represented by the following formula: However, it is not limited to this.

（式中、＊はＲ^７との結合位置を表す。）

(In the formula, * represents a bonding position with R ^7. )

  A liquid crystal aligning agent containing at least one polymer selected from a polyimide precursor obtained by using such a diamine compound represented by the above formula [1] as a raw material and a polyimide obtained by imidizing it is used. As a result, the cross-linking reaction by the photopolymerizable group derived from the diamine compound represented by the above formula [1] and the dimerization reaction by the group causing photodimerization proceed, and the resulting cross-linking site or dimerization site causes the liquid crystal molecules to Since the tilt direction is stored, the response speed of the obtained liquid crystal display element can be increased.

  The diamine compound (specific diamine compound) represented by the above formula [1] used in the present invention is a novel compound unknown in the literature. As a diamine compound represented by the said Formula [1], the diamine compound represented by following formula [2] is mentioned, for example.

（式中、Ｒ^１１は炭素数２〜６のアルキレン基を表し、Ｒ^１２は炭素数２〜４のアルキレン基を表す。）

(In the formula, R ¹¹ represents an alkylene group having 2 to 6 carbon atoms, and R ¹² represents an alkylene group having 2 to 4 carbon atoms.)

  Moreover, the following diamine compound is mentioned as a specific example of the diamine compound represented by the said Formula [2].

  Moreover, as a diamine compound represented by the said Formula [1], the diamine compound represented by following formula [3] is mentioned, for example.

（式［３］中、Ａは以下のものより選ばれる。Ｒ^１３は炭素数２〜６のアルキレン基を表す。）

(In formula [3], A is selected from the following: R ¹³ represents an alkylene group having 2 to 6 carbon atoms.)

（式中、＊はＯとの結合位置を表し、＊＊はＲ^１３との結合位置を表す。）

(In the formula, * represents a bonding position with O, and ** represents a bonding position with R ^13. )

  Moreover, the following diamine compound is mentioned as a specific example of the diamine compound represented by the said Formula [3].

  Moreover, as a diamine compound represented by the said Formula [1], the diamine compound represented by following formula [4] is mentioned, for example.

（式［４］中、Ｂは以下のものより選ばれる。ｋは０〜１、ｌは１〜６の整数、ｍは１（ただし、ｎが０の場合はｍも０）、ｎは０〜６の整数である。）

(In formula [4], B is selected from the following: k is 0 to 1, l is an integer of 1 to 6, m is 1 (provided that n is 0, m is also 0), and n is 0. It is an integer of ~ 6.)

（式中、＊は−（ＣＨ_２）_ｌ−との結合位置を表し、＊＊はＯとの結合位置を表す。）

(In the formula, * represents a bonding position with — (CH ₂ ) ₁ —, and ** represents a bonding position with O.)

  Moreover, the following diamine compound is mentioned as a specific example of the diamine compound represented by the said Formula [4].

  The diamine represented by the above formula [1] contained in the diamine component which is a raw material of at least one polymer selected from the polyimide precursor contained in the liquid crystal aligning agent of the present invention and the polyimide obtained by imidization thereof. The ratio is not particularly limited, but from the viewpoint of improving the response speed, it is preferable to use an amount of 10 mol% to 80 mol% in the diamine component used for the synthesis of the polyimide precursor, more preferably 10 mol of the diamine component. % To 50 mol%, particularly preferably 20 mol% to 50 mol%.

  The method for synthesizing the diamine compound represented by the above formula [1] is not particularly limited. For example, it can be obtained by reducing the nitro group of the dinitro compound represented by the following formula [1a] and converting it to an amino group. it can.

（式［１ａ］中、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は、式［１］の定義と同義である。）

(In formula [1a], R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ have the same definitions as in formula [1].)

  When the dinitro compound represented by the above formula [1a] is reduced, the reduction is performed using a catalyst that does not hydrogenate the double bond. In the reduction reaction, it is preferable to use zinc, tin, tin chloride, iron or the like together with ammonium chloride, hydrogen chloride or the like in a solvent such as ethyl acetate, toluene, tetrahydrofuran, dioxane, or alcohol.

The dinitro compound represented by the above formula [1a] is obtained by, for example, a method in which -R ⁴ -R ⁵ -R ⁶ -R ⁷ -R ⁸ which is a side chain moiety is bonded to dinitrobenzene via R ^3. be able to. For example, when R ³ is an amide bond (—CONH—), dinitrobenzene acid chloride is reacted with an amino compound containing —R ⁴ —R ⁵ —R ⁶ —R ⁷ —R ⁸ in the presence of an alkali. A method is mentioned.

When R ³ is a reverse amide bond (—HNCO—), an amino group-containing dinitrobenzene is reacted with an acid chloride containing —R ⁴ —R ⁵ —R ⁶ —R ⁷ —R ⁸ in the presence of an alkali. The method of letting it be mentioned.

When R ³ is an ester bond (—COO—), a method of reacting dinitrobenzene acid chloride with an alcohol compound containing —R ⁴ —R ⁵ —R ⁶ —R ⁷ —R ⁸ in the presence of an alkali. Is mentioned. When R ³ is an inverted ester bond (—OCO—), a hydroxy group-containing dinitrobenzene and an acid chloride compound containing —R ⁴ —R ⁵ —R ⁶ —R ⁷ —R ⁸ are present in the presence of an alkali. The method of making it react under is mentioned.

When R ³ is an ether bond (—O—), a method of reacting a halogen group-containing dinitrobenzene with an alcohol compound containing —R ⁴ —R ⁵ —R ⁶ —R ⁷ —R ⁸ in the presence of an alkali. Is mentioned.

When R ³ is an amino bond (—NH—), a halogen group-containing dinitrobenzene is reacted with an amino compound containing —R ⁴ —R ⁵ —R ⁶ —R ⁷ —R ⁸ in the presence of an alkali. A method is mentioned.

When R ³ is a carbonyl bond (—CO—), an aldehyde group-containing dinitrobenzene and a boronic acid compound containing —R ⁴ —R ⁵ —R ⁶ —R ⁷ —R ⁸ are present in the presence of a palladium or copper catalyst. The method of performing a coupling reaction under is mentioned.

When R ³ is a carbon bond (—CH ₂ —), it has an unsaturated bond at the end of R ⁴ side of halogen group-containing dinitrobenzene and —R ⁴ —R ⁵ —R ⁶ —R ⁷ —R ^8. The method of utilizing a Heck reaction or Sonogashira cross coupling reaction with a compound is mentioned.

  Examples of the dinitrobenzene acid chloride include 3,5-dinitrobenzoic acid chloride, 3,5-dinitrobenzoic acid, 2,4-dinitrobenzoic acid chloride, 2,4-dinitrobenzoic acid, and 3,5-dinitrobenzyl chloride. 2,4-dinitrobenzyl chloride and amino group-containing nitrobenzene include 2,4-dinitroaniline, 3,5-dinitroaniline, 2,6-dinitroaniline and the like. Examples of the hydroxy group-containing nitrobenzene include 2,4-dinitrophenol, 3,5-dinitrophenol, 2,6-dinitrophenol and the like. Examples of the halogen group-containing dinitrobenzene include 2,4-dinitrofluorobenzene, 3,5-dinitrofluorobenzene, 2,6-dinitrofluorobenzene, 2,4-dinitroiodobenzene, 3,5-dinitroiodobenzene, 2, Examples include 6-dinitroiodobenzene. Examples of the aldehyde group-containing dinitrobenzene include 2,4-dinitroaldehyde, 3,5-dinitroaldehyde, 2,6-dinitroaldehyde and the like.

As a method for synthesizing ^{-R 4 -R 5 -R 6 -R 7} -R 8 is a side chain moiety, a method of synthesizing in listed below methods. For example, when an amide bond (—CONH—) is included in the structure of —R ⁴ —R ⁵ —R ⁶ —R ⁷ —R ⁸ , an acid chloride compound containing —R ⁴ and —R ⁶ —R ⁷ — R ⁸ amino ^compounds, amino compounds containing -R 4 ^-R acid chloride compound containing 5 -R ⁶ and ^-R 7 -R ^8, or ^an acid chloride compound containing ^{-R 4} -R 5 -R 6 -R ⁷ And an amino compound containing —R ⁸ is reacted in the presence of an alkali.

When the structure of —R ⁴ —R ⁵ —R ⁶ —R ⁷ —R ⁸ has a reverse amide bond (—HNCO—), the amino compound containing —R ⁴ and —R ⁶ —R ⁷ —R ⁸ An acid chloride compound containing -R ⁴ -R ⁵ -R ⁶ and an amino compound containing -R ⁷ -R ⁸ , or an amino compound containing -R ⁴ -R ⁵ -R ⁶ -R ⁷ And an acid chloride compound containing -R ⁸ is reacted in the presence of an alkali.

When an ester bond (—COO—) is included in the structure of —R ⁴ —R ⁵ —R ⁶ —R ⁷ —R ⁸ , an acid chloride compound containing —R ⁴ and —R ⁶ —R ⁷ —R ⁸ An alcohol compound containing -R ⁴ -R ⁵ -R ⁶ and an acid chloride compound containing -R ⁷ -R ⁸ , or an acid chloride compound containing -R ⁴ -R ⁵ -R ⁶ -R ⁷ And a method in which an alcohol compound containing -R ⁸ is reacted in the presence of an alkali.

When the structure of —R ⁴ —R ⁵ —R ⁶ —R ⁷ —R ⁸ has a reverse ester bond (—OCO—), an alcohol compound containing —R ⁴ and —R ⁶ —R ⁷ —R ⁸ An acid chloride compound containing -R ⁴ -R ⁵ -R ⁶ and an alcohol compound containing -R ⁷ -R ⁸ , or an alcohol compound containing -R ⁴ -R ⁵ -R ⁶ -R ⁷ And an acid chloride compound containing -R ⁸ is reacted in the presence of an alkali.

When the structure of —R ⁴ —R ⁵ —R ⁶ —R ⁷ —R ⁸ has an ether bond (—O—), a halogen compound containing —R ⁴ and —R ⁶ —R ⁷ —R ⁸ An alcohol compound containing -R ⁴ -R ⁵ -R ⁶ and a halogen compound containing -R ⁷ -R ⁸ , an halogen compound containing -R ⁴ -R ⁵ -R ⁶ -R ⁷ and -R ⁸ An alcohol compound containing -R ⁴ , an alcohol compound containing -R ⁶ -R ⁷ -R ⁸ , an alcohol compound containing -R ⁴ -R ⁵ -R ⁶ and a halogen containing -R ⁷ -R ⁸ Examples thereof include a method in which a compound or an alcohol compound containing -R ⁴ -R ⁵ -R ⁶ -R ⁷ and a halogen compound containing -R ⁸ are reacted in the presence of an alkali.

In the case where the structure of —R ⁴ —R ⁵ —R ⁶ —R ⁷ —R ⁸ has an amino bond (—NH—), a halogen compound containing —R ⁴ and —R ⁶ —R ⁷ —R ⁸ are An amino compound containing, a halogen compound containing -R ⁴ -R ⁵ -R ⁶ and an amino compound containing -R ⁷ -R ⁸ , a halogen compound containing -R ⁴ -R ⁵ -R ⁶ -R ⁷ and -R ⁸ An amino compound containing -R ⁴ , an amino compound containing -R ⁶ and a halogen compound containing -R ⁶ -R ⁷ -R ⁸ , an amino compound containing -R ⁴ -R ⁵ -R ⁶ and a halogen compound containing -R ⁷ -R ⁸ Alternatively, a method in which an amino compound containing —R ⁴ —R ⁵ —R ⁶ —R ⁷ and a halogen compound containing —R ⁸ are reacted in the presence of an alkali can be mentioned.

When the structure of —R ⁴ —R ⁵ —R ⁶ —R ⁷ —R ⁸ has a carbonyl bond (—CO—), an aldehyde compound containing —R ⁴ and —R ⁶ —R ⁷ —R ⁸ are boronic acid compound ^containing, -R 4 ^-R 5 -R ⁶ aldehyde compound comprises a ^-R 7 boronic acid compound containing -R ^8, aldehyde compounds including -R ⁴ -R 5 ^-R 6 -R ⁷ and -R boronic acid compounds containing ^8, aldehyde compounds including boronic acid compounds and ^-R 6 ^-R 7 -R ⁸ including -R ^4, boron acid compound containing ^-R 4 -R 5 -R ⁶ and ^-R 7 -R Examples thereof include a method in which an aldehyde compound containing ⁸ or a boronic acid compound containing -R ⁴ -R ⁵ -R ⁶ -R ⁷ and an aldehyde compound containing -R ⁸ are reacted in the presence of an alkali.

<Diamine compound having a side chain for vertically aligning liquid crystal>
Moreover, the diamine component which is the raw material of the polyimide precursor which the liquid crystal aligning agent of this invention contains, and the polyimide obtained by imidating this is at least 1 sort (s) of a polymer is represented by the said Formula [1]. In addition to the diamine compound, a diamine compound having a side chain for vertically aligning the liquid crystal may be included. Examples of the diamine compound having a side chain for vertically aligning the liquid crystal include a long chain alkyl group, a group having a ring structure or a branched structure in the middle of the long chain alkyl group, a steroid group, and a part of hydrogen atoms of these groups. Or the diamine which has the group which substituted all the fluorine atoms as a side chain, for example, the diamine shown by the following formula [A-1]-a formula [A-24] can be illustrated, However, It is limited to this is not.

（式［Ａ−１］〜式［Ａ−５］中、Ａ_１は、炭素数２〜２４のアルキル基又はフッ素含有アルキル基である。）

(In Formula [A-1] to Formula [A-5], A ₁ is an alkyl group having 2 to 24 carbon atoms or a fluorine-containing alkyl group.)

（式［Ａ−６］及び式［Ａ−７］中、Ａ_２は、−Ｏ−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−ＣＯＯＣＨ_２−、又は−ＣＨ_２ＯＣＯ−を示し、Ａ_３は炭素数１〜２２のアルキル基、アルコキシ基、フッ素含有アルキル基又はフッ素含有アルコキシ基である。）

(In Formula [A-6] and Formula [A-7], A ₂ represents —O—, —OCH ₂ —, —CH ₂ O—, —COOCH ₂ —, or —CH ₂ OCO—, and ₃ is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group.

（式［Ａ−８］〜式［Ａ−１０］中、Ａ_４は、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＯＣＨ_２−、−ＣＨ_２ＯＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、又は−ＣＨ_２−を示し、Ａ_５は炭素数１〜２２のアルキル基、アルコキシ基、フッ素含有アルキル基又はフッ素含有アルコキシ基である。）

(In formula [A-8] to formula [A-10], A ₄ represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH _2. O—, —OCH ₂ —, or —CH ₂ — is shown, and A ₅ is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group, or a fluorine-containing alkoxy group.

（式［Ａ−１１］及び式［Ａ−１２］中、Ａ_６は、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＯＣＨ_２−、−ＣＨ_２ＯＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＨ_２−、−Ｏ−、又は−ＮＨ−を示し、Ａ_７はフッ素基、シアノ基、トリフルオロメタン基、ニトロ基、アゾ基、ホルミル基、アセチル基、アセトキシ基、又は水酸基である。）

(In Formula [A-11] and Formula [A-12], A ₆ represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH _2. O—, —OCH ₂ —, —CH ₂ —, —O—, or —NH— is shown, and A ₇ is fluorine group, cyano group, trifluoromethane group, nitro group, azo group, formyl group, acetyl group, acetoxy Group or hydroxyl group.)

（式［Ａ−１３］及び式［Ａ−１４］中、Ａ_８は、炭素数３〜１２のアルキル基であり、１，４−シクロヘキシレンのシス−トランス異性は、それぞれトランス異性体である。）

(In Formula [A-13] and Formula [A-14], A ₈ is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer. .)

（式［Ａ−１５］及び式［Ａ−１６］中、Ａ_９は、炭素数３〜１２のアルキル基であり、１，４−シクロヘキシレンのシス−トランス異性は、それぞれトランス異性体である。）

(In Formula [A-15] and Formula [A-16], A ₉ is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer. .)

  In addition, specific examples of the diamine compound having a side chain for vertically aligning the liquid crystal include diamines represented by the following formulas [A-25] to [A-30].

（式［Ａ−２５］〜式［Ａ−３０］中、Ａ_１２は、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２−、−Ｏ−、−ＣＯ−、又は−ＮＨ−を示し、Ａ_１３は炭素数１〜２２のアルキル基又はフッ素含有アルキル基を示す。）

(In the formulas [A-25] to [A-30], A ₁₂ represents —COO—, —OCO—, —CONH—, —NHCO—, —CH ₂ —, —O—, —CO—, or It indicates _{-NH-, a 13} represents an alkyl group or a fluorine-containing alkyl group having 1 to 22 carbon atoms.)

  Further, specific examples of the diamine compound having a side chain for vertically aligning the liquid crystal include diamines represented by the following formulas [A-31] to [A-32].

  Among these, [A-1], [A-2], [A-3], [A-4], [A-5], [A-5], [A-5], [A-5], [A-5], [A-5], [A-5], [A-5], [A-5] The diamines of A-25], [A-26], [A-27], [A-28], [A-29], and [A-30] are preferable.

  The diamine may 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.

  It has a side chain that vertically aligns the liquid crystal contained in the diamine component, which is a raw material of at least one polymer selected from the polyimide precursor contained in the liquid crystal aligning agent of the present invention and the polyimide obtained by imidizing it. The proportion of the diamine is not particularly limited, but it is preferable to use an amount of 5 mol% to 70 mol% in the diamine component used for the synthesis of the polyimide precursor, and more preferably 10 mol% to 50 mol% in the diamine component. And particularly preferably 20 to 50 mol%. When the diamine having a side chain for vertically aligning the liquid crystal is used in an amount of 5 mol% to 70 mol% in the diamine component used for the synthesis of the polyimide precursor, the response speed is improved and the alignment of the liquid crystal is fixed. Especially excellent in terms of ability.

<Other diamine compounds>
In addition, the diamine component, which is a raw material of at least one polymer selected from the polyimide precursor contained in the liquid crystal aligning agent of the present invention and the polyimide obtained by imidizing it, is as long as the effects of the present invention are not impaired. In addition to the diamine compound represented by the formula [1] and a diamine having a side chain for vertically aligning the liquid crystal, other diamines may be included. Examples of other diamines include p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, and 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′-diamino Biphenyl, 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 ' -Sulfonyl dianiline, 3,3'-sulfonyl dianiline, bis (4-amino Nophenyl) 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′-diaminobenzophene Non, 3,4′-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2′-diaminobenzophenone, 2,3′-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7 -Diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6 diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis (4-aminophenyl) ethane 1,2-bis (3-aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,3-bis (3-aminophenyl) propane, 1,4-bis (4-aminophenyl) ) Butane, 1,4-bis (3-aminophenyl) butane, bis (3,5-diethyl-4-aminophenyl) methane, 1, 4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (4-aminobenzyl) benzene, 1,3-bis (4-aminophenoxy) benzene, 4,4 ′-[1,4-phenylenebis (methylene)] dianiline, 4,4 ′-[ 1,3-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-phenylenebis [(4-aminophenyl) me Non], 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-amino) Benzoate), bis (4-aminophenyl) terephthalate, bis (3-aminophenyl) terephthalate, bis (4-aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, N, N ′-(1,4 -Phenylene) bis (4-aminobenzamide), N, N '-(1,3-phenylene) bis (4-aminobenz) Amide), 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-aminophenyl) hexafluoropropane, 2,2′-bis ( -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-diaminobenzoic acid, 1,3-bis (4-aminophenoxy) ) Propane, 1,3-bis (3-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, 1,4-bis (3-aminophenoxy) butane, 1,5-bis (4- Aminophenoxy) pentane, 1,5-bis (3-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) hexane, 1,6-bis (3-aminophenoxy) Xanthine, 1,7-bis (4-aminophenoxy) heptane, 1,7- (3-aminophenoxy) heptane, 1,8-bis (4-aminophenoxy) octane, 1,8-bis (3-aminophenoxy) ) Octane, 1,9-bis (4-aminophenoxy) nonane, 1,9-bis (3-aminophenoxy) nonane, 1,10- (4-aminophenoxy) decane, 1,10- (3-aminophenoxy) ) Decane, 1,11- (4-aminophenoxy) undecane, 1,11- (3-aminophenoxy) undecane, 1,12- (4-aminophenoxy) dodecane, 1,12- (3-aminophenoxy) dodecane Such as aromatic diamine, bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, etc. Min, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane Aliphatic diamines such as 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane.

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

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

<Synthesis of polyimide precursor>
The polyimide precursor that can be contained in the liquid crystal aligning agent of the present invention refers to a polyamic acid or a polyamic acid ester.

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

  The organic solvent used in the above reaction is not particularly limited as long as the generated polyamic acid dissolves. Furthermore, even if it is an organic solvent in which a polyamic acid does not melt | dissolve, you may mix and use the said solvent in the range which the produced | generated polyamic acid does not precipitate. In addition, since the water | moisture content in an organic solvent inhibits a polymerization reaction and also causes the produced polyamic acid to hydrolyze, it is preferable to use what dehydrated and dried the organic solvent. Examples of the organic solvent used in the reaction include 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, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl Rosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether , Propylene glycol monobutyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, di Propylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3 -Methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl Ether, dioxane, n-hexane, n-pentane, n-octane, Ethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, Methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl -2-pentanone, 2-ethyl-1-hexanol and the like. 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 making a diamine component and a tetracarboxylic dianhydride component react can select arbitrary temperatures, for example, -20 degreeC-150 degreeC, Preferably it is the range of -5 degreeC-100 degreeC. Moreover, reaction can be performed by arbitrary density | concentrations, for example, the total amount of a diamine component and a tetracarboxylic dianhydride component is 1-50 mass% with respect to the reaction liquid, Preferably it is 5-30 mass%.

  The ratio of the total number of moles of the tetracarboxylic dianhydride component with respect to the total number of moles of the diamine component in the polymerization reaction can be selected according to the molecular weight of the polyamic acid to be obtained. Similar to the 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, as with the general polyamic acid synthesis method, as the tetracarboxylic dianhydride component, a tetracarboxylic acid having a corresponding structure is used. Alternatively, a corresponding polyamic acid can be obtained by reacting by a known method using a tetracarboxylic acid derivative such as tetracarboxylic acid dihalide.

  The polyamic acid ester can be synthesized by the following methods (1) to (3).

(1) When synthesizing from polyamic acid A polyamic acid ester can be synthesized by esterifying a polyamic acid obtained from a tetracarboxylic dianhydride and a diamine component. Specifically, the polyamic acid and the esterifying agent are reacted in the presence of an organic solvent at −20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C., for 30 minutes to 24 hours, preferably 1 to 4 hours. Can be synthesized.

  As the esterifying agent, those that can be easily removed by purification are preferred, and N, N-dimethylformamide dimethyl acetal, N, N-dimethylformamide diethyl acetal, N, N-dimethylformamide dipropyl acetal, N, N-dimethylformamide Dineopentyl butyl acetal, N, N-dimethylformamide di-t-butyl acetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene, 1-propyl-3-p -Tolyltriazene, 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride and the like. The addition amount of the esterifying agent is preferably 2 to 6 molar equivalents per 1 mol of the polyamic acid repeating unit.

  The solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, or γ-butyrolactone from the solubility of the polymer, and these may be used alone or in combination of two or more. Good. The concentration at the time of synthesis is preferably 1 to 30% by mass and more preferably 5 to 20% by mass from the viewpoint that polymer precipitation is unlikely to occur and a high molecular weight body is easily obtained.

(2) When synthesize | combining by reaction with tetracarboxylic-acid diester dichloride and a diamine component Polyamic acid ester is compoundable from a tetracarboxylic-acid diester dichloride and a diamine component. Specifically, the tetracarboxylic acid diester dichloride and the diamine component are -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C, in the presence of a base and an organic solvent, preferably 30 minutes to 24 hours, preferably 1 to 4 hours. It can be synthesized by reacting for a time.

  As the base, pyridine, triethylamine, 4-dimethylaminopyridine and the like can be used, but pyridine is preferable because the reaction proceeds gently. The addition amount of the base is preferably 2 to 4 times the molar amount of the tetracarboxylic acid diester dichloride from the viewpoint of easy removal and high molecular weight.

  The solvent used in the above reaction is preferably N-methyl-2-pyrrolidone or γ-butyrolactone from the solubility of the monomer and polymer, and these may be used alone or in combination. The polymer concentration at the time of synthesis is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass from the viewpoint that polymer precipitation hardly occurs and a high molecular weight body is easily obtained. In order to prevent hydrolysis of the tetracarboxylic acid diester dichloride, the solvent used for the synthesis of the polyamic acid ester is preferably dehydrated as much as possible, and it is preferable to prevent mixing of outside air in a nitrogen atmosphere.

(3) When synthesize | combining by reaction of tetracarboxylic-acid diester and a diamine component Polyamic acid ester is compoundable by polycondensing a tetracarboxylic-acid diester and a diamine component. Specifically, the tetracarboxylic acid diester and the diamine component are added in the presence of a condensing agent, a base, and an organic solvent at 0 ° C. to 150 ° C., preferably 0 ° C. to 100 ° C., for 30 minutes to 24 hours, preferably 3 to 15 hours. It can be synthesized by reacting for a time.

  Examples of the condensing agent include triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N′-carbonyldiimidazole, dimethoxy-1,3,5-triazi Nylmethylmorpholinium, O- (benzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) -N, N , N ′, N′-tetramethyluronium hexafluorophosphate, diphenyl (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate, and the like. It is preferable that the addition amount of a condensing agent is 2-3 times mole with respect to tetracarboxylic-acid diester.

  As the base, tertiary amines such as pyridine and triethylamine can be used. The addition amount of the base is preferably 2 to 4 times the mol of the diamine component from the viewpoint of easy removal and high molecular weight.

  In the above reaction, the reaction proceeds efficiently by adding Lewis acid as an additive. As the Lewis acid, lithium halides such as lithium chloride and lithium bromide are preferable. The addition amount of the Lewis acid is preferably 0 to 1.0 times the mole of the diamine component.

  Among the methods for synthesizing the three polyamic acid esters, since a high molecular weight polyamic acid ester is obtained, the synthesis method (1) or (2) is particularly preferable.

  The polyamic acid ester solution obtained as described above can be polymerized by pouring into a poor solvent while stirring well. Precipitation is performed several times, and after washing with a poor solvent, a purified polyamic acid ester powder can be obtained at room temperature or by heating and drying. Although a poor solvent is not specifically limited, Water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene etc. are mentioned.

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

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

  The catalytic imidation of the polyamic acid can be performed by adding a basic catalyst and an acid anhydride to the polyamic acid solution and stirring at -20 to 250 ° C, preferably 0 to 180 ° C. The amount of the basic catalyst is 0.5 to 30 times mol, preferably 2 to 20 times mol of the amic acid group, and the amount of the acid anhydride is 1 to 50 times mol, preferably 3 to 30 times of the amido acid group. Is a mole. 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 polyamic acid or polyimide from the reaction solution of polyamic acid or polyimide, the reaction solution may be poured into a poor solvent and precipitated. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water. The polymer precipitated in a poor solvent and collected by filtration can be dried by normal temperature or reduced pressure at room temperature or by heating. Moreover, when the polymer which carried out precipitation collection | recovery is re-dissolved in an organic solvent and the operation which carries out reprecipitation collection | recovery is repeated 2 to 10 times, the impurity in a polymer can be decreased. Examples of the 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 this invention is a polyimide precursor obtained by reaction with the diamine component containing the diamine compound represented by the said Formula [1], and a tetracarboxylic dianhydride component, and this polyimide precursor as mentioned above. It contains at least one polymer selected from polyimides obtained by imidizing the body. Obtained by imidizing the polyimide precursor obtained by the reaction of the diamine component containing the diamine compound represented by the above formula [1] and the tetracarboxylic dianhydride component contained in the liquid crystal aligning agent, and the polyimide precursor. The total amount of at least one polymer selected from polyimides to be prepared is preferably 1 to 10 (mass)%.

  Moreover, the liquid crystal aligning agent of this invention is a polyimide precursor obtained by reaction of the diamine component containing the diamine compound represented by the said Formula [1], and a tetracarboxylic dianhydride component, and this polyimide precursor. You may contain other polymers other than the at least 1 type of polymer selected from the polyimide obtained by imidation. In that case, the polyimide precursor obtained by reaction with the diamine component containing the diamine compound represented by the said Formula [1] in all the components of a polymer, and a tetracarboxylic dianhydride component, and this polyimide precursor are imide. The proportion of at least one polymer selected from polyimides obtained by the conversion is preferably 10 (mass)% or more.

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

  There is no limitation in particular in the solvent which a liquid crystal aligning agent contains, The polyimide precursor obtained by reaction of the diamine component containing the diamine compound represented by the said Formula [1], and a tetracarboxylic dianhydride component, and this polyimide What is necessary is just to be able to dissolve or disperse a component such as at least one polymer selected from polyimides obtained by imidizing a precursor. For example, the organic solvent which was illustrated by the synthesis | combination of said polyamic acid can be mentioned. Among these, N-methyl-2-pyrrolidone, γ-butyrolactone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and 3-methoxy-N, N-dimethylpropanamide are soluble. To preferred. Of course, two or more kinds of mixed solvents may be used.

  Moreover, it is preferable to mix and use the solvent which improves the uniformity and smoothness of a coating film in the solvent with the high solubility of the component of a liquid crystal aligning agent. Solvents that improve the uniformity and smoothness of the coating include, for example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol Tolu, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-tert-butyl ether , Dipropylene glycol monomethyl Ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether Dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, dii Butylene, 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, acetic acid Ethyl, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 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, lactate methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n-butyl ester, lactate isoamyl ester, 2-ethyl-1-hexanol and the like. A plurality of these solvents may be mixed. When using these solvents, it is preferable that it is 5-80 mass% of the whole solvent contained in a liquid crystal aligning agent, More preferably, it is 20-60 mass%.

  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 use ratio thereof is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of the total amount of the polymer contained in the liquid crystal aligning agent. 1 part by mass.

  Specific examples of compounds that improve the adhesion between the liquid crystal alignment film and the substrate include functional silane-containing compounds and epoxy group-containing compounds. For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxy Carbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-to Ethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltri Methoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-amino Propyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether , Polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetra Glycidyl-2,4-hexanediol, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′ , N′-tetraglycidyl-4, 4′-diaminodiphenylmethane, 3- (N-allyl-N-glycidyl) aminopropyltrimethoxysilane, 3- (N, N-diglycidyl) aminopropyltrimethoxysilane and the like. . In order to further increase the film strength of the liquid crystal alignment film, a phenol compound such as 2,2'-bis (4-hydroxy-3,5-dihydroxymethylphenyl) propane or tetra (methoxymethyl) bisphenol may be added. When using these compounds, it is preferable that it is 0.1-30 mass parts with respect to 100 mass parts of total amounts of the polymer contained in a liquid crystal aligning agent, More preferably, it is 1-20 mass parts.

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

<Liquid crystal alignment film>
By applying and baking this liquid crystal aligning agent on a substrate, a liquid crystal alignment film for vertically aligning liquid crystals can be formed.

  In this case, the substrate to be used is not particularly limited as long as it is a highly transparent substrate, and a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or 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 simplification of 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 a screen printing method, an offset printing method, a flexographic printing method, an ink jet method, a dip method, a roll coater, a slit coater, and a spinner.

  The baking 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 ° C to 350 ° C, preferably 120 ° C to 300 ° C, and more preferably. Is 150 ° C to 250 ° C. This baking can be performed with 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, and more preferably 10 to 100 nm.

<Liquid crystal display element>
The liquid crystal display element of the present invention is formed by two substrates arranged to face each other, a liquid crystal layer provided between the substrates, and a liquid crystal aligning agent of the present invention provided between the substrate and the liquid crystal layer. A liquid crystal display element comprising a liquid crystal cell having the 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 display element including a liquid crystal cell manufactured by sandwiching a liquid crystal layer composed of liquid crystal between two substrates and irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer. As such a liquid crystal display element of the present invention, various devices such as a twisted nematic (TN) method, a vertical alignment (VA) method, a horizontal alignment (IPS) method, and the like are available. Can be mentioned.

  As described above, the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention is used, and ultraviolet light is applied to the liquid crystal alignment film and the liquid crystal layer while applying voltage to the photopolymerizability of the polyimide precursor and the polyimide side chain. By reacting the group and the group causing photodimerization, that is, the photopolymerizable group derived from the diamine compound represented by the above formula [1] and the group causing photodimerization, the photopolymerizable compound is contained in the liquid crystal aligning agent. Even if not, the alignment of the liquid crystal is more efficiently fixed than the liquid crystal alignment film using the liquid crystal aligning agent containing the photopolymerizable compound, and the liquid crystal display device is remarkably excellent in response speed. Of course, even when a photopolymerizable compound is added to the liquid crystal aligning agent of the present invention, it is possible to obtain a liquid crystal display device having a response speed of the same or higher.

  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 is formed on one side substrate, and a slit pattern or projection pattern is not formed on the opposite substrate. The process can be simplified and high transmittance can be obtained.

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

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

  The liquid crystal 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, negative type liquid crystal such as MLC-6608, MLC-6609 manufactured by Merck Alternatively, MLC-2041 or the like can be used.

  As a method of 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 between the electrodes installed on the substrate to apply an electric field to the liquid crystal alignment film and the liquid crystal layer. And applying ultraviolet rays while maintaining this electric field. Here, the voltage applied between the electrodes is, for example, 5 to 30 Vp-p, preferably 5 to 20 Vp-p. The irradiation amount of ultraviolet rays is, for example, 1 to 60 J, preferably 40 J or less, and the smaller the irradiation amount of ultraviolet rays, the lowering of reliability caused by the destruction of members constituting the liquid crystal display element can be suppressed, and the irradiation time of ultraviolet rays can be reduced. This is preferable because the manufacturing efficiency is improved.

  As described above, when ultraviolet rays are applied while applying a voltage to the liquid crystal alignment film and the liquid crystal layer, the reaction of the photopolymerizable group of the polyimide precursor or the side chain of the polyimide and the group causing photodimerization proceeds, that is, The cross-linking reaction by the photopolymerizable group derived from the diamine compound represented by the formula [1] and the dimerization reaction by the group causing photodimerization proceed, and the direction in which the liquid crystal molecules are inclined is memorized by the resulting cross-linking site or dimerization site As a result, 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 rubbing treatment or photo-alignment treatment. It can also be suitably used for applications of the liquid crystal alignment film to be produced.

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

  Abbreviations and structures of tetracarboxylic dianhydrides and diamines used in the synthesis examples are shown below.

Abbreviations such as organic solvents used in Examples and the like are as follows.
NMP: N-methyl-2-pyrrolidone BCS: butyl cellosolve THF: tetrahydrofuran DMF: N, N-dimethylformamide DMAc: N, N-dimethylacetamide EtOH: ethanol HEMA: 2-hydroxyethyl methacrylate EDC: 1- (3-dimethyl Aminopropyl) -3-ethylcarbodiimide hydrochloride DMAP: 4-dimethylaminopyridine

<Measurement of molecular weight of polymer>
The molecular weight of polyimide or polyamic acid is measured as follows using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) manufactured by Shodex Co., Ltd. and columns (KD-803, KD-805) manufactured by Shodex Co., Ltd. did.
Column temperature: 50 ° C
Eluent: N, N-dimethylformamide (as additives, lithium bromide-hydrate (LiBr · H ₂ O) 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphoric acid) 30 mmol / L, tetrahydrofuran) (THF) is 10 ml / L)
Flow rate: 1.0 mL / minute standard sample for preparing calibration curve: TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation and polyethylene glycol (manufactured by Polymer Laboratories) Molecular weight about 12,000, 4,000, 1,000).

<Measurement of ¹ HNMR>
Apparatus: Fourier transform type superconducting nuclear magnetic resonance apparatus (FT-NMR) INOVA-400 (manufactured by Varian) 400 MHz
Solvent: deuterated dimethyl sulfoxide (DMSO-d ₆ ), deuterated chloroform (CDCl ₃ )
Standard substance: Tetramethylsilane (TMS)

  Example 1 Synthesis of DA-4

  Example 1-1 Synthesis of DA-4 Precursor DA-4-1

  In a 1 L three-necked flask, 102.0 g of trans-p-coumaric acid, 500 mL of ethanol, and 5.8 g of sulfuric acid were added and stirred while heating under reflux. After completion of the reaction, the reaction system was poured into 3 L of water, and the precipitate was filtered, and then the filtrate was dried to obtain 90.0 g of the desired product DA-4-1 (white solid) (yield 75%). ).

  Example 1-2 Synthesis of DA-4 Precursor DA-4-2

  In a 500 mL three-necked flask, 19.2 g of DA-4-1, 250 mL of dimethylformamide, 20.5 g of 6-chloro-1-hexanol, 41.5 g of potassium carbonate, and 1.7 g of potassium iodide were added. Stir at ° C. After completion of the reaction, the reaction system was poured into 1.2 L of water, neutralized with 1N HCl aqueous solution, and the precipitate was filtered. This filtrate was dissolved in 300 mL of ethyl acetate, extracted with saturated brine, dehydrated and filtered by adding anhydrous magnesium sulfate to the organic layer, filtered, and then the solvent was distilled off using a rotary evaporator. .99 g of the desired product DA-4-2 (transparent viscous material) was obtained (yield 92%).

  Example 1-3 Synthesis of DA-1 Precursor DA-4-3

  To a 500 mL three-necked flask, 14.7 g of DA-4-2 and 200 mL of ethanol, 30.0 g of 10 wt% KOH aqueous solution were added and stirred while refluxing. After completion of the reaction, the reaction system was poured into 600 mL of water, neutralized with 1N-HCl aqueous solution, and the precipitate was filtered. The filtrate was washed with ethyl acetate and dried to obtain 11.8 g of the desired product DA-4-3 (white solid) (yield 89%).

  Example 1-4 Synthesis of DA-1 Precursor DA-4-4

To a 300 mL three-necked flask, 11.7 g of DA-4-3, 4.9 g of triethylamine (Et ₃ N), and 200 mL of tetrahydrofuran were added. The system was cooled to 0 ° C., 15.2 g of 3,5-dinitrobenzoyl chloride was added, and the mixture was stirred at room temperature. After completion of the reaction, 50 mL of pure water was added and stirred, and then the organic layer was extracted by adding ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, filtered, and then the solvent was distilled off using a rotary evaporator. went. The residue was recrystallized from ethyl acetate to obtain 7.2 g of the desired product DA-4-4 (yellowish white solid) (yield 35%).

  Example 1-5 Synthesis of DA-4 Precursor DA-4-5

  In a 200 mL three-necked flask, 6.9 g of DA-4-4, 60 mL of tetrahydrofuran, 3.0 g of 2-hydroxyethyl methacrylate (HEMA), 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride ( 4.4 g of EDC) and 0.2 g of 4-dimethylaminopyridine (DMAP) were added and stirred at room temperature. After completion of the reaction, the organic layer was extracted with chloroform, anhydrous magnesium sulfate was added to the organic layer, dehydrated, dried and filtered. Then, the solvent was distilled off using a rotary evaporator, and the residue was isopropyl alcohol / hexane = 1/5. Recrystallization was performed to obtain 5.9 g of the desired product DA-4-5 (yellowish white solid) (yield 69%).

  Example 1-6 Synthesis of DA-4

In a 300 mL three-necked flask, 5.9 g of DA-4-5, 60 mL of tetrahydrofuran and 60 mL of pure water were added, the system was stirred, 13.3 g of tin chloride was added, and the system was heated to 70 ° C. and stirred. did. After completion of the reaction, the reaction system was poured into 300 mL of ethyl acetate, and the pH was adjusted to 7-8 using sodium hydrogen carbonate. The white precipitate was removed by filtration, the organic layer was extracted with ethyl acetate, anhydrous magnesium sulfate was added to the organic layer, dried and filtered, and then the solvent was distilled off using a rotary evaporator. The residue was recrystallized using ethyl acetate / hexane = 1/5 to obtain 5.7 g of the desired product DA-4 (orange solid) (yield 99%). The result of measuring the obtained solid by ¹ H-NMR is shown below. From this result, it was confirmed that the obtained solid was the target DA-4.
¹ H NMR (400 MHz, [D ₆ ] -DMSO): δ 7.54-7.67 (d, 2H), 7.60 (s, 1H), 6.94-6.97 (d, 2H), 6.48-6.52 (d, 1H), 6.42-6.43 (s, 2H), 6.01-6.05 (m, 2H), 5.70 (s, 1H), 4.99 (s, 4H), 4.36-4.40 (m, 4H), 4.15-4.19 (m, 2H), 4.00-4.03 (m, 2H), 1.88 (s, 3H), 1.66-1.75 (m, 4H), 1.36-1.46 (m, 4H)

  Example 2 Synthesis of DA-5

  Example 2-1 Synthesis of DA-5 Precursor DA-5-1

  4-Bromohydroxybenzene (100 g, 578 mmol), tert-butyl acrylate (156 g, 1.21 mol), palladium (II) acetate (2.6 g, 11.6 mmol), tri (o-tolyl) in a 2 L four-necked flask Phosphine (7.0 g, 23.1 mmol), tributylamine (321 g, 1.73 mol), N, N′-dimethylacetamide (hereinafter referred to as DMAc) (500 g) was added, and the mixture was heated and stirred at 100 ° C. The reaction was monitored by HPLC. After completion of the reaction, the reaction solution was poured into 1M aqueous hydrochloric acid (2 L) and stirred for a while. Ethyl acetate (1 L) was added thereto, the aqueous layer was removed by liquid separation operation, the organic layer was washed 3 times with saturated brine (500 mL), the organic layer was dried over magnesium sulfate, filtered, and the solvent was distilled off. Leaving 158 g of DA-5-1 (reddish brown mucus). The obtained compound was directly used in the next step.

  Example 2-2 Synthesis of DA-5 precursor DA-5-2

  In a 500 mL four-necked flask, 22.0 g of DA-5-1, 250 mL of N, N-dimethylformamide, 19.1 g of 6-chloro-1-hexanol, 41.5 g of potassium carbonate, and 1.1 of potassium iodide. 7 g was added and stirred while heating to 100 ° C. After completion of the reaction, the reaction system was poured into 1 L of water, neutralized with 1N-hydrochloric acid aqueous solution, and the precipitate was filtered. This filtrate was washed with isopropyl alcohol and dried to obtain 13.2 g of DA-5-2 (white solid). (Yield 43%)

  Example 2-3 Synthesis of DA-5 Precursor DA-5-3

  To a 300 mL four-necked flask, 6.4 g of DA-5-2, 60 mL of tetrahydrofuran, 3.7 g of 2,4-dinitrofluorobenzene, and 2.4 g of triethylamine were added and stirred while heating to 80 ° C. After completion of the reaction, the reaction system was poured into 500 mL of ethyl acetate and extracted with saturated brine. To the extracted organic layer, anhydrous magnesium sulfate was added, dehydrated and dried, and anhydrous magnesium sulfate was filtered. The obtained filtrate was evaporated using a rotary evaporator, 50 mL of formic acid was added, and the mixture was stirred while heating to 50 ° C. After completion of the reaction, the reaction system was poured into 500 mL of water, and the precipitate was filtered. This filtrate was washed with isopropyl alcohol and dried to obtain 7.4 g of DA-5-3 (yellow solid) (yield 81%).

  Example 2-4 Synthesis of DA-5 precursor DA-5-4

  In a 300 mL four-necked flask, DA-5-3 6.9 g, tetrahydrofuran 70 mL, 2-hydroxyethyl methacrylate 2.5 g, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride 5. 3 g, 0.2 g of 4-dimethylaminopyridine was added and stirred at room temperature. After completion of the reaction, the reaction system was poured into 200 mL of water, and the precipitate was filtered. The filtrate was washed with isopropyl alcohol and dried to obtain 8.6 g of DA-5-4 (yellowish white solid) (yield 96%).

  Example 2-5 Synthesis of DA-5

To a 300 mL four-necked flask, 7.6 g of DA-5-4, 70 mL of ethyl acetate, 70 mL of pure water, 7.8 g of reduced iron, and 6.0 g of ammonium chloride were added and stirred while heating to 60 ° C. After completion of the reaction, reduced iron was filtered and the organic layer was extracted with ethyl acetate. Anhydrous magnesium sulfate was added to the organic layer, followed by dehydration and drying, and anhydrous magnesium sulfate was filtered. The solvent of the obtained filtrate was distilled off using a rotary evaporator. The residue was washed with isopropanol and dried to obtain 5.3 g of DA-5 (yellowish white solid) (yield 78%). The result of measuring the obtained solid by ¹ H-NMR is shown below. From this result, it was confirmed that the obtained solid was the target DA-5.
¹ H NMR (400 MHz, [D ₆ ] -DMSO): δ7.62-7.64 (d, 2H), 7.56-7.68 (d, 1H), 6.91-6.93 (d, 2H), 6.44-6.48 (d, 1H), 6.42 (s, 1H), 6.00 (s, 1H), 5.91 (s, 1H), 5.69-5.72 (d, 2H), 5.66 (s, 1H), 4.36 (s, 2H), 4.32 (s , 2H), 3.96-4.00 (t, 2H), 3.71-3.74 (t, 2H), 1.84 (s, 3H), 1.62-1.72 (m, 4H), 1.40-1.44 (m, 4H)

  Example 3 Synthesis of DA-6

  Example 3-1 Synthesis of DA-6 Precursor DA-6-1

（上記反応式中、Ｍｓはメタンスルホニルを表す。）

(In the above reaction formula, Ms represents methanesulfonyl.)

  To a 500 mL four-necked flask, 23.4 g of 2-hydroxyethyl methacrylate, 22.1 g of triethylamine, and 250 mL of tetrahydrofuran were added. The system was cooled to 0 ° C., 25.0 g of methanesulfonyl chloride was added, and the mixture was stirred at room temperature. After completion of the reaction, 50 mL of pure water was added and stirred, and then the organic layer was extracted by adding ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, filtered, and then the solvent was distilled off using a rotary evaporator. 37.5 g of DA-6-1 (red viscous body) was obtained. The obtained compound was directly used in the next step.

  Example 3-2 Synthesis of DA-6 precursor DA-6-2

（上記反応式中、Ｍｓはメタンスルホニルを表す。）

(In the above reaction formula, Ms represents methanesulfonyl.)

  While adding 22.0 g of DA-5-1, 500 mL of N, N-dimethylformamide, 24.9 g of DA-6-1 and 41.4 g of potassium carbonate to a 1 L four-necked flask, heating to 60 ° C. Stir. After completion of the reaction, the reaction system was poured into 1 L of water, neutralized with 1N aqueous hydrochloric acid, and extracted with ethyl acetate. To the extracted organic layer, anhydrous magnesium sulfate was added, dehydrated and dried, and anhydrous magnesium sulfate was filtered. The obtained filtrate was evaporated using a rotary evaporator, 200 mL of formic acid was added, and the mixture was stirred while heating to 50 ° C. After completion of the reaction, the reaction system was poured into 500 mL of water, and the precipitate was filtered. This filtrate was washed with isopropyl alcohol and dried to obtain 16.5 g of DA-6-2 (white solid) (yield 60%).

  Example 3-3 Synthesis of DA-6 precursor DA-6-3

  In a 300 mL four-necked flask, 11.5 g of DA-6-2, 150 mL of tetrahydrofuran, 23.6 g of 1,6-hexanediol, 11 of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride. 9 g and 0.49 g of 4-dimethylaminopyridine were added and stirred at room temperature. After completion of the reaction, the reaction system was poured into 300 mL of ethyl acetate and extracted with saturated brine. To the extracted organic layer, anhydrous magnesium sulfate was added, dehydrated and dried, and anhydrous magnesium sulfate was filtered. The solvent was distilled off from the obtained filtrate using a rotary evaporator to obtain 15.4 g of DA-6-3 (reddish brown viscous body). The obtained compound was directly used in the next step.

  Example 3-4 Synthesis of DA-6 precursor DA-6-4

  To a 300 mL four-necked flask, add 15.4 g of DA-6-3, 150 mL of N, N-dimethylformamide, 8.2 g of 2,4-dinitrofluorobenzene, and 8.3 g of triethylamine, and heat to 80 ° C. Stir. After completion of the reaction, the reaction system was poured into 500 mL of ethyl acetate and extracted with saturated brine. To the extracted organic layer, anhydrous magnesium sulfate was added, dehydrated and dried, and anhydrous magnesium sulfate was filtered. The solvent of the obtained filtrate was distilled off using a rotary evaporator. The residue was washed with an ethyl acetate / hexane (1: 4) solution and dried to obtain 12.6 g of DA-6-4 (skin colored solid) (yield 56%).

  Example 3-5 Synthesis of DA-6

To a 500 mL four-necked flask, 12.6 g of DA-6-4, 150 mL of ethyl acetate, 150 mL of pure water, 7.7 g of reduced iron, and 9.9 g of ammonium chloride were added and stirred while heating to 60 ° C. After completion of the reaction, reduced iron was filtered and the organic layer was extracted with ethyl acetate. Anhydrous magnesium sulfate was added to the organic layer, followed by dehydration and drying, and anhydrous magnesium sulfate was filtered. The solvent of the obtained filtrate was distilled off using a rotary evaporator. The residue was isolated by silica gel column chromatography (ethyl acetate: hexane = 2: 1 volume ratio) to obtain 7.1 g of DA-6 (reddish brown viscous body) (yield 63%). The result of measuring the obtained viscous body by ¹ H-NMR is shown below. From this result, it was confirmed that the obtained viscous body was the target DA-6.
¹ H NMR (400 MHz, [D ₆ ] -DMSO): δ7.66-7.68 (d, 2H), 7.58-7.62 (d, 1H), 6.99-7.02 (d, 2H), 6.48-6.52 (d, 1H), 6.46 (s, 1H), 6.03 (s, 1H), 5.95 (s, 1H), 5.73-5.76 (d, 1H), 5.70 (s, 1H), 4.40-4.45 (m, 4H), 4.29 -4.34 (m, 4H), 4.12-4.15 (t, 2H), 3.74-3.78 (t, 2H), 1.88 (s, 3H), 1.64-1.68 (m, 4H), 1.42-1.43 (m, 4H)

  Example 4 Synthesis of DA-7

In a reaction vessel, 4-bromohydroxybenzene (100 g, 578 mmol), tert-butyl acrylate (156 g, 1.21 mol), palladium (II) acetate (2.6 g, 11.6 mmol), tri (o-tolyl) phosphine ( 7.0 g, 23.1 mmol), tributylamine (321 g, 1.73 mol), N, N′-dimethylacetamide (hereinafter referred to as DMAc) (500 g) were added, and the mixture was heated and stirred at 100 ° C. The reaction was monitored by HPLC. After completion of the reaction, the reaction solution was poured into 1M aqueous hydrochloric acid (2 L) and stirred for a while. Ethyl acetate (1 L) was added thereto, the aqueous layer was removed by liquid separation operation, the organic layer was washed 3 times with saturated brine (500 mL), the organic layer was dried over magnesium sulfate, filtered, and the solvent was distilled off. This gave compound [1] (158 g). The result of measuring the obtained compound by ¹ H-NMR is shown below. The obtained compound was directly used in the next step.
¹ H-NMR (400 MHz, CDCl ₃ , δ ppm): 7.52 (1H, d), 7.40 (2H, d), 6.76 (1H, d), 6.22 (2H, d), 1.52 (9H, s).

The reaction vessel was charged with compound [1] (20.00 g, 90.8 mmol), triethylamine (11.94 g, 118 mmol), tetrahydrofuran (hereinafter referred to as THF) (200 g), and after nitrogen substitution, the internal temperature was 10 ° C. While being careful not to exceed, a solution of 3,5-dinitrobenzoyl chloride (25.12 g, 109 mmol) in THF (100 g) was added dropwise. The reaction was monitored by HPLC. After completion of the reaction, the reaction solution was poured into distilled water (1.8 L), and the precipitated solid was filtered and washed thoroughly with distilled water to obtain a crude product of compound [2]. Next, methanol (240 g) was added to the obtained crude product, and after heating and refluxing for 30 minutes, the mixture was allowed to cool to room temperature, filtered, and the solid was dried to obtain compound [2] (yield 18.0 g). , Yield 49%). The result of measuring the obtained compound by ¹ H-NMR is shown below.
¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 9.09-9.08 (1H, m), 9.05-9.04 (2H, m), 7.84-7.80 (2H, m), 7.57 (1H, m), 7.46 -7.38 (2H, m), 6.54 (1H, d), 1.46 (9H, s).

Compound [2] (15.82 g, 38.2 mmol) and formic acid (80 g) were added to the reaction vessel, and the mixture was heated and stirred at 40 ° C. The reaction was monitored by HPLC, and after confirming the completion of the reaction, the reaction solution was poured into distilled water (800 mL), and the solid was filtered and thoroughly washed with distilled water. The obtained solid was dried to obtain compound [3] (yield 13.1 g, yield 96%). The result of measuring the obtained compound by ¹ H-NMR is shown below.
¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 12.5 (1H, brs), 9.10-9.09 (1H, m), 9.09-9.04 (2H, m), 7.84-7.80 (2H, m), 7.60 (1H, d), 7.44-7.41 (2H, m), 6.54 (1H, d).

In a reaction vessel, compound [3] (13.07 g, 36.5 mmol), 2-hydroxyethyl methacrylate (hereinafter referred to as HEMA) (5.70 g, 43.8 mmol), 1- (3-dimethylaminopropyl)- 3-ethylcarbodiimide (hereinafter referred to as EDC) (9.09 g, 47.4 mmol), 4-dimethylaminopyridine (hereinafter referred to as DMAP) (0.45 g, 3.65 mmol), THF (200 g) were added, Stirring was performed at room temperature. After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (1.2 L) and extracted with ethyl acetate. The organic layer was washed 3 times with distilled water, dried over magnesium sulfate, filtered, and the solvent was distilled off with an evaporator to obtain compound [4] (yield 16.8 g, yield 98%). The result of measuring the obtained compound by ¹ H-NMR is shown below.
¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 9.09-9.08 (1H, m), 9.06-9.04 (2H, m), 7.88-7.86 (2H, m), 7.69 (1H, d), 7.44 -7.42 (2H, m), 6.68 (1H, d), 6.03-6.02 (1H, m), 5.69-5.67 (1H, m), 4.41-4.39 (2H, m), 4.36-4.34 (2H, m) , 1.86-1.85 (3H, m).

Compound [4] (16.8 g, 35.7 mmol), tin (IV) chloride (48.42 g, 255 mmol), THF (170 g) and distilled water (170 g) were added to the reaction vessel, and the mixture was heated and stirred at 70 ° C. It was. After confirming the completion of the reaction by HPLC, the reaction solution was poured into a beaker containing ethyl acetate (1 L), and the mixture was neutralized by adding sodium bicarbonate powder while stirring. Thereafter, the precipitated solid was removed by filtration, and the filtrate was washed twice with a saturated aqueous sodium hydrogen carbonate solution (200 g) and three times with a saturated saline solution (500 g), and dried over magnesium sulfate. Thereafter, filtration and solvent evaporation were performed to obtain the target compound DA-7 (yield 12.9 g, yield 86%). The result of measuring the obtained compound by ¹ H-NMR is shown below.
¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 7.85-7.84 (3H, m), 7.66 (1H, d), 7.45-7.43 (2H, m), 6.41-6.38 (2H, m), 6.05 -6.01 (2H, m), 5.70-5.63 (1H, m), 4.96 (4H, brs), 4.39-4.38 (2H, m), 4.37-4.35 (2H, m), 1.85-1.84 (3H, m) .

  Example 5 Synthesis of DA-8

A reaction vessel was charged with compound [1] (127.3 g, 578 mmol), triethylamine (70.19 g, 694 mmol) and THF (800 g), and after evacuating with nitrogen, methacryloyl chloride was carefully taken so that the internal temperature did not exceed 10 ° C. A solution of (63.4 g, 607 mmol) in THF (200 g) was added dropwise. After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (3 L) and extracted with ethyl acetate (1.5 L). The organic layer was washed 3 times with saturated brine (500 g), dried over magnesium sulfate, filtered and evaporated to give compound [5]. The result of measuring the obtained compound by ¹ H-NMR is shown below. Compound [5] was used in the next step without purification.
¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 7.78-7.72 (2H, m), 7.53 (1H, d), 7.21-7.18 (2H, m), 6.48 (1H, d), 6.25-6.24 (1H, m), 5.88-5.86 (1H, m), 1.97-1.95 (3H, m), 1.45 (9H, s).

The reaction vessel was charged with compound [5] (166.0 g, 578 mmol) and dichloromethane (hereinafter referred to as DCM) (834 g), and after nitrogen substitution, trifluoroacetic acid (328 g, 2.88 mol) was added dropwise. After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (1 L), and the precipitated solid was filtered to obtain a crude product. Next, the obtained crude product was washed and stirred with a mixed solution (200 g) of ethyl acetate / hexane weight ratio 1: 2, filtered again, and the solid was dried to obtain compound [6] (yield 79.5 g, Yield 59%). The result of measuring the obtained compound by ¹ H-NMR is shown below.
¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 7.74-7.71 (2H, m), 7.57 (1H, d), 7.21-7.18 (2H, m), 6.49 (1H, d), 6.56-6.25 (1H, m), 5.89-5.88 (1H, m), 1.97-1.96 (3H, m).

In a reaction vessel, 2- (2,4-dinitrophenyl) ethanol (43.67 g, 206 mmol), compound [6] (45.53 g, 196 mmol), EDC (48.87 g, 255 mmol), DMAP (2.4 g, 19 mmol) ) And THF (900 g) were added, and the mixture was stirred at room temperature. After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (3 L) and extracted with ethyl acetate (1 L). Thereafter, the organic layer was washed 3 times with distilled water, dried over magnesium sulfate, filtered, and the solvent was distilled off with an evaporator to obtain a crude compound [7]. The obtained crude product was dispersed and washed with methanol (100 mL), filtered and dried under reduced pressure to obtain compound [7]. (Yield 48.3 g, Yield 58%). The result of measuring the obtained compound by ¹ H-NMR is shown below.
¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 8.71 (1H, d), 8.47 (2H, dd), 7.88 (1H, d), 7.75-7.72 (2H, m), 7.59 (1H, d ), 7.23-7.20 (2H, m), 6.49 (1H, d), 6.26-6.25 (1H, m), 5.90-5.88 (1H, m), 4.43 (2H, 5), 3.35 (2H, t), 1.97-1.96 (3H, m).

Compound [7] (48.25 g, 113 mmol), iron (37.91 g, 679 mmol), ethyl acetate (435 g), ammonium chloride (18.15 g, 340 mmol) and distilled water (160 g) were added to the reaction vessel at 70 ° C. The mixture was stirred with heating. After confirming the completion of the reaction by HPLC, the solid was removed by celite filtration and washing with ethyl acetate (1 L). The filtrate was washed 3 times with saturated brine (500 g), the organic layer was dried over magnesium sulfate, and then the solvent was distilled off with an evaporator to obtain a crude product of compound DA-8. The obtained crude product was dispersed and washed with methanol, filtered and dried under reduced pressure to obtain Compound DA-8 (yield 29.8 g, yield 72%). The result of measuring the obtained compound by ¹ H-NMR is shown below.
¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 7.78-7.74 (2H, m), 7.63 (1H, d), 7.24-7.18 (2H, m), 6.59 (1H, d), 6.57 (1H , s), 6.27-6.26 (1H, m), 5.91-5.88 (1H, m), 5.86 (1H, d), 5.76 (1H, dd), 3.99 (4H, brs), 4.14 (2H, t), 2.65 (2H, t), 1.97-1.95 (3H, m).

  Example 6 Synthesis of DA-9

（上記反応式中の●が表記してあるシクロヘキサン環は、立体構造が1,4-trans-シクロヘキサン環であることを表す。）

(The cyclohexane ring indicated by ● in the above reaction formula indicates that the three-dimensional structure is a 1,4-trans-cyclohexane ring.)

In a reaction vessel, trans-4- (4-bromophenyl) cyclohexanol (200 g, 784 mmol), tert-butyl acrylate (211 g, 1.65 mol), palladium (II) acetate (3.5 g, 15.7 mmol), tri (O-Tolyl) phosphine (9.5 g, 31.4 mmol), tributylamine (436 g, 2.35 mol) and DMAc (1000 g) were added, and the mixture was heated and stirred at 100 ° C. After confirming the completion of the reaction by HPLC, the reaction solution was poured into 1M aqueous hydrochloric acid (3.5 L) and stirred for a while. Ethyl acetate (1.5 L) was added thereto, the aqueous layer was removed by liquid separation operation, the organic layer was washed 3 times with saturated brine (500 mL), the organic layer was dried over magnesium sulfate, filtered, and the solvent Was distilled off to obtain compound [8] (yield 208 g, yield 88%). The result of measuring the obtained compound by ¹ H-NMR is shown below.
¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 7.58 (2H, d), 7.50 (1H, d), 7.25 (2H, d), 6.44 (1H, d), 4.59 (1H, d), 3.46-3.36 (1H, m), 2.50-2.46 (1H, m), 1.93-1.90 (2H, m), 1.66-1.73 (2H, m), 1.49-1.26 (13H, m).

The reaction vessel was charged with compound [8] (40.0 g, 132 mmol), triethylamine (16.1 g, 159 mmol), THF (300 g), and after replacing with nitrogen, taking care not to exceed an internal temperature of 10 ° C. A solution of 5-dinitrobenzoyl chloride (32.0 g, 139 mmol) in THF (180 g) was added dropwise. After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (2 L) and stirred for a while. Thereafter, the precipitated solid was filtered and washed well with distilled water to obtain a crude compound [9]. Next, methanol (300 g) was added to the obtained crude product and stirred for 30 minutes at room temperature, followed by filtration and drying of the solid to obtain compound [9] (yield 41.8 g, yield 64%). The result of measuring the obtained compound by ¹ H-NMR is shown below.
¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 9.02-9.01 (1H, m), 8.89-8.88 (2H, m), 7.58 (2H, d), 7.49 (1H, d), 7.28 (2H , d), 6.43 (1H, d), 5.06 (1H, m), 2.47-2.43 (1H, m), 2.17-1.15 (2H, m), 1.88-1.86 (2H, m), 1.75-1.60 (4H , m), 1.44 (9H, s).

Compound [9] (41.80 g, 84.2 mmol) and formic acid (210 g) were added to the reaction vessel, and the mixture was heated and stirred at 40 ° C. After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (2 L), and the solid was filtered and thoroughly washed with distilled water. The obtained solid was dried to obtain compound [10] (yield 37 g, yield 99%). The result of measuring the obtained compound by ¹ H-NMR is shown below.
¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 9.03-9.02 (1H, m), 8.90-8.88 (2H, m), 7.58 (2H, d), 7.55 (1H, d), 7.30 (2H , d), 6.44 (1H, d), 5.07-5.06 (1H, m), 2.64-2.59 (1H, m), 2.17-2.15 (2H, m), 1.88-1.86 (2H, m), 1.75-1.65 (4H, m).

Compound [10] (37.8 g, 85.8 mmol), HEMA (13.4 g, 103 mmol), EDC (21.38 g, 112 mmol), DMAP (1.05 g, 8.6 mmol), THF (570 g) in a reaction vessel And stirred at room temperature. After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (1.8 L) and extracted with ethyl acetate. The organic layer was washed three times with distilled water, dried over magnesium sulfate, filtered, and the solvent was distilled off with an evaporator to obtain a crude compound [11]. The obtained crude product was washed with 2-propanol (100 g) to obtain compound [11] (yield 47.1 g, yield 99%). The result of measuring the obtained compound by ¹ H-NMR is shown below.
¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 9.02-9.01 (1H, m), 8.89-8.88 (2H, m), 7.63-7.55 (3H, m), 7.30 (2H, d), 6.59 (1H, d), 6.01-5.99 (1H, m), 5.69-5.67 (1H, m), 5.15-4.99 (1H, m), 4.37-4.32 (4H, m), 2.64-2.58 (1H, m) , 2.17-2.15 (2H, m), 1.95-1.62 (11H, m).

Compound [11] (47.4 g, 85.8 mmol), tin (IV) chloride (114 g, 601 mmol), THF (470 g), and distilled water (470 g) were added to the reaction vessel, and the mixture was heated and stirred at 70 ° C. After confirming the completion of the reaction by HPLC, the reaction solution was poured into a beaker containing ethyl acetate (1.5 L) and neutralized by adding sodium bicarbonate powder while stirring. Thereafter, the precipitated solid was removed by filtration, and the filtrate was washed twice with a saturated aqueous sodium hydrogen carbonate solution (200 g) and three times with a saturated saline solution (500 g), and dried over magnesium sulfate. Thereafter, filtration and solvent evaporation were performed to obtain the target compound DA-9 (yield 32.5 g, yield 76%). The result of measuring the obtained compound by ¹ H-NMR is shown below.
¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 7.64-7.59 (3H, m), 7.29 (2H, d), 6.58 (1H, d), 6.40-6.39 (2H, m), 6.01-5.98 (2H, m), 5.67-5.66 (1H, m), 4.97 (4H, brs), 4.86-4.81 (1H, m), 4.38-4.33 (4H, m), 2.62-2.46 (1H, m), 2.06 -2.03 (2H, m), 1.99-1.94 (5H, m), 1.66-1.47 (4H, m)

  Example 7 Synthesis of DA-10

（上記反応式中の●が表記してあるシクロヘキサン環は、立体構造が1,4-trans-シクロヘキサン環であることを表す。）

(The cyclohexane ring indicated by ● in the above reaction formula indicates that the three-dimensional structure is a 1,4-trans-cyclohexane ring.)

The reaction vessel was charged with compound [8] (74.43 g, 261 mmol), triethylamine (29.81 g, 295 mmol), THF (1000 g), and after nitrogen substitution, methacryloyl chloride was carefully taken so that the internal temperature did not exceed 10 ° C. A solution of (27.01 g, 258 mmol) in THF (100 g) was added dropwise. After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (3 L) and extracted with ethyl acetate (1.5 L). The organic layer was washed 3 times with saturated brine (500 g), dried over magnesium sulfate, filtered and evaporated to give a crude compound [12]. The obtained crude product was dispersed and washed with methanol (100 g), filtered, and the solid was dried to obtain Compound [12] (yield 72.9 g, yield 80%). The result of measuring the obtained compound by ¹ H-NMR is shown below.
¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 7.56 (2H, d), 7.47 (1H, d), 7.26 (2H, d), 6.42 (1H, d), 4.75-4.69 (1H, m ), 2.59-4.47 (1H, m), 2.01-1.98 (2H, m), 1.85-1.78 (5H, m), 1.59-1.44 (4H, m).

Compound [12] (20.29 g, 54.8 mmol) and DCM (100 g) were charged into a reaction vessel, and after nitrogen substitution, trifluoroacetic acid (31.2 g, 274 mol) was added dropwise. After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (200 mL) and extracted with ethyl acetate (1 L). Thereafter, the organic layer was washed 3 times with saturated brine (200 g), and the organic layer was dried over magnesium sulfate, filtered and evaporated to give a crude product of compound [13]. The obtained crude product was dispersed and washed with methanol (30 g), filtered and dried to obtain compound [13] (yield 10.9 g, yield 64%). The result of measuring the obtained compound by ¹ H-NMR is shown below.
¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 12.32 (1H, brs), 7.58-7.50 (3H, m), 7.27 (2H, d), 6.43 (1H, d), 5.99-5.98 (1H , m), 5.64-5.63 (1H, m), 4.78-4.70 (1H, m), 2.59-2.51 (1H, m), 2.02-1.95 (2H, m), 1.82-1.79 (5H, m), 1.63 -1.42 (4H).

In a reaction vessel, 2- (2,4-dinitrophenyl) ethanol (11.94 g, 56.3 mmol), compound [13] (10.89 g, 35.3 mmol), EDC (11.62 g, 61.0 mmol), DMAP (0.57 g, 4.7 mmol) and THF (130 g) were added, and the mixture was stirred at room temperature. After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (600 mL), and the precipitated solid was filtered and washed with distilled water to obtain a crude compound [14]. The obtained crude product was dispersed and washed with methanol (100 mL), filtered and dried under reduced pressure to obtain Compound [14] (yield 17.1 g, yield 96%). The result of measuring the obtained compound by ¹ H-NMR is shown below.
¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 8.70-8.69 (1H, m), 8.48-8.45 (1H, m), 7.87 (1H, d), 7.58-7.52 (3H, m), 7.27 (2H, d), 6.44 (1H, d), 5.99-5.98 (1H, m), 5.63-5.62 (1H, m), 4.76-4.71 (1H, m), 4.41 (2H, t), 3.34 (2H , t), 2.57-2.54 (1H, m), 2.01-1.97 (2H, m), 1.84-1.78 (5H, m), 1.60-1.45 (4H, m).

Compound [14] (17.00 g, 33.4 mmol), iron (11.2 g, 201 mmol), ethyl acetate (150 g), ammonium chloride (5.35 g, 100 mmol), distilled water (50 g) were added to the reaction vessel, Stirring was performed at 70 ° C. After confirming the completion of the reaction by HPLC, the solid was removed by celite filtration and washing with ethyl acetate (200 mL). The filtrate was washed 3 times with saturated brine (200 g), the organic layer was dried over magnesium sulfate, and then the solvent was distilled off with an evaporator to obtain a crude product of compound DA-10. The obtained crude product was dispersed and washed with methanol (100 g), filtered and dried under reduced pressure to obtain Compound DA-10 (yield 10.3 g, yield 69%). The result of measuring the obtained compound by ¹ H-NMR is shown below.
¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 7.61-7.57 (3H, m), 7.27 (2H, d), 6.58-6.51 (2H, m), 5.99 (1H, s), 5.85 (1H , d), 5.75 (1H, dd), 5.65-5.63 (1H, m), 4.80-4.71 (1H, m), 4.63 (2H, brs), 4.57 (2H, brs), 4.12 (2H, t), 2.64 (2H, t), 2.59-2.53 (1H, m), 2.00-1.98 (2H, m), 1.85-1.79 (5H, m), 1.64-1.44 (4H, m).

  Example 8 Synthesis of DA-11

In a reaction vessel, 4′-bromo- [1,1′-biphenyl] -4-ol (150 g, 602 mmol), tert-butyl acrylate (162 g, 1.26 mol), palladium (II) acetate (2.70 g, 12 0.0 mmol), tri (o-tolyl) phosphine (7.33 g, 24.1 mmol), tributylamine (335 g, 1.81 mol) and DMAc (750 g) were added, and the mixture was heated and stirred at 100 ° C. After confirming the completion of the reaction by HPLC, the reaction solution was poured into 1M aqueous hydrochloric acid (3.5 L) and stirred for a while. Ethyl acetate (1 L) was added thereto, the aqueous layer was removed by liquid separation operation, the organic layer was washed 3 times with saturated brine (500 mL), the organic layer was dried over magnesium sulfate, filtered, and the solvent was distilled off. To give compound [15] (yield 176 g, yield 99%). The result of measuring the obtained compound by ¹ H-NMR is shown below.
¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 9.67 (1H, s), 7.72 (2H, d), 7.62 (2H, d), 7.19-7.54 (3H, m), 6.89-6.82 (2H m), 6.52 (1H, d), 1.49 (9H, s).

The reaction vessel was charged with compound [15] (73.4 g, 318 mmol), triethylamine (36.8 g, 364 mmol), THF (1000 g), and after purging with nitrogen, being careful not to exceed an internal temperature of 10 ° C. A solution of 5-dinitrobenzoyl chloride (73.37 g, 318 mmol) in THF (300 g) was added dropwise. After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (6 L) and stirred for a while. Thereafter, the precipitated solid was filtered and washed well with distilled water to obtain a crude product of compound [16]. Next, methanol (1 L) was added to the resulting crude product and stirred for 30 minutes at room temperature, followed by filtration and drying of the solid to obtain compound [16] (yield 117.9 g, yield 79%). The result of measuring the obtained compound by ¹ H-NMR is shown below.
¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 9.14-9.13 (1H, m), 9.13-9.10 (2H, m), 7.88-7.76 (6H, m), 7.74 (1H, d), 7.52 -7.50 (2H, m), 6.59 (1H, m), 1.50-1.49 (9H, m).

Compound [16] (117.9 g, 240 mmol) and formic acid (1180 g) were added to the reaction vessel, and the mixture was heated and stirred at 40 ° C. After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (3 L), and the solid was filtered and thoroughly washed with distilled water. The obtained solid was dried to obtain Compound [17] (Yield 102 g, Yield 98%). The result of measuring the obtained compound by ¹ H-NMR is shown below.
¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 9.15-9.13 (1H, m), 9.11-9.10 (2H, m), 7.89-7.86 (2H, m), 7.83-7.77 (4H, m) , 7.64 (1H, d), 7.55-7.49 (2H, m), 6.60 (1H, d),

Compound [17] (40.0 g, 92.1 mmol), HEMA (18.0 g, 138 mmol), EDC (22.8 g, 120 mmol), DMAP (1.13 g, 9.2 mmol), THF (600 g) in a reaction vessel And stirred at room temperature. After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (3 L) and extracted with ethyl acetate. The organic layer was washed 3 times with saturated brine (500 g), dried over magnesium sulfate, filtered, and evaporated to give a crude product of compound [18]. The obtained crude product was washed with methanol (300 g) to obtain compound [18] (yield 27.8 g, yield 55%). The result of measuring the obtained compound by ¹ H-NMR is shown below.
¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 9.14-9.12 (1H, m), 9.10-9.09 (2H, m), 7.88-7.84 (4H, m), 7.79-7.71 (3H, m) , 7.52-7.50 (2H, m), 6.73 (1H, d), 6.07-6.06 (1H, m), 5.72-5.71 (1H, m), 4.46-4.43 (2H, m), 4.40-4.38 (2H, m), 1.90-1.89 (3H, m).

Compound [18] (27.8 g, 50.9 mmol), tin (IV) chloride (67.6 g, 357 mmol), THF (280 g) and distilled water (220 g) were added to the reaction vessel, and the mixture was heated and stirred at 70 ° C. It was. After confirming the completion of the reaction by HPLC, the reaction solution was poured into a beaker containing ethyl acetate (2 L), and neutralized by adding sodium bicarbonate powder while stirring. Thereafter, the precipitated solid was removed by filtration, and the filtrate was washed twice with a saturated aqueous sodium hydrogen carbonate solution (200 g) and three times with a saturated saline solution (500 g), and dried over magnesium sulfate. Thereafter, filtration and solvent distillation were performed to obtain the target compound DA-11 (yield 23.9 g, yield 97%). The result of measuring the obtained compound by ¹ H-NMR is shown below.
¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 7.86-7.71 (7H, m), 7.32-7.30 (2H, m), 6.73 (1H, d), 6.61-6.60 (2H, m), 6.12 -6.11 (1H, m), 6.06-6.05 (1H, m), 5.72-5.71 (1H, m), 5.12 (4H, brs), 4.45-4.30 (2H, m), 4.40-4.38 (2H, m) , 1.89-1.87 (3H, m).

  Example 9 Synthesis of DA-12

The reaction vessel was charged with compound [15] (89.15 g, 303 mmol), triethylamine (36.8 g, 364 mmol), THF (1000 g), and after substitution with nitrogen, methacryloyl chloride was carefully taken so that the internal temperature did not exceed 10 ° C. A solution of (33.27 g, 318 mmol) in THF (330 g) was added dropwise. After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (6 L), stirred for a while, and then the precipitated solid was filtered and washed thoroughly with distilled water to obtain a crude compound [19]. Next, methanol (1 L) was added to the resulting crude product, and after stirring at room temperature for 30 minutes, filtration and solid were dried to obtain compound [19] (yield 94.5 g, yield 86%). The result of measuring the obtained compound by ¹ H-NMR is shown below.
¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 7.81-7.73 (6H, m), 7.60 (1H, d), 7.32-7.28 (2H, m), 6.59 (1H, d), 6.33-6.30 (1H, m), 5.93-5.92 (1H, m), 2.02-2.00 (3H, m), 1.49 (9H, s), 1.59-1.44 (4H, m).

Compound [19] (94.51 g, 259 mmol) and formic acid (475 g) were charged into a reaction vessel, and after substitution with nitrogen, heating and stirring were performed at 40 ° C. After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (3.5 L), the precipitated solid was filtered, washed well with distilled water, and the solid was dried under reduced pressure to obtain compound [20] (yield) 74.9 g, 75% yield). The result of measuring the obtained compound by ¹ H-NMR is shown below.
¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 7.81-7.63 (6H, m), 7.64 (1H, d), 7.32-7.28 (2H, m), 6.60 (1H, d), 6.32-6.31 (1H, m), 5.93-5.92 (1H, m), 2.03-2.02 (3H, m).

In a reaction vessel, 2- (2,4-dinitrophenyl) ethanol (41.29 g, 195 mmol), compound [20] (50.00 g, 162 mmol), EDC (40.21 g, 211 mmol), DMAP (1.98 g, 16 0.2 mmol) and THF (600 g) were added, and the mixture was stirred at room temperature. After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (3.6 L), and the precipitated solid was filtered and washed with distilled water to obtain a crude compound [21]. The obtained crude product was dispersed and washed with methanol (300 mL), filtered and dried under reduced pressure to obtain compound [21] (yield 65.1 g, yield 80%). The result of measuring the obtained compound by ¹ H-NMR is shown below.
¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 8.76-8.75 (1H, m), 8.54-8.48 (1H, m), 7.93 (1H, d), 7.82-7.61 (7H, m), 7.31 -7.28 (2H, m), 6.62-6.57 (1H, m), 6.32-6.31 (1H, m), 5.93-5.92 (1H, m), 4.48 (2H, t), 3.39 (2H, t), 2.03 -2.02 (3H, m).

Compound [21] (65.01 g, 130 mmol), tin (IV) chloride (171.9 g, 906 mmol), THF (650 g), and distilled water (520 g) were added to the reaction vessel, and the mixture was heated and stirred at 70 ° C. After confirming the completion of the reaction by HPLC, the reaction solution was poured into a beaker containing ethyl acetate (3.5 L), and neutralized by adding sodium bicarbonate powder while stirring. Thereafter, the precipitated solid was removed by filtration, and the filtrate was washed twice with a saturated aqueous sodium hydrogen carbonate solution (200 g) and three times with a saturated saline solution (500 g), and dried over magnesium sulfate. Thereafter, filtration and solvent distillation were performed to obtain a crude product of the desired compound DA-12. Next, the obtained crude product was dispersed and washed with methanol (200 g), filtered, and the solid was dried to obtain Compound DA-12 (yield 49.5 g, yield 76%). The result of measuring the obtained compound by ¹ H-NMR is shown below.
¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 7.84-7.55 (7H, m), 7.31-7.28 (2H, m), 6.60 (1H, d), 6.53 (1H, d), 6.32-6.30 (1H, m), 5.93-5.91 (2H, m), 5.83-5.81 (1H, m), 4.19-4.18 (2H, m), 2.71-2.70 (2H, m), 3,17 (4H, brs) , 2.03-2.27 (3H, m)

(Example 10) Synthesis of liquid crystal aligning agent 1.90 g (0.0096 mol) of CBDA, 0.27 g (0.0025 mol) of DA-1, 3.06 g (0.0060 mol) of DA-4, DA- 0.57 g (0.0015 mol) of 2 was reacted in 32.91 g of NMP at room temperature for 16 hours to prepare a solution of polyamic acid (PAA-1). This polyamic acid had a number average molecular weight of about 13,000 and a weight average molecular weight of about 44,000. NMP and BCS were added to 10 g of this polyamic acid solution and stirred, and after preparing so that the polyamic acid (PAA-1) was 6% by mass, NMP was 74% by mass, and BCS was 20% by mass, the pore diameter was 1 μm. The liquid crystal alignment agent of Example 10 was obtained by pressure filtration with a membrane filter.

(Example 11) Synthesis of liquid crystal aligning agent 1.94 g (0.0099 mol) of CBDA, 4.34 g (0.0085 mol) of DA-4, 0.57 g (0.0015 mol) of DA-2 and NMP It was made to react at room temperature for 16 hours in 38.83g, and the solution of polyamic acid (PAA-2) was prepared. This polyamic acid had a number average molecular weight of about 9000 and a weight average molecular weight of about 24,000. NMP and BCS were added to 10 g of this polyamic acid solution and stirred, and after preparing so that the polyamic acid (PAA-2) was 6% by mass, NMP was 74% by mass, and BCS was 20% by mass, the pore diameter was 1 μm. The liquid crystal alignment agent of Example 11 was obtained by pressure filtration with a membrane filter.

Example 12 Synthesis of Liquid Crystal Alignment Agent 1.94 g (0.0099 mol) of CBDA and 5.10 g (0.01 mol) of DA-4 were reacted in 39.93 g of NMP at room temperature for 16 hours to obtain a polyamic. A solution of acid (PAA-3) was prepared. This polyamic acid had a number average molecular weight of about 8,000 and a weight average molecular weight of about 19000. NMP and BCS were added to 10 g of this polyamic acid solution and stirred, and after preparing so that the polyamic acid (PAA-3) was 6% by mass, NMP was 74% by mass, and BCS was 20% by mass, the pore diameter was 1 μm. The liquid crystal aligning agent of Example 12 was obtained by pressure filtration with a membrane filter.

(Example 13) Synthesis of liquid crystal aligning agent 1.94 g (0.0099 mol) of CBDA, 4.10 g (0.0080 mol) of DA-4, 0.76 g (0.0020 mol) of DA-2 and NMP It was made to react at room temperature for 16 hours in 38.55g, and the solution of polyamic acid (PAA-6) was prepared. This polyamic acid had a number average molecular weight of about 10,000 and a weight average molecular weight of about 20,000. NMP and BCS were added to 10 g of this polyamic acid solution and stirred, and after preparing so that the polyamic acid (PAA-6) was 6 mass%, NMP was 74 mass%, and BCS was 20 mass%, the pore diameter was 1 μm. The liquid crystal alignment agent of Example 13 was obtained by pressure filtration with a membrane filter.

(Example 14) Synthesis of liquid crystal aligning agent 1.94 g (0.0099 mol) of CBDA, 3.86 g (0.0080 mol) of DA-5, 0.76 g (0.0020 mol) of DA-2 and NMP It was made to react at room temperature for 16 hours in 37.19g, and the solution of polyamic acid (PAA-7) was prepared. This polyamic acid had a number average molecular weight of about 10,000 and a weight average molecular weight of about 20,000. NMP and BCS were added to 10 g of this polyamic acid solution and stirred, and after preparing so that the polyamic acid (PAA-7) was 6% by mass, NMP was 74% by mass, and BCS was 20% by mass, the pore diameter was 1 μm. The liquid crystal aligning agent of Example 14 was obtained by pressure filtration with a membrane filter.

(Example 15) Synthesis of liquid crystal aligning agent 1.94 g (0.0099 mol) of CBDA, 3.86 g (0.0080 mol) of DA-6, 0.76 g (0.0020 mol) of DA-2 and NMP It was made to react at room temperature for 16 hours in 37.19g, and the solution of polyamic acid (PAA-8) was prepared. This polyamic acid had a number average molecular weight of about 9000 and a weight average molecular weight of about 18000. NMP and BCS were added to 10 g of this polyamic acid solution and stirred. After preparing so that the polyamic acid (PAA-8) was 6% by mass, NMP was 74% by mass, and BCS was 20% by mass, the pore diameter was 1 μm. The liquid crystal alignment agent of Example 15 was obtained by pressure filtration with a membrane filter.

Example 16 Synthesis of Liquid Crystal Alignment Agent 1.94 g (0.0099 mol) of CBDA, 2.93 g (0.0080 mol) of DA-8, 0.76 g (0.0020 mol) of DA-2 and NMP It was made to react at room temperature for 16 hours in 31.92 g, and the solution of polyamic acid (PAA-10) was prepared. This polyamic acid had a number average molecular weight of about 8,000 and a weight average molecular weight of about 16000. NMP and BCS were added to 10 g of this polyamic acid solution and stirred, and after preparing so that the polyamic acid (PAA-10) was 6% by mass, NMP was 74% by mass, and BCS was 20% by mass, the pore diameter was 1 μm. The liquid crystal aligning agent of Example 16 was obtained by pressure filtration with a membrane filter.

(Example 17) Synthesis of liquid crystal aligning agent 1.94 g (0.0099 mol) of CBDA, 3.94 g (0.0080 mol) of DA-9, 0.76 g (0.0020 mol) of DA-2 and NMP It was made to react at room temperature for 16 hours in 31.92 g, and the solution of polyamic acid (PAA-11) was prepared. This polyamic acid had a number average molecular weight of about 9000 and a weight average molecular weight of about 22,000. NMP and BCS were added to 10 g of this polyamic acid solution and stirred, and after preparing so that the polyamic acid (PAA-11) was 6 mass%, NMP was 74 mass%, and BCS was 20 mass%, the pore diameter was 1 μm. The liquid crystal aligning agent of Example 17 was obtained by pressure filtration with a membrane filter.

(Example 18) Synthesis of liquid crystal aligning agent 1.94 g (0.0099 mol) of CBDA, 3.59 g (0.0080 mol) of DA-10, 0.76 g (0.0020 mol) of DA-2 and NMP The mixture was reacted in 35.65 g at room temperature for 16 hours to prepare a solution of polyamic acid (PAA-12). This polyamic acid had a number average molecular weight of about 8,000 and a weight average molecular weight of about 23,000. NMP and BCS were added to 10 g of this polyamic acid solution and stirred, and after preparing so that the polyamic acid (PAA-12) was 6 mass%, NMP was 74 mass%, and BCS was 20 mass%, the pore diameter was 1 μm. The liquid crystal alignment agent of Example 18 was obtained by pressure filtration with a membrane filter.

Example 19 Synthesis of Liquid Crystal Alignment Agent 1.94 g (0.0099 mol) of CBDA, 3.89 g (0.0080 mol) of DA-11, 0.76 g (0.0020 mol) of DA-2 and NMP It was made to react at room temperature for 16 hours in 37.37g, and the solution of polyamic acid (PAA-13) was prepared. This polyamic acid had a number average molecular weight of about 7000 and a weight average molecular weight of about 20,000. NMP and BCS were added to 10 g of this polyamic acid solution and stirred, and after preparing so that the polyamic acid (PAA-13) was 6% by mass, NMP was 74% by mass, and BCS was 20% by mass, the pore diameter was 1 μm. The liquid crystal aligning agent of Example 19 was obtained by pressure filtration with a membrane filter.

(Example 20) Synthesis of liquid crystal aligning agent 1.94 g (0.0099 mol) of CBDA, 3.54 g (0.0080 mol) of DA-12, 0.76 g (0.0020 mol) of DA-2 and NMP A reaction was carried out in 35.37 g at room temperature for 16 hours to prepare a solution of polyamic acid (PAA-14). This polyamic acid had a number average molecular weight of about 8,000 and a weight average molecular weight of about 21,000. NMP and BCS were added to 10 g of this polyamic acid solution and stirred, and after preparing so that the polyamic acid (PAA-14) was 6% by mass, NMP was 74% by mass, and BCS was 20% by mass, the pore diameter was 1 μm. The liquid crystal alignment agent of Example 20 was obtained by pressure filtration with a membrane filter.

(Example 21) Synthesis of liquid crystal aligning agent 1.94 g (0.0099 mol) of CBDA and 4.82 g (0.01 mol) of DA-5 were reacted in 38.35 g of NMP at room temperature for 16 hours to obtain a polyamic. A solution of acid (PAA-15) was prepared. This polyamic acid had a number average molecular weight of about 11,000 and a weight average molecular weight of about 21,000. NMP and BCS were added to 10 g of this polyamic acid solution and stirred, and after preparing so that the polyamic acid (PAA-15) was 6% by mass, NMP was 74% by mass, and BCS was 20% by mass, the pore diameter was 1 μm. The liquid crystal alignment agent of Example 21 was obtained by pressure filtration with a membrane filter.

(Example 22) Synthesis of liquid crystal aligning agent 1.94 g (0.0099 mol) of CBDA and 4.82 g (0.01 mol) of DA-6 were reacted in 38.35 g of NMP at room temperature for 16 hours to obtain a polyamic. A solution of acid (PAA-16) was prepared. This polyamic acid had a number average molecular weight of about 10,000 and a weight average molecular weight of about 20,000. NMP and BCS were added to 10 g of this polyamic acid solution and stirred, and after preparing so that the polyamic acid (PAA-16) was 6 mass%, NMP was 74 mass%, and BCS was 20 mass%, the pore diameter was 1 μm. The liquid crystal alignment agent of Example 22 was obtained by pressure filtration with a membrane filter.

(Example 23) Synthesis of liquid crystal aligning agent 1.94 g (0.0099 mol) of CBDA and 3.66 g (0.01 mol) of DA-8 were reacted in 31.76 g of NMP at room temperature for 16 hours to obtain a polyamic. A solution of acid (PAA-18) was prepared. This polyamic acid had a number average molecular weight of about 9000 and a weight average molecular weight of about 18000. NMP and BCS were added to 10 g of this polyamic acid solution and stirred, and after preparing so that the polyamic acid (PAA-18) was 6 mass%, NMP was 74 mass%, and BCS was 20 mass%, the pore diameter was 1 μm. Pressure filtration was performed with a membrane filter to obtain a liquid crystal aligning agent of Example 23.

(Example 24) Synthesis of liquid crystal aligning agent 1.94 g (0.0099 mol) of CBDA and 4.92 g (0.01 mol) of DA-9 were reacted in 38.91 g of NMP at room temperature for 16 hours to obtain a polyamic. A solution of acid (PAA-19) was prepared. This polyamic acid had a number average molecular weight of about 10,000 and a weight average molecular weight of about 24,000. NMP and BCS were added to 10 g of this polyamic acid solution and stirred. After preparing so that the polyamic acid (PAA-19) was 6% by mass, NMP was 74% by mass, and BCS was 20% by mass, the pore diameter was 1 μm. The liquid crystal alignment agent of Example 24 was obtained by pressure filtration with a membrane filter.

(Example 25) Synthesis of liquid crystal aligning agent 1.94 g (0.0099 mol) of CBDA and 4.48 g (0.01 mol) of DA-10 were reacted in 36.42 g of NMP at room temperature for 16 hours to obtain a polyamic. A solution of acid (PAA-20) was prepared. This polyamic acid had a number average molecular weight of about 10,000 and a weight average molecular weight of about 23,000. After adding NMP and BCS to 10 g of this polyamic acid solution and stirring, the polyamic acid (PAA-20) is 6% by mass, NMP is 74% by mass, and BCS is 20% by mass. The liquid crystal alignment agent of Example 25 was obtained by pressure filtration with a membrane filter.

Example 26 Synthesis of Liquid Crystal Alignment Agent 1.94 g (0.0099 mol) of CBDA and 4.86 g (0.01 mol) of DA-11 were reacted in 38.57 g of NMP at room temperature for 16 hours to obtain a polyamic. A solution of acid (PAA-21) was prepared. This polyamic acid had a number average molecular weight of about 9000 and a weight average molecular weight of about 21,000. NMP and BCS were added to 10 g of this polyamic acid solution and stirred, and after preparing so that the polyamic acid (PAA-21) was 6% by mass, NMP was 74% by mass, and BCS was 20% by mass, the pore diameter was 1 μm. A liquid crystal aligning agent of Example 26 was obtained by pressure filtration with a membrane filter.

(Example 27) Synthesis of liquid crystal aligning agent 1.94 g (0.0099 mol) of CBDA and 4.42 g (0.01 mol) of DA-12 were reacted in 36.08 g of NMP at room temperature for 16 hours to obtain a polyamic. A solution of acid (PAA-22) was prepared. This polyamic acid had a number average molecular weight of about 8,000 and a weight average molecular weight of about 21,000. After adding NMP and BCS to 10 g of this polyamic acid solution and stirring, the polyamic acid (PAA-22) is 6 mass%, NMP is 74 mass%, and BCS is 20 mass%. The liquid crystal alignment agent of Example 27 was obtained by pressure filtration with a membrane filter.

Comparative Example 1 Synthesis of Liquid Crystal Alignment Agent 1.94 g (0.0099 mol) of CBDA, 2.23 g (0.0085 mol) of DA-3, 0.57 g (0.0015 mol) of DA-2 and NMP 18 In 97 g, the mixture was reacted at room temperature for 16 hours to prepare a solution of polyamic acid (PAA-4). This polyamic acid had a number average molecular weight of about 8,000 and a weight average molecular weight of about 22,000. NMP and BCS were added to 10 g of this polyamic acid solution and stirred, and after preparing so that the polyamic acid (PAA-4) was 6 mass%, NMP was 74 mass%, and BCS was 20 mass%, the pore diameter was 1 μm. The liquid crystal alignment agent of Comparative Example 1 was obtained by pressure filtration with a membrane filter.

Comparative Example 2 Synthesis of Liquid Crystal Alignment Agent 1.84 g (0.0094 mol) of CBDA and 1.08 g (0.01 mol) of DA-1 were reacted in 26.32 g of NMP at room temperature for 16 hours to obtain a polyamic. A solution of acid (PAA-5) was prepared. This polyamic acid had a number average molecular weight of about 6000 and a weight average molecular weight of about 13,000. NMP and BCS were added to 10 g of this polyamic acid solution and stirred, and after preparing so that the polyamic acid (PAA-5) was 6% by mass, NMP was 74% by mass, and BCS was 20% by mass, the pore diameter was 1 μm. The liquid crystal alignment agent of Comparative Example 2 was obtained by pressure filtration with a membrane filter.

Comparative Example 3 Synthesis of Liquid Crystal Alignment Agent 1.94 g (0.0099 mol) of CBDA, 2.09 g (0.0080 mol) of DA-3, 0.76 g (0.0020 mol) of DA-2 and NMP 18 In 97 g, reaction was performed at room temperature for 16 hours to prepare a solution of polyamic acid (PAA-23). This polyamic acid had a number average molecular weight of about 8,000 and a weight average molecular weight of about 22,000. NMP and BCS were added to 10 g of this polyamic acid solution and stirred, and after preparing so that the polyamic acid (PAA-23) was 6% by mass, NMP was 74% by mass, and BCS was 20% by mass, the pore diameter was 1 μm. Pressure filtration was performed with a membrane filter to obtain a liquid crystal aligning agent of Comparative Example 3.

Comparative Example 4 Synthesis of Liquid Crystal Alignment Agent 1.94 g (0.0099 mol) of CBDA, 3.28 g (0.0080 mol) of DA-7, 0.76 g (0.0020 mol) of DA-2 and NMP It was made to react at room temperature for 16 hours in 33.92 g, and the solution of polyamic acid (PAA-9) was prepared. This polyamic acid had a number average molecular weight of about 7000 and a weight average molecular weight of about 15000. After adding NMP and BCS to 10 g of this polyamic acid solution and stirring, the polyamic acid (PAA-9) is 6% by mass, NMP is 74% by mass, and BCS is 20% by mass. The liquid crystal aligning agent of Comparative Example 4 was obtained by pressure filtration with a membrane filter.

<Production of liquid crystal cell>
The liquid crystal aligning agent of Example 10 is spin-coated on the ITO surface of the ITO electrode substrate on which the ITO electrode pattern having a pixel size of 100 μm × 300 μm and a line / space of 5 μm is formed, and is heated for 90 seconds on a hot plate at 80 ° C. After drying, 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.

  In addition, the liquid crystal aligning agent of Example 10 was spin-coated on the ITO surface on which no electrode pattern was formed, dried on an 80 ° C. hot plate for 90 seconds, and then baked in a hot air circulation oven at 200 ° C. for 30 minutes. A liquid crystal alignment film having a thickness of 100 nm was formed.

  After spraying a 6 μm bead spacer on the liquid crystal alignment film of one of the two substrates, a sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) 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, followed by Isotropic treatment (liquid crystal realignment treatment by heating) in an oven at 120 ° C., and a liquid crystal cell (for vertical alignment mode) An anti-parallel liquid crystal cell) was produced. Similarly, liquid crystal cells were prepared using the liquid crystal aligning agents prepared in Examples 11, 13 to 20 and Comparative Examples 1, 3, and 4, respectively.

  The response speed immediately after preparation of the liquid crystal cell using each obtained liquid crystal aligning agent of Examples 10-11, 13-20 and Comparative Examples 1, 3, 4 was measured by the following method. After that, with a voltage of 20 Vp-p applied to the liquid crystal cell, 10 J UV irradiation through a 313 nm band pass filter was applied from the outside of the liquid crystal cell. Thereafter, the response speed was measured again, and the response speed before and after UV irradiation was compared. Table 1 shows the results of the response speed immediately after the liquid crystal cell was produced (indicated as “initial” in the table) and after UV irradiation (indicated as “after UV” in the table).

"Response speed measurement method"
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 ± 4 V and a frequency of 1 kHz is applied to the liquid crystal cell, and the change until the luminance observed by the light amount detector is saturated is captured by an oscilloscope, and the luminance when no voltage is applied is obtained. A voltage of 0% and ± 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.

As a result, Examples 10 to 11 and 13 to 20 using the diamine compound represented by the above formula [1] having both a photopolymerizable group and a group causing photodimerization as a raw material contain a photopolymerizable compound. Even if not, the response speed was sufficiently fast. In Examples 10 to 11 and 13 to 20, a diamine compound having a photopolymerizable group but not having a group causing photodimerization was used as a raw material instead of the diamine compound represented by the formula [1]. Compared with Comparative Examples 1 and 3 and Comparative Example 4 using a diamine compound in which R ⁴ in Formula [1] is a single bond, the response speed was remarkably high.

<Production of liquid crystal cell>
The liquid crystal aligning agent of Example 12 was spin-coated on two glass substrates with transparent electrodes, dried on a 90 ° C. hot plate for 60 seconds, and then baked in a hot air circulation oven at 200 ° C. for 30 minutes. A liquid crystal alignment film having a thickness of 100 nm was formed. These coatings were placed on a substrate so that UV was passed through a 313 nm band-pass filter and a polarizing plate when the cell was assembled, and the substrate was irradiated from the top to 500 mJ.

  After spraying a 6 μm bead spacer on the liquid crystal alignment film of one of the two substrates, a sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) 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-2041 (trade name, manufactured by Merck & Co., Inc.) was injected into this empty cell by a reduced pressure injection method, and was subjected to Isotropic treatment (liquid crystal realignment treatment by heating) in an oven at 120 ° C. An anti-parallel cell) was produced. Similarly, liquid crystal cells were prepared using the liquid crystal aligning agents prepared in Examples 21 to 27 and Comparative Example 2.

<Evaluation of liquid crystal alignment>
The prepared cell was sandwiched between polarizing plates arranged so as to be crossed Nicols on the backlight, and the cell was observed, and the liquid crystal orientation was evaluated according to the following criteria. The evaluation results are shown in Table 2.
○: No orientation failure is observed.
X: Orientation defect is observed.

  As a result, it was confirmed that the liquid crystal aligning agent of the present invention using the diamine compound represented by the formula [1] as a raw material can also be used as a liquid crystal aligning agent for a horizontal alignment mode.

Claims (3)

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

(In the formula, R ¹¹ represents an alkylene group having 2 to 6 carbon atoms, and R ¹² represents an alkylene group having 2 to 4 carbon atoms.) A diamine compound represented by the following formula [3].

(In formula [3], A is selected from the following: R ¹³ represents an alkylene group having 2 to 6 carbon atoms.)

(In the formula, * represents a bonding position with O, and ** represents a bonding position with R ^13. ) A diamine compound represented by the following formula [4].

(In formula [4], B is selected from the following: k is 0 to 1, l is an integer of 1 to 6, m is 1 (provided that n is 0, m is also 0), and n is 0. It is an integer of ~ 6.)

(In the formula, * represents a bonding position with — (CH ₂ ) ₁ —, and ** represents a bonding position with O.)