JP6478052B2 - Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element - Google Patents

Description

  The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element.

  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. In addition, unreacted photopolymerizable compounds become impurities and cause burn-in, etc. Increasing the amount of UV irradiation to reduce unreacted photopolymerizable compounds damages liquid crystals and other components, and causes damage to liquid crystal display elements. It becomes a cause of reducing reliability.

  An object of the present invention is to solve the above-mentioned problems of the prior art, and a liquid crystal aligning agent capable of improving the response speed of a liquid crystal display element without adding a photopolymerizable compound to the liquid crystal, and the liquid crystal An object is to provide an alignment film, a liquid crystal 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. A polyimide precursor obtained by reaction of a diamine compound represented by the following formula [1] and a diamine component having a side chain for vertically aligning a liquid crystal and a tetracarboxylic dianhydride component, and an imide Liquid crystal aligning agent containing the at least 1 sort (s) of polymer selected from the polyimide obtained by making, and a polymeric compound.

(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 cinnamoyl group, R ⁷ represents a single bond, an alkylene group having 1 to 30 carbon atoms, a divalent carbocycle or a heterocycle, One or more hydrogen atoms of the alkylene group, divalent carbocycle or heterocycle may be replaced with a fluorine atom or an organic group, and R ⁷ may be any of the following groups adjacent to each other: In this case, —CH ₂ — may be replaced by these groups; —O—, —NHCO—, —CONH—, —COO—, —OCO—, —NH—, —NHCONH—, — CO— R ⁸ represents a photopolymerizable group selected from an acrylic group and a methacryl group.)

2. 2. The liquid crystal aligning agent according to 1, wherein the diamine compound represented by the formula [1] is 10 mol% to 90 mol% in the diamine component.

3. The liquid crystal aligning agent according to 1 or 2, wherein the diamine compound having a side chain for vertically aligning the liquid crystal is 10 mol% to 70 mol% in the diamine component.

4). The polymerizable compound according to any one of 1 to 3, wherein the polymerizable compound is a polymerizable compound represented by the following formula:

A liquid crystal aligning film obtained from the liquid crystal aligning agent according to any one of 5.1 to 4.

6.5. A liquid crystal display element comprising the liquid crystal alignment film according to 6.5.

7). A diamine compound represented by the following formula [DA-4].

8). A diamine compound represented by the following formula [DA-10].

9. A diamine compound represented by the following formula [DA-11].

10. A diamine compound represented by the following formula [DA-13].

  ADVANTAGE OF THE INVENTION According to this invention, even if it does not contain a photopolymerizable compound in a liquid crystal, 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. This liquid crystal aligning agent is not limited to the PSA type liquid crystal display element, but can be used for a liquid crystal display element that performs alignment treatment by irradiating polarized ultraviolet rays, for example. It is possible to obtain a liquid crystal alignment film effective in improving the above.

  Hereinafter, the present invention will be described in detail.

  The liquid crystal aligning agent of this invention is obtained by reaction with the diamine component containing the diamine compound represented by the said Formula [1], and the diamine compound which has a side chain which aligns a liquid crystal vertically, and a tetracarboxylic dianhydride component. A polyimide precursor and at least one polymer selected from polyimides obtained by imidizing the polyimide precursor, and a polymerizable compound. The liquid crystal alignment agent is a solution for producing 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 cinnamoyl group, and R ³ is a bonding group to the diaminobenzene skeleton in this spacer site. Represents. 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 ⁷ in the formula [1] is a site where R ⁶ which is a cinnamoyl group and R ⁸ which is a photopolymerizable group selected from any one of an acryl group and a methacryl group are bonded, and R ⁷ is a single bond, Alternatively, 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 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 selected from either an acrylic group or a methacryl group. The photopolymerizable group is a functional group that causes a polymerization reaction by light stimulation.

  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 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 90 mol% in the diamine component used for the synthesis of the polyimide precursor, more preferably 10 mol of the diamine component. % To 60 mol%, particularly preferably 10 mol% to 40 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.

(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 making it include.

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 is 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.

(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.)

(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.

(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.

(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.)

(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. .)

(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].

(In the formulas [A-25] to [A-30], A ₁₂ represents —COO—, —OCO—, —CONH—, —NHCO—, —CH ₂ —, —O—, —CO—, or It shows the _{-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 10 mol% to 70 mol% in the diamine component used for the synthesis of the polyimide precursor, more preferably 10 mol% to 50 mol% in the diamine component. And particularly preferably 20 to 40 mol%. When the amount of the diamine having a side chain for vertically aligning the liquid crystal is 20 mol% to 40 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. It is particularly excellent in terms of its ability to convert.

<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-amino) Phenyl) butane, 1,4-bis (3-aminophenyl) butane, bis (3,5-diethyl-4-aminophenyl) methane, , 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) Thanone], 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) Zamide), 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 3-aminophenyl) hexafluoropropane, 2,2′-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2′-bis (4-aminophenyl) propane, 2,2′-bis ( 3-aminophenyl) propane, 2,2′-bis (3-amino-4-methylphenyl) propane, 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid, 1,3-bis (4-amino) Phenoxy) propane, 1,3-bis (3-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, 1,4-bis (3-aminophenoxy) butane, 1,5-bis (4 -Aminophenoxy) pentane, 1,5-bis (3-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) hexane, 1,6-bis (3-aminophenoxy) Hexane, 1,7-bis (4-aminophenoxy) heptane, 1,7- (3-aminophenoxy) heptane, 1,8-bis (4-aminophenoxy) octane, 1,8-bis (3-amino) Phenoxy) octane, 1,9-bis (4-aminophenoxy) nonane, 1,9-bis (3-aminophenoxy) nonane, 1,10- (4-aminophenoxy) decane, 1,10- (3-amino Phenoxy) decane, 1,11- (4-aminophenoxy) undecane, 1,11- (3-aminophenoxy) undecane, 1,12- (4-aminophenoxy) dodecane, 1,12- (3-aminophenoxy) Alicyclic diamines such as aromatic diamines such as dodecane, bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane Amine, 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 synthesize | combine by making it react for 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 synthesize | combine by making it react for 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>
As described above, the liquid crystal aligning agent of the present invention includes a diamine component containing the diamine compound represented by the above formula [1] and a diamine compound having a side chain for vertically aligning the liquid crystal, and a tetracarboxylic dianhydride component. And at least one polymer selected from polyimides obtained by imidizing the polyimide precursors. It is obtained by a reaction between a diamine compound containing a diamine compound represented by the above formula [1] and a diamine compound having a side chain for vertically aligning a liquid crystal, and a tetracarboxylic dianhydride component. The total amount of at least one polymer selected from a polyimide precursor and a polyimide obtained by imidizing the polyimide precursor is preferably 1 to 10 (mass)%.

  Moreover, the liquid crystal aligning agent of this invention is by reaction of the diamine component containing the diamine compound represented by the said Formula [1], and the diamine compound which has a side chain which aligns a liquid crystal perpendicularly, and a tetracarboxylic dianhydride component. You may contain other polymers other than the polyimide precursor obtained and at least 1 type of polymer selected from the polyimide obtained by imidating this polyimide precursor. In that case, it obtains by reaction with the diamine component and the tetracarboxylic dianhydride component containing the diamine compound which has a side chain which orientates the diamine compound represented by the said Formula [1] in the polymer all components in the perpendicular direction. The proportion of at least one polymer selected from the polyimide precursor obtained and the polyimide obtained by imidizing this polyimide precursor 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%.

<Polymerizable compound>
The liquid crystal aligning agent of the present invention contains a polymerizable compound having a photopolymerizable or photocrosslinkable group at one or more terminals. That is, the polymerizable compound contained in the liquid crystal aligning agent of the present invention is a compound having one or more terminals having a group that undergoes photopolymerization or photocrosslinking. Here, the polymerizable compound having a photopolymerizable group is a compound having a functional group that causes polymerization upon irradiation with light. The polymerizable compound having a photocrosslinking group is a compound having a functional group capable of reacting with the polymer of the present invention and crosslinking with these upon irradiation with light. The polymerizable compound having a photocrosslinkable group also reacts with other polymerizable compounds having a photocrosslinkable group.

  Such a polymerizable compound is obtained by a reaction between a diamine compound represented by the above formula [1] and a diamine component containing a diamine compound having a side chain for vertically aligning a liquid crystal and a tetracarboxylic dianhydride component. The liquid crystal aligning agent is contained together with at least one polymer selected from polyimides obtained by imidizing the polyimide precursor and the polyimide obtained by manufacturing the polyimide precursor, and a liquid crystal display element of a vertical alignment method such as an SC-PVA liquid crystal display is manufactured. Compared to the case where a polymer having a side chain for vertically aligning the liquid crystal and a photoreactive side chain or the use of this polymerizable compound alone is used, the response speed is dramatically improved. The response speed can be sufficiently improved even with a small addition amount of the polymerizable compound.

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

Specific examples of the polymerizable compound include a polymerizable compound having a photopolymerizable group at each of two ends as represented by the following formula (III), and photopolymerization as represented by the following formula (IV). Examples thereof include a polymerizable compound having a terminal having a group and a terminal having a photocrosslinkable group, and a polymerizable compound having a photocrosslinkable group at each of two terminals represented by the following formula (V). In Formula ^{(III) ~ (V),} R 12, Z 1 and ^{Z 2} are the same as ^R 12, ^{Z 1} and ^{Z 2} in the formula (II), ^{Q 1} is a divalent organic group is there. Q ¹ has a ring structure such as a phenylene group (—C ₆ H ₄ —), a biphenylene group (—C ₆ H ₄ —C ₆ H ₄ —), a cyclohexylene group (—C ₆ H ₁₀ —), and the like. Preferably it is. This is because the interaction with the liquid crystal tends to increase.

Specific examples of the polymerizable compound represented by the formula (III) include the following polymerizable compounds. In the formula, V is represented by a single bond or -R ¹ O-, and R ¹ is a linear or branched alkylene group having 1 to 10 carbon atoms, preferably, represented by -R ¹ O- and R ¹ is A linear or branched alkylene group having 2 to 6 carbon atoms. W represents a single bond or —OR ² —, and R ² represents a linear or branched alkylene group having 1 to 10 carbon atoms, and preferably represents —OR ² — and R ² represents a straight chain or It is a branched alkylene group having 2 to 6 carbon atoms. V and W may be the same or different, but if they are the same, synthesis is easy.

  Since the polymerizable compound represented by the above formula is a compound having a specific structure having α-methylene-γ-butyrolactone groups which are polymerizable groups at both ends, the polymer has a rigid structure and the liquid crystal orientation is fixed. As a material for the liquid crystal alignment film, because of its excellent ability, as shown in the examples described later, a polyimide precursor and at least one polymer selected from polyimide obtained by imidizing this polyimide precursor are used. The response speed can be particularly greatly improved by using the liquid crystal display element of the vertical alignment system such as the SC-PVA type liquid crystal display to be used. In general, the process of forming the liquid crystal alignment film includes a step of baking at a high temperature to completely remove the solvent. However, a polymerizable group such as an acrylate group, a methacrylate group, a vinyl group, a vinyloxy group, or an epoxy group is added. The compounds that are possessed have poor thermal stability and are difficult to withstand firing at high temperatures. On the other hand, a polymerizable compound as described in the above formula having α-methylene-γ-butyrolactone groups at both ends is sufficiently resistant to a high temperature, for example, a firing temperature of 200 ° C. or more, because of its poor thermal polymerizability. Can do.

  In addition, even if it is a polymerizable compound having an acrylate group or a methacrylate group instead of an α-methylene-γ-butyrolactone group as a group for photopolymerization or photocrosslinking, this acrylate group or methacrylate group is a spacer such as an oxyalkylene group. If it is a polymerizable compound having a structure bonded to a phenylene group via an alkenyl group, the response speed is greatly improved, as in the case of the polymerizable compound having α-methylene-γ-butyrolactone groups at both ends. be able to. In addition, if the polymerizable compound has a structure in which an acrylate group or a methacrylate group is bonded to a phenylene group via a spacer such as an oxyalkylene group, the stability to heat is improved, or a high temperature, for example, 200 ° C. or higher. Can sufficiently withstand the firing temperature.

  In addition, other specific examples of the polymerizable compound represented by the formula (III) include polymerizable compounds of the following formula.

(In the formula, V represents a single bond or —R ¹ O—, and R ¹ represents a linear or branched alkylene group having 1 to 10 carbon atoms, preferably represented by —R ¹ O— and R ^1. Is a linear or branched alkylene group having 2 to 6 carbon atoms, W is a single bond or —OR ² —, and R ² is a linear or branched alkylene group having 1 to 10 carbon atoms. preferably, -OR 2 ^- synthesis and represented by R ² .V and W is a linear or branched alkylene group having 2 to 6 carbon atoms may be the same or different structure but the same R ¹² is H or an alkyl group having 1 to 4 carbon atoms.)

  These polymerizable compounds are preferably 1% by weight to 30% by weight, and more preferably 1% by weight to 20% by weight, based on the solid content in the liquid crystal aligning agent, from the viewpoint of solubility and the ability to develop a pretilt angle. 1% by weight to 10% by weight is more preferable.

<Method for producing polymerizable compound>
The method for producing such a polymerizable compound is not particularly limited, and for example, it can be produced according to the synthesis examples described later. For example, the polymerizable compound represented by the following formula (1) can be synthesized by combining techniques in organic synthetic chemistry. For example, taraga and the like represented by the following reaction formula are prepared by the method proposed by P. Talaga, M. Schaeffer, C. Benezra and JLStampf, Synthesis, 530 (1990) using SnCl ₂ and 2- (bromomethyl) acrylic acid. It can be synthesized by reacting (2- (bromomethyl) propenoic acid) with aldehyde or ketone. Amberlyst 15 is a strongly acidic ion exchange resin manufactured by Rohm and Haas.

(In the formula, R ′ represents a monovalent organic group.)
In addition, 2- (bromomethyl) acrylic acid is proposed by K. Ramarajan, K. Kamalingam, DJO 'Donnell and KDBerlin, Organic Synthesis, vol. 61, 56-59 (1983). Can be synthesized by the following method.

As a specific synthesis example, when synthesizing a polymerizable compound represented by the above formula (1) in which V is —R ¹ O—, W is —OR ² — and R ¹ and R ² are the same, There are two methods shown in the following reaction formula.

Moreover, when synthesizing the polymerizable compound represented by the above formula (1) in which R ¹ and R ² are different, a method represented by the following reaction formula is exemplified.

  And when synthesize | combining the polymeric compound represented by the said Formula (1) whose V and W are single bonds, the method shown by following Reaction Formula is mentioned.

  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 using these surfactants, the use ratio 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 alignment of the liquid crystal is efficiently fixed, A liquid crystal display device with significantly excellent response speed is obtained. 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, spacers such as beads are spread on the liquid crystal alignment film on one substrate, and the surface on which the liquid crystal alignment film is formed is on the inside. There is a method in which the other substrate is attached 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 ultraviolet irradiation amount is, for example, 1 to 60 J / cm ² , preferably 40 J / cm ² or less, and the smaller the ultraviolet irradiation amount, the lowering of reliability caused by the destruction of the members constituting the liquid crystal display element can be suppressed, and It is preferable because the production efficiency is increased by reducing the ultraviolet irradiation time.

  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.

(Tetracarboxylic dianhydride)
BODA: Bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride TCA: 2,3,5 -Tricarboxycyclopentylacetic acid-1,4: 2,3-dianhydride (diamine)
DBA: 3,5-diaminobenzoic acid 3AMPDA: 3,5-diamino-N- (pyridin-3-ylmethyl) benzamide Photoreactive diamine represented by the following formulas DA-1 to DA-5

下記式ＤＡ−６〜ＤＡ−９で表される垂直配向性ジアミン

Vertically oriented diamines represented by the following formulas DA-6 to DA-9

<Solvent>
NMP: N-methyl-2-pyrrolidone BCS: Butyl cellosolve <Additives>
3AMP: 3-picolylamine <Polymerizable compound>
Polymerizable compounds represented by the following formulas RM1 and RM2

Abbreviations such as organic solvents used in Examples and the like are as follows.
NMP: N-methyl-2-pyrrolidone BCS: Butyl cellosolve The molecular weight measurement conditions for polyimide are as follows.
Apparatus: Room temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Scientific Co., Ltd.
Column: Column made by Shodex (KD-803, KD-805)
Column temperature: 50 ° C
Eluent: N, N′-dimethylformamide (as additives, lithium bromide-hydrate (LiBr · H ₂ O) is 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphoric acid) is 30 mmol / L, Tetrahydrofuran (THF) 10ml / L)
Flow rate: 1.0 ml / standard curve preparation standard sample: Tosoh TSK standard polyethylene oxide (molecular weight about 9,000,150,000, 100,000, 30,000) and polymer laboratory polyethylene glycol ( Molecular weight about 12,000, 4,000, 1,000).

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

Imidation ratio (%) = (1−α · x / y) × 100
<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)

(Synthesis Example 1) Synthesis of DA-1 (Synthesis Example 1-1) Synthesis of DA-1 Precursor DA-1-1

  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. And 158 g of DA-1-1 (reddish brown viscous body) was obtained. The obtained compound was directly used in the next step.

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

  In a 500 mL four-neck flask, 22.0 g of DA-1-1, 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-1-2 (white solid) (43% yield).

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

  To a 300 mL four-necked flask, 6.4 g of DA-1-2, 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. The filtrate was washed with isopropyl alcohol and dried to obtain 7.4 g of DA-1-3 (yellow solid) (yield 81%).

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

  In a 300 mL four-necked flask, 6.9 g of DA-1-3, 70 mL of tetrahydrofuran, 2.5 g of 2-hydroxyethyl methacrylate, and 5. 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride were added. 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. This filtrate was washed with isopropyl alcohol and dried to obtain 8.6 g of DA-1-4 (yellowish white solid) (yield 96%).

  (Synthesis Example 1-5) Synthesis of DA-1

To a 300 mL four-necked flask, 7.6 g of DA-1-4, 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-1 (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-1.
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)

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

  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-2-1 (white solid) (yield 75%). ).

  Synthesis Example 2-2 Synthesis of DA-2 Precursor DA-2-2

  In a 500 mL three-necked flask, 19.2 g of DA-2-1, 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-2-2 (transparent viscous material) was obtained (yield 92%).

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

  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%).

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

To a 300 mL three-necked flask, 11.7 g of DA-2-3, 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-2-4 (yellowish white solid) (yield 35%).

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

  In a 200 mL three-necked flask, 6.9 g of DA-2-4, 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-2-5 (yellowish white solid) (yield 69%).

  (Synthesis Example 2-6) Synthesis of DA-2

Add 5.9 g of DA-2-5, 60 mL of tetrahydrofuran and 60 mL of pure water to a 300 mL three-necked flask, stir the system, add 13.3 g of tin chloride, heat the system to 70 ° C., and stir 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-2 (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)

  Synthesis Example 3 Synthesis of DA-3

(The cyclohexane ring indicated by ● in the above reaction formula indicates that the three-dimensional structure is a 1,4-trans-cyclohexane ring.)
Charge a reaction vessel with compound DA-3-1 (74.43 g, 261 mmol), triethylamine (29.81 g, 295 mmol), THF (1,000 g), and after replacing with nitrogen, be careful not to let the internal temperature exceed 10 ° C. Then, a solution of methacryloyl chloride (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 product of compound DA-3-2. 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 DA-3-2 (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 saline (200 g), and the organic layer was dried over magnesium sulfate, filtered and evaporated to give a crude product of compound DA-3-3. The obtained crude product was dispersed and washed with methanol (30 g), filtered and dried to obtain Compound DA-3-3 (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).

2- (2,4-dinitrophenyl) ethanol (11.94 g, 56.3 mmol), compound DA-3-3 (10.89 g, 35.3 mmol), EDC (11.62 g, 61.0 mmol) in a reaction vessel , DMAP (0.57 g, 4.7 mmol) and THF (130 g) were added and 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 DA-3-4. The obtained crude product was dispersed and washed with methanol (100 mL), filtered and dried under reduced pressure to obtain Compound DA-3-4 (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).

In a reaction vessel, compound DA-3-4 (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). In addition, heating and stirring were 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-3 (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).

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

  In a 500 mL four-necked flask, 21.2 g of 2-methylacrylic acid 6- [4- (2-hydroxycarbonylvinyl) phenyl] -hexyl ester, 300 mL of tetrahydrofuran, and 2- (2,4-dinitrophenyl) ethanol 13.6 g, 18.4 g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and 0.8 g of 4-dimethylaminopyridine (DMAP) were added and stirred at room temperature. After completion of the reaction, the organic layer is extracted with ethyl acetate, anhydrous magnesium sulfate is added to the organic layer, dehydrated, dried, filtered, the solvent is distilled off using a rotary evaporator, and the residue is washed with isopropyl alcohol and dried. As a result, 15.9 g of the desired product DA-4-1 (yellowish white solid) was obtained (yield 47%).

  (Synthesis Example 4-2) Synthesis of DA-4

To a 500 mL four-necked flask, 7.6 g of DA-4-1, 150 mL of ethyl acetate, 150 mL of pure water, 8.4 g of reduced iron, and 6.5 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 13.4 g of the desired product DA-4 (yellowish white solid) (yield 95%). 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): δ7.64-7.66 (d, 2H), 7.58-7.62 (d, 1H), 6.95-6.97 (d, 2H), 6.60-6.62 (d, 1H), 6.44-6.48 (d, 1H), 6.02 (s, 1H), 5.89 (s, 1H), 5.78-5.81 (d, 1H), 5.66 (s, 1H), 4.65 (s, 2H), 4.59 (s, 2H), 4.08-4.17 (m, 4H), 4.00-4.03 (t, 2H), 2.65-2.69 (t, 2H), 1.87 (s, 3H), 1.62-1.74 (m, 4H), 1.39 -1.45 (m, 4H)

  Here, a photoreactive diamine represented by the following formula was further synthesized.

(Synthesis Example 5) Synthesis of DA-10 (Synthesis Example 5-1) Synthesis of DA-10 Precursor DA-10-1

  2-Methylacrylic acid 6- [4,4 ′-(2-hydroxycarbonylvinyl) biphenyl] -octyl ester (100 g, 229 mmol), 3,5-dinitrobenzyl chloride (55 g, 252 mmol), N, N at room temperature -Dimethylformamide (750 g) was added and potassium carbonate (47 g, 344 mmol) was added, followed by heating and stirring at 80 ° C for 3 hours. After cooling to room temperature (<30 ° C.), water (1500 g) was added for crystallization and aging for 30 minutes.

  After filtration, the filtrate was washed 3 times with water (100 g). The filtrate was dried at 30 ° C. full vacuum. After dissolving in tetrahydrofuran (2500 g) and performing a short column with silica gel (50 g), the solvent was distilled off and dried to obtain 142 g of DA-10-1 (brown solid) (yield 100%).

  (Synthesis Example 5-2) Synthesis of DA-10

  A 10% aqueous ammonium chloride solution (37 g, 698 mmol) was added at room temperature, and the atmosphere was replaced with nitrogen. Then, reduced iron (78 g, 1392 mmol) was added, and further nitrogen replacement was performed. A solution of DA-10-1 (72 g, 116 mmol) in tetrahydrofuran (1435 g) was added dropwise, and the mixture was heated to 60 ° C. and stirred for 17.5 hours.

The reaction solution was allowed to cool to room temperature (<30 degrees) and then filtered with a filter aid (KC floc). Ethyl acetate and water were added to the filtrate for liquid separation, and the organic layer was washed with water three times. Activated carbon was added to the organic layer and stirred, followed by filtration with KC floc. The filtrate was washed with water three times and dried over magnesium sulfate, and then the solvent was distilled off. Ethyl acetate (36 g) and hexane (288 g) were added to the residue, and the mixture was stirred at room temperature for crystallization. The filtered product was collected by filtration and dried at 40 ° C. to obtain 107 g of DA-10 (yellow crystals) (yield 83%). The result of measuring the obtained compound by ¹ H-NMR is shown below.

1H NMR (400 MHz, [D6] -DMSO): δ7.79-7.77 (d, 2H), 7.72-7.65 (m, 4H), 7.03-7.00 (d, 2
H), 6.71-6.67 (d, 1H), 6.02 (s, 1H), 5.84-5.83 (d, 2H), 5.79-5.78 (d, 2H), 5.67-5.66 (d, 1H), 4.94 (s, 1H), 4.80 (s, 4H), 4.10-4.07 (t, 2H), 4.01-3.98 (t, 2H), 1.87 (s, 3H), 1.74-1.70 (quint, 2H), 1.63-1.60 (quint, 2H), 1.41-1.33 (m, 8H)

Synthesis Example 6 Synthesis of DA-11 Synthesis Example 6-1 Synthesis of DA-11 Precursor DA-11-1

  2-Methylacrylic acid 6- [4- (2-hydroxycarbonylvinyl) phenyl] -hexyl ester (100 g, 301 mmol), 3,5-dinitrobenzyl chloride (58 g, 331 mmol), N, N-dimethylformamide at room temperature (750 g) was added, potassium carbonate (51 g, 452 mmol) was added, and the mixture was heated to 60 ° C. with stirring and reacted for 1 hour.

  After cooling to room temperature (<30 ° C.), water (1500 g) was added for crystallization and aging for 30 minutes. After filtration, the filtrate was washed 3 times with water (100 g). The filtrate was slurried with acetonitrile (200 g) and dried to obtain 142 g of DA-11-1 (light brown crystals) (yield 92%).

  (Synthesis Example 6-2) Synthesis of DA-11

  A 10% aqueous ammonium chloride solution (77 g, 1659 mmol) was added at room temperature, and the atmosphere was replaced with nitrogen. Then, reduced iron (161 g, 3324 mmol) was added, and further nitrogen replacement was performed. A solution of DA-11-1 (142 g, 277 mmol) in tetrahydrofuran (2126 g) was added dropwise, heated to 60 ° C. and stirred for 18 hours.

The reaction solution was allowed to cool to room temperature (<30 ° C.) and then filtered through KC floc. The filtrate was concentrated, tetrahydrofuran was distilled off, ethyl acetate and activated carbon were added to the residue, and the mixture was stirred and filtered. The filtrate was separated and the organic layer was washed twice with water and dried over sodium sulfate. After concentrating the filtered filtrate, silica gel column purification was performed to obtain 90 g of DA-11 (red oil) (yield 72%). The result of measuring the obtained compound by ¹ H-NMR is shown below.

  1H NMR (400 MHz, [D6] -DMSO): δ7.68-7.65 (d, 2H), 7.64-7.60 (d, 1H), 6.70-6.94 (d, 2H), 6.52-6.48 (d, 1H) , 6.02-6.01 (d, 1H), 5.81 (s, 2H), 5.77-5.76 (d, 2H), 5.67-5.65 (t, 1H), 4.90 (s, 2H), 4.77 (s, 4H), 4.11 -4.08 (t, 2H), 4.02-3.99 (t, 2H), 1.87 (s, 3H), 1.74-1.70 (quint, 2H), 1.66-1.62 (quint, 2H), 1.46-1.38 (m, 4H)

(Synthesis Example 7) Synthesis of DA-13 (Synthesis Example 7-1) Synthesis of DA-13 Precursor DA-13-1

3-Chloro-1-propanol (56 g, 591 mmol) was dissolved in dehydrated N, N-dimethylformamide (1000 ml). 2,4-Dinitrofluorobenzene (100 g, 537 mmol) and triethylamine (109 g, 1074 mmol) were added dropwise. After heating up to 70 ° C., the mixture was stirred for 19.5 hours to react.
After allowing to cool, N, N-dimethylformamide and triethylamine were distilled off under reduced pressure. Ethyl acetate (500 g) and water (200 g) were added for liquid separation, and the organic layer was washed with water three times. The organic layer was evaporated to obtain 137 g of DA-13-1 (yellow oil) (yield 98%).

  Synthesis Example 7-2 Synthesis of DA-13 Precursor DA-13-2

  DA-13-1 (73.9 g, 360 mmol), 2-methylacrylic acid 6- [4- (2-hydroxycarbonylvinyl) phenyl] -hexyl ester (85.9 g, 328 mmol), potassium carbonate (107 g, 984 mmol) , Potassium iodide (3.2 g, 36 mmol) was dissolved in N, N-dimethylformamide (514 g). Heated to 100 ° C. and reacted for 3.5 hours.

  The reaction solution was added dropwise to water (2600 g) and stirred. The precipitate was filtered to obtain 192 g of a yellow filtrate. Acetonitrile (170 g) was added to the obtained filtrate and stirred for 30 minutes, followed by filtration to obtain 162 g of a pale yellow filtrate. The obtained filtrate was dissolved in ethyl acetate (200 g) at 60 ° C., hexane (180 g) was added, and the mixture was cooled to 0 ° C. The precipitate was filtered, washed with hexane and dried to obtain 117 g of DA-13-2 (pale yellow solid) (yield 81%).

  (Synthesis Example 7-3) Synthesis of DA-13

  A 10% aqueous ammonium chloride solution (666 g, 1242 mmol) was added at room temperature, and the atmosphere was replaced with nitrogen. Then, reduced iron (139 g, 2484 mmol) was added, and further nitrogen replacement was performed. A solution of DA-13-2 (115 g, 207 mmol) in tetrahydrofuran (1155 g) was added dropwise, heated to 60 ° C. and stirred for 23 hours.

The reaction solution was allowed to cool to room temperature (<30 ° C.) and then filtered through KC floc. The filtrate was concentrated, tetrahydrofuran was distilled off, ethyl acetate and activated carbon were added to the residue, and the mixture was stirred and filtered. The filtrate was separated, and the organic layer was washed 3 times with water and dried over sodium sulfate. After concentrating the filtered filtrate, silica gel column purification was performed to obtain 41 g of DA-13 (ocher solid) (yield 40%). The result of measuring the obtained compound by ¹ H-NMR is shown below.

  1H NMR (400 MHz, [D6] -DMSO): δ7.67-7.64 (d, 2H), 7.63-7.59 (d, 1H), 6.96-6.94 (d, 2H), 6.51-6.47 (m, 2H) , 6.01 (s, 1H), 5.94 (d, 1H), 5.76-5.73 (t, 1H), 5.66 (s, 1H), 4.47 (s, 2H), 4.35-4.29 (m, 4H), 4.11-4.08 (t, 2H), 4.03-3.99 (t, 2H), 3.89-3.86 (t, 2H), 2.07-2.00 (quint, 2H), 1.87 (s, 2H), 1.76-1.61 (m, 4H), 1.48 -1.35 (m, 4H)

<< Examples 1-4 and Comparative Example 1 >>
Example 1
BODA (1.25 g, 5.0 mmol), DA-1 (3.38 g, 7.0 mmol), DA-6 (1.14 g, 3.0 mmol) were dissolved in NMP (20.1 g) at 60 ° C. Then, CBDA (0.92 g, 4.7 mmol) and NMP (6.7 g) were added and reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution. After adding NMP to this polyamic acid solution (30 g) and diluting to 6% by mass, acetic anhydride (2.2 g) and pyridine (6.9 g) were added as an imidization catalyst, and reacted at 50 ° C. for 3 hours. This reaction solution was poured into methanol (440 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 60 degreeC, and obtained the polyimide powder (A1). The imidation ratio of this polyimide was 50%, the number average molecular weight was 15,000, and the weight average molecular weight was 46,000.

  NMP (22.0 g) was added to the obtained polyimide powder (A) (3.0 g), and dissolved by stirring at 50 ° C. for 3 hours. 3AMP (1 wt% NMP solution) 3.0g, NMP (7.0g), and BCS (15.0g) were added to this solution, and the liquid crystal aligning agent (A1) was obtained by stirring at room temperature for 5 hours.

  Further, 0.06 g of polymerizable compound RM1 (10% by mass with respect to the solid content) is added to 10.0 g of the liquid crystal aligning agent (A1), and the mixture is stirred for 3 hours at room temperature to be dissolved. (A2) was prepared.

(Example 2)
BODA (1.25 g, 5.0 mmol), DA-2 (2.55 g, 5.0 mmol), DA-7 (0.87 g, 2.0 mmol), DBA (0.46 g, 3.0 mmol) were mixed with NMP ( After dissolving in 18.2 g) and reacting at 60 ° C. for 5 hours, CBDA (0.92 g, 4.7 mmol) and NMP (6.1 g) are added, and the mixture is reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution. Obtained. After adding NMP to this polyamic acid solution (29 g) and diluting to 6% by mass, acetic anhydride (2.4 g) and pyridine (7.6 g) were added as an imidization catalyst, and the mixture was reacted at 50 ° C. for 3 hours. This reaction solution was poured into methanol (430 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 60 degreeC, and obtained the polyimide powder (B1). The imidation ratio of this polyimide was 51%, the number average molecular weight was 14,000, and the weight average molecular weight was 39,000.

  NMP (22.0 g) was added to the obtained polyimide powder (B) (3.0 g), and dissolved by stirring at 50 ° C. for 3 hours. 3AMP (1 wt% NMP solution) 3.0g, NMP (7.0g), and BCS (15.0g) were added to this solution, and the liquid crystal aligning agent (B1) was obtained by stirring at room temperature for 5 hours.

  In addition, 0.06 g of polymerizable compound RM2 (10% by mass with respect to the solid content) is added to 10.0 g of the liquid crystal aligning agent (B1), and the mixture is dissolved by stirring for 3 hours at room temperature. (B2) was prepared.

(Example 3)
TCA (1.12 g, 5.0 mmol), DA-3 (2.24 g, 5.0 mmol), DA-8 (1.05 g, 2.0 mmol), 3AMPDA (0.73 g, 3.0 mmol) were added to NMP ( 12.2 g), and after reacting at 80 ° C. for 5 hours, CBDA (0.94 g, 4.8 mmol) and NMP (6.1 g) are added and reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution. Obtained. After adding NMP to this polyamic acid solution (29 g) and diluting to 6% by mass, acetic anhydride (2.4 g) and pyridine (7.6 g) were added as an imidization catalyst, and the mixture was reacted at 50 ° C. for 3 hours. This reaction solution was poured into methanol (430 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 60 degreeC, and obtained the polyimide powder (C1). The imidation ratio of this polyimide was 51%, the number average molecular weight was 11,000, and the weight average molecular weight was 31,000.

  NMP (22.0 g) was added to the obtained polyimide powder (C) (3.0 g), and dissolved by stirring at 50 ° C. for 3 hours. 3AMP (1 wt% NMP solution) 3.0g, NMP (7.0g), and BCS (15.0g) were added to this solution, and the liquid crystal aligning agent (C1) was obtained by stirring at room temperature for 5 hours.

  In addition, 0.06 g of polymerizable compound RM2 (10% by mass with respect to the solid content) is added to 10.0 g of the liquid crystal aligning agent (C1), and the mixture is stirred for 3 hours at room temperature to be dissolved. (C2) was prepared.

Example 4
CBDA (1.92 g, 10.0 mmol), DA-4 (3.73 g, 8.0 mmol), DA-9 (0.80 g, 2.0 mmol) were reacted at room temperature in NMP (36.58 g) for 10 hours. Then, NMP (32.3 g) and BCS (32.3 g) were added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent (D1). The number average molecular weight of this polyamic acid was 9,000, and the weight average molecular weight was 32,000. In addition, 0.06 g of polymerizable compound RM1 (in terms of solid content) with respect to 10.0 g of the liquid crystal aligning agent (D1). The liquid crystal aligning agent (D2) was prepared by stirring at room temperature for 3 hours and dissolving.

(Comparative Example 1)
BODA (1.25 g, 5.0 mmol), DA-5 (1.06 g, 4.0 mmol), DA-9 (1.20 g, 3.0 mmol), DBA (0.46 g, 3.0 mmol) with NMP ( 14.7 g), and after reacting at 60 ° C. for 5 hours, CBDA (0.94 g, 4.8 mmol) and NMP (4.9 g) were added and reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution. Obtained. After adding NMP to this polyamic acid solution (23 g) and diluting to 6% by mass, acetic anhydride (2.4 g) and pyridine (7.4 g) were added as an imidization catalyst, and the mixture was reacted at 50 ° C. for 3 hours. This reaction solution was poured into methanol (350 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 60 degreeC, and obtained the polyimide powder (E). The imidation ratio of this polyimide was 50%, the number average molecular weight was 17000, and the weight average molecular weight was 48,000.

  NMP (22.0 g) was added to the obtained polyimide powder (E) (3.0 g), and dissolved by stirring at 50 ° C. for 3 hours. 3AMP (1 wt% NMP solution) 3.0g, NMP (7.0g), and BCS (15.0g) were added to this solution, and the liquid crystal aligning agent (E1) was obtained by stirring at room temperature for 5 hours.

  In addition, 0.06 g of polymerizable compound RM1 (10% by mass with respect to the solid content) is added to 10.0 g of the liquid crystal aligning agent (E1), and the mixture is stirred for 3 hours at room temperature to be dissolved. (E2) was prepared.

<< Examples 5 to 8 and Comparative Examples 2 to 6 >>
<Production of liquid crystal cell>
(Example 5)
Using the liquid crystal aligning agent (A2) obtained in Example 1, a liquid crystal cell was prepared according to the procedure shown below. The liquid crystal aligning agent (A2) obtained in Example 1 was spin-coated on the ITO surface of an ITO electrode substrate on which an ITO electrode pattern having a pixel size of 100 μm × 300 μm and a line / space of 5 μm was formed, After drying for 90 seconds on this hot plate, 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.

  Moreover, after spin-coating the liquid crystal aligning agent (A2) on the ITO surface on which the electrode pattern is not formed and drying for 90 seconds on a hot plate at 80 ° C., baking is performed 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 4 μm bead spacers on the liquid crystal alignment film of one of the two substrates, a sealant (solvent type thermosetting epoxy resin) was printed thereon. Next, the surface of the other substrate on which the liquid crystal alignment film was formed was faced inward and bonded to the previous substrate, and then the sealing agent was cured to produce an empty cell. Liquid crystal MLC-6608 (trade name, manufactured by Merck & Co., Inc.) was injected into this empty cell by a reduced pressure injection method to produce a liquid crystal cell.

The response speed of the obtained liquid crystal cell was measured by the following method. Thereafter, with a voltage of 40 Vp-p applied to the liquid crystal cell, UV was applied from the outside of the liquid crystal cell through a 365 nm bandpass filter at 10 J / cm ² . Thereafter, the response speed was measured again, and the response speed before and after UV irradiation was compared. Further, the pretilt angle of the pixel portion of the cell after UV irradiation was measured. The results are shown in Table 1.

"Response speed measurement method"
First, a liquid crystal cell was arranged between a pair of polarizing plates in a measuring device configured in the order of a backlight, a set of polarizing plates in a crossed Nicol state, and a light amount detector. At this time, the ITO electrode pattern in which the line / space was formed was at an angle of 45 ° with respect to the crossed Nicols. Then, a rectangular wave with a voltage of ± 6 V and a frequency of 1 kHz is applied to the liquid crystal cell, and the change until the luminance observed by the light quantity detector is saturated is captured by an oscilloscope. The luminance when no voltage is applied is obtained. A voltage of 0% and ± 4 V was applied, the saturated luminance value was set to 100%, and the time taken for the luminance to change from 10% to 90% was defined as the response speed.

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

(Example 6)
The same operation as in Example 5 was performed except that the liquid crystal aligning agent (B2) was used instead of the liquid crystal aligning agent (A2), and the response speeds before and after UV irradiation were compared. The pretilt angle was measured.

(Example 7)
Except for using the liquid crystal aligning agent (C2) instead of the liquid crystal aligning agent (A2), the same operation as in Example 5 was performed to compare the response speed before and after UV irradiation. The pretilt angle was measured.

(Example 8)
The response speed before and after UV irradiation was compared by performing the same operation as in Example 5 except that the liquid crystal aligning agent (D2) was used instead of the liquid crystal aligning agent (A2). The pretilt angle was measured.

(Comparative Example 2)
The response speed before and after UV irradiation was compared by performing the same operation as in Example 5 except that the liquid crystal aligning agent (A1) was used instead of the liquid crystal aligning agent (A2). The pretilt angle was measured.

(Comparative Example 3)
The same operation as in Example 5 was performed except that the liquid crystal aligning agent (B1) was used instead of the liquid crystal aligning agent (A2), and the response speeds before and after UV irradiation were compared. The pretilt angle was measured.

(Comparative Example 4)
Except for using the liquid crystal aligning agent (C1) instead of the liquid crystal aligning agent (A2), the same operation as in Example 5 was performed, and the response speed before and after UV irradiation was compared. The pretilt angle was measured.

(Comparative Example 5)
The same operation as in Example 5 was performed except that the liquid crystal aligning agent (D1) was used instead of the liquid crystal aligning agent (A2), and the response speeds before and after UV irradiation were compared. The pretilt angle was measured.

(Comparative Example 6)
The response speed before and after UV irradiation was compared by performing the same operation as in Example 5 except that the liquid crystal aligning agent (E2) was used instead of the liquid crystal aligning agent (A2). The pretilt angle was measured.

<< Examples 9 to 11 >>
Example 9
BODA (3.50 g, 14.0 mmol), DA-10 (5.85 g, 10.5 mmol), DA-6 (5.33 g, 14.0 mmol), 3AMPDA (2.54 g, 10.5 mmol) with NMP ( 63.8 g), and after reacting at 60 ° C. for 3 hours, CBDA (4.05 g, 20.7 mmol) and NMP (21.3 g) were added and reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution. Obtained. After adding NMP to this polyamic acid solution (95 g) and diluting to 6.5% by mass, acetic anhydride (8.0 g) and pyridine (24.7 g) were added as imidization catalysts, and the mixture was reacted at 50 ° C. for 3 hours. It was. This reaction solution was poured into methanol (1,300 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 60 degreeC, and obtained the polyimide powder (F). The imidation ratio of this polyimide was 60%, the number average molecular weight was 13,000, and the weight average molecular weight was 45,000.

  NMP (44.0 g) was added to the obtained polyimide powder (F) (6.0 g), and the mixture was dissolved by stirring at 50 ° C. for 3 hours. 3AMP (1 wt% NMP solution) 6.0g, NMP (4.0g), and BCS (40.0g) were added to this solution, and the liquid crystal aligning agent (F1) was obtained by stirring at room temperature for 5 hours.

  Further, 0.06 g of polymerizable compound RM1 (10% by mass with respect to the solid content) is added to 10.0 g of the liquid crystal aligning agent (F1), and the mixture is stirred for 3 hours at room temperature to be dissolved. (F2) was prepared.

(Example 10)
BODA (3.50 g, 14.0 mmol), DA-11 (4.75 g, 10.5 mmol), DA-6 (5.33 g, 14.0 mmol), 3AMPDA (2.54 g, 10.5 mmol) with NMP ( 60.5 g), and after reacting at 60 ° C. for 3 hours, CBDA (4.05 g, 20.7 mmol) and NMP (20.2 g) were added and reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution. Obtained. After adding NMP to this polyamic acid solution (95 g) and diluting to 6.5% by mass, acetic anhydride (8.0 g) and pyridine (24.7 g) were added as imidization catalysts, and the mixture was reacted at 50 ° C. for 3 hours. It was. This reaction solution was poured into methanol (1,300 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 60 degreeC, and obtained the polyimide powder (G). The imidation ratio of this polyimide was 60%, the number average molecular weight was 12,000, and the weight average molecular weight was 39,000.

  NMP (44.0 g) was added to the obtained polyimide powder (G) (6.0 g), and the mixture was dissolved by stirring at 50 ° C. for 3 hours. 3AMP (1 wt% NMP solution) 6.0g, NMP (4.0g), and BCS (40.0g) were added to this solution, and the liquid crystal aligning agent (G1) was obtained by stirring at room temperature for 5 hours.

  Further, 0.06 g of polymerizable compound RM1 (10% by mass with respect to the solid content) is added to 10.0 g of the liquid crystal aligning agent (G1), and the mixture is stirred and dissolved at room temperature for 3 hours. (G2) was prepared.

(Example 11)
BODA (3.50 g, 14.0 mmol), DA-13 (5.21 g, 10.5 mmol), DA-6 (5.33 g, 14.0 mmol), 3AMPDA (2.54 g, 10.5 mmol) with NMP ( 61.9 g) and after reacting at 60 ° C. for 3 hours, CBDA (4.05 g, 20.7 mmol) and NMP (20.6 g) were added, and the mixture was reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution. Obtained. After adding NMP to this polyamic acid solution (95 g) and diluting to 6.5% by mass, acetic anhydride (8.0 g) and pyridine (24.7 g) were added as imidization catalysts, and the mixture was reacted at 50 ° C. for 3 hours. It was. This reaction solution was poured into methanol (1,300 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 60 degreeC, and obtained the polyimide powder (H). The imidation ratio of this polyimide was 60%, the number average molecular weight was 10,000, and the weight average molecular weight was 27,000.

  NMP (44.0 g) was added to the obtained polyimide powder (H) (6.0 g), and the mixture was dissolved by stirring at 50 ° C. for 3 hours. 3AMP (1 wt% NMP solution) 6.0g, NMP (4.0g), and BCS (40.0g) were added to this solution, and the liquid crystal aligning agent (H1) was obtained by stirring at room temperature for 5 hours.

  Further, 0.06 g of polymerizable compound RM1 (10% by mass with respect to the solid content) is added to 10.0 g of the liquid crystal aligning agent (H1), and the mixture is dissolved by stirring for 3 hours at room temperature. (H2) was prepared.

<< Examples 12 to 14 >>
<Production of liquid crystal cell>
(Example 12)
Except for using the liquid crystal aligning agent (F2) instead of the liquid crystal aligning agent (A2), the same operation as in Example 5 was performed to compare the response speed before and after UV irradiation. The pretilt angle was measured.

(Example 13)
Except for using the liquid crystal aligning agent (G2) instead of the liquid crystal aligning agent (A2), the same operation as in Example 5 was performed to compare the response speed before and after UV irradiation. The pretilt angle was measured.

(Example 14)
The response speed before and after UV irradiation was compared by performing the same operation as in Example 5 except that the liquid crystal aligning agent (H2) was used instead of the liquid crystal aligning agent (A2). The pretilt angle was measured.

  As shown in Table 1, by using a polymer having a methacrylic group and a cinnamoyl group at the photosensitive side chain site in combination with a polymerizable compound, a sufficient response speed and tilt angle can be obtained even with ultraviolet light having a long wavelength such as 365 nm. Was confirmed to be expressed. This is because the side chain moiety has two photosensitive groups, so that the photoreactivity of the photosensitive side chain moiety immobilized in the polymer is improved, and the polymerizable compound is present free in the system. This is thought to be due to a dramatic improvement in reactivity with

  On the other hand, when the polymerizable compounds of Comparative Examples 2 to 5 are not introduced, although there is an effect of improving the response speed, the photoreaction of the polymerization reaction or the crosslinking reaction does not proceed sufficiently when irradiated with ultraviolet light having a weak energy such as 365 nm. However, sufficient response speed and tilt angle cannot be obtained.

  Further, as shown in Comparative Example 6, even when a polymer having only a methacrylic group at the photosensitive side chain site and a polymerizable compound are used in combination, sufficient response speed improvement and tilt expression ability are obtained by irradiation with 365 nm ultraviolet rays. It was not obtained.

  From this, it is 365 nm by using together the polymer which has both photopolymerizable groups, such as a methacryl group, and photocrosslinkable groups, such as a cinnamoyl group, and a polymeric compound in the photosensitive side chain site like a present Example. It is possible to obtain a sufficient response speed and tilt angle even by irradiation with ultraviolet rays having a long wavelength such as.

Claims (8)

A polyimide precursor obtained by reaction of a diamine compound represented by the following formula [1] and a diamine component having a side chain for vertically aligning a liquid crystal and a tetracarboxylic dianhydride component, and an imide A liquid crystal aligning agent characterized by containing at least one polymer selected from polyimides obtained by crystallization and a polymerizable compound.

(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 cinnamoyl group, R ⁷ represents a single bond, an alkylene group having 1 to 30 carbon atoms, a divalent carbocycle or a heterocycle, One or more hydrogen atoms of the alkylene group, divalent carbocycle or heterocycle may be replaced with a fluorine atom or an organic group, and R ⁷ may be any of the following groups adjacent to each other: In this case, —CH ₂ — may be replaced by these groups; —O—, —NHCO—, —CONH—, —COO—, —OCO—, —NH—, —NHCONH—, — CO— R ⁸ represents a photopolymerizable group selected from an acrylic group and a methacryl group.)   2. The liquid crystal aligning agent according to claim 1, wherein the diamine compound represented by the formula [1] is 10 mol% to 90 mol% in the diamine component.   The liquid crystal aligning agent according to claim 1 or 2, wherein the diamine compound having a side chain for vertically aligning the liquid crystal is 10 mol% to 70 mol% in the diamine component. The liquid crystal aligning agent according to any one of claims 1 to 3, wherein the polymerizable compound is a polymerizable compound represented by the following formula.

  A liquid crystal alignment film obtained from the liquid crystal aligning agent according to any one of claims 1 to 4.   A liquid crystal display element comprising the liquid crystal alignment film according to claim 5. A diamine compound represented by the following formula [DA-4].

A diamine compound represented by the following formula [DA-13].