KR101998907B1 - Liquid crystal orientation agent, liquid crystal orientation membrane, liquid crystal display element, and diamine compound - Google Patents

Abstract

A liquid crystal alignment film comprising a polyimide precursor obtained by a reaction of a diamine component containing a diamine compound represented by the following formula [1] and a tetracarboxylic acid dianhydride component, and a polyimide obtained by imidating the polyimide precursor, My.

(Wherein, R ³ is _{-CH 2 -., -O-, -CONH-} , -NHCO-, -COO-, -OCO-, -NH-, it denotes a group selected from -CO- R ⁴ is C 1 A divalent carbon ring or a heterocyclic ring, and one or more hydrogen atoms of the alkylene group, the divalent carbon ring or the heterocyclic ring may be substituted with a fluorine atom or an organic group, and R ^4, in the case where any one of the groups exemplified in the following do not neighbor each other, -CH ₂ - is optionally are substituted with these; -O-, -NHCO-, -CONH-, -COO- , -OCO-, -NH-, -CO-, and R ⁵ represents any one of -CH ₂ -, -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH-, -CO-, represents. R ⁶ represents a light that causes the dimerization. R ⁷ represents a single bond, or, a C 1 -C alkyl group, a divalent carbocyclic or heterocyclic ring formed by the carbon number of 30, is an alkylene group, a divalent carbocyclic or Heterocyclic . Or or or may a plurality of hydrogen atoms are substituted with a fluorine atom or an organic addition, R ⁷ is In the case of any group exemplified in the following are not adjacent to each other, -CH ₂ - or may have been substituted with the foregoing; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -CO- R ⁸ represents a photopolymerizable group.

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal alignment film, a liquid crystal alignment film, a liquid crystal display device, and a diamine compound,

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

The liquid crystal display element of the system (also referred to as the vertical alignment system) in which the liquid crystal molecules aligned perpendicularly to the substrate are caused to respond by an electric field includes a step of irradiating ultraviolet rays while applying a voltage to the liquid crystal molecules in the manufacturing process There is.

In such a vertical alignment type liquid crystal display device, a photopolymerizable compound is added in advance to a liquid crystal composition and used together with a vertical alignment film such as polyimide to irradiate ultraviolet light while applying a voltage to the liquid crystal cell, (See, for example, Patent Document 1 and Non-Patent Document 1) are known (PSA type liquid crystal display). Generally, the direction in which liquid crystal molecules respond to an electric field is controlled by protrusions formed on a substrate or slits formed on a display electrode, etc. However, when a photopolymerizable compound is added to a liquid crystal composition and ultraviolet rays The polymer structure in which the direction in which the liquid crystal molecules are tilted is formed on the liquid crystal alignment film by irradiation so that the response speed of the liquid crystal display device is faster than the method in which the tilt direction of the liquid crystal molecules is controlled only by the projections or slits It is being referred to.

In this PSA type liquid crystal display element, the solubility of the polymerizable compound to be added to the liquid crystal is low, and there is a problem that precipitation occurs at a low temperature when the addition amount is increased. On the other hand, when the amount of the polymerizable compound to be added is reduced, a good alignment state can not be obtained. In addition, 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. Further, in the UV irradiation process required in the PSA mode, if the irradiation amount is large, the components in the liquid crystal are decomposed to cause a decrease in reliability.

Here, it has been reported that the response speed of a liquid crystal display device is also increased by adding a photopolymerizable compound not in a liquid crystal composition but in a liquid crystal alignment film (SC-PVA type liquid crystal display) (see, for example, Non-Patent Document 2) .

Japanese Patent Application Laid-Open No. 2003-307720

 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 photo-polymerizable compound is added is used. However, since the photo-polymerizable compound does not have a high solubility in the liquid crystal aligning agent, , The storage stability of the liquid crystal aligning agent is adversely affected. Further, if the unreacted photopolymerizable compound is eluted from the liquid crystal alignment film into the liquid crystal, it becomes an impurity, which causes the reliability of the liquid crystal display element to deteriorate.

Disclosure of the Invention The object of the present invention is to solve the problems of the above-described prior art, and it is an object of the present invention to provide a liquid crystal aligning agent, a liquid crystal alignment film, a liquid crystal display element, and a diamine capable of improving the response speed of a liquid crystal display element without adding a photopolymerizable compound ≪ / RTI >

As a result of intensive studies to solve the above problems, the inventors of the present invention found that a diamine component containing a group causing a photo-dimerization reaction and a novel diamine compound having a group causing a photopolymerization reaction in a side chain (hereinafter also referred to as a specific diamine compound) It is possible to solve the above problems by using a liquid crystal aligning agent containing at least one selected from a polyimide precursor obtained by the reaction of a tetracarboxylic acid dianhydride component and a polyimide obtained by imidizing the polyimide precursor. Completed. That is, the present invention has the following points.

1. A polyimide precursor comprising a polyimide precursor obtained by reacting a diamine component containing a diamine compound represented by the following formula [1] with a tetracarboxylic acid dianhydride component and at least one polymer selected from a polyimide obtained by imidating the polyimide precursor, Liquid crystal aligning agent.

[Chemical Formula 1]

(Wherein, R ³ is _{-CH 2 -., -O-, -CONH-} , -NHCO-, -COO-, -OCO-, -NH-, it denotes a group selected from -CO- R ⁴ is C 1 A divalent carbon ring or a heterocyclic ring, and one or more hydrogen atoms of the alkylene group, the divalent carbon ring or the heterocyclic ring may be substituted with a fluorine atom or an organic group, and R ^4, in the case where any one of the groups exemplified in the following do not neighbor each other, -CH ₂ - is optionally are substituted with these; -O-, -NHCO-, -CONH-, -COO- , -OCO-, -NH-, -NHCONH-, -CO-. R ⁵ is -CH ₂ -, -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH-, -CO-, of represents any. R ⁶ represents a light that causes the dimerization. R ⁷ represents a single bond, or, a C 1 -C alkyl group, a divalent carbocyclic or heterocyclic ring formed by carbon atoms 30, in which the alkyl group, 2 Carbon ring or complex Li one or more hydrogen atoms are optionally substituted with a fluorine atom or an organic addition, R ⁷ is In the case of any group exemplified in the following are not adjacent to each other, -CH ₂ -. Or may have been substituted with those -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, -CO- R ⁸ represents a photopolymerizable group.

2. The liquid crystal aligning agent according to item 1, wherein R ⁶ is a divalent group represented by the following formula.

(2)

(Wherein * represents the bonding position with R ⁵ or R ⁷ ).

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

(3)

(Wherein * represents a bonding position to R ⁷ ).

4. The liquid crystal aligning agent according to any one of 1 to 3, wherein the diamine component further comprises a diamine compound having a side chain that vertically aligns the liquid crystal.

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

6. The liquid crystal aligning agent according to any one of 2 to 5, wherein the diamine compound having a side chain which vertically aligns the liquid crystal is 5 mol% to 70 mol% of the diamine component.

(7) A liquid crystal alignment film obtained from the liquid crystal aligning agent described in any one of (1) to (6).

8. A liquid crystal display element comprising a liquid crystal alignment layer.

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

[Chemical Formula 4]

(Wherein R ¹¹ represents an alkylene group having 2 to 6 carbon atoms and R ¹² represents an alkylene group having 2 to 4 carbon atoms.)

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

[Chemical Formula 5]

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

[Chemical Formula 6]

(Wherein * denotes the bonding position with O and ** denotes the bonding position with R < ¹³ >).

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

(7)

K is 0 to 1, 1 is an integer of 1 to 6, m is 1 (m is 0 when n is 0), and n is an integer of 0 to 3. [ It is an integer of 6.

[Chemical Formula 8]

(Wherein * represents a bonding position with - (CH ₂ ) ₁ - and ** denotes a bonding position with O).

According to the present invention, it is possible to provide a liquid crystal aligning agent capable of improving the response speed of a liquid crystal display element, in particular, a liquid crystal display element of a vertical alignment system, even when a photopolymerizable compound is not contained. This liquid crystal aligning agent is not limited to the liquid crystal display element of the vertical alignment system but can be used, for example, in a liquid crystal display element which performs alignment treatment by irradiating with ultraviolet rays of polarized light, It is possible to obtain a liquid crystal alignment film which is effective for improving the afterglow.

Hereinafter, the present invention will be described in detail.

The liquid crystal aligning agent of the present invention comprises a polyimide precursor obtained by reacting a diamine component containing a diamine compound represented by the above formula [1] with a tetracarboxylic acid dianhydride component and a polyimide precursor obtained by imidizing the diamine component and at least one And the like. The liquid crystal aligning agent is a solution for preparing a liquid crystal alignment film, and the liquid crystal alignment film is a film for aligning the liquid crystal in a predetermined direction. Each component contained in the liquid crystal aligning agent of the present invention will be described in detail below.

≪ Specific diamine compound &

The diamine component which is a raw material of at least one kind of polymer selected from the polyimide precursor containing the liquid crystal aligning agent of the present invention and the polyimide obtained by imidizing the diamine includes the diamine compound represented by the above formula [1].

R ³ -R ⁴ -R ⁵ in the formula [1] is a spacer region connecting the diaminobenzene skeleton in the side chain and R ⁶ , which causes photo dimerization, and R ³ is a diamino bond in the diamino Benzene skeleton. This coupler R ³ can be optionally substituted with one or more substituents selected from the group consisting of -CH ₂ - (ie methylene), -O- (ie ether), -CONH- (ie amide), -NHCO- - (i.e., reverse ester), -NH- (i.e., amino), -CO- (i.e., carbonyl). These coupling groups R ³ can be formed by a common organic synthetic method, but -CH ₂ -, -O-, -COO-, -NHCO- and -NH- are preferable from the viewpoint of ease of synthesis.

R ⁴ in the formula [1] is an alkylene group, a divalent carbon ring, or a heterocyclic ring formed as a center of the spacer and having 1 to 30 carbon atoms. However, any hydrogen atom of the alkylene group, divalent carbon ring or heterocyclic ring may be substituted with a fluorine atom or an organic group. The number of hydrogen atoms to be substituted may be one or plural. One or more -CH ₂ - of the alkylene group, divalent carbon ring or heterocyclic ring may be substituted with any of these bonding groups when any one of the bonding groups shown below is not adjacent to each other; O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, -NH, -CO-. This means that R ⁴ may contain an alkylene group, a divalent carbon ring or a heterocyclic-bonding group-alkylene group, a divalent carbon ring or a heterocyclic ring. Furthermore, when R ³ is -CH ₂ -, it means that the terminal on the R ³ side in R ⁴ has a bonding contribution. Likewise, when R ⁵ is -CH ₂ -, the end on the R ⁵ side in R ⁴ means that the bond is also a bond. Thus, R ³ is -CH ₂ - and, also, R ⁵ is -CH ₂ - when, R ⁴ are the coupler - alkylene group, a divalent carbocyclic or heterocyclic-configuration that the coupler or, R ⁴ is the And a coupling unit may be used. Further, -CH ₂ - substituted by the bonding group may be in one site or may be plural sites if the bonding groups are not adjacent to each other. Specific examples of the divalent carbon ring group and the heterocyclic ring include the following structures, but the present invention is not limited thereto.

[Chemical Formula 9]

R ⁵ in the formula [1] represents a bonding group with R ⁶ at the spacer site. This coupler R ⁵ is selected from -CH ₂ -, -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH-, -CO-, and a single bond. These couplers R ⁵ may be formed by a common organic synthetic method, but from the viewpoint of ease of synthesis, -CH ₂ -, -O-, -COO-, -NHCO- and -NH- are preferable.

R ⁶ in the formula [1] represents a divalent organic group composed of a group causing light quantization. The group that causes light dimerization is a functional group that becomes a dimer by reacting by light irradiation. As R ⁶ , for example, a divalent group including a cinnamoyl group, a coumarin group and a chalcone group can be mentioned, and specific examples include a divalent group represented by the following formula, but it is not limited thereto. Further, one or plural hydrogen atoms of the group represented by the following formula may be substituted with an organic group.

[Chemical formula 10]

(Wherein * represents the bonding position with R ⁵ or R ⁷ ).

R ⁷ in the formula [1] is a moiety connecting R ⁶ , which is a group causing light quantization in the side chain, and R ⁸ , which is a photopolymerizable group, and R ⁷ is a single bond or a A divalent carbon ring or a heterocyclic ring. However, any hydrogen atom of the alkylene group, divalent carbon ring or heterocyclic ring may be substituted with a fluorine atom or an organic group. The number of hydrogen atoms to be substituted may be one or plural. One or more -CH ₂ - of the alkylene group, divalent carbon ring or heterocyclic ring may be substituted with any of these bonding groups when any one of the bonding groups shown below is not adjacent to each other; O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, -NH-, -CO-. This is, for example, a structure in which R ⁷ is an alkylene group, a divalent carbon ring or a heterocyclic-bonding group-alkylene group, a divalent carbon ring or a heterocyclic ring, or a bonding group- Or may contain a structure referred to as a heterocyclic ring. Further, -CH ₂ - substituted by the bonding group may be in one site or may be plural sites if the bonding groups are not adjacent to each other. Specific examples of the divalent carbon ring group and the heterocyclic ring include the following structures, but the present invention is not limited thereto.

(11)

R ⁸ in the formula [1] represents a photopolymerizable group. The photopolymerizable group is a functional group that generates polymerization by irradiation of light. R ⁸ is, for example, a monovalent group containing an acrylic group, a methacrylic group, a lactone group, a maleimide group, a vinyl group, an allyl group or a styryl group, specifically, a monovalent group represented by the following formula But the present invention is not limited thereto.

[Chemical Formula 12]

(Wherein * represents a bonding position to R ⁷ ).

By using a liquid crystal aligning agent containing at least one kind of polymer selected from a polyimide precursor obtained by using the diamine compound represented by the above formula [1] as a raw material and a polyimide obtained by imidating the polyimide precursor, The cross-linking reaction by the photopolymerizable group derived from the diamine compound and the dimerization reaction by the group causing the light dimetization proceed, and the direction in which the liquid crystal molecules incline due to the cross-linked site or the dimerized site which is generated as a result is stored, The response speed of the display element can be increased.

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

[Chemical Formula 13]

(Wherein R ¹¹ represents an alkylene group having 2 to 6 carbon atoms and R ¹² represents an alkylene group having 2 to 4 carbon atoms.)

Specific examples of the diamine compound represented by the formula [2] include the following diamine compounds.

[Chemical Formula 14]

The diamine compound represented by the above formula [1] includes, for example, a diamine compound represented by the following formula [3].

[Chemical Formula 15]

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

[Chemical Formula 16]

(Wherein * denotes the bonding position with O and ** denotes the bonding position with R < ¹³ >).

Specific examples of the diamine compound represented by the above formula [3] include the following diamine compounds.

[Chemical Formula 17]

The diamine compound represented by the above formula [1] includes, for example, a diamine compound represented by the following formula [4].

[Chemical Formula 18]

K is 0 to 1, 1 is an integer of 1 to 6, m is 1 (m is 0 when n is 0), and n is an integer of 0 to 3. [ It is an integer of 6.

[Chemical Formula 19]

(Wherein * represents a bonding position with - (CH ₂ ) ₁ - and ** denotes a bonding position with O).

Specific examples of the diamine compound represented by the above formula [4] include the following diamine compounds.

[Chemical Formula 20]

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

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

[Chemical Formula 21]

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

When the dinitro compound represented by the above formula [1a] is reduced, the reduction is carried out using a catalyst in which the double bond is not hydrogenated. The reduction reaction is preferably carried out in a solvent such as ethyl acetate, toluene, tetrahydrofuran, dioxane or alcohol, in combination with ammonium chloride, hydrogen chloride or the like with zinc, tin, tin chloride or iron.

The dinitro compound represented by the above formula [1a] can be obtained by a method of bonding -R ⁴ -R ⁵ -R ⁶ -R ⁷ -R ⁸ , which is a side chain moiety, to dinitrobenzene via R ³ . For example, when R ³ is an amide bond (-CONH-), an amino compound containing dinitrobenzene acid chloride and -R ⁴ -R ⁵ -R ⁶ -R ⁷ -R ⁸ is reacted in the presence of an alkali And the like.

When R ³ is a reverse amide bond (-HNCO-), a method of reacting an amino group-containing dinitrobenzene and an acid chloride containing -R ⁴ -R ⁵ -R ⁶ -R ⁷ -R ⁸ in the presence of an alkali .

When R ³ is an ester bond (-COO-), a method in which an alcohol compound containing dinitrobenzene acid chloride and -R ⁴ -R ⁵ -R ⁶ -R ⁷ -R ⁸ is reacted in the presence of an alkali . When R ³ is a reverse ester bond (-OCO-), an acid chloride compound containing a hydroxyl group-containing dinitrobenzene and -R ⁴ -R ⁵ -R ⁶ -R ⁷ -R ⁸ is reacted with an alkali In the presence of a base.

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

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

When R ³ is a carbonyl bond (-CO-), a boronic acid compound containing an aldehyde group-containing dinitrobenzene and -R ⁴ -R ⁵ -R ⁶ -R ⁷ -R ⁸ is reacted with a palladium or copper catalyst And a coupling reaction is carried out under a nitrogen atmosphere.

When R ³ is a carbon bond (-CH ₂ -), a compound having a halogen group-containing dinitrobenzene and -R ⁴ -R ⁵ -R ⁶ -R ⁷ -R ⁸ having an unsaturated bond at the end on the R ⁴ side , A method using a Heck reaction or a Sonogashira cross coupling reaction can be mentioned.

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

As a method of synthesizing -R ⁴ -R ⁵ -R ⁶ -R ⁷ -R ⁸ which is a side chain moiety, a method of synthesizing by the following exemplified method and the like can be given. For example, in the case of having an amide bond (-CONH-) 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 compound, an acid chloride compound containing -R ⁴ -R ⁵ -R ⁶ and an amino compound containing -R ⁷ -R ⁸ or -R ⁴ -R ⁵ -R ⁶ -R ⁷ And an amino compound containing -R ⁸ are reacted in the presence of an alkali.

(-HNCO-) in the structure of -R ⁴ -R ⁵ -R ⁶ -R ⁷ -R ⁸ , an 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 acid chloride compound containing -R ⁷ -R ⁸ , or -R ⁴ -R ⁵ -R ⁶ -R ⁷ And an acid chloride compound containing -R ⁸ are reacted in the presence of an alkali.

(-COO-) 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 alcohol compound containing -R ⁷ -R ⁸ or an alcohol compound containing -R ⁴ -R ⁵ -R ⁶ -R ⁷ A method in which an acid chloride compound and an alcohol compound containing -R ⁸ are reacted in the presence of an alkali.

(-OCO-) in the structure of -R ⁴ -R ⁵ -R ⁶ -R ⁷ -R ⁸ , 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 acid chloride compound containing -R ⁷ -R ⁸ or an acid chloride compound containing -R ⁴ -R ⁵ -R ⁶ -R ⁷ And an acid chloride compound containing -R < ⁸ > are reacted in the presence of an alkali.

(-O-) in the structure of -R ⁴ -R ⁵ -R ⁶ -R ⁷ -R ⁸ , a halogen compound containing -R ⁴ and -R ⁶ -R ⁷ -R ⁸ are included A halogen compound containing -R ⁴ -R ⁵ -R ⁶ and an alcohol compound containing -R ⁷ -R ⁸ , a halogen compound containing -R ⁴ -R ⁵ -R ⁶ -R ⁷ , alcohol compounds, including R ^8, a halogen compound comprising an alcohol compound containing an -R ⁴ and ^{-R 6 -R 7 -R 8, -R} 4 -R 5 -R ⁶ with an alcohol compound containing a -R ⁷ A halogen compound containing -R ⁸ or a method of reacting an alcohol compound containing -R ⁴ -R ⁵ -R ⁶ -R ⁷ with a halogen compound containing -R ⁸ in the presence of an alkali.

(-NH-) in the structure of -R ⁴ -R ⁵ -R ⁶ -R ⁷ -R ⁸ , a halogen compound containing -R ⁴ and -R ⁶ -R ⁷ -R ⁸ are included A halogen compound containing -R ⁴ -R ⁵ -R ⁶ , an amino compound containing -R ⁷ -R ⁸ , a halogen compound containing -R ⁴ -R ⁵ -R ⁶ -R ⁷ , R ⁸ , an amino compound containing -R ⁴ , a halogen compound containing -R ⁶ -R ⁷ -R ⁸ , an amino compound containing -R ⁴ -R ⁵ -R ⁶ , and an amino compound containing -R ⁷ A halogen compound containing -R ⁸ or a method of reacting an amino compound containing -R ⁴ -R ⁵ -R ⁶ -R ⁷ with a halogen compound containing -R ⁸ in the presence of an alkali.

(-CO-) in the structure of -R ⁴ -R ⁵ -R ⁶ -R ⁷ -R ⁸ , an aldehyde compound containing -R ⁴ and -R ⁶ -R ⁷ -R ⁸ An aldehyde compound containing -R ⁴ -R ⁵ -R ⁶ and a boronic acid compound containing -R ⁷ -R ⁸ , an aldehyde containing -R ⁴ -R ⁵ -R ⁶ -R ⁷ aldehyde compounds including boronic acid compounds and compounds containing a -R ^8, boronic acid compounds including -R ⁴ and -R ⁶ -R ⁷ -R ^8, boron containing -R ⁴ -R ⁵ -R ⁶ aldehyde compounds comprising an acid compound and -R ⁷ -R ^8, or, reacting an aldehyde compound containing a boronic acid compound, including -R ⁴ -R ⁵ -R ⁶ -R ⁷ and -R ^8, under the presence of an alkali .

≪ Diamine compound having side chains for vertically orienting liquid crystal &

The diamine component, which is a raw material of at least one polymer selected from the polyimide precursor containing the liquid crystal aligning agent of the present invention and the polyimide obtained by imidizing the liquid crystal aligning agent, Or a diamine compound having a side chain in which Examples of the diamine compound having a side chain that vertically aligns 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, or a group in which a part or all of hydrogen atoms in these groups are substituted with a fluorine atom Diamines having one group as a side chain, for example, diamines represented by the following formulas [A-1] to [A-24], but the present invention is not limited thereto.

[Chemical Formula 22]

(In the formulas [A-1] to [A-5], A ₁ is an alkyl group having 2 to 24 carbon atoms or a fluorine-

(23)

(In the formulas [A-6] and [A-7], A ₂ represents -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ - or -CH ₂ OCO- and A 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.)

≪ EMI ID =

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

(25)

(Wherein [A-11] and the equation [A-12] of, A ₆ is -COO-, -OCO-, -CONH-, -NHCO-, -COOCH 2 -, -CH 2 OCO-, -CH 2 O _{-, -OCH 2 -, -CH 2} -, -O-, or represents a -NH-, a ₇ is a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, acetyl group, acetoxy Or a hydroxyl group.)

(26)

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

(27)

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

(28)

Specific examples of the diamine compound having a side chain for vertically orienting a liquid crystal include diamines represented by the following formulas [A-25] to [A-30].

[Chemical Formula 29]

(Wherein [A-25] ~ formula [A-30] of, A ₁₂ is -COO-, -OCO-, -CONH-, -NHCO-, -CH 2 -, -O-, -CO-, or - NH-, and A ₁₃ represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.

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

(30)

Among these, [A-1], [A-2], [A-3], [A-4], [A- 5], and [A-2] are preferable from the viewpoints of the ability to vertically align liquid crystals, Diamines of [A-25], [A-26], [A-27], [A- 28], [A- 29] and [A-

The diamine may be used alone or in combination of two or more thereof depending on the properties of the liquid crystal alignment layer, such as liquid crystal alignability, pretilt angle, voltage holding characteristics, and accumulated charge.

The ratio of the diamine having a side chain that vertically aligns the liquid crystal contained in the diamine component, which is the raw material of the polyimide precursor containing the liquid crystal aligning agent of the present invention and at least one polymer selected from the imide of the polyimide, Although not limited, it is preferable to use an amount of 5 mol% to 70 mol% of the diamine component used in the synthesis of the polyimide precursor, more preferably 10 mol% to 50 mol% of the diamine component, Is from 20 mol% to 50 mol%. When the diamine having a side chain that vertically aligns the liquid crystal is used in an amount of 5 mol% to 70 mol% of the diamine component used for the synthesis of the polyimide precursor, an improvement in the response speed and a It is especially excellent in terms of.

≪ Other diamine compounds >

In addition, as long as the effect of the present invention is not impaired, the diamine component, which is a raw material of at least one polymer selected from the polyimide precursor containing the liquid crystal aligning agent of the present invention and the polyimide obtained by imidizing the polyimide precursor, Or a diamine other than the diamine having a side chain for vertically orienting the liquid crystal or the diamine represented by the formula [1]. As other diamines, for example, p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m- , 2,4-dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, Diminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diaminobiphenyl, 3,3'- Diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'- Dicarboxy-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl-4,4'- Diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane , 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'- Aminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2 , 3'-diaminodiphenyl ether, 4,4'-sulfonyldiamine, 3,3'-sulfonyldiamine, bis (4-aminophenyl) silane, bis Aminophenyl) silane, dimethyl-bis (3-aminophenyl) silane, 4,4'-thiodianiline, 3,3'-thiodianiline, 4,4'-diaminodiphenylamine, Diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl (4,4'-diaminodiphenylamine, (3,3'-diaminodiphenyl) amine, N-methyl (3,4'-diaminodiphenyl) amine, N-methyl (2,2'-diamino (2,3'-diaminodiphenyl) amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone , 1,4-diaminonaphthalene, 2,2'-diamine Benzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5- (4-aminophenyl) ethane, 1,2-bis (3-aminophenyl) aminophenol, 2,6- diaminonaphthalene, 2,7- diaminonaphthalene, 2,8- Propane, 1,3-bis (3-aminophenyl) propane, 1,4-bis (4-aminophenyl) butane, 1,4- (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1 Benzene, 1,4-bis (4-aminobenzyl) benzene, 1,3-bis (4-aminophenoxy) benzene, Benzene, 4,4 '- [1,4-phenylenebis (methylene)] dianiline, 4,4' - [1,3-phenylenebis (methylene)] dianiline, 3,4 ' 4,3'- [1,3-phenylenebis (methylene)] dianiline, 3,3 '- [ - [1,4-phenylenebis (methylene)] dianiline, 3,3 '- [1,3-phenylenebis (methylene)] dianiline, Methane], 1,3-phenylenebis [(3-aminophenyl) methanone], 1,3-phenylenebis [ (4-aminobenzoate), 1,4-phenylenebis (3-aminobenzoate), 1,3-phenylenebis Bis (4-aminophenyl) isophthalate, bis (4-aminophenyl) terephthalate, bis (3-aminophenyl) isophthalate, N, N '- (1,4-phenylene) ), N, N '- (1,4-phenylene) bis (3-aminobenzamide) -Bis (4-aminophenyl) terephthalamide, N, N'-bis (3-aminophenyl) (4-aminophenyl) anthracene, N, N'-bis (3-aminophenyl) isophthalamide, N, N'- , 4'-bis (4-aminophenoxy) diphenyl sulfone, 2,2'-bis [4- (4-aminophenoxy) phenyl] propane, 2,2'- (4-aminophenyl) hexafluoropropane, 2,2'-bis (3-aminophenyl) hexafluoropropane, 2,2'-bis Bis (3-aminophenyl) propane, 2,2'-bis (3-aminophenyl) propane, Diaminobenzoic acid, 1,3-bis (4-aminophenoxy) propane, 1,3-bis (3-aminophenoxy) Propane, 1,4-bis (4-aminophenoxy) butane, 1,4-bis (3-aminophenoxy) butane, 1,5- 3-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) hex , 1,7-bis (4-aminophenoxy) heptane, 1,7- (3-aminophenoxy) heptane, (3-aminophenoxy) octane, 1,9-bis (3-aminophenoxy) (3-aminophenoxy) decane, 1,11- (4-aminophenoxy) undecane, 1,11- (4-aminocyclohexyl) methane, bis (4-aminophenoxy) dodecane and the like, aromatic diamines such as 1,12- 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-dia Diaminododecane, 1,12-diamino dioctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diamino undecane, and 1,12-diaminododecane, .

The other diamines may be used alone or in combination of two or more thereof depending on the properties such as liquid crystal alignability, pretilt angle, voltage holding characteristics, and accumulated charge when used as a liquid crystal alignment film.

≪ Tetracarboxylic acid dianhydride component >

In order to obtain the polyimide precursor, the tetracarboxylic acid dianhydride component to be reacted with the diamine component is not particularly limited. Specific examples include pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-anthracene tetracarboxylic acid, 1,2,5,6-anthracene tetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,3,3 (3,4-dicarboxyphenyl) ether, 3,3 ', 4,4'-benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) Sulfone, bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2- (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5- (3,4-dicarboxyphenyl) pyridine, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid Acid, 1,3-diphenyl-1,2,3,4-cyclobutanetetracar Oxydipetetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexane Tetracarboxylic acid, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic acid, 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxyl Acid, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid, 1,2,3,4-cycloheptane tetracarboxylic acid, 2,3,4,5-tetrahydrofuran tetra Carboxylic 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-tetrahydronaphthalene- 2,2,2] octo-7-ene-2,3,5,6-tetracarboxylic acid, 5- (2,5-dioxotetrahydrofuryl) -3-methyl- - cyclohexane-1,2-dicarboxylic acid, tetracyclo [6,2,1,1,0,2,7] dodeca-4,5,9,10-tetracarboxylic acid, 3,5, 6-tricarboxy norbornane-2: 3,5: 6 dicarboxylic acid, and 1,2,4,5-cyclohexanetetracarboxylic acid. Of course, the tetracarboxylic acid dianhydride may be used alone or in combination of two or more, depending on the properties such as liquid crystal aligning property, voltage holding property, and accumulated charge when the liquid crystal alignment film is used.

≪ Synthesis of polyimide precursor >

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

The polyamic acid can be obtained by the reaction of the diamine component and the tetracarboxylic acid dianhydride component by a known synthetic method. In general, the method is a method of reacting a diamine component and a tetracarboxylic acid dianhydride component in an organic solvent. The reaction between the diamine component and the tetracarboxylic acid dianhydride component is advantageous in that it proceeds relatively easily in an organic solvent and does not generate any by-products.

The organic solvent used in the reaction is not particularly limited as long as it dissolves the produced polyamic acid. Further, even if the organic solvent does not dissolve the polyamic acid, it may be mixed with the solvent in the range where the produced polyamic acid is not precipitated. In addition, water in the organic solvent inhibits the polymerization reaction, and further causes hydrolysis of the produced polyamic acid. Therefore, it is preferable to use an organic solvent that is dehydrated and dried. Examples of the organic solvent used in the reaction include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N-methylformamide, Pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide, N- But are not limited to, lactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide,? -Butyrolactone, isopropyl alcohol, methoxymethyl pentanol, dipentene, ethyl amyl ketone, , Methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol , Ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol Propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol, diethylene glycol monoacetate , Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol mono Propyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, di Isobutylene, amyl acetate Butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate Propylene carbonate, methyl lactate, methyl lactate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, methyl pyruvate, methyl 3- Methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 2-methoxypropionate, 3-methoxypropionic acid, -Ethyl-1-hexanol, and the like. These organic solvents may be used alone or in combination.

When the diamine component and the tetracarboxylic acid dianhydride component are reacted in an organic solvent, the solution in which the diamine component is dispersed or dissolved in an organic solvent is stirred and the tetracarboxylic acid dianhydride component is dispersed or dissolved in the organic solvent as it is A method of adding a diamine component to a solution in which a tetracarboxylic acid dianhydride component is dispersed or dissolved in an organic solvent, a method of alternately adding a tetracarboxylic acid dianhydride component and a diamine component, and the like , Or any of these methods may be used. When the diamine component or the tetracarboxylic acid dianhydride component is composed of a plurality of compounds, they may be reacted in advance in a mixed state, or they may be sequentially reacted individually, and the low molecular weight compounds reacted individually may be mixed and reacted, May be used.

The temperature at which the diamine component is reacted with the tetracarboxylic acid dianhydride component may be selected from any temperature, for example, from -20 ° C to 150 ° C, preferably from -5 ° C to 100 ° C. The reaction can be carried out at any concentration. For example, the total amount of the diamine component and the tetracarboxylic acid dianhydride component relative to the reaction solution is 1 to 50 mass%, preferably 5 to 30 mass%.

The ratio of the total molar amount of the tetracarboxylic acid dianhydride component to the total molar amount of the diamine component in the above polymerization reaction can be selected in accordance with the molecular weight of the polyamic acid to be obtained. As in the case of the usual polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the produced polyamic acid. It is 0.8 to 1.2 if it shows a preferable range.

The method for synthesizing the polyamic acid to be used in the present invention is not limited to the above-mentioned method, and it is also possible to use, as the tetracarboxylic acid dianhydride component, tetracarboxylic acid or tetracarboxylic acid The corresponding polyamic acid can also be obtained by using a tetracarboxylic acid derivative such as an acid halide or the like and reacting it by a known method.

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

(1) Synthesis from polyamic acid

The polyamic acid ester can be synthesized by esterifying a polyamic acid obtained from a tetracarboxylic acid dianhydride and a diamine component. Concretely, 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 .

The esterifying agent is preferably one which can be easily removed by purification. Examples of the esterifying agent include N, N-dimethylformamide dimethylacetal, N, N-dimethylformamide diethyl acetal, N, N-dimethylformamide dipropyl acetal, N, N-dimethylformamide dineopentylbutyl acetal, N, N-dimethylformamide di-t-butyl acetal, 1-methyl-3-p-tolyltriazine, , 1-propyl-3-p-tolyltriazine, and 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride. The addition amount of the esterifying agent is preferably 2 to 6 molar equivalents relative to 1 mol of the repeating unit of the polyamic acid.

The solvent to be used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone or γ-butyrolactone from the solubility of the polymer, May be used. The concentration at the time of the synthesis is preferably from 1 to 30 mass%, more preferably from 5 to 20 mass%, from the viewpoint that the precipitation of the polymer does not occur well and the high molecular weight material is easily obtained.

(2) When synthesized by the reaction of a tetracarboxylic acid diester dichloride with a diamine component

The polyamic acid ester can be synthesized with a tetracarboxylic acid diester dichloride and a diamine component. Specifically, the tetracarboxylic acid diester dichloride and the diamine component are reacted in the presence of a base and an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C for 30 minutes to 24 hours, preferably 1 To < / RTI > 4 hours.

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

As the solvent used in the above reaction, N-methyl-2-pyrrolidone and? -Butyrolactone are preferable from the viewpoint of the solubility of the monomer and the polymer, and these solvents may be used alone or in combination of two or more. The concentration of the polymer in the synthesis is preferably from 1 to 30 mass%, more preferably from 5 to 20 mass% from the viewpoint that the precipitation of the polymer does not occur well and the high molecular weight material is easily obtained. In order to prevent the hydrolysis of the tetracarboxylic acid diester dichloride, it is preferable that the solvent used for the synthesis of the polyamic acid ester is dehydrated as much as possible, and it is preferable to prevent the ambient air from being mixed in a nitrogen atmosphere.

(3) When synthesized by the reaction of a tetracarboxylic acid diester and a diamine component

The polyamic acid ester can be synthesized by polycondensation of a tetracarboxylic acid diester and a diamine component. Specifically, the tetracarboxylic acid diester and the diamine component are reacted 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 < / RTI > 15 hours.

Examples of the condensing agent include triphenylphosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3- dimethylaminopropyl) carbodiimide hydrochloride, N, N'-carbonyldiimidazole, dimethoxy- N, N ', N'-tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) 1-yl) -N, N, N ', N'-tetramethyluronium hexafluorophosphate and (2,3-dihydro-2-thioxo-3-benzoxazolyl) . The amount of the condensing agent to be added is preferably 2 to 3 times the mole of the tetracarboxylic acid diester.

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

In addition, 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 from 0 to 1.0 times the amount of the diamine component.

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

The solution of the polyamic acid ester obtained as described above can be precipitated by injecting it into a poor solvent while stirring well. After several times of precipitation and washing with a poor solvent, the purified polyamic acid ester powder can be obtained at room temperature or by heating and drying. Examples of the poor solvent include, but are not limited to, water, methanol, ethanol, hexane, butyl cellosolve, acetone, and toluene.

<Synthesis of soluble polyimide>

Examples of the method of imidizing the polyamic acid into a polyimide include thermal imidization in which a solution of a polyamic acid is heated as it is, and catalyst imidization in which a catalyst is added to a solution of a polyamic acid. In addition, the imidation rate from polyamic acid to polyimide does not necessarily have to be 100%.

The temperature at which the polyamic acid is thermally imidized in the solution is 100 ° C to 400 ° C, preferably 120 ° C to 250 ° C, and it is preferable to carry out the removal while removing the water generated by the imidization reaction out of the system.

The catalyst imidation of polyamic acid can be carried out by adding a basic catalyst and acid anhydride to a solution of polyamic acid and stirring at -20 to 250 ° C, preferably 0 to 180 ° C. The amount of the basic catalyst is 0.5 to 30 times, preferably 2 to 20 times, the molar amount of the amide group, and the amount of the acid anhydride is 1 to 50 times, preferably 3 to 30 times, the molar amount of the amide group. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Of these, pyridine is preferable because it has a basicity suitable for proceeding the reaction. As the acid anhydride, acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like can be given. Among them, acetic anhydride is preferable because the purification after completion of the reaction becomes easy. The imidization rate by the catalyst imidization can be controlled by adjusting the catalyst amount, the reaction temperature, and the reaction time.

In the case of recovering the polyamic acid or polyimide produced from the reaction solution of polyamic acid or polyimide, the reaction solution may be put into a poor solvent and precipitated. Examples of the poor solvent used in the precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene and water. The polymer precipitated by charging into a poor solvent can be recovered by filtration and then dried at normal temperature or under reduced pressure or by heating. In addition, when the polymer precipitated and recovered is redissolved in an organic solvent, and the operation of re-precipitation and recovery is repeated 2 to 10 times, impurities in the polymer can be reduced. As the poor solvent in this case, for example, alcohols, ketones, hydrocarbons and the like can be mentioned, and when three or more poor solvents selected from these are used, the purification efficiency is further improved, which is preferable.

<Liquid Crystal Aligner>

As described above, the liquid crystal aligning agent of the present invention is a polyimide precursor obtained by reacting a diamine component containing a diamine compound represented by the formula [1] and a tetracarboxylic acid dianhydride component, and a polyimide precursor thereof And at least one kind of polymer selected from polyimides obtained by hydrogenation. A polyimide precursor obtained by reacting a diamine component containing a diamine compound represented by the above formula [1] and a tetracarboxylic acid dianhydride component contained in a liquid crystal aligning agent, and a polyimide obtained by imidizing the polyimide precursor The total amount of the at least one kind of polymer is preferably 1 to 10 (mass%).

The liquid crystal aligning agent of the present invention can be obtained by reacting a polyimide precursor obtained by reacting a diamine component containing a diamine compound represented by the above formula [1] with a tetracarboxylic acid dianhydride component, and a polyimide precursor And at least one kind of polymer selected from the group consisting of polyimides obtained by subjecting the polyimide to a polymerization reaction. At this time, a polyimide precursor obtained by reacting a diamine component containing a diamine compound represented by the above formula [1] and a tetracarboxylic acid dianhydride component in the entire polymer components, and a polyimide precursor obtained by imidizing the polyimide precursor The ratio of the at least one polymer selected from the obtained polyimide is preferably 10 (mass)% or more.

The molecular weight of the polymer having the liquid crystal aligning agent is preferably in the range of from 0.1 to 10 parts by weight based on the weight average molecular weight measured by GPC (Gel Permeation Chromatography), considering the strength of the liquid crystal alignment film obtained by applying the liquid crystal aligning agent, The molecular weight is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000.

There is no particular limitation on the solvent contained in the liquid crystal aligning agent, and a polyimide precursor obtained by reacting a diamine component containing a diamine compound represented by the above formula [1] with a tetracarboxylic acid dianhydride component, and a polyimide precursor And at least one kind of polymer selected from polyimides obtained by imidization can be dissolved or dispersed. For example, organic solvents such as those exemplified in the synthesis of the polyamic acid may be mentioned. Among them, N-methyl-2-pyrrolidone,? -Butyrolactone, N-ethyl-2-pyrrolidone, Dimethyl propanamide is preferable from the viewpoint of solubility. Of course, two or more types of mixed solvents may be used.

In addition, it is preferable to use a solvent which improves the uniformity and smoothness of the coating film in a solvent having high solubility of the component containing the liquid crystal aligning agent. Examples of the solvent that improves the uniformity and smoothness of the coating film include isopropyl alcohol, methoxymethyl pentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, butyl cell But are not limited to, sucrose acetate, ethylcellosolve acetate, butylcarbitol, ethylcarbitol, ethylcarbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol mono Propylene glycol monomethyl ether, 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- Propyl ether, isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methyl ethyl ketone, Propyl ether, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl acetate Ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methylethyl 3-ethoxypropionate, 3-methoxy Methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-methoxypropionate, 1-methoxypropionate, 2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2 Ethyl acetate, lactic acid ethyl ester, n-propyl lactate, n-butyl lactate, isoamyl lactate, 2-ethyl-1-pentyl lactate, - hexanol and the like. These solvents may be mixed with a plurality of kinds. When these solvents are used, it is preferably 5 to 80 mass%, more preferably 20 to 60 mass%, of the total solvent contained in the liquid crystal aligning agent.

The liquid crystal aligning agent may contain other components. Examples thereof include a compound which improves film thickness uniformity and surface smoothness when a liquid crystal aligning agent is applied, a compound which improves the adhesion between the liquid crystal alignment film and the substrate, and the like.

Examples of the compound that improves film thickness uniformity and surface smoothness include a fluorine-based surfactant, a silicon-based surfactant, and a nonionic surface-active agent. More specifically, for example, EF301, EF303, EF352 (manufactured by TOKEM PRODUCTS CO., LTD.), Megapuck F171, F173, R-30 (manufactured by Dainippon Ink and Chemicals Inc.), Fluorad FC430 and FC431 manufactured by Sumitomo 3M ), Asahi Guard AG710, Surfron S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Kagaku Co., Ltd.). When these surfactants are used, the proportion thereof is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, based on 100 parts by mass of the total amount of the polymer contained in the liquid crystal aligning agent.

Specific examples of the compound that improves the adhesion between the liquid crystal alignment layer and the substrate include a functional silane-containing compound and an epoxy group-containing compound. For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3 3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxy (3-aminopropyl) Aminopropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, Amine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl Acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N- Bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- Aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neo Pentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6 -Tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl ) N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 3- (N-allyl-N-glycidyl) aminopropyltrimethoxysilane, 3- (N, N-diglycidyl) And the like can be given no trimethoxysilane. 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 these compounds are used, it is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of the polymer contained in the liquid crystal aligning agent.

The liquid crystal aligning agent may be added with a dielectric material or a conductive material for the purpose of changing electric characteristics such as the dielectric constant and conductivity of the liquid crystal alignment film as long as the effect of the present invention is not impaired.

&Lt; Liquid crystal alignment film &

This liquid crystal aligning agent is coated on the substrate and baked to form a liquid crystal alignment film for vertically aligning the liquid crystal.

At this time, the substrate to be used is not particularly limited as long as it is a substrate having high transparency, 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 for liquid crystal driving is formed from the viewpoint of simplifying the process. In the reflection type liquid crystal display device, an opaque material such as a silicon wafer can be used only for a substrate on one side. In this case, a material for reflecting light such as aluminum can also be used as the electrode in this case.

The method of applying the liquid crystal aligning agent is not particularly limited, and examples thereof include screen printing, offset printing, flexographic printing, inkjet, dip, roll coater, slit coater and spinner.

The baking temperature of the coating film formed by applying the liquid crystal aligning agent is not limited and may be, for example, at any temperature of 100 ° C to 350 ° C, preferably 120 ° C to 300 ° C, more preferably 150 ° C To 250 ° C. The firing can be performed by a hot plate, a hot air circulation path, an infrared ray lamp, or the like.

The thickness of the liquid crystal alignment film obtained by baking is not particularly limited, but is preferably 5 to 300 nm, and more preferably 10 to 100 nm.

<Liquid crystal display element>

A liquid crystal display element of the present invention comprises two substrates arranged to face each other, a liquid crystal layer formed between the substrate and the liquid crystal layer, and a liquid crystal cell having the liquid crystal alignment film formed by the liquid crystal aligning agent of the present invention And a liquid crystal layer. More specifically, a liquid crystal alignment film is formed by applying the liquid crystal aligning agent of the present invention on two substrates and firing, and two substrates are arranged so that the liquid crystal alignment films face each other. And a liquid crystal cell formed by sandwiching the constituted liquid crystal layer and irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer. As the liquid crystal display of the present invention, various kinds of liquid crystal display devices such as a twisted nematic (TN) type, a vertical alignment (VA) type, and an in-plane switching (IPS) .

As described above, by using the liquid crystal alignment film formed by the liquid crystal aligning agent of the present invention and irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer, the photopolymerizable groups and the light quantities of side chains of the polyimide precursor and polyimide , That is, by reacting a photopolymerizable group derived from a diamine compound represented by the above formula [1] and a group causing a light dimerization, even when a photopolymerizable compound is not contained in the liquid crystal aligning agent, The orientation of the liquid crystal is more efficiently fixed than the liquid crystal alignment film using the liquid crystal alignment agent and the response speed is remarkably excellent. Of course, it is possible to obtain a liquid crystal display element having the same or higher response speed even if a photopolymerizable compound is added to the liquid crystal aligning agent of the present invention.

The substrate used in the liquid crystal display element of the present invention is not particularly limited as long as it is a substrate having high transparency, but is usually a substrate on which a transparent electrode for driving liquid crystal is formed. Specific examples include the same substrates as those described in the liquid crystal alignment film. A substrate on which a conventional electrode pattern or a projection pattern is formed may be used. In the liquid crystal display element of the present invention, since the liquid crystal aligning agent of the present invention is used as a liquid crystal aligning agent for forming a liquid crystal alignment film, It is possible to operate in a structure in which a line / slit electrode pattern of 10 to 10 mu m is formed and a slit pattern or a projection pattern is not formed in the counter substrate. By the liquid crystal display element of this structure, And a high transmittance can be obtained.

In a high-performance device such as a TFT-type device, a device such as a transistor is formed between an electrode for liquid crystal driving and a substrate.

In the case of a transmissive liquid crystal display device, it is common to use such a substrate as described above. However, in a reflective liquid crystal display device, an opaque substrate such as a silicon wafer can be used as long as it is only on one substrate. At this 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 then firing, and the details are the same 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 liquid crystal materials used in conventional vertical alignment methods such as MLC-6608 and MLC-6609 manufactured by Merck & Or MLC-2041 can be used.

As a method of sandwiching the liquid crystal layer between two substrates, known methods can be mentioned. For example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, spacers such as beads are scattered on the liquid crystal alignment film of one substrate, and the other side of the substrate is bonded (Bonded), and the liquid crystal is injected under reduced pressure and sealed. A pair of substrates on which a liquid crystal alignment film is formed is prepared, a spacer such as beads is dispersed on a liquid crystal alignment film of one of the substrates, and liquid crystal is dropped thereon. Thereafter, A liquid crystal cell can also be manufactured by a method in which one substrate is bonded and sealed. The thickness of the spacer at this time is preferably 1 to 30 占 퐉, more preferably 2 to 10 占 퐉.

The step of producing a liquid crystal cell by irradiating ultraviolet rays while applying a voltage to a liquid crystal alignment film and a liquid crystal layer is performed by applying an electric field to a liquid crystal alignment film and a liquid crystal layer by applying a voltage between electrodes provided on the substrate, And a method of irradiating ultraviolet rays while maintaining the electric field. Here, the voltage applied between the electrodes is, for example, 5 to 30 Vp-p, preferably 5 to 20 Vp-p. The irradiation amount of ultraviolet rays is, for example, 1 to 60 J or less, preferably 40 J or less. When the amount of ultraviolet irradiation is small, reliability deterioration caused by destruction of members constituting the liquid crystal display element can be suppressed The ultraviolet ray irradiation time can be reduced and the production efficiency is increased, which is preferable.

As described above, when ultraviolet rays are irradiated while a voltage is applied to the liquid crystal alignment film and the liquid crystal layer, the reaction of the photopolymerizable group and the group causing the light dimerization of the side chains of the polyimide precursor and polyimide proceeds, 1], the dimerization reaction by the photopolymerizable group originated from the diamine compound and the group causing the light dimerization proceeds, and the direction in which the liquid crystal molecules are inclined due to the crosslinking site or the dimerization site resulting therefrom is memorized , 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 liquid crystal display element of a vertical alignment type such as a PSA type liquid crystal display or an SC-PVA type liquid crystal display, but also a liquid crystal aligning agent produced by rubbing treatment or photo- And can be suitably used for a liquid crystal alignment film.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example

The abbreviations of the tetracarboxylic acid dianhydrides and diamines used in the synthesis examples and their structures are shown below.

(31)

(32)

(33)

(34)

The abbreviations of the organic solvents used in the examples and the like are as follows.

NMP: N-methyl-2-pyrrolidone

BCS: butyl cellosolve

THF: tetrahydrofuran

DMF: N, N-dimethylformamide

DMAc: N, N-dimethylacetamide

EtOH: ethanol

HEMA: 2-hydroxyethyl methacrylate

EDC: 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride

DMAP: 4-dimethylaminopyridine

&Lt; Measurement of molecular weight of polymer &

The molecular weight of the polyimide or polyamic acid was measured as follows using a room temperature gel permeation chromatography (GPC-101) manufactured by Shodex Co., Ltd., and a column (KD-803, KD-805) Respectively.

Column temperature: 50 ° C

Eluent: N, N-dimethylformamide (30 m mol / l of lithium bromide-hydrate (LiBr.H ₂ O) as additive, 30 mmol / l of phosphoric acid anhydrous crystal (o-phosphoric acid) (THF) of 10 ml / l)

Flow rate: 1.0 ml / min

Standard sample for preparing calibration curve: TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000, 30,000) manufactured by Toso Corporation and polyethylene glycol (molecular weight about 12,000, 4,000, 1,000) manufactured by Polymer Laboratories.

< ¹ Measurement of HNMR>

Apparatus: Fourier transform type superconducting nuclear magnetic resonance apparatus (FT-NMR) INOVA-400 (manufactured by Varian) 400 MHz

Solvent: deuterated dimethylsulfoxide (DMSO-d ₆ ), deuterated chloroform (CDCl ₃ )

Standard material: tetramethylsilane (TMS)

(Example 1) Synthesis of DA-4

(Example 1-1) Synthesis of DA-4 precursor DA-4-1

(35)

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. The filtrate was dried to obtain 90.0 g of the target DA-4-1 (white solid) (yield: 75%).

(Example 1-2) Synthesis of DA-4-2 precursor DA-4

(36)

In a 500 ml three-necked flask, 19.2 g of DA-4-1, 250 ml of dimethylformamide, 20.5 g of 6-chloro-1-hexanol, 41.5 g of potassium carbonate and 1.7 g of potassium iodide were added to 60 Lt; 0 &gt; 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. The filtrate was dissolved in 300 ml of ethyl acetate and extracted with saturated brine. Anhydrous magnesium sulfate was added to the organic layer, followed by dehydration drying, filtration, and solvent distillation using a rotary evaporator To obtain 26.99 g of the target DA-4-2 (clear solid) (yield: 92%).

(Example 1-3) Synthesis of precursor DA-4-3 of DA-1

(37)

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

(Example 1-4) Synthesis of precursor DA-4-4 of DA-1

(38)

300 ㎖ 3 necked flask, 11.7 g of DA-4-3, triethylamine (Et ₃ N) to 4.9 g and was added to tetrahydrofuran ㎖ 200. The inside of the system was cooled to 0 占 폚, 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. Then ethyl acetate was added to extract the organic layer. Anhydrous magnesium sulfate was added to the organic layer, followed by dehydration drying and filtration. Thereafter, the solvent was distilled off using a rotary evaporator Respectively. The residue was recrystallized from ethyl acetate to obtain 7.2 g of the target DA-4-4 (yellowish white solid) (yield: 35%).

(Example 1-5) Synthesis of precursor DA-4-5 of DA-4

[Chemical Formula 39]

6.9 g of DA-4-4, 60 ml of tetrahydrofuran, 3.0 g of 2-hydroxyethyl methacrylate (HEMA), 3.0 g of 1- (3-dimethylaminopropyl) -3- 4.4 g of ethyl carbodiimide hydrochloride (EDC) and 0.2 g of 4-dimethylaminopyridine (DMAP) were added, and the mixture was stirred at room temperature. After completion of the reaction, the organic layer was extracted with chloroform, and anhydrous magnesium sulfate was added to the organic layer, followed by dehydration drying, filtration, solvent distillation using a rotary evaporator, and distilling off the residue with isopropyl alcohol / hexane = 1 / 5 to obtain 5.9 g of the target DA-4-5 (a yellowish white solid) (yield 69%).

(Example 1-6) Synthesis of DA-4

(40)

5.9 g of DA-4-5, 60 ml of tetrahydrofuran and 60 ml of pure water were added to a 300 ml three-necked flask, the inside of the system was stirred, and 13.3 g of tin chloride was added. Followed by heating and stirring. After completion of the reaction, the reaction system was poured into 300 ml of ethyl acetate and the pH was adjusted to 7 to 8 using sodium hydrogencarbonate. The white precipitate was removed by filtration, and the organic layer was extracted with ethyl acetate. Anhydrous magnesium sulfate was added to the organic layer, followed by dehydration drying and filtration, followed by solvent distillation using a rotary evaporator. The residue was recrystallized using ethyl acetate / hexane = 1/5 to obtain 5.7 g of the objective DA-4 (orange solid) (yield: 99%). The result of ¹ H-NMR measurement of the obtained solid is shown below. From this result, it was confirmed that the obtained solid was the intended DA-4.

(Example 2) Synthesis of DA-5

(Example 2-1) Synthesis of DA-5-1 precursor DA-5

(41)

Butyl acetate (156 g, 1.21 mol), palladium (II) acetate (2.6 g, 11.6 mmol) and tri (tert-butyldimethylsilyl) N, N'-dimethylacetamide (hereinafter referred to as DMAc) (500 g) was added to the reaction solution, and 100 g of o-tolylphosphine (7.0 g, 23.1 mmol), tributylamine Lt; 0 &gt; C. The reaction was followed by HPLC. After completion of the reaction, the reaction solution was poured into a 1 M aqueous hydrochloric acid solution (2 L) and stirred briefly. The organic layer was washed three times with saturated brine (500 ml), and the organic layer was dried over magnesium sulfate, filtered, and the solvent was distilled off to obtain DA -5-1 (reddish brownish brown). The obtained compound was used in the next step as it is.

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

(42)

In a 500 ml four-necked flask, 22.0 g of DA-5-1, 250 ml of N, N-dimethylformamide, 19.1 g of 6-chloro-1-hexanol, 41.5 g of potassium carbonate, 1.7 g of potassium iodide And the mixture was stirred while heating to 100 캜. After completion of the reaction, the reaction system was poured into 1 liter of water, neutralized with 1 N aqueous hydrochloric acid solution, and the precipitate was filtered. The filtrate was washed with isopropyl alcohol and dried to obtain 13.2 g of DA-5-2 (white solid). (Yield: 43%)

(Example 2-3) Synthesis of precursor DA-5-3 of DA-5

(43)

6.4 g of DA-5-2, 60 ml of tetrahydrofuran, 3.7 g of 2,4-dinitrofluorobenzene and 2.4 g of triethylamine were added to a 300 ml four-necked flask, and while heating to 80 占 폚 Lt; / RTI &gt; After completion of the reaction, the reaction system was poured into 500 ml of ethyl acetate and extracted with saturated brine. Anhydrous magnesium sulfate was added to the extracted organic layer, followed by dehydration drying, and anhydrous magnesium sulfate was filtered. The obtained filtrate was subjected to solvent distillation using a rotary evaporator, 50 ml of formic acid was added, and the mixture was stirred while being heated to 50 캜. 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 (yield: 81%) of DA-5-3 (yellow solid).

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

(44)

In a 300 ml four-necked flask, 6.9 g of DA-5-3, 70 ml of tetrahydrofuran, 2.5 g of 2-hydroxyethyl methacrylate, 2.5 g of 1- (3-dimethylaminopropyl) 5.3 g of MeOH hydrochloride and 0.2 g of 4-dimethylaminopyridine were added, and the mixture was stirred at room temperature. After completion of the reaction, the reaction system was poured into 200 ml of water, and the precipitate was filtered. The filtrate was washed with isopropyl alcohol and dried to obtain 8.6 g (yield: 96%) of DA-5-4 (yellowish white solid).

(Example 2-5) Synthesis of DA-5

[Chemical Formula 45]

7.6 g of DA-5-4, 70 ml of ethyl acetate, 70 ml of pure water, 7.8 g of reduced iron and 6.0 g of ammonium chloride were added to a 300 ml four-necked flask and stirred while being heated to 60 캜. After completion of the reaction, the reducing iron was filtered off, and the organic layer was extracted with ethyl acetate. Anhydrous magnesium sulfate was added to the organic layer, followed by dehydration drying, and anhydrous magnesium sulfate was filtered. The obtained filtrate was subjected to solvent distillation using a rotary evaporator. The residue was washed with isopropanol and dried to give 5.3 g (yield 78%) of DA-5 (yellowish white solid). The result of ¹ H-NMR measurement of the obtained solid is shown below. From this result, it was confirmed that the obtained solid was the intended DA-5.

(Example 3) Synthesis of DA-6

(Example 3-1) Synthesis of DA-6-1 precursor DA-6

(46)

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

In a 500 ml four-necked flask, 23.4 g of 2-hydroxyethyl methacrylate, 22.1 g of triethylamine and 250 ml of tetrahydrofuran were added. The inside of the system was cooled to 0 占 폚, 25.0 g of methanesulfonyl chloride was added, and the mixture was stirred at room temperature. After completion of the reaction, 50 ml of pure water was added and stirred. Ethyl acetate was added to extract the organic layer. Anhydrous magnesium sulfate was added to the organic layer, followed by dehydration drying and filtration. The solvent was distilled off using a rotary evaporator To obtain 37.5 g of DA-6-1 (red colored solid). The obtained compound was used in the next step as it is.

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

(47)

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

22.0 g of DA-5-1, 500 ml of N, N-dimethylformamide, 24.9 g of DA-6-1 and 41.4 g of potassium carbonate were added to a 1 L four-necked flask, Respectively. After completion of the reaction, the reaction system was poured into 1 liter of water, neutralized with a 1N aqueous hydrochloric acid solution, and extracted with ethyl acetate. Anhydrous magnesium sulfate was added to the extracted organic layer, followed by dehydration drying, and anhydrous magnesium sulfate was filtered. The obtained filtrate was subjected to solvent distillation using a rotary evaporator, 200 ml of formic acid was added, and the mixture was stirred while heating to 50 캜. 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 16.5 g (yield: 60%) of DA-6-2 (white solid).

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

(48)

In a 300 ml four-necked flask, 11.5 g of DA-6-2, 150 ml of tetrahydrofuran, 23.6 g of 1,6-hexanediol, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride 11.9 g of 4-dimethylaminopyridine and 0.49 g of 4-dimethylaminopyridine, and the mixture was stirred at room temperature. After completion of the reaction, the reaction system was poured into 300 ml of ethyl acetate and extraction was carried out using saturated brine. Anhydrous magnesium sulfate was added to the extracted organic layer, followed by dehydration drying, and anhydrous magnesium sulfate was filtered. The solvent was distilled off using a rotary evaporator to obtain 15.4 g of DA-6-3 (reddish brownish brown). The obtained compound was used in the next step as it is.

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

(49)

15.4 g of DA-6-3, 150 ml of N, N-dimethylformamide, 8.2 g of 2,4-dinitrofluorobenzene and 8.3 g of triethylamine were added to a 300 ml four-necked flask, Lt; 0 &gt; C. After completion of the reaction, the reaction system was poured into 500 ml of ethyl acetate and extracted with saturated brine. Anhydrous magnesium sulfate was added to the extracted organic layer, followed by dehydration drying, and anhydrous magnesium sulfate was filtered. The obtained filtrate was subjected to solvent distillation using a rotary evaporator. The residue was washed with an ethyl acetate / hexane (1: 4) solution and dried to give 12.6 g (yield 56%) of DA-6-4 (a colorless solid).

(Example 3-5) Synthesis of DA-6

(50)

In a 500 ml four-necked flask, 12.6 g of DA-6-4, 150 ml of ethyl acetate, 150 ml of pure water, 7.7 g of reduced iron and 9.9 g of ammonium chloride were added and stirred while heating to 60 캜. After completion of the reaction, the reducing iron was filtered off, and the organic layer was extracted with ethyl acetate. Anhydrous magnesium sulfate was added to the organic layer, followed by dehydration drying, and anhydrous magnesium sulfate was filtered. The obtained filtrate was subjected to solvent distillation using a rotary evaporator. The residue was isolated by silica gel column chromatography (ethyl acetate: hexane = 2: 1 by volume) to obtain 7.1 g (yield: 63%) of DA-6 (reddish brownish viscous substance). The result of ¹ H-NMR measurement of the obtained tincture is shown below. From this result, it was confirmed that the obtained viscous substance was the intended DA-6.

(Example 4) Synthesis of DA-7

(51)

To the reaction vessel was added 4-bromohydroxybenzene (100 g, 578 mmol), tert-butyl acrylate (156 g, 1.21 mol), palladium (II) acetate (2.6 g, 11.6 mmol) ) (500 g) was added and the reaction mixture was heated at 100 占 폚. The reaction mixture was stirred at room temperature for 3 hours, Followed by stirring. The reaction was followed by HPLC. After completion of the reaction, the reaction solution was poured into a 1 M aqueous hydrochloric acid solution (2 L) and stirred briefly. Ethyl acetate (1 L) was added thereto, and the aqueous layer was removed by separating. The organic layer was washed with saturated brine (500 mL) three times. The organic layer was dried with magnesium sulfate, filtered and the solvent was distilled off to obtain Compound [1] was obtained (158 g). The results of ¹ H-NMR measurement of the obtained compound are shown below. The obtained compound was used in the next step as it is.

Compound (1) (20.00 g, 90.8 mmol), triethylamine (11.94 g, 118 mmol) and tetrahydrofuran (hereinafter referred to as THF) (200 g) were charged in a reaction vessel, A solution of 3,5-dinitrobenzoyl chloride (25.12 g, 109 mmol) in THF (100 g) was added dropwise so that the inner temperature did not exceed 10 ° C. The reaction was monitored by HPLC. After completion of the reaction, the reaction solution was poured into distilled water (1.8 L), the precipitated solid was filtered and washed well with distilled water to obtain the crude product of compound [2]. Next, methanol (240 g) was added to the obtained crude product, and the mixture was heated and refluxed for 30 minutes, then cooled to room temperature, filtered, and the solid was dried to obtain compound [2] (yield: 18.0 g, yield: 49%). The results of ¹ H-NMR measurement of the obtained compound are shown below.

Compound [2] (15.82 g, 38.2 mmol) and formic acid (80 g) were added to the reaction vessel, and the mixture was heated and stirred at 40 占 폚. The reaction was followed by HPLC, and after confirming the completion of the reaction, the reaction solution was poured into distilled water (800 ml), and the solid was filtered and washed well with distilled water. The obtained solid was dried to obtain the compound [3] (yield: 13.1 g, yield: 96%). The results of ¹ H-NMR measurement of the obtained compound are shown below.

(13.07 g, 36.5 mmol), 2-hydroxyethyl methacrylate (hereinafter referred to as HEMA) (5.70 g, 43.8 mmol) and 1- (3-dimethylaminopropyl) (9.09 g, 47.4 mmol), 4-dimethylaminopyridine (hereinafter referred to as DMAP) (0.45 g, 3.65 mmol) and THF (200 g) were added And stirring was carried out at room temperature. After completion of the reaction was confirmed by HPLC, the reaction solution was poured into distilled water (1.2 L) and extracted with ethyl acetate. The organic layer was washed with distilled water three times, dried over magnesium sulfate, filtered, and the solvent was distilled off using an effervescent solvent to obtain a compound [4] (yield: 16.8 g, yield: 98%). The results of ¹ H-NMR measurement of the obtained compound are shown below.

To the reaction vessel was added compound [4] (16.8 g, 35.7 mmol), tin (IV) chloride (48.42 g, 255 mmol), THF (170 g) and distilled water (170 g) Respectively. After confirming the completion of the reaction by HPLC, the reaction solution was poured into a beaker containing ethyl acetate (1 L), and a sodium hydrogen carbonate powder was added with stirring to neutralize. Thereafter, the precipitated solid was removed by filtration, and the filtrate was washed with saturated aqueous sodium hydrogencarbonate solution (200 g) twice, saturated saline solution (500 g) three times, and dried over magnesium sulfate. Thereafter, the mixture was filtered and the solvent was distilled off to obtain the desired compound DA-7 (yield: 12.9 g, yield: 86%). The results of ¹ H-NMR measurement of the obtained compound are shown below.

(Example 5) Synthesis of DA-8

(52)

Compound (1) (127.3 g, 578 mmol), triethylamine (70.19 g, 694 mmol) and THF (800 g) were charged in a reaction vessel, and after replacing the nitrogen, , A solution of methacryloyl chloride (63.4 g, 607 mmol) in THF (200 g) was added dropwise. After completion of the reaction was confirmed 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 three times with saturated brine (500 g), dried over magnesium sulfate, filtered and the solvent was distilled off to obtain a compound [5]. The results of ¹ H-NMR measurement of the obtained compound are shown below. Compound [5] was not subjected to purification and used in the next step.

Compound (5) (166.0 g, 578 mmol) and dichloromethane (hereinafter abbreviated as DCM) (834 g) were charged in a reaction vessel and trifluoroacetic acid (328 g, 2.88 mol) Respectively. After completion of the reaction was confirmed by HPLC, the reaction solution was poured into distilled water (1 L), and the precipitated solid was filtered to obtain crude product. Next, the obtained crude product was washed and stirred with a mixed solution (200 g) of ethyl acetate / hexane 1: 2 by weight ratio, filtered again, and the solid was dried to obtain a compound [6] (yield: 79.5 g, yield: 59% ). The results of ¹ H-NMR measurement of the obtained compound are shown below.

To the reaction vessel was added 2- (2,4-dinitrophenyl) ethanol (43.67 g, 206 mmol), compound [6] (45.53 g, 196 mmol), EDC (48.87 g, 255 mmol), DMAP g, 19 mmol) and THF (900 g), and the mixture was stirred at room temperature. After completion of the reaction was confirmed by HPLC, the reaction solution was poured into distilled water (3 L) and extracted with ethyl acetate (1 L). Thereafter, the organic layer was washed with distilled water three times, dried with magnesium sulfate, filtered, and the solvent was distilled off using a separator to obtain a crude product of the compound [7]. The obtained crude product was dispersed and washed with methanol (100 ml), filtered, and dried under reduced pressure to obtain a compound [7]. (Yield: 48.3 g, yield: 58%). The results of ¹ H-NMR measurement of the obtained compound are shown below.

(48.25 g, 113 mmol), iron powder (37.91 g, 679 mmol), ethyl acetate (435 g), ammonium chloride (18.15 g, 340 mmol) and distilled water (160 g) And the mixture was heated and stirred at 70 占 폚. After completion of the reaction was confirmed by HPLC, the solid was filtered through celite, washed with ethyl acetate (1 L) and removed. The filtrate was washed three times with saturated brine (500 g), and the organic layer was dried over magnesium sulfate, and the solvent was distilled off using a diverter to obtain crude compound DA-8. The obtained crude product was dispersed washed with methanol, filtered and dried under reduced pressure to obtain Compound DA-8 (yield: 29.8 g, yield: 72%). The results of ¹ H-NMR measurement of the obtained compound are shown below.

(Example 6) Synthesis of DA-9

(53)

(In the above-mentioned reaction formula, the cyclohexane ring marked with &amp;bull; indicates that the steric structure is 1,4-trans-cyclohexane ring.)

To the reaction vessel were added trans-4- (4-bromophenyl) cyclohexanol (200 g, 784 mmol), tert-butyl acrylate (211 g, 1.65 mol) and palladium acetate (II) ), Tri (o-tolyl) phosphine (9.5 g, 31.4 mmol), tributylamine (436 g, 2.35 mol) and DMAc (1000 g) were added and heated and stirred at 100 ° C. After completion of the reaction was confirmed by HPLC, the reaction solution was poured into a 1 M aqueous hydrochloric acid solution (3.5 L) and stirred briefly. Ethyl acetate (1.5 L) was added thereto, and the aqueous layer was removed by separating. The organic layer was washed three times with saturated brine (500 mL), and the organic layer was dried over magnesium sulfate, filtered, and the solvent was distilled off, [8] (yield: 208 g, yield: 88%). The results of ¹ H-NMR measurement of the obtained compound are shown below.

To the reaction vessel, compound [8] (40.0 g, 132 mmol), triethylamine (16.1 g, 159 mmol) and THF (300 g) were charged and after nitrogen substitution, , A THF (180 g) solution of 3,5-dinitrobenzoyl chloride (32.0 g, 139 mmol) was added dropwise. After completion of the reaction was confirmed by HPLC, the reaction solution was poured into distilled water (2 L) and stirred for a while. Thereafter, the precipitated solid was filtered and washed well with distilled water to obtain the crude product of the compound [9]. Next, methanol (300 g) was added to the obtained crude product, and the mixture was stirred at room temperature for 30 minutes. The mixture was filtered and the solid was dried to obtain the compound [9] (yield: 41.8 g, yield: 64%). The results of ¹ H-NMR measurement of the obtained compound are shown below.

Compound [9] (41.80 g, 84.2 mmol) and formic acid (210 g) were added to a reaction vessel and the mixture was heated and stirred at 40 占 폚. After completion of the reaction was confirmed by HPLC, the reaction solution was poured into distilled water (2 L), and the solid was filtered and washed well with distilled water. The obtained solid was dried to obtain compound [10] (yield 37 g, yield: 99%). The results of ¹ H-NMR measurement of the obtained compound are shown below.

The reaction vessel was charged with compound [10] (37.8 g, 85.8 mmol), HEMA (13.4 g, 103 mmol), EDC (21.38 g, 112 mmol), DMAP (1.05 g, 8.6 mmol) ) Was added, and stirring was performed at room temperature. After completion of the reaction was confirmed by HPLC, the reaction solution was poured into distilled water (1.8 L) and extracted with ethyl acetate. The organic layer was washed with distilled water three times, dried over magnesium sulfate, filtered, and the solvent was distilled off using a separator to obtain a crude product of the compound [11]. The obtained crude product was washed with 2-propanol (100 g) to obtain a compound [11] (yield: 47.1 g, yield: 99%). The results of ¹ H-NMR measurement of the obtained compound are shown below.

Compound [11] (47.4 g, 85.8 mmol), tin (IV) chloride (114 g, 601 mmol), THF (470 g) and distilled water (470 g) were added to the reaction vessel, Respectively. After confirming the completion of the reaction by HPLC, the reaction solution was poured into a beaker containing ethyl acetate (1.5 L) and neutralized by adding sodium bicarbonate powder while stirring. Thereafter, the precipitated solid was removed by filtration, and the filtrate was washed twice with a saturated aqueous sodium hydrogencarbonate solution (200 g) twice, with saturated brine (500 g) three times, and dried over magnesium sulfate. Thereafter, the mixture was filtered and the solvent was distilled off to obtain the aimed compound DA-9 (yield: 32.5 g, yield: 76%). The results of ¹ H-NMR measurement of the obtained compound are shown below.

(Example 7) Synthesis of DA-10

(54)

(In the above-mentioned reaction formula, the cyclohexane ring marked with &amp;bull; indicates that the steric structure is 1,4-trans-cyclohexane ring.)

To the reaction vessel, compound [8] (74.43 g, 261 mmol), triethylamine (29.81 g, 295 mmol) and THF (1000 g) were charged and after nitrogen substitution, While THF (100 g) solution of methacryloyl chloride (27.01 g, 258 mmol) was added dropwise. After completion of the reaction was confirmed 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 three times with saturated brine (500 g), dried over magnesium sulfate, filtered and the solvent was distilled off to obtain the crude product of the compound [12]. The obtained crude product was dispersed and washed with methanol (100 g), filtered, and the solid was dried to obtain Compound [12] (yield 72.9 g, yield 80%). The results of ¹ H-NMR measurement of the obtained compound are shown below.

Compound [12] (20.29 g, 54.8 mmol) and DCM (100 g) were placed in a reaction vessel, and after replacing the nitrogen, trifluoroacetic acid (31.2 g, 274 mol) was added dropwise. After completion of the reaction was confirmed 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 three times with saturated brine (200 g), and the organic layer was dried over magnesium sulfate, filtered, and evaporated to remove the solvent with a separator to give the crude product of the compound [13]. The obtained crude product was dispersed washed with methanol (30 g), filtered, and dried to obtain Compound [13] (yield: 10.9 g, yield: 64%). The results of ¹ H-NMR measurement of the obtained compound are shown below.

To the reaction vessel was added 2- (2,4-dinitrophenyl) ethanol (11.94 g, 56.3 mmol), compound [13] (10.89 g, 35.3 mmol), EDC (11.62 g, 61.0 mmol), DMAP g, 4.7 mmol) and THF (130 g), and the mixture was stirred at room temperature. After completion of the reaction was confirmed 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 the crude product of the compound [14]. The obtained crude product was dispersed washed with methanol (100 ml), filtered, and dried under reduced pressure to obtain Compound [14] (yield: 17.1 g, yield: 96%). The results of ¹ H-NMR measurement of the obtained compound are shown below.

(17.00 g, 33.4 mmol), iron powder (11.2 g, 201 mmol), ethyl acetate (150 g), ammonium chloride (5.35 g, 100 mmol) and distilled water (50 g) And the mixture was heated and stirred at 70 占 폚. After completion of the reaction was confirmed by HPLC, the solid was filtered through celite and washed with ethyl acetate (200 ml) to remove. The filtrate was washed with saturated brine (200 g) three times. The organic layer was dried over magnesium sulfate, and the solvent was distilled off using a diverter to obtain crude product of compound DA-10. The obtained crude product was dispersed washed with methanol (100 g), filtered, and dried under reduced pressure to obtain Compound DA-10 (yield: 10.3 g, yield 69%). The results of ¹ H-NMR measurement of the obtained compound are shown below.

(Example 8) Synthesis of DA-11

(55)

(150 g, 602 mmol), tert-butyl acrylate (162 g, 1.26 mol), palladium acetate (II) (2.70 g, 12.0 mmol), tri (o-tolyl) phosphine (7.33 g, 24.1 mmol), tributylamine (335 g, 1.81 mol) and DMAc (750 g) Respectively. After completion of the reaction was confirmed by HPLC, the reaction solution was poured into a 1 M aqueous hydrochloric acid solution (3.5 L) and stirred briefly. Ethyl acetate (1 L) was added thereto, and the aqueous layer was removed by separating. The organic layer was washed three times with saturated brine (500 mL), and the organic layer was dried over magnesium sulfate, filtered, and the solvent was distilled off, [15] (yield 176 g, yield 99%). The results of ¹ H-NMR measurement of the obtained compound are shown below.

To the reaction vessel, compound [15] (73.4 g, 318 mmol), triethylamine (36.8 g, 364 mmol) and THF (1000 g) were charged and after nitrogen substitution, Was added dropwise a solution of 3,5-dinitrobenzoyl chloride (73.37 g, 318 mmol) in THF (300 g). After completion of the reaction was confirmed by HPLC, the reaction solution was poured into distilled water (6 L) and stirred for a while. Thereafter, the precipitated solid was filtered and washed well with distilled water to obtain the crude product of the compound [16]. Next, methanol (1 L) was added to the obtained crude product, and the mixture was stirred at room temperature for 30 minutes, followed by filtration and drying of the solid to obtain Compound [16] (yield: 117.9 g, yield: 79%). The results of ¹ H-NMR measurement of the obtained compound are shown below.

Compound [16] (117.9 g, 240 mmol) and formic acid (1180 g) were added to a reaction vessel, and the mixture was heated and stirred at 40 占 폚. After completion of the reaction was confirmed by HPLC, the reaction solution was poured into distilled water (3 L), and the solid was filtered and washed well with distilled water. The obtained solid was dried to obtain a compound [17] (yield: 102 g, yield: 98%). The results of ¹ H-NMR measurement of the obtained compound are shown below.

The reaction vessel was charged with compound [17] (40.0 g, 92.1 mmol), HEMA (18.0 g, 138 mmol), EDC (22.8 g, 120 mmol), DMAP (1.13 g, 9.2 mmol) ) Was added, and stirring was performed at room temperature. After completion of the reaction was confirmed by HPLC, the reaction solution was poured into distilled water (3 L) and extracted with ethyl acetate. The organic layer was washed three times with saturated brine (500 g), dried over magnesium sulfate, filtered and the solvent was distilled off using an effervescent solvent to obtain the crude product of the compound [18]. The obtained crude product was washed with methanol (300 g) to obtain a compound [18] (yield: 27.8 g, yield: 55%). The results of ¹ H-NMR measurement of the obtained compound are shown below.

(27.8 g, 50.9 mmol), tin (IV) chloride (67.6 g, 357 mmol), THF (280 g) and distilled water (220 g) were added to a reaction vessel, Respectively. After confirming the completion of the reaction by HPLC, the reaction solution was poured into a beaker containing ethyl acetate (2 L) and neutralized by adding sodium bicarbonate powder while stirring. Thereafter, the precipitated solid was removed by filtration, and the filtrate was washed twice with a saturated aqueous sodium hydrogencarbonate solution (200 g) twice, with saturated brine (500 g) three times, and dried over magnesium sulfate. Thereafter, the mixture was filtered and the solvent was distilled off to obtain the desired compound DA-11 (yield: 23.9 g, yield: 97%). The results of ¹ H-NMR measurement of the obtained compound are shown below.

(Example 9) Synthesis of DA-12

(56)

The reaction vessel was charged with compound [15] (89.15 g, 303 mmol), triethylamine (36.8 g, 364 mmol) and THF (1000 g) , A solution of methacryloyl chloride (33.27 g, 318 mmol) in THF (330 g) was added dropwise. After completion of the reaction was confirmed by HPLC, the reaction solution was poured into distilled water (6 L), stirred for a while, and the precipitated solid was filtered and washed well with distilled water to obtain the crude product of compound [19]. Next, methanol (1 L) was added to the obtained crude product, followed by stirring at room temperature for 30 minutes, followed by filtration and drying of the solid to obtain compound [19] (yield: 94.5 g, yield 86%). The results of ¹ H-NMR measurement of the obtained compound are shown below.

Compound [19] (94.51 g, 259 mmol) and formic acid (475 g) were charged in a reaction vessel, and after nitrogen substitution, heating and stirring were carried out at 40 ° C. The reaction solution was poured into distilled water (3.5 L) by HPLC, and the precipitated solid was filtered, washed well with distilled water and the solid was dried under reduced pressure to obtain Compound [20] (yield: 74.9 g, yield: 75% ). The results of ¹ H-NMR measurement of the obtained compound are shown below.

To the reaction vessel was added 2- (2,4-dinitrophenyl) ethanol (41.29 g, 195 mmol), compound [20] (50.00 g, 162 mmol), EDC (40.21 g, 211 mmol) g, 16.2 mmol) and THF (600 g) were added, and the mixture was stirred at room temperature. After completion of the reaction was confirmed by HPLC, the reaction solution was poured into distilled water (3.6 L), and the precipitated solid was filtered and washed with distilled water to obtain the crude product of the compound [21]. The obtained crude product was dispersed washed with methanol (300 ml), filtered, and dried under reduced pressure to obtain Compound [21] (yield: 65.1 g, yield: 80%). The results of ¹ H-NMR measurement of the obtained compound are shown below.

To the reaction vessel was added compound [21] (65.01 g, 130 mmol), tin (IV) chloride (171.9 g, 906 mmol), THF (650 g) and distilled water (520 g) Respectively. After confirming the completion of the reaction by HPLC, the reaction solution was poured into a beaker containing ethyl acetate (3.5 L) and neutralized by adding sodium bicarbonate powder while stirring. Thereafter, the precipitated solid was removed by filtration, and the filtrate was washed twice with a saturated aqueous sodium hydrogencarbonate solution (200 g) twice, with saturated brine (500 g) three times, and dried over magnesium sulfate. Thereafter, the mixture was filtered and the solvent was distilled off to obtain the crude product of the desired compound DA-12. Next, the obtained crude product was dispersed washed with methanol (200 g), filtered, and the solid was dried to obtain Compound DA-12 (yield 49.5 g, yield 76%). The results of ¹ H-NMR measurement of the obtained compound are shown below.

(Example 10) Synthesis of liquid crystal aligning agent

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

(Example 11) Synthesis of liquid crystal aligning agent

(PAA-2) was obtained by reacting 1.94 g (0.0099 mol) of CBDA with 4.34 g (0.0085 mol) of DA-4 and 0.58 g (0.0015 mol) of DA- ) Was prepared. This polyamic acid had a number average molecular weight of about 9,000 and a weight average molecular weight of about 24,000. NMP and BCS were added to 10 g of the polyamic acid solution, and the mixture was stirred to prepare 6 mass% of polyamic acid (PAA-2), 74 mass% of NMP and 20 mass% of BCS, Followed by pressure filtration with a membrane filter to obtain the liquid crystal aligning agent of Example 11.

(Example 12) Synthesis of liquid crystal aligning agent

A solution of polyamic acid (PAA-3) was prepared by reacting 1.94 g (0.0099 mol) of CBDA with 5.10 g (0.01 mol) of DA-4 and 39.93 g of NMP at room temperature for 16 hours. This polyamic acid had a number average molecular weight of about 8,000 and a weight average molecular weight of about 19,000. NMP and BCS were added to 10 g of the polyamic acid solution, and the mixture was stirred to prepare 6 mass% of polyamic acid (PAA-3), 74 mass% of NMP and 20 mass% of BCS, Followed by pressure filtration with a membrane filter to obtain the liquid crystal aligning agent of Example 12. [

(Example 13) Synthesis of liquid crystal aligning agent

(PAA-6) was prepared by reacting 1.94 g (0.0099 mol) of CBDA with 4.10 g (0.0080 mol) of DA-4 and 0.76 g (0.0020 mol) ) Was prepared. This polyamic acid had a number average molecular weight of about 10,000 and a weight average molecular weight of about 20,000. NMP and BCS were added to 10 g of the solution of the polyamic acid and stirred to prepare 6 mass% of polyamic acid (PAA-6), 74 mass% of NMP and 20 mass% of BCS, Followed by pressure filtration with a membrane filter to obtain the liquid crystal aligning agent of Example 13.

(Example 14) Synthesis of liquid crystal aligning agent

(PAA-7) was obtained by reacting 1.94 g (0.0099 mol) of CBDA with 3.86 g (0.0080 mol) of DA-5 and 0.76 g (0.0020 mol) of DA-2 in 37.19 g of NMP at room temperature for 16 hours, ) Was prepared. This polyamic acid had a number average molecular weight of about 10,000 and a weight average molecular weight of about 20,000. NMP and BCS were added to 10 g of the solution of the polyamic acid and stirred to prepare 6 mass% of polyamic acid (PAA-7), 74 mass% of NMP and 20 mass% of BCS, Followed by pressure filtration with a membrane filter to obtain the liquid crystal aligning agent of Example 14. [

(Example 15) Synthesis of liquid crystal aligning agent

(Polylactic acid PAA-8) was obtained by reacting 1.94 g (0.0099 mol) of CBDA with 3.86 g (0.0080 mol) of DA-6 and 0.76 g (0.0020 mol) ) Was prepared. This polyamic acid had a number average molecular weight of about 9,000 and a weight average molecular weight of about 18,000. NMP and BCS were added to 10 g of the solution of the polyamic acid and stirred to prepare 6 mass% of polyamic acid (PAA-8), 74 mass% of NMP and 20 mass% of BCS, Followed by pressure filtration with a membrane filter to obtain the liquid crystal aligning agent of Example 15.

(Example 16) Synthesis of liquid crystal aligning agent

(PAA-10) was obtained by reacting 1.94 g (0.0099 mol) of CBDA with 2.93 g (0.0080 mol) of DA-8 and 0.96 g (0.0020 mol) of DA- ) Was prepared. This polyamic acid had a number average molecular weight of about 8,000 and a weight average molecular weight of about 16,000. NMP and BCS were added to 10 g of the solution of the polyamic acid and stirred to prepare 6 mass% of polyamic acid (PAA-10), 74 mass% of NMP and 20 mass% of BCS, Followed by pressure filtration with a membrane filter to obtain the liquid crystal aligning agent of Example 16.

(Example 17) Synthesis of liquid crystal aligning agent

PAA-11 (0.009 mol) was reacted with 1.94 g (0.0099 mol) of CBDA, 3.94 g (0.0080 mol) of DA-9 and 0.96 g (0.0020 mol) of DA- ) Was prepared. This polyamic acid had a number average molecular weight of about 9,000 and a weight average molecular weight of about 22,000. NMP and BCS were added to 10 g of the solution of the polyamic acid and stirred to prepare 6 mass% of polyamic acid (PAA-11), 74 mass% of NMP and 20 mass% of BCS, Followed by pressure filtration with a membrane filter to obtain the liquid crystal aligning agent of Example 17. [

(Example 18) Synthesis of liquid crystal aligning agent

(Polylactic acid PAA-12, manufactured by Nippon Aerosil Co., Ltd.) was reacted at room temperature for 16 hours in an amount of 1.94 g (0.0099 mol) of CBDA, 3.59 g (0.0080 mol) of DA-10 and 0.76 g (0.0020 mol) ) Was prepared. This polyamic acid had a number average molecular weight of about 8,000 and a weight average molecular weight of about 23,000. NMP and BCS were added to 10 g of the polyamic acid solution, and the mixture was stirred to prepare 6 mass% of polyamic acid (PAA-12), 74 mass% of NMP and 20 mass% of BCS, Followed by pressure filtration with a membrane filter to obtain a liquid crystal aligning agent of Example 18.

(Example 19) Synthesis of liquid crystal aligning agent

PAA-13 (0.009 mol) was obtained by reacting 1.94 g (0.0099 mol) of CBDA with 3.89 g (0.0080 mol) of DA-11 and 0.37 g (0.0020 mol) ) Was prepared. This polyamic acid had a number average molecular weight of about 7,000 and a weight average molecular weight of about 20,000. NMP and BCS were added to 10 g of the polyamic acid solution and stirred to prepare 6 mass% of polyamic acid (PAA-13), 74 mass% of NMP and 20 mass% of BCS, Followed by pressure filtration with a membrane filter to obtain the liquid crystal aligning agent of Example 19. [

(Example 20) Synthesis of liquid crystal aligning agent

PAA-14 (0.009 mol) was reacted with 1.94 g (0.0099 mol) of CBDA, 3.54 g (0.0080 mol) of DA-12 and 0.36 g (0.0020 mol) of DA- ) Was prepared. This polyamic acid had a number average molecular weight of about 8,000 and a weight average molecular weight of about 21,000. NMP and BCS were added to 10 g of the solution of the polyamic acid and stirred to prepare 6 mass% of polyamic acid (PAA-14), 74 mass% of NMP and 20 mass% of BCS, Followed by pressure filtration with a membrane filter to obtain the liquid crystal aligning agent of Example 20.

(Example 21) Synthesis of liquid crystal aligning agent

A solution of polyamic acid (PAA-15) was prepared by reacting 1.94 g (0.0099 mol) of CBDA with 4.82 g (0.01 mol) of DA-5 and 38.35 g of NMP at room temperature for 16 hours. This polyamic acid had a number average molecular weight of about 11,000 and a weight average molecular weight of about 21,000. NMP and BCS were added to 10 g of the solution of the polyamic acid and stirred to prepare 6 mass% of polyamic acid (PAA-15), 74 mass% of NMP and 20 mass% of BCS, Followed by pressure filtration with a membrane filter to obtain the liquid crystal aligning agent of Example 21.

(Example 22) Synthesis of liquid crystal aligning agent

A solution of polyamic acid (PAA-16) was prepared by reacting 1.94 g (0.0099 mol) of CBDA with 4.82 g (0.01 mol) of DA-6 and 38.35 g of NMP at room temperature for 16 hours. This polyamic acid had a number average molecular weight of about 10,000 and a weight average molecular weight of about 20,000. NMP and BCS were added to 10 g of the solution of the polyamic acid and stirred to prepare 6 mass% of polyamic acid (PAA-16), 74 mass% of NMP and 20 mass% of BCS, Followed by pressure filtration with a membrane filter to obtain the liquid crystal aligning agent of Example 22.

(Example 23) Synthesis of liquid crystal aligning agent

A solution of polyamic acid (PAA-18) was prepared by reacting 1.94 g (0.0099 mol) of CBDA and 3.66 g (0.01 mol) of DA-8 in 31.76 g of NMP at room temperature for 16 hours. This polyamic acid had a number average molecular weight of about 9,000 and a weight average molecular weight of about 18,000. NMP and BCS were added to 10 g of the solution of the polyamic acid and stirred to prepare 6 mass% of polyamic acid (PAA-18), 74 mass% of NMP and 20 mass% of BCS, Followed by pressure filtration with a membrane filter to obtain the liquid crystal aligning agent of Example 23. [

(Example 24) Synthesis of liquid crystal aligning agent

A solution of polyamic acid (PAA-19) was prepared by reacting 1.94 g (0.0099 mol) of CBDA with 4.92 g (0.01 mol) of DA-9 and 38.91 g of NMP at room temperature for 16 hours. This polyamic acid had a number average molecular weight of about 10,000 and a weight average molecular weight of about 24,000. NMP and BCS were added to 10 g of the solution of the polyamic acid and stirred to prepare 6 mass% of polyamic acid (PAA-19), 74 mass% of NMP and 20 mass% of BCS, Followed by pressure filtration with a membrane filter to obtain the liquid crystal aligning agent of Example 24.

(Example 25) Synthesis of liquid crystal aligning agent

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

(Example 26) Synthesis of liquid crystal aligning agent

A solution of polyamic acid (PAA-21) was prepared by reacting 1.94 g (0.0099 mol) of CBDA and 4.86 g (0.01 mol) of DA-11 in 38.57 g of NMP at room temperature for 16 hours. This polyamic acid had a number average molecular weight of about 9,000 and a weight average molecular weight of about 21,000. NMP and BCS were added to 10 g of the solution of the polyamic acid and stirred to prepare 6 mass% of polyamic acid (PAA-21), 74 mass% of NMP and 20 mass% of BCS, Followed by pressure filtration with a membrane filter to obtain the liquid crystal aligning agent of Example 26. [

(Example 27) Synthesis of liquid crystal aligning agent

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

(Comparative Example 1) Synthesis of liquid crystal aligning agent

PAA-4 (0.0099 mol) was reacted with 1.94 g (0.0099 mol) of CBDA, 2.23 g (0.0085 mol) of DA-3 and 0.57 g (0.0015 mol) of DA- ) Was prepared. This polyamic acid had a number average molecular weight of about 8,000 and a weight average molecular weight of about 22,000. NMP and BCS were added to 10 g of the solution of the polyamic acid and stirred to prepare 6 mass% of polyamic acid (PAA-4), 74 mass% of NMP and 20 mass% of BCS, Followed by pressure filtration with a membrane filter to obtain a liquid crystal aligning agent of Comparative Example 1. [

(Comparative Example 2) Synthesis of liquid crystal aligning agent

A solution of polyamic acid (PAA-5) was prepared by reacting 1.84 g (0.0094 mol) of CBDA and 1.08 g (0.01 mol) of DA-1 in 26.32 g of NMP at room temperature for 16 hours. This polyamic acid had a number average molecular weight of about 6,000 and a weight average molecular weight of about 13,000. NMP and BCS were added to 10 g of the solution of the polyamic acid and stirred to prepare 6 mass% of polyamic acid (PAA-5), 74 mass% of NMP and 20 mass% of BCS, Followed by pressure filtration with a membrane filter to obtain a liquid crystal aligning agent of Comparative Example 2. [

(Comparative Example 3) Synthesis of liquid crystal aligning agent

PAA-23 (0.009 mol) was reacted with 1.94 g (0.0099 mol) of CBDA and 2.09 g (0.0080 mol) of DA-3 and 18.97 g of NMP with 0.76 g (0.0020 mol) ) Was prepared. This polyamic acid had a number average molecular weight of about 8,000 and a weight average molecular weight of about 22,000. NMP and BCS were added to 10 g of the polyamic acid solution, and the mixture was stirred to prepare 6 mass% of polyamic acid (PAA-23), 74 mass% of NMP and 20 mass% of BCS, Followed by pressure filtration with a membrane filter to obtain a liquid crystal aligning agent of Comparative Example 3. [

(Comparative Example 4) Synthesis of liquid crystal aligning agent

PAA-9 (0.009 mol) was obtained by reacting 1.94 g (0.0099 mol) of CBDA with 3.28 g (0.0080 mol) of DA-7 and 0.76 g (0.0020 mol) ) Was prepared. This polyamic acid had a number average molecular weight of about 7,000 and a weight average molecular weight of about 15,000. NMP and BCS were added to 10 g of the solution of the polyamic acid and stirred to prepare 6 mass% of polyamic acid (PAA-9), 74 mass% of NMP and 20 mass% of BCS, Followed by pressure filtration with a membrane filter to obtain a liquid crystal aligning agent of Comparative Example 4. [

&Lt; Production of liquid crystal cell &

The liquid crystal aligning agent of Example 10 was spin-coated on the ITO surface of the ITO electrode substrate on which the ITO electrode pattern having the pixel size of 100 mu m x 300 mu m and the line / space of 5 mu m was formed, Dried for 30 minutes in a hot air circulating oven at 200 ° C to form a liquid crystal alignment film having a thickness of 100 nm.

The liquid crystal aligning agent of Example 10 was spin-coated on an ITO surface on which no electrode pattern was formed, dried for 90 seconds on a hot plate at 80 DEG C, and fired in a hot air circulating oven at 200 DEG C for 30 minutes To form a liquid crystal alignment film having a thickness of 100 nm.

A 6 占 퐉 bead spacer was dispersed on the liquid crystal alignment film of one of the two substrates, and then a sealing agent (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed thereon. Subsequently, after the side of the other substrate on which the liquid crystal alignment film was formed was inwardly bonded to the preceding substrate, the sealing agent was cured to prepare empty cells. In this empty cell, liquid crystal MLC-6608 (trade name, manufactured by Merck & Co., Inc.) was injected by a low pressure injection method and subjected to Isotropic treatment (redistribution treatment of liquid crystal by heating) in an oven at 120 캜 to obtain a liquid crystal cell Anti-parallel liquid crystal cell). In the same manner, liquid crystal cells were prepared using the liquid crystal aligning agents prepared in Examples 11, 13 to 20 and Comparative Examples 1, 3 and 4, respectively.

The response speed of each of the obtained liquid crystal cell using each of the liquid crystal aligning agents of Examples 10 to 11, 13 to 20 and Comparative Examples 1, 3 and 4 was measured by the following method. Thereafter, in a state in which a voltage of 20 Vp-p was applied to the liquid crystal cell, UV rays having passed through a 313 nm band-pass filter were irradiated from the outside of the liquid crystal cell for 10 seconds. Thereafter, the response speed was again measured, and the response speeds before and after the UV irradiation were compared. Table 1 shows the results of the response speeds immediately after the production of the liquid crystal cell (indicated as &quot; initial &quot; in the table) and after the irradiation of UV (indicated as &quot; after UV &quot;

How to measure the response speed

First, a liquid crystal cell was disposed between a set of polarizers in a measuring apparatus comprising a backlight, a set of polarizers in a crossed Nicol state, and a light amount detector in this order. At this time, the pattern of the ITO electrode in which the line / space was formed was made to have an angle of 45 degrees with respect to Cross-Nicol. Then, a rectangular wave having a voltage of +4 V and a frequency of 1 kHz was applied to the liquid crystal cell, and the change until the luminance observed by the light amount detector was saturated was taken in the oscilloscope, and the luminance Was applied with a voltage of 0% and +/- 4 V, the saturation luminance value was taken as 100%, and the time taken for the luminance to change from 10% to 90% was regarded as a response speed.

As a result, in Examples 10 to 11 and 13 to 20 in which the diamine compound represented by the above formula [1] having both of the photopolymerizable group and the photodimerization-causing group was used as a raw material, The response speed was fast. In Examples 10 to 11 and 13 to 20, Comparative Examples 1 and 3 using a diamine compound having a photopolymerizable group but no photodimerization group as a raw material instead of the diamine compound represented by the formula [1] Compared with Comparative Example 4 using a diamine compound in which R ⁴ in the formula [1] was a single bond, the response speed was remarkably faster.

&Lt; Production of liquid crystal cell &

The liquid crystal aligning agent of Example 12 was respectively spin-coated on a glass substrate with two transparent electrodes and dried on a hot plate at 90 DEG C for 60 seconds and then fired in a hot air circulating oven at 200 DEG C for 30 minutes To form a liquid crystal alignment film having a thickness of 100 nm. These coated film surfaces were irradiated with 500 mJ from immediately above by arranging the substrates so as to become antiparallel when the cells were UV-cured by passing through a 313 nm band-pass filter and a polarizing plate.

A 6 占 퐉 bead spacer was dispersed on the liquid crystal alignment film of one of the two substrates, and then a sealing agent (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed thereon. Subsequently, after the side of the other substrate on which the liquid crystal alignment film was formed was inwardly bonded to the preceding substrate, the sealing agent was cured to prepare empty cells. Liquid crystal MLC-2041 (trade name, manufactured by Merck & Co., Inc.) was injected into this empty cell by a low pressure injection method and is subjected to Isotropic treatment (reorientation treatment of liquid crystal by heating) in an oven at 120 캜 to prepare a liquid crystal cell Anti-parallel cell). In the same manner, liquid crystal cells were prepared using the liquid crystal aligning agents prepared in Examples 21 to 27 and Comparative Example 2.

<Evaluation of Liquid Crystal Alignment Property>

The prepared cells were sandwiched between polarizing plates arranged on the backlight so as to become Cross-Nicols, and the cells were observed, and the liquid crystal alignability was evaluated based on the following criteria. The evaluation results are shown in Table 2.

?: No orientation defect was observed.

X: Defective orientation was observed.

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

Claims (11)

A polyimide precursor obtained by reacting a diamine component containing a diamine compound represented by the following formula [1] with a tetracarboxylic acid dianhydride component and at least one polymer selected from a polyimide obtained by imidating the polyimide precursor .
[Chemical Formula 1]

(Wherein, R ³ is _{-CH 2 -., -O-, -CONH-} , -NHCO-, -COO-, -OCO-, -NH-, it denotes a group selected from -CO- R ⁴ is C 1 A divalent carbon ring or a heterocyclic ring, and one or more hydrogen atoms of the alkylene group, the divalent carbon ring or the heterocyclic ring may be substituted with a fluorine atom or an organic group, and R ^4, in the case where any one of the groups exemplified in the following do not neighbor each other, -CH ₂ - is optionally are substituted with these; -O-, -NHCO-, -CONH-, -COO- , -OCO-, -NH-, -NHCONH-, -CO-. R ⁵ is -CH ₂ -, -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH-, -CO-, It represents any of the. R ⁶ Represents a group that causes light quantization. R ⁷ is an alkylene group, a divalent carbon ring or a heterocyclic ring formed by a single bond or a carbon number of 1 to 30, and one or plural hydrogen atoms of the alkylene group, divalent carbon ring or heterocyclic ring may be substituted with a fluorine atom or a Or may be substituted with an organic group. Further, R ⁷ is In the case of any group exemplified in the following are not adjacent to each other, -CH ₂ - is optionally are substituted with these; -O-, -NHCO-, -CONH-, -COO- , - OCO-, -NH-, -NHCONH-, -CO-. R ⁸ represents a photopolymerizable group.) The method according to claim 1,
And R &lt; ⁶ &gt; is a divalent group represented by the following formula.
(2)

(Wherein * represents the bonding position with R ⁵ or R ⁷ ). 3. The method according to claim 1 or 2,
And R &lt; ⁸ &gt; is a monovalent group represented by the following formula.
(3)

(Wherein * represents a bonding position to R ⁷ ). 3. The method according to claim 1 or 2,
Wherein the diamine component further comprises a diamine compound having a side chain that vertically aligns the liquid crystal. 3. The method according to claim 1 or 2,
A liquid crystal aligning agent characterized in that the diamine compound represented by the formula [1] is 10 mol% to 80 mol% of the diamine component. 5. The method of claim 4,
Wherein the diamine compound having a side chain which vertically aligns the liquid crystal is contained in an amount of 5 mol% to 70 mol% of the diamine component. A liquid crystal alignment film obtained from the liquid crystal alignment agent according to claim 1 or 2. A liquid crystal display element comprising the liquid crystal alignment film according to claim 7. A diamine compound characterized by the following formula [2].
[Chemical Formula 4]

(Wherein R ¹¹ represents an alkylene group having 2 to 6 carbon atoms and R ¹² represents an alkylene group having 2 to 4 carbon atoms.) A diamine compound characterized by the following formula [3].
[Chemical Formula 5]

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

(Wherein * denotes the bonding position with O and ** denotes the bonding position with R &lt; ¹³ &gt;). A diamine compound characterized by the following formula [4].
(7)

K is 0 to 1, 1 is an integer of 1 to 6, m is 1 (m is 0 when n is 0), and n is an integer of 0 to 3. [ It is an integer of 6.
[Chemical Formula 8]

(Wherein * represents a bonding position with - (CH ₂ ) ₁ - and ** denotes a bonding position with O).