TW201341428A - Liquid crystal orientation agent, liquid crystal orientation membrane, liquid crystal display element, and diamine compound - Google Patents

Abstract

Provided is a liquid crystal orientation agent comprising at least one polymer selected from polyimide precursors obtained by reacting an amine component comprising a diamine compound represented by formula [1] and a tetracarboxylic dianhydride component, and polyimides obtained by imidation of the same. [1] (In the formula, R3 is a group selected from -CH2-, -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH-, and -CO-. R4 is a C1-30 alkylene group, divalent carbon ring, or heterocycle, and one or a plurality of the hydrogen atoms of the alkylene group, divalent carbon ring, or heterocycle can be optionally substituted by fluorine atoms or organic groups. Moreover, when there are adjacent -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, or -CO-, R4 can be such that these adjacent groups are substituted by -CH2-. R5 is -CH2-, -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH-, -CO-, or a single bond. R6 is a group that goes through photodimerization. R7 is a single bond or a C1-30 alkylene group, divalent carbon ring, or heterocycle, and one or a plurality of the hydrogen atoms of the alkylene group, divalent carbon ring, or heterocycle can be substituted by fluorine atoms or organic groups. Moreover, when there are adjacent -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, or -CO-, R7 can be such that these adjacent groups are substituted by -CH2-. R8 is a photopolymerizable group.)

Description

Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element, and diamine compound

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

In a liquid crystal display device in which liquid crystal molecules which are vertically aligned with respect to a substrate are responsive to an electric field (also referred to as a vertical alignment method), the manufacturing process includes a step of irradiating ultraviolet rays to a liquid crystal molecule while applying a voltage.

In the liquid crystal display device of the above-described vertical alignment type, it is known that a photopolymerizable compound is added to the liquid crystal composition, and a vertical alignment film such as polyimide or the like is used, and ultraviolet rays are applied while applying a voltage to the liquid crystal cell. A technique for accelerating the response speed of a liquid crystal (for example, refer to Patent Document 1 and Non-Patent Document 1) (PSA type liquid crystal display). In general, the tilt direction of the liquid crystal molecules that are responsive to the electric field is controlled by a protrusion provided on the substrate or a slit provided in the display electrode, but by adding a photopolymerizable compound to the liquid crystal composition. The liquid crystal cell is irradiated with ultraviolet light while applying a voltage, so that the polymer structure in which the tilt direction of the liquid crystal molecules has been memorized is formed on the liquid crystal alignment film, and the tilt of the liquid crystal molecules is controlled by the protrusion or the slit only. In the direction of the method, it is known that the response speed of the liquid crystal display element becomes faster.

In the liquid crystal display device of the PSA type, the solubility of the polymerizable compound added to the liquid crystal is low, and if the amount of addition is increased, there is a problem that precipitation occurs at a low temperature. On the contrary, if the amount of the polymeric compound is reduced, it is impossible to obtain A good alignment. Further, the unreacted polymerizable compound remaining in the liquid crystal may cause impurities (contamination) in the liquid crystal, and may also have a problem of lowering the reliability of the liquid crystal display element. Further, in the UV irradiation treatment necessary for the PSA mode, if the amount of irradiation is large, the components in the liquid crystal are decomposed, resulting in a decrease in reliability.

Here, it has been reported that even if a photopolymerizable compound is added to a liquid crystal alignment film instead of a liquid crystal composition, the response speed of the liquid crystal display element becomes faster (SC-PVA type liquid crystal display) (for example, reference) Non-patent document 2).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2003-307720

[Non-patent literature]

[Non-Patent Document 1] K. Hanaoka, SID 04 DIGEST, P.1200-1202

[Non-Patent Document 2] K.H Y.-J.Lee, SID 09 DIGEST, P.666-668

In such an SC-PVA mode, a liquid crystal alignment agent to which a photopolymerizable compound is added is used, but the solubility of the photopolymerizable compound to the liquid crystal alignment agent is not so high, and photopolymerization is added to the liquid crystal alignment agent. If the amount of the compound added is increased, the preservation stability of the liquid crystal alignment agent may not be Good influence. In addition, when the unreacted photopolymerizable compound is eluted from the liquid crystal alignment film into the liquid crystal, it becomes an impurity, and the reliability of the liquid crystal display element is lowered.

An object of the present invention is to provide a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element which can improve the response speed of a liquid crystal display element without adding a photopolymerizable compound, by solving the problems of the above-mentioned conventional techniques. And diamine compounds.

As a result of reviewing the above-mentioned problems, the inventors have found that the above problems can be solved by using a liquid crystal alignment agent, and the present invention can be completed. The liquid crystal alignment agent contains a diamine component and a tetracarboxylic dianhydride of a novel diamine compound (hereinafter also referred to as a specific diamine compound) having a group which initiates photodimerization reaction and a group which initiates photopolymerization in a side chain. At least one selected from the polyimine precursor obtained by the reaction of the component and the polyimine obtained by imidating the precursor. That is, the present invention has the following gist.

A liquid crystal alignment agent characterized by comprising at least one polymer selected from the group consisting of a polyimide precursor and a polyimine obtained by imidating a precursor, the polyimine precursor A reaction obtained by reacting a diamine component of a diamine compound represented by the following formula [1] with a tetracarboxylic dianhydride component.

(wherein R ³ represents a group selected from -CH ₂ -, -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH-, -CO-. R ⁴ is a carbon a 1-alkyl group, a divalent carbon ring or a heterocyclic ring formed by a carbon number of 30, and one or a plurality of hydrogen atoms of the alkyl group, the divalent carbocyclic ring or the heterocyclic ring may be a fluorine atom or Substituted by an organic group. Further, when any of the groups exemplified in R ⁴ are not adjacent to each other, -CH ₂ - may be substituted for such a group: -O-, -NHCO-, -CONH-, - COO-, -OCO-, -NH-, -NHCONH-, -CO-. R ⁵ represents -CH ₂ -, -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH- Any one of -CO- or a single bond. R ⁶ represents a group which initiates photodimerization. R ⁷ is a single bond, or an alkyl group formed by a carbon number of 1 to a carbon number of 30, a divalent carbon ring or a heterocyclic ring, and one or more hydrogen atoms of the alkylene group, the divalent carbocyclic ring or the heterocyclic ring may be substituted by a fluorine atom or an organic group. Further, R ⁷ may be exemplified in any of the subsequent groups. When not adjacent, -CH ₂ - may be substituted for such groups: -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, -CO-. R ⁸ is a photopolymerizable group).

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

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

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

(where * represents the bonding position with R ⁷ ).

4. The liquid crystal alignment agent according to any one of the above aspects, wherein the diamine component further comprises a diamine compound having a side chain which vertically aligns the liquid crystal.

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

6. The liquid crystal alignment agent according to any one of items 2 to 5, wherein The diamine compound crystallized into the side chain of the vertical alignment is 5 mol% to 70 mol% in the diamine component.

A liquid crystal alignment film obtained by the liquid crystal alignment agent according to any one of 1. to 6.

8. A liquid crystal display element comprising a liquid crystal alignment film of 7.

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

(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 represented by the following formula [3].

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

(wherein * indicates the bonding position with O, and ** indicates the bonding position with R ¹³ ).

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

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

(wherein * represents a bonding position with -(CH ₂ ) ₁ -, and ** represents a bonding position with O).

According to the present invention, it is possible to provide a liquid crystal alignment agent which is a liquid crystal alignment agent which enhances the response speed of a liquid crystal display element, particularly a liquid crystal display element of a vertical alignment type, even if it does not contain a photopolymerizable compound. Further, the liquid crystal alignment agent is not limited to a liquid crystal display element of a vertical alignment type, for example, a liquid crystal display element which can be used for irradiating ultraviolet rays to perform alignment treatment, and can obtain a liquid crystal alignment excellent and has an improved alternating current (AC) afterimage. The effect of the liquid crystal alignment film.

[Formation for implementing the invention]

Hereinafter, the present invention will be described in detail.

The liquid crystal alignment agent of the present invention contains at least one polymer selected from the group consisting of a polyimide precursor and a polyimine obtained by imidating a precursor, the polyimine precursor having the above The reaction of the diamine component of the diamine compound represented by the formula [1] with the tetracarboxylic dianhydride component. Further, the liquid crystal alignment agent is a solution for producing a liquid crystal alignment film, and the liquid crystal alignment film is a film for aligning liquid crystal in a predetermined direction. The components and the like contained in the liquid crystal alignment agent of the present invention are described in detail below.

<Specific diamine compound>

The liquid crystal alignment agent of the present invention contains at least one polymer selected from the group consisting of a polyimide precursor and a polyimine obtained by imidating a precursor, wherein the diamine component as a raw material contains the above formula. The diamine compound shown in [1].

The R ³ -R ⁴ -R ⁵ in the side chain of the formula [1] is a spacer portion of the diaminobenzene skeleton in the side chain of the connection with R ⁶ which is a group for initiating photodimerization, and R ³ represents the spacer portion and the second portion. A bonding group bonded to an aminobenzene skeleton. The bonding group R ³ is selected from the group consisting of -CH ₂ - (ie, methylene), -O- (ie, ether), -CONH- (ie, decylamine), -NHCO- (ie, decylamine). , -COO- (meaning ester), -OCO- (meaning reverse ester), -NH- (meaning amine), -CO- (meaning carbonyl). These bonding groups R ³ can be formed by a general organic synthesis method, but from the viewpoint of easiness of synthesis, -CH ₂ -, -O-, -COO-, -NHCO-, - NH- is better.

R ⁴ in the formula [1] is a central portion of the spacer, and is an alkylene group, a divalent carbon ring or a heterocyclic ring formed by a carbon number of 1 to a carbon number of 30. However, any hydrogen atom of the alkyl group, the divalent carbocyclic ring or the heterocyclic ring may be substituted by a fluorine atom or an organic group. Further, the hydrogen atom which may be substituted may be one or more. Further, one or a plurality of -CH ₂ - groups of the alkyl group, the divalent carbocyclic ring or the heterocyclic ring may be substituted for the bonding group for each of the bonding groups which are exemplified later. ;-O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, -NH, -CO-. This means that the R ⁴ group may have an alkylene group, a divalent carbocyclic ring or a heterocyclic ring-bonding group-alkylene group, a divalent carbocyclic ring or a heterocyclic ring. Moreover, when R ³ is -CH ₂ -, it means that the terminal of the R ³ side in R ⁴ may be the bonding group. Similarly, when R ⁵ is -CH ₂ -, it means that the terminal of the R ⁵ side in R ⁴ may be the bonding group. Therefore, when R ³ is -CH ₂ - and R ⁵ is -CH ₂ -, it means that R ⁴ may be the bond group - alkylene group, divalent carbocyclic ring or heterocyclic ring - the constitution of the bonding group Or R ⁴ may be any of the bonding groups. Further, -CH ₂ - substituted with the bonding group may be one place, and if the bonding groups are not adjacent to each other, it may be plural. Specific examples of the divalent carbocyclic ring or heterocyclic ring include the following structures, but are not limited thereto.

R ⁵ in the formula [1] represents a bond group bonded to R ^{6 in the} spacer. The bonding group R ⁵ is selected from -CH ₂ -, -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH-, -CO-, and a single bond. These bonding groups R ⁵ can be formed by a general organic synthesis method, but from the viewpoint of easiness of synthesis, -CH ₂ -, -O-, -COO-, -NHCO-, - NH- is better.

R ⁶ in the formula [1] represents a divalent organic group constituted by a group which initiates photodimerization. The group which initiates photodimerization is a functional group which becomes a dimer by reaction by light irradiation. In the case of R ⁶ , for example, a divalent group containing a cinnamyl group, a coumarin or a ketone group may be mentioned, and specifically, a divalent group represented by the following formula may be mentioned, but it is not limited thereto. . Further, one or a plurality of hydrogen atoms of the group represented by the following formula may be substituted with an organic group.

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

R ⁷ in the formula [1] is a moiety of R ^{6 which} is a group for initiating photodimerization in the side chain of the tie and R ^{8 which is} a photopolymerizable group, and R ⁷ is a single bond or a carbon number of 1 to An alkylene group, a divalent carbon ring or a heterocyclic ring formed by a carbon number of 30. However, any hydrogen atom of the alkyl group, the divalent carbocyclic ring or the heterocyclic ring may be substituted by a fluorine atom or an organic group. Further, the hydrogen atom which may be substituted may be one or more. Further, one or a plurality of -CH ₂ - groups of the alkyl group, the divalent carbocyclic ring or the heterocyclic ring may be substituted for the bonding group for each of the bonding groups which are exemplified later. ;-O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, -NH-, -CO-. This means, for example, that the R ⁷ group comprises an alkylene group, a divalent carbocyclic ring or a heterocyclic ring - the bonding group - an alkylene group, a divalent carbocyclic ring or a heterocyclic ring, or the like - or a bonding group - A structure such as an alkyl group, a divalent carbon ring or a heterocyclic ring. Further, -CH ₂ - may be substituted by one of the bonding groups, or may be plural if the bonding groups are not adjacent to each other. Specific examples of the divalent carbocyclic ring or heterocyclic ring include the following structures, but are not limited thereto.

R ⁸ in the formula [1] represents a photopolymerizable group. The photopolymerizable group is a functional group which causes polymerization by irradiation of light. In the case of R ⁸ , for example, a monovalent group containing an acrylic group, a methacryl group, a lactone group, a maleidino group, a vinyl group, an allyl group or a styryl group may be mentioned, and specific examples thereof may be mentioned. The monovalent group shown by the following formula is not limited thereto.

(where * represents the bonding position with R ⁷ ).

At least one polymer of the polyimine precursor obtained by containing the diamine compound represented by the above formula [1] as a raw material and the polyimine obtained by imidating the precursor oxime As a liquid crystal alignment agent, the photopolymerization group derived from the diamine compound represented by the above formula [1] causes a cross-linking reaction and a dimerization reaction by a photodimerization-based group, and as a result, cross-linking is formed. At the site or the dimerization site, the liquid crystal molecules memorize the oblique direction, and the response speed of the obtained liquid crystal display element can be increased.

Further, 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 following formula [1] is, for example, a diamine compound represented by the following formula [2].

(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).

Further, specific examples of the diamine compound represented by the above formula [2] include the following diamine compounds.

Further, the diamine compound represented by the above formula [1] may, for example, be a diamine compound represented by the following formula [3].

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

(wherein * indicates the bonding position with O, and ** indicates the bonding position with R ¹³ ).

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

Further, the diamine compound represented by the above formula [1] may, for example, be a diamine compound represented by the following formula [4].

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

(wherein * represents a bonding position with -(CH ₂ ) ₁ -, and ** represents a bonding position with O).

Further, specific examples of the diamine compound represented by the above formula [4] include The following diamine compound was obtained.

a diamine component which is a raw material of at least one polymer selected from the group consisting of a polyimine precursor and a polyimine obtained by imidating a precursor, which is contained in the liquid crystal alignment agent of the present invention, The ratio of the diamine represented by the formula [1] is not particularly limited, and from the viewpoint of increasing the response speed, it is 10 mol in the synthetic diamine component for the polyimide precursor. The amount of %~80% by mole is better, more preferably 10% by mole to 50% by mole of the diamine component, particularly preferably 20% by mole to 50% by mole.

The method for synthesizing the diamine compound represented by the above formula [1] is not particularly limited. For example, a nitro group of the dinitro compound represented by the following formula [1a] can be converted into an amine group.

(In the formula [1a], R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are synonymous with the definition of the formula [1]).

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

The dinitro compound represented by the above formula [1a] can be bonded to -R ⁴ -R ⁵ -R ⁶ -R ⁷ -R ⁸ as a side chain moiety via R ³ for dinitrobenzene. The method is obtained etc. For example, when R ³ is a guanamine bond (-CONH-), an amino group containing dinitrobenzoic acid and -R ⁴ -R ⁵ -R ⁶ -R ⁷ -R ^{8 may} be present in the base. The method of the next reaction.

When R ³ is a reverse guanamine bond (-HNCO-), an amine group-containing dinitrobenzene and an acid chloride containing -R ⁴ -R ⁵ -R ⁶ -R ⁷ -R ⁸ may be mentioned as a base. There is a method of reaction.

When R ³ is an ester bond (-COO-), it is exemplified that the dinitrobenzoic acid chloride is reacted with an alcohol compound containing -R ⁴ -R ⁵ -R ⁶ -R ⁷ -R ⁸ in the presence of a base. method. Further, when R ³ is a reverse ester bond (-OCO-), a hydroxyl group-containing dinitrobenzene and an acid chloride compound containing -R ⁴ -R ⁵ -R ⁶ -R ⁷ -R ⁸ may be mentioned. A method of reacting in the presence of a base.

When R ³ is an ether bond (-O-), the halogen compound-containing dinitrobenzene and the alcohol compound containing -R ⁴ -R ⁵ -R ⁶ -R ⁷ -R ⁸ may be mentioned in the presence of a base. The method of reaction.

When R ³ is an amino group bond (-NH-), a halogen group-containing dinitrobenzene and an amine compound containing -R ⁴ -R ⁵ -R ⁶ -R ⁷ -R ⁸ may be mentioned as a base. There is a method of reaction.

When R ³ is a carbonyl bond (-CO-), a nitro group-containing dinitrobenzene and a boric acid compound containing -R ⁴ -R ⁵ -R ⁶ -R ⁷ -R ⁸ may be mentioned. A method of performing a coupling reaction in the presence of palladium or a copper catalyst.

When R ³ is a carbon bond (-CH ₂ -), the end of the halogen-containing dinitrobenzene and the R ⁴ side of -R ⁴ -R ⁵ -R ⁶ -R ⁷ -R ⁸ may be mentioned. A compound having an unsaturated bond utilizes a Heck reaction or a cross-coupling reaction of a steamed bread.

The above dinitrobenzoic acid chloride may, for example, be 3,5-dinitrobenzoic acid chloride, 3,5-dinitrobenzoic acid, 2,4-dinitrobenzoic acid chloride, 2, 4-Dinitrobenzoic acid, 3,5-dinitrobenzyl chloride, 2,4-dinitrobenzyl chloride. Further, examples of the amine group-containing nitrobenzene include 2,4-dinitroaniline, 3,5-dinitroaniline, and 2,6-dinitroaniline. Examples of the hydroxyl group-containing nitrobenzene include 2,4-dinitrophenol, 3,5-dinitrophenol, and 2,6-dinitrophenol. Examples of the halogen-containing dinitrobenzene include 2,4-dinitrofluorobenzene, 3,5-dinitrofluorobenzene, 2,6-dinitrofluorobenzene, and 2,4-dinitro group. Iodobenzene, 3,5-dinitroiodobenzene, 2,6- Dinitroiodobenzene and the like. Examples of the aldehyde group-containing dinitrobenzene include 2,4-dinitroaldehyde, 3,5-dinitroaldehyde, and 2,6-dinitroaldehyde.

Examples of the method of synthesizing -R ⁴ -R ⁵ -R ⁶ -R ⁷ -R ⁸ in the side chain moiety include a method of synthesizing by the method described below. For example, when a guanamine bond (-CONH-) is present in the structure of -R ⁴ -R ⁵ -R ⁶ -R ⁷ R ⁸ , an acid chloride compound containing -R ⁴ may be mentioned as containing -R ⁶ An amine compound of -R ⁷ R ⁸ , an acid chloride compound containing -R ⁴ -R ⁵ -R ⁶ and an amine compound containing -R ⁷ R ⁸ or containing -R ⁴ -R ⁵ -R ⁶ - A method of reacting an acid chloride compound of R ⁷ with an amine compound containing -R ⁸ in the presence of a base.

When the structure of -R ⁴ -R ⁵ -R ⁶ -R ⁷ -R ⁸ has a reverse guanamine bond (-HNCO-), the amine compound containing -R ⁴ may be mentioned as containing -R ⁶ - An acid chloride compound of R ⁷ -R ⁸ , an amine compound containing -R ⁴ -R ⁵ -R ⁶ and an acid chloride compound containing -R ⁷ -R ⁸ or a -R ⁴ -R ⁵ -R A method of reacting an amine compound of ^6- R ⁷ with an acid chloride compound containing -R ⁸ in the presence of a base.

When an ester bond (-COO-) is present in the structure of -R ⁴ -R ⁵ -R ⁶ -R ⁷ -R ⁸ , an acid chloride compound containing -R ⁴ and a -R ⁶ -R may be mentioned. An alcohol compound of ^7- R ⁸ , an acid chloride compound containing -R ⁴ -R ⁵ -R ⁶ and an alcohol compound containing -R ⁷ -R ⁸ or containing -R ⁴ -R ⁵ -R ⁶ -R ⁷ A method of reacting an acid chloride compound with an alcohol compound containing -R ⁸ in the presence of a base.

When a reverse ester bond (-OCO-) is present in the structure of -R ⁴ -R ⁵ -R ⁶ -R ⁷ -R ⁸ , the -R ⁴ -containing alcohol compound and -R ⁶ -R ⁷ may be mentioned. An acid chloride compound of R ⁸ , an alcohol compound containing -R ⁴ -R ⁵ -R ⁶ and an acid chloride compound containing -R ⁷ R ⁸ or a -R ⁴ -R ⁵ -R ⁶ -R ⁷ A method of reacting an alcohol compound with an acid chloride compound containing -R ⁸ in the presence of a base.

When an ether bond (-O-) is contained in the structure of -R ⁴ -R ⁵ -R ⁶ -R ⁷ -R ⁸ , a halogen compound containing -R ⁴ and a -R ⁶ -R ⁷ - may be mentioned. R ⁸ alcohol compound, the halogen-containing compound containing -R ⁴ -R ⁵ -R ⁶ -R alcohol compound of -R ^{8. 7,} the halogen-containing compound -R ⁴ -R ⁵ -R ⁶ -R ⁷ and containing the - An alcohol compound of R ⁸ , an alcohol compound containing -R ⁴ , a halogen compound containing -R ⁶ -R ⁷ -R ⁸ , an alcohol compound containing -R ⁴ -R ⁵ -R ⁶ and a compound containing -R ⁷ -R ⁸ A halogen compound 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 a base.

When the structure of -R ⁴ -R ⁵ -R ⁶ -R ⁷ -R ⁸ has an amino group bond (-NH-), a halogen compound containing -R ⁴ and a -R ⁶ -R ⁷ group are mentioned. -R ⁸ group of the compound, a halogen-containing compound with -R ⁴ -R ⁵ -R ⁶ -R group of the compound ⁷ -R ^8, containing -R ⁴ -R ⁵ -R ⁶ -R ⁷ halogen of the compound And an amine compound containing -R ⁸ , an amine compound containing -R ⁴ and a halogen compound containing -R ⁶ -R ⁷ -R ⁸ , an amine compound containing -R ⁴ -R ⁵ -R ⁶ and containing - A halogen compound of R ⁷ -R ⁸ or a method of reacting an amine compound containing -R ⁴ -R ⁵ -R ⁶ -R ⁷ with a halogen compound containing -R ⁸ in the presence of a base.

When a carbonyl bond (-CO-) is contained in the structure of -R ⁴ -R ⁵ -R ⁶ -R ⁷ -R ⁸ , an aldehyde compound containing -R ⁴ and a -R ⁶ -R ⁷ - may be mentioned. a Boric acid compound of R ⁸ , an aldehyde compound containing -R ⁴ -R ⁵ -R ⁶ and a boric acid compound containing -R ⁷ -R ⁸ , containing -R ⁴ -R ⁵ -R ⁶ - R of an aldehyde compound with ⁷ -R acid (boric acid) ⁸ the compound containing boric acid (boronic acid) compound with an aldehyde compound ⁷ -R -R ^{-R. 6. 8,} the containing of -R ^{-R. 4. 4} -R the boric acid ⁵ -R ⁶ (boric acid) compound with an aldehyde compound ⁷ -R ^{-R. 8} of, containing or -R ⁴ -R ⁵ -R ⁶ -R ⁷ of the boronic acid (boric acid) compound with ^{-R. 8} An aldehyde compound which is reacted in the presence of a base.

<Diamine compound having a side chain which allows liquid crystal to be vertically aligned>

Further, the liquid crystal alignment agent of the present invention contains at least one polymer selected from the group consisting of a polyimide precursor and a polyimine obtained by imidating a precursor, and a diamine component of the raw material, in addition to the above formula In addition to the diamine compound shown in [1], a diamine compound having a side chain in which a liquid crystal is vertically aligned may be contained. In the case of the diamine compound having a side chain in which the liquid crystal is vertically aligned, a group having a ring structure or a branchable structure in the middle of a long-chain alkyl group or a long-chain alkyl group, or a lipo alcohol group may be mentioned. a diamine in which one or both of the hydrogen atoms of the group is substituted with a fluorine atom as a side chain, and a diamine represented by the following formula [A-1] to formula [A-24] can be exemplified, but Not limited to this.

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

(In the formula [A-6] and the formula [A-7], A ₂ represents -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ - or -CH ₂ OCO-, and A ₃ is a carbon number. An alkyl group of 1 to 22, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group).

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

(In the formula [A-11] and the formula [A-12], A ₆ represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O -, -OCH ₂ -, -CH ₂ -, -O-, or -NH-, A ₇ is a fluoro group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a methyl group, an ethyl group, Ethyloxy, or hydroxy).

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

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

Further, specific examples of the diamine compound having a side chain in which the liquid crystal is vertically aligned include a diamine represented by the following formula [A-25] to formula [A-30].

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

Further, specific examples of the diamine compound having a side chain in which the liquid crystal is vertically aligned may be a diamine represented by the following formula [A-31] to formula [A-32].

Among them, the ability to align the liquid crystal vertically is from [A-1], [A-2], [A-3], [A-4], [A-5] from the viewpoint of the response speed of the liquid crystal. ], [A-25], [A-26], [A-27], [A-28], [A-29], [A-30] diamines are preferred.

The above-mentioned diamine is used in the form of a liquid crystal alignment, a pretilt angle, a voltage holding property, and an accumulated charge in the case of the liquid crystal alignment film, and may be used alone or in combination of two or more.

The liquid crystal alignment agent of the present invention contains at least one polymer selected from the group consisting of a polyimide precursor and a polyimine obtained by imidating a precursor, and the diamine component of the raw material contains The ratio of the diamine of the liquid crystal to the side chain of the vertical alignment is not particularly limited, and is used for the polyimide precursor. The amount of 5 mol% to 70 mol% of the synthetic diamine component is preferably, more preferably 10 mol% to 50 mol%, particularly preferably 20 mol% to 50 mol% of the diamine component. ear%. If a diamine having such a side chain which vertically aligns the liquid crystal is used in an amount of from 5 mol% to 70 mol% in the synthetic diamine component for the polyimide precursor, the response speed is It is particularly excellent in terms of lifting or liquid crystal alignment fixing ability.

<Other diamine compounds>

Further, the liquid crystal alignment agent of the present invention contains at least one polymer selected from the group consisting of a polyimide precursor and a polyimine obtained by imidating a precursor, and the diamine component of the raw material is not damaged. Further, in addition to the effect of the present invention, a diamine compound represented by the above formula [1] or a diamine having a side chain in which the liquid crystal is vertically aligned may be contained, and other diamine may be contained. As other diamines, for example, p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylene Diamine, m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-di Aminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6- Diaminoresorcinol, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4 , 4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3, 3'-Difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3' -diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diamino Diphenylmethane, 3,4'-Diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl Ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodi Phenyl ether, 4,4'-sulfonyldiphenylamine, 3,3'-sulfonyldiphenylamine, bis(4-aminophenyl)decane, bis(3-aminophenyl)decane, dimethyl Base-bis(4-aminophenyl)decane, dimethyl-bis(3-aminophenyl)decane, 4,4'-thiodiphenylamine, 3,3'-thiodiphenylamine, 4, 4'-Diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-Diaminodiphenylamine, N-methyl(4,4'-diaminodiphenyl)amine, N-methyl(3,3'-diaminodiphenyl)amine , N-methyl (3,4'-diaminodiphenyl)amine, N-methyl (2,2'-diaminodiphenyl)amine, N-methyl (2,3'-di Aminodiphenyl)amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4 -diaminonaphthalene, 2,2'-diaminobenzophenone, 2, 3'-Diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5 -diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis(4-aminophenyl)ethane, 1, 2-bis(3-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane, 1,3-bis(3-aminophenyl)propane, 1,4-double ( 4-aminophenyl)butane, 1,4-bis(3-aminophenyl)butane, bis(3,5-diethyl-4-aminophenyl)methane, 1,4-double (4-Aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4- Aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4'-[1,4-stretch Phenyl bis(methylene)]diphenylamine, 4,4'- [1,3-phenylene bis(methylene)]diphenylamine, 3,4'-[1,4-phenylenebis(methylene)]diphenylamine, 3,4'-[1,3 -phenylphenylbis(methylene)]diphenylamine, 3,3'-[1,4-phenylenebis(methylene)]diphenylamine, 3,3'-[1,3-phenylene Bis(methylene)]diphenylamine, 1,4-phenylene bis[(4-aminophenyl)methanone], 1,4-phenylene bis[(3-aminophenyl)methanone ], 1,3-phenylene bis[(4-aminophenyl)methanone], 1,3-phenylene bis[(3-aminophenyl)methanone], 1,4-phenylene Bis(4-aminobenzoic acid ester), 1,4-phenylene bis(3-aminobenzoate), 1,3-phenylene bis(4-aminobenzoate) , 1,3-phenylene bis(3-aminobenzoate), bis(4-aminophenyl)terephthalate, bis(3-aminophenyl)terephthalate Ester, bis(4-aminophenyl)isophthalate, bis(3-aminophenyl)isophthalate, N,N'-(1,4-phenylene) bis ( 4-aminobenzamide, N,N'-(1,3-phenylene)bis(4-aminobenzamide), N,N'-(1,4-phenylene) Bis(3-aminobenzamide), N,N'-(1,3-phenylene)bis(3-aminobenzamide), N,N'-bis(4-aminobenzene) Base) p-xylamine, N,N'-bis(3-aminobenzene Benzylguanamine, N,N'-bis(4-aminophenyl)m-xylyleneamine, N,N'-bis(3-aminophenyl)m-xylyleneamine, 9,10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-aminophenoxy)diphenylanthracene, 2,2'-bis[4-(4-aminobenzene) Oxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis(4-aminophenyl)hexafluoropropane , 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2'-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2'-bis (4 -aminophenyl)propane, 2,2'-bis(3-aminophenyl)propane, 2,2'-bis(3-amino-4-methylphenyl)propane, 3,5-di Amino benzoic acid, 2,5- Diamino benzoic acid, 1,3-bis(4-aminophenoxy)propane, 1,3-bis(3-aminophenoxy)propane, 1,4-bis(4-aminophenoxy) Butane, 1,4-bis(3-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,5-bis(3-aminobenzene Oxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-amino group Phenoxy)heptane, 1,7-(3-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-amino Phenoxy)octane, 1,9-bis(4-aminophenoxy)decane, 1,9-bis(3-aminophenoxy)decane, 1,10-(4-amino group Phenoxydecane), 1,10-(3-aminophenoxy)decane, 1,11-(4-aminophenoxy)undecane, 1,11-(3-aminobenzene Aromatic diamines such as oxy)undecane, 1,12-(4-aminophenoxy)dodecane, 1,12-(3-aminophenoxy)dodecane, and bis (4) -Aminocyclohexyl)methane, alicyclic diamine such as bis(4-amino-3-methylcyclohexyl)methane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminodecane, 1,10-diamine Decane, 1,11-undecane diamine, 1,12-dodecane diamine of aliphatic diamine.

The above-mentioned other diamines may be used alone or in combination of two or more kinds in the liquid crystal alignment property, the pretilt angle, the voltage holding property, and the charge accumulated in the liquid crystal alignment film.

<tetracarboxylic dianhydride component>

In order to obtain a polyimine precursor, the tetracarboxylic dianhydride component which reacts with the above-mentioned diamine component is not specifically limited. Specifically, benzene is exemplified Tetraacid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7- Terpene tetracarboxylic acid, 1,2,5,6-nonanetetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4-biphenyltetracarboxylic acid, double (3,4-dicarboxyphenyl)ether, 3,3',4,4'-benzophenone tetracarboxylic acid, bis(3,4-dicarboxyphenyl)anthracene, bis(3,4-di Carboxyphenyl)methane, 2,2-bis(3,4-dicarboxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyl Phenyl)propane, bis(3,4-dicarboxyphenyl)dimethyloxane, bis(3,4-dicarboxyphenyl)diphenylnonane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,3',4,4'-diphenylphosphonium tetracarboxylic acid, 3,4,9,10-decanetetracarboxylic acid, 1, 3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid, oxybisphthalic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3, 4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid 1,2-Dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2 , 3,4-cycloheptane tetracarboxylic acid, 2,3,4,5-tetrahydrofuran tetracarboxylic acid, 3,4-dicarboxy-1-cyclohexyl succinic acid , 2,3,5-tricarboxycyclopentyl acetic 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]nonane-2, 4,7,9-tetracarboxylic acid, bicyclo[4,4,0]nonane-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-di-oxo-tetrahydrofuran-3-yl)-1,2,3,4 - tetrahydronaphthalene-1,2-dicarboxylic acid, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic acid, 5-(2,5-di-side oxygen Tetrahydrofuranyl-3-methyl-3-cyclohexane-1,2-dicarboxylic acid, tetracyclo[6,2,1,1,0,2,7]dodecane-4,5,9, 10-tetracarboxylic acid, 3,5,6-tricarboxynorbornane-2:3,5:6 dicarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid or the like. Of course, the tetracarboxylic dianhydride may be used alone or in combination of two or more kinds in accordance with the characteristics of the liquid crystal alignment property, the voltage retention property, and the charge accumulation in the case of the liquid crystal alignment film.

<Synthesis of Polyimine Precursor>

The polyimine precursor which may be contained in the liquid crystal alignment agent of the present invention means polyamic acid or polyphthalate.

The polyamic acid is obtained by the reaction of the above diamine component with the above tetracarboxylic dianhydride component, and a known synthetic method can be used. In general, a method in which a diamine component and a tetracarboxylic dianhydride component are reacted in an organic solvent is used. The reaction between the diamine component and the tetracarboxylic dianhydride component is preferably carried out in an organic solvent, and it is preferred that no by-products are produced.

The organic solvent used for the above reaction is not particularly limited as long as it is soluble in the produced polylysine. Further, even an organic solvent in which polylysine is insoluble may be used in the above solvent in a range in which the produced polyamine does not precipitate. Further, since the water in the organic solvent hinders the polymerization reaction and further causes hydrolysis of the produced polylysine, the organic solvent is preferably used for dehydrating and drying the organic solvent. The organic solvent used in the reaction may, for example, be N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide or N-methylformamidine. Amine, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-tetrahydroimidazolone, 3-methoxy -N,N-dimethylpropane decylamine, N-methylcaprolactone, dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethylarylene, γ-butyrolactone, Isopropanol, methoxymethylpentanol, dipentane Alkene, ethyl pentanone, methyl fluorenone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropanone, methyl stilbene, ethyl stilbene, methyl sarbuta acetate, Butyl succinate acetate, ethyl sirolimus 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 Acid ester, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl Ethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl Acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate Ester, butyl ether, diisobutyl Ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate Ester, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3- Methyl methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3 -propyl methoxypropionate, butyl 3-methoxypropionate, diethylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, 2-ethyl-1- Hexanol and the like. These organic solvents may be used singly or in combination.

When the diamine component and the tetracarboxylic dianhydride component are reacted in an organic solvent, A method in which a diamine component is dispersed or dissolved in an organic solvent, and a tetracarboxylic dianhydride component is directly added or dispersed or dissolved in an organic solvent, and vice versa. A method in which a tetracarboxylic dianhydride component is dispersed or dissolved in an organic solvent, a method of adding a diamine component, a method of mutually adding a tetracarboxylic dianhydride component and a diamine component, and the like may be used. A method. Further, when a diamine component or a tetracarboxylic dianhydride component is formed of a plurality of kinds of compounds, the reaction can be carried out in a state of being mixed in advance, and the reaction is carried out in an individual order, and the low molecular weight mixed reaction obtained by reacting them individually is carried out. It is a high molecular weight body.

The temperature at which the diamine component and the tetracarboxylic dianhydride component are reacted may be any temperature, for example, -20 ° C to 150 ° C, preferably -5 ° C to 100 ° C. Further, the reaction system can be carried out at any concentration. For example, the total amount of the diamine component and the tetracarboxylic dianhydride component in the reaction liquid is 1 to 50% by mass, preferably 5 to 30% by mass.

In the above polymerization reaction, the ratio of the total number of moles of the tetracarboxylic dianhydride component to the total number of moles of the diamine component can be selected according to the molecular weight of the desired polyamic acid. As in the case of the general polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the produced polyaminic acid becomes. Furthermore, if the preferred range is displayed, it is 0.8 to 1.2.

The method for synthesizing the polyaminic acid used in the present invention is not limited to the above-described method, and similarly to the general method for synthesizing polyglycine, the above-mentioned tetracarboxylic dianhydride component is used even if it is used. A tetracarboxylic acid derivative such as a tetracarboxylic acid or a tetracarboxylic acid dihalide is formed and reacted by a known method to obtain a corresponding polylysine.

The polyglycolate can be synthesized by the methods (1) to (3) shown below.

(1) Synthesis by polyaminic acid

Polyammonium ester is synthesized by esterifying a polyamic acid obtained from a tetracarboxylic dianhydride and a diamine component. Specifically, the polyglycine and the esterifying agent can be 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. It is synthesized for 1 to 4 hours.

In terms of the esterifying agent, it is preferably removed by purification, and examples thereof include N,N-dimethylformamide dimethyl acetal and N,N-dimethylformamide diethyl ester. Acetal, N,N-dimethylformamide dipropyl acetal, N,N-dimethylformamide dinepentyl butyl acetal, N,N-dimethylformamide II T-butyl acetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene, 1-propyl-3-p-tolyltriazole Alkene, 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholine ruthenium chloride, and the like. The amount of the esterifying agent to be added is preferably 2 to 6 mol equivalents per 1 mol of the repeating unit of the polyamic acid.

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

(2) Synthesis by reaction of tetracarboxylic acid diester dichloride with diamine component

Polyammonium esters can be synthesized from tetracarboxylic acid diester dichlorides and diamine components. Specifically, the tetracarboxylic acid diester dichloride and the diamine component can be 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. It is synthesized in hours, preferably 1 to 4 hours.

Among the above-mentioned bases, pyridine, triethylamine, 4-dimethylaminopyridine or the like can be used, and in order to carry out the reaction gently, pyridine is preferred. The amount of the base to be added is preferably from 2 to 4 moles per mole of the tetracarboxylic acid diester dichloride from the viewpoint of easy removal amount and easy availability of a high molecular weight body.

The solvent used in the above reaction is preferably N-methyl-2-pyrrolidone or γ-butyrolactone from the viewpoint of solubility of the monomer and the polymer, and one or a mixture of these may be used. Two or more types are used. The polymer concentration at the time of the synthesis is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass, from the viewpoint that precipitation of the polymer is less likely to occur and a high molecular weight body is easily obtained. Further, in order to avoid hydrolysis of the tetracarboxylic acid diester dichloride, it is preferred that the solvent used in the synthesis of the polyglycolate is dehydrated as much as possible, and it is preferable to avoid the incorporation of outside air in a nitrogen atmosphere.

(3) Synthesis by reaction of a tetracarboxylic acid diester with a diamine component

Polyammonium esters can be synthesized by polycondensation of a tetracarboxylic acid diester with a diamine component. Specifically, the reaction of the tetracarboxylic acid diester and the diamine component in the presence of a condensing agent, a base or an organic solvent at 0 ° C to 150 ° C, preferably 0 ° C to 100 ° C, is 30 minutes to 24 minutes. Hours, preferably 3 to 15 hours Can be synthesized.

As the condensing agent, triphenylphosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride can be used. , N,N'-carbonyldiimidazole, dimethoxy-1,3,5-triazinylmethylmorpholine oxime, O-(benzotriazol-1-yl)-N,N,N' , N'-tetramethyluronium tetrafluoroborate, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphonate, (2 , 3-dihydro-2-thioketo-3-benzoxazolyl)phosphonic acid diphenyl and the like. The amount of the condensing agent to be added is preferably 2 to 3 times the molar amount of the tetracarboxylic acid diester.

As the base, a tertiary amine such as pyridine or triethylamine can be used. The amount of the base to be added is preferably from 2 to 4 moles per mole of the diamine component from the viewpoint of easy removal amount and easy availability of a high molecular weight body.

Further, in the above reaction, the reaction was efficiently carried out by adding Lewis acid as an additive. As the Lewis acid, lithium halide such as lithium chloride or lithium bromide is preferred. The amount of Lewis acid added is preferably from 0 to 1.0 times the molar amount of the diamine component.

In the method for synthesizing the above three polyamidolates, the synthesis method of the above (1) or (2) is particularly preferable because a high molecular weight polyglycolate can be obtained.

The obtained polyamidate solution was poured into a poor solvent while stirring sufficiently to cause precipitation of the polymer. The precipitation is carried out several times, washed with a poor solvent, and then dried at room temperature or by heating to obtain a purified polyphthalate powder. The poor solvent is not particularly limited, and examples thereof include water, methanol, ethanol, hexane, butyl sarbuta, acetone, and toluene.

<Synthesis of Soluble Polyimine>

The method for imidating the above polyphosphonium hydrazide to polyimine is exemplified by hot hydrazine imidization of a solution of poly-proline, or in a solution of poly-proline The catalyst is added to the imidization of the catalyst. Further, the oxime imidization ratio from polyacrylic acid to polyimine is not necessarily 100%.

The temperature at which the polyaminic acid is thermally imidated in the solution is 100 ° C to 400 ° C, preferably 120 ° C to 250 ° C, and the water edge formed by the imidization reaction is removed to the reaction system. It is better to do it outside.

The ruthenium imide of poly-proline can be stirred by adding a basic catalyst and an acid anhydride to a solution of poly-proline, and stirring at -20 to 250 ° C, preferably 0 to 180 ° C. Implementation. The amount of the alkaline catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the prolyl group, and the amount of the acid anhydride is 1 to 50 moles, preferably 3 to the prolyl group. 30 times Mo. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferred because it has moderate alkalinity when the reaction proceeds. Examples of the acid anhydride include anhydrous acetic acid, anhydrous trimellitic acid, and anhydrous pyromellitic acid. Among them, when anhydrous acetic acid is used, purification after completion of the reaction becomes easy, and it is preferable. The rate of ruthenium imidization caused by the imidization of the catalyst can be controlled by the amount of the catalyst and the reaction temperature and reaction time.

When the produced polyamic acid or polyimine is recovered from the reaction solution of polyphosphoric acid or polyimine, the reaction solution may be precipitated by introducing a solvent into a poor solvent. Examples of the poor solvent used in the precipitation include methanol and acetone. Hexane, butyl sirolimus, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water, and the like. The polymer which has been precipitated by the lean solvent and recovered by filtration can be dried under normal pressure or reduced pressure at normal temperature or under heat. Further, the precipitated and recovered polymer is redissolved in an organic solvent, and the reprecipitation recovery operation is repeated 2 to 10 times to reduce impurities in the polymer. In the case of the poor solvent, for example, alcohols, ketones, hydrocarbons, and the like can be used. When three or more kinds of poor solvents selected in the above are used, the purification efficiency can be further improved.

<Liquid alignment agent>

The liquid crystal alignment agent of the present invention contains at least one polymer selected from the group consisting of polyimine, wherein the polyimine compound contains a diamine compound represented by the above formula [1]. The polyimine precursor obtained by the reaction of the diamine component and the tetracarboxylic dianhydride component and the polyimide obtained by imidating the polyimine precursor. The liquid crystal alignment agent contains a polyimine precursor obtained by reacting a diamine component containing a diamine compound represented by the above formula [1] with a tetracarboxylic dianhydride component, and the polyimine precursor It is preferable that the total amount of at least one polymer selected from the polyimide obtained by imidization is 1 to 10% by mass.

Further, the liquid crystal alignment agent of the present invention may contain a polyimine precursor obtained by reacting a diamine component and a tetracarboxylic dianhydride component of the diamine compound represented by the above formula [1], and The polyimine precursor is a polymer other than at least one polymer selected from the polyamidene obtained by imidization. At this time, the diamine compound represented by the above formula [1] is contained in the entire polymer component. The ratio of the polyimine precursor obtained by the reaction of the diamine component to the tetracarboxylic dianhydride component and the at least one polymer selected from the polyimine obtained by imidating the polyimine precursor quinone is It is preferably 10 (mass)% or more.

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

The solvent contained in the liquid crystal alignment agent is not particularly limited, and is a polyimine precursor which can be obtained by reacting a diamine component containing a diamine compound represented by the above formula [1] with a tetracarboxylic dianhydride component. The material and the component containing at least one polymer selected from the polyimine obtained by imidating the polyimine precursor oxime may be dissolved or dispersed. For example, an organic solvent exemplified in the synthesis of the above polylysine may be mentioned. Among them, N-methyl-2-pyrrolidone, γ-butyrolactone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-tetrahydroimidazolidone, 3-methoxy -N,N-dimethylpropane decylamine is preferred from the viewpoint of solubility. Of course, it is also possible to use two or more kinds of mixed solvents.

Further, it is preferred that the solvent is used to improve the uniformity or smoothness of the coating film, and it is preferably used in a solvent having a high solubility in a liquid crystal alignment agent-containing component. Examples of the solvent for improving the uniformity or smoothness of the coating film include, for example, isopropyl alcohol, methoxymethylpentanol, methyl stilbene, ethyl serosol, butyl siroli, methyl sin. Lucas acetate, butyl succinate acetate, ethyl sirolimus acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, B Glycol monoacetate, ethylene glycol monoisopropyl ether, B Glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol Alcohol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate , dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl B Acid ester, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, Butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, lactic acid Ethyl ester, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate 3-ethoxypropionic acid Methyl ethyl ester, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl ester, 3-methoxypropane Butyl butyl ester, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol Monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-B Oxypropoxy)propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, 2-ethyl-1-hexanol, and the like. These solvents can also be mixed with most types. When the solvent is used, it is preferably from 5 to 80% by mass, more preferably from 20 to 60% by mass, based on the total amount of the solvent contained in the liquid crystal alignment agent.

The liquid crystal alignment agent may contain components other than the above. In this example, a compound which improves film thickness uniformity or surface smoothness when a liquid crystal alignment agent is applied, a compound which improves adhesion of a liquid crystal alignment film and a substrate, and the like can be given.

Examples of the compound which improves the uniformity of the film thickness or the surface smoothness include a fluorine-based surfactant, a polyfluorene-based surfactant, and a nonionic surfactant. More specifically, for example, EFTop EF301, EF303, EF352 (manufactured by TOHKEM PRODUCTS), Megafac F171, F173, R-30 (manufactured by Dainippon Ink Co., Ltd.), Florad FC430, FC431 (manufactured by Sumitomo 3M), AashiGuard AG710 , Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.). When the surfactant is used, the use ratio is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the total amount of the polymer contained in the liquid crystal alignment agent.

Specific examples of the compound which improves the adhesion between the liquid crystal alignment film and the substrate include a functional decane-containing compound or an epoxy group-containing compound. For example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, N -(2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-ureido Propyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyl Triethoxy decane, N-triethoxydecyl propyl triethylene triamine, N-three Methoxydecylpropyltriethylenetriamine, 10-trimethoxydecyl-1,4,7-triazadecane, 10-triethoxydecyl-1,4,7-triaza Decane, 9-trimethoxydecyl-3,6-diazadecyl acetate, 9-triethoxydecyl-3,6-diazaindolyl acetate, N-benzoic acid 3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-benzene 3-aminopropyltriethoxydecane, N-bis(oxyethylene)-3-aminopropyltrimethoxydecane, N-bis(oxyethylene)-3-aminopropyltriethoxylate Pyridinium, ethylene glycol diepoxypropyl ether, polyethylene glycol diepoxypropyl ether, propylene glycol diepoxypropyl ether, tripropylene glycol diepoxypropyl ether, polypropylene glycol diepoxypropyl ether, Neopentyl glycol diepoxypropyl ether, 1,6-hexanediol diepoxypropyl ether, glycerol diepoxypropyl ether, 2,2-dibromoneopentyl glycol diepoxypropyl Ether, 1,3,5,6-tetraepoxypropyl-2,4-hexanediol, N,N,N',N'-tetraepoxypropyl-m-xylenediamine, 1 ,3-bis(N,N-diepoxypropylaminomethyl)cyclohexane, N,N,N',N'-four Epoxypropyl-4,4'-diaminodiphenylmethane, 3-(N-allyl-N-epoxypropyl)aminopropyltrimethoxydecane, 3-(N,N- Diepoxypropyl)aminopropyltrimethoxydecane, and the like. Further, in order to further increase the film strength of the liquid crystal alignment film, 2,2'-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane or tetrakis(methoxymethyl)bisphenol may be added. Phenol compound. When the compound is used, it is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of the total amount of the polymer contained in the liquid crystal alignment agent.

Further, in the liquid crystal alignment agent, in addition to the above, the dielectric constant or conductivity of the liquid crystal alignment film may be added within a range that does not impair the effects of the present invention. A change in electrical properties is a dielectric or conductive substance for the purpose.

<Liquid alignment film>

This liquid crystal alignment agent is applied onto a substrate and fired to form a liquid crystal alignment film which vertically aligns the liquid crystal.

In the case of the substrate to be used, the substrate having high transparency is not particularly limited, and a plastic substrate such as a glass substrate, an acrylic substrate or a polycarbonate substrate can be used. Moreover, it is preferable to use a substrate on which an ITO (Indium Tin Oxide) electrode or the like for liquid crystal driving is formed, from the viewpoint of process simplification. Further, if the reflective liquid crystal display element is only a single-sided substrate, an opaque material such as a germanium wafer can be used. In this case, a material such as aluminum that reflects light can be used.

The coating method of the liquid crystal alignment agent is not particularly limited, and examples thereof include a method of screen printing, lithography, flexographic printing, ink jet printing, or the like, or dipping, roll coating, slit coating, and spin coating. Cloth and so on.

The baking temperature of the coating film formed by coating the liquid crystal alignment agent is not limited, and may be, for example, any temperature of from 100 ° C to 350 ° C, preferably from 120 ° C to 300 ° C, and more preferably 150. °C~250°C. This firing can be carried out by using a hot plate, a hot air circulating furnace, a far outer furnace, or the like.

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

<Liquid crystal display element>

The liquid crystal display element of the present invention is provided with a liquid crystal display having a liquid crystal cell The liquid crystal cell having the liquid crystal layer disposed opposite to each other, a liquid crystal layer disposed between the substrates, and the liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention disposed between the substrate and the liquid crystal layer . Specifically, the liquid crystal alignment agent of the present invention is applied to two substrates to be fired to form a liquid crystal alignment film, and two liquid crystal alignment films are arranged to face each other, and the two substrates are disposed on the two substrates. A liquid crystal display element in which a liquid crystal layer composed of a liquid crystal is used and a liquid crystal cell produced by irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer is held. Examples of the liquid crystal display device of the present invention include a TN (Twisted Nematic) method, a Vertical Alignment (VA) method, and an IPS (In-Plane Switching) method.

By using the liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention, ultraviolet rays are applied while applying a voltage to the liquid crystal alignment film and the liquid crystal layer, and light having a side chain of a polyimine precursor or a polyimide is used. The polymerizable group and the group which initiates photodimerization means that the photopolymerizable compound is not contained in the photopolymerizable group and the photodimerization reaction of the diamine compound represented by the above formula [1]. In the liquid crystal alignment agent, the alignment of the liquid crystal alignment film liquid crystal using the liquid crystal alignment agent containing a photopolymerizable compound can be more efficiently immobilized, and the liquid crystal display element is remarkably excellent in response speed. Of course, in the liquid crystal alignment agent of the present invention, even if a photopolymerizable compound is added, a liquid crystal display element having a response speed of the same or higher degree can be obtained.

In the substrate for use in the liquid crystal display device of the present invention, the substrate having high transparency is not particularly limited, and a substrate on which a transparent electrode for liquid crystal is driven on a substrate is usually formed. Specific examples include the above liquid crystal The substrate described in the alignment film is the same. Although a substrate having a conventional electrode pattern or a protrusion pattern can be used, in the liquid crystal display device of the present invention, the liquid crystal alignment agent of the present invention is used as a liquid crystal alignment agent for forming a liquid crystal alignment film on one side. A 1~10 μm line/slit electrode pattern is formed on the substrate, and the opposite substrate can also be operated in a structure in which no slit pattern or a protrusion pattern is formed, and the liquid crystal display element thus constructed can be used. Simplify the manufacturing process and achieve high transmittance.

Further, in a high-performance element such as a TFT-type element, an element such as a transistor can be formed between an electrode for driving a liquid crystal and a substrate.

In the case of a transmissive liquid crystal display device, a substrate as described above is generally used. However, in a reflective liquid crystal display device, an opaque substrate such as a germanium wafer can be used as long as it is a single substrate. At this time, as the electrode formed on the substrate, a material such as aluminum which can reflect light can also be used.

The liquid crystal alignment film is formed by baking the liquid crystal alignment agent of the present invention on the substrate, and is as described above in detail.

The liquid crystal material constituting the liquid crystal layer in the liquid crystal display device of the present invention is not particularly limited, and a liquid crystal material used in a conventional vertical alignment method, for example, a negative liquid crystal such as MLC-6608 or MLC-6609 manufactured by Merck Co., Ltd. can be used. Or MLC-2041 and so on.

A well-known method is mentioned in the method of holding this liquid crystal layer between two board|substrate. For example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, and a space such as beads is spread on a liquid crystal alignment film of one substrate, and the other substrate is bonded to the inner side of the surface on which the liquid crystal alignment film is formed. A method in which a liquid crystal is injected under reduced pressure to be sealed. Also, a liquid crystal alignment film is prepared In the case of one pair of substrates, the liquid crystal is dropped on the liquid crystal alignment film of one substrate, and the liquid crystal is dropped, and then the surface on the side where the liquid crystal alignment film is formed is placed inside to bond the other substrate to be sealed. A liquid crystal cell can be produced. The thickness of the interval at this time is preferably from 1 to 30 μm, more preferably from 2 to 10 μm.

a step of producing a liquid crystal cell by applying ultraviolet light to a liquid crystal alignment film and a liquid crystal layer, for example, applying a voltage between electrodes provided on the substrate to apply an electric field to the liquid crystal alignment film and the liquid crystal layer, and A method of irradiating ultraviolet rays while maintaining this electric field. Here, the voltage applied between the electrodes is, for example, 5 to 30 Vp-p, preferably 5 to 20 Vp-p. The irradiation amount of the ultraviolet ray is, for example, 1 to 60 J, preferably 40 J or less, and the less the amount of the ultraviolet ray is applied, the decrease in reliability due to the destruction of the member constituting the liquid crystal display element can be suppressed, and the ultraviolet irradiation time can be reduced. Manufacturing efficiency is therefore preferred.

In this manner, when a voltage is applied to the liquid crystal alignment film and the liquid crystal layer while irradiating ultraviolet rays, a reaction of a photopolymerizable group having a side chain of a polyimine precursor or a polyimide, and a group for initiating photodimerization proceeds, that is, The cross-linking reaction caused by the photopolymerizable group of the diamine compound represented by the above formula [1] and the dimerization reaction by the group which initiates photodimerization are carried out, and as a result, the cross-linking site or the two which are produced can be produced. The liquid crystal molecules in the polymerization site are stored in an oblique direction, and the response speed of the obtained liquid crystal display element can be accelerated.

Further, the liquid crystal alignment agent can be used not only as a liquid crystal alignment agent for a liquid crystal display element of a vertical alignment type such as a PSA liquid crystal display or an SC-PVA liquid crystal display, but also for use in rubbing treatment or photoalignment processing. The use of liquid crystal alignment film.

The invention is illustrated by the following examples, and the invention is further illustrated in detail, but the invention is not limited thereto.

[Examples]

The outlines of the tetracarboxylic dianhydride and the diamine used in the synthesis examples and the structures thereof are shown below.

The abbreviation of the organic solvent or the like used in the examples and the like is as follows.

NMP: N-methyl-2-pyrrolidone

BCS: Butyl Cyrus

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

<Measurement of molecular weight of polymer>

The molecular weight of polyimine or polylysine is carried out using a normal temperature colloidal permeation chromatography (GPC) apparatus (GPC-101) manufactured by Shodex Co., Ltd., and a pipe column (KD-803, KD-805) manufactured by Shodex. The measurement is as follows.

Column temperature: 50 ° C

Dissolution: N,N-dimethylformamide (additives, lithium bromide-hydrate (LiBr.H ₂ O) system 30 mmol/L, phosphoric acid. Anhydrous crystal (o-phosphoric acid) 30 mmol/L, tetrahydrofuran (THF) ) 10ml/L)

Flow rate: 1.0 mL / min

A standard sample for the calibration curve was prepared: TSK standard polyethylene oxide (molecular weight: about 90,000, 150,000, 100,000, 30,000) manufactured by TOSOH Co., Ltd., and polyethylene glycol (molecular weight: about 12,000, 4,000, 1,000) manufactured by Polymer Laboratories.

<Measurement of ¹ H NMR>

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

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

Reference material: tetramethyl decane (TMS)

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

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

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

In a 500 mL three-necked flask, 19.2 g of DA-4-1, 250 mL of dimethylformamide, 20.5 g of 6-chloro-1-hexanol, 41.5 g of potassium carbonate, and 1.7 g of potassium iodide were placed, and stirred at 60 ° C. . After completion of the reaction, the reaction system was poured into 1.2 L of water, neutralized with a 1 N-HCl aqueous solution, and the precipitate was filtered. The filtrate was dissolved in 300 mL of ethyl acetate, and extracted with saturated brine. After adding anhydrous magnesium sulfate to the organic layer, the mixture was dehydrated, filtered, and then subjected to solvent distillation using a rotary evaporator to obtain 26.99. The target of g, DA-4-2 (transparent slime) (yield 92%).

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

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

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

In a 300 mL three-necked flask, 11.7 g of DA-4-3, 4.9 g of triethylamine (Et ₃ N), and 200 mL of tetrahydrofuran were placed. The inside was cooled to 0 ° C, and 15.2 g of 3,5-dinitrobenzhydryl chloride was added, and stirred at room temperature. After completion of the reaction, 50 mL of pure water was added and stirred, and then ethyl acetate was added to extract an organic layer. After the organic layer was added with anhydrous magnesium sulfate, the mixture was dehydrated, filtered, and then subjected to solvent distillation using a rotary evaporator. The residue was recrystallized from ethyl acetate to give 7.2 g of the desired compound (yield: EtOAc) (yield: 35%).

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

In a 200 mL three-necked flask, 6.9 g of DA-4-4, tetrahydrofuran 60 mL, 2-hydroxyethyl methacrylate (HEMA) 3.0 g, 1-(3-dimethylaminopropyl)-3- Ethylcarbodiimide hydrochloride (EDC) 4.4 g, 4-dimethylaminopyridine (DMAP) 0.2 g, and stirred at room temperature. After the completion of the reaction, the organic layer was extracted with chloroform, and then dried over anhydrous magnesium sulfate, and then dried and filtered, and then evaporated to the solvent using a rotary evaporator. Recrystallization was carried out to obtain 5.9 g of the object DA-4-5 (yellow white solid) (yield 69%).

(Example 1-6) Synthesis of DA-4

Into a 300 mL three-necked flask, 5.9 g of DA-4-5, 60 mL of tetrahydrofuran, and 60 mL of pure water were placed, and the inside was stirred, and 13.3 g of tin chloride was added thereto, and the mixture was stirred until it was heated to 70 ° C. After completion of the reaction, the reaction system was poured into 300 mL of ethyl acetate, and the pH was adjusted to 7-8 with sodium hydrogencarbonate. The white precipitate was removed by filtration, and the organic layer was extracted with ethyl acetate. anhydrous sodium sulfate was added to the organic layer to dryness, and filtered, and then subjected to solvent distillation using a rotary evaporator. The residue was recrystallized from ethyl acetate / hexane = 1 / 5 to afford 5.7 g of the desired product DA-4 (yellow solid) (yield 99%). The results of the measurement of the obtained solid by ¹ H-NMR are shown below. From this result, it was confirmed that the obtained solid was the intended DA-4.

¹ H NMR (400 MHz, [D ₆ ]-DMSO): δ 7.54-7.67 (d, 2H), 7.60 (s, 1H), 6.94-6.97 (d, 2H), 6.48-6.52 (d, 1H), 6.42-6.43(s,2H), 6.01-6.05(m,2H), 5.70(s,1H),4.99(s,4H), 4.36-4.40(m,4H),4.15-4.19(m,2H), 4.00-4.03 (m, 2H), 1.88 (s, 3H), 1.66-1.75 (m, 4H), 1.36-1.46 (m, 4H)

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

In a 2 L four-necked flask, 4-bromohydroxybenzene (100 g, 578 mmol), tert-butyl acrylate (156 g, 1.21 mol), palladium (II) acetate (2.6 g, 11.6 mmol), and tris (o-toluene) were placed. Phosphine (7.0 g, 23.1 mmol), tributylamine (321 g, 1.73 mol), N,N'-dimethylacetamide (hereinafter referred to as DMAc) (500 g), and heating and stirring at 100 °C. The reaction was followed by HPLC. After completion of the reaction, the reaction solution was poured into 1M aqueous hydrochloric acid (2 L) and stirring was continued. After adding ethyl acetate (1 L) and removing the water layer by liquid separation, the organic layer was washed three times with saturated brine (500 mL), dried over magnesium sulfate, and the organic layer was filtered, and the solvent was evaporated to obtain DA. -5-1 (red brown sticky body) 158g. Furthermore, the resulting compound was used directly in the subsequent step.

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

In a 500 mL four-necked flask, 22.0 g of DA-5-1, N,N-dimethylformamide 250 mL, 6-chloro-1-hexanol 19.1 g, potassium carbonate 41.5 g, and potassium iodide 1.7 g were placed, and Stir at 100 ° C while heating. After completion of the reaction, the reaction system was poured into 1 L of water, neutralized with a 1N-hydrochloric acid aqueous solution, and the precipitate was filtered. The filtrate was washed with isopropyl alcohol and dried to give 13.5 g of DA-5-2 (white solid). (yield 43%)

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

In a 300 mL four-necked flask, 6.4 g of DA-5-2, 60 mL of tetrahydrofuran, 3.7 g of 2,4-dinitrofluorobenzene, and 2.4 g of triethylamine were placed, and the mixture was stirred while heating at 80 °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 to dryness, and anhydrous magnesium sulfate was filtered. The obtained filtrate was distilled off in a rotary evaporator, and 50 mL of formic acid was added thereto, and the mixture was stirred while heating at 50 °C. After completion of the reaction, the reaction system was poured into 500 mL of water, and the precipitate was filtered. This filtrate was washed with isopropyl alcohol and dried to give DA-5-3 (yellow solid) 7.4 g (yield 81%).

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

In a 300 mL four-necked flask, 6.9 g of DA-5-3, tetrahydrofuran 70 mL, 2-hydroxyethyl methacrylate 2.5 g, and 1-(3-dimethylaminopropyl)-3-ethyl carbon were placed. Diammine imine hydrochloride 5.3g, 4-dimethylaminopyridine 0.2 g, and, stirred at room temperature. After completion of the reaction, the reaction system was poured into 200 mL of water, and the precipitate was filtered. This filtrate was washed with isopropyl alcohol and dried to give DA-5-4 (yellow white solid) 8.6 g (yield: 96%).

(Example 2-5) Synthesis of DA-5

In a 300 mL four-necked flask, 7.6 g of DA-5-4, 70 mL of ethyl acetate, 70 ml of pure water, 7.8 g of reduced iron, and 6.0 g of ammonium chloride were placed, and the mixture was stirred while heating at 60 °C. After completion of the reaction, the reduced iron was filtered, and the organic layer was extracted with ethyl acetate. Anhydrous magnesium sulfate was added to the organic layer to dryness, and anhydrous magnesium sulfate was filtered. The resulting filtrate was distilled off by a rotary evaporator. The residue was washed with isopropyl alcohol and dried to give 5.3 g (yield: 78%) of DA-5 (yellow white solid). The results of the measurement of the obtained solid by ¹ H-NMR are shown below. From this result, it was confirmed that the obtained solid was the intended DA-5.

¹ H NMR (400 MHz, [D ₆ ]-DMSO): δ 7.62 - 7.64 (d, 2H), 7.56-7.68 (d, 1H), 6.91-6.93 (d, 2H), 6.44-6.48 (d, 1H), 6.42 (s, 1H), 6.00 (s, 1H), 5.91 (s, 1H), 5.69-5.72 (d, 2H), 5.66 (s, 1H), 4.36 (s, 2H), 4.32 (s , 2H), 3.96-4.00 (t, 2H), 3.71-3.74 (t, 2H), 1.84 (s, 3H), 1.62-1.72 (m, 4H), 1.40-1.44 (m, 4H)

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

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

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 placed. The inside was cooled to 0 ° C, 25.0 g of methanesulfonyl chloride was added, and stirred at room temperature. After the completion of the reaction, 50 mL of pure water was added and stirred, and then ethyl acetate was added to extract an organic layer. After the organic layer was added with anhydrous magnesium sulfate, the mixture was dehydrated and dried, and then filtered, and the solvent was distilled off using a rotary evaporator to obtain DA-6. -1 (red body) 37.5 g. Furthermore, the resulting compound was used directly in the subsequent step.

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

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

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

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

In a 300 mL four-necked flask, 11.5 g of DA-6-2, tetrahydrofuran 150 mL, 1,6-hexanediol 23.6 g, and 1-(3-dimethylaminopropyl)-3-ethylcarbamate were placed. 11.9 g of quinone imine hydrochloride and 0.49 g of 4-dimethylaminopyridine were stirred at room temperature. After completion of the reaction, the reaction system was poured into 300 mL of ethyl acetate and extracted with saturated brine. Anhydrous magnesium sulfate was added to the extracted organic layer to dryness, and anhydrous magnesium sulfate was filtered. The obtained filtrate was evaporated to a solvent by a rotary evaporator to obtain a yield of DA-6-3 (red-brown). Furthermore, the resulting compound was used directly in the subsequent step.

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

In a 300 mL four-necked flask, 15.4 g of DA-6-3, N,N-dimethylformamide 150 mL, 2,4-dinitrofluorobenzene 8.2 g, and triethylamine 8.3 g were placed at 80 ° C. Stir while heating. 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 to dryness, and anhydrous magnesium sulfate was filtered. The resulting filtrate was distilled off by a rotary evaporator. The residue was washed with a solution of ethyl acetate / hexane (1: 4) and dried to yield 12.6 g (yield: 56%) of DA-6-4 (yield solid).

(Example 3-5) Synthesis of DA-6

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 placed, and the mixture was stirred while heating at 60 °C. After completion of the reaction, the reduced iron was filtered, and the organic layer was extracted with ethyl acetate. Anhydrous magnesium sulfate was added to the organic layer to dryness, and anhydrous magnesium sulfate was filtered. The resulting filtrate was distilled off by a rotary evaporator. The residue was separated by ruthenium dioxide colloidal column chromatography (ethyl acetate:hexane = 2:1 by volume) to obtain DA-6 (red-brown viscous) 7.1 g (yield: 63%). The results of the measurement of the obtained slim body by ¹ H-NMR are shown below. From this result, it was confirmed that the obtained binder was the intended DA-6.

¹ H NMR (400 MHz, [D ₆ ]-DMSO): δ 7.66-7.68 (d, 2H), 7.58-7.62 (d, 1H), 6.99-7.02 (d, 2H), 6.48-6.52 (d, 1H), 6.46 (S, 1H), 6.03 (s, 1H), 5.95 (s, 1H), 5.73-5.76 (d, 1H), 5.70 (s, 1H), 4.40-4.45 (m, 4H), 4.29 -4.34(m,4H),4.12-4.15(t,2H),3.74-3.78(t,2H),1.88(s,3H),1.64-1.68(m,4H),1.42-1.43(m,4H)

(Example 4) Synthesis of DA-7

4-bromohydroxybenzene (100 g, 578 mmol), tert-butyl acrylate (156 g, 1.21 mol), palladium (II) acetate (2.6 g, 11.6 mmol), and tris(o-tolyl)phosphine were placed in the reaction vessel. (7.0 g, 23.1 mmol), tributylamine (321 g, 1.73 mol), and N,N'-dimethylacetamide (hereinafter referred to as DMAc) (500 g) were heated and stirred at 100 °C. The reaction was followed by HPLC. After completion of the reaction, the reaction solution was poured into 1M aqueous hydrochloric acid (2 L) and stirring was continued. After adding ethyl acetate (1 L) and removing the water layer by liquid separation, the organic layer was washed three times with saturated brine (500 mL), dried over magnesium sulfate, and the organic layer was filtered, and the solvent was evaporated to give a compound. [1] (158g). The results of the measurement of the obtained compound by ¹ H-NMR are shown below. Furthermore, the resulting compound was used directly in the subsequent step.

¹ H-NMR (400 MHz, CDCl ₃ , δ ppm): 7.52 (1H, d), 7.40 (2H, d), 6.76 (1H, d), 6.22 (2H, d), 1.52 (9H, s)

Into the reaction vessel, the compound [1] (20.00 g, 90.8 mmol), triethylamine (11.94 g, 118 mmol), and tetrahydrofuran (hereinafter referred to as THF) (200 g) were placed, and after replacing with nitrogen, the internal temperature was not observed. A solution of 3,5-dinitrobenzimidyl chloride (25.12 g, 109 mmol) in THF (100 g) was added dropwise over 10 °C. The reaction was followed by HPLC. After the completion of the reaction, the reaction solution was poured into distilled water (1.8 L), and the precipitated solid was sufficiently washed with distilled water to obtain a crude product of compound [2]. Next, methanol (240 g) was added to the obtained crude product, and the mixture was heated under reflux for 30 minutes, and then allowed to cool to room temperature. The mixture was filtered and dried to give compound [2] (yield: 18.0 g, yield 49%). The results of the measurement of the obtained compound by ¹ H-NMR are shown below.

^{1 H-NMR (400MHz, DMSO} -d 6, δppm): 9.09-9.08 (1H, m), 9.05-9.04 (2H, m), 7.84-7.80 (2H, m), 7.57 (1H, m), 7.46 -7.38(2H,m), 6.54(1H,d), 1.46(9H,s)

Compound [2] (15.82 g, 38.2 mmol) and formic acid (80 g) were placed in a reaction container, and the mixture was stirred under heating at 40 °C. The reaction was followed by HPLC. After confirming the completion of the reaction, the reaction solution was poured into distilled water (800 mL), and the solid was filtered and washed thoroughly with distilled water. The obtained solid was dried to give the compound [3] (yield: 13.1 g, yield: 96%). The results of the measurement of the obtained compound by ¹ H-NMR are shown below.

^{1 H-NMR (400MHz, DMSO} -d 6, δppm): 12.5 (1H, brs), 9.10-9.09 (1H, m), 9.09-9.04 (2H, m), 7.84-7.80 (2H, m), 7.60 (1H,d), 7.44-7.41(2H,m), 6.54(1H,d)

Compound [3] (13.07 g, 36.5 mmol), 2-hydroxyethyl methacrylate (hereinafter referred to as HEMA) (5.70 g, 43.8 mmol), 1-(3-dimethylamine) were placed in a reaction vessel. Propyl)-3-ethylcarbodiimide (hereinafter referred to as EDC) (9.09 g, 47.4 mmol), 4-dimethylaminopyridine (hereinafter referred to as DMAP) (0.45 g, 3.65 mmol), THF (200 g) was stirred at room temperature. After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (1.2 L), and extracted with ethyl acetate. The organic layer was washed three times with distilled water, dried over magnesium sulfate, filtered, and the solvent was evaporated to give the compound [4] (yield: 16.8 g, yield 98%). The results of the measurement of the obtained compound by ¹ H-NMR are shown below.

^{1 H-NMR (400MHz, DMSO} -d 6, δppm): 9.09-9.08 (1H, m), 9.06-9.04 (2H, m), 7.88-7.86 (2H, m), 7.69 (1H, d), 7.44 -7.42 (2H, m), 6.68 (1H, d), 6.03-6.02 (1H, m), 5.69-5.67 (1H, m), 4.41-4.39 (2H, m), 4.36-4.34 (2H, m) , 1.86-1.85 (3H, m).

Compound [4] (16.8 g, 35.7 mmol), tin (IV) chloride (48.42 g, 255 mmol), THF (170 g), and distilled water (170 g) were placed in a reaction vessel, and the mixture was heated and stirred at 70 °C. After confirming the completion of the reaction by HPLC, the reaction solution was poured into a beaker containing ethyl acetate (1 L), and stirred, and neutralized by adding sodium hydrogencarbonate powder. Then, the precipitated solid was removed by filtration, and the filtrate was washed twice with a saturated aqueous sodium hydrogen carbonate solution (200 g), and washed three times with saturated brine (500 g), and dried over magnesium sulfate. Thereafter, the mixture was filtered, and the solvent was evaporated to give the desired compound DA-7 (yield: 12.9 g, yield 86%). The results of the measurement of the obtained compound by ¹ H-NMR are shown below.

¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 7.85-7.84 (3H, m), 7, 66 (1H, d), 7.45-7.43 (2H, m), 6.41-6.38 (2H, m) , 6.05-6.01 (2H, m), 5.70-5.63 (1H, m), 4.96 (4H, brs), 4.39-4.38 (2H, m), 4.37-4.35 (2H, m), 1.85-1.84 (3H, m).

(Example 5) Synthesis of DA-8

The compound [1] (127.3 g, 578 mmol), triethylamine (70.19 g, 694 mmol), and THF (800 g) were placed in a reaction vessel, and after replacing with nitrogen, the methyl group was not dropped while the internal temperature exceeded 10 ° C. A solution of propylene chloride (63.4 g, 607 mmol) in THF (200 g). After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (3 L) and extracted with ethyl acetate (1.5 L). The organic layer was washed three times with saturated brine (500 g), dried over magnesium sulfate, filtered, and the solvent was evaporated to give compound [5]. The results of the measurement of the obtained compound by ¹ H-NMR are shown below. Further, the compound [5] was used in the next step without purification.

^{1 H-NMR (400MHz, DMSO} -d 6, δppm): 7.78-7.72 (2H, m), 7.53 (1H, d), 7.21-7.18 (2H, m), 6.48 (1H, d), 6.25-6.24 (1H, m), 5.88-5.86 (1H, m), 1.97-1.95 (3H, m), 1.45 (9H, s).

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

¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 7.74-7.71 (2H, m), 7.57 (1H, d), 7.21-7.18 (2H, m), 6.49 (1H, d), 6.56-6.25 (1H, m), 5.89-5.88 (1H, m), 1.97-1.96 (3H, m).

2-(2,4-dinitrophenyl)ethanol (43.67 g, 206 mmol), compound [6] (45.53 g, 196 mmol), EDC (48.87 g, 255 mmol), DMAP (2.4 g) were placed in a reaction vessel. 19 mmol) and THF (900 g) were stirred at room temperature. After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (3 L), and extracted with ethyl acetate (1 L). Thereafter, the organic layer was washed three times with distilled water, dried over magnesium sulfate, filtered, and the solvent was evaporated to give a crude product of compound [7]. The obtained crude product was washed with methanol (100 mL), filtered, and dried under reduced pressure to give Compound [7]. (Yield 48.3 g, yield 58%). The results of the measurement of the obtained compound by ¹ H-NMR are shown below.

^{1 H-NMR (400MHz, DMSO} -d 6, δppm): 8.71 (1H, d), 8.47 (2H, dd), 7.88 (1H, d), 7.75-7.72 (2H, m), 7.59 (1H, d ), 7.23-7.20 (2H, m), 6.49 (1H, d), 6.26-6.25 (1H, m), 5.90-5.88 (1H, m), 4.43 (2H, 5), 3.35 (2H, t), 1.97-1.96 (3H, m).

Compound [7] (48.25 g, 113 mmol), iron (37.91 g, 679 mmol), ethyl acetate (435 g), ammonium chloride (18.15 g, 340 mmol), and distilled water (160 g) were placed in a reaction vessel. Stir at 70 ° C with heating. After confirming the completion of the reaction by HPLC, the solid was filtered over Celite, washed with ethyl acetate (1L) 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 evaporated to give a crude product of compound DA-8. The obtained crude product was washed with methanol, filtered, and dried under reduced pressure to give Compound DA-8 (yield: 29.8 g, yield 72%). The results of the measurement of the obtained compound by ¹ H-NMR are shown below.

¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 7.78-7.74 (2H, m), 7.63 (1H, d), 7.24-7.18 (2H, m), 6.59 (1H, d), 6.57 (1H) , s), 6.27-6.26 (1H, m), 5.91-5.88 (1H, m), 5.86 (1H, d), 5.76 (1H, dd), 3.99 (4H, brs), 4.14 (2H, t), 2.65 (2H, t), 1.97-1.95 (3H, m).

(Example 6) Synthesis of DA-9

(The cyclohexane ring of the above-mentioned reaction formula is a 1,4-trans-cyclohexane ring).

Trans-4-(4-bromophenyl)cyclohexanol (200 g, 784 mmol), tert-butyl acrylate (211 g, 1.65 mol), palladium (II) acetate (3.5 g, 15.7 mmol) were placed in a reaction vessel. Tris(o-tolyl)phosphine (9.5 g, 31.4 mmol), tributylamine (436 g, 2.35 mol), and DMAc (1000 g) were heated and stirred at 100 °C. After confirming the completion of the reaction by HPLC, the reaction solution was poured into a 1 M aqueous hydrochloric acid solution (3.5 L) and stirring was continued. After adding the ethyl acetate (1.5 L) to remove the aqueous layer by liquid separation, the organic layer was washed three times with saturated brine (500 mL), dried over magnesium sulfate, and the organic layer was filtered, and the solvent was evaporated to give a compound. [8] (yield 208 g, yield 88%). The results of the measurement of the obtained compound by ¹ H-NMR are shown below.

^{1 H-NMR (400MHz, DMSO} -d 6, δppm): 7.58 (2H, d), 7.50 (1H, d), 7.25 (2H, d), 6.44 (1H, d), 4.59 (1H, d), 3.46-3.36 (1H, m), 2.50-2.46 (1H, m), 1.93-1.90 (2H, m), 1.66-1.73 (2H, m), 1.49-1.26 (13H, m).

Compound [8] (40.0 g, 132 mmol), triethylamine (16.1 g, 159 mmol), and THF (300 g) were placed in a reaction vessel, and after nitrogen substitution, attention was paid not to allow the internal temperature to exceed 3 ° C to drip 3, A solution of 5-dinitrobenzimidyl chloride (32.0 g, 139 mmol) in THF (180 g). After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (2 L) and stirring was continued. Thereafter, the precipitated solid was sufficiently washed with distilled water to obtain a 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, and the solid was filtered and dried to give compound [9] (yield: 41.8 g, yield: 64%). The results of the measurement of the obtained compound by ¹ H-NMR are shown below.

¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 9.02-9.01 (1H, m), 8.89-8.88 (2H, m), 7.58 (2H, d), 7.49 (1H, d), 7.28 (2H) , d), 6.43 (1H, d), 5.06 (1H, m), 2.47-2.43 (1H, m), 2.7-1.15 (2H, m), 1.88-1.86 (2H, m), 1.75-1.60 (4H , m), 1.44 (9H, s).

Compound [9] (41.80 g, 84.2 mmol) and formic acid (210 g) were placed in a reaction vessel, and the mixture was stirred under heating at 40 °C. After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (2 L), and the solid was filtered and washed thoroughly with distilled water. The obtained solid was dried to give Compound [10] (yield: 37 g, yield: 99%). The results of the measurement of the obtained compound by ¹ H-NMR are shown below.

¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 9.03-9.02 (1H, m), 8.90-8.88 (2H, m), 7.58 (2H, d), 7.55 (1H, d), 7.30 (2H) , d), 6.44 (1H, d), 5.07-5.06 (1H, m), 2.64-2.59 (1H, m), 2.17-2.15 (2H, m), 1.88-1.86 (2H, m), 1.75-1.65 (4H,m).

Compound [10] (37.8 g, 85.8 mmol), HEMA (13.4 g, 103 mmol), EDC (21.38 g, 112 mmol), DMAP (1.05 g, 8.6 mmol), THF (570 g) were placed in the reaction vessel. Stir at a temperature. After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (1.8 L), and extracted with ethyl acetate. The organic layer was washed three times with distilled water, dried over magnesium sulfate, filtered, and evaporated to the solvent to afford the crude product of compound [11]. The obtained crude product was washed with 2-propanol (100 g) to give Compound [11] (yield 47.1 g, yield 99%). The results of the measurement of the obtained compound by ¹ H-NMR are shown below.

¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 9.02-9.01 (1H, m), 8.89-8.88 (2H, m), 7.63-7.55 (3H, m), 7.30 (2H, d), 6.59 (1H, d), 6.01-5.99 (1H, m), 5.69-5.67 (1H, m), 5.15-4.99 (1H, m), 4.37-4.32 (4H, m), 2.64-2.58 (1H, m) , 2.17-2.15 (2H, m), 1.95-1.62 (11H, m).

Compound [11] (47.4 g, 85.8 mmol), tin (IV) chloride (114 g, 601 mmol), THF (470 g), and distilled water (470 g) were placed in a reaction vessel, and the mixture was stirred under heating at 70 °C. After confirming the completion of the reaction by HPLC, the reaction solution was poured into a beaker containing ethyl acetate (1.5 L), and stirred, and neutralized by adding sodium hydrogencarbonate powder. Then, the precipitated solid was removed by filtration, and the filtrate was washed twice with a saturated aqueous solution of sodium hydrogencarbonate (200 g), and washed three times with saturated brine (500 g) and dried over magnesium sulfate. Thereafter, the mixture was filtered, and the solvent was evaporated to give the desired compound DA-9 (yield: 32.5 g, yield 76%). The results of the measurement of the obtained compound by ¹ H-NMR are shown below.

¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 7.64-7.59 (3H, m), 7.29 (2H, d), 6.58 (1H, d), 6.40-6.39 (2H, m), 6.01-5.98 (2H, m), 5.67-5.66 (1H, m), 4.97 (4H, brs), 4.86-4.81 (1H, m), 4.38-4.33 (4H, m), 2.62-2.46 (1H, m), 2.06 -2.03(2H,m), 1.99-1.94(5H,m),1.66-1.47(4H,m)

(Example 7) Synthesis of DA-10

(The cyclohexane ring of the above-mentioned reaction formula is a 1,4-trans-cyclohexane ring).

The compound [8] (74.43 g, 261 mmol), triethylamine (29.81 g, 295 mmol), and THF (1000 g) were placed in a reaction vessel, and after replacing with nitrogen, the methyl group was not dropped while the internal temperature exceeded 10 ° C. A solution of propylene chloride (27.01 g, 258 mmol) in THF (100 g). After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (3 L) and extracted with ethyl acetate (1.5 L). The organic layer was washed three times with saturated brine (500 g), dried over magnesium sulfate, filtered, and evaporated. The obtained crude product was washed with methanol (100 g), filtered, and dried to give compound [12] (yield: 72.9 g, yield: 80%). The results of the measurement of the obtained compound by ¹ H-NMR are shown below.

^{1 H-NMR (400MHz, DMSO} -d 6, δppm): 7.56 (2H, d), 7.47 (1H, d), 7.26 (2H, d), 6.42 (1H, d), 4.75-4.69 (1H, m ), 2.59-4.47 (1H, m), 2.01-1.98 (2H, m), 1.85-1.78 (5H, m), 1.59-1.44 (4H, m).

The compound [12] (20.29 g, 54.8 mmol) and DCM (100 g) were placed in a reaction vessel, and then trifluoroacetic acid (31.2 g, 274 mol) was added dropwise. After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (200 mL) and extracted with ethyl acetate (1 L). Then, the organic layer was washed three times with saturated brine (200 g), and the organic layer was dried over magnesium sulfate, filtered, and the solvent was evaporated to the solvent to obtain the crude product of compound [13]. The obtained crude product was washed with methanol (30 g), and filtered and dried to give compound [13] (yield: 10.9 g, yield: 64%). The results of the measurement of the obtained compound by ¹ H-NMR are shown below.

^{1 H-NMR (400MHz, DMSO} -d 6, δppm): 12.32 (1H, brs), 7.58-7.50 (3H, m), 7.27 (2H, d), 6.43 (1H, d), 5.99-5.98 (1H , m), 5.64-5.63 (1H, m), 4.78-4.70 (1H, m), 2.59-2.51 (1H, m), 2.02-1.95 (2H, m), 1.82-1.79 (5H, m), 1.63 -1.42 (4H).

2-(2,4-dinitrophenyl)ethanol (11.94 g, 56.3 mmol), compound [13] (10.89 g, 35.3 mmol), EDC (11.62 g, 61.0 mmol), DMAP were placed in a reaction vessel. (0.57 g, 4.7 mmol) and THF (130 g) were stirred at room temperature. After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (600 mL), and the precipitated solid was washed with distilled water to obtain a crude product of compound [14]. The obtained crude product was washed with methanol (100 mL), filtered, and dried under reduced pressure to give compound [14] (yield 17.1 g, yield 96%). The results of the measurement of the obtained compound by ¹ H-NMR are shown below.

^{1 H-NMR (400MHz, DMSO} -d 6, δppm): 8.70-8.69 (1H, m), 8.48-8.45 (1H, m), 7.87 (1H, d), 7.58-7.52 (3H, m), 7.27 (2H,d), 6.44(1H,d),5.99-5.98(1H,m),5.63-5.62(1H,m),4.76-4.71(1H,m),4.41(2H,t),3.34(2H , t), 2.57-2.54 (1H, m), 2.01-1.97 (2H, m), 1.84-1.78 (5H, m), 1.60-1.45 (4H, m).

The compound [14] (17.00 g, 33.4 mmol), iron (11.2 g, 201 mmol), ethyl acetate (150 g), ammonium chloride (5.35 g, 100 mmol), and distilled water (50 g) were placed in a reaction vessel. Stir at 70 ° C with heating. After confirming the completion of the reaction by HPLC, the solid was filtered over Celite, washed with ethyl acetate (200 mL) and removed. The filtrate was washed three times with saturated brine (200 g), and the organic layer was dried over magnesium sulfate, and the solvent was evaporated to give a crude product of compound DA-10. The obtained crude product was washed with methanol (100 g), filtered, and dried under reduced pressure to give Compound DA-10 (yield: 10.3 g, yield 69%). The results of the measurement of the obtained compound by ¹ H-NMR are shown below.

¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 7.61-7.57 (3H, m), 7.27 (2H, d), 6.58-6.51 (2H, m), 5.99 (1H, s), 5.85 (1H) , d), 5.75 (1H, dd), 5.65-5.63 (1H, m), 4.80-4.71 (1H, m), 4.63 (2H, brs), 4.57 (2H, brs), 4.12 (2H, t), 2.64 (2H, t), 2.59-2.53 (1H, m), 2.00-1.98 (2H, m), 1.85-1.79 (5H, m), 1.64-1.44 (4H, m).

(Example 8) Synthesis of DA-11

4'-Bromo-[1,1'-biphenyl]-4-ol (150 g, 602 mmol), tert-butyl acrylate (162 g, 1.26 mol), palladium (II) acetate (2.70 g) were placed in the reaction vessel. 12.0 mmol), tris(o-tolyl)phosphine (7.33 g, 24.1 mmol), tributylamine (335 g, 1.81 mol), and DMAc (750 g) were heated and stirred at 100 °C. After confirming the completion of the reaction by HPLC, the reaction solution was poured into a 1 M aqueous hydrochloric acid solution (3.5 L) and stirring was continued. After adding ethyl acetate (1 L) and removing the water layer by liquid separation, the organic layer was washed three times with saturated brine (500 mL), dried over magnesium sulfate, and the organic layer was filtered, and the solvent was evaporated to give a compound. [15] (yield 176 g, yield 99%). The results of the measurement of the obtained compound by ¹ H-NMR are shown below.

^{1 H-NMR (400MHz, DMSO} -d 6, δppm): 9.67 (1H, s), 7.72 (2H, d), 7.62 (2H, d), 7.19-7.54 (3H, m), 6.89-6.82 (2H , m), 6.52 (1H, d), 1.49 (9H, s).

The compound [15] (73.4 g, 318 mmol), triethylamine (36.8 g, 364 mmol), and THF (1000 g) were placed in a reaction vessel, and after nitrogen substitution, attention was paid not to allow the internal temperature to exceed 3 ° C to drip 3, A solution of 5-dinitrobenzimidyl chloride (73.37 g, 318 mmol) in THF (300 g). After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (6 L) and stirring was continued. Thereafter, the precipitated solid was sufficiently washed with distilled water to obtain a 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, and the solid was filtered and dried to give compound [16] (yield: 117.9 g, yield: 79%). The results of the measurement of the obtained compound by ¹ H-NMR are shown below.

¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 9.14 - 9.13 (1H, m), 9.13 - 9.10 (2H, m), 7.78-7.76 (6H, m), 7.74 (1H, d), 7.52 -7.50 (2H, m), 6.59 (1H, m), 1.50-1.49 (9H, m).

Compound [16] (117.9 g, 240 mmol) and formic acid (1180 g) were placed in a reaction vessel, and the mixture was stirred under heating at 40 °C. After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (3 L), and the solid was filtered and washed thoroughly with distilled water. The obtained solid was dried to give Compound [17] (yield: 102 g, yield 98%). The results of the measurement of the obtained compound by ¹ H-NMR are shown below.

¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 9.15-9.13 (1H, m), 9.11-9.10 (2H, m), 7.89-7.86 (2H, m), 7.83-7.77 (4H, m) , 7.64 (1H, d), 7.55-7.49 (2H, m), 6.60 (1H, d),

Compound [17] (40.0 g, 92.1 mmol), HEMA (18.0 g, 138 mmol), EDC (22.8 g, 120 mmol), DMAP (1.13 g, 9.2 mmol), and THF (600 g) were placed in the reaction vessel. Stir at a temperature. After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (3 L), and extracted with ethyl acetate. The organic layer was washed three times with saturated brine (500 g), dried over magnesium sulfate, filtered, and evaporated to the solvent to afford the crude product of compound [18]. The obtained crude product was washed with methanol (300 g) to give Compound [18] (yield: 27.8 g, yield 55%). The results of the measurement of the obtained compound by ¹ H-NMR are shown below.

^{1 H-NMR (400MHz, DMSO} -d 6, δppm): 9.14-9.12 (1H, m), 9.10-9.09 (2H, m), 7.88-7.84 (4H, m), 7.79-7.71 (3H, m) , 7.52-7.50 (2H, m), 6.73 (1H, d), 6.07-6.06 (1H, m), 5.72-5.71 (1H, m), 4.46-4.43 (2H, m), 4.40-4.38 (2H, m), 1.90-1.89 (3H, m).

Compound [18] (27.8 g, 50.9 mmol), tin (IV) chloride (67.6 g, 357 mmol), THF (280 g), and distilled water (220 g) were placed in a reaction vessel, and the mixture was stirred under heating at 70 °C. After confirming the completion of the reaction by HPLC, the reaction solution was poured into a beaker containing ethyl acetate (2 L), and stirred, and neutralized by adding sodium hydrogencarbonate powder. Then, the precipitated solid was removed by filtration, and the filtrate was washed twice with a saturated aqueous solution of sodium hydrogencarbonate (200 g), and washed three times with saturated brine (500 g) and dried over magnesium sulfate. Then, the mixture was filtered, and the solvent was evaporated to give the desired compound DA-11 (yield: 23.9 g, yield 97%). The results of the measurement of the obtained compound by ¹ H-NMR are shown below.

^{1 H-NMR (400MHz, DMSO} -d 6, δppm): 7.86-7.71 (7H, m), 7.32-7.30 (2H, m), 6.73 (1H, d), 6.61-6.60 (2H, m), 6.12 -6.11 (1H, m), 6.06-6.05 (1H, m), 5.72-5.71 (1H, m), 5.12 (4H, brs), 4.45-4.30 (2H, m), 4.40-4.38 (2H, m) , 1.89-1.87 (3H, m).

(Example 9) Synthesis of DA-12

The compound [15] (89.15 g, 303 mmol), triethylamine (36.8 g, 364 mmol), and THF (1000 g) were placed in a reaction vessel, and after nitrogen substitution, the internal temperature was not allowed to drip more than 10 ° C. A solution of methacrylic acid ruthenium chloride (33.27 g, 318 mmol) in THF (330 g). After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (6 L) and stirring was continued, and the precipitated solid was filtered and washed thoroughly with distilled water to obtain a crude product of compound [19]. Next, methanol (1 L) was added to the obtained crude product, and the mixture was stirred at room temperature for 30 minutes, and then filtered and dried to give Compound [19] (yield 94.5 g, yield 86%). The results of the measurement of the obtained compound by ¹ H-NMR are shown below.

¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 7.81 - 7.73 (6H, m), 7.60 (1H, d), 7.32-7.28 (2H, m), 6.59 (1H, d), 6.33-6.30 (1H, m), 5.93-5.92 (1H, m), 2.02-2.00 (3H, m), 1.49 (9H, s), 159-1.44 (4H, m).

The compound [19] (94.51 g, 259 mmol) and formic acid (475 g) were placed in a reaction vessel, and the mixture was replaced with nitrogen, followed by heating and stirring at 40 °C. After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (3.5 L), and the precipitated solid was filtered, washed thoroughly with distilled water, and solid was dried under reduced pressure to give compound [20] (yield: 74.9 g, yield) Rate 75%). The results of the measurement of the obtained compound by ¹ H-NMR are shown below.

¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 7.81 - 7.63 (6H, m), 7.64 (1H, d), 7.32-7.28 (2H, m), 6.60 (1H, d), 6.32-6.31 (1H, m), 5.93-5.92 (1H, m), 2.03-2.02 (3H, m).

2-(2,4-Dinitrophenyl)ethanol (41.29 g, 195 mmol), compound [20] (50.00 g, 162 mmol), EDC (40.21 g, 211 mmol), DMAP (1.98) were placed in a reaction vessel. g, 16.2 mmol) and THF (600 g) were stirred at room temperature. After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (3.6 L), and the precipitated solid was washed with distilled water to obtain a crude product of compound [21]. The obtained crude product was washed with methanol (300 mL), filtered, and dried under reduced pressure to give compound [21] (yield 65.1 g, yield 80%). The results of the measurement of the obtained compound by ¹ H-NMR are shown below.

^{1 H-NMR (400MHz, DMSO} -d 6, δppm): 8.76-8.75 (1H, m), 854-8.48 (1H, m), 7.93 (1H, d), 7.82-7.61 (7H, m), 7.31 -7.28(2H,m),6.62-6.57(1H,m),6.32-6.31(1H,m),5.93-5.92(1H,m),4.48(2H,t),3.39(2H,t),2.03 -2.02 (3H, m).

Compound [21] (65.01 g, 130 mmol), tin (IV) chloride (171.9 g, 906 mmol), THF (650 g), and distilled water (520 g) were placed in a reaction vessel, and the mixture was stirred under heating at 70 °C. After confirming the completion of the reaction by HPLC, the reaction solution was poured into a beaker containing ethyl acetate (3.5 L), and stirred, and neutralized by adding sodium hydrogencarbonate powder. Then, the precipitated solid was removed by filtration, and the filtrate was washed twice with a saturated aqueous solution of sodium hydrogencarbonate (200 g), and washed three times with saturated brine (500 g) and dried over magnesium sulfate. Thereafter, the mixture was filtered, and the solvent was evaporated to give a crude product of the desired compound DA-12. Next, the obtained crude product was washed with methanol (200 g), filtered, and dried to give Compound DA-12 (yield 49.5 g, yield 76%). The results of the measurement of the obtained compound by ¹ H-NMR are shown below.

¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 7.84-7.55 (7H, m), 7.31-7.28 (2H, m), 6.60 (1H, d), 6.53 (1H, d), 6.32-6.30 (1H, m), 5.93-5.91 (2H, m), 5.83-5.81 (1H, m), 4.19-4.18 (2H, m), 2.71-2.70 (2H, m), 3, 17 (4H, brs) , 2.03-2.27 (3H, m)

(Example 10) Synthesis of liquid crystal alignment agent

CBDA 1.90g (0.0096mol), 0.27g DA-1 (0.0025 mol), 3.06g DA-4 (0.0060mol), 0.57g DA-2 (0.0015 mol) in NMP 32.91g, react at room temperature A solution of polyamine acid (PAA-1) was prepared for 16 hours. The polyamido acid coefficient has an 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 solution of the polyamic acid, and the mixture was stirred to prepare a polyamine acid (PAA-1) of 6 mass%, NMP of 74 mass%, and BCS of 20 mass%, and the pore diameter was 1 μm. The membrane filter was pressure-filtered to obtain a liquid crystal alignment agent of Example 10.

(Example 11) Synthesis of liquid crystal alignment agent

CBDA 1.94g (0.0099mol), 4.34g DA-4 (0.0085 mol), 0.57g DA-2 (0.0015mol) in 38.83g of NMP, reacted at room temperature for 16 hours to prepare poly-proline (PAA) -2) solution. The polyamido acid coefficient has an average molecular weight of about 9000 and a weight average molecular weight of about 24,000. After adding NMP and BCS to 10 g of the solution of the polyamic acid, the mixture was stirred to prepare a polyamine acid (PAA-2) of 6 mass%, NMP of 74 mass%, and BCS of 20 mass%, and the pore diameter was 1μm film The filter was subjected to pressure filtration to obtain a liquid crystal alignment agent of Example 11.

(Example 12) Synthesis of liquid crystal alignment agent

CBDA 1.94 g (0.0099 mol) and 5.10 g of DA-4 (0.01 mol) were reacted in NMP 39.93 g at room temperature for 16 hours to prepare a solution of polyamine acid (PAA-3). The polyamido acid coefficient has an average molecular weight of about 8,000 and a weight average molecular weight of about 19,000. After adding NMP and BCS to 10 g of the solution of the polyamic acid, the mixture was stirred to prepare a polyamine acid (PAA-3) of 6 mass%, NMP of 74 mass%, and BCS of 20 mass%, and the pore diameter was A 1 μm membrane filter was subjected to pressure filtration to obtain a liquid crystal alignment agent of Example 12.

(Example 13) Synthesis of liquid crystal alignment agent

CBDA 1.94g (0.0099mol), 4.10g DA-4 (0.0080 mol), 0.76g DA-2 (0.0020mol) in NMP 38.55g, reacted at room temperature for 16 hours to prepare poly-proline (PAA) -6) solution. The polyamido acid coefficient has an average molecular weight of about 10,000 and a weight average molecular weight of about 20,000. After adding NMP and BCS to 10 g of the solution of the polyamic acid, the mixture was stirred to prepare a polyamine acid (PAA-6) of 6 mass%, NMP of 74 mass%, and BCS of 20 mass%, and the pore diameter was A 1 μm membrane filter was subjected to pressure filtration to obtain a liquid crystal alignment agent of Example 13.

(Example 14) Synthesis of liquid crystal alignment agent

CBDA 1.94g (0.0099mol), 3.86g DA-5 (0.0080 mol), 0.76g DA-2 (0.0020mol) in NMP 37.19g, reacted at room temperature for 16 hours to prepare poly-proline (PAA) -7) solution. The polyamido acid coefficient has an average molecular weight of about 10,000 and a weight average molecular weight of about 20,000. After adding NMP and BCS to 10 g of the solution of the polyamic acid, the mixture was stirred to prepare a polyamine acid (PAA-7) of 6 mass%, NMP of 74 mass%, and BCS of 20 mass%, and the pore diameter was A 1 μm membrane filter was subjected to pressure filtration to obtain a liquid crystal alignment agent of Example 14.

(Example 15) Synthesis of liquid crystal alignment agent

CBDA 1.94g (0.0099mol), 3.86g DA-6 (0.0080 mol), 0.76g DA-2 (0.0020mol) in NMP 37.19g, reacted at room temperature for 16 hours to prepare poly-proline (PAA) -8) solution. The polyamido acid coefficient has an average molecular weight of about 9000 and a weight average molecular weight of about 18,000. After adding NMP and BCS to 10 g of the solution of the polyamic acid, the mixture was stirred to prepare a polyamine acid (PAA-8) of 6 mass%, NMP of 74 mass%, and BCS of 20 mass%, and the pore diameter was A 1 μm membrane filter was subjected to pressure filtration to obtain a liquid crystal alignment agent of Example 15.

(Example 16) Synthesis of liquid crystal alignment agent

CBDA 1.94g (0.0099m ol), 2.93g DA-8 (0.0080 mol), 0.76g DA-2 (0.0020mol) in NMP 31.92g, reacted at room temperature for 16 hours to prepare poly-proline ( Dissolution of PAA-10) liquid. The polyamido acid coefficient has an average molecular weight of about 8,000 and a weight average molecular weight of about 16,000. After adding NMP and BCS to 10 g of the solution of the polyamic acid, the mixture was stirred to prepare a polyamine acid (PAA-10) of 6 mass%, NMP of 74 mass%, and BCS of 20 mass%, and the pore diameter was A 1 μm membrane filter was subjected to pressure filtration to obtain a liquid crystal alignment agent of Example 16.

(Example 17) Synthesis of liquid crystal alignment agent

CBDA 1.94g (0.0099mol), 3.94g DA-9 (0.0080 mol), 0.76g DA-2 (0.0020mol) in NMP 31.92g, reacted at room temperature for 16 hours to prepare poly-proline (PAA) -11) solution. The polyamido acid coefficient has an average molecular weight of about 9000 and a weight average molecular weight of about 22,000. After adding NMP and BCS to 10 g of the solution of the polyamic acid, the mixture was stirred to prepare a polyamine acid (PAA-11) of 6 mass%, NMP of 74 mass%, and BCS of 20 mass%, followed by pore diameter. A 1 μm membrane filter was subjected to pressure filtration to obtain a liquid crystal alignment agent of Example 17.

(Example 18) Synthesis of liquid crystal alignment agent

CBDA 1.94g (0.0099mol), 3.59g DA-10 (0.0080 mol), 0.76g DA-2 (0.0020mol) in NMP 35.65g, reacted at room temperature for 16 hours to prepare poly-proline (PAA) -12) solution. The polyamido acid coefficient has an average molecular weight of about 8,000 and a weight average molecular weight of about 23,000. Add NMP to 10 g of this polylysine solution. After BCS, the mixture was stirred to prepare a polyglycolic acid (PAA-12) of 6 mass%, NMP was 74 mass%, and BCS was 20 mass%, and then subjected to pressure filtration using a membrane filter having a pore diameter of 1 μm to obtain an example. 18 liquid crystal alignment agent.

(Example 19) Synthesis of liquid crystal alignment agent

CBDA 1.94g (0.0099mol), 3.89g DA-11 (0.0080 mol), 0.76g DA-2 (0.0020mol) in NMP 37.37g, reacted at room temperature for 16 hours to prepare poly-proline (PAA) -13) solution. The polyamido acid coefficient has an average molecular weight of about 7,000 and a weight average molecular weight of about 20,000. After adding NMP and BCS to 10 g of the solution of the polyamic acid, the mixture was stirred to prepare a polyamine acid (PAA-13) of 6 mass%, NMP of 74 mass%, and BCS of 20 mass%, and the pore diameter was A 1 μm membrane filter was subjected to pressure filtration to obtain a liquid crystal alignment agent of Example 19.

(Example 20) Synthesis of liquid crystal alignment agent

CBDA 1.94g (0.0099mol), 3.54g DA-12 (0.0080 mol), 0.76g DA-2 (0.0020mol) in NMP 35.37g, reacted at room temperature for 16 hours to prepare poly-proline (PAA) -14) solution. The polyamido acid coefficient has an average molecular weight of about 8,000 and a weight average molecular weight of about 21,000. After adding NMP and BCS to 10 g of the solution of the polyamic acid, the mixture was stirred to prepare a polyamine acid (PAA-14) of 6 mass%, NMP of 74 mass%, and BCS of 20 mass%, followed by pore diameter. A 1 μm membrane filter was subjected to pressure filtration to obtain a liquid crystal alignment agent of Example 20.

(Example 21) Synthesis of liquid crystal alignment agent

1.94 g (0.0099 mol) of CBDA and 4.82 g of DA-5 (0.01 mol) were added to 38.35 g of NMP, and the mixture was reacted at room temperature for 16 hours to prepare a solution of polyamine acid (PAA-15). The polyamido acid coefficient has an average molecular weight of about 11,000 and a weight average molecular weight of about 21,000. After adding NMP and BCS to 10 g of the solution of the polyamic acid, the mixture was stirred to prepare a polyamine acid (PAA-15) of 6 mass%, NMP of 74 mass%, and BCS of 20 mass%, and the pore diameter was A 1 μm membrane filter was subjected to pressure filtration to obtain a liquid crystal alignment agent of Example 21.

(Example 22) Synthesis of liquid crystal alignment agent

CBDA 1.94 g (0.0099 mol) and 4.82 g of DA-6 (0.01 mol) were added to 38.35 g of NMP, and allowed to react at room temperature for 16 hours to prepare a solution of polyamine acid (PAA-16). The polyamido acid coefficient has an average molecular weight of about 10,000 and a weight average molecular weight of about 20,000. After adding NMP and BCS to 10 g of the solution of the polyamic acid, the mixture was stirred to prepare a polyamine acid (PAA-16) of 6 mass%, NMP of 74 mass%, and BCS of 20 mass%, and the pore diameter was A 1 μm membrane filter was subjected to pressure filtration to obtain a liquid crystal alignment agent of Example 22.

(Example 23) Synthesis of liquid crystal alignment agent

CBDA 1.94 g (0.0099 mol) and 3.66 g of DA-8 (0.01 mol) were added to NMP 31.76 g, and allowed to react at room temperature for 16 hours to prepare a solution of polyglycine (PAA-18). The polyamido acid coefficient has an average molecular weight of about 9000 and a weight average molecular weight of about 18,000. After adding NMP and BCS to 10 g of the solution of the polyamic acid, the mixture was stirred to prepare a polyamine acid (PAA-18) of 6 mass%, NMP of 74 mass%, and BCS of 20 mass%, and the pore diameter was A 1 μm membrane filter was subjected to pressure filtration to obtain a liquid crystal alignment agent of Example 23.

(Example 24) Synthesis of liquid crystal alignment agent

CBDA 1.94 g (0.0099 mol) and 4.92 g of DA-9 (0.01 mol) were reacted in NMP 38.91 g at room temperature for 16 hours to prepare a solution of polyamidamine (PAA-19). The polyamido acid coefficient has an average molecular weight of about 10,000 and a weight average molecular weight of about 24,000. After adding NMP and BCS to 10 g of the solution of the polyamic acid, the mixture was stirred to prepare a polyamine acid (PAA-19) of 6% by mass, NMP of 74% by mass, and BCS of 20% by mass. A 1 μm membrane filter was subjected to pressure filtration to obtain a liquid crystal alignment agent of Example 24.

(Example 25) Synthesis of liquid crystal alignment agent

1.94 g (0.0099 mol) of CBDA and 4.48 g of DA-10 (0.01 mol) were added to 36.42 g of NMP, and allowed to react at room temperature for 16 hours to prepare a solution of polyglycine (PAA-20). The polyamido acid coefficient has an average molecular weight of about 10,000 and a weight average molecular weight of about 23,000. Polylysine After adding NMP and BCS to 10 g of the solution, the mixture was stirred to prepare a polyamine acid (PAA-20) of 6 mass%, NMP of 74 mass%, and BCS of 20 mass%, and then a membrane filter having a pore diameter of 1 μm. The liquid crystal alignment agent of Example 25 was obtained by pressure filtration.

(Example 26) Synthesis of liquid crystal alignment agent

CBDA 1.94 g (0.0099 mol) and 4.86 g of DA-11 (0.01 mol) were reacted in NMP 38.57 g at room temperature for 16 hours to prepare a solution of polyamidamine (PAA-21). The polyamido acid coefficient has an average molecular weight of about 9000 and a weight average molecular weight of about 21,000. After adding NMP and BCS to 10 g of the solution of the polyamic acid, the mixture was stirred to prepare a polyamine acid (PAA-21) of 6 mass%, NMP of 74 mass%, and BCS of 20 mass%, and the pore diameter was A 1 μm membrane filter was subjected to pressure filtration to obtain a liquid crystal alignment agent of Example 26.

(Example 27) Synthesis of liquid crystal alignment agent

CBDA 1.94 g (0.0099 mol) and 4.42 g of DA-12 (0.01 mol) were reacted in NMP 36.08 g at room temperature for 16 hours to prepare a solution of polyamidamine (PAA-22). The polyamido acid coefficient has an average molecular weight of about 8,000 and a weight average molecular weight of about 21,000. After adding NMP and BCS to 10 g of the solution of the polyamic acid, the mixture was stirred to prepare a polyamine acid (PAA-22) of 6 mass%, NMP of 74 mass%, and BCS of 20 mass%, followed by pore diameter. A 1 μm membrane filter was subjected to pressure filtration to obtain a liquid crystal alignment agent of Example 27.

(Comparative Example 1) Synthesis of liquid crystal alignment agent

1.94 g (0.0099 mol) of CBDA, 2.23 g of DA-3 (0.0085 mol), and 0.57 g of DA-2 (0.0015 mol) were reacted in NMP 18.97 g at room temperature for 16 hours to prepare polylysine (PAA). -4) solution. The polyamido acid coefficient has an average molecular weight of about 8,000 and a weight average molecular weight of about 22,000. After adding NMP and BCS to 10 g of the solution of the polyamic acid, the mixture was stirred to prepare a polyamine acid (PAA-4) of 6 mass%, NMP of 74 mass%, and BCS of 20 mass%, and the pore diameter was A 1 μm membrane filter was subjected to pressure filtration to obtain a liquid crystal alignment agent of Comparative Example 1.

(Comparative Example 2) Synthesis of liquid crystal alignment agent

1.84 g (0.0094 mol) of CBDA and 1.08 g of DA-1 (0.01 mol) were added to 26.32 g of NMP, and the mixture was reacted at room temperature for 16 hours to prepare a solution of polyamine acid (PAA-5). The polyamido acid coefficient has an average molecular weight of about 6,000 and a weight average molecular weight of about 13,000. After adding NMP and BCS to 10 g of the solution of the polyamic acid, the mixture was stirred to prepare a polyamine acid (PAA-5) of 6 mass%, NMP of 74 mass%, and BCS of 20 mass%, and the pore diameter was A 1 μm membrane filter was subjected to pressure filtration to obtain a liquid crystal alignment agent of Comparative Example 2.

(Comparative Example 3) Synthesis of liquid crystal alignment agent

CBDA 1.94g (0.0099mol), 2.09g DA-3 (0.0080 mol), 0.76g DA-2 (0.0020mol) in NMP 18.97g, The reaction was allowed to proceed for 16 hours at room temperature to prepare a solution of polyamine acid (PAA-23). The polyamido acid coefficient has an average molecular weight of about 8,000 and a weight average molecular weight of about 22,000. After adding NMP and BCS to 10 g of the solution of the polyamic acid, the mixture was stirred to prepare a polyamine acid (PAA-23) of 6 mass%, NMP of 74 mass%, and BCS of 20 mass%, and the pore diameter was A 1 μm membrane filter was subjected to pressure filtration to obtain a liquid crystal alignment agent of Comparative Example 3.

(Comparative Example 4) Synthesis of liquid crystal alignment agent

CBDA 1.94g (0.0099mol), 3.28g DA-7 (0.0080 mol), 0.76g DA-2 (0.0020mol) in NMP 33.92g, reacted at room temperature for 16 hours to prepare poly-proline (PAA) -9) solution. The polyamido acid coefficient has an average molecular weight of about 7,000 and a weight average molecular weight of about 15,000. After adding NMP and BCS to 10 g of the solution of the polyamic acid, the mixture was stirred to prepare a polyamine acid (PAA-9) of 6 mass%, NMP of 74 mass%, and BCS of 20 mass%, and the pore diameter was A 1 μm membrane filter was subjected to pressure filtration to obtain a liquid crystal alignment agent of Comparative Example 4.

<Production of liquid crystal cell>

The liquid crystal alignment agent of Example 10 was spin-coated on an ITO surface of an ITO electrode substrate having a pixel size of 100 μm × 300 μm and an ITO electrode pattern of 5 μm in wire/pitch, and dried on a hot plate at 80 ° C for 90 seconds. After the clock, it was baked in a hot air circulating oven at 200 ° C for 30 minutes to form a liquid crystal alignment film having a film thickness of 100 nm.

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

The two substrates described above were spread on a liquid crystal alignment film of a substrate by a bead interval of 6 μm, and then a sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed thereon. Next, the surface on the side where the other substrate is formed with the liquid crystal alignment film is placed inside, and after bonding to the immediately adjacent substrate, the sealant is cured to form an empty cell. Liquid crystal MLC-6608 (trade name, manufactured by Merck Co., Ltd.) was injected into the empty cell by a vacuum injection method, and Isotropic treatment (realignment treatment of liquid crystal by heating) was performed in an oven at 120 ° C to prepare a liquid crystal cell. (Vertical alignment mode uses an anti-parallel liquid crystal cell). Further, in the same manner, the liquid crystal alignment agents prepared in Examples 11, 13 to 20 and Comparative Examples 1, 3, and 4 were used to form liquid crystal cells.

The response speed immediately after the production of the liquid crystal cell obtained by using the liquid crystal alignment agents of Examples 10 to 11, 13 to 20 and Comparative Examples 1, 3 and 4 was measured by the following method. Thereafter, the liquid crystal cell was irradiated with UV 10J passing through a 313 nm band pass filter from the outside of the liquid crystal cell in a state where a voltage of 20 Vp-p was applied. Thereafter, the response speed was measured again, and the response speed before and after the UV irradiation was compared. The results of the response speed immediately after the production of the liquid crystal cell (indicated as "initial" in the table) and after irradiation of UV (indicated as "after UV" in the table) are shown in Table 1.

"Method for measuring response speed"

First, a liquid crystal cell is disposed between a group of polarizing plates in a measuring device comprising a group of polarizing plates and a light amount detector in a state of being backlit or crossed in a prismatic state. At this time, the pattern of the wire/spaced ITO electrode was formed at an angle of 45° to the crossed Nicoles. Further, a rectangular wave having a voltage of ±4 V and a frequency of 1 kHz is applied to the liquid crystal cell described above, and a change in saturation of the luminance observed by the light amount detector is presented to the oscilloscope, and the luminance when the voltage is not applied is 0%. Apply a voltage of ±4V so that the value of the saturation brightness is 100%, and the time required for the brightness to change from 10% to 90% is the 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 a photopolymerizable group and a photodimerization group was used as a raw material, even if no photopolymerizable compound was contained, the response was obtained. The speed is still very fast. Further, in comparison with Comparative Examples 1 and 3 using a diamine compound having a photopolymerizable group instead of the diamine compound of the above formula [1] but having no photodimerization, as compared with the use formula [ 1] Comparative Example 4 in which R ⁴ is a single bond diamine compound, and the response speeds of Examples 10 to 11 and 13 to 20 were remarkably accelerated.

<Production of liquid crystal cell>

The liquid crystal alignment agent of Example 12 was spin-coated on a glass substrate with two transparent electrodes, dried on a hot plate at 90 ° C for 60 seconds, and then fired in a hot air circulating oven at 200 ° C for 30 minutes. A liquid crystal alignment film having a film thickness of 100 nm was formed. These coating surfaces were arranged such that the substrate passing through the 313 nm band pass filter and the UV of the polarizing plate were inverted in parallel with the unit cell, and 500 mJ was irradiated from directly above.

The two substrates described above were spread on a liquid crystal alignment film of a substrate by a bead interval of 6 μm, and then a sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed thereon. Next, the surface on the side where the other substrate is formed with the liquid crystal alignment film is placed inside, and after bonding to the immediately adjacent substrate, the sealant is cured to form an empty cell. Liquid crystal MLC-2041 (trade name, manufactured by Merck) was injected into the empty cell by a vacuum injection method, and isotropic treatment (realignment treatment of liquid crystal by heating) in an oven at 120 ° C to prepare a liquid crystal cell (horizontal The alignment mode uses an anti-parallel cell. Further, in the same manner, liquid crystal cells were prepared using the liquid crystal alignment agents prepared in Examples 21 to 27 and Comparative Example 2.

<Evaluation of liquid crystal alignment>

The prepared unit cell was held between polarizing plates arranged on the backlight to form crossed prisms, and the unit cell was observed, and the liquid crystal alignment property was evaluated on the basis of the following criteria. The evaluation results are shown in Table 2.

○: Failure to observe alignment was observed.

×: Poor alignment was observed.

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

Claims (11)

A liquid crystal alignment agent characterized by containing at least one polymer selected from the group consisting of a polyimide precursor and a polyimine obtained by imidating a precursor, the polyimine precursor being contained The reaction of the diamine component of the diamine compound represented by the formula [1] with the tetracarboxylic dianhydride component; (wherein R ³ represents a group selected from -CH ₂ -, -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH-, -CO-; R ⁴ is a carbon a 1-alkyl group, a divalent carbon ring or a heterocyclic ring formed by a carbon number of 30, and one or a plurality of hydrogen atoms of the alkyl group, the divalent carbocyclic ring or the heterocyclic ring may be a fluorine atom or Substituted by an organic group; further, when R ⁴ is not adjacent to each other, -CH ₂ - may be substituted for such a group: -O-, -NHCO-, -CONH-, - COO-, -OCO-, -NH-, -NHCONH-, -CO-; R ⁵ represents -CH ₂ -, -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH- Any one of -CO- or a single bond; R ⁶ represents a group which initiates photodimerization; R ⁷ is a single bond, or an alkylene group formed by a carbon number of 1 to a carbon number of 30, a divalent carbon ring or a heterocyclic ring, and one or more hydrogen atoms of the alkylene group, the divalent carbocyclic ring or the heterocyclic ring may be substituted by a fluorine atom or an organic group; further, R ⁷ may be exemplified in any of the subsequent groups. When not adjacent, -CH ₂ - may be substituted for such groups: -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, -CO-; R ⁸ represents a photopolymerizable group). The liquid crystal alignment agent of claim 1, wherein R ⁶ is a divalent group represented by the following formula; (wherein * represents the bonding position with R ⁵ or R ⁷ ). The liquid crystal alignment agent of claim 1, wherein R ⁸ is a monovalent group represented by the following formula; (where * represents the bonding position with R ⁷ ). The liquid crystal alignment agent of claim 1, wherein the diamine component is further The step comprises a diamine compound having a side chain that causes the liquid crystal to vertically align. The liquid crystal alignment agent of claim 1, wherein the diamine compound represented by the formula [1] is 10 mol% to 80 mol% in the diamine component. The liquid crystal alignment agent of claim 4, wherein the diamine compound-based diamine component having a side chain in which the liquid crystal is vertically aligned is 5 to 70 mol%. A liquid crystal alignment film obtained by the liquid crystal alignment agent according to any one of claims 1 to 6. A liquid crystal display element characterized by comprising the liquid crystal alignment film of claim 7. a diamine compound characterized by the following formula [2]; (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]; (In the formula [3], A is selected from the group consisting of the following, and R ¹³ is a C 2 to 6 alkyl group) (wherein * indicates the bonding position with O, and ** indicates the bonding position with R ¹³ ). a diamine compound characterized by the following formula [4]; (In the formula [4], B is selected from the following, k is 0 to 1, l is an integer from 1 to 6, and m is 1 (however, when n is 0, m is also 0), n is 0~ 6 integer) (wherein * represents a bonding position with -(CH ₂ ) ₁ -, and ** represents a bonding position with O).