KR101831006B1 - Liquid crystal-aligning agent, liquid crysat-aligning film, liquid crystal display element and method for producing liquid crystal display elements - Google Patents

Abstract

A polyimide precursor having a side chain for vertically orienting a liquid crystal and a photoreactive side chain containing at least one selected from a methacryl group, an acrylic group, a vinyl group and a cinnamoyl group, A liquid crystal aligning agent having at least one polymer selected from the group consisting of polyimides obtained by condensation and a polymerizable compound each having a group capable of photopolymerizing or photo-crosslinking at two or more terminals and a solvent.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal alignment film, a liquid crystal alignment film, a liquid crystal alignment film, a liquid crystal alignment film, a liquid crystal alignment film, a liquid crystal alignment film,

The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, a liquid crystal display element, and a method for producing a liquid crystal display element which can be used for producing a liquid crystal display element of a vertical alignment type manufactured by irradiating ultraviolet rays while applying a voltage to liquid crystal molecules will be.

Among the liquid crystal display elements of the system (also referred to as a vertical alignment (VA) system) in which the liquid crystal molecules vertically aligned with respect to the substrate are caused to respond by an electric field, a process of irradiating ultraviolet rays while applying a voltage to the liquid crystal molecules .

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

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

It has been reported that the response speed of a liquid crystal display device is improved even when a photopolymerizable compound is added to a liquid crystal alignment film not in a liquid crystal composition (SC-PVA type liquid crystal display) (see, for example, Non-Patent Document 2).

Japanese Patent Application Laid-Open No. 2003-307720

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

However, it is desired to further increase the response speed of the liquid crystal display element. It is also conceivable to increase the response speed of the liquid crystal display element by increasing the addition amount of the photopolymerizable compound. However, when this photopolymerizable compound remains unreacted in the liquid crystal, it becomes an impurity and causes the reliability of the liquid crystal display element , A polymerizable compound capable of accelerating the response speed with a small addition amount is preferable.

Disclosure of the Invention The object of the present invention is to solve the above-mentioned problems of the prior art, and it is an object of the present invention to provide a liquid crystal aligning agent, a liquid crystal alignment film, a liquid crystal display element and a liquid crystal display element which can improve the response speed of a liquid crystal display element of a vertical alignment system And to provide a method.

The liquid crystal aligning agent of the present invention for solving the above-mentioned problems is a liquid crystal aligning agent which solves the above-mentioned problems. The liquid crystal aligning agent of the present invention is a liquid crystal aligning agent which has a side chain for vertically orienting a liquid crystal and a photoreactive side chain containing at least one selected from methacrylic group, acrylic group, vinyl group and cinnamoyl group At least one polymer selected from polyimides obtained by imidizing the polyimide precursor and a polymerizable compound each having a group capable of photopolymerizing or photo-crosslinking at two or more terminals and a polymer having a solvent .

It is preferable that the photoreactive side chain contains a group selected from the following formula (I).

[Chemical Formula 1]

(Wherein R < ¹¹ > is H or a methyl group)

It is preferable that the photopolymerization or photo-crosslinking group is selected from the following formula (II).

(2)

(Wherein R ¹² is H or an alkyl group having 1 to 4 carbon atoms, Z ¹ is a bivalent aromatic ring or heterocyclic ring which may be substituted with an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms, and Z ² is a monovalent aromatic ring or heterocyclic ring which may be substituted with an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms)

The liquid crystal alignment film of the present invention is characterized by being obtained by applying the above liquid crystal aligning agent to a substrate and firing.

The liquid crystal display element of the present invention is a liquid crystal display element comprising a liquid crystal cell manufactured by forming a liquid crystal layer by contacting a liquid crystal alignment film obtained by applying and firing the above liquid crystal aligning agent to a substrate and irradiating ultraviolet rays while applying a voltage to the liquid crystal layer .

The method for manufacturing a liquid crystal display element of the present invention is a method for manufacturing a liquid crystal display element comprising the steps of forming a liquid crystal layer by contacting the liquid crystal alignment layer obtained by applying the above liquid crystal aligning agent to a substrate and firing and irradiating ultraviolet rays while applying voltage to the liquid crystal layer, Is produced.

According to the present invention, it is possible to provide a liquid crystal display element of a vertical alignment system having a high response speed. In this liquid crystal aligning agent, even when the amount of the polymerizable compound to be added is small, the response speed can be sufficiently improved.

Hereinafter, the present invention will be described in detail.

The liquid crystal aligning agent of the present invention is a liquid crystal aligning agent comprising a side chain for vertically orienting a liquid crystal and a polyimide precursor having a photoreactive side chain containing at least one selected from the group consisting of methacryl group, acrylic group, vinyl group and cinnamoyl group , A polyimide obtained by imidizing the polyimide precursor, and a polymerizable compound each having a group capable of photopolymerizing or photo-crosslinking at two or more terminals, and a solvent. The liquid crystal aligning agent is a solution for producing a liquid crystal alignment film, and the liquid crystal alignment film is a film for aligning the liquid crystal in a predetermined direction, in the present invention, in the vertical direction.

First, the polymerizable compound contained in the liquid crystal aligning agent of the present invention will be described in detail. The liquid crystal aligning agent of the present invention contains a polymerizable compound each having a group capable of photopolymerizing or photo-crosslinking at two or more terminals. That is, the polymerizable compound contained in the liquid crystal aligning agent of the present invention is a compound having two or more terminals having a photopolymerizable or photo-crosslinkable group. Here, the polymerizable compound having a photopolymerizable group is a compound having a functional group which causes polymerization by irradiation of light. The compound having a photocrosslinking group is a compound having a photocrosslinking group that reacts with at least one polymer selected from a polymer of a polymerizable compound, a polyimide precursor, and a polyimide obtained by imidizing the polyimide precursor, And a functional group capable of crosslinking. The compound having a group capable of photo-crosslinking also reacts with the compound having a group capable of photo-crosslinking.

Such a polymerizable compound is specifically exemplified by a side chain for vertically orienting a liquid crystal to be described later and a side chain having a photoreactive side chain containing at least one selected from methacryl group, acrylic group, vinyl group and cinnamoyl group A polyimide precursor and a polyimide obtained by imidizing the polyimide precursor together with at least one kind of polymer in a liquid crystal aligning agent to prepare a liquid crystal display device of a vertical alignment type such as an SC-PVA type liquid crystal display It is possible to dramatically improve the response speed as compared with the case of using a polymer having a side chain and a photoreactive side chain that vertically align the liquid crystal and the polymerizable compound alone, It is possible to sufficiently improve the response speed even with an added amount.

The photopolymerization or photo-crosslinking group includes a monovalent group represented by the above formula (II).

Specific examples of the polymerizable compound include a compound having a group capable of photopolymerizing at each of two terminals as represented by the following formula (III), a compound having a group capable of photo-crosslinking with a terminal having a photopolymerizable group as shown by the following formula (IV) Compounds having a terminal group, and compounds having a group capable of photo-crosslinking at two terminals as shown by the following formula (V). Further, according to the following formula (Ⅲ) ~ (Ⅴ), R 12, Z 1 and Z ² are the same as R ^12, Z ¹ and Z ² in the formula (Ⅱ) and, Q ¹ is a divalent organic group to be. Q ¹ has a cyclic structure such as a phenylene group (-C ₆ H ₄ -), a biphenylene group (-C ₆ H ₄ -C ₆ H ₄ -) or a cyclohexylene group (-C ₆ H ₁₀ -) . This is because the interaction with the liquid crystal tends to become large.

(3)

[Chemical Formula 4]

[Chemical Formula 5]

Specific examples of the polymerizable compound represented by the formula (III) include a polymerizable compound represented by the following formula (1). In the following formula (1), V is a single bond or -R ¹ O-, R ¹ is a linear or branched alkylene group having 1 to 10 carbon atoms, preferably -R ¹ O- and R ¹ is a linear or branched alkylene group having 2 to 6 carbon atoms. W is a single bond or -OR ² -, R ² is a linear or branched alkylene group having 1 to 10 carbon atoms, preferably -OR ² -, and R ² is a linear or branched Is an alkylene group having 2 to 6 carbon atoms. V and W may have the same structure or different from each other, but if they are the same, synthesis is easy. Further, since the polymerizable compound represented by the following formula (1) is separately filed, it may be excluded from the present invention.

[Chemical Formula 6]

Since the polymerizable compound represented by the above formula (1) is a compound having a specific structure having an? -Methylene-? -Butyrolactone group as a polymerizable group (photopolymerizable group) at both terminals, the polymer has a rigid structure, Or at least one kind of polymer selected from a polyimide precursor and a polyimide obtained by imidizing the polyimide precursor is used as a material for a liquid crystal alignment film as shown in Examples to be described later The liquid crystal display device of the vertical alignment type, such as an SC-PVA type liquid crystal display, can be significantly improved in response speed. In general, a liquid crystal alignment film forming process includes a step of baking at a high temperature to completely remove the solvent, but a compound having a polymerizable group such as an acrylate group, a methacrylate group, a vinyl group, a vinyloxy group and an epoxy group The thermal stability is poor and it is difficult to withstand the firing at high temperature. On the other hand, the polymerizable compound represented by the above-mentioned formula (1) can withstand a structure having poor thermosetting property or can withstand a high temperature, for example, a firing temperature of 200 ° C or more.

Further, even when a polymerizable compound having an acrylate group or a methacrylate group other than an? -Methylene-? -Butyrolactone group as a photopolymerizable or photo-crosslinkable group is used, the acrylate group or the methacrylate group may also include a spacer such as an oxyalkylene group A polymerizable compound having a structure bonded to a phenylene group can remarkably improve the response speed particularly in the same manner as the polymerizable compound having an? -Methylene-? -Butyrolactone group at both terminals. A polymerizable compound having a structure in which an acrylate group or a methacrylate group is bonded to a phenylene group through a spacer such as an oxyalkylene group may be used for the purpose of improving the stability against heat, It can withstand temperatures well.

Among these polymerizable compounds, the compound represented by the following formula is a novel compound.

(7)

The method for producing such a polymerizable compound is not particularly limited and can be produced, for example, according to a synthesis example described later. For example, the polymerizable compound represented by the formula (1) can be synthesized by combining the techniques in organic synthetic chemistry. For example, SnCl ₂ can be used to synthesize 2- (bromomethyl) thiophene by the method proposed by Targa et al. In T. Talaaga, M. Schaeffer, C. Benezra and JL Stampf, Synthesis, ) Acrylic acid (2- (bromomethyl) propenoic acid) with an aldehyde or a ketone. Amberlyst 15 is a strongly acidic ion exchange resin manufactured by Rohm and Haas.

[Chemical Formula 8]

(Wherein R 'represents a monovalent organic group)

In addition, 2- (bromomethyl) acrylic acid can be prepared by a method disclosed in K. Ramarajan, K. Kamalingam, DJO Donnell and KDBerlin, Organic Synthesis, vol. 61, 56-59 (1983) . ≪ / RTI >

[Chemical Formula 9]

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

[Chemical formula 10]

(11)

In the case of synthesizing a polymerizable compound represented by the above formula (1) in which R ¹ and R ² are different from each other, a method represented by the following reaction formula can be mentioned.

[Chemical Formula 12]

In the case of synthesizing a polymerizable compound represented by the above formula (1) in which V and W are single bonds, the following reaction scheme can be mentioned.

[Chemical Formula 13]

The liquid crystal aligning agent of the present invention is a liquid crystal aligning agent having at least one kind selected from a polyimide precursor and a polyimide obtained by imidizing the polyimide precursor and having side chains for vertically aligning liquid crystals and side chains for light- Lt; / RTI > Examples of the polyimide precursor include polyamic acid (also referred to as polyamic acid), polyamic acid ester, and the like.

The side chain for vertically orienting the liquid crystal contained in the polymer is not limited as long as it is a structure capable of aligning the liquid crystal perpendicularly to the substrate. For example, the side chain may have a cyclic structure or branched structure Or a group in which a part or all of the hydrogen atoms of these groups are substituted with a fluorine atom, and the like. Of course, the liquid crystal may have two or more types of side chains for vertically orienting the liquid crystal. The side chain for orienting the liquid crystal vertically may be directly bonded to a polyimide precursor such as a polyamic acid or a polyamic acid ester, or a main chain of a polyimide, that is, a polyamic acid skeleton or a polyimide skeleton. Or may be interposed therebetween. Examples of the side chain for vertically orienting the liquid crystal include a hydrocarbon group having 8 to 30 carbon atoms, preferably 8 to 22 carbon atoms, in which the hydrogen atom may be substituted with fluorine, specifically, an alkyl group, a fluoroalkyl group, an alkenyl group , A phenethyl group, a styrylalkyl group, a naphthyl group, and a fluorophenylalkyl group. Examples of the side chain for vertically orienting other liquid crystals include those represented by the following formula (a).

[Chemical Formula 14]

(In the formula (a), l, m and n each independently represent an integer of 0 or 1, and R ³ represents an alkylene group having 2 to 6 carbon atoms, -O-, -COO-, -OCO-, -NHCO-, -CONH- or an alkylene-ether group having 1 to 3 carbon atoms; R ⁴ , R ⁵ and R ⁶ each independently represent a phenylene group or a cycloalkylene group; R ⁷ represents a hydrogen atom, an alkyl group having 2 to 24 carbon atoms Or a fluorine-containing alkyl group, a monovalent aromatic ring, a monovalent aliphatic ring, a monovalent heterocyclic ring, or a monovalent alicyclic substituent composed thereof)

R ³ in the formula (a) is preferably -O-, -COO-, -CONH-, or an alkylene-ether group having 1 to 3 carbon atoms, from the viewpoint of ease of synthesis.

R ⁴ , R ⁵ and R ⁶ in the formula (a) are preferably 1, m, n, R ⁴ , R ⁵ and R ⁶ shown in the following Table 1 from the viewpoints of ease of synthesis and ability to orient the liquid crystal vertically ⁶ is preferable.

And, l, if at least one is the one of m, n, expression (a) of R ⁷ is preferably a hydrogen atom or an alkyl group or a fluorine-containing alkyl group having 2 to 14, more preferably a hydrogen atom or a carbon atoms An alkyl group having 2 to 12 carbon atoms or a fluorine-containing alkyl group. When all of 1, m and n are 0, R ⁷ is preferably an alkyl group or a fluorine-containing alkyl group having 12 to 22 carbon atoms, a monovalent aromatic ring, a monovalent aliphatic ring, a monovalent heterocyclic ring, More preferably an alkyl group having 12 to 20 carbon atoms or a fluorine-containing alkyl group.

The amount of the side chain that vertically aligns the liquid crystal is not particularly limited as long as the liquid crystal alignment film can orient the liquid crystal vertically. However, in the liquid crystal display device having the liquid crystal alignment film, the abundance of the side chains for vertically orienting the liquid crystal within the range that does not hinder the display characteristics of the device, such as the voltage holding ratio and the accumulation of the residual DC voltage, .

In addition, the ability of a polymer having a side chain to vertically orient liquid crystals to orient liquid crystals vertically differs depending on the structure of side chains that vertically align liquid crystals. Generally, the side chains When the amount is large, the ability to vertically orient the liquid crystal is increased, and when it is decreased, it is decreased. In addition, when a cyclic structure is provided, the ability to vertically align the liquid crystal tends to be higher than in the case where the cyclic structure is not provided.

The polymer comprising at least one of polyimide precursor and polyimide such as polyamic acid and polyamic acid ester contained in the liquid crystal aligning agent of the present invention has a photoreactive side chain. The photoreactive side chain is a side chain having a functional group capable of forming a covalent bond by reaction with light such as ultraviolet (UV) (hereinafter, also referred to as a photoreactive group). In the present invention, And at least one member selected from the group consisting of a methacryl group, an acrylic group, a vinyl group and a cinnamoyl group as a genital group. As described above, when a polymer comprising at least one of a polyimide precursor and a polyimide such as polyamic acid and polyamic acid ester contained in a liquid crystal aligning agent is mixed with at least one selected from methacrylic group, acrylic group, vinyl group and cinnamoyl group As shown in the following Examples, it is possible to remarkably improve the response speed, as shown in Examples described later, by using the polymerizable compound together with the polymerizable compound in the liquid crystal aligning agent.

The photoreactive side chain may be directly bonded to the main chain of the polyimide precursor or polyimide, or may be bonded via a suitable bonding group. Examples of the side chains of photoreactive groups include those represented by the following formula (b).

[Chemical Formula 15]

(In the formula (b), R ⁸ represents a single bond or -CH ₂ -, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N _{(CH 3) -, -CON (} CH 3) -, -N (CH 3) indicates which of the CO-, R ⁹ Represents an alkylene group having 1 to 20 carbon atoms which is substituted by a single bond or an unsubstituted or fluorine atom, and -CH ₂ - of the alkylene group may be optionally substituted with -CF ₂ - or -CH = CH-, In the case where any of the groups shown below are not adjacent to each other, these groups may be substituted; -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, a divalent carbon ring, a divalent heterocyclic ring. R ¹⁰ represents a methacryl group, an acryl group, a vinyl group or a cinnamoyl group)

R ⁸ in the formula (b) may be formed by a conventional organic synthetic method. From the viewpoint of ease of synthesis, -CH ₂ -, -O-, -COO-, -NHCO-, -NH -, -CH ₂ O-.

Specific examples of the carbon ring or heterocyclic ring of the divalent carbon ring or the divalent heterocyclic ring substituting any -CH ₂ - in R ⁹ include, but are not limited to, the following structures .

[Chemical Formula 16]

R ¹⁰ is preferably a methacryl group, an acrylic group or a vinyl group from the viewpoint of photoreactivity.

The above formula (b) is more preferably a structure containing a group selected from the above formula (I).

The existing amount of the photoreactive side chain is preferably within a range capable of accelerating the response speed of the liquid crystal by reacting with ultraviolet light to form a covalent bond and in order to accelerate the response speed of the liquid crystal, As far as possible, it is preferable to have as much as possible.

A polyimide precursor having a side chain for vertically orienting the liquid crystal and a photoreactive side chain containing at least one selected from a methacryl group, an acrylic group, a vinyl group and a cinnamoyl group, and a polyimide precursor Is not particularly limited. For example, in a method of obtaining a polyamic acid by the reaction of a diamine and a tetracarboxylic acid dianhydride, a method in which a liquid crystal A tetracarboxylic acid dianhydride having a side chain for vertically orienting a liquid crystal, or a tetracarboxylic acid dianhydride having at least one selected from a methacryl group, an acrylic group, a vinyl group and a cinnamoyl group A diamine or methacryl group having a photoreactive side chain, an acrylic group, a vinyl group and a cinnamoyl group, And tetracarboxylic acid dianhydride having a photoreactive side chain containing one species may be copolymerized.

Examples of the diamine having a side chain that vertically aligns the liquid crystal include a long-chain alkyl group, a hydrocarbon group such as a group having a ring structure or branched structure or a steroid group in the middle of the long-chain alkyl group, or a part or all of hydrogen atoms in these groups A diamine having a group substituted with a fluorine atom as a side chain, for example, a diamine having a side chain represented by the above formula (a). More specifically, for example, a diamine having a hydrocarbon group of 8 to 30 carbon atoms in which a hydrogen atom may be substituted with fluorine, or a diamine represented by the following formulas (2), (3), (4) But the present invention is not limited thereto.

[Chemical Formula 17]

(1, m, n, and R ³ to R ⁷ in the formula (2) are the same as in the formula (a)

[Chemical Formula 18]

(In the formulas (3) and (4), A ₁₀ represents -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO- or -NH- , A ₁₁ represents a monovalent bond or a phenylene group, a represents the same structure as the side chain for vertically orienting the liquid crystal represented by the formula (a), and a 'represents the orientation of the liquid crystal represented by the formula (a) Represents a divalent group having a structure in which one element of hydrogen or the like is separated from the same structure as the side chain to be subjected to hydrogenation)

[Chemical Formula 19]

(In the formula (5), A ₁₄ is an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, A ₁₅ is a 1,4-cyclohexylene group or a 1,4-phenylene group, A ₁₆ is an oxygen atom , Or -COO- * (provided that the bonding hand to which " * " is bonded is bonded to A ₁₅ ), A ₁₇ represents an oxygen atom or -COO- * (CH ₂ ) a ₂ ), a ₁ is an integer of 0 or 1, a ₂ is an integer of 2 to 10, and a ₃ is an integer of 0 or 1)

The bonding position of two amino groups (-NH ₂ ) in the formula (2) is not limited. Specifically, examples of the bonding group of the side chain include positions 2, 3, 2, 4, 2, 5, 2, 6, 3, 4, 3, 5 on the benzene ring. Among them, 2, 4 position, 2, 5 position, or 3, 5 position is preferable from the viewpoint of reactivity when synthesizing polyamic acid. When the ease of synthesis of the diamine is also added, positions 2 and 4, or positions 3 and 5 are more preferable.

Specific examples of the formula (2) include diamines represented by the following formulas [A-1] to [A-24], but the present invention is not limited thereto.

[Chemical Formula 20]

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

[Chemical Formula 21]

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

[Chemical Formula 22]

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

(23)

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

≪ EMI ID =

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

(25)

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

(26)

Specific examples of the diamine represented by the formula (3) include diamines represented by the following formulas [A-25] to [A-30], but the present invention is not limited thereto.

(27)

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

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

(28)

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

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

The diamine having a side chain that vertically aligns the liquid crystal is preferably used in an amount of 5 to 50 mol% of the diamine component used in the synthesis of the polyamic acid, more preferably 10 to 40 mol% Mol% is a diamine having a side chain that vertically aligns the liquid crystal, and particularly preferably 15 to 30 mol%. The use of the diamine having a side chain for vertically orienting the liquid crystal in an amount of 5 to 50 mol% of the diamine component used for the synthesis of the polyamic acid is particularly excellent in terms of the response speed and the liquid crystal alignment immobilization ability.

Examples of the diamine having a photoreactive side chain containing at least one selected from a methacryl group, an acrylic group, a vinyl group and a cinnamoyl group include diamines having a side chain represented by the above formula (b) . More specifically, for example, diamines represented by the following general formula (6) can be mentioned, but the present invention is not limited thereto.

[Chemical Formula 29]

(Wherein R ⁸ , R ⁹ and R ^{10 in} the formula (6) are the same as in the formula (b)

The bonding position of two amino groups (-NH ₂ ) in the formula (6) is not limited. Specifically, examples of the bonding group of the side chain include positions 2, 3, 2, 4, 2, 5, 2, 6, 3, 4, 3, 5 on the benzene ring. Among them, 2, 4 position, 2, 5 position, or 3, 5 position is preferable from the viewpoint of reactivity when synthesizing polyamic acid. When the ease of synthesis of the diamine is also added, positions 2 and 4, or positions 3 and 5 are more preferable.

Specific examples of the diamine having a photoreactive side chain containing at least one member selected from a methacryl group, an acrylic group, a vinyl group and a cinnamoyl group include, but are not limited to, no.

(30)

(Wherein X ¹ and X ² are each independently a single bond or a bonding group selected from -O-, -COO-, -NHCO-, -NH-, and Y is a carbon number which is substituted by an unsubstituted or fluorine atom An alkylene group having 1 to 20 carbon atoms)

The diamine having a photoreactive side chain containing at least one selected from the methacryl group, the acrylic group, the vinyl group and the cinnamoyl group is preferably used as a liquid crystal alignment layer in a liquid crystal alignment property, a pretilt angle, One kind or two or more kinds of them may be mixed and used depending on characteristics such as charge and the like, response speed of the liquid crystal when the liquid crystal display element is used, and the like.

The diamine having a photoreactive side chain containing at least one selected from the methacryl group, the acrylic group, the vinyl group and the cinnamoyl group is preferably 10 to 70 moles of the diamine component used for the synthesis of the polyamic acid %, More preferably 20 to 60 mol%, and particularly preferably 30 to 50 mol%.

In addition, as long as the effect of the present invention is not impaired, the polyamic acid can be used in combination with other diamines other than the diamine having a photoreactive group, such as a diamine having a side chain that vertically aligns the liquid crystal have. Specific examples include p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m- , 4-dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, , 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diaminobiphenyl, 3,3'-dimethyl- 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'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3'- , 3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diamino Diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3,4'-diaminodiphenyl ether, Bis (4-aminophenyl) silane, dimethyl-bis (4-aminophenyl) silane, -Aminophenyl) silane, dimethyl-bis (3-aminophenyl) silane, 4,4'-thiodianiline, 3,3'- thiodianiline, 4,4'- diaminodiphenylamine, - diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl (4,4'-dia (3,3'-diaminodiphenyl) amine, N-methyl (3,4'-diaminodiphenyl) amine, N-methyl (2,2'-diaminodiphenyl) Phenyl) amine, N-methyl (2,3'-diaminodiphenyl) amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'- 1,4-diaminonaphthalene, 2,2'-diaminobenzophene , 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, Bis (4-aminophenyl) ethane, 1,2-bis (3-aminophenyl) ethane, 2,6-diaminonaphthalene, 2,6-diaminonaphthalene, Bis (4-aminophenyl) propane, 1,3-bis (3-aminophenyl) propane, ) Butane, bis (3,5-diethyl-4-aminophenyl) methane, 1,4-bis (4-aminophenoxy) benzene, (4-aminophenyl) benzene, 1,3-bis (4-aminophenoxy) benzene, 4,4 '- [1,4-phenylenebis (methylene)] dianiline, 4,4' - [ Phenylenebis (methylene)] dianiline, 3,3 '- [1,4-phenanthrene 1,4-phenylenebis [(4-aminophenyl) methanone], 1,4-phenylenebis (methylene)] dianiline, Phenylenebis [(3-aminophenyl) methanone], 1,3-phenylenebis [(4-aminophenyl) methanone] Phenylenebis (4-aminobenzoate), 1,4-phenylenebis (3-aminobenzoate), 1,3- (3-aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, bis , N, N '- (1,4-phenylene) bis (4-aminobenzamide) (4-aminobenzamide), N, N '- (1,3-phenylene) bis (3-aminobenzamide), N, N'- ) Terephthalamide, N, N'-bis (3-aminophenyl) terephthalate Bis (4-aminophenyl) isothiamides, N, N'-bis (3-aminophenyl) isophthalamide, 9,10- Bis [4- (4-aminophenoxy) phenyl] propane, 2,2'-bis [4- Bis (3-aminophenyl) hexafluoropropane, 2,2'-bis (3-aminophenyl) hexafluoropropane, 2,2'- Bis (3-aminophenyl) propane, 2,2'-bis (3-amino- Bis (4-aminophenoxy) propane, 1,3-bis (3-aminophenoxy) propane, Bis (4-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) Bis (4-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) Heptane, 1,7-bis (4-aminophenoxy) heptane, 1,8-bis (4-aminophenoxy) , 1,9-bis (3-aminophenoxy) nonane, 1,10- (4-aminophenoxy) 1,10- (3-aminophenoxy) decane, 1,11- (3-aminophenoxy) undecane, 1,12- Aromatic diamines such as bis (4-aminophenoxy) dodecane and 1,12- (3-aminophenoxy) dodecane, bis (4-aminocyclohexyl) ) Methane, alicyclic diamines such as 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, Aliphatic diamines such as 8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane.

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

The tetracarboxylic acid dianhydride to be reacted with the above diamine component in the synthesis of the polyamic acid is not particularly limited. Specific examples include pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-anthracene tetracarboxylic acid, 1,2,5,6-anthracene tetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,3,3 (3,4-dicarboxyphenyl) ether, 3,3 ', 4,4'-benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) Sulfone, bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2- (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5- (3,4-dicarboxyphenyl) pyridine, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid Acid, 1,3-diphenyl-1,2,3,4-cyclobutanetetracar Oxydipetetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexane Tetracarboxylic acid, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic acid, 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxyl Acid, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid, 1,2,3,4-cycloheptane tetracarboxylic acid, 2,3,4,5-tetrahydrofuran tetra Carboxylic acid, 3,4-dicarboxy-1-cyclohexylsuccinic acid, 2,3,5-tricarboxycyclopentylacetic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene Succinic acid, bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid, bicyclo [4,3,0] nonane-2,4,7,9-tetracarboxylic acid, Bicyclo [4,4,0] decane-2,4,7,9-tetracarboxylic acid, bicyclo [4,4,0] decane-2,4,8,10-tetracarboxylic acid, tricyclo [6.3.0.0 < 2,6 >] undecane-3,5,9,11-tetracarboxylic acid, 1,2 , 3,4-butanetetracarboxylic acid, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, Bicyclo [2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic acid, 5- (2,5-dioxotetrahydrofuryl) -3-methyl- Dicarboxylic acid, tetracyclo [6,2,1,1,0,2,7] dodeca-4,5,9,10-tetracarboxylic acid, 3,5,6-tri Carboxynorbornane-2: 3, 5: 6 dicarboxylic acid, and 1,2,4,5-cyclohexanetetracarboxylic acid. Of course, the tetracarboxylic acid dianhydride may be used alone or in combination of two or more, depending on the properties such as liquid crystal aligning property, voltage holding property, and accumulated charge when the liquid crystal alignment film is used.

When a polyamic acid is obtained by the reaction of the diamine component and the tetracarboxylic acid dianhydride, a known synthesis technique can be used. Generally, this is a method of reacting a diamine component and a tetracarboxylic acid dianhydride in an organic solvent. The reaction between the diamine component and the tetracarboxylic acid dianhydride is advantageous in that it proceeds relatively easily in an organic solvent and does not generate by-products.

The organic solvent used in the reaction is not particularly limited as long as it dissolves the produced polyamic acid. An organic solvent in which the polyamic acid is not dissolved may be mixed with the solvent in the range where the produced polyamic acid is not precipitated. Further, the water content in the organic solvent inhibits the polymerization reaction, and further causes the hydrolysis of the produced polyamic acid, so that the organic solvent is preferably dehydrated and dried. Examples of the organic solvent used in the reaction include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N-methylformamide, Pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide, N- But are not limited to, lactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethyl sulfoxide,? -Butyrolactone, isopropyl alcohol, methoxymethyl pentanol, dipentene, ethyl amyl ketone, , Methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol , Ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, Propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol, diethylene glycol mono Acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol Propylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, Diisobutylene, But are not limited to, ethyl acetate, butyl acetate, butyl acetate, butyl acetate, butyl acetate, butyl acetate, butyl acetate, butyl acetate, Propyleneglycol monoethyl ether, methyl pyruvate, methyl pyruvate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, methyl ethyl ketone, methyl lactate, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 2-ethyl-1-hexanol, and the like. These organic solvents may be used alone or in combination.

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

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

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

The method for synthesizing the polyamic acid to be used in the present invention is not limited to the above method. Instead of the above tetracarboxylic acid dianhydride, a tetracarboxylic acid or tetra The corresponding polyamic acid can also be obtained by reacting it with a known method using a tetracarboxylic acid derivative such as a carboxylic acid dihalide.

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

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

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

The polyamic acid ester can be produced by reacting a tetracarboxylic acid diester dichloride with a diamine in the same manner as in the synthesis of the polyamic acid or by reacting a diamine having the same structure as that of the tetracarboxylic acid diester with the polyamic acid in the presence of a suitable condensing agent or base And the like. Alternatively, a polyamic acid may be synthesized in advance by the above-mentioned method, and a carboxylic acid in the amic acid may be esterified using a polymer reaction. Specifically, for example, the tetracarboxylic acid diester dichloride and the diamine are reacted in the presence of a base and an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C for 30 minutes to 24 hours, And reacting for 1 hour to 4 hours, polyamic acid ester can be synthesized. The polyimide can also be obtained by heating the polyamic acid ester at a high temperature and promoting the alcohol to cause cyclization.

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

As described above, the liquid crystal aligning agent of the present invention comprises a side chain for vertically orienting a liquid crystal and a photoreactive side containing at least one selected from a methacryl group, an acrylic group, a vinyl group and a cinnamoyl group At least one polymer selected from a polyimide precursor having a chain and a polyimide obtained by imidizing the polyimide precursor and a polymerizable compound each having a group capable of photopolymerization or photo-crosslinking at two or more terminals, The content of the polymerizable compound each having a photopolymerizable or photocrosslinkable group at two or more terminals is not particularly limited, and the content of the polymerizable compound having a photopolymerizable group or a photocrosslinkable group at two or more terminals may be appropriately selected depending on the side chain for vertically orienting the liquid crystal and methacrylic group, A polyimide precursor having a photoreactive side chain containing at least one member selected from the group consisting of a polyimide precursor and a neomoyl group, Is preferably from 1 to 50 parts by mass, more preferably from 5 to 30 parts by mass, based on 100 parts by mass of at least one polymer selected from polyimides obtained by imidizing a polyimide. It is also possible to use a polyimide precursor having a side chain for vertically orienting the liquid crystal contained in the liquid crystal aligning agent and a photoreactive side chain containing at least one selected from the group consisting of methacryl group, acrylic group, vinyl group and cinnamoyl group , And the polyimide obtained by imidizing the polyimide precursor is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, and particularly preferably 1% by mass to 20% Is 3% by mass to 10% by mass.

Further, the liquid crystal aligning agent of the present invention is a liquid crystal aligning agent comprising a side chain for vertically orienting a liquid crystal and a polyisocyanate having a photoreactive side chain containing at least one selected from a methacryl group, an acryl group, a vinyl group and a cinnamoyl group And a polymer other than at least one kind of polymer selected from polyimides obtained by imidizing the polyimide precursor. At this time, the content of such another polymer in the entire polymer component is preferably 0.5% by mass to 15% by mass, and more preferably 1% by mass to 10% by mass.

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

The solvent to be contained in the liquid crystal aligning agent is not particularly limited and includes a side chain for vertically orienting the liquid crystal and a photoreactive side chain containing at least one selected from methacryl group, acryl group, vinyl group and cinnamoyl group And at least one polymer selected from polyimides obtained by imidizing the polyimide precursor and a polymerizable compound having a group capable of photopolymerizing or photo-crosslinking at two or more terminals, Or dispersible. For example, organic solvents as exemplified in the synthesis of the polyamic acid described above can be mentioned. Among them, N-methyl-2-pyrrolidone,? -Butyrolactone, N-ethyl-2-pyrrolidone, Dimethyl propanamide is preferable from the viewpoint of solubility. Of course, two or more types of mixed solvents may be used.

In addition, it is preferable to use a solvent which improves the uniformity and smoothness of the coating film in a solvent having high solubility of the component containing the liquid crystal aligning agent. Examples of the solvent that improves the uniformity and smoothness of the coating film include isopropyl alcohol, methoxymethyl pentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, butyl cell Propyleneglycol monobutylether, propyleneglycol monobutylether, propyleneglycol monoacetate, ethyleneglycol monobutylether, propyleneglycol monobutylether, propyleneglycol monoacetate, ethyleneglycol monobutylether, propyleneglycol monoacetate, Propylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl Ether, dipropylene glycol monoacetate monomethyl ether, 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- Propyl ether, diisobutyl ether, diisobutylene, amyl acetate, butyl butylate, butyl ether, diisobutyl ether, diisopropyl ether, diisopropyl ether, N-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol acetate Monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methylethyl 3-ethoxypropionate, 3- Methoxy-2-propanol, 1-ethoxy-2-propanol, 1-methoxypropionic acid, 3- 2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether- Ethyl lactate, n-butyl lactate, n-butyl lactate, isoamyl ester of lactic acid, 2-ethyl-1- (2-ethoxypropoxy) propanol, Hexanol, and the like. These solvents may be mixed with a plurality of kinds. When these solvents are used, it is preferably 5 to 80 mass%, more preferably 20 to 60 mass%, of the total solvent contained in the liquid crystal aligning agent.

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

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

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

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

By applying this liquid crystal aligning agent on the substrate and baking it, a liquid crystal alignment film for vertically aligning the liquid crystal can be formed. The liquid crystal aligning agent of the present invention is a liquid crystal aligning agent comprising a side chain for vertically orienting a liquid crystal and a polyimide precursor having a photoreactive side chain containing at least one selected from the group consisting of methacryl group, acrylic group, vinyl group and cinnamoyl group , And a polyimide obtained by imidizing the polyimide precursor together with a polymerizable compound each having a group capable of photopolymerizing or photo-crosslinking at two or more terminals. Therefore, the liquid crystal alignment layer obtained using the obtained liquid crystal alignment layer The response speed of the display element can be made fast.

For example, a cured film obtained by applying the liquid crystal aligning agent of the present invention to a substrate, drying it if necessary, and baking it may be used as a liquid crystal alignment film as it is. Alternatively, the cured film may be rubbed, irradiated with polarized light or light of a specific wavelength, treated with an ion beam or the like, or UV may be irradiated with a voltage applied to the liquid crystal display element after liquid crystal filling as the PSA orientation film . In particular, it is useful to use it as an alignment film for PSA.

In this case, the substrate to be used is not particularly limited as long as it is a substrate having high transparency and may be a glass plate, polycarbonate, poly (meth) acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, , Plastic substrates such as trimethylpentene, polyolefin, polyethylene terephthalate, (meth) acrylonitrile, triacetylcellulose, diacetylcellulose, and acetate butyrate cellulose can be used. It is preferable to use a substrate on which an ITO electrode or the like for liquid crystal driving is formed from the viewpoint of simplifying the process. In a reflection type liquid crystal display element, if it is only a substrate on one side, it can be used as opaque silicon wafer or the like. In this case, a material that reflects light such as aluminum can also be used.

The method of applying the liquid crystal aligning agent is not particularly limited, and examples thereof include a printing method such as screen printing, offset printing and flexographic printing, an ink jet method, a spray method, a roll coating method, a dip, a roll coater, a slit coater, have. From the viewpoint of productivity, the transfer printing method is widely used industrially and is preferably used in the present invention.

The coating film formed by applying the liquid crystal aligning agent by the above method can be fired to form a cured film. The drying step after the application of the liquid crystal aligning agent is not necessarily required, but it is preferable to carry out the drying step when the time from the application to the firing is not constant for each substrate, or when the firing is not performed immediately after application. This drying is not particularly limited as long as the solvent is removed to such an extent that the shape of the coated film is not deformed by conveyance of the substrate or the like. For example, a method of drying on a hot plate at a temperature of 40 ° C to 150 ° C, preferably 60 ° C to 100 ° C for 0.5 minutes to 30 minutes, preferably for 1 minute to 5 minutes.

The baking temperature of the coating film formed by applying the liquid crystal aligning agent is not particularly limited and may be, for example, at any temperature of 100 to 350 ° C, preferably 120 to 300 ° C, 250 ° C. The firing time can be fired at any time between 5 minutes and 240 minutes. Preferably 10 minutes to 90 minutes, and more preferably 20 minutes to 90 minutes. The heating can be carried out by a commonly known method, for example, a hot plate, a hot air circulation path, an infrared ray or the like.

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

The liquid crystal display element of the present invention can be obtained by forming a liquid crystal alignment film on a substrate by the above method, and then manufacturing a liquid crystal cell by a known method. Specific examples of the liquid crystal display element include a liquid crystal layer formed between the substrate and the liquid crystal layer, a liquid crystal layer formed between the substrate and the liquid crystal layer, and the liquid crystal alignment layer formed by the liquid crystal alignment agent of the present invention, Cell is a liquid crystal display element of a vertical alignment system. Specifically, a liquid crystal alignment film is formed by applying the liquid crystal aligning agent of the present invention on two substrates and firing, and two substrates are arranged so that the liquid crystal alignment films face each other. A liquid crystal layer And a liquid crystal cell which is manufactured by forming a liquid crystal layer by contacting with a liquid crystal alignment film and irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer. As described above, by using the liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention, ultraviolet rays are irradiated while applying voltage to the liquid crystal alignment film and the liquid crystal layer to polymerize the polymerizable compound, and the photo- , By reacting the polymerizable compound with the photoreactive side chain of the polymer, the orientation of the liquid crystal is more efficiently fixed, and the liquid crystal display element is remarkably excellent in the response speed.

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

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

In the case of a transmissive liquid crystal display element, it is common to use such a substrate. In a reflective liquid crystal display element, an opaque substrate such as a silicon wafer can be used as long as it is a substrate on only one side. At this time, a material such as aluminum that reflects light may be used for the electrode formed on the substrate.

The liquid crystal alignment film is formed by applying the liquid crystal aligning agent of the present invention on this substrate and then firing it, and the details are as described above.

The liquid crystal material constituting the liquid crystal layer of the liquid crystal display element of the present invention is not particularly limited and liquid crystal materials used in conventional vertical alignment methods such as MLC-6608 and MLC-6609 manufactured by Merck, Liquid crystal can be used.

As a method of sandwiching this liquid crystal layer between two substrates, known methods can be mentioned. For example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, spacers such as beads are dispersed on the liquid crystal alignment film of one substrate to make the side on the side where the liquid crystal alignment film is formed to be inward, And then the liquid crystal is injected under reduced pressure and sealed. A pair of substrates on which a liquid crystal alignment film is formed is prepared, a spacer such as a bead or the like is dispersed on a liquid crystal alignment film of one of the substrates, the liquid crystal is dropped, and then the side on the side where the liquid crystal alignment film is formed is made inward , The other one of the substrates is bonded to each other and sealing is performed. The thickness of the spacer at this time is preferably 1 to 30 占 퐉, more preferably 2 to 10 占 퐉.

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

As described above, when ultraviolet rays are irradiated while applying a voltage to the liquid crystal alignment film and the liquid crystal layer, the polymerizable compound reacts to form a polymer, and the direction in which the liquid crystal molecules are tilted by this polymer is stored, . When ultraviolet rays are irradiated while a voltage is applied to the liquid crystal alignment film and the liquid crystal layer, a side chain for vertically orienting the liquid crystal and a light containing at least one selected from a methacryl group, an acryl group, a vinyl group and a cinnamoyl group Reactive side chains of a polymer having at least one kind of polymer selected from a polyimide precursor having reactive side chains and a polyimide obtained by imidizing the polyimide precursor, The reaction speed of the obtained liquid crystal display element can be increased.

The liquid crystal aligning agent is not only useful as a liquid crystal aligning agent for producing a liquid crystal display element of a vertical alignment type such as a PSA type liquid crystal display or an SC-PVA type liquid crystal display, but also a liquid crystal aligning agent produced by rubbing treatment or photo- It is also possible to use it as a liquid crystal alignment film.

Example

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited at all by these examples.

<Polymerizable compound>

(Synthesis of polymerizable compound (RM1)

5.0 g (23.8 mmol) of 4,4'-biphenyldicarboxyaldehyde, 7.9 g (47.6 mmol) of 2- (bromomethyl) acrylic acid and 10% hydrochloric acid (aq) were placed in a 300 ml eggplant- , 100 ml of tetrahydrofuran (THF) and 9.5 g (50 mmol) of tin (II) chloride were added to the mixture, and the mixture was stirred and reacted at 70 DEG C for 20 hours. After completion of the reaction, the reaction solution was poured into 300 ml of pure water to obtain a white solid. The obtained solid was separated and purified by recrystallization (hexane / chloroform = 2/1) to obtain 3.5 g of a white solid. This solid was measured by NMR, and it was confirmed that this white solid was the polymerizable compound (RM1) shown in the objective reaction formula shown below. The yield was 72%.

(31)

(Synthesis of polymerizable compound (RM2)

In a 300 ml eggplant-shaped flask equipped with a cooling tube, 6.7 g (35.9 mmol) of 4,4'-biphenol, 15.0 g (71.7 mmol) of 2- (4-bromobutyl) 19.8 g (143 mmol) of potassium carbonate, and 150 ml of acetone were added to the mixture, and the mixture was reacted at 60 DEG C with stirring for 48 hours. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a yellow wet solid. Thereafter, this solid and 200 ml of water were mixed, and 80 ml of chloroform was added to extract. Extraction was carried out three times.

Anhydrous magnesium sulfate was added to the separated organic layer, followed by drying. After filtration, the solvent was distilled off under reduced pressure to obtain a yellow solid. This solid was recrystallized (hexane / chloroform = 4/1 (volume ratio)) to obtain 14.6 g of a white solid. The result of measurement of the obtained white solid by NMR is shown below. Further, the obtained solid was dissolved in deuterated chloroform (CDCl ₃ ) and measured at 300 MHz using a nuclear magnetic resonance apparatus (manufactured by Jiulsoz Co.). From this result, it was confirmed that this white solid was the compound (RM2-A) shown in the following reaction formula. The yield was 92%.

(32)

Next, 13.3 g (30 mmol) of the compound (RM2-A) obtained above, 11.6 g (70 mmol) of 2- (bromomethyl) acrylic acid and 10% aq), 160 ml of tetrahydrofuran (THF) and 13.2 g (70 mmol) of tin (II) chloride were added to the mixture, and the mixture was stirred and reacted at 70 DEG C for 20 hours. After completion of the reaction, the reaction solution was filtered under reduced pressure, mixed with 200 ml of pure water, and 100 ml of dichloroform was added thereto to extract. Extraction was carried out three times.

Anhydrous magnesium sulfate was added to the separated organic layer, followed by drying. The solvent was distilled off from the solution after filtration under reduced pressure to obtain a white solid. This solid was recrystallized (hexane / chloroform = 2/1) to obtain 9.4 g of a white solid. The obtained white solid was measured by NMR in the same manner as described above. As a result, it was confirmed that this white solid was the polymerizable compound (RM2) shown in the objective reaction formula shown below. The yield was 64%.

(33)

(Synthesis of polymerizable compound (RM3)

In a 500 ml eggplant-shaped flask equipped with a cooling tube, 11.2 g (60 mmol) of 4,4'-biphenol, 25.0 g (138 mmol) of 2- (2-bromoethyl) 35.9 g (260 mmol) of potassium carbonate, and 200 ml of acetone were added to the mixture, and the mixture was reacted at 60 DEG C for 48 hours with stirring. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a yellow wet solid. Thereafter, this solid was mixed with 200 ml of water, and 100 ml of chloroform was added to extract it. Extraction was carried out three times.

The organic layer separated was dried over anhydrous magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure to obtain a yellow solid. This solid was dissolved in chloroform and precipitated with hexane (hexane / chloroform = 2/1) to obtain 17.6 g of a white solid. The result of measurement of this solid by NMR is shown below. From this result, it was confirmed that this white solid was the compound (RM3-A) shown in the following reaction formula. The yield was 76%.

(34)

Next, 10.0 g (26 mmol) of the compound (RM3-A) obtained above, 10.0 g (60.6 mmol) of 2- (bromomethyl) acrylic acid, 10% aq), 140 ml of tetrahydrofuran (THF) and 11.4 g (60.6 mmol) of tin (II) chloride were added to the mixture, and the mixture was stirred and reacted at 70 ° C for 20 hours. After completion of the reaction, the reaction mixture was filtered under reduced pressure, mixed with 200 ml of pure water, and 100 ml of chloroform was added thereto to extract the mixture. Extraction was carried out three times.

Anhydrous magnesium sulfate was added to the extracted organic layer, followed by drying. The solvent was distilled off from the solution after filtration under reduced pressure to obtain a white solid. The solid was dissolved in chloroform and precipitated with hexane (hexane / chloroform = 2/1) to give a white solid. This solid was washed with methanol to obtain 4.7 g of a white solid. The result of measurement of this solid by NMR is shown below. From this result, it was confirmed that this white solid was the polymerizable compound (RM3) shown in the objective reaction formula shown below. The yield was 42%.

(35)

(Synthesis of polymerizable compound (RM4)

14.9 g (80.0 mmol) of biphenol, 35 g (167.0 mmol) of 5-bromopentyl acetate, 41.5 g (300 mmol) of potassium carbonate and 250 ml of acetone were added to a 500 ml eggplant- , And the mixture was reacted at 60 캜 for 48 hours with stirring. After completion of the reaction, the reaction solution was poured into 600 ml of pure water to obtain 33.6 g of a white solid. The result of measurement of this solid by NMR is shown below. From this result, it was confirmed that this white solid was the compound (RM4-A) shown in the following reaction formula. The yield was 95%.

(36)

18.0 g (41 mmol) of the compound (RM4-A) obtained above and 100 ml of a 10% sodium hydroxide aqueous solution were added to a 1 L flask equipped with a cooling tube, The reaction was carried out with stirring for a time. After completion of the reaction, 500 ml of water and a reaction solution were added to 1000 ml of the beaker, and the mixture was stirred at room temperature for 30 minutes. 80 ml of a 10% HCl aqueous solution was added dropwise thereto and filtrated to obtain 12.2 g of a white solid. The result of measurement of this solid by NMR is shown below. From this result, it was confirmed that this white solid was the compound (RM4-B) represented by the following reaction formula. The yield was 83%.

(37)

5.0 g (14.0 mmol) of the compound (RM4-B) obtained above was dissolved in 30 ml of THF together with 3.2 g of triethylamine and a small amount of 2,6-di-tert-butyl-p-cresol (BHT) , And a solution prepared by dissolving 3.3 g (32 mmol) of methacryloyl chloride in 20 ml of THF was added dropwise over 15 minutes under cooling with a water bath. After the dropwise addition, the mixture was stirred for 30 minutes, the water bath was removed, and stirring was continued overnight while returning to room temperature. After completion of the reaction, the reaction solution was poured into 200 ml of pure water and filtered to obtain a white solid. This solid was dissolved in chloroform and hexane (hexane / chloroform = 2/1) was precipitated to obtain 2.6 g of a white solid. The result of measurement of this solid by NMR is shown below. From this result, it was confirmed that the white solid was the polymerizable compound (RM4) shown in the following reaction formula. The yield was 38%.

(38)

(Polymerizable compound (RM5))

A known polymerizable compound represented by the following formula was defined as a polymerizable compound (RM5).

[Chemical Formula 39]

(Synthesis of polymerizable compound (RM6)

7.61 g (50.0 mmol) of methyl 4-hydroxybenzoate, 9.1 g (50.0 mmol) of 6-bromo-1-hexanol and 13.8 g (100 mmol) of potassium carbonate were added to a 200- , And acetone (70 ml) were added to the mixture, and the mixture was reacted at 64 占 폚 for 24 hours with stirring. After completion of the reaction, the reaction solution was filtered under reduced pressure, and the solvent was distilled off under reduced pressure to obtain a yellow wet solid. This solid was purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck, eluent: hexane / ethyl acetate = 1/1 (v / v)). The solvent was distilled off from the obtained solution to obtain 11.3 g of a white solid. The NMR measurement results of this solid are shown below. From this result, it was confirmed that this white solid was the compound (RM6-A) shown in the following reaction formula. The yield was 90%.

(40)

Next, 2.2 g (10.0 mmol) of pyridinium chlorochromate (PCC) and 10.0 g of CH ₂ Cl ₂ were added to a 100 ml three-necked flask equipped with a cooling tube (RM6-A) (2.5 g, 10.0 mmol) was dissolved in CH ₂ Cl ₂ And the mixture was further stirred at room temperature for 6 hours. Thereafter, 90 ml of diethyl ether was added to the solution from which the oily substance adhered to the wall of the flask was removed. After filtration under reduced pressure, the solvent was distilled off under reduced pressure to obtain a dark green wet solid. This solid was purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck, eluent: hexane / ethyl acetate = 2/1 (v / v)). The solvent of the obtained solution was distilled off to obtain 1.3 g of a colorless solid. The result of measurement of this solid by NMR is shown below. From this result, it was confirmed that this colorless solid was the compound (RM6-B) shown in the following reaction formula. The yield was 50%.

(41)

Next, a 50 ml eggplant-shaped flask equipped with a condenser tube was charged with 1.25 g (5.0 mmol) of the compound (RM6-B) obtained above, 0.83 g (5.0 mmol) of 2- (bromomethyl) acrylic acid, 0.8 g of 15 (trade name, manufactured by Rohm and Haas), 8.0 ml of THF, 0.95 g (5.0 mmol) of tin (II) chloride and 2.0 ml of pure water were added to the mixture and the mixture was reacted at 70 ° C for 5 hours with stirring. After completion of the reaction, the reaction mixture was filtered under reduced pressure, mixed with 40 ml of pure water, and 50 ml of diethyl ether was added thereto to extract the mixture. Extraction was carried out three times.

Anhydrous magnesium sulfate was added to the extracted organic layer, followed by drying. The solvent was distilled off from the solution after filtration under reduced pressure to obtain 1.5 g of a colorless solid. The NMR measurement results of this solid are shown below. From this result, it was confirmed that this colorless solid was the compound (RM6-C) shown in the following reaction formula. The yield was 94%.

(42)

35 ml of ethanol, 1.5 g (4.7 mmol) of the compound (RM6-C) obtained above and 5 ml of a 10% sodium hydroxide aqueous solution were added to a 100 ml eggplant-shaped flask equipped with a cooling tube, The reaction was carried out with stirring for a time. After completion of the reaction, 300 ml of water and a reaction solution were added to 500 ml of a beaker, and the mixture was stirred at room temperature for 30 minutes. 5 ml of a 10% aqueous solution of HCl was added dropwise and filtered to obtain 1.3 g of a white solid.

Next, 1.1 g of white solid obtained, 1.0 g of Amberlyst (registered trademark) 15 (Rohm &amp; Haas Co.) and 20.0 ml of THF were added to a 50 ml eggplant-shaped flask equipped with a cooling tube, The mixture was reacted with stirring for a period of time. After completion of the reaction, the reaction solution was filtered under reduced pressure, and the solvent was distilled off from the solution to obtain a yellow solid. This yellow solid was purified by recrystallization (hexane / ethyl acetate = 1/1 (v / v)) to obtain 0.9 g of a white solid. The NMR measurement results of this solid are shown below. From this result, it was confirmed that this white solid was the compound (RM6-D) represented by the following reaction formula. The yield was 71%.

(43)

, 21.1 g (69.3 mmol) of the compound (RM6-D) obtained above, 5.0 g (34.7 mmol) of 1,4-cyclohexanedimethanol, 0.35 g of N, N-dimethyl-4-aminopyridine Of BHT was suspended in 100 ml of methylene chloride while stirring at room temperature, 15.5 g (75.0 mmol) of dicyclohexylcarbodiimide (DCC) dissolved in 50 ml of methylene chloride was added, and the mixture was reacted for 48 hours with stirring . After completion of the reaction, the precipitated DCC urea was separated by filtration, and the filtrate was washed successively with 60 ml each of 0.5 N HCl, saturated aqueous sodium hydrogencarbonate solution and saturated brine twice, dried over magnesium sulfate, And recrystallized with ethanol to obtain 20.1 g of a polymerizable compound (RM6) shown in the following reaction formula. The results of measurement by NMR are shown below. The yield was 81%.

(44)

(Synthesis of polymerizable compound (RM7)

(20.0 mmol) of the compound (RM6-D) obtained by the above method, 5.3 g (20.0 mmol) of 4 - [(6-acryloxy) hexyloxy] phenol (SYNTHON Chemicals) -4-aminopyridine (DMAP) and a small amount of BHT were suspended in 100 ml of methylene chloride while stirring at room temperature, and 5.1 g (25.0 mmol) of dicyclohexylcarbodiimide (DCC) was dissolved therein The solution was added and stirred overnight. The precipitated DCC urea was separated by filtration, and the filtrate was washed with 100 ml of 0.5 N HCl, 100 ml of a saturated aqueous sodium hydrogencarbonate solution and 150 ml of saturated brine twice, successively, dried over magnesium sulfate, Removal yielded a yellow solid. This solid was purified by silica column chromatography (column: silica gel 60 0.063-0.200 mm, manufactured by Merck, eluent: hexane / ethyl acetate = 1/1). The solvent of the obtained solution was distilled off to obtain 4.3 g of a polymerizable compound (RM7) shown in the following reaction formula. The results of measurement by NMR are shown below. The yield was 39%.

[Chemical Formula 45]

(Synthesis of polymerizable compound (RM8)

(7.38 mmol) of the compound (RM8-A), 2.5 g (7.3 mmol) of the compound (RM8-B), 0.015 g of DMAP and a small amount of BHT were stirred at room temperature in 30 ml of methylene chloride, After 1.8 g (9.0 mmol) of DCC dissolved in 5 ml of methylene chloride was added thereto, the precipitated DCC urea was separated by filtration, and the filtrate was sequentially saturated with 50 ml of 0.5 N HCl Washed twice with an aqueous solution of sodium hydrogencarbonate and saturated brine, dried over magnesium sulfate, distilled off the solvent, and recrystallized from ethanol to obtain 1.3 g of a polymerizable compound (RM8) shown in the following reaction formula. The results of measurement by NMR are shown below. The yield was 30%.

(46)

(Synthesis of polymerizable compound (RM9)

6.1 g (50 mmol) of 4-hydroxybenzaldehyde, 9.1 g (50 mmol) of 6-bromo-1-hexanol and 13.8 g (100 mmol) of potassium carbonate were added to a 100 ml eggplant- And 100 ml of acetone were added to the mixture, and the mixture was reacted at 64 DEG C for 24 hours with stirring. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a yellow wet solid. Thereafter, this solid was mixed with 70 ml of water, and 50 ml of diethyl ether was added to extract it. Extraction was carried out three times.

The organic layer separated was dried over anhydrous magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure to obtain a yellow solid. This solid was dissolved in 5 ml of ethyl acetate and purified by column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck, eluent: hexane / ethyl acetate = 2/1). The solvent was distilled off from the obtained solution to obtain 7.4 g of a white solid. The result of measurement of this solid by NMR is shown below. From this result, it was confirmed that this white solid was the compound (RM9-A) shown in the following reaction formula. The yield was 67%.

(47)

2.2 g of the compound (RM9-A), 1.7 ml of triethylamine, 0.2 mg of BHT and 10 ml of THF were mixed and dissolved in a 50 ml three-necked flask. Under stirring the solution, a solution of 0.8 ml of acryloyl chloride dissolved in 10 ml of THF was added dropwise over 15 minutes. At that time, the three-necked flask was cooled by water bath (water temperature 20 캜). After the dropwise addition, the mixture was stirred for 30 minutes under the same condition, and then the flask was taken out of the water bath, replaced with nitrogen, and further reacted at room temperature for 3 hours with stirring. The reaction solution was filtered, the filtrate was concentrated to a volume of 3/4 under reduced pressure, and 100 ml of methylene chloride was added. This solution was washed with 100 ml of a saturated sodium carbonate solution, 100 ml of 0.5 N hydrochloric acid and 100 ml of saturated brine, dried over magnesium sulfate, and then the solvent was distilled off to obtain a yellow solid. This solid was dissolved in 3 ml of ethyl acetate and purified by column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck, eluent: hexane / ethyl acetate = 2/1). The solvent was distilled off from the obtained solution to obtain 2.0 g of a white solid. The result of measurement of this solid by NMR is shown below. From this result, it was confirmed that this white solid was the compound (RM9-B) shown in the following reaction formula. The yield was 72%.

(48)

Next, 2.0 g (7 mmol) of the intermediate compound (RM9-B) and 1.2 g (7.0 mmol) of 2- (bromomethyl) acrylic acid obtained in the same manner as above were added to a 50- , 1.4 g (7 mmol) of tin (II) chloride and 2.0 ml of pure water were added to the mixture, and the mixture was stirred at 70 ° C for 24 hours And reacted with stirring. After completion of the reaction, the reaction mixture was filtered under reduced pressure, mixed with 60 ml of pure water, and 50 ml of diethyl ether was added thereto to extract the mixture. Extraction was carried out three times. Anhydrous magnesium sulfate was added to the extracted organic layer, followed by drying. The solvent was distilled off from the solution after filtration under reduced pressure to obtain a pale brown solid.

This solid was dissolved in 3 ml of ethyl acetate and purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck, eluent: hexane / ethyl acetate = 2/1). The solvent was distilled off from the obtained solution to obtain 1.0 g of a white solid. This solid was measured by NMR, and it was confirmed that this white solid was a polymerizable compound (RM9) shown in the following reaction formula. The yield was 40%.

(49)

(Synthesis of polymerizable compound (RM10)

22.0 g (72.4 mmol) of the compound (RM6-D) obtained in the same manner as above, 5.0 g (36.2 mmol) of 1,4-phenyldimethanol and 0.35 g And a small amount of BHT were suspended in 100 ml of methylene chloride while stirring at room temperature, 17.0 g (80.0 mmol) of dicyclohexylcarbodiimide (DCC) dissolved in 50 ml of methylene chloride was added, and the mixture was stirred for 48 hours Lt; / RTI &gt; After completion of the reaction, the precipitated DCC urea was separated by filtration, and the filtrate was washed successively with 60 ml each of 0.5 N HCl and saturated aqueous sodium hydrogencarbonate solution and saturated brine twice, dried over magnesium sulfate, And recrystallized with ethanol to obtain 16.6 g of a polymerizable compound (RM10) shown in the following reaction formula. The results of measurement by NMR are shown below. The yield was 65%.

(50)

(Synthesis of polymerizable compound (RM11)

6.1 g (20.0 mmol) of the compound (RM6-D) obtained in the same manner as described above, 2.1 g (10.0 mmol) of 4,4'-biphenyl dimethanol, 0.15 g and a small amount of BHT were suspended in 50 ml of methylene chloride while stirring at room temperature, and 5.3 g (25.0 mmol) of dicyclohexylcarbodiimide (DCC) dissolved in 25 ml of methylene chloride was added thereto. And reacted with stirring. After completion of the reaction, the precipitated DCC urea was separated by filtration, and the filtrate was washed successively with 60 ml each of 0.5 N HCl and saturated aqueous sodium hydrogencarbonate solution and saturated brine twice, dried over magnesium sulfate, And recrystallized with ethanol to obtain 6.4 g of a polymerizable compound (RM11) shown in the following reaction formula. The results of measurement by NMR are shown below. The yield was 81%.

(51)

(Synthesis of polymerizable compound (RM12)

6.1 g (20.0 mmol) of the compound (RM6-D) obtained in the same manner as the above, 2.1 g (10.0 mmol) of 4,4'-dihydroxybenzophenone, ) And a small amount of BHT were suspended in 80 ml of methylene chloride while stirring at room temperature, and a solution of 5.2 g (24.0 mmol) of dicyclohexylcarbodiimide (DCC) dissolved therein was added thereto and stirred overnight . Precipitated DCC urea was separated by filtration, and the filtrate was washed twice with 50 ml of 0.5 N HCl, 50 ml of a saturated aqueous sodium hydrogen carbonate solution and 100 ml of saturated brine successively, dried over magnesium sulfate, Removal yielded a yellow solid. This solid was purified by recrystallization using ethanol to obtain 6.2 g of a white solid. The result of measurement of this solid by NMR is shown below. From this result, it was confirmed that this white solid was a polymerizable compound (RM12) shown in the following reaction formula. The yield was 79%.

(52)

(Synthesis of polymerizable compound (RM13)

12.2 g (100 mmol) of 4-hydroxybenzaldehyde, 12.2 g (50 mmol) of 1,6-dibromohexane and 16.0 g (116 mmol) of potassium carbonate were added to a 500 ml eggplant- 150 ml of acetone was added to the mixture, and the mixture was reacted at 64 ° C for 48 hours with stirring. After filtration of the reaction solution, the solvent was distilled off under reduced pressure to obtain 15.4 g of a pale brown wet solid. The result of measurement of this solid by NMR is shown below. From this result, it was confirmed that this solid was the compound (RM13-A) shown in the following reaction formula. The yield was 94%.

(53)

Next, 3.3 g (10.0 mmol) of the compound (RM13-A) obtained in the same manner as described above, 3.3 g (20.0 mmol) of 2- (bromomethyl) acrylic acid, 3.0 g of Amberlyst (registered trademark) 15 (product name of Rohm and Haas Company), 32.0 ml of THF, 3.8 g (20.0 mmol) of tin (II) chloride and 8.0 ml of pure water were added to the mixture and stirred at 70 ° C for 24 hours Lt; / RTI &gt; After completion of the reaction, the reaction solution was filtered under reduced pressure, mixed with pure water (60 ml), and thereto was added 70 ml of diethyl ether. Extraction was carried out three times. Anhydrous magnesium sulfate was added to the extracted organic layer, followed by drying. The solvent was distilled off from the solution after filtration under reduced pressure to obtain a pale brown solid.

This solid was dissolved in 10 ml of ethyl acetate and purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck, eluent: hexane / ethyl acetate = 1/1). The solvent was distilled off from the obtained solution to obtain 2.6 g of a white solid. The result of measurement of this solid by NMR is shown below. From this result, it was confirmed that this white solid was the polymerizable compound (RM13) shown in the following reaction formula. The yield was 55%.

(54)

(Synthesis of polymerizable compound (RM14)

7.5 g (50.0 mmol) of terephthalaldehyde acid, 9.1 g (55.0 mmol) of 2- (bromomethyl) acrylic acid, 80.0 ml of THF and 10.5 g of tin (II) chloride were added to a 300 ml eggplant- and 35.0 ml of an aqueous hydrochloric acid solution (10%) were added to the mixture, and the mixture was reacted at 70 ° C for 24 hours with stirring. After completion of the reaction, the mixture was mixed with 200 ml of pure water, and 100 ml of diethyl ether was added to the mixture. Extraction was carried out three times.

Anhydrous magnesium sulfate was added to the extracted organic layer, followed by drying. The solvent was distilled off from the solution after filtration under reduced pressure to obtain 8.3 g of a colorless solid. The NMR measurement results of this solid are shown below. From this result, it was confirmed that this colorless solid was the compound (RM14-A) shown in the following reaction formula. The yield was 76%.

(55)

0.05 g of N, N-dimethyl-4-aminopyridine (DMAP) and a small amount of BHT (DMF) were added to a solution of 2.4 g (11.0 mmol) of the compound (RM14- (10.0 mmol) of dicyclohexylcarbodiimide (DCC) dissolved in 5 ml of methylene chloride was added thereto, followed by stirring and reaction for 48 hours. After completion of the reaction, the precipitated DCC urea was separated by filtration, and the filtrate was washed successively with 60 ml each of 0.5 N HCl and saturated aqueous sodium hydrogencarbonate solution and saturated brine twice, dried over magnesium sulfate, And recrystallization with ethanol was carried out to obtain 1.3 g of a polymerizable compound (RM14) shown in the following reaction formula. The results of measurement by NMR are shown below. The yield was 50%.

(56)

(Synthesis of polymerizable compound (RM15)

6.2 g (28.7 mmol) of PCC and 100.0 ml of CH ₂ Cl ₂ were placed in a 300 ml three-necked flask equipped with a condenser and 8.0 g (28.7 m) of the compound (RM15-A) shown in the following reaction formula ㏖) in CH ₂ Cl ₂ (30.0 mL) was added dropwise, and the mixture was further stirred at room temperature for 2 hours. Thereafter, 150 ml of diethyl ether was added to the solution from which oily water adhered to the wall of the flask was removed, and the mixture was filtered under reduced pressure. The solvent was distilled off under reduced pressure to obtain a wet green solid.

This solid was purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck, eluent: hexane / ethyl acetate = 1/1). The solvent of the obtained solution was distilled off to obtain 5.7 g of a colorless solid. The result of measurement of this solid by NMR is shown below. From this result, it was confirmed that this colorless solid was the compound (RM15-B) shown in the following reaction formula. The yield was 72%.

(57)

Next, to a 100 ml eggplant-shaped flask equipped with a cooling tube was added 5.7 g (20.6 mmol) of the compound (RM15-B) obtained above, 3.4 g (20.6 mmol) of 2- (bromomethyl) acrylic acid, 16 ml of THF, 50 ml of THF, and 3.9 g (20.6 mmol) of tin (II) chloride were added to the mixture, and the mixture was reacted at 70 ° C for 20 hours with stirring. After completion of the reaction, the reaction solution was filtered under reduced pressure, mixed with 100 ml of pure water, and 150 ml of diethyl ether was added thereto for extraction. Extraction was carried out three times.

Anhydrous magnesium sulfate was added to the extracted organic layer, followed by drying. The solvent was distilled off from the solution after filtration under reduced pressure, and recrystallization (hexane / ethyl acetate, 1/1) was carried out to obtain 4.6 g of a colorless solid. The result of measurement of this solid by NMR is shown below. From this result, it was confirmed that this colorless solid was the polymerizable compound (RM15) shown in the following reaction formula. The yield was 65%.

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(Synthesis of polymerizable compound (RM16)

5.0 g (24.0 mmol) of 4-bromobutyl-1,3-dioxolane, 4.5 g (27.0 mmol) of 2- (bromomethyl) acrylic acid, and 10% hydrochloric acid were added to a 200 ml eggplant- 19 ml of an aqueous solution, 60 ml of THF and 4.7 g (27.0 mmol) of tin (II) chloride were added to the mixture, and the mixture was reacted at 70 ° C for 20 hours with stirring. After completion of the reaction, the reaction solution was filtered under reduced pressure, mixed with 100 ml of pure water, and thereto was added 100 ml of diethyl ether. Extraction was carried out three times.

Anhydrous magnesium sulfate was added to the extracted organic layer, followed by drying. The solvent was distilled off from the solution after filtration under reduced pressure to obtain 5.2 g of a colorless liquid. The result of measurement of this liquid by NMR is shown below. From this result, it was confirmed that this colorless liquid was the compound (RM16-A) represented by the following reaction formula. The yield was 93%.

[Chemical Formula 59]

4.7 g (20.0 mmol) of the compound (RM16-A) obtained above, 3.6 g (20.0 mmol) of 4-methoxy cinnamic acid and 5.1 g (40.0 mmol) of potassium carbonate were added to a 100 ml eggplant- And 50 ml of N, N-dimethylformamide (DMF) were added to the mixture, and the mixture was reacted at 110 DEG C for 48 hours with stirring. After completion of the reaction, the mixture was mixed with 200 ml of pure water, and 50 ml of ethyl acetate was added to the mixture. Extraction was carried out three times. Anhydrous magnesium sulfate was added to the extracted organic layer, dried, and the solvent was distilled off from the solution after filtration under reduced pressure to obtain a solid. This solid was dissolved in 10 ml of ethyl acetate and purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck, eluent: hexane / ethyl acetate = 1/1). The solvent was distilled off from the obtained solution to obtain 2.8 g of a white solid. The NMR measurement results of this solid are shown below. From this result, it was confirmed that this solid was a polymerizable compound (RM16) shown in the following reaction formula. The yield was 43%.

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(Synthesis of polymerizable compound (RM17)

9.4 g (45.0 mmol) of 4-bromobutyl-1,3-dioxolane, 10.0 g (45.0 mmol) of trans-4-phenyl cinnamic acid and 12.0 g of potassium carbonate were added to a 200 ml eggplant- 90.0 mmol), and DMF (100 mL) were added to the mixture, and the mixture was reacted at 110 DEG C for 48 hours with stirring. After completion of the reaction, 100 ml of pure water was mixed to obtain a solid. The solid was filtered, and 50 ml of ethanol was added to the mixture, followed by filtration. The solvent was distilled off from the solution after filtration under reduced pressure to obtain 6.2 g of a solid. The NMR measurement results of this solid are shown below. From this result, it was confirmed that this solid was the compound (RM17-A) represented by the following reaction formula. The yield was 40%.

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Next, to a 100 ml eggplant-shaped flask equipped with a cooling tube was added 6.2 g (18.0 mmol) of the compound (RM17-A) obtained above, 3.3 g (20.0 mmol) of 2- (bromomethyl) acrylic acid, 16 ml of THF, 32 ml of THF and 3.8 g (20.0 mmol) of tin (II) chloride were added to the mixture, and the mixture was reacted at 70 ° C for 20 hours with stirring. After completion of the reaction, the reaction mixture was mixed with pure water (100 ml), and thereto was added 50 ml of diethyl ether. Extraction was carried out three times.

The organic layer after the extraction was dried over anhydrous magnesium sulfate, and the solvent was distilled off from the solution after filtration under reduced pressure, and recrystallization (hexane / ethyl acetate, 2/1) was carried out to obtain 3.6 g of a solid. The result of measurement of this solid by NMR is shown below. From this result, it was confirmed that this solid was a polymerizable compound (RM17) shown in the following reaction formula. The yield was 53%.

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(Synthesis of polymerizable compound (RM18)

7.8 g (25.0 mmol) of the compound (RM6-D) obtained above, 4.8 g (25.0 mmol) of ethyl 4-hydroxycinnamate, 0.1 g of N, N-dimethyl- A small amount of BHT was suspended in 100 ml of methylene chloride while stirring at room temperature, and a solution of 6.7 g (32 mmol) of dicyclohexylcarbodiimide (DCC) dissolved therein was added thereto, followed by stirring overnight. Precipitated DCC urea was separated by filtration, and the filtrate was washed twice with 50 ml of 0.5 N HCl, 50 ml of a saturated aqueous sodium hydrogen carbonate solution and 100 ml of saturated brine successively, dried over magnesium sulfate, Removal yielded a yellow solid. This solid was purified by recrystallization using ethanol to obtain 7.1 g of a white solid. The result of measurement of this solid by NMR is shown below. From this result, it was confirmed that this white solid was a polymerizable compound (RM18) shown in the following reaction formula. The yield was 59%.

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(Synthesis of polymerizable compound (RM19)

7.3 g (24.0 mmol) of the compound (RM6-D) obtained above, 5.0 g (24.0 mmol) of methyl 4-hydroxy-3-methoxy cinnamate, ) And a small amount of BHT were suspended in 100 ml of methylene chloride while stirring at room temperature, and a solution of 6.4 g (31.0 mmol) of dicyclohexylcarbodiimide (DCC) dissolved therein was added thereto and stirred overnight . The precipitated DCC urea was separated by filtration, and the filtrate was washed with 100 ml of 0.5 N HCl, 100 ml of a saturated aqueous sodium hydrogencarbonate solution and 150 ml of saturated brine twice, successively, dried over magnesium sulfate, Removal yielded a yellow solid. This solid was purified by recrystallization (ethanol) to obtain 6.1 g of a polymerizable compound (RM19) shown in the following reaction formula. The results of measurement by NMR are shown below. The yield was 51%.

&Lt; EMI ID =

(Polymerizable compound (RM20))

A known polymerizable compound represented by the following formula was used as a polymerizable compound (RM20).

(65)

(Polymerizable compound (RM21))

A known polymerizable compound represented by the following formula was used as a polymerizable compound (RM21).

(66)

(Polymerizable compound (RM22))

A known polymerizable compound represented by the following formula was used as a polymerizable compound (RM22).

(67)

(Polymerizable compound (RM23))

A known polymerizable compound represented by the following formula was used as a polymerizable compound (RM23).

(68)

&Lt; Preparation of liquid crystal aligning agent &

The abbreviations used in the preparation of the following liquid crystal aligning agent are as follows.

BODA: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid dianhydride

CBDA: 1,2,3,4-Cyclobutane tetracarboxylic acid dianhydride

TCA: 2,3,5-tricarboxycyclopentylacetic acid-1,4: 2,3-2 anhydride represented by the following formula

(69)

m-PDA: m-Phenylenediamine

p-PDA: p-phenylenediamine

PCH: 1,3-diamino-4- [4- (4-heptylcyclohexyl) phenoxy] benzene

DA-1: 2- (methacryloyloxy) ethyl 3,5-diaminobenzoate represented by the following formula

(70)

DA-2: the formula N ^1, N ¹ represents the - diallyl benzene-1,2,4-triamine

(71)

DA-3: cholestanyl 3,5-diaminobenzoate represented by the following formula

(72)

NMP: N-methyl-2-pyrrolidone

BCS: butyl cellosolve

The conditions for measuring the molecular weight of the polyimide are as follows.

Apparatus: Room temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Scientific Corporation,

Column: Column (KD-803, KD-805) manufactured by Shodex Co.,

Column temperature: 50 ° C

Eluent: 30 mmol / l of lithium bromide · hydrate (LiBr · H ₂ O), 30 mmol / l of phosphoric anhydride crystal (o-phosphoric acid) as an additive, N, N'-dimethylformamide Furan (THF) of 10 ml / l)

Flow rate: 1.0 ml / min

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

The imidization rate of the polyimide was measured as follows. 20 mg of the polyimide powder was placed in an NMR sample tube (NMR sampling tube standard Φ 5 manufactured by Kusano Scientific Corporation), 1.0 ml of deuterated dimethyl sulfoxide (DMSO-d ₆ , 0.05% TMS mixture) was added, . This solution was subjected to proton NMR measurement at 500 MHz using an NMR measuring device (JNW-ECA500) manufactured by Nippon Denshoku. The proton derived from the structure in which the imidization rate does not change before and after the imidization is defined as the reference proton and the proton peak integration value derived from the NH group of the amic acid appearing in the vicinity of 9.5 to 10.0 ppm and the peak integrated value of this proton is used And was obtained by the following formula. In the following formula, x is the proton peak integration value derived from the NH group of the amic acid, y is the peak integrated value of the reference proton, and? Is the amount of the amic acid in the case where the polyamic acid (imidization ratio is 0% NH &lt; / RTI &gt; group.

Imidization ratio (%) = (1 -? X / y) x 100

(Example 1)

To a solution of BODA (6.01 g, 24.0 mmol), p-PDA (2.60 g, 24.0 mmol), PCH (6.85 g, 18.0 mmol) and DA-1 (4.76 g, 18.0 mmol) in NMP (81.5 g) After reacting at 80 DEG C for 5 hours, CBDA (6.94 g, 35.4 mmol) and NMP (27.2 g) were added and reacted at 40 DEG C for 10 hours to obtain a polyamic acid solution. NMP was added to the polyamic acid solution (135 g) to dilute to 6 mass%, acetic anhydride (18.3 g) and pyridine (23.6 g) were added as an imidization catalyst and reacted at 50 ° C for 3 hours. The reaction solution was poured into methanol (1700 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (A). The imidization ratio of the polyimide was 60%, the number average molecular weight was 12,000, and the weight average molecular weight was 39000.

NMP (74.0 g) was added to the resulting polyimide powder (A) (6.0 g), and the mixture was stirred and dissolved at 50 占 폚 for 12 hours. BCS (20.0 g) was added to this solution and stirred at 50 占 폚 for 5 hours to obtain liquid crystal aligning agent (B).

To 10.0 g of the liquid crystal aligning agent (B), 0.06 g (10% by mass based on the solid matter) of the polymerizable compound (RM1) obtained as described above was added and dissolved by stirring at room temperature for 3 hours to obtain a liquid crystal aligning agent B1 ) Was prepared.

(Example 2)

(10% by mass relative to solid content) of the polymerizable compound (RM2) obtained above was added to 10.0 g of the liquid crystal aligning agent (B), and the mixture was stirred and dissolved at room temperature for 3 hours to prepare a liquid crystal aligning agent (B2) .

(Example 3)

(10% by mass relative to solid content) of the polymerizable compound (RM3) obtained above was added to 10.0 g of the liquid crystal aligning agent (B) and dissolved by stirring at room temperature for 3 hours to prepare a liquid crystal aligning agent (B3) .

(Example 4)

(10% by mass relative to solid content) of the polymerizable compound (RM4) obtained above was added to 10.0 g of the liquid crystal aligning agent (B) and dissolved by stirring at room temperature for 3 hours to prepare a liquid crystal aligning agent (B4) .

(Example 5)

0.06 g (10% by mass relative to solid content) of the polymerizable compound (RM5) obtained above was added to 10.0 g of the liquid crystal aligning agent (B) and dissolved by stirring at room temperature for 3 hours to prepare a liquid crystal aligning agent (B5) .

(Comparative Example 1)

After dissolving BODA (4.38 g, 17.5 mmol), m-PDA (2.65 g, 24.5 mmol) and PCH (4.00 g, 10.5 mmol) in NMP (42.8 g) CBDA (3.22 g, 16.5 mmol) and NMP (14.2 g) were added and reacted at 40 ° C for 10 hours to obtain a polyamic acid solution. NMP was added to the polyamic acid solution (70.0 g) to dilute to 6 mass%, acetic anhydride (17.6 g) and pyridine (5.44 g) were added as an imidation catalyst and reacted at 100 ° C for 3 hours. The reaction solution was poured into methanol (900 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (C). The imidization ratio of the polyimide was 73%, the number average molecular weight was 15,000, and the weight average molecular weight was 47000.

NMP (74.0 g) was added to the obtained polyimide powder (C) (6.0 g), and the mixture was stirred at 50 캜 for 12 hours to dissolve. BCS (20.0 g) was added to this solution and stirred at 50 占 폚 for 5 hours to obtain a polyimide solution (D).

Further, 0.06 g (10% by mass relative to solid content) of the polymerizable compound (RM2) obtained above was added to 10.0 g of the polyimide solution (D) and dissolved by stirring at room temperature for 3 hours to obtain a liquid crystal aligning agent D1 Lt; / RTI &gt;

&Lt; Production of liquid crystal cell &

(Example 6)

Using the liquid crystal aligning agent (B1) obtained in Example 1, the liquid crystal cell was produced in the following order. The liquid crystal aligning agent (B1) obtained in Example 1 was spin-coated on the ITO surface of the ITO electrode substrate on which the ITO electrode pattern having the pixel size of 100 mu m x 300 mu m and the line / space of 5 mu m was formed, And then fired in a hot air circulating oven at 200 캜 for 30 minutes to form a liquid crystal alignment film having a thickness of 100 nm.

The liquid crystal aligning agent B1 was spin-coated on the ITO surface on which the electrode pattern had not been formed and dried on a hot plate at 80 DEG C for 90 seconds and then fired in a hot air circulating oven at 200 DEG C for 30 minutes, A liquid crystal alignment film having a thickness of 100 nm was formed.

A bead spacers of 6 mu m were dispersed on the liquid crystal alignment layers of one of the two substrates, and then a sealing agent (solvent type thermosetting type epoxy resin) was printed thereon. Subsequently, the side of the other substrate on which the liquid crystal alignment film was formed was set inward, and the resultant substrate was laminated with the preceding substrate, and then the sealant was cured to prepare an empty cell. A liquid crystal cell was prepared by injecting liquid crystal MLC-6608 (trade name, manufactured by Merck & Co., Inc.) into the empty cell by a low pressure injection method and performing Isotropic treatment (redistribution treatment of liquid crystal by heating) in an oven at 120 캜.

The response speed immediately after the production of the obtained liquid crystal cell was measured by the following method. Thereafter, in a state in which a voltage of 20 Vp-p was applied to the liquid crystal cell, UV rays having passed through a 313 nm band-pass filter were irradiated from the outside of the liquid crystal cell to 20 J. Thereafter, the response speed was again measured, and the response speeds before and after the UV irradiation were compared. Table 2 shows the results of the response speeds immediately after the preparation of the liquid crystal cell (initial) and after 20 J of UV irradiation (after UV 20 J).

How to measure the response speed

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

(Example 7)

The same operation as in Example 6 was carried out except that the firing temperature was changed from 200 캜 to 140 캜, and the response speeds before and after UV irradiation were compared.

(Example 8)

The same operation as in Example 6 was performed except that the liquid crystal aligning agent (B2) was used in place of the liquid crystal aligning agent (B1), and the response speeds before and after UV irradiation were compared.

(Example 9)

The same operation as in Example 8 was carried out except that the firing temperature was changed from 200 占 폚 to 140 占 폚, and the response speeds before and after UV irradiation were compared.

(Example 10)

The same operation as in Example 6 was performed except that the liquid crystal aligning agent (B3) was used instead of the liquid crystal aligning agent (B1), and the response speeds before and after UV irradiation were compared.

(Example 11)

The same operation as in Example 10 was carried out except that the firing temperature was changed from 200 캜 to 140 캜, and the response speeds before and after UV irradiation were compared.

(Example 12)

The same operation as in Example 6 was performed except that the liquid crystal aligning agent (B4) was used in place of the liquid crystal aligning agent (B1), and the response speeds before and after UV irradiation were compared.

(Example 13)

The same operation as in Example 12 was carried out except that the firing temperature was changed from 200 캜 to 140 캜, and the response speeds before and after UV irradiation were compared.

(Example 14)

The same operation as in Example 6 was carried out except that the liquid crystal aligning agent (B5) was used in place of the liquid crystal aligning agent (B1), and the response speeds before and after UV irradiation were compared.

(Example 15)

The same operation as in Example 14 was carried out except that the firing temperature was changed from 200 캜 to 140 캜, and the response speeds before and after UV irradiation were compared.

(Comparative Example 2)

The same operation as in Example 6 was performed except that the liquid crystal aligning agent (B) was used in place of the liquid crystal aligning agent (B1), and the response speeds before and after UV irradiation were compared.

(Comparative Example 3)

The same operation as in Comparative Example 2 was carried out except that the firing temperature was changed from 200 占 폚 to 140 占 폚, and the response speeds before and after UV irradiation were compared.

(Comparative Example 4)

The same operation as in Example 6 was performed except that the liquid crystal aligning agent (D1) was used in place of the liquid crystal aligning agent (B1), and the response speeds before and after UV irradiation were compared.

(Comparative Example 5)

The same operation as in Comparative Example 4 was carried out except that the firing temperature was changed from 200 캜 to 140 캜, and the response speeds before and after UV irradiation were compared.

As a result, as shown in Table 2, the photoreactive side chain containing the methacryl group and the polymer (polyimide) having the side chains for vertically orienting the liquid crystal and the liquid crystal aligning agent containing the polymerizable compound 6 to 15 show comparative examples 4 and 5 using a liquid crystal aligning agent containing a polymerizable compound but not containing a polymer having a photoreactive side chain, photoreactive side chains containing methacrylic group and liquid crystal vertically The rate of improvement in the response speed before and after ultraviolet irradiation was remarkably higher than that in Comparative Examples 2 and 3 using the liquid crystal aligning agent B containing a polymer (polyimide) having oriented side chains and no polymerizable compound.

Therefore, by using a polymer having a photoreactive side chain containing a methacryl group and a side chain for vertically orienting a liquid crystal and a liquid crystal aligning agent using a polymerizable compound in combination, it is possible to dramatically improve the response speed And it was confirmed that the response speed can be sufficiently improved even with a small addition amount of the polymerizable compound.

In Examples 6 to 11 using a liquid crystal aligning agent containing a polymerizable compound having an? -Methylene-? -Butyrolactone group, which is a polymerizable group at both ends, in Examples 6 to 11, a methacrylate group In Examples 12 to 13 in which a liquid crystal aligning agent containing a polymerizable compound having a structure bonded to a phenylene group via a giba-oxyalkylene group was used (200 DEG C) even at a low firing temperature (140 DEG C) The response speed was dramatically improved.

On the other hand, in Examples 14 to 15 in which a liquid crystal aligning agent having a methacrylate group and having a methacrylate group directly bonded to a phenylene group was used, Respectively. In Examples 6 to 7 in which polymerizable compounds differing from the polymerizable compounds used in Examples 14 to 15 were used, the dependence of the firing temperature on the firing temperature was hardly observed, so that the carbon atoms bonded to the methacrylic groups were in the sp ³ hybrid orbit It is presumed that the thermal stability of the polymerizable compound is improved and the dependence of the response speed improvement rate on the firing temperature is reduced.

(Example 16)

(10% by mass relative to solid content) of the polymerizable compound (RM6) obtained above was added to 10.0 g of the liquid crystal aligning agent (B), and the mixture was stirred and dissolved at room temperature for 3 hours to prepare a liquid crystal aligning agent (B6) .

(Example 17)

(10% by mass relative to solid content) of the polymerizable compound (RM7) obtained above was added to 10.0 g of the liquid crystal aligning agent (B), and the resulting mixture was stirred and dissolved at room temperature for 3 hours to prepare a liquid crystal aligning agent (B7) .

(Example 18)

(10% by mass relative to solid content) of the polymerizable compound (RM8) obtained above was added to 10.0 g of the liquid crystal aligning agent (B) and dissolved by stirring at room temperature for 3 hours to prepare a liquid crystal aligning agent (B8) .

(Example 19)

(10% by mass relative to solid content) of the polymerizable compound (RM9) obtained above was added to 10.0 g of the liquid crystal aligning agent (B), and the mixture was stirred and dissolved at room temperature for 3 hours to prepare a liquid crystal aligning agent (B9) .

(Example 20)

(10% by mass relative to solid content) of the polymerizable compound (RM10) obtained above was added to 10.0 g of the liquid crystal aligning agent (B), and the mixture was stirred and dissolved at room temperature for 3 hours to prepare a liquid crystal aligning agent (B10) .

(Example 21)

(10% by mass relative to solid content) of the polymerizable compound (RM11) obtained above was added to 10.0 g of the liquid crystal aligning agent (B) and dissolved by stirring at room temperature for 3 hours to prepare a liquid crystal aligning agent (B11) .

(Example 22)

(10% by mass relative to solid content) of the polymerizable compound (RM12) obtained above was added to 10.0 g of the liquid crystal aligning agent (B) and dissolved by stirring at room temperature for 3 hours to prepare a liquid crystal aligning agent (B12) .

(Example 23)

(10% by mass relative to solid content) of the polymerizable compound (RM13) obtained above was added to 10.0 g of the liquid crystal aligning agent (B) and dissolved by stirring at room temperature for 3 hours to prepare a liquid crystal aligning agent (B13) .

(Example 24)

(10% by mass relative to solid content) of the polymerizable compound (RM14) obtained above was added to 10.0 g of the liquid crystal aligning agent (B) and dissolved by stirring at room temperature for 3 hours to prepare a liquid crystal aligning agent (B14) .

(Example 25)

(10% by mass relative to solid content) of the polymerizable compound (RM15) obtained above was added to 10.0 g of the liquid crystal aligning agent (B) and dissolved by stirring at room temperature for 3 hours to prepare a liquid crystal aligning agent (B15) .

(Example 26)

(10% by mass relative to solid content) of the polymerizable compound (RM16) obtained above was added to 10.0 g of the liquid crystal aligning agent (B), and the mixture was stirred and dissolved at room temperature for 3 hours to prepare a liquid crystal aligning agent (B16) .

(Example 27)

(10% by mass relative to solid content) of the polymerizable compound (RM17) obtained above was added to 10.0 g of the liquid crystal aligning agent (B) and dissolved by stirring at room temperature for 3 hours to prepare a liquid crystal aligning agent (B17) .

(Example 28)

(10% by mass relative to solid content) of the polymerizable compound (RM18) obtained above was added to 10.0 g of the liquid crystal aligning agent (B), and the resulting mixture was stirred and dissolved at room temperature for 3 hours to prepare a liquid crystal aligning agent (B18) .

(Example 29)

(10% by mass relative to solid content) of the polymerizable compound (RM19) obtained above was added to 10.0 g of the liquid crystal aligning agent (B) and dissolved by stirring at room temperature for 3 hours to prepare a liquid crystal aligning agent (B19) .

(Example 30)

(10% by mass relative to solid content) of the polymerizable compound (RM20) obtained above was added to 10.0 g of the liquid crystal aligning agent (B) and dissolved by stirring at room temperature for 3 hours to prepare a liquid crystal aligning agent (B20) .

(Example 31)

(10% by mass relative to solid content) of the polymerizable compound (RM21) obtained above was added to 10.0 g of the liquid crystal aligning agent (B), and the resulting mixture was stirred and dissolved at room temperature for 3 hours to prepare a liquid crystal aligning agent (B21) .

(Example 32)

(10% by mass relative to solid content) of the polymerizable compound (RM22) obtained above was added to 10.0 g of the liquid crystal aligning agent (B) and dissolved by stirring at room temperature for 3 hours to prepare a liquid crystal aligning agent (B22) .

(Example 33)

0.06 g (10% by mass relative to solid content) of the polymerizable compound (RM23) obtained above was added to 10.0 g of the liquid crystal aligning agent (B) and dissolved by stirring at room temperature for 3 hours to prepare a liquid crystal aligning agent (B23) .

(Example 34)

The same operation as in Example 6 was performed except that the liquid crystal aligning agent (B6) was used in place of the liquid crystal aligning agent (B1), and the response speeds before and after UV irradiation were compared.

(Example 35)

The same operation as in Example 6 was performed except that the liquid crystal aligning agent (B7) was used in place of the liquid crystal aligning agent (B1), and the response speeds before and after UV irradiation were compared.

(Example 36)

The same operation as in Example 6 was carried out except that the liquid crystal aligning agent (B8) was used in place of the liquid crystal aligning agent (B1), and the response speeds before and after UV irradiation were compared.

(Example 37)

The same operation as in Example 6 was performed except that the liquid crystal aligning agent (B9) was used in place of the liquid crystal aligning agent (B1), and the response speeds before and after UV irradiation were compared.

(Example 38)

The same operation as in Example 6 was performed except that the liquid crystal aligning agent (B10) was used in place of the liquid crystal aligning agent (B1), and the response speeds before and after UV irradiation were compared.

(Example 39)

The same operation as in Example 6 was performed except that the liquid crystal aligning agent (B11) was used in place of the liquid crystal aligning agent (B1), and the response speeds before and after UV irradiation were compared.

(Example 40)

The same operation as in Example 6 was carried out except that the liquid crystal aligning agent (B12) was used instead of the liquid crystal aligning agent (B1), and the response speeds before and after UV irradiation were compared.

(Example 41)

The same operation as in Example 6 was performed except that the liquid crystal aligning agent (B13) was used in place of the liquid crystal aligning agent (B1), and the response speeds before and after UV irradiation were compared.

(Example 42)

The same operation as in Example 6 was performed except that the liquid crystal aligning agent (B14) was used in place of the liquid crystal aligning agent (B1), and the response speeds before and after UV irradiation were compared.

(Example 43)

The same operation as in Example 6 was carried out except that the liquid crystal aligning agent (B15) was used in place of the liquid crystal aligning agent (B1), and the response speeds before and after UV irradiation were compared.

(Example 44)

The same operation as in Example 6 was performed except that the liquid crystal aligning agent (B16) was used in place of the liquid crystal aligning agent (B1), and the response speeds before and after UV irradiation were compared.

(Example 45)

The same operation as in Example 6 was carried out except that the liquid crystal aligning agent (B17) was used in place of the liquid crystal aligning agent (B1), and the response speeds before and after UV irradiation were compared.

(Example 46)

The same operation as in Example 6 was performed except that the liquid crystal aligning agent (B18) was used in place of the liquid crystal aligning agent (B1), and the response speeds before and after UV irradiation were compared.

(Example 47)

The same operation as in Example 6 was performed except that the liquid crystal aligning agent (B19) was used in place of the liquid crystal aligning agent (B1), and the response speeds before and after UV irradiation were compared.

(Example 48)

The same operation as in Example 6 was performed except that the liquid crystal aligning agent (B20) was used in place of the liquid crystal aligning agent (B1), and the response speeds before and after UV irradiation were compared.

(Example 49)

The same operation as in Example 6 was performed except that the liquid crystal aligning agent (B21) was used in place of the liquid crystal aligning agent (B1), and the response speeds before and after UV irradiation were compared.

(Example 50)

The same operation as in Example 6 was carried out except that the liquid crystal aligning agent (B22) was used in place of the liquid crystal aligning agent (B1), and the response speeds before and after UV irradiation were compared.

(Example 51)

The same operation as in Example 6 was performed except that the liquid crystal aligning agent (B23) was used in place of the liquid crystal aligning agent (B1), and the response speeds before and after UV irradiation were compared.

(Example 52)

DA-3 (3.14 g, 6.0 mmol), DA-1 (3.17 g, 12.0 mmol) was added to NMP (41.6 g, 12.0 mmol), TCA (3.36 g, 15.0 mmol), p- ), And reacted at 60 ° C for 5 hours. Then, CBDA (2.88 g, 14.7 mmol) and NMP (13.9 g) were added and reacted at 40 ° C for 10 hours to obtain a polyamic acid solution. NMP was added to the polyamic acid solution (68 g) to dilute to 6 mass%, acetic anhydride (6.0 g) and pyridine (11.7 g) were added as imidation catalysts and reacted at 50 ° C for 3 hours. The reaction solution was poured into methanol (850 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (E). The imidization ratio of the polyimide was 50%, the number average molecular weight was 18,000, and the weight average molecular weight was 58,000.

NMP (74.0 g) was added to the obtained polyimide powder (E) (6.0 g), and the mixture was stirred at 50 캜 for 12 hours to dissolve. BCS (20.0 g) was added to this solution and stirred at 50 占 폚 for 5 hours to obtain a liquid crystal aligning agent (F).

Further, 0.06 g (10 wt% based on solid matter) of RM2 was added to 10.0 g of the above liquid crystal aligning agent (F), and the mixture was stirred and dissolved at room temperature for 3 hours to prepare liquid crystal aligning agent (F1).

Further, 0.06 g (10 wt% based on solid content) of RM4 was added to 10.0 g of the above liquid crystal aligning agent (F) and dissolved with stirring at room temperature for 3 hours to prepare liquid crystal aligning agent (F2).

(Example 53)

The same operation as in Example 6 was performed except that the liquid crystal aligning agent (F1) was used in place of the liquid crystal aligning agent (B1), and the response speeds before and after UV irradiation were compared.

(Example 54)

The same operation as in Example 6 was carried out except that the liquid crystal aligning agent (F2) was used in place of the liquid crystal aligning agent (B1), and the response speeds before and after UV irradiation were compared.

(Example 55)

2 (4.88 g, 24.0 mmol) was added to a solution of BODA (5.00 g, 20.0 mmol), p-PDA (0.87 g, 8.0 mmol), PCH (3.04 g, 8.0 mmol) After the mixture was reacted at 80 ° C for 5 hours, CBDA (3.77 g, 19.2 mmol) and NMP (17.56 g) were added and reacted at 40 ° C for 10 hours to obtain a polyamic acid solution. NMP was added to the polyamic acid solution (75 g) to dilute to 6 mass%, acetic anhydride (8.7 g) and pyridine (13.5 g) were added as imidation catalysts and reacted at 50 ° C for 3 hours. The reaction solution was poured into methanol (950 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (G). The imidization ratio of the polyimide was 50%, the number average molecular weight was 20,000, and the weight average molecular weight was 86,000.

NMP (74.0 g) was added to the obtained polyimide powder (G) (6.0 g), and the mixture was stirred and dissolved at 50 占 폚 for 12 hours. BCS (20.0 g) was added to this solution and stirred at 50 占 폚 for 5 hours to obtain liquid crystal aligning agent (G1).

To 10.0 g of the above liquid crystal aligning agent (G1), 0.06 g (10% by mass relative to solid content) of a polymerizable compound RM2 was added and dissolved with stirring at room temperature for 3 hours to prepare a liquid crystal aligning agent (G2).

(Example 56)

The same operation as in Example 6 was performed except that the liquid crystal aligning agent (G2) was used in place of the liquid crystal aligning agent (B1), and the response speeds before and after UV irradiation were compared.

The results of Examples 34 to 51, 53, 54 and 56 are shown in Table 3. As shown in Table 3, the light-reactive side chain containing a methacryl group and the like and the liquid crystal aligning agent containing a polymer (polyimide) having a side chain for vertically orienting the liquid crystal and a polymerizable compound were used in Example 34 To 51, 53, 54 and 56 were different from the polymerizable compound and the polymer, respectively, but the improvement rate of the response speed before and after irradiation with ultraviolet light was remarkably high as in Examples 6 to 15.

Claims (6)

A polyimide precursor having a side chain for vertically orienting a liquid crystal and a photoreactive side chain containing at least one selected from a methacryl group, an acrylic group, a vinyl group and a cinnamoyl group, A liquid crystal aligning agent having at least one kind of polymer selected from polyimide obtained by curing and a polymerizable compound each having a photopolymerizable or photo crosslinking group at two or more terminals and a solvent. The method according to claim 1,
Wherein the side chain of the photoreactive group contains a group selected from the following formula (I).

(Wherein R &lt; ¹¹ &gt; is H or a methyl group) The method according to claim 1,
Wherein the photopolymerizable or photo-crosslinkable group is selected from the following formula (II).

(Wherein R ¹² is H or an alkyl group having 1 to 4 carbon atoms, Z ¹ is a bivalent aromatic ring or heterocyclic ring which may be substituted with an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms, and Z ² is a monovalent aromatic ring or heterocyclic ring which may be substituted with an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms) A liquid crystal alignment film obtained by applying the liquid crystal aligning agent according to any one of claims 1 to 3 to a substrate and firing the liquid crystal aligning agent. A liquid crystal alignment layer according to any one of claims 1 to 3, which is applied to a substrate and fired, is brought into contact with a liquid crystal alignment film to form a liquid crystal layer, and a liquid crystal layer A liquid crystal layer disposed between the first electrode and the second electrode; A liquid crystal alignment layer according to any one of claims 1 to 3, which is obtained by applying a liquid crystal aligning agent to a substrate and firing the liquid crystal alignment layer, is brought into contact with the liquid crystal alignment layer to form a liquid crystal layer. While applying a voltage to the liquid crystal layer, Wherein the liquid crystal display element is a liquid crystal display element.