JPWO2012002511A1 - Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, and method for manufacturing liquid crystal display element - Google Patents

Abstract

A polyimide precursor having a side chain for vertically aligning a liquid crystal and a photoreactive side chain containing at least one selected from a methacryl group, an acryl group, a vinyl group, and a cinnamoyl group, and the polyimide precursor as an imide Liquid crystal aligning agent which has at least 1 type of polymer selected from the polyimide obtained by making it, the polymeric compound which respectively has the group which photopolymerizes or photocrosslinks in two or more terminal, and a solvent.

Description

  The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, a liquid crystal display element, and a liquid crystal display element that can be used in the manufacture of a liquid crystal display element of a vertical alignment method that is manufactured by irradiating ultraviolet rays with voltage applied to liquid crystal molecules. It relates to a manufacturing method.

  In a liquid crystal display element of a method in which liquid crystal molecules aligned perpendicular to a substrate are responded by an electric field (also referred to as a vertical alignment (VA) method), an ultraviolet ray is applied while applying a voltage to the liquid crystal molecules in the manufacturing process. There is a thing including the process of irradiating.

  In such a vertical alignment type liquid crystal display element, a photopolymerizable compound is added to a liquid crystal composition in advance and used together with a vertical alignment film such as polyimide to irradiate ultraviolet rays while applying a voltage to a liquid crystal cell. A technique for increasing the response speed of liquid crystal (see, for example, Patent Document 1 and Non-Patent Document 1) is known (PSA (Polymer sustained Alignment) type liquid crystal display). Usually, the direction in which the liquid crystal molecules tilt in response to an electric field is controlled by protrusions provided on the substrate or slits provided on the display electrode, but a liquid crystal composition is added with a photopolymerizable compound. By irradiating ultraviolet rays while applying voltage to the cell, a polymer structure in which the tilted direction of the liquid crystal molecules is memorized is formed on the liquid crystal alignment film. It is said that the response speed of the liquid crystal display element is faster than the control method.

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

  Here, it has been reported that the response speed of the liquid crystal display element is increased by adding the photopolymerizable compound to the liquid crystal alignment film instead of the liquid crystal composition (SC-PVA liquid crystal display) (for example, Non-Patent Document 2).

JP 2003-307720 A

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

  However, it is desired to further increase the response speed of the liquid crystal display element. Although it is conceivable to increase the response speed of the liquid crystal display element by increasing the amount of the photopolymerizable compound added, if this photopolymerizable compound remains unreacted in the liquid crystal, it becomes an impurity, and the liquid crystal display element Therefore, a polymerizable compound capable of increasing the response speed with a small addition amount is desirable.

  An object of the present invention is to solve the above-described problems of the prior art, and a liquid crystal aligning agent, a liquid crystal alignment film, a liquid crystal display element, and a liquid crystal display capable of improving the response speed of a vertical alignment type liquid crystal display element. The object is to provide a method for manufacturing an element.

  The liquid crystal aligning agent of the present invention that solves the above problems comprises a side chain for vertically aligning liquid crystals 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 polyimide precursor having, at least one polymer selected from polyimides obtained by imidizing this polyimide precursor, and a polymerizable compound each having a photopolymerizable or photocrosslinkable group at two or more terminals, And a solvent.

  And it is preferable that the said photoreactive side chain contains group selected from following formula (I).

(Wherein R ¹¹ is H or a methyl group)

  Further, it is preferable that the photopolymerization or photocrosslinking group is selected from the following formula (II).

(In the formula, R ¹² is H or an alkyl group having 1 to 4 carbon atoms, and Z ¹ is a divalent alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. (It is an aromatic ring or a heterocyclic ring, and Z ² is a monovalent aromatic ring or heterocyclic ring optionally substituted by 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 obtained by applying the above liquid crystal aligning agent to a substrate and baking it.

  The liquid crystal display element of the present invention is produced by applying a liquid crystal layer by contacting the liquid crystal aligning agent obtained above by applying the liquid crystal aligning agent to a substrate and baking it, and irradiating ultraviolet rays while applying a voltage to the liquid crystal layer. The liquid crystal cell is provided.

  And the manufacturing method of the liquid crystal display element of this invention provides the liquid crystal layer by making it contact with the liquid crystal aligning film obtained by apply | coating the said liquid crystal aligning agent to a board | substrate, and baking, and applying ultraviolet-ray, applying a voltage to this liquid crystal layer. To produce a liquid crystal cell.

  ADVANTAGE OF THE INVENTION According to this invention, the liquid crystal display element of a vertical alignment system with a quick response speed can be provided. And in this liquid crystal aligning agent, even if it is a case where the addition amount of a polymeric compound is small, a response speed can fully be improved.

Hereinafter, the present invention will be described in detail.
The liquid crystal aligning agent of the present invention is a polyimide precursor having a side chain for vertically aligning 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, And at least one polymer selected from polyimides obtained by imidizing this polyimide precursor, a polymerizable compound each having a photopolymerizable or photocrosslinking group at two or more terminals, and a solvent It is. The liquid crystal aligning agent is a solution for forming a liquid crystal aligning film, and the liquid crystal aligning film is a film for aligning liquid crystals 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 this invention contains the polymeric compound which has the group respectively photopolymerized or photocrosslinked in two or more terminal. 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 groups that undergo photopolymerization or photocrosslinking. Here, the polymerizable compound having a photopolymerizable group is a compound having a functional group that causes polymerization upon irradiation with light. The compound having a photocrosslinking group is at least one selected from a polymer of a polymerizable compound, a polyimide precursor, and a polyimide obtained by imidizing the polyimide precursor by irradiating light. It is a compound having a functional group capable of reacting with the polymer and crosslinking with these polymers. A compound having a photocrosslinkable group also reacts with a compound having a photocrosslinkable group.

  Such a polymerizable compound has a side chain for vertically aligning a liquid crystal, which will be described in detail later, 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 display of a vertical alignment method such as an SC-PVA liquid crystal display, which is contained in a liquid crystal aligning agent together with a polyimide precursor and at least one polymer selected from polyimide obtained by imidizing the polyimide precursor. Compared to the case where a polymer having a side chain for vertically aligning the liquid crystal and a photoreactive side chain or this polymerizable compound is used alone, the response speed is dramatically improved. The response speed can be sufficiently improved even with a small addition amount of the polymerizable compound.

  Examples of the photopolymerizable or photocrosslinking group include a monovalent group represented by the above formula (II).

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

Specific examples of the polymerizable compound represented by the formula (III) include a polymerizable compound represented by the following formula (1). In the following formula (1), V is represented by a single bond or -R ¹ O-, and R ¹ is a linear or branched alkylene group having 1 to 10 carbon atoms, preferably represented by -R ¹ O-. R ¹ is a linear or branched alkylene group having 2 to 6 carbon atoms. W represents a single bond or —OR ² —, and R ² represents a linear or branched alkylene group having 1 to 10 carbon atoms, and preferably represents —OR ² — and R ² represents a straight chain or It is a branched alkylene group having 2 to 6 carbon atoms. V and W may be the same or different, but if they are the same, synthesis is easy. In addition, about the polymeric compound represented by following formula (1), since it applied for separately, you may remove from this invention.

  Since the polymerizable compound represented by the above formula (1) is a compound having a specific structure having an α-methylene-γ-butyrolactone group which is a polymerizable group (a photopolymerizable group) at both ends, the polymer is rigid. As shown in the examples to be described later, at least one kind selected from a polyimide precursor and a polyimide obtained by imidizing this polyimide precursor By using the polymer for the production of a vertical alignment type liquid crystal display element such as an SC-PVA type liquid crystal display using the liquid crystal alignment film as a material, the response speed can be significantly improved. In general, the process of forming the liquid crystal alignment film includes a step of baking at a high temperature to completely remove the solvent. However, a polymerizable group such as an acrylate group, a methacrylate group, a vinyl group, a vinyloxy group, or an epoxy group is added. The compounds that are possessed have poor thermal stability and are difficult to withstand firing at high temperatures. On the other hand, the polymerizable compound represented by the above formula (1) can sufficiently withstand a high temperature, for example, a firing temperature of 200 ° C. or higher, because of its poor thermal polymerizability.

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

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

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

(In the formula, R ′ represents a monovalent organic group.)

  In addition, 2- (bromomethyl) acrylic acid can be represented by the following reaction formula: K. Ramarajan, K. Kamalingam, DJO 'Donnell and KDBerlin, Organic Synthesis, vol. 61, 56-59 (1983). It can be synthesized by the proposed method.

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

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

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

  The liquid crystal aligning agent of the present invention is at least one selected from a polyimide precursor and a polyimide obtained by imidizing the polyimide precursor, and a side chain and a photoreactive side for vertically aligning liquid crystals. A polymer having a chain. 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 aligning the liquid crystal of the polymer is not limited as long as the liquid crystal can be aligned vertically with respect to the substrate. For example, a long chain alkyl group or a middle of a long chain alkyl group may be used. And a group having a ring structure or a branched structure, a hydrocarbon group such as a steroid group, or a group in which some or all of the hydrogen atoms of these groups are replaced with fluorine atoms. Of course, you may have the side chain which orientates two or more types of liquid crystal vertically. The side chain for vertically aligning the liquid crystal may be directly bonded to a polyimide precursor such as polyamic acid or polyamic acid ester or a main chain of polyimide, that is, a polyamic acid skeleton, a polyimide skeleton, or the like. You may couple | bond together through a coupling group. Examples of the side chain for vertically aligning the liquid crystal include a hydrocarbon group having 8 to 30 carbon atoms, preferably 8 to 22 carbon atoms in which hydrogen atoms may be substituted with fluorine, specifically alkyl groups, fluoro Examples thereof include an alkyl group, an alkenyl group, a phenethyl group, a styrylalkyl group, a naphthyl group, and a fluorophenylalkyl group. Examples of the side chain for vertically aligning other liquid crystals include those represented by the following formula (a).

(In the formula (a), l, m and n each independently represents 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 is a hydrogen atom, 24 represents an alkyl group or a fluorine-containing alkyl group, a monovalent aromatic ring, a monovalent aliphatic ring, a monovalent heterocyclic ring, or a monovalent macrocyclic substituent comprising them.)

R ³ in the above 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 l, m, n, R ⁴ and R ⁵ shown in Table 1 below from the viewpoint of ease of synthesis and ability to align liquid crystals vertically. And a combination of R ⁶ is preferred.

When at least one of l, m and n is 1, R ⁷ in formula (a) is preferably a hydrogen atom, an alkyl group having 2 to 14 carbon atoms or a fluorine-containing alkyl group, more preferably A hydrogen atom, an alkyl group having 2 to 12 carbon atoms, or a fluorine-containing alkyl group. When l, m, and n are all 0, R ⁷ is preferably an alkyl group having 12 to 22 carbon atoms or a fluorine-containing alkyl group, a monovalent aromatic ring, a monovalent aliphatic ring, a monovalent Heterocycles and monovalent macrocyclic substituents made of them, more preferably alkyl groups having 12 to 20 carbon atoms or fluorine-containing alkyl groups.

  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 align the liquid crystal vertically. However, in the liquid crystal display element having the liquid crystal alignment film, the amount of side chains that vertically align the liquid crystal is possible within a range that does not impair the display characteristics of the element such as voltage holding ratio and accumulation of residual DC voltage. As few as possible is preferable.

  The ability of a polymer having side chains for vertically aligning liquid crystals to align liquid crystals vertically varies depending on the structure of the side chains for vertically aligning liquid crystals, but in general, the side chains for vertically aligning liquid crystals. As the amount increases, the ability to align the liquid crystal vertically increases, and as the amount decreases, it decreases. Moreover, when it has a cyclic structure, compared with what does not have a cyclic structure, there exists a tendency for the capability to orientate a liquid crystal vertically.

  Moreover, the polymer which consists of at least 1 type of polyimide precursors, such as polyamic acid and polyamic acid ester, and a polyimide which the liquid crystal aligning agent of this invention contains has a photoreactive side chain. The photoreactive side chain is a side chain having a functional group (hereinafter also referred to as a photoreactive group) that can react by irradiation with light such as ultraviolet rays (UV) to form a covalent bond. Includes at least one selected from a methacryl group, an acryl group, a vinyl group, and a cinnamoyl group as a photoreactive group. Thus, a polymer comprising at least one of polyimide precursors and polyimides such as polyamic acid and polyamic acid ester contained in the liquid crystal aligning agent is at least one selected from methacrylic group, acrylic group, vinyl group and cinnamoyl group. By including the photoreactive side chain in the liquid crystal aligning agent together with the polymerizable compound, the response speed can be remarkably improved as shown in the examples described later.

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

(In the formula (b), R ⁸ is a single bond or —CH ₂ —, —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —CH ₂ O—, —N It represents any one of (CH ₃ ) —, —CON (CH ₃ ) —, —N (CH ₃ ) CO—, and R ⁹ is a single bond, unsubstituted or substituted with a fluorine atom. Represents an alkylene group of ˜20, and —CH ₂ — of the alkylene group may be optionally replaced by —CF ₂ — or —CH═CH—, and when any of the following groups is not adjacent to each other: , may be substituted with these groups; -O -, - COO -, - OCO -, - NHCO -, - CONH -, - NH-, a divalent carbocyclic, divalent heterocyclic ^{.R 10} Represents a methacryl group, an acrylic group, a vinyl group, or a cinnamoyl group.

R ⁸ in the above formula (b) can be formed by a general organic synthetic method, but from the viewpoint of ease of synthesis, —CH ₂ —, —O—, —COO—, —NHCO. _{-, - NH -, - CH} 2 O- are preferable.

Specific examples of the divalent carbocycle or divalent heterocycle carbocycle or heterocycle for replacing any —CH ₂ — in R ⁹ include the following structures, but are not limited thereto. Is not to be done.

R ¹⁰ is preferably a methacryl group, an acryl 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 amount of the photoreactive side chain is preferably within a range in which the response speed of the liquid crystal can be increased by reacting with ultraviolet irradiation to form a covalent bond. In order to further increase the response speed of the liquid crystal As many as possible are preferable as long as other characteristics are not affected.

  A polyimide precursor having a side chain for vertically aligning such a liquid crystal, and a photoreactive side chain containing at least one selected from a methacryl group, an acryl group, a vinyl group, and a cinnamoyl group, and the polyimide precursor The method for producing at least one polymer selected from polyimides obtained by imidizing the body is not particularly limited. For example, in a method of obtaining a polyamic acid by a reaction between a diamine and tetracarboxylic dianhydride, a liquid crystal is used. Photoreactivity including a diamine having a vertically aligned side chain or a tetracarboxylic dianhydride having a vertically aligned liquid crystal or at least one selected from a methacrylic group, an acrylic group, a vinyl group and a cinnamoyl group Diamine or methacryl group, acrylic group, vinyl group and cinnamoy having side chains of The tetracarboxylic acid dianhydride having photoreactive side chain containing at least one selected from the group it is sufficient to copolymerization.

  Examples of the diamine having a side chain for vertically aligning the liquid crystal include a long chain alkyl group, a group having a ring structure or a branched structure in the middle of the long chain alkyl group, a hydrocarbon group such as a steroid group, and the hydrogen of these groups. A diamine having a side chain with a group in which some or all of the atoms are replaced with fluorine atoms, for example, a diamine having a side chain represented by the above formula (a) can be mentioned. More specifically, for example, a diamine having a hydrocarbon group having 8 to 30 carbon atoms in which a hydrogen atom may be substituted with fluorine, or the following formulas (2), (3), (4), (5 The diamine represented by this can be mentioned, However, It is not limited to this.

(The definitions of l, m, n, and R ^{3 to} R ⁷ in Formula (2) are the same as those in Formula (a) above.)

(Equation (3) and the formula _(4), A 10 is -COO -, - OCO -, - CONH -, - NHCO -, - CH 2 -, - O -, - CO-, or -NH- and represents , A ₁₁ represents a single bond or a phenylene group, a represents the same structure as a side chain for vertically aligning the liquid crystal represented by the above formula (a), and a ′ is represented by the above formula (a). (This represents a divalent group having a structure in which one element such as hydrogen is removed from the same structure as the side chain that vertically aligns liquid crystal.)

(Wherein _{(5), A 14} is a fluorine atom may be substituted, an alkyl group having 3 to 20 carbon _{atoms, A 15} is 1,4-cyclohexylene group, or 1,4 A phenylene group, A ₁₆ is an oxygen atom or —COO— * (where a bond marked with “*” is bonded to A ₁₅ ), and A ₁₇ is an oxygen atom or —COO — * ( However, "*" is a bond marked with a _(CH 2) binds to _{a 2.).} Further, _{a 1} is 0, or an integer 1, _{a 2} is an integer from 2 to 10, a ₃ is 0 or an integer of 1.

Binding positions of the two amino group (-NH ₂₎ in equation (2) is not limited. Specifically, with respect to the linking group of the side chain, 2, 3 position, 2, 4 position, 2, 5 position, 2, 6 position, 3, 4 position on the benzene ring, 3, 4 position, 5 positions. Among these, from the viewpoint of reactivity when synthesizing a polyamic acid, positions 2, 4, 2, 5, or 3, 5 are preferable. Considering the ease in synthesizing the diamine, the positions 2, 4 or 3, 5 are more preferable.

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

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

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

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

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

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

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

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

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

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

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

  The diamine may be used alone or in combination of two or more depending on the liquid crystal alignment properties, pretilt angle, voltage holding characteristics, accumulated charge, and the like when the liquid crystal alignment film is formed.

  The diamine having a side chain for vertically aligning the liquid crystal is preferably used in an amount of 5 to 50 mol% of the diamine component used for the synthesis of the polyamic acid, more preferably 10 to 40 mol% of the diamine component. Is a diamine having a side chain for vertically aligning the liquid crystal, particularly preferably 15 to 30 mol%. When the diamine having a side chain for vertically aligning the liquid crystal is used in an amount of 5 to 50 mol% of the diamine component used for the synthesis of the polyamic acid, it is particularly excellent in terms of improving the response speed and the ability to fix the alignment of the liquid crystal. .

  Examples of the diamine having a photoreactive side chain containing at least one selected from a methacryl group, an acryl group, a vinyl group, and a cinnamoyl group include a diamine having a side chain represented by the above formula (b). Can do. More specifically, examples include diamines represented by the following general formula (6), but are not limited thereto.

(The definitions of R ⁸ , R ⁹ and R ¹⁰ in Formula (6) are the same as those in Formula (b) above.)

The bonding position of the two amino groups (—NH ₂ ) in Formula (6) is not limited. Specifically, with respect to the linking group of the side chain, 2, 3 position, 2, 4 position, 2, 5 position, 2, 6 position, 3, 4 position on the benzene ring, 3, 4 position, 5 positions. Among these, from the viewpoint of reactivity when synthesizing a polyamic acid, positions 2, 4, 2, 5, or 3, 5 are preferable. Considering the ease in synthesizing the diamine, the positions 2, 4 or 3, 5 are more preferable.

  Specific examples of the diamine having a photoreactive side chain including at least one selected from a methacryl group, an acryl group, a vinyl group, and a cinnamoyl group include the following compounds, but are not limited thereto. It is not a thing.

Wherein X ¹ and X ² are each independently a single bond or a linking group selected from —O—, —COO—, —NHCO—, —NH—, Y is unsubstituted or substituted by a fluorine atom. Represents 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, acryl group, vinyl group and cinnamoyl group is liquid crystal alignment property, pretilt angle, voltage holding property, accumulation when used as a liquid crystal alignment film. One type or a mixture of two or more types can be used depending on characteristics such as electric charge, response speed of liquid crystal when a liquid crystal display element is used, and the like.

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

  In addition, as long as the polyamic acid does not impair the effect of the present invention, other diamines other than the diamine having a side chain for vertically aligning the liquid crystal and the diamine having a photoreactive group are used as a diamine component. be able to. Specifically, for example, p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl- m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2, 4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl 3,3′-dihydroxy-4,4′-diaminobiphenyl, 3,3′-dicarboxy-4,4′- Aminobiphenyl, 3,3′-difluoro-4,4′-biphenyl, 3,3′-trifluoromethyl-4,4′-diaminobiphenyl, 3,4′-diaminobiphenyl, 3,3′-diaminobiphenyl, 2,2′-diaminobiphenyl, 2,3′-diaminobiphenyl, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 2,2′-diaminodiphenylmethane, 2, 3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4 ' -Sulphonyldianiline, 3,3'-sulfonyl Aniline, bis (4-aminophenyl) silane, bis (3-aminophenyl) silane, dimethyl-bis (4-aminophenyl) silane, dimethyl-bis (3-aminophenyl) silane, 4,4′-thiodianiline, 3 , 3′-thiodianiline, 4,4′-diaminodiphenylamine, 3,3′-diaminodiphenylamine, 3,4′-diaminodiphenylamine, 2,2′-diaminodiphenylamine, 2,3′-diaminodiphenylamine, N-methyl ( 4,4'-diaminodiphenyl) amine, N-methyl (3,4'-diaminodiphenyl) amine, N-methyl (3,4'-diaminodiphenyl) amine, N-methyl (2,2'-diaminodiphenyl) Amine, N-methyl (2,3′-diaminodiphenyl) amine, 4,4′-diamino Benzophenone, 3,3′-diaminobenzophenone, 3,4′-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2′-diaminobenzophenone, 2,3′-diaminobenzophenone, 1,5-diaminonaphthalene, 1, 6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6 diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2- Bis (4-aminophenyl) ethane, 1,2-bis (3-aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,3-bis (3-aminophenyl) propane, 1, 4-bis (4-aminophenyl) butane, 1,4-bis (3-aminophenyl) butane, bis (3 5-diethyl-4-aminophenyl) methane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (4-aminobenzyl) benzene, 1,3-bis (4-aminophenoxy) benzene, 4,4 ′-[1,4-phenylene Bis (methylene)] dianiline, 4,4 ′-[1,3-phenylenebis (methylene)] dianiline, 3,4 ′-[1,4-phenylenebis (methylene)] dianiline, 3,4 ′-[1 , 3-phenylenebis (methylene)] dianiline, 3,3 ′-[1,4-phenylenebis (methylene)] dianiline, 3,3 ′-[1,3-phenylenebis (methylene)] dia Phosphorus, 1,4-phenylenebis [(4-aminophenyl) methanone], 1,4-phenylenebis [(3-aminophenyl) methanone], 1,3-phenylenebis [(4-aminophenyl) methanone], 1,3-phenylenebis [(3-aminophenyl) methanone], 1,4-phenylenebis (4-aminobenzoate), 1,4-phenylenebis (3-aminobenzoate), 1,3-phenylenebis (4 -Aminobenzoate), 1,3-phenylenebis (3-aminobenzoate), bis (4-aminophenyl) terephthalate, bis (3-aminophenyl) terephthalate, bis (4-aminophenyl) isophthalate, bis (3- Aminophenyl) isophthalate, N, N ′-(1,4-phenylene) bis (4-aminobenzamide) ), N, N ′-(1,3-phenylene) bis (4-aminobenzamide), N, N ′-(1,4-phenylene) bis (3-aminobenzamide), N, N ′-(1, 3-phenylene) bis (3-aminobenzamide), N, N′-bis (4-aminophenyl) terephthalamide, N, N′-bis (3-aminophenyl) terephthalamide, N, N′-bis (4 -Aminophenyl) isophthalamide, N, N'-bis (3-aminophenyl) isophthalamide, 9,10-bis (4-aminophenyl) anthracene, 4,4'-bis (4-aminophenoxy) diphenylsulfone, 2,2′-bis [4- (4-aminophenoxy) phenyl] propane, 2,2′-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2, '-Bis (4-aminophenyl) hexafluoropropane, 2,2'-bis (3-aminophenyl) hexafluoropropane, 2,2'-bis (3-amino-4-methylphenyl) hexafluoropropane, 2 , 2′-bis (4-aminophenyl) propane, 2,2′-bis (3-aminophenyl) propane, 2,2′-bis (3-amino-4-methylphenyl) propane, 3,5-diamino Benzoic acid, 2,5-diaminobenzoic acid, 1,3-bis (4-aminophenoxy) propane, 1,3-bis (3-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, 1,4-bis (3-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 1,5-bis (3-aminophenoxy) pentane, 1, -Bis (4-aminophenoxy) hexane, 1,6-bis (3-aminophenoxy) hexane, 1,7-bis (4-aminophenoxy) heptane, 1,7- (3-aminophenoxy) heptane, 1,8-bis (4-aminophenoxy) octane, 1,8-bis (3-aminophenoxy) octane, 1,9-bis (4-aminophenoxy) nonane, 1,9-bis (3-aminophenoxy) Nonane, 1,10- (4-aminophenoxy) decane, 1,10- (3-aminophenoxy) decane, 1,11- (4-aminophenoxy) undecane, 1,11- (3-aminophenoxy) undecane, Aromatic diamines such as 1,12- (4-aminophenoxy) dodecane and 1,12- (3-aminophenoxy) dodecane, bis (4-aminocyclohexyl) E) Alicyclic diamines such as methane and bis (4-amino-3-methylcyclohexyl) methane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, and 1,6-diamino Examples include aliphatic diamines such as xanthone, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane. .

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

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

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

  The organic solvent used in the above reaction is not particularly limited as long as the generated polyamic acid dissolves. Furthermore, even if it is an organic solvent in which a polyamic acid does not melt | dissolve, you may mix and use the said solvent in the range which the produced | generated polyamic acid does not precipitate. In addition, since the water | moisture content in an organic solvent inhibits a polymerization reaction and also causes the produced polyamic acid to hydrolyze, it is preferable to use what dehydrated and dried the organic solvent. Examples of the organic solvent used in the reaction include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N-methylformamide, N-methyl-2-pyrrolidone, N-ethyl-2- Pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide, N-methylcaprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide , Γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl Rosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether , Propylene glycol monobutyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, di Propylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3 -Methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl Ether, dioxane, n-hexane, n-pentane, n-octane, Ethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, Methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl -2-pentanone, 2-ethyl-1-hexanol and the like. These organic solvents may be used alone or in combination.

  When the diamine component and the tetracarboxylic dianhydride component are reacted in an organic solvent, the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic dianhydride component is used as it is or in an organic solvent. A method of adding by dispersing or dissolving in a solvent, a method of adding a diamine component to a solution in which a tetracarboxylic dianhydride component is dispersed or dissolved in an organic solvent, and a tetracarboxylic dianhydride component and a diamine component. The method of adding alternately etc. is mentioned, You may use any of these methods. In addition, when the diamine component or tetracarboxylic dianhydride component is composed of a plurality of types of compounds, they may be reacted in a premixed state, may be individually reacted sequentially, or may be further reacted individually. The body may be mixed and reacted to form a high molecular weight body.

  The temperature at the time of making a diamine component and a tetracarboxylic dianhydride component react can select arbitrary temperatures, for example, -20 degreeC-150 degreeC, Preferably it is the range of -5 degreeC-100 degreeC. Moreover, reaction can be performed by arbitrary density | concentrations, for example, the total amount of a diamine component and a tetracarboxylic dianhydride component is 1-50 mass% with respect to the reaction liquid, Preferably it is 5-30 mass%.

  The ratio of the total number of moles of the tetracarboxylic dianhydride component with respect to the total number of moles of the diamine component in the polymerization reaction can be selected according to the molecular weight of the polyamic acid to be obtained. Similar to the normal polycondensation reaction, the molecular weight of the polyamic acid produced increases as the molar ratio approaches 1.0. If it shows a preferable range, it is 0.8 to 1.2.

  The method for synthesizing the polyamic acid used in the present invention is not limited to the above-described method, and in the same manner as the general polyamic acid synthesis method, instead of the tetracarboxylic dianhydride, a tetracarboxylic acid having a corresponding structure is used. The corresponding polyamic acid can also be obtained by reacting by a known method using a tetracarboxylic acid derivative such as acid or tetracarboxylic acid dihalide.

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

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

  The catalytic imidation of the polyamic acid can be performed by adding a basic catalyst and an acid anhydride to the polyamic acid solution and stirring at -20 to 250 ° C, preferably 0 to 180 ° C. The amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times of the amidic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol of the amido acid group. Is double. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Among them, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated. The imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.

  The polyamic acid ester is a reaction of a tetracarboxylic acid diester dichloride with a diamine similar to the synthesis of the polyamic acid, a suitable condensing agent with a diamine similar to the synthesis of the tetracarboxylic acid diester and the polyamic acid, It can be produced by reacting in the presence of a base or the like. Alternatively, it can also be obtained by previously synthesizing a polyamic acid by the above method and esterifying the carboxylic acid in the amic acid using a polymer reaction. Specifically, for example, tetracarboxylic acid diester dichloride and diamine are -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C in the presence of a base and an organic solvent, for 30 minutes to 24 hours, preferably 1 hour. A polyamic acid ester can be synthesized by reacting for ˜4 hours. The polyimide can also be obtained by heating the polyamic acid ester at a high temperature to promote dealcoholization and ring closure.

  When recovering the polyimide precursor or polyimide such as polyamic acid and polyamic acid ester produced from the polyimide precursor or polyimide reaction solution such as polyamic acid and polyamic acid ester, the reaction solution is poured into a poor solvent and precipitated. You can do it. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water. The polymer precipitated in a poor solvent and collected by filtration can be dried by normal temperature or reduced pressure at room temperature or by heating. Moreover, when the polymer which carried out precipitation collection | recovery is re-dissolved in an organic solvent and the operation which carries out reprecipitation collection | recovery is repeated 2 to 10 times, the impurity in a polymer can be decreased. Examples of the poor solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of poor solvents selected from these because purification efficiency is further improved.

  As described above, the liquid crystal aligning agent of the present invention includes a side chain for vertically aligning 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. A polyimide precursor having, at least one polymer selected from polyimides obtained by imidizing this polyimide precursor, and a polymerizable compound each having a photopolymerizable or photocrosslinkable group at two or more terminals, The amount of the polymerizable compound is not particularly limited as long as it has a solvent, but the content of the polymerizable compound having a photopolymerizable or photocrosslinkable group at two or more terminals respectively aligns the liquid crystal vertically. Polyimide precursor having a side chain and a photoreactive side chain containing at least one selected from a methacryl group, an acryl group, a vinyl group, and a cinnamoyl group And it is preferable that it is 1-50 mass parts with respect to 100 mass parts of at least 1 type of polymers selected from the polyimide obtained by imidating this polyimide precursor, More preferably, it is 5-30 mass parts. . Further, a polyimide precursor having a side chain for vertically aligning a liquid crystal contained in a liquid crystal aligning agent, 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 the content of at least one polymer selected from polyimides obtained by imidizing this polyimide precursor is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, and particularly preferably. 3% by mass to 10% by mass.

  The liquid crystal aligning agent of the present invention is a polyimide precursor having a side chain for vertically aligning a liquid crystal and 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 polymer selected from polyimides obtained by imidizing this polyimide precursor. In that case, 0.5 mass%-15 mass% are preferable, and, as for content of this other polymer in a polymer whole component, More preferably, they are 1 mass%-10 mass%.

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

  The solvent contained in the liquid crystal aligning agent is not particularly limited, and includes a side chain that vertically aligns the liquid crystal, and a photoreactive side chain that includes at least one selected from a methacryl group, an acrylic group, a vinyl group, and a cinnamoyl group. A polyimide precursor having at least one polymer selected from polyimides obtained by imidizing this polyimide precursor, a polymerizable compound having a photopolymerizable group or a photocrosslinkable group at two or more terminals, etc. Any component can be used as long as it can dissolve or disperse. For example, the organic solvent which was illustrated by the synthesis | combination of said polyamic acid can be mentioned. Among these, N-methyl-2-pyrrolidone, γ-butyrolactone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and 3-methoxy-N, N-dimethylpropanamide are soluble. To preferred. Of course, two or more kinds of mixed solvents may be used.

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

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

  Examples of compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. More specifically, for example, F-top EF301, EF303, EF352 (manufactured by Tochem Products), MegaFuck F171, F173, R-30 (manufactured by Dainippon Ink), Florard FC430, FC431 (manufactured by Sumitomo 3M) Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.) and the like. When these surfactants are used, the use ratio thereof is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of the total amount of the polymer contained in the liquid crystal aligning agent. 1 part by mass.

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

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

  By applying and baking this liquid crystal aligning agent on a substrate, a liquid crystal alignment film for vertically aligning liquid crystals can be formed. The liquid crystal aligning agent of the present invention is a polyimide precursor having a side chain for vertically aligning 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, And at least one polymer selected from polyimides obtained by imidizing this polyimide precursor and a polymerizable compound each having a photopolymerizable group or a photocrosslinkable group at two or more terminals, and thus obtained liquid crystal The response speed of the liquid crystal display element using the alignment film can be increased.

  For example, after apply | coating the liquid crystal aligning agent of this invention to a board | substrate, after drying as needed, the cured film obtained by baking can also be used as a liquid crystal aligning film as it is. In addition, the cured film is rubbed, irradiated with polarized light or light of a specific wavelength, or treated with an ion beam, or a voltage is applied to the liquid crystal display element after filling the liquid crystal as a PSA alignment film It is also possible to irradiate with UV. In particular, it is useful to use as an alignment film for PSA.

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

  The method for applying the liquid crystal aligning agent is not particularly limited, and examples thereof include screen printing, offset printing, flexographic printing, and other printing methods, ink jet methods, spray methods, roll coating methods, dip, roll coater, slit coater, and spinner. From the standpoint 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 baked to obtain a cured film. The drying process after applying the liquid crystal aligning agent is not necessarily required, but if the time from application to baking is not constant for each substrate, or if baking is not performed immediately after application, the drying process is performed. It is preferable. The drying is not particularly limited as long as the solvent is removed to such an extent that the shape of the coating film is not deformed by transporting 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 1 minute to 5 minutes.

  The baking temperature of the coating film formed by applying the liquid crystal aligning agent is not limited, and can be performed at an arbitrary temperature of, for example, 100 to 350 ° C., preferably 120 to 300 ° C., more preferably 150 to 250 ° C. Firing can be performed at an arbitrary time of 5 minutes to 240 minutes. Preferably it is 10 minutes-90 minutes, More preferably, it is 20 minutes-90 minutes. Heating can be performed by a generally known method such as a hot plate, a hot air circulating furnace, an infrared furnace, or the like.

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

  And the liquid crystal display element of this invention can produce a liquid crystal cell by a well-known method, after forming a liquid crystal aligning film in a board | substrate by said method. Specific examples of the liquid crystal display element include two substrates disposed so as to face each other, a liquid crystal layer provided between the substrates, and a liquid crystal aligning agent provided between the substrate and the liquid crystal layer. A vertical alignment type liquid crystal display device comprising a liquid crystal cell having the above-described liquid crystal alignment film. Specifically, the liquid crystal aligning agent of the present invention is applied onto two substrates and baked to form a liquid crystal aligning film, and the two substrates are arranged so that the liquid crystal aligning films face each other. A liquid crystal layer composed of liquid crystal is sandwiched between two substrates, that is, a liquid crystal layer is provided in contact with the liquid crystal alignment film, and ultraviolet rays are applied while applying a voltage to the liquid crystal alignment film and the liquid crystal layer. This is a vertical alignment type liquid crystal display device including a liquid crystal cell to be manufactured. As described above, the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention is used to irradiate ultraviolet rays while applying voltage to the liquid crystal alignment film and the liquid crystal layer to polymerize the polymerizable compound, and the light possessed by the polymer. A liquid crystal display device in which the alignment of the liquid crystal is more efficiently fixed and the response speed is remarkably improved by reacting the reactive side chains or the photoreactive side chain of the polymer with the polymerizable compound. It becomes.

  The substrate used in the liquid crystal display element of the present invention is not particularly limited as long as it is a highly transparent substrate, but is usually a substrate on which a transparent electrode for driving liquid crystal is formed. As a specific example, the thing similar to the board | substrate described with the said liquid crystal aligning film can be mentioned. A substrate provided with a conventional electrode pattern or protrusion pattern may be used, but in the liquid crystal display element of the present invention, the liquid crystal aligning agent of the present invention is used as the liquid crystal aligning agent for forming the liquid crystal aligning film. It is possible to operate even in a structure in which a line / slit electrode pattern of 1 to 10 μm, for example, is formed on one side substrate and a slit pattern or projection pattern is not formed on the opposite substrate. This process can be simplified and high transmittance can be obtained.

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

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

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

  The liquid crystal material constituting the liquid crystal layer of the liquid crystal display element of the present invention is not particularly limited, and a liquid crystal material used in a conventional vertical alignment method, for example, a negative type liquid crystal such as MLC-6608 or MLC-6609 manufactured by Merck Can be used.

  As a method of sandwiching the liquid crystal layer between two substrates, a known method can be exemplified. For example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, and spacers such as beads are dispersed on the liquid crystal alignment film on one substrate so that the surface on which the liquid crystal alignment film is formed is on the inside. Then, the other substrate is bonded, and liquid crystal is injected under reduced pressure to seal. Also, a pair of substrates on which a liquid crystal alignment film is formed are prepared, and spacers such as beads are dispersed on the liquid crystal alignment film on one substrate, and then liquid crystal is dropped, and then the surface on which the liquid crystal alignment film is formed A liquid crystal cell can also be produced by a method in which the other substrate is bonded to the inside so as to be inside and sealed. The thickness of the spacer at this time is preferably 1 to 30 μm, more preferably 2 to 10 μm.

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

  Thus, when ultraviolet rays are applied 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 is memorized by this polymer. The response speed of the obtained liquid crystal display element can be increased. In addition, a photoreaction including a side chain that vertically aligns liquid crystal when applied with voltage to the liquid crystal alignment film and the liquid crystal layer, and at least one selected from a methacryl group, an acrylic group, a vinyl group, and a cinnamoyl group Photoreactive side chains possessed by at least one polymer selected from a polyimide precursor having a functional side chain and a polyimide obtained by imidizing the polyimide precursor, and a photoreaction possessed by the polymer Since the reactive side chain and the polymerizable compound react, the response speed of the obtained liquid crystal display element can be increased.

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

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to the examples.

<Polymerizable compound>
(Synthesis of polymerizable compound (RM1))
In a 300 ml eggplant flask equipped with a condenser tube, 5.0 g (23.8 mmol) of 4,4′-biphenyldicarboxaldehyde, 7.9 g (47.6 mmol) of 2- (bromomethyl) acrylic acid, 33 ml of 10% hydrochloric acid (aq), Tetrahydrofuran (THF) 100 ml and tin (II) chloride 9.5 g (50 mmol) were added to form a mixture, which was stirred at 70 ° C. for 20 hours for reaction. 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. As a result of measuring this solid by NMR, it was confirmed that this white solid was a polymerizable compound (RM1) represented by the following reaction formula. The yield was 72%.
¹ H-NMR (CDCl ₃ ) δ: 2.99 (m, 2H), 3.42 (m, 2H), 5.60 (m, 2H), 5.74 (m, 2H), 6.36 (m, 2H), 7.42 (m, 4H ), 7.60 (m, 4H).

(Synthesis of polymerizable compound (RM2))
In a 300 ml eggplant flask with a condenser tube, 6.7 g (35.9 mmol) of 4,4′-biphenol, 15.0 g (71.7 mmol) of 2- (4-bromobutyl) -1,3-dioxolane, 19.8 g of potassium carbonate (143 mmol) and 150 ml of acetone were added to form a mixture, which was reacted at 60 ° 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. Then, this solid and 200 ml of water were mixed and extracted by adding 80 ml of chloroform. Extraction was performed three times.

The separated organic layer was dried over anhydrous magnesium sulfate, filtered, and then the solvent was distilled off under reduced pressure to obtain a yellow solid. The solid was purified by recrystallization (hexane / chloroform = 4/1 (volume ratio)) to obtain 14.6 g of a white solid. The result of having measured the obtained white solid by NMR is shown below. The obtained solid was dissolved in deuterated chloroform (CDCl ₃ ) and measured at 300 MHz using a nuclear magnetic resonance apparatus (manufactured by Diol). From this result, it was confirmed that this white solid was a compound (RM2-A) shown by the following reaction formula. The yield was 92%.
¹ H-NMR (CDCl ₃ ) δ: 1.65 (m, 4H), 1.74 (m, 4H), 1.87 (m, 4H), 3.86 (m, 4H), 3.97 (m, 8H), 4.89 (t, 2H ), 6.92 (m, 4H), 7.44 (m, 4H).

  Next, in a 500 ml eggplant flask equipped with a cooling tube, 13.3 g (30 mmol) of the compound (RM2-A) obtained above, 11.6 g (70 mmol) of 2- (bromomethyl) acrylic acid, 50 ml of 10% hydrochloric acid (aq) , 160 ml of tetrahydrofuran (THF) and 13.2 g (70 mmol) of tin (II) chloride were added to form a mixture, and the mixture was stirred at 70 ° C. for 20 hours to be reacted. After completion of the reaction, the reaction solution was filtered under reduced pressure, mixed with 200 ml of pure water, and extracted with 100 ml of dichlorochloro. Extraction was performed three times.

To the separated organic layer, anhydrous magnesium sulfate was added and dried, and the solvent was distilled off from the solution after filtration under reduced pressure to obtain a white solid. This solid was purified by recrystallization (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 the white solid was a polymerizable compound (RM2) represented by the following reaction formula. The yield was 64%.
¹ H-NMR (CDCl ₃ ) δ: 1.69 (m, 12H), 2.61 (m, 2H), 3.09 (m, 2H), 4.00 (t, 4H), 4.57 (m, 2H), 5.64 (m, 2H ), 6.24 (m, 2H), 6.92 (d, 4H), 7.45 (m, 4H).

(Synthesis of polymerizable compound (RM3))
In a 500 ml eggplant flask equipped with a condenser tube, 11.2 g (60 mmol) of 4,4′-biphenol, 25.0 g (138 mmol) of 2- (2-bromoethyl) -1,3-dioxolane, 35.9 g (260 mmol) of potassium carbonate, And 200 ml of acetone was added to make a mixture, and the mixture was reacted at 60 ° 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 was mixed with 200 ml of water, and extracted with 100 ml of chloroform. Extraction was performed three times.

The separated organic layer was dried by adding anhydrous magnesium sulfate, filtered, and then 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 having measured this solid by NMR is shown below. From this result, it was confirmed that this white solid was a compound (RM3-A) shown by the following reaction formula. The yield was 76%.
¹ H-NMR (CDCl ₃ ) δ: 2.19 (m, 4H), 3.89 (m, 4H), 4.01 (m, 4H), 4.16 (m, 4H), 5.11 (m, 2H), 6.95 (m, 4H ), 7.45 (m, 4H).

  Next, in a 500 ml eggplant flask equipped with a condenser, 10.0 g (26 mmol) of the compound (RM3-A) obtained above, 10.0 g (60.6 mmol) of 2- (bromomethyl) acrylic acid, 10% HCl (aq ) 32 ml, tetrahydrofuran (THF) 140 ml, tin (II) chloride 11.4 g (60.6 mmol) were added to form a mixture, and the mixture was stirred at 70 ° C. for 20 hours for reaction. After completion of the reaction, the reaction solution was filtered under reduced pressure, mixed with 200 ml of pure water, and extracted with 100 ml of chloroform. Extraction was performed three times.

The organic layer after extraction was dried by adding anhydrous magnesium sulfate, and the solvent was distilled off from the solution after filtration under reduced pressure to obtain a white solid. This solid was dissolved in chloroform and precipitated with hexane (hexane / chloroform = 2/1) to obtain a white solid. After this solid was washed with methanol, 4.7 g of a white solid was obtained. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this white solid was the target polymerizable compound (RM3) represented by the following reaction formula. The yield was 42%.
¹ H-NMR (CDCl ₃ ) δ: 2.18 (m, 4H), 2.76 (m, 2H), 3.16 (m, 2H), 4.18 (m, 4H), 4.84 (m, 2H), 5.67 (m, 2H ), 6.27 (m, 2H), 6.95 (d, 4H), 7.46 (m, 4H).

(Synthesis of polymerizable compound (RM4))
To a 500 ml eggplant flask equipped with a condenser tube, 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 obtain a mixture. The reaction was carried out at 48 ° C. with stirring for 48 hours. 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 having measured this solid by NMR is shown below. From this result, it was confirmed that this white solid was a compound (RM4-A) shown by the following reaction formula. The yield was 95%.
1H NMR (CDCl3) δ: 1.57 (m, 4H), 1.74 (m, 4H), 1.86 (m, 4H), 2.06 (s, 6H), 4.02 (t, 4H), 4.12 (t, 4H), 6.95 (d, 4H), 7.47 (d, 4H).

To a 1-liter eggplant flask equipped with a condenser tube was added 250 ml of ethanol, 18.0 g (41 mmol) of the compound (RM4-A) obtained above, and 100 ml of 10% aqueous sodium hydroxide solution to obtain a mixture, and the mixture was stirred at a temperature of 85 ° C. for 5 hours. While reacting. After completion of the reaction, 500 ml of water and the reaction solution were added to a 1000 ml beaker and stirred for 30 minutes at room temperature, and then 80 ml of 10% HCl aqueous solution was added dropwise, followed by filtration to obtain 12.2 g of a white solid. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this white solid was a compound (RM4-B) shown by the following reaction formula. The yield was 83%.
1H NMR (DMSO-d6) δ: 1.46 (m, 8H), 1.71 (m, 4H), 3.41 (m, 4H), 3.98 (m, 4H), 4.39 (m, 2H), 6.96 (m, 4H) , 7.51 (m, 4H).

Compound (RM4-B) (5.0 g, 14.0 mmol) 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) at room temperature. The solution which melt | dissolved 3.3 g (32 mmol) of methacryloyl chloride in 20 ml of THF was dripped over 15 minutes under cooling by a water bath. After dropping, the mixture was stirred for 30 minutes, and 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 precipitated with hexane (hexane / chloroform = 2/1) to obtain 2.6 g of a white solid. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this white solid was a polymerizable compound (RM4) represented by the following reaction formula. The yield was 38%.
¹ H-NMR (CDCl ₃ ) δ: 1.56 (m, 4H), 1.74 (m, 4H), 1.82 (m, 4H), 1.97 (s, 6H), 4.03 (m, 4H), 4.20 (m, 4H ), 5.55 (m, 2H), 6.10 (m, 2H), 6.94 (d, 4H), 7.45 (d, 4H).

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

(Synthesis of polymerizable compound (RM6))
In a 200 ml eggplant flask with a condenser tube, methyl 4-hydroxybenzoate (7.61 g, 50.0 mmol), 6-bromo-1-hexanol, 9.1 g (50.0 mmol), potassium carbonate, 13.8 g (100 mmol), and acetone 70 ml was added to form a mixture, and the mixture was reacted at 64 ° C. with stirring for 24 hours. 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 resulting solution to obtain 11.3 g of a white solid. The NMR measurement result of this solid is shown below. From this result, it was confirmed that this white solid was a compound (RM6-A) shown by the following reaction formula. The yield was 90%.
¹ H-NMR (CDCl ₃ ) δ: 1.3-1.7 (m, 8H), 3.67 (m, 2H), 3.88 (s, 3H), 4.03 (t, 2H), 6.91 (d, 2H), 7.99 (d , 2H).

Next, in a 100 ml three-necked flask equipped with a condenser tube, 2.2 g (10.0 mmol) of pyridinium chlorochromate (PCC) and 15.0 ml of CH ₂ Cl ₂ were stirred and mixed, and the compound obtained above A solution prepared by dissolving 2.5 g (10.0 mmol) of (RM6-A) in 15.0 ml of CH ₂ Cl ₂ was added dropwise and further stirred at room temperature for 6 hours. Thereafter, 90 ml of diethyl ether was added to the solution excluding the oily substance adhering to the flask wall and filtered under reduced pressure, and then 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 having measured this solid by NMR is shown below. From this result, it was confirmed that this colorless solid was a compound (RM6-B) shown by the following reaction formula. The yield was 50%.
¹ H-NMR (CDCl ₃ ) δ: 1.3-1.8 (m, 6H), 2.49 (t, 2H), 3.88 (s, 3H), 3.99 (t, 2H), 6.87 (d, 2H), 7.99 (d , 2H), 9.78 (s, 1H).

  Next, 1.25 g (5.0 mmol) of the compound (RM6-B) obtained above, 0.83 g (5.0 mmol) of 2- (bromomethyl) acrylic acid, Amberlyst (Registered) was added to a 50 ml eggplant flask equipped with a cooling tube. Trademark) 15 (Rohm End Haas Co., Ltd. trade name) 0.8 g, THF 8.0 ml, tin (II) chloride 0.95 g (5.0 mmol) and pure water 2.0 ml were added to form a mixture, and the mixture was kept at 70 ° C. for 5 hours. Stir to react. After completion of the reaction, the reaction solution was filtered under reduced pressure, mixed with 40 ml of pure water, and extracted with 50 ml of diethyl ether. Extraction was performed three times.

The organic layer after extraction was dried by adding anhydrous magnesium sulfate, and 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 result of this solid is shown below. From this result, it was confirmed that this colorless solid was a compound (RM6-C) shown by the following reaction formula. The yield was 94%.
¹ H-NMR (DMSO-d6) δ: 1.3-1.8 (m, 8H), 2.62 (m, 1H), 3.04 (s, 1H), 3.81 (s, 3H), 4.05 (t, 2H), 4.54 ( m, 1H), 5.70 (s, 1H), 6.01 (s, 1H), 7.03 (d, 2H), 7.89 (d, 2H).

To a 100 ml eggplant flask equipped with a condenser tube, 35 ml of ethanol, 1.5 g (4.7 mmol) of the compound (RM6-C) obtained above, and 5 ml of 10% aqueous sodium hydroxide solution were added to obtain a mixture, and the mixture was kept at 85 ° C. for 3 hours. The reaction was carried out with stirring. After completion of the reaction, 300 ml of water and the reaction solution were added to a 500 ml beaker and stirred for 30 minutes at room temperature. Then, 5 ml of 10% HCl aqueous solution was added dropwise, followed by filtration to obtain 1.3 g of a white solid.
Next, 1.1 g of the obtained white solid, Amberlyst (registered trademark) 15 (trade name of Rohm End Haas Co., Ltd.) 1.0 g, and 20.0 ml of THF were added to a 50 ml eggplant flask with a cooling tube to obtain a mixture, For 5 hours with stirring. After completion of the reaction, the solvent was distilled off from the solution after filtering the reaction solution under reduced pressure to obtain a yellow solid. The 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 result of this solid is shown below. From this result, it was confirmed that this white solid was a compound (RM6-D) shown by the following reaction formula. The yield was 71%.
¹ H-NMR (DMSO-d6) δ: 1.2-1.8 (m, 8H), 2.60 (m, 1H), 3.09 (m, 1H), 4.04 (m, 2H), 4.55 (m, 1H), 5.69 ( s, 1H), 6.02 (s, 1H), 6.99 (d, 2H), 7.88 (d, 2H), 12.5 (s, broad, 1H).

21.1 g (69.3 mmol) of the compound (RM6-D) obtained above, 5.0 g (34.7 mmol) of 1,4-cyclohexanedimethanol, N, N-dimethyl-4-aminopyridine (DMAP) 0 .35 g and a small amount of BHT were suspended in 100 ml of methylene chloride under stirring at room temperature, and 15.5 g (75.0 mmol) of dicyclohexylcarbodiimide (DCC) dissolved in 50 ml of methylene chloride was added thereto and stirred for 48 hours. Reacted. After completion of the reaction, the precipitated DCC urea was filtered off, and the filtrate was washed twice with 60 ml of 0.5N HCl, saturated aqueous sodium hydrogen carbonate solution and saturated brine successively, and dried over magnesium sulfate. The solvent was distilled off, and recrystallization with ethanol yielded 20.1 g of a polymerizable compound (RM6) represented by the following reaction formula. The result measured by NMR is shown below. The yield was 81%.
¹ H-NMR (CDCl3) δ: 1.15 (m, 4H), 1.50 (m, 8H), 1.66 (m, 2H), 1.79 (m, 8H), 1.92 (m, 4H), 2.60 (m, 2H) , 3.08 (m, 2H), 4.01 (m, 4H), 4.12 (m, 4H), 4.53 (m, 2H), 5.63 (d, 2H), 6.24 (d, 2H), 6.89 (d, 4H), 7.97 (d, 4H).

(Synthesis of polymerizable compound (RM7))
6.1 g (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), N, N-dimethyl-4-aminopyridine (DMAP) (0.1 g) and a small amount of BHT are suspended in 100 ml of methylene chloride at room temperature with stirring, and 5.1 g (25.0 mmol) of dicyclohexylcarbodiimide (DCC) is dissolved in the suspension. The solution was added and stirred overnight. The precipitated DCC urea was filtered off, and the filtrate was washed twice with 100 ml of 0.5N HCl, 100 ml of saturated aqueous sodium hydrogen carbonate solution and 150 ml of saturated brine successively, dried over magnesium sulfate, and then under reduced pressure. The solvent was distilled off to obtain a yellow solid. This solid was purified by silica column chromatography (column: silica gel 60 0.063-0.200 mm, manufactured by Merck & Co., eluent: hexane / ethyl acetate = 1/1). The solvent of the solution obtained here was distilled off to obtain 4.3 g of a polymerizable compound (RM7) represented by the following reaction formula. The result measured by NMR is shown below. The yield was 39%.
1H NMR (CDCl3) δ: 1.53 (m, 10H), 1.72 (m, 2H), 1.79 (m, 4H), 2.58 (m, 1H), 3.07 (m, 1H), 3.96 (t, 2H), 4.05 (t, 2H), 4.18 (t, 2H), 4.54 (m, 1H), 5.64 (d, 1H), 5.81 (d, 1H), 6.14 (m, 1H), 6.24 (d, 1H), 6.40 ( d, 1H), 6.97 (m, 4H), 7.09 (d, 2H), 8.14 (d, 2H).

(Synthesis of polymerizable compound (RM8))
While stirring 2.1 g (7.3 mmol) of the compound (RM8-A) represented by the following reaction formula, 2.5 g (7.3 mmol) of the compound (RM8-B), 0.015 g of DMAP and a small amount of BHT at room temperature, The suspension was suspended in 30 ml of methylene chloride, and 1.8 g (9.0 mmol) of DCC dissolved in 5 ml of methylene chloride was added thereto and stirred overnight. The precipitated DCC urea was filtered off, and the filtrate was sequentially added to 50 ml of 0. The extract was washed twice with 5N HCl, saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over magnesium sulfate, the solvent was distilled off, and recrystallization with ethanol gave a polymerizable compound represented by the following reaction formula (RM8). ) 1.3 g was obtained. The result measured by NMR is shown below. The yield was 30%.
1H NMR (CDCl3)): δ 1.40-1.90 (m, 14H), 2.64 (m, 1H), 3.07 (m, 1H), 4.00 (t, 2H), 4.05 (t, 2H), 4.18 (t, 2H ), 4.54 (m, 1H), 5.83 (d, 1H), 6.14 (m, 1H), 6.25 (d, 1H), 6.37 (d, 1H), 6.97 (d, 2H), 7.26 (d, 2H) , 7.50 (d, 2H), 7.57 (d, 2H), 8.17 (d, 2H).

(Synthesis of polymerizable compound (RM9))
To a 100 ml eggplant flask equipped with a condenser tube, 6.1 g (50 mmol) of 4-hydroxybenzaldehyde, 9.1 g (50 mmol) of 6-bromo-1-hexanol, 13.8 g (100 mmol) of potassium carbonate, and 100 ml of acetone are added to form a mixture. The reaction was allowed to proceed with stirring at 64 ° C. for 24 hours. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a yellow wet solid. Then, this solid and 70 ml of water were mixed and extracted by adding 50 ml of diethyl ether. Extraction was performed three times.

The separated organic layer was dried by adding anhydrous magnesium sulfate, filtered, and then 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 resulting solution to obtain 7.4 g of a white solid. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this white solid was a compound (RM9-A) shown by the following reaction formula. The yield was 67%.
1H NMR (DMSO-d6) δ: 1.55 (m, 4H), 1.62 (m, 2H), 1.84 (m, 2H), 3.67 (t, 2H), 4.05 (t, 2H), 4.20 (t, 2H) , 7.00 (d, 2H), 7.84 (d, 2H), 9.88 (s, 1H).

In a 50 ml three-necked flask, 2.2 g of compound (RM9-A), 1.7 ml of triethylamine, 0.2 mg of BHT and 10 ml of THF were mixed and dissolved. While stirring this solution, a solution prepared by dissolving 0.8 ml of acryloyl chloride in 10 ml of THF was added dropwise over 15 minutes. At that time, the three-necked flask was cooled in a water bath (water temperature 20 ° C.). After the dropwise addition, the mixture was stirred for 30 minutes as it was, and then the flask was taken out of the water bath, purged with nitrogen, and further reacted by stirring at room temperature for 3 hours. The reaction solution was filtered, the filtrate was concentrated under reduced pressure to a volume of 3/4, and 100 ml of methylene chloride was added. This solution was washed with 100 ml of saturated sodium carbonate solution, 100 ml of 0.5N hydrochloric acid and 100 ml of saturated brine in that order, and 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 solution obtained here to obtain 2.0 g of a white solid. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this white solid was a compound (RM9-B) shown by the following reaction formula. The yield was 72%.
1H NMR (CDCl3) δ: 1.48 (m, 4H), 1.75 (m, 2H), 1.85 (m, 2H), 4.05 (t, 2H), 4.18 (t, 2H), 5.81 (d, 1H), 6.14 (m, 1H), 6.37 (d, 1H), 6.99 (m, 2H), 7.82 (m, 2H), 9.88 (s, 1H).

  Next, 2.0 g (7 mmol) of the intermediate compound (RM9-B) obtained in the same manner as described above was added to a 50 ml eggplant flask equipped with a cooling tube, and 1.2 g (7.0 mmol) of 2- (bromomethyl) acrylic acid. , Amberlyst (registered trademark) 15 (Rohm End Haas Co., Ltd. trade name) 1.2 g, THF 8.0 ml, tin (II) chloride 1.4 g (7 mmol) and pure water 2.0 ml were added to form a mixture at a temperature of 70 ° C. The reaction was allowed to stir for 24 hours. After completion of the reaction, the reaction solution was filtered under reduced pressure and mixed with 60 ml of pure water, and 50 ml of diethyl ether was added thereto for extraction. Extraction was performed three times. The organic layer after extraction was dried by adding anhydrous magnesium sulfate, and the solvent was distilled off from the solution after filtration under reduced pressure to obtain a light 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 solution obtained here to obtain 1.0 g of a white solid. As a result of measuring this solid by NMR, it was confirmed that this white solid was a polymerizable compound (RM9) represented by the following reaction formula. The yield was 40%.
1H NMR (CDCl3) δ: 1.48 (m, 4H), 1.75 (m, 4H), 2.94 (m, 1H), 3.39 (m, 1H), 3.95 (t, 2H), 4.17 (t, 2H), 5.45 (t, 1H), 5.68 (m, 1H), 5.83 (m, 1H), 6.13 (m, 1H), 6.30 (m, 1H), 6.40 (d, 1H), 6.88 (d, 2H), 7.26 ( m, 2H).

(Synthesis of polymerizable compound (RM10))
Compound (RM6-D) 22.0 g (72.4 mmol), 1,4-phenyldimethanol 5.0 g (36.2 mmol) obtained in the same manner as above, N, N-dimethyl-4-aminopyridine (DMAP) 0.35 g and a small amount of BHT were suspended in 100 ml of methylene chloride under stirring at room temperature, and 17.0 g (80.0 mmol) of dicyclohexylcarbodiimide (DCC) dissolved in 50 ml of methylene chloride was added thereto to add 48 The reaction was stirred for an hour. After completion of the reaction, the precipitated DCC urea was filtered off, and the filtrate was washed twice with 60 ml of 0.5N HCl, saturated aqueous sodium hydrogen carbonate solution and saturated brine successively, and dried over magnesium sulfate. The solvent was distilled off, and 16.6 g of a polymerizable compound (RM10) represented by the following reaction formula was obtained by recrystallization with ethanol. The result measured by NMR is shown below. The yield was 65%.
¹ H-NMR (CDCl3) δ: 1.46 (m, 12H), 1.80 (m, 4H), 2.60 (m, 2H), 3.08 (m, 2H), 4.01 (m, 4H), 4.56 (m, 2H) , 5.34 (s, 4H), 5.63 (d, 2H), 6.23 (d, 2H), 6.90 (d, 4H), 7.46 (s, 4H), 8.00 (d, 4H).

(Synthesis of polymerizable compound (RM11))
6.1 g (20.0 mmol) of the compound (RM6-D) obtained in the same manner as above, 2.1 g (10.0 mmol) of 4,4′-biphenyldimethanol, N, N-dimethyl-4-amino To a suspension of 0.15 g of pyridine (DMAP) and a small amount of BHT in 50 ml of methylene chloride at room temperature with stirring, 5.3 g (25.0 mmol) of dicyclohexylcarbodiimide (DCC) dissolved in 25 ml of methylene chloride was added. The reaction was stirred for 48 hours. After completion of the reaction, the precipitated DCC urea was filtered off, and the filtrate was washed twice with 60 ml of 0.5N HCl, saturated aqueous sodium hydrogen carbonate solution and saturated brine successively, and dried over magnesium sulfate. The solvent was distilled off, and 6.4 g of a polymerizable compound (RM11) represented by the following reaction formula was obtained by recrystallization with ethanol. The result measured by NMR is shown below. The yield was 81%.
¹ H-NMR (CDCl3) δ: 1.48 (m, 12H), 1.75 (m, 4H), 2.60 (m, 2H), 3.08 (m, 2H), 4.01 (m, 4H), 4.55 (m, 2H) , 5.38 (s, 4H), 5.63 (d, 2H), 6.23 (d, 2H), 6.89 (d, 4H), 7.51 (d, 4H), 7.62 (d, 4H), 8.05 (d, 4H).

(Synthesis of polymerizable compound (RM12))
6.1 g (20.0 mmol) of the compound (RM6-D) obtained in the same manner as above, 2.1 g (10.0 mmol) of 4,4′-dihydroxybenzophenone, N, N-dimethyl-4-aminopyridine (DMAP) 0.1 g and a small amount of BHT were suspended in 80 ml of methylene chloride under stirring at room temperature, and a solution in which 5.2 g (24.0 mmol) of dicyclohexylcarbodiimide (DCC) was dissolved was added thereto and stirred overnight. did. The precipitated DCC urea was filtered off, and the filtrate was washed with 0.5N-HCl (50 ml), saturated aqueous sodium hydrogen carbonate solution (50 ml) and saturated brine (100 ml) twice in succession, dried over magnesium sulfate, and then under reduced pressure. The solvent was distilled off to obtain a yellow solid. This solid was purified by recrystallization using ethanol to obtain 6.2 g of a white solid. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this white solid was a polymerizable compound (RM12) represented by the following reaction formula. The yield was 79%.
1H NMR (CDCl3) δ: 1.45-1.95 (m, 16H), 2.58 (m, 2H), 3.07 (m, 2H), 4.05 (t, 4H), 4.54 (m, 2H), 5.64 (s, 2H) , 6.24 (s, 2H), 6.98 (d, 4H), 7.32 (d, 4H), 7.91 (d, 4H), 8.18 (d, 4H).

(Synthesis of polymerizable compound (RM13))
To a 500 ml eggplant flask with a condenser tube was added 12.2 g (100 mmol) of 4-hydroxybenzaldehyde, 12.2 g (50 mmol) of 1,6-dibromohexane, 16.0 g (116 mmol) of potassium carbonate, and 150 ml of acetone to obtain a mixture. The reaction was carried out at a temperature of 64 ° C. with stirring for 48 hours. After the reaction solution was filtered, the solvent was distilled off under reduced pressure to obtain 15.4 g of a light brown wet solid. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this solid was a compound (RM13-A) represented by the following reaction formula. The yield was 94%.
¹ H-NMR (CDCl ₃ ) δ: 1.49 (m, 4H), 1.77 (m, 4H), 4.12 (t, 4H), 7.10 (d, 2H), 7.86 (d, 2H), 9.87 (s, 2H ).

Next, in a 100 ml eggplant flask equipped with a cooling tube, 3.3 g (10.0 mmol) of the compound (RM13-A) obtained in the same manner as above, 3.3 g (20.0 mmol) of 2- (bromomethyl) acrylic acid. , Amberlyst (registered trademark) 15 (Rohm End Haas Co., Ltd., product name) 3.0 g, THF 32.0 ml, tin (II) chloride 3.8 g (20.0 mmol), and pure water 8.0 ml to obtain a mixture, the temperature 70 The reaction was allowed to stir at 24 ° C. for 24 hours. After completion of the reaction, the reaction solution was filtered under reduced pressure and mixed with 60 ml of pure water, and 70 ml of diethyl ether was added thereto for extraction. Extraction was performed three times. The organic layer after extraction was dried by adding anhydrous magnesium sulfate, and the solvent was distilled off from the solution after filtration under reduced pressure to obtain a light 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 resulting solution to obtain 2.6 g of a white solid. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this white solid was a polymerizable compound (RM13) represented by the following reaction formula. The yield was 55%.
¹ H-NMR (CDCl ₃ ) δ: 1.54 (m, 4H), 1.80 (m, 4H), 2.94 (m, 2H), 3.35 (m, 2H), 3.97 (t, 4H), 5.47 (m, 2H ), 5.68 (m, 2H), 6.30 (m, 2H), 6.88 (d, 4H), 7.26 (d, 4H).

(Synthesis of polymerizable compound (RM14))
In a 300 ml eggplant flask with a condenser tube, 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, 10.5 g of tin (II) chloride (110 0.0 mmol) and 35.0 ml of aqueous hydrochloric acid solution (10%) were added to form a mixture, which was stirred at 70 ° C. for 24 hours to be reacted. After completion of the reaction, it was mixed with 200 ml of pure water, and extracted with 100 ml of diethyl ether. Extraction was performed three times.

The organic layer after extraction was dried by adding anhydrous magnesium sulfate, and 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 result of this solid is shown below. From this result, it was confirmed that this colorless solid was a compound (RM14-A) shown by the following reaction formula. The yield was 76%.
¹ H-NMR (DMSO-d6) δ: 2.85 (m, 1H), 3.50 (m, 1H), 5.75 (m, 1H), 5.80 (s, 1H), 6.18 (s, 1H), 7.45 (d, 2H), 7.98 (d, 2H), 13.08 (s, 1H).

2.4 g (11.0 mmol) of the compound (RM14-A) obtained above, 0.6 g (5.0 mmol) of 1,6-hexanediol, N, N-dimethyl-4-aminopyridine (DMAP) 0. 05 g and a small amount of BHT were suspended in 10 ml of methylene chloride under stirring at room temperature, 2.5 g (12.0 mmol) of dicyclohexylcarbodiimide (DCC) dissolved in 5 ml of methylene chloride was added thereto, and the reaction was stirred for 48 hours. I let you. After completion of the reaction, the precipitated DCC urea was filtered off, and the filtrate was washed twice with 60 ml of 0.5N HCl, saturated aqueous sodium hydrogen carbonate solution and saturated brine successively, and dried over magnesium sulfate. The solvent was distilled off, and 1.3 g of a polymerizable compound (RM14) represented by the following reaction formula was obtained by recrystallization operation with ethanol. The result measured by NMR is shown below. The yield was 50%.
¹ H-NMR (CDCl3) δ: 1.53 (m, 4H), 1.80 (m, 4H), 2.85 (m, 2H), 3.45 (m, 2H), 4.36 (m, 4H), 5.60 (t, 2H) , 6.72 (d, 2H), 6.34 (d, 2H), 7.40 (d, 4H), 8.06 (d, 4H).

(Synthesis of polymerizable compound (RM15))
In a 300 ml three-necked flask equipped with a condenser tube, 6.2 g (28.7 mmol) of PCC and 100.0 ml of CH ₂ Cl ₂ were stirred and mixed, and then 8.0 g (28) of the compound (RM15-A) represented by the following reaction formula 0.7 mmol) in CH ₂ Cl ₂ (30.0 ml) was added dropwise and further stirred at room temperature for 2 hours. Thereafter, 150 ml of diethyl ether was added to the solution excluding the oily substance adhering to the flask wall and filtered under reduced pressure, and then 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 & Co., 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 having measured this solid by NMR is shown below. From this result, it was confirmed that this colorless solid was a compound (RM15-B) shown by the following reaction formula. The yield was 72%.
1H NMR (CDCl3) δ: 1.50 (m, 2H), 1.70 (m, 2H), 1.85 (m, 2H), 2.45 (m, 2H), 3.80 (s, 3H), 4.00 (t, 2H), 6.25 (d, 1H), 6.83 (d, 2H), 7.45 (d, 2H), 7.84 (d, 1H), 9.80 (s, 1H).

  Next, 5.7 g (20.6 mmol) of the compound (RM15-B) obtained above, 3.4 g (20.6 mmol) of 2- (bromomethyl) acrylic acid, 10% hydrochloric acid was added to a 100 ml eggplant flask equipped with a condenser. An aqueous solution (16 ml), THF (50 ml), and tin (II) chloride (3.9 g, 20.6 mmol) were added to form a mixture, and the mixture was reacted at a temperature of 70 ° C. for 20 hours. After completion of the reaction, the reaction solution was filtered under reduced pressure and mixed with 100 ml of pure water, and 150 ml of diethyl ether was added thereto for extraction. Extraction was performed three times.

To the organic layer after extraction, anhydrous magnesium sulfate was added and dried, followed by filtration under reduced pressure. The solvent was distilled off from the solution, and recrystallization (hexane / ethyl acetate, 1/1) was performed to obtain 4.6 g of a colorless solid. Obtained. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this colorless solid was a polymerizable compound (RM15) represented by the following reaction formula. The yield was 65%.
1H NMR (CDCl3) δ: 1.40-1.90 (m, 8H), 2.60 (m, 1H), 3.05 (m, 1H), 3.80 (s, 3H), 4.02 (t, 2H), 4.55 (m, 1H) , 5.63 (s, 1H), 6.25 (s, 1H), 6.33 (d, 1H), 6.90 (d, 2H), 7.45 (d, 2H), 7.65 (d, 1H).

(Synthesis of polymerizable compound (RM16))
In a 200 ml eggplant flask equipped with a condenser tube, 5.0 g (24.0 mmol) of 4-bromobutyl-1,3-dioxolane, 4.5 g (27.0 mmol) of 2- (bromomethyl) acrylic acid, 19 ml of 10% aqueous hydrochloric acid, 60 ml of THF, Then, 4.7 g (27.0 mmol) of tin (II) chloride was added to form a mixture, and the mixture was reacted by stirring at a temperature of 70 ° C. for 20 hours. After completion of the reaction, the reaction solution was filtered under reduced pressure, mixed with 100 ml of pure water, and extracted with 100 ml of diethyl ether. Extraction was performed three times.

The organic layer after extraction was dried by adding anhydrous magnesium sulfate, and 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 having measured this liquid by NMR is shown below. From this result, it was confirmed that this colorless liquid was a compound (RM16-A) represented by the following reaction formula. The yield was 93%.
1H NMR (CDCl3) δ: 1.64 (m, 4H), 1.96 (m, 2H), 2.06 (m, 1H), 3.07 (m, 1H), 3.44 (t, 2H), 4.55 (m, 1H), 5.65 (s, 1H), 6.25 (s, 1H).

In a 100 ml eggplant flask equipped with a condenser tube, 4.7 g (20.0 mmol) of the compound (RM16-A) obtained above, 3.6 g (20.0 mmol) of 4-methoxycinnamic acid, 5.1 g of potassium carbonate (40 0.0 mmol) and 50 ml of N, N-dimethylformamide (DMF) were added to form a mixture, which was reacted at 110 ° C. with stirring for 48 hours. After completion of the reaction, it was mixed with 200 ml of pure water, and 50 ml of ethyl acetate was added thereto for extraction. Extraction was performed three times. The organic layer after extraction was dried by adding anhydrous magnesium sulfate, 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 solution obtained here to obtain 2.8 g of a white solid. The NMR measurement result of this solid is shown below. From this result, it was confirmed that this solid was a polymerizable compound (RM16) represented by the following reaction formula. The yield was 43%.
1H NMR (CDCl3) δ: 1.50 (m, 2H), 1.75 (m, 4H), 2.63 (m, 1H), 3.05 (m, 1H), 3.85 (s, 3H), 4.20 (t, 2H), 4.55 (m, 1H), 5.65 (s, 1H), 6.23 (s, 1H), 6.50 (d, 1H), 6.90 (d, 2H), 7.45 (d, 2H), 7.66 (d, 1H).

(Synthesis of polymerizable compound (RM17))
In a 200 ml eggplant flask with a condenser tube, 9.4 g (45.0 mmol) of 4-bromobutyl-1,3-dioxolane, 10.0 g (45.0 mmol) of trans-4-phenylcinnamic acid, 12.0 g of potassium carbonate (90 0.0 mmol), and 100 ml of DMF were added to form a mixture, which was reacted at 110 ° C. with stirring for 48 hours. After completion of the reaction, it was mixed with 100 ml of pure water to obtain a solid. The solid was filtered, and 50 ml of ethanol was added to form a 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 result of this solid is shown below. From this result, it was confirmed that this solid was a compound (RM17-A) represented by the following reaction formula. The yield was 40%.
1H NMR (CDCl3) δ: 1.55 (m, 2H), 1.75 (m, 4H), 3.83 (m, 2H), 3.98 (m, 2H), 4.24 (t, 2H), 4.85 (m, 1H), 6.45 (d, 1H), 7.36 (m, 1H), 7.46 (m, 2H), 7.60 (m, 6H), 7.75 (d, 1H).

  Next, in a 100 ml eggplant flask equipped with a condenser, 6.2 g (18.0 mmol) of the compound (RM17-A) obtained above, 3.3 g (20.0 mmol) of 2- (bromomethyl) acrylic acid, 10% hydrochloric acid An aqueous solution (16 ml), THF (32 ml), and tin (II) chloride (3.8 g, 20.0 mmol) were added to form a mixture, and the mixture was stirred at a temperature of 70 ° C. for 20 hours to be reacted. After completion of the reaction, the reaction solution was mixed with 100 ml of pure water, and extracted with 50 ml of diethyl ether. Extraction was performed three times.

To the organic layer after extraction, anhydrous magnesium sulfate was added and dried, followed by filtration under reduced pressure. The solvent was removed from the solution, and recrystallization (hexane / ethyl acetate, 2/1) was performed to obtain 3.6 g of a solid. It was. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this solid was a polymerizable compound (RM17) represented by the following reaction formula. The yield was 53%.
1H NMR (CDCl3) δ: 1.68 (m, 6H), 2.63 (m, 1H), 3.07 (m, 1H), 4.24 (t, 2H), 4.55 (m, 1H), 5.64 (s, 1H), 6.25 (s, 1H), 6.50 (d, 1H), 7.36 (m, 1H), 7.46 (m, 2H), 7.65 (m, 6H), 7.75 (d, 1H).

(Synthesis of polymerizable compound (RM18))
7.6 g (25.0 mmol) of the compound (RM6-D) obtained by the above method, 4.8 g (25.0 mmol) of ethyl 4-hydroxycinnamate, N, N-dimethyl-4-aminopyridine (DMAP) 0 0.1 g and a small amount of BHT were suspended in 100 ml of methylene chloride under stirring at room temperature, and a solution in which 6.7 g (32 mmol) of dicyclohexylcarbodiimide (DCC) was dissolved was added thereto and stirred overnight. The precipitated DCC urea was filtered off, and the filtrate was washed with 0.5N-HCl (50 ml), saturated aqueous sodium hydrogen carbonate solution (50 ml) and saturated brine (100 ml) twice in succession, dried over magnesium sulfate, and then under reduced pressure. The solvent was distilled off to obtain a yellow solid. This solid was purified by recrystallization using ethanol to obtain 7.1 g of a white solid. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this white solid was a polymerizable compound (RM18) represented by the following reaction formula. The yield was 59%.
1H NMR (CDCl3) δ: 1.35 (t, 3H), 1.40-1.90 (m, 8H), 2.60 (m, 1H), 3.08 (m, 1H), 4.05 (t, 2H), 4.25 (m, 2H) , 4.55 (m, 1H), 5.64 (s, 1H), 6.22 (s, 1H), 6.40 (d, 1H), 6.97 (d, 2H), 7.22 (d, 2H), 7.60 (d, 2H), 7.70 (d, 1H), 8.15 (d, 2H).

(Synthesis of polymerizable compound (RM19))
7.3 g (24.0 mmol) of the compound (RM6-D) obtained by the above method, 5.0 g (24.0 mmol) of methyl 4-hydroxy-3-methoxycinnamate, N, N-dimethyl-4-aminopyridine (DMAP) 0.1 g and a small amount of BHT were suspended in 100 ml of methylene chloride under stirring at room temperature, and a solution in which 6.4 g (31.0 mmol) of dicyclohexylcarbodiimide (DCC) was dissolved was added thereto and stirred overnight. did. The precipitated DCC urea was filtered off, and the filtrate was washed twice with 100 ml of 0.5N HCl, 100 ml of saturated aqueous sodium hydrogen carbonate solution and 150 ml of saturated brine successively, dried over magnesium sulfate, and then under reduced pressure. The solvent was distilled off to obtain a yellow solid. This solid was purified by recrystallization (ethanol) to obtain 6.1 g of a polymerizable compound (RM19) represented by the following reaction formula. The result measured by NMR is shown below. The yield was 51%.
1H NMR (CDCl3) δ: 1.40-1.90 (m, 8H), 2.58 (m, 1H), 3.08 (m, 1H), 3.80 (m, 6H), 4.05 (t, 2H), 4.55 (m, 1H) , 5.62 (s, 1H), 6.22 (s, 1H), 6.42 (d, 1H), 6.97 (d, 2H), 7.18 (m, 3H), 7.65 (d, 1H), 8.18 (d, 2H).

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

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

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

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

<Preparation of liquid crystal aligning agent>
The abbreviations used in the preparation of the following liquid crystal aligning agents are as follows.
BODA: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride TCA: represented by the following formula 2,3,5-tricarboxycyclopentylacetic acid-1,4: 2,3-dianhydride

m-PDA: m-phenylenediamine p-PDA: p-phenylenediamine PCH: 1,3-diamino-4- [4- (4-heptylcyclohexyl) phenoxy] benzene DA-1: 2-represented by the following formula (Methacryloyloxy) ethyl 3,5-diaminobenzoate

DA-2: N ¹ , N ¹ -diallylbenzene-1,2,4-triamine represented by the following formula

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

NMP: N-methyl-2-pyrrolidone BCS: Butyl cellosolve

Moreover, the molecular weight measurement conditions of polyimide are as follows.
Apparatus: Room temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Scientific Co., Ltd.
Column: Column made by Shodex (KD-803, KD-805)
Column temperature: 50 ° C
Eluent: N, N′-dimethylformamide (as additives, lithium bromide-hydrate (LiBr · H ₂ O) is 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphoric acid) is 30 mmol / L, Tetrahydrofuran (THF) 10ml / L)
Flow rate: 1.0 ml / min. Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight of about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation, and polyethylene glycol (manufactured by Polymer Laboratories) Molecular weight about 12,000, 4,000, 1,000).

Moreover, the imidation ratio of polyimide was measured as follows. Add 20 mg of polyimide powder to an NMR sample tube (NMR sampling tube standard φ5 manufactured by Kusano Kagaku Co., Ltd.), add 1.0 ml of deuterated dimethyl sulfoxide (DMSO-d ₆ , 0.05% TMS mixture), and apply ultrasonic waves. To dissolve completely. 500 MHz proton NMR was measured for this solution with the NMR measuring device by the JEOL datum company (JNW-ECA500). The imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of amic acid appearing near 9.5 to 10.0 ppm. It calculated | required by the following formula | equation using the integrated value. In the following formula, x is the proton peak integrated value derived from the NH group of the amic acid, y is the peak integrated value of the reference proton, and α is the proton of the NH group of the amic acid in the case of polyamic acid (imidation rate is 0%). This is the ratio of the number of reference protons to one.
Imidation ratio (%) = (1−α · x / y) × 100

Example 1
BODA (6.01 g, 24.0 mmol), p-PDA (2.60 g, 24.0 mmol), PCH (6.85 g, 18.0 mmol), DA-1 (4.76 g, 18.0 mmol) and NMP ( 81.5 g), and after reacting at 80 ° C. for 5 hours, CBDA (6.94 g, 35.4 mmol) and NMP (27.2 g) were added and reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution. Obtained. After adding NMP to this polyamic acid solution (135 g) and diluting to 6% by mass, acetic anhydride (18.3 g) and pyridine (23.6 g) were added as imidization catalysts, and the mixture was reacted at 50 ° C. for 3 hours. This reaction solution was poured into methanol (1700 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (A). The imidation ratio of this polyimide was 60%, the number average molecular weight was 12000, and the weight average molecular weight was 39000.

  NMP (74.0 g) was added to the obtained polyimide powder (A) (6.0 g), and the mixture was dissolved by stirring at 50 ° C. for 12 hours. BCS (20.0g) was added to this solution, and the liquid crystal aligning agent (B) was obtained by stirring at 50 degreeC for 5 hours.

  Further, 0.06 g (10% by mass with respect to the solid content) of the polymerizable compound (RM1) obtained above was added to 10.0 g of the liquid crystal aligning agent (B), and the mixture was stirred at room temperature for 3 hours. To prepare a liquid crystal aligning agent (B1).

(Example 2)
0.06 g (10% by mass with respect to the 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 dissolved by stirring at room temperature for 3 hours. A liquid crystal aligning agent (B2) was prepared.

(Example 3)
0.06 g (10% by mass with respect to the solid content) of the polymerizable compound (RM3) obtained above was added to 10.0 g of the liquid crystal aligning agent (B), and the mixture was dissolved by stirring at room temperature for 3 hours. A liquid crystal aligning agent (B3) was prepared.

Example 4
0.06 g (10% by mass with respect to the solid content) of the polymerizable compound (RM4) obtained above was added to 10.0 g of the liquid crystal aligning agent (B), and the mixture was dissolved by stirring at room temperature for 3 hours. A liquid crystal aligning agent (B4) was prepared.

(Example 5)
0.06 g (10% by mass with respect to the solid content) of the polymerizable compound (RM5) obtained above was added to 10.0 g of the liquid crystal aligning agent (B), and the mixture was dissolved by stirring at room temperature for 3 hours. A liquid crystal aligning agent (B5) was prepared.

(Comparative Example 1)
BODA (4.38 g, 17.5 mmol), m-PDA (2.65 g, 24.5 mmol), PCH (4.00 g, 10.5 mmol), were dissolved in NMP (42.8 g) at 80 ° C. After reacting for 5 hours, 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. After adding NMP to this polyamic acid solution (70.0 g) and diluting to 6% by mass, acetic anhydride (17.6 g) and pyridine (5.44 g) were added as an imidization catalyst and reacted at 100 ° C. for 3 hours. It was. This reaction solution was poured into methanol (900 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (C). The imidation ratio of this polyimide was 73%, the number average molecular weight was 15000 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 dissolved by stirring at 50 ° C. for 12 hours. BCS (20.0 g) was added to this solution, and the polyimide solution (D) was obtained by stirring at 50 degreeC for 5 hours.

  Further, 0.06 g (10% by mass with respect to the solid content) of the polymerizable compound (RM2) obtained above is added to 10.0 g of the polyimide solution (D), and the mixture is dissolved by stirring for 3 hours at room temperature. A liquid crystal aligning agent (D1) was prepared.

<Production of liquid crystal cell>
(Example 6)
Using the liquid crystal aligning agent (B1) obtained in Example 1, a liquid crystal cell was prepared according to the procedure shown below. The liquid crystal aligning agent (B1) obtained in Example 1 was spin-coated on the ITO surface of an ITO electrode substrate on which an ITO electrode pattern having a pixel size of 100 μm × 300 μm and a line / space of 5 μm was formed, After drying for 90 seconds on this hot plate, baking was performed in a hot air circulation oven at 200 ° C. for 30 minutes to form a liquid crystal alignment film having a thickness of 100 nm.

  Moreover, after spin-coating the liquid crystal aligning agent (B1) on the ITO surface in which the electrode pattern is not formed and drying for 90 seconds on a hot plate at 80 ° C., baking is performed in a hot air circulation oven at 200 ° C. for 30 minutes, A liquid crystal alignment film having a thickness of 100 nm was formed.

  After spraying a 6 μm bead spacer on the liquid crystal alignment film of one of the two substrates, a sealant (solvent type thermosetting epoxy resin) was printed thereon. Next, the surface of the other substrate on which the liquid crystal alignment film was formed was faced inward and bonded to the previous substrate, and then the sealing agent was cured to produce an empty cell. Liquid crystal MLC-6608 (trade name, manufactured by Merck & Co., Inc.) was injected into the empty cell by a reduced pressure injection method, and was subjected to Isotropic treatment (realignment treatment of liquid crystal by heating) in an oven at 120 ° C. to produce a liquid crystal cell.

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

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

(Example 7)
Except for changing the firing temperature from 200 ° C. to 140 ° C., the same operation as in Example 6 was performed, and the response speed before and after UV irradiation was compared.

(Example 8)
The response speed before and after UV irradiation was compared by performing the same operation as in Example 6 except that the liquid crystal aligning agent (B2) was used instead of the liquid crystal aligning agent (B1).

Example 9
Except for changing the firing temperature from 200 ° C. to 140 ° C., the same operation as in Example 8 was performed to compare the response speed before and after UV irradiation.

(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)
Except for changing the firing temperature from 200 ° C. to 140 ° C., the same operation as in Example 10 was performed to compare the response speed before and after UV irradiation.

(Example 12)
The response speed before and after UV irradiation was compared by performing the same operation as in Example 6 except that the liquid crystal aligning agent (B4) was used instead of the liquid crystal aligning agent (B1).

(Example 13)
Except for changing the firing temperature from 200 ° C. to 140 ° C., the same operation as in Example 12 was performed, and the response speed before and after UV irradiation was compared.

(Example 14)
The response speed before and after UV irradiation was compared by performing the same operation as in Example 6 except that the liquid crystal aligning agent (B5) was used instead of the liquid crystal aligning agent (B1).

(Example 15)
Except for changing the firing temperature from 200 ° C. to 140 ° C., the same operation as in Example 14 was performed to compare the response speed before and after UV irradiation.

(Comparative Example 2)
Except that the liquid crystal aligning agent (B) was used instead of the liquid crystal aligning agent (B1), the same operation as in Example 6 was performed, and the response speed before and after UV irradiation was compared.

(Comparative Example 3)
Except for changing the firing temperature from 200 ° C. to 140 ° C., the same operation as in Comparative Example 2 was performed to compare the response speed before and after UV irradiation.

(Comparative Example 4)
The same operation as in Example 6 was performed except that the liquid crystal aligning agent (D1) was used instead of the liquid crystal aligning agent (B1), and the response speeds before and after UV irradiation were compared.

(Comparative Example 5)
Except for changing the firing temperature from 200 ° C. to 140 ° C., the same operation as in Comparative Example 4 was performed to compare the response speed before and after UV irradiation.

  As a result, as shown in Table 2, a polymer (polyimide) having a photoreactive side chain containing a methacrylic group and a side chain for vertically aligning the liquid crystal and a liquid crystal aligning agent containing a polymerizable compound were used. Examples 6 to 15 are 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, a photoreactive side chain containing a methacryl group and Compared with Comparative Examples 2 and 3 using a liquid crystal aligning agent B containing a polymer (polyimide) having a side chain for vertically aligning liquid crystal but not adding a polymerizable compound, response speed before and after UV irradiation The improvement rate was significantly higher.

  Accordingly, by using a liquid crystal aligning agent in which a polymer having a photoreactive side chain containing a methacrylic group and a side chain for vertically aligning a liquid crystal and a polymerizable compound is used, the response speed is higher than using each independently. It has been confirmed that the response speed can be improved drastically and the response speed can be sufficiently improved even with a small amount of the polymerizable compound added.

  Further, Examples 6 to 11 using a liquid crystal aligning agent containing a polymerizable compound having an α-methylene-γ-butyrolactone group which is a polymerizable group at both ends, and this methacrylate group having a methacrylate group at both ends. In Examples 12 to 13 using a liquid crystal aligning agent containing a polymerizable compound having a structure in which is bonded to a phenylene group through an oxyalkylene group, the case where the firing temperature is low (140 ° C.) and the case where it is high (200 (C) also dramatically improved the response speed.

On the other hand, in Examples 14 to 15 using a liquid crystal aligning agent having a methacrylate group and a structure in which the methacrylate group is directly bonded to a phenylene group, the improvement rate of the response speed is 140 ° C. when baked at 200 ° C. It was lower than the case of firing with In Examples 6 to 7 using a polymerizable compound that differs only in the polymerizable group from the polymerizable compound used in Examples 14 to 15, since the baking temperature dependency was hardly confirmed, the methacryl group was bonded. It is presumed that the thermal stability of the polymerizable compound is improved when the carbon atom takes the sp ³ hybrid orbital, and the dependency of the response speed improvement rate on the firing temperature is reduced.

(Example 16)
0.06 g (10% by mass with respect to the solid content) of the polymerizable compound (RM6) 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. A liquid crystal aligning agent (B6) was prepared.

(Example 17)
0.06 g (10% by mass with respect to the solid content) of the polymerizable compound (RM7) obtained above is added to 10.0 g of the liquid crystal aligning agent (B), and the mixture is dissolved by stirring at room temperature for 3 hours. A liquid crystal aligning agent (B7) was prepared.

(Example 18)
0.06 g (10% by mass with respect to the 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. A liquid crystal aligning agent (B8) was prepared.

(Example 19)
0.06 g (10% by mass with respect to the solid content) of the polymerizable compound (RM9) 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. A liquid crystal aligning agent (B9) was prepared.

(Example 20)
0.06 g (10% by mass based on the 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 dissolved by stirring at room temperature for 3 hours. A liquid crystal aligning agent (B10) was prepared.

(Example 21)
0.06 g (10% by mass based on the solid content) of the polymerizable compound (RM11) obtained above was added to 10.0 g of the liquid crystal aligning agent (B), and the mixture was dissolved by stirring at room temperature for 3 hours. A liquid crystal aligning agent (B11) was prepared.

(Example 22)
0.06 g (10% by mass with respect to the solid content) of the polymerizable compound (RM12) obtained above was added to 10.0 g of the liquid crystal aligning agent (B), and the mixture was dissolved by stirring at room temperature for 3 hours. A liquid crystal aligning agent (B12) was prepared.

(Example 23)
0.06 g (10% by mass with respect to the solid content) of the polymerizable compound (RM13) obtained above was added to 10.0 g of the liquid crystal aligning agent (B), and the mixture was dissolved by stirring at room temperature for 3 hours. A liquid crystal aligning agent (B13) was prepared.

(Example 24)
0.06 g (10% by mass with respect to the solid content) of the polymerizable compound (RM14) obtained above is added to 10.0 g of the liquid crystal aligning agent (B), and the mixture is dissolved by stirring at room temperature for 3 hours. A liquid crystal aligning agent (B14) was prepared.

(Example 25)
0.06 g (10% by mass with respect to the solid content) of the polymerizable compound (RM15) obtained above is added to 10.0 g of the liquid crystal aligning agent (B), and the mixture is dissolved by stirring at room temperature for 3 hours. A liquid crystal aligning agent (B15) was prepared.

(Example 26)
0.06 g (10% by mass with respect to the solid content) of the polymerizable compound (RM16) 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. A liquid crystal aligning agent (B16) was prepared.

(Example 27)
0.06 g (10% by mass with respect to the solid content) of the polymerizable compound (RM17) obtained above is added to 10.0 g of the liquid crystal aligning agent (B), and the mixture is dissolved by stirring at room temperature for 3 hours. A liquid crystal aligning agent (B17) was prepared.

(Example 28)
0.06 g (10% by mass with respect to the solid content) of the polymerizable compound (RM18) obtained above was added to 10.0 g of the liquid crystal aligning agent (B), and the mixture was dissolved by stirring at room temperature for 3 hours. A liquid crystal aligning agent (B18) was prepared.

(Example 29)
0.06 g (10% by mass with respect to the solid content) of the polymerizable compound (RM19) obtained above is added to 10.0 g of the liquid crystal aligning agent (B), and the mixture is dissolved by stirring at room temperature for 3 hours. A liquid crystal aligning agent (B19) was prepared.

(Example 30)
0.06 g (10% by mass based on the solid content) of the polymerizable compound (RM20) obtained above was added to 10.0 g of the liquid crystal aligning agent (B), and the mixture was dissolved by stirring at room temperature for 3 hours. A liquid crystal aligning agent (B20) was prepared.

(Example 31)
0.06 g (10% by mass with respect to the solid content) of the polymerizable compound (RM21) 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. A liquid crystal aligning agent (B21) was prepared.

(Example 32)
0.06 g (10% by mass with respect to the solid content) of the polymerizable compound (RM22) obtained above was added to 10.0 g of the liquid crystal aligning agent (B), and the mixture was dissolved by stirring at room temperature for 3 hours. A liquid crystal aligning agent (B22) was prepared.

(Example 33)
0.06 g (10% by mass with respect to the solid content) of the polymerizable compound (RM23) obtained above was added to 10.0 g of the liquid crystal aligning agent (B), and the mixture was dissolved by stirring at room temperature for 3 hours. A liquid crystal aligning agent (B23) was prepared.

(Example 34)
The same operation as in Example 6 was performed except that the liquid crystal aligning agent (B6) was used instead of the liquid crystal aligning agent (B1), and the response speeds before and after UV irradiation were compared.

(Example 35)
The response speed before and after UV irradiation was compared by performing the same operation as in Example 6 except that the liquid crystal aligning agent (B7) was used instead of the liquid crystal aligning agent (B1).

(Example 36)
The same operation as in Example 6 was performed except that the liquid crystal aligning agent (B8) was used instead of the liquid crystal aligning agent (B1), and the response speeds before and after UV irradiation were compared.

(Example 37)
The response speed before and after UV irradiation was compared by performing the same operation as in Example 6 except that the liquid crystal aligning agent (B9) was used instead of the liquid crystal aligning agent (B1).

(Example 38)
The response speed before and after UV irradiation was compared by performing the same operation as in Example 6 except that the liquid crystal aligning agent (B10) was used instead of the liquid crystal aligning agent (B1).

(Example 39)
The response speed before and after UV irradiation was compared by performing the same operation as in Example 6 except that the liquid crystal aligning agent (B11) was used instead of the liquid crystal aligning agent (B1).

(Example 40)
Except for using the liquid crystal aligning agent (B12) instead of the liquid crystal aligning agent (B1), the same operation as in Example 6 was performed, and the response speeds before and after UV irradiation were compared.

(Example 41)
The response speed before and after UV irradiation was compared by performing the same operation as in Example 6 except that the liquid crystal aligning agent (B13) was used instead of the liquid crystal aligning agent (B1).

(Example 42)
The response speed before and after UV irradiation was compared by performing the same operation as in Example 6 except that the liquid crystal aligning agent (B14) was used instead of the liquid crystal aligning agent (B1).

(Example 43)
The response speed before and after UV irradiation was compared by performing the same operation as in Example 6 except that the liquid crystal aligning agent (B15) was used instead of the liquid crystal aligning agent (B1).

(Example 44)
The response speed before and after UV irradiation was compared by performing the same operation as in Example 6 except that the liquid crystal aligning agent (B16) was used instead of the liquid crystal aligning agent (B1).

(Example 45)
The response speed before and after UV irradiation was compared by performing the same operation as in Example 6 except that the liquid crystal aligning agent (B17) was used instead of the liquid crystal aligning agent (B1).

(Example 46)
The response speed before and after UV irradiation was compared by performing the same operation as in Example 6 except that the liquid crystal aligning agent (B18) was used instead of the liquid crystal aligning agent (B1).

(Example 47)
The response speed before and after UV irradiation was compared by performing the same operation as in Example 6 except that the liquid crystal aligning agent (B19) was used instead of the liquid crystal aligning agent (B1).

(Example 48)
The response speed before and after UV irradiation was compared by performing the same operation as in Example 6 except that the liquid crystal aligning agent (B20) was used instead of the liquid crystal aligning agent (B1).

(Example 49)
The response speed before and after UV irradiation was compared by performing the same operation as in Example 6 except that the liquid crystal aligning agent (B21) was used instead of the liquid crystal aligning agent (B1).

(Example 50)
The response speed before and after UV irradiation was compared by performing the same operation as in Example 6 except that the liquid crystal aligning agent (B22) was used instead of the liquid crystal aligning agent (B1).

(Example 51)
The response speed before and after UV irradiation was compared by performing the same operation as in Example 6 except that the liquid crystal aligning agent (B23) was used instead of the liquid crystal aligning agent (B1).

(Example 52)
TCA (3.36 g, 15.0 mmol), p-PDA (1.30 g, 12.0 mmol), DA-3 (3.14 g, 6.0 mmol), DA-1 (3.17 g, 12.0 mmol). After mixing in NMP (41.6 g) and reacting at 60 ° C. for 5 hours, CBDA (2.88 g, 14.7 mmol) and NMP (13.9 g) were added and reacted at 40 ° C. for 10 hours to polyamic acid. A solution was obtained. After adding NMP to this polyamic acid solution (68g) and diluting to 6 mass%, acetic anhydride (6.0g) and pyridine (11.7g) were added as an imidation catalyst, and it was made to react at 50 degreeC for 3 hours. This reaction solution was poured into methanol (850 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (E). The imidation ratio of this polyimide was 50%, the number average molecular weight was 18000, 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 dissolved by stirring at 50 ° C. for 12 hours. BCS (20.0g) was added to this solution, and the liquid crystal aligning agent (F) was obtained by stirring at 50 degreeC for 5 hours.

  Moreover, 0.06g (10 wt% with respect to solid content) of RM2 was added with respect to 10.0g of said liquid crystal aligning agent (F), and it stirred and melt | dissolved at room temperature for 3 hours, and prepared the liquid crystal aligning agent (F1). .

  Moreover, 0.06g (10 wt% with respect to solid content) of RM4 was added with respect to 10.0g of said liquid crystal aligning agent (F), and it stirred and melt | dissolved at room temperature for 3 hours, and prepared the 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 instead of the liquid crystal aligning agent (B1), and the response speeds before and after UV irradiation were compared.

(Example 54)
The response speed before and after UV irradiation was compared by performing the same operation as in Example 6 except that the liquid crystal aligning agent (F2) was used instead of the liquid crystal aligning agent (B1).

(Example 55)
BODA (5.00 g, 20.0 mmol), p-PDA (0.87 g, 8.0 mmol), PCH (3.04 g, 8.0 mmol), DA-2 (4.88 g, 24.0 mmol) were added to NMP ( 52.7 g), and after reacting 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. Obtained. After adding NMP to this polyamic acid solution (75g) and diluting to 6 mass%, acetic anhydride (8.7g) and pyridine (13.5g) were added as an imidation catalyst, and it was made to react at 50 degreeC for 3 hours. This reaction solution was poured into methanol (950 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (G). The imidation ratio of this polyimide was 50%, the number average molecular weight was 20000, and the weight average molecular weight was 86000.

  NMP (74.0 g) was added to the obtained polyimide powder (G) (6.0 g), and the mixture was dissolved by stirring at 50 ° C. for 12 hours. BCS (20.0g) was added to this solution, and the liquid crystal aligning agent (G1) was obtained by stirring at 50 degreeC for 5 hours.

  Further, 0.06 g of polymerizable compound RM2 (10% by mass with respect to the solid content) is added to 10.0 g of the liquid crystal aligning agent (G1), and the mixture is stirred and dissolved at room temperature for 3 hours. ) Was prepared.

(Example 56)
The response speed before and after UV irradiation was compared by performing the same operation as in Example 6 except that the liquid crystal aligning agent (G2) was used instead of the liquid crystal aligning agent (B1).

  The results of Examples 34 to 51, 53, 54 and 56 are shown in Table 3. As shown in Table 3, Example 34 using a polymer (polyimide) having a photoreactive side chain containing a methacryl group and the like and a side chain for vertically aligning liquid crystal and a liquid crystal aligning agent containing a polymerizable compound. Although ~ 51, 53, 54, and 56 differ in a polymeric compound and a polymer, respectively, the improvement rate of the response speed before and behind ultraviolet irradiation was remarkably high similarly to Examples 6-15.

Claims (6)

  A polyimide precursor having a side chain for vertically aligning a liquid crystal and a photoreactive side chain containing at least one selected from a methacryl group, an acryl group, a vinyl group, and a cinnamoyl group, and the polyimide precursor as an imide A liquid crystal aligning agent comprising: at least one polymer selected from polyimides obtained by forming a polymerizable compound, a polymerizable compound each having a photopolymerizable or photocrosslinkable group at two or more terminals, and a solvent. The liquid crystal aligning agent according to claim 1, wherein the photoreactive side chain includes a group selected from the following formula (I).

(Wherein R ¹¹ is H or a methyl group) The liquid crystal aligning agent according to claim 1 or 2, wherein the photopolymerizable or photocrosslinking group is selected from the following formula (II).

(In the formula, R ¹² is H or an alkyl group having 1 to 4 carbon atoms, and Z ¹ is a divalent alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. (It is an aromatic ring or a heterocyclic ring, and Z ² is a monovalent aromatic ring or heterocyclic ring optionally substituted by 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 baking it.   A liquid crystal layer is provided in contact with 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 substrate, and ultraviolet rays are applied while applying a voltage to the liquid crystal layer. A liquid crystal display element comprising a liquid crystal cell produced by irradiation.   A liquid crystal layer is provided in contact with 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 substrate, and ultraviolet rays are applied while applying a voltage to the liquid crystal layer. A method for producing a liquid crystal display element, wherein a liquid crystal cell is produced by irradiation.