KR20140109451A - Liquid crystal aligning agent, liquid crystal display element, method for manufacturing liquid crystal display element, and polymerizable compound - Google Patents

Abstract

(식 [1] 중, C 는 탄소수 10 내지 탄소수 30 으로 형성되고, 방향 고리를 함유하는 2 가의 탄소 고리 함유기이며, P, P^' 는 광이량화를 일으키는 구조, L, L^' 는 광 중합성기이다. S¹, S^1', S², S^2' 는 각각 단결합 또는, 탄소수 1 내지 탄소수 10 으로 형성되는 알킬렌기 등이다.)And a polymerizable compound represented by the following formula [1] in which a photopolymerizable group is introduced into the structure and a structure causing light dimerization are introduced as the liquid crystal aligning agent.

(In the formula [1], C represents a divalent carbon ring-containing group having 10 to 30 carbon atoms and containing an aromatic ring, P and P ^' represent structures in which light dimerization occurs, L and L ^' S ¹ , S ^{1 '} , S ² , and S ^2' are each a single bond or an alkylene group having 1 to 10 carbon atoms).

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal aligning agent, a liquid crystal display element, a method for producing the liquid crystal display element, and a polymerizable compound,

The present invention relates to a liquid crystal aligning agent, a liquid crystal display element, a method for producing a liquid crystal display element, and a polymerizable compound which can be used for producing a liquid crystal display element produced by irradiating ultraviolet rays in a state of applying voltage to liquid crystal molecules.

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

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

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

Japanese Patent Application Laid-Open No. 2003-307720

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

However, it is desired to further increase the response speed of the liquid crystal display element. It is conceivable to increase the response speed of the liquid crystal display element by increasing the addition amount of the photopolymerizable compound. However, if the photopolymerizable compound remains in the liquid crystal in an unreacted state, the impurity (contamination) Which causes the reliability of the display element to deteriorate. Thus, a method of using a polymerizable compound capable of accelerating a response speed by adding a small amount to a liquid crystal can be considered, but there is also a limit. Among these backgrounds, there is a demand for a liquid crystal aligning agent capable of accelerating the response speed without containing a polymerizable compound in the liquid crystal.

In addition, since ultraviolet rays irradiating the liquid crystal cell may decompose the liquid crystal and the liquid crystal aligning agent, a liquid crystal aligning agent capable of accelerating the response speed even in the case of a small irradiation amount is required. At the same time, a liquid crystal aligning agent capable of sufficiently reacting with liquid crystal and ultraviolet rays of long wavelength with little possibility of decomposing the liquid crystal aligning agent has been demanded.

The requirement to increase the response speed is not limited to the liquid crystal display element of the vertical alignment system but also exists in other systems such as a twisted nematic (TN) system.

SUMMARY OF THE INVENTION The object of the present invention is to solve the problems of the above-described prior arts, and it is an object of the present invention to provide a liquid crystal display device which does not contain a polymerizable compound in a liquid crystal and has a small irradiation dose, A liquid crystal display element, a method for producing a liquid crystal display element, and a polymerizable compound which can be improved even in the case of a liquid crystal display device.

As a result of intensive studies to solve the above problems, the present inventors have found that a polymerizable compound (hereinafter referred to as a specific polymerizable compound) having a structure that introduces a structure containing an aromatic ring in the central portion and a structure that causes light dimerization, (Hereinafter also referred to as " polymerizable compound "), and the present invention has been accomplished. That is, the present invention has the following points.

1. A liquid crystal aligning agent characterized by containing a polymerizable compound represented by the following formula [1].

[Chemical Formula 1]

(In the formula [1], C is a divalent carbon ring-containing group having 10 to 30 carbon atoms and containing an aromatic ring, and one or plural hydrogen atoms of the carbon ring-containing group is substituted with a fluorine atom or an organic group .

S ¹ and S ^{1 '} are each independently a single bond or an alkylene group having 1 to 10 carbon atoms, and one or plural hydrogen atoms of the alkylene group may be substituted with a fluorine atom or an organic group. Further, in the case where S ^1, S ^{1 ',} the group of which do illustrated in the following are not adjacent to each other, -CH ₂ - is optionally are substituted with these; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -CO-.

P and P ^' are each independently a group which causes divalent light dimerization selected from the following formulas [P-1] to [P-10], and one or a plurality of groups The hydrogen atom may be substituted with an organic group.

(2)

(Of the formulas [P-1] to [P-10], * denotes S ¹ , S ^{1 '} or S ² , S ^2' ).

S ² and S ^{2 '} are each independently a single bond or an alkylene group having 1 to 10 carbon atoms, and one or plural hydrogen atoms of the alkylene group may be substituted with a fluorine atom or an organic group. In addition, S ² and S ^{2 '} may be substituted with -CH ₂ - in the case where any of the groups shown below are not adjacent to each other; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -CO-.

L and L ^' each independently represent a monovalent photopolymerizable group selected from the following formulas [L-1] to [L-11].

(3)

(Of the formulas [L-1] to [L-11], * represents the bonding position with S ² and S ^{2 '} .)

2. The liquid crystal aligning agent according to 1, wherein L and L ^' are monovalent groups selected from the formulas [L-1], [L-2] and [L-7].

3. The liquid crystal aligning agent according to 1 or 2, wherein P and P ^' are divalent groups selected from the formulas [P-1] to [P-3] and [P-5].

4. The liquid crystal aligning agent according to any one of 1 to 3, wherein C is a divalent group selected from the following formulas [C-1] to [C-12].

[Chemical Formula 4]

(In the formulas [C-1] to [C-12], * represents a bonding position with S ¹ and S ^{1 '} .)

5. A liquid crystal aligning agent according to any one of 1 to 4, which has a polymer forming a liquid crystal alignment film for vertically aligning liquid crystals and a solvent.

6. A liquid crystal alignment film obtained from the liquid crystal aligning agent according to any one of 1 to 5.

7. A liquid crystal display element comprising the liquid crystal alignment film according to 7.6.

8. A method for producing a liquid crystal cell, which comprises applying a liquid crystal aligning agent according to any one of 1 to 5 to a substrate to contact with a liquid crystal alignment film obtained by firing to form a liquid crystal layer and irradiating ultraviolet rays while applying a voltage to the liquid crystal layer Wherein the liquid crystal display element is a liquid crystal display element.

9. A polymerizable compound characterized by the following formula [1].

[Chemical Formula 5]

(Wherein C represents a divalent organic group selected from the following formulas [C-2], [C-5] to [C-8] and [C-10]

[Chemical Formula 6]

(In the formulas [C-2], [C-5] to [C-8] and [C-10], * represents the bonding position with S ¹ and S ^{1 '}

S ¹ and S ^{1 '} are each independently a single bond or an alkylene group having 1 to 10 carbon atoms, and one or plural hydrogen atoms of the alkylene group may be substituted with a fluorine atom or an organic group. Further, in the case where S ^1, S ^{1 ',} the group of which do illustrated in the following are not adjacent to each other, -CH ₂ - is optionally are substituted with these; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -CO-.

S ² and S ^{2 '} are each independently a single bond or an alkylene group having 1 to 10 carbon atoms, and one or plural hydrogen atoms of the alkylene group may be substituted with a fluorine atom or an organic group. In addition, S ² and S ^{2 '} may be substituted with -CH ₂ - in the case where any of the groups shown below are not adjacent to each other; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -CO-.

P is a group which causes divalent light dimerization selected from the following formulas [P-1] to [P-3] and [P-5].

(7)

(In the formulas [P-1] to [P-3] and [P-5], * represents the bonding position with S ¹ , S ^{1 '} or S ² and S ^2' .)

L and L ^' are monovalent organic groups selected from the following formulas [L-1], [L-2] and [L-7].

[Chemical Formula 8]

(Of the formulas [L-1], [L-2] and [L-7], * represents the bonding position with S ² and S ^{2 '} .)

10. A polymerizable compound represented by any one of the following formulas.

[Chemical Formula 9]

(Wherein C represents a divalent organic group represented by any one of the following formulas, and n represents an integer of 2 to 4.)

[Chemical formula 10]

According to the present invention, it is possible to provide a liquid crystal display device capable of improving the response speed of a liquid crystal display element without containing a polymerizable compound in the liquid crystal and also in the case of a small irradiation amount and also in an ultraviolet irradiation condition of a longer wavelength Can be provided. In addition, the specific polymerizable compound used in the present invention is a novel compound unknown in the literature.

Hereinafter, the present invention will be described in detail.

The liquid crystal aligning agent of the present invention contains a specific polymerizable compound, a polymer forming a liquid crystal alignment film capable of aligning the liquid crystal, and a solvent. The liquid crystal aligning agent is a solution for producing a liquid crystal alignment film, and the liquid crystal alignment film is a film for aligning the liquid crystal in a predetermined direction, for example, a vertical direction. Hereinafter, each component contained in the liquid crystal aligning agent of the present invention will be described in detail.

≪ Specific polymerizable compound >

The specific polymerizable compound contained in the liquid crystal aligning agent of the present invention is represented by the following formula [1].

(11)

(In the formula [1], C is a divalent carbon ring-containing group having 10 to 30 carbon atoms and containing an aromatic ring, and one or plural hydrogen atoms of the carbon ring-containing group is substituted with a fluorine atom or an organic group .

S ¹ and S ^{1 '} are each independently a single bond or an alkylene group having 1 to 10 carbon atoms, and one or plural hydrogen atoms of the alkylene group may be substituted with a fluorine atom or an organic group. Further, in the case where S ^1, S ^{1 ',} the group of which do illustrated in the following are not adjacent to each other, -CH ₂ - is optionally are substituted with these; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -CO-.

P and P ^' each independently represent a group which causes divalent light dimerization selected from the following formulas [P-1] to [P-10]. One or a plurality of hydrogen atoms of the group in which this divalent light dimerization may be replaced with an organic group.

[Chemical Formula 12]

(In the formulas [P-1] to [P-10], * represents the bonding position with S ¹ , S ^{1 '} or S ² and S ^2' .)

S ² and S ^{2 '} are each independently a single bond or an alkylene group having 1 to 10 carbon atoms, and one or plural hydrogen atoms of the alkylene group may be substituted with a fluorine atom or an organic group. In addition, S ² and S ^{2 '} may be substituted with -CH ₂ - in the case where any of the groups shown below are not adjacent to each other; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -CO-.

L and L ^' each independently represent a monovalent photopolymerizable group selected from the following formulas [L-1] to [L-11].

[Chemical Formula 13]

(Of the formulas [L-1] to [L-11], * represents the bonding position with S ² and S ^{2 '} .)

C in the formula [1] is the core moiety of the polymerizable compound, and C represents a divalent carbon ring-containing group formed from 10 to 30 carbon atoms (for example, C represents a divalent carbon ring formed from 10 to 30 carbon atoms ) to be. Provided that one or plural hydrogen atoms of the carbon ring-containing group may be substituted with a fluorine atom or an organic group. Examples of the organic group include an alkyl group (-R), a hydroxyl group (-OH), an alkoxy group (-OR), a halogen group (-Cl, -Br, -I), a cyano group An alkylamino group (-NR ₂ ), an ester group (-COOR), and a nitro group (-NO ₂ ). Specific examples of the divalent carbon ring-containing group include divalent groups represented by the following formulas [C-1] to [C-12], but the present invention is not limited thereto. Among them, the divalent groups selected from the formulas [C-2], [C-5] to [C-8] and [C-10] are preferable from the standpoint of availability, ease of synthesis, .

[Chemical Formula 14]

(In the formulas [C-1] to [C-12], * represents a bonding position with S ¹ and S ^{1 '} .)

S ¹ and S ^{1 '} in the formula [1] are spacer sites connecting C, which is the core moiety of the polymerizable compound, and P and P ^' , which cause light dimerization, and are single bonds or C 1 to C 10 Alkylene group. Provided that any hydrogen atom of the alkylene group may be substituted with a fluorine atom or an organic group. Examples of the organic group include a hydroxyl group (-OH), an alkoxy group (-OR), a halogen group (-Cl, -Br, -I), a dialkylamino group (-NR ₂ ) ). The number of hydrogen atoms to be substituted may be one or plural. Furthermore, one or more -CH ₂ - groups of the alkylene group may be replaced with -CH ₂ - in the case where any of the bonding groups shown below are not adjacent to each other, -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, -NH-, -CO-. Further, -CH ₂ - substituted by the bonding group may be in one site or may be plural sites if the bonding groups are not adjacent to each other. It is preferable that S ¹ and S ^{1 'each} independently represent an alkylene group - a constitutional unit thereof, or a constituent unit thereof - an alkylene group or an alkylene group - a constituent unit thereof, or an alkylene group - And may include a coupler. S ¹ and S ^{1 '} may have the same structure or different from each other, but if they are the same, synthesis is easy.

P and P ^' in the formula [1] represent a group in which the light dimerization selected in the above formulas [P-1] to [P-10] occurs. The group that causes photodimerization is a functional group that forms a dimer by reacting by irradiation of light. These one or plural hydrogen atoms may be substituted with an organic group. Examples of the organic group include an alkyl group (-R), a hydroxyl group (-OH), an alkoxy group (-OR), a halogen group (-Cl, -Br, -I), a cyano group An alkylamino group (-NR ₂ ), an ester group (-COOR), and a nitro group (-NO ₂ ). Among them, divalent organic groups represented by the above formulas [P-1] to [P-3] and [P-5] are preferably used from the viewpoints of ease of synthesis and manifestation of the effect of the present invention.

S ² and S ^{2 '} in the formula [1] are spacer sites connecting P and P ^' which are sites where light dimerization occurs and L and L ^'which are photopolymerizable groups and are single bonds or formed from 1 to 10 carbon atoms Lt; / RTI > Provided that any hydrogen atom of the alkylene group may be substituted with a fluorine atom or an organic group. Examples of the organic group include a hydroxyl group (-OH), an alkoxy group (-OR), a halogen group (-Cl, -Br, -I), a dialkylamino group (-NR ₂ ) ). The number of hydrogen atoms to be substituted may be one or plural. Furthermore, one or more -CH ₂ - groups of the alkylene group may be replaced with -CH ₂ - in the case where any of the bonding groups shown below are not adjacent to each other, -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, -NH-, -CO-. Further, -CH ₂ - substituted by the bonding group may be in one site or may be plural sites if the bonding groups are not adjacent to each other. It is preferable that S ² and S ^{2 'each} independently represent an alkylene group-a bonding group or a bonding group-an alkylene group or an alkylene group-a bonding group-an alkylene group or a bonding group-an alkylene group And may include a coupler. In addition, S ² and S ^{2 '} may have the same structure or different from each other, but if they are the same, synthesis is easy.

L and L ^' in the formula [1] represent monovalent photopolymerizable groups selected from the following formulas [L-1] to [L-11]. The photopolymerizable group is a functional group that generates polymerization by irradiation of light.

[Chemical Formula 15]

(Of the formulas [L-1] to [L-11], * represents the bonding position with S ² and S ^{2 '} .)

Among them, monovalent photopolymerizable groups represented by the formulas [L-1] and [L-2] are preferred from the viewpoint of ease of synthesis, and monovalent photopolymerizable groups represented by the formula [L-7] , Respectively.

≪ Synthesis method of specific polymerizable compound >

A method for synthesizing the specific polymerizable compound represented by the formula [1] of the present invention is not particularly limited, and examples thereof include the following methods.

For example, when an amide bond (-CONH-) or an inverse amide bond (-HNCO-) is contained in the structure of L ^' -S ^2' -P ^' -S ^1' -CS ¹ -PS ² -L, or C, S ^1, S ^{1 ',} or, P, ^P', or, S ^2, S ² as in the combined chloride group (-COCl) acid at the terminal of the ^"or, L, L ^', or C (-NH ₂ ) is bonded to the ends of S ¹ , S ^{1 '} or P, P ^' or S ² , S ^{2 '} or L, L ^' Method.

For example, when an ester bond (-COO-) or a reverse ester bond (-OCO-) is contained in the structure of L ^' -S ^2' -P ^' -S ^1' -CS ¹ -PS ² -L, or C, S ^1, S ^{1 ',} or, P, ^P', or, S ^2, S ² as in the combined chloride group (-COCl) acid at the terminal of the ^"or, L, L ^', or C (-OH) is bonded to the ends of S ¹ , S ^{1 '} , or P, P ^' , or S ² , S ^{2 '} , or L and L ^' .

For example, when the structure of L ^' -S ^2' -P ^' -S ^1' -CS ¹ -PS ² -L has an ether bond (-O-), C, S ¹ , S ^{1 '} , P, P ^', or, S ^2, S ^2', or, as the bonded L, L ^'terminal halogen atom (-F, -Cl, -Br, -I ) of the, or C, S ¹ , the S ^{1 ',} or, P, ^P', or, S ^2, S ² reacting in that the hydroxyl group (-OH) is bonded at the terminal of the ^"or, L, L ^', under the presence of an alkali .

For example, in the case of having an amino bond (-NH-) in the structure of L ^' -S ^2' -P ^' -S ^1' -CS ¹ -PS ² -L, C or S ¹ , S ^{1 '} (-F, -Cl, -Br, -I) is bonded to the ends of P, P ^' or S ² , S ^2' or L and L ^{' 1,} S ^{1 ',} or, P, ^P', or, S ^2, S ^2, and that the amino group (-NH ₂₎ coupled to a terminal of ^', or, L, ^L', a method of reaction in the presence of an alkali a .

For example, where the structure of the ^{L '-S 2' -P '-S} 1' -CS 1 -PS 2 -L with a carbonyl bond (-CO-), or C, S ^1, S ^{1 '} , Or an aldehyde group (-CHO) is bonded to the end of P, P ^' , or S ² , S ^2' , or L, L ^' , and C or S ¹ , S ^1' , P ^' , or a method in which a boronic acid group (-B (OH) ₂ ) is bonded to the end of S ² , S ^2' or L, L ^'in the presence of an alkali.

Specific examples of the specific polymerizable compound represented by the formula [1] include a polymerizable compound represented by the following formula. Wherein S ¹ , S ^{1 '} , S ² and S ^2' each independently represent an alkylene group having a single bond or a carbon number of 1 to 10, and the alkylene group of the alkylene group One or more hydrogen atoms may be substituted with a fluorine atom or an organic group. In addition, S ² and S ^{2 '} may be substituted with -CH ₂ - in the case where any of the groups shown below are not adjacent to each other; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -CO-.

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

By using the liquid crystal aligning agent containing the polymerizable compound represented by the formula [1] of the present invention, the response speed of the liquid crystal display element can be improved without containing the polymerizable compound in the liquid crystal, , And can be improved even in the ultraviolet irradiation condition of a longer wavelength. The reason why the problems of the present invention can be solved by using the liquid crystal aligning agent containing the polymerizable compound represented by the formula [1] of the present invention is not necessarily clear, but is generally considered as follows. The polymerizable compound represented by the formula [1] of the present invention has a large volume at its center and a functional group containing aromatic rings, or the absorption maximum of the polymerizable compound itself shifts to a long wavelength, It is believed that even in the case of ultraviolet light, it is sufficiently reacted to fix the liquid crystal, and the response speed is increased. Further, the polymerizable compound represented by the formula [1] remains in the film due to the bulky structure or the polymerizable compound does not sublimate even when exposed to high temperatures at the time of film formation of the liquid crystal alignment film. As a result, it is considered that even a small amount of ultraviolet light can sufficiently react to fix the liquid crystal.

≪ Polymer forming liquid crystal alignment film capable of aligning liquid crystals >

The polymer forming the liquid crystal alignment film capable of aligning the liquid crystal contained in the liquid crystal aligning agent of the present invention is not particularly limited as long as it is capable of aligning the liquid crystal on the liquid crystal alignment film formed on the substrate and may be a polyimide precursor, And polyimide obtained by imidizing a polyimide precursor. Examples of the polyimide precursor include polyamic acid (also referred to as polyamide acid) or polyamic acid ester. Such a polyimide precursor can be obtained by reacting a diamine component (for example, a diamine having a side chain for vertically orienting a liquid crystal or a diamine having a photoreactive side chain), and a tetracarboxylic acid dianhydride component For example, a tetracarboxylic acid dianhydride, a tetracarboxylic acid diester dichloride, a tetracarboxylic acid diester, etc.). Specifically, the polyamic acid is obtained by the reaction of the diamine component and the tetracarboxylic acid dianhydride. The polyamic acid ester is obtained by reacting a diamine component with a tetracarboxylic acid diester dichloride in the presence of a base, or by reacting a tetracarboxylic acid diester and a diamine component in the presence of a suitable condensing agent or a base. The polyimide is obtained by subjecting the polyamic acid to dehydration ring closure, or by heating and closing the polyamic acid ester. Such a polyamic acid, a polyamic acid ester, and a polyimide are both useful as a polymer for obtaining a liquid crystal alignment film.

Specific examples of the polymer forming the liquid crystal alignment film capable of aligning the liquid crystal contained in the liquid crystal aligning agent of the present invention include a polymer capable of orienting the liquid crystal on the liquid crystal alignment film formed on the substrate perpendicularly to the substrate . As such a polymer capable of orienting the liquid crystal on the liquid crystal alignment film formed on the substrate perpendicularly to the substrate, a polymer having a side chain for vertically orienting the liquid crystal is preferable, and a polymer having a side chain for vertically orienting the liquid crystal A polyimide precursor and a polyimide obtained by imidizing the polyimide precursor.

The side chain for orienting the liquid crystal vertically is not limited as long as the liquid crystal can be oriented perpendicular to the substrate. For example, the side chain may be a long chain alkyl group, a group having a ring structure or a branch structure in the middle of the long chain alkyl group, A steroid group, a group in which a part or all of the hydrogen atoms of these groups are substituted with a fluorine atom, and the like. The side chains for orienting the liquid crystal vertically may be directly bonded to the main chain of the polymer such as a polyimide precursor or polyimide, or may be bonded via a suitable bonding group. Examples of the side chain for vertically orienting the liquid crystal include those represented by the following formula (a).

[Chemical Formula 22]

(In the formula (a), l, m and n each independently represent an integer of 0 or 1, and R ⁷ represents an alkylene group having 2 to 6 carbon atoms, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or an alkylene group-ether group having 1 to 3 carbon atoms; R ⁸ , R ⁹ and R ¹⁰ each independently represent a phenylene group or a cycloalkylene group; R ¹¹ represents a hydrogen atom, an alkyl group having 2 to 24 carbon atoms Or a fluorine-containing alkyl group, a monovalent aromatic ring, a monovalent aliphatic ring, a monovalent heterocyclic ring, or a monovalent macrocyclic substituent thereof.

R ⁷ in the formula (a) is preferably -O-, -COO-, -CONH- or an alkylene group-ether group having 1 to 3 carbon atoms, from the viewpoint of ease of synthesis.

R ⁸ , R ⁹ and R ¹⁰ in the formula (a) are 1, m, n, R ⁸ , R ⁹ and R ⁹ shown in the following Table 1 from the viewpoints of ease of synthesis and ability to vertically orient the liquid crystal ¹⁰ is preferable.

When at least one of 1, m and n is 1, R ¹¹ in the formula (a) is preferably a hydrogen atom or an alkyl group having 2 to 14 carbon atoms or a fluorine-containing alkyl group, more preferably a hydrogen atom or a carbon number An alkyl group having 2 to 12 carbon atoms or a fluorine-containing alkyl group. When l, m and n are both 0, R ¹¹ is preferably an alkyl group or a fluorine-containing alkyl group having 12 to 22 carbon atoms, a monovalent aromatic ring, a monovalent aliphatic ring, a monovalent heterocyclic ring, , More preferably an alkyl group having 12 to 20 carbon atoms or a fluorine-containing alkyl group.

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

The ability of a polymer having a side chain to vertically align liquid crystals to orient liquid crystals vertically differs depending on the structure of side chains that vertically align liquid crystals, but generally, a side chain As the amount increases, the ability to align the liquid crystal vertically increases, and when it decreases, it decreases. In addition, when a cyclic structure is provided, the ability of aligning the liquid crystal vertically tends to be higher than in the case of not having a cyclic structure.

The polymer forming the liquid crystal alignment film for vertically aligning the liquid crystal preferably has a photoreactive side chain. Having the photoreactive side chain can further improve the response speed. The photoreactive side chain is a side chain having a functional group (hereinafter also referred to as a photoreactive group) capable of reacting by irradiation with ultraviolet light to form a covalent bond, and the structure is not limited as long as it has this ability. Examples of the photoreactive side chain include a side chain having a vinyl group, an acrylic group, a methacrylic group, an allyl group, a styryl group, a cinnamoyl group, a chalconyl group, a coumarin group, a maleimide group, etc. as a photoreactive group . The photoreactive side chain may be directly bonded to the main chain of the polymer such as a polyimide precursor or polyimide, or may be bonded via a suitable bonding group. The photoreactive side chain includes, for example, those represented by the following formula (b).

(23)

(In the formula (b), R ¹² represents a single bond or -CH ₂ -, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N (CH ₃ ) -, -CON (CH ₃ ) -, or -N (CH ₃ ) CO-, and R ¹³ represents a single bond or a substituted or unsubstituted alkyl group having 1 to 20 , -CH ₂ - in the alkylene group may be optionally substituted with -CF ₂ - or -CH═CH-, and in the case where any of the groups shown below are not adjacent to each other, -OCO-, -NHCO-, -CONH-, -NH-, a divalent carbon ring, a divalent heterocyclic ring, R ¹⁴ represents a vinyl group, an acrylic group, a methacrylic group , An allyl group, a styryl group, -N (CH ₂ CH = CH ₂ ) ₂ , or a structure represented by the following formula:

≪ EMI ID =

R ¹² in the formula (b) may be formed by a conventional organic synthetic method, but from the viewpoint of ease of synthesis, -CH ₂ -, -O-, -COO-, -NHCO-, -NH-, -CH ₂ O- is preferred.

Specific examples of the carbon ring or heterocyclic ring of the divalent carbon ring or the divalent heterocyclic ring for substituting any -CH ₂ - in R ¹³ include, but are not limited to, the following structures .

(25)

(26)

R ¹⁴ preferably has a structure represented by a vinyl group, an acrylic group, a methacrylic group, an allyl group, a styryl group, -N (CH ₂ CHCH ₂ ) ₂ or the following formula from the viewpoint of photoreactivity.

(27)

The above formula (b) more preferably has the following structure.

(28)

The abundance of the photoreactive side chain is preferably within a range capable of accelerating the response speed of the liquid crystal by reacting with ultraviolet light to form a covalent bond and in order to accelerate the response speed of the liquid crystal, It is preferable that the number is as large as possible within a range that does not cause a problem.

A method for producing such a polymer forming a liquid crystal alignment film for vertically aligning the liquid crystal is not particularly limited. For example, in the case of producing a polyamic acid having a side chain for vertically orienting a liquid crystal, A method of obtaining a polyamic acid by reaction of a carboxylic acid dianhydride component includes a method of copolymerizing a diamine having a side chain that vertically aligns the liquid crystal or a tetracarboxylic acid dianhydride having a side chain that vertically aligns the liquid crystal This is easy. When the photoreactive side chain is contained in the polymer forming the liquid crystal alignment film for vertically aligning the liquid crystal, a diamine having a photoreactive side chain or a tetracarboxylic dianhydride having a photoreactive side chain may be copolymerized.

Examples of the diamine having a side chain that vertically aligns the liquid crystal include a long-chain alkyl group, a group having a ring structure or branched structure in the middle of the long-chain alkyl group, a steroid group, or a group in which some or all of hydrogen atoms in these groups are substituted with a fluorine atom And a diamine having a side chain, for example, a diamine having a side chain represented by the above formula (a). More specifically, for example, diamines represented by the following formulas (2), (3), (4), and (5) may be mentioned, but the present invention is not limited thereto.

[Chemical Formula 29]

(The definitions of 1, m, n and R ⁷ to R ¹¹ in the formula (2) are the same as those of the formula (a).)

(30)

(31)

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

(32)

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

The bonding position of two amino groups (-NH ₂ ) in the formula (2) is not limited. Specifically, with respect to the coupler of the side chains, positions 2 and 3, positions 2 and 4, positions 2 and 5, positions 2 and 6, positions 3 and 4, positions 3 and 5 on the benzene ring . Among them, from the viewpoint of reactivity in the synthesis of polyamic acid, positions 2 and 4, positions 2 and 5, and positions 3 and 5 are preferable. When the ease of synthesis of the diamine is also considered, positions 2 and 4 or positions 3 and 5 are more preferable.

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

(33)

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

(34)

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

(35)

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

(36)

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

(37)

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

(38)

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

[Chemical Formula 39]

(40)

(41)

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.

(42)

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

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

(43)

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

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

The diamine having a side chain that vertically aligns the liquid crystal is preferably used in an amount of 5 to 50 mol% of the diamine component used in the synthesis of the polyamic acid and the like, 40 mol% is a diamine having a side chain that vertically aligns the liquid crystal, and particularly preferably 15 to 30 mol%. When the diamine having a side chain that vertically aligns 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 or the like in this way, in view of the improvement in the response speed and the ability to fix the orientation of liquid crystals great.

Examples of the diamine having a photoreactive side chain include diamines having a photoreactive group as a side chain such as a vinyl group, an acrylic group, a methacrylic group, an allyl group, a styryl group, a cinnamoyl group, a chalconyl group, a coumarin group, For example, diamines having side chains represented by the above formula (b). More specifically, for example, the diamine represented by the following general formula (6) can be mentioned, but is not limited thereto.

(44)

(The definitions of R ¹² , R ¹³ and R ^{14 in} the formula (6) are the same as those in the formula (b).)

The bonding position of two amino groups (-NH ₂ ) in the formula (6) is not limited. Specifically, with respect to the coupler of the side chains, positions 2 and 3, positions 2 and 4, positions 2 and 5, positions 2 and 6, positions 3 and 4, positions 3 and 5 on the benzene ring . Among them, from the viewpoint of reactivity in the synthesis of polyamic acid, positions 2 and 4, positions 2 and 5, and positions 3 and 5 are preferable. When the ease of synthesis of the diamine is also considered, positions 2 and 4 or positions 3 and 5 are more preferable.

Specific examples of the diamine having a photoreactive group include, but are not limited to, the following compounds.

[Chemical Formula 45]

(Wherein X is a single bond or a bonding group selected from -O-, -COO-, -NHCO-, -NH-, and Y is a single bond or a carbon-carbon double bond, An alkylene group having 1 to 20 carbon atoms.

The diamine having the photoreactive group may be used singly or in combination of two or more types depending on the properties such as liquid crystal alignment property, pretilt angle, voltage holding property, and accumulated charge when used as a liquid crystal alignment film, May be mixed and used.

The diamine having such a photoreactive group is preferably used in an amount of 10 to 70 mol%, more preferably 20 to 60 mol%, particularly preferably 10 to 70 mol% of the diamine component used for the synthesis of polyamic acid and the like Is 30 to 50 mol%.

In addition, as long as the effect of the present invention is not impaired, polyamic acid and the like may be used in combination with other diamines other than the diamine having a photoreactive group, such as a diamine having a side chain that vertically aligns the liquid crystal, as a diamine component . When it is not necessary to orient the liquid crystal vertically, the introduction amount of the diamine having a side chain that vertically aligns the liquid crystal may be reduced. In the case of orienting the liquid crystal horizontally, the side chain Is not used.

Specific examples of the diamine include p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p- Diaminopropanol, 2,4-diaminophenol, 2,3-diaminophenol, 2,6-diaminopropanol, 2,5-diaminopropanol, 5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'- diaminobiphenyl, 3,3'-dimethyl Diaminobiphenyl, 3,3'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, Dicarboxy-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl-4,4'-diamino Biphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diamino Diphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenyl Methane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2 ' (4-aminophenyl) silane, bis (3-aminophenyl) silane, bis (4-aminophenyl) (4-aminophenyl) silane, 4,4'-thiodianiline, 3,3'-thiodianiline, 4,4'-di Aminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N (3,3'-diaminodiphenyl) amine, N-methyl (3,4'-diaminodiphenyl) amine, N-methyl (2,2'-diaminodiphenyl) amine, N-methyl (2,3'-diaminodiphenyl) amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3 , 4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2, Diaminobenzophenone, 2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, Diaminonaphthalene, 2,6-diaminonaphthalene, 2,6-diaminonaphthalene, 2,6-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6- (3-aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,3- Bis (3-aminophenyl) butane, bis (3,5-diethyl-4-aminophenyl) methane, 1,4- Benzene, 1,4-bis (4-aminophenyl) benzene, 1,3-bis (4-aminophenyl) (Aminophenoxy) benzene, 4,4 '- [1,4-phenylenebis (methylene)] dianiline, 4,4' - [1,3-phenylenebis '- [1,4-phenylenebis (methylene)] dianiline, 3,4' - [1,3-phenylenebis Phenylenebis (methylene)] dianiline, 1,3-phenylenebis (methylene)] dianiline, 3,3 '- [ (4-aminophenyl) methanone], 1,3-phenylenebis [(3-aminophenyl) methanone] Phenylene bis (3-aminophenyl) methanone], 1,4-phenylene bis (4-aminobenzoate), 1,4-phenylene bis Bis (4-aminophenyl) terephthalate, bis (4-aminobenzoate), 1,3-phenylene bis Bis (3-aminophenyl) isophthalate, N, N '- (1,4-phenylene) (3-aminobenzamide), N, N '- (1,3-phenylene) bis (3-aminobenzamide) ), N, N'-bis (4-aminophenyl) terephthalamide, N, N'- Bis (4-aminophenyl) isothiamides, N, N'-bis (3-aminophenyl) isophthalamide, 9,10- Bis [4- (4-aminophenoxy) phenyl] propane, 2,2'-bis [4- Aminophenyl) hexafluoropropane, 2,2'-bis (4-aminophenyl) hexafluoropropane, 2,2'-bis Bis (4-aminophenyl) propane, 2,2'-bis (3-aminophenyl) propane, 2,2'-bis (3-amino-4-methylphenyl) propane, 3,5-diaminobenzoic acid, 2,5- Propane, 1,4-bis (4-aminophenoxy) butane, 1,4-bis (3-aminophenoxy) butane, 1,5- Bis (3-aminophenoxy) pentane, 1,6-bis (4-amino (3-aminophenoxy) heptane, 1,7- (3-aminophenoxy) heptane, 1,8- Bis (4-aminophenoxy) octane, 1,9-bis (4-aminophenoxy) Nonane, 1,10- (4-aminophenoxy) decane, 1,10- (3-aminophenoxy) decane, 1,11- (4-aminocyclohexyl) methane, bis (4-aminophenoxy) dodecane and the like, aromatic diamines such as 1,12- Amino-3-methylcyclohexyl) methane; alicyclic diamines such as 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, , 7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane Of an aliphatic diamine.

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

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

The tetracarboxylic acid ester to be reacted with the diamine component in order to obtain the polyamic acid ester contained in the liquid crystal aligning agent used in the present invention is not particularly limited. Specific examples thereof are given below.

Specific examples of the aliphatic tetracarboxylic acid diester include 1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester , 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl Ester, 1,2,3,4-cyclopentanetetracarboxylic acid dialkyl ester, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dialkyl ester, 1,2,4,5-cyclohexanetetracarboxylic acid Dicarboxy-1-cyclohexylsuccinic acid dialkyl ester, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid dialkyl ester, 1,2, Butanetetracarboxylic acid dialkyl ester, bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid dialkyl ester, 3,3 ', 4,4'-dicyclo Diethyl hexyltetracarboxylate Stearyl, 2,3,5-tricarboxycyclopentylacetic acid dialkyl ester, cis-3,7-dibutylcycloocta-1,5-diene-1,2,5,6-tetracarboxylic acid dialkyl ester, Tetracarboxylic acid-3,4: 7,8-dialkyl ester, hexacyclo [6.6.0.12,7.03,6.19,14.010,13 ] Hexadecane-4,5,11,12-tetracarboxylic acid-4,5: 11,12-dialkyl ester, 4- (2,5-dioxotetrahydrofuran- , 3,4-tetrahydronaphthalene-1,2-dicarboxylic alkyl ester, and the like.

Examples of the aromatic tetracarboxylic acid dialkyl ester include pyromellitic acid dialkyl ester, 3,3 ', 4,4'-biphenyltetracarboxylic acid dialkyl ester, 2,2', 3,3'-biphenyltetracarboxylic acid Biphenyltetracarboxylic acid dialkyl ester, 3,3 ', 4,4'-benzophenonetetracarboxylic acid dialkyl ester, 2,3,3', 4 (3,4-dicarboxyphenyl) ether dialkyl ester, bis (3,4-dicarboxyphenyl) sulfonyl alkyl ester, 1,2,5,6-naphthalene tetra Carboxylic acid dialkyl esters, 2,3,6,7-naphthalenetetracarboxylic acid dialkyl esters and the like.

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

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

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

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

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

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

The polyamic acid ester which is a polyimide precursor can be synthesized by the following methods (1) to (3).

(1) Synthesis from polyamic acid

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

Concretely, the polyamic acid and the esterifying agent are reacted in the presence of an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C for 30 minutes to 24 hours, preferably 1 to 4 hours .

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

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

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

Polyamic acid esters can be synthesized from tetracarboxylic acid diester dichloride and diamines.

Specifically, the tetracarboxylic acid diester dichloride and diamine are reacted in the presence of a base and an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C for 30 minutes to 24 hours, For 4 hours.

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

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

(3) When polyamic acid is synthesized from tetracarboxylic acid diester and diamine

The polyamic acid ester can be synthesized by polycondensation of a tetracarboxylic acid diester and a diamine.

Specifically, the tetracarboxylic acid diester and the diamine are reacted in the presence of a condensing agent, a base and an organic solvent at 0 ° C to 150 ° C, preferably 0 ° C to 100 ° C for 30 minutes to 24 hours, For 15 hours.

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

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

In addition, in the above reaction, the reaction proceeds efficiently by adding Lewis acid as an additive. As the Lewis acid, lithium halides such as lithium chloride and lithium bromide are preferable. The addition amount of the Lewis acid is preferably from 0 to 1.0 times the amount of the diamine component.

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

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

Examples of the method of imidizing the polyamic acid or polyamic acid ester into polyimide include thermal imidization in which a solution of a polyamic acid or a polyamic acid ester is directly heated, a catalyst in which a catalyst is added to a solution of a polyamic acid or a polyamic acid ester Imitation can be heard. In addition, the imidation rate from polyamic acid or polyamic acid ester to polyimide does not necessarily have to be 100%.

When the polyamic acid or the polyamic acid ester is thermally imidized in the solution, the temperature is 100 ° C to 400 ° C, preferably 120 ° C to 250 ° C, and the water generated by the imidization reaction is removed while removing it from the system desirable.

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

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

As described above, the liquid crystal aligning agent of the present invention may be any one having a specific polymerizable compound, a polymer forming a liquid crystal alignment film capable of aligning the liquid crystal, and a solvent, and the mixing ratio thereof is not particularly limited. The content of the compound is preferably 1 to 50 parts by mass, more preferably 5 to 30 parts by mass, per 100 parts by mass of the polymer forming the liquid crystal alignment film capable of aligning the liquid crystal. The content of the polymer forming the liquid crystal alignment film capable of aligning the liquid crystal contained in the liquid crystal aligning agent is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, 3 to 10% by mass.

The liquid crystal aligning agent of the present invention may contain a polymer other than the polymer forming the liquid crystal alignment film capable of aligning the liquid crystal. At this time, the content of such another polymer in the entire polymer component is preferably 0.5% by mass to 15% by mass, and more preferably 1% by mass to 10% by mass.

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

<Solvent>

The solvent contained in the liquid crystal aligning agent of the present invention is not particularly limited and any solvent may be used as long as it can dissolve or disperse the components including the specific polymerizable compound and the polymer forming the liquid crystal alignment film capable of aligning the liquid crystal. For example, organic solvents such as those exemplified in the synthesis of the polyamic acid may be mentioned. Among them, N-methyl-2-pyrrolidone,? -Butyrolactone, N-ethyl-2-pyrrolidone, Dimethyl propanamide is preferable from the viewpoint of solubility. Of course, two or more types of mixed solvents may be used.

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

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

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

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

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

This liquid crystal aligning agent is coated on the substrate and baked to form a liquid crystal alignment film capable of aligning liquid crystal such as a liquid crystal alignment film for vertically aligning the liquid crystal. Since the liquid crystal aligning agent of the present invention has a specific polymerizable compound, the response speed of the liquid crystal display element using the obtained liquid crystal alignment film can be made faster without containing a polymerizable compound in the liquid crystal. In addition, when the liquid crystal alignment film is formed by using the liquid crystal alignment agent, the response speed of the liquid crystal display device using the obtained liquid crystal alignment film can be made fast even in the case of firing at a high temperature. Of course, the response speed of the liquid crystal display element can be made fast even when a specific polymerizable compound is contained in the liquid crystal or when it is fired at a low temperature (for example, 140 DEG C or less).

At this time, the substrate to be used is not particularly limited as long as it is a substrate having high transparency, and a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used. In addition, it is preferable to use a substrate on which an ITO (Indium Tin Oxide) electrode for liquid crystal driving is formed from the viewpoint of simplifying the process. In a reflective liquid crystal display element, an opaque material such as a silicon wafer can be used only for a substrate on one side. In this case, a material for reflecting light such as aluminum can also be used as the electrode in this case.

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

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

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

The liquid crystal display element of the present invention comprises two substrates arranged so as to face each other, a liquid crystal layer formed between the substrates, and a liquid crystal alignment layer formed between the substrate and the liquid crystal layer and formed by the liquid crystal aligning agent of the present invention And a vertical alignment method including a liquid crystal cell. More specifically, a liquid crystal alignment film is formed by applying the liquid crystal aligning agent of the present invention on two substrates and firing, and two substrates are arranged so that the liquid crystal alignment films face each other. And a liquid crystal cell produced by sandwiching the constituted liquid crystal layer and irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer. As described above, by using the liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention, ultraviolet rays are irradiated while a voltage is applied to the liquid crystal alignment film and the liquid crystal layer to polymerize the specific polymerizable compound and to align the liquid crystal alignment film Or a polymer of a specific polymerizable compound with a specific polymerizable compound and crosslinking them, a liquid crystal display device having an excellent response speed is obtained.

The substrate used in the liquid crystal display of the present invention is not specifically limited as long as it is a substrate having high transparency, but is usually a substrate on which a transparent electrode for driving liquid crystal is formed. Specific examples include the same substrates as those described in the liquid crystal alignment film. A substrate on which a conventional electrode pattern or a projection pattern is formed may be used. However, in the liquid crystal display element of the present invention, since the liquid crystal aligning agent of the present invention containing a specific polymerizable compound is used as the liquid crystal aligning agent for forming the liquid crystal alignment film , A structure in which a line / slit electrode pattern of 1 to 10 mu m is formed on a unilateral substrate, and a slit pattern or a projection pattern is not formed on the counter substrate, and the liquid crystal display device of this structure Can be simplified, and a high transmittance can be obtained.

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

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

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

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

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

The step of producing a liquid crystal cell by irradiating ultraviolet rays while applying a voltage to a liquid crystal alignment film and a liquid crystal layer is performed by applying an electric field to a liquid crystal alignment film and a liquid crystal layer by applying a voltage between electrodes provided on the substrate, And a method of irradiating ultraviolet rays while maintaining the electric field. Here, the voltage applied between the electrodes is, for example, 5 to 30 Vp-p, preferably 5 to 20 Vp-p. The irradiation amount of ultraviolet rays is, for example, 1 to 60 J or less, preferably 40 J or less. When the amount of ultraviolet irradiation is small, reliability deterioration caused by destruction of members constituting the liquid crystal display element can be suppressed Since the ultraviolet ray irradiation time can be reduced, the manufacturing efficiency is increased, which is suitable. The wavelength of the ultraviolet ray to be irradiated is, for example, 200 nm to 400 nm. In the present invention, since the liquid crystal aligning agent containing the polymerizable compound represented by the formula [1] is used, even when the irradiation condition of the ultraviolet ray is a small irradiation amount, Nm), it is possible to improve the response speed of the liquid crystal display element.

As described above, when ultraviolet rays are irradiated while applying a voltage to the liquid crystal alignment film and the liquid crystal layer, a certain polymerizable compound reacts to form a polymer, and the direction in which the liquid crystal molecules incline is memorized by the polymer, Can speed up.

In the above description, the liquid crystal display device produced by incorporating the specific polymerizable compound into the liquid crystal aligning agent for forming the liquid crystal alignment film has been described. However, the liquid crystal display device of the present invention may be a liquid crystal display, do.

The liquid crystal aligning agent is not only useful as a liquid crystal aligning agent for producing a liquid crystal display element such as a PSA type liquid crystal display or a SC-PVA type liquid crystal display such as a vertical alignment system, And can also be suitably used for a liquid crystal alignment film to be produced.

Example

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

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

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

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

3AMPDA: 3,5-diamino-N- (pyridin-3-ylmethyl) benzamide represented by the following formula

(46)

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

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

(47)

NMP: N-methyl-2-pyrrolidone

BCS: butyl cellosolve

THF: tetrahydrofuran

DMF: N, N-dimethylformamide

EtOH: ethanol

RM1: polymerizable compound represented by the following formula

(48)

RM2: polymerizable compound represented by the following formula

(49)

RM3: polymerizable compound represented by the following formula

(50)

RM4: polymerizable compound represented by the following formula

(51)

RM5: polymerizable compound represented by the following formula

(52)

< ¹ Measurement of HNMR>

The measurement conditions of ¹ HNMR of the polymerizable compound are as follows.

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

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

Standard material: tetramethylsilane (TMS)

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

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

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

Column temperature: 50 ° C

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

Flow rate: 1.0 ml / min

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

The imidization rate of the polyimide was measured as follows. 20 mg of the polyimide powder was placed in an NMR sample tube (NMR sampling tube standard 5 manufactured by Kusano Scientific Co., Ltd.), 1.0 ml of deuterated dimethyl sulfoxide (DMSO-d ₆ , 0.05% TMS mixture) was added and completely dissolved by applying ultrasonic waves . This solution was subjected to proton NMR measurement at 500 MHz using an NMR meter (JNW-ECA500) manufactured by Nippon DATUM Co., The proton derived from the structure which does not change before and after the imidization is defined as a reference proton and the peak integrated value of the proton and the proton peak integrated value derived from the NH group of the amic acid appearing in the vicinity of 9.5 to 10.0 ppm By using the following formula. 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? Is the NH of the amic acid when the polyamic acid (imidation rate is 0%) Is the ratio of the number of reference protons to one proton of the group.

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

&Lt; Synthesis of polymerizable compound &gt;

(Example 1) Synthesis of RM1

(Synthesis Example 1) Synthesis of precursor RM1-1 of RM1

(53)

34.2 g of 2,2-bis (4-hydroxyphenyl) propane, 600 ml of N, N-dimethylformamide, 67.8 g of 4-chlorobutyl acetate, 124.4 g of potassium carbonate, 12.5 g of potassium iodide was added, and the mixture was stirred at 100 캜. After completion of the reaction, the reaction system was poured into 5 L of water, neutralized with 1 N HCl aqueous solution, and the precipitate was filtered and dried. The resulting filtrate was placed in a 1 L three-necked flask, and 600 mL of ethanol and 250.0 g of a 10 wt% KOH aqueous solution were added and stirred while heating under reflux. After completion of the reaction, the reaction system was poured into 3 L of water, neutralized with 1 N HCl aqueous solution, and the precipitate was filtered. The filtrate was dried to obtain 54.1 g of the objective product RM1-1 (white solid) (yield: 97%).

(Synthesis Example 2) Synthesis of precursor RM1-2 of RM1

(54)

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

In a 500 ml three-necked flask, 22.4 g of RM1-1, 200 ml of tetrahydrofuran and 15.8 g of triethylamine were added, the temperature in the system was adjusted to 0 캜, and 17.9 g of methanesulfonyl chloride was added. Lt; / RTI &gt; After completion of the reaction, the reaction system was poured into 1 liter of water, 500 ml of ethyl acetate was added, and extraction was carried out using saturated brine. Anhydrous magnesium sulfate was added to the organic layer, followed by dehydration drying and filtration. Thereafter, the solvent was distilled off using a rotary evaporator to obtain 31.53 g of the objective product RM1-2 (white solid) (yield: 99%).

(Synthesis Example 3) Synthesis of RM3 precursor RM3

(55)

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

In a 300 ml three-necked flask, 7.9 g of RM1-2, 200 ml of N, N-dimethylformamide, 5.4 g of trans-p-coumaric acid and 12.4 g of potassium carbonate were added and stirred at 100 ° C. After completion of the reaction, the reaction system was poured into 1 liter of water, neutralized with 1 N HCl aqueous solution, and the precipitate was filtered. The filtrate was washed with methanol and dried to obtain 9.7 g of the objective RM3 (white solid) (yield: 93%).

(Synthesis Example 4) Synthesis of precursor RM1-4 of RM1

(56)

In a 200 ml three-necked flask, 5.0 g of RM3, 50 ml of ethanol and 10.0 g of a 10 wt% KOH aqueous solution were added and stirred while heating under reflux. After completion of the reaction, the reaction system was poured into 200 ml of water and neutralized with a 1N HCl aqueous solution. The precipitate was filtered and dried to obtain 4.6 g of the objective product RM1-4 (white solid) (yield: 97%). .

(Synthesis Example 5) Synthesis of RM1

(57)

In a 200 ml three-necked flask, 4.6 g of RM1-4, 50 ml of tetrahydrofuran, 2.7 g of 2-hydroxyethyl methacrylate (HEMA) and 0.1 g of 1- (3-dimethylaminopropyl) 4.0 g of the bodymide hydrochloride (EDC) and 0.2 g of 4-dimethylaminopyridine (DMAP) were added, and the mixture was stirred at room temperature. After completion of the reaction, the reaction system was poured into 200 ml of water, and the precipitate was filtered and dried to obtain 6.0 g of the objective RM1 (white solid) (yield: 96%). The results of ¹ H-NMR measurement of the obtained solid are shown below. From this result, it was confirmed that the obtained solid was the intended RM1.

(Example 2) Synthesis of RM5

(Synthesis Example 6) Synthesis of RM5-1 precursor RM5-1

(58)

4,4'-dihydroxybenzophenone (20 g, 93.4 mmol), 4-chlorobutyl acetate (42.1 g, 280.2 mmol) and potassium carbonate (77.4 g, 560.4 mmol) , Potassium iodide (7.8 g, 46.7 mmol), and dimethylformamide (500 ml) were charged and stirred at 100 ° C. After completion of the reaction, the reaction solution was poured into water (2 L), and the precipitated crystals were separated by filtration. The obtained filtrate was placed in a 1 L four-necked flask, and 600 mL of ethanol and 250.0 g of 10 wt% KOH aqueous solution were added and stirred while heating under reflux. After completion of the reaction, the reaction solution was poured into a dilute hydrochloric acid aqueous solution to which was added concentrated hydrochloric acid (510 mL) to 3 L of water, and the precipitated precipitate was filtered and dried to obtain RM5-1 (24.1 g, yield 72%).

(Synthesis Example 7) Synthesis of RM5-2 precursor RM5-2

[Chemical Formula 59]

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

A solution of RM5-1 (24.1 g, 67.2 mmol), methanesulfonyl chloride (20 g, 174.7 mmol), triethylamine (17.8 g, 174.7 mmol) and tetrahydrofuran ), And the mixture was stirred while being cooled to 0 占 폚. After completion of the reaction, the reaction solution was poured into water (2.5 L), and the precipitated crystals were separated by filtration and dried to obtain RM5-2 (34.6 g, yield 99%).

(Synthesis Example 8) Synthesis of RM5-3 precursor RM5

(60)

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

(34.6 g, 67.2 mmol), trans-p-cumyl methyl (22.1 g, 134.4 mmol), potassium carbonate (55.7 g, 403.2 mmol) and dimethylformamide 500 ml) was added, and the mixture was stirred at 100 占 폚. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. After the solvent was distilled off, 600 ml of ethanol and 250.0 g of 10 wt% KOH aqueous solution were added and stirred while heating under reflux. After completion of the reaction, the reaction solution was poured into a dilute hydrochloric acid aqueous solution to which 3 ml of water was added with concentrated hydrochloric acid (510 ml), and the precipitated precipitate was filtered and dried to obtain RM5-3 (35.0 g, yield 80%).

(Synthesis Example 9) Synthesis of RM5

(61)

(35.0 g, 53.8 mmol), 2-hydroxyethyl methacrylate (HEMA) (21.0 g, 161.4 mmol) and 1- (3-dimethylaminopropyl) -3- Ethyl carbodiimide hydrochloride (EDC) (30.9 g, 161.4 mmol), 4-dimethylaminopyridine (DMAP) (0.7 g, 5.4 mmol) and dimethylformamide (600 ml) were added and stirred at room temperature. After completion of the reaction, the reaction solution was poured into water (2 L), and the precipitated crystals were separated by filtration. The obtained crystals were washed with 2-isopropyl alcohol to obtain the objective product RM5 (42.3 g, yield 90%). The results of ¹ H-NMR measurement of the target product are shown below. From this result, it was confirmed that the obtained solid was the intended RM5.

&Lt; Preparation of liquid crystal aligning agent &

(Example 3)

BODA (8.01 g, 32.0 mmol), 3AMPDA (5.81 g, 24.0 mmol), PCH (10.66 g, 28.0 mmol) and BEM-S (7.40 g, 28 mmol) were mixed in NMP (123.4 g) And reacted at 80 ° C for 5 hours. Then CBDA (9.26 g, 47.2 mmol) and NMP (41.1 g) were added and reacted at 40 ° C for 10 hours to obtain a polyamic acid solution. NMP was added to the polyamic acid solution (204 g) to dilute to 6 mass%, acetic anhydride (20.3 g) and pyridine (62.8 g) were added as imidation catalysts and reacted at 50 ° C for 3 hours. The reaction solution was poured into methanol (2700 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (A). The imidization ratio of the polyimide was 60%, the number average molecular weight was 16,000, and the weight average molecular weight was 39000.

NMP (24.0 g) was added to the obtained polyimide powder (A) (6.0 g), and the mixture was stirred and dissolved at room temperature for 5 hours. NMP (30.0 g) and BCS (40.0 g) were added to this solution and stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent (A1).

To 10.0 g of the liquid crystal aligning agent (A1), 60 mg (10% by mass based on the solid matter) of the polymerizable compound RM1 obtained in Example 1 was added and dissolved by stirring at room temperature for 3 hours to obtain a liquid crystal aligning agent A2 ) Was prepared.

(Example 4)

Similarly, 60 mg (10% by mass relative to solid content) of the polymerizable compound RM5 obtained in Example 2 was added to 10.0 g of the liquid crystal aligning agent (A1) and dissolved by stirring at room temperature for 3 hours to obtain a liquid crystal aligning agent (A6) Was prepared.

(Comparative Example 1)

Similarly, to 10.0 g of the liquid crystal aligning agent (A1), 60 mg (10% by mass relative to solid content) of a polymerizable compound RM2 was added and dissolved by stirring at room temperature for 3 hours to prepare a liquid crystal aligning agent (A3).

(Comparative Example 2)

Similarly, to 10.0 g of the liquid crystal aligning agent (A1), 60 mg (10% by mass relative to solid content) of a polymerizable compound RM3 was added and dissolved by stirring at room temperature for 3 hours to prepare a liquid crystal aligning agent A4.

(Comparative Example 3)

Similarly, 60 mg (10% by mass relative to solid content) of a polymerizable compound RM4 was added to 10.0 g of the liquid crystal aligning agent (A1) and dissolved by stirring at room temperature for 3 hours to prepare a liquid crystal aligning agent (A5).

&Lt; Production of liquid crystal cell &

(Example 5)

Using the liquid crystal aligning agent (A2) obtained in Example 3, a liquid crystal cell was produced in the following order. The liquid crystal aligning agent A2 obtained in Example 3 was spin-coated on the ITO surface of the ITO electrode substrate having the ITO electrode pattern having the pixel size of 100 mu m x 300 mu m and the line / space of 5 mu m each formed thereon, , And then fired in a hot-air circulating oven at 200 ° C for 30 minutes to form a liquid crystal alignment film having a thickness of 100 nm.

The liquid crystal aligning agent A2 was spin-coated on an ITO surface on which no electrode pattern was formed, dried for 90 seconds on a hot plate at 80 占 폚 and fired in a hot air circulating oven at 200 占 폚 for 30 minutes, A liquid crystal alignment film having a thickness of 100 nm was formed.

A 6 占 퐉 bead spacer was dispersed on the liquid crystal alignment film of one of the two substrates, and then a sealing agent (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed thereon. Subsequently, the other side of the substrate on the side where the liquid crystal alignment film was formed was inwardly joined with the preceding substrate, and then the sealing agent was cured to prepare empty cells. A negative-type liquid crystal (MLC-6608) was injected into this empty cell by a low-pressure injection method and subjected to a redistribution treatment at 120 占 폚 for 1 hour to prepare a liquid crystal cell.

The response speed of the obtained liquid crystal cell was measured by the following method. Thereafter, in a state in which an AC voltage of 20 Vp-p was applied to this liquid crystal cell, UV emitted from the outside of the liquid crystal cell passed through a 313 nm band-pass filter was irradiated with 500 mJ or 1000 mJ. Thereafter, the response speed was again measured, and the response speeds before and after the UV irradiation were compared. The results are shown in Table 2.

How to measure the response speed

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

(Example 6)

The same operation as in Example 5 was performed except that the liquid crystal aligning agent (A6) was used in place of the liquid crystal aligning agent (A2), and the response speeds before and after UV irradiation were compared.

(Comparative Example 4)

The same operation as in Example 5 was carried out except that the liquid crystal aligning agent (A3) was used in place of the liquid crystal aligning agent (A2), and the response speeds before and after UV irradiation were compared.

(Comparative Example 5)

The same operation as in Example 5 was carried out except that the liquid crystal aligning agent (A4) was used in place of the liquid crystal aligning agent (A2), and the response speeds before and after UV irradiation were compared.

(Example 7)

The same operation as in Example 5 was carried out except that UV rays having passed through a band pass filter of 313 nm from the outside of the liquid crystal cell were irradiated with UV light having passed through a 365 nm band pass filter from the outside of the liquid crystal cell , And the response speeds before and after UV irradiation were compared. The results are shown in Table 3.

(Example 8)

The same operation as in Example 7 was performed except that the liquid crystal aligning agent (A6) was used instead of the liquid crystal aligning agent (A2), and the response speeds before and after UV irradiation were compared.

(Comparative Example 6)

The same operation as in Example 7 was performed except that the liquid crystal aligning agent (A5) was used instead of the liquid crystal aligning agent (A2), and the response speeds before and after UV irradiation were compared.

As a result, as shown in Table 2, in Examples 5 and 6 using a polymerizable compound having both a photopolymerizable group and a group that causes light quantization, the response speed was remarkably improved at an irradiation dose of only 500 mJ . It is considered that this is because the polymerizable compound has both a photopolymerizable group and a group causing a photodimerization in one polymerizable compound, so that the polymerizable compound has a very high sensitivity of the photoreaction and a photoreaction occurs at a high density. On the other hand, from the results of Comparative Examples 4 and 5 using the polymerizable compound having any one of the photopolymerizable groups or the photodimerization groups as in Examples 5 and 6, the response speed was not sufficiently accelerated at a dose of about 1000 mJ . This is presumably due to the fact that the reaction rate of the photopolymerizable group is slow, and that the density of the photoreactive unit causing the light dimerization is low.

As shown in Table 3, from the results of Examples 7 and 8 having two groups in which light quantization occurs and Comparative Example 6 having only one group causing light quantization, the number of groups causing light quantization It can be seen that the density of the photoreactor in which the photodimerization occurs increases the sensitivity of the photoreaction.

Claims (10)

A liquid crystal aligning agent characterized by containing a polymerizable compound represented by the following formula [1].
[Chemical Formula 1]

(In the formula [1], C is a divalent carbon ring-containing group having 10 to 30 carbon atoms and containing an aromatic ring, and one or plural hydrogen atoms of the carbon ring-containing group is substituted with a fluorine atom or an organic group .
S ¹ and S ^{1 '} each independently represents a single bond or an alkylene group having 1 to 10 carbon atoms, and one or plural hydrogen atoms of the alkylene group may be substituted with a fluorine atom or an organic group. Further, in the case where S ^1, S ^{1 ',} the group of which do illustrated in the following are not adjacent to each other, -CH ₂ - is optionally are substituted with these; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -CO-.
P and P ^' are each independently a group which causes divalent light dimerization selected from the following formulas [P-1] to [P-10], and one or a plurality of hydrogen The atom may be substituted with an organic group.
(2)

(In the formulas [P-1] to [P-10], * represents the bonding position with S ¹ , S ^{1 '} or S ² and S ^2' .)
S ² and S ^{2 '} each independently represent a single bond or an alkylene group having 1 to 10 carbon atoms, and one or plural hydrogen atoms of the alkylene group may be substituted with a fluorine atom or an organic group. In addition, S ² and S ^{2 '} may be substituted with -CH ₂ - in the case where any of the groups shown below are not adjacent to each other; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -CO-.
L and L ^' each independently represent a monovalent photopolymerizable group selected from the following formulas [L-1] to [L-11].
(3)

(Of the formulas [L-1] to [L-11], * represents the bonding position with S ² and S ^{2 '} .) The method according to claim 1,
L and L ^' are monovalent groups selected from the formulas [L-1], [L-2] and [L-7]. 3. The method according to claim 1 or 2,
P and P ^' are a divalent group selected from the formulas [P-1] to [P-3] and [P-5]. 4. The method according to any one of claims 1 to 3,
And C is a divalent group selected from the following formulas [C-1] to [C-12].
[Chemical Formula 4]

(In the formulas [C-1] to [C-12], * represents a bonding position with S ¹ and S ^{1 '} .) 5. The method according to any one of claims 1 to 4,
A liquid crystal aligning agent having a polymer and a solvent for forming a liquid crystal alignment film for vertically aligning the liquid crystal. A liquid crystal alignment film obtained from the liquid crystal aligning agent according to any one of claims 1 to 5. A liquid crystal display element comprising the liquid crystal alignment film according to claim 6. A liquid crystal alignment layer according to any one of claims 1 to 5, which is applied to a substrate and fired, is brought into contact with a liquid crystal alignment film to form a liquid crystal layer. While applying a voltage to the liquid crystal layer, Wherein the liquid crystal display element is manufactured by a method comprising the steps of: A polymerizable compound characterized by the following formula [1].
[Chemical Formula 5]

(Wherein C represents a divalent organic group selected from the following formulas [C-2], [C-5] to [C-8] and [C-10]
[Chemical Formula 6]

(In the formulas [C-2], [C-5] to [C-8] and [C-10], * represents the bonding position with S ¹ and S ^{1 '}
S ¹ and S ^{1 '} each independently represents a single bond or an alkylene group having 1 to 10 carbon atoms, and one or plural hydrogen atoms of the alkylene group may be substituted with a fluorine atom or an organic group. Further, in the case where S ^1, S ^{1 ',} the group of which do illustrated in the following are not adjacent to each other, -CH ₂ - is optionally are substituted with these; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -CO-.
S ² and S ^{2 '} each independently represent a single bond or an alkylene group having 1 to 10 carbon atoms, and one or plural hydrogen atoms of the alkylene group may be substituted with a fluorine atom or an organic group. In addition, S ^2, S ^{2 'are} in the case of the groups which do illustrated in the following are not adjacent to each other, -CH ₂ - is optionally are substituted with these; -O-, -NHCO-, -CONH-, - COO-, -OCO-, -NH-, -CO-.
P is a group which causes divalent light dimerization selected from the following formulas [P-1] to [P-3] and [P-5].
(7)

(In the formulas [P-1] to [P-3] and [P-5], * represents the bonding position with S ¹ , S ^{1 '} or S ² and S ^2' .)
L and L ^' are monovalent organic groups selected from the following formulas [L-1], [L-2] and [L-7].
[Chemical Formula 8]

(Of the formulas [L-1], [L-2] and [L-7], * represents the bonding position with S ² and S ^{2 '} .) A polymerizable compound represented by any one of the following formulas.
[Chemical Formula 9]

(Wherein C represents a divalent organic group represented by any one of the following formulas, and n represents an integer of 2 to 4.)
[Chemical formula 10]