TW201634533A - Liquid crystal orienting agent, liquid crystal display element, and method for producing liquid crystal display element - Google Patents

Abstract

Provided are a liquid crystal orienting agent having good residual DC characteristics, a liquid crystal oriented film, a liquid crystal display element, and a method for manufacturing a liquid crystal display element. The liquid crystal orienting agent is intended for use in a liquid crystal display element obtained by photoirradiation of a liquid crystal cell in which a pair of substrates having conductive films that are coated with a liquid crystal orienting agent and heated to form a coating film are arranged in opposition with the coating films facing across an intervening liquid crystal layer. The liquid crystal orienting agent contains the following component (A), component (B), and an organic solvent. Component (A): at least one polymer selected from the group consisting of polyimide precursors having side chains for causing liquid crystals to orient vertically, and polyimides that are imides of such polyimide precursors. Component (B): at least one polymer selected from the group consisting of polyimide precursors that are reaction products of a diamine component and a tetracarboxylic dianhydride component that contains a tetracarboxylic dianhydride selected from the following equations (1) and (1'), and polyimides that are imides of such polyimide precursors. When component (B) has side chains for causing liquid crystals to orient vertically, the component may be a polymer identical to that of component (A). (j and k are 0 or 1, and x and y are single bonds, carbonyl groups, or the like).

Description

Liquid crystal alignment agent, liquid crystal display element, and method of manufacturing liquid crystal display element

The present invention relates to a liquid crystal alignment agent, a liquid crystal display element, and a method for producing a liquid crystal display element which can be used in the production of a liquid crystal display device of a vertical alignment type produced by irradiating ultraviolet rays to liquid crystal molecules.

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

In the liquid crystal display device of such a vertical alignment type, it is known that a photopolymerizable compound is added to a liquid crystal composition in advance, and a vertical alignment film such as polyimide or the like is used together, and a voltage is applied to the liquid crystal cell while irradiating ultraviolet rays. Further, a PSA (Polymer sustained Alignment) element having a fast response speed of liquid crystal (see Patent Document 1 and Non-Patent Document 1).

In general, the tilt direction of the liquid crystal molecules that have responded to the electric field is controlled by a protrusion provided on the substrate or a slit provided in the display electrode. in When a photopolymerizable compound is added to a liquid crystal composition, and a voltage is applied to the liquid crystal cell and ultraviolet rays are simultaneously irradiated, since the polymer structure in which the tilt direction of the liquid crystal molecules is stored is formed on the liquid crystal alignment film, it is generally considered to be The response speed of the liquid crystal display element is faster than the method of controlling the tilt direction of the liquid crystal molecules by the protrusions or the slits.

On the other hand, it has been reported that even when a photopolymerizable compound is added to a liquid crystal alignment film and is not a liquid crystal composition, the response speed of the liquid crystal display element is increased (SC-PVA type liquid crystal display) (refer to Patent Document 2). In addition, in recent years, higher-speed response of PSA-type liquid crystal panels has been discussed. As a technique, one or more monofunctional liquid crystal compounds having an alkenyl group and a fluoroalkenyl group have been tried (hereinafter, The "alkenyl-based liquid crystal" is introduced into a liquid crystal composition (see Patent Documents 2 to 5). However, when the liquid-based composition is introduced into the liquid crystal composition, the reliability is lowered (see Patent Documents 6 to 9), and the voltage holding ratio or the DC charge storage characteristic (residual DC characteristic) tends to be deteriorated.

In particular, the deterioration of the residual DC characteristics causes a burn-in which causes deterioration in display characteristics (after-images) of the liquid crystal display element. As a method for improving residual DC so far, it is known that a salt of a carboxyl group and a nitrogen-containing aromatic heterocyclic ring is formed or referred to as hydrogen bonding, and the promotion of charge transfer by electrostatic interaction or the like. However, there is little knowledge about the method of improving residual DC when an alkenyl liquid crystal is used (see Patent Documents 10 to 12).

[Previous Technical Literature] [Patent Document]

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

[Patent Document 2] International Publication No. 2009/050869

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2010-285499

[Patent Document 4] Japanese Patent Laid-Open No. Hei 9-104644

[Patent Document 5] Japanese Patent Laid-Open No. Hei 6-108053

[Patent Document 6] European Patent No. 0 474 062

[Patent Document 7] U.S. Patent No. 6,066,268

[Patent Document 8] Japanese Patent Laid-Open Publication No. 2014-240486

[Patent Document 9] Japanese Patent Laid-Open Publication No. 2014-224260

[Patent Document 10] Japanese Patent Laid-Open No. Hei 9-316200

[Patent Document 11] Japanese Patent Laid-Open No. Hei 10-104633

[Patent Document 12] Japanese Patent Laid-Open No. Hei 8-76128

[Non-patent literature]

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

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

The object of the present invention is to provide a vertical alignment method The response speed of the liquid crystal display element is improved, and the electrical characteristics and residual DC characteristics of the obtained liquid crystal display element can be improved, and in particular, the residual DC characteristics when the liquid crystal composition containing an alkenyl liquid crystal is used become a good liquid crystal. An alignment agent, a liquid crystal alignment film, a liquid crystal display element, and a method of producing a liquid crystal display element.

In order to solve the above problems, the inventors of the present invention have found a method for solving the above problems as a result of careful study, and have completed the present invention having the following gist.

A liquid crystal alignment agent comprising the following component (A), component (B), and an organic solvent; wherein the liquid crystal display device is formed by light-irradiating a liquid crystal cell, the liquid crystal display device The unit has a substrate having a conductive film coated with a liquid crystal alignment agent on the conductive film of the substrate and heated to form a substrate having a coating film, and the liquid crystal layer is interposed so that the coating film is relatively aligned with the coating film;

(A) component: at least one polymer selected from the group consisting of a polyimine precursor having a side chain which vertically aligns the liquid crystal, and a polyimine which is a quinone imine of the polyimide precursor.

(B) component: a polyimine precursor selected from the group consisting of a reaction product of a tetracarboxylic dianhydride component and a diamine component which are selected from the tetracarboxylic dianhydrides of the following formula (1) and (1'), And at least one polymer of the polyimine of the quinone imine of the polyimine precursor. However, when the component (B) has a side chain which vertically aligns the liquid crystal, it may be the same polymerization as the component (A). Things.

(wherein j and k are each independently 0 or 1, and x and y are each independently a single bond, a carbonyl group, an ester, a phenylene group, a sulfonyl group or a decylamino group.)

2. The liquid crystal alignment agent according to the above 1, wherein the liquid crystal layer in the liquid crystal display element is a liquid crystal layer containing a liquid crystal compound having an alkenyl liquid crystal.

3. The liquid crystal alignment agent according to the above 1 or 2, wherein the content ratio of the component (A) to the component (B) is (A) component at a mass ratio: (B) component = X: (10-X) (X = 1~9).

4. The liquid crystal alignment agent according to any one of the above 1 to 3, wherein the side chain in which the liquid crystal is vertically aligned in the component (A) is represented by the following formula (a).

(l, m and n each independently represent an integer of 0 or 1, and R ¹ represents an alkylene group having 2 to 6 carbon atoms, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or The alkyl-ether group having 1 to 3 carbon atoms, R ² , R ³ and R ⁴ each independently represent a phenyl group, a fluorine-containing phenyl group or a cycloalkyl group, and R ⁵ represents a hydrogen atom and a carbon number of 2 a ~24 alkyl group, a carbon number of 2 to 24 fluorine-containing alkyl group, a monovalent aromatic ring, a monovalent aliphatic ring, a monovalent heterocyclic ring, or a cyclical substituent which constitutes one of the valences .)

A liquid crystal alignment film obtained by the liquid crystal alignment agent according to any one of the above 1 to 4, wherein the film thickness is 5 to 300 nm.

A liquid crystal display element comprising the liquid crystal alignment film of the above 5.

A method of producing a liquid crystal display device, comprising: coating a liquid crystal alignment agent containing a component (A), a component (B), and an organic solvent described below on a substrate having a conductive film; a second step of forming a coating film by heating the second coating film on the film; forming a liquid crystal cell by arranging one of the coating films to form a liquid crystal layer on the substrate, and arranging the coating film in a direction opposite to each other; The liquid crystal cell performs the third step of light irradiation.

(A) component: at least one polymer selected from the group consisting of a polyimine precursor having a side chain in which a liquid crystal is vertically aligned, and a polyimine of a ruthenium imide of the polyimide precursor.

(B) component: a polyfluorene selected from the group consisting of a reaction product of a tetracarboxylic dianhydride component and a diamine containing at least one tetracarboxylic dianhydride selected from the following formulas (1) and (1') At least one polymer of the amine precursor, and the polyimine of the ruthenium imide of the polyimide precursor. However, when the component (B) has a side chain in which the liquid crystal is vertically aligned, it may be the same polymer as the component (A).

(wherein, j, k, x, and y are as described above.)

8. The method of producing a liquid crystal display device according to the above 7, wherein the liquid crystal layer is a liquid crystal layer containing a liquid crystalline compound having an alkenyl liquid crystal.

9. The method of producing a liquid crystal display element according to the above 7 or 8, wherein the ultraviolet ray irradiation amount is 1 to 50 J/cm ² .

10. The method of manufacturing a liquid crystal display element according to any one of the items 7 to 9, wherein the liquid crystal display element is a vertical alignment type display element.

According to the present invention, it is possible to provide a liquid crystal display element of a vertical alignment type in which the liquid crystal has a fast response speed and a small DC residual.

The liquid crystal alignment agent used in the production method of the present invention is a liquid crystal alignment agent for a vertical alignment type liquid crystal display device containing the above-mentioned (A) component, (B) component, and an organic solvent. However, the above component (B) is a polymer which is the same as the component (A).

Further, in the present invention, the liquid crystal alignment agent means a solution for forming a liquid crystal alignment film, and the liquid crystal alignment film means a film for causing the liquid crystal to face in a predetermined direction in the present invention.

[(A) component]

The liquid crystal alignment agent of the present invention contains, as the component (A), a polyarylene selected from the group consisting of a polyimide precursor having a side chain in which a liquid crystal is vertically aligned, and a ruthenium imide of the polyimide precursor. At least one polymer in groups of amines.

<Let the side chain of the liquid crystal vertical alignment>

The side chain in which the liquid crystal is vertically aligned is not limited as long as it is a structure in which the liquid crystal can be vertically aligned with respect to the substrate. For example, a long-chain alkyl group, a group having a ring structure or a branching structure in the middle of a long-chain alkyl group, a steroid group, a group in which one or all of hydrogen atoms of these groups are substituted by a fluorine atom, and the like can be given. The side chain system for vertically aligning the liquid crystal may be directly bonded to the main chain of poly-plylimic acid or polyimine, or may be bonded through a suitable binding group. Examples of the side chain for vertically aligning the liquid crystal include those represented by the following formula (a).

(In the formula (a), l, m and n each independently represent an integer of 0 or 1, and R ¹ represents an alkylene group having 2 to 6 carbon atoms, -O-, -COO-, -OCO-, -NHCO- , -CONH-, or a C 1 to 3 alkyl-ether group, R ² , R ³ , and R ⁴ each independently represent a phenylene group, a fluorine-containing phenyl group or a cycloalkyl group, and R ⁵ represents a hydrogen atom, an alkyl group having 2 to 24 carbon atoms, a fluorine-containing alkyl group having 2 to 24 carbon atoms, a monovalent aromatic ring, a monovalent aliphatic ring, a monovalent heterocyclic ring, or the like A large circular substitute.)

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

Further, from the viewpoints of easiness of synthesis and ability to vertically align the liquid crystal, R ² , R ³ and R ⁴ in the formula (a) are 1, m, n, R ² and R ³ shown in Table 1 below. The combination of R ⁴ is preferred.

When at least one of l, m and n is 1, R ⁵ in the formula (a) is preferably a hydrogen atom, an alkyl group having 2 to 14 carbon atoms, or a fluorine-containing alkyl group having 2 to 14 carbon atoms, more preferably A hydrogen atom, an alkyl group having 2 to 12 carbon atoms, or a fluorine-containing alkyl group having 2 to 12 carbon atoms. Further, when l, m and n are both 0, R ⁵ is preferably an alkyl group having 12 to 22 carbon atoms, a fluorine-containing alkyl group having 12 to 22 carbon atoms, a monovalent aromatic ring, and a monovalent aliphatic ring. A monovalent heterocyclic ring, or a large cyclic substituent having a valence of one or more, more preferably an alkyl group having 12 to 20 carbon atoms or a fluorine-containing alkyl group having 12 to 20 carbon atoms.

The content of the side chain in which the liquid crystal is vertically aligned in the polyimine or polyimine precursor used in the present invention is not particularly limited as long as the liquid crystal alignment film can vertically align the liquid crystal. However, in a liquid crystal display device having a liquid crystal alignment film, when the response speed of the liquid crystal is to be made faster, the content of the side chain in which the liquid crystal is vertically aligned is preferably as small as possible within a range in which the vertical alignment can be maintained.

Further, the ability of the polymer having the side chain which vertically aligns the liquid crystal to vertically align the liquid crystal differs depending on the structure of the side chain in which the liquid crystal is vertically aligned. In general, when the content of the side chain in which the liquid crystal is vertically aligned becomes too large, the ability to vertically align the liquid crystal is increased, and when it is small, it is lowered. Further, the side chain having a ring structure tends to have a higher ability to vertically align the liquid crystal than the side chain having no ring structure.

<Method for Producing (A) Component>

Producing at least one polymer selected from the group consisting of a polyimide precursor having a side chain in which a liquid crystal is vertically aligned, and a polyimine obtained by imidating the polyimine precursor That is, the method of the component (A) is not particularly limited. For example, in the method of obtaining poly-proline by a reaction of a diamine and a tetracarboxylic dianhydride, a diamine having a side chain in which a liquid crystal is vertically aligned may be copolymerized with a tetracarboxylic dianhydride.

Examples of the diamine having a side chain in which the liquid crystal is vertically aligned include an alkyl group having a long chain, a group having a ring structure or a branching structure on the middle of the long-chain alkyl group, a steroid group, and a hydrogen atom of the group. A diamine which is a side chain of a part or all of which is substituted by a fluorine atom, for example, a diamine having a side chain represented by the above formula (a). More specifically, for example, the diamines represented by the following formulas (2), (3), (4), and (5) are exemplified, but are not limited thereto.

(The definitions of l, m, n, and R ¹ to R ^{5 in} the formula (2) are the same as those in the above formula (a).)

(In the formulas (3) and (4), A ₁₀ represents -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO-, or -NH-, A ₁₁ represents a single bond or a phenyl group, and a represents a structure in which the side chain which is perpendicular to the liquid crystal represented by the above formula (a) is the same, and a' represents a vertical alignment of the liquid crystal represented by the above formula (a). The side chain is a divalent group of a structure in which one hydrogen atom or the like is removed in the same structure.)

(In the formula (5), A ₁₄ is an alkyl group having 3 to 20 carbon atoms which may be substituted by a fluorine atom, A ₁₅ is a 1,4 ring extension group or a 1,4-phenyl group, and A ₁₆ is an oxygen atom. Or -COO-* (however, the bond with "*" is attached to A ₁₅ ), A ₁₇ is an oxygen atom or -COO-* (however, the bond with "*" is attached and (CH ₂ ) a _{2 is} combined.) Further, a ₁ is an integer of 0 or 1, and a ₂ is an integer of 2 to 10, and a ₃ is an integer of 0 or 1.

Formula (2) in the two group (-NH ₂₎ of the bonding position is not limited. Specifically, the bonding group with respect to the side chain may, for example, be a position of 2, 3 on the benzene ring, a position of 2, 4, a position of 2, 5, a position of 2, 6, a position of 3, 4, 3,5 position. Among them, from the viewpoint of reactivity in synthesizing polyamic acid, the position of 2, 4, 2, 5 or 3, 5 is preferred. If the ease of synthesizing the diamine is considered, the position of 2, 4 or 3, 5 is more preferable.

The specific structure of the formula (2) may, for example, be a diamine represented by the following formula [A-1] to the formula [A-24], but is not limited thereto.

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

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

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

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

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

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

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

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

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

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

The characteristics of the liquid crystal alignment property, the pretilt angle, the voltage holding property, and the accumulated electric charge in the case of forming the liquid crystal alignment film may be one type or two or more types may be used in combination.

The diamine having such a side chain for vertically aligning the liquid crystal is preferably used in an amount of 5 to 50 mol%, preferably 10 parts, of the diamine component used for the synthesis of the component (A). 40% of the moles, especially good for 15~30%. Therefore, when a diamine having a side chain in which the liquid crystal is vertically aligned is used in an amount of 5 to 50 mol% of the diamine component used for the synthesis of the polyamic acid, it is particularly excellent in the ability to fix the vertical alignment. .

Further, the polyamine can also be used as the diamine component in combination with the diamine having the side chain which vertically aligns the liquid crystal in the range which does not impair the effect of the present invention. Specifically, for example, p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylene Diamine, m-phenylenediamine, 2,4-dimethyl-m-phenylene Amine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5 -diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diaminobiphenyl, 3,3'-dimethyl 4-,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-di Aminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-biphenyl, 3,3'-trifluoro Methyl-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl , 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenyl Methane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodi Phenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonate Diphenylamine, 3,3'-sulfonyldiphenylamine, bis(4-aminophenyl)decane, (3-aminophenyl)decane, dimethyl-bis(4-aminophenyl)decane, dimethyl-bis(3-aminophenyl)decane, 4,4'-thiodiphenylamine, 3 , 3'-thiodiphenylamine, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2 '-Diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl(4,4'-diaminodiphenyl)amine, N-methyl (3,3 '-Diaminodiphenyl)amine, N-methyl(3,4'-diaminodiphenyl)amine, N-methyl(2,2'-diaminodiphenyl)amine, N -Methyl (2,3'-diaminodiphenyl)amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-di Aminobenzophenone, 1,4-diaminonaphthalene, 2,2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene 1,6-Diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-di Amino naphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis(4-aminophenyl)ethane, 1,2- Bis(3-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane, 1,3-bis(3-aminophenyl)propane, 1,4-bis(4 amine Phenyl)butane, 1,4-bis(3-aminophenyl)butane, bis(3,5-diethyl-4-aminophenyl)methane, 1,4-bis(4- Aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminobenzene) Benzene, 1,4-bis(4-aminobenzyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4'-[1,4-phenylene bis( Methylene)]diphenylamine, 4,4'-[1,3-phenylenebis(methylene)]diphenylamine, 3,4'-[1,4-phenylene bis(methylene) Diphenylamine, 3,4'-[1,3-phenylenebis(methylene)]diphenylamine, 3,3'-[1,4-phenylphenylbis(methylene)]diphenylamine, 3,3'-[1,3-phenylenebis(methylene)]diphenylamine, 1,4-phenylphenylbis[(4-aminophenyl)methanone], 1,4-phenylene Bis[(3-aminophenyl)methanone], 1,3-phenylene bis[(4-aminophenyl)methanone], 1,3-phenylene bis[(3-amino) Phenyl)methanone], 1,4-phenylene double (4-Aminobenzoic acid ester), 1,4-phenylphenylbis(3-aminobenzoate), 1,3-phenylphenylbis(4-aminobenzoate), 1 , 3-phenylphenyl bis(3-aminobenzoate), bis(4-aminophenyl)-p- phthalate, bis(3-aminophenyl)-p- phthalate, bis (4- Aminophenyl)isodecanoate, bis(3-aminophenyl)isodecanoate, N,N'-(1,4-phenylene)bis(4-aminobenzylamine), N , N'-(1,3-phenylene) bis(4-aminobenzylamine), N,N'-(1,4-phenylene)bis(3-aminobenzamide), N , N'-(1,3-phenylene) bis(3-aminobenzamide), N,N'-bis(4-aminophenyl)-p-amine, N,N'-double ( 3-aminobenzene Base) p-decylamine, N,N'-bis(4-aminophenyl)isodecylamine, N,N'-bis(3-aminophenyl)isodecylamine, 9,10-double (4-Aminophenyl)anthracene, 4,4'-bis(4-aminophenoxy)diphenylanthracene, 2,2'-bis[4-(4-aminophenoxy)phenyl Propane, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis(4-aminophenyl)hexafluoropropane, 2,2' - bis(3-aminophenyl)hexafluoropropane, 2,2'-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2'-bis(4-aminophenyl) ) propane, 2,2'-bis(3-aminophenyl)propane, 2,2'-bis(3-amino-4-methylphenyl)propane, trans-1,4-bis(4-) Aminophenyl)cyclohexane, 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid, bis(4-aminophenoxy)methane, 1,2-bis(4-amine Phenoxy group) ethane, 1,3-bis(4-aminophenoxy)propane, 1,3-bis(3-aminophenoxy)propane, 1,4-bis(4-amino group) Phenoxy)butane, 1,4-bis(3-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,5-bis(3-amine Phenyloxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7-bis (4- Aminophenoxy) Alkane, 1,7-bis(3-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy) Octane, 1,9-bis(4-aminophenoxy)decane, 1,9-bis(3-aminophenoxy)decane, 1,10-bis(4-aminophenoxy) ) decane, 1,10-bis(3-aminophenoxy)decane, 1,11-bis(4-aminophenoxy)undecane, 1,11-bis(3-aminobenzene Aromatic diamines such as oxy)undecane, 1,12-bis(4-aminophenoxy)dodecane, 1,12-bis(3-aminophenoxy)dodecane; An alicyclic diamine such as (4-aminocyclohexyl)methane or bis(4-amino-3-methylcyclohexyl)methane; 1,3-diaminopropane, 1,4-diamine Butane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diamino An aliphatic diamine such as decane, 1,10-diaminodecane, 1,11-diaminoundecane or 1,12-diaminododecane; 1,3-bis[2-( Urea having a urea structure, such as p-aminophenyl)ethyl]urea, 1,3-bis[2-(p-aminophenyl)ethyl]-1-tertiary butoxycarbonylurea a diamine having a nitrogen-containing unsaturated heterocyclic structure such as Np-aminophenyl-4-p-aminophenyl (third-order butoxycarbonyl)aminomethylpiperidine; N-third stage a diamine having an N-Boc group such as butoxycarbonyl-N-(2-(4-aminophenyl)ethyl)-N-(4-aminobenzyl)amine; the following (B) The at least one diamine selected from the group consisting of the formulae (B-1) to (B-5), and the diamine exemplified as a specific example thereof, as described in the item of the component.

Further, as the other diamine, there may be mentioned a photoreaction comprising at least one selected from the group consisting of methacryloyl group, acryl fluorenyl group, vinyl group, allyl group, coumarin group, styryl group and cinnamyl group. A diamine of a side chain and a diamine having a site in which a side chain has a radical generated by decomposition by ultraviolet irradiation.

Specifically, for example, the diamine having a photoreactive side chain may be a diamine represented by the following general formula (6), but is not limited thereto.

(In the formula (6), R ⁶ represents a single bond, -CH ₂ -, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N (CH ₃ )-, -CON(CH ₃ )-, or -N(CH ₃ )CO-, R ⁷ represents a single bond, or an alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted by a fluorine atom And the alkyl group -CH ₂ - may be optionally substituted by -CF ₂ - or -CH=CH-, and may be substituted by any of the groups exemplified below; O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, a divalent carbocyclic ring, or a divalent heterocyclic ring. R ⁸ represents a photoreactive group selected from the following formula. )

The bonding position of the two amine groups (-NH ₂ ) in the formula (6) is not limited. Specifically, the bonding group with respect to the side chain may, for example, be a position of 2, 3 on the benzene ring, a position of 2, 4, a position of 2, 5, a position of 2, 6, a position of 3, 4, 3,5 position. Among them, from the viewpoint of reactivity in synthesizing polyamic acid, the position of 2, 4, the position of 2, 5, or the position of 3, 5 is also preferable. If the ease of synthesizing the diamine is considered, it is more preferable to use the position of 2, 4 or the position of 3, 5.

a diamine comprising a photoreactive group having at least one selected from the group consisting of a methacryl fluorenyl group, an acryl fluorenyl group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamyl group. The following may be mentioned as a compound, but it is not limited thereto.

(wherein J ¹ is a bond selected from a single bond, -O-, -COO-, -NHCO-, or -NH-, and J ² represents a single bond, or a carbon number which is unsubstituted or substituted by a fluorine atom 1~20 alkyl group.)

The side chain has a diamine which generates a radical by decomposition by ultraviolet irradiation, and examples thereof include a diamine represented by the following general formula (7), but are not limited thereto.

(wherein Ar represents an aromatic hydrocarbon group selected from the group consisting of a stretching phenyl group, a stretching naphthyl group, and a biphenyl group, and these may be substituted by an organic group, and a hydrogen atom may be substituted by a halogen atom. R ⁹ and R ^{The 10} series are each independently an alkyl group or alkoxy group having 1 to 10 carbon atoms, and the T ₁ and T ₂ groups are each independently a single bond, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N(CH ₃ )-, -CON(CH ₃ )-, or -N(CH ₃ )CO-, S is a single bond, or unsubstituted or via The alkyl group having 1 to 20 carbon atoms substituted by a fluorine atom (but the alkyl group -CH ₂ - or CF ₂ - may be optionally substituted by -CH=CH-, without any of the following base phases In the case of ortho, it may be substituted by such a group; -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, a divalent carbocyclic ring, or a divalent heterocyclic ring.) , Q represents the following structure.)

(wherein R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹¹ represents -CH ₂ -, -NR-, -O-, or -S-.)

The bonding position of the two amine groups (-NH ₂ ) in the above formula (7) is not limited. Specifically, the bonding group with respect to the side chain may, for example, be a position of 2, 3 on the benzene ring, a position of 2, 4, a position of 2, 5, a position of 2, 6, a position of 3, 4, 3,5 position. Among them, from the viewpoint of reactivity in synthesizing polyamic acid, the position of 2, 4, the position of 2, 5, or the position of 3, 5 is also preferable. If the ease of synthesizing the diamine is considered, the position of 2, 4 or the position of 3, 5 is more preferable.

In particular, the structure represented by the following formula is preferable in view of ease of synthesis, height of generality, characteristics, and the like, but is not limited thereto.

(where n is an integer from 2 to 8.)

In the case of the properties of the liquid crystal alignment, the pretilt angle, the voltage holding property, and the accumulated electric charge when the liquid crystal alignment film is formed, the other diamines may be used in one type or in a mixture of two or more types.

In the synthesis of polyamic acid, the tetracarboxylic dianhydride which reacts with the above diamine component is not particularly limited. Specific examples thereof include pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, and 1,4,5,8-naphthalenetetracarboxylic acid. 2,3,6,7-decanetetracarboxylic acid, 1,2,5,6-nonanetetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3', 4'-biphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl)ether, 3,3',4,4'-benzophenonetetracarboxylic acid, bis(3,4-dicarboxybenzene Base, bis(3,4-dicarboxyphenyl)methane, 2,2-bis(3,4-dicarboxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2 , 2-bis(3,4-dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)dimethyloxane, bis(3,4-dicarboxyl) Phenyl)diphenylnonane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,3',4,4'-diphenyl Base carboxylic acid, 3,4,9,10-decanetetracarboxylic acid, 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid, oxydiphthalene tetracarboxylate Acid, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2 , 3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,3 - dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cycloheptanetetracarboxylic acid, 2,3,4,5-tetrahydrofurantetracarboxylic acid, 3, 4-dicarboxy-1-cyclohexyl succinic acid, 2,3,5-tricarboxycyclopentyl acetic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid, bicyclo [3,3,0]octane-2,4,6,8-tetracarboxylic acid, bicyclo[4,3,0]nonane-2,4,7,9-tetracarboxylic acid, bicyclo[4,4 , 0] decane-2,4,7,9-tetracarboxylic acid, bicyclo[4,4,0]nonane-2,4,8,10-tetracarboxylic acid, tricyclo[6.3.0.0<2, 6>] undecane-3,5,9,11-tetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)- 1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic acid, 5-(2 , 5-dioxotetrahydrofuranyl-3-methyl-3-cyclohexane-1,2-dicarboxylic acid, tetracyclo[6,2,1,1,0,2,7]t-12-4, 5,9,10-tetracarboxylic acid, 3,5,6-tricarboxynorbornane-2: 3,5:6 dicarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, etc. A carboxylic acid dianhydride. Of course, the tetracarboxylic dianhydride may be one type or two or more types may be used in combination in order to exhibit characteristics such as liquid crystal alignment property, voltage retention property, and accumulated electric charge when the liquid crystal alignment film is formed.

A method of obtaining polyglycine by a reaction of a raw material diamine (also referred to as "diamine component") with a raw material tetracarboxylic dianhydride (also referred to as "tetracarboxylic dianhydride component") can be used. A well-known synthetic technique. One Generally, a method in which a diamine component and a tetracarboxylic dianhydride component are reacted in an organic solvent is used. The reaction between the diamine component and the tetracarboxylic dianhydride component is carried out relatively easily in an organic solvent, and it is advantageous to produce no by-product surface.

The organic solvent used in the above reaction is not particularly limited as long as it dissolves the produced polyamic acid. Further, even if the organic solvent of the polyamic acid is not dissolved, it may be used in the above solvent in a range in which the produced polyamine does not precipitate. Further, since the water in the organic solvent causes the polymerization reaction to be inhibited and the produced polyamic acid is hydrolyzed, it is preferred that the organic solvent be dehydrated.

As an organic solvent, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, N-methylformamide, N-A Base-2-pyrrolidone, N-ethyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-di Methyl acrylamide, N-methyl caprolactam, dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethyl hydrazine, γ-butyrolactone, isopropyl alcohol, A Oxymethylpentanol, dipentene, ethyl amyl ketone, methyl decyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cyproterone, B Kesaisusu, methyl cyproterone acetate, butyl cyproterone acetate, ethyl cyproterone acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene Alcohol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-tert-butyl ether , dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, Ethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, di Propylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate , tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl Ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, Ethyl carbonate, propyl carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3 Methyl methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methyl Propyl oxypropionate, butyl 3-methoxypropionate, diethylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, 2-ethyl-1-hexanol, and the like. These organic solvents may be used singly or in combination.

For example, when a diamine component and a tetracarboxylic dianhydride component are reacted in an organic solvent, a solution in which a diamine component is dispersed or dissolved in an organic solvent is stirred, and a tetracarboxylic dianhydride component is directly added, or a method of dispersing or dissolving in an organic solvent; and a method of adding a diamine component to a solution obtained by dispersing or dissolving a tetracarboxylic dianhydride component in an organic solvent; and mutually adding a tetracarboxylic dianhydride component and Any method such as a method of diamine component can be used. Further, when the diamine component or the tetracarboxylic dianhydride component is composed of a plurality of compounds, it may be reacted in a state of being mixed beforehand, or may be reacted individually or sequentially, or may be individually made. The low molecular weight body obtained by the reaction is subjected to a mixing reaction to form a high molecular weight body.

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

In the above polymerization reaction, the ratio of the total number of moles of the tetracarboxylic dianhydride component to the total number of moles of the diamine component can be selected according to the molecular weight of the polyamic acid to be obtained. Similarly to the usual polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the produced polyamine. The preferred range is from 0.8 to 1.2.

The method for synthesizing the polyamic acid used in the present invention is not limited to the above-described method, and similarly to the general method for synthesizing poly-proline, even if the tetracarboxylic dianhydride is replaced, the corresponding structure of tetracarboxylic acid or tetra is used instead. A tetracarboxylic acid derivative such as a carboxylic acid dihalide can be reacted by a known method to obtain a corresponding polyamic acid.

As a method of producing a polyimine by hydrazine imidization of the above polyamic acid, a hot hydrazine imidization of a polypyridic acid solution and a catalyst for adding a catalyst to a polyaminic acid solution can be mentioned.醯imination. Further, since the ruthenium imidization ratio from polylysine to polyimine can increase the voltage holding ratio, it is preferably 30% or more, and preferably 50 to 99%. On the other hand, from the viewpoint of suppressing the whitening property, that is, suppressing the precipitation of the polymer in the varnish, it is preferably 70% or less. If you consider the characteristics of both, 50 to 80% is preferred.

The temperature at which the polyaminic acid is thermally imidated in the solution is from 100 to 400 ° C, preferably from 120 to 250 ° C, in order to The water to be produced should be removed to the outside of the system and implemented at the same time.

The catalytic ruthenium imidization of polylysine can be carried out by adding a basic catalyst and an acid anhydride to the polyaminic acid solution, and stirring at -20 to 250 ° C, preferably 0 to 180 ° C. The amount of the alkaline catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the prolyl group, and the amount of the anhydride is 1 to 50 moles of the amidate group, preferably 3 to 30 moles. The basic catalyst may, for example, be pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine. Among them, pyridine is preferred because it has a moderate alkalinity in the reaction. Examples of the acid anhydride include anhydrous acetic acid, anhydrous trimellitic acid, and anhydrous pyromellitic acid. Among them, when anhydrous acetic acid is used, purification after completion of the reaction becomes easy, which is preferable. The imidization ratio of the oxime imidization can be controlled by adjusting the amount of the catalyst, the reaction temperature, the reaction time, and the like.

When the produced polyamic acid or polyimine is recovered from the reaction solution of polyamic acid or polyimine, the reaction solution is poured into a poor solvent to precipitate. Examples of the poor solvent used to form the precipitate include methanol, acetone, hexane, butyl cyanidin, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water, and the like. . The polymer which has been poured into a poor solvent and precipitated can be dried under normal pressure or under reduced pressure at normal temperature or under reduced pressure after filtration and recovery. Further, if the polymer which has been precipitated and recovered is redissolved in an organic solvent and the operation of reprecipitation is repeated 2 to 10 times, the impurities in the polymer can be reduced. The poor solvent at this time may, for example, be an alcohol, a ketone or a hydrocarbon. When three or more kinds of poor solvents selected from the above are used, the efficiency of purification is further improved.

[(B) component]

The liquid crystal alignment agent of the present invention contains a reaction selected from the group consisting of a tetracarboxylic dianhydride component containing at least one tetracarboxylic dianhydride selected from the group consisting of the above formulas (1) and (1') and a diamine. As the component (B), at least one polymer of a polyimine precursor and a polyimine obtained by imidating the polyimine precursor.

When a liquid crystal alignment film selected from at least one of tetracarboxylic dianhydrides of the above formulas (1) and (1') is used as a raw material, it is considered to be in a liquid crystal and a liquid crystal alignment film by light irradiation. The interaction between the two can improve the residual DC characteristics.

Examples of the tetracarboxylic dianhydride selected from the above formulas (1) and (1') include the following compounds, but are not limited thereto.

At least one tetracarboxylic dianhydride group selected from the group consisting of the above formulas (1-1) to (1-5) is used for synthesizing polyglycine, that is, a tetracarboxylic dianhydride component used as the component (B). 10~100% is better. It is preferred to use 10 to 60%. Since the voltage holding ratio can be increased, it is more preferably 10 to 40 mol% of the total amount of the tetracarboxylic dianhydride component used in the synthesis of the component (B). Next, at least one tetracarboxylic dianhydride selected from the group consisting of formula (1-1), formula (1-3), and formula (1-5) is used, and more preferably 20 to 40 mol% is used.

Further, the other tetracarboxylic dianhydride described in the component (A) may be used as a raw material of the component (B) without impairing the effects of the present invention. For example, the tetracarboxylic dianhydride having an aliphatic group or an alicyclic group is used in an amount of from 0 to 90 mol% of the tetracarboxylic dianhydride component used in the synthesis of polyamic acid, that is, the component (B). good.

Further, the polymer of the component (B) may be a raw material selected from the group consisting of at least one selected from the group consisting of the following formulas (B-1) to (B-5).

(wherein Y ₁ represents a secondary amine, a tertiary amine, or an organic group having a monovalent structure of a heterocyclic ring structure, Y ₂ represents a secondary amine, a tertiary amine, or a divalent organic group having a heterocyclic structure .)

By using at least one diamine having a high polarity specific configuration selected from the above formulas (B-1) to (B-5), or more separately using a diamine having a carboxyl group and a diamine having a nitrogen-containing aromatic heterocyclic ring More than one type, since salt formation or hydrogen bonding promotes charge transfer by electrostatic interaction, residual DC characteristics can be improved.

The at least one diamine in the group of the above formulas (B-1) to (B-5) is selected, and examples thereof include the following diamines, but are not limited thereto.

Further, the polymer of the component (B) may be a diamine having a side chain which vertically aligns the liquid crystal used in the component (A), or another diamine described in the item of the component (A) as a raw material. .

The at least one diamine group in the group of the above formulas (B-1) to (B-5) is selected to be used in an amount of 10 to 80 mol% of the diamine component used in the synthesis of the poly (protonic acid) component (B). Preferably, it is preferred to use 20 to 70 mol%. The above-exemplified diamine is more preferably used in an amount of from 20 to 70 mol% of the total diamine component used in the synthesis of the component (B), and is selected from the group consisting of 3,5-diamine. Preferably, at least one diamine component of the group consisting of ketone acid and 3,5-diamino-N-(pyridin-3-ylmethyl)benzylamine is preferred.

In the method of producing the component (B), a tetracarboxylic acid containing a tetracarboxylic dianhydride which is selected from the group consisting of the above formulas (1) and (1'), and even other tetracarboxylic dianhydrides which are necessary as necessary Diacetate component, with diamine component By reacting, a polyimine precursor or a polyimine can be obtained.

The method of producing the component (B), except that at least one tetracarboxylic dianhydride selected from the group consisting of the above formulas (1) and (1') is used as a raw material, and the other method and the method for producing the component (A) "the same.

[Liquid alignment agent]

The liquid crystal alignment agent of the present invention is as described above, which has a polyfluorene selected from the group consisting of a polyimide precursor having a side chain which vertically aligns the liquid crystal, and a ruthenium imide of the polyimide precursor. At least one polymer of the imine group, that is, the component (A), and a tetracarboxylic dianhydride component selected from the group consisting of at least one tetracarboxylic dianhydride selected from the group consisting of the above formulas (1) and (1') At least one polymer of the polyimine precursor of the reaction product of the diamine and the polyimine of the ruthenium imide of the polyimide precursor, the component (B), and the organic solvent By.

The total content of the component (A) and the component (B) in the liquid crystal alignment agent of the present invention is not particularly limited, and is preferably 1 to 20% by mass, preferably 3 to 15% by mass, particularly preferably 3 to 10% by mass. %.

Further, the content ratio of the component (A) to the component (B) is not particularly limited. For example, in the mass ratio, the component (A): (B) component = X: 10-X (X = 1 to 9), Good for 2:8~8:2. However, the component (B) can be the same polymer as the component (A) by having a side chain in which the liquid crystal is vertically aligned.

Further, the liquid crystal alignment agent of the present invention may contain other polymers than the components (A) and (B). At this point, the polymer is in its entirety The content of the other polymer is preferably 0.5 to 15% by mass, preferably 1 to 10% by mass.

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

The organic solvent to be contained in the liquid crystal alignment agent is not particularly limited as long as it can dissolve or disperse the components contained in the component (A) or the component (B). For example, an organic solvent exemplified in the synthesis of the above polyamic acid can be mentioned. From the viewpoint of solubility, N-methyl-2-pyrrolidone, γ-butyrolactone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone 3-methoxy-N,N-dimethylpropanamide or the like is preferred. In particular, N-methyl-2-pyrrolidone or N-ethyl-2-pyrrolidone is preferred, but a mixed solvent of two or more types may also be used.

In addition, it is preferred to use a solvent which improves the uniformity or smoothness of the coating film in an organic solvent having high solubility in the component contained in the liquid crystal alignment agent.

Examples of the solvent for improving the uniformity or smoothness of the coating film include, for example, isopropyl alcohol, methoxymethylpentanol, methyl acesulfame, ethyl acesulfame, butyl cycas, and Kesai sulphate, butyl cyanoacetate, ethyl cyproterone acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol , ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propane Alcohol 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 single Ethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3 -methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene , propyl ether, dihexyl ether, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate , propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methyl Propyl propyl propionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1 -phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetic acid Ester, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, 2-ethyl- 1-hexanol and the like. These solvents may also be mixed in a plurality of types. When such a solvent is used, it is preferably 5 to 80% by mass, and more preferably 20 to 60% by mass, based on the total amount of the solvent contained in the liquid crystal alignment agent.

The liquid crystal alignment agent may contain components other than the above. As an example thereof, the film thickness uniformity when the liquid crystal alignment agent is coated or raised may be mentioned. A compound having a surface smoothness, a compound which enhances the adhesion between the liquid crystal alignment film and the substrate, and a compound which enhances the film strength of the liquid crystal alignment film.

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

Specific examples of the compound which improves the adhesion between the liquid crystal alignment film and the substrate include a compound containing a functional decane or an epoxy group-containing compound. For example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane , N-(2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3- Ureapropyl propyl trimethoxy decane, 3-ureidopropyl triethoxy decane, N-ethoxycarbonyl-3-aminopropyl trimethoxy decane, N-ethoxycarbonyl-3-amino group Propyltriethoxydecane, N-triethoxymercaptopropyltriamine, N-trimethoxydecylpropyltriamine, 10-trimethoxyindenyl-1,4 , 7-triazadecane, 10-triethoxyindolyl-1,4,7-triaza Decane, 9-trimethoxyindolyl-3,6-diazaindolyl acetate, 9-triethoxyindolyl-3,6-diazaindolyl acetate, N-benzyl 3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl- 3-aminopropyltriethoxydecane, N-bis(oxyethylene)-3-aminopropyltrimethoxydecane, N-bis(oxyethylene)-3-aminopropyltriethoxydecane , ethylene glycol diepoxypropyl ether, polyethylene glycol diepoxypropyl ether, propylene glycol diepoxypropyl ether, tripropylene glycol diepoxypropyl ether, polypropylene glycol diepoxypropyl ether, neopentyl Diol diglycidyl ether, 1,6-hexanediol diepoxypropyl ether, glycerol diepoxypropyl ether, 2,2-dibromo neopentyl glycol diepoxypropyl ether, 1,3,5,6-tetraepoxypropyl-2,4-hexanediol, N,N,N',N'-tetraepoxypropyl-m-nonanediamine, 1,3-double ( N,N-diepoxypropylaminomethyl)cyclohexane, N,N,N',N'-tetraepoxypropyl-4,4'-diaminodiphenylmethane, 3-( N-allyl-N-epoxypropyl)aminopropyltrimethoxydecane, 3-(N,N-diepoxypropyl)aminopropyltrimethyl Silane-yl and the like.

Further, in order to further increase the film strength of the liquid crystal alignment film, 2,2'-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane or tetrakis(methoxymethyl)bisphenol may be added. Phenolic compound. When the compound is used, it is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of the total amount of the polymer contained in the liquid crystal alignment agent.

In addition to the above, the liquid crystal alignment agent may be added with a dielectric or conductive substance for the purpose of changing the electrical properties such as the dielectric constant or the conductivity of the liquid crystal alignment film, as long as the effect of the present invention is not impaired. .

By applying this liquid crystal alignment agent onto a substrate and baking it, a liquid crystal alignment film which vertically aligns the liquid crystal can be formed.

The liquid crystal alignment agent of the present invention comprises: a polyfluorene imine which is selected from the group consisting of a polyimide precursor having a side chain in which the liquid crystal is vertically aligned, and a polyimide obtained by imidating the polyimide precursor. At least one polymer of the group, that is, the component (A), and a tetracarboxylic dianhydride component selected from the group consisting of at least one tetracarboxylic dianhydride selected from the group consisting of the above formulas (1) and (1') a polyimine precursor obtained by reacting an amine, and at least one polymer of the polyimine obtained by imidating the polyimine precursor, that is, component (B), The residual DC characteristics are made good.

The substrate is not particularly limited as long as it is a substrate having high transparency, and a plastic substrate such as a glass substrate, an acrylic substrate, or a polycarbonate substrate can be used. Further, from the viewpoint of simplification of the process, it is preferred to use a substrate on which an ITO electrode or the like for driving a liquid crystal is formed. Further, in the reflective liquid crystal display device, an opaque material such as a germanium wafer can be used only on a single-sided substrate, and in this case, a material such as aluminum or the like can be used as the electrode.

The coating method of the liquid crystal alignment agent is not particularly limited, and examples thereof include a method of performing screen printing, lithography, flexographic printing, inkjet printing, or the like, or a dipping method, a roll coating method, a slit coating method, and a rotation. Coating method, etc.

The baking temperature of the coating film formed by coating the liquid crystal alignment agent is not limited, and can be carried out, for example, at any temperature of 100 to 350 ° C, preferably 120 to 300 ° C, more preferably 150 to 250 ° C. This firing system can add Hot plate, hot air circulation furnace, infrared furnace, etc.

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

The liquid crystal display device of the present invention comprises a liquid crystal layer having two substrates disposed oppositely, a liquid crystal layer disposed between the substrates, and a liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention disposed between the substrate and the liquid crystal layer. A liquid crystal display element of a vertical alignment mode of a liquid crystal cell. Specifically, it is a liquid crystal display element having a vertical alignment type of a liquid crystal cell, and the liquid crystal alignment unit is formed by applying the liquid crystal alignment agent of the present invention to two substrates and baking it to form a liquid crystal alignment film. In the liquid crystal alignment film, two substrates are disposed opposite to each other, and a liquid crystal layer composed of liquid crystal is sandwiched between the two substrates to be irradiated with ultraviolet rays.

Therefore, it is considered that by using the liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention, the liquid crystal alignment film and the liquid crystal layer are irradiated with ultraviolet rays, and the liquid crystal interacts with the liquid crystal alignment film of the present invention to become a liquid crystal residue. The DC is small, and it is not easy to produce a branded liquid crystal display element.

The substrate used for the liquid crystal display device of the present invention is not particularly limited as long as it is a substrate having high transparency, and is usually a substrate on which a transparent electrode for driving a liquid crystal is formed on a substrate. As a specific example, the same as the substrate described in the liquid crystal alignment film is mentioned.

The liquid crystal display device of the present invention may also use a substrate in which an electrode pattern or a protrusion pattern has been provided in the past, but by using a liquid crystal alignment film formed using the liquid crystal alignment agent of the present invention, even if a single-sided substrate is used, 1~ 10μm line/slit electrode pattern, no slit pattern on the opposite substrate The substrate of the type or the pattern of the protrusion pattern can still be operated, so that the process at the time of component manufacture can be simplified, and high transmittance can be obtained.

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

In the case of a transmissive liquid crystal display device, the above-described substrate is generally used. However, in a reflective liquid crystal display device, an opaque substrate such as a germanium wafer can be used only on a single-sided substrate. At this time, the electrode system formed on the substrate can also use a material such as aluminum that reflects light.

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

As the liquid crystal composition used for the liquid crystal display element of the present invention, a nematic liquid crystal having a negative dielectric anisotropy can be used. For example, a dicyanobenzene liquid crystal, a pyridazine liquid crystal, a Schiff base liquid crystal, an oxy azo liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, a terphenyl liquid crystal, or the like can be used. . Further, it is preferred to use an alkenyl liquid crystal in combination. As such an alkenyl-based liquid crystal, those known in the past can be used. For example, a compound represented by the following formula may be mentioned, but it is not limited thereto.

The liquid crystal composition constituting the liquid crystal layer of the liquid crystal display element of the present invention is not particularly limited as long as it is used in the liquid crystal material in the vertical alignment mode. For example, a liquid crystal composition having a negative dielectric anisotropy manufactured by Merck, that is, MLC-6608, MLC-6609, or the like can be used. Further, a liquid crystal composition containing an alkenyl-based liquid crystal and having a negative dielectric anisotropy, that is, MLC-3022, MLC-3023 (including a photopolymerizable compound (RM)) manufactured by Merck & Co., Ltd., or the like can be used.

A well-known method is mentioned as a method of sandwiching this liquid crystal layer between two board|substrate. For example, a spacer in which a pair of substrates of a liquid crystal alignment film has been formed, a bead or the like is spread on a liquid crystal alignment film of one substrate, and an adhesive is applied around the substrate to form a surface on which the liquid crystal alignment film is formed. A method of bonding to the other substrate toward the inner side, injecting a liquid crystal under reduced pressure, and sealing.

Further, a pair of substrates on which a liquid crystal alignment film has been formed is prepared, and a spacer such as beads is spread on a liquid crystal alignment film of one substrate, and then the liquid crystal is dropped, and then the surface on which the liquid crystal alignment film side is formed faces inward and adheres to the other layer. A substrate and a method of sealing can also manufacture a liquid crystal cell. Thickness of the spacer at this time The degree is preferably 1 to 30 μm, preferably 2 to 10 μm.

The step of producing a liquid crystal cell by irradiating ultraviolet rays to the liquid crystal alignment film and the liquid crystal layer may be performed at any time after the liquid crystal is sealed. The amount of ultraviolet light irradiation is, for example, 1 to 60 J/cm ² , preferably 40 J/cm ² or less, and if the amount of ultraviolet irradiation is small, it is possible to suppress a decrease in reliability due to damage of a member constituting the liquid crystal display element.

The ultraviolet wavelength used is preferably 300 to 500 nm, and preferably 300 to 400 nm.

Moreover, the ultraviolet irradiation of the liquid crystal alignment film and the liquid crystal layer can also be performed in a state where a voltage is applied and the electric field is maintained. Here, the voltage applied between the electrodes is, for example, 5 to 30 Vp-p, preferably 5 to 20 Vp-p.

In the case of a PSA method having a polymerizable compound in a liquid crystal, when a voltage is applied to the liquid crystal alignment film and the liquid crystal layer and ultraviolet rays are simultaneously irradiated, the polymerizable compound reacts to form a polymer, and the liquid crystal molecules are tilted by the polymer. By being memorized, the response speed of the obtained liquid crystal display element can be made faster. Moreover, by containing the component (B), the residual DC characteristics also become good. In this case, if the amount of ultraviolet irradiation is small, the ultraviolet irradiation time can be reduced, and the production efficiency is improved, which is preferable.

Further, the liquid crystal alignment agent can be used not only as a liquid crystal alignment agent for a liquid crystal display element of a vertical alignment type such as a PSA liquid crystal display or an SC-PVA liquid crystal display, but also can be suitably used for production by rubbing treatment or optical alignment. A liquid crystal alignment film formed by treatment.

[Examples]

The invention will be described in more detail by way of the following examples, but the invention is not limited thereto. The abbreviations of the compounds used below are as follows.

(acid dianhydride)

BODA: Bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride.

CBDA: 1,2,3,4-cyclobutane tetracarboxylic dianhydride.

PMDA: pyromellitic dianhydride.

(diamine)

DBA: 3,5-diamino benzoic acid

m-PDA: 1,3-phenylenediamine

p-PDA: 1,4-phenylenediamine

3AMPDA: 3,5-diamino-N-(pyridin-3-ylmethyl)benzylamide

DDM: 4,4'-diaminodiphenylmethane

(In the formula DA-6, t represents trans.)

<solvent>

NMP: N-methyl-2-pyrrolidone.

BCS: Butyl cypress.

<Polymerimide molecular weight measurement>

Device: Normal temperature gel permeation chromatography (GPC) device (SSC-7200) manufactured by Quanzhou Science Co., Ltd., column: Shodex column (KD-803, KD-805), column temperature: 50 ° C, elution Liquid: N,N'-dimethylformamide (as an additive, lithium bromide-hydrate (LiBr‧H ₂ O) is 30 mmol/L, phosphoric acid ‧ anhydrous crystal (o-phosphoric acid) is 30 mmol/L, tetrahydrofuran (THF) ) is 10 ml / L), flow rate: 1.0 ml / min, standard sample for calibration line: TSK standard polyethylene oxide (molecular weight of about 9,000, 150,000, 100,000, and 30,000) made by Tosoh Corporation, and Polyethylene glycol (molecular weight of about 12,000, 4,000, and 1,000) manufactured by Polymer Laboratories.

<Measurement of yttrium imidation rate>

20 mg of polyimine powder was placed in an NMR sample tube (NMR sample tube standard manufactured by Kusano Scientific Co., Ltd. 5) 1.0 ml of deuterated dimethyl hydrazine (DMSO-d ₆ , 0.05% by mass of TMS mixture) was added, and ultrasonic waves were applied thereto to completely dissolve. The 500 MHz proton NMR of this solution was measured in an NMR measuring apparatus (JNW-ECA500 manufactured by JEOL Ltd.). The ruthenium imidization rate is determined by the proton derived from the unaltered structure before and after imidization as the reference proton, and the peak accumulating value of the proton is used, and the proline derived from the vicinity of 9.5 to 10.0 ppm is used. The accumulating value of the proton peak of the NH group is obtained by the following formula. Further, in the following formula, x is the proton peak accumulating value derived from the NH group of the proline, y is the peak accumulating value of the reference proton, and α is the reference proton to the polylysine (the imidization ratio) The ratio of the number of protons of the NH group of the proline acid at 0%).

醯 imidization rate (%) = (1-α‧x/y) × 100

<Synthesis Example 1>

BODA (3.30 g, 13.2 mmol), DA-3 (3.35 g, 8.80 mmol), and m-PDA (1.43 g, 13.2 mmol) were dissolved in NMP (29.8 g), and reacted at 60 ° C for 4 hours. . Thereafter, PMDA (1.85 g, 8.47 mmol) and NMP (9.93 g) were added, and the mixture was reacted at room temperature for 4 hours to obtain a polyaminic acid solution X1. The polyamine has a number average molecular weight of 13,000 and a weight average molecular weight of 39,000.

After adding NMP to 6.5% by mass of this polyaminic acid solution (25 g), anhydrous acetic acid (5.62 g) and pyridine (4.35 g) were added as a ruthenium catalyst, and the reaction was carried out at 80 ° C for 4 hours. This reaction solution was poured into methanol (300 g), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder A. The polyamidimide had a ruthenium iodide ratio of 73%, a number average molecular weight of 13,000, and a weight average molecular weight of 39,000.

To the obtained polyimine powder A (2.0 g), NMP (18.0 g) was added, and the mixture was stirred at 70 ° C for 12 hours to be dissolved. BCS (13.3 g) was added to the solution, and the liquid crystal alignment agent A1 was obtained by stirring at room temperature for 2 hours.

<Synthesis Example 2>

BODA (3.30 g, 13.2 mmol), DA-3 (3.35 g, 8.80 mmol), and m-PDA (1.43 g, 13.2 mmol) were dissolved in NMP (29.2 g), and reacted at 60 ° C for 4 hours. . Thereafter, CBDA (1.66 g, 8.47 mmol) and NMP (9.74 g) were added at 40 ° C. The reaction was carried out for 4 hours to obtain a polyaminic acid solution.

In the same manner as in Synthesis Example 1, except that the polyamic acid solution (25 g) was used, the ruthenium imidization reaction was carried out, and the treatment after the reaction was carried out to obtain a polyimide pigment B. The polyamidimide had a ruthenium iodide ratio of 73%, a number average molecular weight of 13,000, and a weight average molecular weight of 39,000.

The liquid crystal alignment agent U1 was obtained by the same treatment as in Synthesis Example 1 except that the polyimine powder B (2.0 g) was used instead of the polyimine powder A.

Next, BODA (3.75 g, 15 mmol), DA-3 (1.90 g, 4.99 mmol), m-PDA (2.16 g, 20.0 mmol) were dissolved in NMP (29.7 g), and reacted at 60 ° C for 4 hours. Thereafter, PMDA (2.10 g, 9.63 mmol) and NMP (9.92 g) were added, and the mixture was reacted at 40 ° C for 4 hours to obtain a polyaminic acid solution.

In the same manner as in Synthesis Example 1, except that the polyaminic acid solution (25 g) was used, the ruthenium imidization reaction was carried out, and the treatment after the reaction was carried out to obtain a polyamidimide powder C. The polyamidimide had a ruthenium iodide ratio of 73%, a number average molecular weight of 13,000, and a weight average molecular weight of 39,000.

The liquid crystal alignment agent L1 was obtained by the same treatment as in Synthesis Example 1, except that the obtained polyimine powder C was replaced with the polyimine powder A (2.0 g).

5.0 g of the liquid crystal alignment agent U1 was used as the first component, and 5.0 g of the liquid crystal alignment agent L1 was used as the second component and mixed to obtain a liquid crystal alignment. Agent A2.

<Synthesis Example 3>

BODA (22.5 g, 90.0 mmol), DA-4 (62.1 g, 158 mmol), p-PDA (14.6 g, 135 mmol), and 3AMPDA (38.16, 157 mmol) were dissolved in NMP (620 g) and allowed to make at 55 °C. After reacting for 2 hours, CBDA (68.4 g, 349 mmol) and NMP (102 g) were added, and the mixture was reacted at 40 ° C for 4 hours to obtain a polyaminic acid solution.

After adding NMP to 6.5% by mass of this polyaminic acid solution (85 g), anhydrous acetic acid (18.87 g) and pyridine (5.85 g) were added as a ruthenium catalyzed catalyst, and the mixture was reacted at 50 ° C for 3 hours. This reaction solution was poured into methanol (1000 g), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder D. The polyamidimide had a ruthenium iodide ratio of 73%, a number average molecular weight of 13,000, and a weight average molecular weight of 39,000.

The liquid crystal alignment agent U2 was obtained by the same treatment as in Synthesis Example 1 except that the obtained polyimine powder D was replaced with the polyimine powder A (2.0 g).

Next, BODA (123 g, 491 mmol), DBA (127 g, 837 mmol), DA-1 (60.7 g, 148 mmol) were dissolved in NMP (1246 g), and reacted at 55 ° C for 2 hours, and then PMDA (43.0 g) was added. 197 mmol) and NMP (172 g) were reacted at room temperature for 4 hours, and then CBDA (50.6 g, 258 mmol) and NMP were added. (202 g) was allowed to react at room temperature for 4 hours to obtain a polyaminic acid solution.

After adding NMP to the polyamic acid solution (700 g) and diluting it to 8% by mass, anhydrous acetic acid (172 g) and pyridine (54 g) were added as a ruthenium-catalyzed catalyst, and the mixture was reacted at 80 ° C for 4 hours. This reaction solution was poured into methanol (7000 g), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder E. The polyamidimide had a ruthenium iodide ratio of 73%, a number average molecular weight of 13,000, and a weight average molecular weight of 39,000.

The liquid crystal alignment agent L2 was obtained by the same treatment as in Synthesis Example 1, except that the obtained polyimine powder A was replaced with the obtained polyimide pigment A (2.0 g).

5.0 g of the liquid crystal alignment agent U2 obtained was used as the first component, and 5.0 g of the liquid crystal alignment agent L2 was used as the second component, and the liquid crystal alignment agent A3 was obtained.

<Synthesis Example 4>

BODA (1.80 g, 7.19 mmol), DA-3 (2.74 g, 7.20 mmol), 3AMPDA (0.87 g, 3.59 mmol), and DA-2 (2.38 g, 7.20 mmol) were dissolved in NMP (29.7 g). The reaction was allowed to proceed at 60 ° C for 4 hours. Thereafter, CBDA (2.10 g, 10.7 mmol) and NMP (9.89 g) were added, and the mixture was reacted at 40 ° C for 4 hours to obtain a polyaminic acid solution.

This polyglycine solution (25g) was diluted with NMP to a mass of 6.5. After %, anhydrous acetic acid (4.64 g) and pyridine (3.59 g) were added as a ruthenium hydride catalyst, and the mixture was reacted at 80 ° C for 4 hours. This reaction solution was poured into methanol (300 g), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder F. The polyamidimide had an imidization ratio of 74%, a number average molecular weight of 12,500, and a weight average molecular weight of 38,000.

The liquid crystal alignment agent U3 was obtained by the same treatment as in Synthesis Example 1, except that the obtained polyimine powder F was replaced with the polyimine powder A (2.0 g).

Next, BODA (3.15 g, 12.6 mmol), DA-3 (2.40 g, 6.31 mmol), DBA (1.28 g, 8.40 mmol), and 3AMPDA (1.25 g, 6.31 mmol) were dissolved in NMP (30.4 g), The reaction was allowed to proceed at 60 ° C for 4 hours. Thereafter, PMDA (1.79 g, 8.19 mmol) and NMP (10.14 g) were added, and the mixture was reacted at room temperature for 4 hours to obtain a polyaminic acid solution.

After adding NMP to 6.5% by mass of this polyaminic acid solution (25 g), anhydrous acetic acid (5.26 g) and pyridine (4.08 g) were added as a ruthenium amide catalyst, and the mixture was reacted at 80 ° C for 4 hours. This reaction solution was poured into methanol (300 g), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder G. The polyamidimide had a ruthenium iodide ratio of 75%, a number average molecular weight of 13,000, and a weight average molecular weight of 38,500.

The same treatment as in Synthesis Example 1 was carried out except that instead of the polyimine powder A, the obtained polyimine powder G (2.0 g) was used instead. The liquid crystal alignment agent L3 was obtained.

5.0 g of the liquid crystal alignment agent U3 obtained was regarded as the first component, and 5.0 g of the liquid crystal alignment agent L3 was used as the second component, and the liquid crystal alignment agent A4 was obtained.

<Synthesis Example 5>

BODA (3.75 g, 15 mmol), DA-3 (1.90 g, 4.99 mmol), and m-PDA (2.16 g, 20.0 mmol) were dissolved in NMP (29.1 g), and reacted at 60 ° C for 4 hours. Thereafter, CBDA (1.89 g, 9.64 mmol) and NMP (9.71 g) were added, and the mixture was reacted at 40 ° C for 4 hours to obtain a polyaminic acid solution.

In the same manner as in Synthesis Example 1, except that the polyamic acid solution (25 g) was used, the ruthenium imidization reaction was carried out, and the treatment after the reaction was carried out to obtain a polyimine powder H. The polyamidimide had a ruthenium iodide ratio of 73%, a number average molecular weight of 13,000, and a weight average molecular weight of 39,000.

The liquid crystal alignment agent L4 was obtained by the same treatment as in Synthesis Example 1 except that the obtained polyimine powder H was replaced with the polyimine powder A (2.0 g).

5.0 g of the liquid crystal alignment agent U1 obtained in Synthesis Example 2 was regarded as the first component, and 5.0 g of the liquid crystal alignment agent L4 was used as the second component, and the liquid crystal alignment agent A5 was obtained.

<Synthesis Example 6>

BODA (4.12 g, 16.5 mmol), DA-5 (2.87 g, 6.60 mmol), and DBA (2.34 g, 15.4 mmol) were dissolved in NMP (24.8 g), and reacted at 80 ° C for 5 hours. Thereafter, CBDA (1.01 g, 5.15 mmol) and NMP (8.30 g) were added, and the mixture was reacted at 40 ° C for 4 hours to obtain a polyaminic acid solution.

After adding NMP to the polyamic acid solution (38 g) and diluting it to 6 mass%, anhydrous acetic acid (8.43 g) and pyridine (3.27 g) were added as a ruthenium catalyst, and the reaction was carried out at 100 ° C for 3 hours. This reaction solution was poured into methanol (484 g), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder I. The polyamidimide had a ruthenium iodide ratio of 73%, a number average molecular weight of 13,000, and a weight average molecular weight of 39,000.

The liquid crystal alignment agent A6 was obtained by the same treatment as in Synthesis Example 1, except that the polyimine powder A was replaced with the obtained polyimide pigment A (2.0 g).

<Synthesis Example 7>

NMP (10.0 g) was added to the polyamic acid solution X1 (10 g) obtained in Synthesis Example 1, and the mixture was stirred at room temperature for 1 hour, and BCS (13.3 g) was added thereto, and the mixture was stirred at room temperature for 2 hours. Liquid crystal alignment agent A7.

<Synthesis Example 8>

BODA (123g, 491mmol), DBA (127g, 837mmol), DA-1 (60.7 g, 148 mmol) was dissolved in NMP (1246 g), and after reacting at 55 ° C for 2 hours, CA-1 (70.6 g, 197 mmol) and NMP (282 g) were added, and the reaction was carried out at room temperature. After an additional hour, CBDA (50.6 g, 258 mmol) and NMP (202 g) were added, and the mixture was reacted at room temperature for 4 hours to obtain a polyaminic acid solution.

After the polyacrylic acid solution (40 g) was diluted with NMP to 8 mass%, anhydrous acetic acid (9.15 g) and pyridine (2.84 g) were added as a ruthenium catalyzed catalyst, and the mixture was reacted at 80 ° C for 3 hours. This reaction solution was poured into methanol (473 g), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder J. The polyamidimide had an imidization ratio of 74%, a number average molecular weight of 13,500, and a weight average molecular weight of 40,000.

The liquid crystal alignment agent L5 was obtained by the same treatment as in Synthesis Example 1, except that the polyimine powder A was replaced with the polyimine powder A (2.0 g).

5.0 g of the liquid crystal alignment agent U2 obtained in Synthesis Example 3 was regarded as the first component, and 5.0 g of the liquid crystal alignment agent L5 was used as the second component, and the liquid crystal alignment agent A8 was obtained.

<Synthesis Example 9>

BODA (2.38 g, 9.51 mmol), DBA (1.45 g, 9.53 mmol), DA-1 (2.34 g, 5.70 mmol), DA-3 (1.45 g, 3.81 mmol) were dissolved in NMP (30.4 g), After reacting at 55 ° C for 3 hours, CA-1 (2.04 g, 5.69 mmol) and NMP were added. (8.17 g), the mixture was reacted at room temperature for 4 hours, and CBDA (0.60 g, 3.06 mmol) and NMP (2.38 g) were further added thereto, and the mixture was reacted at room temperature for 4 hours to obtain a polyaminic acid solution.

After the polyacrylic acid solution (40 g) was diluted with NMP to 6.5% by mass, anhydrous acetic acid (7.46 g) and pyridine (2.31 g) were added as a ruthenium catalyzed catalyst, and the mixture was reacted at 80 ° C for 3 hours. This reaction solution was poured into methanol (465 g), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder L. The polyimine had a hydrazine imidation ratio of 75%, a number average molecular weight of 13,000, and a weight average molecular weight of 39,500.

The liquid crystal alignment agent L6 was obtained by the same treatment as in Synthesis Example 1 except that the obtained polyimine powder L was replaced with the polyimine powder A (2.0 g).

5.0 g of the liquid crystal alignment agent U2 obtained in Synthesis Example 3 was regarded as the first component, and 5.0 g of the liquid crystal alignment agent L6 was used as the second component, and the liquid crystal alignment agent A9 was obtained.

<Synthesis Example 10>

BODA (2.25 g, 8.99 mmol), DA-2 (2.97 g, 8.99 mmol), and DA-3 (3.43 g, 9.01 mmol) were dissolved in NMP (34.6 g), and reacted at 60 ° C for 4 hours. . Thereafter, CBDA (1.75 g, 8.92 mmol) and NMP (6.99 g) were added, and the mixture was reacted at 40 ° C for 4 hours to obtain a polyaminic acid solution.

This polyglycine solution (40g) was diluted with NMP to a mass of 6.5. After %, anhydrous acetic acid (7.06 g) and pyridine (2.19 g) were added as a ruthenium catalyzed catalyst, and the mixture was reacted at 80 ° C for 4 hours. This reaction solution was poured into methanol (463 g), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder M. The polyamidimide had an imidization ratio of 74%, a number average molecular weight of 12,500, and a weight average molecular weight of 38,500.

The liquid crystal alignment agent U4 was obtained by the same treatment as in Synthesis Example 1, except that the obtained polyimine powder M was replaced with the polyimine powder A (2.0 g).

Next, BODA (1.20 g, 4.80 mmol), DBA (1.46 g, 9.59 mmol), 3AMPDA (1.74 g, 7.18 mmol), and DA-3 (2.74 g, 7.20 mmol) were dissolved in NMP (28.58 g), The reaction was allowed to proceed at 60 ° C for 2 hours. Thereafter, PMDA (1.05 g, 4.81 mmol) and NMP (4.19 g) were added, and the mixture was reacted at room temperature for 4 hours, and then CBDA (2.78 g, 14.18 mmol) and NMP (11.1 g) were added at room temperature. The reaction was carried out for 4 hours to obtain a polyaminic acid solution.

After adding NMP to 6.5% by mass of this polyaminic acid solution (40 g), anhydrous acetic acid (8.90 g) and pyridine (2.76 g) were added as a ruthenium catalyzed catalyst, and the mixture was reacted at 80 ° C for 4 hours. This reaction solution was poured into methanol (472 g), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder N. The polyamidimide had an imidization ratio of 74%, a number average molecular weight of 13,000, and a weight average molecular weight of 39,000.

In addition to replacing the polyimine powder A, the obtained polyimine powder was used instead. Other than N (2.0 g), the same treatment as in Synthesis Example 1 was carried out to obtain a liquid crystal alignment agent L7.

3.0 g of the liquid crystal alignment agent U4 obtained was used as the first component, and 7.0 g of the liquid crystal alignment agent L7 was used as the second component, and the liquid crystal alignment agent A10 was obtained.

<Synthesis Example 11>

BODA (1.20 g, 4.80 mmol), DBA (1.46 g, 9.59 mmol), 3AMPDA (1.74 g, 7.18 mmol), and DA-3 (2.74 g, 7.20 mmol) were dissolved in NMP (28.58 g) at 60 The reaction was allowed to proceed for 2 hours at °C. Thereafter, CA-2 (1.41 g, 4.79 mmol) and NMP (5.65 g) were added, and the mixture was reacted at room temperature for 4 hours, and then CBDA (2.78 g, 14.18 mmol) and NMP (11.1 g) were added thereto. The reaction was carried out for 4 hours at a temperature to obtain a polyaminic acid solution.

After the polyacrylic acid solution (40 g) was diluted with NMP to 6.5% by mass, anhydrous acetic acid (8.61 g) and pyridine (2.67 g) were added as a ruthenium catalyzed catalyst, and the mixture was reacted at 80 ° C for 4 hours. This reaction solution was poured into methanol (470 g), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder O. The polyamidimide had an imidization ratio of 75%, a number average molecular weight of 14,000, and a weight average molecular weight of 39,000.

The liquid crystal alignment agent L8 was obtained by the same treatment as in Synthesis Example 1, except that the polyimine powder A was replaced with the obtained polyimine powder A (2.0 g).

3.0 g of the liquid crystal alignment agent U4 obtained in Synthesis Example 10 was regarded as the first component, and 7.0 g of the liquid crystal alignment agent L8 was used as the second component, and the liquid crystal alignment agent A11 was obtained.

<Synthesis Example 12>

CA-3 (2.42 g, 10.8 mmol), DA-6 (2.40 g, 9.01 mmol), DA-5 (1.56 g, 3.59 mmol), and DA-7 (2.67 g, 5.40 mmol) were dissolved in NMP (31.7). In g), it was allowed to react at 60 ° C for 4 hours. Thereafter, PMDA (1.30 g, 5.94 mmol) and NMP (5.20 g) were added, and the mixture was reacted at room temperature for 4 hours to obtain a polyaminic acid solution.

After the polyacrylic acid solution (40 g) was diluted with NMP to 6.0% by mass, anhydrous acetic acid (2.01 g) and pyridine (1.61 g) were added as a ruthenium catalyzed catalyst, and the mixture was reacted at 110 ° C for 4 hours. This reaction solution was poured into methanol (480 g), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder P. The polyimine had a hydrazine imidation ratio of 55%, a number average molecular weight of 11,000, and a weight average molecular weight of 32,000.

In place of the polyimine powder A, NMP (18.0 g) was added to the obtained polyimine powder P (2.0 g), and the mixture was stirred at 70 ° C for 12 hours to be dissolved. BCS (13.3 g) was added to the solution, and the liquid crystal alignment agent A12 was obtained by stirring at room temperature for 2 hours.

<Synthesis Example 13>

CA-3 (3.83 g, 17.1 mmol), DA-6 (2.40 g, 9.01 mmol), DA-5 (1.56 g, 3.59 mmol) and DA-7 (2.67 g, 5.40 mmol) were dissolved in NMP (31.7 g), and reacted at 60 ° C for 6 hours to obtain a polyaminic acid solution.

After adding NMP to 6.0% by mass of this polyaminic acid solution (40 g), anhydrous acetic acid (2.07 g) and pyridine (1.60 g) were added as a ruthenium-catalyzed catalyst, and the mixture was reacted at 110 ° C for 4 hours. This reaction solution was poured into methanol (480 g), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder Q. The polyimine had a hydrazine imidation ratio of 55%, a number average molecular weight of 10,500, and a weight average molecular weight of 3,500.

To the obtained polyimine powder Q (2.0 g), NMP (18.0 g) was added, and the mixture was stirred at 70 ° C for 12 hours to be dissolved. To the solution, BCS (13.3 g) was added, and the liquid crystal alignment agent U5 was obtained by stirring at room temperature for 2 hours.

Next, CA-3 (2.96 g, 13.2 mmol), DDM (3.49 g, 17.6 mmol), and DA-7 (2.18 g, 4.41 mmol) were dissolved in NMP (34.5 g), and reacted at 60 °C. 4 hours. Thereafter, PMDA (1.54 g, 7.04 mmol) and NMP (6.10 g) were added, and the mixture was reacted at room temperature for 4 hours to obtain a polyaminic acid solution X2. The polyamine has a number average molecular weight of 12,500 and a weight average molecular weight of 34,000.

NMP (10.0 g) was added to the obtained polyamic acid solution X2 (10 g), and the mixture was stirred at room temperature for 1 hour, and BCS (13.3 g) was added thereto, and the liquid crystal alignment agent L9 was obtained by stirring at room temperature for 2 hours. .

5.0 g of the liquid crystal alignment agent U5 obtained was regarded as the first component, and 5.0 g of the liquid crystal alignment agent L9 was used as the second component, and the liquid crystal alignment agent A13 was obtained.

<Making a liquid crystal cell> (Example A)

Using the liquid crystal alignment agent A1 obtained in Synthesis Example 1, a liquid crystal cell was produced by the following procedure. The liquid crystal alignment agent A1 obtained in Synthesis Example 1 was spin-coated on an ITO surface of an ITO electrode substrate having an ITO electrode pattern having a pixel size of 100 μm × 300 μm and having a line/space of 5 μm, respectively, and heated at 80 ° C. After drying on the plate for 90 seconds, it was baked in a hot air circulating oven at 200 ° C for 20 minutes to form a liquid crystal alignment film having a film thickness of 100 nm.

Further, the liquid crystal alignment agent A1 was spin-coated on the ITO surface on which the electrode pattern was not formed, and dried on a hot plate at 80 ° C for 90 seconds, and then fired in a hot air circulating oven at 200 ° C for 20 minutes to form a film. A liquid crystal alignment film having a thickness of 100 nm.

In the above two substrates, a 4 μm bead spacer was spread on the liquid crystal alignment film of one substrate, and a sealant (solvent type thermosetting epoxy resin) was printed thereon. Next, after the surface of the other substrate on which the liquid crystal alignment film side is formed faces inward and is bonded to the previous substrate, the sealant is cured to form an empty cell. Liquid crystal MLC-6608 (trade name, manufactured by Merck), which is a liquid crystal composition containing no alkenyl-based liquid crystal, was injected into the empty cell by a vacuum injection method to prepare a liquid crystal cell. Make the obtained liquid crystal unit at 110 Annealing in a circulating oven at °C for 30 minutes (realignment treatment).

Thereafter, the liquid crystal cell was irradiated with light under the following conditions, and the voltage holding ratio and residual DC were measured under the following conditions. Further, for comparison, under the same conditions, the voltage holding ratio and the residual DC were also measured for the liquid crystal cell which was not irradiated with light.

[light irradiation]

From the outside of the liquid crystal cell, irradiate 6J/cm ² through the UV of the 365 nm band pass filter (the lamp system uses USHIO Super High Pressure Mercury Lamp LL, and ORC UV Light Measure Model UV-M03A (Attachment: UV-35) Measuring illuminance).

[voltage retention rate]

Using VHR-1A manufactured by Dongyang Technology Co., a voltage of 1 V was applied to the obtained liquid crystal cell at 60 ° C for 60 μs, and the ratio of the voltage held after 1667 ms was measured as a voltage holding ratio.

[Evaluation of residual DC]

The liquid crystal cell after the voltage holding rate measurement was applied with an AC voltage of 5.8 Vpp and a DC voltage of 1 V for 48 hours. Immediately after the DC voltage was released, the voltage generated in the liquid crystal cell (residual DC) was obtained by a flicker elimination method. This value is an indicator of the afterimage characteristics, and when the value is ±30 mV or less, it is excellent in afterimage characteristics.

(Example B, Comparative Example A, Reference Example A)

The liquid crystal cell irradiated with light was produced in the same manner as in Example A except that the liquid crystal alignment agent A1 was used instead of the liquid crystal alignment agent A1, and the voltage holding ratio and residual DC were measured.

(Example 1)

A light-irradiated liquid crystal cell was produced in the same manner as in Example A except that instead of MLC-6608, MLC-3022 (commercial name of Merck) which is a liquid crystal composition containing an alkenyl liquid crystal was used, The voltage holding ratio and residual DC were measured.

(Examples 2 to 4, 8 to 14)

The liquid crystal cell irradiated with light was produced in the same manner as in Example 1 except that the liquid crystal alignment agent A1 was used instead of the liquid crystal alignment agent A1, and the voltage holding ratio and residual DC were measured.

(Comparative examples 1 to 2)

The liquid crystal cell irradiated with light was produced in the same manner as in Example 1 except that the liquid crystal alignment agent A1 was used instead of the liquid crystal alignment agent A1, and the voltage holding ratio and residual DC were measured.

(Example 5)

In place of MLC-6608, MLC-3023, which is a liquid crystal composition containing an alkenyl liquid crystal and RM (photopolymerizable compound), is used instead. In addition to the liquid crystal alignment agent A1, the liquid crystal alignment agent A2 was used instead of the liquid crystal alignment agent A1, and the PSA treatment was carried out under the following conditions without performing light irradiation, and the same operation as in Example A was carried out to produce light irradiation. The liquid crystal cell and measure the voltage holding ratio and residual DC.

[PSA treatment]

In a state where a DC voltage of 15 V is applied, from the outside of the liquid crystal cell, 10 J/cm ² is passed through a UV of 325 nm high-pass filter (the lamp system uses USHIO Super High Pressure Mercury Lamp LL, ORC UV Light Measure Model UV- M03A (Attachment: UV-35) measures illuminance). Then, UV (UV lamp: FLR40SUV32/A-1) was irradiated for 30 minutes using a UV-FL irradiation apparatus manufactured by Toshiba Lighting Technology Co., Ltd. without applying a voltage.

(Examples 15 to 19)

The PSA-treated liquid crystal cell was produced in the same manner as in Example 5 except that the liquid crystal alignment agent A2 was used instead of the liquid crystal alignment agent A2, and the voltage holding ratio and residual DC were measured.

(Comparative examples 3 to 4)

The PSA-treated liquid crystal cell was produced in the same manner as in Example 5 except that the liquid crystal alignment agent A2 was used instead of the liquid crystal alignment agent A2, and the voltage holding ratio and residual DC were measured.

(Example 6)

A liquid crystal alignment agent A1 is used instead of the liquid crystal alignment agent A1 instead of the liquid crystal alignment agent A1 instead of the MLC-6608, and the liquid crystal alignment agent A1 is used instead of the liquid crystal alignment agent A1. The same operation was carried out to produce a light-irradiated liquid crystal cell, and the liquid crystal cell was annealed in a circulating oven at 150 ° C for 3 hours, and then the voltage holding ratio and residual DC were measured.

(Example 7)

A liquid crystal alignment agent A1 is used instead of the liquid crystal alignment agent A1 instead of the liquid crystal alignment agent A1 instead of the MLC-6608, and the liquid crystal alignment agent A1 is used instead of the liquid crystal alignment agent A1. The same operation was carried out to produce a light-irradiated liquid crystal cell, and the liquid crystal cell was annealed in a circulating oven at 150 ° C for 3 hours, and after light irradiation was again performed under the same conditions, the voltage holding ratio and residual DC were measured.

Table 2 shows the results of using MLC-6608, which is a liquid crystal of the past which does not contain an alkenyl-based liquid crystal, as Examples A and B, Comparative Example A, and Reference Example A. In Comparative Example A and Reference Example A, which did not use a polymer having a structural unit derived from PMDA, the residual DC was reduced in the past. In the method of Reference A, which uses a highly polar diamine, the accumulation of residual DC is suppressed.

On the other hand, even in Example A and Example B using a polymer having a structural unit derived from PMDA, although there was a difference in the degree of introduction of the structural unit derived from PMDA, the residue was compared with Comparative Example A. The DC is reduced and can be found to be more reduced by light illumination.

Therefore, in the MLC-6608 which is a liquid crystal composition which does not contain an alkenyl-based liquid crystal, the cumulative amount of residual DC which is reduced by the conventional method can be achieved, and even if it contains a polymer having a polymer derived from the structural unit of PMDA, With the alignment film, the cumulative amount of residual DC can still be reduced by light irradiation.

Table 3 shows the results of using MLC-3022 which is a liquid crystal composition containing an alkenyl liquid crystal. Compared with Table 2, it can be seen that the overall voltage retention rate is lowered. Further, in Comparative Example 1 and Comparative Example 2, even in Comparative Example 2 in which MLC-6608 was used and the liquid crystal alignment agent A6 having an effect on residual DC was used, the cumulative amount of residual DC was large regardless of the presence or absence of light irradiation. On the other hand, Example 1, Example 2, Example 3, Example 4, Example 8, Example 9, and implementation using a polymer having a structural unit derived from PMDA, CA-1 or CA-2 In Example 10, Example 11, Example 12, Example 13, and Example 14, the residual DC was not irradiated by light, and the cumulative amount thereof was as large as that of Comparative Example 2, but was greatly reduced by light irradiation.

Table 4 shows the results of using MLC-3023 which is a liquid crystal composition containing an alkenyl liquid crystal and RM. As in Table 3, compared with Table 2, The voltage holding ratio was low, and in Comparative Examples 3 and 4, the amount of residual DC was large regardless of the presence or absence of PSA treatment. However, in Example 5 and Examples 15 to 19 in which a polymer having a structural unit derived from PMDA, CA-1 or CA-2 was used, the residual DC was greatly reduced by performing PSA treatment.

Therefore, in the case of using a liquid crystal composition containing an alkenyl-based liquid crystal, there is no effect in the conventional method of reducing residual DC by using an aggregation comprising a structural unit derived from PMDA, CA-1 or CA-2. The liquid crystal alignment film of the object is treated with PSA to reduce residual DC.

As in the examples shown in Tables 3 and 4, the reason why the residual DC accumulation can be reduced by using a polymer having a structural unit derived from PMDA and performing light irradiation is shown (Table 5).

In Example 5, after the liquid crystal alignment agent A2 containing the polymer having the structural unit derived from PMDA was used and light irradiation was performed, the residual DC was reduced as compared with the non-irradiation. Further, after annealing for 3 hours at 150 ° C after light irradiation, accumulation of residual DC was observed to the same extent as the result of non-irradiation (Example 6).

Since the voltage holding ratio hardly changes before and after annealing, it is considered that the deterioration of the liquid crystal is caused by the elimination of the interaction between the liquid crystal and the liquid crystal alignment film due to light irradiation. Further, after light irradiation was again performed in this state (Example 7), the cumulative amount of residual DC was again decreased. This also shows that an interaction occurs between the liquid crystal and the liquid crystal alignment film due to light irradiation, and thereby, the cumulative amount of residual DC can be reduced.

As described above, as shown in the examples, even in the case of using a low-reliability liquid crystal composition containing an alkenyl-based liquid crystal, the use includes a source. The liquid crystal alignment film of the polymer of the structural unit of the above formula (1) and formula (1') can reduce the accumulation of residual DC after light irradiation or after PSA treatment.

[Industrial Applicability]

The liquid crystal display element obtained by the present invention can be used as a liquid crystal display element of a vertical alignment type such as a PSA type liquid crystal display or an SC-PVA type liquid crystal display.

The entire disclosure of Japanese Patent Application No. 2015-22122, filed on Jan.

Claims (10)

A liquid crystal alignment agent comprising the following component (A), component (B), and an organic solvent; wherein the liquid crystal display device is formed by light-irradiating a liquid crystal cell, and the liquid crystal cell is a substrate having a conductive film formed on a surface of the substrate and coated with a liquid crystal alignment agent and heated to form a coating film, and the liquid crystal layer is interposed to allow the coating film to be relatively opposed to each other; (A) component: At least one polymer of a polyimine precursor having a side chain which vertically aligns the liquid crystal and a polyimine of the quinone imine of the polyimide precursor; (B) component: a polyfluorene imine precursor containing a reaction product of a tetracarboxylic dianhydride component and a diamine component of a tetracarboxylic dianhydride of the following formulas (1) and (1'), and the polyimine a polymer of at least one group of the polyimide of the imide imine of the precursor; however, the component (B) may be the same polymer as the component (A) when having a side chain which vertically aligns the liquid crystal; Each of j and k is independently 0 or 1, and x and y are each independently a single bond, a carbonyl group, an ester, a phenylene group, a sulfonyl group or a decylamino group. The liquid crystal alignment agent of claim 1, wherein the liquid crystal layer in the liquid crystal display element is a liquid crystal layer containing a liquid crystal compound having an alkenyl liquid crystal. The liquid crystal alignment agent of claim 1 or 2, wherein the ratio of the component (A) to the component (B) is (A) component at a mass ratio: (B) component = X: (10-X) (X = 1) ~9). The liquid crystal alignment agent according to any one of claims 1 to 3, wherein a side chain in which the liquid crystal is vertically aligned in the component (A) is represented by the following formula (a); l, m and n each independently represent an integer of 0 or 1, and R ¹ represents an alkylene group having 2 to 6 carbon atoms, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or carbon. The alkylene-ether group having 1 to 3, R ² , R ³ and R ⁴ each independently represent a phenyl group, a fluorine-containing phenyl group or a cycloalkyl group, and R ⁵ represents a hydrogen atom and has a carbon number of 2 to 24 An alkyl group, a fluorine-containing alkyl group having 2 to 24 carbon atoms, a monovalent aromatic ring, a monovalent aliphatic ring, a monovalent heterocyclic ring, or a cyclic substituent having a monovalent value. A liquid crystal alignment film obtained by the liquid crystal alignment agent according to any one of claims 1 to 4 having a film thickness of 5 to 300 nm. A liquid crystal display element having the liquid crystal as claimed in claim 5 Orientation film. A method for producing a liquid crystal display device, comprising: coating a liquid crystal alignment agent containing the component (A), the component (B) and an organic solvent described below on a conductive film having a pair of conductive films on a substrate a second step of forming a coating film by heating the coating film, and forming a liquid crystal cell by arranging one of the coating films to form a liquid crystal layer on the substrate, and arranging the coating film in a direction opposite to each other; The third step of performing light irradiation; (A) component: a polyimine which is selected from the group consisting of a polyimide precursor having a side chain which vertically aligns the liquid crystal, and a ruthenium imide of the polyimide precursor a group of at least one polymer; (B) component: selected from the group consisting of a tetracarboxylic dianhydride component and a diamine containing at least one tetracarboxylic dianhydride selected from the group consisting of the following formulas (1) and (1') At least one polymer of the polyimine precursor of the reaction product and the polyimine of the ruthenium imide of the polyimide precursor, but the component (B) has a liquid crystal vertical When the side chain is aligned, it may be the same polymer as the component (A); In the formula, j and k are each independently 0 or 1, and x and y are each independently a single bond, a carbonyl group, an ester group, a phenylene group, a sulfonyl group or a decylamino group. The method for producing a liquid crystal display element according to claim 7, wherein the liquid crystal layer is a liquid crystal layer containing a liquid crystalline compound having an alkenyl liquid crystal. A method of producing a liquid crystal display element according to claim 7 or 8, wherein the ultraviolet ray irradiation amount is 1 to 50 J/cm ² . The method of manufacturing a liquid crystal display element according to any one of claims 7 to 9, wherein the liquid crystal display element is a vertical alignment type display element.