CN107090300B

CN107090300B - Liquid crystal aligning agent for forming liquid crystal alignment film, and liquid crystal display element using same

Info

Publication number: CN107090300B
Application number: CN201710082955.XA
Authority: CN
Inventors: 大木洋一郎
Original assignee: JNC Corp; JNC Petrochemical Corp
Current assignee: Changsha Dao'anjie New Materials Co ltd
Priority date: 2016-02-18
Filing date: 2017-02-16
Publication date: 2022-01-11
Anticipated expiration: 2037-02-16
Also published as: CN107090300A; KR20170097552A; TW201741395A; JP2017146597A

Abstract

The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film and a liquid crystal display element using the same, wherein the liquid crystal aligning agent contains at least one of a polymer and a compound represented by the following formula (1), and the polymer is at least one selected from polyamic acid obtained by reacting tetracarboxylic dianhydride with a diamine compound and a derivative thereof. By using the liquid crystal aligning agent of the present invention, a liquid crystal alignment film having high film hardness, being difficult to be thinned, and having good liquid crystal alignment properties can be formed.

Description

Liquid crystal aligning agent for forming liquid crystal alignment film, and liquid crystal display element using same

Technical Field

The present invention relates to a liquid crystal aligning agent containing polyamic acid or a derivative thereof and a specific compound, a liquid crystal alignment film formed using the liquid crystal aligning agent, and a liquid crystal display element including the liquid crystal alignment film.

Background

Liquid crystal display elements that are currently being commercialized and generally distributed, such as monitors for personal computers (personal computers), liquid crystal televisions (tvs), View finders for video cameras (video finders), and various display devices for projection displays, and optoelectronic (optoelectronic) related elements such as optical print heads, optical fourier transform elements, and light valves, are mainly display elements that use nematic liquid crystals. As display modes of a Nematic liquid crystal display device, a Twisted Nematic (TN) mode and a Super Twisted Nematic (STN) mode are widely known. In recent years, In order to improve one of the problems of these modes, that is, a narrow viewing angle, a TN-mode liquid crystal display element using an optical compensation film, a Multi-domain Vertical Alignment (MVA) mode using a technique of using Vertical Alignment and a protrusion structure In combination, an In-Plane Switching (IPS) mode, a Fringe Field Switching (FFS) mode, and the like have been proposed and put into practical use.

The development of the technology of the liquid crystal display element has been achieved not only by the improvement of the driving method and the element structure but also by the improvement of the constituent members used in the element. Among the constituent members used in liquid crystal display elements, in particular, liquid crystal alignment films are one of important materials with respect to display quality, and it is important to improve the performance of alignment films in accordance with the improvement in quality of liquid crystal display elements.

The liquid crystal alignment film is formed of a liquid crystal aligning agent. The liquid crystal aligning agent mainly used at present is a solution (varnish) obtained by dissolving polyamic acid, polyamic acid ester, polyimide, or the like in an organic solvent. After the solution is applied onto a substrate, a film is formed by a method such as heating, thereby forming a polyimide-based liquid crystal alignment film. After the film formation, alignment treatment suitable for the display mode is performed as necessary.

A rubbing method capable of industrially and easily performing a large-area high-speed treatment is widely used as an alignment treatment method. The rubbing method is a method in which a cloth implanted with a fiber such as nylon, rayon, or polyester is rubbed on the surface of a liquid crystal alignment film in one direction to obtain uniform alignment of liquid crystal molecules. However, problems such as generation of dust and static electricity by the rubbing method have been pointed out, and an alignment treatment method replacing the rubbing method has been actively developed in recent years.

As an alignment treatment method that replaces the rubbing method, a photo-alignment treatment method in which alignment treatment is performed by irradiating light has been attracting attention. In the photo-alignment treatment method, a large number of alignment mechanisms such as a photo-decomposition method, a photo-isomerization method, a photo-dimerization method, and a photo-crosslinking method have been proposed (for example, see non-patent document 1, and patent document 2). The photo-alignment method has a higher uniformity of alignment than the rubbing method, and is a non-contact alignment treatment method, and thus has advantages such as not damaging a film and reducing causes of display defects of a liquid crystal display element such as dust or static electricity.

A photoalignment film having a photoreactive group that causes photoisomerization, photodimerization, or the like in a polyamic acid structure has been studied (for example, see patent documents 1 to 6). Among them, by applying the photoisomerization techniques described in patent documents 4 to 6, a liquid crystal alignment film having a large anchoring energy, good alignment properties, and good electrical characteristics such as voltage holding ratio can be obtained. However, when such a liquid crystal alignment film is applied to an actual liquid crystal display device, the alignment film is thinned, and the display quality of the liquid crystal display device is deteriorated due to the generated foreign matter.

In order to improve such defects, a method of improving the film hardness of an alignment film by adding a crosslinking agent to a liquid crystal alignment agent is known (for example, see patent documents 7 to 9). However, it is known that: when such a crosslinking agent is added, the film hardness is improved, but the alignment property of the liquid crystal is greatly lowered, and in the case of an FFS mode liquid crystal display element, after driving for a long time, an afterimage is generated. In addition, it is known that: there are also crosslinking agents that do not reduce the alignment of liquid crystals, but such crosslinking agents are insufficient in film hardness, and when used as a panel, the liquid crystal alignment film is thinned, resulting in display defects.

[ Prior art documents ]

[ patent document ]

[ patent document 1] Japanese patent laid-open No. Hei 9-297313

[ patent document 2] Japanese patent laid-open No. Hei 10-251646

[ patent document 3] Japanese patent laid-open No. 2005-275364

[ patent document 4] Japanese patent laid-open No. 2010-049230

[ patent document 5] Japanese patent laid-open No. 2010-197999

[ patent document 6] International publication No. 2013-157463

[ patent document 7] Japanese patent laid-open No. Hei 9-146100

[ patent document 8] Japanese patent laid-open No. Hei 10-333153

[ patent document 9] Japanese patent laid-open No. 2007 & 139949

[ non-patent document ]

[ non-patent document 1] liquid Crystal, Vol.3, No. 4, p.262, 1999

Disclosure of Invention

[ problems to be solved by the invention ]

As described above, by adding a compound having two or more crosslinkable groups such as glycidyl groups to the liquid crystal aligning agent, the film hardness of the alignment film can be improved. However, since the reaction proceeds directly with the carboxylic acid of the polyamic acid, if two or more crosslinking sites are present, a rigid structure is formed, and flexibility is impaired, which causes a problem that liquid crystal alignment properties are greatly reduced. Particularly, in the case of using the element of the lateral electric field system, the deterioration of the afterimage characteristics due to the alignment failure is caused, and the solution is accelerated. The invention provides a liquid crystal aligning agent capable of forming a liquid crystal alignment film with high film hardness, difficult thinning and good liquid crystal alignment performance, and a liquid crystal display element comprising the liquid crystal alignment film formed by the liquid crystal aligning agent.

[ means for solving the problems ]

The inventors of the present invention conducted extensive studies and found that: the use of the liquid crystal aligning agent containing the compound represented by formula (1) of the present invention makes it possible to obtain a liquid crystal alignment film having high film hardness, being difficult to be thinned, and having good liquid crystal alignment properties, and the present invention has been completed.

The present invention includes the following configurations.

[1] A liquid crystal aligning agent comprising at least one polymer selected from the group consisting of polyamic acids obtained by reacting tetracarboxylic dianhydrides with diamine compounds and derivatives thereof, and a compound represented by the following formula (1),

in the formula (1), R₁A monovalent organic group having any one of the following structures linked to N at one site directly or via a linking group;

and, R₂And R₃Each independently a monovalent organic group having any one of the following structures linked directly or via a linking group to N;

[2] the liquid crystal aligning agent according to [1], wherein the compound of formula (1) is at least one compound represented by formula (1-1) to formula (1-4);

in the formula (1-3), R is-CH₃or-CH₂CH₃。

[3] The liquid crystal aligning agent according to [1] or [2], wherein

The tetracarboxylic dianhydride contains at least one selected from the group of compounds represented by the following formulas (AN-I) to (AN-VII);

the diamine includes at least one selected from the group consisting of diamines having no side chain represented by the following formulae (DI-1) to (DI-16), dihydrazides having no side chain represented by the following formulae (DIH-1) to (DIH-3), and diamines having side chain represented by the following formulae (DI-31) to (DI-35);

in the formulae (AN-I), (AN-IV) and (AN-V), X is independently a single bond or-CH₂-; in the formula (AN-II), G is a single bond, alkylene group having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO₂-、-C(CH₃)₂-, or-C (CF)₃)₂-；

In the formulas (AN-II) to (AN-IV), Y is one of the trivalent groups selected from the following independently, a bonding bond is connected with any carbon, and at least one hydrogen of the groups can be substituted by methyl, ethyl or phenyl;

in the formulae (AN-III) to (AN-V), the ring A¹⁰A C3-10 monocyclic hydrocarbon group or a C6-30 condensed polycyclic hydrocarbon group, wherein at least one hydrogen of the group is substituted by a methyl group, an ethyl group or a phenyl group, and a bond to the ring is bonded to an arbitrary carbon constituting the ring, and both bonds may be bonded to the same carbon;

in the formula (AN-VI), X¹⁰An alkylene group having 2 to 6 carbon atoms, Me represents a methyl group, and Ph represents a phenyl group;

in the formula (AN-VII), G¹⁰Independently is-O-, -COO-or-OCO-, and r independently is 0 or 1;

in the formula (DI-1), G²⁰is-CH₂-, at least one-CH₂-may be substituted by-NH-, -O-, m is an integer from 1 to 12, at least one hydrogen of the alkylene group may be substituted by-OH;

in the formulae (DI-3) and (DI-5) to (DI-7), G²¹Independently a single bond, -NH-, -NCH₃-、-O-、-S-、-S-S-、-SO₂-、-CO-、-COO-、-CONCH₃-、-CONH-、-C(CH₃)₂-、-C(CF₃)₂-、-(CH₂)_m-、-O-(CH₂)_m-O-、-N(-CH₃)-(CH₂)_k-N(-CH₃)-、-(O-C₂H₄)_m-O-、-O-CH₂-C(CF₃)₂-CH₂-O-、-O-CO-(CH₂)_m-CO-O-、-CO-O-(CH₂)_m-O-CO-、-(CH₂)_m-NH-(CH₂)_m-、-CO-(CH₂)_k-NH-(CH₂)_k-、-(NH-(CH₂)_m)_k-NH-、-CO-C₃H₆-(NH-C₃H₆)_n-CO-, or-S- (CH)₂)_m-S-, m is independently an integer of 1 to 12, k is an integer of 1 to 5, n is 1 or 2;

in the formula (DI-4), s is independently an integer of 0 to 2;

in formulae (DI-6) and (DI-7), G²²Independently a single bond, -O-, -S-, -CO-, -C (CH)₃)₂-、-C(CF₃)₂-, -NH-, or C1-10 alkylene;

at least one hydrogen of the cyclohexane ring and the benzene ring in the formulae (DI-2) to (DI-7) is selected from the group consisting of-F, -Cl, C1-3 alkyl and-OCH₃、-OH、-CF₃、-CO₂H、-CONH₂、-NHC₆H₅Phenyl, or benzyl, and, in formula (DI-4), at least one hydrogen of the benzene ring may be substituted by one selected from the group of groups represented by the following formulae (DI-4-a) to (DI-4-e); a group whose bonding position is not fixed to a carbon atom constituting the ring in the formula represents that the bonding position on the ring is arbitrary;

-NH₂the bonding position on the cyclohexane ring or benzene ring being other than G²¹Or G²²Any position other than the bonding position of (a);

in the formulae (DI-4-a) and (DI-4-b), R²⁰Independently is hydrogen or-CH₃；

In the formula (DI-11), r is 0 or 1;

in the formulae (DI-8) to (DI-11), the bond to the ring is-NH₂The bonding position of (a) is an arbitrary position;

in the formula (DI-12), R²¹And R²²Independently an alkyl group having 1 to 3 carbon atoms or a phenyl group, G²³Independently an alkylene group having 1 to 6 carbon atoms, a phenylene group or an alkyl-substituted phenylene group, and w is an integer of 1 to 10;

in the formula (DI-13), R²³Independently an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or-Cl, p independently is an integer of 0 to 3, and q is an integer of 0 to 4;

in the formula (DI-14), the ring B is a monocyclic heteroaromatic ring, R²⁴Hydrogen, -F, -Cl, alkyl with 1-6 carbon atoms, alkoxy, vinyl and alkynyl, and q is an integer of 0-4 independently;

in the formula (DI-15), ring C is a monocyclic ring containing a hetero atom;

in the formula (DI-16), G²⁴Is a single bond, alkylene group having 2 to 6 carbon atoms or 1, 4-phenylene group, r is 0 or 1;

a group whose bonding position is not fixed to a carbon atom constituting the ring in the formula represents that the bonding position on the ring is arbitrary;

in the formulae (DI-13) to (DI-16), the bond to the ring is-NH₂The bonding position of (a) is an arbitrary position;

in the formula (DIH-1), G²⁵A single bond, alkylene group having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO₂-、-C(CH₃)₂-, or-C (CF)₃)₂-；

In the formula (DIH-2), ring D is a cyclohexane ring, a benzene ring or a naphthalene ring, and at least one hydrogen of these rings may be substituted with a methyl group, an ethyl group or a phenyl group;

in the formula (DIH-3), the rings E are each independently a cyclohexane ring or a benzene ring, at least one hydrogen of the rings may be substituted by a methyl group, an ethyl group or a phenyl group, and Y is a single bond, an alkylene group having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO₂-、-C(CH₃)₂-, or-C (CF)₃)₂-；

In the formulae (DIH-2) and (DIH-3), -CONHNH bonded to the ring₂The bonding position of (a) is an arbitrary position;

in the formula (DI-31), G²⁶Is a single bond, -O-, -COO-, -OCO-, -CO-, -CONH-, -CH₂O-、-OCH₂-、-CF₂O-、-OCF₂-, or- (CH)₂)_m'-, m' is an integer of 1 to 12;

R²⁵is an alkyl group having 3 to 30 carbon atoms, a phenyl group, a group having a steroid skeleton, or a group represented by the following formula (DI-31-a), wherein at least one hydrogen in the alkyl group is substituted by-F, and at least one-CH₂-may be substituted by-O-, -CH ═ CH-or-C ≡ C-, the hydrogen of the phenyl group may be substituted by-F, -CH, -C₃、-OCH₃、-OCH₂F、-OCHF₂、-OCF₃An alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms, bonded to a benzene ring₂The bonding position of (b) represents an arbitrary position in the ring,

in the formula (DI-31-a), G²⁷、G²⁸And G²⁹Are a bonding group, they are independently a single bond, or an alkylene group having 1 to 12 carbon atoms, one or more-CH of the alkylene group₂-may be substituted by-O-, -COO-, -OCO-, -CONH-, -CH ═ CH-Ring B²¹Ring B²²Ring B²³And ring B²⁴Independently 1, 4-phenylene, 1, 4-cyclohexylene, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl, pyridine-2, 5-diyl, piperidine-1, 4-diyl, naphthalene-1, 5-diyl, naphthalene-2, 7-diyl or anthracene-9, 10-diyl, ring B²¹Ring B²²Ring B²³And ring B²⁴Wherein at least one hydrogen may be replaced by-F or-CH₃And (b) a substituent, s, t and u are independently an integer of 0 to 2, the total of which is 0 to 5, and when s, t or u is 2, the two bonding groups in each bracket may be the same or different, and the two rings may be the same or different, R²⁶Hydrogen, -F, -OH, alkyl group with 1-30 carbon atoms, fluorine substituted alkyl group with 1-30 carbon atoms, alkoxy group with 1-30 carbon atoms, -CN, -OCH₂F、-OCHF₂or-OCF₃At least one-CH of the C1-30 alkyl group₂May be substituted with a divalent group represented by the following formula (DI-31-b),

in the formula (DI-31-b), R²⁷And R²⁸Independently an alkyl group having 1 to 3 carbon atoms, and v is an integer of 1 to 6;

in formulae (DI-32) and (DI-33), G³⁰Independently a single bond, -CO-or-CH₂-，R²⁹Independently is hydrogen or-CH₃，R³⁰Hydrogen, alkyl group having 1 to 20 carbon atoms, or alkenyl group having 2 to 20 carbon atoms;

at least one hydrogen of the benzene ring in the formula (DI-33) may be substituted with an alkyl group having 1 to 20 carbon atoms or a phenyl group,

a group whose bonding position is not fixed to any carbon atom constituting the ring in the formula represents that the bonding position on the ring is arbitrary;

in the formulae (DI-32) and (DI-33), -NH bonded to the benzene ring₂Indicates that the bonding position on the ring is arbitrary;

in formulae (DI-34) and (DI-35), G³¹Independently represents-O-, -NH-or C1-6 alkylene, G³²Is a single bond or C1-3 alkylene, R³¹Is hydrogen or C1-20 alkyl, at least one-CH of the alkyl₂-may be substituted by-O-, -CH ═ CH-, or-C ≡ C-, R³²Is C6-22 alkyl, R³³Hydrogen or C1-22 alkyl, ring B²⁵Is 1, 4-phenylene or 1, 4-cyclohexylene, r is 0 or 1, and-NH bonded to the phenyl ring₂Indicates that the bonding position on the ring is arbitrary.

[4] The liquid crystal aligning agent according to [3], wherein

The tetracarboxylic dianhydride is at least one selected from the following formula (AN-1-1), formula (AN-1-2), formula (AN-1-13), formula (PA-1), formula (AN-3-2), formula (AN-4-5), formula (AN-4-17), formula (AN-4-21), formula (AN-4-29), formula (AN-4-30), formula (AN-5-1), formula (AN-7-2), formula (AN-10-1), formula (AN-11-3), formula (AN-16-1), formula (AN-16-3), and formula (AN-16-4);

the diamine is selected from the group consisting of formula (DI-1-3), formula (DI-2-1), formula (DI-4-2), formula (DI-4-10), formula (DI-4-15), formula (DI-5-1), formula (DI-5-5), formula (DI-5-9), formula (DI-5-12), formula (DI-5-13), formula (DI-5-17), formula (DI-5-28), formula (DI-5-30), formula (DI-6-7), formula (DI-7-3), formula (DI-11-2), formula (DI-13-1), formula (DI-16-1), formula (DI-31-56), And at least one of the group consisting of formula (DIH-2-1);

in the formulas (AN-1-2) and (AN-4-17), m is AN integer of 1-12 independently;

in the formulae (DI-5-1), (DI-5-12), (DI-5-13) and (DI-7-3), m is independently an integer of 1 to 12;

in the formula (DI-5-30), k is an integer of 1 to 5; and also

In the formula (DI-7-3), n is 1 or 2 independently.

[5] The liquid crystal aligning agent according to any one of [1] to [4], wherein the polyamic acid and the derivative thereof are a polymer (a) obtained by reacting at least one of tetracarboxylic dianhydride and diamine with a compound having a photoreactive structure.

[6] The liquid crystal aligning agent according to [5], wherein the photoreactive structure is at least one selected from the group consisting of structures represented by the following formulae (P-1) to (P-7);

in the formula (P-1), R⁶¹Independently hydrogen atom, alkyl group having 1 to 5 carbon atoms, or phenyl group.

[7] The liquid crystal aligning agent according to [6], wherein the compound having the photoreactive structure is at least one tetracarboxylic dianhydride or diamine compound selected from the group consisting of the following formula (II-1), formula (II-2), formula (III-1), formula (III-2), formula (IV-1), formula (IV-2), formula (V-1) to formula (V-3), and formula (VI-1), formula (VI-2);

in the respective formulae, the group whose bonding position is not fixed to any carbon atom constituting the ring means that the bonding position on the ring is arbitrary; in the formula (V-2), R⁶Independently is-CH₃、-OCH₃、-CF₃or-COOCH₃A is an integer of 0 to 2; in the formula (V-3), the ring A and the ring B are each independently at least one member selected from the group consisting of monocyclic hydrocarbons, condensed polycyclic hydrocarbons and heterocycles,R¹¹is a C1-20 linear alkylene group, -COO-, -OCO-, -NHCO-or-N (CH)₃)CO-，R¹²Is a C1-20 linear alkylene group, -COO-, -OCO-, -NHCO-or-N (CH)₃)CO-，R¹¹And R¹²Of linear alkylene-CH₂One or two of (A) and (B) may be substituted by-O-, R⁷～R¹⁰Are independently-F, -CH₃、-OCH₃、-CF₃or-OH, and b to e are each independently an integer of 0 to 4.

[8] The liquid crystal aligning agent according to [7], wherein the diamine compound having the photoreactive structure is represented by the following formula (PDI-7);

in the formula (PDI-7), R⁵¹Are each independently-CH₃、-OCH₃、-CF₃or-COOCH₃And s is an integer of 0 to 2.

[9] The liquid crystal aligning agent according to any one of [5] to [8], which comprises a polymer (a) and further comprises a polymer (b), wherein the polymer (b) is at least one selected from polyamic acids and derivatives thereof obtained by reacting tetracarboxylic dianhydrides having no photoreactive structure and diamines having no photoreactive structure.

[10] The liquid crystal aligning agent according to [9], wherein

The tetracarboxylic dianhydride used in the synthesis of the polymer (b) is selected from the following formulas (AN-1-1), (AN-1-2), (AN-1-13), (PA-1), (AN-3-2), (AN-4-5), (AN-4-17), (AN-4-21), at least one of formula (AN-4-29), formula (AN-4-30), formula (AN-5-1), formula (AN-7-2), formula (AN-10-1), formula (AN-11-3), formula (AN-16-1), formula (AN-16-3), and formula (AN-16-4);

in the formulas (AN-1-2) and (AN-4-17), m is AN integer of 1-12 independently;

in the formula (DI-5-30), k is an integer of 1 to 5; and also

In the formula (DI-7-3), n is 1 or 2 independently.

[11] The liquid crystal aligning agent according to any one of [1] to [10], further comprising at least one selected from the group consisting of an oxazine compound, an oxazoline compound, an epoxy compound other than the compound represented by the formula (1), and a silane coupling agent.

[12] A liquid crystal alignment film formed from the liquid crystal aligning agent according to any one of [1] to [11 ].

[13] A liquid crystal alignment film for a transverse electric field-driven liquid crystal display element, which is formed from the liquid crystal aligning agent according to any one of [1] to [11 ].

[14] A liquid crystal display element comprising the liquid crystal alignment film according to [12] or [13 ].

[ Effect of the invention ]

When the liquid crystal aligning agent containing the compound represented by the formula (1) of the present invention is used, a liquid crystal alignment film having high film hardness and good liquid crystal alignment properties can be obtained. Further, by using the liquid crystal alignment film, a liquid crystal display element which is free from a bright point defect due to a foreign substance and has excellent display characteristics can be obtained.

Detailed Description

< Compound represented by formula (1) >

The invention is a liquid crystal aligning agent, which contains at least one of the following polymer and the compound represented by the following formula (1), wherein the polymer is at least one selected from polyamic acid obtained by reacting tetracarboxylic dianhydride and diamine and the derivative thereof.

In formula (1), R1 is a monovalent organic group having any one of the following structures linked directly or via a linking group to N at x;

the compound represented by formula (1) can be specifically represented by the following formulae (1-1) to (1-4).

The amount of the compound represented by formula (1) added is preferably 0.1 wt% (wt%) or more of the total weight of the polyamic acid or its derivative in order to obtain an effect of preventing thinning at the time of rubbing due to a decrease in film hardness when used in a liquid crystal aligning agent for rubbing. On the other hand, the amount of addition is preferably 10 wt% or less in order to prevent poor alignment associated with a decrease in alignment properties of the liquid crystal alignment film. The amount of the liquid crystal aligning agent to be added for rubbing is more preferably 0.3 to 3 wt%. In addition, when used in a liquid crystal aligning agent for photo-alignment, it is preferable that the polyamic acid or a derivative thereof is 0.1 wt% or more of the total weight in order to obtain an effect of preventing thinning of a film due to a decrease in film hardness. On the other hand, the amount of addition is preferably 30 wt% or less in order to prevent poor alignment associated with a decrease in alignment properties of the liquid crystal alignment film. The amount of the liquid crystal aligning agent to be added is more preferably 5 to 20 wt%.

In order to obtain a liquid crystal alignment film having high liquid crystal alignment properties and high film hardness, among the compounds represented by formula (1), compounds represented by formulae (1-1) to (1-4) are preferably used, and more preferably, a compound represented by formula (1-1) is used.

< liquid Crystal Aligning agent >

The liquid crystal orientation agent is a reaction product of at least one selected from tetracarboxylic dianhydride and derivatives thereof and diamine, and is characterized in that: contains at least one of the following polymers and the compound represented by the formula (1), wherein the polymer is at least one selected from the group consisting of polyamic acid and derivatives thereof. The derivative of polyamic acid is a component which is dissolved in a solvent when a liquid crystal alignment agent described later containing a solvent is prepared, and is a component which can form a liquid crystal alignment film containing polyimide as a main component when the liquid crystal alignment agent is prepared into a liquid crystal alignment film. Examples of the derivative of such a polyamic acid include a soluble polyimide, a polyamic acid ester, and a polyamic acid amide, and more specifically include: 1) a polyimide obtained by subjecting all amino groups of a polyamic acid and a carboxyl group to a dehydration ring-closure reaction, 2) a partial polyimide obtained by partially subjecting the polyamic acid to a dehydration ring-closure reaction, 3) a polyamic acid ester obtained by converting the carboxyl group of a polyamic acid into an ester, 4) a polyamic acid-polyimide copolymer obtained by reacting a tetracarboxylic dianhydride compound in which a part of the acid dianhydride is substituted with an organic dicarboxylic acid, and 5) a polyamideimide obtained by subjecting a part or all of the polyamic acid-polyimide copolymer to a dehydration ring-closure reaction. The polyamic acid and the derivative thereof may be one kind of polymer, or two or more kinds of polymers. The polyamic acid and the derivative thereof may be a polymer having a structure of a reaction product of tetracarboxylic dianhydride and diamine, and may include the following reaction product: the other raw materials are used and obtained by other reactions than the reaction of tetracarboxylic dianhydride and diamine.

The polyamic acid ester can be synthesized by the following method: the polyamic acid may be synthesized by reacting the polyamic acid with a hydroxyl group-containing compound, a halide, an epoxy group-containing compound, or the like, or may be synthesized by reacting a tetracarboxylic acid diester derived from an acid dianhydride or a tetracarboxylic acid diester dichloride with a diamine. The tetracarboxylic acid diester derived from an acid dianhydride can be obtained, for example, by reacting an acid dianhydride with 2 equivalents of an alcohol and ring-opening, and the tetracarboxylic acid diester dichloride can be obtained by reacting a tetracarboxylic acid diester with 2 equivalents of a chlorinating agent (e.g., thionyl chloride, etc.). The polyamic acid ester may have only the amic acid ester structure or may be a partially esterified product in which the amic acid structure and the amic acid ester structure coexist.

The tetracarboxylic dianhydride used for producing the polyamic acid and the derivative thereof contained in the liquid crystal aligning agent of the present invention will be described. The tetracarboxylic dianhydride used in the present invention can be selected from known tetracarboxylic dianhydrides without limitation. Such a tetracarboxylic dianhydride may be a tetracarboxylic dianhydride belonging to any one of the group of an aromatic system (including a heteroaromatic ring system) in which a dicarboxylic anhydride is directly bonded to an aromatic ring, and an aliphatic system (including a heteroaromatic ring system) in which a dicarboxylic anhydride is not directly bonded to an aromatic ring. The tetracarboxylic dianhydride may be reacted with one kind of compound and a diamine, or may be reacted with a diamine by mixing two or more kinds of compounds. In the present specification, the term "tetracarboxylic dianhydride" means not only one kind of compound but also a mixture of two or more kinds of compounds.

The tetracarboxylic dianhydride can be roughly classified into a tetracarboxylic dianhydride having a photoreactive structure and a tetracarboxylic dianhydride not having a photoreactive structure.

As a suitable example of the tetracarboxylic dianhydride not having the photoreactive structure, tetracarboxylic dianhydrides represented by formulae (AN-I) to (AN-VII) can be cited from the viewpoint of easiness of obtaining raw materials, easiness in polymerization of a polymer, and electrical characteristics of a film.

In the formulae (AN-I), (AN-IV) and (AN-V), X is independently a single bond or-CH₂-. In the formula (AN-II), G is a single bond, alkylene group having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO₂-、-C(CH₃)₂-, or-C (CF)₃)₂-. In the formulae (AN-II) to (AN-IV), Y is independently one selected from the group of trivalent groups, a bond is bonded to AN arbitrary carbon, and at least one hydrogen of the groups may be substituted by a methyl group, AN ethyl group or a phenyl group.

In the formulae (AN-III) to (AN-V), the ring A¹⁰The group is a C3-10 monocyclic hydrocarbon group or a C6-30 condensed polycyclic hydrocarbon group, at least one hydrogen of the group may be substituted by a methyl group, an ethyl group or a phenyl group, a bond to the ring may be bonded to any carbon constituting the ring, and both bonds may be bonded to the same carbon. In the formula (AN-VI), X¹⁰An alkylene group having 2 to 6 carbon atoms, Me represents a methyl group, and Ph represents a phenyl group. In the formula (AN-VII), G¹⁰Independently is-O-, -COO-or-OCO-, and r independently is 0 or 1.

More specifically, tetracarboxylic dianhydrides represented by the following formula (AN-1) and formulae (AN-3) to (AN-16-15) are exemplified.

[ tetracarboxylic dianhydride represented by the formula (AN-1) ]

In the formula (AN-1), G¹¹Is a single bond, an alkylene group having 1 to 12 carbon atoms, a1, 4-phenylene group, or a1, 4-cyclohexylene group. X¹¹Independently is a single bond or-CH₂-。G¹²Independently any of the following trivalent groups.

When G is¹²When > CH-, hydrogen of > CH-may be replaced by-CH₃And (4) substitution. When G is¹²When is > N-, G¹¹Not being a single bond and-CH₂-，X¹¹Not a single bond. And, R¹¹Is hydrogen or-CH₃。

Examples of the tetracarboxylic dianhydride represented by the formula (AN-1) include compounds represented by the following formulae.

In the formulae (AN-1-2) and (AN-1-14), m is AN integer of 1 to 12.

[ tetracarboxylic dianhydride represented by the formula (AN-3) ]

In the formula (AN-3), ring A¹¹Is a cyclohexane ring or a benzene ring.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-3) include compounds represented by the following formulae.

[ tetracarboxylic dianhydride represented by the formula (AN-4) ]

In the formula (AN-4), G¹³Is a single bond, - (CH)₂)_m-、-O-、-S-、-C(CH₃)₂-、-SO₂-、-CO-、-C(CF₃)₂-, or represented by the formulaA divalent group represented by (G13-1), and m is an integer of 1 to 12. Ring A¹¹Each independently is a cyclohexane ring or a benzene ring. G¹³May be bonded to ring A¹¹At any arbitrary position of the substrate.

In the formula (G13-1), G^13aAnd G^13bEach independently represents a single bond, -O-, or a divalent group represented by-NHCO-. The phenylene group is preferably a1, 4-phenylene group or a1, 3-phenylene group.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-4) include compounds represented by the following formulae.

In the formula (AN-4-17), m is AN integer of 1-12.

[ tetracarboxylic dianhydride represented by the formula (AN-5) ]

In the formula (AN-5), R¹¹Is hydrogen, or-CH₃. R whose bonding position is not fixed to the carbon atom constituting the benzene ring¹¹Indicates that the bonding position in the benzene ring is arbitrary.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-5) include compounds represented by the following formulae.

[ tetracarboxylic dianhydride represented by the formula (AN-6) ]

In the formula (AN-6), X¹¹Independently is a single bond or-CH₂-。X¹²is-CH₂-、-CH₂CH₂-or-CH ═ CH-. n is 1 or 2. Examples of the tetracarboxylic dianhydride represented by the formula (AN-6) include compounds represented by the following formulae.

[ tetracarboxylic dianhydride represented by the formula (AN-7) ]

In the formula (AN-7), X¹¹Is a single bond or-CH₂-。

Examples of the tetracarboxylic dianhydride represented by the formula (AN-7) include compounds represented by the following formulae.

[ tetracarboxylic dianhydride represented by the formula (AN-8) ]

In the formula (AN-8), X¹¹Is a single bond or-CH₂-。R¹²Is hydrogen, -CH₃、-CH₂CH₃Or phenyl, ring A¹²Is a cyclohexane ring or a cyclohexene ring.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-8) include compounds represented by the following formulae.

[ tetracarboxylic dianhydride represented by the formula (AN-9) ]

In the formula (AN-9), r is 0 or 1 independently.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-9) include compounds represented by the following formulae.

[ tetracarboxylic dianhydrides represented by the formulae (AN-10-1) and (AN-10-2) ]

[ tetracarboxylic dianhydride represented by the formula (AN-11) ]

In the formula (AN-11), ring A11 is independently a cyclohexane ring or a benzene ring.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-11) include compounds represented by the following formulae.

[ tetracarboxylic dianhydride represented by the formula (AN-12) ]

In the formula (AN-12), ring A¹¹Each independently is a cyclohexane ring or a benzene ring.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-12) include compounds represented by the following formulae.

[ tetracarboxylic dianhydride represented by the formula (AN-13) ]

In the formula (AN-13), X¹³Is an alkylene group having 2 to 6 carbon atoms, and Ph represents a phenyl group.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-13) include compounds represented by the following formulae.

[ tetracarboxylic dianhydride represented by the formula (AN-14) ]

In the formula (AN-14), G14 is independently-O-, -COO-or-OCO-, and r is independently 0 or 1.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-14) include compounds represented by the following formulae.

[ tetracarboxylic dianhydride represented by the formula (AN-15) ]

In the formula (AN-15), w is AN integer of 1 to 10.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-15) include compounds represented by the following formulae.

Examples of the tetracarboxylic dianhydride other than the above include the following compounds.

Suitable materials for improving various properties of tetracarboxylic dianhydrides having no photoreactive structure are described.

When importance is attached to the improvement of the orientation of the liquid crystal, the compounds represented by the formulae (AN-1), (AN-3) and (AN-4) are preferable, and the compounds represented by the formulae (AN-1-2), (AN-1-13), (AN-3-2), (AN-4-5), (AN-4-17) and (AN-4-29) are more preferable. In formula (AN-1-2), m is preferably 4 or 8. In formula (AN-4-17), m is preferably 4 or 8, and more preferably m is 8.

Among the tetracarboxylic dianhydrides, those represented by the formulae (AN-1-1), (AN-1-2), (AN-3-1), (AN-4-17), (AN-4-30), (AN-5-1), (AN-7-2), (AN-10-1), (AN-16-3) and (AN-16-4) are preferable in order to increase the transmittance of a liquid crystal display device. In formula (AN-1-2), m is preferably 4 or 8. In formula (AN-4-17), m is preferably 4 or 8, and more preferably m is 8.

Among the tetracarboxylic dianhydrides, compounds represented by the formulae (AN-1-1), (AN-1-2), (AN-3-1), (AN-4-17), (AN-4-30), (AN-7-2), (AN-10-1), (AN-16-3), and (AN-16-4) are preferable in order to increase the Voltage Holding Ratio (VHR) of a liquid crystal display device, and m is preferably 4 or 8 in the formula (AN-1-2). In formula (AN-4-17), m is preferably 4 or 8, and more preferably m is 8.

As one of the methods for preventing burn marks, it is effective to increase the relaxation rate of residual charges (residual DC) in the alignment film by lowering the volume resistance value of the liquid crystal alignment film. Among the tetracarboxylic dianhydrides, those represented by the formulae (AN-1-13), (AN-3-2), (AN-4-21), (AN-4-29) and (AN-11-3) are preferable for the purpose of importance.

The diamine and dihydrazide used for producing the polyamic acid and the derivative thereof contained in the liquid crystal aligning agent of the present invention will be described. The diamine and dihydrazide used in the present invention may be selected from known diamines and dihydrazides without limitation. The diamine may be reacted with one compound or two or more compounds mixed and reacted with the tetracarboxylic dianhydride. In the present specification, the term "diamine" means not only one kind of compound but also a mixture of two or more kinds of compounds. In the present specification, the dihydrazide may be treated as "diamine".

The diamine can be roughly classified into a diamine having a photoreactive structure and a diamine having no photoreactive structure, similarly to the tetracarboxylic dianhydride. Diamines having no photoreactive structure may be classified into two types according to their structures. That is, a diamine having a side chain group branched from the main chain when the skeleton connecting two amino groups is regarded as the main chain, and a diamine having no side chain group. The side chain group is a group having an effect of increasing the pretilt angle. The side chain group having such an effect is required to be a group having 3 or more carbon atoms, and specific examples thereof include: an alkyl group having 3 or more carbon atoms, an alkoxy group having 3 or more carbon atoms, an alkoxyalkyl group having 3 or more carbon atoms, and a group having a steroid skeleton. The group having one or more rings and having, as a substituent, any of an alkyl group having 1 or more carbon atoms, an alkoxy group having 1 or more carbon atoms and an alkoxyalkyl group having 2 or more carbon atoms in the ring at the end thereof also has an effect as a side chain group. In the following description, a diamine having such a side chain group may be referred to as a side chain type diamine. Also, diamines not having such side chain groups may be referred to as non-side chain diamines.

By appropriately separating the non-side chain type diamine from the side chain type diamine, the pretilt angle can be adjusted to each desired one. The side chain type diamine is preferably used in combination to such an extent that the characteristics of the present invention are not impaired. The side chain type diamine and the non-side chain type diamine are preferably used in a manner selected for the purpose of improving the vertical alignment property, voltage holding ratio, burn mark property, and alignment property with respect to the liquid crystal.

Non-side chain type diamines are explained. The known diamines having no side chain include diamines of the following formulae (DI-1) to (DI-16).

In the formula (DI-1), G²⁰is-CH₂-, at least one-CH₂-may be substituted by-NH-, -O-, m is an integer of 1 to 12, and at least one hydrogen of the alkylene group may be substituted by-OH. In the formulae (DI-3) and (DI-5) to (DI-7), G²¹Independently a single bond, -NH-, -NCH₃-、-O-、-S-、-S-S-、-SO₂-、-CO-、-COO-、-CONCH₃-、-CONH-、-C(CH₃)₂-、-C(CF₃)₂-、-(CH₂)_m-、-O-(CH₂)_m-O-、-N(CH₃)-(CH₂)_k-N(CH₃)-、-(O-C₂H₄)_m-O-、-O-CH₂-C(CF₃)₂-CH₂-O-、-O-CO-(CH₂)_m-CO-O-、-CO-O-(CH₂)_m-O-CO-、-(CH₂)_m-NH-(CH₂)_m-、-CO-(CH₂)_k-NH-(CH₂)_k-、-(NH-(CH₂)_m)_k-NH-、-CO-C₃H₆-(NH-C₃H₆)_n-CO-, or-S- (CH)₂)_m-S-, m is independently an integer of 1 to 12, k is independently an integer of 1 to 5, and n is 1 or 2. In the formula (DI-4), s is independently an integer of 0 to 2. In formulae (DI-6) and (DI-7), G²²Independently a single bond, -O-, -S-, -CO-, -C (CH)₃)₂-、-C(CF₃)₂-, -NH-, or C1-10 alkylene. At least one hydrogen of the cyclohexane ring and the benzene ring in the formulae (DI-2) to (DI-7) is selected from the group consisting of-F, -Cl, C1-3 alkyl and-OCH₃、-OH、-CF₃、-CO₂H、-CONH₂、-NHC₆H₅And phenyl or benzyl, and in the formula (DI-4), at least one hydrogen of the cyclohexane ring and the benzene ring may be substituted by one selected from the group of the groups represented by the following formulae (DI-4-a) to (DI-4-e). The group whose bonding position is not fixed to a carbon atom constituting a ring means that the bonding position on the ring is arbitrary. and-NH₂The bonding position on the cyclohexane ring or benzene ring being other than G²¹Or G²²Any position other than the bonding position(s).

In the formulae (DI-4-a) and (DI-4-b), R²⁰Independently is hydrogen or-CH₃。

In the formula (DI-11), r is 0 or 1. In the formulae (DI-8) to (DI-11), the bond to the ring is-NH₂The bonding position of (A) is arbitrary.

Formula (DI-12)In, R²¹And R²²Independently an alkyl group having 1 to 3 carbon atoms or a phenyl group, G²³Independently an alkylene group having 1 to 6 carbon atoms, a phenylene group or a phenylene group substituted with an alkyl group, and w is an integer of 1 to 10. In the formula (DI-13), R²³Independently an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or-Cl, p independently is an integer of 0 to 3, and q is an integer of 0 to 4. In the formula (DI-14), the ring B is a monocyclic heteroaromatic ring, R²⁴Is hydrogen, -F, -Cl, alkyl with 1-6 carbon atoms, alkoxy, vinyl and alkynyl, and q is an integer of 0-4 independently. In the formula (DI-15), ring C is a monocyclic ring containing a hetero atom. In the formula (DI-16), G²⁴Is a single bond, alkylene group having 2 to 6 carbon atoms or 1, 4-phenylene group, and r is 0 or 1. The term "group whose bonding position is not fixed to a carbon atom constituting a ring" means that the bonding position on the ring is arbitrary. In the formulae (DI-13) to (DI-16), the bond to the ring is-NH₂The bonding position of (A) is arbitrary.

Specific examples of the diamines having no side chain of the above formulae (DI-1) to (DI-16) include the following formulae (DI-1-1) to (DI-16-1).

Examples of the diamine represented by the formula (DI-1) are shown below.

In the formulas (DI-1-7) and (DI-1-8), k is independently an integer of 1 to 3.

Examples of diamines represented by the formulae (DI-2) and (DI-3) are shown below.

Examples of the diamines represented by the formula (DI-4) are shown below.

Examples of the diamines represented by the formula (DI-5) are shown below.

In the formula (DI-5-1), m is an integer of 1 to 12.

In the formulae (DI-5-1), (DI-5-12) and (DI-5-13), m is an integer of 1 to 12.

In the formula (DI-5-16), v is an integer of 1 to 6.

In the formula (DI-5-30), k is an integer of 1 to 5.

In the formulas (DI-5-35) to (DI-5-37) and (DI-5-39), m is independently an integer of 1 to 12, k is independently an integer of 1 to 5 in the formulas (DI-5-38) and (DI-5-39), and n is an integer of 1 or 2 in the formula (DI-5-40).

Examples of the diamines represented by the formula (DI-6) are shown below.

Examples of the diamines represented by the formula (DI-7) are shown below.

In the formulas (DI-7-3) and (DI-7-4), m is an integer of 1 to 12, and n is independently 1 or 2.

In the formula (DI-7-12), m is an integer of 1 to 12.

Examples of the diamines represented by the formula (DI-8) are shown below.

Examples of the diamines represented by the formula (DI-9) are shown below.

Examples of diamines represented by the formula (DI-10) are shown below.

Examples of the diamine represented by the formula (DI-11) are shown below.

Examples of the diamines represented by the formula (DI-12) are shown below.

Examples of the diamine represented by the formula (DI-13) are shown below.

Examples of the diamines represented by the formula (DI-14) are shown below.

Examples of the diamines represented by the formula (DI-15) are shown below.

Examples of the diamines represented by the formula (DI-16) are shown below.

The dihydrazide is explained. The known dihydrazides having no side chain include the following formulae (DIH-1) to (DIH-3).

In the formula (DIH-1), G²⁵A single bond, alkylene group having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO₂-、-C(CH₃)₂-, or-C (CF)₃)₂-. In the formula (DIH-2), ring D is a cyclohexane ring, a benzene ring or a naphthalene ring, and at least one hydrogen of these rings may be substituted by a methyl group, an ethyl group or a phenyl group. In the formula (DIH-3), the rings E are each independently a cyclohexane ring or a benzene ring, and at least one hydrogen of these rings may be represented by methyl or ethylSubstituted by a group or a phenyl group, Y is a single bond, an alkylene group having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO₂-、-C(CH₃)₂-, or-C (CF)₃)₂-. In the formulae (DIH-2) and (DIH-3), -CONHNH bonded to the ring₂The bonding position of (A) is arbitrary.

Examples of the formulae (DIH-1) to (DIH-3) are shown below.

In the formula (DIH-1-2), m is an integer of 1-12.

Such non-side chain type diamines and dihydrazides have an effect of improving electrical characteristics such as lowering ion density of a liquid crystal display element. When a non-side-chain diamine and/or dihydrazide is used as the diamine for producing a liquid crystal aligning agent comprising the polyamic acid, polyamic acid ester, or polyimide used in the liquid crystal aligning agent of the present invention, the proportion thereof in the total amount of the diamine and the dihydrazide is preferably from 0 mol% (mole%) to 90 mol%, more preferably from 0 mol% to 50 mol%

The side chain type diamine is explained. Examples of the side chain group of the side chain type diamine include the following groups.

Examples of the side chain group include: alkyl, alkoxy, alkoxyalkyl, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkylaminocarbonyl, alkenyl, alkenyloxy, alkenylcarbonyl, alkenylcarbonyloxy, alkenyloxycarbonyl, alkenylaminocarbonyl, alkynyl, alkynyloxy, alkynylcarbonyl, alkynylcarbonyloxy, alkynyloxycarbonyl, alkynylaminocarbonyl, etc. The alkyl, alkenyl and alkynyl groups in these groups are each a group having 3 or more carbon atoms. However, in the alkoxyalkyl group, the number of carbon atoms in the entire group may be 3 or more. These groups may be linear or branched.

Next, provided that the terminal ring has an alkyl group having 1 or more carbon atoms, an alkoxy group having 1 or more carbon atoms, or an alkoxyalkyl group having 2 or more carbon atoms as a substituent, there may be mentioned: a cyclic structure group such as a phenyl group, a phenylalkyl group, a phenylalkoxy group, a phenoxy group, a phenylcarbonyl group, a phenylcarbonyloxy group, a phenoxycarbonyl group, a phenylaminocarbonyl group, a phenylcyclohexyloxy group, a cycloalkyl group having 3 or more carbon atoms, a cyclohexylalkyl group, a cyclohexyloxy group, a cyclohexyloxycarbonyl group, a cyclohexylphenyl group, a cyclohexylphenylalkyl group, a cyclohexylphenoxy group, a bis (cyclohexyl) oxy group, a bis (cyclohexyl) alkyl group, a bis (cyclohexyl) phenyl group, a bis (cyclohexyl) phenylalkyl group, a bis (cyclohexyl) oxycarbonyl group, a bis (cyclohexyl) phenoxycarbonyl group, and a cyclohexylbis (phenyl) oxycarbonyl group.

Further, there can be mentioned a ring assembly group which is a group having two or more benzene rings, a group having two or more cyclohexane rings, or a group having two or more rings including a benzene ring and a cyclohexane ring, wherein the bonding groups are independently a single bond, -O-, -COO-, -OCO-, -CONH-, or an alkylene group having 1 to 3 carbon atoms, and the terminal ring has an alkyl group having 1 or more carbon atoms, a fluorine-substituted alkyl group having 1 or more carbon atoms, an alkoxy group having 1 or more carbon atoms, or an alkoxyalkyl group having 2 or more carbon atoms as a substituent. Groups having a steroid skeleton are also effective as side chain groups.

The diamine having a side chain includes compounds represented by the following formulae (DI-31) to (DI-35).

In the formula (DI-31), G²⁶Is a single bond, -O-, -COO-, -OCO-, -CO-, -CONH-, -CH₂O-、-OCH₂-、-CF₂O-、-OCF₂-or- (CH)₂)_m'-, m' is an integer of 1 to 12. G²⁶Preferred examples of (B) are a single bond, -O-, -COO-, -OCO-, -CH₂O-, and C1-3 alkylene groups, particularly preferred examples being single bonds, -O-, -COO-, -OCO-, -CH₂O-、-CH₂-and-CH₂CH₂-。R²⁵Is C3-30 alkyl, phenyl, or a group having a steroid skeletonOr a group represented by the following formula (DI-31-a). In the alkyl group, at least one hydrogen may be substituted by-F, and at least one-CH₂-may be substituted by-O-, -CH ═ CH-, or-C ≡ C-. The hydrogen of the phenyl group can be replaced by-F, -CH₃、-OCH₃、-OCH₂F、-OCHF₂、-OCF₃An alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms. -NH bound to a benzene ring₂The bonding position (b) represents an arbitrary position in the ring, and the bonding position is preferably meta-or para-position. I.e. when the radical "R" is substituted²⁵-G²⁶When the bonding position of the group is 1-position, the two bonding positions are preferably 3-and 5-positions or 2-and 5-positions.

In the formula (DI-31-a), G²⁷、G²⁸And G²⁹Are a bonding group, they are independently a single bond, or an alkylene group having 1 to 12 carbon atoms, one or more-CH of the alkylene group₂-may be substituted by-O-, -COO-, -OCO-, -CONH-, -CH ═ CH-. Ring B²¹Ring B²²Ring B²³And ring B²⁴Independently 1, 4-phenylene, 1, 4-cyclohexylene, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl, pyridine-2, 5-diyl, piperidine-1, 4-diyl, naphthalene-1, 5-diyl, naphthalene-2, 7-diyl or anthracene-9, 10-diyl, ring B²¹Ring B²²Ring B²³And ring B²⁴Wherein at least one hydrogen may be replaced by-F or-CH₃And (b) a substituent, s, t and u are independently an integer of 0 to 2, the total of which is 0 to 5, and when s, t or u is 2, the two bonding groups in each parenthesis may be the same or different, and the two rings may be the same or different. R²⁶Hydrogen, -F, -OH, alkyl group with 1-30 carbon atoms, fluorine substituted alkyl group with 1-30 carbon atoms, alkoxy group with 1-30 carbon atoms, -CN, -OCH₂F、-OCHF₂or-OCF₃At least one-CH of the C1-30 alkyl group₂May be substituted with a divalent group represented by the following formula (DI-31-b).

In the formula (DI-31-b), R²⁷And R²⁸Independently an alkyl group having 1 to 3 carbon atoms, and v is an integer of 1 to 6. R²⁶Preferred examples thereof include alkyl groups having 1 to 30 carbon atoms and alkoxy groups having 1 to 30 carbon atoms.

In formulae (DI-32) and (DI-33), G³⁰Independently a single bond, -CO-or-CH₂-，R²⁹Independently is hydrogen or-CH₃，R³⁰Is hydrogen, alkyl group having 1 to 20 carbon atoms, or alkenyl group having 2 to 20 carbon atoms. At least one hydrogen of the benzene ring in the formula (DI-32) and the formula (DI-33) may be substituted by an alkyl group having 1 to 20 carbon atoms or a phenyl group. Further, a group whose bonding position is not fixed to any carbon atom constituting a ring means that the bonding position in the ring is arbitrary. Preference is given to the two radicals "-phenylene-G in the formula (DI-32)³⁰One of the-O- "bonds to the 3-position of the steroid nucleus and the other bonds to the 6-position of the steroid nucleus. Two radicals "-phenylene-G in the formula (DI-33)³⁰The bonding position of-O- "on the phenyl ring is preferably meta or para, respectively, with respect to the bonding position of the steroid nucleus. In the formulae (DI-32) and (DI-33), -NH bonded to the benzene ring₂Indicates that the bonding position in the ring is arbitrary.

In formulae (DI-34) and (DI-35), G³¹Independently represents-O-, -NH-, or C1-C6 alkylene, G³²Is a single bond or C1-3 alkylene. R³¹Is hydrogen or C1-20 alkyl, at least one-CH of the alkyl₂-may be substituted by-O-, -CH ═ CH-, or-C ≡ C-. R³²Is C6-22 alkyl, R³³Is hydrogen or C1-22 alkyl. Ring B²⁵Is 1, 4-phenylene or 14-cyclohexylene radical, r is 0 or 1. and-NH bonded to the benzene ring₂The bond position on the ring is arbitrary, but is preferably independent of and relative to G³¹The bonding position of (A) is meta or para.

Specific examples of the side chain type diamine are shown below. The diamines having side chains of the formulae (DI-31) to (DI-35) include compounds represented by the following formulae (DI-31-1) to (DI-35-3).

Examples of the compounds represented by the formula (DI-31) are shown below.

In the formulae (DI-31-1) to (DI-31-11), R³⁴Independently an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, preferably an alkyl group having 5 to 25 carbon atoms or an alkoxy group having 5 to 25 carbon atoms. R³⁵Independently an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, preferably an alkyl group having 3 to 25 carbon atoms or an alkoxy group having 3 to 25 carbon atoms.

In the formulae (DI-31-12) to (DI-31-17), R³⁶Independently an alkyl group having 4 to 30 carbon atoms, preferably an alkyl group having 6 to 25 carbon atoms. R³⁷Independently an alkyl group having 6 to 30 carbon atoms, preferably an alkyl group having 8 to 25 carbon atoms.

In the formulae (DI-31-18) to (DI-31-43), R³⁸Independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, preferably an alkyl group having 3 to 20 carbon atoms or an alkoxy group having 3 to 20 carbon atoms. R³⁹Independently hydrogen, -F, alkyl group with 1-30 carbon atoms, alkoxy group with 1-30 carbon atoms, -CN, -OCH₂F、-OCHF₂or-OCF₃Preferably, the alkyl group has 3 to 25 carbon atoms or the alkoxy group has 3 to 25 carbon atoms. And, G³³Is an alkylene group having 1 to 20 carbon atoms.

Examples of the compounds represented by the formula (DI-32) are shown below.

Examples of the compounds represented by the formula (DI-33) are shown below.

Examples of the compounds represented by the formula (DI-34) are shown below.

In the formulae (DI-34-1) to (DI-34-14), R⁴⁰Independently hydrogen or alkyl group having 1 to 20 carbon atoms, preferably hydrogen or alkyl group having 1 to 10 carbon atoms, and R⁴¹Independently hydrogen or C1-C12 alkyl.

Examples of the compounds represented by the formula (DI-35) are shown below.

In the formulae (DI-35-1) to (DI-35-3), R³⁷Independently is C6-30 alkyl, R⁴¹Independently hydrogen or C1-C12 alkyl.

As the diamine in the present invention, diamines other than those represented by the formulae (DI-1-1) to (DI-16-1), the formulae (DIH-1-1) to (DIH-3-6), and the formulae (DI-31-1) to (DI-35-3) may be used. Examples of such diamines include compounds represented by the following formulae (DI-36-1) to (DI-36-13).

In the formulae (DI-36-1) to (DI-36-8), R⁴²Each independently represents an alkyl group having 3 to 30 carbon atoms.

In the formulae (DI-36-9) to (DI-36-11), e is an integer of 2 to 10, and in the formula (DI-36-12), R⁴³Independently of each other hydrogen, -NHBoc or-N (Boc)₂，R⁴³At least one of-NHBoc or-N (Boc)₂In the formula (DI-36-13), R⁴⁴is-NHBoc or-N (Boc)₂And m is an integer of 1 to 12. Herein, Boc is tert-butoxycarbonyl.

Suitable materials for enhancing the respective properties of the diamine and the dihydrazide are described.

In order to further enhance the orientation of liquid crystals, it is preferable to use compounds represented by the formulae (DI-1-3), (DI-4-1), (DI-5-5), (DI-5-9), (DI-5-12), (DI-5-13), (DI-5-29), (DI-6-7), (DI-7-3) and (DI-11-2) among the diamines and dihydrazides. More preferred are diamines represented by formula (DI-4-1), formula (DI-5-12), formula (DI-5-13), formula (DI-7-3). In formula (DI-5-1), m is preferably 2,4 or 6, and more preferably m is 4. In formula (DI-5-12), m is preferably 2 to 6, and more preferably 5. In formula (DI-5-13), m is preferably 1 or 2, and more preferably m is 1. In formula (DI-7-3), m is preferably 2, or 3, and n is 1, or 2, more preferably m is 1.

In the case where the transmittance is to be enhanced, among the diamine and the dihydrazide, compounds represented by the formulae (DI-1-3), (DI-2-1), (DI-5-5), (DI-5-17) and (DI-7-3) are preferably used, and a diamine represented by the formula (DI-2-1) is more preferred. In formula (DI-5-1), m is preferably 2,4 or 6, and more preferably m is 4. In formula (DI-7-3), m is preferably 2, or 3, and n is 1, or 2, more preferably m is 1.

In the case where importance is attached to raising the VHR of a liquid crystal display element, among the diamine and the dihydrazide, compounds represented by formula (DI-2-1), formula (DI-4-2), formula (DI-4-10), formula (DI-4-15), formula (DI-5-1), formula (DI-5-28), formula (DI-5-30), and formula (DI-13-1), and formula (DI-31-56) are preferably used, and more preferably compounds represented by formula (DI-2-1), formula (DI-5-1), formula (DI-13-1), and formula (DI-31-56). In formula (DI-5-1), m is preferably 1. In formula (DI-5-30), k is preferably 2.

As one of the methods for preventing burn marks, it is effective to increase the relaxation rate of residual charges (residual DC) in the alignment film by lowering the volume resistance value of the liquid crystal alignment film. Among the diamines and dihydrazides, those represented by the formulae (DI-4-1), (DI-4-2), (DI-4-10), (DI-4-15), (DI-5-1), (DI-5-12), (DI-5-13), (DI-5-28) and (DI-16-1) are preferably used in order to put importance on the object, and those represented by the formulae (DI-4-1), (DI-5-1) and (DI-5-13) are more preferably used. In formula (DI-5-1), m is preferably 2,4 or 6, and more preferably m is 4. In formula (DI-5-12), m is preferably 2 to 6, and more preferably 5. In formula (DI-5-13), m is preferably 1 or 2, and more preferably m is 1.

In each diamine, a part of the diamine may be substituted with a monoamine in a range where the ratio of the monoamine to the diamine is 40 mol% or less. Such substitution can cause termination of the polymerization reaction when the polyamic acid is produced, and can inhibit further progress of the polymerization reaction. Therefore, by such substitution, the molecular weight of the obtained polymer (polyamic acid, polyamic acid ester, or polyimide) can be easily controlled, and for example, the coating property of the liquid crystal aligning agent can be improved without impairing the effect of the present invention. One diamine may be substituted with a monoamine, or two or more diamines may be substituted with a monoamine, as long as the effects of the present invention are not impaired. Examples of the monoamine include: aniline, 4-hydroxyaniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, and n-eicosylamine.

The polyamic acid and the derivative thereof of the present invention may further contain a monoisocyanate compound in a monomer thereof. By containing a monoisocyanate compound in the monomer, the end of the obtained polyamic acid or derivative thereof is modified and the molecular weight is adjusted. By using the end-modified polyamic acid or the derivative thereof, for example, the coating property of the liquid crystal aligning agent can be improved without impairing the effect of the present invention. From the above viewpoint, the content of the monoisocyanate compound in the monomer is preferably 1 to 10 mol% based on the total amount of the diamine and the tetracarboxylic dianhydride in the monomer. Examples of the monoisocyanate compound include: phenyl isocyanate, and naphthyl isocyanate.

In the present invention, polyamic acid having a photoreactive structure and derivatives thereof can be suitably used. Examples of the photoreactive structure include: a photoisomerization structure causing isomerization by ultraviolet irradiation, a photodecomposition structure causing decomposition, a photodimerization structure causing dimerization, and the like.

The polyamic acid having a photoreactive structure and a derivative thereof are referred to as a polymer (a). In the polymer (a), a diamine having a photoreactive structure or a tetracarboxylic dianhydride having a photoreactive structure and a derivative thereof may be used as a raw material, or a diamine having a photoreactive structure and a tetracarboxylic dianhydride having a photoreactive structure and a derivative thereof may be used in combination. The photoreactive structure may be represented by the following formulae (P-1) to (P-7).

Examples of the compound having a photoreactive structure that causes photodegradation and is represented by the formula (P-1) include compounds represented by the following formulae (PA-1) to (PA-6).

In the formulae (PA-3) to (PA-6), R⁶²Independently an alkyl group having 1 to 5 carbon atoms.

Among the compounds represented by the formula (P-1), the above-mentioned formula (PA-1), formula (PA-2) and formula (PA-5) can be suitably used.

The compounds represented by the formulae (PA-1) to (PA-6) can be used as the tetracarboxylic dianhydride not having a photoreactive structure when used as a material for a liquid crystal aligning agent that utilizes liquid crystal aligning ability by photoisomerization reaction, liquid crystal aligning ability by photodimerization, or a liquid crystal aligning agent for rubbing.

Examples of the compound having a photoreactive structure represented by the formulae (P-2) to (P-4) include tetracarboxylic dianhydrides and diamine compounds represented by the formulae (II-1) to (VI-2).

In the respective formulae, the group whose bonding position is not fixed to any carbon atom constituting the ring means that the bonding position on the ring is arbitrary; in the formula (V-2), R⁶Independently is-CH₃、-OCH₃、-CF₃or-COOCH₃A is independently an integer of 0-2; in the formula (V-3), the ring A and the ring B are each independently at least one member selected from the group consisting of monocyclic hydrocarbons, condensed polycyclic hydrocarbons and heterocycles, R¹¹Is a C1-20 linear alkylene group, -COO-, -OCO-, -NHCO-or-N (CH)₃)CO-，R¹²Is a C1-20 linear alkylene group, -COO-, -OCO-, -NHCO-or-N (CH)₃)CO-，R¹¹And R¹²Of linear alkylene-CH₂One or two of (A) and (B) may be substituted by-O-, R⁷～R¹⁰Are independently-F, -CH₃、-OCH₃、-CF₃or-OH, and b to e are each independently an integer of 0 to 4.

From the viewpoint of the photosensitivity, the compounds represented by the above-mentioned formulae (V-1), (V-2) and (VI-2) can be particularly preferably used. From the viewpoint of the above-mentioned orientation, a compound in which the bonding position of the amino group in the formula (V-2) and the formula (VI-2) is para, or a compound in which a in the formula (V-2) is 0, can be more suitably used.

The acid dianhydride or diamine having a structure which can be photoisomerized by irradiation with ultraviolet rays represented by the formulae (II-1) to (VI-2) can be specifically represented by the following formulae (II-1-1) to (VI-2-3).

By using compounds having a structure in which the formula (VI-1-1) to the formula (V-3-8) can be isomerized by ultraviolet irradiation, a liquid crystal aligning agent for photo-alignment having higher sensitivity to ultraviolet irradiation can be obtained. By using compounds having structures which are isomerized by ultraviolet irradiation, the liquid crystal aligning agents for photo-alignment which can align liquid crystal molecules more uniformly can be obtained by using the compounds of the formulae (V-1-1), (V-2-4) to (V-2-11), and (V-3-1) to (V-3-8). By using compounds having a structure in which the formula (V-2-4) to the formula (V-3-8) can be isomerized by ultraviolet irradiation, it is possible to obtain a liquid crystal aligning agent for photo-alignment which can further reduce the coloring of the alignment film to be formed.

Among them, the compound represented by the formula (V-2-1) can be more preferably used from the viewpoint of exhibiting a larger anisotropy when a liquid crystal alignment film is formed.

Examples of the compounds having photoreactive structures represented by the formulae (P-5) to (P-7) include diamine compounds represented by the following formulae (PDI-9) to (PDI-13).

In the formula (PDI-12), R⁵⁴Is an alkyl group or an alkoxy group having 1 to 10 carbon atoms, wherein at least one hydrogen of the alkyl group or the alkoxy group may be substituted by fluorine.

The above-mentioned formulae (PDI-9) to (PDI-11) can be suitably used.

In the case of using a tetracarboxylic dianhydride not having a photoreactive structure (non-photosensitive) and a tetracarboxylic dianhydride having a photoreactive structure (photosensitive) in combination, the photosensitive tetracarboxylic dianhydride is preferably 0 to 70 mol%, particularly preferably 0 to 50 mol%, based on the total amount of tetracarboxylic dianhydrides used as raw materials in the production of the polyamic acid and the derivative thereof of the present invention, in order to prevent a decrease in sensitivity of the liquid crystal alignment film to light. In addition, two or more kinds of photosensitive tetracarboxylic dianhydrides may be used in combination in order to improve various characteristics such as sensitivity to light, electrical characteristics, and image sticking characteristics.

In the case of using a diamine having no photoreactive structure (non-photosensitive) and a diamine having a photoreactive structure (photosensitive) in combination, in order to prevent a decrease in sensitivity of the alignment film to light, the photosensitive diamine is preferably 20 to 100 mol%, particularly preferably 50 to 100 mol%, based on the total amount of diamines used as raw materials in producing the polyamic acid and derivative thereof of the present invention. In addition, two or more kinds of photosensitive diamines may be used in combination in order to improve the various characteristics such as sensitivity to light and image retention characteristics. As described above, in the aspect of the present invention, the total amount of tetracarboxylic dianhydrides is occupied by non-photosensitive tetracarboxylic dianhydrides, and even in this case, the minimum 20 mol% of the total amount of diamines is required to be photosensitive diamine.

In order to improve the various characteristics such as sensitivity to light and image retention characteristics, a photosensitive tetracarboxylic dianhydride and a photosensitive diamine may be used in combination, or two or more kinds may be used in combination.

The polyamic acid and the derivative thereof of the present invention can be obtained by reacting the mixture of tetracarboxylic dianhydrides described with a diamine in a solvent. In the synthesis reaction, the conditions in the synthesis of a polyamic acid can be applied as they are without particular necessity except for the selection of raw materials. The solvent used will be described later.

The polymer contained in the liquid crystal aligning agent of the present invention may be one type, or two or more types may be used by doping. In the case of the form in which two or more polymers are doped, the following cases are included: at least one of the polymers is a polymer (a) obtained by reacting at least one of tetracarboxylic dianhydride and diamine with a raw material monomer having a photoreactive structure, and at least one of the other polymers is a polymer (b) selected from at least one of polyamic acids and derivatives thereof obtained by reacting tetracarboxylic dianhydride having no photoreactive structure and diamine having no photoreactive structure. The polymer (a) has a property of causing the liquid crystal molecules in contact with the polymer film to be aligned in a specific direction (photo-alignment) by changing the structure thereof through isomerization, decomposition, or dimerization of the photoreactive structure by irradiation with energy rays such as ultraviolet rays. Such polymers are sometimes used in admixture with other polymers that do not have photoreactive structures.

The liquid crystal aligning agent of the present invention may further contain other components than polyamic acid or a derivative thereof. The other component may be one or two or more. Examples of the other component include other polymers and compounds described later.

In the case where a plurality of polymers are doped and used, the liquid crystal aligning agent of the present invention can be applied to a substrate and predried by controlling the structures and molecular weights of the respective polymers as described later, whereby, for example, the polymer (a) having the above-described photo-aligning function can be separated into an upper layer of a coating film and the other polymers (b) can be separated into a lower layer of the coating film. In the polymer mixed, it can be controlled by utilizing a phenomenon that a polymer having a small surface energy is separated into an upper layer and a polymer having a large surface energy is separated into a lower layer. Confirmation of layer separation may be confirmed by: the surface energy of the alignment film formed is the same as or similar to that of an alignment film formed using a liquid crystal aligning agent containing only the polymer (a).

The tetracarboxylic acid dianhydride used for synthesizing the polymer (b) can be selected from the tetracarboxylic acid dianhydrides known as tetracarboxylic acid dianhydrides which are essential components for synthesizing the liquid crystal aligning agent of the present invention, i.e., polyamic acid or a derivative thereof, and the same ones as the above-mentioned exemplary tetracarboxylic acid dianhydrides can be cited.

Among these tetracarboxylic dianhydrides, the tetracarboxylic dianhydrides represented by the formulae (AN-3-2), (AN-1-13) and (AN-4-30) are preferred when importance is attached to the improvement of layer separation.

Among the acid dianhydrides, compounds represented by the formulae (AN-1-1), (AN-1-2), (PA-1), (AN-3-1), (AN-4-17), (AN-4-30), (AN-5-1), (AN-7-2), (AN-10-1), (AN-10-2), (AN-16-3), and (AN-16-4) are preferable in order to increase the transmittance of a liquid crystal display element. In formula (AN-1-2), m is preferably 4 or 8. In formula (AN-4-17), m is preferably 4 or 8, and more preferably m is 8.

Among the acid dianhydrides, compounds represented by the formulae (PA-1), (PA-4-17), (AN-7-2), (AN-10-1), (AN-10-2), (AN-16-1), (AN-16-3) and (AN-16-4) are preferable in order to increase the VHR of a liquid crystal display element. In the formulae (AN-1-2) and (AN-4-17), m is preferably 4 or 8.

The tetracarboxylic dianhydride used for synthesizing the polymer (b) preferably contains 10 mol% or more of an aromatic tetracarboxylic dianhydride, and more preferably contains 30 mol% or more of an aromatic tetracarboxylic dianhydride, based on the total amount of the tetracarboxylic dianhydrides.

As the diamine and dihydrazide used for synthesizing the polymer (b), the same ones as those exemplified above as other diamines which are essential components usable for synthesizing the liquid crystal aligning agent of the present invention, i.e., polyamic acid or a derivative thereof can be cited.

Among these diamines and dihydrazides, compounds represented by the formulae (DI-4-1), (DI-4-2), (DI-4-10), (DI-5-1), (DI-5-9), (DI-5-28), and (DIH-2-1) are preferably used in order to further improve the alignment properties of liquid crystals, which is to say, to emphasize layer separability. In formula (DI-5-1), m is preferably 1,2, or 4, and more preferably m is 1 or 2.

Among the diamines and dihydrazides, diamines represented by the formulae (DI-1-2), (DI-2-1), (DI-5-1) and (DI-7-3) are preferably used, and diamines represented by the formula (DI-2-1) are more preferably used when importance is attached to the improvement of transmittance. In formula (DI-5-1), m is preferably 1,2, or 4, and more preferably m is 1 or 2. In formula (DI-7-3), m is preferably 2 or 3, and n is 1 or 2, more preferably m is 1.

In the case where emphasis is placed on raising the VHR of a liquid crystal display element, it is preferable to use diamines represented by the formulae (DI-2-1), (DI-4-2), (DI-4-15), (DI-5-1), (DI-5-28), (DI-5-30), (DI-13-1) and (DI-13-56) among the diamines and dihydrazides. More preferred are diamines represented by formula (DI-2-1), formula (DI-5-1), formula (DI-13-1) and formula (DI-36-14). In the formula (DI-5-1), m is preferably 1 or 2. In the formula (DI-5-30), k is preferably 2.

As one of the methods for preventing burn marks, it is effective to increase the relaxation rate of residual charges (residual DC) in the alignment film by lowering the volume resistance value of the liquid crystal alignment film. Among the diamines and dihydrazides, those represented by the formula (DI-4-1), the formula (DI-4-2), the formula (DI-4-10), the formula (DI-4-15), the formula (DI-5-1), the formula (DI-5-9), the formula (DI-5-12), the formula (DI-5-13), the formula (DI-5-28), the formula (DI-5-30), and the formula (DI-16-1) are preferably used in order to attach importance to the object, and those represented by the formula (DI-4-1), the formula (DI-5-1), and the formula (DI-5-12) are more preferably used. In formula (DI-5-1), m is preferably 1 or 2. In the formula (DI-5-12), m is preferably 2 to 6, and more preferably 5. In formula (DI-5-13), m is preferably 1 or 2, and more preferably m is 1. In the formula (DI-5-30), k is preferably 2.

The diamine used for synthesizing the polymer (b) preferably contains 30 mol% or more of the aromatic diamine with respect to all of the diamines, and more preferably contains 50 mol% or more of the aromatic diamine.

In the liquid crystal aligning agent of the present invention, the proportion of the polymer (a) to the total amount of the polymer (a) and the polymer (b) is preferably 10 to 100% by weight, and more preferably 20 to 100% by weight.

The liquid crystal aligning agent of the present invention may further contain other components than the polyamic acid or the derivative thereof of the present invention. The other component may be one or two or more. Examples of the other component include other polymers and compounds described later.

As other polymers, there may be mentioned: polyesters, polyamides, polysiloxanes, cellulose derivatives, polyacetals, polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylates, and the like. One or more than two kinds may be used. Of these polymers, other polyamic acids or derivatives thereof and polysiloxanes are preferable, and other polyamic acids or derivatives thereof are more preferable.

As the polysiloxane, there may be further contained polysiloxanes disclosed in Japanese patent laid-open No. 2009-036966, Japanese patent laid-open No. 2010-185001, Japanese patent laid-open No. 2011-102963, Japanese patent laid-open No. 2011-253175, Japanese patent laid-open No. 2012-159825, International publication 2008/044644, International publication 2009/148099, International publication 2010/074261, International publication 2010/074264, International publication 2010/126108, International publication 2011/068123, International publication 2011/068127, International publication 2011/068128, International publication 2012/115157, International publication 2012/165354 and the like.

The liquid crystal aligning agent of the present invention may further contain an additive other than the compound represented by formula (1). Examples of the additive other than the compound represented by the formula (1) include an alkenyl-substituted nadimide compound, an oxazine compound, an oxazoline compound, an epoxy compound other than the compound represented by the formula (1), a polymer compound other than polyamic acid and its derivative, and other low-molecular compounds, and can be selected and used according to the respective purposes.

< alkenyl-substituted nadimide Compound >

The liquid crystal aligning agent of the present invention may further contain an alkenyl-substituted nadimide compound for the purpose of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time. One kind of the alkenyl-substituted nadimide compound may be used, or two or more kinds thereof may be used in combination. For the purpose, the content of the alkenyl-substituted nadimide compound is preferably 1 to 100 wt%, more preferably 1 to 70 wt%, and still more preferably 1 to 50 wt% with respect to the polyamic acid or derivative thereof.

Hereinafter, the nadimide compound will be specifically described.

The alkenyl-substituted nadimide compound is preferably a compound that can be dissolved in a solvent in which the polyamic acid or the derivative thereof used in the present invention is dissolved. Examples of such an alkenyl-substituted nadimide compound include compounds represented by the following formula (NA).

In the formula (NA), L¹And L²Independently hydrogen, alkyl with 1-12 carbon atoms, alkenyl with 3-6 carbon atoms, cycloalkyl with 5-8 carbon atoms, aryl with 6-12 carbon atoms or benzyl, and n is 1 or 2.

In the formula (NA), when n is 1, W is alkyl having 1 to 12 carbon atoms, alkenyl having 2 to 6 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, aryl having 6 to 12 carbon atoms, benzyl, or a group represented by the formula-Z¹-(O)_r-(Z²O)_k-Z³H (here, Z)¹、Z²And Z³Independently an alkylene group having 2 to 6 carbon atoms, r is 0 or 1, and k is an integer of 1 to 30), a group represented by- (Z)⁴)_r-B-Z⁵H (here, Z)⁴And Z⁵Independently an alkylene group having 1 to 4 carbon atoms or a cycloalkylene group having 5 to 8 carbon atoms, B is a phenylene group, r is 0 or 1), a group represented by-B-T-B-H (here, B is a phenylene group, and T is-CH₂-、-C(CH₃)₂-, -O-, -CO-, -S-, or-SO₂-) or a group wherein one to three hydrogens of these groups are replaced with-OH groups.

In this case, W is preferably an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 3 to 4 carbon atoms, a cyclohexyl group, a phenyl group, a benzyl group, a poly (ethyleneoxy) ethyl group having 4 to 10 carbon atoms, a phenoxyphenyl group, a phenylmethylphenyl group, a phenylisopropylidenylphenyl group, or a group obtained by substituting one or two hydrogens of these groups with-OH.

In the formula (NA), when n is 2, W is alkylene having 2 to 20 carbon atoms, cycloalkylene having 5 to 8 carbon atoms, arylene having 6 to 12 carbon atoms, or-Z¹-O-(Z²O)_k-Z³- (Here, Z)¹～Z³And k is as defined above), a group represented by-Z⁴-B-Z⁵- (Here, Z)⁴、Z⁵And B is as defined above), a group represented by-B- (O-B)_r-T-(B-O)_r-B- (here, B is phenylene, T is C1-3 alkylene, -O-, or-SO)₂-, r is as defined above), or a group in which one to three hydrogens of these groups are substituted with-OH.

In this case, W is preferably C-C alkylene having 2 to 12 carbon atoms, cyclohexylene, phenylene, benzylidene, xylylene₃H₆-O-(Z²-O)_n-O-C₃H₆- (Here, Z)²Is alkylene having 2 to 6 carbon atoms, n is 1 or 2), a group represented by-B-T-B- (wherein B is phenylene, and T is-CH₂-, -O-or-SO₂-) a group represented by-B-O-B-C₃H₆A group represented by-B-O-B- (wherein, B is a phenylene group), and a group wherein one or both hydrogens of these groups are substituted with-OH.

As such an alkenyl-substituted nadimide compound, for example, as described in Japanese patent No. 2729565, a compound obtained by maintaining an alkenyl-substituted nadimide derivative and a diamine at a temperature of 80 to 220 ℃ for 0.5 to 20 hours, or a commercially available compound can be used. Specific examples of the alkenyl-substituted nadimide compound include the following compounds.

N-methyl-allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N-methyl-allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N-methyl-methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N-methyl-methallylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (2-ethylhexyl) -allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N-methyl-allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (2-ethylhexyl) -allylbicyclo [2.2.1] dicarboximide,

N- (2-ethylhexyl) -allyl (methyl) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N-allyl-allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N-allyl-allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N-allyl-methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N-isopropenyl-allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N-isopropenyl-allyl (methyl) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N-isopropenyl-methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N-cyclohexyl-allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N-cyclohexyl-allyl (methyl) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N-cyclohexyl-methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N-phenyl-allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide,

N-phenyl-allyl (methyl) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N-benzyl-allyl methyl bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N-benzyl-methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (2-hydroxyethyl) -allyl bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (2-hydroxyethyl) -allyl (methyl) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboxyimide, N- (2-hydroxyethyl) -methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboxyimide,

N- (2, 2-dimethyl-3-hydroxypropyl) -allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (2, 2-dimethyl-3-hydroxypropyl) -allyl (methyl) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (2, 3-dihydroxypropyl) -allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (2, 3-dihydroxypropyl) -allyl (methyl) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (3-hydroxy-1-propenyl) -allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboxyimide, N- (4-hydroxycyclohexyl) -allyl (methyl) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboxyimide,

N- (4-hydroxyphenyl) -allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (4-hydroxyphenyl) -allyl (methyl) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (4-hydroxyphenyl) -methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (4-hydroxyphenyl) -methallylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (3-hydroxyphenyl) -allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (3-hydroxyphenyl) -allyl (methyl) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide -ene-2, 3-dicarboximide, N- (p-hydroxybenzyl) -allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- {2- (2-hydroxyethoxy) ethyl } -allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N-bis (p-hydroxybenzyl) hydroxy-ethyl ester, N-bis (p-hydroxy-ethyl) ethyl ester, N-bis (p-hydroxyethoxy) ethyl ester, N-hydroxy-ethyl ester, N-2, 3-dicarboximide, N-bis (p-hydroxy-ethyl ester), N-5-hept-5-ene-2, 3-dicarboximide, N-bis (p-hydroxy-ethyl ester), N-bis (p-hydroxy-ethyl ester), N-bis (p-hydroxy-2, N-hydroxy-bis (p-hydroxy-ethyl ester), N-hydroxy-bis (p-hydroxy-ethyl ester), N-bis (p-2, N-hydroxy-bis (p-hydroxy-ethyl ester), N-hydroxy-bis (p-hydroxy-ethyl ester), N-hydroxy-bis (p-amide) amide, N-bis (p-amide, N-amide,

N- {2- (2-hydroxyethoxy) ethyl } -allyl (methyl) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- {2- (2-hydroxyethoxy) ethyl } -methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- {2- (2-hydroxyethoxy) ethyl } -methallylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- [2- {2- (2-hydroxyethoxy) ethoxy } ethyl ] -allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- [2- {2- (2-hydroxyethoxy) ethoxy } ethyl ] - Allyl (methyl) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- [2- {2- (2-hydroxyethoxy) ethoxy } ethyl ] -methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- {4- (4-hydroxyphenylisopropylidene) phenyl } -allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- {4- (4-hydroxyphenylisopropylidene) phenyl } -allyl (methyl) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- {4- (4-hydroxyphenylisopropylidene) phenyl } -methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboxyimides, oligomers thereof,

N, N ' -ethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide), N ' -ethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide), N ' -ethylene-bis (methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide), N ' -trimethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide), N ' -hexamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-carbo-imide) 2, 3-dicarboximide), N '-dodecamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide), N' -dodecamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide), N '-cyclohexylidene-bis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide), N' -cyclohexylidene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide),

1, 2-bis {3' - (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboxyimide) propoxy } ethane, 1, 2-bis {3' - (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboxyimide) propoxy } ethane, 1, 2-bis {3' - (methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboxyimide) propoxy } ethane, bis [2' - {3' - (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboxyimide) propoxy } ethyl ] ether, bis [2' - {3' - (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboxyimide) propoxy } ethyl ] ether, 3-dicarboximide) propoxy } ethyl ] ether, 1, 4-bis {3'- (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide) propoxy } butane, 1, 4-bis {3' - (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide) propoxy } butane, and mixtures thereof,

N, N ' -p-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide), N ' -p-phenylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide), N ' -m-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide), N ' -m-phenylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide), N ' - { (1-methyl) -2, 4-phenylene } -bis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide), N '-p-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide), N' -p-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide), N '-m-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide), N' -m-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide),

2, 2-bis [4- {4- (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide) phenoxy } phenyl ] propane, 2-bis [4- {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide) phenoxy } phenyl ] propane, 2-bis [4- {4- (methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide) phenoxy } phenyl ] propane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide) phenyl } methane, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboxyimide) phenyl } methane,

Bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide) phenyl } methane, bis {4- (methallylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide) phenyl } methane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide) phenyl } ether, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide) phenyl } ether, bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide) phenyl } ether, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide) phenyl } sulfone, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide) phenyl } sulfone, and,

Bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide) phenyl } sulfone, 1, 6-bis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide) -3-hydroxy-hexane, 1, 12-bis (methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide) -3, 6-dihydroxy-dodecane, 1, 3-bis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide) -5-hydroxy-cyclohexane, 1, 5-bis {3' - (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboxyimide) propoxy } -3-hydroxy-pentane, 1, 4-bis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboxyimide) -2-hydroxy-benzene,

1, 4-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide) -2, 5-dihydroxy-benzene, N '-p- (2-hydroxy) xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide), N' -p- (2-hydroxy) xylylene-bis (allylmethylcyclo [2.2.1] hept-5-ene-2, 3-dicarboximide), N '-m- (2-hydroxy) xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide), N' -m- (2-hydroxy) xylylene-bis (methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboxyimide), N' -p- (2, 3-dihydroxy) benzenedimethyl-bis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboxyimide),

2, 2-bis [4- {4- (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboxyimide) -2-hydroxy-phenoxy } phenyl ] propane, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboxyimide) -2-hydroxy-phenyl } methane, bis {3- (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboxyimide) -4-hydroxy-phenyl } ether, bis {3- (methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboxyimide) -5-hydroxy-phenyl } sulfone, 1,1, 1-tris {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide), phenoxymethylpropane, N' -tris (ethylenemethallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide) isocyanurate, and oligomers thereof.

Further, the alkenyl-substituted nadimide compound used in the present invention may be a compound represented by the following formula containing an asymmetric alkylene-phenylene group.

Preferred compounds among the alkenyl-substituted nadimide compounds are shown below.

N, N ' -p-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide), N ' -p-phenylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide), N ' -m-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide), N ' -m-phenylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide), N ' - { (1-methyl) -2, 4-phenylene } -bis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide), N '-p-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide), N' -p-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide), N '-m-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide), N' -m-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide), 2-bis [4- {4- (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboxyimide) phenoxy } phenyl ] propane, 2-bis [4- {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboxyimide) phenoxy } phenyl ] propane, 2-bis [4- {4- (methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboxyimide) phenoxy } phenyl ] propane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboxyimide) phenyl } methane, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboxyimide) phenyl } methane,

Bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide) phenyl } methane, bis {4- (methallylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide) phenyl } methane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide) phenyl } ether, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide) phenyl } ether, bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide) phenyl } ether, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide) phenyl } sulfone, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide) phenyl } sulfone, bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide) phenyl } sulfone.

The more preferred alkenyl-substituted nadimide compounds are shown below.

2, 2-bis [4- {4- (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide) phenoxy } phenyl ] propane, 2-bis [4- {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide) phenoxy } phenyl ] propane, 2-bis [4- {4- (methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide) phenoxy } phenyl ] propane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide) phenyl } methane, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboxyimide) phenyl } methane, bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboxyimide) phenyl } methane, bis {4- (methallylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboxyimide) phenyl } methane.

Further, as particularly preferred alkenyl-substituted nadimide compounds, there can be mentioned: bis {4- (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboxyimide) phenyl } methane represented by the following formula (NA-1), N '-m-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboxyimide) represented by the formula (NA-2), and N, N' -hexamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboxyimide) represented by the formula (NA-3).

< Compound having a radically polymerizable unsaturated double bond >

The liquid crystal aligning agent of the present invention may further contain a compound having a radical polymerizable unsaturated double bond for the purpose of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time. The compound having a radical polymerizable unsaturated double bond may be one kind of compound, or two or more kinds of compounds. Further, the compound having a radical polymerizable unsaturated double bond does not contain an alkenyl-substituted nadimide compound. For the above purpose, the content of the compound having a radical polymerizable unsaturated double bond is preferably 1 to 100 wt%, more preferably 1 to 70 wt%, and still more preferably 1 to 50 wt% with respect to the polyamic acid or the derivative thereof.

Further, the ratio of the compound having a radical polymerizable unsaturated double bond to the alkenyl-substituted nadimide compound is preferably 0.1 to 10, more preferably 0.5 to 5 in terms of a weight ratio of the compound having a radical polymerizable unsaturated double bond/the alkenyl-substituted nadimide compound in order to reduce an ion density of the liquid crystal display element, suppress an increase in the ion density with time, and further suppress generation of an afterimage.

The compound having a radical polymerizable unsaturated double bond will be specifically described below.

Examples of the compound having a radical polymerizable unsaturated double bond include: (meth) acrylic acid esters, (meth) acrylic acid derivatives such as (meth) acrylamide, and bismaleimides. The compound having a radically polymerizable unsaturated double bond is more preferably a (meth) acrylic acid derivative having two or more radically polymerizable unsaturated double bonds.

Specific examples of the (meth) acrylic acid ester include: cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate.

Specific examples of the difunctional (meth) acrylate include, for example: ethylene bisacrylate, Aronix M-210, Aronix M-240 and Aronix M-6200, which are products of the east Asia synthetic chemical industry (Ltd.), Kayarad HDDA (KAYARAD), Kayarad HX-220, Kayarad R-604 and Kayade R-684, which are products of the Japan chemical industry (Ltd.), V260, V312 and V335HP, which are products of the Osaka organic chemical industry (Ltd.), and Light Acrylate BA-4EA (Light Acrylate-4 EA), Light Acrylate BP-4PA and Light Acrylate BP-2PA, which are products of the Kyoho oil and fat chemical industry (Ltd.).

Specific examples of the trifunctional or higher polyfunctional (meth) acrylate include, for example: 4,4' -methylenebis (N, N-dihydroxyethylene acrylate aniline), Aronics M-400, Aronics M-405, Aronics M-450, Aronics M-7100, Aronics M-8030, and Aronics M-8060, as products of Nippon Chemicals (parts), Kayada TMPTA, Kayada DPCA-20, Kayada DPCA-30, Kayada DPCA-60, and Kayada DPCA-120, as products of Osaka organic chemical industry (parts), and VGPT.

Specific examples of the (meth) acrylamide derivative include: n-isopropylacrylamide, N-isopropylmethacrylamide, N-N-propylacrylamide, N-N-propylmethacrylamide, N-cyclopropylacrylamide, N-cyclopropylmethacrylamide, N-ethoxyethylacrylamide, N-ethoxyethylmethacrylamide, N-tetrahydrofurfuryl acrylamide, N-tetrahydrofurfuryl methacrylamide, N-ethylacrylamide, N-ethyl acrylamide, N-ethyl-N-methylacrylamide, N-diethylacrylamide, N-methyl-N-N-propylacrylamide, N-methyl-N-isopropylacrylamide, N-acryloylpiperidine, N-acryloylpyrrolidine, N' -methylenebisacrylamide, N-isopropylmethacrylamide, N-ethylmethacrylamide, N-isopropylmethacrylamide, N-isopropylmethacrylamide, N-isopropylmethacrylamide, N-isopropylmethacrylamide, N-N-isopropylmethacrylamide, N-isopropylmethacrylamide, N-isopropylmethacrylamide, N-, N, N ' -ethylenebisacrylamide, N ' -dihydroxyethylenebisacrylamide, N- (4-hydroxyphenyl) methacrylamide, N-phenylmethylacrylamide, N-butylmethacrylamide, N- (isobutoxymethyl) methacrylamide, N- [2- (N, N-dimethylamino) ethyl ] methacrylamide, N-dimethylmethacrylamide, N- [3- (dimethylamino) propyl ] methacrylamide, N- (methoxymethyl) methacrylamide, N- (hydroxymethyl) -2-methacrylamide, N-benzyl-2-methacrylamide, and N, N ' -methylenebismethacrylamide.

Among the (meth) acrylic acid derivatives, N ' -methylenebisacrylamide, N ' -dihydroxyethylene-bisacrylamide, ethylene bisacrylate, and 4,4' -methylenebis (N, N-dihydroxyethylene acrylate aniline) are particularly preferable.

Examples of bismaleimides include: BMI-70 and BMI-80 manufactured by KI formation (shares), and BMI-1000, BMI-3000, BMI-4000, BMI-5000 and BMI-7000 manufactured by Dahe formation industry (shares).

< oxazine Compound >

The liquid crystal aligning agent of the present invention may further contain an oxazine compound for the purpose of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time. The oxazine compound may be one compound or two or more compounds. For the purpose, the content of the oxazine compound is preferably 0.1 to 50 wt%, more preferably 1 to 40 wt%, and still more preferably 1 to 20 wt% with respect to the polyamic acid or derivative thereof.

The oxazine compound is specifically described below.

The oxazine compound is preferably soluble in a solvent in which the polyamic acid or derivative thereof is dissolved, and has ring-opening polymerizability.

In addition, the number of oxazine structures in the oxazine compound is not particularly limited.

Various structures are known for oxazine structures. In the present invention, the structure of the oxazine is not particularly limited, and the structure of an oxazine having an aromatic group containing a condensed polycyclic aromatic group, such as benzoxazine or naphthoxazine, may be mentioned as the oxazine structure in the oxazine compound.

Examples of the oxazine compound include compounds represented by the following formulae (OX-1) to (OX-6). Further, in the following formulae, the bond represented toward the center of the ring means that it is bonded to any one of the carbons constituting the ring and to which a substituent may be bonded.

In the formulae (OX-1) to (OX-3), L³And L⁴Is an organic group having 1 to 30 carbon atoms, wherein L is represented by the formulae (OX-1) to (OX-6)⁵～L⁸Is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, wherein Q is represented by the formula (OX-3), the formula (OX-4) or the formula (OX-6)¹Is a single bond, -O-, -S-S-, -SO₂-、-CO-、-CONH-、-NHCO-、-C(CH₃)₂-、-C(CF₃)₂-、-(CH₂)_v-、-O-(CH₂)_v-O-、-S-(CH₂)_v-S-where v is an integer of 1 to 6, in the formulae (OX-5) and (OX-6), Q²Independently a single bond, -O-, -S-, -CO-, -C (CH)₃)₂-、-C(CF₃)₂Or C1-3 alkylene, Q²The hydrogen bonded on the benzene ring and the naphthalene ring in (1) is independent and can be composed of-F and-CH₃、-OH、-COOH、-SO₃H、-PO₃H₂And (4) substitution.

In addition, the oxazine compound includes an oligomer or polymer having an oxazine structure in a side chain, and an oligomer or polymer having an oxazine structure in a main chain.

Examples of the oxazine compound represented by formula (OX-1) include the following oxazine compounds.

In the formula (OX-1-2),L³the alkyl group has preferably 1 to 30 carbon atoms, and more preferably 1 to 20 carbon atoms.

As the oxazine compound represented by formula (OX-2), for example, the following oxazine compounds can be cited.

In the formula, L³The alkyl group has preferably 1 to 30 carbon atoms, and more preferably 1 to 20 carbon atoms.

As the oxazine compound represented by formula (OX-3), an oxazine compound represented by the following formula (OX-3-I) may be mentioned.

In the formula (OX-3-I), L³And L⁴Is an organic group having 1 to 30 carbon atoms, L⁵～L⁸Is hydrogen or C1-6 alkyl, Q¹Is a single bond, -CH₂-、-C(CH₃)₂-、-CO-、-O-、-SO₂-、-C(CH₃)₂-or-C (CF)₃)₂-. Examples of the oxazine compound represented by the formula (OX-3-I) include the following oxazine compounds.

In the formula, L³And L⁴The alkyl group has preferably 1 to 30 carbon atoms, and more preferably 1 to 20 carbon atoms.

As the oxazine compound represented by formula (OX-4), for example, the following oxazine compounds can be cited.

As the oxazine compound represented by formula (OX-5), for example, the following oxazine compounds can be cited.

As the oxazine compound represented by formula (OX-6), for example, the following oxazine compounds can be cited.

Among these, oxazine compounds represented by formula (OX-2-1), formula (OX-3-3), formula (OX-3-5), formula (OX-3-7), formula (OX-3-9), formula (OX-4-1) to formula (OX-4-6), formula (OX-5-3), formula (OX-5-4), and formula (OX-6-2) to formula (OX-6-4) are more preferable.

The oxazine compound can be produced by the same method as that described in International publication No. 2004/009708, Japanese patent laid-open No. Hei 11-12258, Japanese patent laid-open No. 2004-352670.

The oxazine compound represented by formula (OX-1) can be obtained by reacting a phenol compound with a primary amine and an aldehyde (see international publication No. 2004/009708).

The oxazine compound represented by formula (OX-2) may be obtained by: the reaction is carried out by a method of slowly adding a primary amine to formaldehyde, and then a compound having a naphthol-based hydroxyl group is added to the mixture to carry out the reaction (see international publication No. 2004/009708).

The oxazine compound represented by formula (OX-3) may be obtained by: in the presence of a secondary aliphatic amine, a tertiary aliphatic amine or a basic nitrogen-containing heterocyclic compound, 1 mole of a phenol compound, at least 2 moles or more of an aldehyde relative to one phenolic hydroxyl group of the phenol compound, and 1 mole of a primary amine are reacted in an organic solvent (see international publication No. 2004/009708 and japanese patent laid-open publication No. hei 11-12258).

The oxazine compounds represented by formulae (OX-4) to (OX-6) can be obtained by: a dehydration condensation reaction of a diamine having a plurality of benzene rings and organic groups bonded to the benzene rings, such as 4,4' -diaminodiphenylmethane, an aldehyde such as formalin, and phenol in n-butanol at a temperature of 90 ℃ or higher (see Japanese patent laid-open No. 2004-352670).

< oxazoline Compound >

The liquid crystal aligning agent of the present invention may further contain an oxazoline compound for the purpose of stabilizing the electric characteristics of the liquid crystal display element for a long period of time. The oxazoline compound is a compound having an oxazoline structure. The oxazoline compound may be one compound or two or more compounds. For the purpose, the content of the oxazoline compound is preferably 0.1 to 50 wt%, more preferably 1 to 40 wt%, and still more preferably 1 to 20 wt% with respect to the polyamic acid or the derivative thereof. Alternatively, when the oxazoline structure in the oxazoline compound is converted to an oxazoline, the content of the oxazoline compound is preferably 0.1 to 40 wt% with respect to the polyamic acid or the derivative thereof for the above purpose.

The oxazoline compound will be specifically described below.

The oxazoline compound may have only one oxazoline structure in one compound, or may have two or more oxazoline structures. The oxazoline compound may have one oxazoline structure in one compound, but preferably has two or more oxazoline structures. The oxazoline compound may be a polymer having an oxazoline structure in a side chain or a copolymer. The polymer having an oxazoline structure in a side chain may be a homopolymer of a monomer having an oxazoline structure in a side chain, or may be a copolymer of a monomer having an oxazoline structure in a side chain and a monomer having no oxazoline structure. The copolymer having an oxazoline structure in a side chain may be a copolymer of two or more monomers having an oxazoline structure in a side chain, or a copolymer of two or more monomers having an oxazoline structure in a side chain and a monomer having no oxazoline structure.

The oxazoline structure is preferably a structure in which one or both of oxygen and nitrogen in the oxazoline structure and a carbonyl group of the polyamic acid are present in the oxazoline compound in such a manner that they can react.

Examples of oxazoline compounds include: 2,2' -bis (2-oxazoline), 1,2, 4-tris- (2-oxazolinyl-2) -benzene, 4-furan-2-ylmethylene-2-phenyl-4H-oxazol-5-one, 1, 4-bis (4, 5-dihydro-2-oxazolyl) benzene, 1, 3-bis (4, 5-dihydro-2-oxazolyl) benzene, 2, 3-bis (4-isopropenyl-2-oxazolin-2-yl) butane, 2' -bis-4-benzyl-2-oxazoline, 2, 6-bis (isopropyl-2-oxazolin-2-yl) pyridine, 2' -isopropylidenebis (4-tert-butyl-2-oxazoline), 2,2' -isopropylidenebis (4-phenyl-2-oxazoline), 2' -methylenebis (4-tert-butyl-2-oxazoline), and 2,2' -methylenebis (4-phenyl-2-oxazoline). In addition to these oxazoline compounds, polymers or oligomers having an oxazolyl group such as eporos (trade name, manufactured by japan catalyst (stock) can be cited. Among these oxazoline compounds, 1, 3-bis (4, 5-dihydro-2-oxazolyl) benzene is more preferable.

< epoxy Compound >

The liquid crystal aligning agent of the present invention may further contain an epoxy compound other than the compound represented by formula (1) for the purpose of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time. The epoxy compound may be one compound or two or more compounds. For the purpose, the content of the epoxy compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, and still more preferably 1 to 20% by weight, relative to the polyamic acid or a derivative thereof.

The epoxy compound other than the compound represented by the formula (1) will be specifically described below.

Examples of the epoxy compound include various compounds having one or two or more epoxy rings in the molecule. Examples of the compound having one epoxy ring in the molecule include: phenyl glycidyl ether, butyl glycidyl ether, 3,3, 3-trifluoromethylepoxypropane, styrene oxide, hexafluoropropylene oxide, cyclohexene oxide (cyclohexene oxide), 3-glycidoxypropyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, N-glycidylphthalimide, (nonafluoro-N-butyl) epoxide, perfluoroethyl glycidyl ether, epichlorohydrin, epibromohydrin, N-diglycidylaniline, and 3- [2- (perfluorohexyl) ethoxy ] -1, 2-epoxypropane.

Examples of the compound having two epoxy rings in the molecule include: ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2-dibromoneopentyl glycol diglycidyl ether, 3, 4-epoxycyclohexenylmethyl-3 ',4' -epoxycyclohexene carboxylate, and 3- (N, N-diglycidyl) aminopropyltrimethoxysilane.

Examples of the compound having three epoxy rings in the molecule include: 2- [4- (2, 3-epoxypropoxy) phenyl ] -2- [4- [1, 1-bis [4- ([2, 3-epoxypropoxy ] phenyl) ] ethyl ] phenyl ] propane (trade name "iron gram mole vinylidene VG3101L (Techmore VG 3101L)", (manufactured by Mitsui Chemicals (Ltd.)).

Examples of the compound having four epoxy rings in the molecule include: 1,3,5, 6-tetraglycidyl-2, 4-hexanediol, N, N, N ', N ' -tetraglycidyl-m-xylylenediamine, 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N ' -tetraglycidyl-4, 4' -diaminodiphenylmethane, and 3- (N-allyl-N-glycidyl) aminopropyltrimethoxysilane.

In addition to the above, an oligomer or polymer having an epoxy ring may be cited as an example of the compound having an epoxy ring in the molecule. Examples of the monomer having an epoxy ring include: glycidyl (meth) acrylate, 3, 4-epoxycyclohexyl (meth) acrylate, and methyl glycidyl (meth) acrylate.

Examples of the other monomer copolymerizable with the monomer having an epoxy ring include: (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, styrene, methylstyrene, chloromethylstyrene, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, N-cyclohexylmaleimide and N-phenylmaleimide.

Preferable specific examples of the polymer of the monomer having an epoxy ring include polyglycidyl methacrylate and the like. Further, preferable specific examples of the copolymer of the monomer having an epoxy ring and other monomers include: n-phenylmaleimide-glycidyl methacrylate copolymers, N-cyclohexylmaleimide-glycidyl methacrylate copolymers, benzyl methacrylate-glycidyl methacrylate copolymers, butyl methacrylate-glycidyl methacrylate copolymers, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymers, 3-ethyl-3-oxetanyl methyl methacrylate-glycidyl methacrylate copolymers, and styrene-glycidyl methacrylate copolymers.

Among these examples, N, N, N ', N ' -tetraglycidyl-m-xylylenediamine, 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N ' -tetraglycidyl-4, 4' -diaminodiphenylmethane, trade name "Fe gram mole VG310 3101L", 3, 4-epoxycyclohexenylmethyl-3 ',4' -epoxycyclohexene carboxylate, N-phenylmaleimide-glycidyl methacrylate copolymer, and 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane are particularly preferable.

More specifically, examples of the epoxy compound include: glycidyl ether, glycidyl ester, glycidyl amine, epoxy group-containing acrylic resin, glycidyl amide, glycidyl isocyanurate, chain aliphatic epoxy compound, and cyclic aliphatic epoxy compound. The epoxy compound means a compound having an epoxy group, and the epoxy resin means a resin having an epoxy group.

Examples of the epoxy compound include: glycidyl ether, glycidyl ester, glycidyl amine, epoxy group-containing acrylic resin, glycidyl amide, glycidyl isocyanurate, chain aliphatic epoxy compound, and cyclic aliphatic epoxy compound.

Examples of glycidyl ethers include: bisphenol A-type epoxy compound, bisphenol F-type epoxy compound, bisphenol S-type epoxy compound, bisphenol-type epoxy compound, hydrogenated bisphenol-A-type epoxy compound, hydrogenated bisphenol-F-type epoxy compound, hydrogenated bisphenol-S-type epoxy compound, hydrogenated bisphenol-type epoxy compound, brominated bisphenol-A-type epoxy compound, brominated bisphenol-F-type epoxy compound, phenol novolac-type epoxy compound, cresol novolac-type epoxy compound, brominated phenol novolac-type epoxy compound, brominated cresol novolac-type epoxy compound, bisphenol A novolac-type epoxy compound, epoxy compound having a naphthalene skeleton, aromatic polyglycidyl ether compound, dicyclopentadiene phenol-type epoxy compound, alicyclic diglycidyl ether compound, aliphatic polyglycidyl ether compound, aromatic polyglycidyl ether compound, hydrogenated bisphenol A-type epoxy compound, brominated bisphenol F-type epoxy compound, phenol novolac-type epoxy compound, phenol-type epoxy compound, and the like, A polysulfide-type diglycidyl ether compound, and a biphenol-type epoxy compound.

Examples of glycidyl esters include: diglycidyl ester compounds and glycidyl ester epoxy compounds.

Examples of glycidyl amines include: polyglycidyl amine compounds and glycidyl amine type epoxy resins.

Examples of the epoxy group-containing acrylic compound include: homo-and copolymers of monomers with an oxetanyl group.

Examples of glycidyl amides include: glycidyl amide type epoxy compounds.

Examples of the chain aliphatic epoxy compound include: an epoxy group-containing compound obtained by oxidizing a carbon-carbon double bond of an olefin compound.

Examples of the cyclic aliphatic epoxy compound include: an epoxy group-containing compound obtained by oxidizing a carbon-carbon double bond of a cycloolefin compound.

Examples of the bisphenol a type epoxy compound include: jER828, jER1001, jER1002, jER1003, jER1004, jER1007, jER1010 (all trade names, manufactured by Mitsubishi Chemical corporation), Epotohto YD-128 (manufactured by Tokyo Chemical corporation), DER-331, DER-332, and DER-324 (all manufactured by Dow Chemical Company), Epiclone 840 (Epiclon), Epiclone 850, and Epiclone 1050 (all trade names, manufactured by Diesen Chemical corporation), Epomicron R-140(Epomik R-140), Epomicron R-301, and Epomicron R-304 (all trade names, manufactured by Mitsui Chemical corporation).

Examples of the bisphenol F-type epoxy compound include: JeR806, JeR807, and JeR4004P (all trade names, manufactured by Mitsubishi chemical corporation), Epotol YDF-170, Epotol YDF-175S, Epotol YDF-2001 (all trade names, manufactured by Tokyo chemical Co., Ltd.), DER-354 (trade name, manufactured by Dow chemical Co., Ltd.), Epilon 830, and Epilon 835 (all trade names, manufactured by Diesen).

Examples of the bisphenol epoxy compound include: epoxide of 2, 2-bis (4-hydroxyphenyl) -1,1,1,3,3, 3-hexafluoropropane.

Examples of the hydrogenated bisphenol-a type epoxy compound include: ritodol ST-3000(Suntohto ST-3000) (trade name, manufactured by Tokyo Kagaku Kogyo Co., Ltd.), Rikaranin HBE-100 (Rikarelin HBE-100) (trade name, manufactured by Nichikini Kagaku Kogyo Co., Ltd.), and Danacol EX-252(Denacol EX-252) (trade name, manufactured by Nagase Chemtex (Kogyo Co., Ltd.).

Examples of the hydrogenated bisphenol epoxy compound include: hydrogenation of the epoxide of 2, 2-bis (4-hydroxyphenyl) -1,1,1,3,3, 3-hexafluoropropane.

Examples of the brominated bisphenol-a type epoxy compound include: jER5050, jER5051 (both trade names, manufactured by Mitsubishi chemical corporation), Epitottol YDB-360, Epitottol YDB-400 (both trade names, manufactured by Tokyo chemical Co., Ltd.), DER-530, DER-538 (both trade names, manufactured by Dow chemical Co., Ltd.), Epicoclone 152, and Epicoclone 153 (both trade names, manufactured by Diesen).

Examples of the phenol novolac-type epoxy compound include: JeR152, JeR154 (both trade name, manufactured by Mitsubishi chemical corporation), YDPN-638 (trade name, manufactured by Tokyo chemical Co., Ltd.), DEN431, DEN438 (both trade name, manufactured by Dow chemical Co., Ltd.), Epipclone N-770 (trade name, manufactured by Diegon), EPPN-201, and EPPN-202 (both trade name, manufactured by Nippon chemical Co., Ltd.).

Examples of the epoxy compound of the cresol novolak type include: JeR180S75 (trade name, manufactured by Mitsubishi chemical corporation), YDCN-701, YDCN-702 (both trade names, manufactured by Tokyo chemical Co., Ltd.), Epiplone N-665, Epiplone N-695 (both trade names, manufactured by Diesen (stockpile)), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, and EOCN-1027 (both trade names, manufactured by Nippon chemical Co., Ltd.).

Examples of the bisphenol a novolac-type epoxy compound include: JeR157S70 (trade name, manufactured by Mitsubishi chemical corporation), and Aiipclone N-880 (trade name, manufactured by Dietson).

Examples of the epoxy compound having a naphthalene skeleton include: iclone HP-4032, Iclone HP-4700, Iclone HP-4770 (all trade names, manufactured by Diegon, Inc.), and NC-7000 (trade name, manufactured by Nippon Chemicals, Inc.).

Examples of the aromatic polyglycidyl ether compound include: hydroquinone diglycidyl ether (the following formula EP-1), catechol diglycidyl ether (the following formula EP-2), resorcinol diglycidyl ether (the following formula EP-3), 2- [4- (2, 3-epoxypropoxy) phenyl ] -2- [4- [1, 1-bis [4- ([2, 3-epoxypropoxy ] phenyl) ] ethyl ] phenyl ] propane (the following formula EP-4), tris (4-glycidyloxyphenyl) methane (the following formula EP-5), jER1031S, jER1032H60 (both trade names, manufactured by Mitsubishi chemical Co., Ltd.), Taktische-742 (trade name, manufactured by Tao chemical Co., Ltd.), Dana KelEX-201 (trade name, manufactured by Daxan Kazakura chemical Co., Ltd.), DPPN-503, DPPN-502H, DPPN-501H, NC6000 (both trade name, manufactured by Nippon Chemicals (parts), Ltd.), Permoya VG3101L (trade name, manufactured by Mitsui Chemicals (parts), Ltd.), a compound represented by the following formula EP-6, and a compound represented by the following formula EP-7.

Examples of the dicyclopentadiene phenol type epoxy compound include: taktius-556 (trade name, manufactured by Dow chemical Co., Ltd.), and Ipecan HP-7200 (trade name, manufactured by Diegon (Ltd.)).

Examples of the alicyclic diglycidyl ether compound include: cyclohexanedimethanol diglycidyl ether compound, and licarpanew DME-100 (trade name, manufactured by Nissian chemical Co., Ltd.).

Examples of the aliphatic polyglycidyl ether compound include: ethylene glycol diglycidyl ether (the following formula EP-8), diethylene glycol diglycidyl ether (the following formula EP-9), polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether (the following formula EP-10), tripropylene glycol diglycidyl ether (the following formula EP-11), polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether (the following formula EP-12), 1, 4-butanediol diglycidyl ether (the following formula EP-13), 1, 6-hexanediol diglycidyl ether (the following formula EP-14), dibromoneopentyl glycol diglycidyl ether (the following formula EP-15), danakl EX-810, danakl EX-851, danakl EX-8301, danakl EX-911, danakl EX-920, danakl EX-931, and mixtures thereof, Daneker EX-211, daneker EX-212, daneker EX-313 (both trade names and chanozheng (stock)), DD-503 (trade name, adieka (ADEKA) (stock)), licarbazexin W-100 (trade name, xinidai (stock)), 1,3,5, 6-tetraglycidyl-2, 4-hexanediol (formula EP-16), glycerol polyglycidyl ether, sorbitol polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, daneker EX-313, daneker EX-611, daneker EX-321, and daneker EX-411 (both trade names and chanozheng (stock)).

Examples of the polysulfide-type diglycidyl ether compound include: FLDP-50 and FLDP-60 (both trade names, manufactured by Toray Thiokol (Toray Thiokol)).

Examples of the diphenolic epoxy compound include: YX-4000, YL-6121H (both trade name, manufactured by Mitsubishi chemical corporation), NC-3000P, and NC-3000S (both trade name, manufactured by Nippon Chemicals).

Examples of the diglycidyl ester compound include: diglycidyl terephthalate (the following formula EP-17), diglycidyl phthalate (the following formula EP-18), bis (2-methyloxetanylmethyl) phthalate (the following formula EP-19), diglycidyl hexahydrophthalate (the following formula EP-20), a compound represented by the following formula EP-21, a compound represented by the following formula EP-22, and a compound represented by the following formula EP-23.

Examples of the glycidyl ester epoxy compound include: jER871 and jER872 (both trade names, manufactured by mitsubishi chemical (stock)), aibon 200 and aibon 400 (both trade names, manufactured by dear (stock)), dankee EX-711, and dankee EX-721 (both trade names, manufactured by zala chemical (stock)).

Examples of the polyglycidyl amine compound include: n, N-diglycidylaniline (the following formula EP-24), N, N-diglycidy-O-toluidine (the following formula EP-25), N, N-diglycidy-m-toluidine (the following formula EP-26), N, N-diglycidy-2, 4, 6-tribromoaniline (the following formula EP-27), 3- (N, N-diglycidy) aminopropyltrimethoxysilane (the following formula EP-28), N, N, O-triglycidyl-p-aminophenol (the following formula EP-29), N, N, O-triglycidyl-m-aminophenol (the following formula EP-30), N, N, N ', N ' -tetraglycidyl-4, 4' -diaminodiphenylmethane (the following formula EP-31), N, N, N ', N' -tetraglycidyl-m-xylylenediamine (Fertrad-X) (trade name, manufactured by Mitsubishi gas chemical Co., Ltd.), the following formula EP-32), 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane (Fertrad-C (trade name, manufactured by Mitsubishi gas chemical Co., Ltd.), the following formula EP-33), 1, 4-bis (N, N-diglycidylaminomethyl) cyclohexane (following formula EP-34), 1, 3-bis (N, N-diglycidylamino) cyclohexane (following formula EP-35), 1, 4-bis (N, N-diglycidylamino) cyclohexane (following formula EP-36), 1, 3-bis (N, n-diglycidylamino benzene (the following formula EP-37), 1, 4-bis (N, N-diglycidylamino) benzene (the following formula EP-38), 2, 6-bis (N, N-diglycidylaminomethyl) bicyclo [2.2.1] heptane (the following formula EP-39), N, N, N ', N' -tetraglycidyl-4, 4 '-diaminodicyclohexylmethane (the following formula EP-40), 2' -dimethyl- (N, N, N ', N' -tetraglycidyl) -4,4 '-diaminobiphenyl (the following formula EP-41), N, N, N', N '-tetraglycidyl-4, 4' -diaminodiphenyl ether (the following formula EP-42), 1,3, 5-tris (4- (N, N-diglycidylamino) aminophenoxy) benzene (the following formula EP-43), 2,4,4' -tris (N, N-diglycidylamino) diphenyl ether (the following formula EP-44), tris (4- (N, N-diglycidylamino) aminophenyl) methane (the following formula EP-45), 3,4,3',4' -tetrakis (N, N-diglycidylamino) biphenyl (the following formula EP-46), 3,4,3',4' -tetrakis (N, N-diglycidylamino) diphenyl ether (the following formula EP-47), a compound represented by the following formula EP-48, and a compound represented by the following formula EP-49.

Examples of the homopolymer of the monomer having an oxetanyl group include polyglycidyl methacrylate. Examples of the copolymer of the monomer having an oxetanyl group include: n-phenylmaleimide-glycidyl methacrylate copolymer, N-cyclohexylmaleimide-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer, 3-ethyl-3-oxetanyl methacrylate-glycidyl methacrylate copolymer, and styrene-glycidyl methacrylate copolymer.

Examples of the monomer having an oxetanyl group include: glycidyl (meth) acrylate, 3, 4-epoxycyclohexyl (meth) acrylate, and methyl glycidyl (meth) acrylate.

Examples of the monomer other than the monomer having an oxetanyl group in the copolymer of the monomer having an oxetanyl group include: (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, styrene, methylstyrene, chloromethylstyrene, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, N-cyclohexylmaleimide, and N-phenylmaleimide.

Examples of glycidyl isocyanurate include: 1,3, 5-triglycidyl-1, 3, 5-triazine-2, 4,6- (1H,3H,5H) -trione (the following formula EP-50), 1, 3-diglycidyl-5-allyl-1, 3, 5-triazine-2, 4,6- (1H,3H,5H) -trione (the following formula EP-51), and an isocyanurate type epoxy resin.

Examples of the chain aliphatic epoxy compound include: epoxidized polybutadiene, and eboard PB3600(Epolead PB3600) (trade name, manufactured by cellosolve (Daicel) (stock)).

Examples of the cyclic aliphatic epoxy compound include: 3, 4-epoxycyclohexenylmethyl-3 ',4' -epoxycyclohexenecarboxylate (Silohexanide 2021(Celloxide2021) (manufactured by Dacello (Co.)), the following formula EP-52), 2-methyl-3, 4-epoxycyclohexylmethyl-2 ' -methyl-3 ',4' -epoxycyclohexylcarboxylate (the following formula EP-53), 2, 3-epoxycyclopentane-2 ',3' -epoxycyclopentanemether (the following formula EP-54), epsilon-caprolactone-modified 3, 4-epoxycyclohexylmethyl-3 ',4' -epoxycyclohexanecarboxylate, 1,2:8, 9-diepoxy limonene (Celloxide3000 (trade name, manufactured by Dacello (Co.)), the following formula EP-55), compounds represented by The following formula EP-56, CY-175, CY-177, CY-179 (all trade names, manufactured by Ciba-Geigy Chemical Corp., available from Hensman, Japan) (parts), EHPD-3150 (trade name, manufactured by Dacellosolve), and cyclic aliphatic type epoxy resins.

The epoxy compound is preferably at least one of a polyglycidyl amine compound, a bisphenol A novolac type epoxy compound, a cresol novolac type epoxy compound, and a cycloaliphatic type epoxy compound, and more preferably N, N, N ', N ' -tetraglycidyl-m-xylylenediamine, 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N ' -tetraglycidyl-4, 4' -diaminodiphenylmethane, trade name "Fe Kelmethylene VG 3101L", 3, 4-epoxycyclohexenylmethyl-3 ',4' -epoxycyclohexene carboxylate, N-phenylmaleimide-glycidyl methacrylate copolymer, N, N, O-triglycidyl-p-aminophenol, a mixture thereof, and a mixture thereof, One or more of bisphenol A novolac type epoxy compounds and cresol novolac type epoxy compounds.

For example, the liquid crystal aligning agent of the present invention may further contain various additives. Examples of the various additives include a high molecular compound and a low molecular compound other than polyamic acid and its derivative, and they can be selected and used for each purpose.

The polymer compound may be a polymer compound soluble in an organic solvent. From the viewpoint of controlling the electrical characteristics or alignment properties of the formed liquid crystal alignment film, it is preferable to add such a polymer compound to the liquid crystal alignment agent of the present invention. Examples of the polymer compound include: polyamides, polyurethanes, polyureas, polyesters, polyepoxides, polyester polyols, silicone modified polyurethanes, and silicone modified polyesters.

Examples of the low-molecular compound include 1) a surfactant which can achieve the above object when the coatability is desired to be improved, 2) an antistatic agent when the antistatic property is desired to be improved, 3) a silane coupling agent or a titanium-based coupling agent when the adhesion to a substrate is desired to be improved, and 4) an imidization catalyst when imidization is performed at a low temperature.

Examples of the silane coupling agent include: vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyltrimethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, m-aminophenyltrimethoxysilane, m-aminophenyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, p-aminophenyltriethoxysilane, m-aminophenyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-chloropropylmethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, p-glycidoxypropyltrimethoxysilane, p-glycidyloxypropyltrimethoxysilane, p-methoxysilane, N-glycidoxypropyltrimethoxysilane, N-methoxysilane, N-glycidoxypropyltrimethoxysilane, 2-methoxysilane, and a, N- (1, 3-dimethylbutylidene) -3- (triethoxysilyl) -1-propylamine, and N, N' -bis [3- (trimethoxysilyl) propyl ] ethylenediamine. A preferred silane coupling agent is 3-aminopropyltriethoxysilane.

Examples of the imidization catalyst include: aliphatic amines such as trimethylamine, triethylamine, tripropylamine, and tributylamine; aromatic amines such as N, N-dimethylaniline, N-diethylaniline, methyl-substituted aniline, and hydroxy-substituted aniline; and cyclic amines such as pyridine, methyl-substituted pyridine, hydroxy-substituted pyridine, quinoline, methyl-substituted quinoline, hydroxy-substituted quinoline, isoquinoline, methyl-substituted isoquinoline, hydroxy-substituted isoquinoline, imidazole, methyl-substituted imidazole, and hydroxy-substituted imidazole. The imidization catalyst is preferably one or more selected from the group consisting of N, N-dimethylaniline, o-hydroxyaniline, m-hydroxyaniline, p-hydroxyaniline, o-hydroxypyridine, m-hydroxypyridine, p-hydroxypyridine, and isoquinoline.

The silane coupling agent is added in an amount of usually 0 to 20 wt%, preferably 0.1 to 10 wt%, based on the total weight of the polyamic acid or derivative thereof.

The amount of the imidization catalyst added is usually 0.01 to 5 equivalents, preferably 0.05 to 3 equivalents, relative to the carbonyl group of the polyamic acid or its derivative.

The addition amount of the other additives varies depending on the use thereof, but is generally 0 to 100 wt%, preferably 0.1 to 50 wt% of the total weight of the polyamic acid or derivative thereof.

The polyamic acid or the derivative thereof of the present invention can be produced in the same manner as a known polyamic acid or a derivative thereof used for formation of a film of polyimide. The total amount of the tetracarboxylic dianhydride is preferably approximately equimolar to the total number of moles of the diamine (the molar ratio is about 0.9 to 1.1).

The molecular weight of the polyamic acid or derivative thereof of the present invention is preferably 7,000 to 500,000, more preferably 10,000 to 200,000, in terms of a weight average molecular weight (Mw) in terms of polystyrene. The molecular weight of the polyamic acid or its derivative can be determined by measurement using a Gel Permeation Chromatography (GPC) method.

The polyamic acid or derivative thereof of the present invention can be confirmed for its presence by: the solid content obtained by precipitating the polyamic acid or derivative thereof of the present invention in a large amount of a poor solvent is analyzed by Infrared (IR) or Nuclear Magnetic Resonance (NMR). In addition, the monomers used can be confirmed by: the polyamic acid or a derivative thereof is decomposed using an aqueous solution of a strong base such as KOH or NaOH, and an extract extracted from the decomposed product thereof using an organic solvent is analyzed by Gas Chromatography (GC), High Performance Liquid Chromatography (HPLC), or Gas Chromatography-Mass Spectrometry (GC-MS).

In addition, the liquid crystal aligning agent of the present invention may further contain a solvent, for example, from the viewpoint of coatability of the liquid crystal aligning agent or adjustment of the concentration of the polyamic acid or the derivative thereof. The solvent is not particularly limited, and any solvent can be used as long as it has an ability to dissolve the polymer component. The solvent widely includes solvents generally used in the production process or application of polymer components such as polyamic acid and soluble polyimide, and can be appropriately selected depending on the purpose of use. The solvent may be one or a mixture of two or more kinds.

Examples of the solvent include a solvent that is a lipophilic solvent for the polyamic acid or the derivative thereof, and another solvent for the purpose of improving coatability.

Examples of the aprotic polar organic solvent which is a solvent-philic solvent for the polyamic acid or a derivative thereof include: lactones such as N-methyl-2-pyrrolidone, dimethylimidazolidinone (dimethylimidazolidinone), N-methylcaprolactam, N-methylpropanamide, N-dimethylacetamide, dimethyl sulfoxide, N-dimethylformamide, N-diethylformamide, diethylacetamide, and γ -butyrolactone.

Particularly, at least one solvent selected from the group consisting of alcohols, ethers, and ketones is preferably used as the other solvent for the purpose of improving coatability.

As the alcohol, there may be mentioned: butyl cellosolve (ethylene glycol monobutyl ether), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether, 1-butoxy-2-propanol, 2- (2-methoxypropoxy) propanol, ethyl lactate, methyl lactate, propyl lactate, butyl lactate, and the like.

As the ether, there may be mentioned: alkylene glycol dialkyl ethers such as ethylene glycol dimethyl ether and ethylene glycol diethyl ether; dialkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol butyl methyl ether; dialkylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol monoethyl ether; alkylene glycol alkyl ether acetates such as ethylene glycol n-butyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether acetate, and propylene glycol monobutyl ether acetate; propylene glycol monoalkyl ether propionates such as propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, and propylene glycol monobutyl ether propionate; cyclic ethers such as tetrahydrofuran, and the like.

As the ketone, there can be mentioned: methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl isoamyl ketone, diisobutyl ketone, methyl-3-methoxypropionate, and the like.

Among these solvents, N-methyl-2-pyrrolidone, dimethylimidazolidinone, γ -butyrolactone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, diethylene glycol diethyl ether, and 1-butoxy-2-propanol are particularly preferable.

The concentration of the polyamic acid or derivative thereof in the alignment agent of the present invention is preferably 0.1 to 40 wt%. When the alignment agent is applied to a substrate, the polyamic acid contained may need to be diluted with a solvent in advance in order to adjust the film thickness.

The concentration of the solid content in the alignment agent of the present invention is not particularly limited, and an optimum value may be selected in combination with the various coating methods described below. In general, in order to suppress unevenness and pinholes in coating, it is preferably 0.1 to 30% by weight, more preferably 1 to 10% by weight, based on the weight of the varnish.

The viscosity of the liquid crystal aligning agent of the present invention varies depending on the method of application, the concentration of the polyamic acid or derivative thereof, the type of the polyamic acid or derivative thereof used, and the type and ratio of the solvent. For example, when the coating is performed by a printer, the coating is 5 to 100 mPas (more preferably 10 to 80 mPas). When the viscosity is less than 5 mPas, it becomes difficult to obtain a sufficient film thickness; when the viscosity exceeds 100 mPas, the print unevenness is large. When the coating is performed by spin coating, it is preferably 5 to 200 mPas (more preferably 10 to 100 mPas). When the coating is performed using an inkjet coating apparatus, it is preferably 5 to 50mPa · s (more preferably 5 to 20mPa · s). The viscosity of the liquid crystal aligning agent can be measured by a rotational viscosity measuring method, for example, a rotational viscometer (TVE-20L manufactured by Toyobo industries, Ltd.) (measurement temperature is 25 ℃).

The liquid crystal alignment film of the present invention will be described in detail. The liquid crystal alignment film of the present invention is a film formed by heating a coating film of the liquid crystal alignment agent of the present invention. The liquid crystal alignment film of the present invention can be obtained by a general method for producing a liquid crystal alignment film from a liquid crystal aligning agent. For example, the liquid crystal alignment film of the present invention can be obtained by performing a step of forming a coating film of the liquid crystal alignment agent of the present invention, a step of performing heat drying, and a step of performing heat baking. In the liquid crystal alignment film of the present invention, anisotropy can be imparted to the film obtained through the heat drying step and the heat calcining step by rubbing treatment as described later, if necessary. Alternatively, if necessary, anisotropy may be imparted by irradiating light after the coating step, the heat-drying step, or after the heat-calcining step. In addition, the liquid crystal Alignment film can also be used as a liquid crystal Alignment film for Vertical Alignment (VA) without rubbing treatment.

The coating film can be formed by applying the liquid crystal aligning agent of the present invention to a substrate in a liquid crystal display device, in the same manner as in the production of a general liquid crystal alignment film. Examples of the substrate include glass substrates provided with electrodes such as Indium Tin Oxide (ITO), Indium zinc Oxide (In2O3-ZnO, IZO), Indium gallium zinc Oxide (In-Ga-ZnO4, IGZO) electrodes, color filters, and the like.

As a method for applying the liquid crystal aligning agent to the substrate, a spinner method, a printing method, a dipping method, a dropping method, an ink jet method, and the like are generally known. These methods can be equally applied to the present invention.

As the heat drying step, a method of performing heat treatment in an oven or an infrared oven, a method of performing heat treatment on a hot plate, and the like are generally known. The heat-drying step is preferably carried out at a temperature in a range where the solvent is evaporable, and more preferably at a relatively low temperature with respect to the temperature in the heat-calcining step. Specifically, the heating and drying temperature is preferably in the range of 30 to 150 ℃, more preferably in the range of 50 to 120 ℃.

The heating and calcining step may be performed under conditions required for the polyamic acid or derivative thereof to exhibit dehydration-ring closure reaction. As a method for baking the coating film, a method of performing a heating treatment in an oven or an infrared oven, a method of performing a heating treatment on a hot plate, and the like are generally known. These methods can be equally applied to the present invention. It is usually carried out at a temperature of about 100 to 300 ℃ for 1 minute to 3 hours, preferably 120 to 280 ℃, and more preferably 150 to 250 ℃.

In the method for forming a liquid crystal alignment film of the present invention, a known forming method such as a rubbing method or a photo-alignment method can be suitably used as a method for imparting anisotropy to an alignment film in order to align a liquid crystal in one direction with respect to a horizontal direction and/or a vertical direction.

The liquid crystal alignment film of the present invention using the rubbing method may be formed through the following steps: the method for producing a liquid crystal display device includes a step of coating the liquid crystal alignment agent of the present invention on a substrate, a step of heating and drying the substrate coated with the alignment agent, a step of heating and baking the film, and a step of rubbing the film.

The rubbing treatment may be performed in the same manner as in a rubbing treatment used for an alignment treatment of a liquid crystal alignment film in general, and may be performed under conditions that can obtain a sufficient retardation in the liquid crystal alignment film of the present invention. Preferably, the press-in amount of the bristles is 0.2mm to 0.8mm, the table moving speed is 5mm/sec to 250mm/sec, and the roller rotating speed is 500rpm to 2,000 rpm.

The method for forming the liquid crystal alignment film of the present invention by the photo-alignment method will be described in detail. The liquid crystal alignment film of the present invention using the photo-alignment method can be formed by: after the coating film is heated and dried, the coating film is irradiated with linearly polarized light or unpolarized light of radiation to impart anisotropy to the coating film, and then the film is heated and calcined. Alternatively, the coating film may be formed by heating and drying the coating film, heating and baking the coating film, and then irradiating the coating film with linearly polarized light or unpolarized light of radiation. From the viewpoint of orientation, it is preferable to perform the irradiation step of the radiation before the heating and calcining step.

Further, in order to improve the liquid crystal alignment ability of the liquid crystal alignment film, the coating film may be heated and irradiated with linearly polarized light or unpolarized light of radiation. The irradiation with radiation may be performed in the step of heating and drying the coating film, or in the step of heating and calcining the coating film, or may be performed between the heating and drying step and the heating and calcining step. The heating and drying temperature in the above step is preferably in the range of 30 to 150 ℃, more preferably 50 to 120 ℃. And the heating and calcining temperature in the step is preferably in the range of 30-300 ℃, and more preferably in the range of 50-250 ℃.

As the radiation, ultraviolet rays or visible light including light having a wavelength of, for example, 150nm to 800nm, preferably 300nm to 400nm, can be used. Alternatively, linearly polarized or unpolarized light may be used. These lights are not particularly limited as long as they can impart liquid crystal alignment ability to the coating film, and when strong alignment regulating force is to be exerted on the liquid crystal, linear polarization is preferable.

The liquid crystal alignment film of the present invention can exhibit high liquid crystal alignment ability even under low-energy light irradiation. The irradiation amount of the linearly polarized light in the radiation irradiation step is preferably 0.05J/cm²～20J/cm²More preferably 0.5J/cm²～10J/cm². The wavelength of the linearly polarized light is preferably 200nm to 400nm, more preferably 200nm to 400nm300 nm-400 nm. The irradiation angle of the linearly polarized light to the film surface is not particularly limited, and when it is desired to exhibit a strong alignment regulating force to the liquid crystal, it is preferable to make the alignment treatment time as perpendicular as possible to the film surface from the viewpoint of shortening the alignment treatment time. In addition, the liquid crystal alignment film of the present invention can align liquid crystals in a direction perpendicular to the polarization direction of linearly polarized light by irradiating the linearly polarized light.

When the pretilt angle is to be expressed, the light irradiated to the film may be linearly polarized light or unpolarized light, as described above. In the case where a pretilt angle is to be exhibited, the irradiation amount of light with which the film is irradiated is preferably 0.05J/cm²～20J/cm²Particularly preferably 0.5J/cm²～10J/cm²The wavelength is preferably 250nm to 400nm, particularly preferably 300nm to 380 nm. In the case where a pretilt angle is to be expressed, the irradiation angle of light with respect to the film surface to be irradiated to the film is not particularly limited, and is preferably 30 degrees to 60 degrees from the viewpoint of shortening the alignment treatment time.

As the light source used in the step of irradiating linearly polarized light or unpolarized light of radiation, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a Deep ultraviolet (Deep UV) lamp, a halogen lamp, a metal halide lamp, a high power metal halide lamp, a xenon lamp, a mercury xenon lamp, an excimer lamp, a KrF excimer laser, a fluorescent lamp, a Light Emitting Diode (LED) lamp, a sodium lamp, a microwave excited electrodeless lamp, or the like can be used without limitation.

The liquid crystal alignment film of the present invention can be suitably obtained by a method further comprising the steps other than the above-described steps. For example, the liquid crystal alignment film of the present invention does not require a step of cleaning the film after firing or irradiation with a cleaning liquid, but the cleaning step may be provided according to the case of other steps.

Examples of the cleaning method using the cleaning liquid include: brushing, spraying, steam cleaning, ultrasonic cleaning, or the like. These methods may be carried out alone or in combination. As the cleaning liquid, there can be used: examples of the cleaning solution include, but are not limited to, pure water, various alcohols such as methanol, ethanol, and isopropanol, aromatic hydrocarbons such as benzene, toluene, and xylene, halogen solvents such as methylene chloride, and ketones such as acetone and methyl ethyl ketone. Of course, a sufficiently purified cleaning solution having a small amount of impurities can be used as the cleaning solution. Such a cleaning method can also be applied to the cleaning step in forming the liquid crystal alignment film of the present invention.

In order to improve the liquid crystal alignment ability of the liquid crystal alignment film of the present invention, annealing treatment with heat or light may be applied before and after the heating and calcining step, before and after the rubbing step, or before and after irradiation with polarized or unpolarized radiation. In the annealing treatment, the annealing temperature is 30-180 ℃, preferably 50-150 ℃, and the time is preferably 1 minute-2 hours. Examples of the annealing light used for the annealing treatment include a UV lamp, a fluorescent lamp, and an LED lamp. The irradiation amount of light is preferably 0.3J/cm²～10J/cm²。

The thickness of the liquid crystal alignment film of the present invention is not particularly limited, but is preferably 10nm to 300nm, more preferably 30nm to 150 nm. The film thickness of the liquid crystal alignment film of the present invention can be measured by a known film thickness measuring apparatus such as a profilometer or an ellipsometer.

The liquid crystal alignment film of the present invention is characterized by having particularly large anisotropy of alignment. The magnitude of such anisotropy can be evaluated by the method using polarized IR described in Japanese patent laid-open No. 2005-275364 and the like. As shown in the following examples, evaluation can also be performed by a method using ellipsometry (ellipsometry). In detail, a spectroscopic ellipsometer may be used to measure the retardation value of the liquid crystal alignment film. The retardation value of the film increases in proportion to the degree of orientation of the polymer main chain. That is, a film having a large retardation value has a large degree of alignment, and when the alignment film of the present invention is used as a liquid crystal alignment film, it can be considered that the alignment film having a larger anisotropy has a large alignment regulating force for a liquid crystal composition.

The liquid crystal alignment film of the present invention can be suitably used for a liquid crystal display device of a transverse electric field system. In the case of the liquid crystal display element used in the lateral electric field system, the smaller the Pt angle and the higher the liquid crystal alignment ability, the higher the black display level in the dark state and the higher the contrast. The Pt angle is preferably 0.1 DEG or less.

The liquid crystal alignment film of the present invention can be used for alignment control of an optical compensation material or other all liquid crystal materials, in addition to alignment uses of a liquid crystal composition for a liquid crystal display. In addition, the alignment film of the present invention has large anisotropy, and thus can be used alone for optical compensation material applications.

The liquid crystal display device of the present invention will be described in detail.

The invention provides a liquid crystal display element, which comprises a pair of substrates arranged oppositely, electrodes formed on one or both of the opposite surfaces of the pair of substrates, liquid crystal orientation films formed on the opposite surfaces of the pair of substrates, and a liquid crystal layer formed between the pair of substrates, wherein the liquid crystal orientation films are the orientation films of the invention.

The electrode is not particularly limited as long as it is formed on one surface of the substrate. Examples of such an electrode include ITO and a metal vapor deposited film. The electrode may be formed on the entire surface of one surface of the substrate, or may be formed in a desired patterned shape, for example. Examples of the desired shape of the electrode include a comb-like or zigzag structure. The electrode may be formed on one of the pair of substrates, or may be formed on both substrates. The form of the electrode varies depending on the type of the liquid crystal display element, and for example, in the case of an IPS liquid crystal display element, the electrode is disposed on one of the pair of substrates, and in the case of another liquid crystal display element, the electrode is disposed on both of the pair of substrates. Forming the liquid crystal alignment film on the substrate or the electrode.

The liquid crystal layer is formed so as to sandwich the liquid crystal composition between the pair of substrates facing each other, on which the liquid crystal alignment film is formed. In the process of forming the liquid crystal layer, spacers may be interposed between the pair of substrates to form an appropriate interval, such as fine particles or a resin sheet, as necessary.

The liquid crystal composition is not particularly limited, and various liquid crystal compositions having positive or negative dielectric anisotropy can be used. Preferred liquid crystal compositions having positive dielectric anisotropy include: liquid crystal compositions disclosed in Japanese patent 3086228, Japanese patent 2635435, Japanese patent Kokai Hei 5-501735, Japanese patent Kokai Hei 8-157826, Japanese patent Kokai Hei 8-231960, Japanese patent Kokai Hei 9-241644(EP885272A1), Japanese patent Kokai Hei 9-302346(EP806466A1), Japanese patent Kokai Hei 8-199168(EP722998A1), Japanese patent Kokai Hei 9-235552, Japanese patent Kokai Hei 9-255956, Japanese patent Kokai Hei 9-241643(EP885271A1), Japanese patent Kokai Hei 10-204016(EP844229A1), Japanese patent Kokai Hei 10-204436, Japanese patent Kokai Hei 10-231482, Japanese patent Kokai 2000-087040, Japanese patent Kokai-2001-48822 and the like.

The liquid crystal composition having positive or negative dielectric anisotropy may be used without any influence by adding at least one optically active compound.

The liquid crystal composition having negative dielectric anisotropy will be described. The liquid crystal composition having negative dielectric anisotropy includes, for example, a composition containing, as the component 1, at least one liquid crystal compound selected from the group of liquid crystal compounds represented by the following formula (NL-1).

Here, R^1aAnd R^2aIndependently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen is substituted by fluorine, ring A²And ring B²Independently is 1, 4-cyclohexylene, tetrahydropyran (tetrahydropyran) -2, 5-diyl, 1, 3-dioxane-2, 5-diyl, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 2, 5-difluoro-1, 4-phenylene, 2, 3-difluoro-1, 4-phenylene, 2-fluoro-3-chloro-1, 4-phenylene, 2, 3-difluoro-6-methyl-1, 4-phenylene, 2, 6-naphthalenediyl, or 7, 8-difluorochromane (chromane) -2, 6-diyl, where ring A is²And ring B²At least one of (A) and (B) is 2, 3-difluoro-1, 4-phenylene, 2-fluoro-3-chloro-1, 4-phenylene, 2, 3-difluoro-6-methyl-1, 4-phenylene, or 7, 8-difluorochroman-2, 6-diyl, Z¹Independently is a single bond, - (CH)₂)₂-、-CH₂O-, -COO-, or-CF₂O-, j is 1,2, or 3, and when j is 2 or 3, any two rings A²May be the same or different, and any two Z's may be present¹May be the same or different.

The ring A is preferable for improving the dielectric anisotropy²And ring B²2, 3-difluoro-1, 4-phenylene or tetrahydropyran-2, 5-diyl, respectively, ring A being preferred for the purpose of reducing the viscosity²And ring B²Are each 1, 4-cyclohexylene.

Z is preferably selected for improving the dielectric anisotropy¹is-CH₂O-for lowering the viscosity, preferred is Z¹Is a single bond.

J is preferably 1 in order to lower the lower limit temperature, and j is preferably 2 in order to raise the upper limit temperature.

Specific examples of the liquid crystal compound of the formula (NL-1) include compounds represented by the following formulae (NL-1-1) to (NL-1-32).

Here, R^1aAnd R^2aIndependently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen is substituted by fluorine, ring A²¹Ring A²²Ring A²³Ring B²¹And ring B²²Independently of one another are 1, 4-cyclohexylene or 1, 4-phenylene, Z¹¹And Z¹²Independently is a single bond, - (CH)₂)₂-、-CH₂O-, or-COO-.

R is preferably selected to improve stability to ultraviolet light or heat^1aAnd R^2aIs an alkyl group having 1 to 12 carbon atoms or R is preferably R for improving the absolute value of dielectric anisotropy^1aAnd R^2aIs an alkoxy group having 1 to 12 carbon atoms.

Preferred alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl. Further more preferred alkyl groups for viscosity reduction are ethyl, propyl, butyl, pentyl or heptyl.

Preferred alkoxy groups are methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, or heptoxy. Further more preferred alkoxy groups for viscosity reduction are methoxy or ethoxy.

Preferred alkenyl groups are vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl. Still more preferred alkenyl groups for viscosity reduction are vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl. The preferred steric configuration (steric configuration) of the-CH ═ CH-in these alkenyl groups depends on the position of the double bond. Among alkenyl groups such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl, 3-hexenyl, the trans form is preferable from the viewpoint of lowering the viscosity and the like. Among alkenyl groups such as 2-butenyl, 2-pentenyl and 2-hexenyl, cis-form is preferable. Among these alkenyl groups, a linear alkenyl group is preferable as compared with a branched one.

Preferred examples of alkenyl groups in which at least one hydrogen is substituted by fluorine are 2, 2-difluorovinyl, 3-difluoro-2-propenyl, 4-difluoro-3-butenyl, 5-difluoro-4-pentenyl, and 6, 6-difluoro-5-hexenyl. Further more preferable examples for lowering the viscosity are 2, 2-difluorovinyl group and 4, 4-difluoro-3-butenyl group.

For viscosity reduction, ring A is preferred²¹Ring A²²Ring A²³Ring B²¹And a ringB²²Are each 1, 4-cyclohexylene.

Z is preferably selected for improving the dielectric anisotropy¹¹And Z¹²is-CH₂O-for lowering the viscosity, preferred is Z¹¹And Z¹²Is a single bond.

In the liquid crystal composition having negative dielectric anisotropy, the compound (NL-1) which is preferable as the component 1 is a compound (NL-1-1), a compound (NL-1-4), a compound (NL-1-7) or a compound (NL-1-32).

Preferable examples of the liquid crystal composition having negative dielectric anisotropy include Japanese patent laid-open publication No. Sho 57-114532, Japanese patent laid-open publication No. Hei 2-4725, Japanese patent laid-open publication No. Hei 4-224885, Japanese patent laid-open publication No. Hei 8-40953, Japanese patent laid-open publication No. Hei 8-104869, Japanese patent laid-open publication No. Hei 10-168076, Japanese patent laid-open publication No. Hei 10-168453, Japanese patent laid-open publication No. Hei 10-236989, Japanese patent laid-open publication No. Hei 10-236990, Japanese patent laid-open publication No. Hei 10-236992, Japanese patent laid-open publication No. Hei 10-236993, Japanese patent laid-open publication No. Hei 10-236994, Japanese patent laid-open publication No. Hei 10-237000, Japanese patent laid-open publication No. Hei 10-237004, Japanese patent laid-open publication No. Hei 10-237024, Japanese patent laid-open publication No. Hei 10-237035, Japanese patent laid-open publication No. Hei 10-237075, Japanese patent laid-open publication No. Hei 10-237076, Japanese patent laid-open publication No. Hei 10-3583, Japanese patent laid-10-237075, Japanese patent laid-open publication No. Hei 10-3948, Liquid crystal compositions disclosed in Japanese patent laid-open No. Hei 10-237448(EP967261A1), Japanese patent laid-open No. Hei 10-287874, Japanese patent laid-open No. Hei 10-287875, Japanese patent laid-open No. Hei 10-291945, Japanese patent laid-open No. Hei 11-029581, Japanese patent laid-open No. Hei 11-080049, Japanese patent laid-open No. 2000-containing No. 256307, Japanese patent laid-open No. 2001-containing No. 019965, Japanese patent laid-open No. 2001-containing 072626, Japanese patent laid-open No. 2001-containing No. 192657, Japanese patent laid-open No. 2010-containing No. 037428, International publication No. 2011/024666, International publication No. 2010/072370, Japanese patent laid-open No. 2010-containing No. 537010, Japanese patent laid-open No. 2012-containing No. 077201, Japanese patent laid-open No. 2009-containing No. 084362, and the like.

In addition, for example, from the viewpoint of improving the alignment properties, an additive may be further added to the liquid crystal composition used in the device of the present invention. Such additives include photopolymerizable monomers, optically active compounds, antioxidants, ultraviolet absorbers, pigments, antifoaming agents, polymerization initiators, polymerization inhibitors, and the like.

The most preferable structure of the photopolymerizable monomer or oligomer for improving the alignment of the liquid crystal is a structure represented by the formulae (PM-1-1) to (PM-1-6).

In order to exhibit the effect of determining the tilt direction of the liquid crystal after polymerization, the photopolymerizable monomer or oligomer is preferably 0.01 wt% or more. Further, in order to make the orientation effect of the polymer after polymerization suitable or to prevent the unreacted monomer or oligomer from dissolving out into the liquid crystal after irradiation with ultraviolet rays, it is desirable that 30 wt% or less is used.

An optically active compound is mixed in the composition in order to induce a helical structure of the liquid crystal and impart a twist angle. Examples of such compounds are the compounds (PAC-1-1) to (PAC-1-4).

The preferable proportion of the optically active compound is 5 wt% or less. Still more preferred is a range of 0.01 wt% to 2 wt%.

An antioxidant is mixed in the liquid crystal composition in order to prevent a decrease in specific resistance (specific resistance) due to heating in the atmosphere, or in order to maintain a large voltage holding ratio not only at room temperature but also at a high temperature after the device is used for a long time.

Preferable examples of the antioxidant are a compound (AO-1) wherein w is an integer of 1 to 10, and the like. In the compound (AO-1), w is preferably 1,3,5, 7, or 9. Even more preferably w is 1 or 7. The compound (AO-1) having w of 1 is highly volatile and therefore is effective in preventing a decrease in specific resistance due to heating in the atmosphere. Since the compound (AO-1) having w of 7 has low volatility, it can effectively maintain a large voltage holding ratio not only at room temperature but also at a high temperature after the device is used for a long time. In order to obtain the effect, the preferable ratio of the antioxidant is 50ppm or more, and the preferable ratio of the antioxidant is 600ppm or less so that the upper limit temperature is not lowered or the lower limit temperature is not raised. Still more preferably, the content is in the range of 100ppm to 300 ppm.

Preferable examples of the ultraviolet absorber are benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Further, light stabilizers such as sterically hindered amines are also preferred. The preferable ratio of these absorbents or stabilizers is 50ppm or more in order to obtain the effect, and 10000ppm or less in order not to lower the upper limit temperature or to raise the lower limit temperature. Still more preferably, the ratio is in the range of 100ppm to 10000 ppm.

In order to be suitable for a Guest Host (GH) mode element, a dichroic dye (dichromatic dye) such as an azo dye or an anthraquinone dye is mixed in the composition. The preferable ratio of the pigment is in the range of 0.01 wt% to 10 wt%.

In order to prevent foaming, an antifoaming agent such as dimethyl silicone oil or methylphenyl silicone oil is mixed in the composition. The preferable ratio of the defoaming agent is 1ppm or more for obtaining the effect thereof, and the preferable ratio of the defoaming agent is 1000ppm or less for preventing the display failure. Still more preferably, the content is in the range of 1ppm to 500 ppm.

Polymerizable compounds can be mixed in the composition in order to adapt the elements of the Polymer Stabilized Alignment (PSA) mode. Preferable examples of the polymerizable compound are compounds having a polymerizable group such as acrylic acid esters, methacrylic acid esters, vinyl compounds, vinyloxy compounds, propenyl ethers, epoxy compounds (oxetane ) and vinyl ketones. Particularly preferred examples are derivatives of acrylates or methacrylates. Examples of such compounds are the compounds (PM-2-1) to (PM-2-9). The preferable proportion of the polymerizable compound is about 0.05 wt% or more for obtaining the effect thereof, and about 10 wt% or less for preventing the display failure. Even more preferred ratios are in the range of about 0.1 wt% to about 2 wt%.

Here, R^3a、R^4a、R^5aAnd R^6aIndependently is acryloyl or methacryloyl, R^7aAnd R^8aIndependently hydrogen, halogen, or alkyl of 1 to 10 carbon atoms, Z¹³、Z¹⁴、Z¹⁵And Z¹⁶Independently a single bond or alkylene of 1 to 12 carbon atoms, at least one-CH₂-may also be substituted by-O-or-CH ═ CH-, s, t, and u are each independently 0, 1, or 2.

As a substance which is easily generated with a radical or ion and is necessary for initiating the chain polymerization reaction, a polymerization initiator may be mixed. For example, as a photopolymerization initiator, brilliant solid (Irgacure)651 (registered trademark), brilliant solid 184 (registered trademark), or daroka (Darocure)1173 (registered trademark) (Ciba Japan corporation, Japan K.K.) is suitable for radical polymerization. The polymerizable compound preferably contains a photopolymerization initiator in the range of 0.1 to 5 wt%. It is particularly preferable to contain the photopolymerization initiator in the range of 1 to 3 wt%.

In free radical polymerization systems, the polymerization inhibitors can be mixed for the following purposes: the polymerization initiator or the monomer reacts rapidly with a radical generated from the monomer to change into a stable radical or a neutral compound, and as a result, the polymerization reaction is stopped. Polymerization inhibitors can be structurally classified into several types. One of them is a stable free radical by itself such as tris-p-nitrophenylmethyl, di-p-fluorophenyl amine, etc., and the other is one which reacts easily with a free radical existing in the polymerization system to become a stable free radical, and is represented by nitro, nitroso, amino, polyhydroxy compound, etc. Representative examples of the latter include hydroquinone, dimethoxybenzene and the like. The preferable proportion of the polymerization inhibitor is 5ppm or more for obtaining the effect thereof, and 1000ppm or less for preventing the display failure. Still more preferably, the content is in the range of 5ppm to 500 ppm.

The liquid crystal display element of the present invention uses a liquid crystal composition having negative dielectric anisotropy, and thus provides a liquid crystal display element having excellent afterimage characteristics and good alignment stability.

[ examples ]

The present invention will be described below with reference to examples. The evaluation methods and compounds used in the examples are as follows.

< evaluation method >

1. Weight average molecular weight (Mw)

The weight average molecular weight of the polyamic acid is determined as follows: the measurement was performed by a GPC method using a 2695 separation Module 2414 differential refractometer (manufactured by Waters), and then converted into polystyrene. The obtained polyamic acid was diluted with a phosphoric acid-Dimethylformamide (DMF) mixed solution (phosphoric acid/DMF 0.6/100: weight ratio) so that the polyamic acid concentration became about 2 wt%. The column was measured using HSPgel RT MB-M (manufactured by Watt) using the mixed solution as a developing solvent under conditions of a column temperature of 50 ℃ and a flow rate of 0.40 mL/min. As the standard polystyrene, TSK standard polystyrene manufactured by Tosoh (stock) was used.

2. Hardness of pencil

According to JIS specification "JIS-K-5400, 8.4, pencil scratch test". The results are expressed as the hardness of the pencil lead. If the pencil hardness is low, peeling or thinning tends to occur, and if the value is greater than 2H, an alignment film in which thinning or the like is less likely to occur can be obtained.

3. Rub resistance test

The abrasion resistance test was performed using an abrasion processing device (manufactured by nippon corporation, manufactured by Iinuma Gauge). The polyimide film coated on the glass substrate was rubbed with a rubbing cloth (with a fur length of 1.9 mm: rayon) under conditions of a fur press-in amount of 0.40mm, a table moving speed of 60mm/sec, and a roller rotating speed of 1000rpm, and the surface was observed with a microscope to confirm whether or not the polyimide film was shaved. The case where the film was not thinned was set to "o", and the case where the film was thinned was set to "x".

4. Foreign matter test

The foreign matter test of the liquid crystal display element described later was performed using a FORCE measuring instrument (FORCE MEASUREMENT) and DS2-50N (manufactured by IMADA, Inc.). A force of 9.8N was applied to the fabricated liquid crystal display element at 60 times/min for 1 minute. The liquid crystal display element was observed with a microscope to confirm the presence or absence of foreign matter after pressurization.

5. Contrast ratio

The contrast of a liquid crystal display element described later was evaluated using a luminance meter (YOKOGAWA) 3298F. The liquid crystal display element was placed under a polarization microscope in a crossed nicols state, and the luminance that became the minimum was measured as black luminance. Next, an arbitrary rectangular wave voltage is applied to the element, and the maximum luminance is measured as white luminance. The value of the white luminance/black luminance is set as a contrast. The contrast was judged to be poor when the contrast was less than 2500, good when the contrast was not less than 2500, and optimal when the contrast was not less than 3000.

6. Alternating Current (AC) afterimage determination

The luminance-voltage characteristics (B-V characteristics) of the liquid crystal display element described later were measured. This was set as the luminance-voltage characteristic before applying stress: b (front). Then, after applying an alternating current of 4.5V and 60Hz to the element for 20 minutes, the element was short-circuited for 1 second, and then the luminance-voltage characteristics (B-V characteristics) were measured again. The luminance-voltage characteristics after stress application were set as: and B (post). Based on these values, the luminance change rate Δ B (%) is estimated using the following equation.

Δ B (%) - (B (rear) -B (front) ]/B (front) (formula AC1)

These measurements were carried out with reference to the manual of International publication No. 2000/43833. It can be said that the smaller the value of Δ B (%) at a voltage of 0.75V, the more suppressed the generation of AC afterimages, and is preferably 3.0% or less.

< tetracarboxylic dianhydride >

< diamine >

< solvent >

NMP: n-methyl-2-pyrrolidone

BC: butyl Cellosolve (ethylene glycol monobutyl ether)

GBL: gamma-butyrolactone

BP: 1-butoxy-2-propanol

EDM: diethylene glycol ethyl methyl ether

BDM: diethylene glycol butyl methyl ether

EDE (electro-less equipment): diethylene glycol diethyl ether

And (3) DIBK: diisobutyl ketone

< additive >

Ad 1: n, N, N ', N ' -tetraglycidyl-4, 4' -diaminodiphenylmethane

Ad 2: 3, 4-Epoxycyclohexenylmethyl-3 ',4' -epoxycyclohexene carboxylate (Celloxide 2021; manufactured by Dailuon)

Ad 3: 1, 4-butanediol diglycidyl ether

Ad 4: 1,3, 5-triglycidyl-1, 3, 5-triazine-2, 4,6- (1H,3H,5H) -triones

Ad 5: 1, 3-bis (4, 5-dihydro-2-oxazolyl) benzene

As the compound of the formula (1-1), a commercially available product (trade name: DA-MGIC; manufactured by four chemical industries, Ltd.) was used as it is. The compound of the formula (1-3) is synthesized according to the method described in Japanese patent laid-open publication No. 2013-163654. The compound of the formula (1-4) is synthesized according to the method described in Japanese patent laid-open publication No. 2013-151443.

[ Synthesis example ] Synthesis of Compound of formula (1-2)

To a 100mL flask equipped with a cooler and a thermometer equipped with a water separator were added 12.8g (49.7mmol) of 1-allyl-3, 5- (2-hydroxyethyl) isocyanurate, 20.0g of toluene, 0.2g (1.0mmol) of p-toluenesulfonic acid, 0.01g (0.1mmol) of methoxyhydroquinone, and 7.8g (109.4mmol) of acrylic acid. The flask was immersed in an oil bath set at 110 ℃ to heat and stir the reaction solution, and the reaction was carried out for 12 hours while removing the generated water from the reaction system. The reaction solution was cooled to room temperature, and insoluble matter in the reaction solution was removed by filtration. The filtrate was washed twice with 20g of a 10% aqueous sodium bicarbonate solution, and then once with 20g of water, and the solvent of the separated organic layer was distilled off under reduced pressure to obtain a solid substance. The obtained solid was purified by silica gel column chromatography (ethyl acetate/hexane: 5/1, v/v) to obtain 9.4g of 1-allyl-3, 5- (2-vinylcarbonyloxyethyl) isocyanurate (yield 52%, purity 97%).

To a 50mL flask equipped with a thermometer, 365mg (1.0mmol) of 1-allyl-3, 5- (2-vinylcarbonyloxyethyl) isocyanurate and 5.0mL of methylene chloride were added. 0.8g (3.0mmol) of 65% m-chloroperoxybenzoic acid was added thereto under cooling in an ice bath, and the mixture was stirred for 1 hour and then for 9 hours at room temperature. 10mL of chloroform and 30mL of a 10% aqueous sodium sulfite solution were added to the reaction mixture, followed by stirring, and the solvent of the separated organic layer was distilled off under reduced pressure. The obtained concentrate was purified by silica gel column chromatography (ethyl acetate/hexane ═ 1/3, v/v) to obtain 301.3mg of N, N' -bis (acryloylethyl) -N ″ -glycidyl isocyanuric acid (1-2) (yield 79%, purity 99%).

EXAMPLE 1 Synthesis of varnish

0.9004g of the compound represented by formula (DI-4-1) and 1.6507g of the compound represented by formula (DI-5-1) (m ═ 1) were added to a 100mL three-necked flask equipped with a stirring blade and a nitrogen gas inlet tube, and 34.0g of N-methyl-2-pyrrolidone (NMP) was added thereto. After the solution was cooled with ice and the temperature was set to 5 ℃, 1.6328g of the compound represented by the formula (PA-1) and 1.8161g of the compound represented by the formula (AN-3-2) were added thereto, and the mixture was stirred at room temperature for 12 hours. To this were added 40.0g of NMP and 20.0g of Butyl Cellosolve (BC), and the solution was heated and stirred at 60 ℃ until the weight average molecular weight of the polymer of the solute became the desired weight average molecular weight, thereby obtaining varnish 1 having a weight average molecular weight of the solute of about 63,000 and a resin component concentration of 6 wt%.

[ examples 2 to 31]

Varnishes 2 to 31 having a polymer solid content of 6 wt% were prepared according to example 1 except that the tetracarboxylic dianhydride and the diamine were changed. The weight average molecular weights of the tetracarboxylic dianhydrides and diamines used and the polymers obtained are shown in tables 1-1 to 1-3. Example 1 is also disclosed again in Table 1-1.

TABLE 1-1

Tables 1 to 2

Tables 1 to 3

[ example 32]

< preparation of liquid Crystal alignment agent, rubbing resistance test >

110 g of varnish was weighed in a 50mL eggplant type flask, and 0.5 part by weight of the compound represented by the formula (1-1), 7g of N-methyl-2-pyrrolidone and 3g of butyl cellosolve were added to 100 parts by weight of the polymer, and the mixture was shaken for 2 hours to obtain a liquid crystal aligning agent RA-1 having a solid content of 3 wt%.

The obtained liquid crystal aligning agent RA-1 was applied on a substrate with a SiNx/ITO comb electrode by using a spinner, and on the opposite side, the liquid crystal aligning agent RA-1 was applied on a glass substrate with a spacer (height of the spacer: 4 μm). The coating conditions were 2,300rpm for 15 seconds. After the coating, pre-baking was performed at 80 ℃ for about 5 minutes, and then, baking treatment was performed at 200 ℃ for 30 minutes, thereby forming a liquid crystal alignment film having a film thickness of about 100 nm. The obtained polyimide film was subjected to a rubbing treatment using a rubbing treatment apparatus under conditions of a rubbing cloth (wool length: 1.9 mm: rayon) of 0.40mm in wool penetration, a table moving speed of 60mm/sec and a roll rotating speed of 1000rpm, and the film surface was observed, whereby no thinning of the film was observed.

< preparation of FFS cell, confirmation of flow orientation, contrast and AC afterimage measurement >

The substrate subjected to the rubbing treatment was ultrasonically cleaned in ethanol for 5 minutes, and then the surface was cleaned with ultrapure water, and then dried in an oven at 120 ℃ for 30 minutes. The air FFS cell was assembled by facing two substrates each having an alignment film formed on a substrate, with the alignment films formed on the substrates facing each other, forming a gap for injecting a liquid crystal composition between the facing alignment films so that the rubbing directions of the alignment films become parallel to each other, and then bonding the alignment films together. The following positive liquid crystal composition a was vacuum-injected into the prepared empty FFS cell, and the injection port was sealed with a photo-curing agent. Then, a heat treatment was performed at 110 ℃ for 30 minutes to fabricate an FFS liquid crystal display element (FFS cell) 1-1.

< Positive type liquid Crystal composition A >

Physical property values: NI is 100.1 ℃; Δ ε 5.1; Δ n 0.093; eta.25.6 mPas.

The alignment of the liquid crystal in the obtained liquid crystal display element was confirmed, and as a result, no flow alignment was observed. The contrast value was 2800 when measured, and the AC residual image was 2.0% when measured.

Example 33 to example 66

In addition to changing the varnish and additives used, the abrasion resistance, contrast and AC afterimage were measured in accordance with example 32. The measurement results are shown in Table 2-1 together with example 32.

TABLE 2-1

Comparative examples 1 to 4

In addition to the modification of the additives, the abrasion resistance, the contrast ratio, and the AC afterimage were measured in accordance with example 32. The measurement results are shown in Table 2-2.

Tables 2 to 2

Comparing examples 32 to 66 with comparative examples 1 to 4, it is shown that: when the present invention is applied to an FFS liquid crystal display element, the FFS liquid crystal display element can have good rubbing resistance and good contrast and AC image sticking characteristics.

[ example 67]

122.0 g of the varnish synthesized in example 12 and 238.0 g of the varnish synthesized in example 23 were weighed in a 50mL eggplant type flask equipped with a stirring blade and a nitrogen gas inlet tube, and 5.0 parts by weight of the compound represented by the formula (1-1), 5.0g of N-methyl-2-pyrrolidone and 5.0g of butyl cellosolve were added to 100 parts by weight of the polymer, and the mixture was stirred at room temperature for 1 hour to obtain an aligning agent RB-1 having a resin component concentration of 3 wt%.

The obtained orientation agent is processed by a rotatorRB-1 is coated on the glass substrate. After coating, the substrate was heated at 80 ℃ for 3 minutes to evaporate the solvent, and then irradiated with linearly polarized ultraviolet Light from a direction perpendicular to the substrate via a polarizing plate using a Multi-Light ML-501C/B manufactured by a bull tail (Ushio) motor (thigh). The exposure energy at this time was measured using an ultraviolet integrated photometer UIT-150 (light receiver: UVD-S365) manufactured by a cow tail motor (stock) so as to be 1.3J/cm at a wavelength of 365nm²±0.1J/cm²The exposure time is adjusted. The resulting film was calcined at 200 ℃ for 30 minutes to form a liquid crystal alignment film having a film thickness of about 100 nm. The pencil hardness of the obtained substrate was measured, and was 4H.

< FFS cell manufacturing method, flow orientation confirmation, foreign matter generation confirmation, and AC afterimage measurement >

The obtained alignment agent RB-1 was coated on a substrate with SiNx/ITO comb electrodes using a spinner, and on the opposite side, the alignment agent RB-1 was coated on a glass substrate with spacers (height of spacers: 4 μm). After coating, the substrate was heated at 80 ℃ for 3 minutes to evaporate the solvent, and then irradiated with linearly polarized ultraviolet light from a direction perpendicular to the substrate via a polarizing plate using an emchlite ML-501C/B manufactured by a boehail motor (stock). The exposure energy at this time was measured using an ultraviolet integrated photometer UIT-150 (light receiver: UVD-S365) manufactured by a cow tail motor (stock) so as to be 1.3J/cm at a wavelength of 365nm²±0.1J/cm²The exposure time is adjusted. The resulting film was calcined at 200 ℃ for 30 minutes to form a liquid crystal alignment film having a film thickness of about 100 nm. The surfaces of the two alignment film-forming substrates on which the alignment films were formed were opposed to each other, and a void FFS cell having a cell thickness of 4 μm was assembled by forming a gap between the opposed alignment films for injecting a liquid crystal composition and then bonding them so that the polarization directions of linearly polarized light irradiated to the respective alignment films were parallel to each other. The positive liquid crystal composition was vacuum-injected into the prepared empty FFS cell to prepare an FFS liquid crystal display device. The alignment of the liquid crystal in the obtained liquid crystal display element was confirmed, and as a result, no flow alignment was observed. Relay (S)On the other hand, when the liquid crystal display element after the foreign substance test was observed with a microscope, no foreign substance was observed. The contrast value was measured, and the result was 3500, and the AC afterimage was measured, and the Δ B was 2.0%.

[ example 68 to example 96]

Pencil hardness, foreign matter test, contrast, and AC residual image were measured in accordance with example 67, except that the varnish and additives used were changed. The measurement results are shown in Table 3-1 together with example 67.

Example 97 to example 98

The varnish and additives used were changed so that the heat treatment after the ultraviolet irradiation was performed at 110 ℃ for 20 minutes and then at 220 ℃ for 15 minutes, and the pencil hardness, foreign matter test, contrast, and AC afterimage were measured in accordance with example 67. The measurement results are shown in Table 3-1 together with example 67.

[ example 99]

The varnish and additives used were changed so that the heat treatment after the ultraviolet irradiation was carried out at 180 ℃ for 20 minutes and then at 220 ℃ for 15 minutes, and the pencil hardness, foreign matter test, contrast, and AC afterimage were measured in accordance with example 67. The measurement results are shown in Table 3-1 together with example 67.

TABLE 3-1

Comparative examples 5 to 8

Pencil hardness, foreign matter test, contrast, and AC residual image were measured in accordance with example 67, except that the varnish and additives used were changed. The measurement results are shown in Table 3-2.

TABLE 3-2

Comparing examples 67 to 99 with comparative examples 5 to 8, it is shown that: when the present invention is applied to an FFS liquid crystal display element, the FFS liquid crystal display element can suppress the generation of foreign substances and has good contrast and AC image sticking characteristics.

[ liquid Crystal alignment agent for coating by ink jet method ]

By appropriately selecting the solvent to be used, the liquid crystal aligning agent of the present invention is suitable for application by an ink jet method.

[ example 100]

The varnish synthesized in example 12 was poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40 ℃ for 15 hours under reduced pressure, whereby 3g of polyamic acid (PAA-12) was obtained. To the polyamic acid (PAA-12) were added NMP 48.0g, γ -butyrolactone (GBL)12.0g, 1-butoxy-2-propanol (BP)16.0g, diethylene glycol ethyl methyl Ether (EDM)15.0g, diethylene glycol butyl methyl ether (BDM)3.0g, and diisobutyl ketone (DIBK)3.0g to prepare varnish (12-a) having a solid content of 3.0 wt% and a solvent composition of NMP/GBL/BP/EDM/DIBK 48/12/16/15/3/3.

[ example 101]

According to example 100, varnish (23-a) having a solid content concentration of 3.0 wt% and a solvent composition of NMP/GBL/BP/EDM/BDM/DIBK of 48/12/16/15/3/3 was prepared in the same manner as the varnish synthesized in example 23.

[ example 102]

2.0g of the varnish (12-a) prepared in example 100 and 8.0g of the varnish (23-a) prepared in example 101 were weighed, and 15 parts by weight of the compound represented by formula (1-1) was added to 100 parts by weight of the polymer to prepare a liquid crystal aligning agent for ink jet coating (RB-38) having a solid content of 3.0 wt% and a solvent composition of NMP/GBL/BP/EDM/BDM/DIBK 48/12/16/15/3/3.

[ example 103]

152.0 g of the varnish synthesized in example 15 and 258.0 g of the varnish synthesized in example 25 were weighed, and 15 parts by weight of the compound represented by the formula (1-1), 2.2g of NMP, 2.6g of GBL, 1.4g of BC, 1.0g of BDM, and 2.8g of EDE were added to 100 parts by weight of the polymer to prepare a varnish having a solid content of 3.0% by weight and a solvent composition of NMP: GBL: BC: BDM: EDE 48: 13: 17: 5: 14 (RB-39) liquid crystal aligning agent for ink jet coating.

[ example 104]

122.0 g of the varnish synthesized in example 12 and 238.0 g of the varnish synthesized in example 23 were weighed, and 15 parts by weight of the compound represented by the formula (1-1), 2.2g of NMP, 5.2g of GBL, 2.0g of BC, and 0.6g of DIBK were added to 100 parts by weight of the polymer to prepare a mixture having a solid content of 3.0% by weight and a solvent composition of NMP: GBL: BC: DIBK 48: 26: 20: 3 (RB-40) for coating the liquid crystal alignment agent by the ink jet method.

[ example 105]

Pencil hardness, foreign matter test, contrast, and AC afterimage were measured according to example 67, except that the liquid crystal alignment agent for ink jet coating (RB-38) was coated on the glass substrate by an ink jet coating apparatus (manufactured by fuji FILM (FILM) gmbh, DMP-2831). Further, the interval between droplets and the voltage applied to the cartridge (cartridge) were adjusted so that the thickness of the liquid crystal alignment film became 100 nm.

Example 106 to example 107

Pencil hardness, foreign matter test, contrast, and AC residual image were measured according to example 105 except for changing the varnish used. The measurement results are shown in Table 3-3 together with example 105.

Tables 3 to 3

Shows that: when the liquid crystal aligning agent of the present invention is applied to an FFS liquid crystal display element in the case of coating by an ink jet method, the FFS liquid crystal display element can suppress the generation of foreign matter and has excellent contrast and AC image sticking characteristics.

[ example 108]

In a 50mL eggplant type flask equipped with a stirring blade and a nitrogen gas inlet tube, 152.0 g of the varnish synthesized in example 15 and 258.0 g of the varnish synthesized in example 25 were weighed, 5.0 parts by weight of the compound represented by the formula (1-1) per 100 parts by weight of the polymer, 5 parts by weight of the compound of the additive (Ad5) per 100 parts by weight of the polymer, 5.0g of N-methyl-2-pyrrolidone and 5.0g of butyl cellosolve were added, and the mixture was stirred at room temperature for 1 hour to obtain an aligning agent RB-41 having a resin component concentration of 3 wt%.

The obtained alignment agent RB-41 was coated on a glass substrate using a spinner. After coating, the substrate was heated at 80 ℃ for 3 minutes to evaporate the solvent, and then irradiated with ultraviolet linearly polarized light from a direction perpendicular to the substrate via a polarizing plate using an emchlite ML-501C/B manufactured by a boehail motor (stock). The exposure energy at this time was measured using an ultraviolet integrated photometer UIT-150 (light receiver: UVD-S365) manufactured by a cow tail motor (stock) so as to be 1.3J/cm at a wavelength of 365nm²±0.1J/cm²The exposure time is adjusted. The resulting film was calcined at 200 ℃ for 30 minutes to form a liquid crystal alignment film having a film thickness of about 100 nm. The pencil hardness of the obtained substrate was measured, and found to be 5H.

The obtained alignment agent RB-41 was coated on a substrate with SiNx/ITO comb electrodes using a spinner, and on the opposite side, the alignment agent RB-41 was coated on a glass substrate with spacers (height of spacers: 4 μm). After coating, the substrate was heated at 80 ℃ for 3 minutes to evaporate the solvent, and then irradiated with ultraviolet linearly polarized light from a direction perpendicular to the substrate via a polarizing plate using an emchlite ML-501C/B manufactured by a boehail motor (stock). The exposure energy at this time was measured using an ultraviolet integrated photometer UIT-150 (light receiver: UVD-S365) manufactured by a cow tail motor (stock) so as to be 1.3J/cm at a wavelength of 365nm²±0.1J/cm²The exposure time is adjusted. The resulting film was calcined at 200 ℃ for 30 minutes to form a liquid crystal alignment film having a film thickness of about 100 nm. The surfaces of the two alignment film forming substrates on which the alignment films are formed are made to face each other and irradiated with light to the respective alignmentThe films were assembled into an empty FFS cell having a cell thickness of 4 μm by forming a gap between the opposing alignment films for injecting the liquid crystal composition, and then laminating the films so that the polarization directions of linearly polarized light were parallel to each other. The positive liquid crystal composition was vacuum-injected into the prepared empty FFS cell to prepare an FFS liquid crystal display device. The alignment of the liquid crystal in the obtained liquid crystal display element was confirmed, and as a result, no flow alignment was observed. Then, the liquid crystal display element after the foreign substance test was observed with a microscope, and as a result, no foreign substance was observed. The contrast value was measured, and the result was 3300, and the AC afterimage was measured, and the Δ B was 2.3%.

[ example 109]

Pencil hardness, foreign matter test, contrast, and AC afterimage were measured in accordance with example 108, except that the varnish, additives, and the amount used were changed. The measurement results are shown in Table 4-1 together with example 108.

TABLE 4-1

Comparing examples 108 to 109 with comparative examples 5 to 8, it is shown that: when the present invention is applied to an FFS liquid crystal display element, the FFS liquid crystal display element can suppress the generation of foreign substances and has good contrast and AC image sticking characteristics.

[ liquid Crystal alignment agent for coating by ink jet method ]

[ example 110]

162.0 g of the varnish synthesized in example 16 and 268.0 g of the varnish synthesized in example 26 were weighed, and 5 parts by weight of the compound represented by the formula (1-1) and 3 parts by weight of the compound represented by the formula (Ad5) were added to 100 parts by weight of the polymer to prepare a liquid crystal aligning agent for ink-jet coating (RB-43) having a solid content of 3.0 wt% and a solvent composition of NMP/GBL/BP/EDM/BDM/DIBK 48/12/16/15/3/3.

[ example 111]

172.0 g of the varnish synthesized in example 17 and 288.0 g of the varnish synthesized in example 28 were weighed, 8 parts by weight of the compound represented by the formula (1-1) and 2 parts by weight of the compound represented by the formula (Ad1) were added to 100 parts by weight of the polymer, and 2.2g of NMP, 2.6g of GBL, 1.4g of BC, 1.0g of BDM and 2.8g of EDE were added to prepare a varnish having a solid content of 3.0 wt% and a solvent composition of NMP: GBL: BC: BDM: EDE 48: 13: 17: 5: 14 (RB-44) liquid crystal aligning agent for ink jet coating.

[ example 112]

Pencil hardness, foreign matter test, contrast, and AC residual image were measured in accordance with example 111 except that the liquid crystal alignment agent for ink jet coating (RB-43) was coated on the glass substrate by an ink jet coating apparatus (manufactured by fuji photo film gmbh, DMP-2831). Further, the droplet interval and the cartridge application voltage were adjusted so that the film thickness of the liquid crystal alignment film became 100 nm.

[ example 113]

In addition to changing the alignment agent used, the pencil hardness, foreign matter test, contrast, and AC afterimage were measured according to example 109. The measurement results are shown in Table 4-2 together with example 112.

TABLE 4-2

Shows that: when the liquid crystal aligning agent of the present invention is applied to an FFS liquid crystal display element in the case of coating by an ink jet method, the FFS liquid crystal display element can be obtained which can suppress the generation of foreign matter and has excellent contrast and AC image sticking characteristics.

[ Industrial Applicability ]

Confirming that: the liquid crystal aligning agent of the present invention can form a liquid crystal alignment film having high film hardness and exhibiting excellent liquid crystal alignment properties.

Confirming that: the liquid crystal display element including the liquid crystal alignment film formed from the liquid crystal alignment agent of the present invention has excellent characteristics such as being less likely to cause foreign matter generation at the time of touch panel operation, exhibiting high contrast, being less likely to cause AC afterimage, and the like. The liquid crystal aligning agent of the present invention is particularly suitably applicable to a transverse electric field driven type liquid crystal display element.

Claims

1. A liquid crystal aligning agent comprising at least one polymer selected from the group consisting of polyamic acids obtained by reacting tetracarboxylic dianhydrides and diamine compounds and derivatives thereof, and a compound represented by the following formula (1), wherein the amount of the compound represented by the formula (1) is 0.1 to 30% by weight based on the total weight of the polyamic acids or derivatives thereof,

2. the liquid crystal aligning agent according to claim 1, wherein the compound of formula (1) is at least one of compounds represented by formulae (1-1) to (1-4);

in the formula (1-3), R is-CH₃or-CH₂CH₃。

3. The liquid crystal aligning agent according to claim 1 or 2, wherein

in the formulae (AN-I), (AN-IV) and (AN-V), X is independently a single bond or-CH₂-；

In the formula (AN-II), G is a single bond, alkylene group having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO₂-、-C(CH₃)₂-, or-C (CF)₃)₂-；

in the formulae (AN-III) to (AN-V), the ring A¹⁰A C3-10 monocyclic hydrocarbon group or a C6-30 condensed polycyclic hydrocarbon group, wherein at least one hydrogen of the group is substituted by a methyl group, an ethyl group or a phenyl group, and the group is bonded to the ringThe two binding bonds may be bonded to the same carbon;

in the formula (DI-4), s is independently an integer of 0 to 2;

at least one hydrogen of the cyclohexane ring and the benzene ring in the formulae (DI-2) to (DI-7) is selected from the group consisting of-F, -Cl, C1-3 alkyl and-OCH₃、-OH、-CF₃、-CO₂H、-CONH₂、-NHC₆H₅Phenyl, or benzyl, and, in formula (DI-4), at least one hydrogen of the benzene ring may be substituted by one selected from the group of groups represented by the following formulae (DI-4-a) to (DI-4-e);

In the formula (DI-11), r is 0 or 1;

in the formula (DI-13), R²³Independently an alkyl group having 1-5 carbon atoms, an alkoxy group having 1-5 carbon atoms or-Cl, and p independently 0 ℃ -3, q is an integer of 0 to 4;

in the formula (DI-15), ring C is a monocyclic ring containing a hetero atom;

In the formula (DIH-2), ring D is a cyclohexane ring, a benzene ring or a naphthalene ring, at least one hydrogen of the ring may be substituted by a methyl group, an ethyl group or a phenyl group;

in the formula (DIH-3), the rings E are respectively and independently a cyclohexane ring or a benzene ring, at least one hydrogen of the ring can be substituted by methyl, ethyl or phenyl, Y is a single bond, alkylene with 1-20 carbon atoms, -CO-, -O-, -S-, -SO₂-、-C(CH₃)₂-, or-C (CF)₃)₂-；

in the formula (DI-31), G²⁶Is a single bond, -O-, -COO-、-OCO-、-CO-、-CONH-、-CH₂O-、-OCH₂-、-CF₂O-、-OCF₂-, or- (CH)₂)_m'-, m' is an integer of 1 to 12;

in the formula (DI-31-a), G²⁷、G²⁸And G²⁹Are a bonding group, they are independently a single bond, or an alkylene group having 1 to 12 carbon atoms, one or more-CH of the alkylene group₂-optionally substituted by-O-, -COO-, -OCO-, -CONH-, -CH ═ CH-, a ring B²¹Ring B²²Ring B²³And ring B²⁴Independently 1, 4-phenylene, 1, 4-cyclohexylene, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl, pyridine-2, 5-diyl, piperidine-1, 4-diyl, naphthalene-1, 5-diyl, naphthalene-2, 7-diyl or anthracene-9, 10-diyl, ring B²¹Ring B²²Ring B²³And ring B²⁴Wherein at least one hydrogen may be replaced by-F or-CH₃And (b) a substituent, s, t and u are independently an integer of 0 to 2, the total of which is 0 to 5, and when s, t or u is 2, the two bonding groups in each bracket may be the same or different, and the two rings may be the same or different, R²⁶Hydrogen, -F, -OH, alkyl group with 1-30 carbon atoms, fluorine substituted alkyl group with 1-30 carbon atoms, alkoxy group with 1-30 carbon atoms, -CN, -OCH₂F、-OCHF₂or-OCF₃At least one-CH of the C1-30 alkyl group₂May be substituted with a divalent group represented by the following formula (DI-31-b),

at least one hydrogen of the benzene ring in the formula (DI-33) may be substituted by an alkyl group having 1 to 20 carbon atoms or a phenyl group;

4. The liquid crystal aligning agent according to claim 3, wherein

the diamine is selected from the group consisting of formula (DI-1-3), formula (DI-2-1), formula (DI-4-2), formula (DI-4-10), formula (DI-4-15), formula (DI-5-1), formula (DI-5-5), formula (DI-5-9), formula (DI-5-12), formula (DI-5-13), formula (DI-5-17), formula (DI-5-28), formula (DI-5-30), formula (DI-6-7), formula (DI-7-3), formula (DI-11-2), formula (DI-13-1), formula (DI-16-1), At least one of the group consisting of formula (DI-31-56) and formula (DIH-2-1);

in the formulas (AN-1-2) and (AN-4-17), m is AN integer of 1-12 independently;

in the formula (DI-5-30), k is an integer of 1 to 5; and also

In the formula (DI-7-3), n is 1 or 2 independently.

5. The liquid crystal aligning agent according to claim 1 or 2, wherein the polyamic acid and the derivative thereof is a polymer (a) obtained by reacting at least one of the tetracarboxylic dianhydride and the diamine with a compound having a photoreactive structure.

6. The liquid crystal aligning agent according to claim 5, wherein the photoreactive structure is at least one selected from the group consisting of structures represented by the following formulae (P-1) to (P-7);

7. The liquid crystal aligning agent according to claim 6, wherein the compound having the photoreactive structure is at least one tetracarboxylic dianhydride or diamine compound selected from the group consisting of the following formula (II-1), formula (II-2), formula (III-1), formula (III-2), formula (IV-1), formula (IV-2), formula (V-1) to formula (V-3), and formula (VI-1), formula (VI-2);

in the respective formulae, the group whose bonding position is not fixed to any carbon atom constituting the ring means that the bonding position on the ring is arbitrary; in the formula (V-2), R⁶Independently is-CH₃、-OCH₃、-CF₃or-COOCH₃A is an integer of 0 to 2; in the formula (V-3), the ring A and the ring B are each independently at least one member selected from the group consisting of monocyclic hydrocarbons, condensed polycyclic hydrocarbons and heterocycles, R¹¹Is a C1-20 linear alkylene group, -COO-, -OCO-, -NHCO-or-N (CH)₃)CO-，R¹²Is a C1-20 linear alkylene group, -COO-, -OCO-, -NHCO-or-N (CH)₃)CO-，R¹¹And R¹²Of linear alkylene-CH₂One or two of (A) and (B) may be substituted by-O-, R⁷～R¹⁰Are independently-F, -CH₃、-OCH₃、-CF₃or-OH, and b to e are each independently an integer of 0 to 4.

8. The liquid crystal aligning agent according to claim 7, wherein the diamine compound having the photoreactive structure is represented by the following formula (PDI-7);

9. The liquid crystal aligning agent according to claim 5, which comprises the polymer (a) and further comprises a polymer (b), wherein the polymer (b) is at least one selected from polyamic acids and derivatives thereof obtained by reacting tetracarboxylic dianhydrides having no photoreactive structure and diamines having no photoreactive structure.

10. The liquid crystal aligning agent according to claim 9, wherein

The tetracarboxylic dianhydride used in the synthesis of the polymer (b) is selected from the following formula (AN-1-1), formula (AN-1-2), formula (AN-1-13), formula (PA-1), formula (AN-3-2), formula (AN-4-5), formula (AN-4-17), formula (AN-4-21), at least one of formula (AN-4-29), formula (AN-4-30), formula (AN-5-1), formula (AN-7-2), formula (AN-10-1), formula (AN-11-3), formula (AN-16-1), formula (AN-16-3), and formula (AN-16-4);

in the formulas (AN-1-2) and (AN-4-17), m is AN integer of 1-12 independently;

in the formula (DI-5-30), k is an integer of 1 to 5; and also

In the formula (DI-7-3), n is 1 or 2 independently.

11. The liquid crystal aligning agent according to claim 1 or 2, which further comprises at least one selected from the group consisting of oxazine compounds, oxazoline compounds, epoxy compounds other than the compounds represented by the formula (1), and silane coupling agents.

12. A liquid crystal alignment film formed from the liquid crystal aligning agent according to any one of claims 1 to 11.

13. A liquid crystal alignment film for a transverse electric field-driven liquid crystal display element, which is formed from the liquid crystal aligning agent according to any one of claims 1 to 11.

14. A liquid crystal display element comprising the liquid crystal alignment film according to claim 12 or 13.