KR101938923B1

KR101938923B1 - Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element

Info

Publication number: KR101938923B1
Application number: KR1020147014018A
Authority: KR
Inventors: 마사아키 가타야마; 유키 다카야마; 유타 가와노; 고헤이 고토
Original assignee: 닛산 가가쿠 가부시키가이샤
Priority date: 2011-11-01
Filing date: 2012-10-31
Publication date: 2019-04-10
Also published as: KR20140084278A; JPWO2013065755A1; TW201335232A; TWI567107B; CN104081268A; JP2017226647A; WO2013065755A1; JP6465159B2; CN104081268B; JP6183212B2

Abstract

A liquid crystal alignment treatment agent comprising at least one polymer selected from the group consisting of a polyimide precursor having a side chain represented by the formula [1A] or a formula [1B] and a polyimide obtained by imidizing the polyimide precursor.

(Wherein X ₁ and X _{5 each} represent a single bond, -O-, -COO-, -OCO-, -CONH-, -NHCO-, -NH-, -N (R ₁ ) - (wherein R ₁ is a linear or branched alkyl group having 1 to 5 carbon atoms) or -S-, X ₂ and X ₃ each represent a divalent cyclic group selected from a benzene ring, a cyclohexyl ring or a heterocyclic ring, any of the hydrogen atoms on these cyclic group is optionally substituted with an alkyl group having 1 ~ 3. X ₄ is an alkyl group, fluorinated alkyl group, an alkoxyl group or a or a fluorine-containing alkoxyl group having a carbon number of 1 ~ 18. X ₆ is M is 2 to 15, n is 1 to 3, p is 0 to 3, n + p is 1 to 6, and q is 2 to 15.)

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element,

The present invention relates to a novel diamine compound, a polyimide precursor obtained by reacting using the compound as a part of a raw material, a polyimide obtained by imidizing the polyimide precursor, a liquid crystal alignment treatment agent containing the polymer, And a liquid crystal display element having the liquid crystal alignment film.

BACKGROUND ART [0002] Liquid crystal display devices are widely used today as display devices for realizing thinness and light weight. A liquid crystal alignment film is usually used in this liquid crystal display element to determine the alignment state of the liquid crystal.

In this liquid crystal alignment film, a polyimide film is often used. In forming the polyimide film, a method of applying a solution of a polyamic acid or a solvent-soluble polyimide solution, which is a precursor of polyimide, to the substrate and firing is employed. The polyamic acid or solvent-soluble polyimide is generally formed by the reaction of a tetracarboxylic acid derivative such as a tetracarboxylic acid dianhydride with a diamine component.

One of the characteristics required for a liquid crystal alignment film is control of the so-called liquid crystal pretilt angle, in which the alignment tilt angle of the liquid crystal molecules with respect to the substrate surface is maintained at an arbitrary value. It is known that the size of the pretilt angle can be changed by selecting the structure of the polyimide constituting the liquid crystal alignment film. Among techniques for controlling the pretilt angle by the structure of polyimide, the method of using diamines having side chains as a part of raw materials of polyimide can control the pretilt angle according to the use ratio of diamine, It is relatively easy to obtain a pretilt angle and is useful as means for increasing the pretilt angle (see, for example, Patent Document 1).

In addition, as for the diamine component for increasing the pretilt angle of the liquid crystal as described above, the structure has been studied to improve the stability of the pretilt angle and process dependency. As the side chain structure used herein, it has been proposed that a cyclic structure such as a phenyl group or a cyclohexyl group is contained (for example, see Patent Document 2).

In the production of a liquid crystal display element, a step of filling the liquid crystal between the two substrates (cell gap) on which the liquid crystal alignment film is formed is required. Until now, a vacuum injection system for charging a liquid crystal between two substrates by using atmospheric pressure and vacuum pressure difference was generally used for liquid crystal charging. However, in this method, since the liquid crystal injection hole is formed only on one side of the substrate, it takes a long time to fill the liquid crystal between the substrates having cell gaps of 3 to 5 mu m, so that the manufacturing process of the liquid crystal display device is simplified Was difficult. This has become a serious problem particularly in the production of a liquid crystal TV or a large-sized monitor that has been put into practical use recently.

Therefore, in order to solve the above-described problem of the vacuum injection method, a liquid dropping method (also referred to as an ODF method) has been developed. In this method, a liquid crystal is dropped on a substrate having a liquid crystal alignment film formed thereon, bonded to another substrate in a vacuum, and then the liquid crystal is filled by UV curing the sealing material.

On the other hand, it has become necessary to suppress display unevenness as the liquid crystal display element progressively becomes finer. The ODF system has been solved by optimization of the manufacturing process for reducing the influence of the adsorbed water and impurities, such as the dropping amount of the liquid crystal and the improvement of the vacuum at the time of bonding. However, with the enlargement of the liquid crystal display device manufacturing line, there has been a demand for a liquid crystal alignment film which can not suppress display irregularity in the optimization of the manufacturing process so far and which can alleviate unevenness in orientation.

Japanese Patent Application Laid-Open No. 2-282726 Japanese Patent Application Laid-Open No. 9-278724

The liquid crystal alignment film is also used to control the angle of the liquid crystal with respect to the substrate, that is, the control of the pretilt angle of the liquid crystal. However, while the liquid crystal display device has high performance and its use range is enlarged year by year, Not only the quality but also the stability of the pretilt angle becomes more important.

In the manufacturing process of a liquid crystal display element, in order to enhance the alignment uniformity of the liquid crystal, a liquid crystal is sealed (enclosed) and then subjected to a heat treatment to temporarily make the liquid crystal isotropic. However, when the stability of the pretilt angle is low, there arises a problem that the pretilt angle of the desired size is not obtained after the isotropic process, or a deviation occurs in the pretilt angle. Particularly, a liquid crystal display device using a backlight having a large amount of heat for obtaining a high brightness and having a large amount of light irradiation, for example, a car navigation system or a large TV, is used or left in an environment exposed to high temperature and light for a long time have. Under such harsh conditions, when the pretilt angle is gradually changed, initial display characteristics are not obtained, or display irregularity occurs.

In the ODF method, which is a liquid crystal filling process for manufacturing a liquid crystal display device, since liquid crystal is directly dropped onto an alignment film, physical stress is applied to the liquid crystal and the liquid crystal alignment film during liquid crystal alignment or substrate bonding , It is necessary to increase the dropping point of the liquid crystal in the necessity of charging the liquid crystal all over the panel. For this reason, so-called unevenness in orientation, such as droplet traces and lattice unevenness, is liable to occur at a portion where the droplet of the liquid crystal drop or the liquid crystal comes into contact with the adjoining droplet, and in the case of a liquid crystal display device, There has been a problem that unevenness occurs. This uneven alignment is caused by the fact that the number of adsorbed water or impurities adhering to the interface of the liquid crystal alignment film formed on the substrate is gathered by the liquid crystal dropped by the ODF method so that the amount of adsorbed water or impurities Is thought to occur.

The present invention has been made in view of the above circumstances. That is, an object of the present invention is to provide a liquid crystal alignment film which does not change the pretilt angle even when exposed to high temperature and light for a long time, and to provide a liquid crystal alignment film capable of alleviating unevenness of liquid crystal alignment caused by the ODF method have. It is also an object of the present invention to provide a liquid crystal display device having the liquid crystal alignment film, a liquid crystal alignment treatment agent capable of providing the liquid crystal alignment film, a polymer for obtaining the liquid crystal alignment treatment agent, and a diamine compound for obtaining the polymer It is on.

As a result of intensive studies, the present inventors have found out that a liquid crystal alignment treatment agent containing a polymer having a side chain of a specific structure is very effective for achieving the above object, and has completed the present invention.

That is, the present invention has the following points.

(1) at least one polymer selected from the group consisting of a polyimide precursor having a side chain represented by the following formula [1A] or formula [1B] and a polyimide obtained by imidizing the polyimide precursor A liquid crystal alignment treatment agent.

delete

(Formula [1A] of, X ₁ is a single bond, -O-, -COO-, -OCO-, -CONH- , -NHCO-, -NH-, -N (R 1) - (R 1 is C 1 Or a branched alkyl group having 1 to 5 carbon atoms) or -S-, X ₂ represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring or a heterocyclic ring, and the cyclic group any hydrogen atom is optionally substituted with a fluorine-containing alkoxy group or a fluorine atom having a carbon number of 1 to 3 alkyl groups, 1 to 3 carbon atoms, an alkoxyl group, having 1 to 3 fluorine-containing alkyl group, having 1 to 3 carbon atoms in the. X ₃ are benzene An alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, , A fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom X ₄ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 18 carbon atoms, m is an integer of 2 to 15, n is an integer of 1 to 3, p is an integer of 0 to 3, and n + p is an integer of 1 to 6.)

delete

(Formula [1B] of, X ₅ is a single bond, -O-, -COO-, -OCO-, -CONH- , -NHCO-, -NH-, -N (R 2) - (R 2 is C 1 Or a branched alkyl group having 1 to 5 carbon atoms or a branched alkyl group having 1 to 5 carbon atoms, or -S-, X ₆ is an organic group having a steroid skeleton having 12 to 25 carbon atoms, and q is an integer of 2 to 15.)

(2) The liquid crystal alignment treatment agent according to (1), wherein the polyimide precursor is obtained by reacting a diamine component containing a diamine compound having a side chain represented by the formula (1A) or (1B) with a tetracarboxylic acid component.

(3) The liquid crystal alignment treating agent according to (2), wherein the diamine compound having a side chain represented by the above formula (1A) is represented by the following formula [2A].

delete

(Equation [2A] of, X ₁ is a single bond, -O-, -COO-, -OCO-, -CONH- , -NHCO-, -NH-, -N (R 1) - (R 1 is C 1 Or a branched alkyl group having 1 to 5 carbon atoms) or -S-, X ₂ represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring or a heterocyclic ring, and the cyclic group any hydrogen atom is optionally substituted with a fluorine-containing alkoxy group or a fluorine atom having a carbon number of 1 to 3 alkyl groups, 1 to 3 carbon atoms, an alkoxyl group, having 1 to 3 fluorine-containing alkyl group, having 1 to 3 carbon atoms in the. X ₃ are benzene An alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, , A fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom X ₄ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 18 carbon atoms, m is an integer of 2 to 15, n is an integer of 1 to 3, p is an integer of 0 to 3, and n + p is an integer of 1 to 6.)

(4) The liquid crystal alignment treating agent according to (3), wherein the diamine compound represented by the formula (2A) is represented by the following formulas [2a] to [2d].

delete

(In the formula [2a], R ₁ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 18 carbon atoms, And p 1 is an integer of 0 to 3.

In formula [2b], R ₂ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 18 carbon atoms, And p2 is an integer of 0 to 3.

In formula [2c], R ₃ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 18 carbon atoms, N1 is an integer of 1 to 3, p3 is an integer of 0 to 3, and n1 + p3 is an integer of 1 to 6.

In formula [2d], R ₄ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 18 carbon atoms, N2 is an integer of 1 to 3, p4 is an integer of 0 to 3, and n2 + p4 is an integer of 1 to 6.)

(5) The liquid crystal alignment treating agent according to (2), wherein the diamine compound having a side chain represented by the formula [1B] is represented by the following formula [2B].

delete

(Equation [2B] of, X ₅ is a single bond, -O-, -COO-, -OCO-, -CONH- , -NHCO-, -NH-, -N (R 2) - (R 2 is C 1 Or a branched alkyl group having 1 to 5 carbon atoms or a branched alkyl group having 1 to 5 carbon atoms, or -S-, X ₆ is an organic group having a steroid skeleton having 12 to 25 carbon atoms, and q is an integer of 2 to 15.)

(6) The liquid crystal alignment treating agent according to any one of (3) to (5), wherein the diamine compound represented by the formula (2A) or (2B) is from 5 to 80 mol% of the diamine component.

(7) The liquid crystal alignment treating agent according to (4) above, wherein the diamine compound represented by the above formula (2a) to formula (2d) accounts for from 5 to 80 mol% of the diamine component.

(8) The liquid crystal alignment treating agent according to any one of (2) to (7), wherein the tetracarboxylic acid component is a tetracarboxylic acid dianhydride represented by the following formula [3].

delete

(In the formula [3], Z ₁ is a tetravalent organic group having 4 to 13 carbon atoms and further contains a non-aromatic cyclic hydrocarbon group having 4 to 10 carbon atoms)

(9) The liquid crystal alignment treating agent according to (8), wherein the Z ₁ has a structure represented by the following formulas [3a] to [3j].

delete

(Formula [3a] of, Z ₂ ~ Z ₅ is a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, even if each of the same or or different. In the formula [3g] from, Z _6, Z ₇ is a hydrogen atom or a methyl group , They may be the same or different.

(10) The liquid crystal alignment treatment agent according to any one of (1) to (9), wherein the liquid crystal alignment treatment agent contains 80 to 99 mass% of an organic solvent.

(11) The liquid crystal alignment treating agent according to (10), wherein the organic solvent contains 5 to 60 mass% of a poor solvent.

(12) A liquid crystal alignment film obtained from the liquid crystal alignment treatment agent according to any one of (1) to (11).

(13) A liquid crystal alignment film obtained by the ink-jet coating method using the liquid crystal alignment treatment agent according to any one of (1) to (11).

(14) A liquid crystal display element having the liquid crystal alignment film according to (12) or (13).

(15) A liquid crystal composition comprising a liquid crystal layer between a pair of substrates provided with electrodes and containing a polymerizable compound capable of polymerizing by at least one of active energy rays and heat is disposed between the pair of substrates (12) or (13), which is used for a liquid crystal display element manufactured through a step of polymerizing the polymerizable compound while applying a voltage between the electrodes.

(16) A liquid crystal display element having the liquid crystal alignment film according to (15) above.

(17) A liquid crystal display device comprising a liquid crystal layer between a pair of electrodes including an electrode and the liquid crystal alignment film, and a liquid crystal composition containing a polymerizable compound capable of polymerizing by at least one of active energy rays and heat between the pair of substrates A liquid crystal display element according to the above (16), wherein the composition is disposed and the polymerizable compound is polymerized while applying a voltage between the electrodes.

(18) A liquid crystal alignment film comprising a liquid crystal layer between a pair of substrates provided with electrodes, and a liquid crystal alignment film containing a polymerizable group capable of polymerizing by at least one of active energy rays and heat is disposed between the pair of substrates, The liquid crystal alignment film according to (12) or (13), which is used for a liquid crystal display device manufactured through a step of polymerizing the polymerizable group while applying a voltage between the electrodes.

(19) A liquid crystal display element having the liquid crystal alignment film according to (18).

(20) A liquid crystal alignment film comprising a liquid crystal layer between a pair of substrates having electrodes, and a liquid crystal alignment film containing a polymerizable group capable of polymerizing by at least one of an active energy ray and a heat is disposed between the pair of substrates, The liquid crystal display element according to (19), wherein the liquid crystal display element is produced through a step of polymerizing the polymerizable group while applying a voltage between the electrodes.

(21) A diamine compound represented by the above formula [2A].

(22) The diamine compound represented by the above formula [2a] to [2d].

(23) A polyamic acid obtained by reacting a diamine component containing a diamine compound represented by the above formula [2A] or formula [2B] with a tetracarboxylic acid component or a polyimide obtained by subjecting the polyamic acid to dehydration ring closure.

(24) A polyimide obtained by subjecting a diamine component containing a diamine compound represented by the above formula [2a] to [2d] to a tetracarboxylic acid component, or a polyamic acid obtained by dehydrocondensing the polyamic acid.

By using the liquid crystal alignment treatment agent containing a polymer having a side chain of the specific structure of the present invention, the pretilt angle does not change even when exposed to high temperature and light irradiation for a long time, and the liquid crystal alignment irregularity caused by the ODF system is reduced The liquid crystal alignment layer can be provided. Accordingly, by using this liquid crystal alignment film, it is possible to provide a liquid crystal display device having excellent display characteristics and high reliability.

Hereinafter, the present invention will be described in detail.

The present invention relates to a polyimide precursor having side chain (also referred to as specific side chain structure) represented by the following formula [1A] or formula [1B] and at least one selected from the group consisting of polyimide imidized with the polyimide precursor Of a polymer (also referred to as a specific polymer).

delete

The specific side chain structure of the present invention is a structure represented by the above formula [1A] or formula [1B].

The structure represented by the above formula [1A] has a benzene ring, a cyclohexyl ring or a heterocyclic ring. As a result, the stability of the side chain region against heat and ultraviolet rays is improved. Therefore, a liquid crystal alignment film in which the pretilt angle is stable with respect to heat or light can be obtained.

The structure represented by the above formula [1B] has a cyclic group comprising a steroid skeleton. Therefore, the same effect as that of the formula [1A] can be obtained, that is, the stability of the side chain portion against heat and ultraviolet rays is improved, and a liquid crystal alignment film having a stable tilt angle with respect to heat or light can be obtained.

The structure represented by the above formula [1A] has a benzene ring, a cyclohexyl ring or a heterocyclic ring. The structure represented by the above formula [1B] has a cyclic group comprising a steroid skeleton. Since the cyclic group comprising the benzene ring, the cyclohexyl ring or the heterocyclic ring in these formula [1A] and the steroid skeleton in the formula [1B] has a structure similar to that of the liquid crystal, the wet diffusion property . Thereby, it is possible to alleviate the physical stress on the liquid crystal and the liquid crystal alignment film which are generated at the time of substrate adherence. In this respect, the liquid crystal alignment layer having the structure of the formula [1A] or the formula [1B] which is the specific side chain structure of the present invention can alleviate the liquid crystal alignment unevenness caused by the ODF method.

The structure represented by the above formula [1A] has an alkyl group between the polymer main chain and the moiety of - (CH ₂ ) _m -X ₁ - (X ₂ ) _n - (X ₃ ) _p -X ₄ in formula [1A]. That is, the portion of the hydrophobic - (CH ₂ ) _m -X ₁ - (X ₂ ) _n - (X ₃ ) _p -X ₄ exists at a position away from the polymer main chain. Therefore, when the liquid crystal alignment layer is formed, the portion of - (CH ₂ ) _m -X ₁ - (X ₂ ) _n - (X ₃ ) _p -X ₄ efficiently appears at the interface of the alignment film, Can be increased. This makes it possible to suppress the adsorption of water or impurities at the liquid crystal alignment film interface. Further, the moiety of - (CH ₂ ) _m -X ₁ - (X ₂ ) _n - (X ₃ ) _p -X ₄ is present at a position apart from the polymer main chain so that a benzene ring, a cyclohexyl ring or a complex The ring can be efficiently formed at the interface of the alignment film. Therefore, the wettability on the liquid crystal alignment film of the liquid crystal dropped by the above-described ODF method is enhanced.

Likewise, the specific side chain structure in the formula [1B] has the same effect as the specific side chain structure in the formula [1A].

In view of the above, by using the liquid crystal alignment treatment agent containing a polymer having a side chain of the specific structure of the present invention, the pretilt angle does not change even when exposed to high temperature and light irradiation for a long time, Can be reduced in the liquid crystal alignment layer. Further, by using this liquid crystal alignment film, a liquid crystal display device having excellent display characteristics and high reliability can be provided.

At least one member selected from the group consisting of a polyimide precursor which is a specific polymer of the present invention and a polyimide in which the polyimide precursor is imidated has a specific side chain structure represented by the following formula [1A].

delete

Formula [1A] of, X ₁ is a single bond, -O-, -COO-, -OCO-, -CONH- , -NHCO-, -NH-, -N (R 1) - (R 1 is C 1 -C A linear alkyl group having 1 to 5 carbon atoms or a branched alkyl group having 1 to 5 carbon atoms) or -S-. Among them, a single bond, -O-, -COO-, -OCO-, -CONH-, -NHCO-, -NH- or -N (R ₁ ) - (R ₁ is a linear alkyl group having 1 to 5 carbon atoms Or a branched alkyl group having 1 to 5 carbon atoms). More preferably -O-, -CONH-, -NHCO- or -NH-. More preferably -O-, -CONH- or -NHCO-.

In the formula [1A], X ₂ represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring or a heterocyclic ring, and any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms A fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. At that time, X ₂ may be the same or different. Among them, X ₂ is preferably a benzene ring or a cyclohexyl ring.

In formula [1A], X ₃ represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring or a heterocyclic ring, and any hydrogen atom on these cyclic groups may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms A fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. At that time, X ₃ may be the same or different. Among them, X ₃ is preferably a benzene ring or a cyclohexyl ring.

In formula [IA], X ₄ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 18 carbon atoms. Among them, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 10 carbon atoms is preferable. More preferably an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. More preferably an alkyl group having 1 to 10 carbon atoms or an alkoxyl group having 1 to 10 carbon atoms.

In formula [1A], m is an integer of 2 to 15. Among them, an integer of 2 to 10 is preferable. And more preferably an integer of 2 to 7.

In the formula [1A], n is an integer of 1 to 3. Among them, an integer of 1 or 2 is preferable.

In the formula [1A], p is an integer of 0 to 3. Among them, an integer of 0 to 2 is preferable.

In the formula [1A], n + p is an integer of 1 to 6. Among them, an integer of 1 to 4 is preferable.

Preferred combinations of X ₁ , X ₂ , X ₃ , X ₄ , m, n and p in the formula [1A] are as shown in Tables 1 to 36.

Also, at least one selected from the group consisting of a polyimide precursor which is a specific polymer of the present invention and a polyimide in which the polyimide precursor is imidated has a specific side chain structure represented by the following formula [1B].

delete

Formula [1B] of, X ₅ is a single bond, -O-, -COO-, -OCO-, -CONH- , -NHCO-, -NH-, -N (R 2) - (R 2 is C 1 -C A linear alkyl group having 1 to 5 carbon atoms or a branched alkyl group having 1 to 5 carbon atoms) or -S-. Among them, a single bond, -O-, -COO-, -OCO-, -CONH-, -NHCO-, -NH-, or -N (R ₂ ) - (R ₂ represents a linear chain An alkyl group or a branched alkyl group having 1 to 5 carbon atoms). More preferably -O-, -CONH-, -NHCO- or -NH-. More preferably -O-, -CONH- or -NHCO-.

In formula [1B], X ₆ is an organic group having 12 to 25 carbon atoms having a steroid skeleton, and more preferably an organic group having 15 to 25 carbon atoms and having a steroid skeleton.

In the formula [1B], q is an integer of 2 to 15. Among them, an integer of 2 to 10 is preferable. And more preferably an integer of 2 to 7.

&Lt; Specific side chain type diamine compound >

A specific polymer of the present invention, that is, a polyimide precursor obtained by reacting a diamine component and a tetracarboxylic acid component, and a polyimide obtained by dehydrating and cyclizing the polyimide precursor, It is preferable to use a diamine compound represented by the following formula [2A] (also referred to as a specific side chain type diamine compound) as a part of the raw material.

delete

Formula [2A] of, X ₁ is a single bond, -O-, -COO-, -OCO-, -CONH- , -NHCO-, -NH-, -N (R 1) - (R 1 is C 1 -C A linear alkyl group having 1 to 5 carbon atoms or a branched alkyl group having 1 to 5 carbon atoms) or -S-. Among them, a single bond, -O-, -COO-, -OCO-, -CONH-, -NHCO-, -NH- or -N (R ₁ ) - (R ₁ is a linear alkyl group having 1 to 5 carbon atoms Or a branched alkyl group having 1 to 5 carbon atoms). More preferably -O-, -CONH-, -NHCO- or -NH-. More preferably -O-, -CONH- or -NHCO-.

In formula [2A], X ₂ represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring or a heterocyclic ring, and any hydrogen atom on these cyclic groups may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms A fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. At that time, X ₂ may be the same or different. Among them, X ₂ is preferably a benzene ring or a cyclohexyl ring.

In formula [2A], X ₃ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 18 carbon atoms. Among them, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 10 carbon atoms is preferable. More preferably an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. More preferably an alkyl group having 1 to 10 carbon atoms or an alkoxyl group having 1 to 10 carbon atoms.

In the formula [2A], m is an integer of 2 to 15. Among them, an integer of 2 to 10 is preferable. And more preferably an integer of 2 to 7.

In the formula [2A], n is an integer of 1 to 3. Among them, an integer of 1 or 2 is preferable.

In the formula [2A], p is an integer of 0 to 3. Among them, an integer of 0 to 2 is preferable.

In the formula [2A], n + p is an integer of 1 to 6. Among them, an integer of 1 to 4 is preferable.

The bonding position of two amino groups (-NH ₂ ) in the formula [2A] is not limited. Specifically, the position of 2,3, 4, 2, 5, 2, 6, 3, 4 of the benzene ring on the side chain joining group (- (CH ₂ ) _m - Or the positions of 3 and 5, respectively. Among them, from the viewpoint of reactivity when synthesizing a polyimide precursor, positions 2 and 4, positions 2 and 5, or positions 3 and 5 are preferable. More preferably the position of 2 or 4 or the position of 3 or 5, taking advantage of easiness in synthesis of the diamine compound.

Preferred combinations of X ₁ , X ₂ , X ₃ , m, n and p in the formula [2A] are as shown in Tables 1 to 30, similarly to the formula [1A].

A more preferable structure of the side chain type diamine compound of the present invention is a structure represented by the following formulas [2a] to [2d].

delete

In formula [2a], R ₁ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 18 carbon atoms. Among them, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 10 carbon atoms is preferable. More preferably an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. More preferably an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.

In formula [2a], m1 is an integer of 2 to 15. Among them, an integer of 2 to 10 is preferable. And more preferably an integer of 2 to 7.

In formula [2a], p1 is an integer of 0 to 3. Among them, an integer of 0 to 2 is preferable.

In the formula [2b], R ₂ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 18 carbon atoms. Among them, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 10 carbon atoms is preferable. More preferably an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. More preferably an alkyl group having 1 to 10 carbon atoms or an alkoxyl group having 1 to 10 carbon atoms.

In the formula [2b], m2 is an integer of 2 to 15. Among them, an integer of 2 to 10 is preferable. And more preferably an integer of 2 to 7.

In the formula [2b], p2 is an integer of 0 to 3. Among them, an integer of 0 to 2 is preferable.

In the formula [2c], R ₃ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 18 carbon atoms. Among them, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 10 carbon atoms is preferable. More preferably an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. More preferably an alkyl group having 1 to 10 carbon atoms or an alkoxyl group having 1 to 10 carbon atoms.

In the formula [2c], m3 is an integer of 2 to 15. Among them, an integer of 2 to 10 is preferable. And more preferably an integer of 2 to 7.

In the formula [2c], n1 is an integer of 1 to 3. Among them, an integer of 1 or 2 is preferable.

In the formula [2c], p3 is an integer of 0 to 3. Among them, an integer of 0 to 2 is preferable.

In the formula [2c], n1 + p3 is an integer of 1 to 6. Among them, an integer of 1 to 4 is preferable.

In the formula [2d], R ₄ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 18 carbon atoms. Among them, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 10 carbon atoms is preferable. More preferably an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. More preferably an alkyl group having 1 to 10 carbon atoms or an alkoxyl group having 1 to 10 carbon atoms.

In the formula [2d], m4 is an integer of 2 to 15. Among them, an integer of 2 to 10 is preferable. And more preferably an integer of 2 to 7.

In the formula [2d], n2 is an integer of 1 to 3. Among them, an integer of 1 or 2 is preferable.

In the formula [2d], p4 is an integer of 0 to 3. Among them, an integer of 0 to 2 is preferable.

In the formula [2d], n2 + p4 is an integer of 1 to 6. Among them, an integer of 1 to 4 is preferable.

The bonding position of two amino groups (-NH ₂ ) in formulas [2a] to [2d] is not limited. Specifically, the side chain of the coupler _{(- (CH 2) m1~m4 -} ) to about 2 on the benzene ring, in the 3-position, the 2, 4 position, 2, 5-position, 2, 6-position, 3 , The position of 4, or the position of 3, 5. Among them, from the viewpoint of reactivity when synthesizing a polyimide precursor, positions 2 and 4, positions 2 and 5, or positions 3 and 5 are preferable. More preferably the position of 2 or 4 or the position of 3 or 5, taking advantage of easiness in synthesis of the diamine compound.

More specifically, it is a structure represented by the following formulas [2-1] to [2-40], for example.

delete

delete

delete

delete

delete

delete

delete

delete

delete

delete

delete

(In the formulas [2-1] to [2-40], R ₅ is independently an alkyl group having 1 to 10 carbon atoms or an alkoxyl group having 1 to 10 carbon atoms, m ₅ is independently an integer of 2 to 7 ).

Among the above embodiments, [2-1] to [2-5], [2-8], [2-11], [2-12], expressions [2-14], [2-15], [2 -17] to [2-20], [2-25], [2-26], [2-29] and [2-30]

[2-1] to [2-5], [2-8], [2-11], [2-12], [2-14], [2-15], [2-17] -20] is more preferable.

The specific polymer of the present invention may also be used as a part of the starting material of the diamine compound represented by the following formula [2B] (also referred to as a specific side chain type diamine compound as the diamine compound represented by the formula [2A]).

delete

Formula [2B] of, X ₅ is a single bond, -O-, -COO-, -OCO-, -CONH- , -NHCO-, -NH-, -N (R 2) - (R 2 is C 1 -C A linear alkyl group having 1 to 5 carbon atoms or a branched alkyl group having 1 to 5 carbon atoms) or -S-. Among them, a single bond, -O-, -COO-, -OCO-, -CONH-, -NHCO-, -NH- or -N (R ₂ ) - (R ₂ is a linear alkyl group having 1 to 5 carbon atoms or Is a branched alkyl group having 1 to 5 carbon atoms). More preferably -O-, -CONH-, -NHCO- or -NH-. More preferably -O-, -CONH- or -NHCO-.

In formula [2B], X ₆ is an organic group having 12 to 25 carbon atoms having a steroid skeleton, and more preferably an organic group having 15 to 25 carbon atoms and having a steroid skeleton.

In the formula [2B], q is an integer of 2 to 15. Among them, an integer of 2 to 10 is preferable. And more preferably an integer of 2 to 7.

&Lt; Synthesis method of specific side chain type diamine compound >

The method for producing the specific side chain type diamine compound represented by the formula [2A] or the formula [2B] of the present invention is not particularly limited, but can be produced, for example, by the following method.

For example, the specific diamine compound represented by the formula [2A] of the present invention can be obtained by synthesizing a dinitro compound represented by the formula [2-I], further reducing a nitro group to an amino group. There is no particular limitation on the method for reducing the dinitro compound. The method for reducing the dinitro compound is usually carried out by using palladium-carbon, platinum oxide, Raney nickel, platinum black, rhodium-alumina or platinum sulfide carbon as a catalyst and using ethyl acetate, toluene, , Dioxane, or an alcohol-based solvent by hydrogen gas, hydrazine, hydrogen chloride, or the like. X ₁ , X ₂ , X ₃ , X ₄ , m, n and p in the formula [2-I] have the same meanings as defined in the formula [2A].

delete

The dinitro of formula [2-I] is obtained by binding a - (CH ₂ ) _m - moiety of a dinitro group to - (X ₂ ) _n - (X ₃ ) _p -X ₄ via a linking moiety X ₁ Can be obtained.

X ₁ represents a single bond, -O- (ether bond), -COO- (ester bond), -OCO- (reverse ester bond), -CONH- (amide bond), -NHCO- (reverse amide bond) , -NH- (amino bond), -N (R ₁ ) - (R ₁ is a linear alkyl group having 1 to 5 carbon atoms or a branched alkyl group having 1 to 5 carbon atoms) or -S- (S bond ), And these bonding groups can be formed by appropriately selecting and using a known technique in organic synthesis.

delete

For example, X ₁ is -O- (ether bond) in the case, formula [II-2] and Xa is halogen the dinitro group-containing halogen derivative, formula [III-2] Xb is a hydroxyl group of (OH groups) in Is reacted in the presence of an alkali. The halogen of the dinitro group-containing halogen derivative is preferably Cl (chlorine) or Br (bromine). The dinitro group-containing halogen derivative can be obtained by halogenation of the corresponding dinitrobenzyl alcohol. Examples of the halogenating agent to be used at this time include BBr ₃ , BCl ₃ , PBr ₃ , PCl ₃ , PPh ₃ / CBr ₄ , PPh ₃ / CCl ₄ , SOBr ₂ and SOCl ₂ .

If X ₁ is -COO- (ester bond), a group of the formula [II-2] and Xa of the acid chloride the dinitro group-containing acid chloride derivative, formula [III-2] Xb is a hydroxyl group (OH group) of the hydroxyl group And the derivative is allowed to react in the presence of an alkali.

(2) wherein X ₁ in formula [2-II] is a hydroxyl group (OH group) and X 1 in formula [2-III] is an acid chloride A method in which a chloride derivative is reacted in the presence of an alkali.

(2-II) is a compound wherein Xa in formula [2-II] is an acid chloride and an acid chloride derivative in which Xb in formula [2-III] is an amino group (NH ₂ group) when X ₁ is -CONH- And a method of reacting an amino group derivative in the presence of an alkali.

A dinitro group-containing amino group derivative in which Xa in the formula [2-II] is an amino group (NH ₂ group) and X 2 in the formula [2-III] is an acid chloride group when X ₁ is -NHCO- And a method in which an acid chloride derivative is reacted in the presence of an alkali.

(2-II)] wherein Xa in formula [2-II] is a halogen, when X ₁ is -NH- (amino bond) or N (R ₁ ) In which Xb in the formula ( ₁ ) is an amino group (NH ₂ group) or an alkylated amino group (NH (R ₁ ) group) in the presence of an alkali.

In the specific side chain type diamine compound represented by the above formula [2A], a novel compound is also contained.

&Lt; Other diamine compounds >

In the present invention, as long as the effect of the present invention is not impaired, other diamine compounds (other diamine compounds) other than the specific side chain diamine compound may be used as the diamine component. Specific examples thereof are given below.

p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl- Diaminodiphenol, 3,5-diaminophenol, 3,5-diaminobenzyl, 2,4-diaminophenol, 3,5-diaminophenol, Alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, Dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diamino Biphenyl, 3,3'-difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'- diaminobiphenyl, Diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyl Methane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diamino Phenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, Bis (3-aminophenyl) silane, dimethyl-bis (4-aminophenyl) silane, dimethyl- bis (3-aminophenyl) silane, Aminophenyl) silane, 4,4'-thiodianiline, 3,3'-thiodianiline, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'- Diaminodiphenylamine, 2,3-diaminodiphenylamine, N-methyl (4,4'-diaminodiphenyl) amine, N-methyl (3, (2,3'-diaminodiphenyl) amine, N-methyl (3,4'-diaminodiphenyl) amine, N-methyl Diaminodiphenyl) amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2 ' - diaminobenzophenone, 2,3'-diaminobenzophenone, Diaminonaphthalene, 1,6-diaminonaphthalene, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,6-diaminonaphthalene, Bis (4-aminophenyl) ethane, 1, 3-bis (4-aminophenyl) ) Propane, 1,3-bis (3-aminophenyl) propane, 1,4-bis (4-aminophenyl) butane, 1,4- Aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1, (4-aminophenyl) benzene, 1,4-bis (4-aminobenzyl) benzene, Phenylene bis (methylene)] dianiline, 4,4 '- [1,3-phenylenebis (methylene)] dianiline, 3,4' - [ , 4'- [1,3-phenylenebis (methylene)] dianiline, 3,3 '- [1,4-phenylenebis (methylene)] dianiline, Phenylenebis [(3-amino)] phenanthrene [(4-aminophenyl) methanone] Phenylenemethanone], 1,3-phenylenebis [(4-aminophenyl) methanone], 1,3-phenylenebis [ Aminobenzoate), 1,3-phenylenebis (3-aminobenzoate), 1,3-phenylenebis (4-aminobenzoate) Bis (3-aminophenyl) isophthalate, bis (4-aminophenyl) isophthalate, N, N ' Bis (4-aminobenzamide), N, N '- (1,4-phenylene) bis (3-aminobenzamide), N, N '- (1,3-phenylene) bis (3-aminobenzamide), N, N'- Bis (3-aminophenyl) terephthalamide, N, N'-bis (4- (4-aminophenoxy) anthracene, 4,4'-bis (4-aminophenoxy) diphenyl Bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2'-bis [ Bis (3-aminophenyl) hexafluoropropane, 2,2'-bis (3-aminophenyl) hexafluoropropane, 2,2'- Bis (3-aminophenyl) propane, 2,2'-bis (4-aminophenyl) propane, (4-aminophenoxy) propane, 1,3-bis (3-aminophenoxy) propane, 1,4- Bis (4-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) pentane, Aminophenoxy) hexane, 1,7-bis (4-aminophenoxy) heptane, 1,7- Phenoxy) heptane, 1,8-bis (4-aminophenoxy) octane, 1,8-bis -Bis (3-aminophenoxy) nonane, 1,10- (4-aminophenoxy) decane, 1,10- , 1,11- (3-aminophenoxy) undecane, 1,12- (4-aminophenoxy) dodecane, 1,12- , Aromatic diamines such as 3- (aminomethyl) aniline, 4- (2-aminoethyl) aniline or 3- (2-aminoethylaniline); Alicyclic diamines such as bis (4-aminocyclohexyl) methane and bis (4-amino-3-methylcyclohexyl) methane; 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1, Aliphatic diamines such as 9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane.

In addition, as long as the effect of the present invention is not impaired, diamine compounds represented by the following formulas [DA-1] to [DA-31] can be used.

delete

(Wherein R ₁ is -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ - or -CH ₂ OCO-, and R ₂ is a carbon number A linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched alkoxyl group having 1 to 22 carbon atoms, a linear or branched alkyl group having 1 to 22 carbon atoms, or a linear chain type having 1 to 22 carbon atoms Or branched fluorine-containing alkoxyl group)

delete

(Wherein R ₃ is -COO-, -OCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ - or - CH ₂ -, R ₄ is a linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched alkoxyl group having 1 to 22 carbon atoms, a linear or branched alkyl group having 1 to 22 carbon atoms, Or a linear or branched fluorine-containing alkoxyl group having 1 to 22 carbon atoms)

delete

(Wherein [DA-7] and the equation [DA-8] of, R ₅ is _{-COO-, -OCO-, -COOCH 2 -,} -CH 2 OCO-, -CH 2 O-, -OCH 2 -, - CH ₂ - or -O- and R ₆ is a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group or a hydroxyl group)

delete

(Wherein R ₇ is a linear or branched alkyl group having 3 to 12 carbon atoms and the cis-trans isomer of 1,4-cyclohexylene is a trans isomer, respectively, in the formula [DA-9] and the formula [DA-

delete

(In the formulas [DA-11] and [DA-12], R ₈ is a linear or branched alkyl group having 3 to 12 carbon atoms and the cis-trans isomer of 1,4-cyclohexylene is a trans isomer.

delete

(In the formula [DA-13], A ₄ is a linear or branched alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, A ₃ is a 1,4-cyclohexylene group or a 1,4- , A ₂ is -O- or -COO- * (provided that the bonding hands to which "*" is bonded are bonded to A ₃ ), A ₁ is -O- or -COO- * (provided that "*" And the combined hand is combined with (CH ₂ ) a ₂ ). A ₁ is an integer of 0 or 1, a ₂ is an integer of 2 to 10, and a ₃ is an integer of 0 or 1.)

delete

delete

delete

delete

delete

In addition, as long as the effect of the present invention is not impaired, a diamine compound represented by the following formula [DA-32] can be used.

delete

(In the formula [DA-32], A ₁ is -O-, -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON ₃ ) - or -N (CH ₃ ) CO-, A ₂ is a single bond, an aliphatic hydrocarbon group of 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group or an aromatic hydrocarbon group, A ₃ is a single bond, -O-, -NH-, -N (CH 3) -, -CONH-, -NHCO-, -COO-, -OCO-, -CON (CH 3) -, -N (CH 3) CO- or -O (CH ₂ ) _m - (m is an integer of 1 to 5), A ₄ is a nitrogen-containing aromatic heterocyclic ring, and n is an integer of 1 to 4.

In addition, as long as the effect of the present invention is not impaired, a diamine compound having an alkyl group or a fluorine-containing alkyl group in the diamine side chain can be used.

Specifically, diamines represented by the following formulas [DA-33] to [DA-44] can be exemplified.

delete

(In the formulas [DA-33] to [DA-37], A ₁ is a linear or branched alkyl group having 1 to 22 carbon atoms or a linear or branched fluorinated alkyl group having 1 to 22 carbon atoms.

delete

(In the formulas [DA-38] to [DA-43], A ₂ represents -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO- or -NH -, A ₃ is a linear or branched alkyl group having 1 to 22 carbon atoms or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms)

delete

(In the formula [DA-44], p is an integer of 1 to 10)

In addition, as long as the effect of the present invention is not impaired, diamine compounds represented by the following formulas [DA-45] to [DA-52] may be used.

delete

(In the formula [DA-49], m is an integer of 0 to 3. In the formula [DA-52], n is an integer of 1 to 5.)

In addition, as long as the effect of the present invention is not impaired, a diamine compound having a carboxyl group in the molecule represented by the following formulas [DA-53] to [DA-57]

delete

(Wherein [DA-53], m ₁ is an integer of 1 to 4, wherein [DA-54], A ₄ represents a single _{bond, -CH 2 -., -C 2} H 4 -, -C (CH 3 _{) 2 -, -CF 2 -,} -C (CF 3) 2 -, -O-, -CO-, -NH-, -N (CH 3) -, -CONH-, -NHCO-, -CH 2 O -, -OCH ₂ -, -COO-, -OCO-, -CON (CH ₃ ) - or -N (CH ₃ ) CO-, m ₂ and m ₃ are each independently an integer of 0 to 4, m ₂ + m ₃ is an integer from 1 to 4. expression [DA-55] from, m ₄ and m ₅ are in each independently an integer of 1 to 5. the expression [DA-56], a ₅ is C 1 And m ₆ is an integer of 1 to 5. In the formula [DA-57], A ₆ is a single bond, -CH ₂ -, -C ₂ H ₄ -, -C (CH ₃ ) ₂ -, -CF ₂ -, -C (CF ₃ ) ₂ -, -O-, -CO-, -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, _{CH 2 O-, -OCH 2 -,} -COO-, -OCO-, -CON (CH 3) - or a -N (CH ₃₎ CO-, ₇ m is an integer from 1 to 4).

In addition, as long as the effect of the present invention is not impaired, diamine compounds represented by the following formulas [DA-58] and [DA-59] may be used.

delete

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

&Lt; Specific tetracarboxylic acid dianhydride >

In order to obtain the specific polymer of the present invention, it is preferable to use a tetracarboxylic acid dianhydride (also referred to as a specific tetracarboxylic acid dianhydride) represented by the following formula [3] as a part of the starting material.

delete

In the formula [3], Z ₁ is a tetravalent organic group having 4 to 13 carbon atoms and further contains a non-aromatic cyclic hydrocarbon group having 4 to 10 carbon atoms.

Z ₁ is specifically, for example, a tetravalent group represented by the following formulas [3a] to [3j].

delete

In the formula [3a], Z ₂ to Z ₅ are each a group selected from a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different.

In the formula [3g], Z ₆ and Z ₇ are each a hydrogen atom or a methyl group and may be the same or different.

Especially preferred structures of Z _{1 in} the formula [3] are those of the formula [3a], the formula [3c], the formula [3d], the formula [3e], the formula [3f] ] to be. Among them, the formula [3a], the formula [3e], the formula [3f] or the formula [3g] is preferable.

&Lt; Other tetracarboxylic acid dianhydrides >

In the present invention, other tetracarboxylic acid dianhydrides (other tetracarboxylic acid dianhydrides) other than the specific tetracarboxylic acid dianhydrides may be used as long as the effects of the present invention are not impaired . Examples of other tetracarboxylic acid dianhydrides include tetracarboxylic acid dianhydrides of the following tetracarboxylic acids.

Naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, Anthracene tetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4- Biphenyltetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3 ', 4,4'-benzophenonetetracarboxylic acid, bis (3,4- Dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2- Dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5-pyridine tetracarboxylic acid, 2 , 6-bis (3,4-dicarboxyphenyl) pyridine, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 3-diphenyl-1,2,3,4-cyclobutane tetracarboxylic acid.

The above-mentioned specific tetracarboxylic acid dianhydrides and other tetracarboxylic acid dianhydrides may be used alone or in combination of two or more thereof depending on the properties such as liquid crystal aligning property, voltage retention rate, and accumulated charge when the liquid crystal alignment film is used .

&Lt; Specific polymer &

The specific polymer of the present invention is at least one polymer selected from the group consisting of a polyamic acid obtained by reacting a diamine component and a tetracarboxylic acid component, and a polyimide obtained by dehydrocondylating the polyamic acid.

The polyimide precursor has a structure represented by the following formula [A].

delete

(In the formula [A], R ₁ is a tetravalent organic group, R ₂ is a divalent organic group, and A ₁ and A ₂ are each a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and may be the same or different. n represents a positive integer.)

The specific polymer of the present invention is preferably a repeating unit represented by the following formula [D], because it is relatively easily obtained by using the diamine component represented by the following formula [B] and the tetracarboxylic acid dianhydride represented by the following formula [C] Or a polyimide in which the polyamic acid is imidized is preferable.

delete

(In the formulas [B], formula [C] and formula [D], R ₁ and R ₂ have the same meanings as defined in formula [A]

In the formulas [A] and [D], each of R ₁ and R ₂ may be a single kind or a combination of plural kinds of different repeating units having different R ₁ and R ₂ .

In the present invention, a method of synthesizing a specific polymer is not particularly limited. It is usually obtained by reacting a diamine component with a tetracarboxylic acid component. Generally, a polyamic acid is obtained by reacting at least one tetracarboxylic acid component selected from the group consisting of a tetracarboxylic acid and a derivative thereof and a diamine component composed of one or more kinds of diamine compounds. Specifically, there may be mentioned a method of obtaining a polyamic acid by polycondensation of a tetracarboxylic acid dianhydride and a diamine component, a method of obtaining a polyamic acid by dehydration polycondensation reaction of a tetracarboxylic acid and a diamine component, A method of polycondensing a diamine component to obtain a polyamic acid is used.

To obtain the polyamide acid alkyl ester, a method of polycondensation of a tetracarboxylic acid having a carboxylic acid group with a dialkyl ester and a diamine component, a method of polycondensation of a diamine component with a tetracarboxylic dihalide obtained by dialkyl esterifying a carboxylic acid group Or a method of converting a carboxyl group of a polyamic acid into an ester is used.

To obtain the polyimide, a method of converting the above polyamic acid or polyamide acid alkyl ester into a polyimide by ring closure is used.

The liquid crystal alignment film obtained by using the specific polymer of the present invention is preferably such that the content of the specific side chain structure represented by the formula [1A] or the formula [1B] in the diamine component is larger, And the pretilt angle of the liquid crystal can be increased. At this time, it is preferable to use a specific side chain type diamine compound represented by the above formula [2A] or formula [2B] for the diamine component. Particularly preferably, the side chain type diamine compound represented by the formula [2A] is used. For the purpose of enhancing this property, it is preferable that 5 mol% or more and 80 mol% or less of the diamine component is a specific side chain type diamine compound. Of these, from the viewpoint of coating properties of the liquid crystal alignment treatment agent and electric characteristics as a liquid crystal alignment film, it is preferable that 5 mol% or more and 60 mol% or less of the diamine component is a specific side chain type diamine compound.

In order to obtain the specific polymer of the present invention, it is preferable to use the specific tetracarboxylic acid dianhydride represented by the above formula [3] as the tetracarboxylic acid component. In particular, the formula [3] in the Z ₁ is preferable to use a structure in which a tetracarboxylic acid dianhydride represented by the above formula [3a] ~ formula [3j]. At this time, it is preferable that 1 mol% or more of the tetracarboxylic acid component is a specific tetracarboxylic acid dianhydride, more preferably 5 mol% or more, and further preferably 10 mol% or more. In addition, 100 mol% of the tetracarboxylic acid component may be a specific tetracarboxylic acid dianhydride.

The reaction of the diamine component and the tetracarboxylic acid component is usually carried out in an organic solvent. The organic solvent to be used at this time is not particularly limited as long as it dissolves the resulting polyimide precursor. Specific examples thereof are given below.

Examples of the solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, , Methyl ethyl ketone, cyclohexanone, cyclopentanone or 4-hydroxy-4-methyl-2-pentanone.

These may be used alone or in combination. The solvent may be a solvent that does not dissolve the polyimide precursor, or may be mixed with the solvent to the extent that the resulting polyimide precursor does not precipitate. In addition, water in the organic solvent inhibits the polymerization reaction and further causes hydrolysis of the resulting polyimide precursor, and therefore, the organic solvent is preferably dehydrated and dried.

When the diamine component and the tetracarboxylic acid component are reacted in an organic solvent, a method in which a solution in which a diamine component is dispersed or dissolved in an organic solvent is stirred and a tetracarboxylic acid component is added as it is or dispersed or dissolved in an organic solvent , A method of adding a diamine component to a solution in which a tetracarboxylic acid component is dispersed or dissolved in an organic solvent, a method of alternately adding a tetracarboxylic acid component and a diamine component, and the like. May be used. When a plurality of diamine components or tetracarboxylic acid components are used to carry out the reaction, they may be reacted in a preliminarily mixed state, or they may be sequentially reacted individually, or the individually reacted low molecular weight compounds are mixed and reacted, . The polymerization temperature at that time may be any temperature within the range of -20 to 150 ° C, preferably -5 to 100 ° C. The reaction can be carried out at an arbitrary concentration. However, if the concentration is too low, it becomes difficult to obtain a specific polymer having a high molecular weight. If the concentration is too high, the viscosity of the reaction liquid becomes too high, and uniform stirring becomes difficult. Therefore, the content is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass. The reaction may be carried out at a high concentration in the initial stage, and then an organic solvent may be added.

In the polymerization reaction of the polyimide precursor, the ratio of the total molar number of the diamine component to the total molar number of the tetracarboxylic acid component is preferably 0.8 to 1.2. As in the case of the usual polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the resulting polyimide precursor.

The polyimide of the present invention is a polyimide obtained by ring closure of the above polyimide precursor, and is useful as a polymer for obtaining a liquid crystal alignment film.

In the polyimide of the present invention, the closed rate (the imidization rate) of the amidic acid group does not necessarily have to be 100%, but can be arbitrarily adjusted depending on the application and purpose.

Examples of the method for imidizing the polyimide precursor include thermal imidization for directly heating the solution of the polyimide precursor or catalyst imidization for adding a catalyst to a solution of the polyimide precursor.

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

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

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

The molecular weight of the specific polymer of the present invention is preferably 5,000 or more in terms of the weight average molecular weight measured by GPC (Gel Permeation Chromatography) when the strength of the polymer film obtained therefrom, the workability in forming the polymer film, and the uniformity of the polymer film are taken into consideration. To 1,000,000, and more preferably from 10,000 to 150,000.

&Lt; Liquid crystal alignment treatment agent &

The liquid crystal alignment treatment agent of the present invention is a coating liquid for forming a liquid crystal alignment film and is a coating liquid for forming a resin film containing a specific polymer and an organic solvent.

All the polymer components in the liquid crystal alignment treatment agent of the present invention may be all the specific polymers used in the present invention, and the other polymers may be mixed with the specific polymer of the present invention. At this time, the content of the other polymer is 0.5 to 15% by mass, preferably 1 to 10% by mass. Examples of the other polymer include a polyimide precursor or polyimide not containing a specific side chain structure. Further, a polyimide precursor and a polymer other than polyimide, specifically acrylic polymer, methacrylic polymer, polystyrene, polyamide and the like can be given.

The organic solvent in the liquid crystal alignment treatment agent of the present invention preferably has an organic solvent content of 70 to 99 mass%, more preferably 80 to 99 mass%, from the viewpoint of forming a uniform film by coating. This content can be appropriately changed depending on the film thickness of the intended liquid crystal alignment film. The organic solvent at that time is not particularly limited as long as it is an organic solvent capable of dissolving a specific polymer. Specific examples thereof are given below.

Examples of the solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, , Methyl ethyl ketone, cyclohexanone, cyclopentanone, and 4-hydroxy-4-methyl-2-pentanone.

These may be used alone or in combination.

The liquid crystal alignment treatment agent of the present invention may contain a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group, a cyclocarbonate group or the like, a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group, as long as the effect of the present invention is not impaired A crosslinkable compound having at least one kind of substituent selected from the group consisting of a halogen atom, a crosslinkable compound having a polymerizable unsaturated bond, and the like. These substituents and polymerizable unsaturated bonds need to have two or more in the crosslinkable compound.

Examples of the crosslinkable compound having an epoxy group, an isocyanate group and the like include, for example, bisphenol acetone glycidyl ether, phenol novolac epoxy resin, cresol novolak epoxy resin, triglycidyl isocyanurate, tetraglycidyl amino di Phenylene, tetraglycidyl-m-xylenediamine, tetraglycidyl-1,3-bis (aminoethyl) cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoro 1,3-bis (1- (2,3-epoxypropoxy) -1-trifluoromethyl-2,2,2-trifluoromethyl) benzene, 4,4- Bis (2,3-epoxypropoxy) octafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidyl methaxylenediamine, 2- (4- (2,3- Bis (4- (1, 4- (2,3-epoxypropoxy) phenyl) ethyl) phenyl) propane, Epoxypropoxy) phenyl) -1- (4- (1- (4- ( 2,3-epoxypropoxy) phenyl) -1-methylethyl) phenyl) ethyl) phenoxy) -2-propanol.

The crosslinkable compound having an oxetane group is a crosslinkable compound having at least two oxetane groups represented by the following formula [4].

delete

Specifically, it is a crosslinkable compound represented by the following formulas [4-1] to [4-11].

delete

delete

delete

The crosslinkable compound having a cyclocarbonate group is a crosslinkable compound having at least two cyclocarbonate groups represented by the following formula [5].

delete

Specifically, it is a crosslinkable compound represented by the following formulas [5-1] to [5-37].

delete

delete

delete

delete

delete

delete

delete

delete

(In the formula [5-24], n is an integer of 1 to 5. In the formula [5-25], n is an integer of 1 to 5. In the formula [5-36], n is an integer of 1 to 100 In the formula [5-37], n is an integer of 1 to 10.)

Also, a polysiloxane having at least one structure represented by the following formulas [5-38] to [5-40] may be used.

delete

(Wherein R ₁ , R ₂ , R ₃ , R ₄ and R ₅ each independently represent a structure represented by the formula [5], a hydrogen atom, a hydroxyl group, An alkoxyl group, an aliphatic ring or an aromatic ring, and at least one of them is a structure represented by the formula [5]

More specifically, the compounds of the following formulas [5-41] and [5-42] can be mentioned.

delete

(In the formula [5-42], n is an integer of 1 to 10)

Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxyl group include an amino resin having a hydroxyl group or an alkoxyl group such as a melamine resin, Guanamine resin, glycoluril-formaldehyde resin, succinylamide-formaldehyde resin, ethylene urea-formaldehyde resin and the like. Specifically, a melamine derivative in which the hydrogen atom of the amino group is substituted with a methylol group and / or an alkoxymethyl group, a benzoguanamine derivative, glycoluril and the like can be used. The melamine derivative or the benzoguanamine derivative may be present as a dimer or trimer. They preferably have 3 to 6 on average of methylol groups or alkoxymethyl groups per one triazine ring.

Examples of such a melamine derivative or benzoguanamine derivative include MX-750 in which a methoxymethyl group is substituted in an average of 3.7 methoxymethyl groups per one triazine ring of a commercial product, MW having an average of 5.8 methoxymethyl groups per triazine ring -30 (manufactured by Sanwa Chemical Co., Ltd.), methoxymethylated melamine such as Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, Cymel 235, 236, 253 and 254, butoxymethylated melamines such as Cymel 506 and 508, carboxyl-containing methoxymethylated isobutoxymethylated melamines such as Cymel 1141, methoxymethylated ethoxy compounds such as Cymel 1123, Methoxymethylated butoxymethylated benzoguanamines such as methylated benzoguanamine and Cymel 1123-10, butoxymethylated benzoguanamines such as Cymel 1128, carboxyl-containing methoxymethylated methoxymethylated ethoxymethylated benzoates such as Cymel 1125-80 Ana min can be given (or more, between the mid-Mitsui Ana Company). Examples of glycoluril include butoxymethylated glycoluril such as Cymel 1170, methylol glycoluryl such as Cymel 1172, and methoxymethylolglycoluril such as Powderlink 1174, and the like.

Examples of the benzene or phenolic compound having a hydroxyl group or an alkoxyl group include 1,3,5-tris (methoxymethyl) benzene, 1,2,4-tris (isopropoxymethyl) benzene, 1 , 4-bis (sec-butoxymethyl) benzene, 2,6-dihydroxymethyl-p-tert-butylphenol and the like.

More specifically, it is a crosslinkable compound represented by the following formulas [6-1] to [6-48].

delete

delete

delete

delete

delete

delete

Examples of the crosslinkable compound having a polymerizable unsaturated bond include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tri ) Crosslinkable compounds having three polymerizable unsaturated groups such as acryloyloxyethoxy trimethylol propane and glycerin polyglycidyl ether poly (meth) acrylate; Acrylates such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di Acrylates such as di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide bisphenol A type di (meth) acrylate, propylene oxide bisphenol type di (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (Meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, A crosslinkable compound having two polymerizable unsaturated groups in the molecule; Hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (Meth) acryloyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2- And crosslinkable compounds having one polymerizable unsaturated group such as ester and N-methylol (meth) acrylamide in the molecule.

Further, a compound represented by the following formula [7] may also be used.

delete

(Wherein E ₁ represents a group selected from the group consisting of a cyclohexyl ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring and a phenanthrene ring E ₂ is a group selected from the following formulas [7a] and [7b], and n is an integer of 1 to 4.)

delete

The compound is an example of a crosslinking compound, but is not limited thereto. The crosslinkable compound contained in the liquid crystal alignment treatment agent of the present invention may be one kind or two or more kinds.

The content of the crosslinkable compound in the liquid crystal alignment treatment agent of the present invention is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of all the polymer components. More preferably from 0.1 to 100 parts by mass, particularly preferably from 1 to 50 parts by mass, based on 100 parts by mass of all the polymer components, so that the intended effect is exhibited and the orientation property of the liquid crystal is not lowered.

The liquid crystal alignment treatment agent of the present invention is a compound which accelerates charge transfer in the liquid crystal alignment film and promotes charge dropout of the liquid crystal cell using the liquid crystal alignment film as long as the effect of the present invention is not impaired, It is preferable to add a nitrogen-containing heterocyclic amine compound represented by [M156]. The amine compound may be directly added to a solution of a specific polymer, but it is preferable to add the amine compound in an appropriate solvent at a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass. This solvent is not particularly limited as long as it is an organic solvent for dissolving the above-mentioned specific polymer.

delete

delete

delete

delete

delete

delete

The liquid crystal alignment treatment agent of the present invention may contain an organic solvent (also referred to as a poor solvent) or a compound which improves the film thickness uniformity and surface smoothness of the polymer film when the liquid crystal alignment treatment agent is applied, Can be used. Further, a compound or the like which improves the adhesion between the liquid crystal alignment film and the substrate may be used.

Specific examples of the poor solvent for improving the uniformity of the film thickness and the surface smoothness include those shown below.

Butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, Butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl- Butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,3-propanediol, Butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, Ethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4- Ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-ethylhexyl acetoacetate, 2-ethylhexyl acetate, (Methoxymethoxy) ethanol, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether, 2- (hexyloxy) ethanol, furfuryl alcohol, diethylene glycol, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl Propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, Propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl Diethylene glycol, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, acetic acid (such as methyl acetate, ethyl acetate, Ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3- ethylhexyl methoxypropionate, The surface tension of a solvent such as methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, lactic acid methyl ester, lactic acid ethyl ester, n-propyl lactate, n-butyl lactate, It is a low organic solvent.

These poor solvents may be used alone or in combination. When such a poor solvent is used, it is preferably 5 to 80 mass%, more preferably 20 to 60 mass%, of the total amount of the organic solvent contained in the liquid crystal alignment treatment agent.

Examples of the compound that improves film thickness uniformity and surface smoothness include a fluorine-based surfactant, a silicon-based surfactant, and a nonionic surface-active agent.

More specifically, for example, EFTA EF301, EF303, and EF352 (manufactured by TOKEM PRODUCTS CO., LTD.), Megafac F171, F173, R-30 (manufactured by Dainippon Ink and Chemicals Inc.), FLORAD FC430 and FC431 manufactured by Sumitomo 3M ), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.). The use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, based on 100 parts by mass of all the polymer components contained in the liquid crystal alignment treatment agent.

Specific examples of the compound improving the adhesion between the liquid crystal alignment layer and the substrate include the following functional silane-containing compounds and epoxy group-containing compounds.

For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3 3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxy (2-aminoethyl) Aminopropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, Amine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl Acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N- Bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- Aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neo Pentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6 -Tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl ) Cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane and the like.

In the case of using a compound for improving adhesion with a substrate, it is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of all the polymer components contained in the liquid crystal alignment treatment agent. If the amount is less than 0.1 part by mass, the effect of improving the adhesion can not be expected, and if it is more than 30 parts by mass, the alignment property of the liquid crystal may be deteriorated.

The liquid crystal alignment treatment agent of the present invention may contain a crosslinking compound, a poor solvent, a compound which improves the uniformity of the film thickness and the surface smoothness and the compound which improves the adhesion with the substrate, , A dielectric material or a conductive material may be added for the purpose of changing electric characteristics such as dielectric constant and conductivity of the liquid crystal alignment film.

The liquid crystal alignment treatment agent of the present invention can be used as a liquid crystal alignment film after being applied and baked on a substrate, and subjected to an orientation treatment by rubbing treatment, light irradiation, or the like.

In addition, in the case of vertical alignment applications, etc., it can be used as a liquid crystal alignment film without alignment treatment.

The substrate to be used at this time is not particularly limited as long as it is a substrate having high transparency. In addition to the glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate can also be used. From the viewpoint of simplification of the process, it is preferable to use a substrate on which an ITO electrode or the like for liquid crystal driving is formed. In the reflection type liquid crystal display device, an opaque substrate such as a silicon wafer can be used as long as it is a substrate on only one side. As the electrode in this case, a material that reflects light such as aluminum can also be used.

The method of applying the liquid crystal alignment treatment agent is not particularly limited, but screen printing, offset printing, flexographic printing, and inkjet printing are generally used industrially. Examples of other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method, and a spraying method, and they may be used depending on the purpose.

After the liquid crystal alignment treatment agent is coated on the substrate, the solvent is evaporated at 50 to 300 ° C, preferably 80 to 250 ° C by a heating means such as a hot plate, a heat circulation type oven, an IR (infrared) It can be made into a film. When the thickness of the polymer film after firing is too large, the power consumption of the liquid crystal display element is deteriorated. When the thickness of the polymer film is too thin, the reliability of the liquid crystal display element may deteriorate. Therefore, the thickness is preferably 5 to 300 nm, more preferably 10 To 100 nm. When the liquid crystal is horizontally aligned or tilted, the polymer film after firing is subjected to rubbing, polarized ultraviolet irradiation, or the like.

The liquid crystal display element of the present invention is obtained by obtaining a substrate on which a liquid crystal alignment film is formed from the liquid crystal alignment treatment agent of the present invention by the above-mentioned technique, and then manufacturing a liquid crystal cell by a known method to form a liquid crystal display element.

As a manufacturing method of the liquid crystal cell, a pair of substrates on which a liquid crystal alignment film is formed is prepared, a spacer is scattered on the liquid crystal alignment film of the substrate of one substrate, the substrates of the other substrate are laminated so that the liquid crystal alignment film surface is inward, A method in which a liquid crystal is injected under reduced pressure to seal it, a method in which liquid crystal is dropped on the surface of a liquid crystal alignment film on which a spacer is dispersed, and then the substrate is sealed and subjected to sealing.

The liquid crystal alignment treatment agent of the present invention is a liquid crystal alignment treatment agent comprising a liquid crystal layer between a pair of substrates provided with an electrode and containing a polymerizable compound capable of polymerizing by at least one of active energy rays and heat between a pair of substrates The present invention is preferably used for a liquid crystal display device produced by a process of arranging a liquid crystal composition and polymerizing a polymerizable compound by irradiation of an active energy ray and heating while applying a voltage between electrodes. Here, the active energy ray is preferably ultraviolet ray. The ultraviolet ray has a wavelength of 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120 占 폚, preferably 60 to 80 占 폚. In addition, ultraviolet rays and heating may be simultaneously performed.

The liquid crystal display device described above controls the pretilt of liquid crystal molecules by a PSA (Polymer Sustained Alignment) method. In the PSA system, a small amount of a photopolymerizable compound such as a photopolymerizable monomer is mixed into a liquid crystal material, and a liquid crystal cell is assembled. Then, a predetermined voltage is applied to the liquid crystal layer, And controls the pretilt of the liquid crystal molecules by the produced polymer. Since the alignment state of the liquid crystal molecules when the polymer is produced is stored even after the voltage is removed, the pretilt of the liquid crystal molecules can be adjusted by controlling the electric field or the like formed on the liquid crystal layer. In addition, since the rubbing treatment is not required in the PSA system, it is suitable for forming a vertically aligned liquid crystal layer which is difficult to control the pretilt by the rubbing treatment.

That is, the liquid crystal display element of the present invention can be obtained by preparing a substrate on which a liquid crystal alignment film is formed from the liquid crystal alignment treatment agent of the present invention by the above-mentioned technique, and then producing a liquid crystal cell, The alignment of the liquid crystal molecules can be controlled by polymerizing the compound.

For example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, a spacer is dispersed on the liquid crystal alignment film of the substrate of the single chamber, and the liquid crystal alignment film surface is made inward, A method in which a liquid crystal is injected under reduced pressure and sealed, a method in which a liquid crystal is dropped on a surface of a liquid crystal alignment film on which a spacer is dispersed, and then a substrate is bonded and sealed.

The liquid crystal is mixed with a polymerizable compound which polymerizes by irradiation with heat or ultraviolet rays. Examples of the polymerizable compound include a compound having at least one polymerizable unsaturated group such as an acrylate group or a methacrylate group in the molecule. At that time, the amount of the polymerizable compound is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the liquid crystal component. When the amount of the polymerizable compound is less than 0.01 part by mass, the polymerizable compound is not polymerized and the orientation of the liquid crystal can not be controlled. When the amount is larger than 10 parts by mass, unreacted polymerizable compound increases, .

After the liquid crystal cell is manufactured, the polymerizable compound is polymerized by applying heat or ultraviolet rays while applying alternating current or direct current voltage to the liquid crystal cell. Thereby, the orientation of the liquid crystal molecules can be controlled.

The liquid crystal alignment treatment agent of the present invention is a liquid crystal alignment treatment agent comprising a liquid crystal layer between a pair of substrates provided with an electrode and containing a polymerizable group polymerizable by at least one of active energy rays and heat between the pair of substrates It is preferably used for a liquid crystal display element manufactured by arranging a liquid crystal alignment film and applying a voltage between electrodes. Here, the active energy ray is preferably ultraviolet ray. The ultraviolet ray has a wavelength of 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120 占 폚, preferably 60 to 80 占 폚. In addition, ultraviolet rays and heating may be simultaneously performed.

In order to obtain a liquid crystal alignment film containing a polymerizable group polymerizable by at least one of an active energy ray and heat, a method of adding a compound containing this polymerizable group to a liquid crystal alignment treatment agent, a method of using a polymer component containing a polymerizable group Method. Since the liquid crystal alignment treatment agent of the present invention contains a specific compound having a double bonding site that reacts by irradiation with heat or ultraviolet rays, the orientation of the liquid crystal molecules can be controlled by at least one of irradiation with ultraviolet rays and heating have.

For example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, spacers are dispersed on the liquid crystal alignment film of the substrate of one substrate, and the substrates of the other substrate are laminated so that the liquid crystal alignment film surface is inward A method in which a liquid crystal is injected under reduced pressure, a method in which liquid crystal is dropped on a surface of a liquid crystal alignment film on which a spacer is dispersed, and a method in which a substrate is bonded by sealing.

After the liquid crystal cell is manufactured, the orientation of the liquid crystal molecules can be controlled by applying heat or ultraviolet rays while applying alternating current or direct current voltage to the liquid crystal cell.

As described above, the liquid crystal display element manufactured using the liquid crystal alignment treatment agent of the present invention is excellent in reliability, and can be suitably used for a liquid crystal television with a large screen and a high definition.

Example

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

[Synthesis of Specific Side Chain Diamine Compound]

The analytical apparatus and analysis conditions employed in the identification of the specific side chain type diamine compound of the present invention are as follows.

( ¹ H-NMR measurement)

Apparatus: Varian NMR System 400NB (400 MHz) (manufactured by Varian)

Measurement solvents: CDCl ₃ (deuterated chloroform) and DMSO-d ₆ (Deuterated dimethylsulfoxide)

Reference material: TMS (tetramethylsilane) (?: 0.0 ppm, ¹ H) and CDCl ₃ (?: 77.0 ppm, ¹³ C)

&Lt; Example 1 >

Synthesis of Specific Side Chain Diamine Compound (1)

delete

K ₂ CO ₃ (potassium carbonate) (18.1 g, 131 mmol) and KI (potassium iodide) were added to a DMF (dimethylformamide) solution (190 ml) of the phenol derivative (a) (30.0 g, 109 mmol) 1.81 g, 10.9 mmol) was added and the temperature was raised to 60 < 0 > C. Then, propargyl bromide (19.5 g, 164 mmol) was added dropwise and reacted for 24 hours. The reaction solution was then poured into water (360 mL). The precipitated solid was separated by filtration, and the obtained solid was washed with stirring in methanol to obtain crude propargyl ether (b) (yield: 32.5 g, yield: 95%). The obtained crude product was used in the next reaction as it was.

Propargyl ether (b):

delete

PdCl ₂ (PPh ₃ ) ₂ (0.562 g, 0.801 mmol) was added to a THF (tetrahydrofuran) solution (106 ml) of 3,5-dinitroiodobenzene (c) (23.5 g, 80.1 mmol) CuI (copper (I) iodide) (0.305 g, 1.60 mmol), and Et ₂ NH (diethylamine) (7.61 g, 104 mmol) were added followed by cooling in a water bath. To this solution, THF solution (22.0 ml) of propargyl ether (b) (32.5 g, 104 mmol) was added dropwise. After stirring for 1 hour, the reaction solution was poured into water (560 mL). The precipitated solid was separated by filtration, and the obtained solid was recrystallized from a mixed solvent of ethyl acetate and hexane to obtain dinitro compound (d) (yield: 23.6 g, yield: 62%).

Dinitro (d):

delete

Pd / C (palladium carbon) (2.33 g) was added to a mixed solution of dinitro compound (d) (23.3 g, 48.7 mmol) in THF (131 ml) and toluene (134 ml) Stir at room temperature. After reacting for 96 hours, Pd / C was removed by filtration. The filtrate was concentrated and the resulting solid was recrystallized from a mixed solvent of 1,4-dioxane and hexane to obtain a specific side chain diamine compound (1) (yield: 11.9 g, yield: 58%).

Specific side chain type diamine compound (1):

&Lt; Example 2 >

Synthesis of Specific Side Chain Diamine Compound (2)

delete

Phenol derivative (a) in DMF solution (64.0 ㎖) of (30.0 g, 109 m㏖), K 2 CO 3 (27.2 g, 197 m㏖), KI (0.907 g, 5.47 m㏖), and 5-chloro- 1-Pentyne (15.7 g, 153 mmol) was added, and the mixture was heated to 100 DEG C and reacted for 48 hours. Thereafter, DMF (95.0 ml) was added after cooling to 25 ° C, and water (30 ml) was added dropwise to the reaction solution to stop the reaction. The reaction mixture was poured into water (150 ml), and the precipitated solid was separated by filtration. The resulting solid was recrystallized from a mixed solvent of ethyl acetate and methanol to obtain ether (e) (yield: 33.7 g, yield: 91%).

Ether (e):

delete

PdCl ₂ (PPh ₃ ) ₂ (0.477 g, 0.680 mmol), CuI (0.259 g, 0.680 mmol) was added to a THF solution (90 ml) of 3,5- dinitroiodobenzene (c) 1.36 mmol), and Et ₂ NH (6.47 g, 88.4 mmol) were added, followed by cooling in a water bath. To this solution, a THF solution (45.0 ml) of the terminal acetylene form (e) (30.1 g, 88.4 mmol) was added dropwise. After stirring for 20 hours, the reaction solution was poured into water (600 mL). The precipitated solid was separated by filtration, and the resulting solid was recrystallized from a mixed solvent of THF and methanol to obtain a dinitro furane (yield: 30.0 g, yield: 87%).

Dinitro (f):

delete

Pd / C (2.97 g) was added to a mixed solution of dinitrofurf (29.7 g, 58.6 mmol) in THF (167 ml) and toluene (172 ml), and the mixture was stirred under hydrogen atmosphere at room temperature . After reaction for 72 hours, Pd / C was removed by filtration. The filtrate was concentrated, and the resulting solid was recrystallized from a mixed solvent of THF and hexane to obtain a specific side chain type diamine compound (2) (22.1 g, 84%).

Specific side chain type diamine compound (2):

&Lt; Example 3 >

Synthesis of Specific Side Chain Diamine Compound (3)

delete

1 N (80.0 mmol) of catechol borane THF solution (80.0 ml) was added dropwise over 1 hour to a THF solution (96.0 ml) of the terminal acetylene form (e) (17.0 g, 49.9 mmol) And the mixture was stirred at reflux for 24 hours. Thereafter, after cooling to 25 DEG C, a 2N aqueous hydrochloric acid solution (150 mL) was added to the reaction solution, and the mixture was stirred for 2 hours and poured into water (2000 mL). The precipitated solid was separated by filtration and washed with hexane to obtain a boronic acid derivative (h). The obtained boronic acid derivative was used in the next step as it is.

delete

Boronic acid derivative (h) (17.7 g, 45.8 m㏖), 2,4- dinitro-chloro-benzene (k) (8.84 g, 43.6 m㏖), and _{Pd (PPh 3) 4 (0.530} g, 0.459 m㏖) Dioxane solution (55.7 ml) was added 2.0 mol / l potassium carbonate aqueous solution (55.7 ml), and the mixture was stirred at 80 占 폚 for 2 hours. Thereafter, separation was performed between ethyl acetate and water, and the organic layer was dried with magnesium sulfate. The organic layer was concentrated, and the resulting solid was subjected to column chromatography using ethyl acetate and hexane to obtain dinitro compound (m) (13.1 g, 59%).

Dinitro (m):

delete

Pd / C (1.30 g) was added to a THF solution (130 ml) of dinitro compound (m) (13.0 g, 25.6 mmol) and the mixture was stirred under hydrogen atmosphere at room temperature. After reacting for 24 hours, Pd / C was removed by filtration. Activated carbon was added to the filtrate, stirred for 2 hours, and the activated carbon was removed by filtration. Thereafter, the filtrate was concentrated to obtain a specific side chain type diamine compound (3) (11.0 g, 95%).

Specific side chain type diamine compound (3):

[Synthesis of polyimide precursor and polyimide]

The abbreviations of the compounds used in Examples and Comparative Examples are as follows.

(Tetracarboxylic acid dianhydride)

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

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

TCA: tetracarboxylic acid dianhydride represented by the following formula

TDA: tetracarboxylic acid dianhydride represented by the following formula

delete

(Specific side chain type diamine compound)

A-1: Specific side chain type diamine compound (1) obtained by the synthesis route of Example 1

A-2: Specific side chain type diamine compound (2) obtained by the synthesis route of Example 2

A-3: Specific side chain type diamine compound (3) obtained by the synthesis route of Example 3

delete

(Other diamine compounds)

p-PDA: p-phenylenediamine

m-PDA: m-Phenylenediamine

DBA: 3,5-diaminobenzoic acid

AP18: 1,3-Diamino-4-octadecyloxybenzene

delete

(Organic solvent)

NMP: N-methyl-2-pyrrolidone

BCS: butyl cellosolve

Measurement of the molecular weight and measurement of the imidization rate were carried out as follows.

(Molecular weight measurement)

The molecular weight of the polyimide in Synthesis Example was measured using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko K.K.), a column (KD-803, KD-805) And measured as follows.

Column temperature: 50 ° C

Eluent: N, N'- dimethylformamide (lithium bromide as an additive-hydrate (LiBr · H ₂ O) is 30 m㏖ / ℓ, phosphoric acid anhydrous crystal (o- phosphoric acid) is 30 m㏖ / ℓ, tetrahydrofuran (THF) of 10 ml / l)

Flow rate: 1.0 ml / min

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

(Measurement of imidization rate)

20 mg of the polyimide powder was placed in an NMR sample tube (NMR sampling tube standard φ5 (manufactured by Kusano Scientific)) and 0.53 ml of deuterated dimethyl sulfoxide (DMSO-d6, 0.05 mass% TMS (tetramethylsilane) And completely dissolved by applying ultrasonic waves. This solution was subjected to proton NMR measurement at 500 MHz using an NMR measuring instrument (JNW-ECA500) (manufactured by Nippon Denshoku). The proton derived from the structure in which the imidization rate does not change before and after the imidization is defined as the reference proton and the proton peak integrated value derived from the NH group of the amide acid appearing near 9.5 to 10.0 ppm is used And was obtained by the following formula.

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

In the above formula, x is the proton peak integrated value derived from the NH group of the amide acid, y is the peak integrated value of the reference proton, and? Is the NH of the amide acid when the polyamide acid (imidization ratio is 0% The ratio of the number of reference protons to one protopertone.

(1.94 g, 4.6 mmol) and p-PDA (1.99 g, 18.4 mmol) were mixed in NMP (25.3 g) and reacted at 40 ° C for 5.5 hours To obtain a polyamic acid solution (1) having a resin solid content concentration of 25.0 mass%. The polyamic acid had a number average molecular weight of 25,900 and a weight average molecular weight of 78,100.

&Lt; Example 5 >

BODA (3.83 g, 15.3 mmol), A-1 (2.59 g, 6.1 mmol) and DBA (2.17 g, 14.3 mmol) were mixed in NMP (15.8 g) , CBDA (1.00 g, 5.1 mmol) and NMP (12.9 g) were added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%.

Acetic anhydride (2.45 g) and pyridine (1.85 g) as an imidation catalyst were added to the obtained polyamic acid solution (20.1 g), diluted to 6 mass%, and reacted at 80 ° C for 4.5 hours . The reaction solution was poured into methanol (350 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (2). The imidization ratio of the polyimide was 55%, the number average molecular weight was 22,100, and the weight average molecular weight was 60,100.

&Lt; Example 6 >

BODA (2.37 g, 9.5 mmol), A-2 (2.56 g, 5.7 mmol) and DBA (2.02 g, 13.3 mmol) were mixed in NMP (14.6 g) , CBDA (1.86 g, 9.5 mmol) and NMP (11.9 g) were added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution (3) having a resin solid content concentration of 25.0 mass%. The polyamic acid had a number average molecular weight of 23,500 and a weight average molecular weight of 72,600.

&Lt; Example 7 >

NMP was added to the polyamic acid solution (3) (20.0 g) obtained in Example 6 to dilute to 6 mass%, acetic anhydride (4.50 g) and pyridine (3.25 g) were added as an imidation catalyst, Followed by reaction at 90 ° C for 3.5 hours. The reaction solution was poured into methanol (450 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (4). The imidization ratio of the polyimide was 80%, the number average molecular weight was 19,500, and the weight average molecular weight was 50,100.

&Lt; Example 8 >

NMP (13.2 g) was added to BODA (3.04 g, 12.2 mmol), A-3 (2.34 g, 5.2 mmol), m-PDA (0.56 g, 5.2 mmol), and DBA (1.06 g, 7.0 mmol) , CBDA (1.02 g, 5.2 mmol) and NMP (10.8 g) were added and reacted at 40 DEG C for 6.5 hours to obtain a polyamide having a resin solid content concentration of 25.0% by mass To obtain an acid solution.

NMP was added to the obtained polyamic acid solution (20.0 g) to dilute to 6 mass%, acetic anhydride (4.51 g) and pyridine (3.25 g) were added as imidation catalysts and reacted at 90 ° C for 3.5 hours . The reaction solution was poured into methanol (450 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (5). The imidization ratio of the polyimide was 81%, the number average molecular weight was 18,300, and the weight average molecular weight was 47,400.

&Lt; Example 9 >

NMP (12.7 g) was added to BODA (2.11 g, 8.4 mmol), A-3 (2.28 g, 5.1 mmol), p-PDA (0.36 g, 3.3 mmol), and DBA (1.28 g, , CBDA (1.65 g, 8.4 mmol) and NMP (10.5 g) were added and reacted at 40 占 폚 for 6.5 hours to obtain a polyamide having a resin solid content concentration of 25.0% by mass To obtain an acid solution.

NMP was added to the obtained polyamic acid solution (20.0 g) to dilute to 6 mass%, acetic anhydride (4.50 g) and pyridine (3.31 g) were added as imidation catalysts and reacted at 90 ° C for 3.5 hours . The reaction solution was poured into methanol (450 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimide powder (6). The imidization ratio of the polyimide was 68%, the number average molecular weight was 19,300, and the weight average molecular weight was 50,900.

&Lt; Example 10 >

A mixture of TCA (4.48 g, 20.0 mmol), A-1 (1.70 g, 4.0 mmol) and DBA (2.44 g, 16.0 mmol) in NMP (25.8 g) Thereby obtaining a polyamic acid solution (7) having a resin solid content concentration of 25.0 mass%. This polyamic acid had a number average molecular weight of 24,200 and a weight average molecular weight of 75,800.

&Lt; Example 11 >

NMP was added to the polyamide acid solution (7) (20.5 g) obtained in Example 11 to dilute to 6 mass%, acetic anhydride (1.91 g) and pyridine (1.50 g) were added as an imidation catalyst, The reaction was carried out at 80 ° C for 4 hours. The reaction solution was poured into methanol (350 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (8). The imidization ratio of the polyimide was 58%, the number average molecular weight was 20,700, and the weight average molecular weight was 55,100.

&Lt; Example 12 >

NMP (27.2 g) was added to TCA (4.48 g, 20.0 mmol), A-3 (2.72 g, 6.0 mmol), p-PDA (0.65 g, 6.0 mmol), and DBA (1.22 g, 8.0 mmol) , And the mixture was reacted at 40 DEG C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%.

NMP was added to the resulting polyamic acid solution (20.0 g) to dilute to 6 mass%, acetic anhydride (1.90 g) and pyridine (1.45 g) were added as imidation catalysts and reacted at 80 ° C for 4 hours . The reaction solution was poured into methanol (350 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (9). The imidization ratio of the polyimide was 55%, the number average molecular weight was 21,400, and the weight average molecular weight was 56,900.

&Lt; Example 13 >

(1.77 g, 5.9 mmol), A-2 (2.66 g, 5.9 mmol), and DBA (2.09 g, 13.7 mmol) were mixed in NMP (15.2 g) , CBDA (2.68 g, 13.7 mmol) and NMP (12.5 g) were added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%.

NMP was added to the obtained polyamic acid solution (20.0 g) to dilute to 6 mass%, acetic anhydride (4.50 g) and pyridine (3.30 g) were added as imidation catalysts and reacted at 90 ° C for 3.5 hours . The reaction solution was poured into methanol (500 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (10). The imidization ratio of the polyimide was 82%, the number average molecular weight was 19,400, and the weight average molecular weight was 48,300.

&Lt; Example 14 >

PDA (2.05 g, 19.0 mmol) was mixed in NMP (20.5 g) and TEA (4.06 g, 13.5 mmol), A-3 (3.65 g, 8.1 mmol) , CBDA (2.65 g, 13.5 mmol) and NMP (16.8 g) were added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%.

NMP was added to the resulting polyamic acid solution (20.5 g) to dilute to 6 mass%, acetic anhydride (1.95 g) and pyridine (1.50 g) were added as imidation catalysts and reacted at 80 ° C for 4 hours . The reaction solution was poured into methanol (350 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (11). The imidization ratio of the polyimide was 56%, the number average molecular weight was 21,100, and the weight average molecular weight was 52,500.

&Lt; Comparative Example 1 &

BODA (2.36 g, 9.4 mmol), AP18 (2.13 g, 5.7 mmol) and DBA (2.01 g, 13.2 mmol) were mixed in NMP (14.0 g) (1.85 g, 9.4 mmol) and NMP (11.0 g) were added and reacted at 40 占 폚 for 6 hours to obtain a polyamic acid solution (12) having a resin solid content concentration of 25.0 mass%. This polyamic acid had a number average molecular weight of 24,200 and a weight average molecular weight of 74,100.

&Lt; Comparative Example 2 &

NMP was added to the polyamic acid solution (12) (20.0 g) obtained in Synthesis Example 1 to dilute it to 6 mass%, acetic anhydride (4.50 g) and pyridine (3.20 g) were added as an imidation catalyst, Followed by reaction at 90 ° C for 3.5 hours. The reaction solution was poured into methanol (450 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (13). The imidization ratio of the polyimide was 80%, the number average molecular weight was 19,900, and the weight average molecular weight was 51,600.

Table 37 summarizes the polyamic acid and polyimide obtained in Examples 4 to 14 and Comparative Examples 1 and 2.

* 1: Polyamic acid

[Preparation of liquid crystal alignment treatment agent]

In Examples 15 to 25 and Comparative Examples 3 and 4, preparation examples of liquid crystal alignment treatment agents were described. Table 38 summarizes the obtained liquid crystal alignment treatment agent.

(Evaluation of Wettability on Liquid Crystal Alignment Layer of Liquid Crystal), [Production of Liquid Crystal Cell (Normal Cell)], [Production of Liquid Crystal Cell (PSA Cell)] and [ Evaluation of the pretilt angle] was carried out as follows.

The properties of the respective liquid crystal alignment films obtained in Examples 15 to 25 and Comparative Examples 3 and 4 are summarized in Tables 39 to 42.

Table 39 shows the results of evaluation of the hydrophobicity of the liquid crystal alignment film, Table 40 shows the results of evaluation of wettability on the liquid crystal alignment film of the liquid crystal, Table 41 shows the evaluation results of the pretilt angle using normal cells and Table 42 shows the pretilt angles . Fig.

[Production of liquid crystal alignment film]

The liquid crystal alignment treatment agent was spin-coated on the ITO surface of the substrate on which the ITO electrode having a size of 30 mm x 40 mm was formed and subjected to heat treatment at 80 DEG C for 5 minutes and 230 DEG C for 30 minutes in a heat circulation type clean oven, A substrate on which a 100 nm polyimide liquid crystal alignment film was formed was obtained.

[Evaluation of hydrophobicity of liquid crystal alignment film]

[Production of Liquid Crystal Alignment Film] The substrate having the liquid crystal alignment film formed thereon was used to measure the water contact angle. At that time, the higher the water contact angle, the higher the hydrophobicity, and the lower the water contact angle, the lower the hydrophobicity. For measurement of the water contact angle, an automatic contact angle caliper type CA-Z (manufactured by Kyowa Interface Science Co., Ltd.) was used.

[Evaluation of Wettability on Liquid Crystal Alignment Film of Liquid Crystal]

[Manufacture of Liquid Crystal Alignment Film] The contact angle of the liquid crystal was measured using the substrate on which the liquid crystal alignment film was formed. At that time, the contact angle of the liquid crystal after 10 seconds after dropping the liquid crystal was measured and it was found that the liquid crystal alignment film having a lower contact angle of the liquid crystal was superior in wettability on the liquid crystal alignment film of the liquid crystal and the liquid crystal alignment film, And the wetting property on the alignment film was poor. MLC-6608 (manufactured by Merck Japan Co., Ltd.) was used as the liquid crystal, and an automatic contact angle CA-Z type (manufactured by Kyowa Interface Science Co., Ltd.) was used for measuring the contact angle.

[Production of liquid crystal cell (ordinary cell)]

The liquid crystal alignment treatment agent was spin-coated on the ITO surface of the substrate on which the ITO electrode having a size of 30 mm x 40 mm was formed and subjected to heat treatment at 80 DEG C for 5 minutes on a hot plate and 230 DEG C for 45 minutes in a thermocycling type clean oven, An ITO substrate on which a 100 nm polyimide liquid crystal alignment film was formed was obtained. The coated film surface of the ITO substrate was subjected to rubbing under the conditions of a roll speed of 1000 rpm, a roll advancing speed of 50 mm / sec, and an indentation amount of 0.1 mm using a rayon device with a rubbing device having a roll diameter of 120 mm.

Two sheets of the ITO substrates on which the obtained liquid crystal alignment films were formed were prepared, and 6 mu m spacers were interposed therebetween with the liquid crystal alignment film surface on the inner side, and the periphery was bonded with a sealant to prepare blank cells. MLC-6608 (manufactured by Merck Japan) was injected into this empty cell by a vacuum injection method, and the injection port was sealed to obtain a liquid crystal cell (ordinary cell).

The alignment uniformity of the liquid crystal was confirmed by observing a polarizing microscope for the liquid crystal cell obtained in Examples and Comparative Examples. None of the liquid crystal cells had any cutting or orientation defects accompanying the rubbing treatment, and the liquid crystals were uniformly oriented.

[Production of liquid crystal cell (PSA cell)]

The liquid crystal alignment treatment agent was spin-coated on a ITO surface of a substrate having a 10 mm x 10 mm ITO electrode with a pattern interval of 20 m and a substrate with a 10 mm x 40 mm ITO electrode formed thereon, Heat treatment was carried out in a thermocycling type clean oven at 230 캜 for 30 minutes to obtain a polyimide coating film having a thickness of 100 nm. The coated film surface was cleaned with pure water and then subjected to a heat treatment at 100 캜 for 15 minutes in a thermocycling type clean oven to obtain a substrate having a liquid crystal alignment film formed thereon.

The substrate on which this liquid crystal alignment film was formed was assembled by sandwiching 6 mu m of spacers with the liquid crystal alignment film surface inward and bonding the periphery with a sealant to prepare empty cells. The polymerizable compound (1) represented by the following formula was mixed with 0.3% by mass of the polymerizable compound in 100% by mass of MLC-6608 in MLC-6608 (Merck Japan) And then the injection port was sealed to obtain a liquid crystal cell.

delete

A wavelength of 350 nm or less was cut using a metal halide lamp having an illuminance of 60 mW while applying an AC voltage of 5 V to the obtained liquid crystal cell and irradiated with ultraviolet rays of 20 J / cm 2 in terms of 365 nm, To obtain a liquid crystal cell (PSA cell) whose alignment direction was controlled. The temperature in the irradiator when the liquid crystal cell was irradiated with ultraviolet rays was 50 ° C.

The response speeds of the liquid crystal cell before and after ultraviolet irradiation were measured. The response speed was measured from T90 to T10 with a transmittance of 90% and a transmittance of 10%. It was confirmed that the PSA cell obtained in Examples and Comparative Examples had a higher response speed of the liquid crystal cell after ultraviolet irradiation than in the liquid crystal cell before irradiation with ultraviolet rays, so that the alignment direction of the liquid crystal was controlled.

Further, it was confirmed that the liquid crystal was uniformly aligned in any of the liquid crystal cells by observation with a polarizing microscope.

[Evaluation of Pretilt Angle]

[Production of liquid crystal cell (normal cell)] and [Production of liquid crystal cell (PSA cell)] were measured. The pretilt angle was measured after heat treatment at 95 캜 for 5 minutes and after heat treatment at 120 캜 for 5 hours after injecting liquid crystals. After the liquid crystal injection, the liquid crystal cell after heat treatment at 95 캜 for 5 minutes was also measured after irradiating ultraviolet rays of 10 J / cm 2 in terms of 365 nm. The pretilt angle was measured at room temperature using PAS-301 (manufactured by ELSICON). In addition, UV irradiation was conducted using a table-top UV curing apparatus (HCT3B28HEX-1) (manufactured by Senry).

&Lt; Example 15 >

NMP (12.9 g) and BCS (18.8 g) were added to polyamic acid solution (1) (10.0 g) having a resin solid content concentration of 25.0 mass% obtained in Example 4 and stirred at 25 캜 for 3 hours, To obtain an orientation treatment agent (1). It was confirmed that this liquid crystal alignment treatment agent was a homogeneous solution without observing abnormality such as turbidity or precipitation.

Using the obtained liquid crystal alignment treatment agent (1), production and various evaluations of cells were carried out under the above-mentioned conditions.

&Lt; Example 16 >

NMP (18.8 g) and BCS (23.0 g) were added to the polyimide powder (2) (2.51 g) obtained in Example 5 and stirred at 25 占 폚 for 8 hours to obtain a liquid crystal alignment treatment agent (2). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that it was a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent (2), preparation of cells and various evaluations were carried out under the above-mentioned conditions.

&Lt; Example 17 >

NMP (11.4 g) and BCS (21.9 g) were added to polyamic acid solution (3) (10.5 g) having a resin solid content concentration of 25.0 mass% obtained in Example 6 and stirred at 25 캜 for 3 hours, To obtain an orientation treatment agent (3). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that it was a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent (3), production and evaluation of cells were carried out under the above-described conditions.

&Lt; Example 18 >

NMP (22.9 g) and BCS (18.8 g) were added to the polyimide powder (4) (2.50 g) obtained in Example 7 and stirred at 25 占 폚 for 8 hours to obtain a liquid crystal alignment treatment agent (4). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that it was a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent (4), production and various evaluations of cells were carried out under the above-described conditions.

&Lt; Example 19 >

NMP (21.0 g) and BCS (21.0 g) were added to the polyimide powder (5) (2.52 g) obtained in Example 8 and stirred at 25 占 폚 for 8 hours to obtain a liquid crystal alignment treatment agent (5). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that it was a homogeneous solution.

The liquid crystal alignment treatment agent (5) obtained was used to manufacture and evaluate various kinds of cells under the above-described conditions.

&Lt; Example 20 >

NMP (25.0 g) and BCS (16.7 g) were added to the polyimide powder (6) (2.50 g) obtained in Example 9 and stirred at 25 占 폚 for 8 hours to obtain a liquid crystal alignment treatment agent (6). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that it was a homogeneous solution.

The liquid crystal alignment treatment agent (6) obtained was used to manufacture and evaluate various kinds of cells under the above-described conditions.

&Lt; Example 21 >

NMP (15.0 g) and BCS (16.7 g) were added to polyamic acid solution 7 (10.0 g) having a resin solid content concentration of 25.0 mass% obtained in Example 10 and stirred at 25 占 폚 for 3 hours, To obtain an orientation treatment agent (7). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that it was a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent (7), production and various evaluations of cells were carried out under the above-mentioned conditions.

&Lt; Example 22 >

NMP (27.1 g) and BCS (14.6 g) were added to the polyimide powder (8) (2.50 g) obtained in Example 11 and stirred at 25 占 폚 for 8 hours to obtain a liquid crystal alignment treatment agent (8). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that it was a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent (8), production and various evaluations of cells were carried out under the above-mentioned conditions.

&Lt; Example 23 >

NMP (22.9 g) and BCS (18.8 g) were added to the polyimide powder (9) (2.50 g) obtained in Example 12 and stirred at 25 占 폚 for 8 hours to obtain a liquid crystal alignment treatment agent (9). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that it was a homogeneous solution.

The liquid crystal alignment treatment agent (9) obtained was used to manufacture and evaluate various kinds of cells under the above-described conditions.

&Lt; Example 24 >

NMP (25.0 g) and BCS (16.7 g) were added to the polyimide powder (10) (2.50 g) obtained in Example 13 and stirred at 25 占 폚 for 8 hours to obtain a liquid crystal alignment treating agent (10). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that it was a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent 10, production and evaluation of cells were carried out under the above-mentioned conditions.

&Lt; Example 25 >

NMP (23.1 g) and BCS (18.9 g) were added to the polyimide powder (11) (2.52 g) obtained in Example 14 and stirred at 25 占 폚 for 8 hours to obtain a liquid crystal alignment treatment agent (11). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that it was a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent 11, production and various evaluations of cells were carried out under the above-described conditions.

&Lt; Comparative Example 3 &

NMP (10.9 g) and BCS (21.0 g) were added to polyamic acid solution 12 (10.1 g) having a resin solid content concentration of 25.0 mass% obtained in Comparative Example 1 and stirred at 25 캜 for 3 hours, To obtain an orientation treatment agent (12). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that it was a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent 12, production and evaluation of cells were carried out under the above-described conditions.

&Lt; Comparative Example 4 &

NMP (23.1 g) and BCS (18.9 g) were added to the polyimide powder (13) (2.52 g) obtained in Comparative Example 2 and stirred at 25 占 폚 for 8 hours to obtain a liquid crystal alignment treatment agent (13). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that it was a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent 13, production and evaluation of cells were carried out under the above-described conditions.

As can be seen from the above results, the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the embodiment of the present invention is superior in transparency to the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the comparative example even when exposed to high temperature and light (ultraviolet) The change of angle is small. This resulted in the same results for both normal cells and PSA cells. In particular, Comparative Examples 3 and 4, which did not contain a specific side chain type diamine compound, exhibited a large change in the pretilt angle after exposure to a long time at a high temperature. Particularly, the pretilt angle after exposure to light (ultraviolet ray) The change was great.

In the case of using a polyimide precursor having the same constitution and a polyimide, the variation of the pretilt angle was small even after exposure to high temperature and light (ultraviolet rays) for a long time in the embodiment containing a specific side chain type diamine compound. Concretely, it is a comparison between Example 17, Comparative Example 3, and Example 18 and Comparative Example 4 shown in Table 41 in a conventional cell. Comparisons are made in PSA cells of Example 17, Comparative Example 3, and Example 18 and Comparative Example 4 shown in Table 42.

Further, the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the embodiment of the present invention has a larger water contact angle of the liquid crystal alignment film than that of the liquid crystal alignment treatment agent obtained from the liquid crystal alignment treatment agent of the comparative example. That is, the hydrophilic property of the liquid crystal alignment film is high. In particular, Comparative Examples 3 and 4, which do not contain a specific side chain type diamine compound, have a small water contact angle of the liquid crystal alignment film and poor wettability on the liquid crystal alignment film of the liquid crystal (contact angle of the liquid crystal is large).

Further, in the case of using a polyimide precursor and a polyimide having the same constitution, in an embodiment containing a specific side chain-type diamine compound, the contact angle of water of the liquid crystal alignment film is large and the hydrophobic property of the liquid crystal alignment film is high. In addition, in the embodiment containing the specific side chain type diamine compound, the wetting property on the liquid crystal alignment film of the liquid crystal is excellent. Concretely, the evaluation of the water contact angles of the liquid crystal alignment films of Example 17, Comparative Example 3, and Example 18 and Comparative Example 4 shown in Table 39 is compared. The evaluation of wetting diffusivity on the liquid crystal alignment film of liquid crystal of Example 17, Comparative Example 3, and Example 18 and Comparative Example 4 shown in Table 42 is a comparison.

Industrial availability

By using the liquid crystal alignment treatment agent containing a polymer having a side chain of the specific structure of the present invention, the pretilt angle does not change even when exposed to high temperature and light irradiation for a long time, and the liquid crystal alignment irregularity caused by the ODF system is reduced TN devices, STN devices, TFT liquid crystal devices, liquid crystal display devices, and the like, which can provide a highly reliable liquid crystal display device having excellent display characteristics and high reliability by using the liquid crystal alignment film. .

The liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention is also useful in the production of a liquid crystal display element in which ultraviolet rays need to be irradiated when a liquid crystal display element is produced.

The entire contents of the specification, claims, and summary of Japanese Patent Application No. 2011-240340 filed on November 1, 2011 are incorporated herein by reference and the disclosure of the specification of the present invention is hereby incorporated herein by reference.

Claims

A liquid crystal alignment film characterized by containing at least one polymer selected from the group consisting of a polyimide precursor having a side chain represented by the following formula [1A] or formula [1B] and a polyimide obtained by imidizing the polyimide precursor Treatment agent.

(Formula [1A] of, X ₁ is -CONH-, -NHCO-, -NH-, -N ( R 1) - (R 1 is a branched group of 1 to 5 carbon atoms or linear alkyl group having a carbon number of 3-5 of the type X ₂ represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring or a heterocyclic ring, and any hydrogen atom on these cyclic groups may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms, A fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom, X ₃ is a divalent cyclic group selected from a benzene ring, a cyclohexyl ring or a heterocyclic ring , And any hydrogen atom on these cyclic groups may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluoro-containing alkoxyl group having 1 to 3 carbon atoms, X ₄ represents a carbon number An alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 18 carbon atoms, m is an integer of 2 to 15, and n is an integer of 1 to 3 P is an integer of 0 to 3, and n + p is an integer of 1 to 6.)

(In the formula [1B], X ₅ represents -CONH-, -NHCO-, -NH-, -N (R ₂ ) - (R ₂ represents a linear alkyl group having 1 to 5 carbon atoms or a branched alkyl group having 3 to 5 carbon atoms X ₆ is a cyclic group consisting of a steroid skeleton, and q is an integer of 2 to 15.)

The method according to claim 1,
Wherein the polyimide precursor is obtained by reacting a diamine component containing a diamine compound having a side chain represented by the formula [1A] or a formula [1B] with a tetracarboxylic acid component.

3. The method of claim 2,
The diamine compound having a side chain represented by the above formula [1A] is represented by the following formula [2A].

(Equation [2A] of, X ₁ is -CONH-, -NHCO-, -NH-, -N ( R 1) - (R 1 is a branched group of 1 to 5 carbon atoms or linear alkyl group having a carbon number of 3-5 of the type X ₂ represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring or a heterocyclic ring, and any hydrogen atom on these cyclic groups may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms, A fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom, X ₃ is a divalent cyclic group selected from a benzene ring, a cyclohexyl ring or a heterocyclic ring , And any hydrogen atom on these cyclic groups may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluoro-containing alkoxyl group having 1 to 3 carbon atoms, X ₄ represents a carbon number An alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 18 carbon atoms, m is an integer of 2 to 15, and n is an integer of 1 to 3 P is an integer of 0 to 3, and n + p is an integer of 1 to 6.)

delete

3. The method of claim 2,
The liquid crystal alignment treatment agent represented by the following formula [2B] is a diamine compound having a side chain represented by the above formula [1B].

(Equation [2B] of, X ₅ is -CONH-, -NHCO-, -NH-, -N ( R 2) - (R 2 is a branched group of 1 to 5 carbon atoms or linear alkyl group having a carbon number of 3-5 of the type X ₆ is a cyclic group consisting of a steroid skeleton, and q is an integer of 2 to 15.)

The method according to claim 3 or 5,
The diamine compound represented by the formula [2A] or the formula [2B] is contained in an amount of 5 to 80 mol% of the diamine component.

delete

3. The method of claim 2,
Wherein the tetracarboxylic acid component is a tetracarboxylic acid dianhydride represented by the following formula [3].

9. The method of claim 8,
Wherein the Z ₁ is selected from the structures represented by the following formulas [3a] to [3j].

The method according to claim 1,
A liquid crystal alignment treatment agent containing 80 to 99 mass% of an organic solvent in a liquid crystal alignment treatment agent.

11. The method of claim 10,
Wherein the organic solvent contains 5 to 60 mass% of a poor solvent.

A liquid crystal alignment film obtained from the liquid crystal alignment treatment agent according to claim 1.

A liquid crystal alignment film obtained by the inkjet coating method using the liquid crystal alignment treatment agent according to claim 1.

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

The method according to claim 12 or 13,
A liquid crystal composition comprising a liquid crystal layer between a pair of substrates provided with electrodes and containing a polymerizable compound capable of polymerizing by at least one of active energy rays and heat is disposed between the pair of substrates, And the polymerizable compound is polymerized while applying a voltage between the liquid crystal alignment layer and the liquid crystal alignment layer.

A liquid crystal display element having the liquid crystal alignment film according to claim 15.

17. The method of claim 16,
A liquid crystal composition comprising a liquid crystal layer between a pair of substrates provided with electrodes and the liquid crystal alignment film and containing a polymerizable compound capable of polymerizing by at least one of active energy rays and heat between the pair of substrates And polymerizing the polymerizable compound while applying a voltage between the electrodes.

The method according to claim 12 or 13,
A liquid crystal alignment film comprising a liquid crystal layer between a pair of substrates provided with electrodes and having a polymerizable group polymerized by at least one of active energy rays and heat is disposed between the pair of substrates, And the polymerizable group is polymerized while applying a voltage to the liquid crystal alignment layer.

A liquid crystal display element having the liquid crystal alignment film according to claim 18.

20. The method of claim 19,
A liquid crystal alignment film comprising a liquid crystal layer between a pair of substrates provided with electrodes and having a polymerizable group polymerizable by at least one of active energy rays and heat is disposed between the pair of substrates, And polymerizing the polymerizable group while applying a voltage to the liquid crystal display element.

A diamine compound represented by the following formula [2A].

delete

A polyimide obtained by dehydrocondylating a polyamic acid or a polyamic acid obtained by reacting a diamine component containing a diamine compound represented by the following formula [2A] or [2B] with a tetracarboxylic acid component.

delete