WO2011132751A1

WO2011132751A1 - Liquid-crystal alignment agent, liquid-crystal alignment film, and liquid-crystal display element

Info

Publication number: WO2011132751A1
Application number: PCT/JP2011/059867
Authority: WO
Inventors: 徳俊三木; 耕平後藤; 雅章片山; 幸司園山; 和義保坂
Original assignee: 日産化学工業株式会社
Priority date: 2010-04-22
Filing date: 2011-04-21
Publication date: 2011-10-27
Also published as: JPWO2011132752A1; JP5713009B2; KR101775181B1; KR20130091652A; TW201209076A; CN102947752A; JPWO2011132751A1; CN102947753A; TWI486380B; KR101775182B1; WO2011132752A1; CN102947753B; KR20130091651A; JP5936000B2; TW201209077A; TWI447146B; CN102947752B

Abstract

Disclosed is a liquid-crystal alignment agent that contains a polymer obtained through causing the reaction of a tetracarboxylic acid dianhydride and a diamine component containing the diamine compounds of formula 1 and formula 2. X₁ is a divalent organic group selected from -NHCO-, -N(CH₃)CO-, -CONH-, or -CON(CH₃)-. X₂ is a divalent organic group selected from a single bond, a benzene ring, or a cyclohexyl ring. X₃ and X₄ are divalent organic groups selected from a benzene ring or a cyclohexyl ring. X₅ is selected from an alkyl group having a carbon number of 1-18, a fluorine-containing alkyl group having a carbon number of 1-18, an alkoxyl group having a carbon number of 1-18, or a fluorine-containing alkoxyl group having a carbon number of 1-18, and n is an integer from 1 to 4. Y₁ is a divalent organic group selected from a single bond, -(CH₂)_a (a being an integer from 1 to 10), -O-, -CH₂O-, -COO-, or -OCO-. Y₂ is a divalent organic group selected from a single bond or -(CH₂)_b- (b being an integer from 1 to 10). Y₃ is a divalent organic group selected from a single bond, -(CH₂)_c- (c being an integer from 1 to 10), -O-, -CH₂O-, -COO-, or -OCO-. Y₄ indicates a divalent cyclic group selected from a benzene ring, a cyclohexyl ring, or a heterocycle, or indicates a divalent organic group having a carbon number of 12-25 and having a steroid skeleton, and any given hydrogen atom on the aforementioned cyclic groups may be replaced by a group selected from an alkyl group having a carbon number of 1-3, an alkoxyl group having a carbon number of 1-3, a fluorine-containing alkyl group having a carbon number of 1-3, a fluorine-containing alkoxyl group having a carbon number of 1-3, or a fluorine atom. Y₅ indicates a divalent cyclic group selected from a benzene ring, a cyclohexyl ring, or a heterocycle, any given hydrogen atom on these cyclic groups may be replaced by a group selected from an alkyl group having a carbon number of 1-3, an alkoxyl group having a carbon number of 1-3, a fluorine-containing alkyl group having a carbon number of 1-3, a fluorine-containing alkoxyl group having a carbon number of 1-3, or a fluorine atom, and n is an integer from 0 to 4. Y₆ is an alkyl group having a carbon number of 1-18, a fluorine-containing alkyl group having a carbon number of 1-18, an alkoxyl group having a carbon number of 1-18, a fluorine-containing alkoxyl group having a carbon number of 1-18, or a hydrogen atom, and m is an integer from 1 to 4.

Description

Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element

The present invention relates to a liquid crystal alignment treatment agent used for producing a liquid crystal alignment film and a liquid crystal display element using the same.

Currently, in many cases, a polyimide film is used as a liquid crystal alignment film used in a liquid crystal display element. This polyimide film is formed by using a solution of a polyamic acid, which is a precursor of polyimide, or a solution of a solvent-soluble polyimide as a substrate. The method of apply | coating and baking is taken. This polyamic acid or solvent-soluble polyimide is generally synthesized by reacting a tetracarboxylic acid derivative such as tetracarboxylic dianhydride with a diamine.

As one of the characteristics required for the liquid crystal alignment film, there is so-called pretilt angle control of the liquid crystal 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 magnitude of the pretilt angle can be changed by selecting the structure of the polyimide constituting the liquid crystal alignment film.

Among the techniques for controlling the pretilt angle depending on the structure of the polyimide, the method using a diamine having a side chain as a part of the polyimide raw material can control the pretilt angle in accordance with the proportion of the diamine used, so that the desired pretilt angle is obtained. This is relatively easy and is useful as a means for increasing the pretilt angle. Examples of the side chain structure of the diamine that increases the pretilt angle of the liquid crystal include a long-chain alkyl group or a fluoroalkyl group (for example, see Patent Document 1), a cyclic group or a combination of a cyclic group and an alkyl group (for example, see Patent Document 2), A steroid skeleton (see, for example, Patent Document 3) is known.

JP-A-2-282726 Japanese Patent Laid-Open No. 3-179323 JP-A-4-281427

In recent years, MVA (Multi-domain Vertical Alignment) mode capable of obtaining a wide viewing angle has been widely used as a liquid crystal display device that has superior viewing angle characteristics as compared with conventional TN (Twisted Nematic) mode liquid crystal display devices. In this MVA mode, it is necessary to align liquid crystal molecules perpendicularly to the substrate (pretilt angle is set to 90 °), and a liquid crystal alignment film using many diamine components having side chains as described above is required. However, this liquid crystal alignment film reduces the affinity with the liquid crystal and reduces the wettability of the liquid crystal on the liquid crystal alignment film. Specifically, when the liquid crystal is injected by the vacuum injection method, the liquid crystal injection speed is lowered, so that the production efficiency at the time of manufacturing the liquid crystal display element is deteriorated, and when the ODF (One Drop Drop Filling) method is used. However, there is a problem that alignment unevenness is likely to occur in a liquid crystal dropping portion or a fusion portion of liquid crystals, and a display defect of a liquid crystal display element occurs.

The present invention has been made in view of the above circumstances, and improves the liquid crystal wettability on the liquid crystal alignment film, has high production efficiency at the time of manufacturing a liquid crystal display element, and does not cause poor display of alignment unevenness. It is providing a processing agent, a liquid crystal aligning film, and a liquid crystal display element.

As a result of diligent research, the present inventors have achieved the above object by a polyimide precursor having a specific side chain structure and a liquid crystal aligning agent containing polyimide obtained by dehydrating and ring-closing the polyimide precursor. Therefore, the present invention has been found to be extremely effective, and the present invention has been completed.

That is, the present invention has the following gist.
(1)
Liquid crystal alignment treatment comprising a diamine compound represented by the following formula [1] and a polymer obtained by reacting a diamine component containing the diamine compound represented by the following formula [2] with tetracarboxylic dianhydride. Agent.

(In the formula [1], X ₁ is a divalent organic group selected from —NHCO—, —N (CH ₃ ) CO—, —CONH—, —CON (CH ₃ ) —, and X ₂ is a single bond. , A benzene ring or a cyclohexyl ring, X ₃ is a divalent organic group selected from a benzene ring or a cyclohexyl ring, and X ₄ is a cyclohexyl ring, Or a divalent organic group selected from a benzene ring, and X ₅ 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 1 carbon atom. From 18 to 18 fluorine-containing alkoxyl groups, and n is an integer from 1 to 4.

(In the formula [2], Y ₁ represents —O—, —CH ₂ O—, — (CH ₂ ) _a — (a is an integer of 1 to 10), —COO—, —OCO—, or Y ₂ is a divalent organic group selected from a bond, Y ₂ is a single bond or a divalent organic group selected from — (CH ₂ ) _b — (b is an integer of 1 to 10), Y ₃ Is a divalent organic group selected from a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 10), —O—, —CH ₂ O—, —COO—, or —OCO—. Y ₄ represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring, or a heterocyclic ring, or a divalent organic group having 12 to 25 carbon atoms having a steroid skeleton, on the cyclic group Arbitrary hydrogen atoms include 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, The fluorine-containing alkoxyl group having 1 to 3 carbon atoms, may be substituted with one selected from a fluorine atom, Y ₅ represents a divalent cyclic group selected from cyclohexyl ring, a benzene ring or a heterocyclic cyclohexane And any hydrogen atom on these cyclic groups is 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, or fluorine having 1 to 3 carbon atoms An alkoxyl group that may be substituted with a fluorine atom, n is an integer of 0 to 4, Y ₆ is an alkyl group having 1 to 18 carbon atoms, or a fluorine-containing alkyl group having 1 to 18 carbon atoms A group, an alkoxyl group having 1 to 18 carbon atoms, a fluorine-containing alkoxyl group having 1 to 18 carbon atoms, or a hydrogen atom, and m is an integer of 1 to 4).

(2)
The liquid crystal aligning agent according to (1), wherein in formula [1], X ₁ is —NHCO—.

(3)
The liquid crystal aligning agent according to (1) or (2), wherein the tetracarboxylic dianhydride is a tetracarboxylic dianhydride represented by the following formula [3].

(In the formula [3], Z ₁ is a tetravalent organic group having 4 to 13 carbon atoms and contains a non-aromatic cyclic hydrocarbon group having 4 to 6 carbon atoms).

(4)
The liquid crystal aligning agent according to (3), wherein Z ₁ is a structure represented by the following formulas [3a] to [3j].

(In the formula [3a], Z ₂ to Z ₅ are groups selected from a hydrogen atom, a methyl group, a chlorine atom, or a benzene ring, which may be the same or different, and in the formula [3g] Z ₆ and Z ₇ are a hydrogen atom or a methyl group, and each may be the same or different.

(5)
In the liquid crystal aligning agent, a crosslinkable compound having at least one substituent selected from the group consisting of epoxy group, oxetane group, isocyanate group and cyclocarbonate group, hydroxyl group, hydroxyalkyl group, alkoxyl group and lower alkoxyalkyl The liquid crystal alignment treatment according to any one of (1) to (4), having a crosslinkable compound having at least one substituent selected from the group consisting of groups, or a crosslinkable compound having a polymerizable unsaturated bond Agent.

(6)
The liquid crystal aligning agent according to any one of (1) to (5), wherein the polymer in the liquid crystal aligning agent is a polyimide obtained by dehydrating and ring-closing polyamic acid.

(7)
The liquid crystal aligning agent according to any one of (1) to (6), wherein the liquid crystal aligning agent contains 5 to 60% by mass of a poor solvent.

(8)
A liquid crystal alignment film obtained by using the liquid crystal aligning agent according to any one of (1) to (7).

(9)
The liquid crystal display element which has a liquid crystal aligning film as described in (8).

(10)
A liquid crystal alignment film obtained by using the liquid crystal aligning agent according to any one of (1) to (7), wherein a liquid crystal material in which a liquid crystal is mixed with a polymerizable compound that is polymerized by heat or ultraviolet irradiation is used. A liquid crystal alignment film used for a liquid crystal display element, which is a polymer obtained by polymerizing the polymerizable compound while applying a voltage to the liquid crystal layer, and is obtained by a method of controlling the alignment direction of the liquid crystal during driving.

(11)
A liquid crystal display element comprising the liquid crystal alignment film according to (10), wherein the polymerization is performed while applying a voltage to the liquid crystal layer using a liquid crystal material in which a liquid crystal is mixed with a polymerizable compound that is polymerized by heat or ultraviolet irradiation. A liquid crystal display element obtained by polymerizing an organic compound and obtained by a method of controlling the alignment direction of liquid crystal during driving.

By using the liquid crystal aligning agent of the present invention, there is provided a liquid crystal display element having high liquid crystal wettability on the liquid crystal alignment film, high production efficiency at the time of producing the liquid crystal display element, and no display defects of alignment unevenness. be able to.

Hereinafter, the present invention will be described in detail.

The present invention includes a diamine component including a diamine compound represented by the following formula [1] (also referred to as a specific diamine compound) and a diamine compound represented by the following formula [2] (also referred to as a specific side chain diamine compound); A liquid crystal aligning agent containing a polymer obtained by reacting with tetracarboxylic dianhydride, a liquid crystal aligning film obtained using the liquid crystal aligning agent, and a liquid crystal display device having the liquid crystal aligning film is there.

(In the formula [2], Y ₁ is —O—, —CH ₂ O—, — (CH ₂ ) _a — (a is an integer of 1 to 10), —COO—, —OCO—, or a single bond Y ₂ is a single bond or a divalent organic group selected from — (CH ₂ ) _b — (b is an integer of 1 to 10), and Y ₃ is A divalent organic group selected from a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 10), —O—, —CH ₂ O—, —COO—, or —OCO—. , Y ₄ represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring, or a heterocyclic ring, or a divalent organic group having 12 to 25 carbon atoms and having a steroid skeleton. The hydrogen atom is 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, Fluorine-containing alkoxyl group having 1 to 3 carbon atoms, may be substituted with one selected from a fluorine atom, Y ₅ represents a divalent cyclic group selected from cyclohexyl ring, a benzene ring or a heterocyclic cyclohexane, Arbitrary hydrogen atoms on these cyclic groups are alkyl groups having 1 to 3 carbon atoms, alkoxyl groups having 1 to 3 carbon atoms, fluorine-containing alkyl groups having 1 to 3 carbon atoms, or fluorine containing 1 to 3 carbon atoms An alkoxyl group, which may be substituted with one selected from fluorine atoms, n is an integer of 0 to 4, Y ₆ is an alkyl group having 1 to 18 carbon atoms, or a fluorine-containing alkyl group having 1 to 18 carbon atoms , An alkoxyl group having 1 to 18 carbon atoms, a fluorine-containing alkoxyl group having 1 to 18 carbon atoms, or a hydrogen atom, and m is an integer of 1 to 4.

The liquid crystal alignment film obtained from the liquid crystal aligning agent using the specific diamine compound of the present invention and the specific side chain type diamine compound, even when a large amount of diamine components having side chains are used in order to obtain a high pretilt angle, The liquid crystal wettability on the liquid crystal alignment film is increased. Thus, by using the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention, it is possible to provide a liquid crystal display element that has high production efficiency at the time of manufacturing the liquid crystal display element and that does not cause poor display of alignment unevenness. .

<Specific diamine compound>
The specific diamine compound of the present invention is a diamine compound represented by the following formula [1].

In the formula [1], X ₁ is a divalent organic group selected from —NHCO—, —N (CH ₃ ) CO—, —CONH—, —CON (CH ₃ ) —, and in particular, —NHCO— , -CONH- is preferable. More preferred is —NHCO—.

In the formula [1], X ₂ is a divalent organic group selected from a single bond, a benzene ring, or a cyclohexyl ring, that is, a phenylene group or a cyclohexylene group. Among them, a single bond or benzene A ring is preferred.

In the formula [1], X ₃ is a divalent organic group selected from a benzene ring or a cyclohexyl ring.

In the formula [1], X ₄ is a divalent organic group selected from a benzene ring or a cyclohexyl ring.

In the formula [1], X ₅ 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 fluorine-containing 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 fluorine-containing alkoxyl group having 1 to 10 carbon atoms is preferable. More preferably, it is an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. More preferably, it is an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.

In the formula [1], n is an integer of 1 to 4, and an integer of 1 or 2 is particularly preferable.

Preferred combinations of X ₁ , X ₂ , X ₃ , X ₄ and n in the formula [1] are as shown in 1-1 to 1-64 shown in Tables 1 to 5.

<Specific side chain diamine compound>
The specific side chain diamine compound of the present invention is a diamine compound represented by the following formula [2].

In the formula [2], Y ₁ is a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 10), —O—, —CH ₂ O—, —COO—, or —OCO—. It is a divalent organic group selected. Among these, a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, or —COO— is preferable because the side chain structure can be easily synthesized. . More preferably, it is a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 10), —O—, —CH ₂ O—, or —COO—.

In the formula [2], Y ₂ is a single bond or a divalent organic group selected from — (CH ₂ ) _b — (b is an integer of 1 to 15). Among these, a single bond or — (CH ₂ ) _b — (b is an integer of 1 to 0) is preferable.

In the formula [2], Y ₃ is a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ O—, —COO—, or —OCO—. It is a divalent organic group selected. Among these, a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 10), —O—, —CH ₂ O—, —COO—, or —OCO— is preferable because they are easy to synthesize. . More preferably, they are a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 10), —O—, —CH ₂ O—, —COO—, or —OCO—.

In the formula [2], Y ₄ represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring, or a heterocyclic ring, or a divalent organic group having 12 to 25 carbon atoms and having a steroid skeleton, Arbitrary hydrogen atom on the cyclic group is 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, or a fluorine-containing alkoxyl group having 1 to 3 carbon atoms And may be substituted with one selected from fluorine atoms. Of these, an organic group having 12 to 25 carbon atoms having a benzene ring, a cyclohexyl ring or a steroid skeleton is preferable.

In the formula [2], Y ₅ represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring, or a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is an alkyl having 1 to 3 carbon atoms. And a group selected from a group selected from a group, an alkoxyl 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, and a fluorine atom. Of these, a benzene ring or a cyclohexyl ring is preferable.

In the formula [2], Y ₆ represents 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, a fluorine-containing alkoxyl group having 1 to 18 carbon atoms, or It is a hydrogen atom. Among these, 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 fluorine-containing alkoxyl group having 1 to 10 carbon atoms is preferable. More preferably, it is an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. More preferably, it is an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.

In the formula [2], n is an integer of 0 to 4. Preferably, it is an integer of 0-2.

Preferred combinations of Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ , and n in Formula [2] are as shown in Tables 2-1 to 2-629 shown in Tables 6 to 47.

(In the table, c is an integer from 1 to 10)

(In the table, c is an integer from 1 to 10)

(In the table, c is an integer from 1 to 10)

(In the table, a is an integer from 1 to 10)

(In the table, a is an integer from 1 to 10)

(In the table, a is an integer from 1 to 10)

(In the table, a is an integer from 1 to 10)

(In the table, a is an integer from 1 to 10)

(In the table, a and c are each independently an integer of 1 to 10)

(In the table, c is an integer of 1 to 10)

(In the table, c is an integer of 1 to 10)

(In the table, c is an integer of 1 to 10)

(In the table, c is an integer of 1 to 10)

(In the table, c is an integer of 1 to 10)

(In the table, c is an integer of 1 to 10)

(In the table, c is an integer of 1 to 10)

(In the table, b is an integer from 1 to 10)

(In the table, b is an integer from 1 to 10)

(In the table, b is an integer from 1 to 10)

(In the table, b is an integer from 1 to 10)

(In the table, b is an integer from 1 to 10)

(In the table, b is an integer from 1 to 10)

(In the table, b is an integer from 1 to 10)

(In the table, b is an integer from 1 to 10)

(In the table, b is an integer from 1 to 10)

(In the table, b is an integer from 1 to 10)

(In the table, b is an integer from 1 to 10)

(In the table, b is an integer from 1 to 10)

(In the table, b is an integer from 1 to 10)

(In the table, b is an integer from 1 to 10)

(In the table, b is an integer from 1 to 10)

(In the table, b is an integer from 1 to 10)

In the formula [2], m is an integer of 1 to 4. Preferably, it is an integer of 1 to 2.

Specifically, for example, the structure is represented by the following formula [2-1] to formula [2-32].

(In Formula [2-1] and Formula [2-2], R ₁ represents —O—, —OCH ₂ —, —CH ₂ O—, —COOCH ₂ —, —CH ₂ OCO—, and R ₂ Is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group).

(In the formulas [2-3] to [2-5], R ₃ represents —COO—, —OCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH ₂ O—, —OCH ₂ —, Or —CH ₂ —, wherein R ₄ is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group, or a fluorine-containing alkoxy group).

(In the formulas [2-6] and [2-7], R ₅ represents —COO—, —OCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH ₂ O—, —OCH ₂ —, —CH ₂ — or —O—, wherein 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.

(In Formula [2-8] and Formula [2-9], R ₇ is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer, respectively. is there).

(In Formula [2-10] and Formula [2-11], R ₈ is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer, respectively. is there).

(In the formula [2-12], A ₄ represents an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, and A ₃ represents a 1,4-cyclohexylene group or 1, 4 -Phenylene group, A ₂ is an oxygen atom or —COO— * (where a bond marked with “*” is bonded to A ₃ ), and A ₁ is an oxygen atom or —COO— * (However, the bond marked with “*” binds to (CH ₂ ) a _2. ) a ₁ is an integer of 0 or 1, and a ₂ is an integer of 2 to 10. , A ₃ is an integer of 0 or 1).

<Other diamine compounds>
In this invention, unless the effect of this invention is impaired, other diamine compounds other than a specific diamine compound and a specific side chain type diamine compound can be used together as a diamine component. Specific examples are given below.

p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2, 5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4 , 6-diaminoresorcinol, 4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 3,3′-dihydroxy -4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl 3,3′-difluoro-4,4′-biphenyl, 3,3′-trifluoromethyl-4,4′-diaminobiphenyl, 3,4′-diaminobiphenyl, 3,3′-diaminobiphenyl, 2,2 '-Diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'- Diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldi Aniline, 3,3'-sulfonyldianiline, bis ( -Aminophenyl) silane, bis (3-aminophenyl) silane, dimethyl-bis (4-aminophenyl) silane, dimethyl-bis (3-aminophenyl) silane, 4,4'-thiodianiline, 3,3'-thiodianiline 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl (4,4'- Diaminodiphenyl) amine, N-methyl (3,3′-diaminodiphenyl) amine, N-methyl (3,4′-diaminodiphenyl) amine, N-methyl (2,2′-diaminodiphenyl) amine, N-methyl (2,3′-diaminodiphenyl) amine, 4,4′-diaminobenzophenone, 3 , 3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diamino Naphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis ( 4-aminophenyl) ethane, 1,2-bis (3-aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,3-bis (3-aminophenyl) propane, 1,4- Bis (4aminophenyl) butane, 1,4-bis (3-aminophenyl) butane, bis (3,5-diethyl-4 Aminophenyl) methane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenyl) benzene, 1,3-bis ( 4-aminophenyl) benzene, 1,4-bis (4-aminobenzyl) benzene, 1,3-bis (4-aminophenoxy) benzene, 4,4 ′-[1,4-phenylenebis (methylene)] dianiline 4,4 '-[1,3-phenylenebis (methylene)] dianiline, 3,4'-[1,4-phenylenebis (methylene)] dianiline, 3,4 '-[1,3-phenylenebis ( Methylene)] dianiline, 3,3 ′-[1,4-phenylenebis (methylene)] dianiline, 3,3 ′-[1,3-phenylenebis (methylene)] dianiline, 1,4-phenylene [(4-aminophenyl) methanone], 1,4-phenylenebis [(3-aminophenyl) methanone], 1,3-phenylenebis [(4-aminophenyl) methanone], 1,3-phenylenebis [ (3-aminophenyl) methanone], 1,4-phenylenebis (4-aminobenzoate), 1,4-phenylenebis (3-aminobenzoate), 1,3-phenylenebis (4-aminobenzoate), 1, 3-phenylenebis (3-aminobenzoate), bis (4-aminophenyl) terephthalate, bis (3-aminophenyl) terephthalate, bis (4-aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, N , N ′-(1,4-phenylene) bis (4-aminobenzamide), N, N ′-(1,3-phenyl) Enylene) bis (4-aminobenzamide), N, N ′-(1,4-phenylene) bis (3-aminobenzamide), N, N ′-(1,3-phenylene) bis (3-aminobenzamide), N, N'-bis (4-aminophenyl) terephthalamide, N, N'-bis (3-aminophenyl) terephthalamide, N, N'-bis (4-aminophenyl) isophthalamide, N, N'- Bis (3-aminophenyl) isophthalamide, 9,10-bis (4-aminophenyl) anthracene, 4,4′-bis (4-aminophenoxy) diphenylsulfone, 2,2′-bis [4- (4- Aminophenoxy) phenyl] propane, 2,2′-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2′-bis (4-aminophen) ) Hexafluoropropane, 2,2′-bis (3-aminophenyl) hexafluoropropane, 2,2′-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2′-bis (4 -Aminophenyl) propane, 2,2'-bis (3-aminophenyl) propane, 2,2'-bis (3-amino-4-methylphenyl) propane, 3,5-diaminobenzoic acid, 2,5- Diaminobenzoic acid, 1,3-bis (4-aminophenoxy) propane, 1,3-bis (3-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, 1,4-bis (3 -Aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 1,5-bis (3-aminophenoxy) pentane, 1,6-bis (4-aminopheno) B) Hexane, 1,6-bis (3-aminophenoxy) hexane, 1,7-bis (4-aminophenoxy) heptane, 1,7- (3-aminophenoxy) heptane, 1,8-bis ( 4-aminophenoxy) octane, 1,8-bis (3-aminophenoxy) octane, 1,9-bis (4-aminophenoxy) nonane, 1,9-bis (3-aminophenoxy) nonane, 1,10- (4-aminophenoxy) decane, 1,10- (3-aminophenoxy) decane, 1,11- (4-aminophenoxy) undecane, 1,11- (3-aminophenoxy) undecane, 1,12- (4 -Aminophenoxy) dodecane, aromatic diamines such as 1,12- (3-aminophenoxy) dodecane, bis (4-aminocyclohexyl) methane, bis (4-amino No-3-methylcyclohexyl) methane and other alicyclic diamines, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane Aliphatic diamines such as 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane and 1,12-diaminododecane.

Further, as long as the effects of the present invention are not impaired, a diamine 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 [DA1] to [DA12] can be exemplified.

(Wherein [DA1] ~ formula [DA5], _{A 1} is 1 or more carbon atoms 22 an alkyl group, or a fluorine-containing alkyl group).

(In the formulas [DA6] to [DA11], A ₂ represents —COO—, —OCO—, —CONH—, —NHCO—, —CH ₂ —, —O—, —CO—, or —NH—. A ₃ represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group).

(In the formula [DA12], p is an integer of 1 to 10).

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

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

In the formula [3], Z ₁ is a tetravalent organic group having 4 to 13 carbon atoms and contains a non-aromatic cyclic hydrocarbon group having 4 to 6 carbon atoms.

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

In the formula [3a], Z ₂ to Z ₅ are groups selected from a hydrogen atom, a methyl group, a chlorine atom, or a benzene ring, which may be the same or different, and in the formula [3g], Z ₆ and Z ₇ are a hydrogen atom or a methyl group, and may be the same or different.

In formula [3], particularly preferred structure of Z ₁ is represented by formula [3a], formula [3c], formula [3d], formula [3e], formula [3f], or from the viewpoint of polymerization reactivity and ease of synthesis. Formula [3g].

<Other tetracarboxylic dianhydrides>
In this invention, unless the effect of this invention is impaired, other tetracarboxylic dianhydrides other than specific tetracarboxylic dianhydride can be used together. Specific examples thereof are dianhydrides of the following compounds.

Pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7 -Anthracene tetracarboxylic acid, 1,2,5,6-anthracene tetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4-biphenyltetracarboxylic acid, bis ( 3,4-dicarboxyphenyl) ether, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) methane, 2 , 2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3,4-dicarboxyphenyl) pro Bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis (3,4 -Dicarboxyphenyl) pyridine, 3,3 ', 4,4'-diphenylsulfonetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 1,3-diphenyl-1,2,3,4- Cyclobutane tetracarboxylic acid.

The above-mentioned other tetracarboxylic dianhydrides can be used alone or in combination of two or more depending on the properties such as liquid crystal alignment properties, voltage holding ratio, accumulated charge, etc. when the liquid crystal alignment film is formed.

<Polymer>
As described above, the polymer used in the present invention includes a specific diamine compound represented by the above formula [1] and a diamine component containing a specific side chain diamine compound represented by the above formula [2] and a tetracarboxylic acid diester. Polyamide acid obtained by reaction with an anhydride and polyimide obtained by dehydrating and ring-closing this polyamic acid. Both the polyamic acid and the polyimide are useful as a polymer for obtaining a liquid crystal alignment film.

The method for synthesizing the polymer of the present invention is not particularly limited, but a method of reacting a diamine component with tetracarboxylic dianhydride, as in a general polyimide precursor (for example, polyamic acid) or polyimide synthesis method. Can be used. At that time, tetracarboxylic acid derivatives such as tetracarboxylic acid or tetracarboxylic acid dihalide can also be used.

The liquid crystal alignment film obtained by using the polymer of the present invention increases the wettability of the liquid crystal on the liquid crystal alignment film as the content ratio of the specific diamine compound in the diamine component increases. It is possible to provide a liquid crystal display element that is high and does not cause poor display of uneven alignment. In addition, the pretilt angle of the liquid crystal can be increased as the content of the specific side chain diamine compound increases.

For the purpose of enhancing the above properties, the content of the specific side chain diamine compound in the diamine component is preferably 0.01 to 99 mol with respect to 1 mol of the specific diamine compound. More preferably, it is 0.1 to 50 mol, still more preferably 0.5 to 20 mol, and most preferably 0.5 to 10 mol.

In order to obtain the polymer of the present invention, it is preferable to use a specific tetracarboxylic dianhydride represented by the above formula [3] as the tetracarboxylic dianhydride. In that case, it is preferable that 1 mol% or more of tetracarboxylic dianhydrides are specific tetracarboxylic dianhydrides. Furthermore, it is preferable that 5 mol% or more of the tetracarboxylic dianhydride is a specific tetracarboxylic dianhydride, and more preferably 10 mol% or more. Moreover, specific tetracarboxylic dianhydride may be sufficient as 100 mol% of tetracarboxylic dianhydride.

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

The organic solvent used for the reaction between the diamine component and tetracarboxylic dianhydride is not particularly limited as long as the generated polyimide precursor is soluble. Specific examples are given below.

N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylphosphoric triamide, γ-butyrolactone, isopropyl Alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol , Ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl Ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether , Dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether Tellurium, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate , Methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropio Acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, and the like. These may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve a polyimide precursor, you may mix and use the said solvent in the range which the produced | generated polyimide precursor does not precipitate. Moreover, since the water | moisture content in an organic solvent inhibits a polymerization reaction, and also causes the produced polyimide precursor to hydrolyze, it is preferable to use what dehydrated and dried the organic solvent.

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

The polymerization temperature at that time can be selected from -20 ° C. to 150 ° C., but is preferably in the range of −5 ° C. to 100 ° C. The reaction can be carried out at any concentration, but if the concentration is too low, it will be difficult to obtain a high molecular weight copolymer, and if the concentration is too high, the viscosity of the reaction solution will become too high and uniform stirring will occur. Since it becomes difficult, it is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.

In the polymerization reaction of the polyimide precursor, the ratio of the total number of moles of the diamine component and the total number of moles of tetracarboxylic dianhydride is preferably 0.8 to 1.2. Similar to a normal polycondensation reaction, the molecular weight of the polyimide precursor produced increases as the molar ratio approaches 1.0.

The polyimide of the present invention is a polyimide obtained by dehydrating and ring-closing the polyamic acid which is the polyimide precursor, and is useful as a polymer for obtaining a liquid crystal alignment film.

In the polyimide of the present invention, the dehydration cyclization rate (imidation rate) of the amic acid group is not necessarily 100%, and can be arbitrarily adjusted according to the application and purpose.

Examples of the method for imidizing the polyimide precursor include thermal imidization in which the polyimide precursor solution is heated as it is, and catalyst imidization in which a catalyst is added to the polyimide precursor solution.

When the polyimide precursor is thermally imidized in a solution, the temperature is 100 ° C. to 400 ° C., preferably 120 ° C. to 250 ° C., and it is preferable to carry out while removing water generated by the imidation reaction from the system.

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

When recovering the produced polyimide precursor or polyimide from the polyimide precursor or polyimide reaction solution, the reaction solution may be poured into a poor solvent and precipitated. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water. The polymer precipitated in a poor solvent and collected by filtration can be dried by normal temperature or reduced pressure at room temperature or by heating. In addition, when the polymer collected by precipitation is redissolved in an organic solvent and reprecipitation and collection is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the poor solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of poor solvents selected from these because purification efficiency is further improved.

The molecular weight of the polyimide precursor or polyimide contained in the liquid crystal aligning agent of the present invention is determined by considering the strength of the coating film obtained therefrom, the workability at the time of coating film formation, and the uniformity of the coating film. The weight average molecular weight measured by Gel Permeation Chromatography) is preferably 5,000 to 1,000,000, and more preferably 10,000 to 150,000.

<Liquid crystal aligning agent>
The liquid crystal aligning agent of this invention is a coating liquid for forming a liquid crystal aligning film, and is a solution which the resin component for forming a resin film melt | dissolved in the organic solvent. Here, the resin component includes the above-described polymer of the present invention, that is, the diamine component including the specific diamine compound represented by the formula [1] and the specific side chain diamine compound represented by the formula [2]. And a resin component containing at least one polymer selected from polymers obtained by reacting carboxylic acid dianhydride with tetracarboxylic dianhydride. In that case, the content of the resin component is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, and particularly preferably 3% by mass to 10% by mass.

In the present invention, all of the resin components may be the polymer of the present invention, and other polymers may be mixed with the polymer of the present invention. In that case, the content of the polymer other than the polymer of the present invention in the resin component is 0.5 to 15% by mass, preferably 1 to 10% by mass.

Examples of such another polymer include a polyimide precursor or a polyimide that does not use a specific diamine compound and a specific side chain diamine compound as a raw material.

In the liquid crystal alignment treatment agent of the present invention, a crosslinkable compound that is a compound that crosslinks a polymer for the purpose of obtaining a liquid crystal alignment film whose voltage holding ratio does not decrease even under heat or ultraviolet irradiation, specifically, At least one selected from the group consisting of a crosslinkable compound having at least one substituent selected from an epoxy group, an isocyanate group, an oxetane group, and a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group, an alkoxyl group, and a lower alkoxyalkyl group. It is preferable to introduce a crosslinkable compound having a seed substituent or a crosslinkable compound having a polymerizable unsaturated bond. In addition, it is necessary to have two or more of these substituents and polymerizable unsaturated bonds in the crosslinkable compound.

Examples of the crosslinkable compound having an epoxy group or an isocyanate group include bisphenolacetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidylaminodiphenylene, tetraglycidyl-m-xylenediamine, and tetraglycidyl. 1,3-bis (aminoethyl) cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetodiglycidyl ether, 1,3-bis (1- (2,3-epoxypropoxy) -1 -Trifluoromethyl-2,2,2-trifluoromethyl) benzene, 4,4-bis (2,3-epoxypropoxy) octafluorobiphenyl, Liglycidyl-p-aminophenol, tetraglycidylmetaxylenediamine, 2- (4- (2,3-epoxypropoxy) phenyl) -2- (4- (1,1-bis (4- (2,3-epoxy) Propoxy) phenyl) ethyl) phenyl) propane, 1,3-bis (4- (1- (4- (2,3-epoxypropoxy) phenyl) -1- (4- (1- (4- (2,3 -Epoxypropoxy) phenyl) -1-methylethyl) phenyl) ethyl) phenoxy) -2-propanol and the like.

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

Specifically, for example, crosslinkable compounds represented by the following formulas [4a] to [4k].

Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group, an alkoxyl group, and a lower alkoxyalkyl group include, for example, an amino resin having a hydroxyl group, an alkoxyl group, or a lower alkoxyalkyl group, such as a melamine resin. And urea resin, guanamine resin, glycoluril-formaldehyde resin, succinylamide-formaldehyde resin, and ethylene urea-formaldehyde resin. The lower alkoxyalkyl group is, for example, an alkoxyalkyl group having 1 to 4 carbon atoms.

As the crosslinkable compound, for example, a melamine derivative, a benzoguanamine derivative or glycoluril in which a hydrogen atom of an amino group is substituted with a methylol group or an alkoxymethyl group or both can be used. The melamine derivative and benzoguanamine derivative may exist as a dimer or a trimer. These preferably have an average of 3 to 6 methylol groups or alkoxymethyl groups per triazine ring.

Examples of such melamine derivatives or benzoguanamine derivatives include MX-750, which has an average of 3.7 substituted methoxymethyl groups per triazine ring, and an average of 5. methoxymethyl groups per triazine ring. Eight-substituted MW-30 (from Sanwa Chemical Co., Ltd.), methoxymethylated melamines such as Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, Cymel 235, 236 Methoxymethylated butoxymethylated melamine such as 238, 212, 253, 254, butoxymethylated melamine such as Cymel 506, 508, carboxyl group-containing methoxymethylated isobutoxymethylated melamine such as Cymel 1141, Cymel 1123 and the like Methoxymethylated etoxy Methylated benzoguanamine, methoxymethylated butoxymethylated benzoguanamine such as Cymel 1123-10, butoxymethylated benzoguanamine such as Cymel 1128, carboxyl group-containing methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1125-80 Cyanamide). Examples of glycoluril include butoxymethylated glycoluril such as Cymel 1170, methylolated glycoluril such as Cymel 1172, and methoxymethylolated glycoluril such as Powderlink 1174.

Examples of benzene or phenolic compounds 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 formula [6-1] to formula [6-48].

Examples of the crosslinkable compound having a polymerizable unsaturated bond include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane, Crosslinkable compounds having three polymerizable unsaturated groups in the molecule such as glycerin polyglycidyl ether poly (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meta ) Acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (me ) 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, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl ester phthalate di (meth) acrylate, neopentyl glycol dihydroxypivalate Crosslinkable compounds having two polymerizable unsaturated groups in the molecule, such as (meth) acrylate, in addition to 2-hydroxyethyl (meth) acrylate, 2-hydroxy Propyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl Crosslinkable compounds having one polymerizable unsaturated group in the molecule, such as (meth) acrylate, glycerin mono (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate ester and N-methylol (meth) acrylamide It is done.

In addition, a compound represented by the following formula [5] can also be used.

(In the formula [5], A ₁ is an n-valent group selected from a cyclohexyl ring, a bicyclohexyl ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring, or a phenanthrene ring, A ₂ is a group selected from the following formula [5a] or [5b], and n is an integer of 1 to 4.

The above compound is an example of a crosslinkable compound and is not limited thereto. Moreover, the crosslinkable compound contained in the liquid crystal aligning agent of this invention may be one type, and may be combined two or more types.

In the liquid crystal aligning agent of the present invention, the content of the crosslinkable compound is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of the polymer of the present invention made of a polyimide precursor or polyimide. The amount is more preferably 0.1 to 100 parts by weight, particularly 1 to 50 parts by weight, so that the crosslinking reaction proceeds and the desired effect is exhibited and the orientation of the liquid crystal is not lowered.

Nitrogen-containing heterocyclic amine compounds represented by the following formulas [M1] to [M156] are used as compounds that promote charge transfer in the liquid crystal alignment film and promote charge release of a liquid crystal cell using the liquid crystal alignment film. It is preferable to add. The nitrogen-containing heterocyclic amine compound may be added directly to the polymer solution, but it is made into a solution having a concentration of 0.1% by mass to 10% by mass, preferably 1% by mass to 7% by mass with an appropriate solvent. It is preferable to add after adding. The solvent is not particularly limited as long as it is an organic solvent that dissolves the above-described resin component.

The organic solvent used in the liquid crystal aligning agent of the present invention is not particularly limited as long as it is an organic solvent that dissolves the above-described resin component. Examples thereof include N-methyl-2-pyrrolidone and butyl cellosolve.

In addition, the liquid crystal aligning agent of the present invention preferably contains a poor solvent. The poor solvent refers to a solvent that improves film thickness uniformity and surface smoothness when a liquid crystal alignment treatment agent is applied. Specific examples of the poor solvent include the following.

For example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoacetate Isopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dip Pyrene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3 -Methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl Ether, n-hexane, n-pentane, n-octane, diethyl ether , Methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, 3- Ethyl methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy -2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ester Ter-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, lactate methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n-butyl ester, lactyl isoamyl ester, etc. have low surface tension A solvent etc. are mentioned.

These solvents may be used alone or in combination. When the above poor solvent is used, it is preferably 1 to 80% by mass, more preferably 5 to 60% by mass, and further preferably 20 to 60% by mass of the total solvent contained in the liquid crystal aligning agent. %.

The liquid crystal aligning agent of the present invention may contain components other than those described above. Examples thereof include a solvent compound that improves film thickness uniformity and surface smoothness, and a compound that improves the adhesion between the liquid crystal alignment film and the substrate.

Examples of compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.

More specifically, for example, F-top EF301, EF303, EF352 (manufactured by Tochem Products), MegaFuck F171, F173, R-30 (manufactured by Dainippon Ink), Florard FC430, FC431 (manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass) and the like. The use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the resin component contained in the liquid crystal aligning agent.

Specific examples of the compound that improves the adhesion between the liquid crystal alignment film 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-aminopropyltrimethoxysilane N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxy Carbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-to Ethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltri Methoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-amino Propyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, poly Propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl -2,4-hexanediol, N, N, N ′, N ′,-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′ , N ′,-tetraglycidyl-4,4′-diaminodiphenylmethane and the like.

When using a compound to be adhered to these substrates, the amount is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the resin component contained in the liquid crystal aligning agent. It is. If it is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the orientation of the liquid crystal may deteriorate.

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

<Liquid crystal alignment film and liquid crystal display element>
The liquid crystal alignment treatment agent of the present invention can be used as a liquid crystal alignment film without applying an alignment treatment after being applied and baked on a substrate and then subjected to an alignment treatment by rubbing treatment, light irradiation, or the like. In this case, the substrate to be used is not particularly limited as long as it is a highly transparent substrate, and a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used. In addition, it is preferable to use a substrate on which an ITO electrode or the like for driving liquid crystal is formed from the viewpoint of simplifying the process. Further, in the reflection type liquid crystal display element, an opaque material such as a silicon wafer can be used as long as the substrate is only on one side, and in this case, a material that reflects light such as aluminum can be used.

The method for applying the liquid crystal alignment treatment agent is not particularly limited, but industrially, methods such as screen printing, offset printing, flexographic printing, and ink jet are generally used. Other coating methods include dip, roll coater, slit coater, spinner and the like, and these may be used depending on the purpose.

Calcination after applying the liquid crystal aligning agent on the substrate can form a coating film by evaporating the solvent at 50 to 300 ° C., preferably 80 to 250 ° C., by a heating means such as a hot plate. If the thickness of the coating film after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. Therefore, it is preferably 5 to 300 nm, more preferably 10 to 100 nm. When the liquid crystal is horizontally or tilted, the fired coating film is treated by rubbing or irradiation with polarized ultraviolet rays.

The liquid crystal display element of the present invention is a liquid crystal display element obtained by obtaining a substrate with a liquid crystal alignment film from the liquid crystal aligning agent of the present invention by the method described above, and then preparing a liquid crystal cell by a known method.

To give an example of liquid crystal cell production, prepare a pair of substrates on which a liquid crystal alignment film is formed, spray spacers on the liquid crystal alignment film of one substrate, and make the liquid crystal alignment film surface inside. Examples include a method of bonding the other substrate and injecting the liquid crystal under reduced pressure, or a method of sealing the liquid crystal after dropping the liquid crystal on the liquid crystal alignment film surface on which the spacers are dispersed, and the like. . The thickness of the spacer at this time is preferably 1 to 30 μm, more preferably 2 to 10 μm. In addition, since the liquid-crystal aligning agent of this invention has the high wettability of the liquid crystal on a liquid-crystal aligning film, it can inject | pour a liquid crystal quickly, without reducing pressure.

Further, the liquid crystal alignment treatment agent of the present invention is a liquid crystal layer using a liquid crystal display element in which alignment unevenness easily occurs during liquid crystal injection, that is, a liquid crystal material in which a polymerizable compound that is polymerized by heat or ultraviolet irradiation is mixed with liquid crystal. It is also useful for a liquid crystal display device obtained by a method of controlling the alignment direction of liquid crystal during driving with a polymer obtained by polymerizing a polymerizable compound while applying a voltage to the substrate.

In this liquid crystal display element, after obtaining a substrate with a liquid crystal alignment film from the liquid crystal alignment treatment agent of the present invention by the above-described method, a liquid crystal cell is prepared, and a polymerizable compound is polymerized by irradiation with heat or ultraviolet rays. The liquid crystal display element has a controlled orientation.

To give an example of liquid crystal cell production, prepare a pair of substrates on which a liquid crystal alignment film is formed, spray spacers on the liquid crystal alignment film of one substrate, and make the liquid crystal alignment film surface inside. Examples include a method of bonding the other substrate and injecting the liquid crystal under reduced pressure, or a method of sealing the liquid crystal after dropping the liquid crystal on the liquid crystal alignment film surface on which the spacers are dispersed, and the like. . The thickness of the spacer at this time is preferably 1 to 30 μm, more preferably 2 to 10 μm.

In addition, the liquid crystal used in this case is mixed with a polymerizable compound that is polymerized by heat or ultraviolet irradiation. Examples of the polymerizable compound include compounds having at least one polymerizable unsaturated group such as an acrylate group or a methacrylate group in the molecule. In that case, the polymerizable compound is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the liquid crystal component. When the polymerizable compound is less than 0.01 parts by mass, the polymerizable compound is not polymerized and the alignment of the liquid crystal cannot be controlled, and when it exceeds 10 parts by mass, the amount of the unreacted polymerizable compound increases, and the liquid crystal display The burn-in characteristic of the element is deteriorated.

After producing the liquid crystal cell, the orientation of the liquid crystal can be controlled by polymerizing the polymerizable compound by irradiating the liquid crystal cell with heat or ultraviolet rays while applying an AC or DC voltage.

As described above, the liquid crystal display device manufactured using the liquid crystal aligning agent of the present invention has excellent reliability and can be suitably used for a large-screen, high-definition liquid crystal television.

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

"Synthesis of polyimide precursor and polyimide of the present invention"
(Tetracarboxylic dianhydride)
CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride BODA: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride TCA: 2,3,5 -Tricarboxycyclopentylacetic acid-1,4: 2,3-dianhydride TDA: 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride

(Specific diamine compound)
DA-1: 4- (trans-4-heptylcyclohexyl) benzamide-2 ′, 4′-phenylenediamine

(Specific side chain diamine compounds)
PCH7DAB: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene PBCH5DAB: 1,3-diamino-4- {4- [trans-4- (trans-4 -N-pentylcyclohexyl) cyclohexyl] phenoxy} benzene m-PBCH5DABz: 1,3-diamino-5- {4- [4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxymethyl} benzene ColDAB -1: Specific side chain diamine compound represented by the following formula

(Other diamine compounds)
p-PDA: p-phenylenediamine m-PDA: m-phenylenediamine DBA: 3,5-diaminobenzoic acid AP18: 1,3-diamino-4-octadecyloxybenzene

(Crosslinkable compound)
Crosslinkable compound (1): YH-434L (manufactured by Tohto Kasei) (epoxy-based crosslinkable compound)
Crosslinkable compound (2): OXT-221 (manufactured by Toa Gosei) (oxetane-based crosslinkable compound)
Crosslinkable compound (3): crosslinkable compound represented by the following formula (hydroxylated phenol-based crosslinkable compound)

(Organic solvent)
NMP: N-methyl-2-pyrrolidone BCS: Butyl cellosolve

(Measurement of molecular weight of polyimide precursor and polyimide)
The molecular weight of polyimide in the synthesis example is as follows using a normal temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko) and columns (KD-803, KD-805) (manufactured by Shodex). Measured.
Column temperature: 50 ° C
Eluent: N, N′-dimethylformamide (as additives, lithium bromide-hydrate (LiBr · H ₂ O) is 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphoric acid) is 30 mmol / L, Tetrahydrofuran (THF) 10ml / L)
Flow rate: 1.0 ml / min Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000, 30,000) (manufactured by Tosoh), and polyethylene glycol (molecular weight: about 12, 000, 4,000, 1,000) (manufactured by Polymer Laboratories).

(Measurement of imidization rate)
The imidation ratio of polyimide in the synthesis example was measured as follows. Add 20 mg of polyimide powder to an NMR sample tube (NMR sampling tube standard φ5 (Kusano Kagaku)) and add 0.53 ml of deuterated dimethyl sulfoxide (DMSO-d6, 0.05% TMS (tetramethylsilane) mixture) Then, it was completely dissolved by applying ultrasonic waves. This solution was measured for proton NMR at 500 MHz with an NMR measuring instrument (JNW-ECA500) (manufactured by JEOL Datum). The imidation rate is determined by determining a proton derived from a structure that does not change before and after imidation as a reference proton, and the peak integrated value of this proton and the proton peak derived from the NH group of amic acid that appears near 9.5 to 10.0 ppm. It calculated | required by the following formula | equation using the integrated value.
Imidization rate (%) = (1−α · x / y) × 100
In the above formula, x is a proton peak integrated value derived from NH group of amic acid, y is a peak integrated value of reference proton, α is one NH group proton of amic acid in the case of polyamic acid (imidation rate is 0%) Is the number ratio of the reference proton to.

<Synthesis Example 1>
BODA (7.50 g, 30.0 mmol), DA-1 (1.53 g, 3.75 mmol), PCH7DAB (5.71 g, 15.0 mmol), p-PDA (2.03 g, 18.8 mmol) were added to NMP ( 30.1 g), and the mixture was reacted at 80 ° C. for 5 hours. Then, CBDA (1.47 g, 7.50 mmol) and NMP (24.8 g) were added, and the mixture was reacted at 40 ° C. for 6 hours. A polyamic acid solution (1) having a concentration of 24.9% by mass was obtained. The number average molecular weight of this polyamic acid was 25,400, and the weight average molecular weight was 73,300.

<Synthesis Example 2>
After adding NMP to the polyamic acid solution (1) (20.2 g) having a resin solid content concentration of 24.9% by mass obtained in Synthesis Example 1 and diluting to 6% by mass, acetic anhydride ( 2.47 g) and pyridine (1.88 g) were added and reacted at 80 ° C. for 4 hours. This reaction solution was poured into methanol (320 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (2). The imidation ratio of this polyimide was 55%, the number average molecular weight was 21,200, and the weight average molecular weight was 54,400.

<Synthesis Example 3>
BODA (6.89 g, 27.5 mmol), DA-1 (1.40 g, 3.43 mmol), PBCH5DAB (4.47 g, 10.3 mmol), DBA (3.14 g, 20.6 mmol) and NMP (28. 6 g), and after reacting at 80 ° C. for 4.5 hours, CBDA (1.35 g, 6.88 mmol) and NMP (23.4 g) were added, and the mixture was reacted at 40 ° C. for 6 hours. A polyamic acid solution having a concentration of 24.9% by mass was obtained.

After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting to 6% by mass, acetic anhydride (4.53 g) and pyridine (3.31 g) were added as an imidation catalyst, Reacted for hours. This reaction solution was put into methanol (350 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (3). The imidation ratio of this polyimide was 80%, the number average molecular weight was 19,600, and the weight average molecular weight was 49,700.

<Synthesis Example 4>
BODA (3.99 g, 15.9 mmol), DA-1 (1.86 g, 4.56 mmol), m-PBCH5DABz (2.54 g, 5.69 mmol), DBA (1.91 g, 12.6 mmol) and NMP ( 19.3 g), and the mixture was reacted at 80 ° C. for 4 hours. Then, CBDA (1.34 g, 6.83 mmol) and NMP (15.7 g) were added, and the mixture was reacted at 40 ° C. for 6 hours. A polyamic acid solution having a concentration of 25.0% by mass was obtained.

After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting to 6% by mass, acetic anhydride (4.51 g) and pyridine (3.30 g) were added as imidization catalysts, Reacted for hours. This reaction solution was poured into methanol (320 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (4). The imidation ratio of this polyimide was 81%, the number average molecular weight was 20,100, and the weight average molecular weight was 50,200.

<Synthesis Example 5>
BODA (7.09 g, 28.3 mmol), DA-1 (2.89 g, 7.09 mmol), ColDAB-1 (2.62 g, 5.32 mmol), m-PDA (2.49 g, 23.0 mmol) After mixing in NMP (27.9 g) and reacting at 80 ° C. for 4 hours, CBDA (1.39 g, 7.09 mmol) and NMP (22.5 g) were added and reacted at 40 ° C. for 5 hours. A polyamic acid solution having a solid content concentration of 24.6% by mass was obtained.

After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting to 6% by mass, acetic anhydride (2.50 g) and pyridine (1.93 g) were added as an imidization catalyst, Reacted for hours. This reaction solution was put into methanol (300 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (5). The imidation ratio of this polyimide was 55%, the number average molecular weight was 21,200, and the weight average molecular weight was 54,200.

<Synthesis Example 6>
TCA (3.43 g, 15.3 mmol), DA-1 (0.62 g, 1.52 mmol), PCH7DAB (2.33 g, 6.12 mmol), p-PDA (0.83 g, 7.68 mmol) were added to NMP ( 21.6 g) and the mixture was reacted at 40 ° C. for 7 hours to obtain a polyamic acid solution (6) having a resin solid content concentration of 25.0% by mass. This amic acid had a number average molecular weight of 25,900 and a weight average molecular weight of 69,900.

<Synthesis Example 7>
TCA (3.11 g, 13.9 mmol), DA-1 (0.57 g, 1.40 mmol), PBCH5DAB (1.80 g, 4.16 mmol), m-PDA (0.90 g, 8.32 mmol) were added to NMP ( In 19.2 g), the mixture was reacted at 40 ° C. for 7 hours to obtain a polyamic acid solution having a resin solid content concentration of 24.9% by mass.

After adding NMP to the obtained polyamic acid solution (20.5 g) and diluting to 6% by mass, acetic anhydride (2.52 g) and pyridine (1.95 g) were added as an imidization catalyst, Reacted for hours. This reaction solution was put into methanol (300 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (7). The imidation ratio of this polyimide was 52%, the number average molecular weight was 18,800, and the weight average molecular weight was 48,300.

<Synthesis Example 8>
BODA (1.21 g, 4.84 mmol), DA-1 (1.31 g, 3.21 mmol), PBCH5DAB (2.09 g, 4.83 mmol), DBA (1.23 g, 8.08 mmol) and NMP (13. 8 g), the mixture was reacted at 80 ° C. for 1.5 hours, TCA (2.53 g, 11.3 mmol) and NMP (11.3 g) were added, and the mixture was reacted at 40 ° C. for 8 hours. A polyamic acid solution having a concentration of 25.0% by mass was obtained.

After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting to 6% by mass, acetic anhydride (4.50 g) and pyridine (3.32 g) were added as imidization catalysts, Reacted for hours. This reaction solution was put into methanol (300 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (8). The imidation ratio of this polyimide was 82%, the number average molecular weight was 21,300, and the weight average molecular weight was 49,900.

<Synthesis Example 9>
BODA (1.22 g, 4.88 mmol), DA-1 (0.66 g, 1.62 mmol), ColDAB-1 (1.60 g, 3.25 mmol), m-PDA (1.23 g, 11.4 mmol) After mixing in NMP (12.5 g) and reacting at 80 ° C. for 1.5 hours, TCA (2.55 g, 11.4 mmol) and NMP (10.0 g) were added and reacted at 40 ° C. for 7 hours. A polyamic acid solution having a resin solid content concentration of 24.4% by mass was obtained.

After adding NMP to the obtained polyamic acid solution (20.5 g) and diluting to 6% by mass, acetic anhydride (2.52 g) and pyridine (1.91 g) were added as imidization catalysts, The reaction was allowed for 5 hours. This reaction solution was poured into methanol (310 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (9). The imidation ratio of this polyimide was 53%, the number average molecular weight was 22,800, and the weight average molecular weight was 56,100.

<Synthesis Example 10>
TDA (1.49 g, 4.96 mmol), DA-1 (1.35 g, 3.31 mmol), PCH7DAB (2.52 g, 6.62 mmol), DBA (1.01 g, 6.64 mmol) and NMP (14. 2g), the mixture was reacted at 80 ° C for 2 hours, CBDA (2.27g, 11.6mmol) and NMP (11.7g) were added, and the mixture was reacted at 40 ° C for 6 hours. A 25.0 mass% polyamic acid solution was obtained.

After adding NMP to the obtained polyamic acid solution (20.1 g) and diluting to 6% by mass, acetic anhydride (4.50 g) and pyridine (3.33 g) were added as an imidization catalyst, Reacted for hours. This reaction solution was poured into methanol (310 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (10). The imidation ratio of this polyimide was 76%, the number average molecular weight was 18,200, and the weight average molecular weight was 47,800.

<Synthesis Example 11>
BODA (6.79 g, 27.1 mmol), PCH7DAB (5.16 g, 13.6 mmol), p-PDA (2.20 g, 20.3 mmol) were mixed in NMP (25.0 g) and mixed at 80 ° C. for 4 hours. After reacting for a period of time, CBDA (1.33 g, 6.78 mmol) and NMP (20.5 g) were added and reacted at 40 ° C. for 6 hours. The polyamic acid solution (resin solid content concentration was 25.4% by mass) 11) was obtained. The number average molecular weight of this polyamic acid was 24,400, and the weight average molecular weight was 69,400.

<Synthesis Example 12>
After adding NMP to the polyamic acid solution (11) (20.0 g) having a resin solid content concentration of 25.4% by mass obtained in Synthesis Example 11 and diluting to 6% by mass, acetic anhydride ( 2.45 g) and pyridine (1.86 g) were added and reacted at 80 ° C. for 4 hours. This reaction solution was put into methanol (300 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (12). The imidation ratio of this polyimide was 56%, the number average molecular weight was 19,800, and the weight average molecular weight was 51,900.

<Synthesis Example 13>
BODA (6.74 g, 26.9 mmol), DA-1 (1.37 g, 3.36 mmol), AP18 (5.07 g, 13.5 mmol), p-PDA (1.82 g, 16.8 mmol) were added to NMP ( 26.3 g), and reacted at 80 ° C. for 4 hours. Then, CBDA (1.32 g, 6.73 mmol) and NMP (22.8 g) were added and reacted at 40 ° C. for 6 hours to obtain a resin solid content. A polyamic acid solution having a concentration of 24.7% by mass was obtained.

After adding NMP to the obtained polyamic acid solution (20.2 g) and diluting to 6% by mass, acetic anhydride (2.51 g) and pyridine (1.92 g) were added as an imidization catalyst, The reaction was allowed for 5 hours. This reaction solution was poured into methanol (310 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (13). The imidation ratio of this polyimide was 55%, the number average molecular weight was 20,800, and the weight average molecular weight was 50,100.

<Synthesis Example 14>
BODA (6.23 g, 24.9 mmol), DA-1 (5.07 g, 12.4 mmol), p-PDA (2.02 g, 18.7 mmol) were mixed in NMP (24.0 g), and the mixture was mixed at 80 ° C. Then, CBDA (1.22 g, 6.22 mmol) and NMP (19.6 g) were added and reacted at 40 ° C. for 6 hours, and the polyamic acid having a resin solid content concentration of 25.0% by mass was added. A solution was obtained.

After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting to 6% by mass, acetic anhydride (2.48 g) and pyridine (1.90 g) were added as an imidization catalyst, Reacted for hours. This reaction solution was put into methanol (300 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (14). The imidation ratio of this polyimide was 55%, the number average molecular weight was 25,300, and the weight average molecular weight was 62,100.

<Synthesis Example 15>
BODA (1.12 g, 4.48 mmol), ColDAB-1 (1.47 g, 2.98 mmol), m-PDA (1.29 g, 11.9 mmol) were mixed in NMP (10.8 g), and 80 ° C. Then, TCA (2.34 g, 10.4 mmol) and NMP (8.42 g) were added, and the mixture was reacted at 40 ° C. for 8 hours. The polyamic acid having a resin solid content concentration of 24.4 mass% was obtained. A solution was obtained.

After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting to 6% by mass, acetic anhydride (2.43 g) and pyridine (1.85 g) were added as imidization catalysts, Reacted for hours. This reaction solution was put into methanol (300 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (15). The imidation ratio of this polyimide was 52%, the number average molecular weight was 19,200, and the weight average molecular weight was 51,900.

Table 48 shows the polyamic acid and polyimide of the present invention.

“Production of Liquid Crystal Alignment Treatment Agent of the Present Invention”
In Examples 1 to 13 and Comparative Examples 1 to 5 described below, production examples of liquid crystal alignment treatment agents are described. The liquid crystal alignment of the present invention used for evaluation of each liquid crystal alignment treatment agent is described. The treating agents are shown in Table 49 and Table 50.

“Preparation of liquid crystal alignment film”, “Evaluation of wettability of liquid crystal”, “Preparation of liquid crystal cell”, and “Evaluation of liquid crystal alignment and pretilt angle” are as follows. In addition, Tables 51 to 54 show the characteristics of the liquid crystal alignment treatment agents obtained in Examples 1 to 13 and Comparative Examples 1 to 5.

"Production of liquid crystal alignment film"
A liquid crystal alignment treatment agent is spin-coated on the ITO surface of a substrate with 3 × 4 cm ITO electrodes, and is heated on a hot plate at 80 ° C. for 5 minutes, and then heated at 220 ° C. for 30 minutes in a heat-circulating clean oven. A substrate with a 100 nm thick polyimide liquid crystal alignment film was obtained.

"Evaluation of liquid crystal wettability"
Using a substrate with a liquid crystal alignment film obtained in the above-mentioned “Preparation of liquid crystal alignment film”, MLC-6608 (manufactured by Merck Japan), and a fully automatic contact angle meter CA-W (manufactured by Kyowa Interface Science) as the liquid crystal, The wettability of the liquid crystal was evaluated. Evaluation was made by measuring the contact angle of the liquid crystal 10 seconds after the liquid crystal reached the liquid crystal alignment film. The lower the contact angle of the liquid crystal, the higher the wettability of the liquid crystal on the liquid crystal alignment film.

"Production of liquid crystal cell"
The coating film surface of the substrate with the liquid crystal alignment film obtained in the above-mentioned “Preparation of liquid crystal alignment film” was rotated at a rotational speed of 300 rpm, a moving speed of 20 mm / sec, and a pushing amount of 0. The rubbing process was performed under the condition of 2 mm. Prepare two substrates with this liquid crystal alignment film, combine them so that the liquid crystal alignment film surface is on the inside, sandwich a 6μm spacer, and the rubbing direction is reversed. did. MLC-6608 (manufactured by Merck Japan Co., Ltd.) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain an antiparallel aligned nematic liquid crystal cell.

"Evaluation of liquid crystal alignment and pretilt angle"
The liquid crystal cell obtained in the above-mentioned “Preparation of liquid crystal cell” was measured at room temperature using a pretilt angle measuring apparatus PAS-301 (manufactured by ELSICON) at an initial stage after liquid crystal injection and after a heat treatment at 95 ° C. for 5 minutes. . Moreover, about the liquid crystal cell of each condition, the orientation uniformity of the liquid crystal was confirmed by polarizing microscope observation. In any of the liquid crystal cells, there was no shaving or poor alignment due to the rubbing treatment, and the liquid crystal was uniformly aligned.

<Example 1>
The polyamic acid solution (1) (10.5 g), NMP (8.50 g), and BCS (24.6 g) having a resin solid content concentration of 24.9% by mass obtained in Synthesis Example 1 were added at 25 ° C. By mixing for a time, a liquid crystal aligning agent (1) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 2>
The polyimide powder (2) (2.52 g), NMP (22.3 g), and BCS (19.7 g) obtained in Synthesis Example 2 were mixed at 25 ° C. for 8 hours to obtain a liquid crystal aligning agent (2 ) This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 3>
The polyimide powder (3) (2.50 g), NMP (24.0 g), and BCS (17.6 g) obtained in Synthesis Example 3 were mixed at 25 ° C. for 8 hours to obtain a liquid crystal alignment treatment agent (3 ) This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 4>
The polyimide powder (4) (2.51 g), NMP (26.1 g), and BCS (15.7 g) obtained in Synthesis Example 4 were mixed at 25 ° C. for 8 hours to obtain a liquid crystal alignment treatment agent (4 ) This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 5>
The polyimide powder (5) (2.50 g), NMP (29.9 g), and BCS (11.8 g) obtained in Synthesis Example 5 were mixed at 25 ° C. for 8 hours to obtain a liquid crystal alignment treatment agent (5 ) This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 6>
The polyamic acid solution (6) (11.0 g), NMP (11.1 g), and BCS (23.7 g) having a resin solid content concentration of 25.0% by mass obtained in Synthesis Example 6 were obtained at 25 ° C. By mixing for a time, a liquid crystal aligning agent (6) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 7>
The polyimide powder (7) (2.51 g), NMP (30.0 g), and BCS (11.8 g) obtained in Synthesis Example 7 were mixed at 25 ° C. for 8 hours to obtain a liquid crystal alignment treatment agent (7 ) This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 8>
The polyimide powder (8) (2.50 g), NMP (26.0 g), and BCS (15.7 g) obtained in Synthesis Example 8 were mixed at 25 ° C. for 8 hours to obtain a liquid crystal alignment treatment agent (8 ) This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 9>
The polyimide powder (9) (2.50 g), NMP (31.9 g), and BCS (9.80 g) obtained in Synthesis Example 9 were mixed at 25 ° C. for 8 hours to obtain a liquid crystal alignment treatment agent (9 ) This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 10>
The polyimide powder (10) (2.53 g), NMP (30.3 g), and BCS (11.9 g) obtained in Synthesis Example 10 were mixed at 25 ° C. for 8 hours to obtain a liquid crystal alignment treatment agent (10 ) This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 11>
The polyimide powder (2) (2.50 g), NMP (22.1 g), BCS (19.6 g), and crosslinkable compound (1) (0.25 g) obtained in Synthesis Example 2 were added at 25 ° C. The liquid crystal aligning agent (11) was obtained by mixing for 12 hours. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 12>
The polyimide powder (3) (2.50 g), NMP (24.0 g), BCS (17.6 g), and crosslinkable compound (2) (0.50 g) obtained in Synthesis Example 3 were added at 25 ° C. The liquid crystal aligning agent (12) was obtained by mixing for 12 hours. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 13>
The polyimide powder (3) (2.51 g), NMP (24.1 g), BCS (17.7 g), and the crosslinkable compound (3) (0.25 g) obtained in Synthesis Example 3 were added at 25 ° C. It mixed for 12 hours and obtained the liquid-crystal aligning agent (13). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Comparative Example 1>
The polyamic acid solution (11) (10.0 g), NMP (8.50 g), and BCS (23.9 g) having a resin solid content concentration of 25.4% by mass obtained in Synthesis Example 11 were added at 25 ° C. It mixed for a time and the liquid-crystal aligning agent (14) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Comparative Example 2>
The polyimide powder (12) (2.50 g), NMP (22.1 g), and BCS (19.6 g) obtained in Synthesis Example 12 were mixed at 25 ° C. for 8 hours to obtain a liquid crystal alignment treatment agent (15 ) This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Comparative Example 3>
The polyimide powder (13) (2.51 g), NMP (24.1 g), and BCS (17.7 g) obtained in Synthesis Example 13 were mixed at 25 ° C. for 8 hours to obtain a liquid crystal alignment treatment agent (16 ) This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Comparative Example 4>
The polyimide powder (14) (2.50 g), NMP (22.1 g), and BCS (19.6 g) obtained in Synthesis Example 14 were mixed at 25 ° C. for 8 hours to obtain a liquid crystal alignment treatment agent (17 ) This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Comparative Example 5>
The polyimide powder (15) (2.50 g), NMP (29.9 g), and BCS (11.8 g) obtained in Synthesis Example 15 were mixed at 25 ° C. for 8 hours to obtain a liquid crystal alignment treatment agent (18 ) This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

As can be seen from the above results, in the liquid crystal alignment films obtained from the liquid crystal alignment treatment agents of Examples 1 to 13, the liquid crystal wettability on the liquid crystal alignment film is high while the pretilt angle of the liquid crystal is high.

In Comparative Example 1, Comparative Example 2, and Comparative Example 5 using only the specific side chain type diamine compound, the pretilt angle of the liquid crystal is high, but the liquid crystal wettability on the liquid crystal alignment film is low. Further, Comparative Example 3 using a side chain diamine compound other than the specific diamine compound and the specific side chain diamine compound similarly has a high pretilt angle of the liquid crystal, but low wettability of the liquid crystal on the liquid crystal alignment film. As a result. In addition, in Comparative Example 4 using only the specific diamine compound, the liquid crystal wettability on the liquid crystal alignment film was high, but the pretilt angle of the liquid crystal was low.

The liquid crystal alignment treatment agent of the present invention can obtain a liquid crystal alignment film having high liquid crystal wettability on the liquid crystal alignment film. In particular, even when a large amount of a diamine component having a side chain is used to obtain a high pretilt angle, the effect can be obtained. Therefore, by using the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention, it is possible to obtain a liquid crystal display element that has high production efficiency at the time of manufacturing the liquid crystal display element and does not cause poor display of alignment unevenness. As a result, it can be suitably used for a large-screen, high-definition liquid crystal television and the like, and is useful for a TN element, an STN element, a TFT liquid crystal element, particularly a vertical alignment type liquid crystal display element.

Furthermore, the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention is a liquid crystal display element in which alignment unevenness easily occurs during liquid crystal injection, that is, a liquid crystal mixed with a polymerizable compound that is polymerized by heat or ultraviolet irradiation. This is a polymer obtained by polymerizing a liquid crystal layer while applying a voltage to the liquid crystal layer, and is also useful for a liquid crystal display device obtained by a method for controlling the alignment direction of liquid crystal during driving.

Claims

Liquid crystal alignment treatment comprising a diamine compound represented by the following formula [1] and a polymer obtained by reacting a diamine component containing the diamine compound represented by the following formula [2] with tetracarboxylic dianhydride. Agent.

(In the formula [1], X 1 is a divalent organic group selected from —NHCO—, —N (CH 3 ) CO—, —CONH—, —CON (CH 3 ) —, and X 2 is a single bond. , A benzene ring or a cyclohexyl ring, X 3 is a divalent organic group selected from a benzene ring or a cyclohexyl ring, and X 4 is a cyclohexyl ring, Or a divalent organic group selected from a benzene ring, and X 5 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 1 carbon atom. From 18 to 18 fluorine-containing alkoxyl groups, and n is an integer from 1 to 4.

(In the formula [2], Y 1 is —O—, —CH 2 O—, — (CH 2 ) a — (a is an integer of 1 to 10), —COO—, —OCO—, or a single bond Y 2 is a single bond or a divalent organic group selected from — (CH 2 ) b — (b is an integer of 1 to 10), and Y 3 is A divalent organic group selected from a single bond, — (CH 2 ) c — (c is an integer of 1 to 10), —O—, —CH 2 O—, —COO—, or —OCO—. , Y 4 represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring, or a heterocyclic ring, or a divalent organic group having 12 to 25 carbon atoms and having a steroid skeleton. The hydrogen atom is 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, Fluorine-containing alkoxyl group having 1 to 3 carbon atoms, may be substituted with one selected from a fluorine atom, Y 5 represents a divalent cyclic group selected from cyclohexyl ring, a benzene ring or a heterocyclic cyclohexane, Arbitrary hydrogen atoms on these cyclic groups are alkyl groups having 1 to 3 carbon atoms, alkoxyl groups having 1 to 3 carbon atoms, fluorine-containing alkyl groups having 1 to 3 carbon atoms, or fluorine containing 1 to 3 carbon atoms An alkoxyl group, which may be substituted with one selected from fluorine atoms, n is an integer of 0 to 4, Y 6 is an alkyl group having 1 to 18 carbon atoms, or a fluorine-containing alkyl group having 1 to 18 carbon atoms , An alkoxyl group having 1 to 18 carbon atoms, a fluorine-containing alkoxyl group having 1 to 18 carbon atoms, or a hydrogen atom, and m is an integer of 1 to 4.
The liquid crystal aligning agent according to claim 1 , wherein, in the formula [1], X 1 is -NHCO-.
The liquid crystal aligning agent according to claim 1, wherein the tetracarboxylic dianhydride is a tetracarboxylic dianhydride represented by the following formula [3].

(In the formula [3], Z 1 is a tetravalent organic group having 4 to 13 carbon atoms and contains a non-aromatic cyclic hydrocarbon group having 4 to 6 carbon atoms).
The liquid crystal aligning agent according to claim 3, wherein Z 1 has a structure represented by the following formulas [3a] to [3j].

(In the formula [3a], Z 2 to Z 5 are groups selected from a hydrogen atom, a methyl group, a chlorine atom, or a benzene ring, which may be the same or different, and in the formula [3g] Z 6 and Z 7 are a hydrogen atom or a methyl group, and each may be the same or different.
In the liquid crystal aligning agent, a crosslinkable compound having at least one substituent selected from the group consisting of epoxy group, oxetane group, isocyanate group and cyclocarbonate group, hydroxyl group, hydroxyalkyl group, alkoxyl group and lower alkoxyalkyl 5. The liquid crystal alignment treatment according to claim 1, comprising a crosslinkable compound having at least one substituent selected from the group consisting of groups, or a crosslinkable compound having a polymerizable unsaturated bond. Agent.
The liquid crystal aligning agent according to any one of claims 1 to 5, wherein the polymer in the liquid crystal aligning agent is a polyimide obtained by dehydrating and ring-closing polyamic acid.
The liquid crystal aligning agent according to any one of claims 1 to 6, wherein the liquid crystal aligning agent contains 5 to 60% by mass of a poor solvent.
A liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent according to any one of claims 1 to 7.
A liquid crystal display element having the liquid crystal alignment film according to claim 8.
A liquid crystal alignment film obtained by using the liquid crystal aligning agent according to any one of claims 1 to 7, wherein a liquid crystal material in which a liquid crystal is mixed with a polymerizable compound that is polymerized by heat or ultraviolet irradiation is used. A liquid crystal alignment film used for a liquid crystal display element, which is a polymer obtained by polymerizing the polymerizable compound while applying a voltage to the liquid crystal layer, and is obtained by a method of controlling the alignment direction of the liquid crystal during driving.
11. A liquid crystal display element comprising the liquid crystal alignment film according to claim 10, wherein the polymerization is performed while applying a voltage to the liquid crystal layer using a liquid crystal material in which a liquid crystal is mixed with a polymerizable compound that is polymerized by heat or ultraviolet irradiation. A liquid crystal display element obtained by polymerizing an organic compound and obtained by a method of controlling the alignment direction of liquid crystal during driving.