WO2009093704A1

WO2009093704A1 - Diamine compound, liquid crystal aligning agent, and liquid crystal display device using the same

Info

Publication number: WO2009093704A1
Application number: PCT/JP2009/051107
Authority: WO
Inventors: Satoshi Minami; Kohei Goto; Takahiro Suga; Hiroshi Kita
Original assignee: Nissan Chemical Industries, Ltd.
Priority date: 2008-01-25
Filing date: 2009-01-23
Publication date: 2009-07-30
Also published as: KR101738330B1; KR101737122B1; CN101925634B; JP5663876B2; CN101925634A; KR20100103606A; JPWO2009093704A1; TWI490207B; TW200940506A; KR20170010899A

Abstract

Disclosed is a liquid crystal aligning agent which enables formation of a liquid crystal alignment film having high voltage holding ratio, in which film relaxation of residual charges accumulated by a DC voltage is fast even after long-time exposure to high temperatures. Also disclosed are a polyamide acid and/or a polyimide (hereinafter also referred to as a polymer) contained in the liquid crystal aligning agent, a diamine compound which can be used as a raw material for the polyamide acid and/or the polyimide, and a highly reliable liquid crystal display device having the liquid crystal alignment film, which device can endure long-time use in severe environments. Specifically disclosed is a diamine compound represented by Formula [1]. [1] (In Formula [1], X1 represents at least one divalent organic group selected from the group consisting of -O-, -NQ1-, -CONQ1-, -NQ1CO-, -CH2O- and -OCO-; Q1 represents a hydrogen atom or an alkyl group having 1-3 carbon atoms; X2 represents a single bond or at least one divalent organic group selected from the group consisting of aliphatic hydrocarbon groups having 1-20 carbon atoms, non-aromatic cyclic hydrocarbon groups and aromatic cyclic hydrocarbon groups; X3 represents a single bond or at least one divalent organic group selected from the group consisting of -O-, -NQ2-, -CONQ2-, -NQ2CO-, -COO-, -OCO- and -O(CH2)m- (wherein m represents an integer of 1-5); Q2 represents a hydrogen atom or an alkyl group having 1-3 carbon atoms; X4 represents a nitrogen-containing aromatic heterocyclic ring; and n represents an integer of 1-4.)

Description

Diamine compound, liquid crystal aligning agent, and liquid crystal display element using the same

The present invention relates to a diamine compound useful as a raw material for a polymer used in a liquid crystal alignment film, a polyamic acid and a polyimide obtained using the diamine compound, and a liquid crystal alignment treatment agent. Furthermore, the present invention relates to a liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent.

Currently, as a liquid crystal alignment film of a liquid crystal display element, a liquid crystal alignment treatment agent (also referred to as a liquid crystal alignment agent) mainly composed of a polyimide precursor such as polyamic acid or a solution of soluble polyimide is applied to a glass substrate and fired. A so-called polyimide-based liquid crystal alignment film is mainly used.

The liquid crystal alignment film is used for the purpose of controlling the alignment state of the liquid crystal. However, as the liquid crystal display elements have become higher in definition, the liquid crystal alignment film used has a high voltage holding ratio and a direct current voltage has been applied due to demands for suppressing the decrease in contrast of the liquid crystal display elements and reducing the afterimage phenomenon. The characteristic that the residual charge at the time is small and / or the residual charge accumulated by the DC voltage is quickly relaxed has become increasingly important.

In a polyimide-based liquid crystal alignment film, a liquid crystal aligning agent containing a tertiary amine having a specific structure in addition to polyamic acid or an imide group-containing polyamic acid was used as a short time until the afterimage generated by direct current voltage disappears. There are known ones (for example, see Patent Document 1) and those using a liquid crystal aligning agent containing a soluble polyimide using a specific diamine having a pyridine skeleton as a raw material (for example, see Patent Document 2). In addition to polyamic acid and its imidized polymer, a compound containing one carboxylic acid group in the molecule, assuming that the voltage holding ratio is high and the time until the afterimage generated by direct current voltage disappears is short , Using a liquid crystal aligning agent containing a very small amount of a compound selected from a compound containing one carboxylic anhydride group in the molecule and a compound containing one tertiary amine group in the molecule (for example, a patent Document 3) is known.

However, in recent years, large-screen, high-definition liquid crystal televisions have been widely put into practical use, and liquid crystal display elements in such applications are more effective against afterimages than conventional displays that mainly display characters and still images. The requirements are becoming stricter, and characteristics that can withstand long-term use in harsh usage environments are required. Therefore, the liquid crystal alignment film to be used has to be more reliable than conventional liquid crystal alignment films. The electrical characteristics of the liquid crystal alignment film are not only good in initial characteristics but also, for example, at a high temperature for a long time. There is a need to maintain good properties even after exposure.

JP-A-9-316200 JP-A-10-104633 JP-A-8-76128

An object of the present invention is to provide a liquid crystal alignment film for use in the following liquid crystal display element, a liquid crystal alignment treatment agent for forming the liquid crystal alignment film, a polyamic acid and / or a polyimide (hereinafter referred to as heavy metal) contained in the liquid crystal alignment treatment agent. Another object is to provide a diamine compound that can be used as a raw material for the polyamic acid and polyimide.

Furthermore, an object of the present invention is to provide a liquid crystal alignment film having a high voltage holding ratio and capable of obtaining a liquid crystal alignment film in which residual charges accumulated by a DC voltage are quickly relaxed even after being exposed to a high temperature for a long time. An object of the present invention is to provide a treatment agent and to provide a highly reliable liquid crystal display element that has the liquid crystal alignment film and can withstand long-term use in a harsh use environment.

The present inventor conducted extensive research to achieve the above object, and found a novel diamine compound that achieves this. The present invention is based on such knowledge and has the following gist.
(1) A diamine compound represented by the following formula [1].

(Wherein [1], X ₁ is ^{^{-O -, - NQ 1 -,}} - CONQ 1 -, - NQ 1 CO -, - CH 2 O-, and at least one selected from the group consisting of -OCO- A divalent organic group, Q ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X ₂ is a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a non-aromatic cyclic carbonization hydrogen radicals, and at least one divalent organic group selected from the group consisting of an aromatic hydrocarbon group, _{X 3} is a single bond or ^{-O -, - NQ 2 -,} - CONQ 2 -, - NQ ² at least one divalent organic group selected from the group consisting of ₂ CO—, —COO—, —OCO—, and —O (CH ₂ ) _m — (m is an integer of 1 to 5); Q ² is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X ₄ is a nitrogen-containing aromatic heterocyclic ring. , N is an integer from 1 to 4).
(2) The diamine compound according to the above (1), wherein the diamine compound of the formula [1] is at least one selected from the group consisting of compounds represented by the following formulas [1a] to [1f].

(Wherein Q ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X ₂ is a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group, and at least one divalent organic group selected from the group consisting of an aromatic hydrocarbon group, _{X 3} is a single bond or ^{^{-O -, - NQ 2 -,}} - CONQ 2 -, - NQ 2 CO-, And at least one divalent organic group selected from the group consisting of —COO—, —OCO—, and —O (CH ₂ ) _m — (m is an integer of 1 to 5), and Q ² is hydrogen An atom or an alkyl group having 1 to 3 carbon atoms, X ₄ is a nitrogen-containing aromatic heterocyclic ring, and n is an integer of 1 to 4).
(3) The diamine compound according to the above (2), wherein X ₂ in the formulas [1a] to [1f] is a single bond, a linear alkylene group having 1 to 3 carbon atoms, or a benzene ring.
(4) The diamine compound according to (2) or (3) above, wherein X ₃ in the formulas [1a] to [1f] is a single bond, —OCO—, or —OCH ₂ —.
(5) The diamine compound according to any one of (2) to (4) above, wherein X ₄ in the formulas [1a] to [1f] is an imidazole ring, a pyridine ring, or a pyrimidine ring.
(6) The diamine compound according to any one of (2) to (5) above, wherein n in the formula [1a] to formula [1f] is an integer of 1 or 2.
(7) At least one selected from the group consisting of a linear or branched alkylene group having 1 to 10 carbon atoms, a cyclohexane ring, a benzene ring, and a naphthalene ring, wherein X ₂ in the formulas [1a] to [1f] is And X ₃ is a single bond, —O—, —CONH—, —NHCO—, —COO—, —OCO—, and —O (CH ₂ ) _m — (m is an integer of 1 to 5) is at least one selected from the group consisting, X ₄ is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, and a benzimidazole ring The diamine compound according to the above (1) or (2), which is at least one selected from the group consisting of n and n is an integer of 1 or 2.
(8) X ₂ in the formulas [1a] to [1f] is at least one selected from the group consisting of a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms, and a benzene ring, and X ₃ Is selected from the group consisting of a single bond, —O—, —CONH—, —NHCO—, —COO—, —OCO—, and —O (CH ₂ ) _m — (m is an integer of 1 to 5). The above (1) or at least one, wherein X ₄ is at least one selected from the group consisting of a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, and a pyrimidine ring, and n is an integer of 1 or 2. The diamine compound according to (2).
(9) X ₂ in the formulas [1a] to [1f] is at least one selected from the group consisting of a single bond, a linear alkylene group having 1 to 3 carbon atoms, and a benzene ring, and X ₃ is a single group. At least one selected from the group consisting of a bond, —OCO—, and —OCH ₂ —, X ₄ is at least one selected from the group consisting of an imidazole ring, a pyridine ring, and a pyrimidine ring, and n is 1 Or the diamine compound as described in said (1) or (2) which is an integer of 2.
(10) Polyamic acid obtained by reacting the diamine component containing the diamine compound according to any one of (1) to (9) above and tetracarboxylic dianhydride, or dehydrating and ring-closing the polyamic acid. Polyimide obtained.
(11) The polyamic acid or polyimide according to the above (10), wherein the diamine compound represented by the formula [1] is 1 to 80 mol% in the diamine component.
(12) A liquid crystal aligning agent containing at least one of the polyamic acid and the polyimide according to (10) or (11) and a solvent.
(13) The liquid-crystal aligning agent as described in said (12) whose 5-80 mass% in the solvent contained in a liquid-crystal aligning agent is a poor solvent.
(14) A liquid crystal alignment film obtained using the liquid crystal aligning agent according to (12) or (13).
(15) A liquid crystal display device having the liquid crystal alignment film according to (14).

The diamine compound of the present invention can be obtained by a relatively simple method. When the diamine compound is used as a raw material for the polymer constituting the liquid crystal alignment film, the voltage holding ratio is high, and the diamine compound is exposed to a high temperature for a long time. Even after this, a liquid crystal alignment film can be obtained in which the residual charge accumulated by the DC voltage is quickly relaxed. Therefore, the liquid crystal display element having the liquid crystal alignment film obtained from 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.

The present invention is described in detail below.
The present invention provides a diamine compound represented by the formula [1], a polymer obtained by using the diamine compound represented by the formula [1] as a raw material, a liquid crystal alignment treatment agent containing the polymer, and the liquid crystal alignment treatment agent. It is a liquid crystal display element which has a liquid crystal aligning film obtained by using and also this liquid crystal aligning film.
The diamine compound of the present invention is a diamine compound having a nitrogen-containing aromatic heterocycle in the side chain (hereinafter sometimes referred to as a specific diamine compound). This nitrogen-containing aromatic heterocycle functions as an electron hopping site due to its conjugated structure, so in a liquid crystal alignment film produced from a liquid crystal alignment treatment agent containing a polymer obtained from a specific diamine compound, It is possible to promote the movement of charges.
As described above, the liquid crystal aligning agent of the present invention has a high voltage holding ratio when formed into a liquid crystal alignment film, and the residual charge accumulated by a DC voltage even after being exposed to a high temperature for a long time. A liquid crystal alignment film that is quickly relaxed can be obtained.

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

Wherein [1], X ₁ is ^{^{-O -, - NQ 1 -,}} - CONQ 1 -, - NQ 1 CO -, - CH 2 O-, and at least one 2 selected from the group consisting of -OCO- A valent organic group, Q ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X ₂ is a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a non-aromatic cyclic hydrocarbon group, and at least one divalent organic group selected from the group consisting of an aromatic hydrocarbon group, _{X 3} is a single bond or ^{-O -, - NQ 2 -,} - CONQ 2 -, - NQ 2 And at least one divalent organic group selected from the group consisting of CO—, —COO—, —OCO—, and —O (CH ₂ ) _m — (m is an integer of 1 to 5), and Q ² is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X ₄ is a nitrogen-containing aromatic heterocyclic ring, n is an integer of 1 to 4.

The bonding position of the two amino groups (—NH ₂ ) in the formula [1] is not limited. Specifically, when n is an integer of _{1, with} respect to the side chain linking group (X ₁ ), 2, 3 positions, 2, 4 positions, 2, 5 positions on the benzene ring, 2, 6 positions, 3 and 4 positions, and 3 and 5 positions. When n is an integer of 2, the following positions are listed. When the side chain linking group (X ₁ ) is located at 2 positions on the benzene ring with respect to the side chain linking group (X ₁ ), the bonding positions of the two amino groups are the positions 3 and 4, 3 , 5 position, 3, 6 position, and 4, 5 position. In addition, when there is a side chain linking group (X ₁ ) at position 3 on the benzene ring with respect to the side chain linking group (X ₁ ), the bonding positions of the two amino groups are positions 2 and 4 , 2, 5 positions, 4, 5 positions, and 4, 6 positions. Furthermore, when there is a side chain linking group (X ₁ ) at position 4 on the benzene ring with respect to the side chain linking group (X ₁ ), the two amino groups are bound at positions 2, 3 , 2, 5 position, 2, 6 position, 3, 5 position. When n is an integer of 3, the following positions are listed. When the side chain linking group (X ₁ ) is located at 2, 3 positions on the benzene ring with respect to the side chain linking group (X ₁ ), the bonding positions of the two amino groups are positions 4 and 5 , 4, 6 positions. In addition, when the side chain linking group (X ₁ ) is located at 2, 4 positions on the benzene ring with respect to the side chain linking group (X ₁ ), the bonding positions of the two amino groups are 3, 5 , 3, 6 and 5, 6 positions. Furthermore, when there are side chain bonding groups (X ₁ ) at positions 3 and 5 on the benzene ring with respect to the side chain bonding group (X ₁ ), the bonding positions of the two amino groups are 2, 4 Position. When n is an integer of 4, the following positions are listed. When there are side chain bonding groups (X ₁ ) at positions 2, 3, and 4 on the benzene ring with respect to the side chain bonding group (X ₁ ), the bonding positions of the two amino groups are 5, 6 Position. In addition, when there are side chain bonding groups (X ₁ ) at positions 2, 4, and 5 on the benzene ring with respect to the side chain bonding group (X ₁ ), the bonding positions of the two amino groups are 3 , 6 positions. Further, when the side chain linking group (X ₁ ) is located at positions 2, 4, 6 on the benzene ring with respect to the side chain linking group (X ₁ ), the bonding positions of the two amino groups are 3 , 5 positions. Among these, taking into consideration the reactivity when synthesizing the polyamic acid and the ease when synthesizing the diamine compound, when n is an integer of 1, the bonding positions of the two amino groups are 2,4. , 2, 5 position, 3, 5 position, or side chain linking group (X ₁ ) when n is an integer of 2, side chain linking group at position 3 on the benzene ring In the case where (X ₁ ) is present, the positions where the binding positions of the two amino groups are 4, 6 are particularly preferable.

Wherein [1], _{X 1} is ^{^{-O -, - NQ 1 -,}} - CONQ 1 -, - NQ 1 CO -, - CH 2 O-, and at least one 2 selected from the group consisting of -OCO- Valent organic group. Among ^{them, -O -, - NQ 1 -} , - CONQ 1 -, - NQ 1 CO- is preferred. In addition, ^{Q 1} has the formula [1]
The definition is the same.
More specific structures of X ₁ include the following formulas [1a] to [1f].

Among these, the formula [1a], the formula [1b], the formula [1c], and the formula [1d] are preferable. Q ¹ has the same meaning as defined in formula [1].

In the formula [1], X ₂ is a single bond or at least one selected from the group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group, and an aromatic hydrocarbon group. It is a divalent organic group.
The aliphatic hydrocarbon group having 1 to 20 carbon atoms may be linear or branched. Moreover, you may have an unsaturated bond. An aliphatic hydrocarbon group having 1 to 10 carbon atoms is preferred.

Specific examples of the non-aromatic cyclic hydrocarbon group include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, Cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicosane ring, tricycloeicosane ring, tricyclodecosan ring, bicycloheptane ring, decahydro A naphthalene ring, a norbornene ring, an adamantane ring, etc. are mentioned.
Specific examples of the aromatic hydrocarbon group include a benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring, and phenalene ring.

Preferred X ₂ in the formula [1] is a single bond, a linear or branched alkylene group having 1 to 10 carbon atoms, an unsaturated alkylene group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, or a cyclopentane ring. , Cyclohexane ring, cycloheptane ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, fluorene ring, and anthracene ring, more preferably a single bond, linear or branched alkylene having 1 to 10 carbon atoms Group, an unsaturated alkylene group having 1 to 10 carbon atoms, a cyclohexane ring, a norbornene ring, an adamantane ring, a benzene ring, a naphthalene ring, a fluorene ring, and an anthracene ring, and more preferably a single bond and a straight chain having 1 to 10 carbon atoms. Chain or branched alkylene group, cyclohexane ring, benzene ring, naphtha A len ring, particularly preferably a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms, and a benzene ring. Most preferably, they are a single bond, a linear alkylene group having 1 to 3 carbon atoms, or a benzene ring.

Wherein [1], _{X 3} is a single bond or ^{^{-O -, - NQ 2 -,}} - CONQ 2 -, - NQ 2 CO -, - COO -, - OCO-, and -O _(CH _{2) m} - (M is an integer of 1 to 5) is at least one divalent organic group selected from the group consisting of a single bond, —O—, —CONQ ² —, —NQ ² CO—, —COO—, —OCO—, —O (CH ₂ ) _m — (m is an integer of 1 to 5). Most preferably, it is a single bond, —OCO—, or —OCH ₂ —. Q ² has the same meaning as defined in formula [1].

In the formula [1], X ₄ is a nitrogen-containing aromatic heterocyclic ring, and nitrogen containing at least one structure selected from the group consisting of the following formulas [[2a], formulas [2b] and formulas [2c] Containing aromatic heterocycle.

In formula [2c], Y ₁ is a linear or branched alkyl group having 1 to 5 carbon atoms.

Preferable X ₄ in the formula [1] is a pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring. , Pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, thionoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring Acridine ring, more preferably pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyrazoline ring, carbazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring , Triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, more preferably pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benz An imidazole ring and a benzimidazole ring are preferable, and a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, and a pyrimidine ring are particularly preferable. Most preferably, it is an imidazole ring, a pyridine ring, or a pyrimidine ring.

Further, _{X 3} is formulas contained in _{X 4} [2a], it is preferably bonded to a substituent not adjacent to Equation [2b] and the formula [2c].
In the formula [1], n is an integer of 1 to 4, and preferably an integer of 1 to 3 from the viewpoint of reactivity with tetracarboxylic dianhydride. Most preferably, n is an integer of 1 or 2.

A preferred combination of _{_{_{X 1, X 2, X 3}}} , X 4 and n in the formula [1], _{X 1} is ^{^{-O -, - NQ 1 -,}} - CONQ 1 -, - NQ 1 CO -, - CH 2 O And at least one selected from the group consisting of —OCO—, wherein X ₂ is a linear or branched alkylene group having 1 to 10 carbon atoms, an unsaturated alkylene group having 1 to 10 carbon atoms, a cyclopropane ring, cyclobutane X ₃ is at least one selected from the group consisting of a ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a norbornene ring, an adamantane ring, a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, a fluorene ring, and an anthracene ring. single ^{^{bond, -O -, - NQ 2 -}} , - CONQ 2 -, - NQ 2 CO -, - COO -, - OCO-, and -O _(CH ₂₎ m - ₍ m is at least one selected from the group consisting of 1 to 5), and X ₄ is a pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline Ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, tinoline ring, phenanthroline ring, indole ring, quinoxaline It is at least one selected from the group consisting of a ring, a benzothiazole ring, a phenothiazine ring, an oxadiazole ring, and an acridine ring, and n is an integer of 1 or 2.

More preferably _X 1 in the formula _{_{[1], X 2, X}} 3, X 4 and n combinations of, _{X 1} is ^{^{-O -, - NQ 1 -,}} - CONQ 1 -, - NQ 1 CO-, and -CH _At least one selected from the group consisting of ₂ O—, wherein X ₂ is a linear or branched alkylene group having 1 to 10 carbon atoms, an unsaturated alkylene group having 1 to 10 carbon atoms, a cyclohexane ring, a norbornene ring, an adamantane ring a benzene ring, a naphthalene ring, a fluorene ring, and at least one selected from the group consisting of an anthracene ring, _{X 3} is a single ^{bond, -O -, - NQ 2 -} , - CONQ 2 -, - NQ 2 CO- , -COO -, - OCO-, and _{_{-O (CH 2) m - (}} m is from 1 5 is an integer) is at least one selected from the group consisting of, _{X 4} is a pyrrole ring, an imidazole ring At least one selected from the group consisting of pyrazole ring, pyridine ring, pyrimidine ring, pyrazoline ring, carbazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, and benzimidazole ring And n is an integer of 1 or 2.

Further preferred compounds of formula _X 1 in _{_{[1], X 2, X}} 3, the combination of _{X 4} and n, _{X 1} is ^{^{-O -, - NQ 1 -,}} - CONQ 1 -, - NQ 1 CO -, - CH 2 At least one selected from the group consisting of O— and —OCO—, wherein X ₂ is a straight chain or branched alkylene group having 1 to 10 carbon atoms, a cyclohexane ring, a benzene ring, and a naphthalene ring. is at least one selected, _{X 3} is a single ^{^{bond, -O -, - CONQ 2 -}} , - NQ 2 CO -, - COO -, - OCO-, and _{_{-O (CH 2) m - (}} m is 1 is at least one selected from the group consisting of 5 of an integer) from, X ₄ is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, Baie 'S imidazole ring, and at least one selected from the group consisting of benzimidazole ring, n is an integer of 1 or 2.

Particularly preferred _{_{_{X 1, X 2, X 3}}} , the combination of _{X 4} and n in the formula [1], _{X 1} is ^{^{-O -, - NQ 1 -,}} - CONQ 1 -, - NQ 1 CO-, and -CH ₂ is at least one selected from the group consisting of O-, X ₂ is a single bond, at least one selected from the group consisting of linear or branched alkylene group, and benzene rings having 1 to 5 carbon atoms, X ₃ is a single ^{^{bond, -O -, - CONQ 2 -}} , - NQ 2 CO -, - COO -, - OCO-, and -O _(CH ₂₎ m - consists of (m is an integer from 1 to 5) At least one selected from the group, X ₄ is at least one selected from the group consisting of a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, and a pyrimidine ring, and n is an integer of 1 or 2.

The most preferred _X 1 in the formula _{_{[1], X 2, X}} 3, X 4 and n combinations of, _{X 1} is ^{-O -, - NQ 1 -,} - CONQ 1 -, and the group consisting of ^-NQ 1 CO- is at least one more selected, X ₂ is a single bond, a straight-chain alkylene group having 1 to 3 carbon atoms, and at least one selected from the group consisting of benzene ring, X ₃ is a single bond, -OCO- And at least one selected from the group consisting of —OCH ₂ —, X ₄ is at least one selected from the group consisting of an imidazole ring, a pyridine ring, and a pyrimidine ring, and n is an integer of 1 or 2. is there.

Particularly preferred combinations of X ₁ , X ₂ , X ₃ , X ₄ and n in the formula [1] are as shown in Tables 1 to 3 below. Q ¹ and Q ² are the same as defined in formula [1].

<Method for synthesizing specific diamine compound>
Although the method of manufacturing the specific diamine compound represented by Formula [1] of this invention is not specifically limited, The following method is mentioned as a preferable method.

The specific diamine compound of the present invention can be obtained by synthesizing a dinitro compound represented by the formula [4], further reducing the nitro group and converting it to an amino group. The method for reducing the dinitro compound is not particularly limited. Usually, palladium-carbon, platinum oxide, Raney nickel, platinum black, rhodium-alumina, platinum sulfide carbon, etc. are used as a catalyst, ethyl acetate, toluene, tetrahydrofuran, dioxane, There is a method in which hydrogen gas, hydrazine, hydrogen chloride, or the like is used in an alcohol-based solvent. X ₁ , X ₂ , X ₃ , X ₄ and n in the formula [4] are as defined in the formula [1].

In the dinitro compound of the formula [4], X ₂ and X ₄ are bonded via X ₃ and then the dinitro moiety is bonded via X ₁ , and the dinitro moiety is bonded to X ₂ via the linking moiety X _1. It can be obtained by, for example, a method of bonding to X ₄ via X ₃ .

X ₁ is —O— (ether bond), —NQ ¹ — (amino bond), —CONQ ¹ — (amide bond), —NQ ¹ CO— (reverse amide bond), —CH ₂ O— (methylene ether bond). And at least one linking group selected from the group consisting of —OCO— (reverse ester bond), and these linking groups can be formed by ordinary organic synthetic techniques. Q ^{1 of} each linking group is as defined in the formula [1].

For example, when X ₁ is an ether or methylene ether bond, a corresponding dinitro group-containing halogen derivative is reacted with a hydroxyl group derivative containing X ₂ , X ₃ and X ₄ in the presence of an alkali, or a dinitro group-containing hydroxyl group derivative , X ₂ , X ₃ and X ₄ may be reacted in the presence of an alkali.
In the case of an amino bond, a method of reacting a corresponding dinitro group-containing halogen derivative with an amino group-substituted derivative containing X ₂ , X ₃ and X ₄ in the presence of an alkali can be mentioned.

In the case of a reverse ester bond, a method of reacting a corresponding dinitro group-containing hydroxyl group derivative with an acid chloride containing X ₂ , X ₃ and X ₄ in the presence of an alkali can be mentioned.

Examples of the amide bond include a method in which a corresponding dinitro group-containing acid chloride is reacted with an amino group-substituted product containing X ₂ , X ₃ and X ₄ in the presence of an alkali.
In the case of a reverse amide bond, a method in which a corresponding dinitro group-containing amino group-substituted product and an acid chloride product containing X ₂ , X ₃ and X ₄ are reacted in the presence of an alkali can be mentioned.

Specific examples of dinitro group-containing halogen derivatives and dinitro group-containing derivatives include 3,5-dinitrochlorobenzene, 2,4-dinitrochlorobenzene, 2,4-dinitrofluorobenzene, 3,5-dinitrobenzoic acid chloride, 3,5 -Dinitrobenzoic acid, 2,4-dinitrobenzoic acid chloride, 2,4-dinitrobenzoic acid, 3,5-dinitrobenzyl chloride, 2,4-dinitrobenzyl chloride, 3,5-dinitrobenzyl alcohol, 2,4- Dinitrobenzyl alcohol, 2,4-dinitroaniline, 3,5-dinitroaniline, 2,6-dinitroaniline, 2,4-dinitrophenol, 2,5-dinitrophenol, 2,6-dinitrophenol, 2,4- And dinitrophenylacetic acid. In consideration of availability of raw materials and reaction, one or more kinds can be selected and used.

<Polymer>
The polymer of the present invention is a polyamic acid obtained by reaction of a diamine component containing a specific diamine compound and tetracarboxylic dianhydride and a polyimide obtained by dehydrating and ring-closing this polyamic acid. Any of these polyamic acids and polyimides are useful as a polymer for obtaining a liquid crystal alignment film.

The liquid crystal alignment film obtained using the polymer of the present invention has a higher voltage holding ratio as the content ratio of the specific diamine compound in the diamine component increases, and even after being exposed to a high temperature for a long time, The residual charge accumulated by the DC voltage is alleviated faster.

For the purpose of enhancing the above properties, it is preferable that 1 mol% or more of the diamine component is a specific diamine compound. Furthermore, it is preferable that 5 mol% or more of a diamine component is a specific diamine compound, More preferably, it is 10 mol% or more.

Although 100 mol% of the diamine component may be a specific diamine compound, the specific diamine compound is preferably 80 mol% or less of the diamine component, more preferably, from the viewpoint of uniform coatability when applying the liquid crystal aligning agent. It is 40 mol% or less.

In the present invention, a diamine other than the specific diamine compound (hereinafter also referred to as other diamine compound) can be used in combination, and the other diamine compound is not particularly limited. 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'-difluoro-4,4'-biphenyl, 3,3 ' Trifluoromethyl-4,4′-diaminobiphenyl, 3,4′-diaminobiphenyl, 3,3′-diaminobiphenyl, 2,2′-diaminobiphenyl, 2,3′-diaminobiphenyl, 4,4′-diamino Diphenylmethane, 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'-sulfonyldianiline, 3,3'-sulfonyldianiline, bis (4-aminophenyl) silane Bis (3-aminophenyl) Lan, 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'-diaminoben Zophenone, 1,4-diaminonaphthalene, 2,2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 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) B) 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-phenylenebis [(4-aminophenyl) methanone], 1,4-phenyle Bis [(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-amino Phenyl) terephthalate, bis (3-aminophenyl) terephthalate, bis (4-aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, N, N ′-(1,4-phenylene) bis (4-amino) Benzamide), N, N ′-(1,3-phenylene) 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-aminophenyl) hexafluoropropane, 2,2′-bis (3-amino Enyl) hexafluoropropane, 2,2′-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2′-bis (4-aminophenyl) propane, 2,2′-bis (3-amino) Phenyl) propane, 2,2′-bis (3-amino-4-methylphenyl) propane, 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-aminophenoxy) hexane, 1,6-bis (3-aminophenoxy) hexane, 1,7-bis (4-aminophenoxy) heptane, , 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, , 11- (3-aminophenoxy) undecane, 1,12- (4-aminophenoxy) dodecane, 1,12- (3-aminophenoxy) dodecane. Bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane and the like.

Examples of the diamine include a diamine having an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, and a macrocyclic substituent composed of these in the side chain of the diamine. Examples include diamine compounds represented by the formula [DA26] from DA1].

(In Formula [DA1] to Formula [DA5], R ₁ is an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.)

(In the formula [DA6] to formula [DA9], R ₂ represents —COO—, —OCO—, —CONH—, —NHCO—, —CH ₂ —, —O—, —CO—, or —NH—. R ₃ represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.)

(In Formula [DA10] and Formula [DA11], R ₄ represents —O—, —OCH ₂ —, —CH ₂ O—, —COOCH ₂ —, or —CH ₂ OCO—, and R ₅ represents the number of carbon atoms. 1 to 22 alkyl groups, alkoxy groups, fluorine-containing alkyl groups or fluorine-containing alkoxy groups.)

(In the formulas [DA12] to [DA14], R ₆ represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH ₂ O—, — OCH ₂ — or —CH ₂ —, wherein R ₇ 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 Formula [DA15] and Formula [DA16], R ₈ represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH ₂ O—, — OCH ₂ —, —CH ₂ —, —O—, or —NH—, wherein R ₉ 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 addition, diaminosiloxanes represented by the following formula [DA27] can also be exemplified.

(In the formula [DA27], m is an integer of 1 to 10.)

Other diamine compounds may be used alone or in combination of two or more depending on properties such as liquid crystal alignment properties, voltage holding properties, and accumulated charges when the liquid crystal alignment film is formed.
The tetracarboxylic dianhydride reacted with the diamine component to obtain the polyamic acid of the present invention is not particularly limited. Specific examples are given below.

Pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic Acid dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,5,6-anthracene tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic Acid dianhydride, 2,3,3 ′, 4-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride Bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3 , 3-hexafluoro-2,2-bis (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2, 3,4,5-pyridinetetracarboxylic dianhydride, 2,6-bis (3,4-dicarboxyphenyl) pyridine, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3 , 4,9,10-perylenetetracarboxylic dianhydride, 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, oxydiphthaltetracarboxylic dianhydride, 1,2 , 3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarbonate Boronic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic Acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cycloheptanetetracarboxylic dianhydride, 2,3,4, 5-tetrahydrofurantetracarboxylic dianhydride, 3,4-dicarboxy-1-cyclohexylsuccinic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,4-dicarboxy-1, 2,3,4-tetrahydro-1-naphthalene succinic dianhydride, bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride, bicyclo [4,3,0] Nonane-2, 4 , 7,9-tetracarboxylic dianhydride, bicyclo [4,4,0] decane-2,4,7,9-tetracarboxylic dianhydride, bicyclo [4,4,0] decane-2,4 , 8,10-tetracarboxylic dianhydride, tricyclo [6.3.0.0 <2,6>] undecane-3,5,9,11-tetracarboxylic dianhydride, 1,2,3 4-butanetetracarboxylic dianhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydraphthalene-1,2-dicarboxylic dianhydride, bicyclo [ 2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexane- 1,2-dicarboxylic dianhydride, tetracyclo [6,2,1,1, , 2,7] dodeca-4,5,9,10-tetracarboxylic dianhydride, 3,5,6-tricarboxynorbornane-2: 3,5: 6 dicarboxylic dianhydride, 1,2,4 , 5-cyclohexanetetracarboxylic dianhydride and the like.

Tetracarboxylic dianhydride can be used singly or in combination of two or more according to properties such as liquid crystal alignment properties, voltage holding properties, and accumulated charges when formed into a liquid crystal alignment film.
In obtaining the polyamic acid of the present invention by reaction of tetracarboxylic dianhydride and a diamine component, a known synthesis method can be used. In general, tetracarboxylic dianhydride and a diamine component are reacted in an organic solvent. The reaction of tetracarboxylic dianhydride and diamine is advantageous in that it proceeds relatively easily in an organic solvent and no by-product is generated.
The organic solvent used for the reaction between tetracarboxylic dianhydride and diamine is not particularly limited as long as the produced polyamic acid can be dissolved. Specific examples are given below.

N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, 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, 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, 3 -Methyl methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, Examples thereof include propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone and the like. These may be used alone or in combination. Further, even a solvent that does not dissolve the polyamic acid may be used by mixing with the above solvent as long as the produced polyamic acid does not precipitate.
In addition, since water in the organic solvent inhibits the polymerization reaction and further causes hydrolysis of the produced polyamic acid, it is preferable to use a dehydrated and dried organic solvent as much as possible.

When the tetracarboxylic dianhydride and the diamine component 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. In addition, when the tetracarboxylic dianhydride or diamine component 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 is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. Therefore, the total concentration of the tetracarboxylic dianhydride and the diamine component in the reaction solution 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 polyamic acid polymerization reaction, the ratio of the total number of moles of tetracarboxylic dianhydride to the total number of moles of the diamine component is preferably 0.8 to 1.2. Similar to the normal polycondensation reaction, the closer the molar ratio is to 1.0, the higher the molecular weight of the polyamic acid produced.
The polyimide of the present invention is a polyimide obtained by dehydrating and ring-closing the above polyamic acid, 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 polyamic acid include thermal imidization in which the polyamic acid solution is heated as it is, and catalytic imidization in which a catalyst is added to the polyamic acid solution.
The temperature at which the polyamic acid is thermally imidized in the solution 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 catalytic imidation of the polyamic acid can be carried out by adding a basic catalyst and an acid anhydride to the polyamic acid 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 the produced polyamic acid or polyimide is recovered from the polyamic acid 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 recovered by precipitation is redissolved in an organic solvent and the operation of reprecipitation recovery 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 polyamic acid and the 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 when forming the coating film, and the uniformity of the coating film. The weight average molecular weight measured by the Permeation Chromatography method is preferably 5,000 to 1,000,000, and more preferably 10,000 to 150,000.

<Liquid crystal alignment 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 said resin component is a resin component containing at least 1 type of polymer chosen from the polymer of this invention mentioned above. 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 above resin components may be copolymers used in the present invention, and other polymers may be mixed with the polymer of the present invention. At that time, the content of the polymer other than the polymer of the present invention in the resin component is 0.5% by mass to 15% by mass, preferably 1% by mass to 10% by mass.

Examples of such other polymers include polyamic acid or polyimide obtained by using a diamine compound other than the specific diamine compound as a diamine component to be reacted with the tetracarboxylic dianhydride component.
The organic solvent used for the liquid-crystal aligning agent of this invention will not be specifically limited if it is an organic solvent in which a resin component is dissolved. Specific examples are given below.

N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, Dimethyl sulfone, hexamethyl sulfoxide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme, 4 -Hydroxy-4-methyl-2-pentanone and the like. These may be used alone or in combination.

The liquid crystal aligning agent of this invention may contain components other than the above. Examples thereof include solvents and compounds that improve the film thickness uniformity and surface smoothness when a liquid crystal alignment treatment agent is applied, and compounds that improve the adhesion between the liquid crystal alignment film and the substrate.
Specific examples of the solvent (poor solvent) that improves the uniformity of the film thickness and the surface smoothness 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, 1-hexanol, n-hexane, n-pentane, n-octa , Diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate Ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 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 Low 1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, lactate methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n-butyl ester, lactate isoamyl ester Examples include solvents having surface tension.

These poor solvents may be used alone or in combination. When using the above solvent, it is preferable that it is 5 to 80 mass% of the whole solvent contained in a liquid-crystal aligning agent, More preferably, it is 20 to 60 mass%.
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 Co., Ltd.). The use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the resin component contained in the liquid crystal alignment treatment 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 that improves the adhesion to the substrate, the amount used is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the resin component contained in the liquid crystal alignment treatment agent. The amount is preferably 1 to 20 parts by mass. If the amount used is less than 0.1 parts 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. A substance, and further, a crosslinkable compound for the purpose of increasing the hardness and density of the liquid crystal alignment film may be added.

<Liquid crystal alignment film / 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 or a plastic substrate such as an acrylic substrate or a polycarbonate substrate 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.

Firing after applying the liquid crystal aligning agent on the substrate can be performed at 50 to 300 ° C., preferably 80 to 250 ° C. by a heating means such as a hot plate, and the solvent can be evaporated to form a coating film. . If the thickness of the coating film formed 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. It is 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.
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.

EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the interpretation of the present invention is not limited to these examples.
[Synthesis of diamine compound]
<Example 1>
Synthesis of diamine compound (4)

A solution of compound (2) (29.92 g, 277 mmol) and triethylamine (28.03 g, 277 mmol) in tetrahydrofuran (300 g) was cooled to 10 ° C. or lower, and compound (1) (60.76 g, 263 mmol) in tetrahydrofuran (150 g) was cooled. ) The solution was added dropwise taking care of the exotherm. After completion of the dropwise addition, the reaction temperature was raised to 23 ° C. and further reaction was performed. After confirming the completion of the reaction by HPLC (High Performance Liquid Chromatograph), the reaction solution is poured into distilled water (2 L), the precipitated solid is filtered, washed with water, then dispersed and washed with ethanol (450 g) to obtain Compound (3). Obtained (yield: 72.91 g, yield: 92%).
1H-NMR (400 MHz, DMSO-d6, δ ppm): 9.79 (1H, t), 9.10-9.09 (2H, m), 9.00-8.96 (1H, m), 8.61 (1H, broad), 8.50-8.48 (1H , M), 7.79-7.76 (1H, m), 7.40-7.36 (1H, m), 4.57 (2H, s).
Next, a mixture of compound (3) (72.00 g, 238 mmol), 5% palladium carbon (hydrous type, 7.2 g, 10 wt%), and 1,4-dioxane (720 g) was added in the presence of hydrogen in the presence of 60 Stir at ° C. After completion of the reaction, the catalyst was filtered through celite, and then the solvent was distilled off with an evaporator to obtain a crude product. The obtained crude product was dispersed and washed with ethanol (360 g) to obtain a diamine compound (4) (amount obtained: 43.62 g, yield: 76%).
1H-NMR (400 MHz, DMSO-d6, δ ppm): 8.64 (1H, t), 8.50 (1H, d), 8.44 (1H, d), 7.67 (1H, d), 7.34 (1H, q), 6.23 ( 2H, d), 5.94 (1H, s), 4.87 (4H, s), 4.39 (2H, d).

<Example 2>
Synthesis of diamine compound (7)

A solution of compound (5) (40.00 g, 328 mmol) and triethylamine (33.18 g, 328 mmol) in tetrahydrofuran (400 g) was cooled to 10 ° C. or lower, and compound (1) (72.00 g, 312 mmol) in tetrahydrofuran (176 g). ) The solution was added dropwise taking care of the exotherm. After completion of the dropwise addition, the reaction temperature was raised to 23 ° C. and further reaction was performed. After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (3.5 L), the precipitated solid was filtered, washed with water, and then dispersed and washed with methanol (200 g) to obtain compound (6) (obtained). (Amount: 81.4 g, yield: 82%).
1H-NMR (400 MHz, DMSO-d6, δ ppm): 8.83-8.34 (5H, m), 7.83-7.66 (1H, m), 7.39-7.33 (1H, m), 4.69-4.49 (2H, m), 2.91 -2.85 (3H, m).

Next, a mixture of compound (6) (80.00 g, 253 mmol), palladium hydroxide carbon (water-containing type, 8.0 g, 10 wt%), and 1,4-dioxane (1200 g) was added in the presence of hydrogen in the presence of 23 Stir at ° C. After completion of the reaction, the catalyst was filtered through celite, and then the solvent was distilled off with an evaporator to obtain a crude product. The obtained crude product was uniformly dissolved in tetrahydrofuran (150 g), and the solution was dropped into hexane (660 g) at −20 ° C. to precipitate a solid. Then, the diamine compound (7) was obtained by filtration and cold hexane washing (amount obtained: 74.98 g, yield: 98%).
1H-NMR (400 MHz, DMSO-d6, δ ppm): 8.46-8.34 (2H, m), 7.63-7.54 (1H, broad), 7.36-7.33 (1H, m), 5.86-5.76 (3H, m), 4.86 (4H, s), 4.57-4.53 (2H, broad), 2.80 (3H, broad).

<Example 3>
Synthesis of diamine compound (10)

A tetrahydrofuran (200 g) solution of compound (8) (16.69 g, 137 mmol) and triethylamine (13.82 g, 137 mmol) was cooled to 10 ° C. or lower, and tetrahydrofuran (150 g) of compound (1) (30.00 g, 130 mmol) was cooled. ) The solution was added dropwise taking care of the exotherm. After completion of the dropwise addition, the reaction temperature was raised to 23 ° C. and further reaction was performed. After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (2.8 L), the precipitated solid was filtered, washed with water, and then dispersed and washed with ethanol (200 g) to obtain compound (9) (obtained). (Amount: 34.53 g, yield: 84%).
1H-NMR (400 MHz, DMSO-d6, δ ppm): 9.30 (1H, t), 9.01-9.00 (2H, m), 8.95-8.93 (1H, m), 8.47 (1H, d), 8.42 (1H, dd ), 7.69 (2H, d), 7.32 (1H, q), 3.64-3.58 (2H, m), 2.92 (2H, t).

Next, a mixture of compound (9) (32.00 g, 101 mmol), 5% palladium carbon (hydrous type, 3.2 g, 10 wt%), and 1,4-dioxane (320 g) was added in the presence of hydrogen in the presence of 60 Stir at ° C. After completion of the reaction, the catalyst was filtered through celite, and then the solvent was distilled off with an evaporator to obtain a crude product. The obtained crude product was dispersed and washed with tetrahydrofuran (150 g) to obtain a diamine compound (10) (yield: 19.21 g, yield: 74%).
1H-NMR (400 MHz, DMSO-d6, δ ppm): 8.43-8.39 (2H, m), 8.09 (1H, t), 7.63 (1H, d), 7.30 (1H, dd), 6.16 (2H, d), 5.92 (1H, d), 4.84 (4H, s), 3.44-3.28 (3H, m), 2.82 (3H, t).

<Example 4>
Synthesis of diamine compound (14)

A solution of compound (11) (29.84 g, 160 mmol) in tetrahydrofuran (60 g) was added dropwise to a solution of compound (12) (35.00 g, 321 mmol) and triethylamine (97.39 g, 962 mmol) in tetrahydrofuran (240 g). After completion of the dropwise addition, the reaction was followed by HPLC. After confirming the completion of the reaction, dichloromethane (1 L) was added, followed by washing with distilled water (600 mL) three times. The organic layer was dried over anhydrous magnesium sulfate, filtered and evaporated to give a crude compound (13). The obtained crude product was recrystallized from ethyl acetate (500 g) / hexane (1 L) to obtain compound (13) (amount: 38.74 g, yield: 88%).
1H-NMR (400 MHz, CDCl3, δ ppm): 8.79 (1H, d), 8.71 (1H, d), 8.66 (1H, dd), 8.46 (1H, dd), 7.88-7.85 (1H, m), 7.40 ( 1H, q), 7.30 (1H, d), 5.38 (2H, s).

Compound (13) (20.00 g, 72.7 mmol), platinum (IV) oxide (hydrated, 2.0 g, 10 wt%), and ethyl acetate / ethanol (200 g, 100/50 (v / v%)) ) Was stirred at 40 ° C. in the presence of hydrogen. After completion of the reaction, the catalyst was filtered through celite, and then the solvent was distilled off with an evaporator to obtain a crude product of compound (14). The obtained crude product was purified by silica gel column chromatography (the effluent solvent was hexane / ethyl acetate (100/50 v / v%)) to obtain the diamine compound (14) (yield: 15.27 g, obtained). (Rate: 98%).
1H-NMR (400MHz, CDCl3, δppm): 8.66 (1H, d), 8.57 (1H, dd), 7.77-7.73 (1H, m), 7.33-7.29 (1H, m), 6.67 (1H, d), 5.00 (2H, s), 3.37 (4H, s).

<Example 5>
Synthesis of diamine compound (16)

Compound (11) (43.00 g, 231 mmol) was added to a mixed solution of compound (2) (29.98 g, 277 mmol), sodium hydrogen carbonate (29.12 g, 347 mmol), and distilled water (630 g) at 23 ° C. Ethanol (830 g) solution was added dropwise. After completion of the dropwise addition, after confirming the completion of the reaction by HPLC, dichloromethane (2 L) was added and the aqueous layer was removed. Thereafter, the organic layer was washed three times with saturated brine (500 mL), dried over anhydrous magnesium sulfate, and then the solvent was distilled off. The obtained crude product was recrystallized from ethyl acetate (500 g) / hexane (1 L) to obtain compound (15) (yield: 55.28 g, yield: 87%).
1H-NMR (400MHz, CDCl3, δppm): 9.18 (1H, d), 9.17 (1H, broad), 8.66-8.62 (2H, m), 8.29-8.25 (1H, m), 7.69-7.66 (1H, m ), 7.37-7.33 (1H, m), 6.90 (1H, d), 4.68 (2H, m).

Next, a mixture of compound (15) (3.0 g, 10.9 mmol), platinum (IV) oxide (hydrated type, 0.3 g, 10 wt%), and 1,4-dioxane (30 g) was added in the presence of hydrogen. And stirred at 23 ° C. After completion of the reaction, the catalyst was filtered through celite, and then the solvent was distilled off with an evaporator to obtain a diamine compound (16) (amount obtained: 2.30 g, yield: 98%).
1H-NMR (400MHz, CDCl3, δppm): 8.63 (1H, d), 8.52 (1H, dd),
7.71-7.66 (1H, m), 7.28-7.24 (1H, m), 6.53 (1H, d), 6.18-6.11 (2H, m), 4.22 (2H, s), 3.70 (1H, s), 3.56- 3.34 (4H, broad).

<Example 6>
Synthesis of diamine compound (19)

Compound (17) (50.00 g, 170 mmol), potassium carbonate (47.01 g, 340 mmol), copper (I) iodide (6.48 g, 34.0 mmol), N-methylglycine (6.06 g, 68.0 mmol) ) And DMSO (dimethyl sulfoxide) (1 L), Compound (2) (36.78 g, 340 mmol) was added dropwise at 40 ° C. After completion of the dropwise addition, after confirming the completion of the reaction by HPLC, ethyl acetate (4 L) / distilled water (5 L) was added, and then insoluble matters were removed by filtration. Thereafter, the aqueous layer removed by liquid separation was extracted twice with ethyl acetate (500 g), and the organic layers were combined and dried over anhydrous magnesium sulfate. After the solvent was distilled off by an evaporator to obtain a crude product, recrystallization was performed with ethyl acetate (700 mL) / hexane (2 L) to obtain a compound (18) (yield: 23.04 g, yield: 49%). ).
1H-NMR (400 MHz, CDCl3, δ ppm): 8.63 (1H, broad), 8.50-8.49 (1H, broad), 7.95 (1H, t), 7.80-7.76 (3H, m), 7.67 (1H, t), 7.39 (1H, q), 4.52 (2H, d).

Next, a mixture of compound (18) (1.0 g, 3.65 mmol), platinum (IV) oxide (water-containing type, 0.1 g, 10 wt%), and methanol (10 g) was mixed at 23 ° C. in the presence of hydrogen. And stirred. After completion of the reaction, the catalyst was filtered through celite, and then the solvent was distilled off with an evaporator to obtain a diamine compound (19) (amount obtained: 0.97 g, yield: 97%).
1H-NMR (400 MHz, DMSO-d6, δ ppm): 8.52 (1H, d), 8.41 (1H, dd), 7.69 (1H, d), 7.32 (1H, q), 5.60 (1H, t), 5.17 ( 2H, s), 4.37-4.14 (4H, m).

<Example 7>
Synthesis of diamine compound (23)

Under a nitrogen atmosphere, a solution of compound (21) (51.43 g, 281 mmol) in tetrahydrofuran (300 g) was kept at 10 ° C. or lower to obtain compound (20) (50.00 g, 281 mmol), triethylamine (170.5 g, 1.69 mol). A solution of DMAP (4-dimethylaminopyridine) (6.87 g, 56.2 mmol) in tetrahydrofuran (500 g) was added dropwise while paying attention to heat generation. After completion of the dropwise addition, the reaction temperature was raised to 23 ° C., and the mixture was stirred for 1 hour and further heated to reflux. After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (6.4 L), filtered and washed with water to obtain a crude product. The obtained crude product was recrystallized from tetrahydrofuran (243 g) / hexane (1458 g) to obtain compound (22) (amount obtained: 72.58 g, yield: 89%).
1H-NMR (400 MHz, DMSO-d6, δ ppm): 11.25 (1H, s), 9.18 (1H, d), 9.09 (2H, dd), 8.82 (1H, dd), 8.57 (1H, t), 8.38- 8.35 (1H, m), 7.64 (1H, q).

Next, a mixture of compound (22) (20.00 g, 69.4 mmol), 5% palladium carbon (hydrous type, 2.0 g, 10 wt%), and 1,4-dioxane (400 g) was added in the presence of hydrogen. , And stirred at 90 ° C. After completion of the reaction, the catalyst was filtered through celite, and then the solvent was distilled off with an evaporator to obtain a crude product. The obtained crude product was dispersed and washed with ethanol (75 g) to obtain a diamine compound (23) (amount obtained: 10.14 g, yield: 64%).
1H-NMR (400 MHz, DMSO-d6, δ ppm): 9.87 (1H, s), 9.03-9.01 (1H, m), 8.72-8.70 (1H, m), 8.23-8.19 (1H, m), 7.54-7.50 (1H, m), 6.27-6.26 (2H, m), 5.63-5.61 (1H, m), 4.75-4.73 (2H, m).

<Example 8>
Synthesis of diamine compound (26)

Under a nitrogen atmosphere, a solution of compound (21) (20.00 g, 112 mmol) in tetrahydrofuran (120 g) was cooled to 10 ° C. or lower, and compound (24) (20.57 g, 112 mmol), triethylamine (68.18 g, 674 mmol), Then, a solution of DMAP (2.74 g, 22.5 mmol) in tetrahydrofuran (200 g) was added dropwise while paying attention to heat generation. After completion of the dropwise addition, the reaction temperature was raised to 23 ° C., and the mixture was stirred for 1 hour and further heated to reflux for 17 hours. After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (2.6 L), filtered and washed with water to obtain a crude product. The obtained crude product was dispersed and washed with ethanol (40 g), and then filtered and dried to obtain compound (25) (yield: 16.45 g, yield: 51%).
1H-NMR (400 MHz, DMSO-d6, δ ppm): 11.4 (1H, s), 9.15-9.14 (1H, m), 8.86 (1H, d), 8.77 (1H, d), 8.64-8.60 (1H, m ), 8.33 (1H, d), 8.06 (1H, d), 7.66 (1H, q), 2.92 (2H, t).

Next, a mixture of compound (25) (15.00 g, 52.0 mmol), 5% palladium carbon (hydrous type, 1.5 g, 10 wt%), and 1,4-dioxane (150 g) was added in the presence of hydrogen. And stirred at 60 ° C. After completion of the reaction, the catalyst was filtered through celite, and then the solvent was distilled off with an evaporator to obtain a crude product of compound (26). The resulting crude product was purified by silica gel column chromatography (the effluent solvent was hexane / ethyl acetate (100/50 v / v%)), and further purified by recrystallization from tetrahydrofuran (400 g) / hexane (600 g). Compound (26) was obtained (yield: 6.11 g, yield: 51%).
1H-NMR (400 MHz, DMSO-d6, δ ppm): 9.54 (1H, s), 9.10 (1H, d), 8.72 (1H, dd), 8.30-8.27 (1H, m), 7.90 (1H, s), 7.52 (1H, q), 6.75 (1H, d), 6.61 (1H, d), 5.99 (1H, m), 4.65 to 4.59 (4H, m).

<Example 9>
Synthesis of diamine compound (29)

Under a nitrogen atmosphere, compound (12) (21.39 g, 196 mmol) is gradually added dropwise to a tetrahydrofuran (100 g) solution of compound (27) (10.00 g, 49.0 mmol) and triethylamine (59.50 g, 588 mmol). did. After completion of the reaction, the reaction solution was added to distilled water (1 L), filtered and washed with water to obtain a crude compound (28). The obtained crude product was recrystallized from acetonitrile (200 g) / ethyl acetate (300 g) to obtain compound (28) (amount: 11.35 g, yield: 61%).
1H-NMR (400 MHz, DMSO-d6, δ ppm): 8.74-8.73 (3H, m), 8.61 (2H, dd), 7.93 (2H, d), 7.50 (2H, q), 7.44 (1H, s), 5.56 (4H, s).
Next, a mixture of compound (28) (8.00 g, 20.1 mmol), platinum (IV) oxide (hydrated, 0.8 g, 10 wt%), and 1,4-dioxane (80 g) was added in the presence of hydrogen. And stirred at 60 ° C. After completion of the reaction, the catalyst was filtered through celite, and then the solvent was distilled off with an evaporator to obtain a crude product. The obtained crude product was recrystallized from tetrahydrofuran (200 g) / hexane (600 g) to obtain a diamine compound (29) (yield: 4.66 g, yield: 72%).
1H-NMR (400 MHz, DMSO-d6, δ ppm): 8.65 (2H, d), 8.52 (2H, dd), 7.88-7.85 (2H, m), 7.40 (2H, q), 6.68 (1H, s), 6.07 (1H, s), 4.96 (4H, s), 4.25 (4H, s).

<Example 10>
Synthesis of diamine compound (34)

A mixture of compound (31) (81.60 g, 74.1 mmol), calcium hydroxide (18.29 g, 24.7 mmol), and DMSO (375 g) was heated to 50 ° C. under a nitrogen atmosphere, and then compound (30) A solution of (50.00 g, 24.7 mmol) in DMSO (125 g) was added dropwise. After completion of the dropwise addition, the completion of the reaction was confirmed by HPLC, and then the reaction solution was poured into 5% by mass hydrochloric acid ice water (4 L), and the solid was filtered and washed with water to obtain a wet product of compound (32). Thereafter, recrystallization was performed with 2-propanol (205 g) / hexane (335 g) to obtain Compound (32) (amount: 49.0 g, yield: 72%).
1H-NMR (400 MHz, DMSO-d6, δ ppm): 9.73 (1H, s), 8.86 (1H, d), 8.42 (1H, dd), 7.11-7.05 (3H, m), 6.90-6.87 (2H, m ).

Next, a tetrahydrofuran (180 g) solution of the compound (21) (19.34 g, 109 mmol) is cooled to 10 ° C. or lower under a nitrogen atmosphere, and the compound (31) (30.0 g, 109 mmol), triethylamine (33.0 g, 324 mmol) is cooled. ), And DMAP (2.65 g, 21.7 mmol) in DMSO (300 g) were added dropwise while paying attention to heat generation. After completion of the dropwise addition, the reaction temperature was raised to 23 ° C., stirred for 1 hour, and further heated to reflux for 19 hours. After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (3.9 L), filtered, washed with water, and washed with methanol to obtain a crude product. The obtained crude product was dissolved in chloroform, and the insoluble material was filtered off. Thereafter, the filtrate was concentrated and purified by silica gel column chromatography (the effluent solvent was 1,2-dichloroethane / ethyl acetate (100/40 v / v%)) to obtain compound (33) (yield: 35). .8 g, yield: 86%).
1H-NMR (400 MHz, DMSO-d6, δ ppm): 9.29 (1H, dd), 8.92-8.91 (2H, m), 8.52-8.48 (2H, m), 7.69-7.66 (1H, m), 7.53-7.51 (2H, m), 7.44-7.40 (2H, m), 7.24 (1H, d).

Next, a toluene (170 g) solution of the compound (33) (30.00 g, 78.7 mmol) and iron powder (26.36 g, 472 mmol) was heated to 70 ° C. under a nitrogen atmosphere, and then ammonium chloride (12.63 g) was used. , 236 mmol) of 10% by mass aqueous solution was added dropwise. After completion of the reaction, the solid was filtered through celite. Thereafter, the aqueous layer was removed from the filtrate, and then the organic layer was concentrated with an evaporator to obtain a crude product. Next, the obtained crude product was dissolved in ethyl acetate (1 L) and washed three times with distilled water (500 mL). The organic layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off. The resulting crude product of compound (34) was recrystallized from methanol (100 g) / 2-propanol (100 g) to obtain diamine compound (34) (yield: 15.4 g, yield: 61%). .
1H-NMR (400 MHz, DMSO-d6, δ ppm): 9.20 (1H, dd), 8.85 (1H, dd), 8.43-8.40 (1H, m), 7.62-7.59 (1H, m), 7.19-7.16 (2H , M), 6.88-6.84 (2H, m), 6.53 (1H, d), 6.02 (1H, d), 5.81 (1H, dd), 4.69 (2H, s), 4.57 (2H, s).

<Example 11>
Synthesis of diamine compound (37)

Compound (32) (17.00 g, 61.6 mmol), Compound (35) (6.57 mL, 67.7 mmol), and triphenylphosphine (20.99 g, 80.0 mmol) in tetrahydrofuran (340 g) under nitrogen atmosphere The solution was cooled in an ice bath, and a solution of DEAD (diethyl azodicarboxylate) (40 mass% toluene solution, 34.84 mL, 80.0 mmol) was gradually added dropwise. After completion of the dropwise addition, the reaction temperature was gradually raised to 23 ° C. to carry out the reaction. After confirming the completion of the reaction by HPLC, the solvent was distilled off with an evaporator to obtain a crude product. Thereafter, recrystallization was performed twice with 2-propanol (450 g) to obtain compound (36) (amount obtained: 17.77 g, yield: 79%).
1H-NMR (400 MHz, CDCl3, δ ppm): 8.84 (1H, d), 8.71 (1H, broad), 8.63 (1H, dd), 8.30 (1H, dd), 7.80 (1H, d), 7.36 (1H, q), 7.12-7.08 (4H, m), 7.01 (1H, d), 5.04 (2H, s).

Next, under a nitrogen atmosphere, a mixture of compound (36) (15.00 g, 40.8 mmol), platinum (IV) oxide (hydrated, 1.5 g, 10 wt%), and 1,4-dioxane (230 g) The mixture was stirred at 23 ° C. in the presence of hydrogen. After completion of the reaction, the catalyst was filtered through celite, and then the solvent was distilled off with an evaporator to obtain a crude product. The obtained crude product was recrystallized from 2-propanol (60 g) to obtain a diamine compound (37) (yield: 9.66 g, yield 77%).
1H-NMR (400 MHz, CDCl3, δ ppm): 8.66 (1H, d), 8.57 (1H, dd), 7.77 (1H, m), 7.34 (1H, q), 6.87 (4H, s), 6.69 (1H, d), 6.16 (1H, d), 6.07 (1H, dd), 5.02 (2H, s), 3.65-3.48 (4H, broad).

<Synthesis Example 1>
Synthesis of diamine compound (40)

A solution of compound (38) (23.45 g, 190 mmol) and triethylamine (19.23 g, 277 mmol) in tetrahydrofuran (230 g) was cooled to 10 ° C. or lower, and compound (1) (41.68 g, 180 mmol) in tetrahydrofuran (110 g) was cooled. ) The solution was added dropwise taking care of the exotherm. After completion of the dropwise addition, the reaction temperature was raised to 23 ° C. and further reaction was performed. After confirming the completion of the reaction by HPLC (high performance liquid chromatograph), the reaction solution was poured into distilled water (1.5 L), and the precipitated solid was filtered and washed with water. Thereafter, the solid was dispersed and washed with ethanol (380 g) to obtain compound (39) (yield: 50.82 g, yield: 89%).
1H-NMR (400MHz, DMSO-d6, δppm): 9.76 (1H, t), 9.09-9.02 (2H, m), 8.99-8.93 (1H, m), 8.50 (1H, broad), 7.64-7.60 (1H , M), 7.36-7.32 (1H, m), 7.20-7.14 (1H, m), 4.57 (2H, s), 3.35 (2H, s).

Next, a mixture of compound (39) (48.00 g, 151 mmol), 5% palladium carbon (hydrous type, 4.8 g, 10 wt%) and 1,4-dioxane (490 g) was added in the presence of hydrogen in the presence of 60 Stir at ° C. After completion of the reaction, the catalyst was filtered through celite, and then the solvent was distilled off with an evaporator to obtain a crude product. The obtained crude product was dispersed and washed with ethanol (300 g) to obtain a diamine compound (40) (amount: 27.20 g, yield: 70%).
1H-NMR (400 MHz, DMSO-d6, δ ppm): 8.64 (1H, t), 8.50 (1H, d), 8.44 (1H, d), 7.67 (1H, d), 7.34 (1H, q), 6.23 ( 2H, d), 5.94 (1H, s), 4.87 (4H, s), 4.39 (2H, d).

<Synthesis Example 2>
Synthesis of diamine compound (43)

A solution of compound (41) (15.22 g, 142 mmol) and triethylamine (15.09 g, 149 mmol) in tetrahydrofuran (150 g) was cooled to 10 ° C. or lower, and compound (1) (31.1 g, 135 mmol) in tetrahydrofuran (50 g) ) The solution was added dropwise taking care of the exotherm. After completion of the dropwise addition, the reaction temperature was raised to 23 ° C. and further reaction was performed. After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (1 L), and the precipitated solid was filtered and washed with water. Thereafter, the solid was dispersed and washed with ethanol (300 g) to obtain compound (42) (yield: 36.92 g, yield: 90%).
1H-NMR (400 MHz, DMSO-d6, δ ppm): 9.75 (1H, broad), 9.10 (2H, s), 8.97-8.92 (1H, m), 7.40-7.22 (5H, m), 4.59-4.52 (2H , M).

Next, a mixture of compound (42) (36.00 g, 119 mmol), 5% palladium carbon (hydrous type, 3.6 g, 10 wt%), and 1,4-dioxane (300 g) was added in the presence of hydrogen in the presence of 60 Stir at ° C. After completion of the reaction, the catalyst was filtered through celite, and then the solvent was distilled off with an evaporator to obtain a crude product. The obtained crude product was recrystallized from methanol (200 g) to obtain a diamine compound (43) (yield: 21.5 g, yield: 72%).
1H-NMR (400 MHz, DMSO-d6, δ ppm): 8.55 (1H, broad), 7.34-7.17 (5H, m), 6.28 (2H, s), 6.98-6.94 (1H, m), 4.85-4.74 (4H , Broad), 4.42-4.35 (2H, m).

[Synthesis of polyamic acid and polyimide]
Abbreviations of compounds such as tetracarboxylic dianhydride used are shown below.
(Tetracarboxylic dianhydride)
CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride BODA: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride

(Diamine)
p-PDA: p-phenylenediamine AP18: 1,3-diamino (4-n-octadecanoyl) benzene PCH7DAB: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) Phenoxy] benzene

(Organic solvent)
NMP: N-methyl-2-pyrrolidone BCS: Butyl cellosolve <Measurement of molecular weight of polyimide>
The molecular weight of the polyimide in the synthesis example was measured as follows using a normal temperature gel permeation chromatography (GPC) apparatus (GPC-101) manufactured by Showa Denko KK and a column (KD-803, KD-805) manufactured by Shodex.

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 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation and polyethylene glycol (molecular weight manufactured by Polymer Laboratory) About 12,000, 4,000, 1,000).

<Measurement of imidization ratio>
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 manufactured by Kusano Kagaku Co., Ltd.), add 0.53 ml of deuterated dimethyl sulfoxide (DMSO-d6, 0.05% TMS mixture), and apply ultrasonic waves. And completely dissolved. 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.

<Example 12>
BODA (3.33 g, 13.3 mmol), p-PDA (0.67 g, 6.21 mmol), PCH7DAB (3.38 g, 8.87 mmol), and diamine compound (4) (0.64 g, 2.66 mmol) Were mixed in NMP (15.0 g) and reacted at 80 ° C. for 5 hours, then CBDA (0.87 g, 4.44 mmol) and NMP (13.1 g) were added, and reacted at 40 ° C. for 6 hours. A polyamic acid solution (A) having a resin component content of 24% by mass was obtained. The number average molecular weight of this polyamic acid was 17,900, and the weight average molecular weight was 51,800.

<Example 13>
After adding NMP to the polyamic acid solution (A) (20.0 g) obtained in Example 12 and diluting to 6% by mass, acetic anhydride (2.63 g) and pyridine (2.03 g) were used as imidization catalysts. In addition, the mixture was reacted at 80 ° C. for 2 hours. This reaction solution was poured into methanol (250 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 (B). The imidation ratio of this polyimide was 40%, the number average molecular weight was 16,400, and the weight average molecular weight was 44,800.

<Example 14>
BODA (2.33 g, 9.33 mmol), p-PDA (0.94 g, 8.71 mmol), AP18 (0.47 g, 1.24 mmol), and diamine compound (7) (0.64 g, 2.63 mmol) Was mixed in NMP (8.10 g) and reacted at 80 ° C. for 5 hours, then CBDA (0.61 g, 3.11 mmol) and NMP (6.51 g) were added, and reacted at 40 ° C. for 6 hours. An acid solution was obtained.
After adding NMP to the obtained polyamic acid solution (10.0 g) and diluting to 6% by mass, acetic anhydride (1.33 g) and pyridine (1.04 g) were added as an imidization catalyst, and 2 at 80 ° C. Reacted for hours. This reaction solution was poured into methanol (120 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 (C). The imidation ratio of this polyimide was 41%, the number average molecular weight was 17,500, and the weight average molecular weight was 46,400.

<Example 15>
BODA (3.25 g, 13.0 mmol), p-PDA (0.66 g, 6.07 mmol), PCH7DAB (3.30 g, 8.67 mmol), and diamine compound (10) (0.67 g, 2.60 mmol) Were mixed in NMP (14.7 g) and reacted at 80 ° C. for 5 hours, then CBDA (0.85 g, 4.33 mmol) and NMP (12.0 g) were added, and reacted at 40 ° C. for 6 hours. A polyamic acid solution having a resin component content of 25% by mass was obtained (D). The number average molecular weight of this polyamic acid was 18,800, and the weight average molecular weight was 51,800.

<Example 16>
After adding NMP to the polyamic acid solution (D) (20.0 g) obtained in Example 15 and diluting to 6% by mass, acetic anhydride (2.61 g) and pyridine (2.07 g) were used as imidization catalysts. In addition, the mixture was reacted at 80 ° C. for 2 hours. This reaction solution was poured into methanol (220 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 (E). The imidation ratio of this polyimide was 42%, the number average molecular weight was 17,400, and the weight average molecular weight was 45,800.

<Example 17>
BODA (2.22 g, 8.87 mmol), p-PDA (0.58 g, 5.32 mmol), PCH7DAB (1.35 g, 3.55 mmol), and diamine compound (14) (0.64 g, 2.96 mmol) Was mixed in NMP (8.10 g) and reacted at 80 ° C. for 5 hours, then CBDA (0.58 g, 2.96 mmol) and NMP (6.30 g) were added, and reacted at 40 ° C. for 6 hours. An acid solution was obtained.
After adding NMP to the obtained polyamic acid solution (10.1 g) and diluting to 6% by mass, acetic anhydride (1.34 g) and pyridine (1.04 g) were added as an imidization catalyst, and 2 at 80 ° C. Reacted for hours. This reaction solution was poured into methanol (140 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 (F). The imidation ratio of this polyimide was 41%, the number average molecular weight was 18,100, and the weight average molecular weight was 47,300.

<Example 18>
BODA (2.18 g, 8.72 mmol), p-PDA (0.69 g, 6.39 mmol), AP18 (0.66 g, 1.74 mmol), and diamine compound (16) (0.75 g, 3.49 mmol) Was mixed in NMP (10.0 g), reacted at 80 ° C. for 5 hours, CBDA (0.57 g, 2.91 mmol) and NMP (8.30 g) were added, and reacted at 40 ° C. for 6 hours to obtain polyamide. An acid solution was obtained.
After adding NMP to the obtained polyamic acid solution (10.1 g) and diluting to 6% by mass, acetic anhydride (1.35 g) and pyridine (1.07 g) were added as an imidization catalyst, and 2 at 80 ° C. Reacted for hours. This reaction solution was poured into methanol (140 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 (G). The imidation ratio of this polyimide was 40%, the number average molecular weight was 17,500, and the weight average molecular weight was 46,000.

<Example 19>
BODA (2.30 g, 9.18 mmol), p-PDA (0.46 g, 4.28 mmol), PCH7DAB (2.33 g, 6.12 mmol), and diamine compound (19) (0.39 g, 1.84 mmol) Was mixed in NMP (10.5 g) and reacted at 80 ° C. for 5 hours, then CBDA (0.57 g, 2.91 mmol) and NMP (8.00 g) were added, and reacted at 40 ° C. for 6 hours. An acid solution was obtained.
After adding NMP to the obtained polyamic acid solution (10.0 g) and diluting to 6% by mass, acetic anhydride (1.31 g) and pyridine (1.04 g) were added as an imidization catalyst, and 2 at 80 ° C. Reacted for hours. This reaction solution was poured into methanol (140 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 (H). The imidation ratio of this polyimide was 40%, the number average molecular weight was 18,900, and the weight average molecular weight was 49,100.

<Example 20>
BODA (2.33 g, 9.33 mmol), p-PDA (0.47 g, 4.35 mmol), PCH7DAB (2.37 g, 6.22 mmol), and diamine compound (23) (0.43 g, 1.87 mmol) Was mixed in NMP (10.50 g) and reacted at 80 ° C. for 5 hours, then CBDA (0.61 g, 3.11 mmol) and NMP (8.10 g) were added, and reacted at 40 ° C. for 6 hours. An acid solution was obtained.
After adding NMP to the obtained polyamic acid solution (10.2 g) and diluting to 6% by mass, acetic anhydride (1.37 g) and pyridine (1.04 g) were added as an imidization catalyst, and 2 at 80 ° C. Reacted for hours. This reaction solution was put into methanol (150 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (I). The imidation ratio of this polyimide was 42%, the number average molecular weight was 19,900, and the weight average molecular weight was 52,100.

<Example 21>
BODA (2.26 g, 9.03 mmol), p-PDA (0.72 g, 6.62 mmol), AP18 (0.45 g, 1.20 mmol), and diamine compound (26) (0.96 g, 4.21 mmol) Was mixed in NMP (8.10 g), reacted at 80 ° C. for 5 hours, CBDA (0.59 g, 3.01 mmol) and NMP (6.10 g) were added, and reacted at 40 ° C. for 6 hours to obtain polyamide. An acid solution was obtained.
After adding NMP to the obtained polyamic acid solution (10.0 g) and diluting to 6% by mass, acetic anhydride (1.34 g) and pyridine (1.04 g) were added as an imidization catalyst, and 2 at 80 ° C. Reacted for hours. This reaction solution was put into methanol (150 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 (J). The imidation ratio of this polyimide was 40%, the number average molecular weight was 17,900, and the weight average molecular weight was 45,800.

<Example 22>
BODA (2.22 g, 8.87 mmol), p-PDA (1.02 g, 9.46 mmol), AP18 (0.44 g, 1.18 mmol), and diamine compound (29) (0.38 g, 1.18 mmol) Were mixed in NMP (7.00 g) and reacted at 80 ° C. for 5 hours, then CBDA (0.58 g, 2.96 mmol) and NMP (6.50 g) were added, and reacted at 40 ° C. for 6 hours. A polyamic acid solution (K) having a resin component content of 26% by mass was obtained. The number average molecular weight of this polyamic acid was 17,500, and the weight average molecular weight was 45,100.

<Example 23>
BODA (3.25 g, 13.0 mmol), p-PDA (0.56 g, 5.20 mmol), PCH7DAB (3.30 g, 8.67 mmol), and diamine compound (34) (1.11 g, 3.47 mmol) Was mixed in NMP (15.0 g) and reacted at 80 ° C. for 5 hours, then CBDA (0.85 g, 4.33 mmol) and NMP (12.5 g) were added and reacted at 40 ° C. for 6 hours to obtain polyamide. An acid solution was obtained.
After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting to 6% by mass, acetic anhydride (2.65 g) and pyridine (2.07 g) were added as an imidization catalyst, and 2 at 80 ° C. 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 (L). The imidation ratio of this polyimide was 40%, the number average molecular weight was 20,100, and the weight average molecular weight was 53,400.

<Example 24>
BODA (3.25 g, 13.0 mmol), p-PDA (0.66 g, 6.07 mmol), PCH7DAB (3.30 g, 8.67 mmol), and diamine compound (37) (0.80 g, 2.60 mmol) Were mixed in NMP (14.8 g) and reacted at 80 ° C. for 5 hours, then CBDA (0.85 g, 4.33 mmol) and NMP (12.0 g) were added, and reacted at 40 ° C. for 6 hours. A polyamic acid solution (M) having a resin component content of 25% by mass was obtained. The number average molecular weight of this polyamic acid was 19,400, and the weight average molecular weight was 52,800.

<Example 25>
After adding NMP to the polyamic acid solution (M) (20.2 g) obtained in Example 24 and diluting to 6% by mass, acetic anhydride (2.68 g) and pyridine (2.07 g) were used as imidization catalysts. In addition, the mixture was reacted at 80 ° C. for 2 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 (N). The imidation ratio of this polyimide was 41%, the number average molecular weight was 18,100, and the weight average molecular weight was 48,100.

<Synthesis Example 3>
BODA (3.29 g, 13.2 mmol), p-PDA (0.67 g, 6.14 mmol), PCH7DAB (3.34 g, 8.77 mmol), and diamine compound (40) (0.68 g, 2.63 mmol) Were mixed in NMP (15.0 g) and reacted at 80 ° C. for 5 hours, then CBDA (0.86 g, 4.39 mmol) and NMP (11.5 g) were added, and reacted at 40 ° C. for 6 hours. A polyamic acid solution (O) having a resin component content of 25% by mass was obtained. The number average molecular weight of this polyamic acid was 22,600, and the weight average molecular weight was 54,900.

<Synthesis Example 4>
After adding NMP to the polyamic acid solution (O) (20.0 g) obtained in Synthesis Example 3 and diluting to 6% by mass, acetic anhydride (2.65 g) and pyridine (2.08 g) were used as imidization catalysts. In addition, the mixture was reacted at 80 ° C. for 2 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 (P). The imidation ratio of this polyimide was 40%, the number average molecular weight was 18,900, and the weight average molecular weight was 49,200.

<Synthesis Example 5>
BODA (3.22 g, 12.9 mmol), p-PDA (0.65 g, 6.00 mmol), PCH7DAB (3.26 g, 8.57 mmol), and diamine compound (43) (0.62 g, 2.57 mmol) Were mixed in NMP (15.2 g), reacted at 80 ° C. for 5 hours, CBDA (0.84 g, 4.28 mmol) and NMP (11.1 g) were added, and reacted at 40 ° C. for 6 hours. A polyamic acid solution (Q) having a resin component content of 25% by mass was obtained. The number average molecular weight of this polyamic acid was 22,100, and the weight average molecular weight was 53,200.

<Synthesis Example 6>
After adding NMP to the polyamic acid solution (Q) (20.1 g) obtained in Synthesis Example 5 and diluting to 6% by mass, acetic anhydride (2.68 g) and pyridine (2.04 g) were used as imidization catalysts. In addition, the mixture was reacted at 80 ° C. for 2 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 (R). The imidation ratio of this polyimide was 41%, the number average molecular weight was 18,400, and the weight average molecular weight was 49,100.

[Preparation and evaluation of liquid crystal aligning agent]
<Example 26>
NMP (10.2 g) and BCS (20.0 g) were added to the polyamic acid solution [A] (10.0 g) having a content of the resin component obtained in Example 12 of 24% by mass, and 2 at 25 ° C. The liquid crystal aligning agent [1] was obtained by stirring for a period of time. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.

[Production of liquid crystal cell]
The liquid crystal alignment treatment agent [1] obtained above is spin-coated on the ITO surface of the substrate with 3 cm × 4 cm (length × width) ITO electrodes, and baked in a hot air circulation oven at 80 ° C. for 5 minutes and 210 ° C. for 1 hour. A polyimide coating film having a thickness of 100 nm was prepared.
This substrate with a liquid crystal alignment film is subjected to a rubbing treatment with a roll diameter 120 mm, a rayon cloth rubbing device under the conditions of a rotation speed of 300 rpm, a roll traveling speed of 20 mm / sec, and an indentation amount of 0.3 mm. Got.
Two substrates with this liquid crystal alignment film were prepared, and a 6 μm bead spacer was sprayed on the surface of one liquid crystal alignment film, and then a sealant was printed thereon. Another substrate was bonded so that the liquid crystal alignment film surface was inward and the rubbing direction was reversed, and then the sealing agent was cured to produce an empty cell. Liquid crystal MLC-6608 (manufactured by Merck Japan Ltd.) was injected into this empty cell by a reduced pressure injection method to obtain an antiparallel aligned nematic liquid crystal cell.

[Evaluation of voltage holding ratio]
A voltage of 4 V was applied to the liquid crystal cell obtained above at a temperature of 80 ° C. for 60 μs, the voltages after 16.67 ms and 1667 ms were measured, and the voltage holding ratio was calculated as the voltage holding ratio. . The results are shown in Table 7 described later.
[Evaluation of relaxation of residual charge]
A DC voltage of 10 V was applied to the liquid crystal cell after measuring the voltage holding ratio for 30 minutes and short-circuited for 1 second, and then the potential generated in the liquid crystal cell was measured for 1800 seconds. The residual charges after 50 seconds and 1000 seconds were measured. For measurement, a 6254 type liquid crystal property evaluation apparatus manufactured by Toyo Technica Co., Ltd. was used. The results are shown in Table 8 described later.
[Evaluation after leaving at high temperature]
After the residual charge measurement, the liquid crystal cell was left in a high-temperature bath set at 100 ° C. for 7 days, and then the voltage holding ratio and the residual charge were measured. The results are shown in Table 7 and Table 8 described later.

<Example 27>
NMP (36.3 g) was added to the polyimide powder [B] (5.1 g) obtained in Example 13 and dissolved by stirring at 70 ° C. for 40 hours. NMP (18.1g) and BCS (25.6g) were added to this solution, and the liquid-crystal aligning agent [2] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal aligning agent [2], a liquid crystal cell was produced in the same manner as in Example 26, and evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 7 and Table 8 described later.

<Example 28>
NMP (32.8 g) was added to the polyimide powder [C] (5.0 g) obtained in Example 14, and dissolved by stirring at 70 ° C. for 40 hours. NMP (16.4g) and BCS (29.2g) were added to this solution, and the liquid-crystal aligning agent [3] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal aligning agent [3], a liquid crystal cell was produced in the same manner as in Example 26, and evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 7 and Table 8 described later.

<Example 29>
NMP (8.9 g) and BCS (23.6 g) were added to the polyamic acid solution [D] (10.5 g) having a resin component content of 25% by mass obtained in Example 15, and 2 at 25 ° C. The liquid crystal aligning agent [4] was obtained by stirring for a time. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal aligning agent [4], a liquid crystal cell was produced in the same manner as in Example 26, and evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 7 and Table 8 described later.

<Example 30>
NMP (34.1 g) was added to the polyimide powder [E] (5.2 g) obtained in Example 16, and dissolved by stirring at 70 ° C. for 40 hours. NMP (17.1 g) and BCS (30.4 g) were added to this solution, and the mixture was stirred at 25 ° C. for 2 hours to obtain a liquid crystal aligning agent [5]. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal aligning agent [5], a liquid crystal cell was produced in the same manner as in Example 26, and evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 7 and Table 8 described later.

<Example 31>
NMP (35.6 g) was added to the polyimide powder [F] (5.0 g) obtained in Example 17, and dissolved by stirring at 70 ° C. for 40 hours. NMP (17.8g) and BCS (25.1g) were added to this solution, and the liquid-crystal aligning agent [6] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal aligning agent [6], a liquid crystal cell was produced in the same manner as in Example 26, and evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 7 and Table 8 described later.

<Example 32>
NMP (30.1 g) was added to the polyimide powder [G] (5.0 g) obtained in Example 18, and dissolved by stirring at 70 ° C. for 40 hours. NMP (15.2g) and BCS (33.2g) were added to this solution, and the liquid-crystal aligning agent [7] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal aligning agent [7], a liquid crystal cell was produced in the same manner as in Example 26, and evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 7 and Table 8 described later.

<Example 33>
NMP (42.2 g) was added to the polyimide powder [H] (5.5 g) obtained in Example 19, and dissolved by stirring at 70 ° C. for 40 hours. NMP (20.8g) and BCS (22.9g) were added to this solution, and the liquid-crystal aligning agent [8] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal aligning agent [8], a liquid crystal cell was produced in the same manner as in Example 26, and evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 7 and Table 8 described later.

<Example 34>
NMP (30.3 g) was added to the polyimide powder [I] (5.0 g) obtained in Example 20, and dissolved by stirring at 70 ° C. for 40 hours. NMP (14.8g) and BCS (33.8g) were added to this solution, and the liquid-crystal aligning agent [9] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal aligning agent [9], a liquid crystal cell was produced in the same manner as in Example 26, and evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 7 and Table 8 described later.

<Example 35>
NMP (33.0 g) was added to the polyimide powder [J] (5.1 g) obtained in Example 21, and dissolved by stirring at 70 ° C. for 40 hours. NMP (17.1 g) and BCS (29.8 g) were added to this solution, and the mixture was stirred at 25 ° C. for 2 hours to obtain a liquid crystal aligning agent [10]. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal aligning agent [10], a liquid crystal cell was produced in the same manner as in Example 26, and evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 7 and Table 8 described later.

<Example 36>
NMP (15.6 g) and BCS (17.1 g) were added to the polyamic acid solution [K] (10.0 g) having a content of the resin component obtained in Example 22 of 26% by mass, and 2 at 25 ° C. By stirring for a period of time, a liquid crystal aligning agent [11] was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal aligning agent [11], a liquid crystal cell was produced in the same manner as in Example 26, and evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 7 and Table 8 described later.

<Example 37>
NMP (34.5 g) was added to the polyimide powder [L] (5.2 g) obtained in Example 23, and dissolved by stirring at 70 ° C. for 40 hours. NMP (16.5g) and BCS (30.3g) were added to this solution, and the liquid-crystal aligning agent [12] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal aligning agent [12], a liquid crystal cell was produced in the same manner as in Example 26, and evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 7 and Table 8 described later.

<Example 38>
NMP (9.5 g) and BCS (17.3 g) were added to the polyamic acid solution [M] (8.5 g) having a resin component content of 25% by mass obtained in Example 24, and 2 at 25 ° C. By stirring for a period of time, a liquid crystal aligning agent [13] was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal aligning agent [13], a liquid crystal cell was produced in the same manner as in Example 26, and evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 7 and Table 8 described later.

<Example 39>
NMP (35.5 g) was added to the polyimide powder [N] (5.0 g) obtained in Example 25 and dissolved by stirring at 70 ° C. for 40 hours. NMP (17.8g) and BCS (25.1g) were added to this solution, and the liquid-crystal aligning agent [14] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal aligning agent [14], a liquid crystal cell was produced in the same manner as in Example 26, and evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 7 and Table 8 described later.

<Comparative Example 1>
NMP (17.5 g) and BCS (15.3 g) are added to the polyamic acid solution [O] (10.4 g) having a resin component content of 25% by mass obtained in Synthesis Example 3, and 2 at 25 ° C. By stirring for a period of time, a liquid crystal aligning agent [15] was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal aligning agent [15], a liquid crystal cell was produced in the same manner as in Example 26, and evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 7 and Table 8 described later.

<Comparative example 2>
NMP (34.5 g) was added to the polyimide powder [P] (4.5 g) obtained in Synthesis Example 4 and dissolved by stirring at 70 ° C. for 40 hours. NMP (17.2g) and BCS (18.8g) were added to this solution, and the liquid-crystal aligning agent [16] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal aligning agent [16], a liquid crystal cell was produced in the same manner as in Example 26, and evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 7 and Table 8 described later.

<Comparative Example 3>
NMP (18.8 g) and BCS (12.2 g) are added to the polyamic acid solution [Q] (10.0 g) having a resin component content of 25% by mass obtained in Synthesis Example 5, and 2 at 25 ° C. By stirring for a period of time, a liquid crystal aligning agent [17] was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal aligning agent [17], a liquid crystal cell was prepared in the same manner as in Example 26, and evaluation of voltage holding ratio, evaluation of residual charge relaxation, and evaluation after standing at high temperature were performed. The results are shown in Table 7 and Table 8 described later.

<Comparative Example 4>
NMP (38.6 g) was added to the polyimide powder [R] (4.7 g) obtained in Synthesis Example 6, and dissolved by stirring at 70 ° C. for 40 hours. NMP (19.4g) and BCS (15.8g) were added to this solution, and the liquid-crystal aligning agent [18] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal aligning agent [18], a liquid crystal cell was produced in the same manner as in Example 26, and evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 7 and Table 8 described later.

The liquid crystal alignment treatment agent of the present invention has a high voltage holding ratio when formed into a liquid crystal alignment film, and even after being exposed to a high temperature for a long time, the liquid crystal alignment film has a quick relaxation of charges accumulated by a DC voltage. Is obtained. Furthermore, a highly reliable liquid crystal display element that can withstand long-term use in a harsh use environment can be provided. As a result, it is useful for TN elements, STN elements, TFT liquid crystal elements, and liquid crystal display elements of vertical alignment type and horizontal alignment type (IPS).

It should be noted that the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2008-014965 filed on January 25, 2008 are incorporated herein as the disclosure of the specification of the present invention. Is.

Claims

A diamine compound represented by the following formula [1].

(Wherein [1], X 1 is -O -, - NQ 1 -, - CONQ 1 -, - NQ 1 CO -, - CH 2 O-, and at least one selected from the group consisting of -OCO- A divalent organic group, Q 1 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X 2 is a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a non-aromatic cyclic carbonization hydrogen radicals, and at least one divalent organic group selected from the group consisting of an aromatic hydrocarbon group, X 3 is a single bond or -O -, - NQ 2 -, - CONQ 2 -, - NQ 2 at least one divalent organic group selected from the group consisting of 2 CO—, —COO—, —OCO—, and —O (CH 2 ) m — (m is an integer of 1 to 5); Q 2 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X 4 is a nitrogen-containing aromatic heterocyclic ring. , N is an integer from 1 to 4).
The diamine compound according to claim 1, wherein the diamine compound of the formula [1] is at least one selected from the group consisting of compounds represented by the following formulas [1a] to [1f].

(Wherein Q 1 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X 2 is a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group, and at least one divalent organic group selected from the group consisting of an aromatic hydrocarbon group, X 3 is a single bond or -O -, - NQ 2 -, - CONQ 2 -, - NQ 2 CO-, And at least one divalent organic group selected from the group consisting of —COO—, —OCO—, and —O (CH 2 ) m — (m is an integer of 1 to 5), and Q 2 is hydrogen An atom or an alkyl group having 1 to 3 carbon atoms, X 4 is a nitrogen-containing aromatic heterocyclic ring, and n is an integer of 1 to 4).
The diamine compound according to claim 2, wherein X 2 in the formulas [1a] to [1f] is a single bond, a linear alkylene group having 1 to 3 carbon atoms, or a benzene ring.
The diamine compound according to claim 2 or 3, wherein X 3 in the formulas [1a] to [1f] is a single bond, —OCO—, or —OCH 2 —.
The diamine compound according to any one of claims 2 to 4 , wherein X 4 in the formulas [1a] to [1f] is an imidazole ring, a pyridine ring, or a pyrimidine ring.
The diamine compound according to any one of claims 2 to 5, wherein n in the formulas [1a] to [1f] is an integer of 1 or 2.
X 1 in formula [1a] to formula [1f] consists of —O—, —NH—, —CONH—, —NHCO—, —CON (CH 3 ) —, —CH 2 O—, and —OCO—. X 2 is at least one selected from the group consisting of a linear or branched alkylene group having 1 to 10 carbon atoms, a cyclohexane ring, a benzene ring, and a naphthalene ring, 3 is selected from the group consisting of a single bond, —O—, —CONH—, —NHCO—, —COO—, —OCO—, and —O (CH 2 ) m — (m is an integer of 1 to 5). is at least one, X 4 is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, and a benzimidazole ring At least one selected from Ranaru group, the diamine compound according to claim 1 or 2 n is an integer of 1 or 2.
X 1 in the formula [1] is at least one selected from the group consisting of —O—, —NH—, —CONH—, —NHCO—, —CON (CH 3 ) —, and —CH 2 O—. , X 2 is at least one selected from the group consisting of a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms, and a benzene ring, and X 3 is a single bond, —O—, —CONH—, — At least one selected from the group consisting of NHCO-, -COO-, -OCO-, and -O (CH 2 ) m- (m is an integer of 1 to 5), and X 4 is a pyrrole ring, imidazole The diamine compound according to claim 1 or 2, wherein at least one selected from the group consisting of a ring, a pyrazole ring, a pyridine ring, and a pyrimidine ring, and n is an integer of 1 or 2.
X 1 in the formula [1] is at least one selected from the group consisting of —O—, —NH—, —CONH—, —NHCO—, and —CON (CH 3 ) —, and X 2 is a single bond , straight-chain alkylene group having 1 to 3 carbon atoms, and at least one selected from the group consisting of benzene ring, X 3 is a single bond, -OCO-, and -OCH 2 - at least one selected from the group consisting of a species, X 4 is an imidazole ring, at least one selected from the group consisting of pyridine ring, and a pyrimidine ring, a diamine compound according to claim 1 or 2 n is an integer of 1 or 2.
A polyamic acid obtained by reacting the diamine component containing the diamine compound according to any one of claims 1 to 9 with tetracarboxylic dianhydride, or a polyimide obtained by dehydrating and ring-closing the polyamic acid.
The polyamic acid or polyimide according to claim 10, wherein the diamine compound represented by the formula [1] is 1 to 80 mol% in the diamine component.
A liquid crystal aligning agent containing at least one of the polyamic acid and the polyimide according to claim 10 and a solvent, and a solvent.
The liquid crystal aligning agent according to claim 12, wherein 5 to 80% by mass of the solvent contained in the liquid crystal aligning agent is a poor solvent.
A liquid crystal alignment film obtained by using the liquid crystal aligning agent according to claim 12 or 13.
A liquid crystal display element having the liquid crystal alignment film according to claim 14.