WO2012014898A1

WO2012014898A1 - Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element

Info

Publication number: WO2012014898A1
Application number: PCT/JP2011/066980
Authority: WO
Inventors: 保坂　和義; 耕平後藤; 徳俊三木; 雅章片山; 幸司園山
Original assignee: 日産化学工業株式会社
Priority date: 2010-07-26
Filing date: 2011-07-26
Publication date: 2012-02-02
Also published as: CN103119509A; TW201219451A; KR101826380B1; JPWO2012014898A1; TWI522391B; JP5904121B2; KR20130094804A; CN103119509B

Abstract

Disclosed is a liquid crystal aligning agent which contains at least one kind of polymer that is selected from the group consisting of polyimides and polyimide precursors that are obtained by causing a diamine component that contains a diamine compound represented by formula (1) and a diamine compound represented by formula (2) to react with a tetracarboxylic acid dianhydride component. (In formula (1), X¹ represents -O-, -CO-, -NH-, -CONH-, -NHCO-, -CH₂O-, -OCO- or the like; X² represents an alkyl group having 1-5 carbon atoms or a non-aromatic heterocyclic ring containing a nitrogen atom; X³ represents a five-membered or six-membered aromatic heterocyclic ring containing two nitrogen atoms which may be substituted by an alkyl group having 1-5 carbon atoms; and n represents an integer of 1-4. In formula (2), Y¹ represents a single bond, -(CH₂)_a- (wherein a represents an integer of 1-15), -O-, -CH₂O-, -COO- or OCO-; Y² represents a single bond or (CH₂)_b- (wherein b represents an integer of 1-15); Y³ represents a single bond, -(CH₂)_c- (wherein c represents an integer of 1-15), -O-, -CH₂O-, -COO- or OCO-; Y⁴ represents a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and heterocyclic rings or a divalent organic group selected from among organic groups having a steroid skeleton and 12-25 carbon atoms; Y⁵ represents a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and heterocyclic rings; n represents an integer of 0-4; Y⁶ represents an alkyl group having 1-18 carbon atoms, or the like; and m represents an integer of 1-4.)

Description

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

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

Currently, as a liquid crystal alignment film of a liquid crystal display element, a so-called polyimide liquid crystal alignment film obtained by applying and baking a liquid crystal alignment treatment agent mainly composed of a polyimide precursor such as polyamic acid or a soluble polyimide solution is mainly used. ing.
The liquid crystal alignment film is used for the purpose of controlling the alignment state of the liquid crystal. However, as liquid crystal display elements have become higher in definition, the liquid crystal alignment film used has a higher voltage holding ratio and a DC voltage is applied from the viewpoint of suppressing the reduction in contrast of the liquid crystal display elements and reducing the afterimage phenomenon. The characteristic that the accumulated charge at the time is small or the relaxation of the charge accumulated by the DC voltage is fast becomes important.

In a polyimide-based liquid crystal alignment film, a liquid crystal alignment treatment agent containing a tertiary amine having a specific structure in addition to polyamic acid or an imide group-containing polyamic acid is assumed to have a short time until an afterimage generated by a DC voltage disappears. Known ones (for example, see Patent Document 1) and those using a liquid crystal alignment treatment agent containing a soluble polyimide using a specific diamine having a pyridine skeleton as a raw material are known. ing. In addition to polyamic acid and its imidized polymer, etc., one carboxylic acid group is contained 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, a compound containing one carboxylic anhydride group in the molecule, and a compound containing one tertiary amino group in the molecule (For example, refer to Patent Document 3).

Japanese Unexamined Patent Publication No. 9-316200 Japanese Unexamined Patent Publication No. 10-104633 Japanese Unexamined Patent Publication No. 8-76128

In recent years, large-screen, high-definition liquid crystal televisions have been widely put into practical use, and in liquid crystal display elements for such applications, there is a demand for afterimages compared to conventional displays that mainly display characters and still images. Therefore, characteristics that can withstand long-term use in harsh usage environments are required. Therefore, a liquid crystal alignment film to be used is required to have a higher reliability than before. Therefore, not only the initial characteristics of the electrical characteristics of the liquid crystal alignment film, that is, the relaxation characteristics of the charges accumulated by the voltage holding ratio and the direct current voltage are good, for example, after being exposed to backlight light for a long time. Even so, it is required to maintain good characteristics. When the relaxation characteristic of the accumulated charge due to the voltage holding ratio and the direct current voltage is greatly reduced, line burn-in and surface burn-in, which are display defects of the liquid crystal display element, are likely to occur, and a highly reliable liquid crystal display element can be obtained. Can not.

The present invention has been made in view of the above circumstances, and in addition to the initial characteristics, even when exposed to light irradiation for a long time, it suppresses a decrease in voltage holding ratio and further accumulates charges accumulated by a DC voltage. It is an object of the present invention to provide a liquid crystal alignment treatment agent capable of forming a liquid crystal alignment film that can be quickly relaxed, and to provide a highly reliable liquid crystal display element that can withstand long-term use in harsh usage environments.

As a result of diligent research, the present inventors have found that a polyimide precursor having a specific structure and a liquid crystal alignment treatment agent containing a polyimide obtained by dehydrating and ring-closing the polyimide precursor are extremely suitable for achieving the above object. As a result, the present invention has been found to be effective.
That is, the present invention has the following gist.
(1) a diamine component including a diamine compound represented by the following formula [1] (also referred to as a specific diamine compound) and a diamine compound represented by the following formula [2] (also referred to as a specific side chain diamine compound); A liquid crystal aligning agent containing at least one polymer selected from the group consisting of a polyimide precursor obtained by reacting a tetracarboxylic dianhydride component and a polyimide.

(X ¹ is —O—, —CO—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —OCO—, —CON (CH ₃ ) — Or N (CH ₃ ) CO—, X ² is an alkyl group having 1 to 5 carbon atoms or a non-aromatic heterocyclic ring containing a nitrogen atom, and X ³ is an alkyl group having 1 to 5 carbon atoms (It is a 5-membered or 6-membered aromatic heterocycle containing two optionally substituted nitrogen atoms.)

(Y ¹ is a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or OCO—, and Y ² is A single bond or (CH ₂ ) _b — (b is an integer of 1 to 15), Y ³ is a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), — O—, —CH ₂ O—, —COO— or OCO— Y ⁴ represents a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring (any hydrogen on these cyclic groups). The atom is substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. Or a divalent organic group selected from organic groups having 12 to 25 carbon atoms having a steroid skeleton. A group, Y ⁵ is a benzene ring, any hydrogen atom on the divalent cyclic group (these cyclic group selected from the group consisting of hexane ring and the heterocyclic cycloheteroalkyl represents an alkyl group having 1 to 3 carbon atoms N may be substituted with an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom). And Y ⁶ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. And m is an integer of 1 to 4.)

(2) In the formula [1], X ¹ is —O—, —CO—, —NH—, —CONH—, —NHCO—, —CON (CH ₃ ) — or CH ₂ O— ) Liquid crystal aligning agent.
(3) formula [1], ^{X 2} is a liquid crystal alignment treating agent according to (1) or (2) a piperazine ring.
(4) The liquid crystal aligning agent according to any one of (1) to (3), wherein in formula [1], X ³ is an imidazole ring, a pyrazine ring or a pyrimidine ring.
(5) The liquid crystal aligning agent according to any one of (1) to (4), wherein the polymer is a polymer using a tetracarboxylic dianhydride represented by the following formula [3].

(Z ¹ is a tetravalent organic group having 4 to 13 carbon atoms and contains a non-aromatic cyclic hydrocarbon group having 4 to 10 carbon atoms).
(6) The liquid crystal aligning agent according to (5), wherein Z ¹ is a group having a structure represented by the following formulas [3a] to [3j].

(Z ² to Z ⁵ are a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different. Z ⁶ and Z ⁷ are a hydrogen atom or a methyl group, Can be the same or different.)

(7) The polymer is a polyamic acid obtained by reacting a diamine component and a tetracarboxylic dianhydride component and at least one heavy selected from the group consisting of polyimides obtained by dehydrating and ring-closing the polyamic acid. The liquid crystal aligning agent according to any one of the above (1) to (6), which is a coalescence.
(8) The liquid crystal aligning agent according to any one of (1) to (6), wherein the polymer is a polyimide obtained by dehydrating and ring-closing polyamic acid.
(9) A crosslinkable compound having at least one substituent selected from the group consisting of an epoxy group, an oxetane group, a cyclocarbonate group or an isocyanate group, a hydroxyl group and an alkoxyl group in the liquid crystal aligning agent. Or the liquid crystal aligning agent according to any one of the above (1) to (8), which has a crosslinkable compound having a polymerizable unsaturated bond.
(10) The liquid crystal aligning agent according to any one of the above (1) to (9), wherein the liquid crystal aligning agent contains an organic solvent and contains 5 to 80% by mass of a poor solvent as a whole.
(11) A liquid crystal alignment film obtained by using the liquid crystal aligning agent according to any one of (1) to (10).
(12) A liquid crystal display device having the liquid crystal alignment film according to (11).
(13) A liquid crystal composition having a liquid crystal layer between a pair of substrates provided with electrodes and including a polymerizable compound that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates. The liquid crystal alignment film according to (11), which is used for a liquid crystal display device manufactured through a step of polymerizing the polymerizable compound while applying a voltage between the electrodes.

(14) A liquid crystal display device comprising the liquid crystal alignment film according to (13).
(15) A liquid crystal layer is provided between a pair of substrates provided with the liquid crystal alignment film and the electrode according to (11) or (13), and active energy rays and heat are interposed between the pair of substrates. The liquid crystal display device according to the above (14), which is produced through a step of disposing a liquid crystal composition containing a polymerizable compound polymerized by at least one and polymerizing the polymerizable compound while applying a voltage between the electrodes.
(16) A liquid crystal alignment film having a liquid crystal layer between a pair of substrates provided with electrodes and including a polymerizable group that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates. The liquid crystal alignment film according to (11), which is used for a liquid crystal display device manufactured through a step of polymerizing the polymerizable group while applying a voltage between the electrodes.
(17) A liquid crystal display device comprising the liquid crystal alignment film according to (16).
(18) The liquid crystal layer is provided between a pair of substrates provided with electrodes, and the polymerizable substrate is polymerized by at least one of active energy rays and heat between the pair of substrates. The liquid crystal display element according to (17), wherein the liquid crystal display element is manufactured through a step of arranging the liquid crystal alignment film according to 13) and polymerizing the polymerizable group while applying a voltage between the electrodes.

By using the liquid crystal aligning agent of the present invention, in addition to the initial characteristics, even when exposed to light irradiation for a long time, the decrease in the voltage holding ratio is suppressed, and further, the charge accumulated by the DC voltage is quickly relaxed. A liquid crystal alignment film can be obtained. Furthermore, a highly reliable liquid crystal display element that can withstand long-term use in a severe use environment can be provided.

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

In the formula [1], X ¹ represents —O—, —CO—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —OCO—, —CON. (CH ₃ ) — or N (CH ₃ ) CO—. Among these, —O—, —COO—, —NH—, —CONH—, —NHCO—, —CON (CH ₃ ) —, —CH ₂ O— or OCO— is preferable because a diamine compound can be easily synthesized. Particularly preferred is —O—, —CO—, —NH—, —CONH—, —NHCO—, —CON (CH ₃ ) — or CH ₂ O—.

In the formula [1], X ² is a non-aromatic heterocyclic ring containing an alkyl group having 1 to 5 carbon atoms or a nitrogen atom. When X ² is an alkyl group having 1 to 5 carbon atoms, the alkyl group may be linear or branched. In particular, the alkyl group preferably has 1 to 3 carbon atoms. Examples of the case where X ² is a non-aromatic heterocyclic ring containing a nitrogen atom include a pyrrolidine ring, piperidine ring, pyrazolidine ring, quinuclidine ring or imidazolidine ring. In particular, a non-aromatic heterocyclic ring having a 5-membered ring or a 6-membered ring is preferable because good alignment can be obtained when a liquid crystal alignment film is used. In addition, when the non-aromatic heterocycle contains two nitrogen atoms, when a liquid crystal display device is used, ionic impurities in the liquid crystal are adsorbed at the liquid crystal alignment film interface, and the liquid crystal display device has good electrical characteristics. It is desirable to keep.
From the above viewpoint, a piperazine ring is particularly preferable as the non-aromatic heterocyclic ring containing a nitrogen atom. In addition, when X ² is bonded to the nitrogen atom in X ³ or the carbon atom adjacent to the nitrogen atom, the residual charge accumulated by the DC voltage is quickly relaxed when the liquid crystal display element is formed. It is preferable because of its excellent effect.

In the formula [1], X ³ is a 5-membered or 6-membered aromatic heterocyclic ring containing two nitrogen atoms which may be substituted with an alkyl group having 1 to 5 carbon atoms. Examples of the 5-membered or 6-membered aromatic heterocycle containing two nitrogen atoms include an imidazole ring, a pyrazole ring, a pyrazine ring, a pyrimidine ring, and a pyridazine ring. Of these, an imidazole ring, a pyrazine ring or a pyrimidine ring is preferable. Furthermore, when the aromatic heterocycle in X ³ is substituted with an alkyl group, the alkyl group preferably has 1 to 3 carbon atoms.
In the formula [1], n is an integer of 1 to 4. Among these, an integer of 1 or 2 is preferable.
Preferred combinations of X ¹ , X ² , X ³ and n in the formula [1] are as shown in Tables 1 to 14.

Among the combinations of X ¹ , X ² , X ³ and n described in Tables 1 to 14, more preferable combinations are 1-1 to 1-6, 1-19 to 1-24, 1-43 to 1- 48, 1-61 to 1-66, 1-85 to 1-90, 1-103 to 1-108, 1-127 to 1-132, 1-145 to 1-150, 1-169 to 1-174, 1-187 to 1-192, 1-211 to 1-216, 1-229 to 1-234, 1-253 to 1-258, or 1-276. Particularly preferred combinations are 1-1, 1-3, 1-5, 1-19, 1-21, 1-23, 1-43, 1-45, 1-47, 1-61, 1-63, 1 -65, 1-85, 1-87, 1-89, 1-103, 1-105, 1-107, 1-127, 1-129, 1-131, 1-145, 1-147, 1-149 1-169, 1-171, 1-173, 1-187, 1-189, 1-191, 1-211, 1-213, 1-215, 1-229, 1-231, 1-233, 1 -253, 1-255, 1-257, 1-271, 273 or 1-275.

The method for producing the specific diamine compound of the present invention is not particularly limited, but preferred methods include the following methods.
The specific diamine compound of the present invention can be obtained by synthesizing a dinitro compound represented by the following formula [1a], and further reducing the nitro group of the dinitro compound and converting it to an amino group. The method for reducing the dinitro compound is not particularly limited, and usually palladium-carbon, platinum oxide, Raney nickel, platinum black, rhodium-alumina, platinum sulfide carbon, etc. are used as a catalyst, and 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 and n are as defined in the formula [1].)
The dinitro compound represented by the formula [1a] can be obtained by a method in which —X ² —X ³ is bonded to dinitrobenzene via X ¹ .
For example, when X ¹ is an —O— or CH ₂ O— bond, a corresponding dinitro group-containing halogen derivative is reacted with a hydroxyl group derivative containing X ² and X ³ in the presence of an alkali, or a dinitro group-containing hydroxyl group Examples thereof include a method in which a derivative is reacted with a halogen-substituted derivative containing X ² and X ³ in the presence of an alkali.

When X ¹ is —NH— or N (CH ₃ ) —, there is a method in which a corresponding dinitro group-containing halogen derivative is reacted with an amino group-substituted derivative containing X ² and X ³ in the presence of an alkali. .
When X ¹ is an —OCO— bond, a method of reacting a corresponding dinitro group-containing hydroxyl group derivative with an acid chloride containing X ² and X ³ in the presence of an alkali can be mentioned.
In the case where X ¹ is —CONH— or CON (CH ₃ ) —, there is a method in which the corresponding dinitro group-containing acid chloride is reacted with an amino group-substituted product containing X ² and X ³ in the presence of an alkali. It is done.
When X ¹ is —NHCO— or N (CH ₃ ) CO— bond, there is a method of reacting a corresponding amino group-substituted dinitro group and an acid chloride containing X ² and X ³ in the presence of an alkali. Can be mentioned.

Specific examples of the halogen derivative containing dinitro group and the hydroxyl group derivative containing dinitro group 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, , 4-dinitrophenylacetic acid. In consideration of availability of raw materials and reaction, one or more kinds can be selected and used.

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

Wherein [2], ^{Y 1} is a single _{_{bond, - (CH 2) a -}} (a is an integer of 1 ~ 15), - O - , - CH 2 O -, - COO- or OCO- . Among these, a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O— or COO— is preferable because a side chain structure is easily synthesized. More preferably, they are a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 10), —O—, —CH ₂ O— or COO—.
In the formula [2], Y ² is a single bond or (CH ₂ ) _b — (b is an integer of 1 to 15). Among these, a single bond or (CH ₂ ) _b — (b is an integer of 1 to 10) is preferable.

In the formula [2], Y ³ is a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or OCO—. . Among these, a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or OCO— is preferable because they are easily synthesized. More preferably, they are a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 10), —O—, —CH ₂ O—, —COO— or OCO—.
In Formula [2], Y ⁴ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring, and any hydrogen atom on these cyclic groups has 1 carbon atom. It may be substituted with an alkyl group having 3 to 3, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. Y ⁴ is a divalent organic group having 12 to 25 carbon atoms having a steroid skeleton. Y ⁴ is preferably a C 12-25 organic group having a benzene ring, a cyclohexyl ring or a steroid skeleton.
In the formula [2], Y ⁵ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexyl ring and a heterocyclic ring, and any hydrogen atom on these cyclic groups has 1 carbon atom. It may be substituted with an alkyl group having 3 to 3, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom.

In the formula [2], n is an integer of 0 to 4. Preferably, it is an integer of 0-2.
In the formula [2], Y ⁶ represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. is there. Of these, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 10 carbon atoms is preferable. More preferably, it is an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. More preferred is an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.
In the formula [2], m is an integer of 1 to 4. Preferably, it is an integer of 1.
Preferred combinations of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , n and m in the formula [2] are as shown in Tables 15 to 44.

Among the combinations of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , n and m described in Tables 15 to 44, more preferable combinations are 2-25 to 2-96, 2 to 145 to 2-168, 2-217 to 2-240, 2-268 to 2-315, 2-364 to 2-387, 2-436 to 2-483, 2-604 to 2-628, etc., and particularly preferred combinations Are 2-49 to 2-96, 2-145 to 2-168, 2-217 to 2-240, 2-604 to 2-612, and the like.
More specifically, it is a diamine compound having a structure represented by the following formulas [2-1] to [2-31].

(R ¹ represents —O—, —OCH ₂ —, —CH ₂ O—, —COOCH ₂ — or CH ₂ OCO—, and R ² represents an alkyl group having 1 to 22 carbon atoms, an alkoxyl group, fluorine-containing An alkyl group or a fluorine-containing alkoxyl group.)

(R ³ represents —COO—, —OCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH ₂ O—, —OCH ₂ — or CH ₂ —, and R ⁴ represents 1 to 22 carbon atoms. An alkyl group, an alkoxyl group, a fluorine-containing alkyl group or a fluorine-containing alkoxyl group.)

(R ⁵ represents —COO—, —OCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH ₂ O—, —OCH ₂ —, —CH ₂ — or O—, and R ⁶ represents fluorine Group, cyano group, trifluoromethane group, nitro group, azo group, formyl group, acetyl group, acetoxy group or hydroxyl group.)

(R ⁷ is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.)

(R ⁸ is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.)

(A ⁴ is an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, A ³ is a 1,4-cyclohexylene group or a 1,4-phenylene group, and A ² is , An oxygen atom or COO- * (where a bond with “*” is bonded to A ³ ), and A ¹ is an oxygen atom or COO— * (where a bond with “*” is (CH ₂ ) a ₂ )). A ₁ is an integer of 0 or 1, a ₂ is an integer of 2 to 10, and a ₃ is an integer of 0 or 1. )

Of the above formulas [2-1] to [2-31], diamine compounds having particularly preferred structures are represented by the formulas [2-1] to [2-6], the formulas [2-9] to the formulas [2-31]. 13], Formula [2-16], Formula [2-19], Formula [2-23], Formula [2-25], Formula [2-29], and the like.

<Other diamine compounds>
In this invention, unless the effect of this invention is impaired, other diamine compounds other than a specific diamine compound and a specific side chain type diamine compound can be used together as a diamine component. Specific examples are given below.
p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2, 5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4 , 6-diaminoresorcinol, 4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 3,3′-dihydroxy -4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-diph Fluoro-4,4′-biphenyl, 3,3′-trifluoromethyl-4,4′-diaminobiphenyl, 3,4′-diaminobiphenyl, 3,3′-diaminobiphenyl, 2,2′-diaminobiphenyl, 2,3′-diaminobiphenyl, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 2,2′-diaminodiphenylmethane, 2,3′-diaminodiphenylmethane, 4, 4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldianiline, 3,3 '-Sulphonyldianiline, bis (4-aminophenyl) silane, bis (3-amino Nophenyl) silane, dimethyl-bis (4-aminophenyl) silane, dimethyl-bis (3-aminophenyl) silane, 4,4′-thiodianiline, 3,3′-thiodianiline, 4,4′-diaminodiphenylamine, 3, 3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl (4,4'-diaminodiphenyl) amine, N-methyl (3 3'-diaminodiphenyl) amine, N-methyl (3,4'-diaminodiphenyl) amine, N-methyl (2,2'-diaminodiphenyl) amine, N-methyl (2,3'-diaminodiphenyl) amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone 1,4-diaminonaphthalene, 2,2′-diaminobenzophenone, 2,3′-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-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) ben 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (4-amino) Benzyl) 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-phenylene Bis (methylene)] dianiline, 3,3 ′-[1,3-phenylenebis (methylene)] dianiline, 1,4-phenylenebis [(4-aminophenyl) methanone], 1,4-phenylenebis [(3 -Ami Phenyl) methanone], 1,3-phenylenebis [(4-aminophenyl) methanone], 1,3-phenylenebis [(3-aminophenyl) methanone], 1,4-phenylenebis (4-aminobenzoate), 1,4-phenylenebis (3-aminobenzoate), 1,3-phenylenebis (4-aminobenzoate), 1,3-phenylenebis (3-aminobenzoate), bis (4-aminophenyl) terephthalate, bis ( 3-aminophenyl) terephthalate, bis (4-aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, N, N ′-(1,4-phenylene) bis (4-aminobenzamide), N, N '-(1,3-phenylene) bis (4-aminobenzamide), N, N'-(1,4-phenylene) bi (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-aminophenyl) hexafluoropropane, 2,2′-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2′-bis (4-aminophenyl) propane, 2,2′-bis (3-aminophenyl) propane, 2,2 '-Bis (3-amino-4-methylphenyl) propane, 1,3-bis (4-aminophenoxy) propane, 1,3-bis (3-aminophenoxy) propane, 1,4-bis (4-amino) Phenoxy) 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, 1,7- (3-aminophenoxy) heptane 1,8-bis (4-aminophenoxy) octane, 1,8-bis (3-aminophenoxy) octane, 1,9-bis (4-aminophenoxy) nonane, 1,9-bis (3-aminophenoxy) Nonane, 1,10- (4-aminophenoxy) decane, 1,10- (3-aminophenoxy) decane, 1,11- (4-aminophenoxy) undecane, 1,11- (3-aminophenoxy) undecane, 1,12- (4-aminophenoxy) dodecane, 1,12- (3-aminophenoxy) dodecane, 4- (aminomethyl) aniline, 3- (aminomethyl) aniline, 4- (2-aminoethyl) aniline, Aromatic diamine compounds such as 3- (2-aminoethylaniline); bis (4-aminocyclohexyl) methane, bis (4-amino-3-methyl) Cyclohexyl) methane and other alicyclic diamine compounds; 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8 -Aliphatic diamine compounds such as diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane.

Moreover, unless the effect of this invention is impaired, the diamine compound which has an alkyl group or a fluorine-containing alkyl group in a diamine side chain can be used.
Specifically, diamine compounds represented by the following formulas [DA1] to [DA12] can be exemplified.

(A ⁵ is an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.)

(A ⁶ represents —COO—, —OCO—, —CONH—, —NHCO—, —CH ₂ —, —O—, —CO— or NH—, and A ⁷ represents an alkyl having 1 to 22 carbon atoms. Group or fluorine-containing alkyl group.)

(P is an integer of 1 to 10)
In addition, diamine compounds represented by the following formulas [DA13] to [DA20] can be used as long as the effects of the present invention are not impaired.

(M is an integer from 0 to 3, and n is an integer from 1 to 5.)

Furthermore, a diamine compound having a carboxyl group in the molecule represented by the following formulas [DA21] to [DA25] can be used as long as the effects of the present invention are not impaired.

(M ₁ is an integer of 1 to 4, and A ⁸ is a single bond, —CH ₂ —, —C ₂ H ₄ —, —C (CH ₃ ) ₂ —, —CF ₂ —, —C (CF ₃ ) —, —O—, —CO—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO— , -CON (CH ₃ )-or N (CH ₃ ) CO-, m ₂ and m ₃ are each an integer of 0 to 4, and m ₂ + m ₃ is an integer of 1 to 4. m ₄ and m ₅ are each an integer of 1 to 5, A ⁹ is a linear or branched alkyl group having 1 to 5 carbon atoms, and m ₆ is an integer of 1 to 5. A ¹⁰ is Single bond, —CH ₂ —, —C ₂ H ₄ —, —C (CH ₃ ) ₂ —, —CF ₂ —, —C (CF ₃ ) —, —O—, —CO—, —NH—, — N (C _{_{3) -, - CONH -,}} - NHCO -, - CH 2 O -, - OCH 2 -, - COO -, - OCO -, - CON (CH 3) - or _{N (CH} 3) a CO-, m ₇ is an integer of 1 to 4.)
The said other diamine compound can also be used 1 type or in mixture of 2 or more types according to characteristics, such as a liquid crystal aligning property at the time of setting it as a liquid crystal aligning film, a voltage holding rate, and an accumulation charge.

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

In the formula [3], Z ¹ is a tetravalent organic group having 4 to 13 carbon atoms and contains a non-aromatic cyclic hydrocarbon group having 4 to 10 carbon atoms.
Specifically, it is a group having a structure represented by the following formulas [3a] to [3j].

In the formula [3a], Z ² to Z ⁵ are groups selected from a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and each may be the same or different. ⁶ and Z ⁷ are a hydrogen atom or a methyl group, and may be the same or different.
In the formula [3], a particularly preferred group of Z ¹ is represented by the formula [3a], the formula [3c], the formula [3d], the formula [3e], the formula [3f] because of polymerization reactivity and ease of synthesis. Or it is Formula [3g].

<Other tetracarboxylic dianhydrides>
In the present invention, other tetracarboxylic dianhydrides other than the specific tetracarboxylic dianhydride (also referred to as other tetracarboxylic dianhydrides) can be used as long as the effects of the present invention are not impaired. Examples of other tetracarboxylic dianhydrides include tetracarboxylic dianhydrides of the following tetracarboxylic acids.
Pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7 -Anthracene tetracarboxylic acid, 1,2,5,6-anthracene tetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4-biphenyltetracarboxylic acid, bis ( 3,4-dicarboxyphenyl) ether, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) methane, 2 , 2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3,4-dicarboxyphenyl) propane, bi (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis (3,4-dicarboxy) Phenyl) pyridine, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid or 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic Examples include acids.
The other tetracarboxylic dianhydrides may be used alone or in combination of two or more depending on the liquid crystal alignment properties, voltage holding ratio, accumulated charge and the like when the liquid crystal alignment film is formed.

<Specific polymer>
The specific polymer of the present invention is at least one polymer selected from the group consisting of a polyimide precursor and polyimide, and the polyimide precursor has a structure represented by the following formula [A].

(R ⁹ is a tetravalent organic group, R ¹⁰ is a divalent organic group, and A ¹¹ and A ¹² are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and each is the same. Or n may be different, and n represents a positive integer.)
The specific polymer of the present invention is relatively easily obtained by using a diamine component represented by the following formula [B] and a tetracarboxylic dianhydride component represented by the following formula [C] as raw materials. For the reason, a polyamic acid having a structural formula of a repeating unit represented by the following formula [D] or a polyimide obtained by imidizing the polyamic acid is preferable.

(R ⁹ and R ¹⁰ are synonymous with those defined in Formula [A].)

(R ⁹ , R ¹⁰ and n have the same meaning as defined in formula [A].)
In the formula [A] and the formula [D], R ⁹ and R ¹⁰ may be one type each, or may be a combination of different types using different R ⁹ and R ¹⁰ as repeating units.

In the present invention, the method for synthesizing the specific polymer is not particularly limited. Usually, it is obtained by reacting a diamine component with a tetracarboxylic dianhydride component. Generally, at least one tetracarboxylic acid component selected from the group consisting of tetracarboxylic acids and derivatives thereof is reacted with a diamine component consisting of one or more diamine compounds to obtain a polyamic acid. In order to obtain the polyamic acid alkyl ester, a method of converting the carboxyl group of the polyamic acid into an ester is used.
Furthermore, in order to obtain a polyimide, the method of imidating the said polyamic acid or polyamic-acid alkylester to make a polyimide is used.

The liquid crystal alignment film obtained using the specific polymer of the present invention increases the content ratio of the specific diamine compound in the diamine component, even after being exposed to backlight light for a long time in addition to the initial characteristics. The relaxation of the electric charge accumulated by the voltage holding ratio and the DC voltage is fast. Moreover, the pretilt angle of a liquid crystal can be enlarged, so that the content rate of the specific side chain type diamine compound in a diamine component increases. At this time, for the purpose of enhancing the above-described properties, the content of the specific side chain diamine compound in the diamine component is preferably 0.01 to 99 mol with respect to 1 mol of the specific diamine compound. More preferably, it is 0.1 to 50 mol, still more preferably 0.5 to 20 mol, and most preferably 0.5 to 10 mol.
Moreover, in order to obtain the specific polymer of this invention, it is preferable to use specific tetracarboxylic dianhydride for the tetracarboxylic dianhydride component. In that case, it is preferable that 1 mol% or more of a tetracarboxylic dianhydride component is a specific tetracarboxylic dianhydride, More preferably, it is 5 mol% or more, More preferably, it is 10 mol% or more. Further, 100 mol% of the tetracarboxylic dianhydride component may be a specific tetracarboxylic dianhydride.

Reaction of a diamine component and a tetracarboxylic dianhydride component is normally performed in an organic solvent. The organic solvent used at that time is not particularly limited as long as the produced polyimide precursor is 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 or 4-hydroxy-4-methyl-2-pentanone. These may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve a polyimide precursor, you may mix and use the said solvent in the range which the produced | generated polyimide precursor does not precipitate. Moreover, since the water | moisture content in an organic solvent inhibits a polymerization reaction, and also causes the produced polyimide precursor to hydrolyze, it is preferable to use what dehydrated and dried the organic solvent.

When the diamine component and the tetracarboxylic dianhydride 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 component is used as it is or in an organic solvent. A method of adding by dispersing or dissolving in a solvent, a method of adding a diamine component to a solution in which tetracarboxylic dianhydride is dispersed or dissolved in an organic solvent, and a tetracarboxylic dianhydride component and a diamine component These may be used alternately, and any of these methods may be used. Moreover, when making it react using multiple types of diamine component or tetracarboxylic dianhydride component, respectively, you may make it react in the state mixed previously, you may make it react separately one by one, and it was made to react individually further Low molecular weight substances may be mixed and reacted to form a specific polymer. In this case, the polymerization temperature can be selected from -20 to 150 ° C., but is preferably in the range of −5 to 100 ° C. The reaction can be carried out at any concentration, but if the concentration is too low, it will be difficult to obtain a specific polymer having a high molecular weight, and if the concentration is too high, the viscosity of the reaction solution will become too high and uniform stirring will occur. It becomes difficult. Therefore, it is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.

In the polymerization reaction for obtaining the polyimide precursor, the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic dianhydride component is preferably 0.8 to 1.2. Similar to a normal polycondensation reaction, the molecular weight of the polyimide precursor produced increases as the molar ratio approaches 1.0.
The polyimide of the present invention is a polyimide obtained by dehydrating and ring-closing the above polyimide precursor, and is useful as a polymer for obtaining a liquid crystal alignment film.
In the polyimide of the present invention, the dehydration cyclization rate (imidation rate) of the amic acid group is not necessarily 100%, and can be arbitrarily adjusted according to the application and purpose.

Examples of the method for imidizing the polyimide precursor include thermal imidization in which the polyimide precursor solution is heated as it is or catalyst imidization in which a catalyst is added to the polyimide precursor solution.
The temperature at which the polyimide precursor is thermally imidized in the solution is 100 to 400 ° C., preferably 120 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 polyimide precursor can be carried out by adding a basic catalyst and an acid anhydride to the polyimide precursor solution and stirring at -20 to 250 ° C, preferably 0 to 180 ° C. The amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol of the amido acid group. Is double. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Among them, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated. The imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.

When recovering the produced polyimide precursor or polyimide from the polyimide precursor or polyimide reaction solution, the reaction solution may be poured into a solvent and precipitated. Examples of the 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 the solvent can be collected by filtration, and then dried by normal temperature or reduced pressure at room temperature or by heating. In addition, when the polymer collected by precipitation is redissolved in an organic solvent and reprecipitation and collection is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of solvents selected from these because purification efficiency is further improved.

The molecular weight of the specific polymer of the present invention was measured by a GPC (Gel Permeation Chromatography) method in consideration of the strength of the polymer film obtained therefrom, workability at the time of forming the polymer film, and uniformity of the polymer film. The weight average molecular weight is preferably 5,000 to 1,000,000, and more preferably 10,000 to 150,000.

<Liquid crystal aligning agent>
The liquid-crystal aligning agent of this invention is a coating liquid for forming a liquid crystal aligning film, and is a coating liquid containing a specific polymer and an organic solvent.
The polymer component in the liquid crystal aligning agent of the present invention may all be a specific polymer used in the present invention, and other polymers may be mixed with the specific polymer of the present invention. . In that case, the content of the other polymer with respect to the specific polymer is 0.5 to 15% by mass, preferably 1 to 10% by mass.
As other polymers, a polyimide precursor obtained from a diamine component not containing a specific diamine compound and a specific side chain diamine compound and a tetracarboxylic dianhydride component not containing a specific tetracarboxylic dianhydride Or a polyimide obtained from the polyimide precursor. Furthermore, a polyimide precursor and a polymer other than polyimide, specifically, an acrylic polymer, a methacrylic polymer, polystyrene, or polyamide are also included.

The organic solvent in the liquid crystal aligning agent of the present invention preferably has an organic solvent content of 70 to 99% by mass from the viewpoint of forming a uniform polymer film by coating. This content can be appropriately changed depending on the film thickness of the target liquid crystal alignment film. The organic solvent in that case will not be specifically limited if it is an organic solvent in which the specific polymer mentioned above is dissolved. More specifically, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinylpyrrolidone, Dimethyl sulfoxide, tetramethyl urea, 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, Examples thereof include ethylene carbonate, propylene carbonate, diglyme and 4-hydroxy-4-methyl-2-pentanone. These may be used alone or in combination.

The liquid crystal aligning agent of the present invention is at least one selected from the group consisting of a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a hydroxyl group or an alkoxyl group, unless the effects of the present invention are impaired. A crosslinkable compound having a substituent, a crosslinkable compound having a polymerizable unsaturated bond, and the like can also be contained.
Examples of the crosslinkable compound having an epoxy group or an isocyanate group include bisphenolacetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidylaminodiphenylene, tetraglycidyl-m-xylenediamine, tetra Glycidyl-1,3-bis (aminoethyl) cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetodiglycidyl ether, 1,3-bis (1- (2,3-epoxypropoxy)- 1-trifluoromethyl-2,2,2-trifluoromethyl) benzene, 4,4-bis (2,3-epoxypropoxy) octafluorobiphenyl, Liglycidyl-p-aminophenol, tetraglycidylmetaxylenediamine, 2- (4- (2,3-epoxypropoxy) phenyl) -2- (4- (1,1-bis (4- (2,3-epoxy) Propoxy) phenyl) ethyl) phenyl) propane, 1,3-bis (4- (1- (4- (2,3-epoxypropoxy) phenyl) -1- (4- (1- (4- (2,3 -Epoxypropoxyphenyl) -1-methylethyl) phenyl) ethyl) phenoxy) -2-propanol and the like.

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

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

Examples of the crosslinkable compound having a cyclocarbonate group include a crosslinkable compound having at least two cyclocarbonate groups represented by the following formula [5].

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

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

Furthermore, polysiloxanes having at least one structure represented by the following formulas [5-38] to [5-40] can also be mentioned.

(In the formulas [5-38] to [5-40], R ₁ , R ₂ , R ₃ , R ₄ and R ₅ each independently represents a structure represented by the formula [5], a hydrogen atom, a hydroxyl group, An alkyl group having 1 to 10 carbon atoms, an alkoxyl group, an aliphatic ring or an aromatic ring, at least one of which is a structure represented by the formula [5]).
More specifically, compounds of the following formula [5-41] or formula [5-42] can be mentioned.

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

Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group or an alkoxyl group include, for example, amino resins having a hydroxyl group or an alkoxyl group, such as melamine resin, urea resin, guanamine resin, glycoluril. -Formaldehyde resin, succinylamide-formaldehyde resin, ethyleneurea-formaldehyde resin and the like. Specifically, a melamine derivative, a benzoguanamine derivative, or glycoluril in which a hydrogen atom of an amino group is substituted with a methylol group, an alkoxymethyl group, or both can be used. Melamine derivatives or benzoguanamine derivatives can also exist as dimers or trimers. These preferably have an average of 3 to 6 methylol groups or alkoxymethyl groups per triazine ring.

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

Benzene having a hydroxyl group or an alkoxyl group, or a phenolic compound can also be exemplified as the crosslinkable compound. For example, 1,3,5-tris (methoxymethyl) benzene, 1,2,4-tris (isopropoxymethyl) benzene, 1,4-bis (sec-butoxymethyl) benzene or 2,6-dihydroxymethyl-p -Tert-butylphenol and the like.
More specifically, it is a crosslinkable compound represented by the following formulas [6-1] to [6-48].

Examples of the crosslinkable compound having a polymerizable unsaturated bond include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and tri (meth) acryloyloxyethoxytrimethylol. Crosslinkable compounds having three polymerizable unsaturated groups in the molecule such as propane or glycerin polyglycidyl ether poly (meth) acrylate; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) ) Acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di ( ) Acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide bisphenol A type di (meth) acrylate, propylene oxide bisphenol type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di ( (Meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl ester phthalate di (meth) acrylate or neopentyl glycol hydroxypivalate Crosslinkable compounds having two polymerizable unsaturated groups in the molecule such as di (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl Pyr (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl Crosslinkable compounds having one polymerizable unsaturated group in the molecule such as (meth) acrylate, glycerin mono (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate ester or N-methylol (meth) acrylamide It is done.

In addition, a compound represented by the following formula [7] can also be exemplified as the crosslinkable compound.

(E ¹ is a monovalent group consisting of a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring or a phenanthrene ring, and E ² is represented by the following formula [ 7a] or the formula [7b], and n is an integer of 1 to 4.

The said compound is an example of a crosslinkable compound, It is not limited to these. Moreover, the crosslinkable compound contained in the liquid crystal aligning agent of this invention may be one type, and may be combined two or more types.
In the liquid crystal aligning agent of the present invention, the content of the crosslinkable compound is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of the polymer component, and the crosslinking reaction proceeds to exhibit the desired effect. In order not to lower the orientation of the liquid crystal, the amount is more preferably 0.1 to 100 parts by weight, particularly 1 to 50 parts by weight.

A nitrogen-containing heterocyclic amine compound represented by the following formulas [M1] to [M156] is added as a compound that promotes charge transfer in the liquid crystal alignment film and promotes charge loss of a liquid crystal cell using the liquid crystal alignment film. It is preferable to do. The amine compound may be added directly to the solution of the specific polymer, but it is preferable to add the amine compound after making a solution with a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass with an appropriate solvent. . The solvent is not particularly limited as long as it is an organic solvent that dissolves the specific polymer described above.

Unless the effect of this invention is impaired, the liquid-crystal aligning agent of this invention is an organic solvent (it is also called a poor solvent) which improves the uniformity of the film thickness of a polymer film at the time of apply | coating a liquid-crystal aligning agent, and surface smoothness. ) Or a compound. Furthermore, a compound that improves the adhesion between the liquid crystal alignment film and the substrate can also be contained.
Specific examples of poor solvents that improve film thickness uniformity and 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, dipro Lenglycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3 -Methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl Ether, n-hexane, n-pentane, n-octane, diethyl ether Methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, 3-methoxy Ethyl propionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy- 2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether Low surface tension such as ru-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, lactate methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n-butyl ester, lactyl isoamyl ester An organic solvent is mentioned.
These poor solvents may be used alone or in combination. When the above poor solvent is used, it is preferably 5 to 80% by mass, more preferably 20 to 60% by mass, based on the whole organic solvent contained in the liquid crystal alignment treatment agent.

Examples of the compound that improves the uniformity of the film thickness and the surface smoothness include a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant.
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 (Asahi Glass Co., Ltd.) and the like. The use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent. is there.

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-tri Toxisilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxy Silane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyl Trimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, poly Lopylene 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 is preferably 0.1 to 30 parts by mass, more preferably 1 to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent. ~ 20 parts by mass. If it is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the orientation of the liquid crystal may deteriorate.
In the liquid crystal alignment treatment agent of the present invention, in addition to the crosslinkable compound, the poor solvent, and the compound that improves adhesion, the dielectric constant and conductivity of the liquid crystal alignment film are within the range where the effects of the present invention are not impaired. A dielectric material or a conductive material for the purpose of changing the electrical characteristics such as property may be added.

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

The method for applying the liquid crystal aligning 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.

After applying the liquid crystal aligning agent on the substrate, the solvent can be evaporated at 50 to 300 ° C., preferably 80 to 250 ° C., by a heating means such as a hot plate to form a polymer film. If the thickness of the polymer film after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. Is 10 to 100 nm. When the liquid crystal is horizontally or tilted, the polymer film after baking is treated with 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 alignment treatment agent of the present invention by the method described above, and then preparing a liquid crystal cell by a known method.
As a liquid crystal cell manufacturing method, a pair of substrates on which a liquid crystal alignment film is formed are prepared, spacers are dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is on the inside, so that the other Examples include a method in which substrates are attached and liquid crystal is injected under reduced pressure, or a method in which liquid crystal is dropped onto a liquid crystal alignment film surface on which spacers are dispersed and then a substrate is attached and sealed.

Furthermore, the liquid-crystal aligning agent of this invention has a liquid-crystal layer between a pair of board | substrates provided with the electrode, The polymeric compound superposed | polymerized by at least one of an active energy ray and a heat | fever between a pair of board | substrates. The liquid crystal composition is preferably used also for a liquid crystal display device manufactured through a step of polymerizing a polymerizable compound by at least one of irradiation with active energy rays and heating while applying a voltage between electrodes. Here, ultraviolet rays are suitable as the active energy ray.

The liquid crystal display element controls a pretilt angle of liquid crystal molecules by a PSA (Polymer Sustained Alignment) method. In the PSA method, a small amount of a photopolymerizable compound, for example, a photopolymerizable monomer is mixed in a liquid crystal material, and after assembling a liquid crystal cell, a predetermined voltage is applied to the liquid crystal layer and an ultraviolet ray is applied to the photopolymerizable compound. The pretilt angle of the liquid crystal molecules is controlled by the produced polymer. Since the alignment state of the liquid crystal molecules when the polymer is formed is stored even after the voltage is removed, the pretilt angle of the liquid crystal molecules can be adjusted by controlling the electric field formed in the liquid crystal layer. . The PSA method does not require a rubbing process and is suitable for forming a vertical alignment type liquid crystal layer in which it is difficult to control the pretilt angle by the rubbing process.
That is, in the liquid crystal display element of the present invention, a liquid crystal cell is prepared after obtaining a substrate with a liquid crystal alignment film from the liquid crystal alignment treatment agent of the present invention by the above-described method, and a polymerizable compound is obtained by at least one of ultraviolet irradiation and heating. The orientation of liquid crystal molecules can be controlled by polymerizing.

If an example of liquid crystal cell production is given, prepare a pair of substrates on which a liquid crystal alignment film is formed, spread spacers on the liquid crystal alignment film of one substrate, and make the liquid crystal alignment film surface inside, Examples include a method in which the other substrate is attached and liquid crystal is injected under reduced pressure and sealing is performed, or a method in which liquid crystal is dropped on the liquid crystal alignment film surface on which spacers are dispersed and then the substrate is attached and sealed.

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

After the liquid crystal cell is produced, the polymerizable compound is polymerized by irradiating heat or ultraviolet rays while applying an AC or DC voltage to the liquid crystal cell. Thereby, the alignment of liquid crystal molecules can be controlled.
In addition, the liquid crystal aligning agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and is polymerized by at least one of active energy rays and heat between the pair of substrates. It is also preferably used for a liquid crystal display device manufactured through a step of disposing a liquid crystal alignment film containing a group and applying a voltage between the electrodes. Here, ultraviolet rays are suitable as the active energy ray.
In order to obtain a liquid crystal alignment film containing a polymerizable group that is polymerized from at least one of active energy rays and heat, a method of adding a compound containing the polymerizable group to a liquid crystal aligning agent, A method using a coalescing component may be mentioned. Examples of the polymerizable group include polymerizable unsaturated groups such as an acryl group, a methacryl group, a vinyl group, and a maleimide group.

Since the liquid crystal aligning agent of the present invention contains a specific amine compound having a double bond site that reacts by heat or ultraviolet irradiation, the alignment of liquid crystal molecules is controlled by at least one of ultraviolet irradiation and heating. Can do.
If an example of liquid crystal cell production is given, prepare a pair of substrates on which a liquid crystal alignment film is formed, spread spacers on the liquid crystal alignment film of one substrate, and make the liquid crystal alignment film surface inside, Examples include a method in which the other substrate is attached and liquid crystal is injected under reduced pressure and sealing is performed, or a method in which liquid crystal is dropped on the liquid crystal alignment film surface on which spacers are dispersed and then the substrate is attached and sealed.
After the liquid crystal cell is manufactured, the orientation of the liquid crystal molecules can be controlled by irradiating heat or ultraviolet rays while applying an AC or DC voltage to the liquid crystal cell.
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.

The present invention will be described in more detail with reference to the following examples, but is not limited thereto.
"Synthesis of specific diamine compounds"

<Synthesis Example 1>
Synthesis of specific diamine compound (4)

A solution of compound (2) (57.00 g, 455 mmol) and triethylamine (46.08 g, 455 mmol) in tetrahydrofuran (1000 g) was cooled to 10 ° C. or lower, and compound (1) (100.00 g, 434 mmol) in tetrahydrofuran (500 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 (high performance liquid chromatograph), the reaction solution was poured into distilled water (9 L (liter)), the precipitated solid was filtered, washed with water, and washed with 2-propanol (200 g). Dispersion washing was performed to obtain compound (3) (amount obtained: 120.6 g, yield: 89%).
¹ H-NMR ( ¹ H nuclear magnetic resonance spectroscopy) (400 MHz, DMSO-d ₆ , σ (ppm)): 9.21 (1H, t), 9.05 (2H, d), 8.97 (1H, t), 7.66 (1H, s), 7.22 (1H, s), 6.90 (1H, s), 4.05 (2H, t), 3.31 (2H, q), 2. 01 (2H, tt).

Next, a mixture of compound (3) (100.00 g, 313 mmol), 5% palladium carbon (hydrous type, 10.00 g, 10 wt%) and N, N-dimethylformamide (2000 g) was added in the presence of hydrogen in the presence of 23 Stir at ° C. After completion of the reaction, the atmosphere was replaced with nitrogen, activated carbon (10.00 g) was added, and the mixture was stirred at 23 ° C. for 1 hour. Thereafter, the catalyst and activated carbon were removed by filtration, and the solvent was distilled off to obtain crude crystals. 2-Propanol (300 g) was added to the crude crystals, stirred at 23 ° C. for 30 minutes, and dispersed and washed. The dispersed and washed solid was filtered and dried to obtain the specific diamine compound (4) (amount obtained: 76.3 g, yield: 94%).
¹ H-NMR (400 MHz, DMSO-d ₆ , σ (ppm)): 8.05 (1H, t), 7.62 (1H, t), 7.16 (1H, t), 6.85 (1H , T), 6.16 (2H, d), 5.89 (1H, t), 4.82 (4H, broadcast), 3.94 (2H, t), 3.43 (2H, q), 1 .85 (2H, tt).

<Synthesis Example 2>
Synthesis of specific diamine compound (7)

A solution of compound (5) (24.00 g, 195 mmol) and triethylamine (19.72 g, 195 mmol) in tetrahydrofuran (500 g) was cooled to 10 ° C. or lower, and compound (1) (42.80 g, 186 mmol) in tetrahydrofuran (142 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 (3.9 L), the precipitated solid was filtered, washed with water, dispersed and washed with 2-propanol (240 g), and the compound ( 6) was obtained (yield: 51.3 g, yield: 87%).
¹ H-NMR (400 MHz, DMSO-d ₆ , σ (ppm)): 9.87 (1H, broadcast), 9.10 (2H, d), 8.97 (1H, t), 8.57 (1H D), 8.50 (1H, t), 4.65 (2H, s), 2.84 (3H, s).

Next, a mixture of compound (6) (45.00 g, 142 mmol), 5% palladium carbon (hydrated product, 4.5 g, 10 wt%) and 1,4-dioxane (675 g) / DMF (200 g) was added in the presence of hydrogen. And stirred at 70 ° C. After completion of the reaction, the atmosphere was replaced with nitrogen, activated carbon (4.5 g) was added, and the mixture was stirred at 70 ° C. for 1 hour. Thereafter, the catalyst and activated carbon were removed by filtration, and the solvent was distilled off to obtain crude crystals. The obtained crude crystals were dispersed and washed with 2-propanol (100 g) to obtain the specific diamine compound (7) (yield: 33.7 g, yield: 92%).
¹ H-NMR (400 MHz, DMSO-d ₆ , σ (ppm)): 8.60 (1H, t), 8.42 (1H, m), 8.38 (1H, d), 6.22 (2H D), 5.92 (1H, t), 4.84 (4H, s), 4.43 (2H, d), 2.43 (3H, s).

<Synthesis Example 3>
Synthesis of specific diamine compound (10)

A solution of compound (8) (24.00 g, 146 mmol) and triethylamine (14.79 g, 146 mmol) in tetrahydrofuran (332 g) was cooled to 10 ° C. or lower, and compound (1) (32.10 g, 139 mmol) in tetrahydrofuran (100 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 (3.9 L), the precipitated solid was filtered, washed with water, dispersed and washed with 2-propanol (200 g), and the compound ( 9) was obtained (yield: 47.6 g, yield: 95%).
¹ H-NMR (400 MHz, DMSO-d ₆ , σ (ppm)): 8.88 (1H, t), 8.70 (2H, d), 8.40 (2H, t), 6.68 (1H , T), 3.90 (2H, broadcast), 3.75 (4H, broadcast), 3.42 (2H, broadcast).

Next, a mixture of compound (9) (40.00 g, 112 mmol), 5% palladium carbon (hydrated product, 4.0 g, 10 wt%) and DMF (800 g) was stirred at 70 ° 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 dispersed and washed with 2-propanol (12 g) to obtain the specific diamine compound (10) (amount obtained: 1.7 g, yield: 68%).
¹ H-NMR (400 MHz, DMSO-d ₆ , σ (ppm)): 8.35 (2H, d), 6.63 (1H, t), 5.82 (1H, t), 5.75 (2H D), 4.86 (4H, s), 3.70 (4H, broadcast), 3.49 (4H, broadcast).

<Synthesis Example 4>
Synthesis of diamine compound (13)

A solution of compound (11) (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 then the precipitated solid was filtered and washed with water. Thereafter, the solid was dispersed and washed with ethanol (300 g) to obtain compound (12) (yield: 36.92 g, yield: 90%).
¹ H-NMR (400 MHz, DMSO-d ₆ , σ (ppm)): 9.75 (1H, broadcast), 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 (12) (36.00 g, 119 mmol), 5% palladium carbon (hydrous type, 3.6 g, 10 wt%) and 1,4-dioxane (300 g) was added at 60 ° 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 crude product. The obtained crude product was recrystallized from methanol (200 g) to obtain a diamine compound (13) (amount obtained: 21.5 g, yield: 72%).
¹ H-NMR (400 MHz, DMSO-d ₆ , σ (ppm)): 8.55 (1H, broadcast), 7.37-7.17 (5H, m), 6.28 (2H, s), 6 .98-6.94 (1H, m), 4.85-4.74 (4H, broadcast), 4.42-4.35 (2H, m).

<Synthesis Example 5>
Synthesis of diamine compound (16)

A solution of compound (14) (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). 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 (1.5 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 (15) (yield: 50.82 g, yield: 89%).
¹ H-NMR (400 MHz, DMSO-d ₆ , σ (ppm)): 9.76 (1H, t), 9.09-9.02 (2H, m), 8.99-8.93 (1H, m), 8.50 (1H, broadcast), 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 (15) (48.00 g, 151 mmol), 5% palladium carbon (hydrous type, 4.8 g, 10 wt%) and 1,4-dioxane (490 g) was added at 60 ° 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 crude product. The obtained crude product was dispersed and washed with ethanol (300 g) to obtain a diamine compound (16) (amount: 27.20 g, yield: 70%).
¹ H-NMR (400 MHz, DMSO-d ₆ , σ (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 of polyimide precursor and polyimide"
The abbreviations of the compounds used in the examples are as follows.
(Tetracarboxylic dianhydride)
CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride BODA: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride TCA: represented by the following formula Tetracarboxylic dianhydride TDA: tetracarboxylic dianhydride represented by the following formula

(Specific diamine compound)
Specific diamine compound (4): Specific diamine compound obtained by the synthesis route of Synthesis Example 1 Specific diamine compound (7): Specific diamine compound obtained by the synthesis route of Synthesis Example 2 Specific diamine compound (10): Synthesis Example 3 Specific diamine compound (specific side chain type diamine compound) obtained by the synthetic route of
PCH7DAB: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene PBCH5DAB: 1,3-diamino-4- {4- [trans-4- (trans-4 -N-pentylcyclohexyl) cyclohexyl] phenoxy} benzene m-PBCH5DABz: 1,3-diamino-5- {4- [4- (trans-4-n-pentylcyclohexyl) phenyl] phenoxymethyl} benzene ColDAB -1: Specific side chain diamine compound represented by the following formula

(Other diamine compounds)
p-PDA: p-phenylenediamine m-PDA: m-phenylenediamine DBA: 3,5-diaminobenzoic acid AP18: 1,3-diamino-4-octadecyloxybenzene diamine compound (13): Synthesis route of Synthesis Example 4 Diamine Compound Obtained in 1) Diamine Compound (16): Diamine Compound Obtained by the Synthesis Route of Synthesis Example 5

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

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

(Measurement of molecular weight of polyimide precursor and polyimide)
The molecular weight of polyimide in the synthesis example is as follows using a normal temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko KK) and columns (KD-803, KD-805) (manufactured by Shodex). The measurement was performed as described above.
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 (milliliter) / L)
Flow rate: 1.0 ml / min Standard sample for preparing calibration curve: TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000, 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight: about 12, 000, 4,000, 1,000) (manufactured by Polymer Laboratory).

(Measurement of imidization rate)
The imidation ratio of polyimide in the synthesis example was measured as follows. 20 mg of polyimide powder was put into an NMR sample tube (NMR sampling tube standard, φ5 (manufactured by Kusano Kagaku)), and deuterated dimethyl sulfoxide (0.05 mass% TMS (tetramethylsilane) in DMSO-d6) (0.005). 53 ml) was added and completely dissolved by sonication. 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 based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of amic acid appearing in the vicinity of 9.5 to 10.0 ppm. It calculated | required by the following formula | equation using the integrated value.
Imidization rate (%) = (1−α · x / y) × 100
In the above formula, x is a proton peak integrated value derived from NH group of amic acid, y is a peak integrated value of reference proton, α is one NH group proton of amic acid in the case of polyamic acid (imidation rate is 0%) Is the number ratio of the reference proton to.

<Synthesis Example 1>
BODA (5.87 g, 23.5 mmol), specific diamine compound (4) (0.76 g, 2.93 mmol), PCH7DAB (5.58 g, 14.7 mmol), and p-PDA (1.27 g, 11.7 mmol) ) In NMP (24.1 g) and reacted at 80 ° C. for 4.5 hours. Thereafter, CBDA (1.15 g, 5.86 mmol) and NMP (19.7 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution (A) having a resin solid content concentration of 25.0 mass%. It was. The number average molecular weight of this polyamic acid was 27,400, and the weight average molecular weight was 77,300.

<Synthesis Example 2>
After adding NMP to the polyamic acid solution (A) (20.0 g) having a resin solid concentration of 25.0% by mass obtained in Synthesis Example 1 and diluting to 6% by mass, acetic anhydride ( 2.45 g) and pyridine (1.80 g) were added and reacted at 80 ° C. for 3.5 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 (B). The imidation ratio of this polyimide was 55%, the number average molecular weight was 23,200, and the weight average molecular weight was 57,100.

<Synthesis Example 3>
BODA (5.87 g, 23.5 mmol), specific diamine compound (4) (1.52 g, 5.86 mmol), PBCH5DAB (3.81 g, 8.80 mmol), and p-PDA (1.59 g, 14.7 mmol) ) In NMP (23.0 g) and reacted at 80 ° C. for 4.5 hours. Thereafter, CBDA (1.15 g, 5.86 mmol) and NMP (18.8 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%.
After adding NMP to the obtained polyamic acid solution (20.5 g) and diluting to 6% by mass, acetic anhydride (2.42 g) and pyridine (1.81 g) were added as an imidization catalyst at 80 ° C. The reaction was performed for 3.5 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 (C). The imidation ratio of this polyimide was 52%, the number average molecular weight was 21,600, and the weight average molecular weight was 51,700.

<Synthesis Example 4>
BODA (3.42 g, 13.7 mmol), specific diamine compound (4) (1.01 g, 3.91 mmol), m-PBCH5DABz (2.62 g, 5.86 mmol), DBA (1.49 g, 9.77 mmol) Were mixed in NMP (16.0 g) and reacted at 80 ° C. for 4.5 hours, then CBDA (1.15 g, 5.86 mmol) and NMP (13.1 g) were added, and reacted at 40 ° C. for 6 hours. Thus, a polyamic acid solution having a resin solid content concentration of 25.0% by mass was obtained.
After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting to 6% by mass, acetic anhydride (4.55 g) and pyridine (3.30 g) were added as imidization catalysts, Reacted for hours. This reaction solution was poured into methanol (400 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 (D). The imidation ratio of this polyimide was 81%, the number average molecular weight was 22,100, and the weight average molecular weight was 53,200.

<Synthesis Example 5>
BODA (5.72 g, 22.8 mmol), specific diamine compound (7) (0.73 g, 2.86 mmol), ColDAB-1 (2.11 g, 4.28 mmol), and m-PDA (2.32 g, 21 .4 mmol) was mixed in NMP (19.8 g) and reacted at 80 ° C. for 4.5 hours. Thereafter, CBDA (1.12 g, 5.71 mmol) and NMP (16.2 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%.
After adding NMP to the obtained polyamic acid solution (20.5 g) and diluting to 6% by mass, acetic anhydride (2.55 g) and pyridine (1.95 g) were added as an imidization catalyst at 80 ° C. The reaction was performed for 4 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 (E). The imidation ratio of this polyimide was 52%, the number average molecular weight was 20,800, and the weight average molecular weight was 53,100.

<Synthesis Example 6>
TCA (3.51 g, 15.7 mmol), specific diamine compound (4) (0.41 g, 1.57 mmol), PCH7DAB (2.38 g, 6.26 mmol), and p-PDA (0.85 g, 7.83 mmol) ) In NMP (28.6 g) and reacted at 40 ° C. for 8 hours to obtain a polyamic acid solution (F) having a resin solid content concentration of 25.0 mass%. The number average molecular weight of this amic acid was 28,900, and the weight average molecular weight was 75,300.

<Synthesis Example 7>
TCA (3.52 g, 15.7 mmol), specific diamine compound (10) (0.47 g, 1.57 mmol), PBCH5DAB (1.80 g, 4.16 mmol), and m-PDA (0.90 g, 8.32 mmol) ) Was mixed in NMP (21.1 g) and reacted at 40 ° C. for 8 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%.
After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting to 6% by mass, acetic anhydride (2.55 g) and pyridine (1.95 g) were added as an imidization catalyst at 80 ° C. The reaction was performed for 4.5 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 (G). The imidation ratio of this polyimide was 52%, the number average molecular weight was 21,200, and the weight average molecular weight was 51,300.

<Synthesis Example 8>
BODA (1.15 g, 4.60 mmol), specific diamine compound (4) (0.40 g, 1.53 mmol), PBCH5DAB (1.99 g, 4.70 mmol), and DBA (1.40 g, 9.19 mmol). Mix in NMP (12.1 g) and react at 80 ° C. for 3 hours. Thereafter, TCA (2.40 g, 10.7 mmol) and NMP (9.91 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%.
After adding NMP to the obtained polyamic acid solution (20.1 g) and diluting to 6% by mass, acetic anhydride (4.50 g) and pyridine (3.35 g) were added as an imidization catalyst at 90 ° C. The reaction was performed for 3 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 (H). The imidation ratio of this polyimide was 82%, the number average molecular weight was 21,900, and the weight average molecular weight was 51,900.

<Synthesis Example 9>
BODA (1.15 g, 4.60 mmol), specific diamine compound (7) (0.79 g, 3.06 mmol), ColDAB-1 (1.51 g, 3.06 mmol), and DBA (1.40 g, 9.19 mmol) ) In NMP (12.0 g) and reacted at 80 ° C. for 3 hours. Thereafter, TCA (2.40 g, 10.7 mmol) and NMP (9.79 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%.
After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting to 6% by mass, acetic anhydride (2.50 g) and pyridine (1.90 g) were added as an imidization catalyst at 80 ° C. The reaction was performed for 3.5 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 (I). The imidation ratio of this polyimide was 56%, the number average molecular weight was 19,800, and the weight average molecular weight was 53,500.

<Synthesis Example 10>
TDA (1.39 g, 4.63 mmol), specific diamine compound (10) (0.46 g, 1.54 mmol), PCH7DAB (2.35 g, 6.18 mmol), and DBA (1.17 g, 7.72 mmol). Mixed in NMP (12.4 g) and reacted at 80 ° C. for 3 hours. Thereafter, CBDA (2.12 g, 10.8 mmol) and NMP (10.1 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%.
After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting to 6% by mass, acetic anhydride (4.50 g) and pyridine (3.35 g) were added as an imidization catalyst at 90 ° C. The reaction was performed for 3 hours. This reaction solution was poured into methanol (400 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 (J). The imidation ratio of this polyimide was 72%, the number average molecular weight was 20,200, and the weight average molecular weight was 49,800.

<Synthesis Example 11>
BODA (5.87 g, 23.5 mmol), AP18 (5.52 g, 14.7 mmol), and p-PDA (1.59 g, 14.7 mmol) were mixed in NMP (23.3 g) at 80 ° C. The reaction was performed for 4 hours. Thereafter, CBDA (1.15 g, 5.86 mmol) and NMP (19.1 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution (K) having a resin solid content concentration of 25.0 mass%. It was. The number average molecular weight of this polyamic acid was 25,400, and the weight average molecular weight was 70,900.

<Synthesis Example 12>
After adding NMP to the polyamic acid solution (K) (20.1 g) having a resin solid content concentration of 25.0% by mass obtained in Synthesis Example 11 and diluting to 6% by mass, acetic anhydride ( 2.40 g) and pyridine (1.85 g) were added and reacted at 80 ° C. for 4 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 (L). The imidation ratio of this polyimide was 56%, the number average molecular weight was 20,100, and the weight average molecular weight was 54,200.

<Synthesis Example 13>
BODA (5.87 g, 23.5 mmol), PCH7DA (5.58 g, 14.7 mmol), and p-PDA (1.59 g, 14.7 mmol) were mixed in NMP (23.4 g) at 80 ° C. After reacting for 4 hours, CBDA (1.15 g, 5.86 mmol) and NMP (19.1 g) were added and reacted at 40 ° C. for 6 hours, and the polyamic acid solution having a resin solid content concentration of 25.0 mass% Got.
After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting to 6% by mass, acetic anhydride (2.50 g) and pyridine (1.90 g) were added as an imidization catalyst at 80 ° C. The reaction was performed for 4 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 (M). The imidation ratio of this polyimide was 55%, the number average molecular weight was 20,300, and the weight average molecular weight was 49,800.

<Synthesis Example 14>
BODA (5.87 g, 23.5 mmol), PCH7DAB (5.58 g, 14.7 mmol), diamine compound (13) (0.71 g, 2.93 mmol), and p-PDA (1.27 g, 11.7 mmol) Were mixed in NMP (22.2 g) and reacted at 80 ° C. for 4 hours. Thereafter, CBDA (1.15 g, 5.86 mmol) and NMP (18.2 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%.
After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting to 6% by mass, acetic anhydride (2.50 g) and pyridine (1.92 g) were added as an imidization catalyst at 80 ° C. The reaction was performed for 4 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 (N). The imidation ratio of this polyimide was 55%, the number average molecular weight was 20,100, and the weight average molecular weight was 54,100.

<Synthesis Example 15>
BODA (5.87 g, 23.5 mmol), PCH7DAB (5.58 g, 14.7 mmol), diamine compound (16) (0.75 g, 2.93 mmol), and p-PDA (1.27 g, 11.7 mmol) Were mixed in NMP (24.1 g) and reacted at 80 ° C. for 4 hours. Thereafter, CBDA (1.15 g, 5.86 mmol) and NMP (19.7 g) were added and reacted at 40 ° C. for 8 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%.
After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting to 6% by mass, acetic anhydride (2.45 g) and pyridine (1.85 g) were added as an imidization catalyst at 80 ° C. The reaction was performed for 3.5 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 (O). The imidation ratio of this polyimide was 55%, the number average molecular weight was 21,200, and the weight average molecular weight was 52,100.

<Synthesis Example 16>
BODA (5.77 g, 23.0 mmol), specific diamine compound (4) (0.75 g, 2.88 mmol), AP18 (5.43 g, 14.4 mmol), and p-PDA (1.27 g, 11.5 mmol) ) In NMP (23.6 g) and reacted at 80 ° C. for 4 hours. Thereafter, CBDA (1.13 g, 5.76 mmol) and NMP (19.3 g) were added and reacted at 40 ° C. for 8 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%.
After adding NMP to the obtained polyamic acid solution (20.5 g) and diluting to 6% by mass, acetic anhydride (2.50 g) and pyridine (1.90 g) were added as an imidization catalyst at 80 ° C. The reaction was performed for 4 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 (P). The imidation ratio of this polyimide was 54%, the number average molecular weight was 21,900, and the weight average molecular weight was 51,400.
Table 45 shows the polyamic acid and polyimide of the present invention.

* 1: Polyamic acid.

"Manufacture of liquid crystal alignment treatment agent"
Examples 1 to 13 and Comparative Examples 1 to 6 describe production examples of liquid crystal aligning agents. Tables 46 and 47 show the compositions of the produced liquid crystal aligning agent.

“Preparation of liquid crystal cell” and “Evaluation of electrical characteristics” are as follows.
A liquid crystal cell was prepared using each of the liquid crystal alignment treatment agents obtained in Examples 1 to 13 and Comparative Examples 1 to 6, and the electrical characteristics of the obtained liquid crystal cell were evaluated.

"Production of liquid crystal cell"
A liquid crystal alignment treatment agent is spin-coated on the ITO surface of a 30 × 40 mm ITO electrode substrate, and heated at 80 ° C. for 5 minutes on a hot plate and at 230 ° C. for 30 minutes in a heat-circulating clean oven. Thus, a substrate with a polyimide liquid crystal alignment film having a thickness of 100 nm was obtained.
Two substrates with the obtained liquid crystal alignment film were prepared, combined with a 6 μm spacer sandwiched with the liquid crystal alignment film surface on the inside, and the periphery was adhered with a sealant to produce an empty cell. MLC-6608 (manufactured by Merck Japan) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a nematic liquid crystal cell.
When this liquid crystal cell was observed with a polarizing microscope, the liquid crystal was uniformly aligned and no alignment defect was observed.

"Evaluation of electrical characteristics"
A voltage of 1 V was applied to the liquid crystal cell obtained in the above-mentioned “Preparation of liquid crystal cell” at a temperature of 80 ° C. for 60 μm, and the voltage after 16.67 ms and 50 ms was measured. Was calculated as a voltage holding ratio. The measurement was performed using a VHR-1 voltage holding ratio measuring device (manufactured by Toyo Technica Co., Ltd.) with settings of Voltage: ± 1 V, Pulse Width: 60 μs, Frame Period: 16.67 ms or 50 ms.
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 the measurement, a liquid crystal property evaluation apparatus (6254 type) manufactured by Toyo Technica Co., Ltd. was used.
The liquid crystal cell in which the measurement of the voltage holding ratio and the residual charge was completed was irradiated with ultraviolet rays of 50 J / cm ^{2 in} terms of 365 nm, and then the voltage holding ratio and the residual charge were measured under the same conditions as described above. The ultraviolet irradiation was performed using a desktop UV curing device (HCT3B28HEX-1) (SEN LIGHT CORPRATION).

<Example 1>
The polyamic acid solution (A) (10.5 g), NMP (8.50 g), and BCS (24.6 g) having a resin solid content concentration of 24.9% by mass obtained in Synthesis Example 1 were added at 25 ° C. for 6 hours. By mixing, the liquid crystal aligning agent (1) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the obtained liquid crystal aligning agent (1), production of a liquid crystal cell and evaluation of electric characteristics were performed under the above-described conditions.
In Examples 2 to 13 and Comparative Examples 1 to 6, liquid crystal cells were prepared and electrical characteristics were evaluated using the produced liquid crystal alignment treatment agents in the same manner as in Example 1. The results are shown in Tables 48 to 51.

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

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

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

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

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

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

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

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

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

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

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

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

<Comparative Example 1>
The polyamic acid solution (K) (10.0 g), NMP (8.50 g) and BCS (23.9 g) having a resin solid content concentration of 25.4% by mass obtained in Synthesis Example 11 were added at 25 ° C. for 6 hours. The liquid crystal aligning agent (14) was obtained by mixing. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

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

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

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

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

<Comparative Example 6>
The polyimide powder (P) (2.51 g), NMP (28.1 g) and BCS (13.8 g) obtained in Synthesis Example 16 were mixed at 25 ° C. for 8 hours to obtain a liquid crystal alignment treatment agent (19). Got. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

As can be seen from the above results, the liquid crystal alignment films obtained from the liquid crystal alignment treatment agents of Examples 1 to 13 were exposed to ultraviolet rays as compared with the liquid crystal alignment films obtained from the liquid crystal alignment agents of Comparative Examples 1 to 6. Even after being applied, the decrease in the voltage holding ratio is small, and the residual charge accumulated by the DC voltage is quickly relaxed.
In Comparative Examples 1 to 5 that do not contain the specific diamine compound, the voltage holding ratio is greatly lowered after being exposed to ultraviolet rays, and the residual charge accumulated by the DC voltage is slowly relieved. The same result was obtained in Comparative Example 6 that did not contain the specific side chain diamine compound.

From the liquid crystal aligning agent of the present invention, it is possible to obtain a liquid crystal alignment film that suppresses the decrease in the voltage holding ratio even when exposed to light irradiation for a long time and further reduces the charge accumulated by the DC voltage. . The liquid crystal display element having the liquid crystal alignment film of the present invention has excellent reliability and is suitably used for a large-screen, high-definition liquid crystal television and the like, and also has a TN element, an STN element, a TFT liquid crystal element, particularly a vertical liquid crystal display element. This is useful for an alignment type liquid crystal display element.
Furthermore, the liquid crystal aligning film obtained from the liquid crystal aligning agent of this invention can be used for manufacture of the liquid crystal display element which has the process of irradiating an ultraviolet-ray, applying a voltage between electrodes.
The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2010-167371 filed on July 26, 2010 are incorporated herein as the disclosure of the specification of the present invention. Is.

Claims

It comprises a polyimide precursor obtained by reacting a diamine compound represented by the following formula [1] and a diamine component containing the diamine compound represented by the following formula [2] with a tetracarboxylic dianhydride component, and a polyimide. A liquid crystal aligning agent containing at least one polymer selected from the group.

(In the formula [1], X 1 represents —O—, —CO—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —CH 2 O—, —OCO—, — CON (CH 3 ) — or N (CH 3 ) CO—, X 2 is an alkyl group having 1 to 5 carbon atoms or a non-aromatic heterocyclic ring containing a nitrogen atom, and X 3 has 1 carbon atom A 5-membered or 6-membered aromatic heterocycle containing 2 nitrogen atoms optionally substituted with 5 to 5 alkyl groups)

(In Formula [2], Y 1 is a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or OCO—. Y 2 is a single bond or (CH 2 ) b — (b is an integer of 1 to 15), Y 3 is a single bond, — (CH 2 ) c — (c is 1 to 15) Is an integer), —O—, —CH 2 O—, —COO— or OCO— Y 4 is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring (the cyclic group thereof) Arbitrary hydrogen atoms on the group include an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or fluorine Or an organic group having 12 to 25 carbon atoms having a steroid skeleton. A divalent organic group that, Y 5 is a benzene ring, any hydrogen atom on the divalent cyclic group (these cyclic group selected from the group consisting of hexane ring and the heterocyclic cycloheteroalkyl is 1 carbon atoms Or an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. , N is an integer of 0 to 4. Y 6 is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or 1 to 18 carbon atoms. And m is an integer of 1 to 4.)
2. The formula [1], wherein X 1 is —O—, —CO—, —NH—, —CONH—, —NHCO—, —CON (CH 3 ) — or CH 2 O—. Liquid crystal aligning agent.
Wherein [1], X 2 is a liquid crystal alignment treating agent according to claim 1 or 2 is a piperazine ring.
The liquid crystal aligning agent according to any one of claims 1 to 3, wherein in the formula [1], X 3 is an imidazole ring, a pyrazine ring or a pyrimidine ring.
The liquid crystal aligning agent according to any one of claims 1 to 4, wherein the polymer is a polymer using a tetracarboxylic dianhydride represented by the following formula [3].

(In Formula [3], Z 1 is a tetravalent organic group having 4 to 13 carbon atoms and contains a non-aromatic cyclic hydrocarbon group having 4 to 10 carbon atoms.)
6. The liquid crystal aligning agent according to claim 5, wherein Z 1 is a group having a structure represented by the following formulas [3a] to [3j].

(In the formula [3a], Z 2 to Z 5 are a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different. In the formula [3g], Z 6 and Z 7 is a hydrogen atom or a methyl group, and each may be the same or different.
The polymer is at least one polymer selected from the group consisting of a polyamic acid obtained by reacting a diamine component and a tetracarboxylic dianhydride component and a polyimide obtained by dehydrating and ring-closing the polyamic acid. The liquid crystal aligning agent according to any one of claims 1 to 6.
The liquid crystal aligning agent according to any one of claims 1 to 6, wherein the polymer is a polyimide obtained by dehydrating and ring-closing polyamic acid.
In the liquid crystal aligning agent, a crosslinkable compound having at least one substituent selected from the group consisting of an epoxy group, an oxetane group, a cyclocarbonate group or an isocyanate group, a hydroxyl group and an alkoxyl group, or polymerization The liquid crystal aligning agent according to any one of claims 1 to 8, which has a crosslinkable compound having a polymerizable unsaturated bond.
The liquid crystal aligning agent according to any one of claims 1 to 9, wherein the liquid crystal aligning agent contains an organic solvent, and the poor solvent contains 5 to 80% by mass of the whole organic solvent.
A liquid crystal alignment film obtained using the liquid crystal aligning agent according to any one of claims 1 to 10.
A liquid crystal display element having the liquid crystal alignment film according to claim 11.
A liquid crystal composition comprising a liquid crystal layer between a pair of substrates provided with electrodes and comprising a polymerizable compound that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates, and the electrodes The liquid crystal aligning film of Claim 11 used for the liquid crystal display element manufactured through the process of superposing | polymerizing the said polymeric compound, applying a voltage in between.
A polymerizable compound comprising a liquid crystal layer between a pair of substrates provided with the liquid crystal alignment film according to claim 11 and an electrode, and polymerized by at least one of active energy rays and heat between the pair of substrates. The liquid crystal display element manufactured through the process of arrange | positioning the liquid crystal composition containing this and polymerizing the said polymeric compound, applying a voltage between the said electrodes.
A liquid crystal layer between a pair of substrates provided with electrodes, and a liquid crystal alignment film containing a polymerizable group that is polymerized by at least one of active energy rays and heat between the pair of substrates; The liquid crystal aligning film of Claim 11 used for the liquid crystal display element manufactured through the process of superposing | polymerizing the said polymeric group, applying a voltage in between.
The liquid crystal alignment film according to claim 11, comprising a liquid crystal layer between a pair of substrates provided with electrodes, and containing a polymerizable group that is polymerized by at least one of active energy rays and heat between the pair of substrates. And a liquid crystal display device manufactured through a process of polymerizing the polymerizable group while applying a voltage between the electrodes.