KR20190131567A - Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element - Google Patents

Abstract

R¹ 은 수소 원자, 탄소수 1 ∼ 5 의 직사슬 혹은 분기해도 되는 알킬기 또는 아릴기를 나타내고, 동일한 말레이미드 고리 상에 2 개 있는 R¹ 은 서로 동일해도 되고, 상이해도 되고, 2 개 있는 R¹ 이 하나가 되어 탄소수 3 ∼ 6 의 알킬렌을 형성해도 되고, W² 는 2 가의 유기기를 나타내고, W¹ 은 단결합 또는 카르보닐을 나타내고, L¹ 은 탄소수 1 ∼ 20 의 직사슬형 알킬렌기, 탄소수 3 ∼ 20 의 분기형 알킬렌기, 탄소수 3 ∼ 20 의 고리형 알킬렌기, 페닐렌기 및 복소 고리기에서 선택되는 2 가의 기, 또는 당해 2 가의 기가 복수 결합하여 이루어지는 기를 나타내고, 페닐렌기 및 복소 고리기는 각각 독립적으로 알킬기, 알콕시기, 할로알킬기, 할로알콕시기, 할로겐기 및 시아노기에서 선택되는 동일 또는 상이한 1 또는 복수의 치환기로 치환되어 있어도 되고, 당해 2 가의 기끼리의 결합은, 단결합, 에스테르 결합, 아미드 결합, 우레아 결합, 에테르 결합, 티오에테르 결합, 아미노 결합 및 카르보닐에서 선택되는 적어도 1 종이고, 당해 2 가의 기가 복수가 되는 경우에는, 2 가의 기끼리는 동일해도 되고 상이해도 되고, 상기 결합이 복수가 되는 경우에는, 결합끼리는 동일해도 되고 상이해도 되고, R 은 수소 원자 또는 1 가의 유기기를 나타내고, 2 개 있는 R 이 서로 상이해도 되고, 2 개 있는 R 이 하나가 되어 탄소수 1 ∼ 6 의 알킬렌을 형성하고 있어도 되고, 2 개 있는 R 의 양방 또는 어느 일방이 L¹ 에 결합하고 있어도 된다.The liquid crystal aligning agent containing the polymer obtained from the diamine which has a structure represented by following formula (1).

R <^1> represents a hydrogen atom, a C1-C5 linear or branched alkyl group, or an aryl group, and two R <^1> on the same maleimide ring may be mutually same, may differ, and two R <^1> is One may form alkylene having 3 to 6 carbon atoms, W ² represents a divalent organic group, W ¹ represents a single bond or carbonyl, and L ¹ represents a linear alkylene group having 1 to 20 carbon atoms and carbon number. The divalent group selected from a 3-20 branched alkylene group, a C3-C20 cyclic alkylene group, a phenylene group, and a heterocyclic group, or the group which the said bivalent group combines in multiple numbers is shown, A phenylene group and a heterocyclic group Each independently may be substituted with the same or different one or a plurality of substituents selected from an alkyl group, an alkoxy group, a haloalkyl group, a haloalkoxy group, a halogen group and a cyano group, and The bond between divalent groups is at least one selected from a single bond, an ester bond, an amide bond, a urea bond, an ether bond, a thioether bond, an amino bond, and carbonyl, and when the divalent groups are plural, The divalent groups may be the same or different, and in the case where the bonds are plural, the bonds may be the same or different, R represents a hydrogen atom or a monovalent organic group, and two R's may be different from each other, the two R, which is the one and may form an alkylene group having 1 to 6 carbon atoms, or may, and that both or either one of the two R, which joined to L ^1.

Description

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

The present invention provides a polyamic acid, a polyamic acid ester, a polyimide, a liquid crystal aligning agent, a liquid crystal aligning film, and the like obtained by using a novel diamine compound (also referred to simply as a diamine in the present invention) useful as a raw material for a polymer used in a liquid crystal alignment film. It relates to a liquid crystal display element.

BACKGROUND ART Liquid crystal display elements have conventionally been widely used as display units for personal computers, mobile phones, television receivers, and the like. As the driving method thereof, conventional electric field methods such as TN method and VA method, IPS method, and fringe field switching (Fringe) Field switching: A lateral electric field system such as FFS) is known.

In general, in the transverse electric field system in which electrodes are formed only on one side of the substrate and an electric field is applied in a direction parallel to the substrate, a wide viewing angle characteristic is compared with the electric field system in which a liquid crystal is driven by applying a voltage to electrodes formed on the upper and lower substrates. It is easy to obtain the liquid crystal display element which can display high quality. As a method for orienting a liquid crystal in a fixed direction, for example, there is a method of performing a so-called rubbing treatment of forming a polymer film such as polyimide on a substrate and rubbing this surface with a cloth.

As a conventional subject, improvement of voltage retention and improvement of charge accumulation by the DC voltage component applied from an active matrix structure are mentioned. When electric charges accumulate in a liquid crystal display element, it will adversely affect display by the disorder of a liquid crystal orientation, an afterimage, etc., and will reduce the display quality of a liquid crystal display element remarkably. Alternatively, when driving in a state where charge is accumulated, immediately after the driving, control of the liquid crystal molecules is not normally performed, causing flickering or the like.

Moreover, ion density is mentioned as a characteristic calculated | required by the liquid crystal aligning film in order to improve the display quality of a liquid crystal display element. When the ion density is high, the voltage applied to the liquid crystal is lowered, and as a result, the luminance is lowered, which may interfere with normal gradation display. In addition, even if the initial ion density is low, the ion density after the high temperature accelerated test may be increased in some cases. Such deterioration of long-term reliability or residual image accompanying residual charges or ionic impurities reduces the display quality of the liquid crystal.

In the liquid crystal aligning film of a polyimide system, in order to respond to the above request, various proposals have been made. For example, a liquid crystal aligning film whose purpose is to shorten the time until the afterimage generated by DC voltage disappears, and contains a tertiary amine having a specific structure in addition to polyamic acid or imide group-containing polyamic acid. The thing using the liquid crystal aligning agent containing the soluble polyimide which used the thing using the liquid crystal aligning agent to mention (for example, refer patent document 1), and the specific diamine compound which has a pyridine skeleton etc. (for example, patent document 2) is proposed.

Japanese Patent Laid-Open No. 9-316200 Japanese Unexamined Patent Publication No. 10-104633

Although the rubbing process is widely used industrially as a method of orienting a liquid crystal, the phenomenon that what is called a twist angle in which the rubbing direction and the orientation direction of a liquid crystal do not correspond may arise depending on the liquid crystal aligning film to be used. That is, in the transverse electric field element, black display is shown in a state where no voltage is applied, but there is a problem that the luminance is increased even in a state where no voltage is applied by this phenomenon, and as a result, the display contrast is lowered.

According to the present invention, the ion density in the liquid crystal display element can be reduced, and the accumulated charge can be alleviated quickly. In particular, the shift between the rubbing direction and the alignment direction of the liquid crystal, which is a problem in the transverse electric field driving system, can be suppressed. It aims at providing the liquid crystal aligning film which can be obtained, the liquid crystal aligning agent from which such a liquid crystal aligning film is obtained, and the liquid crystal display element etc. which comprise such a liquid crystal aligning film.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, it discovered that various characteristics improve simultaneously by introducing a specific structure in the polymer contained in a liquid crystal aligning agent, and completed this invention. This invention is based on this knowledge and makes the following a summary.

1. The liquid crystal aligning agent containing the polymer obtained from the diamine which has a structure represented by following formula (1).

[Formula 1]

R <^1> represents a hydrogen atom, a C1-C5 linear or branched alkyl group, or an aryl group, and two R <^1> on the same maleimide ring may be mutually same, may differ, and two R <^1> is One may form alkylene having 3 to 6 carbon atoms, W ² represents a divalent organic group, W ¹ represents a single bond or carbonyl, and L ¹ represents a linear alkylene group having 1 to 20 carbon atoms and carbon number. A divalent group selected from a 3-20 branched alkylene group, a C3-C20 cyclic alkylene group, a phenylene group, and a heterocyclic group, or the group which a plurality of said bivalent groups couple | bonded together, a phenylene group and a heterocyclic group Each independently may be substituted with the same or different one or a plurality of substituents selected from alkyl, alkoxy, haloalkyl, haloalkoxy, halogen and cyano; The bond between each other is at least one selected from a single bond, an ester bond, an amide bond, a urea bond, an ether bond, a thioether bond, an amino bond, and carbonyl, and when the divalent group is plural, a divalent group is used. The bonds may be the same or different, and in the case where the bonds are plural, the bonds may be the same or different, R represents a hydrogen atom or a monovalent organic group, and two Rs may be different from each other, R may be combined to form alkylene having 1 to 6 carbon atoms, or both or one of two R's may be bonded to L ¹ .

2. wherein W ¹ represents a single bond, the liquid crystal alignment according to Claim 1.

3. Liquid crystal aligning agent as described in 1. or 2. whose said polymer is at least 1 sort (s) chosen from the polyimide precursor containing the structural unit represented by following formula (3), and the imide.

[Formula 2]

X ¹ represents a tetravalent organic group derived from a tetracarboxylic acid derivative, Y ¹ represents a divalent organic group derived from a diamine containing the structure of Formula (1), and R ⁴ represents a hydrogen atom or C 1-5 An alkyl group is shown.

4. Liquid crystal aligning agent as described in 3. whose structure of X <^1> shows at least 1 sort (s) chosen from the following structure in said Formula (3).

[Formula 3]

5. Liquid crystal aligning agent of 3. whose said polymer is at least 1 sort (s) chosen from polyimide precursor which further contains the structural unit represented by following formula (4), and its imide.

[Formula 4]

In Formula (4), X <^2> represents the tetravalent organic group derived from tetracarboxylic-acid derivative, Y <^2> represents the divalent organic group derived from diamine which does not contain the structure of Formula (1) in a principal chain direction. And R ¹⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ¹⁵ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

6. wherein Y ² is represented by the following formula (11), the liquid crystal alignment according to 5.

[Formula 5]

In formula (11), R ³² represents a single bond or a divalent organic group, R ³³ represents a structure represented _by- (CH ₂ ) _r- , r represents an integer of 2 to 10, and arbitrary -CH ₂ -may be substituted with ether, ester, amide, urea, carbamate bond on the condition that they are not adjacent to each other. R ³⁴ represents a single bond or a divalent organic group. Any hydrogen atom on a benzene ring may be substituted by monovalent organic group.

7. The liquid crystal aligning agent as described in 4. or 5. whose structural unit represented by the said Formula (3) is 10 mol% or more with respect to the whole structural unit of a polymer.

8. Liquid crystal aligning film which contains liquid crystal aligning agent in any one of 8. 1.-7.

The liquid crystal display element which comprises the liquid crystal aligning film of 9. 8 ..

10. Diamine which has a structure represented by following formula (1).

[Formula 6]

R <^1> represents a hydrogen atom, a C1-C5 linear or branched alkyl group, or an aryl group, and two R <^1> on the same maleimide ring may be mutually same, may differ, and two R <^1> is One may form alkylene having 3 to 6 carbon atoms, W ² represents a divalent organic group, W ¹ represents a single bond or carbonyl, and L ¹ represents a linear alkylene group having 1 to 20 carbon atoms and carbon number. The divalent group selected from a 3-20 branched alkylene group, a C3-C20 cyclic alkylene group, a phenylene group, and a heterocyclic group, or the group which the said bivalent group combines in multiple numbers is shown, A phenylene group and a heterocyclic group Each independently may be substituted with the same or different one or a plurality of substituents selected from an alkyl group, an alkoxy group, a haloalkyl group, a haloalkoxy group, a halogen group and a cyano group, and The bond between divalent groups is at least one selected from a single bond, an ester bond, an amide bond, a urea bond, an ether bond, a thioether bond, an amino bond, and carbonyl, and when the divalent groups are plural, The divalent groups may be the same or different, and in the case where the bonds are plural, the bonds may be the same or different, R represents a hydrogen atom or a monovalent organic group, and two R's may be different from each other, the two R, which is the one and may form an alkylene group having 1 to 6 carbon atoms, or may, and that both or either one of the two R, which joined to L ^1.

A polymer made using the diamine of 11. 10.

By using the liquid crystal aligning agent containing the polymer of this invention, while suppressing the ion density in a liquid crystal display element low, it is possible to quickly relieve the electric charge accumulated, and especially rubbing which becomes a problem in a transverse electric field drive system. The liquid crystal aligning film which can suppress the shift | offset | difference of the direction and the orientation direction of a liquid crystal is obtained. Although it is not clear why the said subject can be solved by this invention, it is generally considered as follows. The structure of the said Formula (1) contained in the polymer of this invention has a nitrogen atom. Thereby, for example, in a liquid crystal aligning film, while having the ability to replenish an ionic impurity, the movement of an electric charge can be accelerated | stimulated and relaxation of an accumulation electric charge can be promoted.

The liquid crystal aligning agent of this invention is a liquid crystal aligning agent containing the polymer (henceforth a specific polymer) obtained from the diamine which has a structure (henceforth a specific structure) represented by said Formula (1). Hereinafter, each condition is explained in full detail.

<Diamine having a Specific Structure>

In said formula (1), R <^1> represents a hydrogen atom, a C1-C5 linear or branched alkyl group, or an aryl group, and two R <^1> on the same maleimide ring may mutually be same or different. , Two R ¹ may be one to form a C 3-6 alkylene, W ² represents a divalent organic group, L ¹ represents a single bond or a C 1-20 alkylene, R is hydrogen An atom or a monovalent organic group is represented, two R's may be different from each other, two R's may be one to form an alkylene having 1 to 6 carbon atoms, or both or one of two R's is L ^You may couple to ¹ .

R ¹ is preferably a hydrogen atom, a methyl group, an ethyl group, an iso-propyl group, or a phenyl group, and more preferably a hydrogen atom, a methyl group, or a phenyl group. In addition, the two R ¹ on the alkylene having 3 to 6 carbon atoms which forms is the one, preferably _{- (CH 2) 3 -,} - (CH 2) 4 -, - (CH 2) 5 - and , More preferably-(CH ₂ ) _4- .

The alkylene group of 1 to 20 carbon atoms in the definition of L ¹ is, and may be a straight-chain minutes _{contribution, - (CH 2) n -} ( where, n is 1-20) alkylene of straight-chain or represented by, 1-methylmethane-1,1-diyl, 1-ethylmethane-1,1-diyl, 1-propylmethane-1,1-diyl, 1-methylethane-1,2-diyl, 1-ethylethane-1 , 2-diyl, 1-propylethane-1,2-diyl, 1-methylpropane-1,3-diyl, 1-ethylpropane-1,3-diyl, 1-propylpropane-1,3-diyl, 2 -Methyl propane-1,3-diyl, 2-ethylpropane-1,3-diyl, 2-propylpropane-1,3-diyl, 1-methylbutane-1,4-diyl, 1-ethylbutane-1, 4-diyl, 1-propylbutane-1,4-diyl, 2-methylbutane-1,4-diyl, 2-ethylbutane-1,4-diyl, 2-propylbutane-1,4-diyl, 1- Methylpentane-1,5-diyl, 1-ethylpentane-1,5-diyl, 1-propylpentane-1,5-diyl, 2-methylpentane-1,5-diyl, 2-ethylpentane-1,5 -Diyl, 2-propylpentane-1,5-diyl, 3-methylpentane-1,5-diyl, 3-ethylpentane-1,5-diyl, 3-propylpentane-1,5-diyl, 1-methyl Hexane-1,6- 1-ethylhexane-1,6-diyl, 2-methylhexane-1,6-diyl, 2-ethylhexane-1,6-diyl, 3-methylhexane-1,6-diyl, 3-ethylhexane -1,6-diyl, 1-methylheptan-1,7-diyl, 2-methylheptan-1,7-diyl, 3-methylheptan-1,7-diyl, 4-methylheptan-1,7-diyl And branched alkylenes such as 1-phenylmethane-1,1-diyl, 1-phenylethane-1,2-diyl, and 1-phenylpropane-1,3-diyl. These linear or branched alkylenes may be interrupted 1 to 5 times by an oxygen atom or a sulfur atom on the condition that oxygen atoms or sulfur atoms are not adjacent to each other.

As a C3-C20 branched alkylene group in the definition of L <^1> , For example, i-propylene group, i-butylene group, s-butylene group, t-butylene group, 1-methyl- n-butyl Ethylene group, 2-methyl-n-butylene group, 3-methyl-n-butylene group, 1,1-dimethyl-n-propylene group, 1,2-dimethyl-n-propylene group, 2,2-dimethyl-n- Propylene group, 1-ethyl-n-propylene group, 1-methyl-n-pentylene group, 2-methyl-n-pentylene group, 3-methyl-n-pentylene group, 4-methyl-n-pentylene group, 1, 1-dimethyl-n-butylene group, 1,2-dimethyl-n-butylene group, 1,3-dimethyl-n-butylene group, 2,2-dimethyl-n-butylene group, 2,3-dimethyl-n- Butylene group, 3,3-dimethyl-n-butylene group, 1-ethyl-n-butylene group, 2-ethyl-n-butylene group, 1,1,2-trimethyl-n-propylene group, 1,2,2 In addition to the -trimethyl-n-propylene group, the 1-ethyl-1-methyl-n-propylene group, the 1-ethyl-2-methyl-n-propylene group and the like, the carbon number is in the range of up to 20 and branched at an arbitrary point; And an alkylene group.

As a C3-C20 cyclic alkylene group in the definition of L <^1> , For example, monocyclic rings, such as a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, and a cyclooctylene group And polycyclic alkylene groups such as norbornylene group, tricyclodecylene group, tetracyclododecylene group, and adamantylene group.

As a substituent in the case where the benzene ring in the definition of L <^1> may be substituted by the substituent, Alkyl groups, such as a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group; Haloalkyl groups such as trifluoromethyl group; Alkoxy groups, such as a methoxy group and an ethoxy group; Halogen atoms such as iodine, bromine, chlorine and fluorine; Cyano group etc. are mentioned.

As R, Preferably, they are a hydrogen atom or a C1-C3 linear alkyl group, More preferably, they are a hydrogen atom or a methyl group. In addition, R may be a protecting group which causes a desorption reaction by heat to be replaced by a hydrogen atom, and does not desorb at room temperature from the viewpoint of storage stability of the liquid crystal aligning agent, and is preferably a protecting group that desorbs by heat of 80 ° C. or higher, more preferably. Preferably it is a protecting group which detach | desorbs by heat in 100 degreeC or more. Examples thereof include a 1,1-dimethyl-2-chloroethoxycarbonyl group, a 1,1-dimethyl-2-cyanoethoxycarbonyl group, and a tert-butoxycarbonyl group, and preferably a tert-butoxycarbonyl group.

In addition, the two R a is an alkylene group having 3 to 6 carbon atoms, which is formed in one, preferably _{-CH 2 -, - (CH 2} ) 2 -, - (CH 2) 3 -, - (CH 2 ) ₄ -,-(CH ₂ ) _5- , more preferably-(CH ₂ ) ₂ -or-(CH ₂ ) _3- . A divalent organic group roneun W ^2, to the same as represented by the formula [W ² -1] ~ formula [W ² -152].

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

[Formula 24]

Among them, from the viewpoint of compatibility between ion density suppression and liquid crystal alignment stability, W ² -7, W ² -20, W ² -21, W ² -23, W ² -26, W ² -39, and W ² -51 , W ² -52, W ² -53, W ² -54, W ² -55, W ² -59, W ² -60, W ² -61, W ² -64, W ² -65, W ² -67 , W ² -68, W ² -69, W ² -70, and W ² -71 are preferred.

<Method for Producing Specific Diamine>

Below, the method of obtaining the diamine mentioned above is demonstrated. Of the specific diamine represented by the formula (1) of the present invention, W ^1, a method of synthesizing the single bond of the diamine is not particularly limited, for example, nitro-maleimide compound, the following formula represented by the following formula (A) ( The method of reacting the diamino compound represented by B1) to obtain the aminonitro compound represented by following formula (C1), and reducing this is mentioned.

[Formula 25]

The definitions of R, R ¹ , L ¹ , W ^1, and W ² are the same as in the above formula (1).

It is preferable that it is 0.1 mol-1 mol with respect to 1 mol of the compound represented by Formula (A), and, as for the usage-amount of the compound represented by Formula (B1), it is more preferable that it is 0.4 mol-0.5 mol. By carrying out excess amount of the compound represented by Formula (A), reaction can be advanced smoothly and a by-product can be suppressed.

This reaction is preferably performed in a solvent. The solvent can be used without limitation as long as it is a solvent that does not react with each raw material. For example, aprotic polar organic solvents (DMF, DMSO, DMAc, NMP, etc.); Ethers (Et ₂ O, i-Pr ₂ O, TBME, CPME, THF, dioxane, etc.); Aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.); Aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin and the like); Halogen hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, dichloroethane and the like); Lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.); Nitriles (acetonitrile, propionitrile, butyronitrile, etc.); Etc. can be used. These solvents can be appropriately selected in consideration of the occurrence of reaction and the like, and can be used alone or in combination of two or more thereof. If necessary, the solvent may be dried using a suitable dehydrating agent or desiccant and used as a nonaqueous solvent.

Although the usage-amount (reaction concentration) of a solvent is not specifically limited, It is 0.1-100 mass times with respect to a bismaleimide compound. Preferably they are 0.5 mass times-30 mass times, More preferably, they are 1 mass times-10 mass times. Although reaction temperature is not specifically limited, It is the range from -100 degreeC to the boiling point of the solvent used, Preferably it is -50-150 degreeC. The reaction time is usually 0.05 hours to 350 hours, preferably 0.5 hours to 100 hours.

This reaction can be reacted in the presence of an inorganic base or an organic base, if necessary. As a base used for reaction, Inorganic bases, such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate; bases such as tert-butoxy sodium, tert-butoxy potassium, sodium hydride and potassium hydride; Amines such as trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, diisopropylethylamine, pyridine, quinoline and collidine can be used. Especially, triethylamine, pyridine, tert-butoxy sodium, tert-butoxy potassium, sodium hydride, potassium hydride, etc. are preferable. Although it does not specifically limit as a usage-amount of a base, It is 0.1 mass part-100 mass parts with respect to a bismaleimide compound. Preferably it is 0-30 mass times, More preferably, it is 0-10 mass times.

One embodiment of the compound (B1) is a compound represented by the following formula (B1-1) wherein L ¹ is a divalent organic group, R is a hydrogen atom, and W ¹ is a single bond.

[Formula 26]

R in Formula (B1-1) is a hydrogen atom or a monovalent organic group each independently, Preferably it is a hydrogen atom or a C1-C3 linear alkyl group. L ¹ in the compounds of the formula (B1-1) is, it may be a structure selected from wherein W ² -1 ~ W ² -152. Preferably, although it selects from the following structure, it is not limited to this.

[Formula 27]

In one embodiment of the compound (B1), L ¹ is a divalent organic group, W ¹ is a single bond, R is one to form an alkylene group, or both R are bonded to L ¹ . And a compound represented by the following Formula (B1-2).

[Formula 28]

As a compound of Formula (B1-2), Preferably, it is selected from the following structural formula.

[Formula 29]

One embodiment of the compound (B1) is represented by the following formula (B1-3) in which L ¹ is a divalent organic group, W ¹ is a single bond, and ^one of R is bonded to L ¹ to form a ring. Compound.

[Formula 30]

R in Formula (B1-3) is a hydrogen atom or a monovalent organic group each independently, Preferably it is a hydrogen atom or a C1-C3 linear alkyl group. As a compound of Formula (B1-3), Preferably, the following compound is mentioned.

[Formula 31]

Next, the conditions at the time of manufacturing the specific diamine represented by Formula (1) by reducing the compound represented by said Formula (C1) are described below. As a method of reduction of the compound represented by said Formula (C1), there exists a reduction reaction performed in the coexistence of Fe, Sn, Zn, these salts, and a proton. The amount of Fe, Sn, Zn and salts thereof used is preferably 1 to 100 equivalents, particularly preferably 3 to 50 equivalents based on the compound represented by the formula (1).

As the reaction solvent, any solvent may be used as long as it does not interfere with the target reaction under the reaction conditions. For example, water; Alcohol solvents such as methyl alcohol, ethyl alcohol and tert-butyl alcohol; Aprotic polar organic solvents such as dimethylformamide, dimethyl sulfoxide, dimethylacetamide, and N-methylpyrrolidone; Ethers such as diethyl ether, diisopropyl ether, tert-butylmethyl ether, cyclopentylmethyl ether, tetrahydrofuran and dioxane; Aliphatic hydrocarbons such as pentane, hexane, heptane and petroleum ether; Aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene and tetralin; halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride and dichloroethane; Lower fatty acid esters such as methyl acetate, ethyl acetate, butyl acetate and methyl propionate; Nitriles such as acetonitrile, propionitrile and butyronitrile can be used. These solvents can be appropriately selected in consideration of the occurrence of reaction and the like, and can be used alone or in combination of two or more thereof. In some cases, the solvent may be used as a solvent containing no water using a suitable dehydrating agent or desiccant. Although the usage-amount (reaction concentration) of a solvent is not specifically limited, It is 0.1 mass times-100 mass times with respect to the compound represented by said Formula (C1). Preferably they are 0.5 mass times-50 mass times, More preferably, they are 3 mass times-30 mass times.

Moreover, in order to advance reaction more effectively, you may carry out reaction under pressurization. In this case, in order to avoid the reduction of the benzene nucleus, the reaction is preferably performed in a pressurized range of about 20 atm (kgf), more preferably in a range up to 10 atm. In addition, acids such as hydrochloric acid, sulfuric acid, formic acid, acetic acid, and salts thereof may coexist. Although these usage-amount is not specifically limited, It is 0-10 mass times with respect to the compound represented by said Formula (C1). Preferably they are 0 mass times-5 mass times, More preferably, they are 0 mass times-3 mass times. Reaction temperature, Preferably, although the temperature range from the temperature of the boiling point of the reaction solvent to use from -100 degreeC or more can be selected, More preferably, it is -50 degreeC-150 degreeC, Especially preferably, it is 0 degreeC-100 ℃. The reaction time is 0.1 hour to 1000 hours, more preferably 1 hour to 200 hours. Moreover, as a method of reduction of the compound represented by said Formula (C1), a hydrogenation reaction using palladium-activated carbon, platinum-activated carbon, etc. as a catalyst, the reduction reaction which uses formic acid as a hydrogen source, and the reaction which uses hydrazine as a hydrogen source Etc. Moreover, these reaction can also be performed in combination.

The catalyst used for the reduction reaction is preferably an activated carbon supported metal that can be obtained as a commercially available product, and examples thereof include palladium-activated carbon, platinum-activated carbon, and rhodium-activated carbon. Moreover, it may not necessarily be an activated carbon supported metal catalyst, such as palladium hydroxide, platinum oxide, and Raney nickel. Palladium-activated carbon and platinum-activated carbon which are generally widely used are preferable because good results are obtained.

What is necessary is just what is called catalyst amount, Preferably it is 20 mol% or less with respect to the compound represented by said Formula (C1), Especially preferably, it is 10 mol% or less.

As the reaction solvent, any solvent may be used as long as it does not interfere with the target reaction under the reaction conditions. For example, Alcohol solvent, such as methyl alcohol, ethyl alcohol, tert- butyl alcohol; Aprotic polar organic solvents such as dimethylformamide, dimethyl sulfoxide, dimethylacetamide, and N-methylpyrrolidone; Ethers such as diethyl ether, isopropyl ether, tert-butylmethyl ether, cyclopentylmethyl ether, tetrahydrofuran and dioxane; Aliphatic hydrocarbons such as pentane, hexane, heptane and petroleum ether; Aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene and tetralin; halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride and dichloroethane; Lower fatty acid esters such as methyl acetate, ethyl acetate, butyl acetate and methyl propionate; Nitriles such as acetonitrile, propionitrile and butyronitrile can be used. These solvents can be appropriately selected in consideration of the occurrence of reaction and the like, and can be used alone or in combination of two or more thereof. In some cases, the solvent may be used as a solvent containing no water using a suitable dehydrating agent or desiccant. Although the usage-amount (reaction concentration) of a solvent is not specifically limited, It is 0.1 mass times-100 mass times with respect to the compound represented by said Formula (C1). Preferably they are 0.5 mass times-50 mass times, More preferably, they are 3 mass times-30 mass times. Although reaction temperature is not specifically limited, It is the range from -100 degreeC to the boiling point of the solvent used, Preferably it is -50 degreeC-150 degreeC. The reaction time is usually 0.05 hours to 350 hours, preferably 0.5 hours to 100 hours.

In order to advance reduction reaction more effectively, reaction may be performed in the presence of activated carbon. Although the quantity of the activated carbon to be used at this time is not specifically limited, The range of 1 mass%-30 mass% is preferable with respect to dinitro compound C1, and 10 mass%-20 mass% are more preferable. For the same reason, the reaction may be performed under pressure. In this case, in order to avoid the reduction of a benzene nucleus, it implements in the pressurization range up to 20 atmospheres. Preferably, reaction is performed in the range up to 10 atmospheres. Of the reduction reactions exemplified above, in consideration of the structure of the compound represented by the formula (C1) and the reactivity of the reduction reaction, the use of a hydrogenation reaction is preferred.

When introducing monovalent organic group as R, what is necessary is just to make the compound whose R is a hydrogen atom in the dinitro compound represented by said Formula (C1) react with the compound which can react with amines. Examples of such compounds include acid halides, acid anhydrides, isocyanates, epoxies, oxetanes, aryl halides and alkyl halides, and the hydroxyl groups of the alcohols are OMs, OTf, OTs and the like. Alcohols substituted with a leaving group can be used.

Although there is no restriction | limiting in particular in the method of introduce | transducing monovalent organic group into NH group, The method of making an acid halide react in presence of a suitable base is mentioned. Examples of acid halides include acetyl chloride, propionic acid chloride, methyl chloroformate, ethyl chloroformate, chloroformate n-propyl, chloroformate i-propyl, chloroformate n-butyl, chloroformate i-butyl, chloroformate t-butyl, Chloroformate benzyl and chloroformate-9-fluorenyl. Examples of the base may use the base described above. Reaction solvent and reaction temperature are based on said description.

An acid anhydride may be made to react with NH group, and a monovalent organic group may be introduce | transduced, and examples of an acid anhydride include acetic anhydride, propionic anhydride, dimethyl bicarbonate, diethyl bicarbonate, dibutyl dicarbonate, dibenzyl bicarbonate, and the like. In order to accelerate the reaction, a catalyst may be added or pyridine, collidine, N, N-dimethyl-4-aminopyridine, or the like may be used. The catalytic amount is 0.0001 mol-1 mol with respect to 1 mol of the compound whose R is a hydrogen atom in the dinitro compound represented by said Formula (C1). Reaction solvent and reaction temperature are based on said description.

Isocyanates may be made to react with NH group, and monovalent organic group may be introduce | transduced, and an example of isocyanate is methyl isocyanate, ethyl isocyanate, n-propyl isocyanate, phenyl isocyanate, etc. are mentioned. Reaction solvent and reaction temperature are based on said description.

Epoxy compounds or oxetane compounds may be reacted with NH groups to introduce monovalent organic groups, and examples of the epoxy and oxetanes include ethylene oxide, propylene oxide, 1,2-butylene oxide, trimethylene oxide and the like. Can be. Reaction solvent and reaction temperature are based on said description.

In the presence of a metal catalyst, a ligand, and a base, a halogenated aryl may be reacted with the NH group to introduce a monovalent organic group. Examples of the aryl halide include iodinebenzene, bromobenzene, and chlorobenzene. Examples of metal catalysts include palladium acetate, palladium chloride, palladium chloride-acetonitrile complexes, palladium-activated carbon, bis (dibenzilideneacetone) palladium, tris (dibenzilideneacetone) dipalladium, bis (acetonitrile) dichloropalladium, Although bis (benzonitrile) dichloro palladium, CuCl, CuBr, CuI, CuCN, etc. are mentioned, It is not limited to these. Examples of ligands include triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenyl Phosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,1'-bis (diphenylphosphino) ferrocene, trimethylphosphite, triethylphosphite, triphenylphosphite, tri-tert- Butyl phosphine etc. are mentioned, It is not limited to these. Examples of the base may use the base described above. Reaction solvent and reaction temperature are based on said description.

Alcohols in which the hydroxyl group of the alcohol is substituted with a leaving group such as OMs, OTf, or OTs in the presence of a suitable base to the NH group may be reacted to introduce a monovalent organic group. Examples of the alcohols include methanol, ethanol, 1-propanol, and the like. These alcohols can be reacted with methanesulfonyl chloride, trifluoromethanesulfonyl chloride, paratoluenesulfonic acid chloride and the like to obtain alcohols substituted with leaving groups such as OMs, OTf and OTs. Examples of the base may use the base described above. Reaction solvent and reaction temperature are based on said description.

Monovalent organic groups may be introduced by reacting alkyl halides in the presence of a suitable base in the NH group. Examples of alkyl halides include methyl iodide, ethyl iodide, n-propyl iodide, methyl bromide, ethyl bromide, and n-propyl bromide. Can be mentioned. As an example of a base, in addition to the base mentioned above, metal alkoxides, such as potassium-tert-butoxide and sodium-tert-butoxide, can be used. Reaction conditions, such as a reaction solvent, reaction temperature, and reaction time, are based on said description.

The usage-amount of the compound which can react with said amine can be made into about 1.0 molar equivalent-about 3.0 molar equivalent with respect to 1.0 molar equivalent of the compound whose R is a hydrogen atom in the dinitro compound represented by said Formula (C). Preferably the range of 2.0 molar equivalents-2.5 molar equivalents is preferable. In addition, the compound which can react with said amine can be used individually or in combination. In addition, when the isomer derived from a subsidiary point exists in the diamine compound represented by Formula (1), in this application, each isomer and its mixture shall be contained in the diamine represented by Formula (1). In addition, when two R <^1> in the same maleimide ring of Formula (1) differs from each other, the substitution position of R <^1> differs in the diamine compound represented by Formula (1), In this application, neither isomers nor mixtures thereof All shall be contained in the diamine represented by Formula (1).

[Production method of formula (A)]

Although there is no restriction | limiting in particular in the method of synthesize | combining the compound of Formula (A), For example, the method of making maleic anhydride derivative react with commercially available nitroamine represented by following formula (D) is mentioned.

[Formula 32]

It is preferable that it is 1 mol-1.5 mol with respect to 1 mol of the nitroamine compound represented by Formula (D), and, as for the usage-amount of a maleic anhydride derivative, it is more preferable that it is 1 mol-1.2 mol. By making maleic anhydride an excess, reaction can be advanced smoothly and a by-product can be suppressed. This reaction is preferably performed in a solvent. Preferable solvent and reaction conditions are the same as the manufacturing conditions of the said compound (1). Moreover, as a method of synthesize | combining the diamine whose W <^1> is a single bond among the specific diamine represented by Formula (1) of this invention, the amino maleimide compound represented by following formula (E) and said Formula (B1-1) The method of making the diamino compound shown react is also mentioned.

[Formula 33]

The definitions of R, R ¹ , L ^1, and W ² are the same as in the above formula (1). It is preferable that it is 0.1 mol-1 mol with respect to 1 mol of the compound represented by Formula (E), and, as for the usage-amount of the compound represented by Formula (B1-1), it is more preferable that it is 0.4 mol-0.5 mol. By carrying out excess amount of the compound represented by Formula (E), reaction can be advanced smoothly and a by-product can be suppressed.

This reaction is preferably performed in a solvent. The solvent can be used without limitation as long as it is a solvent that does not react with each raw material. For example, aprotic polar organic solvents (DMF, DMSO, DMAc, NMP, etc.); Ethers (Et ₂ O, i-Pr ₂ O, TBME, CPME, THF, dioxane, etc.); Aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.); Aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin and the like); Halogen hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, dichloroethane and the like); Lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.); Nitriles (acetonitrile, propionitrile, butyronitrile, etc.); Etc. can be used. These solvents can be appropriately selected in consideration of the occurrence of reaction and the like, and can be used alone or in combination of two or more thereof. If necessary, the solvent may be dried using a suitable dehydrating agent or desiccant and used as a nonaqueous solvent. Although the usage-amount (reaction concentration) of a solvent is not specifically limited, It is 0.1 mass times-100 mass times with respect to a bismaleimide compound. Preferably they are 0.5 mass times-30 mass times, More preferably, they are 1 mass times-10 mass times. Although reaction temperature is not specifically limited, It is the range from -100 degreeC to the boiling point of the solvent used, Preferably it is -50 degreeC-150 degreeC. The reaction time is usually 0.05 hours to 350 hours, preferably 0.5 hours to 100 hours.

This reaction can be reacted in the presence of an inorganic base or an organic base, if necessary.

As a base used for reaction, Inorganic bases, such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate; bases such as tert-butoxy sodium, tert-butoxy potassium, sodium hydride and potassium hydride; Amines such as trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, diisopropylethylamine, pyridine, quinoline and collidine can be used. Especially, triethylamine, pyridine, tert-butoxy sodium, tert-butoxy potassium, sodium hydride, potassium hydride, etc. are preferable. Although it does not specifically limit as a usage-amount of a base, It is 0.1 mass times-100 mass times with respect to a bismaleimide compound. Preferably it is 0-30 mass times, More preferably, it is 0-10 mass times.

[Manufacturing Formula (E)]

Although there is no restriction | limiting in particular in the method of synthesize | combining the compound of Formula (E), For example, maleic anhydride derivative in the diamine represented by following formula (F) under the conditions of Unexamined-Japanese-Patent No. 2003-321531, WO2004012735, etc. The method of making it react is mentioned.

[Formula 34]

It is preferable that it is 0.01 mol-1 mol with respect to 1 mol of the diamine compound represented by Formula (F), and, as for the usage-amount of a maleic anhydride derivative, it is more preferable that it is 0.1 mol-1.0 mol. By carrying out excess amount of diamine (F), reaction can be advanced smoothly and a by-product can be suppressed. This reaction is preferably performed in a solvent. Preferable solvent and reaction conditions are the same as the manufacturing conditions of the said compound (1). Moreover, the method of carrying out metal contact reduction of the diamine represented by following formula (A) is also mentioned.

[Formula 35]

This reaction is based on the method of reducing the said compound (C1) and manufacturing the specific diamine represented by Formula (1). In the reduction reaction, in consideration of the structure of the compound represented by the formula (A) and the reactivity of the reduction reaction, a reduction reaction carried out in the coexistence of Fe, Sn, Zn, salts thereof, and protons is preferable.

Although the method of synthesize | combining the diamine whose W <^1> is carbonyl among the specific diamine represented by Formula (1) of this invention is not specifically limited, For example, to the nitromaleimide compound represented by said formula (A), it is a following formula ( After reacting the amine represented by B2) and obtaining the compound represented by following formula (G), it is made to react with the dicarboxylic acid represented by following formula (H), and the dinitro compound represented by following formula (C2) is obtained, and this is reduced. A method is mentioned.

[Formula 36]

The definitions of R, R ¹ , L ^1, and W ² are the same as in the above formula (1).

In addition, expression of the desired L ¹ (H) and the equation (C2) is the same as the preferred L ¹ in the formula (B1-1). The reaction conditions of the compound represented by the formula (B2) and the compound represented by the formula (A) correspond to the reaction conditions of the compound represented by the formula (B1) and the compound represented by the formula (A).

By reacting a compound represented by the formula (G) and a compound in which Z is OH in the formula (H), if necessary, using a solvent inert to the reaction, in the presence of a base, if necessary, using a condensing agent. And the compound represented by general formula (C2) can be obtained.

As for the quantity of a reaction substrate, the compound whose Z is OH in 0.4 equivalent-0.8 equivalent of General formula (H) with respect to 1 equivalent of compound represented by Formula (G) can be used.

The condensing agent is not particularly limited as long as it is used for conventional amide synthesis. For example, mukaiyama reagent (2-chloro-N-methylpyridinium iodide) and DCC (1,3-dicyclohexylcarbodiimide ), WSC (1-ethyl-3- (3-dimethylaminopropyl) -carbodiimide hydrochloride), CDI (carbonyldiimidazole), dimethylpropynylsulfonium bromide, propargyltriphenylphosphonium bromide, DEPC ( Diethyl cyanophosphate) and the like can be used in the amount of 1 to 4 equivalents based on the compound in which Z is OH in the formula (H).

When using a solvent, there will be no restriction | limiting in particular if the solvent used does not inhibit the progress of reaction, For example, aromatic hydrocarbons, such as benzene, toluene, xylene, aliphatic hydrocarbons, such as hexane and heptane, cyclohexane Alicyclic hydrocarbons such as chlorobenzene, aromatic halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,1-trichloroethane, trichloroethylene, tetrachloroethylene Ethers such as aliphatic halogenated hydrocarbons, diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran, 1,4-dioxane, esters such as ethyl acetate and ethyl propionate, and N, N-dimethylform Amides such as amide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, amines such as triethylamine, tributylamine, N, N-dimethylaniline, pyridine and picoline And the like, acetonitrile, dimethyl sulfoxide and the like. These solvents may be used alone, or two or more thereof may be mixed and used.

Although addition of a base is not necessarily necessary, When using a base, For example, Alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide, Alkali metal carbonates, such as sodium carbonate and potassium carbonate, Alkali metals, such as sodium hydrogencarbonate and potassium hydrogencarbonate Bicarbonate, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, 4- (dimethylamino) pyridine, imidazole, 1,8-diazabicyclo [5,4,0] -7-undecene and the like The organic base of may be used in the amount of 1 to 4 equivalents based on the compound where Z is OH in the formula (H).

The reaction temperature can be set at any temperature from -60 ° C to the reflux temperature of the reaction mixture, and the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but is usually set arbitrarily within the range of 5 minutes to 100 hours. Can be.

Generally, 0.4 equivalent-0.8 equivalent of the compound whose Z is OH in said Formula (H) with respect to 1 equivalent of the compound represented by said Formula (G), and 1 equivalent-4 equivalents of WSC (1-ethyl-), for example. Using condensing agents such as 3- (3-dimethylaminopropyl) -carbodiimide hydrochloride) and CDI (carbonyldiimidazole), if necessary, 1 to 4 equivalents of potassium carbonate, triethylamine, pyridine, 4- In the presence of a base such as (dimethylamino) pyridine, it is a solvent-free or a solvent such as dichloromethane, chloroform, diethyl ether, tetrahydrofuran, 1,4-dioxane, etc. In the range, it is preferable to carry out the reaction for 10 minutes to 24 hours.

Further, in the above formula (H), a known method described in the literature from a compound in which Z is OH, for example, a reaction with a chlorinating agent such as thionyl chloride, phosphorus pentachloride or oxalyl chloride, pivaloyl chloride or chlor Formula (H) which can be synthesized using a method of reacting an organic acid halide such as isobutyl formate with a base, if necessary, in the presence of a base, or a method of reacting with carbonyldiimidazole or sulfonyldiimidazole or the like. ), A compound represented by the general formula (C2) by reacting the compound represented by the formula (G) with Z in the above-mentioned formula (G), if necessary, by using a solvent inert to the reaction and, if necessary, in the presence of a base. Can also be synthesized. As for the quantity of a reaction substrate, the compound whose Z is Cl in 0.4 equivalent-0.8 equivalent of General formula (H) with respect to 1 equivalent of compound represented by Formula (G) can be used.

When using a solvent, there will be no restriction | limiting in particular if the solvent used does not inhibit the progress of reaction, For example, aromatic hydrocarbons, such as benzene, toluene, xylene, aliphatic hydrocarbons, such as hexane and heptane, cyclohexane Alicyclic hydrocarbons such as chlorobenzene, aromatic halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,1-trichloroethane, trichloroethylene, tetrachloroethylene Ethers such as aliphatic halogenated hydrocarbons, diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran and 1,4-dioxane, esters such as ethyl acetate and ethyl propionate, and N, N-dimethylform Amides such as amide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, amines such as triethylamine, tributylamine, N, N-dimethylaniline, pyridine and picoline And the like, acetonitrile and water. These solvents may be used alone, or two or more thereof may be mixed and used.

Although addition of a base is not necessarily necessary, When using a base, For example, Alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide, Alkali metal carbonates, such as sodium carbonate and potassium carbonate, Alkali metals, such as sodium hydrogencarbonate and potassium hydrogencarbonate Bicarbonate, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, 4- (dimethylamino) pyridine, imidazole, 1,8-diazabicyclo [5,4,0] -7-undecene and the like The organic base of may be used in the amount of 1 to 4 equivalents based on the compound where Z is Cl in the formula (H). The reaction temperature can be set at any temperature from -60 ° C to the reflux temperature of the reaction mixture, and the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but is usually set arbitrarily within the range of 5 minutes to 100 hours. Can be.

Generally, 1 equivalent-2 equivalents of potassium carbonate, tri, if necessary, is a compound whose Z is Cl in 0.4 equivalent-0.8 equivalent of General formula (H) with respect to 1 equivalent of the compound represented by Formula (G), for example. In the presence of a base such as ethylamine, pyridine or 4- (dimethylamino) pyridine, solvents such as solvent-free or dichloromethane, chloroform, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethyl acetate, acetonitrile It is preferable to perform reaction for 10 minutes-48 hours in the range of 0 degreeC-the reflux temperature of these solvent using. In addition, the reaction conditions at the time of reducing the dinitro compound represented by Formula (C2) to obtain the diamine represented by Formula (1) are the same conditions as the above.

The target object in each step obtained by each of the above reactions may be purified by column chromatography such as distillation, recrystallization, silica gel or the like, or may be provided to the next step without being purified.

<Polymer>

The polymer of this invention is a polymer obtained using the said diamine. As a specific example, polyamic acid, polyamic acid ester, polyimide, polyurea, polyamide, etc. are mentioned, The polyimide precursor containing the structural unit represented by following formula (3) from a viewpoint of use as a liquid crystal aligning agent. And at least one paper selected from polyimides which are imides thereof.

[Formula 37]

In the formula (3), X ¹ is a tetravalent organic group derived from a tetracarboxylic acid derivative, Y ¹ is a divalent organic group derived from a diamine containing the structure of formula (1), and R ⁴ is It is a hydrogen atom or a C1-C5 alkyl group. R ⁴ is preferably a hydrogen atom, a methyl group or an ethyl group in view of ease of imidization by heating.

<Tetracarboxylic dianhydride>

X ¹ is a tetravalent organic group derived from a tetracarboxylic acid derivative, and the structure is not particularly limited. In addition, X <^1> in a polyimide precursor is the grade of the characteristic which is required, such as the solubility to the solvent of a polymer, the coating property of a liquid crystal aligning agent, the orientation of a liquid crystal in the case of using a liquid crystal aligning film, voltage retention, and an accumulated charge. It selects accordingly and one type may be sufficient in the same polymer, and 2 or more types may be mixed.

When the specific example of X <^1> is shown daringly, the structure of Formula (X-1)-(X-46) etc. which are published on pages 13-14 of International Publication 2015/119168 are mentioned. Although the structure of preferable X <^1> is shown below, this invention is not limited to these.

[Formula 38]

Among the structures described above, (A-1) and (A-2) are particularly preferable from the viewpoint of further improving the rubbing resistance, (A-4) is particularly preferred from the viewpoint of further improving the relaxation rate of the accumulated charge, (A-15)-(A-17) etc. are especially preferable from a viewpoint of further improvement of the liquid crystal aligning property and the relaxation rate of an accumulation charge.

<Polymer (Other Structural Unit)>

The polyimide precursor containing the structural unit represented by Formula (3) is at least chosen from the polyimide which is a structural unit represented by following formula (4), and its imide in the range which does not impair the effect of this invention. One kind may be included.

[Formula 39]

In the formula (4), X ² is a tetracarboxylic acid is a tetravalent organic group derived from a derivative thereof, Y ² is a divalent organic group derived from a diamine that does not include the structure of formula (1) in the main chain direction And R ¹⁴ have the same definitions as R ⁴ in the formula (3), and R ¹⁵ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

As a specific example of X <^2> , the same structure as what was illustrated by X <^1> of Formula (3) including a preferable example is mentioned. In addition, Y <^2> in a polyimide precursor is a divalent organic group derived from diamine which does not contain the structure of Formula (1) in a principal chain direction, The structure is not specifically limited. Further, Y ² is selected appropriately depending on the degree of the characteristic that orientation, voltage holding ratio, accumulated charges, etc., required of the liquid crystal in a case where the solubility and the coating of the liquid crystal aligning agent property, the liquid crystal alignment film in a solvent of the polymer, 1 type may be sufficient as the same polymer, and 2 or more types may be mixed.

Represents a specific example of Y ² dare, there may be mentioned groups represented by the formula [W ² -1] ~ formula [W ² -152]. In addition, the structure of Formula (2) published on page 4 of International Publication 2015/119168, and Formula (Y-1)-(Y-97), (Y-101) published on pages 8-12. Structure of (Y-118); A divalent organic group excluding two amino groups from formula (2) published on page 6 of International Publication No. 2013/008906; A divalent organic group excluding two amino groups from formula (1) published on page 8 of International Publication No. 2015/122413; The structure of equation (3) as published on page 8 of International Publication No. 2015/060360; Bivalent organic group except two amino groups from Formula (1) described on page 8 of Unexamined-Japanese-Patent No. 2012-173514; Divalent organic groups remove | excluding two amino groups from formula (A)-(F) published on page 9 of international publication 2010/050523, etc. are mentioned.

A preferred structure of Y ^2, there may be mentioned a structure of the formula (11).

[Formula 40]

In Formula (11), R ³² is a single bond or a divalent organic group, and a single bond is preferable. R ³³ is a structure represented _by- (CH ₂ ) _r- . r is an integer of 2-10 and 3-7 are preferable. In addition, arbitrary —CH ₂ — may be substituted with ether, ester, amide, urea, carbamate bond on the condition that they are not adjacent to each other. R ³⁴ is a single bond or a divalent organic group. Any hydrogen atom on a benzene ring may be substituted by monovalent organic group, and a fluorine atom or a methyl group is preferable. Although the following structures are mentioned specifically as a structure represented by Formula (11), It is not limited to these.

[Formula 41]

[Formula 42]

[Formula 43]

[Formula 44]

[Formula 45]

When the polyimide precursor containing the structural unit represented by Formula (3) simultaneously contains the structural unit represented by Formula (4), while it loosens | stores the accumulated electric charge quickly, the shift | offset | difference of the rubbing direction and the orientation direction of a liquid crystal is carried out. From a viewpoint of controlling, it is preferable that the structural unit represented by Formula (3) is 1 mol%-80 mol% with respect to the sum total of Formula (3) and Formula (4), More preferably, it is 5 mol%-60 mol. %, Especially preferably, it is 10 mol%-40 mol%. Moreover, as a preferable structure of Y <^2>, the structure which has at least 1 sort (s) chosen from the group which consists of an amino group, an imino group, and a nitrogen-containing heterocyclic ring is mentioned.

Such a structure of Y ² includes an amino group, an imino group, and a monomer having at least one kind selected from the group consisting of an amino group, an imino group, and a nitrogen-containing heterocyclic ring, or a thermally leaving group substituted on a nitrogen atom. If it has at least 1 sort (s) of structure chosen from nitrogen heterocycle, the structure is not specifically limited. As a specific example, a divalent organic group having at least one kind of structure selected from the group consisting of an amino group, an imino group, and a nitrogen-containing heterocyclic ring represented by the following formulas (YD-1) to (YD-5) Can be mentioned.

[Formula 46]

In formula (YD-1), A <_1> is a C3-C15 nitrogen atom containing heterocyclic ring, and Z <_1> is a C1-C20 hydrocarbon group which may have a hydrogen atom or a substituent. In Formula (YD-2), V <_1> is a C1-C10 hydrocarbon group, A <_2> is a C3-C15 monovalent organic group which has a nitrogen atom containing heterocyclic ring, or a C1-C6 aliphatic group Substituted di-substituted amino groups. In the formula (YD-3), V ₂ has a carbon number of 6 to 15, and also a divalent organic group having one or two benzene rings, V ₃ is alkylene or a biphenylene of a carbon number of 2 ~ 5, Z ₂ is a hydrogen atom, a C1-C5 alkyl group, a benzene ring, or a heat leaving group, and a is an integer of 0-1. In formula (YD-4), A <_3> is a C3-C15 nitrogen atom containing heterocyclic ring. In formula (YD-5), A <_4> is a C3-C15 nitrogen atom containing heterocyclic ring, V <_5> is C2-C5 alkylene.)

As a C3-C15 nitrogen atom containing heterocyclic ring of Formula (YD-1), (YD-2), (YD-4), and (YD-5) A <_1> , A <_2> , A <_3> , and A <_4> If it is a well-known structure, it will not specifically limit. Among them, pyrrolidine, pyrrole, imidazole, pyrazole, oxazole, thiazole, piperidine, piperazine, pyridine, pyrazine, indole, benzimidazole, quinoline, isoquinoline, piperazine, Piperidine, indole, benzimidazole, imidazole, carbazole, and pyridine are more preferred. In addition, what is necessary is just a substituent which detach | desorbs at the time of baking a oriented film, and is substituted by a hydrogen atom, without thermally leaving group at room temperature, and a tert- butoxycarbonyl group and 9-fluorenyl methoxycarbonyl group are mentioned specifically ,.

Since this Specific examples of such Y ² is, there may be mentioned the following formula (YD-6) ~ (YD -52) with a divalent organic group having a nitrogen atom represented, can suppress charge accumulation by the alternating current drive, Formulas (YD-14) to (YD-21) are more preferable, and (YD-14) and (YD-18) are particularly preferable.

[Formula 47]

J is an integer of 0-3 in a formula (YD-14) and (YD-21).

[Formula 48]

J is an integer of 0-3 in a formula (YD-24), (YD-25), (YD-28), and (YD-29).

[Formula 49]

[Formula 50]

[Formula 51]

[Formula 52]

(M and n are integers of 1-11, respectively, and m + n is an integer of 2-12 in a formula (YD-50).)

<Method for producing polyamic acid>

The polyamic acid which is a polyimide precursor used for this invention can be synthesize | combined by the method shown below. Specifically, tetracarboxylic dianhydride and diamine are in the presence of an organic solvent at -20 ° C to 150 ° C, preferably at 0 ° C to 70 ° C, for 30 minutes to 24 hours, preferably for 1 hour to 12 hours. It can synthesize | combine by making it react. As for the organic solvent used for said reaction, N, N- dimethylformamide, N-methyl- 2-pyrrolidone, (gamma) -butyrolactone, etc. are preferable from the solubility of a monomer and a polymer, These are 1 type or 2 types You may mix and use the above.

The concentration of the polymer is preferably 1% by mass to 30% by mass, more preferably 5% by mass to 20% by mass, from the viewpoint that the precipitation of the polymer does not occur well and the high molecular weight is easily obtained. The polyamic acid obtained as mentioned above can be precipitated and collect | recovered by inject | pouring into a poor solvent, stirring a reaction solution well. In addition, the precipitate can be subjected to several times, and after washing with a poor solvent, the powder of purified polyamic acid can be obtained by normal temperature or heat drying. The poor solvent is not particularly limited, but water, methanol, ethanol, 2-propanol, hexane, butyl cellosolve, acetone, toluene and the like can be given, and water, methanol, ethanol, 2-propanol and the like are preferable.

<Method for producing polyimide>

The polyimide used for this invention can be manufactured by imidating the said polyamic acid. When producing a polyimide from a polyamic acid, chemical imidation which adds a catalyst to the solution of the said polyamic acid obtained by reaction of a diamine component and tetracarboxylic dianhydride is easy. Chemical imidation is preferable since the imidation reaction advances at a comparatively low temperature, and molecular weight fall of a polymer does not occur easily in the process of imidation. Chemical imidation can be performed by stirring the polymer to make it imidate in presence of a basic catalyst and an acid anhydride in an organic solvent. As an organic solvent, the solvent used at the time of the polymerization reaction mentioned above can be used. Pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc. are mentioned as a basic catalyst. Especially, pyridine is preferable because it has a basicity suitable for advancing reaction. Moreover, acetic anhydride, trimellitic anhydride, a pyromellitic dianhydride, etc. are mentioned as an acid anhydride, Especially, since acetic anhydride is used, since refinement | purification after completion | finish of reaction becomes easy, it is preferable.

The temperature at the time of performing an imidation reaction is -20 degreeC-140 degreeC, Preferably it is 0 degreeC-100 degreeC, and reaction time can be implemented in 1 hour-100 hours. The amount of the basic catalyst is 0.5 to 30 times mole, preferably 2 to 20 times mole of the polyamic acid group, and the amount of the acid anhydride is 1 to 50 times mole, preferably 3 times mole of the polyamic acid group. It is-30 times mole. The imidation ratio of the polymer obtained can be controlled by adjusting catalyst amount, temperature, and reaction time. Since the added catalyst etc. remain in the solution after the imidation reaction of a polyamic acid, the imidation polymer obtained is collect | recovered by the means described below, it is redissolved with an organic solvent, and it is set as the liquid crystal aligning agent of this invention. It is preferable.

The polymer of the polyimide obtained as mentioned above can be precipitated by inject | pouring into a poor solvent, stirring well. Precipitation is carried out several times, followed by washing with a poor solvent, followed by normal temperature or heat drying to obtain a powder of a purified polymer. Although the said poor solvent is not specifically limited, Methanol, 2-propanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, etc. are mentioned, methanol, ethanol, etc. are mentioned. , 2-propanol, acetone and the like are preferable.

<Production of Polyimide Precursor-Polyamic Acid Ester>

The polyamic acid ester which is a polyimide precursor used for this invention can be manufactured by the manufacturing method of (1), (2) or (3) shown below.

(1) When manufactured from polyamic acid

Polyamic acid ester can be manufactured by esterifying the polyamic acid manufactured as mentioned above. Specifically, the polyamic acid and the esterifying agent are reacted in the presence of an organic solvent at -20 ° C to 150 ° C, preferably at 0 ° C to 50 ° C for 30 minutes to 24 hours, preferably 1 hour to 4 hours. It can manufacture. As an esterification agent, what can be easily removed by refinement | purification is preferable, N, N- dimethylformamide dimethyl acetal, N, N- dimethylformamide diethyl acetal, N, N- dimethylformamide dipropyl acetal, N, N-dimethylformamide dineopentylbutyl acetal, N, N-dimethylformamide di-t-butylacetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene , 1-propyl-3-p-tolyltriazene, 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride, and the like. As for the addition amount of an esterifying agent, 2 mol equivalent-6 mol equivalent are preferable with respect to 1 mol of repeating units of a polyamic acid.

As the organic solvent, for example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide , Dimethyl sulfoxide or 1,3-dimethyl-imidazolidinone. In addition, when the solvent solubility of a polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl- 2-pentanone, or the following formula [D-1]-a formula The solvent shown by [D-3] can be used. These solvents may be used alone or in combination. Moreover, even if it is a solvent which does not melt a polyimide precursor, you may mix and use it with the said solvent in the range which does not precipitate the produced polyimide precursor. In addition, since water in a solvent inhibits a polymerization reaction and further causes hydrolysis of the produced polyimide precursor, it is preferable to use what dried the solvent for dehydration.

As the solvent used for the above reaction, N, N-dimethylformamide, N-methyl-2-pyrrolidone, or γ-butyrolactone are preferable from the solubility of the polymer, and these are mixed one or two or more. May be used. 1 mass%-30 mass% are preferable, and, as for the density | concentration at the time of precipitation, a polymer does not generate | occur | produce well and it is easy to obtain a high molecular weight body, 5 mass%-20 mass% are more preferable.

(2) When manufactured by reaction of tetracarboxylic acid diester dichloride and diamine

Polyamic acid ester can be manufactured from tetracarboxylic-acid diester dichloride and diamine. Specifically, tetracarboxylic acid diester dichloride and diamine are present in the presence of a base and an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C, for 30 minutes to 24 hours, preferably 1 hour. It can manufacture by making it react for 4 hours. Pyridine, triethylamine, 4-dimethylaminopyridine and the like can be used for the base, but pyridine is preferable because the reaction proceeds mildly. The amount of base added is an amount that is easy to remove, and from the viewpoint of easily obtaining a high molecular weight body, the amount of the base is preferably 2 moles to 4 moles with respect to tetracarboxylic acid diester dichloride.

As for the solvent used for said reaction, N-methyl- 2-pyrrolidone or (gamma) -butyrolactone is preferable from the solubility of a monomer and a polymer, These may be used 1 type or in mixture of 2 or more types. 1 mass%-30 mass% are preferable, and, as for the polymer concentration at the time of precipitation, a polymer does not generate | occur | produce well and it is easy to obtain a high molecular weight body, 5 mass%-20 mass% are more preferable. In addition, in order to prevent hydrolysis of tetracarboxylic-acid diester dichloride, it is preferable that the solvent used for manufacture of a polyamic acid ester is dehydrated as much as possible, and it is preferable to prevent mixing of external air in nitrogen atmosphere.

(3) When manufactured from tetracarboxylic acid diester and diamine

Polyamic acid ester can be manufactured by polycondensing tetracarboxylic-acid diester and diamine. Specifically, tetracarboxylic acid diester and diamine in the presence of a condensing agent, a base, and an organic solvent at 0 ° C to 150 ° C, preferably 0 ° C to 100 ° C, 30 minutes to 24 hours, preferably 3 It can manufacture by making it react for 15 to 15 hours.

Examples of the condensing agent include triphenyl phosphite, dicyclohexyl carbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N'-carbonyldiimidazole, and dimethoxy-1 , 3,5-triazinylmethylmorpholinium, O- (benzotriazol-1-yl) -N, N, N ', N'-tetramethyluronium tetrafluoroborate, O- (benzotriazole- 1-yl) -N, N, N ', N'-tetramethyluronium hexafluorophosphite, (2,3-dihydro-2-thioxo-3-benzooxazolyl) phosphonic acid diphenyl and the like Can be used. As for the addition amount of a condensing agent, 2 times mole-3 times mole are preferable with respect to tetracarboxylic-acid diester.

As the base, tertiary amines such as pyridine and triethylamine can be used. The addition amount of a base is the quantity which is easy to remove, and since it is easy to obtain a high molecular weight body, 2 times-4 times mole is preferable with respect to a diamine component. In the above reaction, the reaction proceeds efficiently by adding Lewis acid as an additive. As the Lewis acid, lithium halides such as lithium chloride and lithium bromide are preferable. As for the addition amount of a Lewis acid, 0-1.0 times mole is preferable with respect to a diamine component. Since the high molecular weight polyamic acid ester is obtained among the manufacturing method of the said three polyamic acid ester, the manufacturing method of said (1) or said (2) is especially preferable. The solution of the polyamic acid ester obtained as mentioned above can deposit a polymer by inject | pouring into a poor solvent, stirring well. Precipitation is carried out several times, followed by washing with a poor solvent, followed by normal temperature or heat drying to obtain a purified polyamic acid ester powder. Although the poor solvent is not specifically limited, Water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene, etc. are mentioned.

In order to manufacture the polymer of this invention, you may use the diamine represented by Formula (1) as said diamine in the said manufacturing method. When the liquid crystal aligning film is obtained from the liquid crystal aligning agent containing the said polymer, the molecular weight of the polyimide precursor which is a polymer contained in the liquid crystal aligning agent of this invention, the strength of the coating film (liquid crystal aligning film) at the time of coating film formation In consideration of workability and uniformity of the coating film, the weight average molecular weight measured by the GPC (Gel Permeation Chromatography) method is preferably 2,000 to 500,000, more preferably 5,000 to 300,000, still more preferably 10,000 to 100,000. Do.

<Liquid crystal aligning agent>

Although the liquid crystal aligning agent of this invention contains the polymer (specific polymer) obtained from the diamine which has a structure represented by Formula (1), in the limit which exhibits the effect as described in this invention, it is 2 types of specific polymers of a different structure. You may contain as above. Moreover, in addition to a specific polymer, you may contain another polymer, ie, the polymer which does not have a bivalent group represented by Formula (1). Examples of other polymers include polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivative, polyacetal, polystyrene or derivatives thereof, and poly (styrene-phenylmaleimide ) Derivatives, poly (meth) acrylates, and the like. When the liquid crystal aligning agent of this invention contains another polymer, it is preferable that the ratio of the specific polymer with respect to all the polymer components is 5 mass% or more, and 5 mass%-95 mass% are mentioned as an example.

A liquid crystal aligning agent is used in order to produce a liquid crystal aligning film, and generally takes the form of a coating liquid from a viewpoint of forming a uniform thin film. Also in the liquid crystal aligning agent of this invention, it is preferable that it is a coating liquid containing said polymer component and the organic solvent which melt | dissolves this polymer component. In that case, the density | concentration of the polymer in a liquid crystal aligning agent can be suitably changed with the setting of the thickness of the coating film to form. It is preferable that it is 1 mass% or more from the point which forms a uniform and defect-free coating film, and it is preferable to set it as 10 mass% or less from the point of the storage stability of a solution. The density | concentration of especially preferable polymer is 2 mass%-8 mass%.

The organic solvent contained in a liquid crystal aligning agent will not be specifically limited if a polymer component melt | dissolves uniformly. Specific examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide and γ-butyro. Lactone, 1, 3- dimethyl- imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, etc. are mentioned. Especially, it is preferable to use N-methyl- 2-pyrrolidone, N-ethyl- 2-pyrrolidone, or (gamma) -butyrolactone.

In addition, as for the organic solvent contained in a liquid crystal aligning agent, it is common to use the mixed solvent which used together the solvent which improves the coating property at the time of apply | coating a liquid crystal aligning agent, and the surface smoothness of a coating film in addition to the above-mentioned solvent, Also in the liquid crystal aligning agent of this invention, such a mixed solvent is used preferably. Although the specific example of the organic solvent used together is given below, it is not limited to these examples. For example, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, Isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1- Butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methyl Cyclohexanol, 3-methylcyclohexanol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, Ethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methylethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2 -Heptanone, 4-heptanone, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, 2- (methoxymethoxy) ethanol, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2- (hexyloxy) ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, propylene Glycol monobutyl ether, 1- (butoxyethoxy) propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl LE, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol mono Ethyl ether acetate, diethylene glycol monobutyl ether acetate, 2- (2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate Ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl, 3-methoxypropionic acid butyl, lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, lactic acid isoamyl ester, the following formula [D -1]-the solvent shown by [D-3], etc. are mentioned.

[Formula 53]

Of the formula ^[D-1], D 1 represents an alkyl group having a carbon number of 1 to 3, wherein ^[D-2], D 2 represents an alkyl group having a carbon number of 1 to 3, formula ^[D-3], D 3 Represents an alkyl group having 1 to 4 carbon atoms.

Among them, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2- Pentanone, ethylene glycol monobutyl ether or dipropylene glycol dimethyl ether is preferably used.

The kind and content of such a solvent are suitably selected according to the coating device of a liquid crystal aligning agent, application | coating conditions, application environment, etc.

The liquid crystal aligning agent of this invention may contain components other than a polymer component and an organic solvent in the range which does not impair the effect of this invention. As such an additional component, the adhesion | attachment adjuvant for improving the adhesiveness of a liquid crystal aligning film and a board | substrate, or the adhesiveness of a liquid crystal aligning film and a sealing material, a crosslinking agent for increasing the intensity | strength of a liquid crystal aligning film, a dielectric material and an electrically conductive material for adjusting the dielectric constant and electrical resistance of a liquid crystal aligning film Etc. can be mentioned. As specific examples of these additional components, various publications have been disclosed in the known literature on liquid crystal aligning agents. However, if one example thereof is shown, pages 53 to 55 of the pamphlet of International Publication No. 2015/060357 are given. And the components disclosed in the above.

<Liquid crystal aligning film>

The liquid crystal aligning film of this invention is obtained from the said liquid crystal aligning agent. For example of a method of obtaining a liquid crystal aligning film from a liquid crystal aligning agent, the method of performing an alignment process by the rubbing process or the photo-alignment process method with respect to the film | membrane obtained by apply | coating the liquid crystal aligning agent of a coating liquid form to a board | substrate, drying, and baking Can be mentioned. As a board | substrate which apply | coats a liquid crystal aligning agent, if it is a board | substrate with high transparency, it will not specifically limit, Plastic board | substrates, such as an acryl substrate and a polycarbonate board | substrate, etc. can also be used with a glass substrate and a silicon nitride substrate. In that case, when the board | substrate with which the ITO electrode etc. for driving a liquid crystal were formed is used, it is preferable at the point of the process simplification. In addition, in the reflective liquid crystal display element, as long as it is only one side board | substrate, even an opaque thing, such as a silicon wafer, can be used, and the material which reflects light, such as aluminum, can also be used for the electrode in this case.

Although the coating method of a liquid crystal aligning agent is not specifically limited, Industrially, screen printing, offset printing, flexographic printing, the inkjet method, etc. are common. Other coating methods include a dip method, a roll coater method, a slit coater method, a spinner method, a spray method, and the like, and may be used depending on the purpose. After apply | coating a liquid crystal aligning agent on a board | substrate, a solvent is evaporated and baked by heating means, such as a hotplate, a thermal cycling oven, and an IR (infrared rays) oven. The drying after apply | coating a liquid crystal aligning agent, and the baking process can select arbitrary temperature and time. Usually, in order to fully remove the solvent contained, baking is carried out at 50 degreeC-120 degreeC for 1 minute-10 minutes, and the conditions baked at 150 degreeC-300 degreeC after that for 5 minutes-120 minutes are mentioned. Although the thickness of the liquid crystal aligning film after baking is not specifically limited, Since the reliability of a liquid crystal display element may fall when too thin, it is preferable that it is 5 nm-300 nm, and 10 nm-200 nm are more preferable. The liquid crystal aligning film of this invention is preferable as a liquid crystal aligning film of the liquid crystal display element of transverse electric field systems, such as an IPS system and a FFS system, and is especially useful as a liquid crystal aligning film of the liquid crystal display element of a FFS system.

<Liquid crystal display element>

After obtaining the board | substrate with a liquid crystal aligning film obtained from the said liquid crystal aligning agent, the liquid crystal display element of this invention produces a liquid crystal cell by a known method, and sets it as an element using the liquid crystal cell. As an example of the manufacturing method of a liquid crystal cell, it demonstrates taking the liquid crystal display element of a passive matrix structure as an example. Moreover, the liquid crystal display element of an active matrix structure in which switching elements, such as TFT (Thin Film Transistor), was formed in each pixel part which comprises an image display may be sufficient. Specifically, the transparent glass substrate is prepared, a common electrode is formed on one board | substrate, and a segment electrode is formed on the other board | substrate. These electrodes can be made into an ITO electrode, for example, and are patterned so that desired image display can be performed. Next, an insulating film is formed on each board | substrate so that a common electrode and a segment electrode may be coat | covered. The insulating film can be, for example, a film made of SiO ₂ -TiO ₂ formed by the sol-gel method. Next, a liquid crystal aligning film is formed on each board | substrate on the conditions similar to the above.

Next, after arrange | positioning an ultraviolet curable sealing material, for example in the predetermined place on one board | substrate among two board | substrates with which the liquid crystal aligning film was formed, and arrange | positioning a liquid crystal to the predetermined resin point on the liquid crystal aligning film surface, so that a liquid crystal aligning film may oppose. A liquid crystal cell is obtained by bonding an other board | substrate together and crimping | bonding and pressing a liquid crystal on the liquid crystal aligning film whole surface, and irradiating an ultraviolet-ray to the whole surface of a board | substrate and hardening a sealing material. Moreover, as a process after forming a liquid crystal aligning film on a board | substrate, when arranging a sealing material in the predetermined place on one board | substrate, after forming the opening part which can fill a liquid crystal from the outside, after bonding a board | substrate without arranging a liquid crystal, A liquid crystal material is injected into a liquid crystal cell through the opening formed in the sealing material, and then the opening is sealed with an adhesive to obtain a liquid crystal cell. The injection of the liquid crystal material may be performed by a vacuum injection method or a method using a capillary phenomenon in the atmosphere.

In any of the above methods, in order to secure a space in which the liquid crystal material is filled in the liquid crystal cell, a columnar protrusion is formed on one substrate, a spacer is dispersed on one substrate, or a spacer is mixed in the sealing material. It is preferable to take a means such as or to combine them.

As said liquid crystal material, a nematic liquid crystal and a smectic liquid crystal are mentioned, Especially, a nematic liquid crystal is preferable and you may use either a positive liquid crystal material or a negative liquid crystal material. Next, the polarizing plate is installed. Specifically, it is preferable to affix a pair of polarizing plate on the surface on the opposite side to the liquid crystal layer of two board | substrates.

In addition, the liquid crystal aligning film and liquid crystal display element of this invention are not limited to said base material, as long as the liquid crystal aligning agent of this invention is used, What was produced by other well-known methods may be sufficient. The process until a liquid crystal display element is obtained from a liquid crystal aligning agent is disclosed also in numerous documents other than pages 17-19 of Japanese Unexamined-Japanese-Patent No. 2015-135393 (Japanese Patent Laid-Open Publication), for example. It is.

EXAMPLE

Although an Example is given to the following and this invention is demonstrated in more detail, this invention is not limited to these.

The symbol of the compound used by the present Example and the comparative example and the method of a characteristic evaluation are as follows.

NMP: N-methyl-2-pyrrolidone

BCS: Butyl Cellosolve

GBL: γ-butyrolactone

NMP: N-methyl-2-pyrrolidone

DA-1-1: the compound represented by following formula DA-1-1

DA-2: compound represented by the following formula DA-2

DA-3: compound represented by the following formula DA-3

CA-1: the compound represented by following formula CA-1

CA-2: Compound represented by the following formula CA-2

[Formula 54]

Example 1A

Synthesis of (DA-1-1)

[Formula 55]

Into the flask, 15.00 g (68.8 mmol) of N- (4-nitrophenyl) maleimide and 300 g of tetrahydrofuran (hereinafter referred to as THF) were added, followed by ice cooling. In the mixture, 3.37 g (33.0 mmol) of N, N'-dimethyl-1,3-propanediamine was added. Then, after gradually returning to room temperature, it stirred at room temperature for 1 day. After confirming that the reaction was completed, 200 g of ethyl acetate was added to the reaction mixture and stirred. The obtained crystal was filtered and dried at 50 degreeC, and 11.1 g of the target nitro body intermediates (DA-1-1-1) were obtained (yield 62%).

In a flask substituted with nitrogen, DA-1-1-1 11.1 g (20.6 mmol), 5% Pd-C 1 g (STD type, wet product, manufactured by N. Chemcat Co., Ltd.) and N, N- After 300 g of dimethylformamide (hereinafter referred to as DMF) was added, the flask was hydrogen-substituted. The reaction mixture was stirred for 3 days at room temperature under hydrogen pressure and normal pressure. After confirming that the reaction was completed, Pd-C was removed from the reaction mixture by filtration, and the filtrate was distilled off under reduced pressure. In the obtained residue, chloroform was added and stirred. The insoluble matter was removed by filtration, and the obtained filtrate was distilled off under reduced pressure, so that 8.93 g (yield 90%) of the desired DA-1-1 was obtained as a viscous liquid.

Example 2A

Synthesis of (DA-1-2)

[Formula 56]

0.1246 g (0.662 mmol) of N- (4-aminophenyl) maleimide and 3 g of THF were added to the flask, followed by ice cooling. In the mixture, 0.0285 g (0.331 mmol) of piperazine was added. Then, after gradually returning to room temperature, it stirred at room temperature for 3 days. After confirming that the reaction was completed, the precipitated crystals were filtered and the crystals were washed with diisopropyl ether (hereinafter referred to as IPA). As a result of drying the obtained crystal at 50 degreeC, 0.067 g of DA-1-2 of the objective was obtained (yield 47%).

Example 3A

Synthesis of (DA-1-3)

[Formula 57]

Into the flask, 2.90 g (15.4 mmol) of N- (4-aminophenyl) maleimide and 30 g of tetrahydrofuran (hereinafter referred to as THF) were added, followed by ice cooling. In this mixture, 1.00 g (7.34 mmol) of 4- (aminomethyl) benzylamine was added. Then, after slowly returning to room temperature, it stirred at room temperature for 3 hours. After confirming that the reaction was completed, the reaction mixture was cooled again, and the precipitated crystals were filtered out. As a result of drying the obtained crystal at 45 degreeC under reduced pressure, 1.59 g of the target compound (DA-1-3) was obtained as yellow crystals (yield 42%).

[Viscosity measurement]

The viscosity of the polyamic-acid solution was measured by the sample amount 1.1 ml and cone rotor TE-1 (1 degrees 34 ', R24) using E-type viscosity meter TVE-22H (made by Toki Sangyo Co., Ltd.).

Example 1

DA-1-1 (3.34 g, 7 mmol) was added to the 50 mL four-necked flask with a stirring apparatus and the nitrogen inlet tube was added, and then N1.531.5g was added, and it stirred and sent out nitrogen and dissolved. CA-1 (1.43 g, 6.58 mmol) was added stirring this diamine solution, 3.5g of NMP was added, and the polyamic-acid solution (PAA-1) was obtained by further stirring under 50 degreeC conditions for 12 hours. . The viscosity at 25 degrees C of this polyamic-acid solution was 270 mPa * s.

Example 2

DA-1-1 (3.34 g, 7 mmol) was added to the 50 ml four-necked flask with a stirring apparatus and the nitrogen inlet tube was added, and then NMP 31.1 g was added, and it stirred and sent out nitrogen and dissolved. CA-1 (0.61 g, 2.8 mmol) and CA-2 (0.75 g, 3.9 mmol) were added stirring this diamine solution, 3.5 g of NMP were added, and also it stirred for 12 hours on 50 degreeC conditions. Thus, a polyamic acid solution (PAA-2) was obtained. The viscosity at 25 degrees C of this polyamic-acid solution was 280 mPa * s.

Comparative Example 1

DA-2 (5.73 g, 20 mmol) was added to the 100 mL four-necked flask with a stirring apparatus and the nitrogen inlet tube was added, 65.1 g of NMP was added, and it stirred and sent out nitrogen and dissolved. CA-1 (4.14 g, 19 mmol) was added stirring this diamine solution, 7.2 g of NMP were added, and also the polyamic-acid solution (PAA-3) was obtained by stirring at room temperature conditions for 18 hours. . The viscosity at 25 degrees C of this polyamic-acid solution was 500 mPa * s.

Comparative Example 2

DA-3 (1.98 g, 10 mmol) was added to the 50 mL four-necked flask with a stirring apparatus and the nitrogen inlet tube was added, and then NMP26.0g was added, and it stirred and sent out nitrogen and dissolved. CA-1 (0.87 g, 4.0 mmol) and CA-2 (1.08 g, 5.5 mmol) are added stirring this diamine solution, 2.9g of NMP are added, and also it stirs for 12 hours on 50 degreeC conditions. Thus, a polyamic acid solution (PAA-4) was obtained. The viscosity at 25 degrees C of this polyamic-acid solution was 300 mPa * s.

Example 3

7.5g of polyamic-acid solutions (PAA-1) obtained in Example 1 were fractionated, and 0.9g of NMP solutions containing 5.6g of NMP, 6.0g of BCS, and 1weight% of 3-aminopropyltriethoxysilane by stirring. It added, and also stirred at room temperature for 2 hours, and obtained the liquid crystal aligning agent (Q-1).

Example 4

7.5g of polyamic-acid solutions (PAA-2) obtained in Example 2 were fractionated, and 0.9g of NMP solutions containing 5.6g of NMP, 6.0g of BCS, and 1weight% of 3-aminopropyltriethoxysilane by stirring. It added, and also stirred at room temperature for 2 hours, and obtained the liquid crystal aligning agent (Q-2).

Comparative Example 3

7.5g of polyamic-acid solutions (PAA-3) obtained by the comparative example 1 were fractionated, and 0.9g of NMP solutions containing 5.6g of NMP, 6.0g of BCS, and 1weight% of 3-aminopropyl triethoxysilane by stirring. It added, and also stirred at room temperature for 2 hours, and obtained the liquid crystal aligning agent (Q-3).

[Comparative Example 4]

7.5g of polyamic-acid solutions (PAA-4) obtained by the comparative example 2 were fractionated, and 0.9g of NMP solutions containing 5.6g of NMP, 6.0g of BCS, and 1weight% of 3-aminopropyl triethoxysilane by stirring. It added, and also stirred at room temperature for 2 hours, and obtained the liquid crystal aligning agent (Q-4).

[Production of Liquid Crystal Cell for Ion Density Measurement]

After filtering the liquid crystal aligning agent with the 1.0 micrometer filter, the board | substrate with which the electrode was formed (30 mm x 40 mm in length, 1.1 mm thick glass substrate. The electrode is a rectangle of width 10 mm x length 40 mm, To ITO electrode having a thickness of 35 nm) by spin coating. After drying for 5 minutes on a 50 degreeC hotplate, baking was performed for 20 minutes by the 230 degreeC IR type oven, the coating film of 100 nm of film thickness was formed, and the board | substrate with a liquid crystal aligning film was obtained. After rubbing this liquid crystal aligning film with a rayon cloth (YA-20R by Yoshikawa Chemical Co., Ltd.) (roller diameter: 120 mm, roller rotation speed: 1000 rpm, moving speed: 20 mm / sec, indentation length: 0.4 mm), it was made into 1 in pure water. Ultrasonic irradiation was performed for a minute, washing | cleaning was carried out, water droplets were removed by air blow, and it dried at 80 degreeC for 15 minutes, and obtained the board | substrate with a liquid crystal aligning film.

After preparing two board | substrates with said liquid crystal aligning film, spread | dispersing a 4 micrometers spacer on the surface of one liquid crystal aligning film, a sealing material is printed from it, and the other one board | substrate has the opposite direction, And after sticking so that a membrane surface may face, the sealing material was hardened and the empty cell was produced. MLC-3019 (Merck Co., Ltd. product) was injected into this empty cell by the pressure reduction injection method, the injection hole was sealed, and the liquid crystal cell was obtained. Then, the obtained liquid crystal cell was heated at 120 degreeC for 1 hour, and was left to stand at 23 degreeC overnight, and the liquid crystal cell for ion density measurement was obtained.

[Ion Density Measurement]

The ion density was measured about the liquid crystal cell produced by the method of the said [production of the liquid crystal cell for ion density measurement]. In ion density measurement, the ion density when the triangle wave of voltage +/- 10V and frequency of 0.01 Hz was applied to the liquid crystal cell was measured. The measurement temperature was performed at 60 degreeC. As a measuring apparatus, the Toyo Technica Corporation 6256 type liquid crystal physical property evaluation apparatus was used. The ion density was measured after the cell was fabricated and after the cell was aged at 60 ° C. under 90% of high temperature and high humidity for 120 hours.

[Production of Liquid Crystal Display Element]

First, a substrate on which electrodes were formed was prepared. The substrate is a glass substrate having a size of 30 mm × 35 mm and a thickness of 0.7 mm. On the board | substrate, the IZO electrode provided with the beta-shaped pattern which comprises a counter electrode as a 1st layer is formed. On the counter electrode of 1st layer, the SiN (silicon nitride) film | membrane formed into a film by CVD method is formed as 2nd layer. The film thickness of the SiN film of 2nd layer is 500 nm, and functions as an interlayer insulation film. On the SiN film of 2nd layer, the comb-tooth shaped pixel electrode formed by patterning an IZO film | membrane as 3rd layer is arrange | positioned, and two pixels of a 1st pixel and a 2nd pixel are formed. The size of each pixel is about 10 mm long and about 5 mm wide. At this time, the counter electrode of the first layer and the pixel electrode of the third layer are electrically insulated by the action of the SiN film of the second layer.

The pixel electrode of 3rd layer has the comb-tooth shaped shape comprised by putting in multiple arrangement | array | sequence the "<"-shaped electrode element in which the center part was bent similarly to the drawing of Unexamined-Japanese-Patent No. 2014-77845. The width | variety of the width direction of each electrode element is 3 micrometers, and the space | interval between electrode elements is 6 micrometers. Since the pixel electrode which forms each pixel is comprised by putting in multiple arrangement | array | sequence the "<"-shaped electrode element in which the center part was bent, the shape of each pixel is not rectangular but is bent in the center part like the electrode element, It has a shape similar to the letter b in bold type. Each pixel is divided up and down on the center of the curved portion, and has a first region above the curved portion and a second region below.

When the 1st area | region and 2nd area | region of each pixel are compared, the formation direction of the electrode element of the pixel electrode which comprises them becomes different. That is, when the rubbing direction of the liquid crystal alignment film described later is used as a reference, the electrode elements of the pixel electrodes are formed to have an angle of + 10 ° (clockwise) in the first region of the pixel, and the electrodes of the pixel electrode in the second region of the pixel. The elements are formed to form an angle of -10 ° (clockwise). That is, in the first region and the second region of each pixel, the directions of rotational operations (in-plane switching) of the liquid crystal caused by voltage application between the pixel electrode and the counter electrode are opposite to each other. It is configured to be.

Next, after filtering the obtained liquid crystal aligning agent with a 1.0 micrometer filter, the ITO film | membrane was formed into a film on the back surface as a counter substrate with the prepared said electrode formation, and each of the glass substrates which have a columnar spacer of 4 micrometers in height. Spin-coated. Subsequently, after drying for 5 minutes on a 80 degreeC hotplate, it baked for 20 minutes at 230 degreeC, and obtained the polyimide film on each board | substrate as a coating film with a film thickness of 60 nm. After rubbing this polyimide film | membrane image on a predetermined rubbing direction with a rayon cloth (roll diameter 120mm, rotation speed 500rpm, movement speed 30mm / sec, indentation amount 0.3mm), ultrasonic irradiation is carried out for 1 minute in pure water. It carried out and dried at 80 degreeC for 10 minutes.

Thereafter, two kinds of substrates on which the liquid crystal alignment film was formed were used to combine the respective rubbing directions so as to be anti-parallel, and the surroundings were sealed leaving a liquid crystal injection hole, thereby producing an empty cell having a cell gap of 3.8 μm. Liquid crystal (MLC-3019, Merck Co., Ltd.) was vacuum-injected into this empty cell at normal temperature, and then the injection hole was sealed and it was set as the liquid crystal cell of anti parallel orientation. The obtained liquid crystal cell comprises a FFS mode liquid crystal display element. Then, the obtained liquid crystal cell was heated at 120 degreeC for 1 hour, and used for each evaluation after leaving to stand overnight.

[Evaluation of Stability of Liquid Crystal Orientation]

Using this liquid crystal cell, an alternating voltage of 10 VPP was applied for 168 hours at a frequency of 30 Hz in a constant temperature environment of 60 ° C. Then, it was made to short-circuit between the pixel electrode and the counter electrode of a liquid crystal cell, and was left to stand at room temperature as it is for one day. After standing, the liquid crystal cell was provided between two polarizing plates arranged so that the polarization axes were orthogonal, the backlight was turned on in the absence of voltage, and the arrangement angle of the liquid crystal cell was adjusted so that the luminance of transmitted light was the smallest. The rotation angle when the liquid crystal cell was rotated from the darkest angle of the second region of the first pixel to the darkest angle of the first region was calculated as the angle Δ. Similarly, the second pixel was compared with the second region to calculate the same angle Δ. And the average value of the angle (DELTA) value of a 1st pixel and a 2nd pixel was computed as angle (DELTA) of a liquid crystal cell. The value of the angle (DELTA) of this liquid crystal cell was 0.15 degrees or less, and the thing higher than 0.15 degrees was evaluated as defect.

[Relief Characteristics of Accumulated Charge]

The liquid crystal cell is provided between two polarizing plates arranged so that the polarization axes are orthogonal, and the LED backlight is irradiated from below the two polarizing plates while the pixel electrode and the counter electrode are short-circuited and measured on two polarizing plates. The angle of the liquid crystal cell was adjusted so that the brightness of LED backlight transmitted light might be minimum. Next, the V-T characteristic (voltage-transmittance characteristic) under the temperature of 23 degreeC was measured, applying the square wave of frequency 30 Hz to this liquid crystal cell, and the AC voltage whose relative transmittance turns into 23% was computed. Since this alternating voltage corresponds to a region where the change in luminance with respect to the voltage is large, it is convenient for evaluating the accumulated charge through the luminance.

Next, after applying the square wave of the frequency of 30 Hz and the frequency of 30 Hz for 5 minutes, the relative transmittance | permeability became 23%, and superimposed the DC voltage of + 1.0V, it was driven for 30 minutes. Thereafter, the DC voltage was turned off, and only a square wave having an alternating transmittance of 23% and a frequency of 30 Hz was applied for 30 minutes. The faster the relaxation of the accumulated charge is, the faster the charge accumulation is for the liquid crystal cell when the DC voltages are superimposed, so that the relaxation characteristics of the accumulated charges are 23% or more from the state in which the relative transmittance immediately after the superimposition of the DC voltages is 30% or more. It evaluated by the time required until it fell to%. The shorter this time, the better the relaxation characteristic of the accumulated charge.

<Examples 5-6 and Comparative Examples 5-6>

Using the liquid crystal aligning agents Q-1 to Q-2 obtained in Examples 3 to 4 and the liquid crystal aligning agents Q3 to Q4 obtained in Comparative Examples 3 to 4, ion density measurement, stability evaluation of liquid crystal alignment, and relaxation characteristics of accumulated charge Was evaluated. The results are shown in Table 1.

Industrial availability

The liquid crystal aligning film of this invention can suppress a low ion density in a liquid crystal display element, and can quickly alleviate the accumulated electric charge especially in the liquid crystal display element of the IPS drive system and FFS drive system which require a rubbing process. Furthermore, since the shift | offset | difference of a rubbing direction and the orientation direction of a liquid crystal can be suppressed, the display performance excellent in afterimage characteristic and contrast can be obtained. Therefore, it is especially useful as a liquid crystal aligning film used for the liquid crystal display element of a IPS drive system or a FFS drive system, a multifunctional mobile phone (smartphone), a tablet type personal computer, a liquid crystal television, etc.

Claims (11)

The liquid crystal aligning agent containing the polymer obtained from the diamine which has a structure represented by following formula (1).

R <^1> represents a hydrogen atom, a C1-C5 linear or branched alkyl group, or an aryl group, and two R <^1> on the same maleimide ring may be mutually same, may differ, and two R <^1> is One may form alkylene having 3 to 6 carbon atoms, W ² represents a divalent organic group, W ¹ represents a single bond or carbonyl, and L ¹ represents a linear alkylene group having 1 to 20 carbon atoms and carbon number. A divalent group selected from a 3-20 branched alkylene group, a C3-C20 cyclic alkylene group, a phenylene group and a heterocyclic group, or a group formed by a plurality of divalent groups bonded thereto, and a phenylene group and a heterocyclic group Each independently may be substituted with the same or different one or a plurality of substituents selected from alkyl, alkoxy, haloalkyl, haloalkoxy, halogen and cyano; The bond between divalent groups is at least one selected from a single bond, an ester bond, an amide bond, a urea bond, an ether bond, a thioether bond, an amino bond, and carbonyl, and when the divalent groups are plural, The divalent groups may be the same or different, and in the case where the bonds are plural, the bonds may be the same or different, R represents a hydrogen atom or a monovalent organic group, and two R's may be different from each other, Two R may become one, and may form C1-C6 alkylene, and both or one of two R may couple | bond with L <^1> . The method of claim 1,
The liquid crystal aligning agent in which said W <^1> shows a single bond. The method according to claim 1 or 2,
Liquid crystal aligning agent whose said polymer is at least 1 sort (s) chosen from the polyimide precursor containing the structural unit represented by following formula (3), and the polyimide which is the imide.

X ¹ represents a tetravalent organic group derived from a tetracarboxylic acid derivative, Y ¹ represents a divalent organic group derived from a diamine containing the structure of formula (1), and R ⁴ represents a hydrogen atom or C 1-5 An alkyl group is shown. The method of claim 3, wherein
In said formula (3), the liquid crystal aligning agent which shows at least 1 sort (s) chosen from the following structure of the structure of X <^1> .

The method of claim 3, wherein
The liquid crystal aligning agent whose said polymer is at least 1 sort (s) chosen from the polyimide precursor which further contains the structural unit represented by following formula (4), and its imide.

In Formula (4), X <^2> represents the tetravalent organic group derived from a tetracarboxylic-acid derivative, Y <^2> represents the divalent organic group derived from diamine which does not contain the structure of Formula (1) in a principal chain direction. And R ¹⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ¹⁵ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The method of claim 5,
Liquid crystal aligning agent in which said Y <^2> is represented by following formula (11).

In formula (11), R ³² represents a single bond or a divalent organic group, R ³³ represents a structure represented _by- (CH ₂ ) _r- , r represents an integer of 2 to 10, and arbitrary -CH ₂ -may be substituted with ether, ester, amide, urea, carbamate bond on the condition that they are not adjacent to each other. R ³⁴ represents a single bond or a divalent organic group. Any hydrogen atom on a benzene ring may be substituted by monovalent organic group. The method according to claim 3 or 4,
The liquid crystal aligning agent whose structural unit represented by the said Formula (3) is 10 mol% or more with respect to the whole structural unit of a polymer. The liquid crystal aligning film containing the liquid crystal aligning agent in any one of Claims 1-7. The liquid crystal display element which comprises the liquid crystal aligning film of Claim 8. Diamine which has a structure represented by following formula (1).

R <^1> represents a hydrogen atom, a C1-C5 linear or branched alkyl group, or an aryl group, and two R <^1> on the same maleimide ring may be mutually same, may differ, and two R <^1> is One may form alkylene having 3 to 6 carbon atoms, W ² represents a divalent organic group, W ¹ represents a single bond or carbonyl, and L ¹ represents a linear alkylene group having 1 to 20 carbon atoms and carbon number. The divalent group selected from a 3-20 branched alkylene group, a C3-C20 cyclic alkylene group, a phenylene group, and a heterocyclic group, or the group which the said bivalent group combines in multiple numbers is represented, A phenylene group and a heterocyclic group Each independently may be substituted with the same or different one or a plurality of substituents selected from an alkyl group, an alkoxy group, a haloalkyl group, a haloalkoxy group, a halogen group and a cyano group, and The bond between divalent groups is at least one selected from a single bond, an ester bond, an amide bond, a urea bond, an ether bond, a thioether bond, an amino bond, and carbonyl, and when the divalent groups are plural, The divalent groups may be the same or different, and in the case where the bonds are plural, the bonds may be the same or different, R represents a hydrogen atom or a monovalent organic group, and two R's may be different from each other, Two R may become one, and may form C1-C6 alkylene, and both or one of two R may couple | bond with L <^1> . The polymer which uses the diamine of Claim 10.