TWI773748B - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Abstract

A liquid crystal aligning agent characterized by comprising a polymer obtained from a diamine having a structure represented by the following formula (1),

R represents a hydrogen atom or a monovalent organic group, and R ¹ represents a hydrogen atom or a straight-chain or branchable alkyl group with 1 to 5 carbon atoms or an aryl group, which is on the same maleimide ring. The two R ^1s can be the same or different from each other, and the two R ^1s can be bonded to each other to form an alkylene group with 3 to 6 carbon atoms, W ¹ represents a single bond or a divalent organic group, W ² It is a divalent organic group, Ar ¹ represents an aromatic ring, and L ¹ represents a single bond, a carbonyl group, a sulfonyl group or an alkylene group having 1 to 20 carbon atoms.

Description

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

The present invention relates to a novel diamine compound (also simply referred to as "diamine" in this specification) that can be used as a raw material for a polymer used in a liquid crystal alignment film, and a polymer (polyamic acid) obtained by using the diamine. , polyamide and polyimide, etc.), liquid crystal alignment agents, liquid crystal alignment films and liquid crystal display elements.

Conventionally, liquid crystal display elements have been widely used as display parts of personal computers, mobile phones, television cameras, and the like. As the driving methods, vertical electric field methods such as TN method and VA method, or IPS method and fringe electric field method are known. Transverse electric field methods such as Fringe Field Switching (hereinafter, referred to as "FFS") method. In general, electrodes are formed only on one side of the substrate, and the horizontal electric field method in which the liquid crystal is driven by applying an electric field in the direction parallel to the substrate is compared with the vertical electric field method in which the liquid crystal is driven by applying a voltage to the electrodes formed on the upper and lower substrates. It has wide viewing angle characteristics, etc., and can easily obtain a liquid crystal display element capable of high-quality display. As a method of aligning liquid crystals in a certain direction, there is a method of forming a polymer film such as polyimide on a substrate, wiping the surface with a cloth, and performing a so-called rubbing treatment.

As a conventional problem, charge accumulation due to a DC voltage component applied by an active matrix structure, and the like are exemplified. When electric charges are excessively accumulated in the liquid crystal display element, the liquid crystal alignment is disordered or an afterimage is generated, which adversely affects the display and reduces the display quality of the liquid crystal display element. Or, in the case of driving the liquid crystal display element in the state of accumulating electric charges, immediately after driving, the control of the liquid crystal molecules cannot be performed normally, and flickering (light flickering) and the like may occur.

Moreover, ion density etc. are mentioned as a characteristic requested|required of a liquid crystal alignment film in order to improve the display quality of a liquid crystal display element. When the ion density is too high, the voltage applied to the liquid crystal during the frame period decreases, and as a result, the luminance may decrease, which may interfere with normal gradation display. In addition, even if the ion density in the initial stage is lowered, the ion density after the high-temperature accelerated test may become high. Such a decrease in long-term reliability or generation of afterimages accompanied by residual charges or ionic impurities may cause a decrease in the display quality of liquid crystals.

In the liquid crystal alignment film of a polyimide type, various proposals have been made in response to the above-mentioned requirements. For example, using a liquid crystal aligning agent containing a tertiary amine with a specific structure in addition to a polyamide acid or a polyamide containing an imide group can shorten the afterimage generated by the DC voltage until it disappears. A liquid crystal alignment film with time (for example, Patent Document 1), or a liquid crystal alignment agent containing a soluble polyimide (for example, Patent Document 2) using a specific diamine compound such as a pyridine skeleton as a raw material is proposed. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Laid-Open No. 9-316200

[Patent Document 2] Japanese Patent Application Laid-Open No. 10-104633

As a method of aligning liquid crystal, rubbing treatment is widely used in industry, but depending on the liquid crystal alignment film used, the rubbing direction is inconsistent with the alignment direction of the liquid crystal, which may cause a phenomenon called twist angle. That is, in the lateral electric field element, a black display is displayed in a state where no voltage is applied, but this phenomenon increases the brightness even in a state where no voltage is applied, and as a result, there is a problem that the display contrast is lowered.

The present invention aims to provide a liquid crystal display device that can control the ion density in a liquid crystal display element to be low, and at the same time, can rapidly relax the accumulated electric charge, and especially can suppress the deviation between the rubbing direction and the alignment direction of the liquid crystal, which is a problem in the lateral electric field driving method ( deviation) of the liquid crystal alignment film for the purpose. Moreover, the present invention can obtain such a liquid crystal alignment film, and aims to provide a diamine, a polymer, and a liquid crystal alignment agent. Furthermore, this invention aims at providing the liquid crystal display element provided with such a liquid crystal alignment film.

As a result of diligent studies to solve the above-mentioned problems, the inventors of the present invention have found that various properties are simultaneously be improved to complete the present invention. The present invention is based on this insight, and the gist is as follows.

1. A liquid crystal aligning agent characterized by comprising a polymer obtained from a diamine having a structure represented by the following formula (1),

R represents a hydrogen atom or a monovalent organic group, R ¹ represents a hydrogen atom or a straight-chain or branchable alkyl group or an aryl group with a carbon number of 1-5, having 2 on the same maleimide ring The R ¹ can be the same or different from each other, and the two R ¹ can be bonded to each other to form an alkylene group with 3 to 6 carbon atoms, W ¹ represents a single bond or a divalent organic group, and W ² represents Represents a divalent organic group, Ar ¹ represents an aromatic ring, and L ¹ represents a single bond, a carbonyl group, a sulfonyl group, or an alkylene group having 1 to 20 carbon atoms.

2. The liquid crystal aligning agent according to 1., wherein the aforementioned Ar ¹ is 1,3-phenylene or 1,4-phenylene.

3. The liquid crystal aligning agent according to 1. or 2., wherein the aforementioned W ¹ is a single bond.

4. The liquid crystal aligning agent according to any one of 1. to 3., wherein the polymer is selected from the group consisting of a polyimide precursor including a structural unit represented by the following formula (3) and the imide compound. at least one of the polyimides,

X ¹ represents a tetravalent organic group derived from a tetracarboxylic acid derivative, Y ¹ represents a divalent organic group derived from a diamine having the structure of the formula (1), and R ⁴ represents a hydrogen atom or a carbon number of 1 to 1 5 of the alkyl group.

5. The liquid crystal aligning agent according to 4., wherein the structure of the aforementioned X ¹ is at least one selected from the following structures,

6. The liquid crystal aligning agent according to any one of 1. to 5., wherein the polymer further comprises a structural unit represented by the following formula (4) selected from a polyimide precursor and the imide compound at least one of the polyimides,

X ² represents a tetravalent organic group derived from a tetracarboxylic acid derivative, Y ² represents a divalent organic group derived from a diamine whose main chain direction does not include the structure of the formula (1), and R ¹⁴ represents each independently A hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ¹⁵ represents each independent hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

7. The liquid crystal aligning agent according to 6., wherein Y ² is represented by the following 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 any -CH ₂ - may not be adjacent to each other. The conditional substitution is ether, ester, amide, urea, urethane bond, R ³⁴ represents a single bond or a divalent organic group, and any hydrogen atom on the benzene ring can be substituted by a monovalent organic group.

8. The liquid crystal aligning agent according to 4. to 7., wherein the structural unit represented by the aforementioned formula (3) is 10 mol % or more relative to the total structural unit of the polymer.

9. A liquid crystal alignment film obtained from the liquid crystal alignment agent according to any one of 1. to 8.

10. A liquid crystal display element comprising the liquid crystal alignment film according to 9.

11. A polymer obtained from a diamine having a structure represented by the following formula (1),

R represents a hydrogen atom or a monovalent organic group, and R ¹ represents a hydrogen atom or a straight-chain or branchable alkyl group with 1 to 5 carbon atoms or an aryl group, which is on the same maleimide ring. The two R ^1s can be the same or different from each other, and the two R ^1s can be bonded to each other to form an alkylene group with 3 to 6 carbon atoms, W ¹ represents a single bond or a divalent organic group, W ² represents a divalent organic group, Ar ¹ represents an aromatic ring, and L ¹ represents a single bond, a carbonyl group, a sulfonyl group, or an alkylene group having 1 to 20 carbon atoms.

12. A diamine characterized by having a structure represented by the following formula (1),

R represents a hydrogen atom or a monovalent organic group, and R ¹ represents a hydrogen atom or a straight-chain or branchable alkyl group with 1 to 5 carbon atoms or an aryl group, which is on the same maleimide ring. The two R ^1s can be the same or different from each other, and the two R ^1s can be bonded to each other to form an alkylene group with 3 to 6 carbon atoms, W ¹ represents a single bond or a divalent organic group, W ² represents a divalent organic group, Ar ¹ represents an aromatic ring, and L ¹ represents a single bond, a carbonyl group, a sulfonyl group, or an alkylene group having 1 to 20 carbon atoms.

By using the liquid crystal aligning agent of the present invention, the ion density in the liquid crystal display element is controlled to be low, and the accumulated charge can be rapidly relaxed, which is especially a problem in the lateral electric field driving method, and the rubbing direction and the rubbing direction can be suppressed. The liquid crystal alignment film of the deviation of the alignment direction of the liquid crystal. A mechanism that can solve the above-mentioned problems of the present invention can be roughly considered as follows. The structure of the above-mentioned formula (1) contained in the polymer of the present invention has a nitrogen atom. Thereby, for example, in a liquid crystal alignment film, while having the ability to supplement the ionic impurities, the transfer of electric charges can be promoted, and the relaxation of the accumulated electric charges can be promoted.

Moreover, by using the diamine of this invention, the said polymer and the said liquid crystal aligning agent can be obtained. And this liquid crystal display element excellent in various characteristics can be obtained by having the said liquid crystal aligning film of this invention.

[Form of implementing the invention]

The liquid crystal aligning agent of the present invention is composed of the above formula (1) The polymer (henceforth, also called a specific polymer) obtained by the diamine of the structure (henceforth a specific structure) shown.

<Diamine with specific structure>

In the above formula (1), R represents a hydrogen atom or a monovalent organic group, and R ¹ represents a hydrogen atom or a straight-chain or branchable alkyl group with 1 to 5 carbon atoms or an aryl group. The 2 R ^1s on the imine ring can be the same or different from each other, the 2 R ^1s can be bonded to each other to form an alkylene group with 3 to 6 carbon atoms, and W ¹ represents a single bond or a divalent In the organic group, W ² represents a divalent organic group, Ar ¹ represents an aromatic ring, and L ¹ represents a single bond, a carbonyl group, a sulfonyl group or an alkylene group with 1 to 20 carbon atoms.

As R, a hydrogen atom or a straight-chain alkyl group having 1 to 3 carbon atoms is preferable, and a hydrogen atom or a methyl group is preferable. In addition, from the viewpoint of the storage stability of the liquid crystal aligning agent, R is a protective group that can be substituted for a hydrogen atom by a desorption reaction generated by heat, and is not desorbed at room temperature, preferably at a temperature of 80°C or higher. The protective group to be removed is preferably a protective group to be removed under heat of 100°C or higher. Examples of this include 1,1-dimethyl-2-chloroethoxycarbonyl, 1,1-dimethyl-2-cyanoethoxycarbonyl, and tert-butoxycarbonyl, preferably tert-butoxy carbonyl.

R ¹ is preferably a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, or a phenyl group, more preferably a hydrogen atom, a methyl group, or a phenyl group. In addition, as the alkylene group having 3 to 6 carbon atoms in which R 1 having two R ^1s can be bonded to each other, -(CH ₂ ) ₃ -, -(CH ₂ ) ₄ -, and -(CH ₂ ) ₅ are preferable. -, preferably -(CH ₂ ) ₄ -.

W ¹ is selected from a single bond, -O-, -COO-, -OCO-, -(CH ₂ ) _p -, -O(CH ₂ ) _q O-, -CONH-, or -NHCO- 2 valences Organic groups are preferred, p represents a natural number from 1 to 10, and q represents a natural number from 1 to 10. As Ar ¹ , a 1,3-phenylene or 1,4-phenylene is preferred.

L ¹ represents a single bond, a carbonyl group, a sulfonyl group, or an alkylene group having 1 to 20 carbon atoms. The alkylene group having 1 to 20 carbon atoms as L ¹ may be straight-chain or branched, and examples thereof include a straight-chain alkylene group represented by -(CH ₂ ) _n - (but, n is 1 to 20) or 1 -Methylmethane-1,1-diyl, 1-ethylmethane-1,1-diyl, 1-propylmethane-1,1-diyl, 1-methylethane-1,2-diyl base, 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-methylpropane-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-methylhexane-1,6-diyl, 1-ethylhexane-1,6-diyl, 2-methyl Hexane-1,6-diyl, 2-ethylhexane-1,6-diyl, 3-methylhexane-1,6-diyl, 3-ethylhexane-1,6-diyl base, 1-methylheptane-1,7-diyl, 2-methylheptane-1,7-diyl, 3-methylheptane-1,7-diyl, 4-methylheptane - Branches of 1,7-diyl, 1-phenylmethane-1,1-diyl, 1-phenylethane-1,2-diyl, 1-phenylpropane-1,3-diyl, etc. alkylene. These linear or branched alkylene groups are interrupted 1 to 5 times by oxygen atoms or sulfur atoms under the condition that oxygen atoms or sulfur atoms are not adjacent to each other.

The divalent organic group W ² is represented by the following formulas [W ² -1] to [W ² -152],

Among them, W ² -7, W ² -20, W ² -21, W ² -23, W ² -26, W ² -39, W ² from the viewpoint of both ion density suppression and liquid crystal alignment stability -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, W ² -71 are preferred.

<Method for producing specific diamine> The method for synthesizing the diamine having a specific structure of the present invention (in this specification, it may be referred to as "specific diamine") is not particularly limited, but can be exemplified by the following formula (A1 ) represented by the maleimide compound reacted with the diamine compound represented by the following formula (B1) to obtain the aminonitro compound represented by the following formula (C1), and the method of reducing it,

R、R¹ 、L¹ 、Ar¹ 、W¹ 及W² 之定義係與上述式(1)相同。

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

For 1 mole of the compound represented by the formula (A1), the usage amount of the compound represented by the formula (B1) is preferably 1-2 moles, more preferably 1-1.2 moles. By using the compound represented by the formula (B1) in excess, the reaction proceeds smoothly and by-products can be suppressed.

The reaction is preferably carried out in a solvent. As long as the solvent does not react with each raw material, it can be used without limitation. For example, aprotic polar organic solvents (DMF, DMSO, DMAc, NMP, etc.); ethers ( _Et2O , i- _Pr2O , TBME, CPME, THF, dioxane, etc.); aliphatic hydrocarbons can be used (pentane, hexane, heptane, petroleum ether, etc.); aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, etc.); halogens Hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.); lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.); nitriles (acetonitrile, propionitrile, butyronitrile, etc.).

These solvents can be appropriately selected in consideration of the easiness of causing the reaction and the like, and can be used alone or in combination of two or more. When necessary, a suitable dehydrating agent or desiccant is used to dry the solvent, and it can also be used as a non-aqueous solvent. The use amount (reaction concentration) of the solvent is not particularly limited, but is 0.1 to 100 times by mass relative to the bismaleimide compound. It is preferably 0.5 to 30 times by mass, more preferably 1 to 10 times by mass. The reaction temperature is not particularly limited, but is in the range from -100°C to the boiling point of the solvent used, preferably -50 to 150°C. The reaction time is generally 0.05 to 350 hours, preferably 0.5 to 100 hours.

If necessary, this reaction can be carried out in the presence of an inorganic base or an organic base. Inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium bicarbonate, potassium bicarbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, etc. can be used as the base system used in the reaction; tert-butyl Bases of sodium alkoxide, potassium tert-butoxide, sodium hydride, potassium hydride, etc.; trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, diisopropylethylamine , amines such as pyridine, quinoline, collidine, etc. Among them, triethylamine, pyridine, sodium tert-butoxide, potassium tert-butoxide, sodium hydride, potassium hydride and the like are preferred. The amount of the base used is not particularly limited, but is 0 to 100 times by mass relative to the bismaleimide compound. It is preferably 0 to 30 times by mass, more preferably 0 to 10 times by mass.

The conditions at the time of reducing the compound represented by formula (C1) and producing the specific diamine represented by formula (1) are as follows. As a method for reducing the compound represented by the above formula (C1), there is a reduction reaction carried out in the coexistence of Fe, Sn, Zn or salts of these and protons. The usage-amount of Fe, Sn, Zn, or these salts is preferably 1 to 100 equivalents, particularly preferably 3 to 50 equivalents, with respect to the compound represented by the above formula (1).

As the reaction solvent in this case, under the reaction conditions, as long as it does not interfere with the solvent for the intended reaction, any one can be used. For example, water; alcohol solvents such as methanol, ethanol, tert-butanol, etc.; aprotic polar organic solvents such as dimethylformamide, dimethylsulfoxide, dimethylacetamide, N-methylpyrrolidone, etc. can be used Solvents; ethers of diethyl ether, diisopropyl ether, tert-butyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran, dioxane, etc.; aliphatic hydrocarbons such as pentane, hexane, heptane, petroleum ether, etc. ; Aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin, etc., halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.; methyl acetate, ethyl acetate, Lower fatty acid esters of butyl acetate, methyl propionate, etc.; nitriles of acetonitrile, propionitrile, butyronitrile, etc. These solvents can be appropriately selected in consideration of easiness of causing the reaction and the like, and can be used alone or in combination of two or more. And depending on the situation, the above-mentioned solvent system can also use a suitable dehydrating agent or a desiccant, and can be used as a solvent which does not contain water. The usage-amount (reaction concentration) of a solvent is not specifically limited, However, It is 0.1-100 mass times with respect to the compound represented by the said formula (C1). It is preferably 0.5 to 50 times by mass, more preferably 3 to 30 times by mass.

Furthermore, in order to carry out the reaction more efficiently, the reaction may be carried out under pressure. In this case, in order to avoid reduction of the benzene nucleus, it is preferable to carry out the reaction in a pressure range of about 20 atmospheric pressure (kgf), and preferably in a range up to 10 atmospheric pressure. Further, acids such as hydrochloric acid, sulfuric acid, formic acid, and acetic acid, and salts thereof are allowed to coexist. The usage-amount of these is not specifically limited, However, It is 0-10 mass times with respect to the compound represented by the said formula (C1). Preferably it is 0 to 5 mass times, more preferably 0 to 3 mass times.

The reaction temperature can be selected to be preferably a temperature range from the temperature of the boiling point of the reaction solvent used above -100°C, but is preferably -50 to 150°C, particularly preferably 0 to 100°C. The reaction time is 0.1 to 1000 hours, preferably 1 to 200 hours.

In addition, as a method for reducing the compound represented by the above formula (C1), there are a hydrogen addition reaction using palladium-activated carbon or platinum-activated carbon as a catalyst, a reduction reaction using formic acid as a hydrogen source, and hydrazine as a hydrogen source. Hydrogen source reaction, etc. In addition, these reactions may be combined and implemented. The catalyst used in the reduction reaction is preferably commercially available activated carbon supporting metals, and examples thereof include palladium-activated carbon, platinum-activated carbon, rhodium-activated carbon, and the like. In addition, palladium hydroxide, platinum oxide, Raney nickel, etc. may not necessarily be an activated carbon-supported metal catalyst. Generally, the widely used palladium-activated carbon or platinum-activated carbon can obtain good results, so it is preferred. The use amount of these catalysts may be a so-called catalyst amount, and is preferably 20 mol % or less, particularly preferably 10 mol % or less, with respect to the compound represented by the above formula (C1).

As the reaction solvent in this case, under the reaction conditions, as long as it does not interfere with the solvent for the intended reaction, any one can be used. For example, alcohol solvents such as methanol, ethanol, and tert-butanol can be used; aprotic polar organic solvents such as dimethylformamide, dimethylsulfoxide, dimethylacetamide, N-methylpyrrolidone, etc. can be used; Ethers of diethyl ether, isopropyl ether, tert-butyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran, dioxane, etc.; aliphatic hydrocarbons such as pentane, hexane, heptane, petroleum ether, etc.; benzene, Aromatic hydrocarbons such as toluene, xylene, mesitylene, tetralin, etc., halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.; methyl acetate, ethyl acetate, butyl acetate , lower fatty acid esters such as methyl propionate; nitriles such as acetonitrile, propionitrile, butyronitrile, etc. These solvents can be appropriately selected in consideration of easiness of causing the reaction and the like, and can be used alone or in combination of two or more. And depending on the situation, the above-mentioned solvent system can also use a suitable dehydrating agent or a desiccant, and can be used as a solvent which does not contain water. The usage-amount (reaction concentration) of a solvent is not specifically limited, However, It is 0.1-100 mass times with respect to the compound represented by the said formula (C1). It is preferably 0.5 to 50 times by mass, more preferably 3 to 30 times by mass. The reaction temperature is not particularly limited, but the range from -100°C to the boiling point of the solvent used is preferably -50 to 150°C. The reaction time is generally 0.05 to 350 hours, preferably 0.5 to 100 hours.

In order to carry out the reduction reaction more efficiently, the reaction may be carried out in the coexistence of activated carbon. In this case, the amount of activated carbon to be used is not particularly limited, but is preferably in the range of 1 to 30 mass %, preferably 10 to 20 mass %, relative to the dinitro compound (C1). For the same reason, the reaction may be carried out under pressure. In this case, in order to avoid the reduction of the benzene nucleus, it is carried out under the pressure range up to 20 atmospheres. It is preferable to carry out the reaction in the range of 10 atmospheres. In the reduction reaction exemplified above, considering the structure of the compound represented by the above (C1) and the reactivity of the reduction reaction, the hydrogen addition reaction is preferably used.

In addition, as a method for obtaining the specific diamine of the present invention, a maleimide compound represented by the following formula (A1) and an aminonitro compound represented by the following formula (B2) are reacted to obtain the following The method for reducing the dinitro compound represented by the formula (C2),

。

.

The reaction conditions of the compound represented by the formula (B2) and the compound represented by the formula (A1) are based on the reaction conditions of the compound represented by the formula (B1) and the compound represented by the formula (A1). In addition, the reaction conditions when reducing the dinitro compound represented by the formula (C2) to obtain the diamine represented by the formula (1) is to reduce the compound represented by the above formula (C1) to produce the compound represented by the formula (1). Conditions for specific diamines.

Moreover, as a method for obtaining the specific diamine of the present invention, a maleimide compound represented by the following formula (A2) and an aminonitro compound represented by the following formula (B2) are reacted to obtain A method of reducing the aminonitro compound represented by the following formula (C3),

。

.

The reaction conditions of the compound represented by the formula (B2) and the compound represented by the formula (A2) are based on the reaction conditions of the compound represented by the formula (B1) and the compound represented by the formula (A1). In addition, the reaction conditions when reducing the amino nitro compound represented by the formula (C3) to obtain the diamine represented by the formula (1) is to reduce the compound represented by the above formula (C1) to produce the compound represented by the formula (1). conditions for specific diamines.

In addition, as a method for obtaining the specific diamine of the present invention, a maleimide compound represented by the following formula (A2) and a diamine group compound represented by the following formula (B1) are reacted to obtain (1) ) method,

以式(B1)表示之化合物與以式(A2)表示之化合物之反應條件係依以式(B1)表示之化合物與以式(A1)表示之化合物之反應條件。

The reaction conditions of the compound represented by the formula (B1) and the compound represented by the formula (A2) are based on the reaction conditions of the compound represented by the formula (B1) and the compound represented by the formula (A1).

As R, when a monovalent organic group is to be introduced, in the dinitro compound represented by the above formula (C2), a compound in which R is a hydrogen atom may be reacted with a compound capable of reacting with amines. Examples of such compounds include acid halides, acid anhydrides, isocyanates, epoxies, propylene oxides, aryl halides, and alkyl halides, and OMs, OMs, etc. Alcohols, etc. of the leaving group of OTf, OTs, etc.

The method of introducing a monovalent organic group into an NH group is not particularly limited, but a method of reacting an acid halide in the presence of an appropriate base can be exemplified. Examples of acid halides include acetyl chloride, propionyl chloride, methyl chloroformate, ethyl chloroformate, n-propyl chloroformate, isopropyl chloroformate, n-butyl chloroformate, and isobutyl chloroformate. , tert-butyl chloroformate, benzyl chloroformate and 9-perylene chloroformate. As an example of the base, the aforementioned bases can be used. The reaction solvent and reaction temperature are as described above.

A monovalent organic group can be introduced by reacting an acid anhydride with an NH group. Examples of the acid anhydride include acetic anhydride, propionic anhydride, dimethyl dicarbonate, diethyl dicarbonate, di-tert-butyl dicarbonate, and dicarbonic acid. Dibenzyl ester, etc. In order to promote the reaction, a catalyst may be added, and pyridine, Collidine, N,N-dimethyl-4-aminopyridine and the like can be used. The catalyst amount is 0.0001 mol to 1 mol relative to 1 mol of the compound in which R is a hydrogen atom in the dinitro compound represented by the above formula (C2). The reaction solvent and reaction temperature are as described above.

A monovalent organic group can be introduced by reacting cyanate esters with an NH group. Examples of isocyanates include methyl isocyanate, ethyl isocyanate, n-propyl isocyanate, phenyl isocyanate and the like. The reaction solvent and reaction temperature are as described above.

Monovalent organic groups can be introduced by reacting epoxy compounds or propylene oxide compounds with NH groups. Examples of epoxy compounds or propylene oxides include ethylene oxide, propylene oxide, and 1,2-butylene oxide. alkene, trimethylene oxide, etc. The reaction solvent and reaction temperature are as described above.

A monovalent organic group can be introduced by reacting an aryl halide to an NH group in the presence of a metal catalyst, a ligand, and a base. Examples of the aryl halide include iodobenzene, bromobenzene, chlorobenzene and the like. Examples of the metal catalyst include palladium acetate, palladium chloride, palladium chloride-acetonitrile complex, palladium-activated carbon, bis(diphenylideneacetone)palladium, and ginseng(diphenylideneacetone)bis Palladium, bis(acetonitrile)dichloropalladium, bis(benzonitrile)dichloropalladium, CuCl, CuBr, CuI, CuCN, etc., are not limited to these. Examples of the ligand include triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, and 1,2-bis(diphenylphosphino)ethane , 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,1'-bis(diphenylphosphino)ferrocene, trimethyl Phosphite, triethylphosphite, triphenylphosphite, tri-tert-butylphosphine, etc. are not limited to these. As an example of the base, the aforementioned bases can be used. The reaction solvent and reaction temperature are as described above.

In the presence of a suitable base, a monovalent organic group can be introduced by substituting the hydroxyl group of the alcohol with alcohols leaving groups such as OMs, OTf, OTs, etc., and reacting with the NH group. Examples of alcohols include methanol, ethanol, 1-propanol, and the like. By combining these alcohols with methanesulfonic acid chloride, trifluoromethanesulfonic acid chloride, paratoluenesulfonic acid chloride ), etc. to react to obtain alcohols substituted into the leaving groups of OMs, OTf, OTs, etc. As an example of the base, the aforementioned bases can be used. The reaction solvent and reaction temperature are as described above.

In the presence of an appropriate base, a monovalent organic group can be introduced by reacting an alkyl halide with an NH group. Examples of alkyl halides include methyl iodide, ethyl iodide, n-propyl iodide, methyl bromide, ethyl bromide, n-propyl bromide, and the like. As an example of the base, metal alkoxides such as potassium tert-butoxide and sodium tert-butoxide can be used in addition to the aforementioned bases. The reaction solvent, reaction temperature and reaction time are as described above.

The usage-amount of the compound which can react with the above-mentioned amines, in the dinitro compound represented by the above-mentioned formula (C2), can be set to 1.0-3.0 molar equivalent relative to 1.0 molar equivalent of the compound in which R is a hydrogen atom about. The range of 2.0 to 2.5 molar equivalents is preferable. Moreover, the compound which can react with the above-mentioned amines can be used individually or in combination.

Furthermore, when there are isomers derived from asymmetric points in the diamine compound represented by the formula (1), in this case, each isomer and a mixture thereof are included in the diamine compound represented by the formula (1). Diamine. In addition, in the case where the two R ¹ of the same maleimide ring of the formula (1) are different from each other, in the diamine compound represented by the formula (1), the substitution positions of R ¹ are different, but in this case the same Isomers and mixtures thereof are also all contained in the diamine represented by the formula (1).

[Production method of formula (A1)] The method for synthesizing the compound of formula (A1) is not particularly limited, but for example, a method of reacting a maleic anhydride derivative with a commercially available nitroamine represented by the following formula (D1) can be mentioned ,

。

.

The amount of the maleic anhydride derivative used is preferably 1 mol to 1.5 mol, more preferably 1 mol to 1.2 mol, relative to 1 mol of the nitroamine compound represented by the formula (D1). By using the maleic anhydride in excess, the reaction can proceed smoothly and by-products can be suppressed. This reaction is preferably carried out in a solvent. The preferable solvent or reaction conditions are the same as those for the production of the above-mentioned compound (1).

[Production method of formula (A2)] The method for synthesizing the compound of formula (A2) is not particularly limited, but for example, it can be listed in the diamine represented by the following formula (D2), which is described in Japanese Patent Laid-Open No. 2003-321531 or A method of reacting a maleic anhydride derivative under the conditions described in the specification of International Publication No. 2004/012735 and the like.

With respect to 1 mol of the diamine compound represented by the formula (D2), the amount of the maleic anhydride derivative used is preferably 0.01-1 mol, more preferably 0.1-1.0 mol. By using the diamine (D2) in excess, the reaction proceeds smoothly and by-products are suppressed. The reaction is preferably carried out in a solvent. The preferable solvent or reaction conditions are the same as those for the production of the above-mentioned compound (1).

Moreover, the method of reducing the diamine represented by following formula (A1) can also be mentioned,

。

.

From the viewpoint of suppressing the reduction of the double bond, the reaction conditions for reducing the nitro compound represented by the formula (A1) to obtain the amine represented by the formula (A2) are described in the reduction of the compound represented by the above formula (C1) In the reaction of the conditions for producing the specific diamine represented by the formula (1), it is preferable to carry out the reduction reaction in the coexistence of Fe, Sn, Zn or a salt thereof and a proton.

Moreover, as the specific diamine system of this invention, the maleimide compound represented by the following formula (A1) and the commercially available amine compound represented by the following formula (E) can be exemplified by ammonia, alkylamine, benzene Methylamine and the like are reacted to obtain a nitro compound represented by the following formula (F), and further, with commercially available nitrobenzyl chloride, nitrobenzyl chloride, nitrobenzenesulfonic acid represented by the following formula (G) Acryloyl chloride or nitrobenzene isocyanate, 4-fluoronitrobenzene, 4-iodonitrobenzene and the like are reacted to obtain the following formula (C2), and the method of reducing it,

以式(E)表示之化合物與以式(A1)表示之化合物之反應條件係依以上述式(B1)表示之化合物與以式(A1)表示之化合物之反應條件。

The reaction conditions of the compound represented by the formula (E) and the compound represented by the formula (A1) are based on the reaction conditions of the compound represented by the formula (B1) and the compound represented by the formula (A1).

If necessary, a compound in which Z is OH and L ¹ is a carbonyl group in the above formula (G) and a compound represented by the above formula (F) are subjected to the reaction using an inert solvent, if necessary, in the presence of a base, by By reacting with a condensing agent, the compound in which L ¹ is a carbonyl group in the general formula (C2) can be obtained. For 1 equivalent of the compound represented by the formula (G), the amount of the reaction substrate can be 0.5 to 2 equivalents of the compound represented by the general formula (F).

With respect to the compound in the above formula (G) in which Z is OH and L ¹ is a carbonyl group, the condensing agent is not particularly limited as long as it is used in general amide synthesis, but for example, 1 to 4 equivalents of mukaiyama reagent (2) can be used. -Chloro-N-picoline iodide), DCC (1,3-dicyclohexylcarbodiimide), WSC (1-ethyl-3-(3-dimethylaminopropyl)-carbon Diimidimide hydrochloride), CDI (carbonyldiimidazole), dimethylpropynyl bromide, propargyl triphenylphosphonium bromide, DEPC (diethyl cyanophosphate), etc.

In the case of using a solvent, as long as it does not interfere with the progress of the reaction, the solvent that can be used is not particularly limited, but, for example, aromatic hydrocarbons such as benzene, toluene, and xylene, and aliphatics such as hexane and heptane can be mentioned. Alicyclic hydrocarbons, alicyclic hydrocarbons such as cyclohexane, aromatic halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1 ,1,1-trichloroethane, trichloroethylene, tetrachloroethylene and other aliphatic halogenated hydrocarbons, diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran, 1,4-dioxane ethers such as ethyl acetate, ethyl propionate and other esters, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, etc. Amines such as amides, triethylamine, tributylamine, N,N-dimethylaniline, etc., pyridines such as pyridine and picoline, acetonitrile and dimethylsulfoxide, etc. These solvents may be used alone or in combination of two or more.

The addition of a base is not necessarily required, but in the case of using a base, with respect to the compound in which Z is OH and L ¹ is a carbonyl group in the above formula (G), for example, 1 to 4 equivalents of sodium hydroxide, potassium hydroxide and other bases can be used Metal hydroxides, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate, triethylamine, tributylamine, N,N-dimethylaniline , pyridine, 4-(dimethylamino)pyridine, imidazole, 1,8-diazabicyclo[5,4,0]-7-undecene and other organic bases. The reaction temperature can be set at any temperature from -60°C to the reflux temperature of the reaction mixture. The reaction time varies according to the concentration of the reaction substrate and the reaction temperature, but generally can be set arbitrarily within the range of 5 minutes to 100 hours. In general, for example, 1 to 20 equivalents of the compound represented by the above formula (F) and ¹ to 4 equivalents of WSC (1- Condensing agents such as ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride), CDI (carbonyldiimidazole), etc., if necessary, in 1~4 equivalents of potassium carbonate, In the presence of a base such as triethylamine, pyridine, 4-(dimethylamino)pyridine, etc., solvent-free or a solvent such as dichloromethane, chloroform, diethyl ether, tetrahydrofuran, 1,4-dioxane, etc. is used , It is better to carry out the reaction for 10 minutes to 24 hours in the range from 0 ℃ to the reflux temperature of the solvent.

In addition, from the compound in the above formula (G) where Z is OH and L ¹ is a carbonyl group or a sulfonyl group, well-known methods described in the literature can be used, for example, thionyl chloride, phosphorus pentachloride or oxalate A method of reacting with a chlorinating agent such as chlorine, a method of reacting with an organic acid halide such as trimethylacetyl chloride or isobutyl chloroformate, and, if necessary, a method of reacting in the presence of a base, or a method of reacting with carbonyldiimidazole or sulfonic acid A compound of the above formula (G) in which Z is Cl and L ¹ is a carbonyl group or a sulfonyl group and a compound represented by the above formula (F), which are synthesized by a method such as a reaction with bisimidazole, etc., are used inert to the reaction if necessary. The solvent of , if necessary, in the presence of a base, can also be synthesized in the compound of the general formula (C2) wherein L ¹ is a carbonyl group or a sulfonyl group. The amount of the reaction substrate can be 0.5 to 2 equivalents of the compound represented by the above formula (F) relative to 1 equivalent of the compound in the above formula (G) wherein Z is Cl and L ¹ is a carbonyl group or a sulfonyl group.

In the case of using a solvent, the solvent that can be used is not particularly limited as long as it does not hinder the progress of the reaction, and examples thereof include aromatic hydrocarbons such as benzene, toluene, and xylene, and aliphatic hydrocarbons such as hexane and heptane. , alicyclic hydrocarbons such as cyclohexane, aromatic halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1, Aliphatic halogenated hydrocarbons such as 1-trichloroethane, trichloroethylene, tetrachloroethylene, ethers such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran, 1,4-dioxane, etc. esters, ethyl acetate, ethyl propionate, etc., N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, etc. amides , Triethylamine, tributylamine, N,N-dimethylaniline and other amines, pyridine, picoline and other pyridines, acetonitrile and water, etc. These solvents may be used alone, or two or more of these may be mixed and used.

The addition of a base is not necessarily required, but in the case of using a base, with respect to the compound in the above formula (G) where Z is Cl and L ¹ is a carbonyl group or a sulfonyl group, 1 to 4 equivalents of, for example, sodium hydroxide, hydrogen Alkali metal hydroxides such as potassium oxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate, triethylamine, tributylamine, N,N -Organic bases such as dimethylaniline, pyridine, 4-(dimethylamino)pyridine, imidazole, 1,8-diazabicyclo[5,4,0]-7-undecene, etc. The reaction temperature can be set at any temperature from -60°C to the reflux temperature of the reaction mixture. The reaction time varies according to the concentration of the reaction substrate and the reaction temperature, but generally can be arbitrarily set in the range of 5 minutes to 100 hours. Generally speaking, if necessary, the compound represented by the above formula (F) is 1 to 10 equivalents relative to 1 equivalent of the compound in which Z is Cl and L1 is ^a carbonyl group in the above formula (G), for example, in 1 to 2 equivalents. In the presence of bases such as potassium carbonate, triethylamine, pyridine, 4-(dimethylamino)pyridine, etc., use solvent-free or dichloromethane, chloroform, diethyl ether, tetrahydrofuran, 1,4-dioxane , ethyl acetate, acetonitrile and other solvents, from 0 ℃ to the range of the reflux temperature of these solvents, it is better to carry out the reaction for 10 minutes to 48 hours.

Relative to formula (G), L ¹ and W ¹ are both single bonds, and Z is F or Cl, and NO ₂ group relative to Z is a nitro compound at the 2-position or 4-position in the presence of an appropriate base , and react with the compound represented by formula (F) to obtain the dinitro body represented by the above formula (C2). The bases used can be, for example, inorganic bases such as sodium bicarbonate, potassium bicarbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, etc.; trimethylamine, triethylamine, tripropylamine, Amines such as triisopropylamine, tributylamine, diisopropylethylamine, pyridine, quinoline, collidine, etc.; bases such as sodium hydride, potassium hydride, etc.

As for the solvent, any one can be used as long as it does not react with the raw material. For example, aprotic polar organic solvents (N,N-dimethylformamide, dimethylsulfoxide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, etc.), Ethers (Et ₂ O, i-Pr ₂ O, tert-butyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran, dioxane, etc.), aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.) ), aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, etc.), halogen hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, etc.) , dichloroethane, etc.), lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.), nitriles (acetonitrile, propionitrile, butyronitrile, etc.). These solvents can be appropriately selected in consideration of easiness of reaction initiation and the like. In this case, the above-mentioned solvent systems may be used alone or in combination of two or more. Depending on the situation, use a suitable dehydrating agent or desiccant, and also use a dehydrating and drying solvent. The reaction temperature can be in the range from -100°C to the boiling point of the solvent used, and any temperature can be selected, but it is preferably in the range of -50 to 150°C. The reaction time can be arbitrarily selected within the range of 0.1 to 1000 hours, but is preferably 0.1 to 100 hours.

As long as Z is a Br or I atom, the NO ₂ group can be in the 2-, 3-, or 4-position relative to X, and contains appropriate metal catalysts and ligands, by using CN cross-coupling reaction in the presence of a base, Obtain the dinitro body. Examples of the metal catalyst include palladium acetate, palladium chloride, palladium chloride-acetonitrile complex, palladium-activated carbon, bis(diphenylideneacetone)palladium, and ginseng(diphenylideneacetone)dipalladium , bis(acetonitrile)dichloropalladium, bis(benzonitrile)dichloropalladium, CuCl, CuBr, CuI, CuCN, etc., but not limited thereto. Examples of the ligand include triphenylphosphine, tri-o-paraphosphine, diphenylmethylphosphine, phenyldimethylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,1'-bis(diphenylphosphino)ferrocene, trimethylidene Phosphate, triethylphosphite, triphenylphosphite, tri-tert-butylphosphine, etc. are not limited to these. As an example of the base, the aforementioned bases can be used. The reaction solvent and reaction temperature are as described above. The target product in each stage obtained by the above-mentioned reactions can be purified by distillation, recrystallization or silica gel column chromatography. In addition, the reaction conditions for reducing the dinitro compound represented by the formula (C2) to obtain the diamine represented by the formula (1) are the same as those described above.

<Polymer> The polymer of the present invention is obtained by using the above-mentioned diamine. Specific examples include polyamic acid, polyamic acid ester, polyimide, polyurea, polyamide and the like, but from the viewpoint of use as a liquid crystal aligning agent, it is more preferable to be selected from the group consisting of the following At least one of the polyimide precursor of the structural unit represented by the formula (3) and the polyimide of the imide compound thereof,

。

.

In the above formula (3), X ¹ represents a tetravalent organic group derived from a tetracarboxylic acid derivative, Y ¹ represents a divalent organic group derived from a diamine having the structure of the formula (1), and R ⁴ represents a hydrogen atom Or an alkyl group with 1 to 5 carbon atoms. R ⁴ is preferably a hydrogen atom, a methyl group or an ethyl group from the viewpoint of easiness of imidization by heating.

<Tetracarboxylic dianhydride> X ¹ in the polyimide precursor depends on the solubility of the polymer in the solvent, the coatability of the liquid crystal alignment agent, the alignment of the liquid crystal in the case of a liquid crystal alignment film, The degree of necessary characteristics such as voltage holding ratio and accumulated charge is appropriately selected, and may be one type of the same polymer, or two or more types may be mixed. In particular, specific examples of X ¹ include structures of formulae (X-1) to (X-46) disclosed in pages 13 to 14 of International Publication No. 2015/119168. In the following, the preferable structure of X ¹ is shown, but the present invention is not limited to these.

Among the above-mentioned structures, (A-1) and (A-2) are particularly preferred from the viewpoint of further improving the friction resistance, and (A-4) is particularly preferred from the viewpoint of further enhancing the relaxation speed of the accumulated charge. (A-15) to (A-17) and the like are particularly preferred from the viewpoint of further improving the liquid crystal alignment and the relaxation speed of the accumulated charge.

<Polymer (other structural unit)>

The polyimide precursor containing the structural unit represented by the formula (3) may contain a structural unit represented by the following formula (4) and an imide compound thereof within the range that does not impair the effects of the present invention. at least one of the polyimides,

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

As a specific example of X ² , a preferable example is also included, and the structure similar to the thing exemplified by X ¹ of Formula (3) can be mentioned. In addition, Y ² in the polyimide precursor is a divalent organic group derived from a diamine that does not include the structure of formula (1) in the main chain direction, and its structure is not particularly limited. Further, Y ² is appropriate to the extent that the solubility of the polymer in the solvent, the coatability of the liquid crystal aligning agent, the alignment of the liquid crystal in the case of a liquid crystal aligning film, the voltage holding ratio, the accumulation of electric charges, etc. are necessary characteristics. Optionally, it may be one type of the same polymer, or two or more types may be mixed.

If a specific example of Y ² is particularly shown, the group represented by the above formula [W ² -1] to formula [W ² -152] can be mentioned. In addition, the structure of formula (2) disclosed on page 4 of International Publication 2015/119168 and formulas (Y-1) to (Y-97) and (Y-101) disclosed on pages 8 to 12 can be cited. )~(Y-118) structure; from the formula (2) disclosed in the International Publication 2013/008906-6 page to remove the divalent organic group of two amine groups; from the International Publication 2015/122413-8 page The disclosed formula (1) removes two divalent organic groups of amine groups; the structure of the formula (3) disclosed in the International Publication 2015/060360-8 page; from the Japanese Laid-Open Patent Publication 2012-173514-8 page The recorded formula (1) removes the divalent organic group of 2 amine groups; from the formulas (A)~(F) disclosed in the 9th page of International Publication 2010-050523, the divalent organic group of 2 amine groups is removed Wait. As a preferable structure of ^Y2 , the structure of following formula (11) is mentioned.

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 to 10, and preferably 3 to 7. In addition, any -CH ₂ - may be substituted with ether, ester, amide, urea, or urethane bond under 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 the benzene ring may be substituted with a monovalent organic group, preferably a fluorine atom or a methyl group. Specifically, the following structures are exemplified as a series of structures represented by the formula (11), but are not limited to these.

When the polyimide precursor containing the structural unit represented by the formula (3) simultaneously contains the structural unit represented by the formula (4), from the viewpoint of controlling the deviation between the rubbing direction and the alignment direction of the liquid crystal In order to rapidly relax the accumulated charge, the structural unit represented by the formula (3) is preferably 1~80 mol% or more, more preferably 5~60 mol%, relative to the total of the formulas (3) and (4). ear % or more, especially preferably 10-40 mol % or more.

Moreover, as a preferable structure of ^Y2 , 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 heterocycle is mentioned. As such, the structure of Y ² has at least one structure selected from the group consisting of an amine group, an imino group, and a nitrogen-containing heterocycle, or if it has an amine group substituted with thermal dissociation on the nitrogen atom The structure of at least one of , imino group and nitrogen-containing heterocycle is not particularly limited. To give this specific example, there can be mentioned at least one selected from the group consisting of an amino group represented by the following formulae (YD-1) to (YD-5), an imino group, and a nitrogen-containing heterocycle The structure of the 2-valent organic group.

In formula (YD-1), A ₁ represents a nitrogen atom-containing heterocycle with 3 to 15 carbon atoms, and Z ₁ represents a hydrogen atom or a hydrocarbon group with 1 to 20 carbon atoms which may have a substituent. In formula (YD-2), V ₁ represents a hydrocarbon group with 1 to 10 carbon atoms, and A ₂ represents a monovalent organic group with 3 to 15 carbon atoms or a carbon number 1 to 6 in a heterocyclic ring containing nitrogen atoms. The aliphatic group is substituted with the disubstituted amine group. In the formula (YD-3), V ₂ represents a divalent organic group with 6 to 15 carbon atoms and 1 to 2 benzene rings, and V ₃ represents an alkylene group or biphenyl with 2 to 5 carbon atoms, Z ₂ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a benzene ring, or thermal dissociation, and a represents an integer of 0 to 1. In formula (YD-4), A ₃ represents a nitrogen atom-containing heterocyclic ring having 3 to 15 carbon atoms. In formula (YD-5), A ₄ represents a nitrogen atom-containing heterocyclic ring having 3 to 15 carbon atoms, and V ₅ represents an alkylene group having 2 to 5 carbon atoms.

A nitrogen atom-containing heterocyclic ring having 3 to 15 carbon atoms as A ₁ , A ₂ , A ₃ and A ₄ of formulas (YD-1), (YD-2), (YD-4) and (YD-5) If it is a well-known structure, it is not particularly limited. 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 preferred. In addition, the thermally dissociable system does not dissociate at room temperature, but only needs to be dissociated when the alignment film is fired and replaced with a hydrogen atom, and specific examples thereof include tert-butoxycarbonyl and 9-intenylmethoxycarbonyl.

式(YD-14)及(YD-21)中，j係表示0~3之整數，Specific examples of such Y ² include organic groups having a divalent nitrogen atom represented by the following formulae (YD-6) to (YD-52). In order to suppress charge accumulation by AC drive, the formula (YD-14) ~ formula (YD-21) is preferred, (YD-14) and (YD-18) are particularly preferred,

In formulas (YD-14) and (YD-21), j represents an integer from 0 to 3,

式(YD-24)、(YD-25)、(YD-28)及(YD-29)中，j係表示0~3之整數，

In formulas (YD-24), (YD-25), (YD-28) and (YD-29), j represents an integer from 0 to 3,

式(YD-50)中，m、n係表示各自1~11之整數，m+n係表示2~12之整數。

In formula (YD-50), m and n each represent an integer of 1 to 11, and m+n represents an integer of 2 to 12.

<Method for producing polyamic acid> The polyimide precursor used in the present invention, that is, polyamic acid, can be synthesized by the method shown below. Specifically, in the presence of an organic solvent, tetracarboxylic dianhydride and diamine can be carried out at -20 to 150° C., preferably 0 to 70° C., for 30 minutes to 24 hours, preferably 1 to 100° C. 12 hours reaction to synthesize. The organic solvent used in the above reaction is preferably N,N-dimethylformamide, N-methyl-2-pyrrolidone, γ-butyrolactone, etc., from the viewpoint of the solubility of monomers and polymers. These can be used alone or in combination of two or more. The concentration of the polymer is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass, from the viewpoint of hardly causing precipitation of the polymer and easily obtaining a high molecular weight body.

The polyamic acid obtained as described above can be poured into a poor solvent while sufficiently stirring the reaction solution, whereby the polymer can be precipitated and recovered. In addition, after performing precipitation several times, washing with a poor solvent, and drying at room temperature or heating, a powder of purified polyamic acid can be obtained. The poor solvent is not particularly limited, and examples thereof include water, methanol, ethanol, 2-propanol, hexane, butyl cellosolve, acetone, toluene and the like, and water, methanol, ethanol, 2-propanol and the like are preferable.

<Method for producing polyimide> The polyimide used in the present invention can be produced by imidizing the aforementioned polyimide. In the case of producing polyimide from polyimide, chemical imidization by adding a catalyst to the solution of the above-mentioned polyimide obtained by the reaction of a diamine component and tetracarboxylic dianhydride is simple. Chemical imidization is preferable because the imidization reaction is carried out at a relatively low temperature, and the molecular weight of the polymer is not easily reduced during the imidization process. Chemical imidization can be performed by stirring the polymer to be imidized in an organic solvent in the presence of a basic catalyst and an acid anhydride. As the organic solvent, the solvent used in the aforementioned polymerization reaction can be used. As a basic catalyst, pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc. are mentioned. Among them, pyridine is preferable because it has a moderate basicity for the reaction. Moreover, acetic anhydride, trimellitic anhydride, pyromellitic anhydride etc. are mentioned as an acid anhydride, and it is preferable to use an acetic anhydride because purification after completion|finish of reaction becomes easy.

The temperature for the imidization reaction is -20 to 140°C, preferably 0 to 100°C, and the reaction time can be 1 to 100 hours. The amount of the alkaline catalyst is 0.5~30 times the mole of the polyamide base, preferably 2~20 times the mole, and the amount of the acid anhydride is 1~50 times the mole of the polyamide base, preferably 3~ 30 times moles. The imidization rate of the obtained polymer can be controlled by adjusting the amount of catalyst, temperature and reaction time. Since the added catalyst and the like remain in the solution after the imidization reaction of the polyamic acid, the obtained imidized polymer is recovered by the means described below, and redissolved in an organic solvent, and It is preferable to be the liquid crystal alignment agent of the present invention.

The solution of the polyimide obtained as described above can be poured into a poor solvent with sufficient stirring, whereby the polymer can be precipitated. After several times of precipitation, washing with a poor solvent, and drying at room temperature or heating, a purified polymer powder can be obtained. The above-mentioned poor solvent is not particularly limited, and examples thereof include methanol, 2-propanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and the like. Methanol, ethanol, 2-propanol, acetone, etc. are preferred.

<Production of Polyimide Precursor—Polyurethane> The polyimide precursor used in the present invention, that is, the polyimide, can be prepared by using one of (1), (2) or (3) shown below. Manufacturing method.

(1) In the case of production from polyamic acid Polyamic acid ester can be produced by esterification to produce polyamic acid as described above. Specifically, the polyamide acid and the esterifying agent can be mixed in the presence of an organic solvent at -20°C to 150°C, preferably 0°C to 50°C, for 30 minutes to 24 hours, preferably 1 to 100°C. 4 hour reaction to manufacture. The esterification agent is preferably one that can be easily removed by purification, and examples thereof include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dimethylformamide diethyl acetal, and N,N-dimethylformamide dimethyl acetal. ,N-dimethylformamide dipropyl acetal, N,N-dimethylformamide di-neopentyl butyl acetal, N,N-dimethylformamide di-t-butyl acetal Acetal, 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-methylmorpholine hydrochloride (Morpholinium chloride) and the like. The addition amount of the esterifying agent is preferably 2-6 mol equivalents relative to 1 mol of the repeating unit of the polyamide acid.

Examples of the organic solvent include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylethyl acetate amide, dimethylsulfoxide or 1,3-dimethyl-tetrahydroimidazolone. In addition, when the solvent solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formula [ D-1] ~ the solvent represented by formula [D-3].

These vehicles may be used alone or in combination. Furthermore, even if it is a solvent that does not dissolve the polyimide precursor, it can be mixed with the above-mentioned solvent in the range where the polyimide precursor produced does not precipitate. In addition, since the water in the solvent inhibits the polymerization reaction and further causes hydrolysis of the polyimide precursor produced, it is preferable that the solvent is dehydrated and dried. The solvent used in the above reaction is preferably N,N-dimethylformamide, N-methyl-2-pyrrolidone or γ-butyrolactone in view of the solubility of the polymer, and one of these can be used. Or use a mixture of two or more. The concentration at the time of production is preferably 1 to 30 mass %, and more preferably 5 to 20 mass %, from the viewpoint that precipitation of the polymer is unlikely to occur and a high molecular weight body is easily obtained.

(2) When produced by the reaction of tetracarboxylic acid diester dichloride and diamine Polyamic acid ester can be produced from tetracarboxylic acid diester dichloride and diamine. Specifically, tetracarboxylic acid diester dichloride and diamine can be carried out at -20°C to 150°C, preferably 0°C to 50°C for 30 minutes to 24 hours in the presence of a base and an organic solvent. Preferably, it is produced by reaction for 1 to 4 hours. Among the aforementioned bases, pyridine, triethylamine, 4-dimethylaminopyridine, and the like can be used, but pyridine is preferred in order to conduct the reaction stably. The addition amount of the base is preferably 2 to 4 times mol relative to the tetracarboxylic acid diester dichloride from the viewpoint of an amount that can be easily removed and a high molecular weight product is easily obtained.

The solvent used in the above-mentioned reaction is preferably N-methyl-2-pyrrolidone or γ-butyrolactone in view of solubility of the monomer and polymer, and these may be used alone or in combination of two or more. The polymer concentration at the time of production is preferably 1 to 30 mass %, and more preferably 5 to 20 mass % from the viewpoint that precipitation of the polymer is unlikely to occur and a high molecular weight body is easily obtained. In addition, in order to prevent the hydrolysis of the tetracarboxylic acid diester dichloride, the solvent used in the manufacture of the polyamic acid ester is preferably dehydrated as much as possible, and it is better to prevent the mixing of external air in a nitrogen environment.

(3) When produced from tetracarboxylic acid diester and diamine Polyamic acid ester can be produced by polycondensation of tetracarboxylic acid diester and diamine. Specifically, the tetracarboxylic acid diester and diamine can be carried out at 0°C to 150°C, preferably 0°C to 100°C for 30 minutes to 24 hours in the presence of a condensing agent, a base and an organic solvent, preferably It is produced by reaction for 3 to 15 hours. Among the aforementioned condensing agents, triphenyl phosphite, dicyclohexylcarbodiimide (Carbodiimide), 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide salt can be used acid, N,N'-carbonyldiimidazole, dimethoxy-1,3,5-triazinylmethylmorpholinium, O-(benzotriazol-1-yl)-N,N,N ',N'-tetramethyluronium tetrafluoroborate, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate, (2 , 3-dihydro-2-sulfanyl (thioxo)-3-benzoxazolyl) diphenyl phosphonate and the like. The addition amount of the condensing agent is preferably 2 to 3 times moles relative to the tetracarboxylic acid diester.

As the aforementioned bases, tertiary amines such as pyridine and triethylamine can be used. The addition amount of the alkali is preferably 2 to 4 times mol relative to the diamine component from the viewpoint of an amount that can be easily removed and a high molecular weight body is easily obtained. In addition, in the above-mentioned reaction, the reaction proceeds efficiently by adding a Lewis acid as an additive. As the Lewis acid, lithium halides such as lithium chloride and lithium bromide are preferable. The addition amount of the Lewis acid is preferably 0 to 1.0 times mol relative to the diamine component. Among the above-mentioned three methods for producing a polyamic acid ester, a high-molecular-weight polyamic acid ester is obtained, so the above-mentioned production method (1) or the above-mentioned (2) is particularly preferable.

A polymer can be precipitated by pouring the solution of the polyamic acid ester obtained as described above into a poor solvent while stirring well. After performing several precipitations, washing with a poor solvent, and drying at room temperature or heating, a powder of purified polyamide can be obtained. Although the poor solvent is not particularly limited, water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene, and the like are exemplified.

In the production of the polymer of the present invention, in the above-mentioned production method, the diamine represented by the formula (1) may be used as the diamine. The polymer contained in the liquid crystal alignment agent of the present invention is the molecular weight of the polyimide precursor or polyimide, and the liquid crystal alignment film is obtained from the liquid crystal alignment agent containing the polymer, considering the coating film (liquid crystal alignment The strength of the film), the workability during the formation of the coating film and the uniformity of the coating film, the weight average molecular weight measured by GPC (Gel Permeation Chromatography) method is preferably 2,000~500,000, preferably 5,000~300,000, more preferably 10,000~ 100,000.

<Liquid crystal aligning agent> The liquid crystal aligning agent of this invention contains the polymer (specific polymer) obtained from the diamine which has the structure represented by Formula (1). Moreover, as long as the effects described in the present invention are exhibited, two or more specific polymers of different structures may be included. Moreover, in addition to a specific polymer, another polymer may be contained, and the polymer which does not have the divalent group represented by Formula (1) may be contained. Examples of other polymers include polyamide, polyimide, polyamide, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivatives, polyacetal, Polystyrene or its derivatives, 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 a specific polymer with respect to the whole polymer component is 5 mass % or more, As an example, 5-95 mass % is mentioned.

The liquid crystal aligning agent is used for producing a liquid crystal aligning film, and is generally in the form of a coating liquid from the viewpoint of forming a uniform thin film. Even in the liquid crystal aligning agent of the present invention, a coating liquid containing the aforementioned polymer component and an organic solvent for dissolving the polymer component is preferable. At this time, the concentration of the polymer in the liquid crystal aligning agent can be appropriately changed by setting the thickness of the coating film to be formed. From the viewpoint of forming a uniform and defect-free coating film, 1 mass % or more is preferable, and from the viewpoint of the storage stability of the solution, it is preferable to be 10 mass % or less. The concentration of the particularly preferred polymer is 2 to 8 mass %.

The organic solvent contained in the liquid crystal aligning agent is not particularly limited as long as it dissolves the polymer component uniformly. Specific examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, Methylidene, γ-butyrolactone, 1,3-dimethyl-tetrahydroimidazolone, methyl ethyl ketone, cyclohexanone, cyclopentanone, etc. Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone is preferably used.

In addition, the organic solvent contained in the liquid crystal aligning agent is generally used in addition to the above-mentioned solvents, and a mixed solvent of a solvent that improves the coating property when coating the liquid crystal aligning agent or the surface smoothness of the coating film is also used. The liquid crystal alignment agent of the present invention is also suitable to use such mixed solvent. Specific examples of the organic solvent used in combination are listed below, but are not limited to these examples. For example, ethanol, isopropanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1 -Butanol, isoamyl alcohol, tert-amyl 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, cycloheptanol Hexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol Alcohol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methane Ethyl-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, diethylene glycol diethyl ether, 4-hydroxy-4 - methyl-2-pentanone, diethylene glycol methyl ethyl 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 mono Hexyl ether, 2-(hexyloxy)ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, propylene glycol monobutyl ether, 1-(butoxyethoxy) propanol, propylene glycol monomethyl ether acetate, diethylene glycol Propylene Glycol, Dipropylene Glycol Monomethyl Ether, Dipropylene Glycol Monoethyl Ether, Dipropylene Glycol Dimethyl Ether, Tripropylene Glycol Monomethyl Ether, Ethylene Glycol Monomethyl Ether Acetate, Ethylene Glycol Monoethyl Ether Acetic Acid Esters, Ethylene Glycol Monobutyl Ether Acetate, Ethylene Glycol Monoacetate, Ethylene Glycol Diacetate, Diethylene Glycol Monoethyl Ether Acetate, Diethylene Glycol Monobutyl Ether Ethyl acid ester, 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, Methyl 3-Methoxypropionate , methyl ethyl 3-ethoxy propionate, ethyl 3-methoxy propionate, 3-ethoxy propionic acid, 3-methoxy propionic acid, propyl 3-methoxy propionate, 3 -Butyl methoxypropionate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, represented by the following formulae [D-1]~[D-3] solvent, etc.

式[D-1]中，D¹ 表示碳數1~3之烷基，式[D-2]中，D² 表示碳數1~3之烷基，式[D-3]中，D³ 表示碳數1~4之烷基。

In formula [D-1], D ¹ represents an alkyl group with 1 to 3 carbon atoms, in formula [D-2], D ² represents an alkyl group with 1 to 3 carbon atoms, and in 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 are preferred. The type and content of such a solvent are appropriately selected according to the coating apparatus, coating conditions, coating environment, and the like of the liquid crystal alignment agent.

The liquid crystal aligning agent of the present invention may additionally contain components other than the polymer component and the organic solvent within the range that does not impair the effects of the present invention. Examples of such additional components include adhesion aids for improving the adhesion between the liquid crystal alignment film and the substrate or adhesion between the liquid crystal alignment film and the sealing material, crosslinking agents for improving the strength of the liquid crystal alignment film, Dielectric materials or conductive substances used to adjust the permittivity or resistance of liquid crystal alignment films. Specific examples of these additional components are disclosed in various well-known documents related to liquid crystal aligning agents, but if one example is to be shown, pages 53 [0105] to 55 of International Publication No. 2015/060357 can be cited. The ingredients disclosed on page [0116], etc.

<Liquid crystal alignment film> The liquid crystal alignment film of the present invention is obtained from the aforementioned liquid crystal alignment agent. As an example of a method for obtaining a liquid crystal alignment film from a liquid crystal alignment agent, a film obtained by applying a liquid crystal alignment agent in the form of a coating solution to a substrate, drying, and firing can be rubbed or photo-aligned. Treatment method A method of performing alignment treatment. The substrate on which the liquid crystal alignment agent is applied is not particularly limited as long as it is a substrate with high transparency, and plastic substrates such as acrylic substrates and polycarbonate substrates can also be used together with glass substrates and silicon nitride substrates. In this case, it is preferable to use a substrate on which ITO electrodes or the like for driving the liquid crystal are formed, from the viewpoint of simplification of the process. In addition, if the reflective liquid crystal display element is a substrate with only one side, even an opaque material such as a silicon wafer can be used. In this case, a light-reflecting material such as aluminum can also be used for the electrode.

The coating method of the liquid crystal aligning agent is not particularly limited, but industrially, generally, screen printing, offset printing, flexographic printing, inkjet method, etc. are used. As another coating method, there exist a dipping method, a roll coating method, a slit coating method, a spin coating method, a spraying method, etc., and these can be used according to the objective. After coating the liquid crystal aligning agent on the substrate, it is fired by evaporating the solvent by heating means such as a hot plate, a thermal cycle oven, and an IR (infrared) oven. The drying and firing steps after coating the liquid crystal aligning agent can choose any temperature and time. Generally, in order to fully remove the contained solvent, the conditions of baking at 50-120 degreeC for 1-10 minutes, and then baking at 150-300 degreeC for 5-120 minutes are mentioned. The thickness of the liquid crystal alignment film after firing is not particularly limited, but if it is too thin, the reliability of the liquid crystal display element may be reduced, so 5-300 nm is preferable, and 10-200 nm is preferable. The liquid crystal alignment film of the present invention is suitable as a liquid crystal alignment film for a lateral electric field mode liquid crystal display element such as an IPS mode or an FFS mode, and especially can be used as a liquid crystal alignment film for an FFS mode liquid crystal display device.

<Liquid crystal display element> The liquid crystal display element of this invention can be obtained using this liquid crystal cell in order to manufacture a liquid crystal cell by a known method after obtaining the board|substrate with a liquid crystal alignment film obtained from the said liquid crystal aligning agent. As an example of the manufacturing method of a liquid crystal cell, the liquid crystal display element of a passive matrix structure is demonstrated as an example. Furthermore, it can also be a liquid crystal display element of an active matrix structure in which switching elements such as TFT (Thin Film Transistor) are provided in each pixel portion constituting the image display. Specifically, a transparent glass substrate is prepared, a common electrode is provided on one side of the substrate, and a segment electrode is provided on the other side of the substrate. These electrodes can be, for example, ITO electrodes, patterned in such a way that a desired image can be displayed. Next, an insulating film is provided on each substrate so as to cover the common electrode and the segment electrode. The insulating film can be, for example, a film composed of SiO ₂ -TiO ₂ formed by a sol-gel method. Next, a liquid crystal alignment film is formed on each of the substrates under the aforementioned conditions.

Next, a UV-curable sealing material, for example, is placed on a specific spot on one of the two substrates forming the liquid crystal alignment film, and then liquid crystals are placed on specific spots on the surface of the liquid crystal alignment film. The other side of the substrate is attached so that the liquid crystal alignment film is opposed, and the liquid crystal is pressed and diffused on the front of the liquid crystal alignment film, and then the entire surface of the substrate is irradiated with ultraviolet rays to cure the sealing material to obtain a liquid crystal cell. Or as a step after forming the liquid crystal alignment film on the substrate, when disposing the sealing material at a specific point on one side of the substrate, the opening of the liquid crystal can be filled from the outside first, and the substrate is laminated without the liquid crystal. The liquid crystal material is injected into the liquid crystal cell by being provided in the opening of 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 a vacuum injection method or a method utilizing capillary phenomenon in the atmosphere.

Even in any of the above methods, in order to secure a space for filling the liquid crystal cell with the liquid crystal material, columnar protrusions are provided on one substrate, spacers are scattered on one substrate, or the sealing material is mixed Separator, or a combination of these means is preferred. As the above-mentioned liquid crystal material, nematic liquid crystal and smectic liquid crystal can be mentioned, among them, nematic liquid crystal is preferable, and either a positive type liquid crystal material or a negative type liquid crystal material can be used. Next, set the polarizer. Specifically, it is preferable to attach a pair of polarizing plates to the surface opposite to the liquid crystal layer of the two substrates. Furthermore, the liquid crystal alignment film and the liquid crystal display element of the present invention are not limited to the above description, as long as the liquid crystal alignment agent of the present invention is used, and other well-known methods can be used. The steps from a liquid crystal aligning agent to obtaining a liquid crystal display element are also disclosed in many documents except for example, pages 17 [0074] to 19 [0081] of JP 2015-135393 A. [Example]

Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these. The abbreviations of the compounds used in the Examples and Comparative Examples and the method for evaluating the properties are as follows. NMP: N-methyl-2-pyrrolidone BCS: butyl cellosolve GBL: γ-butyl lactone BCS: butyl cellosolve DA-1-1: a compound represented by the following formula DA-1-1 DA-2: the following The compound DA-3 represented by the formula DA-2: the compound CA-1 represented by the following formula DA-3: the compound represented by the following formula CA-1 CA-2: the compound represented by the following formula CA-2

[Example 1] Synthesis of (DA-1-1)

After adding 15.00 g (68.8 mmol) of N-(4-nitrophenyl)maleimide and 300 g of tetrahydrofuran (hereinafter, THF) to the flask, it was cooled with ice. To this mixture, 10.84 g (72.2 mmol) of 4-(2-methylaminoethyl)aniline was added. Then, after returning to room temperature gradually, it stirred at room temperature for 3 hours. After confirming the completion of the reaction, THF was distilled off under reduced pressure. To the obtained residue, n-hexane was added and stirred. The obtained precipitate was filtered. After drying the obtained crystals at 50°C, 21.7 g (84% yield) of the intended nitro body intermediate (DA-1-1-1) was obtained. 1H-NMR (D6-DMSO, δppm): 8.36 (d, 2H), 7.61 (d, 2H), 6.88 (d, 2H), 6.49 (d, 2H), 4.84 (brs, 2H), 4.20-4.25 ( m, 1H), 2.91-3.00 (m, 1H), 2.65-2.83 (m, 3H), 2.54-2.61 (m, 2H), 2.37 (s, 3H)

In the flask after nitrogen substitution, 10 g (27.1 mmol) of (DA1-1-1), 1 g of 5% Pd-C (STD type, wet product, manufactured by ne-chemcat) and 250 g of THF were added to the flask. Hydrogen substitution. The reaction mixture was stirred at room temperature for 2 days under hydrogen pressure and atmospheric pressure. After confirming the completion of the reaction, Pd-C was removed from the reaction mixture by filtration, and the filtrate was distilled off under reduced pressure. To the obtained residue, 50 g of diisopropanol (hereinafter, IPA) was added and stirred. The obtained crystals were filtered and dried at 50° C. to obtain 7.9 g (86% yield) of the target product (DA-1-1) as pale red crystals. 1H-NMR (D6-DMSO, δppm): 6.87 (d, 2H), 6.81 (d, 2H), 6.58 (d, 2H), 6.48 (d, 2H), 5.30 (brs, 2H), 4.83 (brs, 2H), 4.06-4.12(m, 1H), 2.81-2.90(m, 1H), 2.60-2.73(m, 3H), 2.52-2.59(m, 2H), 2.31(s, 3H)

[Example 2] Synthesis of (DA-1-2)

In the flask, 10.00 g (45.8 mmol) of N-(4-nitrophenyl)maleimide and 200 g of THF were added, followed by ice-cooling. To this mixture, 22.4 g (50.0 mmol) of a 7%-methylamine-THF solution was dropped. Then, it was stirred under ice-cooling for 3 hours. After confirming the completion of the reaction, THF was distilled off under reduced pressure to quantitatively obtain the intended intermediate (DA-1-2-1) as a white crystal. 1H-NMR (D6-DMSO, δppm): 8.38 (d, 2H), 7.62 (d, 2H), 3.81-3.87 (m, 1H), 3.03-3.14 (m, 1H), 2.56-2.66 (m, 1H) ), 2.66(brs, 1H), 2.42(s, 3H)

In the flask, 11.4 g (45.7 mmol) of (DA-1-2-1), 200 g of THF, and 5.10 g (50.4 mmol) of triethylamine were added, followed by cooling with ice. To this mixture, 8.08 g (43.5 mol) of 4-nitrobenzyl chloride was added, and the mixture was stirred under ice-cooling for 3 hours. After confirming the completion of the reaction, the precipitate was filtered. The obtained filtrate was distilled off under reduced pressure to obtain (DA-1-2-2) as a crude product. To the obtained crude product, 600 g of IPA and 100 g of pure water were added and stirred. The obtained crystals were filtered and then dried under reduced pressure at 45°C to obtain the intended dinitro compound (DA-1-2-2) as white crystals. 1H-NMR (D6-DMSO, δppm): 8.32-8.44 (m, 4H), 7.73-7.81 (m, 2H), 7.58-7.68 (m, 2H), 4.93-5.13 (m, 1H), 3.00-3.37 (m+s, 2H+3H)

In the flask after nitrogen substitution, add (DA-1-2-2) 2g (5.02mmol), 5% Pd-C 0.5g (STD type, wet product, ne-chemcat (stock)) and N, N - After 20 g of dimethylformamide (hereinafter, DMF), hydrogen was replaced in the flask. The reaction mixture was stirred at room temperature for 2 days under hydrogen pressure and atmospheric pressure. After confirming the completion of the reaction, Pd-C was removed from the reaction mixture by filtration, and the filtrate was distilled off under reduced pressure. To the obtained residue, 50 g of methanol and 2 g of activated carbon (manufactured by Japan Enviro Chemicals Co., Ltd., trade name: special egret) were added, and the mixture was filtered. The filtrate was distilled off under reduced pressure, and 50 g of IPA was added to the resulting residue to crystallize. The obtained crystals were filtered and dried under reduced pressure at 45°C to obtain 1.2 g of white crystals (DA-1-2) (yield: 71%) 1H-NMR (D6-DMSO, δppm): 7.19-7.25(m, 2H), 6.83-6.88(m, 2H), 6.53-6.62(m, 4H), 5.93(brs, 2H), 5.31(brs, 2H), 4.50-4.90(m, 1H), 2.98-3.20(m, 3H), 2.71-2.96(m, 2H)

[Example 3] Synthesis of (DA-1-3)

In the flask, 15.66 g (71.8 mmol) of N-(4-nitrophenyl)maleimide and 300 g of THF were added, followed by cooling with ice. To this mixture, 35.0 g (78.9 mmol) of a 7%-methylamine-THF solution was dropped. Then, it was stirred under ice-cooling for 3 hours. After confirming the completion of the reaction, when THF was distilled off under reduced pressure, the intended intermediate (DA-1-2-1) was quantitatively obtained as a white crystal.

In the flask, 17.8 g (71.4 mmol) of (DA-1-2-1) obtained above, 300 g of THF, and 7.99 g (79.0 mmol) of triethylamine were added, followed by cooling with ice. To this mixture, 15.1 g (68.1 mol) of 4-nitrobenzenesulfonyl chloride was added, and the mixture was stirred at 40°C for 14 hours. After confirming the completion of the reaction, the precipitate was filtered. The obtained filtrate was distilled off under reduced pressure to obtain (DA-1-3-1) as a crude product. To the obtained crude product, 200 g of methanol and 30 g of pure water were added, and the mixture was stirred at 50° C. for 1 hour. After cooling, the obtained crystals were filtered. The obtained crystals were added to 250 g of methanol, and the mixture was stirred at 50°C for 1 hour. Repeat this assignment twice. The obtained crystal was dried under reduced pressure at 45°C to obtain 19.5 g of the intended dinitro compound (DA-1-3-1) as a purple crystal. 1H-NMR (D6-DMSO, δppm): 8.43-8.8.48 (m, 2H), 8.34-8.41 (m, 2H), 8.12-8.17 (m, 2H), 7.57-7.63 (m, 2H), 5.48 -5.55(m, 1H), 3.04-3.14(m, 1H), 2.91-3.02(m, 1H), 2.86(s, 3H)

In the flask after nitrogen substitution, add (DA-1-3-1) 1 g (2.30 mmol), 5% Pd-C 0.5 g (STD type, wet product, ne-chemcat (stock)) and N, N - After 10 g of dimethylformamide (hereinafter, DMF) and 5 g of methanol, hydrogen was replaced in the flask. The reaction mixture was stirred at room temperature for 5 days under hydrogen pressure and atmospheric pressure. After confirming the completion of the reaction, Pd-C was removed from the reaction mixture by filtration, and the filtrate was distilled off under reduced pressure. To the obtained residue, 20 g of THF and 1 g of activated carbon (manufactured by Japan Enviro Chemicals Co., Ltd., trade name: special white heron) were added and filtered. The filtrate was distilled off under reduced pressure, and 10 g of ethanol was added to the resulting residue to crystallize. The obtained crystals were filtered and dried under reduced pressure at 45°C to obtain 0.56 g (DA-1-3) of the objective (yield 65%) as yellow crystals. 1H-NMR (D6-DMSO, δppm): 7.42-7.48(m, 2H), 6.80-6.86(m, 2H), 6.61-6.68(m, 2H), 6.54-6.60(m, 2H), 6.10(brs, 2H), 5.32(brs, 2H), 5.14-5.20(m, 1H), 2.66-2.79(m, 1H), 2.60(s, 3H), 2.51-2.59(m, 1H)

[Viscosity measurement] In the following examples or comparative examples, the viscosity of the polyamic acid solution was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), with a sample volume of 1.1 mL, a cone rotor TE-1 (1°34', R24) measurement.

[Example 4] Synthesis of polyamide acid solution (PAA-1) was placed in a 50ml four-necked flask with a stirring device and a nitrogen introduction tube, 2.36g (7mmol) of (DA-1-1) was added, and 25.0 g of NMP was added, and the mixture was dissolved by stirring while supplying nitrogen. While stirring this diamine solution, 1.43 g (6.58 mmol) of CA-1 was added, and 2.8 g of NMP was added, followed by stirring at 50° C. for 12 hours to obtain a polyamic acid solution (PAA-1). The viscosity of this polyamide solution at 25°C is 250mPa. s.

[Example 5] Synthesis of polyamide acid solution (PAA-2) was placed in a 50ml four-necked flask with a stirring device and a nitrogen introduction tube, after adding (DA-1-1) 2.36g (7mmol), and adding 24.6 g of NMP was dissolved with stirring while feeding nitrogen. While stirring the diamine solution, 0.61 g (2.8 mmol) of CA-1, 0.75 g (3.9 mmol) of CA-2, and 2.7 g of NMP were added, and the mixture was stirred at 50° C. for 12 hours to obtain polyamide Amino acid solution (PAA-2). The viscosity of this polyamide solution at 25°C is 230 mPa. s.

[Comparative Example 1] Synthesis of polyamide acid solution (PAA-3) In a 100 ml four-neck flask with a stirring device and a nitrogen introduction tube, 5.73 g (20 mmol) of (DA-2) was added, and 65.1 g of NMP was added , while feeding nitrogen and stirring to dissolve. While stirring this diamine solution, 4.14 g (19 mmol) of CA-1 was added, and 7.2 g of NMP was added, followed by stirring at room temperature for 18 hours to obtain a polyamic acid solution (PAA-3). The viscosity of this polyamide solution at 25°C is 500mPa. s.

[Comparative Example 2] Synthesis of polyamide acid solution (PAA-4) was placed in a 50ml four-necked flask with a stirring device and a nitrogen introduction tube, after adding (DA-3) 1.98g (10mmol), and adding NMP26. 0 g, which was dissolved by stirring while feeding nitrogen. While stirring this diamine solution, 0.87 g (4.0 mmol) of CA-1, 1.08 g (5.5 mmol) of CA-2, and 2.9 g of NMP were added, and the mixture was stirred at 50° C. for 12 hours to obtain polyamide Amino acid solution (PAA-4). The viscosity of this polyamide solution at 25°C is 300mPa. s.

[Example 6] Preparation of Liquid Crystal Alignment Agent (Q-1) 7.5 g of the polyamic acid solution (PAA-1) obtained in Example 4 was used for isolation, and the mixture containing NMP 5.6 g, BCS 6.0 g, 3 -0.9 g of an NMP solution of 1 wt % of aminopropyltriethoxysilane, and further stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent (Q-1).

[Example 7] Preparation of Liquid Crystal Alignment Agent (Q-2) 7.5 g of the polyamic acid solution (PAA-2) obtained in Example 5 was used, and 7.5 g of NMP 5.6 g, BCS 6.0 g, 3 -0.9 g of an NMP solution of 1 wt % of aminopropyltriethoxysilane, and further stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent (Q-2).

[Comparative example 3] Preparation of liquid crystal alignment agent (Q-3) 7.5 g of the polyamic acid solution (PAA-3) obtained in -0.9 g of an NMP solution of 1 wt % of aminopropyltriethoxysilane, and further stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent (Q-3).

[Comparative Example 4] Preparation of Liquid Crystal Alignment Agent (Q-4) 7.5 g of the polyamic acid solution (PAA-4) obtained in Comparative Example 2 was isolated and added with stirring including NMP 5.6 g, BCS 6.0 g, 3 -0.9 g of an NMP solution of 1 wt % of aminopropyltriethoxysilane, and further stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent (Q-4).

[Preparation of liquid crystal cell for ion density measurement] After filtering the liquid crystal alignment agent with a 1.0 μm filter, it was placed on a substrate with electrodes (30 mm in width × 40 mm in length, and a glass substrate with a thickness of 1.1 mm. The electrodes were A rectangle with a width of 10 mm × a length of 40 mm, and an ITO electrode with a thickness of 35 nm), was coated by spin coating. After drying on a hot plate at 50° C. for 5 minutes, firing was performed in an IR oven at 230° C. for 20 minutes to form a coating film with a thickness of 100 nm to obtain a substrate with a liquid crystal alignment film. This liquid crystal alignment film was rubbed with rayon cloth (YA-20R manufactured by Yoshikawa Chemical Co., Ltd.) (roll diameter: 120 mm, roll rotation number: 1000 rpm, moving speed: 20 mm/sec, extrusion length: 0.4 mm), and then rubbed with pure water for 1 After being irradiated with ultrasonic waves for 1 minute, washed, and water droplets were removed by blowing air, and then dried at 80° C. for 15 minutes to obtain a substrate with a liquid crystal alignment film.

Prepare 2 sheets of the above-mentioned substrates with liquid crystal alignment films, spread 4 μm spacers on the liquid crystal alignment film surface of one sheet, print the sealing material from them, and rub the other substrate with the rubbing direction as the reverse direction, and the film surface is the same. After laminating in a face-to-face manner, the sealing material is hardened to create an empty unit cell. Here, MLC-3019 (manufactured by Merck & Co., Ltd.) was injected into the empty cell by the reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell. Then, the obtained liquid crystal cell was heated at 110 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 for the liquid crystal cell produced by the method described in the above-mentioned [Production of a liquid crystal cell for ion density measurement]. In the ion density measurement, the ion density was measured when a triangular wave with a voltage of ±10 V and a frequency of 0.01 Hz was applied to the liquid crystal cell. The measurement temperature was carried out at 60°C. As a measuring apparatus, the 6256 type liquid crystal physical property evaluation apparatus made by Toyo Technica was used. The measurement of the ion density was performed after the liquid crystal cell was produced and the liquid crystal cell was aged for 120 hours under the high temperature and high humidity conditions of 60° C. and 90%. Furthermore, the ion density was measured for the liquid crystal cell produced using the liquid crystal aligning agent (Q-1) of Example 6 and the liquid crystal cell produced using the liquid crystal aligning agent (Q-3) of Comparative Example 3.

[Fabrication of liquid crystal display element] First, prepare the substrate with electrodes. The substrate is a glass substrate with a size of 30mm×35mm and a thickness of 0.7mm. On the substrate, as a first layer, an IZO electrode having a monolithic pattern constituting a counter electrode was formed. As a second layer, a SiN (silicon nitride) film formed by a CVD method is formed on the opposite electrode of the first layer. The SiN film of the second layer has a film thickness of 500 nm and is used as an interlayer insulating film. On the SiN film of the second layer, as the third layer, a comb-shaped pixel electrode formed by patterning the IZO film is arranged, and two pixels of a first pixel and a second pixel are formed. The size of each pixel is 10 mm in length and about 5 mm in width. At this time, the counter electrode of the first layer and the pixel electrode of the third layer are electrically insulated by the function of the SiN film of the second layer.

The pixel electrode of the third layer is the same as the drawing described in Japanese Patent Application Laid-Open No. 2014-77845, and has a comb-like shape formed by arranging a plurality of electrode elements having a zigzag shape with a curved center portion. The width of each electrode element in the lateral direction was 3 μm, and the interval between the electrode elements was 6 μm. The pixel electrode that forms each pixel is composed of a plurality of electrode elements with a curved center portion of the く shape, so the shape of each pixel is not a rectangular shape, but is similar to the electrode element. shape. Furthermore, each pixel is divided into upper and lower parts with the curved portion at the center thereof as a border, and has a first area on the upper side of the curved portion and a second area on the lower side.

When the first region and the second region of each pixel are compared, the direction in which the electrode elements constituting the pixel electrodes are formed is different. That is, taking the rubbing direction of the liquid crystal alignment film described later as a reference, in the first region of the pixel, the electrode element of the pixel electrode is formed at an angle of +10° (clockwise), and in the second region of the pixel, The electrode elements of the pixel electrode are formed so that the angle (clockwise) of -10° is formed. That is, the first area and the second area of each pixel are configured in the direction of the rotation operation (in-plane/switching) of the liquid crystal in the substrate plane by the voltage application between the pixel electrode and the counter electrode. become opposite to each other.

Next, the obtained liquid crystal alignment agent was filtered with a 1.0 μm filter, spin-coated on the prepared substrate with electrodes and the opposite substrate, respectively, and an ITO film was formed on the back surface with a columnar height of 4 μm. Glass substrate for spacers. Next, after drying on a hot plate at 80° C. for 5 minutes, it was fired at 230° C. for 20 minutes to obtain a polyimide film on each substrate as a coating film with a thickness of 60 nm. The polyimide film was rubbed with a rayon cloth in a specific rubbing direction (roll diameter 120 mm, number of revolutions 500 rpm, moving speed 30 mm/sec, extrusion amount 0.3 mm), and then rubbed in pure water for 1 10 minutes ultrasonic irradiation and drying at 80°C for 10 minutes.

Then, using the above-mentioned two types of substrates with liquid crystal alignment films, the respective rubbing directions were combined so that the respective rubbing directions became anti-parallel, and the liquid crystal injection port was left to seal the periphery to produce an empty cell with a cell gap of 3.8 μm. After the liquid crystal (MLC-3019, manufactured by Merck & Co., Ltd.) was injected into the empty cell under vacuum at room temperature, the injection port was sealed to serve as an antiparallel alignment liquid crystal cell. The obtained liquid crystal cell constitutes an FFS mode liquid crystal display element. Then, the obtained liquid crystal cell was heated at 120 degreeC for 1 hour, and was used for each evaluation after standing overnight.

[Assessment of the stability of liquid crystal alignment] Using this liquid crystal cell, an AC voltage of 10VPP was applied for 168 hours at a frequency of 30Hz in a constant temperature environment of 60°C. Then, it was set as the state which short-circuited between the pixel electrode of a liquid crystal cell and a counter electrode, and was left to stand at room temperature for one day. After standing, the liquid crystal cell is placed between two polarizers arranged with the polarization axis vertical, the backlight is turned on with no voltage applied, and the arrangement of the liquid crystal cell is adjusted so that the brightness of the transmitted light is minimized. angle. Then, from the angle at which the second area of the first pixel becomes the darkest to the angle at which the first area becomes the darkest, the rotation angle when the liquid crystal cell is rotated is calculated as the angle Δ. The same is true for the second pixel, the second area and the first area are compared, and the same angle Δ is calculated. Then, the average value of the angle Δ values between the first pixel and the second pixel was calculated as the angle Δ of the liquid crystal cell. The value of the angle Δ of this liquid crystal cell is 0.15° or less, and is evaluated as good, and the value higher than 0.15° is evaluated as poor.

[Relaxing characteristics of accumulated charge] The above-mentioned liquid crystal cell is placed between two polarizers arranged so that the polarization axis is vertical, and the pixel electrode and the counter electrode are short-circuited to become the same potential state, from the two polarizers. The LED backlight is irradiated below, and the angle of the liquid crystal cell is adjusted so that the luminance of the transmitted light from the LED backlight measured on the two polarizers becomes the smallest. Next, while applying a rectangular wave with a frequency of 30 Hz to this liquid crystal cell, the V-T characteristic (voltage-transmittance characteristic) at a temperature of 23° C. was measured, and an AC voltage with a relative transmittance of 23% was calculated. Since this AC voltage corresponds to a region with a large change in luminance with respect to the voltage, it is precisely used to evaluate the accumulated charge through the luminance.

Next, after applying an AC voltage with a relative transmittance of 23% for 5 minutes, and a rectangular wave with a frequency of 30 Hz, a DC voltage of +1.0 V was superimposed and driven for 30 minutes. Then, the DC voltage was cut off, and only the AC voltage with a relative transmittance of 23% and a rectangular wave with a frequency of 30 Hz was applied again for 30 minutes. Since the faster the relaxation of the accumulated charges, the faster the charge accumulation in the liquid crystal cell when the DC voltage is superimposed, the relaxation characteristics of the accumulated charges are reduced from the state of 30% or more to 23% in the relative transmittance immediately after the superimposition of the DC voltage. % time required to evaluate. The shorter this time is, the better the relaxation characteristics of the accumulated charge are.

<Examples 1 to 4> Using the liquid crystal alignment agents Q1 to Q4 of Examples 6 to 7 and Comparative Examples 3 to 4, ion density measurement, evaluation of the stability of liquid crystal alignment, and evaluation of the relaxation properties of accumulated charges were performed. The results are shown in Table 1. In the table, the liquid crystal cells produced using the liquid crystal alignment agents Q1 to Q2 were used as the respective Examples 8 to 9, and the liquid crystal cells produced using the liquid crystal alignment agents Q3 to Q4 were used as the respective Comparative Examples 5 to 6.

[產業上之可利用性]

[Industrial Availability]

The liquid crystal alignment film of the present invention, especially in the liquid crystal display element of the IPS driving method or the FFS driving method, which requires rubbing treatment, can obtain display performance with excellent afterimage characteristics or contrast. Therefore, it is particularly useful as a liquid crystal alignment film used in a liquid crystal display element of an IPS driving method or an FFS driving method, a multi-function mobile phone (smart phone), a tablet personal computer, a liquid crystal television, and the like.

Claims (14)

A liquid crystal aligning agent characterized by comprising a polymer obtained from a diamine having a structure represented by the following formula (1),

R represents a hydrogen atom or a monovalent organic group, R ¹ represents a hydrogen atom or a straight-chain or branchable alkyl group or an aryl group with a carbon number of 1-5, having 2 on the same maleimide ring The R ¹ can be the same or different from each other, and the two R ¹ can be bonded to each other to form an alkylene group with 3 to 6 carbon atoms, W ¹ represents a single bond or a divalent organic group, and W ² represents Represents a divalent organic group, Ar ¹ represents an aromatic ring, and L ¹ represents a carbonyl group, a sulfonyl group, or an alkylene group having 1 to 20 carbon atoms. The liquid crystal aligning agent according to claim 1, wherein the aforementioned Ar ¹ is 1,3-phenylene or 1,4-phenylene. The liquid crystal aligning agent according to claim 1, wherein the aforementioned W ¹ is a single bond. The liquid crystal aligning agent according to claim 1, wherein the polymer is at least 1 selected from the group consisting of a polyimide precursor including a structural unit represented by the following formula (3) and a polyimide of the imide compound kind,

X ¹ represents a tetravalent organic group derived from a tetracarboxylic acid derivative, Y ¹ represents a divalent organic group derived from a diamine having the structure of the formula (1), and R ⁴ represents a hydrogen atom or a carbon number of 1 to 1 5 of the alkyl group. The liquid crystal aligning agent of claim 4, wherein the structure of the aforementioned X ¹ is at least one selected from the following structures,

The liquid crystal aligning agent according to claim 1, wherein the polymer is at least one selected from the group consisting of a polyimide precursor and a polyimide of the imide compound further comprising a structural unit represented by the following formula (4). 1 type,

X ² represents a tetravalent organic group derived from a tetracarboxylic acid derivative, Y ² represents a divalent organic group derived from a diamine whose main chain direction does not include the structure of the formula (1), and R ¹⁴ represents each independently A hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ¹⁵ represents each independent hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The liquid crystal aligning agent according to claim 6, wherein Y ² is represented by the following 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 any -CH ₂ - may not be adjacent to each other. The conditional substitution is ether, ester, amide, urea, urethane bond, R ³⁴ represents a single bond or a divalent organic group, and any hydrogen atom on the benzene ring can be substituted by a monovalent organic group. The liquid crystal aligning agent according to claim 4, wherein the structural unit represented by the aforementioned formula (3) is 10 mol% or more relative to the total structural unit of the polymer. A liquid crystal alignment film obtained from the liquid crystal alignment agent according to any one of claims 1 to 8. A liquid crystal display element comprising the liquid crystal alignment film of claim 9. A polymer characterized by being obtained from a diamine having a structure represented by the following formula (1),

R represents a hydrogen atom or a monovalent organic group, and R ¹ represents a hydrogen atom or a straight-chain or branchable alkyl group with 1 to 5 carbon atoms or an aryl group, which is on the same maleimide ring. The two R ^1s can be the same or different from each other, and the two R ^1s can be bonded to each other to form an alkylene group with 3 to 6 carbon atoms, W ¹ represents a single bond or a divalent organic group, W ² represents a divalent organic group, Ar ¹ represents an aromatic ring, and L ¹ represents a carbonyl group, a sulfonyl group, or an alkylene group having 1 to 20 carbon atoms. The polymer of claim 11, wherein W ¹ in the aforementioned formula (1) is a single bond. A diamine characterized by having a structure represented by the following formula (1),

R represents a hydrogen atom or a monovalent organic group, and R ¹ represents a hydrogen atom or a straight-chain or branchable alkyl group with 1 to 5 carbon atoms or an aryl group, which is on the same maleimide ring. The two R ^1s can be the same or different from each other, and the two R ^1s can be bonded to each other to form an alkylene group with 3 to 6 carbon atoms, W ¹ represents a single bond or a divalent organic group, W ² represents a divalent organic group, Ar ¹ represents an aromatic ring, and L ¹ represents a carbonyl group, a sulfonyl group or an alkylene group having 1 to 20 carbon atoms. The diamine of claim 13, wherein W ¹ in the aforementioned formula (1) is a single bond.