WO2018159733A1

WO2018159733A1 - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element

Info

Publication number: WO2018159733A1
Application number: PCT/JP2018/007686
Authority: WO
Inventors: 司藤枝; 一平福田; 美希豊田; 雄介山本
Original assignee: 日産化学株式会社
Priority date: 2017-03-02
Filing date: 2018-03-01
Publication date: 2018-09-07
Also published as: CN114609830A; JP7096534B2; KR20190125992A; JPWO2018159733A1; CN114609830B; CN110573952A; TW201842172A; KR102588036B1; JP2022113743A; TWI767870B; TW202214749A; TWI752177B; JP7409431B2; CN110573952B

Abstract

The present invention provides a liquid crystal alignment agent whereby a liquid crystal alignment film is obtained in which the ability thereof to align liquid crystals vertically is not reduced even when the liquid crystal alignment film is exposed to excessive heating, and provides a liquid crystal alignment agent whereby a liquid crystal alignment film is obtained in which the ability thereof to align liquid crystals vertically is not reduced even when some foreign matter touches or damages the film. The present invention provides a liquid crystal alignment agent containing a diamine component containing a diamine represented by formula [1] (In formula [1], X represents a single bond or –O- or another divalent group, Y represents a group represented by formula [1-1], and Y1 through Y6 represent specific groups described in the specification.), and at least one species of polymer selected from a polyimide precursor and a polyimide that is an imidization product of the polyimide precursor, the polyimide precursor being a product of reaction with a tetracarboxylic acid component.

Description

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

The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, and a liquid crystal display element, which are excellent in the ability to align liquid crystal vertically.

A liquid crystal display element of a method in which liquid crystal molecules aligned perpendicular to the substrate respond by an electric field (also referred to as a vertical alignment (VA) method) is irradiated with ultraviolet rays while applying a voltage to the liquid crystal molecules in the manufacturing process. There is a thing including the process to do.

In such a vertical alignment type liquid crystal display element, a photopolymerizable compound is previously added to the liquid crystal composition, and a polyimide-based vertical alignment film is used, and ultraviolet rays are applied while applying a voltage to the liquid crystal cell. Therefore, a technique for increasing the response speed of liquid crystal (PSA (Polymer Sustained Alignment) type element, for example, see Patent Document 1 and Non-Patent Document 1) is known.

As a liquid crystal aligning agent used in such a PSA element, a liquid crystal aligning agent using a side chain having a specific ring structure has been proposed (see Patent Document 2). This specific ring structure has a high ability to align the liquid crystal vertically, and the vertical alignment type liquid crystal display element using this liquid crystal aligning agent has good display characteristics.

JP 2003-307720 A WO2006 / 070819

However, in recent vertical alignment type liquid crystal display elements, due to the reduction in thickness and size of the substrate used, a temperature difference occurs between different parts of the same substrate during firing, and the liquid crystal in the excessively heated part The alignment film has a problem in that the ability to align the liquid crystal vertically decreases, and as a result, the obtained liquid crystal display element partially causes a display defect.
In addition, in the liquid crystal panel manufacturing process, the liquid crystal alignment film and the column spacer come into contact with each other, and the liquid crystal alignment film is damaged, so that an alignment defect (bright spot) is generated in that portion.

An object of the present invention is to provide a liquid crystal aligning agent capable of obtaining a liquid crystal alignment film in which the ability to align liquid crystals vertically does not decrease even when exposed to excessive heating.
Another object of the present invention is to provide a liquid crystal aligning agent capable of obtaining a liquid crystal alignment film that does not deteriorate the ability to align liquid crystals vertically even when some foreign matter comes into contact with the film and is damaged.

The inventors have found that the object can be achieved by a liquid crystal aligning agent having the following constitution, and completed the present invention.
That is, the configuration of the present invention is as follows.
1. A liquid crystal containing at least one polymer selected from a polyimide precursor which is a reaction product of a diamine component containing a diamine represented by the following formula [1] and a tetracarboxylic acid component and a polyimide which is an imidized product thereof. Alignment agent.

In the formula [1], X represents a single bond, —O—, —C (CH ₃ ) ₂ —, —NH—, —CO—, —NHCO—, —COO—, — (CH ₂ ) _m —, — It represents a divalent organic group composed of SO ₂ — and any combination thereof, and m represents an integer of 1 to 8.
Y independently represents a structure of the following formula [1-1].

In formula [1-1], Y ¹ and Y ³ each independently represent a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O— , -CONH-, -NHCO-, -COO-, and -OCO-.
Y ² represents a single bond or — (CH ₂ ) _b — (b is an integer of 1 to 15) (provided that Y ¹ or Y ³ is a single bond, — (CH ₂ ) _a — ² is a single bond, and Y ¹ is at least one selected from the group consisting of —O—, —CH ₂ O—, —CONH—, —NHCO—, —COO—, and —OCO—, and / or Or when Y ³ is at least one selected from the group consisting of —O—, —CH ₂ O—, —CONH—, —NHCO—, —COO— and —OCO—, Y ² is a single bond or — ( CH ₂ ) _b — (provided that when Y ¹ is —CONH—, they are Y ² and Y ³ single bonds)).
Y ⁴ represents at least one divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton and a tocophenol skeleton, The optional hydrogen atom on the cyclic group includes an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, and a fluorine-containing alkoxy group having 1 to 3 carbon atoms. Alternatively, it may be substituted with a fluorine atom.
Y ⁵ represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, a carbon number of 1 It may be substituted with 1 to 3 alkoxy groups, 1 to 3 fluorine-containing alkyl groups, 1 to 3 fluorine-containing alkoxy groups or fluorine atoms.
Y ⁶ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and 1 to 18 carbon atoms. And at least one selected from the group consisting of fluorine-containing alkoxy groups. n represents an integer of 0 to 4.

According to the present invention, it is possible to provide a liquid crystal aligning agent capable of obtaining a liquid crystal alignment film that does not deteriorate the ability to align liquid crystals vertically even when exposed to excessive heating.
Further, according to the present invention, in addition to the above effects or in addition to the above effects, a liquid crystal aligning agent capable of obtaining a liquid crystal alignment film that does not deteriorate the ability to align liquid crystal vertically even when some foreign matter comes into contact with the film and is damaged. Can be provided.
Furthermore, according to the present invention, a liquid crystal alignment film obtained from the liquid crystal alignment agent and a method for obtaining a liquid crystal alignment film using the liquid crystal alignment agent can be provided.

The liquid crystal aligning agent of the present invention contains a diamine represented by the above formula [1] (hereinafter, the “diamine represented by the above formula [1]” may be abbreviated as “specific diamine”). And at least one polymer selected from a polyimide precursor that is a reaction product with a tetracarboxylic acid component and a polyimide that is an imidized product thereof (hereinafter sometimes abbreviated as “specific polymer”).

The specific polymer contains a specific diamine, but may have a diamine other than the specific diamine.
The amount of the specific diamine and other diamines is such that the specific diamine is 5 mol% to 70 mol%, preferably 10 mol% to 50 mol%, more preferably 10 mol% to 40 mol% in the specific polymer. It is good.
Moreover, the liquid crystal aligning agent of this invention may contain "polyimide which is a polyimide precursor and / or its imidized substance" other than a specific polymer.
Hereinafter, “specific diamine” will be described, and then diamines other than “specific diamine” will be described.

<Specific diamine>
The specific diamine used for the liquid crystal aligning agent of this invention is represented by following formula [1].

In the formula [1], X represents a single bond, —O—, —C (CH ₃ ) ₂ —, —NH—, —CO—, —NHCO—, —COO—, — (CH ₂ ) _m —, — It represents a divalent organic group composed of SO ₂ — and any combination thereof, and m represents an integer of 1 to 8.
As “any combination thereof”, —O— (CH ₂ ) _m —O—, —O—C (CH ₃ ) ₂ —, —CO— (CH ₂ ) _m —, —NH— (CH ₂ ) _m -, -SO _2- (CH ₂ ) _m- , -CONH- (CH ₂ ) _m- , -CONH- (CH ₂ ) _m -NHCO-, -COO- (CH ₂ ) _m -OCO-, etc. However, it is not limited to these.
X is preferably a single bond, —O—, —NH—, —O— (CH ₂ ) _m —O—.

In formula [1], Y may be in the meta position or in the ortho position from the position of X, but is preferably in the ortho position. That is, the formula [1] is preferably the following formula [1 ′].

The position of “—NH ₂ ” in the above formula [1] may be any position as shown in formula [1], but preferably the following formula [1] -a1, [1] -a2, [ 1] -a3 is preferable, and [1] -a1 is more preferable.

From the above formulas [1] -a1 to [1] -a3 and the above formula [1 ′], the above formula [1] may be any structure selected from the following formulas, preferably the formula [1] ] -A1-1 is preferable.

Y independently represents the structure of the following formula [1-1].

Examples of the group represented by the above formula [1-1] include, but are not limited to, the following groups [1-1] -1 to [1-1] -22. Of these, [1-1] -1 to [1-1] -4, [1-1] -8, and [1-1] -10 are preferable. Note that * indicates the position of bonding with the phenyl group in the above formula [1], the above formula [1 '], the above formula [1] -a1 to the above formula [1] -a3. m represents an integer of 1 to 15, and n represents an integer of 0 to 18.

<Photoreactive side chain>
The polymer contained in the liquid crystal aligning agent of the present invention may have a photoreactive side chain.
The photoreactive side chain is possessed by “polyimide precursor and / or imidized product thereof” which is a polymer other than “specific polymer”, even if “specific polymer” has. May be.
<Diamine containing photoreactive side chain>
In order to introduce a photoreactive side chain into a polymer other than the “specific polymer” and / or “specific polymer”, a diamine having a photoreactive side chain is used as a part of the diamine component. Good. Examples of the diamine having a photoreactive side chain include, but are not limited to, a diamine having a side chain represented by Formula [VIII] or Formula [IX].

The bonding positions of the two amino groups (—NH ₂ ) in Formula [VIII] and Formula [IX] are not limited. Specifically, with respect to the linking group of the side chain, 2, 3 position, 2, 4 position, 2, 5 position, 2, 6 position, 3, 4 position on the benzene ring, 3, 4 position, 5 positions. Among these, from the viewpoint of reactivity when synthesizing a polyamic acid, positions 2, 4, 2, 5, or 3, 5 are preferable. Considering the ease in synthesizing the diamine, the positions 2, 4 or 3, 5 are more preferable.

The definitions of R ⁸ , R ⁹ and R ¹⁰ in formula [VIII] are as follows.
That is, R ⁸ is a single bond, —CH ₂ —, —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —CH ₂ O—, —N (CH ₃ ). —, —CON (CH ₃ ) —, or —N (CH ₃ ) CO— is represented. In particular, R ⁸ is preferably a single bond, —O—, —COO—, —NHCO—, or —CONH—.
R ⁹ represents a single bond or an alkylene group having 1 to 20 carbon atoms which may be substituted with a fluorine atom, and —CH ₂ — in the alkylene group is optionally substituted with —CF ₂ — or —CH═CH—. If any of the following groups are not adjacent to each other, these groups may be substituted; —O—, —COO—, —OCO—, —NHCO—, —CONH—, — NH-, divalent carbocyclic or heterocyclic ring.
Specific examples of the divalent carbocycle or heterocycle include, but are not limited to, the following.

R ⁹ can be formed by a general organic synthetic method, but a single bond or an alkylene group having 1 to 12 carbon atoms is preferable from the viewpoint of ease of synthesis.
R ¹⁰ represents a photoreactive group selected from the following formulae.

R ¹⁰ is preferably a methacryl group, an acryl group or a vinyl group from the viewpoint of photoreactivity.

In addition, the definitions of Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , and Y _{6 in} the formula [IX] are as follows.
That is, Y ₁ represents —CH ₂ —, —O—, —CONH—, —NHCO—, —COO—, —OCO—, —NH—, or —CO—.
Y ₂ is an alkylene group having 1 to 30 carbon atoms, a divalent carbocycle or a heterocycle, and one or more hydrogen atoms of the alkylene group, divalent carbocycle or heterocycle are fluorine atoms or organic It may be substituted with a group. In Y ₂ , when the following groups are not adjacent to each other, —CH ₂ — may be substituted with these groups; —O—, —NHCO—, —CONH—, —COO—, —OCO—, —NH—, —NHCONH—, —CO—.
Y ₃ represents —CH ₂ —, —O—, —CONH—, —NHCO—, —COO—, —OCO—, —NH—, —CO—, or a single bond.
Y ₄ represents a cinnamoyl group. Y ₅ is a single bond, an alkylene group having 1 to 30 carbon atoms, a divalent carbocycle or a heterocycle, and one or more hydrogen atoms of the alkylene group, divalent carbocycle or heterocycle are fluorine atoms Alternatively, it may be substituted with an organic group.
In Y ₅ , when the following groups are not adjacent to each other, —CH ₂ — may be substituted with these groups; —O—, —NHCO—, —CONH—, —COO—, —OCO—, —NH—, —NHCONH—, —CO—.
Y ₆ represents a photopolymerizable group which is an acrylic group or a methacryl group.

Specific examples of the diamine having a photoreactive side chain include, but are not limited to, the following. In the following formulae, X ⁹ and X ¹⁰ are each independently a single bond, a bonding group that is —O—, —COO—, —NHCO—, or —NH—, and Y may be substituted with a fluorine atom Represents an alkylene group having 1 to 20 carbon atoms.

Also, examples of the diamine having a photoreactive side chain include a diamine having a group causing a photodimerization reaction and a group causing a photopolymerization reaction represented by the following formula in the side chain.

In the above formula, Y ₁ to Y ₆ are the same as defined above.
The diamine having a photoreactive side chain depends on the liquid crystal alignment property when it is used as a liquid crystal alignment film, the pretilt angle, the voltage holding property, the characteristics such as accumulated charge, the response speed of the liquid crystal when it is used as a liquid crystal display device, etc. 1 type or 2 types or more can be mixed and used.

The diamine having a photoreactive side chain is preferably used in an amount of 10 to 70 mol%, more preferably 20 to 60 mol%, particularly preferably 30 to 50 mol% of the diamine component used for the synthesis of the polyamic acid. It is.
Examples of the diamine having a photoreactive side chain include a diamine having a side chain having a site having a radical generating structure that is decomposed by ultraviolet irradiation to generate radicals.

Ar, R ₁ , R ₂ , T ₁ , T ₂ , S and Q in the above formula (1) have the following definitions.
That is, Ar represents an aromatic hydrocarbon group selected from phenylene, naphthylene, and biphenylene, in which an organic group may be substituted, and a hydrogen atom may be substituted with a halogen atom.
R ₁ and R ₂ are each independently an alkyl or alkoxy group having 1 to 10 carbon atoms.
T1 and T2 are each independently a single bond or —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —CH ₂ O—, —N (CH ₃ ) —, It is a bonding group of —CON (CH ₃ ) — and —N (CH ₃ ) CO—.
S is a single bond, unsubstituted or an alkylene group having 1 to 20 carbon atoms substituted by a fluorine atom. However, the alkylene group —CH ₂ — or —CF ₂ — may be optionally replaced with —CH═CH—, and when any of the following groups is not adjacent to each other, these groups are replaced with these groups: -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, a divalent carbocycle, and a divalent heterocycle.
Q is a structure selected from the following (in the structural formula, R represents water, an elementary atom, or an alkyl group having 1 to 4 carbon atoms, and R ₃ represents —CH ₂ —, —NR—, —O—, or —S Represents-).

In the above formula (I), Ar to which carbonyl is bonded is involved in the absorption wavelength of ultraviolet rays. Therefore, when the wavelength is increased, a structure having a long conjugate length such as naphthylene or biphenylene is preferable. Ar may be substituted with a substituent, and the substituent is preferably an electron-donating organic group such as an alkyl group, a hydroxyl group, an alkoxy group, and an amino group.

In the formula (I), when Ar has a structure such as naphthylene or biphenylene, the solubility becomes worse and the difficulty of synthesis becomes higher. If the ultraviolet wavelength is in the range of 250 nm to 380 nm, a phenyl group is most preferable because sufficient characteristics can be obtained even with a phenyl group.

R ₁ and R ₂ are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group, a benzyl group, or a phenethyl group. In the case of an alkyl group or an alkoxy group, R ₁ and R ₂ are May be formed.

In the formula (I), Q is preferably an electron donating organic group, and the above group is preferable.
In the case where Q is an amino derivative, there is a possibility that in the polymerization of polyamic acid which is a precursor of polyimide, there is a possibility that a carboxylic acid group generated and an amino group form a salt. Or it is an alkoxyl group.

The diaminobenzene in the formula (1) may have any structure of o-phenylenediamine, m-phenylenediamine, or p-phenylenediamine. However, in terms of reactivity with acid dianhydride, m-phenylenediamine, or p-Phenylenediamine is preferred.

Specifically, the structure represented by the following formula is most preferable from the viewpoints of ease of synthesis, high versatility, and characteristics. In the formula, n is an integer of 2 to 8.

<Other diamines>
As another diamine component for obtaining the specific polymer, a diamine other than the specific diamine represented by the formula [1] (hereinafter also referred to as other diamine) may be contained. Such a diamine is represented by the following general formula [2]. Other diamines may be used alone or in combination of two or more.

In the above formula [2], A ₁ and A ₂ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms. It is. From the viewpoint of monomer reactivity, A ₁ and A ₂ are preferably a hydrogen atom or a methyl group. An example of the structure of Y ₁ is as follows.

In the formula, n is an integer of 1 to 6 unless otherwise specified. In the following formula, Boc represents a tert-butoxycarbonyl group.

Other diamine components used in the liquid crystal aligning agent of the present invention are not particularly limited, but (Y-7), (Y-8), from the viewpoints of coatability, voltage holding ratio characteristics, residual DC voltage characteristics, and the like. (Y-16), (Y-17), (Y-21), (Y-22), (Y-28), (Y-37), (Y-38), (Y-60), (Y -67), (Y-68), (Y-71) to (Y-73), and (Y-160) to (Y-180) are particularly preferably selected and used in combination.

(Tetracarboxylic acid component)
Examples of the tetracarboxylic acid component for obtaining the specific polymer include tetracarboxylic acid, tetracarboxylic dianhydride, tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester, and tetracarboxylic acid dialkyl ester dihalide. Then, these are also collectively referred to as a tetracarboxylic acid component.
Examples of the tetracarboxylic acid component include tetracarboxylic dianhydride and its derivatives, tetracarboxylic acid, tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester, and tetracarboxylic acid dialkyl ester dihalide (collectively, 1 tetracarboxylic acid component).

<Tetracarboxylic dianhydride>
Examples of tetracarboxylic dianhydrides include aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, and aromatic tetracarboxylic dianhydrides. Specific examples of these include the following groups [1] to [5].

[1] As aliphatic tetracarboxylic dianhydride, for example, 1,2,3,4-butanetetracarboxylic dianhydride;

[2] Examples of alicyclic tetracarboxylic dianhydrides include acid dianhydrides such as the following formulas (X1-1) to (X1-13),

In formulas (X1-1) to (X1-4), R ₃ to R ₂₃ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, carbon An alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group, which may be the same or different,
In the above formula, R _M represents a hydrogen atom or a methyl group,
Xa is a tetravalent organic group represented by the following formulas (Xa-1) to (Xa-7).

[3] 3-Oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 ′-(tetrahydrofuran-2 ′, 5′-dione), 3,5,6-tricarboxy- 2-carboxymethylnorbornane-2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.02,6] undecane-3,5,8,10-tetraone and the like;

[4] As aromatic tetracarboxylic dianhydrides, for example, pyromellitic anhydride, 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic Acid dianhydrides, acid dianhydrides represented by the following formulas (Xb-1) to (Xb-10), and the like, and

[5] Further, acid dianhydrides represented by the formulas (X1-44) to (X1-52) and tetracarboxylic dianhydrides described in JP-A-2010-97188 can be exemplified.

In addition, the said tetracarboxylic dianhydride can be used individually by 1 type or in combination of 2 or more types.
The tetracarboxylic dianhydride component used in the liquid crystal aligning agent of the present invention is not particularly limited, but from the viewpoints of coatability, voltage holding ratio characteristics, residual DC voltage characteristics, etc., (X1-1), (X1- 2), (X1-3), (X1-6), (X1-7), (X1-8), (X1-9), (Xa-2), pyromellitic anhydride, 3,3 ′, It is preferable to select and use a tetracarboxylic dianhydride selected from 4,4′-diphenylsulfonetetracarboxylic dianhydride, (Xb-6) and (Xb-9).

<Method for producing polymer>
The method for producing these polymers is usually obtained by reacting a diamine component and a tetracarboxylic acid component. A polyamic acid is obtained by reacting at least one tetracarboxylic acid component selected from the group consisting of a tetracarboxylic dianhydride and a derivative of the tetracarboxylic acid and a diamine component composed of one or more diamines. A method is mentioned. Specifically, a method is used in which polycarboxylic acid is obtained by polycondensation of tetracarboxylic dianhydride and primary or secondary diamine.

In order to obtain a polyamic acid alkyl ester, a method of polycondensing a tetracarboxylic acid obtained by dialkyl esterifying a carboxylic acid group with a primary or secondary diamine, a tetracarboxylic acid dihalide obtained by halogenating a carboxylic acid group and a primary Alternatively, a method of polycondensation with a secondary diamine or a method of converting a carboxy group of a polyamic acid into an ester is used.
In order to obtain polyimide, a method is used in which the polyamic acid or polyamic acid alkyl ester is cyclized to form polyimide.

The reaction of the diamine component and the tetracarboxylic acid component is usually performed in a solvent. The solvent used at that time is not particularly limited as long as the produced polyimide precursor is soluble. Although the specific example of the solvent used for reaction below is given, it is not limited to these examples.
Examples include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide or 1,3-dimethyl-imidazolidinone. It is done. Further, when the solvent solubility of the polyimide precursor is high, it is represented by methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formulas [D-1] to [D-3]. Can be used.

In the formula [D-1], D ¹ represents an alkyl group having 1 to 3 carbon atoms, and in the formula [D-2], D ² represents an alkyl group having 1 to 3 carbon atoms, and the formula [D-3] In the formula, D ³ represents an alkyl group having 1 to 4 carbon atoms.

These solvents may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve a polyimide precursor, you may mix and use it for the said solvent in the range which the produced | generated polyimide precursor does not precipitate. Moreover, since the water | moisture content in a solvent inhibits a polymerization reaction and also causes the produced | generated polyimide precursor to be hydrolyzed, it is preferable to use what dehydrated and dried the solvent.

When the diamine component and the tetracarboxylic acid component are reacted in the solvent, the solution in which the diamine component is dispersed or dissolved in the solvent is stirred, and the tetracarboxylic acid component is added as it is or dispersed or dissolved in the solvent. Methods, conversely, a method of adding a diamine component to a solution in which a tetracarboxylic acid component is dispersed or dissolved in a solvent, a method of adding a diamine component and a tetracarboxylic acid component alternately, and the like. May be used. In addition, when reacting using a plurality of diamine components or tetracarboxylic acid components, they may be reacted in a premixed state, individually or sequentially, or further individually reacted low molecular weight substances. May be mixed and reacted to form a polymer.

The temperature for polycondensation of the diamine component and the tetracarboxylic acid component can be selected from -20 to 150 ° C., but is preferably in the range of −5 to 100 ° C. The reaction can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring becomes difficult. . Therefore, it is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The initial reaction is carried out at a high concentration, and then a solvent can be added.
In the polymerization reaction of the polyimide precursor, the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic acid component is preferably 0.8 to 1.2. Similar to a normal polycondensation reaction, the molecular weight of the polyimide precursor formed increases as the molar ratio approaches 1.0.

Polyimide is a polyimide obtained by ring closure of the polyimide precursor, and in this polyimide, the ring closure rate (also referred to as imidation rate) of the amic acid group is not necessarily 100%. It can be adjusted as desired.
Examples of the method for imidizing the polyimide precursor include thermal imidization in which the polyimide precursor solution is heated as it is, or catalytic imidization in which a catalyst is added to the polyimide precursor solution.

The temperature when the polyimide precursor is thermally imidized in a solution is 100 to 400 ° C., preferably 120 to 250 ° C., and a method of removing water generated by the imidation reaction from the system is preferable. The catalytic imidation of the polyimide precursor can be carried out by adding a basic catalyst and an acid anhydride to the polyimide precursor solution and stirring at -20 to 250 ° C, preferably 0 to 180 ° C.

The amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times the amidic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol times the amido group. 30 mole times.
Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Of these, pyridine is preferable because it has a basicity suitable for advancing the reaction.
Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. In particular, it is preferable to use acetic anhydride because purification after completion of the reaction is easy.
The imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.

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

More specific methods for producing the polyamic acid alkyl ester of the present invention are shown in the following (1) to (3).
(1) Method of producing by polyamic acid esterification reaction Polyamic acid is produced from a diamine component and a tetracarboxylic acid component, and the carboxy group (COOH group) is subjected to a chemical reaction, that is, an esterification reaction. This is a method for producing an alkyl ester.
The esterification reaction is a method in which a polyamic acid and an esterifying agent are reacted at −20 to 150 ° C. (preferably 0 to 50 ° C.) for 30 minutes to 24 hours (preferably 1 to 4 hours) in the presence of a solvent. is there.

The esterifying agent is preferably one that can be easily removed after the esterification reaction. N, N-dimethylformamide dimethyl acetal, N, N-dimethylformamide diethyl acetal, N, N-dimethylformamide dipropyl acetal, N, N-dimethylformamide dineopentyl butyl acetal, N, N-dimethylformamide di-t-butyl 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-methylmorpholinium chloride and the like. The amount of the esterifying agent used is preferably 2 to 6 molar equivalents per 1 mol of the polyamic acid repeating unit. Of these, 2 to 4 molar equivalents are preferred.

Examples of the solvent used for the esterification reaction include a solvent used for the reaction of the diamine component and the tetracarboxylic acid component from the viewpoint of solubility of the polyamic acid in the solvent. Of these, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone is preferable. These solvents may be used alone or in combination of two or more.
The concentration of the polyamic acid in the solvent in the esterification reaction is preferably 1 to 30% by mass from the viewpoint that the polyamic acid does not easily precipitate. Among these, 5 to 20% by mass is preferable.

(2) Method of producing by reaction of diamine component and tetracarboxylic acid diester dichloride Specifically, the diamine component and tetracarboxylic acid diester dichloride are −20 to 150 ° C. (preferably in the presence of a base and a solvent) (0 to 50 ° C.) for 30 minutes to 24 hours (preferably 1 to 4 hours).
As the base, pyridine, triethylamine, 4-dimethylaminopyridine and the like can be used. Of these, pyridine is preferable because the reaction proceeds gently. The amount of the base used is preferably an amount that can be easily removed after the reaction, and is preferably 2 to 4 moles relative to the tetracarboxylic acid diester dichloride. Of these, 2 to 3 moles are more preferred.

Examples of the solvent include a solvent used for the reaction of the diamine component and the tetracarboxylic acid component from the viewpoint of solubility of the obtained polymer, that is, the polyamic acid alkyl ester in the solvent. Of these, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone is preferable. These solvents may be used alone or in combination of two or more.
The concentration of the polyamic acid alkyl ester in the solvent in the reaction is preferably 1 to 30% by mass from the viewpoint that precipitation of the polyamic acid alkyl ester hardly occurs. Among these, 5 to 20% by mass is preferable. In order to prevent hydrolysis of the tetracarboxylic acid diester dichloride, it is preferable that the solvent used for preparing the polyamic acid alkyl ester is dehydrated as much as possible. Furthermore, the reaction is preferably performed in a nitrogen atmosphere to prevent outside air from being mixed.

(3) Method of producing by reaction of diamine component and tetracarboxylic acid diester Specifically, the diamine component and tetracarboxylic acid diester are heated at 0 to 150 ° C. (preferably in the presence of a condensing agent, a base and a solvent). 0 to 100 ° C.) for 30 minutes to 24 hours (preferably 3 to 15 hours).

Condensation agents include triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N′-carbonyldiimidazole, dimethoxy-1,3,5-triazinyl Methylmorpholinium, O- (benzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium hexafluorophosphate, (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate diphenyl, and the like can be used. The amount of the condensing agent used is preferably 2 to 3 moles, and more preferably 2 to 2.5 moles, based on the tetracarboxylic acid diester.

As the base, tertiary amines such as pyridine and triethylamine can be used. The amount of the base used is preferably an amount that can be easily removed after the polycondensation reaction, preferably 2 to 4 times by mole, more preferably 2 to 3 times by mole with respect to the diamine component.
Examples of the solvent used for the polycondensation reaction include a solvent used for the reaction of the diamine component and the tetracarboxylic acid component from the viewpoint of the solubility of the resulting polymer, that is, the polyamic acid alkyl ester, in the solvent. Of these, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone is preferable. These solvents may be used alone or in combination of two or more.

In the polycondensation reaction, the reaction proceeds efficiently by adding Lewis acid as an additive. As the Lewis acid, lithium halides such as lithium chloride and lithium bromide are preferable. The amount of Lewis acid used is preferably 0.1 to 10 times the mole of the diamine component. Among these, 2.0 to 3.0 moles are preferable.

When recovering the polyamic acid alkyl ester from the polyamic acid alkyl ester solution obtained by the methods (1) to (3) above, the reaction solution may be poured into a solvent and precipitated. Examples of the solvent used for precipitation include water, methanol, ethanol, 2-propanol, hexane, butyl cellosolve, acetone, toluene and the like. The polymer deposited in the solvent is preferably washed with the solvent several times for the purpose of removing the additives and catalysts used above. After washing, filtration and recovery, the polymer can be dried at normal temperature or reduced pressure at room temperature or with heating. In addition, the impurities in the polymer can be reduced by re-dissolving the polymer recovered by precipitation in a solvent and repeating the operation of re-precipitation recovery 2 to 10 times.
The production method of (2) or (3) above is preferable for the polyamic acid alkyl ester.

<Liquid crystal aligning agent>
The liquid crystal aligning agent of this invention contains the above-mentioned specific polymer, Preferably it is a solution for forming a liquid crystal aligning film. The content of the polymer in the liquid crystal aligning agent is preferably 2 to 10% by mass and more preferably 3 to 8% by mass in the liquid crystal aligning agent.

All the polymer components in the liquid crystal aligning agent of the present invention may all be the specific polymer of the present invention, or other polymers may be mixed. Examples of other polymers include cellulose polymers, acrylic polymers, methacrylic polymers, polystyrenes, polyamides, polysiloxanes, etc., in addition to polyimides and polyimide precursors. The content of the other polymer is preferably 1 to 90% by mass and more preferably 30 to 80% by mass in the resin component contained in the liquid crystal aligning agent.

The good solvent used for the liquid crystal aligning agent of this invention will not be specifically limited if the specific polymer of this invention melt | dissolves. Although the specific example of the solvent used for a liquid crystal aligning agent below is given, it is not limited to these examples.
Examples include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide or 1,3-dimethyl-imidazolidinone. It is done.
Further, when the solvent solubility of the polyimide precursor is high, it is represented by methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or the above formula [D-1] to formula [D-3]. The solvent used can also be used.
The said good solvent may be used by 1 type, and may be used by the combination and ratio which are more suitable according to the application | coating method.
The good solvent in the liquid crystal aligning agent of the present invention is preferably 20 to 99% by mass of the whole solvent contained in the liquid crystal aligning agent. Of these, 20 to 90% by mass is preferable. More preferred is 30 to 80% by mass.

The liquid crystal aligning agent of this invention can use the solvent (it is also called a poor solvent) which improves the coating property and surface smoothness of a liquid crystal aligning film at the time of apply | coating a liquid crystal aligning agent. Specific examples are given below.
For example, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 2,6- Dimethyl 4-heptanol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3- Butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, diisopropyl ether, 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 Tyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, 2,6-dimethyl-4-heptanone, 4,6-dimethyl-2-heptanone, 3-ethoxybutyl Acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, 2- (methoxymethoxy) ethanol, ethylene Glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2- (hexyloxy) ethanol, furfuryl alcohol, diethylene glycol, Lopylene glycol, propylene glycol monobutyl ether, 1- (butoxyethoxy) propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, di Propylene glycol dimethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether Acetate, diethylene glycol monobutyl ether acetate, 2- (2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, Ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methylethyl 3-ethoxypropionate, 3-methoxypropionic acid Ethyl, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl lactate, milk Ethyl ester, lactic acid n- propyl ester, lactate n- butyl ester, lactic acid isoamyl ester, the formula [D-1] ~ can be exemplified solvents represented by [D-3].

Among these, preferred solvent combinations include N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ- Butyrolactone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether, N- Methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether, 2,6-dimethyl-4-heptanone, N-methyl-2-pyrrolidone, γ-butyrolactone, and propylene glycol Monobutyl ether and diisopropyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether and 2,6-dimethyl-4-heptanol, N-methyl-2-pyrrolidone, γ-butyrolactone and dipropylene glycol dimethyl ether , Etc. These poor solvents are preferably 1 to 80% by mass, more preferably 10 to 80% by mass, and particularly preferably 20 to 70% by mass with respect to the total solvent contained in the liquid crystal aligning agent. The kind and content of such a solvent are appropriately selected according to the application device, application conditions, application environment, and the like of the liquid crystal aligning agent.

In addition to the above, the liquid crystal aligning agent of the present invention includes a polymer other than the polymer described in the present invention, a dielectric for the purpose of changing electrical properties such as dielectric constant and conductivity of the liquid crystal aligning film, Silane coupling agent for the purpose of improving adhesion to the substrate, crosslinkable compound for the purpose of increasing the hardness and density of the liquid crystal alignment film, and heating of the polyimide precursor when the coating film is baked An imidization accelerator for the purpose of efficiently proceeding imidization by the above may be contained.

Examples of the compound that improves the adhesion between the liquid crystal alignment film and the substrate include a functional silane-containing compound and an epoxy group-containing compound, such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- Glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2- Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl- 3-aminopropyltrimethoxy Sisilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10 -Triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-amino Propyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3 Aminopropyltrimethoxysilane, -Bis (oxyethylene) -3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol di Glycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ', N',-Tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane or N, N, N ', N',-tetraglycyl Such as Gilles-4,4'-diaminodiphenylmethane and the like.

In addition, the following additives may be added to the liquid crystal aligning agent of the present invention in order to increase the mechanical strength of the liquid crystal aligning film.

The above-mentioned additive is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent. If the amount is less than 0.1 parts by mass, the effect cannot be expected. If the amount exceeds 30 parts by mass, the orientation of the liquid crystal is lowered.

<Liquid crystal alignment film and liquid crystal display element>
The liquid crystal alignment film of the present invention can be formed by applying the liquid crystal aligning agent of the present invention on a substrate and baking it.
For example, after apply | coating the liquid crystal aligning agent of this invention to a board | substrate, after drying as needed, the cured film obtained by baking can also be used as a liquid crystal aligning film as it is. In addition, the cured film is rubbed, irradiated with polarized light or light of a specific wavelength, or treated with an ion beam, or a voltage is applied to the liquid crystal display element after filling the liquid crystal as a PSA alignment film It is also possible to irradiate with UV. In particular, it is useful to use as an alignment film for PSA.

In this case, the substrate to be used is not particularly limited as long as it is a highly transparent substrate. Glass plate, polycarbonate, poly (meth) acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, polyetherketone , Plastic substrates such as trimethylpentene, polyolefin, polyethylene terephthalate, (meth) acrylonitrile, triacetyl cellulose, diacetyl cellulose, and acetate butyrate cellulose can be used. In addition, it is preferable to use a substrate on which an ITO electrode or the like for driving liquid crystal is formed from the viewpoint of simplifying the process. Further, in the reflection type liquid crystal display element, an opaque material such as a silicon wafer can be used as long as the substrate is only on one side, and in this case, a material that reflects light such as aluminum can be used.

The method for applying the liquid crystal aligning agent is not particularly limited, and examples thereof include printing methods such as screen printing, offset printing, flexographic printing, ink jet method, spray method, roll coating method, dip, roll coater, slit coater, and spinner. From the standpoint of productivity, the transfer printing method is widely used industrially, and is preferably used in the present invention.

The coating film formed by applying the liquid crystal aligning agent by the above method can be baked to obtain a cured film. The drying process after applying the liquid crystal aligning agent is not necessarily required, but if the time from application to baking is not constant for each substrate, or if baking is not performed immediately after application, the drying process is performed. It is preferable. The drying is not particularly limited as long as the solvent is removed to such an extent that the shape of the coating film is not deformed by transporting the substrate or the like. For example, a method of drying on a hot plate at a temperature of 40 ° C. to 150 ° C., preferably 60 ° C. to 100 ° C., for 0.5 minutes to 30 minutes, preferably 1 minute to 5 minutes.

The baking temperature of the coating film formed by applying the liquid crystal aligning agent is not limited, and is, for example, 100 to 350 ° C, preferably 120 to 350 ° C, and more preferably 150 ° C to 330 ° C. The firing time is 5 minutes to 240 minutes, preferably 10 minutes to 90 minutes, and more preferably 10 minutes to 30 minutes. Heating can be performed by a generally known method such as a hot plate, a hot air circulating furnace, an infrared furnace, or the like.

The thickness of the liquid crystal alignment film obtained by firing is not particularly limited, but is preferably 5 to 300 nm, more preferably 20 to 200 nm.

The liquid crystal display element can produce a liquid crystal cell by a known method after forming a liquid crystal alignment film on a substrate by the above method. As a specific example of the liquid crystal display element, the two substrates disposed so as to face each other, the liquid crystal layer provided between the substrates, and the liquid crystal alignment agent provided between the substrate and the liquid crystal layer are formed by the above-described liquid crystal display element. A liquid crystal display element of a vertical alignment system including a liquid crystal cell having a liquid crystal alignment film. Specifically, a liquid crystal alignment film is formed by applying and baking a liquid crystal alignment agent on two substrates, and the two substrates are arranged so that the liquid crystal alignment films face each other. This is a vertical alignment type liquid crystal display element including a liquid crystal cell manufactured by sandwiching a liquid crystal layer composed of liquid crystal between substrates.

Using the liquid crystal alignment film formed of the liquid crystal alignment agent containing the specific polymer of the present invention, the polymerizable compound contained in the liquid crystal is reacted by irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer. As a result, a PSA type liquid crystal display element having a remarkably excellent vertical alignment ability is obtained.

The substrate of the liquid crystal display element is not particularly limited as long as it is a highly transparent substrate, but is usually a substrate in which a transparent electrode for driving liquid crystal is formed on the substrate. As a specific example, the thing similar to the board | substrate described with the said liquid crystal aligning film can be mentioned. A substrate provided with a conventional electrode pattern or protrusion pattern may be used. However, in the PSA type liquid crystal display element, the liquid crystal aligning agent containing the polyimide polymer of the present invention is used. It is possible to operate even in a structure in which a line / slit electrode pattern of 1 to 10 μm is formed and no slit pattern or protrusion pattern is formed on the counter substrate. The liquid crystal display element of this structure simplifies the manufacturing process. And high transmittance can be obtained.

As a high-performance element such as a TFT type element, an element in which an element such as a transistor is formed between an electrode for driving a liquid crystal and a substrate is used.
In the case of a transmissive liquid crystal display element, it is common to use a substrate as described above. However, in a reflective liquid crystal display element, if only one substrate is used, an opaque substrate such as a silicon wafer may be used. Is possible. At that time, a material such as aluminum that reflects light may be used for the electrode formed on the substrate.

The liquid crystal material constituting the liquid crystal layer of the liquid crystal display element is not particularly limited, and the liquid crystal material used in the conventional vertical alignment method, for example, negative types such as MLC-6608, MLC-6609, MLC-3023 manufactured by Merck The liquid crystal can be used. In the PSA type liquid crystal display element, for example, a polymerizable compound-containing liquid crystal represented by the following formula can be used.

As a method for sandwiching the liquid crystal layer between two substrates, a known method can be exemplified. For example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, and spacers such as beads are dispersed on the liquid crystal alignment film on one substrate so that the surface on which the liquid crystal alignment film is formed is on the inside. Then, the other substrate is bonded, and liquid crystal is injected under reduced pressure to seal. Also, a pair of substrates on which a liquid crystal alignment film is formed are prepared, and spacers such as beads are dispersed on the liquid crystal alignment film on one substrate, and then liquid crystal is dropped, and then the surface on which the liquid crystal alignment film is formed A liquid crystal cell can also be produced by a method in which the other substrate is bonded to each other so as to be inside, and sealing is performed. The thickness of the spacer is preferably 1 to 30 μm, more preferably 2 to 10 μm.

The step of producing a liquid crystal cell by irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer includes, for example, applying an electric field between the electrodes installed on the substrate to apply an electric field to the liquid crystal alignment film and the liquid crystal layer. And applying ultraviolet rays while maintaining this electric field. Here, the voltage applied between the electrodes is, for example, 5 to 30 Vp-p, preferably 5 to 20 Vp-p. The irradiation amount of ultraviolet rays is, for example, 1 to 60 J, preferably 40 J or less, and the smaller the irradiation amount of ultraviolet rays, the lowering of reliability caused by the destruction of the members constituting the liquid crystal display element can be suppressed, and the irradiation time of ultraviolet rays can be reduced. This is preferable because the manufacturing efficiency is increased.

As described above, when ultraviolet rays are irradiated while applying a voltage to the liquid crystal alignment film and the liquid crystal layer, the polymerizable compound reacts to form a polymer, and the direction in which the liquid crystal molecules are tilted is stored by this polymer. Thus, the response speed of the obtained liquid crystal display element can be increased. In addition, a polyimide precursor having a side chain for vertically aligning liquid crystal and a photoreactive side chain when irradiated with ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer, and the polyimide precursor as an imide Since the photoreactive side chains of at least one polymer selected from the polyimide obtained by the reaction or the photoreactive side chains of the polymer react with the polymerizable compound, the liquid crystal display element obtained The response speed can be increased.

The present invention will be described in more detail with reference to the following examples, but the present invention should not be construed as being limited thereto. Abbreviations of the compounds used are as follows.
(liquid crystal)
MLC-3023 (manufactured by Merck, liquid crystal containing negative polymerizable compound)

(Specific side chain diamine component)
W-A1: Compound W-A2 represented by the formula [W-A1]: Compound W-A3 represented by the formula [W-A2]: Compound W-A4 represented by the formula [W-A3]: Formula Compound W-A5 represented by [W-A4]: Compound W-A6 represented by formula [W-A5]: Compound W-A7 represented by formula [W-A6]: Formula [W-A7] Compound W-A8 represented by the formula: Compound W-A9 represented by the formula [W-A8]: Compound W-A10 represented by the formula [W-A9]: Compound represented by the formula [W-A10]

(Other side chain diamine compounds)
A1: Compound represented by Formula [A1] A2: Compound represented by Formula [A2] A3: Compound represented by Formula [A3]

(Other diamine compounds)
C1: Compound represented by formula [C1] C2: Compound represented by formula [C2] C3: Compound represented by formula [C3] C4: Compound represented by formula [C4] C5: Formula [C5] Compound represented by formula C6: Compound represented by formula [C6] C7: Compound represented by formula [C7] C8: Compound represented by formula [C8] C9: Compound represented by formula [C9] C10 : Compound represented by the formula [C10]

(Tetracarboxylic acid component)
D1: 1,2,3,4-cyclobutanetetracarboxylic dianhydride D2: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride D3: pyromellitic dianhydride D4: 2,3,5-tricarboxycyclopentyl acetic acid dianhydride D5: 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride

(solvent)
NMP: N-methyl-2-pyrrolidone BCS: ethylene glycol monobutyl ether NEP: N-ethyl-2-pyrrolidone (crosslinking agent)
E1: Cross-linking agent (additive) represented by the following formula (E1)
E2: 3-picolylamine

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

(Measurement of imidization ratio of polyimide)
20 mg of polyimide powder was put into an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, φ5 (manufactured by Kusano Kagaku)), and deuterated dimethyl sulfoxide (DMSO-d6, 0.05 mass% TMS (tetramethylsilane)). (Mixed product) (0.53 ml) was added and completely dissolved by applying ultrasonic waves. This solution was measured for proton NMR at 500 MHz with an NMR measuring instrument (JNW-ECA500) (manufactured by JEOL Datum). The imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of amic acid appearing in the vicinity of 9.5 to 10.0 ppm. It calculated | required by the following formula | equation using the integrated value.
Imidization rate (%) = (1−α · x / y) × 100
In the above formula, x is a proton peak integrated value derived from NH group of amic acid, y is a peak integrated value of reference proton, α is one NH group proton of amic acid in the case of polyamic acid (imidation rate is 0%) Is the number ratio of the reference proton to.

(Viscosity measurement)
In the synthesis example or the comparative synthesis example, the viscosity of the polyimide polymer is an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), a sample amount of 1.1 mL, a cone rotor TE-1 (1 ° 34 ′, R24), measured at a temperature of 25 ° C.

W-A1 to W-A3 and W-A4 to W-A10 are novel compounds that have not been disclosed yet, and the synthesis method will be described in detail below.
The products described in Synthesis Examples 1 to 3 and Synthesis Examples 4 to 10 were identified by ¹ H-NMR analysis (analysis conditions are as follows).
Instrument: Varian NMR System 400 NB (400 MHz).
Measurement solvent: CDCl _3, DMSO-d ₆ .
Reference material: Tetramethylsilane (TMS) (δ0.0 ppm for ¹ H).

<< Synthesis Example 1 Synthesis of W-A1 >>

<Synthesis of Compound [1] and Compound [2]>
In tetrahydrofuran (165.6 g), 4,4′-dinitro-1,1′-biphenyl-2,2′-dimethanol (41.1 g, 135 mmol) and triethylamine (31.5 g) were charged and ice-cooled in a nitrogen atmosphere. Under conditions, methanesulfonyl chloride (33.2 g) was added dropwise and reacted for 1 hour to obtain Compound [1]. Subsequently, p- (trans-4-heptylcyclohexyl) phenol (77.8 g) dissolved in tetrahydrofuran (246.6 g) was added, stirred at 40 ° C. for 1 hour, and then dissolved in pure water (233 g). Potassium oxide (41.0 g) was added at the same temperature and allowed to react for 21 hours. After completion of the reaction, 1.0 M hydrochloric acid aqueous solution (311 ml) and pure water (1050 g) were added to precipitate a crude product, and the crude product was collected by filtration. The obtained crude product was dissolved in tetrahydrofuran (574 g) with heating at 50 ° C., methanol (328 g) was added to precipitate crystals, filtered and dried to obtain compound [2] (yield: 97.9 g, yield). Rate: 89%).
¹ H-NMR (400 MHz) in CDCl ₃ : 0.87-0.90 ppm (m, 6H), 0.96-1.05 ppm (m, 4H), 1.19-1.39 ppm (m, 30H), 6.80-1.85 ppm (m, 8H), 2.32-2.40 ppm (m, 2H), 4.77 ppm (s, 4H), 6.66-6.70 ppm (m, 4H), 02-7.06 ppm (m, 4H), 7.40 ppm (d, 2H, 8.4), 8.25 ppm (dd, 2H, J = 2.4 Hz, J = 8.4 Hz), 8.54 ppm (d , 2H, J = 2.4 Hz).

<Synthesis of W-A1>
Compound [2] (74.3 g, 90.9 mmol) and 3% platinum carbon (5.94 g) were charged in tetrahydrofuran (1783 g), and reacted in a hydrogen atmosphere at room temperature. After completion of the reaction, the reaction mixture was filtered, and the filtrate was concentrated under reduced pressure to adjust the total internal weight to 145 g. Subsequently, methanol (297 g) was added to the concentrated solution, stirred under ice-cooling, filtered and dried to obtain W-A1 (yield: 59.2 g, yield: 86%).
¹ H-NMR (400 MHz) in CDCl ₃ : 0.87-0.90 ppm (m, 6H), 0.96-1.05 ppm (m, 4H), 1.19-1.40 ppm (m, 30H), 1.81-1.84 ppm (m, 8H), 2.32-2.38 ppm (m, 2H), 3.67 ppm (s, 4H), 4.69 ppm (d, 2H, J = 12.0 Hz), 4.74 ppm (d, 2H, J = 11.6 Hz), 6.62 ppm (dd, 2H, J = 2.4 Hz, J = 8.0 Hz), 6.70-6.75 ppm (m, 4H), 6 .91 ppm (d, 2H, J = 2.4 Hz), 6.97-7.03 ppm (m, 6H).

<< Synthesis Example 2 Synthesis of WA-2 >>

<Synthesis of Compound [3]>
4,4′-Dinitro-2,2′-diphenic acid (40.9 g, 123 mmol) and p- (trans-4-heptylcyclohexyl) phenol (72.1 g), 4-dimethyl in tetrahydrofuran (327.2 g) Aminopyridine (1.50 g) was charged, and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (56.6 g) was added under a nitrogen atmosphere at room temperature, followed by reaction for 3 hours. After completion of the reaction, the reaction solution was poured into pure water (1226 g) to precipitate a crude product, which was collected by filtration. Subsequently, the crude product was subjected to slurry washing with methanol (245 g) and filtered, and the obtained crude product was dissolved in tetrahydrofuran (245 g) by heating at 60 ° C. After removing insoluble matter by filtration, the total internal weight was reduced to 232 g by concentration under reduced pressure, methanol (163 g) was added to precipitate crystals, and the mixture was stirred under ice-cooling conditions, filtered and dried to give compound [3] (Yield: 73.9 g, Yield: 71%).
¹ H-NMR (400 MHz) in CDCl ₃ : 0.87-0.90 ppm (m, 6H), 0.98-1.06 ppm (m, 4H), 1.18-1.43 ppm (m, 30H), 1.83-1.86 ppm (m, 8H), 2.41-2.47 ppm (m, 2H), 6.89-6.92 ppm (m, 4H), 7.17-7.20 ppm (m, 4H) ), 7.48 ppm (d, 2H, 8.4), 8.49 ppm (dd, 2H, J = 2.4 Hz, J = 8.4 Hz), 9.11 ppm (d, 2H, J = 2.4 Hz) .

<Synthesis of W-A2>
Compound [3] (73.9 g, 87.4 mmol) and 5% palladium carbon (8.80 g) were charged in tetrahydrofuran (443 g) and methanol (73.9 g), and reacted in a hydrogen atmosphere at room temperature. After completion of the reaction, palladium carbon was removed by filtration, and the total internal weight was reduced to 171 g by concentration under reduced pressure. Subsequently, methanol (222 g) was added to the concentrated solution to precipitate crystals, stirred under ice cooling, filtered and dried to obtain WA2 (yield: 66.6 g, yield: 97%).
¹ H-NMR (400 MHz) in CDCl ₃ : 0.87-0.90 ppm (m, 6H), 0.96-1.05 ppm (m, 4H), 1.17-1.42 ppm (m, 30H), 1.82-1.85 ppm (m, 8H), 2.38-2.44 ppm (m, 2H), 3.77 ppm (s, 4H), 6.80-6.87 ppm (m, 6H), 7. 08-7.13 ppm (m, 6H), 7.41 ppm (d, 2H, J = 2.4 Hz).

<< Synthesis Example 3 Synthesis of W-A3 >>

<Synthesis of Compound [4] and Compound [5]>
Charge 4- (trans-4-heptylcyclohexyl) -benzoic acid (73.1 g, 242 mmol) and N, N-dimethylformamide (0.73 g) in toluene (366 g), and thionyl chloride under nitrogen atmosphere at 50 ° C. (35.9 g) was added dropwise. After the dropwise addition, the mixture was reacted at the same temperature for 1 hour, and then the reaction solution was concentrated under reduced pressure to obtain compound [4]. Subsequently, 4,4′-dinitro-1,1′-biphenyl-2,2′-dimethanol (35.0 g, 115 mmol) and triethylamine (26.8 g) were charged in tetrahydrofuran (210 g), and the nitrogen atmosphere ice was charged. Compound [4] dissolved in tetrahydrofuran (73.1 g) was added dropwise under cold conditions. After completion of the dropwise addition, the reaction temperature was set to room temperature and the reaction was allowed to proceed for 18 hours. After completion of the reaction, triethylamine hydrochloride was removed by filtration, and an oily compound was obtained by concentration under reduced pressure. The obtained oily compound was added into pure water (1015 g) to precipitate crystals, and the crude product was collected by filtration. Subsequently, the obtained crude product was washed with slurry at room temperature with methanol (291 g), washed with slurry at room temperature with ethyl acetate (175 g), filtered and dried to obtain compound [5] (yield: 92.7 g, yield). Rate: 92%).
¹ H-NMR (400 MHz) in CDCl ₃ : 0.89-0.91 ppm (m, 6H), 0.99-1.09 ppm (m, 4H), 1.20-1.47 ppm (m, 30H), 1.85-1.88 ppm (m, 8H), 2.46-2.52 ppm (m, 2H), 5.14 ppm (s, 4H), 7.23-7.26 ppm (m, 4H), 7. 45ppm (d, 2H, J = 8.4Hz), 7.83-7.86ppm (m, 4H), 8.27ppm (dd, 2H, J = 2.4Hz, J = 8.4Hz), 8.47ppm (D, 2H, J = 2.4 Hz).

<Synthesis of W-A3>
Compound [5] (80.5 g, 92.2 mmol) and 3% platinum carbon (6.44 g) were charged in tetrahydrofuran (484 g) and methanol (161 g), and reacted in a hydrogen atmosphere at room temperature. After completion of the reaction, platinum carbon was removed by filtration, and the solvent was removed by concentration under reduced pressure, so that the total internal weight was 96.6 g. Subsequently, methanol (322 g) was added to the concentrated solution to precipitate crystals, stirred under ice cooling, and filtered to obtain a crude product. Subsequently, the obtained crude product was heated and dissolved in ethyl acetate (322 g) at 60 ° C., methanol (700 g) was added, crystals were precipitated under ice-cooling conditions, filtered and dried to obtain WA-3. (Yield: 67.9 g, Yield: 91%).
¹ H-NMR (400 MHz) in CDCl ₃ : 0.87-0.91 ppm (m, 6H), 0.98-1.08 ppm (m, 4H), 1.19-1.47 ppm (m, 30H), 1.84 to 1.87 ppm (m, 8H), 2.44 to 2.51 ppm (m, 2H), 3.71 ppm (s, 4H), 5.02 ppm (d, 2H, J = 12.8 Hz), 5.09ppm (d, 2H, J = 12.4Hz), 6.66ppm (dd, 2H, J = 2.4Hz, J = 8.0Hz), 6.84ppm (d, 2H, J = 2.4Hz) 7.03 ppm (d, 2H, J = 8.0 Hz), 7.19-7.25 ppm (m, 4H), 7.89-7.92 ppm (m, 4H).

<< Synthesis Example 4 Synthesis of W-A4 >>

<Synthesis of Compound [6] and Compound [7]>
In toluene (134 g), trans, trans-4′-amylbicyclohexyl-4-carboxylic acid (26.7 g, 95.1 mmol) and N, N-dimethylformamide (0.401 g) were charged under a nitrogen atmosphere at 50 ° C. Below, thionyl chloride (13.6 g, 114 mmol) was added dropwise. After the dropwise addition, the mixture was reacted at the same temperature for 1 hour, and then the reaction solution was concentrated under reduced pressure to obtain compound [6]. Subsequently, 4,4′-dinitro-1,1′-biphenyl-2,2′-dimethanol (12.6 g, 41.4 mmol) and triethylamine (10.9 g, 108 mmol) in tetrahydrofuran (63.0 g) The compound [6] dissolved in tetrahydrofuran (12.6 g) was added dropwise under ice-cooling conditions in a nitrogen atmosphere. After completion of the dropwise addition, the reaction temperature was raised to room temperature and reacted for 17 hours. After completion of the reaction, the reaction solution was added to pure water (731 g) to precipitate crystals. After filtration, pure water washing, and methanol washing, the crude product was recovered. Subsequently, the obtained crude product is dissolved by heating in toluene (56.0 g), hexane (112 g) is added to precipitate crystals, and the mixture is stirred at room temperature, filtered, and dried to obtain compound [7]. Obtained (yield: 17.0 g, 20.6 mmol, yield: 50%).
¹ H-NMR (400 MHz) in CDCl ₃ : 0.82-1.38 ppm (m, 44H), 1.67-1.81 ppm (m, 12H), 1.90-1.98 ppm (m, 4H), 2.19-2.25 ppm (m, 2H), 4.82 ppm (d, 2H, J = 13.6 Hz), 4.88 ppm (d, 2H, J = 13.6 Hz), 7.39 ppm (d, 2H) , J = 8.4 Hz), 8.26 ppm (dd, 2H, J = 2.4 Hz, J = 8.4 Hz), 8.38 ppm (d, 2H, J = 2.0 Hz)

<Synthesis of W-A4>
Compound [7] (17.0 g, 20.6 mmol) and 3% platinum carbon (1.36 g) were charged in tetrahydrofuran (136 g) and methanol (34.0 g), and allowed to react for about 41 hours in a hydrogen atmosphere at room temperature. It was. After completion of the reaction, the total internal weight was adjusted to 40 g by filtration and concentration under reduced pressure. Subsequently, methanol (68.0 g) was added to precipitate crystals, which was filtered and dried to obtain WA-4 (yield: 15.2 g, 19.9 mmol, yield: 97%).
¹ H-NMR (400 MHz) in CDCl ₃ : 0.81-1.39 ppm (m, 44H), 1.67-1.78 ppm (m, 12H), 1.90-1.97 ppm (m, 4H), 2.14-2.20 ppm (m, 2H), 3.71 ppm (br, 4H), 4.73 ppm (d, 2H, J = 12.4 Hz), 4.78 ppm (d, 2H, J = 12.4 Hz) ), 6.62 ppm (dd, 2H, J = 2.4 Hz, J = 8.0 Hz), 6.73 ppm (d, 2H, J = 2.8 Hz), 6.94 ppm (d, 2H, J = 8. 0Hz)

<< Synthesis Example 5 Synthesis of W-A5 >>

<Synthesis of Compound [8]>
Trans-1-bromo-4- (4-heptylcyclohexyl) benzene (45.4 g, 135 mmol) and lithium bis (trimethylsilyl) amide (about 26% tetrahydrofuran solution, about 1.30 mol / L, 218 mL) in toluene (227 g) ), Tri-tert-butylphosphonium tetrafluoroborate (1.58 g, 5.44 mmol), bis (dibenzylideneacetone) palladium (0) (3.14 g, 5.46 mmol), and a nitrogen atmosphere at room temperature. The reaction was carried out for 17 hours. After completion of the reaction, a 5.7 mol / L aqueous hydrochloric acid solution (80.0 mL) was added to precipitate crystals, and the hydrochloride of compound [8] was recovered by filtration. The obtained hydrochloride was dispersed in a mixed solution of toluene (300 g), ethyl acetate (200 g) and tetrahydrofuran (100 g), and separated with a 3.0 mol / L aqueous sodium hydroxide solution (200 g), and the organic phase was saturated. Washed with brine. Subsequently, activated carbon (brand: special white birch, 2.27 g) was added to the organic phase and stirred, and then the activated carbon was removed by filtration. The obtained filtrate was concentrated under reduced pressure to obtain an oily compound. The oily compound was dispersed in hexane (100 g), crystals were precipitated under dry ice / ethanol cooling conditions, filtered and dried to obtain compound [8] (yield: 27.5 g, 101 mmol, yield: 75%).
¹ H-NMR (400 MHz) in CDCl ₃ : 0.87-1.43 ppm (m, 20H), 1.83-1.85 ppm (m, 4H), 2.31-2.38 ppm (m, 1H), 3.54 ppm (br, 2H), 6.62-6.65 ppm (m, 2H), 6.99-7.02 ppm (m, 2H)

<Synthesis of Compound [9]>
4,4′-dinitro-2,2′-diphenic acid (14.9 g, 45.0 mmol) and compound [8] (25.8 g, 94.3 mmol) in tetrahydrofuran (120 g) and methylene chloride (60.0 g). ), 4-dimethylaminopyridine (0.550 g, 4.50 mmol), 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (20.0 g, 104 mmol), and 14 under nitrogen atmosphere at room temperature. Reacted for hours. After completion of the reaction, the reaction mixture was diluted with ethyl acetate (375 g), washed with the organic phase three times with pure water (149 g), and the obtained organic phase was dehydrated with magnesium sulfate. Subsequently, the organic phase was concentrated under reduced pressure, the internal total weight was adjusted to 112 g, methanol (120 g) was added to precipitate crystals, filtered and dried to obtain compound [9] (yield: 28.0 g, (33.2 mmol, yield: 74%)
¹ H-NMR (400 MHz) in CDCl ₃ : 0.87-1.43 ppm (m, 40H), 1.82-1.84 ppm (m, 8H), 2.37-2.44 ppm (m, 2H), 7.10ppm (d, 4H, J = 8.8Hz), 7.26-7.30ppm (m, 4H), 7.40ppm (d, 2H, J = 8.4Hz), 8.27ppm (dd, 2H) , J = 2.4 Hz, J = 8.4 Hz), 8.53 ppm (d, 2H, J = 2.4 Hz), 9.10 ppm (s, 2H)

<Synthesis of W-A5>
Compound [9] (28.0 g, 33.2 mmol) and 5% palladium carbon (2.10 g) were charged in tetrahydrofuran (140 g) and methanol (56.0 g) and allowed to react for about 3 days in a hydrogen atmosphere at room temperature. It was. After completion of the reaction, palladium carbon was removed by filtration and the total internal weight was 122 g by concentrating under reduced pressure. Methanol (168 g) was added to the resulting solution to precipitate crystals, which was filtered and dried to obtain WA5 (yield: 23.8 g, 30.4 mmol, yield: 92%).
¹ H-NMR (400 MHz) in CDCl ₃ : 0.87-1.42 ppm (m, 40H), 1.81-1.84 ppm (m, 8H), 2.36-2.42 ppm (m, 2H), 3.73 ppm (br, 4H), 6.58-6.60 ppm (m, 2H), 6.88-6.90 ppm (m, 4H), 7.07-7.09 ppm (m, 4H), 7. 34-7.36 ppm (m, 4H), 8.85 ppm (s, 2H)

<< Synthesis Example 6 Synthesis of WA-6 >>

<Synthesis of Compound [10]>
4,4′-dinitro-2,2′-diphenic acid (25.0 g, 75.4 mmol) and cholesterol (61.7 g, 160 mmol), 4-dimethylaminopyridine in tetrahydrofuran (113 g) and methylene chloride (113 g) (0.919 g, 7.54 mmol), 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (33.6 g, 175 mmol) were charged and allowed to react for 18 hours in a nitrogen atmosphere at room temperature. After completion of the reaction, methylene chloride (375 g) was added to the reaction solution, the organic phase was washed three times with saturated brine (200 g), and the organic phase was dehydrated with magnesium sulfate. Subsequently, the obtained solution was concentrated under reduced pressure to obtain a brown oily compound, a mixed solution of ethyl acetate (200 g) and isopropyl alcohol (200 g) was added to precipitate crystals, and a crude product was obtained by filtration. The obtained crude product was recrystallized twice with a mixed solution of chloroform (500 g) and methanol (600 g), filtered and dried to obtain compound [10] (yield: 41.8 g, 39.1 mmol, yield). : 52%).
¹ H-NMR (400 MHz) in CDCl ₃ : 0.67-2.21 ppm (m, 86H), 4.58-4.63 ppm (m, 2H), 5.31-5.33 ppm (m, 2H), 7.37-7.39 ppm (m, 2H), 8.42-8.44 ppm (m, 2H), 8.93 ppm (m, 2H)

<Synthesis of W-A6>
Compound [10] (40.4 g, 37.8 mmol) and 5% palladium carbon (3.03 g) were charged in tetrahydrofuran (320 g) and methanol (80.8 g), and reacted for about 3 days in a hydrogen atmosphere at room temperature. It was. After completion of the reaction, the palladium carbon was removed by filtration, and the total internal weight was 112 g by concentrating under reduced pressure. Methanol (160 g) was added to the resulting solution to precipitate crystals, which was filtered and dried to obtain WA6 (yield: 35.0 g, 34.7 mmol, yield: 92%).
¹ H-NMR (400 MHz) in CDCl ₃ : 0.66-2.17 ppm (m, 86H), 3.74 ppm (br, 4H), 4.50-4.56 ppm (m, 2H), 5.28 ppm ( m, 2H), 6.78-6.80 ppm (m, 2H), 6.95-6.97 ppm (m, 2H), 7.26-7.28 ppm (m, 2H)

<< Synthesis Example 7 Synthesis of WA-7 >>

<Synthesis of Compound [11] and Compound [12]>
In tetrahydrofuran (152 g), 4,4′-dinitro-1,1′-biphenyl-2,2′-dimethanol (40.0 g, 132 mmol) and triethylamine (36.6 g, 362 mmol) were charged and iced in a nitrogen atmosphere. Ethanesulfonyl chloride (44.4 g, 345 mmol) was added dropwise under cold conditions. After completion of the dropwise addition, compound [11] was obtained by stirring the reaction temperature at 40 ° C. for 3 hours. Subsequently, potassium hydroxide (85.0% product, 45%) dissolved in p- (trans-4-propylcyclohexyl) phenol (63.1 g, 289 mmol) and pure water (228 g) dissolved in tetrahydrofuran (240 g). 0.1 g, 683 mmol) was added to the reaction solution of compound [11], and the mixture was heated to 50 ° C. and reacted for 39 hours. After completion of the reaction, the reaction solution was poured into pure water (1500 g) to precipitate a crude product, followed by filtration and washing with pure water. Subsequently, slurry washing was performed with a mixed solution of pure water (378 g) and methanol (378 g), followed by filtration and washing with methanol again. The obtained crude crystal was dissolved in tetrahydrofuran (600 g) with heating at 60 ° C., methanol (400 g) was added to precipitate crystals, and the mixture was stirred at room temperature, filtered and dried to obtain compound [12]. (Yield: 77.7 g, 110 mmol, yield: 83%).
¹ H-NMR (400 MHz) in CDCl ₃ : 0.87 to 0.97 ppm (m, 6H), 0.97 to 1.05 ppm (m, 4H), 1.12 to 1.62 ppm (m, 14H), 1.81-1.87 ppm (m, 8H), 2.34-2.40 ppm (m, 2H), 4.77 ppm (s, 4H), 6.67-6.69 ppm (m, 4H), 00-7.05ppm (m, 4H), 7.40ppm (d, 2H, J = 8.0Hz), 8.25ppm (dd, 2H, J = 2.0Hz, J = 8.4Hz), 8.54ppm (S, 2H).

<Synthesis of WA-7>
Compound [12] (77.7 g, 110 mmol) and 3% platinum carbon (6.22 g) were charged in tetrahydrofuran (741 g) and methanol (155 g), and reacted under a hydrogen atmosphere at room temperature for about 2 days. After completion of the reaction, platinum carbon was removed by filtration, and the filtrate was concentrated under reduced pressure. Tetrahydrofuran (122 g) was added to the resulting concentrated crude product and dissolved by heating at 60 ° C., acetonitrile (159 g) was added to precipitate crystals, and the mixture was stirred at room temperature, filtered and dried to obtain WA7. (Yield: 58.6 g, 88.1 mmol, Yield: 80%).
¹ H-NMR (400 MHz) in CDCl ₃ : 0.86-0.91 ppm (m, 6H), 0.96-1.06 ppm (m, 4H), 1.12-1.44 ppm (m, 14H), 1.81-1.84 ppm (m, 8H), 2.32-2.34 ppm (m, 2H), 3.71-3.75 ppm (br, 4H), 4.67-4.76 ppm (q, 4H) , J = 10.0 Hz), 6.61-6.64 ppm (m, 2H), 6.71-6.75 ppm (m, 4H), 6.91-6.92 ppm (m, 2H), 6.97 −7.03 ppm (m, 6H).

<< Synthesis Example 8 W-A8 Synthesis >>

<Synthesis of Compound [11] and Compound [13]>
In tetrahydrofuran (156 g), 4,4′-dinitro-1,1′-biphenyl-2,2′-dimethanol (39.2 g, 129 mmol) and triethylamine (35.0 g, 346 mmol) were charged and iced in a nitrogen atmosphere. Ethanesulfonyl chloride (34.8 g, 271 mmol) was added dropwise under cold conditions. After the dropwise addition, the reaction temperature was stirred at 40 ° C. for 3 hours to obtain compound [11]. Subsequently, 4-cyclohexylphenol (50.0 g, 284 mmol) dissolved in tetrahydrofuran (230 g) and potassium hydroxide (85.0% product, 47.1 g, 714 mmol) dissolved in pure water (231 g) were compounded. In addition to the reaction solution of [11], the mixture was heated to 50 ° C. and reacted for 39 hours. After completion of the reaction, the reaction solution was poured into pure water (660 g) and subjected to liquid separation extraction with chloroform (588 g × 4 times). The collected organic phase was concentrated under reduced pressure, the crude product was dissolved in tetrahydrofuran (118 g) by heating at 60 ° C., methanol (235 g) was added to precipitate crystals, and the mixture was stirred at room temperature and filtered. The crystal was washed with a cake with pure water / methanol = 1/1 mixed solvent (118 g) and methanol (118 g × 2 times) and dried to obtain compound [13] (yield: 67.6 g, 120 mmol, yield) : 93%).
¹ H-NMR (400 MHz) in CDCl ₃ : 1.18-1.30 ppm (m, 2H), 1.31-1.38 ppm (m, 8H), 1.71-1.75 ppm (m, 2H), 1.80-1.82 ppm (m, 8H), 2.36-2.44 ppm (m, 2H), 4.77 ppm (s, 4H), 6.67-6.70 ppm (m, 4H), 03-7.06ppm (m, 4H), 7.40ppm (d, 2H, J = 8.4Hz), 8.24ppm (d, 1H, J = 2.0Hz), 8.26ppm (d, 1H, J = 2.0 Hz), 8.54 ppm (d, 2H, J = 2.0 Hz).

<Synthesis of W-A8>
Compound [13] (65.0 g, 105 mmol) and 3% platinum carbon (5.20 g) were charged in tetrahydrofuran (325 g) and methanol (65.0 g), and reacted under a hydrogen atmosphere at room temperature for about 2 days. After completion of the reaction, the platinum carbon was removed by filtration and concentrated under reduced pressure. The crude product was dissolved in tetrahydrofuran (70.4 g) with heating at 60 ° C., methanol (130 g) was added to precipitate crystals, and the mixture was stirred at room temperature and filtered. The crystals were cake washed with methanol (130 g × 2 times) and dried to obtain WA8 (yield: 54.2 g, 96.7 mmol, yield: 92%).
¹ H-NMR (400 MHz) in CDCl ₃ : 1.19-1.28 ppm (m, 2H), 1.31-1.41 ppm (m, 8H), 1.70-1.73 ppm (m, 2H), 1.79-1.87 ppm (m, 8H), 1.87-2.39 ppm (m, 2H), 3.60-3.79 ppm (br, 4H), 4.67-4.76 ppm (q, 4H) , J = 9.6 Hz), 6.61-6.64 ppm (m, 2H), 6.72-6.75 ppm (m, 4H), 6.91-6.92 ppm (d, 2H, J = 2. 4 Hz), 6.97-7.03 ppm (m, 6H).

<< Synthesis Example 9 Synthesis of W-A9 >>

<Synthesis of Compound [11] and Compound [14]>
In tetrahydrofuran (83.6 g), 4,4′-dinitro-1,1′-biphenyl-2,2′-dimethanol (20.9 g, 68.7 mmol) and triethylamine (15.3 g, 151 mmol) were charged. Ethanesulfonyl chloride (18.6 g, 145 mmol) was added dropwise under ice-cooling conditions in a nitrogen atmosphere. After the dropwise addition, the reaction temperature was stirred at 40 ° C. for 3 hours to obtain compound [11]. Subsequently, 4-[(trans, trans) -4′-pentyl [1,1′-bicyclohexyl] -4-yl] phenol (48.6 g, 149 mmol) dissolved in tetrahydrofuran (188 g) and pure water ( Potassium hydroxide (85.0% product, 20.9 g, 317 mmol) dissolved in 119.2 g) was added to the reaction solution of compound [11] and allowed to react for 20 hours. After completion of the reaction, the reaction solution was poured into pure water (800 g) to precipitate a crude product, followed by filtration and washing with pure water. Subsequently, slurry washing was performed with a mixed solution of pure water (100 g) and methanol (100 g), followed by filtration and washing with pure water and methanol again. The crude product was dissolved in tetrahydrofuran (400 g) with heating at 60 ° C., methanol (100 g) was added to precipitate crystals, and the mixture was stirred at room temperature, filtered and dried to obtain compound [14] (yield: 49 0.7 g, 53.9 mmol, yield: 78%).
¹ H-NMR (400 MHz) in CDCl ₃ : 0.83-1.34 ppm (m, 44H), 1.71-1.85 ppm (m, 16H), 2.29-2.36 ppm (m, 2H), 4.77 ppm (s, 4H), 6.66-6.68 ppm (m, 4H), 7.01-7.03 ppm (m, 4H), 7.39 ppm (d, 2H, J = 8.0 Hz), 8.24 ppm (dd, 2H, J = 2.0 Hz, J = 8.4 Hz), 8.54 ppm (d, 2H, J = 2.4 Hz)

<Synthesis of WA9>
Compound [14] (45.1 g, 48.7 mmol) and 3% platinum carbon (3.60 g) were charged in tetrahydrofuran (361 g) and methanol (90.2 g), and the pressure was 0.4 MPa under a hydrogen pressure atmosphere at 40 ° C. The reaction was performed for about 9 hours. After completion of the reaction, the solvent was removed by filtration and concentration under reduced pressure, and methanol (135 g) was added to carry out slurry washing. Subsequently, the crude product obtained by filtration was dissolved in tetrahydrofuran (180 g) with heating at 60 ° C., ethyl acetate (120 g) was added, and the mixture was stirred under room temperature conditions to precipitate crystals. -A9 was obtained (yield: 17.8 g, 20.7 mmol, yield: 43%).
¹ H-NMR (400 MHz) in CDCl ₃ : 0.88-1.34 ppm (m, 44H), 1.71-1.86 ppm (m, 16H), 2.29-2.36 ppm (m, 2H), 3.69 ppm (br, 4H), 4.70 ppm (d, 2H, J = 12.4 Hz), 4.76 ppm (d, 2H, J = 12.4 Hz), 6.62 ppm (dd, 2H, J = 2) .4 Hz, J = 8.0 Hz), 6.71-6.73 ppm (m, 4H), 6.91 ppm (d, 2H, J = 2.4 Hz), 6.96-6.99 ppm (m, 6H)

<< Synthesis Example 10 Synthesis of WA10 >>

<Synthesis of Compound [15]>
In N-methylpyrrolidone (540 g), 2-fluoro-5-nitrotoluene (91.0 g, 587 mmol), 1,3-propanediol (22.3 g, 291 mmol), potassium hydroxide (85.0% product, 71. 6 g, 1.08 mol), and stirred at 80 ° C. for 20 hours under a nitrogen atmosphere. After completion of the reaction, pure water (1440 g) is added to perform water split crystallization, and after filtration, the crystals are washed with cake with pure water (540 g × 3 times) and methanol (360 g × 2 times), respectively, and dried to give a compound. [15] was obtained (yield: 57.2 g, 165 mmol, yield: 54%).

<Synthesis of Compound [16]>
Compound [15] (40.0 g, 116 mmol), N-bromosuccinimide (45.2 g, 254 mmol), 2,2′-azobis (isobutyronitrile) (3.79 g) in 1,2-dichloroethane (540 g) 23.1 mmol), and after purging with nitrogen, the mixture was stirred at 100 ° C. for about 7 days. The reaction solution was filtered to remove insoluble succinimide, ethyl acetate (250 g) was added to the filtrate, liquid separation extraction and washing were performed with pure water (250 g × 3 times), and the organic phase was recovered and concentrated. The obtained concentrate was crystallized from ethyl acetate (346 g) and hexane (395 g) and filtered to collect crystals. Further, the filtrate was concentrated, recrystallized and filtered again with chloroform (223 g) and hexane (434 g), and dried to obtain a crude product of compound [16] (crude yield: 21.3 g, crude yield). : 37%).

<Synthesis of Compound [17]>
In N, N-dimethylacetamide (96.0 g), p- (trans-4-heptylcyclohexyl) phenol (24.0 g, 87.5 mmol) and potassium carbonate (12.1 g, 87.5 mmol) were charged at 100 ° C. Stir. Compound [16] crude product (20.0 g) dissolved in N, N-dimethylacetamide (54.0 g) was added dropwise and reacted for 24 hours. Crystals precipitated from the reaction solution were separated by filtration, washed with slurry with methanol (66.0 g) and pure water (67.0 g), respectively, filtered and dried again to obtain compound [17] (yield: 4). .23 g, 4.75 mmol, yield: 4.1% (yield based on charged compound [15])).
¹ H-NMR (400 MHz) in CDCl ₃ : 0.89 ppm (t, 6H, J = 6.8 Hz), 0.99-1.07 ppm (m, 4H), 1.19-1.43 ppm (m, 30H) ), 1.84-1.87 ppm (m, 8H), 2.36-2.44 ppm (m, 4H), 4.29 ppm (t, 4H, J = 6.0 Hz), 5.04 ppm (s, 4H) ), 6.84-6.90 ppm (m, 6H), 7.10-7.13 ppm (m, 4H), 8.17 ppm (dd, 2H, J = 3.2 Hz, 9.0 Hz), 8.38 ppm (D, 2H, J = 2.8 Hz).

<Synthesis of WA-10>
Compound [17] (3.60 g, 4.04 mmol) and 3% platinum carbon (0.290 g) were charged in tetrahydrofuran (28.8 g) and methanol (7.5 g) under a hydrogen atmosphere at a pressure of 0.4 MPa. And stirred at 40 ° C. for 3 hours. After completion of the reaction, the platinum carbon was removed by filtration and concentrated under reduced pressure. Crystals were precipitated by adding ethyl acetate and methanol to the crude product, stirred under room temperature conditions, filtered and dried to obtain WA10 (yield: 2.05 g, 2.47 mmol, yield: 54). %).
¹ H-NMR (400 MHz) in CDCl ₃ : 0.89 ppm (t, 6H, J = 6.8 Hz), 0.98-1.06 ppm (m, 4H), 1.18-1.44 ppm (m, 30H) ), 1.83 to 1.86 ppm (m, 8H), 2.15 to 2.21 ppm (m, 2H), 2.36-2.42 ppm (m, 2H), 3.42 ppm (br, 4H), 4.09 ppm (t, 4H, J = 6.0 Hz), 5.00 ppm (s, 4H), 6.55-6.57 ppm (m, 2H), 6.70 ppm (d, 2H, J = 8.8 Hz) ), 6.82-6.89 ppm (m, 6H), 7.07-7.10 ppm (m, 4H).

<Synthesis of polyimide polymer>
[Synthesis Example 1]
D2 (2.50 g, 10.0 mmol), W-A1 (3.03 g, 4.00 mmol), C1 (1.73 g, 16.0 mmol) were mixed in NMP (36.2 g) and mixed at 60 ° C. 3 After reacting for hours, D1 (1.78 g, 9.10 mmol) was added and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution having a resin solid content concentration of 20 mass%. It was 840 mPa * s when the viscosity of this polyamic-acid solution was measured.
After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting to 6.5% by mass, acetic anhydride (4.43 g) and pyridine (1.37 g) were added as an imidization catalyst at 80 ° C. The reaction was performed for 3 hours. This reaction solution was put into methanol (382 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (1). The imidation ratio of this polyimide was 76.4%, the number average molecular weight was 16,165, and the weight average molecular weight was 49,988.

[Synthesis Example 2]
D2 (2.50 g, 10.0 mmol), W-A2 (3.14 g, 4.00 mmol), C1 (1.84 g, 16.0 mmol) were mixed in NMP (36.9 g) and 3 ° C. at 60 ° C. After reacting for hours, D1 (1.84 g, 9.38 mmol) was added and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution having a resin solid content concentration of 20 mass%. The viscosity of this polyamic acid solution was measured and found to be 658 mPa · s.
After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting to 6.5% by mass, acetic anhydride (4.38 g) and pyridine (1.36 g) were added as an imidization catalyst at 80 ° C. The reaction was performed for 3 hours. This reaction solution was put into methanol (382 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (2). The imidation ratio of this polyimide was 75.8%, the number average molecular weight was 15,430, and the weight average molecular weight was 45,756.

[Synthesis Example 3]
D2 (2.50 g, 10.0 mmol), W-A3 (3.25 g, 4.00 mmol), C1 (1.73 g, 16.0 mmol) were mixed in NMP (37.3 g) and 3 at 60 ° C. After reacting for hours, D1 (1.84 g, 9.38 mmol) was added and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution having a resin solid content concentration of 20 mass%. It was 656 mPa * s when the viscosity of this polyamic-acid solution was measured.
After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting to 6.5% by mass, acetic anhydride (4.32 g) and pyridine (1.34 g) were added as an imidization catalyst at 80 ° C. The reaction was performed for 3 hours. This reaction solution was put into methanol (382 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (3). The imidation ratio of this polyimide was 74.7%, the number average molecular weight was 13,340, and the weight average molecular weight was 41,948.

[Control Synthesis Example 1]
D2 (1.50 g, 6.0 mmol), C2 (1.83 g, 12.0 mmol), C3 (2.18 g, 9.0 mmol), A1 (3.43 g, 9.0 mmol) NMP (41.1 g) After dissolving for 3 hours at 60 ° C., D3 (1.31 g, 6.0 mmol) was added followed by D1 (3.47 g, 17.7 mmol) and NMP (13.71 g) at 25 ° C. For 10 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (50 g) and diluting to 6.5% by mass, acetic anhydride (11.1 g) and pyridine (3.4 g) were added as an imidization catalyst and reacted at 60 ° C. for 3 hours. It was. This reaction solution was poured into methanol (700 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (4). The imidation ratio of this polyimide was 79%, the number average molecular weight was 11000, and the weight average molecular weight was 24000.

[Comparative Synthesis Example 1]
D2 (2.88 g, 11.5 mmol), A1 (3.50 g, 9.20 mmol), C1 (1.49 g, 13.8 mmol) were mixed in NMP (40.2 g) and reacted at 60 ° C. for 3 hours. Then, D1 (2.19 g, 11.2 mmol) was added and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution having a resin solid content concentration of 20 mass%. It was 680 mPa * s when the viscosity of this polyamic-acid solution was measured.
After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting to 6.5% by mass, acetic anhydride (4.64 g) and pyridine (1.44 g) were added as an imidization catalyst at 80 ° C. The reaction was performed for 3 hours. This reaction solution was put into methanol (382 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder (R1). The imidation ratio of this polyimide was 75.1%, the number average molecular weight was 15,322, and the weight average molecular weight was 45,800.

[Synthesis Example 5]
D2 (2.50 g, 10.0 mmol), W-A4 (4.62 g, 6.00 mmol), C1 (1.51 g, 14.0 mmol) were mixed in NMP (24.5 g) and mixed at 60 ° C. with 3 After reacting for hours, D1 (1.92 g, 9.80 mmol) was added and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution having a resin solid content concentration of 20 mass%. The viscosity of this polyamic acid solution was measured and found to be 783 mPa · s.
After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting to 6.5% by mass, acetic anhydride (3.86 g) and pyridine (1.20 g) were added as an imidization catalyst at 80 ° C. The reaction was performed for 3 hours. This reaction solution was poured into methanol (233 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (5). The imidation ratio of this polyimide was 76.7%, the number average molecular weight was 14,399, and the weight average molecular weight was 38,573.

[Synthesis Example 6]
D2 (2.50 g, 10.0 mmol), W-A5 (4.70 g, 6.00 mmol) and C1 (1.51 g, 14.0 mmol) were mixed in NMP (24.9 g) and 3 After reacting for hours, D1 (1.92 g, 9.80 mmol) was added and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution having a resin solid content concentration of 20 mass%. When the viscosity of this polyamic acid solution was measured, it was 769 mPa · s.
After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting to 6.5% by mass, acetic anhydride (3.83 g) and pyridine (1.19 g) were added as an imidization catalyst at 80 ° C. The reaction was performed for 3 hours. This reaction solution was put into methanol (232 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (6). The imidation ratio of this polyimide was 73.4%, the number average molecular weight was 13,841, and the weight average molecular weight was 37,284.

[Synthesis Example 7]
D2 (6.26 g, 25.0 mmol), WA6 (5.05 g, 5.00 mmol), C1 (4.87 g, 45.0 mmol) were mixed in NMP (62.0 g) and mixed at 60 ° C. with 3 After reacting for hours, D1 (4.51 g, 23.0 mmol) was added and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution having a resin solid content concentration of 20 mass%. The viscosity of this polyamic acid solution was measured and found to be 658 mPa · s.
After adding NMP to the obtained polyamic acid solution (75.0 g) and diluting to 6.5% by mass, acetic anhydride (18.2 g) and pyridine (5.6 g) were added as an imidization catalyst at 80 ° C. The reaction was performed for 3 hours. This reaction solution was poured into methanol (1000 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (7). The imidation ratio of this polyimide was 72.9%, the number average molecular weight was 13,362, and the weight average molecular weight was 38,725.

[Synthesis Example 8]
D2 (6.26 g, 25.0 mmol), WA-7 (8.06 g, 12.5 mmol), C1 (4.06 g, 37.5 mmol) were mixed in NMP (69.2 g) and 3 After reacting for hours, D1 (4.71 g, 24.0 mmol) was added and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution having a resin solid content concentration of 20 mass%. The viscosity of this polyamic acid solution was measured and found to be 725 mPa · s.
After adding NMP to the obtained polyamic acid solution (75.0 g) and diluting to 6.5% by mass, acetic anhydride (16.5 g) and pyridine (5.1 g) were added as an imidization catalyst at 80 ° C. The reaction was performed for 3 hours. This reaction solution was poured into methanol (1000 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (8). The imidation ratio of this polyimide was 73.1%, the number average molecular weight was 13,628, and the weight average molecular weight was 39,937.

[Synthesis Example 9]
D2 (6.26 g, 25.0 mmol), WA8 (7.01 g, 12.5 mmol), C1 (4.06 g, 37.5 mmol) were mixed in NMP (66.1 g) and 3 After reacting for hours, D1 (4.71 g, 24.0 mmol) was added and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution having a resin solid content concentration of 20 mass%. The viscosity of this polyamic acid solution was measured and found to be 674 mPa · s.
After adding NMP to the obtained polyamic acid solution (75.0 g) and diluting to 6.5% by mass, acetic anhydride (17.2 g) and pyridine (5.3 g) were added as an imidization catalyst at 80 ° C. The reaction was performed for 3 hours. This reaction solution was poured into methanol (1000 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (9). The imidation ratio of this polyimide was 73.2%, the number average molecular weight was 10,425, and the weight average molecular weight was 37,759.

[Synthesis Example 10]
D2 (6.26 g, 25.0 mmol), WA-9 (2.16 g, 2.5 mmol), C1 (5.14 g, 47.5 mmol) were mixed in NMP (54.8 g) and 3 After reacting for hours, D1 (4.71 g, 24.0 mmol) was added and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution having a resin solid content concentration of 20 mass%. When the viscosity of this polyamic acid solution was measured, it was 823 mPa · s.
After adding NMP to the obtained polyamic acid solution (75.0 g) and diluting to 6.5% by mass, acetic anhydride (20.7 g) and pyridine (6.4 g) were added as an imidization catalyst at 80 ° C. The reaction was performed for 3 hours. This reaction solution was poured into methanol (1000 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (10). The imidation ratio of this polyimide was 71.5%, the number average molecular weight was 13,732, and the weight average molecular weight was 38,921.

[Synthesis Example 11]
D2 (2.50 g, 10.0 mmol), WA10 (3.31 g, 4.00 mmol), C1 (1.73 g, 16.0 mmol) were mixed in NMP (30.2 g) and mixed at 60 ° C. with 3 After reacting for hours, D1 (1.84 g, 9.40 mmol) was added and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution having a resin solid content concentration of 20 mass%. The viscosity of this polyamic acid solution was measured and found to be 695 mPa · s.
After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting to 6.5% by mass, acetic anhydride (4.35 g) and pyridine (1.35 g) were added as an imidization catalyst at 80 ° C. The reaction was performed for 3 hours. This reaction solution was put into methanol (235 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (11). The imidation ratio of this polyimide was 76.1%, the number average molecular weight was 12,913, and the weight average molecular weight was 39,182.

[Synthesis Example 12]
D2 (25.0 g, 100 mmol), W-A1 (37.9 g, 50.0 mmol), C3 (12.1 g, 50.0 mmol), C8 (33.0 g, 100 mmol) were mixed in NMP (432 g). After reacting at 60 ° C. for 3 hours, D1 (18.8 g, 96.0 mmol) was added and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution having a resin solid content concentration of 20 mass%. It was 721 mPa * s when the viscosity of this polyamic-acid solution was measured.
After adding NMP to the obtained polyamic acid solution (100 g) and diluting to 6.5% by mass, acetic anhydride (16.0 g) and pyridine (4.96 g) were added as an imidization catalyst, and the mixture was heated at 80 ° C. for 3 hours. Reacted. This reaction solution was poured into methanol (1150 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (12). The imidation ratio of this polyimide was 75.1%, the number average molecular weight was 14,736, and the weight average molecular weight was 39,645.

[Synthesis Example 13]
D2 (25.0 g, 100 mmol), W-A1 (37.9 g, 50.0 mmol), C6 (20.5 g, 60.0 mmol), C8 (6.61 g, 20, 0 mmol), C7 (27.9 g, 70,0 mmol) in NMP (471 g) and reacted at 60 ° C. for 3 hours, and then D1 (18.8 g, 96.0 mmol) was added and reacted at 40 ° C. for 3 hours to obtain a resin solid concentration of 20 A mass% polyamic acid solution was obtained. It was 771 mPa * s when the viscosity of this polyamic-acid solution was measured.
After adding NMP to the obtained polyamic acid solution (100 g) and diluting to 6.5% by mass, acetic anhydride (14.9 g) and pyridine (4.63 g) were added as an imidization catalyst, and the mixture was heated at 80 ° C. for 3 hours. Reacted. This reaction solution was poured into methanol (1150 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 60 degreeC, and obtained the polyimide powder (13). The imidation ratio of this polyimide was 76.2%, the number average molecular weight was 15,835 and the weight average molecular weight was 39,145.

[Synthesis Example 14]
D2 (25.0 g, 100 mmol), W-A1 (37.9 g, 50.0 mmol), C6 (17.0 g, 50.0 mmol), C8 (16.5 g, 50.0 mmol), C3 (12.1 g, 50.0 mmol) was mixed in NMP (434 g) and reacted at 60 ° C. for 3 hours, then D1 (18.8 g, 96.0 mmol) was added and reacted at 40 ° C. for 3 hours to obtain a resin solid content concentration of 20 A mass% polyamic acid solution was obtained. The viscosity of this polyamic acid solution was measured and found to be 701 mPa · s.
After adding NMP to the obtained polyamic acid solution (100 g) and diluting to 6.5% by mass, acetic anhydride (16.0 g) and pyridine (4.97 g) were added as an imidization catalyst, and the mixture was heated at 80 ° C. for 3 hours. Reacted. This reaction solution was poured into methanol (1150 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 60 degreeC, and obtained the polyimide powder (14). The imidation ratio of this polyimide was 74.8%, the number average molecular weight was 17,635 and the weight average molecular weight was 41,647.

[Synthesis Example 15]
D4 (43.9 g, 196 mmol), W-A1 (30.3 g, 40.0 mmol), C4 (13.9 g, 70.0 mmol), C8 (16.5 g, 50.0 mmol), C5 (7.59 g, 40.0 mmol) was mixed in NMP (455 g) and reacted at 60 ° C. for 15 hours to obtain a polyamic acid solution having a resin solid content concentration of 20 mass%. The viscosity of this polyamic acid solution was measured and found to be 662 mPa · s.
After adding NMP to the obtained polyamic acid solution (100 g) and diluting to 6.5% by mass, acetic anhydride (17.9 g) and pyridine (5.55 g) were added as imidization catalysts, and the mixture was heated at 100 ° C. for 3 hours. Reacted. This reaction solution was put into methanol (1160 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 60 degreeC, and obtained the polyimide powder (15). The imidation ratio of this polyimide was 71.7%, the number average molecular weight was 13,329, and the weight average molecular weight was 40,527.

[Synthesis Example 16]
D2 (25.0 g, 100 mmol), C2 (21.3 g, 140 mmol), C10 (24.6 g, 60.0 mmol) were dissolved in NMP (284 g), reacted at 60 ° C. for 3 hours, and then D5 ( 14.3 g, 40.0 mmol) followed by D1 (11.0 g, 56.0 mmol) and NMP (100 g) were added and reacted at 25 ° C. for 10 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (100 g) and diluting to 6.5% by mass, acetic anhydride (21.0 g) and pyridine (6.52 g) were added as imidization catalysts, and the mixture was reacted at 80 ° C. for 3 hours. It was. This reaction solution was poured into methanol (1170 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (16). The imidation ratio of this polyimide was 75.8%, the number average molecular weight was 14679, and the weight average molecular weight was 35747.

[Synthesis Example 17]
D2 (25.0 g, 100 mmol), C6 (50.0 g, 120 mmol), C9 (15.1 g, 60.0 mmol), W-A1 (15.1 g, 20.0 mmol) were dissolved in NMP (385 g). After reacting at 60 ° C. for 3 hours, D1 (18.8 g, 96.0 mmol) and NMP (75.3 g) were added and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution having a resin solid content concentration of 20% by mass. Got. The viscosity of this polyamic acid solution was measured and found to be 753 mPa · s.
After adding NMP to this polyamic acid solution (100 g) and diluting to 6.5% by mass, acetic anhydride (17.6 g) and pyridine (5.47 g) were added as imidization catalysts, and the mixture was reacted at 80 ° C. for 3 hours. It was. This reaction solution was poured into methanol (1160 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 60 degreeC, and obtained the polyimide powder (17). The imidation ratio of this polyimide was 71.1%, the number average molecular weight was 17635, and the weight average molecular weight was 38427.

[Comparative Synthesis Example 2]
D2 (6.26 g, 25.0 mmol), A2 (12.23 g, 30.0 mmol) and C1 (2.16 g, 20.0 mmol) were mixed in NMP (76.7 g) and reacted at 80 ° C. for 5 hours. Then, D1 (4.90 g, 25.0 mmol) was added and reacted at 40 ° C. for 12 hours to obtain a polyamic acid solution having a resin solid content concentration of 20 mass%. The viscosity of this polyamic acid solution was measured and found to be 338 mPa · s.
After adding NMP to the obtained polyamic acid solution (75.0 g) and diluting to 6.5% by mass, acetic anhydride (15.0 g) and pyridine (4.6 g) were added as an imidization catalyst at 80 ° C. The reaction was performed for 3 hours. This reaction solution was poured into methanol (1000 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder (R2). The imidation ratio of this polyimide was 73.0%, the number average molecular weight was 10,175, and the weight average molecular weight was 23,642.

[Comparative Synthesis Example 3]
D2 (6.26 g, 25.0 mmol), A3 (7.06 g, 25.0 mmol) and C1 (2.70 g, 25.0 mmol) were mixed in NMP (62.8 g) and reacted at 80 ° C. for 5 hours. Then, D1 (4.90 g, 25.0 mmol) was added and reacted at 40 ° C. for 12 hours to obtain a polyamic acid solution having a resin solid content concentration of 20 mass%. It was 446 mPa * s when the viscosity of this polyamic-acid solution was measured.
After adding NMP to the obtained polyamic acid solution (75.0 g) and diluting to 6.5% by mass, acetic anhydride (18.3 g) and pyridine (5.7 g) were added as an imidization catalyst at 80 ° C. The reaction was performed for 3 hours. This reaction solution was poured into methanol (1000 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder (R3). The imidation ratio of this polyimide was 72.2%, the number average molecular weight was 11,636, and the weight average molecular weight was 24,624.
Table 1 summarizes the compositions of the polyimide powders obtained in the synthesis examples and comparative synthesis examples.

<Preparation of liquid crystal aligning agent>
In Examples and Comparative Examples, preparation examples of liquid crystal alignment treatment agents are described. Using the liquid-crystal aligning agent obtained by the Example and the comparative example, preparation of a liquid crystal display element and various evaluation were performed.

<Example 1>
NMP (28.2 g) was added to the polyimide powder (1) (3.00 g) obtained in Synthesis Example 1, and dissolved by stirring at 70 ° C. for 24 hours. NMP (g) and BCS (18.8 g) were added to this solution, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent (V-1). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 2> and <Example 3>
In Example 1, using the polyimide powders (2) and (3) in place of the polyimide powder (1), the liquid crystal aligning agents (V-2) and (V-3) were prepared in the same procedure as in Example 1. Got. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Control 1>
In Example 1, using the polyimide powder (4) obtained in Control Synthesis Example 1 instead of the polyimide powder (1), the liquid crystal aligning agent (V-4) was obtained by the same procedure as in Example 1. It was. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 4>
3.0 g of the liquid crystal aligning agent (V-1) obtained from Example 1 was mixed as the first component, and 7.0 g of the liquid crystal aligning agent (V-4) obtained in Control 1 was mixed as the second component. The liquid crystal aligning agent (V-5) was obtained by stirring for 1 hour.

<Example 5> to <Example 6>
In Example 4, using the liquid crystal aligning agent (V-2) or (V-3) instead of the liquid crystal aligning agent (V-1) as the first component, respectively, by the same procedure as in Example 4, respectively. Liquid crystal aligning agents (V-6) and (V-7) were obtained.

<Comparative Example 1>
NMP (28.2 g) and BCS (18.8 g) were added to the polyimide powder (R1) (3.00 g) obtained in Comparative Synthesis Example 1, and the mixture was stirred at 70 ° C. for 24 hours to obtain a liquid crystal alignment treatment agent ( R-V1) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the obtained liquid crystal aligning agent (R-V1), production of a liquid crystal display element, evaluation of vertical alignment, evaluation of pretilt angle, evaluation of voltage holding ratio, and evaluation of afterimage characteristics were performed.

<Example 7>
NMP (22.0 g) was added to the polyimide powder (5) (3.00 g) obtained in Synthesis Example 5, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, 3.0 g of E2 (1 wt% NMP solution) and BCS (20.0 g) were added and stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent (V-8). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormalities such as turbidity and precipitation.

<Examples 8 to 13, 15 to 17, 19, 20 and Comparative Examples 2 to 4>
Polyimide powders (6) to (11), (13) to (13) obtained in Synthesis Examples 6 to 11, 13 to 15, and 17 and Comparative Synthesis Examples 1 to 3 and Control Synthesis Example 1 in the same manner as in Example 7. Liquid crystal alignment agents (V-9 to V-21) and (R-V2 to R-V4) were prepared using 15), (17), (R1 to R3), and (4).

<Example 14>
NEP (22.0 g) was added to the polyimide powder (12) (3.00 g) obtained in Synthesis Example 12, and dissolved by stirring at 70 ° C. for 24 hours. NEP (3.0 g) and BCS (20.0 g) were added to this solution, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent (V-15). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormalities such as turbidity and precipitation.

<Example 18>
For the polyimide powder (16) obtained in Synthesis Example 16, the same operation as in Example 14 was performed to obtain a liquid crystal alignment film treating agent (V-19).

<Example 21>
3.0 g of the liquid crystal aligning agent (V-15) obtained from Example 14 as the first component, 7.0 g of the liquid crystal aligning agent (V-19) obtained in Example 18 as the second component, The cross-linking agent E1 was mixed at 5% by weight with respect to the resin component in the liquid crystal alignment film agent, and stirred for 1 hour to obtain a liquid crystal aligning agent (W-2).

<Examples 22 to 24>
Liquid crystal alignment agents (W-3) to (W-5) were obtained in the same manner as in Example 21 for the liquid crystal alignment agents (V-16) to (V-21) obtained in Examples 15 to 20. It was.

Using the liquid crystal aligning agent obtained in the examples and the liquid crystal aligning agent obtained in the comparative example, production of a liquid crystal display element, evaluation of vertical alignment, scratch test, evaluation of pretilt angle, evaluation of voltage holding ratio Afterimage characteristics were evaluated.

<Production of liquid crystal display element for measuring voltage holding ratio>
The liquid crystal aligning agent obtained in the examples and the liquid crystal aligning agent obtained in the comparative example were subjected to pressure filtration with a membrane filter having a pore diameter of 1 μm. The obtained solution was spin-coated on an ITO surface of a 40 mm × 30 mm ITO electrode glass substrate (length: 40 mm, width: 30 mm, thickness: 1.1 mm) washed with pure water and IPA (isopropyl alcohol), Heat treatment was performed on a hot plate at 70 ° C. for 90 seconds and in a heat circulation type clean oven at 230 ° C. for 30 minutes to obtain an ITO substrate with a liquid crystal alignment film having a film thickness of 100 nm. Two obtained ITO substrates with a liquid crystal alignment film were prepared, and bead spacers (manufactured by JGC Catalysts & Chemicals Co., Ltd., true ball, SW-D1) having a diameter of 4 μm were applied to the liquid crystal alignment film surface of one of the substrates.
Next, the periphery was coated with a sealant (XN-1500T manufactured by Mitsui Chemicals). Next, the surface of the other substrate on which the liquid crystal alignment film was formed was faced inward and bonded to the previous substrate, and then the sealing material was cured to create an empty cell. Liquid crystal MLC-3023 (trade name, manufactured by Merck & Co., Inc.) was injected into this empty cell by a reduced pressure injection method to prepare a liquid crystal cell.
After that, in the state where a DC voltage of 15 V was applied to the obtained liquid crystal cell, ultraviolet light passing through a band pass filter with a wavelength of 365 nm was irradiated at 15 J / cm ² using an ultraviolet irradiation device using a high pressure mercury lamp as a light source. Thus, a vertically aligned liquid crystal display element was obtained. The UV irradiation amount was measured by connecting a UV-35 light receiver to UV-M03A manufactured by ORC.

<Preparation of liquid crystal display element for pretilt angle and afterimage evaluation>
The liquid crystal aligning agent obtained in the examples was filtered under pressure through a membrane filter having a pore diameter of 1 μm. The obtained solution was washed with pure water and IPA (isopropyl alcohol), and an ITO electrode substrate (vertical: 35 mm, horizontal: 30 mm) on which an ITO electrode pattern having a pixel size of 200 μm × 600 μm and a line / space of 3 μm was formed. , Thickness: 0.7 mm) and on the ITO surface of a glass substrate with ITO electrodes (length: 35 mm, width: 30 mm, thickness: 0.7 mm) on which a photo spacer having a height of 3.2 μm is patterned, respectively. Spin coating was performed, and heat treatment was performed on a hot plate at 70 ° C. for 90 seconds and in a heat circulation type clean oven at 230 ° C. for 30 minutes to obtain an ITO substrate with a liquid crystal alignment film having a film thickness of 100 nm.
The ITO electrode substrate on which the ITO electrode pattern is formed is divided into four in a cross checker (checkered) pattern, and can be driven separately for each of the four areas.
Next, the periphery was coated with a sealant (XN-1500T manufactured by Mitsui Chemicals). Next, the surface of the other substrate on which the liquid crystal alignment film was formed was faced inward and bonded to the previous substrate, and then the sealing material was cured to create an empty cell. Liquid crystal MLC-3023 (trade name, manufactured by Merck & Co., Inc.) was injected into this empty cell by a reduced pressure injection method to prepare a liquid crystal cell.
Thereafter, a DC voltage of 15 V was applied to the obtained liquid crystal cell, and all the pixel areas were driven and passed through a band-pass filter having a wavelength of 365 nm using an ultraviolet irradiation device using a high-pressure mercury lamp as a light source. A vertical alignment type liquid crystal display device was obtained by irradiation with ultraviolet rays at 10 J / cm ² . A UV-35 light receiver was connected to UV-M03A manufactured by ORC for measurement of the amount of ultraviolet irradiation.
Further, in Examples 1 to 3 and Comparative Example 1, in addition to the standard conditions described above, vertical alignment was performed under the same conditions as described above except that the liquid crystal alignment film was formed under severe conditions by heating at 230 ° C. for 120 minutes. Type liquid crystal display element was prepared.

<Evaluation>
(Vertical alignment)
The liquid crystal orientation of the liquid crystal display element was observed with a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation), and it was confirmed whether or not the liquid crystal was vertically aligned. Specifically, those in which no defects due to liquid crystal flow or bright spots due to alignment defects were observed were considered good. The evaluation results are shown in Table 2.

(Voltage holding ratio)
The voltage holding ratio (%) after applying 1V voltage to the liquid crystal display element for evaluating the voltage holding ratio produced above with an application time of 60 microseconds at an interval of 1667 milliseconds and 1667 milliseconds after release of the application. Was measured. The measurement device used was VHR-1 manufactured by Toyo Technica. The evaluation results are shown in Table 2.

(Pretilt angle)
Using an LCD analyzer (LCA-LUV42A manufactured by Meiryo Technica Co., Ltd.), among the liquid crystal display elements for pretilt angle evaluation prepared above, liquid crystal display elements in which defects due to liquid crystal flow were not observed were measured. . The evaluation results are shown in Table 2.

(Afterimage characteristics)
Using the afterimage evaluation liquid crystal display element produced above, 60 Hz, 20 Vp-p AC voltage was applied to two diagonal areas of the four pixel areas, and the device was driven at a temperature of 23 ° C. for 168 hours. Thereafter, all four pixel areas were driven with an AC voltage of 5 Vp-p, and the luminance difference of the pixels was visually observed. A state in which almost no difference in luminance was confirmed was considered good. The evaluation results are shown in Table 3.

(Scratch test)
A scratch test was performed on the alignment film surface of the substrate with the polyimide coating film obtained in the example using UMT-2 (Bruker AXS Co., Ltd.).
FVL was selected as the UMT-2 sensor, and a 1.6 mm sapphire sphere was attached to the tip of the scratch part.
A scratch test was conducted by changing the load from 1 mN to 20 mN over 100 seconds in a range of 0.5 mm in width and 2.0 mm in length with the tip of the scratch part in contact with the surface of the liquid crystal alignment film at a load of 1 mN. At this time, the moving direction of the tip of the scratch part was reciprocating to the side, and the moving speed was 5.0 mm / sec. The scratch area was moved in the vertical direction by moving the substrate with the liquid crystal alignment film in the vertical direction at 20 μm / second.
After the scratch test, MLC-3022 (a negative type liquid crystal manufactured by Merck & Co., Inc.) was dropped onto the liquid crystal alignment film surface that had been scratch-tested. Thereto, another substrate with a liquid crystal alignment film obtained in Example 1 and a 4 μm spacer dispersed thereon was superimposed so that the liquid crystal alignment film surfaces face each other, and the dropped MLC-3022 was sandwiched.
In a state where the polarization axis of the upper and lower polarizing plates of the polarizing microscope (ECLIPSE E600WPOL) (made by Nikon Corporation) is set to 90 ° (crossed Nicols), the place where the scratch test was performed is observed, and whether light is transmitted. Observed. Regarding the spot where the scratch test was performed, the state where no bright spot or light omission was observed was indicated as ◯, the state where a slight luminescent spot or light omission was observed was indicated as △, and the state where the entire scratched area was exposed to light was indicated as x. Table 6 shows.

As a result of the above, specifically, as can be seen from the comparison between Examples 1 to 3 and Comparative Example 1 shown in Table 4, the liquid crystal display element using the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention is It was found that the pretilt angle was not changed even under severe conditions, and the liquid crystal orientation was good.
Further, as shown in Table 5, it was found that in Example 4 to Example 6 in which the liquid crystal aligning agent (V-4) was mixed, the afterimage characteristics were satisfactory.
Furthermore, from this example, it was found that the liquid crystal alignment film obtained using a specific side chain diamine was excellent in pretilt angle stability even when baked under severe conditions. It was also confirmed that even when there was physical contact with the liquid crystal alignment film as in the scratch test, good vertical alignment could be maintained with little damage to the alignment film.

A liquid crystal display element using a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention can be suitably used for a liquid crystal display element. These elements are also useful in liquid crystal displays for display purposes, and in light control windows and optical shutters for controlling transmission and blocking of light.

Claims

A liquid crystal containing at least one polymer selected from a polyimide precursor which is a reaction product of a diamine component containing a diamine represented by the following formula [1] and a tetracarboxylic acid component and a polyimide which is an imidized product thereof. Alignment agent:
In the formula [1], X represents a single bond, —O—, —C (CH 3 ) 2 —, —NH—, —CO—, — (CH 2 ) m —, —SO 2 —, and any of them And m represents an integer of 1 to 8, and each Y independently represents a structure of the following formula [1-1];
In formula [1-1], Y 1 and Y 3 each independently represent a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O— , -CONH-, -NHCO-, -COO-, and -OCO-, at least one selected from the group consisting of;
Y 2 represents a single bond or — (CH 2 ) b — (b is an integer of 1 to 15) (provided that Y 1 or Y 3 is a single bond, — (CH 2 ) a — 2 is a single bond, and Y 1 is at least one selected from the group consisting of —O—, —CH 2 O—, —CONH—, —NHCO—, —COO—, and —OCO—, and / or Or when Y 3 is at least one selected from the group consisting of —O—, —CH 2 O—, —CONH—, —NHCO—, —COO— and —OCO—, Y 2 is a single bond or — ( CH 2 ) b — (provided that when Y 1 is —CONH—, they are Y 2 and Y 3 single bonds));
Y 4 represents at least one divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton and a tocophenol skeleton, The optional hydrogen atom on the cyclic group includes an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, and a fluorine-containing alkoxy group having 1 to 3 carbon atoms. Or may be substituted with a fluorine atom;
Y 5 represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, a carbon number of 1 Substituted with an alkoxy group having 3 to 3, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom;
Y 6 represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and a fluorine-containing alkoxy group having 1 to 18 carbon atoms. At least one selected from the group consisting of groups;
n represents an integer of 0 to 4.
The liquid crystal aligning agent of Claim 1 by which the diamine represented by the said Formula [1] is represented by following formula [1 '].
The diamine represented by the formula [1] is represented by the following formula [1] -a1, the following formula [1] -a2, or the following formula [1] -a3. Liquid crystal aligning agent.
The diamine represented by the formula [1] is represented by the following formula [1] -a1-1, the following formula [1] -a2-1 to the following formula [1] -a2-4, the following formula [1] -a3- 4. The liquid crystal aligning agent according to claim 1, which is represented by 1 or the following formula [1] -a3-2.
Y represented by the structure of the formula [1-1] is represented by the following formulas [1-1] -1 to [1-1] -22 (wherein * represents the formula [1], the formula [1] '] Represents the position of bonding to the phenyl group in the formula [1] -a1 to the formula [1] -a3; m represents an integer of 1 to 15, and n represents an integer of 0 to 18 The liquid crystal aligning agent according to any one of claims 1 to 4, which is represented by any one of
The diamine component further contains a diamine represented by the following formula [2] (in the formula [2], A 1 and A 2 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Represents an alkenyl group having 2 to 5 carbon atoms or an alkynyl group having 2 to 5 carbon atoms;
Y 1 represents a divalent organic group. )
The liquid crystal aligning agent according to any one of claims 1 to 5.
A liquid crystal alignment film formed using the liquid crystal aligning agent according to any one of claims 1 to 6.
Applying the liquid crystal aligning agent according to any one of claims 1 to 6 on a substrate to form a coating film;
Baking the coating film; and aligning the film obtained by baking;
A method for producing a liquid crystal alignment film, which comprises forming a liquid crystal alignment film.
A liquid crystal display device comprising: a liquid crystal alignment film according to claim 7; or a liquid crystal alignment film obtained by the production method according to claim 8.