KR102588036B1 - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display device - Google Patents

Abstract

The present invention provides a liquid crystal aligning agent that yields a liquid crystal aligning film that does not deteriorate in its ability to vertically align the liquid crystal even when exposed to excessive heating, and further maintains the liquid crystal even when the film is damaged by contact with any foreign matter. A liquid crystal aligning agent is provided that yields a liquid crystal aligning film in which the ability to align vertically is not reduced.
This invention is a diamine represented by formula [1] ⁽ In formula [1], ⁶ represents a specific group described in the specification), a diamine component containing a polyimide precursor that is a reaction product with a tetracarboxylic acid component, and a polyimide that is an imidate thereof. Liquid crystal alignment containing at least one kind of polymer selected from It provides offerings.

Description

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

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

A liquid crystal display device in which liquid crystal molecules aligned perpendicularly to a substrate are responded to by an electric field (also called vertical alignment (VA) method) involves a process of irradiating ultraviolet rays while applying a voltage to the liquid crystal molecules during the manufacturing process. There is something that includes .

In such a vertically aligned liquid crystal display device, a photopolymerizable compound is added to the liquid crystal composition in advance, a vertical alignment film such as a polyimide-based film is used, and ultraviolet rays are irradiated while applying a voltage to the liquid crystal cell to change the response of the liquid crystal. Technology for increasing the speed (PSA (Polymer Sustained Alignment) type device, for example, see Patent Document 1 and Non-Patent Document 1) is known.

As a liquid crystal aligning agent used in such PSA type devices, 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 had a high ability to vertically align the liquid crystal, and the vertically aligned liquid crystal display element in which this liquid crystal aligning agent was used had good display characteristics.

Japanese Patent Publication No. 2003-307720 WO2006/070819

K. Hanaoka, SID 04 DIGEST, P.1200-1202

However, in recent vertical alignment type liquid crystal display elements, due to the influence of thinner and larger substrates used, a temperature difference occurs between different parts of the same substrate during firing, and the liquid crystal alignment film in the excessively heated part causes the liquid crystal to form. The ability to align vertically decreases, and as a result, a problem arises in which the resulting liquid crystal display element partially causes display defects.

Moreover, in the liquid crystal panel manufacturing process, it is also a problem that the liquid crystal alignment film and the column spacer come into contact, and the liquid crystal alignment film is scratched, causing an alignment defect (bright spot) to occur in that portion.

The present invention is to provide a liquid crystal aligning agent that yields a liquid crystal aligning film in which the ability to vertically align the liquid crystal does not decrease even when exposed to excessive heating.

Moreover, the object is to provide a liquid crystal aligning agent that can be used to obtain a liquid crystal aligning film in which the ability to vertically align the liquid crystal does not decrease even when any foreign matter comes into contact with the film and a scratch occurs.

The inventors discovered that the objective could be achieved with a liquid crystal aligning agent of the following structure, and completed this invention.

That is, the structure of the present invention is as follows.

1. Liquid crystal alignment containing at least one type of polymer selected from a polyimide precursor that is a reaction product with a diamine component containing diamine represented by the following formula [1] and a tetracarboxylic acid component, and a polyimide that is its imidate. my.

[Formula 1]

_{In formula [} 1] _, represents a divalent organic group consisting of SO ₂ - and any combination thereof, and m represents an integer of 1 to 8.

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

In formula [1-1], Y ¹ and Y ³ are each independently a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, - It represents at least one type selected from the group consisting of CONH-, -NHCO-, -COO-, and -OCO-.

Y ² represents a single bond or -(CH ₂ ) _b - (b is an integer from 1 to 15) (however, when Y ¹ or Y ³ is a single bond or -(CH ₂ ) _a -, Y ² represents is a single bond, Y ¹ is at least one selected from the group consisting of -O-, -CH ₂ O-, -CONH-, -NHCO-, -COO- and -OCO-, and/or Y ³ is - In the case of at least one member 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- ( However, when Y ¹ is -CONH-, Y ² and Y ³ are single bonds)).

Y ⁴ represents at least one type of divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocycle, or a divalent organic group of 17 to 51 carbon atoms having a steroid skeleton and a tocophenol skeleton, and the cyclic group Any hydrogen atom may be substituted with 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, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or 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 heterocycle, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. group, 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 is a group consisting of a hydrogen atom, an alkyl group with 1 to 18 carbon atoms, an alkenyl group with 2 to 18 carbon atoms, a fluorine-containing alkyl group with 1 to 18 carbon atoms, an alkoxy group with 1 to 18 carbon atoms, and a fluorine-containing alkoxy group with 1 to 18 carbon atoms. Represents at least one species selected from. n represents an integer from 0 to 4.

According to the present invention, a liquid crystal aligning agent can be provided that yields a liquid crystal aligning film in which the ability to vertically align the liquid crystal does not decrease even when exposed to excessive heating.

Moreover, according to the present invention, in addition to the above effects or in addition to the above effects, a liquid crystal aligning agent is provided in which the ability to vertically align the liquid crystal is not reduced even when any foreign matter comes into contact with the film and the film is scratched. can do.

Furthermore, according to this invention, the liquid crystal aligning film obtained from the said liquid crystal aligning agent, and the method of obtaining a liquid crystal aligning film using the said liquid crystal aligning agent can be provided.

The liquid crystal aligning agent of this invention contains a diamine component containing the diamine (hereinafter, "diamine represented by said formula [1]" may be abbreviated as "specific diamine") represented by said formula [1], and tetracarboxylic It contains at least one type of polymer (hereinafter sometimes abbreviated as “specific polymer”) selected from a polyimide precursor that is a reaction product with a boxylic acid component and a polyimide that is its imidide.

The specific polymer contains a specific diamine, but may have diamines other than the specific diamine.

The amount of specific diamine and other diamines 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 desirable to have a specific diamine.

Moreover, the liquid crystal aligning agent of this invention may contain "the polyimide which is a polyimide precursor and/or its imidate" 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 the following formula [1].

[Formula 2]

_{In formula [} 1] _, represents a divalent organic group consisting 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-, -OC(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., but these It is not limited to

X is preferably a single bond, -O-, -NH-, -O-(CH ₂ ) _m -O-.

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

[Formula 3]

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

[Formula 4]

From the formula [1]-a1 to formula [1]-a3 and the formula [1'], the formula [1] is preferably any structure selected from the following formulas, and is preferably formula [1]- The structure represented by a1-1 is preferable.

[Formula 5]

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

[Formula 6]

In formula [1-1], Y ¹ and Y ³ are each independently a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, - It represents at least one type selected from the group consisting of CONH-, -NHCO-, -COO-, and -OCO-.

Y ² represents a single bond or -(CH ₂ ) _b - (b is an integer from 1 to 15) (however, when Y ¹ or Y ³ is a single bond or -(CH ₂ ) _a -, Y ² represents is a single bond, Y ¹ is at least one selected from the group consisting of -O-, -CH ₂ O-, -CONH-, -NHCO-, -COO- and -OCO-, and/or Y ³ is - In the case of at least one member 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- ( However, when Y ¹ is -CONH-, Y ² and Y ³ are single bonds)).

Y ⁴ represents at least one type of divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocycle, or a divalent organic group of 17 to 51 carbon atoms having a steroid skeleton and a tocophenol skeleton, and the cyclic group Any hydrogen atom may be substituted with 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, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or 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 heterocycle, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. group, 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 is a group consisting of a hydrogen atom, an alkyl group with 1 to 18 carbon atoms, an alkenyl group with 2 to 18 carbon atoms, a fluorine-containing alkyl group with 1 to 18 carbon atoms, an alkoxy group with 1 to 18 carbon atoms, and a fluorine-containing alkoxy group with 1 to 18 carbon atoms. Represents at least one species selected from. n represents an integer from 0 to 4.

Examples of the group represented by the formula [1-1] include the following groups [1-1]-1 to [1-1]-22, but are not limited to these. Among these, [1-1]-1 to [1-1]-4, [1-1]-8, and [1-1]-10 are preferable. In addition, * represents the position bonded to 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 from 1 to 15, and n represents an integer from 0 to 18.

[Formula 7]

＜Photo-reactive side chain＞

The polymer contained in the liquid crystal aligning agent of this invention may have a photoreactive side chain.

The photoreactive side chain may be possessed by a “specific polymer,” or a “polyimide precursor and/or its imidized product,” which is a polymer other than the “specific polymer.”

<Diamine containing photoreactive side chains>

In order to introduce a photoreactive side chain into a polymer other than the “specific polymer” and/or the “specific polymer,” it is preferable to use a diamine with a photoreactive side chain as part of the diamine component. As diamine which has a photoreactive side chain, the diamine which has a side chain represented by formula [VIII] or formula [IX] is mentioned, but is not limited to these.

[Formula 8]

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 in the side chain, the positions 2 and 3, positions 2 and 4, positions 2 and 5, positions 2 and 6, positions 3 and 4, and positions 3 and 5 on the benzene ring. I can hear it. Among them, from the viewpoint of reactivity when synthesizing polyamic acid, the positions 2 and 4, the positions 2 and 5, or the positions 3 and 5 are preferable. Considering the ease of synthesizing diamine, positions 2 and 4, or positions 3 and 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-. In particular, R ⁸ is preferably a single bond, -O-, -COO-, -NHCO-, or -CONH-.

R ⁹ represents a single bond and an alkylene group having 1 to 20 carbon atoms which may be substituted with a fluorine atom, and -CH ₂ - of the alkylene group may be optionally substituted with -CF ₂ - or -CH=CH-, and If any groups are not adjacent to each other, they may be substituted with these groups; -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, divalent carbon ring or heterocycle.

In addition, the above-mentioned divalent carbon ring or heterocycle can specifically exemplify the following, but is not limited to these.

[Formula 9]

R ⁹ can be formed by conventional organic synthesis methods, but from the viewpoint of ease of synthesis, a single bond or an alkylene group having 1 to 12 carbon atoms is preferable.

R ¹⁰ represents a photoreactive group selected from the following formula.

[Formula 10]

R ¹⁰ is preferably a methacrylic group, an acrylic 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 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 carbon ring, or a heterocyclic ring, and one or more hydrogen atoms of the alkylene group, a divalent carbon ring, or a heterocyclic ring may be substituted with a fluorine atom or an organic group. . In Y ₂ , -CH ₂ - may be substituted with the following groups if they are not adjacent to each other; -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 Cinnamo Diary. Y ₅ is a single bond, an alkylene group having 1 to 30 carbon atoms, a divalent carbon ring, or a heterocyclic ring, and one or more hydrogen atoms of the alkylene group, a divalent carbon ring, or a heterocyclic ring are substituted with a fluorine atom or an organic group. You can stay.

Y ₅ may have -CH ₂ - substituted with the following groups if they are not adjacent to each other; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, -CO-.

Y ₆ represents a photopolymerizable group that is an acrylic group or a methacryl group.

Diamines having photoreactive side chains specifically include the following, but are not limited to these. In the formula below, X ^{9 and} Represents an alkylene group.

[Formula 11]

Moreover, the diamine which has a photoreactive side chain also includes the diamine which has in the side chain a group which causes a photodimerization reaction and a group which causes a photopolymerization reaction shown by the following formula.

[Formula 12]

In the above formula, Y ₁ to Y ₆ are the same as the definitions above.

The diamine having the photoreactive side chain is one type depending on the characteristics such as liquid crystal orientation when used as a liquid crystal alignment film, pretilt angle, voltage holding characteristics, and accumulated charge, and the response speed of the liquid crystal when used as a liquid crystal display element. Alternatively, two or more types can be mixed and used.

Moreover, as for the diamine which has a photoreactive side chain, it is preferable to use 10-70 mol% of the diamine component used for synthesis of a polyamic acid, More preferably, it is 20-60 mol%, Especially preferably, it is 30-70 mol%. It is 50 mol%.

Moreover, examples of diamines having a photoreactive side chain include diamines having a site in the side chain that has a radical generating structure that decomposes when irradiated with ultraviolet rays and generates radicals.

[Formula 13]

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, which may be substituted with an organic group, and the hydrogen atom may be substituted with a halogen atom.

R ₁ and R ₂ are each independently an alkyl group or an alkoxy group having 1 to 10 carbon atoms.

T ₁ and T ₂ are each independently a single bond or -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N(CH ₃ )- , -CON(CH ₃ )-, -N(CH ₃ )CO-.

S is a single bond or an alkylene group with 1 to 20 carbon atoms that is unsubstituted or substituted with a fluorine atom. However, -CH ₂ - or -CF ₂ - of the alkylene group may be optionally substituted with -CH=CH-, and may be substituted with any of the following groups in cases where they are not adjacent to each other; -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, divalent carbon ring, divalent heterocycle.

Q is a structure selected from the following (in the structural formula, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₃ represents -CH ₂ -, -NR-, -O-, or -S-. ).

[Formula 14]

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

In formula (I), if Ar has a structure like naphthylene or biphenylene, solubility deteriorates and the difficulty of synthesis also increases. If the wavelength of ultraviolet rays is in the range of 250 nm to 380 nm, sufficient characteristics can be obtained even with a phenyl group, so a phenyl group is most preferable.

In addition, R ₁ and R ₂ are each independently an alkyl group, an alkoxy group, a benzyl group, or a phenethyl group having 1 to 10 carbon atoms. In the case of an alkyl group or an alkoxy group, R ₁ and R ₂ may form a ring. do.

In formula (I), Q is preferably an electron-donating organic group, and the above groups are preferable.

When Q is an amino derivative, problems such as the carboxylic acid group formed during the polymerization of polyamic acid, which is the precursor of polyimide, may form a salt due to the amino group, so it is more preferable to use a hydroxyl group or an alkoxy group. It's a practical skill.

Diaminobenzene in formula (1) may have any structure of o-phenylenediamine, m-phenylenediamine, or p-phenylenediamine, but in terms of reactivity with acid dianhydride, m-phenylene diamine Diamine, or p-phenylenediamine, is preferred.

Specifically, in terms of ease of synthesis, high versatility, characteristics, etc., the structure represented by the formula below is most preferable. In addition, in the formula, n is an integer of 2 to 8.

[Formula 15]

＜Other diamines＞

As other diamine components for obtaining a specific polymer, you may contain diamines (hereinafter also referred to as other diamines) other than the specific diamine represented by the above formula [1]. Such diamine is represented by the following general formula [2]. Other diamines may be used singly or in combination of two or more types.

[Formula 16]

In the formula [2], A ₁ and A ₂ each independently represent a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an alkynyl group with 2 to 5 carbon atoms. From the viewpoint of monomer reactivity, A ₁ and A ₂ are preferably hydrogen atoms or methyl groups. The structure of Y ₁ is exemplified as follows.

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

[Formula 24]

[Formula 25]

[Formula 26]

[Formula 27]

[Formula 28]

[Formula 29]

[Formula 30]

[Formula 31]

[Formula 32]

[Formula 33]

[Formula 34]

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

[Formula 35]

Other diamine components used in the liquid crystal aligning agent of the present invention are not particularly limited, but are selected from the viewpoint of coating properties, voltage retention characteristics, residual DC voltage characteristics, etc. (Y-7), (Y-8), (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), and it is particularly preferable to select and use them together.

(tetracarboxylic acid component)

Examples of the tetracarboxylic acid component for obtaining a specific polymer include tetracarboxylic acid, tetracarboxylic dianhydride, tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester, or tetracarboxylic acid dialkyl ester dihalide. In the present invention, these are collectively referred to as tetracarboxylic acid components.

The tetracarboxylic acid component includes tetracarboxylic acid dianhydride, its derivative, tetracarboxylic acid, tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester, or tetracarboxylic acid dialkyl ester dihalide (collectively referred to as these). , referred to as the first tetracarboxylic acid component) can also be used.

＜Tetracarboxylic dianhydride＞

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

[1] Aliphatic tetracarboxylic dianhydride, such as 1,2,3,4-butanetetracarboxylic dianhydride;

[2] Alicyclic tetracarboxylic dianhydrides, for example, acid dianhydrides of the following formulas (X1-1) to (X1-13), etc.,

[Formula 36]

In formulas (X1-1) to (X1-4), R ₃ to R ₂₃ are each independently a hydrogen atom, a halogen atom, an alkyl group with 1 to 6 carbon atoms, an alkenyl group with 2 to 6 carbon atoms, or a C 2 to 6 alkyl group. an alkynyl group, a monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group, and may be the same or different,

In the above formula, R _M is a hydrogen atom or a methyl group,

Xa is a tetravalent organic group represented by the following formulas (Xa-1) to (Xa-7).

[Formula 37]

[3] 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 3,5,6-tricarboxy -2-carboxymethylnorbornane-2:3,5:6-2 anhydride, 4,9-dioxatricyclo[5.3.1.02,6]undecane-3,5,8,10-tetraone, etc.;

[4] Aromatic tetracarboxylic dianhydride, for example, pyromellitic anhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 3,3',4,4'-diphenyl sulfone Tetracarboxylic dianhydride, acid dianhydride represented by the following formulas (Xb-1) to (Xb-10), etc., and

[Formula 38]

[5] Additionally, acid dianhydrides represented by formulas (X1-44) to (X1-52) and tetracarboxylic dianhydrides described in Japanese Patent Application Publication No. 2010-97188 can be mentioned.

[Formula 39]

In addition, the said tetracarboxylic dianhydride can be used individually 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 is selected from the viewpoint of coating properties, voltage retention characteristics, residual DC voltage characteristics, etc. (X1-1) and (X1-2) , (X1-3), (X1-6), (X1-7), (X1-8), (X1-9), (Xa-2), pyromellitic anhydride, 3,3',4,4 It is preferable to select and use a tetracarboxylic dianhydride selected from '-diphenylsulfone tetracarboxylic dianhydride, (Xb-6), and (Xb-9).

＜Production method of polymer＞

The method for producing these polymers is usually obtained by reacting a diamine component and a tetracarboxylic acid component. Polyamic acid is produced by reacting at least one tetracarboxylic acid component selected from the group consisting of tetracarboxylic dianhydride and tetracarboxylic acid derivatives with a diamine component consisting of one or more types of diamines. Here's how to get it. Specifically, a method of obtaining polyamic acid by polycondensing tetracarboxylic dianhydride and primary or secondary diamine is used.

To obtain polyamic acid alkyl ester, polycondensation of a tetracarboxylic acid in which the carboxylic acid group has been dialkyl esterified and a primary or secondary diamine, or polycondensation of a tetracarboxylic acid dihalide in which the carboxylic acid group has been halogenated and a primary or secondary diamine. A method of polycondensing a secondary diamine or a method of converting the carboxyl group of polyamic acid into an ester is used.

To obtain polyimide, a method of ring-closing the above-mentioned polyamic acid or polyamic acid alkyl ester to obtain polyimide is used.

The reaction between 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 it dissolves the produced polyimide precursor. Specific examples of solvents used in the reaction are given below, but the solvent is not limited to these examples.

For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide or and 1,3-dimethyl-imidazolidinone. In addition, when the polyimide precursor has high solvent solubility, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or the following formula [D-1] to formula [D A solvent represented by -3] can be used.

[Formula 40]

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

These solvents may be used individually or may be used in combination. Moreover, even if it is a solvent which does not dissolve a polyimide precursor, you may mix it with the said solvent and use it to the extent that the produced polyimide precursor does not precipitate. Moreover, since moisture in the solvent inhibits the polymerization reaction and further causes hydrolysis of the produced polyimide precursor, it is preferable to use a solvent that has been dehydrated and dried.

When reacting a diamine component and a tetracarboxylic acid component in a solvent, a solution in which the diamine component is dispersed or dissolved in the solvent is stirred, and the tetracarboxylic acid component is added as is or as dispersed or dissolved in the solvent. Conversely, tetracarboxylic acid component is added as is or as dispersed or dissolved in the solvent. Examples include a method of adding a diamine component to a solution in which the carboxylic acid component is dispersed or dissolved in a solvent, a method of adding the diamine component and the tetracarboxylic acid component alternately, and any of these methods may be used. In addition, when reacting using multiple types of diamine component or tetracarboxylic acid component, they may be reacted in a premixed state, may be reacted individually sequentially, or the individually reacted low molecular weight substances may be mixed and reacted to form a polymer. You can also do this.

The temperature at which the diamine component and the tetracarboxylic acid component are polycondensed can be selected at any temperature 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 becomes difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high, making uniform stirring difficult. Therefore, it is preferably 1 to 50 mass%, more preferably 5 to 30 mass%. The reaction may be initially carried out at a high concentration, and then a solvent may be added.

In the polymerization reaction of the polyimide precursor, the ratio of the total number of moles of the diamine component and the total number of moles of the tetracarboxylic acid component is preferably 0.8 to 1.2. As with a typical polycondensation reaction, the closer this molar ratio is to 1.0, the larger the molecular weight of the polyimide precursor produced.

Polyimide is a polyimide obtained by ring-closing the above-mentioned polyimide precursor, and in this polyimide, the ring-closure ratio of the amic acid group (also referred to as the imidization ratio) does not necessarily have to be 100%, but can be arbitrarily determined depending on the use or purpose. It can be adjusted.

Methods for imidizing a polyimide precursor include thermal imidization in which the solution of the polyimide precursor is heated as is, or catalyst imidization in which a catalyst is added to the solution of the polyimide precursor.

The temperature in the case of thermally imidating a polyimide precursor in a solution is 100-400 degreeC, Preferably it is 120-250 degreeC, and the method of carrying out while removing the water produced|generated by an imidation reaction to the outside of the system is preferable. Catalyst imidization of the polyimide precursor can be performed by adding a basic catalyst and an acid anhydride to the solution of the polyimide precursor and stirring the solution at -20 to 250°C, preferably 0 to 180°C.

The amount of the basic catalyst is 0.5 to 30 mole times the amic acid group, preferably 2 to 20 mole times, and the amount of the acid anhydride is 1 to 50 mole times the amic acid group, preferably 3 to 30 mole times.

Basic catalysts include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferable because it has an appropriate basicity to proceed with the reaction.

Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. In particular, the use of acetic anhydride is preferable because purification after completion of the reaction becomes easy.

The imidization rate by catalyst imidization can be controlled by adjusting the catalyst amount, 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 added to a solvent to cause precipitation. Solvents 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 by adding it to the solvent can be recovered by filtration and then dried under normal or reduced pressure, at room temperature, or by heating. Additionally, if the precipitation-recovered polymer is re-dissolved in a solvent and the reprecipitation-recovery operation is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of solvents at this time include alcohols, ketones, hydrocarbons, etc. It is preferable to use three or more types of solvents selected from these because the purification efficiency further increases.

More specific methods for producing the polyamic acid alkyl ester of the present invention are shown in (1) to (3) below.

(1) Method for producing polyamic acid by esterification reaction

This is a method of producing a polyamic acid alkyl ester by producing a polyamic acid from a diamine component and a tetracarboxylic acid component and subjecting the carboxy group (COOH group) to a chemical reaction, that is, an esterification reaction.

The esterification reaction is a method in which polyamic acid and an esterifying agent are reacted in the presence of a solvent at -20 to 150°C (preferably 0 to 50°C) for 30 minutes to 24 hours (preferably 1 to 4 hours). am.

The esterification agent is preferably one that can be easily removed after the esterification reaction, and includes N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, and N,N-dimethylformamide dimethylformamide. Propylacetal, N,N-dimethylformamidedineopentylbutylacetal, N,N-dimethylformamidedi-t-butylacetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p- Tolyltriazene, 1-propyl-3-p-tolyltriazene, 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride, etc. You can. The amount of the esterifying agent used is preferably 2 to 6 molar equivalents per 1 mole of repeating units of polyamic acid. Among these, 2 to 4 molar equivalents are preferable.

Examples of the solvent used in the esterification reaction include a solvent used in the reaction between the diamine component and the tetracarboxylic acid component in view of the solubility of the polyamic acid in the solvent. Among them, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone is preferable. These solvents may be used singly 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 because precipitation of the polyamic acid does not occur easily. Especially, 5 to 20 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 reacted in the presence of a base and a solvent at -20 to 150°C (preferably 0 to 50°C) for 30 minutes to 24 hours (preferably 1 ~ 4 hours).

As the base, pyridine, triethylamine, 4-dimethylaminopyridine, etc. can be used. Among them, pyridine is preferable because the reaction proceeds gently. The amount of base used is preferably an amount that can be easily removed after the reaction, and is preferably 2 to 4 times the mole relative to the tetracarboxylic acid diester dichloride. Among these, 2 to 3 times the mole is more preferable.

Examples of the solvent include solvents used for the reaction between the diamine component and the tetracarboxylic acid component in view of the solubility of the obtained polymer, that is, polyamic acid alkyl ester, in the solvent. Among them, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone is preferable. These solvents may be used singly 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 because precipitation of the polyamic acid alkyl ester does not occur easily. Especially, 5 to 20 mass % is preferable. Moreover, in order to prevent hydrolysis of the tetracarboxylic acid diester dichloride, it is preferable that the solvent used in producing the polyamic acid alkyl ester is as dehydrated as possible. Additionally, it is desirable to carry out the reaction in a nitrogen atmosphere and prevent mixing of external air.

(3) Method of producing by reaction of diamine component and tetracarboxylic acid diester

Specifically, the diamine component and the tetracarboxylic acid diester are reacted in the presence of a condensing agent, a base, and a solvent at 0 to 150°C (preferably 0 to 100°C) for 30 minutes to 24 hours (preferably 3 ~ 15 hours) This is a method of polycondensation reaction.

Condensing agents include triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, N,N'-carbonyldiimidazole, dimethoxy-1, 3,5-Triazinylmethylmorpholinium, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluroniumtetrafluoroborate, O-(benzotriazole-1 -1)-N,N,N',N'-tetramethyluronium hexafluorophosphate, (2,3-dihydro-2-thioxo-3-benzooxazolyl)diphenyl phosphonate, etc. can be used. there is. The amount of the condensing agent used is preferably 2 to 3 times the mole, and especially 2 to 2.5 times the mole of 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, and is preferably 2 to 4 times the mole, and more preferably 2 to 3 times the mole, relative to the diamine component.

The solvent used in the polycondensation reaction includes the solvent used in the reaction between the diamine component and the tetracarboxylic acid component in view of the solubility of the obtained polymer, that is, polyamic acid alkyl ester, in the solvent. Among them, 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.

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

When recovering the polyamic acid alkyl ester from the solution of the polyamic acid alkyl ester obtained by the methods (1) to (3) above, the reaction solution may be added to a solvent to cause precipitation. Solvents used for precipitation include water, methanol, ethanol, 2-propanol, hexane, butyl cellosolve, acetone, toluene, etc. The polymer precipitated by adding it to the solvent is preferably washed with the solvent multiple times for the purpose of removing the additives and catalysts used above. After washing, filtration, and recovery, the polymer can be dried under normal or reduced pressure, at room temperature, or by heating. Additionally, impurities in the polymer can be reduced by re-dissolving the polymer that has been precipitated and recovered in a solvent and repeating the reprecipitation and recovery operation 2 to 10 times.

For the polyamic acid alkyl ester, the production method of (2) or (3) above is preferable.

＜Liquid crystal alignment agent＞

The liquid crystal aligning agent of this invention contains the specific polymer mentioned above, It is preferable that it is a solution for preferably forming a liquid crystal aligning film. In the liquid crystal aligning agent, 2-10 mass % is preferable and, as for content of the polymer in a liquid crystal aligning agent, 3-8 mass % is more preferable.

As for all the polymer components in the liquid crystal aligning agent of this invention, all may be the specific polymers of this invention, and other polymers other than that may be mixed. Other polymers include, in addition to polyimide and polyimide precursors, cellulose polymers, acrylic polymers, methacrylic polymers, polystyrene, polyamides, and polysiloxanes. Among the resin components contained in a liquid crystal aligning agent, 1-90 mass % is preferable, and, as for content of other polymers other than that, 30-80 mass % is more preferable.

The good solvent used for the liquid crystal aligning agent of this invention will not be specifically limited as long as the specific polymer of this invention dissolves. Although specific examples of the solvent used for the liquid crystal aligning agent are given below, it is not limited to these examples.

For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide or and 1,3-dimethyl-imidazolidinone.

In addition, when the polyimide precursor has high solvent solubility, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or the above formula [D-1] to formula [D A solvent represented by -3] can also be used.

The above-mentioned good solvents may be used as one type, or may be used in a more suitable combination and ratio according to the application method, etc.

It is preferable that the good solvent in the liquid crystal aligning agent of this invention is 20-99 mass % of the whole solvent contained in a liquid crystal aligning agent. Especially, 20 to 90 mass% is preferable. More preferable is 30 to 80 mass%.

The liquid crystal aligning agent of the present invention can use a solvent (also referred to as a poor solvent) that improves the coating properties and surface smoothness of the liquid crystal aligning film when the liquid crystal aligning agent is applied. Here is a specific example.

For example, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, Isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1- Butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methyl Cyclohexanol, 3-methylcyclohexanol, 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 ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone Tanone, 4-heptanone, 2,6-dimethyl-4-heptanone, 4,6-dimethyl-2-heptanone, 3-ethoxybutylacetate, 1-methylpentylacetate, 2-ethylbutylacetate, 2- Ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, 2-(methoxymethoxy)ethanol, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2 -(hexyloxy)ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, propylene glycol monobutyl ether, 1-(butoxyethoxy)propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, diethylene glycol mono. Ethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether 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 acetate, methyl pyruvate, ethyl pyruvate, 3-Methoxypropionate, ethyl 3-ethoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl, 3- Butyl methoxypropionate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, solvents represented by the above formulas [D-1] to [D-3], etc. You can.

Among them, preferred solvent combinations include N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone, and ethylene glycol monobutyl ether, N- Methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone, propylene glycol monobutyl ether, N-methyl-2-pyrrolidone, and γ-butyro Lactone, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol diethyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether, and 2,6-dimethyl- 4-heptanone, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether, diisopropyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone, and propylene glycol. Monobutyl ether, 2,6-dimethyl-4-heptanol, N-methyl-2-pyrrolidone, γ-butyrolactone, dipropylene glycol dimethyl ether, etc. are mentioned. 1-80 mass % of the whole solvent contained in a liquid crystal aligning agent is preferable, 10-80 mass % of these poor solvents is more preferable, and 20-70 mass % is especially preferable. The type and content of such a solvent are appropriately selected depending on the coating device, application conditions, application environment, etc. of the liquid crystal aligning agent.

In addition to the above, the liquid crystal aligning agent of the present invention includes polymers other than the polymer described in the present invention, a dielectric for the purpose of changing the electrical properties such as dielectric constant and conductivity of the liquid crystal aligning film, and a silane couple for the purpose of improving the adhesion between the liquid crystal aligning film and the substrate. Contains a ring agent, a crosslinkable compound for the purpose of increasing the hardness and density of the film when used as a liquid crystal alignment film, and an imidization accelerator for the purpose of efficiently advancing imidization by heating the polyimide precursor when baking the coating film. You can do it.

Compounds that improve the adhesion between the liquid crystal alignment film and the substrate include functional silane-containing compounds and epoxy group-containing compounds, for example, 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-ureido Propyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimeth Toxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltri Ethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethylene)-3-aminopropyltrimethoxysilane, N-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 diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N -diglycidylaminomethyl)cyclohexane or N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, etc.

Moreover, you may add the following additives to the liquid crystal aligning agent of this invention in order to increase the mechanical strength of a liquid crystal aligning film.

[Formula 41]

It is preferable that the said additive is 0.1-30 mass parts with respect to 100 mass parts of the polymer components contained in a liquid crystal aligning agent. If it is less than 0.1 parts by mass, no effect can be expected, and if it exceeds 30 parts by mass, the orientation of the liquid crystal is lowered. Therefore, the amount is more preferably 0.5 to 20 parts by mass.

＜Liquid crystal alignment film and liquid crystal display device＞

The liquid crystal aligning film of this invention can be formed by apply|coating the liquid crystal aligning agent of this invention on a board|substrate and baking.

For example, after apply|coating the liquid crystal aligning agent of this invention to a board|substrate, it dries as needed, and the cured film obtained by baking can also be used as a liquid crystal aligning film as it is. In addition, it is possible to rub this cured film, irradiate it with polarized light or light of a specific wavelength, treat it with an ion beam, or irradiate UV while applying a voltage to the liquid crystal display element after liquid crystal charging as an alignment film for PSA. do. In particular, it is useful to use as an alignment film for PSA.

At this time, the substrate used is not particularly limited as long as it is a substrate with high transparency, and includes glass plates, polycarbonate, poly(meth)acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, and polyether. Plastic substrates such as ketone, trimethylpentene, polyolefin, polyethylene terephthalate, (meth)acrylonitrile, triacetylcellulose, diacetylcellulose, and acetate butylate cellulose can be used. In addition, it is preferable to use a substrate on which ITO electrodes for driving liquid crystal are formed, from the viewpoint of process simplification. Additionally, in a reflective liquid crystal display device, an opaque material such as a silicon wafer can be used as long as it is used as a substrate on only one side, and a light-reflecting material such as aluminum can also be used as the electrode in this case.

The application method of the liquid crystal aligning agent is not particularly limited, and includes printing methods such as screen printing, offset printing, and flexo printing, inkjet methods, spray methods, roll coat methods, dip, roll coater, slit coater, and spinner. there is. In terms of productivity, transfer printing is widely used industrially, and is also 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 form a cured film. The drying process after applying the liquid crystal aligning agent is not necessarily necessary, but it is preferable to perform the drying process when the time from application to baking is not constant for each substrate, or when baking is not performed immediately after application. This drying only requires the solvent to be removed to the extent that the shape of the coating film is not deformed by transport of the substrate, etc., and the drying means is not particularly limited. 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, is used for 0.5 minutes to 30 minutes, preferably for 1 minute to 5 minutes.

The baking temperature of the coating film formed by applying a liquid crystal aligning agent is not limited, and is for example 100-350 degreeC, Preferably it is 120-350 degreeC, More preferably, it is 150-330 degreeC. 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 commonly known method, for example, a hot plate, a hot air circulation furnace, an infrared furnace, etc.

Moreover, although the thickness of the liquid crystal aligning film obtained by baking is not specifically limited, Preferably it is 5-300 nm, More preferably, it is 20-200 nm.

After forming a liquid crystal alignment film on a board|substrate by the said method, a liquid crystal display element can produce a liquid crystal cell by a well-known method. A specific example of the liquid crystal display element includes a liquid crystal cell having two substrates arranged to face each other, a liquid crystal layer formed between the substrates, and the liquid crystal alignment film formed between the substrate and the liquid crystal layer and formed with a liquid crystal aligning agent. It is a vertically aligned liquid crystal display device. Specifically, a liquid crystal alignment film is formed by applying a liquid crystal aligning agent onto two substrates and baking them, placing the two substrates so that the liquid crystal alignment films face each other, and sandwiching a liquid crystal layer made of liquid crystal between the two substrates. It is a vertically aligned liquid crystal display device having a manufactured liquid crystal cell.

By using a liquid crystal alignment film formed from a liquid crystal alignment agent containing a specific polymer of the present invention and irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer to react the polymerizable compound contained in the liquid crystal, the vertical alignment ability is significantly increased. It becomes an excellent PSA type liquid crystal display device.

The substrate of the liquid crystal display element is not particularly limited as long as it is a substrate with high transparency, but is usually a substrate on which a transparent electrode for driving liquid crystal is formed. Specific examples include the same substrate as the liquid crystal alignment film described above. A substrate on which a conventional electrode pattern or protrusion pattern is formed may be used, but in the PSA type liquid crystal display element, a liquid crystal aligning agent containing the polyimide-based polymer of the present invention is used, so for example, 1 to 1 on one side of the substrate. It is possible to operate even in a structure in which a 10 μm line/slit electrode pattern is formed and no slit pattern or protrusion pattern is formed in the opposing substrate, and the manufacturing process can be simplified by using a liquid crystal display device of this structure. High transmittance can be obtained.

Additionally, in high-performance devices such as TFT-type devices, devices such as transistors formed between an electrode for driving liquid crystal and a substrate are used.

In the case of a transmissive liquid crystal display element, it is common to use a substrate as described above, but in a reflective liquid crystal display element, it is possible to use an opaque substrate such as a silicon wafer as long as it is only on one side. 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 includes negative liquid crystal materials used in conventional vertical alignment methods, such as MLC-6608, MLC-6609, and MLC-3023 manufactured by Merck & Co., Ltd. Type liquid crystal can be used. In addition, in the PSA type liquid crystal display element, for example, a liquid crystal containing a polymerizable compound represented by the following formula can be used.

[Formula 42]

A known method can be used as a method of sandwiching the liquid crystal layer between two substrates. For example, prepare a pair of substrates on which a liquid crystal alignment film is formed, spread a spacer such as a bead on the liquid crystal alignment film of one substrate, and bond the other substrate so that the surface on which the liquid crystal alignment film is formed is inside. and a method of injecting liquid crystal under reduced pressure and sealing it. In addition, a pair of substrates on which a liquid crystal alignment film was formed was prepared, a spacer such as a bead was spread on the liquid crystal alignment film of one of the substrates, and then the liquid crystal was dropped so that the surface on which the liquid crystal alignment film was formed was inside so that the other side was formed. A liquid crystal cell can also be produced by bonding one side of the substrate and sealing it. The thickness of the spacer is preferably 1 to 30 μm, more preferably 2 to 10 μm.

The process of manufacturing 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 to the liquid crystal alignment film and the liquid crystal layer by applying a voltage between electrodes provided on a substrate, and One example is a method of irradiating ultraviolet rays while maintaining an electric field. Here, the voltage applied between the electrodes is, for example, 5 to 30 Vp-p, preferably 5 to 20 Vp-p. The amount of ultraviolet rays is, for example, 1 to 60 J, preferably 40 J or less. A smaller amount of ultraviolet rays can suppress the decrease in reliability caused by destruction of the members constituting the liquid crystal display element, and can also suppress the ultraviolet rays. This is desirable because manufacturing efficiency increases by reducing irradiation time.

As described above, when ultraviolet rays are irradiated while applying 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 remembered by this polymer, resulting in a response of the liquid crystal display element. The speed can be increased. Moreover, when ultraviolet rays are irradiated while applying voltage to the liquid crystal alignment film and the liquid crystal layer, a polyimide precursor having a side chain that vertically aligns the liquid crystal and a photoreactive side chain, and a polyimide obtained by imidizing this polyimide precursor Since the photoreactive side chains of at least one type of polymer selected from the above or the photoreactive side chains of the polymer react with the polymerizable compound, the response speed of the resulting liquid crystal display element can be increased.

Example

The present invention will be described in more detail below with reference to examples, but the present invention should not be construed as being limited to these examples. The abbreviations of the compounds used are as follows.

(liquid crystal)

MLC-3023 (manufactured by Merck & Co., liquid crystal containing negative polymerizable compound)

(Specific side chain diamine component)

W-A1: Compound represented by the formula [W-A1]

W-A2: Compound represented by the formula [W-A2]

W-A3: Compound represented by the formula [W-A3]

W-A4: Compound represented by the formula [W-A4]

W-A5: Compound represented by the formula [W-A5]

W-A6: Compound represented by the formula [W-A6]

W-A7: Compound represented by the formula [W-A7]

W-A8: Compound represented by the formula [W-A8]

W-A9: Compound represented by the formula [W-A9]

W-A10: Compound represented by the formula [W-A10]

[Formula 43]

(Other side chain diamine compounds)

A1: Compound represented by formula [A1]

A2: Compound represented by formula [A2]

A3: Compound represented by formula [A3]

[Formula 44]

(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 the formula [C4]

C5: Compound represented by formula [C5]

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]

[Formula 45]

(tetracarboxylic acid component)

D1: 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride

D2: Bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic acid dianhydride

D3: Pyromellitic dianhydride

D4: 2,3,5-tricarboxycyclopentylacetic acid dianhydride

D5: 3,3',4,4'-diphenylsulfone tetracarboxylic acid dianhydride

[Formula 46]

(menstruum)

NMP: N-methyl-2-pyrrolidone

BCS: Ethylene glycol monobutyl ether

NEP: N-ethyl-2-pyrrolidone

(Cross-linking agent)

E1: Crosslinking agent represented by the following formula (E1)

(additive)

E2: 3-picolylamine

[Formula 47]

(Molecular weight measurement)

The molecular weight of the polyimide precursor and polyimide was determined using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko) and columns (KD-803, KD-805) (manufactured by Shodex). , was measured as follows.

Column temperature: 50℃

Eluent: N,N'-dimethylformamide (as an additive, lithium bromide-hydrate (LiBr·H ₂ O) is 30 mmol/L (liter), phosphoric acid/anhydrous crystal (o-phosphoric acid) is 30 mmol/L, tetra Hydrofuran (THF) is 10 mL/L)

Flow rate: 1.0 mL/min

Standard samples for creating a calibration curve: TSK standard polyethylene oxide (molecular weight: approximately 900,000, 150,000, 100,000, and 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight: approximately 12,000, 4,000, and 1,000) (manufactured by Polymer Laboratories).

(Measurement of imidization rate of polyimide)

20 mg of polyimide powder was placed in an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, ϕ5 (manufactured by Kusano Science Co., Ltd.)) and mixed with deuterated dimethyl sulfoxide (DMSO-d6, 0.05 mass% TMS (tetramethylsilane)). (0.53 ml) was added and ultrasonic waves were applied to completely dissolve it. Proton NMR at 500 MHz was measured for this solution using an NMR measuring device (JNW-ECA500) (manufactured by JEOL Datum Co., Ltd.). The imidization rate is determined as a reference proton using a proton derived from a structure that does not change before and after imidization, and the peak integrated value of this proton and the integrated peak value of the proton derived from the NH group of amidic acid appearing around 9.5 to 10.0 ppm are used. It was obtained using the formula below.

Imidation rate (%) = (1 - α·x/y) × 100

In the above formula, x is the integrated peak value of the proton derived from the NH group of amidic acid, y is the integrated peak value of the reference proton, and α is NH of amidic acid in the case of polyamic acid (imidation rate of 0%). It is the ratio of the number of standard protons to one basic proton.

(Viscosity measurement)

In the synthesis example or comparative synthesis example, the viscosity of the polyimide polymer was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), sample amount 1.1 ml, 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 new compounds that have not been disclosed in the literature or the like, and the synthesis method is described in detail below.

The products described in Synthesis Examples 1 to 3 and Synthesis Examples 4 to 10 below were identified by ¹ H-NMR analysis (analysis conditions were as follows).

Equipment: 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>>

[Formula 48]

<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 injected Compound [1] was obtained by adding methanesulfonyl chloride (33.2 g) dropwise and reacting for 1 hour under ice-cooling conditions in a nitrogen atmosphere. Subsequently, p-(trans-4-heptylcyclohexyl)phenol (77.8 g) dissolved in tetrahydrofuran (246.6 g) was added, and after stirring at 40°C for 1 hour, hydroxyl phenol dissolved in pure water (233 g) was added. Potassium (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 the crude product, and the crude product was recovered by filtration. The obtained crude product was dissolved in tetrahydrofuran (574 g) by heating at 50°C, methanol (328 g) was added, crystals were precipitated, filtered, and dried to obtain compound [2] (quantity: 97.9 g, yield: 89%). ).

＜Synthesis of W-A1＞

Compound [2] (74.3 g, 90.9 mmol) and 3% platinum carbon (5.94 g) were added into tetrahydrofuran (1783 g), and reacted at room temperature in a hydrogen atmosphere. After completion of the reaction, the reaction mixture was filtered, and the filtrate was concentrated under reduced pressure to bring the total internal weight to 145 g. Subsequently, methanol (297 g) was added to the concentrated solution, cooled on ice, stirred, filtered, and dried to obtain W-A1 (amount: 59.2 g, yield: 86%).

<<Synthesis Example 2 Synthesis of W-A2>>

[Formula 49]

＜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) in tetrahydrofuran (327.2 g), 4 -Dimethylaminopyridine (1.50 g) was added, and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (56.6 g) was added under nitrogen atmosphere and room temperature conditions, and reacted for 3 hours. After completion of the reaction, the reaction solution was poured into pure water (1226 g), and the crude product was precipitated and recovered by filtration. Subsequently, the crude product was slurry washed with methanol (245 g), filtered, and the obtained crude product was dissolved in tetrahydrofuran (245 g) by heating at 60°C. After removing insoluble matters by filtration, the total internal weight was adjusted to 232 g by concentration under reduced pressure, methanol (163 g) was added to precipitate crystals, stirred under ice-cooling conditions, filtered, and dried to obtain compound [3]. Obtained (quantity: 73.9 g, yield: 71%).

＜Synthesis of W-A2＞

Compound [3] (73.9 g, 87.4 mmol) and 5% palladium carbon (8.80 g) were added into tetrahydrofuran (443 g) and methanol (73.9 g), and reacted at room temperature in a hydrogen atmosphere. After completion of the reaction, palladium carbon was removed by filtration, and the total internal weight was adjusted to 171 g by concentration under reduced pressure. Subsequently, methanol (222 g) was added to the concentrated solution to precipitate crystals, ice-cooled, stirred, filtered, and dried to obtain W-A2 (yield: 66.6 g, yield: 97%).

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

[Formula 50]

<Synthesis of compound [4] and compound [5]>

In toluene (366 g), 4-(trans-4-heptylcyclohexyl)-benzoic acid (73.1 g, 242 mmol) and N,N-dimethylformamide (0.73 g) were added, and chloride was added under nitrogen atmosphere at 50°C. Thionyl (35.9 g) was added dropwise. After dropwise addition, reaction was performed at the same temperature for 1 hour, and then the reaction solution was concentrated under reduced pressure to obtain compound [4]. Subsequently, in tetrahydrofuran (210 g), 4,4'-dinitro-1,1'-biphenyl-2,2'-dimethanol (35.0 g, 115 mmol) and triethylamine (26.8 g) was injected, and compound [4] dissolved in tetrahydrofuran (73.1 g) was added dropwise under ice-cooling conditions in a nitrogen atmosphere. After the dropwise addition was completed, 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 then concentrated under reduced pressure to obtain an oily compound. The obtained oil-like compound was added to pure water (1015 g) to precipitate crystals, and the crude product was recovered by filtration. Subsequently, the obtained crude product was subjected to room temperature slurry washing with methanol (291 g), room temperature slurry washing with ethyl acetate (175 g), filtration, and drying to obtain compound [5] (yield: 92.7 g, yield: 92%).

＜Synthesis of W-A3＞

Compound [5] (80.5 g, 92.2 mmol) and 3% platinacarbon (6.44 g) were added into tetrahydrofuran (484 g) and methanol (161 g), and reacted under room temperature conditions in a hydrogen atmosphere. After completion of the reaction, platinum carbon was removed by filtration and the solvent was removed by concentration under reduced pressure, thereby adjusting the total internal weight to 96.6 g. Subsequently, methanol (322 g) was added to the concentrated solution to precipitate crystals, cooled with ice, stirred, and filtered to obtain a crude product. Subsequently, the obtained crude product was dissolved by heating at 60°C with ethyl acetate (322 g), methanol (700 g) was added, crystals were precipitated under ice-cooling conditions, filtered, and dried to obtain W-A3 (quantity: 67.9 g) , yield: 91%).

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

[Formula 51]

<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 added, and nitrogen atmosphere was added for 50 minutes. Thionyl chloride (13.6 g, 114 mmol) was added dropwise under temperature conditions. After dropwise addition, reaction was performed at the same temperature for 1 hour, and then the reaction solution was concentrated under reduced pressure to obtain compound [6]. Subsequently, in tetrahydrofuran (63.0 g), 4,4'-dinitro-1,1'-biphenyl-2,2'-dimethanol (12.6 g, 41.4 mmol) and triethylamine (10.9 g, 108 mmol) was injected, and 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 set to room temperature and the reaction was allowed to proceed for 17 hours. After completion of the reaction, crystals were precipitated by adding the reaction solution to pure water (731 g), and the crude product was recovered after filtration, washing with pure water, and washing with methanol. Subsequently, the obtained crude product was heated and dissolved in toluene (56.0 g), hexane (112 g) was added, crystals were precipitated, stirred under room temperature conditions, filtered, and dried to obtain compound [7] (quantity: 17.0 g) , 20.6 mmol, yield: 50%).

＜Synthesis of W-A4＞

Compound [7] (17.0 g, 20.6 mmol) and 3% platinacarbon (1.36 g) were added into tetrahydrofuran (136 g) and methanol (34.0 g), and reacted for about 41 hours under room temperature conditions in a hydrogen atmosphere. 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 were filtered and dried to obtain W-A4 (quantity: 15.2 g, 19.9 mmol, yield: 97%).

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

[Formula 52]

＜Synthesis of compound [8]＞

In toluene (227 g), 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), tri-tert-butylphosphonium tetrafluoroborate (1.58 g, 5.44 mmol), and bis(dibenzylideneacetone)palladium (0) (3.14 g, 5.46 mmol) were injected, and nitrogen The reaction was carried out for 17 hours under ambient room temperature conditions. After completion of the reaction, 5.7 mol/L hydrochloric acid aqueous solution (80.0 mL) was added to precipitate crystals, and the hydrochloride salt of compound [8] was recovered by filtration. The obtained hydrochloride salt was dispersed in a mixed solution of toluene (300 g), ethyl acetate (200 g), and tetrahydrofuran (100 g), separated with 3.0 mol/L aqueous sodium hydroxide solution (200 g), and the organic phase was further dissolved in saturated saline solution. Washed with . Subsequently, activated carbon (item: special egret, 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 oil-like 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] (quantity: 27.5 g, 101 mmol, yield: 75%).

＜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) and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (20.0 g, 104 mmol) were added, and reacted for 14 hours under nitrogen atmosphere and room temperature conditions. I ordered it. After completion of the reaction, it was diluted with ethyl acetate (375 g), the organic phase was washed three times with pure water (149 g), and the obtained organic phase was subjected to magnesium sulfate dehydration. Subsequently, the organic phase was concentrated under reduced pressure, the total internal weight was adjusted to 112 g, methanol (120 g) was added, crystals were precipitated, filtered, and dried to obtain compound [9] (quantity: 28.0 g, 33.2 mmol, yield) : 74%)

＜Synthesis of W-A5＞

Compound [9] (28.0 g, 33.2 mmol) and 5% palladium carbon (2.10 g) were added into tetrahydrofuran (140 g) and methanol (56.0 g), and reacted for about 3 days under room temperature conditions in a hydrogen atmosphere. After completion of the reaction, palladium carbon was removed by filtration, and the total internal weight was adjusted to 122 g by concentrating under reduced pressure. Methanol (168 g) was added to the obtained solution to precipitate crystals, which were filtered and dried to obtain W-A5 (quantity: 23.8 g, 30.4 mmol, yield: 92%).

<<Synthesis Example 6 Synthesis of W-A6>>

[Formula 53]

＜Synthesis of compound [10]＞

4,4'-dinitro-2,2'-diphenic acid (25.0 g, 75.4 mmol) and cholesterol (61.7 g, 160 mmol) in tetrahydrofuran (113 g) and methylene chloride (113 g), 4- Dimethylaminopyridine (0.919 g, 7.54 mmol) and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (33.6 g, 175 mmol) were added, and the reaction was allowed to proceed for 18 hours under nitrogen atmosphere and room temperature conditions. After completion of the reaction, methylene chloride (375 g) was added to the reaction solution, the organic phase was washed three times with saturated saline solution (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, and a mixed solution of ethyl acetate (200 g) and isopropyl alcohol (200 g) was added to precipitate crystals and filtered to obtain a crude product. The obtained crude product was recrystallized twice from a mixed solution of chloroform (500 g) and methanol (600 g), filtered, and dried to obtain compound [10] (quantity: 41.8 g, 39.1 mmol, yield: 52%).

＜Synthesis of W-A6＞

Compound [10] (40.4 g, 37.8 mmol) and 5% palladium carbon (3.03 g) were added into tetrahydrofuran (320 g) and methanol (80.8 g), and reacted for about 3 days under room temperature conditions in a hydrogen atmosphere. After completion of the reaction, palladium carbon was removed by filtration, and the total internal weight was adjusted to 112 g by concentrating under reduced pressure. Methanol (160 g) was added to the obtained solution to precipitate crystals, which were filtered and dried to obtain W-A6 (quantity: 35.0 g, 34.7 mmol, yield: 92%).

<<Synthesis Example 7 Synthesis of W-A7>>

[Formula 54]

<Synthesis of compound [11] and compound [12]>

4,4'-dinitro-1,1'-biphenyl-2,2'-dimethanol (40.0 g, 132 mmol) and triethylamine (36.6 g, 362 mmol) in tetrahydrofuran (152 g) was injected, and ethanesulfonyl chloride (44.4 g, 345 mmol) was added dropwise under ice-cooling conditions under a nitrogen atmosphere. After the dropwise addition was completed, the reaction temperature was stirred at 40°C for 3 hours to obtain compound [11]. Subsequently, p-(trans-4-propylcyclohexyl)phenol (63.1 g, 289 mmol) dissolved in tetrahydrofuran (240 g) and potassium hydroxide (85.0% weight, 45.1 g) dissolved in pure water (228 g). , 683 mmol) was added to the reaction solution of compound [11], heated to 50°C, and reacted for 39 hours. After completion of the reaction, the reaction solution was poured into pure water (1500 g), the crude product was precipitated, and filtered and washed with pure water. Subsequently, slurry washing was performed with a mixed solution of pure water (378 g) and methanol (378 g), and the slurry was again filtered and washed with methanol. The obtained crude crystal was dissolved in tetrahydrofuran (600 g) by heating at 60°C, methanol (400 g) was added to precipitate crystals, stirred under room temperature conditions, filtered, and dried to obtain compound [12] (quantity: 77.7 g, 110 mmol, yield: 83%).

＜Synthesis of W-A7＞

Compound [12] (77.7 g, 110 mmol) and 3% platinum carbon (6.22 g) were added into tetrahydrofuran (741 g) and methanol (155 g), and reacted at room temperature in a hydrogen atmosphere 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 obtained concentrated crude, heated and dissolved at 60°C, acetonitrile (159 g) was added to precipitate crystals, stirred under room temperature conditions, filtered, and dried to obtain W-A7 ( Quantity: 58.6 g, 88.1 mmol, yield: 80%).

<<Synthesis Example 8 Synthesis of W-A8>>

[Formula 55]

<Synthesis of compound [11] and compound [13]>

4,4'-dinitro-1,1'-biphenyl-2,2'-dimethanol (39.2 g, 129 mmol) and triethylamine (35.0 g, 346 mmol) in tetrahydrofuran (156 g) was injected, and ethanesulfonyl chloride (34.8 g, 271 mmol) was added dropwise under ice-cooling conditions under a nitrogen atmosphere. After dropwise addition, compound [11] was obtained by stirring the reaction temperature at 40°C for 3 hours. Subsequently, 4-cyclohexylphenol (50.0 g, 284 mmol) dissolved in tetrahydrofuran (230 g) and potassium hydroxide (85.0% weight, 47.1 g, 714 mmol) dissolved in pure water (231 g) were added to the compound [ 11] was added to the reaction solution, 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 the liquid was separated and extracted with chloroform (588 g × 4 times). The recovered 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 crystals were cake washed with pure water/methanol = 1/1 mixed solvent (118 g) and methanol (118 g x 2 times) and dried to obtain compound [13] (quantity: 67.6 g, 120 mmol, yield: 93%). ).

＜Synthesis of W-A8＞

Compound [13] (65.0 g, 105 mmol) and 3% platinum carbon (5.20 g) were added to tetrahydrofuran (325 g) and methanol (65.0 g), and reacted at room temperature under a hydrogen atmosphere for about 2 days. . After completion of the reaction, platinum carbon was removed by filtration and concentrated under reduced pressure. The crude product was dissolved in tetrahydrofuran (70.4 g) by heating at 60°C, methanol (130 g) was added to precipitate crystals, and the mixture was stirred under room temperature conditions and then filtered. The crystals were cake washed with methanol (130 g x 2 times) and dried to obtain W-A8 (quantity: 54.2 g, 96.7 mmol, yield: 92%).

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

[Formula 56]

<Synthesis of compound [11] and compound [14]>

4,4'-dinitro-1,1'-biphenyl-2,2'-dimethanol (20.9 g, 68.7 mmol) and triethylamine (15.3 g, 151 mmol) in tetrahydrofuran (83.6 g) was injected, and ethanesulfonyl chloride (18.6 g, 145 mmol) was added dropwise under ice-cooling conditions in a nitrogen atmosphere. After dropwise addition, compound [11] was obtained by stirring the reaction temperature at 40°C for 3 hours. Subsequently, 4-[(trans,trans)-4'-pentyl[1,1'-bicyclohexyl]-4-yl]phenol (48.6 g, 149 mmol) dissolved in tetrahydrofuran (188 g) and Potassium hydroxide (85.0% weight, 20.9 g, 317 mmol) dissolved in pure water (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), the crude product was precipitated, and then filtered and washed with pure water. Subsequently, slurry washing was performed with a mixed solution of pure water (100 g) and methanol (100 g), filtered again, and washing with pure water and methanol. The crude product was dissolved in tetrahydrofuran (400 g) by heating at 60°C, methanol (100 g) was added, crystals were precipitated, stirred under room temperature conditions, filtered, and dried to obtain compound [14] (quantity: 49.7 g). , 53.9 mmol, yield: 78%).

＜Synthesis of W-A9＞

In tetrahydrofuran (361 g) and methanol (90.2 g), compound [14] (45.1 g, 48.7 mmol) and 3% platinum carbon (3.60 g) were injected, and the mixture was heated for about 9 minutes under the conditions of 0.4 MPa hydrogen pressure atmosphere and 40°C. reacted over time. After completion of the reaction, the solvent was removed by filtration and concentration under reduced pressure, and methanol (135 g) was added to perform slurry washing. Subsequently, the crude product obtained by filtration was dissolved in tetrahydrofuran (180 g) by heating at 60°C, ethyl acetate (120 g) was added, and the crystals were precipitated by stirring under room temperature conditions, followed by filtration and drying to produce W-A9. was obtained (quantity: 17.8 g, 20.7 mmol, yield: 43%).

<<Synthesis Example 10 Synthesis of W-A10>>

[Formula 57]

＜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% by volume, 71.6 g, 1.08 mol) was injected and stirred at 80°C for 20 hours under a nitrogen atmosphere. After completion of the reaction, pure water (1440 g) was added and water crystallization was performed. After filtration, the crystals were cake washed with pure water (540 g × 3 times) and methanol (360 g × 2 times), respectively, and dried. Compound [15] was obtained (quantity: 57.2 g, 165 mmol, yield: 54%).

＜Synthesis of compound [16]＞

In 1,2-dichloroethane (540 g), compound [15] (40.0 g, 116 mmol), N-bromosuccinimide (45.2 g, 254 mmol), 2,2'-azobis(isobutyro) Nitrile) (3.79 g, 23.1 mmol) was added, purged with nitrogen, and stirred at 100°C for about 7 days. After filtering the reaction liquid to remove insoluble succinimide, ethyl acetate (250 g) was added to the filtrate, the liquid was separated, extracted and washed with pure water (250 g x 3 times), and the organic phase was recovered and concentrated. . The obtained concentrate was crystallized and filtered using ethyl acetate (346 g) and hexane (395 g), and the crystals were recovered. Additionally, the filtrate was concentrated, crystallized again with chloroform (223 g) and hexane (434 g), filtered, and dried to obtain a crude product of compound [16] (crude quantity: 21.3 g, crude (粗) 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 added and stirred at 100°C. . The crude compound [16] (20.0 g) dissolved in N,N-dimethylacetamide (54.0 g) was added dropwise and allowed to react 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), filtered again, and dried to obtain compound [17] (quantity: 4.23 g, 4.75 mmol, yield) : 4.1% (yield based on injection compound [15]).

＜Synthesis of W-A10＞

Compound [17] (3.60 g, 4.04 mmol) and 3% platinum carbon (0.290 g) were injected into tetrahydrofuran (28.8 g) and methanol (7.5 g), and the mixture was reacted at 40°C under pressurized conditions of 0.4 MPa in a hydrogen atmosphere. It was stirred for 3 hours. After completion of the reaction, platinum carbon was removed by filtration and concentrated under reduced pressure. Ethyl acetate and methanol were added to the crude product to precipitate crystals, stirred under room temperature conditions, filtered, and dried to obtain W-A10 (quantity: 2.05 g, 2.47 mmol, yield: 54%).

＜Synthesis of polyimide polymer＞

[Synthesis Example 1]

D2 (2.50 g, 10.0 mmol), W-A1 (3.03 g, 4.00 mmol), and C1 (1.73 g, 16.0 mmol) were mixed in NMP (36.2 g), and reacted at 60°C for 3 hours, then D1 (1.78 g) g, 9.10 mmol) was added and reacted at 40°C for 3 hours to obtain a polyamic acid solution with a resin solid content concentration of 20% by mass. The viscosity of this polyamic acid solution was measured and found to be 840 mPa·s.

After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting it to 6.5% by mass, acetic anhydride (4.43 g) and pyridine (1.37 g) were added as imidization catalysts, and reaction was carried out at 80°C for 3 hours. . This reaction solution was added to methanol (382 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (1). The imidation rate 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), and C1 (1.84 g, 16.0 mmol) were mixed in NMP (36.9 g), and reacted at 60°C for 3 hours, then D1 (1.84 g, g, 9.38 mmol) was added and reacted at 40°C for 3 hours to obtain a polyamic acid solution with a resin solid content concentration of 20% by 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 it to 6.5% by mass, acetic anhydride (4.38 g) and pyridine (1.36 g) were added as an imidization catalyst, and the reaction was carried out at 80°C for 3 hours. . This reaction solution was added to methanol (382 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (2). The imidation rate 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), and C1 (1.73 g, 16.0 mmol) were mixed in NMP (37.3 g), and reacted at 60°C for 3 hours, then D1 (1.84 g, 9.38 mmol) was added and reacted at 40°C for 3 hours to obtain a polyamic acid solution with a resin solid content concentration of 20% by mass. The viscosity of this polyamic acid solution was measured and found to be 656 mPa·s.

After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting it to 6.5% by mass, acetic anhydride (4.32 g) and pyridine (1.34 g) were added as imidization catalysts, and reaction was carried out at 80°C for 3 hours. . This reaction solution was added to methanol (382 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (3). The imidation rate 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) were dissolved in NMP (41.1 g) and incubated at 60°C for 3 hours. After reaction, D3 (1.31 g, 6.0 mmol), followed by D1 (3.47 g, 17.7 mmol) and NMP (13.71 g) were added, and the reaction was carried out at 25°C for 10 hours to obtain a polyamic acid solution.

After adding NMP to this polyamic acid solution (50 g) and diluting it to 6.5 mass%, acetic anhydride (11.1 g) and pyridine (3.4 g) were added as imidization catalysts, and the reaction was allowed to proceed at 60°C for 3 hours. This reaction solution was added to methanol (700 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (4). The imidation rate 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), and 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 with a resin solid content concentration of 20% by mass. The viscosity of this polyamic acid solution was measured and found to be 680 mPa·s.

After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting it to 6.5% by mass, acetic anhydride (4.64 g) and pyridine (1.44 g) were added as an imidization catalyst, and the reaction was carried out at 80°C for 3 hours. . This reaction solution was added to methanol (382 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (R1). The imidation rate 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), and C1 (1.51 g, 14.0 mmol) were mixed in NMP (24.5 g), and reacted at 60°C for 3 hours, then D1 (1.92 g) g, 9.80 mmol) was added and reacted at 40°C for 3 hours to obtain a polyamic acid solution with a resin solid content concentration of 20% by 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 it to 6.5% by mass, acetic anhydride (3.86 g) and pyridine (1.20 g) were added as imidization catalysts, and reaction was carried out at 80°C for 3 hours. . This reaction solution was poured into methanol (233 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (5). The imidation rate 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 reacted at 60°C for 3 hours, then D1 (1.92 g) g, 9.80 mmol) was added and reacted at 40°C for 3 hours to obtain a polyamic acid solution with a resin solid content concentration of 20% by mass. The viscosity of this polyamic acid solution was measured and found to be 769 mPa·s.

After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting it to 6.5% by mass, acetic anhydride (3.83 g) and pyridine (1.19 g) were added as imidization catalysts, and reaction was carried out at 80°C for 3 hours. . This reaction solution was poured into methanol (232 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (6). The imidation rate 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), W-A6 (5.05 g, 5.00 mmol), and C1 (4.87 g, 45.0 mmol) were mixed in NMP (62.0 g), and reacted at 60°C for 3 hours, then D1 (4.51 g, 23.0 mmol) was added and reacted at 40°C for 3 hours to obtain a polyamic acid solution with a resin solid content concentration of 20% by 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 it to 6.5% by mass, acetic anhydride (18.2 g) and pyridine (5.6 g) were added as an imidization catalyst, and reaction was carried out at 80°C for 3 hours. . This reaction solution was poured into methanol (1000 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (7). The imidation rate 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), W-A7 (8.06 g, 12.5 mmol), and C1 (4.06 g, 37.5 mmol) were mixed in NMP (69.2 g), and reacted at 60°C for 3 hours, then D1 (4.71 g, 24.0 mmol) was added and reacted at 40°C for 3 hours to obtain a polyamic acid solution with a resin solid content concentration of 20% by 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 it to 6.5% by mass, acetic anhydride (16.5 g) and pyridine (5.1 g) were added as an imidization catalyst, and reaction was carried out at 80°C for 3 hours. . This reaction solution was poured into methanol (1000 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (8). The imidation rate 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), W-A8 (7.01 g, 12.5 mmol), and C1 (4.06 g, 37.5 mmol) were mixed in NMP (66.1 g), and reacted at 60°C for 3 hours, then D1 (4.71 g) g, 24.0 mmol) was added and reacted at 40°C for 3 hours to obtain a polyamic acid solution with a resin solid content concentration of 20% by 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 it to 6.5% by mass, acetic anhydride (17.2 g) and pyridine (5.3 g) were added as an imidization catalyst, and reaction was carried out at 80°C for 3 hours. . This reaction solution was poured into methanol (1000 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (9). The imidation rate 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), W-A9 (2.16 g, 2.5 mmol), and C1 (5.14 g, 47.5 mmol) were mixed in NMP (54.8 g) and reacted at 60°C for 3 hours, then D1 (4.71 g, 24.0 mmol) was added and reacted at 40°C for 3 hours to obtain a polyamic acid solution with a resin solid content concentration of 20% by mass. The viscosity of this polyamic acid solution was measured and found to be 823 mPa·s.

After adding NMP to the obtained polyamic acid solution (75.0 g) and diluting it to 6.5 mass%, acetic anhydride (20.7 g) and pyridine (6.4 g) were added as an imidization catalyst, and reaction was carried out at 80°C for 3 hours. . This reaction solution was poured into methanol (1000 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (10). The imidation rate 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), W-A10 (3.31 g, 4.00 mmol), and C1 (1.73 g, 16.0 mmol) were mixed in NMP (30.2 g), and reacted at 60°C for 3 hours, then D1 (1.84 g, 9.40 mmol) was added and reacted at 40°C for 3 hours to obtain a polyamic acid solution with a resin solid content concentration of 20% by 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 it to 6.5% by mass, acetic anhydride (4.35 g) and pyridine (1.35 g) were added as imidization catalysts, and reaction was carried out at 80°C for 3 hours. . This reaction solution was poured into methanol (235 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (11). The imidation rate 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) and incubated at 60°C. After reacting 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 with a resin solid content concentration of 20% by mass. The viscosity of this polyamic acid solution was measured and found to be 721 mPa·s.

After adding NMP to the obtained polyamic acid solution (100 g) and diluting it to 6.5% by mass, acetic anhydride (16.0 g) and pyridine (4.96 g) were added as imidization catalysts, and reaction was carried out at 80°C for 3 hours. . This reaction solution was poured into methanol (1150 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (12). The imidation rate 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) were incubated with NMP (471 After mixing in g) and reacting at 60°C for 3 hours, D1 (18.8 g, 96.0 mmol) was added and reaction was performed at 40°C for 3 hours to obtain a polyamic acid solution with a resin solid content concentration of 20% by mass. The viscosity of this polyamic acid solution was measured and found to be 771 mPa·s.

After adding NMP to the obtained polyamic acid solution (100 g) and diluting it to 6.5% by mass, acetic anhydride (14.9 g) and pyridine (4.63 g) were added as imidization catalysts, and reaction was carried out at 80°C for 3 hours. . This reaction solution was poured into methanol (1150 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 60°C to obtain polyimide powder (13). The imidation rate 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) were incubated with NMP (434). After mixing in g) and reacting at 60°C for 3 hours, D1 (18.8 g, 96.0 mmol) was added and reaction was performed at 40°C for 3 hours to obtain a polyamic acid solution with a resin solid content concentration of 20% by mass. 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 it to 6.5% by mass, acetic anhydride (16.0 g) and pyridine (4.97 g) were added as an imidization catalyst, and reaction was carried out at 80°C for 3 hours. . This reaction solution was poured into methanol (1150 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 60°C to obtain polyimide powder (14). The imidation rate 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) were reacted with NMP (455 g) and reacted at 60°C for 15 hours to obtain a polyamic acid solution with a resin solid content concentration of 20% by 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 it to 6.5% by mass, acetic anhydride (17.9 g) and pyridine (5.55 g) were added as imidization catalysts, and reacted at 100°C for 3 hours. . This reaction solution was poured into methanol (1160 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 60°C to obtain polyimide powder (15). The imidation rate 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), and C10 (24.6 g, 60.0 mmol) were dissolved in NMP (284 g) and reacted at 60°C for 3 hours, then D5 (14.3 g, 40.0 mmol), then 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 it to 6.5% by mass, acetic anhydride (21.0 g) and pyridine (6.52 g) were added as imidization catalysts, and reaction was performed at 80°C for 3 hours. This reaction solution was added to methanol (1170 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (16). The imidation rate 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) and incubated at 60°C. After reacting 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 with a resin solid content concentration of 20% by mass. 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 it to 6.5 mass%, acetic anhydride (17.6 g) and pyridine (5.47 g) were added as imidization catalysts, and the reaction was allowed to proceed at 80°C for 3 hours. This reaction solution was added to methanol (1160 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 60°C to obtain polyimide powder (17). The imidation rate 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 with a resin solid content concentration of 20% by 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 it to 6.5% by mass, acetic anhydride (15.0 g) and pyridine (4.6 g) were added as an imidization catalyst, and reaction was carried out at 80°C for 3 hours. . This reaction solution was poured into methanol (1000 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (R2). The imidation rate 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 with a resin solid content concentration of 20% by mass. The viscosity of this polyamic acid solution was measured and found to be 446 mPa·s.

After adding NMP to the obtained polyamic acid solution (75.0 g) and diluting it to 6.5% by mass, acetic anhydride (18.3 g) and pyridine (5.7 g) were added as an imidization catalyst, and reaction was carried out at 80°C for 3 hours. . This reaction solution was poured into methanol (1000 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (R3). The imidation rate of this polyimide was 72.2%, the number average molecular weight was 11,636, and the weight average molecular weight was 24,624.

The composition of the polyimide powder obtained in the synthesis examples and comparative synthesis examples is summarized in Table 1.

<Preparation of liquid crystal aligning agent>

In the examples and comparative examples, preparation examples of the liquid crystal aligning agent are described. Using the liquid crystal alignment agent obtained in the Examples and Comparative Examples, a liquid crystal display element was produced and various evaluations were performed.

<Example 1>

NMP (28.2 g) was added to polyimide powder (1) (3.00 g) obtained in Synthesis Example 1, and stirred at 70°C for 24 hours to dissolve. NMP (g) and BCS (18.8 g) were added to this solution, and it stirred at room temperature for 5 hours, and obtained a liquid-crystal aligning agent (V-1). Abnormalities such as cloudiness and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

<Example 2> and <Example 3>

In Example 1, polyimide powders (2) and (3) were used instead of polyimide powder (1), and liquid crystal aligning agents (V-2) and (V-3) were applied in the same manner as in Example 1. ) was obtained. Abnormalities such as cloudiness and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

＜Control 1＞

In Example 1, instead of polyimide powder (1), polyimide powder (4) obtained in Control Synthesis Example 1 was used, and a liquid crystal aligning agent (V-4) was obtained through the same procedure as Example 1. . Abnormalities such as cloudiness and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

<Example 4>

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

<Example 5> to <Example 6>

In Example 4, liquid crystal aligning agent (V-2) or (V-3) was used as the first component instead of liquid crystal aligning agent (V-1), and liquid crystal alignment was carried out respectively by the same procedure as in Example 4. Treatment agents (V-6) and (V-7) were obtained.

<Comparative Example 1>

NMP (28.2 g) and BCS (18.8 g) were added to polyimide powder (R1) (3.00 g) obtained in Comparative Synthesis Example 1, stirred at 70°C for 24 hours, and liquid crystal aligning agent (R-V1) was added. got it Abnormalities such as cloudiness and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

Using the obtained liquid crystal aligning agent (R-V1), production of a liquid crystal display element, evaluation of vertical alignment, evaluation of the pretilt angle, evaluation of voltage retention, and evaluation of afterimage characteristics were performed.

<Example 7>

NMP (22.0 g) was added to polyimide powder (5) (3.00 g) obtained in Synthesis Example 5, and stirred at 70°C for 24 hours to dissolve. To this solution, 3.0 g of E2 (1 wt% NMP solution) and BCS (20.0 g) were added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid-crystal aligning agent (V-8). No abnormalities such as cloudiness or precipitation were observed in this liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

<Examples 8 to 13, 15 to 17, 19, 20, Comparative Examples 2 to 4>

Polyimide powders (6) to (11), (13) to (15) obtained in Synthesis Examples 6 to 11, 13 to 15, and 17, Comparative Synthesis Examples 1 to 3, and Control Synthesis Example 1 by the same operation as Example 7. , (17), (R1 to R3), and (4) were used to prepare liquid crystal aligning agents (V-9 to V-21) and (R-V2 to R-V4).

<Example 14>

NEP (22.0 g) was added to polyimide powder (12) (3.00 g) obtained in Synthesis Example 12, and stirred at 70°C for 24 hours to dissolve. NEP (3.0 g) and BCS (20.0 g) were added to this solution, and it stirred at room temperature for 5 hours, and obtained a liquid-crystal aligning agent (V-15). No abnormalities such as cloudiness or precipitation were observed in this liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

<Example 18>

The same operation as Example 14 was performed also on the polyimide powder (16) obtained in Synthesis Example 16, and a liquid crystal aligning film treatment agent (V-19) was obtained.

<Example 21>

3.0 g of the liquid-crystal aligning agent (V-15) obtained in Example 14 as a first component, 7.0 g of the liquid-crystal aligning agent (V-19) obtained in Example 18 as a second component, and crosslinking agent E1 as the resin in the liquid crystal aligning agent. The liquid-crystal aligning agent (W-2) was obtained by mixing so that it might become 5 weight% with respect to the component, and stirring for 1 hour.

<Examples 22 to 24>

About liquid-crystal aligning agents (V-16) - (V-21) obtained in Examples 15 - 20, liquid-crystal aligning agents (W-3) - (W-5) were obtained by the same operation as Example 21.

Using the liquid crystal aligning agent obtained in the Example 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 retention, and evaluation of afterimage characteristics were performed. did.

＜Manufacturing of a liquid crystal display device for voltage retention measurement＞

The liquid-crystal aligning agent obtained in the Example and the liquid-crystal aligning agent obtained in the comparative example were pressure-filtered using a membrane filter with a pore diameter of 1 μm. The obtained solution was spin-coated on the ITO side of a 40 mm × 30 mm glass substrate with ITO electrodes (length: 40 mm, width: 30 mm, thickness: 1.1 mm) washed with pure water and IPA (isopropyl alcohol) Heat processing was performed on a hot plate at 70°C for 90 seconds and at 230°C for 30 minutes in a thermal circulation type clean oven to obtain an ITO substrate with a liquid crystal alignment film with a film thickness of 100 nm. Two obtained ITO substrates with a liquid crystal aligning film were prepared, and a bead spacer with a diameter of 4 μm (Nikki Catalyst Chemical Co., Ltd., Jinsa District, SW-D1) was applied to the liquid crystal aligning film surface of one of the substrates.

Next, the surrounding area was applied 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 turned inward and bonded to the previous substrate, and then the seal material was cured to produce an empty cell. Liquid crystal MLC-3023 (trade name manufactured by Merck & Co., Ltd.) was injected into this empty cell by a reduced-pressure injection method to produce a liquid crystal cell.

Thereafter, with a direct current voltage of 15 V applied to the obtained liquid crystal cell, 15 J/cm2 of ultraviolet rays passed through a band-pass filter with a wavelength of 365 nm was irradiated using an ultraviolet irradiation device using a high-pressure mercury lamp as a light source. , a vertically aligned liquid crystal display device was obtained. In addition, for measuring the amount of ultraviolet irradiation, a UV-35 photoreceptor was connected to UV-M03A manufactured by ORC and used.

＜Manufacturing of liquid crystal display elements for pretilt angle and afterimage evaluation＞

The liquid crystal aligning agent obtained in the example was pressure-filtered using a membrane filter with a pore diameter of 1 μm. The obtained solution was washed with pure water and IPA (isopropyl alcohol), and an ITO electrode substrate with an ITO electrode pattern with a pixel size of 200 ㎛ × 600 ㎛ and a line/space of 3 ㎛ was formed (length: 35 mm, width: Spin-coated on the ITO side of an ITO electrode-attached glass substrate (length: 35 mm, width: 30 mm, thickness: 0.7 mm) on which photospacers of 30 mm, thickness: 0.7 mm) and 3.2 μm in height were patterned, respectively. , heat treatment was performed on a hot plate at 70°C for 90 seconds and at 230°C for 30 minutes in a thermal circulation type clean oven to obtain an ITO substrate with a liquid crystal alignment film with a film thickness of 100 nm.

Additionally, the ITO electrode substrate on which this ITO electrode pattern is formed is divided into four sections in a cross-checker pattern, and each of the four areas can be driven separately.

Next, the surrounding area was applied 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 turned inward and bonded to the previous substrate, and then the seal material was cured to produce an empty cell. Liquid crystal MLC-3023 (trade name manufactured by Merck & Co., Ltd.) was injected into this empty cell by a reduced-pressure injection method to produce a liquid crystal cell.

After that, a direct current voltage of 15 V was applied to the obtained liquid crystal cell, and while all pixel areas were driven, ultraviolet rays were passed through a band-pass filter with a wavelength of 365 nm using an ultraviolet irradiation device using a high-pressure mercury lamp as a light source. was irradiated at 10 J/cm2 to obtain a vertically aligned liquid crystal display element. To measure the amount of ultraviolet irradiation, a UV-35 photoreceptor was connected to UV-M03A manufactured by ORC and used.

In addition, in Examples 1 to 3 and Comparative Example 1, in addition to the above standard conditions, heat treatment was performed at 230° C. for 120 minutes as an overheating condition to form a liquid crystal alignment film, and a vertical alignment film was formed under the same conditions as above. A liquid crystal display device was manufactured.

＜Evaluation＞

(vertical orientation)

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 the liquid crystal was oriented vertically. Specifically, those in which defects due to liquid crystal flow or bright spots due to orientation defects were not observed were considered good. The evaluation results are shown in Table 2.

(Voltage maintenance rate)

A voltage of 1 V was applied to the liquid crystal display device for voltage retention evaluation manufactured above at an application time of 60 microseconds and at an interval of 1667 milliseconds, and then the voltage retention rate (%) was measured 1667 milliseconds after the application was released. The measuring 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 Mayo Technica), measurements were performed on liquid crystal display elements for which no defects due to liquid crystal flow were observed among the liquid crystal display elements for pretilt angle evaluation produced above. The evaluation results are shown in Table 2.

(afterimage characteristics)

Using the liquid crystal display element for afterimage evaluation produced above, an alternating voltage of 60 Hz and 20 Vp-p was applied to two diagonal areas among the four pixel areas, and the device was driven at a temperature of 23°C for 168 hours. After that, all four pixel areas were driven with an alternating voltage of 5 Vp-p, and the difference in luminance of the pixels was observed with the naked eye. A state in which the luminance difference could hardly be 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 polyimide coated substrate obtained in the example using UMT-2 (manufactured by Burka AXS Co., Ltd.).

FVL was selected as the sensor of UMT-2, and a 1.6 mm sapphire sphere was installed at the tip of the scratch area.

With the tip of the scratch part in contact with the surface of the liquid crystal alignment film under a load of 1 mN, a scratch test was performed in a range of 0.5 mm in width and 2.0 mm in height by changing the load from 1 mN to 20 mN over 100 seconds. At this time, the moving direction of the tip of the scratch part was horizontal reciprocation, 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/sec.

After the scratch test, MLC-3022 (negative liquid crystal manufactured by Merck & Co., Ltd.) was dropped on the surface of the liquid crystal alignment film on which the scratch test was completed. A 4 µm spacer was spread on another substrate with a liquid crystal aligning film obtained in Example 1, which was overlapped so that the liquid crystal aligning film surfaces faced each other, and the dropwise MLC-3022 was sandwiched between them.

The point where the scratch test was performed was observed under a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon) with the polarization axes of the upper and lower polarizers being 90° (Cross-Nicol), and whether light was transmitted was observed. Regarding the points where the scratch test was performed, the state in which no bright spots or light leakage is visible at all is marked as ○, the state in which some bright spots or light leakage is visible is marked as △, and the state in which the entire scratched spot has light leakage is marked as ×, as shown in Table 6. .

As can be seen from the above results, specifically, a comparison between Examples 1 to 3 and Comparative Example 1 shown in Table 4, the liquid crystal display element using the liquid crystal aligning film obtained from the liquid crystal aligning agent of the present invention is free even under harsh conditions. There was no change in the tilt angle, and it was found that the liquid crystal orientation was good.

Moreover, as shown in Table 5, in Example 4 - Example 6 which mixed the liquid-crystal aligning agent (V-4), it turned out that the afterimage characteristic gave a favorable result.

Furthermore, from this example, it was found that the liquid crystal alignment film obtained using a specific side chain type diamine was excellent in the stability of the pretilt angle even when baked under harsh conditions. In addition, it was also confirmed that even when there was physical contact with the liquid crystal alignment film as in the scratch test, there was little damage to the alignment film and good vertical alignment could be maintained.

The liquid crystal display element using the liquid crystal aligning film obtained from the liquid crystal aligning agent of this invention can be used suitably for a liquid crystal display element. Additionally, these elements are useful in liquid crystal displays for display purposes, and also in light dimming windows and optical shutters that control the transmission and blocking of light.

Claims (14)

A liquid crystal aligning agent containing at least one type of polymer selected from a polyimide precursor that is a reaction product with a diamine component containing diamine represented by the following formula [1] and a tetracarboxylic acid component, and a polyimide that is its imidized product:
_{In formula [} 1 _{] ,} represents a divalent organic group consisting of a combination of, m represents an integer of 1 to 8, and Y each independently represents a structure of the following formula [1-1];
In formula [1-1], Y ¹ and Y ³ are each independently a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, - Represents at least one member selected from the group consisting of CONH-, -NHCO-, -COO-, and -OCO-;
Y ² represents a single bond or -(CH ₂ ) _b - (b is an integer from 1 to 15) (however, when Y ¹ or Y ³ is a single bond or -(CH ₂ ) _a -, Y ² represents is a single bond, Y ¹ is at least one selected from the group consisting of -O-, -CH ₂ O-, -CONH-, -NHCO-, -COO- and -OCO-, and/or Y ³ is - In the case of at least one member 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- ( However, when Y ¹ is -CONH-, Y ² and Y ³ are single bonds));
Y ⁴ represents at least one type of divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocycle, or a divalent organic group of 17 to 51 carbon atoms having a steroid skeleton and a tocophenol skeleton, and the cyclic group Any hydrogen atom may be substituted with 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, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or 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 heterocycle, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. group, 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 is at least selected from the group consisting of an alkyl group with 1 to 18 carbon atoms, an alkenyl group with 2 to 18 carbon atoms, a fluorine-containing alkyl group with 1 to 18 carbon atoms, an alkoxy group with 1 to 18 carbon atoms, and a fluorine-containing alkoxy group with 1 to 18 carbon atoms. Indicates 1 species;
n represents an integer from 0 to 4.

According to claim 1,
A liquid crystal aligning agent in which the diamine represented by the formula [1] is represented by the following formula [1'] (wherein the definitions of X and Y are the same as those described in Claim 1).

According to claim 1,
The diamine represented by the above formula [1] is the following formula [1]-a1, the following formula [1]-a2, or the following formula [1]-a3 (wherein the definitions of The liquid crystal aligning agent represented by (same as).
According to claim 1,
The diamine represented by the formula [1] is the following formula [1]-a1-1, the following formula [1]-a2-1 to the following formula [1]-a2-4, the following formula [1]-a3-1, or A liquid crystal aligning agent represented by the following formula [1]-a3-2 (wherein the definitions of X and Y are the same as those described in claim 1).

According to claim 1,
Y represented by the structure of the formula [1-1] is represented by the following formulas [1-1]-1 to [1-1]-22 (where * is a bond with the phenyl group in the formula [1]) The liquid crystal aligning agent represented by any of the following: represents the position being made; m represents the integer of 1-15, and n represents the integer of 0-18.

According to claim 1,
The diamine component further contains diamine represented by the following formula [2]
(In formula [2], A ₁ and A ₂ each independently represent a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an alkynyl group with 2 to 5 carbon atoms;
Y ₁ represents a divalent organic group.)
Liquid crystal orientation agent.

A liquid crystal aligning film formed using the liquid crystal aligning agent according to any one of claims 1 to 6. A process of applying the liquid crystal aligning agent according to any one of claims 1 to 6 on a substrate to form a coating film;
A step of baking the coating film; and
A step of performing orientation treatment on the film obtained by firing;
The manufacturing method of a liquid crystal aligning film which forms a liquid crystal aligning film by having. A liquid crystal aligning film formed using the liquid crystal aligning agent according to any one of claims 1 to 6; Or the process of apply|coating the liquid crystal aligning agent of any one of Claims 1-6 on a board|substrate and forming a coating film; A step of baking the coating film; and a step of orientation treatment of the film obtained by firing; Liquid crystal aligning film obtained by the manufacturing method of a liquid crystal aligning film which forms a liquid crystal aligning film by having; A liquid crystal display device comprising: Diamine represented by the following formula [1]:
_{In formula [} 1 _{] ,} represents a divalent organic group consisting of a combination of, m represents an integer of 1 to 8, and Y each independently represents a structure of the following formula [1-1];
In formula [1-1], Y ¹ and Y ³ are each independently a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, - Represents at least one member selected from the group consisting of CONH-, -NHCO-, -COO-, and -OCO-;
Y ² represents a single bond or -(CH ₂ ) _b - (b is an integer from 1 to 15) (however, when Y ¹ or Y ³ is a single bond or -(CH ₂ ) _a -, Y ² represents is a single bond, Y ¹ is at least one selected from the group consisting of -O-, -CH ₂ O-, -CONH-, -NHCO-, -COO- and -OCO-, and/or Y ³ is - In the case of at least one member 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- ( However, when Y ¹ is -CONH-, Y ² and Y ³ are single bonds));
Y ⁴ represents at least one type of divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocycle, or a divalent organic group of 17 to 51 carbon atoms having a steroid skeleton and a tocophenol skeleton, and the cyclic group Any hydrogen atom may be substituted with 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, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom;
Y ⁵ represents at least one cyclic group selected from the group consisting of a cyclohexane ring and a heterocycle, and any hydrogen atom on these cyclic groups is an alkyl group with 1 to 3 carbon atoms, an alkoxy group with 1 to 3 carbon atoms, or a carbon number. It may be substituted with 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 is at least selected from the group consisting of an alkyl group with 1 to 18 carbon atoms, an alkenyl group with 2 to 18 carbon atoms, a fluorine-containing alkyl group with 1 to 18 carbon atoms, an alkoxy group with 1 to 18 carbon atoms, and a fluorine-containing alkoxy group with 1 to 18 carbon atoms. Indicates 1 species;
n represents an integer from 0 to 4.
Diamine represented by the following formula [1]:
_{In formula} [ _{1 ] ,} Represents a divalent organic group consisting of a combination of,
k represents an integer from 1 to 8,
Y each independently represents the following formula [1-1]-1 to [1-1]-22 (wherein * represents the position bonded to the phenyl group in the following formula [1]; m is 1 represents an integer from 0 to 15, and n represents an integer from 0 to 18.

Diamine represented by any of the following formulas W-A1 to W-A10.
At least one type of polymer selected from a polyimide precursor that is a reaction product of a diamine component containing the diamine according to any one of claims 10 to 12 and a tetracarboxylic acid component, and a polyimide that is an imidate thereof. According to claim 13,
The diamine component further contains diamine represented by the following formula [2]
(In formula [2], A ₁ and A ₂ each independently represent a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an alkynyl group with 2 to 5 carbon atoms;
Y ₁ represents a divalent organic group.)
polymer.