KR20230109658A - Liquid crystal aligning agent, polymer manufacturing method, liquid crystal aligning film, liquid crystal display element - Google Patents

Abstract

(각 치환기에 대해서는 명세서에서 정의된 바와 같다.)While the liquid crystal aligning film which has high voltage retention is obtained, the risk of whitening by moisture absorption is reduced and the liquid crystal aligning agent excellent in mass-production stability and the liquid crystal display element provided with this liquid crystal aligning film are provided.
The liquid crystal aligning agent characterized by containing the following (A) component.
Component (A): A copolymer having a repeating unit represented by the following formula (a), a repeating unit represented by the following formula (1), and a repeating unit represented by the following formula (2), and a polyimide that is an imide of the copolymer. As at least one type of polymer (A) selected from the group consisting of
At least one of the repeating unit represented by the following formula (a), the repeating unit represented by the following formula (1), and the repeating unit represented by the following formula (2) has a divalent organic group represented by the following formula (EG).

(Each substituent is as defined in the specification.)

Description

Liquid crystal aligning agent, polymer manufacturing method, liquid crystal aligning film, liquid crystal display element

This invention relates to a liquid crystal aligning agent, the manufacturing method of a polymer, a liquid crystal aligning film, and a liquid crystal display element.

A liquid crystal display element used in a liquid crystal television, a navigator, a smart phone, or the like usually has a liquid crystal alignment film formed inside the element to control the arrangement of liquid crystals. A liquid crystal aligning film has a function of controlling orientation of liquid crystal molecules in a fixed direction in a liquid crystal display element. For example, a liquid crystal display element has a structure in which liquid crystal molecules constituting a liquid crystal layer are sandwiched by a liquid crystal alignment film formed on each surface of a pair of substrates. There, liquid crystal molecules are oriented in a fixed direction by the liquid crystal alignment film, and respond by application of a voltage to an electrode formed between the substrate and the liquid crystal alignment film. As a result, the liquid crystal display element displays a desired image by utilizing the orientation change due to the response of the liquid crystal molecules. As a liquid crystal alignment film, until now, a polyimide-based liquid crystal alignment film obtained by applying a liquid crystal aligning agent containing a polyimide precursor such as polyamic acid (polyamic acid) or a solution of soluble polyimide as a main component to a glass substrate or the like and firing has been mainly used. there is.

In recent years, in a liquid crystal aligning film, in addition to excellent liquid crystal orientation, a liquid crystal aligning film having a high voltage retention is required for power saving of a liquid crystal display element.

In order to meet the said demand|requirement, the proposal of the liquid crystal aligning agent containing the polyimide obtained by using a specific diamine component for reaction is made in patent document 1.

International Publication No. 2019-082975

On the other hand, organic polar solvents, such as N-methylpyrrolidone and (gamma)-butyrolactone, are generally used for the liquid crystal aligning agent containing polyimide. However, these solvents have a high solubility but high hygroscopicity. Therefore, when handling a liquid crystal aligning agent containing polyimide with low solubility in a high-humidity environment, there is a risk of moisture absorption whitening that polyimide precipitates at the time of application and the film becomes white, so there was a problem in terms of mass production stability. .

In view of the above, while the liquid crystal aligning film which has high voltage retention is obtained, the risk of moisture absorption whitening is reduced, and this invention provides the liquid crystal aligning agent excellent in mass production stability, and the liquid crystal display element provided with the liquid crystal aligning film in view of the above. make it a task to do

As a result of earnestly researching in order to achieve the said subject, this inventor discovered that the liquid crystal aligning agent containing a specific component was effective in order to achieve the said objective, and came to complete this invention.

This invention is based on this knowledge, and makes the following a summary.

The liquid crystal aligning agent characterized by containing the following (A) component.

Component (A): A copolymer having a repeating unit represented by the following formula (a), a repeating unit represented by the following formula (1), and a repeating unit represented by the following formula (2), and a polyimide that is an imide of the copolymer. As at least one type of polymer (A) selected from the group consisting of

At least one of the repeating unit represented by the following formula (a), the repeating unit represented by the following formula (1), and the repeating unit represented by the following formula (2) has a divalent organic group represented by the following formula (EG).

[Formula 1]

(X represents a tetravalent organic group. Y represents a divalent organic group derived from diamine. The two R's each independently represent a hydrogen atom or a monovalent organic group. The two Z's each independently represent a hydrogen atom or a monovalent organic group.)

[Formula 2]

(A ₁ is a divalent organic group, A _1' is a divalent organic group derived from diamine, and C ₁ and C _1' are each independently a hydrogen atom or a monovalent organic group.)

[Formula 3]

(A ₂ is a divalent organic group, and A _2' is a divalent organic group obtained by removing hydrogen atoms contained in two hydroxyl groups from an organic diol.)

[Formula 4]

(R represents a hydrogen atom or a methyl group. n is an integer of 3 to 40.)

According to the liquid crystal aligning agent of this invention, the liquid crystal aligning film which has high voltage retention is obtained, and the liquid crystal display element provided with this liquid crystal aligning film can be obtained. Furthermore, the liquid crystal aligning agent excellent in mass production stability in which the risk of whitening by moisture absorption was reduced can be obtained. Moreover, according to the liquid crystal aligning agent of this invention, a liquid crystal display element with few display defects can be obtained.

The mechanism by which the above effect of the present invention is obtained is not necessarily clear, but is roughly estimated as follows. That is, since the introduction of a urea group and a urethane group into the polymer results in a moderately strong hydrogen bond, the voltage retention property is improved, and the introduction of a hydrophilic polyethylene glycol chain into the polymer improves the solubility in water. It is thought that the effect is obtained.

Below, each component contained in the liquid crystal aligning agent of this indication and the other component mix|blended arbitrarily as needed are demonstrated. In addition, in this specification, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned as a halogen atom.

<Polymer (A)>

The liquid crystal aligning agent of the present invention is a copolymer having a repeating unit represented by the above formula (a), a repeating unit represented by the above formula (1), and a repeating unit represented by the above formula (2) (hereinafter referred to as polyimide precursor (A) ) and at least one kind of polymer (A) selected from the group consisting of polyimide which is an imide product of the copolymer, the repeating unit represented by the formula (a) or the repeating unit represented by the formula (1) , and at least one of the repeating units represented by the formula (2) has a divalent organic group represented by the formula (EG).

In the formula (EG), the upper limit of n is preferably 40, more preferably 30, and particularly preferably 20, from the viewpoint of improving the liquid-crystal orientation. As for the lower limit of n, 3 is preferable and 4 is more preferable from a viewpoint of improving liquid-crystal orientation.

(repeating unit represented by formula (a))

In the formula (a), Y represents a divalent organic group derived from diamine. As this diamine, the following diamines are mentioned. This diamine may be used individually by 1 type, and may be used in combination of 2 or more type.

diamine represented by the following formula (O); Diamine which has an optical orientation group, such as 4,4'- diaminoazobenzene or diaminotran; diamines having amide bonds or urea bonds, such as diamines represented by the following formulas (h-1) to (h-6); 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 1,4-bis(4 - Diamine represented by aminophenyl) benzene, 1, 3-bis (4-aminophenyl) benzene, 1, 4-bis (4-aminobenzyl) benzene, and a following formula (do ₎ ; diamine having at least one nitrogen atom-containing structure (hereinafter, also referred to as a specific nitrogen atom-containing structure) selected from the group consisting of a nitrogen atom-containing heterocycle, a secondary amino group, and a tertiary amino group; 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol; 4,4'-diamino-3,3'-dihydroxybiphenyl, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid and the following formula (3b-1) Diamine which has a carboxy group, such as diamine represented by - Formula (3b-4); 4-(2-(methylamino)ethyl)aniline, 4-(2-aminoethyl)aniline, 1-(4-aminophenyl)-1,3,3-trimethyl-1H-indan-5-amine, 1- (4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-inden-6-amine; diamines having photopolymerizable groups such as 2-(2,4-diaminophenoxy)ethyl methacrylate and 2,4-diamino-N,N-diallylaniline at terminals; Cholestanyloxy-3,5-diaminobenzene, Cholestanyloxy 3,5-diaminobenzene, Cholestanyloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestanyl, 3 diamines having a steroid skeleton, such as 5-diaminobenzoic acid cholestenyl, 3,5-diaminobenzoic acid lanostanil, and 3,6-bis(4-aminobenzoyloxy)cholestane; diamines represented by the following formulas (V-1) to (V-6); Groups such as the following formulas (5-1) to (5-11) "-N(D)-" (D represents a protecting group that is desorbed by heating and replaced with a hydrogen atom, and is preferably a tert-butoxycarbonyl group. ) diamine having; diamines having siloxane bonds such as 1,3-bis(3-aminopropyl)-tetramethyldisiloxane and diamine represented by the following formula (Ds-1); Diamine which has an oxazoline structure, such as following formula (Ox-1) - (Ox-2); Metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-diaminocyclohexane, 4,4' - Methylene bis (cyclohexylamine), diamine etc. which two amino groups couple|bonded with the group represented by any of formula (Y-1) - (Y-167) of International Publication No. 2018/117239.

[Formula 5]

(Ar represents a divalent benzene ring, biphenyl structure, or naphthalene ring. The two Ars may be the same or different, and any hydrogen atom of the benzene ring, biphenyl structure, or naphthalene ring is a monovalent group. p is an integer of 0 or 1. Q ₂ is -(CH ₂ ) _n - (n is an integer of 2 to 18), or -(CH ₂ ) _n - of -CH ₂ - Represents a group at least partially substituted with -O-, -C(=O)-, or -OC(=O)-, provided, however, that when Q ₂ has an ether bond, the total number of ether bonds possessed by Q ₂ should be 3 or less.)

[Formula 6]

[Formula 7]

(A plurality of m may be the same or different, respectively.)

[Formula 8]

(In formula (3b-1), A ¹ is a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON( CH ₃ )- or -N(CH ₃ )CO-, m1 and m2 are each independently an integer of 0 to 4, and m1+m2 is an integer of 1 to 4. In the formula (3b-2), m3 and m4 are each independently an integer of 1 to 5. In formula (3b-3), A ² represents a linear or branched alkyl group having 1 to 5 carbon atoms, and m5 is an integer of 1 to 5. Formula (3b-3) In -4), A ³ and A ⁴ are each independently a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) _2- , -O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON(CH ₃ )- or N-(CH ₃ )CO-, and m6 is an integer of 1 to 4.)

[Formula 9]

(X ^v1 to X ^v4 and X ^p1 to X ^p2 are each independently -(CH ₂ ) _a - (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON(CH ₃ )-, -NH-, -O-, -CH ₂ O-, -CH ₂ OCO-, -COO-, or -OCO-, and X ^v5 is -O-, -CH ₂ O-, -CH ₂ Represents OCO-, -COO-, or -OCO- Xa is a single bond, -O-, -NH-, or -O-(CH ₂ ) _m -O- (m represents an integer of 1 to 6) .), R ^v1 to R ^v4 and R ^1a to R ^1b each independently represent an alkyl group of 1 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, or an alkoxyalkyl group of 2 to 20 carbon atoms. Formula (V In -6), the two k's may be the same or different.)

[Formula 10]

(Boc represents a tert-butoxycarbonyl group.)

[Formula 11]

[Formula 12]

As diamine represented by the said formula ( _do ), diamine represented by the following formula (do _- 1) - (do _- 6) from a viewpoint of improving liquid-crystal orientation, 3,3'- diamino diphenyl ether, 3, 4'-diaminodiphenyl ether and 4,4'-diaminodiphenyl ether are preferred.

[Formula 13]

In the diamine represented by the formula (O), arbitrary hydrogen atoms in the benzene ring, the biphenyl structure, or the naphthalene ring may be substituted with a monovalent group. Examples of the monovalent group include a halogen atom, an alkyl group of 1 to 10 carbon atoms, an alkenyl group of 2 to 10 carbon atoms, an alkoxy group of 1 to 10 carbon atoms, a fluoroalkyl group of 1 to 10 carbon atoms, and a carbon atom of 2 to 10 carbon atoms. A fluoroalkenyl group, a C1-C10 fluoroalkoxy group, a C1-C10 alkyloxycarbonyl group, a cyano group, a nitro group, etc. are mentioned.

As diamine represented by the said formula (O), the diamine represented by the following formula (o-1) - (o-16) is preferable from a viewpoint of improving liquid-crystal orientation.

[Formula 14]

[Formula 15]

[Formula 16]

(In formula (o-14), two m's may be the same or different.)

Examples of the nitrogen atom-containing heterocycle that the diamine having the specific nitrogen atom-containing structure may have include pyrrole, imidazole, pyrazole, triazole, pyridine, pyrimidine, pyridazine, pyrazine, indole, and benzoimine. dazole, purine, quinoline, isoquinoline, naphthyridine, quinoxaline, phthalazine, triazine, carbazole, acridine, piperidine, piperazine, pyrrolidine, hexamethyleneimine and the like. Among these, pyridine, pyrimidine, pyrazine, piperidine, piperazine, quinoline, carbazole or acridine is preferable.

The secondary amino group and tertiary amino group that the diamine having the specific nitrogen atom-containing structure may have are represented by the following formula (n), for example.

[Formula 17]

In the formula (n), R represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. "*" represents a bond bonded to a hydrocarbon group, and at least one bond to an aromatic hydrocarbon group.

Examples of the monovalent hydrocarbon group of R in the formula (n) include an alkyl group such as a methyl group, an ethyl group, and a propyl group; Cycloalkyl groups, such as a cyclohexyl group; Aryl groups, such as a phenyl group and a methylphenyl group, etc. are mentioned. R is preferably a hydrogen atom or a methyl group.

Specific examples of the diamine having the specific nitrogen atom-containing structure include, for example, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, and 3,6-diamino. Carbazole, N-methyl-3,6-diaminocarbazole, 1,4-bis-(4-aminophenyl)-piperazine, 3,6-diaminoacridine, N-ethyl-3,6-dia Minocarbazole, N-phenyl-3,6-diaminocarbazole, diamine represented by the following formulas (Dp-1) to (Dp-8), and represented by the following formulas (z-1) to formula (z-18) Diamine is mentioned.

[Formula 18]

[Formula 19]

[Formula 20]

When the repeating unit (a) has a divalent organic group represented by the formula (EG), it preferably has a divalent organic group represented by the formula (EG) in at least one of X and Y. When said Y has a divalent organic group represented by said formula (EG), as said Y, for example, 2 derived from diamine which has an amino group via an aromatic group at both ends of the divalent organic group represented by said formula (EG) The organic group of GA is mentioned. A benzene ring, a biphenyl structure, or a naphthalene ring is mentioned as this aromatic group. Said Y is more preferably a divalent organic group derived from diamine represented by the following formula (d _EG ).

[Formula 21]

Ar each independently represents a divalent aromatic group or a condensed cyclic group, and may be the same or different. One or more hydrogen atoms on this aromatic group or condensed ring group may be substituted with a monovalent group. Specific examples of Ar include a benzene ring, a biphenyl structure, or a naphthalene ring. Examples of the monovalent group include a halogen atom, an alkyl group of 1 to 10 carbon atoms, an alkenyl group of 2 to 10 carbon atoms, an alkoxy group of 1 to 10 carbon atoms, a fluoroalkyl group of 1 to 10 carbon atoms, and a fluoroalkenyl group of 2 to 10 carbon atoms. , a fluoroalkoxy group of 1 to 10 carbon atoms, a carboxy group, a hydroxyl group, an alkyloxycarbonyl group of 1 to 10 carbon atoms, a cyano group, a nitro group, and the like. n represents the integer of 3-40. The upper limit of n is preferably 30, more preferably 20.

In addition, throughout the specification, the m-valent "aromatic group" refers to an m-valent group formed by removing m hydrogen atoms from the ring portion of an aromatic ring. The m-valent "condensed ring group" refers to an m-valent group formed by removing m hydrogen atoms from the ring portion of the condensed ring.

Y is diamine represented by the formula (O), diamine having an amide bond or urea bond, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-dia Minodiphenylmethane, 4,4'-diaminobenzophenone, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-amino) Benzyl)benzene, diamine represented by the formula ( _do ), 4-(2-(methylamino)ethyl)aniline, 4-(2-aminoethyl)aniline, group "-N(D)-" (D is heating represents a protecting group that is desorbed and substituted with a hydrogen atom, preferably a tert-butoxycarbonyl group), and a divalent organic group derived from a diamine selected from the group consisting of diamines represented by the formula (d _EG ) desirable. When Y satisfies this configuration, the effect of reducing the pretilt angle of the liquid crystal and the afterimage generated by long-term alternating current driving and also increasing the relaxation characteristic of stored charge is obtained, which is preferable.

In the formula (a), X represents a tetravalent organic group. X preferably represents a tetravalent organic group derived from tetracarboxylic dianhydride or a derivative thereof. As the tetravalent organic group, a tetravalent organic group derived from acyclic aliphatic tetracarboxylic dianhydride or a derivative thereof, a tetravalent organic group derived from alicyclic tetracarboxylic dianhydride or a derivative thereof, or aromatic tetracarboxylic and tetravalent organic groups derived from acid dianhydride or derivatives thereof.

Here, acyclic aliphatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups bonded to a chain hydrocarbon structure. However, it is not necessary to be composed only of a chain-like hydrocarbon structure, and may have an alicyclic structure or an aromatic ring structure in part. Alicyclic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups including at least one carboxy group bonded to an alicyclic structure. However, none of these four carboxyl groups are bonded to an aromatic ring. Moreover, it is not necessary to be comprised only of an alicyclic structure, and may have a chain-like hydrocarbon structure or an aromatic ring structure in part. Aromatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups including at least one carboxy group bonded to an aromatic ring. Examples of the derivative of tetracarboxylic dianhydride include tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester, and tetracarboxylic acid dialkyl ester dihalide.

This tetracarboxylic dianhydride or its derivative(s) may be used individually by 1 type, and may be used in combination of 2 or more type.

The acyclic aliphatic or alicyclic tetracarboxylic dianhydride or these derivatives are at least one selected from the group consisting of a cyclobutane ring structure, a cyclopentane ring structure, and a cyclohexane ring structure, from the viewpoint of improving the liquid crystal orientation, among others. It is preferably a tetracarboxylic dianhydride or a derivative thereof having a species partial structure.

Said X is preferably a tetravalent organic group derived from tetracarboxylic dianhydride or its derivative represented by the following formula (t).

[Formula 22]

In the formula, X ₁ is a structure selected from the following formulas (X1-1) to (X1-25). * represents a bonding hand.

[Formula 23]

[Formula 24]

[Formula 25]

[Formula 26]

In formulas (X1-1) to (X1-4), R ₁ to R ₂₁ are each independently a hydrogen atom, a halogen atom, an alkyl group of 1 to 6 carbon atoms, an alkenyl group of 2 to 6 carbon atoms, or a carbon atom of 2 to 6 carbon atoms. A 6-membered alkynyl group, a monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group. * represents a bonding hand. From the viewpoint of enhancing the liquid-crystal orientation, R ₁ to R ₂₁ are preferably a hydrogen atom, a halogen atom, a methyl group, or an ethyl group, and more preferably a hydrogen atom or a methyl group.

In formulas (X1-24) to (X1-25), j and k are integers of 0 or 1, and A ₁ and A ₂ are each independently a single bond, -O-, -CO-, - COO-, phenylene, sulfonyl group, or amide group is shown. A plurality of A ₂ may be the same or different, respectively.

Specific examples of the formula (X1-1) include the following formulas (1-1) to (1-6). From a viewpoint of improving liquid-crystal orientation, formula (1-1) and (1-2) are especially preferable. * has the same meaning as above.

[Formula 27]

Preferred specific examples of the above formulas (X1-24) and (X1-25) include the following formulas (X1-26) to (X1-41). * has the same meaning as above.

[Formula 28]

[Formula 29]

From the viewpoint of enhancing the liquid-crystal orientation, X ₁ is represented by the formulas (X1-1) to (X1-10), (X1-18) to (X1-23), (X1-24) to (X1-25), Or (X1-26) to (X1-30) are preferable, and the above formulas (X1-1), (X1-5), (X1-7) to (X1-10), (X1-21), (X1 -23), (X1-24) to (X1-25), or (X1-26) to (X1-30) are more preferable, and the above formulas (1-1), (1-2), (X1- 5), (X1-7), (X1-9), or (X1-26) to (X1-30) are more preferred.

As described above, when the repeating unit (a) has a divalent organic group represented by the formula (EG), it preferably has a divalent organic group represented by the formula (EG) in at least one of X and Y. When the X has a divalent organic group represented by the formula (EG), examples of the X include a tetracarboxylic dianhydride represented by the following or a tetravalent organic group derived from a derivative thereof.

[Formula 30]

As the monovalent organic group for R and Z in the formula (a), a monovalent hydrocarbon group having 1 to 20 carbon atoms and a methylene group of the hydrocarbon group are -O-, -S-, -CO-, and -COO -, -COS-, -NR ³ - (provided that R ³ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms), -CO-NR ³ - (provided that R ³ is a hydrogen atom or a carbon number It is a monovalent hydrocarbon group of 1 to 10.), -Si(R ³ ) ₂ - (where R ³ is a hydrogen atom or a monovalent hydrocarbon group of 1 to 10 carbon atoms), -SO ₂ -, etc. At least one hydrogen atom bonded to a monovalent group A, a monovalent hydrocarbon group, or a carbon atom of the monovalent group A is a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), a hydroxy group, 1 formed by substitution with an alkoxy group, a nitro group, an amino group, a mercapto group, a nitroso group, an alkylsilyl group, an alkoxysilyl group, a silanol group, a sulfino group, a phosphino group, a carboxy group, a cyano group, a sulfo group, an acyl group, etc. A valent group and a monovalent group having a heterocyclic ring are exemplified. Examples of the monovalent organic group for R and Z in the formula (a) include, among others, an alkyl group of 1 to 10 carbon atoms, an alkenyl group of 2 to 10 carbon atoms, an alkynyl group of 2 to 10 carbon atoms, tert-butoxy A carbonyl group or a 9-fluorenylmethoxycarbonyl group is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is even more preferable.

From the viewpoint of obtaining the effect of the present invention, R and Z are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group.

In the formula (a), X, Y, R, and Z may be one type or two or more types, respectively.

(repeating unit represented by formula (1))

In the formula (1), A ₁ is a divalent organic group. Examples of A ₁ include divalent organic groups derived from diisocyanate. This diisocyanate may be used individually by 1 type, and may be used in combination of 2 or more type.

Here, as diisocyanate, aromatic diisocyanate and aliphatic diisocyanate are mentioned, for example.

Here, "aromatic diisocyanate" means diisocyanate having at least one aromatic group. Moreover, "aliphatic diisocyanate" means the diisocyanate which has an aliphatic group and does not have an aromatic group.

As A ₁ , for example, (i) 2 derived from an aromatic diisocyanate in which R is an organic group having 6 to 30 carbon atoms and having at least one benzene ring in the diisocyanate structure (O=C=NRN=C=O); 2 derived from a valent organic group or (ii) an aliphatic diisocyanate in which R in the diisocyanate structure (O=C=NRN=C=O) is an organic group having 4 to 30 carbon atoms in which R has an aliphatic group and does not have an aromatic group; The organic group of GA is mentioned.

Moreover, an aliphatic group includes both an acyclic aliphatic group and an alicyclic group.

Specific examples of A ₁ include o-phenylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, and toluene diisocyanate (eg, 2,4-diisocyanate tolylene, 2,6-di tolylene isocyanate), 1,4-diisocyanate-2-methoxybenzene, 2,5-xylene diisocyanate, 3,3'-dimethyl-4,4'-diisocyanate biphenyl, 4,4 '-diisocyanate diphenyl ether, 2,2'-bis (4-diisocyanate phenyl) propane, 4,4'-diisocyanate diphenylmethane (4,4'-diphenylmethane diisocyanate), 4, In aromatic diisocyanates such as 4'-diisocyanate diphenyl ether, 4,4'-diisocyanate diphenylsulfone, 3,3'-diisocyanate diphenylsulfone and 2,2'-diisocyanate benzophenone and divalent organic groups derived from aliphatic diisocyanates such as isophorone diisocyanate, norbornene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and tetramethylene diisocyanate.

In the formula (1), A _1' is a divalent organic group derived from diamine. As diamine, the diamine illustrated with the said repeating unit (a) is mentioned, The preferable aspect is the same as the above.

When the formula (1) has a divalent organic group represented by the formula (EG), it is preferable that at least one of A ₁ and A _1' has a divalent organic group represented by the formula (EG).

When A _1' has a divalent organic group represented by the formula (EG), as a specific structure of A _1' , in the diamine having a divalent organic group represented by the formula (EG) exemplified by the repeating unit (a), A divalent organic group derived from it, or its preferable aspect is mentioned.

When the A ₁ has a divalent organic group represented by the formula (EG), examples of the A ₁ include a divalent organic group derived from diisocyanate represented by the following.

[Formula 31]

Examples of the monovalent organic group of C ₁ and C _1' in the formula (1) include the structures exemplified by R and Z of the repeating unit (a). From the viewpoint of obtaining the effect of the present invention, C ₁ and C _1' each independently preferably have a hydrogen atom or an alkyl group of 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group.

In the above formula (1), A ₁ , A _1' , C ₁ , and C _1' may be one type or two or more types, respectively.

(repeating unit represented by formula (2))

In the formula (2), A ₂ is a divalent organic group. Examples of the A ₂ include divalent organic groups derived from diisocyanate, and the structures exemplified as A ₁ in the repeating unit (1) are exemplified, and the preferred embodiments are also the same as those of A ₁ .

In the formula (2), A _2' is a divalent organic group obtained by removing hydrogen atoms contained in two hydroxy groups from an organic diol. These organic diols may be used individually by 1 type, or may be used in combination of 2 or more type. diol containing a divalent organic group represented by the formula (EG) as the organic diol; Ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl-1, 5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexane alkylene diols such as diol and 1,4-cyclohexanedimethanol; Dimethylolpropionic acid (2,2-bis(hydroxymethyl)propionic acid), dimethylolbutanoic acid (2,2-bis(hydroxymethyl)butanoic acid), 2,3-dihydroxybenzoic acid, 2,4-dihydroxy carboxy group-containing diols such as hydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, and 3,5-dihydroxybenzoic acid; random copolymers of polytetramethylene glycol, tetramethylene glycol and neopentyl glycol; Polyester diol obtained by making a polyhydric alcohol and polybasic acid react; Polycarbonate diol which has a carbonate skeleton; polycaprolactonediol obtained by subjecting lactones such as γ-butyllactone, ε-caprolactone, and δ-valerolactone to a ring-opening addition reaction; Ethylene oxide adducts of bisphenol A and bisphenol A; propylene oxide adducts of bisphenol A; hydrogenated bisphenol A and ethylene oxide adducts of hydrogenated bisphenol A; The propylene oxide adduct of hydrogenated bisphenol A, etc. are mentioned.

The diol containing the divalent organic group represented by the formula (EG) is not particularly limited as long as the molecule contains the formula (EG), but is preferably a diol having hydrogen atoms bonded to both ends of the formula (EG). In the diol in which hydrogen atoms are bonded to both ends of the above formula (EG), the upper limit of n is preferably 40, more preferably 30, and particularly preferably 20 from the viewpoint of improving the liquid crystal orientation. As for the lower limit of n, 3 is preferable and 4 is more preferable from a viewpoint of improving liquid-crystal orientation. More specifically, the diol containing the divalent organic group represented by the formula (EG) is tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, trade names PEG-300, PEG-400, PEG-600 manufactured by Sanyo Chemical Industry Co., Ltd.; PEG-1000, PEG-1500, PEG-2000, PEG-4000N, PEG-4000S, PEG-6000E, PEG-6000P, PEG-10000, PEG-13000, PEG-20000; Product names PEG300, PEG1000, PEG2000, PEG4000, PEG6000, PEG8000, PEG10000, PEG12000, PEG20000, PEG35000 manufactured by Merck; Product numbers P2139, P3265, P3515, 81210, 81240, 81260, 81285, 81310, 181986, 181994, 182001, 182028, 189456, 202304, 202312, manufactured by SIGMA-ALDRICH 202320, 202339, 202398, 202421, 202436, 202444, 202452, 295906, 309028, 372773, 372781, 373001, 412325, 435406, 435422, 435457, 637726; Trade names SINOPOL PEG600, SINOPOL PEG1500, and SINOPOL PEG4000 manufactured by Chunichi Synthetic Chemical Co., Ltd.; Product names PEG#300, PEG#400, PEG#600, PEG#1000, PEG#1500, PEG#1540, PEG#4000, PEG#6000M manufactured by Lion Specialty Chemicals, PEG#6000M, product name Polyethylene Glycol 400 manufactured by Tokyo Chemical Industry Co., Ltd. Polyethylene glycol represented by what is commercially available as Polyethylene Glyco 1600, or tripropylene glycol, tetrapropylene glycol, polypropylene glycol (more preferably polypropylene glycol having an average molecular weight of 300 to 10,000), and an average molecular weight of 200 to 10,000. and copolymers composed of 5000 ethylene oxide and propylene oxide. As the polyethylene glycol or polypropylene glycol, those obtained by subjecting ethylene oxide or propylene oxide to anionic ring-opening polymerization may be used. The polymerization reaction can be carried out using a polymerization initiator (eg, water, ethylene glycol, propylene glycol, etc.) and a catalytic amount of base (eg, potassium hydroxide). As preferred specific examples of diols in which hydrogen atoms are bonded to both ends of the formula (EG), tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, trade names PEG-300, PEG-400, PEG-600, and PEG-300 manufactured by Sanyo Chemical Industry Co., Ltd. 1000, product name PEG300, PEG1000 manufactured by Merck, PEG1000 manufactured by Chunichi Synthetic Chemical Co., Ltd., trade name SINOPOL PEG600, trade name manufactured by Lion Specialty Chemicals, PEG#300, PEG#400, PEG#600, PEG#1000, Tokyo Chemical Industrial company's product names include Polyethylene Glycol 400 and Polyethylene Glycol 600.

In addition, the average molecular weight of the glycol illustrated in the diol containing a divalent organic group represented by the above (EG) is a weight average molecular weight obtained on the basis of polystyrene by gel permeation chromatography (GPC).

When the formula (2) has a divalent organic group represented by the formula (EG), it is preferable that at least one of A ₂ and A _2' has a divalent organic group represented by the formula (EG).

When A ₂ has a divalent organic group represented by the formula (EG), the specific structure of A ₂ is derived from a diisocyanate having a divalent organic group represented by the formula (EG) exemplified by the repeating unit (1) The divalent organic group which does is mentioned.

When the A _2' has a divalent organic group represented by the formula (EG), as a specific structure of A _2' , two hydroxys from a diol containing a divalent organic group represented by the formula (EG) described in detail above. A divalent organic group from which hydrogen atoms contained in the hydroxy group have been removed is exemplified.

In the above formula (2), A ₂ and A _2' may be one type or two or more types, respectively.

(Repeating units constituting polymer (A))

The polymer (A) in the present invention is a copolymer having a repeating unit represented by the formula (a), a repeating unit represented by the formula (1), and a repeating unit represented by the formula (2), and a copolymer thereof At least one type of polymer selected from the group consisting of polyimide, which is a polyimide (provided that the repeating unit represented by the above formula (a), the repeating unit represented by the above formula (1), and the repeating unit represented by the above formula (2)) At least one of has a divalent organic group represented by the above formula (EG)). The polymer (A) may have a repeating unit represented by the formula (a), a repeating unit represented by the formula (1), a repeating unit represented by the formula (2), and an end group.

Here, a terminal group means the group couple|bonded with the terminal of the repeating unit which comprises the said polymer (A). Examples of the terminal group include an amino group, a carboxy group, an acid anhydride group, an isocyanate group, or derivatives thereof. An amino group, a carboxy group, an acid anhydride group, and an isocyanate group are obtained by a normal condensation reaction, and the derivative can be obtained by modifying the terminal group using, for example, an end capping agent as described later.

2-98 mol% of the whole repeating unit which comprises a polymer (A) is preferable, and, as for the content rate of the repeating unit represented by Formula (a), 10-96 mol% is more preferable.

1-49 mol% of the whole repeating unit which comprises a polymer (A) is preferable, and, as for the content rate of the repeating unit represented by Formula (1), 2-45 mol% is more preferable.

1-49 mol% of the whole repeating unit which comprises a polymer (A) is preferable, and, as for the content rate of the repeating unit represented by Formula (2), 2-45 mol% is more preferable.

<Polymer (B)>

From the viewpoint of improving electrical properties, the liquid crystal aligning agent of the present invention further contains a polymer (B) different from the polymer (A) as at least one polymer selected from the group consisting of a polyimide precursor and an imidized polymer thereof You can do it.

The polymer (B) is preferably at least one polymer selected from the group consisting of a polyimide precursor having a repeating unit represented by the following formula (b) and an imidized polymer thereof.

[Formula 32]

(X _b represents a tetravalent organic group. Y _b represents a divalent organic group. The two R _bs each independently represent a hydrogen atom or a monovalent organic group. The two Z _bs each independently represent hydrogen represents an atom or a monovalent organic group.)

The polymer (B) preferably does not have at least one of a repeating unit selected from the group consisting of a repeating unit represented by the above formula (1) and a repeating unit represented by the above formula (2).

As the tetravalent organic group for X _b , a tetravalent organic group derived from acyclic aliphatic tetracarboxylic dianhydride, a tetravalent organic group derived from alicyclic tetracarboxylic dianhydride, or aromatic tetracarboxylic acid 2 A tetravalent organic group derived from an anhydride is mentioned, and as a specific example, the tetravalent organic group illustrated by X _<1> of the said formula (a) is mentioned. From the viewpoint of efficiently obtaining the effects of the present invention, tetravalent organic groups represented by the formulas (X1-1) to (X1-25) (these are collectively referred to as specific tetravalent organic groups) are preferable.

From the viewpoint of efficiently obtaining the effects of the present invention, the polymer (B) preferably contains 5 mol% or more of the repeating unit in which X _b is the above-mentioned specific tetravalent organic group of the total repeat unit contained in the polymer (B), , It is more preferable to include 10 mol% or more.

Specific examples of Y _b include divalent organic groups derived from the diamines exemplified for the polymer (A) above. From the viewpoint of improving the electrical properties, the polymer ( _B ) contains diamine, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2 4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid and the above formula (3b-1) to A divalent organic group selected from the group consisting of a divalent organic group obtained by removing two amino groups from a diamine having a carboxyl group such as a diamine compound represented by Formula (3b-4) (these are collectively referred to as specific divalent organic groups). It is preferable that it is a polymer containing a unit.

Polymer (B) may contain 1 mol% or more of the repeating units contained in Polymer (B), or 5 mol% or more of a repeating unit in which Y _b is the above-mentioned specific divalent organic group, from the viewpoint of improving electrical properties. do.

From the viewpoint of enhancing electrical properties, the content ratio of component (A) and component (B) may be 10/90 to 90/10, or 20/80 in mass ratio of [component (A)]/[component (B)] -90/10 may be sufficient, and 20/80 - 80/20 may be sufficient.

<Preparation of Polymer (A) and Polymer (B)>

The polyimide precursor (A), which is the above-mentioned polymer (A), includes, for example, a component (o) containing an organic diol having two hydroxyl groups in a molecule and a compound containing two isocyanate groups in a molecule ( a) reacting component to synthesize a terminal isocyanate compound, then reacting component (b) containing a compound containing two primary or secondary amino groups in a molecule to synthesize a terminal amineurea oligomer, and adding It can manufacture by the method including the process of making the (c) component containing tetracarboxylic dianhydride or its derivative(s) react. Here, at least one of the compounds constituting the component (o), component (a), component (b) and component (c) has a partial structure represented by the following formula (EG) in a molecule.

[Formula 33]

(R represents a hydrogen atom or a methyl group. n is an integer of 3 to 40.)

On the other hand, the polyimide precursor (A) has a step of reacting component (a) and component (b) to obtain a terminal isocyanate compound, and a step of reacting component (o) and component (c) to obtain a terminal diol compound, , It can also manufacture by making the obtained terminal isocyanate compound and terminal diol compound react after that.

In addition, the polyimide precursor (A) has a step of reacting component (b) and component (c) to obtain an amine-terminated amic acid oligomer or a derivative thereof, and adding component (o) thereto to form a mixed solution, , It can also manufacture by passing through the process of making component (a) react further.

Component (o), component (a), component (b), and component (c) may be one type or two or more types, respectively.

(o) As a component, the organic diol illustrated by the repeating unit represented by the said formula (2) is mentioned, for example, "HA _2' -H" (A _2' in Formula (2) It is the same as A _2' .) Diol compound represented by is mentioned.

Examples of the component (a) include a diisocyanate compound represented by O=C=NA ₁ -N=C=O (A ₁ is the same as A ₁ in Formula (1)). there is.

(b) As a component, the diamine represented by the following formula (mb) is mentioned, for example.

[Formula 34]

(In formula (mb), C ₁ , C _1' and A _1' are the same as C ₁ , C _1' and A _1' in formula (1).)

As a specific example of the compound represented by the said formula (mb), the diamine illustrated by the repeating unit represented by the said formula (a) is mentioned, for example.

(c) As tetracarboxylic dianhydride or its derivative(s) contained in component, tetracarboxylic dianhydride or its derivative(s) represented by the following formula (mc), for example (tetracarboxylic acid dihalide, tetracarboxylic acid dihalide) alkyl esters or tetracarboxylic acid dialkyl ester dihalides).

[Formula 35]

(In the formula (mc), X is the same as X in the formula (a).)

More specifically, X in the formula (mc) is a tetravalent organic group derived from an acyclic aliphatic tetracarboxylic dianhydride or a derivative thereof, exemplified by the repeating unit represented by the formula (a), or an alicyclic tetravalent organic groups derived from formula tetracarboxylic dianhydride or derivatives thereof, or tetravalent organic groups derived from aromatic tetracarboxylic dianhydride or derivatives thereof; The acyclic aliphatic or alicyclic tetracarboxylic dianhydride or a derivative thereof is at least selected from the group consisting of a cyclobutane ring structure, a cyclopentane ring structure, and a cyclohexane ring structure, from the viewpoint of having high liquid crystal orientation. It is preferable that they are tetracarboxylic dianhydride or derivatives thereof which have one kind of partial structure. (c) As tetracarboxylic dianhydride or its derivative(s) contained in component, tetracarboxylic dianhydride or its derivative(s) represented by the said formula (t) is especially preferable.

It is preferable that tetracarboxylic dianhydride or its derivative(s) represented by a formula (t) is 1 mol% or more of the whole (c) component. More preferably, it is 5 mol% or more, and especially preferably, it is 10 mol% or more.

When at least one of the compounds constituting the component (o), component (a), component (b) and component (c) has the partial structure represented by the formula (EG) in the molecule, "HA _2' -H" A _2' in the diol compound represented by O=C=NA ₁ -N=C=O in the diisocyanate compound represented by A ₁ , A _1' in the diamine represented by the formula (mb) above At least one of X in tetracarboxylic dianhydride represented by formula (mc) has the partial structure represented by the said formula (EG) in a molecule|numerator. Preferable specific examples thereof are as described above.

The reaction of component (o), component (a), component (b), and component (c) is usually performed in an organic solvent. The organic solvent used in that case is not particularly limited as long as the produced polyimide precursor dissolves therein. Specific examples include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methyl-ε-caprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, Dimethylsulfone, hexamethylphosphate triamide, γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone , methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl Ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol Monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3 -Methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone , methylcyclohexene, propyl ether, dihexyl ether, 1,4-dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate , methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, 3-methoxymethylpropionate, 3-ethoxymethylpropionate, 3-ethoxyethylpropionate, 3-methoxy ethyl propionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropylpropionate, 3-methoxybutylpropionate, diglyme, or 4-hydroxy-4-methyl-2-pentanone; and the like. . These may be used independently or may be used in mixture. Moreover, even if it is a solvent which does not dissolve a polyimide precursor, you may use it by mixing with the said solvent in the range in which the produced|generated polyimide precursor does not precipitate. Further, since moisture in the organic solvent inhibits the polymerization reaction and causes the resulting polyimide precursor to hydrolyze, it is preferable to use a dehydrated organic solvent.

<Method for synthesizing terminal isocyanate compound>

A method for synthesizing a terminal isocyanate compound obtained by reacting component (o) containing an organic diol used in the present invention with component (a) containing a diisocyanate compound containing two isocyanate groups in a molecule, comprising: (a) Organic solvent so that the blending amount of the component is such that the ratio of the number of hydroxyl groups to the number of isocyanate groups is isocyanate group/hydroxyl group = 1.01 or more, preferably 1.1 or more and 2.4 or less, more preferably 1.1 or more and 2.1 or less. It is obtained by reacting in

Moreover, when using two or more types of organic diols, reaction with a diisocyanate compound may be performed after mixing two or more types of organic diols, or each organic diol and diisocyanate compound may be reacted separately. Moreover, after making an organic diol and a diisocyanate compound react, you may make the obtained terminal isocyanate compound react with another organic diol compound, and also make this react with a diisocyanate compound. Moreover, it is the same also when using 2 or more types of diisocyanate compound. In this way, a desired terminal isocyanate compound can be manufactured.

It is preferable to set it as 0-160 degreeC, and, as for the reaction temperature of component (o) and (a) component, it is more preferable to set it as 10-150 degreeC. The reaction time can be appropriately selected depending on the reaction scale and the reaction conditions employed. Further, if necessary, the reaction may be performed in the presence of a catalyst such as a metal or semimetal compound such as tertiary amines, alkali metals, alkaline earth metals, tin, zinc, titanium, and cobalt. The concentration of the total amount of component (o) and component (a) is preferably 1 to 50% by mass, more preferably 5 to 30% by mass in the reaction solution. The initial stage of the reaction may be performed at a high concentration, and then an organic solvent may be added.

<Synthesis method of terminal amine urea oligomer>

A method for synthesizing a terminal amineurea oligomer obtained by reacting a component (b) containing a compound containing two primary or secondary amino groups in a molecule with a terminal isocyanate compound obtained by the above method, in an organic solvent obtained by reacting The reaction temperature is preferably 0 to 160°C, and more preferably 10 to 150°C. The reaction time can be appropriately selected depending on the reaction scale and the reaction conditions employed. The reaction concentration is preferably 1 to 50% by mass, more preferably 5 to 30% by mass in the reaction solution. At the initial stage of the reaction, it may be carried out at a high concentration, and then an organic solvent may be added.

<Synthetic method for obtaining polyimide precursor (A) from terminal amineurea oligomer>

Component (c) containing tetracarboxylic dianhydride or a derivative thereof in the terminal amineurea oligomer obtained by the above method, and optionally containing two primary or secondary amino groups in the molecule. A polyimide precursor (A) can be obtained by reacting the (b) component containing a compound. The reaction is preferably carried out in an organic solvent, and the reaction temperature is preferably from 20 to 100°C, more preferably from 20 to 80°C. The reaction time can be appropriately selected depending on the reaction scale and the reaction conditions employed. The reaction concentration is preferably 1 to 50% by mass, more preferably 5 to 30% by mass in the reaction solution. At the initial stage of the reaction, it may be carried out at a high concentration, and then an organic solvent may be added.

The ratio of the (o) component, (a) component, (b) component, and (c) component to be reacted is, for example, in a molar ratio, the total amount of (a) component and (c) component: (o) component and ( b) It is preferable that the total amount of components = 0.8:1 to 1.2:1. It is preferable that it is 2-98 mol%, and, as for the ratio of (a) component to the total amount of component (a) and (c) component, it is more preferable that it is 10-96 mol%. Moreover, it is preferable that it is 1-49 mol%, and, as for the ratio of component (o) to the total amount of component (o) and (b) component, it is more preferable that it is 2-45 mol%.

Polyamic acid, polyamic acid ester, etc. are mentioned as a polyimide precursor which is the said polymer (B). The polyimide precursor which is the said polymer (B) is compoundable by the well-known method described in international publication WO2013/157586, for example.

[Terminal modifier]

In synthesizing the polymers (A) and (B) in the present invention, the above component (o), component (a), component (b), component (c) and, if necessary, a suitable terminal modifying agent It is good also as synthesizing the polymer of the terminal modification type using.

Examples of the terminal modifying agent include acetic anhydride, maleic anhydride, nadic anhydride, phthalic anhydride, itaconic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, trimellitic anhydride, the following formula (m -1) The compound represented by - (m-6), 3-(3-trimethoxysilyl)propyl)-3,4-dihydrofuran-2,5-dione, 4,5,6,7-tetrafluoro Acid 1 anhydrides, such as a leuisobenzofuran 1, 3-dione and 4-ethynyl phthalic anhydride;

[Formula 36]

diester 2 carbonate compounds such as di-tert-butyl 2 carbonate and diallyl 2 carbonate; Chlorocarbonyl compounds, such as acryloyl chloride, methacryloyl chloride, and nicotinic acid chloride; Aniline, 2-aminophenol, 3-aminophenol, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, cyclohexylamine, n-butylamine , monoamine compounds such as n-pentylamine, n-hexylamine, n-heptylamine, and n-octylamine; Monoisocyanate compounds, such as ethyl isocyanate, phenyl isocyanate, and naphthyl isocyanate, etc. are mentioned.

The proportion of the terminal modifier used is preferably 20 parts by mole or less, more preferably 10 parts by mole or less, based on 100 parts by mole in total of the diamine component used and the organic diol component used as necessary.

Further, polyimide can be obtained by subjecting the polyimide precursor (A) of the polymer (A) or the polyimide precursor of the polymer (B) (hereinafter collectively referred to simply as "polyimide precursor") to ring closure (imidization). there is. In addition, the imidation rate as used herein is the ratio of the imide group to the total amount of the imide group derived from tetracarboxylic dianhydride or its derivative(s) and a carboxy group (or its derivative(s)). The imidization rate does not necessarily have to be 100% and can be arbitrarily adjusted according to the use or purpose.

As a method of imidating the polyimide precursor, thermal imidation in which the solution of the polyimide precursor is heated as it is or catalyst imidation in which a catalyst is added to the solution of the polyimide precursor is exemplified.

The temperature in the case of thermal imidation of the polyimide precursor in the solution is preferably 100 to 400 ° C., more preferably 120 to 250 ° C., and it is preferable to carry out while removing water generated by the imidation reaction to the outside of the system do.

Catalytic imidation of the polyimide precursor can be performed by adding a basic catalyst and an acid anhydride to a solution of the polyimide precursor, followed by stirring at preferably -20 to 250°C, more preferably 0 to 180°C. The amount of the basic catalyst is preferably 0.5 to 30 mole times, more preferably 2 to 20 mole times the amount of the amic acid group, and the amount of the acid anhydride is preferably 1 to 50 mole times, more preferably 3 to 30 mole times the amic acid group. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like, and among these, pyridine is preferable because it has appropriate basicity for advancing the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like, and among these, acetic anhydride is preferable because purification after completion of the reaction becomes easy. The imidation rate by catalyst imidation is controllable by adjusting the catalyst amount, reaction temperature, and reaction time.

What is necessary is just to throw in the reaction solution into a solvent and just to precipitate it, when collect|recovering the produced|generated polyimide precursor or polyimide from the polyimide precursor or the reaction solution of a polyimide. Examples of 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 pouring into the solvent can be recovered by filtration, and then dried by heating or at room temperature under normal pressure or reduced pressure. In addition, the impurities in the polymer can be reduced by re-dissolving the polymer recovered by precipitation in an organic solvent and repeating the operation of re-precipitation and recovery 2 to 10 times, for example. Examples of the solvent at this time include alcohols, ketones, hydrocarbons, and the like, and it is preferable to use three or more types of solvents selected from among these because the efficiency of purification is further increased.

The molecular weight of the polymers (A) and (B) used in the present invention is the weight measured by the GPC (Gel Permeation Chromatography) method when considering the strength of the liquid crystal alignment film obtained therefrom, workability at the time of film formation, and coating properties The average molecular weight is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000.

Although the compounding ratio of the polymer component used in the manufacturing method of the liquid crystal aligning film of this invention is not specifically limited, For example, the total amount of the polymer component contained in a liquid crystal aligning agent is Preferably 0.1-30 mass %, more preferably is 3 to 10% by mass.

Although content of the polymer (A) in a liquid crystal aligning agent can be changed suitably according to the coating method of a liquid crystal aligning agent, or the film thickness of the liquid crystal aligning film made into the objective, it is preferable that it is 0.1-30 mass %, and especially 0.5-9.5 Mass % is preferred.

Moreover, in addition to a polymer (A) and a polymer (B), other polymers other than these may be mixed with the liquid crystal aligning agent used for manufacture of a liquid crystal aligning film. In that case, content of another polymer is 0.5-15 mass % of the total amount of polymer components, Preferably it is 1-10 mass %. Examples of other polymers include acrylic polymers, methacrylic polymers, polystyrenes, polyamides, or polysiloxanes.

The solvent contained in the liquid crystal aligning agent is not particularly limited as long as it can dissolve the polymer (A), and examples thereof include lactone solvents such as γ-valerolactone and γ-butyrolactone; γ-butyrolactam, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-(n-propyl)-2-pyrrolidone, N-isopropyl-2-pyrrolidone , N-(n-butyl)-2-pyrrolidone, N-(tert-butyl)-2-pyrrolidone, N-(n-pentyl)-2-pyrrolidone, N-methoxypropyl-2 - Lactam solvents such as pyrrolidone, N-ethoxyethyl-2-pyrrolidone, N-methoxybutyl-2-pyrrolidone, and N-cyclohexyl-2-pyrrolidone; N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethyllactoamide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, amide solvents such as; 4-hydroxy-4-methyl-2-pentanone, 2,6-dimethyl-4-heptanone (diisobutyl ketone), methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isobaric acid lactate Wheat, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl Ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, di Ethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene Glycol monobutyl ether, propylene glycol diacetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, isoamylpropionate, isoamyliso Butyrate, diisopropyl ether, diisopentyl ether; Carbonate solvents such as ethylene carbonate and propylene carbonate, 1-hexanol, cyclohexanol, 1,2-ethanediol, 2,6-dimethyl-4-heptanol (diisobutylcarbinol), 1,3-dimethyl- 2-imidazolidinone etc. are mentioned. These can be used individually or in mixture of 2 or more types.

Preferred solvent combinations include N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone and ethylene glycol monobutyl ether, and N-methyl-2 -Pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and 4 -Hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether, N-ethyl-2-pyrrolidone and N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2- Pentanone, N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and 2,6-dimethyl-4-heptanone, N-methyl-2-pyrrolidone and 4-hydroxy Roxy-4-methyl-2-pentanone and dipropylene glycol monomethyl ether, N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and propylene glycol monobutyl ether, N-methyl- 2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and propylene glycol diacetate, γ-butyrolactone and 4-hydroxy-4-methyl-2-pentanone and 2,6-dimethyl-4 -Heptanone, γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone, propylene glycol diacetate, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether, 2,6-dimethyl-4-heptanone, N-methyl-2-pyrrolidone and γ-butyrolactone, propylene glycol monobutyl ether and diisopropyl ether, N-methyl-2-pyrrolidone and γ- Butyrolactone, propylene glycol monobutyl ether, 2,6-dimethyl-4-heptanol, N-methyl-2-pyrrolidone, γ-butyrolactone, dipropylene glycol dimethyl ether, N-methyl-2-p Rolidone, propylene glycol monobutyl ether, dipropylene glycol dimethyl ether, N-methyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monobutyl ether, and the like. The type and content of such a solvent are appropriately selected depending on the application device, application conditions, and application environment of the liquid crystal aligning agent.

<liquid crystal aligning agent>

The liquid crystal aligning agent of this invention may add other components other than the above, for example, a crosslinkable compound, a functional silane compound, surfactant, the compound which has a photopolymerizable group, etc. as needed.

A crosslinkable compound can be used for the purpose of enhancing the strength of the liquid crystal aligning film. As such a crosslinkable compound, at least one selected from the group consisting of compounds having an isocyanate group or a cyclocarbonate group described in paragraphs [0109] to [0113] of International Publication WO2016/047771, or a lower alkoxyalkyl group. In addition to the compound having a group, a compound having a block isocyanate group and the like are exemplified.

The compound having a block isocyanate group can be obtained as a commercial item, for example, Colonate AP Stable M, Colonate 2503, 2515, 2507, 2513, 2555, Milionate MS-50 (above, manufactured by Tosoh Corporation), Takenate B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (above, manufactured by Mitsui Chemicals), etc. can be used preferably.

As a specific example of a preferable crosslinkable compound, the compound represented by the following formula (CL-1) - (CL-11) is mentioned.

[Formula 37]

The above is an example of a crosslinkable compound, and is not limited thereto. Moreover, 1 type may be sufficient as the crosslinkable compound used for the liquid crystal aligning agent of this invention, and you may combine it 2 or more types.

Content of other crosslinkable compounds in the liquid crystal aligning agent of this invention is 0.1-150 mass parts, or 0.1-100 mass parts, or 1-50 mass parts with respect to 100 mass parts of all polymer components.

A functional silane compound can be used for the purpose of improving the adhesiveness of a liquid crystal aligning film and a base substrate. As a specific example, the silane compound of international publication 2014/119682 Paragraph [0019] is mentioned. The content of the functional silane compound is preferably from 0.1 to 30 parts by mass, more preferably from 0.5 to 20 parts by mass, based on 100 parts by mass of all polymer components.

Surfactant can be used for the purpose of improving the uniformity and surface smoothness of the film thickness of a liquid crystal aligning film. As said compound, a fluorochemical surfactant, silicone type surfactant, a nonionic surfactant, etc. are mentioned. These specific examples include the surfactant described in paragraph [0117] of International Publication WO2016/047771. The amount of surfactant used is preferably from 0.01 to 2 parts by mass, more preferably from 0.01 to 1 part by mass with respect to 100 parts by mass of all the polymer components contained in the liquid crystal aligning agent.

Examples of the compound having a photopolymerizable group include compounds having one or more polymerizable unsaturated groups such as an acrylate group and a methacrylate group in a molecule.

Further, in the liquid crystal aligning agent of the present invention, international publication WO2011/132751 (published on October 27, 2011), paragraphs [0194] to [ 0200], nitrogen atom-containing heterocyclic amine compounds represented by formulas [M1] to formula [M156], more preferably 3-picolylamine and 4-picolylamine can be added. Although this amine compound may be directly added to a liquid crystal aligning agent, it may be added, for example after setting it as a solution of 0.1-10 mass % of density|concentration preferably 1-7 mass % preferably. This solvent is not particularly limited as long as it dissolves the polymer component.

You may add an imidation promoter etc. to the liquid crystal aligning agent of this invention for the purpose of advancing imidation by heating efficiently, when baking a coating film.

The solid content concentration (ratio of the total mass of components other than the solvent of the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent) in the liquid crystal aligning agent is appropriately selected in consideration of viscosity, volatility, etc., but is preferably 0.5 to 15 It is mass %, More preferably, it is the range of 1-10 mass %.

The range of a particularly preferable solid content concentration differs according to the method used when apply|coating a liquid crystal aligning agent to a board|substrate. For example, in the case of the spinner method, the solid content concentration is particularly preferably in the range of 1.5 to 4.5% by mass. In the case of using the printing method, it is particularly preferable to set the solid content concentration in the range of 3 to 9% by mass, thereby setting the solution viscosity in the range of 12 to 50 mPa·s. In the case of the inkjet method, it is particularly preferable to set the solid content concentration in the range of 1 to 5% by mass, thereby setting the solution viscosity in the range of 3 to 15 mPa·s.

<Liquid crystal alignment film/liquid crystal display element>

A liquid crystal aligning film can be manufactured by using the said liquid crystal aligning agent. Moreover, the liquid crystal display element which concerns on this invention is provided with the liquid crystal aligning film formed using the said liquid crystal aligning agent. The operation mode of the liquid crystal display element according to the present invention is not particularly limited, and examples thereof include TN (Twisted Nematic) type, STN type, vertical alignment type (including VA-MVA type and VA-PVA type), and in-plane type. It can be applied to various operating modes such as switching type (IPS type), Fringe Field Switching (FFS) type, and optical compensation bend type (OCB type).

The liquid crystal display element of the present invention is, for example, a method including the following steps (1) to (4), steps (1) to (2) and (4), steps (1) to (3), and (4) It can manufacture by the method including -2) and (4-4), or the method including steps (1) - (3), (4-3) and (4-4).

<Process (1): The process of applying a liquid crystal aligning agent on a board|substrate>

The liquid crystal aligning agent of the present invention is applied to one surface of a substrate on which a patterned transparent conductive film is formed, for example, by a suitable coating method such as a roll coater method, a spin coat method, a printing method, or an inkjet method. Here, the substrate is not particularly limited as long as it is a substrate having high transparency, and a plastic substrate such as an acrylic substrate or a polycarbonate substrate may be used in addition to a glass substrate or a silicon nitride substrate. In addition, in the reflective liquid crystal display element, as long as it is only a substrate on one side, an opaque material such as a silicon wafer can be used, and a material that reflects light such as aluminum can also be used for the electrode in this case. In the case of manufacturing an IPS type or FFS type liquid crystal device, a substrate formed with electrodes made of a comb-shaped transparent conductive film or metal film and a counter substrate without electrodes are used.

Screen printing, offset printing, flexographic printing, an inkjet method, or a spray method etc. are mentioned as a method of apply|coating a liquid crystal aligning agent to a board|substrate and forming a film. Among them, application by an inkjet method and a film formation method can be preferably used.

<Process (2): The process of baking the applied liquid crystal aligning agent>

A process (2) is a process of baking the liquid crystal aligning agent apply|coated on the board|substrate, and forming a film. After the liquid crystal aligning agent is applied on the substrate, the solvent is evaporated or the polyamic acid or polyamic acid ester is thermally imidated by a heating means such as a hot plate, a heat circulation oven or an IR (infrared ray) oven. can be done or done. The drying and baking process after apply|coating the liquid crystal aligning agent of this invention can select arbitrary temperature and time, and may be performed a plurality of times. As temperature which reduces the solvent of a liquid crystal aligning agent, it can implement at 40-180 degreeC, for example. You may carry out at 40-150 degreeC from a viewpoint of shortening a process. Although it does not specifically limit as baking time, 1 to 10 minutes or 1 to 5 minutes are mentioned. When heat imidating a polyamic acid or polyamic acid ester, you may add the process of baking in the temperature range of 150-300 degreeC, or 150-250 degreeC after the said process, for example. Although it does not specifically limit as baking time, A baking time of 5 to 40 minutes or 5 to 30 minutes is mentioned.

Since the reliability of a liquid crystal display element may fall when the membranous substance after baking is too thin, 5-300 nm is preferable and 10-200 nm is more preferable.

<Process (3): Process of orientation-treating the film obtained in process (2)>

Step (3) is a step of subjecting the film obtained in step (2) to orientation treatment depending on the case. That is, in a liquid crystal display element of a horizontal alignment type such as an IPS system or an FFS system, an orientation ability providing process is performed with respect to the coating film. On the other hand, in vertical alignment type liquid crystal display elements, such as VA system or PSA mode, although the formed coating film can be used as a liquid crystal aligning film as it is, you may perform orientation ability provision process with respect to the coating film. As a method for orientation treatment of the liquid crystal aligning film, a rubbing treatment method and a photo-alignment treatment method are exemplified. As the photo-alignment treatment method, the surface of the membranous material is irradiated with radiation polarized in a certain direction, and in some cases, preferably, a heat treatment is performed at a temperature of 150 to 250 ° C. ) can be given. As radiation, ultraviolet rays or visible rays having a wavelength of 100 to 800 nm can be used. Among them, it is an ultraviolet ray having a wavelength of preferably 100 to 400 nm, more preferably 200 to 400 nm.

As for the irradiation amount of the said radiation, 1-10,000 mJ/cm<2> is preferable. Especially, 100-5,000 mJ/cm<2> is preferable. Moreover, when irradiating radiation, in order to improve liquid-crystal orientation, you may irradiate, heating the board|substrate which has the said membranous substance at 50-250 degreeC. The said liquid crystal aligning film produced in this way can orientate liquid crystal molecules stably in a fixed direction.

Further, in the above method, the liquid crystal alignment film irradiated with polarized radiation may be subjected to a contact treatment using water or a solvent, or the liquid crystal alignment film irradiated with radiation may be subjected to heat treatment.

The solvent used for the contact treatment is not particularly limited as long as it dissolves a decomposition product generated from a membranous substance by irradiation with radiation. Specific examples include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, methyl lactate , diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, cyclohexyl acetate, and the like. Among them, water, 2-propanol, 1-methoxy-2-propanol, or ethyl lactate is preferable, and water, 1-methoxy-2-propanol, or ethyl lactate is more preferable, from the viewpoint of versatility and safety of the solvent. . One type of solvent may be sufficient, and it may combine two or more types.

The temperature of the heat treatment of the coating film irradiated with the radiation is more preferably 50 to 300°C, and still more preferably 120 to 250°C. As time of heat treatment, it is preferable to set it as 1 to 30 minutes.

<Process (4): Process of producing a liquid crystal cell>

As mentioned above, two board|substrates with a liquid crystal aligning film are prepared, and a liquid crystal is arrange|positioned between the two board|substrates which arranged oppositely. Specifically, the following two methods are mentioned. The 1st method arranges two board|substrates facing each other through a clearance gap (cell gap) so that each liquid crystal aligning film may oppose first. Next, the peripheral portions of the two substrates are bonded together using a sealant, and a liquid crystal composition is injected and filled into the substrate surface and the cell gap partitioned by the sealant to bring them into contact with the film surfaces, and then the injection hole is sealed.

In addition, the second method is a method called ODF (One Drop Fill) method. For example, an ultraviolet curable sealing agent is applied to a predetermined place on one of the two substrates on which the liquid crystal alignment film is formed, and the liquid crystal composition is dropped onto several predetermined points on the liquid crystal alignment film surface. Then, the other board|substrate is bonded together so that the liquid crystal aligning film may oppose, the liquid crystal composition is pressed and spread|spread on the whole surface of a board|substrate, and it is made to contact a film surface. Next, the entire surface of the substrate is irradiated with ultraviolet light to cure the sealing compound. In either case, it is preferable to remove the flow alignment during liquid crystal charging by further heating to a temperature at which the used liquid crystal composition exhibits an isotropic phase and then slowly cooling to room temperature.

In the case where the coating film is subjected to the rubbing treatment, the two substrates are disposed facing each other so that the rubbing directions in each coating film are at a predetermined angle, for example, orthogonal or antiparallel to each other.

As the sealing agent, for example, an epoxy resin containing aluminum oxide spheres as a curing agent and a spacer can be used. Examples of liquid crystals include nematic liquid crystals and smectic liquid crystals, and among these, nematic liquid crystals are preferable.

The liquid crystal aligning agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and contains a polymerizable compound that polymerizes by at least one of active energy rays and heat between the pair of substrates. It is also preferably used for a liquid crystal display device (PSA type liquid crystal display device) manufactured through a step of polymerizing a polymerizable compound by disposing a liquid crystal composition and applying at least one of active energy ray irradiation and heating while applying a voltage between electrodes. do.

Moreover, the liquid crystal aligning agent of this invention has a liquid crystal layer between a pair of board|substrates provided with electrodes, and the polymeric group which superposes|polymerizes by at least one of an active energy ray and heat between said pair of board|substrates is formed. It is suitably used also for the liquid crystal display element (SC-PVA mode liquid crystal display element) manufactured through the process of arrange|positioning the containing liquid crystal aligning film and applying a voltage between electrodes.

(4-2) In case of PSA type liquid crystal display element

It is the same as the above (4) except that the liquid crystal composition containing the polymerizable compound is injected or dropped.

(4-3) In case of SC-PVA mode type liquid crystal display element

After carrying out similarly to said (4), you may employ|adopt the method of manufacturing a liquid crystal display element through the process of irradiating an ultraviolet-ray mentioned later. According to this method, a liquid crystal display element excellent in response speed can be obtained with a small amount of light irradiation, similarly to the case of manufacturing the PSA type liquid crystal display element. The compound having a polymerizable group may be a compound having at least one polymerizable unsaturated group such as an acrylate group or a methacrylate group in a molecule, and the content thereof is preferably 0.1 to 30 parts by mass based on 100 parts by mass of all polymer components. , more preferably 1 to 20 parts by mass. Moreover, the said polymeric group may have the polymer used for a liquid crystal aligning agent, and as such a polymer, the polymer obtained by using for reaction the diamine component containing the diamine which has the said photopolymerizable group at the terminal, for example is mentioned. there is.

Step (4-4): Step of irradiating ultraviolet rays

The liquid crystal cell is irradiated with light in a state where a voltage is applied between the conductive films of the pair of substrates obtained in the above (4-2) or (4-3). The voltage applied here can be, for example, 5 to 50 V direct current or alternating current. Further, as the light to be irradiated, for example, ultraviolet rays and visible rays containing light with a wavelength of 150 to 800 nm can be used, but ultraviolet rays containing light with a wavelength of 300 to 400 nm are preferable. As the light source for irradiation light, for example, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser or the like can be used. As an irradiation amount of light, Preferably it is 1,000-200,000 J/m<2>, More preferably, it is 1,000-100,000 J/m<2>.

And a liquid crystal display element can be obtained by bonding a polarizing plate together to the outer surface of a liquid crystal cell as needed. Examples of the polarizing plate bonded to the outer surface of the liquid crystal cell include a polarizing plate in which a polarizing film called "H film" in which iodine is absorbed while polyvinyl alcohol is stretched and oriented is sandwiched between cellulose acetate protective films or a polarizing plate made of the H film itself. can

The liquid crystal display device of the present invention can be effectively applied to various devices, such as watches, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smart phones, It can be used for various display devices, such as various monitors, liquid crystal televisions, and information displays. In addition, the polymer composition contained in the liquid crystal aligning agent is a liquid crystal aligning film for retardation films, a liquid crystal aligning film for scanning antennas or liquid crystal array antennas, or a liquid crystal aligning film for transmission scattering type liquid crystal light control elements, or uses other than these, examples For example, it can be used for the protective film of color filters, the gate insulating film of flexible displays, and substrate materials.

Example

Below, the present invention will be specifically described by giving examples and the like, but the present invention is not limited to these examples. In addition, the symbol of a compound and a solvent is as follows.

(organic solvent)

NMP: N-methyl-2-pyrrolidone

GBL: γ-butyrolactone

BCS: ethylene glycol monobutyl ether

(diamine)

DA-1 to DA-8: Compounds represented by the following structural formulas (DA-1) to (DA-8), respectively

(acid dianhydride)

CA-1 to CA-5: Compounds represented by the following structural formulas (CA-1) to (CA-5), respectively

(Diisocyanate)

DI-1: 4,4'-diphenylmethane diisocyanate

(Dior)

EG-1: tetraethylene glycol

EG-2: Polyethylene Glycol 400 (manufactured by Tokyo Chemical Industry Co., Ltd.)

EG-3: Polyethylene Glycol 600 (manufactured by Tokyo Chemical Industry Co., Ltd.)

[Formula 38]

[Formula 39]

<Viscosity>

In the synthesis example, the viscosity of the polymer solution was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) at a sample amount of 1.1 mL, a cone rotor TE-1 (1 ° 34', R24), and a temperature of 25 ° C. did

<Measurement of imidization rate of polyimide>

The imidation rate of the polyimide in the synthesis example was measured as follows. 30 mg of polyimide powder was placed in an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, φ5 (manufactured by Kusano Scientific Co., Ltd.)), and deuterated dimethylsulfoxide (DMSO-d6, 0.05% by mass TMS (tetramethylsilane)) was mixed. product) (0.53 mL) was added, and ultrasonic was applied to completely dissolve it. A 500 MHz proton NMR was measured for this solution with an NMR measuring device (JNW-ECA500) (manufactured by Nippon Electronics Datum Co., Ltd.). For the imidation rate, a proton derived from a structure that does not change before and after imidization is determined as a reference proton, and the peak integrated value of this proton and the proton peak integrated value derived from the NH group of the amic acid appearing around 9.5 to 10.0 ppm was obtained using the following formula.

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

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

[Synthesis of Polymer]

(Synthesis Example 1)

EG-1 (0.32 g, 1.65 mmol) was weighed into a 50 mL eggplant flask equipped with a stirrer and a nitrogen inlet pipe, NMP (1.3 g) was added, and the mixture was stirred and dissolved while blowing nitrogen. While stirring this solution under water cooling, DI-1 (0.83 g, 3.30 mmol) and NMP (3.30 g) were added, and the mixture was stirred under a nitrogen atmosphere at 70°C for 3 hours. Then, NMP (22.0 g) was added and diluted, and it stirred for further 30 minutes. After that, a solution of DA-6 (1.85 g, 9.35 mmol) in NMP (5.00 g) was added, further NMP (2.50 g) was added, and the mixture was stirred under a nitrogen atmosphere at 23°C for 2 hours. Subsequently, CA-2 (1.49 g, 7.59 mmol) and NMP (6.30 g) were added, and a solution of polymer (polymer-1) was obtained by stirring under a nitrogen atmosphere at 23°C for 2 hours (viscosity: 32 mPa·s). ).

(Synthesis Examples 2 to 5)

Polyurethaneamic acid (Polymer-2) to (Polymer- 5) was obtained. In Table 1, the numerical value indicated under the compound name represents the mass of each compound used in the synthesis, and the numerical value in parentheses represents the amount (molar parts) of each compound relative to 100 molar parts of the total amount of the diamine component and the diol component.

(Synthesis Example 6)

EG-2 (0.34 g, 0.84 mmol) and NMP (1.9 g) were weighed into a 100 mL eggplant flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring while blowing nitrogen. While stirring this solution under water cooling, DI-1 (0.42 g, 1.68 mmol) and NMP (2.24 g) were added, and the mixture was stirred under a nitrogen atmosphere at 70°C for 3 hours. Then, NMP (20.0g) and GBL (20.0g) were added and diluted, and it stirred for further 30 minutes. After that, a solution of DA-5 (5.77 g, 20.2 mmol) in NMP (10.9 g) and GBL (15.1 g) were added, and the mixture was stirred under a nitrogen atmosphere at 23°C for 2 hours. Subsequently, CA-2 (3.67 g, 18.7 mmol), NMP (2.25 g) and GBL (2.25 g) were added, and the mixture was stirred under a nitrogen atmosphere at 23°C for 2 hours. After completion of the reaction, NMP (8.50 g) and GBL (8.50 g) were added to adjust the solution concentration and stirred for 1 hour to obtain a polymer (polymer-6) solution (viscosity: 112 mPa·s).

(Synthesis Examples 7 to 14)

Polymers (Polymer-7) to (Polymer-14) shown in Table 2 below were obtained by carrying out in the same procedure as in Synthesis Example 6 using the diamine, acid dianhydride, diisocyanate and diol shown in Table 2 below. got a solution. In Table 2, the numerical value indicated under the compound name represents the mass of each compound used in the synthesis, and the numerical value in parentheses represents the amount of each compound used (parts by mole) relative to 100 parts by mole of the total amount of the diamine component and the diol component.

(Synthesis Example 15)

DA-5 (3.16 g, 11.0 mmol) and NMP (28.5 g) were weighed into a 100 mL eggplant flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring while blowing nitrogen. While stirring this solution under water cooling, CA-2 (1.67 g, 8.52 mmol) and NMP (6.98 g) were added, and the mixture was stirred under a nitrogen atmosphere at 23°C for 2 hours. EG-3 (0.58 g, 0.96 mmol) and NMP (4.22 g) were then added into the stirred solution. Subsequently, DI-1 (0.48 g, 1.92 mmol) and NMP (3.52 g) were added and stirred at 50°C for 3 hours under a nitrogen atmosphere to obtain a polymer (polymer-15) solution (viscosity: 178 mPa·s). .

(Synthesis Example 16)

DA-5 (7.45 g, 26.0 mmol), NMP (33.5 g) and GBL (33.5 g) were weighed into a 100 mL eggplant flask equipped with a stirrer and a nitrogen inlet tube, and stirred while feeding nitrogen. dissolved While stirring this diamine solution under water cooling, CA-2 (4.74 g, 24.2 mmol), NMP (11.2 g) and GBL (11.2 g) are added and stirred under a nitrogen atmosphere for 2 hours to obtain polyamic acid (PAA-1) A solution was obtained (viscosity: 182 mPa·s).

(Synthesis Example 17)

DA-5 (7.45 g, 26.0 mmol), NMP (33.5 g) and GBL (33.5 g) were weighed into a 100 mL eggplant flask equipped with a stirrer and a nitrogen inlet tube, and stirred while feeding nitrogen. dissolved While stirring this diamine solution under water cooling, CA-3 (5.42 g, 24.2 mmol), NMP (13.8 g) and GBL (13.8 g) were added and stirred under a nitrogen atmosphere for 2 hours to obtain polyamic acid (PAA-2). A solution was obtained (viscosity: 167 mPa·s).

(Synthesis Example 18)

DA-4 (11.7 g, 40.2 mmol), DA-2 (8.73 g, 21.9 mmol), DA-3 (6.10 g, 11.0 mmol), and NMP (113.2 g) were weighed and dissolved by stirring while passing nitrogen. CA-1 (9.40 g, 47.5 mmol) and NMP (32.4 g) were added stirring this diamine solution under water cooling, and it stirred at 50 degreeC in nitrogen atmosphere for 2 hours. Further, a solution of polyamic acid (PAA-3) was obtained by adding CA-2 (4.61 g, 23.5 mmol) and NMP (16.6 g) and stirring at 23°C under a nitrogen atmosphere for 2 hours (viscosity: 1230 mPa·s). .

In a 200 mL Erlenmeyer flask containing a stirrer, the solution (100 g) of polyamic acid (PAA-3) obtained above was weighed, and di-tert-butyl 2 carbonate (hereinafter also referred to as Boc ₂ O) as a terminal modifying agent was added. (1.32 g, 6.05 mmol) was added, and the mixture was stirred at 40°C for 15 hours to obtain a solution of terminal-modified polyamic acid (PAA-3-1).

In a 200 mL Erlenmeyer flask containing a stirrer bar, aliquot the solution (100 g) of the above (PAA-3-1), add NMP (66.7 g), acetic anhydride (12.9 g) and pyridine (4.27 g), and stir at room temperature. After stirring for 30 minutes, it was made to react at 60 degreeC for 4 hours. This reaction solution was poured into methanol (640 g), and the obtained precipitate was separated by filtration. After washing this precipitate with methanol, it was made to dry under reduced pressure at 80 degreeC, and the powder of polyimide (imidation rate: 91%) was obtained.

Further, in a 100 mL Erlenmeyer flask with a stirrer, the polyimide powder (9.60 g) was fractionated, NMP (70.4 g) was added, stirred at 70 ° C. for 24 hours to dissolve, and polyimide (SPI-1) of the solution was obtained.

(Synthesis Example 19)

DA-1 (8.04 g, 40.2 mmol), DA-2 (4.36 g, 10.9 mmol), DA-3 (12.2 g, 21.9 mmol) and NMP (98.4 g) was weighed and dissolved by stirring while passing nitrogen. CA-1 (9.40 g, 47.5 mmol) and NMP (37.6 g) were added stirring this diamine solution under water cooling, and it stirred at 50 degreeC in nitrogen atmosphere for 2 hours. Further, CA-2 (4.65 g, 23.7 mmol) and NMP (18.6 g) were added and stirred at 23°C for 2 hours under a nitrogen atmosphere to obtain a solution of polyamic acid (PAA-4) (viscosity: 1230 mPa·s). .

In a 200 mL Erlenmeyer flask containing a stirrer, take the solution (100 g) of the polyamic acid (PAA-4) obtained above, add Boc ₂ O (1.24 g, 5.68 mmol), and stir at 40°C for 15 hours. , to obtain a solution of terminal-modified polyamic acid (PAA-4-1).

In a 200 mL Erlenmeyer flask containing a stirrer, a solution (100 g) of the above (PAA-4-1) was aliquoted, NMP (66.7 g), acetic anhydride (14.2 g) and pyridine (4.70 g) were added and stirred at room temperature. After stirring for 30 minutes, it was made to react at 60 degreeC for 4 hours. This reaction solution was poured into methanol (650 g), and the obtained precipitate was separated by filtration. After wash|cleaning this precipitate with methanol, by making it dry under reduced pressure at 80 degreeC, the powder of polyimide (imidation rate: 90%) was obtained.

Further, in a 100 mL Erlenmeyer flask with a stirrer, the polyimide powder (9.60 g) was fractionated, NMP (70.4 g) was added, stirred at 70 ° C. for 24 hours to dissolve, and polyimide (SPI-2) of the solution was obtained.

(Synthesis Example 20)

DA-7 (4.03 g, 16.5 mmol), DA-8 (3.29 g, 16.5 mmol), and NMP (65.9 g) were weighed into a 100 mL eggplant flask equipped with a stirrer and a nitrogen inlet tube, The mixture was dissolved by stirring while blowing nitrogen. While stirring this diamine solution under water cooling, CA-4 (6.19 g, 24.8 mmol) was added, NMP (10.7 g) was further added, and the mixture was stirred at 50°C under a nitrogen atmosphere for 3 hours. Further, CA-5 (2.04 g, 6.93 mmol) was added, NMP (11.6 g) was further added, and the mixture was stirred under a nitrogen atmosphere at 70°C for 6 hours to obtain a solution of polymer (PAA-5) (viscosity: 495 mPa·s).

[Preparation of liquid crystal aligning agent]

(Example 1)

A solution (6.60 g) of the polymer (Polymer-1) obtained in Synthesis Example 1 was weighed into a 50 mL conical flask containing a stirrer, and NMP (0.06 g), GBL (9.34 g) and BCS (4.00 g) were added. In addition, the liquid crystal aligning agent (1) was obtained by stirring at room temperature for 2 hours.

(Examples 2 to 16, Comparative Examples 1 to 4)

Liquid crystal aligning agents (2)-(20) were obtained by performing operation similar to Example 1 except having changed so that the polymer fluid to be used and the kind and quantity of solvent may be shown in Table 3.

Below, the manufacturing method of the liquid crystal display element for evaluating voltage retention is shown.

[Production of Liquid Crystal Display Element]

First, a substrate with electrodes was prepared. The substrate is a glass substrate having a size of 30 mm x 40 mm and a thickness of 1.1 mm. An ITO electrode having a film thickness of 35 nm is formed on the substrate, and the electrode has a stripe pattern of 40 mm in length and 10 mm in width.

Next, after filtering the liquid crystal aligning agent obtained above with a filter having a hole diameter of 1.0 μm, it was applied to the prepared substrate with electrodes by spin coating. After drying for 2 minutes on an 80 degreeC hot plate, it baked in 230 degreeC IR type oven for 20 minutes, the coating film of 100 nm in film thickness was formed, and the board|substrate with a liquid crystal aligning film was obtained. After rubbing this liquid crystal alignment film with a rayon cloth (roller diameter: 120 mm, roller rotation speed: 1000 rpm, moving speed: 20 mm/sec, press-fitting length: 0.4 mm), ultrasonic irradiation was performed for 1 minute in pure water to perform cleaning And after removing water droplets by air blow, it was made to dry at 80 degreeC for 10 minute(s) and the board|substrate with a liquid crystal aligning film was obtained. After preparing these two board|substrates with a liquid crystal aligning film and spread|dispersing a 4 micrometer-diameter spacer (made by Nikki Catalyst Chemicals Co., Ltd., Jinsagu, SW-D1) on the one liquid crystal aligning film surface, from thereon, a thermosetting sealing agent ( XN-1500T manufactured by Mitsui Chemicals Co., Ltd.) was printed, and the rubbing direction of another board|substrate was reversed, and after bonding together with the film surfaces facing each other, the sealing compound was hardened and the blank cell was produced. Negative liquid crystal MLC-7026 (manufactured by Merck & Co., Ltd.) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell. Then, after heating the obtained liquid crystal cell at 120 degreeC for 1 hour and leaving it to stand at 23 degreeC overnight, it was used for each evaluation.

<voltage retention rate>

A voltage of 1 V was applied to the liquid crystal display element for 60 μsec under a temperature of 60° C., the voltage after 16.67 msec was measured, and how much the voltage was maintained was evaluated as voltage retention. A result is shown in Table 4. The higher the value of the voltage holding ratio, the better. Further, it is known that line burn-in, which is one of the display defects of the liquid crystal display element, becomes less likely to occur when the voltage holding ratio, which is one of the electrical characteristics of the liquid crystal display element, increases.

<Evaluation of whitening characteristics>

0.1 mL of liquid crystal aligning agents (1)-(20) was dripped on the chromium vapor deposition board|substrate, and it left still in the environment of the temperature of 23 degreeC, and the humidity of 70%. After a predetermined time elapsed after the dripping, the edges and the central portion of the droplet were observed under an optical microscope to confirm whether or not whitening had occurred. A result is shown in Table 5. In this evaluation, a whitening phenomenon is defined as a phenomenon in which liquid droplets become cloudy due to precipitation or aggregation of dissolved polyimide. A state in which the droplet was not whitened at all was evaluated as "○", a state in which only the edge of the droplet was whitened was evaluated as "Δ", and a state in which the entire surface of the droplet was whitened was evaluated as "x". The longer the time to become ○, the better.

Normally, when a negative type liquid crystal is used as a liquid crystal material, the voltage holding ratio is lowered, and display defects (line burn-in) tend to occur. However, by using the liquid crystal aligning agent of Examples of the present invention, even when a negative type liquid crystal is used as a liquid crystal material, a liquid crystal display element having a high voltage retention (namely, a liquid crystal display element having a low incidence of display defects (line burn)) is obtained. lost.

In addition, since the liquid crystal aligning agent described in the examples of the present invention does not easily cause whitening by moisture absorption, it is difficult to cause foreign matter or clogging even when obtaining a coating film, and the resulting film has little surface roughness, and furthermore , Even if it dries and heats, the characteristic of an original liquid crystal aligning film can be exhibited.

In addition, all the content of the JP Patent application 2020-192467, claim, drawing, and abstract for which it applied on November 19, 2020 is referred here, and it takes in as an indication of the specification of this invention.

Claims (16)

The liquid crystal aligning agent characterized by containing the following (A) component.
Component (A): A copolymer having a repeating unit represented by the following formula (a), a repeating unit represented by the following formula (1), and a repeating unit represented by the following formula (2), and a polyimide that is an imide of the copolymer. As at least one type of polymer (A) selected from the group consisting of
At least one of the repeating unit represented by the following formula (a), the repeating unit represented by the following formula (1), and the repeating unit represented by the following formula (2) has a divalent organic group represented by the following formula (EG).

(X represents a tetravalent organic group. Y represents a divalent organic group derived from diamine. The two R's each independently represent a hydrogen atom or a monovalent organic group. The two Z's each independently represent a hydrogen atom or a monovalent organic group.)

(A ₁ is a divalent organic group, A _1' is a divalent organic group derived from diamine, and C ₁ and C _1' are each independently a hydrogen atom or a monovalent organic group.)

(A ₂ is a divalent organic group, and A _2' is a divalent organic group obtained by removing hydrogen atoms contained in two hydroxyl groups from an organic diol.)

(R represents a hydrogen atom or a methyl group. n is an integer of 3 to 40.) According to claim 1,
X in the formula (a) is a tetravalent organic group derived from tetracarboxylic dianhydride or a derivative thereof, and A ₁ in the formula (1) is a divalent organic group derived from diisocyanate And, A ₂ in the formula (2) is a divalent organic group derived from diisocyanate. According to claim 1 or 2,
The liquid crystal aligning agent whose n is an integer of 4-40 in the said Formula (EG). According to any one of claims 1 to 3,
Y in the formula (a) and A _1' in the formula (1) are each independently a diamine represented by the following formula (O), a diamine having an amide bond or a urea bond, or 3,3'- Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminobenzophenone, 1,4-bis(4-aminophenyl)benzene , 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene, diamine represented by the following formula ( _do ), 4-(2-(methylamino)ethyl)aniline, 4-(2-aminoethyl)aniline, a diamine having a group “-N(D)-” (D represents a protecting group that is desorbed by heating and replaced with a hydrogen atom), and a diamine represented by the following formula (d _EG ) The liquid crystal aligning agent which is a divalent organic group derived from the diamine chosen from the group which consists of.

(Ar represents a divalent benzene ring, biphenyl structure, or naphthalene ring. The two Ars may be the same or different, and any hydrogen atom of the benzene ring, biphenyl structure, or naphthalene ring is a monovalent group. p is an integer of 0 or 1. Q ₂ is -(CH ₂ ) _n - (n is an integer of 2 to 18), or -(CH ₂ ) _n - of -CH ₂ - Represents a group at least partially substituted with -O-, -C(=O)-, or -OC(=O)-, provided, however, that when Q ₂ has an ether bond, the total number of ether bonds possessed by Q ₂ should be 3 or less.)

(A plurality of m may be the same or different, respectively.)

(Ar each independently represents a divalent aromatic group or a condensed cyclic group, which may be the same or different. One or more hydrogen atoms on the aromatic group or condensed cyclic group may be substituted with a monovalent group. n is 3 to 40 represents the integer of .) According to any one of claims 1 to 4,
A ₁ in the formula (1) and A ₂ in the formula (2) are each independently (i) in the diisocyanate structure (O=C=NRN=C=O), where R is benzene A divalent organic group derived from an aromatic diisocyanate, which is an organic group having at least one ring and having 6 to 30 carbon atoms, or (ii) in the diisocyanate structure (O=C=NRN=C=O), R has an aliphatic group, Furthermore, the liquid crystal aligning agent which is a divalent organic group derived from aliphatic diisocyanate which is a C4-C30 organic group which does not have an aromatic group. According to any one of claims 1 to 5,
A 1 in said formula ( ₁ ) and A ₂ in said formula (2) are each independently a divalent organic group derived from diisocyanate selected from the following, The liquid crystal aligning agent.

According to any one of claims 1 to 6,
A liquid crystal aligning agent in which the organic diol in the formula (2) is diol containing a divalent organic group represented by the formula (EG). According to claim 7,
The liquid crystal aligning agent in which the diol containing the divalent organic group represented by the said formula (EG) is diol in which the hydrogen atom couple|bonded with the both ends of the divalent organic group represented by the said formula (EG). According to any one of claims 1 to 8,
X in the above (a) is a tetravalent organic group derived from acyclic aliphatic tetracarboxylic dianhydride or a derivative thereof, a tetravalent organic group derived from alicyclic tetracarboxylic dianhydride or a derivative thereof, or aromatic The liquid crystal aligning agent which is a tetravalent organic group derived from tetracarboxylic dianhydride or its derivative(s). According to any one of claims 1 to 9,
A liquid crystal aligning agent in which X in the above (a) is a tetravalent organic group derived from tetracarboxylic dianhydride represented by formula (t) or a derivative thereof.

In the formula, X ₁ is a structure selected from the following formulas (X1-1) to (X1-25). * represents a bonding hand.

(In the formulas (X1-1) to (X1-4), R ₁ to R ₂₁ are each independently a hydrogen atom, a halogen atom, an alkyl group of 1 to 6 carbon atoms, an alkenyl group of 2 to 6 carbon atoms, or a carbon atom of 2 to 6 alkynyl groups, monovalent organic groups having 1 to 6 carbon atoms containing a fluorine atom, or phenyl groups.
In formulas (X1-24) to (X1-25), j and k are integers of 0 or 1, and A ₁ and A ₂ are each independently a single bond, -O-, -CO-, - COO-, phenylene, sulfonyl group, or amide group is shown. A plurality of A ₂ may be the same or different, respectively.) According to any one of claims 1 to 10,
The content of the repeating unit represented by the formula (a) is 2 to 98 mol% of the total repeating units constituting the polymer (A), and the content of the repeating unit represented by the formula (1) constitutes the polymer (A). It is 1-49 mol% of the whole repeating unit which does, and the content rate of the repeating unit represented by Formula (2) is 1-49 mol% of the whole repeating unit which comprises a polymer (A). According to any one of claims 1 to 11,
The said liquid crystal aligning agent contains (B) component further, The liquid crystal aligning agent characterized by the above-mentioned.
Component (B): A polymer (B) different from the polymer (A) as at least one polymer selected from the group consisting of a polyimide precursor and its imidized polymer. A terminal isocyanate compound is synthesized by reacting component (o) containing an organic diol having two hydroxyl groups in a molecule with component (a) containing a compound containing two isocyanate groups in a molecule, Reacting component (b) containing a compound containing two primary or secondary amino groups to synthesize a terminal amine urea oligomer, and further reacting component (c) containing tetracarboxylic dianhydride or a derivative thereof At least one of the compounds constituting the component (o), (a), (b) and (c) has a partial structure represented by the following formula (EG) in the molecule The manufacturing method of A).

(R represents a hydrogen atom or a methyl group. n is an integer of 3 to 40.) According to claim 13,
Component (o) containing a diol compound represented by "HA _2' -H" (A _2' is the same as A _2' in formula (2) defined in claim 1), and O=C =NA ₁ -N=C=O (A ₁ is the same as A ₁ in formula (1) defined in claim 1.) Component (a) containing a diisocyanate compound represented by the reaction is reacted, and the terminal An isocyanate compound is synthesized, and then a component (b) containing a diamine represented by the following formula (mb) is reacted to synthesize a terminal amine urea oligomer, and then tetracarboxylic dianhydride or a derivative thereof represented by the following formula (mc) A method for producing a polymer comprising a step of reacting a component (c) containing, wherein at least one of A ₁ , A _1' , A _2' and X has a partial structure represented by the formula (EG) in a molecule. .

(In formula (mb), C ₁ , C _1' , A _1' are the same as C ₁ , C _1' , A _1' in formula (1) defined in claim 1, respectively.)

(In formula (mc), X is the same as X in formula (a) defined in claim 1.) The liquid crystal aligning film formed using the liquid crystal aligning agent in any one of Claims 1-12. A liquid crystal display element provided with the liquid crystal aligning film of Claim 15.