WO2023074391A1

WO2023074391A1 - Polymer composition, liquid crystal aligning agent, resin film, liquid crystal alignment film, method for producing liquid crystal display element, and liquid crystal display element

Info

Publication number: WO2023074391A1
Application number: PCT/JP2022/038192
Authority: WO
Inventors: 崇仲井; 佳道森本
Original assignee: 日産化学株式会社
Priority date: 2021-10-28
Filing date: 2022-10-13
Publication date: 2023-05-04
Also published as: TW202330691A

Abstract

The present invention provides a polymer composition that is suitable for a liquid crystal aligning agent which enables the achievement of a liquid crystal alignment film that has excellent resistance to an AC afterimage and a low pretilt angle.　This polymer composition is characterized by containing the following (A) component and (B) component. (A) component: at least one polymer (A) which is selected from the group consisting of a polyimide precursor having a repeating unit represented by formula (a) and a polyimide that is an imidized product of the polyimide precursor. (B) component: a polyester (B) which has a repeating unit represented by formula (b1) but does not have the repeating unit represented by formula (a) and an imidized structure thereof. Formula (a) (The definition of each symbol is as described in the description.) Formula (b1) (The definition of each symbol is as described in the description.)

Description

Polymer composition, liquid crystal alignment agent, resin film, liquid crystal alignment film, method for manufacturing liquid crystal display element, and liquid crystal display element

The present invention relates to a polymer composition, a liquid crystal alignment agent, a resin film, a liquid crystal alignment film, a method for manufacturing a liquid crystal display element, and a liquid crystal display element.

Liquid crystal display elements used in liquid crystal televisions, navigators, smartphones, etc. are usually provided with a liquid crystal alignment film for controlling the alignment state of liquid crystals. A liquid crystal alignment film has a function of controlling the alignment of liquid crystal molecules in a certain direction in a liquid crystal display element. For example, a liquid crystal display element has a structure in which liquid crystal molecules forming a liquid crystal layer are sandwiched between liquid crystal alignment films formed on respective surfaces of a pair of substrates. There, the liquid crystal molecules are aligned in a certain direction by the liquid crystal alignment film and respond by applying a voltage to the electrodes provided between the substrate and the liquid crystal alignment film. As a result, the liquid crystal display element displays a desired image by utilizing the alignment change due to the response of the liquid crystal molecules. Until now, liquid crystal alignment films have mainly been polyimide-based liquid crystal alignment films, which are obtained by applying a liquid crystal alignment agent whose main component is a polyimide precursor such as polyamic acid (polyamic acid) or a solution of soluble polyimide to a glass substrate or the like and baking it. used.
In recent years, as the performance of liquid crystal display elements has improved, in addition to applications such as large-screen, high-definition liquid crystal televisions, it is also used in automotive applications such as car navigation systems, meter panels, surveillance cameras, and medical camera monitors. A liquid crystal display device is used, and lateral electric field methods such as an IPS (In Plane Switching) method and an FFS (Fringe Field Switching) method are being studied because of the demand for viewing angle characteristics (Patent Document 1).

International Publication No. 2019-082975

Liquid crystal alignment films used in liquid crystal display elements of the IPS driving method and the FFS driving method require an alignment regulating force for suppressing afterimages (hereinafter also referred to as AC afterimages) generated by long-term AC driving. In the liquid crystal display devices, which are rapidly becoming higher in definition, high display quality is regarded as important, and specifications for display defects such as "afterimages" are becoming more and more severe.
In addition, as liquid crystal display elements are applied to automotive applications such as car navigation systems, meter panels, surveillance cameras, and medical camera monitors, from the viewpoint of further improving viewing angle characteristics, pretilt angles that are lower than before are becoming more popular. has become required.

In view of the above, the present invention provides a polymer composition suitable for a liquid crystal alignment agent that provides a liquid crystal alignment film having excellent resistance to AC afterimage and a low pretilt angle, the liquid crystal alignment agent, the liquid crystal alignment film, and An object of the present invention is to provide a liquid crystal display device having the liquid crystal alignment film.

As a result of intensive research to achieve the above object, the present inventors have found that forming a resin film using a polymer composition containing specific components is effective for achieving the above object. We found a certain thing and came to complete the present invention.

The present invention is based on such findings, and has the following gist.
A polymer composition characterized by containing the following components (A) and (B).
Component (A): At least one polymer (A) selected from the group consisting of a polyimide precursor having a repeating unit represented by the following formula (a) and a polyimide which is an imidized product of the polyimide precursor.
Component (B): Polyester (B) which has a repeating unit represented by the following formula (b1) and does not have a repeating unit represented by the following formula (a) and its imidized structure.

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

(X _ar represents a tetravalent organic group derived from an aromatic tetracarboxylic dianhydride or a derivative thereof. Each of the two R independently represents a hydrogen atom or a monovalent organic group. E is A divalent organic group obtained by removing hydrogen atoms contained in two hydroxy groups from an organic diol, wherein the organic diol contains a divalent organic group represented by the following formula (EG).)

(n is an integer of 5 or more. R represents a hydrogen atom or a methyl group.)

ADVANTAGE OF THE INVENTION According to this invention, the polymer composition suitable for the liquid-crystal aligning agent which can obtain the liquid-crystal aligning film which has excellent resistance to AC afterimage and has a low pretilt angle, this liquid-crystal aligning agent, this liquid-crystal aligning film, and this liquid crystal A liquid crystal display element having an alignment film can be obtained. Further, the liquid crystal display element has high display quality with few display defects.
Although the mechanism by which the above effects of the present invention are obtained is not necessarily clear, it is estimated as follows. That is, it is considered that the introduction of the specific alkylene glycol chain into the specific polyester improved the stretchability of the film and improved the flatness of the film surface, and thus the above effects were obtained.

Each component contained in the polymer composition of the present disclosure and other components optionally blended as necessary will be described below.
As used herein, halogen atoms include fluorine, chlorine, bromine and iodine atoms. Boc represents a tert-butoxycarbonyl group.

<Polymer (A)>
The polymer composition of the present invention is a polyimide precursor having a repeating unit represented by the above formula (a) (hereinafter also referred to as a polyimide precursor (A)) and a polyimide that is an imidized product of the polyimide precursor It contains at least one polymer (A) selected from the group consisting of: The polymer (A) may be of one type or two or more types.

(Repeating unit represented by formula (a))
In the above formula (a), Y represents a divalent organic group derived from diamine. The divalent organic group derived from diamine includes, for example, a divalent organic group obtained by removing two amino groups from diamine. Examples of the diamine include the following diamines. The diamines may be used singly or in combination of two or more.

diamines represented by the following formula (O); diamines having a photoalignable group such as 4,4'-diaminoazobenzene or diaminotran; diamines represented by the following formulas (h-1) to (h-6), etc. 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, a diamine represented by the following formula (d _o ); 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, 1,4-bis-(4-aminophenyl)-piperazine, 3,6 -diaminoacridine, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N-[3-(1H-imidazol-1-yl)propyl] 3,5-diaminobenzamide, 4 -[4-[(4-aminophenoxy)methyl]-4,5-dihydro-4-methyl-2-oxazolyl]-benzenamine, 4-[4-[(4-aminophenoxy)methyl]-4,5 -dihydro-2-oxazolyl]-benzenamine, 1,4-bis(p-aminobenzyl)piperazine, 4,4'-propane-[1,3-diylbis(piperidine-1,4-diyl)]dianiline, 4 -(4-aminophenoxycarbonyl)-1-(4-aminophenyl)piperidine, 2,5-bis(4-aminophenyl)pyrrole, 4,4'-(1-methyl-1H-pyrrole-2,5- diyl)bis[benzenamine], 1,4-bis-(4-aminophenyl)-piperazine, 2-N-(4-aminophenyl)pyridine-2,5-diamine, 2-N-(5-aminopyridine -2-yl)pyridine-2,5-diamine, 2-(4-aminophenyl)-5-aminobenzimidazole, 2-(4-aminophenyl)-6-aminobenzimidazole, 5-(1H-benzimidazole -2-yl)benzene-1,3-diamine, heterocycle-containing diamines such as diamines represented by the following formulas (z-1) to (z-5), or 4,4′-diaminodiphenylamine, 4,4'-diaminodiphenyl-N-methylamine, N,N'-bis(4-aminophenyl)-benzidine, N,N'-bis(4-aminophenyl)-N,N'-dimethylbenzidine, or , N,N'-Bis(4-aminophenyl)-N,N'-dimethyl-1,4-benzenediamine containing a nitrogen atom, represented by diamines having a diphenylamine structure, secondary or at least one nitrogen atom-containing structure selected from the group consisting of tertiary amino groups (wherein -N(D)-(D represents a protecting group that is eliminated by heating and replaced with a hydrogen atom); ) except amino groups derived from Hereinafter, it is also referred to as a specific nitrogen atom-containing structure. ); 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, 4,4'-diaminobiphenyl-3-carboxylic acid, 4,4'-diamino Diphenylmethane-3-carboxylic acid, 1,2-bis(4-aminophenyl)ethane-3-carboxylic acid, 4,4'-diaminobiphenyl-3,3'-dicarboxylic acid, 4,4'-diaminobiphenyl-2 ,2′-dicarboxylic acid, 3,3′-diaminobiphenyl-4,4′-dicarboxylic acid, 3,3′-diaminobiphenyl-2,4′-dicarboxylic acid, 4,4′-diaminodiphenylmethane-3,3 diamines having a carboxy group such as '-dicarboxylic acid, 1,2-bis(4-aminophenyl)ethane-3,3'-dicarboxylic acid, 4,4'-diaminodiphenyl ether-3,3'-dicarboxylic acid;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; 2-(2,4-diaminophenoxy)ethyl methacrylate and 2,4-diamino-N, Diamines having a photopolymerizable group at the end, such as N-diallylaniline; diamines having a steroid skeleton such as cholestanyl, 5-diaminobenzoate, cholestenyl 3,5-diaminobenzoate, lanostanyl 3,5-diaminobenzoate and 3,6-bis(4-aminobenzoyloxy)cholestane; Diamine represented by V-1) to (V-2); group "-N(D)-" (D represents a protective group that is eliminated by heating and replaced with a hydrogen atom, preferably a tert-butoxycarbonyl group ), preferably diamines represented by the following formulas (d-1) to (d-7): 1,3-bis(3-aminopropyl)-tetramethyldisiloxane, the following formula (Ds- 1) diamines having a siloxane bond, such as diamines represented by; 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), a group represented by any of the formulas (Y-1) to (Y-167) described in International Publication No. 2018/117239 2 A diamine having two amino groups bonded thereto, and the like.

(Ar represents a divalent benzene ring, biphenyl structure, or naphthalene ring. The two Ars may be the same or different, and any hydrogen atom in 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 the —(CH ₂ ) _n — represents a group in which at least part of -CH ₂ - is replaced with -O-, -C(=O)- or -O-C(=O)-.)

(In formula (z-2), two m may be the same or different.)

(When there are two or more m, the two or more m may be the same or different. One or more hydrogen atoms on the benzene ring may be substituted with a monovalent group.)

(In formula (V-1), m and n are each independently an integer of 0 to 3 (provided that 1 ≤ m + n ≤ 4.), j is an integer of 0 or 1, and X ¹ is -(CH ₂ ) _a - (a is an integer of 1 to 15), -CONH-, -NHCO-, -CO-N(CH ₃ )-, -NH-, -O-, - represents CH ₂ O—, —CH ₂ —OCO—, —COO—, or —OCO—, R ¹ is a fluorine atom, a fluorine atom-containing alkyl group having 1 to 10 carbon atoms, or a fluorine atom having 1 to 10 carbon atoms; represents an alkoxy group containing, an alkyl group having 3 to 10 carbon atoms, an alkoxy group having 3 to 10 carbon atoms, or an alkoxyalkyl group having 3 to 10 carbon atoms, when there are two m, n, X ¹ and R ¹ , each independently having the above definition In formula (V-2), X ² represents -O-, -CH ₂ O-, -CH ₂ -OCO-, -COO-, or -OCO-. )

(In formulas (d-2), (d-6) and (d-7), R is a hydrogen atom or -(CH ₂ ) _k -Boc (k is an integer of 0 to 3. In addition, k is 0, (CH ₂ ) _k represents a single bond.)

In the above formula (d _o ), the monovalent group includes a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms. fluoroalkyl group, fluoroalkenyl group having 2 to 10 carbon atoms, fluoroalkoxy group having 1 to 10 carbon atoms, carboxy group, hydroxy group, alkyloxycarbonyl group having 1 to 10 carbon atoms, cyano group, nitro group and the like. be done.
As the diamine represented by the above formula (d _o ), diamines represented by the following formulas (d _o -1) to (d _o -6), 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether and 4,4'-diaminodiphenyl ether are preferred.

In the diamine represented by formula (O) above, any hydrogen atom in the benzene ring, biphenyl structure, or naphthalene ring may be replaced with a monovalent group. Examples of the monovalent group include a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, Examples include a fluoroalkenyl group having 2 to 10 carbon atoms, a fluoroalkoxy group having 1 to 10 carbon atoms, an alkyloxycarbonyl group having 1 to 10 carbon atoms, a cyano group, a nitro group and the like.

As the diamine represented by the above formula (O), the following formulas (o-1) to (o-8), p-phenylenediamine, 2,3,5,6-tetramethyl- p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 1,4-diamino-2,5-dimethoxybenzene, 2,5-diamino toluene, 2,6-diaminotoluene, 4-aminobenzylamine, 2-(6-amino-2-naphthyl)ethylamine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl- 4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3-trifluoromethyl-4,4'-diaminobiphenyl, 2-trifluoromethyl-4,4'-diaminobiphenyl , 3-fluoro-4,4′-diaminobiphenyl, 2-fluoro-4,4′-diaminobiphenyl, 2,2′-difluoro-4,4′-diaminobiphenyl, 3,3′-difluoro-4,4 '-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,3'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,4'- diaminobiphenyl, 4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1 ,7-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene or 2,7-diaminonaphthalene are preferred.

(In formula (o-8), two m may be the same or different.)

Y is a diamine represented by the formula (O), a diamine having an amide bond or a urea bond, 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, the formula (d _o ), 4-(2-(methylamino)ethyl)aniline, 4-(2-aminoethyl)aniline, and the group “-N(D)-” (D is eliminated by heating to form a hydrogen atom represents a protecting group to be substituted, preferably a tert-butoxycarbonyl group), and is preferably a divalent organic group derived from a diamine selected from the group consisting of diamines. When Y satisfies this configuration, it is possible to obtain the effect of reducing afterimages that occur during long-term AC driving, which is preferable.

In the above formula (a), X represents a tetravalent organic group. X preferably represents a tetravalent organic group derived from a tetracarboxylic dianhydride or a derivative thereof. The tetravalent organic group derived from a tetracarboxylic dianhydride or a derivative thereof includes, for example, a tetravalent organic group obtained by removing four carboxy groups from the corresponding tetracarboxylic acid. As the tetravalent organic group, a tetravalent organic group derived from an acyclic aliphatic tetracarboxylic dianhydride or a derivative thereof, a tetravalent organic group derived from an alicyclic tetracarboxylic dianhydride or a derivative thereof, A tetravalent organic group derived from an organic group or an aromatic tetracarboxylic dianhydride or a derivative thereof can be mentioned.
Here, the acyclic aliphatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups bonded to a chain hydrocarbon structure. However, it does not need to be composed only of a chain hydrocarbon structure, and may have an alicyclic structure or an aromatic ring structure in part thereof.
An 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 carboxy groups are bonded to the aromatic ring. Moreover, it is not necessary to consist only of an alicyclic structure, and a part thereof may have a chain hydrocarbon structure or an aromatic ring structure.
An 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. However, it is not necessary to consist only of an aromatic ring structure, and a part thereof may have a chain hydrocarbon structure or an alicyclic structure.
Examples of the tetracarboxylic dianhydride derivatives include tetracarboxylic acid dihalides, tetracarboxylic acid dialkyl esters, and tetracarboxylic acid dialkyl ester dihalides.
The tetracarboxylic dianhydride or derivative thereof may be used singly or in combination of two or more.

The above-mentioned acyclic aliphatic or alicyclic tetracarboxylic dianhydrides, or derivatives thereof, are selected from the group consisting of a cyclobutane ring structure, a cyclopentane ring structure and a cyclohexane ring structure from the viewpoint of enhancing the liquid crystal orientation. It is preferably a tetracarboxylic dianhydride having at least one partial structure or a derivative thereof.

The above X is preferably a tetravalent organic group derived from a tetracarboxylic dianhydride represented by the following 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 bond. Incidentally, the tetracarboxylic dianhydride represented by the formula (t) in which X ₁ is a formula (X1-1) to (X1-23) is an acyclic aliphatic or alicyclic tetracarboxylic dianhydride is an example of Further, tetracarboxylic dianhydrides represented by formula (t) in which X ₁ is one of formulas (X1-24) to (X1-25) are examples of aromatic tetracarboxylic dianhydrides.

In formulas (X1-1) to (X1-4), R ₁ to R ₂₁ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, It represents an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group. * represents a bond. R ₁ to R ₂₁ are preferably a hydrogen atom, a halogen atom, a methyl group, or an ethyl group, more preferably a hydrogen atom or a methyl group, from the viewpoint of enhancing liquid crystal orientation.
In formulas (X1-24) to (X1-25), j and k are integers of 0 or 1, A ₁ and A ₂ are each independently a single bond, -O-, -CO-, -COO-, represents a phenylene group, a sulfonyl group, or an amide group. A plurality of A ₂ may be the same or different.

Specific examples of formula (X1-1) include the following formulas (1-1) to (1-6). Formulas (1-1) and (1-2) are particularly preferred from the viewpoint of enhancing liquid crystal orientation. * has the same meaning as above.

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.

From the viewpoint of enhancing the liquid crystal orientation, the above X ₁ is represented by the above formulas (X1-1) to (X1-10), (X1-18) to (X1-23), (X1-24) to (X1-25) , or (X1-26) to (X1-30) are preferred, 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 the monovalent organic group for R and Z in the above formula (a), a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the methylene group of the hydrocarbon group is -O-, -S-, -CO- , —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 monovalent hydrocarbon group having 1 to 10 carbon atoms.), -Si(R ³ ) ₂ - (where R ³ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms). is a hydrocarbon group.), a monovalent group A substituted with —SO ₂ —, etc., a monovalent hydrocarbon group, or at least one hydrogen atom bonded to a carbon atom of the monovalent group A is a halogen atom , hydroxy group, alkoxy group, nitro group, amino group, mercapto group, nitroso group, alkylsilyl group, alkoxysilyl group, silanol group, sulphino group, phosphino group, carboxy group, cyano group, sulfo group, acyl group, etc. a monovalent group having a heterocyclic ring. Examples of monovalent organic groups for R and Z in the above formula (a) include, among others, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a tert-butoxy A carbonyl group or a 9-fluorenylmethoxycarbonyl group is preferred, an alkyl group having 1 to 3 carbon atoms is more preferred, and a methyl group is even more preferred.
From the viewpoint of obtaining the effects of the present invention, R and Z are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group.

In the above formula (a), each of X, Y, R, and Z may be of one type or two or more types.
The content of the polymer (A) is preferably 70 to 99 parts by mass, more preferably 80 to 98 parts by mass, based on 100 parts by mass of the polymer composition.

(Repeating Unit Constituting Polymer (A))
The polymer (A) in the present invention is at least one polymer selected from the group consisting of a polyimide precursor having a repeating unit represented by the above formula (a) and a polyimide which is an imidized product of the polyimide precursor. be. The polymer (A) may have a repeating unit represented by formula (a) and a terminal group.

Here, the term "terminal group" refers to a group bonded to the terminals of the repeating units constituting the polymer (A). Examples of terminal groups include amino groups, carboxy groups, acid anhydride groups, isocyanate groups, or derivatives thereof. An amino group, a carboxyl group, an acid anhydride group, and an isocyanate group can be obtained by a normal condensation reaction, and the above derivatives can be obtained, for example, by blocking terminal groups with a terminal blocking agent, as described later. can be done.

The total of the repeating unit represented by formula (a) and its imidized structure is preferably 10 mol% or more, more preferably 20 mol% or more, of the total repeating units constituting the polymer (A).

(Repeating unit represented by formula (U))
The polymer (A) in the invention may further have a repeating unit represented by the following formula (U).

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

In formula (U) above, _U1 is a divalent organic group. Examples of U ₁ include divalent organic groups derived from diisocyanates. The diisocyanate may be used alone or in combination of two or more.
Here, examples of diisocyanates include aromatic diisocyanates and aliphatic diisocyanates.
Here, "aromatic diisocyanate" means a diisocyanate having at least one aromatic group. Moreover, "aliphatic diisocyanate" means a diisocyanate having an aliphatic group and not having an aromatic group.
U ₁ is, for example, (i) a diisocyanate structure (O=C=N-R-N=C=O) in which R is an organic group having 6 to 30 carbon atoms and having at least one benzene ring. A divalent organic group derived from a diisocyanate, or (ii) in the diisocyanate structure (O=C=N-R-N=C=O), R has an aliphatic group and does not have an aromatic group. A divalent organic group derived from an aliphatic diisocyanate, which is an organic group having a number of 4 to 30, can be mentioned.
In addition, an aliphatic group includes both an acyclic aliphatic group and an alicyclic group.
Specific examples of _U1 include o-phenylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, toluene diisocyanates (eg, tolylene 2,4-diisocyanate, tolylene 2,6-diisocyanate), 1,4- Diisocyanate-2-methoxybenzene, 2,5-diisocyanate xylenes, 3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 4,4′-diisocyanatodiphenyl ether, 2,2′-bis(4-diisocyanate acid phenyl)propane, 4,4'-diphenylmethane diisocyanate (4,4'-diphenylmethane diisocyanate), 4,4'-diphenyl diisocyanate ether, 4,4'-diphenyl sulfone diisocyanate, 3,3'-diphenyl diisocyanate Divalent organic groups derived from aromatic diisocyanates such as sulfone and benzophenone 2,2′-diisocyanate, aliphatic diisocyanates such as isophorone diisocyanate, norbornene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and tetramethylene diisocyanate and divalent organic groups.

In the above formula (U), U _1' is a divalent organic group derived from diamine. Examples of the diamine include the diamines exemplified for the repeating unit (a) above, and preferred embodiments are the same as above.

Examples of the monovalent organic groups of C ₁ and C _1′ in the formula (U) include the structures exemplified for R and Z in the repeating unit (a). From the viewpoint of obtaining the effects of the present invention, C ₁ and C _1′ are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group.

In the above formula (U), each of U ₁ , U _1′ , C ₁ , and C _1′ may be of one kind, or two or more kinds thereof.

When the polymer (A) in the present invention has a repeating unit represented by the above formula (U), the content of the repeating unit represented by the formula (U) is, from the viewpoint of obtaining the effect of the present invention, the above With respect to the total 100 mol% of the repeating unit (a), the imidized structure of the repeating unit (a) and the repeating unit represented by the above formula (U), 1 to 30 mol% is preferable, and 2 to 25 mol% is more preferred.

<Polyester (B)>
The polymer composition of the present invention contains a polyester (B) having a repeating unit represented by the above formula (b1) and having no repeating unit represented by the above formula (a) and its imidized structure. do. Polyester (B) may be used alone or in combination of two or more.

X _ar in the above formula (b1) represents a tetravalent organic group derived from an aromatic tetracarboxylic dianhydride or a derivative thereof.
The 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. However, it is not necessary to consist only of an aromatic ring structure, and a part thereof may have a chain hydrocarbon structure or an alicyclic structure.
X _ar in the above formula (b1) is preferably a tetravalent organic group derived from a tetracarboxylic dianhydride represented by the following formula (t) or a derivative thereof.

(In the formula, X ₁ is a structure selected from the following formulas (X1-24) and (X1-25). * represents a bond.)

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

In the above formula (b1), E is a divalent organic group obtained by removing hydrogen atoms contained in two hydroxy groups from an organic diol, and the organic diol is a divalent group represented by the above formula (EG). contains an organic group of The organic diol containing a divalent organic group represented by the above formula (EG) is not particularly limited as long as it contains the above formula (EG) in the molecule, but a diol having hydrogen atoms bonded to both ends of the above formula (EG) is more preferred. In the diol having hydrogen atoms bonded to both ends of the above formula (EG), the upper limit of n is preferably set so that the upper limit of the weight average molecular weight of the diol is 5,000 or less. More preferably, the upper limit of the molecular weight is set to 4,000 or less, and more preferably, the upper limit of the weight average molecular weight of the diol is set to 3,000 or less. From the viewpoint of enhancing liquid crystal orientation, the upper limit of n is preferably 40, more preferably 30, and particularly preferably 20. The lower limit of n is preferably 5, more preferably 6, from the viewpoint of enhancing liquid crystal orientation. More specifically, the diol containing a divalent organic group represented by the above formula (EG) includes pentaethylene glycol, hexaethylene glycol, trade names PEG-300, PEG-400, PEG- 600, PEG-1000, PEG-1500, PEG-2000, PEG-4000N, PEG-4000S, PEG-6000E, PEG-6000P, PEG-10000, PEG-13000, PEG-20000; product name PEG300 manufactured by Merck; PEG1000, PEG2000, PEG4000, PEG6000, PEG8000, PEG10000, PEG12000, PEG20000, PEG35000; product numbers P2139, P3265, P3515, 81210, 81240, 81260, 81285, 81310, 18 from SIGMA-ALDRICH 1986, 181994, 182001, 182028, 189456, 202304, 202312, 202320, 202339, 202398, 202421, 202436, 202444, 202452, 295906, 309028, 372773, 372781, 373001, 412325, 435406, 43 5422, 435457, 637726; trade name SINOPOL manufactured by Chunichi Synthetic Chemical Co., Ltd. PEG600, SINOPOL PEG1500, SINOPOL PEG4000; brand names PEG#300, PEG#400, PEG#600, PEG#1000, PEG#1500, PEG#1540, PEG#4000, PEG#6000M manufactured by Lion Specialty Chemicals, Commercially available products such as Polyethylene Glycol 400 and Polyethylene Glycol 600 manufactured by Tokyo Kasei Kogyo Co., Ltd. can be mentioned. Preferred specific examples of the diol having hydrogen atoms bonded to both ends of the above formula (EG) include pentaethylene glycol, hexaethylene glycol, Sanyo Chemical Industries Co., Ltd. trade names PEG-300, PEG-400, PEG-600, PEG- 1000, product names PEG300 and PEG1000 manufactured by Merck, product names PEG300 manufactured by Merck, trade names SINOPOL PEG600 and SINOPOL PEG1000 manufactured by Chunichi Synthetic Chemicals, trade names PEG#300 and PEG manufactured by Lion Specialty Chemicals # 400, PEG # 600, PEG # 1000, the product name of Tokyo Chemical Industry Co., Ltd. Polyethylene Glycol 400, Polyethylene Glycol 600, polyethylene glycol represented by, or pentapropylene glycol, hexapropylene glycol, polypropylene glycol (more preferable average Polypropylene glycol with an average molecular weight of 400 to 5,000), copolymers of ethylene oxide and propylene oxide with an average molecular weight of 500 to 5,000, and the like. The above-mentioned polyethylene glycol and polypropylene glycol may be those obtained by subjecting ethylene oxide and propylene oxide to an anionic ring-opening polymerization reaction. The polymerization reaction can be carried out using water, ethylene glycol, propylene glycol, etc. and a catalytic amount of a base (eg, potassium hydroxide).
The average molecular weight of the glycol exemplified in the diol containing a divalent organic group represented by (EG) above is the weight average molecular weight obtained based on polystyrene by gel permeation chromatography (GPC).

The content of the repeating unit represented by the above formula (b1) is preferably 10 mol% or more, more preferably 20 mol% or more, of the total repeating units constituting the polyester (B). When other repeating units are included, the upper limit is more preferably 90 mol % or less, and even more preferably 80 mol % or less.

(Repeating unit represented by formula (b2))
Polyester (B) may further have a repeating unit represented by the following formula (b2). Polyester (B) may not have a repeating unit represented by the following formula (b2).

( _A1 is a divalent organic group derived from diisocyanate. _A2 is a divalent organic group obtained by removing hydrogen atoms contained in two hydroxy groups from an organic diol.)

In the above formula (b2), _A1 is a divalent organic group derived from diisocyanate. The divalent organic group derived from diisocyanate includes, for example, a divalent organic group obtained by removing two isocyanate groups (-N=C=O) from diisocyanate. The diisocyanate may be used alone or in combination of two or more.
Examples of the diisocyanate include diisocyanate (DI EG ) having a divalent organic group represented by the above formula ( _EG ), aromatic diisocyanate other than diisocyanate (DI _EG ), and aliphatic diisocyanate.
Here, "aromatic diisocyanate" means a diisocyanate having at least one aromatic group. Moreover, "aliphatic diisocyanate" means a diisocyanate having an aliphatic group and not having an aromatic group.
Examples of the diisocyanate (DI _EG ) include diisocyanates represented below.

Examples of aromatic diisocyanates and aliphatic diisocyanates other than diisocyanate (DI _EG ) include (i) a diisocyanate structure (O=C=N—R—N=C=O) in which R is the above formula (EG) An aromatic diisocyanate which is an organic group having 6 to 30 carbon atoms and has at least one benzene ring, or (ii) a diisocyanate structure (O=C=N-R —N=C=O), R is an organic group having 4 to 30 carbon atoms and having an aliphatic group and having no divalent organic group or aromatic group represented by the above formula (EG). Aliphatic diisocyanates can be mentioned.
In addition, an aliphatic group includes both an acyclic aliphatic group and an alicyclic group.
Specific examples of aromatic diisocyanates and aliphatic diisocyanates other than diisocyanate (DI _EG ) include o-phenylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, toluene diisocyanates (e.g., 2,4-diisocyanate tolylene, 2 ,6-diisocyanate tolylene), 1,4-diisocyanate-2-methoxybenzene, 2,5-diisocyanate xylenes, 3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 4,4′-diisocyanate Diphenyl ether, 2,2′-bis(4-phenyl diisocyanate)propane, 4,4′-diphenylmethane diisocyanate (4,4′-diphenylmethane diisocyanate), 4,4′-diphenyl sulfone diisocyanate, 3,3′- Aromatic diisocyanates such as diphenylsulfone diisocyanate and benzophenone 2,2′-diisocyanate, aliphatic diisocyanates such as isophorone diisocyanate, norbornene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and tetramethylene diisocyanate.

In the above formula (b2), _A2 is a divalent organic group obtained by removing hydrogen atoms contained in two hydroxy groups from an organic diol. The organic diols may be used singly or in combination of two or more. Examples of the organic diol include a diol containing a divalent organic group represented by the above formula (EG); and a diol containing no divalent organic group represented by the above formula (EG).
Specific examples of diols not containing a divalent organic group represented by formula (EG) include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, and 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, Alkylene diols such as 8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol; dimethylolpropionic acid (2,2-bis(hydroxy methyl)propionic acid), dimethylolbutanoic acid (2,2-bis(hydroxymethyl)butanoic acid), 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2, Carboxy group-containing diols such as 6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid and 3,5-dihydroxybenzoic acid; polypropylene glycol; random copolymer of polypropylene glycol and neopentyl glycol; polyhydric alcohol and polybasic polyester diol obtained by reacting with an acid; polycarbonate diol having a carbonate skeleton; polycaprolactone diol obtained by ring-opening addition reaction of lactones such as γ-butyl lactone, ε-caprolactone and δ-valerolactone; propylene oxide adduct of bisphenol A; hydrogenated bisphenol A; propylene oxide adduct of hydrogenated bisphenol A;
Specific examples of the diol containing a divalent organic group represented by the above formula (EG) include the diols exemplified for the repeating unit (b1) above, including preferred embodiments.

(Repeating unit constituting polyester (B))
The polyester (B) in the present invention is a polyester that has a repeating unit represented by the above formula (b1) and does not have a repeating unit represented by the above formula (a) and its imidized structure. The polyester (B) in the present invention may have the repeating units and terminal groups described above. The end groups are as described above.

When the polyester (B) contains the repeating unit represented by the formula (b2), the content of the repeating unit represented by the formula (b2) is 10 mol% of the total repeating units constituting the polyester (B). The above is preferable, and 20 mol % or more is more preferable. Moreover, it is more preferably 90 mol % or less, and even more preferably 80 mol % or less.
Further, when _A2 is a divalent organic group derived from a diol having hydrogen atoms bonded to both ends of the above formula (EG), the content of repeating units represented by the formula (b2) is the polyester (B) is preferably 10 mol % or more, more preferably 20 mol % or more, and even more preferably 50 mol % or more of the entire repeating units constituting Moreover, the upper limit is more preferably 90 mol % or less, and even more preferably 80 mol % or less.

In the above formula (b2), A ₁ and A ₂ may each be one type, or two or more types.
The content of the polyester (B) in the present invention is preferably 1 to 30 parts by mass, more preferably 2 to 20 parts by mass, based on 100 parts by mass of the polymer composition.

<Production of polymer (A)>
Examples of the polyimide precursor, which is the polymer (A), include polyamic acids and polyamic acid esters.
A polyamic acid (a polyimide precursor having a repeating unit represented by the formula (a) in which R in the formula (a) is a hydrogen atom) can be produced by the following method. Specifically, the tetracarboxylic acid component containing the tetracarboxylic dianhydride or derivative thereof and the diamine component containing the diamine are mixed in the presence of an organic solvent at a temperature of preferably −20 to 150° C., more preferably 0 to 50° C. °C, preferably 30 minutes to 24 hours, more preferably 1 to 12 hours (polycondensation). When the polyamic acid has the repeating unit (U), it is represented by O=C=NU ₁ -N=C=O (U ₁ is the same as U ₁ in formula (U).) can be synthesized by reacting the diisocyanate compound obtained with the above tetracarboxylic acid component and the above diamine component.
Specific examples of the organic solvent used in the above reaction include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, 1,3-dimethyl-2-imidazolidinone can be mentioned. Further, when the polymer has high solvent solubility, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formulas [D-1] to [D-3] Any of the indicated solvents can be used. These may be used in combination of two or more.

(In formula [D-1], D ¹ represents an alkyl group having 1 to 3 carbon atoms; in formula [D-2], D ² represents an alkyl group having 1 to 3 carbon atoms; ], D ³ represents an alkyl group having 1 to 4 carbon atoms.).
The reaction can be carried out at any concentration, preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The initial stage of the reaction can be carried out at a high concentration, and then the solvent can be added. In the reaction, the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic acid component is preferably 0.8 to 1.2. Similar to a normal polycondensation reaction, the closer this molar ratio is to 1.0, the greater the molecular weight of the polyamic acid produced.

The polyamic acid obtained in the above reaction can be recovered by precipitating the polyamic acid by injecting the reaction solution into a poor solvent while stirring well. Further, a purified polyamic acid powder can be obtained by performing precipitation several times, washing with a poor solvent, and drying at room temperature or by heating. Poor solvents include, but are not limited to, water, methanol, ethanol, hexane, butyl cellosolve, acetone, and toluene.

When the polyimide precursor is a polyamic acid ester (a polyimide precursor having a repeating unit represented by the formula (a) in which at least one of R in the formula (a) is a monovalent organic group), ( 1) a method of esterifying a polyamic acid obtained from a tetracarboxylic dianhydride and a diamine, (2) a method of reacting a tetracarboxylic acid diester dichloride and a diamine, and (3) a polycondensation of a tetracarboxylic acid diester and a diamine. It can be manufactured by a known method such as a method of causing

[Terminal blocking agent]
When synthesizing the polymer (A) in the present invention, a tetracarboxylic acid component containing a tetracarboxylic dianhydride or a derivative thereof, a diamine component, and optionally a diisocyanate compound are end-blocked using an appropriate end-blocking agent. A stop-type polymer may be synthesized.

Terminal blockers include, for example, acetic anhydride, maleic anhydride, nadic anhydride, phthalic anhydride, itaconic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, trimellitic anhydride, 3- (3-trimethoxysilyl)propyl)-3,4-dihydrofuran-2,5-dione, 4,5,6,7-tetrafluoroisobenzofuran-1,3-dione, 4-ethynylphthalic anhydride, etc. di-tert-butyl dicarbonate, dicarbonic acid diester compounds such as diallyl dicarbonate; acryloyl chloride, methacryloyl chloride, chlorocarbonyl compounds such as 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, n-pentylamine, n-hexylamine , n-heptylamine, n-octylamine and other monoamine compounds; ethyl isocyanate, phenyl isocyanate, naphthyl isocyanate, 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate and other unsaturated bonds monoisocyanate compounds such as isocyanate; and isothiocyanate compounds such as ethyl isothiocyanate and allyl isothiocyanate.

The proportion of the end blocking agent used is preferably 20 mol parts or less, and preferably 10 mol parts or less, with respect to a total of 100 mol parts of the diamine component used and the organic diol component used as necessary. is more preferred. The proportion of the terminal blocker used is preferably 0.01 mol part or more, more preferably 0.1 mol part or more, with respect to a total of 100 mol parts of the diamine component used.

Polyimide can also be obtained by ring-closing (imidizing) the polyimide precursor (A) of the polymer (A). The imidization ratio as used herein means the ratio of imide groups to the total amount of imide groups derived from tetracarboxylic dianhydride or derivatives thereof and carboxy groups (or derivatives thereof). The imidization rate does not necessarily have to be 100%, and can be arbitrarily adjusted according to the application and purpose.

Examples of methods for imidizing the polyimide precursor include thermal imidization in which the solution of the polyimide precursor is heated as it is, and catalytic imidization in which a catalyst is added to the solution of the polyimide precursor.

The temperature when the polyimide precursor is thermally imidized in the solution is preferably 100 to 400° C., more preferably 120 to 250° C., and it is preferable to remove water generated by the imidization reaction from the system. .

Catalytic imidization of the polyimide precursor is carried out by adding a basic catalyst and an acid anhydride to the solution of the polyimide precursor, preferably -20 to 250°C, more preferably stirring at 0 to 180°C. can be done. The amount of the basic catalyst is preferably 0.5 to 30 times the molar amount of the amic acid group, more preferably 2 to 20 times the molar amount, and the amount of the acid anhydride is preferably 1 to 50 times the molar amount of the amic acid group. It is preferably 3 to 30 molar times. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc. Among them, pyridine is preferable because it has appropriate basicity for advancing the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among them, acetic anhydride is preferable because it facilitates purification after the reaction is completed. The imidization rate by catalytic imidization can be controlled by adjusting the catalyst amount, reaction temperature, and reaction time.

When recovering the generated polyimide precursor or polyimide from the polyimide precursor or polyimide reaction solution, the reaction solution may be put into a solvent to precipitate. 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 putting it into a solvent can be filtered and recovered, and then dried at room temperature or under heat under normal pressure or reduced pressure. In addition, the impurities in the polymer can be reduced by redissolving the precipitated and recovered polymer in an organic solvent and repeating the operation of reprecipitating and recovering, for example, 2 to 10 times. Solvents in this case include, for example, alcohols, ketones, hydrocarbons, and the like, and it is preferable to use three or more kinds of solvents selected from these, because the purification efficiency is further improved.

The molecular weight of the polymer (A) 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, the workability during film formation, and the coating property. The average molecular weight is preferably from 5,000 to 1,000,000, more preferably from 10,000 to 150,000.

<Production of polyester (B)>
The polyester (B) is, for example, a component (o) containing an organic diol having two hydroxy groups in the molecule, and a tetracarboxylic dianhydride having a tetravalent organic group represented by _Xar in the molecule. or obtained by reacting with component (c) containing a derivative thereof. Here, the component (o) includes an organic diol (o) having a partial structure represented by the following formula (EG) in its molecule.

(n is an integer of 5 or more. R represents a hydrogen atom or a methyl group.)

Further, when the polyester (B) contains a repeating unit represented by the formula (b2), in addition to the monomer component, a component (i) containing a compound containing two isocyanate groups in the molecule obtained by reacting

The (o) component, the (c) component, and the optionally used (i) component may each be of one type or two or more types.

Examples of the organic diol (o) include organic diols exemplified by the repeating unit represented by the above formula (b1), and "H-EH" (E is synonymous with E in formula (b1). There is a diol compound represented by.

When using the diol (o') that does not contain the partial structure represented by the formula (EG), the monomer component for obtaining the polyester (B) contains the diol (o').

Component (i) includes, for example, diisocyanate compounds represented by O=C=NA ₁ -N=C=O (A ₁ is the same as A ₁ in formula (b2)).

The reaction of the (o) component, the (c) component and the optionally used (i) component is usually carried out in an organic solvent. The organic solvent used at that time is not particularly limited as long as it dissolves the produced polyester (B). Specific examples include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methyl-ε-caprolactam, dimethylsulfoxide, Tetramethylurea, pyridine, dimethylsulfone, hexamethylphosphoric acid 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 mono Acetate 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, methyl 3-methoxypropionate, 3-ethoxy methyl propionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme or 4-hydroxy- 4-methyl-2-pentanone and the like. These may be used alone or in combination. Furthermore, even a solvent that does not dissolve the polyester (B) may be used by mixing with the above solvent. Moreover, since moisture in the organic solvent inhibits the polymerization reaction, it is preferable to use the organic solvent after dehydration and drying.

In the method for synthesizing the polyester (B) obtained by reacting the (o) component and the (c) component used in the present invention, the blending amount of the (o) component and the (c) component is determined by the number of hydroxy groups and tetracarboxylic The ratio (group (am)/hydroxy group) of the sum of the groups of the amic acid group or derivative thereof possessed by the acid dianhydride (hereinafter also referred to as group (am)) is preferably 0.8 or more and 1.2 or less. , more preferably 0.9 or more and 1.2 or less, more preferably 0.9 or more and 1.1 or less, in an organic solvent.

Further, when the above-mentioned (i) component is included as a monomer component of the polyester (B), a method for synthesizing the polyester (B) obtained by reacting the (o) component, the (c) component and the (i) component is the ratio of the number of hydroxy groups to the total number of isocyanate groups and groups (am) ((isocyanate groups + groups (am))/hydroxy groups ) is preferably 0.8 or more and 1.2 or less, more preferably 0.9 or more and 1.2 or less, still more preferably 0.9 or more and 1.1 or less, obtained by reacting in an organic solvent. be done.

Further, when two or more organic diols are used, the reaction with a diisocyanate compound or tetracarboxylic dianhydride or a derivative thereof may be performed after mixing two or more organic diols. A diisocyanate compound or a tetracarboxylic dianhydride or a derivative thereof may be reacted separately. Further, after reacting an organic diol with a diisocyanate compound, or a tetracarboxylic dianhydride or a derivative thereof, the resulting terminal isocyanate compound or amic acid terminal or derivative thereof is further reacted with another organic diol compound, and This may be reacted with a diisocyanate compound or a tetracarboxylic dianhydride or derivative thereof. The same applies to the case of using two or more kinds of diisocyanate compounds or tetracarboxylic dianhydrides or derivatives thereof. Thus, the desired polyester (B) can be produced.

The reaction temperature of component (o) with component (c) and component (i) used as necessary is preferably 0 to 160°C, more preferably 10 to 150°C. The reaction time can be appropriately selected depending on the reaction scale and reaction conditions employed. In addition, if necessary, the reaction may be carried out in the presence of a catalyst such as tertiary amines, alkali metals, alkaline earth metals, tin, zinc, titanium, cobalt or other metals or metalloid compounds. The total concentration of components (o) and (i) in the reaction solution is preferably 1 to 50 mass %, more preferably 5 to 30 mass %. The initial stage of the reaction may be carried out at a high concentration, and then the organic solvent may be added.

The molecular weight of the polyester (B) used in the present invention is the weight average measured by the GPC (Gel Permeation Chromatography) method when considering the strength of the liquid crystal alignment film obtained therefrom, workability during film formation and coating film properties. The molecular weight is preferably 4,000 to 80,000, more preferably 6,000 to 60,000.
The polyester used in the present invention preferably has a viscosity at 25° C. of 10 to 5,000 mPa·s, more preferably 100 to 3,000 mPa·s. The above viscosity is a preferable value when the solid content concentration in the polyester solution is in the range of 10 to 50% by mass.
It is preferable that the viscosity is within the above range from the viewpoint of suitably obtaining the effects of the present invention. The above viscosity is a value measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) with a sample amount of 1.1 mL and a cone rotor TE-1 (1°34', R24) at a temperature of 25 ° C. is.

The polymer composition of the present invention may contain polymers other than the polymer (A) and other than the polyester (B). Specific examples of other polymers include polyesters other than polyester (B), polysiloxanes, polyamides, polyureas, polyorganosiloxanes, cellulose derivatives, polyacetals, polystyrene derivatives, and poly(styrene-maleic anhydride) copolymers. , poly(isobutylene-maleic anhydride) copolymer, poly(vinyl ether-maleic anhydride) copolymer, poly(styrene-phenylmaleimide) derivative, polymer selected from the group consisting of poly(meth)acrylate, etc. are mentioned. Specific examples of poly(styrene-maleic anhydride) copolymers include SMA1000, 2000, 3000 (manufactured by Cray Valley), GSM301 (manufactured by Gifu Shellac Co., Ltd.), etc. Poly(isobutylene-maleic anhydride) ) copolymers include Isoban-600 (manufactured by Kuraray Co., Ltd.), and specific examples of poly(vinyl ether-maleic anhydride) copolymers include GANTREZ AN-139 (methyl vinyl ether maleic anhydride resin , manufactured by ISP Japan).
Other polymers may be used singly or in combination of two or more. The content of other polymers is preferably 90 parts by mass or less, more preferably 10 to 90 parts by mass, and more preferably 20 to 80 parts by mass with respect to the total 100 parts by mass of the polymer contained in the polymer composition. More preferred.

The polymer composition according to the present invention is preferably a liquid composition in which the polymer (A) and polyester (B) are dissolved or dispersed in an organic solvent. Specifically, the organic solvent contained in the polymer composition is not particularly limited as long as it uniformly dissolves the polymer components, but N,N-dimethylformamide, N,N-dimethylacetamide, N , N-dimethyllactamide, N,N-dimethylpropionamide, tetramethylurea, N,N-diethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylsulfoxide, γ-butyrolactone, γ -valerolactone, 1,3-dimethyl-2-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, 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-3-methoxypropyl-2-pyrrolidone, N-(2-ethoxyethyl)-2-pyrrolidone, N-(4-methoxybutyl)-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone (these may be collectively referred to as a “good solvent”). Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide and γ-butyrolactone are preferred. The content of the good solvent is preferably 20 to 99% by mass, more preferably 20 to 90% by mass, particularly preferably 30 to 80% by mass, of the total solvent contained in the polymer composition.
The total content of the polymer (A) and the polyester (B) used in the present invention is preferably 1 to 100 parts by mass with respect to the total 100 parts by mass of the polymer contained in the liquid crystal aligning agent, and 10 to 100 parts by mass. 100 parts by mass is more preferable, and 20 to 100 parts by mass is particularly preferable.
Further, the total content of the polymer (A) and the polyester (B) may be 90 parts by mass or less, or 80 parts by mass or less with respect to the total 100 parts by mass of the polymer contained in the liquid crystal aligning agent. good.

In addition to the above solvents, the organic solvent contained in the polymer composition is a solvent (also referred to as a poor solvent) that improves the coatability and surface smoothness of the coating film when the polymer composition is applied. It is preferred to use a mixed solvent. Specific examples of the poor solvent used in combination are shown below, but are not limited thereto. The content of the poor solvent is preferably 1 to 80% by mass, more preferably 10 to 80% by mass, particularly preferably 20 to 70% by mass, of the total solvent contained in the polymer composition. The type and content of the poor solvent are appropriately selected according to the coating apparatus, coating conditions, coating environment, and the like of the polymer composition.

Examples of poor solvents include diisopropyl ether, diisobutyl ether, diisobutylcarbinol (2,6-dimethyl-4-heptanol), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, -hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol mono Acetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, 1-(2-butoxyethoxy) -2-propanol, 2-(2-butoxyethoxy)-1-propanol, propylene glycol monomethyl ether acetate, propylene glycol diacetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, propylene glycol diacetate, n-butyl acetate, acetic acid Propylene glycol monoethyl ether, cyclohexyl acetate, 4-methyl-2-pentyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionate Butyl acid, n-butyl lactate, isoamyl lactate, diethylene glycol monoethyl ether, diisobutyl ketone (2,6-dimethyl-4-heptanone) and the like.

Among them, diisobutyl carbinol, propylene glycol monobutyl ether, propylene glycol diacetate, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monobutyl ether, ethylene Glycol monobutyl ether acetate or diisobutyl ketone are preferred.

Preferred solvent combinations of a good solvent and a poor solvent include N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone and ethylene glycol monobutyl ether, N-methyl-2- Pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone, N-ethyl-2- pyrrolidone and propylene glycol diacetate, N,N-dimethyllactamide and diisobutyl ketone, N-methyl-2-pyrrolidone and ethyl 3-ethoxypropionate, N-ethyl-2-pyrrolidone and ethyl 3-ethoxypropionate, N- Methyl-2-pyrrolidone and ethyl 3-ethoxypropionate and dipropylene glycol monomethyl ether, N-ethyl-2-pyrrolidone and 3-ethoxyethyl propionate and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone and 3-ethoxy Ethyl Propionate and Diethylene Glycol Monopropyl Ether, N-Ethyl-2-Pyrrolidone and 3-Ethoxy Ethyl Propionate and Diethylene Glycol Monopropyl Ether, N-Methyl-2-Pyrrolidone and Ethylene Glycol Monobutyl Ether Acetate, N-Ethyl-2- Pyrrolidone and dipropylene glycol dimethyl ether, N,N-dimethyl lactamide and ethylene glycol monobutyl ether, N,N-dimethyl lactamide and propylene glycol diacetate, N-ethyl-2-pyrrolidone and diethylene glycol diethyl ether, N-ethyl-2 - pyrrolidone and diethylene glycol monoethyl ether and butyl cellosolve acetate, N-methyl-2-pyrrolidone and diethylene glycol monomethyl ether and butyl cellosolve acetate, N,N-dimethyllactamide and diethylene glycol diethyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone 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-ethyl-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 diisobutyl ketone, N-methyl-2-pyrrolidone and 4-hydroxy-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 ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and propylene glycol diacetate, N-ethyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and dipropylene glycol dimethyl ether, γ-butyrolactone and 4-hydroxy-4-methyl-2-pentanone and diisobutyl ketone, γ-butyrolactone and 4-hydroxy-4-methyl-2 -pentanone and propylene glycol diacetate, N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether and diisobutyl ketone, N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether and diisopropyl ether, N- Methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether and diisobutyl carbinol, N-methyl-2-pyrrolidone, γ-butyrolactone and dipropylene glycol dimethyl ether, N-methyl-2-pyrrolidone, propylene glycol monobutyl ether and diisobutyl carbinol Propylene glycol dimethyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether and dipropylene glycol monomethyl ether, N-ethyl-2-pyrrolidone and diethylene glycol diethyl ether and dipropylene glycol monomethyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether and propylene glycol diacetate, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether and diisobutyl ketone, N-ethyl-2-pyrrolidone and γ-butyrolactone and diisobutyl ketone, N-ethyl-2-pyrrolidone and N, N-dimethyl lactamide and diisobutyl ketone, N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether and ethylene glycol monobutyl ether acetate, γ-butyrolactone and ethylene glycol monobutyl ether acetate and dipropylene glycol dimethyl ether, N-ethyl-2 -pyrrolidone and ethylene glycol monobutyl ether acetate and propylene glycol dimethyl ether, N-methyl-2-pyrrolidone and 4-methyl-2-pentyl acetate and ethylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and cyclohexyl acetate and diacetone alcohol , N,N-dimethylpropionamide and 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylpropionamide and propylene glycol diacetate, tetramethylurea and 4-hydroxy-4-methyl-2-pentanone, Tetramethylurea and propylene glycol diacetate, N,N-dimethylpropionamide and propylene glycol monobutyl ether, Tetramethylurea and propylene glycol monobutyl ether, Tetramethylurea and cyclohexanone and propylene glycol monomethyl ether, N,N-dimethylpropionamide and Propylene glycol monomethyl ether, N,N-dimethylpropionamide and ethylene glycol monobutyl ether acetate, N,N-dimethylpropionamide and ethylene glycol monobutyl ether, Tetramethylurea and propylene glycol monomethyl ether, N,N-dimethylpropionamide and cyclohexanone and diethylene glycol diethyl ether, N,N-diethylformamide and propylene glycol monomethyl ether, N,N-diethylformamide and 4-hydroxy-4-methyl-2-pentanone, N,N-diethylformamide and propylene glycol monomethyl ether, cyclohexanone and Examples include propylene glycol monomethyl ether, cyclopentanone and propylene glycol monomethyl ether, N-methyl-2-pyrrolidone, cyclohexanone and propylene glycol monomethyl ether.

The polymer composition of the present invention may additionally contain components other than the polymer component and the organic solvent (hereinafter also referred to as additive components). Such additive components include, for example, crosslinkable compounds, functional silane compounds, metal chelate compounds, curing accelerators, surfactants, antioxidants, sensitizers, preservatives, dielectric constant and electrical resistance of resin films. A compound for adjustment and the like can be mentioned.
Examples of the crosslinkable compound include a crosslinkable compound (c-1) having at least one substituent selected from an epoxy group, an isocyanate group, an oxetanyl group, a cyclocarbonate group, a blocked isocyanate group, a hydroxy group and an alkoxy group. , and at least one crosslinkable compound selected from the group consisting of the crosslinkable compound (c-2) having a polymerizable unsaturated group.
By containing the crosslinkable compound, it is possible to obtain a liquid crystal display element in which the occurrence of so-called flicker or the like, which occurs when the liquid crystal display element is irradiated with backlight immediately after the liquid crystal is driven, is reduced. You can also get the effect of being able to do it.

Preferred specific examples of the crosslinkable compounds (c-1) and (c-2) include the following compounds.
Examples of the epoxy group-containing compound (c-1) include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, Epicoat 828 (manufactured by Mitsubishi Chemical Corporation), etc. bisphenol A type epoxy resin, bisphenol F type epoxy resin such as Epicoat 807 (manufactured by Mitsubishi Chemical Corporation), hydrogenated bisphenol A type epoxy resin such as YX-8000 (manufactured by Mitsubishi Chemical Corporation), YX6954BH30 (manufactured by Mitsubishi Chemical Corporation), etc. biphenyl skeleton-containing epoxy resins, EPPN-201 (manufactured by Nippon Kayaku Co., Ltd.) and other phenol novolac-type epoxy resins, and EOCN-102S (manufactured by Nippon Kayaku Co., Ltd.) and other (o, m, p-) cresol novolac-type epoxy resins. , tetrakis(glycidyloxymethyl)methane, N,N,N′,N′-tetraglycidyl-1,4-phenylenediamine, N,N,N′,N′-tetraglycidyl-2,2′-dimethyl-4 .4'-diaminobiphenyl, 2,2-bis[4-(N,N-diglycidyl-4-aminophenoxy)phenyl]propane, N,N,N',N'-tetraglycidyl-4,4'-diamino Compounds in which a tertiary nitrogen atom is bound to an aromatic carbon atom such as diphenylmethane; N,N,N',N'-tetraglycidyl-1,2-diaminocyclohexane, N,N,N',N'-tetraglycidyl -1,3-diaminocyclohexane, N,N,N',N'-tetraglycidyl-1,4-diaminocyclohexane, bis(N,N-diglycidyl-4-aminocyclohexyl)methane, bis(N,N-diglycidyl) -2-methyl-4-aminocyclohexyl)methane, bis(N,N-diglycidyl-3-methyl-4-aminocyclohexyl)methane, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, 1, 4-bis(N,N-diglycidylaminomethyl)cyclohexane, 1,3-bis(N,N-diglycidylaminomethyl)benzene, 1,4-bis(N,N-diglycidylaminomethyl)benzene, 1 , 3,5-tris(N,N-diglycidylaminomethyl)cyclohexane, 1,3,5-tris(N,N-diglycidylaminomethyl)benzene, etc. where the tertiary nitrogen atom is bonded to the aliphatic carbon atom compounds, isocyanurate compounds such as triglycidyl isocyanurate such as TEPIC (manufactured by Nissan Chemical Industries, Ltd.), compounds described in paragraph [0037] of JP-A-10-338880, compounds described in WO2017/170483, etc. ;
As the compound having an isocyanate group, the diisocyanate compound described above;
As the compound (c-1) having an oxetanyl group, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene (arone oxetane OXT-121 (XDO)), di[2-(3 -oxetanyl)butyl] ether (aron oxetane OXT-221 (DOX)), 1,4-bis[(3-ethyloxetane-3-yl)methoxy]benzene (HQOX), 1,3-bis[(3-ethyl Oxetan-3-yl)methoxy]benzene (RSOX), 1,2-bis[(3-ethyloxetan-3-yl)methoxy]benzene (CTOX), paragraphs [0170] to [0175] of WO2011/132751 compounds having two or more oxetanyl groups according to;
N,N,N',N'-tetrakis[(2-oxo-1,3-dioxolan-4-yl)methyl]-4,4'-diaminodiphenylmethane as the compound (c-1) having a cyclocarbonate group , N,N'-bis[(2-oxo-1,3-dioxolan-4-yl)methyl]-1,3-phenylenediamine and compounds described in WO2011/155577;
Examples of compounds having a blocked isocyanate group include Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (manufactured by Tosoh Corporation), Takenate B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (manufactured by Mitsui Chemicals, Inc.), two pieces described in paragraphs [0046] to [0047] of Japanese Patent Application Laid-Open No. 2014-224978 compounds having the above protected isocyanate groups, compounds having three or more protected isocyanate groups described in paragraphs [0119] to [0120] of WO2015/141598;
As the compound (c-1) having a hydroxy group and/or an alkoxy group, N,N,N',N'-tetrakis(2-hydroxyethyl)adipamide, 2,2-bis(4-hydroxy-3,5- dihydroxymethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethoxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)-1,1,1, 3,3,3-hexafluoropropane, WO 2015/072554, the compound described in paragraph [0058] of JP 2016-118753, the compound described in JP 2016-200798, WO2010 / 074269 compounds and the like;
As the crosslinkable compound (c-2) having a polymerizable unsaturated group, glycerin mono(meth)acrylate, glycerin di(meth)acrylate (1,2-, 1,3-body mixture), glycerin tris(meth)acrylate , glycerol 1,3-diglycerolate di(meth)acrylate, pentaerythritol tri(meth)acrylate, diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, tetraethylene glycol mono(meth)acrylate, penta ethylene glycol mono(meth)acrylate, hexaethylene glycol mono(meth)acrylate and the like.

The crosslinkable compounds (c-1) and (c-2) are, among others, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidyl aminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, Takenate B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N , B-874N, B-882N, 1,3,5-tris(2-hydroxyethyl)isocyanurate, triglycidyl isocyanurate, N,N,N′,N′-tetrakis(2-hydroxyethyl)adipamide, 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethoxymethylphenyl)propane, 2,2-bis(4-hydroxy- 3,5-dihydroxymethylphenyl)-1,1,1,3,3,3-hexafluoropropane is preferred.

The above are examples of crosslinkable compounds, and are not limited to these. Moreover, the crosslinkable compound used in the polymer composition of the present invention may be of one type or a combination of two or more types.
The content of the crosslinkable compound in the polymer composition of the present invention is 0.1 to 150 parts by mass, or 0.1 to 100 parts by mass, or 1 to 50 parts by mass with respect to 100 parts by mass of all polymer components. part by mass.

Examples of compounds for adjusting the dielectric constant and electrical resistance of the resin film include monoamines having a nitrogen atom-containing aromatic heterocycle such as 3-picolylamine. When a monoamine having a nitrogen-containing aromatic heterocycle is used, it is preferably 0.1 to 30 parts by mass, more preferably 0.1 part by mass with respect to 100 parts by mass of the polymer component contained in the polymer composition. ~20 parts by mass.

Preferred specific examples of functional silane compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane. Silane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxy silane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxysilane sidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, ethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, tris(3-trimethoxysilylpropyl)isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3 -isocyanatopropyltriethoxysilane and the like. When a functional silane compound is used, the amount used is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 30 parts by mass, based on 100 parts by mass of the polymer component contained in the polymer composition. 20 parts by mass.

The solid content concentration in the polymer composition (ratio of the total mass of components other than the solvent of the polymer composition to the total mass of the polymer composition) is appropriately selected in consideration of viscosity, volatility, etc. , preferably in the range of 1 to 10 mass %. That is, the polymer composition is applied to the surface of the substrate as described later, and preferably heated to form a resin film.

A particularly preferred solid content concentration range varies depending on the method used to apply the polymer composition to the substrate. For example, when a spin coating method is used, the solid content concentration is particularly preferably in the range of 1.5 to 4.5% by mass. When the printing method is used, 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 ink jet 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. The temperature in preparing the polymer composition is preferably 10-50°C, more preferably 20-30°C.

<Application and resin film>
The polymer composition described above can be applied, for example, onto a substrate and preferably subjected to heat treatment to volatilize the solvent component, thereby forming a resin film. The polymer composition and resin film according to the present invention can be effectively applied to various technical applications, such as liquid crystal aligning agents, electronic circuit materials, semiconductor materials, electrical insulation materials, wire coating materials, lighting applications, and molding. It can be applied to various uses such as materials. Specifically, it can be applied to various resin films including display elements, semiconductor elements, actuators such as motors, various sensors such as piezoelectric sensors and pyroelectric sensors, and liquid crystal alignment films (liquid crystal alignment films for retardation films). , liquid crystal alignment films for scanning antennas and liquid crystal array antennas, or liquid crystal alignment films for transmission scattering type liquid crystal light control elements), protective films (e.g. protective films for color filters), spacer films, interlayer insulating films, antireflection films, wiring coating films, antistatic films, electric motor insulating films (gate insulating films of flexible displays), and the like. Among these, the polymer composition according to the present invention can be preferably applied as a liquid crystal aligning agent.

<Liquid crystal aligning agent>
The liquid crystal aligning agent according to the present invention comprises the polymer composition according to the present invention. That is, the liquid crystal aligning agent which concerns on this invention contains the said polymer (A) and polyester (B) similarly to a polymer composition. Moreover, it is preferable to contain at least one of other polymers, organic solvents and additive components. For specific examples of the polymer (A), polyester (B), other polymers, organic solvents, and additive components, the blending ratio, solid content concentration, etc., the description of the polymer composition is applied. be able to.

[Liquid crystal alignment film and liquid crystal display element]
A liquid crystal alignment film can be manufactured as a resin film by using the said polymer composition or the said liquid crystal aligning agent. Moreover, the liquid crystal display element which concerns on this invention comprises the liquid crystal aligning film formed using the said polymer composition or said liquid crystal aligning agent. The operation mode of the liquid crystal display device according to the present invention is not particularly limited. It can be applied to various operation modes such as type (IPS type), FFS type, and optical compensation bend type (OCB type).

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

<Step (1): Step of applying a liquid crystal aligning agent onto a substrate>
A process (1) is a process of apply|coating the liquid crystal aligning agent of this invention on a board|substrate. A specific example of step (1) is as follows.
The liquid crystal aligning agent of the present invention is applied to one surface of the substrate provided with the patterned transparent conductive film by an appropriate coating method such as a roll coater method, a spin coat method, a printing method, an inkjet method, or the like. Here, the substrate is not particularly limited as long as it is highly transparent, and in addition to a glass substrate and a silicon nitride substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate can also be used. In addition, in the reflective liquid crystal display element, if only one substrate is used, an opaque material such as a silicon wafer can be used, and in this case, a light-reflecting material such as aluminum can be used for the electrodes. In the case of manufacturing an IPS-type or FFS-type liquid crystal display element, a substrate provided with electrodes made of a transparent conductive film or a metal film patterned in a comb shape and a counter substrate provided with no electrodes are used. and

Screen printing, offset printing, flexographic printing, inkjet method, spray method, etc., can be used as methods for applying the liquid crystal aligning agent to the substrate and forming a film. Among them, the coating method and the film-forming method by the inkjet method can be preferably used.

<Step (2): Step of firing 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|membrane. A specific example of step (2) is as follows.
After the liquid crystal aligning agent is applied onto the substrate in step (1), a heating means such as a hot plate, thermal circulation oven or IR (infrared) oven is used to evaporate the solvent or heat the polyamic acid or polyamic acid ester. Thermal imidization can be performed. The drying and baking steps after applying the liquid crystal aligning agent of the present invention can be performed at any desired temperature and time, and may be performed multiple times. The temperature for reducing the solvent of the liquid crystal aligning agent can be, for example, 40 to 180°C. From the viewpoint of shortening the process, it may be carried out at 40 to 150°C. The firing time is not particularly limited, but may be 1 to 10 minutes or 1 to 5 minutes. When thermal imidization of polyamic acid or polyamic acid ester is performed, a step of baking at a temperature range of 150 to 300° C. or 150 to 250° C. may be added after the above step. The firing time is not particularly limited, but may be 5 to 40 minutes or 5 to 30 minutes.
The thickness of the film-like material after baking is preferably 5 to 300 nm, more preferably 10 to 200 nm, because if it is too thin, the reliability of the liquid crystal display element may be lowered.

<Step (3): Step of subjecting the film obtained in Step (2) to orientation treatment>
Step (3) is a step of subjecting the film obtained in step (2) to orientation treatment. That is, in a horizontally aligned liquid crystal display element such as an IPS system or an FFS system, the coating film is subjected to an alignment ability imparting treatment. On the other hand, in a vertical alignment type liquid crystal display element such as VA mode or PSA mode, the formed coating film can be used as a liquid crystal alignment film as it is, but the coating film may be subjected to an alignment ability imparting treatment. Examples of the alignment treatment method for the liquid crystal alignment film include a rubbing treatment method and a photo-alignment treatment method. As the photo-alignment treatment method, the surface of the film-like material is irradiated with radiation polarized in a certain direction, and in some cases, heat treatment is performed to impart liquid crystal alignment (also referred to as liquid crystal alignment ability). be done. As radiation, ultraviolet light or visible light having a wavelength of 100 to 800 nm can be used. Among them, ultraviolet rays having a wavelength of 100 to 400 nm, more preferably 200 to 400 nm are preferred.

The radiation dose is preferably 1 to 10,000 mJ/cm ² , more preferably 100 to 5,000 mJ/cm ² . In the case of irradiation with radiation, the substrate having the film-like material may be irradiated while being heated at 50 to 250° C. in order to improve liquid crystal orientation. The liquid crystal alignment film thus produced can stably orient liquid crystal molecules in a fixed direction.
Furthermore, the liquid crystal alignment film irradiated with polarized radiation can be subjected to contact treatment using water or a solvent, or the liquid crystal alignment film irradiated with radiation can be heat-treated.

The solvent used in the contact treatment is not particularly limited as long as it dissolves the decomposed product produced from the film-like material 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, 3- methyl methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, cyclohexyl acetate and the like. Among them, water, 2-propanol, 1-methoxy-2-propanol and ethyl lactate are preferred, and water, 1-methoxy-2-propanol and ethyl lactate are more preferred, from the viewpoint of versatility and solvent safety. Solvents may be used singly or in combination of two or more.

The temperature of the heat treatment for the above radiation-irradiated coating film is more preferably 50 to 300°C, more preferably 120 to 250°C. The heat treatment time is preferably 1 to 30 minutes.

<Step (4): Step of producing a liquid crystal cell>
Two substrates on which liquid crystal alignment films are formed as described above are prepared, and liquid crystal is arranged between the two substrates facing each other. Specifically, the following two methods are mentioned.
In the first method, first, two substrates are arranged to face each other with a gap (cell gap) interposed therebetween so that the respective liquid crystal alignment films face each other. Next, the peripheries of the two substrates are bonded together using a sealing agent, and a liquid crystal composition is injected and filled into the cell gap defined by the substrate surface and the sealing agent to contact the film surface, and then the injection hole is sealed. stop.
The liquid crystal composition is not particularly limited, and various liquid crystal compositions containing at least one liquid crystal compound (liquid crystal molecule) and having positive or negative dielectric anisotropy can be used. In the following description, a liquid crystal composition with a positive dielectric anisotropy is also referred to as a positive liquid crystal, and a liquid crystal composition with a negative dielectric anisotropy is also referred to as a negative liquid crystal.
The above liquid crystal composition contains a fluorine atom, a hydroxy group, an amino group, a fluorine atom-containing group (e.g., trifluoromethyl group), a cyano group, an alkyl group, an alkoxy group, an alkenyl group, an isothiocyanate group, a heterocyclic ring, a cycloalkane, A liquid crystal compound having a cycloalkene, a steroid skeleton, a benzene ring, or a naphthalene ring may be included, and a compound having two or more rigid sites (mesogenic skeleton) exhibiting liquid crystallinity in the molecule (for example, two rigid biphenyl structure, or a bimesogenic compound in which a terphenyl structure is linked by an alkyl group). The liquid crystal composition may be a liquid crystal composition exhibiting a nematic phase, a liquid crystal composition exhibiting a smectic phase, or a liquid crystal composition exhibiting a cholesteric phase.
In addition, the liquid crystal composition may further contain an additive from the viewpoint of improving liquid crystal orientation. Such additives include photopolymerizable monomers such as compounds having a polymerizable group (meth(a)acryloyl group, etc.); optically active compounds (eg, S-811 manufactured by Merck Co., Ltd.); Antioxidants; ultraviolet absorbers; dyes; antifoaming agents; polymerization initiators;
Positive liquid crystals include ZLI-2293, ZLI-4792, MLC-2003, MLC-2041, MLC-3019 and MLC-7081 manufactured by Merck.
As the negative liquid crystal, for example, MLC-6608, MLC-6609, MLC-6610, MLC-6882, MLC-6886, MLC-7026, MLC-7026-000, MLC-7026-100, or MLC- 7029 and the like.
In addition, in the PSA mode, MLC-3023 manufactured by Merck Co., Ltd. can be used as a liquid crystal containing a compound having a polymerizable group.

The second method is a method called ODF (One Drop Fill) method. A predetermined place on one of the two substrates on which the liquid crystal alignment film is formed is coated with, for example, an ultraviolet light-curing sealant, and a liquid crystal composition is applied to several predetermined places on the surface of the liquid crystal alignment film. drip. Thereafter, the other substrate is attached so that the liquid crystal alignment films face each other, and the liquid crystal composition is spread over the entire surface of the substrate and brought into contact with the film surface. Next, the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant. In any method, it is desirable to remove the flow orientation at the time of liquid crystal filling by heating to a temperature at which the liquid crystal composition used takes an isotropic phase and then slowly cooling to room temperature.
When the coating film is subjected to the rubbing treatment, the two substrates are arranged opposite to each other so that the rubbing directions of the respective coating films are at a predetermined angle, for example, orthogonal or antiparallel.
As the sealant, for example, an epoxy resin or the like containing aluminum oxide spheres as a curing agent and a spacer can be used. Liquid crystals include nematic liquid crystals and smectic liquid crystals, among which nematic liquid crystals are preferred.

The liquid crystal aligning agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and a liquid crystal composition containing a polymerizable compound polymerized by at least one of active energy rays and heat between the pair of substrates. A liquid crystal display element (PSA type liquid crystal display element) manufactured through a process of polymerizing a polymerizable compound by at least one of irradiating an active energy ray and heating while placing an object and applying a voltage between electrodes. It is preferably used.
Further, the liquid crystal aligning agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and a polymerizable group polymerized by at least one of active energy rays and heat is placed between the pair of substrates. It is also preferably used in a liquid crystal display element (SC-PVA mode type liquid crystal display element) manufactured through a process of arranging a liquid crystal alignment film containing a liquid crystal and applying a voltage between electrodes.

<Step (4-2): For PSA type liquid crystal display element>
The procedure is the same as in (4) above except that a liquid crystal composition containing a polymerizable compound is injected or dropped. Examples of the polymerizable compound include polymerizable compounds having one or more polymerizable unsaturated groups such as acrylate groups and methacrylate groups in the molecule.

<Step (4-3): For SC-PVA mode liquid crystal display element>
A method of manufacturing a liquid crystal display element may be employed in which a step of irradiating ultraviolet rays, which will be described later, is performed after performing the same as in (4) above. According to this method, a liquid crystal display device excellent in response speed can be obtained with a small amount of light irradiation, as in the case of manufacturing the PSA type liquid crystal display device. The compound having a polymerizable group may be a compound having one or more polymerizable unsaturated groups in the molecule, and its content is 0.1 to 30 per 100 parts by mass of all polymer components. It is preferably parts by mass, more preferably 1 to 20 parts by mass. Further, the polymerizable group may be possessed by the polymer used for the liquid crystal aligning agent, and such a polymer includes, for example, a diamine component containing a diamine having the photopolymerizable group at its end, and used for the reaction. The polymer obtained is mentioned.

<Step (4-4): Step of irradiating with ultraviolet rays>
The liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates obtained in (4-2) or (4-3) above. The voltage applied here can be, for example, 5 to 50 V direct current or alternating current. As the light to be irradiated, for example, ultraviolet rays and visible rays containing light having a wavelength of 150 to 800 nm can be used, but ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferable. As a 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. The irradiation amount of light is preferably 1,000 to 200,000 J/m ² , more preferably 1,000 to 100,000 J/m ² .

Then, a liquid crystal display element can be obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell as necessary. As the polarizing plate to be attached to the outer surface of the liquid crystal cell, a polarizing film called "H film" in which polyvinyl alcohol is stretched and oriented while absorbing iodine is sandwiched between cellulose acetate protective films, or the H film itself. A polarizing plate consisting of

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.

EXAMPLES The present invention will be specifically described below with reference to examples, etc., but the present invention is not limited to these examples. Abbreviations of compounds and solvents are as follows.
(organic solvent)
NMP: N-methyl-2-pyrrolidone GBL: γ-butyrolactone BCS: ethylene glycol monobutyl ether (diamine)
DA-1 to DA-3: Compounds (tetracarboxylic dianhydrides) represented by the following formulas (DA-1) to (DA-3), respectively
CA-1 to CA-2: compounds (diisocyanates) represented by the following formulas (CA-1) to (CA-2), respectively
DI-1: 4,4'-diphenylmethane diisocyanate (diol)
EG-1: Polyethylene Glycol 600 (manufactured by Tokyo Chemical Industry Co., Ltd.)
(Additive)
AD-1: a compound represented by the following formula (AD-1)

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

[Synthesis of polymer]
(Synthesis example 1)
DA-1 (4.81 g, 16.8 mmol), DA-3 (1.25 g, 4.20 mmol), NMP (27.3 g) and GBL (27 .3 g) was weighed out and dissolved by stirring with nitrogen sparging. While stirring this diamine solution under water cooling, CA-1 (3.83 g, 19.5 mmol), NMP (17.2 g) and GBL (17.2 g) were added and stirred for 2 hours under a nitrogen atmosphere. , to obtain a polyamic acid solution (PAA-1) (viscosity: 108 mPa·s).
(Synthesis example 2)
DA-1 (3.15 g, 11.0 mmol), DA-2 (2.69 g, 11.0 mmol), NMP (26.3 g) and GBL (26 .3 g) was weighed out and dissolved by stirring with nitrogen sparging. While stirring this diamine solution under water cooling, CA-1 (4.01 g, 20.5 mmol), NMP (18.1 g) and GBL (18.1 g) were added and stirred for 2 hours under a nitrogen atmosphere. , to obtain a polyamic acid solution (PAA-2) (viscosity: 119 mPa·s).
(Synthesis Example 3)
EG-1 (15.0 g, 25.0 mmol), NMP (11.3 g) and GBL (11.3 g) were weighed into a 100 mL eggplant flask equipped with a stirrer and a nitrogen inlet tube, and stirred while supplying nitrogen. to dissolve. While stirring this diamine solution under water cooling, CA-2 (4.09 g, 18.8 mmol), NMP (3.07 g) and GBL (3.07 g) were added and stirred at 70° C. for 20 hours under a nitrogen atmosphere. . Then, DI-1 (1.38 g, 5.50 mmol), NMP (1.03 g) and GBL (1.03 g) were added and stirred at 23° C. for 6 hours under a nitrogen atmosphere to obtain a polymer solution. (Viscosity: 423 mPa·s).
Dispense the polymer solution (5.0 g) obtained above into a 30 mL Erlenmeyer flask equipped with a stirrer, add NMP (7.5 g) and GBL (7.5 g), and stir at room temperature for 2 hours. Thus, a diluted polymer solution (Polymer-1) was obtained.
(Synthesis Example 4)
EG-1 (15.0 g, 25.0 mmol), NMP (11.3 g) and GBL (11.3 g) were weighed into a 100 mL eggplant flask equipped with a stirrer and a nitrogen inlet tube, and stirred while supplying nitrogen. to dissolve. While stirring this diamine solution under water cooling, CA-2 (2.73 g, 12.5 mmol), NMP (2.04 g) and GBL (2.04 g) were added and stirred at 70° C. for 20 hours under a nitrogen atmosphere. . Then, DI-1 (2.94 g, 11.8 mmol), NMP (1.03 g) and GBL (1.03 g) were added and stirred at 23° C. for 6 hours under a nitrogen atmosphere to obtain a polymer solution. (Viscosity: 520 mPa·s).
Dispense the polymer solution (5.0 g) obtained above into a 30 mL Erlenmeyer flask equipped with a stirrer, add NMP (7.5 g) and GBL (7.5 g), and stir at room temperature for 2 hours. Thus, a diluted polymer solution (Polymer-2) was obtained.
(Synthesis Example 5)
EG-1 (15.0 g, 25.0 mmol), NMP (11.3 g) and GBL (11.3 g) were weighed into a 100 mL eggplant flask equipped with a stirrer and a nitrogen inlet tube, and stirred while supplying nitrogen. to dissolve. While stirring this diamine solution under water cooling, CA-2 (1.64 g, 7.50 mmol), NMP (1.23 g) and GBL (1.23 g) were added and stirred at 70° C. for 20 hours under a nitrogen atmosphere. . Then, DI-1 (4.19 g, 16.8 mmol), NMP (3.14 g) and GBL (3.14 g) were added and stirred at 23° C. for 6 hours under a nitrogen atmosphere to obtain a polymer solution. (Viscosity: 367 mPa·s).
Dispense the polymer solution (5.0 g) obtained above into a 30 mL Erlenmeyer flask equipped with a stirrer, add NMP (7.5 g) and GBL (7.5 g), and stir at room temperature for 2 hours. Thus, a diluted polymer solution (Polymer-3) was obtained.
(Synthesis Example 6)
EG-1 (15.0 g, 25.0 mmol), NMP (11.3 g) and GBL (11.3 g) were weighed into a 100 mL eggplant flask equipped with a stirrer and a nitrogen inlet tube, and stirred while supplying nitrogen. to dissolve. While stirring this diamine solution under water cooling, CA-2 (0.82 g, 3.75 mmol), NMP (0.61 g) and GBL (0.61 g) were added and stirred at 70° C. for 20 hours under a nitrogen atmosphere. . Then, DI-1 (5.13 g, 20.5 mmol), NMP (3.85 g) and GBL (3.85 g) were added and stirred at 23° C. for 6 hours under a nitrogen atmosphere to obtain a polymer solution. (Viscosity: 1120 mPa·s).
Dispense the polymer solution (5.0 g) obtained above into a 30 mL Erlenmeyer flask equipped with a stirrer, add NMP (7.5 g) and GBL (7.5 g), and stir at room temperature for 2 hours. Thus, a diluted polymer solution (Polymer-4) was obtained.
(Synthesis Example 7)
EG-1 (15.0 g, 25.0 mmol), NMP (11.3 g) and GBL (11.3 g) were weighed into a 100 mL eggplant flask equipped with a stirrer and a nitrogen inlet tube, and stirred while supplying nitrogen. to dissolve. While stirring this diamine solution under water cooling, CA-2 (5.34 g, 24.5 mmol), NMP (4.00 g) and GBL (4.00 g) are added and stirred at 70° C. for 20 hours under nitrogen atmosphere. Thus, a polymer solution was obtained (viscosity: 375 mPa·s).
Dispense the polymer solution (5.0 g) obtained above into a 30 mL Erlenmeyer flask equipped with a stirrer, add NMP (7.5 g) and GBL (7.5 g), and stir at room temperature for 2 hours. Thus, a diluted polymer solution (Polymer-5) was obtained.
Table 1 shows specifications of the polymer solutions obtained in the above synthesis examples. In Table 1, the numbers in parentheses for the solvent composition represent the amount (parts by mass) of each solvent with respect to a total of 100 parts by mass of the solvents in each solution.

[Preparation of Liquid Crystal Aligning Agent]
(Example 1)
A 50 mL Erlenmeyer flask containing a stirrer was charged with the polyamic acid solution (PAA-1) (6.00 g) obtained in Synthesis Example 1 and the diluted solution of the polymer obtained in Synthesis Example 3 (Polymer-1) (0 .48 g), NMP (1.31 g), GBL (3.91 g), BCS (4.00 g), and NMP solution (additive solution) (0.30 g) containing 10% by mass of AD-1 The liquid crystal aligning agent (1) was obtained by adding and stirring at room temperature for 2 hours.

(Examples 2-10, Comparative Examples 1-2)
Liquid crystal aligning agents (2) to (12) were obtained in the same manner as in Example 1, except that the types and amounts of the polymer solution and solvent used were changed as shown in Table 2 below.

[Fabrication of FFS driven liquid crystal cell]
A liquid crystal cell having a configuration of a fringe field switching (FFS) mode liquid crystal display element was produced.
First, a substrate with electrodes was prepared. A glass substrate having a size of 30 mm×35 mm and a thickness of 0.7 mm was used as the substrate. An ITO electrode having a solid pattern is formed on the substrate as a first layer to form a counter electrode, and a CVD (chemical vapor deposition) electrode is formed as a second layer on the first layer counter electrode. A SiN (silicon nitride) film formed by the method was formed. The SiN film of the second layer has a film thickness of 300 nm and functions as an interlayer insulating film. On the SiN film of the second layer, a comb-shaped pixel electrode formed by patterning an ITO film is arranged as a third layer, and two pixels of a first pixel and a second pixel are formed. The size of each pixel was 10 mm long and about 5 mm wide. At this time, the counter electrode of the first layer and the pixel electrode of the third layer were electrically insulated by the action of the SiN film of the second layer.
The pixel electrode of the third layer has a comb shape in which a plurality of electrode elements each having a width of 3 μm and having a central portion bent at an internal angle of 160° are arranged in parallel with an interval of 6 μm. Each pixel had a first region and a second region bounded by a line connecting bent portions of a plurality of electrode elements.
Comparing the first region and the second region of each pixel, the forming directions of the electrode elements of the pixel electrodes constituting them were different. That is, when the direction connecting the bent portions of the plurality of electrode elements is taken as a reference, the electrode elements of the pixel electrode are formed so as to form an angle of 80° clockwise in the first region of the pixel, and the electrode elements of the pixel electrode are formed in the second region of the pixel. The electrode elements of the pixel electrode are formed so as to form an angle of 80° counterclockwise. That is, in the first region and the second region of each pixel, the directions of the rotational movement (in-plane switching) of the liquid crystal induced by the voltage application between the pixel electrode and the counter electrode in the plane of the substrate are mutually different. It was configured in the opposite direction.
Next, after filtering the liquid crystal aligning agent obtained above with a filter having a pore size of 1.0 μm, an ITO film is formed on the surface and the back surface of the substrate with electrodes (first glass substrate) prepared above. It was applied to the surface of a glass substrate (second glass substrate) having columnar spacers with a height of 4 μm, by a spin coating method. Then, after drying on a hot plate at 80° C. for 5 minutes, baking was performed in a hot air circulating oven at 230° C. for 20 minutes to obtain a polyimide film with a thickness of 100 nm. This polyimide film is rubbed with a rayon cloth (Yoshikawa Kako, YA-20R) (roller diameter: 120 mm, roller rotation speed: 500 rpm, moving speed: 30 mm / sec, indentation length: 0.3 mm, rubbing direction: 3rd layer 180° to the direction connecting the bent portions of the plurality of electrode elements of the pixel electrode of the eye), ultrasonic irradiation is performed for 1 minute in pure water for cleaning, and water droplets are removed by air blow. bottom. Then, it dried for 15 minutes on an 80 degreeC hotplate, and obtained the board|substrate with a liquid crystal aligning film. These two substrates with a liquid crystal alignment film are used as one set, and a sealant (XN-1500T manufactured by Mitsui Chemicals, Inc.) is printed on the substrate with the liquid crystal injection port left. They were laminated so that the surfaces faced each other and the rubbing directions were anti-parallel. After that, a heat treatment was performed at 150° C. for 60 minutes to cure the sealant, thereby producing an empty cell with a cell gap of 4 μm. A negative type liquid crystal MLC-7026-100 (manufactured by Merck & Co.) was injected into this empty cell by a vacuum injection method, and the injection port was sealed to obtain an FFS liquid crystal cell. After that, the obtained liquid crystal cell was heated at 120° C. for 1 hour and allowed to stand at 23° C. overnight before being used for evaluation.
[Evaluation of alignment stability by long-term AC drive]
This evaluation evaluates afterimages (also referred to as AC afterimages) caused by deterioration of the alignment performance of the liquid crystal alignment film during long-term AC driving.
Using the liquid crystal cell produced above, an AC voltage of ±12 V was applied at a frequency of 60 Hz for 120 hours on a high-brightness backlight (luminous intensity: 20000 cd/m ² ) having a surface temperature of 50°C. After that, the pixel electrode and the counter electrode of the liquid crystal cell were short-circuited and left at room temperature for one day. After standing, the liquid crystal cell is placed between two polarizing plates arranged so that the polarizing axes are orthogonal to each other, the backlight is turned on with no voltage applied, and the transmitted light of the first region of the first pixel is obtained. The angle of rotation required when the arrangement angle of the liquid crystal cell is adjusted so that the intensity is minimized and then the liquid crystal cell is rotated so that the transmitted light intensity of the second region of the first pixel is minimized is defined as the angle Δθ. Calculated. Similarly, for the second pixel, the first region and the second region were compared to calculate a similar angle Δθ. Then, the average value of the angle Δθ between the first pixel and the second pixel was calculated as the rotation angle Δθ of the liquid crystal cell. It can be said that the smaller the rotation angle Δθ, the better the stability of the liquid crystal alignment. As evaluation criteria, if the value of the rotation angle Δθ of the liquid crystal cell obtained above is 0.10 degrees or less, "◯", if it exceeds 0.10 degrees and is 0.20 degrees or less, "Δ", When exceeding 0.20 degrees, it was evaluated as "x". Table 3 shows the results.
[Preparation of liquid crystal cell for pretilt angle evaluation]
First, a substrate with electrodes was prepared. The substrate is a glass substrate with a size of 30 mm×40 mm and a thickness of 1.1 mm. An ITO electrode having a film thickness of 35 nm was formed on the substrate, and the electrode had a stripe pattern with an interval of 40 mm in length and 10 mm in width.
Next, each of the liquid crystal aligning agents obtained above was filtered through a filter having a pore size of 1.0 μm, and then applied to the electrode-attached substrate prepared above by a spin coating method. Then, after drying on a hot plate at 80° C. for 2 minutes, baking was performed in an infrared heating furnace at 230° C. for 20 minutes to form a coating film having a thickness of 100 nm to obtain a substrate with a liquid crystal alignment film. After rubbing the liquid crystal alignment film with a rayon cloth (manufactured by Yoshikawa Kako, YA-20R) (roller diameter: 120 mm, roller rotation speed: 1000 rpm, moving speed: 20 mm / sec, pushing length: 0.4 mm), pure water The substrate was cleaned by irradiating ultrasonic waves for 1 minute inside, water droplets were removed by an air blow, and dried at 80° C. for 10 minutes to obtain a substrate with a liquid crystal alignment film. Two substrates with the liquid crystal alignment film were prepared, and spherical spacers with a particle size of 4 μm were sprayed on the surface of one of the liquid crystal alignment films. 1500T) was printed thereon, and another substrate was pasted with the rubbing direction reversed and the film surfaces facing each other. After that, a heat treatment was performed at 150° C. for 60 minutes to cure the sealant to prepare an empty cell. A negative type liquid crystal MLC-7026 (manufactured by Merck & Co.) was injected into this empty cell by a vacuum injection method, and the injection port was sealed to obtain a liquid crystal cell. After that, the obtained liquid crystal cell was heated at 120° C. for 1 hour and allowed to stand at 23° C. overnight before being used for each evaluation.
[Measurement of pretilt angle]
A pretilt angle in the liquid crystal cell was measured using an AxoScan Muller matrix polarimeter manufactured by Optometrics. The lower the pretilt angle value, the better. Table 3 shows the results.

A pretilt angle of 1.5 degrees or less was obtained by using the liquid crystal aligning agent of the example of the present invention. Moreover, normally, when a negative liquid crystal is used as a liquid crystal material, it is difficult to obtain good liquid crystal orientation, but by using the liquid crystal aligning agent of the example of the present invention, when a negative liquid crystal is used as a liquid crystal material, However, a liquid crystal display element having good liquid crystal orientation (that is, having excellent AC afterimage properties) was obtained.

In addition, the entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2021-176518 filed on October 28, 2021 are cited here, and as a disclosure of the specification of the present invention, It is taken in.

Claims

A polymer composition characterized by containing the following components (A) and (B).
Component (A): At least one polymer (A) selected from the group consisting of a polyimide precursor having a repeating unit represented by the following formula (a) and a polyimide which is an imidized product of the polyimide precursor.
Component (B): Polyester (B) which has a repeating unit represented by the following formula (b1) and does not have a repeating unit represented by the above formula (a) and its imidized structure.

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

(X ar represents a tetravalent organic group derived from an aromatic tetracarboxylic dianhydride or a derivative thereof. Each of the two R independently represents a hydrogen atom or a monovalent organic group. E is A divalent organic group obtained by removing hydrogen atoms contained in two hydroxy groups from an organic diol, wherein the organic diol contains a divalent organic group represented by the following formula (EG).)

(n is an integer of 5 or more. R represents a hydrogen atom or a methyl group.)
The polymer composition according to claim 1, wherein n is an integer of 5 to 40 in the formula (EG).
The polymer composition according to claim 1 or 2, wherein the organic diol in formula (b1) is a diol in which hydrogen atoms are bonded to both ends of the divalent organic group represented by formula (EG).
X ar in the formula (b1) is a tetravalent organic group derived from a tetracarboxylic dianhydride represented by the following formula (t) or a derivative thereof, according to any one of claims 1 to 3 The polymer composition described.

(In the formula, X 1 is a structure selected from the following formulas (X1-24) and (X1-25). * represents a bond.)

In formulas (X1-24) to (X1-25), j and k are integers of 0 or 1, A 1 and A 2 are each independently a single bond, -O-, -CO-, -COO-, phenylene, sulfonyl group, or amido group; A plurality of A 2 may be the same or different. )
5. The polymer composition according to claim 4, wherein the formulas (X1-24) and (X1-25) are any one of the following formulas (X1-26) to (X1-41).
The liquid crystal aligning agent according to any one of claims 1 to 5, wherein the polyester (B) further has a repeating unit represented by the following formula (b2).

( A1 is a divalent organic group derived from diisocyanate. A2 is a divalent organic group obtained by removing hydrogen atoms contained in two hydroxy groups from an organic diol.)
Y in the above formula (a) is a diamine represented by the following formula (O), a diamine having an amide bond or a urea bond, 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, A diamine represented by the following formula (d o ), 4-(2-(methylamino)ethyl)aniline, 4-(2-aminoethyl)aniline, and the group “—N(D)—” (D is heated to The polymer composition according to any one of claims 1 to 6, which is a divalent organic group derived from a diamine selected from the group consisting of diamines having a protecting group that is eliminated and replaced with a hydrogen atom. .

(Ar represents a divalent benzene ring, biphenyl structure, or naphthalene ring. The two Ars may be the same or different, and any hydrogen atom in 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 the —(CH 2 ) n — represents a group in which at least part of -CH 2 - is replaced with -O-, -C(=O)- or -O-C(=O)-.)

(When there are two or more m, the two or more m may be the same or different. One or more hydrogen atoms on the benzene ring may be substituted with a monovalent group.)
A 1 in the formula (b2) is a diisocyanate (DI EG ) having a divalent organic group represented by the formula ( EG ), an aromatic diisocyanate other than the diisocyanate (DI EG ), or a diisocyanate other than the diisocyanate (DI EG ) The polymer composition according to any one of claims 6 to 7, which is a divalent organic group derived from an aliphatic diisocyanate.
The polymer composition according to any one of claims 6 to 8, wherein the organic diol in formula (b2) is a diol containing a divalent organic group represented by formula (EG).
The diol containing a divalent organic group represented by the above formula (EG) is a diol in which hydrogen atoms are bonded to both ends of the divalent organic group represented by the above formula (EG), according to claim 9. polymer composition.
X in the above (a) is a tetravalent organic group derived from an acyclic aliphatic tetracarboxylic dianhydride or a derivative thereof, a tetravalent organic group derived from an alicyclic tetracarboxylic dianhydride or a derivative thereof or a tetravalent organic group derived from an aromatic tetracarboxylic dianhydride or a derivative thereof.
The polymer according to any one of claims 1 to 11, wherein X in (a) is a tetravalent organic group derived from a tetracarboxylic dianhydride represented by formula (t) or a derivative thereof. Combined composition.

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

(In formulas (X1-1) to (X1-4), R 1 to R 21 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms , represents an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group, * represents a bond.
In formulas (X1-24) to (X1-25), j and k are integers of 0 or 1, A 1 and A 2 are each independently a single bond, -O-, -CO-, -COO-, phenylene, sulfonyl group, or amido group; A plurality of A 2 may be the same or different. )
The polymer composition according to any one of claims 1 to 12, wherein the polymer (A) further has a repeating unit represented by the following formula (U).

(U 1 is a divalent organic group, U 1' is a divalent organic group derived from a diamine, and C 1 and C 1' are each independently a hydrogen atom or a monovalent organic group. .)
The polymer composition according to any one of claims 1 to 13, wherein the polymer (A) is a terminal-capped polymer.
The polymer composition according to any one of claims 5 to 14, wherein the content of the repeating unit represented by the formula (b1) is 10 mol% or more of the total repeating units constituting the polyester (B). thing.
A group consisting of crosslinkable compounds, functional silane compounds, metal chelate compounds, curing accelerators, surfactants, antioxidants, sensitizers, preservatives, and compounds for adjusting the dielectric constant and electrical resistance of resin films The polymer composition according to any one of claims 1 to 15, further comprising at least one additive component selected from
The liquid crystal aligning agent according to claim 1, wherein the polyester (B) does not have a repeating unit represented by the following formula (b2).

( A1 is a divalent organic group derived from diisocyanate. A2 is a divalent organic group obtained by removing hydrogen atoms contained in two hydroxy groups from an organic diol.)
A liquid crystal aligning agent comprising the polymer composition according to any one of claims 1 to 17.
A resin film obtained using the polymer composition according to any one of claims 1 to 17.
A liquid crystal alignment film formed using the liquid crystal alignment agent according to claim 18.
A liquid crystal display element comprising the liquid crystal alignment film according to claim 20.
A method for manufacturing a liquid crystal display device, comprising the following steps (1) to (3).
Step (1): A step of applying the liquid crystal aligning agent according to claim 18 onto a substrate Step (2): A step of baking the applied liquid crystal aligning agent to obtain a film Step (3): In step (2) a step of subjecting the obtained film to orientation treatment;