WO2023032753A1

WO2023032753A1 - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element

Info

Publication number: WO2023032753A1
Application number: PCT/JP2022/031699
Authority: WO
Inventors: 政太郎大田; 悟志南
Original assignee: 日産化学株式会社
Priority date: 2021-09-01
Filing date: 2022-08-23
Publication date: 2023-03-09
Also published as: TW202317741A; CN117957488A; JPWO2023032753A1

Abstract

Provided are: a liquid crystal alignment agent containing a new solvent component that is suitable for liquid crystal alignment agents; a liquid crystal alignment film obtained from the liquid crystal alignment agent; and a liquid crystal display element using same. Also provided is a liquid crystal display element from which superior display characteristics are obtained even when a liquid crystal alignment film is caused to have an improved application property with respect to end portions and is used for a liquid crystal display element having a large display surface.　This liquid crystal alignment agent contains: at least one polymer (P) selected from the group consisting of polyimide precursors and polyimides that are imidized products of said polyimide precursors; and a solvent component containing a compound (a) represented by formula (A).

Description

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

The present invention relates to a liquid crystal aligning agent, a liquid crystal aligning film obtained from the liquid crystal aligning agent, and a liquid crystal display element having the liquid crystal aligning film.

Conventionally, as a liquid crystal display element, various driving methods with different electrode structures and physical properties of the liquid crystal molecules used have been developed. ) type, IPS type (In Plane Switching), and FFS (Fringe Field Switching) type. These liquid crystal display elements have a liquid crystal alignment film for aligning liquid crystal molecules. Polyimide precursors such as polyamic acids and polyamic acid esters, and polymers typified by polyimides are known as materials for liquid crystal alignment films.

In the VA type liquid crystal display element, which is one of the driving methods of the liquid crystal display element, a photopolymerizable compound is added in advance to the liquid crystal composition, and a vertical alignment film such as a polyimide system is used, and a voltage is applied to the liquid crystal cell. There is known a technique (PSA (Polymer Sustained Alignment) type element) (see, for example, Patent Document 1 and Non-Patent Document 1) that increases the response speed of liquid crystal by irradiating ultraviolet rays while the liquid crystal is being irradiated. Further, a photopolymerizable compound is added to a polyimide-based vertical liquid crystal aligning agent, and a liquid crystal cell provided with a liquid crystal aligning film obtained from the liquid crystal aligning agent is irradiated with ultraviolet rays while applying a voltage, thereby improving the response of the liquid crystal. A technique for increasing the speed (SC-PVA method (see, for example, Non-Patent Document 2)) is also known.

The liquid crystal alignment agent, which is the material for forming the liquid crystal alignment film, has a polymer component dissolved in a solvent, and the liquid crystal alignment film is formed by applying the liquid crystal alignment agent to the substrate and heating it. Here, as the solvent for the liquid crystal aligning agent, an organic solvent in which the polymer is highly soluble, for example, an aprotic polar solvent such as N-methyl-2-pyrrolidone or γ-butyrolactone is generally used.

Japanese Patent Application Laid-Open No. 2003-307720

The above N-methyl-2-pyrrolidone and γ-butyrolactone are used in many technical fields regardless of the liquid crystal aligning agent, so it is expected that their usage will continue to increase in the future. If it does so, it will be necessary to search for a new solvent component suitable for the liquid crystal aligning agent because there is a possibility that supply will be insufficient in the future.

Furthermore, in recent years, liquid crystal display elements have been used for applications such as smartphones and tablet terminals. A sealant is present at a position close to the edge of the liquid crystal alignment film. Therefore, if the coating properties at the edges of the liquid crystal alignment film are reduced, that is, if the area where the edges of the liquid crystal alignment film are raised (unevenness in film thickness at the edges) is wide, the contrast at the edges of the liquid crystal alignment film fluctuates, degrading the display characteristics of the liquid crystal display element.

In view of the above circumstances, an object of the present invention is to provide a liquid crystal aligning agent containing a novel solvent component suitable for the liquid crystal aligning agent, a liquid crystal aligning film obtained from the liquid crystal aligning agent, and a liquid crystal display device using the same. to do. A further object of the present invention is to provide a liquid crystal display device which can improve the coating properties of the end portion of the liquid crystal alignment film and obtain high display characteristics even when applied to a liquid crystal display device having a large display surface.

The present invention is based on such findings, and has the following gist.

At least one polymer (P) selected from the group consisting of a polyimide precursor and a polyimide that is an imidized product of the polyimide precursor, and a solvent component containing a compound (a) represented by the following formula (A), Liquid crystal aligning agent containing.

In this specification, * represents a bond in any case. Boc represents a tert-butoxycarbonyl group. Halogen atoms include fluorine, chlorine, bromine and iodine atoms. Carbamate-based protective groups include a tert-butoxycarbonyl group and a 9-fluorenylmethoxycarbonyl group.

By using the compound (a) as at least part of the solvent component of the liquid crystal aligning agent of the present invention, it is possible to improve the coatability of the polyimide precursor and polyimide. More specifically, the uniformity of the film thickness at the edges of the obtained liquid crystal alignment film is improved, and high display characteristics can be obtained even when applied to a liquid crystal display element having a large display surface. In addition to this, the liquid crystal alignment film of the present invention achieves both high film thickness uniformity and high liquid crystal alignment.

Although the mechanism by which the above effects of the present invention are obtained is not necessarily clear, the following factors are conceivable. Compound (a) has a higher boiling point and viscosity than N-methyl-2-pyrrolidone, which is mainly used in liquid crystal aligning agents. Furthermore, since it has a polarized structure, precipitation of polyimide precursors and polyimide is suppressed. Therefore, the liquid crystal aligning agent using the compound (a) does not cause deposition of the polyimide precursor or polyimide during printing, and the coating size is highly controlled, so it is considered that the above effect was obtained.

It is a figure showing the polyimide film and film thickness nonuniformity printed on the Cr vapor deposition board|substrate. It is the figure which showed the film thickness nonuniformity of the polyimide film edge part which expanded the dotted line part of FIG. 1 with the optical microscope.

Below, each component contained in the liquid crystal aligning agent of this indication, and the other component arbitrarily mix|blended as needed are demonstrated.
<Polymer (P)>
The liquid crystal aligning agent of the present invention contains at least one polymer (P) selected from the group consisting of polyimide precursors and polyimides which are imidized products of the polyimide precursors. Examples of the polyimide precursor include polyamic acid and polyamic acid ester. Moreover, as the tetracarboxylic acid component for obtaining the polymer (P), not only tetracarboxylic dianhydride, but also tetracarboxylic acid, tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester, or tetracarboxylic acid dialkyl ester di Derivatives of tetracarboxylic dianhydrides such as halides can also be used.

(polyamic acid)
Polyamic acid (P′), which is a polyimide precursor of polymer (P), can be obtained by a polymerization reaction between a diamine component and a tetracarboxylic acid component containing tetracarboxylic dianhydride or its derivative.

(diamine)
Various diamines can be used as the diamine component used in the production of the polyamic acid (P′) depending on the purpose. Incidentally, the diamines used in the production of the polyamic acid (P') may be used singly or in combination of two or more. Preferred specific examples of the diamine (hereinafter also referred to as diamine (p)) used for producing the polyamic acid (P′) include the following diamines.

Aromatic diamine (d), p-phenylenediamine, 2,3,5,6-tetramethyl-p represented by "AXJ" (definitions of A, X, and J will be described later) -phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,2'- Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-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, 2,7-diaminonaphthalene, bis(4-aminophenoxy)methane, 1,2-bis(4-aminophenyl)ethane, 1,2-bis(4-aminophenoxy)ethane, 1,3-bis(3- aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,4-bis(4-amino-2-methylphenyloxy)butane, 1,4-bis(3-aminophenyl)butane, bis (3,5-diethyl-4-aminophenyl)methane, 1,5-bis(4-aminophenoxy)pentane, 1,5-bis(3-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy) ) hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,7-bis(3-aminophenoxy)heptane, 1,8-bis( 4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)nonane, 1,9-bis(3-aminophenoxy)nonane, 1,10- Bis(4-aminophenoxy)decane, 1,10-bis(3-aminophenoxy)decane 1,11-bis(4-aminophenoxy)undecane, 1,11-bis(3-aminophenoxy)undecane, 1,12-bis(4-aminophenoxy)dodecane, 1,12-bis(3-amino phenoxy)dodecane, 3-[2-[2-(4-aminophenoxy)ethoxy]ethoxy]benzenamine, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene , 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 4,4′-bis(4-aminophenoxy)biphenyl, 4,4′-bis(4- aminophenoxy)diphenyl ether, 1,4-bis[4-(4-aminophenoxy)phenoxy]benzene, 1,2-bis(6-amino-2-naphthyloxy)ethane, 1,2-bis(6-amino- 2-naphthyl)ethane, 6-[2-(4-aminophenoxy)ethoxy]-2-naphthylamine, 4′-[2-(4-aminophenoxy)ethoxy]-[1,1′-biphenyl]-4- Amine, 1,4-bis[2-(4-aminophenyl)ethyl]butanedioate, 1,6-bis[2-(4-aminophenyl)ethyl]hexanedioate, 1,4-phenylenebis(4 -aminobenzoate), 1,4-phenylenebis(3-aminobenzoate), 1,3-phenylenebis(4-aminobenzoate), 1,3-phenylenebis(3-aminobenzoate), bis(4-aminophenyl ) terephthalate, bis(3-aminophenyl)terephthalate, bis(4-aminophenyl)isophthalate, bis(3-aminophenyl)isophthalate (hereinafter, these diamines are also referred to as diamine (1). ); 4,4′-diaminoazobenzene, diaminotolan, 4,4′-diaminochalcone, or [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo- prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, or [4-[(E)-3-[[5-amino-2-[4-amino-2-[ [(E)-3-[4-[4-(4,4,4-trifluorobutoxy)benzoyl]oxyphenyl]prop-2-enoyl]oxymethyl]phenyl]phenyl]methoxy]-3-oxo-propa -1-enyl]phenyl]4-(4,4,4-trifluorobutoxy) diamines having a photoalignable group such as aromatic diamines having a cinnamate structure in the side chain typified by benzoate; methacrylic acid 2- (2,4-diaminophenoxy)ethyl and diamines terminated with photopolymerizable groups such as 2,4-diamino-N,N-diallylaniline; 1-(4-(2-(2,4-diaminophenoxy) ethoxy)phenyl)-2-hydroxy-2-methylpropanone, 2-(4-(2-hydroxy-2-methylpropanoyl)phenoxy)ethyl-3,5-diaminobenzoate, benzoin or its alkyl Diamines (hereinafter also referred to as diamines having a radical initiation function) having groups in the molecule that exhibit a radical polymerization initiator function, such as etherates, benzyl ketals, acetophenones, acylphosphine oxides, benzophenones, or aminobenzophenones. ); diamines having an amide bond such as 4,4′-diaminobenzanilide, 1,3-bis(4-aminophenyl)urea, 1,3-bis(4-aminobenzyl)urea, 1,3-bis Diamines having a urea bond such as (4-aminophenethyl)urea; 4,4'-sulfonyldianiline, 3,3'-sulfonyldianiline, bis(4-aminophenyl)silane, bis(3-aminophenyl)silane , dimethyl-bis(4-aminophenyl)silane, dimethyl-bis(3-aminophenyl)silane, 4,4′-thiodianiline, 3,3′-thiodianiline, 3,3′-diaminodiphenyl ether, 3,4′- Diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy) c)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4- methylphenyl)hexafluoropropane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)propane, 2,2-bis(3-amino-4-methylphenyl)propane, 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; 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, 1,4-bis(p-aminobenzyl)piperazine, 4,4'-[propane-1,3-diylbis(piperidine-1,4-diyl)]dianiline, 4- (4-aminophenoxycarbonyl)-1-(4-aminophenyl)piperidine, diamines represented by the following formulas (z-1) to (z-5), 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-amino Phenyl)pyridine-2,5-diamine, 2-N-(5-aminopyridin-2-yl)pyridine-2,5-diamine, 2-(4-aminophenyl)-5-aminobenzimidazole, 2-( 4-aminophenyl)-6-aminobenzimidazole, 5-(1H-benzimidazol-2-yl)benzene-1,3-diamine, heterocycle-containing diamines, or 4,4′-diaminodiphenylamine, 4, 4'-Diaminodiphenyl-N-methyl Lamine, N,N'-bis(4-aminophenyl)-1,4-benzenediamine, N,N'-bis(4-aminophenyl)-benzidine, N,N'-bis(4-aminophenyl)- N,N'-dimethylbenzidine or nitrogen-containing diamines having a diphenylamine structure such as N,N'-bis(4-aminophenyl)-N,N'-dimethyl-1,4-benzenediamine At least one nitrogen-containing structure selected from the group consisting of heterocycles, secondary amino groups and tertiary amino groups (hereinafter also referred to as specific nitrogen-containing structure). ) (provided that the molecule does not have an amino group bonded with a protective group that is eliminated by heating and replaced with a hydrogen atom.); 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3, 5-diaminobenzoic acid, 4,4'-diaminobiphenyl-3-carboxylic acid, 4,4'-diaminodiphenylmethane-3-carboxylic acid, 4,4'-diaminodiphenylethane-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'-diamino biphenyl-2,4′-dicarboxylic acid, 4,4′-diaminodiphenylmethane-3,3′-dicarboxylic acid, 1,2-bis(4-aminophenyl)ethane-3,3′-dicarboxylic acid, and 4, Diamines having a carboxyl group such as 4'-diaminodiphenyl ether-3,3'-dicarboxylic acid; 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol , 4,6-diaminoresorcinol, 4,4′-diamino-3,3′-dihydroxybiphenyl; 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-indene-6- Amine; N,N'-bis(2-tert-butoxycarbonylamino-4-aminophenyl)adipamide, 4-amino-N-(2-tert-butoxycarbonylamino-4-aminophenyl)benzamide, carbamic acid, N -[(2,5-diaminophenyl)methyl]-,1,1-dimethylethyl ester, carbamic acid, N-[3-(2,5-diaminophenyl)propyl]-,1,1-dimethylethyl ester, carbamic acid, N,N-[(2,5-diamino-1,3-phenylene)di-3,1-propanediyl]bis-,C,C-bis(1,1-dimethylethyl) ester, N- tert-butoxycarbonyl-N-(2-(4-aminophenyl)ethyl)-N-(4-aminobenzyl)amine, benzoic acid, 4-amino-2-tert-butoxycarbonylamino-, 1,1'- [(1,1,3,3-tetramethyl-1,3-di siloxanediyl)di-4,1-butanediyl]ester, carbamic acid, N-[2-(4
-aminophenyl)ethyl]-N-[[[2-(4-aminophenyl)ethyl]amino]carbonyl]-, 1,1-dimethylethyl ester, carbamic acid, N-(4-aminophenyl)-N- Groups such as [[1-(4-aminophenyl)-4-piperidinyl]methyl]-, 1,1-dimethylethyl ester "-N(D)-" (D is eliminated by heating and replaced with a hydrogen atom represents a protecting group, preferably a tert-butoxycarbonyl group.); Diaminobenzene, 1-hexadecanoxy-2,4-diaminobenzene, 1-octadecanoxy-2,4-diaminobenzene, 1-dodecanoxy-2,5-diaminobenzene, 1-tetradecanoxy-2,5-diaminobenzene, 1-pentadecanoxy -Aromatic diamines (tn ); 1,3-bis(3-aminopropyl)-tetramethyldisiloxane, 1,3-bis[3-(p-aminophenylcarbamoyl)propyl]tetramethyldisiloxane and other diamines having a siloxane bond; diamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine) , a diamine in which two amino groups are bonded to a group represented by any of the formulas (Y-1) to (Y-167) described in WO 2018/117239, etc.

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

In the aromatic diamine (d) above, A represents a monovalent group in which two primary amino groups are bonded to an aromatic group. Specific examples of aromatic groups include benzene rings, naphthalene rings, and biphenyl structures. X is a single bond, —(CH ₂ ) _a — (a is an integer of 1 to 15), —CONH—, —NHCO—, —CO—N(CH ₃ )—, —NH—, —O -, -COO-, -OCO- or -(A ₀ ) _m0 -((CH ₂ ) _a1 -A ₁ ) _m1 -(a1 is an integer of 1 to 15, and A _{0 and} A ₁ are each independently represents an oxygen atom or -COO-, m0 is an integer of 0 or 1, and m1 is an integer of 1 to 2. When m1 is 2, a plurality of a1 and _A1 are each independently defined above ).

J represents a monovalent organic group having at least one group selected from the group consisting of an alicyclic hydrocarbon group having 4 to 40 carbon atoms and an aromatic hydrocarbon group having 6 to 40 carbon atoms. However, at least one of the hydrogen atoms of the alicyclic hydrocarbon group and the aromatic hydrocarbon group is a halogen atom, a halogen atom-containing alkyl group, a halogen atom-containing alkoxy group, an alkyl group having 3 to 10 carbon atoms, a carbon It is substituted with a substituent (v) which is either an alkoxy group having 3 to 10 carbon atoms or an alkenyl group having 3 to 10 carbon atoms. Further, any carbon-carbon single bond in these substituents (v) (excluding halogen atoms) may be interrupted by -O-. In addition to the above alicyclic hydrocarbon group and aromatic hydrocarbon group, J is an alicyclic hydrocarbon group that is unsubstituted or substituted with a substituent other than the above substituent (v) and an aromatic It may further have at least one group selected from the group consisting of hydrocarbon groups.

Examples of halogen atom-containing alkyl groups include halogen atom-containing alkyl groups having 1 to 10 carbon atoms.

Examples of halogen atom-containing alkoxy groups include halogen atom-containing alkoxy groups having 1 to 10 carbon atoms.

Examples of the alicyclic hydrocarbon group for J include cyclobutane ring, cyclopentane ring, cyclohexane ring, cyclodecane ring, steroid skeleton (e.g., cholestanyl group, cholesteryl group, lanostanyl group, etc.), and the like. A benzene ring, a naphthalene ring, etc. can be mentioned as a hydrogen group. When J has at least one of a cyclohexane ring and a benzene ring, examples of the group "-XJ" include the following structure (S1), and more preferred structures are the following formulas (S1-1) to (S1-5) can be mentioned.

X ¹ is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -CONH-, -CO-N(CH ₃ )-, -NH-, -O-, - COO—, or —(A ₀ ) _m0 —((CH ₂ ) _a1 —A ₁ ) _m1 — (a1 is an integer of 1 to 15, and A ₀ and A ₁ are each independently an oxygen atom or —COO -, m0 is an integer of 0 or 1, and m1 is an integer of 1 to 2. When m1 is 2, multiple a1 and _A1 each independently have the above definition.) .

G ¹ represents a divalent cyclic group selected from a phenylene group and a cyclohexylene group. Any hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a fluorine-containing alkoxy group having 1 to 3 carbon atoms. Alternatively, it may be substituted with a fluorine atom.

m is an integer of 1-4. When m is 2 or more, multiple X ¹ and G ¹ each independently have the above definition.

R ¹ is a fluorine atom, a fluorine atom-containing alkyl group having 1 to 10 carbon atoms, a fluorine atom-containing alkoxy group having 1 to 10 carbon atoms, an alkyl group having 3 to 10 carbon atoms, an alkoxy group having 3 to 10 carbon atoms, or carbon represents an alkoxyalkyl group of numbers 3 to 10;

X ¹ and R ¹ are synonymous with X ¹ and R ¹ in formula (S1) above.
Specific examples of the aromatic diamine (d) include diamines represented by the following formulas (d-1) and (d-2). More preferred specific examples are the groups of formulas (d-1) to (d-1) to ( diamines represented by d-2), and cholestanyloxy-3,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, and 3,5-diaminobenzo diamines having a steroid skeleton such as cholestanyl acid, cholestenyl 3,5-diaminobenzoate, lanostanyl 3,5-diaminobenzoate and 3,6-bis(4-aminobenzoyloxy)cholestane.

X and J have the same definitions as X and J of the aromatic diamine (d) above, including preferred embodiments. In the above formula (d-2), two X and J may be the same or different.
As the diamine (p), for example, it is possible to appropriately select and use from the above diamines according to the drive mode of the liquid crystal display element to be manufactured. Specifically, by using the diamine (1), the diamine having the specific nitrogen-containing structure, or the diamine having the urea bond as the diamine (p), an IPS type or FFS type liquid crystal display element can be obtained. A suitable liquid crystal aligning agent can be produced. Further, by using the diamine (1) and the aromatic diamine (tn), a liquid crystal aligning agent suitable for TN-type liquid crystal display elements can be produced, and the aromatic diamine (d) is used. Thereby, a liquid crystal aligning agent suitable for VA type liquid crystal display elements can be produced. Further, by using the diamine having a radical initiation function and the diamine having a photopolymerizable group at the terminal, a liquid crystal aligning agent suitable for PSA type or SC-PVA type liquid crystal display elements can be produced. .
In addition, when imparting photo-orientation to the polyamic acid (P'), the diamine having the photo-orientation group can be used as the diamine (p). Furthermore, when imparting solubility to the polyamic acid (P'), the diamine having the carboxy group, the diamine having the group "-N(D)-", or -Ar-K-Ar- (Ar represents an unsubstituted or substituted phenylene group; K represents -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -O-, or -CH ₂ -; Ar—K—Ar— is formed in the main chain direction of the polymer.) can be used. Specific examples of the diamine (K) include 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl] Propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-aminophenyl)hexafluoro Propane, 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)propane, 2,2 -bis(3-amino-4-methylphenyl)propane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane and the like.

When the aromatic diamine (d) is used as the diamine (p), it is preferably 5 to 95 mol%, preferably 10 to 90 mol%, of the total diamine component used to produce the polyamic acid (P'). is more preferred.
When the diamine (1), the diamine having the specific nitrogen-containing structure, or the diamine having the urea bond is used as the diamine (p), the diamine component used to produce the polyamic acid (P') It is preferably 5 to 95 mol %, more preferably 10 to 90 mol % of the whole.
As the diamine (p), when using a diamine having a photo-orientation group, a diamine having a radical initiation function, or a diamine having a photopolymerizable group at the end, the diamine used for producing the polyamic acid (P') It is preferably 5 to 60 mol %, more preferably 10 to 60 mol %, of the entire component.
As the diamine (p), when using the diamine having the carboxyl group or the diamine having the group "-N(D)-", the total diamine component used for producing the polyamic acid (P'), 5 to 90 mol % is preferred, and 10 to 80 mol % is more preferred.

(tetracarboxylic dianhydride)
Tetracarboxylic dianhydrides that can be used in the synthesis of the polyamic acid (P′) include acyclic aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, and aromatic tetracarboxylic acids. At least one compound selected from the group consisting of dianhydrides is included. Among them, it is more preferable to contain a tetracarboxylic dianhydride having at least one partial structure selected from the group consisting of a benzene ring, a cyclobutane ring structure, a cyclopentane ring structure and a cyclohexane ring structure, and a cyclobutane ring structure and a cyclopentane ring. It is more preferable to contain a tetracarboxylic dianhydride having at least one partial structure selected from the group consisting of a structure and a cyclohexane ring structure.
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.
An 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.
As the tetracarboxylic acid component that can be used for synthesizing the polyamic acid (P'), the following tetracarboxylic dianhydrides or derivatives thereof (hereinafter collectively referred to as specific tetracarboxylic acid derivatives) are preferred. .)including.

The tetracarboxylic dianhydride or derivative thereof may be used alone or in combination of two or more.

Acyclic aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride; 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl -1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3 ,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-difluoro-1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 1,3-bis(trifluoromethyl)-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3′,4,4′-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride product, 4-(2,5-dioxotetrahydrofuran-3-yl)tetrahydronaphthalene-1,2-dicarboxylic dianhydride, 5-(2,5-dioxotetrahydrofuran-3-yl)-3a, 4, 5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-dioxotetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydro naphtho[1,2-c]furan-1,3-dione, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2 .2]octane-2,3,5,6-tetracarboxylic dianhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride alicyclic tetracarboxylic dianhydrides such as products; pyromellitic dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 3,3′,4,4′-biphenylsulfone Tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-biphenyl ethertetracarboxylic dianhydride, 3,3′,4,4′-perfluoroisopropylidene diphthalic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 2,2 ',3,3'-biphenyltetracarboxylic dianhydride, 4,4'- Bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, ethylene glycol bis-anhydrotrimellitate, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 4,4'-carbonyldiphthalic acid Fragrances such as anhydride, 4,4'-oxydi(1,4-phenylene)bis(phthalic acid) dianhydride, or 4,4'-methylenedi(1,4-phenylene)bis(phthalic acid) dianhydride group tetracarboxylic dianhydrides; other tetracarboxylic dianhydrides described in JP-A-2010-97188.

Preferred examples of the above specific tetracarboxylic acid derivatives include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl -1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl- 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-difluoro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-bis(trifluoromethyl)-1 , 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3, 3′,4,4′-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5-(2,5-dioxotetrahydrofuran-3-yl)-3a,4, 5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-dioxotetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydro naphtho[1,2-c]furan-1,3-dione, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, pyromellit acid dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 3,3′,4,4′-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8- naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3′,4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3′,4, 4′-biphenyltetracarboxylic dianhydride and 2,2′,3,3′-biphenyltetracarboxylic dianhydride.

The proportion of the above-mentioned specific tetracarboxylic acid derivative used is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 50 mol% or more, relative to 1 mol of the total tetracarboxylic acid component used.

(Synthesis of polyamic acid)
Synthesis of polyamic acid is carried out by reacting a diamine component containing the diamine and a tetracarboxylic acid component containing the tetracarboxylic dianhydride or its derivative in an organic solvent. The ratio of the tetracarboxylic dianhydride and the diamine used in the synthetic reaction of the polyamic acid is such that the acid anhydride group of the tetracarboxylic dianhydride is 0.5 to 2 per equivalent of the amino group of the diamine. A ratio that provides equivalents is preferred, and a ratio that provides 0.8 to 1.2 equivalents is more preferred. As in ordinary polycondensation reactions, the closer the equivalent of the acid anhydride group in this tetracarboxylic dianhydride to one equivalent, the greater the molecular weight of the resulting polyamic acid.

The reaction temperature in the polyamic acid synthesis reaction is preferably -20 to 150°C, more preferably 0 to 100°C. Also, the reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours.

The polyamic acid synthesis 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.

Specific examples of the organic solvent include compound (a), cyclohexanone, cyclopentanone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N -dimethylacetamide, dimethylsulfoxide, 1,3-dimethyl-2-imidazolidinone. In addition, when the solvent solubility of the polymer is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Glycol monopropyl ether, diethylene glycol monomethyl ether, or diethylene glycol monoethyl ether can be used

(Synthesis of Polyamic Acid Ester)
Polyamic acid esters are produced by, for example, [I] a method of reacting the polyamic acid obtained by the above method with an esterifying agent, [II] a method of reacting a tetracarboxylic acid diester with a diamine, [III] a tetracarboxylic acid It can be obtained by a known method such as a method of reacting a diester dihalide and a diamine.

(Synthesis of polyimide)
Moreover, a polyimide can be obtained by ring-closing (imidating) a polyimide precursor such as the above polyamic acid or polyamic acid ester. 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. For example, from the viewpoint of ensuring the solubility of polyimide, the imidization rate may be 30% or more, 40 to 99%, or 50 to 99%.

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.

When the polyimide precursor is thermally imidized in the solution, the temperature is preferably 100 to 400° C., more preferably 120 to 250° C., and water produced by the imidization reaction is removed from the system. is preferred.

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 preferably used 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 adding it to the solvent can be filtered and recovered, and then dried at room temperature or under heat under normal pressure or reduced pressure.

<Terminal blocking agent>
When synthesizing the polyimide precursor or polyimide in the present invention, a tetracarboxylic acid component containing a tetracarboxylic acid dianhydride or a derivative thereof, and a diamine component containing the diamine, together with an appropriate terminal blocker to end block It is also possible to synthesize a polymer of the type The end-blocking polymer has effects of improving the film hardness of the liquid crystal alignment film obtained by the coating film and improving the adhesion properties between the sealing agent and the liquid crystal alignment film.

Examples of the ends of the polyimide precursors and polyimides in the present invention include amino groups, carboxy groups, acid anhydride groups, and groups derived from end blocking agents described later. An amino group, a carboxyl group, and an acid anhydride group can be obtained by a normal condensation reaction, or can be obtained by terminal blocking using the following terminal blocking agents.

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. Acid anhydrides; dicarbonic acid diester compounds such as di-tert-butyl dicarbonate and diallyl dicarbonate; chlorocarbonyl compounds such as acryloyl chloride, methacryloyl chloride and nicotinic acid chloride; aniline, 2-aminophenol, 3-aminophenol, 4 -aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n - monoamine compounds such as heptylamine and n-octylamine; ethyl isocyanate, phenyl isocyanate, naphthyl isocyanate, or having unsaturated bonds such as 2-acryloyloxyethyl isocyanate and 2-methacryloyloxyethyl isocyanate Isocyanate and the like can be mentioned.

The proportion of the end blocking agent used is preferably 0.01 to 20 mol parts, more preferably 0.01 to 10 mol parts, per 100 mol parts in total of the diamine components used.

The polystyrene equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the polyimide precursor and polyimide is preferably 1,000 to 500,000, more preferably 2,000 to 300,000. is. In addition, the molecular weight distribution (Mw/Mn) represented by the ratio of Mw to the polystyrene equivalent number average molecular weight (Mn) measured by GPC is preferably 15 or less, more preferably 10 or less. By having the molecular weight within such a range, it is possible to ensure good orientation of the liquid crystal display element.

(Liquid crystal aligning agent)
The liquid crystal aligning agent of the present invention contains the polymer (P) and the compound (a) represented by the formula (A) as a solvent component.
The liquid crystal aligning agent is used for producing a liquid crystal aligning film, and preferably takes the form of a coating liquid from the viewpoint of forming a uniform thin film. The concentration of the polymer in the liquid crystal aligning agent can be appropriately changed by setting the thickness of the coating film to be formed. From the viewpoint of forming a uniform and defect-free coating film, the concentration of the polymer in the liquid crystal aligning agent (the total concentration of the polymer components) is preferably 1% by mass or more, and from the viewpoint of the storage stability of the solution, 10% by mass or less is preferable. A particularly preferred polymer concentration is 2 to 8% by weight.
The content of compound (a) can be appropriately adjusted depending on the purpose. For example, from the viewpoint of improving printability, it may be 0.1% by mass or more, 1% by mass or more, or 5% by mass or more with respect to the total amount of solvent components contained in the liquid crystal aligning agent. It is good also as 10 mass % or more. In addition, from the viewpoint of printability, the upper limit of the content may be 90% by mass or less, 85% by mass or less, or 80% by mass with respect to the total amount of the solvent component contained in the liquid crystal aligning agent. The following may be used.
The compound (a) may contain impurities such as levoglucosan and levoglucosenone. In such a case, the preferable range of the content ratio of compound (a) is defined as the amount of compound (a) including such impurities. Compound (a) may be a single stereoisomer or a mixture containing multiple stereoisomers. Examples of commercially available products of compound (a) include Cyrene (trademark) manufactured by Merck & Co., Inc.

As the solvent used for preparing the liquid crystal aligning agent of the present invention, a solvent other than the above compound (a) may be used. Examples of the other solvent include lactone solvents such as γ-valerolactone, γ-butyrolactone, α,α-dimethyl-γ-butyrolactone; γ-butyrolactam, N-methyl-2-pyrrolidone, N-ethyl-2- pyrrolidone, N-(n-propyl)-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-(n-butyl)-2-pyrrolidone, N-(tert-butyl)-2-pyrrolidone, N-(n -pentyl)-2-pyrrolidone, N-(3-methoxypropyl)-2-pyrrolidone, N-(2-ethoxyethyl)-2-pyrrolidone, N-(4-methoxybutyl)-2-pyrrolidone, N-cyclohexyl -lactam solvents such as 2-pyrrolidone, N-acetyl-ε-caprolactam (N-acetyl-2-oxohexamethyleneimine), N-methyl-ε-caprolactam; N,N-dimethylformamide, N,N-diethylformamide , N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylpropionamide, N,N-dimethylisobutyramide (N,N,2-trimethylpropionamide), N,N-diethylpropionamide, N,N-dipropylacetamide, N,N-diisopropylacetamide, N,N-dibutylacetamide, N,N-dimethyllactamide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N- Amide solvents such as dimethylpropanamide; tetramethylurea, N,N'-dimethylpropyleneurea, N-propionylmorpholine, 4-oxotetrahydropyran (tetrahydro-4H-pyran-4-one), tetramethylene sulfoxide, trimethyl phosphate , triethyl phosphate, hexamethylphosphoric acid triamide, 3-methyl-2-oxazolidone, 1,3-dimethyl-2-imidazolidinone (N,N'-dimethylethyleneurea), 1,4-diacetylpiperazine, cyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), isopropyl acetate, n-butyl acetate, isobutyl acetate, tert-butyl acetate, propylene glycol acetate monoethyl ether, cyclohexyl acetate, 4-methyl-2-pentyl acetate, 3-methoxybutyl acetate (3-methoxybutyl acetate), isopropyl lactate, n-butyl lactate, iso lactate Butyl, tert-butyl lactate, isoamyl lactate (isopentyl lactate), 2-(2-ethoxyethoxy)ethyl acetate (ethylene glycol monoethyl ether acetate), methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-methoxy ethyl propionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate (methyl 2-hydroxy-2-methylpropionate), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, ethylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol diacetate, propylene glycol monomethyl Ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol diacetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol methyl propyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, diethylene glycol monomethyl ether , diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate (2-(2-ethoxyethoxy) ethyl acetate, carbitol acetate), diethylene glycol monobutyl ether acetate (butyl carbitol acetate) ), dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, 1-(2-butoxyethoxy)-2-propanol, 2-(2-butoxyethoxy)-1-propanol, diisobutylcarbinol ( 2,6-dimethyl-4-heptanol), diisobutyl ketone, isoamyl propionate (isoamyl propionate), isoamyl isobutyrate (isoamyl isobutyrate), diisobutyrate butyl ether, ethylene carbonate, propylene carbonate, and the like. These can be used in combination of two or more.

In the liquid crystal aligning agent of the present invention, γ-valerolactone, γ-butyrolactone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-(n-propyl)-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-(n-butyl)-2-pyrrolidone, N-(tert-butyl)-2-pyrrolidone, N-(n-pentyl )-2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, N-ethoxyethyl-2-pyrrolidone, N-methoxybutyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, the above amide solvents, 1,3-dimethyl -2-imidazolidinone, tetramethylurea, hexamethylphosphortriamide, cyclohexanone, and a solvent selected from the group consisting of cyclopentanone (hereinafter collectively referred to as "solvent (1)"). may contain. The content of the solvent (1) is preferably 20 to 99% by mass, more preferably 20 to 90% by mass, and particularly preferably 30 to 80% by mass of the total solvent contained in the liquid crystal aligning agent. .

The liquid crystal aligning agent of the present invention contains, as a solvent component, 4-hydroxy-4-methyl-2-pentanone, n-butyl acetate, propylene glycol monoethyl ether acetate, cyclohexyl acetate, from the viewpoint of improving the printability of the liquid crystal aligning agent. 4-methyl-2-pentyl acetate, n-butyl lactate, isoamyl lactate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Butyl, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol diacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, diisobutylcarbinol, a solvent selected from the group consisting of diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisopentyl ether, ethylene carbonate, and propylene carbonate (hereinafter collectively referred to as "solvent (2)"); may contain. The content of the solvent (2) is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and particularly preferably 10 to 50% by mass of the total solvent contained in the liquid crystal aligning agent. .

The solvent component contained in the liquid crystal aligning agent of the present invention may contain a combination of multiple solvents. For example, a solvent component containing the compound (a) and the solvent (1), a solvent component containing the compound (a) and the solvent (2), a compound (a), the solvent (1) and the solvent (2) and a solvent component containing Among them, more preferable specific examples include solvent components including the following aspects. In the following embodiments, BCS is ethylene glycol monobutyl ether, PB is propylene glycol monobutyl ether, DAA is 4-hydroxy-4-methyl-2-pentanone, DIBK is diisobutyl ketone, BCA is ethylene glycol monobutyl ether acetate, and PGME is Propylene glycol monomethyl ether, PGMEA for propylene glycol monomethyl ether acetate, PGA for propylene glycol diacetate, DEDE for diethylene glycol diethyl ether, DPM for dipropylene glycol monomethyl ether, NMP for N-methyl-2-pyrrolidone, GBL for γ-butyrolactone, CHN is cyclohexanone, CPN is cyclopentanone, 3MDP is 3-methoxy-N,N-dimethylpropanamide, 3BDP is 3-butoxy-N,N-dimethylpropanamide, DP is N,N-dimethylpropionamide, TMP is represents N,N,2-trimethylpropionamide.

Compound (a) and BCS, Compound (a) and GBL and BCS, Compound (a) and trimethyl phosphate and BCS, Compound (a) and triethyl phosphate and BCS, Compound (a) and PB, Compound (a) and GBL and PB, compound (a) and NMP and PB, compound (a) and DAA, compound (a) and GBL and DAA, compound (a) and DAA and BCS, compound (a) and N,N-dimethylisobutyramide and DAA, compound (a) and NMP and DAA, compound (a) and N-ethyl-2-pyrrolidone and DAA, compound (a) and N,N-dimethyllactamide and DAA, compound (a) and trimethyl phosphate and DAA, compound (a) and triethyl phosphate and DAA, compound (a) and DAA and 3MDP, compound (a) and DAA and 3BDP, compound (a) and DIBK, compound (a) and GBL and DIBK, compound ( a) and γ-valerolactone and DIBK, compound (a) and DIBK and 3MDP, compound (a) and DIBK and 3BDP, compound (a) and DIBK and DAA, compound (a) and DIBK and PB, compound (a) and DEDE, compound (a) and GBL and DEDE, compound (a) and 1,3-dimethyl-2-imidazolidinone and DEDE, compound (a) and NMP and DEDE, compound (a) and N-butyl-2 -pyrrolidone and DEDE, compound (a) and DEDE and DAA, compound (a) and DEDE and DIBK, compound (a) and DEDE and BCS, compound (a) and DEDE and butyl lactate, compound (a) and NMP and GBL and PB and DIBK, compound (a) and DPM, compound (a) and DPM and DAA, compound (a) and PB and DPM, compound (a) and PGA, compound (a) and PGA and DAA, compound (a) and PGA and PB, compound (a) and diisopropyl ether, compound (a) and PB and diisopropyl ether, compound (a) and diisopentyl ether, compound (a) and NMP and diisopentyl ether, compound (a) and N-ethyl-2-pyrrolidone and diisopentyl ether, compound (a) and N-butyl-2-pyrrolidone and diisopentyl ether, compound (a) and diisobutylcarbinol, compound (a) and diisobutylcarbinol and DIBK , compound (a) and diisobutylcarbinol and PB, compound (a) and dipropylene glycol dimethyl ether, compound (a) and dipropylene glycol dimethyl ether and PB, compound (a) and diethylene glycol ethyl methyl ether , compound (a) and diethylene glycol ethyl methyl ether and DIBK, compound (a) and diethylene glycol ethyl methyl ether and PB, compound (a) and diethylene glycol ethyl propyl ether, compound (a) and diethylene glycol butyl ethyl ether, compound (a) and CPN and PGME, compound (a) and CPN and PB, compound (a) and CPN and diethylene glycol monoethyl ether, compound (a) and CPN and PGA, compound (a) and CPN and DIBK, compound (a) and CPN and n-butyl acetate, compound (a) and CHN and n-butyl acetate, compound (a) and CHN and BCS, compound (a) and CHN and PGME, compound (a) and tetramethylurea and PGMEA, compound (a) and CHN and PB, compound (a) and CHN and diethylene glycol monoethyl ether, compound (a) and CHN and DIBK, compound (a) and methyl isobutyl ketone and PB, compound (a) and methyl ethyl ketone and PB, compound (a) and CPN and DAA, compound (a) and CPN and DEDE, compound (a) and CHN and DAA, compound (a) and CHN and DEDE, compound (a) and CHN and PGA, compound (a) and tetramethylurea and PGME, compound (a) and tetramethylurea and PGA, compound (a) and tetramethylurea and PB, compound (a) and tetramethylurea and CHN and PGME, compound (a) and DP and PGME, compound (a) and DP and PGMEA, compound (a) and DP and PB, compound (a) and DP and BCS, compound (a) and DP and DEDE, compound (a) and N,N-diethylformamide and PGME, compound (a) and N,N-diethylformamide and DAA, compound (a) and N,N-diethylpropionamide and PGME, compound (a) and TMP and PGME, compound (a) and TMP and PGMEA, compound (a) and TMP and PB, compound (a) and TMP and BCS, compound (a) and TMP and DEDE, compound (a) and BCA, compound (a) and BCS and BCA, compound (a) and ethyl 3-ethoxypropionate, compound ( a) and GBL and ethyl 3-ethoxypropionate, compound (a) and CHN and ethyl 3-ethoxypropionate, compound (a) and propylene carbonate and ethyl 3-ethoxypropionate, compound (a) and DP and 3- ethyl ethoxypropionate, compound (a) and tetramethylurea and ethyl 3-ethoxypropionate, and and compound (a) with trimethyl phosphate and ethyl 3-ethoxypropionate.

In addition, the liquid crystal aligning agent of the present invention may contain components other than those mentioned above, if necessary. Examples of the component include at least one selected from a polymer (Q) other than the polymer (P) described above, an epoxy group, an oxetanyl group, an oxazoline group, a cyclocarbonate group, a blocked isocyanate group, a hydroxy group, and an alkoxy group. At least one crosslinkable compound selected from the group consisting of a crosslinkable compound (c-1) having one substituent and a crosslinkable compound (c-2) having a polymerizable unsaturated group, and a functional silane compound , metal chelate compounds, curing accelerators, surfactants, antioxidants, sensitizers, preservatives, and compounds for adjusting the dielectric constant and electrical resistance of the liquid crystal alignment film.

Specific examples of other polymers (Q) include polysiloxanes, polyesters, polyamides, polyureas, polyorganosiloxanes, cellulose derivatives, polyacetals, polystyrene derivatives, poly(styrene-maleic anhydride) copolymers, poly( isobutylene-maleic anhydride) copolymers, poly(vinyl ether-maleic anhydride) copolymers, poly(styrene-phenylmaleimide) derivatives, polymers selected from the group consisting of poly(meth)acrylates, and the like. . Specific examples of poly(styrene-maleic anhydride) copolymers include SMA1000, SMA2000, SMA3000 (manufactured by Cray Valley), GSM301 (manufactured by Gifu Shellac Manufacturing Co., Ltd.) and the like. 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 anhydride). maleic acid resin, manufactured by Ashland).

The other polymer (Q) may be used alone or in combination of two or more. The content of the other polymer (Q) is preferably 50 parts by mass or less, more preferably 1 to 50 parts by mass, more preferably 5 to 40 parts by mass with respect to the total 100 parts by mass of the polymer contained in the liquid crystal aligning agent. Part is more preferred.
Preferred specific examples of the crosslinkable compounds (c-1) and (c-2) include the following compounds.

Examples of epoxy group-containing compounds 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, and 1,6-hexane. Diol diglycidyl ether, glycerin diglycidyl ether, 2,2-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) and the like biphenyl skeleton-containing epoxy resins, phenol novolac type epoxy resins such as EPPN-201 (manufactured by Nippon Kayaku Co., Ltd.), (o, m, p-) cresol novolac type epoxy resins such as EOCN-102S (manufactured by Nippon Kayaku Co., Ltd.), 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'-diaminodiphenylmethane compounds in which a tertiary nitrogen atom is bound to an aromatic carbon atom such as; 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) Tertiary nitrogen such as lysidylaminomethyl)benzene, 1,3,5-tris(N,N-diglycidylaminomethyl)cyclohexane, 1,3,5-tris(N,N-diglycidylaminomethyl)benzene Compounds whose atoms are bonded to aliphatic carbon atoms, isocyanurate compounds such as triglycidyl isocyanurate such as TEPIC (manufactured by Nissan Chemical Co., Ltd.), compounds described in paragraph [0037] of JP-A-10-338880, and international compounds described in Publication No. 2017/170483;
As compounds having an oxetanyl group, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene (aron oxetane OXT-121 (XDO)), di[2-(3-oxetanyl)butyl] Ether (aron oxetane OXT-221 (DOX)), 1,4-bis[(3-ethyloxetan-3-yl)methoxy]benzene (HQOX), 1,3-bis[(3-ethyloxetan-3-yl ) methoxy]benzene (RSOX), 1,2-bis[(3-ethyloxetan-3-yl)methoxy]benzene (CTOX), described in paragraphs [0170] to [0175] of WO 2011/132751 compounds having two or more oxetanyl groups;
Compounds having an oxazoline group include compounds such as 2,2'-bis(2-oxazoline) and 2,2'-bis(4-methyl-2-oxazoline), and Epocross (trade name, manufactured by Nippon Shokubai Co., Ltd.). Polymers and oligomers having an oxazoline group, such as compounds described in paragraph [0115] of Japanese Patent Application Laid-Open No. 2007-286597;
As compounds having a cyclocarbonate group, N,N,N',N'-tetra[(2-oxo-1,3-dioxolan-4-yl)methyl]-4,4'-diaminodiphenylmethane, N,N' -Di[(2-oxo-1,3-dioxolan-4-yl)methyl]-1,3-phenylenediamine and paragraphs [0025] to [0030] and [0032] of WO2011/155577 compounds, etc.;
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 compounds having a hydroxy group and 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-dimethoxymethylphenyl)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, WO 2010/074269 compounds described;
As crosslinkable compounds 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, pentaethylene glycol mono(meth)acrylate ) acrylate, hexaethylene glycol mono(meth)acrylate and the like.

The content of the crosslinkable group-containing compounds (c-1) and (c-2) contained in the liquid crystal aligning agent of the present invention is It is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, still more preferably 1 to 10 parts by mass.

Compounds for adjusting the dielectric constant and electrical resistance include monoamines having nitrogen-containing aromatic heterocycles such as 3-picolylamine. When using a monoamine having a nitrogen-containing aromatic heterocycle, it is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 100 parts by mass relative to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent. 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-(trimethoxysilyl)propyl]isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane , 3-isocyanatopropyltriethoxysilane and the like. When using a functional silane compound, it is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the polymer component contained in the liquid crystal alignment agent. .

The solid content concentration in the liquid crystal aligning agent (ratio of the total mass of components other than the solvent of the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc., but preferably It is 1 to 10% by mass. A particularly preferable solid content concentration range varies depending on the method used when applying the liquid crystal aligning agent to the substrate. For example, when a spin coating method is used, the solid content concentration is particularly preferably 1.5 to 4.5% by mass. When the printing method is used, it is particularly preferable to set the solid content concentration to 3 to 9% by mass and thereby the solution viscosity to 12 to 50 mPa·s. In the case of the inkjet method, it is particularly preferable to set the solid content concentration to 1 to 5% by mass and thereby the solution viscosity to 3 to 15 mPa·s.

<Liquid crystal alignment film>
The liquid crystal alignment film of the present invention is obtained from the above liquid crystal alignment agent. The liquid crystal alignment film of the present invention can be used as a horizontal alignment type or vertical alignment type liquid crystal alignment film. As the vertical alignment type liquid crystal alignment film, a liquid crystal alignment film used for a vertical alignment type liquid crystal display element such as a VA system, a PSA system, or an SC-PVA system is preferable. Further, the liquid crystal aligning agent of the present invention can be used as a liquid crystal alignment film for a retardation film, a liquid crystal alignment film for a scanning antenna or a liquid crystal array antenna, a liquid crystal alignment film for a transmission scattering type liquid crystal light control element, or other applications. , for example, a protective film for a color filter, a gate insulating film for a flexible display, and a substrate material.

<Liquid crystal display element>
The liquid crystal display element of the present invention comprises the liquid crystal alignment film. 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. It is also preferably used for a liquid crystal display element manufactured through a process of polymerizing a polymerizable compound by at least one of irradiation with an active energy ray and heating while placing a substance and applying a voltage between electrodes.

The liquid crystal display device of the present invention can be manufactured, for example, by performing the following steps (1) to (3) or steps (1) to (4) in this order.
(1) A step of applying a liquid crystal aligning agent on at least one of a pair of substrates having a conductive film to form a coating film. A substrate provided with a patterned transparent conductive film. The liquid crystal aligning agent of the present invention is coated on one surface of the substrate by an appropriate coating method such as a roll coater method, a spin coat method, a printing method, an ink jet method, or the like to prepare a coating film. 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 a 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.
(2) Step of Baking Coating Film After applying the liquid crystal aligning agent, the coating film is baked for the purpose of preventing dripping of the applied aligning agent. Preferably, preheating (prebaking) is performed first. The prebaking temperature is preferably 30 to 200°C, more preferably 40 to 150°C, and particularly preferably 40 to 100°C. The pre-baking time is preferably 0.25-10 minutes, more preferably 0.5-5 minutes. Then, a heating (post-baking) step is preferably performed. The post-bake temperature is preferably 80-300°C, more preferably 120-250°C. The post-bake time is preferably 5-200 minutes, more preferably 10-100 minutes. The thickness of the film thus formed is preferably 5 to 300 nm, more preferably 10 to 200 nm.

The coating film formed in the above steps (1) and (2) can be used as it is as a liquid crystal alignment film, but the coating film may be subjected to an alignment ability imparting treatment. Alignment imparting treatment includes rubbing treatment in which the coating film is rubbed in a fixed direction with a roll wrapped with a cloth made of fibers such as nylon, rayon, cotton, etc., and photo-alignment treatment in which the coating film is irradiated with polarized or non-polarized radiation. processing and the like.

In the photo-alignment treatment, ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm can be used as the radiation to irradiate the coating film. When the radiation is polarized, it may be linearly polarized or partially polarized. Further, when the radiation used is linearly polarized or partially polarized, the irradiation may be performed from a direction perpendicular to the substrate surface, from an oblique direction, or a combination thereof. When non-polarized radiation is applied, the direction of irradiation is oblique.
(3) Step of forming a liquid crystal layer between the pair of substrates to produce a liquid crystal cell (3-1) When manufacturing a VA liquid crystal display element Two substrates having the liquid crystal alignment film of the present invention formed on at least one of them are prepared, and a liquid crystal is arranged between the two substrates facing each other. Specifically, the following two methods are mentioned. The first method is a conventionally known 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, a sealant is applied to the periphery of the two substrates and attached to each other, and a liquid crystal composition is injected and filled into the cell gap defined by the substrate surface and the sealant to contact the film surface, and then the injection hole is opened. Seal.
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 described below; optically active compounds (eg, S-811 manufactured by Merck Co., Ltd.); antioxidants; UV absorbers; dyes; antifoaming agents; polymerization initiators; or polymerization inhibitors.
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 the 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 the liquid crystal composition to a temperature at which the used liquid crystal composition assumes an isotropic phase and then slowly cooling to room temperature. (3-2) Production of PSA type liquid crystal display device The procedure of (3-1) above is repeated except that the liquid crystal composition containing a compound having a polymerizable group is injected or dropped. Examples of compounds having a polymerizable group include compounds having a mesogenic structure and two or more photopolymerizable groups or thermally polymerizable groups. The mesogenic structure includes a structure in which two or more aromatic groups or aliphatic groups are linked, such as a biphenyl structure, a terphenyl structure, a naphthalene ring, a group obtained by removing two hydroxy groups from bisphenol A, or any of these A fluorine atom-containing structure in which a part of the hydrogen atoms of the structure are replaced with fluorine atoms can be mentioned. Specific compounds include 4,4'-dimethacryloxybiphenyl or 3-fluoro-1,1'-biphenyl-4,4'-diyl dimethacrylate.
(3-3) When a coating film is formed on a substrate using a liquid crystal aligning agent containing a compound having a polymerizable group (SC-PVA method)
A method of manufacturing a liquid crystal display element may be adopted by carrying out the same as the above (3-1) and then performing a step of irradiating ultraviolet rays, which will be described later. According to this method, a liquid crystal display device having an excellent 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 the polymerizable group described above, and the content thereof is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of all polymer components. , more preferably 1 to 20 parts by mass. Further, the polymerizable group may be present in the polymer used for the liquid crystal alignment agent, and such a polymer includes, for example, a diamine component containing a diamine having a photopolymerizable group at the end thereof, which is used in the reaction. The polymer obtained is mentioned.
(4) Step of irradiating the liquid crystal cell with light The liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates obtained in (3-2) or (3-3) above. The voltage applied here can be, for example, 5 to 50 V direct current or alternating current. As the light for irradiation, for example, ultraviolet light containing light with a wavelength of 150 to 800 nm and visible light can be used, but ultraviolet light containing light with a wavelength of 300 to 400 nm is preferable. A low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used as the light source for the irradiation light. 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 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.

The present invention will be described in more detail based on examples below, but the present invention is not limited to these examples. The abbreviations of the compounds used and methods for measuring physical properties are as follows.
(solvent)
NMP: N-methyl-2-pyrrolidone BCS: ethylene glycol monobutyl ether Cyrene: (1S,5R)-6,8-dioxabicyclo[3.2.1]octan-4-one (corresponding to compound (a))

(tetracarboxylic dianhydride)
CA-1 to CA-2: compounds represented by the following formulas (CA-1) to (CA-2), respectively

(diamine)
DA-1 to DA-2: compounds represented by the following formulas (DA-1) to (DA-2), respectively

<Measurement of molecular weight>
Measurement was performed using the following normal temperature GPC (gel permeation chromatography) apparatus, and Mn and Mw were calculated as values converted to polyethylene glycol and polyethylene oxide. GPC apparatus: SSC-7200 (manufactured by Senshu Kagaku), column: GPC KD-803, GPC KD-805 (manufactured by Showa Denko) in series, column temperature: 50 ° C., eluent: N,N-dimethylformamide (addition As agents, lithium bromide monohydrate (LiBr.H ₂ O) is 30 mmol/L, phosphoric acid/anhydride crystals (o-phosphoric acid) is 30 mmol/L, and tetrahydrofuran (THF) is 10 mL/L), flow rate: 1.0 mL/min Standard sample for creating a calibration curve: TSK standard polyethylene oxide (molecular weight; about 900,000, 150,000, 100,000 and 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight; 000, 4,000 and 1,000) (manufactured by Polymer Laboratories).

<Measurement of imidization rate>
20 mg of polyimide powder was placed in an NMR sample tube (NMR sampling tube standard, φ5 (manufactured by Kusano Kagaku Co., Ltd.)) and deuterated dimethyl sulfoxide ([D ₆ ]-DMSO, 0.05% tetramethylsilane (TMS) mixture). 1.0 mL was added and sonicated to completely dissolve. This solution was subjected to proton NMR at 500 MHz using a Fourier transform superconducting nuclear magnetic resonance spectrometer (FT-NMR) "AVANCE III" (manufactured by BRUKER).

(Chemical) imidization rate is determined by protons derived from a structure that does not change before and after imidization as reference protons, and is derived from the peak integrated value of this proton and the NH group of amic acid appearing around 9.5 to 10.0 ppm. It was obtained by the following formula using the proton peak integrated value. In the following formula, x indicates the proton peak integrated value derived from the NH group of the amic acid, y indicates the peak integrated value of the reference proton, and α is the amic acid in the case of polyamic acid (imidization rate is 0%). shows the ratio of the number of reference protons to one proton of the NH group of .

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

[Synthesis of polymer]
<Synthesis Example 1>
DA-1 (5.09 g, 11.7 mmol), DA-2 (4.15 g, 27.3 mmol), CA-2 (7.32 g, 29.3 mmol) and NMP (66.2 g) were added, and the mixture was stirred at 80°C for 3 hours while purging with nitrogen. Then, after cooling to room temperature, CA-1 (1.87 g, 9.54 mmol) and NMP (7.49 g) were added and stirred at 40° C. for 18 hours to obtain a polyamic acid solution.
NMP (103 g), acetic anhydride (10.8 g) and pyridine (3.34 g) were added to the polyamic acid solution (50.0 g) obtained above, and the mixture was stirred at room temperature for 30 minutes and then at 80°C for 5 hours. reacted. This reaction solution was poured into methanol (587 g), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 60° C. to obtain polyimide (SPI-1) powder. The imidization rate of this polyimide powder was 81%, Mn was 12,502, and Mw was 36,348.

[Preparation of Liquid Crystal Aligning Agent]
<Example 1>
NMP (8.00 g) was added to polyimide (SPI-1) powder (2.00 g) and dissolved by stirring at 70° C. for 15 hours to obtain a polyimide solution. Using the polyimide solution, diluted with Cyrene and BCS and stirred at room temperature for 2 hours, the mass ratio of the polymer solid content and each solvent (polymer solid content: Cyrene: NMP: BCS) was 6:30: A liquid crystal aligning agent (AL-1) with a ratio of 24:40 was obtained.

<Example 2>
Cyrene (11.3 g) was added to polyimide (SPI-1) powder (2.00 g) and dissolved by stirring at 70° C. for 15 hours to obtain a polyimide solution.
Using the polyimide solution, diluted with Cyrene and BCS and stirred at room temperature for 2 hours, the mass ratio of the polymer solid content and each solvent (polymer solid content: Cyrene: BCS) was 6: 54: 40. A liquid crystal aligning agent (AL-2) was obtained.

<Comparative Example 1>
NMP (11.3 g) was added to polyimide (SPI-1) powder (2.00 g) and dissolved by stirring at 70° C. for 15 hours to obtain a polyimide solution. Using the above polyimide solution, dilute with NMP and BCS and stir at room temperature for 2 hours, so that the mass ratio of the polymer solid content and each solvent (polymer solid content: NMP: BCS) is 6: 54: 40. A liquid crystal aligning agent (AL-3) was obtained.

Table 1 shows the specifications of each liquid crystal aligning agent prepared above.

[Evaluation of printability]
After filtering the liquid crystal aligning agents AL-1 to AL-3 obtained in Examples 1 to 2 and Comparative Example 1 with a filter having a pore size of 1.0 μm, an alignment film printer (Japan A printability test was performed by performing flexographic printing using "Angstromer" manufactured by Photo Printing Co., Ltd.).
Specifically, about 1.0 mL of liquid crystal aligning agent was dropped on an anilox roll, and after performing idle operation five times, printing was performed on one Cr vapor deposition substrate (length 100 mm × width 100 mm, thickness 1.0 mm). Printing is performed under the conditions of a set size of 80 mm × 80 mm and a printing pressure of 0.2 mm, and the substrate after printing is left on a hot plate at 70 ° C. for 90 seconds to temporarily dry the coating film, and the film state is observed. bottom. The film thickness unevenness at the edges was observed visually and with an optical microscope ("ECLIPSE ME600" manufactured by Nikon Corporation) at a magnification of 50 times. As an evaluation criterion, select the portion where the size of the film thickness unevenness is the largest at the edge of the printed coating film. ×”. More specifically, in the polyimide film (Fig. 1) printed on the Cr-deposited substrate, the portion where the size of the film thickness unevenness is the largest (dotted line portion in Fig. 1) is selected, and the magnification of the optical microscope is 50 times. The length of A in FIG. 2 of the polyimide film image obtained by observation was measured. The length of A corresponds to the width of the film thickness unevenness. Table 2 shows the results.

[Production of liquid crystal cell]
Using the liquid crystal aligning agent obtained above, a liquid crystal cell was produced in the following procedure. The liquid crystal aligning agent is spin-coated on a glass substrate with ITO electrodes (width 3 cm × length 4 cm), dried on a hot plate at 70 ° C. for 90 seconds, and then baked in an infrared heating furnace at 230 ° C. for 20 minutes to obtain a film thickness. A liquid crystal alignment film of 100 nm was formed. Two substrates with the liquid crystal alignment film were prepared, and a bead spacer with a diameter of 4 μm (manufactured by Nikki Shokubai Kasei Co., Ltd., Shinshikyu, SW-D1) was applied onto one of the liquid crystal alignment films, leaving a liquid crystal injection port. A thermosetting sealant (XN-1500T manufactured by Mitsui Chemicals, Inc.) was printed around the periphery. Next, the surface of the other substrate on which the liquid crystal alignment film was formed was turned inside, and after bonding with the previous substrate, the sealant was cured to prepare an empty cell. Liquid crystal MLC-3023 (manufactured by Merck) was injected into this empty cell by a vacuum injection method to prepare a liquid crystal cell. Next, while a DC voltage of 15 V was applied to the liquid crystal cell, ultraviolet rays having a wavelength of 325 nm or less and passed through a cut filter were irradiated from the outside of the liquid crystal cell at 10 J/cm ² . The ultraviolet illuminance was measured using an ultraviolet illuminance meter/photometer UV-M03A manufactured by Oak Manufacturing Co., Ltd. Thereafter, for the purpose of deactivating the unreacted polymerizable compound remaining in the liquid crystal cell, ultraviolet rays (UV lamp: FLR40SUV32/ A-1) was irradiated for 30 minutes.

[Evaluation of liquid crystal orientation]
The liquid crystal orientation of the liquid crystal display device was observed with a polarizing microscope ("ECLIPSE E600WPOL" manufactured by Nikon Corporation) to confirm whether or not the liquid crystal was vertically aligned. As the evaluation criteria, the case where no defects due to liquid crystal flow or bright spots due to orientation defects were observed was rated as "Good", and the case where defects due to liquid crystal flow or bright spots due to alignment defects were observed was rated as "Poor". Table 2 shows the evaluation results.

As shown in Table 2, Examples 1 and 2 using a liquid crystal aligning agent containing the compound (a) represented by the formula (A) used a liquid crystal aligning agent containing no compound (a). As compared with Comparative Example 1, the printability was good, and no problem was observed in the liquid crystal alignment characteristics.

In addition, the entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2021-142711 filed on September 1, 2021 are cited here, and as a disclosure of the specification of the present invention, It is taken in.

Claims

At least one polymer (P) selected from the group consisting of a polyimide precursor and a polyimide that is an imidized product of the polyimide precursor, and a solvent component containing a compound (a) represented by the following formula (A), Liquid crystal aligning agent containing.
The liquid crystal aligning agent according to claim 1, wherein the content of the compound (a) is 5% by mass or more with respect to the total amount of solvent components contained in the liquid crystal aligning agent.
The liquid crystal aligning agent according to claim 1 or 2, wherein the polymer (P) is a polymer obtained by a polymerization reaction of a diamine component and a tetracarboxylic acid component containing tetracarboxylic dianhydride.
The polymer (P) is obtained by a polymerization reaction of a diamine component and a tetracarboxylic acid component containing a tetracarboxylic dianhydride, and the tetracarboxylic dianhydride is an acyclic aliphatic tetracarboxylic dianhydride. 4. The liquid crystal aligning agent according to any one of claims 1 to 3, which is at least one compound selected from a compound, an alicyclic tetracarboxylic dianhydride, and an aromatic tetracarboxylic dianhydride.
Claim 3 or 4, wherein the tetracarboxylic acid component contains a tetracarboxylic dianhydride having at least one partial structure selected from the group consisting of a benzene ring, a cyclobutane ring structure, a cyclopentane ring structure and a cyclohexane ring structure. The liquid crystal aligning agent described.
The solvent component further includes γ-valerolactone, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-(n-propyl )-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-(n-butyl)-2-pyrrolidone, N-(tert-butyl)-2-pyrrolidone, N-(n-pentyl)-2-pyrrolidone, N-(3-methoxypropyl)-2-pyrrolidone, N-(2-ethoxyethyl)-2-pyrrolidone, N-(4-methoxybutyl)-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N - dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylpropionamide, N,N-dimethylisobutyramide (N,N,2-trimethylpropionamide ), N,N-diethylpropionamide, N,N-dipropylacetamide, N,N-diisopropylacetamide, N,N-dibutylacetamide, N,N-dimethyllactamide, 3-methoxy-N,N-dimethylpropane Amide, 3-butoxy-N,N-dimethylpropanamide, tetramethylurea, hexamethylphosphortriamide, cyclohexanone, and a solvent selected from the group consisting of cyclopentanone, any one of claims 1 to 5 The liquid crystal aligning agent according to the item.
The solvent component further includes 4-hydroxy-4-methyl-2-pentanone, n-butyl acetate, propylene glycol monoethyl ether acetate, cyclohexyl acetate, 4-methyl-2-pentyl acetate, n-butyl lactate, and isoamyl lactate. (isopentyl lactate), methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether , ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol diacetate, diethylene glycol dimethyl ether, diethylene glycol Diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, diisobutyl carbinol, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate , diisopentyl ether, ethylene carbonate, and a liquid crystal aligning agent according to any one of claims 1 to 6, comprising a solvent selected from the group consisting of propylene carbonate.
The liquid crystal aligning agent according to any one of claims 3 to 7, containing an aromatic diamine (d) represented by "AXJ" as the diamine component.
(A represents a monovalent group in which two primary amino groups are bonded to an aromatic group. X is a single bond, —(CH 2 ) a — (a is an integer of 1 to 15), -CONH-, -NHCO-, -CO-N(CH 3 )-, -NH-, -O-, -COO-, -OCO- or -(A 0 ) m0 -((CH 2 ) a1 -A 1 ) m1- (a1 is an integer of 1 to 15, A 0 and A 1 each independently represent an oxygen atom or —COO—, m0 is an integer of 0 or 1, m1 is an integer of 1 to 2 When m1 is 2, a1 and A1 each independently have the above definition).
J represents a monovalent organic group having at least one group selected from the group consisting of an alicyclic hydrocarbon group having 4 to 40 carbon atoms and an aromatic hydrocarbon group having 6 to 40 carbon atoms. However, at least one of the hydrogen atoms of the alicyclic hydrocarbon group and the aromatic hydrocarbon group is a halogen atom, a halogen atom-containing alkyl group, a halogen atom-containing alkoxy group, an alkyl group having 3 to 10 carbon atoms, a carbon It is substituted with a substituent (v) which is either an alkoxy group having 3 to 10 carbon atoms or an alkenyl group having 3 to 10 carbon atoms. Further, any carbon-carbon single bond in these substituents (v) (excluding halogen atoms) may be interrupted by -O-. In addition to the above alicyclic hydrocarbon group and aromatic hydrocarbon group, J is an alicyclic hydrocarbon group that is unsubstituted or substituted with a substituent other than the above substituent (v) and an aromatic It may further have at least one group selected from the group consisting of hydrocarbon groups. )
9. The liquid crystal aligning agent according to claim 8, wherein in the aromatic diamine (d), the group "-XJ" has the following structure (S1).

(X 1 is a single bond, —(CH 2 ) a — (a is an integer of 1 to 15), —CONH—, —CO—N(CH 3 )—, —NH—, —O—, -COO- or -(A 0 ) m0 -((CH 2 ) a1 -A 1 ) m1 - (a1 is an integer of 1 to 15, and A 0 and A 1 are each independently an oxygen atom or - represents COO-, m0 is an integer of 0 or 1, and m1 is an integer of 1 to 2. When m1 is 2, multiple a1 and A1 each independently have the above definition. show.
G 1 represents a divalent cyclic group selected from a phenylene group and a cyclohexylene group. Any hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a fluorine-containing alkoxy group having 1 to 3 carbon atoms. Alternatively, it may be substituted with a fluorine atom.
m is an integer of 1-4. When m is 2 or more, multiple X 1 and G 1 each independently have the above definition.
R 1 is a fluorine atom, a fluorine atom-containing alkyl group having 1 to 10 carbon atoms, a fluorine atom-containing alkoxy group having 1 to 10 carbon atoms, an alkyl group having 3 to 10 carbon atoms, an alkoxy group having 3 to 10 carbon atoms, or carbon represents an alkoxyalkyl group of numbers 3 to 10; )
10. The liquid crystal aligning agent according to claim 8, wherein the aromatic diamine (d) is a diamine represented by the following formulas (d-1) to (d-2).

(X and J are the same as defined in claim 8. In the formula (d-2), two X and J may be the same or different.)
Used for forming horizontal or vertical alignment type liquid crystal alignment films, liquid crystal alignment films for retardation films, liquid crystal alignment films for scanning antennas and liquid crystal array antennas, and liquid crystal alignment films for transmission scattering type liquid crystal light control elements. The liquid crystal aligning agent according to any one of claims 1 to 10.
A liquid crystal alignment film obtained from the liquid crystal alignment agent according to any one of claims 1 to 11.
A liquid crystal display element comprising the liquid crystal alignment film according to claim 12.
A method for manufacturing a liquid crystal display device, comprising performing the following steps (1) to (3) in this order.
Step (1): A step of applying the liquid crystal aligning agent according to any one of claims 1 to 11 onto at least one of a pair of substrates having a conductive film to form a coating film. Step (2). : Step of baking the coating film Step (3): Step of forming a liquid crystal layer between the pair of substrates to produce a liquid crystal cell
15. The method of manufacturing a liquid crystal display element according to claim 14, further comprising performing the following step (4) after steps (1) to (3).
Step (4): Step of irradiating the liquid crystal cell with light