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

Abstract

Provided are: a liquid crystal alignment film which has good liquid crystal alignment properties and excellent pretilt angle performance; a liquid crystal display element which comprises the liquid crystal alignment film; and a liquid crystal alignment agent which imparts the liquid crystal alignment film. The present invention provides a liquid crystal aligning agent comprising a compound as component (A), a polyamic acid as component (B), and a solvent, the compound having a structure represented by formula (pa-1) (in the formula, A represents a phenylene group or the like; r1 is-COO <-> or-OCO <->; r < 2 > is cyclohexane-1, 4-diyl; r < 3 > is a cyclohexane-1, 4-diyl group; r4 represents a linear or branched alkyl group having 1-40 carbon atoms, and some or all of hydrogen atoms in the alkyl group may be substituted by fluorine atoms; d represents an oxygen atom, a sulfur atom, or-NRd-; a represents an integer of 0-3; and * represents a bonding position. ), and a thermally crosslinkable group, the thermally crosslinkable group being a group capable of reacting with a carboxyl group to form a covalent bond. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a liquid crystal aligning agent, a liquid crystal aligning film obtained therefrom, and a liquid crystal display element having the obtained liquid crystal aligning film. More specifically, it relates to a liquid crystal aligning agent capable of providing a liquid crystal aligning film having good liquid crystal orientation, excellent pretilt angle performance, and high reliability, and a liquid crystal display element having excellent display quality. Background Art

[0002] In a liquid crystal display element, a liquid crystal alignment film plays the role of orienting liquid crystals in a certain direction. Currently, the main liquid crystal alignment film used in industry is produced by applying a polyimide-based liquid crystal alignment agent formed from a solution of polyamic acid (also called polyamic acid), polyamic acid ester, or polyimide as a polyimide precursor to a substrate and forming a film.

[0003] When the liquid crystal is aligned parallel or obliquely with respect to the substrate surface, the surface is further stretched by brushing after film formation.

[0004] On the other hand, when the liquid crystal is oriented vertically relative to the substrate (called vertical alignment (VA) mode), a liquid crystal alignment film is obtained by introducing hydrophobic groups such as long-chain alkyl groups, cyclic groups or a combination of cyclic groups and alkyl groups (for example, see Patent Document 1), steroid skeletons (for example, see Patent Document 2) into the side chains of polyimide. At this time, when a voltage is applied between the substrates to tilt the liquid crystal molecules in a direction parallel to the substrate, it is necessary to tilt the liquid crystal molecules from the normal direction of the substrate toward one direction in the substrate surface. As means for this, the following methods are proposed, for example: a method of providing a protrusion on the substrate; a method of providing a slit in the display electrode; a method of pre-tilting the liquid crystal molecules from the normal direction of the substrate toward one direction in the substrate surface by brushing; and a method of pre-adding a photopolymerizable compound to the liquid crystal composition, using it together with a vertical alignment film of polyimide, etc., applying a voltage to the liquid crystal unit while irradiating ultraviolet rays, thereby pre-tilting the liquid crystal (for example, see Patent Document 3), etc.

[0005] In recent years, as a method to replace the formation of protrusions or slits in the liquid crystal orientation control of the VA method and the PSA technology, a method (photo-orientation method) using anisotropic photochemical reactions based on polarized ultraviolet irradiation or the like has been proposed. That is, it is known that by irradiating a photoreactive vertically oriented polyimide film with polarized ultraviolet rays, an orientation control capability and pre-tilt angle performance are imparted, thereby enabling the tilt direction of the liquid crystal molecules when a voltage is applied to be uniformly controlled (see Patent Document 4).

[0006] VA-type liquid crystal display elements are used in TV and car displays because of their high contrast and wide viewing angle. Liquid crystal display elements for TV use use a backlight with a large heat release in order to obtain high brightness, or liquid crystal display elements used in car applications, such as car navigation systems and instrument panels, are sometimes used or placed in a high-temperature environment for a long time. Under such harsh conditions, when the pretilt angle changes slowly, the initial display characteristics may not be obtained or the display may be uneven. Furthermore, the voltage retention characteristics and charge accumulation characteristics during liquid crystal driving are also affected by the liquid crystal alignment film, resulting in the following phenomenon: when the voltage retention rate is low, the contrast of the display screen will be reduced, and when the charge accumulation relative to the DC voltage is large, the display screen will burn.

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application Laid-Open No. 3-179323

[0010] Patent Document 2: Japanese Patent Application Laid-Open No. 4-281427

[0011] Patent Document 3: Japanese Patent No. 4504626

[0012] Patent Document 4: Japanese Patent No. 4995267 Summary of the invention

[0013] Problem that the invention aims to solve

[0014] The present invention is made in view of the above situation, and its object is to provide a liquid crystal orientation film whose pretilt angle changes little even after long-term driving, has excellent display reliability and high voltage retention characteristics, and can reduce charge accumulation, a liquid crystal display element having the liquid crystal orientation film, and a liquid crystal orientation agent that provides the liquid crystal orientation film.

[0015] Solutions for solving problems

[0016] The present inventors have found that <x>The main technical solution.

[0017] <x>A liquid crystal alignment agent comprises a compound as component (A), a polyamic acid as component (B), and a solvent, wherein the compound comprises a photo-alignment group represented by the following formula (pa-1) and a thermally crosslinkable group, wherein the thermally crosslinkable group is a group capable of reacting with a carboxyl group to form a covalent bond.

[0018]

[0019] In the formula, A represents a pyrimidine-2,5-diyl group, a pyridine-2,5-diyl group, a thiophene-2,5-diyl group, a furan-2,5-diyl group, a 1,4-naphthylene group or a phenylene group, or a 2,6-naphthylene group or a phenylene group, and the pyrimidine-2,5-diyl group, the pyridine-2,5-diyl group, the thiophene-2,5-diyl group, the furan-2,5-diyl group, the 1,4-naphthylene group or a phenylene group, or the 2,6-naphthylene group or a phenylene group is substituted by a group selected from a fluorine atom, a chlorine atom and a cyano group, or by a group having 1 carbon atom. wherein R1 is -COO- or -OCO-; R2 is cyclohexane-1,4-diyl; R3 is cyclohexane-1,4-diyl; R4 is a linear or branched alkyl group having 1 to 40 carbon atoms, wherein a part or all of the hydrogen atoms of the alkyl group are optionally substituted by fluorine atoms; and D represents an oxygen atom, a sulfur atom or -NR d -(Here, R d represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms); a is an integer of 0 to 3; * represents a bonding position. X and Y are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or an alkyl group having 1 to 3 carbon atoms, wherein a part or all of the hydrogen atoms of the alkyl group may be substituted with fluorine atoms.

[0020] Effects of the Invention

[0021] According to the present invention, a liquid crystal alignment film and a liquid crystal alignment agent having good liquid crystal alignment properties and excellent pretilt angle expression ability and pretilt angle stability can be provided.

[0022] Moreover, the liquid crystal display element manufactured by the method of this invention has excellent display characteristics. DETAILED DESCRIPTION

[0023] The liquid crystal alignment agent of the present invention comprises a compound as component (A) (hereinafter also referred to as a specific compound), a polyamic acid as component (B), and a solvent, wherein the compound comprises a photo-alignment group and a thermally crosslinkable group represented by formula (pa-1), and the thermally crosslinkable group is a compound that is a group that can react with a carboxyl group to form a covalent bond.

[0024] The compound as the component (A) contained in the liquid crystal aligning agent of the present invention has a photoalignment group and a thermally crosslinkable group. Here, the photoalignment group has high sensitivity to light, and therefore can exhibit alignment control capability even in polarized ultraviolet irradiation with a low exposure dose.

[0025] In addition, the compound as (A) component is hydrophobic due to the photo-alignment group, therefore, when the liquid crystal aligning agent is applied to the substrate, the polyamic acid as (B) component is gathered to the substrate side, and the compound as (A) component is gathered to the surface side. Thus, in the coating film obtained using the liquid crystal aligning agent of the present invention, the photo-alignment group is concentrated to the surface layer, therefore, even if the content of the compound as (A) component is reduced, good orientation can be obtained. In addition, by making the thermal cross-linking group of (A) component a group that can react with a carboxyl group to form a covalent bond, even if the firing time of the liquid crystal aligning agent is short, the cross-linking reaction of the compound as (A) component and (B) component can also occur. Thus, when the photo-alignment site shows anisotropy by photoreaction, the liquid crystal aligning film is easily left (preserved) with anisotropy, so that the liquid crystal orientation can be improved and the pre-tilt angle of the liquid crystal is shown.

[0026] Moreover, the liquid crystal aligning agent of this invention can also aim at improvement of electric characteristics, such as improvement of voltage holding ratio and suppression of accumulation of residual charge, by containing the polyamic acid as (B) component.

[0027] Hereinafter, each constituent condition of the present invention will be described in detail.

[0028] <(A) Component: Specified Compound>

[0029] The specific compound as component (A) of the liquid crystal aligning agent of the present invention is a compound having a photo-alignment group and a thermally crosslinkable group represented by formula (pa-1), wherein the thermally crosslinkable group is a group capable of reacting with a carboxyl group to form a covalent bond. Such a specific compound is preferably a compound represented by formula (a-1).

[0030] M a -S a -I a (a-1)

[0031] In formula (a-1), M a The thermally crosslinkable group includes an organic group selected from the group consisting of an epoxy moiety-containing group, an oxetane moiety-containing group, a thiirane moiety-containing group and a cyclocarbonate group.

[0032] In the above formula (a-1), S a I represents a spacer group; a It means that it is bonded to the thermally crosslinkable group optionally via a spacer.

[0033] S a For example, it can be represented by the structure of the following formula (Sp).

[0034] ---W1—A1-W2-A2-W3----- (Sp)

[0035] In formula (Sp),

[0036] The key on the left side of W1 indicates the same a Keys;

[0037] The key on the right side of W3 represents the same a Keys;

[0038] W1, W2 and W3 each independently represent a single bond, a divalent heterocycle, -(CH2) n -(wherein n represents 1 to 20), -OCH2-, -CH2O-, -COO-, -OCO-, -CH=CH-, -CF=CF-, -CF2O-, -OCF2-, -CF2CF2- or -C≡C-, in which one or more non-adjacent CH2 groups may be independently substituted by -O-, -CO-, -CO-O-, -O-CO-, -Si(CH3)2-O-Si(CH3)2-, -NR-, -NR-CO-, -CO-NR-, -NR-CO-O-, -OCO-NR-, -NR-CO-NR-, -CH=CH-, -C≡C- or -O-CO-O- (wherein R independently represents hydrogen or a linear or branched alkyl group having 1 to 5 carbon atoms);

[0039] A1 and A2 are each independently a group selected from a single bond, an alkylene group, a divalent aromatic group, a divalent alicyclic group or a divalent heterocyclic group, and each group is unsubstituted or one or more hydrogen atoms are optionally substituted by a fluorine atom, a chlorine atom, a cyano group, a methyl group or a methoxy group.

[0040] Examples of the aromatic group in A1 and A2 include aromatic hydrocarbon groups having 6 to 18 carbon atoms, such as a benzene ring, a biphenyl structure, and a naphthalene ring. Examples of the alicyclic group in A1 and A2 include alicyclic hydrocarbon groups having 6 to 12 carbon atoms, such as a cyclohexane ring and a bicyclohexane structure. Examples of the heterocyclic ring in A1 and A2 include nitrogen-containing heterocyclic rings, such as a pyridine ring, a piperidine ring, and a piperazine ring. Examples of the alkylene group in A1 and A2 include linear or branched alkylene groups having 1 to 10 carbon atoms.

[0041] In formula (a-1), I a It is a monovalent organic group represented by formula (pa-1).

[0042]

[0043] In the formula, A represents a pyrimidine-2,5-diyl group, a pyridine-2,5-diyl group, a thiophene-2,5-diyl group, a furan-2,5-diyl group, a 1,4-naphthylene group or a phenylene group, or a 2,6-naphthylene group or a phenylene group, and the pyrimidine-2,5-diyl group, the pyridine-2,5-diyl group, the thiophene-2,5-diyl group, the furan-2,5-diyl group, the 1,4-naphthylene group or a phenylene group, or the 2,6-naphthylene group or a phenylene group is substituted by a group selected from a fluorine atom, a chlorine atom and a cyano group, or by a group having 1 carbon atom. wherein R1 is -COO- or -OCO-; R2 is cyclohexane-1,4-diyl; R3 is cyclohexane-1,4-diyl; R4 is a linear or branched alkyl group having 1 to 40 carbon atoms, wherein a part or all of the hydrogen atoms of the alkyl group are optionally substituted by fluorine atoms; and D represents an oxygen atom, a sulfur atom or -NR d -(Here, R d represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms); a is an integer of 0 to 3; * represents a bonding position. X and Y are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or an alkyl group having 1 to 3 carbon atoms, wherein a part or all of the hydrogen atoms of the alkyl group may be substituted with fluorine atoms. From the viewpoint of being able to exhibit good vertical alignment control ability and a stable pretilt angle, a is preferably an integer of 1 to 3.

[0044] From the viewpoint of being able to express good vertical alignment controllability and a stable pretilt angle, the group represented by the above (pa-1) is preferably a group represented by the following (pa-1-a), but is not limited thereto.

[0045]

[0046] In formula (pa-1-a),

[0047] Z is an oxygen atom or a sulfur atom.

[0048] X a and X b Each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or an alkyl group having 1 to 3 carbon atoms, wherein a part or all of the hydrogen atoms of the alkyl group may be substituted with fluorine atoms.

[0049] R1 is -COO- or -OCO-.

[0050] R2 is cyclohexane-1,4-diyl.

[0051] R3 is cyclohexane-1,4-diyl.

[0052] R4 is a linear or branched alkyl group having 1 to 40 carbon atoms, and a part or all of the hydrogen atoms of the alkyl group may be substituted with fluorine atoms.

[0053] R5 is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine atom or a cyano group, and is preferably a methyl group, a methoxy group or a fluorine atom. When there are a plurality of R5 groups, the plurality of R5 groups may be the same or different.

[0054] a is an integer of 0-3, and b is an integer of 0-4.

[0055] In formula (a-1), as S a The group is a linear or branched alkylene group having 1 to 10 carbon atoms, preferably a linear or branched alkylene group having 1 to 8 carbon atoms, for example, preferably a methylene group, an ethylene group, a n-propylene group, a n-butylene group, a tert-butylene group, a n-pentylene group, a n-hexylene group, a n-heptylene group, or a n-octylene group.

[0056] As S a Examples of the divalent aromatic group include 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, and 2,3,5,6-tetrafluoro-1,4-phenylene.

[0057] In formula (a-1), as S a Examples of the divalent alicyclic group include trans-1,4-cyclohexylene and trans-trans-1,4-bicyclohexylene.

[0058] As S a Examples of the divalent heterocyclic group include pyridine-2,6-diyl, pyridine-3,5-diyl, furan-2,5-diyl, piperazine-1,4-diyl and piperidine-1,4-diyl.

[0059] S a An alkylene group having 1 to 8 carbon atoms is preferred, an alkylene group having 1 to 6 carbon atoms is more preferred, and an alkylene group having 1 to 4 carbon atoms is further preferred.

[0060] In the above formula (a-1), regarding S as a spacer a , preferably -CH2-.

[0061] Examples of the linear or branched alkyl group having 1 to 40 carbon atoms represented by R4 include linear or branched alkyl groups having 1 to 20 carbon atoms, in which a part or all of the hydrogen atoms may be substituted with fluorine atoms. Examples of the alkyl group include methyl, ethyl, n-propyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-lauryl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, 4,4,4-trifluorobutyl, 4,4,5,5,5-pentafluoropentyl, 4,4,5,5,6,6,6-heptafluorohexyl, 3,3,4,4,5,5,5-heptafluoropentyl, 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl, 2-(perfluorobutyl)ethyl, 2-(perfluorooctyl)ethyl, and 2-(perfluorodecyl)ethyl.

[0062] The specific compound as component (A) includes, but is not limited to, compounds represented by formula (paa-1-ma1) to (paa-1-ma4). In the formula, "E" represents the E form, and "t" represents that the cyclohexyl group is a trans form.

[0063]

[0064] <Method for producing specific compound>

[0065] The specific compound as the component (A) can be produced by combining known reactions, and specifically, can be produced by the method described in the "Specific Compound Synthesis Example" described later or a method based thereon.

[0066] <(B) Component>

[0067] The liquid crystal aligning agent of this invention contains the polyamic acid (P) as (B) component.

[0068] The said polyamic acid (P) can be obtained by the polymerization reaction of the tetracarboxylic acid component containing a diamine component and tetracarboxylic dianhydride.

[0069] (Diamine)

[0070] The diamine component for producing the above-mentioned polyamic acid (P) can use various diamines according to the purpose. It should be noted that the diamine for producing polyamic acid (P) can be used alone or in combination of two or more. As a preferred specific example of the diamine for producing polyamic acid (P) (hereinafter also referred to as diamine (p)), the following diamines can be listed.

[0071] Aromatic diamine (d) represented by "AXJ" (described later), p-phenylenediamine, 2,3,5,6-tetramethyl-p-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-amino 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) -aminophenoxy) undecane, 1,11-bis(3-aminophenoxy) undecane, 1,12-bis(4-aminophenoxy) dodecane, 1,12-bis(3-aminophenoxy) dodecane, 3-[2-[2-(4-aminophenoxy)ethoxy]ethoxy]aniline, 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]succinate, 1,6-bis[2-(4-aminophenyl)ethyl]adipate, 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 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-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate diamines having a photo-aligning group such as an aromatic diamine having a cinnamate structure in the side chain; diamines having a photopolymerizable group at the end such as 2-(2,4-diaminophenoxy)ethyl methacrylate and 2,4-diamino-N,N-diallylaniline; diamines having a group that functions as a free radical polymerization initiator in the molecule such as benzoin represented by 1-(4-(2-(2,4-diaminophenoxy)ethoxy)phenyl)-2-hydroxy-2-methylacetone, 2-(4-(2-hydroxy-2-methylpropionyl)phenoxy)ethyl-3,5-diaminobenzoate or its alkyl ether, benzyl ketals, acetophenones, acylphosphine oxides, benzophenones or aminobenzophenones; 4,4'-diamino diamines having an amide bond such as 1,3-bis(4-aminophenyl)urea, 1,3-bis(4-aminobenzyl)urea, 1,3-bis(4-aminophenethyl)urea, etc.; 4,4'-sulfonyl diphenylamine, 3,3'-sulfonyl diphenylamine, bis(4-aminophenyl)silane, bis(3-aminophenyl)silane, dimethyl-bis(4-aminophenyl)silane, dimethyl-bis(3-aminophenyl)silane, 4,4'-thiodiphenylamine, 3,3'-thiodiphenylamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 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)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]-aniline, 1,4-bis(p-aminobenzyl)piperazine, 4,4'-propane-1,3-diylbis(piperidin-1,4-diyl)diphenylamine, 4-(4-aminophenoxy) diamines containing a heterocyclic ring such as 2-(4-aminophenyl)-1-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[aniline], 1,4-bis-(4-aminophenyl)-piperazine, 2-N-(4-aminophenyl)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, or 4,4'-diaminodiphenylamine, 4,4'-diaminodiphenyl-N diamines having a diphenylamine structure, such as N,N'-bis(4-aminophenyl)-1,4-phenylenediamine, N,N'-bis(4-aminophenyl)-benzidine, N,N'-bis(4-aminophenyl)-N,N'-dimethylbenzidine, or N,N'-bis(4-aminophenyl)-N,N'-dimethyl-1,4-phenylenediamine, having at least one nitrogen-containing structure selected from the group consisting of a nitrogen-containing heterocycle, a secondary amino group, and a tertiary amino group (wherein the molecule does not have an amino group bonded to a protecting group, the protecting group being released upon heating and replaced by a hydrogen atom); 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,4'-diaminobiphenyl-3-carboxylic acid, 4,diamines having a carboxyl group, such as 4'-diaminodiphenylmethane-3-carboxylic acid, 1,2-bis(4-aminophenyl)ethane-3-carboxylic acid, 4,4'-diaminobiphenyl-3,3'-dicarboxylic acid, 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid, 3,3'-diaminobiphenyl-4,4'-dicarboxylic acid, 3,3'-diaminobiphenyl-2,4'-dicarboxylic acid, 4,4'-diaminodiphenylmethane-3,3'-dicarboxylic acid, 1,2-bis(4-aminophenyl)ethane-3,3'-dicarboxylic acid, and 4,4'-diaminodiphenyl ether-3,3'-dicarboxylic acid; 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminobenzyl alcohol Hydroquinone, 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-indan-6-amine; N1,N6-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-disiloxanediyl)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- diamines having a "-N(D)-" group (D represents a protecting group which is released by heating and replaced by a hydrogen atom, preferably a tert-butoxycarbonyl group) such as [[1-(4-aminophenyl)-4-piperidinyl]methyl]-, 1,1-dimethylethyl ester, 1-dodecyloxy-2,4-diaminobenzene, 1-tetradecyloxy-2,4-diaminobenzene, 1-pentadecyloxy-2,4-diaminobenzene, 1-hexadecyloxy-2,4-diaminobenzene, 1-octadecyloxy-2,4-diaminobenzene, 1-dodecyloxy-2,5-diaminobenzene, 1-tetradecyloxy-2,5-diaminobenzene, 1-pentadecyloxy-2,5-diaminobenzene, 1-hexadecyloxy-2,5-diaminobenzene, 1-octadecyloxy-2,4-diaminobenzene,Aromatic diamines (tn) having a long-chain alkyl group having 12 to 20 carbon atoms, represented by 5-diaminobenzene; diamines having a siloxane bond, such as 1,3-bis(3-aminopropyl)-tetramethyldisiloxane and 1,3-bis[3-(p-aminophenylcarbamoyl)propyl]tetramethyldisiloxane; meta-phenylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), and diamines having two amino groups bonded to the group represented by any of the formulas (Y-1) to (Y-167) described in International Publication No. 2018 / 117239. ,

[0072]

[0073] In the aromatic diamine (d) represented by "AXJ" above, A represents a monovalent group having two primary amino groups bonded to an aromatic group. Specific examples of the aromatic group include a benzene ring, a naphthalene ring, and a biphenyl structure. X represents a single bond, -(CH2) a -(a is an integer of 1 to 15), -CONH-, -NHCO-, -CO-N(CH3)-, -NH-, -O-, -COO-, -OCO- or -(A0) m0 -((CH2) a1 -A1) m1 -(a1 is an integer of 1 to 15, A0 and A1 represent 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 a1s and A1s each independently have the above definition.).

[0074] 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. At least one hydrogen atom possessed by the alicyclic hydrocarbon group and the aromatic hydrocarbon group is substituted by a substituent (v), and the substituent (v) is any of a halogen atom, an alkyl group containing a halogen atom, an alkoxy group containing a halogen atom, an alkyl group having 3 to 10 carbon atoms, an alkoxy group having 3 to 10 carbon atoms, and an alkenyl group having 3 to 10 carbon atoms. Furthermore, any carbon-carbon single bond in these substituents (v) (excluding halogen atoms) may be interrupted by -O-. In addition, J may have at least one group selected from the group consisting of an alicyclic hydrocarbon group and an aromatic hydrocarbon group which are unsubstituted or substituted by a substituent other than the substituent (v).

[0075] Examples of the halogen atom-containing alkyl group include halogen atom-containing alkyl groups having 1 to 10 carbon atoms.

[0076] Examples of the alkoxy group containing a halogen atom include alkoxy groups containing a halogen atom having 1 to 10 carbon atoms.

[0077] Examples of alicyclic hydrocarbon groups of J include cyclobutane ring, cyclopentane ring, cyclohexane ring, cyclodecane ring, steroid skeleton (for example, cholesteryl, cholesteryl, lanostanyl, etc.), and examples of aromatic hydrocarbon groups include benzene ring, naphthalene ring, etc. When J has at least one of a cyclohexane ring and a benzene ring, examples of the "-XJ" group include the following structure (S1), and more preferably, the following formulas (S1-1) to (S1-5) are listed (wherein, X 1 , R 1 , * and X in formula (S1) 1 , R 1 , * have the same meaning).

[0078]

[0079] Where, X 1 Represents a single bond, -(CH2) a -(a is an integer of 1 to 15), -CONH-, -CO-N(CH3)-, -NH-, -O-, -COO- or -(A0) m0 -((CH2) a1 -A1) m1 -(a1 is an integer of 1 to 15, A0 and A1 represent 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 a1s and A1s each independently have the above definition. * represents a bonding position.).

[0080] G 1 represents a divalent cyclic group selected from phenylene and cyclohexylene. Any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorinated alkyl group having 1 to 3 carbon atoms, a fluorinated alkoxy group having 1 to 3 carbon atoms, or a fluorine atom.

[0081] m is an integer of 1 to 4. When m is 2 or more, a plurality of X 1 , G 1 Each independently has the above definition.

[0082] R 1 It represents a fluorine atom, an alkyl group having 1 to 10 carbon atoms and containing a fluorine atom, an alkoxy group having 1 to 10 carbon atoms and containing a fluorine atom, an alkyl group having 3 to 10 carbon atoms, an alkoxy group having 3 to 10 carbon atoms, or an alkoxyalkyl group having 3 to 10 carbon atoms.

[0083]

[0084] Specific examples of the aromatic diamine (d) include diamines represented by the following formulas (d-1) to (d-2). More preferred specific examples include diamines represented by formulas (d-1) to (d-2) in which the "-XJ" group is any of the above structures (S1) or (S1-1) to (S1-5), and diamines having a steroid skeleton such as cholesteryloxy-3,5-diaminobenzene, cholesteryloxy-3,5-diaminobenzene, cholesteryloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholesteryl ester, 3,5-diaminobenzoic acid cholesteryl ester, 3,5-diaminobenzoic acid lanosteryl ester, and 3,6-bis(4-aminobenzoyloxy)cholestane.

[0085]

[0086] X and J, including preferred embodiments, have the same meanings as X and J in the above aromatic diamine (d). In the above formula (d-2), two X and J may be the same or different.

[0087] When the aromatic diamine (d) is used as the diamine (p), the amount is preferably 5 to 95 mol %, more preferably 10 to 90 mol %, based on the total amount of the diamine component used to produce the polyamic acid (P).

[0088] (Tetracarboxylic dianhydride)

[0089] The tetracarboxylic dianhydride that can be used to synthesize the above-mentioned polyamic acid (P) can include at least one compound selected from the group consisting of non-cyclic aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride and aromatic tetracarboxylic dianhydride. Among them, it is more preferred to include 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 it is further preferred to include a tetracarboxylic dianhydride having at least one partial structure selected from the group consisting of a cyclobutane ring structure, a cyclopentane ring structure and a cyclohexane ring structure.

[0090] As a tetracarboxylic acid component which can be used for synthesizing the polyamic acid (P), it is preferable to contain the following tetracarboxylic dianhydride (these are also collectively referred to as specific tetracarboxylic dianhydride hereinafter).

[0091] In addition, the above-mentioned tetracarboxylic dianhydride may be used alone or in combination of two or more.

[0092] Non-cyclic 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 dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)tetrahydronaphthalene-1,2-dicarboxylic anhydride, 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-tetrahydronaphtho[1,2-c]furan-1,3-dione alicyclic tetracarboxylic dianhydrides such as 1,3-pyran-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; pyromellitic tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride Aromatic tetracarboxylic acid dianhydrides such as dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 2,2',3,3'-biphenyltetracarboxylic acid dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, ethylene glycol bis(trimellitic acid anhydride), 4,4'-(hexafluoroisopropylidene)phthalic anhydride, 4,4'-carbonylphthalic anhydride, 4,4'-(1,4-phenylenedioxy)bis(phthalic anhydride) or 4,4'-(1,4-phenylenedimethylene)bis(phthalic anhydride); and tetracarboxylic acid dianhydrides described in Japanese Patent Application Laid-Open No. 2010-97188.

[0093] Preferred examples of the 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-dicarboxy)cyclopentylacetic dianhydride, oxotetrahydrofuran-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-tetrahydronaphtho[1,2-c]furan-1,3-dione, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, Pyromellitic acid dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic acid dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic acid dianhydride, 3,3',4,4'-biphenyl tetracarboxylic acid dianhydride, 2,2',3,3'-biphenyl tetracarboxylic acid dianhydride.

[0094] The usage ratio of the said specific tetracarboxylic dianhydride is preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 50 mol% or more, based on 1 mol of all tetracarboxylic acid components used.

[0095] (Synthesis of Polyamic Acid)

[0096] The synthesis of polyamic acid is carried out by reacting a diamine component containing the above-mentioned diamine with a tetracarboxylic acid component containing the above-mentioned tetracarboxylic dianhydride or a derivative thereof in an organic solvent. The ratio of the tetracarboxylic dianhydride and the diamine used in the synthesis reaction of polyamic acid is preferably 0.5 to 2 equivalents of the anhydride group of the tetracarboxylic dianhydride relative to 1 equivalent of the amino group of the diamine, and more preferably 0.8 to 1.2 equivalents. As in the usual polycondensation reaction, the closer the equivalent of the anhydride group of the tetracarboxylic dianhydride is to 1 equivalent, the greater the molecular weight of the generated polyamic acid becomes.

[0097] The reaction temperature in the synthesis reaction of the polyamic acid is preferably -20 to 150° C., and more preferably 0 to 100° C. The reaction time is preferably 0.1 to 24 hours, and more preferably 0.5 to 12 hours.

[0098] The synthesis reaction of the polyamic acid can be carried out at any concentration, but is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The reaction is carried out at a high concentration in the initial stage, and a solvent may be added thereafter.

[0099] 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, dimethyl sulfoxide, and 1,3-dimethyl-2-imidazolidinone. In addition, when the polymer has high solvent solubility, 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.

[0100] <Capping Agent>

[0101] When synthesizing the polyamic acid in the present invention, a tetracarboxylic acid component including tetracarboxylic dianhydride or its derivative and a diamine component including the above-mentioned diamine can be used, and an appropriate end-capping agent can be used to synthesize an end-capped polymer. The end-capped polymer has the effect of increasing the film hardness of the oriented film obtained by coating and improving the adhesion between the sealant and the oriented film.

[0102] Examples of the terminal of the polyamic acid in the present invention include amino groups, carboxyl groups, acid anhydride groups, or groups derived from the terminal blocking agent described below. The amino groups, carboxyl groups, and acid anhydride groups can be obtained by a common condensation reaction or by sealing the terminals using the following terminal blocking agents.

[0103] Examples of the end-capping agent include acid anhydrides such as 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, and 4-ethynylphthalic anhydride; dicarbonic acid diester compounds such as di-tert-butyl dicarbonate and diallyl dicarbonate; acryloyl chloride, methacryloyl chloride, and nicotinoyl chloride. Chlorocarbonyl compounds such as chlorine; monoamine compounds such as aniline, 2-aminophenol, 3-aminophenol, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, and n-octylamine; isocyanates having unsaturated bonds such as ethyl isocyanate, phenyl isocyanate, naphthyl isocyanate, or 2-acryloyloxyethyl isocyanate and 2-methacryloyloxyethyl isocyanate, etc.

[0104] The usage ratio of the terminal blocking agent is preferably 0.01 to 20 parts by mole, more preferably 0.01 to 10 parts by mole, based on 100 parts by mole of the total of the diamine components used.

[0105] The weight average molecular weight (Mw) of the polyamic acid measured by gel permeation chromatography (GPC) in terms of polystyrene is preferably 1,000 to 500,000, more preferably 2,000 to 300,000. In addition, the molecular weight distribution (Mw / Mn) represented by the ratio of Mw to the number average molecular weight (Mn) in terms of polystyrene measured by GPC is preferably 15 or less, more preferably 10 or less. By being in this molecular weight range, good orientation of the liquid crystal display element can be ensured.

[0106] The content of the specific compound as the component (A) in the liquid crystal aligning agent of the present invention is preferably 0.5 to 30 parts by mass, more preferably 0.8 to 20 parts by mass, and further preferably 1 to 10 parts by mass, based on 100 parts by mass of the polyamic acid component as the component (B).

[0107] [Preparation of Liquid Crystal Alignment Agent]

[0108] The liquid crystal alignment agent used in the present invention is preferably prepared as a coating liquid in order to be suitable for forming a liquid crystal alignment film. That is, the liquid crystal alignment agent of the present invention is preferably prepared as a solution obtained by dissolving a resin component for forming a resin coating in an organic solvent. Here, the resin component refers to the specific compound as the (A) component and the polyamic acid as the (B) component already described. At this time, the total content of the specific compound of the (A) component and the content of the polyamic acid as the (B) component is preferably 0.5 to 20% by mass relative to the entire liquid crystal alignment agent, more preferably 1 to 20% by mass, further preferably 1 to 15% by mass, and particularly preferably 1 to 10% by mass.

[0109] <Solvent>

[0110] The solvent contained in the liquid crystal aligning agent used in the present invention is not particularly limited as long as it is a solvent that dissolves the (A) component and the (B) component. The solvent contained in the liquid crystal aligning agent can be one kind, or two or more kinds can be mixed and used. In addition, even if it is not a solvent that dissolves the (A) component and the (B) component, it can also be used in combination with a solvent that dissolves the (A) component and the (B) component. At this time, if the surface energy of the solvent that does not dissolve the (A) component and the (B) component is less than the solvent that dissolves the (A) component and the (B) component, the coating property of the liquid crystal aligning agent for the substrate can be improved, so it is preferred.

[0111] Specific examples include water, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and other N-alkyl-2-pyrrolidone; N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-ε-caprolactam, tetramethylurea, 3-methoxy-N,N-dimethylpropionamide, 3-ethoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, 1,3-dimethyl-2-imidazolidinone and other dialkyl imidazolidinone; lactones such as γ-butyrolactone, γ-valerolactone, δ-valerolactone; carbonates such as ethylene carbonate and propylene carbonate. ; ketones such as methanol, ethanol, propanol, isopropanol, 3-methyl-3-methoxybutanol, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, isopentyl methyl ketone, methyl isopropyl ketone, diisobutyl ketone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, 4-hydroxy-4-methyl-2-pentanone; compounds represented by the following formula (Sv-1) and compounds represented by the following formula (Sv-2), 4-methyl-2-pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, 2-methylcyclohexyl acetate, butyl butyrate, isopentyl butyrate, diisobutyl carbinol, diisopentyl ether, etc.

[0112]

[0113] In formulas (Sv-1) to (Sv-2), Y1 and Y2 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, X1 is an oxygen atom or -COO-, X2 is a single bond or a carbonyl group, and R1 is an alkanediyl group having 2 to 4 carbon atoms. n1 is an integer of 1 to 3. When n1 is 2 or 3, multiple R1s may be the same or different. Z1 is a divalent hydrocarbon group having 1 to 6 carbon atoms, and Y3 and Y4 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms.

[0114] In formula (Sv-1), examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms for Y1 and Y2 include monovalent chain hydrocarbon groups having 1 to 6 carbon atoms, monovalent alicyclic hydrocarbon groups having 1 to 6 carbon atoms, and monovalent aromatic hydrocarbon groups having 1 to 6 carbon atoms. Examples of the monovalent chain hydrocarbon group having 1 to 6 carbon atoms include alkyl groups having 1 to 6 carbon atoms. The alkanediyl group for R1 may be linear or branched.

[0115] In the formula (Sv-2), examples of the divalent hydrocarbon group having 1 to 6 carbon atoms represented by Z1 include an alkanediyl group having 1 to 6 carbon atoms.

[0116] Examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms for Y3 and Y4 include monovalent chain hydrocarbon groups having 1 to 6 carbon atoms, monovalent alicyclic hydrocarbon groups having 1 to 6 carbon atoms, and monovalent aromatic hydrocarbon groups having 1 to 6 carbon atoms. Examples of the monovalent chain hydrocarbon group having 1 to 6 carbon atoms include alkyl groups having 1 to 6 carbon atoms.

[0117] Specific examples of the solvent represented by formula (Sv-1) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monohexyl ether, ethylene glycol dimethyl ether, ethylene glycol monoacetate, ethylene glycol diacetate, ethylene glycol ethyl ether acetate, 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, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether, propylene glycol diacetate, ethylene glycol, 1,4-butanediol, 3-methoxybutyl acetate, 3-ethoxybutyl acetate, and the like;

[0118] Specific examples of the solvent represented by (Sv-2) include methyl glycolate, ethyl glycolate, butyl glycolate, ethyl lactate, butyl lactate, isoamyl lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, and butyl 3-methoxypropionate.

[0119] The boiling point of the solvent is preferably 80 to 200° C., more preferably 80 to 180° C., and preferred solvents include N,N-dimethylformamide, tetramethylurea, 3-methoxy-N,N-dimethylpropionamide, propanol, isopropanol, 3-methyl-3-methoxybutanol, ethyl amyl ketone, methyl ethyl ketone, isoamyl methyl ketone, methyl isopropyl ketone, diisobutyl ketone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, 4-hydroxy-4-methyl-2-pentanone, 4-methyl-2-pentyl acetate, 2-ethylbutyl acetate, cyclohexyl acetate, 2-methylcyclohexyl acetate, butyl butyrate, isoamyl butyrate, diisobutyl carbinol, diisoamyl ether, ethylene glycol monomethyl ether, ethylene glycol Monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol monoacetate, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether, 3-methoxybutyl acetate, methyl glycolate, ethyl glycolate, butyl glycolate, ethyl lactate, butyl lactate, isopentyl lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, etc.

[0120] Particularly when a liquid crystal aligning agent containing the above solvent is applied on a plastic substrate to be described later, it is preferable that the boiling point is within the above range.

[0121] <Other ingredients>

[0122] The liquid crystal aligning agent used in the present invention may contain other components in addition to the above-mentioned (A) component and (B) component. As such other components, crosslinking catalysts, compounds that improve the uniformity of film thickness or surface smoothness when coated with the liquid crystal aligning agent, compounds that improve the adhesion between the liquid crystal aligning film and the substrate, etc. can be listed, but are not limited to this.

[0123] <Crosslinking Catalyst>

[0124] In the liquid crystal alignment agent used in the present invention, a crosslinking catalyst may be added for the purpose of promoting the reaction between the thermally crosslinkable group and the carboxyl group. Examples of such crosslinking catalysts include p-toluenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, p-phenolsulfonic acid, 2-naphthalenesulfonic acid, mesitylenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H,1H,2H,2H-perfluorooctanesulfonic acid, perfluoro(2-ethoxyethane)sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, dodecylbenzenesulfonic acid and other sulfonic acids or their hydrates, salts and the like. Examples of the compound that generates an acid by heat include bis(toluenesulfonyloxy)ethane, bis(toluenesulfonyloxy)propane, bis(toluenesulfonyloxy)butane, p-nitrobenzyl toluenesulfonate, o-nitrobenzyl toluenesulfonate, 1,2,3-phenylenetri(methylsulfonate), pyridinium p-toluenesulfonate, morpholinium p-toluenesulfonate, ethyl p-toluenesulfonate, propyl p-toluenesulfonate, butyl p-toluenesulfonate, isobutyl p-toluenesulfonate, methyl p-toluenesulfonate, phenylethyl p-toluenesulfonate, cyanomethyl p-toluenesulfonate, 2,2,2-trifluoroethyl p-toluenesulfonate, 2-hydroxybutyl p-toluenesulfonate, and N-ethyl-p-toluenesulfonamide.

[0125] [Compounds that improve uniformity of film thickness and surface smoothness]

[0126] Examples of the compound that improves uniformity of film thickness and / or surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.

[0127] Specific examples include Eftop (registered trademark) 301, EF303, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Megafack (registered trademark) F171, F173, R-30 (manufactured by DIC Corporation), Fluorad FC430, FC431 (manufactured by 3M Company), AsahiGuard (registered trademark) AG710 (manufactured by AGC Corporation), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGCSEIMI CHEMICAL CO., LTD.), and the like.

[0128] The usage ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, based on 100 parts by mass of the resin component contained in the polymer composition.

[0129] [Compound for Improving Adhesion Between Liquid Crystal Alignment Film and Substrate]

[0130] As a specific example of the compound which improves the adhesiveness of a liquid crystal aligning film and a substrate, the functional silane-containing compound etc. shown below are mentioned.

[0131] Examples thereof include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-3-triethoxysilylpropyltriethylenetetramine, N -3-trimethoxysilylpropyltriethylenetetramine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane and other amino silane-containing compounds.

[0132] When a compound that improves adhesion to a substrate is used, the amount thereof used is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the resin component contained in the polymer composition.

[0133] In one embodiment, in order to improve the photoreactivity of the photo-alignment group, a photosensitizer may be used as an additive, and specific examples thereof include aromatic 2-hydroxyketone (benzophenone), coumarin, ketocoumarin, carbonyl dicoumarol, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenone ketal.

[0134] <Liquid crystal alignment film and liquid crystal display element>

[0135] The liquid crystal alignment agent of the present invention can be coated on a substrate and fired, and then oriented by brushing, light irradiation, etc. to form a liquid crystal alignment film, or it can be formed without orientation treatment in some vertical alignment applications. As a substrate, glass such as float glass and soda-lime glass can be used; transparent substrates formed of plastics such as polyethylene terephthalate, polybutylene terephthalate, polypropylene, polystyrene, polyether sulfone, polycarbonate, poly (alicyclic olefin), polyvinyl chloride, polyvinylidene chloride, polyether ether ketone (PEEK) resin film, polysulfone (PSF), polyether sulfone (PES), polyamide, polyimide, acrylic acid and triacetyl cellulose can be used.

[0136] As the transparent conductive film provided on one side of the substrate, a NESA film (registered trademark of PPG, USA) containing tin oxide (SnO 2 ), an ITO film containing indium oxide-tin oxide (In 2 O 3 —SnO 2 ), or the like can be used.

[0137] <Coating Film Forming Step>

[0138] The coating method of the liquid crystal aligning agent of the present invention is not particularly limited, and there are screen printing, flexographic printing, offset printing, inkjet, dip coating, roller coating, slit coating, spin coating, etc., which can be used according to the purpose. After being coated on the substrate by these methods, the solvent is evaporated by heating means such as a heating plate, so that a coating film can be formed. It should be noted that in the coating film of the liquid crystal aligning agent formed in the coating film forming process, (A) component is partially present on the film surface due to the hydrophobicity of the photo-orientation group, therefore, even if the content of (A) component is reduced, good liquid crystal orientation is also shown.

[0139] The calcination after applying the liquid crystal aligning agent can be performed at any temperature of 40 to 300° C., preferably 40 to 250° C., more preferably 40 to 230° C. In this step, the thermally crosslinkable group of the specific compound as the component (A) reacts with the carboxyl group of the polyamic acid as the component (B), and the aligning group is fixed.

[0140] The film thickness of the coating film formed on the substrate is preferably 5 to 1,000 nm, more preferably 10 to 500 nm or 10 to 300 nm. The calcination can be performed using a hot plate, a hot air circulation furnace, an infrared furnace, or the like.

[0141] <Light irradiation step>

[0142] In one embodiment, the alignment treatment can be performed by light irradiation, which may include, for example, the following steps: a step of coating the liquid crystal alignment agent on a substrate to form a coating film; and a step of irradiating the coating film with light in a state where the coating film is not in contact with the liquid crystal layer or in a state where the coating film is in contact with the liquid crystal layer.

[0143] As the light irradiated in the alignment treatment based on light irradiation, for example, ultraviolet rays including light with a wavelength of 150 to 800 nm, visible light, etc. can be listed. Among these, ultraviolet rays including light with a wavelength of 300 to 400 nm are preferred. The irradiated light may be polarized light or non-polarized light. As polarized light, light including linearly polarized light is preferably used.

[0144] When the light used is polarized light, the light irradiation may be performed from a direction perpendicular to the substrate surface, from an oblique direction, or a combination thereof. When non-polarized light is irradiated, it is preferably performed from an oblique direction relative to the substrate surface.

[0145] The irradiation amount of light is preferably set to 0.1 mJ / cm 2 Above and less than 1,000mJ / cm 2 , more preferably 1 to 500 mJ / cm 2 , and more preferably 2 to 200 mJ / cm 2 .

[0146] The liquid crystal display element of the present invention can be made by a common method, and its preparation method is not particularly limited. The above-mentioned pair of substrates are opposite to each other at an appropriate interval, and for the purpose of making the thickness of the liquid crystal sandwiched between the substrates uniform, it is preferred to configure a spacer between the substrates. As the spacer, known spacer materials such as the spacer formed by the photosensitive spacer formation composition can be used, in addition, the concavoconvex formed on the layer containing the liquid crystal cured product can also be used as a spacer.

[0147] <Liquid crystal clamping process>

[0148] In order to sandwich a liquid crystal between substrates to form a liquid crystal unit, for example, the following two methods can be cited. As a first method, the following method can be cited: a pair of substrates are arranged opposite to each other with a gap (cell gap) in between so that each liquid crystal alignment film is opposite to each other, the peripheral portions of the pair of substrates are bonded together using a sealant, and after injecting liquid crystal into the cell gap divided by the substrate surface and the appropriate sealant, the injection hole is sealed, thereby manufacturing a liquid crystal unit.

[0149] As a second method, the following method (ODF (One Drop Fill) method) can be listed: a UV-curable sealant, for example, is applied to a specified portion on one of two substrates on which a liquid crystal alignment film is formed, and then liquid crystal is dropped at specified locations on the surface of the liquid crystal alignment film. The other substrate is bonded so that the liquid crystal alignment film is opposite, and the liquid crystal is pushed and spread over the entire surface of the substrate, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant, thereby manufacturing a liquid crystal unit.

[0150] As liquid crystals, fluorine-based liquid crystals, cyano-based liquid crystals, or liquid crystal compounds or liquid crystal compositions that are polymerized by at least one of heating and light irradiation (hereinafter also referred to as polymerizable liquid crystals or curable liquid crystal compositions) having positive or negative dielectric anisotropy can be used depending on the application.

[0151] In one embodiment, the step of forming the coating film of the liquid crystal aligning agent may be performed by a roll-to-roll method. If the roll-to-roll method is used, the manufacturing process of the liquid crystal display element can be simplified and the manufacturing cost can be reduced.

[0152] Furthermore, by attaching polarizing plates to both outer surfaces of the liquid crystal cell, a liquid crystal display element can be obtained.

[0153] Examples of the polarizing plate used outside the liquid crystal cell include a polarizing plate formed by sandwiching a polarizing film called "H film" made by stretching and aligning polyvinyl alcohol while absorbing iodine with cellulose acetate protective films, or a polarizing plate formed of the H film itself.

[0154] The liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention as described above has good liquid crystal alignment, excellent pretilt angle expression ability, and high reliability. In addition, the liquid crystal display element manufactured by the method of the present invention has excellent display characteristics.

[0155] Example

[0156] The present invention will be described in further detail below based on examples, but the present invention is not limited to these examples. The abbreviations of the compounds used are as follows.

[0157] (Photo-aligning monomer)

[0158] EP1 to EP5: compounds represented by the following formulae [EP1] to [EP5], respectively. In the formulae (EP1) to (EP5), "t" indicates that the cyclohexyl group is in the trans form.

[0159]

[0160] <Tetracarboxylic dianhydride>

[0161] A1 to A2: compounds represented by the following formulas [A1] to [A2], respectively

[0162]

[0163] <Side Chain Diamine>

[0164] B1 to B2: compounds represented by the following formulas [B1] to [B2], respectively

[0165]

[0166] <Other diamines>

[0167] C1 to C2: compounds represented by the following formulas [C1] to [C2] respectively

[0168]

[0169] In addition, the abbreviations of the reagents used in the present examples are shown below.

[0170] (Solvent)

[0171] CH2Cl2: dichloromethane

[0172] THF: Tetrahydrofuran

[0173] MeOH: Methanol

[0174] EtOH: ethanol

[0175] AcOEt: Ethyl acetate

[0176] MeCN: Acetonitrile

[0177] CHCl3: Chloroform

[0178] NMP: N-methyl-2-pyrrolidone

[0179] BCS: Butyl Cellosolve

[0180] <Synthesis of Monomer>

[0181] EP5 was synthesized by the method described in Japanese Patent Application Laid-Open No. 2011-133825. EP1 to EP4 are novel compounds not disclosed in literature, etc., and their synthesis methods are described in detail in the following Monomer Synthesis Examples 1 to 4.

[0182] < 1 H-NMR determination>

[0183] Apparatus: Fourier transform superconducting nuclear magnetic resonance apparatus (FT-NMR) "AVANCE III" (manufactured by BRUKER), 500 MHz.

[0184] Solvents: deuterated dimethyl sulfoxide (DMSO-d6), deuterated chloroform (CDCl3).

[0185] Standard substance: tetramethylsilane (TMS).

[0186] (Monomer Synthesis Example 1: Synthesis of [EP1])

[0187]

[0188] In a 300mL four-necked flask, trans, trans-4'-pentyldicyclohexyl-4-carboxylic acid (11.2g, 40.0mmol), p-toluenesulfonyl chloride (9.2g, 48.0mmol) and CH2Cl2 (110g) were added, 1-methylimidazole (9.9g, 120mmol) was added dropwise in an ice bath, and stirred at room temperature (25°C) for 3 hours. Next, 4-hydroxy-trans-tert-butyl cinnamate (8.8g, 40.0mmol) dissolved in CH2Cl2 (56g) was added dropwise in an ice bath, and stirred at room temperature. After the reaction was completed, the reaction solution was concentrated, THF (30g) was added to the residue, and it was injected into pure water (90g), and the precipitate was filtered out. MeOH (100 g) was added to the obtained crude product, and the mixture was reslurried and washed at room temperature. AcOEt (100 g) was then added to the crude product, and the mixture was reslurried and washed at 0°C to obtain [EP1-1] (17.1 g, 35.4 mmol, yield: 89%).

[0189] [EP1-1] (17.1 g, 35.4 mmol) and formic acid (260 g) were added to a 500 mL four-necked flask and stirred at 50°C. After the reaction was completed, the reaction solution was poured into pure water (1500 g) and the precipitate was filtered out. MeCN (300 g) was added to the obtained crude product and reslurried and washed at room temperature to obtain [EP1-2] (14.8 g, 34.7 mmol, yield: 98%).

[0190] [EP1-2] (14.8 g, 34.7 mmol), p-toluenesulfonyl chloride (7.9 g, 42.0 mmol) and CH2Cl2 (150 g) were placed in a 500 mL four-necked flask, 1-methylimidazole (8.5 g, 104 mmol) was added dropwise in an ice bath, and the mixture was stirred at room temperature for 3 hours. Next, glycidol (2.8 g, 38.0 mmol) dissolved in CH2Cl2 (74 g) was added dropwise in an ice bath, and the mixture was stirred at room temperature. After the reaction was completed, the reaction solution was concentrated, THF (50 g) was added to the residue, and the mixture was injected into pure water (500 g), and the precipitate was filtered out. Next, the crude product was separated by silica gel column chromatography (AcOEt: Heptane = 1:10 (volume ratio)) to obtain the target [EP1] (white solid) (5.1 g, 10.5 mmol, yield: 30%). The target product is shown below. 1 H-NMR results: From these results, it was confirmed that the obtained solid was the target [EP1].

[0191] 1 H-NMR (500MHz, CDCl3): δ (ppm=)7.69-7.72(d,1H),7.53-7.55(d,2H),7.09-7.11(d,2H) ,6.41-6.44(d,1H),4.53-4.56(m,1H),4.04-4.07(m,1H),3.28-3.30(m,1H),2.88-2.90( t,1H),2.70-2.71(m,1H),2.45-2.49(m,1H),2.14-2.16(d,2H),1.85-1.87(d,2H),1.71 -1.78(m,4H),1.50-1.57(m,2H),1.22-1.32(m,6H),0.95-1.17(m,9H),0.84-0.90(m,5H)

[0192] (Monomer Synthesis Example 2: Synthesis of [EP2])

[0193]

[0194] Into a 300mL four-necked flask, trans, trans-4'-propyldicyclohexyl-4-carboxylic acid (10.1g, 40.0mmol), p-toluenesulfonyl chloride (9.2g, 48.0mmol) and CH2Cl2 (101g) were added, 1-methylimidazole (9.9g, 120mmol) was added dropwise in an ice bath, and stirred at room temperature for 3 hours. Next, 4-hydroxy-trans-tert-butyl cinnamate (8.8g, 40.0mmol) dissolved in CH2Cl2 (51g) was added dropwise in an ice bath, and stirred at room temperature. After the reaction was completed, the reaction solution was concentrated, THF (30g) was added to the residue, injected into pure water (90g), and the precipitate was filtered out. MeOH (100 g) was added to the obtained crude product, and the mixture was reslurried and washed at room temperature. AcOEt (100 g) was then added to the crude product, and the mixture was reslurried and washed at 0°C to obtain [EP2-1] (16.6 g, 36.6 mmol, yield: 92%).

[0195] [EP2-1] (16.6 g, 36.6 mmol) and formic acid (250 g) were placed in a 500 mL four-necked flask and stirred at 50°C. After the reaction was completed, the reaction solution was poured into pure water (1500 g) and the precipitate was filtered out. MeCN (150 g) was added to the obtained crude product and reslurried and washed at room temperature to obtain [EP2-2] (14.4 g, 36.2 mmol, yield: 99%).

[0196] [EP2-2] (14.1 g, 35.3 mmol), p-toluenesulfonyl chloride (8.1 g, 42.0 mmol) and CH2Cl2 (140 g) were placed in a 500 mL four-necked flask, 1-methylimidazole (8.7 g, 106.0 mmol) was added dropwise in an ice bath, and the mixture was stirred at room temperature for 3 hours. Next, glycidol (2.9 g, 39.0 mmol) dissolved in CH2Cl2 (70 g) was added dropwise in an ice bath, and the mixture was stirred at room temperature. After the reaction was completed, the reaction solution was concentrated, THF (50 g) was added to the residue, and the mixture was injected into pure water (500 g), and the precipitate was filtered out. Next, the crude product was separated by silica gel column chromatography (AcOEt: Heptane = 1:10 (volume ratio)) to obtain the target [EP2] (white solid) (8.5 g, 18.6 mmol, yield: 53%). The target product is shown below. 1 H-NMR results: From these results, it was confirmed that the obtained solid was the target [EP2].

[0197] 1 H-NMR (500MHz, CDCl3): δ (ppm=)7.69-7.72(d,1H),7.53-7.55(d,2H),7.09-7.11(d,2H) ,6.41-6.44(d,1H),4.53-4.56(m,1H),4.04-4.07(m,1H),3.29-3.29(m,1H),2.88-2.90( t,1H),2.69-2.71(m,1H),2.44-2.48(m,1H),2.14-2.16(d,2H),1.85-1.87(d,2H),1.71 -1.78(m,4H),1.50-1.56(m,2H),1.27-1.33(m,2H),0.95-1.16(m,9H),0.84-0.89(m,5H)

[0198] (Monomer Synthesis Example 3: Synthesis of [EP3])

[0199]

[0200] In a 1L four-necked flask, trans, trans-4'-(4,4,4-trifluorobutyl)[1,1'-bicyclohexyl]-4-carboxylic acid (30.0 g, 94.0 mmol), p-toluenesulfonyl chloride (21.4 g, 112 mmol) and CH2Cl2 (300 g) were added dropwise to 1-methylimidazole (23.1 g, 281.0 mmol) in an ice bath, and stirred at room temperature for 3 hours. Next, 4-hydroxy-trans-tert-butyl cinnamate (22.7 g, 103 mmol) dissolved in CH2Cl2 (150 g) was added dropwise to the ice bath, and stirred at room temperature. After the reaction was completed, the reaction solution was concentrated, THF (150 g) was added to the residue, and injected into pure water (1000 g), and the precipitate was filtered out. AcOEt (200 g) was added to the obtained crude product, and reslurry washing was performed at 0°C to obtain [EP3-1] (46.5 g, 88.9 mmol, yield: 95%).

[0201] [EP3-1] (46.5 g, 88.9 mmol) and formic acid (700 g) were added to a 2L four-necked flask and stirred at 50°C. After the reaction was completed, the reaction solution was poured into pure water (2000 g) and the precipitate was filtered out. MeCN (300 g) was added to the obtained crude product and reslurried and washed at room temperature to obtain [EP3-2] (41.3 g, 88.6 mmol, yield: 99%).

[0202] Into a 300mL four-necked flask, [EP3-2] (10.0g, 21.4mmol), (2S)-(+)-glycidyl toluenesulfonate (5.4g, 23.6mmol), cesium carbonate (8.4g, 25.7mmol) and NMP (100g) were placed and stirred at 40°C. After the reaction, the reaction solution was injected into pure water (600g), and after making it weakly acidic using 1N-hydrochloric acid aqueous solution, the precipitate was filtered out. MeOH (300g) was added to the obtained crude product, and the product was re-slurried and washed at room temperature. Next, the obtained crude product was separated by silica gel column chromatography (CHCl3:MeCN=100:1 (volume ratio)), thereby obtaining the target [EP3] (white solid) (5.3g, 10.1mmol, yield: 48%). The target material is shown below. 1 H-NMR results: From these results, it was confirmed that the obtained solid was the target [EP3].

[0203] 1 H-NMR (500MHz, CDCl3): δ (ppm=)7.69-7.72(d,1H),7.53-7.55(d,2H),7.09-7.11(d,2H),6.4 1-6.44(d,1H),4.54-4.57(m,1H),4.03-4.07(m,1H),3.28-3.30(m,1H),2.88-2.90(t,1H),2. 70-2.71(m,1H),2.44-2.49(m,1H),2.14-2.17(d,2H),2.01-2.07(m,2H),1.85-1.87(d,2H), 1.73-1.79(m,4H),1.52-1.58(m,4H),1.22-1.26(m,2H),0.96-1.18(m,7H),0.85-0.92(m,2H)

[0204] (Monomer Synthesis Example 4: Synthesis of [EP4])

[0205]

[0206] In a 200 mL four-necked flask, trans, trans-4'-(4,4,4-trifluoropropyl)[1,1'-bicyclohexyl]-4-carboxylic acid (9.2 g, 30.0 mmol), 4-hydroxy-trans-tert-butyl cinnamate (6.6 g, 30.0 mmol), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (8.6 g, 45.0 mmol), 4-dimethylaminopyridine (0.4 g, 3.0 mmol) and THF (92 g) were added and stirred at room temperature. After the reaction was completed, the reaction solution was injected into pure water (1500 g) and the precipitate was filtered out. MeOH (300 g) was added to the obtained crude product, and reslurry washing was performed at room temperature to obtain [EP4-1] (13.7 g, 26.9 mmol, yield: 90%).

[0207] [EP4-1] (13.7 g, 26.9 mmol) and formic acid (205 g) were placed in a 1L four-necked flask and stirred at 50°C. After the reaction was completed, the reaction solution was poured into pure water (1000 g) and the precipitate was filtered out. MeCN (300 g) was added to the obtained crude product and reslurried and washed at room temperature to obtain [EP4-2] (11.9 g, 26.2 mmol, yield: 98%).

[0208] [EP4-2] (6.0 g, 13.3 mmol), p-toluenesulfonyl chloride (3.0 g, 15.9 mmol) and CH2Cl2 (60 g) were placed in a 200 mL four-necked flask, 1-methylimidazole (3.3 g, 40.0 mmol) was added dropwise in an ice bath, and the mixture was stirred at room temperature for 3 hours. Next, glycidol (1.1 g, 14.6 mmol) dissolved in CH2Cl2 (30 g) was added dropwise in an ice bath, and the mixture was stirred at room temperature. After the reaction was completed, the reaction solution was concentrated, AcOEt (600 g) was added to the residue, the organic layer was washed with pure water (1200 g), and the mixture was concentrated. Next, AcOEt (30 g) and EtOH (150) were added to the obtained crude product, and the mixture was re-slurried and washed at 0°C to obtain the target [EP4] (white solid) (3.1 g, 6.0 mmol, yield: 45%). The target product is shown below. 1 H-NMR results: From these results, it was confirmed that the obtained solid was the target [EP4].

[0209] 1 H-NMR (500MHz, CDCl3): δ (ppm=)7.69-7.72(d,1H),7.53-7.55(d,2H),7.09-7.11(d,2H),6.4 1-6.44(d,1H),4.54-4.57(m,1H),4.03-4.07(m,1H),3.28-3.30(m,1H),2.88-2.90(t,1H),2. 70-2.71(m,1H),2.44-2.49(m,1H),2.15-2.17(d,2H),2.05-2.10(m,2H),1.85-1.87(d,2H), 1.75-1.79(m,4H),1.52-1.57(m,2H),1.42-1.50(m,2H),1.20-1.22(m,1H),0.88-1.14(m,8H)

[0210] <Synthesis of Polyamic Acid>

[0211] (Synthesis example 1)

[0212] C1 (2.16 g, 20.00 mmol) and A1 (4.35 g, 19.4 mmol) were dissolved in NMP (26.2 g), and the mixture was reacted at 60° C. for 10 hours to obtain a polyamic acid solution (PAA-1A) having a solid content concentration of 20% by mass.

[0213] NMP (20.0 g) and BCS (20.0 g) were added to the obtained polyamic acid solution (PAA-1A) (10.0 g), and the mixture was stirred at room temperature for 2 hours to obtain a polyamic acid solution (PAA-1) having a solid content concentration of 4% by mass.

[0214] (Synthesis Examples 2 to 3)

[0215] According to the composition shown in Table 1, polyamic acid solutions (PAA-2) to (PAA-3) were synthesized by the same method as in Synthesis Example 1.

[0216] [Table 1]

[0217] surface

[0218]

[0219] (Synthesis Example 4)

[0220] B1 (0.76 g, 2.00 mmol), C1 (1.95 g, 18.00 mmol), and A1 (4.35 g, 19.4 mmol) were dissolved in NMP (28.2 g), and reacted at 60° C. for 10 hours to obtain a polyamic acid solution (PAA-4A) having a solid content concentration of 20% by mass.

[0221] NMP (20.0 g) and BCS (20.0 g) were added to the obtained polyamic acid solution (PAA-4A) (10.0 g), and the mixture was stirred at room temperature for 2 hours to obtain a polyamic acid solution (PAA-4) having a solid content concentration of 4% by mass.

[0222] (Synthesis Example 5)

[0223] According to the composition shown in Table 2, a polyamic acid solution (PAA-5) was synthesized by the same method as in Synthesis Example 4.

[0224] [Table 2]

[0225] Table 2.

[0226]

[0227] <Preparation of Liquid Crystal Alignment Agent>

[0228] (Example 1)

[0229] EP1 (0.03 g) was added to the polyamic acid solution (PAA-1) (50.0 g) obtained in Synthesis Example 1, and a liquid crystal aligning agent (AL-1) was obtained by stirring at room temperature.

[0230] (Examples 2 to 5)

[0231] As shown in Table 3, liquid crystal aligning agents (AL-2) to (AL-5) were obtained in the same manner as in Example 1, except that (PAA-2) to (PAA-5) were used instead of the polyamic acid solution (PAA-1).

[0232] (Examples 6 to 8)

[0233] As shown in Table 3, liquid crystal aligning agents (AL-6) to (AL-8) were obtained in the same manner as in Example 1, except that (EP2) to (EP4) were used in place of the photo-alignment monomer (EP1).

[0234] [Table 3]

[0235] Table 3.

[0236]

[0237] (Comparative Example 1)

[0238] EP5 (0.06 g) was added to the polyamic acid solution (PAA-1) (10.0 g) obtained in Synthesis Example 1, and the mixture was stirred at room temperature to obtain a liquid crystal aligning agent (AL-R1).

[0239] (Comparative Examples 2 to 5)

[0240] As shown in Table 4, liquid crystal aligning agents (AL-R2) to (AL-R5) were obtained in the same manner as in Comparative Example 1, except that (PAA-2) to (PAA-5) were used instead of the polyamic acid solution (PAA-1).

[0241] [Table 4]

[0242] Table 4.

[0243]

[0244] <Production of Liquid Crystal Display Element>

[0245] The liquid crystal aligning agents (AL-1) to (AL-8) obtained in Examples and the liquid crystal aligning agents (AL-R1) to (AL-R5) obtained in Comparative Examples were pressure-filtered using a membrane filter having a pore diameter of 1 μm.

[0246] The obtained solution was spin-coated on the ITO surface of a glass substrate having a transparent electrode formed of an ITO film, dried on a 70°C hot plate for 90 seconds, and then fired on a 200°C hot plate for 30 minutes to form a liquid crystal alignment film with a film thickness of 100 nm.

[0247] Next, the coating surface was irradiated with light at an angle of 40° from the normal direction of the substrate through a polarizing plate with an intensity of 4.3 mW / cm 2 Linearly polarized ultraviolet light with a wavelength of 313nm 50mJ / cm 2 The linearly polarized ultraviolet light is modulated by passing the ultraviolet light from a high pressure mercury lamp through a band pass filter with a wavelength of 313 nm and then through a polarizing plate with a wavelength of 313 nm.

[0248] Two of the above substrates were prepared, and after 4 μm bead spacers were spread on the liquid crystal alignment film of one substrate, a sealant (XN-1500T manufactured by Mitsui Chemicals, Inc.) was applied. Next, another substrate was attached in a manner that the liquid crystal alignment film faces each other and the orientation direction is 180°, and the sealant was thermally cured at 120°C for 90 minutes to prepare an empty cell. Liquid crystal (MLC-3022 manufactured by Merck) was injected into the empty cell by a reduced pressure injection method to obtain a liquid crystal display element.

[0249] <Evaluation>

[0250] (Liquid Crystal Orientation)

[0251] After the obtained liquid crystal display element was subjected to an isotropic treatment at 120° C. for 1 hour, the cell was observed using a polarizing microscope. As an evaluation criterion, the absence of poor orientation such as light leakage and domain generation, and the ability to obtain uniform liquid crystal drive when a voltage was applied to the liquid crystal cell were considered "good". The evaluation results are shown in Table 5.

[0252] (Pretilt Angle)

[0253] The pretilt angle of the liquid crystal cell was measured by the Mueller Matrix method using AxoScan manufactured by Axometrics. Table 5 shows the evaluation results.

[0254] (Evaluation of Pretilt Angle Change)

[0255] A 15 V DC voltage was applied to the liquid crystal display element after the pretilt angle was measured, and the pretilt angle was measured again after 24 hours. The pretilt angle change (Δ pretilt ). The evaluation results are shown in Table 5.

[0256] [Table 5]

[0257] Table 5.

[0258]

[0259] According to the results in Table 5, it can be seen that the liquid crystal alignment film obtained by adding the specific compounds EP1 to EP4 to the polyamic acid has a higher tilt angle stability than the liquid crystal alignment film of the comparative example. Specifically, the comparison is between Examples 1 and 7 and Comparative Example 1, Example 2 and Comparative Example 2, Example 3 and Comparative Example 3, Example 4 and Comparative Example 4, and Example 5 and Comparative Example 5.

[0260] Industrial Applicability

[0261] The liquid crystal display element obtained using the liquid crystal aligning agent of the present invention or the liquid crystal aligning film obtained from the liquid crystal aligning agent can be suitably used for a liquid crystal display element requiring durability such as vehicle-mounted use.< / x> < / x>

Claims

1. A liquid crystal aligning agent comprising a compound as component (A), a polyamic acid as component (B), and a solvent, wherein the compound comprises a photo-alignment group represented by the following formula (pa-1) and a thermally crosslinkable group, wherein the thermally crosslinkable group is a group capable of reacting with a carboxyl group to form a covalent bond, In formula (pa-1), A represents pyrimidine-2,5-diyl, pyridine-2,5-diyl, thiophene-2,5-diyl, furan-2,5-diyl, 1,4-naphthylene or phenylene, or 2,6-naphthylene or phenylene, and the pyrimidine-2,5-diyl, pyridine-2,5-diyl, thiophene-2,5-diyl, furan-2,5-diyl, 1,4-naphthylene or phenylene, or 2,6-naphthylene or phenylene is substituted by a group selected from a fluorine atom, a chlorine atom and a cyano group or by a carbon atom. wherein the alkoxy group or the straight-chain or branched-chain alkyl residue having 1 to 5 carbon atoms is substituted by one cyano group or one or more halogen atoms as appropriate; R1 is -COO- or -OCO-; R2 is cyclohexane-1,4-diyl; R3 is cyclohexane-1,4-diyl; R4 is a straight-chain or branched-chain alkyl group having 1 to 40 carbon atoms, a part or all of the hydrogen atoms of the alkyl group are optionally substituted by fluorine atoms; D represents an oxygen atom, a sulfur atom or -NR d -, where R d represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; a is an integer of 0 to 3; * represents a bonding position; X and Y are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or an alkyl group having 1 to 3 carbon atoms, wherein a part or all of the hydrogen atoms of the alkyl group may be substituted with fluorine atoms.

2. The liquid crystal alignment agent according to claim 1, wherein The heat-crosslinkable group of the component (A) is a group selected from the group consisting of an epoxy moiety-containing group, an oxetane moiety-containing group, a thiirane moiety-containing group and a cyclocarbonate group.

3. The liquid crystal alignment agent according to claim 1, wherein The thermally crosslinkable group of the component (A) is a group containing an epoxy moiety. 4 . A liquid crystal alignment film formed using the liquid crystal aligning agent according to claim 1 .

5. A method for manufacturing a liquid crystal alignment film, comprising: A step of applying the liquid crystal alignment agent according to any one of claims 1 to 3 on a substrate to form a coating film; as well as A step of irradiating the coating film with light in a state where the coating film is not in contact with the liquid crystal layer or in a state where the coating film is in contact with the liquid crystal layer. 6 . A liquid crystal display element comprising the liquid crystal alignment film according to claim 4 or a liquid crystal alignment film obtained by the production method according to claim 5 .

7. A compound having a photo-alignment group represented by the following formula (pa-1) and a thermally crosslinkable group, wherein the thermally crosslinkable group is a group capable of reacting with a carboxyl group to form a covalent bond, In formula (pa-1), A represents pyrimidine-2,5-diyl, pyridine-2,5-diyl, thiophene-2,5-diyl, furan-2,5-diyl, 1,4-naphthylene or phenylene, or 2,6-naphthylene or phenylene, and the pyrimidine-2,5-diyl, pyridine-2,5-diyl, thiophene-2,5-diyl, furan-2,5-diyl, 1,4-naphthylene or phenylene, or 2,6-naphthylene or phenylene is substituted by a group selected from a fluorine atom, a chlorine atom and a cyano group or by a carbon atom. wherein the alkoxy group or the straight-chain or branched-chain alkyl residue having 1 to 5 carbon atoms is substituted by one cyano group or one or more halogen atoms as appropriate; R1 is -COO- or -OCO-; R2 is cyclohexane-1,4-diyl; R3 is cyclohexane-1,4-diyl; R4 is a straight-chain or branched-chain alkyl group having 1 to 40 carbon atoms, a part or all of the hydrogen atoms of the alkyl group are optionally substituted by fluorine atoms; D represents an oxygen atom, a sulfur atom or -NR d -, where R d represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; a is an integer of 0 to 3; * represents a bonding position; X and Y are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or an alkyl group having 1 to 3 carbon atoms, wherein a part or all of the hydrogen atoms of the alkyl group may be substituted with fluorine atoms.

8. The compound according to claim 7, wherein The heat-crosslinkable group is a group selected from the group consisting of an epoxy site-containing group, an oxetane site-containing group, a thiirane site-containing group and a cyclocarbonate group.

9. A compound represented by any of the following formulae (paa-1-ma1) to (paa-1-ma4):

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