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

Abstract

The present invention provides: a liquid crystal alignment film which has good liquid crystal alignment properties, while having excellent pretilt angle developability; a liquid crystal display element which is provided with this liquid crystal alignment film; and a liquid crystal aligning agent which enables the achievement of this liquid crystal alignment film. The present invention provides a liquid crystal aligning agent which contains: a component (A) that is composed of a compound having a photo-alignment group represented by formula (pa-1) and a thermally crosslinkable group that is capable of forming a covalent bond by being reacted with a carboxy group; and a component (B) that is composed of a polyamic acid and a solvent. (In the formula, A represents a phenylene group or the like; R1 represents a single bond, an oxygen atom or the like; R2 represents a divalent aromatic group or the like; R3 represents a single bond, an oxygen atom or the like; R4 represents a linear or branched alkyl group having 1 to 40 carbon atoms or a monovalent organic group containing an alicyclic group and having 3 to 40 carbon atoms; D represents an oxygen atom, a sulfur atom or -NRd-; a represents an integer of 0 to 3; and * represents a bonding position.)

Description

[Technical Field]

[0001] The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film obtained thereby, and a liquid crystal display element comprising the obtained liquid crystal alignment film. More specifically, the present invention relates to a liquid crystal alignment agent capable of providing a liquid crystal alignment film that exhibits good liquid crystal alignment, excellent pre-tilt angle generation ability, and high reliability, and to a liquid crystal display element with excellent display quality. [Background technology]

[0002] In liquid crystal display elements, the liquid crystal alignment film plays the role of aligning the liquid crystals in a specific direction. Currently, the main liquid crystal alignment films used industrially are fabricated by coating a substrate with a polyimide-based liquid crystal alignment agent, which consists of polyimide precursors such as polyamic acid (also called polyamic acid), polyamic acid esters, or a solution of polyimide. Furthermore, when the liquid crystal is aligned parallel or at an angle to the substrate surface, a surface stretching treatment by rubbing is performed after film formation.

[0003] On the other hand, when aligning liquid crystals perpendicular to the substrate (called the vertical alignment (VA) method), a liquid crystal alignment film is used in which hydrophobic groups such as long-chain alkyl groups, cyclic groups, or combinations of cyclic groups and alkyl groups (see, for example, Patent Document 1), or steroid skeletons (see, for example, Patent Document 2) are introduced into the side chains of polyimide. In this case, when a voltage is applied between the substrates and the liquid crystal molecules tilt toward a direction parallel to the substrate, it is necessary to ensure that the liquid crystal molecules tilt toward one direction within the substrate plane from the direction normal to the substrate. As means to achieve this, for example, a method of providing protrusions on the substrate, a method of providing slits in the display electrodes, a method of slightly tilting the liquid crystal molecules toward one direction within the substrate plane from the direction normal to the substrate by rubbing (pre-tilting), and a method of pre-tilting the liquid crystal by adding a photopolymerizable compound to the liquid crystal composition in advance and using it together with a vertical alignment film such as polyimide, and irradiating the liquid crystal cell with ultraviolet light while applying a voltage (see, for example, Patent Document 3).

[0004] In recent years, methods such as the formation of protrusions and slits in the liquid crystal alignment control of the VA mode, and methods using anisotropic photoreactions such as polarized ultraviolet irradiation as an alternative to the PSA technique (photoalignment method) have also been proposed. That is, it is known that by irradiating a vertically aligning polyimide film having photoreactivity with polarized ultraviolet light and imparting alignment control ability and pretilt angle expression ability, the tilt direction of liquid crystal molecules when a voltage is applied can be uniformly controlled (see Patent Document 4).

[0005] VA-mode liquid crystal display elements are used in TVs and in-vehicle displays because of their high contrast and wide viewing angle. Liquid crystal display elements for TVs use a backlight with a large amount of heat generation to obtain high brightness, or liquid crystal display elements used in in-vehicle applications, for example, in car navigation systems and meter panels, may be used or left in a high-temperature environment for a long time. Under such harsh conditions, when the pretilt angle gradually changes, problems such as the inability to obtain the initial display characteristics or the occurrence of unevenness in the display may occur. Furthermore, the voltage holding characteristics and charge storage characteristics when driving the liquid crystal are also affected by the liquid crystal alignment film. When the voltage holding ratio is low, the contrast of the display screen decreases, and when the charge accumulation with respect to the DC voltage is large, a phenomenon such as the display screen being burned occurs.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0007] The present invention has been made in view of the above circumstances, and its objective is to provide a liquid crystal alignment film that exhibits minimal change in pre-tilt angle even after long-term operation, excellent display reliability, high voltage retention characteristics, and reduced charge accumulation, a liquid crystal display element having the same, and a liquid crystal alignment agent that provides the same. [Means for solving the problem]

[0008] The inventors of the present invention have identified the following: <x>I have discovered an invention whose gist is as follows. <x>A liquid crystal alignment agent comprising (A) a compound having a photo-aligning group and a thermally crosslinkable group represented by the following formula (pa-1), wherein the thermally crosslinkable group is a group that can react with a carboxyl group to form a covalent bond, and (B) a polyamic acid and a solvent.

[0009] [ka]

[0010] In formula (pa-1), A is optionally a group selected from a fluorine atom, a chlorine atom, and a cyano group, or a pyrimidine-2,5-diyl group, pyridine-2,5-diyl group, thiophene-2,5-diyl group, furan-2,5-diyl group, 1,4- or 2,6-naphthylene group, or phenylene group, which are substituted with a carbon-1 to carbon-5 alkoxy group, a linear or branched alkyl residue (which is optionally substituted with one cyano group or one or more halogen atoms). R1 is a single bond, an oxygen atom, -COO- or -OCO-, R2 is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group, or a divalent fused cyclic group, R3 is a single bond, an oxygen atom, -COO- or -OCO-, R4 is a monovalent organic group having 3 to 40 carbon atoms, including a linear or branched alkyl group or alicyclic group having 1 to 40 carbon atoms, some or all of the hydrogen atoms of this alkyl group may be substituted with fluorine atoms, and D is an oxygen atom, a sulfur atom, or -NR d -(Here, R d R1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, a is an integer from 0 to 3, and * represents the bond position. If a is 2 or more, multiple R1 and R2 groups each independently have the above definition. 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, and some or all of the hydrogen atoms of this alkyl group may be substituted with fluorine atoms. The "wavy lines" between "C" and "A," and between "C" and "X," may be in E-form or Z-form. In this specification, "wavy line" has the same meaning as above. [Effects of the Invention]

[0011] The present invention provides a liquid crystal alignment film and a liquid crystal alignment agent that exhibit good liquid crystal alignment properties and excellent pre-tilt angle generation capabilities. Furthermore, the liquid crystal display element manufactured by the method of the present invention has excellent display characteristics. [Modes for carrying out the invention]

[0012] The liquid crystal alignment agent of the present invention contains, as component (A), a compound having a photo-aligning group represented by formula (pa-1) and a thermally crosslinkable group, wherein the thermally crosslinkable group is a group that can react with a carboxyl group to form a covalent bond (hereinafter also referred to as a specific compound), as component (B), a polyamic acid, and a solvent.

[0013] The compound that is component (A) contained in the liquid crystal alignment agent of the present invention has a photo-aligning group and a thermally crosslinkable group. Here, since the photo-aligning group is highly sensitive to light, it can exhibit alignment control ability even under low exposure dose polarized ultraviolet irradiation. Furthermore, because the photo-aligning group of component (A) is hydrophobic, when the liquid crystal alignment agent is applied to a substrate, the polyamic acid of component (B) accumulates on the substrate side, and the compound of component (A) accumulates on the surface side. As a result, the coating film obtained using the liquid crystal alignment agent of the present invention has the photo-aligning groups concentrated on the surface, so good alignment can be obtained even if the content of the compound of component (A) is reduced. In addition, because the thermally crosslinkable group of component (A) is a group that can react with a carboxyl group to form a covalent bond, a crosslinking reaction between the compound of component (A) and component (B) is possible even when the firing time of the liquid crystal alignment agent is short. As a result, when the photo-aligning portion exhibits anisotropy due to the photoreaction, the anisotropy is more likely to remain (memory) in the liquid crystal alignment film, thereby improving liquid crystal alignment and enabling the expression of the liquid crystal pre-tilt angle.

[0014] Furthermore, by including polyamic acid, which is component (B), the liquid crystal alignment agent of the present invention can also improve electrical properties such as voltage retention and suppression of residual charge accumulation. Hereinafter, each component of the present invention will be described in detail.

[0015] <Component (A): Specific Compound> The specific compound which is the component (A) of the liquid crystal aligning agent of the present invention has a photo-aligning group and a thermally crosslinkable group represented by the formula (pa-1), and the thermally crosslinkable group is a group capable of reacting with a carboxy group to form a covalent bond. Such a specific compound is preferably, for example, a compound represented by the formula (a-1).

[0016] [Chemical Formula]

[0017] In the formula (a-1), M a represents a thermally crosslinkable group. Examples of the thermally crosslinkable group include organic groups selected from the group consisting of an epoxy moiety-containing group, an oxetanyl group, a thiiranyl group, and a cyclocarbonate group.

[0018] In the above formula (a-1), S a represents a spacer, and I a indicates that it is optionally bonded to the thermally crosslinkable group via a spacer. S a can be represented, for example, by the structure of the following formula (Sp).

[0019] [Chemical Formula]

[0020] In the formula (Sp), the left bond of W1 represents the bond to M a , the right bond of W3 represents the bond to I a , W1, W2 and W3 are each independently a single bond, a divalent heterocyclic ring, -(CH2) n -(wherein n represents 1 to 20), -OCH2-, -CH2O-, -COO-, -OCO-, -CH=CH-, -CF=CF-, -CF2O-, -OCF2-, -CF2CF2-, or -C≡C-, but in these substituents, one or more non-adjacent CH2 groups can be independently substituted with -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 a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms). A1 and A2 are each independently selected from a single bond, an alkylene group, a divalent aromatic group, a divalent alicyclic group, or a divalent heterocyclic group, and each group may be unsubstituted or one or more hydrogen atoms may be substituted with a fluorine atom, a chlorine atom, a cyano group, a methyl group, or a methoxy group.

[0021] Examples of aromatic groups in A1 and A2 include aromatic hydrocarbon groups having 6 to 18 carbon atoms, such as benzene rings, biphenyl structures, and naphthalene rings. Examples of alicyclic groups in A1 and A2 include alicyclic hydrocarbon groups having 6 to 12 carbon atoms, such as cyclohexane rings and bicyclohexane structures. Examples of heterocycles in A1 and A2 include nitrogen-containing heterocycles such as pyridine rings, piperidine rings, and piperazine rings. Examples of alkylene groups in A1 and A2 include linear or branched alkylene groups having 1 to 10 carbon atoms.

[0022] In formula (a-1), I a This is a monovalent organic group represented by formula (pa-1).

[0023] [ka]

[0024] In formula (pa-1), A is optionally a group selected from a fluorine atom, a chlorine atom, and a cyano group, or a pyrimidine-2,5-diyl group, pyridine-2,5-diyl group, thiophene-2,5-diyl group, furan-2,5-diyl group, 1,4- or 2,6-naphthylene group, or phenylene group, which are substituted with a carbon-1 to carbon-5 alkoxy group, a linear or branched alkyl residue (which is optionally substituted with one cyano group or one or more halogen atoms). R1 is a single bond, an oxygen atom, -COO- or -OCO-, R2 is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group, or a divalent fused cyclic group, R3 is a single bond, an oxygen atom, -COO- or -OCO-, R4 is a monovalent organic group having 3 to 40 carbon atoms, including a linear or branched alkyl group or alicyclic group having 1 to 40 carbon atoms, some or all of the hydrogen atoms of this alkyl group may be substituted with fluorine atoms, and D is an oxygen atom, a sulfur atom, or -NR d -(Here, R d R1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, a is an integer from 0 to 3, and * represents the bond position. If a is 2 or more, multiple R1 and R2 groups each independently have the above definition. 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, and some or all of the hydrogen atoms of this alkyl group may be substituted with fluorine atoms.

[0025] From the viewpoint of achieving good vertical orientation control and a stable pre-tilt angle, the group represented by (pa-1) above is preferably the group represented by (pa-1-a) below, but is not limited thereto.

[0026] [ka]

[0027] In formula (pa-1-a), Z is either an oxygen atom or a sulfur atom. X a and X b Each of these is independently a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, or an alkyl group having 1 to 3 carbon atoms, and some or all of the hydrogen atoms of this alkyl group may be substituted with fluorine atoms. R1 is a single bond, an oxygen atom, -COO- or -OCO-. R2 is a divalent aromatic group, a divalent alicyclic group, or a divalent heterocyclic group. R3 is a single bond, an oxygen atom, -COO- or -OCO-. R4 is a linear or branched alkyl group having 1 to 40 carbon atoms, or a monovalent organic group having 3 to 40 carbon atoms including an alicyclic group, and some or all of the hydrogen atoms of this alkyl group may be substituted with fluorine atoms. 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, preferably a methyl group, a methoxy group, or a fluorine atom. a is an integer between 0 and 3, and b is an integer between 0 and 4.

[0028] In formula (a-1), S a The linear or branched alkylene group having 1 to 10 carbon atoms is preferably a linear or branched alkylene group having 1 to 8 carbon atoms, for example, a methylene group, an ethylene group, an n-propylene group, an n-butylene group, a t-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, or an n-octylene group. S a Examples of divalent aromatic groups include 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, and 2,3,5,6-tetrafluoro-1,4-phenylene group.

[0029] In formula (a-1), S a Examples of divalent alicyclic groups include trans-1,4-cyclohexylene and trans-trans-1,4-bicyclohexylene. S a Examples of divalent heterocyclic groups include pyridine-2,6-diyl group, pyridine-3,5-diyl group, furan-2,5-diyl group, piperazine-1,4-diyl group, and piperidine-1,4-diyl group. S a It is preferably an alkylene group having 1 to 8 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms. In the above equation (a-1), the spacer S a -CH2- is preferred.

[0030] In formula (pa-1), examples of the divalent aromatic group of R2 include 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 2,3,5,6-tetrafluoro-1,4-phenylene group, naphthylene group, etc. Examples of the divalent alicyclic group of R2 include trans-1,4-cyclohexylene and trans-trans-1,4-bicyclohexylene. Examples of divalent heterocyclic groups for R2 include pyridine-2,6-diyl group, pyridine-3,5-diyl group, furan-2,5-diyl group, piperazine-1,4-diyl group, and piperidine-1,4-diyl group. R2 is preferably a 1,4-phenylene group, a trans-1,4-cyclohexylene group, or a trans-trans-1,4-bicyclohexylene group.

[0031] Examples of linear or branched alkyl groups having 1 to 40 carbon atoms in R4 include linear or branched alkyl groups having 1 to 20 carbon atoms, and some or all of the hydrogen atoms in this alkyl group may be substituted with fluorine atoms. Examples of such alkyl groups include, for example, methyl group, ethyl group, n-propyl, n-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-lauryl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, 4,4, Examples include 4-trifluorobutyl group, 4,4,5,5,5-pentafluoropentyl group, 4,4,5,5,6,6,6-heptafluorohexyl group, 3,3,4,4,5,5,5-heptafluoropentyl group, 2,2,2-trifluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, 2-(perfluorobutyl)ethyl group, 2-(perfluorooctyl)ethyl group, and 2-(perfluorodecyl)ethyl group.

[0032] Examples of monovalent organic groups having 3 to 40 carbon atoms that include the alicyclic group R4 include the cholestenyl group, cholestanyl group, adamantyl group, and groups represented by the following formulas (Alc-1) or (Alc-2) (wherein R7 is a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 20 carbon atoms, respectively, and any hydrogen atom of the alkyl group having 1 to 20 carbon atoms may be substituted with a fluorine atom, and * indicates the bond position).

[0033] [ka]

[0034] Furthermore, if at least one of X and Y in formula (pa-1) is a group other than a hydrogen atom among the groups defined in this application, the oxidation of the C=C double bond substituted by X and Y is suppressed, thereby improving the stability of the film after coating and firing of the orientation agent.

[0035] (A) Examples of specific compounds that are components include, but are not limited to, the compounds represented by formulas (paa-1-ma1) to (paa-1-ma22). In the formulas, "(E)" indicates that it is the E-isomer, "(E,Z)" indicates that it is either the E-isomer or the Z-isomer, and "t" indicates that the cyclohexyl group is in the trans form.

[0036] [ka]

[0037] [ka]

[0038] <Method for producing specific compounds> (A) The specific compound that is component (A) can be produced by combining known reactions, and specifically, it can be produced by the method described in "Examples of Specific Compound Synthesis" below, or by a similar method.

[0039] <(B) component> The liquid crystal alignment agent of the present invention contains polyamic acid (P) as component (B). The above polyamic acid (P) can be obtained by a polymerization reaction between a diamine component and a tetracarboxylic acid component containing a tetracarboxylic dianhydride. Note that the polyamic acid (P), which is component (B), only needs to retain carboxyl groups that react with the thermally crosslinkable groups contained in component (A), and may be partially imidized or esterified.

[0040] (Diamine) The diamine component used in the production of the above-mentioned polyamic acid (P) can be various diamines depending on the purpose. The diamine used in the production of polyamic acid (P) may be used alone or in combination of two or more types. Preferred specific examples of diamines used in the production of polyamic acid (P) (hereinafter also referred to as diamine (p)) include the following diamines.

[0041] Aromatic diamines represented by "AXJ" (d) (details below), 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 phenyl, 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-diaminobiphenyl Minonaphthalene, 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-aminophenoxy)dodecane, 3-[2-[2-(4-aminophenoxy)ethoxy]ethoxy]benzeneamine, 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-amino Phenoxy)diphenyl, 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]butanediate, 1,6-bi S[2-(4-aminophenyl)ethyl]hexanediate, 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; 4,4'-diaminoazobenzene, diaminotran, 4,4'-diaminochalcone, or [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-propa-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]propa-2-enoyl]oxymethyl]phenyl]phenyl]methoxy]-3-oxo-propa-1-enyl]phenyl]4-(4,4,Diamines having photo-directing groups, such as aromatic diamines with a cinnamate structure in the side chain, represented by 4-trifluorobutoxy)benzoate; diamines having photopolymerizable groups at the terminal, such as 2-(2,4-diaminophenoxy)ethyl methacrylate and 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 Diamines having a group in the molecule that exhibits radical polymerization initiator function, such as benzoin or its alkyl ether derivatives, benzyl ketals, acetophenones, acylphosphine oxides, benzophenones, or aminobenzophenones, represented by 3,5-diaminobenzoate; diamines having an amide bond, such as 4,4'-diaminobenzanilide; diamines having a urea bond, such as 1,3-bis(4-aminophenyl)urea, 1,3-bis(4-aminobenzyl)urea, 1,3-bis(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'-di Aminodiphenyl 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 n, 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-diaminoacridin, N- Tyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N-[3-(1H-imidazole-1-yl)propyl]-3,5-diaminobenzamide, 4-[4-[(4-aminophenoxy)methyl]-4,5-dihydro-4-methyl-2-oxazolyl]benzeneamine, 1,4-bis(p-aminobenzyl)piperazine, 4,4'-propane-1,3-diylbis(piperidine-1,4-diyl)dianiline , 4-(4-aminophenoxycarbonyl)-1-(4-aminophenyl)piperidine, diamine 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[benzeneamine], 1,4-bis-(4-aminophenyl)-piperazine, 2-N-(4-aminophenyl)pyridine-2,5-diamine, 2-N-(5-aminopyridine-2-yl ) Heterocyclic diamines such as pyridine-2,5-diamine, 2-(4-aminophenyl)-5-aminobenzimidazole, 2-(4-aminophenyl)-6-aminobenzimidazole, 5-(1H-benzimidazole-2-yl)benzene-1,3-diamine, or 4,4'-diaminodiphenylamine, 4,4'-diaminodiphenyl-N-methylamine, N,N'-bis(4-aminophenyl)-1,4-benzenediamine, N,N'-bis(4-aminophenyl)-benzidine, N,N'-bis(4-aminophenyl)-N,N'-dimethylbenzidine, or N,N'-bis(4-aminophenyl)-N,N'-dimethyl-1,Diamines having a diphenylamine structure, such as 4-benzenediamine, which have 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 (however, they do not have amino groups to which protecting groups that are removed by heating and replaced by hydrogen atoms are attached in the molecule); 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,4'-diaminobiphenyl-3-carboxylic acid, 4,4'-diaminodiphenylmethane-3-carboxylic acid, 1,2-bis(4- Diamines having a carboxyl group, such as 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-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;N1,N 6-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-[[1-(4-aminophenyl)-4-piperidinyl]methyl]-,1,1-dimethylethyl ester, etc. The group "-N(D)-" (D is removed by heating and placed on a hydrogen atom) A diamine having a long-chain alkyl group with 12 to 20 carbon atoms, such as 1-dodecanoxy-2,4-diaminobenzene, 1-tetradecanoxy-2,4-diaminobenzene, 1-pentadecanoxy-2,4-diaminobenzene, 1-hexadecanoxy-2,4-diaminobenzene, 1-octadecanoxy-2,4-diaminobenzene, 1-dodecanoxy-2,5-diaminobenzene, 1-tetradecanoxy-2,5-diaminobenzene, 1-pentadecanoxy-2,5-diaminobenzene, 1-hexadecanoxy-2,5-diaminobenzene, and 1-octadecanoxy-2,5-diaminobenzene (tn ); Diamines having siloxane bonds such as 1,3-bis(3-aminopropyl)-tetramethyldisiloxane and 1,3-bis[3-(p-aminophenylcarbamoyl)propyl]tetramethyldisiloxane; metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), and diamines in which two amino groups are bonded to a group represented by any of the formulas (Y-1) to (Y-167) described in International Publication No. 2018 / 117239.

[0042] [ka]

[0043] In the aromatic diamine (d) represented as "AXJ" 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 represents a single bond, -(CH2) a -(a is an integer between 1 and 15), -CONH-, -NHCO-, -CO-N(CH3)-, -NH-, -O-, -COO-, -OCO-, or -(A0) m0 -((CH2) a1 -A1) m1 -(a1 is an integer from 1 to 15, A 0、 A1 represents an oxygen atom or -COO-, m0 is an integer of 0 or 1, and m1 is an integer of 1 to 2. If m1 is 2, then multiple a1 and A1 each have the above definition independently. J represents a monovalent organic group having at least one group selected from the group consisting of alicyclic hydrocarbon groups having 4 to 40 carbon atoms and aromatic hydrocarbon groups having 6 to 40 carbon atoms. However, at least one of the hydrogen atoms in the above alicyclic hydrocarbon group and aromatic hydrocarbon group is substituted by a substituent (v) which is one of the following: a halogen atom, a halogen atom-containing alkyl group, a halogen atom-containing alkoxy group, an alkyl group having 3 to 10 carbon atoms, an alkoxy group having 3 to 10 carbon atoms, or an alkenyl group having 3 to 10 carbon atoms. Furthermore, any carbon-carbon single bond in these substituents (v) (except for halogen atoms) may be interrupted by -O-. In addition, J may further have at least one group selected from the group consisting of alicyclic hydrocarbon groups and aromatic hydrocarbon groups that are unsubstituted or substituted with substituents other than the substituents (v) described above.

[0044] 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.

[0045] Examples of alicyclic hydrocarbon groups of J include cyclobutane rings, cyclopentane rings, cyclohexane rings, cyclodecane rings, and steroid skeletons (e.g., cholestanil group, cholesteryl group, lanostanil group, etc.), while examples of aromatic hydrocarbon groups include benzene rings and naphthalene rings. When J has at least one of a cyclohexane ring and a benzene ring, the group "-XJ" can be represented by, for example, the following structure (S1), and more preferred structures can be represented by the following formulas (S1-1) to (S1-5).

[0046] [ka]

[0047] In formula (S1), X 1 This is a single bond, -(CH2) a -(a is an integer between 1 and 15), -CONH-, -CO-N(CH3)-, -NH-, -O-, -COO-, or -(A0) m0 -((CH2) a1 -A1) m1 -(a1 is an integer from 1 to 15, A 0、 A1 represents an oxygen atom or -COO-, m0 is an integer of 0 or 1, and m1 is an integer of 1 to 2. If m1 is 2, multiple a1 and A1 each have the above definition independently. * represents a bond position. G 1 represents a divalent cyclic group selected from a phenylene group and a cyclohexylene group. Any hydrogen atom on the cyclic group may be substituted with a C1-C3 alkyl group, a C1-C3 alkoxy group, a C1-C3 fluorine atom-containing alkyl group, a C1-C3 fluorine atom-containing alkoxy group, or a fluorine atom. m is an integer between 1 and 4. If m is 2 or greater, multiple X 1 , G 1 Each of these has its own independent definition. R 1 This represents 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 an alkoxyalkyl group having 3 to 10 carbon atoms. Note that in equations (S1-1) to (S1-5), X 1 , R 1 * represents X in the above equation (S1). 1 , R 1 This is synonymous with *.

[0048] [ka]

[0049] Specific examples of the above aromatic diamine (d) include diamines represented by the following formulas (d-1) to (d-2). More preferred examples include diamines represented by formulas (d-1) to (d-2) in which the group "-XJ" is one of the above structure (S1) or the above formulas (S1-1) to (S1-5), as well as diamines having a steroid skeleton such as cholestanyloxy-3,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestanyl 3,5-diaminobenzoate, cholestenyl 3,5-diaminobenzoate, lanostanyl 3,5-diaminobenzoate, and 3,6-bis(4-aminobenzoyloxy)cholestane. X and J are synonymous with X and J of the aromatic diamine (d) described above, including in preferred embodiments. In formula (d-2), the two X and J may be the same or different from each other.

[0050] [ka]

[0051] When the above aromatic diamine (d) is used as the above diamine (p), 5 to 95 mol% and more preferably 10 to 90 mol% of the total diamine component used to produce the polyamic acid (P) is preferred.

[0052] (Tetracarboxylic acid dianhydride) The tetracarboxylic dianhydrides that can be used in the synthesis of the above polyamic acid (P) include at least one compound selected from the group consisting of acyclic aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, and aromatic tetracarboxylic dianhydrides. Here, an acyclic aliphatic tetracarboxylic dianhydride is an acidic dianhydride obtained by intramolecular dehydration of four carboxyl groups bonded to a chain-like hydrocarbon structure. However, it does not need to consist solely of a chain-like hydrocarbon structure; it may also contain alicyclic or aromatic ring structures as part of it. Alicyclic tetracarboxylic dianhydrides are acidic dianhydrides obtained by intramolecular dehydration of four carboxyl groups, including at least one carboxyl group bonded to the alicyclic structure. However, none of these four carboxyl groups are bonded to an aromatic ring. Furthermore, the structure does not need to consist solely of alicyclic structures; it may also contain a chain-like hydrocarbon structure or an aromatic ring structure in part. The above acyclic aliphatic tetracarboxylic dianhydrides and alicyclic tetracarboxylic dianhydrides may be used individually or in combination of two or more types. Aromatic tetracarboxylic dianhydrides are acidic dianhydrides obtained by intramolecular dehydration of four carboxyl groups, including at least one carboxyl group bonded to the aromatic ring.

[0053] The tetracarboxylic dianhydrides that can be used in the synthesis of the above polyamic acid (P) are more preferably tetracarboxylic dianhydrides having at least one substructure selected from the group consisting of a benzene ring, a cyclobutane ring structure, a cyclopentane ring structure, and a cyclohexane ring structure, and even more preferably tetracarboxylic dianhydrides having at least one substructure selected from the group consisting of a cyclobutane ring structure, a cyclopentane ring structure, and a cyclohexane ring structure. The tetracarboxylic acid components that can be used in the synthesis of polyamic acid (P) preferably include the following tetracarboxylic dianhydrides (hereinafter collectively referred to as specific tetracarboxylic dianhydrides). Furthermore, the above-mentioned tetracarboxylic dianhydrides may be used individually or in combination of two or more types.

[0054] 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 dianhydride, 1,2,4,5-cyclohexanetetracarboxylic Dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)tetrahydronaphthalene-1,2-dicarboxylic acid anhydride, 5-(2,5-dioxotetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-di On, 5-(2,5-dioxotetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, bicyclo[2.2.2]octa-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] Alicyclic tetracarboxylic dianhydrides such as octane-2:4,6:8-dianhydride; pyromellitic acid dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-diphenylethertetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride Aromatic tetracarboxylic dianhydrides such as rubonic acid dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, ethylene glycol bisanhydrotrimellitate, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 4,4'-carbonyldiphthalic anhydride, 4,4'-(1,4-phenylenedioxy)bis(phthalic anhydride), or 4,4'-(1,4-phenylenedimethylene)bis(phthalic anhydride); and other tetracarboxylic dianhydrides described in Japanese Patent Publication No. 2010-97188.

[0055] Preferred examples of the above-mentioned specific tetracarboxylic acid derivatives include 1,2,3,4-butanetetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-difluoro-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-bis(trifluoromethyl)-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentylacetic acid 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-tetrahydronaphtho[1,2-c]furan-1,3-dione, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, pyromellitic dianhydride, 3,3',4,4 These are '-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-diphenylethertetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 2,2',3,3'-biphenyltetracarboxylic dianhydride.

[0056] The proportion of the above-mentioned specific tetracarboxylic dianhydride used is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 50 mol% or more, based on 1 mole of the total tetracarboxylic acid component used.

[0057] (Synthesis of polyamic acids) The synthesis of polyamic acids 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 tetracarboxylic dianhydride to diamine used in the synthesis reaction of polyamic acids is preferably such that the acid anhydride groups of the tetracarboxylic dianhydride are in the proportion of 0.5 to 2 equivalents, and more preferably 0.8 to 1.2 equivalents, per 1 equivalent of amino groups of the diamine. As with ordinary polycondensation reactions, the closer the equivalent amount of acid anhydride groups of the tetracarboxylic dianhydride is to 1 equivalent, the larger the molecular weight of the resulting polyamic acid. The reaction temperature for the synthesis of polyamic acids 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. The synthesis reaction of polyamic acids can be carried out at any concentration, but preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The reaction can be carried out at a high concentration initially, and then the solvent can be added.

[0058] Specific examples of the above organic solvents include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and 1,3-dimethyl-2-imidazolidinone. Furthermore, if 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.

[0059] <End capping agent> In synthesizing the polyamic acid in the present invention, a tetracarboxylic acid component containing a tetracarboxylic acid dianhydride or its derivative, and a diamine component containing the above-mentioned diamine, may be used together with a suitable end-sealing agent to synthesize a end-sealed polymer. The end-sealed polymer has the effect of improving the film hardness of the orientation film obtained by the coating film and improving the adhesion characteristics between the sealant and the orientation film. Examples of the terminals of polyamic acids in the present invention include amino groups, carboxyl groups, acid anhydride groups, or groups derived from end-capturing agents described later. Amino groups, carboxyl groups, and acid anhydride groups can be obtained by conventional condensation reactions or by encapsulating the ends using the following end-capturing agents.

[0060] Examples of end-capturing agents include acid anhydrides such as acetic anhydride, maleic anhydride, nadic anhydride, phthalic anhydride, itaconic anhydride, cyclohexanedicarboxylic acid 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; dicarbonate diester compounds such as di-tert-butyl dicarbonate and diallyl dicarbonate; chlorocarbonyl compounds such as acryloyl chloride, methacryloyl chloride, and nicotinic acid chloride; and aniline Examples include monoamine compounds such as n-aminophenol, 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; and isocyanates having unsaturated bonds such as ethyl isocyanate, phenyl isocyanate, naphthyl isocyanate, or 2-acryloyloxyethyl isocyanate and 2-methacryloyloxyethyl isocyanate.

[0061] The proportion of end-capturing agent used is preferably 0.01 to 20 moles, and more preferably 0.01 to 10 moles, per 100 moles of the total diamine components used.

[0062] The weight-average molecular weight (Mw) of polyamic acid, measured by gel permeation chromatography (GPC) in terms of polystyrene, is preferably 1,000 to 500,000, and more preferably 2,000 to 300,000. Furthermore, the molecular weight distribution (Mw / Mn), expressed as the ratio of Mw to the number-average molecular weight (Mn) measured by GPC in terms of polystyrene, is preferably 15 or less, and more preferably 10 or less. Being within this molecular weight range ensures good orientation of the liquid crystal display element.

[0063] The content of the specific compound that is component (A) in the liquid crystal alignment agent of the present invention is preferably 1 to 50 parts by mass, more preferably 3 to 30 parts by mass, and even more preferably 5 to 20 parts by mass, per 100 parts by mass of the polyamic acid component (B).

[0064] [Preparation of liquid crystal alignment agent] The liquid crystal alignment agent used in the present invention is preferably prepared as a coating solution 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 in which a resin component for forming a resin film is dissolved in an organic solvent. Here, the resin component is the specific compound which is component (A) and the polyamic acid which is component (B) as described above. In this case, the total amount of the specific compound which is component (A) and the polyamic acid which is component (B) is preferably 0.5 to 20% by mass, more preferably 1 to 20% by mass, even more preferably 1 to 15% by mass, and particularly preferably 1 to 10% by mass, relative to the total amount of the liquid crystal alignment agent.

[0065] <Solvent> The solvent contained in the liquid crystal alignment agent used in the present invention is not particularly limited as long as it is a solvent that dissolves components (A) and (B). The liquid crystal alignment agent may contain only one type of solvent, or two or more types may be mixed and used. Furthermore, a solvent that does not dissolve components (A) or (B) can be used in combination with a solvent that dissolves components (A) or (B). In this case, it is preferable that the surface energy of the solvent that does not dissolve components (A) or (B) is lower than that of the solvent that dissolves components (A) or (B), as this improves the coatability of the liquid crystal alignment agent on the substrate.

[0066] Specific examples include water, N-alkyl-2-pyrrolidones such as N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-ε-caprolactam, tetramethylurea, dialkylimidazolidinones such as 3-methoxy-N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, and 1,3-dimethyl-2-imidazolidinone, lactones such as γ-butyrolactone, γ-valerolactone, and δ-valerolactone, carbonates such as ethylene carbonate and propylene carbonate, methanol, ethanol, and propano Examples include ketones such as ethanol, isopropanol, 3-methyl-3-methoxybutanol, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, isoamyl methyl ketone, methyl isopropyl ketone, diisobutyl ketone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, and 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, isoamyl butyrate, diisobutylcarbinol, and diisopentyl ether.

[0067] [ka]

[0068] 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 from 1 to 3. If n1 is 2 or 3, the 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.

[0069] In formula (Sv-1), examples of monovalent hydrocarbon groups having 1 to 6 carbon atoms for Y1 and Y2 include monovalent linear hydrocarbon groups having 1 to 6 carbon atoms, monovalent alicyclic hydrocarbon groups having 3 to 6 carbon atoms, and phenyl groups. Examples of monovalent linear hydrocarbon groups having 1 to 6 carbon atoms include alkyl groups having 1 to 6 carbon atoms. The alkanediyl group of R1 may be linear or branched.

[0070] In formula (Sv-2), the divalent hydrocarbon group having 1 to 6 carbon atoms in Z1 can be, for example, an alkanediyl group having 1 to 6 carbon atoms. Examples of monovalent hydrocarbon groups having 1 to 6 carbon atoms in Y3 and Y4 include monovalent linear hydrocarbon groups having 1 to 6 carbon atoms, monovalent alicyclic hydrocarbon groups having 3 to 6 carbon atoms, and phenyl groups. Examples of monovalent linear hydrocarbon groups having 1 to 6 carbon atoms include alkyl groups having 1 to 6 carbon atoms.

[0071] Specific examples of solvents represented by formula (Sv-1) include, for example, 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 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 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, etc. Specific examples of solvents represented by (Sv-2) include, for example, methyl glycolate, ethyl glycolate, butyl glycolate, ethyl lactate, butyl lactate, isoamyl lactate, ethyl-3-ethoxypropionate, methyl-3-methoxypropionate, ethyl 3-methoxypropionate, ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, and butyl 3-methoxypropionate.

[0072] The solvent is preferably one with a boiling point of 80 to 200°C. More preferably, it is 80 to 180°C. Preferred solvents include N,N-dimethylformamide, tetramethylurea, 3-methoxy-N,N-dimethylpropanamide, 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, and butyrate. Examples include isoamyl acid, diisobutylcarbinol, diisopentyl ether, 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 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, isoamyl lactate, ethyl-3-ethoxypropionate, methyl-3-methoxypropionate, ethyl 3-methoxypropionate, etc. Having a boiling point within this range is particularly preferable when the liquid crystal alignment agent containing the solvent is applied to a plastic substrate, as described later.

[0073] <Other ingredients> The liquid crystal alignment agent used in the present invention may contain components other than the above-mentioned components (A), (B), and solvent. Examples of such other components include, but are not limited to, crosslinking catalysts, compounds that improve film thickness uniformity and surface smoothness when the liquid crystal alignment agent is applied, and compounds that improve adhesion between the liquid crystal alignment film and the substrate.

[0074] <Crosslinking catalyst> A crosslinking catalyst may be added to the liquid crystal alignment agent used in the present invention for the purpose of promoting the reaction between the thermally crosslinkable group and the carboxyl group. Examples of such crosslinking catalysts include sulfonic acids or their hydrates or salts, such as p-toluenesulfonic acid, camphosulfonic 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, and dodecylbenzenesulfonic acid. Examples of compounds that generate acid upon heating include bis(tosyloxy)ethane, bis(tosyloxy)propane, bis(tosyloxy)butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, 1,2,3-phenylentris(methylsulfonate), pyridinium salt of p-toluenesulfonate, morphonium salt of p-toluenesulfonate, ethyl p-toluenesulfonate, propyl p-toluenesulfonate, butyl p-toluenesulfonate, isobutyl p-toluenesulfonate, methyl p-toluenesulfonate, phenethyl p-toluenesulfonate, cyanomethyl p-toluenesulfonate, 2,2,2-trifluoroethyl p-toluenesulfonate, 2-hydroxybutyl p-toluenesulfonate, and N-ethyl-p-toluenesulfonamide.

[0075] [Compounds that improve film thickness uniformity and surface smoothness] Compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. Specifically, examples include F-Top® 301, EF303, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Megafac® F171, F173, R-30 (manufactured by DIC Corporation), Florard FC430, FC431 (manufactured by 3M Corporation), Asahiguard® AG710 (manufactured by AGC Corporation), Surflon® S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical Co., Ltd.), and others. The proportion of these surfactants used is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the resin component contained in the polymer composition.

[0076] [Compounds that improve the adhesion between liquid crystal alignment films and substrates] Specific examples of compounds that improve the adhesion between the liquid crystal alignment film and the substrate include the functional silane-containing compounds shown below. For example, 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-triethoxysilylpropyltriethylene Examples of amino silane-containing compounds include ntetramine, 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, and N-phenyl-3-aminopropyltriethoxysilane. When using a compound to improve adhesion to the substrate, the amount used is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass, per 100 parts by mass of the resin component contained in the polymer composition.

[0077] In one embodiment, a photosensitizer may be used as an additive to improve the photoreactivity of the photo-directing group. Specific examples include aromatic 2-hydroxyketones (benzophenone), coumarin, ketocoumarin, carbonylbiscoumarin, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenone ketal.

[0078] <Liquid crystal alignment film and liquid crystal display element> The liquid crystal alignment agent of the present invention can be applied to a substrate, fired, and then subjected to alignment treatment by rubbing or light irradiation, or, in some vertical alignment applications, without any alignment treatment, to form a liquid crystal alignment film. Suitable substrates include glass such as float glass and soda glass; and transparent substrates made of plastics such as polyethylene terephthalate, polybutylene terephthalate, polypropylene, polystyrene, polyethersulfone, polycarbonate, poly(alicyclic olefin), polyvinyl chloride, polyvinylidene chloride, polyetheretherketone (PEEK) resin film, polysulfone (PSF), polyethersulfone (PES), polyamide, polyimide, acrylic, and triacetylcellulose. As the transparent conductive film provided on one surface of the substrate, a NESA film (registered trademark of PPG Corporation, USA) made of tin oxide (SnO2), or an ITO film made of indium oxide-tin oxide (In2O3-SnO2) can be used.

[0079] <Coating film formation process> The method for applying the liquid crystal alignment agent of the present invention is not particularly limited, but can include screen printing, flexographic printing, offset printing, inkjet printing, dip coating, roll coating, slit coating, spin coating, etc., and these may be used depending on the purpose. After applying the agent to a substrate by these methods, the solvent can be evaporated using a heating means such as a hot plate to form a coating film. In this coating film formation process, the liquid crystal alignment agent coating film formed exhibits good liquid crystal alignment even with a low content of component (A), because component (A) is unevenly distributed on the film surface due to the hydrophobicity of the photo-aligning groups.

[0080] The firing after coating with the liquid crystal alignment agent can be carried out at any temperature between 40 and 300°C, but is preferably between 40 and 250°C, and more preferably between 40 and 230°C. In this step, the thermally crosslinkable group of the specific compound, which is component (A), reacts with the carboxyl group of the polyamic acid, which is component (B), and the aligning group is fixed. The thickness of the coating film formed on the substrate is preferably 5 to 1,000 nm, and more preferably 10 to 500 nm or 10 to 300 nm. This firing can be carried out using a hot plate, a hot air circulation furnace, an infrared furnace, etc.

[0081] <Light irradiation process> In one embodiment, the orientation treatment may be performed by light irradiation, for example, and may include the steps of applying the above-mentioned liquid crystal alignment agent onto a substrate to form a coating film, and irradiating the coating film with light either when the coating film is not in contact with the liquid crystal layer or when it is in contact with the liquid crystal layer.

[0082] Examples of light used in the orientation treatment by light irradiation include ultraviolet light and visible light with wavelengths of 150 to 800 nm. Of these, ultraviolet light with wavelengths of 300 to 400 nm is preferred. The irradiated light may be polarized or unpolarized. As for polarization, it is preferable to use light that includes linear polarization.

[0083] When polarized light is used, the light irradiation may be performed perpendicular to the substrate surface, at an oblique angle, or a combination of both. When unpolarized light is used, it is preferable to irradiate the substrate surface at an oblique angle. The light intensity is 0.1 mJ / cm². 2 More than 1,000mJ / cm 2 It is preferable to keep it below 1 to 500 mJ / cm². 2 It is more preferable to do so, at a concentration of 2-200 mJ / cm². 2 It is even more preferable to do so.

[0084] The liquid crystal display element of the present invention can be manufactured by conventional methods, and the manufacturing method is not particularly limited. The pair of substrates face each other with an appropriate gap between them, and it is preferable to place a spacer between the substrates in order to make the thickness of the liquid crystal sandwiched between the substrates uniform. As this spacer, known spacer materials such as conventional scattered spacers and spacers formed from photosensitive spacer-forming compositions can be used, and it is also possible to use irregularities formed on a layer made of liquid crystal curing material as a spacer.

[0085] <Liquid crystal clamping process> Two methods can be used to construct a liquid crystal cell by sandwiching liquid crystal between substrates. As a first method, a pair of substrates are placed facing each other with a gap (cell gap) in between so that each liquid crystal alignment film faces the other, the peripheral portions of the pair of substrates are bonded together using a sealant, liquid crystal is injected and filled into the substrate surface and the cell gap partitioned by a suitable sealant, and then the injection hole is sealed to manufacture a liquid crystal cell.

[0086] A second method involves applying, for example, an ultraviolet-curable sealant to a predetermined location on one of two substrates on which a liquid crystal alignment film is formed, then dropping liquid crystal onto several predetermined locations on the surface of the liquid crystal alignment film, bonding the other substrate so that the liquid crystal alignment films face each other, spreading the liquid crystal across the entire surface of the substrate, and then curing the sealant by irradiating the entire surface of the substrate with ultraviolet light to manufacture a liquid crystal cell (ODF (One Drop Fill) method).

[0087] As the liquid crystal, depending on the application, fluorine-based liquid crystals or cyano-based liquid crystals having positive or negative dielectric anisotropy, or liquid crystal compounds or liquid crystal compositions that polymerize by at least one of heating and light irradiation (hereinafter also referred to as polymerizable liquid crystals or curable liquid crystal compositions) may be used. In one embodiment, the process of forming the liquid crystal alignment agent coating may be carried out by a roll-to-roll method. Using a roll-to-roll method simplifies the manufacturing process of the liquid crystal display element and reduces manufacturing costs. Then, by attaching polarizing plates to both outer surfaces of the liquid crystal cell, a liquid crystal display element can be obtained.

[0088] Polarizing plates used on the outside of liquid crystal cells include polarizing plates in which a polarizing film called an "H film," which is made by stretching and oriented polyvinyl alcohol and absorbing iodine, is sandwiched between cellulose acetate protective films, or polarizing plates made of the H film itself. As described above, the liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention exhibits good liquid crystal alignment, excellent pre-tilt angle generation ability, and high reliability. Furthermore, the liquid crystal display element manufactured by the method of the present invention has excellent display characteristics. [Examples]

[0089] The present invention will be described in further detail below based on the examples, but the present invention is not limited in any way by these examples. The abbreviations for the compounds used are as follows. (Specific compound) EP1~EP10: Compounds represented by the following formulas [EP1]~[EP10], respectively.

[0090] [ka]

[0091] <Tetracarboxylic acid dianhydride> A1-A9: Compounds represented by the following formulas [A1]-[A9], respectively.

[0092] [ka]

[0093] <Side-chain diamines> B1~B8: Compounds represented by the following formulas [B1]~[B8], respectively (corresponding to aromatic diamine (d) above)

[0094] [ka]

[0095] <Other Diamines> C1~C25: Compounds represented by the following formulas [C1]~[C25], respectively (where Boc represents the tert-butoxycarbonyl group).

[0096] [ka]

[0097] The abbreviations for the reagents used in this embodiment are shown below. (solvent) NMP:N-methyl-2-pyrrolidone BCS: Butyl cellosolve THF: Tetrahydrofuran DMAc: N,N-dimethylacetamide DMF: N,N-dimethylformamide DMSO: Dimethyl sulfoxide AcOEt: Ethyl acetate MeCN: Acetonitrile PhMe: Toluene Heptane: CHCl3: Chloroform CH2Cl2: Methylene chloride

[0098] <Synthesis of specific compounds> EP1 was synthesized using the method described in Japanese Patent Publication No. 2011-133825. EP2 to EP10 are novel compounds not previously published in the literature, and their synthesis methods are described in detail in the following examples of specific compound synthesis 1 to 9. < 1 H-NMR measurement> Equipment: Fourier transform superconducting nuclear magnetic resonance spectrometer (FT-NMR) "AVANCE III" (manufactured by BRUKER) 500MHz. Solvents: Deuterated dimethyl sulfoxide (DMSO-d6), deuterated chloroform (CDCl3) Standard substance: Tetramethylsilane (TMS).

[0099] (Example of specific compound synthesis 1: Synthesis of [EP2])

[0100] [ka]

[0101] 1-bromo-4-(trans-4-pentylcyclohexyl)-benzene (6.2 g, 20 mmol), methacrylic acid (3.4 g, 40 mmol), tripropylamine (8.6 g, 60 mmol), and DMAc (30 g) were charged into a 200 mL four-necked flask. After purging with nitrogen, palladium acetate (0.09 g, 0.4 mmol) and tri(o-tolyl)phosphine (0.24 g, 0.8 mmol) were added, and the mixture was stirred at 100°C. After the reaction was complete, the palladium catalyst was removed by filtering the reaction mixture. Subsequently, the obtained filtrate was poured into AcOEt (200 g), and the organic layer was washed with 1 N aqueous hydrochloric acid (200 g) and pure water (200 g), and then concentrated. AcOEt (30g) was added to the crude product obtained, and recrystallization was performed at 50°C to obtain [EP2-1] (3.9g, 12.4 mmol, yield: 62%).

[0102] In a 100 mL four-necked flask, [EP2-1] (5.0 g, 16 mmol), epichlorohydrin (7.4 g, 80 mmol), tetrabutylammonium chloride (0.66 g, 2.4 mmol), and MeCN (25 g) were charged and stirred at 80°C. After the reaction was complete, PhMe (100 g) was added to the reaction mixture, the organic layer was washed with pure water (300 g), and the mixture was concentrated. Next, the crude mixture obtained, potassium carbonate (3.2 g, 24 mmol), and MeCN (60 g) were charged into a 200 mL four-necked flask and stirred at 80°C. After the reaction was complete, the reaction mixture was filtered off, and the filtrate was concentrated. Subsequently, the resulting residue was isolated by silica gel column chromatography (AcOEt:Heptane = 1:20 (volume ratio)) to obtain the target [EP2] (white solid) (4.4 g, 11.9 mmol, yield: 74%). Object 1 The results of the 1H-NMR spectrum are shown below. From these results, it was confirmed that the obtained solid was the target [EP2]. 1 H-NMR (500MHz, CDCl3): δ(ppm)=7.71(s,1H),7.34-7.36(d,2H),7.23-7.26( m,2H),4.53-4.56(m,1H),4.04-4.08(m,1H),3.30-3.32(m,1H),2.88-2.90( m,1H),2.70-2.71(m,1H),2.46-2.51(m,1H),2.15(s,3H),1.87-1.91(m,4H) ,1.42-1.49(m,2H),1.22-1.33(m,9H),1.02-1.10(m,2H),0.88-0.91(t,3H)

[0103] (Example of specific compound synthesis 2: Synthesis of [EP3])

[0104] [ka]

[0105] [EP1] (12.6 g, 36 mmol), lithium bromide (0.15 g, 1.8 mmol), and NMP (130 g) were charged into a 300 mL four-necked flask. The reaction system was purged with carbon dioxide and stirred at 100 °C. After the reaction was complete, AcOEt (600 g) was added to the reaction mixture, the organic layer was washed with pure water (1500 g), and the mixture was concentrated. Subsequently, the resulting residue was isolated by silica gel column chromatography (AcOEt:Heptane = 1:2 (volume ratio)) to obtain the target [EP3] (white solid) (13.3 g, 33.1 mmol, yield: 92%). 1 The results of the 1H-NMR spectrum are shown below. From these results, it was confirmed that the obtained solid was the target [EP3]. 1 H-NMR(500MHz,DMSO-d6):δ(ppm)=7.63-7.67(m,3H),7.27-7.29(d,2H),6.58-6.61(d,1H),5.10-5.11(m,1H),4.59-4.63(t,1H),4.44-4 .47(m,1H),4.33-4.39(m,2H),2.50(s,1H),1.78-1.83(m,4H),1.40- 1.48(m,2H),1.18-1.31(m,9H),1.00-1.07(m,2H),0.86-0.88(t,3H)

[0106] (Example of specific compound synthesis 3: Synthesis of [EP4])

[0107] [ka]

[0108] 39.4 g, 100 mmol of 4-[(1E)-2-carboxyethenyl]phenyl 4-(4,4,4-trifluorobutoxy)benzoate, 0.073 g, 1 mmol of DMF, and 200 g of THF were charged into a 500 mL four-necked flask. Oxalyl chloride (16.5 g, 130 mmol) was added dropwise in an ice bath, and the reaction was carried out at room temperature (25°C). After the reaction was complete, the unreacted oxalyl chloride was removed by distillation, and THF (400 g) was added to the residue to prepare an acid chloride solution. Subsequently, glycidol (14.8 g, 200 mmol) and pyridine (15.8 g, 200 mmol) were added dropwise in that order in an ice bath, and the mixture was stirred at room temperature (25°C). After the reaction was complete, the reaction system was poured into 1500 g of pure water, and the precipitate was filtered off. Next, the crude product obtained was isolated by silica gel column chromatography (AcOEt:Heptane = 1:4 (volume ratio)) to obtain the target [EP4] (white solid) (15.6 g, 34.6 mmol, yield: 35%). 1 The results of the 1H-NMR spectrum are shown below. From these results, it was confirmed that the obtained solid was the target [EP4]. 1 H-NMR(500MHz,DMSO-d6):δ(ppm)=8.08-8.10(d,2H),7.84-7.86(d,2H),7. 72-7.75(d,1H),7.33-7.35(d,2H),7.14-7.15(d,2H),6.69-6.73(d,1H),4 .51-4.55(m,1H),4.16-4.19(t,2H),3.95-3.99(m,1H),3.27-3.31(m,1H), 2.82-2.84(m,1H),2.70-2.71(m,1H),2.41-2.50(m,2H),1.96-2.02(m,2H)

[0109] (Example of specific compound synthesis 4: Synthesis of [EP5])

[0110] [ka]

[0111] In a 300 mL four-necked flask, trans-4-[4-[(1E)-2-carboxyethenyl]phenyl]cyclohexyl 4,4,4-trifluorobutanate (25.9 g, 70 mmol), epichlorohydrin (32.4 g, 350 mmol), tetrabutylammonium chloride (2.92 g, 10.5 mmol), and DMSO (100 g) were charged and stirred at 80°C. After the reaction was complete, AcOEt (500 g) was added to the reaction mixture, the organic layer was washed with pure water (1500 g), and the mixture was concentrated. Subsequently, the crude mixture obtained, potassium carbonate (14.5 g, 105 mmol), and MeCN (100 g) were charged into a 300 mL four-necked flask and stirred at 80°C. After the reaction was complete, the reaction mixture was filtered off, and the filtrate was concentrated. Next, the obtained residue was isolated by silica gel column chromatography (AcOEt:Heptane = 1:3 (volume ratio)) to obtain the target [EP5] (white solid) (23.6 g, 55.3 mmol, yield: 79%). 1 The results of the 1H-NMR spectrum are shown below. From these results, it was confirmed that the obtained solid was the target [EP5]. 1 H-NMR(500MHz,DMSO-d6):δ(ppm)=7.65-7.68(m,3H),7.30-7.32(d,2H),6. 61-6.65(d,1H),4.74-4.78(m,1H),4.49-4.52(m,1H),3.93-3.96(m,1H),3 .25-3.28(m,1H),2.81-2.83(t,1H),2.68-2.70(m,1H),2.50-2.57(m,5H), 2.00-2.02(d,2H),1.82-1.84(d,2H),1.57-1.64(m,2H),1.45-1.53(m,2H)

[0112] (Example of specific compound synthesis 5: Synthesis of [EP6])

[0113] [ka]

[0114] 1-bromo-4-[(trans,trans)-4c-pentyl[1,1'-bicyclohexyl]-4-yl]benzene (19.6 g, 50 mmol), acrylic acid (5.4 g, 75 mmol), tripropylamine (21.5 g, 150 mmol), and DMAc (39 g) were charged into a 200 mL four-necked flask. After purging with nitrogen, palladium acetate (0.23 g, 1.0 mmol) and tri(o-tolyl)phosphine (0.61 g, 2.0 mmol) were added, and the mixture was stirred at 100°C. After the reaction was complete, the palladium catalyst was removed by filtering the reaction mixture. Subsequently, the filtrate was poured into 1000 g of 1 N hydrochloric acid solution, the precipitate was filtered, dissolved in THF (600 g), and insoluble matter was filtered off. The obtained filtrate was concentrated, and the resulting crude product was mixed with CHCl3 (250 g) and repulped and washed at 0°C to obtain [EP6-1] (14.2 g, 37.2 mmol, yield: 74%).

[0115] In a 200 mL four-necked flask, [EP6-1] (14.2 g, 37 mmol), epichlorohydrin (142.3 g), and 10 wt% benzyltrimethylammonium chloride aqueous solution (0.22 g, 0.1 mmol) were charged and stirred at 120°C. After the reaction was complete, the reaction mixture was concentrated, EtOH (140 g) was added to the residue, and repulping was performed at 0°C. Subsequently, the resulting crude product was dissolved in THF (100 g), the insoluble matter was filtered off, and the resulting filtrate was concentrated to obtain [EP6] (12.0 g, 27.4 mmol, yield: 74%). 1 The results of the 1H-NMR spectrum are shown below. From these results, it was confirmed that the obtained solid was the target [EP6]. 1 H-NMR (500MHz, CDCl3): δ(ppm)=7.69-7.73(d,1H),7.45-7.46(d,2H),7.22-7.26(m,2H),6.4 1-6.44(d,1H),4.52-4.55(m,1H),4.03-4.07(m,1H),3.28-3.30(m,1H),2.87-2.89(t,1H),2. 69-2.71(m,1H),2.44-2.49(t,1H),1.90-1.92(d,2H),1.84-1.86(d,2H),1.73-1.78(t,4H), 1.41-1.43(m,2H),1.24-1.31(m,6H),1.15-1.17(m,6H),0.96-1.07(m,3H),0.83-0.90(m,5H)

[0116] (Example of specific compound synthesis 6: Synthesis of [EP7])

[0117] [ka]

[0118] 1-bromo-4-(trans-4-pentylcyclohexyl)-benzene (22.0 g, 71 mmol), crotonic acid (24.5 g, 285 mmol), tripropylamine (51.0 g, 356 mmol), and DMAc (110 g) were charged into a 300 mL four-necked flask. After purging with nitrogen, palladium acetate (0.32 g, 1.4 mmol) and tri(o-tolyl)phosphine (0.86 g, 2.8 mmol) were added, and the mixture was stirred at 140 °C. After the reaction was complete, the palladium catalyst was removed by filtering the reaction mixture. Subsequently, the filtrate was poured into 1 N aqueous hydrochloric acid (700 g), the precipitate was filtered, and then dissolved in THF (400 g), after which insoluble matter was filtered off. The obtained filtrate was concentrated, and heptane (400 g) was added to the crude product, and it was repulped and washed at 0 °C. Furthermore, MeCN (50g) was added to the obtained crude product and repulped and washed at 0°C to obtain [EP7-1] (12.4g, 39.5 mmol, yield: 55%).

[0119] [EP7-1] (10.1 g, 32 mmol), epichlorohydrin (100.6 g), and 10% by mass aqueous solution of benzyltrimethylammonium chloride (0.18 g, 0.1 mmol) were charged into a 300 mL four-necked flask and stirred at 120°C. After the reaction was complete, the reaction mixture was concentrated, EtOH (80 g) was added to the residue, insoluble matter was filtered off, and the mixture was concentrated. EtOH (40 g) was added to the obtained residue, and recrystallization was performed by cooling to -20°C. Furthermore, MeOH (40 g) was added to the obtained crude product, and [EP7] was obtained by repulping and washing at -20°C (5.8 g, 15.7 mmol, yield: 49%). 1 The results of the 1H-NMR spectrum are shown below. From these results, it was confirmed that the obtained solid was the target [EP7]. 1 H-NMR(500MHz,DMSO-d6):δ(ppm)=7.51-7.53(d,2H),7.26-7.27(d,2H),6. 19-6.20(s,1H),4.44-4.47(m,1H),3.88-3.92(m,1H),3.23-3.26(m,1H),2 .80-2.81(t,1H),2.67-2.68(m,1H),2.47-2.51(m,4H),1.78-1.83(t,4H), 1.40-1.48(m,2H),1.18-1.31(m,9H),1.00-1.07(m,2H),0.86-0.89(t,3H)

[0120] (Example of specific compound synthesis 7: Synthesis of [EP8])

[0121] [ka]

[0122] 1-bromo-4-[(trans,trans)-4'-pentyl[1,1'-bicyclohexyl]-4-yl]benzene (39.1 g, 100 mmol), crotonic acid (34.4 g, 400 mmol), tripropylamine (71.6 g, 500 mmol), and mesitylene (100 g) were charged into a 200 mL four-necked flask. After purging with nitrogen, palladium acetate (0.44 g, 2.0 mmol) and tri(o-tolyl)phosphine (1.2 g, 4.0 mmol) were added, and the mixture was stirred at 140 °C. After the reaction was complete, the palladium catalyst was removed by filtering the reaction mixture. Subsequently, the filtrate was poured into MeCN (300 g), neutralized with 12 N hydrochloric acid aqueous solution, and the precipitate was filtered off. The crude product obtained was mixed with THF (180 g) and CHCl3 (360 g) and repulped and washed at 0°C to obtain [EP8-1] (11.0 g, 27.7 mmol, yield: 28%).

[0123] [EP8-1] (1.8 g, 4.5 mmol), epichlorohydrin (17.9 g), and 10% by mass aqueous solution of benzyltrimethylammonium chloride (0.025 g, 0.014 mmol) were charged into a 200 mL four-necked flask and stirred at 120°C. After the reaction was complete, the reaction mixture was concentrated, MeOH (60 g) was added to the residue, and repulping was performed at 0°C. Subsequently, the crude product obtained was isolated by silica gel column chromatography (THF:AcOEt:Heptane = 0.5:0.5:20 (volume ratio)) to obtain [EP8] (0.6 g, 1.3 mmol, yield: 28%). 1 The results of the 1H-NMR spectrum are shown below. From these results, it was confirmed that the obtained solid was the target [EP8]. 1 H-NMR (500MHz, CDCl3): δ(ppm)=7.41-7.43(d,2H),7.21-7.22(d,2H),6.18(s,1H),4.45- 4.48(m,1H),4.00-4.04(m,1H),3.26-3.28(m,1H),2.86-2.88(t,1H),2.69-2.70(m,1H),2 .58(s,3H)2.44-2.49(t,1H),1.90-1.93(d,2H),1.84-1.86(d,2H),1.73-1.78(t,4H),1.4 2-1.44(m,2H),1.25-1.29(m,6H),1.15-1.23(m,6H),0.99-1.08(m,3H),0.83-0.90(m,5H)

[0124] (Example of specific compound synthesis 8: Synthesis of [EP9])

[0125] [ka]

[0126] 4-(trans-4-pentylcyclohexyl)benzaldehyde (47.6 g, 184 mmol), ethyl cyanoethyl (25.6 g, 221 mmol), potassium tert-butoxide (3.1 g, 28 mmol), and tert-butyl methyl ether (330 g) were charged into a 500 mL four-necked flask and stirred at 55°C. After the reaction was complete, the reaction mixture was poured into AcOEt (700 g), and the organic layer was washed with 1 N aqueous hydrochloric acid (500 g) and pure water (1000 g), and then concentrated. MeOH (150 g) was added to the crude product and dissolved at 50°C. After concentration until a solid precipitate formed, the mixture was cooled to 0°C and the precipitate was filtered off to obtain [EP9-1] (48.1 g, 136.2 mmol, yield: 74%).

[0127] [EP9-1] (48.1 g, 136.2 mmol), 10% potassium hydroxide aqueous solution (80.2 g, 143.0 mmol), and EtOH (480 g) were charged into a 2 L four-necked flask and stirred at 50°C. After the reaction was complete, the reaction mixture was filtered to separate the precipitate. Pure water (500 g) was poured into the filtrate, and 12 N hydrochloric acid aqueous solution was added until the pH was 3-4, and the solid was filtered off. MeCN (750 g) was added to the obtained crude product and dissolved at 60°C. After concentrating until a solid precipitate formed, the mixture was cooled to 0°C and the precipitate was filtered off to obtain [EP9-2] (33.6 g, 103.3 mmol, yield: 76%).

[0128] In a 300 mL four-necked flask, [EP9-2] (16.3 g, 50 mmol), DMF (0.04 g, 0.05 mmol), and THF (120 g) were charged. Oxalyl chloride (7.6 g, 60 mmol) was added dropwise in an ice bath, and the reaction was carried out at room temperature (25°C). After the reaction was complete, the unreacted oxalyl chloride was removed by distillation of the solvent, and THF (120 g) was added to the residue to prepare an acid chloride solution. Next, glycidol (4.4 g, 60 mmol) and pyridine (5.9 g, 75 mmol) were added dropwise in that order in an ice bath, and the mixture was stirred at room temperature (25°C). After the reaction was complete, the reaction system was poured into AcOEt (250 g), the organic layer was washed with pure water (500 g), and the mixture was concentrated. Next, the crude product obtained was isolated by silica gel column chromatography (AcOEt:Heptane = 1:50 (volume ratio)) to obtain the target [EP9] (pale yellow solid) (9.2 g, 23.9 mmol, yield: 48%). 1 The results of the 1H-NMR spectrum are shown below. From these results, it was confirmed that the obtained solid was the target [EP9]. 1 H-NMR(500MHz,DMSO-d6):δ(ppm)=8.39(s,1H),8.00-8.02(d,2H),7.46- 7.47(d,2H),4.64-4.67(d,1H),4.07-4.11(m,1H),3.30-3.32(m,1H),2.8 4-2.86(m,1H),2.74-2.75(m,1H),2.55-2.59(m,1H),1.80-1.84(m,4H),1 .43-1.50(m,2H),1.18-1.31(m,9H),1.02-1.07(m,2H),0.86-0.89(t,3H)

[0129] (Example of specific compound synthesis 9: Synthesis of [EP10])

[0130] [ka]

[0131] 4-(trans-4-pentylcyclohexyl)benzaldehyde (7.8 g, 30 mmol), 3,3,3-trifluoropropionic acid (5.8 g, 45 mmol), and THF (80 g) were charged into a 300 mL four-necked flask. Titanium(IV) tetrachloride / CH2Cl2 solution (90 mL, 90 mmol) was added dropwise at 0°C and the mixture was stirred for 1 hour. Subsequently, triethylamine (18.2 g, 180 mmol) was added dropwise at 0°C and the mixture was stirred at room temperature (25°C). After the reaction was complete, the reaction mixture was poured into AcOEt (400 g), and the organic layer was washed with 1 N aqueous hydrochloric acid (400 g) and pure water (800 g), and then concentrated. MeCN (150 g) was added to the crude product, and the mixture was repulped and washed at 0°C to obtain [EP10-1] (7.2 g, 19.5 mmol, yield: 65%).

[0132] In a 300 mL four-necked flask, [EP9-2] (7.2 g, 20 mmol), DMF (0.04 g, 0.05 mmol), and THF (50 g) were charged. Oxalyl chloride (3.0 g, 24 mmol) was added dropwise in an ice bath, and the reaction was carried out at room temperature (25°C). After the reaction was complete, the unreacted oxalyl chloride was removed by distillation of the solvent, and THF (50 g) was added to the residue to prepare an acid chloride solution. Next, glycidol (1.8 g, 24 mmol) and pyridine (2.4 g, 30 mmol) were added dropwise in that order in an ice bath, and the mixture was stirred at room temperature (25°C). After the reaction was complete, the reaction system was poured into AcOEt (200 g), the organic layer was washed with pure water (400 g), and the mixture was concentrated. Next, the crude product obtained was isolated by silica gel column chromatography (AcOEt:Heptane = 1:20 (volume ratio)) to obtain the target [EP10] (pale yellow solid) (1.2 g, 2.82 mmol, yield: 14%). 1 The results of the 1H-NMR spectrum are shown below. From these results, it was confirmed that the obtained solid was the target [EP10]. 1 H-NMR(500MHz,DMSO-d6):δ(ppm)=8.19(s,1H),7.42-7.43(d,2H),7.33- 7.35(d,2H),4.62-4.65(d,1H),4.06-4.10(m,1H),3.30-3.32(m,1H),2.8 2-2.84(m,1H),2.72-2.73(m,1H),2.50-2.54(m,1H),1.79-1.83(m,4H),1 .43-1.46(m,2H),1.19-1.31(m,9H),1.02-1.04(m,2H),0.86-0.88(t,3H)

[0133] <Synthesis of polyamic acids> (Synthesis Example 1) B1 (0.76 g, 2.00 mmol), C1 (1.95 g, 18.00 mmol), and A6 (4.34 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-1A) with a solid content of 20% by mass. To the obtained polyamic acid solution (PAA-1A) (10.0 g), NMP (20.0 g) and BCS (20.0 g) were added and stirred at room temperature (25°C) for 2 hours to obtain a polyamic acid solution (PAA-1) with a solid content concentration of 4% by mass.

[0134] (Synthesis Examples 2-40) Polyamic acid solutions (PAA-2) to (PAA-40) were synthesized using the same method as in Synthesis Example 1, with the compositions shown in Table 1-1.

[0135] [Table 1]

[0136] (Synthesis Example 41) C2 (2.16 g, 20.00 mmol) and A6 (4.35 g, 19.4 mmol) were dissolved in NMP (26.2 g) and reacted at 60°C for 10 hours to obtain a polyamic acid solution (PAA-41A) with a solid content of 20% by mass. To the obtained polyamic acid solution (PAA-41A) (10.0 g), NMP (20.0 g) and BCS (20.0 g) were added, and the mixture was stirred at room temperature (25°C) for 2 hours to obtain a polyamic acid solution (PAA-41) with a solid content of 4% by mass.

[0137] (Synthesis examples 42-43) Polyamic acid solutions (PAA-42) to (PAA-43) were synthesized using the same method as in Synthesis Example 1, with the compositions shown in Table 1-2.

[0138] [Table 2]

[0139] <Preparation of liquid crystal alignment agent> (Example 1) To the polyamic acid solution (PAA-1) (10.0 g) obtained in Synthesis Example 1, EP1 (0.06 g) was added and stirred at room temperature (25°C) to obtain the liquid crystal alignment agent (AL-1).

[0140] (Examples 2-40) As shown in Table 2-1, liquid crystal alignment agents (AL-2) to (AL-40) were obtained by following the same procedure as in Example 1, except that (PAA-2) to (PAA-40) were used instead of the polyamic acid solution (PAA-1).

[0141] (Examples 41-44) As shown in Table 2-1, liquid crystal alignment agents (AL-41) to (AL-44) were obtained by carrying out the procedure in the same manner as in Example 1, except that (EP2) to (EP5) were used instead of the specific compound (EP1).

[0142] (Examples 45-57) As shown in Table 2-2, liquid crystal alignment agents (AL-45) to (AL-57) were obtained by carrying out the same procedure as in Example 1, except that the type of polyamic acid solution and specific compound used were changed.

[0143] [Table 3]

[0144] [Table 4]

[0145] (Comparative Example 1) To the polyamic acid solution (PAA-1A) (10.0 g) obtained in Synthesis Example 1, EP1 (0.06 g) and tetrabutylammonium bromide (0.20 g) were added and the mixture was reacted at 120°C for 4 hours. This reaction solution was added to methanol, and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyamic acid ester powder (E). 6.0 g of the obtained polyamic acid ester powder (E) was mixed with 44.0 g of NMP and stirred at 70°C for 20 hours to dissolve. 40.0 g of NMP and 60.0 g of BCS were added to this solution and stirred at room temperature (25°C) for 5 hours to obtain the liquid crystal alignment agent (AL-R1).

[0146] (Comparative Examples 2-4) As shown in Table 3, liquid crystal alignment agents (AL-R2) to (AL-R4) were obtained by following the same procedure as in Comparative Example 1, except that (PAA-2A), (PAA-10A), and (PAA-34A) were used instead of the polyamic acid solution (PAA-1A).

[0147] (Comparative Example 5) As shown in Table 3, a liquid crystal alignment agent (AL-R5) was obtained by following the same procedure as in Comparative Example 1, except that (EP4) was used instead of the specific compound (EP1). (Comparative Example 6) As shown in Table 3, a liquid crystal alignment agent (AL-R6) was obtained by following the same procedure as in Comparative Example 1, except that (PAA-41A) was used instead of the polyamic acid solution (PAA-1A).

[0148] [Table 5]

[0149] <Fabrication of liquid crystal display elements> The liquid crystal alignment agents (AL-1), (AL-2), (AL-10), (AL-34), (AL-42), (AL-43), (AL-48) obtained in the examples, and the liquid crystal alignment agents (AL-R1) to (AL-R6) obtained in the comparative examples were each subjected to pressure filtration through a membrane filter with a pore size of 1 μm. The obtained solution was spin-coated onto the ITO surface of a glass substrate with a transparent electrode made of ITO film, dried on a 70°C hot plate for 90 seconds, and then baked on a 200°C hot plate for 30 minutes to form a liquid crystal alignment film with a thickness of 100 nm. Next, an irradiation intensity of 4.3 mW / cm² is applied to the coating surface via a polarizing plate. 2 Linearly polarized ultraviolet light with a wavelength of 313 nm is applied at an angle of 40° tilted from the substrate normal direction at a rate of 50 mJ / cm². 2 Irradiation was performed to obtain a substrate with a liquid crystal alignment film. Linearly polarized ultraviolet light was prepared by passing ultraviolet light from a high-pressure mercury lamp through a 313 nm bandpass filter, and then through a 313 nm polarizer. Two of the above substrates were prepared. 4 μm bead spacers were scattered onto the liquid crystal alignment film of one substrate, and then a sealant (Mitsui Chemicals, XN-1500T) was applied. Next, the other substrate was bonded to the first substrate so that the liquid crystal alignment film surfaces faced each other and the alignment direction was 180°. An empty cell was then fabricated by heat curing the sealant at 120°C for 90 minutes. Liquid crystal (Merck, MLC-3022) was injected into this empty cell using a reduced-pressure injection method to obtain a liquid crystal display element.

[0150] <Rating> (Liquid crystal alignment) The liquid crystal display elements obtained above were subjected to isotropic phase treatment at 120°C for 1 hour, and then observed using a polarizing microscope. As an evaluation criterion, "good" was defined as the absence of alignment defects such as light loss or domain formation, and the acquisition of uniform liquid crystal drive when voltage was applied to the liquid crystal cell. "Poor" was defined as the presence of alignment defects such as light loss or domain formation, or the failure to acquire uniform liquid crystal drive when voltage was applied to the liquid crystal cell. The evaluation results are shown in Table 4.

[0151] [Table 6]

[0152] As can be seen from the results in Table 4, compared to liquid crystal alignment agents using polyamic acid esters obtained by reacting polyamic acid with photoreactive monomers, the liquid crystal alignment agent using photoreactive monomers as additives without reaction showed no generation of bright spots or poor alignment, and exhibited high vertical alignment. Specifically, this is a comparison between Example 1 and Comparative Example 1, Example 2 and Comparative Example 2, Example 10 and Comparative Example 3, Example 34 and Comparative Example 4, Example 43 and Comparative Example 5, and Example 48 and Comparative Example 6.

[0153] <Fabrication of liquid crystal display elements for evaluating resistance to external loads> The liquid crystal alignment agents (AL-48), (AL-51), (AL-56), and (AL-57) obtained in the examples were each subjected to pressure filtration through a membrane filter with a pore size of 1 μm. The obtained solution was spin-coated onto the ITO surface of a glass substrate with a transparent electrode made of ITO film, dried on a 70°C hot plate for 90 seconds, then baked on a 200°C hot plate for 30 minutes to form a liquid crystal alignment film with a thickness of 100 nm, and then exposed to air for 5 days. Next, an irradiation intensity of 4.3 mW / cm² is applied to the coating surface via a polarizing plate. 2 Linearly polarized ultraviolet light with a wavelength of 313 nm is applied at an angle of 40° tilted from the substrate normal direction at a rate of 50 mJ / cm². 2 Irradiation was performed to obtain a substrate with a liquid crystal alignment film. Linearly polarized ultraviolet light was prepared by passing ultraviolet light from a high-pressure mercury lamp through a 313 nm bandpass filter, and then through a 313 nm polarizer. Two of the above substrates were prepared. 4 μm bead spacers were scattered onto the liquid crystal alignment film of one substrate, and then a sealant (Mitsui Chemicals, XN-1500T) was applied. Next, the other substrate was bonded to the substrate so that the liquid crystal alignment film surfaces faced each other and the alignment direction was 180°. An empty cell was then fabricated by heat curing the sealant at 120°C for 90 minutes. Liquid crystal (Merck, MLC-3022) was injected into this empty cell using a reduced-pressure injection method to obtain a liquid crystal display element for evaluating storage resistance.

[0154] <Rating> (Liquid crystal alignment) The liquid crystal display elements obtained above were subjected to isotropic phase treatment at 120°C for 1 hour, and then observed using a polarizing microscope. As an evaluation criterion, "good" was defined as the absence of alignment defects such as light loss or domain formation, and the acquisition of uniform liquid crystal drive when voltage was applied to the liquid crystal cell. "Poor" was defined as the presence of alignment defects such as light loss or domain formation, or the failure to acquire uniform liquid crystal drive when voltage was applied to the liquid crystal cell. The evaluation results are shown in Table 5.

[0155] [Table 7]

[0156] As can be seen from the results in Table 5, compared to liquid crystal alignment agents using photoreactive monomers without substituted cinnamoyl groups as additives, liquid crystal alignment agents using additives with substituted cinnamoyl groups showed no generation of bright spots or poor alignment, and exhibited high vertical alignment. Specifically, this is a comparison between Example 48 and Examples 51, 56, and 57. [Industrial applicability]

[0157] The liquid crystal alignment agent of the present invention, and the liquid crystal alignment film obtained therefrom, can be suitably used in liquid crystal display elements.< / x> < / x>

Claims

1. (A) The component is as follows (pa-1) (In the formula, A is a pyrimidine-2,5-diyl, pyridine-2,5-diyl, thiophene-2,5-diyl, furan-2,5-diyl, 1,4- or 2,6-naphthylene or phenylene, which may be substituted with a group selected from a fluorine atom, a chlorine atom, and a cyano group, or with an alkoxy group having 1 to 5 carbon atoms, a linear or branched alkyl residue (which may be substituted with one cyano group or one or more halogen atoms), and R １ R is a single bond, an oxygen atom, -COO- or -OCO-, ２ R is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group, or a divalent fused cyclic group. ３ R is a single bond, an oxygen atom, -COO- or -OCO-, ４ is a linear or branched alkyl group having 1 to 40 carbon atoms, or a monovalent organic group having 3 to 40 carbon atoms including an alicyclic group, wherein some or all of the hydrogen atoms of this alkyl group may be substituted with fluorine atoms, and D is an oxygen atom, a sulfur atom, or -NR ｄ - (Here, R ｄ (where represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), a is an integer from 0 to 3, and * represents the bond position. If a is 2 or more, multiple R １ and R ２ Each of the above definitions is independent of the others. X and Y are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, or a C1-C3 alkyl group, and some or all of the hydrogen atoms in this alkyl group may be substituted with fluorine atoms. At least one of X and Y is a group other than a hydrogen atom among the groups defined above. A liquid crystal alignment agent comprising a compound having a photo-aligning group and a thermally crosslinkable group, wherein the thermally crosslinkable group is a group that can react with a carboxyl group to form a covalent bond, a polyamic acid as component (B), and a solvent. 【Chemistry 1】

2. The liquid crystal alignment agent according to claim 1, wherein the thermally crosslinkable group of component (A) is a group selected from epoxy moiety-containing groups, oxetanyl groups, thyranyl groups, and cyclocarbonate groups.

3. The liquid crystal alignment agent according to claim 1, wherein the thermally crosslinkable group of component (A) is an epoxy group.

4. A liquid crystal alignment film formed using the liquid crystal alignment agent described in any one of claims 1 to 3.

5. A method for manufacturing a liquid crystal alignment film, comprising the steps of: applying a liquid crystal alignment agent according to any one of claims 1 to 3 onto a substrate to form a coating film; and irradiating the coating film with light either when the coating film is not in contact with the liquid crystal layer or when it is in contact with the liquid crystal layer.

6. A liquid crystal display element comprising the liquid crystal alignment film described in claim 4.

7. The following formula (pa-1) (where A is optionally a group selected from a fluorine atom, a chlorine atom, and a cyano group, or is substituted with an alkoxy group having 1 to 5 carbon atoms, a linear or branched alkyl residue (which may be substituted with 1 cyano group or 1 or more halogen atoms), and represents pyrimidine-2,5-diyl, pyridine-2,5-diyl, thiophene-2,5-diyl, furan-2,5-diyl, 1,4- or 2,6-naphthylene or phenylene, R １ is a single bond, an oxygen atom, -COO- or -OCO-, R ２ is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed ring group, R ３ is a single bond, an oxygen atom, -COO- or -OCO-, R ４ is a linear or branched alkyl group having 1 to 40 carbon atoms, or a monovalent organic group having 3 to 40 carbon atoms containing an alicyclic group, and part or all of the hydrogen atoms of this alkyl group may be substituted with fluorine atoms, D is an oxygen atom, a sulfur atom or -NR ｄ -(where R ｄ represents a hydrogen atom or an alkyl having 1 to 3 carbon atoms), a is an integer from 0 to 3, and * represents the bonding position. When a is 2 or more, a plurality of R １ and R ２ each independently have the above definitions. 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, and part or all of the hydrogen atoms of this alkyl group may be substituted with fluorine atoms. At least one of X and Y is a group other than a hydrogen atom among the groups defined above.) A compound having a photo-orienting group and a thermally crosslinkable group, wherein the thermally crosslinkable group can react with a carboxyl group to form a covalent bond. 【Chemistry 2】

8. The compound according to claim 7, wherein the thermally crosslinkable group is selected from an epoxy moiety-containing group, an oxetanyl group, a thyranyl group, and a cyclocarbonate group.

9. A compound selected from the group consisting of EP2, EP7 to EP10 below. 【Transformation 3】

Images