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

Abstract

Provided are: a liquid crystal alignment film which has good liquid crystal alignment properties and excellent pretilt angle performance; a liquid crystal display element which has the liquid crystal alignment film; and a liquid crystal alignment agent which provides the liquid crystal alignment film. The invention provides a liquid crystal aligning agent. The liquid crystal aligning agent contains a compound which is used as a component (A) and has a photo-aligning group represented by the following formula (pa-1), an oxetanyl group and a polar group; a polyamic acid as component (B); and a solvent. [Formula 1] (In formula (pa-1), A represents a phenylene group or the like, R1 represents-COO-or-OCO-, R2 represents a cyclohexane-1, 4-diyl, R3 represents a cyclohexane-1, 4-diyl, R4 represents a linear or branched alkyl group having 1-40 carbon atoms, some or all of the hydrogen atoms of the alkyl group may be substituted by fluorine atoms, D represents an oxygen atom, a sulfur atom or-NRd-, and a represents an integer of 0-3 and represents a bonding position).

Description

Technical Field

[0001] This invention relates to a liquid crystal alignment agent, a liquid crystal alignment film obtained therefrom, and a liquid crystal display element having the obtained liquid crystal alignment film. More specifically, this invention relates to a liquid crystal alignment agent capable of providing a liquid crystal alignment film with good liquid crystal alignment, excellent pretilt angle performance, and high reliability, and 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 crystal in a certain direction. Currently, the main liquid crystal alignment films used in industry are made by coating a polyimide-based liquid crystal alignment agent containing a solution of polyamide acid (also known as polyamic acid) as a polyimide precursor, polyamic acid ester, or polyimide onto a substrate.

[0003] In addition, when the liquid crystal is aligned parallel or tilted relative to the substrate surface, a surface stretching process using friction is further performed after film formation.

[0004] On the other hand, when the liquid crystal is oriented perpendicularly to the substrate (referred to as 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 (e.g., see Patent Document 1), or steroid backbones (e.g., see Patent Document 2) are introduced into the side chains of the polyimide. In this case, when a voltage is applied between the substrates to tilt the liquid crystal molecules in a direction parallel to the substrate, it is necessary to tilt the liquid crystal molecules from the substrate normal direction in a direction inward toward the substrate surface. As methods for this purpose, for example, methods have been proposed such as providing protrusions on the substrate, providing slits on the display electrodes, slightly tilting the liquid crystal molecules from the substrate normal direction in a direction inward toward the substrate surface by friction (pre-tilting), and adding a photopolymerizable compound to the liquid crystal composition in advance, using it together with a vertical alignment film such as polyimide, and applying a voltage to the liquid crystal cell while irradiating with ultraviolet light, thereby pre-tilting the liquid crystal (e.g., see Patent Document 3), etc.

[0005] In recent years, as an alternative to the VA method for liquid crystal alignment control, methods utilizing anisotropic photochemical reactions based on polarized ultraviolet irradiation (photoalignment method) have also been proposed for the formation of protrusions or slits and PSA technology. Specifically, it is known that by irradiating a photoreactive, vertically oriented polyimide film with polarized ultraviolet light, alignment confinement capability and pretilt angle performance are imparted, thereby enabling uniform control of the tilt direction of liquid crystal molecules when a voltage is applied (see Patent Document 4).

[0006] VA-type liquid crystal display elements are used in TVs and automotive displays due to their high contrast and wide viewing angle. TV-use liquid crystal display elements use backlights that generate significant heat to achieve high brightness. Similarly, liquid crystal display elements used in automotive applications, such as in car navigation systems and dashboards, are often used or placed in high-temperature environments for extended periods. Under such harsh conditions, with gradual changes in the pretilt angle, problems such as loss of initial display characteristics or uneven display can occur. Furthermore, the voltage holding characteristics and charge accumulation characteristics during liquid crystal driving are also affected by the liquid crystal alignment film. Low voltage holding results in reduced contrast, while high charge accumulation relative to the DC voltage leads to screen burn-in.

[0007] Existing technical documents

[0008] Patent documents

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

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

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

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

[0013] The technical problem that the invention aims to solve

[0014] The present invention was made in view of the above circumstances, and its technical objective is to provide a liquid crystal alignment film with excellent vertical alignment and high voltage retention characteristics, a liquid crystal display element having the liquid crystal alignment film, and a liquid crystal alignment agent for providing the liquid crystal alignment film.

[0015] Technical solutions for solving technical problems

[0016] The inventors have discovered an invention based on the following <X>.

[0017] <X> A liquid crystal alignment agent comprising: a compound having a photo-alignment group, an oxobutyl group and a polar group as shown in formula (pa-1) as component (A); a polyamic acid as component (B); and a solvent.

[0018] [Chemistry 1]

[0019]

[0020] In formula (pa-1), A represents pyrimidin-2,5-diyl, pyridin-2,5-diyl, thiophene-2,5-diyl, furan-2,5-diyl, 1,4-naphthylene, 2,6-naphthylene, or phenylene. This group A can be substituted by a group selected from fluorine, chlorine, cyano, alkoxy groups with 1 to 5 carbon atoms, straight-chain alkyl groups with 1 to 5 carbon atoms, and branched-chain alkyl groups with 1 to 5 carbon atoms. This alkyl group can be substituted by one cyano or one or more halogen atoms; R R1 represents a single bond, an oxygen atom, -COO-, or -OCO-; R2 represents a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group, or a divalent fused-ring group; R3 represents a single bond, an oxygen atom, -COO-, or -OCO-; R4 represents a straight-chain or branched alkyl group with 1 to 40 carbon atoms, or a monovalent organic group with 3 to 40 carbon atoms containing an alicyclic group, wherein some or all of the hydrogen atoms of the alkyl group may be replaced by fluorine atoms; D represents an oxygen atom, a sulfur atom, or -NR. d -, where R d Indicates an alkyl group having 1 to 3 hydrogen atoms or carbon atoms; a is an integer from 0 to 3; Indicates the bonding position. When a is 2 or more, multiple R1 and R2 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 some or all of the hydrogen atoms of the above alkyl groups may be replaced by fluorine atoms.

[0021] The wavy lines between “C” and “A”, and between “C” and “X”, indicate that it can be either an E-type isomer or a Z-type isomer.

[0022] Invention Effects

[0023] According to the present invention, it is possible to provide a liquid crystal alignment film with good vertical alignment and high voltage retention, as well as a liquid crystal alignment agent for providing the alignment film.

[0024] Furthermore, the liquid crystal display element manufactured by the method of the present invention has excellent display characteristics. Detailed Implementation

[0025] The liquid crystal alignment agent of the present invention contains, as component (A), a compound having a photo-alignment group, an oxobutyl group and a polar group as shown in the following formula (pa-1) (hereinafter also referred to as a specific compound); as component (B), a polyamic acid; and a solvent.

[0026] The liquid crystal alignment agent of the present invention contains a compound as component (A) that has a photoalignment group, an oxobutyl group, and a polar group. Here, the photoalignment group has high sensitivity to light, thus exhibiting alignment control capability even under low-exposure polarized ultraviolet irradiation.

[0027] Furthermore, the photo-alignment groups of the compound as component (A) are hydrophobic. Therefore, when the liquid crystal alignment agent is coated onto the substrate, the polyamic acid as component (B) concentrates on the substrate side, while the compound as component (A) concentrates on the surface side. Thus, the photo-alignment groups of the coating obtained using the liquid crystal alignment agent of the present invention are concentrated on the surface layer, so good alignment can be obtained even with a reduced content of the compound as component (A). Additionally, the oxetane group of component (A) is a group capable of reacting with carboxyl groups to form covalent bonds, thereby enabling crosslinking reactions between the compound as component (A) and component (B) to occur even with a short sintering time for the liquid crystal alignment agent. Furthermore, the presence of polar groups in component (A) acts as a catalyst for the reaction between the oxetane group and carboxyl groups, promoting the crosslinking reaction. Therefore, when anisotropy is exhibited at the photo-alignment sites through photoreaction, anisotropy is easily retained (stored) in the liquid crystal alignment film, thus improving liquid crystal alignment and exhibiting a liquid crystal pretilt angle.

[0028] Furthermore, the liquid crystal alignment agent of the present invention, by containing polyamic acid as component (B), can also achieve improvements in electrical properties such as improved voltage retention rate and suppression of residual charge accumulation.

[0029] The constituent elements of the present invention will now be described in detail.

[0030] <(A) Ingredients: Specific Compounds>

[0031] The specific compound of the liquid crystal alignment agent of the present invention as component (A) is a compound having a photoalignment group, an oxobutyl group, and a polar group as shown in formula (pa-1). Such a specific compound is preferably, for example, a compound shown in formula (a-1).

[0032] [Chemistry 2]

[0033]

[0034] In equation (a-1), M a This indicates a group containing an oxocyclic butyl group and a polar group. Examples of polar groups include hydroxyl, thiol, amino, monoalkylamino, dialkylamino, carboxyl, sulfonyl, pyridyl, imidazolyl, and triazolyl, with hydroxyl, thiol, and dialkylamino being preferred.

[0035] In the above formula (a-1), S a I represents a spacer group. a This indicates that M is arbitrarily bonded with a spacer group in between. a .

[0036] S a For example, it can be represented by the structure of the following formula (Sp).

[0037] [Chemistry 3]

[0038]

[0039] In formula (Sp),

[0040] The key to the left of W1 indicates the relationship with M. a Bonded bonds,

[0041] The key to the right of W3 indicates the same as I. a Bonded bonds,

[0042] W1, W2, and W3 independently represent a single bond, a divalent heterocycle, and -(CH2), respectively. n -(where n represents 1 to 20), -OCH2-, -CH2O-, -COO-, -OCO-, -CH=CH-, -CF=CF-, -CF2O-, -OCF2-, -CF2CF2- or -C≡C-, wherein one or more of the non-adjacent CH2 groups among these substituents can be independently replaced by -O-, -CO-, -CO-O-, -O-CO-, -Si(CH3)2-O-Si(CH3)2-, -NR-, -NR-CO-, -CO-NR-, -NR-CO-O-, -OCO-NR-, -NR-CO-NR-, -CH=CH-, -C≡C- or -O-CO-O- (where R independently represents hydrogen or a straight-chain or branched alkyl group having 1 to 5 carbon atoms),

[0043] A1 and A2 are each independently selected from single bonds, alkylene groups, divalent aromatic groups, divalent alicyclic groups, or divalent heterocyclic groups. Each group is unsubstituted or one or more hydrogen atoms may be substituted by fluorine atoms, chlorine atoms, cyano groups, methyl groups, or methoxy groups.

[0044] Examples of aromatic groups in A1 and A2 include aromatic hydrocarbon groups with 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 with 6 to 12 carbon atoms, such as cyclohexane rings and bicyclohexane structures. Examples of heterocyclic groups in A1 and A2 include nitrogen-containing heterocyclic rings such as pyridine rings, piperidine rings, and piperazine rings. Examples of alkylene groups in A1 and A2 include straight-chain or branched alkylene groups with 1 to 10 carbon atoms.

[0045] In equation (a-1), I a It is a monovalent organic group represented by formula (pa-1).

[0046] [Chemistry 4]

[0047]

[0048] In formula (pa-1), A represents pyrimidin-2,5-diyl, pyridin-2,5-diyl, thiophene-2,5-diyl, furan-2,5-diyl, 1,4-naphthylene, 2,6-naphthylene, or phenylene. This group A can be substituted by a group selected from fluorine, chlorine, cyano, alkoxy groups with 1 to 5 carbon atoms, straight-chain alkyl groups with 1 to 5 carbon atoms, and branched-chain alkyl groups with 1 to 5 carbon atoms. This alkyl group can be substituted by one cyano or one or more halogen atoms; R R1 represents a single bond, an oxygen atom, -COO-, or -OCO-; R2 represents a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group, or a divalent fused-ring group; R3 represents a single bond, an oxygen atom, -COO-, or -OCO-; R4 represents a straight-chain or branched alkyl group with 1 to 40 carbon atoms, or a monovalent organic group with 3 to 40 carbon atoms containing an alicyclic group, wherein some or all of the hydrogen atoms of the alkyl group may be replaced by fluorine atoms; D represents an oxygen atom, a sulfur atom, or -NR. d -, where R d Indicates an alkyl group having 1 to 3 hydrogen atoms or carbon atoms; a is an integer from 0 to 3; Indicates the bonding position. When a is 2 or more, multiple R1 and R2 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 some or all of the hydrogen atoms of the above alkyl groups may be replaced by fluorine atoms.

[0049] The wavy lines between “C” and “A”, and between “C” and “X”, indicate that it can be either the E-type isomer or the Z-type isomer. It should be noted that in this specification, the “wavy line” has the same meaning as described above.

[0050] From the perspective of being able to exhibit good vertical orientation control and a stable pretilt angle, a is preferably an integer from 1 to 3.

[0051] From the viewpoint that it can exhibit good vertical orientation control and stable pretilt angle, the group shown in (pa-1) above is preferably the group shown in (pa-1-a) below, but is not limited thereto.

[0052] [Chemistry 5]

[0053]

[0054] In formula (pa-1-a),

[0055] Z represents either an oxygen atom or a sulfur atom.

[0056] X a and X bEach of the following is independently a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, or an alkyl group having 1 to 3 carbon atoms, wherein some or all of the hydrogen atoms of the alkyl group may be replaced by fluorine atoms.

[0057] R1 is a single bond, an oxygen atom, -COO-, or -OCO-.

[0058] R2 is a divalent aromatic group, a divalent alicyclic group, or a divalent heterocyclic group.

[0059] R3 is a single bond, an oxygen atom, or -COO- or -OCO-.

[0060] R4 is a straight-chain or branched alkyl group with 1 to 40 carbon atoms, or a monovalent organic group with 3 to 40 carbon atoms containing an alicyclic group, wherein some or all of the hydrogen atoms of the alkyl group may be replaced by fluorine atoms.

[0061] R5 is an alkyl group with 1 to 3 carbon atoms, an alkoxy group with 1 to 3 carbon atoms, a fluorine atom, or a cyano group, preferably a methyl group, a methoxy group, or a fluorine atom.

[0062] When there are two or more R1, R2, or R5, they can be the same or different from each other.

[0063] a is an integer from 0 to 3, and b is an integer from 0 to 4.

[0064] In equation (a-1), S is used as a The alkylene group having a straight chain or branched chain with 1 to 10 carbon atoms, preferably a straight chain or branched chain with 1 to 8 carbon atoms, such as methylene, ethylene, n-propylene, n-butylene, tert-butylene, n-pentylene, n-hexylene, n-heptylene, or n-octylene.

[0065] As S a Divalent aromatic groups, for example, include 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 2,3,5,6-tetrafluoro-1,4-phenylene, etc.

[0066] In equation (a-1), S is used as a The divalent alicyclic group, for example, trans-1,4-cyclohexylene, trans-trans-1,4-bicyclohexylene, etc.

[0067] As S a Examples of divalent heterocyclic groups include pyridine-2,6-diyl, pyridine-3,5-diyl, furan-2,5-diyl, piperazine-1,4-diyl, and piperidine-1,4-diyl.

[0068] S aPreferably, it is 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.

[0069] In the above formula (a-1), S serves as the spacer group. a , preferably -CH2-.

[0070] In formula (pa-1), the divalent aromatic group of R2 can be, for example, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 2,3,5,6-tetrafluoro-1,4-phenylene, naphthylene, etc.

[0071] Examples of divalent alicyclic groups that can be represented by R2 include trans-1,4-cyclohexylene and trans-trans-1,4-bicyclohexylene.

[0072] Examples of divalent heterocyclic groups that can be represented by R2 include pyridine-2,6-diyl, pyridine-3,5-diyl, furan-2,5-diyl, piperazine-1,4-diyl, and piperidine-1,4-diyl.

[0073] R2 is preferably 1,4-phenylene, trans-1,4-cyclohexylene, and trans-trans-1,4-bicyclohexylene.

[0074] As R4, a straight-chain or branched alkyl group having 1 to 40 carbon atoms, for example, a straight-chain or branched alkyl group having 1 to 20 carbon atoms, may have some or all of its hydrogen atoms replaced by fluorine atoms. Examples of alkyl groups include methyl, ethyl, n-propyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-lauryl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecanyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecanyl, n-eicosyl, 4,4,4-trifluorobutyl, 4,4,5,5,5-pentafluoropentyl, 4,4,5,5,6,6,6-heptafluorohexyl, 3,3,4,4,5,5,5-heptafluoropentyl, 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl, 2-(perfluorobutyl)ethyl, 2-(perfluorooctyl)ethyl, 2-(perfluorodecyl)ethyl, etc.

[0075] Specific compounds that are components of (A) may be represented by compounds shown in formulas (AD-1) to (AD-4), but are not limited to these.

[0076] [Chemistry 6]

[0077]

[0078] <Methods for manufacturing specific compounds>

[0079] The specific compound that is component (A) can be produced by combining known reactions, specifically by the method described in the “Example of Additive Synthesis” below, or by a method based on that method.

[0080] <(B) Component>

[0081] The liquid crystal alignment agent of the present invention contains polyamic acid (P) as component (B).

[0082] The aforementioned polyamic acid (P) can be obtained by polymerization of a diamine component with a tetracarboxylic acid component containing a tetracarboxylic acid dianhydride.

[0083] (Diamine)

[0084] The diamine component used in the manufacture of the aforementioned polyamic acid (P) can be of various types depending on the purpose. It should be noted that the diamine used in the manufacture of polyamic acid (P) can be used alone or in combination of two or more. The following diamines are preferred examples of the diamines (hereinafter also referred to as diamine (p)) used in the manufacture of polyamic acid (P).

[0085] The aromatic diamines (d) indicated by “AXJ” (details are described below), p-phenylenediamine, 2,3,5,6-tetramethylp-phenylenediamine, 2,5-dimethylp-phenylenediamine, m-phenylenediamine, 2,4-dimethylm-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 3,3′-dihydroxy-4,4′-diaminobiphenyl, 2,2′-difluoro-4,4′-diaminobiphenyl, 3,3′-difluoro-4,4′-diaminobiphenyl, 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl, 3,3′-bis(trifluoromethyl)-4,4′-diaminobiphenyl, 3,4′-diaminobiphenyl, 4,4′-diaminobiphenyl, 3,3′-diaminobiphenyl, 2,2′-diaminobiphenyl, 2,3′-diaminobiphenyl, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, bis(4-aminophenoxy)methane, 1,2-bis(4-aminophenyl)ethane, 1,2-bis(4-aminophenoxy)ethane, 1,3-bis(3-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,4-bis(4-amino-2-methylphenyloxy)butane, 1,4-bis(3- (Aminophenyl)butane, bis(3,5-diethyl-4-aminophenyl)methane, 1,5-bis(4-aminophenoxy)pentane, 1,5-bis(3-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,7-bis(3-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)nonane, 1,9-bis(3-aminophenoxy)nonane, 1,10-bis(4-aminophenoxy)decane, 1,10-bis(3-aminophenoxy)decane, 1,11-bis( 4-Aminophenoxy)undecane, 1,11-bis(3-aminophenoxy)undecane, 1,12-bis(4-aminophenoxy)dodecane, 1,12-bis(3-aminophenoxy)dodecane, 3-[2-[2-(4-aminophenoxy)ethoxy]ethoxy]aniline, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 4,4′-bis(4-aminophenoxy)biphenyl, 4,4′-bis(4-aminophenoxy)diphenyl ether, 1,4-bis[4-(4-aminophenoxy)phenoxy]benzene, 1,2-bis(6-amino-2-naphthoxy)ethane, 1,2-Di(6-amino-2-naphthyl)ethane, 6-[2-(4-aminophenoxy)ethoxy]-2-naphthylamine, 4′-[2-(4-aminophenoxy)ethoxy]-[1,1′-biphenyl]-4-amine, 1,4-bis[2-(4-aminophenyl)ethyl]succinate, 1,6-bis[2-(4-aminophenyl)ethyl]hexadiate, 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) isophthalic acid esters; 4,4′-diaminoazobenzene, diaminodiphenylacetylene, 4,4′-diaminochalcone, or [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, or [4-[(E)-3-[[5-amino-2-[4-amino-2-[[(E)-3-[4-[4-(4,4,4-trifluorobutoxy)benzoyl]oxyphenyl]prop-2-enyl]oxymethyl]phenyl]phenyl]methoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, representing aromatic compounds with cinnamic acid ester structures on the side chain. Diamines with photo-oriented groups, such as aromatic diamines; diamines with photopolymerizable groups at the end, such as 2-(2,4-diaminophenoxy)ethyl methacrylate and 2,4-diamino-N,N-diallyl aniline; diamines with groups exhibiting free radical polymerization initiator function, such as benzoin or its alkyl ethers represented by 1-(4-(2-(2,4-diaminophenoxy)ethoxy)phenyl)-2-hydroxy-2-methylpropionanone, 2-(4-(2-hydroxy-2-methylpropionyl)phenoxy)ethyl-3,5-diaminobenzoate; benzoin ketals, acetophenones, phosphine oxides, benzophenones, or aminobenzophenones; diamines with amide bonds, such as 4,4′-diaminobenzoylaniline; 1, Diamines containing urea bonds, such as 3-bis(4-aminophenyl)urea, 1,3-bis(4-aminobenzyl)urea, and 1,3-bis(4-aminophenylethyl)urea; 4,4′-sulfonyl diphenylamine, 3,3′-sulfonyl diphenylamine, bis(4-aminophenyl)silane, bis(3-aminophenyl)silane, dimethyl-bis(4-aminophenyl)silane, dimethyl-bis(3-aminophenyl)silane, 4,4′-thiodiphenylamine, 3,3′-thiodiphenylamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)propane, 2,2-bis(3-amino-4-methylphenyl)propane, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 4,4′-diaminodibenzophenone, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene; 2,6-diaminopyridine, 3,4-di... Aminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, 1,4-bis-(4-aminophenyl)-piperazine, 3,6-diaminoacridine, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N-[3-(1H-imidazol-1-yl)propyl]-3,5-diaminobenzamide, 4-[4-[(4-aminophenoxy)methyl]-4,5-dihydro-4-methyl-2-oxazolyl]-aniline, 1,4-bis(p-aminobenzyl)piperazine, 4,4′-propane-1,3-diyl-bis(piperidin-1,4-diyl)diphenylamine, 4-(4-aminophenoxycarbonyl)-1-(4-aminophenyl)piperidine, and the following formula (z- 1) Diamines of formula (z-5), 2,5-bis(4-aminophenyl)pyrrole, 4,4′-(1-methyl-1H-pyrrole-2,5-diyl)bis[aniline], 1,4-bis(4-aminophenyl)piperazine, 2-N-(4-aminophenyl)pyridin-2,5-diamine, 2-N-(5-aminopyridin-2-yl)pyridin-2,5-diamine, 2-(4-aminophenyl)-5-aminobenzimidazole, 2-(4-aminophenyl)-6-aminobenzimidazole, 5-(1H-benzimidazol-2-yl)phenyl-1,3-diamine and other heterocyclic diamines, or 4,4′-diaminodiphenylamine, 4,4′-diaminodiphenyl-N-methylamine, N,N′-bis(4-aminophenyl)-1,4-benzyldiphenylamine, etc. Amines, such as N,N′-bis(4-aminophenyl)-benzidine, N,N′-bis(4-aminophenyl)-N,N′-dimethylbenzidine, or N,N′-bis(4-aminophenyl)-N,N′-dimethyl-1,4-phenylenediamine, which have a diphenylamine structure, are representative of diamines selected from nitrogen-containing heterocycles, secondary amino groups, and tertiary amino groups. These diamines do not contain an amino group bonded to a hydrogen atom that can be removed by heating. Examples include 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-aminophenyl)ethane-3-carboxylic acid, and 4,Diamines with carboxyl groups, such as 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-indane-5-amine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indane-6-amine; N1,N6-bis(2-tert-butoxycarbonylamino-4-aminophenyl)hexamethylenediamine, 4-amino-N-(2-tert-butoxycarbonylamino-4-aminophenyl)benzamide, N-[(2,5-diaminophenyl)methyl]-1,1-dimethylethyl ester of carbamate, N-[3-(2,5-diaminophenyl)propyl]-1,1-dimethylethyl ester of carbamate, 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, carbamate-N-[2-(4-aminophenyl)ethyl]-N-[[[2-(4-aminophenyl)ethyl]amino]carbonyl]-1,1-dimethylethyl ester, carbamate-N-(4-aminophenyl)-N-[[1-(4-aminophenyl)-4-piperidinyl]methyl]-1,1-dimethylethyl ester, etc., all have the group "-N(D)-" (D indicates that it is produced by heating). Aromatic diamines (tn) having long-chain alkyl groups having 12 to 20 carbon atoms, represented by 1,3-bis(3-aminopropyl)-tetramethyldisiloxane, 1-dodecyloxy-2,4-diaminobenzene, 1-tetradecyloxy-2,4-diaminobenzene, 1-pentadecanyloxy-2,4-diaminobenzene, 1-hexadecyloxy-2,4-diaminobenzene, 1-octadecyloxy-2,4-diaminobenzene, 1-dodecyloxy-2,5-diaminobenzene, 1-tetradecyloxy-2,5-diaminobenzene, 1-pentadecanyloxy-2,5-diaminobenzene, 1-hexadecyloxy-2,5-diaminobenzene, and 1-octadecyloxy-2,5-diaminobenzene; 1,3-bis(3-aminopropyl)-tetramethyldisiloxane, 1,Diamines containing siloxane bonds, such as 3-bis[3-(p-aminophenylcarbamoyl)propyl]tetramethyldisiloxane; diamines containing two amino groups bonded to the groups shown in any of the formulas (Y-1) to (Y-167) as described in International Publication No. 2018 / 117239.

[0086] [Chemistry 7]

[0087]

[0088] In the aromatic diamine (d) represented by "AXJ" above, A represents a monovalent group formed by two primary amino groups bonded to an aromatic group. Specific examples of aromatic groups include benzene rings, naphthyl rings, and biphenyl structures. X represents a single bond, -(CH2). a -(a is an integer from 1 to 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, A0 and A1 represent oxygen atoms or -COO-, m0 is an integer of 0 or 1, and m1 is an integer from 1 to 2. When m1 is 2, multiple a1 and A1 independently have the above definitions).

[0089] J represents a monovalent organic group having at least one group selected from alicyclic hydrocarbon groups with 4 to 40 carbon atoms and aromatic hydrocarbon groups with 6 to 40 carbon atoms. In this group, at least one hydrogen atom of the aforementioned alicyclic hydrocarbon group and aromatic hydrocarbon group is substituted by a substituent (v), said substituent (v) being any one of a halogen atom, a halogen-containing alkyl group, a halogen-containing alkoxy group, an alkyl group with 3 to 10 carbon atoms, an alkoxy group with 3 to 10 carbon atoms, and an alkenyl group with 3 to 10 carbon atoms. Furthermore, any carbon-carbon single bond in these substituents (v) (wherein excluding halogen atoms) can be interrupted by -O-. It should be noted that J may also be unsubstituted or have at least one group selected from alicyclic hydrocarbon groups and aromatic hydrocarbon groups substituted by substituents other than those described above, in addition to the aforementioned alicyclic hydrocarbon groups and aromatic hydrocarbon groups.

[0090] Examples of alkyl groups containing halogen atoms include alkyl groups containing halogen atoms with 1 to 10 carbon atoms.

[0091] Examples of alkoxy groups containing halogen atoms include alkoxy groups with 1 to 10 carbon atoms.

[0092] Examples of alicyclic hydrocarbon groups for J include cyclobutane rings, cyclopentane rings, cyclohexane rings, cyclodecane rings, and steroid skeletons (examples include cholesteryl groups, lanostane groups, etc.). Examples of aromatic hydrocarbon groups include benzene rings and naphthalene rings. When J has at least one of cyclohexane rings and benzene rings, the group "-XJ" can be represented by structures such as (S1), and more preferably by formulas (S1-1) to (S1-5) (where X...). 1 R 1 , X of equation (S1) 1 R 1 , (Same meaning)

[0093] [Chemistry 8]

[0094]

[0095] In the formula, X 1 Indicates a single bond, -(CH2) a -(a is an integer from 1 to 15), -CONH-, -CO-N(CH3)-, -NH-, -O-, -COO-, or -(A0) m0 -((CH2) a1 -A1) m1 -(a1 is an integer from 1 to 15, A0 and A1 represent oxygen atoms or -COO-, m0 is an integer of 0 or 1, and m1 is an integer from 1 to 2. When m1 is 2, multiple a1 and A1 independently have the above definitions.) (Indicates the bonding location).

[0096] G1 represents a divalent cyclic group selected from phenylene and cyclohexylene. Any hydrogen atom on the above cyclic group can be replaced by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorinated alkyl group having 1 to 3 carbon atoms, a fluorinated alkoxy group having 1 to 3 carbon atoms, or a fluorine atom.

[0097] m is an integer from 1 to 4. When m is 2 or greater, there are multiple X... 1 G 1 Each of them independently possesses the above definition.

[0098] R 1 It refers to a fluorine atom, an alkyl group containing fluorine atoms with 1 to 10 carbon atoms, an alkoxy group containing fluorine atoms with 1 to 10 carbon atoms, an alkyl group with 3 to 10 carbon atoms, an alkoxy group with 3 to 10 carbon atoms, or an alkoxyalkyl group with 3 to 10 carbon atoms.

[0099] [Chemistry 9]

[0100]

[0101] Specific examples of the above-mentioned aromatic diamines (d) include the diamines shown in formulas (d-1) to (d-2) below. More preferred examples include diamines shown in formulas (d-1) to (d-2) whose group "-XJ" is any one of the above structures (S1) or formulas (S1-1) to (S1-5), as well as diamines having a steroid skeleton such as cholesteryloxy-3,5-diaminobenzene, cholesteryloxy-3,5-diaminobenzene, cholesteryloxy-2,4-diaminobenzene, cholesteryl 3,5-diaminobenzoate, cholesteryl 3,5-diaminobenzoate, cholesteryl 3,5-diaminobenzoate, lanostane 3,5-diaminobenzoate, and 3,6-bis(4-aminobenzoyloxy)cholestane.

[0102] [Chemistry 10]

[0103]

[0104] X and J have the same meaning as X and J in the above-mentioned aromatic diamine (d), including the preferred embodiment. In the above formula (d-2), the two X and J can be the same or different from each other.

[0105] When the above-mentioned aromatic diamine (d) is used as the above-mentioned diamine (p), it is preferred to be 5 to 95 mol% of the total diamine component used to manufacture polyamic acid (P), more preferably 10 to 90 mol%.

[0106] (Tetracarboxylic acid dianhydride)

[0107] The tetracarboxylic dianhydrides that can be used in the synthesis of the aforementioned polyamic acid (P) include at least one compound selected from acyclic aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, and aromatic tetracarboxylic dianhydrides. More preferably, it comprises a tetracarboxylic dianhydride having at least one partial structure selected from benzene rings, cyclobutane rings, cyclopentane rings, and cyclohexane rings; even more preferably, it comprises a tetracarboxylic dianhydride having at least one partial structure selected from cyclobutane rings, cyclopentane rings, and cyclohexane rings.

[0108] As a tetracarboxylic acid component that can be used in the synthesis of polyamic acid (P), it is preferable to include the following tetracarboxylic dianhydride (hereinafter, also collectively referred to as specific tetracarboxylic dianhydrides).

[0109] It should be noted that the aforementioned tetracarboxylic acid dianhydrides can be used alone or in combination with two or more.

[0110] Acyclic aliphatic tetracarboxylic anhydrides such as 1,2,3,4-butanetetracarboxylic anhydride; 1,2,3,4-cyclobutanetetracarboxylic anhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic anhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic anhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic anhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic anhydride, 1,3-difluoro-1,2,3,4-cyclobutanetetracarboxylic anhydride, 1 3-Bis(trifluoromethyl)-1,2,3,4-cyclobutanetetracarboxylic anhydride, 1,2,3,4-cyclopentanetetracarboxylic anhydride, 1,2,4,5-cyclohexanetetracarboxylic anhydride, 3,3′,4,4′-dicyclohexyltetracarboxylic anhydride, 2,3,5-tricarboxycyclopentylacetic anhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)tetrahydronaphtho[1,2-dicarboxylic anhydride, 5-(2,5-dioxotetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan -1,3-dione, 5-(2,5-dioxotetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, bicyclic [2.2.2]oct-7-en-2,3,5,6-tetracarboxylic dianhydride, bicyclic [2.2.2]octane-2,3,5,6-tetracarboxylic dianhydride, 2,4,6,8-tetracarboxylic bicyclic [3.3.0]octane-2:4,6:8-dianhydride and other alicyclic tetracarboxylic dianhydrides; pyromellitic dianhydride, 3,3′ 4,4′-benzophenone tetracarboxylic dianhydride, 3,3′,4,4′-diphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3′,4,4′-diphenyl ether tetracarboxylic dianhydride, 3,3′,4,4′-biphenyl tetracarboxylic dianhydride, 2,2′,3,3′-biphenyl tetracarboxylic dianhydride, 4,4′-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, ethylene glycol bis(triphenylene oxide) tricarboxylic anhydride Aromatic tetracarboxylic acid dianhydrides such as bis(anhydrotrimellitate), 4,4′-(hexafluoroisopropylidene) bis(phthalic anhydride), 4,4′-carbonyl bis(phthalic anhydride), 4,4′-(1,4-phenylenedioxy)bis(phthalic anhydride), or 4,4′-(1,4-phenylenedimethyl)bis(phthalic anhydride); and tetracarboxylic acid dianhydrides as described in Japanese Patent Application Publication No. 2010-97188.

[0111] Preferred examples of the aforementioned specific tetracarboxylic acid derivatives include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-difluoro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-bis(trifluoromethyl)-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3′,4,4′-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxylated cyclopentylacetic acid dianhydride, and 5-(2,5-dioxo) Tetrahydrofuran-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-tetracarboxylic acid bicyclo[3.3.0]octane-2:4,6:8-dianhydride, etc. Benzenetetracarboxylic dianhydride, 3,3′,4,4′-benzophenone tetracarboxylic dianhydride, 3,3′,4,4′-diphenylsulfone tetracarboxylic 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.

[0112] The specific proportion of tetracarboxylic acid dianhydride used is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 50 mol% or more, out of a total of 100 mol% of tetracarboxylic acid components used.

[0113] (Synthesis of polyamic acid)

[0114] The synthesis of polyamic acid is carried out by reacting a diamine component containing the aforementioned diamine with a tetracarboxylic acid component containing the aforementioned tetracarboxylic dianhydride or its derivative in an organic solvent. The ratio of tetracarboxylic dianhydride to diamine used in the polyamic acid synthesis reaction is preferably 0.5 to 2 equivalents of the anhydride group of the tetracarboxylic dianhydride relative to 1 equivalent of the amino group of the diamine, more preferably 0.8 to 1.2 equivalents. Similar to conventional polycondensation reactions, the closer the equivalent of the anhydride group of the tetracarboxylic dianhydride is to 1 equivalent, the larger the molecular weight of the resulting polyamic acid.

[0115] The reaction temperature in the synthesis of polyamic acid is preferably -20 to 150°C, more preferably 0 to 100°C. Furthermore, the reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours.

[0116] The synthesis reaction of polyamic acid can be carried out at any concentration, preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The reaction is initially carried out at a high concentration, and then a solvent can be added.

[0117] Specific examples of the aforementioned organic solvents include compound (a), cyclohexanone, cyclopentanone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and 1,3-dimethyl-2-imidazolinone. Furthermore, when the polymer has high solvent solubility, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, diethylene glycol monomethyl ether, or diethylene glycol monoethyl ether can be used.

[0118] <End-capping agent>

[0119] In synthesizing the polyamic acid of this invention, a suitable end-capping agent can be used together with a tetracarboxylic acid component containing tetracarboxylic dianhydride or a derivative thereof and a diamine component containing the aforementioned diamine to synthesize a capped polymer. The capped polymer has the effect of improving the film hardness of the oriented film obtained by coating and improving the adhesion properties between the sealant and the oriented film.

[0120] Examples of the ends of the polyamic acid in this invention include amino, carboxyl, anhydride, or groups derived from the capping agents described below. Amino, carboxyl, and anhydride groups can be obtained through conventional condensation reactions, or by sealing the ends using the capping agents described below.

[0121] Examples of capping agents include acetic anhydride, maleic anhydride, nadic anhydride, phthalic anhydride, itaconic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, trimellitic anhydride, 3-(3-trimethoxysilyl)propyl-3,4-dihydrofuran-2,5-dione, 4,5,6,7-tetrafluoroisobenzofuran-1,3-dione, 4-ethynyl phthalic anhydride, etc.; dicarbonate diesters such as ditert-butyl dicarbonate and diallyl dicarbonate; acryloyl chloride, methacryloyl chloride, etc. Chlorocarbonyl compounds such as nicotinyl chloride; monoamine compounds such as aniline, 2-aminophenol, 3-aminophenol, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, etc.; isocyanates with unsaturated bonds such as ethyl isocyanate, phenyl isocyanate, naphthyl isocyanate, or 2-acryloyloxyethyl isocyanate and 2-methacryloyloxyethyl isocyanate, etc.

[0122] The proportion of the capping agent used is preferably 0.01 to 20 moles, more preferably 0.01 to 10 moles, relative to the total 100 moles of the diamine component used.

[0123] The weight-average molecular weight (Mw) of polyamic acid converted from polystyrene by gel permeation chromatography (GPC) is preferably 1,000 to 500,000, 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) of polystyrene determined by GPC, is preferably 15 or less, more preferably 10 or less. By maintaining the molecular weight within the above range, good orientation of the liquid crystal display element can be ensured.

[0124] Relative to 100 parts by mass of polyamic acid component (B), the content of the specific compound in the liquid crystal alignment agent of the present invention as component (A) is preferably 0.5 to 30 parts by mass, more preferably 0.8 to 20 parts by mass, and even more preferably 1 to 10 parts by mass.

[0125] [Preparation of Liquid Crystal Alignment Agent]

[0126] The liquid crystal alignment agent used in this invention is preferably prepared as a coating liquid in a manner suitable for forming a liquid crystal alignment film. That is, the liquid crystal alignment agent of this invention is preferably prepared in the form of a solution in which the resin component for forming the resin coating is dissolved in an organic solvent. Here, the resin component refers to the specific compound as component (A) and the polyamic acid as component (B) as described above. In this case, the total content of the specific compound as component (A) and the content of the polyamic acid as component (B) relative to the liquid crystal alignment agent as a whole 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.

[0127] <Solvent>

[0128] The solvent contained in the liquid crystal alignment agent used in this invention is not particularly limited as long as it is a solvent that dissolves both component (A) and component (B). The liquid crystal alignment agent may contain one type of solvent, or a mixture of two or more types. Furthermore, even a solvent that does not dissolve component (A) or component (B) can be used in conjunction with a solvent that does dissolve component (A) or component (B). In this case, if the surface energy of the solvent that does not dissolve component (A) or component (B) is lower than that of the solvent that dissolves component (A) or component (B), the liquid crystal alignment agent can be coated well on the substrate, which is therefore preferable.

[0129] 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, 3-methoxy-N,N-dimethylpropionamide, 3-ethoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, 1,3-dimethyl-2-imidazolinone and other dialkylimidazolinones, lactones such as γ-butyrolactone, γ-valerolactone, and δ-valerolactone, carbonates such as ethylene carbonate and propylene carbonate, methanol, ethanol, propanol, and isopropyl alcohol. Alcohols, 3-methyl-3-methoxybutanol, ethylpentyl ketone, methyl nonyl ketone, methyl ethyl ketone, isopentylmethyl ketone, methyl isopropyl ketone, diisobutyl ketone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, 4-hydroxy-4-methyl-2-pentanone and other ketones, compounds shown in formula (Sv-1) and formula (Sv-2) below, 4-methyl-2-pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, 2-methylcyclohexyl acetate, butyl butyrate, isopentyl butyrate, diisobutylcarbinol, diisopentyl ether, etc.

[0130] [Chemistry 11]

[0131]

[0132] In formulas (Sv-1) to (Sv-2), Y1 and Y2 are each independently a hydrogen atom or a monovalent hydrocarbon group with 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 with 2 to 4 carbon atoms. n1 is an integer from 1 to 3. When n1 is 2 or 3, multiple R1s can be the same or different. Z1 is a divalent hydrocarbon group with 1 to 6 carbon atoms, and Y3 and Y4 are each independently a hydrogen atom or a monovalent hydrocarbon group with 1 to 6 carbon atoms.

[0133] In formula (Sv-1), examples of monovalent hydrocarbon groups with 1 to 6 carbon atoms in Y1 and Y2 include monovalent chain hydrocarbon groups with 1 to 6 carbon atoms, monovalent alicyclic hydrocarbon groups with 1 to 6 carbon atoms, and monovalent aromatic hydrocarbon groups with 1 to 6 carbon atoms. Examples of monovalent chain hydrocarbon groups with 1 to 6 carbon atoms include alkyl groups with 1 to 6 carbon atoms. The alkidine group of R1 can be straight-chain or branched.

[0134] In formula (Sv-2), the divalent hydrocarbon group with 1 to 6 carbon atoms as Z1 can be exemplified by alkyl diols with 1 to 6 carbon atoms.

[0135] Examples of monovalent hydrocarbon groups with 1 to 6 carbon atoms in Y3 and Y4 include monovalent chain hydrocarbon groups with 1 to 6 carbon atoms, monovalent alicyclic hydrocarbon groups with 1 to 6 carbon atoms, and monovalent aromatic hydrocarbon groups with 1 to 6 carbon atoms. Examples of monovalent chain hydrocarbon groups with 1 to 6 carbon atoms include alkyl groups.

[0136] Specific examples of solvents represented by formula (Sv-1) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monohexyl ether, ethylene glycol dimethyl ether, ethylene glycol monoacetate, ethylene glycol diacetate, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether, propylene glycol diacetate, ethylene glycol, 1,4-butanediol, 3-methoxybutyl acetate, 3-ethoxybutyl acetate, etc.

[0137] Specific examples of the solvents shown in (Sv-2) include methyl glycolate, ethyl glycolate, butyl glycolate, ethyl lactate, butyl lactate, isoamyl lactate, ethyl-3-ethoxypropionate, methyl-3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, etc.

[0138] The preferred boiling point for the solvent is 80–200°C. More preferably, it is 80–180°C. Examples of preferred solvents include N,N-dimethylformamide, tetramethylurea, 3-methoxy-N,N-dimethylpropionamide, propanol, isopropanol, 3-methyl-3-methoxybutanol, ethylpentyl ketone, methyl ethyl ketone, isopentylmethyl 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, isopentyl butyrate, diisobutylmethanol, diisopentyl ether, and ethylene glycol monomethyl ether. Dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol monoacetate, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether, 3-methoxybutyl acetate, methyl glycolate, ethyl glycolate, butyl glycolate, ethyl lactate, butyl lactate, isoamyl lactate, ethyl-3-ethoxypropionate, methyl-3-methoxypropionate, ethyl 3-methoxypropionate, etc.

[0139] A boiling point within this range is particularly preferred when the liquid crystal alignment agent containing the solvent is coated onto a plastic substrate described later.

[0140] <Other Ingredients>

[0141] The liquid crystal alignment agent used in this invention may also contain other components besides components (A) and (B) described above. Examples of such other components include component (C) below, crosslinking catalysts, compounds that improve film thickness uniformity and surface smoothness when coating the liquid crystal alignment agent, and compounds that improve the adhesion between the liquid crystal alignment film and the substrate, but it is not limited to these.

[0142] <(C) Ingredients>

[0143] Component (C) is a compound represented by the following formula (c-1) and whose 5% weight reduction temperature (Td5) is less than 250°C. By including component (C) in the liquid crystal alignment agent used in this invention, the voltage retention rate of the obtained liquid crystal alignment film can be improved.

[0144] [Chemistry 12]

[0145]

[0146] In equation (c-1), M c X represents a monovalent group containing a group that reacts with the polyamic acid of component (B). c Indicates a single bond, -(CH2) a -(a is an integer from 1 to 8), -CONH-, -CO-N(CH3)-, -NH-, -O-, -COO-, or -(A0) m0 -((CH2) a1 -A1) m1 -(a1 is an integer from 1 to 8, A0 and A1 each independently represent -O- or -COO-, m0 is an integer of 0 or 1, and m1 is an integer from 1 to 2. When m1 is 2, multiple a1 and A1 independently have the above definitions). G c R represents a divalent cyclic group selected from phenylene and cyclohexylene, wherein any hydrogen atom on the aforementioned cyclic group may be substituted by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorinated alkyl group having 1 to 3 carbon atoms, a fluorinated alkoxy group having 1 to 3 carbon atoms, or a fluorine atom. c This represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms, wherein some or all of the hydrogen atoms of the alkyl and alkoxy groups may be replaced by fluorine atoms. m is an integer from 1 to 2. When m is 2, multiple X... c G c Each of them independently possesses the above definition.

[0147] In equation (c-1), M c Preferably, it is a monovalent group containing a group that reacts with the carboxyl group or the amino group at the polymer terminus of the polyamic acid contained in component (B). Examples of groups that react with the carboxyl group include epoxy, oxetane, thiopropane, and cyclic carbonate groups. Examples of groups that react with the amino group include carboxyl, methyl ester, and ethyl ester groups. From a reactivity point of view, M c More preferably, it contains an epoxy group or an oxobutyric group.

[0148] In equation (c-1), R c The alkyl groups having 1 to 8 carbon atoms can be either straight-chain or branched, and examples include methyl, ethyl, n-propyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl. b Alkoxy groups with 1 to 8 carbon atoms can be either straight-chain or branched, and examples include methoxy, ethoxy, n-propoxy, n-butoxy, tert-butoxy, n-pentoxy, n-hexoxy, n-heptoxy, and n-octoxy.

[0149] The aforementioned 5% weight reduction temperature was determined using a differential thermal-thermogravimetric analysis (DTA / DSC 3+) apparatus (manufactured by Mettler Toredo). More specifically, the sample was weighed into an aluminum pan. The pan was mounted in the apparatus, and the temperature was increased from 25°C to 400°C at a rate of 10°C / min under a dry nitrogen atmosphere. The temperature at which the sample weight decreased by 5% compared to its initial weight was defined as the 5% weight reduction temperature.

[0150] When using component (C), from the viewpoint of improving the vertical alignment of the liquid crystal alignment film, the vertical alignment capability of component (C) is preferably lower than that of component (A).

[0151] The molecular weight of the compound used as component (C) is preferably 340 or less, more preferably 310 or less.

[0152] The compound represented by formula (c-1) is preferably a compound represented by formulas (c-1-1) to (c-1-4) below.

[0153] [Chemistry 13]

[0154]

[0155] In equations (c-1-1) to (c-1-4), M c X c R c M in the above formula (c-1) c X c R c They have the same meaning.

[0156] When using component (C), the proportion of component (C) used is preferably 1 to 30 parts by mass relative to 100 parts by mass of polyamic acid component (B), more preferably 3 to 20 parts by mass, and even more preferably 5 to 15 parts by mass.

[0157] <Cross-linking catalyst>

[0158] To promote the reaction between the oxobutyl group and the carboxyl group, a crosslinking catalyst can also be added to the liquid crystal alignment agent used in this invention. Examples of such crosslinking catalysts include p-toluenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, p-phenolsulfonic acid, 2-naphthalenesulfonic acid, mesitylenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H,1H,2H,2H-perfluorooctanesulfonic acid, perfluoro(2-ethoxyethane)sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, dodecylbenzenesulfonic acid, and other sulfonic acids or their hydrates or salts. Examples of compounds that produce acids through heat include: bis(toluenesulfonyloxy)ethane, bis(toluenesulfonyloxy)propane, bis(toluenesulfonyloxy)butane, p-nitrobenzyl toluenesulfonate, o-nitrobenzyl toluenesulfonate, 1,2,3-phenylenetris(methylsulfonate), pyridinium salt of p-toluenesulfonate, morpholinium salt of p-toluenesulfonate, ethyl p-toluenesulfonate, propyl p-toluenesulfonate, butyl p-toluenesulfonate, isobutyl p-toluenesulfonate, methyl p-toluenesulfonate, phenylethyl p-toluenesulfonate, cyanomethyl p-toluenesulfonate, 2,2,2-trifluoroethyl p-toluenesulfonate, 2-hydroxybutyl p-toluenesulfonate, N-ethyl-p-toluenesulfonamide, etc.

[0159] [Compounds that improve film thickness uniformity and surface smoothness]

[0160] Compounds that can improve film thickness uniformity and surface smoothness include fluorinated surfactants, organosilicon surfactants, and nonionic surfactants.

[0161] Specifically, examples include EFTOP (registered trademark) 301, EF303, EF352 (manufactured by Mitsubishi Materials Electronics & Chemicals Co., Ltd.), MEGAFAC (registered trademark) F171, F173, R-30 (manufactured by DIC Corporation), Fluorad FC430, FC431 (manufactured by 3M Corporation), AsahiGuard (registered trademark) AG710 (manufactured by AGC Corporation), and SURFLON (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimei Chemical Co., Ltd.).

[0162] The proportion of these surfactants used is preferably 0.01 to 2 parts by mass relative to 100 parts by mass of the resin component contained in the polymer composition, more preferably 0.01 to 1 part by mass.

[0163] [Compounds that improve the adhesion between the liquid crystal alignment film and the substrate]

[0164] Specific examples of compounds that improve the adhesion between the liquid crystal alignment film and the substrate include compounds containing functional silanes, as shown below.

[0165] Examples include: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureopropyltrimethoxysilane, 3-ureopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, and N-3-triethoxysilylpropyltriethyltriethene. Compounds containing amino silanes, such as tetraamine, N-3-trimethoxysilylpropyltriethylenetetramine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonylacetate, 9-triethoxysilyl-3,6-diazanonylacetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltriethoxysilane.

[0166] When using a compound that improves adhesion to the substrate, the amount used is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the resin component contained in the polymer composition.

[0167] In one embodiment, a photosensitizer may be used as an additive to improve the photoreactivity of the photooriented group. Specific examples include aromatic 2-hydroxy ketones (benzophenone), coumarins, coumarin ketones, carbonyl dicoumarins, acetophenones, anthraquinones, xanthones, thioxanthones, and acetophenone ketals.

[0168] <Liquid crystal alignment film and liquid crystal display element>

[0169] The liquid crystal alignment agent of the present invention can be coated and sintered on a substrate, and then aligned by means of friction treatment, light irradiation, etc., or in some applications such as vertical alignment, liquid crystal alignment films can be formed without alignment treatment. As a substrate, for example, glass such as float glass and soda glass can be used; transparent substrates containing 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 acid, and triacetyl cellulose can be used.

[0170] As a transparent conductive film disposed on one side of a substrate, NESA film (a registered trademark of PPG Industries, Inc.) containing tin oxide (SnO2) and ITO film containing indium oxide-tin oxide (In2O3-SnO2) can be used.

[0171] <Coating Formation Process>

[0172] The coating method for the liquid crystal alignment agent of the present invention is not particularly limited, and includes screen printing, flexographic printing, offset printing, inkjet printing, dip coating, roll coating, slot coating, spin coating, etc., which can be used depending on the purpose. After being coated onto a substrate by these methods, a coating film can be formed by evaporating the solvent through a heating unit such as a hot plate. It should be noted that the (A) component of the liquid crystal alignment agent coating film formed by the coating film forming process is unevenly distributed on the film surface due to the hydrophobicity of the photo-alignment groups, therefore, even if the content of the (A) component is reduced, good liquid crystal alignment is still exhibited.

[0173] Sintering after coating with the liquid crystal alignment agent can be carried out at any temperature from 40 to 300°C, preferably from 40 to 250°C, and more preferably from 40 to 230°C. In this process, the oxetane group of a specific compound as component (A) reacts with the carboxyl group of polyamic acid as component (B), thereby fixing the alignment groups.

[0174] The thickness of the coating film formed on the substrate is preferably 5–1000 nm, more preferably 10–500 nm or 10–300 nm. This sintering can be carried out using a hot plate, a hot air circulating furnace, an infrared furnace, etc.

[0175] <Light Irradiation Process>

[0176] In one embodiment, alignment processing can be performed using light irradiation, which may include: a step of coating the above-mentioned liquid crystal alignment agent onto a substrate to form a coating film; and a step of irradiating the coating film with light while the coating film is not in contact with the liquid crystal layer or while it is in contact with the liquid crystal layer.

[0177] Examples of light used in the orientation process involving illumination include ultraviolet light and visible light, which have wavelengths of 150 to 800 nm. Ultraviolet light with wavelengths of 300 to 400 nm is preferred. The illumination light can be polarized or unpolarized. As polarized light, linearly polarized light is preferred.

[0178] When using polarized light, the light can be irradiated from a direction perpendicular to the substrate surface, from an inclined direction, or a combination thereof. When irradiating unpolarized light, it is preferable to irradiate from a direction inclined relative to the substrate surface.

[0179] The light irradiation dose is preferably set to 0.1 mJ / cm. 2 Above and below 1000 mJ / cm 2 More preferably, the value is set to 1–500 mJ / cm. 2 Further optimization was performed with a range of 2–200 mJ / cm². 2 .

[0180] The liquid crystal display element of the present invention can be manufactured using conventional methods, and the manufacturing method is not particularly limited. The two substrates are positioned opposite each other with a suitable gap. To ensure uniform thickness of the liquid crystal sandwiched between the substrates, a spacer is preferably disposed between the substrates. As this spacer, in addition to conventionally known spacer materials such as distributed spacers or spacers formed from photosensitive spacer forming compositions, unevenness formed on a layer formed from a liquid crystal cured material can also be used as a spacer.

[0181] <Liquid Crystal Clamping Process>

[0182] When a liquid crystal cell is formed by sandwiching liquid crystal between substrates, the following two methods can be cited as examples. As the first method, a pair of substrates are arranged opposite each other with a gap (cell gap) between them, with each liquid crystal alignment film facing each other. The periphery of the pair of substrates is bonded together with a sealant. After liquid crystal is injected into the cell gap divided by the substrate surface and an appropriate sealant, the injection hole is sealed, thereby manufacturing a liquid crystal cell.

[0183] As a second method, the following method can be cited: a sealant, such as an ultraviolet light curable sealant, is applied to a specified area on one of the two substrates on which a liquid crystal alignment film is formed. Liquid crystal is then dropped onto a specified number of points on the surface of the liquid crystal alignment film. The other substrate is then attached with the liquid crystal alignment film facing each other, and the liquid crystal is spread to the entire surface of the substrate. Then, the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant, thereby manufacturing a liquid crystal cell (ODF (One DropFill) method).

[0184] As liquid crystals, fluorine-based liquid crystals, cyanide-based liquid crystals, or liquid crystal compounds or liquid crystal compositions polymerized by at least one of heating and light irradiation (hereinafter also referred to as polymerizable liquid crystals or curable liquid crystal compositions) with positive or negative dielectric anisotropy may also be used, depending on the application.

[0185] In one embodiment, the process of forming the coating film of the liquid crystal alignment agent can be performed 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.

[0186] Then, by attaching polarizing plates to both outer sides of the liquid crystal cell, a liquid crystal display element can be obtained.

[0187] Examples of polarizing plates used on the outside of a liquid crystal cell include polarizing plates made by using a cellulose acetate protective film to hold a polarizing film called an "H film" that absorbs iodine while stretching and oriented polyvinyl alcohol, or polarizing plates made of the H film itself.

[0188] As described above, the liquid crystal alignment film obtained by the liquid crystal alignment agent of the present invention exhibits good liquid crystal alignment, excellent pretilt angle performance, and high reliability. Furthermore, the liquid crystal display element manufactured by the method of the present invention possesses excellent display characteristics.

[0189] Example

[0190] The present invention will now be described in further detail based on the embodiments, but is not limited to these embodiments in any way. The abbreviations of the compounds used are shown below.

[0191] (Additives (specific compounds))

[0192] AD-1 to AD-4: Compounds represented by the formulas [AD-1] to [AD-4] respectively.

[0193] [Chemistry 14]

[0194]

[0195] (Other additives)

[0196] AD-R1~AD-R2: Compounds represented by the following formulas [AD-R1]~[AD-R2] respectively.

[0197] [Chemistry 15]

[0198]

[0199] <Tetracarboxylic dianhydride>

[0200] A1~A2: Compounds represented by the formulas [A1]~[A2] below, respectively.

[0201] [Chemistry 16]

[0202]

[0203] <Side chain diamine>

[0204] B1~B2: Compounds represented by the formulas [B1]~[B2] respectively.

[0205] [Chemistry 17]

[0206]

[0207] <Other Diamines>

[0208] C1~C2: Compounds represented by the formulas [C1]~[C2] below.

[0209] [Chemistry 18]

[0210]

[0211] Furthermore, the abbreviations of the reagents used in this embodiment are shown below.

[0212] (solvent)

[0213] THF: Tetrahydrofuran

[0214] DMF: Dimethylformamide

[0215] MeOH: Methanol

[0216] EtOH: Ethanol

[0217] AcOEt: Ethyl acetate

[0218] NMP: N-methyl-2-pyrrolidone

[0219] BCS: Butyl Solvent

[0220] (Reaction reagents)

[0221] EDC·HCl: 1-(3-Dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride

[0222] DMAP: 4-Dimethylaminopyridine

[0223] <Synthesis of Additives>

[0224] AD-1 to AD-4 and AD-R1 to AD-R2 are novel compounds not disclosed in the literature. The products of the additives synthesized in Examples 1 to 6 below are obtained through... 1Identification was performed using H-NMR analysis. The analytical conditions are as follows.

[0225] Device: BRUKER ADVANCE III-500MHz

[0226] Determination solvent: Deuterated dimethyl sulfoxide (DMSO-d6)

[0227] Standard substance: Tetramethylsilane (TMS) (δ 0.0 ppm for 1 H)

[0228] (Example 1: Synthesis of AD-1)

[0229] [Chemistry 19]

[0230]

[0231] (2E)-3-[4-(trans-4-pentylcyclohexyl)phenyl]-2-acrylic acid (6.0 g, 20 mmol), (3-(bromomethyl)oxetane-3-yl)methanol (4.3 g, 24 mmol), potassium carbonate (K₂CO₃, 4.2 g, 30 mmol), and DMF (48 g) were added to a 200 mL four-necked flask and stirred at 80 °C. After the reaction was complete, AcOEt (250 g) was added to the reaction solution, and the organic phase was washed with pure water (250 g) and concentrated. EtOH (75 g) was added to the crude product and dissolved at 40 °C. The insoluble matter was filtered off, the filtrate was cooled to 0 °C, the precipitate was filtered off, and dried under reduced pressure at 40 °C to obtain [AD-1] (4.9 g, 12.2 mmol, yield: 61%).

[0232] 1 H-NMR(500MHz) in DMSO-d6: δ (ppm) = 7.63-7.66 (m, 3H), 7.26-7.28 (d, 2H), 6.58-6.61 (d, 1H), 4.99-5.01 (t, 1H), 4.36-4.38 (m, 4H), 4.33 (s, 2H), 3.6 5-3.66(d, 2H), 2.46-2.50(m, 1H), 1.78-1.82(t, 4H), 1.40-1.47(m, 2H), 1.19-1.29(m, 9H), 0.99-1.06(m, 2H), 0.86-0.88(t, 3H).

[0233] (Example 2: Synthesis of AD-2)

[0234] [Chemistry 20]

[0235]

[0236] In a 200 mL four-necked flask, 3-[4-(trans-4-pentylcyclohexyl)phenyl]-2-butenoic acid (7.2 g, 23 mmol), (3-(bromomethyl)oxetane-3-yl)methanol (5.0 g, 28 mmol), potassium carbonate (K₂CO₃, 4.8 g, 35 mmol), and DMF (58 g) were added and stirred at 80 °C. After the reaction was complete, AcOEt (290 g) was added to the reaction solution, and the organic phase was washed with pure water (60 g) and concentrated. Then, the residue was separated by silica gel column chromatography (AcOEt:heptane = 1:2 (v / v)) to give [AD-2] (1.2 g, 2.8 mmol, yield: 12%).

[0237] 1 H-NMR(500MHz) in DMSO-d6: δ (ppm) = 7.50-7.51 (d, 2H), 7.25-7.27 (d, 2H), 6.17 (s, 1H), 4.99-5.01 (t, 1H), 4.35-4.37 (m, 4H), 4.28 (s, 2H), 3.63- 3.64(d, 2H), 2.46-2.50(m, 4H), 1.78-1.83(t, 4H), 1.39-1.46(m, 2H), 1.17-1.30(m, 9H), 0.99-1.06(m, 2H), 0.86-0.88(t, 3H).

[0238] (Example 3: Synthesis of AD-3)

[0239] [Chemistry 21]

[0240]

[0241] (2E)-3-[4-[(trans,trans)-4'-pentyl[1,1'-bicyclohexane]-4-yl]phenyl]-2-acrylic acid (7.7 g, 20 mmol), (3-(bromomethyl)oxetane-3-yl)methanol (4.3 g, 24 mmol), potassium carbonate (K₂CO₃, 4.2 g, 30 mmol), and DMF (62 g) were added to a 200 mL four-necked flask and stirred at 80 °C. After the reaction was complete, AcOEt (300 g) was added to the reaction solution, and the organic phase was washed with pure water (300 g) and concentrated. AcOEt (150 g) was added to the crude product and dissolved at 40 °C. The insoluble matter was filtered off, the filtrate was cooled to 0 °C, the precipitate was filtered off, and dried under reduced pressure at 40 °C to obtain [AD-3] (4.9 g, 10.0 mmol, yield: 50%).

[0242] 1H-NMR(500MHz) in DMSO-d6: δ (ppm) = 7.62-7.66 (m, 3H), 7.26-7.27 (d, 2H), 6.58-6.61 (d, 1H), 4.99-5.01 (t, 1H), 4.37 (s, 4H), 4.32 (s, 2H) 3.65-3.66 (d , 2H), 2.45-2.50(t, 1H), 1.70-1.83(m, 8H), 1.40-1.42(m, 2H), 1.21-1.28(m, 6H), 1.13(s, 6H), 0.95-1.05(m, 3H), 0.84-0.87(m, 5H).

[0243] (Example 4: Synthesis of AD-4)

[0244] [Chemistry 22]

[0245]

[0246] In a 200 mL four-necked flask, 3-[4-[(trans, trans)-4'-pentyl[1,1'-bicyclohexane]-4-yl]phenyl]-2-butenoic acid (9.1 g, 23 mmol), (3-(bromomethyl)oxetane-3-yl)methanol (5.0 g, 28 mmol), potassium carbonate (K₂CO₃, 4.8 g, 35 mmol), and DMF (82 g) were added and stirred at 80 °C. After the reaction was complete, the precipitate was filtered off, and AcOEt (450 g) was added to the filtrate. The organic phase was washed with pure water (90 g) and concentrated. Then, separation was performed by silica gel column chromatography (AcOEt:heptane = 1:2 (v / v)). Then, MeOH (10 g) was added to the crude product and the product was re-slurryed and washed at room temperature (25 °C) to obtain [AD-4] (3.1 g, 6.2 mmol, yield: 28%).

[0247] 1 H-NMR(500MHz) in DMSO-d6: δ (ppm) = 7.49-7.51 (d, 2H), 7.25-7.26 (d, 2H), 6.16 (s, 1H), 4.99-5.01 (t, 1H), 4.34-4.37 (m, 4H), 4.27 (s, 2H), 3.63-3.64 (d , 2H), 2.44-2.51(m, 4H), 1.70-1.83(m, 8H), 1.37-1.44(m, 2H), 1.19-1.29(m, 6H), 1.13(s, 6H), 0.95-1.05(m, 3H), 0.83-0.87(m, 5H).

[0248] (Example 5: Synthesis of AD-R1)

[0249] [Chemistry 23]

[0250]

[0251] In a 200 mL four-necked flask, (2E)-3-[4-(trans-4-pentylcyclohexyl)phenyl]-2-acrylic acid (9.0 g, 30 mmol), 3-ethyl-3-(hydroxymethyl)oxetane (3.8 g, 33 mmol), EDC·HCl (8.6 g, 45 mmol), DMAP (0.3 g, 3 mmol), and THF (90 g) were added and stirred at room temperature (25 °C). After the reaction was complete, the reaction solution was concentrated, and AcOEt (250 g) was added to the residue. The organic phase was washed with pure water (200 g) and concentrated. Then, the residue was separated by silica gel column chromatography (AcOEt:heptane = 1:10 (v / v)). Subsequently, MeOH (100 g) was added to the crude product, and the mixture was washed again at -20 °C to obtain [AD-R1] (9.2 g, 23 mmol, yield: 77%).

[0252] 1 H-NMR(500MHz) in DMSO-d6: δ (ppm) = 7.63-7.66 (m, 3H), 7.26-7.28 (d, 2H), 6.58-6.62 (d, 1H), 4.39-4.40 (d, 2H), 4.31-4.32 (m, 4H), 2.47-2.5 0 (m, 1H), 1.78-1.83 (t, 4H), 1.69-1.73 (m, 2H), 1.40-1.47 (m, 2H), 1.18-1.30 (m, 9H), 0.99-1.06 (m, 2H), 0.86-0.90 (t, 6H).

[0253] (Example 6: Synthesis of AD-R2)

[0254] [Chemistry 24]

[0255]

[0256] In a 200 mL four-necked flask, 3-[4-(trans-4-pentylcyclohexyl)phenyl]-2-butenoic acid (9.4 g, 30 mmol), 3-ethyl-3-(hydroxymethyl)oxetane (3.8 g, 33 mmol), EDC·HCl (8.6 g, 45 mmol), DMAP (0.3 g, 3 mmol), and THF (94 g) were added and stirred at room temperature (25 °C). After the reaction was complete, the reaction solution was concentrated, and AcOEt (250 g) was added to the residue. The organic phase was washed with pure water (200 g) and concentrated. Then, the residue was separated by silica gel column chromatography (AcOEt:heptane = 1:10 (v / v)). Subsequently, MeOH (100 g) was added to the crude product, and the mixture was washed again at -20 °C to obtain [AD-R2] (8.3 g, 20 mmol, yield: 66%).

[0257] 1 H-NMR(500MHz) in DMSO-d6: δ (ppm) = 7.50-7.51 (d, 2H), 7.25-7.27 (d, 2H), 6.17 (s, 1H), 4.39-4.40 (d, 2H), 4.31-4.32 (m, 4H), 2.46-2.50 (m , 4H), 1.78-1.83(t, 4H), 1.69-1.73(m, 2H), 1.40-1.47(m, 2H), 1.18-1.30(m, 9H), 0.99-1.06(m, 2H), 0.86-0.90(t, 6H).

[0258] <Synthesis of Polyamic Acid>

[0259] (Synthesis example 1)

[0260] C1 (3.04 g, 20.00 mmol) and A2 (3.75 g, 15.00 mmol) were dissolved in NMP (24.5 g) and reacted at 60 °C for 5 hours. Then, A1 (0.86 g, 4.40 mmol) and NMP (6.1 g) were added and reacted at room temperature (25 °C) for 10 hours to obtain a polyamic acid solution (PAA-1A) with a solid content of 20% by mass.

[0261] NMP (20.0 g) and BCS (20.0 g) were added to the obtained polyamic acid solution (PAA-1A) (10.0 g), and the mixture was stirred at room temperature (25 °C) for 2 hours to obtain a polyamic acid solution (PAA-1) with a solid component concentration of 4% by mass.

[0262] (Synthesis example 2)

[0263] Using the same method as in Synthesis Example 1, a polyamic acid solution (PAA-2) was synthesized with the composition shown in Table 1.

[0264] (Synthesis example 3)

[0265] B1 (0.76 g, 2.00 mmol), C1 (2.74 g, 18.00 mmol), and A2 (3.75 g, 15.0 mmol) were dissolved in NMP (26.0 g) and reacted at 60 °C for 5 hours. Then, A1 (0.86 g, 4.0 mmol) and NMP (6.5 g) were added, and the mixture was reacted at room temperature (25 °C) for 10 hours to obtain a polyamic acid solution (PAA-3A) with a solid content of 20% by mass.

[0266] NMP (20.0 g) and BCS (20.0 g) were added to the obtained polyamic acid solution (PAA-3A) (10.0 g), and the mixture was stirred at room temperature (25 °C) for 2 hours to obtain a polyamic acid solution (PAA-3) with a solid component concentration of 4% by mass.

[0267] (Synthesis Examples 4 to 6)

[0268] Polyamic acid solutions (PAA-4) to (PAA-6) were synthesized using the same method as in Synthesis Example 3, with the compositions shown in Table 1.

[0269] [Table 1]

[0270]

[0271] <Preparation of Liquid Crystal Alignment Agent>

[0272] (Example 1)

[0273] AD-1 (0.12 g) was added to the polyamic acid solution (PAA-1) (50.0 g) obtained in Synthesis Example 1, and the mixture was stirred at room temperature (25 °C) to obtain the liquid crystal alignment agent (AL-1).

[0274] (Examples 2-24, Comparative Examples 1-12)

[0275] As shown in Table 2, the polyamic acid solution, type and amount of additives used were changed, but otherwise the same procedure as in Example 1 was performed to obtain liquid crystal alignment agents (AL-2) to (AL-24) and (AL-R1) to (AL-R12).

[0276] [Table 2]

[0277]

[0278] <Fabrication of Liquid Crystal Display Components>

[0279] The liquid crystal alignment agents (AL-1) to (AL-24) obtained in the examples and the liquid crystal alignment agents (AL-R1) to (AL-R12) obtained in the comparative examples were pressure filtered using membrane filters with a pore size of 1 μm.

[0280] The obtained solution was spin-coated onto the ITO side of a glass substrate with a transparent electrode containing an ITO film. After drying on a hot plate at 70°C for 90 seconds, it was sintered on a hot plate at 200°C for 30 minutes to form a liquid crystal alignment film with a thickness of 100 nm.

[0281] Next, the coating surface was irradiated with an intensity of 4.3 mW / cm through a polarizing plate. 2 Linearly polarized ultraviolet light with a wavelength of 313 nm is irradiated from the substrate at an angle of 40° from the normal direction, at a concentration of 50 mJ / cm². 2 A substrate with a liquid crystal alignment film was obtained. Linearly polarized ultraviolet light was prepared by passing ultraviolet light from a high-pressure mercury lamp through a bandpass filter with a wavelength of 313 nm, and then through a polarizer with a wavelength of 313 nm.

[0282] Two substrates as described above were prepared. On one substrate, 4μm bead-like spacers were dispersed on the liquid crystal alignment film, and then a sealant (Mitsui Chemicals, XN-1500T) was applied. Next, the other substrate was bonded together so that the liquid crystal alignment film surfaces faced each other and the alignment direction was 180°. The sealant was then heat-cured at 120°C for 90 minutes to create an empty cell. Liquid crystal (Merck, MLC-3022) was injected into the empty cell using a reduced-pressure injection method to obtain a liquid crystal display element.

[0283] <Evaluation>

[0284] (Liquid crystal alignment)

[0285] 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, a condition where there was no light leakage or domain region formation (indicating poor alignment) and uniform liquid crystal driving was obtained when a voltage was applied to the liquid crystal cell was rated as "good". The evaluation results are shown in Table 3.

[0286] (Voltage retention rate (VHR))

[0287] The evaluation of VHR involves applying a voltage of 1V to the liquid crystal cell fabricated above at a temperature of 60°C for 60μs, measuring the voltage after 1667ms, and calculating how much of the voltage can be maintained as the voltage retention rate.

[0288] It should be noted that the voltage holding rate was measured using a voltage holding rate measuring device VHR-1 manufactured by Toyo Technica Co., Ltd. The evaluation results are shown in Table 3.

[0289] [Table 3]

[0290]

[0291] As shown in Table 3, the liquid crystal alignment film obtained by adding specific compounds AD-1 to AD-4 to polyamic acid as a liquid crystal alignment agent exhibits superior vertical alignment and VHR compared to the liquid crystal alignment film of the comparative examples. Specifically, the comparisons are between Example 1 and Comparative Example 1, Example 2 and Comparative Example 2, Example 5 and Comparative Example 3, Example 6 and Comparative Example 4, Example 9 and Comparative Example 5, Example 10 and Comparative Example 6, Example 13 and Comparative Example 7, Example 14 and Comparative Example 8, Example 17 and Comparative Example 9, Example 18 and Comparative Example 10, Example 21 and Comparative Example 11, and Example 22 and Comparative Example 12.

[0292] Industrial applicability

[0293] The liquid crystal alignment agent of the present invention and the liquid crystal display element using the liquid crystal alignment film obtained therefrom are suitable for use in automotive and other applications requiring durability.

Claims

1. A liquid crystal alignment agent, characterized in that, contain: Compounds having a photo-oriented group, an oxobutyric group, and a polar group as shown in formula (pa-1) as component (A); Polyamic acid as component (B); as well as solvent, In formula (pa-1), A represents pyrimidin-2,5-diyl, pyridin-2,5-diyl, thiophene-2,5-diyl, furan-2,5-diyl, 1,4-naphthylene, 2,6-naphthylene, or phenylene, wherein the group A is or is not substituted by a group selected from fluorine atom, chlorine atom, cyano, alkoxy with 1 to 5 carbon atoms, straight-chain alkyl with 1 to 5 carbon atoms, and branched alkyl with 1 to 5 carbon atoms, wherein the alkyl group is or is not substituted by one cyano 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-ring group; R3 is a single bond, an oxygen atom, -COO-, or -OCO-; R4 is a straight-chain or branched alkyl group with 1 to 40 carbon atoms, or a monovalent organic group with 3 to 40 carbon atoms containing an alicyclic group, wherein some or all of the hydrogen atoms of the above alkyl groups are replaced by fluorine atoms or not; D represents an oxygen atom, a sulfur atom, or -NR. d -, where R d Indicates an alkyl group having 1 to 3 hydrogen atoms or carbon atoms; a is an integer from 0 to 3; Indicates the bonding position; when a is 2 or more, multiple R1 and R2 independently have the above definitions; X and Y are each independently a hydrogen atom, fluorine atom, chlorine atom, cyano group, or alkyl group having 1 to 3 carbon atoms, wherein some or all of the hydrogen atoms of the above alkyl group are replaced by fluorine atoms or not. The wavy lines between "C" and "A" and between "C" and "X" indicate either the E-type isomer or the Z-type isomer.

2. The liquid crystal alignment agent according to claim 1, wherein, (A) The polar group of the component is selected from hydroxyl, thiol, amino, monoalkylamino, dialkylamino, carboxyl, sulfonyl, pyridyl, imidazole and triazolyl groups.

3. The liquid crystal alignment agent according to claim 1, wherein, (A) The polar group of component A is hydroxyl.

4. A liquid crystal alignment film, characterized in that, It is formed using the liquid crystal alignment agent according to any one of claims 1 to 3.

5. A method for manufacturing a liquid crystal alignment film, characterized in that, include: The process of coating a substrate with the liquid crystal alignment agent as described in any one of claims 1 to 3 to form a coating film; as well as The process of irradiating the coating with light while the coating is not in contact with the liquid crystal layer or while the coating is in contact with the liquid crystal layer.

6. A liquid crystal display element, characterized in that, It comprises the liquid crystal alignment film as described in claim 4 or the liquid crystal alignment film obtained by the manufacturing method described in claim 5.

7. A compound, characterized in that, It has a photo-orientation group, an oxetyl group, and a polar group as shown in the following formula (pa-1). In formula (pa-1), A represents pyrimidin-2,5-diyl, pyridin-2,5-diyl, thiophene-2,5-diyl, furan-2,5-diyl, 1,4-naphthylene, 2,6-naphthylene, or phenylene, wherein the group A is or is not substituted by a group selected from fluorine atom, chlorine atom, cyano, alkoxy with 1 to 5 carbon atoms, straight-chain alkyl with 1 to 5 carbon atoms, and branched alkyl with 1 to 5 carbon atoms, wherein the alkyl group is or is not substituted by one cyano 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-ring group; R3 is a single bond, an oxygen atom, -COO-, or -OCO-; R4 is a straight-chain or branched alkyl group with 1 to 40 carbon atoms, or a monovalent organic group with 3 to 40 carbon atoms containing an alicyclic group, wherein some or all of the hydrogen atoms of the above alkyl groups are replaced by fluorine atoms or not; D represents an oxygen atom, a sulfur atom, or -NR. d -, where R d Indicates an alkyl group having 1 to 3 hydrogen atoms or carbon atoms; a is an integer from 0 to 3; Indicates the bonding position; when a is 2 or more, multiple R1 and R2 independently have the above definitions; X and Y are each independently a hydrogen atom, fluorine atom, chlorine atom, cyano group, or alkyl group having 1 to 3 carbon atoms, wherein some or all of the hydrogen atoms of the above alkyl group are replaced by fluorine atoms or not. The wavy lines between "C" and "A" and between "C" and "X" indicate either the E-type isomer or the Z-type isomer.

8. The compound according to claim 7, wherein, The polar group is selected from hydroxyl, thiol, amino, monoalkylamino, dialkylamino, carboxyl, sulfonyl, pyridyl, imidazole, and triazolyl groups.

9. A compound represented by any one of the following formulas (AD-1) to (AD-4): 。

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